JPH02160755A - Cyclohexanenitriles - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (Y is H, OH, group shown by formula II, double line is double bond when Y is H and single bond when Y is other group). EXAMPLE:3-(2,2,3R-Trimethyl-6-methylenecyclohexyl)acrylonitrile. USE:A synthetic intermediate for alpha- or beta-irones. Useful as durable fragrance and flavor imparter or modifier. PREPARATION:(+)-Citronellic acid alkyl ester shown by formula III (R<a> is alkyl) as a starting substance is successively reacted and derived into a 3-(2,2,3R- trinethyl-6-methylenecyclohexyl)-2-phenylselenylpropionitrile shown by formula IV. Then the compound is reacted with hydrogen peroxide in the presence of a base in an organic solvent at 0-50 deg.C to give a compound shown by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is useful as an intermediate for the production of a- or β-ylones, known compounds of natural origin, and is also useful as a long-lasting aroma and flavor imparting or modulating agent. This invention relates to compounds, their production methods, and further their uses.

More specifically, (+)2R26R, which has not been described in the prior literature and is represented by the following formula (2),
- The following formula (1) is characterized in that trans-γ-ylon is brought into contact with an acid catalyst. The present invention relates to compounds which have not been described in the literature and are useful as flavor imparting or modulating agents, in which one of the amounts is a double bond and the other is a single bond, methods for their production, and uses thereof.

The above formula (1) compound includes the following formulas (1)' and (1)" compounds (-)-2R, 61'L -) lance-α-ironny (extra-6R-β-ironny) the above formula ( The compound represented by formula (1) consisting of α- or β-ylons of 1)' and (1)
spallida, Ir1s germanica)
Cheiranthus cheiri is a known substance in an optically active form that naturally exists in the rhizome oil of Cheiranthus cheiri, the flower essential oil of Cheiranthus cheiri, etc., and is an expensive and difficult-to-obtain naturally-sourced fragrance substance.

In this oil, there are three isomers of α-1β-1γ-, cis- and trans-isomers derived from the three-dimensional structure of the side chain, and optical isomers, and there are many iron isomers. It is usually used in the form of a mixture.

←)-2R of the formula (1)' is a key substance in the oil.

6 R-) raysu α-10 and the above formula (1) “
←)-6R-β-yron is the most excellent violet fragrance.

However, to date, there have been no reports of production using synthetic methods; only that it is known to exist naturally. For example, J.Org.

Chem, Vol. 34, p. 153, states that racemic forms d and l can be obtained from dimethylhebutenone through multiple steps and complicated operations.
A method for synthesizing -alpha-iron is described. Also, J
, Am, Chem, Soc, vol. 131, 29
No. 05 describes a method for synthesizing racemic d,I-α-ylon from α-pinene in multiple steps and through complicated operations. Furthermore, J, Org.

Chem, Vol. 45, p. 16 describes a method for synthesizing a racemic form, and there are many other reports, but all of them are only methods for synthesizing racemic irone.

The present inventors have discovered the (-3-2R, 6R, -)u/su-alpha-ylon and (
Research was conducted to provide a method for synthesizing +)-6R-β-iron.

As a result, the present inventors took an entirely new synthetic route (−
)-2J6-trans-α-iron and (t)-6
It has been discovered that R-β-ylon can be produced industrially advantageously.

According to the research conducted by the present inventors, it has been discovered that the α- or I-iron of the above formula (1) can be synthesized, for example, as follows.

((1)-Represented by the following formula (141), where R represents a lower alkyl group, which can be easily produced from citronellal (
g)-The following formula (13), which has not been described in any prior literature, can be formed by contacting an alkyl cutronellilate with a methylating agent in the presence of a base catalyst, where 几2 represents a lower alkyl group. 2, 3R,? -) Rimeteru 6
- By contacting an alkyl octenoate with a methylating agent in the presence of a base catalyst and then hydrolyzing it, the following formula 1 is obtained:
2, represented by 2, 2, 314, ? -Tetramethyl-6-octenoic acid can be produced.

The compound of formula (12) that can be obtained by pressing as described above is obtained by contacting it with a halogenating agent and then subjecting it to a ring-closing reaction in the presence of a Friedel-Crafts catalyst to obtain the compound represented by the following formula (11): 2, 2.3R-)rimether-6-(1-methyl-1-chloroethyl)cyclohexanone can be formed, and by contacting the compound of formula (11) with a dehydrohalogenating agent, the compound represented by the following formula (103) can be formed. 2, 2.
8R-) dimethyl-6-ingropylidenecyclohexone can be produced.

The compound of formula (1o) that can be obtained as described above is obtained by contacting it with a reducing reagent, acetylating the product, and then subjecting it to onion decomposition treatment to form 2R represented by the following formula (9). -acetyloxy-3,3゜4R-trimethylcyclohexanone, after reacting the compound of formula (9) with Ph3P=CHOCH, (Ph represents a phenyl group) and treating the product with an oxidizing agent. By fusion with a deacetoxylation agent, a compound of the following formula (8) can be obtained.

8,3. expressed by the above formula (8) that can be obtained as described above. AFL-) samethyl-1-cyclohexenylcarbaldehyde is contacted with a reducing reagent and then
By contacting the product with ethyl vinyl ether in the presence of mercury acetate, 3,3,4R-)dimethyl-1-cyclohexeral methyl vinyl ether represented by the following formula ('?) can be obtained, and the formula (7) By subjecting the compound to thermal rearrangement, 2,2. SR-trimethyl-6-methylene-1-cyclohexylacetaldehyde is obtained, and the compound of formula (6) is converted into 8-represented by the following formula (5) by contacting it with potassium cyanide in the presence of acetic acid.
It can be converted to (2,2,3R,-trimethyl-6-methylenecyclohexyl)-2-hydroxypropionitrile.

The compound of formula (4) obtainable as described above can be prepared by contacting it with mesyl chloride in the presence of a base and then contacting the product with sodium selenophenoxide. ), a−(2
,2,3B,-)trimethyl-6-methylenecyclohexyl]-2-phenylselenylpropionitrile, and the compound of formula (4) can be obtained by contacting it with hydrogen peroxide in the presence of a base. , the following formula (3), converting to (+)-2R,6R-) lance-γ-ylon represented by 3-(2,2,3R-)rimether-6-metelenichexyl)acrylonitrile represented by the following formula (3). Can be done.

