CN106048648A - Electrochemical catalysis synthesis method of 3-sulfonyl substituted oxo indoles compound - Google Patents
Electrochemical catalysis synthesis method of 3-sulfonyl substituted oxo indoles compound Download PDFInfo
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Abstract
The invention discloses an electrochemical catalysis synthesis method of a 3-sulfonyl substituted oxo indoles compound, and belongs to synthesis of compounds. The method uses a sulfoacid reagent represented by a formula (III) or sulfonyl hydrazine represented by a formula (V) or N-substituted acrylamide represented by a formula (II) as a raw material in a single-cell electrolytic tank; and in presence of an electrocatalyst, the raw material is electrolyzed in electrolyte at a certain temperature to obtain the 3-sulfonyl substituted oxo indoles compound represented by a formula (I). The method firstly adopts an operation-simple electrochemical catalysis indirect electrolysis method to synthesize the 3-sulfonyl substituted oxo indoles compound, uses the single-cell electrolytic tank and constant-current electrolysis, uses a cheap and easy-obtained graphite piece as a working electrode, largely reduces the cost, in particular, reduces heavy metal or chemical-metered oxidant, prevents generation of chemical wastes, is simpler in operation, and is more suitable for industrial production.
Description
Technical field
The present invention relates to the electrochemical catalysis synthetic method of a kind of 3-sulfonic group substituted oxindole compounds, belong to
The synthesis of compound.
Background technology
3-sulfonic group substituted oxindole compounds pharmaceutical chemistry and synthesis chemistry in be widely used, therefore such
The synthesis of compound is always focus of concern.
Chemical method is the method for synthesis 3-sulfonic group substituted oxindole compounds:
One, Wei wei et al. (Ref.Wei wei, Jiangwei wen, Daoshan Yang et al.Green
Chem., 2014,16,2988-2991) report and a kind of nonmetal catalyzed be directly synthesized the substituted Oxoindole of 3-sulfonic group
Compounds.The method is as solvent with acetonitrile-water (1/2), under the conditions of 80 DEG C, and potassium peroxydisulfate (K stoichiometrically2S2O8)
For oxidant, the substituted Methacrylamide of N-reacts with sulfinic acid, generates 3-sulfonic group substituted oxindole compounds.
The subject matter that the method exists is as follows:
(1) the method must stoichiometrically have corrosive potassium peroxydisulfate (K2S2O8) it is oxidant, easily endanger
Danger, and react terminate after produce substantial amounts of inorganic salt sodium sulfate (Na2SO4), the generation of chemical waste can be caused；
(2) it is sulfonic source due to the method with sulfinic acid sodium, course of reaction has certain penetrating odor,
Therefore environment, human body are harmful to.
Two, Tao shen et al. (Ref.Tao Shen, Yizhi Yuan, Song Song et al.Chem.Commun.,
2014,50,4115-4118) report and be directly synthesized 3-sulfonic group substituted oxindole class with metallic iron as catalyst
Compound.The method is using acetonitrile as solvent, under the conditions of 100 DEG C, with the Fe (NO of catalytic amount3)3·9H2O is catalyst, and N-replaces
Methacrylamide react with sulfinic acid, generate 3-sulfonic group substituted oxindole compounds.The master that the method exists
Want problem as follows:
(1) the method must be with metal Fe (NO3)3·9H2O is as catalyst, and the chemical waste of generation can cause a huge sum of money
Belong to and polluting；
(2) the method is sulfonic source with sulfinic acid sodium equally, has certain penetrating odor in course of reaction,
Therefore environment, human body are harmful to.
Three, Xiaoqing Li et al. (Ref.Xiaoqing Li, Xiangsheng Xu, Peizhu Hu et
Al.J.Org.Chem.2013,78,7343-7348) report with non-metallic catalyst KI, 18-crown-6 and stoichiometric
TBHP is that oxidant is directly synthesized 3-sulfonic group substituted oxindole compounds.The method using water as reaction dissolvent, 80
Under the conditions of DEG C, with KI and 18-crown-6 of catalytic amount as catalyst, TBHP stoichiometrically is oxidant, the substituted first of N-
Base acrylamide reacts with hydrazine sulphonate, generates 3-sulfonic group substituted oxindole compounds.What the method existed mainly asks
Inscribe as follows:
(1) the method must TBHP stoichiometrically as oxidant, there is certain corrosivity and danger.
(2) the method must need extra raw material system using the hydrazine sulphonate of sense dough in advance as sulfonic source
Preparation Method.
At present, 3-sulfonic group substituted oxidized indole compounds electrochemistry under single compartment electrolytic cell and constant current conditions is urged
It is combined to method and there is not yet domestic and foreign literature report.
Summary of the invention
It is an object of the invention to provide a kind of simple to operate and 3-sulfonic group substituted oxindole class chemical combination of low cost
The electrochemical catalysis synthetic method of thing, its step is to represent sulfonating reagent or formula (V) with formula (III) in single compartment electrolytic cell
Represent that the N-substituted acrylamide that sulfohydrazide and formula (II) represent is raw material, in the presence of eelctro-catalyst, certain temperature and electricity
Solve electrolysis in liquid and obtain the 3-sulfonic group substituted oxindole compounds that formula (I) represents.
Wherein, R1Represent-H, halogen, alkyl or aryl；R2Represent-H or-alkyl；R3Expression-alkyl ,-aryl or-acyl
Base；R4Expression-alkyl ,-acyl group or-aryl；R5Represent-H or-alkyl；R6Represent-H or-alkyl；R7Expression-alkyl or-virtue
Base；M is expressed as-OH or-ONa.
Any one in tetraalkylphosphonium halide amine, alkali halide, ammonium halide of eelctro-catalyst.
Above-mentioned tetraalkylphosphonium halide amine is tetrabutylammonium iodide, tetrabutyl ammonium bromide ammonium or tetraethylammonium bromide.
Above-mentioned alkali halide is sodium iodide, potassium iodide, sodium bromide or potassium bromide.
Above-mentioned ammonium halide is ammonium iodide or ammonium bromide.
The consumption of eelctro-catalyst is preferably N-substituted acrylamide: the mol ratio of eelctro-catalyst is 1:0.1.
Eelctro-catalyst is preferably ammonium bromide.
