JP3280447B2 - Method for producing allyl chloride - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to geranyl chloride,
The present invention relates to a method for producing a mixture of neryl chloride and linalyl chloride (hereinafter abbreviated as allyl chloride; Linalool is represented by L, geranyl chloride is represented by GC, neryl chloride is represented by NC, and linalyl chloride is represented by LC in a chemical reaction formula). These compounds are useful, for example, as a raw material for synthesizing geranyl sulfone, which is a raw material for vitamin A (JP-A-63-227564,
JP-A-63-227565).

[0002]

2. Description of the Related Art Conventionally, as a method for producing allyl chloride, a method using myrcene or geraniol, nerol and linalool as raw materials has been widely known . As a method using myrcene as a raw material, a method of reacting hydrogen chloride in the presence of a copper catalyst is known (for example, US Pat. No. 3,016,408). As an improvement of this method, a method of adding amines to a reaction system (Japanese Patent Laid-Open No.
0-41623, JP-A-61-112033) and a method of adding sulfides (JP-A-63-25)
No. 0328). Also, when using geraniol, nerol and linalool as raw materials, in the presence of a base such as pyridine, an equivalent or more of thionyl chloride,
A method of causing a so-called chlorinating agent such as phosphorus trichloride to act is known (see Reference Example). However, when using myrcene as a raw material, myrcene itself may be produced from a raw material derived from a natural product, and there is uncertainty in supply in terms of industrial mass use. On the other hand, when geraniol, nerol, and linalool are used as raw materials, they are manufactured stably using petrochemicals, so there is no concern about supply in comparison with myrcene. On the other hand, there is a disadvantage that it is necessary to use an expensive chlorinating agent such as thionyl chloride or phosphorus trichloride.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to reduce the cost of linalool, which is industrially mass-produced, without using expensive halogenating agents, thionyl chloride and phosphorus trichloride. To provide a method for producing allyl chloride.

[0004]

Embedded image

[0005]

According to the present invention, the object is to provide a linalool with a copper compound and a compound of the general formula

[0006]

Embedded image (Wherein R ₁ , R ₂ and R ₃ are each a hydrogen atom,
Child provide a manufacturing process comprising represents a carbon hydrocarbon radical, R _1, the total number of carbon atoms in R ₂ and R ₃ exerts hydrogen chloride in the presence of an amine represented by 6 or more is)
It was found to be achieved by the.

The copper compounds used in the present invention include copper halides such as copper chloride, copper bromide, and copper iodide; copper carbonate; copper formate;
It is a cuprous salt or a cupric salt such as copper carboxylate such as copper acetate. Particularly cuprous chloride is preferred. The copper compound is used in an amount of 0.01 mol% or more, preferably 0.05 to 10 mol%, based on linalool, but may be used in an amount larger than 0.01 mol%.

Further, the amines used in the present invention are represented by the above general formula. R _1, R ₂ and R ₃ each <br/> hydrogen atom, or represents a carbon hydrocarbon group. Examples of the hydrocarbon group include linear or branched such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, undecyl, decyl, dodecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, and tetracosyl. Aliphatic hydrocarbon groups; aryl groups including ortho, meta or para isomers such as phenyl, tolyl, xylyl, naphthyl and biphenyl;
Aralkyl groups such as benzyl and phenethyl; cycloalkyl groups such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. R ₁ , R ₂ and R ₃ have a total carbon number of 6 or more. Typical of such amines are triethylamine, 2-ethylhexylamine, diisobutylamine, di-2-ethylhexylamine, trihexylamine, trioctylamine, tridecylamine, distearylmethylamine, dicyclohexylamine, N,
N-dimethylaniline, N, N-diethylaniline, diphenylamine, phenylethylamine, methylbenzylamine and the like. These amines are used in an amount of 0.1 mol% or more, preferably 0.5 mol%, based on linalool.
-10 mol%.

The reaction of the present invention can be carried out in the absence of a solvent. Of course, a solvent such as methylene chloride may be used as long as the reaction is not hindered. A system reaction is recommended.

The reaction is carried out, for example, by blowing hydrogen chloride into a mixture of linalool, a copper compound and an amine, or a mixture to which a solvent is added as required, with stirring. The amount of hydrogen chloride blown is 0.9 to 1.2 mol times relative to linalool. The reaction is from -10 ° C to 50
Performed at ° C. When the reaction temperature is increased, hydrogen chloride is significantly added to the terminal double bond of linalool, which is disadvantageous for the reaction. Therefore, the preferred reaction temperature is between -5C and 20C. The progress of the reaction can be monitored, for example, by gas chromatography (OV-17, 3 m, 100 → 150 ° C., temperature rise at 10 ° C./min). It is important to control the amount of hydrogen chloride to be blown in by tracking the reaction and not to blow an excessive amount of hydrogen chloride into the reaction system more than necessary. Excess hydrogen chloride is added to the double bond of the product allyl chloride, which results in a decrease in the yield of allyl chloride. The reaction proceeds simultaneously with the blowing of hydrogen chloride. Therefore, when the predetermined amount of blowing is completed, the reaction is considerably advanced. However, in order to drive the reaction sufficiently, it is preferable to stop the reaction after further continuing stirring under the conditions. Usually, the time required to drive the reaction is within 10 hours.

By the above reaction, geranyl chloride,
A mixture of neryl chloride and linalyl chloride is obtained. These formation ratios vary greatly depending on the reaction temperature, reaction time, type and amount of the copper compound or amine, and the like. For example, cuprous chloride 0.5 to linalool
mol%, trioctylamine 0.05 mol%, and the production ratio when blowing hydrogen chloride 1.14 mol times at a reaction temperature of 5 to 10 ° C. is geranyl chloride / neryl chloride / linalyl chloride = 5
1/27/22.

[0012] After the reaction, water is added to the reaction solution to separate a desired oil component. The oil may be extracted using an extractant such as hexane or toluene. The oil or the extracted oil is washed with 5% aqueous ammonium chloride, then with 5% aqueous sodium bicarbonate and water, and when an extractant is used, the extractant is distilled off. can do.
When the allyl chloride thus produced is used, for example, in the synthesis of geranyl sulfone as a vitamin A raw material, it can be used as it is without purification.

[0013]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 15.4 g of linalool in a 100 ml three-necked flask
(0.1 mol), 0.05 g of cuprous chloride (0.5 mm
ol) and 0.19 g (0.5 m) of trioctylamine
mol), and mechanically stirred. Then, while keeping the reaction temperature at 5 to 10 ° C, hydrogen chloride was slowly blown into the liquid through a thin tube. The internal temperature gradually rises,
The color of the liquid has become blackish. 4.16 g of hydrogen chloride (0.
114 mol) over about 1 hour. After completion of the blowing, stirring was continued at that temperature for about 4 hours. Next, the reaction mixture was transferred to a 300-ml separatory funnel, 50 g of hexane and 50 g of a 5% ammonium chloride solution were added, and the mixture was shaken well. Separate the lower layer and add another 5%
Was washed with 50 g of an ammonium chloride solution. The lower layer was separated, and the upper layer was washed with 50 g of 5% aqueous sodium bicarbonate and then with 50 g of water. Hexane was distilled off under reduced pressure using an evaporator to obtain 16.1 g of a brown oil. The product was analyzed by gas chromatography according to the internal standard method, and was determined to be a mixture of geranyl chloride, neryl chloride and linalyl chloride.
It contained 3.4 g. The yield was 77.7% and the conversion of linalool was 98.1%. The production ratio of geranyl chloride, neryl chloride and linalyl chloride was geranyl chloride / neryl chloride / linalyl chloride = 51/27/22.

Gas Chromatography Conditions Column: 0 V-17, 3 m Column temperature: 100-150 ° C., heated at 10 ° C./min Internal standard substance: hexadecane

Examples 2 to 5 Reactions, treatments and analyzes were carried out in the same manner as in Example 1 except that the types of copper compounds and amines and the amounts used thereof were changed. Table 1 shows the results. In the table, (mol
%) Is based on linalool.

[0017]

[Table 1]

Reference Example 15.4 g of linalool in a 100 ml three-necked flask
(0.1 mol), 9.5 g of pyridine (0.12 mol
1) was taken, and the internal temperature was adjusted to 5 ° C. Next, 12.5 g (0.105 mol) of thionyl chloride was added dropwise with stirring over about 30 minutes. A white precipitate formed upon dropping. During the dropwise addition, the reaction temperature was maintained at 5 to 10 ° C. After completion of the dropwise addition, the mixture was further stirred at this temperature for 2 hours.

Next, the reaction mixture was transferred to a 300 ml separating funnel, and 50 g of water was added to wash the mixture thoroughly. The lower layer was separated, and the upper layer was treated with 50 g of 5% aqueous sodium bicarbonate and 50 g of water.
g. Hexane was distilled off under reduced pressure using an evaporator to obtain 15.9 g of a brown oil. The product was found to contain 12.9 g of a mixture of geranyl chloride, neryl chloride and linalyl chloride by gas chromatography analysis using the same internal standard method as in Example 1. Yield 74.9%. The production ratio of geranyl chloride, neryl chloride and linalyl chloride was calculated as follows: geranyl chloride / neryl chloride / linalyl chloride = 56
/ 21/23.

[0020]

According to the present invention, linalool is treated with hydrogen chloride in the presence of a copper compound and amines to produce geranyl chloride, neryl chloride, and geranyl chloride, which are useful as raw materials for geranyl sulfone, which can be a raw material for vitamin A. Linalyl chloride can be produced in good yield and at low cost.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-60-41623 (JP, A) JP-A-60-58930 (JP, A) JP-B-31-2976 (JP, B1) (58) Field (Int.Cl. ⁷ , DB name) C07C 17/16 C07C 21/19 C07B 61/00 300 C07B 39/00

Claims (1)

(57) [Claims] 1. A linalool containing a copper compound and a general formula (Wherein R ₁ , R ₂ and R ₃ are each a hydrogen atom,
Represents a carbon hydrocarbon radical, R _1, geranyl R total number of carbon atoms of _2, and R ₃ is characterized by the action of hydrogen chloride in the presence of an amine represented by 6 or more is) chloride, Nerirukuroraido And a method for producing a linalyl chloride mixture.