CN110041236A - The synthetic method of thio-ether type compounds - Google Patents
The synthetic method of thio-ether type compounds Download PDFInfo
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- CN110041236A CN110041236A CN201810036163.3A CN201810036163A CN110041236A CN 110041236 A CN110041236 A CN 110041236A CN 201810036163 A CN201810036163 A CN 201810036163A CN 110041236 A CN110041236 A CN 110041236A
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- thio
- type compounds
- ether type
- phenylene
- sulfoxide compound
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- C—CHEMISTRY; METALLURGY
- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D235/28—Sulfur atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
- C07D335/12—Thioxanthenes
- C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
- C07D335/16—Oxygen atoms, e.g. thioxanthones
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Abstract
The invention discloses a kind of synthetic methods of thio-ether type compounds, the following steps are included: phosphorus trichloride is uniformly mixed with the solvent for being evenly distributed with sulfoxide compound, it is reacted 0.5~6 hour after mixing in 20~25 DEG C, obtain thio-ether type compounds, wherein, the solvent is acetonitrile, compared with the prior art, synthetic method of the invention has raw material cheap and easily-available, and reducing agent is cheap and easy to get, is easy to a series of the advantages of saving and capable of obtaining thio-ether type compounds.
Description
Technical field
The invention belongs to technical field of organic synthesis, relate in particular to a kind of synthetic method of thio-ether type compounds.
Background technique
It restores to obtain thio-ether type compounds by sulfoxide compound and is important organic chemistry transformations, conventional method is to pass through
Low-valent metal reagent, metal hydride, halogen ion, phosphorus compound, Woollin reagent and phosphine/chlorination reagent realize this
Conversion.However, most methods have the disadvantages that 1) agents useful for same is expensive, 2) functional group's tolerance is poor, 3) be difficult to processing or
Severe reaction conditions.Therefore, it is necessary to develop the method for more effective and atom economy.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of synthetic methods of thio-ether type compounds, should
Synthetic method can obtain a series of thio-ether type compounds.
It is a further object to provide a kind of synthetic methods to improve the application in thio-ether type compounds yield, should
Synthetic method can improve the yield highest of thio-ether type compounds to 99%.
The purpose of the present invention is what is be achieved by following technical proposals.
A kind of synthetic method of thio-ether type compounds, comprising the following steps: by phosphorus trichloride and be evenly distributed with sulfoxide type
The solvent of compound uniformly mixes, and reacts 0.5~6 hour after mixing in 20~25 DEG C, obtains thio-ether type compounds,
Wherein, the solvent is acetonitrile,
The ratio of the amount of the substance of the sulfoxide compound and phosphorus trichloride is 1:1.05, and the thio-ether type compounds lead to
Formula are as follows:
The sulfoxide compound are as follows:
The R1For aryl or alkyl, the R2For aryl or alkyl.
In the above-mentioned technical solutions, it is detected by contact plate and determines the reaction time.
In the above-mentioned technical solutions, the sulfoxide compound is 1- (butylsulfinyl) -4- methylbenzene, 1- (isopropyl
Base sulfinyl) -4- methylbenzene, cyclopropyl sulfinyl benzene, 1- (allyl sulfinyl) -4- methylbenzene, 1- methyl -4-
(propyl- 2- alkynes -1- base sulfinyl) benzene, 1- (Benzylsulfinyl) -4- methylbenzene, 1- benzyl -2- (Benzylsulfinyl) -
1H- benzo [d] imidazoles, 2- (p-methylphenyl sulfinyl) ethyl acetate, 1- methyl -3- trifluoromethyl sulphinyl base -1H- Yin
Diindyl, 3- difluoromethyl sulfinyl -1H- indoles, diphenyl sulfoxide, two (4- nitrobenzophenone) sulfoxides, two (4- methoxyphenyls)
Sulfoxide, two (2,6- 3,5-dimethylphenyl) sulfoxides, 9H- thioxanthene-9-one -10- oxide, 1- methyl -3- (p-tolysulfinyl) -
1H- indoles, dibenzyl sulfoxide, dibutyl sulfoxide, 2- (p-methylphenyl sulfinyl) acetic acid, 4,4 '-sulfinyl biphenols, N,
N- diethyl -2- (to methylbenzene sulfinyl) acetamide or bis- (4,1- phenylene) diacetate esters of sulfenyl.
In the above-mentioned technical solutions, in the solvent that sulfoxide compound is distributed with, the sulfoxide compound
The ratio of the volume of the amount and solvent of substance is 1:(2~4), the unit of the amount of the substance is mmol, and the unit of the volume is
mL。
In the above-mentioned technical solutions, after obtaining thio-ether type compounds, the petroleum ether and acetic acid that are 10:1 by volume ratio
Ethyl ester uniformly mixes and is incorporated as mobile phase, is eluted with the mobile phase to the thio-ether type compounds.
Above-mentioned synthetic method is in the application being prepared in thio-ether type compounds.
In the above-mentioned technical solutions, the yield of the thio-ether type compounds is 66~99%.
