JPH0581240B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides general formulas (-l) and (-l)

【formula】

[Formula] (In the formula, R ₁ represents an alkyl group, alkenyl group, or alkynyl group, and R ₂ represents an acyloxyl group of an aliphatic carboxylic acid. However, R ₁ at the 2-position
and the methyl group at the 3-position are cis-coordinated. ) This is a method for producing l-4-cyclopentenones shown in the following. The l-4-cyclopentenones represented by the above general formulas (-l) and (-l) are not only useful as agricultural chemicals and intermediates thereof, but also as intermediates for fragrances and pharmaceuticals. ,
For example, by rearranging l-2-substituted-3-hydroxy-3-methyl-4-cyclopentenone represented by the general formula (-l) while maintaining its steric configuration, 2 has an S(+) structure. -Substitution-4-
Hydroxy-3-methyl-2-cyclopentenone can be synthesized stereoselectively and is extremely useful as a pyrethroid intermediate. In addition, l-2-substituted-3-acyloxy-3-methyl-4-cyclopentenone is hydrolyzed into d-2-substituted-3-hydroxy-3-methyl-4-cyclopentenone, Further, by rearrangement while maintaining the steric configuration, 2-substituted-4-hydroxy-3-methyl-2-cyclopentenone having R(-) can be obtained.
This can be used as a raw material for prostaglandin derivatives, and can also be induced into cyclopentenone having an S(+) structure by inverting the hydroxyl group at the 4-position. Moreover l
-2-substituted-3-acyloxy-3-methyl-4-
dl-2- Substituted-4-acyloxy (or hydroxy)-3-
It can also be methyl-4-cyclopentenone. Regarding the method for producing such useful l-4-cyclopentenones, the present inventors have previously prepared dl-2-substituted-3
- Methyl-3-acetoxy-4-cyclopentenone is used as a raw material, and the target l-
He discovered that 4-cyclopentenones could be obtained and filed a patent application (Japanese Patent Application No. 41207-1983).
After further investigation, we found that, even if other than pig liver esterase, enzymes or microorganisms that have the ability to hydrolyze only the d-form in the raw material dl-form were used as the hydrolyzing agent. -4-
The inventors discovered that cyclopentenones can be easily obtained, leading to the present invention. That is, the present invention is based on the general formula ()

[Formula, R ₁ and R ₂ have the same meanings as above,
R ₁ at the 2-position and the methyl group at the 3-position are in cis coordination. ) is reacted with an enzyme or microorganism capable of hydrolyzing only the d-isomer of the cyclopentenone (provided that R ₂ in the above general formula is l-4-cyclopentenones represented by the above general formulas (-l) and (-l), which are characterized by hydrolyzing the acetoxy group (excluding combinations in which the enzyme is pig liver esterase) The present invention provides a method for manufacturing. In the present invention, dl-4 used as a raw material
- Cyclopentenones can be easily produced, for example, by the method shown below.

[Chemical formula] The hydrolysis reaction in the present invention is carried out using an enzyme or microorganism that has the ability to hydrolyze only d-4-cyclopentenones among the above-mentioned dl-4-cyclopentenones, and such hydrolysis reaction Enzymes obtained from animals and plants are used as enzyme sources, and their usage forms include purified enzymes, crude enzymes,
It can be used in various forms as needed, such as enzyme-containing materials, microbial culture solutions, cultures, microbial cells, culture mouth fluids, and processed products thereof, and enzymes and microorganisms can also be used in combination. Such enzymes include, for example, animal hydrolytic enzymes such as beef liver esterase, pig pancreatic esterase, dog liver esterase, and pig phosphatase, β-amylase obtained from barley and potato,
Lipase obtained from wheat (manufactured by Sigma, Wheat
Examples include plant hydrolytic enzymes such as Germ), and further examples include microorganisms belonging to each genus, lichens, algae, and other microorganisms as exemplified below, or hydrolytic enzymes obtained from these microorganisms. Rhodotorula sp., Trichoderma sp., Candida
Genus, Hansenula, Bacillus, Achromobacter
Genus, Nocardia genus, Chromobacterium genus,
Genus Flavobacterium, Genus Rizopus, Genus Mucor,
Genus Aspergillus, Genus Alkaligenes, Genus Torulopsis,
Corynebactrium sp., Endomyces sp.
