CN106256818B - A kind of indone with trifluoromethylthio and its derivative and preparation method thereof - Google Patents
A kind of indone with trifluoromethylthio and its derivative and preparation method thereof Download PDFInfo
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- CN106256818B CN106256818B CN201610546956.0A CN201610546956A CN106256818B CN 106256818 B CN106256818 B CN 106256818B CN 201610546956 A CN201610546956 A CN 201610546956A CN 106256818 B CN106256818 B CN 106256818B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
Abstract
The invention discloses the preparation method of a kind of indone with trifluoromethylthio He its derivative, it is raw material that this method, which chooses acetylenic ketone compounds and fluoroform sulfane alcohol silver compound, oxidant is used as using persulfate reagent, using HMPA as stabilizer, in reaction dissolvent, in reaction temperature be 80oReacted under C, react 12h, react and obtain indanone compounds through post processing after terminating, the preparation method solves solution amide-type and heterocycle directly generates the technical barrier of indanone compounds, and the preparation method has many advantages, such as economic economical, stability is high, reaction condition is gentle, the reaction time is short, raw material is cheap and easy to get, product yield and purity are high.
Description
Technical field
The invention belongs to technical field of organic synthesis, especially a kind of indone with trifluoromethylthio and its derivative and
Its preparation method.
Background technology
Trifluoromethylthio (- SCF3) has strong sucting electronic effect, highly lipophilic（Hydrophobic Parameters）With it is good
The characteristics such as good bioactivity, therefore compound chemical stability and generation can be significantly changed by being introduced into organic compound
Thank to stability.Therefore ,-SCF is contained3The compound of base has greatly potential in medicine, the field such as agricultural chemicals and material
Application value.For example, Coccidiostatic Drug Toltrazuril（Toltrazuril）, insecticide (Vaniliprole) and anorexia
Medicine Tiflorex (Tiflorex), antihypertensive Losartan (Losartan analogue) etc., all contain fluoroform
Sulfenyl, shown in following article chemical structural formula：
Good characteristic based on trifluoromethylthio, people show extensive interest to trifluoromethylthioization reaction.For example,
Researcher, which has researched and developed, is prepared for a variety of arylations, alkylene, and carbonylation etc. carries the related compound of trifluoromethylthio.
Arylation reaction, the trifluoro methyl mercaptan CF found such as Harris3Addition reactions of the SH to fluoroolefins, the reaction is in X
Then ray or the lower generation trifluoromethylthio free radical of ultraviolet irradiation carry out addition to fluoroolefins.But there is raw material hardly possible in the reaction
With preserve, reaction condition is more harsh the shortcomings of；As Billard is usedN-The indoles of trifluoro-methylthio aniline and electron rich is to first
Electrophilic reaction occurs in the presence of benzene sulfonic acid and solvent DCM, carries out olefination, the indoles of generation trifluoromethylthio substitution
Compound；But but due toN-Trifluoro-methylthio aniline raw material is difficult to prepare, and its can only with the indole reaction of electron rich, therefore react
Limitation is larger；Carbonylation, such as Munavalli, S have found under study for action, CF3Under SCl illumination can with trimethyl silicane
Radical reaction, generation occur for base enol ether2-Trifluoromethylthio cyclohexanone,2,2- two trifluoromethylthio cyclohexanone and2,6Two or three
Fluorine methyl mercapto cyclohexanone etc., but its generation product is not single-minded, and CF3SCl is unstable, and toxicity is big.In view of above-mentioned arylation, alkene
Following various limitations be present in the reactions such as change, carbonylation：Material toxicity is big, raw material is unstable, severe reaction conditions, must use purple
Outer lamp or illumination could be participated in reacting and substrate spectrum adaptability is not extensive etc., and the present invention is used trifluoromethylthio
This active fragment is grafted onto the method on indanone compounds and a series of carries fluoroform benzo-thiophene ketone compounds to prepare.
The content of the invention
For overcome the deficiencies in the prior art, green, safe and efficient a kind of band is prepared the invention provides a kind of
The indone of trifluoromethylthio and the preparation method of its derivative, the preparation method, which solves, directly generates indanone compounds process
Present in cost is too high and the technical barrier of substrate bad adaptability etc.；And the preparation method has that cost is low, stability is high, anti-
Answer many advantages, such as mild condition, reaction time are short, raw material is cheap and easy to get, product yield and purity are high.
To achieve these goals, the technical solution adopted by the present invention is：A kind of indone with trifluoromethylthio spreads out with it
The preparation method of biology, it is characterised in that comprise the following steps：Choose acetylenic ketone compounds and fluoroform mercaptan silver compound
For raw material, using persulfate reagent as oxidant, using HMPA as stabilizer, in reaction dissolvent, in reaction
Temperature is to be reacted at 80 DEG C, reacts 12h, reacts and obtains such as following formula through post processing after terminating（II）Indanone compounds,
Its chemical equation is as follows,
The formula（I）In R1For any one in hydrogen, alkyl, halogen radical.Alkyl using saturated alkyl be it is preferred, can be with
It is that straight chained alkyl can also be branched alkyl, persulfate reagent can use potassium peroxydisulfate, sodium peroxydisulfate etc. common examination
Agent, but be preferred using potassium peroxydisulfate.
Further, the halogen radical is any one in-F ,-Cl ,-Br.
Further, the reaction dissolvent is acetonitrile, DMF（DMF）, dimethyl sulfoxide (DMSO)（DMSO）, third
In ketone at least any one.
Further, the acetylenic ketone compounds and the mol ratio of fluoroform sulfane alcohol silver compound are 1:1.5.
Further, the acetylenic ketone compounds and the mol ratio of HMPA stabilizer are 1:0.1.
Further, the acetylenic ketone compounds and the mol ratio of persulfate are 1:1-5.
Further, the post processing after reaction terminates comprises the following steps, after completion of the reaction, with Rotary Evaporators from reaction
Solvent is removed in the mixture obtained after end, residue is purified to obtain target product, post layer with 300-400 mesh silica gel column chromatographies
Analysis process can determine suitably to elute terminal with TLC tracing and monitorings.
Another object of the present invention is to provide it is a kind of as obtained by above-mentioned preparation method with trifluoromethylthio
Indone and its derivative, it is characterised in that comprising-SCF3Functional group, chemical structural formula are as follows：Comprising-SCF3Functional group,
Chemical structural formula is as follows：
R1For hydrogen, R2For hydrogen, alkyl or halogen radical.
Using such scheme, synthetic method of the invention is with acetylenic ketone compounds and fluoroform mercaptan silver compound
（AgSCF3Because its stability is high, economical and easily available, it is to provide the ideal chose of trifluoromethylthio）For raw material, persulfate is used
Reagent as oxidant and to other technological parameters carry out suitably select and combine, by persulfate produce free radical and
Monovalence silver is aoxidized to divalence, so as to produce trifluoromethylthio free radical, is further cyclized and is eliminated by β-H, so as to which a step obtains
The indanone compounds with trifluoromethylthio are arrived；In the reaction system, raw material converts completely, only generates target product, does not have
The generation of other impurities, Atom economy is high, and cost is low, reaction condition is simple, and directly can carry out in atmosphere, relatively
Security is higher；The last handling process after terminating is reacted except the above method, can also use crystallization, column chromatography purification, extraction
Any one of processing means or a variety of processing means combination.The preparation method has that reaction condition is gentle, the reaction time
Short, many advantages, such as raw material is cheap and easy to get, product yield and purity are high, it is the preparation of new trifluoromethylthio indanone compounds
Effective synthetic method is provided, there is good researching value and application prospect.Use one-step synthesis indone class chemical combination at present
The method of thing, its applicability is poor, cannot react than band electron deficient benzene ring type compounds as described above, therefore, be not particularly suited for
Trifluoromethylthio is introduced directly into indanone compounds by preparation, and because temperature is higher, the easier oxidation of trifluoromethylthio,
So causing yield relatively low, present invention adds the stabilizer that HMPA is trifluoromethylthio, coordinates persulfate to improve synthesis
Target product yield, therefore it solves present in current anamorphic zone trifluoromethylthio indanone compounds method
Series technique problem.
The invention will be further described below in conjunction with the accompanying drawings.
Brief description of the drawings
Accompanying drawing 1 is product 3- (4- methylbenzenes) -2- in the specific embodiment of the invention one to five, embodiment 15 to 17
The nuclear magnetic spectrogram of ((trifluoromethyl) sulphur) -1H- 1-Indanones；
Accompanying drawing 2 is product 3- (4- methylbenzenes) -2- in the specific embodiment of the invention one to five, embodiment 15 to 17
The nuclear magnetic spectrogram of ((trifluoromethyl) sulphur) -1H- 1-Indanones；
Accompanying drawing 3 is product 3- (4- methylbenzenes) -2- in the specific embodiment of the invention one to five, embodiment 15 to 17
The nuclear magnetic spectrogram of ((trifluoromethyl) sulphur) -1H- 1-Indanones；
Accompanying drawing 4 is product 3- (3- methylbenzenes) -2- ((trifluoromethyl) sulphur) -1H- indenes -1- in the specific embodiment of the invention six
Ketone nuclear magnetic spectrogram；
Accompanying drawing 5 is product 3- (3- methylbenzenes) -2- ((trifluoromethyl) sulphur) -1H- indenes -1- in the specific embodiment of the invention six
Ketone nuclear magnetic spectrogram；
Accompanying drawing 6 is product 3- (3- methylbenzenes) -2- ((trifluoromethyl) sulphur) -1H- indenes -1- in the specific embodiment of the invention six
Ketone nuclear magnetic spectrogram；
Accompanying drawing 7 is product 3- (4- ethylo benzenes) -2- ((trifluoromethyl) sulphur) -1H- indenes -1- in the specific embodiment of the invention seven
Ketone nuclear magnetic spectrogram；
Accompanying drawing 8 is product 3- (4- ethylo benzenes) -2- ((trifluoromethyl) sulphur) -1H- indenes -1- in the specific embodiment of the invention seven
Ketone nuclear magnetic spectrogram；
Accompanying drawing 9 is product 3- (4- ethylo benzenes) -2- ((trifluoromethyl) sulphur) -1H- indenes -1- in the specific embodiment of the invention seven
Ketone nuclear magnetic spectrogram；
Accompanying drawing 10 be the specific embodiment of the invention eight in product 3- (4- propylbenzenes) -2- ((trifluoromethyl) sulphur) -1H- indenes -
1- ketone nuclear magnetic spectrograms；
Accompanying drawing 11 be the specific embodiment of the invention eight in product 3- (4- propylbenzenes) -2- ((trifluoromethyl) sulphur) -1H- indenes -
1- ketone nuclear magnetic spectrograms；
Accompanying drawing 12 be the specific embodiment of the invention eight in product 3- (4- propylbenzenes) -2- ((trifluoromethyl) sulphur) -1H- indenes -
1- ketone nuclear magnetic spectrograms；
Accompanying drawing 13 is product 3- (4- butyl benzenes) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones in the embodiment of the present invention nine
Nuclear magnetic spectrogram；
Accompanying drawing 14 is product 3- (4- butyl benzenes) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones in the embodiment of the present invention nine
Nuclear magnetic spectrogram；
Accompanying drawing 15 is product 3- (4- butyl benzenes) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones in the embodiment of the present invention nine
Nuclear magnetic spectrogram；
Accompanying drawing 16 is product 3- (4- fluorobenzene) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones in the embodiment of the present invention 11
Nuclear magnetic spectrogram；
Accompanying drawing 17 is product 3- (4- fluorobenzene) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones in the embodiment of the present invention 11
Nuclear magnetic spectrogram；
Accompanying drawing 18 is product 3- (4- fluorobenzene) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones in the embodiment of the present invention 11
Nuclear magnetic spectrogram；
Accompanying drawing 19 is product 3- (3- chlorobenzenes) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones in the embodiment of the present invention 12
Nuclear-magnetism is composed；
Accompanying drawing 20 is product 3- (3- chlorobenzenes) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones in the embodiment of the present invention 12
Nuclear-magnetism is composed；
Accompanying drawing 21 is product 3- (3- chlorobenzenes) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones in the embodiment of the present invention 12
Nuclear-magnetism is composed；
Accompanying drawing 22 is product 3- (4- bromobenzenes) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones in the embodiment of the present invention 13
Nuclear magnetic spectrogram；
Accompanying drawing 23 is product 3- (4- bromobenzenes) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones in the embodiment of the present invention 13
Nuclear magnetic spectrogram；
Accompanying drawing 24 is that product 3- benzene -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones nuclear-magnetism is composed in the embodiment of the present invention 14
Figure；
Accompanying drawing 25 is that product 3- benzene -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones nuclear-magnetism is composed in the embodiment of the present invention 14
Figure；
Accompanying drawing 26 is that product 3- benzene -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones nuclear-magnetism is composed in the embodiment of the present invention 14
Figure；
Accompanying drawing 27 is product 3- (4- tert-butyl benzenes) -2- ((trifluoromethyl) sulphur) -1H- indenes -1- in the embodiment of the present invention ten
Ketone nuclear magnetic spectrogram；
Accompanying drawing 28 is product 3- (4- tert-butyl benzenes) -2- ((trifluoromethyl) sulphur) -1H- indenes -1- in the embodiment of the present invention ten
Ketone nuclear magnetic spectrogram；
Accompanying drawing 29 is product 3- (4- tert-butyl benzenes) -2- ((trifluoromethyl) sulphur) -1H- indenes -1- in the embodiment of the present invention ten
Ketone nuclear magnetic spectrogram.
Brief description of the drawings
Accompanying drawing 1 is product 3- (4- methylbenzenes) -2- in the specific embodiment of the invention one to five, embodiment 15 to 17
The nuclear magnetic spectrogram of ((trifluoromethyl) sulphur) -1H- 1-Indanones；
Accompanying drawing 2 is product 3- (4- methylbenzenes) -2- in the specific embodiment of the invention one to five, embodiment 15 to 17
The nuclear magnetic spectrogram of ((trifluoromethyl) sulphur) -1H- 1-Indanones；
Accompanying drawing 3 is product 3- (4- methylbenzenes) -2- in the specific embodiment of the invention one to five, embodiment 15 to 17
The nuclear magnetic spectrogram of ((trifluoromethyl) sulphur) -1H- 1-Indanones；
Accompanying drawing 4 is product 3- (3- methylbenzenes) -2- ((trifluoromethyl) sulphur) -1H- indenes -1- in the specific embodiment of the invention six
Ketone nuclear magnetic spectrogram；
Accompanying drawing 5 is product 3- (3- methylbenzenes) -2- ((trifluoromethyl) sulphur) -1H- indenes -1- in the specific embodiment of the invention six
Ketone nuclear magnetic spectrogram；
Accompanying drawing 6 is product 3- (3- methylbenzenes) -2- ((trifluoromethyl) sulphur) -1H- indenes -1- in the specific embodiment of the invention six
Ketone nuclear magnetic spectrogram；
Accompanying drawing 7 is product 3- (4- ethylo benzenes) -2- ((trifluoromethyl) sulphur) -1H- indenes -1- in the specific embodiment of the invention seven
Ketone nuclear magnetic spectrogram；
Accompanying drawing 8 is product 3- (4- ethylo benzenes) -2- ((trifluoromethyl) sulphur) -1H- indenes -1- in the specific embodiment of the invention seven
Ketone nuclear magnetic spectrogram；
Accompanying drawing 9 is product 3- (4- ethylo benzenes) -2- ((trifluoromethyl) sulphur) -1H- indenes -1- in the specific embodiment of the invention seven
Ketone nuclear magnetic spectrogram；
Accompanying drawing 10 be the specific embodiment of the invention eight in product 3- (4- propylbenzenes) -2- ((trifluoromethyl) sulphur) -1H- indenes -
1- ketone nuclear magnetic spectrograms；
Accompanying drawing 11 be the specific embodiment of the invention eight in product 3- (4- propylbenzenes) -2- ((trifluoromethyl) sulphur) -1H- indenes -
1- ketone nuclear magnetic spectrograms；
Accompanying drawing 12 be the specific embodiment of the invention eight in product 3- (4- propylbenzenes) -2- ((trifluoromethyl) sulphur) -1H- indenes -
1- ketone nuclear magnetic spectrograms；
Accompanying drawing 13 is product 3- (4- butyl benzenes) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones in the embodiment of the present invention nine
Nuclear magnetic spectrogram；
Accompanying drawing 14 is product 3- (4- butyl benzenes) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones in the embodiment of the present invention nine
Nuclear magnetic spectrogram；
Accompanying drawing 15 is product 3- (4- butyl benzenes) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones in the embodiment of the present invention nine
Nuclear magnetic spectrogram；
Accompanying drawing 16 is product 3- (4- fluorobenzene) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones in the embodiment of the present invention 11
Nuclear magnetic spectrogram；
Accompanying drawing 17 is product 3- (4- fluorobenzene) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones in the embodiment of the present invention 11
Nuclear magnetic spectrogram；
Accompanying drawing 18 is product 3- (4- fluorobenzene) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones in the embodiment of the present invention 11
Nuclear magnetic spectrogram；
Accompanying drawing 19 is product 3- (3- chlorobenzenes) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones in the embodiment of the present invention 12
Nuclear-magnetism is composed；
Accompanying drawing 20 is product 3- (3- chlorobenzenes) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones in the embodiment of the present invention 12
Nuclear-magnetism is composed；
Accompanying drawing 21 is product 3- (3- chlorobenzenes) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones in the embodiment of the present invention 12
Nuclear-magnetism is composed；
Accompanying drawing 22 is product 3- (4- bromobenzenes) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones in the embodiment of the present invention 13
Nuclear magnetic spectrogram；
Accompanying drawing 23 is product 3- (4- bromobenzenes) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones in the embodiment of the present invention 13
Nuclear magnetic spectrogram；
Accompanying drawing 24 is that product 3- benzene -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones nuclear-magnetism is composed in the embodiment of the present invention 14
Figure；
Accompanying drawing 25 is that product 3- benzene -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones nuclear-magnetism is composed in the embodiment of the present invention 14
Figure；
Accompanying drawing 26 is that product 3- benzene -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones nuclear-magnetism is composed in the embodiment of the present invention 14
Figure；
Accompanying drawing 27 is product 3- (4- tert-butyl benzenes) -2- ((trifluoromethyl) sulphur) -1H- indenes -1- in the embodiment of the present invention ten
Ketone nuclear magnetic spectrogram；
Accompanying drawing 28 is product 3- (4- tert-butyl benzenes) -2- ((trifluoromethyl) sulphur) -1H- indenes -1- in the embodiment of the present invention ten
Ketone nuclear magnetic spectrogram；
Accompanying drawing 29 is product 3- (4- tert-butyl benzenes) -2- ((trifluoromethyl) sulphur) -1H- indenes -1- in the embodiment of the present invention ten
Ketone nuclear magnetic spectrogram.
Embodiment
The present invention is not limited to above-mentioned embodiment, and persons skilled in the art are according to disclosed by the invention interior
Hold, other a variety of embodiments can be used to implement the present invention, or every design structure and think of using the present invention
Road, simple change or change are done, both falls within protection scope of the present invention.
The specific embodiment of the present invention is as follows：
The course of reaction is as follows：It is raw material to choose acetylenic ketone compounds A and fluoroform sulfane alcohol silver compound B, with over cure
Silicate reagent is as oxidant, with HMPA (HMPA) for stabilizer, in reaction dissolvent, in reaction temperature be 80oReacted under C, react 12h, reacted and obtain indanone compounds through post processing after terminating.
Table 1- embodiment raw material proportionings
Instantiation one：Using 3- (4- (methyl) benzene) -1- phenyl propyl- 2- alkynes -1- ketone and the silver synthesis of fluoroform sulfane alcohol
3- (4- (methyl) benzene) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones；
By raw material A, raw material B, potassium peroxydisulfate, HMPA is 1 in molar ratio:1.5:1:0.1 weighs, wherein（A）Compound is
0.1 mmol.Reaction solution uses DMSO, by reaction system 80oStirring reaction 12 hours under C.Reaction cools down after terminating, and uses
Saturated sodium-chloride water solution, which is washed, to be cleaned, and anhydrous sodium sulfate water removal, short silicagel column filters, and filtrate revolving, removes potassium peroxydisulfate,
Solvent is removed, residue silica gel column chromatography, petroleum ether elution, TLC detections, merges the efflux containing product, rotary evaporation
Solvent is distilled off in instrument, and vacuum drying obtains the target product of brown color, yield 35%, purity 99.1%（HPLC）.Nuclear-magnetism is total to
Vibration wave is composed：1H NMR (500 MHz, CDCl3) δ 7.66 (d, J = 6.7 Hz, 1H), 7.52 (d, J = 8.1
Hz, 2H), 7.44 (ddd, J = 10.3, 7.7, 3.9 Hz, 2H), 7.38 (d, J = 7.9 Hz, 2H),
7.27 (d, J = 7.4 Hz, 1H), 2.47 (s, 3H). 113C NMR (125 MHz, CDCl3) δ 192.14,
170.09, 143.38, 141.64, 133.65, 130.90, 130.83, 129.51, 128.80 (q,J =308,1C,
SCF3),128.61, 127.85, 123.71, 123.17, 117.17, 21.67. 19F NMR (471 MHz, CDCl3) δ
-40.33 (s).。
Instantiation two：Using 3- (4- (methyl) benzene) -1- phenyl propyl- 2- alkynes -1- ketone and the silver synthesis of fluoroform sulfane alcohol
3- (4- (methyl) benzene) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones；
By raw material A, raw material B, potassium peroxydisulfate, HMPA is 1 in molar ratio:1.5:2:0.1 weighs, wherein（A）Compound is
0.1 mmol.Reaction solution uses DMSO, by reaction system 80oStirring reaction 12 hours under C.Reaction cools down after terminating, and uses
Saturated sodium-chloride water solution, which is washed, to be cleaned, and anhydrous sodium sulfate water removal, short silicagel column filters, and filtrate revolving, removes potassium peroxydisulfate,
Solvent is removed, residue silica gel column chromatography, petroleum ether elution, TLC detections, merges the efflux containing product, rotary evaporation
Solvent is distilled off in instrument, and vacuum drying obtains the target product of brown color, yield 65%, purity 99.1%（HPLC）.Nuclear-magnetism is total to
Vibration wave is composed：1H NMR (500 MHz, CDCl3) δ 7.66 (d, J = 6.7 Hz, 1H), 7.52 (d, J = 8.1
Hz, 2H), 7.44 (ddd, J = 10.3, 7.7, 3.9 Hz, 2H), 7.38 (d, J = 7.9 Hz, 2H),
7.27 (d, J = 7.4 Hz, 1H), 2.47 (s, 3H). 113C NMR (125 MHz, CDCl3) δ 192.14,
170.09, 143.38, 141.64, 133.65, 130.90, 130.83, 129.51, 128.80 (q,J =308,1C,
SCF3),128.61, 127.85, 123.71, 123.17, 117.17, 21.67. 19F NMR (471 MHz, CDCl3) δ
-40.33 (s).。
Instantiation three：Using 3- (4- (methyl) benzene) -1- phenyl propyl- 2- alkynes -1- ketone and the silver synthesis of fluoroform sulfane alcohol
3- (4- (methyl) benzene) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones；
By raw material A, raw material B, potassium peroxydisulfate, HMPA is 1 in molar ratio:1.5:3:0.1 weighs, wherein（A）Compound is
0.1 mmol.Reaction solution uses DMSO, by reaction system 80oStirring reaction 12 hours under C.Reaction cools down after terminating, and uses
Saturated sodium-chloride water solution, which is washed, to be cleaned, and anhydrous sodium sulfate water removal, short silicagel column filters, and filtrate revolving, removes potassium peroxydisulfate,
Solvent is removed, residue silica gel column chromatography, petroleum ether elution, TLC detections, merges the efflux containing product, rotary evaporation
Solvent is distilled off in instrument, and vacuum drying obtains the target product of brown color, yield 84%, purity 99.1%（HPLC）.Nuclear-magnetism is total to
Vibration wave is composed：1H NMR (500 MHz, CDCl3) δ 7.66 (d, J = 6.7 Hz, 1H), 7.52 (d, J = 8.1
Hz, 2H), 7.44 (ddd, J = 10.3, 7.7, 3.9 Hz, 2H), 7.38 (d, J = 7.9 Hz, 2H),
7.27 (d, J = 7.4 Hz, 1H), 2.47 (s, 3H). 113C NMR (125 MHz, CDCl3) δ 192.14,
170.09, 143.38, 141.64, 133.65, 130.90, 130.83, 129.51, 128.80 (q,J =308,1C,
SCF3),128.61, 127.85, 123.71, 123.17, 117.17, 21.67. 19F NMR (471 MHz, CDCl3) δ
-40.33 (s).。
Instantiation four：Using 3- (4- (methyl) benzene) -1- phenyl propyl- 2- alkynes -1- ketone and the silver synthesis of fluoroform sulfane alcohol
3- (4- (methyl) benzene) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones；
By raw material A, raw material B, potassium peroxydisulfate, HMPA is 1 in molar ratio:1.5:4:0.1 weighs, wherein（A）Compound is
0.1 mmol.Reaction solution uses DMSO, by reaction system 80oStirring reaction 12 hours under C.Reaction cools down after terminating, and uses
Saturated sodium-chloride water solution, which is washed, to be cleaned, and anhydrous sodium sulfate water removal, short silicagel column filters, and filtrate revolving, removes potassium peroxydisulfate,
Solvent is removed, residue silica gel column chromatography, petroleum ether elution, TLC detections, merges the efflux containing product, rotary evaporation
Solvent is distilled off in instrument, and vacuum drying obtains the target product of brown color, yield 83%, purity 99.1%（HPLC）.Nuclear-magnetism is total to
Vibration wave is composed：1H NMR (500 MHz, CDCl3) δ 7.66 (d, J = 6.7 Hz, 1H), 7.52 (d, J = 8.1
Hz, 2H), 7.44 (ddd, J = 10.3, 7.7, 3.9 Hz, 2H), 7.38 (d, J = 7.9 Hz, 2H),
7.27 (d, J = 7.4 Hz, 1H), 2.47 (s, 3H). 113C NMR (125 MHz, CDCl3) δ 192.14,
170.09, 143.38, 141.64, 133.65, 130.90, 130.83, 129.51, 128.80 (q,J =308,1C,
SCF3),128.61, 127.85, 123.71, 123.17, 117.17, 21.67. 19F NMR (471 MHz, CDCl3) δ
-40.33 (s).。
Instantiation five：Using 3- (4- (methyl) benzene) -1- phenyl propyl- 2- alkynes -1- ketone and the silver synthesis of fluoroform sulfane alcohol
3- (4- (methyl) benzene) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones；
By raw material A, raw material B, potassium peroxydisulfate, HMPA is 1 in molar ratio:1.5:5:0.1 weighs, wherein（A）Compound is
0.1 mmol.Reaction solution uses DMSO, by reaction system 80oStirring reaction 12 hours under C.Reaction cools down after terminating, and uses
Saturated sodium-chloride water solution, which is washed, to be cleaned, and anhydrous sodium sulfate water removal, short silicagel column filters, and filtrate revolving, removes potassium peroxydisulfate,
Solvent is removed, residue silica gel column chromatography, petroleum ether elution, TLC detections, merges the efflux containing product, rotary evaporation
Solvent is distilled off in instrument, and vacuum drying obtains the target product of brown color, yield 81%, purity 99.1%（HPLC）.Nuclear-magnetism is total to
Vibration wave is composed：1H NMR (500 MHz, CDCl3) δ 7.66 (d, J = 6.7 Hz, 1H), 7.52 (d, J = 8.1
Hz, 2H), 7.44 (ddd, J = 10.3, 7.7, 3.9 Hz, 2H), 7.38 (d, J = 7.9 Hz, 2H),
7.27 (d, J = 7.4 Hz, 1H), 2.47 (s, 3H). 113C NMR (125 MHz, CDCl3) δ 192.14,
170.09, 143.38, 141.64, 133.65, 130.90, 130.83, 129.51, 128.80 (q,J =308,1C,
SCF3),128.61, 127.85, 123.71, 123.17, 117.17, 21.67. 19F NMR (471 MHz, CDCl3) δ
-40.33 (s).。
Above-described embodiment one to five, when R1 is methyl, i.e., with using 3- (4- (methyl) benzene) -1- phenyl propyl- 2- alkynes -1- ketone
With fluoroform sulfane alcohol silver synthesis 3- (4- (methyl) benzene) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones；Wherein variable is acetylenic ketone
The mol ratio of class compound and persulfate, wherein, when mol ratio is 1:During 2-5, yield reaches more than 65%, illustrates both it
Between mol ratio there is material impact effect to yield.
Specific embodiment six：Using 1- phenyl -3- p-methylphenyls propyl- 2- alkynes -1- ketone and fluoroform sulfane alcohol silver synthesis 3-
Tolyl -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones；
By raw material A, raw material B, potassium peroxydisulfate, HMPA is 1 in molar ratio:1.5:3:0.1 weighs, wherein（A）Compound is
0.1 mmol.Reaction solution uses DMSO, by reaction system 80oStirring reaction 12 hours under C.Reaction cools down after terminating, and uses
Saturated sodium-chloride water solution, which is washed, to be cleaned, and anhydrous sodium sulfate water removal, short silicagel column filters, and filtrate revolving, removes potassium peroxydisulfate,
Solvent is removed, residue silica gel column chromatography, petroleum ether elution, TLC detections, merges the efflux containing product, rotary evaporation
Solvent is distilled off in instrument, and vacuum drying obtains the target product of brown color, yield 84%, purity 99.1%（HPLC）.Nuclear-magnetism is total to
Vibration wave is composed：1H NMR (500 MHz, CDCl3) δ 7.66 (d, J = 6.7 Hz, 1H), 7.52 (d, J = 8.1
Hz, 2H), 7.44 (ddd, J = 10.3, 7.7, 3.9 Hz, 2H), 7.38 (d, J = 7.9 Hz, 2H),
7.27 (d, J = 7.4 Hz, 1H), 2.47 (s, 3H). 113C NMR (125 MHz, CDCl3) δ 192.14,
170.09, 143.38, 141.64, 133.65, 130.90, 130.83, 129.51, 128.80 (q,J =308,1C,
SCF3),128.61, 127.85, 123.71, 123.17, 117.17, 21.67. 19F NMR (471 MHz, CDCl3) δ
-40.33 (s).。
Instantiation seven：Using 3- (4- (ethyl) benzene) -1- phenyl propyl- 2- alkynes -1- ketone and the silver synthesis of fluoroform sulfane alcohol
3- (4- (ethyl) benzene) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones；
By raw material A, raw material B, potassium peroxydisulfate, HMPA is 1 in molar ratio:1.5:3:0.1 weighs, wherein（A）Compound is
0.1 mmol.Reaction solution uses DMSO, by reaction system 80oStirring reaction 12 hours under C.Reaction cools down after terminating, and uses
Saturated sodium-chloride water solution, which is washed, to be cleaned, and anhydrous sodium sulfate water removal, short silicagel column filters, and filtrate revolving, removes potassium peroxydisulfate,
Solvent is removed, residue silica gel column chromatography, petroleum ether elution, TLC detections, merges the efflux containing product, rotary evaporation
Solvent is distilled off in instrument, and vacuum drying obtains the target product of brown color, yield 86%, purity 99.1%（HPLC）.Nuclear-magnetism is total to
Vibration wave is composed：1H NMR (500 MHz, CDCl3) δ 7.58 (d, J = 6.6 Hz, 1H), 7.48 (d, J = 7.9
Hz, 2H), 7.45 – 7.28 (m, 4H), 7.20 (dd, J = 10.0, 5.5 Hz, 1H), 2.69 (dd, J =
15.0, 7.4 Hz, 2H), 1.25 (t, J = 5.6 Hz, 3H). 13C NMR (125 MHz, CDCl3) δ
192.11, 170.01, 147.80, 143.40, 133.61, 130.91, 130.78, 128.80(q,J =310,1C,
SCF3),128.70, 128.29, 128.08, 123.67, 123.20, 117.18, 28.93, 15.13. 19F NMR
(471 MHz, CDCl3) δ -40.30 (s).。
Instantiation eight：Using 3- (4- (propyl group) benzene) -1- phenyl propyl- 2- alkynes -1- ketone and the silver synthesis of fluoroform sulfane alcohol
3- (4- (propyl group) benzene) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones；
By raw material A, raw material B, potassium peroxydisulfate, HMPA is 1 in molar ratio:1.5:3:0.1 weighs, wherein（A）Compound is
0.1 mmol.Reaction solution uses DMSO, by reaction system 80oStirring reaction 12 hours under C.Reaction cools down after terminating, and uses
Saturated sodium-chloride water solution, which is washed, to be cleaned, and anhydrous sodium sulfate water removal, short silicagel column filters, and filtrate revolving, removes potassium peroxydisulfate,
Solvent is removed, residue silica gel column chromatography, petroleum ether elution, TLC detections, merges the efflux containing product, rotary evaporation
Solvent is distilled off in instrument, and vacuum drying obtains the target product of brown color, yield 89%, purity 99.1%（HPLC）.Nuclear-magnetism is total to
Vibration wave is composed：1H NMR (500 MHz, CDCl3) δ 7.66 (d, J = 6.9 Hz, 1H), 7.55 (d, J = 8.0
Hz, 2H), 7.42 (ddd, J = 19.9, 13.5, 7.8 Hz, 4H), 7.29 (d, J = 7.2 Hz, 1H),
2.76 – 2.67 (m, 2H), 1.73 (dd, J = 15.1, 7.5 Hz, 2H), 1.00 (t, J = 7.3 Hz,
3H).13C NMR (125 MHz, CDCl3) δ 192.13, 170.00, 146.37, 143.40, 133.62, 130.86
(d, J = 17.3 Hz), 128.87 , 128.82(q,J =310,1C,SCF3), 128.62, 128.07, 123.67,
123.23, 117.13, 38.09, 24.25, 13.86.19F NMR (471 MHz, CDCl3) δ -40.29 (s).。
Instantiation nine：Using 3- (4- (butyl) benzene) -1- phenyl propyl- 2- alkynes -1- ketone and the silver synthesis of fluoroform sulfane alcohol
3- (4- (butyl) benzene) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones；
By raw material A, raw material B, potassium peroxydisulfate, HMPA is 1 in molar ratio:1.5:3:0.1 weighs, wherein（A）Compound is
0.1 mmol.Reaction solution uses DMSO, by reaction system 80oStirring reaction 12 hours under C.Reaction cools down after terminating, and uses
Saturated sodium-chloride water solution, which is washed, to be cleaned, and anhydrous sodium sulfate water removal, short silicagel column filters, and filtrate revolving, removes potassium peroxydisulfate,
Solvent is removed, residue silica gel column chromatography, petroleum ether elution, TLC detections, merges the efflux containing product, rotary evaporation
Solvent is distilled off in instrument, and vacuum drying obtains the target product of brown color, yield 88%, purity 99.1%（HPLC）.Nuclear-magnetism is total to
Vibration wave is composed：1H NMR (500 MHz, CDCl3) δ 7.58 (d, J = 6.8 Hz, 1H), 7.47 (d, J = 8.0
Hz, 2H), 7.34 (ddd, J = 19.9, 13.4, 7.8 Hz, 4H), 7.21 (d, J = 7.1 Hz, 1H),
2.69 – 2.59 (m, 2H), 1.69 – 1.57 (m, 2H), 1.42 – 1.29 (m, 2H), 0.90 (t, J =
7.4 Hz, 3H).13C NMR (125 MHz, CDCl3) δ 191.11, 168.98, 145.58, 142.38, 132.59,
129.91, 129.76, ,127.79(q,J =308,1C,SCF3) ,127.79, 127.61, 127.00 , 122.20,
122.05, 116.11, 34.72, 32.27, 21.40, 12.91.19F NMR (471 MHz, CDCl3) δ -40.29
(s).。
Instantiation ten：Closed using 3- (4- (tert-butyl group) benzene) -1- phenyl propyl- 2- alkynes -1- ketone and fluoroform sulfane alcohol silver
Into 3- (4- (tert-butyl group) benzene) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones；
By raw material A, raw material B, potassium peroxydisulfate, HMPA is 1 in molar ratio:1.5:3:0.1 weighs, wherein（A）Compound is
0.1 mmol.Reaction solution uses DMSO, by reaction system 80oStirring reaction 12 hours under C.Reaction cools down after terminating, and uses
Saturated sodium-chloride water solution, which is washed, to be cleaned, and anhydrous sodium sulfate water removal, short silicagel column filters, and filtrate revolving, removes potassium peroxydisulfate,
Solvent is removed, residue silica gel column chromatography, petroleum ether elution, TLC detections, merges the efflux containing product, rotary evaporation
Solvent is distilled off in instrument, and vacuum drying obtains the target product of brown color, yield 87%, purity 99.1%（HPLC）.Nuclear-magnetism is total to
Vibration wave is composed：1H NMR (500 MHz, CDCl3) δ 7.68 – 7.64 (m, 1H), 7.58 (s, 4H), 7.47 –
7.39 (m, 2H), 7.31 (d, J = 7.1 Hz, 1H), 1.40 (s, 9H).13C NMR (125 MHz, CDCl3)
δ 192.14, 169.85, 154.70, 143.40, 133.60, 130.94, 130.78 128.83 (q,J =308,1C,
SCF3),128.52, 127.81 , 125.74, 123.67, 123.29, 117.16. 35.11, 31.18. 19F NMR
(471 MHz, CDCl3) δ -40.23 (s).。
Instantiation 11：Using 3- (4- fluorobenzene) -1- phenyl propyl- 2- alkynes -1- ketone and fluoroform sulfane alcohol silver synthesis 3-
(4- fluorobenzene) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones；
By raw material A, raw material B, potassium peroxydisulfate, HMPA is 1 in molar ratio:1.5:3:0.1 weighs, wherein（A）Compound is
0.1 mmol.Reaction solution uses DMSO, by reaction system 80oStirring reaction 12 hours under C.Reaction cools down after terminating, and uses
Saturated sodium-chloride water solution, which is washed, to be cleaned, and anhydrous sodium sulfate water removal, short silicagel column filters, and filtrate revolving, removes potassium peroxydisulfate,
Solvent is removed, residue silica gel column chromatography, petroleum ether elution, TLC detections, merges the efflux containing product, rotary evaporation
Solvent is distilled off in instrument, and vacuum drying obtains the target product of brown color, yield 79%, purity 99.1%（HPLC）.Nuclear-magnetism is total to
Vibration wave is composed：1H NMR (500 MHz, CDCl3) δ 7.68 (dd, J = 6.9, 0.9 Hz, 1H), 7.66 – 7.59
(m, 2H), 7.51 – 7.41 (m, 2H), 7.32 – 7.25 (m, 2H), 7.23 (d, J = 6.7 Hz, 1H)
.13C NMR (125 MHz, CDCl3) δ 191.76, 168.89, 164.19(J=251,C-F), 143.14, 133.81,
131.05,130.82(J=8.75,C-F), 130.68, 128.69(q,J =310,1C,SCF3), 126.75 (d, J =
3.4 Hz), 123.92, 122.95, 117.92,116.20(J=21,C-F).19F NMR (471 MHz, CDCl3) δ -
40.22, -107.88 .。
Instantiation 12：Using 3- (3- chlorobenzenes) -1- phenyl propyl- 2- alkynes -1- ketone and fluoroform sulfane alcohol silver synthesis 3-
(3- chlorobenzenes) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones；
By raw material A, raw material B, potassium peroxydisulfate, HMPA is 1 in molar ratio:1.5:3:0.1 weighs, wherein（A）Compound is
0.1 mmol.Reaction solution uses DMSO, by reaction system 80oStirring reaction 12 hours under C.Reaction cools down after terminating, and uses
Saturated sodium-chloride water solution, which is washed, to be cleaned, and anhydrous sodium sulfate water removal, short silicagel column filters, and filtrate revolving, removes potassium peroxydisulfate,
Solvent is removed, residue silica gel column chromatography, petroleum ether elution, TLC detections, merges the efflux containing product, rotary evaporation
Solvent is distilled off in instrument, and vacuum drying obtains the target product of brown color, yield 73%, purity 99.1%（HPLC）.Nuclear-magnetism is total to
Vibration wave is composed：1H NMR (500 MHz, CDCl3) δ 7.58 (t, J = 7.5 Hz, 1H), 7.52 – 7.32 (m,
6H), 7.14 (t, J = 10.6 Hz, 1H).13C NMR (125 MHz, CDCl3) δ 191.52, 168.34,
142.97, 134.96, 133.99, 132.38, 131.14, 130.92, 130.42, 130.24, 128.61(q,J =
310,1C,SCF3) ,128.33 , 126.67, 124.06, 122.90, 118.79. 19F NMR (471 MHz, CDCl3)
δ -40.02 (s).。
Instantiation 13：Using 3- (4- bromobenzenes) -1- phenyl propyl- 2- alkynes -1- ketone and fluoroform sulfane alcohol silver synthesis 3-
(4- bromobenzenes) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones；
By raw material A, raw material B, potassium peroxydisulfate, HMPA is 1 in molar ratio:1.5:3:0.1 weighs, wherein（A）Compound is
0.1 mmol.Reaction solution uses DMSO, by reaction system 80oStirring reaction 12 hours under C.Reaction cools down after terminating, and uses
Saturated sodium-chloride water solution, which is washed, to be cleaned, and anhydrous sodium sulfate water removal, short silicagel column filters, and filtrate revolving, removes potassium peroxydisulfate,
Solvent is removed, residue silica gel column chromatography, petroleum ether elution, TLC detections, merges the efflux containing product, rotary evaporation
Solvent is distilled off in instrument, and vacuum drying obtains the target product of brown color, yield 78%, purity 99.1%（HPLC）.Nuclear-magnetism is total to
Vibration wave is composed：1H NMR (500 MHz, CDCl3) δ 7.72 (d, J = 8.4 Hz, 2H), 7.68 (d, J = 6.5
Hz, 1H), 7.55 – 7.36 (m, 4H), 7.21 (d, J = 7.1 Hz, 1H).13C NMR (125 MHz,
CDCl3) δ 191.60, 168.76, 142.95,133.88, 132.22, 131.12, 130.57, 130.05,
129.53,128.61(q,J =310,1C,SCF3) , 125.55, 124.01, 122.88, 118.30. 19F NMR (471
MHz, CDCl3) δ -40.11 (s).。
Instantiation 14：Using 1,3- hexichol -2- propargyl -1- ketone and fluoroform sulfane alcohol silver synthesis 3- phenyl -2-
((trifluoromethyl) sulphur) -1H- 1-Indanones；
By raw material A, raw material B, potassium peroxydisulfate, HMPA is 1 in molar ratio:1.5:3:0.1 weighs, wherein（A）Compound is
0.1 mmol.Reaction solution uses DMSO, by reaction system 80oStirring reaction 12 hours under C.Reaction cools down after terminating, and uses
Saturated sodium-chloride water solution, which is washed, to be cleaned, and anhydrous sodium sulfate water removal, short silicagel column filters, and filtrate revolving, removes potassium peroxydisulfate,
Solvent is removed, residue silica gel column chromatography, petroleum ether elution, TLC detections, merges the efflux containing product, rotary evaporation
Solvent is distilled off in instrument, and vacuum drying obtains the target product of brown color, yield 77%, purity 99.1%（HPLC）.Nuclear-magnetism is total to
Vibration wave is composed：1H NMR (500 MHz, CDCl3) δ 7.69 – 7.65 (m, 1H), 7.62 – 7.55 (m, 5H),
7.49 – 7.40 (m, 2H), 7.26 – 7.22 (m, 1H) 19F NMR (471 MHz, CDCl3) δ -40.24
(s).13C NMR (126 MHz, CDCl3) δ 190.97, 168.96, 142.35, 132.73, 129.94, 129.88,
129.72, 129.70, , 127.77 (s), 128.73 (q,J =308,1C,SCF3), 127.48, 122.79,
122.10, 116.86.19F NMR (471 MHz, CDCl3) δ -40.24 (s).。
Above-described embodiment seven to 14 is contrasted with embodiment three and understood, raw material A, raw material B, potassium peroxydisulfate, between HMPA
Proportioning is 1 in molar ratio:1.5:3:0.1, solvent uses DMSO, and the R in raw material A1Straight chained alkyl, branch has been respectively adopted
Alkyl group, hydrogen, halogen radical, its yield are high and stably, and illustrating the substrate of the present invention has good adaptability.
Instantiation 15：Closed using 3- (4- (methyl) benzene) -1- phenyl propyl- 2- alkynes -1- ketone and fluoroform sulfane alcohol silver
Into 3- (4- (methyl) benzene) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones；
By raw material A, raw material B, potassium peroxydisulfate, HMPA is 1 in molar ratio:1.5:3:0.1 weighs, wherein（A）Compound is
0.1 mmol.Reaction solution uses DMF, by reaction system 80oStirring reaction 12 hours under C.Reaction cools down after terminating, with full
Wash and cleaned with sodium-chloride water solution, anhydrous sodium sulfate water removal, short silicagel column filters, and filtrate revolving, removes potassium peroxydisulfate, removes
Solvent is removed, residue silica gel column chromatography, petroleum ether elution, TLC detections, merges the efflux containing product, Rotary Evaporators
Solvent is distilled off, vacuum drying obtains the target product of brown color, yield 84%, purity 99.1%（HPLC）.Nuclear magnetic resonance
Wave spectrum：1H NMR (500 MHz, CDCl3) δ 7.66 (d, J = 6.7 Hz, 1H), 7.52 (d, J = 8.1 Hz,
2H), 7.44 (ddd, J = 10.3, 7.7, 3.9 Hz, 2H), 7.38 (d, J = 7.9 Hz, 2H), 7.27
(d, J = 7.4 Hz, 1H), 2.47 (s, 3H). 113C NMR (125 MHz, CDCl3) δ 192.14, 170.09,
143.38, 141.64, 133.65, 130.90, 130.83, 129.51, 128.80 (q,J =308,1C,SCF3),
128.61, 127.85, 123.71, 123.17, 117.17, 21.67. 19F NMR (471 MHz, CDCl3) δ -
40.33 (s).。
Instantiation 16：Closed using 3- (4- (methyl) benzene) -1- phenyl propyl- 2- alkynes -1- ketone and fluoroform sulfane alcohol silver
Into 3- (4- (methyl) benzene) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones；
By raw material A, raw material B, potassium peroxydisulfate, HMPA is 1 in molar ratio:1.5:3:0.1 weighs, wherein（A）Compound is
0.1 mmol.Reaction solution uses acetonitrile, by reaction system 80oStirring reaction 12 hours under C.Reaction cools down after terminating, and uses
Saturated sodium-chloride water solution, which is washed, to be cleaned, and anhydrous sodium sulfate water removal, short silicagel column filters, and filtrate revolving, removes potassium peroxydisulfate,
Solvent is removed, residue silica gel column chromatography, petroleum ether elution, TLC detections, merges the efflux containing product, rotary evaporation
Solvent is distilled off in instrument, and vacuum drying obtains the target product of brown color, yield 35%, purity 99.1%（HPLC）.Nuclear-magnetism is total to
Vibration wave is composed：1H NMR (500 MHz, CDCl3) δ 7.66 (d, J = 6.7 Hz, 1H), 7.52 (d, J = 8.1
Hz, 2H), 7.44 (ddd, J = 10.3, 7.7, 3.9 Hz, 2H), 7.38 (d, J = 7.9 Hz, 2H),
7.27 (d, J = 7.4 Hz, 1H), 2.47 (s, 3H). 113C NMR (125 MHz, CDCl3) δ 192.14,
170.09, 143.38, 141.64, 133.65, 130.90, 130.83, 129.51, 128.80 (q,J =308,1C,
SCF3),128.61, 127.85, 123.71, 123.17, 117.17, 21.67. 19F NMR (471 MHz, CDCl3) δ
-40.33 (s).。
Instantiation 17：Closed using 3- (4- (methyl) benzene) -1- phenyl propyl- 2- alkynes -1- ketone and fluoroform sulfane alcohol silver
Into 3- (4- (methyl) benzene) -2- ((trifluoromethyl) sulphur) -1H- 1-Indanones；
By raw material A, raw material B, potassium peroxydisulfate, HMPA is 1 in molar ratio:1.5:3:0.1 weighs, wherein（A）Compound is
0.1 mmol.Reaction solution uses acetone, by reaction system 80oStirring reaction 12 hours under C.Reaction cools down after terminating, and uses
Saturated sodium-chloride water solution, which is washed, to be cleaned, and anhydrous sodium sulfate water removal, short silicagel column filters, and filtrate revolving, removes potassium peroxydisulfate,
Solvent is removed, residue silica gel column chromatography, petroleum ether elution, TLC detections, merges the efflux containing product, rotary evaporation
Solvent is distilled off in instrument, and vacuum drying obtains the target product of brown color, yield 15%, purity 99.1%（HPLC）.Nuclear-magnetism is total to
Vibration wave is composed: 1H NMR (500 MHz, CDCl3) δ 7.66 (d, J = 6.7 Hz, 1H), 7.52 (d, J = 8.1
Hz, 2H), 7.44 (ddd, J = 10.3, 7.7, 3.9 Hz, 2H), 7.38 (d, J = 7.9 Hz, 2H),
7.27 (d, J = 7.4 Hz, 1H), 2.47 (s, 3H). 113C NMR (125 MHz, CDCl3) δ 192.14,
170.09, 143.38, 141.64, 133.65, 130.90, 130.83, 129.51, 128.80 (q,J =308,1C,
SCF3),128.61, 127.85, 123.71, 123.17, 117.17, 21.67. 19F NMR (471 MHz, CDCl3) δ
-40.33 (s).。
Above-described embodiment ten five-ten seven is contrasted with embodiment three and understood, raw material A, raw material B, potassium peroxydisulfate, between HMPA
Proportioning is 1 in molar ratio:1.5:3:0.1, and the R1 in raw material A uses methyl, its variable is then to choose different reactions
Solvent, from above-described embodiment, the selection of solvent has significant impact to yield, as DMF and DMSO have higher yields, and
The target product yield that solvent acetonitrile and acetone obtain is relatively low, and its yield to the present invention has different results, therefore of the invention
Solvent selection be based on drawing, without generality, only there is idioadaptation on the creative experiment basis of technical staff
Property.
Claims (7)
1. the preparation method of a kind of indone with trifluoromethylthio and its derivative, it is characterised in that comprise the following steps：Choose
Acetylenic ketone compounds and fluoroform mercaptan silver compound are raw material, using persulfate reagent as oxidant, with hempa
Acyl triamine is stabilizer, in reaction dissolvent, is to be reacted at 80 DEG C in reaction temperature, reacts 12h, reaction passes through after terminating
Post processing obtains such as following formula（II）Indanone compounds, its chemical equation is as follows,
Picture 2
The formula（I）In R1For any one in hydrogen, alkyl, halogen radical.
2. the preparation method of the indone according to claim 1 with trifluoromethylthio and its derivative, it is characterised in that：Institute
Halogen radical is stated as any one in-F ,-Cl ,-Br.
3. the preparation method of the indone according to claim 1 with trifluoromethylthio and its derivative, it is characterised in that：Institute
Reaction dissolvent is stated as acetonitrile, N,N-dimethylformamide（DMF）, dimethyl sulfoxide (DMSO)（DMSO）, in acetone at least any one.
4. the preparation method of the indone with trifluoromethylthio and its derivative according to claim 1-3 any one, its
It is characterised by：The acetylenic ketone compounds and the mol ratio of fluoroform sulfane alcohol silver compound are 1:1.5.
5. the preparation method of the indone with trifluoromethylthio and its derivative according to claim 1-3 any one, its
It is characterised by：The acetylenic ketone compounds and the mol ratio of HMPA stabilizer are 1:0.1.
6. the preparation method of the indone with trifluoromethylthio and its derivative according to claim 1-3 any one, its
It is characterised by：The acetylenic ketone compounds and the mol ratio of persulfate are 1:1-5.
7. the preparation method of the indone according to claim 1 with trifluoromethylthio and its derivative, it is characterised in that：Instead
Post processing after should terminating comprises the following steps, after completion of the reaction, the mixture obtained after being terminated with Rotary Evaporators from reaction
Middle removing solvent, residue purify to obtain target product with 300-400 mesh silica gel column chromatographies, column chromatography procedure can with TLC with
Track monitors and determines suitable elution terminal.
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Application publication date: 20161228 Assignee: INSTITUTE OF NEW MATERIALS & INDUSTRIAL TECHNOLOGY, WENZHOU University Assignor: Wenzhou University Contract record no.: X2020330000095 Denomination of invention: The invention relates to an indene with trifluoromethylthio group and its derivatives and a preparation method thereof Granted publication date: 20171226 License type: Common License Record date: 20201112 |
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Effective date of registration: 20230216 Address after: 325200 pan Dai Chemical Industrial Zone, Jinhu street, Rui'an City, Wenzhou City, Zhejiang Province Patentee after: BAOYUAN CHEMICAL INDUSTRY Co.,Ltd. Address before: 325000 Wenzhou City National University Science Park incubator, No. 38 Dongfang South Road, Ouhai District, Wenzhou, Zhejiang Patentee before: Wenzhou University |
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