CN108558734A - 一种铜催化合成2-芳基-3-芳基磺酰基-1h-吲哚的方法 - Google Patents
一种铜催化合成2-芳基-3-芳基磺酰基-1h-吲哚的方法 Download PDFInfo
- Publication number
- CN108558734A CN108558734A CN201810423907.7A CN201810423907A CN108558734A CN 108558734 A CN108558734 A CN 108558734A CN 201810423907 A CN201810423907 A CN 201810423907A CN 108558734 A CN108558734 A CN 108558734A
- Authority
- CN
- China
- Prior art keywords
- aryl
- benzene
- azidos
- method described
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 22
- 239000010949 copper Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910001868 water Inorganic materials 0.000 claims abstract description 29
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012046 mixed solvent Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000007800 oxidant agent Substances 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 239000000376 reactant Substances 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 72
- -1 aryl ethane Chemical compound 0.000 claims description 41
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 24
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 24
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 13
- 239000012074 organic phase Substances 0.000 claims description 13
- 239000012043 crude product Substances 0.000 claims description 12
- 239000003480 eluent Substances 0.000 claims description 12
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 12
- 238000010898 silica gel chromatography Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000741 silica gel Substances 0.000 claims description 11
- 229910002027 silica gel Inorganic materials 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- UORYAOZFMGBGAC-UHFFFAOYSA-N n-methylbenzenesulfonohydrazide Chemical compound CN(N)S(=O)(=O)C1=CC=CC=C1 UORYAOZFMGBGAC-UHFFFAOYSA-N 0.000 claims description 8
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 7
- 238000005292 vacuum distillation Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- GZWXEFRPSWBAGC-UHFFFAOYSA-N copper;trifluoromethanesulfonic acid Chemical compound [Cu].OS(=O)(=O)C(F)(F)F GZWXEFRPSWBAGC-UHFFFAOYSA-N 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- VJRITMATACIYAF-UHFFFAOYSA-N benzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC=C1 VJRITMATACIYAF-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 4
- 125000004391 aryl sulfonyl group Chemical group 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 abstract 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 abstract 1
- 125000000524 functional group Chemical group 0.000 abstract 1
- 231100000053 low toxicity Toxicity 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 30
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 238000001514 detection method Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000000926 separation method Methods 0.000 description 12
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 238000001819 mass spectrum Methods 0.000 description 10
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical class OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 10
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 10
