JPH0348895B2 - - Google Patents

Description

[Detailed Description of the Invention] (Industrial Application Field) The present invention relates to a method for producing 11-tetradecenyl acetate, particularly a method for producing 11-tetradecenyl acetate, which is synthesized from sodium acetylide.
The present invention relates to a method for producing 11-tetradecenyl acetate, which is useful as a sex pheromone for trillworms, in a short process and with high yield via a 11-tetradecyl derivative.

(Prior art) It is well known that 11-tetradecenyl acetate, which is a sex pheromone compound of the leafworm, can be obtained from a 11-tetradecine derivative. (CH ₂ ) ₄ OCH ₂ OCH ₃ and
CH ₃ CH ₂ C≡C(CH ₂ ) ₆ Cl and cuprous chloride (CuCl)
A method of reacting in tetrahydrofuran in the presence of (Chemical Abstracts 100 , 15622/S
), using HO(CH ₂ ) ₁₂ OH as the starting material.
Br ₂ CH ₂ CHBr(CH ₂ ) ₁₀ CH≡ using OH as an intermediate
Alkylation method leading to C(CH ₂ ) ₁₀ OH (see Chemical Abstracts 102 , 203564j)
However, these methods all have the drawbacks of long steps, low yields, and the raw materials are expensive and difficult to obtain.

(Structure of the Invention) The present invention relates to a method for producing 11-tetradecenyl acetate that solves these disadvantages, and is a method for producing 11-tetradecenyl acetate by converting sodium acetylide represented by the formula CH ₃ CH ₂ C≡CNa in the presence of liquid ammonia. _{Below is} the general formula By reacting with a halogen compound, the general formula
CH ₃ CH ₂ C≡C(CH ₂ ) ₁₀ A 11-tetradecine derivative represented by Y (Y is the same as above), which is then directly or after deprotecting the functional group Y, hydrogenated and acetylated. It is characterized by:

That is, the present inventors investigated various methods for efficiently producing 11-tetradecine derivatives as intermediates in the production of 11-tetradecenyl acetate, and found that the above sodium acetylide was added to 1-bromo as a starting material. General formula X (CH ₂ ) ₁₀ Y (X, Y are as above) such as -10-chlorodecane
A 11-tetradecine derivative can be easily obtained by reacting the compound represented by, and by hydrogenating and acetylating this directly or after deprotecting the functional group Y, the desired 11 −
The inventors discovered that tetradecenyl acetate can be obtained in a high yield in a short process, and completed the present invention by conducting research on the types and reaction conditions of each component to be used.

Sodium acetylide, which is used as an initiator in the method of the present invention, is represented by the formula CH ₃ CH ₂ C≡CNa, which is prepared by finely dispersing metallic sodium in an inert solvent. It can be obtained by adding ethyl acetylene or 1,2-butadiene and reacting under heating. Examples of this inert solvent include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane and octane, and ethers such as dibutyl ether and diphenyl ether. The amount may be 100 to 1000 g, preferably 200 to 400 g. In addition, this metallic sodium has a diameter of 1000 μm or less, preferably 100 μm.
It is sufficient if they are dispersed into fine particles as shown below, and the amount of ethylacetylene and 1,2-butadiene to be reacted with the metallic sodium is 1 to 3 mol, preferably 1.5 to 2 mol, per 1 mol of metallic sodium. good. Note that this reaction temperature should be in the range of 80 to 130 degrees Celsius, as the reaction rate slows down at low temperatures and the sodium acetylide produced decomposes at temperatures above 130 degrees Celsius, but this preferred range is 95 to 130 degrees Celsius.
It is said to be 115℃.

This sodium acetylide then has the general formula
(CH ₂ ) ₁₀ Y, where X is a bromine atom or an iodine atom, Y is a chlorine atom, a bromine atom, or an ether such as methyl ether, methoxymethyl ether, or tetrahydropyranyl ether, or an organoleptic such as trimethylsilyl or tert-butyldimethylsilyl. It is reacted with a halogen compound, which is a silyl-protected hydroxyl group, and the halogen compounds include 1-bromo-10-chlorodecane, 10
-bromodecane-1-ortetrahydropyranyl ether, 1-chloro-10-iododecane, 1,
Examples include 10-dibromudecane and 10-iododecane-1-ol tetrahydropyranyl ether. However, since this reaction is characterized by the addition of liquid ammonia to form a mixed solvent system with an inert solvent, it must be carried out in the presence of liquid ammonia. The amount of ammonia added may be 0.2 to 2 times the volume of the inert solvent used in the production of sodium acetylide. The reaction between sodium acetylide and this halogen compound is carried out by adding 0.8 to 12 moles of the halogen compound to 1 mole of sodium acetylide, allowing the reaction to occur in a temperature range of -20 to 20°C, recovering ammonia, and washing. By distillation, the desired 11-tetradecine derivatives, such as 11-tetradecinyl chloride, 11-tetradecinyl bromide, 11-tetradecin-1-ol tetrahydropyranyl ether, etc., can be easily obtained with a yield of 65 to 85% based on sodium metal. Obtainable.

By hydrogenating and acetylating the 11-tetradecine derivative thus obtained, it can be easily converted into 11-tetradecenyl acetate, which is useful as a sex ferrocene agent for trichophytes. However, either the hydrogenation or acetylation step may be performed first. Therefore, this
11-Tetradecine derivatives as they are, or those whose functional group Y has been deprotected,
You can first hydrogenate and then acetylate,
Conversely, it may be acetylated to form 11-tetradecine acetate and then hydrogenated to form 11-tetradecenyl acetate. The acetylation method for this hydrogenation may be carried out by a conventional method, but this hydrogenation may be carried out in the presence of, for example, a Lindlar catalyst or a Pd-BaSO ₄ catalyst. It may be acetylated with an acetic acid-pyridine system, an acetyl chloride-pyridine system, or, in the case of a halide, with potassium acetate, sodium acetate, etc.

Next, examples of the present invention will be given.

Example 1 (1) Synthesis of 11-tetradecynyl chloride Add 250 g of xylene and 23 g of metallic sodium dispersed to a particle size of 20 μm or less into a reactor.
When heated to 110℃ and blown ethyl acetylene gas at a flow rate of 1/min for 1 hour,
62.7 g of sodium acetylide was obtained almost quantitatively.

Next, this xylene dispersion of sodium acetylide was charged into an autoclave with an internal volume of 2, and after adding 600 g of liquid ammonia, the temperature was maintained at -10 to -5°C and the pressure was 3.5 to 4 Kg/cm ³ ·G. Bromo-10-chlorodecane
255.5g was dripped over 1 hour, and after the dripping was completed -
After stirring at 5°C for 2 hours, ammonia was recovered by distillation, the reaction product was poured into 20% HCl water, the organic layer was separated and the xylene was removed, and this concentrate was distilled under reduced pressure, resulting in a boiling point of 121-125. °C/4mm
Hg 11-tetradecynyl chloride 172g (yield
75%) was obtained.

(2) Synthesis of 11-tetradecynyl acetate 11-tetradecynyl chloride 172 obtained above
g into a reactor, add 230 g of anhydrous potassium acetate,
Add 260g of glacial acetic acid and heat to 160℃ under nitrogen gas atmosphere.
After the reaction, the mixture was poured into 500ml of water to separate the layers, and the organic layer was distilled under reduced pressure.The boiling point was 140-145℃/4mm.
226 g of 11-tetradecynyl acetate (yield 90%) was obtained using Hg.

(3) Synthesis of z-11-tetradecenyl acetate Next, 226 g of 11-tetradecenyl acetate obtained above was charged into autoclave 1.
Add 300 ml of methanol and 5% Pd-BaSO ₄ 10 to this.
After adding 40 g of hydrogen, hydrogen was introduced at a pressure of 5 kg.
11-tetradecynyl acetate was hydrogenated with stirring at ~50°C, and after confirming the theoretical amount of hydrogen absorption, the reaction product was concentrated and distilled to give 140
220 g (96% yield) of z-11-tetradecenyl acetate was obtained at ~142°C/4 mmHg.

Example 2 (1) Synthesis of 11-tetradecin-1-ol A xylene dispersion of sodium acetylide produced in the same manner as in Example 1 was charged into an autoclave with an internal volume of 2, and after adding 600 g of liquid ammonia, the temperature was lowered to -10~ -5℃, pressure 4.0~4.2
Kg/ ^cm3・G, here 10-bromodecane-1-ortetrahydropyranyl ether 321
g was added dropwise over 1 hour, and after the addition was completed, the mixture was stirred at -5°C for 2 hours, and the ammonia was distilled and recovered.
The obtained 11-tetradecin-1-ol tetrahydropyranyl ether was poured into 20% HCl water, and the organic layer was separated to remove xylene. Next, 600 ml of methanol and 2 g of p-toluenesulfonic acid were added to this, and the mixture was stirred under reflux for 4 hours. After the reaction, the pressure was reduced to recover methanol.
After washing with 500 ml of NaHCO ₃ water and distilling, 142 g (yield 67%) of 11-tetradecin-1-ol, which is a deprotected product of the above ether, was obtained at 136-138°C/4 mmHg.

(2) Synthesis of z-11-tetradecen-1-ol 11-tetradecen-1-ol obtained above
Put 142g into autoclave 1, add 200ml of n-hexane and 1g of Lindlar catalyst.
was added, and hydrogen gas was introduced into it at a pressure of 5 kg.
The hydrogenation reaction was carried out by stirring at 40 to 50°C, and the end point of the reaction was confirmed by gas chromatographic analysis of the sampled sample.The reaction product was then decanted to remove the catalyst, and n-hexane was removed under reduced pressure. After distillation, the result was 132-138℃/4mm.
135g of z-11-tetradecen-1-ol in Hg
(yield 95%) was obtained.

(3) Synthesis of z-11-tetradecenyl acetate 135 g of z-11-tetradecen-1-ol obtained above, 600 ml of n-hexane, and 67 g of triethylamine were charged into a reactor, and the mixture was heated to 10 to 15°C. 52 g of acetyl chloride was added dropwise, and after the addition was completed, the mixture was stirred at 20°C for about 1 hour to acetylate z-tetradecen-1-ol. 600 ml of pure water was added to dissolve the resulting triethylamine hydrochloride and the liquid was separated. Then, when n-hexane was removed from the organic layer under reduced pressure and distilled, the temperature was 140-142℃/4
z-11-tetradecenyl acetate 145 in mmHg
g (yield 90%) was obtained.

Claims (1)

[Claims] 1 Sodium acetylide represented by the formula CH ₃ CH ₂ C≡CNa is prepared by the general formula X in the presence of liquid ammonia.
(CH ₂ ) ₁₀ Y (where X is a bromine atom or an iodine atom,
Y is a chlorine atom, a bromine atom, or an ether group such as methyl ether, tetrahydropyranyl ether, trimethylsilyl ether, or a hydroxyl group protected by an organosilyl group) to form a compound with the general formula CH ₃ CH ₂ C≡ A 11-tetradecine derivative represented by C(CH ₂ ) ₁₀ Y (where Y is the same as above) is then hydrogenated and acetylated either directly or after deprotecting the functional group Y. Characteristic method for producing 11-tetradecenyl acetate. 2 Sodium acetylide represented by the formula CH ₃ CH ₂ C≡CNa is converted to the general formula X in the presence of liquid ammonia.
(CH ₂ ) ₁₀ Y (where X is a bromine atom or an iodine atom,
Y is a chlorine atom, a bromine atom, or an ether group such as methyl ether, tetrahydropyranyl ether, trimethylsilyl ether, or a hydroxyl group protected by an organosilyl group) to form a compound with the general formula CH ₃ CH ₂ C≡ A 11-tetradecine derivative represented by C(CH ₂ ) ₁₀ Y (where Y is the same as above), which is then directly or after deprotecting the functional group Y, acetylated, and hydrogenated. A method for producing 11-tetradecenyl acetate.