JP2010163414A - Method for producing cyclic aliphatic diamine having trans-structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a cyclic aliphatic diamine having a trans-structure, useful as a raw material monomer for a polyurethane resin or a polyamide resin and as an intermediate of a raw material for pharmaceuticals and agrichemicals. <P>SOLUTION: The method for producing a cyclic aliphatic diamine having a trans-structure by imidizing a dihalogenated compound comprising a trans-structure and a cis-structure represented by formula (1) using an imide compound and subsequently subjecting the reaction product to a decomposition reaction, uses a basic compound in an amount of 1.0 to 10.0 moles relative to 1 mole of the dihalogenated compound having a cis-structure upon imidizing the above compound (in the formula, the dotted line represents a single bond or a double bond, Xs each independently represents a chlorine, a bromine, or an iodine atom, and n represents 0 or 1). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel process for producing a cycloaliphatic diamine having a trans isomer structure. The cycloaliphatic diamine having a trans isomer structure produced in the present invention is useful as an intermediate of a polyurethane resin or a polyamide resin monomer raw material or a medical or agricultural chemical raw material.

  In recent years, a polyurethane resin using a cyclic aliphatic diisocyanate having an aliphatic hydrocarbon having a cyclic structure as a raw material has no yellowing, weather resistance, and rigidity, and has attracted attention as a paint or an adhesive. Since the three-dimensional structure of the isocyanate group of the cycloaliphatic diisocyanate affects the physical properties of the resin, it is expected to have a trans structure. In general, since the three-dimensional structure of the diisocyanate group retains the three-dimensional structure of the amino group of the diamine used as a raw material, it is desired that the cyclic aliphatic diamine used as the raw material of the cyclic aliphatic diisocyanate has a trans isomer structure. .

  For example, trans-2,3-bis (aminomethyl) -bicyclo- (2,2,1) -heptane is known as the cycloaliphatic diamine having such a trans structure, and cyclopentadiene or dicyclopentadiene. A Diels-Alder reaction is performed using maleic anhydride and maleic anhydride, followed by methyl esterification, epimerization, hydrogenation, imination, and hydrogenation again. 1), cyclopentadiene or dicyclopentadiene and fumaronitrile are reacted and then hydrogenated (for example, see Patent Document 1).

  However, the route of Non-Patent Document 1 requires the epimerization treatment at an ultra-low temperature of −78 ° C. in order to take the structure of the trans isomer, and there is a problem that a complicated and special reaction apparatus is required. Furthermore, when the epimerization treatment is not sufficient, there is a problem that a cis isomer remains and the purity of the trans isomer of the target cycloaliphatic diamine is lowered. Further, in the route of Patent Document 1, it is necessary to use expensive fumaronitrile. Furthermore, when fumaronitrile contains maleonitrile, which is a structural isomer, there is a problem that the purity of the trans isomer of the desired cycloaliphatic diamine cannot be maintained. .

Tetrahedron: Asymmetry 2003 14 14 1167

Japanese Patent No. 3185807 (Claims)

  The present invention has been made in view of the above-mentioned problems, and its purpose is to use a readily available raw material in which a trans isomer and a cis isomer are mixed, and without a complicated and special process, a polyurethane resin or a polyamide resin. By selectively producing a cycloaliphatic diamine having a trans-form structure useful as an intermediate for monomers for pharmaceuticals and an intermediate for raw materials for pharmaceuticals and agricultural chemicals, and providing a method for increasing the efficiency of use of imide compounds in the imidization process is there.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found a novel method for producing a cycloaliphatic diamine having a trans isomer structure and have completed the present invention. That is, this invention is a novel manufacturing method of cycloaliphatic diamine which has the trans body structure represented by following General formula (2).

（式中、点線は単結合又は二重結合を表し、ｍは０又は１を表す。）
以下、本発明について詳細に説明する。

(In the formula, a dotted line represents a single bond or a double bond, and m represents 0 or 1.)
Hereinafter, the present invention will be described in detail.

  A novel method for producing a cycloaliphatic diamine having a trans isomer structure represented by the general formula (2) of the present invention comprises a dihalide comprising a trans isomer structure and a cis isomer structure represented by the following general formula (1): A process for producing a cycloaliphatic diamine having a trans isomer structure represented by the general formula (2), which is imidized with an imide compound and then decomposed, with respect to 1 mol of a dihalide having a cis isomer structure at the time of imidization The basic compound is used in an amount of 1.0 to 10 mol.

（式中、点線は単結合又は二重結合を示し、Ｘはそれぞれ独立して塩素原子、臭素原子又はヨウ素原子を表し、ｎは０又は１を表す。）
本発明の製造法で製造される上記一般式（２）で表されるトランス体構造を有する環状脂肪族ジアミンとしては、例えば、トランス−２，３−ビス（アミノメチル）−ビシクロ−（２，２，１）−ヘプタン、トランス−２，３−ビス（アミノメチル）−ビシクロ−（２，２，１）−ヘプト−５−エン、トランス−２，３−ビス（アミノメチル）−１α，２，３，４α，４ａα，５β，６，７，８β，８ａα−デカヒドロ−１，４：５，８−ジメタノナフタレン、トランス−２，３−ビス（アミノメチル）−１α，２，３，４α，４ａα，５β，８β，８ａα−オクタヒドロ−１，４：５，８−ジメタノナフタレン等があげられる。これらのうち、原料の入手及び合成が容易なこと、さらに環状脂肪族ジアミン自体の安定性が高いことから、トランス−２，３−ビス（アミノメチル）−ビシクロ−（２，２，１）−ヘプタンが好ましい。