The preparation method of thiobis (4,1- phenylene) diacetate esters, comprising the following steps:
Phosphorus trichloride is uniformly mixed with the acetonitrile for being evenly distributed with bis- (4, the 1- phenylene) diacetate esters of sulfenyl, is mixed
It is reacted at least 0.5 hour in 20~25 DEG C afterwards, obtains thiobis (4,1- phenylene) diacetate esters,
Wherein, the ratio of the amount of the substance of bis- (4, the 1- phenylene) diacetate esters of the sulfenyl and phosphorus trichloride is 1:
1.05。
In the above-mentioned technical solutions, it is detected by contact plate and determines the reaction time.
In the above-mentioned technical solutions, the body of the amount of the substance of bis- (4, the 1- phenylene) diacetate esters of the sulfenyl and acetonitrile
Long-pending ratio is 1:(2~4), the unit of the amount of the substance is mmol, and the unit of the volume is mL.
It in the above-mentioned technical solutions, is 10:1 by volume ratio after obtaining thiobis (4,1- phenylene) diacetate esters
Petroleum ether and ethyl acetate uniformly mix be incorporated as mobile phase, with the mobile phase to the thiobis (4,1- phenylene) two
Acetic acid esters is eluted.
Application of the above-mentioned preparation method in synthesis thiobis (4,1- phenylene) diacetate esters, yield are more than or equal to
93%.
Compared with the prior art, synthetic method of the invention has the beneficial effect that
1, raw material is cheap and easily-available；
2, the reducing agent used is phosphorus trichloride, cheap and easy to get, is easy to save；
3, this reaction obtains a series of thio-ether type compounds.
Detailed description of the invention
Fig. 1 is the general structure of thio-ether type compounds of the invention.
Specific embodiment
The general structure of thio-ether type compounds of the present invention are as follows:
Wherein, R1For aryl or alkyl, the R2For aryl or alkyl.
It is reacted in solvent in the presence of phosphorus trichloride using sulfoxide compound, synthesizes a series of thioether class
Compound.Composite formula are as follows:
The reaction mechanism is as follows shown in formula by the present invention:
The typical thio-ether type compounds that synthetic method of the invention is prepared are as follows:
Normal-butyl (p-methylphenyl) thioether；
Isopropyl (p-methylphenyl) thioether；
Cyclopropyl (phenyl) thioether；
Allyl (p-methylphenyl) thioether；
Propargyl (p-methylphenyl) thioether；
Benzyl (p-methylphenyl) thioether；
1- benzyl -2- (benzylthio) -1H- benzo [d] imidazoles；
2- (p-methylphenyl sulfenyl) ethyl acetate；
1- methyl -3- trifluoromethylthio -1H- indoles；
3- difluoro methyl mercapto -1H- indoles；
Diphenylsulfide；
Two (4- nitrobenzophenone) thioethers；
Two (4- methoxyphenyl) thioethers；
Two (2,6- 3,5-dimethylphenyl) thioethers；
9H- thioxanthene-9-one；
1- methyl -3- (to Tolylsulfanvl) -1H- indoles；
Dibenzyl sulfide；
Di-n-butyl thioether
2- (to methylphenyl-sulfanyl) acetic acid
4,4 '-thiodiphenols
N, N- diethyl -2- (to methylphenyl-sulfanyl) acetamide
Thiobis (4,1- phenylene) diacetate esters
After synthetic method of the invention, chromatographed by column by thio-ether type compounds and solvent and POCl3It separates, column layer
The specific steps of analysis technology are as follows: mix 30 grams of silica gel (specification 200-300 mesh) with 100 milliliters of petroleum ethers thoroughly after, be further filled with pillar
In, then repressurization elutes pillar bubble-free into silicagel column, after later being dissolved sample with 2 milliliters of methylene chloride, then uses glue
The solution that head dropper shifts is uniformly added into along chromatography column wall, is then 10:1 with respective volume ratio after loading
Petroleum ether: ethyl acetate is eluted as mobile phase.
In a specific embodiment of the invention, the step of contact plate detects are as follows:
It uses capillary to draw 10 microlitres of reaction mixtures and uses 0.5 milliliter of methylene chloride dissolved dilution as solution to be measured,
Solution point to be measured is drawn on the baseline of thin-layer chromatography silica gel plate with capillary, and silica gel plate lower part is placed in (petroleum ether: acetic acid second
Ester volume ratio is 2:1 as mobile phase) it opens up in cylinder, solvent is expanded to away from 5 millimeters at the top of silica gel, is taken out silica gel plate, is waved to solvent
Hair to the greatest extent, be placed in raw material under ultraviolet lamp (wavelength 254nm) in observing response system whether fully reacting.
Following yield measuring methods: weighing the quality of product first, with the quality of product divided by the molal weight of product,
Obtain the amount of the substance of product.It then, must with the amount of the substance of product divided by the amount of the substance of sulfoxide compound in raw material
To the yield of the product.
Instrument and model NMR spectrum (1H NMR) tester of nuclear magnetic resonance, Brucker ARX 400
(400MHz), chemical shift uses tetramethylsilane as internal standard.
