JPS626696B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides the following formula (1), which is useful as a fruit-based aroma and flavor component and which has not been described in any prior literature. However, in the formula, R represents a hydrogen atom or a C ₁ to C ₄ alkyl group, R ¹ represents a hydrogen atom or a group - COR ² , and R ² represents a hydrogen atom or a C ₁ to C ₄ alkyl group. However, in the above, when R is a _C2 alkyl group, ^R1 represents a group ^-COR2 , 3-substituted-cis- or 3-substituted-trans-4-octenoic acid or its esters, represented by Regarding its manufacturing method and its use. Some of the present inventors have proposed the following formula (A), However, in the formula, Q represents a hydrogen atom or _-COCH3 , cis- or trans-5-octene-1,3-diol and 3-hydroxy-cis- or 3-hydroxy-trans-5-octene- 1-yl-acetate was extracted and isolated from natural apples as a key flavor of apple aroma and flavor, and its synthesis method and its usefulness as a long-lasting aroma and flavor imparting or modulating agent were discovered. , Japanese Patent Application Publication No. 84511 (1972)
No. 151652). As a result of further research, the inventors found that the above formula
3-Substituted-cis- shown in (1) and not described in the conventional literature
or that 3-substituted-trans-4-octenoic acid or its esters can be easily synthesized;
and the compound is a unique and useful component as a fruit-based aroma or flavor component, has an excellent persistent aroma or flavor, and is a compound that deserves attention as a persistent aroma or flavor imparting or modulating agent. In this way, it has been discovered that it can be an excellent long-lasting aroma and flavor imparting or modulating agent in a wide range of fields of use, such as food and drink (including luxury goods), cosmetics, health care, hygiene, and pharmaceuticals. Therefore, an object of the present invention is to provide 3-substituted-cis- or 3-substituted-trans-4-octenoic acid represented by the above formula (1) or esters thereof, a process for producing the same, and uses thereof. 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 present invention has the following formula (1), It can be expressed as In formula (1), R and R ¹ have the same meanings as described above, and when R is a C ₁ -C ₄ alkyl group and R ¹
When represents a group ^-COR2 and ^R2 is a _C1 - _C4 alkyl group, specific examples of the alkyl group include methyl, ethyl, n-propyl, iso-propyl,
Examples include n-butyl, tert-butyl, and sec-butyl. Specific examples of these new compounds of formula (1) include: a Methyl 3-hydroxy-cis-4-octenoate b Methyl 3-hydroxy-trans-4-octenoate e Propyl 3-hydroxy-cis-4-octenoate , f Propyl 3-hydroxy-trans-4-octenoate g Butyl 3-hydroxy-cis-4-octenoate h Isobutyl 3-hydroxy-trans-4-octenoate i 3-Methylcarbonyloxy-cis-4-octenoic acid Methyl j 3-methylcarbonyloxy-trans-4
-Methyl octenoate k 3-Methylcarbonyloxy-cis-4-ethyl octenoate l 3-ethylcarbonyloxy-trans-4
-Methyl octenoate m 3-propylcarbonyloxy-cis-4-
Propyl octenoate n 3-propylcarbonyloxy-trans-
Methyl 4-octenoate o 3-butylcarbonyloxy-cis-4-ethyl octenoate p 3-butylcarbonyloxy-trans-4
Preferred examples include propyl octenoate. The above exemplified compound is a transparent oily substance,
Its boiling point is as follows. (a) 86~89℃/3mmHg (b) 88~90℃/3mmHg (e) 96~97℃/3mmHg (f) 94~96℃/3mmHg (g) 99~100℃/3mmHg (h) 97~ 99℃/3mmHg (i) 96～99℃/2mmHg (j) 95～96℃/2mmHg (k) 118～120℃/2mmHg (l) 122～125℃/2mmHg (m) 148～149℃/2mmHg ( n) 130-133°C/2mmHg (o) 105-149°C/2mmHg (p) 151-152°C/2mmHg The compound of the formula (1) of the present invention has the following formula (1)' and the formula
(1)”Includes compounds. In the above formulas (1)′ and (1)″, R and R ² are defined by the formula (1)
It has the same meaning as described above. And the above formula
(1)' In the compound, the cis-form is, for example, 2-hexinal represented by the following formula (3) C ₃ H ₇ -C≡C-CHO (3), the following formula (4), X'CH ₂ COOR (4) However, in the formula, R has the same meaning as above, and X' represents a halogen atom, and the following formula (6) is formed by reacting with haloacetic acid or its functional derivative represented by However, in the formula, R has the same meaning as described above, and it can be formed by catalytic hydrogen reduction of 3-hydroxy-4-octynoic acid or its ester represented by the following in the presence of a reduction catalyst. In addition, in the above formula (1)' compound, the trans-form is, for example, the trans-2-hexenal represented by the following formula (5), C ₃ H ₇ -CH=CH-CHO (5), and the trans-2-hexenal represented by the following formula (5). 