According to the method of the present invention, the compound of formula (2), which can be obtained as described above, is brought into contact with an acid catalyst to synthesize the compound of formula (1) with the compound listed in formula (1). ) It has been found that in addition to being useful as a synthetic intermediate for compounds, it is also useful as a persistent aroma and flavor imparting or modulating agent.

However, in the formula, R represents a hydrogen atom or a lower alkyl group, FLl represents a hydrogen atom or a methyl group, and here,
An octanoic acid derivative in which R and 1 are not hydrogen atoms at the same time.

However, in the formula, X is an oxygen atom, O■-■ group or 0COC
R, represents a group, where when X is an oxygen atom, 2 represents a double bond (=), and when X is another group, 2 represents a single bond (... A cyclohexane derivative represented by showing a bow.

The following formula (C), where R2 is CHO, CH20H or CH, O
A cyclohexene derivative represented by: CH=CH.

The following formula (D), however, in the formula, Z represents an oxygen atom or CH2, and when Z is an oxygen atom, the layer 3 is ----- OCOCH
3 groups, and when Z is CH2, R3 is CI-I, C
A cyclohexane derivative represented by HO group.

The following formula (E), where Y is a hydrogen atom, an OH group or an atom, = represents a double bond (=), and when Y is another group, = represents a single bond (- ), cyclohexane nitriles represented by

Therefore, the object of the present invention is to obtain the (-) of the optically active substance of formula (1), which was successfully synthesized by the present inventor for the first time.
-2R,,6R-) lance-α-iron and (+)-
The object of the present invention is to provide undocumented intermediates useful for the production of 6R-β-irono long strips; a method for producing them; and a long-lasting flavor imparting or modulating agent using them.

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

Formula (1) of the present invention (-)-2,6R,-)lance-
α-Iron and (+)-6R,-β-Iron, for example, can be industrially advantageously produced from the compound of formula (14) obtained from (di-citronellal) as shown in the reaction process diagram below. Can be done.

Hereinafter, the production of the compound of formula (1) will be explained in more detail using the above embodiment as an example.

2.3R of the above formula (13), ? -) It can be easily obtained in good yield by methylating lower alkyl riftyl-6 acid (eg, methyl, ethyl, etc.) with a methylating agent.

The reaction can be carried out, for example, by contacting with a methylating agent in an organic solvent in the presence of a base catalyst. The organic solvent used in this case is preferably an anhydrous or substantially anhydrous organic solvent.

The reaction temperature of the above methylation reaction can be selected as appropriate and is also selected depending on the type of organic solvent used, but for example,
A temperature range of about -7oO to about 100°C can be exemplified.

More preferably, a reaction temperature of about -60' to about 50°C can be exemplified. There are no particular restrictions on the reaction time, but the reaction time may be, for example, about 1 to about 4 hours.

Specific examples of organic solvents used in the reaction include benzene,
Examples include toluene, xylene, and tetrahydrofuran. These solvents can be used alone or in combination of two or more.

There is no particular restriction on the amount of these solvents used, but the formula (
For example, the amount used is about 1 to about 20 times the weight of 14).

Specific examples of the base catalyst used in the above reaction include alkali metal amides such as potassium amide, indium amide, lithium amide, and lithium diimpropylamide. The amount of these base catalysts to be used is preferably about 1 to about 1θ times the mole of the compound of formula 4, more preferably about 1 to about 8
A double molar ratio is often adopted.

Furthermore, examples of the methylating agent used in the above reaction include methyl halides such as methyl iodide, methyl bromide, and methyl chloride, as well as dimethyl sulfate. The amount of these methylating agents used is:
For the compound of formula (14), preferably about 1 to about 5
An example is a range of twice the molar range. After the reaction is completed, for example, extraction with an organic solvent, washing with water, distilling off the solvent, and then distillation under reduced pressure is performed to obtain a boiling point of 68° to 70°C.
The compound of formula (18) having 1 walt can be obtained.

Next, 2. of the formula (12) is obtained from the compound of the formula (13).
2.3R,? -Tetramethyl-6-octenoic acid is synthesized by bringing the compound of formula (13) into contact with a methylating agent in the presence of a base catalyst to synthesize the formula (12-1),
This can then be easily carried out in good yield by alkaline hydrolysis using a conventional method.

Methylation in the above reaction can be carried out by hydrolyzing with an alkali similar to the method for synthesizing the compound of formula (13) from formula (14), with a boiling point of 85 to 88°C/
The compound of formula (12) of 2 IuHr can be produced.

Furthermore, from the compound of formula (12), 2,2.3R-)dimethyl-6-(1-methyl-
1-Chloroethyl) cyclohexano/For total synthesis,
The halogenation reaction can be carried out by bringing the compound of formula (12) into contact with a halogenating agent and then subjecting the compound to a ring-closing reaction in the presence of a Friedel-Crafts catalyst.The halogenation reaction is preferably carried out in an organic solvent; Specific examples of organic solvents include benzene, xylene, toluene, etc. There are no particular restrictions on the amount used, but for example, it is preferably about 5 to An example of the amount used is about 20 times the weight.

Specific examples of the halogenating agent used in the reaction include oxypril chloride, thionyl chloride, phosphorus trichloride, and phosphorus pentachloride.

The amount of these halogenating agents used is the formula (12)
For example, the amount used may be about 1 to about 20 times the amount of the compound, preferably about 2 to about 10 times the amount by mole. The reaction temperature and reaction time can be appropriately selected, and for example, although they vary depending on the organic solvent used, a reaction temperature of about 1 to about 00°C and a reaction time of about 2 to about 5 hours can be exemplified.

Further, the Friedel-Clafuso catalyst and material used in the ring-closing reaction are, for example, AlCl, , sbc+, , Feel
, ,TeCI, ,S nCI, , '1'' iCI
,,ZnCI, ,HF, H,S04,H3PO4,
Examples include combinations thereof. The amount used is, for example, about 1 to
A range of about 20 molar times is often adopted. At this time, it is preferable to carry out the reaction in the presence of an organic solvent, and examples thereof include organic solvents such as dichloromethane and trichloromethane. As the reaction source) f, for example, a range of about -70° to about 100°C can be exemplified.

After the reaction is completed, it is washed by a conventional method, for example by distillation, and the formula (having a boiling point of 70 to 75°C (oil bath temperature + 15.Hp)
11) A compound can be obtained.

Furthermore, the formula (10) 2,2. aJ small=i mountain i tip To produce cetyl-6-itubropylidene-7 chlorohexanone, for example, the formula (
11) It can be easily produced in good yield by contacting the compound with a dehydrohalogenating agent, preferably in an organic solvent.

This dehydrohalogenation reaction may be carried out by any means known per se, but in the present invention, a solid adsorbent or a solid adsorbent such as a basic ion exchange resin may be used in basic or under basic conditions. The reaction is preferably carried out in the presence of a hydrogen halide agent or a solid hydrogen halide receptor.

Specific examples of such solid dehydrohalogenation agents or solid hydrogen halide receptors include alumina, silica gel, activated clay, zeolite, lithium carbonate, and the like. These are optionally used in the form of basic solid adsorbents pretreated with a base, preferably a base such as pyridine, triethylamine, diethylamine, pyrrolidine, piperidine, piperazine, morpholine, dimethylacetamide, etc.; It can be used in the form of a solid adsorbent under basic conditions in which such a base is present in the reaction system.

There are no particular restrictions on the amount of such solid dehydrohalogenation agent or solid hydrogen halide acceptor;
It can be selected and implemented as appropriate. For example, the formula (11
) The amount used may be in the range of about 0.1 to about 20 times the weight of the compound, more preferably about 0.1 to about 10 times the weight of the compound.

The reaction can be carried out by bringing the compound of formula (11) into contact with a solid dehydrogenation agent or a solid hydrogen halide acceptor as described above, and the reaction temperature is as follows:
For example, about Oo to about 200°C, more preferably about 40° to
A temperature of about 60° C. can be exemplified. Specific examples of solvents used in the reaction include benzene, toluene, xylene, cyclohexane, cyclopentane,
Examples include diethyl ether, tetrahydrofuran, and methyl ethyl ketone. The amount of these solvents to be used can be selected as appropriate, and may be, for example, about 1 to about 30 times the weight. The reaction time is
For example, it is preferable to adopt a reaction time of about 5 to about 50 hours. After the reaction is complete, it is extracted with an appropriate solvent and distilled to obtain the formula (
10) The compound can be obtained in good yield.

The formula (932R-acetoxy-3,3゜4R-
) to synthesize rimethercyclohexano/, the formula (10
] Preferably in the presence of an organic solvent 3R-)IJ Methylcyclohexane-1S-ol is acetylated to produce the compound of formula (9-13), and then the compound is subjected to ozonolysis treatment, preferably in an organic solvent. The impropylidene bond is cleaved by contact with ozone, and the compound of formula (9) can be easily produced.

Preferred examples of the reducing reagent used in the above reduction reaction include lithium aluminum hydride, lithium boron hydride, and sodium poron hydride. The amount of these reducing reagents to be used is determined by the formula (lO)
A preferred example is about 1 to about 10 times the amount of the compound.

At this time, it is preferable to carry out the reduction reaction in an organic solvent.

Examples of such organic solvents include ether and tetrahydrofuran, and the amount used is, for example, about 1 to 50 times the weight of the compound of formula (10). The reaction temperature is about 0.6 to about 1
A temperature range of about 00°C is often employed, and the reaction time is, for example, about 1 to about 5 hours. In this way, the compound of formula (9-2) can be easily obtained in good yield (boiling point 80°C (oil bath temperature) / 5 wHf
).

Next, by reacting the compound of formula (9-23) with acetic anhydride in the presence of pyridine, for example, the compound of formula (9-23) is reacted with acetic anhydride in the presence of pyridine.
-13 compound can be easily produced with good yield (boiling point: 70° C. (oil bath temperature): 15 mHy).

Furthermore, 2.2.3R-)dimethyl-6 of the formula (9-1)
~Impropylidene-1S-acetoxin clohexa/
The compound of formula (9) can be easily synthesized by contacting, for example, with ozone in an organic solvent.

The above-mentioned contact with ozone is preferably carried out at a low temperature, for example, about -780 to about +30°C, more preferably about -7°C.
Examples of low temperature reaction temperatures, such as from 8 DEG to about -30 DEG C., can be achieved. The reaction time can also be changed as appropriate depending on the flow rate of ozone used, the reaction temperature, etc., and can be exemplified by a reaction time of about 1 to about 20 hours.

The amount of ozone used in the above reaction can also be appropriately selected; for example, about 0.8
An example of the amount used is about 3 mol to about 3 mol.

Specific examples of the solvent used in the embodiment in which contact with ozone is carried out in the presence of a solvent include pentane, hexane, cyclohexane, carbon tetrachloride, chloroform, methylene dichloride, and the like. There is no particular restriction on the amount of these solvents used, but if the above formula (9-1)
Preferably, the amount used is about 10 to about 50 times the weight of the compound.

After the reaction is complete, extract with a suitable organic solvent such as ether,
After washing with water, the solvent is distilled off, and the product is purified by, for example, a silica gel column (n-hexane:ether) for 20 minutes, and then recrystallized from hexane to form colorless needle-like crystals (melting point: 70-71°C).
) can be easily synthesized.

3.3.4R-)IJ methyl-1- of the formula (8) from the compound of the formula (9) that can be obtained as described above.
To produce cyclohexenyl rubaldehyde, the formula (
9) Compound, for example, methoxymethylenetriphenylphosphorane prepared in advance in an organic solvent, Ph, P=C
I (OCR, (Ph represents a phenyl group)) to form 1-methoxymethylene-2R-acetoxy-3,3
,4R-trimethyl7chlorohexane and then
For example, treatment with an acid such as perchloric acid to form 2R-acetoxy-3.4R-IJ methyl-1-cyclohexenyl carbaldehyde is followed by contact with a deacetoxy agent such as alumina to form the formula [8 ) compounds can be easily produced.

The contact reaction between the compound of formula (9) and methoxymethylenetriphenylphosphorane is preferably carried out in an organic solvent, and specific examples of the solvent include benzene, toluene,
Examples include xylene and tetrahydrofuran. There are no special restrictions on the amount of solvent used, but for example,
A range of approximately 1 to 10 times the weight of the compound of formula (9) is often employed. The amount of methoxymethylenetriphenylphosphorane to be used is preferably in the range of, for example, about 1 to about 10 times the mole of the compound of formula (9).

The reaction temperature and reaction time can be appropriately selected depending on the type of solvent used, and examples thereof include a temperature of about 5 to about 50°C and a time of about 5 to about 30 hours.

