CN110067006A - A kind of methods and applications of electrochemistry formated sulfonyl diazanyl Benzazole compounds - Google Patents
A kind of methods and applications of electrochemistry formated sulfonyl diazanyl Benzazole compounds Download PDFInfo
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Abstract
A kind of method that the present invention discloses electrochemistry formated sulfonyl diazanyl Benzazole compounds; it is synthesized using the method for no metal and anaerobic agent; under mild electrochemical conditions; sulfohydrazide carries out selective sulfonylation and hydrazine to indoles; obtain a series of sulfonyl diazanyl Benzazole compounds with pharmacological activity; and screened by anti tumor activity in vitro, it is found that the sulfonyl diazanyl Benzazole compounds of synthesis have good anti-tumor activity.The method of the present invention carries out in a undivided cell, replaces exogenous oxidized dose using constant current, by-product is hydrogen and nitrogen.In addition, under mild no catalyst electrochemical conditions, the problem of being effectively prevented from the detosylation or excessive oxidation of sulfonyl, the method for the present invention is more environmentally protective compared with traditional synthetic method.
Description
Technical field
The present invention relates to the synthetic method of compound, specifically a kind of electrochemistry formated sulfonyl diazanyl Benzazole compounds
Methods and applications.
Background technique
Indoles skeleton is widely present in various natural products, due to its special chemistry and biological property, it is considered to be
" dominance structure " with medicine in related major class compound.Since synthesizing chemical developer, the functionalization of indole derivatives
The great interest of organic chemist is caused with synthesis, has the document report efficient synthesis of indoles.However, these sides
Method requires greatly equivalent oxidant or excess catalyst.
In addition, the indole derivatives containing sulfonyl are widely present in natural products and drug molecule.For example, 3- sulphonyl
Base -1H- Benzazole compounds are HIV-1 non-nucleoside reverse transcriptase inhibitor (NNRTIs) and 5-HT6 receptors ligand, in the treatment
In pivot nervous system disease (schizophrenia, depression and Alzheimer disease) have better effects (J.Med.Chem.,
1993,36,1291；Bioorg.Med.Chem.Lett.,2004,14,5499).
Currently, drug available on the market, as isoniazid, rice phosphonate, hydrazine piperazine and benzene plug draw piperazine all to contain hydrazine functional group.
Hydrazine skeleton has multiple biological activities, such as Antischistosomal Activity, anticancer activity, antibacterial activity, anti-inflammatory activity and antioxidant activity
(Res.2014,113,437；Bioorg.Med.Chem.Lett., 2015,23,1651；E.J.Mol.Struct., 2014,
1075,566；Bioorg.Med.Chem.Lett., 2015,25,1420；Med.Chem., 2014,10,521；).Therefore, by hydrazine
It is a significant job that functional group, which introduces indole ring, but has no document report at present.
Summary of the invention
The object of the present invention is to provide a kind of methods and applications of electrochemistry formated sulfonyl diazanyl Benzazole compounds, adopt
It is synthesized with the method for no metal and anaerobic agent, under mild electrochemical conditions, sulfohydrazide carries out selective sulphur to indoles
Acylated and hydrazine, obtains a series of sulfonyl diazanyl Benzazole compounds with pharmacological activity.
Realizing the technical solution of the object of the invention is:
A kind of method of electrochemistry formated sulfonyl diazanyl Benzazole compounds, synthetic method general formula are as follows:
Wherein, R1, R2=aromatic radical, fat-based etc.；
Electrolyte are as follows: NH4I、NH4Br、Bu4NPF6、NH4Cl or KI etc.；
Solvent are as follows: acetonitrile, methanol or ethyl alcohol etc..
The universal synthesis method of the sulfonyl diazanyl Benzazole compounds, includes the following steps:
(A) respectively by the indoles of 0.5mmol 1, the electrolyte of 1mmol benzene sulfonyl hydrazide 2 and 1mmol are added to 10mL three-necked bottle
In, the dissolution of 8mL solvent is added, makees anode with Reticulated Vitreous body carbon RVC, platinized platinum Pt makees cathode, in undivided cell, with
10-30mA constant current, argon gas are protected, and 3-5h is stirred to react under the conditions of 50-70 DEG C, and TLC monitors reaction process；
(B) to after the reaction was completed, extract mixture, organic layer anhydrous Na with 10mL ethyl acetate2SO4It is dry, with rotation
Evaporimeter removes solvent, and residue obtains product 3 through Flash silica column chromatographic purifying.
Step (B) the Flash silica column chromatographic purifying, eluant, eluent volume ratio are ethyl acetate: petroleum ether=1:3-6.
In the preparation of antitumor drugs the invention also includes compound shown in above-mentioned formula 3 or its pharmaceutically acceptable salt
Using.
It is anti-the invention also includes being prepared using compound shown in above-mentioned formula 3 or its pharmaceutically acceptable salt as active constituent
Tumour medicine.
The method of the present invention, under mild electrochemical conditions, sulfohydrazide carries out selective sulfonylation to indoles and hydrazineization is anti-
A series of sulfonyl diazanyl Benzazole compounds should have been synthesized, and have been screened by anti tumor activity in vitro, have found the sulphonyl of synthesis
Base diazanyl Benzazole compounds have good anti-tumor activity.In numerous oxidants for oxidative coupling reaction, electric current
It is generally the least expensive, most effective and environmental-friendly one of oxidant.The method of the present invention carries out in a undivided cell, uses
Constant current replaces exogenous oxidized dose, and by-product is hydrogen and nitrogen.In addition, under mild no catalyst electrochemical conditions,
The problem of being effectively prevented from the detosylation or excessive oxidation of sulfonyl obtains and a series of has no sulfonyl hydrazine reported in the literature
Base Benzazole compounds.And the method for the present invention is compared with traditional synthetic method, and it is more environmentally protective.
Specific embodiment
Below with reference to the synthesis of embodiment sulfonyl diazanyl Benzazole compounds and structure, characterization to the content of present invention make into
The explanation of one step, but be not limitation of the invention.
Embodiment 1:
The synthesis and characterization of 4- methyl-N'- (3- p-toluenesulfonyl -1H- indoles -2- base) benzene sulfonyl hydrazide (3aa):
Respectively by the indoles of 0.5mmol, 1mmol unifor and 1mmol NH4I is added in 10mL three-necked bottle, is added
Enter the dissolution of 8mL acetonitrile, make anode with Reticulated Vitreous body carbon RVC, platinized platinum Pt makees cathode, in undivided cell, in 10mA perseverance
Electric current, argon gas are protected, and 3h is stirred to react under the conditions of 50 DEG C, and TLC monitors reaction process；
To after the reaction was completed, extract mixture, organic layer anhydrous Na with 10mL ethyl acetate2SO4It is dry, it is steamed with rotation
It sends out instrument and removes solvent, residue chromatographs (eluant, eluent volume ratio is ethyl acetate: petroleum ether=1:3) purifying through Flash silica column,
Obtain white solid 3aa；
.mp:125.0-125.6 DEG C of White solid (85%, 193.4mg),1H NMR(400MHz,DMSO-d6)δ
11.73 (s, 1H), 9.97 (s, 1H), 7.92 (s, 1H), 7.85-7.75 (m, 2H), 7.72-7.65 (m, 2H), 7.58-7.50
(m,2H),7.48–7.40(m,1H),7.38–7.32(m,2H),7.30–7.24(m,1H),7.10–6.90(m,2H),2.44
(s,3H),2.33(s,3H).13C NMR(100MHz,DMSO-d6)δ148.3,144.4,142.9,141.2,133.9,132.0,
129.9,129.6,128.0,125.3,124.7,121.3,120.7,116.1,111.3,89.8,21.1,20.9.HRMS(m/
z)(ESI):calcd for C22H22N3O4S2[M+H]+456.1052,found 456.1036。
Embodiment 2:
The synthesis and characterization of N'- (3- (benzenesulfonyl) -1H- indoles -2- base) benzene sulfonyl hydrazide (3ab):
Respectively by the indoles of 0.5mmol, 1mmol benzene sulfonyl hydrazide and 1mmol NH4Br is added in 10mL three-necked bottle, is added
The dissolution of 8mL methanol, makees anode with Reticulated Vitreous body carbon RVC, and platinized platinum Pt makees cathode, in undivided cell, in the permanent electricity of 15mA
Stream, argon gas are protected, and 4h is stirred to react under the conditions of 55 DEG C, and TLC monitors reaction process；
To after the reaction was completed, extract mixture, organic layer anhydrous Na with 10mL ethyl acetate2SO4It is dry, it is steamed with rotation
It sends out instrument and removes solvent, residue chromatographs (eluant, eluent volume ratio is ethyl acetate: petroleum ether=1:4) purifying through Flash silica column,
Obtain white solid 3ab；
.mp:112.4-113.7 DEG C of White solid (78%, 166.5mg),1H NMR(500MHz,DMSO-d6)δ
11.77(s,1H),10.08(s,1H),8.04(s,1H),7.91–7.87(m,2H),7.81–7.75(m,3H),7.74–7.68
(m,2H),7.60–7.52(m,3H),7.47–7.43(M,1H),7.28–7.24(m,1H),7.04–6.94(m,2H).13C NMR
(125MHz,DMSO-d6)δ148.5,144.0,136.9,133.9,132.5,132.0,129.4,129.2,127.9,125.2,
124.7,121.3,120.8,116.1,111.3,89.4.HRMS(m/z)(ESI):calcd for C20H18N3O4S2[M+H]+
428.0739,found 428.0725。
Embodiment 3:
The synthesis and characterization of 2- methyl-N'- (3- (adjacent tosyl) -1H- indoles -2- base) benzene sulfonyl hydrazide (3ac):
Respectively by the indoles of 0.5mmol, 1mmol neighbour's toluene sulfonyl hydrazide and 1mmol Bu4NPF6It is added in 10mL three-necked bottle,
The dissolution of 8mL ethyl alcohol is added, makees anode with Reticulated Vitreous body carbon RVC, platinized platinum Pt makees cathode, in undivided cell, in 20mA
Constant current, argon gas are protected, and 5h is stirred to react under the conditions of 60 DEG C, and TLC monitors reaction process；
To after the reaction was completed, extract mixture, organic layer anhydrous Na with 10mL ethyl acetate2SO4It is dry, it is steamed with rotation
It sends out instrument and removes solvent, residue chromatographs (eluant, eluent volume ratio is ethyl acetate: petroleum ether=1:5) purifying through Flash silica column,
Obtain white solid 3ac；
.mp:131.5-132.9 DEG C of White solid (45%, 102.4mg),1H NMR(400MHz,DMSO-d6)δ
11.78(s,1H),10.02(s,1H),8.00-7.90(m,1H),7.82(s,1H),7.75–7.70(m,2H),7.52–7.45
(m,3H),7.44–7.38(m,1H),7.34–7.28(m,2H),7.14–7.08(m,1H),7.02–6.88(m,2H),2.42
(s,3H),2.35(s,3H).13C NMR(100MHz,DMSO-d6)δ149.0,144.3,141.2,136.8,133.9,132.6,
132.5,132.0,129.9,127.9,127.8,126.3,124.7,121.2,120.8,115.8,111.4,87.8,21.1,
19.4.HRMS(m/z)(ESI):calcd for C22H22N3O4S2[M+H]+456.1052,found 456.1038。
Embodiment 4:
The synthesis and characterization of 3- methyl-N'- (3- (tosyl) -1H- indoles -2- base) benzene sulfonyl hydrazide (3ad):
Respectively by the indoles of 0.5mmol, toluene sulfonyl hydrazide and 1mmol KI are added in 10mL three-necked bottle between 1mmol, are added