Specific embodiment further illustrates technical solution of the present invention with reference to the accompanying drawings and examples.
Embodiment 1
The thio-ether type compounds of synthesis are as follows:(normal-butyl (p-methylphenyl) thioether)
Sulfoxide compound (0.5mmol) and acetonitrile (2.0mL) are added into dry 15mL schlenck pipe, then
At 25 DEG C, phosphorus trichloride (0.525mmol) is added drop-wise in schlenck pipe with syringe, is detected by contact plate and determine reaction
Time (i.e. after fully reacting) is 0.5h, after reaction, is chromatographed by column by thio-ether type compounds and solvent and POCl3Separation
It opens, obtains colourless oil liquid, the yield of thio-ether type compounds is 97%.Nuclear magnetic data1H NMR(400MHz,CDCl3):
δ 7.24-7.21 (m, 2H), 7.06 (d, J=8.0Hz, 2H), 2.86 (t, J=7.4Hz, 2H), 2.28 (s, 3H), 1.62-1.53
(m, 2H), 1.47-1.37 (m, 2H), 0.90 (t, J=7.4Hz, 3H)；13C NMR(100MHz,CDCl3):δ135.7,133.3,
129.7,129.6,34.0,31.4,22.0,21.0,13.7.
Wherein, sulfoxide compound is 1- (butylsulfinyl) -4- methylbenzene, source: pacifies resistance to Jilin Chemical, structural formula
Are as follows:
Embodiment 2
The thio-ether type compounds of synthesis are as follows:(isopropyl (p-methylphenyl) thioether)
Sulfoxide compound (0.5mmol) and acetonitrile (1.0mL) are added into dry 15mL schlenck pipe, then
At 25 DEG C, phosphorus trichloride (0.525mmol) is added drop-wise in schlenck pipe with syringe, is detected by contact plate and determine reaction
Time (i.e. after fully reacting) is 0.5h, after reaction, is chromatographed by column and separates thio-ether type compounds with solvent and POCl3
It opens, after reaction, is chromatographed by column by thio-ether type compounds and solvent and POCl3It separates, obtains colourless oil liquid i.e.
Can, the yield of thio-ether type compounds is 95%.Nuclear magnetic data1H NMR(400MHz,CDCl3):δ7.32-7.29(m,2H),
7.11-7.09 (m, 2H), 3.34-3.24 (m, 1H), 2.32 (s, 3H), 1.26 (d, J=6.8Hz, 6H)；13C NMR(100MHz,
CDCl3):δ137.1,132.9,131.8,129.7,38.8,23.3,21.2.
Wherein, sulfoxide compound is 1- (isopropylsulphinyl) -4- methylbenzene, source: pacifies resistance to Jilin Chemical, structural formula
Are as follows:
Embodiment 3
The thio-ether type compounds of synthesis are as follows:(cyclopropyl (phenyl) thioether)
Sulfoxide compound (0.5mmol) and acetonitrile (2.0mL) are added into dry 15mL schlenck pipe, then
At 25 DEG C, phosphorus trichloride (0.525mmol) is added drop-wise in schlenck pipe with syringe, is detected by contact plate and determine reaction
Time (i.e. after fully reacting) is 0.5h, after reaction, is chromatographed by column by thio-ether type compounds and solvent and POCl3Separation
It opens, obtains colourless oil liquid, the yield of thio-ether type compounds is 88%.Nuclear magnetic data1H NMR(400MHz,CDCl3):
δ 7.37-7.34 (m, 2H), 7.26 (t, J=7.2Hz, 2H), 7.13-7.09 (m, 1H), 2.20-2.14 (m, 1H), 1.06-
1.01(m,2H),0.70-0.65(m,2H)；13C NMR(100MHz,CDCl3):δ138.9,128.8,126.8,125.1,
12.3,8.6.
Wherein, sulfoxide compound is cyclopropyl sulfinyl benzene, source: pacifies resistance to Jilin Chemical, structural formula are as follows:
Embodiment 4
The thio-ether type compounds of synthesis are as follows:(allyl (p-methylphenyl) thioether)
Sulfoxide compound (0.5mmol) and acetonitrile (2.0mL) are added into dry 15mL schlenck pipe, then
At 25 DEG C, phosphorus trichloride (0.525mmol) is added drop-wise in schlenck pipe with syringe, is detected by contact plate and determine reaction
Time (i.e. after fully reacting) is 0.5h, after reaction, is chromatographed by column by thio-ether type compounds and solvent and POCl3Separation
It opens, obtains yellow solid, the yield of thio-ether type compounds is 89%.Nuclear magnetic data1H NMR(400MHz,CDCl3):δ
7.27-7.26 (m, 1H), 7.26-7.24 (m, 1H), 7.10 (d, J=8.0Hz, 2H), 5.92-5.81 (m, 1H), 5.11-5.06
(m,1H),5.06-5.02(m,1H),3.52-3.49(m,2H),2.31(s,3H)；13C NMR(100MHz,CDCl3):δ
136.6,134.0,132.3,130.9,129.7,117.5,38.1,21.2.
Wherein, sulfoxide compound is 1- (allyl sulfinyl) -4- methylbenzene, source: pacifies resistance to Jilin Chemical, structural formula
Are as follows:
Embodiment 5
The thio-ether type compounds of synthesis are as follows:(propyl- 2- alkynes -1- base (p-methylphenyl) thioether)
Sulfoxide compound (0.5mmol) and acetonitrile (2.0mL) are added into dry 15mL schlenck pipe, then
At 25 DEG C, phosphorus trichloride (0.525mmol) is added drop-wise in schlenck pipe with syringe, is detected by contact plate and determine reaction
Time (i.e. after fully reacting) is 0.5h, after reaction, is chromatographed by column by thio-ether type compounds and solvent and POCl3Separation
It opens, obtains yellow oily liquid, the yield of thio-ether type compounds is 73%.Nuclear magnetic data1H NMR(400MHz,CDCl3):
δ 7.39-7.36 (m, 2H), 7.14 (d, J=8.0Hz, 2H), 3.55 (d, J=2.8Hz, 2H), 2.34 (s, 3H), 2.22 (t, J
=1.2Hz, 1H)；13C NMR(100MHz,CDCl3):δ137.5,131.4,131.3,129.9,80.2,71.6,23.5,
21.2.
Wherein, sulfoxide compound is 1- methyl -4- (propyl- 2- alkynes -1- base sulfinyl) benzene, and source: pacifying resistance to Jilin Chemical,
Structural formula are as follows:
Embodiment 6
The thio-ether type compounds of synthesis are as follows:(benzyl (p-methylphenyl) thioether)
Sulfoxide compound (0.5mmol) and acetonitrile (2.0mL) are added into dry 15mL schlenck pipe, then
At 25 DEG C, phosphorus trichloride (0.525mmol) is added drop-wise in schlenck pipe with syringe, is detected by contact plate and determine reaction
Time (i.e. after fully reacting) is 0.5h, after reaction, is chromatographed by column by thio-ether type compounds and solvent and POCl3Separation
It opens, obtains white solid, the yield of thio-ether type compounds is 99%.Nuclear magnetic data1H NMR(400MHz,CDCl3):δ
7.25-7.18 (m, 7H), 7.04 (d, J=8.0Hz, 2H), 4.04 (s, 2H), 2.28 (s, 3H)；13C NMR(100MHz,
CDCl3):δ138.0,136.7,132.7,130.9,129.7,129.0,128.6,127.2,40.0,21.2.
Wherein, sulfoxide compound is 1- (Benzylsulfinyl) -4- methylbenzene, source: pacifies resistance to Jilin Chemical, structural formula
Are as follows:
Embodiment 7
The thio-ether type compounds of synthesis are as follows:(1- benzyl -2- (benzylthio) -1H- benzo [d]
Imidazoles)
Sulfoxide compound (0.5mmol) and acetonitrile (1.0mL) are added into dry 15mL schlenck pipe, then
At 25 DEG C, phosphorus trichloride (0.525mmol) is added drop-wise in schlenck pipe with syringe, is detected by contact plate and determine reaction
Time (i.e. after fully reacting) is 0.5h, after reaction, is chromatographed by column by thio-ether type compounds and solvent and POCl3Separation
It opens, obtains white solid, the yield of thio-ether type compounds is 95%.Nuclear magnetic data1H NMR(400MHz,CDCl3):δ
7.74 (d, J=8.0Hz, 1H), 7.41-7.37 (m, 2H), 7.31-7.26 (m, 3H), 7.26-7.20 (m, 4H), 7.17-7.15
(m,2H),7.10-7.08(m,2H),5.23(s,2H),4.62(s,2H)；13C NMR(100MHz,CDCl3):δ151.8,
143.8,136.9,136.3,135.8,129.2,128.9,128.8,128.0,127.8,127.0,122.3,122.2,
118.6,109.4,47.7,37.7.
Wherein, sulfoxide compound is 1- benzyl -2- (Benzylsulfinyl) -1H- benzo [d] imidazoles, source: An Naiji
Chemistry, structural formula are as follows:
Embodiment 8
The thio-ether type compounds of synthesis are as follows:(2- (p-methylphenyl sulfenyl) ethyl acetate)
Sulfoxide compound (0.5mmol) and acetonitrile (2.0mL) are added into dry 15mL schlenck pipe, then
At 25 DEG C, phosphorus trichloride (0.525mmol) is added drop-wise in schlenck pipe with syringe, is detected by contact plate and determine reaction
Time (i.e. after fully reacting) is 0.5h, after reaction, is chromatographed by column by thio-ether type compounds and solvent and POCl3Separation
It opens, obtains colourless oil liquid, the yield of thio-ether type compounds is 81%.Nuclear magnetic data1H NMR(400MHz,CDCl3):
δ 7.34-7.31 (m, 2H), 7.10 (d, J=8.0Hz, 2H), 4.15 (q, J=7.2Hz, 2H), 3.57 (s, 2H), 2.31 (s,
3H), 1.22 (t, J=7.2Hz, 3H)；13C NMR(100MHz,CDCl3):δ169.9,137.4,131.4,131.1,129.9,
61.5,37.6,21.1,14.2.
Wherein, sulfoxide compound is 2- (p-methylphenyl sulfinyl) ethyl acetate, source: pacifies resistance to Jilin Chemical, structure
Formula are as follows:
Embodiment 9
The thio-ether type compounds of synthesis are as follows:(1- methyl -3- trifluoromethylthio -1H- indoles)
Sulfoxide compound (0.5mmol) and acetonitrile (2.0mL) are added into dry 15mL schlenck pipe, then
At 25 DEG C, phosphorus trichloride (0.525mmol) is added drop-wise in schlenck pipe with syringe, is detected by contact plate and determine reaction
Time (i.e. after fully reacting) is 0.5h, after reaction, is chromatographed by column by thio-ether type compounds and solvent and POCl3Separation
It opens, obtains yellow oily liquid, the yield of thio-ether type compounds is 75%.Nuclear magnetic data1H NMR(400MHz,CDCl3):
δ 7.79 (d, J=7.6Hz, 1H), 7.38-7.25 (m, 4H), 3.83 (s, 3H)；13C NMR(100MHz,CDCl3):δ137.4,
137.1,130.4,129.6 (q, J=308.0Hz, 1C), 123.1,121.4,119.6,110.0,93.3 (q, J=2.0Hz,
1C),33.4；19F NMR(376MHz,CDCl3):δ-44.96(s,3F).
Wherein, sulfoxide compound is 1- methyl -3- trifluoromethyl sulphinyl base -1H- indoles, and source: pacifying resistance to Jilin Chemical,
Structural formula are as follows:
Embodiment 10
The thio-ether type compounds of synthesis are as follows:(3- difluoro methyl mercapto -1H- indoles)
Sulfoxide compound (0.5mmol) and acetonitrile (2.0mL) are added into dry 15mL schlenck pipe, then
At 25 DEG C, phosphorus trichloride (0.525mmol) is added drop-wise in schlenck pipe with syringe, is detected by contact plate and determine reaction
Time (i.e. after fully reacting) is 0.5h, after reaction, is chromatographed by column by thio-ether type compounds and solvent and POCl3Separation
It opens, obtains brown oil liquid, the yield of thio-ether type compounds is 93%.Nuclear magnetic data1H NMR(400MHz,CDCl3):
δ 8.45 (s, 1H), 7.80-7.78 (m, 1H), 7.46 (d, J=2.8Hz, 1H), 7.42-7.40 (m, 1H), 7.30-7.23 (m,
2H), 6.68 (t, J=57.6Hz, 1H)；13C NMR(100MHz,CDCl3):δ136.2,132.0,129.8,123.4,121.4,
121.2 (t, J=274.0Hz, 1C), 119.4,111.8,96.7 (t, J=3.7Hz, 1C)；19F NMR(376MHz,CDCl3):δ
=-91.96 (d, J=60.1Hz, 2F)
Wherein, sulfoxide compound is 3- difluoromethyl sulfinyl -1H- indoles, source: pacifies resistance to Jilin Chemical, structural formula
Are as follows:
Embodiment 11
The thio-ether type compounds of synthesis are as follows:(diphenylsulfide)
Sulfoxide compound (0.5mmol) and acetonitrile (2.0mL) are added into dry 15mL schlenck pipe, then
At 25 DEG C, phosphorus trichloride (0.525mmol) is added drop-wise in schlenck pipe with syringe, is detected by contact plate and determine reaction
Time (i.e. after fully reacting) is 0.5h, after reaction, is chromatographed by column by thio-ether type compounds and solvent and POCl3Separation
It opens, obtains colourless oil liquid, the yield of thio-ether type compounds is 99%.Nuclear magnetic data1H NMR(400MHz,CDCl3):
δ7.34-7.31(m,5H),7.29-7.25(m,3H),7.23-7.19(m,2H)；13C NMR(100MHz,CDCl3):δ136.0,
131.2,129.3,127.1.
Wherein, sulfoxide compound is diphenyl sulfoxide, source: pacifies resistance to Jilin Chemical, structural formula are as follows:
Embodiment 12
The thio-ether type compounds of synthesis are as follows:(two (4- nitrobenzophenone) thioethers)
Sulfoxide compound (0.5mmol) and acetonitrile (2.0mL) are added into dry 15mL schlenck pipe, then
At 25 DEG C, phosphorus trichloride (0.525mmol) is added drop-wise in schlenck pipe with syringe, is detected by contact plate and determine reaction
Time (i.e. after fully reacting) is 6h, after reaction, is chromatographed by column by thio-ether type compounds and solvent and POCl3Separation
It opens, obtains yellow oily liquid, the yield of thio-ether type compounds is 93%.Nuclear magnetic data1H NMR(400MHz,d6-
DMSO): δ 8.25 (dd, J=8.4,1.6Hz, 4H), 7.64 (dd, J=8.4,2.0Hz, 4H)；13C NMR(100MHz,d6-
DMSO):δ146.7,142.2,131.3,124.8.
Wherein, sulfoxide compound is two (4- nitrobenzophenone) sulfoxides, source: pacifies resistance to Jilin Chemical, structural formula are as follows:
Embodiment 13
The thio-ether type compounds of synthesis are as follows:(two (4- methoxyphenyl) thioethers)
Sulfoxide compound (0.5mmol) and acetonitrile (2.0mL) are added into dry 15mL schlenck pipe, then
At 25 DEG C, phosphorus trichloride (0.525mmol) is added drop-wise in schlenck pipe with syringe, is detected by contact plate and determine reaction
Time (i.e. after fully reacting) is 0.5h, after reaction, is chromatographed by column by thio-ether type compounds and solvent and POCl3Separation
It opens, obtains white solid, the yield of thio-ether type compounds is 99%.Nuclear magnetic data1H NMR(400MHz,CDCl3):δ
7.29-7.25(m,4H),6.85-6.81(m,4H),3.78(s,6H)；13C NMR(100MHz,CDCl3):δ159.2,132.9,
127.6,114.9,55.5.
Wherein, sulfoxide compound is two (4- methoxyphenyl) sulfoxides, source: pacifies resistance to Jilin Chemical, structural formula are as follows:
Embodiment 14
The thio-ether type compounds of synthesis are as follows:(two (2,6- 3,5-dimethylphenyl) thioethers)
Sulfoxide compound (0.5mmol) and acetonitrile (2.0mL) are added into dry 15mL schlenck pipe, then
At 25 DEG C, phosphorus trichloride (0.525mmol) is added drop-wise in schlenck pipe with syringe, is detected by contact plate and determine reaction
Time (i.e. after fully reacting) is 0.5h, after reaction, is chromatographed by column by thio-ether type compounds and solvent and POCl3Separation
It opens, obtains white solid, the yield of thio-ether type compounds is 99%.Nuclear magnetic data1H NMR(400MHz,CDCl3):δ
7.06-6.99(m,6H),2.22(s,12H)；13C NMR(100MHz,CDCl3):δ140.5,134.5,128.6,127.0,
21.8.
Wherein, sulfoxide compound is two (2,6- 3,5-dimethylphenyl) sulfoxides, source: pacifies resistance to Jilin Chemical, structural formula are as follows:
Embodiment 15
The thio-ether type compounds of synthesis are as follows:(9H- thioxanthene-9-one)
Sulfoxide compound (0.5mmol) and acetonitrile (2.0mL) are added into dry 15mL schlenck pipe, then
At 25 DEG C, phosphorus trichloride (0.525mmol) is added drop-wise in schlenck pipe with syringe, is detected by contact plate and determine reaction
Time (i.e. after fully reacting) is 0.5h, after reaction, is chromatographed by column by thio-ether type compounds and solvent and POCl3Separation
It opens, obtains yellow solid, the yield of thio-ether type compounds is 99%.Nuclear magnetic data1H NMR(400MHz,CDCl3):δ
8.64-8.61(m,2H),7.65-7.57(m,4H),7.51-7.47(m,2H)；13C NMR(100MHz,CDCl3):δ180.1,
137.4,132.4,130.0,129.5,126.4,126.1.
Wherein, sulfoxide compound is 9H- thioxanthene-9-one -10- oxide, source: pacifies resistance to Jilin Chemical, structural formula are as follows:
Embodiment 16
The thio-ether type compounds of synthesis are as follows:(1- methyl -3- (to Tolylsulfanvl) -1H- indoles)
Sulfoxide compound (0.5mmol) and acetonitrile (2.0mL) are added into dry 15mL schlenck pipe, then
At 25 DEG C, phosphorus trichloride (0.525mmol) is added drop-wise in schlenck pipe with syringe, is detected by contact plate and determine reaction
Time (i.e. after fully reacting) is 0.5h, after reaction, is chromatographed by column by thio-ether type compounds and solvent and POCl3Separation
It opens, obtains white solid, the yield of thio-ether type compounds is 70%.Nuclear magnetic data1H NMR(400MHz,CDCl3):δ
7.61 (dd, J=7.6,0.4Hz, 1H), 7.38-7.35 (m, 1H), 7.31 (s, 1H), 7.30-7.26 (m, 1H), 7.17-7.13
(m,1H),7.03-7.00(m,2H),6.97-6.95(m,2H),3.82(s,3H),2.24(s,3H)；13C NMR(100MHz,
CDCl3):δ137.6,136.1,134.9,134.6,130.0,129.5,126.3,122.6,120.5,119.9,109.8,
101.4,33.1,20.9.
