CN109134326B - Synthetic method of S-aryl thiosulfone compound - Google Patents
Synthetic method of S-aryl thiosulfone compound Download PDFInfo
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- CN109134326B CN109134326B CN201811191188.7A CN201811191188A CN109134326B CN 109134326 B CN109134326 B CN 109134326B CN 201811191188 A CN201811191188 A CN 201811191188A CN 109134326 B CN109134326 B CN 109134326B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 30
- 238000010189 synthetic method Methods 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 30
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 23
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012954 diazonium Substances 0.000 claims abstract description 16
- 150000001989 diazonium salts Chemical class 0.000 claims abstract description 16
- XPPWLXNXHSNMKC-UHFFFAOYSA-N phenylboron Chemical compound [B]C1=CC=CC=C1 XPPWLXNXHSNMKC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000001308 synthesis method Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical group [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 5
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 5
- 238000009423 ventilation Methods 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Chemical group 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000004440 column chromatography Methods 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 claims description 2
- 229940043349 potassium metabisulfite Drugs 0.000 claims description 2
- 235000010263 potassium metabisulphite Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- RMVRSNDYEFQCLF-UHFFFAOYSA-N phenyl mercaptan Natural products SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 abstract description 25
- -1 thiophenol anions Chemical class 0.000 abstract description 18
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 abstract description 4
- 150000003254 radicals Chemical class 0.000 abstract description 4
- FULZLIGZKMKICU-UHFFFAOYSA-N N-phenylthiourea Chemical class NC(=S)NC1=CC=CC=C1 FULZLIGZKMKICU-UHFFFAOYSA-N 0.000 abstract description 2
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
- 238000007259 addition reaction Methods 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 239000003504 photosensitizing agent Substances 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- PVLNHYPAZWPHDM-UHFFFAOYSA-N (4-chlorophenyl)boron Chemical compound [B]C1=CC=C(Cl)C=C1 PVLNHYPAZWPHDM-UHFFFAOYSA-N 0.000 description 1
- YGGMQWSJXSNGDT-UHFFFAOYSA-N (4-fluorophenyl)boron Chemical compound [B]C1=CC=C(F)C=C1 YGGMQWSJXSNGDT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910004879 Na2S2O5 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical group C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
- C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of S-aryl thiosulfone compounds, which comprises the steps of carrying out addition reaction on phenyl boron tetrafluoride diazonium salt and thiourea in an organic solvent to form phenyl isothiourea salt to obtain thiophenol anions, and oxidizing the thiophenol anions into thiophenol free radicals by excited Rodamin6G under the irradiation of a light source; the single electron transfer of the phenyl boron tetrafluoride diazonium salt and the low-valence Rodamin6G occurs to obtain a phenyl radical, and the combination of the phenyl radical and the sulfur dioxide solid substitute obtains a benzenesulfonyl radical; the thiophenol free radical and the benzene sulfonyl free radical are coupled to generate a corresponding target product. The method has the advantages of mild conditions, simplicity, high efficiency, high reaction yield, good product purity, convenience for separation and purification and good application value.
Description
Technical Field
The invention belongs to the technical field of organic chemistry, and particularly relates to a synthetic method of an S-aryl thiosulfone compound.
Background
Because of the potential biological activity and application value of the compounds containing thioether and sulfonyl frameworks, the sulfur-containing compounds are always key intermediates in organic synthesis. And the S-aryl thiosulfone compounds which can be used as the sources of the benzenesulfonyl fragments and the phenylsulfide fragments are well attracted by organic chemists. Due to the dual nature of this class of compounds, there has been extensive research into the synthetic routes and reaction properties of these compounds. The synthetic route for the S-aryl thiosulfone compounds can be generally summarized as two points: (1) selective oxidation of disulfides by means of oxidation strategies, (2) coupling with thioethers by means of existing sulphonyl reagents. Both strategies are widely used due to their mature and stable operation. The invention aims to develop a method for synthesizing S-aryl thiosulfone compounds by using simple and easily-obtained raw materials under mild conditions without oxidation conditions.
Thiourea is a very simple and readily available small molecule compound that is commonly used to synthesize reactions in which the hydrogen on the nitrogen atom is replaced. Or reacting with nucleophilic reagent to remove one molecule of urea to obtain a series of alkyl sulfur negative intermediates. According to the reaction, thiourea is added by utilizing the electrophilicity of the phenyl boron tetrafluoride diazonium salt, and the benzenethiol negative ion is obtained after the urea is removed. The thiophenol anions are oxidized by an excited photosensitizer to obtain thiophenol free radicals. On the other hand, the phenyl boron tetrafluoride diazonium salt reduced by the low-valence photosensitizer generates a phenyl radical, and the phenyl radical and the pyrosulfite are combined to obtain the phenylsulfonyl radical. And (3) coupling the two free radicals to obtain the S-aryl thiosulfone compound.
