JPS6148815B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention has a fresh green note or a sweet fresh green note and is useful in the fragrance field as a unique fruity and green aroma or flavor imparting or modulating agent, and is also useful as a flavor imparting or modulating agent for other flavoring substances. Also useful as a synthetic intermediate for
The following formula (1), which has not been described in conventional literature, However, in the formula, R is a C ₁ to C ₁₅ alkyl group and a C ₈
This invention relates to a 4-substituted nonanal represented by the following formula, which represents a group selected from the group consisting of _-C10 aralkyl groups, and a method for producing the same. The present inventors have continued research on the aroma and flavor components of watermelon for many years. As a result, the following formula
(A) We have succeeded in extracting and separating 4-oxononanal, represented by Japanese Patent Application No. 141173 (filed on November 2, 1974; title of the invention: "4-oxononanal, intermediates thereof, and methods for producing them")
No. 65839]. As a result of further research, the present inventors determined that the above formula
It is possible to synthesize the 4-substituted nonanals represented by (1), which have not been described in the literature, and that the compound of formula (1) has a fresh green note or a sweet fresh green note, and has a fruity aroma, especially a fruit-based one. Unique watermelon-like and green aroma It has excellent sustainability as a flavor imparting or modulating agent, and thus has a wide range of applications such as food and beverages (including luxury goods), cosmetics, health, hygiene, and pharmaceuticals. It was discovered that it is useful as an excellent long-lasting aroma and flavor imparting or flavor modulating agent. Furthermore, the compound of formula (1) is disclosed in a patent application for acetals of 4-substituted nonanal, which has not been described in any prior literature, filed on the same date as the present application.
No. 54-170295, JP-A No. 56-95141; December 1972
It has been found that the present invention is useful as an intermediate for the production of 4-substituted nonanal acetals and their production method (filed on May 28, 2008) and as an intermediate for the synthesis of other fragrance substances. Therefore, an object of the present invention is to provide 4-substituted nonanals of the formula (1) and a method for producing the same. In the formula (1) compound of the present invention, it is selected from the group consisting of a _C1 - _C15 alkyl group and a _C8 - _C10 aralkyl group. Specific examples of such suitable alkyl groups include methyl, ethyl, propyl, isopropyl,
Butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl,
Neopentyl, 1-methylbutyl, 1,2-dimethylpropyl, 1-ethylpropyl, hexyl,
Examples include _C1 - _C15 alkyl groups such as heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl and the like. Specific examples of such suitable aralkyl groups include _C8 to _C10 aralkyl groups such as phenylethyl, phenylpropyl, phenylbutyl, and the like. Specific examples of such compounds of formula (1) include the following compounds that have not been described in any prior literature. For example, (1) 4-methoxynonanal, (2) 4-ethoxynonanal, (3) 4-propoxynonanal, (4) 4-butoxynonanal, (5) 4-pentyloxynonanal, (6) )4-hexyloxononanal, (7)4-heptyloxononanal, (8)4-
Octyloxynonanal, (9) 4-nonyloxynonanal, (10) 4-decyloxynonanal, (11)
4-undecyloxynonanal, (12) 4-dodecyloxynonanal, (13) 4-phenethyloxynonanal, (14) 4-phenylpropyloxynonanal, (15) 4-phenylbutyl Oxynonanal. The compound of formula (1) as exemplified above is usually a transparent oily substance, and the physicochemical constants of typical examples thereof are as follows.

[Table] The 4-substituted nonanals of formula (1) of the present invention have a green note tone in common, although there are differences in their nuances. The green note tone of the above-mentioned exemplified compounds is illustrated below.

[Table] Note The 4-substituted nonanals of the formula (1) of the present invention are:
As shown in the diagram below, it can be produced, for example, by bringing the 5-substituted-1-decene of formula (2) into contact with ozone and reductively decomposing the product in the presence of a reducing agent. The compound can be formed, for example, by contacting 1-decen-5-ol of formula (3) with a halogen compound of formula (4) in the presence of a base, and the compound of formula (3) can be formed by, for example, 1-decene-5 in formula (5)
The compound of formula (5) can be formed by contacting -one with a reducing agent, and the compound of formula (5) can be formed by, for example,
-Alkyl oxooctanoate in the presence of a base,
It can be formed by contacting with the allyl halide of formula (6), followed by saponification and decarboxylation. In the above scheme, R has the same meaning as in formula (1), R ¹ represents a lower alkyl group, and X represents a halogen atom. Hereinafter, using the embodiment shown in the above diagram as an example, the present invention formula
The production of the compound (1) will be explained in more detail. The alkyl 3-oxooctanoate of the above formula (7) is
For example, a well-known method of reacting 2-heptanone with dialkyl carbonate in the presence of a base can yield a good yield.
It can be easily produced with good purity, and specific examples of R ¹ include C ₁ -C ₆ lower alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl and the like. The 1-decen-5-one of the above formula (5) is, for example, the 3-decen-5-one of the formula (7).
Contacting the alkyl oxooctanoate with the allyl halide of formula (6) above in the presence of a base,
It can be easily formed in good yield by saponification and decarboxylation. The condensation reaction in which the compound of formula (6) is brought into contact can be carried out, for example, in an inert organic solvent at a temperature of about 0°C to about 100°C, more preferably about 10°C to about 30°C.
It can be carried out at a temperature of about 100 mL for about 3 to about 60 hours, for example. Specific examples of the base used in the condensation reaction with the compound of formula (6) include sodium methoxide, sodium ethoxide, sodium propoxide,
Sodium isopropoxide, sodium t-butoxide, potassium methoxide, potassium ethoxide, potassium t-butoxide, sodium hydride, potassium hydride, lithium hydride, sodium amide, potassium amide, lithium amide, butyllithium, lithium dialkylamide There are many examples of this. The amount of these bases used is
It is sufficient to use about 1 to about 3 moles per mole of the compound of formula (7) as a raw material, and more preferably about 1 to about 3 moles.
About 1.5 mol is often employed. Further, examples of the allyl halide of formula (6) used in the above condensation reaction include allyl chloride, allyl bromide, allyl iodide, etc., and the amounts of these to be used can also be selected as appropriate. For example, about 1 to about 3 mol is often employed per 1 mol of the compound of formula (7) as a raw material. Further, specific examples of the inert organic solvent used in the above condensation reaction include methanol, ethanol, propanol, isopropyl alcohol, butanol, t-butyl alcohol, tetrahydrofuran, ether,
Examples include 1,2-dimethoxyethane, dioxane, benzene, toluene, xylene, liquid ammonia, and dimethyl sulfoxide. These solvents can be used alone or in combination of two or more. There are no special restrictions on the amount of these solvents used, but for the compound of formula (7) as a raw material,
The amount used is preferably about 2 to about 100 times by weight, more preferably about 3 to about 10 times by weight. After the compound of formula (7) and the allyl halide of formula (6) are brought into contact as described above, saponification and decarboxylation reactions can be carried out by a conventional method. for example,
The condensation reaction product formed as described above can be saponified and decarboxylated by refluxing in the presence of an acid. Saponification can be carried out, for example, by contacting with a basic catalyst such as caustic soda or caustic potash for hydrolysis. Further, decarboxylation can be easily carried out, for example, by heating with hydrochloric acid acidity, observing the generation of carbon dioxide gas, and refluxing until the generation of carbon dioxide gas stops. After performing the saponification and decarboxylation reactions, for example, the reaction product is poured into water, neutralized, extracted with an extraction solvent such as benzene, the solvent layer is washed with water, dried, and concentrated, 1-decen-5-one represented by formula (5) can be obtained with high yield and high purity. If desired, further purification can be carried out, for example, by means such as vacuum distillation or column chromatography. 1-decene-5-ol of the formula (3) is, for example, 1-decene-5-ol of the formula (5), which can be formed as described above.
The 5-one can be easily prepared in good yield and selectivity by contacting the 5-one with a suitable reducing agent, for example in an inert organic solvent. The reaction temperature of the reaction can be selected as appropriate, for example, from about -20 to about
Temperature range of about 100°C, more preferably about 0 to about
A reaction temperature of about 30°C can be exemplified. The reaction time can be changed as appropriate depending on the reaction temperature and the like, and for example, a reaction time of about 1 to about 20 hours can be exemplified. Examples of the reducing agent used in the above reduction reaction include metal hydrides such as lithium aluminum hydride and sodium borohydride; metal alcoholates such as aluminum isopropoxide; and the like. Specific examples of the inert organic solvent include methanol, ethanol, propanol, isopropyl alcohol, butanol, water, ether, tetrahydrofuran, dioxane, benzene, hexane, petroleum ether, and pentane. 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 amount is about 1 to about 50 times the weight of the compound of formula (5), more preferably about 2 times the weight of the compound of formula (5).
An example of the usage amount is about 10 times the weight. After the completion of the above reaction, for example, by injecting the reaction product into water or removing the catalyst, extracting with an extraction solvent such as benzene, washing the solvent layer with water, drying, and concentrating, the formula ( 1-decyn-5-ol represented by 3) can be obtained with high yield and high purity. If desired, further purification can be carried out by means such as vacuum distillation or column chromatography. The 5-substituted-1-decene of the formula (2) used in the production of the 4-substituted nonanal of the formula (1) of the present invention is, for example, the 1-decyne of the formula (3) that can be obtained as described above. -5-ol, for example, in the presence of a base,
It can be formed by contacting with a halide of formula (4). This reaction can be expressed, for example, by formula (3)
Under conditions in which a compound is converted or formed into its alkali metal salt by means of an alkali metal base,
This can be carried out by contacting the halide of formula (4) in an inert organic solvent. The reaction temperature for the reaction for forming the compound of formula (2) above can be selected as appropriate, for example, a temperature range of about 0°C to about 100°C, more preferably a reaction temperature of about 20 to about 80°C. . The reaction time can be changed as appropriate depending on the reaction temperature, etc., for example,
An example of a reaction time is about 1 to about 20 hours. Specific examples of the alkali metal base used in the reaction include lithium hydride, sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, or sodium and potassium in a suitable alcohol. can. The amount of these bases to be used can be selected as appropriate, for example, from about 1 to about 3 to 1 mole of the compound of formula (3).
A molar amount is sufficient, more preferably about 1 to
A value of about 1.2 mol is often employed. The amount of the halide of formula (4) used in the above reaction can also be appropriately selected, and may be, for example, about 1 to about 2 moles per 1 mole of the compound of formula (3). Further, specific examples of the inert organic solvent used in the above reaction include benzene, toluene, xylene, dimethyl formaldehyde, ether, tetrahydrofuran, methanol, ethanol, propanol, isopropyl alcohol, butanol, t-butyl alcohol, etc. be able to. These solvents can be used alone or in combination of two or more.
There are no special restrictions on the amount of these solvents used, but
About 2 to about 50 times the weight of the compound of formula (3),
More preferably, the amount used is about 3 to about 10 times the weight. After the completion of the above reaction, for example, the reaction product is poured into water, neutralized, extracted with an extraction solvent such as benzene, and the solvent layer is washed with water.
By drying and concentrating, the 5-substituted-1-decene represented by formula (2) can be obtained with high yield and high purity. If desired, it can be further purified by means such as vacuum distillation or column chromatography. According to the present invention, for example, the 5-substituted-1-decene of formula (2) that can be obtained as described above is brought into contact with ozone, and the product is reductively decomposed in the presence of a reducing agent. By this method, 4-substituted nonanals of formula (1) which have not been described in any literature can be produced. This reaction can be carried out in the presence or absence of a solvent. The reaction temperature of the ozone oxidation reaction mentioned above can be selected as appropriate, for example, a temperature range of about -78 to about +30°C,
More preferably, a reaction temperature of about -30 to about -78°C can be exemplified. The reaction time can be changed as appropriate depending on the ozone flow rate, reaction temperature, etc., and for example, a reaction time of about 30 to about 10 hours can be exemplified. When carrying out the above ozone oxidation reaction, the amount of ozone used can be appropriately selected, and for example, about 0.8 to about 1.5 mol is often employed per 1 mol of the compound of formula (2). Specific examples of inert organic solvents used in the reaction include pentane, hexane, cyclohexane, benzene, carbon tetrachloride, chloroform, methylene dichloride, ethyl chloride, ether, tetrahydrofuran, ethyl acetate, Examples include acetone, nitromethane, and formaldehyde. Among the above-mentioned solvents, examples of active solvents include formic acid, acetic acid, propionic acid, methanol, ethanol, propanol, and water. 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 amount used is about 2 to about 20 times, more preferably about 10 to about 30 times the weight of the compound of formula (2). can do. Further, specific examples of the reducing agent used in the reductive decomposition reaction using the above reducing agent include zinc dust, triphenylphosphine, dimethyl sulfide, sodium iodide, ferrous sulfate, catalytic hydrogenation catalyst, etc. can be mentioned. The amount of these reducing agents to be used can be selected as appropriate; for example, about 1 to about 40 mol is sufficient per 1 mol of the compound of formula (2), and more preferably about 1 to about 10 mol. often adopted. The reductive decomposition reaction can be carried out, for example, by dropping the ozone oxidation product little by little into a mixed solution of zinc dust and glacial acetic acid. The temperature of the reduction reaction can also be selected appropriately, for example, a temperature range of about -30 to about +20°C, more preferably a reaction temperature of about -10 to about 0°C. The reaction time can be changed as appropriate depending on the reaction temperature and the like, and for example, a reaction time of about 1 to about 5 hours can be exemplified. After the completion of the above reaction, for example, the reaction product is injected into water, dried, and concentrated to produce the target compound, 4-substituted nonanal represented by the above formula (1), in high yield and high purity. Obtainable. If desired, further purification can be carried out, for example, by means such as vacuum distillation or column chromatography. Hereinafter, several aspects of the present invention will be explained in more detail with reference to Examples. Reference Example 1 Production of 1-decene-5-ol [formula (5)] 5.5 g (0.24 mol) of metallic sodium and 120 ml of anhydrous ethyl alcohol were placed in a reaction vessel.
Prepare sodium ethoxide ( _C2H5ONa ) under _reflux . Next, ethyl 3-oxooctanoate44
g (0.24 mol) and stirred and reacted for about 1 hour while refluxing at a temperature of about 80°C. Furthermore, under reflux,
It took about 40 minutes to produce 17.6g (0.23g) of allyl chloride.
mol) dropwise. After dropping, continue under reflux for about 3
Stir for a time to react. After the reaction is completed, the solution is cooled, the resulting salt precipitate is filtered off by suction, and the solution is concentrated.
Next, add 200ml of 7.5% sodium hydroxide aqueous solution,
Hydrolyze for about 2 hours under reflux. After hydrolysis, the mixture is made acidic with sulfuric acid, and then decarboxylated under reflux for about 1 hour. After the reaction is complete, the reaction product is neutralized and extracted with benzene. Wash the extract with alkaline, water,
Dry and concentrate. By distilling the obtained residue under reduced pressure, 25 g of pure 1-decen-5-one was obtained.
(boiling point: 95-109°C/22mmHg, yield: 70%). Reference Example 2 Production of 1-decen-5-ol [Formula (3)] 7.9 g (0.21 mol) of sodium borohydride (NaBH ₄ ) and 300 ml of 95% ethyl alcohol are charged into a reaction vessel. Next, while stirring under water cooling, 200 ml of an ethyl alcohol solution containing 42.5 g (0.28 mol) of 1-decen-5-one was added dropwise over about 1 hour. After the addition, the mixture is stirred and reacted at room temperature for about 2 hours. After the reaction is complete, the reaction product is poured into dilute hydrochloric acid and extracted with benzene. Wash the extract with water, dry, and concentrate. By distilling the obtained residue under reduced pressure,
Pure 1-decene-5-ol 37.4g (boiling point: 70
~80°C/3mmHg, yield: 85%). Reference Example 3 Production of 5-ethoxy-1-decene [formula (2)] 4.3 g (0.18 mol) of sodium hydride and 100 ml of toluene were placed in a reaction vessel and stirred. next,
23 g (0.15 mol) of 1-decen-5-ol is added dropwise over a period of 5 minutes. After the addition is complete, the mixture is further stirred and refluxed for 2 hours. Next, under stirring and reflux, ethyl bromide 21.8
g (0.2 mol) was added dropwise. After dropping, the reaction is further continued for 5 hours. After the reaction is completed, the reaction product is poured into water, extracted with benzene, washed with water, dried, and concentrated. By distilling the obtained residue under reduced pressure, 22g of pure 5-ethoxy-1-decene (boiling point: 90~
100°C/18mmHg, yield: 80%). Reference Examples 4 to 10 Production of 5-substituted-1-decenes [formula (2)] According to the method of Reference Example 3, various 5-substituted-1
-Obtained decenes. The results are shown in Table.

[Table] Examples 1 to 12 Production of 4-ethyloxynonanal [formula (1)]:
- Charge 500 ml of a methylene chloride solution of 22 g (0.12 mol) of 5-ethoxy-1-decene into a reaction vessel. −
At a reaction temperature of 40° to -20°C, add 60ml of ozone gas/
React for 30 minutes at a rate of 30 minutes. After the reaction is complete,
The reaction product is gradually added dropwise to a mixture of 40 g of zinc powder and 100 ml of glacial acetic acid at a temperature of about 0° C. while stirring. After the dropwise addition was completed, the reaction was further stirred for 2 hours. After the reaction is completed, the reaction product is extracted with a solvent, washed, dried, and concentrated. Pure 4-ethoxynonanal is obtained by distilling the obtained residue under reduced pressure.
17.4g (boiling point: 75-85℃/4mmHg, yield: 78
%). Production of 4-substituted nonanals [formula (1)]: - According to the method of Example 1, various 4-substituted nonanals were obtained. The results are shown in Table.

【table】

Claims (1)

[Claims] 1. The following formula (1) However, in the formula, R is a C ₁ to C ₁₅ alkyl group and a C ₈
A 4-substituted nonanal represented by: a group selected from the group consisting of ~ _C10 aralkyl groups.