SU370206A1 - METHOD OF OBTAINING HYDROXYL-CONTAINING 1,3-DIOXOLANE OR 1,4-DIOXANE - Google Patents

Description

one

A new method for producing hydroxyl-containing 1,3-dioxolanes or 1,4-dioxanes, which are used in chemical synthesis, is proposed.

In the literature, there is no data on the addition of alcohols to divinyl or vinyl alkyl or vinyl aryl ethers by a radical mechanism. Typically, 1,3-dioxolanes or their derivatives are obtained by reacting a diol with an aldehyde.

According to the proposed method, new hydroxyl-containing 1,3-dioxolanes or 1,4-dioxanes of the general formula are obtained

HE

/

H CH-CHj-C-Rj

R.

Ohs- °

%one

or

, 0

RI-HC- | VCHR -HC- O

where Ri, R2,

Ra and R4 are hydrogen, alkyl, aryl. aralkyl

The method consists in the fact that 1,1- or 1,2-diol divinyl ether is reacted with alcohol in the presence of Greg-butyl peroxide to isolate the target product using known techniques. Output 44-47 Undesirable divinyl ether and alcohol to take in the ratio of 1:30, and the process is carried out when heated to 118-130 ° C.

The proposed reaction proceeds in a peculiar way, because instead of the expected 1,2-adducts in one isha of both types of hydroxyl-containing hydroxyl-containing dioxo-cycles.

Example 1. Synthesis of 5-methyl-4- (2-methyl-2ol-propyl) dioxolane-1,3.

10.7 g (0.107 mol) of methylene glycol divinyl ether, 172 g (2.9 mol) of isopropyl alcohol and 1.8 g (0.012 mol) of tert-butyl peroxide are heated for 40 hours at 118-125 ° C. Distillation yields 5.6 g of product with m.p. 104.5-106 ° C / 6 mm Hg. v .; 1.4469; 1.0321; MRo found 41.47; calculated 41.96.

Paydeno,%: C 59.80; P 10.15; 10.01.

SzN.Oz

Calculated,%: C 59.97; H 10.06.

175.5 g of a mixture consisting mainly of isopropyl alcohol and unreacted divinyl ether is returned. In addition, 6.3 g of oligomer are obtained. The yield of the target product is 47%, considering the methylene glycol divinyl ether, which entered into the reaction. Example 2. Synthesis of 2-methyl-3- (2-met11L-2ol-propyl) dioxane-1,4. 7.8 g (0.068 mol) of ethylene glycol dvinyl ether, 125 g (2.08 mol) of isopropyl alcohol and 1.3 g (0.008 mol) of tregbutyl peroxide are heated for 46 hours at 118-130 ° C. Distillation yields 4 g of product with m.p. 95.5-96.5 ° С / 9 mm Hg. v .; 1,4492 each; 1.0094, MRo found 46.32; calculated 46.60. 127.5 g of a mixture consisting of isopropyl alcohol and unreacted divinyl ether are returned. In addition, 4.2 g of oligomer, a very viscous substance, soluble in IB water are obtained. The yield of the target product 44%. The structure of the compounds obtained is confirmed by IR and PMR spectra. In the IR spectrum of 2-methyl-3- (2-methyl-2-ol-propyl) dioxane-1.4, there are no bands that characterize the Vipyloxy group, and in the 1047-II20 region there is a group of maxima inherent in the dioxane structure. A strong narrow peak of 3510 slg- and frequencies in the region of 13200-1410, 1155 confirm the presence of a tertiary hydroxyl. The PMR spectra correspond to the spectra of 1,4-dioxanes and 1,3-dioxolanes of similar structure described earlier. 4 Subject of the invention 1. Method of producing hydroxyl-containing 1,3-dioxolanes or 1,4-dioxanes of the general formula CHON-CH-HC-tg-CH-CH-C-Cd 0 .0 RI R Na-HC- | -% CH-CH ; -C N. where RI, Ra, Ks and R4 are hydrogen, alkyl, aryl, aralkyl, characterized in that 1,1- or 1,2- | DIOL divine yloxy ester is subjected to (interaction with alcohol in the form of peroxide g / 7g-butyl with 2. Isolation of the desired product by known methods. 2. The method of claim 1, wherein the ratio of divinyl ether and alcohol is 1: 30. 3. The method of claim 1 and 2, characterized in that the process is carried out by heating to 118 130 ° C.