SU1397449A1 - Method of producing spiroorthoethers - Google Patents

Abstract

The invention relates to oxygen-heterocyclic substances, in particular the preparation of spiro-ortho-esters of the general formula (W2) О O-C-o-Shg-ashg-o where K is CH, R ,; R is Cl or in; and -0-Sat 4-OCH-CH-0-CX-0-6lj ;, CfeHjO; (CH,) -, which as monomers can be used in the production of non-shrink polymers. The goal is to increase the yield of target products and expand their range. Synthesis is carried out by the reaction of y-butyrolactone with the epoxy compound of the total f-ly R 2 CH 2 CH-CH j O where B is C1; CgHyO or O-CHg-CH-OO O- (in the presence of the Fridel-Crafts catalyst — SnCI, j, pretreated with 1-2 molar equivalents of lower aliphatic alcohol, methanol, ethanol, followed by deactivation of the catalyst by pyridine treatment. The method allows to increase yield of target substances up to 82-94% and simplify the process of their separation. 1 epf f-ly. (L with co 4; 4 CO

Description

This invention relates to a graduated process for the preparation of Toether of the formula

K, -CH2-CH Sh2

 II

oh oh

,

/ o. sn

-Snp

which can be found as monomers for the preparation of non-shrink polymers.

The aim of the invention is to increase the yield and expansion of the range of 1-spiro-ortho-esters, as well as to simplify the process,

The goal is achieved by using four tin chloride as a catalyst, preliminarily treated with 1-2 molar equivalents of the lower aliphatic alcohol, co: corresponding to epoxidized, and pyridine is used as a base for deactivating the catalyst.

; Example I. To 43.05 g (0.5 mol) of J-butyrolactone were added: Gu catalytic system, consisting of p, 30 g (5 10 mol) of SnCl and 0.23 g (5 10 mol) of ethanol, and while stirring and chilling the solution, up to 10–15 s are added: 4 b, 5 g (0.5 mol) of epichlorgia, Chryn "Then the mixture is kept at room temperature for 72 hours. After that, add to the solution 05.79 g (1 x X.) pyridine, otfil75The precipitate of the catalyst complex with pyridine. After distillation in vacuum, the yield of 2-chloromethyl-1 j4,6 - TpHOKcacnnpo (454) nonane (t. K1 p. Mm Hg 93%..

Example 2. Synthesis of 2 Chlorome-, 4,6-trioxaspiropy (4.4) nbnan is carried out according to the procedure of Example 1 with the fact that the catalytic system consists of 1.30 g of (5-) SnCl and (5-10 ms ) methanol, Yield 94%.

Example 3. Synthesis of 2-Fensh-1-hydroxymethyl-, 4,6-trioxaspiro (4.4) nonane is carried out according to the same procedure as in Example 1 with the difference that 75.09 g (mole) of a mixture of J-butyrolactone and the catalytic system is attached. phenyl

0

- ,,

0 from 0 h

..

.

glycidyl ether, T. kip. 156 C / 2 mmHg, Art., T. Pl. 80-81 ° C. Yield 93%.

c Example 4. Synthesis of 2-phenyl-hydroxymethyl-, 4,, 6-trioxaspiro (454) nonane is carried out as described in Example 3 with the difference that the catalytic system consists of 1.30 g 0 (5 10 mol) SnCl and 0 , 23 g (5 x X 10 mol) of methanol. T. pl. 80-81 C. Yield 94%.

Example 5. Synthesis of 2-phenyl-hydroxymethylene-1,4,6-trioxaspiro (4.4) nonane was carried out as described in Example 3 with the difference that the catalytic system consists of 1.30 g of (5) SnCl and 0.46 g (1 x x). 90% yield

Example 6. To 43.05 g (0.5 mol) of jf-butyrolactone is added

a catalytic system consisting of 1.30 g (5 10 mol) of SnCl and 0.16 g (5 10 mol) of methanol, and while stirring and cooling the solution to 10–15 ° C, 55.5 g (0.25 mol) are added a) diglycidyl ester of resorcinol. The mixture is then kept at room temperature for 120 hours. The yield of 1,3-bis- {l, 4,6-trioxaspiro (4,4) non-3-yl methyl6xy benzene is 94%. After recrystallization from dimethylformamide, the yield of bis-spnroortoether is 82%. T. pl. (Output by a known method of 5%).

Example 7. Synthesis of 2-chloromethyl-1,4,6-trioxaspiro-ortho (4,4) nonane was carried out as described in Example 1 with the difference that the catalytic system consists of 1.30 g (5 x 10 mol ) SnCl4 and 0.05 g (1 x 10 X mol) of ethanol. Exit 63%.

Example 8. Synthesis of 2-chloromethyl-1,4,6-trioxaspiro (4.4) nonane is carried out as described in Example 1 with

the difference is that the catalytic system

,,

consists of 1.30 g (5 - 10 mol) SnCl and 2.30 g (5 10 mol) of ethanol. Yield 57%.

EXAMPLE 9 Synthesis of 2-chloromethyl-1,4,6-trioxaspiro (4.4) nonane is carried out according to the method of example 1 with the difference that the reaction is carried out in - carbon tetrachloride. (332 g) After distilling off the solvent, the yield is 87%.

Example 10. To 43.05 g of J-butyrrolactone, 0.71 g of boron trifluoride etherate and 15 ml of chitfech were added.

carbon chloride. When mixing - Replacing the aqueous solution of alkali on

Research Institute and cooling this solution to- 15 ° C, a solution consisting of 55.5 g of resorcinol diglycyl ether and 150 ml of CC1 is added dropwise. Then the solution is kept at room temperature for 2 hours. The spectral yield of the bis-spiro-ortho ester is 22%. 250 ml of a 10% KOH solution are added to the reaction mixture, the organic layer is separated, washed with water until neutral. The solvent is then distilled off and semi-pyridine is recrystallized when the catalyst is deactivated.

from the stage of washing the reaction mixture with water until neutral reaction, which is accompanied by partial gidrolysis of the obtained spiro-ortho esters. Pyridine forms a solid complex with a catalyst that is easily separated from the reaction mixture by filtration. After the separation of the pyridine complex of the catalyst, the reaction mixture represents a practically pure chenylo-spiro-ortho-ester from dimethyl-5 the desired product,

formamide. The output of 1,3-bis-Tfl 6 Thus, the proposed method is trioxaspiro (4,4) non-3-yl methyloxyT benzene 5%,

Pyridine is used to deactivate the SnCl catalyst. Deactivation 20 is that pyridine forms a strong complex with SnCl, which allows to increase the yield of the target product to 82-94% and simplify the process of its isolation,

The almost quantitative yield of spiro orthoesters ensures their high purity, which makes it possible to use, in cationic polymerization processes, monomers obtained by the reaction, this complex is insoluble in the reaction medium. Deactivation of the catalyst is carried out after the end of the synthesis process, therefore it does not directly affect the increase in the yield of the target product. The use of pyridine as a kata deactivator

lysing instead of washing with water - 30 formula

the thief of alkali simplifies the technology of allocating the target produhst compared with the known method

You can bind SnClq to the complex with other amines, but usually these compounds are soluble in the reaction medium, and the complex with pyridine in the form of crystalline powder precipitates, which can be easily filtered.

The ratio of the components of the catalytic system SnCl4 ROH affects the yield of the final reaction products, since outside the specified ratio, the yield of spiro-orthoesters decreases (examples 7, 8). spiro ortho ester cue,

CHg-CHj

Carrying out the reaction of preparing ortho esters in a solvent medium does not lead to a change in the yield of the product, gg; the interaction of J - butyrolactone with

However, it necessitates the post-epoxy compound in the presence of a catalytic distillation of the reaction products of the Friedel-Crafts lysator, which significantly complicates the process by suppressing the deactivation of the catalyst, which reduces the yield of the active compound, no.

pyridine during catalyst deactivation allows to refuse long-term

stages of washing the reaction mixture with water until neutral, which is accompanied by partial gidrolysis of the obtained spiro ortho esters. Pyridine forms a strong complex with the catalyst, which is easily separated from the reaction mixture by filtration. The reaction mixture after separation of the pyridine catalyst complex predg Thus, the proposed method

mixtures

allows to increase the yield of the target product to 82-94% and simplify the process of its selection,

An almost quantitative yield of spiro-ortho-esters ensures their high purity, which makes it possible to use the obtained reaction mixtures as monomers in cationic polymerization processes,

Claims (1)

Formula of O brie n i mixed mixtures . Method for producing spiro-ortho esters .CHi-CH-CHa  / WITH / oh CHj-CHj OCHgCHCHa 0o with 0 CHz 1I CHg-CHj J - Butyro 51397449 6 by the fact that, in order to increase the quality of the catalyst, there is a chain of celestial product, to simplify the tin chloride process, preliminarily assay and expand the assortment, used in 1-2 molar equivalents of epoxy compound, they use lower aliphatic alcohol, and compound of the formula as a base for deactivating / fr C11 (catalyst TLC  H / reedin. ABOUT  Kj - Pho- or 2. The method according to claim 1, about t l and h and l and u with the fact that as  (IL) lower aliphatic alcohol, methanol or ethanol is used.