Above-mentioned electrolyte is acetonitrile: water (v/v=1/1) or Isosorbide-5-Nitrae-dioxane: water (v/v=1/1), preferably Isosorbide-5-Nitrae-two
Oxygen six ring: water (v/v:1/1).
The anode of above-mentioned electrolysis is graphite flake electrode, glass-carbon electrode or gauze platinum electrode, preferably graphite flake electrode.
The negative electrode of above-mentioned electrolysis is graphite flake electrode, aluminium flake electrode, iron plate electrode, copper plate electrode or zinc metal sheet electrode,
Preferably graphite flake electrode.
Above-mentioned temperature is 70-80 DEG C.
Preferably N-substituted acrylamide: the mol ratio of sulfonating reagent or sulfohydrazide is 1:(3-4).
Under preferably N-substituted acrylamide, the concentration in electrolyte is 0.05-0.1mol/L, such as 0.0830.05-0.1mol/
L。
The inventive method compared with prior art, has the advantages that
(1) the indirect electrolytic method using electrochemical catalysis simple to operate has synthesized the substituted oxindole of 3-sulfonic group
Compounds, using the eelctro-catalyst (especially ammonium bromide) of catalytic amount as catalyst, using electronics as " oxidising agent ", it is to avoid
Heavy metal and the use of stoichiometric oxidant, meanwhile, single compartment electrolytic cell device is simple, with common beaker, and yield height.
(2) using constant-current electrolysis method, the method equipment needed thereby low cost, operation the most relatively potentiostatic deposition is the simplest
Single, meanwhile, constant-current electrolysis is more suitable for industrialized production.
(3) working electrode is graphite flake cheap and easy to get so that cost is substantially reduced.
(4) the inventive method uses industrial common reagent and conventional working condition, and reaction condition is gentle, operation letter
Single, electrode material is cheap and easy to get simultaneously.Using electronics as oxidant in course of reaction, it also it is the production process of a kind of cleaning.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but the present invention is not limited to following example.
The electrochemical synthesis of embodiment 1:1,3-dimethyl-3-((4-toluene sulfonic acide base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-methyl-N-phenylmethyl acrylamide (1.0mmol), to methylbenzene Asia
Sodium sulfonate (3mmol) and ammonium bromide (0.1mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, altogether in the solution of 12mL, with 2.5
×1cm2Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h, stops electricity
Solving, solvent is sloughed in rotation steaming, extracts three times with dichloromethane, through column chromatography for separation, obtains 1,3-dimethyl-3-((4-methylbenzene sulphur
Acidic group) methyl) indolone.Yield: 73%.
White solid；mp:131-133℃；1H NMR(400MHz,CDCl3)δ1.40(s,3H),2.41(s,3H),
3.18 (s, 3H), 3.68 (d, J=14.4Hz, 1H), 3.87 (d, J=14.4Hz, 1H), 6.86 (d, J=7.6Hz, 1H), 6.94
(t, J=7.6Hz, 1H), 7.10 (d, J=7.2Hz, 1H), 7.18 (d, J=8.0Hz, 2H), 7.31 (t, J=10.8Hz, 1H),
7.40 (d, J=8.0Hz, 2H)；13C NMR(100MHz,CDCl3)δ21.6,25.6,34.9,45.6,61.8,108.5,
122.2,124.1,128.4,129.5,129.8,142.3,144.3,177.3.
The electrochemical synthesis of embodiment 2:1,3-dimethyl-3-((4-toluene sulfonic acide base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-methyl-N-phenylmethyl acrylamide (1.0mmol), to methylbenzene Asia
Sodium sulfonate (3mmol) and ammonium bromide (0.5mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, altogether in the solution of 12mL, with 2.5
×1cm2Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h, stops electricity
Solving, solvent is sloughed in rotation steaming, extracts three times with dichloromethane, through column chromatography for separation, obtains 1,3-dimethyl-3-((4-methylbenzene sulphur
Acidic group) methyl) indolone.Yield: 71%.
The electrochemical synthesis of embodiment 3:1,3-dimethyl-3-((4-toluene sulfonic acide base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-methyl-N-phenylmethyl acrylamide (1.0mmol), to methylbenzene Asia
Sodium sulfonate (3mmol) and ammonium bromide (0.5mmol) join acetonitrile: water=1:1, altogether in the solution of 12mL, with 2.5 × 1cm2's
Graphite flake is anode and negative electrode, at 2mA/cm2Being electrolysed under constant current, 80 DEG C of stirrings, as energising 8h, stop electrolysis, rotation is steamed
Slough solvent, extract three times with dichloromethane, through column chromatography for separation, obtain 1,3-dimethyl-3-((4-toluene sulfonic acide base) first
Base) indolone.Yield: 52%.
The electrochemical synthesis of embodiment 4:1,3-dimethyl-3-((4-toluene sulfonic acide base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-methyl-N-phenylmethyl acrylamide (1.0mmol), to methylbenzene Asia
Sodium sulfonate (3mmol) and ammonium iodide (0.5mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, altogether in the solution of 12mL, with 2.5
×1cm2Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h, stops electricity
Solving, solvent is sloughed in rotation steaming, extracts three times with dichloromethane, through column chromatography for separation, obtains 1,3-dimethyl-3-((4-methylbenzene sulphur
Acidic group) methyl) indolone.Yield: 19%.
The electrochemical synthesis of embodiment 5:1,3-dimethyl-3-((4-toluene sulfonic acide base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-methyl-N-phenylmethyl acrylamide (1.0mmol), to methylbenzene Asia
Sodium sulfonate (3mmol) and sodium iodide (0.5mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, altogether in the solution of 12mL, with 2.5
×1cm2Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h, stops electricity
Solving, solvent is sloughed in rotation steaming, extracts three times with dichloromethane, through column chromatography for separation, obtains 1,3-dimethyl-3-((4-methylbenzene sulphur
Acidic group) methyl) indolone.Yield: 18%.
The electrochemical synthesis of embodiment 6:1,3-dimethyl-3-((4-toluene sulfonic acide base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-methyl-N-phenylmethyl acrylamide (1.0mmol), to methylbenzene Asia
Sodium sulfonate (3mmol) and tetraethylammonium bromide (0.5mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, altogether the solution of 12mL
In, with 2.5 × 1cm2Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h
Time, stopping electrolysis, rotation steaming is sloughed solvent, is extracted three times with dichloromethane, through column chromatography for separation, obtain 1,3-dimethyl-3-
((4-toluene sulfonic acide base) methyl) indolone.Yield: 40%.
