CN109134326A - A kind of synthetic method of S- arylthio sulfone compound - Google Patents
A kind of synthetic method of S- arylthio sulfone compound Download PDFInfo
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- CN109134326A CN109134326A CN201811191188.7A CN201811191188A CN109134326A CN 109134326 A CN109134326 A CN 109134326A CN 201811191188 A CN201811191188 A CN 201811191188A CN 109134326 A CN109134326 A CN 109134326A
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- arylthio
- phenyl
- synthetic method
- free radical
- sulfone compound
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 16
- -1 phenyl tetrafluoride boron diazonium salt Chemical class 0.000 claims abstract description 39
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- RMVRSNDYEFQCLF-UHFFFAOYSA-N phenyl mercaptan Natural products SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims abstract description 31
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000012954 diazonium Substances 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 11
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 230000008878 coupling Effects 0.000 claims abstract description 4
- 238000010168 coupling process Methods 0.000 claims abstract description 4
- 238000005859 coupling reaction Methods 0.000 claims abstract description 4
- 150000003254 radicals Chemical class 0.000 claims abstract description 4
- 230000005284 excitation Effects 0.000 claims abstract description 3
- 230000027756 respiratory electron transport chain Effects 0.000 claims abstract description 3
- FULZLIGZKMKICU-UHFFFAOYSA-N N-phenylthiourea Chemical class NC(=S)NC1=CC=CC=C1 FULZLIGZKMKICU-UHFFFAOYSA-N 0.000 claims abstract 2
- 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
- 239000007789 gas Substances 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
- 229910052786 argon Inorganic materials 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000006073 displacement reaction Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 229910004879 Na2S2O5 Inorganic materials 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000004440 column chromatography Methods 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 239000012973 diazabicyclooctane Substances 0.000 claims description 2
- 150000001989 diazonium salts Chemical class 0.000 claims description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 238000000926 separation method Methods 0.000 claims description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000003504 photosensitizing agent Substances 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 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
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 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 kind of synthetic methods of S- arylthio sulfone compound, this method is by organic solvent, after phenyl tetrafluoride boron diazonium salt and thiocarbamide carry out addition formation phenyl isothiourea salt, obtain benzenethiol anion, under light source irradiation, benzenethiol anionic is generated benzenethiol free radical by the Rodamin 6G of excitation state；The Rodamin 6G of phenyl tetrafluoride boron diazonium salt and lower valency occurs single electron transfer and obtains phenyl radical, and the combination of phenyl radical and sulfur dioxide solid substitute obtains benzene sulfonyl free radical；The coupling of free radical occurs for benzenethiol free radical and benzene sulfonyl free radical, obtains corresponding target product.The method of the present invention mild condition, is simple and efficient, and reaction yield is high, and product purity is good, is convenient for separating-purifying, has good application value.
Description
Technical field
The invention belongs to technical field of organic chemistry, and in particular to a kind of synthesis side of S- arylthio sulfone compound
Method.
Background technique
Due to the potential bioactivity of compound and application value containing thioether and sulphonyl class skeleton, this kind of sulfur-bearing chemical combination
Object is always intermediate crucial in organic synthesis.And wherein there is the source that not only can be used as benzene sulfonyl segment, but also can make
For the deep concern by organic chemist of S- arylthio sulfone compound in diphenyl sulfide segment source.Due to pair of such compound
Principal characteristic matter, synthetic route and reaction property in relation to this kind of compound have obtained in-depth study.About S- arylthio sulfone
The synthetic route of class compound can substantially be summarized as two o'clock: (1) using oxidation strategy that the oxidation of disulfide selectivity, (2) are sharp
It is coupled with existing sulphonyl reagent with thio-ether type compounds.Both strategies obtain extensively because of its mature and stable operation
Application.The present invention is directed to develop under a kind of temperate condition, it is not necessarily to oxidizing condition, removes synthesis S- virtue using raw material simple and easy to get
The thio sulfone compound of base.