(In the formula, a dotted line represents a single bond or a double bond, X represents each independently a chlorine atom, a bromine atom or an iodine atom, and n represents 0 or 1).
Examples of the cycloaliphatic diamine having the trans isomer structure represented by the general formula (2) produced by the production method of the present invention include trans-2,3-bis (aminomethyl) -bicyclo- (2, 2,1) -heptane, trans-2,3-bis (aminomethyl) -bicyclo- (2,2,1) -hept-5-ene, trans-2,3-bis (aminomethyl) -1α, 2 , 3,4α, 4aα, 5β, 6,7,8β, 8aα-decahydro-1,4: 5,8-dimethananaphthalene, trans-2,3-bis (aminomethyl) -1α, 2,3,4 , 4aα, 5β, 8β, 8aα-octahydro-1,4: 5,8-dimethanonaphthalene and the like. Among these, since it is easy to obtain and synthesize raw materials and the stability of the cycloaliphatic diamine itself is high, trans-2,3-bis (aminomethyl) -bicyclo- (2,2,1)- Heptane is preferred.

  Examples of the dihalide having a trans isomer structure and a cis isomer structure represented by the general formula (1) used in the production method of the present invention include 2,3-bis (chloromethyl) -bicyclo- (2,2, 1) -heptane, 2,3-bis (bromomethyl) -bicyclo- (2,2,1) -heptane, 2,3-bis (iodomethyl) -bicyclo- (2,2,1) -heptane, 2,3 -Bis (chloromethyl) -bicyclo- (2,2,1) -hept-5-ene, 2,3-bis (bromomethyl) -bicyclo- (2,2,1) -hept-5-ene, 2, 3-bis (iodomethyl) -bicyclo- (2,2,1) -hept-5-ene, trans-2,3-bis (chloromethyl) -1α, 2,3,4α, 4aα, 5β, 6,7 , 8β, 8aα-decahydro-1,4: 5,8-dimethano Phthalene, 2,3-bis (bromomethyl) -1α, 2,3,4α, 4aα, 5β, 6,7,8β, 8aα-decahydro-1,4: 5,8-dimethanonaphthalene, 2,3-bis (Iodomethyl) -1α, 2,3,4,4aα, 5β, 6,7,8β, 8aα-decahydro-1,4: 5,8-dimethanonaphthalene, 2,3-bis (chloromethyl) -1α, 2,3,4α, 4aα, 5β, 8β, 8aα-octahydro-1,4: 5,8-dimethanonaphthalene, 2,3-bis (bromomethyl) -1α, 2,3,4α, 4aα, 5β, 8β , 8aα-octahydro-1,4: 5,8-dimethanonaphthalene, 2,3-bis (iodomethyl) -1α, 2,3,4a, 4aα, 5β, 8β, 8aα-octahydro-1,4: 5 Trans-body structures such as 8-dimethanonaphthalene and Dihalides made from the body structure and the like. Here, among these, since the raw materials are easy to obtain and can be produced simply and efficiently, 2,3-bis (chloromethyl) -bicyclo- (2) in which both X in the general formula (1) are chlorine atoms. , 2,1) -heptane, 2,3-bis (chloromethyl) -bicyclo- (2,2,1) -hept-5-ene, 2,3-bis (chloromethyl) -1α, 2,3 4α, 4aα, 5β, 6,7,8β, 8aα-decahydro-1,4: 5,8-dimethananaphthalene, 2,3-bis (chloromethyl) -1α, 2,3,4a, 4aα, 5β, A dihalide consisting of a trans structure and a cis structure of 8β, 8aα-octahydro-1,4: 5,8-dimethanonaphthalene is preferable, and since n is 0 in general formula (1) because it is particularly stable. Some 2,3-bis (chloromethyl) Bicyclo - (2,2,1) - dihalides consisting trans structures and cis structures of heptane is more preferred.

  The dihalide having a trans isomer structure and a cis isomer structure represented by the general formula (1) used in the production method of the present invention is a dihalide having a trans isomer structure represented by the following general formula (3). Further, it may be a mixture of a dihalide having a cis isomer structure represented by the following general formula (4) and a dihalide having a cis isomer structure represented by the following general formula (5).

（式中、点線は単結合又は二重結合を示し、Ｘ_１はそれぞれ独立して塩素原子、臭素原子又はヨウ素原子を表し、ｎ_１は０又は１を表す。）

(In the formula, a dotted line represents a single bond or a double bond, X ₁ independently represents a chlorine atom, a bromine atom or an iodine atom, and n ₁ represents 0 or 1.)

（式中、点線は単結合又は二重結合を示し、Ｘ_２はそれぞれ独立して塩素原子、臭素原子又はヨウ素原子を表し、ｎ_２は０又は１を表す。）

(In the formula, a dotted line represents a single bond or a double bond, X ₂ independently represents a chlorine atom, a bromine atom or an iodine atom, and n ₂ represents 0 or 1).

（式中、点線は単結合又は二重結合を示し、Ｘ_３はそれぞれ独立して塩素原子、臭素原子又はヨウ素原子を表し、ｎ_３は０又は１を表す。）
ここで、上記一般式（３）で表されるトランス体構造を有するジハロゲン化物としては、例えばトランス−２，３−ビス（クロロメチル）−ビシクロ−（２，２，１）−ヘプタン、トランス−２，３−ビス（ブロモメチル）−ビシクロ−（２，２，１）−ヘプタン、トランス−２，３−ビス（ヨードメチル）−ビシクロ−（２，２，１）−ヘプタン、トランス−２，３−ビス（クロロメチル）−ビシクロ−（２，２，１）−ヘプト−５−エン、トランス−２，３−ビス（ブロモメチル）−ビシクロ−（２，２，１）−ヘプト−５−エン、トランス−２，３−ビス（ヨードメチル）−ビシクロ−（２，２，１）−ヘプト−５−エン、トランス−２，３−ビス（クロロメチル）−１α，２，３，４α，４ａα，５β，６，７，８β，８ａα−デカヒドロ−１，４：５，８−ジメタノナフタレン、トランス−２，３−ビス（ブロモメチル）−１α，２，３，４α，４ａα，５β，６，７，８β，８ａα−デカヒドロ−１，４：５，８−ジメタノナフタレン、トランス−２，３−ビス（ヨードメチル）−１α，２，３，４α，４ａα，５β，６，７，８β，８ａα−デカヒドロ−１，４：５，８−ジメタノナフタレン、トランス−２，３−ビス（クロロメチル）−１α，２，３，４α，４ａα，５β，８β，８ａα−オクタヒドロ−１，４：５，８−ジメタノナフタレン、トランス−２，３−ビス（ブロモメチル）−１α，２，３，４α，４ａα，５β，８β，８ａα−オクタヒドロ−１，４：５，８−ジメタノナフタレン、トランス−２，３−ビス（ヨードメチル）−１α，２，３，４α，４ａα，５β，８β，８ａα−オクタヒドロ−１，４：５，８−ジメタノナフタレン等があげられる。ここで、上記一般式（３）で表されるトランス体構造を有するジハロゲン化物のハロゲン化メチル基、例えばクロロメチル基は立体化学的にエンド−エキソ体とも称される。これらのうち、原料入手が容易で、簡便に効率よく製造できることから、上記一般式（３）におけるＸ_１が両方とも塩素原子であるトランス−２，３−ビス（クロロメチル）−ビシクロ−（２，２，１）−ヘプタン、トランス−２，３−ビス（クロロメチル）−ビシクロ−（２，２，１）−ヘプト−５−エン、トランス−２，３−ビス（クロロメチル）−１α，２，３，４α，４ａα，５β，６，７，８β，８ａα−デカヒドロ−１，４：５，８−ジメタノナフタレン、トランス−２，３−ビス（クロロメチル）−１α，２，３，４α，４ａα，５β，８β，８ａα−オクタヒドロ−１，４：５，８−ジメタノナフタレンが好ましく、特に安定性が高いことから、一般式（３）におけるｎ_１が０であるトランス−２，３−ビス（クロロメチル）−ビシクロ−（２，２，１）−ヘプタンがさらに好ましい。

(In the formula, a dotted line represents a single bond or a double bond, X ₃ independently represents a chlorine atom, a bromine atom or an iodine atom, and n ₃ represents 0 or 1).
Here, examples of the dihalide having a trans isomer structure represented by the general formula (3) include trans-2,3-bis (chloromethyl) -bicyclo- (2,2,1) -heptane, trans- 2,3-bis (bromomethyl) -bicyclo- (2,2,1) -heptane, trans-2,3-bis (iodomethyl) -bicyclo- (2,2,1) -heptane, trans-2,3- Bis (chloromethyl) -bicyclo- (2,2,1) -hept-5-ene, trans-2,3-bis (bromomethyl) -bicyclo- (2,2,1) -hept-5-ene, trans -2,3-bis (iodomethyl) -bicyclo- (2,2,1) -hept-5-ene, trans-2,3-bis (chloromethyl) -1α, 2,3,4α, 4aα, 5β, 6,7,8β, 8aα-decahide -1,4: 5,8-dimethanonaphthalene, trans-2,3-bis (bromomethyl) -1α, 2,3,4α, 4aα, 5β, 6,7,8β, 8aα-decahydro-1,4: 5,8-dimethananaphthalene, trans-2,3-bis (iodomethyl) -1α, 2,3,4α, 4aα, 5β, 6,7,8β, 8aα-decahydro-1,4: 5,8-di Methanonaphthalene, trans-2,3-bis (chloromethyl) -1α, 2,3,4α, 4aα, 5β, 8β, 8aα-octahydro-1,4: 5,8-dimethananaphthalene, trans-2,3 Bis (bromomethyl) -1α, 2,3,4α, 4aα, 5β, 8β, 8aα-octahydro-1,4: 5,8-dimethananaphthalene, trans-2,3-bis (iodomethyl) -1α, 2 , 3, 4α, 4aα, 5β, 8β, 8 α- octahydro-1,4: 5,8-dimethanol naphthalene, and the like. Here, the halogenated methyl group of the dihalide having the trans isomer structure represented by the general formula (3), for example, the chloromethyl group is stereochemically referred to as an endo-exo form. Among these, since raw materials are easy to obtain and can be easily and efficiently produced, trans-2,3-bis (chloromethyl) -bicyclo- (2 in which X ₁ in the general formula (3) is both a chlorine atom. , 2,1) -heptane, trans-2,3-bis (chloromethyl) -bicyclo- (2,2,1) -hept-5-ene, trans-2,3-bis (chloromethyl) -1α, 2,3,4α, 4aα, 5β, 6,7,8β, 8aα-decahydro-1,4: 5,8-dimethananaphthalene, trans-2,3-bis (chloromethyl) -1α, 2,3 4α, 4aα, 5β, 8β, 8aα-octahydro-1,4: 5,8-dimethananaphthalene is preferred, and since it has particularly high stability, trans-2, in which n ₁ in the general formula (3) is 0 3-bis (chloromethyl) -bi Black - (2,2,1) - heptane is more preferred.

