CA1139259A - Process for preparing 2-alkoxyethyl mercaptans - Google Patents
Process for preparing 2-alkoxyethyl mercaptansInfo
- Publication number
- CA1139259A CA1139259A CA000352868A CA352868A CA1139259A CA 1139259 A CA1139259 A CA 1139259A CA 000352868 A CA000352868 A CA 000352868A CA 352868 A CA352868 A CA 352868A CA 1139259 A CA1139259 A CA 1139259A
- Authority
- CA
- Canada
- Prior art keywords
- vinyl ether
- reaction
- alkoxyethyl
- mercaptan
- mercaptans
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/04—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by addition of hydrogen sulfide or its salts to unsaturated compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Process for preparing 2-alkoxyethyl mercaptans by reacting an alkyl vinyl ether with an excess of hydrogen sulfide in the liquid phase in the presence of ultraviolet radiation.
The products are important ingredients for veterinary drugs.
Process for preparing 2-alkoxyethyl mercaptans by reacting an alkyl vinyl ether with an excess of hydrogen sulfide in the liquid phase in the presence of ultraviolet radiation.
The products are important ingredients for veterinary drugs.
Description
1~3~2S9 This invention relates to a process for preparing 2-alkoxyethyl mercaptans which are important materials in the preparation of veterinary drugs.
The first known preparation of this class of compounds was reported by Chapman and Owen in J. CHEM. SOC. 1950, 579~85;
(C. A. 43, 7424 d; C. A. 44, 6811c). They prepared 2-methoxy-ethyl mercaptan by a three-step process, with a product yield of less than 40% of theory. Prelexhaeva, Shapiro, and Shostakovski reported in C.A. 46, 3494g the reaction of butyl vinyl ether with hydrogen sulfide in dioxane as a solvent with hydrogen chloride and piperidine as catalysts to produce 2-butoxyethyl mercaptan, with a yield of only 15% and with various sulfides and cleavage products as the major products of the reaction. Several years later Castonguay and Rousseau reported in CAN. J. CHEM. 49, 2125 (1971) that when hydrogen sulfide and methyl vinyl ether were reacted in the vapor phase with ultraviolet irradiation as a catalyst, only cleavage products were obtained from the reaction.
In an attempt to make 2-methoxyethyl mercaptan by react-ing hydrogen sulfide and methyl vinyl ether using triethylamine as a catalyst in this laboratory there was recovered a two-layer liquid in which methanol was the principal component in both layers. Carbon disulfide and diethyl sulfide were also found as products of this reaction.
It is an object of the present invention to provide an improved method for producing 2-alkoxyethyl mercaptans from hydrogen sulfide and alkyl vinyl ethers. It is another object of this invention to provide a process for preparing 2-alkoxy-;,
The first known preparation of this class of compounds was reported by Chapman and Owen in J. CHEM. SOC. 1950, 579~85;
(C. A. 43, 7424 d; C. A. 44, 6811c). They prepared 2-methoxy-ethyl mercaptan by a three-step process, with a product yield of less than 40% of theory. Prelexhaeva, Shapiro, and Shostakovski reported in C.A. 46, 3494g the reaction of butyl vinyl ether with hydrogen sulfide in dioxane as a solvent with hydrogen chloride and piperidine as catalysts to produce 2-butoxyethyl mercaptan, with a yield of only 15% and with various sulfides and cleavage products as the major products of the reaction. Several years later Castonguay and Rousseau reported in CAN. J. CHEM. 49, 2125 (1971) that when hydrogen sulfide and methyl vinyl ether were reacted in the vapor phase with ultraviolet irradiation as a catalyst, only cleavage products were obtained from the reaction.
In an attempt to make 2-methoxyethyl mercaptan by react-ing hydrogen sulfide and methyl vinyl ether using triethylamine as a catalyst in this laboratory there was recovered a two-layer liquid in which methanol was the principal component in both layers. Carbon disulfide and diethyl sulfide were also found as products of this reaction.
It is an object of the present invention to provide an improved method for producing 2-alkoxyethyl mercaptans from hydrogen sulfide and alkyl vinyl ethers. It is another object of this invention to provide a process for preparing 2-alkoxy-;,
- 2 -1139~jg ethyl mercaptans in very high yields. It is another object of this invention to provide a process for preparing 2-alkoxyethyl mercaptan in the absence of any substantial amount of by-products.
Still other objects will appear from the more detailed descrip-tion of this invention which follows.
In accordance with this invention there is provided a process for the preparation of 2-alkoxyethyl mercaptans by the reaction of an excess (on a molar basis) of hydrogen sulfide with an alkyl vinyl ether in the liquid phase in the presence of ultraviolet radiation. The reaction products are easily distilled to produce 2-alkoxyethyl mercaptans in high yield. In specific embodiments of this invention the reaction temperature is 10 -60C, the reaction time is lO minutes to 3 hours, and the mol ratio of hydrogen sulfide to alkyl vinyl ether is 5-lO.
It is important that the reaction be conducted in the liquid phase since it was found that substantially none of the desired product was obtained when the reaction was conducted in the vapor phase. In order to maintain the reaction mixture as a liquid it is necessary to adjust the temperature and pressure of the reaction mixture to keep it in the liquid phase. Except for this requirement the temperatures and pressures of the reaction are not critical. It is preferred to operate at temperatures of 10-60C and pressures of 300-700 psig although operation can be conducted at 0-75 C.
The catalyst for the reaction is ultraviolet radiation which can be obtained with any of a variety of commercially available lamps. The length of time to which the reaction is 11~9~
exposed to such irradiation has been found to produce differences in the yield of desired product. In general it may be said that the irradiation time should be from about 10 minutes to about 3 hours with the preferred exposure time ranging from about 30 minutes to 2 hours. The optimum time is easily determined for any given system.
The products of this r~action, 2-alkoxyethyl mercaptans, are valuable starting materials for the preparation of proprie-tary veterinary drugs. The highest homologs, for example, where the alkoxy group contains C8 to C18 carbon atoms, are also of interest as surface active agents.
The process of this invention is illustrated in the following examples where, unless otherwise specified, parts and percentages are by weight and temperatures are in degrees centri-grade. It is not intended that these examples will limit the invention in any way since the described embodiments are merely illustrative of the invention.
Into a 3.78 liter stainless steel reactor there was charged 470 grams of methyl vinyl ether and sufficient hydrogen sulfide to provide 6 mols of hydrogen sulfide per mol of methyl vinyl ether. The temperature was raised to 40C and the pressure to 370 psig to produce a liquid reaction mixture which was then agitated while being subjected to ultraviolet radiation (Hanovia lamp #6515-32, 200 watts) for 120 minutes. The following data were obtained from this run:
~39ZS9 Irradiation~ Conversion to Time-2- Me~thoxyethyl Mercaptan 20 min. 88%
60 min. 99%
120 min. 92%
The conclusions to be drawn are that at these reaction conditions, in the liquid phase, reaction occurs very rapidly, and the optimum conversion is at an irradiation time of approxi-mately 60 minutes.
The procedure of Example 1 was repeated employing 390 grams methyl vinyl ether and a mol ratio of 7.7 mols hydrogen sulfide per mol methyl vinyl ether at a reaction temperature of 36C, a reaction pressure of 410 psig., and an irradiation time of 135 minutes. The yield of 2-methoxyethyl mercaptan was 90%.
The procedure of Example 1 was repeated using 150 grams methyl vinyl ether and a mol ratio of 8 mols hydrogen sulfide per mol methyl vinyl ether at a reaction pressure of 420 psig., and an irradia~ion time of 150 minutes. The yield of 2-methoxyethyl mercaptan was found to be 89.7%. Distillation gave a 98-99%
pure product, according ~o gas chromatographic analysis, and the following elemental analysis:
Found Theory % Carbon 39.3 39.13 % Hydrogen 8.88 8.76 ~L39ZS~
.
Found Theory % Mercaptan Sulfur 34.80 34.7 % Total Sulfur 35.0 34.7 In place of the methyl vinyl ether used in the above examples, butyl vinyl ether may be used to prepare 2-butoxyethyl mercaptan, octyl vinyl ether may be used to prepare 2-octoxyethyl mercaptan, dodecyl vinyl ether may be used to prepare 2-dodecoxy-ethyl mercaptan, and octodecyl vinyl ether may be used to make 2-octadecoxyethyl mercaptan. The alkyl group may be straight-chain, branched, or cyclic, and may be substituted by a groupthat does not interfere with the reaction. For example, cyclo-hexyl vinyl ether may be used in the process of the invention.
Although the invention has been described in considerable detail with reference to certain preferred embodiments thereof, it will be understood that variations and modifications can be effected with the spirit and scope of the invention as described herein above and as defined in thQ appended claims.
Still other objects will appear from the more detailed descrip-tion of this invention which follows.
In accordance with this invention there is provided a process for the preparation of 2-alkoxyethyl mercaptans by the reaction of an excess (on a molar basis) of hydrogen sulfide with an alkyl vinyl ether in the liquid phase in the presence of ultraviolet radiation. The reaction products are easily distilled to produce 2-alkoxyethyl mercaptans in high yield. In specific embodiments of this invention the reaction temperature is 10 -60C, the reaction time is lO minutes to 3 hours, and the mol ratio of hydrogen sulfide to alkyl vinyl ether is 5-lO.
It is important that the reaction be conducted in the liquid phase since it was found that substantially none of the desired product was obtained when the reaction was conducted in the vapor phase. In order to maintain the reaction mixture as a liquid it is necessary to adjust the temperature and pressure of the reaction mixture to keep it in the liquid phase. Except for this requirement the temperatures and pressures of the reaction are not critical. It is preferred to operate at temperatures of 10-60C and pressures of 300-700 psig although operation can be conducted at 0-75 C.
The catalyst for the reaction is ultraviolet radiation which can be obtained with any of a variety of commercially available lamps. The length of time to which the reaction is 11~9~
exposed to such irradiation has been found to produce differences in the yield of desired product. In general it may be said that the irradiation time should be from about 10 minutes to about 3 hours with the preferred exposure time ranging from about 30 minutes to 2 hours. The optimum time is easily determined for any given system.
The products of this r~action, 2-alkoxyethyl mercaptans, are valuable starting materials for the preparation of proprie-tary veterinary drugs. The highest homologs, for example, where the alkoxy group contains C8 to C18 carbon atoms, are also of interest as surface active agents.
The process of this invention is illustrated in the following examples where, unless otherwise specified, parts and percentages are by weight and temperatures are in degrees centri-grade. It is not intended that these examples will limit the invention in any way since the described embodiments are merely illustrative of the invention.
Into a 3.78 liter stainless steel reactor there was charged 470 grams of methyl vinyl ether and sufficient hydrogen sulfide to provide 6 mols of hydrogen sulfide per mol of methyl vinyl ether. The temperature was raised to 40C and the pressure to 370 psig to produce a liquid reaction mixture which was then agitated while being subjected to ultraviolet radiation (Hanovia lamp #6515-32, 200 watts) for 120 minutes. The following data were obtained from this run:
~39ZS9 Irradiation~ Conversion to Time-2- Me~thoxyethyl Mercaptan 20 min. 88%
60 min. 99%
120 min. 92%
The conclusions to be drawn are that at these reaction conditions, in the liquid phase, reaction occurs very rapidly, and the optimum conversion is at an irradiation time of approxi-mately 60 minutes.
The procedure of Example 1 was repeated employing 390 grams methyl vinyl ether and a mol ratio of 7.7 mols hydrogen sulfide per mol methyl vinyl ether at a reaction temperature of 36C, a reaction pressure of 410 psig., and an irradiation time of 135 minutes. The yield of 2-methoxyethyl mercaptan was 90%.
The procedure of Example 1 was repeated using 150 grams methyl vinyl ether and a mol ratio of 8 mols hydrogen sulfide per mol methyl vinyl ether at a reaction pressure of 420 psig., and an irradia~ion time of 150 minutes. The yield of 2-methoxyethyl mercaptan was found to be 89.7%. Distillation gave a 98-99%
pure product, according ~o gas chromatographic analysis, and the following elemental analysis:
Found Theory % Carbon 39.3 39.13 % Hydrogen 8.88 8.76 ~L39ZS~
.
Found Theory % Mercaptan Sulfur 34.80 34.7 % Total Sulfur 35.0 34.7 In place of the methyl vinyl ether used in the above examples, butyl vinyl ether may be used to prepare 2-butoxyethyl mercaptan, octyl vinyl ether may be used to prepare 2-octoxyethyl mercaptan, dodecyl vinyl ether may be used to prepare 2-dodecoxy-ethyl mercaptan, and octodecyl vinyl ether may be used to make 2-octadecoxyethyl mercaptan. The alkyl group may be straight-chain, branched, or cyclic, and may be substituted by a groupthat does not interfere with the reaction. For example, cyclo-hexyl vinyl ether may be used in the process of the invention.
Although the invention has been described in considerable detail with reference to certain preferred embodiments thereof, it will be understood that variations and modifications can be effected with the spirit and scope of the invention as described herein above and as defined in thQ appended claims.
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS POLLOWS:
1. Process for the preparation of 2-alkoxyethyl mer-captans which comprises reacting an excess of hydrogen sulfile (on a molar basis) with a Cl to C18 alkyl or cycloalkyl vinyl ether in the liquid phase in the presence of ultraviolet radiation and recovering as the reaction product, a 2-alkoxyethyl mercaptan, in which the alkoxy group contains from 1 to 18 carbon atoms.
2. The process of Claim 1 wherein the reaction tempera-ture is 10°-60°C.
3. The process of Claim 1 wherein the reaction time is 10 minutes to 3 hours.
4. The process of Claim 1 wherein the mol ratio of hydro-ger. sulfide to alkyl vinyl ether is 5-10.
5. The process of Claim 1 wherein the alkyl vinyl ether is methyl vinyl ether and the reaction product is 2-methoxy ethyl mercaptan.
6. The process of claim 1, wherein the cycloalkyl vinyl ether is cyclohexyl vinyl ether.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US4349779A | 1979-05-29 | 1979-05-29 | |
| US043,497 | 1979-05-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1139259A true CA1139259A (en) | 1983-01-11 |
Family
ID=21927460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000352868A Expired CA1139259A (en) | 1979-05-29 | 1980-05-28 | Process for preparing 2-alkoxyethyl mercaptans |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5632451A (en) |
| BE (1) | BE883505A (en) |
| CA (1) | CA1139259A (en) |
| DE (1) | DE3020488A1 (en) |
| FR (1) | FR2457856A1 (en) |
| GB (1) | GB2049669B (en) |
| IT (1) | IT1144063B (en) |
| NL (1) | NL8002178A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4942848A (en) * | 1987-04-30 | 1990-07-24 | Nissan Motor Co., Ltd. | Air-fuel ratio control system for automotive internal combustion engine or the like with fuel type discrimination capabilities |
| US7404928B2 (en) * | 2002-07-29 | 2008-07-29 | The United States Of America As Represented By The Secretary Of The Navy | Thiol terminated monodisperse ethylene oxide oligomer capped gold nanoclusters |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL34486A (en) * | 1969-06-04 | 1973-10-25 | Stauffer Chemical Co | The preparation of mercaptans |
-
1980
- 1980-03-28 GB GB8010627A patent/GB2049669B/en not_active Expired
- 1980-04-15 NL NL8002178A patent/NL8002178A/en not_active Application Discontinuation
- 1980-05-12 IT IT48653/80A patent/IT1144063B/en active
- 1980-05-28 BE BE0/200784A patent/BE883505A/en not_active IP Right Cessation
- 1980-05-28 CA CA000352868A patent/CA1139259A/en not_active Expired
- 1980-05-28 FR FR8011823A patent/FR2457856A1/en active Granted
- 1980-05-28 JP JP7023880A patent/JPS5632451A/en active Pending
- 1980-05-29 DE DE19803020488 patent/DE3020488A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| GB2049669A (en) | 1980-12-31 |
| IT8048653A0 (en) | 1980-05-12 |
| GB2049669B (en) | 1983-09-07 |
| FR2457856A1 (en) | 1980-12-26 |
| FR2457856B1 (en) | 1985-04-26 |
| JPS5632451A (en) | 1981-04-01 |
| DE3020488A1 (en) | 1980-12-11 |
| IT1144063B (en) | 1986-10-29 |
| BE883505A (en) | 1980-09-15 |
| NL8002178A (en) | 1980-12-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |