CN108752363B - A kind of synthetic method of benzothiophene [3,2-b] indole derivatives - Google Patents
A kind of synthetic method of benzothiophene [3,2-b] indole derivatives Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
Abstract
The invention discloses a kind of synthetic methods of benzothiophene [3,2-b] indole derivatives, include the following steps: N-R3- 2- ((2- bromophenyl) acetenyl) aniline (II) is dissolved in dimethyl sulfoxide, it reacts under the action of CuBr and TBHP with KSC (S) OEt and obtains benzothiophene [3,2-b] indole derivatives (I)；
Description
Technical field
The present invention relates to a kind of synthetic methods of benzothiophene [3,2-b] indole derivatives.
Background technique
Simultaneously [3,2-b] indoles is a kind of important heterocyclic compound to benzothiophene, this special skeleton is in macromolecule material
It is had potential application in material and biologically active drug.For example, BTCN is the different tetracycline of dicyanoethenyl
Close object.Calculated result and experimental data show that DFT has minimum non-occupied molecular orbital, it is thus possible to be a kind of potential n
Type or bipolarity organic semiconductor.[1]Benzothiophene simultaneously [3,2-b] benzothiophene diindyl compound A and ER α and ER β have it is good
Good binding affinity, can simulate the effect of estrogen, have in terms for the treatment of menopause symptom and Postmenopausal Osteoporosis
There is potential value[2].Compound B can stimulate the synthesis of zoxazolamine hydroxylase to mitigate caused by zoxazolamine
Young rat paralysis[3].In addition, compound C has proved to be amyloid binding compound, can be used for detecting and quantitatively including A Erci
The amyloid beta deposition (seeing below structural formula) in disease including the silent disease in sea and Down's syndrome.[4]
It is specifically shown in below with reference to document:
[1]Du,C.；Chen,J.；Guo,Y.；Lu,K.；Ye,S.；Zheng,J.；Liu,Y.；Shuai,Z.；Yu,
G.J.Org.Chem.2009,74,7322.
[2]Ji,Q.G.；Gao,H.；Wang,J.；Yang,C.C.；Hui,X.；Yan,X.M.；Wu,X.H.；Xie,Y.Y.；
Wang,M.W.Bioorg.Med.Chem.Lett.2005,15,2891.
[3]Buu-Hoi,N.P.；Hien,D.P.Biochem.Pharmacol.1968,17,1227.
[4]Kolb,H.C.；Walsh,J.C.；Zhang W.；Gangadharmath,U.B.；Kasi,D.；Chen,K.；
Sinha,A.；Wang,E.；Chen,G.；Mocharla,V.P.；Scott,P.J.H.；Padgett,H.C.；Liang,Q.；
Gao,Z.；Zhao,T.；Xia,C.WO 2010/011964A2.
Chemical synthesis for benzothiophene simultaneously [3,2-b] Benzazole compounds, has a series of relevant reports, now enumerates
It is as follows:
[1]Ferreira,I.C.F.R.；Queiroz,M.J.R.P.；Kirsch,G.Tetrahedron 2003,59,
3737.
[2]Saito,K.；Chikkade,P.K.；Kanai,M.；Kuninobu,Y.Chem-Eur.J.2015,21,
8365.
[3]Cadogan,J.I.G.Synthesis 1969,11.
[4]Cadogan,J.I.G.C.-W.,M.；Mackie,R.K.；Searle,R.J.G.J.Chem.Soc.1965,
4831.
[5]Takamatsu,K.；Hirano,K.；Satoh,T.；Miura,M.Org Lett 2014,16,2892.
[6]Parisien-Collette,S.；Cruche,C.；Abel-Snape,X.；Collins,
S.K.Green.Chem.2017,19,4798.
[7]Kamimoto,N.；Schollmeyer,D.；Mitsudo,K.；Suga,S.；Waldvogel,S.R.Chem-
Eur.J.2015,21,8257.