Thiocarbamide is a kind of small molecule compound very simple and easy to get, and it is substituted to be usually used to hydrogen on synthesis nitrogen-atoms
Reaction.It is either reacted with nucleopilic reagent, sloughs a molecule urea, obtain a series of negative class intermediate of alkyl sulfides.This reaction utilizes
The electrophilicity of phenyl tetrafluoride boron diazonium salt carries out addition to thiocarbamide, benzenethiol anion is obtained after urea of leaving away.Benzenethiol is negative
Ion aoxidizes to obtain benzenethiol free radical in the photosensitizer for the state that is excited.On the other hand, the benzene restored by lower valency photosensitizer
Base tetrafluoride boron diazonium salt generates phenyl radical, and phenyl radical and pyrosulfite, which combine, obtains benzene sulfonyl free radical.Two
S- arylthio sulfone compound can be obtained in the coupling of a free radical.
Based on this, present invention employs one kind under visible light conditions, using photosensitizer catalysis, with phenyl tetrafluoride boron
Reaction between three component of diazonium salt, thiocarbamide and sulfur dioxide solid substitute.
Summary of the invention
It is an object of that present invention to provide a series of a kind of synthesis sides of easy, efficient S- arylthio sulfone compounds
Method.
The method of the present invention utilizes base tetrafluoride boron diazonium salt, sulfur dioxide solid substitute and thiocarbamide, under visible light, into
Capable catalysis radical reaction efficiently constructs a series of S- arylthio sulfone compounds.
The present invention is realized especially by following technical scheme:
A kind of synthetic method of S- arylthio sulfone compound, it is in organic solvent, at room temperature, glimmering with 35 watts
Light lamp is as light source, and using Rodamin 6G as photosensitizer, phenyl tetrafluoride boron diazonium salt first carries out addition with thiocarbamide and forms benzene
After base isothiuronium salts, benzenethiol anion is obtained.Under the irradiation of 35 watts of fluorescent lamps, the Rodamin 6G of excitation state is by benzenethiol
Anionic generates benzenethiol free radical.On the other hand, the Rodamin 6G of phenyl tetrafluoride boron diazonium salt and lower valency is sent out
Raw single electron transfer obtains phenyl radical, and the combination of phenyl radical and sulfur dioxide solid substitute obtains benzene sulfonyl freedom
Base.The coupling of free radical occurs for benzenethiol free radical and benzene sulfonyl free radical, obtains corresponding target product.
The specific chemical equation of the synthetic method is as follows:
In formula, " SO2"=Na2S2O5、K2S2O5Or DABSO；
R is the fragrant ring substituents of electrophilic or supplied for electronic or is alkane, electron-withdrawing group have fluorine, chlorine, bromine, ester group,
Acyl group, cyano, trifluoromethyl and its corresponding aryl substituent group, electron-donating group are alkyl, methoxyl group, phenyl and its corresponding
Aromatic substituent group.
The synthetic method of above-mentioned S- arylthio sulfone compound specifically includes the following steps:
1) phenyl tetrafluoride boron diazonium salt, sulfur dioxide solid substitute, sulphur at room temperature, are successively added into reaction tube
Urea and Rodamin 6G, are placed in displacement gas in high pure nitrogen or argon gas so that system be in after oxygen free condition be added it is organic molten
Agent is placed in around light source until stirring to complete reaction；
2) after TLC monitors reaction completely, reaction solution is directly concentrated under reduced pressure, and carry out column chromatography for separation, using petroleum
Corresponding S- arylthio sulfone compound can be obtained as mobile phase in the mixed liquor of ether and ethyl acetate.
Further, organic solvent described in reaction system is selected from 1,2- dichloroethanes (DCE) or acetonitrile (MeCN).
Further, meter, sulfur dioxide solid substitute are worked as 1.0 with phenyl tetrafluoride boron diazonium salt in reaction system
Dosage be 2 equivalents, the dosage of thiocarbamide is 1.5 equivalents.
The sulfur dioxide solid substitute is sodium pyrosulfite (Na2S2O5), potassium metabisulfite (K2S2O5) and
DABCO.(SO2)2Or DABSO.
Further, the reaction temperature of reaction system is 25 DEG C of room temperature；Reaction time is 12 hours；Reacting required light source is
35 watts of fluorescent lamps, other visible light sources such as Blue LED are also applied for the reaction.
The invention has the benefit that
The present invention reacts under the conditions of visible light catalytic as mild as a dove, using thiocarbamide as S- arylthio sulfone class chemical combination
The source of sulphur in object, using pyrosulfite as the source of sulfuryl in S- arylthio sulfone compound.Simply and efficiently structure
A series of S- arylthio sulfone compounds are built.Industrial very cheap and easily-available raw material (thiocarbamide, Jiao Ya have been selected in the reaction
Sulfate) synthesize the S- arylthio sulfone compound with wide application prospect.The reaction avoids traditional sulphonyl class
The use for closing object synthesis middle strong acidity raw material, can be used for large-scale industrially prepared, have in scientific research and industrial circle fine
Application prospect.
Specific embodiment
Below in conjunction with specific embodiment of the present invention, technical solution of the present invention is clearly and completely described, is shown
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention
Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to
In the scope of protection of the invention.
Embodiment 1
At room temperature, phenyl tetrafluoride boron diazonium salt, the 0.4mmol coke sulfurous of 0.4mmol are successively added into reaction tube
The Rodamin6G of sour sodium, the thiocarbamide of 1.5mmol and 2.0mmol% is stoppered reaction tube with plug and is placed on high pure nitrogen or argon
Displacement gas in gas stirs so that system is in 1, the 2- dichloroethanes of addition 2mL after oxygen free condition being placed in around 35 watts of fluorescent lamps
It mixes until complete reaction.Target product example 1, yield 63% can be obtained.
The target product structural formula that the present embodiment is prepared is as follows:
The structural characterization of target compound:
1H NMR(400MHz,CDCl3): δ 7.56 (d, J=8.0Hz, 2H), 7.51-7.30 (m, 6H).
13C NMR(101MHz,CDCl3): δ 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。
Embodiment 2
At room temperature, 4- chlorphenyl tetrafluoride boron diazonium salt, the 0.4mmol that 0.4mmol is successively added into reaction tube are burnt
The Rodamin 6G of sodium sulfite, the thiocarbamide of 1.5mmol and 2.0mmol%, is stoppered reaction tube with plug and is placed on high pure nitrogen
Or displacement gas in argon gas is being placed in 35 watts of fluorescent lamps so that system is in 1, the 2- dichloroethanes of addition 2mL after oxygen free condition
Until surrounding stirring to complete reaction.Target product example 2 can be obtained.
The target product structural formula that the present embodiment is prepared is as follows:
The structural characterization of 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): δ 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.
Embodiment 3
At room temperature, 4- fluorophenyl tetrafluoride boron diazonium salt, the 0.4mmol that 0.4mmol is successively added into reaction tube are burnt
The Rodamin 6G of sodium sulfite, the thiocarbamide of 1.5mmol and 2.0mmol%, is stoppered reaction tube with plug and is placed on high pure nitrogen
Or displacement gas in argon gas is being placed in 35 watts of fluorescent lamps so that system is in 1, the 2- dichloroethanes of addition 2mL after oxygen free condition
Until surrounding stirring to complete reaction.Target product example 3 can be obtained.
The target product structural formula that the present embodiment is prepared is as follows:
The 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): δ 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.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understand without departing from the principles and spirit of the present invention can to these examples carry out it is a variety of variation, modification, replacement and
Modification, the scope of the present invention is defined by the appended.
Claims (8)
1. a kind of synthetic method of S- arylthio sulfone compound, which is characterized in that in organic solvent, phenyl tetrafluoride boron
After diazonium salt and thiocarbamide carry out addition formation phenyl isothiourea salt, benzenethiol anion is obtained, under light source irradiation, excitation state
Benzenethiol anionic is generated benzenethiol free radical by Rodamin 6G；Phenyl tetrafluoride boron diazonium salt and lower valency
Rodamin 6G occurs single electron transfer and obtains phenyl radical, and the combination of phenyl radical and sulfur dioxide solid substitute obtains
To benzene sulfonyl free radical；The coupling of free radical occurs for benzenethiol free radical and benzene sulfonyl free radical, obtains corresponding target product.
2. a kind of synthetic method of S- arylthio sulfone compound according to claim 1, which is characterized in that described
The specific chemical equation of synthetic method is as follows:
In formula, " SO2"=Na2S2O5、K2S2O5Or DABSO；
R is the fragrant ring substituents of electrophilic or supplied for electronic or is alkane；
Electron-withdrawing group is selected from fluorine, chlorine, bromine, ester group, acyl group, cyano or trifluoromethyl and its corresponding aryl substituent group；
Electron-donating group is selected from alkyl, methoxyl group or phenyl and its corresponding aromatic substituent group.
3. a kind of synthetic method of S- arylthio sulfone compound according to claim 1, which is characterized in that described
Synthetic method specifically includes the following steps:
1) at room temperature, successively into reaction tube be added phenyl tetrafluoride boron diazonium salt, sulfur dioxide solid substitute, thiocarbamide and
Rodamin 6G is placed in displacement gas in high pure nitrogen or argon gas, so that organic solvent is added after being in oxygen free condition in system, sets
Stirring until reacting completely around light source；
2) after TLC monitors reaction completely, reaction solution is directly concentrated under reduced pressure, and carry out column chromatography for separation, using petroleum ether and
Corresponding S- arylthio sulfone compound can be obtained as mobile phase in the mixed liquor of ethyl acetate.
4. a kind of synthetic method of S- arylthio sulfone compound described in any one of claim 1 to 3, feature
It is, organic solvent described in reaction system is selected from 1,2- dichloroethanes or acetonitrile.
5. a kind of synthetic method of S- arylthio sulfone compound described in any one of claim 1 to 3, feature
It is, work as meter with phenyl tetrafluoride boron diazonium salt in reaction system for 1.0, the dosage of sulfur dioxide solid substitute is worked as 2
Amount, the dosage of thiocarbamide are 1.5 equivalents.
6. a kind of synthetic method of S- arylthio sulfone compound described in any one of claim 1 to 3, feature
It is, the sulfur dioxide solid substitute is sodium pyrosulfite, potassium metabisulfite, DABCO. (SO2)2Or DABSO.
7. a kind of synthetic method of S- arylthio sulfone compound described in any one of claim 1 to 3, feature
It is, the reaction temperature of reaction system is 25 DEG C of room temperature；Reaction time is 12 hours.
8. a kind of synthetic method of S- arylthio sulfone compound described in any one of claim 1 to 3, feature
It is, light source needed for reacting is selected from 35 watts of fluorescent lamps.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110683971A (en) * | 2019-09-29 | 2020-01-14 | 台州学院 | Method for synthesizing aryl acetylene alkyl sulfone compounds based on Hantzsch esters |
| CN111138323A (en) * | 2019-12-19 | 2020-05-12 | 台州学院 | Preparation method of sulfonamide compound |
| CN111170905A (en) * | 2019-12-28 | 2020-05-19 | 台州学院 | Synthetic method of sulfonamide compound |
| CN112812046A (en) * | 2020-12-29 | 2021-05-18 | 中国科学院西北高原生物研究所 | Preparation method of thiosulfonate compound |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110683971A (en) * | 2019-09-29 | 2020-01-14 | 台州学院 | Method for synthesizing aryl acetylene alkyl sulfone compounds based on Hantzsch esters |
| CN111138323A (en) * | 2019-12-19 | 2020-05-12 | 台州学院 | Preparation method of sulfonamide compound |
| CN111138323B (en) * | 2019-12-19 | 2022-04-29 | 台州学院 | Preparation method of sulfonamide compound |
| CN111170905A (en) * | 2019-12-28 | 2020-05-19 | 台州学院 | Synthetic method of sulfonamide compound |
| CN111170905B (en) * | 2019-12-28 | 2022-04-29 | 台州学院 | Synthetic method of sulfonamide compound |
| CN112812046A (en) * | 2020-12-29 | 2021-05-18 | 中国科学院西北高原生物研究所 | Preparation method of thiosulfonate 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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