JP7255010B2 - 8-undecenyl nucleophile, method for producing same, and method for producing 9-dodecenal compound - Google Patents

Description

The present invention relates to an 8-undecenyl nucleophile, a method for producing the same, and a method for producing a 9-dodecenal compound. The present invention also relates to an 11-halo-3-undecene compound, a method for producing the same, and a method for producing a 9-dodecenal compound.

The Nettle caterpillars Setothosea asigna and Setora nitens are important pests of palm trees in Southeast Asia. there is In addition, since these insect pests damage young trees, they pose a serious problem in the cultivation of plantations. At present, pesticides are used for control, but since coconut oil is also used as food, residual pesticides may become a problem. Therefore, biological control methods are attracting attention, and one of them is expected to be the use of sex pheromone substances (Non-Patent Documents 1 and 2).

The sex pheromone of Setothosea asigna is reported to be a mixture of (9E)-9,11-dodecadienal and (9E)-9-dodecenal (Non-Patent Document 1). It has also been reported that the sex pheromone of Setora nitens is a mixture of (9Z)-9,11-dodecadienal and (9Z)-9-dodecenal (Non-Patent Document 2).

As methods for producing these sex pheromones, for example, the following methods are known. It has been reported that (9E)-9-dodecenal, a sex pheromone substance of Setothosea asigna , can be produced by pyridinium chlorochromate (PCC) oxidation of (9E)-9-dodecenol (Non-Patent Document 1). It has been reported that (9Z)-9-dodecenal, the sex pheromone substance of Setora nitens , can be produced by pyridinium chlorochromate (PCC) oxidation or Swern oxidation of (9Z)-9-dodecenol (non Patent Documents 2 and 3).

Gerhard Gries et al, 1997,J. Chem. Ecol. 23(9):2187-2196. Gerhard Gries et al, 2000,J. Chem. Ecol. 26(8):1969-1981. Tidwell Thomas T. , 1990, Organic Reactions, 39, "Oxidation of Alcohols to Carbonyl compounds via Alkoxysulfonium Ylides: The Moffatt, Swern, and Related Oxidations"

However, the production methods reported in Non-Patent Documents 1 and 2 include an oxidation reaction using a chromium compound that has a very large environmental load, and the oxidation reaction is often accompanied by the danger of explosion. Difficult to implement.
In addition, the production method reported in Non-Patent Document 3 produces carbon monoxide, which is a toxic gas, and dimethyl sulfide, which emits a foul odor, as by-products. Therefore, a special reactor is required, and it is difficult to implement on an industrial scale. . Another problem is that the yield in the reaction is as low as 19%.

An object of the present invention is to solve the above problems, and an 8-undecenyl nucleophile useful as an intermediate for a nucleophile used in synthesizing a 9-dodecenal compound, a method for producing the same, and the 8- A method for producing a 9-dodecenal compound using an undecenyl nucleophile is provided. Further, with the object of solving the above problems, the present invention provides a 11-halo-3-undecene compound useful as an intermediate for a nucleophilic reagent used in synthesizing a 9-dodecenal compound, and a method for producing the same. and a method for producing a 9-dodecenal compound using the 11-halo-3-undecene compound.

As a result of intensive studies, the present inventors have found an 8-undecenyl nucleophile, and by using the 8-undecenyl nucleophile, it is possible to produce a 9-dodecenal compound with good yield and high geometric purity. found out, and came to make the present invention. In addition, the present inventors have made intensive studies, and as a result, have found an 11-halo-3-undecene compound. In addition, the present inventors have found that it can be produced with good geometric purity, and have completed the present invention.

（式中、Ｒは互いに同じであっても異なっていてもよい炭素数１～６のアルキル基を表す。）
で表されるオルトギ酸エステル化合物との求核置換反応により、下記一般式（３）
ＣＨ_３ＣＨ_２ＣＨ＝ＣＨ（ＣＨ_２）_７ＣＨ（ＯＲ）_２ （３）
（式中、Ｒは、上記で定義した通りである。）
で表される１，１－ジアルコキシ－９－ドデセン化合物を得る工程と、
前記１，１－ジアルコキシ－９－ドデセン化合物（３）の加水分解反応により、下記一般式（４）
ＣＨ_３ＣＨ_２ＣＨ＝ＣＨ（ＣＨ_２）_７ＣＨＯ （４）
で表される９－ドデセナール化合物を得る工程と
を少なくとも含む、９－ドデセナール化合物（４）の製造方法が提供される。
また、本発明の更に他の態様によれば、上記の８－ウンデセニル求核試薬（１）の製造方法及び上記の９－ドデセナール化合物（４）の製造方法において、前記１－ハロ－５－ハロペンタン化合物（６）において、Ｘ^３が臭素原子であり、且つＸ^４が塩素原子であってもよく、前記１１－ハロ－３－ウンデセン化合物（７）において、Ｘ^１が塩素原子であってもよい。
また、本発明の更に他の態様によれば、上記の８－ウンデセニル求核試薬（１）の製造方法において、
３－ヘキセニル求核試薬（５）が、下記一般式（５－１）

（式中、Ｍ^２は上記で定義された通りである。）
で表される（３Ｅ）－３－ヘキセニル求核試薬であってもよく、
１１－ハロ－３－ウンデセン化合物（７）が、下記一般式（７－１）

（式中、Ｘ^１は上記で定義された通りである。）
で表される（３Ｅ）－１１－ハロ－３－ウンデセン化合物であってもよく、並びに、
８－ウンデセニル求核試薬（１）が、下記一般式（１－１）

（式中、Ｍ^１は上記で定義された通りである。）
で表される（８Ｅ）－８－ウンデセニル求核試薬であってもよい。
また、本発明の更に他の態様によれば、上記の９－ドデセナール化合物（４）の製造方法において、
３－ヘキセニル求核試薬（５）が、下記一般式（５－１）

（式中、Ｍ^２は上記で定義された通りである。）
で表される（３Ｅ）－３－ヘキセニル求核試薬であってもよく、
１１－ハロ－３－ウンデセン化合物（７）が、下記一般式（７－１）

（式中、Ｘ^１は上記で定義された通りである。）
で表される（３Ｅ）－１１－ハロ－３－ウンデセン化合物であってもよく、
８－ウンデセニル求核試薬（１）が、下記一般式（１－１）

（式中、Ｍ^１は上記で定義された通りである。）
で表される（８Ｅ）－８－ウンデセニル求核試薬であってもよく、
１，１－ジアルコキシ－９－ドデセン化合物（３）が、下記一般式（３－１）

（式中、Ｒは、上記で定義した通りである。）
で表される（９Ｅ）－１，１－ジアルコキシ－９－ドデセン化合物であってもよく、
９－ドデセナール化合物（４）が、下記一般式（４－１）

で表される（９Ｅ）－９－ドデセナール化合物であってもよい。 According to one aspect of the present invention, in the presence of a monovalent copper halide and a C 3-9 trialkyl phosphite compound,
General formula (5) below
_{CH3CH2CH =} CH( _CH2 ) _2M2 ( ⁵ )
(Wherein, ^M2 represents Li or ^MgZ2 , and ^Z2 represents a halogen atom or a 3-hexenyl group.)
and a 3-hexenyl nucleophile represented by the following general formula (6)
^X3 ( _CH2 ) _5X4 ⁽ 6)
(In the formula, ^X3 and ^X4 represent halogen atoms which may be the same or different.)
By a coupling reaction with a 1-halo-5-halopentane compound represented by the following general formula (7)
_{CH3CH2CH =} CH( _CH2 ) _7X1 ( ⁷ )
(In the formula, X ¹ represents a halogen atom.)
obtaining a 11-halo-3-undecene compound represented by
From the 11-halo-3-undecene compound (7), the following general formula (1)
_{CH3CH2CH =} CH( _CH2 ) _7M1 ( ¹ )
(Wherein, M ¹ represents Li or MgZ ¹ , and Z ¹ represents a halogen atom or an 8-undecenyl group.)
A method for producing an 8-undecenyl nucleophile (1) is provided, comprising at least the step of preparing an 8-undecenyl nucleophile represented by
Further, according to another aspect of the present invention, a method for producing the above-described 8-undecenyl nucleophile (1);
The 8-undecenyl nucleophile (1) and the following general formula (2)

(In the formula, R represents an alkyl group having 1 to 6 carbon atoms which may be the same or different.)
By a nucleophilic substitution reaction with an orthoformate compound represented by the following general formula (3)
_CH3CH2CH =CH( _CH2 ) _{7CH (} OR) ₂ (3)
(wherein R is as defined above.)
A step of obtaining a 1,1-dialkoxy-9-dodecene compound represented by
By hydrolysis reaction of the 1,1-dialkoxy-9-dodecene compound (3), the following general formula (4)
_{CH3CH2CH =} CH( _CH2 ) _7CHO (4)
A method for producing a 9-dodecenal compound (4) is provided, comprising at least a step of obtaining a 9-dodecenal compound represented by
According to still another aspect of the present invention, in the method for producing the 8-undecenyl nucleophile (1) and the method for producing the 9-dodecenal compound (4), the 1-halo-5-halopentane In the compound (6), X ³ may be a bromine atom and X ⁴ may be a chlorine atom, and in the 11-halo-3-undecene compound (7), X ¹ may be a chlorine atom. .
Further, according to still another aspect of the present invention, in the method for producing the above 8-undecenyl nucleophile (1),
3-hexenyl nucleophile (5) is represented by the following general formula (5-1)

(wherein ^M2 is as defined above.)
It may be a (3E)-3-hexenyl nucleophile represented by
11-halo-3-undecene compound (7) has the following general formula (7-1)

(Where X ¹ is as defined above.)
(3E)-11-halo-3-undecene compound represented by
8-undecenyl nucleophile (1) is represented by the following general formula (1-1)

(wherein M ¹ is as defined above.)
(8E)-8-undecenyl nucleophile represented by
Further, according to still another aspect of the present invention, in the method for producing the above 9-dodecenal compound (4),
3-hexenyl nucleophile (5) is represented by the following general formula (5-1)

(wherein ^M2 is as defined above.)
It may be a (3E)-3-hexenyl nucleophile represented by
11-halo-3-undecene compound (7) has the following general formula (7-1)

(Where X ¹ is as defined above.)
It may be a (3E)-11-halo-3-undecene compound represented by
8-undecenyl nucleophile (1) is represented by the following general formula (1-1)

(wherein M ¹ is as defined above.)
(8E)-8-undecenyl nucleophile represented by
1,1-dialkoxy-9-dodecene compound (3) has the following general formula (3-1)

(wherein R is as defined above.)
It may be a (9E)-1,1-dialkoxy-9-dodecene compound represented by
9-dodecenal compound (4) is represented by the following general formula (4-1)

It may be a (9E)-9-dodecenal compound represented by

（式中、Ｒは互いに同じであっても異なっていてもよい炭素数１～６のアルキル基を表す。）
で表されるオルトギ酸エステル化合物との求核置換反応により、下記一般式（３）
ＣＨ_３ＣＨ_２ＣＨ＝ＣＨ（ＣＨ_２）_７ＣＨ（ＯＲ）_２ （３）
（式中、Ｒは、上記で定義した通りである。）
で表される１，１－ジアルコキシ－９－ドデセン化合物を得る工程と、
前記１，１－ジアルコキシ－９－ドデセン化合物（３）の加水分解反応により、下記一般式（４）
ＣＨ_３ＣＨ_２ＣＨ＝ＣＨ（ＣＨ_２）_７ＣＨＯ （４）
で表される９－ドデセナール化合物を得る工程と
を少なくとも含む、９－ドデセナール化合物（４）の製造方法が提供される。 According to another aspect of the present invention, the following general formula (1)
_{CH3CH2CH =} CH( _CH2 ) _7M1 ( ¹ )
(Wherein, M ¹ represents Li or MgZ ¹ , and Z ¹ represents a halogen atom or an 8-undecenyl group.)
and an 8-undecenyl nucleophile represented by the following general formula (2)

(In the formula, R represents an alkyl group having 1 to 6 carbon atoms which may be the same or different.)
By a nucleophilic substitution reaction with an orthoformate compound represented by the following general formula (3)
_CH3CH2CH =CH( _CH2 ) _{7CH (} OR) ₂ (3)
(wherein R is as defined above.)
A step of obtaining a 1,1-dialkoxy-9-dodecene compound represented by
By hydrolysis reaction of the 1,1-dialkoxy-9-dodecene compound (3), the following general formula (4)
_{CH3CH2CH =} CH( _CH2 ) _7CHO (4)
A method for producing a 9-dodecenal compound (4) is provided, comprising at least a step of obtaining a 9-dodecenal compound represented by

Further, according to another aspect of the present invention, the following general formula (5)
_{CH3CH2CH =} CH( _CH2 ) _2M2 ( ⁵ )
(Wherein, ^M2 represents Li or ^MgZ2 , and ^Z2 represents a halogen atom or a 3-hexenyl group.)
and a 3-hexenyl nucleophile represented by the following general formula (6)
^X3 ( _CH2 ) _5X4 ⁽ 6)
(In the formula, ^X3 and ^X4 represent halogen atoms which may be the same or different.)
By a coupling reaction with a 1-halo-5-halopentane compound represented by the following general formula (7)
_{CH3CH2CH =} CH( _CH2 ) _7X1 ( ⁷ )
(In the formula, X ¹ represents a halogen atom.)
obtaining the 11-halo-3-undecene compound represented by the following.
Also according to another aspect of the present invention, the above 9 further comprising the step of preparing said 8-undecenyl nucleophile (1) from said 11-halo-3-undecene compound (7). - A process for the preparation of dodecenal compound (4) is provided.

According to one aspect of the present invention, the following general formula (5)
_{CH3CH2CH =} CH( _CH2 ) _2M2 ( ⁵ )
(Wherein, ^M2 represents Li or ^MgZ2 , and ^Z2 represents a halogen atom or a 3-hexenyl group.)
and a 3-hexenyl nucleophile represented by the following general formula (6)
^X3 ( _CH2 ) _5X4 ⁽ 6)
(In the formula, ^X3 and ^X4 represent halogen atoms which may be the same or different.)
By a coupling reaction with a 1-halo-5-halopentane compound represented by the following general formula (7)
_{CH3CH2CH =} CH( _CH2 ) _7X1 ( ⁷ )
(In the formula, X ¹ represents a halogen atom.)
obtaining the 11-halo-3-undecene compound represented by the following.

Also, according to another aspect of the present invention,
a method for producing the above 11-halo-3-undecene compound (7);
From the above 11-halo-3-undecene compound (7), the following general formula (1)
_{CH3CH2CH =} CH( _CH2 ) _7M1 ( ¹ )
(Wherein, M ¹ represents Li or MgZ ¹ , and Z ¹ represents a halogen atom or an 8-undecenyl group.)
A method for producing an 8-undecenyl nucleophile (1) is provided, comprising at least the step of preparing an 8-undecenyl nucleophile represented by

（式中、Ｒは互いに同じであっても異なっていてもよい炭素数１～６のアルキル基を表す。）
で表されるオルトギ酸エステル化合物との求核置換反応により、下記一般式（３）
ＣＨ_３ＣＨ_２ＣＨ＝ＣＨ（ＣＨ_２）_７ＣＨ（ＯＲ）_２ （３）
（式中、Ｒは、上記で定義した通りである。）
で表される１，１－ジアルコキシ－９－ドデセン化合物を得る工程と、
上記１，１－ジアルコキシ－９－ドデセン化合物（３）の加水分解反応により、下記一般式（４）
ＣＨ_３ＣＨ_２ＣＨ＝ＣＨ（ＣＨ_２）_７ＣＨＯ （４）
で表される９－ドデセナール化合物を得る工程と
を少なくとも含む、９－ドデセナール化合物（４）の製造方法が提供される。
代替的には、本発明の他の態様によれば、下記一般式（７）
ＣＨ_３ＣＨ_２ＣＨ＝ＣＨ（ＣＨ_２）_７Ｘ^１ （７）
（式中、Ｘ^１はハロゲン原子を表す。）
で表される１１－ハロ－３－ウンデセン化合物から、下記一般式（１）
ＣＨ_３ＣＨ_２ＣＨ＝ＣＨ（ＣＨ_２）_７Ｍ^１ （１）
（式中、Ｍ^１はＬｉ又はＭｇＺ^１を表し、Ｚ^１はハロゲン原子又は８－ウンデセニル基を表す。）
で表される８－ウンデセニル求核試薬を調製する工程と、
上記８－ウンデセニル求核試薬と、上記一般式（２）で表されるオルトギ酸エステル化合物との求核置換反応により、下記一般式（３）
ＣＨ_３ＣＨ_２ＣＨ＝ＣＨ（ＣＨ_２）_７ＣＨ（ＯＲ）_２ （３）
（式中、Ｒは、上記で定義した通りである。）
で表される１，１－ジアルコキシ－９－ドデセン化合物を得る工程と、
上記１，１－ジアルコキシ－９－ドデセン化合物（３）の加水分解反応により、下記一般式（４）
ＣＨ_３ＣＨ_２ＣＨ＝ＣＨ（ＣＨ_２）_７ＣＨＯ （４）
で表される９－ドデセナール化合物を得る工程と
を少なくとも含む、９－ドデセナール化合物（４）の製造方法が提供される。 Also, according to another aspect of the present invention,
A method for producing the above 8-undecenyl nucleophile (1);
The above 8-undecenyl nucleophile and the following general formula (2)

(In the formula, R represents an alkyl group having 1 to 6 carbon atoms which may be the same or different.)
By a nucleophilic substitution reaction with an orthoformate compound represented by the following general formula (3)
_CH3CH2CH =CH( _CH2 ) _{7CH (} OR) ₂ (3)
(wherein R is as defined above.)
A step of obtaining a 1,1-dialkoxy-9-dodecene compound represented by
By hydrolysis reaction of the 1,1-dialkoxy-9-dodecene compound (3), the following general formula (4)
_{CH3CH2CH =} CH( _CH2 ) _7CHO (4)
A method for producing a 9-dodecenal compound (4) is provided, comprising at least a step of obtaining a 9-dodecenal compound represented by
Alternatively, according to another aspect of the present invention, general formula (7) below
_{CH3CH2CH =} CH( _CH2 ) _7X1 ( ⁷ )
(In the formula, X ¹ represents a halogen atom.)
from the 11-halo-3-undecene compound represented by the following general formula (1)
_{CH3CH2CH =} CH( _CH2 ) _7M1 ( ¹ )
(Wherein, M ¹ represents Li or MgZ ¹ , and Z ¹ represents a halogen atom or an 8-undecenyl group.)
preparing an 8-undecenyl nucleophile represented by
The nucleophilic substitution reaction between the 8-undecenyl nucleophile and the orthoformate compound represented by the general formula (2) gives the following general formula (3)
_CH3CH2CH =CH( _CH2 ) _{7CH (} OR) ₂ (3)
(wherein R is as defined above.)
A step of obtaining a 1,1-dialkoxy-9-dodecene compound represented by
By hydrolysis reaction of the 1,1-dialkoxy-9-dodecene compound (3), the following general formula (4)
_{CH3CH2CH =} CH( _CH2 ) _7CHO (4)
A method for producing a 9-dodecenal compound (4) is provided, comprising at least a step of obtaining a 9-dodecenal compound represented by

Further, according to another aspect of the present invention, the following general formula (7)
_{CH3CH2CH =} CH( _CH2 ) _7X1 ( ⁷ )
(In the formula, X ¹ represents a halogen atom.)
An 11-halo-3-undecene compound represented by is provided.

The 11-halo-3-undecene compound (7) of the present invention is useful in the production of 9-dodecenal compound (4).
Moreover, according to the present invention, the 9-dodecenal compound (4) can be produced in good yield without using an oxidation reaction.

First, the 11-halo-3-undecene compound (7), which is the starting material for preparing the 8-undecenyl nucleophile (1), will be described.
The 11-halo-3-undecene compound (7) is represented by the following general formula (6) with a 3-hexenyl nucleophile represented by the following general formula (5), as represented by the chemical reaction formula below. It can be synthesized by a step of obtaining 11-halo-3-undecene compound (7) through a coupling reaction with a 1-halo-5-halopentane compound.

（３Ｅ）－３－ヘキセニル求核試薬（５－１）の具体例としては、（３Ｅ）－３－ヘキセニルリチウム；（３Ｅ）－３－ヘキセニルマグネシウム＝クロリド、（３Ｅ）－３－ヘキセニルマグネシウム＝ブロミド、（３Ｅ）－３－ヘキセニルマグネシウム＝ヨージド等の（３Ｅ）－３－ヘキセニルマグネシウム＝ハライド試薬（グリニャール試薬）等が挙げられ、汎用性の観点から、（３Ｅ）－３－ヘキセニルマグネシウム＝ハライド試薬が好ましい。
（３Ｚ）－３－ヘキセニル求核試薬（５－２）の具体例としては、（３Ｚ）－３－ヘキセニルリチウム；（３Ｚ）－３－ヘキセニルマグネシウム＝クロリド、（３Ｚ）－３－ヘキセニルマグネシウム＝ブロミド、（３Ｚ）－３－ヘキセニルマグネシウム＝ヨージド等の（３Ｚ）－３－ヘキセニルマグネシウム＝ハライド試薬（グリニャール試薬）等が挙げられ、汎用性の観点から、（３Ｚ）－３－ヘキセニルマグネシウム＝ハライド試薬が好ましい。
３－ヘキセニル求核試薬（５）は、１種類又は２種類以上を使用してもよい。
３－ヘキセニル求核試薬（５）として、例えば、（３Ｅ）－３－ヘキセニル求核試薬（５－１）と（３Ｚ）－３－ヘキセニル求核試薬（５－２）の混合物を用いることにより、（３Ｅ）－１１－ハロ－３－ウンデセン化合物と（３Ｚ）－１１－ハロ－３－ウンデセン化合物との混合物を合成することができる。
また、３－ヘキセニル求核試薬（５）は、市販されているものであってもよく、また独自に合成したものであってもよい。
３－ヘキセニル求核試薬（５）は、下記化学反応式中の一般式（８）で表される１－ハロ－３－ヘキセン化合物から３－ヘキセニル求核試薬（５）を調製する工程により調製することができる。 ^M2 in the 3-hexenyl nucleophile (5) represents Li or ^MgZ2 , and ^Z2 represents a halogen atom or a 3-hexenyl group. Halogen atoms ^Z2 include chlorine, bromine and iodine atoms.
The 3-hexenyl nucleophiles (5) include (3E)-3-hexenyl nucleophiles represented by the following general formula (5-1), and (3Z) represented by the following general formula (5-2). -3-hexenyl nucleophiles, and mixtures thereof.

Specific examples of (3E)-3-hexenyl nucleophiles (5-1) include (3E)-3-hexenyllithium; (3E)-3-hexenylmagnesium=chloride, (3E)-3-hexenylmagnesium= (3E)-3-hexenylmagnesium=halide reagents (Grignard reagents) such as bromide, (3E)-3-hexenylmagnesium=iodide, and the like; Reagents are preferred.
Specific examples of (3Z)-3-hexenyl nucleophiles (5-2) include (3Z)-3-hexenyllithium; (3Z)-3-hexenylmagnesium=chloride, (3Z)-3-hexenylmagnesium= (3Z)-3-hexenylmagnesium=halide reagents (Grignard reagents) such as bromide, (3Z)-3-hexenylmagnesium=iodide, etc., and from the viewpoint of versatility, (3Z)-3-hexenylmagnesium=halide Reagents are preferred.
The 3-hexenyl nucleophile (5) may be used alone or in combination of two or more.
As the 3-hexenyl nucleophile (5), for example, by using a mixture of (3E)-3-hexenyl nucleophile (5-1) and (3Z)-3-hexenyl nucleophile (5-2) , (3E)-11-halo-3-undecene compounds and (3Z)-11-halo-3-undecene compounds can be synthesized.
Also, the 3-hexenyl nucleophile (5) may be commercially available or independently synthesized.
The 3-hexenyl nucleophile (5) is prepared by preparing a 3-hexenyl nucleophile (5) from a 1-halo-3-hexene compound represented by the general formula (8) in the chemical reaction formula below. can do.

For example, 3-hexenylmagnesium halide reagents (5:M 2 =MgZ 2 ) such as (3E)-3-hexenylmagnesium halide reagent and (3Z)-3-hexenylmagnesium halide reagent (5:M ² =MgZ ² ) can be used in the chemical reaction Prepared by reacting a 1-halo-3-hexene compound (8) with magnesium in a solvent to give a 3-hexenylmagnesium halide reagent (5: M ² =MgZ ² ), as shown in the formula be able to.

（３Ｅ）－１－ハロ－３－ヘキセン化合物（８－１）の具体例としては、（３Ｅ）－１－クロロ－３－ヘキセン、（３Ｅ）－１－ブロモ－３－ヘキセン、（３Ｅ）－１－ヨード－３－ヘキセン等が挙げられる。
（３Ｚ）－１－ハロ－３－ヘキセン化合物（８－２）の具体例としては、（３Ｚ）－１－クロロ－３－ヘキセン、（３Ｚ）－１－ブロモ－３－ヘキセン、（３Ｚ）－１－ヨード－３－ヘキセン等が挙げられる。
１－ハロ－３－ヘキセン化合物（８）は、１種類又は２種類以上を使用してもよい。
（３Ｅ）－１－ハロ－３－ヘキセン化合物（８－１）と（３Ｚ）－１－ハロ－３－ヘキセン化合物（８－２）の混合物を用いることにより、（３Ｅ）－３－ヘキセニル求核試薬と（３Ｚ）－３－ヘキセニル求核試薬との混合物を調製することができる。
また、１－ハロ－３－ヘキセン化合物（８）は、市販されているものであってもよく、また独自に合成したものであってもよい。
１－ハロ－３－ヘキセン化合物（８）から、３－ヘキセニルマグネシウム＝ハライド試薬（５：Ｍ^２＝ＭｇＺ^２）を調製する際に用いるマグネシウムの使用量は、反応完結の観点から、１－ハロ－３－ヘキセン化合物（８）１ｍｏｌに対して、好ましくは１．０～２．０グラム原子である。
１－ハロ－３－ヘキセン化合物（８）から、３－ヘキセニルマグネシウム＝ハライド試薬（５：Ｍ^２＝ＭｇＺ^２）を調製する際に用いる溶媒としては、テトラヒドロフラン、ジエチル＝エーテル、４－メチルテトラヒドロピラン等のエーテル系溶媒、トルエン、キシレン、ヘキサン等の炭化水素系溶媒等が挙げられるが、グリニャール試薬生成の反応速度の観点から、テトラヒドロフランが好ましい。
該溶媒は、１種類又は２種類以上を使用してもよい。また、該溶媒は、市販されているものであってもよく、また独自に合成したものであってもよい。
該溶媒の使用量は、反応性の観点から、１－ハロ－３－ヘキセン化合物（８）１ｍｏｌに対して、好ましくは１００～２０００ｇである。
１－ハロ－３－ヘキセン化合物（８）から、３－ヘキセニルマグネシウム＝ハライド試薬（５：Ｍ^２＝ＭｇＺ^２）を調製する際の反応温度は、用いる溶媒により異なるが、反応性の観点から、好ましくは３０～１２０℃である。
１－ハロ－３－ヘキセン化合物（８）から、３－ヘキセニルマグネシウム＝ハライド試薬（５：Ｍ^２＝ＭｇＺ^２）を調製する際の反応時間は、用いる溶媒又は反応スケールにより異なるが、反応性の観点から、好ましくは１～５０時間である。 X ² in the 1-halo-3-hexene compound (8) represents a halogen atom. The halogen atom ^X2 includes a chlorine atom, a bromine atom, an iodine atom, and the like.
The 1-halo-3-hexene compound (8) includes a (3E)-1-halo-3-hexene compound represented by the following general formula (8-1), and a (3E)-1-halo-3-hexene compound represented by the following general formula (8-2). (3Z)-1-halo-3-hexene compounds, and mixtures thereof.

Specific examples of (3E)-1-halo-3-hexene compound (8-1) include (3E)-1-chloro-3-hexene, (3E)-1-bromo-3-hexene, (3E) -1-iodo-3-hexene and the like.
Specific examples of (3Z)-1-halo-3-hexene compound (8-2) include (3Z)-1-chloro-3-hexene, (3Z)-1-bromo-3-hexene, (3Z) -1-iodo-3-hexene and the like.
The 1-halo-3-hexene compound (8) may be used alone or in combination of two or more.
By using a mixture of (3E)-1-halo-3-hexene compound (8-1) and (3Z)-1-halo-3-hexene compound (8-2), (3E)-3-hexenyl Mixtures of nucleating reagents and (3Z)-3-hexenyl nucleophiles can be prepared.
Also, the 1-halo-3-hexene compound (8) may be commercially available or may be independently synthesized.
From the viewpoint of reaction completion, the amount of magnesium used in preparing 3-hexenylmagnesium=halide reagent (5: M ² =MgZ ² ) from 1-halo-3-hexene compound (8) It is preferably 1.0 to 2.0 gram atoms per 1 mol of -3-hexene compound (8).
Solvents used in preparing 3-hexenylmagnesium halide reagent (5: M ² =MgZ ² ) from 1-halo-3-hexene compound (8) include tetrahydrofuran, diethyl ether, and 4-methyltetrahydropyran. and hydrocarbon solvents such as toluene, xylene, hexane, etc., but tetrahydrofuran is preferred from the viewpoint of the reaction rate of Grignard reagent production.
The solvent may be used alone or in combination of two or more. In addition, the solvent may be commercially available or may be independently synthesized.
From the viewpoint of reactivity, the amount of the solvent to be used is preferably 100 to 2000 g per 1 mol of the 1-halo-3-hexene compound (8).
The reaction temperature for preparing 3-hexenylmagnesium=halide reagent (5:M ² =MgZ ² ) from 1-halo-3-hexene compound (8) varies depending on the solvent used, but from the viewpoint of reactivity, It is preferably 30 to 120°C.
The reaction time for preparing 3-hexenylmagnesium=halide reagent (5: M ² =MgZ ² ) from 1-halo-3-hexene compound (8) varies depending on the solvent used or the scale of the reaction. From the point of view, it is preferably 1 to 50 hours.

For example, 3-hexenyllithium reagents (5:M = Li), such as (3E)-3-hexenyllithium and ( ^3Z )-3-hexenyllithium, can react with 1-halo It can be prepared by reacting the -3-hexene compound (8) with an organic lithium reagent in a solvent to give a 3-hexenyllithium reagent (5: M ² =Li).

Examples of organic lithium reagents include linear organic lithium reagents such as methyllithium, ethyllithium, n-propyllithium, n-butyllithium and n-pentyllithium, and branched organic lithium reagents such as sec-butyllithium and tert-butyllithium. Examples include organic lithium reagents, and from the viewpoint of versatility, methyllithium, n-butyllithium, sec-butyllithium, and tert-butyllithium are preferred.
From the viewpoint of reactivity, the amount of the organolithium reagent to be used is preferably 1.0 to 4.0 mol per 1 mol of the 1-halo-3-hexene compound (8).
Solvents used in preparing the 3-hexenyllithium reagent (5: M ² = Li) from the 1-halo-3-hexene compound (8) include ethers such as tetrahydrofuran, diethyl ether, and 4-methyltetrahydropyran. Hydrocarbon solvents such as system solvents, toluene, xylene, and hexane, etc., may be mentioned, and preferred solutions vary depending on the organolithium reagent used, but generally tetrahydrofuran, toluene, and hexane are preferred from the viewpoint of reactivity.
The solvent may be used alone or in combination of two or more. In addition, the solvent may be commercially available or may be independently synthesized.
From the viewpoint of reactivity, the amount of the solvent used is preferably 50 to 5000 g per 1 mol of the 1-halo-3-hexene compound (8).
N,N,N',N'- ^{tetramethylethylenediamine} (TMEDA), hexa Methylphosphoric acid triamide (HMPA), N,N'-dimethylpropylene urea (DMPU) or the like may be added to improve the reaction rate.
The reaction temperature for preparing the 3-hexenyllithium reagent (5: M ² = Li) from the 1-halo-3-hexene compound (8) varies depending on the solvent used, but from the viewpoint of reactivity, preferably - 78-25°C.
The reaction time for preparing the 3-hexenyllithium reagent (5: M ² = Li) from the 1-halo-3-hexene compound (8) varies depending on the solvent used or the reaction scale. It is preferably 1 to 50 hours.

In the above coupling reaction, the amount of the 3-hexenyl nucleophile (5) used is preferably 0.8 to 1 mol per 1 mol of the 1-halo-5-halopentane compound (6) from the viewpoint of economy. .4 mol.

X ³ and X ⁴ in the 1-halo-5-halopentane compound (6) represent halogen atoms which may be the same or different. Halogen atoms ^X3 and ^X4 include a chlorine atom, a bromine atom and an iodine atom.
Combinations of ^X3 and ^X4 include a chlorine atom and a chlorine atom, a bromine atom and a chlorine atom, a chlorine atom and an iodine atom, a bromine atom and a bromine atom, a bromine atom and an iodine atom, and an iodine atom and an iodine atom. .
Specific examples of the 1-halo-5-halopentane compound (6) include 1,5-dichloropentane, 1-bromo-5-chloropentane, 1-chloro-5-iodopentane, 1,5-dibromopentane, 1 -bromo-5-iodopentane, 1,5-diiodopentane and the like.
The 1-halo-5-halopentane compound (6) may be used alone or in combination of two or more. Also, the 1-halo-5-halopentane compound (6) may be commercially available or may be synthesized independently.
When X ³ and X ⁴ are different from each other, the coupling reaction can be performed while preferentially reacting the one with higher reactivity by appropriately selecting the catalyst or reaction temperature described below. For example, when using a 1-halo-5-halopentane compound (6) in which the combination of X ³ and X ⁴ different from each other is a chlorine atom and a bromine atom or a chlorine atom and an iodine atom, the 11-halo-3-undecene compound X ¹ in (7) can be a chlorine atom. Further, when using a 1-halo-5-halopentane compound (6) in which the combination of X ³ and X ⁴ different from each other is a bromine atom and an iodine atom, X ¹ in the 11-halo-3-undecene compound (7) is It can be an atom.

A solvent may be used for the coupling reaction, if necessary. Examples of the solvent include hydrocarbon solvents such as toluene, xylene and hexane, ether solvents such as tetrahydrofuran, 4-methyltetrahydropyran and diethyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, N- Polar solvents such as methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, and acetonitrile can be mentioned, but from the viewpoint of reactivity, toluene, tetrahydrofuran, 4-methyltetrahydropyran, and acetonitrile are preferred, and tetrahydrofuran is more preferred.
The solvent may be used alone or in combination of two or more. Moreover, a commercially available solvent can be used.
From the viewpoint of reactivity, the amount of the solvent to be used is preferably 30 to 3000 g per 1 mol of the 1-halo-5-halopentane compound (6).
A catalyst may be used for the coupling reaction, if necessary. Examples of the catalyst include monovalent copper halides such as cuprous chloride, cuprous bromide and cuprous iodide; From the viewpoint of reactivity, monovalent copper halide is preferred, and cuprous iodide is more preferred.
The catalyst may be used alone or in combination of two or more. In addition, as the catalyst, a commercially available one can be used.
The amount of the catalyst to be used is preferably 0.003 to 0.300 mol per 1 mol of the 1-halo-5-halopentane compound (6) from the viewpoint of reaction rate and post-treatment.
When using a catalyst for the coupling reaction, a co-catalyst may be used as necessary. Examples of the cocatalyst include phosphorous compounds such as trialkylphosphite compounds having 3 to 9 carbon atoms such as triethyl phosphite and triarylphosphine compounds having 18 to 21 carbon atoms such as triphenylphosphine. From the viewpoint of reactivity, triethyl phosphite is preferred.
The cocatalyst may be used alone or in combination of two or more. In addition, the co-catalyst may be commercially available.
The amount of the cocatalyst to be used is preferably 0.001-0.500 mol, more preferably 0.001-0.050 mol, per 1 mol of the 1-halo-5-halopentane compound (6).
When using a catalyst for the coupling reaction, lithium halide may be added as necessary. Lithium halides include lithium chloride, lithium bromide, lithium iodide and the like, and lithium chloride is preferred from the viewpoint of reactivity.
From the viewpoint of reactivity, the amount of lithium halide used in the coupling reaction is preferably 0.005 to 0.250 mol per 1 mol of the 1-halo-5-halopentane compound (6).
The reaction temperature in the coupling reaction varies depending on the 3-hexenyl nucleophile (5) used, but from the viewpoint of reactivity, it is preferably -78 to 70°C, more preferably -20 to 25°C.
The reaction time in the coupling reaction varies depending on the solvent used or the reaction scale, but is preferably 1 to 55 hours from the viewpoint of reactivity.

１１－ハロ－３－ウンデセン化合物（７）におけるＸ^１は、ハロゲン原子を表す。該ハロゲン原子Ｘ¹としては、塩素原子、臭素原子及びヨウ素原子等が挙げられる。
（３Ｅ）－１１－ハロ－３－ウンデセン化合物（７－１）の具体例としては、（３Ｅ）－１１－クロロ－３－ウンデセン、（３Ｅ）－１１－ブロモ－３－ウンデセン、（３Ｅ）－１１－ヨード－３－ウンデセン等が挙げられる。
（３Ｚ）－１１－ハロ－３－ウンデセン化合物（７－２）の具体例としては、（３Ｚ）－１１－クロロ－３－ウンデセン、（３Ｚ）－１１－ブロモ－３－ウンデセン、（３Ｚ）－１１－ヨード－３－ウンデセン等が挙げられる。 The 11-halo-3-undecene compound (7) includes a (3E)-11-halo-3-undecene compound represented by the following general formula (7-1), and a (3E)-11-halo-3-undecene compound represented by the following general formula (7-2). (3Z)-11-halo-3-undecene compounds, and mixtures thereof.

X ¹ in the 11-halo-3-undecene compound (7) represents a halogen atom. The halogen atom X ¹ includes a chlorine atom, a bromine atom, an iodine atom and the like.
Specific examples of the (3E)-11-halo-3-undecene compound (7-1) include (3E)-11-chloro-3-undecene, (3E)-11-bromo-3-undecene, (3E) -11-iodo-3-undecene and the like.
Specific examples of the (3Z)-11-halo-3-undecene compound (7-2) include (3Z)-11-chloro-3-undecene, (3Z)-11-bromo-3-undecene, (3Z) -11-iodo-3-undecene and the like.

Next, the method for producing the 1,1-dialkoxy-9-dodecene compound (3), which is part of the method for producing the 9-dodecenal compound (4) and is represented by the following chemical reaction formula, will be described below. . The production method comprises a nucleophilic substitution reaction between an 8-undecenyl nucleophile represented by the following general formula (1) and an orthoformate compound represented by the following general formula (2) to produce 1,1-di including obtaining an alkoxy-9-dodecene compound (3).

（８Ｅ）－８－ウンデセニル求核試薬（１－１）の具体例としては、（８Ｅ）－８－ウンデセニルリチウム、（８Ｅ）－８－ウンデセニルマグネシウム＝クロリド、（８Ｅ）－８－ウンデセニルマグネシウム＝ブロミド、（８Ｅ）－８－ウンデセニルマグネシウム＝ヨージド等の（８Ｅ）－８－ウンデセニルマグネシウム＝ハライド試薬（グリニャール試薬）が挙げられ、汎用性の観点から、（８Ｅ）－８－ウンデセニルマグネシウム＝ハライド試薬が好ましい。
（８Ｚ）－８－ウンデセニル求核試薬（１－２）の具体例としては、（８Ｚ）－８－ウンデセニルリチウム、（８Ｚ）－８－ウンデセニルマグネシウム＝クロリド、（８Ｚ）－８－ウンデセニルマグネシウム＝ブロミド、（８Ｚ）－８－ウンデセニルマグネシウム＝ヨージド等の（８Ｚ）－８－ウンデセニルマグネシウム＝ハライド試薬（グリニャール試薬）が挙げられ、汎用性の観点から、（８Ｚ）－８－ウンデセニルマグネシウム＝ハライド試薬が好ましい。
８－ウンデセニル求核試薬（１）は、１種類又は２種類以上を使用してもよい。
８－ウンデセニル求核試薬（１）として、例えば、（８Ｅ）－８－ウンデセニル求核試薬（１－１）と（８Ｚ）－８－ウンデセニル求核試薬（１－２）の混合物を用いることにより、（９Ｅ）－１，１－ジアルコキシ－９－ドデセン化合物と（９Ｚ）－１，１－ジアルコキシ－９－ドデセン化合物との混合物を合成することができる。
また、８－ウンデセニル求核試薬（１）は、独自に合成したものであってもよい。
８－ウンデセニル求核試薬（１）は、上記の１１－ハロ－３－ウンデセン化合物（７）から８－ウンデセニル求核試薬（１）を調製する工程により調製することができる。 M ¹ in the 8-undecenyl nucleophile (1) represents Li or MgZ ¹ , and Z ¹ represents a halogen atom or an 8-undecenyl group. The halogen atom ^Z1 includes a chlorine atom, a bromine atom, an iodine atom, and the like.
As the 8-undecenyl nucleophile (1), (8E)-8-undecenyl nucleophile represented by the following general formula (1-1), (8Z) represented by the following general formula (1-2) -8-undecenyl nucleophiles, and mixtures thereof.

Specific examples of (8E)-8-undecenyl nucleophiles (1-1) include (8E)-8-undecenyllithium, (8E)-8-undecenylmagnesium chloride, (8E)-8 (8E)-8-undecenylmagnesium=halide reagents (Grignard reagents) such as -undecenylmagnesium=bromide, (8E)-8-undecenylmagnesium=iodide, and from the viewpoint of versatility, ( 8E)-8-Undecenylmagnesium halide reagent is preferred.
Specific examples of (8Z)-8-undecenyl nucleophiles (1-2) include (8Z)-8-undecenyllithium, (8Z)-8-undecenylmagnesium chloride, (8Z)-8 (8Z)-8-undecenylmagnesium=halide reagents (Grignard reagents) such as -undecenylmagnesium=bromide and (8Z)-8-undecenylmagnesium=iodide, and from the viewpoint of versatility, ( 8Z)-8-undecenylmagnesium halide reagent is preferred.
The 8-undecenyl nucleophile (1) may be used alone or in combination of two or more.
As the 8-undecenyl nucleophile (1), for example, by using a mixture of (8E)-8-undecenyl nucleophile (1-1) and (8Z)-8-undecenyl nucleophile (1-2) , (9E)-1,1-dialkoxy-9-dodecene compounds and (9Z)-1,1-dialkoxy-9-dodecene compounds can be synthesized.
In addition, the 8-undecenyl nucleophile (1) may be one synthesized independently.
8-Undecenyl nucleophile (1) can be prepared by the process of preparing 8-undecenyl nucleophile (1) from 11-halo-3-undecene compound (7) described above.

8-undecenylmagnesium=halide reagents such as (8E)-8-undecenylmagnesium=halide reagent and (8Z)-8-undecenylmagnesium=halide reagent (1:M ¹ =MgX ¹ ) is a 8-undecenylmagnesium=halide reagent (1:M ¹ =MgX It can be prepared by the process of obtaining ¹ ).

The 11-halo-3-undecene compound (7) may be used alone or in combination of two or more.
For example, by using a mixture of (3E)-11-halo-3-undecene and (3Z)-11-halo-3-undecene compounds, (8E)-8-undecenyl nucleophiles and (8Z)-8 - Mixtures of undecenyl nucleophiles can be prepared.
Also, the 11-halo-3-undecene compound (7) may be synthesized independently.
The amount of magnesium used in preparing 8-undecenylmagnesium=halide reagent (1:M ¹ =MgX ¹ ) from 11-halo-3-undecene compound (7) is 11- It is preferably 1.0 to 2.0 gram atoms per 1 mol of the halo-3-undecene compound (7).
Examples of the solvent include ether solvents such as tetrahydrofuran, diethyl ether, and 4-methyltetrahydropyran, and hydrocarbon solvents such as toluene, xylene, and hexane. Tetrahydrofuran is preferred.
The amount of the solvent to be used is preferably 100 to 2000 g per 1 mol of the 11-halo-3-undecene compound (7) from the viewpoint of reactivity.
The reaction temperature for preparing the 8-undecenylmagnesium halide reagent (1:M ¹ =MgX ¹ ) from the 11-halo-3-undecene compound (7) varies depending on the solvent used, but from the viewpoint of reactivity , preferably 30 to 120°C.
The reaction time for preparing the 8-undecenylmagnesium halide reagent (1:M ¹ =MgX ¹ ) from the 11-halo-3-undecene compound (7) varies depending on the solvent used or the reaction scale, but the reactivity from the point of view, it is preferably 1 to 50 hours.

For example, (8E)-8-undecenyllithium and (8Z)-8-undecenyllithium reagents (1:M ¹ =Li) such as (8E)-8-undecenyllithium can be prepared using the following chemistry As shown in the reaction formula, the 11-halo-3-undecene compound (7) is reacted with an organolithium reagent in a solvent to give (8E)-8-undecenyllithium reagent (1:M ¹ =Li). can be prepared by the process of obtaining

Examples of organic lithium reagents include linear organic lithium reagents such as methyllithium, ethyllithium, n-propyllithium, n-butyllithium and n-pentyllithium, and branched organic lithium reagents such as sec-butyllithium and tert-butyllithium. Examples include organic lithium reagents, and from the viewpoint of versatility, methyllithium, n-butyllithium, sec-butyllithium, and tert-butyllithium are preferred.
From the viewpoint of reactivity, the amount of the organolithium reagent to be used is preferably 1.0 to 4.0 mol per 1 mol of the 11-halo-3-undecene compound (7).
Solvents used in preparing (8E)-8-undecenyllithium reagent (1:M ¹ =Li) from 11-halo-3-undecene compound (7) include tetrahydrofuran, diethyl ether, 4- Examples thereof include ether solvents such as methyltetrahydropyran, and hydrocarbon solvents such as toluene, xylene, and hexane. Preferred solutions vary depending on the organolithium reagent used. , hexane is preferred.
The solvent may be used alone or in combination of two or more. In addition, the solvent may be commercially available or may be independently synthesized.
From the viewpoint of reactivity, the amount of the solvent used is preferably 50 to 5000 g per 1 mol of the 11-halo-3-undecene compound (7).
In preparing the (8E)-8-undecenyllithium reagent ( ¹ :M = Li) from the 11-halo-3-undecene compound (7), N,N,N',N'-tetramethyl Ethylenediamine (TMEDA), hexamethylphosphoric acid triamide (HMPA), N,N'-dimethylpropylene urea (DMPU), etc. may be added to improve the reaction rate.
The reaction temperature for preparing the (8E)-8-undecenyllithium reagent (1:M ¹ =Li) from the 11-halo-3-undecene compound (7) varies depending on the solvent used. From the point of view, it is preferably -78 to 25°C.
The reaction time for preparing the (8E)-8-undecenyllithium reagent (1:M ¹ =Li) from the 11-halo-3-undecene compound (7) varies depending on the solvent used or the reaction scale. From the viewpoint of reactivity, it is preferably 1 to 50 hours.

The amount of the 8-undecenyl nucleophile (1) to be used is preferably 0.5 to 1.5 mol per 1 mol of the orthoformate compound (2) from the viewpoint of economy.

The three R's in the orthoformic acid ester compound (2) represent an alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, which may be the same or different.
Examples of alkyl groups having 1 to 6 carbon atoms include linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group and n-hexyl group, isopropyl group and isobutyl group. and branched alkyl groups such as
Examples of the orthoformate compound (2) include methyl orthoformate, ethyl orthoformate, propyl orthoformate, butyl orthoformate, pentyl orthoformate, and hexyl orthoformate. , and ethyl orthoformate are preferred.
The orthoformic acid ester compound (2) may be used alone or in combination of two or more. In addition, as the orthoformic acid ester compound (2), commercially available products can be used.

Examples of the solvent used for the nucleophilic substitution reaction include hydrocarbon solvents such as toluene, xylene and hexane, and ether solvents such as tetrahydrofuran, 4-methyltetrahydropyran and diethyl ether. Alternatively, 4-methyltetrahydropyran is preferred.
The solvent may be used alone or in combination of two or more. Moreover, a commercially available solvent can be used.
When the 8-undecenyl nucleophile (1) is diluted with a solvent, or when a solvent is used in preparing the 8-undecenyl nucleophile (1), these solvents and the solvent used in the nucleophilic substitution reaction may be the same or different.
Moreover, when the solvent is different, it may be substituted with a solvent that increases the reactivity of the nucleophilic substitution reaction.
For example, when tetrahydrofuran is used as a solvent when preparing 8-undecenyl nucleophile (1), and toluene is selected as a solvent for the nucleophilic substitution reaction, 8-undecenyl nucleophile (1) containing tetrahydrofuran is used. After addition to a reactor containing the orthoformate compound and toluene, the solvent in the reaction system may be replaced with toluene by distilling off tetrahydrofuran in the process of raising the reaction temperature.
From the viewpoint of reactivity, the amount of the solvent used is preferably 100 to 6000 g per 1 mol of the orthoformate compound (2).
The reaction temperature in the nucleophilic substitution reaction is preferably 75 to 130° C. from the viewpoint of allowing the reaction to proceed smoothly and preventing evaporation of the solvent.
The reaction time in the nucleophilic substitution reaction varies depending on the solvent used or the reaction scale, but is preferably 1 to 100 hours.

１，１－ジアルコキシ－９－ドデセン化合物（３）におけるＲは、オルトギ酸エステル化合物（２）のＲと同じである。
（９Ｅ）－１，１－ジアルコキシ－９－ドデセン化合物（３－１）の具体例としては、（９Ｅ）－ １，１－ジメトキシ－９－ドデセン、（９Ｅ）－１，１－ジエトキシ－９－ドデセン、（９Ｅ）－１，１－ジプロポキシ－９－ドデセン、（９Ｅ）－ １，１－ジブトキシ－９－ドデセン等が挙げられる。
（９Ｚ）－１，１－ジアルコキシ－９－ドデセン化合物（３－２）の具体例としては、（９Ｚ）－ １，１－ジメトキシ－９－ドデセン、（９Ｚ）－１，１－ジエトキシ－９－ドデセン、（９Ｚ）－１，１－ジプロポキシ－９－ドデセン、（９Ｚ）－ １，１－ジブトキシ－９－ドデセン等が挙げられる。 As the 1,1-dialkoxy-9-dodecene compound (3), (9E)-1,1-dialkoxy-9-dodecene compound represented by the following general formula (3-1), the following general formula (3 -2) and (9Z)-1,1-dialkoxy-9-dodecene compounds and mixtures thereof.

R in the 1,1-dialkoxy-9-dodecene compound (3) is the same as R in the orthoformate compound (2).
Specific examples of (9E)-1,1-dialkoxy-9-dodecene compounds (3-1) include (9E)-1,1-dimethoxy-9-dodecene, (9E)-1,1-diethoxy- 9-dodecene, (9E)-1,1-dipropoxy-9-dodecene, (9E)-1,1-dibutoxy-9-dodecene and the like.
Specific examples of (9Z)-1,1-dialkoxy-9-dodecene compounds (3-2) include (9Z)-1,1-dimethoxy-9-dodecene, (9Z)-1,1-diethoxy- 9-dodecene, (9Z)-1,1-dipropoxy-9-dodecene, (9Z)-1,1-dibutoxy-9-dodecene and the like.

Next, the method for producing 9-dodecenal compound (4), which is part of the method for producing 9-dodecenal compound (4) and is represented by the following chemical reaction formula, will be described below. The production method includes a step of hydrolyzing 1,1-dialkoxy-9-dodecene compound (3) to obtain 9-dodecenal compound (4).

The 1,1-dialkoxy-9-dodecene compound (3) may be used alone or in combination of two or more.
As the 1,1-dialkoxy-9-dodecene compound (3), for example, (9E)-1,1-dialkoxy-9-dodecene compound and (9Z)-1,1-dialkoxy-9-dodecene compound can be used to synthesize a mixture of (9E)-9-dodecenal and (9Z)-9-dodecenal.
The hydrolysis reaction can be performed using, for example, an acid, water, and optionally a solvent.
Acids used in the hydrolysis reaction include inorganic acids such as hydrochloric acid and hydrobromic acid, p-toluenesulfonic acid, trifluoroacetic acid, acetic acid, formic acid, oxalic acid, iodotrimethylsilane, and titanium tetrachloride. From the viewpoint of reactivity, acetic acid, formic acid or oxalic acid is preferred.
One or more of these acids may be used. In addition, as the acid, a commercially available one can be used.
The amount of the acid to be used is preferably 0.01-10.0 mol per 1 mol of the 1,1-dialkoxy-9-dodecene compound (3).
The amount of water used in the hydrolysis reaction is preferably 18 to 3000 g per 1 mol of the 1,1-dialkoxy-9-dodecene compound (3) from the viewpoint of reactivity.
Solvents used in the hydrolysis reaction include hydrocarbon solvents such as toluene, xylene and hexane, ether solvents such as tetrahydrofuran and diethyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone. , acetonitrile, γ-butyrolactone, dichloromethane, chloroform, and other polar solvents, and methanol, ethanol, and other alcoholic solvents.
The solvent may be used alone or in combination of two or more. Also, as the solvent, a commercially available one can be used.
Although the optimum solvent varies depending on the acid used, for example, when oxalic acid is used as the acid, tetrahydrofuran is preferred from the viewpoint of reactivity.
The amount of the solvent used is preferably 0 to 3000 g per 1 mol of the 1,1-dialkoxy-9-dodecene compound (3) from the viewpoint of reactivity.
The reaction temperature in the hydrolysis reaction varies depending on the acid or solvent used, but is preferably 5 to 180°C from the viewpoint of reactivity.
The reaction time in the hydrolysis reaction varies depending on the solvent used or the reaction scale, but is preferably 1 to 55 hours from the viewpoint of reactivity.

The 9-dodecenal compound (4) includes (9E)-9-dodecenal represented by the following formula (4-1), (9Z)-9-dodecenal represented by the following formula (4-2), and these mixtures.

[Example]
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.
In the following, "purity" indicates the area percentage obtained by gas chromatography (GC) analysis unless otherwise specified, and "production ratio" indicates the relative ratio of the area percentage obtained by GC analysis. "Yield" was calculated based on the area percentage obtained by GC analysis.
In each example, reaction monitoring and yield calculation were performed according to the following GC conditions.
GC conditions: GC: Shimadzu Corporation capillary gas chromatograph GC-2014, column: DB-5, 0.25 mm x 0.25 mmφ x 30 m, carrier gas: He (1.55 mL/min), detector: FID, column temperature: 150°C to 5°C /min Temperature rise 230°C.

Yield was calculated according to the following formula, taking into account the purity (% GC) of the starting material and product.
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

[Example 1]
<Production of (3Z)-11-chloro-3-undecene (7-2: X ¹ = Cl)>

At room temperature, magnesium (114.82 g, 4.73 gram-atoms), tetrahydrofuran (1350 g) were added to the reactor and stirred at 60-65°C for 20 minutes. Next, (3Z)-1-chloro-3-hexene (8-2:X ² =Cl) (533.70 g, 4.50 mol) was added dropwise to the reactor at 60 to 75°C. (3Z)-3-hexenylmagnesium=chloride (5-2: M ² =MgCl) was prepared by stirring at 75-80° C. for 2 hours.
Subsequently, cuprous iodide (8.57 g, 0.045 mol), triethyl phosphite (17.95 g, 0.11 mol), tetrahydrofuran (450 g), 1-bromo-5-chloropentane were added to another reactor. (6: X ³ = Br, X ⁴ = Cl) (776.28 g, 4.19 mol) was added, and the above prepared (3Z)-3-hexenylmagnesium chloride (5- 2: M ² =MgCl) was added dropwise. After the dropwise addition was completed, the mixture was stirred at 5 to 15°C for 3.5 hours. Next, a mixture of acetic acid (562.50 g) and water (1687.50 g) was added to the reaction solution to separate the layers, and the aqueous layer was removed. Then, the organic layer was concentrated under reduced pressure, and the residue was distilled under reduced pressure to obtain (3Z)-11-chloro-3-undecene (7-2:X ¹ =Cl) (740.43 g, 3.92 mol, purity 100%) was obtained with a yield of 93.75%.

Spectral data of (3Z)-11-chloro-3-undecene (7-2:X ¹ =Cl) obtained above are shown below.
[Nuclear magnetic resonance spectrum] ¹ H-NMR (500 MHz, CDCl ₃ ): δ 0.95 (3H, t, J = 7.6 Hz), 1.28-1.38 (6H, m), 1.39-1 .46 (2H, m), 1.77 (2H, tt-like, J=7.3Hz), 1.99-2.07 (4H, m), 3.53 (2H, t, J=6. 7 _Hz ), 5.28-5.40 (2H ^, m); , 29.60, 32.62, 45.13, 129.12, 131.64
[Mass spectrum] EI-mass spectrum (70 eV): m/z 188 (M ⁺ ), 104, 83, 69, 55, 41, 27
[Infrared absorption spectrum] (NaCl): νmax 2961, 2930, 2856, 1463, 726, 654

[Example 2]
<Production of (3E)-11-chloro-3-undecene (7-1: X ¹ = Cl)>

At room temperature, magnesium (54.91 g, 2.26 gram-atoms), tetrahydrofuran (645.60 g) were added to the reactor and stirred at 60-65°C for 25 minutes. Next, (3E)-1-chloro-3-hexene (8-1:X ² =Cl) (255.23 g, 2.15 mol) was added dropwise to the reactor at 60 to 75°C. (3E)-3-hexenylmagnesium=chloride (5-1:M ² =MgCl) was prepared by stirring at 75-80° C. for 2 hours.
Subsequently, cuprous iodide (4.10 g, 0.022 mol), triethyl phosphite (8.58 g, 0.052 mol), tetrahydrofuran (215.20 g), 1-bromo-5- Chloropentane (6: X ³ = Br, X ⁴ = Cl) (371.23 g, 2.00 mol) was added, and (3E)-3-hexenyl magnesium = chloride prepared above was added at -5 to 15°C. Dripped. After the dropwise addition was completed, the mixture was stirred at 5 to 15°C for 3 hours. Next, a mixture of acetic acid (269.00 g) and water (807.00 g) was added to the reaction liquid, and the layers were separated, and the aqueous layer was removed. Then, the organic layer was concentrated under reduced pressure, and the residue was distilled under reduced pressure to give (3E)-11-chloro-3-undecene (7-1:X ¹ =Cl) (341.43 g, 1.81 mol, purity 100%) was obtained with a yield of 90.40%.

Spectral data of (3E)-11-chloro-3-undecene (7-1:X ¹ =Cl) obtained above are shown below.
[Nuclear magnetic resonance spectrum] ¹ H-NMR (500 MHz, CDCl ₃ ): δ 0.96 (3H, t, J = 7.5 Hz), 1.27-1.38 (6H, m), 1.38-1 .46 (2H, m), 1.76 (2H, tt, J = 7.3 Hz, 7.3 Hz), 1.94-2.03 (4H, m), 3.53 (2H, t, J = 6.9 Hz), 5.38 (1 H, dt, J = 15.2 Hz, 6.2 Hz), 5.44 (1 H, dt, J = 15.2 Hz, 6.1 Hz); ¹³ C-NMR (125 MHz, _CDCl3 ): δ 13.97, 25.58, 26.83, 28.74, 28.93, 29.49, 32.48, 32.62, 45.14, 129.17, 132.00
[Mass spectrum] EI-mass spectrum (70 eV): m/z 188 (M ⁺ ), 104, 83, 69, 55, 41, 27
[Infrared absorption spectrum] (NaCl): νmax 2960, 2928, 2855, 1462, 966, 726, 654

[Example 3]
<Production of (9Z)-1,1-diethoxy-9-dodecene (3-2: R=Et)>

At room temperature, magnesium (73.99 g, 3.05 mol), tetrahydrofuran (870.00 g) were added to the reactor and stirred at 60-65° C. for 20 minutes. After stirring, (3Z)-11-chloro-3-undecene (7-2:X ¹ =Cl) (547.35 g, 2.90 mol) was added dropwise to the reactor at 60 to 75°C. (8Z)-8-undecenyl=magnesium chloride (1-2: M ¹ =MgCl) was prepared by stirring at 75-80° C. for 2.5 hours.
Subsequently, toluene (1348.50 g) and ethyl orthoformate (2: R=Et) (558.71 g, 3.77 mol) were added dropwise to the reactor at 75-85°C. Stir at 100° C. for 16 hours. Thereafter, the mixture was cooled to 30 to 45° C., a mixture of acetic acid (362.50 g) and water (1087.50 g) was added to the reaction liquid, and the layers were separated to remove the aqueous layer. Then, the organic layer was concentrated under reduced pressure, and the residue was distilled under reduced pressure to give a crude product of (9Z)-1,1-diethoxy-9-dodecene (3-2: R=Et) (641.06 g, 2.34 mol, 93.65% purity) was obtained in a crude yield of 80.73%.

Spectral data of (9Z)-1,1-diethoxy-9-dodecene (3-2: R=Et) obtained above are shown below.
[Nuclear magnetic resonance spectrum] ¹ H-NMR (500 MHz, CDCl ₃ ): δ 0.94 (3H, t, J = 7.5 Hz), 1.19 (6H, t, J = 7.1 Hz), 1.24 -1.37 (10H, m), 1.59 (2H, dt, J = 9.2Hz, 6.0Hz), 2.01 (4H, sext-like, J = 7.2Hz), 3.47 ( 2H, dq, J = 7.1Hz, 8.2Hz), 3.62 (2H, dq, J = 7.1Hz, 8.2Hz), 4.46 (1H, t, J = 5.8Hz), 5 .27-5.38 ₍ 2H ^, m); , 29.70, 33.54, 60.75, 102.92, 129.24, 131.48
[Mass spectrum] EI-mass spectrum (70 eV): m/z 211 (M ⁺ -45), 103, 75, 47, 29
[Infrared absorption spectrum] (NaCl): νmax 2973, 2927, 2855, 1463, 1373, 1344, 1127, 1064, 723

[Example 4]
<Production of (9E)-1,1-diethoxy-9-dodecene (3-1: R=Et)>

At room temperature, magnesium (35.93 g, 1.48 mol), tetrahydrofuran (422.40 g) were added to the reactor and stirred at 60-65° C. for 16 minutes. After stirring, (3E)-11-chloro-3-undecene (7-1:X ¹ =Cl) (265.75 g, 1.41 mol) was added dropwise to the reactor at 60 to 75°C. (8E)-8-undecenyl=magnesium chloride (1-1:M ¹ =MgCl) was prepared by stirring at 75-80° C. for 3 hours.
Subsequently, toluene (654.72 g) and ethyl orthoformate (2: R=Et) (271.27 g, 1.83 mol) were added dropwise to the reactor at 75-85°C. Stir at 100° C. for 13 hours. After that, the mixture was cooled to 30 to 45° C., a mixture of acetic acid (176.00 g) and water (528.00 g) was added to the reaction liquid, and the layers were separated to remove the aqueous layer. Then, the organic layer was concentrated under reduced pressure, and the residue was distilled under reduced pressure to give crude product (312.66 g, 312.66 g, 1.15 mol, 93.91% purity) was obtained in a crude yield of 81.33%.

Spectral data of (9E)-1,1-diethoxy-9-dodecene (3-1:R=Et) obtained above are shown below.
[Nuclear magnetic resonance spectrum] ¹ H-NMR (500 MHz, CDCl ₃ ): δ 0.95 (3H, t, J = 7.3 Hz), 1.19 (6H, t, J = 7.1 Hz), 1.24 -1.36 (10H, m), 1.59 (2H, dt, J = 9.2Hz, 6.2Hz), 1.97 (4H, sext-like, J = 7.6Hz), 3.48 ( 2H, dq, J = 7.3Hz, 8.4Hz), 3.62 (2H, dq, J = 7.3Hz, 8.4Hz), 4.47 (1H, t, J = 5.8Hz), 5 .37 (1H, dt, J=15.7 Hz, 6.1 Hz), 5.42 (1 H, dt, J=15.7 Hz, 6.1 Hz); ¹³ C-NMR (125 MHz, CDCl ₃ ): δ13. 97, 15.33, 24.73, 25.57, 29.05, 29.40, 29.42, 29.59, 32.51, 33.56, 60.76, 102.93, 129.30, 131.85
[Mass spectrum] EI-mass spectrum (70 eV): m/z 211 (M ⁺ -45), 103, 75, 47, 29
[Infrared absorption spectrum] (NaCl): νmax 2974, 2926, 2874, 2854, 1461, 1443, 1373, 1344, 1128, 1063, 966

[Example 5]
<Production of (9Z)-9-dodecenal (4-2)>

At room temperature, the crude product of (9Z)-1,1-diethoxy-9-dodecene (3-2: R=Et) obtained in Example 3 (641.06 g, 2.34 mol, purity 93.65%), oxalic acid dihydrate (590.26 g, 4.68 mol), tetrahydrofuran (1638.70 g) and pure water (1638.70 g) were added and stirred at 60-65° C. for 6 hours. After stirring, the reaction mixture was cooled to 50° C., hexane (688.49 g) was added and stirred for 30 minutes. After that, the reaction liquid was liquid-separated and the water layer was removed. Then, the organic layer was concentrated under reduced pressure, and the residue was distilled under reduced pressure to give (9Z)-9-dodecenal (4-2) (410.32 g, 2.21 mol, purity 98.10%) in two steps ( That is, the yield of the two steps of Examples 3 and 5) was 76.15%.

Spectral data of (9Z)-9-dodecenal (4-2) obtained above are shown below.
[Nuclear magnetic resonance spectrum] ¹ H-NMR (500 MHz, CDCl ₃ ): δ 0.94 (3H, t, J = 7.6 Hz), 1.25-1.36 (8H, m), 1.61 (2H , quin-like, J=7.3 Hz), 2.01 (4H, sext-like, J=7.3 Hz), 2.40 (2H, dt, J=1.9 Hz, 7.5 Hz), 5. 26-5.38 (2H, m), 9.75 (1H, t, J=1.9 Hz); ¹³ C-NMR (125 MHz, CDCl ₃ ): δ 14.33, 20.46, 22.01, 26 .97, 28.97, 29.08, 29.19, 29.60, 43.85, 129.10, 131.58, 202.85
[Mass spectrum] EI-mass spectrum (70 eV): m/z 182 (M ⁺ ), 164, 135, 121, 111, 98, 81, 67, 55, 41, 29
[Infrared absorption spectrum] (NaCl): νmax 2962, 2929, 2855, 1727, 1463, 724

[Example 6]
<Production of (9E)-9-dodecenal (4-1)>

At room temperature, the crude product of (9E)-1,1-diethoxy-9-dodecene (3-1: R=Et) obtained in Example 4 (312.66 g, 1.15 mol, purity 93.91%), oxalic acid dihydrate (462.55 g, 3.67 mol), tetrahydrofuran (1223.00 g) and pure water (1223.00 g) were added and stirred at 60 to 65°C for 5.5 hours. . After stirring, the reaction mixture was cooled to 50° C., hexane (359.68 g) was added and stirred for 30 minutes. After that, the reaction liquid was liquid-separated and the water layer was removed. Then, the organic layer was concentrated under reduced pressure, and the residue was distilled under reduced pressure to obtain (9E)-9-dodecenal (4-1) (198.10 g, 1.07 mol, purity 98.65%) in two steps ( That is, the yield of the two steps of Examples 4 and 6) was 76.15%.

Spectral data of (9E)-9-dodecenal (4-1) obtained above are shown below.
[Nuclear magnetic resonance spectrum] ¹ H-NMR (500 MHz, CDCl ₃ ): δ 0.95 (3H, t, J = 7.5 Hz), 1.23-1.36 (8H, m), 1.61 (2H , quin-like, J=7.3 Hz), 1.97 (4H, sext-like, J=7.7 Hz), 2.40 (2H, dt, J=1.9 Hz, 7.4 Hz), 5. 36 (1H, dt, J = 15.3Hz, 6.1Hz), 5.42 (1H, dt, J = 15.3Hz, 5.8Hz), 9.75 (1H, t, J = 1.9Hz) ¹³ C-NMR (125 MHz, CDCl ₃ ): δ 13.94, 22.01, 25.55, 28.86, 29.07, 29.17, 29.48, 32.45, 43.86, 129. 15, 131.94, 202.86
[Mass spectrum] EI-mass spectrum (70 eV): m/z 182 (M ⁺ ), 164, 135, 121, 111, 98, 82, 69, 55, 41, 29
[Infrared absorption spectrum] (NaCl): νmax 2961, 2927, 2854, 1727, 1462, 967

（式中、Ｒは互いに同じであっても異なっていてもよい炭素数１～６のアルキル基を表す。）
で表されるオルトギ酸エステル化合物との求核置換反応により、下記一般式（３）
ＣＨ_３ＣＨ_２ＣＨ＝ＣＨ（ＣＨ_２）_７ＣＨ（ＯＲ）_２ （３）
（式中、Ｒは、上記で定義した通りである。）
で表される１，１－ジアルコキシ－９－ドデセン化合物を得る工程と、
前記１，１－ジアルコキシ－９－ドデセン化合物（３）の加水分解反応により、下記一般式（４）
ＣＨ_３ＣＨ_２ＣＨ＝ＣＨ（ＣＨ_２）_７ＣＨＯ （４）
で表される９－ドデセナール化合物を得る工程と
を少なくとも含む、９－ドデセナール化合物（４）の製造方法。
［２］
下記一般式（５）
ＣＨ_３ＣＨ_２ＣＨ＝ＣＨ（ＣＨ_２）_２Ｍ^２ （５）
（式中、Ｍ^２はＬｉ又はＭｇＺ^２を表し、Ｚ^２はハロゲン原子又は３－ヘキセニル基を表す。）
で表される３－ヘキセニル求核試薬と、下記一般式（６）
Ｘ^３（ＣＨ_２）_５Ｘ^４ （６）
（式中、Ｘ^３及びＸ^４は互いに同じであっても異なっていてもよいハロゲン原子を表す。）
で表される１－ハロ－５－ハロペンタン化合物とのカップリング反応により、下記一般式（７）
ＣＨ_３ＣＨ_２ＣＨ＝ＣＨ（ＣＨ_２）_７Ｘ^１ （７）
（式中、Ｘ^１はハロゲン原子を表す。）
で表される１１－ハロ－３－ウンデセン化合物を得る工程と、
前記１１－ハロ－３－ウンデセン化合物（７）から上記の８－ウンデセニル求核試薬（１）を調製する工程と
を更に含む、項１に記載の９－ドデセナール化合物の製造方法。
［３］
下記一般式（５）
ＣＨ_３ＣＨ_２ＣＨ＝ＣＨ（ＣＨ_２）_２Ｍ^２ （５）
（式中、Ｍ^２はＬｉ又はＭｇＺ^２を表し、Ｚ^２はハロゲン原子又は３－ヘキセニル基を表す。）
で表される３－ヘキセニル求核試薬と、下記一般式（６）
Ｘ^３（ＣＨ_２）_５Ｘ^４ （６）
（式中、Ｘ^３及びＸ^４は互いに同じであっても異なっていてもよいハロゲン原子を表す。）
で表される１－ハロ－５－ハロペンタン化合物とのカップリング反応により、下記一般式（７）
ＣＨ_３ＣＨ_２ＣＨ＝ＣＨ（ＣＨ_２）_７Ｘ^１ （７）
（式中、Ｘ^１はハロゲン原子を表す。）
で表される１１－ハロ－３－ウンデセン化合物を得る工程と
を少なくとも含む、１１－ハロ－３－ウンデセン化合物（７）の製造方法。
［４］
下記一般式（７）
ＣＨ_３ＣＨ_２ＣＨ＝ＣＨ（ＣＨ_２）_７Ｘ^１ （７）
（式中、Ｘ^１はハロゲン原子を表す。）
で表される１１－ハロ－３－ウンデセン化合物。 One embodiment of the invention is represented by the following.
[1]
General formula (1) below
_{CH3CH2CH =} CH( _CH2 ) _7M1 ( ¹ )
(Wherein, M ¹ represents Li or MgZ ¹ , and Z ¹ represents a halogen atom or an 8-undecenyl group.)
and an 8-undecenyl nucleophile represented by the following general formula (2)

(In the formula, R represents an alkyl group having 1 to 6 carbon atoms which may be the same or different.)
By a nucleophilic substitution reaction with an orthoformate compound represented by the following general formula (3)
_CH3CH2CH =CH( _CH2 ) _{7CH (} OR) ₂ (3)
(wherein R is as defined above.)
A step of obtaining a 1,1-dialkoxy-9-dodecene compound represented by
By hydrolysis reaction of the 1,1-dialkoxy-9-dodecene compound (3), the following general formula (4)
_{CH3CH2CH =} CH( _CH2 ) _7CHO (4)
A method for producing a 9-dodecenal compound (4), comprising at least a step of obtaining a 9-dodecenal compound represented by
[2]
General formula (5) below
_{CH3CH2CH =} CH( _CH2 ) _2M2 ( ⁵ )
(Wherein, ^M2 represents Li or ^MgZ2 , and ^Z2 represents a halogen atom or a 3-hexenyl group.)
and a 3-hexenyl nucleophile represented by the following general formula (6)
^X3 ( _CH2 ) _5X4 ⁽ 6)
(In the formula, ^X3 and ^X4 represent halogen atoms which may be the same or different.)
By a coupling reaction with a 1-halo-5-halopentane compound represented by the following general formula (7)
_{CH3CH2CH =} CH( _CH2 ) _7X1 ( ⁷ )
(In the formula, X ¹ represents a halogen atom.)
obtaining a 11-halo-3-undecene compound represented by
Item 2. The method for producing the 9-dodecenal compound according to Item 1, further comprising the step of preparing the 8-undecenyl nucleophile (1) from the 11-halo-3-undecene compound (7).
[3]
General formula (5) below
_{CH3CH2CH =} CH( _CH2 ) _2M2 ( ⁵ )
(Wherein, ^M2 represents Li or ^MgZ2 , and ^Z2 represents a halogen atom or a 3-hexenyl group.)
and a 3-hexenyl nucleophile represented by the following general formula (6)
^X3 ( _CH2 ) _5X4 ⁽ 6)
(In the formula, ^X3 and ^X4 represent halogen atoms which may be the same or different.)
By a coupling reaction with a 1-halo-5-halopentane compound represented by the following general formula (7)
_{CH3CH2CH =} CH( _CH2 ) _7X1 ( ⁷ )
(In the formula, X ¹ represents a halogen atom.)
A method for producing an 11-halo-3-undecene compound (7) comprising at least a step of obtaining an 11-halo-3-undecene compound represented by
[4]
The following general formula (7)
_{CH3CH2CH =} CH( _CH2 ) _7X1 ( ⁷ )
(In the formula, X ¹ represents a halogen atom.)
11-halo-3-undecene compound represented by.

（式中、Ｒは互いに同じであっても異なっていてもよい炭素数１～６のアルキル基を表す。）
で表されるオルトギ酸エステル化合物との求核置換反応により、下記一般式（３）
ＣＨ_３ＣＨ_２ＣＨ＝ＣＨ（ＣＨ_２）_７ＣＨ（ＯＲ）_２ （３）
（式中、Ｒは、上記で定義した通りである。）
で表される１，１－ジアルコキシ－９－ドデセン化合物を得る工程と、
前記１，１－ジアルコキシ－９－ドデセン化合物（３）の加水分解反応により、下記一般式（４）
ＣＨ_３ＣＨ_２ＣＨ＝ＣＨ（ＣＨ_２）_７ＣＨＯ （４）
で表される９－ドデセナール化合物を得る工程と
を少なくとも含む、９－ドデセナール化合物（４）の製造方法。
［１３］
前記１－ハロ－５－ハロペンタン化合物（６）において、Ｘ^３が臭素原子であり、且つＸ^４が塩素原子であり、
前記１１－ハロ－３－ウンデセン化合物（７）において、Ｘ^１が塩素原子である、
項１１又は１２に記載の方法。
［１４］
下記一般式（７）
ＣＨ_３ＣＨ_２ＣＨ＝ＣＨ（ＣＨ_２）_７Ｘ^１ （７）
（式中、Ｘ^１はハロゲン原子を表す。）
で表される１１－ハロ－３－ウンデセン化合物から、下記一般式（１）
ＣＨ_３ＣＨ_２ＣＨ＝ＣＨ（ＣＨ_２）_７Ｍ^１ （１）
（式中、Ｍ^１はＬｉ又はＭｇＺ^１を表し、Ｚ^１はハロゲン原子又は８－ウンデセニル基を表す。）
で表される８－ウンデセニル求核試薬を調製する工程と、
前記８－ウンデセニル求核試薬と、下記一般式（２）

（式中、Ｒは互いに同じであっても異なっていてもよい炭素数１～６のアルキル基を表す。）
で表されるオルトギ酸エステル化合物との求核置換反応により、下記一般式（３）
ＣＨ_３ＣＨ_２ＣＨ＝ＣＨ（ＣＨ_２）_７ＣＨ（ＯＲ）_２ （３）
（式中、Ｒは、上記で定義した通りである。）
で表される１，１－ジアルコキシ－９－ドデセン化合物を得る工程と、
前記１，１－ジアルコキシ－９－ドデセン化合物（３）の加水分解反応により、下記一般式（４）
ＣＨ_３ＣＨ_２ＣＨ＝ＣＨ（ＣＨ_２）_７ＣＨＯ （４）
で表される９－ドデセナール化合物を得る工程と
を少なくとも含む、９－ドデセナール化合物（４）の製造方法。
［１５］
前記１１－ハロ－３－ウンデセン化合物（７）において、Ｘ^１が塩素原子である、
項１４に記載の方法。 Another embodiment of the invention is represented by the following.
[11]
General formula (5) below
_{CH3CH2CH =} CH( _CH2 ) _2M2 ( ⁵ )
(Wherein, ^M2 represents Li or ^MgZ2 , and ^Z2 represents a halogen atom or a 3-hexenyl group.)
and a 3-hexenyl nucleophile represented by the following general formula (6)
^X3 ( _CH2 ) _5X4 ⁽ 6)
(In the formula, ^X3 and ^X4 represent halogen atoms which may be the same or different.)
By a coupling reaction with a 1-halo-5-halopentane compound represented by the following general formula (7)
_{CH3CH2CH =} CH( _CH2 ) _7X1 ( ⁷ )
(In the formula, X ¹ represents a halogen atom.)
obtaining a 11-halo-3-undecene compound represented by
From the 11-halo-3-undecene compound (7), the following general formula (1)
_{CH3CH2CH =} CH( _CH2 ) _7M1 ( ¹ )
(Wherein, M ¹ represents Li or MgZ ¹ , and Z ¹ represents a halogen atom or an 8-undecenyl group.)
A method for producing an 8-undecenyl nucleophile (1), comprising at least the step of preparing an 8-undecenyl nucleophile represented by
[12]
A method for producing the 8-undecenyl nucleophile (1) according to Item 11;
The 8-undecenyl nucleophile (1) and the following general formula (2)

(In the formula, R represents an alkyl group having 1 to 6 carbon atoms which may be the same or different.)
By a nucleophilic substitution reaction with an orthoformate compound represented by the following general formula (3)
_CH3CH2CH =CH( _CH2 ) _{7CH (} OR) ₂ (3)
(wherein R is as defined above.)
A step of obtaining a 1,1-dialkoxy-9-dodecene compound represented by
By hydrolysis reaction of the 1,1-dialkoxy-9-dodecene compound (3), the following general formula (4)
_{CH3CH2CH =} CH( _CH2 ) _7CHO (4)
A method for producing a 9-dodecenal compound (4), comprising at least a step of obtaining a 9-dodecenal compound represented by
[13]
In the 1-halo-5-halopentane compound (6), X ³ is a bromine atom and X ⁴ is a chlorine atom,
In the 11-halo-3-undecene compound (7), X ¹ is a chlorine atom,
13. The method according to Item 11 or 12.
[14]
The following general formula (7)
_{CH3CH2CH =} CH( _CH2 ) _7X1 ( ⁷ )
(In the formula, X ¹ represents a halogen atom.)
from the 11-halo-3-undecene compound represented by the following general formula (1)
_{CH3CH2CH =} CH( _CH2 ) _7M1 ( ¹ )
(Wherein, M ¹ represents Li or MgZ ¹ , and Z ¹ represents a halogen atom or an 8-undecenyl group.)
preparing an 8-undecenyl nucleophile represented by
The 8-undecenyl nucleophile and the following general formula (2)

(In the formula, R represents an alkyl group having 1 to 6 carbon atoms which may be the same or different.)
By a nucleophilic substitution reaction with an orthoformate compound represented by the following general formula (3)
_CH3CH2CH =CH( _CH2 ) _{7CH (} OR) ₂ (3)
(wherein R is as defined above.)
A step of obtaining a 1,1-dialkoxy-9-dodecene compound represented by
By hydrolysis reaction of the 1,1-dialkoxy-9-dodecene compound (3), the following general formula (4)
_{CH3CH2CH =} CH( _CH2 ) _7CHO (4)
A method for producing a 9-dodecenal compound (4), comprising at least a step of obtaining a 9-dodecenal compound represented by
[15]
In the 11-halo-3-undecene compound (7), X ¹ is a chlorine atom,
Item 15. The method according to Item 14.

Claims (7)

in the presence of a monovalent copper halide and a trialkyl phosphite compound having 3 to 9 carbon atoms,
General formula (5) below
_{CH3CH2CH =} CH( _CH2 ) _2M2 ( ⁵ )
(Wherein, ^M2 represents Li or ^MgZ2 , and ^Z2 represents a halogen atom or a 3-hexenyl group.)
and a 3-hexenyl nucleophile represented by the following general formula (6)
^X3 ( _CH2 ) _5X4 ⁽ 6)
(In the formula, ^X3 and ^X4 represent halogen atoms which may be the same or different.)
By a coupling reaction with a 1-halo-5-halopentane compound represented by the following general formula (7)
_{CH3CH2CH =} CH( _CH2 ) _7X1 ( ⁷ )
(In the formula, X ¹ represents a halogen atom.)
obtaining a 11-halo-3-undecene compound represented by
From the 11-halo-3-undecene compound (7), the following general formula (1)
_{CH3CH2CH =} CH( _CH2 ) _7M1 ( ¹ )
(Wherein, M ¹ represents Li or MgZ ¹ , and Z ¹ represents a halogen atom or an 8-undecenyl group.)
A method for producing an 8-undecenyl nucleophile (1), comprising at least the step of preparing an 8-undecenyl nucleophile represented by A method for producing the 8-undecenyl nucleophile (1) according to claim 1;
The 8-undecenyl nucleophile (1) and the following general formula (2)

(In the formula, R represents an alkyl group having 1 to 6 carbon atoms which may be the same or different.)
By a nucleophilic substitution reaction with an orthoformate compound represented by the following general formula (3)
_CH3CH2CH =CH( _CH2 ) _{7CH (} OR) ₂ (3)
(wherein R is as defined above.)
A step of obtaining a 1,1-dialkoxy-9-dodecene compound represented by
By hydrolysis reaction of the 1,1-dialkoxy-9-dodecene compound (3), the following general formula (4)
_{CH3CH2CH =} CH( _CH2 ) _7CHO (4)
A method for producing a 9-dodecenal compound (4), comprising at least a step of obtaining a 9-dodecenal compound represented by In the 1-halo-5-halopentane compound (6), X ³ is a bromine atom and X ⁴ is a chlorine atom,
In the 11-halo-3-undecene compound (7), X ¹ is a chlorine atom,
The method of claim 1. 3-hexenyl nucleophile (5) is represented by the following general formula (5-1)

(wherein ^M2 is as defined above.)
is a (3E)-3-hexenyl nucleophile represented by
11-halo-3-undecene compound (7) has the following general formula (7-1)

(Where X ¹ is as defined above.)
(3E)-11-halo-3-undecene compound represented by
8-undecenyl nucleophile (1) is represented by the following general formula (1-1)

(wherein M ¹ is as defined above.)
is a (8E)-8-undecenyl nucleophile represented by
The method of claim 1. 3-hexenyl nucleophile (5) is represented by the following general formula (5-1)

(wherein ^M2 is as defined above.)
is a (3E)-3-hexenyl nucleophile represented by
11-halo-3-undecene compound (7) has the following general formula (7-1)

(Where X ¹ is as defined above.)
(3E)-11-halo-3-undecene compound represented by
8-undecenyl nucleophile (1) is represented by the following general formula (1-1)

(wherein M ¹ is as defined above.)
(8E)-8-undecenyl nucleophile represented by
1,1-dialkoxy-9-dodecene compound (3) has the following general formula (3-1)

(wherein R is as defined above.)
(9E)-1,1-dialkoxy-9-dodecene compound represented by
9-dodecenal compound (4) is represented by the following general formula (4-1)

is a (9E)-9-dodecenal compound represented by
3. The method of claim 2. In the 1-halo-5-halopentane compound (6), X ³ is a bromine atom, and X ⁴ is a chlorine atom, and
In the 11-halo-3-undecene compound (7), X ¹ is a chlorine atom,
3. The method of claim 2. 3-hexenyl nucleophile (5) is represented by the following general formula (5-1)

(wherein ^M2 is as defined above.)
is a (3E)-3-hexenyl nucleophile represented by
11-halo-3-undecene compound (7) has the following general formula (7-1)

(Where X ¹ is as defined above.)
(3E)-11-halo-3-undecene compound represented by
8-undecenyl nucleophile (1) is represented by the following general formula (1-1)

(wherein M ¹ is as defined above.)
(8E)-8-undecenyl nucleophile represented by
1,1-dialkoxy-9-dodecene compound (3) has the following general formula (3-1)

(wherein R is as defined above.)
(9E)-1,1-dialkoxy-9-dodecene compound represented by
9-dodecenal compound (4) is represented by the following general formula (4-1)

is a (9E)-9-dodecenal compound represented by
7. The method of claim 6 .