The electrochemical synthesis of embodiment 7:1,3-dimethyl-3-((4-toluene sulfonic acide base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-methyl-N-phenylmethyl acrylamide (1.0mmol), to methylbenzene Asia
Sodium sulfonate (3mmol) and tetrabutyl ammonium bromide (0.5mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, altogether the solution of 12mL
In, with 2.5 × 1cm2Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h
Time, stopping electrolysis, rotation steaming is sloughed solvent, is extracted three times with dichloromethane, through column chromatography for separation, obtain 1,3-dimethyl-3-
((4-toluene sulfonic acide base) methyl) indolone.Yield: 37%.
The electrochemical synthesis of embodiment 8:1,3-dimethyl-3-((4-toluene sulfonic acide base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-methyl-N-phenylmethyl acrylamide (1.0mmol), to methylbenzene Asia
Sodium sulfonate (3mmol) and ammonium bromide (0.1mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, altogether in the solution of 12mL, with 2.5
×1cm2Graphite flake be anode and 2.5 × 1cm2Aluminium flake be negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings,
As energising 8h, stopping electrolysis, rotation steaming is sloughed solvent, is extracted three times with dichloromethane, through column chromatography for separation, obtain 1,3-diformazan
Base-3-((4-toluene sulfonic acide base) methyl) indolone.Yield: 35%.
The electrochemical synthesis of embodiment 9:1,3-dimethyl-3-((4-toluene sulfonic acide base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-methyl-N-phenylmethyl acrylamide (1.0mmol), to methylbenzene Asia
Sodium sulfonate (3mmol) and ammonium bromide (0.1mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, altogether in the solution of 12mL, with 2.5
×1cm2Graphite flake be anode and 2.5 × 1cm2Iron plate be negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings,
As energising 8h, stopping electrolysis, rotation steaming is sloughed solvent, is extracted three times with dichloromethane, through column chromatography for separation, obtain 1,3-diformazan
Base-3-((4-toluene sulfonic acide base) methyl) indolone.Yield: 41%.
The electrochemical synthesis of embodiment 10:1,3-dimethyl-3-((4-toluene sulfonic acide base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-methyl-N-phenylmethyl acrylamide (1.0mmol), to methylbenzene Asia
Sodium sulfonate (3mmol) and ammonium bromide (0.1mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, altogether in the solution of 12mL, with 2.5
×1cm2Graphite flake be anode and 2.5 × 1cm2Copper sheet be negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings,
As energising 8h, stopping electrolysis, rotation steaming is sloughed solvent, is extracted three times with dichloromethane, through column chromatography for separation, obtain 1,3-diformazan
Base-3-((4-toluene sulfonic acide base) methyl) indolone.Yield: 30%.
The electrochemical synthesis of embodiment 11:1,3-dimethyl-3-((4-toluene sulfonic acide base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-methyl-N-phenylmethyl acrylamide (1.0mmol), to methylbenzene Asia
Sodium sulfonate (3mmol) and ammonium bromide (0.1mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, altogether in the solution of 12mL, with 2.5
×1cm2Graphite flake be anode and 2.5 × 1cm2Zinc metal sheet be negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings,
As energising 8h, stopping electrolysis, rotation steaming is sloughed solvent, is extracted three times with dichloromethane, through column chromatography for separation, obtain 1,3-diformazan
Base-3-((4-toluene sulfonic acide base) methyl) indolone.Yield: 37%.
The electrochemical synthesis of embodiment 12:1,3-dimethyl-3-((4-toluene sulfonic acide base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-methyl-N-phenylmethyl acrylamide (1.0mmol), to methylbenzene Asia
Sodium sulfonate (3mmol) and ammonium bromide (0.1mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, altogether in the solution of 12mL, with 2.5
×1cm2Glass carbon be anode and 2.5 × 1cm2Graphite flake be negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings,
As energising 8h, stopping electrolysis, rotation steaming is sloughed solvent, is extracted three times with dichloromethane, through column chromatography for separation, obtain 1,3-diformazan
Base-3-((4-toluene sulfonic acide base) methyl) indolone.Yield: 52%.
The electrochemical synthesis of embodiment 13:1,3-dimethyl-3-((4-toluene sulfonic acide base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-methyl-N-phenylmethyl acrylamide (1.0mmol), to methylbenzene Asia
Sodium sulfonate (3mmol) and ammonium bromide (0.1mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, altogether in the solution of 12mL, with 2.5
×1cm2Platinum guaze be anode and 2.5 × 1cm2Aluminium flake be negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, when
During energising 8h, stopping electrolysis, rotation steaming is sloughed solvent, is extracted three times with dichloromethane, through column chromatography for separation, obtain 1,3-diformazan
Base-3-((4-toluene sulfonic acide base) methyl) indolone.Yield: 55%.
The electrochemical synthesis of embodiment 14:1,3-dimethyl-3-((4-toluene sulfonic acide base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-methyl-N-phenylmethyl acrylamide (1.0mmol), to toluene Asia sulphur
Acid (3mmol) and ammonium bromide (0.1mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, in the solution of common 12mL, with 2.5 ×
1cm2Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h, stops electrolysis,
Solvent is sloughed in rotation steaming, extracts three times with dichloromethane, through column chromatography for separation, obtains 1,3-dimethyl-3-((4-toluene sulfonic acide
Base) methyl) indolone.Yield: 35%.
The electrochemical synthesis of embodiment 15:1,3-dimethyl-3-((benzenesulfonic acid base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-methyl-N-phenylmethyl acrylamide (1.0mmol), benzenesulfinic acid
(3mmol) Isosorbide-5-Nitrae-dioxane is joined with ammonium bromide (0.1mmol): water=1:1, altogether in the solution of 12mL, with 2.5 × 1cm2
Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h, stops electrolysis, rotation
Solvent is sloughed in steaming, extracts three times with dichloromethane, through column chromatography for separation, obtains 1,3-dimethyl-3-((benzenesulfonic acid base) methyl)
Indolone.Yield: 45%.
