CN114591207A - Synthetic method of naphthenic base aryl thioether compound - Google Patents
Synthetic method of naphthenic base aryl thioether compound Download PDFInfo
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- CN114591207A CN114591207A CN202210239915.2A CN202210239915A CN114591207A CN 114591207 A CN114591207 A CN 114591207A CN 202210239915 A CN202210239915 A CN 202210239915A CN 114591207 A CN114591207 A CN 114591207A
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- catalyst
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- naphthenic base
- led lamp
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- 150000004832 aryl thioethers Chemical class 0.000 title claims abstract description 8
- 238000010189 synthetic method Methods 0.000 title claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- VJRITMATACIYAF-UHFFFAOYSA-N benzenesulfonohydrazide Chemical class NNS(=O)(=O)C1=CC=CC=C1 VJRITMATACIYAF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 230000004913 activation Effects 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 48
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 9
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 8
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 8
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 7
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 7
- 150000001924 cycloalkanes Chemical class 0.000 claims description 6
- 239000004914 cyclooctane Substances 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 claims description 3
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910021590 Copper(II) bromide Inorganic materials 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(II) bromide Substances [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- LMGZGXSXHCMSAA-UHFFFAOYSA-N cyclodecane Chemical compound C1CCCCCCCCC1 LMGZGXSXHCMSAA-UHFFFAOYSA-N 0.000 claims description 2
- GPTJTTCOVDDHER-UHFFFAOYSA-N cyclononane Chemical compound C1CCCCCCCC1 GPTJTTCOVDDHER-UHFFFAOYSA-N 0.000 claims description 2
- KYTNZWVKKKJXFS-UHFFFAOYSA-N cycloundecane Chemical compound C1CCCCCCCCCC1 KYTNZWVKKKJXFS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 40
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 10
- 238000012512 characterization method Methods 0.000 description 10
- 238000004440 column chromatography Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000012044 organic layer Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- -1 cycloalkylaryl sulfides Chemical class 0.000 description 4
- LWSWHXZQBIFYLZ-UHFFFAOYSA-N cyclohexylsulfanylbenzene Chemical compound C1CCCCC1SC1=CC=CC=C1 LWSWHXZQBIFYLZ-UHFFFAOYSA-N 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- UIWFWZLAICURGT-UHFFFAOYSA-N 4-Methoxybenzenesulfonohydrazide Chemical compound COC1=CC=C(S(=O)(=O)NN)C=C1 UIWFWZLAICURGT-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 125000004367 cycloalkylaryl group Chemical group 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- DJYQZQAOJUWOCX-UHFFFAOYSA-N 1-chloro-4-cyclohexylsulfanylbenzene Chemical compound C1=CC(Cl)=CC=C1SC1CCCCC1 DJYQZQAOJUWOCX-UHFFFAOYSA-N 0.000 description 1
- PAGDATIJJABJDZ-UHFFFAOYSA-N 1-cyclohexylsulfanyl-4-methoxybenzene Chemical compound C1=CC(OC)=CC=C1SC1CCCCC1 PAGDATIJJABJDZ-UHFFFAOYSA-N 0.000 description 1
- GXOJPYYZNHTODC-UHFFFAOYSA-N 1-cyclohexylsulfanyl-4-methylbenzene Chemical compound C1=CC(C)=CC=C1SC1CCCCC1 GXOJPYYZNHTODC-UHFFFAOYSA-N 0.000 description 1
- RWSRMWXKMKGWQZ-UHFFFAOYSA-N 1-cyclohexylsulfanyl-4-nitrobenzene Chemical compound C1=CC([N+](=O)[O-])=CC=C1SC1CCCCC1 RWSRMWXKMKGWQZ-UHFFFAOYSA-N 0.000 description 1
- LCVVGGBBIXUXSZ-UHFFFAOYSA-N 1-cyclopentylsulfanyl-4-methoxybenzene Chemical compound C1=CC(OC)=CC=C1SC1CCCC1 LCVVGGBBIXUXSZ-UHFFFAOYSA-N 0.000 description 1
- HFPYBIDKCVNOMY-UHFFFAOYSA-N 1-cyclopentylsulfanyl-4-methylbenzene Chemical compound C1=CC(C)=CC=C1SC1CCCC1 HFPYBIDKCVNOMY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000010499 C–H functionalization reaction Methods 0.000 description 1
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
- C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a synthetic method of naphthenic base aryl thioether. Substituted benzene sulfonyl hydrazide and cyclane are used as raw materials, cheap metal is used as a catalyst, and C-H bond activation is carried out at a certain temperature under the irradiation of an LED lamp in an oxygen atmosphere to synthesize the naphthenic base aryl thioether. The method has the advantages of easily obtained raw material cycloparaffin, cheap metal catalyst and green, simple and convenient photocatalysis method.
Description
Technical Field
The invention relates to a synthetic method of naphthenic base aryl thioether compounds, in particular to a synthetic method for constructing naphthenic base aryl thioether by utilizing C-H bond activation reaction of aryl sulfonyl hydrazide and cyclane under the catalysis of cheap metal under the photocatalysis.
Background
Sulfur-containing compounds play an important role in chemical engineering, medicine, biology and the like, so the development of the C-S bond construction method has important significance for promoting organic synthesis, medicine synthesis and new material preparation. The traditional C-S bond is constructed by either metal-catalyzed cross-coupling reactions or nucleophilic substitution reactions, which can be carried out by relatively expensive halocarbons prepared in advance (Yamada, T.; Hashimoto Y.; Tanaka III K.; Morita N.; Tamura, O.J. Org. chem.2020,85(19), 12315). The preparation of cycloalkylaryl sulfides by decarboxylation of aliphatic hydrocarbon carboxylic acids and radical reaction of thiophenols has also been developed in recent years (Zhuang, y.; Qu, j.; Kang, y.j. org. chem.2020,85(6),4386.Cai, y.; Nie, f.; Song, q.j. org. chem.2021,86(17), 12419.). C-H bond activation reaction has been advanced in recent years, and the construction of a C-S bond by C-H bond activation has also attracted attention. For example, the direct reaction of thiophenol and cyclohexane to produce cyclohexyl phenyl sulfide (Tatsuhiro, U.; Yurina, H.; Kazushi, T.; Takahiko, A.ACS Organic & Inorganic Au 2021,1, (1),23), the reaction of phenyl disulfide and cyclohexane under the action of peroxide to produce cyclohexyl phenyl sulfide (ZHao, J.; Fang, H.; Han, J.; Pan, Y.; Li, G.Adv Synth & Cat, 2014,356,2719), the reaction of arylsulfonylhydrazide and cycloalkane under the action of palladium catalysis at 120 ℃ to form cycloalkyl aryl sulfide (Guo, S.; He, W.; Xiang, J.; Yuan, Y.Chem.Comm.2014,50,8578.) is a green reaction process, which avoids the production of by-products as compared to the high-temperature heating reaction. The present patent will utilize a green process to synthesize the cycloalkyl aryl sulfide.
Disclosure of Invention
The invention aims to solve the problem of providing a novel method for synthesizing naphthenic base aryl thioether, which has easily obtained raw material naphthenic hydrocarbon, cheap metal catalyst, and simple, convenient and green by using a photocatalysis method.
The applicant intends to show that the technical solution of the present invention is accomplished under the funding of basic equity research project (LY18B020003) in zhejiang province, which herein means thank you.
The synthesis method takes substituted benzenesulfonyl hydrazide and cycloalkane as raw materials, takes cheap metal as a catalyst, and generates C-H bond activation at a certain temperature under the irradiation of an LED lamp in an oxygen atmosphere to synthesize the cycloalkyl aryl thioether, and the specific reaction formula is as follows:
preferably, the above reaction formula is substituted benzenesulfonyl hydrazide where R ═ hydrogen, halogen, alkoxy, nitro, cyano, C1-C6And the R substituent group is at any position of the ortho, meta and para of the sulfonyl.
Preferably, the above formula cycloalkane, n ═ 1 to 8, includes cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, and cyclododecane.
Preferably, the catalyst is copper catalyst selected from the group consisting of CuCl and the like2、CuBr2CuO, CuBr and CuCl, and the amount of the catalyst is 1-20%.
Preferably, the ratio of substituted benzenesulfonyl hydrazide to cycloalkane is from 1:5 to 1:30.
Preferably, the wavelength of the Led lamp is 400-480nm, and the power of the Led lamp is 3-60W.
Preferably, the reaction temperature is 30-60 ℃.
Preferably, the reaction time is 5 to 24 hours.
The invention provides a simple and convenient green reaction method for synthesizing cycloalkyl aryl thioether. The reaction directly reacts with cyclane for C-H activation reaction under oxygen atmosphere and by means of light irradiation, and the reaction yield reaches 40-95%.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1: to a dry Schlenk reaction tube were added a stirring magneton, p-methylbenzenesulfonylhydrazide (95.68mg,0.5mmol), cyclopentane (5.0mmol), and CuBr (0.05 mmol). The reaction tube was evacuated and filled with oxygen, sealed, placed in a glass dish wrapped with 12w Led lamp (420-. After completion of the reaction, the mixture was extracted with dichloromethane three times, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. And (5) separating and purifying by using column chromatography to obtain the product 1 with the yield of 74%. The structure and characterization data are as follows:
1-cyclopentylsulfanyl-4-methyl-benzene(1)
1H NMR(400MHz,CDCl3)δ7.37(d,J＝7.9Hz,2H),7.18(d,J＝7.6Hz,2H),3.62(s,1H),2.41(s,3H),2.09(s,2H),1.79(s,2H),1.67-1.60(m,4H)；13C NMR(101MHz,CDCl3)δ136.1,133.2,130.9,129.6,46.6,33.5,24.7,21.1ppm.
example 2: to a dry Schlenk reaction tube were added a stirring magneton, p-methylbenzenesulfonylhydrazide (95.68mg,0.5mmol), cyclohexane (5.0mmol), and CuCl (0.05 mmol). The reaction tube was evacuated and filled with oxygen, sealed, placed in a glass dish wrapped with 12w Led (420-. After completion of the reaction, the mixture was extracted with dichloromethane three times, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. And (5) separating and purifying by using column chromatography to obtain the product 2 with the yield of 82%. The structure and characterization data are as follows:
1-cyclohexylsulfanyl-4-methyl-benzene(2)
1H NMR(400MHz,CDCl3)δ7.32(d,J＝8.0Hz,2H),7.10(d,J＝7.9Hz,2H),3.02(s,1H),2.33(s,3H),1.97(d,J＝10.4Hz,2H),1.77(dd,J＝5.9,4.2Hz,2H),1.62-1.58(m,1H)，1.39-1.22(m,5H)；13C NMR(101MHz,CDCl3)δ136.8,132.8,131.2,129.5,47.1,33.4,26.1,25.8,21.1ppm.
example 3: to a dry Schlenk reaction tube, a stirring magneton, p-methylbenzenesulfonylhydrazide (95.68mg,0.5mmol), cycloheptane (3.0mmol), and CuBr (0.1mmol) were added. Vacuumizing and filling oxygen into the reaction tube, sealing, placing the reaction tube in a glass dish wrapped by 18w Led (420-. After completion of the reaction, the mixture was extracted with dichloromethane three times, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. And (5) separating and purifying by using column chromatography to obtain the product 3 with the yield of 75%. The structure and characterization data are as follows:
p-tolylsulfanyl-cycloheptane(3)
1H NMR(400MHz,CDCl3)δ7.29(d,J＝8.1Hz,2H),7.10(d,J＝7.9Hz,2H),3.26(s,1H),2.33(s,3H),2.00(dd,J＝8.6,5.4Hz,2H),1.76-1.67(m,2H),1.60–1.51(m,2H)；1.49-1.38(m,6H)；13C NMR(101MHz,CDCl3)δ136.6,132.3,132.1,129.6,48.2,34.7,28.2,25.9,21.1ppm.