- 238000010828 elution Methods 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- BULFKQNIZODZDC-UHFFFAOYSA-N 3-sulfonylindole Chemical class C1=CC=C2C(=S(=O)=O)C=NC2=C1 BULFKQNIZODZDC-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000005311 nuclear magnetism Effects 0.000 description 4
- MEJAPGGFIJZHEJ-UHFFFAOYSA-N 5-acetamido-1,3,4-thiadiazole-2-sulfonyl chloride Chemical compound CC(=O)NC1=NN=C(S(Cl)(=O)=O)S1 MEJAPGGFIJZHEJ-UHFFFAOYSA-N 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 150000002475 indoles Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- TYQQUJVRDDRJIR-UHFFFAOYSA-N 3-(4-methylphenyl)sulfonyl-2-phenyl-1h-indole Chemical class C1=CC(C)=CC=C1S(=O)(=O)C1=C(C=2C=CC=CC=2)NC2=CC=CC=C12 TYQQUJVRDDRJIR-UHFFFAOYSA-N 0.000 description 2
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical class C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 2
- 125000001041 indolyl group Chemical group 0.000 description 2
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- LYFRUBQVZGVXPR-UHFFFAOYSA-N 1h-indole-3-thiol Chemical class C1=CC=C2C(S)=CNC2=C1 LYFRUBQVZGVXPR-UHFFFAOYSA-N 0.000 description 1
- NUNHASVOYPUZPP-UHFFFAOYSA-N 2-sulfonyl-1,3-dihydroindole Chemical class C1=CC=C2NC(=S(=O)=O)CC2=C1 NUNHASVOYPUZPP-UHFFFAOYSA-N 0.000 description 1
- 238000005679 Batcho-Leimgruber synthesis reaction Methods 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 229930195212 Fischerindole Natural products 0.000 description 1
- 241000713772 Human immunodeficiency virus 1 Species 0.000 description 1
- 208000019695 Migraine disease Diseases 0.000 description 1
- 229940123730 Orexin receptor antagonist Drugs 0.000 description 1
- 241000255964 Pieridae Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000003797 alkaloid derivatives Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 239000005557 antagonist Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 206010027599 migraine Diseases 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 239000002858 neurotransmitter agent Substances 0.000 description 1
- 229940042402 non-nucleoside reverse transcriptase inhibitor Drugs 0.000 description 1
- 239000002726 nonnucleoside reverse transcriptase inhibitor Substances 0.000 description 1
- 239000002767 noradrenalin uptake inhibitor Substances 0.000 description 1
- 229940127221 norepinephrine reuptake inhibitor Drugs 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 1
- GQHWSLKNULCZGI-UHFFFAOYSA-N trifluoromethoxybenzene Chemical compound FC(F)(F)OC1=CC=CC=C1 GQHWSLKNULCZGI-UHFFFAOYSA-N 0.000 description 1
- SEDZOYHHAIAQIW-UHFFFAOYSA-N trimethylsilyl azide Chemical compound C[Si](C)(C)N=[N+]=[N-] SEDZOYHHAIAQIW-UHFFFAOYSA-N 0.000 description 1
- ZISSAWUMDACLOM-UHFFFAOYSA-N triptane Chemical class CC(C)C(C)(C)C ZISSAWUMDACLOM-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Indole Compounds (AREA)
Abstract
本发明公开了一种铜催化合成2‑芳基‑3‑芳基磺酰基‑1H‑吲哚的方法:以三氟甲磺酸铜为催化剂,过氧化苯甲酸叔丁酯为氧化剂,1‑叠氮基‑2‑(芳基乙炔基)苯以及芳基磺酰肼为反应物,乙腈与水(VMeCN:H2O=2:1)为混合溶剂,室温下搅拌8h,反应结束后反应液后处理得到2‑芳基‑3‑芳基磺酰基‑1H‑吲哚。本发明的合成方法具有催化剂用量小、毒性小,原料易制得,官能团普适性较好等特点。
Description
技术领域
本发明属于有机合成领域,具体涉及一种铜催化合成2-芳基-3-芳基磺酰基-1H-吲哚的方法。
背景技术
吲哚类化合物广泛存在于自然界中,尤其是含有吲哚结构的生物碱在生物体内展现出优越的生物活性,例如triptan类药物具有治疗偏头痛的药效;aplysinopsin类化合物可以作为拮抗剂;色胺类化合物是一种抑制性神经递质。自1866年Baeyer首次分离出吲哚类化合物后,吲哚类化合物的合成方法研究就一直没有中断(蒋金芝,王艳.Fischer吲哚合成法的研究进展[J].有机化学,2006,08.)。常见的吲哚类合成方法有:Bartoli、Batcho-Leimgruber、Fischer、 Nenitzescu、Reissert等反应和过渡金属催化的合成方法(Bartoli,G.;Dalpozzo,R.;Nardi,M. Chem.Soc.Rev.2014,43,4728)。其中,3-磺酰基吲哚衍生物由于独特的生物活性和潜在的应用价值受到了合成工作者的关注。例如,5-氯-3-(苯基磺酰基)-1H-吲哚-2-甲酰胺是一种新的HIV-1非核苷逆转录酶抑制剂;N,N-二甲基-2-(3-苯基磺酰基)-4-乙胺基-1H-吲哚可用作去甲肾上腺素再摄取抑制剂或5-HT2A受体拮抗剂;N,N-二甲基-2-(3-苯基磺酰基)-1- 乙酰胺基吲哚是一种食欲素受体拮抗剂。
到目前为止,合成3-磺酰基吲哚衍生物的方法大致有三种(式1)。第一种,过渡金属催化下特定的前体发生环化反应得到吲哚环产物[(a)Nakamura,I.;Yamagishi,U.;Song,D.;Konta,S.; Yamamoto,Y.Angew.Chem.,Int.Ed.2007,46,2284.(b)Stokes,B.J.;Liu,S.;Driver,T.G.J.Am.Chem.Soc. 2011,133,4702.];第二种,吲哚化合物C3位直接磺酰基化得到目标产物(Qiu,J.K.;Hao,W.J.;Wang, D.C.;Wei,P.;Sun,J.;Jiang,B.;Tu,S.J.Chem.Commun.2014,50,14782.);第三种,3-巯基吲哚衍生物氧化得到3-磺酰基吲哚衍生物[(a)Chen,Y.;Cho,C.H.;Shi,F.;Larock,R.C.J.Org.Chem.2009,74,6802.(b)Vedejs,E.;Little,J.D.J.Org.Chem.2004,69,1794.]。但是上述方法大多需要昂贵的金属催化剂(例如:金等),复杂的实验操作或是苛刻的反应条件,而这些特殊的条件限制了这些方法在合成中的应用。
式1已报道的3-磺酰基吲哚合成方法发明内容
因此,开发利用廉价微量催化剂、易得的原料合成2-芳基-3-芳基磺酰基-1H-吲哚的方法具有重要的价值。
发明内容
本发明的目的在于提供一种铜催化合成2-芳基-3-芳基磺酰基-1H-吲哚的方法,该方法具有原料廉价易得,催化剂廉价、用量小,条件温和,反应操作简便,具有良好的工业应用前景等优点。
为实现上述目的,本发明采用如下技术方案:
一种铜催化合成2-芳基-3-芳基磺酰基-1H-吲哚的方法,其特征在于:在氮气氛中以三氟甲磺酸铜为催化剂,过氧化苯甲酸叔丁酯为氧化剂,1-叠氮基-2-(芳基乙炔基)苯以及芳基磺酰肼为反应物,乙腈与水(VMeCN:H2O=2:1)为混合溶剂,反应后得到2-苯基-3-甲苯磺酰基-1H-吲哚,化学反应式是:
其中,R1选自氢、烷基、卤素、氰基等;R2选自芳基、取代芳基、杂环芳基等;R3选自烷基、硝基、卤素、三氟甲基、三氟甲氧基、芳杂环等。
优选的,芳基磺酰肼为下述式1-14中的任意一种,1-叠氮基-2-(芳基乙炔基)苯为下述式15-26中的任意一种;
最优的为对甲苯磺酰肼与3-(2-叠氮基苯基乙炔基)噻吩制得2-(3-噻吩基)-3-对甲苯磺酰基-1H-吲哚。
所述的铜催化合成2-芳基-3-芳基磺酰基-1H-吲哚的方法具体步骤如下:在氮气氛围下向反应试管中加入三氟甲磺酸铜、过氧化苯甲酸叔丁酯、对甲基苯磺酰肼、1-叠氮基-2-(芳基乙炔基)苯和乙腈与水的混合溶剂,并放入聚四氟乙烯磁石一粒,室温下搅拌反应8h后, TLC检测反应完成,把反应液用乙酸乙酯萃取后,有机相完全转移至圆底烧瓶中,加适量 200-300目硅胶,减压蒸馏除去有机溶剂,得到的粗产物通过硅胶柱层析,以乙酸乙酯和石油醚为洗脱剂进行洗脱,得到2-芳基-3-芳基磺酰基-1H-吲哚。所述的三氟甲磺酸铜、过氧化苯甲酸叔丁酯、对甲基苯磺酰肼、1-叠氮基-2-(芳基乙炔基)苯的摩尔比为0.2:2.5:2:1。
本发明的有益效果在于:本发明原料1-叠氮基-2-(芳基乙炔基)苯以及芳基苯磺酰肼的制取非常容易,催化剂用量非常小,普遍收率较好,并且操作简单,具有良好的工业应用前景。
具体实施方式
为了使本发明所述的内容更加便于理解,下面结合具体实施例对本发明所述的技术方案作进一步的说明,但本发明不仅限于此。
原料芳基磺酰肼的制取:氮气氛围下,芳基磺酰氯(1.0equiv,2mmol)加入到装有磁力搅拌子和四氢呋喃溶液的50mL圆底烧瓶中。将烧瓶置于冰水浴,逐滴加入水合肼(2.5equiv,5mmol)。冰水浴下反应30分钟后,加入乙酸乙酯淬灭反应。用饱和食盐水和乙酸乙酯萃取,有机相用无水硫酸钠干燥,过滤。将滤液在正己烷溶液中重结晶,收集固体,即芳基磺酰肼。
原料1-叠氮基-2-(苯基乙炔基)苯的制取:将取代的卤代烃(1.0equiv,10mmol)、双三苯基膦二氯化钯(0.02equiv,0.14g)、碘化亚铜(0.01equiv,0.019g)加入到装有磁力搅拌子的100mL圆底烧瓶中,氮气保护,再加入40mL三乙胺。室温下搅拌加入取代的炔烃(1.2 equiv,12mmol),然后升温至50℃,反应2-5小时。TLC检测反应至完全,用乙酸乙酯和蒸馏水萃取,再用饱和食盐水洗涤,加入无水硫酸钠干燥,将溶剂旋干进行柱层析分离得到2- (芳基乙炔基)苯胺。随后将2-(芳基乙炔基)苯胺(1.0equiv,5mmol)加入到50mL圆底烧瓶中,加入25mL乙腈和搅拌子,置于冰水浴中。逐滴加入亚硝酸叔丁酯(1.5equiv,7.5mmol),搅拌5分钟后再逐滴加入叠氮三甲基硅烷(1.2equiv,6mmol)。反应2小时后,TLC 检测反应完全。过滤,滤液旋干进行柱层析分离得到1-叠氮基-2-(苯基乙炔基)苯。
实施例1
在氮气氛围下向反应试管中加入0.04mmol三氟甲磺酸铜、0.5mmol过氧化苯甲酸叔丁酯、0.4mmol对甲基苯磺酰肼、0.2mmol1-叠氮基-2-(苯基乙炔基)苯,2mL乙腈与水(VMeCN:H2O=2:1)的混合溶剂和聚四氟乙烯磁石一粒,室温下搅拌反应8h后,TLC检测反应完成,把反应液用乙酸乙酯萃取后,有机相完全转移至圆底烧瓶中,加适量200-300目硅胶,减压蒸馏除去有机溶剂,得到的粗产物通过硅胶柱层析,以乙酸乙酯和石油醚为洗脱剂进行洗脱,得到2-苯基-3-对甲苯基磺酰基-1H-吲哚(分离产率88%)。以下是产物的核磁共振表征数据和高分辨质谱数据:
1H NMR(400MHz,CDCl3)δ9.10(s,1H),8.24–8.13(m,1H),7.53–7.46(m,4H),7.39(t,J=7.2Hz,1H),7.35–7.29(m,3H),7.23(m,2H),7.05(d,J=8.0Hz,2H),2.28(s,3H).13CNMR(100MHz,CDCl3)δ143.0,142.6,141.1,134.7,130.2,130.1,129.7,129.3,128.0,126.3, 125.9,123.8,122.5,120.7,112.8,111.5,21.4.HRMS(ESI):m/z[M+H]+calcd forC21H18NO2S+: 348.1053,found:348.1057.
