CN107620088B - A kind of method for electrochemical catalytic oxidation synthesis of 3-mercaptoindole compounds - Google Patents
A kind of method for electrochemical catalytic oxidation synthesis of 3-mercaptoindole compounds Download PDFInfo
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Abstract
The invention discloses a kind of methods of electrochemical catalytic oxidation synthesis 3- sulfydryl indole class compound, and using three-electrode system, cathode and anode are graphite electrode, using the silver nitrate acetonitrile solution of 0.1mol/L as reference electrode；In sodium tetrafluoroborate acetonitrile solution, Benzazole compounds, disulfide and potassium iodide are added, after cell reaction 3~for 24 hours is stirred under 45~75 DEG C of temperature, the constant-pressure conditions of 0.2~0.6V, reaction solution is post-treated to obtain product 3- sulfydryl indole class compound.Synthetic method of the present invention, easy to operate and safe, product 3- sulfydryl indole class compound yield is high；Reaction condition is milder；Having used clean electric energy is reductant-oxidant, greatly reduces Environmental costs.
Description
Technical field
The present invention relates to a kind of methods of electrochemical catalytic oxidation synthesis 3- sulfydryl indole class compound.
Background technique
3- sulfydryl indole class compound has extraordinary bioactivity, has irreplaceable role in drug.Its
Treating cancer, HIV, allergy, heart disease, in terms of significant therapeutic effect be concerned.More than ten years in past close
It can be mainly divided into two kinds at the strategy of 3- sulfydryl indole class compound, one is prepare 3- sulfydryl indole class by cyclization
Compound；Another kind is to react synthesis 3- sulfydryl indole class compound with the nucleopilic reagent of sulfur-bearing by Benzazole compounds.
It is main when the nucleopilic reagent using sulfur-bearing reacts synthesis 3- sulfydryl indole class compound with Benzazole compounds
Sulphur source can be divided into following several: (1) phthalimide of N- virtue vulcanization；(2) sulfinic acid；(3) benzene sulfinic acid sodium salt；(4)
Benzene sulfonyl chloride；(5) disulfide；(6) mercaptan.Most common of them and what is be easy to get is disulfide and mercaptan, but mercaptan compound is general
Foul smelling, effect on environment are very big.In addition, the nucleopilic reagent in sulfur-bearing reacts synthesis 3- sulfydryl indole class with Benzazole compounds
In the reaction of compound, the oxidant of transition-metal catalyst or stoichiometry is often used, is also needed in many cases
Compare harsh reaction condition, these leverage it in the application of actual production.
In recent years, with the tremendous development of Green Chemistry, electrochemistry formated have become important green synthesis method it
One.Under electrochemical conditions, selected reductant-oxidant is electric energy, is the reductant-oxidant of cleaning green.And in electrification
It learns in reaction system and other oxidants is not added, be conducive to the separating-purifying of product.Document (Angewandte Chemie
International Edition, 2017,56:3009-3013) it reports using Benzazole compounds and mercaptan as raw material, through straight
The method for connecing electrochemistry formated 3- sulfydryl indole class compound.But reaction need to carry out under higher current potential, easily cause in this way
The peroxidating of the electropolymerization and mercaptan of Benzazole compounds；And aliphatic mercaptan when making substrate reaction substantially without；In addition,
Mercaptan used in amounts is twice of indoles substrate.
Summary of the invention
The object of the present invention is to provide one kind using Benzazole compounds and disulfide as raw material, passes through electrocatalysis oxidation reaction
The method for preparing 3- sulfydryl indole class compound.
To achieve the above object, the present invention adopts the following technical scheme: a kind of electrochemical catalytic oxidation synthesizes 3- sulfydryl Yin
The method of diindyl class compound, using three-electrode system, cathode and anode are graphite electrode, with the silver nitrate acetonitrile of 0.1mol/L
Solution is as reference electrode；It is characterized by: in sodium tetrafluoroborate acetonitrile solution, be added Benzazole compounds, disulfide and
Potassium iodide, after stirring cell reaction 3~for 24 hours under 45~75 DEG C of temperature, the constant-pressure conditions of 0.2~0.6V, reaction solution is after
Reason obtains product 3- sulfydryl indole class compound.
Shown in the structural formula such as formula (II) of the reaction substrate Benzazole compounds, the reaction substrate disulfide compound
Structural formula such as formula (III), shown in obtained product structure formula such as formula (I)；
In formula (I) and formula (II), R1For H or C1~C4 alkyl, preferably R1For H or methyl；R2For H, C1~C4 alkyl, benzene
Base or substituted-phenyl, preferably R2For H, methyl or phenyl；R3For for H, F, Cl, Br, NO2, C1~C4 alkyl or C1~C2 alcoxyl
Base, preferably R1For H, Br, methyl or methoxy.
In formula (I) and formula (III), R4It is fragrant for C1~C4 alkyl, phenyl, substituted phenyl, heteroaryl perfume base, substituted heteroaryl
Base, naphthalene or substituted naphthalene.The heteroaryl perfume base can be ring and include the heteroatomic aromatic radical such as N, O, S.Described takes
The phenyl in generation, substituted heteroaryl perfume base and substituted naphthalene refer to that the hydrogen on phenyl ring, miscellaneous aromatic rings and naphthalene nucleus is one or more
Substituent group replace, the substituent group is each independently selected from one of following: halogen, the alkyl of C1~C4, C1-C4 alkoxy,
Amino and hydroxyl.It is preferred that R4Replace for n-propyl, phenyl, halogenophenyl, alkyl-substituted phenyl, alkoxy substituted phenyl, amino
Phenyl, hydroxyl substituted-phenyl, pyridyl group or thienyl.
The concentration of synthetic method of the present invention, preferably sodium tetrafluoroborate in acetonitrile is 0.05~0.2mol/L.
Recommend the quality dosage of acetonitrile for 20~120 times of the reaction substrate Benzazole compounds quality.
Molar ratio 100:40~60:2~8 of the reaction substrate Benzazole compounds and disulfide, potassium iodide, preferably
For 100:45~55:4~6.
It is preferred that the electrolysis temperature is 55~65 DEG C；It is preferred that decomposition voltage be 0.3~0.5V, the reaction time be 5~
15h。
The method of the usually described reaction solution post-processing are as follows: after reaction, evaporating solvent under reduced pressure, then carry out column chromatography point
From using ethyl acetate/n-hexane volume ratio 1:100 mixed liquor as eluant, eluent, eluent of the collection containing target compound is evaporated off
Solvent is up to product 3- sulfydryl indole class compound.
Specifically recommend synthetic method of the present invention are as follows: reaction uses three-electrode system, and cathode and anode are graphite
Electrode, the silver nitrate acetonitrile solution of 0.1mol/L is as reference electrode.In 0.05~0.2mol/L sodium tetrafluoroborate acetonitrile solution
In, Benzazole compounds, disulfide and potassium iodide is added, electricity is stirred under 55~65 DEG C of temperature, the constant-pressure conditions of 0.3~0.5V
After 5~15h of solution reaction, evaporating solvent under reduced pressure, then column chromatography for separation is carried out, it is mixed with ethyl acetate/n-hexane volume ratio 1:100
Conjunction liquid is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off up to product 3- sulfydryl indole class compound.It is described
The ratio between the amount of substance 100:45~55:4~6 of reaction substrate Benzazole compounds and disulfide, potassium iodide.
Synthetic method of the present invention, easy to operate and safe, its advantages essentially consist in:
(A) product 3- sulfydryl indole class compound yield is high.
(B) reaction condition is milder.
(C) having used clean electric energy is reductant-oxidant, greatly reduces Environmental costs.
Specific embodiment
Below by specific embodiment, the invention will be further described, but the scope of protection of the present invention is not limited thereto.
