JPS6339579B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention produces cis-diasmone, which is important as a diasmine fragrance, in high yield and with high purity, using inexpensive and easily available raw materials and reagents, and through easy operations and simple steps. Concerning new synthetic methods that can be manufactured.

Conventionally, the following formula (2) 1-(5-methyl-2-furyl)-
Cis-3-hexene is contacted with an acid catalyst in an aqueous polar organic solvent to cause a ring-opening reaction, and then cyclized with an alkali to form the following formula (). It is known to produce cis-diasmones represented by The production of the above formula (2) raw material compound involves various disadvantages such as disadvantageous operations using expensive reagents and process disadvantages, and
Improvement is also desired in the yield of the compound.

For example, J.Org.Chem., 31 , (3), pp. 977-978,
In 1966, the following formula, Therefore, the highly unstable intermediate 2-lithio-5- is produced using expensive n-butyllithium reagents and cis-3-hexenyl bromide under extremely low temperature conditions, such as -20°C, which are disadvantageous in industrial operations. It is described that the above formula (2) compound is formed via methylfuran. Moreover, the yield of the compound of formula (2) is as low as about 60% even when the process is carried out carefully, accepting the use of expensive reagents and the disadvantages in operation.

Furthermore, in Japanese Patent Publication No. 45-25885, unstable propylenetriphenylphosphorane obtained by reacting expensive n-propyltriphenylphosphonium halide with a base and 3-(5-methyl-2-
Frill) and propanal are subjected to a Wittig reaction under inert atmosphere conditions.
It has been proposed to produce the compound of formula (2) using expensive reagents and by means requiring complicated operational precautions. The yield is at best 80
up to about %.

The present inventors have conducted research to overcome the bottleneck in producing the compound of formula (2) in cis-diasmone synthesis. As a result, by a new synthesis method that was completely unknown in the past, the following formula () 2-(1,3-pentadienyl)-
3-methyl-2-cyclopenten-1-one,
The following formula () Mx (CO) y (arene) z () However, in the formula, M represents a metal atom selected from the group consisting of Cr, Mo and W, arene represents an arene ligand, and x represents 1 or 2, and y is 3
The above formula ( 2) It was discovered that cis-diasmone can be converted to cis-diasmone all at once and almost quantitatively without going through the compound process.

Furthermore, although there are no particular restrictions on the method for producing the compound of formula () above, according to the research of the present inventors,
The compound of formula () is represented by the following formula () 1-(5
-Methyl-2-furyl)-2,4-hexadiene is brought into contact with an acid catalyst in an aqueous polar organic solvent to cause a ring-opening reaction, and then a cyclization reaction is carried out with an alkali to produce it easily and in a good yield. It was also discovered that it is possible.

Therefore, an object of the present invention is to provide an industrially advantageous method for producing cis-diasmone using new synthetic processes and means. The above objects and many other objects and advantages of the present invention will become more apparent from the following description.

The formation of cis-diasmone using a catalytic hydrogenation reaction using a metal carbonyl compound or an arene complex thereof in the present invention can be shown as follows by a process formula including the production mode of the compound of formula () described above.

The above formula () known compound 1-(5-methyl-2
-Furyl)-2,4-hexadiene is, for example,
The following formula, Accordingly, it can be easily produced with good yield. That is, 3-(5-methyl-2-furyl)
-Propanal can be easily obtained by causing a Grignard reaction with propenylmagnesium halide, such as bromide, and then dehydrating it by an appropriate means, such as by contacting it with concentrated mineral acid, anhydrous copper sulfate, or other dehydrating agent. can. The above is an example, and there are no particular restrictions on the means for producing the known compound.

When carrying out the method of the present invention according to the above-mentioned process scheme, for example, the compound of formula () obtained as described above is brought into contact with an acid catalyst in an aqueous polar organic solvent to cause a ring-opening reaction. can be converted into a compound of formula () by carrying out a cyclization reaction with an alkali. The contact with the acid catalyst is carried out in an aqueous polar organic solvent,
As such a polar organic solvent, any inert organic solvent that can dissolve the compound of formula () and that is miscible with water can be used. Examples of such organic solvents include methanol, ethanol, n-
Or iso-propyl alcohol, butanol,
Alcohols such as ethylene glycol, propylene glycol, etc.; organic acids such as _C1 to _C4 organic carboxylic acids; water-soluble organic solvents such as acetone, dioxane, tetrahydrofuran, etc., and these may be used alone. However, multiple types can be used together. In addition, examples of acid catalysts include:
A wide range of inorganic or organic acids can be used, including mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and organic acids such as paratoluenesulfonic acid, oxalic acid, and the like.

The ring-opening reaction can be easily carried out by adding and stirring a small amount of the acid catalyst as exemplified above to a solution of the compound of formula () in an aqueous solution of an organic solvent as exemplified above. The amount of acid catalyst used can be small;
For example, it can be used in an amount of about 0.5 to about 10% by weight, more preferably about 1 to about 5% by weight, based on the compound of formula (). The reaction is preferably carried out under heating conditions, e.g. from about 50°C to about 100°C.
For example, the temperature of The reaction time is usually about 2 to about 15 hours. After the reaction is completed, the ring-opened product can be separated and recovered by means such as distillation.

The resulting ring-opened product can be easily cyclized and converted into a compound of formula () by treatment with an alkali. This cyclization reaction most commonly uses water as a solvent, but since the ring-opened product is poorly soluble in water, other solvents can be used alone or in combination with water. Examples of such other solvents include lower alcohols such as methanol, ethanol, propanol and butanol; ethers such as dioxane and tetrahydrofuran; and other water-soluble organic solvents such as acetone. Examples of the alkali include alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, potassium carbonate, sodium methylate, ethylate, sodium hydride, and sodium acid. Examples include hydroxides, carbonates, alcoholates, hydrides, amides, and the like. The amount of alkali to be used can be selected as appropriate, but 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 5°C to about 120°C are employed. The amount of solvent to be used can be selected as appropriate, and can be used in an amount ranging from about 3 times to about 20 times the weight of the ring-opened product.

For example, a compound of formula () obtained as described above is treated in the presence of a metal carbonyl compound represented by formula () or an arene complex catalyst thereof,
A catalytic hydrogenation reaction is carried out to produce a compound of formula (). The catalytic hydrogenation reaction is preferably carried out in the presence of any inert organic medium capable of dissolving the compound of formula (), such as methanol, ethanol, propanol, butanol, ethylene glycol,
Alcohols such as propylene glycol, glycerin, benzyl alcohol, phenylethyl alcohol; esters such as ethyl formate, ethyl acetate, methyl propionate, ethyl propionate; pentane,
Aliphatic hydrocarbons such as hexane, heptane, cyclopentane, and cyclohexane; Aromatic hydrocarbons such as benzene, toluene, and xylene; Halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and dichloroethane; Examples include organic media such as halogenated aromatic hydrocarbons such as chlorobenzene, bromobenzene, dichlorobenzene, and dibromobenzene, alone or in combination. The reaction is e.g.
About 130° to about 230°C, more preferably about 140° to about
Under heating conditions of approximately 200℃ and appropriate hydrogen pressure conditions,
For example, it can be carried out under hydrogen pressure conditions of about 2 to about 100 kg/cm ³ . The reaction can be carried out, for example, in a reaction time of about 1/2 hour to about 3 hours,
Cis-diasmone of the formula () compound can be obtained almost quantitatively. A compound of formula () can be purified by means such as distillation.

Examples of the metal carbonyl compound of formula () or arene complex catalyst thereof used in the reaction include hexacarbonyl chromium, benzenetricarbonyl chromium, thiofentricarbonyl chromium, pyridine tricarbonyl chromium, anisole tricarbonyl chromium, and chlorobenzene. Tricarbonylchromium, methylbenzoatetricarbonylchromium, hydride-π-cyclopentadienyltricarbonylchromium, π-cyclopentadienylmethyltricarbonylchromium, cycloheptanetrientrycarbonylchromium, cyclooctatrientrycarbonylchromium, mesitylenetricarbonylchromium Chromium, stilbene hexacarbonyl chromium, acetophenone tricarbonyl chromium, benzene tricarbonyl molybdenum, mesitylene tricarbonyl molybdenum, pyridine tricarbonyl molybdenum, azulene hexacarbonyl molybdenum, cycloheptane tricarbonyl molybdenum, cyclooctatritricarbonyl molybdenum, di-π -Cyclopentadienylhexacarbonyldimolybdenum, hydride-π-cyclopentadienyltricarbonylmolybdenum,
Examples include benzenetricarbonyltungsten, tritricarbonyltungsten, pyridinepentacarbonyltungsten, cyclooctadienetetracarbonyltungsten, mesitylenetricarbonyltungsten, and the like. The amount of the formula () catalyst to be used for the formula () compound is small; for example, for the formula () compound, the amount of the formula () catalyst used is approximately
A content of about 10 ^-5 to about 10 ^-1 % by weight is sufficient.

Hereinafter, several examples of implementing the method of the present invention will be illustrated in more detail with reference to Examples.

Reference Example 1 [Production of compound of formula ()] 24.5 g (0.15 mol) of 1-(5-methyl-2-furyl)-2,4-hexadiene, 246 ml of methanol,
Charge 12.3 g of concentrated sulfuric acid and 12.3 g of water, and react for 2 hours under refluxing methanol. After the reaction was completed and cooled to room temperature, the reaction solution was poured into a 10% aqueous sodium hydroxide solution.
React at 60-70°C for 2 hours. After the reaction is completed, the mixture is cooled to room temperature and the aqueous layer is extracted twice with 100 ml of methylene chloride. The methylene chloride layer was washed with 200 ml of saturated saline, dried with Glauber's salt, and after recovering the methylene chloride, distilled under reduced pressure to obtain 2-(1,3-pentadienyl)-3-methyl-2-cyclopentene-1-. On got 19g. The structure was confirmed by GLC-MS.

Example 1 2.2g of hexacarbonylchromium in an autoclave
(0.01 mol), 2-(1,3-pentadienyl)-
3-Methyl-2-cyclopenten-1-one 32g
(0.2 mol), 30 ml of n-hexane, and hydrogen pressure
React at 80Kg/cm ³ at 190-200°C for 4 hours. After the reaction was completed, the reaction mixture was washed with 50 ml of diluted acid, and then 5%
After washing with 50 ml of sodium bicarbonate aqueous solution, drying with Glauber's salt, recovering hexane, and distilling under reduced pressure.
28.5 g of a fraction of ~97°C/3 mmHg was obtained. As a result of GLC-MS analysis, the obtained substance was found to be cis-diasmone. pair 2-(1,3-pentadienyl)-3-
Theoretical yield of methyl-2-cyclopenten-2-one
87%.

Example 2 Hexacarbonyl molybdenum in an autoclave
Charge 7.8g (0.03mol), 32g (0.2mol) of 2-(1,3-pentadienyl)-3-methyl-2-cyclopenten-1-one, and 200ml of benzene, and heat at 120 to 140℃ under hydrogen pressure of 100Kg/ ^cm3. , react for 5 hours. After the reaction was completed, post-treatment and vacuum distillation were carried out in the same manner as in Example 1 to obtain 28 g of a fraction having a temperature of 95 to 97°C/3 mmHg. As a result of GLC-MS analysis, the obtained substance was found to be cis-diasmone. vs. 2-(1,3-pentadienyl)
-3-Methyl-2-cyclopenten-2-one theoretical yield 85%.

Example 3 In an autoclave, 0.035 g (0.0001 mol) of hexacarbonyltungsten, 2-(1,3-pentadienyl)-3-methyl-2-cyclopentene-1
Charge 3.2 g (0.02 mol) of 100 ml and 3 ml of methanol, and react at 190 to 200°C for 4 hours at a hydrogen pressure of 50 Kg/cm ³ . After the reaction was completed, post-treatment and vacuum distillation were performed in the same manner as in Example 1 to obtain 29 g of a fraction having a temperature of 95 to 97°C/3 mmHg. When this fraction was analyzed by GLC, it was found to be a mixture of 96% cis-diasmone and 4% trans-diasmone.

Claims (1)

[Claims] 1. The following formula () 2-(1,3-pentadienyl)-
3-methyl-2-cyclopenten-1-one,
The following formula () Mx (CO) y (arene) z () However, in the formula, M represents a metal atom selected from the group consisting of Cr, Mo and W, arene represents an arene ligand, and x represents 1 or 2, and y is 3
The following formula () is characterized in that an integer of ~6 is subjected to a catalytic hydrogenation reaction in the presence of a metal carbonyl compound or an arene complex catalyst thereof represented by: where z represents O or an integer of 1 to 3, The manufacturing method of Sis-Jiasmon expressed as .