实施例2
在氮气氛围下向反应试管中加入0.04mmol三氟甲磺酸铜、0.5mmol过氧化苯甲酸叔丁酯、0.4mmol对氟苯磺酰肼、0.2mmol 1-叠氮基-2-(苯基乙炔基)苯,2mL乙腈与水(VMeCN:H2O=2:1)的混合溶剂和聚四氟乙烯磁石一粒,室温下搅拌反应8h后,TLC检测反应完成,把反应液用乙酸乙酯萃取后,有机相完全转移至圆底烧瓶中,加适量200-300目硅胶,减压蒸馏除去有机溶剂,得到的粗产物通过硅胶柱层析,以乙酸乙酯和石油醚为洗脱剂进行洗脱,得到3–(4-氟苯基磺酰基)-2-苯基-1H-吲哚(分离产率80%)。以下是产物的核磁共振表征数据和高分辨质谱数据:
1H NMR(400MHz,CDCl3)δ8.73(s,1H),8.32–8.21(m,1H),7.67-7.63(m,2H),7.55(d,J=7.2Hz,2H),7.51–7.38(m,4H),7.36–7.28(m,2H),6.95(t,J=8.4Hz,2H).13C NMR(100MHz,CDCl3)δ142.6,134.5,130.1(d,2JC-F=22.9Hz),129.9,129.1(d,3JC-F=9.3Hz),128.5, 128.3,125.8,124.1,122.8,120.8,118.1(d,1JC-F=252Hz),115.8(d,2JC-F=22.4Hz),111.3.HRMS (ESI):m/z[M+H]+calcd for C20H15FNO2S:352.0802,found:352.0808.
实施例3
在氮气氛围下向反应试管中加入0.04mmol三氟甲磺酸铜、0.5mmol过氧化苯甲酸叔丁酯、0.4mmol对甲基苯磺酰肼、0.2mmol 1-叠氮基-4-氟-2-(苯基乙炔基)苯,2mL乙腈与水 (VMeCN:H2O=2:1)的混合溶剂和聚四氟乙烯磁石一粒,室温下搅拌反应8h后,TLC检测反应完成,把反应液用乙酸乙酯萃取后,有机相完全转移至圆底烧瓶中,加适量200-300目硅胶,减压蒸馏除去有机溶剂,得到的粗产物通过硅胶柱层析,以乙酸乙酯和石油醚为洗脱剂进行洗脱,得到5-氟-2-苯基-3-甲苯磺酰基-1H-吲哚(分离产率86%)。以下是产物的核磁共振表征数据和高分辨质谱数据:
1H NMR(400MHz,CDCl3)δ9.20(s,1H),7.85(d,J=9.6Hz,1H),7.50–7.43(m,4H),7..41-7.37(m,1H),7.34–7.25(m,3H),7.07(d,J=8.0Hz,2H),7.00-6.95(m,1H),2.30(s,3H). 13C NMR(100MHz,CDCl3)δ159.2(d,1JC-F=237Hz),143.9,143.3,140.8,131.1,130.1,129.9, 129.8,129.4,128.1,126.6(d,3JC-F=13Hz),126.2,112.5(3JC-F=10Hz),112.5(2JC-F=26.4Hz), 112.3,106.1(2JC-F=25.9Hz),21.5.HRMS(ESI):m/z[M+H]+calcd forC21H17FNOS:366.0959, found:366.0962.
实施例4
在氮气氛围下向反应试管中加入0.04mmol三氟甲磺酸铜、0.5mmol过氧化苯甲酸叔丁酯、0.4mmol对甲基苯磺酰肼、0.2mmol 1-叠氮基-4-氯-2-(苯基乙炔基)苯,2mL乙腈与水 (VMeCN:H2O=2:1)的混合溶剂和聚四氟乙烯磁石一粒,室温下搅拌反应8h后,TLC检测反应完成,把反应液用乙酸乙酯萃取后,有机相完全转移至圆底烧瓶中,加适量200-300目硅胶,减压蒸馏除去有机溶剂,得到的粗产物通过硅胶柱层析,以乙酸乙酯和石油醚为洗脱剂进行洗脱,得到5-氯-2-苯基-3-甲苯磺酰基-1H-吲哚(分离产率85%)。以下是产物的核磁共振表征数据和高分辨质谱数据:
1H NMR(400MHz,CDCl3)δ8.63(s,1H),8.29(s,1H),7.58–7.42(m,7H),7.31-7.27(m,2H),7.11(d,J=8.4Hz,2H),2.32(s,3H).13C NMR(100MHz,CDCl3)δ143.4,143.3,140.8,132.8,130.1,130.0,129.7,129.4,128.6,128.3,126.9,126.4,124.5,120.5,112.2,21.5.HRMS (ESI):m/z[M+H]+calcd for C21H17ClNO2S:382.0663,found:382.0669.
实施例5
在氮气氛围下向反应试管中加入0.04mmol三氟甲磺酸铜、0.5mmol过氧化苯甲酸叔丁酯、0.4mmol对甲基苯磺酰肼、0.2mmol 1-叠氮基-2-(对甲苯基乙炔基)苯,2mL乙腈与水 (VMeCN:H2O=2:1)的混合溶剂和聚四氟乙烯磁石一粒,室温下搅拌反应8h后,TLC检测反应完成,把反应液用乙酸乙酯萃取后,有机相完全转移至圆底烧瓶中,加适量200-300目硅胶,减压蒸馏除去有机溶剂,得到的粗产物通过硅胶柱层析,以乙酸乙酯和石油醚为洗脱剂进行洗脱,得到2-(对甲苯基)-3-对甲苯磺酰基-1H-吲哚(分离产率80%)。以下是产物的核磁共振表征数据和高分辨质谱数据:
1H NMR(400MHz,DMSO)δ12.40(s,1H),8.03(d,J=6.8Hz,1H),7.63–7.45(m,5H),7.35-7.25(m,6H),2.42(s,3H),2.28(s,3H).13C NMR(100MHz,DMSO)δ143.5,143.4, 141.9,139.6,135.5,130.6,130.0,128.9,127.8,126.1,125.9,123.7,122.4,120.1,112.7,111.2, 21.4,21.3.HRMS(ESI):m/z[M+H]+calcd for C22H20NO2S:362.1209,found:362.1215.
实施例6
在氮气氛围下向反应试管中加入0.04mmol三氟甲磺酸铜、0.5mmol过氧化苯甲酸叔丁酯、0.4mmol对甲基苯磺酰肼、0.2mmol 3-((2-叠氮基苯基)乙炔基)噻吩,2mL乙腈与水(VMeCN:H2O=2:1)的混合溶剂和聚四氟乙烯磁石一粒,室温下搅拌反应8h后,TLC检测反应完成,把反应液用乙酸乙酯萃取后,有机相完全转移至圆底烧瓶中,加适量200-300目硅胶,减压蒸馏除去有机溶剂,得到的粗产物通过硅胶柱层析,以乙酸乙酯和石油醚为洗脱剂进行洗脱,得到2-(3-噻吩基)-3-对甲苯磺酰基-1H-吲哚(分离产率92%)。以下是产物的核磁共振表征数据和高分辨质谱数据:
1H NMR(400MHz,DMSO)δ12.45(s,1H),8.10–8.08(m,2H),7.72–7.70(m,1H), 7.59(d,J=8.4Hz,2H),7.55–7.53(m,1H),7.50–7.47(m,1H),7.30-7.23(m,4H),2.26(s,3H).13C NMR(100MHz,CDCl3)δ148.2,146.3,142.7,140.1,135.2,134.8,134.2,131.3,130.8,128.6, 127.2,124.9,117.3,115.7,26.1.HRMS(ESI):m/z[M+H]+calcd for C19H15NO2S2:353.0544, found:353.0550.
实施例7
在氮气氛围下向反应试管中加入0.04mmol三氟甲磺酸铜、0.5mmol过氧化苯甲酸叔丁酯、0.4mmol对三氟甲基苯磺酰肼、0.2mmol 1-叠氮基-2-(苯基乙炔基)苯,2mL乙腈与水 (VMeCN:H2O=2:1)的混合溶剂和聚四氟乙烯磁石一粒,室温下搅拌反应8h后,TLC检测反应完成,把反应液用乙酸乙酯萃取后,有机相完全转移至圆底烧瓶中,加适量200-300目硅胶,减压蒸馏除去有机溶剂,得到的粗产物通过硅胶柱层析,以乙酸乙酯和石油醚为洗脱剂进行洗脱,得到2-苯基-3–(对三氟甲基苯基磺酰基)-1H-吲哚(分离产率75%)。以下是产物的核磁共振表征数据和高分辨质谱数据:
1H NMR(400MHz,CDCl3)δ8.95(s,1H),8.26–8.20(m,1H),7.72(d,J=8.4Hz,2H),7.56–7.49(m,4H),7.47(d,J=7.2Hz,1H),7.43-7.39(m,3H),7.36–7.28(m,2H).13C NMR(100MHz,CDCl3)δ147.2,143.3,134.6,134.1,133.8,130.2.130.1,129.7,128.3,126.8,125.9, 125.8,125.7,124.3,123.7(q,1JC-F=127.1Hz)123.0,120.6,111.6.HRMS(ESI):m/z[M+ H]+calcd for C21H15F3NO2S:402.0770,found:402.0772.
实施例8
在氮气氛围下向反应试管中加入0.04mmol三氟甲磺酸铜、0.5mmol过氧化苯甲酸叔丁酯、0.4mmol对三氟甲氧基苯磺酰肼、0.2mmol 1-叠氮基-2-(苯基乙炔基)苯,2mL乙腈与水(VMeCN:H2O=2:1)的混合溶剂和聚四氟乙烯磁石一粒,室温下搅拌反应8h后,TLC检测反应完成,把反应液用乙酸乙酯萃取后,有机相完全转移至圆底烧瓶中,加适量200-300目硅胶,减压蒸馏除去有机溶剂,得到的粗产物通过硅胶柱层析,以乙酸乙酯和石油醚为洗脱剂进行洗脱,得到2-苯基-3-(对氟甲氧基苯基磺酰基)-1H-吲哚(分离产率71%)。以下是产物的核磁共振表征数据和高分辨质谱数据:
1H NMR(400MHz,CDCl3)δ9.12(s,1H),8.28–8.14(m,1H),7.62(d,J=8.4Hz,2H),7.50–7.26(m,8H),7.07(d,J=8.4Hz,2H).13C NMR(100MHz,CDCl3)δ151.8,143.0,142.1,134.6,133.8,130.2,129.9,129.8,128.5,128.4,128.2,125.7,124.1,122.9,120.6,120.2(q, 1JC-F=257.7Hz)112.2,111.6.HRMS(ESI):m/z[M+H]+calcd for C21H15F3NO3S:418.0719,found: 418.0723.
实施例9
在氮气氛围下向反应试管中加入0.04mmol三氟甲磺酸铜、0.5mmol过氧化苯甲酸叔丁酯、0.4mmol对硝基苯磺酰肼、0.2mmol 1-叠氮基-2-(苯基乙炔基)苯,2mL乙腈与水(VMeCN:H2O=2:1)的混合溶剂和聚四氟乙烯磁石一粒,室温下搅拌反应8h后,TLC检测反应完成,把反应液用乙酸乙酯萃取后,有机相完全转移至圆底烧瓶中,加适量200-300目硅胶,减压蒸馏除去有机溶剂,得到的粗产物通过硅胶柱层析,以乙酸乙酯和石油醚为洗脱剂进行洗脱,得到2-苯基-3-(对基苯基磺酰基)-1H-吲哚(分离产率70%)。以下是产物的核磁共振表征数据和高分辨质谱数据:
1H NMR(400MHz,CDCl3)δ8.40(s,1H),8.21(d,J=8.8Hz,2H),7.71(d,J=8.0Hz,1H),7.58(d,J=8.8Hz,2H),7.48(d,J=8.0Hz,1H),7.42-7.37(m,5H),7.30(t,J=7.2Hz,1H), 7.22(t,J=7.2Hz,1H).13C NMR(100MHz,CDCl3)δ145.9,142.7,136.0,131.9,130.3,129.1, 128.6,128.5,123.9,123.3,121.3,119.1,111.3.HRMS(ESI):m/z[M+H]+calcd forC20H15N2O4S: 379.0747,found:379.0752.
实施例10
在氮气氛围下向反应试管中加入0.04mmol三氟甲磺酸铜、0.5mmol过氧化苯甲酸叔丁酯、0.4mmol对硝基苯磺酰肼、0.2mmol 4-叠氮基-3-(苯基乙炔基)苯腈,2mL乙腈与水(VMeCN:H2O=2:1)的混合溶剂和聚四氟乙烯磁石一粒,室温下搅拌反应8h后,TLC检测反应完成,把反应液用乙酸乙酯萃取后,有机相完全转移至圆底烧瓶中,加适量200-300目硅胶,减压蒸馏除去有机溶剂,得到的粗产物通过硅胶柱层析,以乙酸乙酯和石油醚为洗脱剂进行洗脱,得到2-苯基-3-(对甲苯基磺酰基)-1H-吲哚-5-甲腈(分离产率65%)。以下是产物的核磁共振表征数据和高分辨质谱数据:
1H NMR(400MHz,DMSO)δ13.03(s,1H),8.47(s,1H),7.70–7.51(m,9H),7.27(d,J=8.4Hz,2H),2.30(s,3H).13C NMR(100MHz,DMSO)δ145.7,143.9,140.9,137.3,130.7,130.5,130.2,129.7,128.5,126.6,126.4,125.6,125.4,120.3,114.3,112.6,104.9,21.4.HRMS (ESI):m/z[M+H]+calcd for C22H17N2O2S:373.1005,found:373.1011。
Claims (9)
1.一种铜催化合成2-芳基-3-芳基磺酰基-1H-吲哚的方法,其特征在于:以三氟甲磺酸铜为催化剂,过氧化苯甲酸叔丁酯为氧化剂,1-叠氮基-2-(芳基乙炔基)苯以及芳基磺酰肼为反应物,在溶剂中反应一段时间,得到2-芳基-3-芳基磺酰基-1H-吲哚;
所述的1-叠氮基-2-(芳基乙炔基)苯以及芳基磺酰肼的结构通式分别为:
其中,R1选自氢、烷基、卤素、氰基;R2选自芳基、取代芳基、杂环芳基;R3选自烷基、硝基、卤素、三氟甲基、三氟甲氧基、芳杂环。
2.根据权利要求1所述的方法,其特征在于:芳基磺酰肼为下述式1-14中的任意一种;
3.根据权利要求1所述的方法,其特征在于:1-叠氮基-2-(芳基乙炔基)苯为下述式15-26中的任意一种
4.根据权利要求2所述的方法,其特征在于:芳基磺酰肼为对甲基苯磺酰肼。
5.根据权利要求3所述的方法,其特征在于:1-叠氮基-2-(芳基乙炔基)苯为1-叠氮基-2-(苯基乙炔基)苯。
6.根据权利要求1所述的方法,其特征在于:所述的溶剂为乙腈与水的混合溶剂,乙腈与水的体积比为2:1。
7.根据权利要求1所述的方法,其特征在于:反应在室温、搅拌条件下进行,反应时间为8h。
8.根据权利要求1所述的方法,其特征在于:三氟甲磺酸铜、过氧化苯甲酸叔丁酯、对甲基苯磺酰肼、1-叠氮基-2-(芳基乙炔基)苯的摩尔比为0.2:2.5:2:1。
9.根据权利要求1所述的方法,其特征在于:具体步骤如下:在氮气氛围下按0.2:2.5:2:1的比例向反应试管中加入三氟甲磺酸铜、过氧化苯甲酸叔丁酯、芳基磺酰肼和1-叠氮基-2-(芳基乙炔基)苯,再加入乙腈与水的混合溶剂,并放入聚四氟乙烯磁石一粒,室温下搅拌反应,TLC检测至反应完成,反应液用乙酸乙酯萃取后,有机相完全转移至圆底烧瓶中,加适量200-300目硅胶,减压蒸馏除去有机溶剂,得到的粗产物通过硅胶柱层析,以乙酸乙酯和石油醚为洗脱剂进行洗脱,得到2-芳基-3-芳基磺酰基-1H-吲哚。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810423907.7A CN108558734A (zh) | 2018-05-07 | 2018-05-07 | 一种铜催化合成2-芳基-3-芳基磺酰基-1h-吲哚的方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810423907.7A CN108558734A (zh) | 2018-05-07 | 2018-05-07 | 一种铜催化合成2-芳基-3-芳基磺酰基-1h-吲哚的方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN108558734A true CN108558734A (zh) | 2018-09-21 |
Family
ID=63537857
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810423907.7A Pending CN108558734A (zh) | 2018-05-07 | 2018-05-07 | 一种铜催化合成2-芳基-3-芳基磺酰基-1h-吲哚的方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108558734A (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110067006A (zh) * | 2019-06-05 | 2019-07-30 | 广西师范大学 | 一种电化学合成磺酰基肼基吲哚类化合物的方法和应用 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006100479A1 (en) * | 2005-03-22 | 2006-09-28 | University College Cardiff Consultants Limited | Methods for the synthesis of heteroaromatic compounds |
CN104262213A (zh) * | 2014-08-29 | 2015-01-07 | 浙江工业大学 | 一种合成α-芳基-β-磺酰基酰胺的方法 |
-
2018
- 2018-05-07 CN CN201810423907.7A patent/CN108558734A/zh active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006100479A1 (en) * | 2005-03-22 | 2006-09-28 | University College Cardiff Consultants Limited | Methods for the synthesis of heteroaromatic compounds |
CN104262213A (zh) * | 2014-08-29 | 2015-01-07 | 浙江工业大学 | 一种合成α-芳基-β-磺酰基酰胺的方法 |
Non-Patent Citations (3)
Title |
---|
FEI CHEN ET,AL.: "tert-Butyl Hydroperoxide (TBHP)-Initiated Vicinal Sulfonamination of Alkynes: A Radical Annulation toward 3‑Sulfonylindoles", 《ORGANIC LETTERS》 * |
