JPS6152810B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides the following formula (2), which has not been previously described in any known literature, and which is useful as a synthetic intermediate for the aromatic flavor component in natural apples and the compound represented by the following formula (1), which is known as a synthetic intermediate thereof. However, in the formula, R is

[Formula] group,

The present invention relates to a compound represented by the formula: and a group selected from the group consisting of a CH ₃ CH ₂ C≡CCH ₂ - group, and X represents a halogen, and a method for producing the same. 3-hydroxy-1-octyl acetate and 3-hydroxy-cis (or trans)-5-octen-1-yl acetate included in the formula (1) below are compounds isolated from apple essential oil of natural origin. It is one of the important aroma and flavor components of apple essential oil, and is highly valuable as a base material for flavor preparations and other aroma and flavor imparting or modulating agents. Furthermore, 3-hydroxy-5 included in the formula (1) below
-Octin-1-yl acetate is produced by a known hydrogenation method to produce 3-hydroxy-cis-5
- capable of producing octen-1-yl acetate;
It is an important intermediate. Regarding the intermediate and its manufacturing method, please refer to Japanese Patent Application No. 52-251652 (Japanese Patent Application No. 54-84511).
This is disclosed in the proposal of According to this proposal, the following diagram: However, R″ is

【formula】

[Formula] or CH ₃ CH ₂ C≡C-CH ₂ - group,
R' represents a CH ₃ - group or a CH ₃ CH ₂ - group. In addition, X represents halogen, and the compound of formula (1) can be synthesized as illustrated in the following. The present inventors conducted research to provide a method for synthesizing the compound of formula (1) in an industrially more advantageous manner and in a shortened process compared to the above proposal. As a result, compared to the raw material compound in the above conventional method, _{β- expressed} by the following formula (3) From halogenopropanal, the following formula (2) can be produced with high yield and purity using an industrially shortened process. However, R in the formula is

【formula】

[Formula] or CH ₃ CH ₂ C≡CCH ₂ - group, X represents halogen, 1-halogeno-3 which has not been described in the conventional literature
-We discovered that hydroxy linear _C8 compounds can be synthesized. Therefore, an object of the present invention is to provide a method for producing the compound of formula (1), which is useful as, for example, an aroma and flavor imparting or modulating agent. Another object of the present invention is to provide a compound of formula (2) which is useful for use in such a production method and which has not been described in any prior literature, and a method for producing the same. The above objects and many other objects and advantages of the present invention will become more apparent from the following description. The 1-halogeno-3-hydroxy linear _C8 compound of the above formula (2) of the present invention is, for example, the following formula (4), RMgY (4) where R has the same meaning as above, and Y represents a halogen. A halogenated magnesium compound represented by
By contacting with β- _{halogenopropanal} represented by the following formula ( ₃ ), It can be manufactured using Moreover, the above formula (4) halogenated magnesium compound is, for example, the following formula
(5), RY (5) where R and Y have the same meanings as above, and can be easily obtained by a Grignard reagent forming means known per se, which brings an organic halide represented by the following into contact with metallic magnesium. I can do it. An embodiment of the method of the present invention can be illustrated as shown in the process diagram below. β-halogenopropanal of the above formula (3) is a known compound obtained by adding hydrogen halide to acrolein, and the compound of formula (2), which has not been described in the conventional literature of the present invention, is as described above. It can be formed by bringing a halogenated magnesium compound of formula (4), which can be obtained by formula (4), into contact with β-halogenopropanal of formula (3). When carrying out the above formula (2) compound formation reaction, for example, formula (3) is added to a solution of formula (4) compound in an inert organic solvent.
By bringing the compounds into contact dropwise, the compound of formula (2) can be formed in good yield and selectivity. At this time, if desired, the reaction may be carried out in the presence of a hydrogen halide trapping agent such as pyridine. The reaction can be carried out over a wide temperature range, for example from about -80°C to about +200°C, and from about -80°C to about 30°C.
A more preferable example is a temperature range of about 0.degree. Further, the dropping time and the reaction time can be changed as appropriate depending on the reaction temperature, etc., for example, about 1 to about 50
An example of the reaction time is about hours. Although the amount of the compound of formula (4) used in the Grignard reaction can be selected as appropriate, the compound of formula (3) 1
For example, the amount used can be about 1 to about 2 moles based on the mole. Further, specific examples of the inert organic solvent used in the Grignard reaction include ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, dimethoxyethane, diglyme, tetrahydrofuran, and dioxane, and also benzene, toluene, Examples include hydrocarbon solvents such as n-hexane. 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, for example, about 1 to about 200 times, more preferably about 5 to about 50 times, the weight of the compound of formula (4) as the raw material. I can give an example. After the completion of the Grignard reaction, for example, the reaction product is injected into saturated ammonium chloride water, the reaction solution is decomposed, extracted with an appropriate solvent, the solvent layer is washed with water, dried, and concentrated, so that the formula (2 ) New compounds can be obtained in high yield and purity. If desired, it can be further purified, for example by distillation under reduced pressure. In the present invention, the compound of formula (2) that can be derived from the compound of formula (3) and the compound of formula (4) as described above, for example, is an oily compound that has not been described in any literature. Specific examples of such compounds of formula (2) include b 1-chloro-trans-5-octene-3-
All c 1-chloro-5-octyn-3-ol d 1-bromo-cis-5-octen-3-ol and the like can be mentioned. The boiling points of these new compounds are listed below. Compound Boiling point b 90~93℃/3mmHg c 94~96℃/3mmHg d 93~95℃/3mmHg Formula (2) of the present invention which can be obtained as described above
The compound is useful as an intermediate for producing the known compound of formula (1). The compound of formula (1) is subjected to a desalting reaction by reacting the compound of formula (2) with an alkali metal acetate in an organic inert solvent such as dimethylformamide or dimethyl sulfoxide,
It can be easily produced with good yield and selectivity. This desalting reaction can be carried out, for example, at a temperature range of about 10 to about 200°C, and a more preferable example is a temperature range of about 50 to about 150°C. The reaction time can be appropriately changed depending on the reaction temperature and the like, and can be exemplified by a reaction time of about 1 to about 50 hours. Specific examples of the alkali metal acetate used in the desalting reaction include sodium acetate, potassium acetate, lithium acetate, and the like. Although the amount of these alkali metal acetates to be used can be changed as appropriate, for example, the amount used can be about 1 to about 5 times the mole of the compound of formula (2). More preferably, about 1 to about 2 times the mole is often employed. Examples of solvents used in the reaction include, in addition to the dimethylformamide and dimethyl sulfoxide, hydrocarbon solvents such as benzene, xylene, toluene, and hexane, and diethyl ether, diisopropyl ether, dimethoxyethane, and the like. Examples include ether solvents such as dimethoxymethane, tetrahydrofuran, and dioxane. These solvents can be used alone or in combination. There is no particular restriction on the amount of these solvents used, but the amount used is, for example, about 1 to about 50 times, more preferably about 3 to about 30 times the weight of the compound of formula (2). can do. After completion of the desalting reaction, for example, the reaction product is injected into water, extracted with an appropriate solvent, and the solvent layer is washed with water, dried, and concentrated to obtain the linear C ₈ of formula (1).
The 3-hydroxy-1-acetoxy linear _C8 compound can be obtained in high yield and purity. If desired, it can be further purified 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. Example 1 [1-Bromosis 5-octen-3-ol] A Grignard reagent is prepared from 8 g (0.33 gram atom) of metallic magnesium, 31.35 g (0.3 mol) of cis-2-pentenyl chloride, and 100 ml of tetrahydrofuran. On the other hand, 11g of hydrogen bromide gas in 60ml of ether
Then, 16.8 g (0.3 mol) of acrolein was added dropwise at a reaction temperature of 0 to 10°C, and the reaction was further continued for 20 minutes at the same temperature to prepare β-bromopropanal. After adding 3 g of pyridine to the Grignard reagent, the ether solution of β-bromopropanal is added dropwise at a reaction temperature of -10° to 0°C. After the dropwise addition was completed, stirring was continued for another 1.0 hour at the same temperature to complete the reaction. The reaction solution was poured into saturated aqueous ammonium chloride for decomposition, and the organic layers were extracted with ether and combined. After washing with brine and drying, the solvent was recovered to obtain 31 g of crude 1-bromosis 5-octen-3-ol. Distillation under reduced pressure yielded 29 g of pure 1-bromosis 5-octen-3-ol having a boiling point of 93-95°C/3 mmHg (66% yield). Reference example Obtained 1-bromosis 5-octene-3
3-Hydroxy-
Cis-5-octen-1-yl acetate (boiling point
93-94°C/2mmHg) was obtained in a yield of 40%. Example 2 [1-chloro-trans・5-octene-3-
By using trans-2-pentenyl-chloride in place of cis-2-pentenyl-chloride in Example 1 and carrying out the same reaction procedure, 1-chloro-trans having a boiling point of 90 to 93°C/3 mmHg was obtained.・5-octene-3-ol 28.5
(65% yield). Reference Example The obtained 1-chloro-trans-5-octen-3-ol was desalted to yield 3-hydroxy-trans-5-octen-1-yl acetate (boiling point 91-93°C/2mmHg). obtained at a rate of 47%. Example 3 [1-Chlor-5-octen-3-ol] Using 2-pentynyl bromide in place of cis-2-pentenyl-chloride in Example 1,
By performing the same reaction operation below, the boiling point
27 g of 1-chloro-5-octin-3-ol with a temperature of 94-96°C/3 mmHg was obtained (62% yield). Reference Example The obtained 1-chloro-5-octyn-3-ol was desalted to form 3-hydroxy-5-octyn-1-yl acetate (boiling point 113-115℃/
3 mmHg) was obtained in a yield of 29%.

Claims (1)

[Claims] 1. The following formula (2) However, in the formula, R represents a group selected from the group consisting of [Formula] group, [Formula] group, and CH ₃ CH ₂ C≡CCH ₂ - group, and X represents halogen, 1-halogeno- 3-hydroxy straight chain
_C8 compound. 2 The following formula (4) RMgY (4) In the formula, R represents a group selected from the group consisting of a [formula] group, a [formula] group, and a CH ₃ CH ₂ C≡CCH ₂ - group, and Y represents a halogen A halogenated magnesium compound represented by the following formula (3), XCH ₂ CH ₂ CHO (3) in which X represents a halogen, is brought into contact with β-halogenopropanal represented by Characterized by the following formula (2) However, in the formula, R and X have the same meanings as above, and a 1-halogeno-3-hydroxy straight chain represented by
Method for producing _C8 compounds.