JPS5835509B2 - 2-[ω,ω-bis(alkylthio)-or ω,ω-(alkylenedithio)-alkyl]-3-methyl-2-cyclopenten-1-one and its production method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is useful in itself for applications such as long-lasting fragrance substances, flavoring and modulating agents, and is also useful in the field of intermediates for cis-jasmone fragrance substances and other useful compounds. The present invention also relates to a useful new compound 2-[ω·ω-bis(alkylthio)- or ω·ω(alkylenedithio)-alkylio-3-methyl-2-cyclopenten-1-one and a method for producing the same.

The compound of the present invention is represented by the following formula [■] However, in the formula, R may be the same or different and represent a husband, a lower alkyl group, or an aralkyl group, or two SRs together represent the formula %. % or C2 to C4 lower alkylene group,)n is O
2-[ω・ω-bis(alkylthio) or ω・ω-(alkylenedithio)-alkylyo 3-
This compound is methyl-2-cyclopenten-1-one and has not been described in any literature.

The above formula CI) compound has the following formula (II), where R
may be the same or different and represent a lower alkyl group or an aralkyl group, or the two SR together may be of the formula \R/ (where R' is a lower alkylene group, preferably 8 / or represents a C2-C4 lower alkylene group,)n is O
A ω·ω-bis(alkylthio)- or ω·ω-(alkylenedithio)-2,5-dioxoalkane represented by an integer of ~4 is subjected to a cyclization reaction in a solvent in the presence of an alkali. This allows for easy production with high yield and high purity.

Therefore, the object of the present invention is to use the formula CI which is useful in the above-mentioned fields.
) new compound 2-[ω・ω-bis(alkylthio)-
Alternatively, ω·ω-(alkylene group thi,t)-alkylio-3-methyl-2-cyclopenten-1-one is provided.

Another object of the present invention is to provide a method for easily producing the compound of formula CI) with high yield and high purity.

The above objects and many other objects and advantages of the present invention will become more apparent from the following description.

For details of the above formula [II, l compound and its manufacturing method, see the application filed on the same date by the same applicant (Japanese Unexamined Patent Publication No. 53-25514 (Japanese Patent Application No. 51-100232) [Name of the invention: ω・ω
2-[ω·ω- bis(alkylthio)- or ω
・ω-(alkylenedithio)-alkyl2-5-methylfuran and its production method are disclosed in the application filed on the same date by the same applicant (Japanese Unexamined Patent Publication No. 53-25554 (Japanese Patent Application No. 51-1002).
No. 31) [Title of the invention: 2-[ω・ω-bis(alkylthio)- or ω・ω-(alkylenedithio)-alkyl2-5-methylfuran and its production method], but below: I will summarize and explain.

The above formula (n) compound is a known compound represented by the following formula (2)
, where n represents an integer of O to 4, in the presence of an acid catalyst,
-valent or polyvalent lower thiol, preferably with a thiol number selected from the group consisting of C1 to C4 monovalent lower thiols, aralkylthiols in which the number of carbon atoms in the thiol is C1 or C2, and polyvalent lower thiols in which the number of carbon atoms in the thiol is C2 to C4. The following formula (1) obtained by 2-[ω・ω-bis(alkylthio) or ω・ω-(alkylenedithio)-alkyl2-5-
Methylfuran can be prepared by ring opening in a water-miscible organic solvent in the presence of water and an acid catalyst.

The water produced as a by-product in the reaction between the aldehyde compound of the formula (2) and the thiols can be removed from the fibers if desired during the reaction, which often yields favorable results.

The reaction with the thiol can also be carried out in the absence of a solvent.

The reaction can, if desired, be carried out using inert organic solvents, for example aromatic hydrocarbons and their derivatives such as benzene-xylene, toluene, halogenated benzenes, nitrobenzene; chloroform, methylene chloride, trichloroethane, hexane, Aliphatic hydrocarbons such as heptane and derivatives thereof can be mentioned.

Other organic solvents such as dioxane, tetrahydrofuran, ether can also be used if desired.

The reaction is preferably carried out under heating conditions, for example, heating conditions of about 0° C. to about the boiling point of the thiol or solvent used, and preferably under heating reflux conditions.

The reaction is usually carried out under atmospheric or naturally occurring pressure conditions, although elevated or reduced pressure conditions can be employed if desired.

