SU402525A1 - METHOD OF OBTAINING ALKENYL DERIVATIVES ——— - Google Patents

Description

one

The invention relates to the field of production of epoxy compounds, in particular, to a method for the preparation of epoxy compounds, alkenyl derivatives of eichlorohydrin, which can be widely used in the production of epoxy resins.

The proposed method, like the obtained compounds, is new and useful, since it allows to obtain compounds of the general formula 1

ABOUT

/ R-CH CH-CH2-CH-CH-CHX-R

where X C1, Br, I; R R H, alkyl, cycloalkyl, which when combined with epoxy resins increase their strength and heat resistance, as well as increase their elasticity.

The method consists in that the aliphatic or alicyclic cc-olefin is reacted with a, p-dichloraldehyde in the presence of a catalyst — Lewis acids at a temperature of from-5 ° C to 20 ° C, followed by alkali treatment of the resulting chlorohydrin and isolation of the target product by known methods.

The yield of the target product to 80% of theoretical.

Example 1. 1,2-dichloro-3-ol-4-nonene (I).

In a three-necked flask equipped with a thermometer, a stirrer, and a reflux condenser with a calcium chloride tube, 15 g (Q, mole) of 1,2-dichloropropionic aldehyde, 25 ml of dry benzene and 23 g (0.23 mol) of hexene-1 are placed. To the mixture, cooled to temperature, in portions within 30 minutes, is added 1.5 g of aluminum chloride. Then the mixture is stirred at a temperature of -4 + 10 ° C for 3, 4 hours. After this time, the reaction mixture was washed with water and a solution of hydrochloric acid, with a 3% Na2COz solution, again with water and dried with sodium sulfate. After distilling off the benzene mixture with unreacted n-hexene, the residue is distilled in vacuo.

14.9 g (I) are isolated.

Yield 65% (but 1,2-dichloropropionic aldehyde), t. Kip. 105-107 ° C (1 mm Hg),

nfjO 1.4855, d2 1.1103; MR: found 54.54, calculated 54.55.

Found,%: C 51.00; H 7.51; C1 33.1. CgHie AXIS.

Calculated,%: C, 51.20; And 7.63; C1 33.58.

In the IR spectrum of the product there are bands 3374-3421, characteristic for (ace. OH-groups) and a band of 972 cm for (trans-CH-CH) CONNECT.

1-chloro-2,3-epoxy-4-nonene (II). To a mixture of 11.2 g (0.2 mol) KOH and 300 ml

ether, while stirring, 21.1 g (0.1 mol) (I) was added dropwise, kept for 3 hours at 18-20 ° C and 3 hours at the boiling point of ether. After filtering off KCl and distilling off the ether, the residue is distilled under vacuum. Received 14.9 g (85.74% of theoretical) (II), t. Kip. 84-85 ° C (1 mm Hg. Art.).

-,20

1.4644; d204 1.0030. MR

found:

B

D

48.08; MR d, calculated 47.60.

Found,%: C 62,19; P 8,47; C1 20.00. CgnisOCl.

Calculated,%: C, 61.88; P 8.65; From 20.29.

In the IR spectrum of the product, there are bands of 830, 863, 900, and 1262 cm - characteristic of the epoxy ring, and 972 cm characteristic of the (trans-CH-CH-) bond.

The purity of the epoxy compounds (II) is determined by chromatography and is 97.8%.

Example 2. 1,2-dichloro-3-ol-4-decene (III).

To a mixture of 19 g (0.15 mol) of 1,2-dichloropropionic aldehyde and 30 ml of dry benzene was added 4 g of chlorine tin (the mixture is gradually heated). After the reaction mixture was cooled to room temperature, 29.5 g (0.3 mol) of heptene-1 was added, stirred for 12-15 hours and after treatment as described in example 1, 23 g of product (70% of chloraldehyde) was isolated by vacuum distillation. m.p. 116-118 ° C (I mm RT. Art.); 1.4836; d

1.0975; MR o found: 58.65; MR), calculated: 59.17.

Found,%: C 53.10; H 8.01; C1 31.11. CioHisOCls

Calculated,%: C 53.34; H 8.05; C1 31.49.

In the IR spectrum of the product, there is a wide band of 3383 cm, characteristic for the OH group, and band 969 for the (trans-CH-CH-) bond.

1-chloro-2,3-epoxy-4-decene (IV):.

The experiment was carried out using the procedure described in Example I (P). From 11,) KOH, 22.5 g (0.1 mol) (III) but received Lb, 2 g (86.24% of theoretical) (IV), t. Kip. 91-92 ° C (0.8 mmHg. Art.) P 20 1.4647; 0.9906, MR d

found: 52.63; MR ,, calculated: 52,22. Found,%: C 63.12; H 9.00; C1 18.90

C | OH, 7OS1.

Calculated,%: C 63.65; H 9.09; C1 18.78. The frequencies found in the IR spectrum are 831, 855,

898, 922 and 1261 slg

characteristic of the oxide ring, 968 cm for (trans-CH-CH -) bonds.

The purity of the epoxy compounds (IV) is determined by chromatography and is 98%.

 the invention

The method of obtaining alkenyl derivatives of epichlorohydrin sheath; her formula:

ABOUT

/ R-CH CH-CH2-CH-CH-CHX-Ri

where R R H, alkyl, cycloalkyl,

X C1, Br, I, characterized in that the aliphatic or alicyclic a-olefin is reacted with a, p-dichloro aldehyde in the presence of a catalyst — Lewis acids at a temperature of from -5 ° C to 20 ° C, followed by alkali treatment of the resulting chlorohydrin and isolation target product known techniques.