In addition, there are also for benzothiophene, simultaneously the derivative of [3.2-b] Benzazole compounds synthesize and to its biology
The report that activity is studied.
Relevant report enumerates as follows:
[1]Du,C.；Chen,J.；Guo,Y.；Lu,K.；Ye,S.；Zheng,J.；Liu,Y.；Shuai,Z.；Yu,
G.J.Org.Chem.2009,74,7322.
[2]Ji,Q.G.；Gao,H.；Wang,J.；Yang,C.C.；Hui,X.；Yan,X.M.；Wu,X.H.；Xie,Y.Y.；
Wang,M.W.Bioorg.Med.Chem.Lett.2005,15,2891.
[3]Buu-Hoi,N.P.；Hien,D.P.Biochem.Pharmacol.1968,17,1227.
[4]Kolb,H.C.；Walsh,J.C.；Zhang W.；Gangadharmath,U.B.；Kasi,D.
[5]N.P.Buu–Hor；Do-Phuoc Hien.Biochem.Pharm.1968,17,1227-1236.
However, in all these synthetic methods, there is not yet with N-R3- 2- ((2- bromophenyl) acetenyl) aniline (II) chemical combination
Object is raw material, and the oxidative coupling of gradually connecting that substrate occurs with ehtyl potassium xanthate under the action of oxidant and catalyst is anti-
It answers, while realizing the synthesis of indole ring and thiphene ring.A kind of similar method is with 2- (2- iodophenyl) -1 hydrogen-indoles in iodine list
Matter, potassium sulfide and cuprous iodide (Huang, H.；Dang,P.；Wu,L.J.；Liang,Y.；Liu,J.B.Tetrahedron
Lett.2016,57,574) such compound is obtained under the action of, but this method only realizes the synthesis of thiphene ring.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of simple realization substrate gradually to connect oxidative coupling
Benzothiophene [3,2-b] indole derivatives synthetic method.
Technical solution of the present invention is summarized as follows:
A kind of synthetic method of benzothiophene [3,2-b] indole derivatives, includes the following steps: N-R3- 2- ((2- bromine
Phenyl) acetenyl) aniline (II) is dissolved in dimethyl sulfoxide, reacts under the action of CuBr and TBHP with KSC (S) OEt
Obtain benzothiophene [3,2-b] indole derivatives (I)；
In formula:
R1For hydrogen atom, methyl, fluorine atom, chlorine atom or bromine atom；
R2For hydrogen atom, methyl, methoxyl group, fluorine atom, chlorine atom, bromine atom or trifluoromethyl；
R3For p-toluenesulfonyl, mesyl, benzenesulfonyl, to chlorobenzenesulfonyl, brosyl or to methoxy
Base benzenesulfonyl；
The CuBr is cuprous bromide；TBHP is writing a Chinese character in simplified form for tert-butyl hydroperoxide；KSC (S) OEt is ehtyl potassium xanthate
Write a Chinese character in simplified form.
KSC (S) OEt, the CuBr and TBHP and N-R3The molar ratio of -2- ((2- bromophenyl) acetenyl) aniline (II) is excellent
It is selected as 2:0.2:3:1.
Reaction yield highest when reaction temperature is 60-100 DEG C, 80 DEG C.
The present invention has the advantages that easy to operate, raw material is cheap and easy to get, and yield is more satisfactory, and cost is relatively low.
Specific embodiment
Ehtyl potassium xanthate (KSC (S) OEt) is commercially available 97+The ehtyl potassium xanthate of %.
Tert-butyl hydroperoxide (TBHP) is with the anhydrous tert-butyl hydroperoxide obtained after petroleum ether extraction.
Cuprous bromide (CuBr) is commercially available cuprous bromide.
Dimethyl sulfoxide (DMSO) is commercially available analysis absolute dimethyl sulfoxide.
Required reaction raw materials, i.e. N-R in embodiment3- 2- ((2- bromophenyl) acetenyl) aniline (II), for referring to text
The method of offering prepares ([1] Bhunia, S.；Ghorpade,S.；Huple,D.B.；Liu,R.-S.Angew.Chem.,
Int.Ed.2012,51,2939.[2]Odedra,A.；Datta,S.；Liu,R.-S.J.Org.Chem.2007,72,3289.
[3]Shu,C.；Chen,C.-B.；Chen,W.-X.；Ye,L.-W.Org.Lett.2013,15,5542.
The present invention is further illustrated combined with specific embodiments below.
Embodiment 1
The preparation of 10- p-toluenesulfonyl -10H- benzo [4,5] thiophene [3,2-b] indoles (I-a)
N- p-toluenesulfonyl -2- ((2- bromophenyl) acetenyl) aniline (II-a) (1mmol, 426mg) is dissolved in 4mL bis-
In methyl sulfoxide (DMSO), be added at one time ehtyl potassium xanthate (2mmol, 320mg) and cuprous bromide (0.2mmol,
28.6mg), tert-butyl hydroperoxide (3mmol, 270mg) is then slowly added dropwise, the reaction at 80 DEG C is until TLC display substrate is complete
Full response.Stop heating, be cooled to room temperature, is extracted three times with water and ethyl acetate, merge organic phase, be washed with brine organic phase,
It is dry that anhydrous sodium sulfate is added, organic column silica gel that was added to is evaporated, and column chromatography (ethyl acetate: petroleum ether=3:97) separates
To white solid (I-a) 294mg, yield 78%.Fusing point is 157-159 DEG C of1H NMR(600MHz,CDCl3)δ8.97(d,J
=8.4Hz, 1H), 8.41 (d, J=8.4Hz, 1H), 7.85 (d, J=8.4Hz, 1H), 7.58 (d, J=7.8Hz, 1H), 7.53
(t, J=7.2Hz, 1H), 7.50 (d, J=8.4Hz, 2H), 7.44-7.39 (m, 2H), 7.34 (t, J=7.2Hz, 1H), 6.99
(d, J=8.4Hz, 2H), 2.21 (s, 3H)13C NMR(150MHz,CDCl3)δ144.8,142.6,141.4,135.3,
134.2,129.6,128.2,126.7,126.6,125.9,125.4,125.4,124.8,124.6,124.0,123.9,
119.4,117.0,21.5.HRMS(ESI)calcd forC21H15NNaO2S2 +[M+Na+]400.0436,found400.0436.
For 10- p-toluenesulfonyl -10H- benzo [4,5] thiophene [3,2-b] indoles (I-a).
With N- benzenesulfonyl -2- ((2- bromophenyl) acetenyl) aniline, N- brosyl -2- ((2- bromophenyl) second
Alkynyl) aniline, N- substitute the N- of the present embodiment to toluene sulphur to MethOxybenzenesulfonyl -2- ((2- bromophenyl) acetenyl) aniline
Acyl group -2- ((2- bromophenyl) acetenyl) aniline, other same the present embodiment are prepared respectively: 10- benzenesulfonyl -10H- benzo
[4,5] thiophene [3,2-b] indoles, 10- brosyl -10H- benzo [4,5] thiophene [3,2-b] indoles, 10- are to methoxyl group
Benzenesulfonyl -10H- benzo [4,5] thiophene [3,2-b] indoles.