Saccaromyces spp., Arthrobacter spp.
Metshnikowia sp., Pleurotus sp., Streptomyces
Genus, Proteus, Gliocladium, Acetobacter
Genus, Helminthosporium, Brevibacterium,
Escherichia sp., Citrobacter sp., Absidia sp.
Genus Micrococcus, Genus Pediococcus, Genus Klebsiella,
Genus Geotrichun. Examples of microorganisms belonging to each of these genera include the following. Rhodotorula minuta IFO−0387, IFO−
0412, Rhodotorula rubra IFO−0870,
Rhodotolura minuta var texensis IFO−0879,
Trichoderma longibrachiatum IFO−4847,
Candida kruseiout−6007, Candida
cylindracea, Candida tropicalis PK 233,
Candida utilus IFO 1086, Hansenula
anomala var ciferrii out 6095, Hansenula
anomala IFO−0118, Hansenulapoly mopha
IFO−1475, Bacillus cereus IFO−3466,
Bacillus subtilis ATCC 6633, Bacillus
pulmilus IFO−12092, Bacillus subtilis var
niger IFO 3108, Achromobacter lyticus
ATCC−21456, Achromobacter parvulus IFO
13181, Achromobacter sinplex IFO 12069,
Nocardia uniformis subtsuya−marenus
ATCC−21806, Nocardia uniformis ifo
13072, chromobacterium chocolatum IFO−
3758, Chromobacterium iodinum IFO−3558,
Chromobacterum violaceum IFO−12614,
Flavobacterium lutescens IFO 3084,
Flavobacterinm arbonescens IFO 3750,
Flavobacterium heparinum IFO−12017,
Flavobacterium capsulatum IFO−12533,
Rizopus chinensis IFO 4768, Mucor pusillus
IFO 9856, Aspergillus niger ATCC−9642,
Alkaligenes faecalis IFO 12669,
Torulopsisernobii IFO−0654, Torulopsis
candida IFO−0768, Corynebacterium
sepedonicum IFO−13763, Endomyces
geotrichum IFO 9542, Saccaromyces
carrvisial IFO−0334, Arthrobacter
globiformis IFO−12137, Metschnilcowia
pulcherrima IFO 0561, Pleurotus ostreatus
IFO 7051, Streptomyces grisens IFO−3356,
Proteus vulgaris IFO−3851, Proteus
unigavic 11D−874, Gliocladium rosew IFO
5422, Gliocladium virens IFO−6355, Aceto
bacterium aurantius IFO−3247,
Helminthosporium sp ATCC−20154,
Brevibacterium ammoniagenes IFO 12072,
Brevibacterium divaricatum ATCC−14020
Escherichia coli IFO−12713, IFO−3302,
IFO−13168, Citrobacter freundii IFO−
12681, Micrococcus varianaes ifo 3765,
Micrococcus lutens IFO 3066, Pediococus
acidilacticie IFO−3076, Klebsiella
pneumorial IFO−12059, Absidia hyalospora
IFO−8082, Geotrichun candidum IFO−4597. Among these enzymes or microorganisms, l-4
- Particularly preferably used to obtain cyclopentenones with good optical purity include, for example:
Hydrolytic enzyme obtained from Candida cylindracea (manufactured by Sigma), Hansenula anomala var
ciferrii OUT−6095, Metshnikowia
Pulcherrima IFO−0561, Pleurotus Ostreatus
IFO−7051, cholesterol esterase (from Schizophyllum commune), Candida
Examples include krusei out 6007. The hydrolysis reaction in the present invention is usually carried out by vigorously stirring the dl-4-cyclopentenone and the above-mentioned enzyme or microorganism in a buffer solution. As the buffer, commonly used buffers of inorganic acid salts such as sodium phosphate and potassium phosphate, buffers of organic acid salts such as sodium citrate, etc. are used, and the pH thereof is 4 to 10, preferably 5. ~
9, and the concentration is usually in the range of 0.05-2M, preferably 0.05-0.5M. The reaction temperature is usually 20 to 40°C, and the reaction time is generally 10 to 70 hours, but is not limited thereto. This hydrolysis reaction is important for the raw material dl in terms of optical yield.
-50% reaction rate for 4-cyclopentenones
It is preferable to end with less than By performing such a hydrolysis reaction, only d-4-cyclopentenone, which is one optical isomer of dl-4-cyclopentenone, which is a raw material, is hydrolyzed, resulting in the formation of the general formula (-l ) 1-2-substituted-3-hydroxy-3-methyl-
4-cyclopentenone is produced, and l-4-cyclopentenone, the other optical isomer of the raw materials, is converted into l-2-substituted-3- as shown by the general formula (-l). It remains as acyloxy-3-methyl-4-cyclopentenone, and the reaction product is ultimately obtained as a mixture of the above-mentioned l-4-cyclopentenones. After the reaction is complete, in order to classify the two from the reaction solution, the hydrolyzed solution is extracted with a solvent such as methyl isobutyl ketone, ethyl acetate, or ethyl ether, and the solvent is distilled off from the resulting organic layer. By treating the concentrated residue with column chromatography, 1-2-substituted-3-hydroxy-3-methyl-4-cyclopentenone and 1-2-substituted-3-acyloxyl-3-methyl-
4-cyclopentenone can be released. Thus, from the dl-4-cyclopentenones,
-4-Cyclopentenones are easily obtained, but
In the case of a tertiary alcohol such as l-2-substituted-3-hydroxy-3-methyl-4-cyclopentenone of general formula (-l), chemical means such as asymmetric reduction are required because it is a tertiary alcohol. Considering that it is not possible to synthesize these optically active substances, it can be said that it is extremely difficult to obtain these optically active substances. However, as in the present invention, 3 such as dl-4-cyclopentenones represented by the general formula ()
It has not been previously known that l- alcohol esters can be hydrolyzed with high optical purity, and it is also possible to easily hydrolyze l-
It has extremely high utility value in that it yields 2-substituted-3-hydroxy-3-methyl-4-cyclopentenone. Specific examples of the l-4-cyclopentenones thus obtained are as follows. l-3-hydroxy-2,3-dimethyl-4-
Cyclopentenone, l-2-ethyl-3-hydroxy-3-thymel-4-cyclopentenone, 2-
n-propyl-3-hydroxy-3-methyl-4
-cyclopentenone, l-2-isopropyl-3
-Hydroxy-3-methyl-4-cyclopentenone, l-2-n-butyl-3-hydroxy-3-
Methyl-4-cyclopentenone, l-2-isobutyl-3-hydroxy-3-methyl-4-cyclopentenone, l-2-n-pentyl-3-hydroxy-3-methyl-4-cyclopentenone, l-
2-Isopentyl-3-hydroxy-3-methyl-4-cyclopentenone, l-2-n-hexyl-3-hydroxy-3-methyl-4-cyclopentenone, l-2-n-heptyl-3- Hydroxy-3-methyl-4-cyclopentenone, l-2-
Allyl-3-hydroxy-3-methyl-4-cyclopentenone, l-2-ω-butenyl-3-hydroxy-3-methyl-4-cyclopentenone, l
-2-(2-cis-butenyl)-3-hydroxy-
3-methyl-4-cyclopentenone, l-2-
(2-cis-pentenyl)-3-hydroxy-3-
Methyl-4-cyclopentenone, l-2-(2-
trans-pentenyl)-3-hydroxy-3-
Methyl-4-cyclopentenone, l-2-(3-
cis-hexenyl)-3-hydroxy-3-methyl-4-cyclopentenone, l-2-(α-methylallyl)-3-hydroxy-3-methyl-4-
Cyclopentenone, l-2-propargyl-3-
l- such as hydroxy-3-methyl-4-cyclopentenone, l-2-(2-pentynyl)-3-hydroxy-3-methyl-4-cyclopentenone,
2-substituted-3-hydroxy-3-methyl-4-cyclopentenones, l-3-acetoxy-2,3-dimethyl-4-
Cyclopentenone, l-2-ethyl-3-acetoxy-3-methyl-4-cyclopentenone, l-
2-n-propyl-3-acetoxy-3-methyl-4-cyclopentenone, l-2-isopropyl-3-acetoxy-3-methyl-4-cyclopentenone, l-2-n-butyl-3- Acetoxy
3-Methyl-4-cyclopentenone, l-2-isobutyl-3-acetoxy-3-methyl-4-cyclopentenone, l-2-n-pentyl-3-acetoxy-3-methyl-4-cyclopene tenon,
l-2-isopentyl-3-acetoxy-3-methyl-4-cyclopentenone, l-2-n-hexyl-3-acetoxy-3-methyl-4-cyclopentenone, l-2-n-heptyl- 3-acetoxy-3-methyl-4-cyclopentenone, l-
2-allyl-3-acetoxy-3-methyl-4-
Cyclopentenone, l-2-ω-butenyl-3-
Acetoxy-3-methyl-4-cyclopentenone, l-2-(2-cis-butenyl)-3-acetoxy-3-methyl-4-cyclopentenone, l-
2-(2-cis-pentenyl)-3-acetoxy-
3-methyl-4-cyclopentenone, l-2-
(2-trans-pentenyl)-3-acetoxy-
3-methyl-4-cyclopentenone, l-2-
(3-cis-hexenyl)-3-acetoxy-3-
Methyl-4-cyclopentenone, l-2-(α-
methylallyl)-3-acetoxy-3-methyl-
4-cyclopentenone, l-2-propargyl-
3-acetoxy-3-methyl-4-cyclopentenone, l-2-(2-pentynyl)-3-acetoxy-3-methyl-4-cyclopentenone, and the acetoxy group at the 3-position in each of the above compounds. l-2-substituted-3-acyloxy substituted with propionyloxy group or octanoyloxy group
3-Methyl-4-cyclopentenones. The present invention will be explained below with reference to Examples. Example 1 500g of raw beef liver ground in a mixer was added to 1.5ml of acetone, stirred at 5-10°C for 1 hour, and then the acetone was removed. Add another 1.5 g of acetone to the residue, wash, and filter.
Repeat this operation twice. The collected beef liver was dried at room temperature to obtain 148 g of powdered beef liver. Add 1 portion of 0.1M phosphate buffer (PH6.0) to 100 g of this powdered beef liver and stir at 10°C. After stirring for about 8 hours, the mixture was centrifuged to obtain a supernatant liquid as a hydrolyzing enzyme solution. 2 g of dl-3-acetoxy-2-allyl-3-methyl-4-cyclopentenone was added to 80 ml of this hydrolyzing enzyme solution, and the mixture was vigorously stirred at 30-35°C for 20 hours. After the reaction is completed, extract with 40 ml of methyl isobutyl ketone three times. The solvent was distilled off from the obtained organic material, and the concentrated residue was purified by column chromatography using a mixture of ethyl acetate and toluene = 3:5 to obtain l-2-allyl-3-hydroxy-3-methyl-4-cyclo Pentenone 0.72g (yield ^46.00 %) [Optical rotation α] ²⁰ _D −
6.9° (C=1, chloroform), n ²⁰ _D 1.4978] and l-
3-acetoxy-2-allyl-3-methyl-4-
Cyclopentenone 0.98g [optical rotation °α] ²⁶ _D −19.6° (C
= 1, chloroform), n] ²⁶ _D 1.4801] was obtained. 0.5 g of the above l-2-allyl-3-hydroxy-3-methyl-4-cyclopentenone, alumina 10
g and 30 ml of benzene are stirred at 50-60°C for 6 hours. Separate the alumina and add 10ml of methanol.
Wash twice. The liquids were combined and concentrated, and the residue was purified by column chromatography using a mixture of toluene and ethyl acetate = 5:2 to obtain S(+)-2-allyl-4-
Hydroxy-3-methyl-4-cyclopentenone
0.43g was obtained. The optical purity of this product was 28.5%. [Analysis method of optical purity: Agric.Biol.Chem., 41
(10), 2003-6 (1977)] Example 2 200 ml of nutrient liquid medium in a 500 ml Sakaguchi flask (medium composition: glucose 1%, yeast extract 0.3%,
After sterilization, Candida Krusei Out-
6007 was inoculated and cultured with shaking at 30°C for 2 days. To this was added 4 g of dl-3-acetoxy-2-allyl-3-methyl-4-cyclopentenone, and the mixture was cultured with shaking at 30°C for 24 hours to effect hydrolysis. After the reaction is completed, the reaction solution is centrifuged, and the resulting supernatant is extracted four times with 70 ml of methyl isobutyl ketone. The solvent was distilled off from the organic layer, and the concentrated residue was purified by column chromatography using a mixture of ethyl acetate and toluene = 3:5.
