CN103553860A - Method for synthesizing sulfamide compounds - Google Patents
Method for synthesizing sulfamide compounds Download PDFInfo
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- CN103553860A CN103553860A CN201310536289.4A CN201310536289A CN103553860A CN 103553860 A CN103553860 A CN 103553860A CN 201310536289 A CN201310536289 A CN 201310536289A CN 103553860 A CN103553860 A CN 103553860A
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- 238000000034 method Methods 0.000 title claims abstract description 28
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical class NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 title abstract 3
- 230000002194 synthesizing effect Effects 0.000 title description 2
- -1 nitryl compound Chemical class 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 239000010949 copper Substances 0.000 claims abstract description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052802 copper Inorganic materials 0.000 claims abstract description 28
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 5
- 239000004327 boric acid Substances 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 11
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005749 Copper compound Substances 0.000 claims description 5
- 150000001880 copper compounds Chemical class 0.000 claims description 5
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical group COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 5
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- 229960001701 chloroform Drugs 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 3
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 claims description 3
- 229960004418 trolamine Drugs 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 abstract 1
- 229940124530 sulfonamide Drugs 0.000 description 21
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 19
- 239000000047 product Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 10
- 229940045803 cuprous chloride Drugs 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000003814 drug Substances 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 238000010189 synthetic method Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 150000002828 nitro derivatives Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- ULZGIKROFVTVFP-UHFFFAOYSA-N C1(=CC=CC=C1)S(=O)O.C[Na] Chemical compound C1(=CC=CC=C1)S(=O)O.C[Na] ULZGIKROFVTVFP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 3
- CFBYEGUGFPZCNF-UHFFFAOYSA-N 2-nitroanisole Chemical compound COC1=CC=CC=C1[N+]([O-])=O CFBYEGUGFPZCNF-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000005957 chlorosulfonylation reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 241001120493 Arene Species 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- YIOCZJQJUCUDGA-UHFFFAOYSA-L [Na+].C1(=CC=CC=C1)S(=O)[O-].[Cl+].C1(=CC=CC=C1)S(=O)[O-] Chemical compound [Na+].C1(=CC=CC=C1)S(=O)[O-].[Cl+].C1(=CC=CC=C1)S(=O)[O-] YIOCZJQJUCUDGA-UHFFFAOYSA-L 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001543 aryl boronic acids Chemical class 0.000 description 1
- 125000004421 aryl sulphonamide group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007345 electrophilic aromatic substitution reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000005913 hydroamination reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- RHDUOFVTCTUTFX-UHFFFAOYSA-N methanesulfinic acid;sodium Chemical compound [Na].CS(O)=O RHDUOFVTCTUTFX-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- RBWSWDPRDBEWCR-RKJRWTFHSA-N sodium;(2r)-2-[(2r)-3,4-dihydroxy-5-oxo-2h-furan-2-yl]-2-hydroxyethanolate Chemical compound [Na+].[O-]C[C@@H](O)[C@H]1OC(=O)C(O)=C1O RBWSWDPRDBEWCR-RKJRWTFHSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing sulfamide compounds. The method comprises the following steps: reacting a nitryl compound with sulfinic acid or salt thereof in the presence of a composite catalytic system of copper catalyst/organic borate; adding quaternary ammonium salt promoter to promote the reaction, so that the reaction time is remarkably shortened, and the sulfamide compounds can be prepared with high yield. The method has the remarkable advantages of high reaction yield, strong universality and the like, is low in reaction temperature and short in time, and has excellent industrial prospect and industrial enlargement value.
Description
Technical field
The preparation method who the present invention relates to the synthetic field of medicine sulfamide compound, relates more specifically to a kind of method that-sulfinate and nitro-compound react synthetic sulfamide compound under the effect of copper catalyst/organic boric acid ester composite catalyst system.
Background technology
Sulfamide compound, as a kind of very important pharmaceutical intermediate, be now widely used in the fields such as biological medicine, organic synthesis, and sulfonamide structure is also prevalent among pharmaceutical preparation.According to statistics in 2011, in the medicine of world rankings front 100, there is 10% applied medicine nearly need contain the minor structure of sulphonamide.Therefore, sulphonamide has become one of important construction unit of medicine and bioactive compounds.Traditional sulphonamide synthetic method adopts acyl chlorides to react with amine to realize the synthetic of sulphonamide, but adopts SULPHURYL CHLORIDE often to cause raw material to be difficult to the shortcoming of preserving, response stimulus is strong as raw material, makes the method leave hidden danger in amplificationization is produced.In addition, in precursor SULPHURYL CHLORIDE synthetic, usually adopt the electrophilic aromatic substitution reaction of (1) chlorsulfonic acid and the oxidation chlorination of (2) organosulfur compound, these reactions relate to harsh reaction conditions and poisonous reaction reagent etc. and have limited its application.As can be seen here, the synthetic method of developing a kind of high yield, sulfamide compound that universality is strong is the urgent difficult problem that vast organic chemistry, medicine study on the synthesis personnel face.
The existing many relevant reports of the synthetic method of relevant sulfamide compound or technique in prior art, for example:
Tang Xiaodong etc. (" Copper-catalyzed sulfonamides formation from sodiu m sulfinates and amines ", Chem.Commun, 2013,49, a kind of synthetic method of sulphonamide 6102-6104) is disclosed.Described method take-sulfinate and amine as raw material, to take oxygen or methyl-sulphoxide be oxygenant, under the effect of copper catalyst, through oxidative coupling reaction, prepares corresponding sulfonamide compounds.
J.Robb DeBergh etc. (" Synthesis of Aryl Sulfonamides via Palladium-Cat alyzed Chlorosulfonylation of Arylboronic Acids ", J.Am.Chem.Soc., 2013,135, a kind of preparation method of sulphonamide 10638-10641) is disclosed.Described method is that aryl boric acid chlorosulfonylation reaction occurs under palladium catalyst effect prepares sulfonyl chloride intermediate; and then generate corresponding sulphonamide with amine reaction in－situ; this reaction conditions is gentle, raw material is easy to get, but need to use expensive palladium catalytic reagent, is difficult to industrialization.
J.S.Yadav etc. (" Iodine-catalyzed ontermolecular hydroamination of vinyl arenes ", Tetrahedron letters, 2009,50,5351-5353) disclose a kind of synthetic method of sulphonamide, it adopts iodine is solvent as catalyzer, toluene, and benzsulfamide is reacted 2.5 hours with vinylbenzene at 110 ℃, can obtain 90% yield, but this temperature of reaction is high, alkene is easy to polymerization and cause by product to increase.
The Patent Application Publication of CN102675163A a kind of preparation method of sulphonamide.It is by-sulfinic acid or-sulfinate and nitro-compound under atmosphere of inert gases, and the copper compound of take has been realized the preparation of sulphonamide as catalyzer.But the method has specificity for the combination of catalyst/solvent, even if adopt identical copper compound catalyzer, and due to the difference of solvent all can inducing reaction property huge deviation, cause product yield difference huge, even cannot carry out, above-mentioned reason makes the method narrow application range, universality poor, is difficult to industrial applications.
Organoboron reagent is usually in the middle of the reaction for catalytic preparation of amide, for example: boric acid and aryl boric acid directly catalysis carboxylic acid and amine react synthesizing amide [referring to H.Charville, D.Jackson, G.Hodges and A.Whiting, Chem.Commun., 2010,46,1813 – 182].But these usually react long reaction time, condition is harsh.In addition, in prior art, yet there are no that organic borane reagent reacts with nitro-compound for catalysis-sulfinate and the relevant report of preparing sulphonamide.
The many defects that exist for prior art and the specificity feature of organic catalytic reaction, the present invention is intended to find one, and cost is low, yield is high, be suitable for the novel preparation method of the sulfamide compound of suitability for industrialized production, to meet vast medical synthetic work person's demand, and realize Economic concept green, environmental protection.
Summary of the invention
For many defects of above-mentioned existence, the inventor, after having paid a large amount of creative works, has developed a kind of novel preparation method of sulfamide compound through further investigation.Surprisingly, the present invention adopts composite catalyst system (copper catalyst/organoboron reagent composite catalyst system, "/" wherein represent " with " relation), and carry out suitable and rational processing parameter to select and obtained beyond thought technique effect.The method of the invention has the plurality of advantages such as reaction yield is high, cost is low, universality is good, has good industrialization prospect.
Particularly, the invention provides the preparation method of sulfamide compound shown in a kind of formula (I),
Described method comprises: under the composite catalyst system effect of copper catalyst/organic boric acid ester, formula (II) compound and formula (III) compound react in organic solvent,
Wherein, R
1, R
2be selected from independently of one another with substituting group or unsubstituted C
1-C
6alkyl, with substituting group or unsubstituted C
1-C
6alkoxyl group, with substituting group or unsubstituted C
5-C
12aryl or with substituting group or unsubstituted C
4-C
12heteroaryl; Described C
5-C
12aryl or C
4-C
12heteroaryl is phenyl, naphthyl, pyridyl, pyrryl, thienyl or furyl; Described substituting group is halogen, C
1-C
6alkyl, C
1-C
6alkoxyl group; Described substituting group is preferably halogen, methyl, ethyl, n-propyl, sec.-propyl, the tertiary butyl, methoxy or ethoxy;
M is H, NH
4 +or metallic cation; Be preferably H, NH
4 +, alkali metal cation or alkaline earth metal cation; More preferably H, NH
4+, Li
+, Na
+, K
+, Ru
+or Cs
+.
In described method of the present invention, halogen atom refers to fluorine, chlorine, bromine or iodine atom.
In described method of the present invention, C
1-C
6alkyl refers to the alkyl with 1-6 carbon atom, and it can be straight or branched, and indefiniteness ground is such as can be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, n-hexyl etc.
In described method of the present invention, C
1-C
6alkoxyl group refers to " C defined above
1-C
6alkyl " group after being connected with O atom.
In described method of the present invention, organic solvent when formula (II) is reacted with (III) is not particularly limited, can be any conventional solvent using in organic synthesis field, for example can be to indefiniteness benzene, toluene, N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO), dimethyl formamide (DMF), acetonitrile, methyl-phenoxide, dioxane, ethylene dichloride, methylene dichloride, trichloromethane, tetracol phenixin, normal hexane, tetrahydrofuran (THF) (THF), ether, methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, amylalcohol, one or more in hexanol etc., be preferably toluene, N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO), dimethyl formamide (DMF), acetonitrile, methyl-phenoxide, dioxane, tetrahydrofuran (THF), trichloromethane.
In described method of the present invention, described formula (II) is 1-2.5:1 with the mol ratio of formula (III) compound, this scope has comprised any sub-range scope wherein, as 1.1-2.4:1,1.2-2.3:1,1.3-2.2:1,1.4-2.1:1,1.5-2.0:1,1.6-1.9:1, also comprise any concrete point value wherein, exemplarily for example can be 1.1:1,1.2:1,1.4:1,1.6:1,1.8:1,2:1,2.2:1,2.4:1 or 2.5:1.
In described method of the present invention, described copper catalyst is elemental copper or copper compound, is preferably Cu, CuCl
2, CuCl, CuBr
2, CuBr, CuI
2, CuI, CuCO
3, Cu (OTf)
2, CuOAc or Cu (OAc)
2in any one.
In described method of the present invention, described organic boric acid ester is trimethyl borate, triethyl borate, trolamine boric acid ester, B (OCH
2cF
3)
3in any one.
In described method of the present invention, the mole dosage of described copper catalyst is (II) and (III) 0.5-5% of both integral molar quantities, this scope has comprised any sub-range scope wherein, as 1-4%, 2-3%, also comprise any concrete point value wherein, exemplarily for example can be (II) and 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5% of (III) both integral molar quantities.
In described method of the present invention, the mol ratio of described copper catalyst and organic boric acid ester is 1:1-2, for example, can be 1:1.1,1:1.2,1:1.3,1:1.4,1:1.5,1:1.6,1:1.7,1:1.8,1:1.9 or 1:2.0.
Preferably, reaction is carried out under atmosphere of inert gases, and described rare gas element is any one in nitrogen, argon gas.
More preferably, except using above-mentioned copper catalyst and organic boric acid ester, also can in reaction system, further add promotor, described promotor is quaternary ammonium salt, can be to indefiniteness any one in benzyltriethylammoinium chloride (TEBA), Tetrabutyl amonium bromide, tetrabutylammonium chloride, tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride.When adding promotor, unexpectedly further shortened the reaction times.Wherein in mass, promotor can be 1-3:1 with the ratio of copper catalyst, as 1:1,1.5:1,2:1,2.5:1 or 3:1, and preferred 2-1:1.
In described method of the present invention, reaction times there is no special restriction, for example can determine the suitable reaction times by the residual per-cent of liquid chromatographic detection object product or raw material, it typically is 1-18 hour, is indefiniteness for example 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours or 18 hours.
In described method of the present invention, temperature of reaction is 60-120 ℃, for example can be to indefiniteness 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃.
Reaction finishes, and obtains after crude product, can adopt conventional means to purify, for example, reaction system can be cooled to room temperature, cross that silica gel chromatographic column is separated, eluting solvent is removed in evaporation, vacuum-drying and obtain target sulphonamide product
The present invention is by using the composite catalyst system of copper catalyst/organic boric acid ester, and preferably further add promotor, and effectively make formula II and III compound react, thereby high yield prepare sulfamide compound, and have reaction temperature and, the plurality of advantages such as universality is good, there is good prospects for commercial application and marketable value.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail, but these exemplary embodiments not form any type of any restriction to real protection scope of the present invention.
Embodiment 1
In 100ml flask, add successively 60ml N-Methyl pyrrolidone, 8mmol oil of mirbane, and 10mmol is to methyl sodium benzene sulphinate, under heated and stirred, be incorporated as the 0.09mmol cuprous chloride of two kinds of reaction raw materials integral molar quantities 5% and the trimethyl borate of 0.09mmol, stirring reaction 10h under 80 ℃, nitrogen atmosphere, be cooled to after completion of the reaction room temperature, cross silica gel chromatographic column separation, evaporate and remove eluting solvent, vacuum-drying obtains target sulphonamide product, and yield is 95%.
1H-NMR(CDCl
3,300MHz)δ：2.41(s,3H)，4.12(s,1H)，6.70(d,2H)，6.91(t,1H)，7.18(d,2H)，7.42(d,2H)，7.81(d,2H)。
MS?m/z：247.09(M+1,100)。
Embodiment 2
In 100ml flask, add successively 50ml N-Methyl pyrrolidone, 10mmol to methoxy nitrobenzene, and 12mmol is to methyl sodium benzene sulphinate, under heated and stirred, be incorporated as 0.66mmol cuprous chloride and the 0.99mmol triethyl borate of two kinds of reaction raw materials integral molar quantities 3%, stirring reaction 10h under 100 ℃, nitrogen atmosphere, be cooled to after completion of the reaction room temperature, cross silica gel chromatographic column separation, evaporate and remove eluting solvent, vacuum-drying obtains target sulphonamide product, and yield is 92%.
1H-NMR(CDCl
3,300MHz)δ：2.40(s,3H)，3.79(s,3H)，4.09(s,1H)，6.68(d,2H)，6.97(d,2H)，7.39(d,2H)，7.76(d,2H)。
MS?m/z：277.10(M+1,100)。
Embodiment 3
In 100ml flask, add successively 75ml N-Methyl pyrrolidone, 12mmol to methoxy nitrobenzene, and 24mmol is to chlorine benzene sulfinic acid sodium salt, under heated and stirred, be incorporated as 1.44mmol cuprous chloride and the 2.88mmol trolamine boric acid ester of two kinds of reaction raw materials integral molar quantities 4%, stirring reaction 15h under 120 ℃, nitrogen atmosphere, be cooled to after completion of the reaction room temperature, cross silica gel chromatographic column separation, evaporate and remove eluting solvent, vacuum-drying obtains target sulphonamide product, and yield is 91%.
1H-NMR(CDCl
3,300MHz)δ：3.81(s,3H)，4.05(s,1H)，6.70(d,2H)，7.02(d,2H)，7.59(d,2H)，7.78(d,2H)。
MS?m/z：297.06(M+1,100)。
Embodiment 4
In 100ml flask, once add 55ml N-Methyl pyrrolidone, 6mmol4-nitropyridine, and 9mmol is to methyl sodium benzene sulphinate, is incorporated as 0.3mmol cuprous chloride and the 0.6mmol B (OCH of two kinds of reaction raw materials integral molar quantities 2% under heated and stirred
2cF
3)
3, stirring reaction 12h under 110 ℃, nitrogen atmosphere, is cooled to after completion of the reaction room temperature, crosses that silica gel chromatographic column is separated, eluting solvent is removed in evaporation, and vacuum-drying obtains target sulphonamide product, and yield is 93%.
1H-NMR(CDCl
3,300MHz)δ：2.38(s,3H)，4.06(s,1H)，7.04(d,2H)，7.43(d,2H)，7.80(d,2H)，8.51(d,2H)。
MS?m/z：248.11(M+1,100)。
Embodiment 5
In 100ml flask, once add 65ml N-Methyl pyrrolidone, 8mmol oil of mirbane, and 12mmol methyl-sulfinic acid sodium, under heated and stirred, be incorporated as 0.2mmol cuprous chloride and the 0.2mmol trimethyl borate of two kinds of reaction raw materials integral molar quantities 1%, stirring reaction 16h under 90 ℃, nitrogen atmosphere, be cooled to after completion of the reaction room temperature, cross silica gel chromatographic column separation, evaporate and remove eluting solvent, vacuum-drying obtains target sulphonamide product, and yield is 94%.
1H-NMR(CDCl
3,300MHz)δ：2.97(s,3H)，4.07(s,1H)，6.71(d,2H)，6.85(t,1H)，7.23(d,2H)。
MS?m/z：171.08(M+1,100)。
Embodiment 6-13
With the same way as of embodiment 1, carried out embodiment 6-13 respectively, difference part is to adopt different reaction solvents.Concrete outcome sees the following form 1.
Table 1. adopts the product yield under different solvents
Embodiment 14-23
With the same way as of embodiment 1, carried out embodiment 14-23 respectively, difference part is to adopt different catalyst system, and concrete outcome sees the following form 2.
Table 2. adopts the product yield under different copper catalysts
Embodiment 24-29
With the same way as of embodiment 1, carried out embodiment 24-29 respectively, difference part is also in reaction system, to have added different promotors, and wherein promotor and copper catalyst are that the mass ratio of cuprous chloride is distinguished as follows:
Embodiment 24 is 1:1; Embodiment 25 is 2:1; Embodiment 26 is 3:1; Embodiment 27 is 1.5:1; Embodiment 28 is 2.5:1; Embodiment 29 is 3:1.
Adopt gas-chromatography-liquid chromatography coupling assaying reaction yield, concrete outcome sees the following form 3.
Table 3. adopts the product yield under different promotors
As can be seen here:
Copper catalyst/organic boric acid ester catalyst system is applied to nitro-compound and reacts the reaction type of preparing sulphonamide with-sulfinate, through large quantity research, draw following result:
1,, from above-described embodiment 1-5, adopt copper catalyst, and while adding various organic boric acid ester, reaction has all obtained high yield (>91%), has confirmed the excellent catalytic performance of copper catalyst/organic boric acid ester system.
2, by above-mentioned table 1, can be found out, adopt this reaction of cuprous chloride/trimethyl borate catalysis, under differential responses solvent, react and all can carry out, and obtained suitable high yield, and yield reach as high as 93%;
3, by above-mentioned table 2, can be found out, when adopting different copper catalysts, product yield is all kept, and has confirmed that the catalysis that under the cooperation of organic boric acid ester various copper compounds or simple substance all can high yields prepares sulphonamide.
4, by above-mentioned table 3, can be found out, when adding various quaternary ammonium salt promotor in reaction system, not only improved yield, and obviously shortened the reaction times, the reaction times shortens at most half.
Therefore, method of the present invention compared with prior art, by the use of copper catalyst/organic boric acid ester catalyst system, not only makes reaction yield high, and makes various copper catalysts, the reaction solvent all can be practical, thereby has expanded the scope of application of reaction; In addition, by introducing quaternary ammonium salt promotor, shorten significantly the time of reaction, obtained beyond thought technique effect, for amplification or the suitability for industrialized production of sulfamide compound, there is very strong industrial prospect and economic benefit.Although organic catalytic reaction has certain not predictability, but the inventor has worked out the preparation method of a kind of high yield, sulfamide compound that universality is strong through a large amount of creative works, and produced obvious positively effect, there is research and using value significantly.
The purposes that should be appreciated that these embodiment only limits the scope of the invention for the present invention being described but not being intended to.In addition; also should understand; after having read technology contents of the present invention, those skilled in the art can make various changes, modification and/or modification to the present invention, within these all equivalent form of values fall within the protection domain that the application's appended claims limits equally.
Claims (10)
1. a preparation method for sulfamide compound shown in formula (I),
Described method comprises: under the composite catalyst system effect of copper catalyst/organic boric acid ester, formula (II) compound and formula (III) compound react in organic solvent,
Wherein, R
1, R
2be selected from independently of one another with substituting group or unsubstituted C
1-C
6alkyl, with substituting group or unsubstituted C
1-C
6alkoxyl group, with substituting group or unsubstituted C
5-C
12aryl or with substituting group or unsubstituted C
4-C
12heteroaryl.
2. the preparation method of sulfamide compound shown in a kind of formula (I) according to claim 1, is characterized in that: described C
5-C
12aryl or C
4-C
12heteroaryl is phenyl, naphthyl, pyridyl, pyrryl, thienyl or furyl; Described halogen atom refers to fluorine, chlorine, bromine or iodine atom.
3. according to the preparation method of sulfamide compound shown in a kind of formula (I) described in claim 1 or 2, it is characterized in that: described copper catalyst is elemental copper or copper compound.
4. according to the preparation method of sulfamide compound shown in a kind of formula (I) described in claim 1-3 any one, it is characterized in that: formula (II) is 1-2.5:1 with the mol ratio of formula (III) compound.
5. according to the preparation method of sulfamide compound shown in a kind of formula (I) described in claim 1-4 any one, it is characterized in that: the mole dosage of described copper catalyst is (II) and (III) 0.5-5% of both integral molar quantities; The mol ratio of described copper catalyst and organic boric acid ester is 1:1-2.
6. according to the preparation method of sulfamide compound shown in a kind of formula (I) described in claim 1-5 any one, it is characterized in that: described organic solvent is one or more in benzene, toluene, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), dimethyl formamide, acetonitrile, methyl-phenoxide, dioxane, ethylene dichloride, methylene dichloride, trichloromethane, tetracol phenixin, normal hexane, tetrahydrofuran (THF), ether, methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, amylalcohol, hexanol.
7. according to the preparation method of sulfamide compound shown in a kind of formula (I) described in claim 1-6 any one, it is characterized in that: described copper catalyst is Cu, CuCl
2, CuCl, CuBr
2, CuBr, CuI
2, CuI, CuCO
3, Cu (OTf)
2, CuOAc or Cu (OAc)
2in any one.
8. according to the preparation method of sulfamide compound shown in a kind of formula (I) described in claim 1-7 any one, it is characterized in that: described organic boric acid ester is trimethyl borate, triethyl borate, trolamine boric acid ester, B (OCH
2cF
3)
3in any one.
9. according to the preparation method of sulfamide compound shown in a kind of formula (I) described in claim 1-8 any one, it is characterized in that: except using above-mentioned copper catalyst and boric acid ester, also in reaction system, further add promotor, described promotor is quaternary ammonium salt.
10. the preparation method of sulfamide compound shown in a kind of formula (I) according to claim 9, is characterized in that: described promotor is any one in benzyltriethylammoinium chloride (TEBA), Tetrabutyl amonium bromide, tetrabutylammonium chloride, tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride; Wherein in mass, promotor is 1-3:1 with the ratio of copper catalyst.
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| CN108440345A (en) * | 2018-04-08 | 2018-08-24 | 西北师范大学 | A kind of preparation method of sulfamide compound |
| CN110372463A (en) * | 2019-07-12 | 2019-10-25 | 浙江大学 | A kind of method of nitro-aromatic and boronic acid compounds coupling synthesis sulfonamide compounds |
| CN111170905A (en) * | 2019-12-28 | 2020-05-19 | 台州学院 | Synthetic method of sulfonamide compound |
| CN114057616A (en) * | 2021-11-12 | 2022-02-18 | 温州大学 | Method for synthesizing N-substituted benzene sulfonamide compound |
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