The structural formula of 3- sulfydryl indole class compound obtained by following embodiments is respectively as shown in formula (1)~(26):
The preparation of embodiment 1:2- methyl -3- thiophenyl -1H- indoles (formula 1)
Acetonitrile solution (15mL), the 2- Methyl-1H-indole of 0.1mol/L sodium tetrafluoroborate are added in the beaker of 30ml
(1mmol), Diphenyl disulfide ether (0.5mmol) and potassium iodide (0.05mmol).60 DEG C, potentiostatic deposition under 0.4V is anti-after 6h
It should terminate.Evaporating solvent under reduced pressure, then column chromatography for separation is carried out, it is to wash with ethyl acetate/n-hexane volume ratio 1:100 mixed liquor
De- agent, collects the eluent containing target compound, solvent is evaporated off up to product 2- methyl -3- thiophenyl -1H- indoles.Separation is received
Rate is 94%.
The preparation of embodiment 2:2- methyl -3- thiophenyl -1H- indoles (formula 1)
Reaction step is with embodiment 1, except that voltage is changed to 0.6V, reacts 5h, 2- methyl -3- thiophenyl -1H- Yin
The separation yield of diindyl is 94%.
The preparation of embodiment 3:2- methyl -3- thiophenyl -1H- indoles (formula 1)
Reaction step is with embodiment 1, except that voltage is changed to 0.2V, reacts for 24 hours, 2- methyl -3- thiophenyl -1H-
The separation yield of indoles is 90%.
The preparation of embodiment 4:2- methyl -3- thiophenyl -1H- indoles (formula 1)
Reaction step is with embodiment 1, except that reaction temperature is changed to 45 DEG C, reacts 12h, 2- methyl -3- thiophenyl -
The separation yield of 1H- indoles is 92%.
The preparation of embodiment 5:2- methyl -3- thiophenyl -1H- indoles (formula 1)
Reaction step is with embodiment 1, except that reaction temperature is changed to 75 DEG C, reacts 5h, 2- methyl -3- thiophenyl -
The separation yield of 1H- indoles is 94%.
The preparation of embodiment 6:2- methyl -3- thiophenyl -1H- indoles (formula 1)
Reaction step is with embodiment 1, except that reaction temperature is changed to 65 DEG C, voltage is changed to 0.5V, reacts 7h, 2- first
The separation yield of base -3- thiophenyl -1H- indoles is 93%.
The preparation of embodiment 7:2- methyl -3- thiophenyl -1H- indoles (formula 1)
Reaction step is with embodiment 1, except that Diphenyl disulfide ether dosage is changed to 0.6mmol, voltage is changed to 0.3V,
9h is reacted, the separation yield of 2- methyl -3- thiophenyl -1H- indoles is 86%.
The preparation of embodiment 8:2- methyl -3- thiophenyl -1H- indoles (formula 1)
Reaction step is with embodiment 1, except that Diphenyl disulfide ether dosage is changed to 0.4mmol, 2- methyl -3- benzene sulphur
The separation yield of base -1H- indoles is 72%.
The preparation of embodiment 9:2- methyl -3- thiophenyl -1H- indoles (formula 1)
Reaction step is with embodiment 1, except that Diphenyl disulfide ether dosage is changed to 0.55mmol, iodate potassium application rate changes
For 0.04mmol, the separation yield of 2- methyl -3- thiophenyl -1H- indoles is 88%.
The preparation of embodiment 10:2- methyl -3- thiophenyl -1H- indoles (formula 1)
Reaction step is with embodiment 1, except that Diphenyl disulfide ether dosage is changed to 0.45mmol, iodate potassium application rate changes
For 0.06mmol, the separation yield of 2- methyl -3- thiophenyl -1H- indoles is 88%.
The preparation of embodiment 11:2- methyl -3- thiophenyl -1H- indoles (formula 1)
Reaction step is with embodiment 1, except that voltage is changed to 0.6V, iodate potassium application rate is changed to 0.8mmol, reaction
The separation yield of 3h, 2- methyl -3- thiophenyl -1H- indoles is 82%.
The preparation of embodiment 12:2- methyl -3- thiophenyl -1H- indoles (formula 1)
Reaction step is with embodiment 1, except that iodate potassium application rate is changed to 0.2mmol, reacts 15h, 2- methyl -3- benzene
The separation yield of sulfenyl -1H- indoles is 86%.
The preparation of embodiment 13:2- methyl -3- thiophenyl -1H- indoles (formula 1)
Reaction step is with embodiment 1, except that the acetonitrile solution concentration of sodium tetrafluoroborate is changed to 0.2mol/L reaction
The separation yield of 6h, 2- methyl -3- thiophenyl -1H- indoles is 94%.
The preparation of embodiment 14:2- methyl -3- thiophenyl -1H- indoles (formula 1)
Reaction step is with embodiment 1, except that the acetonitrile solution concentration of sodium tetrafluoroborate is changed to 0.05mol/L reaction
The separation yield of 9h, 2- methyl -3- thiophenyl -1H- indoles is 87%.
The preparation of embodiment 15:2- methyl -3- thiophenyl -1H- indoles (formula 1)
Reaction step is with embodiment 1, except that the acetonitrile solution dosage of sodium tetrafluoroborate is changed to 35mL, 2- methyl-
The separation yield of 3- thiophenyl -1H- indoles is 94%.
The preparation of embodiment 16:2- methyl -3- thiophenyl -1H- indoles (formula 1)
Reaction step is with embodiment 1, except that the acetonitrile solution dosage of sodium tetrafluoroborate is changed to 6mL, 2- methyl -3-
The separation yield of thiophenyl -1H- indoles is 72%.
Preparation of the embodiment 17:2- methyl -3- to chlorophenylsulfanyl -1H- indoles (formula 2)
Acetonitrile solution (15mL), the 2- Methyl-1H-indole of 0.1mol/L sodium tetrafluoroborate are added in the beaker of 30ml
(1mmol), two (rubigan) disulfides (0.5mmol) and potassium iodide (0.05mmol).60 DEG C, potentiostatic deposition under 0.4V,
Reaction terminates after 6h.Evaporating solvent under reduced pressure, then column chromatography for separation is carried out, with ethyl acetate/n-hexane volume ratio 1:100 mixing
Liquid is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off up to product 2- methyl -3- to chlorophenylsulfanyl -1H- Yin
Diindyl.Separation yield is 90%.
The preparation of chlorophenylsulfanyl -1H- indoles (formula 3) between embodiment 18:2- methyl -3-
Acetonitrile solution (15mL), the 2- Methyl-1H-indole of 0.1mol/L sodium tetrafluoroborate are added in the beaker of 30ml
(1mmol), two (chlorphenyl) disulfides (0.5mmol) and potassium iodide (0.05mmol).60 DEG C, potentiostatic deposition under 0.4V,
Reaction terminates after 6h.Evaporating solvent under reduced pressure, then column chromatography for separation is carried out, with ethyl acetate/n-hexane volume ratio 1:100 mixing
Liquid is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off up to chlorophenylsulfanyl -1H- Yin between product 2- methyl -3-
Diindyl.Separation yield is 97%.
The preparation of embodiment 19:2- methyl -3- neighbour's chlorophenylsulfanyl -1H- indoles (formula 4)
Acetonitrile solution (15mL), the 2- Methyl-1H-indole of 0.1mol/L sodium tetrafluoroborate are added in the beaker of 30ml
(1mmol), two (Chloro-O-Phenyl) disulfides (0.5mmol) and potassium iodide (0.05mmol).60 DEG C, potentiostatic deposition under 0.4V,
Reaction terminates after 6h.Evaporating solvent under reduced pressure, then column chromatography for separation is carried out, with ethyl acetate/n-hexane volume ratio 1:100 mixing
Liquid is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off up to product 2- methyl -3- neighbour chlorophenylsulfanyl -1H- Yin
Diindyl.Separation yield is 92%.
Preparation of the embodiment 20:2- methyl -3- to bromophenylthio -1H- indoles (formula 5)
Acetonitrile solution (15mL), the 2- Methyl-1H-indole of 0.1mol/L sodium tetrafluoroborate are added in the beaker of 30ml
(1mmol), two (p-bromophenyl) disulfides (0.5mmol) and potassium iodide (0.05mmol).60 DEG C, potentiostatic deposition under 0.4V,
Reaction terminates after 6h.Evaporating solvent under reduced pressure, then column chromatography for separation is carried out, with ethyl acetate/n-hexane volume ratio 1:100 mixing
Liquid is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off up to product 2- methyl -3- to bromophenylthio -1H- Yin
Diindyl.Separation yield is 97%.
Preparation of the embodiment 21:2- methyl -3- to chlorophenylthio -1H- indoles (formula 6)
Acetonitrile solution (15mL), the 2- Methyl-1H-indole of 0.1mol/L sodium tetrafluoroborate are added in the beaker of 30ml
(1mmol), two (p-fluorophenyl) disulfides (0.5mmol) and potassium iodide (0.05mmol).60 DEG C, potentiostatic deposition under 0.4V,
Reaction terminates after 6h.Evaporating solvent under reduced pressure, then column chromatography for separation is carried out, with ethyl acetate/n-hexane volume ratio 1:100 mixing
Liquid is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off up to product 2- methyl -3- to chlorophenylthio -1H- Yin
Diindyl.Separation yield is 90%.
Preparation of the embodiment 22:2- methyl -3- to Methoxv-phenylsulfanvl -1H- indoles (formula 7)
Acetonitrile solution (15mL), the 2- Methyl-1H-indole of 0.1mol/L sodium tetrafluoroborate are added in the beaker of 30ml
(1mmol), two (p-methoxyphenyl) disulfides (0.5mmol) and potassium iodide (0.05mmol).60 DEG C, constant potential electricity under 0.4V
It solves, reacting after 6h terminates.Evaporating solvent under reduced pressure, then column chromatography for separation is carried out, with ethyl acetate/n-hexane volume ratio 1:100
Mixed liquor is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off up to product 2- methyl -3- to methoxybenzene sulphur
Base -1H- indoles.Separation yield is 96%.
The preparation of embodiment 23:2- methyl -3- meta-methoxy thiophenyl -1H- indoles (formula 8)
Acetonitrile solution (15mL), the 2- Methyl-1H-indole of 0.1mol/L sodium tetrafluoroborate are added in the beaker of 30ml
(1mmol), two (m-methoxyphenyl) thiophenols (0.5mmol) and potassium iodide (0.05mmol).60 DEG C, constant potential electricity under 0.4V
It solves, reacting after 7h terminates.Evaporating solvent under reduced pressure, then column chromatography for separation is carried out, with ethyl acetate/n-hexane volume ratio 1:100
Mixed liquor is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off up to product 2- methyl -3- meta-methoxy benzene sulphur
Base -1H- indoles.Separation yield is 90%.
The preparation of embodiment 24:2- methyl -3- O-methoxy thiophenyl -1H- indoles (formula 9)
Acetonitrile solution (15mL), the 2- Methyl-1H-indole of 0.1mol/L sodium tetrafluoroborate are added in the beaker of 30ml
(1mmol), two (o-methoxyphenyl) disulfides (0.5mmol) and potassium iodide (0.05mmol).60 DEG C, constant potential electricity under 0.4V
It solves, reacting after 6h terminates.Evaporating solvent under reduced pressure, then column chromatography for separation is carried out, with ethyl acetate/n-hexane volume ratio 1:100
Mixed liquor is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off up to product 2- methyl -3- O-methoxy benzene sulphur
Base -1H- indoles.Separation yield is 94%.
Preparation of the embodiment 25:2- methyl -3- to methylphenyl-sulfanyl -1H- indoles (formula 10)
Acetonitrile solution (15mL), the 2- Methyl-1H-indole of 0.1mol/L sodium tetrafluoroborate are added in the beaker of 30ml
(1mmol), two (p-methylphenyl) disulfides (0.5mmol) and potassium iodide (0.05mmol).60 DEG C, constant potential electricity under 0.4V
It solves, reacting after 6h terminates.Evaporating solvent under reduced pressure, then column chromatography for separation is carried out, with ethyl acetate/n-hexane volume ratio 1:100
Mixed liquor is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off up to product 2- methyl -3- to methylbenzene sulphur
Base -1H- indoles.Separation yield is 96%.
The preparation of embodiment 26:2- methyl -3- p-isopropyl thiophenyl -1H- indoles (formula 11)
Acetonitrile solution (15mL), the 2- Methyl-1H-indole of 0.1mol/L sodium tetrafluoroborate are added in the beaker of 30ml
(1mmol), two (p-isopropyl phenyl) disulfides (0.5mmol) and potassium iodide (0.05mmol).60 DEG C, constant potential electricity under 0.4V
It solves, reacting after 7h terminates.Evaporating solvent under reduced pressure, then column chromatography for separation is carried out, with ethyl acetate/n-hexane volume ratio 1:100
Mixed liquor is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off up to product 2- methyl -3- cumic aldehyde sulphur
Base -1H- indoles.Separation yield is 90%.
The preparation of embodiment 27:2- methyl -3- p-aminophenyl sulfenyl -1H- indoles (formula 12)
Acetonitrile solution (15mL), the 2- Methyl-1H-indole of 0.1mol/L sodium tetrafluoroborate are added in the beaker of 30ml
(1mmol), two (p-aminophenyl) disulfides (0.5mmol) and potassium iodide (0.05mmol).60 DEG C, constant potential electricity under 0.4V
It solves, reacting after 8h terminates.Evaporating solvent under reduced pressure, then column chromatography for separation is carried out, with ethyl acetate/n-hexane volume ratio 1:100
Mixed liquor is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off up to product 2- methyl -3- p-aminophenyl sulphur
Base -1H- indoles.Separation yield is 92%.
The preparation of hydroxy benzenes sulfenyl -1H- indoles (formula 13) between embodiment 28:2- methyl -3-
Acetonitrile solution (15mL), the 2- Methyl-1H-indole of 0.1mol/L sodium tetrafluoroborate are added in the beaker of 30ml
(1mmol), two (hydroxy phenyl) disulfides (0.5mmol) and potassium iodide (0.05mmol).60 DEG C, constant potential electricity under 0.4V
It solves, reacting after 12h terminates.Evaporating solvent under reduced pressure, then column chromatography for separation is carried out, with ethyl acetate/n-hexane volume ratio 1:100
Mixed liquor is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off up to hydroxyphenyl thio between product 2- methyl -3-
Base -1H- indoles.Separation yield is 93%.
The preparation of embodiment 29:2- methyl -3- (2- thienyl) sulfenyl -1H- indoles (formula 14)
Acetonitrile solution (15mL), the 2- Methyl-1H-indole of 0.1mol/L sodium tetrafluoroborate are added in the beaker of 30ml
(1mmol), two (2- thienyl) disulfides (0.5mmol) and potassium iodide (0.05mmol).60 DEG C, potentiostatic deposition under 0.4V,
Reaction terminates after 9h.Evaporating solvent under reduced pressure, then column chromatography for separation is carried out, with ethyl acetate/n-hexane volume ratio 1:100 mixing
Liquid is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off up to product 2- methyl -3- (2- thienyl) sulfenyl -
1H- indoles.Separation yield is 86%.
The preparation of embodiment 30:2- methyl -3- (2- pyridyl group) sulfenyl -1H- indoles (formula 15)
Acetonitrile solution (15mL), the 2- Methyl-1H-indole of 0.1mol/L sodium tetrafluoroborate are added in the beaker of 30ml
(1mmol), two (2- pyridyl group) disulfides (0.5mmol) and potassium iodide (0.05mmol).60 DEG C, potentiostatic deposition under 0.4V,
Reaction terminates after 6h.Evaporating solvent under reduced pressure, then column chromatography for separation is carried out, with ethyl acetate/n-hexane volume ratio 1:100 mixing
Liquid is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off up to product 2- methyl -3- (2- pyridyl group) sulfenyl -
1H- indoles.Separation yield is 95%.
The preparation of embodiment 31:2- methyl -3- positive rosickyite base -1H- indoles (formula 16)
Acetonitrile solution (15mL), the 2- Methyl-1H-indole of 0.1mol/L sodium tetrafluoroborate are added in the beaker of 30ml
(1mmol), diη-propyl disulfide (0.5mmol) and potassium iodide (0.05mmol).60 DEG C, potentiostatic deposition under 0.4V, after 6h
Reaction terminates.Evaporating solvent under reduced pressure, then column chromatography for separation is carried out, it is with ethyl acetate/n-hexane volume ratio 1:100 mixed liquor
Eluant, eluent collects the eluent containing target compound, solvent is evaporated off up to product 2- methyl -3- positive rosickyite base -1H- indoles.Point
It is 82% from yield.
The preparation of embodiment 32:1- methyl -3- thiophenyl -1H- indoles (formula 17)
Acetonitrile solution (15mL), the 1- Methyl-1H-indole of 0.1mol/L sodium tetrafluoroborate are added in the beaker of 30ml
(1mmol), Diphenyl disulfide ether (0.5mmol) and potassium iodide (0.05mmol).60 DEG C, potentiostatic deposition under 0.4V is anti-after 6h
It should terminate.Evaporating solvent under reduced pressure, then column chromatography for separation is carried out, it is to wash with ethyl acetate/n-hexane volume ratio 1:100 mixed liquor
De- agent, collects the eluent containing target compound, solvent is evaporated off up to product 1- methyl -3- thiophenyl -1H- indoles.Separation is received
Rate is 92%.
Preparation of the embodiment 33:1- methyl -3- to chlorophenylsulfanyl -1H- indoles (formula 18)
Acetonitrile solution (15mL), the 1- Methyl-1H-indole of 0.1mol/L sodium tetrafluoroborate are added in the beaker of 30ml
(1mmol), two (rubigan) disulfides (0.5mmol) and potassium iodide (0.05mmol).60 DEG C, potentiostatic deposition under 0.4V,
Reaction terminates after 6h.Evaporating solvent under reduced pressure, then column chromatography for separation is carried out, with ethyl acetate/n-hexane volume ratio 1:100 mixing
Liquid is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off up to product 1- methyl -3- to chlorophenylsulfanyl -1H- Yin
Diindyl.Separation yield is 95%.
Preparation of the embodiment 34:1- methyl -3- to methylphenyl-sulfanyl -1H- indoles (formula 19)
Acetonitrile solution (15mL), the 1- Methyl-1H-indole of 0.1mol/L sodium tetrafluoroborate are added in the beaker of 30ml
(1mmol), two (p-methylphenyl) disulfides (0.5mmol) and potassium iodide (0.05mmol).60 DEG C, constant potential electricity under 0.4V
It solves, reacting after 6h terminates.Evaporating solvent under reduced pressure, then column chromatography for separation is carried out, with ethyl acetate/n-hexane volume ratio 1:100
Mixed liquor is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off up to product 1- methyl -3- to Tolylsulfanvl -
1H- indoles.Separation yield is 83%.
The preparation of embodiment 35:3- thiophenyl -1H- indoles (formula 20)
Be added in the beaker of 30ml the acetonitrile solution (15mL) of 0.1mol/L sodium tetrafluoroborate, 1H- indoles (1mmol),
Diphenyl disulfide ether (0.5mmol) and potassium iodide (0.05mmol).60 DEG C, potentiostatic deposition under 0.4V, reacting after 12h terminates.
Evaporating solvent under reduced pressure, then column chromatography for separation is carried out, using ethyl acetate/n-hexane volume ratio 1:100 mixed liquor as eluant, eluent, receive
Collect the eluent containing target compound, solvent is evaporated off up to product 3- thiophenyl -1H- indoles.Separation yield is 86%.
The preparation of embodiment 36:5- methyl -3- thiophenyl -1H- indoles (formula 21)
Acetonitrile solution (15mL), the 5- Methyl-1H-indole of 0.1mol/L sodium tetrafluoroborate are added in the beaker of 30ml
(1mmol), Diphenyl disulfide ether (0.5mmol) and potassium iodide (0.05mmol).60 DEG C, potentiostatic deposition under 0.4V is anti-after 12h
It should terminate.Evaporating solvent under reduced pressure, then column chromatography for separation is carried out, it is to wash with ethyl acetate/n-hexane volume ratio 1:100 mixed liquor
De- agent, collects the eluent containing target compound, solvent is evaporated off up to product 5- methyl -3- thiophenyl -1H- indoles.Separation is received
Rate is 95%.
Preparation of the embodiment 37:5- methyl -3- to chlorophenylsulfanyl -1H- indoles (formula 22)
Acetonitrile solution (15mL), the 5- Methyl-1H-indole of 0.1mol/L sodium tetrafluoroborate are added in the beaker of 30ml
(1mmol), two (rubigan) disulfides (0.5mmol) and potassium iodide (0.05mmol).60 DEG C, potentiostatic deposition under 0.4V,
Reaction terminates after 12h.Evaporating solvent under reduced pressure, then column chromatography for separation is carried out, it is mixed with ethyl acetate/n-hexane volume ratio 1:100
Conjunction liquid is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off up to product 5- methyl -3- to chlorophenylsulfanyl -1H-
Indoles.Separation yield is 93%.
Preparation of the embodiment 38:5- methyl -3- to methylphenyl-sulfanyl -1H- indoles (formula 23)
Acetonitrile solution (15mL), the 5- Methyl-1H-indole of 0.1mol/L sodium tetrafluoroborate are added in the beaker of 30ml
(1mmol), two (p-methylphenyl) disulfides (0.5mmol) and potassium iodide (0.05mmol).60 DEG C, constant potential electricity under 0.4V
It solves, reacting after 12h terminates.Evaporating solvent under reduced pressure, then column chromatography for separation is carried out, with ethyl acetate/n-hexane volume ratio 1:100
Mixed liquor is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off up to product 5- methyl -3- to methylbenzene sulphur
Base -1H- indoles.Separation yield is 94%.
The preparation of embodiment 39:5- methoxyl group -3- thiophenyl -1H- indoles (formula 24)
Acetonitrile solution (15mL), the 5- Methyl-1H-indole of 0.1mol/L sodium tetrafluoroborate are added in the beaker of 30ml
(1mmol), Diphenyl disulfide ether (0.5mmol) and potassium iodide (0.05mmol).60 DEG C, potentiostatic deposition under 0.4V is anti-after 12h
It should terminate.Evaporating solvent under reduced pressure, then column chromatography for separation is carried out, it is to wash with ethyl acetate/n-hexane volume ratio 1:100 mixed liquor
De- agent, collects the eluent containing target compound, solvent is evaporated off up to product 5- methoxyl group -3- thiophenyl -1H- indoles.Separation
Yield is 84%.
The preparation of embodiment 40:1- methyl -2- phenyl -3- thiophenyl -1H- indoles (formula 25)
Acetonitrile solution (15mL), the 1- methyl -2- phenyl-of 0.1mol/L sodium tetrafluoroborate are added in the beaker of 30ml
1H- indoles (1mmol), Diphenyl disulfide ether (0.5mmol) and potassium iodide (0.05mmol).60 DEG C, potentiostatic deposition under 0.4V,
Reaction terminates after 12h.Evaporating solvent under reduced pressure, then column chromatography for separation is carried out, it is mixed with ethyl acetate/n-hexane volume ratio 1:100
Conjunction liquid is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off up to product 1- methyl -2- phenyl -3- thiophenyl -
1H- indoles.Separation yield is 89%.
The preparation of the bromo- 3- thiophenyl -1H- indoles (formula 26) of embodiment 41:5-
The bromo- 1H- indoles of acetonitrile solution (15mL), 5- of 0.1mol/L sodium tetrafluoroborate is added in the beaker of 30ml
(1mmol), Diphenyl disulfide ether (0.5mmol) and potassium iodide (0.05mmol).60 DEG C, potentiostatic deposition under 0.6V is anti-after 20h
It should terminate.Evaporating solvent under reduced pressure, then column chromatography for separation is carried out, it is to wash with ethyl acetate/n-hexane volume ratio 1:100 mixed liquor
De- agent, collects the eluent containing target compound, solvent is evaporated off up to the bromo- 3- thiophenyl -1H- indoles of product 5-.Separation yield
It is 67%.
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