-2-allyl-3-hydroxy-3-methyl-4
- 1.5 g of cyclopentenone (yield 48%) [optical rotation -
21.7° (C = 1, chloroform) and 1.96 g of l-3-acetoxy-2-allyl-3-methyl-4-cyclopentenone [optical rotation α] ²⁰ _D -82.6° (C = 1, chloroform)] The optical purity of the l-2-allyl-3-hydroxy-3-methyl-4-cyclopentenone was 91%. Example 3 dl-3-acetoxy-2-allyl in Example 2 dl-3-acetoxy-2-propargyl-3- instead of 3-methyl-4-cyclopentenone
The reaction, post-treatment and purification were carried out in the same manner as in Example 2 except that 3 g of methyl-4-cyclopentenone was used
3-hydroxy-2-propargyl-3-methyl-4-cyclopentenone 0.75 g (yield 32%) [optical rotation α] ²⁰ _D -118° (C = 1, chloroform)] and l
-3-acetoxy-2-propargyl-3-methyl-4-cyclopentenone 1.65 g [optical rotation α] ²⁰ _D
-12.2° (C=1, chloroform)]. The above l-3-hydroxy-2-propargyl-
d-4-hydroxy-2-propargyl obtained by rearranging 3-methyl-4-cyclopentenone
The optical purity of 3-methyl-2-cyclopentenone is
It was 84.6%. Example 4 dl-3-acetoxy-2-n-pentyl-3- instead of dl-3-acetoxy-2-allyl-3-methyl-4-cyclopentenone in Example 2
The reaction, post-treatment and purification were carried out in the same manner as in Example 2 except that 4 g of methyl-4-cyclopentenone was used
3-hydroxy-2-n-pentyl-3-methyl-4-cyclopentenone 0.97 g [optical rotation α] ²⁰ _D −
16.1° (C = 1, chloroform)] and 2.2 g of l-3-acetoxy-2-n-pentyl-3-methyl-4-cyclopentenone [optical rotation α] ²⁰ _D -60.2° (C =
1, chloroform)] was obtained. The above l-3-hydroxy-2-n-pentyl-
d-4-hydroxy-2-n-pentyl- obtained by rearranging 3-methyl-4-cyclopentenone
The optical purity of 3-methyl-2-cyclopentenone is
It was 86.2%. Example 5 In place of dl-3-acetoxy-2-allyl-3-methyl-4-cyclopentenone in Example 2, dl-3-acetoxy-2-ω-butenyl-3-
The reaction, post-treatment and purification were carried out in the same manner as in Example 2 except that 3 g of methyl-4-cyclopentenone was used
3-hydroxy-2-ω-butenyl-3-methyl-4-cyclopentenone 1.07g (yield 44.5%)
[Optical rotation α] ²⁰ _D −20.1 (C=1, chloroform), n ²⁰
_D
1.4995] and l-3-acetoxy-2ω-butenyl-3-methyl-4-cyclopentenone 1.41 g [optical rotation α] ²⁰ _D -73.2° (C = 1, chloroform), n ²⁰ _D
1.4817] was obtained. The above l-3-hydroxy-2-ω-butenyl-
d-4-hydroxy-2-ω-butenyl-3- obtained by rearrangement of 3-methyl-4-cyclopentenone
The optical purity of methyl-4-cyclopentenone is 89.2
It was %. Example 6 200 ml of nutrient liquid medium (medium composition: same as Example 2) was placed in a 500 ml Sakaguchi flask, and after sterilization,
Hansenula anomala var ciferrii out-6095 was inoculated and cultured with shaking at 30°C for 2 days. Then dl−
3-acetoxy-2-allyl-3-methyl-4-
Add 4 g of cyclopentenone and culture with shaking at 30°C for 24 hours to perform hydrolysis. After the reaction, the supernatant obtained by centrifugation was diluted with 70 ml of methyl isobutyl ketone.
Extract times. The solvent was distilled off from the obtained organic layer,
The concentrated residue was purified by column chromatography using a mixture of ethyl acetate and toluene = 3:5 to obtain l-2-allyl-
3-hydroxy-3-methyl-4-cyclopentenone 1.63 g (yield 50.9% optical purity 90.2%) [optical rotation α] ²⁰ _D −21.5° (C = 1, chloroform) and l-3-
Acetoxy-2-allyl-3-methyl-4-cyclopentenone 1.80 g [optical rotation α] ²⁰ _D -87.4° (C=
1, chloroform)] was obtained. Example 7 Microorganisms used for hydrolysis
The reaction, post-treatment and purification were carried out in the same manner as in Example 6 except that Metschnikowia pulcherrima IFO-0561 was used to obtain 1.25 g of l-3-hydroxy-2-allyl-3-methyl-4-cyclopentenone (optical purity 85.6).
%) and l-3-acetoxy-2-allyl-3
-Methyl-4-cyclopentenone 2.01g [α] ²⁰ _D
−84.2°] was obtained. Example 8 Microorganisms used for hydrolysis
The reaction, post-treatment and purification were carried out in the same manner as in Example 6 except that Pleurotusostreatus IFO-7051 was used.
-Hydroxy-2-allyl-3-methyl-4-cyclopentenone 0.96 g (optical purity 92.3%) and l-3-acetoxy-2-allyl-3-methyl-
2.32 g [α] ²⁰ _D -77.2°] of 4-cyclopentenone was obtained. Examples 9-15 Hansenula as a microorganism used for hydrolysis
Table-1 in place of anomala var ciferrii out-6095
Table 1 shows the results obtained by performing the reaction, post-treatment, and purification in the same manner as in Example 6, except for using the microorganism shown in . However, the culture medium composition of the bacterial nutrient medium used in Examples 9 to 12 is as follows: glucose 1%, yeast extract 0.5%, peptone 0.1%, K ₂ HPO ₄ 0.05% PH 7.0%

[Table] Example 16 dl-3-acetoxy-2- as a raw material for hydrolysis
The reaction, post-treatment and purification were carried out in the same manner as in Example 6 except that 3 g of propargyl-3-methyl-4-cyclopentenone was used.
g (optical purity 90.1%) and 1.6 g (α] ²⁰ _D -17.6°) of 1-3-acetoxy-2-propargyl-3-methyl-4-cyclopentenone were obtained. Example 17 dl-3-acetoxy-2- as a raw material for hydrolysis
l-3-hydroxy-2-n-pentyl-3-methyl-4- Cyclopentenone 1.12
g (optical purity 88.1%) and 1.35 g (α] ²⁰ _D -58.2°) of l-3-acetoxy-2-n-pentyl-3-methyl-4-cyclopentenone were obtained. Example 18 1 g of dl-3-acetoxy-2-allyl-3-methyl-4-cyclopentenone, 0.2 g of esterase (Lipase from Wheat Germ manufactured by Sigma) and 10 ml of 0.1M phosphorus-3-buffer were mixed,
Stir at 25-30°C for 35 hours. After the reaction is completed, the reaction solution is extracted three times with 10 ml of methyl isobutyl ketone. The solvent was distilled off from the obtained organic layer, and the concentrated residue was purified by column chromatography using a mixture of ethyl acetate and toluene = 3:5 to obtain l-2-allyl-3-hydroxy-3-methyl-4-cyclo Pentenone 0.18
g [Optical rotation α] ²⁰ _D −20.3° (C=1, chloroform)
]
l-3-acetoxy-2-allyl-3-methyl-
4-cyclopentenone 0.68g [optical rotation α] ²⁶ _D −
51.2° (C=1., chloroform) was obtained. The optical purity of the above l-2-allyl-3-hydroxy-3-methyl-4-cyclopentenone is 80.2%.
It was hot. Example 19 The reaction, post-treatment and purification were carried out in the same manner as in Example 18, except that 0.2 g of cholesterol esterase (from Schizophyllum commune, manufactured by Toyobo Co., Ltd.) was used as the hydrolase and the reaction time was 30 hours. 2-allyl-3-hydroxy-3-methyl-
4-cyclopentenone 0.21g (optical purity 92.4%)
and l-2-allyl-3-acetoxy-3-methyl-4-cyclopentenone 0.68 g (α) ²⁰ _D −
51.2°) was obtained. Example 20 Esterase (from
The reaction, post-treatment, and purification of l-2-allyl-3
-Hydroxy-3-methyl-4-cyclopentenone 0.2 g (optical purity 81.2%) and l-2-allyl-3-acetoxy-3-methyl-4-cyclopentenone 0.59 g (α) ²⁰ _D -49.3° ) was obtained. Examples 21-23 Table 2 in place of the hydrolytic enzyme in Example 18
Table 2 shows the results obtained by performing the reaction, post-treatment, and purification in the same manner as in Example 18, except for using the hydrolase described in Example 18.