Based on the method, the invention adopts a reaction catalyzed by a photosensitizer under the condition of visible light and using three components of phenyl boron tetrafluoride diazonium salt, thiourea and sulfur dioxide solid substitute.
Disclosure of Invention
The invention aims to provide a simple and efficient synthesis method of a series of S-aryl thiosulfone compounds.
The method utilizes boron tetrafluoride diazonium salt, sulfur dioxide solid substitute and thiourea to carry out catalytic free radical reaction under visible light, and efficiently constructs a series of S-aryl thiosulfone compounds.
The invention is realized by the following technical scheme:
a synthesis method of S-aryl thiosulfone compounds comprises the steps of taking a 35W fluorescent lamp as a light source, taking Rodamin6G as a photosensitizer and adding phenyl boron tetrafluoride diazonium salt with thiourea to form phenyl isothiourea salt in an organic solvent at room temperature to obtain thiophenol anions. Under the irradiation of a 35W fluorescent lamp, excited state Rodamin6G oxidized thiophenol anion to generate thiophenol free radical. On the other hand, the phenyl boron tetrafluoride diazonium salt and low-valence Rodamin6G generate single electron transfer to obtain phenyl free radical, and the phenyl free radical is combined with sulfur dioxide solid substitute to obtain benzenesulfonyl free radical. The thiophenol free radical and the benzene sulfonyl free radical are coupled to generate a corresponding target product.
The specific chemical reaction formula of the synthesis method is as follows:
in the formula, "SO2"＝Na2S2O5、K2S2O5Or DABSO;
r is an electron-withdrawing or electron-supplying aromatic ring substituent or alkane, the electron-withdrawing group comprises fluorine, chlorine, bromine, ester group, acyl, cyano, trifluoromethyl and corresponding aryl substituent groups, and the electron-supplying group comprises alkyl, methoxy, phenyl and corresponding aromatic substituent groups.
The synthesis method of the S-aryl thiosulfone compound specifically comprises the following steps:
1) at room temperature, sequentially adding boron phenyl tetrafluoride diazonium salt, sulfur dioxide solid substitute, thiourea and Rodamin6G into a reaction tube, placing the reaction tube in high-purity nitrogen or argon for ventilation, adding an organic solvent after the system is in an anaerobic condition, placing the system around a light source, and stirring until complete reaction;
2) and after TLC monitoring complete reaction, directly carrying out reduced pressure concentration on the reaction liquid, carrying out column chromatography separation, and taking the mixed liquid of petroleum ether and ethyl acetate as a mobile phase to obtain the corresponding S-aryl thiosulfone compound.
Further, the organic solvent in the reaction system is selected from 1, 2-Dichloroethane (DCE) or acetonitrile (MeCN).
Furthermore, the usage amount of the sulfur dioxide solid substitute is 2 equivalents and the usage amount of the thiourea is 1.5 equivalents based on 1.0 equivalent of the phenyl boron tetrafluoride diazonium salt in the reaction system.
The sulfur dioxide solid substitute is sodium metabisulfite (Na)2S2O5) Potassium metabisulfite (K)2S2O5) And DABCO (SO)2)2Or DABSO.
Further, the reaction temperature of the reaction system is 25 ℃ at room temperature; the reaction time is 12 hours; the light source required for the reaction was a 35 watt fluorescent lamp, other visible light sources such as Blue LED are also suitable for the reaction.
The invention has the beneficial effects that:
according to the invention, under a very mild visible light catalysis condition, thiourea is used as a source of sulfur in the S-aryl thiosulfone compound, and pyrosulfite is used as a source of a sulfone group in the S-aryl thiosulfone compound. A series of S-aryl thiosulfone compounds are simply and efficiently constructed. The reaction selects the raw materials (thiourea and pyrosulfite) which are very cheap and easily obtained industrially to synthesize the S-aryl thiosulfone compound with wide application prospect. The reaction avoids the use of strong acid raw materials in the synthesis of the traditional sulfonyl compounds, can be used for large-scale industrial preparation, and has good application prospect in the fields of scientific research and industry.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
At room temperature, 0.4mmol of phenyl boron tetrafluoride diazonium salt, 0.4mmol of sodium metabisulfite, 1.5mmol of thiourea and 2.0mmol percent of Rodamin6G are added into a reaction tube in sequence, the reaction tube is plugged by a plug and placed in high-purity nitrogen or argon for ventilation, 2mL of 1, 2-dichloroethane is added after the system is in an anaerobic condition, and the mixture is placed around a 35 watt fluorescent lamp and stirred until complete reaction. The desired product, example 1, was obtained in 63% yield.
The target product prepared in this example has the following structural formula:
structural characterization of the target compound:
1H NMR(400MHz,CDCl3)：7.56(d,J＝8.0Hz,2H),7.51–7.30(m,6H)。
13C NMR(101MHz,CDCl3)：143.0,136.5,133.6,131.4,129.4,128.8,127.8,127.5。
HRMS(ESI)calcd for C12H11O2S2 +:251.0195(M+H+),found:251.0188。
example 2
At room temperature, 0.4mmol of 4-chlorophenyl boron tetrafluoride diazonium salt, 0.4mmol of sodium metabisulfite, 1.5mmol of thiourea and 2.0mmol percent of Rodamin6G are sequentially added into a reaction tube, the reaction tube is plugged by a plug and then placed in high-purity nitrogen or argon for ventilation, 2mL of 1, 2-dichloroethane is added after the system is in an anaerobic condition, and the mixture is placed around a 35 watt fluorescent lamp and stirred until complete reaction. The target product, example 2, was obtained.
The target product prepared in this example has the following structural formula:
structural characterization of the target compound:
1H NMR(400MHz,CDCl3)：7.52(d,J＝8.4Hz,2H),7.43(d,J＝8.4Hz,2H),7.34(q,J＝8.4Hz,4H).
13C NMR(101MHz,CDCl3)：141.3,140.6,138.6,137.7,129.9,129.3,128.9,126.0.
HRMS(ESI)calcd for C12H9Cl2O2S2 +:318.9416(M+H+),found:318.9426.
example 3
At room temperature, 0.4mmol of 4-fluorophenyl boron tetrafluoride diazonium salt, 0.4mmol of sodium metabisulfite, 1.5mmol of thiourea and 2.0mmol percent of Rodamin6G are sequentially added into a reaction tube, the reaction tube is plugged by a plug and then placed in high-purity nitrogen or argon for ventilation, 2mL of 1, 2-dichloroethane is added after the system is in an anaerobic condition, and the mixture is placed around a 35 watt fluorescent lamp and stirred until complete reaction. The desired product, example 3, was obtained.
The target product prepared in this example has the following structural formula:
structural characterization of compound example 3:
1H NMR(400MHz,CDCl3)：7.56–7.46(m,2H),7.33–7.25(m,2H),7.05(t,J＝8.5Hz,2H),6.98(t,J＝8.6Hz,2H).
13C NMR(101MHz,CDCl3)：166.9,166.1,164.3,163.6,138.9,138.8,130.5,130.4,117.0,116.8,116.3,116.1.
HRMS(ESI)calcd for C12H9F2O2S2 +:287.0007(M+H+),found:287.0011.
although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (4)
1. The synthesis method of the S-aryl thiosulfone compound is characterized by comprising the following steps:
1) at room temperature, sequentially adding phenyl boron tetrafluoride diazonium salt, sulfur dioxide solid substitute, thiourea and rhodamine 6G into a reaction tube, placing the reaction tube in high-purity nitrogen or argon for ventilation, adding an organic solvent after the system is in an anaerobic condition, placing the system around a light source, and stirring until the reaction is completed;
2) after TLC monitoring complete reaction, directly decompressing and concentrating the reaction liquid, carrying out column chromatography separation, and obtaining the corresponding S-aryl thiosulfone compound by adopting a mixed liquid of petroleum ether and ethyl acetate as a mobile phase;
the structural formula of the phenyl boron tetrafluoride diazonium salt is as follows:
the structural formula of the S-aryl thiosulfone compound is as follows:
wherein R is selected from fluorine, chlorine, bromine, alkyl or methoxy;
the organic solvent is selected from 1, 2-dichloroethane or acetonitrile;
the sulfur dioxide solid substitute is sodium metabisulfite, potassium metabisulfite or DABSO.
2. The method for synthesizing S-aryl thiosulfone compounds as claimed in claim 1, wherein the amount of the sulfur dioxide solid substitute is 2 equivalents and the amount of the thiourea is 1.5 equivalents, based on 1.0 equivalent of the boron phenyl tetrafluoride diazonium salt in the reaction system.
3. The method for synthesizing the S-aryl thiosulfone compound as claimed in claim 1, wherein the reaction temperature of the reaction system is 25 ℃ at room temperature; the reaction time was 12 hours.
4. The method for synthesizing S-aryl thiosulfone compounds as claimed in claim 1, wherein the light source required for the reaction is a 35W fluorescent lamp.
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| CN111170905B (en) * | 2019-12-28 | 2022-04-29 | 台州学院 | Synthetic method of sulfonamide compound |
| CN112812046B (en) * | 2020-12-29 | 2022-09-13 | 中国科学院西北高原生物研究所 | Preparation method of thiosulfonate compound |
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