CN109369645A - A kind of green synthesis method of the 3- arylthio -7- azaindole compounds of base catalysis - Google Patents
A kind of green synthesis method of the 3- arylthio -7- azaindole compounds of base catalysis Download PDFInfo
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Abstract
A kind of green synthesis method of the 3- arylthio -7- azaindole compounds of base catalysis, 7- azaindole and arylthio reagent are added in solvent, then catalyst is added, 2~14h is reacted at 60~120 DEG C, obtains 3- arylthio -7- azaindole compounds;Wherein, arylthio reagent is aryl thiophenol.Method of the invention is easy to operate, high conversion rate, selectivity is good, does not need the iodine using transition-metal catalyst or stoichiometry, does not need anhydrous and oxygen-free system, the alkali for only needing to be added catalytic amounts can be gone on smoothly, and be the route of synthesis of a cleaning green.
Description
Technical field
The present invention relates to organic syntheses and field of natural product chemistry, and in particular to a kind of 3- arylthio-of base catalysis
The green synthesis method of 7- azaindole.
Background technique
Azaindole (1H- pyrrolo- [2,3-b] pyridine) is a kind of aromatic organic compounds, is widely present in natural production
In object, derivative is widely used in material science and field of medicinal chemistry.As its derivative, 3- arylthio -7- azepine
Benzazole compounds are in terms of the control of disease especially heart disease, allergy, cancer, HIV and obesity etc. and treatment
(P.C.Unangst,et.al.Journal of Medicinal Chemistry,1989,32,1360;C.D.Funk,
Nature Reviews Drug discovery,2005,4,664;R.Ragno,et.al.Journal of Medicinal
Chemistry,2006,49,3172;G.La Regina,et.al.Journal of Medicinal Chemistry,2007,
50,2865.) there is very high application value.
The synthesis of 3- arylthio -7- azaindoles usually starts at 7- azaindole skeleton, by one
The thio reaction (nucleophilic substitution) of regioselectivity is carried out under fixed condition to realize.Review literature, it is reported from 7- nitrogen
Miscellaneous indoles, which sets out, usually requires transition by the method that 3- carbon atom vulcanizations prepare 3- arylthio -7- azaindole compounds
The promotor or catalyst as reaction such as metallic copper, stoichiometry/excessive highly basic, iodine or trifluoroacetic anhydride.
In these methods, a variety of arylthio reagents are contained, it is anti-can to carry out parental materials with 7- azaindole
Should obtain target product, these arylthio thio reagents include: diphenylsulfide (be related to transition metal copper catalysis, referring to:
A.Coluccia,et.al.Journal of Medicinal Chemistry,2016,59,9760;H.Liao,
et.al.Current Organic Chemistry,2017,21,2509;It is related to the reaction that the alkali of stoichiometry promotes, referring to:
J.Porter,et.al.Bioorganic&Medicinal Chemistry Letters,2009,19,2780;G.C.Visor,
et.al.PCT Int.Appl.WO 2010129570A1,Nov 11,2010;P.Sang,et.al.Green Chemistry,
2013,15,2096;J.Zhang,et.al.PCT Int.Appl.WO2014145051A1,Sep 18,2014;
I.T.Bharathan, et.al.PCT Int.Appl.WO 2015108861A1, Jul 23,2015.), benzenethiol (be related to iodine
Simple substance catalysis, referring to: H.Zhang, et.al.Tetrahedron, 2015,71,8885;It is related to excessive sodium hydroxide as alkali
The reaction of promotion, referring to Y.Liu, et.al.RSC Advances, 2014,4,35528.), methyl phenyl sulfoxide (is related to trifluoro
Acetic anhydride and methylene chloride are reacted at -78 DEG C, referring to: R.C.Bernotas, et.al.PCT Int.Appl.WO
2003101990 A1,Dec 11 2003;R.C.Bernotas,et.al.PCT Int.Appl.WO 2004009600A1,Jan
29 2004;R.C.Bernotas, et.al.Bioorganic&Medicinal Chemistry, 2009,17,5153.), benzene is sub-
Sulfonic acid (it is related to elemental iodine catalysis, referring to: C.Liu, et.al.Chinese Journal of Chemistry, 2018,36,
