JPH062756B2 - Method for optical resolution of glycidyl compound - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for optical resolution of a glycidyl compound.

(Prior Art) Glycidyl compounds are used as intermediates in the synthesis of various derivatives.
In addition, it is a substance having a high industrial value as a monomer for polymerization.

In recent years, it is well known that one of optical isomers of a chemical substance having a physiological function has a special meaning, and an optically active glycidyl compound is used as an intermediate for the synthesis of such a physiologically functional substance. It is of great significance to obtain. Also in the polymer chemistry industry, synthesizing a polymer having only a specific three-dimensional structure is significant because a polymer having a specific function can be obtained thereby.

Obtaining an optically active glycidyl compound is industrially very important, but conventionally, to produce an optically active glycidyl compound, a natural optically active substance is used as a starting material or a microbiological agent is used. Of an optically active precursor with the aid of various methods, and using this as a raw material to obtain a glycidyl compound synthetically or by chemically reacting with an optically active compound to change it to another substance once, and then again by the chemical reaction to obtain the target compound. Attempts have been made to obtain

However, these methods are extremely inefficient and have irrational problems such as low optical purity and the fact that one enantiomer cannot be obtained.

The present inventors use a 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol derivative of the compound of the following formula (I) used in the present invention to give a cyclic ketone having an alkyl substituent, etc. Have already been reported to be completely resolvable (J. Am. Chem. Soc. 1983 5151). However, an optical resolution method of a glycidyl compound using this method has not yet been known.

(Object of the Invention) An object of the present invention is to provide a method for easily and completely optically resolving an optically active glycidyl compound from a racemic glycidyl compound.

(Structure of the Invention) The present invention is a method of performing optical resolution by contacting a racemic glycidyl compound with an optically active compound to form a complex in which only one antipode is incorporated from the racemic glycidyl compound. That is, a racemic glycidyl compound and the following general formula (I) (However, in the formula (I), X and Y are an atom or a group selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group and an alkylthio group, and X and Y are the same as hexadiyne. X and Y are not the same atom or group when they are bonded at the same position with respect to the carbon of each phenyl group bonded to carbon.) 1,1,6,6 -Tetraphenylhexa-2,4-diyne-1,6-diol derivative to form a complex incorporating the glycidyl compound, and an optically active glycidyl compound is extracted from the complex. It is a division method.

The glycidyl compound that is the subject of the present invention includes a wide range of compounds, and glycidyl esters and glycidyl ethers are particularly preferable because they form a stable complex.

Specific examples of the glycidyl esters include glycidyl acetate, glycidyl propionate, glycidyl butyrate, glycidyl benzoate, glycidyl cinnamate, glycidyl naphthoate, glycidyl naphthoxyacetate, glycidyl acrylate, glycidyl methacrylate, and the like. As a specific example, methyl glycidyl ether,
Allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, naphthyl glycidyl ether, etc. are mentioned.

The above formula (I) compound used in the present invention is already known, and the following formula (II) compound which is a precursor is oxidatively coupled, for example, air oxidation is carried out in an acetone solution in the presence of a cuprous chloride-pyridine catalyst. Can be easily manufactured.

Further, the above formula (II) compound is produced from the corresponding ketone and acetylene by an ethynylation reaction.

Specific examples of the above formula (I) compound include 1,6-di-o-chlorophenyl-1,6-diphenylhexa-2,4-diyne-1,6-diol 1,6-di-o- Fluorophenyl-1,6-diphenylhexa-2,4-diyne-1,6-diol 1,6-di-p-chlorophenyl-1,6-diphenylhexa-2,4-diyne-1,6-diol 1 , 6-di-pt-butylphenyl-1,6-diphenylhexa-2,4-diyne-1,6-diol 1,6-di-o-methoxyphenyl-1,6-diphenylhexa-2, 4-diyne-1,6-diol 1,6-di-p-phenylthiophenyl-1,6-diphenylhexa-2,4-diyne-1,6-diol and the like can be mentioned.

