CN117843536A - Preparation method of diphenyl sulfone derivative - Google Patents
Preparation method of diphenyl sulfone derivative Download PDFInfo
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- CN117843536A CN117843536A CN202211207360.XA CN202211207360A CN117843536A CN 117843536 A CN117843536 A CN 117843536A CN 202211207360 A CN202211207360 A CN 202211207360A CN 117843536 A CN117843536 A CN 117843536A
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- diphenyl sulfone
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- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical class C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 85
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 333
- 238000006243 chemical reaction Methods 0.000 claims abstract description 191
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000007864 aqueous solution Substances 0.000 claims abstract description 38
- -1 aryl primary alcohol Chemical class 0.000 claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000005286 illumination Methods 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 171
- 239000000203 mixture Substances 0.000 claims description 33
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000003504 photosensitizing agent Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 198
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 99
- 239000008367 deionised water Substances 0.000 description 67
- 229910021641 deionized water Inorganic materials 0.000 description 67
- 239000012043 crude product Substances 0.000 description 36
- 239000000243 solution Substances 0.000 description 36
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 35
- 239000007789 gas Substances 0.000 description 34
- 239000012074 organic phase Substances 0.000 description 34
- 229910001220 stainless steel Inorganic materials 0.000 description 34
- 239000010935 stainless steel Substances 0.000 description 34
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 32
- 238000000605 extraction Methods 0.000 description 31
- 238000001704 evaporation Methods 0.000 description 29
- 230000008020 evaporation Effects 0.000 description 28
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 20
- 239000002245 particle Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- WEAYCYAIVOIUMG-UHFFFAOYSA-N 1-methyl-4-(4-methylphenyl)sulfonylbenzene Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C1=CC=C(C)C=C1 WEAYCYAIVOIUMG-UHFFFAOYSA-N 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- MVOSNPUNXINWAD-UHFFFAOYSA-N 1-(4-chlorophenyl)ethanol Chemical compound CC(O)C1=CC=C(Cl)C=C1 MVOSNPUNXINWAD-UHFFFAOYSA-N 0.000 description 2
- WYTRYIUQUDTGSX-UHFFFAOYSA-N 1-phenylpropan-2-ol Chemical compound CC(O)CC1=CC=CC=C1 WYTRYIUQUDTGSX-UHFFFAOYSA-N 0.000 description 2
- BDCFWIDZNLCTMF-UHFFFAOYSA-N 2-phenylpropan-2-ol Chemical compound CC(C)(O)C1=CC=CC=C1 BDCFWIDZNLCTMF-UHFFFAOYSA-N 0.000 description 2
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 description 2
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 2
- KMTDMTZBNYGUNX-UHFFFAOYSA-N 4-methylbenzyl alcohol Chemical compound CC1=CC=C(CO)C=C1 KMTDMTZBNYGUNX-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 206010024229 Leprosy Diseases 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- JESIHYIJKKUWIS-UHFFFAOYSA-N 1-(4-Methylphenyl)ethanol Chemical compound CC(O)C1=CC=C(C)C=C1 JESIHYIJKKUWIS-UHFFFAOYSA-N 0.000 description 1
- IMYRNVBKJGQWQX-UHFFFAOYSA-N 1-[4-(chloromethyl)phenyl]ethanol Chemical compound CC(O)C1=CC=C(CCl)C=C1 IMYRNVBKJGQWQX-UHFFFAOYSA-N 0.000 description 1
- PLVUIVUKKJTSDM-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)sulfonylbenzene Chemical compound C1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(F)C=C1 PLVUIVUKKJTSDM-UHFFFAOYSA-N 0.000 description 1
- GEGSSUSEWOHAFE-UHFFFAOYSA-N 2-(4-chlorphenoxy)-ethanol Chemical compound OCCOC1=CC=C(Cl)C=C1 GEGSSUSEWOHAFE-UHFFFAOYSA-N 0.000 description 1
- DAVFJRVIVZOKKS-UHFFFAOYSA-N 2-(4-methylphenyl)ethanol Chemical compound CC1=CC=C(CCO)C=C1 DAVFJRVIVZOKKS-UHFFFAOYSA-N 0.000 description 1
- MWUVGXCUHWKQJE-UHFFFAOYSA-N 4-fluorophenethyl alcohol Chemical compound OCCC1=CC=C(F)C=C1 MWUVGXCUHWKQJE-UHFFFAOYSA-N 0.000 description 1
- IUUULXXWNYKJSL-UHFFFAOYSA-N 4-methoxy-alpha-methylbenzyl alcohol Chemical compound COC1=CC=C(C(C)O)C=C1 IUUULXXWNYKJSL-UHFFFAOYSA-N 0.000 description 1
- 241000238876 Acari Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 241000713772 Human immunodeficiency virus 1 Species 0.000 description 1
- 206010061598 Immunodeficiency Diseases 0.000 description 1
- 208000029462 Immunodeficiency disease Diseases 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000000078 anti-malarial effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 239000001961 anticonvulsive agent Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000007813 immunodeficiency Effects 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003151 ovacidal effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229930015704 phenylpropanoid Natural products 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of diphenyl sulfone derivative, which takes aryl primary alcohol or aryl secondary alcohol and photosensitive sulfide as raw materials, acetonitrile aqueous solution as solvent, and reacts for 0.5-24h under the action of ammonia gas and oxygen-containing atmosphere and under the illumination at 0-80 ℃ to prepare the diphenyl sulfone derivative in one step. The yield of diphenyl sulfone derivative is more than 80%. The preparation system of the diphenyl sulfone derivative has the advantages of wide raw material sources, simple and convenient operation, high reaction activity, safety, environmental protection, simple post-treatment and great industrial application value.
Description
Technical Field
The invention relates to the technical field of preparation of diphenyl sulfone derivatives, in particular to a method for preparing diphenyl sulfone derivatives by oxidizing and bond breaking of aryl primary alcohol or secondary alcohol under photocatalysis.