Embodiment 2
The preparation of 3- methyl-1 0- p-toluenesulfonyl -10H- benzo [4,5] thiophene [3,2-b] indoles (I-b)
By N- (2- (2- bromophenyl) acetenyl) -4- aminomethyl phenyl) -4- methyl benzenesulfonamide (II-b) (1mmol,
It 440mg) is dissolved in 4mL dimethyl sulfoxide (DMSO), is added at one time ehtyl potassium xanthate (2mmol, 320mg) and cuprous bromide
Tert-butyl hydroperoxide (TBHP) (3mmol, 270mg) is then slowly added dropwise in (0.2mmol, 28.6mg), reacts straight at 80 DEG C
It is reacted completely to TLC display substrate.Stop heating, be cooled to room temperature, is extracted three times with water and ethyl acetate, merge organic phase, used
Anhydrous sodium sulfate drying is added in salt water washing organic phase, and organic column silica gel that was added to is evaporated, and column chromatographs (ethyl acetate: petroleum
Ether=2:98) isolated white solid (I-b) 196mg, yield 50%.Fusing point is 171-172 DEG C of1H NMR(600MHz,
CDCl3) δ 8.96 (d, J=8.4Hz, 1H), 8.27 (d, J=8.4Hz, 1H), 7.85 (d, J=8.4Hz, 1H), 7.53 (td, J
=7.8,1.2Hz, 1H), 7.48 (d, J=8.4Hz, 2H), 7.40 (td, J=7.2,1.2Hz, 1H), 7.37 (s, 1H), 7.23
(d, J=8.4Hz, 1H), 6.99 (d, J=8.4Hz, 2H), 2.45 (s, 3H), 2.21 (s, 3H)13C NMR(150MHz,
CDCl3)δ144.7,142.5,139.5,135.3,134.5,134.1,129.6,128.3,127.2,126.7,126.6,
125.5,125.3,124.7,124.0,123.8,119.4,116.7,21.5,21.3.HRMS(ESI)calcd
forC22H17NNaO2S2 +[M+Na+] 414.0593, found414.0596. be 3- methyl-1 0- p-toluenesulfonyl -10H- benzo
[4,5] thiophene [3,2-b] indoles (I-b)
Embodiment 3
The preparation of chloro- 10- p-toluenesulfonyl -10H- benzo [4,5] thiophene [3,2-b] indoles (I-c) of 3-
By N- (2 (2- bromophenyl) acetenyl) -4- chlorphenyl) -4- methyl benzenesulfonamide (II-c) (1mmol, 460mg) is molten
In 4mL dimethyl sulfoxide (DMSO), it is added at one time ehtyl potassium xanthate (2mmol, 320mg) and cuprous bromide
Tert-butyl hydroperoxide (TBHP) (3mmol, 270mg) is then slowly added dropwise in (0.2mmol, 28.6mg), reacts straight at 80 DEG C
It is reacted completely to TLC display substrate.Stop heating, be cooled to room temperature, is extracted three times with water and ethyl acetate, merge organic phase, used
Anhydrous sodium sulfate drying is added in salt water washing organic phase, and organic column silica gel that was added to is evaporated, and column chromatographs (ethyl acetate: petroleum
Ether=2:98) isolated white solid (I-c) 313mg, yield 76%, fusing point is 198-199 DEG C.1H NMR(600MHz,
CDCl3) δ 8.96 (d, J=8.4Hz, 1H), 8.33 (d, J=9.0Hz, 1H), 7.85 (d, J=7.8Hz, 1H), 7.57-7.52
(m, 2H), 7.48 (d, J=8.4Hz, 2H), 7.42 (t, J=7.8,1.2Hz, 1H), 7.37 (dd, J=9.0,2.4Hz, 1H),
7.02 (d, J=8.4Hz, 2H), 2.23 (s, 3H)13C NMR(150MHz,CDCl3)δ145.2,142.8,139.6,136.4,
133.9,130.5,129.7,127.8,126.6,126.5,125.9,125.5,125.5,125.3,124.1,124.1,
119.1,118.0,21.6.HRMS(ESI)calcd forC21H14 35ClNNaO2S2 +[M+Na+]434.0047,
It found434.0049. is chloro- 10- p-toluenesulfonyl -10H- benzo [4,5] thiophene [3,2-b] indoles (I-c) of 3-.
With N- (2 (2- bromophenyl) acetenyl) -4- fluorophenyl) -4- methyl benzenesulfonamide or with N- (2 (2- bromophenyl) second
Alkynyl) -4- bromophenyl) -4- methyl benzenesulfonamide substitutes N- (2 (2- bromophenyl) acetenyl) -4- chlorphenyl of the present embodiment) -
4- methyl benzenesulfonamide, other same the present embodiment, is prepared: fluoro- 10- p-toluenesulfonyl -10H- benzo [4, the 5] thiophene of 3-
[3,2-b] indoles or bromo- 10- p-toluenesulfonyl -10H- benzo [4,5] thiophene [3,2-b] indoles of 3-.
Embodiment 4
The preparation of 7- methyl-1 0- p-toluenesulfonyl -10H- benzo [4,5] thiophene [3,2-b] indoles (I-d)
By N- (2- (the bromo- 4- aminomethyl phenyl of 2-) ethynyl phenyl) -4- methyl benzenesulfonamide (II-d) (1mmol, 440mg)
It is dissolved in 4mL dimethyl sulfoxide (DMSO), is added at one time ehtyl potassium xanthate (2mmol, 320mg) and cuprous bromide
Tert-butyl hydroperoxide (TBHP) (3mmol, 270mg) is then slowly added dropwise in (0.2mmol, 28.6mg), reacts straight at 80 DEG C
It is reacted completely to TLC display substrate.Stop heating, be cooled to room temperature, is extracted three times with water and ethyl acetate, merge organic phase, used
Anhydrous sodium sulfate drying is added in salt water washing organic phase, and organic column silica gel that was added to is evaporated, and column chromatographs (ethyl acetate: petroleum
Ether=3:97) isolated white solid (I-d) 313mg, yield 80%, fusing point is 136-137 DEG C.1H NMR(600MHz,
CDCl3) δ 8.83 (d, J=8.4Hz, 1H), 8.39 (d, J=8.4Hz, 1H), 7.63 (s, 1H), 7.53 (d, J=7.8Hz,
1H), 7.49 (d, J=8.4Hz, 2H), 7.39 (t, J=7.8Hz, 1H), 7.34-7.30 (m, 2H), 6.97 (d, J=7.8Hz,
2H),2.50(s,3H),2.19(s,3H).13C NMR(150MHz,CDCl3)δ144.8,143.0,141.1,135.2,135.0,
134.2,129.6,127.0,126.6,125.9,125.7,125.5,124.6,124.0,123.5,119.2,116.9,21.5,
21.5.HRMS(ESI)calcd forC22H17NNaO2S2 +[M+Na+] 0- pairs of 414.0593, found414.0598.7- methyl-1
Tosyl -10H- benzo [4,5] thiophene [3,2-b] indoles (I-d)
With N- (2- (the bromo- 4- methoxyphenyl of 2-) ethynyl phenyl) -4- methyl benzenesulfonamide, N- (2- (the bromo- 4- tri- of 2-
Trifluoromethylphenyl) ethynyl phenyl) -4- methyl benzenesulfonamide substitutes N- (2- (the bromo- 4- aminomethyl phenyl of 2-) acetylene of the present embodiment
Base phenyl) -4- methyl benzenesulfonamide, other same the present embodiment prepare: 7- methoxyl group -10- p-toluenesulfonyl -10H- benzo
[4,5] thiophene [3,2-b] indoles or 7- Trifluoromethyl-1 0- p-toluenesulfonyl -10H- benzo [4,5] thiophene [3,2-b] Yin
Diindyl.
Embodiment 5
The preparation of bromo- 10- p-toluenesulfonyl -10H- benzo [4,5] thieno [3-2-b] indoles (I-e) of 7-
By N- (2 (- (2,4- dibromo phenyl) acetenyl) phenyl) -4- methyl benzenesulfonamide (II-e) (1mmol, 502mg)
It is dissolved in 4mL dimethyl sulfoxide (DMSO), is added at one time ehtyl potassium xanthate (2mmol, 320mg) and cuprous bromide
Tert-butyl hydroperoxide (TBHP) (3mmol, 270mg) is then slowly added dropwise in (0.2mmol, 28.6mg), reacts straight at 80 DEG C
It is reacted completely to TLC display substrate.Stop heating, be cooled to room temperature, is extracted three times with water and ethyl acetate, merge organic phase, used
Anhydrous sodium sulfate drying is added in salt water washing organic phase, and organic column silica gel that was added to is evaporated, and column chromatographs (ethyl acetate: petroleum
Ether=3:97) isolated white solid (I-e) 360mg, yield 79%, fusing point is 182-183 DEG C.1H NMR(600MHz,
CDCl3) δ 8.83 (d, J=9.0Hz, 1H), 8.40 (d, J=8.4Hz, 1H), 7.96 (d, J=1.8Hz, 1H), 7.62 (dd, J
=9.0,1.8Hz, 1H), 7.56 (d, J=7.8Hz, 1H), 7.48-7.42 (m, 3H), 7.34 (t, J=7.2Hz, 1H), 7.00
(d, J=8.4Hz, 2H), 2.21 (s, 3H)13C NMR(150MHz,CDCl3)δ145.1,143.9,141.3,134.6,
134.0,129.7,128.7,127.0,126.9,126.6,126.5,126.2,125.0,125.0,124.8,119.4,
118.5,117.0,21.5.HRMS(ESI)calcd forC21H14 79BrNNaO2S2 +[M+Na+]477.9542,
It found477.9548. is bromo- 10- p-toluenesulfonyl -10H- benzo [4,5] thieno [3-2-b] indoles (I-e) of 7-
With N- (2 (- (the bromo- 4- chlorphenyl of 2-) acetenyl) phenyl) -4- methyl benzenesulfonamide or N- (2 (- (the bromo- 4- fluorine of 2-
Phenyl) acetenyl) phenyl) -4- methyl benzenesulfonamide replaces N- (2 (- (2,4- dibromo phenyl) acetenyl) benzene of the present embodiment
Base) -4- methyl benzenesulfonamide, other same the present embodiment prepare: chloro- 10- p-toluenesulfonyl -10H- benzo [4, the 5] thiophene of 7-
Pheno simultaneously [3-2-b] indoles or fluoro- 10- p-toluenesulfonyl -10H- benzo [4,5] thieno [3-2-b] indoles of 7-.
Embodiment 6
The preparation of 10- mesyl -10H- benzo [4,5] thiophene [3,2-b] indoles (I-f)
It is sub- that N- (2 (2- bromophenyl) acetenyl) phenyl methanesulfonamide amide (II-f) (1mmol, 349mg) is dissolved in 4mL dimethyl
In sulfone (DMSO), it is added at one time ehtyl potassium xanthate (2mmol, 320mg) and cuprous bromide (0.2mmol, 28.6mg), then
Tert-butyl hydroperoxide (TBHP) (3mmol, 270mg) is slowly added dropwise, the reaction at 80 DEG C is until TLC display substrate is completely anti-
It answers.Stop heating, be cooled to room temperature, is extracted three times with water and ethyl acetate, merge organic phase, be washed with brine organic phase, be added
Anhydrous sodium sulfate is dry, and organic column silica gel that was added to is evaporated, and it is isolated white that column chromatographs (ethyl acetate: petroleum ether=3:97)
Color solid (I-f) 214mg, yield 71%, fusing point are 163-165 DEG C.1H NMR(600MHz,CDCl3) δ 8.73 (d, J=
8.4Hz, 1H), 8.26 (dd, J=7.2,1.2Hz, 1H), 7.90 (d, J=7.8Hz, 1H), 7.73 (dd, J=7.8,1.2Hz,
1H), 7.49 (t, J=7.2Hz, 1H), 7.46-7.39 (m, 3H), 2.98 (s, 3H)13C NMR(150MHz,CDCl3)δ
142.7,141.2,134.8,127.6,126.1,125.9,125.4,125.0,124.9,124.7,124.2,123.5,
119.6,116.3,39.5.HRMS(ESI)calcd forC15H11NNaO2S2 +[M+Na+]324.0123,found324.0125.