4), X′CH ₂ COOR (4) However, in the formula, R has the same meaning as above, and X′ represents a halogen atom. can. Furthermore, the above formula (1)'' compound is a compound of the following formula (2), ( ^R2CO ) _o X (2) However, in the formula, R ² represents a hydrogen atom or a C ₁ to C ₄ alkyl group, and X represents -OH, a halogen atom, or an oxygen atom, where when can be obtained by reacting with a carboxylic acid or a functional derivative thereof, where n=1 and n=2 when X is an oxygen atom. 1) The production process of the compounds (formulas (1)′ and (1)″) can be shown as follows. In the present invention, 3-hydroxy-cis- or 3-hydroxy-trans-4-octinoic acid or its esters of formula (6) are produced by reacting the above formula (3) compound and formula (4) compound. This can be carried out using the Reformatsky reaction, which is known per se, according to the following formula. 2-hexinal of formula (3) is, for example, ERH
, Jones et.al.J.Chem.Soc., pp. 1054-1059,
(1958), by reacting 1-pentyne with ethylmagnesium bromide and N,N-dimethylformamide. In addition, the haloacetic acid or its functional derivative (alkyl ester) of the above formula (4) can be used with the corresponding R depending on the type of R in the desired formula (6) to be produced.
A compound of formula (4) having the following may be selected. An expression like this
(4) In addition to haloacetic acid, examples of compounds include methyl haloacetate, propyl haloacetate, butyl haloacetate, and examples of halogens include chloro, bromine, iodine, etc. be able to. Haloacetic acid esters can be easily obtained by esterifying haloacetic acid with a corresponding alcohol by a conventional method. Among the haloacetic acid esters, bromoacetic acid esters are preferably used. The amount of haloacetic acid or its functional derivative of formula (4) to be used can be selected as appropriate, but for example, 2-
An example of an amount used is about 0.5 to about 5 times the mole, more preferably about 0.8 to about 1.5 times the mole of hexinal. The reformaski reaction between the compound of formula (3) and the compound of formula (4) can be carried out in the presence or absence of a solvent, but it is preferably carried out in the presence of a solvent. Examples of the inert organic solvent used include hydrocarbons such as benzene, toluene, and xylene; ethers such as diethyl ether, tetrahydrofuran, and dimethoxyethane; and the like. These solvents can be used alone or in combination. There are no particular restrictions on the use of the solvent and the amount thereof, and a desired solvent can be used and a desired amount suitable for the reaction operation can be appropriately selected and utilized. For example, the amount used may be about 0.5 to about 10 times (by weight), more preferably about 2 to about 4 times (by weight) relative to 2-hexinal of formula (3). In addition, when using a commercially available zinc as the zinc used in the Reformasky reaction, commercially available zinc in the form of powder, granules, flakes, or hairs may be activated by washing with a dilute aqueous hydrochloric acid solution and drying. It is better to use The amount used is, for example, preferably about 0.5 to about 3 gram atoms, more preferably about 0.9 to about 1.4 gram atoms, per mol of the compound of formula (3). The temperature of the Reformasky reaction is, for example, about 5° to about 150°C, more preferably about 30°C.
An example is a temperature of about 80°C. Further, the reaction time can be changed as appropriate depending on the type and amount of the haloacetic acid or its functional derivative used, the solvent, the reaction temperature, etc. After the reaction, the reaction product is cooled and then poured into, for example, a dilute aqueous sulfuric acid solution, the target product is extracted with an appropriate solvent, and the extracted solvent layer is washed with water, deuterated sodium chloride, or water to remove the solvent. The reaction product 3-hydroxy-4-octynoic acid or its ester of formula (6) can be obtained by, for example, distillation under reduced pressure. The obtained compound of formula (6) is subjected to catalytic hydrogen reduction in the presence of a reduction catalyst to convert the compound of formula (1)'
can be converted into 3-hydroxy-cis-4-octenoic acid or its ester. The catalytic hydrogen reduction can be carried out under relatively mild conditions, for example, the compound of formula (6) is reacted with a reducing catalyst such as poisoned palladium in an inert organic solvent,
The catalytic hydrogen reduction reaction can be easily carried out with good yield and excellent selectivity. The reaction proceeds satisfactorily even at room temperature, for example, from about 5°C to about 40°C.