In the present invention, a racemic glycidyl compound and (I)
The complex is formed with the formula compound by mixing them directly or as a solution. The conditions of the complex-forming reaction differ depending on the substance, but the reaction is usually performed at room temperature to the reflux temperature of the solvent. The reaction time may be appropriately determined depending on the precipitation of the complex that is formed as a solid crystal. The complex is usually produced as a compound having a molar ratio of the glycidyl compound to the compound of formula (I) of 3: 1 to 1: 3.

As the solvent used in the above reaction, aliphatic hydrocarbons, aromatic hydrocarbons, ethers or a mixed solvent thereof is generally used.

To take out the optically active glycidyl compound from the above-obtained complex, the precipitate formed by the reaction is filtered off and, if necessary, purified by recrystallization, and then heated, distilled, replaced with a polar solvent, or chromatographed. Thus, one of the optically active glycidyl compounds can be easily released and isolated.

Further, the other optical isomer can be easily obtained from the filtrate after the precipitation filtration.

(Effect of the Invention) According to the present invention, both optically active antipodes can be easily obtained from a racemic glycidyl compound, and the obtained optically active glycidyl compound is of extremely high purity.

Examples Example 1 Optically pure levorotatory 1,6-di-o-chlorophenyl-1,6-diphenyl-hexa-2,4-diyne-1,
6-diol ([α] _D −122 °, mp 127-129 ° C.) 9.66 g
(0.22 mol) and racemic glycidyl butyrate 5.76 g (0.04
Mol) was dissolved in a mixed solvent of 10 ml of ether and 20 ml of petroleum ether and refluxed for 12 hours. After cooling, 11.0 g of colorless prism crystals was collected by filtration (yield 88%). This crystal is a complex in which the above compound has a molar ratio of 1: 1 and its melting point is
Specific rotation [α] _D measured at 72-75 ℃ in methanol solution
(The same solvent was used in the following measurements) was -93.5 °.

Next, the crystals were decomposed by heating under reduced pressure to distill out levorotatory glycidyl butyrate. This is [α] _D- 5.
It was 7 °.

The prism crystal obtained by recrystallizing the prism 5 times had a melting point of 72 to 75 ° C and [α] _D- 94.1 °. This was heated and decomposed under reduced pressure in the same manner as above to obtain levorotatory glycidyl [α] _D -11.8 °.

On the other hand, the filtrate from which prism crystals were separated was distilled to obtain 3.2 g of dextrorotatory glycidyl butyrate. This one is [α] _D +
It was 4.26 °.

Example 2 The same levorotatory 1,6-di-o-chlorophenyl-1,6-diphenyl-hexa-2,4-diyne-as in Example 1.
4.83 g (0.01 mol) of 1,6-diol and 3.0 g (0.02 mol) of racemic phenylglycidyl ether were dissolved in a mixed solvent of 5 ml of ether and 20 ml of petroleum ether and refluxed for 12 hours. After cooling, 4.65 g (yield 73%) of colorless prism crystals, which is a complex of the above compound in a molar ratio of 1: 1 was obtained. This product had a melting point of 79-80 ℃ and was measured with a methanol solution [α] _D
Was -90.6 °.

Then, the crystals were distilled under reduced pressure to obtain levorotatory phenyl glycidyl ether [α] _D -1.4 °.

The product obtained by recrystallizing the prism crystal once had a melting point of 79 to 81 ° C and [α] _D -92.9 °. The crystals were distilled under reduced pressure to obtain [α] _D -2.7 ° phenylglycidyl ether.

Claims (1)

[Claims] 1. A racemic glycidyl compound and the following general formula
From the optically active 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol derivative represented by (I), a complex incorporating the above glycidyl compound is formed, and from this complex Method for optical resolution of glycidyl compound characterized by taking out optically active glycidyl compound (However, in the formula (I), X and Y are atoms or groups selected from a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, and an alkylthio group, and X and Y are the same as hexadiyne. (X and Y are not the same atom or group when they are bonded at the same position with respect to the carbon of each phenyl group bonded to the carbon.)