The dissolution of 8mL acetonitrile, makees anode with Reticulated Vitreous body carbon RVC, and platinized platinum Pt makees cathode, in undivided cell, in the permanent electricity of 25mA
Stream, argon gas are protected, and 3h is stirred to react under the conditions of 65 DEG C, and TLC monitors reaction process；
To after the reaction was completed, extract mixture, organic layer anhydrous Na with 10mL ethyl acetate2SO4It is dry, it is steamed with rotation
It sends out instrument and removes solvent, residue chromatographs (eluant, eluent volume ratio is ethyl acetate: petroleum ether=1:6) purifying through Flash silica column,
Obtain white solid 3ad；
.mp:125.3-125.8 DEG C of White solid (78%, 177.5mg),1H NMR(400MHz,DMSO-d6)δ
11.76(s,1H),10.04(s,1H),8.01(s,1H),7.77–7.66(m,3H),7.65–7.61(m,1H),7.62–7.53
(m,2H),7.47–7.37(m,3H),7.31–7.25(m,1H),7.06–6.97(m,2H),2.37(s,3H),2.34(s,3H)
.13C NMR(100MHz,DMSO-d6)δ148.5,144.0,139.2,139.0,136.8,134.4,133.2,132.1,
129.3,129.0,128.1,125.4,124.9,124.7,122.5,121.3,120.9,116.2,111.3,89.5,20.9,
20.8.HRMS(m/z)(ESI):calcd for C22H22N3O4S2[M+H]+456.1052,found 456.1038。
Embodiment 5:
The synthesis and characterization of the fluoro- N'- of 4- (3- (4- fluorophenyl) sulfonyl -1H- indoles -2- base) benzene sulfonyl hydrazide (3ae):
Respectively by the indoles of 0.5mmol, 1mmol is to fluorobenzene sulfohydrazide and 1mmol NH4I is added in 10mL three-necked bottle, is added
Enter the dissolution of 8mL methanol, make anode with Reticulated Vitreous body carbon RVC, platinized platinum Pt makees cathode, in undivided cell, in 30mA perseverance
Electric current, argon gas are protected, and 4h is stirred to react under the conditions of 70 DEG C, and TLC monitors reaction process；
After the reaction was completed, mixture, organic layer anhydrous Na are extracted with 10mL ethyl acetate2SO4It is dry, use rotary evaporation
Instrument removes solvent, and residue chromatographs (eluant, eluent volume ratio is ethyl acetate: petroleum ether=1:3) purifying through Flash silica column, obtains
To white solid 3ae；
.mp:165.1-162.8 DEG C of White solid (65%, 150.5mg),1H NMR(500MHz,DMSO-d6)δ
11.76(s,1H),10.14(s,1H),8.31(s,1H),7.99–7.92(m,2H),7.91–7.85(m,2H),7.62–7.56
(m,2H),7.52–7.38(m,3H),7.32–7.24(m,1H),7.06–6.98(m,2H).13C NMR(125MHz,DMSO-d6)
δ 165.7 (d, J=252.1Hz), 164.7 (d, J=251.1Hz), 148.9,141.0 (d, J=3.1Hz), 133.9 (d, J=
2.7Hz), 132.4,131.7 (d, J=9.9Hz), 128.5 (d, J=9.7Hz), 125.1,121.7,121.2,117.0 (d, J
=23.1Hz), 116.8 (d, J=22.9Hz), 116.4,111.7,89.69.HRMS (m/z) (ESI): calcd for
C20H14F2N3O4S2[M–H]-462.0394,found 462.0395。
Embodiment 6:
The synthesis and characterization of the chloro- N '-of 4- (3- (4- chlorphenyl) sulfonyl -1H- indoles -2- base) benzene sulfonyl hydrazide (3af):
Respectively by the indoles of 0.5mmol, 1mmol is to chlorobenzenesulfonyl hydrazine and 1mmol NH4Br is added in 10mL three-necked bottle, is added
Enter the dissolution of 8mL ethyl alcohol, make anode with Reticulated Vitreous body carbon RVC, platinized platinum Pt makees cathode, in undivided cell, in 10mA perseverance
Electric current, argon gas are protected, and 5h is stirred to react under the conditions of 50 DEG C, and TLC monitors reaction process；
To after the reaction was completed, extract mixture, organic layer anhydrous Na with 10mL ethyl acetate2SO4It is dry, it is steamed with rotation
It sends out instrument and removes solvent, residue chromatographs (eluant, eluent volume ratio is ethyl acetate: petroleum ether=1:4) purifying through Flash silica column,
Obtain white solid 3af；
.mp:209.2-210.0 DEG C of White solid (75%, 175.6mg), 1H NMR (500MHz, DMSO-d6) δ
11.78 (s, 1H), 10.22 (s, 1H), 8.44 (s, 1H), 7.92-7.87 (m, 2H), 7.86-7.80 (m, 4H), 7.70-7.64
(m,2H),7.52–7.47(m,1H),7.32–7.27(m,1H),7.08–6.98(m,2H).13C NMR(125MHz,DMSO-
D6) 148.8 δ, 143.0,138.7,137.5,136.1,132.1,130.0,129.5,129.4,127.1,124.7,121.5,
120.9,116.1,111.4,89.1.HRMS(m/z)(ESI):calcd for C20H14Cl2N3O4S2[M–H]-493.9803,
found 493.9805。
Embodiment 7:
The synthesis and characterization of the bromo- N'- of 4- (3- (4- bromophenyl) sulfonyl -1H- indoles -2- base) benzene sulfonyl hydrazide (3ag):
Respectively by the indoles of 0.5mmol, 1mmol brosyl hydrazine and 1mmol Bu4NPF6It is added in 10mL three-necked bottle,
The dissolution of 8mL acetonitrile is added, makees anode with Reticulated Vitreous body carbon RVC, platinized platinum Pt makees cathode, in undivided cell, in 15mA
Constant current, argon gas are protected, and 3h is stirred to react under the conditions of 55 DEG C, and TLC monitors reaction process；
To after the reaction was completed, extract mixture, organic layer anhydrous Na with 10mL ethyl acetate2SO4It is dry, it is steamed with rotation
It sends out instrument and removes solvent, residue chromatographs (eluant, eluent volume ratio is ethyl acetate: petroleum ether=1:5) purifying through Flash silica column,
Obtain yellow solid 3ag；
.mp:219.5-221.0 DEG C of Yellow solid (60%, 175.5mg), 1H NMR (500MHz, DMSO-d6) δ
11.76(s,1H),10.21(s,1H),8.42(s,1H),7.98–7.93(m,2H),7.82–7.78(m,4H),7.78–7.73
(m,2H),7.50–7.43(m,1H),7.32–7.26(m,1H),7.06–6.98(m,2H).13C NMR(125MHz,DMSO-
d6)δ148.8,143.4,136.6,132.4,132.3,132.1,130.0,127.8,127.2,126.4,124.7,121.5,
120.9,116.1,111.4,89.0.HRMS(m/z)(ESI):HRMS(m/z)(ESI):calcd for C20H14Br2N3O4S2
[M–H]-583.8772,found 583.8774。
Embodiment 8:
The synthesis of 4- methoxyl group-N'- (3- (4- methoxyphenyl) sulfonyl -1H- indoles -2- base) benzene sulfonyl hydrazide (3ah)
And characterization:
Respectively by the indoles of 0.5mmol, 1mmol is added in 10mL three-necked bottle methoxybenzene sulfohydrazide and 1mmol KI,
The dissolution of 8mL methanol is added, makees anode with Reticulated Vitreous body carbon RVC, platinized platinum Pt makees cathode, in undivided cell, in 20mA
Constant current, argon gas are protected, and 4h is stirred to react under the conditions of 60 DEG C, and TLC monitors reaction process；
To after the reaction was completed, extract mixture, organic layer anhydrous Na with 10mL ethyl acetate2SO4It is dry, it is steamed with rotation
It sends out instrument and removes solvent, residue chromatographs (eluant, eluent volume ratio is ethyl acetate: petroleum ether=1:6) purifying through Flash silica column,
Obtain white solid 3ah；
.mp:189.1-189.9 DEG C of White solid (72%, 175.3mg), 1H NMR (500MHz, DMSO-d6) δ
11.71(s,1H),9.90(s,1H),7.90–7.83(m,3H),7.80–7.70(m,2H),7.46–7.40(m,1H),7.30–
7.22(m,3H),7.12–7.05(m,2H),7.04–6.96(m,2H),3.87(s,3H),3.79(s,3H).13C NMR
(125MHz,DMSO-d6)δ163.3,162.4,148.1,135.9,132.1,130.3,128.2,127.5,124.7,121.2,
120.7,116.1,114.7,114.4,111.3,90.2,55.9,55.7.HRMS(m/z)(ESI):calcd for
C22H22N3O6S2[M+H]+488.0950found 488.0932。
Embodiment 9:
The conjunction of 4- tert-butyl-N '-(3- (4- (tert-butyl) phenyl) sulfonyl -1H- indoles -2- base) benzene sulfonyl hydrazide (3ai)
At and characterization:
Respectively by the indoles of 0.5mmol, 1mmol is to tert-butyl benzene sulfohydrazide and 1mmol NH4Cl is added to 10mL three-necked bottle
In, the dissolution of 8mL ethyl alcohol is added, makees anode with Reticulated Vitreous body carbon RVC, platinized platinum Pt makees cathode, in undivided cell,
25mA constant current, argon gas are protected, and 5h is stirred to react under the conditions of 65 DEG C, and TLC monitors reaction process；
To after the reaction was completed, extract mixture, organic layer anhydrous Na with 10mL ethyl acetate2SO4It is dry, it is steamed with rotation
It sends out instrument and removes solvent, residue chromatographs (eluant, eluent volume ratio is ethyl acetate: petroleum ether=1:3) purifying through Flash silica column,
Obtain white solid 3ai；
.mp:193.5-194.0 DEG C of White solid (63%, 169.8mg), 1H NMR (500MHz, DMSO-d6) δ
11.71(s,1H),10.01(s,1H),8.02(s,1H),7.90–7.80(m,2H),7.77–7.65(m,4H),7.60–7.50
(m,2H),7.50–7.40(m,1H),7.30–7.20(m,1H),7.05–6.90(m,2H),1.29(s,9H),1.26(s,9H)
.13C NMR(125MHz,DMSO-d6)δ156.9,155.6,148.2,141.2,134.0,132.0,127.9,126.2,
126.0,125.7,125.5,125.1,124.6,121.2,120.7,116.1,111.3,89.7,35.0,34.8,34.7,
30.8,30.7,30.7.HRMS(m/z)(ESI):calcd for C28H33N3O4S2[M–H]-538.1834found
538.1832。
Embodiment 10:
N'- (3- ([1,1'- xenyl] -4- sulfonyl) -1H- indoles -2- base)-[1,1'- xenyl] -4- benzene sulfonyl hydrazide
The synthesis and characterization of (3aj):
Respectively by the indoles of 0.5mmol, 1mmol 4- biphenyl sulfohydrazide and 1mmol NH4Br is added in 10mL three-necked bottle,
The dissolution of 8mL acetonitrile is added, makees anode with Reticulated Vitreous body carbon RVC, platinized platinum Pt makees cathode, in undivided cell, in 30mA
Constant current, argon gas are protected, and 3h is stirred to react under the conditions of 70 DEG C, and TLC monitors reaction process；
To after the reaction was completed, extract mixture, organic layer anhydrous Na with 10mL ethyl acetate2SO4It is dry, it is steamed with rotation
It sends out instrument and removes solvent, residue chromatographs (eluant, eluent volume ratio is ethyl acetate: petroleum ether=1:4) purifying through Flash silica column,
Obtain white solid 3aj；
.mp:220.4-221.0 DEG C of White solid (60%, 173.7mg), 1H NMR (500MHz, DMSO-d6) δ
11.81 (s, 1H), 10.15 (s, 1H), 8.25 (s, 1H), 8.10-7.95 (m, 4H), 7.93-7.89 (m, 2H), 7.87-7.83
(m,2H),7.80–7.76(m,2H),7.71–7.67(m,2H),7.57–7.49(m,4H),7.48–7.39(m,4H),7.35–
7.25(m,1H),7.10–6.95(m,1H).13C NMR(125MHz,DMSO-d6)δ148.6,145.2,144.2,142.8,
138.5,138.2,135.8,132.1,129.2,129.1,128.8,128.7,128.5,127.5,127.2,127.1,
125.9,124.8,121.4,120.9,116.2,111.4,99.5,89.56.HRMS(m/z)(ESI):calcd for
C32H24N3O4S2[M–H]-578.1208found 578.1210。
Embodiment 11:
The synthesis and characterization of N'- (3- (2- naphthalene sulfonyl base) -1H- indoles -2- base) -2- naphthalene sulfonyl hydrazine (3ak):
Respectively by the indoles of 0.5mmol, 1mmol 2- naphthalene sulfonyl hydrazine and 1mmol Bu4NPF6It is added in 10mL three-necked bottle, adds
Enter the dissolution of 8mL methanol, make anode with Reticulated Vitreous body carbon RVC, platinized platinum Pt makees cathode, in undivided cell, in 10mA perseverance
Electric current, argon gas are protected, and 4h is stirred to react under the conditions of 50 DEG C, and TLC monitors reaction process；
To after the reaction was completed, extract mixture, organic layer anhydrous Na with 10mL ethyl acetate2SO4It is dry, it is steamed with rotation
It sends out instrument and removes solvent, residue chromatographs (eluant, eluent volume ratio is ethyl acetate: petroleum ether=1:5) purifying through Flash silica column,
Obtain white solid 3ak；
.mp:209.7-210.3 DEG C of White solid (65%, 171.3mg), 1H NMR (500MHz, DMSO-d6) δ
11.82 (s, 1H), 10.25 (s, 1H), 8.65-8.60 (m, 1H), 8.55-8.50 (m, 1H), 8.31 (s, 1H), 8.26-8.22
(m,1H),8.19–8.14(m,1H),8.13–8.07(m,2H),8.07–8.03(m,1H),8.02–7.92(m,2H),7.78–
7.70(m,3H),7.69–7.60(m,2H),7.54–7.48(m,1H),7.35–7.25(m,1H),7.05–6.90(m,2H)
.13C NMR(125MHz,DMSO-d6)δ148.8,140.9,134.8,134.2,132.1,131.7,131.7,129.6,
129.4,129.4,129.4,129.2,128.7,128.0,127.8,127.6,125.7,124.7,122.9,121.3,
120.8,116.1,111.3,89.3.HRMS(m/z)(ESI):calcd for C28H21N3O4S2[M–H]-526.0895found
526.0892。
Embodiment 12:
The synthesis and characterization of N'- (3- (2- thiophen sulfuryl) -1H- indoles -2- base) -2- thiophenesulfonyl hydrazine (3al):
Respectively by the indoles of 0.5mmol, 1mmol 2- thiophenesulfonyl hydrazine and 1mmol KI are added in 10mL three-necked bottle, are added
The dissolution of 8mL ethyl alcohol, makees anode with Reticulated Vitreous body carbon RVC, and platinized platinum Pt makees cathode, in undivided cell, in the permanent electricity of 15mA
Stream, argon gas are protected, and 5h is stirred to react under the conditions of 55 DEG C, and TLC monitors reaction process；
To after the reaction was completed, extract mixture, organic layer anhydrous Na with 10mL ethyl acetate2SO4It is dry, it is steamed with rotation
It sends out instrument and removes solvent, residue chromatographs (eluant, eluent volume ratio is ethyl acetate: petroleum ether=1:6) purifying through Flash silica column,
Obtain white solid 3al；
.mp:203.4-203.9 DEG C of White solid (86%, 188.72mg), 1H NMR (500MHz, DMSO-d6) δ
11.82(s,1H),10.21(s,1H),8.18–8.12(m,2H),7.89–7.83(m,1H),7.79–7.73(m,1H),7.67–
7.63(m,1H),7.52–7.46(m,1H),7.37–7.32(m,1H),7.32–7.27(m,1H),7.16–7.11(m,1H),
7.10–7.00(m,2H).13C NMR(125MHz,DMSO-d6)δ148.2,145.6,136.8,135.2,134.2,132.5,
132.1,130.3,128.2,127.8,124.5,121.4,121.0,116.3,111.4,90.1.HRMS(m/z)(ESI):
calcd for C16H12N3O4S4[M–H]-437.9711found 437.9712。
Embodiment 13:
The synthesis and characterization of N'- (3- (benzylsulphonyl) -1H- indoles -2- base) -1- benzylsulphonyl (3am):
Respectively by the indoles of 0.5mmol, 1mmol benzyl sulfohydrazide and 1mmol NH4Cl is added in 10mL three-necked bottle, is added
The dissolution of 8mL acetonitrile, makees anode with Reticulated Vitreous body carbon RVC, and platinized platinum Pt makees cathode, in undivided cell, in the permanent electricity of 20mA
Stream, argon gas are protected, and 5h is stirred to react under the conditions of 60 DEG C, and TLC monitors reaction process；
To after the reaction was completed, extract mixture, organic layer anhydrous Na with 10mL ethyl acetate2SO4It is dry, it is steamed with rotation
It sends out instrument and removes solvent, residue chromatographs (eluant, eluent volume ratio is ethyl acetate: petroleum ether=1:3) purifying through Flash silica column,
Obtain yellow solid 3am；
.mp:197.1-198.9 DEG C of Yellow solid (40%, 91.0mg), 1H NMR (400MHz, DMSO-d6) δ
11.54(s,1H),9.64(s,1H),8.17(s,1H),7.48–7.43(m,1H),7.41–7.37(m,5H),7.31–7.27
(m, 1H), 7.26-7.22 (m, 3H), 7.19-7.13 (m, 2H), 7.01-6.93 (m, 2H), 4.45-4.40 (m, 4H) .13C
NMR(100MHz,DMSO-d6)δ149.3,131.7,131.1,130.9,130.8,129.6,128.7,128.6,128.4,
