JPH07252190A - Hexadienone derivative and its production - Google Patents

Abstract

PURPOSE:To provide a novel compound useful as an intermediate for perfumes or medicines. CONSTITUTION:This new compound is 2,6-diacetoxy-6-methoxy-1,3-hexadiene-5- one of formula I. The compound of formula I is obtained by reacting aldehyde- D-glucose pentaacetate of formula II with methanol in the presence of a basic compound (preferably triethylamine) preferably at 0-30 deg.C for 3-72hrs. The basic compound is preferably used in an amount of 1-4 times that of the compound of formula II as the raw material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The hexadienone derivative represented by the chemical formula 1 relating to the present invention is a novel compound synthesized by the present inventors for the first time and is a valuable compound as an intermediate for perfumes and pharmaceuticals.

[0002]

2. Description of the Related Art The hexadienone derivative represented by Chemical formula 1 has never been synthesized in the past.

[0003]

The problem to be solved is the conversion of naturally abundantly produced saccharides into useful synthetic raw materials by a simple method.

[0004]

DISCLOSURE OF THE INVENTION In the present invention, the reaction of aldehyde-D-glucose pentaacetate shown in Chemical formula 2 with methanol in the presence of a base compound was examined. It was found that a hexadienone derivative was obtained, and the present invention was completed.

That is, the gist of the present invention is that the hexadienone derivative represented by Chemical formula 1 and the aldehyde-D-glucose pentaacetate represented by Chemical formula 2 are reacted with methanol in the presence of a basic compound in an organic solvent. It is a method for producing the hexadienone derivative represented by Chemical formula 1.

[0006] Such a reaction is a novel reaction first revealed by the present inventor.

In this reaction, the aldehyde-D-glucose pentaacetate represented by Chemical formula 2 used as a raw material is commercially available D-glucopyranose.
M. L. Method of Wolfrom [METHODS I
N CARBOHYDRATECHEMISTRY, I
I, 427 (1963)].

The reaction of aldehyde-D-glucose pentaacetate represented by Chemical formula 2 with methanol in the presence of a base compound is carried out in an organic solvent.

As the organic solvent, a commonly used organic solvent can be used. Chloroform, acetone, which has a high solubility of D-glucofuranurono-6,3-lactone triacetate represented by Chemical formula 2, which is a substrate for the reaction, It is desirable to use acetonitrile or dichloromethane.

As the basic compound, 1,8-diazabicyclo [5.4.0] -undec-7-ene (DBU),
Typical organic base compounds such as triethylamine, N-methylpyrrolidine, N, N-dimethylbenzylamine, N, N-diethylaniline and tri-n-butylamine are exemplified, but triethylamine is particularly preferable.

The amount of the basic compound used is usually 2
Although it is 2 to 10 times the molar amount of the compound represented by
Particularly, 1 to 4 times the molar amount is suitable.

The amount of methanol used is usually 1 mol based on the compound of the chemical formula 2 as a raw material.

The reaction temperature is optional between 0 and 100 ° C, but is preferably around 0 to 30 ° C. The reaction time is optional from 3 to 72 hours depending on the reaction temperature.

By such a reaction, the hexadienone derivative represented by Chemical formula 1 which is a compound of the present invention can be easily obtained, and can be separated by usual separation means such as extraction, liquid separation, concentration, thin layer chromatography, column chromatography and the like. Can be isolated and purified from the reaction mixture.

[0015]

Example 1 To 0.195 g of aldehyde-D-glucose pentaacetate, 3 ml of chloroform, 0.02 ml of methanol and 0.21 ml of triethylamine were added, and the mixture was stirred at room temperature for 17 hours for reaction. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, and 2,6-diacetoxy-1-methoxy-1,3-hexadien-5-one was isolated from the obtained oil by thin layer chromatography. (Yield 27.8%)

The IR spectrum data of the hexadienone derivative represented by Chemical Formula 1 relating to the present invention is as follows. IR (NaCl); 2930, 2850, 17
30, 1720, 1700, 1640, 1410, 13
60, 1210, 1040, 1020, 920, 730
cm ^-1

[0017]

Example 2 Chloroform (3 ml) and triethylamine (0.21 ml) were added to aldehyde-D-glucose pentaacetate (0.195 g), and the mixture was reacted at room temperature for 3 days with stirring. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, and 2,6-diacetoxy-1-methoxy-1,3-hexadien-5-one was isolated from the obtained oil by column chromatography. (Yield 74.3
%)

[0018]

Example 3 Chloroform (3 ml), methanol (0.02 ml) and triethylamine (0.28 ml) were added to aldehyde-D-glucose pentaacetate (0.195 g), and the mixture was stirred at room temperature for 3 days for reaction. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, and 2,6-diacetoxy-1-methoxy-1,3-hexadien-5-one was isolated from the resulting oil by column chromatography. (Yield 78.2%)

Claims (2)

[Claims] Claims: Hexadienone derivative represented by Chemical formula 1 2. [Chemical formula 2] A method for producing the hexadienone derivative represented by Chemical formula 1, wherein the aldehyde-D-glucose pentaacetate represented by Chemical formula 2 is reacted with methanol in the presence of a base compound.