JPS5931506B2 - 2-[ω,ω-bis(alkylthio)-or ω,ω-(alkylenedithio)-alkyl]-5-methylfuran 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 agents, modulators, etc., and is also useful in the field of intermediates for sysudium-based fragrance substances and other useful compounds. A new compound 2-[ω・ω-bis(alkylthio)- or ω
-Relating to ω-(alkylenedithio)-alkyl]-5-methylfuran and its production method.

The compound of the present invention has the following formula [1], where R may be the same or different, and is a lower alkyl group, preferably a C1 to C4 lower alkyl group, or an aralkyl group, preferably << )-4CH2h ．． [However, m represents an aralkyl group represented by 1 or 2], or two SRs taken together represent the formula W (where w is / ゛lower alkylene group, preferably C
2-[ω・ω-bis(alkylthio) or ω・ω-1(alkylenedithio)-alkyl]-5-methyl, where n represents an integer of 0 to 4) It is a compound that has not been described in any literature.

The above formula [1] compound is a known raw material compound of the following formula [
], where n is the same as described above, in the presence of an acid catalyst,
Monovalent or polyvalent lower thiol, preferably C1-C4
Monovalent lower thiol, the number of carbon atoms in the thiol is C, or C2
By reacting with thiols selected from the group consisting of aralkyl thiols and C2 to C4 polyvalent lower thiols, it can be easily produced with high yield and high purity.

Therefore, the object of the present invention is to obtain the formula [
I] Novel compound 2-[ω・ω-bis(alkylthio)
1 or ω・ω-(alkylenedithio)-alkyl]
-5-Methylfuran.

Another object of the present invention is to provide a method for easily producing the compound of formula [1] 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.

The novel compound of the formula [1] of the present invention is, for example, the novel compound of the following formula [
] wherein n represents an integer of O to 4, an aldehyde compound represented by the following is reacted in the presence of an acid catalyst,
It can be obtained by reacting with a monovalent or polyvalent lower thiol.

The above reaction can be carried out in the presence of an inert organic solvent, if necessary. Water produced as a by-product in the reaction between the aldehyde compound of the above formula [] and thiol can be removed from the system if desired during the reaction, which often yields favorable results. The resulting compound of formula [I] can be used, for example, in Japanese Patent Application Laid-Open No. 5325514 (Japanese Patent Application No. 1983-1989) filed on the same date by the same applicant.
No. 100232) [Name of the invention: ω・ω-bis(alkylthio)- or ω・ω-(alkylenedithio)-2
- 5-dioxoalkane and its production method]. As a specific example of the compound of the above formula [], as a compound in the case of n-0, for example, 5-
Methyl 2-furylacetaldehyde; as a compound when n=1, for example, 3-(5-methyl-2furyl)
Propanal; as a compound when n=2, for example, 4-(5-methyl-2-furyl)butanal: n-3
For example, 5-(5-methyl-
2-furyl)pentanal: Examples of the compound in the case of n-4 include 6-(5-methyl-2-furyl)hexanal.

To give some examples of the production of these compounds of the known formula [], for example, the compound of n-0 in the formula [], such as 5-methyl-2-furylacetaldehyde, is 5-methyl-2-furylacetaldehyde, which is available at low cost.
-2-(2-nitroethyl) obtained by condensing methyl-furfural with nitromethane and then catalytic reduction
It can be obtained in high yield by hydrolyzing 5-methylfuran.
In addition, the compound of n1 in formula [], for example, 3-(5-
Methyl-2-furyl)propanal can be produced in high yield and at low cost by condensing acrolein with 2-methylfuran obtained by reducing furfural, which is inexpensive and easily available. For example, hydrazone obtained by reacting furfural with hydrazine hittride in ethylene glycol is heated in the presence of caustic alkali, and acrolein is condensed with the above-mentioned 2-methylfuran in the presence of an acid catalyst. It can be produced with high yield. Furthermore, the expression []
For example, 4-(5-methyl-
2-furyl)butanal can be obtained by reacting the above-mentioned 5-methyl-2furyl acetaldehyde with acetaldehyde in the presence of a dilute alkali, and then selectively reducing only the side chain unsaturated bonds, and n=3. For example, a compound of
Similarly, 5-(5-methyl-2-furyl)pentanal is obtained by reacting the above-mentioned 3(5-methyl-2-furyl)propanal with acetaldehyde in the presence of a dilute alkali, and then removing only the unsaturated bonds in the side chain. It can be obtained by selective reduction. In addition, the compound n-4, for example, 6-(5-methyl-2-furyl)hexanal, is also used in the same manner as above 4-(
It can be obtained by reacting 5-methyl-2-furyl)butanal with acetaldehyde in the presence of a dilute alkali, and then selectively reducing only the side chain unsaturated bonds. The reaction of the compound of formula [] with a monovalent or polyvalent lower thiol in the presence of the above-mentioned acid catalyst in the production of the compound of formula [] can 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. 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 5'C to 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/Cr! i ~ about 1m7! LHg
For example, pressurization or depressurization conditions within the range of . The reaction time is, for example, about 2 hours to about 15 hours. Preferred examples of the monovalent or polyvalent lower thiol include methanethiol, ethanethiol, n- or IsO-propanethiol, n- 1sO- or T
Examples include C1 to C4 monovalent lower thiols such as ert-butanethiol; C2 to C4 polyvalent lower thiols such as ethanedithiol, propanedithiol, and 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.

The amount of these acid catalysts used may be small, for example, about 0.1% by weight 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 of the compound of formula []. 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 above formula [1 ] of 2-[ω・ω-bis(alkylthio)- or ω・ω-(alkylenedithio)-alkyl]-5-
Methylfuran can be obtained.

The obtained compound can be further purified by distillation under reduced pressure, if desired. The above formula [1] obtained by the method of the present invention
The compound itself is useful as a long-lasting fragrance substance, a flavoring/modulating agent, and the like, and is also useful as an intermediate for sysudium-based fragrance substances and other useful compounds.

Furthermore, an application filed on the same date by the same applicant [Patent Application No. 511: ω・ω-bis(alkylthio)-
Alternatively, it is also useful as a raw material for producing the compounds detailed in ω・ω-(Alkylene dithio-2,5-dioxoalkane and its production method).Hereinafter, the number of production and uses of the compound of formula [1] of the present invention will be explained. The example will be explained in more detail.

Production Example 1 Production of 2-[3,3-bis(methylthio)propyl]-5-methylfuran 3-(5-methyl-2-furyl)propanal 1387 (1 mol), benzene 1', p-toluenesulfonic acid 2.07 was added, and 1447 (3 mol) of methanethiol was introduced from the cylinder at 25-30°C for 3 hours.

After further reacting at the same temperature for 2 hours, the reaction solution was washed with water,
When benzene is distilled off and then distilled under reduced pressure, the boiling point is 110-112
/3mmHg. n25ゝ
ゝDl. 5352, d+1.
The title compound of 0893 is ※※195y (theoretical yield 9
0%) obtained. Production Example 2 Production of 2-[3,3-bis(probylthio)propyl]5-methylfuran 3-(5-methyl-2-furyl)propanal 138y (1 mol), propylthiol 212
y (2 mol), benzene 11, and para-toluenesulfonic acid 2.0 y are added, and the mixture is heated to reflux with stirring using an Azeo apparatus.

The reaction is stopped when an equal amount of water has been distilled into the Azeo apparatus (about 2 hours). Pour water, extract with benzene, and distill under reduced pressure, resulting in a boiling point of 138-140℃/3m77! HgJM
l. 5l55, d: Rl. The title compound of Ol49 is 23
17 (theoretical yield 85%) is obtained. 5 Production Example 3 In the same manner as in Production Example 1 or 2 above, the compound of formula [I] shown in Table 1 below was obtained.

Claims (1)

[Claims] 1 The following formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] However, in the formula, R may be the same or different, and may represent a husband, lower alkyl group, or aralkyl group. or two SRs taken together ▲ has a mathematical formula, chemical formula, table, etc. ▼ (where R' represents a lower alkylene group), n represents an integer from 0 to 4, 2- [ω·ω-bis(alkylthio)-or ω·ω-(alkylenedithio)-alkyl]-5-methylfuran. 2 The lower alkyl group is a C_1 to C_4 lower alkyl group, the aralkyl group is an aralkyl group represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [where m is 1 or 2], and the lower alkylene group is The compound according to claim 1, which is a C_2 to C_4 lower alkylene group. 3 The following formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] However, in the formula, n
represents an integer from 0 to 4. The following formula (I) is characterized by reacting an aldehyde compound represented by with a monovalent or polyvalent lower thiol in the presence of an acid catalyst. There are mathematical formulas, chemical formulas, tables, etc., where: R may be the same or different,
Fufu, represents a lower alkyl group or an aralkyl group, or two OR together ▲A mathematical formula, a chemical formula, a table, etc.▼ (where R' represents a lower alkylene group)
, n is an integer from 0 to 4, expressed as 2-[ω・ω
A method for producing -bis(alkylthio)- or ω·ω-(alkylenedithio)-alkyl]-5-methylfuran. 4 The monovalent or polyvalent lower thiol is C_1 to C_4
Monovalent lower thiol, the number of carbon atoms in the thiol is C_1 or C
The method according to claim 3, wherein the thiol is selected from the group consisting of aralkyl thiols of _2 and polyvalent lower thiols of C_2 to C_4.