GB2080801A

GB2080801A - Polyhalogenated unsaturated esters and alcohols

Info

Publication number: GB2080801A
Application number: GB8122314A
Authority: GB
Original assignee: Anic SpA
Current assignee: Anic SpA
Priority date: 1980-07-29
Filing date: 1981-07-20
Publication date: 1982-02-10
Also published as: NO812555L; IT8023777A0; SE8104583L; FR2487822A1; DK328881A; NO820484L; IT1194814B; BE889769A; NL8103587A; JPS5753436A

Abstract

Polyhalogenated unsaturated esters of the general formula: <IMAGE> in which R1, R2, R3, and R4 are hydrogen or aliphatic alkyl, preferably methyl, X is Br or Cl, Y is H, Br or Cl, and n is 0, 1 or 2, are produced by reacting novel alcohols of the general formula: <IMAGE> with compounds of the formula: <IMAGE> in which Z' is -OH, -OCH3, -OC2H5 or -Cl.

Description

SPECIFICATION Polyhalogenated unsaturated esters and alcohols This invention relates to polyhalogenated unsaturated esters, and to polyhalogenated unsaturated alcohols for use in the preparation of the esters.

The polyhalogenated unsaturated esters of the invention are those having the general formula:

in which R1, R2, R3 and R4 are the same or different and each is a hydrogen atom or an alphatic alkyl group, preferably a methyl group, X is a chlorine or bromine atom, Y is a hydrogen, chlorine or bromine atom, and n is 0, 1 or 2.

As the above esters possess a reactive unsaturated bond of olefinic type, they are able to homopolymerise with themselves or to copolymerise with other unsaturated monomers, for example styrene, acrylonitrile and methylmethacrylate, in the presence of radical initiators such as dibenzoyl peroxide and azo-bisisobutyronitrile.

The esters, in particular those in which R1 = R2=CH3, can be produced by reacting an alcohol having the following general formula:

or, more generally, the following general formula:

in which R1, R2, X, Y and n are as defined above, with an acid, ester or acyl halide having the general formula:

in which R3 and R4 are each a hydrogen atom or a saturated alkyl group, preferably a methyl group, and Z' is, for example, a hydroxy group, a methoxy group, an ethoxy group or a chlorine atom.

The unsaturated alcohols of formulae (II) and (Ill) can be prepared by halogenating the corresponding acetylenic alcohols, e.g. alcohols of general formulae:

The unsaturated alcohols of formula (III) are new compounds.

The esters of formula (I) in which n is 1 can be produced by reacting the alcohols of general formula (III) with acyl halides, with acids, or with lower alkoxy esters by means of transesterification, whereas those of, formula (I) in which n is 0 are preferably produced by reaction of the alcohols with acyl halides.

The reaction between the alcohdls and the acyl halides; -generally acyl chlorides, is usually carried out at ambient temperature in the presence of a base (e.g. anhydrous Na2CO3, pyridine ortriethylarnitre); whereas the direct esterification with the acids and the transesterification which are preferable for the alcohols oi' formula (III), are usually carried out in the presence of an acid (e.g. p-toluenesulphonic acid) and in the presence of a base (e.g. sodium alcolate), respectively.

The invention will now be illustrated by the folllowing Examples.

EXAMPLE 1 Preparation of 1-bromo-3-methyl-3-(ss-hydroxyethoxy)- 1-butyne 116 g of 3-methyl-3-(B-hydroxyethoxy)-l -butyne:

were dripped into a solution of potassium hypobromite (consisting of 320 g of KOH, 51.2 ml of bromine and 600 ml of water) kept stirred at 0 C. Stirring was continued at 0 C for 2 hours, and then the organic phase was separated and extracted with chloroform (200 ml, three times). The extract was added to the previously separated organic phase and washed with water until neutral. It was dried over MgSO4, and the solvent was then eliminated under reduced pressure. The residue is distilled at 1 mmHg (B.P. 74 C) to give 150 g of 1 -bromo-3-methyl-3-(ss-hydroxyethoxy)-1 -butyne.The theoretical composition of C7H11O2 O2 is 40.68% of C and 5.31% of H. The found values were 40.30% of C and 5.15% of H. IR analysis (film) gave bands at 3410 cm-1 (OH) and at 2200 cm-1 (C=C).

By the above procedure using a solution of sodium hypochlorite instead of potassium hypobromite, 1-chloro-bromo-3-methyl-3-(ss-hydroxyethoxy)-1 -butyne of formula:

was prepared. It had a B.P. of 66-68 C (at 3 mmHg). The theoretical composition for C7H11ClO2 is 51.68% of C and 6.82% of H. The found values were 51.90% of C and 6.50% of H. IR analysis (film) gave bands at 3410 cm-1(OH) and at 2200 cm-1(C=C).

EXAMPLE 2 (a) Preparation of 1,1,2-tribromo-3-methyl-3-(ss-hydroxyethoxy)-1-butyne 25 ml of bromine were dripped into a solution of 1-bromo-3-methyl-3-(ss-hydroxyethoxy)-1-butyne (103 g) in chloroform (500 ml) while stirring at 40 C. The reaction mixture was left at 40 C for 2 hours and then washed with a sodium sulphite solution (2 gin 100 ml of water). It was dried over MgSO4, and 3 g of tin dibutylmaleate and 0.2 g of 2,6-diterbutylcresol were added, the solvent then being climated under reduced pressure to obtain 170 g of 1,1,2-tribromo-3-methyl-3-(ss-hydroxyethoxy)-1-butene.IR analyse(film) gave bands at 3400 cm-(OH) and at 1540 cm-1(C#C) (b) Preparation of 1,2-dibromo-3-methyl-3-(ss-hydroxyethoxy)-1-butyne 47.5 ml of bromine were dripped into a solution consisting of 3-methyl-3-(ghydroxyethoxy)-l -butyne (115 g), KBr (0.8 g) and H2O (100 ml), while stirring at 20-250C. Stirring was continued at ambient temperature for 2 hours, and then sodium sulphite was added until a colourless mixture was obtained. The organic phase was separated, washed with water until neutral, and dried over MgSO4 to obtain 195 g of 1 ,2-dibromo-3 methyl-3-(hydrnxyethoxy)-1 -butyne of B.P. 84 C(0.1 mmHg).The theoretical composition for C7H12Br202 is 29.17% of 0,4.2% of H and 55.5% of Br. The found values were 29.30% of C,4.5% of H and 55.2% of Br. IR analysis (film) gave bands at 3420 cm-' (OH), at 3100 cm-' C=CH) and at 1570 cm-1 (C=C). The product consisted of a trans-cis mixture in the proportion of about 95:5.

The same procedure was used to prepare 1,2-dichloro-3-methyl-3-(ss-hydroxyethoxy)-1 -butyne having a B.P. of 55-58oC (0.1 mmHg). The theoretical composition for C7H12Ci202 is 42.21% of C, 6.07% of H and 35.62% of Cl. The found values were 42.35% of C, 6.20% of H and 35.40% of Cl.IR analysis (film) gave bands at 3420 cm-' (OH), at 3090 cm-' (C=CH) and at 1580 cm-1 (C=C) EXAMPLE 3 (a) Preparation ofthe acrylic ester of 1,1,2-tribromo-3-methyl-3-(ss-hydroxyethoxy)- 1-butene A solution of 1,1,2-tribromo-3-methyl-3-(ss-hydroxyethoxy)-1 -butene (142 g), p-toluenesulphonic acid (7 g), acrylic acid (34.1 ml) and 2,6-diterbutylcresol (0.5 g) in benzene (300 ml) was heated to boiling under a nitrogen atmosphere until the water (7.5 ml) had been completely removed.The solvent and excess acrylic acid were eliminated under reduced pressure, the residue was washed with a saturated sodium bicarbonate solution and then with water until neutral, and was then dried over MgSO4 to obtain 120 g of the acrylic ester of 1,1,2-tribromo-3-methyl-3-(ss-hydroxyethoxy)-1-butyne having a B.P. of 125 C (0.1 mmHg with decomposition). l.R. analysis (film) gave a band at 1720 cm~1 (C=O).

(b) Preparation of the acrylic ester of 1,2-dibromo-3-methyl-3-(ss-hydroxyethoxy)- 1-butyne A solution consisting of 1,2-dibromo-3-methyl-3-(ss-hydroxyethoxy)-1 -butyne (57.4 g), ethyl acrylate (40 ml), sodium ethylate (0.5 ml of 1 N solution in ethanol) and 2,6-diterbutyl cresol (0.4 g) was heated to boiling under a nitrogen atmosphere until the temperature of the distillate remained at about 80 C (12 ml were collected over a period of 4 hours). The excess ethyl acrylate was eliminated, the residue was dissolved in ethyl ether, was washed with water until neutral, was dried over MgS04, and the solvent was then eliminated under reduced pressure to obtain 55 g of the acrylic ester of 1 ,2-dibromo-3-methyl-3-(8- hydroxyethoxy)-1 -butene, having a B.P. of 104-105 C (0.1 mmHg).The theoretical composition for C10H14Br203 is 35.09% of 0, 4.12% of H and 46.73% of Br. The found valeus were 35.40% of C, 3.90% of H and 46.40% of Br. IR analysis (film) gave bands at 3100 cm-1(C=CH), at 1720 cm-'(C=O), at 1620-1630 cm-' (C=CH2) and at 1670 cm-1(C=C).

EXAMPLE 4 (a) Preparation of the acrylic ester of 1,1,2-tribromo-3-methyl- l-buten-3-ol A mixture of 1,1 ,2-tribromo-3-methyl-1 -buten3-ol (360 g), acryloyl chloride (150 ml) CuCI (0.5 g) and anhydrous sodium carbonate (100 g) was stirred at ambient temperature under an inert atmosphere for 90 hours. It was slowly poured into water/ice (1 litre) and the organic phase was separated. The product was dissolved in chloroform (500 ml), washed with water until neutral, and dried over MgS04. The solvent was then eliminated under reduced pressure to obtain 340 g of crude acrylic ester of 1,1,2-tribromo-3-methyl-1- buten-3-ol, having a B.P. of 96-98 C (0.1 mmHg with decomposition).IR analysis (film) gave a band at 1720 cm (C=O).

(b) Preparation of the acrylic ester of 1,2-dichloro-3-methyl-3-(ss-hydroxyethoxy)- 1-butene 18 g of acryloyl chloride were dripped into a solution of 1,2-dichloro-3-methyl-3-(ss-hydroxyethoxy)- butene (39.8 g) and anhydrous pyridine (16 g) in anhydrous benzene (100 ml). The reaction mixture was kept at 0 C for 30 minutes, and then at ambient temperature for 2 hours. It was filtered, and the solvent was eliminated under reduced pressure. The residue was distilled at 0.1 mmHg (B.P. 80-84'C) to obtain 40 g of the acrylic ester of 1 ,2-dichloro-3-(P-hydroxyethoxy)-1 -butene. The theoretical composition of C10H14Cl2O3 is 47.42% of C and 5.57% of H. The found values were 47.50% of C and 5.60% of H.IR analysis (film) gave bands at 3080 cm-' (C=C-H), at 1720 cm-' (C=O), at 1620-1630 cm-1(C=CH2) and at 1580 cm~1(C=C-CI).

An analogous procedure was used to prepare the methacrylic ester of 1 ,2-dibromo-3-methyl-3-(8- hydroxyethoxy)-1 -butene, having a B.P. at 0.05 mmHg of 98-100 C (with decomposition). The theoretical composition of C11H16Br203 is 37.80% of 0,4.53% of H and 44.89% of Br. The found values were 37.60% of C, 4.45% of H and 44.95% of Br. IR analysis (film) gave bands at 3080 cm~1(C=CH), at 1715 cm~1(C=O), at 1630 cm-1(CCH3=C) and at 1570 cm~1(C=C).

The same procedure was used to prepare the crotonic ester of 1,2-dibromo-3-methyl-3-(ss-hydroxyethoxy)- 1 -butene, having a B.P. at 0.05 mmHg of 100-104 C (with decomposition). The theoretical composition of C11H16Br203 is 37.8% of C, 4.53% of H and 44.89% of Br. The found values were 37.95% of 0,4.40% of H and 44.75% of Br. IR analaysis (film) gave bands at 3080 cm~1(C=CH), at 1710 cm-1(C=O), at 1650 cm-'(C=CCH3) and at 1570 cm-1(C=C)

Claims

1. A polyhalogenated unsaturated ester having the general formula:

in which R1, R2, P3 and R4 are the same or different and each is a hydrogen atom or an aliphatic alkyl group, X is a chlorine or bromine atome, Y is a hydrogen, chlorine or bromine atom, and n is 1 or 2.

2. A polyhalogenated unsaturated alcohol having the general formula:

in which R1, R2, X, Y and n are as defined in claim 1.

3. The acrylic ester of 1,1 ,2-tribromo-3-methyl-3-(B-hydroxyethoxy) -butene.

4. The acrylic ester of 1,2-dibromo-3-methyl-3-(ss-hydroxyethoxy)-1-butene.

5. The acrylic ester of 1,1 ,2-tribromo-3-methyl-1 -butene3-ol.

6. The acrylic ester of 1,2-dichloro-3-methyl-3-(ss-hydroxyethoxy)-1-butene.

7. The methacrylic ester of 1 ,2-dibrnmo-3-methyl-3-(frhydroxyethoxy)-1 -butene.

8. The crotonic ester of 1,2-dibromo-3-methyl-3-(ss-hydroxyethoxy)-1-butene.

9. 1,1,2-Tribromo-3-methyl-3-(ss-hydroxyethoxy)-1-butene.

10. 1,2-Dibromo-3-methyl-3-(ss-hydroxyethoxy)-1-butene.

11. 1,2-Dichloro-3-methyl-3-(ss-hydroxyethoxy)-1-butene.

12. A process for preparing a polyhalogenated unsaturated ester as claimed in claim 1, which comprises reacting a polyhalogenated unsaturated alcohol as claimed in claim 2 with an unsaturated carboxylic acid or an ester or halide thereof.

13. A process according to claim 12, wherein the alcohol is reacted with a compound having the general formula:

in which P3 and R4 are as defined in claim 1 and 2 is a carboxylic acid group, a carboxylic ester group or an acyl halide group.

14. A process according to claim 12, substantially as described in either of the foregoing Examples 3 and 4.

15. A process for preparing a polyhalogenated unsaturated alcohol as claimed in claim 2, which comprises halogenating an acetylenic alcohol having the general formula:

in which R1, P2, Y and n are as defined in claim 1.

16. A process according to claim 15, substantially as described in the foregoing Example 2