CN108658934A - A kind of bis- sulphur -3- 40 thione derivatives of 1,2- of copper catalysis trifluoropropyne defluorinate sulphur Cyclization - Google Patents
A kind of bis- sulphur -3- 40 thione derivatives of 1,2- of copper catalysis trifluoropropyne defluorinate sulphur Cyclization Download PDFInfo
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- CN108658934A CN108658934A CN201810585488.7A CN201810585488A CN108658934A CN 108658934 A CN108658934 A CN 108658934A CN 201810585488 A CN201810585488 A CN 201810585488A CN 108658934 A CN108658934 A CN 108658934A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
- C07D339/02—Five-membered rings
- C07D339/04—Five-membered rings having the hetero atoms in positions 1 and 2, e.g. lipoic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
Abstract
The invention discloses the 1 of a kind of copper catalysis trifluoropropyne defluorinate sulphur Cyclization, 2 two sulphur, 3 40 thione derivatives, with 2 chlorine 3,3,3 trifluoro, 1 propen compounds are as substrate, it is used as catalyst by the way that cuprous bromide is added in substrate, cesium carbonate is as alkali, and tetramethylethylenediamine is as ligand, elemental sulfur is as sulphur source in solvent N, in N dimethylformamides, at 120 DEG C, it is stirred to react 12 hours；After reaction, filtering reacting liquid, it is used in combination saturated nacl aqueous solution to be extracted twice filtrate, back extraction is primary, after separating obtained organic phase is dried with anhydrous sodium sulfate, it filters again, and filtrate is removed into solvent with Rotary Evaporators and obtains residue, chromatography is carried out to residue by silicagel column, and eluted through eluent, the efflux containing target product is collected, efflux is merged and obtains target product by being concentrated in vacuo removing solvent.The present invention has raw material simple and easy to get, preparation process is novel, simple, pollution less, the advantage that energy consumption is low, yield is high.
Description
Technical field
The present invention relates to organic chemistry filed, more particularly to a kind of copper catalysis trifluoropropyne defluorinate sulphur cyclisation is closed
At bis- sulphur -3- 40 thione derivatives of 1,2-.
Background technology
1,2- bis- sulphur -3- thioketones is the important structural unit of a variety of drugs, has significant biology and medicinal properties, including
Chemotherapy, anti-oxidant and Study On The Radioprotective.For example, it is difficult to understand for draw hereby have HIV-resistant activity (referring to
Biochem.Biophys.Res.Comm.1996,221,548), NOSH-1 shows the anti-inflammatory effect for having excellent
(ACSMed.Chem.Lett.2012,3,257), S- danshensus have male sterility certain therapeutic effect (CN
102417501A), Anethol Trithione ADT is used as cholagogic (Rev.SuissePraxisMed.1979,68,1063).
In the prior art, 1,2-, bis- sulphur -3- thioketones is by end alkynes and CS2And S8Multistep reaction obtains at -78 DEG C
(TetrahedronLett.2014,55,5283).Or by 'beta '-ketoester or ketone and specific sulfiding reagent such as P2S5、CS2Or
Lawesson reagents through multistep reaction obtain (Tetrahedron Lett.1993,34,3703. and J.Org.Chem.2002,
67,6461).2016, Singh and his colleague reported one kind and being catalyzed α-allyl disulfide ester and elementary sulfur by indium trichloride
Efficiently synthesize the method (J.Org.Chem.2016,81,11594) of bis- sulphur -3- 40 thione derivatives of 1,2-.However, since these are anti-
Answer condition harsher, wherein some need is reacted at -78 DEG C, and reaction condition is difficult；Some raw materials are not easy to prepare, economic cost
It is excessively high；A variety of causes results in the practicability of these methods and applicability is restricted, and can not really promote on a large scale.
Invention content
In view of the deficienciess of the prior art, this hair is designed to provide a kind of copper catalysis trifluoropropyne defluorinate sulphur cyclisation
Bis- sulphur -3- the 40 thione derivatives of 1,2- of synthesis；Its raw material is easy to prepare, and economic cost is low, and reaction condition is easy, and can be direct
1,2-, bis- sulphur -3- 40 thione derivatives are synthesized, without detaching intermediate product, economy is high.To achieve the above object, the present invention provides
Following technical solution：A kind of 1,2-, bis- sulphur -3- 40 thione derivatives of copper catalysis trifluoropropyne defluorinate sulphur Cyclization, 1,2- bis-
The molecular formula of sulphur -3- 40 thione derivatives is：
It is by chloro- tri- fluoro- 1 propen compounds of 3,3,3- of 2-, sulphur simple substance in catalyst action
Under, it is reacted in the reaction system containing ligand and alkali；The molecule of the compound of chloro- tri- fluoro- 1 propylene of 3,3,3- of 2-
Formula is：
Wherein-R is phenyl, 2- aminomethyl phenyls, 3- aminomethyl phenyls, 4- aminomethyl phenyls, 2,4-
3,5-dimethylphenyl, 4- ethylo benzenes, 3- methoxyphenyls, 4- methoxyphenyls, 4- sulfidomethyls phenyl, 4- tert-butyl-phenyls, 4- benzene
Base phenyl, 4- Phenoxyphenyls, 3- fluorophenyls, 3- chlorphenyls, 3- bromophenyls, 2- methyl -3- fluorophenyls, 4- trifluoromethylbenzenes
Any one in base, 1- naphthalenes, 2- naphthalenes, 2- thienyls, 2- furyls.
The catalyst is any one in cuprous bromide, cuprous acetate, stannous chloride and cuprous iodide.
Reaction temperature is 80-120 DEG C, reaction time 12h.
The ligand is any one in tetramethylethylenediamine, 1,10 ferrosins and bipyridyl.
The alkali is any one in cesium carbonate and potassium phosphate.
Entire reaction carries out in a solvent, and the solvent is in n,N-Dimethylformamide, acetonitrile and dimethyl sulfoxide (DMSO)
Any one.
In reaction, the molfraction of each substance addition is：
1 part of the compound containing chloro- tri- fluoro- 1 propylene of 3,3,3- of 2-；
0.1-0.2 parts of catalyst；
2 parts of alkali；
0.2-0.4 parts of ligand；
1-1.5 parts of sulphur simple substance.
2- chloro- 3,3,3- tri- fluoro- 1 propen compounds and sulphur simple substance are after reaction, described by filtering purification process
Filtering purification process is：Filtering, extraction, organic phase is dry, filtering, evaporates, chromatography, finally the efflux after elution
It is concentrated in vacuo to obtain product.
The extract liquor is saturated nacl aqueous solution.
By carrying out chromatography with silicagel column；The eluent is the mixed solution that petroleum ether and ethyl acetate form,
Its volume ratio is 30:1.
Beneficial effects of the present invention：Target product can be directly synthesized, without detaching intermediate product, need to only be stirred under normal pressure
It mixes reaction and both can get object, yield can reach 88%, enormously simplify process engineering, reduce energy expenditure, have
There is the advantages of high yield；And discard solution is less in reaction process, does not also give off other polluted gas and liquid, therefore this hair
The bright discharge for reducing discard solution has the advantages that environmental protection and ensures operator's health；Furthermore, it is possible to prepare a system
1,2-, the bis- sulphur -3- 40 thione derivatives of 5- phenyl substitution are arranged, this method has stronger substrate universality.So present invention supplement
The blank for preparing 1, the 2- bis- mercaptan -3- 40 thione derivatives methods of 5 substitutions at this stage, promotes bis- sulphur of polysubstituted 1,2- -
The development of 3- 40 thione derivatives provides sound assurance containing 1,2-, bis- sulphur -3- 40 thione derivatives drugs for exploitation, is also fluoride
Transformation to sulfide is offered reference.
Description of the drawings
Fig. 1 is the reaction mechanism figure of the present invention.
Specific implementation mode
Specific embodiment one：By 41.3 milligrams (0.2mmol) (chloro- 3,3,3- trifluoro propyl- 1- alkene -1- bases of 2-) benzene, 5.6 millis
Gram cuprous bromide (20mmol%), 76.9 milligrams of (0.3mmol) S8, 9.3 milligrams of (40%mmol) tetramethylethylenediamines, 130.0
Milligram cesium carbonate, is added in 2mL solvent n,N-Dimethylformamide.It reacts 12 hours at 120 DEG C, cools down after reaction,
Reaction solution is filtered and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, and separating obtained organic phase is used
It is for re-filtering after anhydrous sodium sulfate is dried, filtrate is rotated, solvent is removed and obtains residue, residue is used
Silica gel column chromatography is 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, efflux is collected by actual gradient,
TLC is detected, and merges the efflux containing product, and solvent is distilled off in Rotary Evaporators, and vacuum drying obtains red solid 5- benzene
Bis- 37.0 milligrams of sulphur -3- thioketones of base -3H-1,2-, yield 88%.m.p.122-124℃.1H NMR(500MHz,CDCl3)δ7.57
(d, J=7.0Hz, 2H), 7.47 (d, J=7.0Hz, 2H), 7.42-7.39 (m, 1H), 7.35 (s, 1H)13C NMR(125MHz,
CDCl3) δ 215.5,172.8,135.9,132.1,131.6,129.5,126.8.LRMS (EI 70ev) m/z (%):210(M+,
79),146(20),145(100),122(29).
Specific embodiment two：By 44.1 milligrams of (0.2mmol) 1- (the chloro- 3,3,3- trifluoros propyl- 1- alkene -1- bases of 2-) -2- first
Base benzene, 5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 9.3 milligrams of (40%mmol) tetramethyl second
Diamines, 130.0 milligrams of cesium carbonates are added in 2mL solvent n,N-Dimethylformamide.It is reacted 12 hours at 120 DEG C, reaction knot
Beam postcooling filters reaction solution and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, detaches institute
After organic phase is dried with anhydrous sodium sulfate, it is for re-filtering, filtrate is rotated, remove solvent obtain it is remaining
Object, residue silica gel column chromatography are 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, by actual gradient
Efflux is collected, TLC detections merge the efflux containing product, and solvent is distilled off in Rotary Evaporators, and vacuum drying obtains red
Bis- 33.6 milligrams of sulphur -3- thioketones of color oily liquids 5- (o-tolyl) -3H-1,2-, yield 75%.1H NMR(500MHz,
CDCl3)δ7.36-7.32(m,2H),7.26-7.22(m,2H),7.06(s,1H),2.36(s,3H).13CNMR(125MHz,
CDCl3)δ215.8,172.9,139.3,136.0,131.4,131.0,130.6,129.2,126.4,20.4.LRMS(EI
70ev) m/z (%):224(M+,100),191(27),159(48),147(17).
Specific embodiment three：By 44.1 milligrams of (0.2mmol) 1- (the chloro- 3,3,3- trifluoros propyl- 1- alkene -1- bases of 2-) -3- first
Base benzene, 5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 9.3 milligrams of (40%mmol) tetramethyl second
Diamines, 130.0 milligrams of cesium carbonates are added in 2mL solvent n,N-Dimethylformamide.It is reacted 12 hours at 120 DEG C, reaction knot
Beam postcooling filters reaction solution and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, detaches institute
After organic phase is dried with anhydrous sodium sulfate, it is for re-filtering, filtrate is rotated, remove solvent obtain it is remaining
Object, residue silica gel column chromatography are 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, by actual gradient
Efflux is collected, TLC detections merge the efflux containing product, and solvent is distilled off in Rotary Evaporators, and vacuum drying obtains
36.8 milligrams of bis- sulphur -3- thioketones of red oil 5- (m- tolyls) -3H-1,2-, yield 82%.1H NMR(500MHz,
CDCl3)δ7.38-7.36(m,3H),7.30-7.29(m,2H),2.35(s,3H).13C NMR(125MHz,CDCl3)δ215.5,
S 173.1,139.6,135.8,132.9,131.6,129.4,127.4,124.0,21.3.LRM (EI 70ev) m/z (%):224
(M+,86),207(15),159(100),115(42).
Specific embodiment four：By 44.1 milligrams of (0.2mmol) 1- (the chloro- 3,3,3- trifluoros propyl- 1- alkene -1- bases of 2-) -4- first
Base benzene, 5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 9.3 milligrams of (40%mmol) tetramethyl second
Diamines, 130.0 milligrams of cesium carbonates are added in 2mL solvent n,N-Dimethylformamide.It is reacted 12 hours at 120 DEG C, reaction knot
Beam postcooling filters reaction solution and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, detaches institute
After organic phase is dried with anhydrous sodium sulfate, it is for re-filtering, filtrate is rotated, remove solvent obtain it is remaining
Object, residue silica gel column chromatography are 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, by actual gradient
Efflux is collected, TLC detections merge the efflux containing product, and solvent is distilled off in Rotary Evaporators, and vacuum drying obtains red
Bis- 27.8 milligrams of sulphur -3- thioketones of color solid 5- (p-methylphenyl) -3H-1,2-, yield 62%.m.p.117-119℃.1HNMR
(500MHz,CDCl3) δ 7.47 (d, J=8.0Hz, 2H), 7.35 (s, 1H), 7.21 (d, J=8.0Hz, 2H), 2.34 (s, 3H)
.13C NMR(125MHz,CDCl3)δ215.4,173.1,143.1,135.4,130.3,128.9,126.8,21.5.LRMS(EI
70ev) m/z (%):224(M+,86),207(80),159(100),116(23).
Specific embodiment five：By 46.9 milligrams of (0.2mmol) 1- (the chloro- 3,3,3- trifluoros propyl- 1- alkene -1- bases of 2-) -2,4-
Dimethyl benzene, 5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 9.3 milligrams of (40%mmol) tetramethyls
Base ethylenediamine, 130.0 milligrams of cesium carbonates are added in 2mL solvent n,N-Dimethylformamide.React 12 hours at 120 DEG C, instead
It should terminate postcooling, reaction solution is filtered and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, point
It is for re-filtering after being dried with anhydrous sodium sulfate from gained organic phase, filtrate is rotated, solvent is removed and is remained
Excess, residue silica gel column chromatography are 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, by practical ladder
Degree collects efflux, and TLC detections merge the efflux containing product, and solvent is distilled off in Rotary Evaporators, and vacuum drying obtains
Bis- 38.1 milligrams of sulphur -3- thioketones of red solid 5- (2,4- 3,5-dimethylphenyl) -3H-1,2-, yield 80%.m.p.79-81℃.1H
NMR(500MHz,CDCl3) δ 7.26 (d, J=8.0Hz, 1H), 7.07-7.06 (m, 2H), 7.03 (d, J=8.0Hz, 1H),
2.33(s,3H),2.30(s,3H).13C NMR(125MHz,CDCl3)δ215.8,173.4,141.5,139.1,135.8,
132.2,129.2,127.8,127.2,21.2,20.4.LRMS (EI 70ev) m/z (%):238(M+,94),224(72),205
(25),173(47).
Specific embodiment six：By 46.9 milligrams of (0.2mmol) 1- (the chloro- 3,3,3- trifluoros propyl- 1- alkene -1- bases of 2-) -4- second
Base benzene, 5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 9.3 milligrams of (40%mmol) tetramethyl second
Diamines, 130.0 milligrams of cesium carbonates are added in 2mL solvent n,N-Dimethylformamide.It is reacted 12 hours at 120 DEG C, reaction knot
Beam postcooling filters reaction solution and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, detaches institute
After organic phase is dried with anhydrous sodium sulfate, it is for re-filtering, filtrate is rotated, remove solvent obtain it is remaining
Object, residue silica gel column chromatography are 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, by actual gradient
Efflux is collected, TLC detections merge the efflux containing product, and solvent is distilled off in Rotary Evaporators, and vacuum drying obtains red
Bis- 37.1 milligrams of sulphur -3- thioketones of color solid 5- (4- ethylphenyls) -3H-1,2-, yield 78%.m.p.115-116℃.1H NMR
(500MHz,CDCl3) δ 7.51 (d, J=8.0Hz, 2H), 7.36 (s, 1H), 7.24 (d, J=8.0Hz, 2H), 2.66-2.62
(m,2H),1.21-1.18(m,3H).13C NMR(125MHz,CDCl3)δ215.4,173.2,149.3,135.4,129.1,
127.0,126.9,28.8,15.1.LRMS (EI 70ev) m/z (%):238(M+,89),209(25),173(100),115
(36).HRMS(ESI)Calcd for C11H11S3 +([M+H]+)239.0017,found 239.0019.
Specific embodiment seven：By 47.3 milligrams of (0.2mmol) 1- (the chloro- 3,3,3- trifluoros propyl- 1- alkene -1- bases of 2-) -3- first
Oxygroup benzene, 5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 9.3 milligrams of (40%mmol) tetramethyls
Ethylenediamine, 130.0 milligrams of cesium carbonates are added in 2mL solvent n,N-Dimethylformamide.It reacts 12 hours, reacts at 120 DEG C
Terminate postcooling, reaction solution is filtered and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, separation
It is for re-filtering after gained organic phase is dried with anhydrous sodium sulfate, filtrate is rotated, solvent is removed and obtains residue
Object, residue silica gel column chromatography are 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, by actual gradient
Efflux is collected, TLC detections merge the efflux containing product, and solvent is distilled off in Rotary Evaporators, and vacuum drying obtains red
Bis- 30.2 milligrams of sulphur -3- thioketones of color solid 5- (3- methoxyphenyls) -3H-1,2-, yield 63%.m.p.113-115℃.1H
NMR(500MHz,CDCl3) δ 7.35-7.30 (m, 2H), 7.16 (d, J=7.5Hz, 1H), 7.06 (s, 1H), 7.01 (d, J=
8.5Hz,1H),3.79(s,3H).13C NMR(125MHz,CDCl3)δ215.5,172.7,160.3,136.0,132.8,
130.7,119.3,117.7,112.3,55.5.LRMS (EI 70ev) m/z (%):240(M+,100),209(20),207
(100),175(82).
Specific embodiment eight：By 47.3 milligrams of (0.2mmol) 1- (the chloro- 3,3,3- trifluoros propyl- 1- alkene -1- bases of 2-) -4- first
Oxygroup benzene, 5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 9.3 milligrams of (40%mmol) tetramethyls
Ethylenediamine, 130.0 milligrams of cesium carbonates are added in 2mL solvent n,N-Dimethylformamide.It reacts 12 hours, reacts at 120 DEG C
Terminate postcooling, reaction solution is filtered and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, separation
It is for re-filtering after gained organic phase is dried with anhydrous sodium sulfate, filtrate is rotated, solvent is removed and obtains residue
Object, residue silica gel column chromatography are 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, by actual gradient
Efflux is collected, TLC detections merge the efflux containing product, and solvent is distilled off in Rotary Evaporators, and vacuum drying obtains red
Bis- 26.4 milligrams of sulphur -3- thioketones of color solid 5- (4- methoxyphenyls) -3H-1,2-, yield 55%.m.p.110-111℃.1H
NMR(500MHz,CDCl3) δ 7.54 (d, J=8.5Hz, 2H), 7.31 (s, 1H), 6.90 (d, J=8.5Hz, 2H), 3.81 (s,
3H).13C NMR(125MHz,CDCl3)δ215.1,172.9,162.9,134.6,128.5,124.2,115.0,55.6.LRMS
(EI 70ev) m/z (%):240(M+,75),208(20),207(100),175(69).
Specific embodiment nine：By 50.5 milligrams (0.2mmol) (4- (the chloro- 3,3,3- trifluoros propyl- 1- alkene -1- bases of 2-) phenyl)
(methyl) sulfane, 5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.03mmol) S8, 9.3 milligrams of (40%mmol) four
Methyl ethylenediamine, 130.0 milligrams of cesium carbonates are added in 2mL solvent n,N-Dimethylformamide.It is reacted 12 hours at 120 DEG C,
It cools down after reaction, reaction solution is filtered and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary,
It is for re-filtering after separating obtained organic phase is dried with anhydrous sodium sulfate, filtrate is rotated, solvent is removed and obtains
Residue, residue silica gel column chromatography are 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, by practical
Gradient collects efflux, and TLC detections merge the efflux containing product, and Rotary Evaporators are distilled off solvent, are dried in vacuo
To red solid 5- (4- (methyl mercapto) phenyl) bis- 26.6 milligrams of sulphur -3- thioketones of -3H-1,2-, yield 52%.m.p.86-89℃
.1H NMR(500MHz,CDCl3) δ 7.57 (d, J=8.0Hz, 2H), 7.43 (s, 1H), 7.29 (d, J=8.0Hz, 2H), 2.54
(s,3H).13C NMR(125MHz,CDCl3)δ215.3,172.4,145.2,135.2,127.8,127.0,126.2,
14.9.LRMS (EI 70ev) m/z (%):256(M+,89),224(73),241(35),209(24).HRMS(ESI)Calcd
for C10H9S4 +([M+H]+)256.9582,found 256.9575.
Specific embodiment ten：By 52.5 milligrams of (0.2mmol) 1- (tert-butyl) -4- (chloro- 3,3,3- trifluoros propyl- 1- of 2-
Alkene -1- bases) benzene, 5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 9.3 milligrams of (40%mmol) four
Methyl ethylenediamine, 130.0 milligrams of cesium carbonates are added in 2mL solvent n,N-Dimethylformamide.It is reacted 12 hours at 120 DEG C,
It cools down after reaction, reaction solution is filtered and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary,
It is for re-filtering after separating obtained organic phase is dried with anhydrous sodium sulfate, filtrate is rotated, solvent is removed and obtains
Residue, residue silica gel column chromatography are 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, by practical
Gradient collects efflux, and TLC detections merge the efflux containing product, and Rotary Evaporators are distilled off solvent, are dried in vacuo
To red oil 5- (4- (tertiary butyl) phenyl) bis- 30.3 milligrams of sulphur -3- thioketones of -3H-1,2-, yield 57%.1HNMR
(500MHz,CDCl3) δ 7.52 (d, J=8.0Hz, 2H), 7.42 (d, J=8.0Hz 2H), 7.37 (s, 1H), 1.28 (s, 9H)
.13C NMR(125MHz,CDCl3)δ215.5,173.1,156.1,135.4,128.9,126.7,126.6,35.1,
31.0.LRMS (EI 70ev) m/z (%):266(M+,100),251(57),201(36),171(19).
Specific embodiment 11：By 56.5 milligrams of (0.2mmol) 4- (the chloro- 3,3,3- trifluoros propyl- 1- alkene -1- bases of 2-) -1,
1'- biphenyl, 5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 9.3 milligrams of (40%mmol) tetramethyls
Ethylenediamine, 130.0 milligrams of cesium carbonates are added in 2mL solvent n,N-Dimethylformamide.It reacts 12 hours, reacts at 120 DEG C
Terminate postcooling, reaction solution is filtered and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, separation
It is for re-filtering after gained organic phase is dried with anhydrous sodium sulfate, filtrate is rotated, solvent is removed and obtains residue
Object, residue silica gel column chromatography are 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, by actual gradient
Efflux is collected, TLC detections merge the efflux containing product, and solvent is distilled off in Rotary Evaporators, and vacuum drying obtains red
Color solid 5- ([1,1'- biphenyl] -4- bases) bis- 24.0 milligrams of sulphur -3- thioketones of -3H-1,2-, yield 42%.m.p.119-122℃
.1H NMR(500MHz,CDCl3) δ 7.68-7.63 (m, 4H), 7.55 (d, J=7.5Hz, 2H), 7.43-7.40 (m, 3H), 7.34
(d, J=7.0Hz, 1H)13C NMR(125MHz,CDCl3)δ215.5,172.4,145.1,139.4,1357,130.5,
(129.1,128.5,128.2,127.4,127.1.LRMS EI70ev) m/z (%):286(M+,100),254(21),209
(37),153(45).
Specific embodiment 12：By 59.7 milligrams of (0.2mmol) 1- (the chloro- 3,3,3- trifluoros propyl- 1- alkene -1- bases of 2-) -4-
Phenoxy group benzene, 5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 9.3 milligrams of (40%mmol) tetramethyls
Base ethylenediamine, 130.0 milligrams of cesium carbonates are added in 2mL solvent n,N-Dimethylformamide.React 12 hours at 120 DEG C, instead
It should terminate postcooling, reaction solution is filtered and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, point
It is for re-filtering after being dried with anhydrous sodium sulfate from gained organic phase, filtrate is rotated, solvent is removed and is remained
Excess, residue silica gel column chromatography are 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, by practical ladder
Degree collects efflux, and TLC detections merge the efflux containing product, and solvent is distilled off in Rotary Evaporators, and vacuum drying obtains
Bis- 47.7 milligrams of sulphur -3- thioketones of red solid 5- (4- Phenoxyphenyls) -3H-1,2-, yield 79%.m.p.130-132℃.1H
NMR(500MHz,CDCl3) δ 7.53 (d, J=9.0Hz, 2H), 7.35-7.31 (m, 3H), 7.16-7.13 (m, 1H), 7.00 (d,
J=8.0Hz, 2H), 6.96 (d, J=8.0Hz, 2H)13C NMR(125MHz,CDCl3)δ215.2,172.3,161.4,
155.3,135.1,130.1,128.6,125.9,124.8,120.1,118.4.LRMS (EI 70ev) m/z (%):302(M+,
100),270(27),225(52),209(31).HRMS(ESI)Calcd for C15H11OS3 +([M+H]+)302.9967,
found 32.9972.
Specific embodiment 13：By 44.9 milligrams of (0.2mmol) 1- (the chloro- 3,3,3- trifluoros propyl- 1- alkene -1- bases of 2-) -3-
Fluorobenzene, 5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 9.3 milligrams of (40%mmol) tetramethyl second
Diamines, 130.0 milligrams of cesium carbonates are added in 2mL solvent n,N-Dimethylformamide.It is reacted 12 hours at 120 DEG C, reaction knot
Beam postcooling filters reaction solution and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, detaches institute
After organic phase is dried with anhydrous sodium sulfate, it is for re-filtering, filtrate is rotated, remove solvent obtain it is remaining
Object, residue silica gel column chromatography are 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, by actual gradient
Efflux is collected, TLC detections merge the efflux containing product, and solvent is distilled off in Rotary Evaporators, and vacuum drying obtains red
Bis- 29.6 milligrams of sulphur -3- thioketones of color solid 5- (3- fluorophenyls) -3H-1,2-, yield 65%.m.p.126-128℃.1HNMR
(500MHz,CDCl3) δ 7.43-7.37 (m, 2H), 7.33 (s, 1H), 7.28 (d, J=9.0Hz, 1H), 7.20-7.17 (m,
1H).13C NMR(125MHz,CDCl3)δ215.5,170.7,163.0(q,JC-F=247.5Hz), 136.5,133.6,131.4,
122.7,119.0(d,JC-F=21.3Hz), 114.0 (d, JC-F=23.8Hz) .LRMS (EI 70ev) m/z (%):228(M+,
81),207(36),163(100),120(32).
Specific embodiment 14：By the 48.2 milligrams of chloro- 3- of (0.2mmol) 1- (chloro- 3,3,3- trifluoros propyl- 1- alkene -1- of 2-
Base) benzene, 5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 9.3 milligrams of (40%mmol) tetramethyl second
Diamines, 130.0 milligrams of cesium carbonates are added in 2mL solvent n,N-Dimethylformamide.It is reacted 12 hours at 120 DEG C, reaction knot
Beam postcooling filters reaction solution and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, detaches institute
After organic phase is dried with anhydrous sodium sulfate, it is for re-filtering, filtrate is rotated, remove solvent obtain it is remaining
Object, residue silica gel column chromatography are 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, by actual gradient
Efflux is collected, TLC detections merge the efflux containing product, and solvent is distilled off in Rotary Evaporators, and vacuum drying obtains black
Bis- 31.3 milligrams of sulphur -3- thioketones of color solid 5- (3- chlorphenyls) -3H-1,2-, yield 64%.m.p.106-108℃.1HNMR
(500MHz,CDCl3)δ7.56(s,1H),7.47-7.44(m,2H),7.38-7.34(m,1H),7.32(s,1H).13C NMR
(125MHz,CDCl3)δ215.4,170.5,136.4,135.7,133.2,131.9,130.8,126.9,125.0.LRMS(EI
70ev) m/z (%):244(M+,100),209(53),212(62),137(27).
Specific embodiment 15：By the 57.1 milligrams of bromo- 3- of (0.2mmol) 1- (chloro- 3,3,3- trifluoros propyl- 1- alkene -1- of 2-
Base) benzene, 5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 9.3 milligrams of (40%mmol) tetramethyl second
Diamines, 130.0 milligrams of cesium carbonates are added in 2mL solvent n,N-Dimethylformamide.It is reacted 12 hours at 120 DEG C, reaction knot
Beam postcooling filters reaction solution and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, detaches institute
After organic phase is dried with anhydrous sodium sulfate, it is for re-filtering, filtrate is rotated, remove solvent obtain it is remaining
Object, residue silica gel column chromatography are 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, by actual gradient
Efflux is collected, TLC detections merge the efflux containing product, and solvent is distilled off in Rotary Evaporators, and vacuum drying obtains black
Bis- 47.9 milligrams of sulphur -3- thioketones of color solid 5- (3- bromophenyls) -3H-1,2-, yield 83%.m.p.123-125℃.1HNMR
(500MHz,CDCl3) δ 7.12 (s, 1H), 7.60 (d, J=8.0Hz, 1H), 7.51 (d, J=7.5Hz, 1H), 7.31-7.28
(m,2H).13C NMR(125MHz,CDCl3)δ215.4,170.4,136.4,134.8,133.5,131.0,129.7,125.4,
123.6.LRMS (EI 70ev) m/z (%):289(M+,83),256(41),209(35),156(28).HRMS(ESI)Calcd
for C9H6BrS3 +([M+H]+)288.8810,found288.8812.
Specific embodiment 16：By 47.7 milligrams of (0.2mmol) 1- (the chloro- 3,3,3- trifluoros propyl- 1- alkene -1- bases of 2-) -3-
Fluoro-2-methylbenzene, 5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 9.3 milligrams of (40%mmol) four
Methyl ethylenediamine, 130.0 milligrams of cesium carbonates are added in 2mL solvent n,N-Dimethylformamide.It is reacted 12 hours at 120 DEG C,
It cools down after reaction, reaction solution is filtered and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary,
It is for re-filtering after separating obtained organic phase is dried with anhydrous sodium sulfate, filtrate is rotated, solvent is removed and obtains
Residue, residue silica gel column chromatography are 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, by practical
Gradient collects efflux, and TLC detections merge the efflux containing product, and Rotary Evaporators are distilled off solvent, are dried in vacuo
To bis- 36.8 milligrams of sulphur -3- thioketones of red solid 5- (3- fluoro-2-methylbenzenes base) -3H-1,2-, yield 76%.m.p.115-117
℃.1H NMR(500MHz,CDCl3)δ7.21-7.16(m,2H),7.13-7.10(m,1H),7.04(s,1H),2.27(s,3H)
.13C NMR(125MHz,CDCl3)δ215.7,170.9,161.5(d,JC-F=245.0Hz), 139.6,132.7,127.6,
124.4,123.8(d,JC-F=18.2Hz), 117.6 (d, JC-F=22.5Hz), 12.1.LRMS (EI 70ev) m/z (%):242
(M+,100),209(24),177(54),133(84).HRMS(ESI)Calcd for C10H8FS3 +([M+H]+)242.9767,
found 242.9756.
Specific embodiment 17：By 54.9 milligrams of (0.2mmol) 1- (the chloro- 3,3,3- trifluoros propyl- 1- alkene -1- bases of 2-) -4-
(trifluoromethyl) benzene, 5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of S8(0.3mmol), 9.3 milligrams (40%mmol)
Tetramethylethylenediamine, 130.0 milligrams of cesium carbonates are added in 2mL solvent n,N-Dimethylformamide.Reaction 12 is small at 120 DEG C
When, it cools down after reaction, reaction solution is filtered and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction one
It is secondary, it is for re-filtering after separating obtained organic phase is dried with anhydrous sodium sulfate, filtrate is rotated, solvent is removed
Residue is obtained, residue silica gel column chromatography is 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, is pressed
Actual gradient collects efflux, and TLC detections merge the efflux containing product, and solvent is distilled off in Rotary Evaporators, and vacuum is dry
It is dry to obtain red oil 5- (4- (trifluoromethyl) phenyl) bis- 25.0 milligrams of sulphur -3- thioketones of -3H-1,2-, yield 45%.1H
NMR(500MHz,CDCl3) (s, the 1H) of δ 7.72 (d, J=8.5Hz, 2H), 7.69 (d, J=8.5Hz, 2H), 7.3713C NMR
(125MHz,CDCl3)δ215.5,170.1,137.0,135.0,133.6(q,JC-F=32.5Hz), 127.3,126.6,123.4
(q,JC-F=271.0Hz) .LRMS (EI 70ev) m/z (%):278(M+,68),213(100),170(16).
Specific embodiment 18：By 51.3 milligrams of (0.2mmol) 1- (chloro- 3,3,3- trifluoro propyl- 1- alkene -1- bases of 2-) naphthalene,
5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 9.3 milligrams of (40%mmol) tetramethylethylenediamines,
130.0 milligrams of cesium carbonates are added in 2mL solvent n,N-Dimethylformamide.React 12 hours at 120 DEG C, after reaction
It is cooling, reaction solution is filtered and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, separating obtained to have
It is for re-filtering after machine is mutually dried with anhydrous sodium sulfate, filtrate is rotated, solvent is removed and obtains residue, remain
Excess silica gel column chromatography is 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, is collected by actual gradient
Efflux, TLC detections merge the efflux containing product, and solvent is distilled off in Rotary Evaporators, and vacuum drying obtains red solid
Bis- 38.5 milligrams of sulphur -3- thioketones of body 5- (naphthalene -1- bases) -3H-1,2-, yield 74%.m.p.140-142℃.1H NMR
(500MHz,CDCl3) δ 7.97-7.95 (m, 1H), 7.89 (d, J=8.5Hz, 1H), 7.83-7.81 (m, 1H), 7.56 (d, J=
7.0Hz,1H),7.48-7.47(m,2H),7.44-7.40(m,1H),7.24(s,1H).13CNMR(125MHz,CDCl3)δ
215.5,171.7,139.9,133.7,131.7,130.1,128.6,128.5,127.8,127.7,126.9,124.4.LRMS
(EI 70ev) m/z (%):260(M+,100),228(37),196(12),152(21).
Specific embodiment 19：By 51.3 milligrams of (0.2mmol) 2- (chloro- 3,3,3- trifluoro propyl- 1- alkene -1- bases of 2-) naphthalene,
5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 9.3 milligrams of (40%mmol) tetramethylethylenediamines,
130.0 milligrams of cesium carbonates are added in 2mL solvent n,N-Dimethylformamide.React 12 hours at 120 DEG C, after reaction
It is cooling, reaction solution is filtered and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, separating obtained to have
It is for re-filtering after machine is mutually dried with anhydrous sodium sulfate, filtrate is rotated, solvent is removed and obtains residue, remain
Excess silica gel column chromatography is 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, is collected by actual gradient
Efflux, TLC detections merge the efflux containing product, and solvent is distilled off in Rotary Evaporators, and vacuum drying obtains red solid
Bis- 37.4 milligrams of sulphur -3- thioketones of body 5- (naphthalene -2- bases) -3H-1,2-, yield 72%.m.p.68-71℃.1H NMR(500MHz,
CDCl3) δ 8.11 (s, 1H), 7.86-7.80 (m, 3H), 7.59 (d, J=8.5Hz, 1H), 7.55-7.51 (m, 2H), 7.49 (s,
1H).13C NMR(125MHz,CDCl3)δ215.6,172.8,136.1,134.8,133.0,129.6,129.0,128.9,
128.4,127.9,127.6,127.2,123.4.LRMS (EI 70ev) m/z (%):260(M+,100),228(43),196
(32),151(21).
Specific embodiment 20：By 42.5 milligrams of (0.2mmol) 2- (the chloro- 3,3,3- trifluoros propyl- 1- alkene -1- bases of 2-) thiophene
Pheno, 5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 9.3 milligrams of (40%mmol) tetramethyl second two
Amine, 130.0 milligrams of cesium carbonates are added in 2mL solvent n,N-Dimethylformamide.It is reacted 12 hours at 120 DEG C, reaction terminates
Postcooling filters reaction solution and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, separating obtained
It is for re-filtering after organic phase is dried with anhydrous sodium sulfate, filtrate is rotated, solvent is removed and obtains residue,
Residue silica gel column chromatography is 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, is received by actual gradient
Collect efflux, TLC detections merge the efflux containing product, and solvent is distilled off in Rotary Evaporators, and vacuum drying obtains red
Bis- 24.2 milligrams of sulphur -3- thioketones of solid 5- (thiophene -2- bases) -3H-1,2-, yield 56%.m.p.129℃.1H NMR
(500MHz,CDCl3) δ 7.52 (d, J=5.0Hz, 1H), 7.47 (d, J=3.5Hz, 1H), 7.26 (s, 1H), 7.09-7.07
(m,1H).13C NMR(125MHz,CDCl3)δ214.6,165.0,134.7,134.0,130.9,129.1,129.0.LRMS(EI
70ev) m/z (%):216(M+,100),184(47),133(25),108(32).
Specific embodiment 21：By 39.3 milligrams of (0.2mmol) 2- (the chloro- 3,3,3- trifluoros propyl- 1- alkene -1- bases of 2-) furan
It mutters, 5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 9.3 milligrams of (40%mmol) tetramethyl second two
Amine, 130.0 milligrams of cesium carbonates are added in 2mL solvent n,N-Dimethylformamide.It is reacted 12 hours at 120 DEG C, reaction terminates
Postcooling filters reaction solution and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, separating obtained
It is for re-filtering after organic phase is dried with anhydrous sodium sulfate, filtrate is rotated, solvent is removed and obtains residue,
Residue silica gel column chromatography is 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, is received by actual gradient
Collect efflux, TLC detections merge the efflux containing product, and solvent is distilled off in Rotary Evaporators, and vacuum drying obtains red
Bis- 20.8 milligrams of sulphur -3- thioketones of solid 5- (furans -2- bases) -3H-1,2-, yield 52%.m.p.110-113℃.1HNMR
(500MHz,CDCl3) δ 7.57 (d, J=1.5Hz, 1H), 7.29 (s, 1H), 6.91 (d, J=3.5Hz, 1H), 6.54-6.53
(m,1H).13C NMR(125MHz,CDCl3)δ214.3,159.9,146.5,146.3,133.1,113.3,113.2.LRMS(EI
70ev) m/z (%):200(M+,100),135(93),82(22),69(28).
Specific embodiment 22：By 41.3 milligrams (0.2mmol) (chloro- 3,3,3- trifluoro propyl- 1- alkene -1- bases of 2-) benzene,
4.9 milligrams of cuprous acetates (20mmol%), 76.9 milligrams of (0.3mmol) S8, 130.0 milligrams of cesium carbonates, addition 2mL solvents N, N-
In dimethylformamide.It reacts 12 hours at 120 DEG C, cools down after reaction, reaction solution is filtered and obtains filtrate；With saturation
Filtrate is extracted twice by sodium chloride solution, and back extraction is primary, after separating obtained organic phase is dried with anhydrous sodium sulfate, carries out again
Secondary filtering, rotates filtrate, removes solvent and obtains residue, residue silica gel column chromatography, with petroleum ether and acetic acid second
Ester volume ratio is 30:1 mixed solution elution collects efflux by actual gradient, and TLC detections merge the outflow containing product
Solvent is distilled off in liquid, Rotary Evaporators, and vacuum drying obtains bis- sulphur -3- thioketones of red solid 5- phenyl 3H-1,2-, 20.1 milli
Gram, yield 49%.
Specific embodiment 23：By 41.3 milligrams (0.2mmol) (chloro- 3,3,3- trifluoro propyl- 1- alkene -1- bases of 2-) benzene,
4.0 milligrams of stannous chlorides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 130.0 milligrams of cesium carbonates, addition 2mL solvents N, N-
In dimethylformamide.It reacts 12 hours at 120 DEG C, cools down after reaction, reaction solution is filtered and obtains filtrate；With saturation
Filtrate is extracted twice by sodium chloride solution, and back extraction is primary, after separating obtained organic phase is dried with anhydrous sodium sulfate, carries out again
Secondary filtering, rotates filtrate, removes solvent and obtains residue, residue silica gel column chromatography, with petroleum ether and acetic acid second
Ester volume ratio is 30:1 mixed solution elution collects efflux by actual gradient, and TLC detections merge the outflow containing product
Solvent is distilled off in liquid, Rotary Evaporators, and vacuum drying obtains bis- sulphur -3- thioketones of red solid 5- phenyl 3H-1,2-, 17.6 milli
Gram, yield 42%.
Specific embodiment 24：By 41.3 milligrams (0.2mmol) (chloro- 3,3,3- trifluoro propyl- 1- alkene -1- bases of 2-) benzene,
5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 130.0 milligrams of cesium carbonates, addition 2mL solvents N, N-
In dimethylformamide.It reacts 12 hours at 120 DEG C, cools down after reaction, reaction solution is filtered and obtains filtrate；With saturation
Filtrate is extracted twice by sodium chloride solution, and back extraction is primary, after separating obtained organic phase is dried with anhydrous sodium sulfate, carries out again
Secondary filtering, rotates filtrate, removes solvent and obtains residue, residue silica gel column chromatography, with petroleum ether and acetic acid second
Ester volume ratio is 30:1 mixed solution elution collects efflux by actual gradient, and TLC detections merge the outflow containing product
Solvent is distilled off in liquid, Rotary Evaporators, and vacuum drying obtains bis- sulphur -3- thioketones of red solid 5- phenyl 3H-1,2-, 24.5 milli
Gram, yield 59%.
Specific embodiment 25：By 41.3 milligrams (0.2mmol) (chloro- 3,3,3- trifluoro propyl- 1- alkene -1- bases of 2-) benzene,
7.9 milligrams of cuprous iodides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 130.0 milligrams of cesium carbonates, addition 2mL solvents N, N-
In dimethylformamide.It reacts 12 hours at 120 DEG C, cools down after reaction, reaction solution is filtered and obtains filtrate；With saturation
Filtrate is extracted twice by sodium chloride solution, and back extraction is primary, after separating obtained organic phase is dried with anhydrous sodium sulfate, carries out again
Secondary filtering, rotates filtrate, removes solvent and obtains residue, residue silica gel column chromatography, with petroleum ether and acetic acid second
Ester volume ratio is 30:1 mixed solution elution collects efflux by actual gradient, and TLC detections merge the outflow containing product
Solvent is distilled off in liquid, Rotary Evaporators, and vacuum drying obtains bis- sulphur -3- thioketones of red solid 5- phenyl 3H-1,2-, 18.0 milli
Gram, yield 43%.
Specific embodiment 26：By 41.3 milligrams (0.2mmol) (chloro- 3,3,3- trifluoro propyl- 1- alkene -1- bases of 2-) benzene,
5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 1,10- 14.4 milligrams of ferrosin (40%mmol),
130.0 milligrams of cesium carbonates are added in 2mL solvent n,N-Dimethylformamide.React 12 hours at 120 DEG C, after reaction
It is cooling, reaction solution is filtered and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, separating obtained to have
It is for re-filtering after machine is mutually dried with anhydrous sodium sulfate, filtrate is rotated, solvent is removed and obtains residue, remain
Excess silica gel column chromatography is 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, is collected by actual gradient
Efflux, TLC detections merge the efflux containing product, and solvent is distilled off in Rotary Evaporators, and vacuum drying obtains red solid
Bis- 23.5 milligrams of sulphur -3- thioketones of body 5- phenyl 3H-1,2-, yield 56%.
Specific embodiment 27：By 41.3 milligrams (0.2mmol) (chloro- 3,3,3- trifluoro propyl- 1- alkene -1- bases of 2-) benzene,
5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 12.5 milligrams of bipyridyls (40%mmol), 130.0
Milligram cesium carbonate, is added in 2mL solvent n,N-Dimethylformamide.It reacts 12 hours at 120 DEG C, cools down after reaction,
Reaction solution is filtered and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, and separating obtained organic phase is used
It is for re-filtering after anhydrous sodium sulfate is dried, filtrate is rotated, solvent is removed and obtains residue, residue is used
Silica gel column chromatography is 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, efflux is collected by actual gradient,
TLC is detected, and merges the efflux containing product, and solvent is distilled off in Rotary Evaporators, and vacuum drying obtains red solid 5- benzene
Bis- 26.0 milligrams of sulphur -3- thioketones of base 3H-1,2-, yield 62%.
Specific embodiment 28：By 41.3 milligrams (0.2mmol) (chloro- 3,3,3- trifluoro propyl- 1- alkene -1- bases of 2-) benzene,
5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 9.3 milligrams of tetramethylethylenediamines (40%mmol),
55.2 milligrams of potassium carbonate are added in 2mL solvent n,N-Dimethylformamide.It is reacted 12 hours at 120 DEG C, it is cold after reaction
But, reaction solution is filtered and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, separating obtained organic
It is for re-filtering after being mutually dried with anhydrous sodium sulfate, filtrate is rotated, solvent is removed and obtains residue, it is remaining
Object silica gel column chromatography is 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, is collected by actual gradient and is flowed
Go out liquid, TLC detections merge the efflux containing product, and solvent is distilled off in Rotary Evaporators, and vacuum drying obtains red solid
Bis- 26.0 milligrams of sulphur -3- thioketones of 5- phenyl 3H-1,2-, yield 62%.
Specific embodiment 29：By 41.3 milligrams (0.2mmol) (chloro- 3,3,3- trifluoro propyl- 1- alkene -1- bases of 2-) benzene,
5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 9.3 milligrams of tetramethylethylenediamines (40%mmol),
85.0 milligrams of potassium phosphates are added in 2mL solvent n,N-Dimethylformamide.It is reacted 12 hours at 120 DEG C, it is cold after reaction
But, reaction solution is filtered and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, separating obtained organic
It is for re-filtering after being mutually dried with anhydrous sodium sulfate, filtrate is rotated, solvent is removed and obtains residue, it is remaining
Object silica gel column chromatography is 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, is collected by actual gradient and is flowed
Go out liquid, TLC detections merge the efflux containing product, and solvent is distilled off in Rotary Evaporators, and vacuum drying obtains red solid
Bis- 15.1 milligrams of sulphur -3- thioketones of 5- phenyl 3H-1,2-, yield 36%.
Specific embodiment 30：By 41.3 milligrams (0.2mmol) (chloro- 3,3,3- trifluoro propyl- 1- alkene -1- bases of 2-) benzene, 5.6
Milligram cuprous bromide (20mmol%), 76.9 milligrams of (0.3mmol) S8, 9.3 milligrams of tetramethylethylenediamines (40%mmol),
130.0 milligrams of cesium carbonates are added in 2mL dimethyl sulfoxide solvents.It reacts 12 hours at 120 DEG C, cools down after reaction, it is right
Reaction solution filtering obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, separating obtained organic phase nothing
It is for re-filtering after aqueous sodium persulfate is dried, filtrate is rotated, solvent is removed and obtains residue, residue silicon
Plastic column chromatography is 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, efflux is collected by actual gradient,
TLC is detected, and merges the efflux containing product, and solvent is distilled off in Rotary Evaporators, and vacuum drying obtains red solid 5- benzene
Bis- 27.3 milligrams of sulphur -3- thioketones of base 3H-1,2-, yield 65%.
Specific embodiment 31：By 41.3 milligrams (0.2mmol) (chloro- 3,3,3- trifluoro propyl- 1- alkene -1- bases of 2-) benzene,
5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 9.3 milligrams of tetramethylethylenediamines (40%mmol),
130.0 milligrams of cesium carbonates are added in 2mL acetonitrile solvents.It reacts 12 hours, cools down after reaction, to reaction solution at 120 DEG C
Filtering obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, separating obtained organic phase anhydrous slufuric acid
It is for re-filtering after sodium is dried, filtrate is rotated, solvent is removed and obtains residue, residue silica gel column layer
Analysis is 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution collects efflux by actual gradient, and TLC is detected,
Merge the efflux containing product, solvent is distilled off in Rotary Evaporators, and vacuum drying obtains red solid 5- phenyl 3H-1,2-
Two 9.7 milligrams of sulphur -3- thioketones, yield 23%.
Specific embodiment 32：By 41.3 milligrams (0.2mmol) (chloro- 3,3,3- trifluoro propyl- 1- alkene -1- bases of 2-) benzene,
5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 9.3 milligrams of tetramethylethylenediamines (40%mmol),
130.0 milligrams of cesium carbonates are added in 2mL toluene solvants.It reacts 12 hours, cools down after reaction, to reaction solution at 120 DEG C
Filtering obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, separating obtained organic phase anhydrous slufuric acid
It is for re-filtering after sodium is dried, filtrate is rotated, solvent is removed and obtains residue, residue silica gel column layer
Analysis is 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution collects efflux by actual gradient, and TLC is detected,
Merge the efflux containing product, solvent is distilled off in Rotary Evaporators, and vacuum drying obtains trace red solid 5- phenyl 3H-
Bis- sulphur -3- thioketones yields of 1,2- are less than 10%.
Specific embodiment 33：By 41.3 milligrams (0.2mmol) (chloro- 3,3,3- trifluoro propyl- 1- alkene -1- bases of 2-) benzene,
5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 9.3 milligrams of tetramethylethylenediamines (40%mmol),
130.0 milligrams of cesium carbonates are added in 2mL solvent n,N-Dimethylformamide.React 12 hours at 100 DEG C, after reaction
It is cooling, reaction solution is filtered and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, separating obtained to have
It is for re-filtering after machine is mutually dried with anhydrous sodium sulfate, filtrate is rotated, solvent is removed and obtains residue, remain
Excess silica gel column chromatography is 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, is collected by actual gradient
Efflux, TLC detections merge the efflux containing product, and solvent is distilled off in Rotary Evaporators, and vacuum drying obtains red solid
Bis- 26.5 milligrams of yields 63% of sulphur -3- thioketones of body 5- phenyl 3H-1,2-.
Specific embodiment 34：By 41.3 milligrams (0.2mmol) (chloro- 3,3,3- trifluoro propyl- 1- alkene -1- bases of 2-) benzene,
5.6 milligrams of cuprous bromides (20mmol%), 76.9 milligrams of (0.3mmol) S8, 9.3 milligrams of tetramethylethylenediamines (40%mmol),
130.0 milligram cesium carbonate is added in 2mL solvent n,N-Dimethylformamide.It is reacted 12 hours at 80 DEG C, it is cold after reaction
But, reaction solution is filtered and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, separating obtained organic
It is for re-filtering after being mutually dried with anhydrous sodium sulfate, filtrate is rotated, solvent is removed and obtains residue, it is remaining
Object silica gel column chromatography is 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, is collected by actual gradient and is flowed
Go out liquid, TLC detections merge the efflux containing product, and solvent is distilled off in Rotary Evaporators, and vacuum drying obtains red solid
Bis- 21.0 milligrams of yields 50% of sulphur -3- thioketones of 5- phenyl 3H-1,2-.
Specific embodiment 35：By 41.3 milligrams (0.2mmol) (chloro- 3,3,3- trifluoro propyl- 1- alkene -1- bases of 2-) benzene,
5.6 milligrams of cuprous bromides (20mmol%), 1.2 61.4 milligrams of equivalent S8, 9.3 milligrams of tetramethylethylenediamines (40%mmol),
130.0 milligrams of cesium carbonates are added in 2mL solvent n,N-Dimethylformamide.React 12 hours at 120 DEG C, after reaction
It is cooling, reaction solution is filtered and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, separating obtained to have
It is for re-filtering after machine is mutually dried with anhydrous sodium sulfate, filtrate is rotated, solvent is removed and obtains residue, remain
Excess silica gel column chromatography is 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, is collected by actual gradient
Efflux, TLC detections merge the efflux containing product, and solvent is distilled off in Rotary Evaporators, and vacuum drying obtains red solid
Bis- 30.2 milligrams of yields 72% of sulphur -3- thioketones of body 5- phenyl 3H-1,2-.
Specific embodiment 36：By 41.3 milligrams (0.2mmol) (chloro- 3,3,3- trifluoro propyl- 1- alkene -1- bases of 2-) benzene,
5.6 milligrams of cuprous bromides (20mmol%), 1.0 51.2 milligrams of equivalent S8, 9.3 milligrams of tetramethylethylenediamines (40%mmol),
130.0 milligram cesium carbonate is added in 2mL solvent n,N-Dimethylformamide.React 12 hours at 120 DEG C, after reaction
It is cooling, reaction solution is filtered and obtains filtrate；Filtrate is extracted twice with saturated nacl aqueous solution, back extraction is primary, separating obtained to have
It is for re-filtering after machine is mutually dried with anhydrous sodium sulfate, filtrate is rotated, solvent is removed and obtains residue, remain
Excess silica gel column chromatography is 30 with petroleum ether and ethyl acetate volume ratio:1 mixed solution elution, is collected by actual gradient
Efflux, TLC detections merge the efflux containing product, and solvent is distilled off in Rotary Evaporators, and vacuum drying obtains red solid
Bis- 28.6 milligrams of yields 68% of sulphur -3- thioketones of body 5- phenyl 3H-1,2-.
The embodiment of the present invention is using the compound containing chloro- tri- fluoro- 1 propylene of 3,3,3- of 2- as substrate and 1.0-1.5 equivalent sulphur
Simple substance reacts, and the molar range of cuprous bromide is 10%~20%, and the tetramethylethylenediamine that ligand is 20~40%, alkali is carbonic acid
Caesium, solvent is based on n,N-Dimethylformamide.Wherein embodiment one to 17 is using different substituted-phenyls as variable.It is worth note
It anticipates, the method for the present invention can also have been used well by inhaling electrical substituent group by force on phenyl；Embodiment 18 to 21 with
Substituent R is naphthalene and heterocycle is variable；Embodiment 22 to 25 is using catalyst mantoquita as variable；Embodiment 20
Six to 27 using ligand as variable；Embodiment 28 to 29 is using alkali as variable；Embodiment 30 to 32 is with molten
Agent is variable；Embodiment 33 to 34 is using temperature as variable；Embodiment 35 to 36 is with the amount of sulphur simple substance
Variable.
The present invention reaction equation be：
The reaction mechanism of the present invention makes detailed description to reaction mechanism referring to Fig.1：
First, S8Dissociation reaction occurs under alkaline condition, SO can be generated3 2-And S2-, S2-Can further with S8Reaction life
At the polysulfide containing-S-S-.Then, contain 2- chloro- 3, the compound (hereinafter referred to as substrate 1) of 3,3- tri- fluoro- 1 propylene is in alkali
Under the action of can slough a molecule-Cl, generate HCl, and the double bond in substrate 1 becomes three keys, derives to form trifluoropropyne
Object, trifluoropropyne derivative and S2-It is reacted under catalyst, a fluorine can be sloughed to generate intermediate A.Then, intermediate A
In will continue to slough a fluorine and form thio acyl fluorides active species B, the thio active species B of acyl fluorides by the effect with catalyst,
With S2-To obtain intermediate C, intermediate C is eliminated the ligand exchange of oxidation addition and polysulfide by reduction, sloughs CuBr
Obtain D；Finally under the influence of nucleation in the molecule, sulfide carries out cyclization with three keys and protonates, and forms cyclisation
Product 2.
It can directly synthesize target product 1 in the present invention, bis- sulphur -3- 40 thione derivatives of 2-, without detaching intermediate product, only
It need to be stirred to react under normal pressure and both can get object；And with the compound and sulphur simple substance of chloro- tri- fluoro- 1 propylene of 3,3,3- containing 2-
As raw material, reactant is easy to get, and manufacturing cost is low；And by the way that alkali and ligand are added in system, reaction temperature is controlled
At 80-120 DEG C, reaction time 12h can greatly improve yield, and yield can reach 88%, enormously simplify technique work
Journey reduces energy expenditure, has the advantages that high yield；And discard solution is less in reaction process, does not also give off other dirts
Gas and liquid are contaminated, therefore The present invention reduces the discharges of discard solution, with environmental protection and ensure operator's health
Advantage；Furthermore, it is possible to prepare a series of 1,2-, the bis- sulphur -3- 40 thione derivatives of 5- phenyl substitutions, this method has stronger bottom
Object universality.So sky of the present invention supplemented with the bis- mercaptan -3- 40 thione derivatives methods of 1,2- for preparing 5 substitutions at this stage
In vain, the development for promoting bis- sulphur -3- 40 thione derivatives of polysubstituted 1,2-, to develop the bis- sulphur -3- 40 thione derivatives drugs containing 1,2-
Sound assurance is provided, the also transformation for fluoride to sulfide is offered reference.
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned implementation
Example, all technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It should be pointed out that for the art
Those of ordinary skill for, several improvements and modifications without departing from the principles of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of 1,2-, the bis- sulphur -3- 40 thione derivatives of copper catalysis trifluoropropyne defluorinate sulphur Cyclization, it is characterised in that：1,2-
The molecular formula of two sulphur -3- 40 thione derivatives is：It is propylated by the chloro- 3,3,3- tri- fluoro- 1 of 2-
It closes object, sulphur simple substance under the action of catalyst, is reacted in the reaction system containing ligand and alkali；The chloro- 3,3,3- of 2-
The molecular formula of three fluoro- 1 propen compounds is：
Wherein-R is phenyl, 2- aminomethyl phenyls, 3- aminomethyl phenyls, 4- aminomethyl phenyls, 2,4- dimethyl
Phenyl, 4- ethylo benzenes, 3- methoxyphenyls, 4- methoxyphenyls, 4- sulfidomethyls phenyl, 4- tert-butyl-phenyls, 4- phenyls,
4- Phenoxyphenyls, 3- fluorophenyls, 3- chlorphenyls, 3- bromophenyls, 2- methyl -3- fluorophenyls, 4- trifluoromethyls, 1- naphthalenes
Any one in base, 2- naphthalenes, 2- thienyls, 2- furyls.
2. a kind of bis- sulphur -3- thioketones of copper catalysis trifluoropropyne defluorinate sulphur Cyclization 1,2- according to claim 1 derives
The method of object, it is characterised in that：The catalyst is arbitrary in cuprous bromide, cuprous acetate, stannous chloride and cuprous iodide
It is a kind of.
3. a kind of bis- sulphur -3- thioketones of copper catalysis trifluoropropyne defluorinate sulphur Cyclization 1,2- according to claim 1 derives
Object, it is characterised in that：Reaction temperature is 80-120 DEG C, reaction time 12h.
4. a kind of bis- sulphur -3- thioketones of copper catalysis trifluoropropyne defluorinate sulphur Cyclization 1,2- according to claim 1 derives
Object, it is characterised in that：The ligand is any one in tetramethylethylenediamine, 1,10 ferrosins and bipyridyl.
5. a kind of bis- sulphur -3- thioketones of copper catalysis trifluoropropyne defluorinate sulphur Cyclization 1,2- according to claim 1 derives
Object, it is characterised in that：The alkali is any one in cesium carbonate and potassium phosphate.
6. a kind of bis- sulphur -3- thioketones of copper catalysis trifluoropropyne defluorinate sulphur Cyclization 1,2- according to claim 5 derives
Object, it is characterised in that：Entire reaction carries out in a solvent, and the solvent is that n,N-Dimethylformamide, acetonitrile and dimethyl are sub-
Any one in sulfone.
7. a kind of bis- sulphur -3- thioketones of copper catalysis trifluoropropyne defluorinate sulphur Cyclization 1,2- according to claim 5 derives
Object, it is characterised in that：In reaction, the molfraction of each substance addition is：
Chloro- tri- 1 part of fluoro- 1 propen compounds of 3,3,3- of 2-；
0.1-0.2 parts of catalyst；
2 parts of alkali；
0.2-0.4 parts of ligand；
1-1.5 parts of sulphur simple substance.
8. a kind of bis- sulphur -3- thioketones of copper catalysis trifluoropropyne defluorinate sulphur Cyclization 1,2- according to claim 7 derives
Object, it is characterised in that：2- chloro- 3,3,3- tri- fluoro- 1 propen compounds and sulphur simple substance purify work after reaction, by filtering
Sequence, the filtering purification process are：Filtering, extraction, organic phase is dry, filtering, evaporates, chromatography, finally after elution
Efflux be concentrated in vacuo to obtain product.
9. a kind of bis- sulphur -3- thioketones of copper catalysis trifluoropropyne defluorinate sulphur Cyclization 1,2- according to claim 8 derives
Object, it is characterised in that：The extract liquor is saturated nacl aqueous solution.
10. a kind of bis- sulphur -3- thioketones of copper catalysis trifluoropropyne defluorinate sulphur Cyclization 1,2- according to claim 9 derives
Object, it is characterised in that：By carrying out chromatography with silicagel column；The eluent is the mixing that petroleum ether and ethyl acetate form
Solution, volume ratio 30:1.
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| CN109776489A (en) * | 2019-02-26 | 2019-05-21 | 温州大学 | The method of copper catalysis bis- sulphur -3- 40 thione derivatives of phenylpropyl alcohol ynamine sulphur Cyclization 1,2- |
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| DE3636157A1 (en) * | 1986-10-24 | 1988-04-28 | Basf Ag | New methylenedithiolenequinone dyes, and thin, radiation-sensitive coating films containing them |
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| DE3636157A1 (en) * | 1986-10-24 | 1988-04-28 | Basf Ag | New methylenedithiolenequinone dyes, and thin, radiation-sensitive coating films containing them |
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| CN109776489A (en) * | 2019-02-26 | 2019-05-21 | 温州大学 | The method of copper catalysis bis- sulphur -3- 40 thione derivatives of phenylpropyl alcohol ynamine sulphur Cyclization 1,2- |
| CN109776489B (en) * | 2019-02-26 | 2021-03-30 | 温州大学 | Method for synthesizing 1, 2-disulfide-3-thioketone derivative by copper-catalyzed thiocyclization of amphetamine |
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