Can be carried out at temperatures around 10℃ to 30℃
It is more preferable to adopt a temperature range of . Although the reaction proceeds satisfactorily under normal pressure, pressurized conditions can also be employed, and a pressure range of about 1 to about 20 kg/cm ² is often employed. Catalysts such as poisoned palladium suitable for use in the above catalytic reduction reaction include, for example:
Palladium poisoned with lead acetate (Rindler catalyst)
and palladium-barium acetate to which quinoline or the like is added. The amount of these catalysts to be used is, for example, approximately
About 0.1 to about 20% by weight, more preferably about 0.5 to about
A content of around 10% by weight is most often employed. In addition, examples of the inert solvent used in the catalytic hydrogen reduction reaction include methanol, ethanol, n-propanol, isopropanol,
Ethyl acetate, n-hexane, petroleum ether and the like can be mentioned. These solvents may be used alone or in a mixture of two or more. There is no particular restriction on the amount of these solvents used, but for example, about 5 to about
About 300 times the weight, preferably about 10 to about 100 times the weight, is often employed. In the present invention, the compound of formula (1)' can also be represented by the following formula:
(5), C ₃ H ₇ -CH=CH-CHO (5) Trans-2-hexenal represented by the following formula (4), X′CH ₂ COOR (4) where R is a hydrogen atom or It can be obtained by reacting with a haloacetic acid or a functional derivative thereof represented by the following formula, which represents a C ₁ -C ₄ alkyl group, and X' represents a halogen atom. According to this embodiment, 3-hydroxy-trans-4-octenoic acid or its ester in formula (1)' can be formed without performing the catalytic hydrogen reduction in the above embodiment. This reaction can be carried out in the same manner as described above for the reaction of forming a compound of formula (6) from a compound of formula (3) and a compound of formula (4), and instead of a compound of formula (3), a compound of formula (5) is used. It can be carried out in exactly the same manner except for using a compound. In the method of the present invention, in formula (1), the following formula (1)'', However, in the formula, R and R ² have the same meanings as described for formula (1). In formula (1), the compound ^represented by ) nX (2) However, in the formula, R ² has the same meaning as above, and X represents -OH, a halogen atom or an oxygen atom,
Here, when X is -OH or a halogen atom, n=1, and when X is an oxygen atom, n=
It can be formed from the compound of formula (1)' in formula (1) by reacting it with a carboxylic acid represented by the formula (2) or a functional derivative thereof. Examples of the above formula (2) compounds include acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, and their corresponding acid anhydrides, or R such as acid chloride or acid bromide. Preferred examples include compounds in which ² is a C ₁ -C ₄ alkyl group, and their acid anhydrides or acid halides. The reaction is easily carried out by bringing the above formula (1)′ and formula (2) (R ² CO) nX into contact in the presence or absence of a catalyst, in the presence or absence of a solvent. be able to. Several aspects are shown below. (i) When (R ² CO)nX is a carboxylic acid or an acid anhydride: - the above formula (1)'3-hydroxy-cis- or -trans-4-octenoic acid or its ester,
It can be carried out by reacting with the carboxylic acid or acid anhydride in formula (2) in a solvent or in the absence of a solvent in the presence of a catalyst. The amount of the carboxylic acid or acid anhydride of formula (2) to be used is, for example, about 1 to about 1 mole of the compound of formula (1)'.
About 10 moles, preferably about 2 to about 3 moles, are employed. Examples of solvents include pentane, hexane,
Aliphatic hydrocarbons such as cyclohexane and petroleum ether; aromatic hydrocarbons such as benzene, toluene and xylene; and ethers such as diethyl ether, diisopropyl ether and tetrahydrofuran. There are no particular restrictions on the use of the solvent and the amount thereof, and a desired amount suitable for the reaction operation can be selected and used. For example, a range of about 0.5 to about 50 times (by weight), more preferably about 5 to about 15 times (by weight) of the compound of formula (1)' is most commonly employed. Examples of catalysts include sulfuric acid, hydrochloric acid,
Examples include inorganic protonic acids such as phosphoric acid; acidic catalysts such as organic protonic acids such as methanesulfonic acid and p-toluenesulfonic acid; and basic catalysts such as pyridine, sodium acetate, and sodium propionate. The amount of catalyst used is, for example, according to the above formula
For example, about 0.5 to about 40% (by weight), preferably about 3 to about 10% (by weight) of the compound (1)' is employed. The reaction temperature can be appropriately selected depending on the type and amount of the carboxylic acid or acid anhydride, catalyst and solvent used, and is, for example, about 10°C to about 150°C, preferably about 50°C to about 80°C. The reaction time can be changed as appropriate depending on the carboxylic acid or acid anhydride used, the type and amount of the catalyst, the reaction temperature, etc. After the reaction, the reaction product is introduced into water, the target product is extracted and collected with an appropriate solvent, the extracted solvent layer is further washed with water as desired, the solvent is removed, and the above formula (1) "new" is obtained by, for example, column chromatography separation. (ii) When (R ² CO)nX is an acid halide: - The above formula (1)'3-hydroxy-cis- or -trans-4-octenoic acid or its ester can be obtained in a solvent or It may be brought into contact with the acid halide of formula (2) in a solvent-free environment.The amount of acid halide used is, for example, about 0.5 to about 5 moles based on the compound of formula (1)'.
Examples of solvents include aliphatic hydrocarbons such as pentane, hexane, cyclohexane, petroleum ether, etc.
Examples include ethers such as diethyl ether, diisopropyl ether, and tetrahydrofuran. Also, as a catalyst, pyridine, picoline,
Examples include nitrogen-containing compounds that do not have a hydrogen atom on a nitrogen atom, such as N,N-dimethylaniline and quinoline. The amount of these catalysts used is determined by the formula above.
About 0.5 to about 40% (by weight), preferably about 2 to 10% (by weight) of the compound (1)' is employed. There is no particular restriction on the amount of solvent to be used, and a desired amount suitable for the reaction operation can be appropriately selected and used. quantity is adopted. Usually, the reaction can be carried out directly or by dropping an acid halide onto the compound of formula (1)' dissolved in a solvent and allowing the reaction to occur at a predetermined temperature for a predetermined period of time. After the reaction, for example, the reaction solution is introduced into water and, if desired, extracted using an extraction solvent. For example, the extract can be washed with water, the solvent removed, and distilled under reduced pressure to obtain a new compound of formula (1).The dropwise addition of the acid halide and the reaction temperature depend on the type of acid halide and solvent used. It can be changed as appropriate depending on the amount etc., but for example, from about -20℃ to
It can be carried out at a temperature of about 10°C. Furthermore, in the method of the present invention, the above formula (6), formula
After obtaining compounds of formula (1)′ and formula (1)″, in these formulas, R
is a hydrogen atom into other compounds represented by these formulas where R is an alkyl group, or alternatively, a step can be added to convert compounds where R is a hydrogen atom into other compounds represented by these formulas where R is an alkyl group. A step of converting into a compound in which R is a hydrogen atom or a compound in which R represented by these formulas is another alkyl group can be added. For example, a compound represented by formula (6), formula (1)' or formula (1)'' in which R is an alkyl group in the presence of an acid catalyst such as sulfuric acid, hydrochloric acid, phosphoric acid, etc.
They can be converted by hydrolysis to the corresponding compounds in which R is a hydrogen atom. In addition, the thus obtained compound in which R is a hydrogen atom or the compound in which R is a hydrogen atom in these formulas is prepared by using an alcohol having a desired alkyl group,
It can be converted into a compound having a desired alkyl group by esterification using a conventional method. The above hydrolysis reaction is carried out, for example, in the presence of benzene at a temperature range of about 40 to 60°C for a reaction time of about 3
This can be carried out for about 5 hours. or,
The above esterification reaction can be carried out, for example, in the presence of sulfuric acid,
A compound of formula (6), formula (1)′, or formula (1)″ in which R is a hydrogen atom is heated and reacted in benzene while removing the desired alkyl alcohol and a theoretical amount of water from the reaction system. Furthermore, the compounds in which R is an alkyl group in formula (6), formula (1)', and formula (1)'' may be prepared according to other embodiments, in which R is another group. It can also be converted into a compound that is an alkyl group. In this aspect, for example,
This can be carried out by bringing the transesterification reaction into contact with an alkyl alcohol having another desired alkyl group in the presence of a basic catalyst such as sodium methylate, sodium ethylate, or aluminum alcoholate. The compound represented by the formula (1) of the present invention has excellent persistence and unique flavor as a fruit aroma or flavor component. Thus, according to the present invention, the following formula (1) However, in the formula, R and R ¹ have the same meanings as defined above; A modulating agent can be provided. Further, by utilizing this persistent aroma flavor imparting or flavor modulating agent, food and drink products containing the compound of formula (1) as an aroma component, and foods and drinks containing the compound of formula (1) as an aroma component. A soap characterized by
It is possible to provide detergents, cosmetics, health care products, hygiene products, pharmaceutical products, etc., which contain the compound of formula (1) as an aromatic flavor component. For example, beverages such as juices, fruit alcoholic drinks, milk drinks, carbonated drinks, etc.; frozen desserts such as ice creams and ice cream cakes; Japanese and Western sweets; jams; chewing gum; breads; coffee, cocoa, and tea. It is possible to provide food and drink products containing a variety of foods, instant beverages, and food products, including favorite foods such as tea, etc., in an appropriate amount capable of imparting the unique aroma and flavor. Also, for example, shampoo, hair rinses, hair creams,
Bases for pomades and other hair cosmetics: Cosmetics can be provided by blending bases for cosmetic soaps and other cosmetic detergents in appropriate amounts to impart their unique aromas. Furthermore, its unique scent can be used in various health and hygiene products such as laundry detergents, disinfectant detergents, deodorant cleaning products, and other health and hygiene products; and various health and hygiene materials such as toothpaste, tissue paper, and toilet paper, as well as pharmaceutical products. It is possible to provide health, sanitary, and pharmaceutical products that are blended or applied in an appropriate amount to impart flavor. Reference Example 1 Synthesis of 2-hexinal A mixed solution of 17 g (0.25 mol) of 1-bentine in 50 ml of ether is added dropwise into 150 ml of an ether solution of ethylmagnesium bromide prepared from 6 g (0.25 mol) of metallic magnesium and excess ethyl bromide. After the dropwise addition is complete, reflux is continued for 1 hour. Next, a solution of 55 g of DMF and 100 ml of ether is added dropwise under cooling. After the dropwise addition was completed, the reaction was continued for an additional hour at 20°C. After completion, add the reaction solution to 1 part of 5% sulfuric acid water,
Stir at room temperature for 10 hours. Ether 500% organic layer
Extract in ml. ether layer into soda ash aqueous solution
After washing with 300 ml, dry over anhydrous magnesium sulfate, remove ether, and distill the residue. Boiling point 50-51℃/25mmHg 12g (yield 51%) Reference example 2 Alkyl 3-hydroxy-4-octinoate (1) 15g (0.23 gram atom) of activated powdered zinc and ethyl 3-hydroxy-4-octinoate Pour dry tetrahydrofuran, put a mixed solution of 34 g (0.2 mol) of ethyl bromoacetate in 100 ml of tetrahydrofuran into the dropping funnel, add about 20 ml, warm the flask, and start the reaction, which will continue for about 40 minutes. Then, the remaining mixture was added dropwise to the extent that the contents slowly refluxed. After dripping, 2
-20 g (0.2 mol) of hexinal was added dropwise from the dropping funnel until the contents slowly refluxed (about 1 hour). After the reaction is complete, add 300ml of 5% hydrochloric acid aqueous solution to the reaction solution.
The reaction solution was extracted with 500 ml of ether.
After neutralizing and washing the extract with 100 ml of sodium chloride water, the solvent was removed and distilled under reduced pressure to obtain a boiling point of 110°C to 115°C/2.
Ethyl 3-hydroxy-4-octinoate with mmHg (Structure confirmed by IR, MS and NMR)
30g (theoretical yield: 80%) was obtained. (2) Propyl 3-hydroxy-4-octinate (1) Using propyl bromoacetate instead of ethyl bromoacetate, react in the same manner as in (1) to obtain the corresponding propyl 3-hydroxy-4-octate. Ta. (3) According to the methods (1) and (2) of Reference Example 2, various alkyl 3-hydroxy-4-octoates were produced using various alkyl haloacetates. Examples are shown in the table below.

