GB2049669A - Process for Preparing 2-Alkoxy- or-Cycloalkoxy Ethyl Mercaptans - Google Patents
Process for Preparing 2-Alkoxy- or-Cycloalkoxy Ethyl Mercaptans Download PDFInfo
- Publication number
- GB2049669A GB2049669A GB8010627A GB8010627A GB2049669A GB 2049669 A GB2049669 A GB 2049669A GB 8010627 A GB8010627 A GB 8010627A GB 8010627 A GB8010627 A GB 8010627A GB 2049669 A GB2049669 A GB 2049669A
- Authority
- GB
- United Kingdom
- Prior art keywords
- reaction
- alkyl
- cycloalkyl
- vinyl ether
- hydrogen sulfide
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 9
- 239000007791 liquid phase Substances 0.000 claims abstract description 7
- 230000005855 radiation Effects 0.000 claims abstract description 6
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 12
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000007858 starting material Substances 0.000 claims description 2
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims 2
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical compound C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 claims 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical class CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims 1
- QDXBVEACAWKSFL-UHFFFAOYSA-N ethenethiol Chemical class SC=C QDXBVEACAWKSFL-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 description 9
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 4
- VHXDADVHQVXSKC-UHFFFAOYSA-N 2-methoxyethanethiol Chemical compound COCCS VHXDADVHQVXSKC-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- -1 cycloalkyl vinyl ether Chemical compound 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- NSBQEXGAGSBJGY-UHFFFAOYSA-N 2-butoxyethanethiol Chemical compound CCCCOCCS NSBQEXGAGSBJGY-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 239000000273 veterinary drug Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 description 1
- XXCVIFJHBFNFBO-UHFFFAOYSA-N 1-ethenoxyoctane Chemical compound CCCCCCCCOC=C XXCVIFJHBFNFBO-UHFFFAOYSA-N 0.000 description 1
- UNBYWYATNFOIAZ-UHFFFAOYSA-N 2-dodecoxyethanethiol Chemical compound CCCCCCCCCCCCOCCS UNBYWYATNFOIAZ-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- PIFZZFPFFSPLLJ-UHFFFAOYSA-N 2-octoxyethanethiol Chemical compound CCCCCCCCOCCS PIFZZFPFFSPLLJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
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
2-Alkoxy-or-cycloalkoxy ethyl mercaptans are prepared by reacting an alkyl (or cycloalkyl) vinyl ether with a molar excess of hydrogen sulfide, the reaction being carried out in the liquid phase in the presence of ultraviolet radiation.
Description
SPECIFICATION
Process for preparing 2-Alkoxyethyl
Mercaptans
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; A. 44, 6811c). They prepared 2-methoxy- ethyl mercaptan by a three-step process, with a product yield of less than 40% of theory.
Prelezhaeva, 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 reacting 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.
In accordance with the present invention, it has been discovered that 2-alkoxyethyl mercaptans can be prepared in high yield and without any substantial amount of by-products by reacting an alkyl or cycloalkyl vinyl ether in liquid phase with a molar excess of hydrogen sulfide, the reaction being performed 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 100--600C, the reaction time is 10 minutes to 3 hours, and the mol ratio of hydrogen sulfide to alkyl vinyl ether is 510.
Generally, the alkyl vinyl ether used in the process of this invention will contain from 1-1 8 carbon atoms in the alkyl or cycloalkyl moiety.
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 1 0-6O0C and pressures of 300-700 psig although operation can be conducted at 0--750C.
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 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 reaction, 2-alkoxyethyl
mercaptans, are valuable starting materials for
the preparation of proprietary veterinary drugs.
The highest homologs, for example, where the
alkoxy group contains C8 to C,8 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 centigrade. It is
not intended that these examples will limit the
invention in any way since the described
embodiments are merely illustrative of the
invention.
Example 1
Into a 3.78 liter stainless steel reactor there was charged 470 grams of methyl vinyl ether and sufficient hydrogen sulfide to provide 6 mois of
hydrogen sulfide per mol of methyl vinyl ether.
The temperature was raised to 400C 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:
% Conversion to
Irradiation 2-Methoxyethyl
Time 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 approximately 60 minutes.
Example 2
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 360C, a reaction pressure of 410 psig., and an irradiation time of 135 minutes. The yield of 2methoxyethyl mercaptan was 90%.
Example 3
The procedure of Example 1 was repeated using 1 50 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 irradiation time of 1 50 minutes. The yield of 2methoxyethyl mercaptan was found to be 89.7%.
Distillation gave a 9899% pure product, according to gas chromatographic analysis, and the following elemental analysis:
Found Theory
% Carbon 39.3 39.13
% Hydrogen 8.88 8.76
% 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-dodecoxyethyl mercaptan, and octodecyl vinyl ether may be used to make 2octadecoxyethyl mercaptan. The alkyl group may be straight-chain, branched, or cyclic, and may be substituted by a group that does not interfere with the reaction.
Claims (1)
- Claims1. A process for the preparation of alkyl (or cycloalkyl) vinyl mercaptans containing from 118 carbon atoms in the alkyl (or cycloalkyl) moiety, which comprises reacting a C1-C18 alkyl (or cycloalkyl) vinyl ether in the liquid phase with a molar excess. of hydrogen sulfide, the reaction being carried out under the influence of ultraviolet radiation.2. A process according to claim 1, wherein the reaction is performed at a temperature of from 1O-600C.3. A process according to claim 1 or 2, wherein the reaction period is from 10 minutes to 3 hours.4. A process according to claim 1,2 or 3, wherein the molar ratio of hydrogen sulfide to the alkyl (or cycloalkyl) vinyl sulfide is from 5:1 to 10:1.5. A process according to any one of the preceding claims, wherein the starting material is methyl vinyl ether.6. A process according to claim 1, substantially as hereinbefore described in any one of the Examples.New Claims or Amendments to Claims filed on 12 August 1980.Superseded Claim 1 New or Amended Claim:-1. A process for the preparation of alkyl (or cycloalkyl) ethyl mercaptans containing from 118 carbon atoms in the alkyl (or cycloalkyl) moiety, which comprises reacting a C1-C18 alkyl (or cycloalkyl) vinyl ether in the liquid phase with a molar excess of hydrogen sulfide, the reaction being carried out under the influence of ultraviolet radiation.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US4349779A | 1979-05-29 | 1979-05-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2049669A true GB2049669A (en) | 1980-12-31 |
| GB2049669B GB2049669B (en) | 1983-09-07 |
Family
ID=21927460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8010627A Expired GB2049669B (en) | 1979-05-29 | 1980-03-28 | Process for preparing 2-alkoxy or cycloalkoxy ethyl 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) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Families Citing this family (1)
| 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 |
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 FR FR8011823A patent/FR2457856A1/en active Granted
- 1980-05-28 BE BE0/200784A patent/BE883505A/en not_active IP Right Cessation
- 1980-05-28 JP JP7023880A patent/JPS5632451A/en active Pending
- 1980-05-28 CA CA000352868A patent/CA1139259A/en not_active Expired
- 1980-05-29 DE DE19803020488 patent/DE3020488A1/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3020488A1 (en) | 1980-12-11 |
| CA1139259A (en) | 1983-01-11 |
| FR2457856B1 (en) | 1985-04-26 |
| FR2457856A1 (en) | 1980-12-26 |
| GB2049669B (en) | 1983-09-07 |
| JPS5632451A (en) | 1981-04-01 |
| BE883505A (en) | 1980-09-15 |
| IT8048653A0 (en) | 1980-05-12 |
| NL8002178A (en) | 1980-12-02 |
| IT1144063B (en) | 1986-10-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |