JPS6232739B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel cyclopentenedione compound and a method for producing the same.

More specifically, the present invention relates to a novel cyclopentenedione compound represented by the following general formula (), which is a useful intermediate for agricultural chemicals, and a method for producing the same.

(In the formula, R represents an alkenyl group or an alkynyl group.) Allethrin, which is known as a useful agricultural chemical, is
Invented by MS Schechter in 1949, it is widely used throughout the world due to its excellent insecticidal activity and low toxicity, and various studies have been conducted on its synthesis method. Among these, various proposals have been made regarding methods for synthesizing the alcohol component of allethrin, some of which are used in actual production.

However, these have various drawbacks in terms of yield, complexity of operation, and environmental issues, and are not necessarily industrially satisfactory.

Against this background, the present inventors have conducted intensive studies on the production method of cyclopentenolones, which are used as intermediates for this insecticidal compound, and have discovered a novel and extremely advantageous method for producing them. Based on this, we have completed the present invention by conducting various studies on the important intermediates and their manufacturing methods.

That is, the present invention provides a novel cyclopentenedione compound represented by the general formula () and a method for producing the same, which is represented by the general formula (). (In the formula, R has the same meaning as above.) It provides a manufacturing method characterized by oxidizing a cyclopentenone compound represented by the following formula.

The compound of the present invention represented by the general formula () can be easily led to cyclopentenolones represented by the general formula (), which are important intermediates for agricultural chemicals, by the method shown below, for example, and is an extremely useful intermediate. It is.

(In the formula, R has the same meaning as above.) That is, the compound of the present invention represented by the general formula () is reacted with methylmagnesium iodide to obtain the compound represented by the general formula (), and then alumina is By this action, cyclopentenolones represented by the general formula () can be obtained.

Furthermore, the compound of the present invention represented by the general formula () can also be an intermediate for prostaglandins, which are known as pharmaceuticals, in addition to the above-mentioned cyclopentenolones, and its role as an intermediate is extremely important. is important.

Further, the compound represented by the general formula (), which is the starting material of the present invention, undergoes a Grignard reaction with furfural () to obtain a furylcarbinol compound represented by the following general formula (), which is then added to a mixed solvent of water and an organic solvent. It can be easily obtained by treating the system with an acid.

In the compound of the present invention represented by the general formula (), specific examples of R include allyl, 2-butenyl, etc. as the alkenyl group, and propargyl, ethynyl, etc. as the alkynyl group.

In addition, in the method for producing a cyclopentenedione compound represented by the general formula () according to the present invention, the oxidizing agent may include chromic anhydride, chromate, dichromic acid, dichromate, chromyl chloride, chromate ester, manganese dioxide. , activated manganese dioxide,
Potassium permanganate, aluminum i-propoxide, aluminum t-butoxide, lead tetraacetate, ruthenium tetroxide, N-halocarboxylic acid amide, oxygen, hydrogen peroxide, organic peroxide, nitric acid, nitrous acid, dimethyl sulfoxide, quinone silver carbonate (), silver oxide (), copper oxide (), copper hydroxide (), cerium () salt, vanadate, cobalt () salt, ozone, etc., preferably manganese dioxide, activated dioxide Manganese, chromic anhydride, chromate, dichromic acid, dichromate, chromyl chloride, chromic acid ester, chromium oxide pyridine complex, N-halocarboxylic acid amide, oxygen, aluminum t-butoxide, aluminum i-propoxide. can give.

The reaction solvent varies depending on the oxidizing agent used; for example, petroleum ether, ether, acetone, methylene chloride, pentane, benzene, chloroform, 5% methanol-chloroform solution, etc. for manganese dioxide and activated manganese dioxide, and ether-water mixture, benzene for chromic acids. , acetone, pyridine, water, dilute sulfuric acid, acetic acid, tetrahydrofuran,
dioxane, ether, chlorobenzene, carbon tetrachloride, etc. For N-halocarboxylic acid amides, t-butyl alcohol-pyridine solution, aqueous acetone,
Hydrous dioxane, etc. For oxygen, n-heptane, petroleum benzine, ethyl acetate, dioxane, acetone, water, etc. For aluminum t-butoxide and aluminum i-propoxide, benzene, toluene, benzene-acetone solution, toluene-acetone solution, etc.・For 3-dichloro-5,6-dicyano-1,4-benzoquinone, dioxane,
Carbon tetrachloride, tetrahydrofuran, ether, etc., and potassium permanganate such as water, acetone, ethanol, t-butyl alcohol, pyridine, chloroform, isooctane, benzene, petroleum ether, methylcyclohexane, etc. are often used.

The reaction temperature is not particularly limited, but is generally -20
A range of 0°C to 180°C, preferably 0°C to 120°C is suitable.

Furthermore, when oxidizing with oxygen, the reaction can proceed efficiently by using a catalyst such as platinum-activated carbon or platinum black.

Next, the present invention will be explained in more detail with reference to examples, but it goes without saying that the present invention is not limited to these examples.

Example 1 1.9 g of chromic anhydride is dissolved in 5.4 g of water, and then 1.6 ml of concentrated sulfuric acid is added to the solution under ice cooling and mixed and dissolved.
Next, this mixed solution was mixed with 3.7 g of 4-hydroxy-5-allyl-2-cyclopentenone and 8 ml of acetone.
It was added dropwise to a solution consisting of under ice cooling for 2 hours. After the dropwise addition, stirring was continued under ice-cooling for another hour, then extracted with ether, and the extract was diluted with an aqueous solution of sodium bicarbonate,
Wash with saturated saline solution. Next, this was dried over anhydrous sodium sulfate, and then the solvent was distilled off to obtain 3.2 g of a concentrated residue. Add this to silica gel (Wakogel C-
200) Separation and purification by column chromatography using 40 g (eluent: ethyl acetate:n-hexane = 2:3 (volume)) yields 2.91 g of 4-keto-5-allyl-2-cyclopentenone. (yield 80.0
%) n ²⁰ _D 1.5065 NMR data (CDCl ₃ , internal standard TMS, δ
ppm, 90MHz) 7.32 (s, 2H, 2-H & 3-H) 5.65 (complex m, 1H, -CH ₂ -CH =
CH _a H _b ) 5.11 (m, 1H, -CH ₂ -CH=CH _a H _b ) 4.95 (m, 1H, -CH ₂ -CH=CH _a H _b ) 2.88 (m, 1H, 5-H) 2.52 (t, 2H, -CH ₂ -CH=CH _a H _b ) Example 2 4.0 g of 4-hydroxy-5-propargyl-2-cyclopentenone was dissolved in 200 ml of chloroform, and 25 g of activated manganese dioxide was added thereto. and stirred at room temperature for 4 hours. The reaction mixture was then filtered;
Wash the upper product thoroughly with chloroform, combine the washings with the previous solution, concentrate, and obtain a pale yellow 4-keto-5-
3.6 g of propargyl-2-cyclopentenone was obtained.

(Yield 91%) Elemental analysis values C: 71.6%, H: 4.5% Example 3 4-hydroxy-5-propargyl-2-cyclopentenone instead of 4-hydroxy-5-allyl-2-cyclopentenone The same operation as in Example 1 was performed except that 4-keto-5-propargyl-2-cyclopentenone was obtained in a yield of 72%.

Example 4 In a solution of 150 ml of dry benzene and 100 ml of acetone,
1.5 g of -hydroxy-5-allyl-2-cyclopentenone was dissolved, 3 g of freshly distilled aluminum i-propoxide was added thereto, and the mixture was heated under reflux for 12 hours. It was cooled to room temperature, washed twice with 30% sulfuric acid, and then washed with water until neutral. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure.
Distillation of the residue yielded 1.2 g of 4-keto-5-allyl-2-cyclopentenone.

Yield 81% Boiling point 53℃/4mmHg Example 5 500mg of 4-hydroxy-5-allyl-2-cyclopentenone and 450mg of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone were added to 6ml of dioxane. After dissolving and standing at room temperature for 16 hours, the precipitated 2,3-dichloro-5,6-dicyanohydroquinone was separated off.

Wash the upper material with methylene chloride, combine the liquid and the washing liquid, and concentrate. Dissolve the residue in 50 ml of methylene chloride and wash with 10% aqueous sodium hydroxide solution.
Wash with water until neutral. After drying over anhydrous sodium sulfate, the solvent was distilled off, and this was separated and purified by column chromatography using 20 g of silica gel (Wako Gel C-200) (eluent: ethyl acetate: n-hexane = 2:3 (volume) ) 450 mg of 4-
Keto-5-allyl-2-cyclopentenone was obtained.

(Yield 91%) Reference Example 1 10g of 2-(1-hydroxy-3-butenyl)furan was dissolved in water-acetone (water:acetone=1:
6 (volume)) Dissolve in 350ml and heat under reflux (55℃)
Add 6.6 g of polyphosphoric acid dropwise. After stirring at the same temperature for 48 hours, the acetone was distilled off and the mixture was extracted twice with 300 ml of ether.