Wherein, sulfoxide compound is 1- methyl -3- (p-tolysulfinyl) -1H- indoles, and source: pacifying resistance to Jilin Chemical,
Structural formula are as follows:
Embodiment 17
The thio-ether type compounds of synthesis are as follows:(dibenzyl sulfide)
Sulfoxide compound (0.5mmol) and acetonitrile (2.0mL) are added into dry 15mL schlenck pipe, then
At 25 DEG C, phosphorus trichloride (0.525mmol) is added drop-wise in schlenck pipe with syringe, is detected by contact plate and determine reaction
Time (i.e. after fully reacting) is 0.5h, after reaction, is chromatographed by column by thio-ether type compounds and solvent and POCl3Separation
It opens, obtains white solid, the yield of thio-ether type compounds is 93%.Nuclear magnetic data1H NMR(400MHz,CDCl3):δ
7.33-7.22(m,10H),3.60(s,4H)；13C NMR(100MHz,CDCl3):δ138.3,129.1,128.6,127.1,
35.8.
Wherein, sulfoxide compound is dibenzyl sulfoxide, source: pacifies resistance to Jilin Chemical, structural formula are as follows:
Embodiment 18
The thio-ether type compounds of synthesis are as follows:(butyl sulfide)
Sulfoxide compound (0.5mmol) and acetonitrile (2.0mL) are added into dry 15mL schlenck pipe, then
At 25 DEG C, phosphorus trichloride (0.525mmol) is added drop-wise in schlenck pipe with syringe, is detected by contact plate and determine reaction
Time (i.e. after fully reacting) is 0.5h, after reaction, is chromatographed by column by thio-ether type compounds and solvent and POCl3Separation
It opens, obtains colourless oil liquid, the yield of thio-ether type compounds is 82%.Nuclear magnetic data1H NMR(400MHz,CDCl3):
δ 2.53-2.49 (m, 4H), 1.61-1.53 (m, 4H), 1.46-1.36 (m, 4H), 0.92 (t, J=7.6Hz, 6H)；13C NMR
(100MHz,CDCl3):δ32.0,22.2,13.8.
Wherein, sulfoxide compound is dibutyl sulfoxide, source: pacifies resistance to Jilin Chemical, structural formula are as follows:
Embodiment 19
The thio-ether type compounds of synthesis are as follows:(2- (to methylphenyl-sulfanyl) acetic acid)
Sulfoxide compound (0.5mmol) and acetonitrile (2.0mL) are added into dry 15mL schlenck pipe, then
At 25 DEG C, phosphorus trichloride (0.525mmol) is added drop-wise in schlenck pipe with syringe, is detected by contact plate and determine reaction
Time (i.e. after fully reacting) is 0.5h, after reaction, is chromatographed by column by thio-ether type compounds and solvent and POCl3Separation
It opens, obtains yellow solid, the yield of thio-ether type compounds is 81%.Nuclear magnetic data1H NMR(400MHz,CDCl3):δ
11.17 (s, 1H), 7.33 (d, 2H, J=8.20Hz), 7.11 (d, 2H, J=8.20Hz), 3.60 (s, 2H), 2.32 (s, 3H)；13C NMR(100MHz,CDCl3):δ175.6,137.6,131.1,131.0,130.1,37.5,21.2.
Wherein, sulfoxide compound is 2- (p-methylphenyl sulfinyl) acetic acid, source: pacifies resistance to Jilin Chemical, structural formula are as follows:
Embodiment 20
The thio-ether type compounds of synthesis are as follows:(4,4 '-thiodiphenol)
Sulfoxide compound (0.5mmol) and acetonitrile (2.0mL) are added into dry 15mL schlenck pipe, then
At 25 DEG C, phosphorus trichloride (0.525mmol) is added drop-wise in schlenck pipe with syringe, is detected by contact plate and determine reaction
Time (i.e. after fully reacting) is 0.5h, after reaction, is chromatographed by column by thio-ether type compounds and solvent and POCl3Separation
It opens, obtains white solid, the yield of thio-ether type compounds is 94%.Nuclear magnetic data1H NMR(400MHz,d6-DMSO):δ
9.62 (s, 1H), 7.14 (d, 2H, J=8.64Hz), 6.73 (d, 2H, J=8.64Hz)；13C NMR(100MHz,d6-DMSO):δ
157.0,132.7,124.7,116.3.
Wherein, source: sulfoxide compound 4,4 '-sulfinyl biphenols pacify resistance to Jilin Chemical, structural formula are as follows:
Embodiment 21
The thio-ether type compounds of synthesis are as follows:(N, N- diethyl -2- (to methylphenyl-sulfanyl)
Acetamide)
Sulfoxide compound (0.5mmol) and acetonitrile (2.0mL) are added into dry 15mL schlenck pipe, then
At 25 DEG C, phosphorus trichloride (0.525mmol) is added drop-wise in schlenck pipe with syringe, is detected by contact plate and determine reaction
Time (i.e. after fully reacting) is 0.5h, after reaction, is chromatographed by column by thio-ether type compounds and solvent and POCl3Separation
It opens, obtains colourless oil liquid, the yield of thio-ether type compounds is 66%.Nuclear magnetic data1H NMR(400MHz,CDCl3):
δ 7.36 (d, 2H, J=8.12Hz), 7.10 (d, 2H, J=8.12Hz), 3.68 (s, 2H) .3.36 (q, 2H, J=7.12Hz),
3.31 (q, 2H, J=7.16Hz), 2.32 (s, 3H), 1.18 (t, 3H, J=7.16Hz), 1.10 (t, 3H, J=7.12Hz)；13C
NMR(100MHz,CDCl3):δ167.7,137.3,131.5,129.8,42.6,40.4,37.8,21.1,14.5,13.0.
Wherein, sulfoxide compound N, N- diethyl -2- (to methylbenzene sulfinyl) acetamide, source: An Naiji
Chemistry, structural formula are as follows:
Embodiment 22
The thio-ether type compounds of synthesis are as follows:(thiobis (4,1- phenylene) diethyl
Acid esters)
Sulfoxide compound (0.5mmol) and acetonitrile (2.0mL) are added into dry 15mL schlenck pipe, then
At 25 DEG C, phosphorus trichloride (0.525mmol) is added drop-wise in schlenck pipe with syringe, is detected by contact plate and determine reaction
Time (i.e. after fully reacting) is 0.5h, after reaction, is chromatographed by column by thio-ether type compounds and solvent and POCl3Separation
It opens, obtains white solid, the yield of thio-ether type compounds is 93%.Nuclear magnetic data1H NMR(400MHz,CDCl3):δ
7.34 (d, 2H, J=8.76Hz), 7.04 (d, 2H, J=8.76Hz), 2.30 (s, 3H)；13C NMR(100MHz,CDCl3):δ
169.3,150.1,133.0,132.3,122.6,21.2. high resolution mass spectrum data HRMS (MS) m/z calcd for
C16H14O4S(M+H)+303.0686,found 303.0674.
Wherein, sulfoxide compound is bis- (4, the 1- phenylene) diacetate esters of sulfenyl, source: pacifies resistance to Jilin Chemical, structural formula are as follows:
Illustrative description has been done to the present invention above, it should explanation, the case where not departing from core of the invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent replacement of creative work equal
Fall into protection scope of the present invention.
Claims (10)
1. a kind of synthetic method of thio-ether type compounds, which comprises the following steps: by phosphorus trichloride be uniformly distributed
There is the solvent of sulfoxide compound uniformly to mix, reacted 0.5~6 hour after mixing in 20~25 DEG C, obtain thio-ether type compounds,
Wherein, the solvent is acetonitrile,
The ratio of the amount of the substance of the sulfoxide compound and phosphorus trichloride is 1:1.05, the general formula of the thio-ether type compounds
Are as follows:
The sulfoxide compound are as follows:
The R1For aryl or alkyl, the R2For aryl or alkyl.
2. synthetic method according to claim 1, which is characterized in that detected by contact plate and determine the reaction time.
3. synthetic method according to claim 1, which is characterized in that in the solvent that sulfoxide compound is distributed with
In, the ratio of the volume of the amount and solvent of the substance of the sulfoxide compound is 1:(2~4), the unit of the amount of the substance is
Mmol, the unit of the volume are mL.
4. synthetic method according to claim 1, which is characterized in that after obtaining thio-ether type compounds, by volume ratio
For 10:1 petroleum ether and ethyl acetate uniformly mix be incorporated as mobile phase, with the mobile phase to the thio-ether type compounds into
Row elution.
5. synthetic method as described in claim 1 is preparing the application in thio-ether type compounds, which is characterized in that by the sulphur
The yield of ether compound is improved to 66~99%.
The preparation method of thiobis 6. (4,1- phenylene) diacetate esters, which comprises the following steps:
Phosphorus trichloride is uniformly mixed with the acetonitrile for being evenly distributed with bis- (4, the 1- phenylene) diacetate esters of sulfenyl, after mixing in
20~25 DEG C are reacted at least 0.5 hour, and thiobis (4,1- phenylene) diacetate esters are obtained,
Wherein, the ratio of the amount of the substance of bis- (4, the 1- phenylene) diacetate esters of the sulfenyl and phosphorus trichloride is 1:1.05.
7. preparation method according to claim 6, which is characterized in that detected by contact plate and determine the reaction time.
8. preparation method according to claim 7, which is characterized in that bis- (4, the 1- phenylene) diacetate esters of sulfenyl
The amount of substance and the ratio of volume of acetonitrile be 1:(2~4), the unit of the amount of the substance is mmol, the unit of the volume
For mL.
9. preparation method according to claim 8, which is characterized in that obtaining thiobis (4,1- phenylene) diacetate esters
Later, petroleum ether and ethyl acetate that volume ratio is 10:1 are uniformly mixed and is incorporated as mobile phase, with the mobile phase to described
Thiobis (4,1- phenylene) diacetate esters are eluted.
10. application of the preparation method as claimed in claim 9 in synthesis thiobis (4,1- phenylene) diacetate esters, special
Sign is, the yield of the thiobis (4,1- phenylene) diacetate esters is risen above equal to 93%.
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| CN111116436A (en) * | 2020-01-17 | 2020-05-08 | 信阳师范学院 | Synthetic method of thioether compound containing 1, 4-naphthoquinone structure |
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