128.1,125.8,121.0,120.4,116.4,111.1,87.4,61.7,55.5.HRMS(m/z)(ESI):calcd for
C22H20N3O4S2[M–H]-454.0895found 454.0899。
Embodiment 14:
The synthesis of 4- methyl-N'- (5- methyl -3- tosyl -1H- indoles -2- base) benzene sulfonyl hydrazide (3ba) and table
Sign:
Respectively by the 5- methyl indol of 0.5mmol, 1mmol unifor and 1mmol NH4Br is added to tri- neck of 10mL
In bottle, the dissolution of 8mL methanol being added, makees anode with Reticulated Vitreous body carbon RVC, platinized platinum Pt makees cathode, in undivided cell,
25mA constant current, argon gas are protected, and 4h is stirred to react under the conditions of 65 DEG C, and TLC monitors reaction process；
To after the reaction was completed, extract mixture, organic layer anhydrous Na with 10mL ethyl acetate2SO4It is dry, it is steamed with rotation
It sends out instrument and removes solvent, residue chromatographs (eluant, eluent volume ratio is ethyl acetate: petroleum ether=1:4) purifying through Flash silica column,
Obtain white solid 3ba；
.mp:184.3-185.2 DEG C of White solid (77%, 180.6mg), 1H NMR (400MHz, DMSO-d6) δ
11.61(s,1H),9.93(s,1H),7.85(s,1H),7.82–7.76(m,2H),7.70–7.64(m,2H),7.56–7.50
(m,2H),7.39–7.34(m,2H),7.26–7.22(m,1H),7.18–7.13(m,1H),6.84–6.78(m,1H),2.44
(s,3H),2.34(s,3H),2.31(s,3H).13C NMR(100MHz,DMSO-d6)δ148.3,144.4,142.9,141.3,
133.9,130.2,130.0,129.9,129.6,127.9,125.2,124.9,121.9,116.1,111.0,89.4,21.3,
21.1,20.9.HRMS(m/z)(ESI):calcd for C23H22N3O4S2[M–H]-468.1052found 468.1053。
Embodiment 15:
The synthesis of 4- methyl-N'- (6- methyl -3- tosyl -1H- indoles -2- base) benzene sulfonyl hydrazides (3ca) and table
Sign:
Respectively by the 6- methyl indol of 0.5mmol, 1mmol unifor and 1mmol Bu4NPF6It is added to tri- neck of 10mL
In bottle, the dissolution of 8mL ethyl alcohol being added, makees anode with Reticulated Vitreous body carbon RVC, platinized platinum Pt makees cathode, in undivided cell,
30mA constant current, argon gas are protected, and 5h is stirred to react under the conditions of 70 DEG C, and TLC monitors reaction process；
To after the reaction was completed, extract mixture, organic layer anhydrous Na with 10mL ethyl acetate2SO4It is dry, it is steamed with rotation
It sends out instrument and removes solvent, residue is residual through Flash silica column chromatography (eluant, eluent volume ratio is ethyl acetate: petroleum ether=1:5) purifying
Excess obtains white solid 3ca；
.mp:145.2-145.9 DEG C of White solid (67%, 157.1mg), 1H NMR (400MHz, DMSO-d6) δ
11.61(s,1H),9.94(s,1H),7.85–7.75(m,3H),7.70–7.62(m,2H),7.60–7.50(m,2H),7.40–
7.25(m,3H),7.08(s,1H),6.90–6.80(m,1H),2.43(s,3H),2.33(s,3H),2.30(s,3H).13C
NMR (100MHz, DMSO-d6) δ 148.0,144.4,142.9,141.2,133.9,132.4,129.9,129.9,129.6,
128.0,125.2,122.5,122.4,115.9,111.4,89.5,21.2,21.1,20.9.HRMS(m/z)(ESI):calcd
for C23H24N3O4S2[M+H]+470.1208found 470.1198。
Embodiment 16:
The synthesis of 4- methyl-N'- (7- methyl -3- tosyl -1H- indoles -2- base) benzene sulfonyl hydrazide (3da) and table
Sign:
The 7- methyl indol of 0.5mmol, 1mmol unifor and 1mmol KI are added to 10mL three-necked bottle respectively
In, the dissolution of 8mL acetonitrile is added, makees anode with Reticulated Vitreous body carbon RVC, platinized platinum Pt makees cathode, in undivided cell,
10mA constant current, argon gas are protected, and 3h is stirred to react under the conditions of 50 DEG C, and TLC monitors reaction process；
To after the reaction was completed, extract mixture, organic layer anhydrous Na with 10mL ethyl acetate2SO4It is dry, it is steamed with rotation
It sends out instrument and removes solvent, residue chromatographs (eluant, eluent volume ratio is ethyl acetate: petroleum ether=1:6) purifying through Flash silica column,
Obtain white solid 3da；
.mp:134.3-135.0 DEG C of White solid (58%, 136.0mg), 1H NMR (400MHz, DMSO-d6) δ
11.32(s,1H),9.86(s,1H),7.83(s,1H),7.80–7.73(m,2H),7.72–7.65(m,2H),7.50–7.42
(m, 2H), 7.40-7.32 (m, 2H), 7.30-7.20 (m, 1H), 6.95-6.87 (m, 1H), 6.85-6.75 (m, 1H), 2.38
(s,6H),2.33(s,3H).13C NMR(100MHz,DMSO-d6)δ148.2,144.4,143.0,141.0,134.0,
131.0,129.8,129.6,127.9,125.3,124.4,122.3,121.5,120.8,113.8,90.4,21.1,20.9,
17.0.HRMS(m/z)(ESI):calcd for C23H22N3O4S2[M–H]-468.1052found 468.1054。
Embodiment 17:
The synthesis of N'- (5- methoxyl group -3- tosyl -1H- indoles -2- base) -4- toluene sulfonyl hydrazide (3ea) and table
Sign:
Respectively by the 5- methyl indol of 0.5mmol, 1mmol unifor and 1mmol NH4Cl is added to tri- neck of 10mL
In bottle, the dissolution of 8mL methanol being added, makees anode with Reticulated Vitreous body carbon RVC, platinized platinum Pt makees cathode, in undivided cell,
