JPS584733A - Preparation of alkynyl compound - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as an intermediate for agricultural chemicals, etc. industrially and advantageously, by synthesizing sodium acetylide in an insoluble organic solvent, adding liquid ammonia to the reaction system, and reacting the sodium acetylide with a halogenated organic compound. CONSTITUTION:A compound of the formula R<1>C CH (R<1> is H, alkyl, alkenyl, aryl, preferably H, phenyl or 1-10C straight chain alkyl) or the formula R<2>CH= C=CH2 (R<2> is alkyl, preferably CH3) is reacted with a finely dispersed metallic sodium to synthesize sodium acetylide. Liquid ammonia is then added to the reaction system, and a compound of the formula R<3>X(R<3> is substituted or unsubstituted monofunctional hydrocarbon residue; X is Br or I) is reacted with the sodium acetylide to afford the aimed alkynyl compound corresponding to the raw material. This method requires no cryogenic refrigerator, and the ammonia can be easily separated and recovered.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing alkynyl compounds, and in particular provides an advantageous method for synthesizing alkynyl compounds that are useful as synthetic intermediates for agricultural chemicals, pharmaceuticals, synthetic fragrances, etc. be.

Conventionally, as a method for obtaining an alginic compound by reacting sodium acetylide with a halogenated organic compound, for example, (1) sodium acetylide is synthesized in liquid ammonia, and the alkyne compound is further reacted with an alkyl halide at -40°C. How to obtain (J, Ohem,
Boa,, 115 (1950)] Arike, (
2) Synthesize sodium acetylide in xylene and N
, A method for obtaining alkyne compounds by reacting with an alkyl halide at 30°C using N-dimethylformamide as a co-solvent (J, Org, Ohem, ,
24, 840 (1959)] is known.

However, in the case of the former method (1), since sodium acetylide is synthesized in liquid ammonia, acetylene is contained in the recovered liquid ammonia. Since it is difficult to separate this acetylene from the liquid ammonia, the recovered liquid ammonia containing this acetylene poses a safety problem when stored or reused. Furthermore, since the reaction temperature is 140'C, a powerful refrigerator is required, and therefore method (1) cannot necessarily be said to be a two-industry production method. On the other hand, the latter method (2) has the advantage of not requiring a powerful refrigerator like the method (]), but since it uses N,N-dimethylformamide, there is a problem in its recovery. .

That is, since N',N-dimethylformamide is a water-soluble organic solvent, when the reaction solution is hydrolyzed after the reaction is completed, most of the N,N-dimethylformamide migrates to the aqueous layer. As a result, in order to dispose of this aqueous layer, it is necessary to separate and recover the N,N-dimethylformamide contained in it in advance by means such as solvent extraction method and distillation recovery method due to the requirement of pollution prevention. is quite difficult, so method (2) cannot necessarily be said to be an industrial method either.

The present invention aims to solve these conventional disadvantages and provide an advantageous method for producing the target alkynyl compound, which is (a) in an inert organic solvent.

Acetylene compound represented by the general formula R' OmiOH (R1 in the formula represents a hydrogen atom, an alkyl group, an aryl group, or an alkenyl group), or a general formula F120) 1=O=O
1 represented by H2 (R2 in the formula represents an alkyl group)
, a step of reacting a 2-diene compound with finely dispersed metallic sodium to produce sodium acetylide, and then (b) adding liquid ammonia to this reaction thread, followed by a step of reacting with the general formula R3X (BS in the formula is substituted or unsubstituted). A step of adding a halogenated organic compound represented by a monovalent hydrocarbon group (wherein X represents an odorant or iodine atom) and reacting it with the sodium acetylide.

The present invention relates to a method for producing an alkynyl compound characterized by comprising:

According to the method of the present invention, (1) the reaction system can be pressurized (acetylene is not included) when adding liquid ammonia, and the temperature of one reactor can be set at -20°C to 20°C; , a cryogenic refrigerator is not required; an ordinary refrigerator is sufficient. ■Separation and recovery of ammonia is easily performed by simple distillation from the reactor. ■The separated and recovered ammonia does not contain any impurities, so it has the advantage of being able to be reused as is.

To explain the method of the present invention in detail, sodium acetylide is synthesized by reacting masses. Specifically, this method involves finely dispersing metallic sodium in an inert organic solvent, and adding the raw material acetylene compound or A 1.2-diene compound may be gradually added under heating to react and generate sodium acetylide. Examples of inert organic solvents used here include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, heptane and octane, and ethers such as dibutyl ether and diphenyl ether. For example, the amount of inert M: organic solvent used is metal sodium 1
100 to 1000y-(preferably 2()) per mole
0~400. P), and the particle size of the dispersed sodium metal is preferably 1000 μm or less (especially 100 μm).
1 or less) is deplorable.

-1 The raw material acetylene compound or 1,2-diene compound to be reacted with this finely dispersed gold-sodium is shown in the general formula above, and this acetylene compound includes acetylene, methylacetylene, ethylaretylene, etc. Arylacetylenes such as alkyl acetylene and phenylacetylene, arylacetylenes such as 4-hexen-1-yne, etc., and 1,2-diene compounds include argyl-1, such as 1,2-butadiene and 1,2-pentadiene, etc. Examples include 2-diene and the like.

The molar ratio in which the above raw material compound and the above metal sodium are reacted is 1 to 0.3 mol (
The amount is preferably 0.7 to 0.5 mol). In addition, when the reaction temperature is low, the reaction rate becomes slow; on the other hand, 13
If the temperature exceeds 0℃, the generated sodium acetylide will decompose, so the temperature should be 80~130℃ (preferably 95~130℃).
The wetting range is preferably 115° C.), and usually it is preferably carried out at a temperature higher than the melting point of metallic sodium (97° C.).

Next, liquid ammonia is added to the reaction system in which sodium acetylide is produced by the reaction as described above, and then a halogenated organic compound represented by the general formula R3X is added and reacted with the sodium acetylide. The purpose of adding liquid ammonia at this time is to form a mixed solvent system with an inert organic solvent by adding this liquid ammonia, so the liquid ammonia is added to 0.5 liters of inert organic solvent. It is preferable to add in a range of 2 to 2 (capacity ratio).

The halogenated organic compound added after liquid ammonia is added is represented by the general formula above, where R3 represents a substituted or unsubstituted monovalent hydrocarbon group.
1 This includes alkyl groups, alkenyl groups, aryl groups, and alkyl groups, alkenyl groups, and aryl groups having functional groups such as halogen atoms, ether groups, ester groups, and silyl groups; Indicates an iodine atom.

Such halogenated organic compounds include ethyl bromide, butyl iodide, 1-chloro-3-bromopropane, 1-chloro-4-bromobutane, 1,4-dibromobutane, phenyl bromide, and 6-promohegyl biranyl ether. , 6-70 mohexyl acetate, 2-butenyl bromide, ]-bromo-4-trimethylsilylbutane, and the like.

In comparison with the reaction molar ratio between the halogenated organic compound described in Section 2 and the sodium acetylide, the amount of the halogenated organic compound may be 08 to 1.2 mol per mol of sodium atom. In addition, the reaction temperature may be in the range of -2()℃ to 20℃.
: If the temperature is lower than -20℃, the reaction rate is slow, and if it is manufactured industrially, it is necessary to equip a cryogenic refrigerator.
This is disadvantageous both economically and in terms of operation, and if the temperature is higher than 20°C, the reaction pressure becomes high, which is disadvantageous in terms of equipment and operation.

After the reaction is completed, ammonia is collected, washed with water, and the organic layer is distilled (distilled under reduced pressure if necessary) to obtain the target alkynyl compound.

By the method of the present invention, it is possible to advantageously obtain an alkynyl compound that is useful as an intermediate in the synthesis of agricultural chemicals, medicines, synthetic fragrances, and the like.

For example, by using pentylacetylene as a starting material, reacting it with metallic sodium according to the method of the present invention to obtain sodium hebutynylide, and then reacting it with bromochloropropane, 1-chloro-4-decyne can be obtained in a similar yield. can get. This 1-chloro-4-decine is derived from “Douglas,” which is known as a pest in forests in the United States.
``Z-6-heneikosen-11-:ton'', which is the sex pheromone of ``-firtussook moth''
It can be induced with high yield, and recently, efforts have been made to use this sex pheromone to control these pests.

Next, a specific example will be given.

Example 1 A flask with a content M of 500 was charged with 250y of xylene and metallic sodium dispersed in a particle size of 20μ or less,
Acetylene gas li/ at reaction temperature 100-110℃
When the reaction system was blown into the reaction system at a flow rate of 100 min for 1 hour, sodium acetylide was obtained quantitatively relative to metallic sodium. This xylene dispersion of sodium acetylide was charged into an autoclave with an internal volume of 2 mm, and 600 Y of liquid ammonia was added thereto, and 171.57 of 1-chloro-4-bromobutane was added at a reaction temperature of -1θ°C to -5°C. It took some time to drip. The reaction pressure at this time is 3.5-4
It was Kf/crrf G. After the dropwise addition was completed, the mixture was stirred at -5°C for 2 hours, and then ammonia was distilled and recovered from the reaction system. The reaction residue was poured into 200 d of 20% aqueous hydrochloric acid solution, the layers were separated, and the organic layer was distilled under reduced pressure to obtain 93 y of 6-chloro-1-hexyne. The yield was 80% based on sodium metal.

Example 2 In Example 1, 1.2-
When the reaction was carried out under substantially the same conditions as shown in the same example except that butadiene gas was used, 115 units of 1-chloro-5-octyne were obtained.

The yield was 79.6% based on Kinpo sodium.

Example 3 In Example 1, when phenylacetylene 1537 was added dropwise instead of acetylene gas and reacted in accordance with the same example, 1-chloro-6-phenyl-5-hexyne was converted to 13! M' was obtained.

The yield was 70% based on sodium metal.

1 applicant for patent Shin-Etsu Chemical Co., Ltd. agent Patent attorney Ryo Yamamoto

Claims (1)

[Claims] 1. (a) In an inert organic solvent, the general formula R' O30H
(R1 in the formula is a hydrogen atom, an alkyl group, an alkenyl group,
(represents an aryl group), or an acetylene compound represented by the general formula R0M-0-OH2 (in the formula R2 represents an alkyl group)
A step of reacting the 1,2-diene compound represented by the formula with finely dispersed metallic sodium to produce sodium acetylide, and then (b) adding liquid ammonia to this reaction system, followed by the general formula R3X (in which R3 is an alkynyl compound characterized by the step of adding a herogenated organic compound represented by a substituted or unsubstituted monovalent hydrocarbon group (X represents a bromine or iodine atom) and reacting it with the sodium acetylide. manufacturing method. 2. A method for producing an alkynyl compound represented by the formula R"O'EO)T, wherein R1 is a hydrogen atom, in the method according to claim 1. 3. A method according to claim 1. A method for producing an alkynyl compound represented by the formula 0H30H,03OR'', wherein R2 is a methyl group. 4. A method for producing an alkynyl compound represented by the formula 06H,C2OR, wherein C5R is a phenyl group in the method described in claim @1. 5. The method according to claim 1, wherein R1 is a linear alkyl group having 1 to 10 carbon atoms,
30 A method for producing an alkynyl compound represented by R''.