JPS6022696B2 - Cyclopentenone derivatives and their production method - Google Patents

Description

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

The compound of the present invention is a novel compound that has not yet been published in the literature, and is represented by the formula [wherein R represents a CH3CH2CH=CHC group]. )-2-cyclobentenone.

The compound is useful as an intermediate for synthesizing methyl dehydrodiasmonate, which is useful as a raw material for perfumery. The compound of the present invention can be synthesized by various methods, but one preferred example is the compound of the formula cis-4.
The condensation reaction of methyl 4-dimethoxy-2-phthenate and methyl acetoacetate produces 2-acetyl-3 represented by the formula
- Dimethyl dimethoxymethylglutarate is obtained, and then the compound of formula (V) is reacted with bentenyl bromide to obtain the formula [
Dimethyl 2-acetyl-3-dimethoxymethyl-2-(2-benbenyl)glutarate represented by the formula (R' represents a CH3C&C3CC ratio group) was obtained, and then dimethyl
) was catalytically reduced in the presence of Lindlar's catalyst to obtain 2-acetyl-3-dimethoxymethyl-2-(2-acetyl-3-dimethoxymethyl-2-(
Dimethyl cis-2-bentenyl)glutarate was obtained, and the compound of formula (m) was further hydrolyzed to obtain 2-acetyl-3-formyl-2-(cis-2-bentenyl)glutaric acid represented by the formula [wherein R is the same as above] The compound of the present invention represented by formula (1) is produced by obtaining methyl and finally trapping the compound of formula (D).

The compound of formula (W) is produced, for example, by electrolytically oxidizing furfural or furfuryl alcohol, which is readily available, in methanol.

The condensation reaction between the compound of formula (river) and methyl acetoacetate can be performed using aliphatic alcohols such as methanol, ethanol, and propanol, aliphatic ketones such as acetone and methyl ethyl ketone, aliphatic cyclic ethers such as tetrahydrofuran and dioxane, dichloromethane, and dichloroethane. It is carried out in the presence of a basic catalyst such as potassium carbonate, sodium carbonate, lithium carbonate, sodium bicarbonate, sodium fluoride, potassium fluoride, or quaternary ammonium fluoride salt in an organic solvent such as a halogenated hydrocarbon such as . Among these, it is particularly preferable to carry out the reaction in a methanol solvent in the presence of at least one basic catalyst selected from sodium carbonate, lithium carbonate and potassium fluoride. The ratio of the compound of formula (W) and methyl acetoacetate to be used is not particularly limited and is appropriately selected from a wide range, but the latter is usually equimolar to 5 times the former, preferably equimolar to 2 times the molar amount. It is better to The amount of the basic catalyst to be used is not particularly limited and is appropriately selected from a wide range, but it is generally used from 0.1 to 3 moles, preferably from 0.6 to 2.6 moles, relative to the compound of formula (1). It is better. The reaction temperature for this reaction is not particularly limited, and the reaction is carried out at room temperature or under heating, but it is generally preferable to carry out the reaction at 40 to 65 qo, preferably at reflux temperature. The reaction time varies depending on the reaction conditions, but is usually about 10 to 7 q hours.
The reaction between the compound of formula (V) and 2-bentinyl bromide is usually preferably carried out in an organic solvent in the presence of a basic catalyst.

Such organic solvents include aliphatic alcohols such as methanol, ethanol, and propanol; aliphatic ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone;
Examples include aliphatic cyclic ethers such as tetrahydrofuran and dioxane, and halogenated hydrocarbons such as dichloromethane and dichloroethane. Compound of formula (V) and bromide 2
-The proportion of Bentinyl used is not particularly limited and is appropriately selected from a wide range, but the latter is usually equimolar to the former.
It is preferable to use twice the molar amount, preferably 1.1 to 1.3 tomolar. Examples of the basic catalyst include potassium carbonate, sodium carbonate, lithium carbonate, and sodium hydrogen carbonate. The amount of the basic catalyst to be used is not particularly limited and is appropriately selected from a wide range, but it is usually used in an amount of 1 to 7 times the mole of the compound of formula (V), preferably 4 to 5 times the amount of the compound of formula (V). . The reaction temperature for this reaction is not particularly limited and may be appropriately selected from a wide range, but it is generally preferred to carry out the reaction at a temperature of 50 to 15 pO, preferably 60 to 80 pO. The reaction time varies depending on the reaction conditions, but is usually about 6 to 2 hours.
Catalytic reduction of the compound of formula (W) is carried out in the presence of Lindlar catalyst.