15mA constant current, argon gas are protected, and 3h is stirred to react under the conditions of 55 DEG C, and TLC monitors reaction process；
To after the reaction was completed, extract mixture, organic layer anhydrous Na with 10mL ethyl acetate2SO4It is dry, it is steamed with rotation
It sends out instrument and removes solvent, residue is residual through Flash silica column chromatography (eluant, eluent volume ratio is ethyl acetate: petroleum ether=1:3) purifying
Excess obtains white solid 3ea；
.mp:156.9-157.6 DEG C of White solid (54%, 131.0mg), 1H NMR (400MHz, DMSO-d6) δ
11.57(s,1H),9.94(s,1H),7.87(s,1H),7.83–7.77(m,2H),7.72–7.66(m,2H),7.57–7.50
(m,2H),7.40–7.34(m,2H),7.20–7.14(m,1H),6.99–6.93(m,1H),6.67–6.57(m,1H),3.72
(s,3H),2.44(s,3H),2.34(s,3H).13C NMR(100MHz,DMSO-d6)δ154.9,148.5,144.4,143.0,
141.2,134.0,129.9,129.6,128.0,126.6,125.6,125.2,112.0,108.6,100.2,89.9,55.4,
21.1,20.9.HRMS(m/z)(ESI):calcd for C23H22N3O5S2[M–H]-484.1001found 484.1003。
Embodiment 18:
The synthesis and characterization of N'- (the chloro- 3- tosyl -1H- indoles -2- base of 6-) -4- toluene sulfonyl hydrazide (3fa):
Respectively by the 6- chloro-indole of 0.5mmol, 1mmol unifor and 1mmol NH4Br is added to 10mL three-necked bottle
In, the dissolution of 8mL ethyl alcohol is added, makees anode with Reticulated Vitreous body carbon RVC, platinized platinum Pt makees cathode, in undivided cell,
20mA constant current, argon gas are protected, and 4h is stirred to react under the conditions of 60 DEG C, and TLC monitors reaction process；
To after the reaction was completed, extract mixture, organic layer anhydrous Na with 10mL ethyl acetate2SO4It is dry, it is steamed with rotation
It sends out instrument and removes solvent, residue is residual through Flash silica column chromatography (eluant, eluent volume ratio is ethyl acetate: petroleum ether=1:4) purifying
Excess obtains white solid 3fa；
.mp:132.3-132.9 DEG C of White solid (75%, 183.4mg), 1H NMR (400MHz, DMSO-d6) δ
11.82 (s, 1H), 10.03 (s, 1H), 8.12 (s, 1H), 7.81-7.76 (m, 2H), 7.72-7.67 (m, 2H), 7.58-7.50
(m, 2H), 7.46-7.41 (m, 1H), 7.39-7.34 (m, 2H), 7.29-7.26 (m, 1H), 7.08-7.02 (m, 1H), 2.44
(s,3H),2.34(s,3H).13C NMR(100MHz,DMSO-d6)δ148.9,144.4,143.2,140.9,133.9,
132.7,129.8,129.7,128.0,125.3,125.0,123.6,121.4,117.3,111.0,89.9,21.1,
20.9.HRMS(m/z)(ESI):calcd for C22H19ClN3O4S2[M-H]-488.0505,found 488.0508。
Embodiment 19:
The synthesis and characterization of N'- (the fluoro- 3- tosyl -1H- indoles -2- base of 6-) -4- toluene sulfonyl hydrazide (3ga):
Respectively by the 6- fluoro indole of 0.5mmol, 1mmol unifor and 1mmol Bu4NPF6It is added to 10mL three-necked bottle
In, the dissolution of 8mL acetonitrile is added, makees anode with Reticulated Vitreous body carbon RVC, platinized platinum Pt makees cathode, in undivided cell,
25mA constant current, argon gas are protected, and 5h is stirred to react under the conditions of 65 DEG C, and TLC monitors reaction process；
To after the reaction was completed, extract mixture, organic layer anhydrous Na with 10mL ethyl acetate2SO4It is dry, it is steamed with rotation
It sends out instrument and removes solvent, residue is residual through Flash silica column chromatography (eluant, eluent volume ratio is ethyl acetate: petroleum ether=1:5) purifying
Excess obtains white solid 3ga；
.mp:127.5-128.2 DEG C of White solid (55%, 130.1mg), 1H NMR (400MHz, DMSO-d6) δ
11.80(s,1H),9.99(s,1H),8.00(s,1H),7.81–7.76(m,2H),7.72–7.65(m,2H),7.60–7.50
(m,2H),7.44–7.34(m,3H),7.10–7.00(m,1H),6.92–6.84(m,1H),2.44(s,3H),2.34(s,3H)
.13C NMR (100MHz, DMSO-d6) δ 158.5 (d, J=234.6Hz), 157.3,149.3 (d, J=1.8Hz), 144.8,
(143.5,141.4,134.4,132.7 d, J=12.5Hz), 130.3,130.1,128.4,125.7,121.6,117.3 (d, J
=9.7Hz), 109.2 (d, J=23.5Hz), 98.7 (d, J=26.9Hz), 90.00,21.5,21.3.HRMS (m/z) (ESI):
calcd for C22H19FN3O4S2[M-H]-472.0801,found 472.0802。
Embodiment 1-19 compound pharmacology activity research
Using MTT screened compound 3aa-3am and 3ba-3ga to 4 kinds of cancer cell line (MGC-803, T-24, HepG-2,
And SK-OV-3) and 1 plant of human normal cell line (WI-38) external inhibitory activity.Using 5-FU as positive control.Experimental result table
Bright majority of compounds has good inhibitory activity, wherein inhibition of the compound 3ae to tumor cell line to tumor cell line
Effect is best.As shown in table 1, IC of the compound 3ae to T-24 and HepG-250Value is respectively 12.4 ± 1.4 and 15.3 ± 0.9 μ
M.In addition, compound 3ae is obvious to inhibiting effect comparison normal person's WI -38 cell strain of tumour cell.
IC of 1. compound of table to five plants of cell strains50It is worth (μM)
| MGC-803 | T-24 | HepG-2 | SK-OV-3 | WI-38 | |
| 3aa | >40 | 30.5±1.4 | 25.5±1.7 | 35.9±1.8 | >40 |
| 3ab | 20.4±1.2 | 29.8±0.9 | 21.6±0.5 | 39.5±1.1 | 39.1±0.3 |
| 3ac | 27.8±0.4 | 28.1±0.5 | >40 | >40 | >40 |
| 3ad | 25.3±0.8 | >40 | >40 | >40 | >40 |
| 3ae | 20.7±0.7 | 12.4±1.4 | 15.3±0.9 | 25.1±2.3 | >40 |
| 3af | >40 | >40 | >40 | >40 | >40 |
| 3ag | >40 | >40 | >40 | >40 | >40 |
| 3ah | 29.2±2.3 | 32.9±1.6 | >40 | 35.7±0.3 | 37.9±1.5 |
| 3ai | >40 | >40 | >40 | >40 | >40 |
| 3aj | >40 | >40 | >40 | >40 | >40 |
| 3ak | 23.7±0.6 | 27.2±1.9 | 32.9±1.8 | >40 | 35.4±1.7 |
| 3al | >40 | 29.4± | >40 | 38.1±1.8 | >40 |
| 3am | >40 | >40 | >40 | >40 | >40 |
| 3ba | 21.5±1.2 | 25.3±0.5 | 34.5±0.7 | >40 | >40 |
| 3ca | 19.4±0.9 | 33.2±1.6 | >40 | >40 | >40 |
| 3da | >40 | >40 | >40 | 32.5±0.9 | >40 |
| 3ea | >40 | 30.7±1.5 | >40 | >40 | >40 |
| 3fa | >40 | >40 | >40 | >40 | >40 |
| 3ga | 17.6±1.5 | 27.1±2.2 | >40 | 34.0±0.6 | >40 |
| 5-FU | 35.2±0.8 | 38.4±1.1 | >40 | >40 | >40 |
It is studied using anti-tumor activity of the mtt assay to all compounds, the experimental results showed that majority of compounds
There is good inhibitory activity to tumor cell line, wherein compound 3ae is best to the inhibitory effect of tumor cell line.
Claims (5)
1. a kind of method of electrochemistry formated sulfonyl diazanyl Benzazole compounds, which is characterized in that synthetic method general formula is as follows:
Wherein, R1, R2=aromatic radical, fat-based；
Electrolyte are as follows: NH4I、NH4Br、Bu4NPF6、NH4Cl or KI；
Solvent are as follows: acetonitrile, methanol or ethyl alcohol；
The universal synthesis method of the sulfonyl diazanyl Benzazole compounds, includes the following steps:
(A) respectively by the indoles of 0.5mmol (1), the electrolyte of 1mmol benzene sulfonyl hydrazide (2) and 1mmol are added to 10mL three-necked bottle
In, the dissolution of 8mL solvent is added, makees anode with Reticulated Vitreous body carbon RVC, platinized platinum Pt makees cathode, in undivided cell, with
10-30mA constant current, argon gas are protected, and 3-5h is stirred to react under the conditions of 50-70 DEG C, and TLC monitors reaction process；
(B) to after the reaction was completed, extract mixture, organic layer anhydrous Na with 10mL ethyl acetate2SO4It is dry, use rotary evaporation
Instrument removes solvent, and residue obtains product (3) through Flash silica column chromatographic purifying.
2. the method for electrochemistry formated sulfonyl diazanyl Benzazole compounds according to claim 1, it is characterised in that: step
Suddenly (B) the Flash silica column chromatographic purifying, eluant, eluent volume ratio are ethyl acetate: petroleum ether=1:3-6.
3. the sulfonyl diazanyl Benzazole compounds of -2 described in any item electrochemical method for synthesizing synthesis according to claim 1,
It is characterized in that, the structure of sulfonyl diazanyl Benzazole compounds is as follows:
4. sulfonyl diazanyl Benzazole compounds or its pharmaceutically acceptable salt described in claim 3 are preparing anti-tumor drug
In application.
5. being prepared using sulfonyl diazanyl Benzazole compounds described in claim 3 or its pharmaceutically acceptable salt as active constituent
Anti-tumor drug.
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| CN111170924A (en) * | 2020-02-18 | 2020-05-19 | 广西师范大学 | Method for electrochemically synthesizing hexafluoroisopropoxy indole compound |
| CN111286748A (en) * | 2020-02-12 | 2020-06-16 | 齐鲁工业大学 | Method for electrochemically synthesizing carbazole compounds |
| CN114507866A (en) * | 2022-03-02 | 2022-05-17 | 南京先进生物材料与过程装备研究院有限公司 | Electrochemical-mediated synthesis method of 2-arylbenzofuran compounds |
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