SU1449566A1 - Complex of cupric sulfide with divinylbenzene-linked copolimer of butylvinylsulfoxide and 4-vinylpyridine as heterogeneous catalyst of ethoxycarbonyl carbene penetration reaction - Google Patents

Abstract

The invention relates to the creation of a polymeric complex of copper sulphate with a crosslinked divinylbenzene copolymer of butyl vinyl sulfoxide and 4-vinylpyridine. The invention makes it possible to create a heterogeneous, multiple-action catalyst for the etoxycarbonylcarbene incorporation reaction. The proposed catalyst has a new structure of the general formula -ffCHj-CH-i-C, Tyi Hj-c i-CHivvAT | Y; G I JaL CttSoJ (/) where X is 3.6-18 May; At 6.88, 9 wt.%, Z 75.2-87.5 May. 73.4-79.4 Mac.% I b 20.6-. 26.6% by weight. 3 tab.

Description

;about

SP

SP

. sn

CttHg-S 0

CH-CH2.vN

CaSO / t

but

Ch | e X 3.6-18 wt.%;

6.8–8.9 masD; ; Z 75.2-87.5 wt.% I and 73.4-79.4 wt.%; I b 20,6-26,6 wt.%,

which can be used as a heterogeneous catalyst

15 ethoxycarbonylcarbene incorporation reaction by C-N bond in aliphatic 2,7-octadienylamines

xQ, .. +, CHCO t-xO-XX.x

rfje X Oh, CH ..

The specified polymer complex and eifo properties are not described in the literature.

The aim of the invention is to develop a high-performance, multiple-action catalyst and safe handling for the reaction.

 CH2 S S O

-CH-CHoWV

i

where X is 3.6-18 wt.%;

at 6.8–8.9 May.% i

Z 75.2-87.5 Mac.% I

and 73,4-79,4 wt.%.

B 20.6-26.6 wt.%. The content of SIOh, complexed on the polymer matrix, should be 20.6-26.6 wt.%, Better than 23.2 wt.%. The deposition of CuSO less than 210.6 wt.% Leads to a sharp decrease in (and catalytic activity), which is due to a decrease in the catalytic centers of copper responsible for conversion. More than 26.6% deposition on the BVCO H 4-VP copolymer leads to a significant increase in the yield of the target product.

The catalyst is a hemne blue powder, insoluble in organic solvents, such Isac benzene, toluene, sulfuric ether, hexane, chloroform, as well as in products

incorporation of ethoxycarbonylcarbene over, C-N bonds in aliphatic 2,7-octa-dienylamines.

The goal is achieved by a heterogeneous catalyst of the general formula

Casott

but

reactions of interaction of ethyl diazoacetate with octadienylamines.

The catalyst is prepared as follows.

Synthesis of crosslinked copolymer BVSO and 4-VP.

In a 200 ml 3-gram flask equipped with a stirrer, a cooler, and an introductory nitrogen supply tube, 100 g are placed, dissolved with and under stirring under a nitrogen atmosphere, 0.15 g of polyvinyl alcohol. Then the mixture is cooled to room temperature and, with vigorous stirring, BVSO, 4-VP, divinylbenzene (DVB) and linear nitrile of azo-iso-malic acid are introduced (DAI in a certain ratio (Table 1). The temperature of the reaction mass is raised to 90 ° for 1 hour C and a copolymerization process is carried out for 2 hours. The copolymer obtained is washed with alcohol and dried in a vacuum to

constant mass. The results of the experiment are summarized in table. one.

Preparation of a copper sulphate complex with a crosslinked BVSO copolymer and 4 VP.

The catalyst — CuSO, a light-knitted bond on the BVSO and 4-VP copolymer, crosslinked with DVB — is a 50 ml flat-bottom flask with a capacity of 50 ml and placed 1 g of the copolymer to an aqueous solution of copper sulphate (0.68 g of a light blue powder, does not require special CuS04 in 20 ml of water). The process of complex conditions for storage and non-thermogenesis is carried out for 8 hours while it is active for 5-6 months.

natal temperature and with stirring. Then the complex is filtered, washed with alcohol and dried to constant weight under vacuum at 40 ° C, CoX / 2) N- W v + N2CH

Have

where X Oh, CH,

It takes place in benzene medium with stirring and at 50-80 ° C for 2 hours with the release of ethyl amino acids 38-46% of the esters of unrivaled amino acids. Target products can be separated by simple decanting, since the complex is copper sulfate with crosslinked copolymer BVSO and 4-VP does not dissolve in the reaction products. The separated catalyst can be reused. After 10 test cycles, the catalyst does not lose its properties. the yield of ethyl esters of unsaturated amino acids is not significantly reduced and amounts to 42-43%.

Example 1 1. Preparation of a catalyst for the reaction of the introduction of ethoxycarbonylcarbene via a C-N bond in aliphatic 2,7-octadienylamines.

a) Obtaining a crosslinked copolymer of BVSO and 4-VP.

The copolymerization process is carried out in suspension, the emulsifier is polyvinyl alcohol.

A 200 ml 3-necked flask, equipped with a stirrer, a cooler and an introductory tube for nitrogen supply, is poured into 100 ml, with stirring and at 60 ° C, 0.15 g of polyvinyl alcohol is removed. Then the mixture is cooled to room temperature and with vigorous stirring 20 g (47.6%) of BVSO, 20 g (47.6% by weight) of 4-VP, 2 g (4.8% by weight) are introduced. DVB is a crosslinking agent and 1 wt.% Of all DAK-initiator monomers.

The temperature of the reaction mass is raised within 1 hour before and

the holding of CuSO in the copolymer is determined by the scaffold method and is. 20.6-26.6 wt.% Depending on the content of pyridine and sulfoxide groups in the copolymer.

The catalyst — CuSO, a lightly bound catalyst on BVSO and 4-VP copolymer, crosslinked with DVB — is a dark blue powder, does not require special conditions for storage, and does not require

blue powder does not require special storage conditions and does not require

Rety its activity for 5-6 months.

Reaction of introduction of ethoxycarbonyl-carbene bond in aliphatic 2,7-hctadienylamines

t (

0

five

with

0

five

0

five

/ hL

sn-a

The copolymerization process is carried out for 2 hours. The polymer is washed with alcohol and dried to constant weight. The output of copolymer 53% (23.g).

The composition of the copolymer is calculated on the basis of elemental analysis and is, wt.%: BVSO .11; 4-VP. 81.7, DVB 7.3,

Cross-linked copolymers with a different ratio of components in the copolymer are obtained in this way:

b) The composition of the initial mixture, g (wt.%):

BVSO 30 (71.4)

4-VP 10 (23.8). DVB 2.. (4.8)

DAK 0.4 (1 wt.% From monomers)

The composition of the copolymer, wt.%:

Bwso. 18.0

4-VP 75.2

DVB6,8

The output of the copolymer of 17.6 g (44%).

at). The composition of the initial mixture, g (wt.%):

10 (23.8) 30 (71.4) 2 (4.8)

0.4 (1 wt.% From monomers)

The composition of the copolymer, wt.% (G):

BVSO 3.6. (1,15)

4-BG 87.5 (28,000)

DVB 8.9 (2.848)

The output of the copolymer 32 g (80%).

The crosslinked BVCO copolymer with 4-VP is a light yellow powder, insoluble in organic solvents, such as benzene, toluene, hexane, sulfuric ester, and

BVSO 4-VP DVB DAK

in the products of the interaction of ethyldiazofactat with octadienylamines,

2. Preparation of a complex of sulfate IU, and with a crosslinked BVSO copolymer and.

In a flat bottom flask with a capacity of 50 ml, another 1 g of copolymer and aqueous pafcTBop copper sulfate (0.68 g

04 to 20 MP of water). The process is complex for further transformations.

in TC. chekie 2 hours. The cooled reaction mass is filtered, the catalyst is separated from the reaction mass. The filtrate is evaporated, the residue is distilled in vacuum and analyzed by chromatographic comparison with a limestone. The catalyst separated from the reaction mass can be used.

Si

The processes are carried out for 8 hours at room temperature and during reuse. Then the complex is filtered, washed with alcohol and dried to 40.

constant mass in vacuum at

° s The percentage of CuS04 in the co-polymer is determined by the weight method. The results of the experiment are summarized. in tab. 2c

I20

1 Example 2, In a batch reactor with a periodic effect to a solution of N-2,7- - (ktadienylamine in benzene and catalyst, from Table 2)

The results of the experiment are summarized in Table 3, where, for comparison, the yields of the target products obtained on a homogeneous catalytic system with the system are shown: Cu (ac - (, OS (, and), - A1) (1: 2 : 4 (mol),

Claims (1)

For catalyst J containing 23.2% CuSO., 10 test cycles were carried out at 60 ° C. At the same time, it retains its properties: the yield of ethyl esters of unsaturated amino acids is 42-43%. Invention Formula Copper sulphate complex with Sshich cut through a dropping funnel of the addition of 25 divinylbenzene copolymer of butylsinyl sulfoxide and 4-vin1 pnridine of the general formula ethyaschioacetate in benzene is placed, the reaction proceeds at 50-80 ° C  -4CH2-CH "-CHrCHVf). CH-CH V4A gde X 3.6-18 wt.%, at 6j8-8.9 wt.% | 2 75.2-87.5 Mac,% j and 73.4-79.4 Mac.% I B 20.6-26.6 wt.%, As a heterogeneous catalyst for the reactions of ethoxycarbonylcarbene. I, 1 sample1 1 7.1.4 23.8 4.8 44 18.0 75.2 6.8 76j6 6.8 .tO, 0 4.4 1050 (S 0) 710, 750  47.6 4.8 53 11.0 7.3 78.2 6.9 10.9 2.7 1570, 1605 323.8 71.4 4.8 80 3.6 87.5 8.9 79.9 7.1 11.7 0.9 (5j) Note. DAK - 1% by weight of monomers, Table 2 in TC. chekie 2 hours. The cooled reaction mass is filtered, the catalyst is separated from the reaction mass. The filtrate is evaporated, the residue is distilled in vacuum and analyzed by chromatographic comparison with a limestone. The catalyst separated from the reaction mass can be used. CuSOtj a l