GB2164939A - Synthesis of thioglycolic acid - Google Patents
Synthesis of thioglycolic acid Download PDFInfo
- Publication number
- GB2164939A GB2164939A GB08523818A GB8523818A GB2164939A GB 2164939 A GB2164939 A GB 2164939A GB 08523818 A GB08523818 A GB 08523818A GB 8523818 A GB8523818 A GB 8523818A GB 2164939 A GB2164939 A GB 2164939A
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- GB
- United Kingdom
- Prior art keywords
- acid
- reaction zone
- hydrosulfide
- monochloroacetic
- dichloroacetic
- 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.)
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Thioglycolic acid is made by contacting in a reaction zone at elevated pressure of H2S gas of at least 250 psig (1723 kPa) a mixture of monochloroacetic acid and dichloroacetic acid with a molar excess of an alkali metal or alkaline earth metal hydrosulfide to form the metal salt of thioglycolic acid, acidifying said salt and removing the free thioglycolic acid. The ratio of monochloroacetic acid to dichloroacetic acid is 99:1 to 75:25 by weight, the molar ratio of hydrosulfide to monochloroacetic acid is at least 2.1 and the under ratio of hydrosulfide to dichloroacetic acid is at least 3.1. A preferred process further requires separating any formed thiodiglycolic acid from the resultant liquid phase materials and recycling said acid to the reaction zone.
Description
SPECIFICATION
Synthesis of thioglycolic acid
The present invention is directed to a process for forming thioglycolic acid in high yields by reacting mixtures of monochloroacetic acid and dichloroacetic acid with an alkali metal hydrosu Ifide under conditions described herein below.
Thioglycolic acid is a highly desired product having various commercial applications. It forms the active ingredient of most hair waving preparations. It is also used extensively in cosmetic depilatories and in commercial agents used to remove hair from hides and the like. Various other commercial uses are made of thioglycolic acid in addition to those described above. The large and varied demands for thioglycolic acid provide a great need for forming this material in the most effective and economical method.
Thioglycolic acid is presently prepared commercially by reacting pure monochloroacetic acid with sodium hydrosulfide in an aqueous medium. After acidification, thioglycolic acid is extracted from the reaction mixture with some suitable organic solvent and purified by distillation. This process was first described by Carius in Ann. 124, 43 (1862) and later improved by Klason and
Carlson in Ber. 39, 732-738 (1906). The later authors taught that the process is best carried out using a sodium hydrosulfide liquor of not more than 15 percent by weight and a weak monochloroacetic acid solution containing the acid in not more than 20 percent by weight.
Alternate methods have been suggested. These include a two step synthesis of initially reacting monochloroacetic acid with sodium thiosulfate followed by hydrolysis of the resulting
Bunte salt (See U.S. Patents 2,594,030; 2,413,361 and British Patent 624,568). Another proposed synthesis (German Patent 180,875) involves the reaction of monochloroacetic acid with an alkali polysulfide and then reducing the formed dithiodiglycolic acid by means of zinc and mineral acid. U.S. Patent 3,860,641 described a process of forming thioglycolic acid by heating an alkali hydrosulfide with a xanthogenic acid.
Recent patents directed to modifications of the Klason and Carlson process for forming thioglycolic acid include U.S. Patents 3,927,085 and 4,082,790. U.S. Patent 3,927,085 describes a modification which requires the presence of aqueous sodium or ammonium hydroxide, a partial pressure of hydrogen sulfide and pure monochloroacetic or monochloropropionic acid in 4-12 mol. percent.
U.S. 4,082,790 teaches that mono, di or tri mercaptans of the formula R(SH), can be formed by reacting the corresponding mono, di or tri chloride or bromide, R(X), with H7S and ammonia or an amine in aqueous systems to give the corresponding mercaptan R(SH),. R can represent an aliphatic carboxylic acid and a represents an integer of 1 to 3.
The process most commonly used is that described by Klason and Carlson. The starting carboxylic acid is pure monochloroacetic acid either as the free acid or as its alkali metal salt.
The acid feed is required to be free of polyhalo acids to avoid the formation of the corresponding polythiols as suggested in U.S. Patent 4,082,790. In view of the fact that the chloroacetic acid is normally formed as a mixture of mono and dihalo acids, the presently known art requires separation and purification of the monochloroacetic acid prior to its use in order to achieve high yields of the desired product.
It would be highiy desired to have a process of forming the desired thioglycolic acid product which utilizes a combination of mono and polychloroacetic acids as feed reactant. Such a process would provide a more effective and economical mode of producing the desired product.
SUMMARY OF THE INVENTION
The present invention is directed to a process for forming thioglycolic acid in high yields by reacting, in an aqueous medium and under and elevated pressure of at least 250 psig (1723 kPa) provided by hydrogen sulfide, a mixture of monochloroacetic acid and dichloroacetic acid or their alkali metal salts with alkali or alkaline earth metal hydrosulfide.
DETAILED DESCRIPTION OF THE INVENTION
The subject invention is directed to an effective process for forming thioglycolic acid in high yields by reacting, in an aqueous medium and under elevated pressure of at least 250 psig (1723 kPa), a mixture of mono- and dichloroacetic acid with sodium hydrosulfide under the conditions described herein below. The present process provides a means of achieving very high yields of the desired product while using a mixture of chloride substituted acetic acids. This process eliminates the previously required purification of monochloroacetic acid for use as a feed in commercial formation of thioglycolic acid.
The halogenated organic acid feed used in the present process is a mixture of monochloroacetic acid and dichloroacetic acid. The weight ratio of mono to di substituted acetic acids in the feed can range from about 99:1 to 75:25 and from about 98:2 to 95:5 being preferred. The inclusion of the dichloroacetic acid as part of the feed has, under the present conditions, been unexpectedly found not to be detrimental to but, instead, to aid in producing thioglycolic acid in high yields.
The mixed organic acid feed can be introduced into the reaction zone, as described below, in aqueous medium. The concentration of the mixed organic acid feed can be any concentration which provides a homogeneous liquid phase under the reaction conditions. The organic acid feed can be from about 5 to 35 weight percent with from about 20 to 35 weight percent being preferred based on the aqueous liquid system introduced into the reaction zone.
The mixed organic acid feed can be introduced in the form of the free acids. The free acid is the preferred feed although the acids may be partially or totally in the form of their alkali metal, such as sodium, salt when introduced into the reaction zone.
The alkali or alkaline earth metal hydrosulfide reactant can be readily formed in known manners. It is preferred to use sodium hydrosulfide although other alkali metal hydrosulfides, such as potassium hydrosulfide, or alkaline earth metal hydrosulfides, such as calcium hydrosulfide, may be used. The alkali or alkaline earth metal hydrosulfide should be in water soluble concentrations of from 7 to about 40 weight percent and preferably from 25 to 35 weight percent in the aqueous system in the reaction zone.
The aqueous feeds of (1) the mixed chloroacetic acids and (2) the metal hydrosulfide should be introduced into the reaction zone so that there is a molar excess of the metal hydrosulfide to the mixed mono and di chloroacetic acids. The molar ratio of the metal hydrosulfide to monochloroacetic acid (as free acid) in the feed should be at least 2. 1 or, when supplied as salt, should be at least 1. 1. The molar ratio of metal hydrosulfide to dichloroacetic acid (as free acid) in the feed should be at least 3.1 and, if supplied as the salt, should be at least 2.1 Higher ratios can be used. The preferred molar ratio of metal hydrosulfide to monochloroacetic acid is from 2.1 to about 3 and the dichloroacetic acid is from 3.1 to about 4. Even higher ratios can be used.
The reaction is carried out at a pressure of at least 250 psig (1723 kPa) with pressure from 250 to about 500 (about 1723 to about 3448 kPa) being found to provide the best yields. It is critical that the reaction be conducted under the described elevated pressures of hydrogen sulfide to cause the process to produce the desired product in high yields. The pressure can be achieved by the autogeneous pressure of the reactants or with the addition of supplemental hydrogen sulfide gas.
In contrast to the criticality of elevated pressure conditions, it has been observed that when using the present reactants, the reaction can be carried out at low temperatures. The reaction can be carried out a temperatures ranging from ambient to about 150 C and preferably from ambient to 100 C and most preferably from ambient to 60 C. The ability to carry out the process at low temperatures is another beneficial aspect of the invention to unexpectedly provide an economically effective process.
The length of time for the reactants to be contained within the reaction zone can be readily determined by those skilled in this art in order to optimize the yield. Normally the time will vary depending upon the size and configuration of the reactor and whether the process is run in a batch or continuous mode. Normally residence times of at least about 20 minutes provides good yields with times greater than about 40 minutes showing substantially no further increase in yields. Greater or less times may be appropriate under varying reaction zone conditions.
The reaction zone can be any reactor capable of causing contact among the reactants in either a batch or continuous process mode. For example, a conventional tubular reactor or its equivalent can be used to carry out the reaction in a continuous manner while a pressure reaction vessel can be used for batch operation.
The feed streams (one containing a mixture of organic acids and one containing alkali metal hydrosulfide) can be mixed prior to entry into the reaction zone. Mixing may be accomplished by various conventional means for liquid-liquid mixing such as vortex mixers or static mixers with stainless steel gauze coils or the like. The mixed feeds are introduced into a reaction zone.
When the process is carried out on a continuous basis, a high pressure metering pump or the like can be used to introduce the fluid feeds into the reaction zone at a rate so as to have the reactants maintained in the reaction zone for a residence time sufficient to permit the reactants to form thioglycolic acid product in high yields.
The reaction zone is required to be maintained at a pressure of at least 250 psig or 1723 kPa (preferably from 250 to 500 psig or 1 723 to 3448 kPa) and can be at temperatures ranging from ambient to about 150"C (preferably ambient to 100-C and most preferably from ambient to 80WC) as described above.
The liquid material is removed from the reaction zone. For example, in a continuous process the removal can be effected by flashing the liquid through a back pressure regulator or the like to atmospheric pressure. The off gases which are produced in the reactor (mainly H2S) are then removed and normally passed through caustic scrubbers.
The aqueous liquid removed from the reaction zone contains thioglycolic acid as the main (normally greater than 90% yield) reaction product and may also contain small amounts of thiodiglycolic acid as by-product. The liquid removed from the reaction zone can be treated with an inorganic mineral acid such as sulfuric acid to convert the organic acid alkali metal salts to the free acid material.
It has been further unexpectedly found that the major by-product, thiodiglycolic acid, can be removed, recycled and introduced into the reaction zone as part of the feed. When recycling the thiodiglycolic acid by-product under the process conditions of the present invention, one achieves overall yields of the desired product of about 95-100 percent. The formation of thioglycolic acid from the thiodiglycolic acid has been hypothesized to occur (this theory is not meant as a limitation on the subject invention but merely as a suggested mode) by the disproportionation of the thiodiglycolic acid according to the following reaction: NaOOCH2SCH2COONa + H2S .2 HSCH2COONa
The following examples illustrate the invention. All parts and percentages are by weight unless otherwise indicated.
EXAMPLE I
The process was performed in a continuous manner using a tubular reactor. It consisted of a 17 ft. (5.2 m) long, 1/8" IDX1/4" OD (3.2X6.4 mm tubular reactor coiled in a spiral so that it fit into a high temperature oil bath. The temperature of the bath, T2 and that of the product, T, were closely monitored by two thermocouples and controlled by an automatic temperature controller. The pressure of the reactor system was controlled by a back-pressure regulator with a range of 0-500 psi (0 to 3448 kPa) and was closely monitored by two pressure gauges, with a range of 0-600 psig (0 to 4137 kPa), located at the entrance and exit of the tubular reactor.
The alkali metal hydrosulfide (as NaSH) and the mixed mono and dichloroacetic acid feeds were introduced into the tubular reactor from reservoirs via separate dual-piston high pressure metering pumps with flow capacities from 0.12 ml/min to 3.6 ml/min per head. The feeds were initially mixed using a dual tube mixer. The NaSH stream was introduced through the insert charge tube with the organic acid stream coming from the outside. The two streams were then passed through a static mixer having coils of stainless steel gauze to achieve further mixing. The liquid phase product from the reactor was flashed through a back-pressure regulator to atmospheric pressure. It was then acidified with 75% sulfuric acid before being collected in a caustic stainless steel receiver. The off gases were then passed through two caustic scrubbing solutions in series to remove the hydrogen sulfide.Samples of the liquid product were analyzed by standard technique for thioglycolic acid (TGA), thiodiglycolic acid (TDGA) and dithiodiglycolic acid (DTDGA) using high pressure liquid chromatography. The thioglygolic acid can be recovered by extraction using methylisobutylketone followed by distillation.
Using the apparatus described above a series of runs were conducted using a commercial mixture of monochloroacetic acid (MCA) and dichloroacetic acid (DCA) in a molar ratio of 97:3.
the reactions were each run at a pressure of 400 psig (2758 kPa) (inlet and exit pressure) and a residence time of 40 minutes. The temperatures of the runs were varied between 25 C and 80"C by monitering the reaction and exit temperature. The results of the runs are given in Table
I below.
TABLE I
Run Temp. MCA DCA NaSH TGA TDGA DTDGA cc molar conc. S yield
1 25 3.0 0.09 6.6 91.4 4.5
2 50 3.0 0.09 6.6 87.3 6.3
3 80 3.0 0.09 6.6 90.3 8.6
EXAMPLE II
A series of runs were conducted in the same manner as described in Example I above except that the temperature was maintained at 25'C while the pressure in the reaction zone was varied in each run. The results given in Table II below show that the present process must be carried out at elevated pressure of at least about 250 psig (1723 kPa) (primarily due to H2S) to provide the desired thioglycolic acid in high yields. Reactions carried out at lower pressures (even at much longer reaction times) does not provide the high yields desired.
TABLE II
Run Temp. Pressure Residence Yield cc psig(kPa) Time (min.) TGA S 4 25 0 70 57
5 25 150 (1034) 70 88
6 25 250 (1723) 40 92
7 25 Iroo (2758) 40 95
EXAMPLE 111
A series of runs is conducted in the same manner as described in Example I above except that the thioether of'glycolic acid (TDGA) is recovered as the still bottom from the distillation and recovery of the thioglycolic acid. The recovered thioether is introduced back into the reaction zone as part of the mixed organic acid feed stream. The resultant overall yield of thioglycolic acid product is increased by about 3.5 to 5 percent.
Claims (12)
1. A process for forming thioglycolic acid which comprises contacting in a reaction zone, under an elevated pressure of at least 250 psig (1723 kpa) formed by hydrogen sulfide gas, a mixture of monochloroacetic acid and dichloroacetic acid or their alkali metal salts in a weight ratio of from 99:1 75:25 with an alkali or alkaline earth metal hydrosulfide such that the molar ratio of said metal hydrosulfide to monochloroacetic acid as free acid is at least 2.1 and to dichloroacetic acid is at least 3.1; separating the liquid products and recovering the thioglycolic acid therefrom.
2. The process of claim 1 wherein the reaction zone pressure is from 250 to 500 psig (1723 to 3488 kPa).
3. The process of claim 1 or 2 wherein the reaction zone is at a temperature of from ambient to about 150'C.
4. The process of claim 3 wherein the reaction zone is at a temperature of from ambient to about 100 C.
5. The process of claim 4 wherein the reaction zone is at a temperature of from ambient to 60 C.
6. The process of any of claims 1 to 5 wherein the ratio of the metal hydrosulfide to the combined mixture of mono and dichloroacetic acid is from 2.1 to about 3 with respect to the monochloroacetic acid component and from 3.1 to about 4 for the dichloroacetic acid component.
7. The process of any of claims 1 to 6 wherein the ratio of the hydrosulfide to the combined mono and dichloroacetic acid as acid salt is from 1.1 to about 1.9 and said hydrosulfide is introduced to the reaction zone as sodium hydrosulfide.
8. The process of any of claims 1 to 7 wherein the molar ratio of monochloroacetic to dichloroacetic acid is from 99:1 to 75:25.
9. The process of claim 8 wherein the molar ratio of monochloroacetic to dichloroacetic acid is from 98:2 to 95:5.
10. The process of any of claims 1 to 9 which further comprises separating and recovering thiodiglycolic acid from the reaction zone liquid products and reintroducing at least a portion of the recovered thiodiglycolic acid to the reaction zone.
11. The process of claim 1 substantially as described in any one of the Examples.
12. Thioglycolic acid when produced by the process of any of the preceding claims.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US65558684A | 1984-09-28 | 1984-09-28 |
Publications (2)
Publication Number | Publication Date |
---|---|
GB8523818D0 GB8523818D0 (en) | 1985-10-30 |
GB2164939A true GB2164939A (en) | 1986-04-03 |
Family
ID=24629498
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB08523818A Withdrawn GB2164939A (en) | 1984-09-28 | 1985-09-27 | Synthesis of thioglycolic acid |
Country Status (9)
Country | Link |
---|---|
JP (1) | JPS61118358A (en) |
BE (1) | BE903323A (en) |
DE (1) | DE3534612A1 (en) |
FR (1) | FR2571051A1 (en) |
GB (1) | GB2164939A (en) |
IT (1) | IT1201473B (en) |
LU (1) | LU86097A1 (en) |
NL (1) | NL8502488A (en) |
SE (1) | SE8504416L (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2135836T3 (en) * | 1995-12-21 | 1999-11-01 | Akzo Nobel Nv | PROCEDURE FOR THE PREPARATION OF THIOGLICOLICO ACID. |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5129440A (en) * | 1974-09-05 | 1976-03-12 | Otsuka Kagaku Yakuhin | CHIOGURIKOORUSANNOSEIZOHO |
DE2711867A1 (en) * | 1977-03-18 | 1978-09-21 | Hoechst Ag | Thioglycolic acid prepn. - by reacting mono-chloroacetic acid with e.g. Gp=IA or Gp=IIA metal bi:sulphide in aq. medium under carbon di:oxide pressure |
-
1985
- 1985-09-11 NL NL8502488A patent/NL8502488A/en not_active Application Discontinuation
- 1985-09-24 SE SE8504416A patent/SE8504416L/en not_active Application Discontinuation
- 1985-09-25 LU LU86097A patent/LU86097A1/en unknown
- 1985-09-25 JP JP60210346A patent/JPS61118358A/en active Granted
- 1985-09-26 IT IT22282/85A patent/IT1201473B/en active
- 1985-09-26 BE BE0/215640A patent/BE903323A/en not_active IP Right Cessation
- 1985-09-26 DE DE19853534612 patent/DE3534612A1/en not_active Withdrawn
- 1985-09-27 FR FR8514387A patent/FR2571051A1/en not_active Withdrawn
- 1985-09-27 GB GB08523818A patent/GB2164939A/en not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
SE8504416L (en) | 1986-03-29 |
IT1201473B (en) | 1989-02-02 |
SE8504416D0 (en) | 1985-09-24 |
FR2571051A1 (en) | 1986-04-04 |
DE3534612A1 (en) | 1986-04-17 |
IT8522282A0 (en) | 1985-09-26 |
LU86097A1 (en) | 1986-03-11 |
NL8502488A (en) | 1986-04-16 |
JPH0584307B2 (en) | 1993-12-01 |
GB8523818D0 (en) | 1985-10-30 |
BE903323A (en) | 1986-01-16 |
JPS61118358A (en) | 1986-06-05 |
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Legal Events
Date | Code | Title | Description |
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WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |