TR2022001274T2 - FLUENSULPHONE PREPARATION METHOD - Google Patents
FLUENSULPHONE PREPARATION METHODInfo
- Publication number
- TR2022001274T2 TR2022001274T2 TR2022/001274 TR2022001274T2 TR 2022001274 T2 TR2022001274 T2 TR 2022001274T2 TR 2022/001274 TR2022/001274 TR 2022/001274 TR 2022001274 T2 TR2022001274 T2 TR 2022001274T2
- Authority
- TR
- Turkey
- Prior art keywords
- catalyst
- oxide
- formula
- aqueous phase
- acidic aqueous
- Prior art date
Links
- 238000002360 preparation method Methods 0.000 title claims description 18
- 238000000034 method Methods 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 12
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 12
- 239000011541 reaction mixture Substances 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 30
- 230000002378 acidificating effect Effects 0.000 claims description 27
- 239000008346 aqueous phase Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 15
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 12
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 12
- 125000000623 heterocyclic group Chemical group 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 claims description 6
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 claims description 6
- YGNGABUJMXJPIJ-UHFFFAOYSA-N thiatriazole Chemical compound C1=NN=NS1 YGNGABUJMXJPIJ-UHFFFAOYSA-N 0.000 claims description 6
- 229930192474 thiophene Natural products 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Chemical group 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Chemical group 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Chemical group 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical group [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical group [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical group [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Chemical group 0.000 claims description 3
- 239000010937 tungsten Chemical group 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical group [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 2
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 claims description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910003449 rhenium oxide Inorganic materials 0.000 claims description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical group [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 37
- 230000003647 oxidation Effects 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 150000003457 sulfones Chemical class 0.000 abstract description 6
- 230000001590 oxidative effect Effects 0.000 description 31
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 19
- 239000012071 phase Substances 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 125000001174 sulfone group Chemical group 0.000 description 4
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 125000006416 CBr Chemical group BrC* 0.000 description 3
- 125000006414 CCl Chemical group ClC* 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910020350 Na2WO4 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- -1 thiazole-2-yl Chemical group 0.000 description 3
- LULAYUGMBFYYEX-UHFFFAOYSA-N 3-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 2
- 125000006415 CF Chemical group FC* 0.000 description 2
- 125000006417 CH Chemical group [H]C* 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000002051 biphasic effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- USSBDBZGEDUBHE-UHFFFAOYSA-L magnesium;2-oxidooxycarbonylbenzoate Chemical compound [Mg+2].[O-]OC(=O)C1=CC=CC=C1C([O-])=O USSBDBZGEDUBHE-UHFFFAOYSA-L 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229960001922 sodium perborate Drugs 0.000 description 2
- 229940045872 sodium percarbonate Drugs 0.000 description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- SCVJRXQHFJXZFZ-KVQBGUIXSA-N 2-amino-9-[(2r,4s,5r)-4-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-3h-purine-6-thione Chemical class C1=2NC(N)=NC(=S)C=2N=CN1[C@H]1C[C@H](O)[C@@H](CO)O1 SCVJRXQHFJXZFZ-KVQBGUIXSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- UPTYCYWTFGTCCG-UHFFFAOYSA-N 5-(1-piperazinylsulfonyl)isoquinoline Chemical compound C=1C=CC2=CN=CC=C2C=1S(=O)(=O)N1CCNCC1 UPTYCYWTFGTCCG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 241000244206 Nematoda Species 0.000 description 1
- 239000012425 OXONE® Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000011575 calcium Chemical group 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Chemical group 0.000 description 1
- 239000011777 magnesium Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000007248 oxidative elimination reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001706 oxygenating effect Effects 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000011591 potassium Chemical group 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Chemical group 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000003375 sulfoxide group Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
Abstract
Bu buluş, 5-kloro-2-((3,4,4-triflorobut-3-en-1-il)tio)-1?3,3?2-tiyazol ve analoglarının, bir oksitleyici ve metal oksit bazlı bir katalizör kullanarak, karşılık gelen sülfon ile oksidasyonu için bir yönteme yöneliktir.This invention includes 5-chloro-2-((3,4,4-trifluorobut-3-en-1-yl)thio)-1?3,3?2-thiazole and its analogs as an oxidizer and a metal oxide-based catalyst. Towards a method for oxidation with the corresponding sulfone using
Description
TARIFNAME FLUENSULFON HAZIRLAMA YONTEMI TEKNIK ALAN gelen analoglarina karsilik gelen, metal oksit bazli kataliz'orler ve bir oksitleyici kullanarak oksidasyonu için bir yöntem ile ilgilidir. DESCRIPTION FLUENSULFON PREPARATION METHOD TECHNICAL FIELD using metal oxide-based catalysts and an oxidizer corresponding to the corresponding analogues It relates to a method for oxidation.
BU LUSUN ALT YAPISI bahçe ürünlerinde bir dizi bitki paraziti nematoduna karsi etkili bir nematisittir. Sentezinin bir 3-klorobenzoik asit veya hidrojen peroksit gibi peroksijen reaktifleri ile oksidasyonunu tarif 60°C'de asetik asit içinde 3 esdeger H202 ile reaksiyonun %76 verimle Fluensülfon verdigi Sülfürün, aktif oksidan olarak potasyum peroksimonosülfat ile üçlü bir tuz olan Oxone veya Caroat ile oksidasyonu,2KH805-KHSO4-K2804 ile iyilestirilmis verimler rapor edilmistir (US olusumuna karsi reaksiyonda önemli miktarda çevreye zararli sülfat tuzlari eklenir ve olusturulur. oksidasyonunun önemli ölçüde daha düsük bir verime yol açmasidir. Bu nedenle, sülfoksitin sülfona daha fazla oksidasyonu, yalnizca kademeli ve yavas bir sekilde gerçeklesir ve daha yüksek sicakliklar ve daha uzun reaksiyon süreleri gerektirir. Daha da sorunlu olan, sülfon bir kez olustugunda, istenmeyen yan ürünler olarak 3-((5-klor0-1A3,3i\2-tiazoI-2- il)sülfonil)propanoik asit ve HF'yi vererek florlu çift bagin oksidatif bölünmesi yoluyla daha da reaksiyona girmesidir. Bu reaksiyonun, çogunlukla sülfonun çift bagina H202'nin katalitik olmayan nükleofilik saldirisinin bir sonucu oldugu varsayilmistir; bu, flor ikame edicilerinin ve komsu sülfon grubunun varligindan dolayi çok elektrofiliktir. Böylece, sülfonun H202 ile herhangi bir katalizör olmadan da reaksiyona sokulmasi 'üzerine, çift bagin bölünmesine bagli istenmeyen bir yan reaksiyon, reaktif oksijenleyici perasitlerin yerinde olusturuldugu formik asit veya asetik asit mevcudiyetinde veya yaygin olarak kullanilan molibdat veya tungstat katalizörlerinin mevcudiyetinde H202 ile de meydana gelir. analoglarina, ak'oz bir bifazik reaksiyon ortaminda oksitleyici ajan/oksijen donör'u olarak aköz H202 kullanilarak seçici oksidasyonunu saglar. INFRASTRUCTURE OF THIS INSTRUCTION It is an effective nematicide against a number of plant parasitic nematodes in garden crops. A synthesis of Describe its oxidation with peroxygen reagents such as 3-chlorobenzoic acid or hydrogen peroxide Reaction with 3 equivalents of H2O2 in acetic acid at 60°C yielded Fluenesulfone in 76% yield. Oxone or Oxone, a ternary salt of sulfur with potassium peroxymonosulfate as the active oxidant. Oxidation with caroate and improved yields with 2KH805-KHSO4-K2804 have been reported (US In the reaction against its formation, a significant amount of environmentally harmful sulphate salts are added and is created. oxidation leads to a significantly lower yield. Therefore, sulfoxide Further oxidation to the sulfone occurs only gradually and slowly and is more Requires higher temperatures and longer reaction times. Even more problematic, a sulfone once formed, 3-((5-chloro0-1A3,3i\2-thiazoI-2-) as undesirable byproducts further via oxidative cleavage of the fluorinated double bond yielding yl)sulfonyl)propanoic acid and HF. is to react. This reaction is mostly caused by the catalytic reaction of H2O2 to the double bond of the sulphone. assumed to be a result of non-nucleophilic attack; this means that fluorine substituents and It is very electrophilic due to the presence of the adjacent sulfone group. Thus, the sulphone is combined with H2O2. upon reaction without any catalyst, due to the cleavage of the double bond an undesirable side reaction is formic acid, where reactive oxygenating peracids are formed in situ or in the presence of acetic acid or the commonly used molybdate or tungstate It also occurs with H2O2 in the presence of catalysts. aqueous analogues as oxidizing agent/oxygen donor in an aqueous biphasic reaction environment. It provides selective oxidation using H2O2.
Aköz bir iki fazli reaksiyon ortaminin kullanilmasindaki özel bir avantaj, katalizörü içeren su fazini ve istenen 'ürünü içeren organik fazi ayirmanin kolay olmasidir. Bu sekilde katalizbr oldukça basit bir sekilde geri kazanilabilir ve yeniden kullanilabilir. A particular advantage in using an aqueous two-phase reaction medium is the water containing the catalyst. It is easy to separate the organic phase containing the phase and the desired product. In this way it catalyzes It can be recovered and reused quite simply.
BULUSUN KISA AÇIKLAMASI Bir düzenlemede bu bulus, Formülün (I) yapisi ile temsil edilen bir bilesigin hazirlanmasi için bir yöntem saglar: burada R, tiyofen, tiyazol, izotiyazol, tiadiazol ve tiatriazolden seçilen heterosiklik halkadir, burada heterosiklik halka istege bagli olarak halojenlenir; ve n, 1 ile 6 arasinda bir tamsayidir ve bir reaksiyon karisiminda Form'L'iI'i'Jn (la) yapisi ile temsil edilen bir bilesigin temas ettirilmesi adimini içerir: R-S-(CH2)n%\ F burada R ve n, bir katalizbr varliginda asidik bir aköz fazda H202 ile yukarida tanimlandigi varliginda asidik aköz fazda H202 ile temas ettirilmesi için bir yöntem saglar. BRIEF DESCRIPTION OF THE INVENTION In one embodiment, this invention is for the preparation of a compound represented by the structure of Formula (I). provides a method: where R is the heterocyclic ring selected from thiophene, thiazole, isothiazole, thiadiazole and thiatriazole, wherein the heterocyclic ring is optionally halogenated; and n is an integer between 1 and 6 and contacting a compound represented by the structure of Form'L'iI'i'Jn (Ia) in a reaction mixture It includes the step: R-S-(CH2)n%\ F where R and n are defined above by H2O2 in an acidic aqueous phase in the presence of a catalyst It provides a method for contacting H2O2 in the acidic aqueous phase in the presence of
Bir düzenlemede bu bulus, Formülün (I) yapisi ile temsil edilen bir bilesigin hazirlanmasi için bir yöntem saglar: R-s-(CH2)n%F burada R, tiyofen, tiyazol, izotiyazol, tiadiazol ve tiatriazolden seçilen heterosiklik halkadir, burada heterosiklik halka istege bagli olarak halojenlenir; ve n, 1 ile 6 arasinda bir tamsayidir ve bir reaksiyon karisiminda Formül (Ia)'nin yapisi ile temsil edilen bir bilesigin temas ettirilmesi adimini içerir: R-S-(CH2)n4\/J\F burada R ve n, bir katalizör mevcudiyetinde asidik bir aköz fazda bir peroksijen oksidan ile varliginda asidik akbz fazda peroksijen oksitleyici ile temas ettirilmesi için bir yöntem saglar. In one embodiment, this invention is for the preparation of a compound represented by the structure of Formula (I). provides a method: R-s-(CH2)n%F where R is the heterocyclic ring selected from thiophene, thiazole, isothiazole, thiadiazole and thiatriazole, wherein the heterocyclic ring is optionally halogenated; and n is an integer between 1 and 6 and contacting a compound represented by the structure of Formula (Ia) in a reaction mixture It includes the step: R-S-(CH2)n4\/J\F where R and n are combined with a peroxygen oxidant in an acidic aqueous phase in the presence of a catalyst. It provides a method of contacting peroxygen oxidizer in the presence of acidic aqueous phase.
SEKILLERIN KISA AÇIKLAMASI Bulus olarak kabul edilen konu, spesifikasyonun sonuç bölümünde özellikle belirtilmis ve açikça talep edilmistir. Bununla birlikte, bulus, amaçlari, özellikleri ve avantajlari ile birlikte hem organizasyon hem de çalisma yöntemi açisindan, en iyi sekilde, asagidaki ayrintili açiklamaya atifta bulunularak ve asagidaki çizimlerle birlikte okundugunda anlasilabilir: bulusun bir islemini sunar; bu bulus 3-((5-kl0ro-1A3,3)\2-tiyazol-2-il)sülfonil)propanoik asidin yan ürününün olusumunu engeller. BRIEF DESCRIPTION OF THE FIGURES The subject matter accepted as an invention is specifically stated in the conclusion section of the specification and has been explicitly requested. However, the invention, along with its purposes, features and advantages, is both In terms of both organization and working method, it is best to refer to the detailed description below. It can be understood by referring to it and reading it with the following illustrations: presents a process of the invention; This invention is based on the side effects of 3-((5-chloro-1A3,3)\2-thiazol-2-yl)sulfonyl)propanoic acid. It prevents the formation of the product.
Gösterimin basitligi ve netligi için sekillerde gösterilen ögelerin mutlaka ölçege göre çizilmedigi takdir edilecektir. Ornegin, bazi elemanlarin boyutlari, açiklik için diger elemanlara göre abartili olabilir. Ayrica, uygun görüldügünde, karsilik gelen veya benzer elemanlari belirtmek için sekiller arasinda referans numaralari tekrar edilebilir. For simplicity and clarity of illustration, the elements shown in the figures are not necessarily drawn to scale. It will be appreciated. For example, the dimensions of some elements are exaggerated relative to other elements for clarity. it could be. Also, where appropriate, to indicate corresponding or similar elements Reference numbers may be repeated between figures.
BU LUSUN AYRINTILI AÇIKLAMASI Asagidaki ayrintili açiklamada, bulusun tam olarak anlasilmasini saglamak için çok sayida ayrintilar olmadan da uygulanabilecegi anlasilacaktir. Diger durumlarda, iyi bilinen yöntemler, prosedürler ve bilesenler, mevcut bulusu karartmamak için ayrintili olarak tarif edilmemistir. gelen analoglarina, metal oksit bazli katalizbrler ve bir oksitleyici kullanarak oksidasyonu için bir yöntem ile ilgilidir. Baska bir düzenlemede oksidan, bir peroksijen oksidandir. Baska bir Bir düzenlemede, bu bulusun yöntemi bir oksidandan yararlanir. Baska bir düzenlemede oksidan, suda çözünür bir peroksijen oksidandir. Suda çözünür bir peroksijen oksidanin sinirlayici olmayan örnekleri arasinda HzOz, magnezyum monoperoksiftalat, sodyum perborat, sodyum perkarbonat, üre hidrojen peroksit (UHP) veya bunlarin herhangi bir kombinasyonu yer alir. Baska bir düzenlemede peroksijen oksidan, HzOz'CIIF. Baska bir düzenlemede peroksijen oksidan, magnezyum monoperoksiftalattir. Baska bir düzenlemede peroksijen oksidan, sodyum perborattir. Baska bir düzenlemede peroksijen oksidan, sodyum perkarbonattir. Baska bir düzenlemede peroksijen oksidan, üre hidrojen peroksittir (UHP). DETAILED DESCRIPTION OF THIS INSTRUCTION In the detailed description below, there are many details to ensure a full understanding of the invention. It will be understood that it can be applied without any details. In other cases, well-known methods, The procedures and components are not described in detail so as not to obscure the present invention. For the oxidation of the corresponding analogues, metal oxide-based catalysts and using an oxidizer It is about a method. In another embodiment, the oxidant is a peroxygen oxidant. Another In one embodiment, the method of the present invention utilizes an oxidant. In another arrangement The oxidant is a water-soluble peroxygen oxidant. A water-soluble peroxygen oxidant Non-limiting examples include HzO2, magnesium monoperoxyphthalate, sodium perborate, sodium percarbonate, urea hydrogen peroxide (UHP), or any combination thereof takes place. In another embodiment, the peroxygen oxidant is HzO2CIIF. In another arrangement The peroxygen oxidant is magnesium monoperoxyphthalate. In another embodiment, peroxygen The oxidant is sodium perborate. In another embodiment, the peroxygen oxidant is sodium percarbonate. In another embodiment, the peroxygen oxidant is urea hydrogen peroxide (UHP).
Baska bir düzenlemede peroksijen oksidan, asidik reaksiyon kosullari altinda hidrojen peroksit olusturur. In another embodiment, the peroxygen oxidant produces hydrogen peroxide under acidic reaction conditions. creates.
Bir düzenlemede bu bulus, Formülün (I) yapisi ile temsil edilen bir bilesigin hazirlanmasi için bir yöntem saglar: R-s-(CH2›n%\F burada R, tiyofen, tiyazol, izotiyazol, tiadiazol ve tiatriazolden seçilen heterosiklik halkadir, burada heterosiklik halka istege bagli olarak halojenlenir; ve n, 1 ile 6 arasinda bir tamsayidir ve bir reaksiyon karisiminda Formülün (la) yapisi ile temsil edilen bir bilesigin temas ettirilmesi adimini içerir: R-S-(CH2)n-%F burada R ve n, bir katalizbr varliginda asidik bir aköz fazda HzOz ile yukarida tanimlandigi Bir düzenlemede bu bulus, Formülün (l) yapisi ile temsil edilen bir bilesigin hazirlanmasi için bir yöntem saglar: R-s-(CH2›n%F burada R, tiyofen, tiyazol, izotiyazol, tiadiazol ve tiatriazolden seçilen heterosiklik halkadir, burada heterosiklik halka istege bagli olarak halojenlenir; ve n, 1 ile 6 arasinda bir tamsayidir ve bir reaksiyon karisiminda Form'ul'un (la) yapisi ile temsil edilen bir bilesigin temas ettirilmesi adimini içerir: R-S-(CH2)r% F burada R ve n, bir katalizör mevcudiyetinde asidik bir aköz fazda bir peroksijen oksidan ile Bir diger düzenlemede bu bulus, Formul'un (I) yapisi ile temsil edilen bir bilesigin hazirlanmasi için bir yöntem saglar: X3'S H X2: %s (0 zin burada Xl-Xß'ün her biri bagimsiz olarak asagidakilerden seçilir: C-H, C-F, C-Cl, C-Br, C-l ve N; ve n, 1 ile 6 arasinda bir tamsayidir; (Ila) veya (llla) yapisi ile temsil edilen bir bilesigin bir reaksiyon karisiminda temas ettirilmesi adimini içerir: (ile) veya (llla) bir katalizör varliginda asidik bir akbz tazda H202 ile; burada X1-X3 ve n yukarida tanimlandigi Baska bir düzenlemede bu bulus, Formüllerin (II) veya (III) yapisi ile temsil edilen bir bilesigin hazirlanmasi için bir yöntem saglar: Bir diger düzenlemede bu bulus, Formülün (I) yapisi ile temsil edilen bir bilesigin hazirlanmasi için bir yöntem saglar: X3/s ii *X1 0 F burada X1-X3'ün her biri bagimsiz olarak asagidakilerden seçilir: C-H, C-F, C-Cl, C-Br, C-l ve N; ve n, 1 ile 6 arasinda bir tamsayidir; (Ila) veya (Illa) yapisi ile temsil edilen bir bilesigin bir reaksiyon karisiminda temas ettirilmesi adimini içerir: (lla) veya (illa) bir katalizörün mevcudiyetinde asidik bir aköz fazda bir peroksijen oksidan ile; burada Xl-X3 ve n yukarida tanimlandigi gibidir. In one embodiment, this invention is for the preparation of a compound represented by the structure of Formula (I). provides a method: R-s-(CH2›n%\F where R is the heterocyclic ring selected from thiophene, thiazole, isothiazole, thiadiazole and thiatriazole, wherein the heterocyclic ring is optionally halogenated; and n is an integer between 1 and 6 and contacting a compound represented by the structure of Formula (Ia) in a reaction mixture It includes the step: R-S-(CH2)n-%F where R and n are defined above with HzO2 in an acidic aqueous phase in the presence of a catalyst In one embodiment, this invention is for the preparation of a compound represented by the structure of Formula (1). provides a method: R-s-(CH2›n%F where R is the heterocyclic ring selected from thiophene, thiazole, isothiazole, thiadiazole and thiatriazole, wherein the heterocyclic ring is optionally halogenated; and n is an integer between 1 and 6 and contacting a compound represented by the structure of Formula (Ia) in a reaction mixture It includes the step: R-S-(CH2)r%F where R and n are combined with a peroxygen oxidant in an acidic aqueous phase in the presence of a catalyst. In another embodiment, this invention involves the preparation of a compound represented by the structure of Formula (I). Provides a method for: X3'S H X2: %s (0 z where Xl-Xß is each independently selected from: C-H, C-F, C-Cl, C-Br, C-l and N; and n is an integer between 1 and 6; A compound represented by the structure (Ila) or (lla) It includes the step of contacting the reaction mixture: (with) or (llla) with H2O2 in an acidic liquid in the presence of a catalyst; where X1-X3 and n are defined above In another embodiment, this invention relates to the use of a compound represented by the structure of Formulas (II) or (III). Provides a method for preparing: In another embodiment, this invention involves the preparation of a compound represented by the structure of Formula (I). Provides a method for: X3/s ii *X1 0F where X1-X3 are each independently selected from: C-H, C-F, C-Cl, C-Br, C-1 and N; and n is an integer between 1 and 6; A compound represented by the structure (Ila) or (Ila) It includes the step of contacting the reaction mixture: (lla) or (illa) with a peroxygen oxidant in an acidic aqueous phase in the presence of a catalyst; where Xl-X3 and n is as defined above.
Baska bir düzenlemede, X3 asagidakilerden seçilir: C-H, C-F, C-Cl, C-Br ve C-l ve C-l; ve X1 ve X2'nin her biri bagimsiz olarak C-H ve N'den seçilir. oksit bazli katalizörler ve bir oksitleyici kullanarak oksidasyonu için bir yöntem ile ilgilidir. Baska bir düzenlemede oksidan, bir peroksijen oksidandir. Baska bir düzenlemede oksidan, H202'dir. tiyazol veya bir kataliz'or varliginda asidik bir ak'oz fazda akbz H202 ile Formüllerin (la, IIa veya hazirlanmasi için bir yönteme yöneliktir. Baska bir düzenlemede mevcut bulus, 5-kloro-2- ((3,4,4-triflorobut-3-en-1-iI)tio)-1A3,3)\2-tiyazolün karisiminin bir katalizör varliginda asidik aköz fazda HzOz ile temas ettirilmesi için bir yöntem ile ilgilidir. tiyazol veya bir katalizör varliginda asidik bir aköz fazda suda çözünür bir peroksijen oksidan ile Formüllerin (la, lla veya Ila) karsilik gelen analoglarini reaksiyon karisimi içinde temas ettirme adimini içeren hazirlanmasi için bir yönteme ybneliktir. Baska bir düzenlemede mevcut kataliz'or varliginda asidik aköz fazda suda çözünür bir peroksijen oksidan ile temas ettirilmesi tiyazol veya bunun analoglarinin hazirlanmasina yönelik yontem, bir katalizör kullanir. Baska bir düzenlemede katalizör, en az bir metal oksit veya metal oksit tuzudur. Baska bir düzenlemede metal oksit sunlari içerir: tungsten oksit, molibden oksit, vanadyum oksit, niyobyum oksit, tantal oksit, renyum oksit, titanyum oksit, zirkonyum oksit, krom oksit, hafniyum oksit veya bunlarin kombinasyonudur. In another embodiment, X3 is selected from: C-H, C-F, C-Cl, C-Br and C-1 and C-1; and X1 and X2 is each independently selected from C-H and N. It relates to a method for oxidation using oxide-based catalysts and an oxidizer. Another In one embodiment, the oxidant is a peroxygen oxidant. In another embodiment, the oxidant is H 2 O 2 . Formulas (Ia, IIa or It is intended for a method of preparation. In another embodiment, the present invention contains 5-chloro-2- The mixture of ((3,4,4-trifluorobut-3-ene-1-yl)thio)-1A3,3)\2-thiazole in the presence of a catalyst is acidic aqueous. It relates to a method for contacting the phase with HzOz. a water-soluble peroxygen oxidant in an acidic aqueous phase in the presence of thiazole or a catalyst contact the corresponding analogues of the formulas (Ia, Ila or Ila) in the reaction mixture. It is directed to a method for its preparation that includes the step of Available in another arrangement contacting a water-soluble peroxygen oxidant in the acidic aqueous phase in the presence of a catalyst The method for preparing the thiazole or its analogues uses a catalyst. Another In one embodiment, the catalyst is at least one metal oxide or metal oxide salt. Another in the embodiment the metal oxide includes: tungsten oxide, molybdenum oxide, vanadium oxide, niobium oxide, tantalum oxide, rhenium oxide, titanium oxide, zirconium oxide, chromium oxide, hafnium oxide or a combination thereof.
Baska bir düzenlemede, katalizör MqM'Ox formülüne sahip en az bir metal oksit tuzudur, M, hidrojen, bir alkali veya toprak alkali metaldir; M' titanyum, vanadyum, krom, zirkonyum, niyobyum, molibden, hafniyum, tantal, renyum veya tungsten; x, 2 - 6 arasinda bir tamsayidir; ve q 1 - 4 arasinda bir tamsayidir. In another embodiment, the catalyst is at least one metal oxide salt of the formula MqM'Ox, M is hydrogen, an alkali or alkaline earth metal; M' titanium, vanadium, chromium, zirconium, niobium, molybdenum, hafnium, tantalum, rhenium or tungsten; x is an integer from 2 to 6; And q is an integer between 1 and 4.
MqM'Ox formülünün baska bir düzenlemesinde M, hidrojen, alkali veya toprak alkali metaldir. In another embodiment of the formula MqM'Ox, M is hydrogen, alkali or alkaline earth metal.
Baska bir düzenlemede M, hidrojen, sodyum, potasyum, kalsiyum veya magnezyumdur. In another embodiment, M is hydrogen, sodium, potassium, calcium or magnesium.
Baska bir düzenlemede MqM'OX formülüne sahip M' titanyum, vanadyum, krom, zirkonyum, niyobyum, molibden, hafniyum, tantal, renyum veya tungstendir. MqM'OX formülünün baska bir düzenlemesinde x, 2-6 arasinda bir tamsayidir. Baska bir düzenlemede x, 2, 3, 4, 5 veya 6'dir. In another embodiment, M' having the formula MqM'OX is titanium, vanadium, chromium, zirconium, niobium, molybdenum, hafnium, tantalum, rhenium or tungsten. Another version of the MqM'OX formula In this embodiment, x is an integer between 2 and 6. In another embodiment, x is 2, 3, 4, 5 or 6.
MqM'Ox formülünün baska bir düzenlemesinde q, 1-4 arasinda bir tamsayidir. Baska bir düzenlemede q, 1, 2, 3, veya 4'tür. In another embodiment of the formula MqM'Ox, q is an integer between 1 and 4. Another In one embodiment, q is 1, 2, 3, or 4.
Baska bir düzenlemede en az bir metal oksit tuzu, sodyum vanadat, sodyum molibdat veya sodyum tungstat veya bunlarin kombinasyonudur. Baska bir düzenlemede metal oksit tuzu, sodyum tungstattir. In another embodiment, at least one metal oxide salt is sodium vanadate, sodium molybdate, or sodium tungstate or a combination thereof. In another embodiment, the metal oxide salt is sodium tungstate.
Baska bir düzenlemede, katalizör hidratlanir. In another embodiment, the catalyst is hydrated.
Baska bir düzenlemede, reaksiyon karisimindaki katalizör konsantrasyonu, baslangiç veya IIIa) analoglarina göre %001-20 mol arasindadir. Baska bir düzenlemede, reaksiyon tiyazol veya Formüllerin (la, Ila veya IIIa) analoglarina göre %1-10 mol arasindadir. Baska bir düzenlemede, reaksiyon karisimindaki katalizör konsantrasyonu, 5-kloro-2-((3,4,4-triflorobut- 3-en-1-il)ti0)- analoglarina göre %1-5 mol arasindadir. Baska bir düzenlemede, reaksiyon karisimindaki katalizör konsantrasyonu, 5- analoglarina göre %0.01-1 mol arasindadir. Baska bir düzenlemede, reaksiyon karisimindaki Formüllerin (la, Ila veya Illa) analoglarina göre %0.01-2 mol arasindadir. Baska bir düzenlemede, reaksiyon karisimindaki katalizör konsantrasyonu, 5-klor0-2-((3,4,4-trifl0robut- arasindadir. Baska bir düzenlemede, reaksiyon karisimindaki katalizör konsantrasyonu, 5- analoglarina göre %0.01-4 mol arasindadir. Baska bir düzenlemede, reaksiyon karisimindaki Formüllerin (la, IIa veya Illa) analoglarina göre %0.01-5 mol arasindadir. Baska bir düzenlemede, reaksiyon karisimindaki kataliz'or konsantrasyonu, 5-kloro-2-((3,4,4-trifl0robut- arasindadir. Baska bir düzenlemede, reaksiyon karisimindaki kataliz'or konsantrasyonu, 5- analoglarina göre %0.01-10 mol arasindadir. In another embodiment, the catalyst concentration in the reaction mixture is or IIIa) is between 001-20 mol% compared to its analogues. In another embodiment, the reaction It is between 1-10 mol% depending on the thiazole or analogues of Formulas (Ia, IIa or IIIa). Another In one embodiment, the catalyst concentration in the reaction mixture is 5-chloro-2-((3,4,4-trifluorobut- 1-5 mol% relative to 3-en-1-yl)thiO)- analogues is between. In another embodiment, the catalyst concentration in the reaction mixture is 5- It is between 0.01-1 mol% compared to its analogues. In another embodiment, the reaction mixture It is between 0.01-2 mol% depending on the analogues of the formulas (Ia, Ila or Ila). Another In the embodiment, the catalyst concentration in the reaction mixture is 5-chloro-2-((3,4,4-trifluorobut- is between. In another embodiment, the catalyst concentration in the reaction mixture is 5- It is between 0.01-4 mol% compared to its analogues. In another embodiment, the reaction mixture It is between 0.01-5 mol% depending on the analogues of the formulas (Ia, IIa or IIIa). Another In the embodiment, the catalyst concentration in the reaction mixture is 5-chloro-2-((3,4,4-trifluorobut- is between. In another embodiment, the catalyst concentration in the reaction mixture is 5- It is between 0.01-10 mol% compared to its analogues.
Baska bir düzenlemede, katalizör geri dönüstürülür ve yeniden kullanilir. Baska bir düzenlemede, katalizör yeniden kullanilir. Baska bir düzenlemede, katalizör izole edilmez ve reaksiyon karisimi içinde yeniden kullanilir. In another embodiment, the catalyst is recycled and reused. Another In the embodiment, the catalyst is reused. In another embodiment, the catalyst is not isolated and is reused in the reaction mixture.
Formüllerin (I, II veya III) analoglarinin hazirlanmasina yönelik yöntem, asidik ak'oz bir solüsyondan faydalanir. Asidik aköz çözelti kullaniminin hidrojen peroksit oksidanin, `Özellikle bitisik bir sülfon veya sülfoksit gruplari oldugunda ve böylece H202 gibi bir peroksijen oksidan asit yan ürününün veya bunun analoglarinin olusumunu engellediginde (örnegin Formüller (Ib- daha az reaktif hale getirdigi bulunmustur. Baska bir düzenlemede Formüller (I)-(III) ile temsil edilen bilesigin hazirlanmasina yönelik yöntem: (i) ; (Il) veya Formüller (lb)-(Illb) ile temsil edilen karsilik gelen yan ürün bilesiklerinin agirlikça %15'inden daha azini verir: R-s-(CHzin-COOH X3'S ii ii / S-(CH2)n-COOH x2`_ 1 Il X2: fî (C zin burada R, X1-X3 ve n yukarida tanimlandigi gibidir. Baska bir düzenlemede Formüllerin (lb)- (lllb) bilesigi için verim, agirlikça %0-2 arasindadir. Baska bir düzenlemede Formüllerin (lb)- (Illb) bilesigi için verim, agirlikça %2-5 arasindadir. Baska bir düzenlemede Formüllerin (lb)- (Illb) bilesigi için verim, agirlikça %5-10 arasindadir. Baska bir düzenlemede Formüllerin (lb)- (Illb) bilesigi için verim, agirlikça %10-15 arasindadir. Baska bir düzenlemede 5-kl0r0-2- tiyazoI-2-iI)sülf0nil)pr0pan0ik asit yan ürününün agirlikça %2'sinden daha azini verir. The method for the preparation of analogues of the formulas (I, II or III) is based on an acidic aqueous solution. uses the solution. The use of acidic aqueous solution may cause oxidation of hydrogen peroxide, `Especially when there is an adjacent sulfone or sulfoxide groups and thus a peroxygen oxidant such as H2O2 when it prevents the formation of the acid by-product or its analogues (e.g. Formulas (Ib- It has been found that it makes it less reactive. In another embodiment, it is represented by Formulas (I)-(III). Method for preparing the compound: (I) ; (II) or Less than 15 wt% of the corresponding by-product compounds represented by formulas (lb)-(IIIb) gives less: R-s-(CHzine-COOH X3'S ii ii / S-(CH2)n-COOH x2`_ 1 Year X2: fi (C zin where R, X1-X3 and n are as defined above. In another embodiment, Formulas (lb)- The yield for compound (llb) is between 0-2% by weight. In another embodiment, Formulas (lb)- The yield for compound (IIIb) is between 2-5% by weight. In another embodiment, Formulas (lb)- The yield for compound (IIIb) is between 5-10% by weight. In another embodiment, Formulas (lb)- The yield for compound (IIIb) is between 10-15% by weight. In another embodiment 5-kl0r0-2- It yields less than 2% by weight of the thiazole-2-yl)sulfonyl)propanic acid byproduct.
Formüllerin (I-III) analoglarinin hazirlanmasina yönelik yöntem, asidik akbz bir solüsyondan faydalanir. Baska bir düzenlemede asidik aköz faz, HCI, HBr, HzSO4, H3P04, Me803H, CFsSOsH veya bunlarin kombinasyonunu içerir. Baska bir düzenlemede asidik akoz faz, HzSO4içerir. Baska bir düzenlemede asidik aköz fazdaki asidin konsantrasyonu 0.5-8 IVi arasindadir. Baska bir düzenlemede asidik ak'oz fazdaki asit konsantrasyonu 1-6 M arasindadir. Baska bir düzenlemede asidik aköz fazdaki asit konsantrasyonu 2-5 M arasindadir. tiyazol veya bunun analoglarinin hazirlanmasina yönelik yöntem, bir oksitleyici kullanir. Baska bir düzenlemede oksidan, bir peroksijen oksidandir. Baska bir düzenlemede oksidan, H202'dir. The method for the preparation of analogues of formulas (I-III) from an acidic aqueous solution benefits. In another embodiment, the acidic aqueous phase consists of HCl, HBr, HzSO4, H3PO4, Me8O3H, Contains CFsSOsH or combination thereof. In another embodiment, the acidic aqueous phase, Contains HzSO4. In another embodiment, the concentration of acid in the acidic aqueous phase is 0.5-8 Ivi is between. In another embodiment, the acid concentration in the acidic aqueous phase is 1-6 M is between. In another embodiment, the acid concentration in the acidic aqueous phase is 2-5 M is between. The method for preparing the thiazole or its analogs uses an oxidant. Another In one embodiment, the oxidant is a peroxygen oxidant. In another embodiment, the oxidant is H 2 O 2 .
Formüllerin (la-lila) analoglarina göre 2-10 mol oksidanin esdegeri eklenir. Baska bir mol oksidanin esdegeri eklenir. Baska bir düzenlemede, 5-kl0ro-2-((3,4,4-triflorobut-3-en-1- il)tio)-1)\3,3)\2-tiyazol veya Formüllerin (la-lila) analoglarina göre 12-35 mol oksidanin esdegeri eklenir. Baska bir düzenlemede, kullanilan ak'oz hidrojen peroksidin konsantrasyonu, hacimce düzenlemede, kullanilan aköz hidrojen peroksidin konsantrasyonu, agirlik bakimindan %20 ila tiyazol veya bunun analoglarinin hazirlanmasina yönelik reaksiyon karisimi, bifaziktir. Baska bir düzenlemede iki fazli, bir oksidan, bir kataliz'or ve bir asit içeren aköz bir faza ve sülfid substrati, sülfon ürünü ve istege bagli olarak suyla karismayan bir organik solvent içeren bir organik faza karsilik gelir. Baska bir düzenlemede iki fazli, bir oksidan, bir katalizbr ve bir asit içeren aköz bir fazi ve su ile karismayan bir organik solvent olmaksizin sülfid substrati ve sülfon ürününü içeren bir organik fazi ifade eder. The equivalent of 2-10 moles of oxidant is added according to the analogs of the formulas (la-lila). Another equivalent mole of oxidant is added. In another embodiment, 5-chloro-2-((3,4,4-trifluorobut-3-ene-1- Equivalent of 12-35 moles of oxidant according to yl)thio)-1)\3,3)\2-thiazole or analogs of Formulas (1a-lila) is added. In another embodiment, the concentration of aqueous hydrogen peroxide used is In one embodiment, the concentration of aqueous hydrogen peroxide used is 20 to 20% by weight. The reaction mixture for the preparation of the thiazole or its analogues is biphasic. Another In one embodiment, the two phases have an aqueous phase containing an oxidant, a catalyst and an acid, and a sulfide phase. a substrate, sulfone product, and optionally a water-immiscible organic solvent. corresponds to the organic phase. In another embodiment, the two-phase consists of an oxidant, a catalyst and an acid. sulfide substrate and sulfone without a water-immiscible organic solvent and an aqueous phase containing It refers to an organic phase containing the product.
Formüllerin (I, II veya III) analoglarinin hazirlanmasina yönelik yöntem, tek fazli bir reaksiyondur. The method for the preparation of analogues of the formulas (I, II or III) is a single-phase is the reaction.
Formüllerin (I-III) analoglarinin hazirlanmasi için reaksiyon karisimi su içerir ve suyla karismayan bir organik çözücü içermez. Baska bir düzenlemede reaksiyon karisimi, su ve su ile karismayan organik çözücü içerir. Suyla karismayan organik çözücülerin sinirlayici olmayan 'Örnekleri, heksan, pentan, toluen, metilsikloheksan, klorobenzen, etil asetat ve çesitli eterleri içerir. Baska bir düzenlemede reaksiyon karisimi, su ve suyla karisabilen solvent ve/veya yüzey aktif madde içerir. Suyla karisabilen bir çözücünün sinirlayici olmayan örnekleri, asetonitril, metanol, etanol, aseton, dimetilformamid, dimetilasetamid, n-metil pirolidon veya bunlarin kombinasyonunu içerir. Baska bir düzenlemede reaksiyon karisimi, su ve suyla karismayan organik çözücü vei'veya yüzey aktif madde içerir. The reaction mixture for the preparation of analogues of formulas (I-III) contains water and is It does not contain any immiscible organic solvents. In another embodiment, the reaction mixture is water and water Contains incompatible organic solvent. Limitation of water-immiscible organic solvents Non-'Examples include hexane, pentane, toluene, methylcyclohexane, chlorobenzene, ethyl acetate and miscellaneous Contains ethers. In another embodiment, the reaction mixture consists of water and a water-miscible solvent. and/or contain surfactants. Non-limiting examples of a water-miscible solvent are: acetonitrile, methanol, ethanol, acetone, dimethylformamide, dimethylacetamide, n-methyl pyrrolidone or contains a combination of these. In another embodiment, the reaction mixture is diluted with water and Contains immiscible organic solvent and surfactant.
Bazi düzenlemelerde, yüzey aktif madde poli alkilen glikol, alkoksilatli alkol, alkil sülfat tuzu veya bunlarin herhangi bir kombinasyonunu içerebilir ancak bunlarla sinirli degildir. Bazi düzeneklerde yüzey aktif madde, poli alkilen glikol, alkoksilatli alkol, alkil sülfat tuzu veya bunlarin herhangi bir kombinasyonunu içerir. Yüzey aktif maddelerin sinirlayici olmayan sülfat tuzu (SDS gibi) bulunur. tiyazol veya bunun analoglarinin hazirlanmasina yönelik yöntem, O“C ila 100°C arasinda degisen bir sicaklikta gerçeklestirilir. Baska bir düzenlemede, 20°C ila 40°C arasindaki bir sicakliktadir. Baska bir düzenlemede, 20C ila 50°C arasindaki bir si cakliktadir. Baska bir düzenlemede, 20t ila 60%: arasindaki bir sicaklikt adir. Baska bir düzenlemede, 20“C ila 70°C arasindaki bir sicakliktadir. Baska bir düzenlemede 25% ila 40°C arasindaki bir sicakliktadir. Baska bir düzenlemede 25°C ila 50°C arasindaki bir sic akliktadir. Baska bir düzenlemede 25°C ila BO“C arasindaki bir sicaklikta dir. Baska bir düzenlemede 25°C ila 70°C arasindaki bir sicakliktadir. Baska bir düzenlemede 26°C ila 100°C arasindaki bir si cakliktadir. In some embodiments, the surfactant is poly alkylene glycol, alkoxylated alcohol, alkyl sulfate salt. or any combination thereof, but are not limited to. Some In embodiments, the surfactant is poly alkylene glycol, alkoxylated alcohol, alkyl sulfate salt, or includes any combination of these. Non-limiting properties of surfactants sulfate salt (such as SDS) is present. Method for the preparation of thiazole or its analogues, between 0°C and 100°C It is carried out at a varying temperature. In another embodiment, a temperature between 20°C and 40°C It is in the temperature. In another embodiment, it is at a temperature between 20°C and 50°C. Another In one embodiment, it is a temperature between 20 and 60%. In another embodiment, 20°C to It is at a temperature between 70°C. In another embodiment, a temperature between 25% and 40°C It is in the temperature. In another embodiment, a temperature between 25°C and 50°C is maintained. Another In one embodiment it is at a temperature between 25°C and 10°C. 25°C to 70°C in another embodiment It is at a temperature between. In another embodiment it is at a temperature between 26°C and 100°C.
Baska bir düzenlemede 30“C ila 80“C arasindaki bir sic akliktadir. Baska bir düzenlemede °C ila BO“C arasindaki bir sicakliktadir. Ba ska bir düzenlemede 200 ila 80°C arasinda bir sicaklikta, baska bir düzenlemede 10“(3 ila SO“C arasinda bir sicak Iiktadir. Baska bir düzenlemede, 15°C ila 35“C arasindaki bir sicaklikt adir. Baska bir düzenlemede, en az 15t: sicakliktadir. Baska bir düzenlemede, en az 200 sicakliktadir. Ba ska bir düzenlemede, en az °C sicakliktadir. In another embodiment, a temperature between 30°C and 80°C is maintained. In another arrangement It has a temperature between °C and BO“C. In another embodiment, a temperature between 200 and 80°C in temperature, in another embodiment it is at a temperature between 10°C (3 to 5°C). In another In one embodiment, it is a temperature between 15°C and 35°C. In another embodiment, at least 15t: It is in the temperature. In another embodiment, it is at least 200 degrees. In another embodiment, at least °C temperature.
Formüllerin (I-III) analoglari ile ilgilidir ve bu bulusun prosesi ile hazirlanir. Bir diger veya bunun analoglari, bu bulusun prosesi hazirlanir, 3-((5-kloro-1A3,3i\2-tiazoI-2-il) sülfonil)propanoik asit veya bunun analoglarinin agirlikça %1'den fazla degildir ve Formüller (lb-lllb) ile temsil edilir; baska bir düzenlemede, 3-((5-klor0-1)\3,3i\2- tiyazol-2- il)sülfonil)propan0ik asit veya bunun analoglari agirlikça %2'den azdir ve Formüller (Ib-Illb) ile temsil edilir, burada Formüller (Ib-Illb) yukarida açiklanir. It relates to analogues of formulas (I-III) and is prepared by the process of the present invention. Another or analogs thereof, prepared by the process of the present invention, 3-((5-chloro-1A3,3i\2-thiazolI-2-yl) not more than 1% by weight of sulfonyl)propanoic acid or its analogues and Formulas It is represented by (lb-lllb); In another embodiment, 3-((5-chloro-1)\3,3i\2-thiazole-2- yl)sulfonyl)propanic acid or its analogs is less than 2% by weight and is defined by Formulas (Ib-IIIb). is represented, where Formulas (Ib-IIIb) are explained above.
Asagidaki örnekler, bulusun tercih edilen düzenlemelerini daha tam olarak açiklamak için sunulmustur. Bununla birlikte, hiçbir sekilde bulusun genis kapsamini sinirlayici olarak yorumlanmamalidirlar. The following examples are intended to more fully illustrate preferred embodiments of the invention. has been presented. However, it is in no way limiting the broad scope of the invention. They should not be interpreted.
ORNEKLER sülfürik asit, 780 mg Na2WO4 (2.3 mmol, %4 mol) karisimi hazirlanmis ve ardindan 2 saatlik reaksiyon karisiminin HPLC ile analizi, baslangiç materyalinin toplam dönüsümünü ve istenen Fluensülfon. sülfürik asit, 780 mg Na2WO4 (2.3 mmol, %4 mol) karisimi hazirlanmis ve ardindan 2 saatlik reaksiyon karisiminin HPLC ile analizi, baslangiç materyalinin toplam dönüsümünü ve istenen göstermistir. reaksiyon karisiminin HPLC ile analizi, baslangiç materyalinin toplam dönüsümünü ve istenen göstermistir. fosforik asit, 780 mg Na2WO4 (2.3 mmol, %4 mol) karisimi hazirlanmis ve ardindan 2 saatlik reaksiyon karisiminin HPLC ile analizi, baslangiç materyalinin toplam dönüsümünü ve istenen kapsamli ayrismasi nedeniyle %75 seçicilikle göstermistir. EXAMPLES A mixture of sulfuric acid, 780 mg Na2WO4 (2.3 mmol, 4 mol%) was prepared and then incubated for 2 hours. Analysis of the reaction mixture by HPLC determines the total conversion of the starting material and the desired Fluenesulfone. A mixture of sulfuric acid, 780 mg Na2WO4 (2.3 mmol, 4 mol%) was prepared and then incubated for 2 hours. Analysis of the reaction mixture by HPLC determines the total conversion of the starting material and the desired has shown. Analysis of the reaction mixture by HPLC determines the total conversion of the starting material and the desired has shown. A mixture of phosphoric acid, 780 mg Na2WO4 (2.3 mmol, 4 mol%) was prepared and then incubated for 2 hours. Analysis of the reaction mixture by HPLC determines the total conversion of the starting material and the desired It showed 75% selectivity due to its extensive separation.
Aköz faz geri dönüsüm deneyleri eklenmistir. 22C'de 20 saat sonra reaksiyon kari siminin HPLC ile analizi, baslangiç materyalinin toplam dönüsümünü ve istenen flüensülfon, 5-kloro-2-((3,4,4-triflorobut-3-en-1- il)sülfoniI)-1A3,3)\2-tiyazol olusumunu %96 seçicilikle göstermistir. Organik fazin (organik çözücü içermeyen sülfon ürünü içeren) aköz fazdan ayrilmasindan sonra, baslangiçtaki tutmak için su fazinin %33'ü çikarilmistir. Bu sekilde gerçeklestirilen geri dönüsüm deneyleri, seçiciligin, ± %1 araliginda ayni oldugunu ortaya çikarmistir. 1OI3'de 1.5 saatlik bir süre içinde damlatilarak eklenmistir. Reaksiyon karisimi, oda sicakliginda 30 dakika karistirilmis ve daha sonra 40°C'ye kadar ilitilmis ve 13 saat karistirilmistir. Reaksiyon karisiminin HPLC ile analizi, baslangiç materyalinin toplam olusumunu göstermistir. Ürün, %97 seçicilik ile %77 verimle izole edilmistir. Aqueous phase recycling experiments has been added. HPLC analysis of the reaction mixture after 20 hours at 22C, initial the total conversion of the material and the desired fluorenesulfone, 5-chloro-2-((3,4,4-trifluorobut-3-ene-1- It showed the formation of yl)sulfonyl)-1A3,3)\2-thiazole with 96% selectivity. Organic phase (organic After separation from the aqueous phase (containing a solvent-free sulphone product), the initial 33% of the water phase was removed to retain Recycling experiments carried out in this way, revealed that the selectivity was the same within the range of ± 1%. 1OI3 was added dropwise over a period of 1.5 hours. Reaction mixture, room temperature for 30 minutes and then warmed to 40°C and incubated for 13 hours. mixed. Analysis of the reaction mixture by HPLC showed that the total amount of the starting material showed its formation. The product was isolated in 77% yield with 97% selectivity.
Bulusun belirli özellikleri burada gösterilmis ve tarif edilmis olsa da simdi bu konuda siradan bilgiye sahip kisiler için birçok modifikasyon, ikame, degisiklik ve esdeger gerçeklesecektir. Bu nedenle, ekteki istemlerin, bulusun gerçek ruhuna uygun olarak tüm bu tür modifikasyonlari ve degisiklikleri kapsamasinin amaçlandigi anlasilmalidir.Although certain features of the invention have been shown and described herein, we do not now have to Many modifications, substitutions, alterations and equivalents will occur for those with the knowledge. This Therefore, the appended claims exclude all such modifications and modifications in accordance with the true spirit of the invention. It should be understood that it is intended to cover the changes.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TR2022001274T2 true TR2022001274T2 (en) | 2022-02-21 |
Family
ID=
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2021024253A1 (en) | Process for the preparation of fluensulfone | |
| BR102015031482A2 (en) | process for the preparation of alkyl mercaptans | |
| CN1229341C (en) | Method for oxidizing thioether group into sulfoxide group | |
| TR2022001274T2 (en) | FLUENSULPHONE PREPARATION METHOD | |
| US3597459A (en) | New organo-metallic peroxidic derivatives of molybdenum and tungsten and their process of manufacture | |
| CN104761512A (en) | Method for producing heterocyclic fluoroalkenyl sulfones | |
| US4026908A (en) | Catalytic epoxidation process | |
| US6031108A (en) | Process for the preparation of 2-(methylsulfonyl)-5-(trifluoromethyl)-1,3,4-thiadiazole (TDA sulfone) | |
| CA1095065A (en) | Process for the epoxydation of olefins by hydrogen peroxide | |
| CA2254623C (en) | Synthesis of 2-(methylsulfonyl)-5-(trifluoromethyl)-1,3,4-thiadiazole via oxidation of 2-(methylthio)-5-(trifluoromethyl)-1,3,4-thiadiazole with glacial acetic acid | |
| CA2254597A1 (en) | Synthesis of sulfoxides via selective oxidation of sulfides with a perborate or a percarbonate | |
| US3670002A (en) | Oxidation of thiols to thiolsulfonates and sulfonic acids | |
| US5965737A (en) | Approach to the conversion of 2-(methylthio)-5-(trifluoromethyl)-1,3,4-thiadiazole (TDA) to 2-(methylsulfonyl)-5-(trifluoromethyl)-1,3,4-thiadiazole (TDA sulfone) | |
| JPS63258844A (en) | Production of trifluoromethanesulfonic acid | |
| CA2254579C (en) | Synthesis of 2-(methylsulfonyl)-5-(trifluoromethyl)-1,3,4-thiadiazole via oxidation of 2-(methylthio)-5-(trifluoromethyl)-1,3,4-thiadiazole with a molybdenum or tungsten catalyst | |
| EP0256486B1 (en) | A method of producing alkali metal benzenesulfinates | |
| AU621076B2 (en) | Process for preparation of sulfone derivatives | |
| US4849138A (en) | Method of producing alkali metal benzenesulfinates | |
| US3522311A (en) | Alkylsulfinylpropanediols | |
| MXPA99008292A (en) | An improved procedure for the conversion de2- (metiltio) -5- (trifluoromethyl) -1,3,4-tiadiazol (tda)) in 2- (metilsulfonil) -5- (trifluoromethyl) -1,3,4-tiadiazol ( tda sulfo | |
| US11897853B2 (en) | Synthesis of 1,1,2-trifluoro-4-(substituted sufonyl)-but-1-ene | |
| JP4247388B2 (en) | Process for producing 1,2-benzisothiazoline-3-one-1-oxide compound | |
| KR20230098155A (en) | Method for producing 1,2-benzisothiazolin-3-one |