JP3312414B2 - Process for producing dienoic halides - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing dienoic halides by allowing an organic phosphine to act on cyclopropanecarboxylic acid halides to cause isomerization.

[0002]

2. Description of the Related Art Dienoic halides are useful as intermediates in fine chemicals such as medicines, agricultural chemicals, and fragrances. Thus, a cyclic nitrogen-containing compound can be derived, and can be an intermediate for the production of medical and agricultural chemicals. Also, 2,2, -dimethyl-3- (2'-methylpropenyl) cyclopropanecarboxylic acid halide is known as an intermediate for producing terpene-based flavors such as mugwort alcohol and artemisia ketone. Further, as the dienoic halides, 2,2, -dimethyl-3- (2'-methylpropenyl) cyclopropanecarboxylic acid halide is reacted with a Lewis acid such as aluminum chloride to cause isomerization.
2,5-trimethyl hepta-3,5-diene carboxylic acid halide, are also known to produce small amounts as a by-product (Journal of Japan Agricultural Pharmaceutical Society 15,473 (1990)).

[0003]

The present inventors have conducted intensive studies on isomerization catalysts in order to efficiently produce dienoic acid halides from cyclopropane carboxylic acid halides. As a result, a specific compound called organic phosphine was obtained. By using, it has been found that the desired product can be easily produced at a high yield, and the present invention has been completed by further various studies.

[0004] be such KazuSatoshi, the present invention provides a compound of formula (I) (In the formula, R1, R2, R3, and R4 each independently represent a hydrogen atom or a lower alkyl group, and X represents a halogen atom.)

A compound of the formula [II] characterized in that the compound is isomerized by reacting an organic phosphine with a cyclopropanecarboxylic acid halide represented by the formula (II): (Wherein, R ¹ , R ² , R ³ , R ⁴ , and X have the same meanings as described above), which provides an industrially excellent method for producing dienoic halides.

Next, the present invention will be described in more detail. Examples of the substituents R ¹ , R ² , R ³ and R ⁴ of the cyclopropanecarboxylic acid halides [I] as the raw material of the present invention include, for example, a hydrogen atom, methyl, ethyl, n-propyl, i-propyl, n -
Lower alkyl groups such as butyl, i-butyl, sec-butyl and t-butyl are exemplified. X is, for example, a halogen atom such as chlorine or bromine.

More specific cyclopropanecarboxylic acid halides [I] include, for example, 2,2-dimethyl-3- (2 '
-Methylpropenyl) cyclopropanecarboxylic acid, 3-
(2'-methylpropenyl) cyclopropanecarboxylic acid, 3-
Chloride such as (1-propenyl) cyclopropanecarboxylic acid and 3- (1-butenyl) cyclopropanecarboxylic acid, bromide and the like can be mentioned. These may be either the cis form or the trans form, or a mixture thereof.

The organic phosphine which is an isomerization catalyst includes, for example, aryl phosphines such as triphenylphosphine and tris (2-tolyl) phosphine, and tri-n-
Butyl phosphine, alkyl phosphines such as triisopropyl phosphine, tricyclohexyl phosphine,
And cyclohexylphosphines such as dicyclohexylphenylphosphine. The amount used is usually based on cyclopropanecarboxylic acid halides [I].
It is 0.01 to 1 mole times.

Iodine can also be used as an isomerization promoter. The amount of use is usually 0.01 to 1 mol times based on the cyclopropanecarboxylic acid halide [I].

[0010] The isomerization reaction is usually carried out in the presence of a solvent. Such solvents include, for example, acetonitrile,
An aprotic polar solvent such as dimethyl sulfoxide, dimethylformamide, diglyme and the like is preferably used.
The amount used is usually about 0.5 to 100 times by weight based on the cyclopropanecarboxylic acid halide [I]. The reaction temperature is usually from room temperature to the boiling point of the solvent, preferably from 40 to 12
The temperature range is 0 ° C.

The progress of the reaction is determined by gas chromatography,
It can be confirmed by analytical means such as thin layer chromatography and nuclear magnetic resonance spectrum. After completion of the reaction, the target substance can be recovered, for example, by distilling off the solvent or the like from the reaction mass and then using a separation means such as distillation. The target substance can also be recovered in the form of an ester derivative, a carboxylic acid, or the like by treating the reaction mass with alcohol, water, alkaline water, or the like.

[0012]

According to the method of the present invention, a dienoic halide [II] can be easily produced from a cyclopropanecarboxylic acid halide [I] in a high yield by using an organic phosphine as a catalyst.

[0013]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 Under a nitrogen atmosphere, 2,2-dimethyl-3- (2 '
-Methylpropenyl) cyclopropanecarboxylic acid chloride (cis / trans = 35/65) 20 g and acetonitrile 100 ml were added, and triphenylphosphine 5.64 g was added.
Stirred for hours. The reaction mass was sampled, the acid chloride was converted to ethyl ester according to a conventional method, and analyzed by gas chromatography. It was confirmed that no raw material acid chloride was present in the reaction mass.

After distilling off the solvent from the reaction mass under reduced pressure, the residue was distilled under reduced pressure to obtain 18.3 g of 2,2,5-trimethylhepta-3,5-dienecarboxylic acid chloride. . bp 48 ~52 ℃ / 0.4 ~0.6mmHg ethyl ester derivative of _{^{1 H-NMR (90MH Z)}} δ (ppm, CDCl 3): 5.9 (dd, 2H), 4.9 (s, 2H), 4.1 (q, 2H ), 2.35
(s, 2H), 1.85 (s, 3H), 1.3 (t, 3H), 1.2 (s, 6H)

A mixture of 10 g of the above acid chloride and 100 g of water was cooled to 10 ° C., and 10% caustic soda water was added to the mixture to adjust the pH to 9%.
Then, the mixture was stirred at the same temperature for 2 hours. Then, after extraction with toluene, the aqueous layer was separated, and acetic acid was added thereto to adjust the pH.
= 3. Then, toluene extraction was performed, and the organic layer was separated, washed with water, dried over anhydrous sodium sulfate, concentrated, and distilled under reduced pressure to obtain 8.07 g of 2,2,5-trimethylheptane.
3,5-Dienecarboxylic acid was obtained. bp.77 ℃ / 0.2mmHg

Example 2 In Example 1, except that 4.34 g of tri-n-butylphosphine was used instead of triphenylphosphine,
By carrying out according to Example 1, 11.6 g of 2,2,
5-Trimethylhepta-3,5-dienecarboxylic acid chloride was obtained.

Example 3 2 g of 2- (1-butenyl) cyclopropanecarboxylic acid chloride and 2 g of acetonitrile were placed in a 50 ml flask under a nitrogen atmosphere.
After adding 0 ml, 1.65 g of triphenylphosphine and 0.64 g of iodine were added, and the mixture was stirred at 80 ° C. for 6 hours. After the reaction, 5.8 g of ethanol and 3 g of pyridine were added, and the mixture was stirred, followed by silica gel column chromatography (developing solvent: hexane-
Purification using an ethyl acetate mixed solvent) gave 1.27 g of oily ethyl octa-3,5-dienecarboxylate. δ (ppm, CDCl ₃ ): 5.3 to 6.1 (m, 4H), 4.15 (q, 2H), 2.4 (m, 2
H), 1.7 (d, 3H), 1.3 (t, 3H), 0.9-1.1 (m, 2H)

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Takeo Suzugamo 2-10-1 Tsukahara, Takatsuki-shi, Osaka Sumitomo Chemical Co., Ltd. (56) Reference JP-A-58-67648 (JP, A) JP-A-58-67648 58-67634 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 51/62 C07C 57/66

Claims (2)

(57) [Claims] 1. The formula [I] (Wherein, R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom or a lower alkyl group, and X represents a halogen atom). To cause isomerization, a formula (II) (Wherein R ¹ , R ² , R ³ , R ⁴ , and X represent the same meaning as described above). 2. The method according to claim 1, which is carried out in the coexistence of iodine.