JPS5934718B2 - Method for producing ethyl acetylene magnesium haquid - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention particularly relates to a novel method for producing ethylacetylene magnesium halide, which is important as an intermediate for synthesizing hexyne-3-ol-1.

Hexene-3-ol-1 is produced by a partial hydrogenation reaction using a Lindlar catalyst to produce cis-hexene-3-ol-1 (commonly known as green leaf alcohol), which has a strong green aroma.
However, the method for producing hexyne-3-ol-1 is a method of reacting butynyl sodium with ethylene oxide as shown in the following formula (Journal of Chemical Society 195).
0, p. 877) Liquid ammonia C2H5C3CHC2H5C triethylene oxide CNaC2H5C= C-CH2CH20Na->C2H5C■C-CH2C
H2OH is known.

This method has disadvantages such as 1 long step, 2 pressure-resistant equipment required as liquid ammonia (boiling point -33°C) is used as the solvent, and 3 low yield (approximately 50%). Yes, it is not industrial. In addition, this manufacturing method includes 1,
A method of producing a halogenated magnesium salt of hexyne-3-ol-1 from butynyl sodium using 2-butadiene as a starting material through butynylmagnesium halide according to the following formula, and hydrolyzing this (Japanese Patent Application Laid-Open No. 50-184
(Refer to No. 06) CH3・CH=C=CH2−〉C2H5
C Mi C Na Mg
5C3C-CH2CH2OH is also known, but this has an industrial disadvantage in that it takes 5 to 7 hours at a reaction temperature of 50 to 120 DEG C. to produce butynylmagnesium halide.

As a result of intensive research aimed at solving these conventional disadvantages, the present inventors have established a method for producing ethylacetylene magnesium halide, which is considered to be extremely useful as an intermediate for synthesizing hexyne-3-ol-1.

That is, the present invention relates to a method for producing ethylacetylene magnesium halide, which is characterized by reacting 2-propynesulfonic acid ester and methylmagnesium halide.

The ethyl acetylene magnesium halide obtained by the method of the present invention can be easily and inexpensively produced by adding ethylene oxide to this substance to generate a halogenated magnesium salt of hexyne-3-ol-1, and hydrolyzing this. Hexyne-3-ol-1 can be obtained as follows. The method of the present invention will be explained in detail below.
First, 2-propynesulfonic acid ester as a starting material is obtained by, for example, causing an esterification reaction between propargyl alcohol and an aliphatic sulfonic acid such as methanesulfonic acid or an aromatic sulfonic acid such as p-toluenesulfonic acid. can be obtained easily and inexpensively,
Examples of the methylmagnesium halide to be reacted with this 2propynesulfonic acid ester include methylmagnesium chloride, methylmagnesium bromide, and methylmagnesium iodide.

The desired ethylacetylene magnesium halide is obtained by reacting both of the above raw materials, and the reaction formula is as follows.

In the formula, R is an alkyl group such as a methyl group, ethyl group, or propyl group, or an aryl group such as a phenyl group or tolyl group,
X is a chlorine, bromine or iodine atom.

This reaction is carried out by combining, for example, magnesium metal and methyl halide in anhydrous tetrahydrofuran or tetrahydrofuran and an inert organic solvent such as benzene, toluene, etc.
It is carried out by a method in which methylmagnesium halide is prepared by reacting in a mixed solvent such as xylene or n-hexane by a conventional method, and 2-propynesulfonic acid ester is added to this solution and reacted with the methylmagnesium halide. However, in this case, the amounts of 2-propynesulfonic acid ester and methylmagnesium halide used are:
Methylmagnesium halide is in the range of 2.0 to 2.5 mol per mol of 2-propynesulfonic acid ester, and the reaction temperature is -50°C to +60°C, preferably -40°C.
The reaction may be carried out by stirring at a temperature in the range of ~+10°C for 0.5 to 5 hours.

In this case, cuprous chloride or the like may be used as a catalyst for the purpose of promoting the reaction, and the amount used may be in the range of 0.1 to 109% per mole of methylmagnesium halide. Ethylacetylene magnesium halide obtained in this way is useful as an intermediate raw material in various synthetic reactions, but in particular hexyne-3-
It is important as an intermediate for obtaining all-1.

To explain this specifically, ethylene oxide is introduced into a solution of ethylacetylene magnesium halide obtained by the method of the present invention and reacted to form a halogenated magnesium salt of hexyne-3-ol-1. The amount of ethylene oxide used in this reaction is preferably in the range of 0.5 to 1 mole per mole of methylmagnesium halide used in the above reaction, and the reaction is preferably carried out at a temperature in the range of 0 to 40°C. An ammonium chloride aqueous solution is added to the solution of the magnesium halide salt of hexyne-3-ol-1 obtained in this manner, and hydrolysis is carried out in a conventional manner to obtain the desired hexyne-3-ol-1.
1 is obtained. In addition to being able to use inexpensive raw materials as described above, the method of the present invention does not require high-temperature and long-term reactions unlike conventional methods; It is extremely advantageous industrially because the desired product can be obtained in high yield in a short reaction time (by cooling). Next, examples of the present invention will be given.

Example 1 Internal volume 50 with stirrer, thermometer, drip load and cooling tube with drying tube (calcium chloride) at the tip
Anhydrous tetrahydrofuran 2 in a 0ml Yotsuro flask
00m11 10.69 (0.44 mol) of metallic magnesium and a very small amount of iodine pieces are charged, and 0.48 mol of methyl chloride is blown into this to produce a methylmagnesium chloride complex, and cuprous chloride is added to this solution. 0.19 and p-tolyl ester of 2-propynesulfonic acid 34.9 was added to this while maintaining the temperature at 0°C.
(0.18 mol) was gradually added with stirring, and after the addition was completed, the reaction was completed by stirring at 30° C. for 1 hour to obtain a solution of ethyl acetylene magnesium chloride.

The reaction is quantitative and can be used as is in the next step.
Example 2 The same procedure as in Example 1 was carried out except that methyl bromide was used instead of methyl chloride, and a solution of ethylacetylene magnesium bromide was quantitatively obtained.

Example 3 The same procedure as in Example 1 was carried out except that methyl iodide was used instead of methyl chloride, and a solution of ethyl acetylene magnesium iodide was quantitatively obtained.

Application Example Ethylene oxide 179 was added to the ethyl acetylene magnesium chloride solution obtained in Example 1 at 0°C and stirred at room temperature for 4 hours to obtain a solution of magnesium chloride salt of hexyne-3-ol-1.

Claims (1)

[Claims] 1. A method for producing ethylacetylene magnesium halide, which comprises reacting 2-propynesulfonic acid ester and methylmagnesium halide.