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JP2022022960A5
JP2022022960A5 JP2021011957A JP2021011957A JP2022022960A5 JP 2022022960 A5 JP2022022960 A5 JP 2022022960A5 JP 2021011957 A JP2021011957 A JP 2021011957A JP 2021011957 A JP2021011957 A JP 2021011957A JP 2022022960 A5 JP2022022960 A5 JP 2022022960A5
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methyl
acyloxy
represented
heptadiene
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JP2022022960A (en
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Priority to US17/368,996 priority Critical patent/US11795133B2/en
Priority to EP21184426.1A priority patent/EP3936500A1/en
Priority to CN202110778909.XA priority patent/CN113912494A/en
Publication of JP2022022960A publication Critical patent/JP2022022960A/en
Publication of JP2022022960A5 publication Critical patent/JP2022022960A5/ja
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下記一般式（１）
Figure 2022022960000001
 （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）
Figure 2022022960000002
 （式中、Ｍは、Ｌｉ、ＭｇＺ１、ＺｎＺ１、Ｃｕ、ＣｕＺ１又はＣｕＬｉＺ１を表し、Ｚ１は、ハロゲン原子又はＣＨ２ＣＨ２ＣＨ（ＣＨ３）ＣＨ２ＣＨ２ＯＲ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）
Figure 2022022960000003
 （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前記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）
Figure 2022022960000004
 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、
前記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）
Figure 2022022960000005
 （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。 General formula (1) below
Figure 2022022960000001
 (In the formula, X represents an acyloxy group having 1 to 10 carbon atoms including the carbon of the carbonyl group, an alkanesulfonyloxy group having 1 to 10 carbon atoms, an arenesulfonyloxy group having 6 to 20 carbon atoms, or a halogen atom. )
and a 2-methyl-2,6-heptadiene compound having a leaving group X at the 1-position, represented by the following general formula (2)
Figure 2022022960000002
 (wherein M represents Li, MgZ 1 , ZnZ 1 , Cu, CuZ 1 or CuLiZ 1 , Z 1 represents a halogen atom or a CH 2 CH 2 CH(CH 3 )CH 2 CH 2 OR group, and R represents a hydroxyl-protecting group.)
Represented by a nucleophilic substitution reaction with a 3-methylpentyl nucleophilic reagent having a hydroxyl group protected at the 5-position, the following general formula (3)
Figure 2022022960000003
 (wherein R is as defined above.)
obtaining a 6-isopropenyl-3-methyl-9-decene compound having a hydroxyl group protected at the 1-position represented by
By deprotection reaction of the 6-isopropenyl-3-methyl-9-decene compound (3) having a hydroxyl group protected at the 1-position, the following formula (4)
Figure 2022022960000004
 obtaining 6-isopropenyl-3-methyl-9-decenol represented by
The 6-isopropenyl-3-methyl-9-decenol (4) is acetylated to give the following formula (5)
Figure 2022022960000005
 (In the formula, Ac represents an acetyl group.)
A process for producing 6-isopropenyl-3-methyl-9-decenyl acetate (5), comprising at least a step of obtaining 6-isopropenyl-3-methyl-9-decenyl acetate represented by 下記式（６）
Figure 2022022960000006
 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を有する前記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、請求項１に記載の、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。 Formula (6) below
Figure 2022022960000006
 By converting the hydroxyl group of 2-methyl-2,6-heptadienol represented by to X (where X is as defined above), the 2- The process for producing 6-isopropenyl-3-methyl-9-decenyl acetate (5) according to claim 1, further comprising the step of obtaining methyl-2,6-heptadiene compound (1). 下記一般式（１）
Figure 2022022960000007
 （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）
Figure 2022022960000008
 （式中、Ｍは、Ｌｉ、ＭｇＺ１、ＺｎＺ１、Ｃｕ、ＣｕＺ１又はＣｕＬｉＺ１を表し、Ｚ１は、ハロゲン原子又はＣＨ２ＣＨ２ＣＨ（ＣＨ３）ＣＨ２ＣＨ２ＯＲ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）
Figure 2022022960000009
 （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前記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）
Figure 2022022960000010
 （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。 General formula (1) below
Figure 2022022960000007
 (In the formula, X represents an acyloxy group having 1 to 10 carbon atoms including the carbon of the carbonyl group, an alkanesulfonyloxy group having 1 to 10 carbon atoms, an arenesulfonyloxy group having 6 to 20 carbon atoms, or a halogen atom. )
and a 2-methyl-2,6-heptadiene compound having a leaving group X at the 1-position, represented by the following general formula (2)
Figure 2022022960000008
 (wherein M represents Li, MgZ 1 , ZnZ 1 , Cu, CuZ 1 or CuLiZ 1 , Z 1 represents a halogen atom or a CH 2 CH 2 CH(CH 3 )CH 2 CH 2 OR group, and R represents a hydroxyl-protecting group.)
Represented by a nucleophilic substitution reaction with a 3-methylpentyl nucleophilic reagent having a hydroxyl group protected at the 5-position, the following general formula (3)
Figure 2022022960000009
 (wherein R is as defined above.)
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 protected hydroxyl group at the 1-position is subjected to an acetylation reaction to give the following formula (5)
Figure 2022022960000010
 (In the formula, Ac represents an acetyl group.)
A process for producing 6-isopropenyl-3-methyl-9-decenyl acetate (5), comprising at least a step of obtaining 6-isopropenyl-3-methyl-9-decenyl acetate represented by 下記式（６）
Figure 2022022960000011
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を有する前記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、請求項３に記載の、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。 Formula (6) below
Figure 2022022960000011
By converting the hydroxyl group of 2-methyl-2,6-heptadienol represented by to X (where X is as defined above), the 2- The method for producing 6-isopropenyl-3-methyl-9-decenyl acetate (5) according to claim 3, further comprising the step of obtaining methyl-2,6-heptadiene compound (1). 下記一般式（１’）
Figure 2022022960000012
 （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。 The following general formula (1')
Figure 2022022960000012
 (Wherein, 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 前記アシルオキシ基が、直鎖状の脂肪族アシルオキシ基、分岐状の脂肪族アシルオキシ基、ハロゲン化アシルオキシ基及び芳香族アシルオキシ基、並びにこれらと異性体の関係にあるアシルオキシ基から成る群から選択される、請求項５に記載の、１位にＸ’を有する２－メチル－２，６－ヘプタジエン化合物。The acyloxy group is selected from the group consisting of a linear aliphatic acyloxy group, a branched aliphatic acyloxy group, a halogenated acyloxy group, an aromatic acyloxy group, and an isomeric acyloxy group thereof. The 2-methyl-2,6-heptadiene compound having X' at the 1-position according to Claim 5. 前記アシルオキシ基が直鎖状の脂肪族アシルオキシ基又はこれらと異性体の関係にあるアシルオキシ基であり、該直鎖状の脂肪族アシルオキシ基が、ホルミルオキシ基、アセトキシ基、プロパノイルオキシ基、ブタノイルオキシ基、ペンタノイルオキシ基、ヘキサノイルオキシ基、ヘプタノイルオキシ基、オクタノイルオキシ基、ノナノイルオキシ基、デカノイルオキシ基及びクロトニルオキシ基から成る群から選択されてもよい、請求項６に記載の、１位にＸ’を有する２－メチル－２，６－ヘプタジエン化合物。The acyloxy group is a linear aliphatic acyloxy group or an acyloxy group having an isomer relationship therewith, and the linear aliphatic acyloxy group is a formyloxy group, an acetoxy group, a propanoyloxy group, a may be selected from the group consisting of a noyloxy group, a pentanoyloxy group, a hexanoyloxy group, a heptanoyloxy group, an octanoyloxy group, a nonanoyloxy group, a decanoyloxy group and a crotonyloxy group; 2-methyl-2,6-heptadiene compounds having X' at the 1-position as described. 前記アシルオキシ基が分岐状の脂肪族アシルオキシ基又はこれらと異性体の関係にあるアシルオキシ基であり、該分岐状の脂肪族アシルオキシ基が、２－メチルプロパノイルオキシ基、ピバロイルオキシ基、２－メチルブタノイルオキシ基、３－メチル－２－ブテノイルオキシ基及び３－メチル－３－ブテノイルオキシ基から成る群から選択されてもよい、請求項６に記載の、１位にＸ’を有する２－メチル－２，６－ヘプタジエン化合物。The acyloxy group is a branched aliphatic acyloxy group or an acyloxy group having an isomer relationship therewith, and the branched aliphatic acyloxy group is a 2-methylpropanoyloxy group, a pivaloyloxy group, or a 2-methylbutyraloxy group. 2-Methyl-2 having X' at position 1, according to claim 6, which may be selected from the group consisting of a noyloxy group, a 3-methyl-2-butenoyloxy group and a 3-methyl-3-butenoyloxy group. , 6-heptadiene compounds. 前記アシルオキシ基がハロゲン化アシルオキシ基又はこれらと異性体の関係にあるアシルオキシ基であり、該ハロゲン化アシルオキシ基がトリクロロアセトキシ基及びトリフルオロアセトキシ基から成る群から選択されてもよい、請求項６に記載の、１位にＸ’を有する２－メチル－２，６－ヘプタジエン化合物。7. According to claim 6, wherein the acyloxy group is a halogenated acyloxy group or an acyloxy group having an isomer relationship therewith, and the halogenated acyloxy group may be selected from the group consisting of a trichloroacetoxy group and a trifluoroacetoxy group. 2-methyl-2,6-heptadiene compounds having X' at the 1-position as described. 前記アシルオキシ基が芳香族アシルオキシ基又はこれらと異性体の関係にあるアシルオキシ基であり、該芳香族アシルオキシ基がベンゾイルオキシ基から成る群から選択されてもよい、請求項６に記載の、１位にＸ’を有する２－メチル－２，６－ヘプタジエン化合物。7. The 1-position according to claim 6, wherein the acyloxy group is an aromatic acyloxy group or an acyloxy group in an isomeric relationship thereof, and the aromatic acyloxy group may be selected from the group consisting of a benzoyloxy group. 2-methyl-2,6-heptadiene compounds having X' in 前記アシルオキシ基がホルミルオキシ基、アセトキシ基、プロパノイルオキシ基、ピバロイルオキシ基、２－メチルプロパノイルオキシ基及びベンゾイルオキシ基から成る群から選択される、請求項６に記載の、１位にＸ’を有する２－メチル－２，６－ヘプタジエン化合物。X' at position 1 according to claim 6, wherein said acyloxy group is selected from the group consisting of formyloxy, acetoxy, propanoyloxy, pivaloyloxy, 2-methylpropanoyloxy and benzoyloxy groups. 2-methyl-2,6-heptadiene compound having 下記一般式（１’’）
Figure 2022022960000013
 （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。 The following general formula (1'')
Figure 2022022960000013
 (Wherein, X'' represents an alkanesulfonyloxy group having 1 to 10 carbon atoms or an arenesulfonyloxy group having 6 to 20 carbon atoms.)
A 2-methyl-2,6-heptadiene compound having X'' at the 1-position, represented by
JP2021011957A 2020-07-10 2021-01-28 Process for preparing 6-isopropenyl-3-methyl-9-decenyl acetate, and intermediates therefor Pending JP2022022960A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US17/368,996 US11795133B2 (en) 2020-07-10 2021-07-07 Process for preparing 6-isopropenyl-3-methyl-9-decenyl acetate, and intermediates therefor
EP21184426.1A EP3936500A1 (en) 2020-07-10 2021-07-08 Process for preparing 6-isopropenyl-3-methyl-9-decenyl acetate, and intermediates therefor
CN202110778909.XA CN113912494A (en) 2020-07-10 2021-07-09 Preparation method of 6-isopropenyl-3-methyl-9-decenyl acetate and intermediate thereof

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JP2020119194 2020-07-10
JP2020119194 2020-07-10

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JP2022022960A JP2022022960A (en) 2022-02-07
JP2022022960A5 true JP2022022960A5 (en) 2023-04-25

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