JPH0615504B2 - Optically active 4-cyclopentenones - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention has the general formula (I) (In the formula, R represents an acetoxyl group, and R ₁ represents an alkyl group, an alkenyl group, or an alkynyl group.
The substituent R ₁ at the position and the methyl group at the 3 position are in the cis configuration. ) Related to d-4-cyclopentenones.

The d-4-cyclopentenones represented by the general formula (I) are novel compounds synthesized by the present inventors for the first time, and the compounds are not only useful as pesticides and their intermediates, It is also useful as an intermediate for fragrances and pharmaceuticals.

Such d-4-cyclopentenones have the general formula (II) (In the formula, R ₁ has the same meaning as described above, and R ₁ and 3 at the 2-position
The methyl group at the position indicates cis coordination. ) To dl-4-cyclopentenones represented by Pseudomona
It can be produced by allowing a microorganism belonging to the s genus or an enzyme obtained from the same to act and hydrolyze it.

Dl used as a raw material in the above hydrolysis reaction
-4-Cyclopentenones can be easily produced, for example, by the method shown below.

Further, in this hydrolysis reaction, Pseu having the ability to hydrolyze only 1-4-cyclopentenones, which is one of the optical isomers of the dl-4-cyclopentenones.
Microorganisms of the genus domonas such as Pseudomonas fragi or enzymes obtained therefrom are used, and the forms of use are purified enzymes, crude enzymes, enzyme-containing products, microbial culture solutions, cultures, bacterial cells, culture filtrates, and treated products thereof. It may be used in various forms as necessary, and the enzyme and the microorganism may be used in combination. The hydrolysis reaction is
The above-mentioned microorganism of the genus Pseudomonas or the enzyme obtained therefrom and dl-4-cyclopentenones are usually stirred vigorously in a buffer solution. As the buffer solution, a commonly used buffer solution of an inorganic acid salt such as sodium phosphate and potassium phosphate, a buffer solution of an organic acid salt such as sodium citrate and the like can be used. Its pH is 5-1
0, preferably in the range of 6 to 9, and the concentration is usually 0.0
It is in the range of 5 to 2M, preferably 0.1 to 0.5M.
The reaction temperature is usually about 20 to 40 ° C., and the reaction time is generally about 10 to 70 hours, but it is not limited thereto.

This hydrolysis reaction is carried out by the raw material dl-4 from the viewpoint of optical yield.
-It is preferable that the reaction rate of cyclopentenones is less than 50%.

By carrying out such a hydrolysis reaction, only 1-4-cyclopentenones, which is one of the optical isomers of the dl-4-cyclopentenones represented by the general formula (II), which is a raw material for the hydrolysis reaction, is hydrolyzed. Decomposed, general formula (III) (In the formula, R ₁ has the same meaning as described above, provided that the substituent R _{1 at} the 2-position and the methyl group at the 3-position are cis-coordinated.) The other optical isomer of the starting material, d-4-cyclopentenone, which has been produced, remains as it is, and eventually d-4-cyclopentenone represented by the general formula (I) as an unreacted product. You can get the kind. After completion of the reaction, in order to separate the two from the reaction solution, the hydrolysis reaction solution is subjected to extraction treatment with a solvent such as methyl isobutyl ketone, ethyl acetate, ethyl ether, etc., and the solvent is distilled off from the obtained organic layer. By a method such as treating the concentrated residue with column chromatography, the desired d-4-cyclopentenone represented by the general formula (I) and d-4-cyclopentenone represented by the general formula (III) are obtained. Alcohols can be separated.

Hereinafter, the present invention will be described with reference to examples.

Example 1 Bacterial medium 200 m in a 500 m Sakaguchi flask
(0.05M phosphate buffer; pH 7.0) was added, and after sterilization Pse
udomonas fragi (IFO-3458) was inoculated and cultured at 30 ° C for 2 days with shaking. 1.5 g of dl-3-acetoxy-2-allyl-3-methyl-4-cyclopentenone was added to this, and 3
Hydrolysis is performed by shaking culture at 0 ° C for 24 hours. This is extracted 4 times with 50 m of methyl isobutyl ketone. The solvent was distilled off from the obtained organic layer, and the concentrated residue was purified by column chromatography with a mixed solution of ethyl acetate: toluene = 3: 5 and d-2-allyl-3-hydroxy-3-methyl-4-. Cyclopentenone 0.28 g (yield 24%) [Optical rotation ▲ [α] ²⁰ _D ▼ + 22.5 °, (c = 1, chloroform), refractive index ▲ n ²⁰ _D ▼ 1.4978] and d-3-acetoxy- 2-allyl-3-methyl-4-cyclopentenone 0.75
g [optical rotation ▲ [α] ²⁰ _D ▼ + 80.7 °, (c = 1, chloroform), refractive index ▲ n ²⁰ _D ▼ 1.4801] was obtained.

The above d-2-allyl-3-hydroxy-3-methyl-
The coordination of allethlorone obtained by rearranging 4-cyclopentenone with triethylamine was R (-), and the optical purity was 94%.

(Analytical method of optical purity: Agri.Biol.Chem., 41 (10), 2003
~ 2006 (1977))) Example 2 2.0 g of dl-3-acetoxy-2-n-pentyl-3-methyl-4-cyclopentenone was added to the culture solution prepared according to Example 1 at 30 ° C. Hydrolysis is performed by shaking culture for 30 hours. 40m of this methyl isobutyl ketone
Extract twice with. Then, post-treatment and purification were carried out according to Example 1 to obtain d-3-hydroxy-2-n-pentyl-
0.48 g of 3-methyl-4-cyclopentenone (yield 30
%) [Optical rotation ▲ [α] ²⁰ _D ▼ + 17.5 °, (c = 1, chloroform), refractive index ▲ n ²⁰ _D ▼ 1.4811] and d-3-acetoxy-2-n-pentyl-3-methyl This gave 0.84 g of -4-cyclopentenone [optical rotation ▲ [α] ²⁰ _D ▼ + 60.8 °, (c = 1, chloroform), refractive index ▲ n ²⁰ _D ▼ 1.4703].

Optical of 4-hydroxy-2-n-pentyl-3-methyl-2-cyclopentenone obtained by rearranging the above d-3-hydroxy-2-n-pentyl-3-methyl-4-cyclopentenone The purity was 91%.

Example 3 dl-3-acetoxy-2-allyl-in Example 1
Dl-3-instead of 3-methyl-4-cyclopentenone
D-3-Hydroxy-2-propargyl-3-methyl was reacted, worked up and purified in the same manner as in Example 1 except that 1.5 g of acetoxy-2-propargyl-3-methyl-4-cyclopentenone was used. -4-Cyclopentenone 0.19g
(Yield 16%) [Optical rotation ▲ [α] ²⁰ _D ▼ + 124.0 °, (c = 1, chloroform), refractive index ▲ n ²⁰ _D ▼ 1.5103] and d-3-acetoxy-2-propargyl-3. There was obtained 0.82 g of -methyl-4-cyclopentenone [optical rotation ▲ [α] ²⁰ _D ▼ + 14.6 °, (c = 1, chloroform), refractive index ▲ n ²⁰ _D ▼ 1.4943].

The optical purity of 4-hydroxy-2-propargyl-3-methyl-2-cyclopentenone obtained by rearranging the above d-3-hydroxy-2-propargyl-3-methyl-4-cyclopentenone is 93%. Met.

Example 4 2.0 g of dl-3-acetoxy-2-ω-butenyl-3-methyl-4-cyclopentenone was added to the culture solution prepared according to Example 1, and the mixture was cultivated with shaking at 30 ° C. for 20 hours. Hydrolyze. 40m of this methyl isobutyl ketone
Extract twice with. Thereafter, post-treatment and purification were carried out according to Example 1 to give d-3-hydroxy-2-ω-butenyl-.
0.32 g of 3-methyl-4-cyclopentenone (yield 20
%) [Optical rotation ▲ [α] ²⁰ _D ▼ + 21.1 °, (c = 1, chloroform), refractive index ▲ n ²⁰ _D ▼ 1.4983] and d-3-acetoxy-2-ω-butenyl-3-methyl -4-cyclopentenone 1.02 g [optical rotation ▲ [α] ²⁰ _D ▼ + 62 °, (c = 1, chloroform), refractive index ▲ n ²⁰ _D ▼ 1.4806] was obtained.

d-3-Hydroxy-2-ω-butenyl-3-methyl-
The optical purity of 4-hydroxy-2-ω-butenyl-3-methyl-2-cyclopentenone obtained by rearranging 4-cyclopentenone was 92%.

Claims (1)

[Claims] 1. A general formula (In the formula, R represents an acetoxyl group, and R ₁ represents an alkyl group, an alkenyl group, or an alkynyl group.
The substituent R ₁ at the position and the methyl group at the 3 position are in the cis configuration. ) D-4-cyclopentenones