JP2022022960A - Process for preparing 6-isopropenyl-3-methyl-9-decenyl acetate, and intermediates therefor - Google Patents

Abstract

To provide a process for preparing 6-isopropenyl-3-methyl-9-decenyl acetate.SOLUTION: According to the process, a compound (3) is prepared from a compound (1) and a compound (2), and is subjected to a deprotection reaction and then an acetylating reaction, resulting in a compound (5) (where X is an acyloxy group or the like; M is Li or the like; R is a protective group of a hydroxy group).SELECTED DRAWING: None

Description

The present invention relates to a method for producing 6-isopropenyl-3-methyl-9-decenyl-acetate, which is a sex pheromone substance of California red scale (scientific name: Aonidiella aurantii ), which is a pest of citrus fruits, and an intermediate thereof.

Insect sex pheromones are bioactive substances that normally have the function of attracting male individuals by female individuals, and exhibit high attractive activity even in small amounts. Sex pheromones are widely used as a means for predicting outbreaks and confirming geographical spread (invasion into specific areas), and as a means for controlling pests. As means for controlling pests, mass trapping, attracted insecticide (Lure and kill or Acttract and kill), attracted infection (Lure and impact or Tract and insect), and communication disturbance method (called Mart). Control methods are widely used in practical use. Since the amount of sex pheromones that can be extracted from one insect is extremely small, it is difficult to use naturally-derived sex pheromones for communication disturbance, etc., and the necessary amount of sex pheromones is artificially produced when using sex pheromones. What is needed for basic research and even for application.

California red scale is a pest that is widely distributed all over the world and harms citrus fruits. As a sex pheromone of California red scale , (3S, 6R) -6-isopropenyl-3-methyl-9-decenyl-acetate has been reported (Non-Patent Document 1 below). As 6-isopropenyl-3-methyl-9-decenyl = acetate, (3R, 6R) -6-isopropenyl-3-methyl-9-decenyl = acetate, (3R, 6S) -6-isopropenyl-3 -Methyl-9-decenyl = acetate, (3S, 6R) -6-isopropenyl-3-methyl-9-decenyl = acetate, (3S, 6S) -6-isopropenyl-3-methyl-9-decenyl = acetate There are 4 isomers of. It has been reported that California red scale is also attracted by these tetraisomer mixtures (Non-Patent Document 1 below).
As a method for producing 6-isopropenyl-3-methyl-9-decenyl-acetate, for example, selenium dioxide and tert-butyl hydroperoxide are used to oxidize and introduce a trisubstituted double bond moiety of citronellol acetate. Is chlorinated with triphenylphosphine and carbon tetrachloride, and then a method for synthesizing (3S, 6RS) -6-isopropenyl-3-methyl-9-decenyl-acetate by nucleophilic substitution reaction has been reported. (Non-Patent Document 2 below). In addition, a sulfide compound is derived from citronellol acetate, followed by a 1,2-Stevens rearrangement reaction by strong base treatment, and then an oxidation reaction using metachloroperbenzoic acid to synthesize a sulfone compound, followed by trialkylation and reduction of the sulfone. A method for synthesizing 6-isopropenyl-3-methyl-9-decenyl-acetate by target elimination has been reported (Non-Patent Document 3 below).
Furthermore, (-)-dihydrocarboxylic acid was introduced into a silylenol ether compound, and then by eight steps including ozone oxidation, then reduction with sodium borohydride, and methylation of the carboxylic acid with diazomethane, (2S, 5R) -5. -Isopropenyl-2-methyl-8-nonenyl-iodide is synthesized, and then (3S, 6R) -6-isopropenyl-3-methyl-9 is subjected to four steps including the step of deriving a nitrile compound with sodium cyanide. -A method for synthesizing decenyl-acetate has also been reported (Non-Patent Document 4).

M. J. GIESELMANN et al. , J. Insect. Physiol. 26,179 (1980) Panagiotis Kefalas et al. , Synthesis. 644 (1995) V. A. Dragan et al. , Russ. Chem. Bull. 38,1038 (1989) R. Bodyday et al. , Tetrahedron. 44,471 (1988)

However, Non-Patent Document 2 uses selenium dioxide and tert-butyl hydroperoxide in the oxidation reaction of citronellol acetate, which are not preferable from the viewpoint of the environment because they give toxic and environmentally friendly waste. In addition, the oxidation reaction is difficult to carry out industrially because it may cause an explosion, and the yield of the oxidation reaction is as low as 52%.
In Non-Patent Document 3, metachloroperbenzoic acid is used for oxidation of sulfide, which may cause an explosion, and hexamethylphosphoric-triamide, which is highly toxic, is used as an alkylation solvent. , Industrial implementation is difficult. In addition, the yield after all eight steps is as low as 12.3%.
In the case of Non-Patent Document 4, the synthesis of the intermediate (2S, 5R) -5-isopropenyl-2-methyl-8-nonenyl-iodide requires 8 steps, which makes ozone oxidation difficult to carry out industrially. , Explosive and highly toxic diazomethane is used, which is not industrially advantageous. Also, regarding the step of deriving (3S, 6R) -6-isopropenyl-3-methyl-9-decenyl-acetate from (2S, 5R) -5-isopropenyl-2-methyl-8-nonenyl-iodide. In addition to requiring all four steps, it is difficult to carry out industrially because highly toxic sodium cyanide is used.

As described above, it was considered very difficult to industrially produce a sufficient amount of 6-isopropenyl-3-methyl-9-decenyl-acetate by the conventional production method.

The present invention has been made in view of the above circumstances, and does not require an oxidation reaction in order to supply a sufficient amount of the drug substance necessary for biological or agricultural activity testing and / or actual application or utilization. It is an object of the present invention to provide a method for efficiently and industrially producing 6-isopropenyl-3-methyl-9-decenyl-acetate.

As a result of diligent studies to solve the above problems, the present inventors have conducted 2-methyl-2,6 as a useful intermediate in the production of 6-isopropenyl-3-methyl-9-decenyl-acetate. -We have found a heptadiene compound, and further found that 6-isopropenyl-3-methyl-9-decenyl-acetate can be industrially obtained using the intermediate, and have made the present invention.

（式中、Ｘはカルボニル基の炭素を含めた炭素数１～１０のアシルオキシ基、炭素数１～１０のアルカンスルホニルオキシ基、炭素数６～２０のアレーンスルホニルオキシ基、又はハロゲン原子を表す。）
で表される、１位に脱離基Ｘを有する２－メチル－２，６－ヘプタジエン化合物と、下記一般式（２）

（式中、Ｍは、Ｌｉ、ＭｇＺ^１、ＺｎＺ^１、Ｃｕ、ＣｕＺ^１又はＣｕＬｉＺ^１を表し、Ｚ^１は、ハロゲン原子又はＣＨ_２ＣＨ_２ＣＨ（ＣＨ_３）ＣＨ_２ＣＨ_２ＯＲ基を表し、かつＲは水酸基の保護基を表す。）
で表される、５位に保護された水酸基を有する３－メチルペンチル求核試薬との求核置換反応により、下記一般式（３）

（式中、Ｒは、上記で定義した通りである。）
で表される、１位に保護された水酸基を有する６－イソプロペニル－３－メチル－９－デセン化合物を得る工程と、
１位に保護された水酸基を有する上記６－イソプロペニル－３－メチル－９－デセン化合物（３）の脱保護反応により、下記式（４）

で表される６－イソプロペニル－３－メチル－９－デセンを得る工程と、
上記６－イソプロペニル－３－メチル－９－デセン（４）をアセチル化して、下記式（５）

（式中、Ａｃはアセチル基を表す。）
で表される６－イソプロペニル－３－メチル－９－デセニル＝アセテートを得る工程と
を少なくとも含む、６－イソプロペニル－３－メチル－９－デセニル＝アセテート（５）の製造方法が提供される。 According to one aspect of the present invention, the following general formula (1)

(In the formula, X represents an acyloxy group having 1 to 10 carbon atoms including carbon of a carbonyl group, an alkanesulfonyloxy group having 1 to 10 carbon atoms, an allene sulfonyloxy group having 6 to 20 carbon atoms, or a halogen atom. )
A 2-methyl-2,6-heptadiene compound having a leaving group X at the 1-position represented by the following general formula (2).

(In the formula, M represents Li, MgZ ¹ , ZnZ ¹ , Cu, CuZ ¹ or CuLiZ ¹ , and Z ¹ represents a halogen atom or CH ₂ CH ₂ CH (CH ₃ ) CH ₂ CH ₂ OR group. And R represents a hydroxyl-protecting group.)
The following general formula (3) is obtained by a nucleophilic substitution reaction with a 3-methylpentyl nucleophile having a hydroxyl group protected at the 5-position represented by.

(In the formula, R is as defined above.)
A step of obtaining a 6-isopropenyl-3-methyl-9-decene compound having a hydroxyl group protected at the 1-position represented by
The following formula (4) is obtained by the deprotection reaction of the above 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position.

The step of obtaining 6-isopropenyl-3-methyl-9-decene represented by
The above 6-isopropenyl-3-methyl-9-decene (4) is acetylated to the following formula (5).

(In the formula, Ac represents an acetyl group.)
Provided is a method for producing 6-isopropenyl-3-methyl-9-decenyl-acetate (5), which comprises at least a step of obtaining 6-isopropenyl-3-methyl-9-decenyl-acetate represented by. ..

（式中、Ｘはカルボニル基の炭素を含めた炭素数１～１０のアシルオキシ基、炭素数１～１０のアルカンスルホニルオキシ基、炭素数６～２０のアレーンスルホニルオキシ基、又はハロゲン原子を表す。）
で表される、１位に脱離基Ｘを有する２－メチル－２，６－ヘプタジエン化合物と、下記一般式（２）

（式中、Ｍは、Ｌｉ、ＭｇＺ^１、ＺｎＺ^１、Ｃｕ、ＣｕＺ^１又はＣｕＬｉＺ^１を表し、Ｚ^１は、ハロゲン原子又はＣＨ_２ＣＨ_２ＣＨ（ＣＨ_３）ＣＨ_２ＣＨ_２ＯＲ基を表し、かつＲは水酸基の保護基を表す。）
で表される、５位に保護された水酸基を有する３－メチルペンチル求核試薬との求核置換反応により、下記一般式（３）

（式中、Ｒは、上記で定義した通りである。）
で表される、１位に保護された水酸基を有する６－イソプロペニル－３－メチル－９－デセン化合物を得る工程と、
１位に保護された水酸基を有する上記６－イソプロペニル－３－メチル－９－デセン化合物（３）をアセチル化反応に付して、下記式（５）

（式中、Ａｃはアセチル基を表す。）
で表される６－イソプロペニル－３－メチル－９－デセニル＝アセテートを得る工程と
を少なくとも含む、６－イソプロペニル－３－メチル－９－デセニル＝アセテート（５）の製造方法が提供される。 Further, in another aspect of the present invention, the following general formula (1)

(In the formula, X represents an acyloxy group having 1 to 10 carbon atoms including carbon of a carbonyl group, an alkanesulfonyloxy group having 1 to 10 carbon atoms, an allene sulfonyloxy group having 6 to 20 carbon atoms, or a halogen atom. )
A 2-methyl-2,6-heptadiene compound having a leaving group X at the 1-position represented by the following general formula (2).

(In the formula, M represents Li, MgZ ¹ , ZnZ ¹ , Cu, CuZ ¹ or CuLiZ ¹ , and Z ¹ represents a halogen atom or CH ₂ CH ₂ CH (CH ₃ ) CH ₂ CH ₂ OR group. And R represents a hydroxyl-protecting group.)
The following general formula (3) is obtained by a nucleophilic substitution reaction with a 3-methylpentyl nucleophile having a hydroxyl group protected at the 5-position represented by.

(In the formula, R is as defined above.)
A step of obtaining a 6-isopropenyl-3-methyl-9-decene compound having a hydroxyl group protected at the 1-position represented by
The above 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position is subjected to an acetylation reaction and the following formula (5) is applied.

(In the formula, Ac represents an acetyl group.)
Provided is a method for producing 6-isopropenyl-3-methyl-9-decenyl-acetate (5), which comprises at least a step of obtaining 6-isopropenyl-3-methyl-9-decenyl-acetate represented by. ..

で表される２－メチル－２，６－ヘプタジエノールの水酸基をＸ（Ｘは、上記に定義したとおりである。）に変換することにより、１位に脱離基Ｘを有する上記２－メチル－２，６－ヘプタジエン化合物（１）を得る工程をさらに含む、６－イソプロペニル－３－メチル－９－デセニル＝アセテート（５）の製造方法が提供される。 Further, in another aspect of the present invention, the following formula (6)

By converting the hydroxyl group of 2-methyl-2,6-heptadienol represented by (X is as defined above) to X (X is as defined above), the above 2- having a leaving group X at the 1-position. Provided is a method for producing 6-isopropenyl-3-methyl-9-decenyl-acetate (5), further comprising the step of obtaining the methyl-2,6-heptadiene compound (1).

（式中、Ｘ’は、カルボニル基の炭素を含めた炭素数１～１０のアシルオキシ基を表す。）
で表される、１位にＸ’を有する２－メチル－２，６－ヘプタジエン化合物が提供される。 Further, in another aspect of the present invention, the following general formula (1')

(In the formula, X'represents an acyloxy group having 1 to 10 carbon atoms including the carbon of the carbonyl group.)
A 2-methyl-2,6-heptadiene compound having X'at the 1-position represented by is provided.

（式中、Ｘ’’は炭素数１～１０のアルカンスルホニルオキシ基又は炭素数６～２０のアレーンスルホニルオキシ基を表す。）
で表される、１位にＸ’’を有する２－メチル－２，６－ヘプタジエン化合物が提供される。 Further, in another aspect of the present invention, the following general formula (1 ″)

(In the formula, X'' represents an alkanesulfonyloxy group having 1 to 10 carbon atoms or an arene sulfonyloxy group having 6 to 20 carbon atoms.)
A 2-methyl-2,6-heptadiene compound having an X'' at the 1-position represented by is provided.

According to the present invention, 6-isopropenyl-3-methyl-9-decenyl = which eliminates the need for an oxidation reaction which is difficult to carry out industrially in terms of safety, economy and environmental load, and efficiently and industrially. A method for producing acetate can be provided. Further, according to the present invention, 2-methyl-2,6-heptadiene compound (1') and 2-methyl, which are useful intermediates for producing 6-isopropenyl-3-methyl-9-decenyl = acetate, are used. -2,6-Heptadiene compound (1 ″) can also be provided.

Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited thereto. Further, in the chemical formulas of intermediates, reagents and objects in the present specification, there are structurally possible stereoisomers such as enantioisomers or diastereoisomers, but unless otherwise specified, any of them will be present. In the case of, each chemical formula shall represent all of these isomers. Moreover, these isomers may be alone or may be a mixture.

The present inventors considered a synthetic scheme of 6-isopropenyl-3-methyl-9-decenyl-acetate (5), as described below.

In the reaction formula of the above-mentioned retrosynthetic analysis, the white arrow represents the transform in the retrosynthetic analysis. Further, Ac represents an acetyl group, R represents a hydroxyl group protective group, X represents an acyloxy group having 1 to 10 carbon atoms including a carbon of a carbonyl group, an alkanesulfonyloxy group having 1 to 10 carbon atoms, and a carbon number of carbon atoms. 6 to 20 arene sulfonyloxy groups or halogen atoms, M represents Li, MgZ ¹ , ZnZ ¹ , Cu, CuZ ¹ or CuLiZ ¹ and Z ¹ is a halogen atom or CH ₂ CH ₂ CH ( CH ₃ ) CH ₂ CH ₂ OR group, and R represents a hydroxyl group protective group.

(Step D') The target compound of the present invention, 6-isopropenyl-3-methyl-9-decenyl-acetate (5), acetylates 6-isopropenyl-3-methyl-9-decenol (4). It is thought that it can be synthesized by this.

The above formula (5) is represented by the following formula (5a) (3R, 6R) -6-isopropenyl-3-methyl-9-decenyl = acetate, and is represented by the following formula (5b) (3R, 6S). ) -6-Isopropenyl-3-methyl-9-decenyl = acetate, represented by the following formula (5c) (3S, 6R) -6-isopropenyl-3-methyl-9-decenyl = acetate, or the following formula Represents (3S, 6S) -6-isopropenyl-3-methyl-9-decenyl-acetate represented by (5d), or a combination of two or more thereof.

The above formula (4) is represented by the following formula (4a) (3R, 6R) -6-isopropenyl-3-methyl-9-decenol and the following formula (4b) (3R, 6S)-. 6-isopropenyl-3-methyl-9-decenol, represented by the following formula (4c) (3S, 6R) -6-isopropenyl-3-methyl-9-decenol, or represented by the following formula (4d). (3S, 6S) -6-isopropenyl-3-methyl-9-decenol, or a combination of two or more thereof.

(Step C') The target compound, 6-isopropenyl-3-methyl-9-decenol (4), is a 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position. ) Can be synthesized by deprotecting.

The above general formula (3) is a (3R, 6R) -6-isopropenyl-3-methyl-9-decene compound having a hydroxyl group protected at the 1-position represented by the following general formula (3a), and the following general. A (3R, 6S) -6-isopropenyl-3-methyl-9-decene compound having a hydroxyl group protected at the 1-position represented by the formula (3b), the 1-position represented by the following general formula (3c). It has a (3S, 6R) -6-isopropenyl-3-methyl-9-decene compound having a hydroxyl group protected by, or a hydroxyl group protected at the 1-position represented by the following general formula (3d) (3S). , 6S) -6-isopropenyl-3-methyl-9-decene compound, or a combination of two or more thereof.

(Step B') The target compound, 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position, is 3-methylpentyl having a hydroxyl group protected at the 5-position. It is considered that the nucleating reagent (2) can be synthesized by regioselectively reacting with the carbon atom at the 3-position of the 2-methyl-2,6-heptadiene compound (1) having a leaving group X at the 1-position. ..

The above general formula (2) is represented by the following general formula (2a), the (R) -3-methylpentyl nucleophile having a hydroxyl group protected at the 5-position, or the following general formula (2b). Represents (S) -3-methylpentyl nucleophile having a hydroxyl group protected at the 5-position, or a combination thereof. Regarding the naming of each nucleophile of the above general formulas (2a) and (2b), the priority of atoms in the RS notation was set to M> O.

The above general formula (1) is a (Z) -2-methyl-2,6-heptadiene compound having a leaving group X at the 1-position represented by the following general formula (1a), or the following general formula (1b). It represents an (E) -2-methyl-2,6-heptadiene compound having a leaving group X at the 1-position represented, or a combination thereof.

(Step A') The target compound, the 2-methyl-2,6-heptadiene compound (1) having a leaving group X at the 1-position, is the hydroxyl group of 2-methyl-2,6-heptadienol (6). It is considered that it can be synthesized by the conversion reaction of.

The above formula (6) is represented by the following formula (6a) (Z) -2-methyl-2,6-heptadienol and the following formula (6b) (E) -2-methyl-2. , 6-Heptadienol, or a combination thereof.

Then, considering the reaction formula of the above-mentioned retrosynthetic analysis, the chemical reaction formula according to one embodiment of the present invention is shown as follows.

That is, the above chemical reaction formula is a 2-methyl-2,6-heptadiene compound having a desorbing group X at the 1-position obtained by the conversion reaction of the hydroxyl group of 2-methyl-2,6-heptadienol (6). Step A for synthesizing (1); Next, a 3-methylpentyl nucleophilic reagent (2) having a hydroxyl group protected at the 5-position is used as a 2-methyl-2,6-2-methyl-2,6-with a removing group X at the 1-position. A 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position is obtained by performing a nucleophilic substitution reaction on the carbon atom at the 3-position of the heptadiene compound (1) in a position-selective manner. Step B for synthesis; and step C for deprotecting the 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position; finally, the target compound of the present invention 6 Includes step D to synthesize 6-isopropenyl-3-methyl-9-decenyl-acetate (5) by acetylating -isopropenyl-3-methyl-9-decenol (4).

Hereinafter, the above steps A to D as embodiments of the present invention will be described in detail. First, step B for synthesizing the 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position, and then 6-isopropenyl-3-methyl-9-decenol (4). Step C, and step D for synthesizing 6-isopropenyl-3-methyl-9-decenyl-acetate (5), which is the target compound of the present invention, and finally, the starting material of the above-mentioned step B. Step A for synthesizing the 2-methyl-2,6-heptadiene compound (1) having a desorbing group X at the 1-position will be described in this order. In the step B, the useful intermediates 2-methyl-2,6-heptadiene compound (1') and 2-methyl-2,6-heptadiene compound (1 ″) will also be described.

[1] Step B
The step B for obtaining the 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position will be described below. The 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position has a leaving group X at the 1-position as shown in the following chemical reaction formula. It is obtained by a nucleophilic substitution reaction between a methyl-2,6-heptadiene compound (1) and a 3-methylpentyl nucleophile (2) having a hydroxyl group protected at the 5-position.

First, a 2-methyl-2,6-heptadiene compound having a leaving group X at the 1-position represented by the following general formula (1) will be described.