For 10- mesyl -10H- benzo [4,5] thiophene [3,2-b] indoles (I-f).
Embodiment 7
Preparation of the 10- to chlorobenzenesulfonyl -10H- benzo [4,5] thiophene [3,2-b] indoles (I-g)
By N- (2- (2- bromophenyl) acetenyl) phenyl) -4- chlorobenzene sulfonamide (II-g) (1mmol, 446mg) is dissolved in 4mL
In dimethyl sulfoxide (DMSO), be added at one time ehtyl potassium xanthate (2mmol, 320mg) and cuprous bromide (0.2mmol,
28.6mg), tert-butyl hydroperoxide (TBHP) (3mmol, 270mg) is then slowly added dropwise, the reaction at 80 DEG C is until TLC is shown
Substrate reacts completely.Stop heating, be cooled to room temperature, is extracted three times with water and ethyl acetate, merge organic phase, be washed with brine
Anhydrous sodium sulfate drying is added in machine phase, and organic column silica gel that was added to is evaporated, and column chromatographs (ethyl acetate: petroleum ether=3:97)
Isolated white solid (I-g) 231mg, yield 58%, fusing point are 164-165 DEG C.1H NMR(600MHz,CDCl3)δ
8.92 (d, J=8.4Hz, 1H), 8.38 (d, J=8.4Hz, 1H), 7.87 (d, J=7.8Hz, 1H), 7.60 (d, J=7.8Hz,
1H), 7.55 (t, J=7.8Hz, 1H), 7.52 (d, J=9.0Hz, 2H), 7.46-7.40 (m, 2H), 7.37 (t, J=7.8Hz,
1H), 7.18 (d, J=8.4Hz, 2H)13C NMR(150MHz,CDCl3)δ142.6,141.3,140.5,135.1,135.0,
129.3,128.1,128.0,127.5,126.1,125.6,125.5,125.1,125.0,124.2,123.7,119.6,
117.0.HRMS(ESI)calcd forC20H12 35ClNNaO2S2 +[M+Na+] 419.9890, found419.9890. be 10- pairs
Chlorobenzenesulfonyl -10H- benzo [4,5] thiophene [3,2-b] indoles (I-g).
The above is only section Example of the invention, not does limitation in any form to the present invention, all
It is any simple modification made according to the technical essence of the invention to above-described embodiment, equivalent variations and modification, belongs to this
Within the scope of inventive technique scheme.
Claims (1)
1. a kind of synthetic method of benzothiophene [3,2-b] indole derivatives, it is characterized in that including the following steps: N-R3-2-
((2- bromophenyl) acetenyl) aniline (II) is dissolved in dimethyl sulfoxide, is sent out under the action of CuBr and TBHP with KSC (S) OEt
Raw reaction obtains benzothiophene [3,2-b] indole derivatives (I)；
In formula:
R1For hydrogen atom, methyl, fluorine atom, chlorine atom or bromine atom；
R2For hydrogen atom, methyl, methoxyl group, fluorine atom, chlorine atom, bromine atom or trifluoromethyl；
R3For p-toluenesulfonyl, mesyl, benzenesulfonyl, to chlorobenzenesulfonyl, brosyl or to methoxybenzene sulphur
Acyl group；
The CuBr is cuprous bromide；TBHP is writing a Chinese character in simplified form for tert-butyl hydroperoxide；KSC (S) OEt is the letter of ehtyl potassium xanthate
It writes.
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