Examples of the dihalide having a cis isomer structure represented by the general formula (4) and the dihalide having a cis isomer structure represented by the general formula (5) include cis-2,3-bis (chloro Methyl) -bicyclo- (2,2,1) -heptane, cis-2,3-bis (bromomethyl) -bicyclo- (2,2,1) -heptane, cis-2,3-bis (iodomethyl) -bicyclo -(2,2,1) -heptane, cis-2,3-bis (chloromethyl) -bicyclo- (2,2,1) -hept-5-ene, cis-2,3-bis (bromomethyl)- Bicyclo- (2,2,1) -hept-5-ene, cis-2,3-bis (iodomethyl) -bicyclo- (2,2,1) -hept-5-ene, cis-2,3-bis (Chloromethyl) -1α, 2,3,4α, 4aα, 5β, 6 7,8β, 8aα-decahydro-1,4: 5,8-dimethanonaphthalene, cis-2,3-bis (bromomethyl) -1α, 2,3,4α, 4aα, 5β, 6,7,8β, 8aα Decahydro-1,4: 5,8-dimethananaphthalene, cis-2,3-bis (iodomethyl) -1α, 2,3,4α, 4aα, 5β, 6,7,8β, 8aα-decahydro-1, 4: 5,8-dimethanonaphthalene, cis-2,3-bis (chloromethyl) -1α, 2,3,4α, 4aα, 5β, 8β, 8aα-octahydro-1,4: 5,8-dimethano Naphthalene, cis-2,3-bis (bromomethyl) -1α, 2,3,4α, 4aα, 5β, 8β, 8aα-octahydro-1,4: 5,8-dimethanonaphthalene, cis-2,3-bis (Iodomethyl) -1α, 2, 3, 4α, 4aα, 5β, 8 β, 8aα-octahydro-1,4: 5,8-dimethananaphthalene and the like can be mentioned. Here, a methyl halide group, for example, a chloromethyl group, of the dihalide having a cis structure represented by the general formula (4) is stereochemically classified as an exo-exo form, and the general formula (5). A methyl halide group, for example, a chloromethyl group, of a dihalide having a cis isomer structure represented by the formula is stereochemically classified as an endo-endo isomer. Among these, since it is easy to obtain raw materials and can be easily and efficiently produced, cis-2, wherein each of X ₂ and X _{3 in} the general formula (4) and the general formula (5) is a chlorine atom, 3-bis (chloromethyl) -bicyclo- (2,2,1) -heptane, cis-2,3-bis (chloromethyl) -bicyclo- (2,2,1) -hept-5-ene, cis- 2,3-bis (chloromethyl) -1α, 2,3,4α, 4aα, 5β, 6,7,8β, 8aα-decahydro-1,4: 5,8-dimethananaphthalene, cis-2,3- Bis (chloromethyl) -1α, 2,3,4α, 4aα, 5β, 8β, 8aα-octahydro-1,4: 5,8-dimethanonaphthalene is preferred, and since it has particularly high stability, ), each of _n 2, _{n 3} is in the general formula (5) Cis-2,3-bis (chloromethyl) is - bicyclo - (2,2,1) - heptane is more preferred.

  The ratio of the dihalide having a trans isomer structure to the dihalide having a cis isomer structure in the mixture used in the production method of the present invention is not particularly limited, but the yield of the cycloaliphatic diamine having a trans isomer structure is increased. Therefore, it is preferably 99: 1 to 30:70, and more preferably 99: 1 to 50:50.

  The imide compound used for imidization in the production method of the present invention is not particularly limited. For example, sodium phthalimide, potassium phthalimide, phthalimide cesium, sodium tetrachlorophthalimide, potassium tetrachlorophthalimide, tetrachlorophthalimide cesium, sodium nitrophthalimide, Nitrophthalimide potassium, nitrophthalimide cesium, aminophthalimide sodium, aminophthalimide potassium, aminophthalimide cesium, bromophthalimide sodium, bromophthalimide potassium, bromophthalimide cesium, naphthalimide sodium, naphthalimide potassium, naphthalimide cesium, ethosuximide sodium, ethos Kusimid potassium, ethosuximidocesium, koha Sodium acid imide, potassium succinimide, sodium cesium imide, maleimide sodium, maleimide potassium, maleimide cesium, sodium glutarimide, glutarimide potassium, glutarimide cesium, dimethyl glutarimide sodium, dimethyl glutarimide potassium, dimethyl glutarimide cesium, Examples include sodium tetramethylene glutarimide, potassium tetramethylene glutarimide, and cesium tetramethylene glutarimide.

  The amount of the imide compound used in the imidization is not particularly limited, but it is preferable because the amount of waste derived from the imide compound can be suppressed and the imidization can be efficiently performed in addition to suppressing the amount of expensive imide compound used. The amount of the imide compound is 2.0 to 4.0 mol, more preferably 2.0 to 2.5 mol with respect to 1 mol of the dihalide having a trans isomer structure.

  In the production method of the present invention, 1.0 to 10.0 mol of a basic compound is used with respect to 1 mol of a dihalide having a cis structure at the time of imidization. By using a basic compound, a dihalide having a cis structure is selectively dehalogenated and removed from the reaction system as a side reaction product. Therefore, a cycloaliphatic diamine having a trans isomer structure is selectively produced. When the amount of the basic compound used is less than 1.0 mol, the imide compound is consumed by the dihalide having a cis structure, so a large amount of the imide compound is necessary. The dihalide having a body structure also undergoes a dehalogenation reaction, and the yield of the cycloaliphatic diamine having a trans body structure is lowered. Since the cycloaliphatic diamine having a trans body structure is more selectively obtained and the amount of the imide compound used can be further suppressed, it is preferably 1.5 to 5.0 mol, more preferably 2.0 to 3.0 mol. It is.

  Although it does not specifically limit as a basic compound, For example, Alkali metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide; Alkali metal carbonates, such as sodium carbonate and potassium carbonate; Sodium Alkali metal alkoxides such as methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, lithium-t-butoxide, sodium-t-butoxide, potassium-t-butoxide; lithium hydride, sodium hydride, potassium hydride And alkali metal hydrides such as methyl lithium and butyl lithium; alkali metal amides such as lithium amide and sodium amide; organic bases such as pyridine, lutidine and toluidine. These basic compounds can be used alone or in combination of two or more. Of these, alkali metal hydroxides are preferably used, and sodium hydroxide is more preferably used because a cycloaliphatic diamine having a trans isomer structure is selectively obtained.

  The imidization can be performed in a solvent. Examples of such a solvent include, but are not limited to, water; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cyclooctane and decahydronaphthalene; aromatic hydrocarbons such as benzene, toluene and xylene; ethyl ether, tetrahydrofuran, dioxane, diglyme, triglyme, etc. Ethers such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol; ketones such as acetone and methyl ethyl ketone; N-methylpyrrolidone and dimethylform Bromide, amides such as dimethylacetamide; dimethylsulfoxide; dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, halogenated hydrocarbons such as tetrachloroethane and the like. These solvents can be used alone or in combination of two or more. Of these solvents, amides such as N-methylpyrrolidone, dimethylformamide, and dimethylacetamide are preferable, and dimethylformamide is more preferable because the reaction proceeds easily.

  There is no restriction | limiting in particular in the temperature in imidation, For example, it is -50-300 degreeC, Preferably it is 0-200 degreeC. The reaction pressure is not particularly limited, but is usually 0.001 to 30 MPa in absolute pressure, preferably 0.1 to 15 MPa. The reaction time depends on the temperature and the substrate concentration of the raw material and cannot be determined in general, but is usually 1 second to 100 hours. Although the atmosphere during the reaction is not particularly limited, it is desirable to perform the reaction while avoiding air. For example, the reaction is preferably performed in an inert gas atmosphere such as nitrogen, argon, or helium.

  There is no restriction | limiting in particular in the method of imidation, It has the trans body structure represented by the di-halide which consists of the trans body structure and cis body structure which are the raw material represented by General formula (1), and also General formula (3) A reaction apparatus comprising a dihalide, a mixture of a dihalide having a cis-form structure represented by the general formula (4) and a dihalide having a cis-form structure represented by the general formula (5), an imide compound, a basic compound and a solvent It is possible to carry out any of a batch system charged in the above, a continuous system in which the mixture as a raw material, an imide compound, a basic compound and a solvent are continuously supplied and an unreacted raw material and a reaction liquid are continuously extracted. In addition, the raw material charging order is not particularly limited, the raw material mixture, the imide compound, the basic compound and the solvent are mixed at once, and the raw material mixture, the basic compound and the solvent are contacted in advance. And a method of mixing with an imide compound. Among these, since the use amount of the imide compound can be suppressed, a method in which the mixture, which is a raw material, a basic compound, and if necessary, a solvent is contacted in advance and then mixed with the imide compound is preferable.

  After completion of the reaction, the product can be separated by a known separation method. For example, the product can be separated by distillation or precipitation from a solvent and filtration.

  In the present invention, the product imidized with the imide compound is then subjected to a decomposition reaction to produce a cycloaliphatic diamine having a trans structure represented by the general formula (2). Although it does not specifically limit as a reactive agent used by a decomposition reaction, For example, an acid, a base, or hydrazine is mentioned.

  Examples of the acid include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, carboxylic acids such as formic acid, acetic acid, propionic acid, and oxalic acid, phenol, and the like. Examples of the base include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate , Rubidium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate, cesium bicarbonate, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate And inorganic bases such as barium bicarbonate. Examples of hydrazines include hydrazine, methyl hydrazine, ethyl hydrazine, propyl hydrazine, phenyl hydrazine, o-tolyl hydrazine, m-tolyl hydrazine, p-tolyl hydrazine and the like. Among these, the reaction is easy and the cycloaliphatic diamine represented by the general formula (2) can be obtained in a high yield, so that lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide are obtained. An inorganic base such as hydrazine is preferable, and hydrazine is more preferable.

  The charging ratio of the imidized product and the reactant used in the decomposition reaction is not particularly limited, but since it can be efficiently decomposed, it is based on 1 mol of the dihalide mixture represented by the general formula (1). The amount of the reactant used in the decomposition reaction is 2 to 100 mol, preferably 2 to 50 mol, more preferably 2 to 20 mol.

  The decomposition with the reactant used in the decomposition reaction can be carried out in a solvent. Examples of such a solvent include, but are not limited to, water; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cyclooctane, decahydronaphthalene; aromatic hydrocarbons such as benzene, toluene, xylene; ethyl ether, tetrahydrofuran, dioxane, diglyme, triglyme, etc. Ethers such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol; ketones such as acetone and methyl ethyl ketone; N-methylpyrrolidone and dimethylform Bromide, amides such as dimethylacetamide; dimethylsulfoxide; dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, halogenated hydrocarbons such as tetrachloroethane and the like. These solvents can be used alone or in combination of two or more. Of these solvents, water is preferably used because the reaction easily proceeds; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol; N-methyl Amides such as pyrrolidone, dimethylformamide, and dimethylacetamide are preferred, and methanol, ethanol, and dimethylformamide are more preferred.