Background
Sulfone compounds are important active substances in the fields of pesticides and medicines, and have broad-spectrum biological activities, such as disinsection, sterilization, weeding, mite killing, anti-tumor, anti-HIV-1, anti-malaria, leprosy treatment and the like. Among them, diphenyl sulfone and its derivatives are an important class of pharmaceutical, agricultural chemical and chemical intermediates. Can be used as a curing agent for epoxy resins. The preparation method is used for preparing antiepileptic drugs in medicine, synthesizing drugs such as thiofu Song Na, sodium glucose sulfone, phenylpropanoid sulfone and the like, can also be used for treating leprosy, and has the activity of inhibiting replication of immunodeficiency virus type I (HIV-1) in vitro. The diphenyl sulfone has high ovicidal activity to mites in the aspect of pesticides, and can also be used as an intermediate of pesticides. As an important chemical intermediate, it can be used for synthesizing downstream products such as plasticizer, etc.
At present, the traditional diphenyl sulfone derivative is reported to be prepared, the synthesis steps are numerous, the process is complex, the yield is low, the acid-base waste liquid is discharged in a large amount, the environment is not friendly, and the industrialization prospect is limited. In order to solve the problems, a novel synthesis method of diphenyl sulfone derivatives is invented, and the diphenyl sulfone derivatives are synthesized in one step with high yield. The preparation system of the diphenyl sulfone derivative has the advantages of wide raw material sources, simple and convenient operation, high reaction activity, safety, environmental protection, simple post-treatment and great industrial application value.
Disclosure of Invention
In order to solve the problems of complicated steps, complex process, low yield, large discharge of acid-base waste liquid, environment friendliness and the like in the conventional preparation process of the diphenyl sulfone derivative, a novel synthesis method of the diphenyl sulfone derivative is invented, and the diphenyl sulfone derivative is synthesized in one step with high yield. The preparation system of the diphenyl sulfone derivative has the advantages of wide raw material sources, simple and convenient operation, high reaction activity, safety, environmental protection, simple post-treatment and great industrial application value.
The invention is realized by the following technical scheme:
a preparation method of diphenyl sulfone derivative is characterized in that aryl alcohol and photosensitive sulfide are used as raw materials, acetonitrile aqueous solution (V/V=1:0.1-1:10) is used as solvent, and the diphenyl sulfone derivative is prepared by reacting for 0.5-24h at 0-80 ℃ under the action of ammonia gas and oxygen-containing atmosphere in one step. The aryl alcohol is one or more than two of aryl primary alcohol or aryl secondary alcohol; the ratio of the amount of sulfur and aryl alcohol in the photosensitive sulfide material in the reaction system is (0.5-20): 1.
In the above preparation method of diphenyl sulfone derivative, the aryl primary alcohol compound is one or more than two of the following compounds, wherein R is 1 Halogen (F, cl, br), alkyl (formula C) n H 2n+1 ，n＝1-10) Alkoxy (of the formula OC) n H 2n+1 N=1 to 10), an alkylhalo group (formula C n H 2n X, n=1-10, x=f, cl, br); m represents the number of carbon atoms, m=1-2; the number of R1 is 1-5.
The aryl secondary alcohol compound is one or more than two of the following compounds, wherein R is 2 Halogen (F, cl, br), alkyl (formula C) n H 2n+1 N=1 to 10), alkoxy (formula OC n H 2n+1 N=1 to 10), an alkylhalo group (formula C n H 2n X, n=1-10, x=f, cl, br); r is R 2 The number of the components is 1 to 5;
in the preparation method of the diphenyl sulfone derivative, the sulfide is taken as a photosensitizer and a raw material in a system and is CdS and CdS/A (A is SiO) 2 、TiO 2 、C 3 N 4 One or more than two of CdS is loaded on A, the CdS loading amount in CdS/A is 1wt percent to 40wt percent, preferably 20wt percent to 40wt percent), znS and Zn 2 CdS 3 、ZnIn 2 S 4 、M-ZnIn 2 S 4 (m=ru and or Mn), zn 2 In 2 S 5 、Zn 2 In 2 S 5 B (B is SiO) 2 、TiO 2 、C 3 N 4 One or more of Zn 2 In 2 S 5 B is supported on B, zn 2 In 2 S 5 Zn in/B 2 In 2 S 5 The loading is one or more than two of 1wt% to 40wt%, preferably 20wt% to 40 wt%; in the above preparation method of diphenyl sulfone derivative, the volume ratio (V/V) of acetonitrile to water in acetonitrile aqueous solution is 1:0.1-1:10, preferably 1:0.1-1:0.5, and the dosage of acetonitrile aqueous solution required per millimole of aryl alcohol is 1.0mL-5.0mLPreferably 1.0mL-1.5mL; the oxygen-containing atmosphere comprises air, oxygen or a mixture of one or more of other nitrogen, argon, carbon dioxide and helium and one or more of oxygen, wherein the oxygen volume content is 10-100%, preferably 20-50%.
In the above preparation method of diphenyl sulfone derivative, the light source is one of visible light purple light (390 nm-435 nm), visible light blue light (more than 435nm-490 nm) and visible light green light (more than 490nm-560 nm), preferably visible light blue light source (more than 435nm-490 nm)
In the preparation method of the diphenyl sulfone derivative, the reaction temperature is 0-80 ℃, preferably 25-50 ℃; the reaction time is 0.5 to 24 hours, preferably 3 to 12 hours. In the preparation method of the diphenyl sulfone derivative, the molar ratio of the aryl alcohol to the sulfur element in the catalyst is as follows: 1:0.5-20, preferably 1:0.5 to 4; the molar ratio of the aryl alcohol to the oxygen is as follows: 1:1 to 30, preferably 1:2 to 5; the molar ratio of the aryl alcohol to the ammonia gas is as follows: 1:1 to 30, preferably 1:2 to 5.
The yield of diphenyl sulfone derivative is more than 80%. The preparation system of the diphenyl sulfone derivative has the advantages of wide raw material sources, simple and convenient operation, high reaction activity, safety, environmental protection, simple post-treatment and great industrial application value.
Detailed Description
The present invention will be described in further detail with reference to the following specific embodiments, but the scope of the invention includes, but is not limited to, the following examples, and any modifications made to the details and form of the technical solution of the present invention fall within the scope of the present invention without departing from the meaning and scope of the present application.
Example 1
2-Phenylethanol (20 mmol) and cadmium sulfide (22 mmol) were weighed into a stainless steel reactor, and 24mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 40mmol of ammonia gas was charged, 40mmol of gas was again charged (the mass of the reaction vessel was determined before and after charging), the reaction vessel was placed in a water bath at 30 c, the reaction solution was irradiated with a blue light source at 455nm at 30W,after 12h of reaction, acetonitrile was removed by rotary evaporation, 10mL of deionized water was added, extraction was performed three times with ethyl acetate (20 mL. Times.3), the organic phases were combined and concentrated to give a crude product, and the crude product was purified by a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure diphenyl sulfone with yield of 85%. 1 H NMR(CDCl3,400MHz)δ7.95(d,4H,J＝7.6Hz),7.56(t,2H,J＝7.6Hz),7.50ppm(t,4H,J＝7.6Hz)； 13 C NMR(CDCl3,101MHz)δ141.7,133.3,129.4,127.8ppm。
Comparative example 1
2-Phenylethanol (20 mmol) and sodium sulfide (22 mmol) were weighed into a stainless steel reactor, and 24mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 40mmol of ammonia gas was filled, 40mmol of gas was again filled (the mass of the reaction vessel was determined before and after filling), the reaction vessel was placed in a water bath at 30 ℃, the reaction solution was irradiated with a blue light source at 455nm of 30W, after 12h of reaction, 10mL of deionized water was added after spin evaporation to remove acetonitrile, extraction was performed three times (20 ml×3) with ethyl acetate, the organic phases were combined, concentrated, and analyzed by GC-MS analysis and TLC plate control, and no diphenyl sulfone product was produced.
Comparative example 2
2-Phenylethanol (20 mmol) and cadmium sulfide (22 mmol) were weighed into a stainless steel reactor, and 24mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 40mmol of nitrogen gas was filled, 40mmol of oxygen gas was again filled (the mass of the reaction vessel was determined before and after the filling), the reaction vessel was placed in a water bath at 30 ℃, the reaction solution was irradiated with a blue light source at 455nm of 30W, after 12 hours of reaction, acetonitrile was removed by spin evaporation, 10mL of deionized water was added, extraction was performed three times with ethyl acetate (20 ml×3), the organic phases were combined, and concentrated to give a crude product, and a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure diphenyl sulfone with yield of 10%. 1 H NMR(CDCl3,400MHz)δ7.95(d,4H,J＝7.6Hz),7.56(t,2H,J＝7.6Hz),7.50ppm(t,4H,J＝7.6Hz)； 13 C NMR(CDCl3,101MHz)δ141.7,133.3,129.4,127.8ppm。
Comparative example 3
Weighing and weighing2-Phenylethanol (20 mmol) and cadmium sulfide (22 mmol) were placed in a stainless steel reactor, and 24mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 40mmol of ammonia gas was charged, 80mmol of nitrogen-oxygen mixer gas was charged again (the volume content of oxygen in the mixer was 5%, the mass of the reaction vessel was determined before and after charging), the reaction vessel was placed in a water bath at 30 ℃, the reaction solution was irradiated with a blue light source at 455nm of 30W, after 12 hours of reaction, 10mL of deionized water was added after removal of acetonitrile by spin evaporation, extraction with ethyl acetate was performed three times (20 ml×3), the organic phase was combined, and concentrated to obtain a crude product, and a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure diphenyl sulfone with 20% yield. 1 H NMR(CDCl3,400MHz)δ7.95(d,4H,J＝7.6Hz),7.56(t,2H,J＝7.6Hz),7.50ppm(t,4H,J＝7.6Hz)； 13 C NMR(CDCl3,101MHz)δ141.7,133.3,129.4,127.8ppm。
Comparative example 4
2-Phenylethanol (20 mmol) and cadmium sulfide (22 mmol) were weighed into a stainless steel reactor, and 24mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 10mmol of ammonia gas was charged, 40mmol of gas was charged again (the mass of the reaction vessel was determined before and after charging), the reaction vessel was placed in a water bath at 30 ℃, the reaction solution was irradiated with a blue light source at 455nm of 30W, after 12 hours of reaction, acetonitrile was removed by spin evaporation, 10mL of deionized water was added, extraction was performed three times (20 ml×3) with ethyl acetate, the organic phases were combined, and concentrated to give a crude product, and a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure diphenyl sulfone with yield of 28%. 1 H NMR(CDCl3,400MHz)δ7.95(d,4H,J＝7.6Hz),7.56(t,2H,J＝7.6Hz),7.50ppm(t,4H,J＝7.6Hz)； 13 C NMR(CDCl3,101MHz)δ141.7,133.3,129.4,127.8ppm。
Comparative example 5
2-Phenylethanol (20 mmol) and cadmium sulfide (22 mmol) were weighed into a stainless steel reactor, and 24mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 40mmol of ammonia gas was charged, and 40mmol of oxygen gas was again charged (the mass of the reaction vessel before and after charging determines the gas quality)The amount) was measured, the reaction vessel was placed in a water bath at-10℃and was irradiated with a 30W 455nm blue light source, after 12 hours of reaction, acetonitrile was removed by spin evaporation, 10mL of deionized water was added, extraction was performed three times (20 mL. Times.3) with ethyl acetate, the organic phases were combined, and concentrated to give a crude product, and the crude product was purified by a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure diphenyl sulfone with yield of 18%. 1 H NMR(CDCl3,400MHz)δ7.95(d,4H,J＝7.6Hz),7.56(t,2H,J＝7.6Hz),7.50ppm(t,4H,J＝7.6Hz)； 13 C NMR(CDCl3,101MHz)δ141.7,133.3,129.4,127.8ppm。
Comparative example 6
2-Phenylethanol (20 mmol) and cadmium sulfide (22 mmol) were weighed into a stainless steel reactor, and 10mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 40mmol of ammonia gas was charged, 40mmol of gas was again charged (the mass of the reaction vessel was determined before and after charging), the reaction vessel was placed in a water bath at 30 ℃, the reaction solution was irradiated with a blue light source at 455nm of 30W, after 12 hours of reaction, acetonitrile was removed by spin evaporation, 10mL of deionized water was added, extraction was performed three times (20 ml×3) with ethyl acetate, the organic phases were combined, and concentrated to give a crude product, and a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure diphenyl sulfone with yield of 38%. 1 H NMR(CDCl3,400MHz)δ7.95(d,4H,J＝7.6Hz),7.56(t,2H,J＝7.6Hz),7.50ppm(t,4H,J＝7.6Hz)； 13 C NMR(CDCl3,101MHz)δ141.7,133.3,129.4,127.8ppm。