[Table] Isobutyl tinate
Reference example 3 Alkyl 3-hydroxy-cis or trans-4-octenoate (1) Ethyl 3-hydroxy-cis-4-octenoate 20 g of ethyl 3-hydroxy-4-octanoate
A solution prepared by adding 2 g of quinoline to 100 ml of methanol and 1 g of Lindlar catalyst were charged into an autoclave, and catalytic hydrogen reduction was performed at a hydrogen pressure of 1 to 10 Kg/cm ² (room temperature). The reaction was terminated when the theoretical amount of hydrogen was absorbed, and after removing the catalyst and methanol, 100 ml of ether was added, and the mixture was washed with 20 c.c. of 5% aqueous hydrochloric acid solution, and then neutralized and washed with deuterium chloride water. Remove the solvent and distill under reduced pressure, boiling point 92℃
19 g (theoretical yield: 95%) of ethyl 3-hydroxy-cis-4-octenoate (structure confirmed by IR, MS and NMR) having a temperature of ~95°C/2 mmHg was obtained. (2) Ethyl 3-hydroxy-trans-4-octenoate 15 g activated powdered zinc (0.23 gram atom)
and dry tetrahydrofuran, and into the dropping funnel, put a mixed solution of 34 g (0.2 mol) of ethyl bromoacetate in 100 ml of tetrahydrofuran, and add about
After adding about 20 ml and warming the flask to start the reaction, the remaining mixture was added dropwise over about 40 minutes to the extent that the contents slowly refluxed. After dropping, add 20g of trans-2-hexenal (0.2
mol) was added dropwise from the dropping funnel until the contents slowly refluxed (about 1 hour). After the reaction was completed, the reaction solution was poured into 300 ml of 5% aqueous hydrochloric acid solution, and the reaction solution was extracted with 500 ml of ether. After neutralizing and washing the extract with 100 ml of sodium chloride water, remove the solvent.
Distillation was carried out under reduced pressure to obtain 31 g (80% theoretical yield) of ethyl 3-hydroxy-trans-4-octenoate (structure confirmed by IR, MS and NMR) having a boiling point of 90-93°C/3 mmHg. Example 1 According to the methods (1) and (2) of Reference Example 3, various 3-
Hydroxy-cis- or -trans-4-octenoic acids were produced. Examples are shown in the table below.

[Table] Butyl ctenoate

[Table] Butyl Example 2 Alkyl 3-alkylcarbonyloxy-cis- or -trans-4-octenoate (1) Methyl 3-methylcarbonyloxy-cis-5-octenoate Obtained in Example 1 in a reaction flask Methyl 3-hydroxy-cis-4-octenoate 17.2g
(0.1 mol) dissolved in 50 ml of dry pyridine, and added to this with stirring, 9.5 g of acetyl chloride.
(0.12 mol) in 20 ml of dry ether was added dropwise over 30 minutes. After reacting at the same temperature for 1 hour, the contents were poured into ice water and extracted with ether. The ether layer was washed with water, diluted hydrochloric acid and water, and then dried over anhydrous sodium sulfate. After removing the desiccant, remove the ether and distill under reduced pressure to reduce the boiling point to 96.
18.8 g (88% theoretical yield) of methyl 3-methylcarbonyloxy-cis-4-octenoate (structure confirmed by IR, MS and NMR) having a temperature of ~99°C/2 mmHg was obtained. (2) 3-methylcarbonyloxy-trans-4
-Methyl octenoate 11.2 g (0.11 mol) of acetic anhydride in the reaction flask.
and 1.2 g of 10% phosphoric acid-acetic anhydride were added thereto, 17.2 g (0.1 mol) of methyl 3-hydroxy-trans-4-octenoate obtained in Example 1 was added dropwise over 1 hour, and the mixture was heated at 55°C to 60°C. After 4 hours of reaction,
Water was added and treated at 80°C for 1 hour. The cooled reaction solution was extracted with ether, and the ether layer was washed with water, sodium chloride, water, and dried over anhydrous sodium sulfate.
After separating the desiccant, the ether is recovered using an evaporator, and the recovered residue is distilled under reduced pressure to reduce the boiling point to 95.