example 4: to a dry Schlenk reaction tube were added a stirring magneton, p-methylbenzenesulfonylhydrazide (95.68mg,0.5mmol), cyclooctane (3.0mmol), and CuBr (0.1 mmol). Vacuumizing and filling oxygen into the reaction tube, sealing, placing the reaction tube in a glass dish wrapped by a 18w Led (420-. After completion of the reaction, the mixture was extracted with dichloromethane three times, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. And (5) separating and purifying by using column chromatography to obtain the product 4 with the yield of 72%. The structure and characterization data are as follows:
p-tolylsulfanyl-cyclooctane(4)
1H NMR(400MHz,CDCl3)δ7.29(d,J＝8.1Hz,2H),7.10(d,J＝8.0Hz,2H),3.32(s,1H),2.32(s,3H),1.98-1.89(m,2H),1.60-1.44(m,12H)；13C NMR(101MHz,CDCl3)δ136.6,132.3,132.2，129.5,48.3,31.9,27.2,25.9,25.2,21.1ppm.
example 5: to a dry Schlenk reaction tube were added stirring magnetons, p-methylbenzenesulfonylhydrazide (95.68mg,0.5mmol), cyclododecane (3mmol), and CuO (0.1 mmol). The reaction tube is vacuumized, filled with oxygen, sealed, placed in a glass dish wrapped by a 24w Led lamp (420-. After completion of the reaction, the mixture was extracted with dichloromethane three times, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. And (5) separating and purifying by using column chromatography to obtain the product with the yield of 75%. The structure and characterization data are as follows:
p-tolylsulfanyl-cyclododecane(5)
1H NMR(400MHz,CDCl3)δ7.29(d,J＝8.0Hz,2H),7.10(d,J＝7.9Hz,2H),3.19(s,1H),2.33(s,3H),1.72-1.63(m,2H),1.59-1.55(m,2H),1.44-1.27(m,18H)；13C NMR(101MHz,CDCl3)δ136.5,132.10,132.0,129.5,45.3,29.9,24.2,23.8,23.4,23.3,22.1,21.0ppm.
example 6: to the Schlenk reaction tube were added a stirring magneton, p-methoxybenzenesulfonylhydrazide (104.67mg,0.5mmol), cyclopentane (5.0mmol), and CuBr (0.05 mmol). The reaction tube was evacuated and filled with oxygen, sealed, placed in a glass dish wrapped with 12w Led (420-. After completion of the reaction, the mixture was extracted with dichloromethane three times, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. And (5) separating and purifying by using column chromatography to obtain the product 6 with the yield of 77%. The structure and characterization data are as follows:
1-cyclopentylsulfanyl-4-methoxy-benzene(6)
1H NMR(400MHz,CDCl3)δ7.37(d,J＝8.8Hz,2H),6.84(d,J＝8.7Hz,2H),3.79(s,3H),3.42(s,1H),1.99-1.89(m,2H),1.76(s,2H),1.57(s,4H)；13C NMR(101MHz,CDCl3)δ158.9,134.1,126.9,114.3,55.3,47.9,33.4,24.6ppm.
example 7: to the Schlenk reaction tube were added a stirring magneton, p-methoxybenzenesulfonylhydrazide (104.67mg,0.5mmol), cyclohexane (5.0mmol), and CuCl (0.05 mmol). The reaction tube was evacuated and filled with oxygen, sealed, placed in a glass dish wrapped with 12w Led lamp (420-. After completion of the reaction, the mixture was extracted with dichloromethane three times, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. And (4) separating and purifying by using column chromatography to obtain the product 7 with the yield of 79%. The structure and characterization data are as follows:
1-cyclohexylsulfanyl-4-methoxy-benzene(7)
1H NMR(400MHz,CDCl3)δ7.38(d,J＝8.6Hz,2H),6.84(d,J＝8.5Hz,2H),3.80(s,3H),2.90(s,1H),1.93(d,J＝10.4Hz,2H),1.75(d,J＝5.8Hz,2H),1.61-1.57(m,1H),1.37-1.19(m,5H)；13C NMR(101MHz,CDCl3)δ158.3,134.6,123.9,113.5,54.3,46.8,32.3,25.1,24.7ppm.
example 8: to the Schlenk reaction tube were added a stirring magneton, benzenesulfonylhydrazide (95.65mg,0.5mmol), cyclohexane (5.0mmol), and CuBr (0.05 mmol). The reaction tube was evacuated and filled with oxygen, sealed, placed in a glass dish wrapped with 12w Led lamp (420-. After completion of the reaction, the mixture was extracted with dichloromethane three times, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. And (5) separating and purifying by using column chromatography to obtain the product 8 with the yield of 89%. The structure and characterization data are as follows:
cyclohexylsulfanyl-benzene(8)
1H NMR(400MHz,CDCl3)δ7.46(d,J＝7.2Hz,2H),7.36(d,J＝7.9Hz,2H),7.29(d,J＝7.2Hz,1H),3.22-3.11(m,1H),2.05(d,J＝10.9Hz,2H),1.84(d,J＝9.0Hz,1H),1.50-1.18(m,5H)；13C NMR(101MHz,CDCl3)δ135.2,131.8,128.7,126.5,46.5,33.4,26.1,25.8ppm.
example 9: to the Schlenk reaction tube were added a stirring magneton, p-nitrobenzenesulfonylhydrazide (118.45mg,0.5mmol), cyclohexane (5.0mmol), and CuBr (0.05 mmol). The reaction tube was evacuated and filled with oxygen, sealed, placed in a glass dish wrapped with 12w Led lamp (420-. After the reaction, the mixture was extracted with dichloromethane three times, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. And (5) separating and purifying by using column chromatography to obtain the product 9 with the yield of 85%. The structure and characterization data are as follows:
1-cyclohexylsulfanyl-4-nitro-benzene(9)
1H NMR(400MHz,CDCl3)δ8.11(d,J＝8.8Hz,2H),7.33(d,J＝11.7Hz,2H),3.36(s,1H),2.06(d,J＝11.0Hz,2H),1.89-1.75(m,2H),1.60-1.27(m,6H)；13C NMR(101MHz,CDCl3)δ146.9,127.6,125.8,123.9,44.8,32.9,25.8,25.6ppm.
example 10: to the Schlenk reaction tube were added a stirring magneton, p-chlorobenzenesulfonylhydrazide (112.82mg,0.5mmol), cyclohexane (5.0mmol), and CuCl (0.05 mmol). The reaction tube is vacuumized, filled with oxygen, sealed, placed in a glass dish wrapped by an 18w Led lamp (420-. After completion of the reaction, the mixture was extracted with dichloromethane three times, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The product 13 is obtained with a yield of 84% by column chromatography separation and purification, and the structure and characterization data are as follows:
1-chloro-4-cyclohexylsulfanyl-benzene(10)
1H NMR(400MHz,CDCl3)δ7.39(d,J＝8.5Hz,2H),7.32(d,J＝8.7Hz,2H),3.13(s,1H),2.01(t,J＝11.8Hz,2H),1.73-1.60(m,3H),1.43-1.22(m,5H)；13C NMR(101MHz,CDCl3)δ134.7,132.6,132.4,128.9,46.9,33.2,26.0,25.7ppm.
Claims (8)
1. a new synthetic method of naphthenic base aryl thioether compounds has the following specific reaction formula, and the method takes substituted benzene sulfonyl hydrazide and cyclane as raw materials, takes cheap metal as a catalyst, and generates C-H bond activation to synthesize corresponding compounds under the oxygen atmosphere and under the irradiation of an LED lamp at a certain temperature.
2. The method of claim 1, wherein the substituted benzenesulfonyl hydrazide is selected from the group consisting of hydrogen, halogen, alkoxy, nitro, cyano, and C1-C6And the R substituent group is at any position of the ortho, meta and para of the sulfonyl.
3. The method of claim 1, wherein the cycloalkane, n-1-8, comprises cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, and cyclododecane.
4. The method of claim 1, wherein the catalyst is a copper catalyst selected from the group consisting of CuCl and a low cost metal catalyst2、CuBr2CuO, CuBr and CuCl, and the amount of the catalyst is 1-20%.
5. The method of claim 1, wherein the ratio of substituted benzenesulfonylhydrazide to cycloalkane is from 1:5 to 1:30.
6. The method as set forth in claim 1, wherein the Led lamp has a wavelength of 400-480nm and a power of 3-60W.
7. The method of claim 1, wherein the reaction temperature is from 30 ℃ to 60 ℃.
8. The method of claim 1, wherein the reaction time is from 5 to 24 hours.
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