The extract was washed with an aqueous sodium bicarbonate solution and saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain 9.5 g of a concentrate. The concentrate was then subjected to distillation to remove unreacted 2-(1-hydroxy-
4.2 g (78°C/10 mmHg) of (3-butenyl)furan and 3.8 g (97°C/0.7 mmHg) of the target 4-hydroxy-5-allyl-2-cyclopentenone were obtained.
(Yield 65.5% vs. raw materials consumed) Reference Example 2 0.8 g of metallic magnesium and 20 ml of ether were placed in a flask, and 1.9 g of methyl iodide was added dropwise to this at room temperature while stirring for 2 hours. Stir for an hour. The Grignard reagent thus prepared was then converted into 4-keto-5-allyl-
The mixture was added dropwise to a solution of 2.0 g of 2-cyclopentenone and 10 ml of ether with stirring at room temperature for 2 hours. After the addition was completed, the mixture was stirred for an additional hour, and then 30 ml of a saturated aqueous ammonium chloride solution was added under ice cooling and stirred for 1 hour. The reaction solution is separated, the aqueous layer is extracted twice with 30 ml of ether, and the extract is combined with the ether layer and washed with an aqueous sodium bicarbonate solution and saturated brine. Next, after drying over anhydrous sodium sulfate, the ether was distilled off to obtain 2.2 g of residue. Add this to silica gel (Wakogel C-
200) Purified by column chromatography using 20g (eluent toluene:ether = 2:1
(volume)), 1.5 g of 4-hydroxy-4-methyl-5-allyl-2-cyclopentenone was obtained.
(yield 67%) NMR data (CCl ₄ , internal standard TMS, δppm,
60MHz) 7.32 (d, 1H, 3-H) 5.92 (d, 1H, 2-H) 5.81 (complex m, 1H, -CH ₂ -CH =
CH _a H _b ) 5.12 (m, 1H, -CH ₂ -CH=CH _a H _b ) 4.93 (m, 1H, -CH ₂ -CH=CH _a H _b ) 4.12 (broad s, 1H, 4-O H ) 2.37 (m, 3H, 5-H&-C H ₂ -CH=
CH _a H _b ) 1.28 (s, 3H, 4-CH ₃ ) Reference example 3 4-Hydroxy-4-methyl-5-allyl-
Add 4.0 g of 2-cyclopentenone to a suspension of 20 g of activated alumina for 300 mesh column chromatography (Wako Pure Chemical Industries) in a mixture of 100 ml of toluene-ether solution (1:1 (volume)) and 2.4 g of water. 24 at 30℃
After stirring for an hour, remove the alumina and add the removed alumina to a toluene-ether solution (1:1 (volume)).
Extract 3 times with 50 ml, filter, and combine the extract with the previous solution and concentrate. Rectify the concentrated liquid (155℃/1mmHg)
2.5 g of 2-allyl-3-methyl-4-hydroxy-2-cyclopentenone was obtained.

(yield 62.5%) NMR data (CDCl ₃ , internal standard TMS, δppm
90MHz) 5.71 (complex m, 1H, _-CH2 - CH =
CH _a H _b ) 5.06 (m, 1H, -CH ₂ -CH=CH _a H _b ) 4.93 (m, 1H, -CH ₂ -CH=CH _a H _b ) 4.74 (broad d, 1H, 4-H ) 3.94 (broad s, 1H, 4- OH ) 2.96 (d, 2H, -CH ₂ -CH=CH _a H _b ) 2.85 (d of d, 1H, 5-H) 2.27 (d of d, 1H , 5-H) 2.11 (s, 3H, 3-C H ₃ ) Reference Example 4 12 g of 2-(1-hydroxy-3-cis-hexenyl)furan was dissolved in water-acetone [water:acetone = 1:6 (by volume) )] Dissolve in 350 ml, and add 6.6 g of polyphosphoric acid dropwise while heating and refluxing. After stirring at the same temperature for 48 hours, the acetone was distilled off, and the residue was extracted twice with 300 ml of ether. The extracted oil layers were combined and the solvent was distilled off to obtain 10.8 g of concentrated residue.

This concentrated residue was purified by column chromatography using 150 g of silica gel (distillate: toluene:(ethyl acetate = 5:3)) to obtain 4-hydroxy-5-(2-cis-pentenyl)-2-cyclo 6.24 g (yield 52%) of pentenone was obtained.

b.p145~150℃/3mmHg Example 6 Dissolve 4g of 4-hydroxy-5-(2-cis-pentenyl)-2-cyclopentenone in 150ml of dichloromethane, and add 40% of activated manganese dioxide.
After adding g, stir at 30°C for 10 hours.

Thereafter, the manganese dioxide was removed and the liquid was concentrated to obtain 3.4 g of pale yellow 4-keto-5-(2-cis-pentenyl)-2-cyclopentenone (yield: 86
%)

Claims (1)

[Claims] 1. General formula (In the formula, R represents an alkenyl group or an alkynyl group.) A cyclopentenedione compound represented by the following. 2. The compound according to claim 1, wherein R is an allyl group. 3 General formula (In the formula, R represents an alkenyl group or an alkynyl group.) A general formula characterized by oxidizing a cyclopentenone compound represented by (In the formula, R has the same meaning as above.) A method for producing a cyclopentenedione compound represented by the following.