  The decomposition temperature by the reactant used in the decomposition reaction is not particularly limited, and is, for example, −50 to 200 ° C., preferably 0 to 150 ° C. The reaction pressure is not particularly limited, but is usually 0.1 to 30 MPa in absolute pressure, and preferably 0.1 to 10 MPa. The reaction time depends on the temperature and the substrate concentration of the raw material and cannot be determined in general, but is usually 1 minute to 100 hours. The atmosphere during the reaction is not particularly limited, but it is desirable to perform the reaction while avoiding air. For example, the reaction is preferably performed in an inert gas atmosphere such as nitrogen, argon, or helium.

  There are no particular restrictions on the method of decomposition by the reactant used in the decomposition reaction, and the batch, imidization product, and decomposition reaction in which the imidized product, the reactant and solvent used in the decomposition reaction are charged into the reactor at once. In addition to continuously supplying the reactants, the solvent, and the like used in 1), any of the unreacted raw material and the reaction solution can be continuously extracted. The reaction state is not particularly limited, but can be performed in a liquid phase or a solid-liquid mixed state.

  After completion of the reaction, a cyclic aliphatic diamine having a trans isomer structure represented by the general formula (2) can be obtained by a known separation method such as distillation.

  A dihalide having a trans isomer structure and a cis isomer structure represented by the general formula (1) used in the present invention, particularly a dihalide having a trans isomer structure represented by the general formula (3), represented by the general formula (4). The mixture of the dihalide having a cis isomer structure and the dihalide having a cis isomer structure represented by the general formula (5) may be produced by any method. For example, cyclopentadiene or dicyclopentadiene By reacting with 1,4-dihalogeno-2-butene represented by the following general formula (6), a dihalide having a double bond can be produced efficiently. Further, by dihydrating a dihalide having a double bond with hydrogen, it is possible to produce a dihalide whose ring structure is entirely composed of single bonds.

（式中、Ｙはそれぞれ独立して塩素原子、臭素原子又はヨウ素原子を表す。）
ここで、トランス体構造を有するジハロゲン化物とシス体構造を有するジハロゲン化物の比を高めるためには、原料として用いる１，４−ジハロゲノ−２−ブテンの立体構造が重要で、トランス体がシス体よりも比率の高い１，４−ジハロゲノ−２−ブテンを用いることが好ましい。

(In formula, Y represents a chlorine atom, a bromine atom, or an iodine atom each independently.)
Here, in order to increase the ratio of the dihalide having a trans isomer structure to the dihalide having a cis isomer structure, the three-dimensional structure of 1,4-dihalogeno-2-butene used as a raw material is important, and the trans isomer is a cis isomer. It is preferable to use 1,4-dihalogeno-2-butene having a higher ratio.

  The cycloaliphatic diamine having a trans body structure produced in the present invention can be suitably used as a monomer raw material for polyurethane resins and polyamide resins and an intermediate for raw materials for medical and agricultural chemicals.

  The present invention provides a selective and efficient method for producing a cycloaliphatic diamine having a trans-form structure, which is useful as an intermediate for raw materials of polyurethane and polyamide resins and raw materials for pharmaceuticals and agricultural chemicals. Useful for.

  Examples of the present invention are shown below, but the present invention is not limited to these examples.

  The measurement methods used in the examples are shown below.

<Gas chromatographic analysis>
Gas chromatograph (GC-1700, Shimadzu Corporation) equipped with FID detector (hydrogenation ionization detector) using TC-1 column (trade name) manufactured by GL Sciences, with N-methylpyrrolidone added as an internal standard to the reaction solution. Was injected with 0.4 μl of the reaction solution, and the analysis was performed under the conditions of a vaporization chamber temperature of 250 ° C. and a detector temperature of 320 ° C.

<GC-MS measurement>
Using a gas chromatograph mass spectrometer (GC part; manufactured by Hewlett-Packard, trade name HP6890, MS part; manufactured by JEOL, trade name JMS-700), measurement was performed under conditions of a vaporization chamber temperature of 250 ° C. and a detector temperature of 320 ° C. went.

^<13 C-nuclear magnetic resonance ^{(hereinafter,} referred to as 13 C-NMR) measurement>
Using a nuclear magnetic resonance apparatus (trade name GSX400, manufactured by JEOL Ltd.), the sample was dissolved in deuterated chloroform solvent and measured.

Synthesis example 1
(Synthesis of cycloaliphatic dihalides having double bonds in the ring)
A 2-liter autoclave was charged with 212 g (1.6 mol) of dicyclopentadiene and 800 g (6.4 mol) of 1,4-dichloro-2-butene (trans isomer: cis isomer = 90: 10). After the inside was purged with nitrogen, the temperature was raised to 170 ° C. with stirring, and the mixture was heated and stirred as it was for 5 hours to carry out Diels-Alder reaction. After completion of the reaction, the temperature was lowered to 25 ° C., and the reaction solution was taken out from the autoclave. The reaction solution was a brown solution. The obtained brown solution was distilled under a reduced pressure of 0.4 kPa, and a distillate in the range of 80 to 93 ° C. was collected to obtain 2,3-bis (chloromethyl) -bicyclo- (94 wt. 2,2,1) -Hept-5-ene was obtained as a colorless solution of 365 g (yield based on dicyclopentadiene: 60%).
(Synthesis of cycloaliphatic dihalides whose ring structures are all single bonds)
In a 300 ml autoclave, 150 g of 2,3-bis (chloromethyl) -bicyclo- (2,2,1) -hept-5-ene obtained above and 50 g of ethanol and 5 wt% Pd / C2 manufactured by N.E. 0.0 g was added and the atmosphere was replaced with nitrogen. Thereafter, the temperature in the autoclave was raised to 50 ° C. while stirring, hydrogen was supplied and maintained at 1.0 MPa, and the reaction solution was taken out after 2 hours. The reaction solution obtained was filtered and distilled under a reduced pressure of 0.4 kPa, and the distillate in the range of 88 to 90 ° C. was collected and analyzed by gas chromatography. As a result, 2,3-bis (chloromethyl) -bicyclo- ( 2,2,1) -Hept-5-ene is completely converted to 2,3-bis (chloromethyl) -bicyclo- (2,2,1) -heptane (trans isomer: cis isomer = 81: 19). The selectivity of was 91%.

Example 1
In a 1 L glass separable flask, 218 g of dimethylformamide, 75 g (0.41 mol) of potassium phthalimide and 12.5 ml of 8N aqueous sodium hydroxide solution (0.10 mol, 1 mol of dihalide having a cis structure): 2.3 mol And 2,3-bis (chloromethyl) bicyclo- (2,2,1)-obtained in Synthesis Example 1
50 g of heptane (0.259 mol, breakdown: trans isomer 0.192 mol, cis isomer 0.044 mol, other 0.023 mol) was added, the temperature in the separable flask was raised to 150 ° C. with stirring, and the mixture was heated and stirred for 8 hours. . After completion of the reaction, the mixture was cooled to room temperature, 100 g of water was added, and the mixture was stirred for 30 minutes. After stirring, the solid content was separated by suction filtration using a membrane filter. The solid content separated by filtration was transferred to a separable flask, 150 g of ethanol was added, and the mixture was heated and stirred at 80 ° C., and 118 g (2.36 mol) of hydrazine monohydrate was added under ethanol reflux. After stirring with heating at 80 ° C. for 2 hours, the mixture was cooled to room temperature and suction filtered with a membrane filter. As a result of analyzing the filtrate by gas chromatography, 2,3-bis (chloromethyl) -bicyclo- (2,2,1) -heptane was completely converted to 2,3-bis (aminomethyl) -bicyclo- The yield of (2,2,1) -heptane was 71%.

  As a result of measuring GC-MS of the product after the decomposition reaction, the main component was confirmed to have a molecular ion peak at m / e154.

As a result of ¹³ C-NMR measurement, peaks based on methylene groups at δ 44.4 ppm and 47.6 ppm, 22.2 ppm, 30.0 ppm, 36.8 ppm, 38.6 ppm, 39.9 ppm, 49.6 ppm, 52.0 ppm A peak based on the hydrocarbon of the norbornane ring was observed, and 2,3-bis (aminomethyl) -bicyclo- (2,2,1) -heptane obtained by this reaction was a trans isomer. Here, of the raw material 2,3-bis (chloromethyl) bicyclo- (2,2,1) -heptane mixed with the trans isomer and the cis isomer, the yield based on the trans isomer raw material was 87%. .

Example 2
Except for using 18.8 ml of 8N sodium hydroxide aqueous solution (0.15 mol, amount based on 1 mol of dihalide having a cis structure: 3.4 mol), imidization and decomposition reaction were performed in the same manner as in Example 1, Trans-2,3-bis (aminomethyl) -bicyclo- (2,2,1) -heptane was obtained. The yield of trans-2,3-bis (aminomethyl) -bicyclo- (2,2,1) -heptane was 70%. The yield based on the trans isomer raw material was 86%. No cis isomer was observed.

Example 3
Except for using 25.0 ml of an 8N aqueous sodium hydroxide solution (0.20 mol, an amount based on 1 mol of a dihalide having a cis structure: 4.6 mol), an imidization and decomposition reaction was performed in the same manner as in Example 1, Trans-2,3-bis (aminomethyl) -bicyclo- (2,2,1) -heptane was obtained. The yield of trans-2,3-bis (aminomethyl) -bicyclo- (2,2,1) -heptane was 69%. The yield based on the trans isomer raw material was 84%. No cis isomer was observed.

Example 4
An imidization and decomposition reaction was performed in the same manner as in Example 1 except that 6.3 ml of an 8N aqueous sodium hydroxide solution (0.05 mol, an amount based on 1 mol of a dihalide having a cis isomer structure: 1.1 mol) was used. Trans-2,3-bis (aminomethyl) -bicyclo- (2,2,1) -heptane was obtained. The yield of trans-2,3-bis (aminomethyl) -bicyclo- (2,2,1) -heptane was 65%. The yield based on the trans isomer raw material was 80%. No cis isomer was observed.

Comparative Example 1
Except that 150 g (0.816 mol) of potassium phthalimide was used and sodium hydroxide was not used, imidization and decomposition reactions were performed in the same manner as in Example 1, and trans-2,3-bis (aminomethyl) -bicyclo- ( 2,2,1) -Heptane was obtained. The yield of trans-2,3-bis (aminomethyl) -bicyclo- (2,2,1) -heptane was 70%. The yield based on the trans isomer raw material was 86%. No cis isomer was observed. Although a high trans yield was obtained, a large amount of potassium phthalimide was required as compared with Example 1.

