AU2008334034B2 - Sulfur containing fluoroalkyl amines and isocyanates - Google Patents
Sulfur containing fluoroalkyl amines and isocyanates Download PDFInfo
- Publication number
- AU2008334034B2 AU2008334034B2 AU2008334034A AU2008334034A AU2008334034B2 AU 2008334034 B2 AU2008334034 B2 AU 2008334034B2 AU 2008334034 A AU2008334034 A AU 2008334034A AU 2008334034 A AU2008334034 A AU 2008334034A AU 2008334034 B2 AU2008334034 B2 AU 2008334034B2
- Authority
- AU
- Australia
- Prior art keywords
- chosen
- fluoroalkyl
- amine
- amide
- amide intermediate
- 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.)
- Ceased
Links
- -1 fluoroalkyl amines Chemical class 0.000 title claims abstract description 58
- 229910052717 sulfur Inorganic materials 0.000 title claims description 42
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 33
- 239000011593 sulfur Substances 0.000 title claims description 33
- 239000012948 isocyanate Substances 0.000 title claims description 10
- 150000002513 isocyanates Chemical class 0.000 title description 6
- 150000001408 amides Chemical class 0.000 claims description 76
- 150000003573 thiols Chemical class 0.000 claims description 38
- 230000020176 deacylation Effects 0.000 claims description 32
- 238000005947 deacylation reaction Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 31
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims description 26
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 26
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 150000002540 isothiocyanates Chemical class 0.000 claims description 7
- 125000000743 hydrocarbylene group Chemical group 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000000543 intermediate Substances 0.000 description 94
- 150000001412 amines Chemical class 0.000 description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000005160 1H NMR spectroscopy Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 17
- 238000007254 oxidation reaction Methods 0.000 description 17
- 238000005481 NMR spectroscopy Methods 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 150000002978 peroxides Chemical class 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000003039 volatile agent Substances 0.000 description 7
- 125000003277 amino group Chemical group 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 125000004434 sulfur atom Chemical group 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 238000007342 radical addition reaction Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 4
- 125000004354 sulfur functional group Chemical group 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 150000003141 primary amines Chemical group 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 229940086542 triethylamine Drugs 0.000 description 3
- 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 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- 235000019502 Orange oil Nutrition 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- QLZHNIAADXEJJP-UHFFFAOYSA-L dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [O-]P([O-])(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-L 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- MWSPFHZPVVWJCO-UHFFFAOYSA-M hydron;methyl(trioctyl)azanium;sulfate Chemical compound OS([O-])(=O)=O.CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC MWSPFHZPVVWJCO-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- PNLUGRYDUHRLOF-UHFFFAOYSA-N n-ethenyl-n-methylacetamide Chemical compound C=CN(C)C(C)=O PNLUGRYDUHRLOF-UHFFFAOYSA-N 0.000 description 2
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000010502 orange oil Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- MRPSASLEFZGUCD-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,6,6-undecafluoro-8-iodooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)CC(F)(F)CCI MRPSASLEFZGUCD-UHFFFAOYSA-N 0.000 description 1
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 description 1
- YFOXQTKUONVNNH-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-1-(1,1,2,2,3,3,3-heptafluoropropoxy)-4-iodobutane Chemical compound FC(F)(F)C(F)(F)C(F)(F)OC(F)(F)C(F)(F)CCI YFOXQTKUONVNNH-UHFFFAOYSA-N 0.000 description 1
- FWRSDSURSFDRBJ-UHFFFAOYSA-N 1-[2-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctylsulfanyl)ethyl]pyrrolidin-2-one Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCSCCN1CCCC1=O FWRSDSURSFDRBJ-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- JYWKEVKEKOTYEX-UHFFFAOYSA-N 2,6-dibromo-4-chloroiminocyclohexa-2,5-dien-1-one Chemical compound ClN=C1C=C(Br)C(=O)C(Br)=C1 JYWKEVKEKOTYEX-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- DDDLXTOBCVXQRL-UHFFFAOYSA-N 2-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctylsulfonyl)ethanamine Chemical compound NCCS(=O)(=O)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F DDDLXTOBCVXQRL-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- SMUQAHYSAIQWNW-UHFFFAOYSA-N 2-[3,3,4,4-tetrafluoro-4-(1,1,2,2,3,3,3-heptafluoropropoxy)butyl]sulfanylethanamine Chemical compound NCCSCCC(F)(F)C(F)(F)OC(F)(F)C(F)(F)C(F)(F)F SMUQAHYSAIQWNW-UHFFFAOYSA-N 0.000 description 1
- XRXANEMIFVRKLN-UHFFFAOYSA-N 2-hydroperoxy-2-methylbutane Chemical compound CCC(C)(C)OO XRXANEMIFVRKLN-UHFFFAOYSA-N 0.000 description 1
- BFSUQRCCKXZXEX-UHFFFAOYSA-N 2-methoxypropan-2-ol Chemical compound COC(C)(C)O BFSUQRCCKXZXEX-UHFFFAOYSA-N 0.000 description 1
- GTPHVVCYEWPQFE-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1-thiol Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCS GTPHVVCYEWPQFE-UHFFFAOYSA-N 0.000 description 1
- SUAUZSMELAKHAC-UHFFFAOYSA-N 3,3,5,5,6,6,7,7,8,8,8-undecafluorooctane-1-thiol Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)CC(F)(F)CCS SUAUZSMELAKHAC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 101100167062 Caenorhabditis elegans chch-3 gene Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 101710178035 Chorismate synthase 2 Proteins 0.000 description 1
- 241000518994 Conta Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101710152694 Cysteine synthase 2 Proteins 0.000 description 1
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 description 1
- 229920006063 Lamide® Polymers 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 101100006982 Mus musculus Ppcdc gene Proteins 0.000 description 1
- LEHYKWBQYJDYLB-UHFFFAOYSA-N N-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctylsulfanyl)ethanamine Chemical compound FC(CCSNCC)(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)F LEHYKWBQYJDYLB-UHFFFAOYSA-N 0.000 description 1
- BAWFJGJZGIEFAR-NNYOXOHSSA-N NAD zwitterion Chemical compound NC(=O)C1=CC=C[N+]([C@H]2[C@@H]([C@H](O)[C@@H](COP([O-])(=O)OP(O)(=O)OC[C@@H]3[C@H]([C@@H](O)[C@@H](O3)N3C4=NC=NC(N)=C4N=C3)O)O2)O)=C1 BAWFJGJZGIEFAR-NNYOXOHSSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- ZRVIMDQCIXXVBA-UHFFFAOYSA-N [N].NC(N)=S Chemical compound [N].NC(N)=S ZRVIMDQCIXXVBA-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- AXTPGQHJFRSSQJ-UHFFFAOYSA-N dichloro-ethoxy-methylsilane Chemical compound CCO[Si](C)(Cl)Cl AXTPGQHJFRSSQJ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Substances NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 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
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- SFUCAQIVQHAVSK-UHFFFAOYSA-N n-[2-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctylsulfanyl)ethyl]acetamide Chemical compound CC(=O)NCCSCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SFUCAQIVQHAVSK-UHFFFAOYSA-N 0.000 description 1
- HGUJTFZRHBSOJZ-UHFFFAOYSA-N n-[2-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctylsulfanyl)ethyl]formamide Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCSCCNC=O HGUJTFZRHBSOJZ-UHFFFAOYSA-N 0.000 description 1
- UMNPMAFGXXWWJA-UHFFFAOYSA-N n-[2-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctylsulfinyl)ethyl]formamide Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCS(=O)CCNC=O UMNPMAFGXXWWJA-UHFFFAOYSA-N 0.000 description 1
- ZNZRCCLAVZQXID-UHFFFAOYSA-N n-[2-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctylsulfonyl)ethyl]formamide Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCS(=O)(=O)CCNC=O ZNZRCCLAVZQXID-UHFFFAOYSA-N 0.000 description 1
- JOTZNMDLKOCTKR-UHFFFAOYSA-N n-[2-[3,3,4,4-tetrafluoro-4-(1,1,2,2,3,3,3-heptafluoropropoxy)butyl]sulfanylethyl]formamide Chemical compound FC(F)(F)C(F)(F)C(F)(F)OC(F)(F)C(F)(F)CCSCCNC=O JOTZNMDLKOCTKR-UHFFFAOYSA-N 0.000 description 1
- FMNAKWKJCDLWEN-UHFFFAOYSA-N n-ethyl-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1-sulfinamide Chemical compound CCNS(=O)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F FMNAKWKJCDLWEN-UHFFFAOYSA-N 0.000 description 1
- OVFLGDGIKOKYGR-UHFFFAOYSA-N n-methyl-n-[2-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctylsulfanyl)ethyl]acetamide Chemical compound CC(=O)N(C)CCSCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F OVFLGDGIKOKYGR-UHFFFAOYSA-N 0.000 description 1
- SHIGCAOWAAOWIG-UHFFFAOYSA-N n-prop-2-enylformamide Chemical compound C=CCNC=O SHIGCAOWAAOWIG-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- DUYAAUVXQSMXQP-UHFFFAOYSA-M thioacetate Chemical compound CC([S-])=O DUYAAUVXQSMXQP-UHFFFAOYSA-M 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C317/28—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/16—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of hydrogen sulfide or its salts to unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/18—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of thiols to unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- 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
- C07C323/23—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 nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/24—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 nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/25—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 nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
- C07C331/16—Isothiocyanates
- C07C331/18—Isothiocyanates having isothiocyanate groups bound to acyclic carbon atoms
- C07C331/20—Isothiocyanates having isothiocyanate groups bound to acyclic carbon atoms of a saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
- C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
- C07D207/27—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US524107P | 2007-12-03 | 2007-12-03 | |
| US61/005,241 | 2007-12-03 | ||
| US12/273,091 | 2008-11-18 | ||
| US12/273,091 US8153846B2 (en) | 2007-12-03 | 2008-11-18 | Sulfur containing fluoroalkyl amines and isocyanates |
| PCT/US2008/085100 WO2009073592A2 (en) | 2007-12-03 | 2008-12-01 | Sulfur containing fluoroalkyl amines and isocyanates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU2008334034A1 AU2008334034A1 (en) | 2009-06-11 |
| AU2008334034B2 true AU2008334034B2 (en) | 2013-06-06 |
Family
ID=40676434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2008334034A Ceased AU2008334034B2 (en) | 2007-12-03 | 2008-12-01 | Sulfur containing fluoroalkyl amines and isocyanates |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US8153846B2 (enExample) |
| EP (2) | EP2215056B1 (enExample) |
| JP (1) | JP5497659B2 (enExample) |
| KR (1) | KR20100101126A (enExample) |
| CN (1) | CN101939294A (enExample) |
| AU (1) | AU2008334034B2 (enExample) |
| CA (1) | CA2706610A1 (enExample) |
| NZ (1) | NZ585414A (enExample) |
| WO (1) | WO2009073592A2 (enExample) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8865843B2 (en) * | 2009-09-28 | 2014-10-21 | Axalta Coating Systems Ip Co., Llc | Fluorinated sag control agent and use thereof |
| EP2707356A4 (en) * | 2011-05-13 | 2014-10-15 | Univ Nanyang Tech | PROCESS FOR MODIFYING ORGANIC MOLECULES |
| FR3091870B1 (fr) | 2019-01-18 | 2021-11-05 | Adisseo France Sas | Agent pour l’initiation d’une reaction d’addition radicalaire et procede le mettant en œuvre |
| GB2597200B (en) * | 2019-05-09 | 2022-12-14 | Entreprises Nolk Inc | Portable fire pit and grill assembly |
| CN116836094A (zh) * | 2023-06-09 | 2023-10-03 | 福建三农新材料有限责任公司 | 一种全氟己基乙基硫醇的制备方法 |
Family Cites Families (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3655732A (en) * | 1967-05-16 | 1972-04-11 | Du Pont | Fluorinated acrylic monomers containing hetero atoms and their polymers |
| NL6908449A (enExample) * | 1969-06-03 | 1970-12-07 | ||
| US4126633A (en) * | 1973-09-12 | 1978-11-21 | Pennwalt Corporation | Fluorinated aliphatic sulfides |
| JPS5289633A (en) | 1976-01-17 | 1977-07-27 | Neos Kk | Perfluoroalkenyl aryl thioether derivatives |
| US4171282A (en) * | 1977-12-07 | 1979-10-16 | Ciba-Geigy Corporation | Fluorinated nonionic surfactants |
| JPS57108063A (en) | 1980-12-26 | 1982-07-05 | Sagami Chem Res Center | Perfluoroalkylsulfinyl compound and its preparation |
| US4490304A (en) * | 1982-12-29 | 1984-12-25 | Ciba-Geigy Corporation | Perfluoroalkyl thioalkylene amphoteric compounds |
| FR2592648B1 (fr) * | 1986-01-07 | 1988-07-29 | Atochem | Composes polyfluoroalkylthio-methyliques, leurs procedes de preparation et leurs applications comme agents tensio-actifs ou precurseurs de ces derniers. |
| FR2609463B1 (fr) * | 1987-01-13 | 1990-11-30 | Atochem | Synthese des perfluoroalkyl-2 ethanethiols |
| US5411766A (en) * | 1989-12-29 | 1995-05-02 | E. I. Du Pont De Nemours And Company | Substrates treated with polyfluoro nitrogen containing organic compounds |
| DE4007048A1 (de) * | 1990-03-07 | 1991-09-12 | Hoechst Ag | N-acyl-aminoalkyl-2-hydroxyethylsulfide und ein verfahren zu ihrer herstellung |
| DE59303252D1 (de) * | 1992-12-02 | 1996-08-22 | Hoechst Ag | Di-(3-(2-chlorethylsulfonyl)-l-propyl)-amin-Hydrochlorid und Verfahren zu seiner Herstellung |
| DE69413985T2 (de) | 1993-07-29 | 1999-04-22 | E.I. Du Pont De Nemours And Co., Wilmington, Del. | Verfahren zur herstellung von perfluoroalkyljodid |
| US5466877A (en) * | 1994-03-15 | 1995-11-14 | Minnesota Mining And Manufacturing Company | Process for converting perfluorinated esters to perfluorinated acyl fluorides and/or ketones |
| US5728887A (en) * | 1996-04-10 | 1998-03-17 | E. I. Du Pont De Nemours And Company | Catalytic hydrogenolysis of organic thiocyanates and disulfides to thiols |
| DE19807791A1 (de) * | 1998-02-19 | 1999-08-26 | Schering Ag | Kombinationspräparat aus Östrogen und Antiöstrogen |
| DE10108543C1 (de) | 2001-02-22 | 2002-04-04 | Wacker Chemie Gmbh | Verfahren zur Herstellung von Isocyanatgruppen aufweisenden Organosiliciumverbindungen |
| DE10332197A1 (de) | 2003-07-15 | 2005-02-10 | Synthopol Chemie Dr.Rer.Pol. Koch Gmbh & Co Kg | Harze mit chemisch gekoppelten Perfluoralkylverbindung(en) und Verfahren zu ihrer Herstellung |
| DE10332198A1 (de) | 2003-07-15 | 2005-02-10 | Synthopol Chemie Dr.Rer.Pol. Koch Gmbh & Co Kg | Harze mit chemisch gekoppelten Perfluoralkansäureamid(en) und Verfahren zu ihrer Herstellung |
| DE10332152A1 (de) | 2003-07-15 | 2005-02-03 | Degussa Ag | (Poly-)Uretdione mit chemisch gekoppelten Perfluoralkylverbindungen und Verfahren zu ihrer Herstellung |
| US7470745B2 (en) | 2006-11-13 | 2008-12-30 | E. I. Du Pont De Nemours And Company | Perfluoroether based polymers |
-
2008
- 2008-11-18 US US12/273,091 patent/US8153846B2/en not_active Expired - Fee Related
- 2008-12-01 NZ NZ585414A patent/NZ585414A/en not_active IP Right Cessation
- 2008-12-01 EP EP08857668.1A patent/EP2215056B1/en not_active Not-in-force
- 2008-12-01 KR KR1020107014616A patent/KR20100101126A/ko not_active Withdrawn
- 2008-12-01 AU AU2008334034A patent/AU2008334034B2/en not_active Ceased
- 2008-12-01 CN CN2008801190129A patent/CN101939294A/zh active Pending
- 2008-12-01 JP JP2010537003A patent/JP5497659B2/ja not_active Expired - Fee Related
- 2008-12-01 CA CA2706610A patent/CA2706610A1/en not_active Abandoned
- 2008-12-01 WO PCT/US2008/085100 patent/WO2009073592A2/en not_active Ceased
- 2008-12-01 EP EP13179255.8A patent/EP2662354A2/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| CN101939294A (zh) | 2011-01-05 |
| JP2011505421A (ja) | 2011-02-24 |
| US20090143608A1 (en) | 2009-06-04 |
| WO2009073592A2 (en) | 2009-06-11 |
| EP2215056A2 (en) | 2010-08-11 |
| AU2008334034A1 (en) | 2009-06-11 |
| KR20100101126A (ko) | 2010-09-16 |
| WO2009073592A3 (en) | 2009-07-30 |
| CA2706610A1 (en) | 2009-06-11 |
| JP5497659B2 (ja) | 2014-05-21 |
| EP2215056B1 (en) | 2013-10-30 |
| NZ585414A (en) | 2011-09-30 |
| US8153846B2 (en) | 2012-04-10 |
| EP2662354A2 (en) | 2013-11-13 |
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Legal Events
| Date | Code | Title | Description |
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| FGA | Letters patent sealed or granted (standard patent) | ||
| MK14 | Patent ceased section 143(a) (annual fees not paid) or expired |