CN106146358B - 一种合成氨基‑(n‑烷基)苯磺酰胺的方法 - Google Patents
一种合成氨基‑(n‑烷基)苯磺酰胺的方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 11
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 title abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 39
- YAZSBRQTAHVVGE-UHFFFAOYSA-N 2-aminobenzenesulfonamide Chemical compound NC1=CC=CC=C1S(N)(=O)=O YAZSBRQTAHVVGE-UHFFFAOYSA-N 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 7
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 33
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 33
- 229910021640 Iridium dichloride Inorganic materials 0.000 claims description 30
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- -1 aminomethyl phenyl Chemical group 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 3
- 150000002431 hydrogen Chemical class 0.000 claims 1
- WQIQNKQYEUMPBM-UHFFFAOYSA-N pentamethylcyclopentadiene Chemical compound CC1C(C)=C(C)C(C)=C1C WQIQNKQYEUMPBM-UHFFFAOYSA-N 0.000 claims 1
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 abstract description 61
- 239000002904 solvent Substances 0.000 abstract description 59
- 239000000203 mixture Substances 0.000 abstract description 30
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 238000002390 rotary evaporation Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 112
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 84
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 56
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 56
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 28
- 238000005160 1H NMR spectroscopy Methods 0.000 description 28
- 238000004440 column chromatography Methods 0.000 description 28
- 230000006837 decompression Effects 0.000 description 28
- 229910052757 nitrogen Inorganic materials 0.000 description 28
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical class NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 22
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 0 *[N+](c1cccc(**I)c1)([O-])[O+] Chemical compound *[N+](c1cccc(**I)c1)([O-])[O+] 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- XXRNQEBDIQPZRC-UHFFFAOYSA-N 4-amino-n-butylbenzenesulfonamide Chemical compound CCCCNS(=O)(=O)C1=CC=C(N)C=C1 XXRNQEBDIQPZRC-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- KLCQXXAKURQDOV-UHFFFAOYSA-N chlorobenzene methanol Chemical group CO.CO.ClC1=CC=CC=C1 KLCQXXAKURQDOV-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 150000003456 sulfonamides Chemical class 0.000 description 2
- PBLNHHSDYFYZNC-UHFFFAOYSA-N (1-naphthyl)methanol Chemical compound C1=CC=C2C(CO)=CC=CC2=C1 PBLNHHSDYFYZNC-UHFFFAOYSA-N 0.000 description 1
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 1
- GJDQKHHRAOFNEH-UHFFFAOYSA-N 2-amino-n-benzylbenzenesulfonamide Chemical compound NC1=CC=CC=C1S(=O)(=O)NCC1=CC=CC=C1 GJDQKHHRAOFNEH-UHFFFAOYSA-N 0.000 description 1
- 125000006280 2-bromobenzyl group Chemical group [H]C1=C([H])C(Br)=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000006282 2-chlorobenzyl group Chemical group [H]C1=C([H])C(Cl)=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- 125000006512 3,4-dichlorobenzyl group Chemical group [H]C1=C(Cl)C(Cl)=C([H])C(=C1[H])C([H])([H])* 0.000 description 1
- BUBJRDZLVJJKLT-UHFFFAOYSA-N 3-amino-n-benzylbenzenesulfonamide Chemical compound NC1=CC=CC(S(=O)(=O)NCC=2C=CC=CC=2)=C1 BUBJRDZLVJJKLT-UHFFFAOYSA-N 0.000 description 1
- JPVKCHIPRSQDKL-UHFFFAOYSA-N 3-aminobenzenesulfonamide Chemical class NC1=CC=CC(S(N)(=O)=O)=C1 JPVKCHIPRSQDKL-UHFFFAOYSA-N 0.000 description 1
- 125000006497 3-methoxybenzyl group Chemical group [H]C1=C([H])C(=C([H])C(OC([H])([H])[H])=C1[H])C([H])([H])* 0.000 description 1
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 1
- YLYKCJFMRJGOEB-UHFFFAOYSA-N 4-amino-N-(cyclohexylmethyl)benzenesulfonamide Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NCC1CCCCC1 YLYKCJFMRJGOEB-UHFFFAOYSA-N 0.000 description 1
- ZEKCGNUOGJACDL-UHFFFAOYSA-N 4-amino-N-[[4-(trifluoromethoxy)phenyl]methyl]benzenesulfonamide Chemical compound FC(OC1=CC=C(CNS(=O)(=O)C2=CC=C(C=C2)N)C=C1)(F)F ZEKCGNUOGJACDL-UHFFFAOYSA-N 0.000 description 1
- NEQKXAKFVIBBTH-UHFFFAOYSA-N 4-amino-N-benzyl-3,5-dibromobenzenesulfonamide Chemical compound NC1=C(C=C(C=C1Br)S(=O)(=O)NCC1=CC=CC=C1)Br NEQKXAKFVIBBTH-UHFFFAOYSA-N 0.000 description 1
- HHEXVLXMZIVFSS-UHFFFAOYSA-N 4-amino-n-(2-ethylhexyl)benzenesulfonamide Chemical compound CCCCC(CC)CNS(=O)(=O)C1=CC=C(N)C=C1 HHEXVLXMZIVFSS-UHFFFAOYSA-N 0.000 description 1
- RHQIZSFKTPJDLA-UHFFFAOYSA-N 4-amino-n-(3-methylbutyl)benzenesulfonamide Chemical compound CC(C)CCNS(=O)(=O)C1=CC=C(N)C=C1 RHQIZSFKTPJDLA-UHFFFAOYSA-N 0.000 description 1
- SUSCUGLPFPVRNN-UHFFFAOYSA-N 4-amino-n-(naphthalen-1-ylmethyl)benzenesulfonamide Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NCC1=CC=CC2=CC=CC=C12 SUSCUGLPFPVRNN-UHFFFAOYSA-N 0.000 description 1
- ZPRDNXGWBTZSEE-UHFFFAOYSA-N 4-amino-n-(thiophen-2-ylmethyl)benzenesulfonamide Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NCC1=CC=CS1 ZPRDNXGWBTZSEE-UHFFFAOYSA-N 0.000 description 1
- MPGUXCPHUIVGNG-UHFFFAOYSA-N 4-amino-n-[(2-bromophenyl)methyl]benzenesulfonamide Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NCC1=CC=CC=C1Br MPGUXCPHUIVGNG-UHFFFAOYSA-N 0.000 description 1
- BBUWLCGYMZNPLY-UHFFFAOYSA-N 4-amino-n-[(2-chlorophenyl)methyl]benzenesulfonamide Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NCC1=CC=CC=C1Cl BBUWLCGYMZNPLY-UHFFFAOYSA-N 0.000 description 1
- CPWBFUYREIJPAR-UHFFFAOYSA-N 4-amino-n-[(3,4-dichlorophenyl)methyl]benzenesulfonamide Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NCC1=CC=C(Cl)C(Cl)=C1 CPWBFUYREIJPAR-UHFFFAOYSA-N 0.000 description 1
- GUJCQDJRUBKPDO-UHFFFAOYSA-N 4-amino-n-[(3-methoxyphenyl)methyl]benzenesulfonamide Chemical compound COC1=CC=CC(CNS(=O)(=O)C=2C=CC(N)=CC=2)=C1 GUJCQDJRUBKPDO-UHFFFAOYSA-N 0.000 description 1
- YXJZDNBXDIPOBQ-UHFFFAOYSA-N 4-amino-n-[(4-bromophenyl)methyl]benzenesulfonamide Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NCC1=CC=C(Br)C=C1 YXJZDNBXDIPOBQ-UHFFFAOYSA-N 0.000 description 1
- SWVGTNYFDHQAOW-UHFFFAOYSA-N 4-amino-n-[(4-chlorophenyl)methyl]benzenesulfonamide Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NCC1=CC=C(Cl)C=C1 SWVGTNYFDHQAOW-UHFFFAOYSA-N 0.000 description 1
- RSKLWIXTGFLDDB-UHFFFAOYSA-N 4-amino-n-[(4-methoxyphenyl)methyl]benzenesulfonamide Chemical compound C1=CC(OC)=CC=C1CNS(=O)(=O)C1=CC=C(N)C=C1 RSKLWIXTGFLDDB-UHFFFAOYSA-N 0.000 description 1
- FMALNZIYCSTSQU-UHFFFAOYSA-N 4-amino-n-[(4-methylphenyl)methyl]benzenesulfonamide Chemical compound C1=CC(C)=CC=C1CNS(=O)(=O)C1=CC=C(N)C=C1 FMALNZIYCSTSQU-UHFFFAOYSA-N 0.000 description 1
- WXHOKZKFJXZCMO-UHFFFAOYSA-N 4-amino-n-[(4-propan-2-ylphenyl)methyl]benzenesulfonamide Chemical compound C1=CC(C(C)C)=CC=C1CNS(=O)(=O)C1=CC=C(N)C=C1 WXHOKZKFJXZCMO-UHFFFAOYSA-N 0.000 description 1
- ONKJCPSNRASOFV-UHFFFAOYSA-N 4-amino-n-benzyl-3,5-dichlorobenzenesulfonamide Chemical compound C1=C(Cl)C(N)=C(Cl)C=C1S(=O)(=O)NCC1=CC=CC=C1 ONKJCPSNRASOFV-UHFFFAOYSA-N 0.000 description 1
- WSTTZKUMEAQEIP-UHFFFAOYSA-N 4-amino-n-benzyl-3-bromobenzenesulfonamide Chemical compound C1=C(Br)C(N)=CC=C1S(=O)(=O)NCC1=CC=CC=C1 WSTTZKUMEAQEIP-UHFFFAOYSA-N 0.000 description 1
- ZHKXBELKPQXYEH-UHFFFAOYSA-N 4-amino-n-benzylbenzenesulfonamide Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NCC1=CC=CC=C1 ZHKXBELKPQXYEH-UHFFFAOYSA-N 0.000 description 1
- TWDXGFYTZRHHCF-UHFFFAOYSA-N 4-amino-n-cyclohexylbenzenesulfonamide Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1CCCCC1 TWDXGFYTZRHHCF-UHFFFAOYSA-N 0.000 description 1
- XNPAQSUBTOJSLM-UHFFFAOYSA-N 4-amino-n-cyclopentylbenzenesulfonamide Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1CCCC1 XNPAQSUBTOJSLM-UHFFFAOYSA-N 0.000 description 1
- BLAWZIRICNQARU-UHFFFAOYSA-N 4-amino-n-hexylbenzenesulfonamide Chemical compound CCCCCCNS(=O)(=O)C1=CC=C(N)C=C1 BLAWZIRICNQARU-UHFFFAOYSA-N 0.000 description 1
- NFFFEINZRAHCOK-UHFFFAOYSA-N 4-amino-n-octylbenzenesulfonamide Chemical compound CCCCCCCCNS(=O)(=O)C1=CC=C(N)C=C1 NFFFEINZRAHCOK-UHFFFAOYSA-N 0.000 description 1
- 125000006281 4-bromobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Br)C([H])([H])* 0.000 description 1
- 125000006283 4-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Cl)C([H])([H])* 0.000 description 1
