GB2053203A - Preparation of 3-(2-chloroethyl) sulphonyl propanoic acid - Google Patents
Preparation of 3-(2-chloroethyl) sulphonyl propanoic acid Download PDFInfo
- Publication number
- GB2053203A GB2053203A GB8017280A GB8017280A GB2053203A GB 2053203 A GB2053203 A GB 2053203A GB 8017280 A GB8017280 A GB 8017280A GB 8017280 A GB8017280 A GB 8017280A GB 2053203 A GB2053203 A GB 2053203A
- Authority
- GB
- United Kingdom
- Prior art keywords
- acid
- oxidation
- chloroethyl
- reaction
- chlorination
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
- D06M16/006—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with wool-protecting agents; with anti-moth agents
Abstract
A method for the preparation of 3-(2-chloroethyl) sulphonyl propanoic acid or acid halide which comprises chlorinating, oxidizing, and hydrolysing an alkayl 3-(2-hydroxyethyl) thiopropanoate ester, wherein the alkyl radical is from 1 to 4 carbon atoms and is preferably ethyl or methyl. The chlorination, oxidation and hydrolysis reactions may be carried out in any desired order, and the products are useful as intermediates in the production of fibre reactive dyestuffs and fibre reactive moth- proofing agents for wool.
Description
SPECIFICATION
Preparation of propanoic acid derivatives
This invention relates to a process for the preparation of 3-(2-chloroethyl)sulphonylpropanoic acid or acid chloride from alkyl 3-(2-hydroxyethyl) thiopropanoates esters.
A prior art method, French Patent, 1,363,046, utilizes 2-chloroethanesulphonylchloride and acrylic acid as starting materials to produce crude 3-(2-chloroethyl) sulphonylpropanoic acid by a three step reaction sequence in 70% yield. In contrast, in the present invention 3-(2-chloroethyl) sulphonylpropanoic acid is produced by a three step reaction sequence in very high yields, above 90%, usually 94% to 96%.
According to the present invention there is provided a method for the production of 3-(3-chloroethyl) sulphonylpropanoic acid or acid halide which comprises the steps of chlorinating, oxidizing and hydrolysing an alkyl 3-(2-hydroxyethyl)thiopropanoate ester.
The course of the reactions can be represented by the following equations:
where R is an alkyl radical of 1 to 4 carbon atoms. Preferably R is a methyl or ethyl radical and most preferably R is a methyl radical.
Alkyl 3-(2-hydroxyethyl)thiopropanoates which are used as starting materials are described in the literature or can be prepared in accordance with known methods, e.g. Hurd, C.P., and Gershbein, L.L.. J.
Amer. Chem. Soc.. 2328.69. 1947.
It is to be understood that in order to prepare the compounds (IV) and (V) by the processes of the invention it is not necessary to carry out the chlorination. oxidiation, hydrolysis and chlorination reactions as described by the equations (1) (2), 13) and (4) in the above sequence. For example alternative reaction pathways represented by the following equations also give high yields of (V):
Many suitable chlorinating agents for carrying out the reaction in steps (1), (4) and (7) are known to those skilled in the art, thionyl chloride and phosphorus pentachioride being particularly suitable. The chlorination reaction optionally may be carried out in the presence of an inert solvent or diluent.Generally equimolar amounts of the reagents are used and the reaction allowed to proceed at a temperature between 20 C and 160"C, preferably between 80-C and 120 C. The by-products from the chlorination and, when used, the solvent or diluent are generally removed under reduced pressure. In the case of reaction (1) the resulting alkyl 3-(2-chloroethyl) thiopropanoate may be used without further purification in reaction step (2).
Oxidizing agents most suitable for performing the reaction in steps (2). (6) and (9) are peroxides, such as hydrogen peroxide, sodium peroxide and the like; peroxy acids, such as performic acid, peraceatic acid and the like; or halogens, such as chlorine and bromine. Other oxidizing agents known to those skilled in the art may also be used.
The oxidation reaction is generally allowed to proceed in the presence of a solvent or diluent and, optionally, in the presence of water. Generally the oxidizing agent is employed slightly in excess of the stoichiometric amount required to perform the oxidation and is added to the reaction vessel containing the sulphide in small portions. The temperature of the oxidation reaction is generally determined by the boiling point of the reaction mixture and lies between 20 C and 150-C. Under the preferred conditions the reaction temperature rises from ambient to 100 C-120 C due the exotherm of the reaction and Is held at this temperature till all the oxidant has been consumed.