Comparative Example 2
Except that no 8N aqueous sodium hydroxide solution was added, imidization and decomposition were performed in the same manner as in Example 1 to obtain trans-2,3-bis (aminomethyl) -bicyclo- (2,2,1) -heptane. Obtained. The yield of trans-2,3-bis (aminomethyl) -bicyclo- (2,2,1) -heptane was 47%. The yield based on the trans isomer raw material was 57%. No cis isomer was observed.

Synthesis example 2
(Synthesis of cyclic dihalides having double bonds in the ring)
Trans isomer: cis isomer = 95: 5 except that 1,4-dichloro-2-butene was used, Diels-Alder reaction and the like were performed in the same manner as in Synthesis Example 1 to obtain 2,3-bis (chloro Methyl) -bicyclo- (2,2,1) -hept-5-ene was obtained as a colorless solution of 350 g. The obtained 2,3-bis (chloromethyl) -bicyclo- (2,2,1) -hept-5-ene was trans isomer: cis isomer = 90: 10. Further, the cis form was only an endo-endo form, and no exo-exo form was included.
(Synthesis of cycloaliphatic dihalides whose ring structures are all single bonds)
Using 150 g of 2,3-bis (chloromethyl) -bicyclo- (2,2,1) -hept-5-ene obtained above, a hydrogenation reaction or the like was performed in the same manner as in Synthesis Example 1. 2,3-bis (chloromethyl) -bicyclo- (2,2,1) -hept-5-ene is completely converted to 2,3-bis (chloromethyl) -bicyclo- (2,2,1) -The selectivity of heptane (trans isomer: cis isomer = 90: 10) was 88%. Further, the cis form was only an endo-endo form, and no exo-exo form was included.

Example 6
Instead of 50 g of 2,3-bis (chloromethyl) -bicyclo- (2,2,1) -heptane obtained in Synthesis Example 1, 2,3-bis (chloromethyl)-obtained in Synthesis Example 2 Except for using 48 g of bicyclo- (2,2,1) -hept-5-ene, imidization and decomposition were carried out in the same manner as in Example 1 to obtain trans-2,3-bis (aminomethyl) -bicyclo- (2,2,1) -Hept-5-ene was obtained. The yield of trans-2,3-bis (aminomethyl) -bicyclo- (2,2,1) -hept-5-ene was 80%. Note that. The yield based on the trans isomer raw material was 89%. No cis isomer was observed.

Example 7
Instead of 50 g of 2,3-bis (chloromethyl) -bicyclo- (2,2,1) -heptane obtained in Synthesis Example 1, 2,3-bis (chloromethyl)-obtained in Synthesis Example 2 Except for using 50 g of bicyclo- (2,2,1) -heptane, an imidization and decomposition reaction was performed in the same manner as in Example 1, and trans-2,3-bis (aminomethyl) -bicyclo- (2,2 , 1) -Heptane was obtained. The yield of trans-2,3-bis (aminomethyl) -bicyclo- (2,2,1) -heptane was 83%. Note that. The yield based on the trans isomer raw material was 92%. No cis isomer was observed.

Claims (7)

A cycloaliphatic having a trans isomer structure represented by the following general formula (2), wherein a dihalide having a trans isomer structure and a cis isomer structure represented by the following general formula (1) is imidized with an imide compound and then decomposed. A method for producing a diamine, which is represented by the general formula (2), wherein 1.0 to 10.0 mol of a basic compound is used per 1 mol of a dihalide having a cis structure at the time of imidization. A process for producing a cycloaliphatic diamine having a trans isomer structure.

(In the formula, a dotted line represents a single bond or a double bond, X represents each independently a chlorine atom, a bromine atom or an iodine atom, and n represents 0 or 1).

(In the formula, a dotted line represents a single bond or a double bond, and m represents 0 or 1.) The dihalide represented by the general formula (1) is a dihalide having a trans isomer structure represented by the following general formula (3), a dihalide having a cis isomer structure represented by the following general formula (4), and the following general formula: 2. The method for producing a cycloaliphatic diamine having a trans isomer structure according to claim 1, which is a mixture of dihalides having a cis isomer structure represented by (5).

(In the formula, a dotted line represents a single bond or a double bond, X ₁ independently represents a chlorine atom, a bromine atom or an iodine atom, and n ₁ represents 0 or 1.)

(In the formula, a dotted line represents a single bond or a double bond, X ₂ independently represents a chlorine atom, a bromine atom or an iodine atom, and n ₂ represents 0 or 1).

(In the formula, a dotted line represents a single bond or a double bond, X ₃ independently represents a chlorine atom, a bromine atom or an iodine atom, and n ₃ represents 0 or 1). The ratio of the dihalide having a trans isomer structure to the dihalide having a cis isomer structure is 99: 1 to 30:70, The cycloaliphatic diamine having a trans isomer structure according to claim 1 or 2, Manufacturing method. The method for producing a cycloaliphatic diamine having a trans structure according to any one of claims 1 to 3, wherein both X in the general formula (1) are chlorine atoms, and n is 0. . Each of X ₁ , X ₂ , and X ₃ in General Formula (3), General Formula (4), and General Formula (5) is a chlorine atom, and each of n ₁ , n ₂ , and n ₃ is 0 The method for producing a cycloaliphatic diamine having a trans isomer structure according to any one of claims 1 to 4. The method for producing a cycloaliphatic diamine having a trans isomer structure according to any one of claims 1 to 5, wherein the basic compound is an alkali metal hydroxide. The method for producing a cycloaliphatic diamine having a trans isomer structure according to any one of claims 1 to 6, wherein the decomposition reaction is a decomposition reaction with hydrazine.