Shown below.

[Table] Example 24 dl-3-acetoxy-2,3-dimethyl-4- instead of dl-3-acetoxy-2-allyl-3-methyl-4-cyclopentenone in Example 19
Example 19 except that 1 g of cyclopentenone was used.
Reacted and post-treated in the same manner as l-3-hydroxy-2,3-dimethyl-4-cyclopentenone.
0.17g [α] ²⁰ _D −24.7° (C=1, chloroform),
n ²⁰ _D 1.4796] and l-3-acetoxy-2,3
-Dimethyl-4-cyclopentenone 0.63g [α]
²⁰ _D −20.8° (C=1, chloroform), n ²⁰ _D 1.4716]
I got it. The above l-3-hydroxy-2,3-dimethyl-
d-4 obtained by rearranging 4-cyclopentenone
-Hydroxy-2,3-dimethyl-2-cyclopentenone had an optical purity of 90.5%. Examples 25-34 10 ml of nutrient medium B or Y with the following medium composition
After sterilization, the microorganisms shown in Table 3 were inoculated and cultured with shaking at 30°C for 2 days. to this
dl-3-acetoxy-2-allyl-3-methyl-
70 ml of 4-cyclopentenone was added and cultured with shaking at 80°C for 24 hours to perform hydrolysis. The results of the hydrolysis rate are shown in Table 3. Nutrient medium B Glucose 1%, yeast extract 0.5%, peptone 0.1%, K ₂ HPO ₄ 0.05%, PH 7.0 Nutrient medium Y Glucose 1%, yeast extract 0.3% Malt extract 0.3%, peptone 0.5%, PH 5.6

【table】

Claims (1)

[Claims] 1 General formula: (In the formula, R ₁ represents an alkyl group, an alkenyl group, or an alkynyl group, and R ₂ represents an acyloxyl group of an aliphatic carboxylic acid. However, the 2-position R ₁
and the methyl group at the 3-position is cis-coordinated). (However, in the above general formula,
[Formula] and [Formula] (wherein _{R 1 and} R ₂ are the above-mentioned has the same meaning as
The 2-position and the 3-position are cis-coordinated. ) A method for producing l-4-cyclopentenones represented by: Beef liver esterase, microorganisms belonging to the genus Candida or hydrolase obtained therefrom,
Microorganisms belonging to the genus Hansenula or hydrolases obtained therefrom; microorganisms belonging to the genus Metschnikowia or hydrolases obtained therefrom; microorganisms belonging to the genus Pleurotus or hydrolases obtained therefrom; microorganisms belonging to the genus Bacillus or hydrolases obtained therefrom; the resulting hydrolytic enzyme,
A microorganism belonging to the genus Achromobacter or a hydrolase obtained therefrom, a microorganism belonging to the genus Flavobacterium or a hydrolase obtained therefrom, a microorganism belonging to the genus Chromobacterium or a hydrolase obtained therefrom,
Microorganisms belonging to the genus Nocardia or hydrolytic enzymes obtained therefrom; microorganisms belonging to the genus Torulopsis or hydrolytic enzymes obtained therefrom;
Microorganisms belonging to the genus Trichoderma or hydrolase obtained therefrom, lipase obtained from wheat, microorganisms belonging to the genus Schizophyllum or hydrolase obtained therefrom, animal pancreatic esterase, β-amylase, phosphatase,
Microorganisms belonging to the genus Rhodotorula or hydrolytic enzymes obtained therefrom; microorganisms belonging to the genus Rizopus or hydrolytic enzymes obtained therefrom;
Microorganisms belonging to the genus Mucor or hydrolytic enzymes obtained therefrom; microorganisms belonging to the genus Aspergillus or hydrolytic enzymes obtained therefrom;
Microorganisms belonging to the genus Geotrichun or hydrolytic enzymes obtained therefrom; microorganisms belonging to the genus Proteus or hydrolytic enzymes obtained therefrom;
A microorganism belonging to the genus Citrobacter or a hydrolase obtained therefrom, a microorganism belonging to the genus Micrococcus or a hydrolase obtained therefrom, a microorganism belonging to the genus Gliocladium or a hydrolase obtained therefrom.