上記一般式（１）において、Ｘは脱離基を表す。

In the above general formula (1), X represents a leaving group.

The 2-methyl-2,6-heptadiene compound (1) having a desorbing group X at the 1-position has a desorbing group X at the 1-position represented by the following general formula (1a) (Z) -2-. Methyl-2,6-heptadiene compounds, which may exist as (E) -2-methyl-2,6-heptadiene compounds having a elimination group X at the 1-position represented by the following general formula (1b), are present. The isomers of may be alone or may be a mixture.

The leaving group X represents an acyloxy group having 1 to 10 carbon atoms including carbon of a carbonyl group, an alkane sulfonyloxy group having 1 to 10 carbon atoms, an allene sulfonyloxy group having 6 to 20 carbon atoms, or a halogen atom. From these, an appropriate one can be selected in consideration of reactivity, reaction selectivity, availability of raw materials, ease of synthesis, storage stability, dramatic toxicity, and / or price and the like.

Examples of the acyloxy group having 1 to 10 carbon atoms including the carbon of the carbonyl group include a formyloxy group, an acetoxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, a hexanoyloxy group and a heptanoyloxy group. Linear aliphatic acyloxy groups such as octanoyloxy group, nonanoyloxy group, decanoyyloxy group and crotonyloxy group; 2-methylpropanoloxy group, pivaloyloxy group, 2-methylbutanoyloxy group, 3-methyl Branched aliphatic acyloxy groups such as -2-butenoyloxy group and 3-methyl-3-butenoyloxy group; halogenated acyloxy groups such as trichloroacetoxy group and trifluoroacetoxy group; and aromatic acyloxy groups such as benzoyloxy group. Etc., and an acyloxy group having an isomer relationship with these may be used. Further, a part of the hydrogen atom of these acyloxy groups may be substituted with a methyl group, an ethyl group, a halogen atom or the like, and examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom.
Among the above acyloxy groups, a formyloxy group, an acetoxy group, a propanoyloxy group, a pivaloyloxy group, a 2-methylpropanoyloxy group and a benzoyloxy group are preferable from the viewpoint of easy availability.

Examples of the alkanesulfonyloxy group having 1 to 10 carbon atoms include a methanesulfonyloxy group, an ethanesulfonyloxy group, a 1-butanesulfonyloxy group, a 1-pentanesulfonyloxy group, a 1-hexanesulfonyloxy group and a 1-heptanesulfonyloxy group. , 1-octanesulfonyloxy group, 1-nonansulfonyloxy group, 1-decanesulfonyloxy group, allylsulfonyloxy group, 10-campersulfonyloxy group, trifluoromethanesulfonyloxy group, α-benzylsulfonyloxy group and the like. , Alkanesulfonyloxy groups having an isomer relationship with these may be used. Further, a part of the hydrogen atom of these alkanesulfonyloxy groups may be substituted with a methyl group, an ethyl group, a halogen atom or the like, and examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom.
Among the above alkane sulfonyl oxy groups, a methane sulfonyl oxy group and an ethane sulfonyl oxy group are preferable from the viewpoint of easy availability.

Examples of the arene sulfonyloxy group having 6 to 20 carbon atoms include a benzenesulfonyloxy group, a 4-chlorobenzenesulfonyloxy group, a 4-methoxybenzenesulfonyloxy group, a 2-nitrobenzenesulfonyloxy group, and a 2,4,6-trimethylbenzenesulfonyloxy group. Examples thereof include a group, a p-toluenesulfonyloxy group, a 1-naphthalenesulfonyloxy group and a 2-naphthalenesulfonyloxy group, and an allenesulfonyloxy group having an isomer relationship with these may be used. Further, a part of the hydrogen atom of these allene sulfonyloxy groups may be substituted with a methyl group, an ethyl group, a halogen atom or the like, and examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom.
Among the above arene sulfonyl oxy groups, a benzene sulfonyl oxy group and a p-toluene sulfonyl oxy group are preferable from the viewpoint of easy availability.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Among the above halogen atoms, chlorine atom and bromine atom are preferable from the viewpoint of easy availability.

で表される２－メチル－２，６－ヘプタジエン化合物が特に好ましい。
一般式（１’）において、Ｘ’はカルボニル基の炭素を含めた炭素数１～１０のアシルオキシ基を表す。
カルボニル基の炭素を含めた炭素数１～１０のアシルオキシ基の具体例としては、上記脱離基Ｘにおけるカルボニル基の炭素を含めた炭素数１～１０のアシルオキシ基と同じである。 Among the 2-methyl-2,6-heptadiene compounds (1) having a leaving group X at the 1-position, the following general formula (1') is used from the viewpoint of reactivity and / or economy.

The 2-methyl-2,6-heptadiene compound represented by is particularly preferable.
In the general formula (1'), X'represents an acyloxy group having 1 to 10 carbon atoms including the carbon of the carbonyl group.
Specific examples of the acyloxy group having 1 to 10 carbon atoms including the carbon of the carbonyl group are the same as those of the acyloxy group having 1 to 10 carbon atoms including the carbon of the carbonyl group in the leaving group X.

で表される２－メチル－２，６－ヘプタジエン化合物も好ましい。
一般式（１’’）において、Ｘ’’は炭素数１～１０のアルカンスルホニルオキシ基、又は炭素数６～２０のアレーンスルホニルオキシ基を表す。
炭素数１～１０のアルカンスルホニルオキシ基及び炭素数６～２０のアレーンスルホニルオキシ基の具体例としては、上記Ｘにおける炭素数１～１０のアルカンスルホニルオキシ基及び炭素数６～２０のアレーンスルホニルオキシ基と同じである。 In addition to the above 2-methyl-2,6-heptadiene compound (1'), the following general formula (1 ″) is used from the viewpoint of obtaining raw materials.

A 2-methyl-2,6-heptadiene compound represented by is also preferable.
In the general formula (1 ″), X ″ represents an alkanesulfonyloxy group having 1 to 10 carbon atoms or an arene sulfonyloxy group having 6 to 20 carbon atoms.
Specific examples of the alkanesulfonyloxy group having 1 to 10 carbon atoms and the alkanesulfonyloxy group having 6 to 20 carbon atoms include the alkanesulfonyloxy group having 1 to 10 carbon atoms and the allenesulfonyloxy group having 6 to 20 carbon atoms in X. It is the same as the group.

Here, since the 2-methyl-2,6-heptadiene compound (1) having a leaving group X at the 1-position has the leaving group X at the allyl position, 3-methyl having a hydroxyl group protected at the 5-position. As an attack site for the 2-methyl-2,6-heptadiene compound (1) having a leaving group X at the 1-position by the pentyl nucleophilic reagent (2), the carbon atom at the 1-position to which the leaving group X is bonded It is considered to be a carbon atom at the 3-position.
The 3-methylpentyl nucleophile (2) having a hydroxyl group protected at the 5-position attacks the carbon atom at the 3-position of the 2-methyl-2,6-heptadiene compound (1) having a leaving group X at the 1-position. In this case (so-called NS _2'mechanism ), a nucleophilic substitution reaction accompanied by an allyl rearrangement occurs, and the 6-isopropenyl-3-methyl-9-decene compound having a hydroxyl group protected at the 1-position position (3). Is generated.
On the other hand, the 3-methylpentyl nucleophile (2) having a hydroxyl group protected at the 5-position has a carbon atom at the 1-position of the 2-methyl-2,6-heptadiene compound (1) having a leaving group X at the 1-position. In the case of attacking (so-called NS 2 mechanism), a 3,7-dimethyl- _7,11 -dodecadiene compound having a hydroxyl group protected at the 1-position represented by the following general formula (3') is produced. do.

Therefore, in step B, the 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position and the 3,7-dimethyl-7,11-dodecadien compound (3') Can conflict with generation. Therefore, under the conditions of the nucleophilic substitution reaction described later, the by-product of the 3,7-dimethyl-7,11-dodecadien compound (3') having a hydroxyl group protected at the 1-position is suppressed and protected at the 1-position. The optimum conditions for obtaining the 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group in a good yield may be selected. The optimum conditions are, for example, acyloxy having 1 to 10 carbon atoms in which the leaving group X in the 2-methyl-2,6-heptadiene compound (1) having the leaving group X at the 1-position includes the carbon of the carbonyl group. The protective group in the 3-methylpentyl nucleophilic reagent (2) having a 2-methyl-2,6-heptadienine compound (1'), which is a group, and having a hydroxyl group protected at the 5-position is 1-ethoxy. Use a 5- (1-ethoxyethyloxy) -3-methylpentylmagnesium-halide compound, which is an ethyl group, and a combination of copper halide and a lithium salt as a combination of catalysts used for the nucleophilic substitution reaction. Can be mentioned. It is believed that this combination of catalysts suppresses the formation of by-products and increases the yield of the desired product (see, for example, Examples 6 and 7 below).

The 3-methylpentyl nucleophilic reagent (2) having a hydroxyl group protected at the 5-position is represented by the following general formula (2a) when the priority of atoms in the RS notation is M> O. (R) -3-methylpentyl nucleophilic reagent having a hydroxyl group protected by, and (S) -3-methylpentyl nucleophilic having a hydroxyl group protected at the 5-position represented by the following general formula (2b). Can exist as a reagent. These isomers may be alone or mixed, but preferably contain (2a) which has the same skeleton as the natural sex pheromone of females of California red scale .

The 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position has a hydroxyl group protected at the 1-position represented by the following general formula (3a) (3R, 6R) -6-isopropenyl-3-methyl-9-decene compound, represented by the following general formula (3b), having a hydroxyl group protected at the 1-position (3R, 6S) -6-isopropenyl-3- Methyl-9-decene compound, (3S, 6R) -6-isopropenyl-3-methyl-9-decene compound having a hydroxyl group protected at the 1-position represented by the following general formula (3c), and the following general. It can exist as a (3S, 6S) -6-isopropenyl-3-methyl-9-decene compound having a hydroxyl group protected at the 1-position represented by the formula (3d). These isomers may be alone or mixed, but preferably contain (3c) which has the same skeleton as the natural sex pheromone of females of California red scale .

The 3,7-dimethyl-7,11-dodecadien compound (3') having a hydroxyl group protected at the 1-position, which is by-produced in the nucleophilic substitution reaction, is represented by the following formula (3'a) at the 1-position. (R, Z) -3,7-dimethyl-7,11-dodecadien compound having a hydroxyl group protected by, and having a hydroxyl group protected at the 1-position represented by the following formula (3'b) (R, E) -3,7-dimethyl-7,11-dodecadien compound, having a hydroxyl group protected at the 1-position represented by the following formula (3'c) (S, Z) -3,7-dimethyl-7. , 11-Dodecadien compound, (S, E) -3,7-dimethyl-7,11-dodecadien compound having a hydroxyl group protected at the 1-position represented by the following formula (3'd), or 2 thereof. It can exist as a mixture of species or more.

R in the 3-methylpentyl nucleophile (2) having a hydroxyl group protected at the 5-position represents a protecting group for the hydroxyl group. As the protecting group, an appropriate protecting group of known hydroxyl groups that is stable during the desired reaction, post-treatment and storage and is easy to deprotect can be selected. Suitable protective groups R include, for example, methoxymethyl group, 2-methoxyethoxymethyl group, benzyloxymethyl group, p-methoxybenzyloxymethyl group, 2,2,2-trichloroethoxymethyl group, 1-ethoxyethyl group. And an oxyalkyl group such as a tetrahydropyranyl group, and an oxyalkyl group having an isomer relationship with these may be used. Further, a part of the hydrogen atom of these protecting groups may be substituted with a methyl group, an ethyl group or the like. Examples of other protective groups include trialkylsilyl groups such as trimethylsilyl group, triethylsilyl group, triisopropylsilyl group and t-butyldimethylsilyl group, and monoalkyldiarylsilyl groups such as t-butyldiphenylsilyl group. , A silyl group having an isomer relationship with these may be used. Further, a part of the hydrogen atom of these silyl groups may be substituted with a methyl group, an ethyl group, a halogen atom or the like. Examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom.
As the protecting group R, a tetrahydropyranyl group and a 1-ethoxyethyl group are preferable from the viewpoint of reactivity and / or economy.
In the 3-methylpentyl nucleophile (2) having a hydroxyl group protected at the 5-position, M represents Li, MgZ ¹ , ZnZ ¹ , Cu, CuZ ¹ or CuLiZ ¹ , and Z ¹ is a halogen atom or CH ₂ . CH ₂ CH (CH ₃ ) CH ₂ CH ₂ OR group, and R represents a hydroxyl group protecting group.
The 3-methylpentyl nucleophilic reagent (2) having a 5-position protected hydroxyl group has a 5-position protected hydroxyl group from the viewpoints of reactivity, selectivity, and / or ease of preparation. Organic lithium reagents such as 3-methylpentyllithium compounds, and organic magnesium reagents such as 3-methylpentylmagnesium = halide compounds (Grignard reagents) having a hydroxyl group protected at the 5-position are preferable, and 3-methylpentylmagnesium = halide compounds in particular. (Grignard reagent) is preferred.

As a specific example of the halide of the 3-methylpentylmagnesium = halide compound having a hydroxyl group protected at the 5-position, the 3-methylpentylmagnesium = chloride compound having a hydroxyl group protected at the 5-position is a hydroxyl group protected at the 5-position. Examples thereof include a 3-methylpentylmagnesium = bromide compound having a hydroxyl group and a 3-methylpentylmagnesium = iodide compound having a hydroxyl group protected at the 5-position.
The 3-methylpentyl nucleophile (2) having a hydroxyl group protected at the 5-position is, for example, a 3-methylpentyl-halide compound having a hydroxyl group protected at the 5-position, which is a corresponding halide, by a conventional method. Prepared. Examples of the 3-methylpentyl-halide compound having a hydroxyl group protected at the 5-position include a 3-methylpentyl-chloride compound having a hydroxyl group protected at the 5-position and 3-methyl having a hydroxyl group protected at the 5-position. Examples thereof include a pentyl = bromide compound and a 3-methylpentyl = iodide compound having a hydroxyl group protected at the 5-position, and a 3-methylpentyl nucleophilic reagent (2) having a hydroxyl group protected at the 5-position is prepared. From the viewpoint of ease and / or stability of the compound, 3-methyl-pentyl = chloride compound having a hydroxyl group protected at the 5-position and 3-methyl-pentyl-bromid compound having a hydroxyl group protected at the 5-position are used. preferable.

The 3-methylpentyl nucleophilic reagent (2) having a hydroxyl group protected at the 5-position is a metal exchange using a chemical quantitative amount (1 mol or more) of a transition metal compound from an organic lithium reagent or an organic magnesium reagent. ) It may be prepared and used by a reaction, or it may be produced and used in a reaction system by a reaction between an organic lithium reagent or a Grinard reagent and a transition metal compound in a catalytic amount.

Examples of the transition metal compound include transition metal compounds containing copper, iron, nickel, palladium, zinc, titanium, silver and the like, and copper (I) chloride, copper (I) bromide and copper (I) iodide. Monovalent copper halides such as: copper (II) chloride, copper (II) bromide and copper (II) divalent such as copper iodide; copper (I) cyanide and copper (II) cyanide. Such as copper cyanide; copper oxide such as copper (I) oxide and copper (II) oxide; and copper compounds such as dilithium = tetrachlorocuplate (Li ₂ CuCl ₄ ) are preferable, and from the viewpoint of reactivity, one Valuable copper halides are particularly preferred.
The amount of the transition metal compound used ranges from a catalytic amount (0.0001 to 0.999 mol) to a stoichiometric amount (1 mol) or an excess amount (more than 1 and 100 mol or less), but from 0.0001 to The use of 10 mol is preferred.

The R in the 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position is the same as the R defined in the general formula (2).

For nucleophilic substitution reaction between 2-methyl-2,6-heptadiene compound (1) having a leaving group X at the 1-position and 3-methylpentyl nucleophile (2) having a hydroxyl group protected at the 5-position. Usually, an organic metal reagent containing a group I or group II metal element or a transition metal element is used.
When a transition metal compound is used in the nucleophilic substitution reaction, from the viewpoint of improving the solubility of the transition metal compound in a solvent, trialkyl phosphite such as triethyl phosphate or triarylphosphine such as triphenylphosphine may be used. A co-catalyst such as a phosphorus compound may be preferably used in an amount of 0.001 to 1000 parts with respect to 100 parts of the transition metal compound.

In the nucleophilic substitution reaction, as a reaction catalyst, lithium salts such as lithium chloride, lithium bromide and lithium iodide are used as a 2-methyl-2,6-heptadiene compound (1) having a leaving group X at the 1-position. 0.001 to 1,000 mols may coexist with respect to 1 mol.
In the nucleophilic substitution reaction, a combination of a monovalent copper halide and a lithium salt is particularly preferable from the viewpoint of reactivity including the production ratio of the target substance and a by-product (see Examples 6 and 7 below). ).

The amount of the 3-methylpentyl nucleophilic reagent (2) having a hydroxyl group protected at the 5-position depends on the type of reagent, reaction conditions, reaction yield, economic efficiency such as intermediate price, and / or reaction generation. Although it is arbitrarily determined in consideration of the ease of isolation and purification of the target compound from the substance, preferably 0.2 to 100 mol with respect to 1 mol of the 2-methyl-2,6-heptadiene compound (1). It is more preferably 0.5 to 20 mol, still more preferably 0.8 to 5 mol.

The nucleophilic substitution reaction is carried out in a solvent by cooling or heating as necessary.
The solvent used for the nucleophilic substitution reaction includes ethers such as diethyl = ether, di-n-butyl = ether, t-butyl = methyl = ether, cyclopentyl = methyl = ether, tetrahydrofuran and 1,4-dioxane; hexane. , Heptane, benzene, toluene, xylene and cumene; and N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N, N-dimethylpropionamide, 1,3-dimethyl-2- Examples thereof include aprotonic polar solvents such as imidazolidinone (DMI), dimethyl-sulfoxide (DMSO) and hexamethylphosphoric-triamide (HMPA), and ethers are preferable from the viewpoint of reactivity. As the solvent, the ethers may be used alone, or, if necessary, a mixed solvent containing the ethers and one or more selected from the above solvents other than the ethers may be used. As the solvent, a commercially available solvent can be used.
The amount of the solvent used is not particularly limited, but is preferably 10 to 1,000,000 g, more preferably 10 to 1,000,000 g, based on 1 mol of the 3-methylpentyl nucleophile (2) having a hydroxyl group protected at the 5-position. It is 100 to 100,000 g, more preferably 150 to 10,000 g.

The reaction temperature in the nucleophilic substitution reaction is preferably −78 ° C. to the boiling point temperature of the solvent, more preferably −78 ° C. to 100 ° C.
The reaction time in the nucleophilic substitution reaction can be set arbitrarily, but it is preferable to use gas chromatography (GC) or thin layer chromatography (TLC) to track and optimize the progress of the reaction, usually from 5 minutes to. 240 hours is preferred.

If the 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position obtained in the nucleophilic substitution reaction has sufficient purity, it is a crude product. It may be used as it is in the next step, or it may be appropriately selected and purified from the purification methods in ordinary organic synthesis such as distillation or various chromatographies, and distillation is particularly preferable from the viewpoint of industrial economic efficiency.

[2] Step C
The step C for obtaining 6-isopropenyl-3-methyl-9-decenol (4) will be described below. 6-Isopropenyl-3-methyl-9-decenol (4) is 6-isopropenyl-3 having a 1-position protected hydroxyl group obtained in Step B as shown in the following chemical reaction formula. It is obtained by the deprotection reaction of the -methyl-9-decene compound (3).

In the deprotection reaction, the double bond of the isopropenyl group in the 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position represented by the following formula (4') is 4 An isomer that has moved to the substitution side (hereinafter, also referred to as "isomer (4')") can be by-produced. Therefore, among the conditions of the deprotection reaction described later, the optimum conditions for suppressing the by-product of the isomer (4') and obtaining 6-isopropenyl-3-methyl-9-decenol (4) in a good yield. You just have to choose. The optimum conditions are, for example, that the R of the 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position is a 1-ethoxyethyl group, and an acid is used. In the deprotection reaction, acetic acid is used as an acid, water is used together with the acid, and the reaction temperature is 120 ° C. or lower.

The 6-isopropenyl-3-methyl-9-decene compound (4) is represented by the following formula (4a) (3R, 6R) -6-isopropenyl-3-methyl-9-decenol, the following formula (4b). (3R, 6S) -6-isopropenyl-3-methyl-9-decenol, represented by the following formula (4c) (3S, 6R) -6-isopropenyl-3-methyl-9- It may exist as decenol and (3S, 6S) -6-isopropenyl-3-methyl-9-decenol represented by the following formula (4d). These isomers may be alone or mixed, but preferably contain (4c) having the same skeleton as the natural sex pheromone of females of California red scale .

The isomer (4') is represented by the following formula (4'a) (R) -isomer (4') and the following formula (4'b) (S) -isomer (4'). ), Or both of them.

For the deprotection reaction, appropriate conditions may be selected depending on the type of protecting group in the 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position. For example, when the protecting group is an oxyalkyl group such as a methoxymethyl group, a deprotection reaction by solvolysis using an acid or the like can be applied. Further, for example, when the protecting group is a silyl group such as t-butyldimethylsilyl group, a deprotection reaction using a fluoride ion can be applied in addition to a deprotection reaction such as solvolysis using an acid.