819.), benzene sulfonyl chloride (is related to transition metal copper catalysis, referring to Z.Wu.et.al.Asian Journal of Organic
, Chemistry, 2016,5,625.) benzene sulfonyl hydrazide (be related to the pyroreaction in aqueous medium, referring to Y.Yang,
, et.al.Green Chemistry, 2016,18,2609.) benzene sulfonyl hydroxamic acid (is related to elemental iodine catalysis, referring to F.-
X.Wang, et.al.Organic&Biomolecular Chemistry, 2017,15,5284.) and nation's spy's sodium salt (is related to
Elemental iodine catalysis, referring to: H.Qi, et.al.Journal of Organic Chemistry, 2016,81,4262;M.Luo,
et.al.Faming Zhuanli Shenqing,CN 105418481 A,Mar 23,2016.)。
In addition, in the conversion process, 7- azaindole can also be reacted at 3 with elemental iodine first and carry out iodo, so
It is reacted to obtain corresponding product with aryl thiophenol again afterwards and (step 1: carries out iodo with elemental iodine;Step 2: in transition gold
Belong to and carries out arylthio under copper catalytic action, referring to: R.C.Bernotas, et.al.PCT Int.Appl.WO 2003101990
A1,Dec 11 2003;H.Tian,et.al.Faming Zhuanli Shenqing,CN 103613591A,Mar 05,
2014;W.McCoull,et.al.et.al.MedChemComm,2014,5,1533;N.Liu,et.al.Bioorganic
Chemistry,2016,65,146.)。
In conclusion in previous report, usually using more complicated compound as arylthio reagent;Anti-
During answering, it usually needs transition metal, elemental iodine or excessive highly basic is added to promote the progress of nucleophilic substitution, has
A little reactions even also need to carry out under the conditions of anhydrous and oxygen-free, therefore, the synthesis 3- arylthio -7- azepine of exploitation cleaning green
The method of benzazolyl compounds is extremely urgent.
Summary of the invention
In order to more be efficiently obtained target product, the limit of the conditions such as transition metal, elemental iodine even anhydrous and oxygen-free is overcome
System, the purpose of the present invention is to provide a kind of green synthesis methods of the 3- arylthio -7- azaindole of base catalysis, entire to close
It is simple and efficient at process, is easy to operate, efficiently synthesizing for 3- arylthio -7- azaindole compounds is realized by one kettle way.
To achieve the above object, the present invention adopts the following technical scheme that:
A kind of green synthesis method of the 3- arylthio -7- azaindole compounds of base catalysis, by 7- azaindole and
Arylthio reagent is added in solvent, and base catalyst is then added, and 2~14h is reacted at 60~120 DEG C, obtains 3- aryl
Thio -7- azaindole compounds;Wherein, arylthio reagent is aryl thiophenol.
A further improvement of the present invention lies in that solvent is dichloroethanes, n,N-Dimethylformamide, dimethyl sulfoxide, second
One of nitrile.
A further improvement of the present invention lies in that base catalyst is potassium carbonate, cesium carbonate, cesium hydroxide, cesium acetate, sodium acetate
One or more of.
A further improvement of the present invention lies in that aryl thiophenol is benzenethiol, 4- methylbenzene phenyl-sulfhydrate, 4- chlorothio-phenol, 4- fluorine
Benzenethiol, 2,4- thiophenol dimethyl benzene or 3- methylbenzene phenyl-sulfhydrate.
A further improvement of the present invention lies in that after 7- azaindole and arylthio reagent are added in solvent, solvent
The molar concentration of middle 7- azaindole is 0.05~0.5mol/L.
A further improvement of the present invention lies in that the mass ratio of the material of 7- azaindole and aryl thiophenol be 1:(1.1~
1.5)。
A further improvement of the present invention lies in that the mass ratio of the material of 7- azaindole and base catalyst be 1:(0.1~
0.5)。
A further improvement of the present invention lies in that the pressure of reaction is 0.1MPa.
Compared with prior art, the invention has the benefit that synthesis process of the present invention is simple and efficient, reaction is without adding
Enter transition-metal catalyst, without using elemental iodine, it is only necessary to which the alkali that catalytic amounts are added ensures that the smooth of reaction;It is logical
Cross to reaction transition state the study found that during the reaction, alkali can be catalyzed aryl thiophenol and undergo coupling reaction to produce two virtues
Base sulfide intermediate, then the intermediate obtains corresponding target production with 7- 7-azaindole derivatives generation electrophilic substitution reaction
Object;This synthetic route selectivity is strong, cleaning is green, and combined coefficient is high;Reaction raw materials are cheap and easy to get;With wide potential application
Prospect.
Specific embodiment
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the present invention is described further, the implementation
Example for explaining only the invention, does not restrict the protection scope of the present invention.
Using 7- azaindole and its derivative and arylthio reagent as raw material in the present invention, alkali is catalyst, is given simultaneously
Reaction provides alkaline environment, prepares corresponding 3- arylthio compound at a certain temperature in a solvent.
A kind of reaction equation of the green synthesis method of the 3- arylthio -7- azaindole compounds of base catalysis are as follows:
7- azaindole and arylthio reagent are added in solvent, catalyst is then added, it is anti-at 60~120 DEG C
2~14h is answered, 3- arylthio -7- azaindole compounds are obtained;
Wherein, arylthio reagent is aryl thiophenol;Specifically: benzenethiol, 4- methylbenzene phenyl-sulfhydrate, 4- chlorothio-phenol, 4-
Fluoro thiophenol, 2,4- thiophenol dimethyl benzene or 3- methylbenzene phenyl-sulfhydrate.
Catalyst is alkali, specially one or more of potassium carbonate, cesium carbonate, cesium hydroxide, cesium acetate, sodium acetate;
Solvent is one of dichloroethanes, N,N-dimethylformamide, dimethyl sulfoxide, acetonitrile.
The molar concentration of 7- azaindole in a solvent is 0.05~0.5mol/L.
The mass ratio of the material of 7- azaindole and arylthio reagent is 1:(1.1~1.5).
The mass ratio of the material of 7- azaindole and catalyst alkali is 1:(0.1~0.5).
The pressure of reaction is 0.1MPa.
Embodiment 1
The synthesis of 3- (phenyl) 1H- pyrrolo- [2,3-b] pyridine: 7- azaindole 0.118g is weighed respectively
(1mmol), benzenethiol 0.165g (1.5mmol), cesium acetate;The mass ratio of the material of 7- azaindole and cesium acetate is 1:0.1;Amount
5mL dimethyl sulfoxide is taken, load weighted reactant is sequentially added in the 25mL reaction tube with magneton, under room temperature in magnetic
On power blender stirring until system be in homogeneous phase solution, be then slowly heated to 120 DEG C, with thin-layer chromatography monitoring reaction into
Journey.At 0.1MPa, stops reaction after 2h, be cooled to room temperature.By mixture with 0.1mol/L hydrochloric acid (5mL), and use second
Acetoacetic ester (3 × 10mL) extraction, merges organic phase.Organic phase is washed with saturated salt solution (5mL) solution, and anhydrous sodium sulfate is added
Concentration is dried, filtered, is separated with column chromatography chromatogram, using the silica gel of 300~400 mesh as stationary phase, acetic acid in varing proportions
The mixed solvent of ethyl ester and petroleum ether purifies product as eluant, eluent, yield 86%.
Gained compound is known compound, and physical property and characterize data are as follows:
Yellow solid;1H NMR(400MHz,CDCl3) δ/ppm=12.26 (br s, 1H), 7.66 (d, J=7.6Hz,
1H), 7.50 (d, J=2.8Hz, 1H), 7.46 (d, J=8.4Hz, 1H), 7.33-7.28 (m, 1H), 7.23-7.08 (m, 6H);13CNMR(101MHz,CDCl3) δ/ppm=139.9,137.0,131.4,129.4,126.5,125.2,123.8,121.6,
120.3,118.2,103.5.
Embodiment 2
The synthesis of 3- [(4- methylbenzene) is thio] 1H- pyrrolo- [2,3-b] pyridine: 7- azaindole 0.118g is weighed respectively
(1mmol), 4- thiocresol 0.186g (1.5mmol), cesium acetate;The mass ratio of the material of 7- azaindole and cesium acetate is 1:
0.1;5mL dimethyl sulfoxide is measured, load weighted reactant is sequentially added in the 25mL reaction tube with magneton, room temperature condition
Under on magnetic stirring apparatus stirring until system be in homogeneous phase solution, be then slowly heated to 120 DEG C, with thin-layer chromatography monitor react
Process.At 0.1MPa, stops reaction after 3h, be cooled to room temperature.By mixture with 0.1mol/L hydrochloric acid (5mL), and
It is extracted with ethyl acetate (3 × 10mL), merges organic phase.Organic phase is washed with saturated salt solution (5mL) solution, and anhydrous sulphur is added
Sour sodium dries, filters concentration, is separated with column chromatography chromatogram, using the silica gel of 300~400 mesh as stationary phase, in varing proportions
The mixed solvent of ethyl acetate and petroleum ether purifies product as eluant, eluent, yield 82%.
Gained compound is known compound, and physical property and characterize data are as follows:
Yellow solid;1H NMR(400MHz,DMSO-d6) δ/ppm=12.23 (s, 1H), 8.29 (s, 1H), 7.90 (d, J
=2.3Hz, 1H), 7.76 (dd, J=7.8Hz, J=1.3Hz, 1H), 7.11 (dd, J=7.8Hz, J=4.7Hz, 1H), 7.02
(d, J=8.2Hz, 2H), 6.96 (d, J=8.3Hz, 2H), 2.19 (s, 3H);13C NMR (101MHz, DMSO) δ/ppm=
148.9,143.6,134.8,134.5,132.7,129.6,126.7,126.1,122.2,116.5,99.4,20.4。
Embodiment 3
The synthesis of 3- [(4- fluorobenzene) is thio] 1H- pyrrolo- [2,3-b] pyridine: 7- azaindole 0.118g is weighed respectively
(1mmol), 4- fluoro thiophenol 0.192g (1.5mmol), cesium acetate;The mass ratio of the material of 7- azaindole and cesium acetate is 1:
0.1;5mL dimethyl sulfoxide is measured, load weighted reactant is sequentially added in the 25mL reaction tube with magneton, room temperature condition
Under on magnetic stirring apparatus stirring until system be in homogeneous phase solution, be then slowly heated to 120 DEG C, with thin-layer chromatography monitor react
Process.At 0.1MPa, stops reaction after 6h, be cooled to room temperature.By mixture with 0.1mol/L hydrochloric acid (5mL), and
It is extracted with ethyl acetate (3 × 10mL), merges organic phase.Organic phase is washed with saturated salt solution (5mL) solution, and anhydrous sulphur is added
Sour sodium dries, filters concentration, is separated with column chromatography chromatogram, using the silica gel of 300~400 mesh as stationary phase, in varing proportions
The mixed solvent of ethyl acetate and petroleum ether purifies product as eluant, eluent, yield 79%.
Gained compound is known compound, and physical property and characterize data are as follows:
Yellow solid;1H NMR(400MHz,CDCl3) δ/ppm=12.30 (s, 1H), 8.32 (s, 1H), 7.94 (s, 1H),
7.80 (d, J=7.7Hz, 1H), 7.16-7.03 (m, 5H);13C NMR(101MHz,CDCl3) δ/ppm=148.8,142.8,
133.6,130.2 (d, J=248.2Hz), 127.9,127.6 (d, J=7.8Hz), 124.9,117.2,115.5 (d, J=
22.0Hz),115.3,100.3。
Embodiment 4
The synthesis of 3- [(4- chlorobenzene) is thio] 1H- pyrrolo- [2,3-b] pyridine: 7- azaindole 0.118g is weighed respectively
(1mmol), 4- chlorothio-phenol 0.219g (1.5mmol), cesium hydroxide;The mass ratio of the material of 7- azaindole and cesium hydroxide is
1:0.2;5mL dimethyl sulfoxide is measured, load weighted reactant is sequentially added in the 25mL reaction tube with magneton, room temperature item
It is stirred on magnetic stirring apparatus under part until system is then slowly heated to 100 DEG C in homogeneous phase solution, instead with thin-layer chromatography monitoring
The process answered.At 0.1MPa, stops reaction after 6h, be cooled to room temperature.By mixture with 0.1mol/L hydrochloric acid (5mL),
And extracted with ethyl acetate (3 × 10mL), merge organic phase.Organic phase is washed with saturated salt solution (5mL) solution, is added anhydrous
Sodium sulphate dries, filters concentration, is separated with column chromatography chromatogram, using the silica gel of 300~400 mesh as stationary phase, in varing proportions
Ethyl acetate and the mixed solvent of petroleum ether product is purified as eluant, eluent, yield 77%.
Gained compound is known compound, and physical property and characterize data are as follows:
Yellow solid;1H NMR(400MHz,DMSO-d6) δ/ppm=12.33 (s, 1H), 8.32 (dd, J=4.7Hz, J=
1.5Hz, 1H), 7.96 (d, J=2.3Hz, 1H), 7.79 (dd, J=7.8Hz, J=1.3Hz, 1H), 7.27 (d, J=8.6Hz,
2H), 7.14 (dd, J=7.9Hz, J=4.7Hz, 1H), 7.04 (d, J=8.6Hz, 2H);13C NMR(101MHz,DMSO)δ/
Ppm=148.9,143.8,137.8,133.5,129.6,128.9,127.1,126.7,120. 8,116.8,98.0.
Embodiment 5
The synthesis of 3- [(2,4- dimethyl benzene) is thio] 1H- pyrrolo- [2,3-b] pyridine: 7- azaindole is weighed respectively
0.118g (1mmol), 2,4- thiophenol dimethyl benzene 0.207g (1.5mmol), cesium acetate;The substance of 7- azaindole and cesium acetate
Amount ratio be 1:0.2;5mL dimethyl sulfoxide is measured, load weighted reactant is sequentially added to the 25mL reaction tube with magneton
In, it is stirred on magnetic stirring apparatus under room temperature until system is then slowly heated to 120 DEG C, uses thin layer in homogeneous phase solution
The process of chromatogram monitoring reaction.At 0.1MPa, stops reaction after 6h, be cooled to room temperature.By mixture 0.1mol/L hydrochloric acid
It dilutes (5mL), and is extracted with ethyl acetate (3 × 10mL), merge organic phase.Organic phase is washed with saturated salt solution (5mL) solution
It washs, anhydrous sodium sulfate is added and dries, filters concentration, is separated with column chromatography chromatogram, using the silica gel of 300~400 mesh as stationary phase,
The mixed solvent of ethyl acetate and petroleum ether in varing proportions purifies product as eluant, eluent, yield 72%.
Gained compound is known compound, and physical property and characterize data are as follows:
Yellow solid;1H NMR(400MHz,CDCl3) δ/ppm=12.34 (s, 1H), 8.44 (d, J=5.9Hz, 1H),
7.96 (d, J=9.2Hz, 1H), 7.71 (s, 1H), 7.20-7.15 (m, 1H), 7.01 (s, 1H), 6.78 (d, J=8.8Hz,
1H), 6.70 (d, J=9.4Hz, 1H), 2.50 (s, 3H), 2.26 (s, 3H);13C NMR(101MHz,CDCl3) δ/ppm=
148.4,142.5,134.3,134.2,133.7,131.5,130.4,128.1,126.6,125.5,121.9,116.2,
100.4,20.3,19.5。
Embodiment 6
The synthesis of 3- [(3- methylbenzene) is thio] 1H- pyrrolo- [2,3-b] pyridine: 7- azaindole 0.118g is weighed respectively
The mass ratio of the material of (1mmol), 3- methylbenzene phenyl-sulfhydrate 0.187g (1.5mmol), cesium acetate, 7- azaindole and cesium acetate is 1:
0.2;5mL dimethyl sulfoxide is measured, load weighted reactant is sequentially added in the 25mL reaction tube with magneton, room temperature condition
Under on magnetic stirring apparatus stirring until system be in homogeneous phase solution, be then slowly heated to 120 DEG C, with thin-layer chromatography monitor react
Process.At 0.1MPa, stops reaction after 6h, be cooled to room temperature.By mixture with 0.1mol/L hydrochloric acid (5mL), and
It is extracted with ethyl acetate (3 × 10mL), merges organic phase.Organic phase is washed with saturated salt solution (5mL) solution, and anhydrous sulphur is added
Sour sodium dries, filters concentration, is separated with column chromatography chromatogram, using the silica gel of 300~400 mesh as stationary phase, in varing proportions
The mixed solvent of ethyl acetate and petroleum ether purifies product as eluant, eluent, yield 65%.
Gained compound is known compound, and physical property and characterize data are as follows:
Yellow solid;1H NMR(400MHz,CDCl3) δ/ppm=11.88 (s, 1H), 8.41 (d, J=4.7Hz, 1H),
7.97 (dd, J=7.9Hz, J=1.4Hz, 1H), 7.71 (s, 1H), 7.16 (dd, J=7.9Hz, J=4.8Hz, 1H), 7.05
(d, J=7.6Hz, 1H), 6.96 (s, 1H), 6.89 (d, J=7.7Hz, 2H), 2.23 (s, 3H);13C NMR(101MHz,
CDCl3) δ/ppm=149.4,143.5,138.8,138.7,132.0,128.8,128.7,126.7,126. 2,123.3,
122.4,116.9,101.8,21.5。
Embodiment 7
7- azaindole and arylthio reagent are added in solvent, the molar concentration of 7- azaindole is 0.05mol/
L;Then catalyst is added, reacts 14h at 0.1MPa, 60 DEG C, obtains 3- arylthio -7- azaindole compounds;
Wherein, solvent is dichloroethanes.
Catalyst is potassium carbonate.
The mass ratio of the material of 7- azaindole and catalyst is 1:0.5.
Arylthio reagent is benzenethiol.
The mass ratio of the material of 7- azaindole and aryl thiophenol is 1:1.1.
Embodiment 8
7- azaindole and arylthio reagent are added in solvent, the molar concentration of 7- azaindole is 0.5mol/
L;Then catalyst is added, reacts 12h at 0.1MPa, 120 DEG C, obtains 3- arylthio -7- azaindole compounds;
Wherein, solvent is n,N-Dimethylformamide.
Catalyst is cesium carbonate.
The mass ratio of the material of 7- azaindole and catalyst is 1:0.2.
Arylthio reagent is 4- methylbenzene phenyl-sulfhydrate.
The mass ratio of the material of 7- azaindole and aryl thiophenol is 1:1.3.
Embodiment 9
7- azaindole and arylthio reagent are added in solvent, the molar concentration of 7- azaindole is 0.3mol/
L;Then catalyst is added, reacts 10h at 0.1MPa, 80 DEG C, obtains 3- arylthio -7- azaindole compounds;
Wherein, solvent is acetonitrile.
Catalyst is sodium acetate.
The mass ratio of the material of 7- azaindole and catalyst is 1:0.3.
Arylthio reagent is 4- chlorothio-phenol.
The mass ratio of the material of 7- azaindole and aryl thiophenol is 1:1.5.
Embodiment 10
7- azaindole and arylthio reagent are added in solvent, the molar concentration of 7- azaindole is 0.1mol/
L;Then catalyst is added, reacts 10h at 0.1MPa, 100 DEG C, obtains 3- arylthio -7- azaindole compounds;
Wherein, solvent is n,N-Dimethylformamide.
Catalyst is potassium carbonate.
The mass ratio of the material of 7- azaindole and catalyst is 1:0.1.
Arylthio reagent is 2,4- thiophenol dimethyl benzene.
The mass ratio of the material of 7- azaindole and aryl thiophenol is 1:1.2.
The present embodiments relate to the material arrived, reagent and experimental facilities, are to meet organic compound unless otherwise instructed
The commercial product in object synthesis field.
The above is merely a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, under the premise of not departing from core of the invention technology, improvements and modifications can also be made, what retouching these, which improve, is also answered
When belonging to scope of patent protection of the invention.With any change in the comparable meaning and scope of claims of the present invention,
It is all considered as including within Claims scope.
Claims (8)
1. a kind of green synthesis method of the 3- arylthio -7- azaindole compounds of base catalysis, which is characterized in that by 7- nitrogen
Miscellaneous indoles and arylthio reagent are added in solvent, and base catalyst is then added, and 2~14h is reacted at 60~120 DEG C, is obtained
To 3- arylthio -7- azaindole compounds;Wherein, arylthio reagent is aryl thiophenol.
2. a kind of green syt side of the 3- arylthio -7- azaindole compounds of base catalysis according to claim 1
Method, which is characterized in that solvent is one of dichloroethanes, n,N-Dimethylformamide, dimethyl sulfoxide, acetonitrile.
3. a kind of green syt side of the 3- arylthio -7- azaindole compounds of base catalysis according to claim 1
Method, which is characterized in that base catalyst is one or more of potassium carbonate, cesium carbonate, cesium hydroxide, cesium acetate, sodium acetate.
4. a kind of green syt side of the 3- arylthio -7- azaindole compounds of base catalysis according to claim 1
Method, which is characterized in that aryl thiophenol is benzenethiol, 4- methylbenzene phenyl-sulfhydrate, 4- chlorothio-phenol, 4- fluoro thiophenol, 2,4- dimethyl
Benzenethiol or 3- methylbenzene phenyl-sulfhydrate.
5. a kind of green syt side of the 3- arylthio -7- azaindole compounds of base catalysis according to claim 1
Method, which is characterized in that after 7- azaindole and arylthio reagent are added in solvent, mole of 7- azaindole in solvent
Concentration is 0.05~0.5mol/L.
6. a kind of green syt side of the 3- arylthio -7- azaindole compounds of base catalysis according to claim 1
Method, which is characterized in that the mass ratio of the material of 7- azaindole and aryl thiophenol is 1:(1.1~1.5).
7. a kind of green syt side of the 3- arylthio -7- azaindole compounds of base catalysis according to claim 1
Method, which is characterized in that the mass ratio of the material of 7- azaindole and base catalyst is 1:(0.1~0.5).
8. a kind of green syt side of the 3- arylthio -7- azaindole compounds of base catalysis according to claim 1
Method, which is characterized in that the pressure of reaction is 0.1MPa.
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---|---|---|---|---|
CN110759907A (en) * | 2019-10-29 | 2020-02-07 | 陕西科技大学 | Selective deoxythionation of 7-azaindole-nitrogen oxide region |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107382819A (en) * | 2017-08-11 | 2017-11-24 | 赣南师范大学 | A kind of preparation method of 3 thioindole class compound |
CN108530339A (en) * | 2018-05-07 | 2018-09-14 | 青岛农业大学 | A kind of synthetic method of the compound of class containing Benzenesulfonylindole |
-
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107382819A (en) * | 2017-08-11 | 2017-11-24 | 赣南师范大学 | A kind of preparation method of 3 thioindole class compound |
CN108530339A (en) * | 2018-05-07 | 2018-09-14 | 青岛农业大学 | A kind of synthetic method of the compound of class containing Benzenesulfonylindole |
Non-Patent Citations (4)
Title |
---|
PENG SANG 等: "K2CO3 promoted direct sulfenylation of indoles: a facile approach towards 3-sulfenylindoles", 《GREEN CHEM.》 * |
SONG SONG 等: "Cs2CO3-Catalyzed Aerobic Oxidative Cross-Dehydrogenative Coupling of Thiols with Phosphonates and Arenes", 《ANGEW. CHEM. INT. ED.》 * |
YUANZU YU 等: "An efficient t-BuOK promoted C3-chalcogenylation of indoles with dichalcogenides", 《ORG. BIOMOL. CHEM.》 * |
YUNYUN LIU 等: "Synthesis of 3-sulfenylated indoles by simple NaOH promoted sulfenylation reaction", 《RSC ADVANCES》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN110759907A (en) * | 2019-10-29 | 2020-02-07 | 陕西科技大学 | Selective deoxythionation of 7-azaindole-nitrogen oxide region |
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