QINGSHAN TIAN ET,AL.: "Copper-catalyzed arylsulfonylation of N-arylsulfonyl-acrylamides with arylsulfonohydrazides: synthesis of sulfonated oxindoles", 《ORGANIC & BIOMOLECULAR CHEMISTRY》 * |
XIN-YU ZHU ET,AL.: "Copper-catalyzed Oxidative Cyclization of Alkynes with Sulfonylhydrazides Leading to 2-Sulfonated 9H-Pyrrolo[1,2-a]indol-9-ones", 《THE JOURNAL OF ORGANIC CHEMISTRY》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110067006A (zh) * | 2019-06-05 | 2019-07-30 | 广西师范大学 | 一种电化学合成磺酰基肼基吲哚类化合物的方法和应用 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Galenko et al. | Fe (II)/Au (I) relay catalyzed propargylisoxazole to pyridine isomerization: Access to 6-halonicotinates | |
Lechel et al. | Synthesis of 5‐Acetyloxazoles and 1, 2‐Diketones from β‐Alkoxy‐β‐ketoenamides and Their Subsequent Transformations | |
Chen et al. | An efficient, microwave-assisted, one-pot synthesis of indoles under Sonogashira conditions | |
Li et al. | Rhodium-catalyzed oxidative synthesis of quinoline-fused sydnones via 2-fold C–H bond activation | |
Huang et al. | Copper-mediated [3+ 2] oxidative cyclization reaction of N-tosylhydrazones and β-ketoesters: synthesis of 2, 3, 5-trisubstituted furans | |
Guo et al. | Recent advances in organic synthesis applying elemental selenium | |
Hossain et al. | Cu (I)-catalyzed reaction of diazo compounds with terminal alkynes: a direct synthesis of trisubstituted furans | |
Zhang et al. | An efficient synthesis of gem-diiodoolefins and (E)-iodoalkenes from propargylic amides with a Cu (I)/Cu (III) cycle | |
Shu et al. | Facile and controllable synthesis of multiply substituted benzenes via a formal [3+ 3] cycloaddition approach | |
Chen et al. | Silver-mediated three-component cycloaddition reaction for direct synthesis of 1-N-vinyl-substituted 1, 2, 3-triazoles | |
Tang et al. | Ir (iii)-catalyzed C–H alkynylation of arenes under chelation assistance | |
Liu et al. | Pd (0)‐Catalyzed Tandem One‐Pot Reaction of Biphenyl Ketones/Aldehydes to the Corresponding Di‐substituted Aryl Olefins | |
Song et al. | Environmentally benign and user-friendly in situ generation of nitrile imines from hydrazones for 1, 3-dipolar cycloaddition | |
Ge et al. | CuBr‐Promoted Tandem Cyclization/Trifluoromethylation of 2‐Alkynylanilines: Efficient Synthesis of 3‐Trifluoromethylindoles | |
Kumar et al. | Unprecedented Transformation of a Directing Group Generated In Situ and Its Application in the One‐Pot Synthesis of 2‐Alkenyl Benzonitriles | |
Upadhyay et al. | Palladium‐Catalyzed Carboperfluoroalkylation of Alkynes with Fluoroalkyl Iodides and Arylstannanes | |
CN108558734A (zh) | 一种铜催化合成2-芳基-3-芳基磺酰基-1h-吲哚的方法 | |
Zhang et al. | Copper (I)‐Catalyzed Intramolecular N‐N Coupling of Cyclopropyl O‐Acyl Ketoximes: Synthesis of Spiro‐fused Pyrazolin‐5‐ones | |
CN110511189B (zh) | 5-氨基-1,2,4-噁二唑类衍生物及其合成方法 | |
CN108864164B (zh) | 一种一级胺导向的2-炔基吲哚类化合物的合成方法 | |
CN108409743B (zh) | 一种烷基腈取代的吡咯并[1,2-a]喹喔啉化合物的制备方法 | |
CN110483524A (zh) | 吲哚并咔唑类化合物的制备方法 | |
CN109535140A (zh) | 一种基于肟酯与吲哚构建双吲哚取代二氢吡咯酮类衍生物的方法 | |
CN105646326B (zh) | 一种多取代的吲哚‑2‑酮类化合物的制备方法 | |
CN108440373B (zh) | 一种铁催化的氰烷基吲哚啉及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180921 |