1-Methoxymethylene-2R- which can be obtained above
The catalytic reaction of acetoxy-3,8,4R-)rimethercyclohexane with a conventional acid system such as perchloric acid can be carried out, for example, at a rate of about 0.00
It can be carried out at a temperature of about 100° C. to about 100° C. and for a time of about 1 to 5 hours, for example. At this time, it is preferable to carry out the reaction in an organic solvent such as ether or tetrahydrofuran. Next, the reaction in which the obtained acetoxy-3,3,4R-)dimethyl-1-chlorine\xenylaldehyde is brought into contact with a deacetoxy agent such as Flumina can be carried out using a column method, a batch method, etc. You can choose to do so. The reaction temperature is, for example, about 5° to about 5°
Temperatures of about 0°C can be mentioned. At this time, it is preferable to use an organic solvent such as cyclopentane, hexane, pen/tane, or ether. After the reaction is completed, the compound of formula (8) can be easily obtained by employing purification means such as silica gel column chromatography.

In order to produce the above formula (7) 3,8.4R-trimethyl-1-7 chlorohexenyl methyl vinyl ether from the W notation formula (8) compound, the above formula (7) compound is brought into contact with a reducing reagent. -113,3,4R-)dumethyl-l-cyclohexenylmethanol and then formula (7
This can be easily accomplished by contacting the -13 compound with ethyl vinyl ether in the presence of mercury acetate. Examples of the reducing reagent used in this reduction reaction include lithium aluminum hydride, lithium poron hydride, and aluminum boron hydride. The amount used is, for example, about 1 to
A preferable example is about 10 times the amount by mole.

Wear. Assuming the amount used, for the compound of formula (8),
For example, the amount used may be about 1 to about 10 times the weight.

The reaction temperature and reaction time can be appropriately selected depending on the solvent employed, and examples thereof include a temperature of about 0° to about 100°C and a reaction time of about 1 to about 10 hours.

The amount of ethyl vinyl ether used to produce the compound of formula (η) from the compound of formula (7-17) is as follows:
For example, the amount used can be about 6.1 to about 5 times the mole of Compound 7-13. Further, the amount of mercury acetate used at this time can be, for example, about 1 to about 1.theta. times the amount of ethyl vinyl ether by mole.

The reaction may be carried out, for example, at a temperature of about 10° to about 40°C and about 1
This can be carried out for about 0 to about 100 hours. After the reaction is complete, extract with an organic solvent such as ether,
The compound of formula (7) can be easily produced by washing with water and distilling off the solvent.

The 2,2.3-trimethyl-6-methylenecyclohexylacetaldehyde of the formula (6) can be easily produced by subjecting the compound of the formula (7) to a heating rearrangement reaction. The reaction is carried out, for example, from about 100° to about 30°
It can be carried out at a temperature of about 0° C. and for a time of about 1 to about 10 hours, for example.

At this time, it is desirable to conduct the reaction in a closed system. After the reaction, the compound of formula (6) can be easily obtained by separation and purification using purification means such as column chromatography.

8-(2,2,3-trimethyl-6- of the formula (5))
(methylene S÷ocyclohexyl) -2-≠two; Bio= ) IJ # can be easily prepared, for example, by contacting the compound of formula (6) obtainable as described above with acetic acid and potassium cyanide, preferably in an organic solvent. The reaction can preferably be carried out at a temperature of, for example, about 30° C. to about 150° C. and a reaction time of, for example, about 1 to about 5 hours. Specific examples of the organic solvent used in the reaction include methanol, ethanol, propatool, and the like. There are no special restrictions on the amount of organic solvent used, but
It is preferable to use, for example, about 1 to about 10 times the weight of the compound of formula (6). The amount of potassium cyanide to be used is, for example, about 1 to about 30 times the amount of the compound of formula (6) by mole. Further, the amount of acetic acid to be used may be, for example, about 1 to about 10 times the amount of potassium cyanide by mole. After completion of the reaction, the compound of formula (5) is extracted with an organic solvent such as ether, neutralized with a suitable alkali, washed with water, distilled off the solvent, and purified using a purification means such as column chromatography. can be easily manufactured.

8-(2,2゜3R,-trimethyl-6-methylene/-1-cyclohexyl]-2- represented by the formula (4) from the compound of formula 〇) which can be obtained as described above.
To produce phenylselenylpropionitrile, a compound of formula (5) is contacted with mesyl chloride in the presence of a base catalyst to form a mesylate of the compound of formula (5), and this mesylate compound is then treated with a pre-prepared solvent. It can be easily produced by contacting with dium selenophenoxide.

Examples of the base catalyst used in the above reaction include pyridine,
Preferred examples include piperidine, triethylamine, and pyrolisif. The amount of these base catalysts to be used is, for example, about 1 to about 5 times the mole of mesyl chloride. The amount of mesyl chloride used in the reaction is preferably about 1 to about 10 moles per mole of the compound of formula (5). The reaction is carried out, for example, at about -5° to about +50°C.
The reaction can be preferably carried out at a temperature of about 100 mL and a reaction time of about 1 to 5 hours, for example. The amount of sodium chloride to be brought into contact with the mesylate compound of formula (5) obtained above is as follows:
For example, the amount used may be about 1 to about 10 moles.

The reaction is preferably carried out in an organic solvent such as ethanol, and the reaction temperature and reaction time can be appropriately selected depending on the type of solvent used, but for example, from about -50 to about +10
Examples include temperatures of about 0° C. and reaction times of about 1 to about 10 hours. After completion of the reaction, the compound of formula (4) can be easily produced by extracting with an organic solvent such as ether, washing with water, distilling off the solvent, and purifying using a purification means such as column chromatography. can.

For example, to produce 3-(2,2,3R,-trimethyl-6-methylene-1-cyclohexyl)2-acrylonitrile of the formula (3) from the compound obtained as described above, , can be easily carried out by bringing the compound of formula (4) into contact with aqueous hydrogen peroxide in the presence of a base. The reaction is preferably carried out in an organic solvent, for example at a reaction temperature of about 0° to about 50°C. Specific examples of the solvent to be used include dichloromethane, trichloromethane, and carbon tetrachloride.

Preferred examples of the base used include pyridine, piperidine, and triethylamine. An example of the amount of hydrogen peroxide used is about 4 times, for example, about 1 to about 10 times the amount of the compound of formula (4). After the reaction, the compound of formula (3) can be easily synthesized by extracting with an organic solvent such as ether, washing with an aqueous copper sulfate solution and water, and distilling off the solvent, using a purification method such as column chromatography.

In order to produce lance-r-ylon of the following formula (represented by ←)-2R,,6R-) from the compound of the above-mentioned size that can be obtained as described above, the compound of formula (3) is converted into methyl This can be easily achieved by contacting with lithium. The reaction is preferably carried out in an organic solvent, and organic solvents such as flJ ether, tetrahydrofuran, etc. can be preferably employed. The reaction temperature and reaction time can be appropriately selected depending on the solvent used, but for example, from about -600 to
A reaction temperature of about +50° C. and a reaction time of, for example, about 1 to about 5 hours can be exemplified. The amount of methyllithium used in the above reaction is preferably in the range of, for example, about 1 to about 10 moles relative to the compound of formula (3).

After the reaction is completed, the product is treated with ammonium chloride, extracted with an organic solvent such as ether, washed with water, and the solvent is distilled off.
For example, using purification means such as column chromatography, formula (2)
Compounds can be easily produced.

According to the present invention, for example, by contacting the formula (2) obtainable as described above with an acid catalyst, the (-)-2R,6-trans represented by the following formula (1), -α-ylon and (-β-ylon) can be produced. By isomerizing the two compounds of formula (2) in the presence of an acid catalyst, the compound of formula (1) can be easily produced. Specific examples of acid catalysts used in the reaction include sulfuric acid, phosphoric acid, hydrochloric acid, and p-toluenesulfonic acid. Amounts in the range of about .01 to about 1 weight percent, more preferably about 0.1 to about 0.3 weight percent, are often employed.

The reaction temperature can be, for example, about -10°C to about +80°C, and the reaction time can be, for example, about 5 to +80°C.
An example of this is about 10 hours.

After the reaction is completed, the compound of formula (1) is extracted with an organic solvent such as ether, washed with an appropriate alkaline aqueous solution and water, and the organic solvent is distilled off. Compounds can be easily produced. The light absorption degree of the compound of formula (1) is [α)” knee 318° (C, 0,326,
Solvent CH, C1,) and NMR,, IR, Mas
's was completely consistent with that of the natural product.

Furthermore, the MR, IR, and Mass of the compound of formula (2) completely matched those of the natural product.

In the present invention, the synthesized compound of formula (1) is widely used as an aroma and flavor component similar to the known natural source compound of formula (1). As such, they are useful as persistent aroma and flavor imparting or flavor modulating agents. These compounds are useful in, for example, fields of application such as food and beverages, luxury goods, feeds, health care and pharmaceuticals, and cosmetics.

Reference Example l Synthesis of (+)-3R-methylcitronellaic acid (+)-
Dissolve citronellal (xa31Rg, t, 9 mmol) in acetone (3 m/). Add a small amount of Celite. Add John's reagent (about 2 coats!) with OC and stir for 1 hour with OC. Methanol is then added with OC to reduce excess chromic acid, ether is added to the reaction mixture and extracted with IN sodium hydroxide. The aqueous layer was made acidic with 7% hydrochloric acid,
Extract ether. The organic layer was washed with water and saturated brine, dried, and then the solvent was distilled off to obtain +)-38-methylcitronellaic acid. (Yield 150 74%) Reference
Example 2 Synthesis of compound of formula (14) (+)-38-methylcitronellaic acid (16,74t, 9B, 5m, tnol) obtained as described above
) to a methanol (300 ml) solution was added 0.2 at of concentrated sulfur, and refluxed day and night. After distilling off the methanol, ether is added, neutralized with aqueous sodium bicarbonate solution, and extracted with ether. The organic layer was washed with water and saturated brine, and after drying, the solvent was distilled off, and the obtained oil was distilled under reduced pressure.
).

Boiling point 71'-73 C/mmIl gIR; 1
740α-1 NMR; δ(, CC14) to oMH.

0.96 (d, 3H,,7=6), 1.2-1.5
(m, 2H), 1.60 (8, 3H), 1.70 (s
, 3H), 1.8-2.5 (?7L, 5H), 3.
66 (S, 3H), 5.10 (t, tH)
Analysis value Calculated value as CllH2O02: C, 71,69%; B, 10.94% Measured value:
C, 71,57%: H, 11,23% lol Example
1 Formula (13)2. aR,7-)rifthyl-6-omo Under a stream of argon, diisopropylamine (16,51R1, l
18 mmol) of anhydrous tetrahydrofuran (10
0m+/) solution at -60C.
3xi, 94.4 mmol) f dropwise and stirred at -60C for 30 minutes. The methyl ester formula (14) compound (14,4) obtained as in Reference Example 2 was added to this solution.
9t, 7B,, Tmmol) in anhydrous tetrahydrofuran (60 sy/) is added at -60C and stirred at -60° to -400 for 1 hour. Next, reaction solution 1-60
Cool to C and add methyl iodide (9,8xi).

15? mmol)'fr: Add gradually, and after dropping, stir at -60° to -400 for 1 hour. Ether and water are added to the reaction mixture, the organic layer is washed with water, and the aqueous layer is extracted with ether. The organic layers are combined, washed with water and saturated saline, and dried. After distilling off the solvent, the obtained oil was distilled under reduced pressure to obtain the formula (13) (13,46f).

86%).

Boiling point 68-70 C/ 1 mxli g Example 2 Formula (12-1) 2,2.3R,? -tetramethyl-6-
Synthesis of methyl octenoate Diisopropylamine (5.9 m/!
, 42 mmol) of anhydrous tetrahydrofuran (40
m/) solution at -600 n-butyllithium (22-4
ml, 33.6 mmol) f dropwise and stirred for 30 minutes. Add monomethyl formula (13) (5,54t) to this solution.
, 28.0 mmot) of anhydrous tetrahydrofuran (
30s + t) Add the bath solution at -50C and boil for about 2 hours.
The temperature was raised to c-i, cooled again to -60C, and methyl iodide (41d, 64 mmol) was added, and the mixture was incubated for 1 hour. Add ether and water to the reaction mixture, wash the organic layer with water, and re-extract the aqueous layer with ether.

The organic layers are combined, washed with water and saturated saline, and dried.

After distilling off the solvent, the obtained oil was separated and purified using silica gel column chromatography (n-hexane:ether = 20:1) to obtain oily dimethyl ester (5,54F, 93%).
get.

bp 85-88 C/2 mgHgIR; ν(
liquid film) 1740.1380cm-'NMR, δ(CC1
4 solution) 100Ml120.85 (d, 3H, J=
7), t, os (s.

MgX2), 1.60 (S, 3B), 1.70 (s,
3H), 1.0~Z2 (m, 5H), 3.64
(1,3H), 5.08 (1!, IB) Analysis value CI>B
Calculated value as 2402: C, 73,53%; #, 11.399 Measured value: C, 73,29%; H, 11,23% Implemented
Example 3 Equation (12) 2, 2, 3/'i',? -tetramethyl-6
-Synthesis of octenoic acid, dimethyl ester formula (12-1) (5,36f).

25.3 mmol) of ethanol (t 20 a
) Potassium hydroxide (14,2y, 253m
mot) Dissolve in as little water as possible (approximately 25 R/ml) and add.

The ethanol is refluxed for 3 days under argon. Most of the ethanol is distilled off and ether is added to the remaining oil. Extract the organic layer with water three or four times. Merging the water layers 7
After making it acidic with hydrochloric acid, extract it with Able. After washing the organic layer with water and saturated brine and drying, the bath portion is distilled off to obtain an oily carboxylic acid (4,98S', 99%).

IR; ν (liquid film) 2400-3500.

1700m-1 NMR; δ (CCt, solution) 100A/Hg0.91
(d, 3H, J='l) t, to (s, 6#) 1.59 (S, 3#) 1.69 (S, 3H) 1.2~z2 (m, 5H) 5.05 ( t, 1#) 11.8-12.2 (fi, LH) Example 4 Formula (11) Synthesis of 2,2.3R-trimethyl-6-(1-methyl-1-chloroethyl)cyclohexanone Nicarboxylic acid formula (12) (12-88P, 65.1mm
Oxalyl chloride (17 m/, 195 mmol) was added to an anhydrous penzea (250 tri) solution of ot) at room temperature, stirred at room temperature for 1.5 hours, and then refluxed for 3 hours. After distilling off the tofu, the oily residue is dissolved in anhydrous methylene chloride (250d). To this solution under a stream of argon,
Stannic chloride (7,511Lt, 65.1mmol)
A solution of anhydrous methylene chloride (15i+l) was added dropwise at -650C, and the mixture was heated at -65 to -50C for 3 hours. A saturated aqueous sodium hydrogen carbonate solution was added at -500 °C and the temperature was raised to OC.

Celite Shen #? Apply suction using fPa and wash the precipitate thoroughly with ether. Extract P solution with ether, wash with water and saturated saline, and dry. The crude product obtained by distilling #k off is 70
Minute F using lysyl column chromatography (developing solvent n-hexane)
fI to obtain an oily ketone (10.76f, 76%).

HP? 0C (-oil bath temperature) 15flHgIR, ν(
liquid film) 1710 cIn-” NMR, δ (cct4 solution) 100 A (Hzto (sH
), t, 54 (a, aH), 1.71 (s, 3B), 1
4~! ? (m.

lH), 2.92 and 3.04 (t.

total lH, J=5) Analysis value C,, H2, calculated value as QCl: C, 66,50%; H', 9.77%-
Cl, 16.36% Measured value: C, 66,44%; H, 9,72%; Cj, 1
6.29% Example 5 Formula (10) 2,2,37i'-13methyl-6-
Synthesis of itupropyl+1de/cyclohegisanone Lithium carbonate ([50f, 115mtnol) was added to a solution of the knee ketone formula (11) (zsor, l L5 mmol) in anhydrous dimethylacetamide (100 l), and the mixture was heated at 100C.
Heat for 6 hours. The reaction mixture is filtered with suction, and the F solution is extracted with ether. Wash the organic layer with water, water #? Extract with ether. Combine the organic layers (5), wash with water and saturated saline, and dry. When the bath fs is distilled off, an oily enone (Z06F,
A crude yield of 99%) is obtained.

IR; ν (CCI, solution) 169.0c+a-Otori NM
R: δ (CCt4 solution) 60 MHz, g ~1.
2 (Mex3) 1.73 (6υs, 611) 1.5~Z8 (m, SR) Example 6, Formula (9-2) a-<u propylidene)-2°2.
3R-trimethylcyclohexane-1B-;4-:
- enone formula 1017) crude product (ZO6fJl11.4m
In anhydrous ether (100 mg) solution of water-accumulating lithium aluminum A (433j9, 11.4 mmol)
) 'r: Add with Or and stir for 30 minutes under an argon stream. Add 1 portion of ether and then 1 portion of water to the reaction mixture.
Decompose β-residue lithium aluminum hydride. The reaction mixture was filtered through Celite, subjected to AM, and dried over anhydrous magnesium chloride. When the solvent is distilled off, an oily alcohol (2,13F quantitative) is obtained.

bp 80G (oil bath temperature) 15 Dragon Hgν (liquid film) 35
00.1380 (1!l1l-breath δ (CCt, solution)
100 Dragon Hz o, 83 (s, 3B), 1.01 (g, 3H)
, 1.13 (d, 3H, J=6), 1.2~Z O(
m, 4B), 1.70 (S, 3H), 1,75 (S
, 3H), 11-14 (771, 2H), 4.10 (
5,1B) Analysis value Total p-value as Cl211□O: C, 79,06%; H, IL16% Measured value: C, 78,91%; H, 1140% 2.3R-)limethyl-IS-cyclohexyl Cetate: crude product of monoalcohol formula (9-2) (zx3t.

Approximately 11.4 mmol), anhydrous vinegar L'eR (8,8
m/) and Bi1) Shin (2216)'r: Mix and heat to 70C under argon flow for 8 hours. Water and ice were added to the reaction mixture, and the mixture was vigorously stirred for 2 hours under OC, and the reaction solution was extracted with ether. Wash with organic #all water and extract with water If ether. The dominant layer is combined, washed with 10% steel sulfate aqueous solution and saturated saline, and dried. When the solvent is distilled off, oily acetate-1-(targeting zs3r concentration) is obtained.

hp ToC (oil bath temperature) 151 blade HgIR: ν(
Liquid film) 1740m-1 HMR, δ (CCt, solution) l OOMIj zO,
92CMeX2), 1.12 (d.

3H, J=7), 1.3-1.6 (m.

3H), t, 7t (s, 3B), 1.78 (S, 3H)
, 1.98 (5,3B), 1.1~1.2 (m, 2
H), s, aa (s.

lH) Analysis value Calculated value as Cl482402: C, 74,95%; H, 10,78% Measured value:
C, 74,64%; R, 10,62%
Example 8 Synthesis of formula (9) 2R-acetoxy-3,3,4R-)limethylcyclohexanone Niacetate Crude product (z53) of formula (9-1) in reactor water cyclized methylene (100i+/) solution Pass ozone through at -78C for 30 minutes. The temperature was raised from -78C to OC and water (20
Add 100ml of water and heat at 60 tlC for 1 hour. Extract the Iy reaction solution with ether. Wash with organic #7 water and saturated saline and dry. After distilling off the solution, the resulting crude product was purified by silica gel column chroma) (11-hegisan:ether = 2
: l) and the so-called luketoacetate <2. ．． 12
f, total yield of 93% from ketone 9). Recrystallize from hexane to obtain hot plate needle-shaped crystals (l?'', φ7o-7xr).

1: ν (CCt4 solution) 1760.1740c
m-'FJMill! , ; δ (CC14 solution) s
o M'Hzo, 73 (S, 3H), 1.03 (
8, 3H) 0.98 (d, 3H, J=7)
, 1.2~t9 (m, 3#), ZO8 (S, 3
H), -22~Z5 (m, 211), 4.7
5 (S.

Example 9 Formula (8) Synthesis of 3,3.4R-trimethyl-1-cyclohegysenyl-rubaldehyde Methoxymethyltrifvonylphosphonium chloride (6,86, 20 mmot), anhydrous toluene (401R)) is added. This solution was added to n-butyllithium (1011/, 15?) under an argon stream.
FL Perforation o1) was added dropwise at room temperature, and the mixture was stirred for 7.2 hours at room temperature. Ketoacetate formula (9) (2,005
', 10. Anhydrous toluene (201R
1) Add the bath solution at room temperature. Then 18-crown-6
(1,06f, 4°02'mmol) w7In and stirred at room temperature overnight. Extend the reaction mixture with ether.

The entire organic layer is washed with water, and the water waste is extracted with ether. ;1jW
Combine j→, wash with water and saturated saline, and dry. Molten N
? The residue obtained by distillation was dissolved in ether (4 omH) and 30% hydrogen peroxide solution (approximately 10 drops) was added at 0''C.
Stir in the chamber for a minute. The solution was passed through a neutral alumina column to remove the precipitate, and the remaining solution was evaporated with ether (40 wj) containing monohydric acid.
Add the mixture at step C and stir for 2 hours using a shaker. Pour the reaction solution into water and extract with ether. The organic layer is washed with 11 um of sodium bicarbonate, water, and saturated saline, and dried. The solvent was distilled off [the two residues were passed through a neutral alumina column using P/T/:ether=2:1. V from which 18 was distilled off, preparative silica gel thin-
Chromatography (hexane:ether = 7:t) to prepare an oily conjugated aldehyde (9903!f, 6) with molecules rj 8.
5%).

IR; ν (liquid film) 27 thickness 0,1690.1645c1
4-' NMR, δ (CC14 solution) 100ME'.

0.94 (&eX2) 1.11 (6, 3H) 1.2-1.5 (m, 5H) 6.30 (bvs 1H) 9.41 (5, IB) Analysis value 2, 4-dinitrophenyl Hydrazone (melting point 1
55~15? C) Calculated value as C+aH2o□+#a: C, 57,82%; B, 6.07%; #, 16.
86% Measured value: C, 57, 91%; H, 6, 13%; N, 16
．． ss% Example 10 Synthesis of formula (?-1) 3,3,4R-)samethyl-l-cyclohexenylethanol: - Conjugated aldehyde formula (8) (99oW9.a, stmmol) in anhydrous ether (50ml) ) To the solution, add +1 tium aluminum hydride (247 Iv, 6.51 mmoj) in OC and stir for 30 minutes in OC under a stream of argon. Ether and water are added to the reaction bath liquid using OC to decompose the purified +1 tium aluminum hydride.

The reaction mixture is suction-filtered through Celite and the solvent is distilled off to obtain oily alcohol (986N9 is quantitative).

6p 80' (warm oil bath) / 5 *w HgIR;
v (Liquid Fil') 3300CII-1HMR; δ
(CCI4 solution) LOOMflZo, 82 (1,3R)
, 0.91 (d, 3H.

J=6), 0.98 (8,3H), 1.2-1.7 (t
yt, :(#), I80(br8゜lH), 1.97
(t 1ike, 2h), 3.86 (S,
2B), 5.30 (8, IB') Example 11 Formula (?) 3,3.4R-) + 1 Methyl-1-Schiff alcohol Dissolved in vinyl ether (60m/), acetic acid water @ (
250 Da) and reflux for 3 days.

The reaction mixture was added to an aqueous solution of hydrogen carbonate and extracted with ether. The organic layer is washed with water and saturated saline, and dried. When 1 s of the solution is distilled off, vinyl ether (1,408
9) is obtained.

Synthesis of heptaldehyde, crude production of vinyl ether formula (7)! +(1,41?) in a sealed tube 18
0~! Heat to 85C for 3 hours. A silica gel thin layer chromatograph (n-hex ratio 61%) was obtained for preparative fractionation of the infiltration fraction.

-IR; ν (liquid film) 1725, 1380.890m
-1 NMR; δ (CCt, solution) 100MHz, 8-1
．． 0 (MgX3) 1.2-1.8 (m, 3Ii') 11-22-4
(,2B) 2.5~ze (m, 3H) 4.85 tbV8, 1#) 4.92 (bhis, IH) 9.97 (t, 11-1.J=2) Analysis f0" 1
Calculated value as 2B200: C, 79,94%; /7, 11.18% Measured value: C, go, to%; B, 11.35% Implementation
Example 13 Synthesis of formula (5) 3-(2,2,3R-)samethyl-6-methylene/-1-cyclohexyl)-2-hydroxypropionitrile Ni-aldehyde formula (6) (185iIg, 1.03m
Vinegar with OC in an ethanol (6 ml) solution of
! (2at) and cyan dead power 11um (t, 34f
, 20.6 mmol) and stirred under OC for 2 hours at room temperature.

The reaction mixture is extracted with ether. The 44th layer was washed with water, an aqueous sodium bicarbonate solution, water until neutral, and finally washed with saturated saline and dried.

When the solvent is distilled off, an oily cyanhydride 7 (222 Da) is obtained quantitatively. It is a diastereomeric mixture of about 12! by thin layer chromatography.

hp 85C (oil bath temperature) / 0.8 degrees HgIR;
ν (liquid film) 3450.9003-'NMR;a (C
CI, solution) t 00MHz0.8~1.1 (M
gX2) 1.1-Z4 (77L, 8H) 14-18 (m, 1H) 4.0-4.5 (m, IH) 4.7-5.0
(m, 2H) Analysis value C,, H,, Calculated value as ON: C, 75,31%; H, 10,21%; #,
6.76% Measured value: C, 75, 6'J, ; H, 9, 889; #,
7.07% Example 14 Formula (4) Synthesis of 3-(2,2,3R-)limethyl-6-methyl-1-cyclohexyl)-2-phenylselenylpropionitrile Nicyanhydrin Formula ( 5) crude 11iZm (222In
9 (approximately 1.03 mmol) of pyridine (1+t)M
iJ liquid Nimesil alide (232Al, 3.1 mrn
, 01) and stirred for 3 hours under OC under an argon stream. Reaction mixture? Add to water and extract with ether. The entire organic layer is washed with a 10% aqueous sulfuric acid solution, water, and saturated saline, and dried. When the solvent was distilled off, oily mesylate (32
1■) Get 7. Meanwhile, under an argon atmosphere, sodium borohydride (58519, 1,54 mtnol) f was added to a solution of 1 mmol of diphenyl diselenide (241q, O, ?') in ethanol (3 ml) at room temperature and stirred. When the solution became colorless and transparent, the crude mesylate (321111F) was added to ethanol (15
ml) solution'? Add toC and stir at room temperature for 2 hours. The reaction mixture is added to water and extracted with ether. The organic layer is washed with water and saturated saline, and then dried.

After distilling off the solvent, a silica gel chromatograph (n
-hexane:ether=15:1) to obtain oily selenide (264119, total yield 74% from aldehyde ■J).

IR; ν (liquid film) 2250.900 cm-'NMR, δ
(CCt4 solution) 100MHz, 82(t, 6H)
, 0.84 (d , 3#.

J=8), 1.2~Z2 (m, 8H), 3.24
~3.44 <m, LH), 4.80 (brs,
'1li), 7.2-7.8 (m.

5H) Example 5 Synthesis of formula (3) 3-(2,z,3R-trimethyl-6-methylene-1-cyclohexyl)=4=acrylonitrile Methylene chloride of niselenide formula (4) (94m9, 0.2Tmmol) Pyridine (50μg) and 15% hydrogen peroxide solution (6lO, μt, Z 7mm) were added to the (1ml) solution.
ol) at room temperature and stir at room temperature. The reaction mixture is extracted with ether. The organic layer was dissolved in lθ% steel sulfate aqueous solution, water,
Wash with saturated saline and dry. After dissolving and completely distilling off, preparative silica gel thin layer chromatography (n-hexane:ether=
15:1) and purified for minutes to an oily conjugated nitrile (45 m
g, 88%).

6p90C (oil bath temperature) / 3 llm11' gI
R; ν (liquid film) 2250,970,900α-1HMR
;δ(CCt4 solution) l O0Ml1 zo, 81(
s, 3#), 0.88 (d, 3H.

J=7), 0.94 (S, 3H), 1.2-1.8 (m
, 3H), λl~13(m.

2H), 2.61 (d, LH, J=93.4.66
(6?s, tH), 4.78(s.

tH), 5.29 (d, tHsJ=16),! lL
90 (dd, LH, J=9, 16)20
mass m7g 206 (M) ν (liquid film) 1
690,1610.1175°890α-1δ (CCt, solution) 0.8-1.1 (mass)!
, 2~zo (m, 3H) 131 (8, 3E) 12~Z5 (tn, 2H) 4.19 (d, lH, J=s) 4.84 (6?
-8,2H) 6.1 to 6.6 (m, 2H) Analysis value c, 3H,. Calculated value as N: C, 8L 48%; H, 10, 12%; N,
7.40% Measured value: C08λ49%: H, 10, 23%; N,
? , so% Example 16 Formula (2) (+)-27i! ,6A! -) 5y Su-
Synthesis of r-ion Conjugated nitrile formula (3) (490m9.'!-59mm0
Methyllithium (6a!, about 6.7 mmol) was added to the anhydrous ether (20 w, l) solution of 1) at -55C, and the temperature was gradually raised to Oc. Ether and an aqueous ammonium chloride solution were added to the reaction solution using OC, followed by extraction with ether. The organic layer is washed with water and saturated saline and dried.

The solvent was distilled off, and the residue was separated and purified using preparative silica gel thin layer chromatography (n-hexane:ether=lo:l) to obtain 275M 9.52%.

HP 100C (oil bath temperature) 70.8-Shun mass
m/e 206 (M) [α)B +s7°
(C, 0,333° solvent CH, C1,) IR; ν (liquid film) 1680, 1620.1380° 89
0m-' NMR, δ (CDC1, solution) 100#//g0.83
(s, 3H), 0.87 (d, 2B.

J=8), 0.91 (1,3H), 1.2-1.8 (m
, 3H), 12-14 (m.

2H), Z25(8,3H), 266 (d, lli, J=9), 4.59 (brs.

lH), 4.78 (br s, tH), 6.1
2 (d, lH, J=16), 7.10 (dd
, IH, J=9, 16) Actual example
17 Synthesis of formula (1)' (-)-2R,6R-trans-α-ylon and formula (1)''(+)-6R-β-ylon nee trans-r-ylon formula (2) (?Osp, 0.34tntn
ol) f Dissolve in 85% phosphoric acid (1,5me) and stir at room temperature for 6 hours.

Ether and water are added to the reaction mixture and extracted.

``The organic layer is washed with an aqueous sodium bicarbonate solution, water, and saturated saline, and dried. The solvent was distilled off and purified by preparative silica gel thin layer chromatography (n-hexane:ether=IO:1) to obtain a mixture (9
3 near) (58■, 83 hits') was obtained.

NMR, IR1MαS of these formulas (1)' and (1)"
S completely matched the natural product.

The optical rotation of the mixture obtained by distilling the mixture (boiling point 95C (oil bath temperature)/6 Hg) is ((ffi)3 = -318° (C, 0,326, solvent CH, C1,) 81: 1-

Claims (1)

[Claims] The following formula (E), ▲There are mathematical formulas, chemical formulas, tables, etc.▼(E) However, in the formula, Y represents a hydrogen atom, an OH group, or a ▲There are mathematical formulas, chemical formulas, tables, etc.▼ group. , where Y
Cyclohexane nitriles represented by: When is a hydrogen atom, ■ represents a double bond (■), and when Y is another group, ■ represents a single bond (■).