A typical Lindlar catalyst is a palladium-calcium carbonate catalyst encapsulated with lead acetate and quinoline.
The amount of Lindlar catalyst to be used is not particularly limited and is appropriately selected from a wide range, but is generally used in an amount of 10 to 15% by weight, preferably 40 to 6% by weight, based on the compound of formula (W). do it. The reaction is preferably carried out in an organic solvent, and such organic solvents include aliphatic alcohols such as methanol, ethanol, and propanol, aliphatic ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and fatty acids such as tetrahydrofuran and dioxane. Examples include cyclic ethers, aliphatic hydrocarbons such as n-hexane and n-heptane, and halogenated hydrocarbons such as dichloromethane and dichloroethane. The reaction may be carried out either at normal pressure or under increased pressure, but it is preferably carried out under increased pressure. The reaction temperature is not particularly limited, and may be carried out at room temperature, under cooling, or under heating, but it is generally preferred to carry out the reaction at 10 to 60°C, preferably 30 to 4°C. . Hydrolysis of the compound of formula (m) is preferably carried out in the presence of an acidic catalyst.

Examples of acidic catalysts include hydronic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid; peracids such as perchloric acid, perbromic acid, and periodic acid; organic sulfonic acids such as benzenesulfonic acid and paratoluenesulfonic acid;
Examples include strongly acidic ion exchange resins. The amount of the acidic catalyst to be used is not particularly limited and is appropriately selected from a wide range, but generally it may be present in the reaction system in an amount of 0.1 to 10% by weight, preferably 0.5 to 2% by weight. Tetrahydrofuran, methanol, water, etc. are preferably used as the reaction solvent. The reaction temperature for this reaction is not particularly limited and may be carried out at room temperature, under cooling, or under heating, but generally 1
It is best to carry out the test at 0 to 6 pi○, preferably from 20 to 4 pi. The reaction time varies depending on the reaction conditions, but is usually about 6 to 2 hours. The ring reaction of the compound of formula (0) is preferably carried out in the presence of a base.

Examples of the base used in this case include organic amine salts of organic acids such as formic acid-morpholine salt, formic acid-piveridine salt, formic acid-pyridine salt, acetic acid-morpholine salt, acetic acid-piveridine salt, and acetic acid-pyridine salt. The amount of such base to be used is not particularly limited and may be selected from a wide range as appropriate;
The amount is usually 0.5 to 2 times the amount of the compound of formula (D), preferably 1.1 to 1. It is better to use Kang Yin Mol. The reaction is carried out using aromatic hydrocarbons such as benzene, toluene, xylene, etc.
It is preferable to carry out the reaction in an organic solvent such as an aliphatic hydrocarbon such as -hexane or n-heptane. The reaction temperature of the reaction is not particularly limited and is appropriately selected from a wide range, but is usually 50 to
15 pi○, preferably 70 to 100°C. The reaction time varies depending on the reaction conditions and cannot be generalized, but it is usually 3 to 30 minutes.
About 1 year old. The compound of the present invention thus obtained can be easily isolated by applying known conventional means such as extraction, washing, distillation, etc. When the compound of the present invention is decarboxylated under heating, it becomes useful as an active ingredient of perfume [formula R and M]
Methyl dehydrojasmonate (methyl-4,5-dihyde) represented by e is the same as above].

jasmonate). Examples are given below to further clarify the present invention. Example '1' Preparation of compound of formula (V) Into a reaction vessel of 20 parts were added 2.5 parts of potassium evolution, 5 parts of dry methanol, 2 parts of methyl cis-4,4-dimethoxy-2-butenoate. Add Matsuyu and 2.7 ml of methyl acetoacetate and mix thoroughly.

The reaction mixture is stirred vigorously for 3 days while heating to 8-0 degrees with oil. After the reaction was completed, the reaction mixture was allowed to cool to room temperature,
Then methanol is removed under reduced pressure. Dissolve the concentrated residue in ethyl acetate and wash with saturated brine. The ethyl acetate solution was dehydrated with E nitrate, and then the ethyl acetate was distilled off under reduced pressure. If the concentrated residue is distilled under reduced pressure with 4 tons of Hg, the crab content will be 100 to 1.
3.69 ta of cold-colored liquid of dimethyl 2-acetyl-3-dimethoxymethylglutarate, which is 2 pi○, is obtained. This corresponds to 97% of the theoretical yield. IR: 1735 (C=○)
, 1715 (C=○), 1202 (C-0), 11 balls (
C-0), 1066 (C-.

) Skin-INMR (CDC13) 6 2.24 (3 days, CH3CO), 2.51 (2 days,
C ratio COO), 2.95 (IH, CH-C-COO),
3.33 (J=3HZ, QH, CH30), 3. Congee (thin, CH80CO), 379 (J=8ce, IH, CH-C
O), 4, Spot (J = 5. Fine Z, IH, 0-CH-〇) Elemental analysis value Actual value C: 52.20%, H: 7.20% Theoretical value C
: 52.17%, H: 7.24%'21 Preparation of compound of formula (W) 9.37 g of potassium carbonate and 170 g of acetone were added to a 500 g. ,
Slowly add an aqueous solution of 3.11 dimethyl 2-acetyl-3-dimethoxymethylglutarate diluted with 170% acetone.

Then, after adding 2.16 hours of bentenyl bromide, the reaction mixture was allowed to react under reflux for 1 hour. After the reaction is completed, the reaction mixture is allowed to cool to room temperature, and then subjected to separation in a furnace to remove potassium carbonate. Concentrate the furnace liquor under reduced pressure. If the concentrated residue is distilled under reduced pressure at 0.5 Hg, a colorless liquid of dimethyl 2-acetyl-3-dimethoxymethyl-2-(2-bentinyl)glutarate with a distillate temperature of 110 to 115°C will be obtained.
You can get it. This corresponds to 71.5% of the theoretical yield. IR;
2 spots 7 (CQO), 1729 (C=0), 1710 (C
D0), 1430 (CH2), 13th string (CH30), 1
317 (CH30), 1257 (C-0), 120 (C
-0), 1161 (C-.

), 1074 (C-.) enemy-INMR (CC14) 61
．． 11 (J=7-2HZ, milk day, CH3-C), 1.8
1-2.26 (plaque, CH2-C=, CH3CO), 2.
26-2.55 (2 days, CH2-COO), 2.55-
2.85 (2 days, C-ro-C=), 2.98-3.48 (
7th, C ratio ○, CH-C-COO), 3.61, 3.6
5 (string, CH, OCO), 4.15-4. Me (IH, O
CHO) Actual elemental analysis value C: 59.60%, H; 7
．． 70% theoretical value C; 59.65%, H; 7.60%'
3- Preparation of compound of formula (m) In a reaction vessel, dimethyl 2-acetyl-3-dimethoxymethyl-2-(2-bentinyl)glutarate dissolved in 20% n-hexane 1.
On the 27th, add Lindler catalyst 5.23 on the 23rd.

Hydrogen gas is introduced under the chick trunk, and the reaction is terminated when the theoretical amount has been absorbed. After the reaction, the reaction liquid is separated in a furnace to remove the catalyst, and then the furnace liquid is extracted with n-hexane. The extract is washed with saturated saline and dried over sodium sulfate. After removing the sodium sulfate, the furnace liquid is concentrated under reduced pressure. If the concentrated residue is distilled under reduced pressure at 0.5 skin Hg, a colorless liquid of dimethyl 2-acetyl-3-dimethoxymethyl-2-(cis-2-pentenyl)glutarate with fractions of 100 to 0 is obtained. 1.28 ta is obtained. This corresponds to 99.7% of the theoretical yield. IR;2
835 (CH30), 1733 (C=○), 1708 (
C=0), 1436 (CH2), 1216 (C-0),
11 Mouse (C-.

), 1073 (C-.) Gong-INMR60.95 (J=
7.4Hz, 3 days, CH3-C), 1.76-2.32
(arc, CH3C0, CH2-C=), 2.37-2.8
6 (4 days, CH2-C=, CH2-COO), 2.95
~3.50 (7th, CH30, CH1C1COO), 3
．． 66, 3.71 (fence, CH30CO), 4.27 (J
=4. Plate Z, IH, 0-CH-0), 4.88-5.8
3 (Crime, HC=CH) Elemental analysis value Actual value C: 59.30%, H: 820% Theoretical value C:
59.30%, H: 8.13% [4' Preparation of compound of formula (b) 5.29 g of dimethyl 2-acetyl-3-dimethoxymethyl-2-(cis-2-bentenyl)glutarate was placed in a reaction vessel, Tetrahydrofuran 200 [,
Add 200ml of 1% aqueous perchloric acid solution to make a homogeneous solution.

Next, the mixture is incubated for one hour while maintaining the reaction temperature at 25-270°C. After the reaction is complete, the mixture is neutralized with sodium hydrogen aqueous solution to adjust the pH.
7 and then concentrated under reduced pressure to a total volume of 200 kg. Add brine to the concentrated residue and extract with ethyl acetate. The extract is dehydrated with anhydrous sodium sulfate and concentrated under reduced pressure. When the concentrated residue is distilled under reduced pressure at 0.1 air Hg, methyl 2-acetyl-3-formyl-2-(cis-2-bentenyl)glutarate having a crab content of 100 to 105 qo is obtained as a colorless liquid. This corresponds to 73.2% of the theoretical yield. IR; 2 bags 1 (CHO), 1
7 papers (C=0), 1716 (C ni.

) En-INMR (CC14) 69.65 (CHO) Elemental analysis value Actual value C; 60.42%, H; 7.40% Theoretical value C; 60.39%, H; 7.43% '5' formula (1
) Production of compound 2-acetyl-3-formyl-2-(
Methyl cis-2-bentenyl)glutarate (50%), 500% dry benzene, 10% acetic acid, and 10% piverizine were charged into a reaction vessel, and the reaction was carried out under reflux for 6 hours.

After the reaction is completed, the reaction mixture is allowed to cool to room temperature, and then the solvent is removed under reduced pressure. The residue is dissolved in ethyl acetate, washed with 10% aqueous hydrochloric acid, hydrogenated sodium chloride solution, and saturated saline in this order, and then dried over anhydrous sodium sulfate. After removing the sodium sulfate, the solvent is concentrated under reduced pressure, and the resulting residue is distilled under reduced pressure at 0.015 mm to give 5-methoxycarbonyl-4-methoxycarbonylmethyl, which has a volume of 80 to 83 oo. 1.86 ta of 5-(cis-2-bentenyl)-2-cyclobentenone is obtained as a colorless liquid. This corresponds to 49.3% of the theoretical yield. IR; 1736 (C=○
), 1710 (C=○), 1597 (C=C), 143
6 (CH2), 1366 (CH3), 1218 (C-0
), 1172 (C-0), Group 10 (C-0) C is -1N
MR (CC14)

Claims (1)

[Claims] 1. 5-methoxycarbonyl-4-methoxycarbonylmethyl-5-(cis- 2-pentenyl)
-2-cyclopentenone. 2 Formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R represents a CH_3CH_2CH=CHCH_2- group] 2-acetyl-3-formyl-2-
5-Methoxycarbonyl-4-methoxycarbonyl represented by a formula characterized by ring-closing (cis-2-pentenyl) methyl glutarate ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R is the same as above] Methyl-5-(cis-2-pentenyl)-2-
Method for producing cyclopentenone. 3. Dimethyl 2-acetyl-3-dimethoxymethyl-2-(cis-2-pentenyl)glutarate represented by formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, R represents CH_3CH_2CH=CHCH_2- group] Hydrolyzed to obtain methyl 2-acetyl-3-formyl-2-(cis-2-pentenyl)glutarate, which is represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R is the same as above] Next, there are formulas characterized by ring-closing the compound of formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, R is the same as above] 5-methoxycarbonyl-4-methoxycarbonylmethyl-5 -(cis-2-pentenyl)-2-
Method for producing cyclopentenone. 4 Formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R' represents a CH_3CH_2C≡CCH_2- group] Dimethyl 2-acetyl-3-dimethoxymethyl-2-(2-pentynyl)glutarate is converted to Lindlar. Through catalytic reduction in the presence of a catalyst, the formula ▲mathematical formula, chemical formula,
There are tables etc. ▼ [In the formula, R is CH_3CH_2CH=C
2-acetyl-3 represented by HCH_2- group]
Dimethyl -dimethoxymethyl-2-(cis-2-pentenyl)glutarate is obtained, and then the compound of formula (III) is hydrolyzed to form the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R is the same as above. ] A formula characterized by obtaining methyl 2-acetyl-3-formyl-2-(cis-2-pentenyl)glutarate represented by and then ring-closing the compound of formula (II) ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R is the same as above] 5-methoxycarbonyl-4-methoxycarbonylmethyl-5-(cis-2-pentenyl)-2-
Method for producing cyclopentenone. 5 Dimethyl 2-acetyl-3-dimethoxyglutarate, represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼, is reacted with pentynyl bromide to form the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [R' in the formula is CH_3CH_2C≡CCH_2- group] to obtain dimethyl 2-acetyl-3-dimethoxymethyl-2-(2-pentynyl)glutarate,
Next, the compound of formula (IV) is catalytically reduced in the presence of Lindlar catalyst to produce 2-acetyl-3 represented by the formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R represents a CH_3CH_2CH=CHCH_2- group] -Dimethoxymethyl-2-(cis-2-pentenyl)dimethyl glutarate was obtained, and then the compound of formula (III) was hydrolyzed to obtain the compound of formula ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R is the same as above] We obtained methyl 2-acetyl-3-formyl-2-(cis-2-pentenyl)glutarate, which was further expressed by the formula (
Formula ▲ Formula characterized by ring-closing the compound II),
There are chemical formulas, tables, etc. ▼ [In the formula, R is the same as above] 5-methoxycarbonyl-4-methoxycarbonylmethyl-5-(cis-2-pentenyl)-2-
Method for producing cyclopentenone. 6 The condensation reaction of methyl cis-4,4-dimethoxy-2-butenoate and methyl acetoacetate represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Dimethyl 2-acetyl-3-dimethoxymethylglutarate represented by the formula is obtained, and then the compound of formula (V) is reacted with pentynyl bromide to obtain the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R' is CH_3CH_2C≡CCH_2- represents dimethyl 2-acetyl-3-dimethoxymethyl-2-(2-pentynyl)glutarate,
Next, the compound of formula (IV) is catalytically reduced in the presence of Lindlar's catalyst to produce 2-acetyl-3 represented by the formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R represents a CH_3CH_2CH=CHCH_2- group] Dimethyl -dimethoxymethyl-2-(cis-2-pentenyl)glutarate was obtained, and the compound of formula (III) was further hydrolyzed to form the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R is the same as above. ] A formula characterized by obtaining methyl 2-acetyl-3-formyl-2-(cis-2-pentenyl)glutarate represented by and finally ring-closing the compound of formula (II) etc.▼ [In the formula, R is the same as above] 5-methoxycarbonyl-4-methoxycarbonylmethyl-5-(cis-2-pentenyl)-2-
Method for producing cyclopentenone.