Example 2
2- (4-methylphenyl) ethanol (20 mmol) and cadmium sulfide (22 mmol) were weighed into a stainless steel reaction vessel, and 24mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 40mmol of ammonia gas was charged, 40mmol of gas was again charged (the mass of the reaction vessel was determined before and after charging), the reaction vessel was placed in a water bath at 30 ℃, the reaction solution was irradiated with a blue light source at 455nm of 30W, after 12 hours of reaction, acetonitrile was removed by spin evaporation, 10mL of deionized water was added, extraction was performed three times (20 ml×3) with ethyl acetate, the organic phases were combined, and concentrated to give a crude product, and a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure 4,4' -dimethyl diphenyl sulfone with yield of 87%. 1 H NMR(CDCl 3 ,400MHz)δ7.79(d,4H,J＝7.9Hz),7.25(d,4H,J＝7.9Hz),2.36ppm(s,6H)； 13 C NMR(CDCl 3 ,101MHz)δ143.9,139.0,129.8,127.5,21.4ppm。
Example 3
4-Chlorophenoxyethanol (20 mmol) and cadmium sulfide (22 mmol) were weighed into a stainless steel reactor, and 24mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 40mmol of ammonia gas was charged, 40mmol of gas was again charged (the mass of the reaction vessel was determined before and after charging), the reaction vessel was placed in a water bath at 30 ℃, the reaction solution was irradiated with a blue light source at 455nm of 30W, after 12 hours of reaction, acetonitrile was removed by spin evaporation, 10mL of deionized water was added, extraction was performed three times (20 ml×3) with ethyl acetate, the organic phases were combined, and concentrated to give a crude product, and a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure 4,4' -dichloro diphenyl sulfone with yield of 81%. 1 H NMR(CDCl 3 ,400MHz)δ7.86(d,4H,J＝7.9Hz),7.48(d,4H,J＝7.9Hz)； 13 C NMR(CDCl 3 ,101MHz)δ140.1,139.8,129.7,129.1ppm。
Example 4
4-Fluorophenethyl alcohol (20 mmol) and cadmium sulfide (22 mmol) were weighed into a stainless steel reaction vessel, and 24mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =3:1), the reaction vessel was closed, 40mmol of ammonia gas was charged, 40mmol of gas was again charged (the mass of the reaction vessel was determined before and after charging), the reaction vessel was placed in a water bath at 50 ℃, the reaction solution was irradiated with a blue light source at 455nm of 30W, after 12 hours of reaction, acetonitrile was removed by spin evaporation, 10mL of deionized water was added, extraction was performed three times (20 ml×3) with ethyl acetate, the organic phases were combined, and concentrated to give a crude product, and a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure 4,4' -difluorodiphenyl sulfone with 82% yield. 1 H NMR(CDCl 3 ,400MHz)δ7.95(d,4H,J＝7.9Hz),7.19(d,4H,J＝7.9Hz)； 13 C NMR(CDCl 3 ,101MHz)δ170.6,160.4,137.7,137.6,130.7,130.3,117.2,116.3ppm。
Example 5
2-Phenylethanol (20 mmol) and Zn were weighed out 2 CdS 3 (15 mmol) was placed in a stainless steel reaction vessel, and 24mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 40mmol of ammonia gas was charged, 40mmol of gas was again charged (the mass of the reaction vessel was determined before and after charging), the reaction vessel was placed in a water bath at 30 ℃, the reaction solution was irradiated with a blue light source at 455nm of 30W, after 12 hours of reaction, acetonitrile was removed by spin evaporation, 10mL of deionized water was added, extraction was performed three times (20 ml×3) with ethyl acetate, the organic phases were combined, and concentrated to give a crude product, and a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure diphenyl sulfone with yield of 90%. 1 H NMR(CDCl3,400MHz)δ7.95(d,4H,J＝7.6Hz),7.56(t,2H,J＝7.6Hz),7.50ppm(t,4H,J＝7.6Hz)； 13 C NMR(CDCl3,101MHz)δ141.7,133.3,129.4,127.8ppm。
Example 6
2-Phenylethanol (20 mmol) and cadmium sulfide (30 mmol) were weighed into a stainless steel reactor, and 24mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 40mmol of ammonia gas was charged, 40mmol of gas was again charged (the mass of the reaction vessel was determined before and after charging), the reaction vessel was placed in a water bath at 30 ℃, the reaction solution was irradiated with a blue light source at 455nm of 30W, after 12 hours of reaction, acetonitrile was removed by spin evaporation, 10mL of deionized water was added, extraction was performed three times (20 ml×3) with ethyl acetate, the organic phases were combined, and concentrated to give a crude product, and a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure diphenyl sulfone with yield of 95%. 1 H NMR(CDCl3,400MHz)δ7.95(d,4H,J＝7.6Hz),7.56(t,2H,J＝7.6Hz),7.50ppm(t,4H,J＝7.6Hz)； 13 C NMR(CDCl3,101MHz)δ141.7,133.3,129.4,127.8ppm。
Example 7
Alpha-methyl phenethyl alcohol (20 mmol) and cadmium sulfide (30 mmol) were weighed into a stainless steel reaction kettle, and 24mL acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 40mmol of ammonia gas was charged, 40mmol of gas was again charged (the mass of the reaction vessel was determined before and after charging), the reaction vessel was placed in a water bath at 30 ℃, the reaction solution was irradiated with a blue light source at 455nm of 30W, after 12 hours of reaction, acetonitrile was removed by spin evaporation, 10mL of deionized water was added, extraction was performed three times (20 ml×3) with ethyl acetate, the organic phases were combined, and concentrated to give a crude product, and a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure diphenyl sulfone with 93% yield. 1 H NMR(CDCl3,400MHz)δ7.95(d,4H,J＝7.6Hz),7.56(t,2H,J＝7.6Hz),7.50ppm(t,4H,J＝7.6Hz)； 13 C NMR(CDCl3,101MHz)δ141.7,133.3,129.4,127.8ppm。