18 g of methyl 3-methylcarbonyloxy-trans-4-octenoate (structure confirmed by IR, MS and NMR) with temperature between 96°C and 2mmHg
(85% yield). (3) Various alkyl 3-alkylcarbonyloxy-cis- or -trans-4-octenoates were produced according to the method of (2) above using various esterifying agents. Examples are shown in the table below.

[Table] Reference Example 4 The following components (weight) were mixed as an apple-like aroma composition. Ethyl acetate 50 Ethyl propionate 20 Ethyl butyrate 30 Ethyl isovalerate 60 Isoamyl acetate 30 Butyl alcohol 150 Amyl alcohol 50 Butyl propionate 70 Butyl butyrate 10 2-Hexenol 100 2-Hexenyl acetate 180 Isobutyric acid 40 Vanillin 20 Hexyl Butyrate 10 Ethyl alcohol 180 total 1000 Add 3-hydroxy-cis-4 to 100 g of the above composition.
- By adding 20 g of methyl octenoate, a new aroma composition with excellent apple aroma and flavor components was obtained. Similar results were obtained by substituting 3-methyl 3-hydroxy-cis-4-octenoate for methyl 3-hydroxy-cis-4-octenoate.
Methyl hydroxy-trans-4-octenoate,
Propyl 3-hydroxy-cis-4-octenoate, propyl 3-hydroxy-trans-4-octenoate, methyl 3-methylcarbonyloxy-trans-4-octenoate, 3-methylcarbonyloxy-cis-4-octenoic acid It was obtained by using methyl, propyl 3-propylcarbonyloxy-cis-4-octenoate, and methyl 3-propylcarbonyloxy-trans-4-octenoate. Reference Example 5 The following components (by weight) were mixed as apple-like aroma components. Ethyl acetate 50 Ethyl butyrate 150 Ethyl acetyl acetate 90 Ethyl cinnamate 20 Linalool 10 Amyl butyrate 30 Amyl acetate 40 Ethyl propionate 40 Ionone 10 Benzyl acetate 30 Linalyl acetate 20 Ethyl isovalerate 40 Vanillin 10 Maltol 20% PG 400 Cis -3-Hexenol 40 Isobutyric acid 20 total 1000 By adding 20 g of butyl 3-hydroxy-cis-4-octenoate to the above composition, it is very effective as an apple aroma and flavor component with a fresh light grassy aroma. An excellent new composition was obtained. Similar results were obtained by substituting butyl 3-hydroxy-cis-4-octenoate, ethyl 3-hydroxy-cis-4-octenoate, 3-hydroxy-trans-4-
Ethyl octenoate, 3-hydroxy-trans-
Isobutyl 4-octenoate, ethyl 3-methylcarbonyloxy-cis-4-octenoate, methyl 3-ethylcarbonyloxy-trans-4-octenoate, 3-butylcarbonyloxy-cis-
Obtained by using ethyl 4-octenoate. Reference Example 6 Composition for Soap A Narcissus-like fragrance composition was produced by mixing the following components (parts by weight). Bergamot oil 20 Ylang-ylang oil 5 Linalool 25 Benzyl acetate 5 Benzyl alcohol 22 Terpineol 10 Paracresyl acetate 1 Cinnamic alcohol 4 Eugenol 3 Heliotropin 3 Absolute diasmine 2 total 100 Add 3-butyl carbonyloxy to 98 g of the above composition A fragrance composition was prepared by mixing 2 g of propyl -trans-4-octenoate. This product had a novel composition with an excellent floral and long-lasting fragrance.
Similar results were obtained using methyl 3-ethylcarbonyloxy-trans-4-octenoate, 3-methylcarbonyloxy-cis-
It was obtained by using ethyl 4-octenoate and methyl 3-methylcarbonyloxy-cis-4-octenoate, respectively.

Claims (1)

[Claims] 1. The following formula (1) However, in the formula, R represents a hydrogen atom or a C ₁ to C ₄ alkyl group, R ¹ represents a hydrogen atom or a group - COR ² , and R ² represents a hydrogen atom or a C ₁ to C ₄ alkyl group. , However, in the above, when R is a C ₂ alkyl group, R ¹ represents a group -COR ^2. A 3-substituted-cis- or -trans-4-octenoic acid or its esters represented by: