TWI710548B - 2,2,2-三氟乙硫醇之合成 - Google Patents
2,2,2-三氟乙硫醇之合成 Download PDFInfo
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- TWI710548B TWI710548B TW104125725A TW104125725A TWI710548B TW I710548 B TWI710548 B TW I710548B TW 104125725 A TW104125725 A TW 104125725A TW 104125725 A TW104125725 A TW 104125725A TW I710548 B TWI710548 B TW I710548B
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- RYRLLAOLJVDVNN-UHFFFAOYSA-N 2,2,2-trifluoroethanethiol Chemical compound FC(F)(F)CS RYRLLAOLJVDVNN-UHFFFAOYSA-N 0.000 title description 9
- 230000015572 biosynthetic process Effects 0.000 title description 8
- 238000003786 synthesis reaction Methods 0.000 title description 3
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- -1 Na or K Chemical class 0.000 claims abstract description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 70
- 238000000034 method Methods 0.000 claims description 59
- 239000002904 solvent Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 26
- 239000006227 byproduct Substances 0.000 claims description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 239000007795 chemical reaction product Substances 0.000 claims description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 14
- 239000003444 phase transfer catalyst Substances 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 239000012429 reaction media Substances 0.000 claims description 10
- 239000003495 polar organic solvent Substances 0.000 claims description 7
- 150000005621 tetraalkylammonium salts Chemical group 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 229940113088 dimethylacetamide Drugs 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 abstract description 2
- 229910052708 sodium Inorganic materials 0.000 abstract description 2
- 125000005843 halogen group Chemical group 0.000 abstract 1
- 239000000047 product Substances 0.000 description 22
- 239000011541 reaction mixture Substances 0.000 description 20
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 17
- CYXIKYKBLDZZNW-UHFFFAOYSA-N 2-Chloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)CCl CYXIKYKBLDZZNW-UHFFFAOYSA-N 0.000 description 16
- 238000005481 NMR spectroscopy Methods 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000460 chlorine Substances 0.000 description 12
- 239000007858 starting material Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 235000011089 carbon dioxide Nutrition 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- ZNKXTIAQRUWLRL-UHFFFAOYSA-M sodium;sulfane;hydroxide Chemical compound O.[Na+].[SH-] ZNKXTIAQRUWLRL-UHFFFAOYSA-M 0.000 description 5
- 238000004293 19F NMR spectroscopy Methods 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- 239000012038 nucleophile Substances 0.000 description 3
- 238000003408 phase transfer catalysis Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013545 self-assembled monolayer Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003573 thiols Chemical group 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-M toluenesulfonate group Chemical class C=1(C(=CC=CC1)S(=O)(=O)[O-])C LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 description 1
- 229910052725 zinc Inorganic materials 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
-
- 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
- C07C323/01—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton
- C07C323/02—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton having sulfur atoms of thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/03—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton having sulfur atoms of thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
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)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201462034214P | 2014-08-07 | 2014-08-07 | |
| US62/034,214 | 2014-08-07 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201605781A TW201605781A (zh) | 2016-02-16 |
| TWI710548B true TWI710548B (zh) | 2020-11-21 |
Family
ID=55264366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW104125725A TWI710548B (zh) | 2014-08-07 | 2015-08-07 | 2,2,2-三氟乙硫醇之合成 |
Country Status (9)
| Country | Link |
|---|---|
| US (2) | US20170210706A1 (enExample) |
| EP (1) | EP3177280B1 (enExample) |
| JP (1) | JP6620142B2 (enExample) |
| KR (1) | KR102417295B1 (enExample) |
| CN (1) | CN106659699B (enExample) |
| ES (1) | ES2781077T3 (enExample) |
| MX (1) | MX2017001672A (enExample) |
| TW (1) | TWI710548B (enExample) |
| WO (1) | WO2016022408A1 (enExample) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210116544A (ko) | 2019-01-18 | 2021-09-27 | 바스프 에스이 | 티오카르보네이트의 제조 방법 |
| CN109880075B (zh) * | 2019-03-06 | 2021-10-08 | 山东益丰生化环保股份有限公司 | 一种高巯基多硫醇固化剂的制备方法 |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2252867A (en) * | 1939-04-21 | 1941-08-19 | Hooker Electrochemical Co | Process for production of alkali metal sulphide and hydrosulphide of high purity and concentration |
| US2894991A (en) * | 1956-12-10 | 1959-07-14 | Pennsalt Chemicals Corp | Fluoroalkyl sulfur compounds |
| US3006964A (en) * | 1959-09-24 | 1961-10-31 | Pennsalt Chemicals Corp | Process for fluoroalkyl sulfides |
| US3088849A (en) * | 1961-12-11 | 1963-05-07 | Minnesota Mining & Mfg | Fluorocarbon-substituted mercaptans |
| DE4333058A1 (de) * | 1993-09-29 | 1995-03-30 | Hoechst Ag | Verfahren zur Herstellung von Trifluorethylschwefelverbindungen aus Thiolaten und 1-Chlor-2,2,2-trifluorethan |
| US6765109B1 (en) * | 1998-06-29 | 2004-07-20 | Roche Colorado Corporation | Preparation of S-aryl-cysteine and its derivatives |
| CN1432566A (zh) * | 2002-01-10 | 2003-07-30 | 王春煜 | 一种二巯基丙磺酸钠的制造及纯化方法 |
| US6680398B1 (en) * | 2002-08-16 | 2004-01-20 | Dow Corning Corporation | Method of making mercaptoalkylalkoxysilanes |
| CN1218939C (zh) * | 2002-12-25 | 2005-09-14 | 南化集团研究院 | 一种制取巯基乙酸的方法 |
| JP2012056898A (ja) * | 2010-09-09 | 2012-03-22 | Sumitomo Seika Chem Co Ltd | アルカンチオールの製造方法 |
-
2015
- 2015-07-31 ES ES15829587T patent/ES2781077T3/es active Active
- 2015-07-31 KR KR1020177003454A patent/KR102417295B1/ko active Active
- 2015-07-31 JP JP2017506657A patent/JP6620142B2/ja active Active
- 2015-07-31 CN CN201580042244.9A patent/CN106659699B/zh active Active
- 2015-07-31 US US15/500,654 patent/US20170210706A1/en not_active Abandoned
- 2015-07-31 EP EP15829587.3A patent/EP3177280B1/en active Active
- 2015-07-31 WO PCT/US2015/043060 patent/WO2016022408A1/en not_active Ceased
- 2015-07-31 MX MX2017001672A patent/MX2017001672A/es unknown
- 2015-08-07 TW TW104125725A patent/TWI710548B/zh active
-
2019
- 2019-01-03 US US16/238,548 patent/US10717707B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| WO2016022408A1 (en) | 2016-02-11 |
| JP2017523217A (ja) | 2017-08-17 |
| CN106659699B (zh) | 2022-10-11 |
| US20170210706A1 (en) | 2017-07-27 |
| EP3177280A4 (en) | 2018-01-03 |
| KR20170041732A (ko) | 2017-04-17 |
| TW201605781A (zh) | 2016-02-16 |
| MX2017001672A (es) | 2017-08-15 |
| JP6620142B2 (ja) | 2019-12-11 |
| EP3177280B1 (en) | 2020-02-26 |
| EP3177280A1 (en) | 2017-06-14 |
| KR102417295B1 (ko) | 2022-07-07 |
| CN106659699A (zh) | 2017-05-10 |
| US20190135740A1 (en) | 2019-05-09 |
| US10717707B2 (en) | 2020-07-21 |
| ES2781077T3 (es) | 2020-08-28 |
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