JPS6122073A - Production of vicinal-dihaloalkyl glycidiyl ether - Google Patents

Abstract

PURPOSE:In the presence of an alkaline earth metal hydroxide, the dehydrohalogenation of 3-chloro-2-hydroxypropyl vicinal-dihaloalkyl ether is effected to enable high-yield production of the titled compound of high purity. CONSTITUTION:The dehydrochlorination of 3-chloro-2-hydroxypropyl vicinal- dihaloalkyl ether of formula I (R<1>, R<2> are H, alkyl; R<3> is H, alkyl; X is halogen) is effected using 0.4-2.0 moles, per mole of the starting compound, of an alkaline earth hydroxide such as magnesium hydroxide, calcium hydroxide, strontium hydroxide or barium hydroxide to produce a vicinal-dihaloalkyl glycidyl ether.

Description

Detailed Description of the Invention A. Field of Industrial Application The present invention relates to 3-chloro-2-
The present invention relates to a method for producing vicinal dihaloalkyl glycisole ether represented by general formula (2) from hydroxyprobyl vicinal dihaloalkyl glycisol ether in high yield.

(1)'
(2n (in the formula, n is 0 or an integer of 1 to 5, R1 and R2 are H or an alkyl group having 1 to 2 carbon atoms, R3 is H or an alkyl group having 1 to 5 carbon atoms) It is well known that alkyl 2,3-diglomopropyl ether (4) can be produced by bromine addition of alkylaryl ether (3). (Conventional Law A: Patent Publication 1973)
3-36444 specification).

[Conventional method A]

R: Alkyl group (4) The present inventors applied conventional method A to the compound of general formula (5).

An attempt was made to produce the compound of general formula (2) using -1, but
The selectivity of the reaction was low due to side reactions involving the opening of the epoxy ring. Moreover, it is difficult to remove by-products by distillation, and it is difficult to obtain pure compound (2), while the general formula (
It is also a known technique that the alkyl glycidyl ether represented by 7) can be produced by reacting the chlorohydrin ether represented by the general formula (6) with an alkali metal hydroxide such as sodium hydroxide in water or diethyl ether. (Conventional method B; British Patent No. 827450)
number specification etc.).

[Conventional method B]

(6) ' (7)
'However, when conventional method B is applied to the compound of general formula (1) containing a vicinal dihalo structure in the alkyl chain, the elimination reaction in the alkyl chain takes precedence over the reaction to form an epoxy ring, and the general formula Compound (2) could hardly be obtained. N. N. Mamedov et al.
Attempts have been made to synthesize dibromzolopyl glycidyl ether using potassium hydroxide in diethyl ether, but most of the products are de-HBrized and only 5.5% of the product is produced.
% yield (N, N, Mamed
ov, 1. M, Akhmedov, Azerb*
Khim, Zh., 1974. 97.
).

C.1 Means for Solving the Problems The present inventors have conducted intensive studies to improve the drawbacks of the conventional method as described above. The present invention was completed based on the discovery that the yield of the target compound (2) can be dramatically increased by using an earth metal hydroxide.

Hereinafter, embodiments of the present invention will be explained in detail.

The alkaline earth metals used in the present invention are magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide, and these metals may be used alone or in combination of two or more. The amount used is not necessarily strictly limited, but is generally 0.4 per mol of raw material compound (1).
A suitable amount is about 2.0 mol.

The reaction of the present invention can be carried out without a solvent or using a suitable organic solvent. It is also very effective to add water to increase the reaction rate.

The amount of water added is 0.0 per 1 part by weight of raw material compound (1).
Approximately 5 to 2.0 parts by weight is suitable.

・The reaction temperature in the present invention is not necessarily strictly limited, but is usually 20 to 120°C, preferably 30 to 100°C.
°C is appropriate.

The reaction of the present invention is usually carried out by mixing the required amount of raw material compound (1), alkaline earth metal hydroxide, and if necessary, appropriate amounts of water and organic solvent, and adjusting the reaction temperature to the required temperature while stirring. This is carried out by allowing the reaction to continue for a period of time (usually 2 to 10 hours).

Compound (2) can usually be isolated by filtering the reaction mixture after completion of the reaction, adding an appropriate organic solvent to the P solution, and distilling the extracted product under reduced pressure.

2. Examples Examples and comparative examples will be shown and explained below.

Example 1 3-chloro-2-hydroxypropyl 213'-dipromoglobyl ether soom (1,61 mol), calcium hydroxide 89.5 g (1,21 mol), water 200 ml
The mixture of 1 was stirred in a 100°C oil bath for 4 hours. The reaction mixture was suction filtered, and the filtrate was diisozolobyl ether 5
00ml was added and extracted, and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off, followed by distillation under reduced pressure to obtain 2,3-dibromzolopylglycidyl ether. Boiling point 108-110℃/1. Om
mHg o yield 354I0 yield 80.2ch.

Example 2 In Example 1, when strontium hydroxide octahydrate was used as a substitute for calcium hydroxide, the yield was 80.0.
% of 2,3-diglomopropyl glycidyl ether was obtained.

Example 3 In Example 1, 3-chloro-2-hydroxypropyl 2/, 3/-diglomzolobyl ether was substituted with 3
When -chloro-2-hydroxypropyl z1.3/-dichloroglobyl, -thyl was used, 2,3-dichloropropyl glycidyl ether was obtained in a yield of 84.9%.

Comparative Example 1 3-chloro-2-hydroxypropyl Z/, 3/-dibromzolobyl ether 500.9 (1,61 mol), sodium hydroxide 77.3 g (1,93 mol) and water 20
0ml of the mixture was stirred in a 100°C oil bath for 4 hours.

The reaction mixture was extracted with 500 ml of diisozorobyl ether and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off, followed by vacuum distillation; however, 2,3-diglomopropyl glycidyl ether was not obtained at all, and a compound (8 ) and (9) were obtained. boiling point 7
5-120'C7/1, 0 mmHg.

Comparative Example 2 While stirring 3-chloro-2-hydroxypropyl Z/, 3/-dibromopropyl ether 500.9 (1,61 mol) in an ice water bath, 77.3 mol of sodium hydroxide was added.
,! A solution of i' (1,93 mo#) in water (2 ooml) was added, and the mixture was stirred at 0-5° C. for 1 hour and roughly at room temperature for 4 hours. Diisozorobyl ether 5001 was added to the reaction mixture for extraction, and the mixture was dried over anhydrous magnesium sulfate. After the desiccant was removed, the solvent was distilled off and vacuum distillation was subsequently performed, but 2,3-dibromopropyl glycidyl ether was not obtained at all, and compounds (8) and (9) were obtained in the same manner as in Comparative Example 2.
) was obtained. Boiling point 75-120℃/1
．． OmmHg.

Comparative Example 3 Allyl glycidyl ether 57.1.9 (0,500
mol) was dissolved in 300 ml of diethyl ether, and 80.7.9 (0,505 mol) of bromine was added dropwise over 3 hours while stirring in an ice-water bath. 1K after completion of dripping
6. Stir in ice bath and rise from 1 °0""1""' to 1.
and stirred for 5 minutes. After distilling off the solvent under reduced pressure, vacuum distillation was performed, but only a fraction of 55.99 was obtained, which contained about 20% of 2,3-dibromopropyl glycidyl ether and two by-products of unknown structure. Ta.

Residue 73. , 1/1 was a viscous reddish-brown liquid and did not contain 2,3-diglomzolobyl glycidyl ether.

We also tried using potassium bromide as a catalyst, but
No improvement in selectivity was observed.

Effects of the present invention According to the method of the present invention, the dehalation reaction in the alkyl chain, which is a side reaction, is difficult to occur, and the epoxy ring formation reaction takes priority, so that the compound (2) with high purity can be obtained by conventional methods. It is possible to obtain high yields that were previously impossible.

Claims (1)

[Claims] 1. A method for producing vicinal-dihaloalkyl glycidyl ether, which comprises subjecting 3-chloro-2-hydroxypropyl vicinal-dihaloalkyl ether to a dehydrochlorination reaction in the presence of an alkaline earth metal hydroxide.