For example, atmospheric pressure or about 50 kg/crrL to about lm
Examples include pressurized or reduced pressure conditions within the mHg range.

The reaction time is, for example, about 2 hours to about 15 hours.

Preferred examples of the above-mentioned -valent or polyvalent lower thiols include C1-C4 monovalent lower thiols such as methanethiol, ethanethiol, n- or 1so-propanethiol, n-1so- or tert-butanethiol; dithiol, propanedithiol,
Examples include C2 to C4 polyvalent lower thiols such as butanedithiol.

A wide range of inorganic or organic acids can be used as the acid catalyst, and examples include mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, etc., and organic acids such as para-toluenesulfonic acid, oxalic acid, etc.

These acid catalysts may be used in small amounts (for example, about 0.1% to about 10% by weight based on the monovalent or polyvalent lower thiol or the solvent used).

The amount of the thiol used is generally about 1 to about 20 times the weight based on the formula (2 compounds).

After the reaction, water is poured into the reaction product system, and a water-immiscible organic solvent such as benzene, toluene, hexane, etc. is added for extraction. After washing with water, the organic solvent is distilled off to obtain the formula (
2-[ω·ω-bis(alkylthio)- or ω·ω-(alkylenedithio)-alkyl2-5-methylfuran of 1) can be obtained.

The obtained compound can be further purified by distillation under reduced pressure, if desired.

2[ω
- The ring-opening reaction of ω-bis(alkylthio)- or ω·ω-(alkylenedithio)-alkylio-5-methylfuran can be carried out in a water-miscible organic solvent in the presence of water and an acid catalyst.

The reaction is preferably carried out under heating conditions, for example heating conditions ranging from about 0° C. to the boiling point of the organic solvent used, preferably under heating reflux conditions.

The reaction is usually carried out under atmospheric or naturally occurring pressure conditions, although elevated or reduced pressure conditions can be employed if desired.

For example, pressurized or reduced pressure conditions within the range of atmospheric pressure or about 50 kg/crrf to about 1 miHg can be exemplified.

The reaction time is, for example, about 2 hours to about 15 hours.

Examples of the water-miscible organic solvents include lower alcohols such as methanol, ethanol, n- or lso-propyl alcohol, n-liso- or tert-butanol; acetone, dioxane, tetrahydrofuran, and C1-C4 organic carboxylic acids. etc. can be exemplified.

A wide range of inorganic or organic acids can be used as the acid catalyst, and examples include mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, etc., and organic acids such as para-toluenesulfonic acid, oxalic acid, etc.

The amount of these acid catalysts used may be small, for example, about 0.5% to about 20% by weight based on the solvent used.

In addition, the amount of the solvent used is based on the compound of formula (1),
It is usually used at about 1 to about 20 times the weight.

Further, the amount of water is usually equivalent to the weight of the compound of formula [■] to about % times the weight of the above-mentioned solvent.

After the reaction, water is poured into the reaction product system, and organic solvents such as benzene, toluene, methylene chloride, etc. are added to extract it.
After washing with water, the organic solvent is distilled off to obtain the ω·ω-bis(alkylthio) or ω·ω-(alkylenedithio)-2·5-dioxoalkane of formula (II).

The obtained compound can be further purified by distillation under reduced pressure, if desired.

In the present invention, the formula (
The ω・ω-bis(alkylthio)- or ω・ω-(alkylenedithio)2,5-dioxoalkane represented by II) is subjected to a cyclization reaction in a solvent in the presence of an alkali, resulting in a smooth cyclization reaction with a good yield. can be converted into a highly pure compound of formula CI).

Water is most commonly used as a solvent, but raw material formula [■
] If the compound is poorly soluble in water under the reaction conditions, other solvents may be used alone or in combination with water.

Examples of such other solvents include, for example, methanol,
Examples include lower alcohols such as ethanol, propatool, and butanol; ethers such as ether, dioxane, and tetrahydrofuran; and water-soluble organic solvents such as acetone.

Examples of the alkali include alkali metal or alkaline earth metal water such as sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, potassium carbonate, sodium methylate or ethylate, sodium hydride, and sodium amide. Oxides; Carbonates, alcoholades, hydrides, amides, etc. can be mentioned.

The amount of alkali to be used can be selected as appropriate, and for example, it can be used in an amount of about 1% to about 20% based on the weight of the solvent used.

Since the reaction proceeds even at room temperature, heating is not particularly required, but heating conditions are preferably employed.

Generally, temperatures in the range of about 120°C to about 120°C are employed.

The amount of solvent to be used can be selected as appropriate and there are no particular restrictions, but it is usually about 3 times to about 2 times the weight of the compound of formula [■].
Amounts in the range of about 0x are utilized.

As an example of using a compound of formula CI[) that is as sparingly soluble in water as possible, side light is 8,8-bis(alkylthio)- or 8,8-(alkylenedithio)-2.
When using 5-dioxooctane, 2 to 5-dioxooctane is used based on the raw material.
Add a mixture of caustic soda aqueous solution with a concentration of 1 to 10% of 20 times the weight and methanol of 0.5 to 5 times the weight to make 1 to 10
If left at room temperature or heated under reflux for an hour, the compound 2-[2,2-bis(alkylthio)ethyl] or 2[2,2-(alkylenedithio)ethyl)-3 when n=1 in the formula CI) -Methyl-2-cyc□pentene-1
-one can be obtained quantitatively and as a single product.

The compounds of formula CI) of the invention are also useful as intermediates in the synthesis of perfume materials.

For example, cis-jasmine, which is important as a jasmine fragrance, can be obtained in good yield and high purity by reacting with 2-formylmethyl-3-methyl-2-cyclopentene-1-one, propyltriphenylphosphonium halide, and a base. However, the 2-formylmethyl-3methyl-2-cyclopenten-1-one could only be produced by a method that is associated with many disadvantages and deficiencies.

That is, conventionally, the above-mentioned known compound 2-formylmethyl-
For the production of 3-methyl-2-cyclopenten-1-one, 2-methoxycarbonylmethyl-3-methyl-
A method for producing 2-cyclopenten-1one by reducing it using expensive diisobutylaluminum hydride under extremely low temperature conditions of -70°C (Au5t, J, Ch
Em, 26.2671 (1973)) and the expensive allethrone [3-methyl-2-(2-propenyl)
A method for producing -2-cyclo-r-penten-1-one by ozone oxidation at a low temperature of -20°C (Agr.

Biol, Chem, 39 1887 (197
Only two methods (5)) have been reported.

The former method has the disadvantage of using diisobutylaluminum hydride, which is expensive and difficult to handle, as well as the drawbacks of requiring low-temperature reaction operations of 70°C and special refrigeration equipment, making it difficult to use on an industrial scale. This is extremely disadvantageous for implementation.

In addition, the latter method has the disadvantages of equipment and operation, as it requires an ozone generator due to the use of ozone and a refrigeration equipment necessary for the low temperature reaction of 20°C, and like the former method, it cannot be used on an industrial scale. It is inappropriate for implementation.

Furthermore, both methods yield unsatisfactory results in terms of yield and purity of the target product.

However, if 2-[2,2-bis(alkylthio)ethyl]- or 2[2,2-(alkylenedithio)ethyl-2-3methyl-2-cyclopenten-1-one obtained by the method of the present invention is used, known hydration Decomposition methods, for example, in the presence of (1) mercuric chloride-mercuric oxide in a water-containing water-miscible organic solvent, such as acetone, acetonitrile, (2) N-bromosuccinimide or N -chlorosuccinimide-in the presence of silver sulfate, (3)
If cupric chloride is reacted in the presence of cupric oxide, it will be hydrolyzed by any of the above methods, and 2-formylmethyl-3-methyl-2-cyclopenten-1-one will be produced in high yield and purity. Can be manufactured at low cost.

Therefore, using the present invention, 2-[2,2-bis(alkylthio)ethyl]- or 2-[2,2-(alkylenedithio)ethyl-3-methyl-2-cyclopenten-1-one can be converted into a hydrous organic 2-formylmethyl-3-methyl, characterized in that it undergoes a hydrolysis reaction in the presence of a mercuric salt or a cupric salt, or an oxidative hydrolysis reaction in the presence of an N-halosuccinimide in a solvent. A method for producing -2-cyclopefunten-1-one can also be provided.

The above reaction proceeds even at room temperature, but preferably from 5°C to 10°C.
Temperatures in the range of about 0°C can be used.

Hereinafter, some examples of the production and use of the compound of formula CI) of the present invention will be described in more detail.

Production Example 1 Production of 2-(2,2-bis(methylthio)ethyl-3-methyl-2-cyclopenten-1-one) 8,8-Bis(ethylthio)-2,5-dioquino-so-octane 262S'(1,0 mol) in a mixture of 500ml of 5% aqueous sodium hydroxide solution and 500P of methanol, and heated under reflux for 5 hours.

After cooling, extract with methylene chloride, wash with water, distill off methylene chloride, and distill under reduced pressure to obtain a boiling point of 120-122℃/3.
mmHgn”; , == i, 5608 d
"i", -1,1252 shows the title compound 222S' (
A theoretical yield of 91%) is obtained.

Production Example 2 Production of 2-C2.2-(ethylenedithio)ethyl-3-methyl-2-cyclopenten-1-one 8.8-(ethylenedithio)-2.5-dioxooctane 232P (1.0 mol) 5% caustic soda aqueous solution 50
Pour into a mixture of 0ml and 50ml of methanol and heat under reflux for 5 hours.

After cooling, extraction with 1 ml of methylene chloride, washing with water, distilling off the methylene chloride, and distillation under reduced pressure resulted in a boiling point of 142-145°C/
3 mmHg n25=1.5864 a4 snow-1,
199 g of the title compound showing 2047 (theoretical yield 93%)
is obtained.

Production Example 3 In the same manner as Production Example 1 or 2 above, formula CI in Table 1 below was prepared.
A compound is obtained.

Application example 1 Production of 2-formylmethyl-3-methyl-2-cyclopenten-1-one 2-[2,2-bis(methylthio) obtained in Production Example 1
3-methyl-2-cyclopenten-1-one 214f (1 mol) to cupric chloride 340S' (2 mol)
, cupric oxide 311' (4 mol), 2% hydrated acetone 1
00 (l) and heated under reflux for 1 hour.

After cooling, add water, extract with methylene chloride, wash with saturated brine, dry, remove methylene chloride, and distill under reduced pressure.
Boiling point 101-104℃/3mmHg, nj'=1.5
123, the title compound 127f exhibiting a value of 1.0989?
(92% theoretical yield) is obtained.

Application example 2 An application example of a flavoring composition in which 2-[2,2-bis(propylthio)ethylio-3-methyl-2-cyclopenten-1-one obtained in Production Example 3 is applied to pineapple flavor is shown below. show.

Ingredients Ethyl butyrate 0 1,1-dimethyltylphenyl butyrate Allyl butyrate phenoxyethyl caproate Butyrate 6 3-Hydroxy-2-methylpyrone (maltol) Gamma- 0 2-[2,2-bis(furobylthio)ethyl yo 3 -Methyl-2-cyclopenten-1-one 00 When a flavored product is flavored with a flavor obtained by diluting the above base to 5 to 10% with a solvent depending on the purpose, the ripeness of pineapple is significantly improved.

Claims (1)

[Claims] 1 Formula CI) or ω·ω-(alkylenedithio)-alkyl2-3-methyl-2-cyclopenten-1-one. 2. The compound according to claim 1, wherein the lower alkyl group is a C1-C4 lower alkyl group, the aralkyl group is an aralkyl group of the formula, and the lower alkylene group is a C2-C4 lower alkylene group. 3 The following formula (II) However, in the formula, R may be the same or different and represent a husband, a lower alkyl group, or an aralkyl group, or two SRs together form the formula /R'('' j”e, R’+!
lower a/Iz #L/ 7 groups ・)S, where n is an integer of 0 to 4, ω・ω-bis(alkylthio)- or ω・ω-(alkylenedithio)-2 represented by・The following formula [■], which is characterized by cyclizing 5-dioxoalkane in a solvent in the presence of an alkali, represents a lower alkyl group or an aralkyl group, or two SRs are the same. Becomes the formula /R/ (here, R' is a lower grade A'ki v7
2-[ω・ω-bis(alkylthio)- or ω・ω-(alkylenedithio)-alkylyo 3
-Production method of methyl-2-cyclopenten-1-one. 14 The above formula (
4. The method according to claim 3, wherein the lower alkyl group in the ID compound is a C1-C4 lower alkyl group, and the aralkyl group in the aralkyl group is a C2-C4 lower alkylene group.