SU619480A1 - Method of preparing dimethylvinylethinylcarbinol - Google Patents

Description

The invention relates to a process for the preparation of dimethylium and ethynyl carbinop, which is used in organic synthesis and polymer chemistry.

A known method for the preparation of vinyletinyl carbinol is the dehydration of symmetric and asymmetrical acetylene glycols with OO% sulfuric acid at 70 ° C. The yield of the target products is 5O-6O%.

A known method for the preparation of vinylsiline carbinols by the condensation of enclaimethylene with ketones in the presence of powdered caustic potash in ether or benzene. Yield 90% 2. A disadvantage of the known methods is the low yield of the target product.

The purpose of the present invention is to achieve a better yield, vinyl ethe sharbvi1) pa.

The goal is to achieve the use of the method of obtaining vinyl ethyl carbinol, the distinctive feature of KOTopwo is that 2-mvlhexadii-3, 5-ol-2 is subjected to hydrogenation with hydrogen in the presence of a skeleton

nickel catalyst containing 4-50 wt.% tungsten and 5O-96 wt.% nickel at temperatures from -15 to-60.

The yield of the target product reaches 98%.

Example. Hydrogenation of 2-methylhexadiin-3, 5-ol-2 is carried out in a cataclyactic duck at 80O-90O swings per minute on a skeletal nickel catalyst prepared from 0.4 g of the initial alloy, having a composition, wt.% 5O, W 2. The initial alloy is ground, a fraction of 175-4OO mesh is taken out, leached with a 2O% KOH solution in a boiling water bath for 2 hours. After leaching, a skeleton catalyst of the following composition is obtained, wt.%: N i 96, W 4. Hydrogenation of sample 1, O8 g (O, O1 mol) 2-methyl exadiyn-3, 5-ol-2 in 30 ml of methanol is carried out on the washed catalyst, in 30 ml of methanol at –15 ° C hydrogen m at atmospheric pressure. The complete process is completed within 45 minutes. Polupiot 1, O78 g (98%) dimethylvinyl etillarcarbinol

(2-methylhexazin-3-en-5-ol-2) with a bp 53-54 ° C at 10 mm PT.CT., p 1.477

Found,%: C 76.26; H 9.17;

.before.

Calculated,%: C, 76.36; H 9.09,

Example 2. Under the conditions of Example 1, on a skeleton catalyst of composition, wt.%: Ni84, W 16, wrinkled by leaching 0.4 g of the alloy H -A2 V, having the composition, wt.%: Ni 42, AE50, W 8, 30 ml of methanol is hydrogenated

1.08 g (0, O1 mol) 2-methylhexaain-3, 5-ol-2 at -15 ° C. The reaction is complete within 1 hour. Get 1, O67 g (97%) of dimethylvinylamine.

Example 3. Under the conditions of example 1. hydrogenation of 1.08 g (0.01 mol) of 2-methylhexadiin-3,5-ol-2 on a skeleton catalyst composition, weight,%: Wi 96, W-4, npH-30 ° C for 1 hour

1, O75 g (97.7%) of dimethylvnnethenylcarbinop is obtained.

Example4. In example 1, hydriding 1, O8 g (O, O1 mol) 2-methylhexadiin-3,5-ol-2 on the skeletal catalyst composition, wt.%: Mi 84, W 16 at -30 ° C for 1 h 2O min get 1, O7 g (97%) of carbinol.

Example 5. Under the conditions of example 1, hydrogenation of 1, O8 g (O, 1 mol of 2-methylhexadiin-3,5-ol-2 on a skeletal catalyst composition, wt.%: N "5O W SO for 1 h 45 mi receive 1 , 05 g (95%) of carbinol.

Example. In the conditions of example 1 by hydrogenation 1, O8 g (0.01 mol) 2-methylhexadiin-3,5-ol-2- on the skeleton catalyst composition, weight,%: NJ 96, W 4, at - 60 ° C within 1 h 25 min get 1, O6 g (96%) of carbinol.

Example 7. In the conditions of Example 1 by hydrogenation 1, O8 g (0.01 mol) of 2-meth lhexadiin-3,5-ol-2 on a skeleton catalyst of composition, wt.%: V 84, W16, at - 60 ° C for 1 h 40 min get 1, O45 g (95%) of carbinol.

Claims (1)

1.Vartan Mr. S.A.Piren Mr. S.K., Tszhmadzh Mr. V.V., .zh., 1966, 19, 9, p. 711. 2, Nazarov I.N. Synthesis of vinylacetylene and its transformation. Izv. Academy of Sciences of the USSR, ser. Chem., 1933, No. 3, p. 683.