Example 8
Alpha-methylphenylethanol (20 mmol) and ZnIn were weighed out 2 S 4 (7.5 mmol) was placed in a stainless steel reaction vessel, and 24mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 40mmol of ammonia gas was charged, 40mmol of gas was again charged (the mass of the reaction vessel was determined before and after charging), the reaction vessel was placed in a water bath at 30 ℃, the reaction solution was irradiated with a blue light source at 455nm of 30W, after 12 hours of reaction, acetonitrile was removed by spin evaporation, 10mL of deionized water was added, extraction was performed three times (20 ml×3) with ethyl acetate, the organic phases were combined, and concentrated to give a crude product, and a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure diphenyl sulfone with yield of 88%. 1 H NMR(CDCl3,400MHz)δ7.95(d,4H,J＝7.6Hz),7.56(t,2H,J＝7.6Hz),7.50ppm(t,4H,J＝7.6Hz)； 13 C NMR(CDCl3,101MHz)δ141.7,133.3,129.4,127.8ppm。
Example 9
Alpha-methylphenylethanol (20 mmol) and Zn were weighed out 2 In 2 S 5 /SiO 2 40 (7.8 g, 30mmol containing sulfur) was placed in a stainless steel reaction vessel and 24mL of acetonitrile in water (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 40mmmol of ammonia gas was charged, 40mol of gas was again charged (the mass of the reaction vessel before and after charging determines the mass of the gas), the reaction vessel was placed in a water bath at 30 ℃, and a blue light source at 455nm at 30W was used to irradiate the reaction vesselThe reaction solution was reacted for 12 hours, then solid particles were removed by filtration, acetonitrile was removed by rotary evaporation, 10mL of deionized water was added, extraction was performed three times with ethyl acetate (20 mL. Times.3), the organic phases were combined, and then the mixture was concentrated to obtain a crude product, and the crude product was purified by a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure diphenyl sulfone with 93% yield. 1 H NMR (CDCl3,400MHz)δ7.95(d,4H,J＝7.6Hz),7.56(t,2H,J＝7.6Hz),7.50ppm(t,4H,J＝7.6Hz)； 13 C NMR(CDCl3,101MHz)δ141.7,133.3,129.4,127.8ppm。
Example 10
Alpha-methyl phenethyl alcohol (20 mmol) and ZnS (30 mmol) were weighed into a stainless steel reaction vessel, and 24mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 40mmol of ammonia gas was charged, 40mmol of gas was again charged (the mass of the reaction vessel was determined before and after charging), the reaction vessel was placed in a water bath at 30 ℃, the reaction solution was irradiated with a blue light source at 455nm of 30W, after 12 hours of reaction, acetonitrile was removed by spin evaporation, 10mL of deionized water was added, extraction was performed three times (20 ml×3) with ethyl acetate, the organic phases were combined, and concentrated to give a crude product, and a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure diphenyl sulfone with yield of 81%. 1 H NMR(CDCl3,400MHz)δ7.95(d,4H,J＝7.6Hz),7.56(t,2H,J＝7.6Hz),7.50ppm(t,4H,J＝7.6Hz)； 13 C NMR(CDCl3,101MHz)δ141.7,133.3,129.4,127.8ppm。
Example 11
1- (4-chlorophenyl) ethanol (20 mmol) and CdS (30 mmol) were weighed into a stainless steel reaction vessel, and 24mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 40mmol of ammonia gas was charged, 40mmol of gas was again charged (the mass of the reaction vessel was determined before and after charging), the reaction vessel was placed in a water bath at 30 ℃, the reaction solution was irradiated with a blue light source at 455nm of 30W, after 12 hours of reaction, acetonitrile was removed by spin evaporation, 10mL of deionized water was added, extraction was performed three times (20 ml×3) with ethyl acetate, the organic phases were combined, and concentrated to give a crude product, and a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) is recrystallized twice, finally obtaining4,4' -dichloro diphenyl sulfone, yield 88%. 1 H NMR(CDCl 3 ,400MHz)δ7.86(d,4H,J＝7.9Hz),7.48(d,4H,J＝7.9Hz)； 13 C NMR(CDCl 3 ,101MHz)δ140.1,139.8,129.7,129.1ppm。
Example 12
1- (4-chlorophenyl) ethanol (20 mmol) and CdS (30 mmol) were weighed into a stainless steel reaction vessel, and 24mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 40mmol of ammonia gas was charged, 40mmol of gas was again charged (the mass of the reaction vessel was determined before and after charging), the reaction vessel was placed in a water bath at 30 ℃, the reaction solution was irradiated with a blue light source at 455nm of 30W, after 24 hours of reaction, acetonitrile was removed by spin evaporation, 10mL of deionized water was added, extraction was performed three times with ethyl acetate (20 ml×3), the organic phases were combined, and concentrated to give a crude product, and a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) was recrystallized twice to finally yield 4,4' -dichlorodiphenyl sulfone in 95% yield. 1 H NMR(CDCl 3 ,400MHz)δ7.86(d,4H,J＝7.9Hz),7.48(d,4H,J＝7.9Hz)； 13 C NMR(CDCl 3 ,101MHz)δ140.1,139.8,129.7,129.1ppm。
Example 13
1- (4-methylphenyl) -1-ethanol (20 mmol) and CdS (30 mmol) were weighed into a stainless steel reaction vessel, and 24mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 40mmol of ammonia gas was charged, 40mmol of gas was again charged (the mass of the reaction vessel was determined before and after charging), the reaction vessel was placed in a water bath at 30 ℃, the reaction solution was irradiated with a blue light source at 455nm of 30W, after 24 hours of reaction, acetonitrile was removed by spin evaporation, 10mL of deionized water was added, extraction was performed three times with ethyl acetate (20 ml×3), the organic phases were combined, and concentrated to give a crude product, and a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) was recrystallized twice to finally yield 4,4' -dimethyldiphenyl sulfone with a yield of 93%. 1 HNMR(CDCl 3 ,400MHz)δ7.79(d,4H,J＝7.9Hz),7.25(d,4H,J＝7.9Hz),2.36ppm(s,6H)； 13 C NMR(CDCl 3 ,101MHz)δ143.9,139.0,129.8,127.5,21.4ppm。
Example 14
2-Phenylethanol (20 mmol) and cadmium sulfide (22 mmol) were weighed into a stainless steel reactor, and 20mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =2:1), the reaction vessel was closed, 40mmol of ammonia gas was charged, 40mmol of gas was again charged (the mass of the reaction vessel was determined before and after charging), the reaction vessel was placed in a water bath at 30 ℃, the reaction solution was irradiated with a blue light source at 455nm of 30W, after 12 hours of reaction, acetonitrile was removed by spin evaporation, 10mL of deionized water was added, extraction was performed three times with ethyl acetate (20 ml×3), the organic phases were combined, and concentrated to give a crude product, and a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure diphenyl sulfone with yield of 83%. 1 H NMR(CDCl3,400MHz)δ7.95(d,4H,J＝7.6Hz),7.56(t,2H,J＝7.6Hz),7.50ppm(t,4H,J＝7.6Hz)； 13 C NMR(CDCl3,101MHz)δ141.7,133.3,129.4,127.8ppm。
Example 15
2-Phenylethanol (20 mmol) and cadmium sulfide (22 mmol) were weighed into a stainless steel reactor, and 40mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 40mmol of ammonia gas was charged, 40mmol of gas was again charged (the mass of the reaction vessel was determined before and after charging), the reaction vessel was placed in a water bath at 30 ℃, the reaction solution was irradiated with a blue light source at 455nm of 30W, after 12 hours of reaction, acetonitrile was removed by spin evaporation, 10mL of deionized water was added, extraction was performed three times (20 ml×3) with ethyl acetate, the organic phases were combined, and concentrated to give a crude product, and a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure diphenyl sulfone with yield of 75%. 1 H NMR(CDCl3,400MHz)δ7.95(d,4H,J＝7.6Hz),7.56(t,2H,J＝7.6Hz),7.50ppm(t,4H,J＝7.6Hz)； 13 C NMR(CDCl3,101MHz)δ141.7,133.3,129.4,127.8ppm。
Example 16
2-Phenylethanol (20 mmol) and cadmium sulfide (22 mmol) were weighed into a stainless steel reactor, and 24mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 40mmol of ammonia gas was charged, 80mmol of gas was again charged (the mass of the reaction vessel was determined before and after charging), and the reaction vessel was subjected to the reactionPlacing the kettle in 30deg.C water bath, irradiating the reaction solution with 30W 455nm blue light source, reacting for 12 hr, removing acetonitrile by rotary evaporation, adding 10mL deionized water, extracting with ethyl acetate three times (20 mL×3), mixing the organic phases, concentrating to obtain crude product, mixing with ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure diphenyl sulfone with yield of 90%. 1 H NMR(CDCl3,400MHz)δ7.95(d,4H,J＝7.6Hz),7.56(t,2H,J＝7.6Hz),7.50ppm(t,4H,J＝7.6Hz)； 13 C NMR(CDCl3,101MHz)δ141.7,133.3,129.4,127.8ppm。
Example 17
2-Phenylethanol (20 mmol) and cadmium sulfide (22 mmol) were weighed into a stainless steel reactor, and 24mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 40mmol of ammonia gas was charged, 40mmol of gas was again charged (the mass of the reaction vessel was determined before and after charging), the reaction vessel was placed in a water bath at 30 ℃, the reaction solution was irradiated with a 390nm violet light source at 30W, after 12 hours of reaction, acetonitrile was removed by rotary evaporation, 10mL of deionized water was added, extraction was performed three times (20 ml×3) with ethyl acetate, the organic phase was combined, and concentrated to give a crude product, and a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure diphenyl sulfone with yield of 81%. 1 H NMR(CDCl3,400MHz)δ7.95(d,4H,J＝7.6Hz),7.56(t,2H,J＝7.6Hz),7.50ppm(t,4H,J＝7.6Hz)； 13 C NMR(CDCl3,101MHz)δ141.7,133.3,129.4,127.8ppm。
Example 18
2-Phenylethanol (20 mmol) and cadmium sulfide (10 mmol) were weighed into a stainless steel reactor, and 24mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 40mmol of ammonia gas was charged, 40mmol of gas was again charged (the mass of the reaction vessel was determined before and after charging), the reaction vessel was placed in a water bath at 30 ℃, the reaction solution was irradiated with a blue light source at 455nm of 30W, after 12 hours of reaction, acetonitrile was removed by spin evaporation, 10mL of deionized water was added, extraction was performed three times (20 ml×3) with ethyl acetate, the organic phases were combined, and concentrated to give a crude product, and a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure diphenyl sulfone with yield of 72%. 1 H NMR(CDCl3,400MHz)δ7.95(d,4H,J＝7.6Hz),7.56(t,2H,J＝7.6Hz),7.50ppm(t,4H,J＝7.6Hz)； 13 C NMR(CDCl3,101MHz)δ141.7,133.3,129.4,127.8ppm。
Example 19
2-Phenylethanol (20 mmol) and cadmium sulfide (22 mmol) were weighed into a stainless steel reactor, and 24mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 60mmol of ammonia gas was charged, 40mmol of gas was charged again (the mass of the reaction vessel was determined before and after charging), the reaction vessel was placed in a water bath at 30 ℃, the reaction solution was irradiated with a blue light source at 455nm of 30W, after 12 hours of reaction, acetonitrile was removed by spin evaporation, 10mL of deionized water was added, extraction was performed three times (20 ml×3) with ethyl acetate, the organic phases were combined, and concentrated to give a crude product, and a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure diphenyl sulfone with 92% yield. 1 H NMR(CDCl3,400MHz)δ7.95(d,4H,J＝7.6Hz),7.56(t,2H,J＝7.6Hz),7.50ppm(t,4H,J＝7.6Hz)； 13 C NMR(CDCl3,101MHz)δ141.7,133.3,129.4,127.8ppm。
Example 20
2-Phenylethanol (20 mmol) and cadmium sulfide (22 mmol) were weighed into a stainless steel reactor, and 24mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 40mmol of ammonia gas was filled, 100mmol of air was further filled (the mass of the reaction vessel was determined before and after the filling), the reaction vessel was placed in a water bath at 30 ℃, the reaction solution was irradiated with a blue light source at 455nm of 30W, after 12 hours of reaction, acetonitrile was removed by spin evaporation, 10mL of deionized water was added, extraction was performed three times with ethyl acetate (20 ml×3), the organic phases were combined, and concentrated to give a crude product, and a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure diphenyl sulfone with 82% yield. 1 H NMR(CDCl3,400MHz)δ7.95(d,4H,J＝7.6Hz),7.56(t,2H,J＝7.6Hz),7.50ppm(t,4H,J＝7.6Hz)； 13 C NMR(CDCl3,101MHz)δ141.7,133.3,129.4,127.8ppm。
Example 21
2-Phenylethanol (20 mmol) and cadmium sulfide (22 mmol) were weighed into a stainless steel reactor, and 24mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 40mmol of ammonia gas was charged, 50mmol of nitrogen-oxygen mixer gas was charged again (the volume content of oxygen in the mixer was 50%, the mass of the reaction vessel was determined before and after charging), the reaction vessel was placed in a water bath at 30 ℃, the reaction solution was irradiated with a blue light source of 455nm at 30W, after 12 hours of reaction, 10mL of deionized water was added after removal of acetonitrile by spin evaporation, extraction with ethyl acetate was performed three times (20 ml×3), the organic phase was combined, and concentrated to obtain a crude product, and a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure diphenyl sulfone with yield of 72%. 1 H NMR(CDCl3,400MHz)δ7.95(d,4H,J＝7.6Hz),7.56(t,2H,J＝7.6Hz),7.50ppm(t,4H,J＝7.6Hz)； 13 C NMR(CDCl3,101MHz)δ141.7,133.3,129.4,127.8ppm。
Example 22
2-Phenylethanol (20 mmol) and cadmium sulfide (22 mmol) were weighed into a stainless steel reactor, and 24mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 40mmol of ammonia gas was charged, 40mmol of gas was again charged (the mass of the reaction vessel was determined before and after charging), the reaction vessel was placed in a water bath at 50 ℃, the reaction solution was irradiated with a blue light source at 455nm of 30W, after 12 hours of reaction, acetonitrile was removed by spin evaporation, 10mL of deionized water was added, extraction was performed three times (20 ml×3) with ethyl acetate, the organic phases were combined, and concentrated to give a crude product, and a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure diphenyl sulfone with 89% yield. 1 H NMR(CDCl3,400MHz)δ7.95(d,4H,J＝7.6Hz),7.56(t,2H,J＝7.6Hz),7.50ppm(t,4H,J＝7.6Hz)； 13 C NMR(CDCl3,101MHz)δ141.7,133.3,129.4,127.8ppm。
Example 23
Weighing 4-methylbenzyl alcohol (20 mmol) and Zn 2 In 2 S 5 /C 3 N 4 20 (15.6 g, 30mmol containing sulfur) was placed in a stainless steel reaction vessel, and 24mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 30mmmol of ammonia gas was charged, 40mol of gas was charged again (the mass of the reaction vessel was determined before and after charging), the reaction vessel was placed in a water bath at 30 ℃, the reaction solution was irradiated with a blue light source at 455nm of 30W, after 12 hours of reaction, solid particles were filtered off, acetonitrile was removed by spin evaporation, 10mL of deionized water was added, extraction with ethyl acetate was performed three times (20 ml×3), the organic phase was combined, and concentrated to obtain a crude product, and a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) was recrystallized twice to finally yield 4,4' -dimethyldiphenyl sulfone in 90.5% yield. 1 H NMR(CDCl3,400MHz)δ7.95(d,4H,J＝7.6Hz),7.56(t,2H,J＝7.6Hz),7.50ppm(t,4H,J＝7.6Hz)； 13 C NMR(CDCl3,101MHz)δ141.7,133.3,129.4,127.8ppm。
Example 24
Weighing 4-chloromethyl phenethyl alcohol (20 mmol) and CdS/TiO 2 40 (containing 40mmol of sulfur) was placed in a stainless steel reaction vessel, and 24mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 30mmmol of ammonia gas was charged, 40mol of gas was charged again (the mass of the reaction vessel was determined before and after charging), the reaction vessel was placed in a water bath at 30 ℃, the reaction solution was irradiated with a blue light source at 455nm of 30W, after 12 hours of reaction, solid particles were filtered off, acetonitrile was removed by spin evaporation, 10mL of deionized water was added, extraction with ethyl acetate was performed three times (20 ml×3), the organic phase was combined, and concentrated to obtain a crude product, and a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure 4,4' -dichloro methyl diphenyl sulfone with yield of 93%. 1 H NMR(CDCl3,400MHz)δ7.84(d,4H,J＝7.5Hz),7.45(d,4H,J＝7.5Hz),4.64(s,4H)； 13 C NMR(CDCl3,101MHz)δ46.2,128.5,129.6,141.4,142.8ppm。
Example 25
Weighing 4-methylbenzyl alcohol (20 mmol) and Ru-ZnIn 2 S 4 (containing 15mmol of sulfur) was placed in a stainless steel reaction vessel, and 24mL of an aqueous acetonitrile solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 30mmmol of ammonia gas was charged, 40mol of gas was again charged (the mass of the reaction vessel was determined to be the mass of the gas before and after charging), and the reaction vessel was placed at 3Irradiating the reaction solution with 30W 455nm blue light source in water bath at 0deg.C, reacting for 12 hr, filtering to remove solid particles, rotary evaporating to remove acetonitrile, adding 10mL deionized water, extracting with ethyl acetate three times (20 mL×3), mixing the organic phases, concentrating to obtain crude product, mixing with ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure 4,4' -dimethyl diphenyl sulfone with yield of 96.6%. 1 H NMR(CDCl3,400MHz)δ7.95(d,4H,J＝7.6Hz),7.56(t,2H,J＝7.6Hz),7.50ppm(t,4H,J＝7.6Hz)； 13 C NMR(CDCl3,101MHz)δ141.7,133.3,129.4,127.8ppm。
Example 26
1- (4-chloromethylphenyl) -1-ethanol (20 mmol) and ZnS (30 mmol) were weighed into a stainless steel reactor, and 24mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 30mmmol of ammonia gas was filled, 40mol of gas was again filled (the mass of the reaction vessel was determined before and after filling), the reaction vessel was placed in a water bath at 30 ℃, the reaction solution was irradiated with a 390nm violet light source at 30W, after 12 hours of reaction, solid particles were filtered off, acetonitrile was removed by spin evaporation, 10mL of deionized water was added, extraction with ethyl acetate was performed three times (20 ml×3), the organic phase was combined, and concentrated to obtain a crude product, and a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure 4,4' -dichloro methyl diphenyl sulfone with yield of 95.2%. 1 H NMR(CDCl 3 ,400MHz)δ7.86(d,4H,J＝7.9Hz),7.48(d,4H,J＝7.9Hz)； 13 C NMR(CDCl 3 ,101MHz)δ140.1,139.8,129.7,129.1ppm。
Example 27
Weighing 4-methoxybenzyl alcohol (20 mmol) and Mn-ZnIn 2 S 4 (containing 12mmol of sulfur) was placed in a stainless steel reaction vessel, and 24mL of an aqueous acetonitrile solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 30mmmol of ammonia gas was charged, 40mol of gas was charged again (the mass of the reaction vessel was determined before and after charging), the reaction vessel was placed in a water bath at 30 ℃, the reaction solution was irradiated with a blue light source at 455nm of 30W, after 12 hours of reaction, solid particles were removed by filtration, acetonitrile was removed by rotary evaporation, 10mL of deionized water was added, and acetic acid was addedExtracting with ethyl ester three times (20 mL. Times.3), mixing the organic phases, concentrating to obtain crude product, and mixing with ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure 4,4' -dimethoxy diphenyl sulfone with yield of 92.6%. 1 H NMR(DMSO-d6,400MHz)δ7.13(d,4H,J＝7.6Hz),6.72(d,4H,J＝7.6Hz),2.49(s,6H)ppm； 13 C NMR(DMSO-d6,101MHz)δ164.5,118.4,130.5,137.4ppm。
Example 28
1- (4-methoxyphenyl) -1-ethanol (20 mmol) and CdS/SiO were weighed out 2 30 (30 mmol containing sulfur) was placed in a stainless steel reaction vessel, and 24mL of acetonitrile aqueous solution (V Acetonitrile /V Water and its preparation method =5:1), the reaction vessel was closed, 30mmmol of ammonia gas was charged, 40mol of gas was charged again (the mass of the reaction vessel was determined before and after charging), the reaction vessel was placed in a water bath at 30 ℃, the reaction solution was irradiated with a blue light source at 455nm of 30W, after 12 hours of reaction, solid particles were filtered off, acetonitrile was removed by spin evaporation, 10mL of deionized water was added, extraction with ethyl acetate was performed three times (20 ml×3), the organic phase was combined, and concentrated to obtain a crude product, and a mixture of ethanol and deionized water (V Ethanol ：V Water and its preparation method =9:1) and re-crystallizing twice to obtain pure 4,4' -dimethoxy diphenyl sulfone with yield of 95.6%. 1 H NMR(DMSO-d6,400MHz)δ7.13(d,4H,J＝7.6Hz),6.72(d,4H,J＝7.6Hz),2.49(s,6H)ppm； 13 C NMR(DMSO-d6,101MHz)δ164.5,118.4,130.5,137.4ppm。
Claims (7)
1. A preparation method of diphenyl sulfone derivative is characterized in that,
aryl alcohol and photosensitive sulfide are used as raw materials, acetonitrile aqueous solution is used as a solvent, and under the action of ammonia gas and oxygen-containing atmosphere, the reaction is carried out for 0.5 to 24 hours at the temperature of 0 to 80 ℃ under the illumination, and the diphenyl sulfone derivative is prepared in one step;
the aryl alcohol is one or more than two of aryl primary alcohol or aryl secondary alcohol; the ratio of the amount of sulfur and aryl alcohol in the photosensitive sulfide in the reaction system is (0.5-20): 1.
2. A process for producing a diphenyl sulfone derivative as defined in claim 1, wherein,
the aryl primary alcohol compound is one or more than two of the following compounds, wherein R is 1 Halogen (F, cl, br), alkyl (formula C) n H 2n+1 N=1 to 10), alkoxy (formula OC n H 2n+1 N=1 to 10), an alkylhalo group (formula C n H 2n X, n=1-10, x=f, cl, br); m represents the number of carbon atoms, m=1-2; r is R 1 The number of the components is 1 to 5;
the aryl secondary alcohol compound is one or more than two of the following compounds, wherein R is 2 Halogen (F, cl, br), alkyl (formula C) n H 2n+1 N=1 to 10), alkoxy (formula OC n H 2n+1 N=1 to 10), an alkylhalo group (formula C n H 2n X, n=1-10, x=f, cl, br); r is R 2 The number of the components is 1 to 5;
3. a process for producing a diphenyl sulfone derivative as defined in claim 1, wherein,
the sulfide is used as both photosensitizer and raw material in the system and is selected from CdS and CdS/A (A is selected from SiO 2 、TiO 2 、C 3 N 4 One or more than two of CdS is loaded on A, the CdS loading amount in CdS/A is 1wt percent to 40wt percent, preferably 20wt percent to 40wt percent), znS and Zn 2 CdS 3 、ZnIn 2 S 4 、M-ZnIn 2 S 4 (m=ru and/or Mn), zn 2 In 2 S 5 、Zn 2 In 2 S 5 B (B is selected from SiO 2 、TiO 2 、C 3 N 4 One or more of Zn 2 In 2 S 5 B is supported on B, zn 2 In 2 S 5 Zn in/B 2 In 2 S 5 The loading is one or more than two of 1wt% to 40wt%, preferably 20wt% to 40 wt%.
4. A process for producing a diphenyl sulfone derivative as defined in claim 1, wherein,
the volume ratio (V/V) of acetonitrile to water in the acetonitrile aqueous solution is 1:0.1-1:10, preferably 1:0.1-1:0.5, and the dosage of the acetonitrile aqueous solution required for every millimole of aryl alcohol is 1.0mL-5.0mL, preferably 1.0mL-1.5mL;
the oxygen-containing atmosphere comprises air, oxygen or a mixture of one or more of other nitrogen, argon, carbon dioxide and helium and one or more of oxygen, wherein the oxygen volume content is 10-100%, preferably 20-50%.
5. The method for producing a diphenyl sulfone derivative as set forth in claim 1, characterized in that:
the light source is one of visible light purple light (390 nm-435 nm), visible light blue light (more than 435nm-490 nm) and visible light green light (more than 490nm-560 nm), preferably visible light blue light source (more than 435nm-490 nm).
6. The method for producing a diphenyl sulfone derivative as set forth in claim 1, characterized in that:
the reaction temperature is 0-80 ℃, preferably 25-50 ℃;
the reaction time is 0.5 to 24 hours, preferably 3 to 12 hours.
7. A process for producing a diphenyl sulfone derivative as set forth in claim 1 or 4, characterized in that,
the molar ratio of the aryl alcohol to the sulfur element in the catalyst is as follows: 1:0.5-20, preferably 1:0.5 to 4;
the molar ratio of the aryl alcohol to oxygen in the oxygen-containing atmosphere is as follows: 1:1 to 30, preferably 1:2 to 5;
the molar ratio of the aryl alcohol to the ammonia gas is as follows: 1:1 to 30, preferably 1:2 to 5.
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