In the case of a deprotection reaction using an acid, 6-isopropenyl-3-methyl-9-decenol (4) is a 6-isopropenyl-3-methyl-9-decene compound having a hydroxyl group protected at the 1-position. It can be synthesized by adding an acid and, if necessary, water or a solvent to 3) and cooling or heating.
Examples of the acid used for the deprotection reaction include inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitrate and phosphoric acid or salts thereof; formic acid, acetic acid, propionic acid, oxalic acid and trifluoro. Organic acids such as acetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid (p-TsOH) and naphthalenesulfonic acid or salts thereof; lithium tetrafluoroborate, boron trifluoride, boron trichloride, triodor Lewis acids such as boron oxide, aluminum trichloride, zinc chloride, zinc bromide, zinc iodide, tin tetrachloride, tin tetrabromide, tin dichloride, titanium tetrachloride, titanium tetrabromide and trimethylsilyl iodide; alumina, Oxides such as silica gel and titania; and minerals such as montmorillonite can be mentioned.
As the acid used for the deprotection reaction, acetic acid can be mentioned as a preferable example from the viewpoint of economy, reactivity, and / or suppression of by-product of the isomer (4').
The acid may be used alone or in combination of two or more, if necessary. Further, as the acid, a commercially available acid can be used.
The amount of the acid used is preferably small from the viewpoint of economic efficiency, and can be arbitrarily set as long as a practically sufficient reaction rate can be obtained, but 6-isopropenyl-3-methyl- having a hydroxyl group protected at the 1-position is used. The amount is preferably 0.00001 to 10,000 mol, more preferably 0.0001 to 1,000 mol, still more preferably 0.001 to 100 mol, based on 1 mol of the 9-decene compound (3).

When water is further used in the deprotection reaction with the acid, the amount of water is relative to 1 mol of 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position. It is preferably 1 to 10,000 mol, more preferably 1 to 1,000 mol, and even more preferably 1 to 500 mol.

Examples of the solvent in the deprotection reaction using an acid include ethers such as diethyl = ether, dibutyl = ether, tetrahydrofuran and 1,4-dioxane; and hydrocarbons such as hexane, heptane, benzene, toluene, xylene and cumene. Chlorine-based solvents such as methylene chloride, chloroform and trichloroethylene; Ketones such as acetone and methyl = ethyl = ketone; N, N-dimethylformamide (DMF), 1,3-dimethyl-2-imidazolidinone (DMI) , Aprotonic polar solvents such as dimethyl = sulfoxide (DMSO) and hexamethylphosphoric = triamide (HMPA); nitriles such as acetonitrile, propionitrile; esters such as ethyl acetate and n-butyl acetate; Examples thereof include alcohols such as methanol, ethanol and t-butyl = alcohol.
The solvent may be used alone or in combination of two or more, if necessary. Further, as the solvent, a commercially available solvent can be used.
When water or alcohols are used as the solvent for deprotection, the compound in which alcohol is added to the double bond moiety of 6-isopropenyl-3-methyl-9-decenol (4) and / or isomer (4') Can be a by-product. This side reaction can be suppressed by selecting appropriate conditions from the type of acid used and / or the reaction temperature. Suitable conditions include, for example, the use of acetic acid as the acid to be used and / or the reaction temperature of 120 ° C. or lower.
The amount of the solvent used for the deprotection reaction using an acid is preferably from 10 g to 1 mol of the 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position. It is 10,000 g.

The reaction temperature of the deprotection reaction using an acid depends on the reaction conditions, but is preferably −78 to 160 ° C., more preferably −50 to 140 ° C., and even more preferably −30 to 120 ° C.
The reaction time of the deprotection reaction using an acid can be set arbitrarily, but it is possible to follow the reaction and complete the reaction by using gas chromatography (GC) or thin layer chromatography (TLC). It is desirable from the viewpoint, and it is usually about 0.5 to 24 hours.

When the protecting group is a silyl group and the protecting group is deprotected with fluoride ions, 6-isopropenyl-3-methyl-9-decenol (4) has a hydroxyl group protected at the 1-position. -Isopropenyl-3-methyl-9-decene compound (3) can be synthesized by adding a reagent as a fluoride ion source and, if necessary, a solvent, and cooling or heating. Further, the deprotection reaction can be carried out in combination with the acid described in the deprotection reaction with an acid.

Fluoride ion sources include inorganic acids such as hydrofluoric acid; amine complexes such as pyridine / nHF and triethylamine / nHF; cesium fluoride, potassium fluoride, lithium borofluoride (LiBF ₄ ) and fluoride. Inorganic salts such as ammonium; organic salts such as tetrabutylammonium fluoride (TBAF) can be mentioned.
The reagent used as the fluoride ion source may be one type or, if necessary, two or more types. Further, as the reagent serving as the fluoride ion source, a commercially available reagent can be used.
The amount of the reagent used in the deprotection reaction with fluoride ions is preferably 0.1 with respect to 1 mol of the 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position. It is in the range of ~ 500 mol, more preferably 0.1-50 mol.

As for the solvent, the amount of the solvent used, the reaction time and the reaction temperature in the deprotection reaction with fluoride ions, the acid of the 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position. It is the same as the solvent, the amount of the solvent used, the reaction time and the reaction temperature described in the deprotection reaction by.

Alcohol compounds can be by-produced by the deprotection reaction. For example, when deprotecting the 1-ethoxyethoxy group, ethanol is by-produced as an alcohol compound. When the alcohol compound is by-produced, the deprotection reaction may be carried out while removing the by-produced alcohol compound from the reaction system by a method such as distillation.

If the 6-isopropenyl-3-methyl-9-decenol (4) obtained by the deprotection reaction has sufficient purity, the crude product may be used as it is in the next step. Alternatively, it may be appropriately selected and purified from the purification methods in ordinary organic synthesis such as distillation or various chromatographies, and distillation is particularly preferable from the viewpoint of industrial economic efficiency.

[3] Step D
The step D for obtaining 6-isopropenyl-3-methyl-9-decenyl = acetate (5) will be described below. 6-Isopropenyl-3-methyl-9-decenyl-acetate (5) is the 6-isopropenyl-3-methyl-9-decenol obtained in Step C as shown in the following chemical reaction formula. It is obtained by acetylating 4).

6-Isopropenyl-3-methyl-9-decenyl = acetate (5) is represented by the following formula (5a) (3R, 6R) -6-isopropenyl-3-methyl-9-decenyl = acetate, below. (3R, 6S) -6-isopropenyl-3-methyl-9-decenyl = acetate represented by the formula (5b), (3S, 6R) -6-isopropenyl-3 represented by the following formula (5c) It may exist as -methyl-9-decenyl = acetate and (3S, 6S) -6-isopropenyl-3-methyl-9-decenyl = acetate represented by the following formula (5d). These isomers may be alone or mixed, but preferably contain (5c) having the same skeleton as the natural sex pheromone of females of California red scale .

Acetylation includes known methods for producing acetate, such as (i) reaction with an acetylating agent, (ii) dehydration reaction with acetic acid, (iii) ester exchange reaction with acetic acid ester, and (iv) 6-iso. A reaction in which propenyl-3-methyl-9-decenol (4) is converted into an alkylating agent and then acetic acidized with acetic acid or the like can be applied.

(I) Reaction with an acetylating agent In the reaction with an acetylating agent, 6-isopropenyl-3-methyl-9-decenol (4) is added to the acetylating agent and a base in a single solution or a mixed solvent of two or more kinds. In the order of or vice versa, a method of reacting with an acetylating agent and a base at the same time, or a method of reacting 6-isopropenyl-3-methyl-9-decenol (4) with an acetylating agent in the presence of a catalyst. Can be applied.
Examples of the acetylating agent include acetic acid chloride, bromide acetate, acetic anhydride and the like.
The amount of the acetylating agent used is preferably 1 mol to 500 mol, more preferably 1 mol to 50 mol, based on 1 mol of 6-isopropenyl-3-methyl-9-decenol (4). Is in the range of 1-5 mol.

Examples of the base used for the reaction with the acetylating agent include amines such as triethylamine, pyridine, N, N-dimethylaminopyridine and N, N-dimethylaniline; and organic lithium compounds such as n-butyllithium, methyllithium and phenyllithium. Metal hydroxides such as sodium hydroxide and potassium hydroxide; and metal carbonates such as potassium carbonate, sodium carbonate and sodium hydrogencarbonate.
The amount of the base used is preferably 1 to 500 mol with respect to 1 mol of 6-isopropenyl-3-methyl-9-decenol (4).

When anhydrous acetic acid is used as the acetylating agent, inorganic acids such as hydrochloric acid, hydrobromic acid, nitrate and sulfuric acid; trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and the like can be used as catalysts. Organic acids; aluminum trichloride, aluminum = ethoxydo, aluminum = isopropoxide, aluminum oxide, boron trifluoride, boron trichloride, boron tribromide, magnesium chloride, magnesium bromide, magnesium iodide, zinc chloride, odor Zinc bromide, zinc iodide, tin tetrachloride, tin tetrabromide, dibutyl tin dichloride, dibutyl tin = dimethoxydo, dibutyl tin = oxide, titanium tetrachloride, titanium tetrabromide, titanium (IV) = methoxyd, titanium (IV) ) = Ethoxydo, titanium (IV) = Lewis acids such as isopropoxide and titanium oxide (IV); and metal acetates such as sodium acetate and potassium acetate.
The amount of the catalyst used in the reaction with the acetylating agent is preferably 0.0001 to 100 mol with respect to 1 mol of 6-isopropenyl-3-methyl-9-decenol (4).

As the solvent in the reaction with the acetylating agent, halogen-based solvents such as methylene chloride and chloroform; hydrocarbon-based solvents such as hexane, heptane, benzene and toluene; diethyl = ether, tetrahydrofuran, 1,4-dioxane and ethylene. = Glycol = dimethyl = ether solvents such as ether; nitrile solvents such as acetonitrile; ketone solvents such as acetone, methyl = ethyl = ketone and diisobutyl = ketone; ester solvents such as ethyl acetate and butyl acetate; Also mentioned are aprotonic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl-sulfoxide and hexamethylphosphoric-triamide.
The solvent may be used alone or in combination of two or more, if necessary. Depending on the acetylating agent, the reaction can be carried out without using a solvent. Further, as the solvent, a commercially available solvent can be used.
The amount of the solvent used is preferably 0 to 2000 g, more preferably 0 to 500 g, based on 1 mol of 6-isopropenyl-3-methyl-9-decenol (4).

The reaction temperature in the reaction with the acetylating agent is preferably −50 ° C. to the boiling point temperature of the solvent, and more preferably −30 ° C. to 80 ° C. from the viewpoint of reactivity and yield.
The reaction time in the reaction with the acetylating agent can be set arbitrarily, but it is preferable to track and optimize the progress of the reaction by using gas chromatography (GC) or thin layer chromatography (TLC), usually from 5 minutes to. 240 hours is preferred.

(Ii) Dehydration reaction with acetic acid The dehydration reaction between 6-isopropenyl-3-methyl-9-decenol (4) and acetic acid can generally be carried out in the presence of an acid or a Lewis acid catalyst.
Inorganic acids such as hydrochloric acid, hydrobromic acid, nitrate and sulfuric acid; organic acids such as trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid; aluminum trichloride as catalysts in the dehydration reaction. , Aluminum = ethoxydo, aluminum = isopropoxide, aluminum oxide, boron trifluoride, boron trichloride, boron tribromide, magnesium chloride, magnesium bromide, magnesium iodide, zinc chloride, zinc bromide, zinc iodide, Tin tetrachloride, tin tetrabromide, dibutyl tin dichloride, dibutyl tin = dimethoxydo, dibutyl tin = oxide, titanium tetrachloride, titanium tetrabromide, titanium (IV) = methoxydo, titanium (IV) = ethoxydo, titanium (IV) ) = Lewis acids such as isopropoxide and titanium oxide (IV).
The acid may be used alone or in combination of two or more, if necessary. Further, as the acid, a commercially available acid can be used.
The amount of the catalyst used in the dehydration reaction is preferably 0.001 to 1 mol with respect to 1 mol of 6-isopropenyl-3-methyl-9-decenol (4), and is 0.01 from the viewpoint of economy and reactivity. More preferably, mol to 0.1 mol.

The dehydration reaction with acetic acid can be carried out while removing water produced as a by-product of the reaction. For example, a method of azeotropically distilling off the reaction solvent to be used and water under normal pressure or reduced pressure, or a method of adding a dehydrating agent such as anhydrous magnesium sulfate, molecular sieve, or dicyclohexylcarbodiimide into the reaction system, etc. Can be mentioned.

As the solvent in the dehydration reaction, halogen-based solvents such as methylene chloride and chloroform; hydrocarbon solvents such as hexane, heptane, benzene and toluene; diethyl = ether, tetrahydrofuran, 1,4-dioxane and ethylene = glycol = dimethyl. = Ether solvents such as ether; nitrile solvents such as acetonitrile; ketone solvents such as acetone, methyl = ethyl = ketone and diisobutyl = ketone; and ester solvents such as ethyl acetate and butyl acetate. ..
The solvent may be used alone or in combination of two or more, if necessary. Further, depending on the reaction conditions of the dehydration reaction, the dehydration reaction can be carried out without using a solvent. As the solvent, a commercially available solvent can be used.
The amount of the solvent used in the dehydration reaction is preferably 0 to 2000 g, more preferably 0 to 500 g, based on 1 mol of 6-isopropenyl-3-methyl-9-decenol (4).

The reaction temperature in the dehydration reaction can be selected from an appropriate reaction temperature depending on the type of catalyst used, but is generally preferably −50 to 200 ° C., more preferably −20 to 100 ° C. from the viewpoint of reactivity and yield. .. When water produced as a by-product of the reaction is azeotropically distilled with a solvent, it is preferably carried out under normal pressure or reduced pressure at a reaction temperature equal to or higher than the azeotropic point of the solvent and water.
The reaction time in the dehydration reaction can be set arbitrarily, but it is preferable to track and optimize the progress of the reaction by using gas chromatography (GC) or thin layer chromatography (TLC), and usually 5 minutes to 240 hours is preferable. ..

(Iii) Transesterification reaction with acetic acid ester The transesterification reaction is generally carried out in the presence of a catalyst, and the alcohol produced as a by-product from the acetic acid ester is removed during the reaction under normal pressure or reduced pressure to promote the reaction. be able to.
As the acetic acid ester in the ester exchange reaction, for example, acetic acid esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate and phenyl acetate can be used. Of these acetates, ethyl acetate is preferred from the viewpoint of economy, reactivity, and ease of removal of alcohol by-produced from the acetate.
The amount of the acetate ester used in the transesterification reaction is preferably 1 to 50 mol, more preferably 1 to 5 mol, relative to 1 mol of 6-isopropenyl-3-methyl-9-decenol (4).

As catalysts in the ester exchange reaction, inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid and nitric acid; organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid; sodium = Basics such as methoxydo, sodium = ethoxydo, potassium = t-butoxide and 4-dimethylaminopyridine; such as sodium broth, potassium broth, sodium acetate, potassium acetate, calcium acetate, tin acetate, aluminum acetate, aluminum acetoacetate and alumina. Salts; as well as aluminum trichloride, aluminum = ethoxydo, aluminum = isopropoxide, aluminum oxide, boron trifluoride, boron trichloride, boron tribromide, magnesium chloride, magnesium bromide, magnesium iodide, zinc chloride, odor Zinc bromide, zinc iodide, tin tetrachloride, tin tetrabromide, dibutyl tin dichloride, dibutyl tin = dimethoxydo, dibutyl tin = oxide, titanium tetrachloride, titanium tetrabromide, titanium (IV) methoxyd, titanium (IV) = Ethoxydo, titanium (IV) = isopropoxide and Lewis acids such as titanium oxide (IV) can be mentioned.
The catalyst may be used alone or in combination of two or more, if necessary. Further, as the catalyst, a commercially available catalyst can be used.
The amount of the catalyst used in the transesterification reaction is preferably 0.001 mol to 1 mol, more preferably 0.01 to 0. With respect to 1 mol of 6-isopropenyl-3-methyl-9-decenol (4). It is 05 mol.

The solvents used in the ester exchange reaction are halogen-based solvents such as methylene chloride and chloroform; hydrocarbon solvents such as hexane, heptane, benzene and toluene; diethyl = ether, tetrahydrofuran, 1,4-dioxane and ethylene = glycol = dimethyl. = Ether solvents such as ether; nitrile solvents such as acetonitrile; ketone solvents such as acetone, methyl = ethyl = ketone and diisobutyl = ketone; ester solvents such as ethyl acetate and butyl acetate.
The solvent may be used alone or in combination of two or more, if necessary. Further, depending on the reaction conditions of the transesterification reaction, it can be carried out only with the alcohol compound, the acetate ester and the catalyst produced by the transesterification reaction without using a solvent. As the solvent, a commercially available solvent can be used.
The amount of the solvent used in the transesterification reaction is preferably 0 to 2000 g, more preferably 0 to 500 g, based on 1 mol of 6-isopropenyl-3-methyl-9-decenol (4).

The reaction temperature in the transesterification reaction can be appropriately selected depending on the type of acetic acid ester and catalyst. Generally, the reaction temperature is preferably 0 ° C to 200 ° C, more preferably 50 ° C to 160 ° C. When the alcohol produced as a by-product from the acetic acid ester is removed during the reaction to promote the reaction, it is preferable to carry out the reaction at a reaction temperature equal to or higher than the boiling point of the alcohol to be removed under normal pressure or reduced pressure.
The reaction time in the transesterification reaction can be set arbitrarily, but it is preferable to track and optimize the progress of the reaction by using gas chromatography (GC) or thin layer chromatography (TLC), and usually 5 minutes to 240 hours. preferable.

(Iv) Reaction of converting 6-isopropenyl-3-methyl-9-decenol (4) into an alkylating agent and then acetic acidizing with acetic acid or the like 6-isopropenyl-3-methyl-9-decenol (4) Is converted into an alkylating agent, and then acetic acidized with acetic acid or the like. And halides such as iodide; after conversion to an alkylating agent such as a sulfonic acid ester such as a methane sulfonic acid ester, a benzene sulfonic acid ester and a p-toluene sulfonic acid ester, the obtained alkylating agent is used in the presence of a base. It can be carried out by reacting with acetic acid. Further, instead of acetic acid, available metal acetate salts such as sodium acetate and potassium acetate may be used without using a base.
In the step of converting 6-isopropenyl-3-methyl-9-decenol (4) into an alkylating agent and the step of acetoxylating with acetic acid or the like, 6-isopropenyl-3-methyl-9-decenol (4) is used. After the step of converting to an alkylating agent, a step of acetoxylation may be performed as it is in a one-step step. Further, after stopping the reaction of converting 6-isopropenyl-3-methyl-9-decenol (4) into an alkylating agent, the organic layer is washed, the solvent is removed, and if necessary, the alkylating agent is purified. , Acetoxylation with acetic acid or the like may be performed.

The reaction to convert 6-isopropenyl-3-methyl-9-decenol (4) to the corresponding alkylating agent is to convert 6-isopropenyl-3-methyl-9-decenol (4) to the corresponding alkylating agent using a halogenating agent. Examples thereof include a reaction for converting chloride, bromide or iodide, or a reaction for converting an alcohol compound into a sulfonic acid ester using a sulfonylating agent.
Halogenating agents include hydrochloric acid, phosphorus trichloride, thionyl chloride, carbon tetrachloride, methanesulfonyl = chloride and p-toluenesulfonyl = chloride and other chlorinating agents; hydrobromic acid, phosphorus tribromide, thionyl bromide and Bromine agents such as carbon tetrabromide; and iodizing agents such as hydroiodic acid, potassium iodide and phosphorus triiodide can be mentioned.
Examples of the sulfonylating agent include methanesulfonyl = chloride, benzenesulfonyl = chloride, p-toluenesulfonyl = chloride and the like.
In the reaction for converting 6-isopropenyl-3-methyl-9-decenol (4) to an alkylating agent, the amount of the halogenating agent or sulfonylating agent used is 6-isopropenyl-3-methyl-9-decenol (4). 4) 1 to 50 mol is preferable with respect to 1 mol, and 1 to 10 mol is more preferable from the viewpoint of economic efficiency.

The solvent in the reaction for converting 6-isopropenyl-3-methyl-9-decenol (4) into an alkylating agent is a halogen-based solvent such as methylene chloride and chloroform; a hydrocarbon-based solvent such as hexane, heptane, benzene and toluene. Solvents; ether solvents such as diethyl = ether, tetrahydrofuran, 1,4-dioxane and ethylene = glycol = dimethyl = ether; nitrile solvents such as acetonitrile; ketones such as acetone, methyl = ethyl = ketone and diisobutyl = ketone System solvents; ester solvents such as ethyl acetate and butyl acetate; and aprotonic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl = sulfoxide and hexamethylphosphoric = triamide. Can be mentioned.
The solvent may be used alone or in combination of two or more, if necessary. It is also possible to react without using a solvent. As the solvent, a commercially available solvent can be used.
The amount of solvent used in the reaction to convert 6-isopropenyl-3-methyl-9-decenol (4) to an alkylating agent was 1 mol of 6-isopropenyl-3-methyl-9-decenol (4). , 0 to 2000 g is preferable, and 0 to 500 g is more preferable from the viewpoint of economic efficiency.

The reaction temperature in the reaction for converting 6-isopropenyl-3-methyl-9-decenol (4) to an alkylating agent is preferably -30 to 250 ° C. in terms of reactivity and yield, and the reactivity and yield are preferably -30 to 250 ° C. From the viewpoint, 0 to 180 ° C. is more preferable.

The amount of acetic acid or metal acetate used in the acetic acidization reaction of the obtained alkylating agent is preferably 1 mol to 50 mol, more preferably 1 to 10 mol, based on 1 mol of the alkylating agent. ..
The base in the acetoxylation reaction of the obtained alkylating agent is amines such as triethylamine, pyridine, N, N-dimethylaminopyridine and dimethylaniline; organic lithium compounds such as n-butyllithium, methyllithium and phenyllithium; water. Examples thereof include metal hydroxides such as sodium oxide and potassium hydroxide; metal carbonates such as potassium carbonate, sodium carbonate and sodium hydrogencarbonate; and metal hydrides such as sodium hydride and potassium hydride.
The amount of the base used in the acetoxylation reaction of the obtained alkylating agent is preferably 1 to 50 mol, more preferably 1 to 10 mol, with respect to 1 mol of the alkylating agent.

The solvent in the acetoxylation reaction of the obtained alkylating agent is a halogen-based solvent such as methylene chloride and chloroform; a hydrocarbon solvent such as hexane, heptane, benzene and toluene; diethyl = ether, tetrahydrofuran, 1,4-. Ether-based solvents such as dioxane and ethylene = glycol = dimethyl = ether; nitrile-based solvents such as acetonitrile; ketone-based solvents such as acetone, methyl = ethyl = ketone and diisobutyl = ketone; ester-based solvents such as ethyl acetate and butyl acetate. Solvents; and aproton polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl = sulfoxide and hexamethylphosphoric = triamide.
The solvent may be used alone or in combination of two or more, if necessary. Further, depending on the type of the alkylating agent, the reaction can be carried out without using a solvent.
The amount of the solvent used in the acetoxylation reaction of the obtained alkylating agent is preferably 0 to 2000 g, more preferably 0 to 500.0 g per 1 mol of the alkylating agent, from the viewpoint of economic efficiency.

The reaction temperature of the obtained alkylating agent in the acetoxylation reaction is preferably −30 to 250 ° C. from the viewpoint of reactivity and yield, and more preferably 25 to 180 ° C. from the viewpoint of reactivity and yield.

The reaction time in the acetoxylation can be set arbitrarily, but it is preferable to use gas chromatography (GC) or thin layer chromatography (TLC) to track and optimize the progress of the reaction, usually 5 minutes to 240 hours. Is preferable.

Regarding the purification of 6-isopropenyl-3-methyl-9-decenyl-acetate (5) obtained by the acetoxylation, purification is appropriately selected from purification methods in ordinary organic synthesis such as distillation or various chromatographies. Distillation is particularly preferable from the viewpoint of industrial economic efficiency.

[4] Step A
The step A for obtaining the 2-methyl-2,6-heptadiene compound (1) will be described below. The 2-methyl-2,6-heptadiene compound (1) is prepared by converting the hydroxyl group of the above-mentioned 2-methyl-2,6-heptadienol (6) as shown in the following chemical reaction formula. can get.

2-Methyl-2,6-heptadienol (6) is represented by (Z) -2-methyl-2,6-heptadienol represented by the following formula (6a) and the following formula (6b). (E) May exist as -2-methyl-2,6-heptadienol. These isomers may be alone or as a mixture.

The method for producing 2-methyl-2,6-heptadienol (6) is not particularly limited, but it can be obtained, for example, by a reduction reaction between the 2-methyl-2,6-heptadienoic acid ester compound and a reducing agent.

When the leaving group X is an acyloxy group, an esterification reaction is carried out as a conversion reaction of the hydroxyl group of 2-methyl-2,6-heptadienol (6). The esterification reaction includes known methods for producing an ester, for example, (i) reaction with an acylating agent, (ii) reaction with a carboxylic acid, (iii) ester exchange reaction, (iv) 2-methyl-2, A method of converting the hydroxyl group of 6-heptadienol (6) into a leaving group and then reacting with a carboxylic acid can be applied.

(I) Reaction with acylating agent In the reaction with the acylating agent, 2-methyl-2,6-heptadienol (6) is added to the acylating agent and the base in a single solution or a mixed solvent of two or more kinds. A method of reacting in order or vice versa, or at the same time as the acylating agent and the base can be applied.
As the acylating agent, halogenated acyls such as acyl chloride and acyl bromide; carboxylic acid anhydride, carboxylic acid trifluoroacetic acid mixed acid anhydride, carboxylic acid methanesulfonic acid mixed acid anhydride, and carboxylic acid trifluoromethanesulfonic acid mixture. Examples thereof include carboxylic acid mixed acid anhydrides such as acid anhydrides, carboxylic acid benzenesulfonic acid mixed acid anhydrides and carboxylic acid p-toluenesulfonic acid mixed acid anhydrides; and carboxylic acid p-nitrophenyl.
Specific examples of the acyl chloride include acetyl = chloride, propionyl = chloride, crotonoyl = chloride, benzoyl = chloride and the like. Examples of the carboxylic acid anhydride include acetic anhydride and propionic anhydride.
The amount of the acylating agent used is preferably 1 to 500 mol, more preferably 1 to 50 mol, still more preferably 1 to 5 mol, based on 1 mol of 2-methyl-2,6-heptadienol (6). Is the range of.

Examples of the base used for the reaction with the acylating agent include N, N-diisopropylethylamine, N, N-dimethylaniline, N, N-diethylaniline, pyridine, 2-ethylpyridine and 4-dimethylaminopyridine.
The amount of the base used is 1 to 500 mol per 1 mol of 2-methyl-2,6-heptadienol (6).

As the solvent used for the reaction with the acylating agent, the above base may be used as a solvent, or chlorine-based solvents such as methylene chloride, chloroform and trichloroethylene; hexane, heptane, benzene, toluene, xylene and cumene and the like. Hydrocarbons; diethyl = ether, dibutyl = ether, diethylene glycol = diethyl = ether, diethylene glycol = dimethyl = ether, ethers such as tetrahydrofuran and 1,4-dioxane; nitriles such as acetonitrile; ketones such as acetone and 2-butanone Classes; esters such as ethyl acetate and n-butyl acetate; and aprotonic polar solvents such as N, N-dimethylformamide, dimethyl = sulfoxide and hexamethylphosphoric = triamide.
The solvent may be used alone or in combination of two or more, if necessary. Further, as the solvent, a commercially available solvent can be used.
The amount of the solvent used is preferably 10 to 1,000,000 g with respect to 1 mol of 2-methyl-2,6-heptadienol (6).

In the reaction using an acylating agent such as carboxylic acid anhydride, carboxylic acid mixed acid anhydride and carboxylic acid p-nitrophenyl, the reaction can be carried out under an acid catalyst instead of the base.
Acid catalysts include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid and nitric acid; organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid; aluminum trichloride, aluminum. = Ethoxydo, aluminum = isopropoxide, aluminum oxide, boron trifluoride, boron trichloride, boron tribromide, magnesium chloride, magnesium bromide, magnesium iodide, zinc chloride, zinc bromide, zinc iodide, tetrachloride Tin, tin tetrabromide, dibutyl tin dichloride, dibutyl tin = dimethoxydo, dibutyl tin = oxide, titanium tetrachloride, titanium tetrabromide, titanium (IV) = methoxyd, titanium (IV) = ethoxydo, titanium (IV) = Examples thereof include Lewis acids such as isopropoxide and titanium oxide (IV).
The acid catalyst may be used alone or in combination of two or more, if necessary. Further, as the acid catalyst, a commercially available one can be used.
The amount of the acid catalyst used for the reaction with the acylating agent such as carboxylic acid anhydride, carboxylic acid mixed acid anhydride and carboxylic acid p-nitrophenyl is preferably 0.0001 to 100 mol.

As the reaction temperature in the reaction with the acylating agent, an appropriate reaction temperature can be selected depending on the type of acylating agent used and / or the reaction conditions, but in general, the boiling temperature of the solvent is preferably −50 ° C. to −20 ° C. More preferably, the temperature is from ° C to room temperature (5 ° C to 35 ° C, the same applies hereinafter).
The reaction time in the reaction with the acylating agent can be set arbitrarily, but it is preferable to use gas chromatography (GC) or thin layer chromatography (TLC) to track and optimize the progress of the reaction, usually from 5 minutes to 240 hours is preferred.

(Ii) Reaction with carboxylic acid The reaction with carboxylic acid is a dehydration reaction between 2-methyl-2,6-heptadienol (6) and carboxylic acid, and is generally carried out in the presence of an acid catalyst. Is.

Specific examples of the carboxylic acid in the reaction of 2-methyl-2,6-heptadienol (6) with the carboxylic acid include linear saturation of formic acid, acetic acid, propionic acid, butyric acid, valeric acid and caproic acid. Carboxylic acid; branched saturated carboxylic acid such as isobutyric acid, isovaleric acid, 4-methylpentanoic acid, 2-methylbutanoic acid and pivalic acid; linear unsaturated such as acrylic acid, crotonic acid and 3-butenoic acid Carboxylic acid; branched unsaturated carboxylic acid such as methacrylic acid, senesioic acid, tigric acid, angelic acid, 3-methyl-4-pentenic acid and 4-methyl-4-pentenic acid; and aromatics such as benzoic acid. Carboxylic acid and the like can be mentioned.
The amount of the carboxylic acid used is preferably 1 to 500 mol, more preferably 1 to 50 mol, still more preferably 1 to 5 mol, relative to 1 mol of 2-methyl-2,6-heptadienol (6). be.

When using the reaction of 2-methyl-2,6-heptadienol (6) with a carboxylic acid, an acid catalyst may be used. The acid catalyst is the same as the acid catalyst used in the reaction with the above-mentioned acylating agent.
The amount of the acid catalyst used is preferably 0.0001 to 100 mol, more preferably 0.001 to 1 mol, still more preferably 0.001 to 1 mol, based on 1 mol of 2-methyl-2,6-heptadienol (6). It is 0.01 to 0.05 mol.

The solvent used for the reaction between 2-methyl-2,6-heptadienol (6) and the carboxylic acid and the amount used thereof are the same as the solvent used for the reaction with the acylating agent and the amount used thereof.
As the reaction temperature of 2-methyl-2,6-heptadienol (6) and the carboxylic acid, an appropriate reaction temperature can be selected depending on the reaction conditions, but in general, the boiling temperature of the solvent is preferably -50 ° C. , Room temperature to boiling temperature of the solvent is more preferable.
Further, a solvent containing hydrocarbons such as hexane, heptane, benzene, toluene, xylene and cumene may be used to proceed the reaction while removing the generated water from the reaction system by azeotropic boiling. In this case, water may be distilled off while refluxing at the boiling point of the solvent at normal pressure, or water may be distilled off at a temperature lower than the boiling point under reduced pressure.
The reaction time in the reaction with the carboxylic acid can be set arbitrarily, but it is preferable to track and optimize the progress of the reaction by using gas chromatography (GC) or thin layer chromatography (TLC), and usually 5 minutes to 240 minutes. Time is preferred.

(Iii) Transesterification reaction The transesterification reaction is carried out by reacting 2-methyl-2,6-heptadienol (6) with an alkyl carboxylate in the presence of a catalyst to remove the resulting alcohol.
As the alkyl carboxylic acid, a primary alkyl ester of a carboxylic acid is preferable, and methyl carboxylate, ethyl carboxylate and n-propyl carboxylate are more preferable from the viewpoint of price and / or ease of progress of the reaction.
Examples of the carboxylic acid include the same compounds as the carboxylic acid in the esterification reaction with the carboxylic acid.
The amount of the alkyl carboxylate used is preferably 1 to 500 mol, more preferably 1 to 50 mol, still more preferably 1 to 5 mol, relative to 1 mol of 2-methyl-2,6-heptadienol (6). Is.

Catalysts used in the ester exchange reaction include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid and nitric acid, organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid; sodium. = Basics such as methoxyd, sodium = ethoxydo, potassium = t-butoxide and 4-dimethylaminopyridine; sodium broth, potassium broth, sodium acetate, potassium acetate, calcium acetate, tin acetate, aluminum acetate, aluminum acetoacetate and alumina, etc. Salts of: Aluminum trichloride, Aluminum = ethoxydo, Aluminum = isopropoxide, Aluminum oxide, Boron trifluoride, Boron trichloride, Boron tribromide, Magnesium chloride, Magnesium bromide, Magnesium iodide, Zinc chloride, Bromide Zinc, zinc iodide, tin tetrachloride, tin tetrabromide, dibutyl tin dichloride, dibutyl tin = dimethoxydo, dibutyl tin = oxide, titanium tetrachloride, titanium tetrabromide, titanium (IV) methoxyd, titanium (IV) = Lewis acids such as ethoxydo, titanium (IV) = isopropoxide and titanium oxide (IV) can be mentioned.
The catalyst may be used alone or in combination of two or more, if necessary. Further, as the catalyst, a commercially available catalyst can be used.
The amount of the catalyst used is preferably 0.0001 to 100 mol, more preferably 0.001 to 1 mol, still more preferably 0, based on 1 mol of 2-methyl-2,6-heptadienol (6). It is 0.01 to 0.05 mol.

The transesterification reaction may be carried out without a solvent using the alkyl carboxylate itself as a reaction reagent as a solvent, or the solvent may be used as an auxiliary. In the case of no solvent, it is preferable to use no solvent because no extra concentration and operation such as recovery of the medium is required.
The solvents used in the ester exchange reaction include hydrocarbons such as hexane, heptane, benzene, toluene, xylene and cumene; and diethyl = ether, dibutyl = ether, diethylene = glycol = diethyl = ether, diethylene = glycol = dimethyl. = Ethers such as ether, tetrahydrofuran and 1,4-dioxane can be mentioned.
The solvent may be used alone or in combination of two or more, if necessary. Further, as the solvent, a commercially available solvent can be used.
The amount of the solvent used is preferably 10 to 1,000,000 g with respect to 1 mol of 2-methyl-2,6-heptadienol (6).

As the reaction temperature in the transesterification reaction, an appropriate reaction temperature can be selected depending on the type of alkyl carboxylate used and / or the reaction conditions, and the reaction is usually carried out under heating. From the viewpoint of the ease of progress of the reaction, the reaction was carried out near the boiling point of a low boiling point lower alcohol having 1 to 3 carbon atoms, that is, methanol, ethanol, 1-propanol, etc., which was generated by the transesterification reaction. It is preferable to carry out while distilling off the lower alcohol. Alcohol may be distilled off under reduced pressure at a temperature lower than the boiling point.
The reaction time in the transesterification reaction can be set arbitrarily, but it is preferable to use gas chromatography (GC) or thin layer chromatography (TLC) to track and optimize the progress of the reaction, usually 5 minutes to 240 hours. Is preferable.

(Iv) Method of converting the hydroxyl group of 2-methyl-2,6-heptadienol (6) into a leaving group and then reacting with a carboxylic acid 2-methyl-2,6-heptadienol (6) In the method of converting a hydroxyl group into a leaving group and then reacting with a carboxylic acid, for example, the hydroxyl group of 2-methyl-2,6-heptadienol (6) is converted into a halogen atom such as chloride, bromide and iodide, or methane. Converts to a leaving group such as an alkanesulfonyloxy group such as sulfonate, trifluoromethanesulfonate, arenesulfonyloxy such as benzenesulfonate and p-toluenesulfonate, and with these and a carboxylic acid in the presence of a base in the solvent. To react. Further, instead of using a base, available carboxylic acid metal salts such as sodium carboxylate and potassium carboxylate may be used instead of the carboxylic acid.
Examples of the carboxylic acid include compounds similar to the carboxylic acid in the reaction with the carboxylic acid.
The amount of the carboxylic acid used is preferably 1 to 500 mol, more preferably 1 to 50 mol, still more preferably 1 to 5 mol, relative to 1 mol of 2-methyl-2,6-heptadienol (6). be.
Examples of the above-mentioned bases include amines such as triethylamine, pyridine, N, N-dimethylaminopyridine and dimethylaniline; organic lithium compounds such as n-butyllithium, methyllithium and phenyllithium; sodium hydroxide and potassium hydroxide. Examples thereof include metal hydroxides; metal carbonates such as potassium carbonate, sodium carbonate and sodium hydrogencarbonate; and metal hydrides such as sodium hydride and potassium hydride.
The amount of the base used is preferably 1 to 50 mol, more preferably 1 to 10 mol, with respect to 1 mol of the alkylating agent.

The solvent used in the method of converting the hydroxyl group of 2-methyl-2,6-heptadienol (6) into a leaving group and then reacting with the carboxylic acid, the amount of the solvent used, the reaction time and the reaction temperature are as follows. , 2-Methyl-2,6-Heptadienol (6) is the same as the solvent, the amount of the solvent used, the reaction time and the reaction temperature described in the reaction with the acylating agent.

Instead of reacting the carboxylic acid in the solvent in the presence of a base, a carboxylate such as sodium carboxylate, lithium carboxylate, potassium carboxylate and ammonium carboxylate may be used. The amount of the carboxylic acid salt used is the same as the amount of the carboxylic acid used in the esterification reaction of reacting with the carboxylic acid.

When the leaving group X is an alkanesulfonyloxy group, an alkanesulfonylating agent is used to carry out a conversion reaction of the hydroxyl group of 2-methyl-2,6-heptadienol (6). In the reaction with the alkane sulfonylating agent, 2-methyl-2,6-heptadienol (6) is added to the alkane sulfonylating agent, and then to the base, or vice versa, in a single solution or in a mixed solvent of two or more kinds. A method of reacting with an alkane sulfonylating agent and a base at the same time can be applied.
As the alkane sulfonyl agent, an alkane sulfonic acid anhydride having a substituent such as methane sulfonic acid anhydride, ethane sulfonic acid anhydride and trifluoromethane sulfonic acid anhydride; and methanesulfonyl = chloride, ethanesulfonyl. = Alkane sulfonic acid halide and the like which may have a substituent such as chloride and trifluoromethanesulfonyl = chloride.
The amount of the alkanesulfonylating agent used is preferably 1 to 500 mol, more preferably 1 to 50 mol, still more preferably 1 to 5 mol, relative to 1 mol of 2-methyl-2,6-heptadienol (6). It is in the range of moles.

Examples of the base used for the reaction with the alkaline sulfonylating agent include diethylamine, triethylamine, diisopropylethylamine, tri-n-propylamine, tri-n-butylamine, diazabicyclononen (DBN), diazabicycloundecene (DBU), and the like. Amines such as N-methylmorpholin and N, N-dimethylaniline; pyridines such as pyridine, methylethylpyridine, lutidine and N, N-dimethyl-4-aminopyridine; organic bases such as imidazole and pyrazoles; water Alkaline or alkaline earth metal hydroxides such as lithium oxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and barium hydroxide; sodium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate And alkali metals such as barium carbonate or carbonates of alkaline earth metals; metal alkoxides such as sodium = ethoxydo; alkali metal amides such as sodium = amide and lithium = amide; and hydrogenation of sodium hydride and lithium hydride and the like. Examples thereof include inorganic bases such as alkali metals, and preferred examples thereof include pyridine and triethylamine.
The amount of the base used is preferably 1 to 500 mol with respect to 1 mol of 2-methyl-2,6-heptadienol (6).

As the solvent used for the reaction with the alcan sulfonylating agent, the above base may be used as a solvent, or chlorine-based solvents such as methylene chloride, chloroform and trichloroethylene; hexane, heptane, benzene, toluene, xylene and cumene and the like. Hydrocarbons; diethyl = ether, dibutyl = ether, diethylene glycol = diethyl = ether, diethylene glycol = dimethyl = ether, ethers such as tetrahydrofuran and 1,4-dioxane; nitriles such as acetonitrile; acetone and 2-butanone, etc. Examples include ketones; esters such as ethyl acetate and n-butyl acetate; and aprotonic polar solvents such as N, N-dimethylformamide, dimethyl = sulfoxide and hexamethylphosphoric = triamide.
The solvent may be used alone or in combination of two or more, if necessary. Further, as the solvent, a commercially available solvent can be used.
The amount of the solvent used is preferably 10 to 1,000,000 g with respect to 1 mol of 2-methyl-2,6-heptadienol (6).

As the reaction temperature in the reaction with the alcan sulfonyl agent, an appropriate reaction temperature can be selected depending on the type of the alcan sulfonyl agent used and / or the reaction conditions, but in general, the boiling temperature of the solvent is preferably −50 ° C. -20 ° C to room temperature (5 ° C to 35 ° C) is more preferable.
The reaction time in the reaction with the alkane sulfonylating agent can be set arbitrarily, but it is preferable to use gas chromatography (GC) or thin layer chromatography (TLC) to track and optimize the progress of the reaction, usually for 5 minutes. ~ 240 hours is preferable.

When the leaving group X is an arene sulfonyloxy group, a conversion reaction of the hydroxyl group of 2-methyl-2,6-heptadienol (6) is carried out using an arene sulfonyl agent. In the reaction with the arene sulfonylating agent, 2-methyl-2,6-heptadienol (6) is added to the arene sulfonylating agent, and then to the base, or vice versa, in a single solution or in a mixed solvent of two or more kinds. A method of reacting with an arene sulfonylating agent and a base at the same time can be applied.
Examples of the arene sulfonyl agent include allene sulfonic acid anhydrides such as benzenesulfonic acid anhydride and p-toluenesulfonic acid anhydride; and allene sulfonic acid halides such as benzenesulfonyl = chloride and p-toluenesulfonyl = chloride. Can be mentioned.
The amount of the arene sulfonylating agent used is preferably 1 to 500 mol, more preferably 1 to 50 mol, still more preferably 1 to 5 mol, relative to 1 mol of 2-methyl-2,6-heptadienol (6). It is in the range of moles.

The bases used for the reaction with the arene sulfonylating agent, the amount of the base used, the solvent, the amount of the solvent used, the reaction time and the reaction temperature were 2-methyl-2,6-heptadienol (6) and the alcan sulfonylating agent. It is the same as the base, the amount of the base used, the solvent, the amount of the solvent used, the reaction time and the reaction temperature described in the reaction with.

When the leaving group X is a halogen atom, a halogenating agent is used to carry out a conversion reaction of the hydroxyl group of 2-methyl-2,6-heptadienol (6). In the reaction with the halogenating agent, 2-methyl-2,6-heptadienol (6) is subjected to the halogenating agent, and then the base, or vice versa, or halogenation in a single solvent or a mixed solvent of two or more kinds. The agent and the base are reacted at the same time.
Examples of the halogenating agent include thionyl halides such as thionyl chloride and thionyl bromide; phosphorus halide compounds such as phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride and phosphorus pentabromide; phosphorus oxychloride and phosphorus oxybromated. Oxyhalogenated phosphorus compounds such as; and aromatic halogenated phosphorus compounds such as dichlorotriphenylphosphoran and dibromotriphenylphosphoran.
Further, when a sulfonic acid halide such as methanesulfonyl = chloride, ethanesulfonyl = chloride and trifluoromethanesulfonyl = chloride is used instead of the above-mentioned halogenating agent, 2-methyl-2,6-heptadienol (6). The hydroxyl group is sulfonylated, after which the sulfonyloxy group can be converted to the halogen atom corresponding to the sulfonic acid halide by heating as needed.
Further, even when the hydroxyl group is sulfonylated with a sulfonyl agent other than the above sulfonic acid halide, or when the hydroxyl group is halogenated with the above halogenating agent, after that, a halogen such as a metal halide or a quaternary onium salt is used. Agents can be added to convert to the corresponding halides.
Examples of the metal halide include lithium bromide, sodium bromide, potassium bromide, lithium iodide, sodium iodide, potassium iodide and the like.
Examples of the quaternary onium salt include tetraethylammonium = bromide, tetrabutylammonium = bromide, tetrabutylphosphonium = bromide, tetraethylammonium = iodide, tetrabutylammonium = iodide, tetrabutylphosphonium = iodide and the like.
The amount of the halogenating agent used is preferably 1 to 500 mol, more preferably 1 to 50 mol, still more preferably 1 to 5 mol, relative to 1 mol of 2-methyl-2,6-heptadienol (6). Is the range of.

The base used for the reaction with the halogenating agent, the amount of the base used, the solvent, the amount of the solvent used, the reaction time and the reaction temperature were 2-methyl-2,6-heptadienol (6) and the alcan sulfonylating agent. It is the same as the base, the amount of the base used, the solvent, the amount of the solvent used, the reaction time and the reaction temperature described in the above reaction.

When the 2-methyl-2,6-heptadiene compound (1) having a leaving group X at the 1-position obtained in the hydroxylation conversion reaction has sufficient purity, it remains as a crude product and is as follows. It may be used in the above steps, or it may be appropriately selected and purified from the purification methods in ordinary organic synthesis such as distillation or various chromatographies, and distillation is particularly preferable from the viewpoint of industrial economic efficiency.

In the above steps A to D as one embodiment of the present invention, in the step C, the 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position is deprotected. By subjecting to the reaction, 6-isopropenyl-3-methyl-9-decenol (4) was obtained, and then in step D, 6-isopropenyl-3-methyl-9-decenol (4) was acetylated to obtain acetylation. The target compound, 6-isopropenyl-3-methyl-9-decenyl-acetate (5), can be obtained. As shown in the following chemical reaction formula, the present inventors used an acetylating agent under deprotection reaction conditions instead of the above steps C and D, without going through the above steps D. It was further found that -isopropenyl-3-methyl-9-decenyl-acetate (5) can be obtained. That is, it is considered that an acetylation reaction occurs following the deprotection reaction by using an acetylating agent under the deprotection reaction conditions. Therefore, 6-isopropenyl-3-methyl-9-decenyl = acetate (5). ) Can be obtained in one step. Whether or not an acetylation reaction occurs following the deprotection reaction depends on, for example, the type of protecting group of the 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position. do. Examples of the protecting group include those that can be deprotected with an acid, and specific examples thereof include an oxyalkyl group such as a 1-ethoxyethyl group. For example, inorganic acids such as hydrochloric acid, hydrobromic acid, nitrate and sulfuric acid; organic acids such as trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid; aluminum trichloride, aluminum = ethoxydo, Aluminum = isopropoxide, aluminum oxide, boron trifluoride, boron trichloride, boron tribromide, magnesium chloride, magnesium bromide, magnesium iodide, zinc chloride, zinc bromide, zinc iodide, tin tetrachloride, quaternary Tin bromide, dibutyl tin dichloride, dibutyl tin = dimethoxydo, dibutyl tin = oxide, titanium tetrachloride, titanium tetrabromide, titanium (IV) = methoxyd, titanium (IV) = ethoxydo, titanium (IV) = isopropoxide And Lewis acids such as titanium oxide (IV); and the above deprotection by adding an acetylating agent such as anhydrous acetic acid to the reaction system in the presence of an acid catalyst such as sodium acetate and metal acetate salts such as potassium acetate. Following the reaction, the acetylation reaction can proceed in one step. Preferably, by adding an acetylating agent such as acetic anhydride to the reaction system in the presence of an acid catalyst such as p-toluenesulfonic acid, the acetylation reaction can be allowed to proceed in one step following the deprotection reaction. Yes (see Example 19 below).

As described above, an efficient and industrial method for producing 6-isopropenyl-3-methyl-9-decenyl-acetate (5), and its useful intermediate 2-methyl-2,6-heptadiene compound ( 1') and 2-methyl-2,6-heptadiene compound (1 ″) are provided.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples.
In the following, unless otherwise specified, "purity" indicates the area percentage obtained by gas chromatography (GC) analysis, and "production ratio" indicates the relative ratio of the area percentage obtained by GC analysis. .. The "yield" indicates the yield calculated based on the area percentage obtained by the GC analysis.
Samples for spectral measurement of compounds are optionally obtained by purifying the crude product.
In each example, reaction monitoring and yield calculation were performed according to the following GC conditions.
GC conditions: GC: Shimadzu Capillary Gas Chromatograph GC-2014, Column: DB-5,0.25 mmx0.25 mmφx30 m, Carrier gas: He (1.55 mL / min), Detector: FID, Column temperature: 100 ° C. 10 ° C. / Minute temperature rise 230 ° C.
In each example, reaction monitoring may have been performed by thin layer chromatography (TLC). The solvent in parentheses shown in the TLC indicates the elution solvent or developing solvent used, and the ratio represents the volume ratio.
The yield was calculated according to the following formula, taking into account the purity of the raw material and the product (% GC).
Yield (%) = {[(Weight of product obtained by reaction x% GC) / Molecular weight of product]
÷ [(Weight of starting material in reaction x% GC) / Molecular weight of starting material]} x 100
The "crude yield" means a yield calculated without purification.

Example 1
Production of 2-Methyl-2,6-Heptadienyl = Acetate (1': X'= OAc)

In a nitrogen atmosphere, 2-methyl-2,6-heptadienol (6) (3.00 g: 0.021 mol), pyridine (5.81 g: 0.73 mol), acetic anhydride (Ac ₂ ) were placed in the reactor. O) (3.59 g: 0.029 mol) and acetonitrile (MeCN) (10 ml) were charged and stirred at room temperature for 14 hours and 40 minutes. Then, pure water (20 g) and hexane (20 g) were added, and the mixture was stirred for 30 minutes, and then the organic layer was separated. The separated organic layer is post-treated by conventional washing, drying and concentration to give a crude product (3.60 g) of 2-methyl-2,6-heptadienyl = acetate (1': X'= OAc). ) Was obtained. The crude yield was 90.45%.

The spectral data of 2-methyl-2,6-heptadienyl = acetate (1': X'= OAc) obtained above is shown below.
IR (D-ATR): ν = 3078,2975,2922,1741,1641,1440,1367,1233,1023,984,957,913,634,607,560cm ^-1 .
^{1 1} H-NMR (500 MHz, CDCl ₃ ): δ = 1.74 (3H, s-like), 2.06 (3H, s), 2.07-2.19 (4H, m), 4.57 ( 2H, s), 4.94-5.03 (2H, m), 5.39 (1H, t, J = 7.6Hz), 5.75-5.83 (1H, m) ppm.
¹³ C-NMR (125 MHz, CDCl ₃ ): δ = 20.90, 21.37, 27.09, 33.75, 63.12, 113.89, 129.98, 130.15, 137.93, 171 .08 ppm.
GC-MS (EI, 70eV): 27,43,55,67,79,93,108,126,140,153,168.

Example 2
Production of 2-methyl-2,6-heptadienyl = isobutyrate (1': X'= OC (= O) CH (CH ₃ ) ₂ )

In a nitrogen atmosphere, 2-methyl-2,6-heptadienol (6) (3.00 g: 0.017 mol), pyridine (6.64 g: 0.84 mol), isobutyric acid anhydride ( 5.32 g: 0.034 mol) and acetonitrile (MeCN) (10 ml) were charged and stirred at room temperature for 7 hours. Then, pure water (20 g) and hexane (20 g) were added, and the mixture was stirred for 30 minutes, and then the organic layer was separated. The separated organic layer is post-treated by conventional washing, drying and concentration to 2-methyl-2,6-heptadienyl = isobutyrate (1': X'= OC (= O) CH (CH ₃ ) ₂ ). ) Was obtained (4.62 g). The crude yield was 100%.

The spectral data of 2-methyl-2,6-heptadienyl = isobutyrate (1': X'= OC (= O) CH (CH ₃ ) ₂ ) obtained above is shown below.
IR (D-ATR): ν = 3078, 2975, 2938, 2879, 1814, 1736, 1641, 1471, 1388, 1354, 1252, 1190, 1154, 1117, 1068, 1021, 965, 913, 756, 642 cm ^-1 ..
^{1 1} H-NMR (500 MHz, CDCl ₃ ): δ = 1.16 (6H, d, J = 7.3 Hz), 1.73 (3H, s-like), 2.06-2.20 (4H, m) ), 2.51-2.59 (1H, m), 4.57 (2H, s), 4.94-5.03 (2H, m), 5.39 (1H, t, J = 7.5Hz) ), 5.75-5.83 (1H, m) ppm.
¹³ C-NMR (125 MHz, CDCl ₃ ): δ = 18.24, 18.97, 21.30, 27.09, 33.79, 34.02, 62.96, 114.86, 129.66, 130 .41, 137.98, 177.10 ppm.
GC-MS (EI, 70eV): 27,43,55,71,81,93,108,126,142,155,168,181,196.

Example 3
Production of 2-Methyl-2,6-Heptadienyl-bromid (1: X = Br)

Under a nitrogen atmosphere, triphenylphosphine (PPh ₃ ) (7.73 g: 0.029 mol) and acetonitrile (MeCN) (16.8 g) were charged in the reactor and cooled to an internal temperature of −5 to 5 ° C. Then, while maintaining the internal temperature at -5 to 5 ° C., bromine (Br ₂ ) (4.50 g: 0.028 mol) was added dropwise to the reactor over 15 minutes, and the internal temperature was -5 to 10 ° C. Was stirred for 3 hours. Then, while keeping the internal temperature at -5 to 10 ° C., 2-methyl-2,6-heptadienol (6) (3.00 g: 0.021 mol) and triethylamine (Et ₃ N) (Et 3 N) ( The mixed solution with 2.97 g (0.029 mol) was added dropwise over 30 minutes, and the mixture was stirred at an internal temperature of −5 to 10 ° C. for 1 hour, and then stirred at room temperature for 14 hours. Then, pure water (20 g) and hexane (20 g) were added to the reactor, and the mixture was stirred for 30 minutes, and then the organic layer was separated. The separated organic layer is post-treated by conventional washing, drying and concentration to give a crude product (3.33 g) of 2-methyl-2,6-heptadienyl-bromid (1: X = Br). rice field. The crude yield was 71.43%.

The spectral data of 2-methyl-2,6-heptadienyl = bromide (1: X = Br) obtained above is shown below.
IR (D-ATR): ν = 3078, 3028, 2975, 2919, 2856, 2735, 1830, 1739, 1641, 1438, 1379, 1205, 1119, 1065,992,913,847,811,769,721,696 , 636,542 cm ^-1 .
^{1 1} H-NMR (500 MHz, CDCl ₃ ): δ = 1.84 (3H, s-like), 2.07-2.19 (4H, m), 3.98 (2H, s), 4.97- 5.03 (2H, m), 5.39 (1H, t-like, J = 6.8Hz), 5.75-5.85 (1H, m) ppm.
¹³ C-NMR (125 MHz, CDCl ₃ ): δ = 21.84, 27.39, 32.24, 33.24, 115.06, 130.79, 131.92, 137.83 ppm.
GC-MS (EI, 70eV): 27,41,55,67,79,93,109,119,133,147,162,175,188.

Example 4
Production of 2-Methyl-2,6-Heptadienyl-Chloride (1: X = Cl)

2-Methyl-2,6-heptadienol (6) (8.00 g: 0.056 mol), pyridine (7.97 g: 0.101 mol) and dimethylformamide (DMF) were placed in the reactor under a nitrogen atmosphere. (10 ml) was charged, cooled to an internal temperature of −5 to 5 ° C., and stirred for 15 minutes. Then, methanesulfonyl chloride (MsCl) (8.98 g: 0.078 mol) was added dropwise to the reactor over 10 minutes while maintaining the internal temperature at −5 to 5 ° C. After completion of the dropping, the mixture was stirred at an internal temperature of −5 to 5 ° C. for 1 hour, and then at room temperature for 12 hours. Then, pure water (20 g) and hexane (20 g) were added to the reactor, and the mixture was stirred for 30 minutes, and then the organic layer was separated. The separated organic layer is post-treated by conventional washing, drying and concentration to obtain a crude product (4.36 g) of 2-methyl-2,6-heptadienyl chloride (1: X = Cl). Obtained. The crude yield was 48.21%.

The spectral data of 2-methyl-2,6-heptadienyl-chloride (1: X = Cl) obtained above is shown below.
IR (D-ATR): ν = 3078, 2975, 2934, 2921, 284, 2735, 1831, 1728, 1641, 1443, 1380, 1257, 1119, 1077, 992, 913,850, 815, 700, 641 cm ^-1 ..
^{1 1} H-NMR (500 MHz, CDCl ₃ ): δ = 1.83 (3H, s-like), 2.07-2-21 (4H, m), 4.06 (2H, s), 4.97- 5.03 (2H, m), 5.39 (1H, t-like, J = 7.2Hz), 5.75-5.85 (1H, m) ppm.
¹³ C-NMR (125 MHz, CDCl ₃ ): δ = 21.84, 27.25, 32.24, 33.55, 115.04, 130.39, 131.71, 137.84 ppm.
GC-MS (EI, 70eV): 27,41,53,67,75,87,95,103,116,129,144.

Example 5
Preparation of 3-Methyl-5- (Tetrahydropyran-2-yloxy) Pentyl Magnesium-Chloride (2: M = MgZ ¹ , Z ¹ = Cl, R = 2-Tetrahydropyranyl Group (THP)), and Tetrahydro-2 -Production of -(6-isopropenyl-3-methyl-9-decenyloxy) -2H-pyran (3: R = THP)

Under a nitrogen atmosphere, the reactor was charged with magnesium (0.19 g: 0.0078 mol) and tetrahydrofuran (THF) (0.7 g), heated to 60 ° C., and stirred for 15 minutes. Then, in the reactor, a mixed solution of tetrahydro-2- (5-chloro-3-methylpentyloxy-2H-pyran (1.7 g: 0.007 mol)) and tetrahydrofuran (THF) (1.5 g) was added. The solution was added dropwise over 30 minutes. After the addition was completed, the mixture was stirred at an internal temperature of 50 to 60 ° C. for 3 hours to obtain 3-methyl-5- (tetrahydropyran-2-yloxy) pentylmagnesium = chloride (2: M = MgZ). ¹ , Z ¹ = Cl, R = THF) were prepared, and the resulting 3-methyl-5- (tetrahydropyran-2-yloxy) pentylmagnesium = chloride (2: M = MgZ ¹ , Z ¹ = Cl) was prepared. , R = THF) was cooled to room temperature.

Copper iodide (1) (CuI) (0.002 g), triethyl phosphate (P (OEt) ₃ ) (0.003 g), tetrahydrofuran (THF) (4 ml) and in another reactor under a nitrogen atmosphere. 2-Methyl-2,6-heptadienyl-bromid (1: X = Br) (0.80 g: 0.004 mol) obtained according to Example 3 was added, stirred, and cooled to −78 ° C. to −50 ° C. bottom. Then, in the other reactor, the total amount of 3-methyl-5- (tetrahydropyran-2-yloxy) pentylmagnesium = chloride (2: M = MgZ ¹ , Z ¹ = Cl, R = THP) prepared above. Was added dropwise at −50 ° C. or lower over 30 minutes. After completion of the dropping, the mixture was stirred for 3 hours, an aqueous solution of pure water (10 g) and ammonium chloride (1 g) was added to the other reactor, and the mixture was stirred for 30 minutes, after which the organic layer was separated. The separated organic layer is post-treated by conventional washing, drying and concentration to tetrahydro-2- (6-isopropenyl-3-methyl-9-decenyloxy) -2H-pyran (3: R = THP). Crude product (1.24 g: 0.04 mol) was obtained. The crude yield was 10.00%. Tetrahydro-2- (6-isopropenyl-3-methyl-9-decenyloxy) -2H-pyran (3: R = THP) and tetrahydro-2- (3,7-dimethyl-7,11-dodecadienyloxy) The production ratio with -2H-pyran was 72:28.

Spectral data of the crude product of tetrahydro-2- (6-isopropenyl-3-methyl-9-decenyloxy) -2H-pyran (3: R = THP) obtained above are shown below.
IR (D-ATR): ν = 3072, 2928, 2870, 1642, 1453, 1441, 1376, 1353, 1323, 1260, 1201, 1184, 1136, 1122, 1078, 1035, 991, 970, 908, 888, 870 , 815 cm ^-1 .
^{1 1} H-NMR (500 MHz, CDCl ₃ ): δ = 0.86-0.89 (3H, m), 1.00-1.08 (1H, m), 1.16-2.10 (20H, m) ), 3.34-3.43 (1H, m), 3.47-3.53 (1H, m), 3.72-3.80 (1H, m), 3.83-3.89 (1H). , M), 4.55-4.57 (1H, m), 4.63-4.65 (1H, m), 4.72-4.73 (1H, m), 4.90-5.02 (2H, m), 5.75-5.83 (1H, m) ppm.
¹³ C-NMR (125MHz, CDCl ₃ ): δ = 17.68, 17.70, 17.79, 19.49, 19.62, 19.64, 19.73, 19.80, 19.92, 25 .42, 25.48, 29.83, 30.03, 30.11, 30.53, 30.56, 30.63, 30.66, 30.77, 31.66, 32.56, 32.71 , 34.70, 34.75, 34.78, 34.88, 36.38, 36.47, 36.82, 36.86, 46.95, 47.00, 47.07, 47.10, 62 .28, 65.82, 65.86, 65.98, 94.61, 98.73, 98.91, 111.64, 111.73, 114.13, 139.08, 147.20, 147.32 ppm ..
GC-MS (EI, 70eV): 27,41,55,69,85,109,123,149,163,182,196,210,224,240,261,276,294.

Example 6
Preparation of 3-Methyl-5- (Tetrahydropyran-2-yloxy) Pentyl Magnesium-Chloride (2: M = MgZ ¹ , Z ¹ = Cl, R = THP), and Tetrahydro-2- (6-isopropenyl-3) Production of -Methyl-9-decenyloxy) -2H-pyran (3: R = THP)

Under a nitrogen atmosphere, the reactor was charged with magnesium (0.26 g: 0.011 mol) and tetrahydrofuran (THF) (1 g), heated to 60 ° C., and stirred for 10 minutes. Then, a mixed solution of tetrahydro-2- (5-chloro-3-methylpentyloxy-2H-pyran (2.21 g: 0.01 mol) and tetrahydrofuran (THF) (2 g)) was placed in the reactor for 10 minutes. 3-Methyl-5- (tetrahydropyran-2-yloxy) pentylmagnesium = chloride (2: M = MgZ ¹ , by stirring at an internal temperature of 50 to 60 ° C. for 3 hours after the completion of the dropping. Z ¹ = Cl, R = THF) was prepared, and the resulting 3-methyl-5- (tetrahydropyran-2-yloxy) pentylmagnesium = chloride (2: M = MgZ ¹ , Z ¹ = Cl, R) was prepared. = THF) was cooled to −5 to 0 ° C.

A mixed solution of copper (I) cyanide (CuCN) (0.90 g), lithium bromide (LiBr) (1.74 g) and tetrahydrofuran (THF) (10 ml) was added dropwise to the reactor over 10 minutes. Then, the temperature was cooled to −78 to −50 ° C. Then, the reactor was mixed with 2-methyl-2,6-heptadienyl-chloride (1: X = Cl) (0.50 g: 0.002 mol) obtained according to Example 4 and THF (10 ml). The solution was added dropwise over 20 minutes. After completion of the dropping, the mixture was stirred at −78 ° C. to −50 ° C. for 1 hour. Then, a mixture of pure water (20 g) and ammonium chloride (2 g) was added to the reactor, and the mixture was stirred for 30 minutes, and then the organic layer was separated. The separated organic layer is post-treated by conventional washing, drying and concentration to tetrahydro-2- (6-isopropenyl-3-methyl-9-decenyloxy) -2H-pyran (3: R = THP). (1.86 g: 0.003 mol) was obtained. The crude yield was 100%. Tetrahydro-2- (6-isopropenyl-3-methyl-9-decenyloxy) -2H-pyran (3: R = THP) and tetrahydro-2- (3,7-dimethyl-7,11-dodecadienyloxy) The production ratio with -2H-pyran was 99: 1.

The spectral data of the obtained tetrahydro-2- (6-isopropenyl-3-methyl-9-decenyloxy) -2H-pyran (3: R = THP) is the same as the spectral data obtained in Example 5. there were.

Example 7
Preparation of 3-Methyl-5- (Tetrahydropyran-2-yloxy) Pentyl Magnesium-Chloride (2: M = MgZ ¹ , Z ¹ = Cl, R = THP), and Tetrahydro-2- (6-isopropenyl-3) Production of -Methyl-9-decenyloxy) -2H-pyran (3: R = THP)

Under a nitrogen atmosphere, the reactor was charged with magnesium (0.26 g: 0.01 mol) and tetrahydrofuran (THF) (1 g), heated to 60 ° C., and stirred for 15 minutes. Then, a mixed solution of tetrahydro-2- (5-chloro-3-methylpentyloxy-2H-pyran (2.21 g: 0.01 mol) and tetrahydrofuran (THF) (2 g)) was placed in the reactor for 30 minutes. 3-Methyl-5- (tetrahydropyran-2-yloxy) pentylmagnesium = chloride (2: M = MgZ ¹ , by stirring at an internal temperature of 50 to 60 ° C. for 3 hours after the completion of the dropping. Z ¹ = Cl, R = THF) was prepared, and the resulting 3-methyl-5- (tetrahydropyran-2-yloxy) pentylmagnesium = chloride (2: M = MgZ ¹ , Z ¹ = Cl, R) was prepared. = THF) was cooled to room temperature.

Obtained according to Example 4 with copper (I) bromide (CuBr) (1.29 g), lithium bromide (LiBr) (1.56 g), tetrahydrofuran (THF) (10 ml) in another reactor under a nitrogen atmosphere. The obtained 2-methyl-2,6-heptadienyl-chloride (1: X = Cl) (0.50 g: 0.003 mol) was added, stirred, and cooled to −78 ° C. to −50 ° C. Then, in the other reactor, the total amount of 3-methyl-5- (tetrahydropyran-2-yloxy) pentylmagnesium = chloride (2: M = MgZ ¹ , Z ¹ = Cl, R = THP) prepared above. Was added dropwise at −50 ° C. or lower over 50 minutes. After completion of the dropping, the mixture was stirred for 3 hours, and a mixture of pure water (20 g) and ammonium chloride (2 g) was added to the other reactor, and the mixture was further stirred for 30 minutes, and then the organic layer was separated. The separated organic layer is post-treated by conventional washing, drying and concentration to tetrahydro-2- (6-isopropenyl-3-methyl-9-decenyloxy) -2H-pyran (3: R = THP). (2.13 g: 0.004 mol) was obtained. The crude yield was 100%. Tetrahydro-2- (6-isopropenyl-3-methyl-9-decenyloxy) -2H-pyran (3: R = THP) and tetrahydro-2- (3,7-dimethyl-7,11-dodecadienyloxy) The production ratio with -2H-pyran was 99: 1.

The spectral data of the obtained tetrahydro-2- (6-isopropenyl-3-methyl-9-decenyloxy) -2H-pyran (3: R = THP) is the same as the spectral data obtained in Example 5. there were.

Example 8
Preparation of 3-methyl-5- (tetrahydropyran-2-yloxy) pentylmagnesium chloride (2: M = MgZ ¹ , Z ¹ = Cl, R = THP) and tetrahydro-2- (6-isopropenyl-) Production of 3-Methyl-9-decenyloxy) -2H-pyran (3: R = THP)

Under a nitrogen atmosphere, the reactor was charged with magnesium (0.26 g: 0.01 mol) and tetrahydrofuran (THF) (1 g), heated to 60 ° C., and stirred for 10 minutes. Then, a mixed solution of tetrahydro-2- (5-chloro-3-methylpentyloxy-2H-pyran (2.21 g: 0.01 mol) and tetrahydrofuran (THF) (2 g)) was added to the reactor for 5 minutes. 3-Methyl-5- (tetrahydropyran-2-yloxy) pentylmagnesium = chloride (2: M = MgZ ¹ , by stirring at an internal temperature of 50 to 60 ° C. for 3 hours after the completion of the dropping. Z ¹ = Cl, R = THF) was prepared, and the resulting 3-methyl-5- (tetrahydropyran-2-yloxy) pentylmagnesium = chloride (2: M = MgZ ¹ , Z ¹ = Cl, R) was prepared. = THF) was cooled to room temperature.

Titanium tetraisopropoxide (Ti (OiPr) ₄ ) (2.89 g) and tetrahydrofuran (THF) (10 ml) were added to another reactor under a nitrogen atmosphere, and the mixture was cooled to −10 to −5 ° C. Then, the total amount of 3-methyl-5- (tetrahydropyran-2-yloxy) pentylmagnesium = chloride (2) prepared above was added dropwise at −5 ° C. or lower over 15 minutes. After completion of the dropping, a mixed solution of copper (I) iodide (CuI) (0.10 g), lithium bromide (LiBr) (0.09 g) and THF (10 ml) was placed in the other reactor at -5 ° C or lower. It was dropped over 2 minutes. After completion of the dropping, 2-methyl-2,6-heptadienyl-chloride (1: X = Cl) (1.45 g: 0.009 mol) obtained according to Example 4 was added over 20 minutes at -5 ° C or lower. Dropped. After completion of the dropping, the mixture was stirred at −10 to −5 ° C. for 2 hours, and then further stirred at room temperature for 24 hours. Then, an aqueous solution of pure water (20 g) and ammonium chloride (2 g) was added to the other reactor, and the mixture was stirred for 30 minutes, and then the organic layer was separated. The separated organic layer is post-treated by conventional washing, drying and concentration to tetrahydro-2- (6-isopropenyl-3-methyl-9-decenyloxy) -2H-pyran (3: R = THP). (2.13 g: 0.004 mol) was obtained. The crude yield was 50.0%. Tetrahydro-2- (6-isopropenyl-3-methyl-9-decenyloxy) -2H-pyran (3: R = THP) and tetrahydro-2- (3,7-dimethyl-7,11-dodecadienyloxy) The production ratio with -2H-pyran was 94: 6.

The spectral data of the obtained tetrahydro-2- (6-isopropenyl-3-methyl-9-decenyloxy) -2H-pyran (3: R = THP) is the same as the spectral data obtained in Example 5. there were.

Example 9
Preparation of 3-Methyl-5- (Tetrahydropyran-2-yloxy) Pentyl Magnesium-Chloride (2: M = MgZ ¹ , Z ¹ = Cl, R = THP), and Tetrahydro-2- (6-isopropenyl-3) Production of -Methyl-9-decenyloxy) -2H-pyran (3: R = THP)

Under a nitrogen atmosphere, the reactor was charged with magnesium (0.087 g: 0.0035 mol) and tetrahydrofuran (THF) (0.3 g), heated to 60 ° C., and stirred for 5 minutes. Then, in the reactor, a mixed solution of tetrahydro-2- (5-chloro-3-methylpentyloxy-2H-pyran (0.74 g: 0.003 mol) and tetrahydrofuran (THF) (0.7 g)) was added. The solution was added dropwise over 15 minutes. After the addition was completed, the mixture was stirred at an internal temperature of 50 to 60 ° C. for 3 hours to obtain 3-methyl-5- (tetrahydropyran-2-yloxy) pentylmagnesium = chloride (2: M = MgZ). ¹ , Z ¹ = Cl, R = THF) were prepared, and the resulting 3-methyl-5- (tetrahydropyran-2-yloxy) pentylmagnesium = chloride (2: M = MgZ ¹ , Z ¹ = Cl) was prepared. , R = THF) was cooled to −5 to 5 ° C.

Zinc chloride (ZnCl ₂ ) (0.08 g), copper (II) chloride (CuCl ₂ ) (0.08 g) and lithium chloride (LiCl) (0.05 g) were added to the above reactor, and then Examples. A mixed solution of 2-methyl-2,6-heptadienyl-chloride (1: X = Cl) (0.50 g: 0.003 mol) obtained according to No. 4 and THF (10 ml) was added dropwise over 10 minutes. After completion of the dropping, the mixture is stirred at −5 to 5 ° C. for 5 hours, an aqueous solution of pure water (20 g) and ammonium chloride (2 g) is added to the reactor, and the mixture is stirred for 30 minutes, and then the organic layer is added. separated. The separated organic layer is post-treated by conventional washing, drying and concentration to tetrahydro-2- (6-isopropenyl-3-methyl-9-decenyloxy) -2H-pyran (3: R = THP). (1.86 g: 0.003 mol) was obtained. The crude yield was 50.0%. Tetrahydro-2- (6-isopropenyl-3-methyl-9-decenyloxy) -2H-pyran (3: R = THP) and tetrahydro-2- (3,7-dimethyl-7,11-dodecadienyloxy) The production ratio with -2H-pyran was 78:22.

The spectral data of the obtained tetrahydro-2- (6-isopropenyl-3-methyl-9-decenyloxy) -2H-pyran (3: R = THP) is the same as the spectral data obtained in Example 5. there were.

Example 10
Preparation of 5- (1-ethoxyethoxy) -3-methylpentylmagnesium = chloride (2: M = MgZ ¹ , Z ¹ = Cl, R = ethoxyethyl group (EE)), and tetrahydro-2- (6-iso) Production of propenyl-3-methyl-9-decenyloxy) -2H-pyran (3: R = EE)

Under a nitrogen atmosphere, the reactor was charged with magnesium (31.84 g: 1.31 mol) and tetrahydrofuran (THF) (126 g), heated to 60 ° C., and stirred for 40 minutes. Then, a mixed solution of 5-chloro-1- (1-ethoxyethoxy) -3-methylpentane (262.83 g: 1.26 mol) and tetrahydrofuran (THF) (252 g) was added to the reactor over 5 hours. Dropped. After completion of the dropping, the mixture was stirred at an internal temperature of 60 to 70 ° C. for 3 hours to obtain 5- (1-ethoxyethoxy) -3-methylpentylmagnesium = chloride (2: M = MgZ ¹ , Z ¹ = Cl, R =). EE) was prepared. Then, the obtained 5- (1-ethoxyethoxy) -3-methylpentylmagnesium = chloride (2: M = MgZ ¹ , Z ¹ = Cl, R = EE) was cooled to room temperature.

Copper (I) bromide (CuBr) (72.30 g), lithium chloride (LiCl) (42.73 g) and tetrahydrofuran (THF) (756 g) were added to another reactor under a nitrogen atmosphere, and at room temperature. The mixture was stirred for 15 minutes and then cooled to 0-10 ° C. Then, 2-methyl-2,6-heptadienyl-acetate (1': X'= OAc) (144.32 g: 0.84 mol) obtained according to Example 1 was added to the other reactor and stirred. Then, it was cooled to −5 ° C. to 5 ° C. Then, in the other reactor, the total amount of 5- (1-ethoxyethoxy) -3-methylpentylmagnesium = chloride (2: M = MgZ ¹ , Z ¹ = Cl, R = EE) obtained above was charged. The mixture was added dropwise at −5 ° C. to 5 ° C. over 11 hours and 35 minutes. After completion of the dropping, the mixture was stirred at 10 to 15 ° C. for 2 hours, and then further stirred at room temperature for 12 hours. Then, a mixture of pure water (630 g), ammonium chloride (63 g) and a 20 wt% hydrogen chloride aqueous solution (126 g) is added to the other reactor, and then n-hexane (500 ml) is added and stirred for 30 minutes. And then the organic layer was separated. The separated organic layer is post-treated by conventional washing, drying and concentration to give 1- (1-ethoxyethoxy) -6-isopropenyl-3-methyl-9-decene (3: R = EE). A crude product (320.21 g: 0.623 mol) was obtained. The crude yield was 74.17%. 1- (1-ethoxyethoxy) -6-isopropenyl-3-methyl-9-decene (3: R = EE) and 1- (1-ethoxyethoxy) -3,7-dimethyl-7,11-dodecadien ( The production ratio with 3': R = EE) was 96: 4.

The spectral data of 1- (1-ethoxyethoxy) -6-isopropenyl-3-methyl-9-decene (3: R = EE) obtained above are shown below.
IR (D-ATR): ν = 3074,2975,2928,2872,1643,1453,1377,1339,1134,1101,1087,1062,992,932,909,889,845,640,554 cm ^-1 .
^{1 1} H-NMR (500 MHz, CDCl ₃ ): δ = 0.86-0.88 (3H, m), 0.98-1.08 (1H, m), 1.16-1.69 (17H, m) ), 1.89-2.07 (3H, m), 3.38-3.50 (2H, m), 3.51-3.73 (2H, m), 4.64-4.69 (2H) , M), 4.72-4.74 (1H, m), 4.90-5.00 (2H, m), 5.75-5.83 (1H, m) ppm.
¹³ C-NMR (125 MHz, CDCl ₃ ): δ = 15.30, 17.69, 17.80, 19.47, 19.52, 19.76, 19.80, 19.85, 29.75, 29 .80, 29.94, 29.97, 30.52, 30.65, 31.66, 32.58, 32.73, 34.68, 34.73, 34.81, 34.86, 36.62 , 36.86, 36.98, 37.00, 46.99, 47.02, 47.11, 47.13, 60.58, 60.59, 63.40, 99.46, 99.50, 99 .52, 111.65, 111.74, 114.15, 139.06, 147.19, 147.31 ppm.
GC-MS (EI, 70eV): 29,45,59,73,95,109,123,149,163,177,194,208,237,267,282.

Example 11
Preparation of 5- (1-ethoxyethoxy) -3-methylpentylmagnesium = chloride (2: M = MgZ ¹ , Z ¹ = Cl, R = EE), and tetrahydro-2- (6-isopropenyl-3-methyl) Production of -9-decenyloxy) -2H-pyran (3: R = EE)

Under a nitrogen atmosphere, the reactor was charged with magnesium (3.49 g: 0.14 mol) and tetrahydrofuran (THF) (13.8 g), heated to 60 ° C., and stirred for 15 minutes. Next, 100 mixed solutions of 5-chloro-1- (1-ethoxyethoxy) -3-methylpentane (30.82 g: 0.14 mol) and tetrahydrofuran (THF) (27.6 g) were placed in the reactor. It was dropped over a minute. After completion of the dropping, the mixture was stirred at an internal temperature of 60 to 70 ° C. for 6 hours to obtain 5- (1-ethoxyethoxy) -3-methylpentylmagnesium = chloride (2: M = MgZ ¹ , Z ¹ = Cl, R =). EE) was prepared. Then, the obtained 5- (1-ethoxyethoxy) -3-methylpentylmagnesium = chloride (2: M = MgZ ¹ , Z ¹ = Cl, R = EE) was cooled to room temperature.

Copper (I) bromide (CuBr) (7.92 g), lithium chloride (LiCl) (4.68 g) and tetrahydrofuran (THF) (82.80 g) were added to another reactor under a nitrogen atmosphere, and at room temperature. After stirring for 100 minutes, the mixture was cooled to 10 ° C to 15 ° C. Then, 2-methyl-2,6-heptadienyl-isobutyrate (1: X = isobutyryloxy) (20.00 g: 0.09 mol) obtained according to Example 2 was added to the other reactor. Stirred. Then, in the other reactor, the total amount of 5- (1-ethoxyethoxy) -3-methylpentylmagnesium = chloride (2: M = MgZ ¹ , Z ¹ = Cl, R = EE) obtained above was charged. The mixture was added dropwise at 10 ° C to 15 ° C over 4 hours. After completion of the dropping, the mixture was stirred at 10 to 15 ° C. for 18 hours. Then, a mixture of pure water (41 g), ammonium chloride (4.1 g) and a 20 wt% hydrogen chloride aqueous solution (13.8 g) was added to the other reactor. Subsequently, n-hexane (138 g) was added, the mixture was stirred for 30 minutes, and then the organic layer was separated. The separated organic layer is post-treated by conventional washing, drying and concentration to give a crude product of 1- (1-ethoxyethoxy) -6-isopropenyl-3-methyl-9-decene (3). 36.04 g) was obtained. The crude yield was 54.44%. 1- (1-ethoxyethoxy) -6-isopropenyl-3-methyl-9-decene (2: M = MgZ ¹ , Z ¹ = Cl, R = EE) and 1- (1-ethoxyethoxy) -3, The production ratio with 7-dimethyl-7,11-dodecadien was 65:35.

Example 12
Production of 2-methyl-2,6-heptadienyl = methanesulfonate (1'': X'' = OMs) and 5- (1-ethoxyethoxy) -3-methylpentylmagnesium = chloride (2: M = MgZ) Preparation of ¹ , Z ¹ = Cl, R = EE) and production of tetrahydro-2- (6-isopropenyl-3-methyl-9-decenyloxy) -2H-pyran (3: R = EE).

Under a nitrogen atmosphere, the reactor was charged with 2-methyl-2,6-heptadienol (10.00 g: 0.074 mol), triethylamine (11.23 g: 0.111 mol) and toluene (65 g). The mixture was cooled to a temperature of −5 to 5 ° C. and stirred for 20 minutes. Then, while keeping the internal temperature at -5 to 5 ° C., a mixed solution of methanesulfonyl = chloride (MsCl) (12.71 g: 0.111 mol) and toluene (80 g) was sprinkled on the reactor for 90 minutes. And dropped. After completion of the dropping, the mixture was stirred at an internal temperature of −5 to 5 ° C. for 8 hours. Then, pure water (130 g) was added to the reactor, the mixture was stirred for 30 minutes, and then the organic layer was separated. The separated organic layer is post-treated by conventional washing, drying and filtration to toluene as a crude product of 2-methyl-2,6-heptadienyl = methanesulfonate (1 ″: X ″ = OMs). A solution (190.97 g) was obtained.

The Rf values and spectral data of the thin layer chromatography of the crude product of 2-methyl-2,6-heptadienyl = methanesulfonate (1'': X'' = OMs) obtained above are shown below.
Thin layer chromatography (TLC): Rf = 0.19 (hexane: ethyl acetate = 10: 1).
^{1 1} H-NMR (500 MHz, CDCl ₃ ): δ = 1.83 (3H, s-like), 2.11-2.25 (4H, m), 3.00 (3H, s), 4.75 ( 2H, s), 4.98-5.09 (2H, m), 5.54 (1H, t-like, J = 7.3Hz), 5.75-5.84 (1H, m) ppm.
GC-MS (EI, 70eV): 27,41,55,67,79,93,108,121,135,150,163,176,204.

Under a nitrogen atmosphere, the reactor was charged with magnesium (2.96 g: 0.12 mol) and tetrahydrofuran (THF) (11.7 g), heated to 60 ° C., and stirred for 10 minutes. Then, a mixed solution of 5-chloro-1- (1-ethoxyethoxy) -3-methylpentane (26.13 g: 0.12 mol) and tetrahydrofuran (THF) (23.4 g) was added to the reactor for 115 minutes. Dropped over. After completion of the dropping, the mixture was stirred at an internal temperature of 60 to 70 ° C. for 2 hours to obtain 5- (1-ethoxyethoxy) -3-methylpentylmagnesium = chloride (2: M = MgZ ¹ , Z ¹ = Cl, R =). EE) was prepared. Then, the obtained 5- (1-ethoxyethoxy) -3-methylpentylmagnesium = chloride (2: M = MgZ ¹ , Z ¹ = Cl, R = EE) was cooled to room temperature.

Copper (I) bromide (CuBr) (5.59 g), lithium chloride (LiCl) (3.31 g) and tetrahydrofuran (THF) (35.10 g) were added to another reactor under a nitrogen atmosphere, and at room temperature. After stirring for 90 minutes, the mixture was cooled to 10 ° C to 15 ° C. Then, a toluene solution (100.00 g) of a crude product of 2-methyl-2,6-heptadienyl = methanesulfonate (1: X = OMs) obtained above was added to the other reactor and stirred. .. Then, in the other reactor, the total amount of 5- (1-ethoxyethoxy) -3-methylpentylmagnesium = chloride (2: M = MgZ ¹ , Z ¹ = Cl, R = EE) obtained above was charged. The mixture was added dropwise at −5 ° C. to 5 ° C. over 3 hours. After completion of the dropping, the mixture was stirred at 10 to 15 ° C. for 14 hours. Then, a mixture of pure water (100 g), ammonium chloride (4 g) and a 20 wt% hydrogen chloride aqueous solution (4 g) was added to the other reactor. Subsequently, n-hexane (100 g) was added and stirred for 30 minutes, after which the organic layer was separated. The separated organic layer is post-treated by conventional washing, drying and concentration to give 1- (1-ethoxyethoxy) -6-isopropenyl-3-methyl-9-decene (3: R = EE). A crude product (21.55 g) was obtained. The crude yield from 2-methyl-2,6-heptadienol was 30.77%. With 1- (1-ethoxyethoxy) -6-isopropenyl-3-methyl-9-decene (3: R = EE) and 1- (1-ethoxyethoxy) -3,7-dimethyl-7,11-dodecadien The production ratio of was 63:37.

Example 13
Preparation of 2-methyl-2,6-heptadienyl = p-toluenesulfonate (1 ″: X'' = p-toluenesulfonyloxy groups (OTs)) and 5- (1-ethoxyethoxy) -3-methyl Preparation of pentylmagnesium = chloride (2: M = MgZ ¹ , Z ¹ = Cl, R = EE) and tetrahydro-2- (6-isopropenyl-3-methyl-9-decenyloxy) -2H-pyran (3) : R = EE)

Under a nitrogen atmosphere, the reactor was charged with 2-methyl-2,6-heptadienol (10.00 g: 0.074 mol), triethylamine (11.23 g: 0.111 mol) and toluene (65 g). The mixture was cooled to a temperature of −5 to 5 ° C. and stirred for 50 minutes. Then, while keeping the internal temperature at -5 to 5 ° C., a mixed solution of p-toluenesulfonyl = chloride (TsCl) (21.16 g: 0.111 mol) and toluene (80 g) was added to the reactor for 90 minutes. Dropped over. After completion of the dropping, the mixture was stirred at an internal temperature of −5 to 5 ° C. for 7 hours. Then, pure water (130 g) was added to the reactor, the mixture was stirred for 30 minutes, and then the organic layer was separated. The separated organic layer is post-treated by conventional washing, drying and filtration to produce a crude product of 2-methyl-2,6-heptadienyl = p-toluenesulfonate (1 ″: X'' = OTs). Toluene solution (185.69 g) was obtained.

The Rf values and spectral data of the crude product of 2-methyl-2,6-heptadienyl = p-toluenesulfonate (1 ″: X ″ = OTs) obtained above are shown below.
Thin layer chromatography (TLC): Rf = 0.21 (hexane: ethyl acetate = 10: 1).
^{1 1} H-NMR (500 MHz, CDCl ₃ ): δ = 1.70 (3H, s-like), 2.00-2.08 (4H, m), 2.46 (3H, s), 4.55 ( 2H, s), 4.96-5.01 (2H, m), 5.41-5.44 (1H, m), 5.69-5.78 (1H, m), 7.35 (2H, 2H,) d, J = 8.0 Hz), 7.82 (2H, d, J = 8.4 Hz) ppm.

Under a nitrogen atmosphere, the reactor was charged with magnesium (3.03 g: 0.12 mol) and tetrahydrofuran (THF) (12.0 g), heated to 60 ° C., and stirred for 10 minutes. Then, a mixed solution of 5-chloro-1- (1-ethoxyethoxy) -3-methylpentane (2,6.80 g: 0.12 mol) and tetrahydrofuran (THF) (24.0 g) was placed in the reactor. It was added dropwise over 120 minutes. After completion of the dropping, the mixture was stirred at an internal temperature of 60 to 70 ° C. for 2 hours to obtain 5- (1-ethoxyethoxy) -3-methylpentylmagnesium = chloride (2: M = MgZ ¹ , Z ¹ = Cl, R =). EE) was prepared. Then, the obtained 5- (1-ethoxyethoxy) -3-methylpentylmagnesium = chloride (2: M = MgZ ¹ , Z ¹ = Cl, R = EE) was cooled to room temperature.

Copper (I) bromide (CuBr) (5.74 g), lithium chloride (LiCl) (3.39 g) and tetrahydrofuran (THF) (36.00 g) were added to another reactor under a nitrogen atmosphere, and at room temperature. After stirring for 120 minutes, the mixture was cooled to 10 ° C to 15 ° C. Then, in the other reactor, a toluene solution (100.00 g) of a crude product of 2-methyl-2,6-heptadienyl = p-toluenesulfonate (1 ″: X ″ = OTs) obtained above. ) Was added and stirred. Then, in the other reactor, the total amount of 5- (1-ethoxyethoxy) -3-methylpentylmagnesium = chloride (2: M = MgZ ¹ , Z ¹ = Cl, R = EE) obtained above was charged. The mixture was added dropwise at −5 ° C. to 5 ° C. over 3 hours. After completion of the dropping, the mixture was stirred at 10 to 15 ° C. for 14 hours. Then, a mixture of pure water (100 g), ammonium chloride (4 g) and a 20 wt% hydrogen chloride aqueous solution (4 g) is added to the other reactor, and then n-hexane (100 g) is added and stirred for 30 minutes. And then the organic layer was separated. The separated organic layer is post-treated by conventional washing, drying and concentration to give 1- (1-ethoxyethoxy) -6-isopropenyl-3-methyl-9-decene (3: R = EE). A crude product (25.55 g) was obtained. The crude yield from 2-methyl-2,6-heptadienol was 43.30%. With 1- (1-ethoxyethoxy) -6-isopropenyl-3-methyl-9-decene (3: R = EE) and 1- (1-ethoxyethoxy) -3,7-dimethyl-7,11-dodecadien The production ratio of was 59:41.

The spectral data of the obtained 1- (1-ethoxyethoxy) -6-isopropenyl-3-methyl-9-decene (3: R = EE) was the same as the spectral data obtained in Example 10. rice field.

Example 14
Preparation of 5- (t-butyldimethylsilyloxy) -3-methylpentylmagnesium = chloride (2: M = MgZ ¹ , Z ¹ = Cl, R = tert-butyldimethylsilyl (TBS)) and 1-( Production of t-butyldimethylsilyloxy) -6-isopropenyl-3-methyl-9-decene (3: R = TBS)

Under a nitrogen atmosphere, the reactor was charged with magnesium (1.07 g: 0.044 mol) and tetrahydrofuran (THF) (4.2 g), heated to 60 ° C., and stirred for 50 minutes. Then, in the reactor, a mixed solution of 5-chloro-1- (t-butyldimethylsilyloxy) -3-methylpentane (10.80 g: 0.042 mol) and tetrahydrofuran (THF) (8.4 g) was added. Was added dropwise over 40 minutes. After completion of the dropping, the mixture was stirred at an internal temperature of 60 to 70 ° C. for 4 hours to obtain 5- (t-butyldimethylsilyloxy) -3-methylpentylmagnesium = chloride (2: M = MgZ ¹ , Z ¹ = Cl, R = TBS) was prepared. Then, the obtained 5- (t-butyldimethylsilyloxy) -3-methylpentylmagnesium = chloride (2: M = MgZ ¹ , Z ¹ = Cl, R = TBS) was cooled to room temperature.

Copper (I) bromide (CuBr) (2.32 g), lithium chloride (LiCl) (1.37 g) and tetrahydrofuran (THF) (24.4 g) were added to another reactor under a nitrogen atmosphere, and at room temperature. Was stirred for 10 minutes, and then cooled to 0 to 10 ° C. Then, 2-methyl-2,6-heptadienyl-acetate (1': X'= OAc) (4.66 g: 0.027 mol) was added to the other reactor and stirred, and the mixture was stirred at 0 ° C to 5 ° C. Cooled down to. Then, the entire amount of 5- (t-butyldimethylsilyloxy) -3-methylpentylmagnesium = chloride (2) obtained above was added dropwise to the other reactor at -5 ° C to 5 ° C over 3 hours. bottom. After completion of the dropping, the mixture was stirred at 10 to 15 ° C. for 15 hours. Then, a mixture of pure water (13.5 g), ammonium chloride (1.35 g) and a 20 wt% hydrogen chloride aqueous solution (4.59 g) is added to the other reactor, and then toluene (10 g) is added. In addition, the mixture was stirred for 30 minutes and the organic layer was separated. The separated organic layer is post-treated by conventional washing, drying and concentration to 1- (t-butyldimethylsilyloxy) -6-isopropenyl-3-methyl-9-decene (3: R = TBS). ) Was obtained (11.89 g). The crude yield was 55.56%. 1- (t-butyldimethylsilyloxy) -6-isopropenyl-3-methyl-9-decene (3: R = TBS) and 1- (t-butyldimethylsilyloxy) -3,7-dimethyl-7, The production ratio with 11-dodecazien was 75:25.

The spectral data of 1- (t-butyldimethylsilyloxy) -6-isopropenyl-3-methyl-9-decene (3: R = TBS) obtained above are shown below.
IR (D-ATR): ν = 3074,2955,2928,2857,1643,1472,1462,1376,1361,1255,1097,1005,992,939,909,890,836,811,775,731,662 cm ^-1 .
^{1 1} H-NMR (500 MHz, CDCl ₃ ): δ = 0.05 (6H, s), 0.84-0.87 (3H, m), 0.89 (9H, s), 0.98-1. 09 (1H, m), 1.15-1.1.43 (6H, m), 1.46-1.61 (5H, m), 1.88-2.04 (3H, m), 3. 58-3.68 (2H, m), 4.66 (1H, s-like), 4.73-4.75 (1H, m), 4.91-5.01 (2H, m), 5. 76-5.84 (1H, m) ppm.
¹³ C-NMR (125 MHz, CDCl ₃ ): δ = -5.29, 17.72, 17.81, 18.33, 19.58, 19.89, 25.97, 29.42, 29.54, 30.61, 30.69, 31.70, 32.61, 32.75, 34.78, 34.86, 39.72, 40.12, 47.02, 47.11, 61.45, 61. 47, 111.65, 111.73, 114.14, 139.11, 147.25, 147.36 ppm.
GC-MS (EI, 70eV): 29,55,75,95,113,129,157,173,191,213,233,249,267.

Example 15
Production of 6-isopropenyl-3-methyl-9-decenol (4)

In a nitrogen atmosphere, the reactor was charged with tetrahydro-2- (6-isopropenyl-3-methyl-9-decenyloxy) -2H-pyran (3: R = THP) (27.47 g: 0) obtained according to Example 7. .69 mol), p-toluenesulfonic acid (5.36 g) and methanol (93 g) were charged, and the mixture was stirred at an internal temperature of 50 to 60 ° C. for 4 hours. After the stirring was completed, the solvent was recovered by concentration, and then methanol (93 g) was charged into the reactor and stirred at room temperature for 12 hours. Then, the mixture was stirred at an internal temperature of 50 to 60 ° C. for 2 hours, and the solvent was recovered by concentration. Subsequently, pure water (150 g) and n-hexane (100 g) were added to the reactor, and the mixture was stirred for 30 minutes, and then the organic layer was separated. The separated organic layer was post-treated by conventional washing, drying and concentration to give a crude product (18.46 g) of 6-isopropenyl-3-methyl-9-decenol (4). The crude yield was 72.46%.

The spectral data of 6-isopropenyl-3-methyl-9-decenol (4) obtained above are shown below.
IR (D-ATR): ν = 3332, 3074, 2928, 2871, 1642, 1452, 1376, 1058, 994,909, 889, 641 cm ^-1 .
^{1 1} H-NMR (500 MHz, CDCl ₃ ): δ = 0.87-0.90 (3H, m), 1.00-1.09 (1H, m), 1.17-1.69 (12H, m) ), 1.87-2.08 (3H, m), 3.60-3.70 (2H, m), 4.66 (1H, s-like), 4.74 (1H, s-like), 4.90-5.02 (2H, m), 5.75-5.84 (1H, m) ppm.
¹³ C-NMR (125 MHz, CDCl ₃ ): δ = 17.63, 17.79, 18.52, 19.77, 29.29, 29.61, 30.46, 30.64, 30.65, 32 .56, 32.74, 34.62, 34.88, 39.63, 40.04, 46.91, 47.10, 61.11, 61.14,111.70, 111.81, 114.17 , 139.04, 139.06, 147.21, 147.28 ppm.
GC-MS (EI, 70eV): 29,41,55,69,81,95,109,123,135,149,167,182,195,210.

Example 16
Production of 6-isopropenyl-3-methyl-9-decenol (4)

In a nitrogen atmosphere, the reactor was charged with 1- (1-ethoxyethoxy) -6-isopropenyl-3-methyl-9-decene (3: R = EE) (273.79 g: 0.59 mol), acetic acid (35 mol). .52 g), tetrahydrofuran (THF) (250 g) and pure water (266.4) were charged, and the mixture was stirred at an internal temperature of 70 to 80 ° C. for 7 hours. Then, the reactor was cooled to room temperature, pure water (500 g) and toluene (200 g) were added, and the mixture was stirred for 30 minutes, and then the organic layer was separated. The separated organic layer was post-treated by conventional washing, drying and concentration to obtain a crude product (216.33 g) of 6-isopropenyl-3-methyl-9-decenol (4). The crude yield was 100%.

The spectral data of the obtained 6-isopropenyl-3-methyl-9-decenol (4) was the same as the spectral data obtained in Example 15.

Example 17
Production of 6-isopropenyl-3-methyl-9-decenol (4)

In a nitrogen atmosphere, the reactor was charged with 1- (t-butyldimethylsilyloxy) -6-isopropenyl-3-methyl-9-decene (3: R = TBS) (2.00 g:) obtained according to Example 14. 0.003 mol) and tetrahydrofuran (THF) (30 g) were charged and stirred at room temperature for 5 minutes. Then, a THF solution of tetrabutylammonium fluoride (5.4 mL: 0.005 mol) was added dropwise to the reactor over 10 minutes. After completion of the dropping, the mixture is stirred at room temperature for 5 hours, then pure water (30 g), salt (3 g) and n-hexane (30 g) are added to the reactor, and the mixture is further stirred for 30 minutes, and the organic layer is separated. bottom. The separated organic layer was post-treated by conventional washing, drying and concentration to obtain a crude product (1.99 g) of 6-isopropenyl-3-methyl-9-decenol (4). The crude yield was 100%.

The spectral data of the obtained 6-isopropenyl-3-methyl-9-decenol (4) was the same as the spectral data obtained in Example 15.

Example 18
Production of 6-isopropenyl-3-methyl-9-decenyl-acetate (5)

In a nitrogen atmosphere, the reactor was charged with 6-isopropenyl-3-methyl-9-decenol (4) (215.33 g: 0.77 mol), pyridine (213.45 g), acetic anhydride obtained according to Example 16. (131.78 g) and acetonitrile (220 g) were charged and stirred at room temperature for 4 hours and 45 minutes. Then, pure water (600 g) and n-hexane (300 g) were added to the reactor, and the mixture was stirred for 30 minutes, and then the organic layer was separated. The separated organic layer was post-treated by conventional washing, drying and concentration to obtain a crude product (245.31 g) of 6-isopropenyl-3-methyl-9-decenyl-acetate (5). .. The crude product was distilled under reduced pressure to obtain the target compound 6-isopropenyl-3-methyl-9-decenyl-acetate (5) (142.32 g: 0.55 mol). The yield calculated from all fractions including the initial distillation fraction was 83.27%.

The spectral data of 6-isopropenyl-3-methyl-9-decenyl-acetate (5) obtained above are shown below.
IR (D-ATR): ν = 3073, 2928, 2871, 1742, 1642, 1454, 1367, 1239, 1037, 995, 909, 889, 636,606 cm ^-1 .
^{1 1} H-NMR (500 MHz, CDCl ₃ ): δ = 0.87-0.90 (3H, m), 1.01-1.09 (1H, m), 1.18-1.54 (7H, m) ), 1.56-1.58 (3H, m), 1.59-1.68 (1H, m), 1.89-2.01 (3H, m), 2.02 (3H, s), 4.01-4.12 (2H, m), 4.65 (1H, s-like), 4.74 (1H, s-like), 4.91-5.01 (2H, m), 5. 74-5.83 (1H, m) ppm.
¹³ C-NMR (125 MHz, CDCl ₃ ): δ = 17.63, 17.77, 19.32, 19.63, 20.99, 29.68, 29.96, 30.43, 30.56, 31 .62, 31.65, 32.56, 32.72, 34.49, 34.64, 35.19, 35.64, 46.89, 47.04, 62.98, 63.02, 111.77 , 111.86, 114.19, 138.99, 147.03, 147.15, 171.16 ppm.
GC-MS (EI, 70eV): 29,43,55,67,81,95,109,123,135,149,163,177,192,209,223,237,252.

Example 19
Production of 6-isopropenyl-3-methyl-9-decenyl-acetate (5)

Acetic anhydride (24.50 g) and p-toluenesulfonic acid (0.05 g) were charged into the reactor under a nitrogen atmosphere, and the mixture was stirred at room temperature for 5 minutes. Then, in the reactor, 1- (1-ethoxyethoxy) -6-isopropenyl-3-methyl-9-decene (3: R = EE) (10.00 g: 0.023 mol) obtained according to Example 10 was added. ) Was added dropwise over 1 minute, and the mixture was stirred at an internal temperature of 90 ° C. for 6 hours. Then, pure water (10 g) and n-hexane (50 g) were added to the reactor, and the mixture was stirred for 30 minutes. After the stirring was completed, the organic layer was separated. The separated organic layer was post-treated by conventional washing, drying and concentration to obtain a crude product (9.50 g) of 6-isopropenyl-3-methyl-9-decenyl-acetate (5). .. The crude yield was 100%.

The spectral data of 6-isopropenyl-3-methyl-9-decenyl-acetate (5) obtained in the above was the same as the spectral data obtained in Example 18.

（式中、Ｘはカルボニル基の炭素を含めた炭素数１～１０のアシルオキシ基、炭素数１～１０のアルカンスルホニルオキシ基、炭素数６～２０のアレーンスルホニルオキシ基、又はハロゲン原子を表す。）
で表される、１位に脱離基Ｘを有する２－メチル－２，６－ヘプタジエン化合物と、下記一般式（２）

（式中、Ｍは、Ｌｉ、ＭｇＺ^１、ＺｎＺ^１、Ｃｕ、ＣｕＺ^１又はＣｕＬｉＺ^１を表し、Ｚ^１は、ハロゲン原子又はＣＨ_２ＣＨ_２ＣＨ（ＣＨ_３）ＣＨ_２ＣＨ_２ＯＲ基を表し、かつＲは水酸基の保護基を表す。）
で表される、５位に保護された水酸基を有する３－メチルペンチル求核試薬との求核置換反応により、下記一般式（３）

（式中、Ｒは、上記で定義した通りである。）
で表される、１位に保護された水酸基を有する６－イソプロペニル－３－メチル－９－デセン化合物を得る工程と、
１位に保護された水酸基を有する上記６－イソプロペニル－３－メチル－９－デセン化合物（３）の脱保護反応により、下記式（４）

で表される６－イソプロペニル－３－メチル－９－デセノールを得る工程と、
上記６－イソプロペニル－３－メチル－９－デセノール（４）をアセチル化して、下記式（５）

（式中、Ａｃはアセチル基を表す。）
で表される６－イソプロペニル－３－メチル－９－デセニル＝アセテートを得る工程と
を少なくとも含む、６－イソプロペニル－３－メチル－９－デセニル＝アセテート（５）の製造方法が提供される。 According to one aspect of the present invention, the following general formula (1)

(In the formula, X represents an acyloxy group having 1 to 10 carbon atoms including carbon of a carbonyl group, an alkanesulfonyloxy group having 1 to 10 carbon atoms, an allene sulfonyloxy group having 6 to 20 carbon atoms, or a halogen atom. )
A 2-methyl-2,6-heptadiene compound having a leaving group X at the 1-position represented by the following general formula (2).

(In the formula, M represents Li, MgZ ¹ , ZnZ ¹ , Cu, CuZ ¹ or CuLiZ ¹ , and Z ¹ represents a halogen atom or CH ₂ CH ₂ CH (CH ₃ ) CH ₂ CH ₂ OR group. And R represents a hydroxyl-protecting group.)
The following general formula (3) is obtained by a nucleophilic substitution reaction with a 3-methylpentyl nucleophile having a hydroxyl group protected at the 5-position represented by.

(In the formula, R is as defined above.)
A step of obtaining a 6-isopropenyl-3-methyl-9-decene compound having a hydroxyl group protected at the 1-position represented by
The following formula (4) is obtained by the deprotection reaction of the above 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position.

The step of obtaining 6-isopropenyl-3-methyl-9- decenol represented by
The above 6-isopropenyl-3-methyl-9- decenol (4) is acetylated to the following formula (5).

(In the formula, Ac represents an acetyl group.)
Provided is a method for producing 6-isopropenyl-3-methyl-9-decenyl-acetate (5), which comprises at least a step of obtaining 6-isopropenyl-3-methyl-9-decenyl-acetate represented by. ..

That is, the above chemical reaction formula is a 2-methyl-2,6-heptadiene compound having a desorbing group X at the 1-position obtained by the conversion reaction of the hydroxyl group of 2-methyl-2,6-heptadienol (6). Step A for synthesizing (1); Next, a 3-methylpentyl nucleophilic reagent (2) having a hydroxyl group protected at the 5-position is used, and 2-methyl-2,6-with a desorbing group X at the 1-position. A 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position is obtained by performing a nucleophilic substitution reaction on the carbon atom at the 3-position of the heptadiene compound (1) in a position-selective manner. Step B to synthesize; and step C to deprotect the 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position; finally , 6-isopropenyl-3-methyl. A step D of synthesizing 6-isopropenyl-3-methyl-9-decenyl-acetate (5) , which is the target compound of the present invention, by acetylating -9-decenol (4) is included.

Therefore, in step B, the 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position and the 3,7-dimethyl-7,11-dodecadien compound (3') Can conflict with generation. Therefore, under the conditions of the nucleophilic substitution reaction described later, the by-product of the 3,7-dimethyl-7,11-dodecadien compound (3') having a hydroxyl group protected at the 1-position is suppressed and protected at the 1-position. The optimum conditions for obtaining the 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group in a good yield may be selected. The optimum conditions are, for example, acyloxy having 1 to 10 carbon atoms in which the leaving group X in the 2-methyl-2,6-heptadiene compound (1) having the leaving group X at the 1-position includes the carbon of the carbonyl group. The group used is the 2-methyl-2,6- heptadiene compound (1'), and the protective group in the 3-methylpentyl nucleophilic reagent (2) having a 5-protected hydroxyl group is 1-. Using a 5- (1-ethoxyethyloxy) -3-methylpentylmagnesium-halide compound, which is an ethoxyethyl group, and using a combination of copper halide and a lithium salt as a combination of catalysts used for the nucleophilic substitution reaction. The use of combinations can be mentioned. It is believed that this combination of catalysts suppresses the formation of by-products and increases the yield of the desired product (see, for example, Examples 6 and 7 below).

The 3-methylpentyl nucleophilic reagent (2) having a hydroxyl group protected at the 5-position is represented by the following general formula (2a) when the priority of atoms in the RS notation is M> O. (R) -3-methylpentyl nucleophilic reagent having a hydroxyl group protected by, and (S) -3-methylpentyl nucleophilic having a hydroxyl group protected at the 5-position represented by the following general formula (2b). Can exist as a reagent. These isomers, which may be alone or in admixture, have a 5-protected hydroxyl group with the same skeleton as the natural sex pheromone of females of California red scale (R). ) -3-Methylpentyl nucleophile (2a) is preferably contained.

The 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position has a hydroxyl group protected at the 1-position represented by the following general formula (3a) (3R, 6R) -6-isopropenyl-3-methyl-9-decene compound, represented by the following general formula (3b), having a hydroxyl group protected at the 1-position (3R, 6S) -6-isopropenyl-3- Methyl-9-decene compound, (3S, 6R) -6-isopropenyl-3-methyl-9-decene compound having a hydroxyl group protected at the 1-position represented by the following general formula (3c), and the following general. It can exist as a (3S, 6S) -6-isopropenyl-3-methyl-9-decene compound having a hydroxyl group protected at the 1-position represented by the formula (3d). These isomers, which may be alone or in mixtures, have a 1-position protected hydroxyl group having the same skeleton as the natural sex pheromone of females of California red scale (3S). , 6R) -6-isopropenyl-3-methyl-9-decene compound (3c) is preferably contained.

As a specific example of the 3-methylpentylmagnesium = halide compound having a hydroxyl group protected at the 5-position, the 3-methylpentylmagnesium = chloride compound having a hydroxyl group protected at the 5-position has a hydroxyl group protected at the 5-position. Examples thereof include 3-methylpentylmagnesium = bromide compound and 3-methylpentylmagnesium = iodide compound having a hydroxyl group protected at the 5-position.
The 3-methylpentyl nucleophile (2) having a hydroxyl group protected at the 5-position is, for example, a 3-methylpentyl-halide compound having a hydroxyl group protected at the 5-position, which is a corresponding halide, by a conventional method. Prepared. Examples of the 3-methylpentyl-halide compound having a hydroxyl group protected at the 5-position include a 3-methylpentyl-chloride compound having a hydroxyl group protected at the 5-position and 3-methyl having a hydroxyl group protected at the 5-position. Examples thereof include a pentyl = bromide compound and a 3-methylpentyl = iodide compound having a hydroxyl group protected at the 5-position, and a 3-methylpentyl nucleophilic reagent (2) having a hydroxyl group protected at the 5-position is prepared. From the viewpoint of ease and / or stability of the compound, 3-methyl-pentyl = chloride compound having a hydroxyl group protected at the 5-position and 3-methyl-pentyl-bromid compound having a hydroxyl group protected at the 5-position are used. preferable.

6-Isopropenyl-3-methyl-9- decenol (4) is represented by the following formula (4a) (3R, 6R) -6-isopropenyl-3-methyl-9-decenol, the following formula ( (3R, 6S) -6-isopropenyl-3-methyl-9-decenol represented by 4b), (3S, 6R) -6-isopropenyl-3-methyl-9 represented by the following formula (4c) -It may exist as desenol and (3S, 6S) -6-isopropenyl-3-methyl-9-decenol represented by the following formula (4d). These isomers, either alone or in admixture, have the same skeleton as the natural sex pheromones of females of California red scale (3S, 6R) -6-isopropenyl-3. -Methyl-9-decenol (4c) is preferably contained.

6-Isopropenyl-3-methyl-9-decenyl-acetate (5) is represented by the following formula (5a) (3R, 6R) -6-isopropenyl-3-methyl-9-decenyl = acetate, below. (3R, 6S) -6-isopropenyl-3-methyl-9-decenyl = acetate represented by the formula (5b), (3S, 6R) -6-isopropenyl-3 represented by the following formula (5c) It may exist as -methyl-9-decenyl = acetate and (3S, 6S) -6-isopropenyl-3-methyl-9-decenyl = acetate represented by the following formula (5d). These isomers, either alone or in admixture, have the same skeleton as the natural sex pheromones of females of California red scale (3S, 6R) -6-isopropenyl-3. -Methyl-9-decenyl = acetate (5c) is preferably contained.

(Iii) Transesterification reaction with acetic acid ester The transesterification reaction is generally carried out in the presence of a catalyst, and the alcohol produced as a by-product from the acetic acid ester is removed during the reaction under normal pressure or reduced pressure to promote the reaction. be able to.
As the acetic acid ester in the ester exchange reaction, for example, acetic acid esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate and phenyl acetate can be used. Of these acetates, methyl acetate and ethyl acetate are preferable from the viewpoints of economy, reactivity, and ease of removal of alcohol by-produced from the acetate.
The amount of the acetate ester used in the transesterification reaction is preferably 1 to 50 mol, more preferably 1 to 5 mol, relative to 1 mol of 6-isopropenyl-3-methyl-9-decenol (4).

(Iv) Method of converting the hydroxyl group of 2-methyl-2,6-heptadienol (6) into a leaving group and then reacting with a carboxylic acid 2-methyl-2,6-heptadienol (6) In the method of converting a hydroxyl group into a leaving group and then reacting with a carboxylic acid, for example, the hydroxyl group of 2-methyl-2,6-heptadienol (6) is converted into a halogen such as a chlorine atom, a bromine atom and an iodine atom . It is converted to an atomic, an alkanesulfonyloxy group such as methanesulfonate, trifluoromethanesulfonate, a leaving group such as arenesulfonyloxy such as benzenesulfonate and p-toluenesulfonate, and with these in the solvent in the presence of a base. React with carboxylic acid. Further, instead of using a base, available carboxylic acid metal salts such as sodium carboxylate and potassium carboxylate may be used instead of the carboxylic acid.
Examples of the carboxylic acid include compounds similar to the carboxylic acid in the reaction with the carboxylic acid.
The amount of the carboxylic acid used is preferably 1 to 500 mol, more preferably 1 to 50 mol, still more preferably 1 to 5 mol, relative to 1 mol of 2-methyl-2,6-heptadienol (6). be.
Examples of the above-mentioned bases include amines such as triethylamine, pyridine, N, N-dimethylaminopyridine and dimethylaniline; organic lithium compounds such as n-butyllithium, methyllithium and phenyllithium; sodium hydroxide and potassium hydroxide. Examples thereof include metal hydroxides; metal carbonates such as potassium carbonate, sodium carbonate and sodium hydrogen carbonate; and metal hydrides such as sodium hydride and potassium hydride.
The amount of the base used is preferably 1 to 50 mol, more preferably 1 to 10 mol, with respect to 1 mol of the alkylating agent.

When the leaving group X is a halogen atom, a halogenating agent is used to carry out a conversion reaction of the hydroxyl group of 2-methyl-2,6-heptadienol (6). In the reaction with the halogenating agent, 2-methyl-2,6-heptadienol (6) is subjected to the halogenating agent, and then the base, or vice versa, or halogenation in a single solvent or a mixed solvent of two or more kinds. The agent and the base are reacted at the same time.
Examples of the halogenating agent include thionyl halides such as thionyl chloride and thionyl bromide; phosphorus halide compounds such as phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride and phosphorus pentabromide; phosphorus oxychloride and phosphorus oxybromated. Oxyhalogenated phosphorus compounds such as; and aromatic halogenated phosphorus compounds such as dichlorotriphenylphosphoran and dibromotriphenylphosphoran.
Further, when a sulfonic acid halide such as methanesulfonyl = chloride, ethanesulfonyl = chloride and trifluoromethanesulfonyl = chloride is used instead of the above-mentioned halogenating agent, 2-methyl-2,6-heptadienol (6). The hydroxyl group is sulfonylated, after which the sulfonyloxy group can be converted to the halogen atom corresponding to the sulfonic acid halide by heating as needed.
Further, even when the hydroxyl group is sulfonylated with a sulfonylating agent other than the above-mentioned sulfonic acid halide, or when the hydroxyl group is halogenated with the above-mentioned halogenating agent, a metal halide, a quaternary onium salt, or the like is subsequently used. A halogenating agent can be added to convert to the corresponding halide.
Examples of the metal halide include lithium bromide, sodium bromide, potassium bromide, lithium iodide, sodium iodide, potassium iodide and the like.
Examples of the quaternary onium salt include tetraethylammonium = bromide, tetrabutylammonium = bromide, tetrabutylphosphonium = bromide, tetraethylammonium = iodide, tetrabutylammonium = iodide, tetrabutylphosphonium = iodide and the like.
The amount of the halogenating agent used is preferably 1 to 500 mol, more preferably 1 to 50 mol, still more preferably 1 to 5 mol, relative to 1 mol of 2-methyl-2,6-heptadienol (6). Is the range of.

In the above steps A to D as one embodiment of the present invention, in the step C, the 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position is deprotected. By subjecting to the reaction, 6-isopropenyl-3-methyl-9-decenol (4) was obtained, and then in step D, 6-isopropenyl-3-methyl-9-decenol (4) was acetylated to obtain acetylation. The target compound, 6-isopropenyl-3-methyl-9-decenyl-acetate (5), can be obtained. By using an acetylating agent under deprotection reaction conditions instead of the steps C and D shown in the above chemical reaction formula, the present inventors did not go through the above step D. It was further found that -isopropenyl-3-methyl-9-decenyl-acetate (5) can be obtained. That is, it is considered that an acetylation reaction occurs following the deprotection reaction by using an acetylating agent under the deprotection reaction conditions. Therefore, 6-isopropenyl-3-methyl-9-decenyl = acetate (5). ) Can be obtained in one step. Whether or not the acetylation reaction occurs following the deprotection reaction depends on, for example, the type of protecting group of the 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position. do. Examples of the protecting group include those that can be deprotected with an acid, and specific examples thereof include an oxyalkyl group such as a 1-ethoxyethyl group. For example, inorganic acids such as hydrochloric acid, hydrobromic acid, nitrate and sulfuric acid; organic acids such as trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid; aluminum trichloride, aluminum = ethoxydo, Aluminum = isopropoxide, aluminum oxide, boron trifluoride, boron trichloride, boron tribromide, magnesium chloride, magnesium bromide, magnesium iodide, zinc chloride, zinc bromide, zinc iodide, tin tetrachloride, quaternary Tin bromide, dibutyl tin dichloride, dibutyl tin = dimethoxydo, dibutyl tin = oxide, titanium tetrachloride, titanium tetrabromide, titanium (IV) = methoxyd, titanium (IV) = ethoxydo, titanium (IV) = isopropoxide And Lewis acids such as titanium oxide (IV); and the above deprotection by adding an acetylating agent such as anhydrous acetic acid to the reaction system in the presence of an acid catalyst such as sodium acetate and metal acetate salts such as potassium acetate. Following the reaction, the acetylation reaction can proceed in one step. Preferably, by adding an acetylating agent such as acetic anhydride to the reaction system in the presence of an acid catalyst such as p-toluenesulfonic acid, the acetylation reaction can be allowed to proceed in one step following the deprotection reaction. Yes (see Example 19 below).

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples.
In the following, unless otherwise specified, "purity" indicates the area percentage obtained by gas chromatography (GC) analysis, and "production ratio" indicates the relative ratio of the area percentage obtained by GC analysis. .. Further, "yield" indicates a yield calculated based on the area percentage obtained by GC analysis.
Samples for spectral measurement of compounds are optionally obtained by purifying the crude product.
In each example, reaction monitoring and yield calculation were performed according to the following GC conditions.
GC conditions: GC: Shimadzu Capillary Gas Chromatograph GC-2014, Column: DB-5,0.25 μ mx0.25 mmφx30 m, Carrier gas: He (1.55 mL / min), Detector: FID, Column temperature: 100 ° C. 10 ° C / min temperature rise 230 ° C.
In each example, reaction monitoring may have been performed by thin layer chromatography (TLC). The solvent in parentheses shown in the TLC indicates the elution solvent or developing solvent used, and the ratio represents the volume ratio.
The yield was calculated according to the following formula, taking into account the purity of the raw material and the product (% GC).
Yield (%) = {[(Weight of product obtained by reaction x% GC) / Molecular weight of product]
÷ [(Weight of starting material in reaction x% GC) / Molecular weight of starting material]} x 100
The "crude yield" means a yield calculated without purification.

Under a nitrogen atmosphere, the reactor was charged with magnesium (3.03 g: 0.12 mol) and tetrahydrofuran (THF) (12.0 g), heated to 60 ° C., and stirred for 10 minutes. Then, a mixed solution of 5-chloro-1- (1-ethoxyethoxy) -3-methylpentane ( 26.80 g: 0.12 mol) and tetrahydrofuran (THF) (24.0 g) was added to the reactor for 120 minutes. Dropped over. After completion of the dropping, the mixture was stirred at an internal temperature of 60 to 70 ° C. for 2 hours to obtain 5- (1-ethoxyethoxy) -3-methylpentylmagnesium = chloride (2: M = MgZ ¹ , Z ¹ = Cl, R =). EE) was prepared. Then, the obtained 5- (1-ethoxyethoxy) -3-methylpentylmagnesium = chloride (2: M = MgZ ¹ , Z ¹ = Cl, R = EE) was cooled to room temperature.

In a nitrogen atmosphere, the reactor was charged with 1- (1-ethoxyethoxy) -6-isopropenyl-3-methyl-9-decene (3: R = EE) (273.79 g: 0.59 mol), acetic acid (35 mol). .52 g), tetrahydrofuran (THF) (250 g) and pure water (266.4 g ) were charged, and the mixture was stirred at an internal temperature of 70 to 80 ° C. for 7 hours. Then, the reactor was cooled to room temperature, pure water (500 g) and toluene (200 g) were added, and the mixture was stirred for 30 minutes, and then the organic layer was separated. The separated organic layer was post-treated by conventional washing, drying and concentration to obtain a crude product (216.33 g) of 6-isopropenyl-3-methyl-9-decenol (4). The crude yield was 100%.

The spectral data of the obtained 6- isopropenyl -3-methyl-9-decenyl-acetate (5) was the same as the spectral data obtained in Example 18.

Claims (6)

The following general formula (1)

(In the formula, X represents an acyloxy group having 1 to 10 carbon atoms including carbon of a carbonyl group, an alkane sulfonyloxy group having 1 to 10 carbon atoms, an allene sulfonyloxy group having 6 to 20 carbon atoms, or a halogen atom. )
A 2-methyl-2,6-heptadiene compound having a leaving group X at the 1-position represented by the following general formula (2).

(In the formula, M represents Li, MgZ ¹ , ZnZ ¹ , Cu, CuZ ¹ or CuLiZ ¹ , and Z ¹ represents a halogen atom or CH ₂ CH ₂ CH (CH ₃ ) CH ₂ CH ₂ OR group. And R represents a hydroxyl-protecting group.)
The following general formula (3) is obtained by a nucleophilic substitution reaction with a 3-methylpentyl nucleophile having a hydroxyl group protected at the 5-position represented by.

(In the equation, R is as defined above.)
A step of obtaining a 6-isopropenyl-3-methyl-9-decene compound having a hydroxyl group protected at the 1-position represented by
The following formula (4) is obtained by the deprotection reaction of the 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position.

The step of obtaining 6-isopropenyl-3-methyl-9-decenol represented by
The 6-isopropenyl-3-methyl-9-decenol (4) is acetylated to the following formula (5).

(In the formula, Ac represents an acetyl group.)
A method for producing 6-isopropenyl-3-methyl-9-decenyl-acetate (5), which comprises at least a step of obtaining 6-isopropenyl-3-methyl-9-decenyl-acetate represented by. The following formula (6)

By converting the hydroxyl group of 2-methyl-2,6-heptadienol represented by (X is as defined above) to X (X is as defined above), the 2-methyl-2,6-heptadienol has a leaving group X at the 1-position. The method for producing 6-isopropenyl-3-methyl-9-decenyl-acetate (5) according to claim 1, further comprising a step of obtaining the methyl-2,6-heptadiene compound (1). The following general formula (1)

(In the formula, X represents an acyloxy group having 1 to 10 carbon atoms including carbon of a carbonyl group, an alkane sulfonyloxy group having 1 to 10 carbon atoms, an allene sulfonyloxy group having 6 to 20 carbon atoms, or a halogen atom. )
A 2-methyl-2,6-heptadiene compound having a leaving group X at the 1-position represented by the following general formula (2).

(In the formula, M represents Li, MgZ ¹ , ZnZ ¹ , Cu, CuZ ¹ or CuLiZ ¹ , and Z ¹ represents a halogen atom or CH ₂ CH ₂ CH (CH ₃ ) CH ₂ CH ₂ OR group. And R represents a hydroxyl-protecting group.)
The following general formula (3) is obtained by a nucleophilic substitution reaction with a 3-methylpentyl nucleophile having a hydroxyl group protected at the 5-position represented by.

(In the equation, R is as defined above.)
A step of obtaining a 6-isopropenyl-3-methyl-9-decene compound having a hydroxyl group protected at the 1-position represented by
The 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position is subjected to an acetylation reaction and the following formula (5) is applied.

(In the formula, Ac represents an acetyl group.)
A method for producing 6-isopropenyl-3-methyl-9-decenyl-acetate (5), which comprises at least a step of obtaining 6-isopropenyl-3-methyl-9-decenyl-acetate represented by. The following formula (6)

By converting the hydroxyl group of 2-methyl-2,6-heptadienol represented by, to X (X is as defined above), the 2-position having a leaving group X at the 1-position is described above. The method for producing 6-isopropenyl-3-methyl-9-decenyl-acetate (5) according to claim 3, further comprising the step of obtaining the methyl-2,6-heptadiene compound (1). The following general formula (1')

(In the formula, X'represents an acyloxy group having 1 to 10 carbon atoms including the carbon of the carbonyl group.)
A 2-methyl-2,6-heptadiene compound having X'at the 1-position represented by. The following general formula (1'')

(In the formula, X'' represents an alkanesulfonyloxy group having 1 to 10 carbon atoms or an arene sulfonyloxy group having 6 to 20 carbon atoms.)
2-Methyl-2,6-heptadiene compound having X'' at the 1-position represented by.