White solid；mp:149-150℃；1H NMR(400MHz,CDCl3)δ1.41(s,3H),3.19(s,3H),
3.71 (d, J=14.4Hz, 1H), 3.90 (d, J=14.4Hz, 1H), 6.86-6.93 (m, 2H), 7.05-7.07 (m, 1H),
7.30-7.32(m,1H),7.38-7.41(m,2H),7.50-7.57(m,3H)；13C NMR(100MHz,CDCl3)δ25.5,
26.6,45.6,61.8,108.4,122.6,124.0,127.8,128.6,128.9,129.4,133.4,143.3,177.6.
The electrochemical synthesis of embodiment 16:1,3-dimethyl-3-((4-chlorobenzenesulfonic acid base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-methyl-N-phenylmethyl acrylamide (1.0mmol), to chlorobenzene Asia sulphur
Acid (3mmol) and ammonium bromide (0.1mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, in the solution of common 12mL, with 2.5 ×
1cm2Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h, stops electrolysis,
Solvent is sloughed in rotation steaming, extracts three times with dichloromethane, through column chromatography for separation, obtains 1,3-dimethyl-3-((4 chlorobenzenesulfonic acid base)
Methyl) indolone.Yield: 49%.
White solid；mp:143-144℃；1H NMR(400MHz,CDCl3)δ1.38(s,3H),3.19(s,3H),
3.70 (d, J=14.4Hz, 1H), 3.92 (d, J=14.4Hz, 1H), 6.87 (d, J=7.6Hz, 1H), 6.93 (t, J=
7.6Hz, 1H), 7.02 (d, J=7.2Hz, 1H), 7.30 (d, J=7.6Hz, 1H), 7.34 (d, J=8.4Hz, 2H), 7.40 (d,
J=8.4Hz, 2H)；13C NMR(100MHz,CDCl3)δ25.5,26.6,45.5,61.9,108.5,122.5,123.9,
128.8,129.1,129.3,138.2,140.0,143.3,177.5.
The electrochemical synthesis of embodiment 17:1,3-dimethyl-3-((pyrovinic acid base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-methyl-N-phenylmethyl acrylamide (1.0mmol), methyl sulfinic acid
(3mmol) Isosorbide-5-Nitrae-dioxane is joined with ammonium bromide (0.1mmol): water=1:1, altogether in the solution of 12mL, with 2.5 × 1cm2
Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h, stops electrolysis, rotation
Solvent is sloughed in steaming, extracts three times with dichloromethane, through column chromatography for separation, obtains 1,3-dimethyl-3-((pyrovinic acid base) first
Base) indolone.Yield: 38%.
White solid；mp:108-109℃；1H NMR(400MHz,CDCl3)δ1.47(s,3H),2.61(s,3H),
3.27 (s, 3H), 3.60 (d, J=14.4Hz, 1H), 3.72 (d, J=14.8Hz, 1H), 6.93 (d, J=8.0Hz, 1H), 7.13
(t, J=7.6Hz, 1H), 7.34-7.37 (m, 2H)；13C NMR(100MHz,CDCl3)δ260.6,27.0,42.0,45.6,
60.8,108.9,122.6,123.6,129.1,130.1,143.4,177.7.
The electrochemical synthesis of embodiment 18:1,3-dimethyl-3-((4-toluene sulfonic acide base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-methyl-N-phenylmethyl acrylamide (1.0mmol), tolysulfonyl
Hydrazine (3mmol) and ammonium bromide (0.1mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, altogether in the solution of 12mL, with 2.5 ×
1cm2Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h, stops electrolysis,
Solvent is sloughed in rotation steaming, extracts three times with dichloromethane, through column chromatography for separation, obtains 1,3-dimethyl-3-((4-toluene sulfonic acide
Base) methyl) indolone.Yield: 40%.
The electrochemical synthesis of embodiment 19:1,3-dimethyl-3-((benzenesulfonic acid base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-methyl-N-phenylmethyl acrylamide (1.0mmol), phenylsulfinyl hydrazine
(3mmol) Isosorbide-5-Nitrae-dioxane is joined with ammonium bromide (0.1mmol): water=1:1, altogether in the solution of 12mL, with 2.5 × 1cm2
Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h, stops electrolysis, rotation
Solvent is sloughed in steaming, extracts three times with dichloromethane, through column chromatography for separation, obtains 1,3-dimethyl-3-((benzenesulfonic acid base) methyl)
Indolone.Yield: 35%.
The electrochemical synthesis of embodiment 20:1,3-dimethyl-3-((4-first chlorobenzenesulfonic acid base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-methyl-N-phenylmethyl acrylamide (1.0mmol), to chlorobenzenesulfonyl
Hydrazine (3mmol) and ammonium bromide (0.1mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, altogether in the solution of 12mL, with 2.5 ×
1cm2Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h, stops electrolysis,
Solvent is sloughed in rotation steaming, extracts three times with dichloromethane, through column chromatography for separation, obtains 1,3-dimethyl-3-((4-chlorobenzenesulfonic acid base)
Methyl) indolone.Yield: 39%.
The electrochemical synthesis of embodiment 21:1,3-dimethyl-3-((pyrovinic acid base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-methyl-N-phenylmethyl acrylamide (1.0mmol), sulfonyloxy methyl hydrazine
(3mmol) Isosorbide-5-Nitrae-dioxane is joined with ammonium bromide (0.1mmol): water=1:1, altogether in the solution of 12mL, with 2.5 × 1cm2
Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h, stops electrolysis, rotation
Solvent is sloughed in steaming, extracts three times with dichloromethane, through column chromatography for separation, obtains 1,3-dimethyl-3-((pyrovinic acid base) first
Base).Yield: 29%.
The electrochemical synthesis of embodiment 22:1-methyl-3-acetyl group-3-((benzenesulfonic acid base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-ethyl, N-phenyl ethyl acrylamide (1.0mmol), to methylbenzene Asia
Sodium sulfonate (3mmol) and ammonium bromide (0.1mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, altogether in the solution of 12mL, with 2.5
×1cm2Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h, stops electricity
Solving, solvent is sloughed in rotation steaming, extracts three times with dichloromethane, through column chromatography for separation, obtains 1-methyl-3-ethyl-3-((4-methyl
Benzenesulfonic acid base) methyl) indolone.Yield: 47%.
white solid；mp:178-180℃.1H NMR(CDCl3,400MHz):δ1.97(s,3H),3.17(s,3H),
3.88 (d, J=18.4Hz, 1H), 3.94 (d, J=17.6Hz, 1H), 4.03 (d, J=14.8Hz, 1H), 4.31 (d, J=
14.8Hz, 1H), 6.93-6.85 (m, 2H), 7.09 (d, J=7.6Hz, 1H), 7.33 (t, J=7.6Hz, 1H), 7.40 (t, J=
7.6Hz,2H),7.58-7.50(m,3H)；13C NMR(CDCl3,100MHz):δ20.5,26.6,49.2,58.0,67.1,
108.5,122.5,125.1,125.2,127.8,128.9,129.4,133.5,139.7,143.9,169.9,174.3.
The embodiment 23:1-ethyl-3-methylol-3-(electrochemical synthesis of ((benzenesulfonic acid base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by 2-methylol-N-ethyl, N-phenyl ethyl acrylamide (1.0mmol), benzene
Sulfinic acid sodium (3mmol) and ammonium bromide (0.1mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, altogether in the solution of 12mL, with
2.5×1cm2Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h, stops
Electrolysis, rotation steaming is sloughed solvent, is extracted three times with dichloromethane, through column chromatography for separation, obtain 1-ethyl-3-methylol-3-((4-
Toluene sulfonic acide base) methyl) indolone.Yield: 39%.
white solid；mp:172-174℃.1H NMR(CDCl3,400MHz):δ2.63(brs,1H),3.20(s,
3H),7.57-7.54(m,3H)；(3.64 d, J=11.2Hz, 1H), 3.72 (d, J=10.8Hz, 1H), 3.88 (d, J=
14.8Hz, 1H), 4.08 (d, J=14.8Hz, 1H), 6.96-6.87 (m, 2H), 7.10 (d, J=7.6Hz, 1H), 7.33 (t, J
=8.0Hz, 1H), 7.40 (t, J=7.6Hz, 2H)；13C NMR(CDCl3,100MHz):δ26.5,50.8,58.2,67.5,
108.6,122.7,124.7,125.5,127.7,128.9,129.2,133.4,140.0,143.9,176.3.
The electrochemical synthesis of embodiment 24:1,3-dimethyl-3-(1-methyl isophthalic acid-(benzenesulfonic acid base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by 2-methylol-N-ethyl, N-phenyl ethyl acrylamide (1.0mmol), benzene
Sulfinic acid sodium (3mmol) and ammonium bromide (0.1mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, altogether in the solution of 12mL, with
2.5×1cm2Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h, stops
Electrolysis, rotation steaming sloughs solvent, extracts three times with dichloromethane, through column chromatography for separation, obtain 1,3-dimethyl-3-(1-methyl isophthalic acid-
(4-toluene sulfonic acide base) methyl) indolone.Yield: 39%.
yellow oil；1H NMR(CDCl3, 400MHz): δ 1.73 (d, J=8.0Hz, 3H), 3.06 (s, 3H), 3.22
(s, 3H), 3.75 (q, J=7.2Hz, 1H), 6.86 (d, J=7.6Hz, 1H), 7.11 (t, J=8.4Hz, 1H), 7.53 (t, J=
7.6Hz, 2H), 7.81 (d, J=8.0Hz, 1H), 7.85 (d, J=8.8Hz, 2H), 7.96 (d, J=8.4Hz, 2H)；13C NMR
(CDCl3,100MHz):δ12.3,23.6,26.4,44.4,63.9,108.0,123.0,126.6,127.3,128.3,128.5,
129.1,129.4,133.5,133.7,178.2.
The electrochemical synthesis of embodiment 25:1,3-dimethyl-3-(1-ethyl-1-(benzenesulfonic acid base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by 2-methylol-N-ethyl, N-phenyl ethyl acrylamide (1.0mmol), right
Methyl sodium benzene sulphinate (3mmol) and ammonium bromide (0.1mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, altogether the solution of 12mL
In, with 2.5 × 1cm2Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h
Time, stopping electrolysis, rotation steaming is sloughed solvent, is extracted three times with dichloromethane, through column chromatography for separation, obtain 1,3-dimethyl-3-(1-
Ethyl-1-(4-toluene sulfonic acide base) methyl) indolone.Yield: 43%.
colorless oil；1H NMR(CDCl3, 400MHz): δ 0.98 (t, J=7.6Hz, 3H), 1.41 (s, 3H),
2.31-2.23 (m, 2H), 3.24 (s, 3H), 3.80 (t, J=5.6Hz, 1H), 6.90 (d, J=8.0Hz), 7.04-7.00 (m,
1H), 7.36-7.28 (m, 2H), 7.44 (t, J=7.2Hz, 2H), 7.64-7.54 (m, 1H), 7.67-7.65 (m, 2H)；13C
NMR(CDCl3,100MHz):δ14.6,19.6,25.0,26.6,48.8,71.7,108.7,122.2,124.1,128.5,
128.6,128.8,130.2,133.3,140.1,143.5,179.5.
(electrochemical synthesis of ((4-toluene sulfonic acide base) methyl) indolone exists embodiment 26:1-ethyl-3-methyl-3-
In the single compartment electrolytic cell of 50mL, by N-ethyl-N-phenylmethyl acrylamide (1.0mmol), to methyl sodium benzene sulphinate
(3mmol) Isosorbide-5-Nitrae-dioxane is joined with ammonium bromide (0.1mmol): water=1:1, altogether in the solution of 12mL, with 2.5 × 1cm2
Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h, stops electrolysis, rotation
Solvent is sloughed in steaming, extracts three times with dichloromethane, through column chromatography for separation, obtains 1-ethyl-3-methyl-3-(((4-methylbenzene sulphur
Acidic group) methyl) indolone.Yield: 64%.
White solid；mp:138-140℃；1H NMR(400MHz,CDCl3) δ 1.32 (t, J=7.2Hz, 3H), 1.40
(s,3H),2.41(s,3H),3.65-3.73(m,2H),3.78-3.87(m,2H),6.88-6.91(m,2H),7.05-7.07
(m, 1H), 7.18 (d, J=8.0Hz, 2H), 7.26-7.30 (m, 2H), 7.42 (d, J=8.0Hz, 2H)；13C NMR(100MHz,
CDCl3)δ12.3,21.6,25.6,34.9,45.6,61.8,108.5,122.2,124.2,127.7,128.5,129.5,
129.9,137.3,142.4,144.3,177.3.
The embodiment 27:1-phenyl-3-methyl-3-(electrochemical synthesis of ((4-toluene sulfonic acide base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N, N-diphenyl methyl acrylamide (1.0mmol), to toluenesulfinic acid
Sodium (3mmol) and ammonium bromide (0.1mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, altogether in the solution of 12mL, with 2.5 ×
1cm2Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h, stops electrolysis,
Solvent is sloughed in rotation steaming, extracts three times with dichloromethane, through column chromatography for separation, obtains 1-phenyl-3-methyl-3-(((4-methylbenzene
Sulfonic group) methyl) indolone.Yield: 75%.
White solid；mp:135-157℃；1H NMR(400MHz,CDCl3)δ1.52(s,3H),2.40(s,3H),
3.77 (d, J=14.4Hz, 2H), 4.00 (d, J=14.4Hz, 2H), 6.84-6.92 (m, 2H), 7.03-7.05 (m, 1H),
7.17-7.23 (m,3H),7.44-7.46(m,3H),7.51-7.58(m,4H)；13C NMR(100MHz,CDCl3)δ21.6,
25.8,45.8,62.4,109.7,122.8,124.0,126.9,127.7,128.5,129.3,129.7,134.6,137.3,
143.6,144.3,177.4.IR(KBr)(cm-1):ν2983,2935,1657,1625,1148,713.HRMS calcd for
C13H22NO3S:392.1320,found:392.1318.
The embodiment 28:1-benzyl-3-methyl-3-(electrochemical synthesis of ((4-toluene sulfonic acide base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-phenyl-N-benzyl methacrylamide (1.0mmol), to methylbenzene Asia
Sodium sulfonate (3mmol) and ammonium bromide (0.1mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, altogether in the solution of 12mL, with 2.5
×1cm2Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h, stops electricity
Solving, solvent is sloughed in rotation steaming, extracts three times with dichloromethane, through column chromatography for separation, obtains 1-benzyl-3-methyl-3-(((4-methyl
Benzenesulfonic acid base) methyl) indolone.Yield: 65%.
White solid；mp:141-143℃；1H NMR(400MHz,CDCl3)δ1.46(s,3H),2.41(s,3H),
3.73 (d, J=14.4Hz, 2H), 3.92 (d, J=14.4Hz, 2H), 4.80 (d, J=15.6Hz, 2H), 5.01 (d, J=
16.0Hz, 2H), 6.71 (d, J=7.6Hz, 1H), 6.86 (d, J=7.6Hz, 1H), 7.05 (d, J=7.2Hz, 1H), 7.13-
(7.19 m, 3H), 7.26-7.29 (m, 2H), 7.32-7.39 (m, 5H), 7.43 (d, J=8.4Hz, 2H)；13C NMR(100MHz,
CDCl3)δ21.6,26.0,44.2,45.8,61.7,109.5,122.5,124.0,127.4,127.6,127.8,129.6,
129.6,135.9,137.2,142.4,144.3,177.9.
The embodiment 29:1,3,5-trimethyl-3-(electrochemical synthesis of ((4-toluene sulfonic acide base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-methyl-N-(4-aminomethyl phenyl) Methacrylamide (1.0mmol), right
Methyl sodium benzene sulphinate (3mmol) and ammonium bromide (0.1mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, altogether the solution of 12mL
In, with 2.5 × 1cm2Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h
Time, stopping electrolysis, rotation steaming is sloughed solvent, is extracted three times with dichloromethane, through column chromatography for separation, obtain 1,3,5-trimethyl-3-
(((4-toluene sulfonic acide base) methyl) indolone.Yield: 70%.
White solid；mp:107-108℃；1H NMR(400MHz,CDCl3)δ1.37(s,3H),2.15(s,3H),
2.41 (s, 3H), 3.19 (s, 3H), 3.66 (d, J=14.8Hz, 2H), 3.89 (d, J=14.8Hz, 2H), 6.67 (s, 1H),
6.75 (d, J=7.6Hz, 1H), 7.06 (d, J=8.0Hz, 1H), 7.14 (d, J=8.0Hz, 2H), 7.31 (d, J=8.0Hz,
2H)；13C NMR(100MHz,CDCl3)δ20.9,21.5,26.6,45.6,61.9,108.1,124.7,127.8,128.8,
129.3,129.4,131.8,137.0,141.0,144.1,177.6.
The embodiment 30:1,3-dimethyl-5-methoxyl group-3-(electrochemistry of ((4-toluene sulfonic acide base) methyl) indolone
Synthesis
In the single compartment electrolytic cell of 50mL, by N-methyl-N-(4-methoxyphenyl) Methacrylamide (1.0mmol),
Methyl sodium benzene sulphinate (3mmol) and ammonium bromide (0.1mmol) are joined Isosorbide-5-Nitrae-dioxane: water=1:1,12mL's is molten altogether
In liquid, with 2.5 × 1cm2Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h
Time, stopping electrolysis, rotation steaming is sloughed solvent, is extracted three times with dichloromethane, through column chromatography for separation, obtain 1,3-dimethyl-5-first
Epoxide-3-(((4-toluene sulfonic acide base) methyl) indolone.Yield: 70%.
White solid；mp:144-136℃；1H NMR(400MHz,CDCl3)δ1.38(s,3H),2.40(s,3H),
3.17 (s, 3H), 3,63-3.67 (m, 4H), 3.87 (d, J=14.4Hz, 1H), 6.52 (d, J=2.0Hz, 1H), 6.74-6.81
(m, 2H), 7.16 (d, J=8.0Hz, 2H), 7.35 (d, J=8.4Hz, 2H)；13C NMR(100MHz,CDCl3)δ21.5,
25.4,26.6,46.0,55.4,61.9,108.7,110.9,113.2,127.8,129.4,130.6,136.8,137.1,
144.2,155.8,177.3.
The chloro-3-of the embodiment 31:1,3-dimethyl-5-(electrochemical synthesis of ((4-toluene sulfonic acide base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-methyl-N-(4-chlorphenyl) Methacrylamide (1.0mmol), to first
Base benzene sulfinic acid sodium salt (3mmol) and ammonium bromide (0.1mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, altogether the solution of 12mL
In, with 2.5 × 1cm2Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h
Time, stopping electrolysis, rotation steaming is sloughed solvent, is extracted three times with dichloromethane, through column chromatography for separation, obtain 1, and 3-dimethyl-5-is chloro-
3-(((4-toluene sulfonic acide base) methyl) indolone.Yield: 54%.
White solid；mp:154-155℃；1H NMR(400MHz,CDCl3)δ1.37(s,3H),2.43(s,3H),
3.24 (s, 3H), 3.66 (d, J=14.8Hz, 1H), 3.90 (d, J=14.8Hz, 1H), 6.72 (d, J=2.0Hz, 1H), 6.79
(d, J=8.4Hz, 1H), 7.18 (d, J=8.0Hz, 2H), 7.22-7.24 (m, 1H), 7.32 (d, J=8.0Hz, 2H)；13C
NMR(100MHz,CDCl3)δ26.6,45.6,61.6,109.2,124.2,126.7,127.4,127.5,127.8,128.4,
129.5,130.8,136.6,141.9,144.6,177.1.
Embodiment 32:1-methyl isophthalic acid-(((4-toluene sulfonic acide base) methyl)-5,6-dihydro-4H-pyrroles [3,2,1-ij]
The electrochemical synthesis of quinolinone
In the single compartment electrolytic cell of 50mL, by 1-methylacryloyl-1,2,3,4-tetrahydroquinolines (1.0mmol), to first
Base benzene sulfinic acid sodium salt (3mmol) and ammonium bromide (0.1mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, altogether the solution of 12mL
In, with 2.5 × 1cm2Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h
Time, stopping electrolysis, rotation steaming is sloughed solvent, is extracted three times with dichloromethane, through column chromatography for separation, obtain 1-methyl isophthalic acid-(((4-first
Base benzenesulfonic acid base) methyl)-5,6-dihydro-4H-pyrroles [3,2,1-ij] quinolinone.Yield: 83%.
White solid；mp:144-145℃；1H NMR(400MHz,CDCl3)δ1.35(s,3H),1.93-2.00(m,
2H),2.34(s,3H),2.73(m,2H),3.53-3.59(m,1H),3.62-3.63(m,2H),3.66-3.80(m,1H),
6.75 (t, J=7.6Hz, 1H), 6.87 (d, J=7.6Hz, 1H), 6.97 (d, J=7.6Hz, 1H), 7.13 (d, J=8.0Hz,
2H), 7.35 (d, J=7.6Hz, 2H)；13C NMR(100MHz,CDCl3)δ21.0,24.5,24.9,25.0,39.0,44.7,
61.8,120.3,121.8,121.9,127.2,127.7,128.1,137.1,139.0,144.2,176.4.
The embodiment 33:1,3-dimethyl-3-(electrochemical synthesis of ((4-chlorobenzenesulfonic acid base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-methyl-N-phenylmethyl acrylamide (1.0mmol), to chlorobenzene Asia sulphur
Acid sodium (3mmol) and ammonium bromide (0.1mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, in the solution of common 12mL, with 2.5 ×
1cm2Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h, stops electrolysis,
Solvent is sloughed in rotation steaming, extracts three times with dichloromethane, through column chromatography for separation, obtains 1,3-dimethyl-3-(((4-chlorobenzenesulfonic acid
Base) methyl) indolone.Yield: 69%.
The electrochemical synthesis of embodiment 34:1,3-dimethyl-3-((benzenesulfonic acid base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-methyl-N-phenylmethyl acrylamide (1.0mmol), benzene sulfinic acid sodium salt
(3mmol) Isosorbide-5-Nitrae-dioxane is joined with ammonium bromide (0.1mmol): water=1:1, altogether in the solution of 12mL, with 2.5 × 1cm2
Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h, stops electrolysis, rotation
Solvent is sloughed in steaming, extracts three times with dichloromethane, through column chromatography for separation, obtains 1,3-dimethyl-3-((benzenesulfonic acid base) methyl)
Indolone.Yield: 55%.
The electrochemical synthesis of embodiment 35:1,3-dimethyl-3-((pyrovinic acid base) methyl) indolone
In the single compartment electrolytic cell of 50mL, by N-methyl-N-phenylmethyl acrylamide (1.0mmol), methyl sulfinic acid
Sodium (3mmol) and ammonium bromide (0.1mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, altogether in the solution of 12mL, with 2.5 ×
1cm2Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h, stops electrolysis,
Solvent is sloughed in rotation steaming, extracts three times with dichloromethane, through column chromatography for separation, obtains 1,3-dimethyl-3-(pyrovinic acid base) first
Base) indolone.Yield: 85%.
Embodiment 36:1,3-dimethyl-3-(ethylsulfonic acid base) methyl) electrochemical synthesis of indolone
In the single compartment electrolytic cell of 50mL, by N-methyl-N-phenylmethyl acrylamide (1.0mmol), ethyl sulfinic acid
Sodium (3mmol) and ammonium bromide (0.1mmol) join Isosorbide-5-Nitrae-dioxane: water=1:1, altogether in the solution of 12mL, with 2.5 ×
1cm2Graphite flake be anode and negative electrode, at 2mA/cm2It is electrolysed under constant current, 80 DEG C of stirrings, as energising 8h, stops electrolysis,
Solvent is sloughed in rotation steaming, extracts three times with dichloromethane, through column chromatography for separation, obtains 1,3-dimethyl-3-(ethylsulfonic acid base) first
Base) indolone.Yield: 77%.
White solid；mp:126-127℃；1H NMR(400MHz,CDCl3) δ 1.33 (t, J=7.2Hz, 3H), 1.47
(s, 3H), 2.83 (q, J=7.2Hz, 2H), 3.26 (s, 3H), 3.51 (d, J=14.4Hz, 1H), 3.65 (d, J=14.4Hz,
1H), 6.80 (d, J=8.0Hz, 1H), 7.38-7.44 (m, 1H), 7.46-7.51 (m, 2H)；13C NMR(100MHz,CDCl3)δ
6.4,25.0,26.7,45.6,49.8,57.5,110.2,115.3,126.9,131.8,132.6,142.4,177.5。
Claims (10)
1. the electrochemical catalysis synthetic method of a 3-sulfonic group substituted oxindole compounds, it is characterised in that step
It is to represent that the N-that sulfonating reagent or formula (V) represent that sulfohydrazide and formula (II) represent replaces with formula (III) in single compartment electrolytic cell
Acrylamide is raw material, and in the presence of eelctro-catalyst, in certain temperature and electrolyte, electrolysis obtains the 3-sulfonic acid that formula (I) represents
Base substituted oxindole compounds；
Wherein, R1Represent-H, halogen, alkyl or aryl；R2Represent-H or-alkyl；R3Expression-alkyl ,-aryl or-acyl group；R4Table
Show-alkyl ,-acyl group or-aryl；R5Represent-H or-alkyl；R6Represent-H or-alkyl；R7Expression-alkyl or-aryl；M represents
For-OH ,-ONa or-NHNH2。
Method the most according to claim 1, it is characterised in that described electrolyte is acetonitrile: water v/v=1/1 or Isosorbide-5-Nitrae-dioxy
Six rings: water v/v=1/1.
Method the most according to claim 1, it is characterised in that described eelctro-catalyst is selected from tetraalkylphosphonium halide amine, alkali metal halogen
Any one in compound, ammonium halide.
Method the most according to claim 3, it is characterised in that tetraalkylphosphonium halide amine is tetrabutylammonium iodide, tetrabutyl ammonium bromide
Ammonium or tetraethylammonium bromide；Alkali halide is sodium iodide, potassium iodide, sodium bromide or potassium bromide；Ammonium halide be ammonium iodide or
Ammonium bromide.
Method the most according to claim 1, it is characterised in that the anode of electrolysis is graphite flake electrode, glass-carbon electrode or platinum guaze
Electrode.
Method the most according to claim 1, it is characterised in that the negative electrode of electrolysis is graphite flake electrode, aluminium flake electrode, iron plate electricity
Pole, copper plate electrode or zinc metal sheet electrode.
Method the most according to claim 1, it is characterised in that N-substituted acrylamide: the mol ratio of eelctro-catalyst is 1:0.1.
Method the most according to claim 1, it is characterised in that N-substituted acrylamide: sulfonating reagent or sulfohydrazide mole
Ratio is 1:(3-4).
Method the most according to claim 1, it is characterised in that described temperature is 70-80 DEG C.
Method the most according to claim 1, it is characterised in that under N-substituted acrylamide, the concentration in electrolyte is 0.05-
0.1mol/L。
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Cited By (9)
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| CN106567104A (en) * | 2016-10-31 | 2017-04-19 | 华南理工大学 | Electrochemical synthesis method of 1,1'-diindolylmethane derivatives |
| CN107620088A (en) * | 2017-09-14 | 2018-01-23 | 浙江工业大学 | A kind of method that electrochemical catalytic oxidation synthesizes 3 sulfydryl indole class compounds |
| CN110067006A (en) * | 2019-06-05 | 2019-07-30 | 广西师范大学 | A kind of methods and applications of electrochemistry formated sulfonyl diazanyl Benzazole compounds |
| CN110616439A (en) * | 2019-10-31 | 2019-12-27 | 安阳师范学院 | Method for synthesizing 4-sulfonic acid substituted isoquinolone derivative through electrochemical oxidation |
| CN110714208A (en) * | 2019-10-30 | 2020-01-21 | 常州工学院 | Method for preparing 6- (sulfonyl methyl) phenanthridine compound through electrocatalysis |
| CN112062706A (en) * | 2020-10-26 | 2020-12-11 | 南京先进生物材料与过程装备研究院有限公司 | Method for continuously preparing indolone compounds by using microchannel reaction device |
| CN114232013A (en) * | 2021-11-12 | 2022-03-25 | 华南理工大学 | Method for synthesizing indoloquinoline compound under electrochemical condition |
| CN115094449A (en) * | 2022-06-08 | 2022-09-23 | 上海交通大学 | Method for synthesizing and marking halogenated indolone by using freon type methane as carbon-carbon synthesizer and application thereof |
| CN115595051A (en) * | 2022-08-11 | 2023-01-13 | 赵子龙（Cn） | Preparation method of two-component coating composition |
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| CN106567104B (en) * | 2016-10-31 | 2018-12-11 | 华南理工大学 | The electrochemical method for synthesizing of 1,1 '-di-indole methyl hydride analog derivatives |
| CN106567104A (en) * | 2016-10-31 | 2017-04-19 | 华南理工大学 | Electrochemical synthesis method of 1,1'-diindolylmethane derivatives |
| CN107620088A (en) * | 2017-09-14 | 2018-01-23 | 浙江工业大学 | A kind of method that electrochemical catalytic oxidation synthesizes 3 sulfydryl indole class compounds |
| CN110067006A (en) * | 2019-06-05 | 2019-07-30 | 广西师范大学 | A kind of methods and applications of electrochemistry formated sulfonyl diazanyl Benzazole compounds |
| CN110714208B (en) * | 2019-10-30 | 2020-12-29 | 常州工学院 | Method for preparing 6- (sulfonyl methyl) phenanthridine compound through electrocatalysis |
| CN110714208A (en) * | 2019-10-30 | 2020-01-21 | 常州工学院 | Method for preparing 6- (sulfonyl methyl) phenanthridine compound through electrocatalysis |
| CN110616439A (en) * | 2019-10-31 | 2019-12-27 | 安阳师范学院 | Method for synthesizing 4-sulfonic acid substituted isoquinolone derivative through electrochemical oxidation |
| CN112062706A (en) * | 2020-10-26 | 2020-12-11 | 南京先进生物材料与过程装备研究院有限公司 | Method for continuously preparing indolone compounds by using microchannel reaction device |
| CN114232013A (en) * | 2021-11-12 | 2022-03-25 | 华南理工大学 | Method for synthesizing indoloquinoline compound under electrochemical condition |
| CN115094449A (en) * | 2022-06-08 | 2022-09-23 | 上海交通大学 | Method for synthesizing and marking halogenated indolone by using freon type methane as carbon-carbon synthesizer and application thereof |
| CN115094449B (en) * | 2022-06-08 | 2024-02-23 | 上海交通大学 | Method for synthesizing and marking halogenated indolone by using freon-type methane as carbon-synthesis son and application thereof |
| CN115595051A (en) * | 2022-08-11 | 2023-01-13 | 赵子龙（Cn） | Preparation method of two-component coating composition |
| CN115595051B (en) * | 2022-08-11 | 2023-12-05 | 浙江创赢新材料有限公司 | Preparation method of two-component coating composition |
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