JPH0363540B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula () (In the formula, _R1 represents a hydrogen atom or a lower alkyl group, and _R2 represents a _C1 - _C8 alkyl group, a C2 _{- C8} alkenyl group, a _C2 - _C8 alkynyl group, a _C3 - _C8 Represents a cycloalkyl group, phenyl group or benzyl group, A is a lower alkoxy lower alkyl group, C ₁
~ _C18 alkyl or alkenyl group, lower alkynyl group, hydroxy lower alkyl group; N, N-
lower dialkylamino lower alkyl group, furfuryl group, thenyl group; _C3 - _C6 cycloalkyl group optionally substituted with lower alkyl group and/or hydroxy group; substituted with lower alkyl group and/or lower alkenyl group; or a phenyl group or phenyl lower alkyl group which may have a hydroxy group, a halogen atom, a sulfamoyl group, a lower alkyl group, a lower alkoxy group or a methylenedioxy group. ) relates to a method for producing an ether derivative of cyclopentenones. Ether derivatives of cyclopentenones represented by the general formula () are not only useful as agricultural chemicals and intermediates thereof, but also valuable as intermediates for perfumes and pharmaceuticals. The present invention provides a method for producing such ether derivatives of cyclopentenones at low cost and industrially advantageously. Conventionally, as a method for synthesizing ether derivatives of cyclopentenones, for example, Tetrahedron, Vol. 36,
No.5661 (1980) The method R′ C ₁₁ H ₂₃ C ₇ H ₁₅ C ₁₁ H ₂₃ R CH ₃ CH ₃ H is described. However, the only alcohol used in this method is methanol, and there is no mention of other alcohols.
The reactivity with phenols and other higher alcohols is completely unknown. Furthermore, this method has various drawbacks such as the difficulty in producing the raw material α,β-unsaturated-γ-diketone and the poor yield, making it unsatisfactory as an industrial method for producing compounds of general formula (). It's not possible. Under these circumstances, the inventor has developed the general formula ()
As a result of research into a new method for producing compounds, the inventors discovered that the target compound can be obtained easily and in extremely good yields using a novel reaction method that was previously unknown, leading to the present invention. That is, the present invention is based on the general formula () (wherein R ₁ and R ₂ have the same meanings as above) and 3-hydroxy-4-cyclopentenones represented by the general formula A-OH (wherein A has the same meanings as above). ) This is a method for producing an ether derivative of cyclopentenones represented by the general formula (), which comprises reacting the ether derivative with a compound having a hydroxyl group represented by the formula (). Compounds of general formula () obtained by the method of the present invention are new compounds that have not been described in literature except when substituent A is a methyl group. When A has a phenyl group, it can be used as an ester of chrysanthemum acid, and it can be used not only as a new agricultural chemical, but also as a fragrance when A has a geranyl group, and can also be used as a new derivative of prostaglandin. It is an extremely valuable compound. The present invention will be explained in detail below. The 3-hydroxy-4-cyclopentenones represented by the general formula () used as raw materials in the present invention can be easily obtained, for example, by rearranging furancarbinols as shown in the following formula. (In the above formula, R ₁ and R ₂ have the same meanings as above.) In addition, as the compound having a hydroxyl group, which is the other reaction raw material, any organic compound having a hydroxyl group can be used without particular restriction, such as ethanol. , isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, n-octyl alcohol, dodecyl alcohol, ethylene glycol, 1,3-propanediol, allyl alcohol, 2-pentenyl alcohol, 3-hexenyl alcohol, geraniol, nerol, Farnesyl alcohol, cyclopentanol, cyclohexanol, 2-cyclohexenyl alcohol, cyclopropylmethyl alcohol, l-menthol, propargyl alcohol, 2-pentyn-1-ol, 1,4-cyclohexanediol, dimethylaminoethanol, dimethyl Aminopropanol, diethylaminoethanol, furfuryl alcohol, thenyl alcohol, 2,2-
Dimethyl-3(2-methyl-1-propenyl)-cyclopropyl-1-methanol

Alcohols such as [formula], phenol, cresol, 4-chlorophenol,
2,4-dichlorophenol, 4-dimethylaminophenol, 4-sulfamoylphenol,
Catechol, resorcinol, hydroquinone, sesamol, phenols such as 4-methoxyphenol, benzyl alcohol, l-α-methyl-benzyl alcohol, d-α-methyl-benzyl alcohol, 3,4-methylenedioxybenzyl alcohol, 2, 4-dichlorobenzyl alcohol,
Examples include aralkyl alcohols such as 3,4-dimethoxybenzyl alcohol and β-phenethyl alcohol. 3-hydroxy-4- represented by general formula ()
The reaction between cyclopentenones and an organic compound having a hydroxyl group is carried out using a catalyst in the presence or absence of a solvent. When using a solvent, examples of the solvent include water,
Dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, DMF, DMSO, benzene,
Examples include solvents inert to the reaction, such as aliphatic or aromatic hydrocarbons such as toluene, chloroform dichloromethane, ether, and ethyl acetate, ethers, esters, and halogenated hydrocarbons, either alone or as a mixture. Alternatively, an organic compound having an excess amount of hydroxyl groups may be used as the solvent. Examples of catalysts used include common acid catalysts such as toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, potassium carbonate, sodium hydrogen carbonate, triethylamine, pyridine, collidine, quinine, Common bases such as sodium methylate, sodium ethylate, metals such as sodium, potassium, and lithium or their hydrides, metal nitrates, sulfates, chlorides, phosphates, oxides, or organic quaternary ammonium An example is salt. These may be used alone or as a mixture of two or more. The amount of the catalyst to be used is not particularly limited, but is usually in the range of 1/500 to 1/2 times the weight of the compound of general formula () as a raw material. The reaction temperature is arbitrary in the range of 0 to 200°C, but preferably in the range of 20 to 160°C, and the reaction time is not particularly limited. Thus, by the method of the present invention, the desired ether derivatives of cyclopentenones represented by the general formula () can be obtained easily and in good yields, and these can be obtained by conventional separation means such as extraction and separation, concentrated,
It can be easily isolated from the reaction mixture by distillation or the like. The present invention will be explained below with reference to Examples. Example 1 0.1 mole of 2-ethyl 3-hydroxy-4-cyclopentenone () was added to a four-necked flask equipped with a stirrer and a thermometer, and 3 parts by weight of ethanol and 1/50 part by weight. of sodium ethylate and stirred at 20-40°C for 2 hours. After the reaction is completed, the mixture is neutralized with 1N-HCl water and the solvent is distilled off.
The concentrated residue was extracted with toluene, and toluene was distilled off from the resulting organic layer to obtain 2-ethyl-4-ethoxy-2-cyclopentenone in a yield of 98%. n ²⁰ _D 1.4767 Example 2 Into the same apparatus as in Example 1, 0.1 mol of 2-allyl-3-hydroxy 3-methyl-4-cyclopentenone () and 5 parts by weight of 2-cis- Add pentenol and 1/30 part by weight of sodium hydride, and stir at 10 to 15°C for 1 hour. After the reaction was completed, post-treatment was carried out according to Example 1, and 2-
Allyl-3-methyl-4-(2-cispentenyloxy)-2-cyclopentenone was obtained with a yield of 97%. n ¹⁵ _D 1.4946 Example 3 In the same apparatus as in Example 1, 2-n-pentyl-
0.1 mol of 3-hydroxy-3-methyl-4-cyclopentenone (), 5 times the weight of n-propyl alcohol and 1/20 times the weight of p
- Add toluenesulfonic acid and stir at 40-70°C for 5 hours. Thereafter, post-treatment was performed according to Example 1 to obtain 2-n-pentyl-3-methyl-4-n-propoxy-2-cyclopentenone in a yield of 96%. n ¹⁹ _D 1.4792 Example 4 Using the same apparatus as in Example 1, 2-allyl-3
- Hydroxy-3-methyl-4-cyclopentenone () 0.1 mole is added to a solution of 4 times the weight of 3,4-dimethoxybenzyl alcohol and the same weight of tetrahydrofuran as 1/40 times the weight of hydrogen. at 10-20°C in a mixture with added sodium chloride.
Add in 30 minutes. After the dropwise addition was completed, the mixture was stirred at the same temperature for 1 hour. After the reaction was completed, the mixture was post-treated in the same manner as in Example 1 to obtain 2-allyl-3-methyl-4-(3,4-dimethoxybenzyloxy)-2-cyclopentenone in a yield of 96%. n ²⁰ _D 1.5514 Example 5 Into the same apparatus as in Example 1, 0.1 mole of 2-allyl-3-hydroxy-3-methyl-4-cyclopentenone (), 6 parts by weight of phenol and 1 Add /5 parts by weight of triethylamine and stir at 50 to 80°C for 4 hours. Following the post-treatment according to Example 1, 2-allyl-
3-Methyl-4-phenoxy-2-cyclopentenone was obtained with a yield of 95%. n ²⁰ _D 1.5539 Example 6 Into the same apparatus as in Example 1, 0.1 mol of 2-allyl-3-hydroxy-3-methyl-4-cyclopentenone (), 5 parts by weight of resorcin, 1 Add /2 parts by weight of tetrahydrofuran and 1/10 parts by weight of triethylamine,
React at ℃ for 2 hours. After the reaction is completed, toluene and water are added to the reaction mixture, and the organic layer is further washed with a 5% aqueous sodium carbonate solution. Toluene was distilled off from the resulting organic layer to obtain 2-allyl-3-methyl-4(3-hydroxyphenoxy)-2-cyclopentenone in a yield of 95%. Chromatographic purification with chloroform-methanol (5/2=V/V) gives a pure product. n ²⁰ _D 1.5707 Examples 7 to 25 Table 1 shows the results obtained according to the above examples. The amounts of catalyst, solvent, and alcohol used in the table are all expressed in terms of weight times the starting material () compound in each reaction.

【table】

[Table] Example 26 In a four-necked flask similar to that used in Example 1, two
-n-pentyl-3-hydroxy-3-methyl-
To 0.1 mole of 4-cyclopentenone (), 5 parts by weight of methanol and 1/40 part by weight of sodium methylate were added, and the mixture was heated to 20 to 50°C.
Stir for an hour. After the reaction is completed, the mixture is neutralized with 1N-HCl water and the solvent is distilled off. The concentrated residue is extracted with hexane, and the hexane is distilled off from the resulting organic layer.
-n-pentyl-3-methyl-4-methoxy-2
- Cyclopentenone was obtained with a yield of 97%. n ²⁰ _D 1.4758 Example 27 In the same manner as in Example 26, 0.1 mol of 2-allyl-3-hydroxy-3-methyl-4-cyclopentenone (), 4 parts by weight of methanol and 1/ Add 20 parts by weight of p-toluenesulfonic acid, and continue stirring at 30 to 60°C for 3 hours. After the reaction was completed, it was neutralized with 1N-NaOH water, and the following examples were prepared.
After treatment according to 26, 2-allyl-3-methyl-
4-Methoxy-2-cyclopentenone was obtained with a yield of 95%. n ²⁰ _D 1.4922

Claims (1)

[Claims] 1. General formula (In the formula, _R1 represents a hydrogen atom or a lower alkyl group, and _R2 represents a _C1 - _C8 alkyl group, a C2 _{- C8} alkenyl group, a _C2 - _C8 alkynyl group, a _C3 - _C8 cycloalkyl group, phenyl group or benzyl group) and the general formula A-OH (wherein A is a lower alkoxy lower alkyl group, C ₁ to C ₁₈ Alkyl or alkenyl group, lower alkynyl group, hydroxy lower alkyl group;
N,N-lower dialkylamino lower alkyl group,
Furfuryl group, thenyl group; may be substituted with lower alkyl group and/or hydroxy group
C ₃ - C ₆ cycloalkyl group; lower cycloalkyl lower alkyl group which may be substituted with lower alkyl group and/or lower alkenyl group; or hydroxy group, halogen atom, sulfamoyl group, lower alkyl group, lower alkoxy group or Indicates a phenyl group or a phenyl lower alkyl group which may have a methylenedioxy group. ) A general formula characterized by reacting with a compound having a hydroxyl group represented by (In the formula, R ₁ , R ₂ and A have the same meanings as above.) A method for producing an ether derivative of cyclopentenones.