- 125000002528 4-isopropyl benzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- OIGWAXDAPKFNCQ-UHFFFAOYSA-N 4-isopropylbenzyl alcohol Chemical compound CC(C)C1=CC=C(CO)C=C1 OIGWAXDAPKFNCQ-UHFFFAOYSA-N 0.000 description 1
- 125000004217 4-methoxybenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1OC([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000006181 4-methyl benzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000173 4-trifluoromethoxy benzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1OC(F)(F)F)C([H])([H])* 0.000 description 1
- DBNFARXVXNBKPO-UHFFFAOYSA-N 5-amino-n-benzyl-2-methylbenzenesulfonamide Chemical compound CC1=CC=C(N)C=C1S(=O)(=O)NCC1=CC=CC=C1 DBNFARXVXNBKPO-UHFFFAOYSA-N 0.000 description 1
- SOCSWWWQOUGPEZ-UHFFFAOYSA-N Nc(cc1)ccc1S(NCC(CC1Cl)=CC=C1Cl)(=O)=O Chemical compound Nc(cc1)ccc1S(NCC(CC1Cl)=CC=C1Cl)(=O)=O SOCSWWWQOUGPEZ-UHFFFAOYSA-N 0.000 description 1
- 229910018105 SCl2 Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- JIJWRJCVLPNOHM-UHFFFAOYSA-N bromo(phenyl)methanol Chemical compound OC(Br)C1=CC=CC=C1 JIJWRJCVLPNOHM-UHFFFAOYSA-N 0.000 description 1
- MOFLDTNKLMFGSU-UHFFFAOYSA-N bromobenzene;methanol Chemical compound OC.BrC1=CC=CC=C1 MOFLDTNKLMFGSU-UHFFFAOYSA-N 0.000 description 1
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- VSSAZBXXNIABDN-UHFFFAOYSA-N cyclohexylmethanol Chemical compound OCC1CCCCC1 VSSAZBXXNIABDN-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
本发明公开了一种合成氨基‑(N‑烷基)苯磺酰胺的方法。包括如下步骤：在反应容器中，加入氨基苯磺酰胺、铱络合物催化剂、碱、化合物醇、溶剂叔戊醇，反应混合物在120‑150 oC下反应数小时后，冷却到室温，旋转蒸发除去溶剂，然后通过柱分离，得到目标化合物。本发明使用商品化的氨基苯磺酰胺和近于无毒的化合物醇为起始原料；反应只生成水为副产物，无环境危害；反应原子经济性高。
Description
技术领域
本发明属有机合成化学技术领域，具体涉及一种合成氨基-(N-烷基)苯磺酰胺的方法。
背景技术
N-烷基磺酰胺衍生物代表着一类重要的含氮化合物,展现了广泛的的生理和药理活性。((a)Bissinger,E.M.；Heinke,R.；Spannhoff,A.；Eberlin,A.；Metzger,E.；Cura,V.；Hassenboehler,P.；Cavarelli,J.；Schüle,R.；Bedford,M.T.；Sippl,W.；Jung,M.Bioorg.Med.Chem.2001,19,3717.(b)Ghosh,A.K.；Chapsal,B.D.；Parham,G.L.；Steffey,M.；Agniswamy,J.；Wang,Y.；Amano,M.；Weber,I.T.；Mitsuya,H.J.Med.Chem.2011,54,5890.(c)Agniswamy,J.；Shen,C.；Wang,Y.；Ghosh,A.K.；Rao,K.V.；Xu,C.；Sayer,J.M.；Louis,J.M.；Weber,I.T.J.Med.Chem.2013,56,4017.(d)Ghosh,A.K.；Parham,G.L.；Martyr,C.D.；Nyalapatla,P.R.；Osswald,H.L.；Agniswamy,J.；Wang,Y.；Amano,M.；Weber,I.T.；Mitsuya,H.J.Med.Chem.2013,56,6792.)
传统的方法合成氨基-(N-烷基)苯磺酰胺是通过多步反应，使用大量的有毒试剂才能实现，反应的原子经济性低。
发明内容
本发明的目的在于提供一种合成氨基-(N-烷基)苯磺酰胺的新方法。
本发明通过下述技术方案实现：一种合成氨基-(N-烷基)苯磺酰胺(式Ⅰ)的新方法
其包含使氨基苯磺酰胺(式Ⅱ)
与化合物醇(式Ⅲ)反应
反应是在铱络合物催化剂和碱存在下发生，其反应通式为
其中，R1代表氢、单或多取代基团，优选卤素或甲基。
R2，R3代表氢、C4-C8烷基、单或多取代芳基，优选甲基苯基、异丙基苯基、甲氧基苯基、三氟甲基苯基、三氟甲氧基苯基、卤代苯基、噻吩基或萘基。
具体的，本发明的目标产物是通过如下步骤制备：
在反应容器中，加入氨基苯磺酰胺、铱络合物催化剂、碱、化合物醇、溶剂叔戊醇，反应混合物在120-150℃下反应数小时后，冷却到室温，旋转蒸发除去溶剂，然后通过柱分离，得到目标化合物。
其中，铱络合物催化剂为[Cp*IrCl2]2(Cp*＝pentamethylcyclopentadienyl)。
碱选自碳酸钾、碳酸铯和磷酸钾中任意一种；铱络合物催化剂用量相对于氨基苯磺酰胺的摩尔比为1mol％；碱相对于氨基苯磺酰胺摩尔比为0.2-0.4equiv.；化合物醇相对于氨基苯磺酰胺摩尔比为1.2:1；反应温度优选120℃；反应时间为12小时以上。
同现有技术相比，本发明从从氨基苯磺酰胺出发，通过和化合物醇发生反应，得到氨基-(N-烷基)苯磺酰胺反应展现出三个显著的优点：1)使用商品化的氨基苯磺酰胺和近于无毒的化合物醇为起始原料；2)反应只生成水为副产物，无环境危害；3)反应原子经济性高；因此，该反应符合绿色化学的要求，具有广阔的发展前景。
具体实施方式
展示一下实例来说明本发明的某些实施例，且不应解释为限制本发明的范围。对本发明公开的内容可以同时从材料，方法和反应条件上进行许多改进，变化和改变。所有这些改进，变化和改变均确定地落入本发明的精神和范围之内。
实施例1:4-氨基-N-苄基苯磺酰胺
4-amino-N-benzylbenzenesulfonamide
氮气保护下，将4-氨基苯磺酰胺(172mg,1mmol)，[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(65mg,0.2mmol)，苯甲醇(130mg,1.2mmol)，叔戊醇(1mL)依次加到25mLSchlenk反应瓶中。混合物在120℃下反应12小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：88％。
1H NMR(500MHz,DMSO-d6)δ7.62(br s,1H,NH),7.44(d,J＝8.6Hz,2H,ArH),7.31-7.20(m,5H,ArH),6.60(d,J＝8.6Hz,2H,ArH),5.92(s,2H,NH2),3.87(s,2H,NCH2)；13C NMR(125MHz,DMSO-d6)δ152.4,138.0,128.4,127.5,127.0,125.6,112.6,46.0.
实施例2:N-(4-甲基苄基)-4-氨基苯磺酰胺
N-(4-methylbenzyl)-4-aminobenzenesulfonamide
氮气保护下，将4-氨基苯磺酰胺(172mg,1mmol)，[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(65mg,0.2mmol),对甲基苯甲醇(147mg,1.2mmol)，叔戊醇(1.0mL)依次加到25mL Schlenk反应瓶中。混合物在120℃下反应12小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：86％。
1H NMR(500MHz,DMSO-d6)δ7.55(br s,1H,NH),7.43(d,J＝8.6Hz,2H,ArH),7.10(q,J＝7.4Hz,4H,ArH),6.60(d,J＝8.6Hz,2H,ArH),5.91(s,2H,NH2),3.81(s,2H,NCH2),2.26(s,3H,CH3)；13C NMR(125MHz,DMSO-d6)δ152.4,136.0,135.0,128.7,128.4,127.5,125.6,112.6,45.8,20.6；HRMS-EI(70eV)m/z calcd for C14H16N2O2SNa[M+Na]+299.0830,found 299.0828.
实施例3:N-(4-异丙基苄基)-4-氨基苯磺酰胺
N-(4-isopropylbenzyl)-4-aminobenzenesulfonamide
氮气保护下，将4-氨基苯磺酰胺(172mg,1mmol)，[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(65mg,0.2mmol)，对异丙基苯甲醇(180mg,1.2mmol)，叔戊醇(1.0mL)依次加到25mL Schlenk反应瓶中。混合物在120℃下反应12小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：80％。
1H NMR(500MHz,DMSO-d6)δ7.55(br s,1H,NH),7.43(d,J＝8.5Hz,2H,ArH),7.14(s,4H,ArH),6.60(d,J＝8.5Hz,2H,ArH),5.91(s,2H,NH2),3.82(s,2H,NCH2),2.90-2.79(heptet,J＝6.9Hz,1H,CH),1.17(d,J＝7.0Hz,6H,2xCH3)；13C NMR(125MHz,DMSO-d6)δ152.4,147.2,135.3,128.4,127.6,126.0,125.6,112.6,45.9,33.1,23.9；HRMS-EI(70eV)m/z calcd for C16H20N2O2SNa[M+Na]+327.1143,found 327.1152.
实施例4:N-(3-甲氧基苄基)-4-氨基苯磺酰胺
N-(3-methoxybenzyl)-4-aminobenzenesulfonamide
氮气保护下，将4-氨基苯磺酰胺(172mg,1mmol)，[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(65mg,0.2mmol)，间甲氧基苯甲醇(166mg,1.2mmol)，叔戊醇(1.0mL)依次加到25mL Schlenk反应瓶中。混合物在120℃下反应12小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：84％。
1H NMR(500MHz,DMSO-d6)δ7.61(t,J＝6.3Hz,1H,NH),7.43(d,J＝8.6Hz,2H,ArH),7.19(t,J＝7.7Hz,1H,ArH),6.82-6.76(m,3H,ArH),6.60(d,J＝8.6Hz,2H,ArH),5.92(s,2H,NH2),3.85(d,J＝6.3Hz,2H,NCH2),3.70(s,3H,CH3)；13C NMR(125MHz,DMSO-d6)δ159.2,152.4,139.6,129.2,128.4,125.6,119.7,112.9,112.66,112.64,54.9,46.0；HRMS-EI(70eV)m/z calcd for C14H16N2O3SNa[M+Na]+315.0779,found315.0772.
实施例5:N-(4-甲氧基苄基)-4-氨基苯磺酰胺
N-(4-methoxybenzyl)-4-aminobenzenesulfonamide
氮气保护下，将4-氨基苯磺酰胺(172mg,1mmol)，[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(65mg,0.2mmol)，对甲氧基苯甲醇(166mg,1.2mmol)，叔戊醇(1.0mL)依次加到25mL Schlenk反应瓶中。混合物在120℃下反应12小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：85％。
1H NMR(500MHz,DMSO-d6)δ7.51(br s,1H,NH),7.43(d,J＝6.5Hz,2H,ArH),7.14(d,J＝5.9Hz,2H,ArH),6.84(d,J＝6.2Hz,2H,ArH),6.60(d,J＝6.8Hz,2H,ArH),5.90(s,2H,NH2),3.79(s,2H,NCH2),3.71(s,3H,OCH3)；13C NMR(125MHz,DMSO-d6)δ158.4,152.4,129.9,129.0,128.5,125.8,113.6,112.7,55.1,45.7；HRMS-EI(70eV)m/zcalcd forC14H16N2O3SNa[M+Na]+315.0779,found 315.0778.
实施例6:N-(2-氯苄基)-4-氨基苯磺酰胺
N-(2-chlorobenzyl)-4-aminobenzenesulfonamide
氮气保护下，将4-氨基苯磺酰胺(172mg,1mmol)，[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(65mg,0.2mmol)，邻氯苯甲醇(171mg,1.2mmol)，叔戊醇(1.0mL)依次加到25mL Schlenk反应瓶中。混合物在120℃下反应12小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：87％。
1H NMR(500MHz,DMSO-d6)δ7.71(br s,1H,NH),7.45(d,J＝8.6Hz,3H,ArH),7.40-7.37(m,1H,ArH),7.33-7.25(m,2H,ArH),6.60(d,J＝8.7Hz,2H,ArH),5.95(s,2H,NH2),3.95(s,2H,NCH2)；13C NMR(125MHz,DMSO-d6)δ152.5,135.3,131.9,129.6,128.9,128.8,128.5,127.0,125.2,112.7,43.5；HRMS-EI(70eV)m/z calcd for C13H13N2O2SClNa[M+Na]+319.0284,found 319.0276.
实施例7:N-(4-氯苄基)-4-氨基苯磺酰胺
N-(4-chlorobenzyl)-4-aminobenzenesulfonamide
氮气保护下，将4-氨基苯磺酰胺(172mg,1mmol)，[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(65mg,0.2mmol)，对氯苯甲醇(171mg,1.2mmol)，叔戊醇(1.0mL)依次加到25mL Schlenk反应瓶中。混合物在120℃下反应12小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：91％。
1H NMR(500MHz,DMSO-d6)δ7.68(br s,1H,NH),7.42(d,J＝8.7Hz,2H,ArH),7.34(d,J＝8.4Hz,2H,ArH),7.26(d,J＝8.5Hz,2H,ArH),6.60(d,J＝8.7Hz,2H,ArH),5.94(s,2H,NH2),3.86(s,2H,NCH2)；13C NMR(125MHz,DMSO-d6)δ152.5,137.2,131.5,129.3,128.4,128.1,125.4,112.6,42.3.
实施例8:N-(3,4-二氯苄基)-4-氨基苯磺酰胺
N-(3,4-dichlorobenzyl)-4-aminobenzenesulfonamide
氮气保护下，将4-氨基苯磺酰胺(172mg,1mmol)，[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(65mg,0.2mmol)，3,4-二氯苯甲醇(212mg,1.2mmol)，叔戊醇(1.0mL)依次加到25mL Schlenk反应瓶中。混合物在120℃下反应12小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：92％。
1H NMR(500MHz,DMSO-d6)δ7.75(br s,1H,NH),7.54(d,J＝8.2Hz,1H,ArH),7.45(d,J＝1.3Hz,1H,ArH),7.40(d,J＝8.7Hz,2H,ArH),7.24(dd,J＝8.3Hz and 1.4Hz,1H,ArH),6.59(d,J＝8.7Hz,2H,ArH),5.94(s,2H,NH2),3.90(s,2H,NCH2)；13C NMR(125MHz,DMSO-d6)δ152.6,139.6,130.7,129.4,128.4,127.8,125.4,112.6,44.8；HRMS-EI(70eV)m/z calcd for C13H12N2O2SCl2Na[M+Na]+352.9894,found 352.9881.
实施例9:N-(2-溴苄基)-4-氨基苯磺酰胺
N-(2-bromobenzyl)-4-aminobenzenesulfonamide
氮气保护下，将4-氨基苯磺酰胺(172mg,1mmol)，[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(65mg,0.2mmol)，邻溴苯甲醇(224mg,1.2mmol)，叔戊醇(1.0mL)依次加到25mL Schlenk反应瓶中。混合物在120℃下反应12小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：83％。
1H NMR(500MHz,DMSO-d6)δ7.73(br s,1H,NH),7.55(d,J＝7.9Hz,1H,ArH),7.45(d,J＝8.1Hz,3H,ArH),7.35(t,J＝7.4Hz,1H,ArH),7.20(t,J＝7.4Hz,1H,ArH),6.61(d,J＝8.3Hz,2H,ArH),5.95(s,2H,NH2),3.92(s,2H,NCH2)；13C NMR(125MHz,DMSO-d6)δ152.6,136.8,132.2,129.5,129.0,128.5,127.6,125.2,122.3,112.7,47.0；HRMS-EI(70eV)m/zcalcd for C13H13N2O2SBrNa[M+Na]+362.9779,found 362.9783.
实施例10:N-(4-溴苄基)-4-氨基苯磺酰胺
N-(4-bromobenzyl)-4-aminobenzenesulfonamide
氮气保护下，将4-氨基苯磺酰胺(172mg,1mmol)，[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(65mg,0.2mmol)，对溴苯甲醇(224mg,1.2mmol)，叔戊醇(1.0mL)依次加到25mL Schlenk反应瓶中。混合物在120℃下反应12小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：88％。
1H NMR(500MHz,DMSO-d6)δ7.68(t,J＝6.4Hz,1H,NH),7.48(d,J＝8.3Hz,2H,ArH),7.42(d,J＝8.6Hz,2H,ArH),7.20(d,J＝8.2Hz,2H,ArH),6.60(d,J＝8.6Hz,2H,ArH),5.93(s,2H,NH2),3.84(s,2H,NCH2)；13C NMR(125MHz,DMSO-d6)δ152,5,137.7,131.0,129.7,128.5,125.5,120.0,112.7,45.4；HRMS-EI(70eV)m/z calcd for C13H13N2O2SBrNa[M+Na]+362.9779,found 362.9768.
实施例11:N-(4-三氟甲氧基苄基)-4-氨基苯磺酰胺
N-(4-(trifluoromethoxy)benzyl)-4-aminobenzenesulfonamide
氮气保护下，将4-氨基苯磺酰胺(172mg,1mmol)，[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(65mg,0.2mmol)，对三氟甲氧基苯甲醇(231mg,1.2mmol)，叔戊醇(1.0mL)依次加到25mL Schlenk反应瓶中。混合物在120℃下反应12小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：90％。
1H NMR(500MHz,DMSO-d6)δ7.70(br s,1H,NH),7.42(d,J＝8.3Hz,2H,ArH),7.37(d,J＝7.3Hz,2H,ArH),7.28(d,J＝7.4Hz,2H,ArH),6.60(d,J＝7.7Hz,2H,ArH),5.93(s,2H,NH2),3.91(s,2H,NCH2)；13C NMR(125MHz,DMSO-d6)δ152.5,147.3,137.7,129.3,128.4,125.5,120.7,120.0(q,JC-F＝254.3Hz),112.6,45.2；HRMS-EI(70eV)m/z calcd forC14H13N2O3F3SNa[M+Na]+369.0497,found 369.0491.
实施例12:4-氨基-N-(萘-1-甲基)苯磺酰胺
4-amino-N-(naphthalen-1-ylmethyl)benzenesulfonamide
氮气保护下，将4-氨基苯磺酰胺(172mg,1mmol)，[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(65mg,0.2mmol)，1-萘甲醇(190mg,1.2mmol)，叔戊醇(1.0mL)依次加到25mL Schlenk反应瓶中。混合物在120℃下反应12小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：87％。
1H NMR(500MHz,DMSO-d6)δ8.07-8.03(m,1H,ArH),7.95-7.91(m,1H,ArH),7.85(dd,J＝7.5Hz and 1.8Hz,1H,ArH),7.64(br s,1H,NH),7.56-7.50(m,4H,ArH),7.45-7.40(m,2H,ArH),6.65(d,J＝8.5Hz,2H,ArH),5.96(s,2H,NH2),4.29(s,2H,NCH2)；13C NMR(125MHz,DMSO-d6)δ152.6,133.2,133.0,131.0,128.6,128.4,128.0,126.5,126.1,125.8,125.32,125.26,123.6,44.4；HRMS-EI(70eV)m/z calcd for C17H16N2O2SNa[M+Na]+335.0830,found 335.0831.
实施例13:4-氨基-N-二茂铁甲基苯磺酰胺
4-amino-N-(ferrocenemethyl)benzenesulfonamide
氮气保护下，将4-氨基苯磺酰胺(172mg,1mmol)，[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(65mg,0.2mmol)，二茂铁甲醇(259mg,1.2mmol)，叔戊醇(1.0mL)依次加到25mL Schlenk反应瓶中。混合物在120℃下反应12小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：80％。
1H NMR(500MHz,DMSO-d6)δ7.43(d,J＝8.6Hz,2H,ArH),7.28(t,J＝6.2Hz,1H,NH),6.61(d,J＝8.6Hz,2H,ArH),5.90(s,2H,NH2),4.11(s,5H,ferrocene H),4.08(t,J＝1.6Hz,2H,ferrocene H),4.05(t,J＝1.7Hz,2H,ferrocene H),3.62(d,J＝6.1Hz,2H,NCH2)；13C NMR(125MHz,DMSO-d6)δ152.3,128.4,125.8,112.6,84.4,68.3,68.1,67.4,42.0；HRMS-EI(70eV)m/z calcd for C17H18N2O2SFeSNa[M+Na]393.0336,found393.0346.
实施例14:4-氨基-N-(2-噻吩甲基)苯磺酰胺
4-amino-N-(thiophen-2-ylmethyl)benzenesulfonamide
氮气保护下，将4-氨基苯磺酰胺(172mg,1mmol)，[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(130mg,0.4mmol)，2-噻吩甲醇(137mg,1.2mmol)，叔戊醇(1.0mL)依次加到25mL Schlenk反应瓶中。混合物在120℃下反应12小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：74％。
1H NMR(500MHz,DMSO-d6)δ7.75(t,J＝6.1Hz,1H,NH),7.43(d,J＝8.4Hz,2H,ArH),7.40-7.38(m,1H,ArH),6.92-6.88(m,2H,ArH),6.60(d,J＝8.5Hz,2H,ArH),5.94(s,2H,NH2),4.05(d,J＝6.3Hz,2H,NCH2)；13C NMR(125MHz,DMSO-d6)δ152.5,141.1,128.5,126.6,125.6,125.4,125.3,112.7,41.4；HRMS-EI(70eV)m/z calcd for C11H12N2O2S2Na[M+Na]+291.0238,found 291.0245.
实施例15:4-氨基-N-丁基苯磺酰胺
4-amino-N-butylbenzenesulfonamide
氮气保护下，将4-氨基苯磺酰胺(172mg,1mmol)，[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(130mg,0.4mmol)，正丁醇(148mg,2mmol)，叔戊醇(1.0mL)依次加到25mLSchlenk反应瓶中。混合物在120℃下反应12小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：81％。
1H NMR(500MHz,DMSO-d6)δ7.40(d,J＝8.5Hz,2H,ArH),7.01(t,J＝5.2Hz,1H,NH),6.60(d,J＝8.5Hz,2H,ArH),5.88(s,2H,NH2),2.63(quart,J＝6.5Hz,2H,NCH2),1.31(quint,J＝7.0Hz,2H,CH2),1.22(sext,J＝7.2Hz,2H,CH2),0.79(t,J＝7.2Hz,3H,CH3)；13CNMR(125MHz,DMSO-d6)δ152.4,128.4,125.8,112.7,42.2,31.0,19.3,13.5.
实施例16:4-氨基-N-正己基苯磺酰胺
4-amino-N-hexylbenzenesulfonamide
氮气保护下，将4-氨基苯磺酰胺(172mg,1mmol)，[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(130mg,0.4mmol)，正己醇(204mg,2mmol)，叔戊醇(1.0mL)依次加到25mLSchlenk反应瓶中。混合物在120℃下反应12小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：78％。
1H NMR(500MHz,DMSO-d6)δ7.39(d,J＝8.4Hz,2H,ArH),7.02(t,J＝5.4Hz,1H,NH),6.60(d,J＝8.4Hz,2H,ArH),5.89(s,2H,NH2),2.62(quart,J＝6.5Hz,2H,NCH2),1.32(quint,J＝6.7Hz,2H,CH2),1.25-1.11(m,6H,3xCH2),0.82(t,J＝6.8Hz,3H,CH3)；13C NMR(125MHz,DMSO-d6)δ152.3,128.4,125.6,112.6,42.4,30.8,28.8,25.8,21.9,13.8；HRMS-EI(70eV)m/z calcd for C12H20N2O2SNa[M+Na]+279.1143,found279.1151.
实施例17:4-氨基-N-正辛基苯磺酰胺
4-amino-N-octylbenzenesulfonamide
氮气保护下，将4-氨基苯磺酰胺(172mg,1mmol)，[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(130mg,0.4mmol)，正辛醇(260mg,2mmol)，叔戊醇(1.0mL)依次加到25mLSchlenk反应瓶中。混合物在120℃下反应12小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：78％。
1H NMR(500MHz,DMSO-d6)δ7.39(d,J＝7.6Hz,2H,ArH),7.01(t,J＝5.3Hz,1H,NH),6.59(d,J＝7.6Hz,2H,ArH),5.88(s,2H,NH2),2.62(quart,J＝5.8Hz,2H,NCH2),1.36-1.12(m,12H,6xCH2),0.84(t,J＝6.1Hz,3H,CH3)；13C NMR(125MHz,DMSO-d6)δ152.33,128.35,125.60,112.58,42.42,31.16,28.83,28.54,28.51,26.09,22.05,13.93.
实施例18:4-氨基-N-异戊基苯磺酰胺
4-amino-N-isopentylbenzenesulfonamide
氮气保护下，将4-氨基苯磺酰胺(172mg,1mmol)，[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(130mg,0.4mmol)，异戊醇(176mg,2mmol)，叔戊醇(1.0mL)依次加到25mLSchlenk反应瓶中。混合物在120℃下反应12小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：80％。
1H NMR(500MHz,DMSO-d6)δ7.39(d,J＝8.5Hz,2H,ArH),6.98(t,J＝5.3Hz,1H,NH),6.60(d,J＝8.6Hz,2H,ArH),5.87(s,2H,NH2),2.64(quart,J＝6.6Hz,2H,NCH2),1.53(heptet,J＝6.6Hz,1H,CH),1.22(quart,J＝7.1Hz,2H,CH2),0.77(d,J＝6.6Hz,6H,2xCH3)；13C NMR(125MHz,DMSO-d6)δ152.4,128.4,125.7,112.7,40.7,37.8,24.9,22.2.
实施例19:4-氨基-N-(2-乙基己基)苯磺酰胺
4-amino-N-(2-ethylhexyl)benzenesulfonamide
氮气保护下，将4-氨基苯磺酰胺(172mg,1mmol)，[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(130mg,0.4mmol)，2-乙基己醇(260mg,2mmol)，叔戊醇(1.0mL)依次加到25mL Schlenk反应瓶中。混合物在120℃下反应12小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：85％。
1H NMR(500MHz,DMSO-d6)δ7.39(s,2H,ArH),6.97(s,1H,NH),6.59(s,2H,ArH),5.87(s,2H,NH2),2.52(s,2H,NCH2),1.32-1.05(m,9H,CH and 4xCH2),0.83(s,3H,CH3),0.73(s,3H,CH3)；13C NMR(125MHz,DMSO-d6)δ152.3,128.3,125.8,112.6,45.3,38.5,30.0,28.1,23.3,22.4,13.9,10.5；HRMS-EI(70eV)m/z calcd for C14H24N2O2SNa[M+Na]+307.1456,found 307.1464.
实施例20:4-氨基-N-(环己基甲基)苯磺酰胺
4-amino-N-(cyclohexylmethyl)benzenesulfonamide
氮气保护下，将4-氨基苯磺酰胺(172mg,1mmol)，[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(130mg,0.4mmol)，环己基甲醇(228mg,2mmol)，叔戊醇(1.0mL)依次加到25mL Schlenk反应瓶中。混合物在120℃下反应12小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：83％。
1H NMR(500MHz,DMSO-d6)δ7.39(d,J＝7.5Hz,2H,ArH),7.05(br s,1H,NH),6.59(d,J＝8.1Hz,2H,ArH),5.89(s,2H,NH2),2.45(t,J＝5.9Hz,2H,NCH2),1.67-1.52(m,5H,2xCH2,CH),1.35-1.20(m,1H,CH),1.18-1.01(m,3H,CH2,CH),0,82-0.70(m,2H,CH2)；13C NMR(125MHz,DMSO-d6)δ152.3,128.4,125.9,112.7,48.8,37.2,30.3,26.0,25.3；HRMS-EI(70eV)m/z calcd for C13H20N2O2SNa[M+Na]+291.1143,found291.1146.
实施例21:4-氨基-N-(环戊基)苯磺酰胺
4-amino-N-(cyclopentyl)benzenesulfonamide
氮气保护下，将4-氨基苯磺酰胺(172mg,1mmol)，[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(65mg,0.2mmol)，环戊醇(172mg,2mmol)，叔戊醇(1.0mL)依次加到25mLSchlenk反应瓶中。混合物在150℃下反应24小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：50％。
1H NMR(500MHz,DMSO-d6)δ7.40(d,J＝8.6Hz,2H,ArH),7.10(d,J＝7.0Hz,1H,NH),6.59(d,J＝8.6Hz,2H,ArH),5.88(s,2H,NH2),3.27(sext,J＝6.7Hz,1H,NCH),1.59-1.46(m,4H,2xCH2),1.40-1.31(m,2H,CH2),1.30-1.22(m,2H,CH2)；13C NMR(125MHz,DMSO-d6)δ152.3,128.4,126.6,112.6,54.3,32.4,22.8.
实施例22:4-氨基-N-(环己基)苯磺酰胺
4-amino-N-(cyclohexyl)benzenesulfonamide
氮气保护下，将4-氨基苯磺酰胺(172mg,1mmol)，[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(65mg,0.2mmol)，环己醇(200mg,2mmol)，叔戊醇(1.0mL)依次加到25mLSchlenk反应瓶中。混合物在150℃下反应24小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：56％。
1H NMR(500MHz,DMSO-d6)δ7.41(d,J＝8.4Hz,2H,ArH),7.10(d,J＝7.0Hz,1H,NH),6.58(d,J＝8.4Hz,2H,ArH),5.87(s,2H,NH2),2.78(s,1H,NCH),1.61-1.50(m,4H,2xCH2),1.46-1.38(m,1H,CH),1.14-0.98(m,5H,CH and 2xCH2)；13C NMR(125MHz,DMSO-d6)δ152.2,128.2,127.3,112.6,51.8,33.2,25.0,24.4
实施例23:4-氨基-N-苄基-3-溴苯磺酰胺
4-amino-N-benzyl-3-bromobenzenesulfonamide
氮气保护下，将4-氨基-3-溴苯磺酰胺(251mg,1mmol)，[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(65mg,0.2mmol)，苯甲醇(130mg,1.2mmol)，叔戊醇(1.0mL)依次加到25mL Schlenk反应瓶中。混合物在120℃下反应12小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：82％。
1H NMR(500MHz,DMSO-d6)δ7.82(br s,1H,NH),7.68(s,1H,ArH),7.46(d,J＝7.5Hz,1H,ArH),7.30-7.20(m,5H,ArH),6.83(d,J＝8.4Hz,1H,ArH),6.12(s,2H,NH2),3.91(s,2H,NCH2)；13C NMR(125MHz,DMSO-d6)δ149.3,137.7,131.1,128.1,127.6,127.3,127.0,114.1,105.8,46.1；HRMS-EI(70eV)m/z calcd for C13H13BrN2O2SNa[M+Na]+362.9774,found 362.9779.
实施例24:4-氨基-N-苄基-3,5-二溴苯磺酰胺
4-amino-N-benzyl-3,5-dibromobenzenesulfonamide
氮气保护下，将4-氨基-3,5-二溴苯磺酰胺(330mg,1mmol)，[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(65mg,0.2mmol)，苯甲醇(130mg,1.2mmol)，叔戊醇(1.0mL)依次加到25mL Schlenk反应瓶中。混合物在120℃下反应12小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：84％。
1H NMR(500MHz,DMSO-d6)δ8.00(br s,1H,NH),7.70(s,2H,ArH),7.29-7.18(m,5H,ArH),6.12(s,2H,NH2),3.97(s,2H,NCH2)；13C NMR(125MHz,DMSO-d6)δ146.2,137.4,130.3,128.9,128.1,127.6,127.1,106.3,46.1；HRMS-EI(70eV)m/z calcd for C13H12Br2N2O2SNa[M+Na]+440.8884,found 440.8877.
实施例25:4-氨基-N-苄基-3,5-二氯苯磺酰胺
4-amino-N-benzyl-3,5-dichlorobenzenesulfonamide
氮气保护下，将4-氨基-3,5-二氯苯磺酰胺(241mg,1mmol),[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(65mg,0.2mmol)，苯甲醇(130mg,1.2mmol)，叔戊醇(1.0mL)依次加到25mL Schlenk反应瓶中。混合物在120℃下反应12小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：86％。
1H NMR(500MHz,DMSO-d6)δ7.99(br s,1H,NH),7.53(s,2H,ArH),7.29-7.18(m,5H,ArH),6.33(s,2H,NH2),3.97(s,2H,NCH2)；13C NMR(125MHz,DMSO-d6)δ144.6,137.4,128.1,127.6,127.5,127.1,126.5,117.1,46.2；HRMS-EI(70eV)m/z calcd for C13H12Cl2N2O2SNa[M+Na]+352.9894,found 352.9893.
实施例26:3-氨基-N-苄基苯磺酰胺
3-amino-N-benzylbenzenesulfonamide
氮气保护下，将3-氨基苯磺酰胺(172mg,1mmol)，[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(65mg,0.2mmol)，苯甲醇(130mg,1.2mmol)，叔戊醇(1.0mL)依次加到25mLSchlenk反应瓶中。混合物在120℃下反应12小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：83％。
1H NMR(500MHz,DMSO-d6)δ7.94(t,J＝6.3Hz,1H,NH),7.33-7.17(m,6H,ArH),7.02(s,1H,ArH),6.91(d,J＝7.5Hz,1H,ArH),6.76(dd,J＝8.0Hz and 1.5Hz,1H,ArH),5.57(s,2H,NH2),3.94(d,J＝6.5Hz,2H,NCH2)；13C NMR(125MHz,DMSO-d6)δ149.3,141.1,137.9,129.5,128.2,127.5,127.1,117.2,113.2,111.1,46.1.
实施例27:5-氨基-N-苄基-2-甲基苯磺酰胺
5-amino-N-benzyl-2-methylbenzenesulfonamide
氮气保护下，将5-氨基-2-甲基苯磺酰胺(186mg,1mmol)，[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(65mg,0.2mmol)，苯甲醇(130mg,1.2mmol)，叔戊醇(1.0mL)依次加到25mL Schlenk反应瓶中。混合物在120℃下反应12小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：79％。
1H NMR(500MHz,DMSO-d6)δ7.97(br s,1H,NH),7.38-7.08(m,6H,ArH),6.99(s,1H,ArH),6.67(s,1H,ArH),5.29(s,2H,NH2),3.98(s,2H,NCH2),2.37(s,3H,CH3)；13CNMR(125MHz,DMSO-d6)δ146.8,138.7,138.1,132.8,128.1,127.4,127.0,122.0,117.2,113.8,45.7,18.7；HRMS-EI(70eV)m/z calcd for C14H16N2O2SNa[M+Na]+299.0830,found299.0838.
实施例28:2-氨基-N-苄基苯磺酰胺
2-amino-N-benzylbenzenesulfonamide
氮气保护下，将邻氨基苯磺酰胺(172mg,1mmol)，[Cp*IrCl2]2(8mg,0.01mmol,1mol％)，碳酸铯(65mg,0.2mmol)，苯甲醇(130mg,1.2mmol)，叔戊醇(1.0mL)依次加到25mLSchlenk反应瓶中。混合物在120℃下反应12小时后，冷却到室温，真空减压除去溶剂。然后通过柱层析(展开剂：乙酸乙酯/正己烷)得到纯净的目标化合物，产率：76％。
1H NMR(500MHz,DMSO-d6)δ8.04(br s,1H,NH),7.51(dd,J＝8.0Hz and 1.4Hz,1H,ArH),7.30-7.19(m,6H,ArH),6.81(dd,J＝8.2Hz and 0.7Hz,1H,ArH),6.63-6.57(m,1H,ArH),5.93(s,2H,NH2),3.93(s,2H,NCH2)；13C NMR(125MHz,DMSO-d6)δ146.2,137.7,133.4,129.0,128.1,127.4,127.0,120.0,116.8,115.1,45.6；HRMS-EI(70eV)m/zcalcd forC13H14N2O2SNa[M+Na]+285.0674,found 285.0672.
实施例29:
除用碳酸钾(27.6mg,0.2mmol,0.2equiv.)代替碳酸铯，其它反应原料，条件和产物同实施例1，产率：88％
实施例30:
除用磷酸钾(42.4mg,0.2mmol,0.2equiv.)代替碳酸铯，其它反应原料，条件和产物同实施例1，产率：88％
实施例31:
除反应温度为110℃,其它反应原料，条件和产物同实施例1，产率：79％.
实施例32:
除Cs2CO3用量为(0.1equiv),其它反应原料，条件和产物同实施例1，产率：77％。
Claims (4)
1.一种合成氨基‐(N‐烷基)苯磺酰胺的方法，其特征在于，所述产物
是通过氨基苯磺酰胺Ⅱ
与化合物醇Ⅲ
在铱络合物催化剂[Cp*IrCl2]2和碱碳酸铯的存在下发生反应，
其中，R1代表卤素和甲基中任一基团；R2、R3代表氢、C4‐C8烷基、甲基苯基、异丙基苯基、甲氧基苯基、三氟甲基苯基、三氟甲氧基苯基、卤代苯基、噻吩基和萘基中任一基团；Cp*＝五甲基环戊二烯基。
2.如权利要求1所述的合成氨基‐(N‐烷基)苯磺酰胺的方法，其特征在于，铱络合物催化剂用量相对于氨基苯磺酰胺的摩尔比为1mol％；碱相对于氨基苯磺酰胺摩尔比为0.2‐0.4当量；化合物醇相对于氨基苯磺酰胺摩尔比为1.2:1。
3.如权利要求1所述的合成氨基‐(N‐烷基)苯磺酰胺的方法，其特征在于，反应在120‐150℃下进行。
4.如权利要求1所述的合成氨基‐(N‐烷基)苯磺酰胺的方法，其特征在于，反应在120℃下进行。
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| CN107739322B (zh) * | 2017-10-19 | 2020-06-23 | 济南大学 | 一种磺酰胺类化合物的合成方法 |
| CN110857301B (zh) * | 2018-08-23 | 2022-07-22 | 南京理工大学 | 一种制备tnni3k抑制剂的方法 |
| CN112047865B (zh) * | 2019-06-05 | 2022-12-02 | 南京理工大学 | 一种在水中合成n-烷基磺酰胺的方法 |
| CN110499091B (zh) * | 2019-08-16 | 2021-04-27 | 安徽省优亲科技发展有限公司 | 一种纳米银-壳聚糖改性聚苯磺酰胺抗菌涂层及其制法 |
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