The hydrolysis of the estergroup in the reaction steps (3) and (8) of generally performed in the presence of a catalyst. The most suitable catalysts are strong mineral acids such as hydrochloric acid, hydrobromic acid and the like.
To effect the hydrolysis the reaction mixture is generally heated under reflux for three to six hours.
3-12-chloroethyllsulphonylpropanoic acid produced according to this invention is useful as an intermediate in the production of fibre-reactive dyestuffs and fibre-reactive mothproofing agents for wool.
The foliowing examples illustrate the invention.
Example 1
Thionyl chloride (117 g, 1.5 mole) was added dropwise to a solution of methyl 3-(2-hydroxyethyl) thiopropanoate 1150 g, 1 mole) in toluene (200 ml) heated under reflux. After the evolution of hydrogen chloride and sulphur dioxide ceased the mixture was heated a further 30 minutes and then the solvent and excess thionyl chloride was removed under reduced pressure. Acetic acid (300 mali was added and the mixture stirred while hydrogen peroxide (30 ;O in H?O, 240 ml, 2.1 mole) was added dropwise.During the addition of the peroxide the temperature of the reaction mixture was allowed to rise to 120-C and was then controlled by refluxing the acetic acid solvent. 30 minutes after the completion of the addition of peroxide hydrochloric acid (10 M, 600 ml) was added, the mixture heated under reflux for 5 hours and the solvent removed to yield 3-(2-chlornethyl)sulphonylprnpanoI.c acid (188 G, 94%. mpt = 136-137 C after recrystallized from conc. HCI).
Example 2
Thionyl chloride (1799, 1.5 M) was added to a solution of 3-(2-chloroethyl)sulphonylpropanoic acid (200 g, 1 M), prepared as in Example 1, in anhydrous acetonitrile(100 ml). The mixture was heated under reflux for 5 h, the solvent and excess thionyl chloride removed under reduced pressure and the 3-(2 chloroethyl)sulphonylpropanoyl chloride recrystallized from toluene-hexane.
Example 3
Thionyl chloride (117 g, 1.5 mole) was added dropwise to a solution of ethyl 3-(2-hydroxyethyl} thiopropanate (164 g, 1 mole) in toluene (200 ml) heated under reflux. After the evolution of HCI and S)2 had ceased the mixture was heated for a further 30 minutes and the solvent and excess thionyl chloride removed under reduced pressure. HCI (10 M, 500 ml) was added to the residue and the mixture heated under reflux for 5 hours. The hydrochloric acid was removed and the residue dissolved in acetic acid (300 ml) and stirred while hydrogen peroxide (30% in H2O, 240 ml, 2.1 mole) was added dropwise.The temperature of the reaction rose to 120"C and was maintained at this temperature by refluxing the acetic acid solvent. 30 minutes after the completion of the addition of the peroxide the acetic acid was removed under reduced pressure to yield crude 3-(2-chloroethyl)sulphonyl propanoic acid (178 g, 89%).
Example 4
To a stirred solution of ethyl 3-(2-hydroxyethyl) thiopropanate (164 g, 1 mole) in acetic acid (300 ml) was added dropwise hydrogen peroxide (30% in H2O, 240 ml, 2.1 mole). The reaction temperature rose to 1200C and was maintained at this temperature by refluxing the acetic acid. 30 minutes after the completion of the addition of the peroxide the acetic acid was removed under reduced pressure. Toluene (200 ml) and thionyl chloride (117 g, 1.5 mole) was added to the residue and the mixture heated under reflux. When the evolution of HCI and SO2 ceased the solvent and excess thionyl chloride was removed and the residue hydrolysed by heating in refluxing HCI (10 M, 500 ml) for 5-6 hours to yield 3-(2-chloroethyl)sulphonyl propanoic acid (183 g, 91%).
Claims (24)
1. A method for the production of 3-(3-chloroethyl)sulphonylpropanoic acid or acid halide which comprises the steps of chlorinating, oxidizing, and hydrolysing an alkyl 3-(2-hydroxyethyl) thiopropanoate ester.
2. A method as claimed in claim 1 in which the alkyl 3-(2-hydroxyethyl)thiopropanoate ester contains an alkyl radical of 1 to 4 carbon atoms.
3. A method as claimed in claim 2 in which the alkyl radical is methyl or ethyl.
4. A method as claimed in any one of claims 1 to 3 in which the chlorinating agent is thionyl chloride or phosphorus pentachloride.
5. A method as claimed in any of claims 1 to 4 in which the chlorination reaction is carried out in the presence of an inert solvent or diluent.
6. A method as claimed in any one of claims 1 to 5 in which the chlorination reaction employs equimolar amounts of the reagents.
7. A method as claimed in any one of claims 1 to 6 in which the chlorination reaction proceeds at a temperature between 20"C and 160"C.
8. A method as claimed in claim 7 in which the temperature is betweeen 80"C and 120"C.
9. A method as claimed in any one of claims 1 to 8 in which the oxidizing step employs an oxidizing agent.
10. A method as claimed in claim 9 in which the agent is hydrogen peroxide, sodium peroxide, performic acid, peraceatic acid, chlorine or bromine.
11. A process as claimed in any one of claims 1 to 10 in which the oxidation reaction proceeds in the presence of a solvent or diluent.
12. A process as claimed in claim 11 in which water is additionally present.
13. A method as claimed in anyone of claims 1 to 12 in which the oxidizing agent is employed slightly in excess of the stoichiometric amount required to perform the oxidation.
14. A method as claimed in any one of claims 1 to 13 in which the temperature of the oxidation reaction is between 20"C and 150 C.
15. A method as claimed in claim 14 in which the temperature of oxidation is determined by the boiling point of the oxidation reaction mixture.
16. A method as claimed in any one of claims 1 to 15 in which the hydrolysis reaction is performed in the presence of catalysts.
17. A method as claimed in claim 16 in which the catalyst is hydrochloric acid or hydrobromic acid.
18. A method as claimed in any one of claims 1 to 17 in which the hydrolysis is effected by heating the reaction mixture under reflux for three to six hours.
19. A method as claimed in any one of claims 1 to 18 in which the reactions are carried out in the sequence chlorination, oxidation, and hydrolysis, and the product is 3-(2-chloroethyl)sulphonyl propanoic acid.
20. A method as claimed in any of claims 1 to 18 in which the reactions are carried out in the sequence oxidation, hydrolysis and chlorination.
21. A method as claimed in any of claims 1 to 18 in which the reactions are carried out in the sequence chlorination, hydrolysis and oxidation.
22. A method as claimed in any of claims 19 to 20 in which a second chlorination reaction is carried out at the end of the reaction sequence, and the product is 3-(2-chloroethyl)sulphonyl propanoic acid chloride.
23. A method for making 3-(2-chloroethyl) sulphonyl propanoic acid or acid chloride substantially as hereinbefore described with reference to and as illustrated in the forgoing examples.
24. 3-(2-chloroethyl) sulphonyl propanoic acid or acid halide whenever made by a method as claimed in any one of claims 1 to 23.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AUPD919579 | 1979-06-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB2053203A true GB2053203A (en) | 1981-02-04 |
Family
ID=3768141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8017280A Withdrawn GB2053203A (en) | 1979-06-13 | 1980-05-27 | Preparation of 3-(2-chloroethyl) sulphonyl propanoic acid |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS56167662A (en) |
| AU (1) | AU5926980A (en) |
| DE (1) | DE3022072A1 (en) |
| GB (1) | GB2053203A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2687400A1 (en) * | 1992-02-17 | 1993-08-20 | Atochem Elf Sa | NOVEL (METH) ACRYLIC COMPOUNDS, PROCESS FOR PREPARING THEM AND THEIR USE IN THE SYNTHESIS OF NOVEL POLYMERS. |
-
1979
- 1979-06-13 AU AU59269/80A patent/AU5926980A/en not_active Abandoned
-
1980
- 1980-05-27 GB GB8017280A patent/GB2053203A/en not_active Withdrawn
- 1980-06-12 DE DE19803022072 patent/DE3022072A1/en not_active Withdrawn
- 1980-06-13 JP JP7918480A patent/JPS56167662A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2687400A1 (en) * | 1992-02-17 | 1993-08-20 | Atochem Elf Sa | NOVEL (METH) ACRYLIC COMPOUNDS, PROCESS FOR PREPARING THEM AND THEIR USE IN THE SYNTHESIS OF NOVEL POLYMERS. |
| US5457172A (en) * | 1992-02-17 | 1995-10-10 | Elf Atochem S.A. | (Meth)acrylic compounds, process for their preparation and their application to the synthesis of new polymers |
| US5587499A (en) * | 1992-02-17 | 1996-12-24 | Elf Atochem S.A. | (Meth) acrylic compounds, process for their preparation and their application to the synthesis of new polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3022072A1 (en) | 1980-12-18 |
| AU5926980A (en) | 1980-12-18 |
| JPS56167662A (en) | 1981-12-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |