CN114874157B - Method for preparing 3- ((aryl mercapto/alkyl mercapto) methyl) ethylene oxide - Google Patents

Method for preparing 3- ((aryl mercapto/alkyl mercapto) methyl) ethylene oxide Download PDF

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CN114874157B
CN114874157B CN202210695575.4A CN202210695575A CN114874157B CN 114874157 B CN114874157 B CN 114874157B CN 202210695575 A CN202210695575 A CN 202210695575A CN 114874157 B CN114874157 B CN 114874157B
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methyl
phenyl
arylmercapto
alkylmercapto
oxirane
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CN114874157A (en
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孙松
柏君雪
沙宇
李渺
高万旭
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Changzhou University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/34—Compounds containing oxirane rings with hydrocarbon radicals, substituted by sulphur, selenium or tellurium atoms
    • 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
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Abstract

The invention relates to the fields of medicine, organic chemical industry and fine chemical industry, in particular to a method for preparing 3- ((aryl mercapto/alkyl mercapto) methyl) ethylene oxide. Allyl alcohol and N- (arylmercapto/alkylmercapto) succinimide are used as raw materials, a metal catalyst or any other additive is not needed, alcohol is used as a solvent, and the reaction is carried out for 2.5 hours at room temperature to obtain the product. The product after the reaction is subjected to simple post-treatment to obtain a series of functionalized 3- ((aryl mercapto/alkyl mercapto) methyl) oxirane compounds in high yield. Allyl alcohol and N- (arylmercapto/alkylmercapto) succinimide containing different substituents can be used as reaction substrates to give the corresponding 3- ((arylmercapto/alkylmercapto) methyl) oxirane compounds.

Description

Method for preparing 3- ((aryl mercapto/alkyl mercapto) methyl) ethylene oxide
Technical Field
The invention relates to the fields of medicine, organic synthesis and fine chemical industry, in particular to a method for preparing 3- ((aryl mercapto/alkyl mercapto) methyl) ethylene oxide.
Background
3- ((aryl mercapto/alkyl mercapto) methyl) epoxy ethane is an important organic synthesis intermediate, and the derivative product has good pharmacological activity, has wide application in the fields of medicine and biology, can be used as antitumor, antioxidant and antibacterial medicines and the like, so that the effective synthesis of the compound has higher application value. (see: secci, F.; arca, M.; front gia, A.; et al, tetrazole amides as hydrogen-bonding donor catalysts in the chemoselective oxidation of sulphides and disulphides [ J ]. Catalysis Science & Technology 2014,4 (5): 1407-1415.).
In the prior report, the synthesis method of the compound mainly usesAcid-catalyzed enantioselective oxysulfonylation of enols with organosulfur reagents is obtained (see: guan, H.; wang, N.; huang, D.S.; et al Enantioselective oxysulfenylation and oxyselenenylation of olefins catalyzed by chiral Bronsted acids [ J)]Tetrahedron 2012,68 (12): 2728-2735); or potassium persulfate (K) 2 S 2 O 8 ) Initiated silver triflate thiols (AgSCF) 3 ) As a radical source with alkynylaromatic esters (see: zeng, y.f.; tan, d.h.; chen, y.y.; et al direct radical trifluoromethylthiolation and thiocyanation of aryl alkynoate esters:mild and facile synthesis of 3-trifluoromethylthiolated and 3-thiocyanated coumarins[J]Organic Chemistry Frontiers 2015,2 (11): 1511-1515.). Or in a chiral Lewis base-catalyzed asymmetric oxysulfide cyclization of a hydroxy or carboxyolefin with a sulfur reagent (see Denmark, S.E.; kornfilt, D.J.; vogler, P.T.; catalytic Asymmetric Thiofunctionalization of Unactivated Alkenes [ J.)]Journal of the American Chemical Society 2011,133 2011,133 (39): 15308-15311.) can be used to construct epoxy sulfur compounds. However, the existing method has more severe reaction conditions, and the obtained compound structure is mainly quaternary, five-membered and six-membered epoxy or aza-heterocyclic thioether compounds, and no ternary oxa-heterocyclic thioether compound is reported. In addition, in the structure, the construction of the product of the ternary cyclic thioether is realized by a simple and easily obtained raw material and a mild reaction condition method, the structure type of the cyclic thioether is greatly expanded, and the preparation method has higher medicinal value.
Disclosure of Invention
In view of the shortcomings of the background art, the invention takes the cheap and easily available allyl alcohol and N- (arylmercapto/alkylmercapto) succinimide as the starting materials, takes alcohol as the solvent, and synthesizes a series of 3- ((arylmercapto/alkylmercapto) methyl) oxirane compounds through continuous protonation reaction, free radical addition reaction and intramolecular cyclization reaction at room temperature for 2.5 hours. The method has the advantages of wide sources of raw materials, simple and convenient operation method, easy separation and purification and higher yield.
The specific process of the reaction is as follows:
r on allyl alcohol 1 Is one of phenyl, naphthyl and benzyl; when R is 1 When the phenyl is phenyl, the substituent is one of hydrogen, methyl, tertiary butyl, phenyl, fluorine and chlorine; r is R 2 ，R 3 Is one of aryl, alkyl and cycloalkyl.
N- (arylmercapto/alkylmercapto) succinimide is one of aryl, naphthyl, heteroaryl, and alkyl.
The alcohol used in the reaction is one of trifluoroethanol, ethanol and Hexafluoroisopropanol (HFIP), and a metal catalyst or any other additive is not needed;
the molar ratio of the allyl alcohol to the N- (arylmercapto/alkylmercapto) succinimide is 1:1.3-2.0.
The structural formula of the allyl alcohol used is:wherein: r is R 1 Is one of phenyl, naphthyl and benzyl; when R is 1 When the phenyl is phenyl, the substituent is one of hydrogen, methyl, tertiary butyl, phenyl, fluorine and chlorine; r is R 2 ,R 2 Is one of aryl, alkyl and cycloalkyl.
The structure of the N- (arylmercapto/alkylmercapto) succinimide used is:r is one of aryl, naphthyl, heteroaryl and alkyl.
The reaction post-treatment is simple and convenient, and the pure 3- ((aryl mercapto/alkyl mercapto) methyl) ethylene oxide can be obtained by using a simple column chromatography separation method and using a mixed solvent of petroleum ether and ethyl acetate as an eluent.
The starting materials allyl alcohol and N- (arylmercapto/alkylmercapto) succinimide employed in the present invention are synthesized in accordance with literature (Bunescu, A.; wang, Q; zhu, J.; synthesis of Functionalized Epoxides by Copper-Catalyzed Alkylative Epoxidation of Allylic Alcohols with Alkyl Nitriles [ J)].Organic Letters 2015,17(8):1890-1893.；Wang,Z.；Li,Y.；Chen,F.；et al.The intramolecular reaction of acetophenone N-tosylhydrazone and vinyl:acid-promoted cationic cyclization toward polysubstituted indenes[J].Chemical Communications 2021,57(14):1810-1813.；Wei,L.；Wu,C.；Tung,C.；et al.Decarboxylative sulfenylation of amino acids via metallaphotoredox catalysis[J].Organic Chemistry Frontiers 2019,6(18):3224-3227.)。
The beneficial effects are that:
the invention adopts allyl alcohol and N- (arylmercapto/alkylmercapto) succinimide as initial raw materials for the first time, takes alcohol as solvent, and synthesizes a series of 3- ((arylmercapto/alkylmercapto) methyl) oxirane through continuous protonation reaction, free radical addition reaction and cyclization reaction.
The method has the advantages of wide sources of raw materials, simple and convenient operation method, easy separation and purification and higher yield. Provides a simpler and feasible way for synthesizing 3- ((aryl mercapto/alkyl mercapto) methyl) epoxy ethane, and has important application value.
Drawings
FIG. 1 is a graph of the diffuse reflectance spectrum of thiooxirane from UV-Vis;
FIG. 2 is a Photoluminescence (PL) spectrum of thiooxirane.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 12, 2-dimethyl-3-phenyl-3- ((phenylthio) methyl) oxirane
2,2-Dimethyl-3-((phenylthio)methyl)oxirane
2-methyl-3-phenyl-3-en-2-ol (0.2 mmol,32.42 mg), 1- (phenylthio) succinimide (0.4 mmol,82.81 mg) and HFIP (2.0 mL) were added to a20 mL Schlenk tube equipped with a Teflon cap. Then, the Schlenk tube was reacted at room temperature for 2.5 hours. Thereafter, the mixture was concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 20/1) to give the desired product in 91% yield. Nuclear magnetic data: 1 H NMR(CDCl 3 ,400MHz):δ7.38–7.36(m,2H),7.33–7.28(m,3H),7.25–7.24(m,2H,overlapped with CDCl 3 ),7.21–7.18(m,2H),7.14–7.11(m,1H),3.55(d,J＝13.0Hz,1H),3.40(d,J＝13.0Hz,1H),1.51(s,3H),1.00(s,3H). 13 C NMR(CDCl 3 delta 138.7,136.6,129.4,128.6,127.8,127.3,126.9,125.9,68.1,64.6,40.5,22.1,20.6 mass spectral data: MS (EI) 271.1 (M) + )。
Example 22, 2-dimethyl-3- ((phenylsulfanyl) methyl) -3- (p-tolyl) oxirane
2,2-Dimethyl-3-((phenylthio)methyl)-3-(p-toly)oxirane
2-methyl-3-p-tolyl-3-en-2-ol (0.2 mmol,35.22 mg), 1- (phenylthio) succinimide (0.26 mmol,53.82 mg) and HFIP (2.0 mL) were added to a20 mL Schlenk tube equipped with a Teflon cap. Then, the Schlenk tube was reacted at room temperature for 2.5 hours. Thereafter, the mixture was concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 20/1) to give the desired product in 56% yield. Nuclear magnetic data: 1 H NMR(CDCl 3 400MHz):δ7.25–7.24(m,4H,overlapped with CDCl 3 ),7.21–7.17(m,2H),7.12–7.10(m,3H),3.53(d,J＝12.9Hz,1H),3.37(d,J＝12.8Hz,1H),2.32(s,3H),1.49(s,3H),1.00(s,3H). 13 C NMR(101MHz,CDCl 3 ) Delta 137.0,136.7,135.8,129.5,128.7,128.6,126.9,126.0,68.1,64.7,40.7,22.2,21.2,20.7 mass spectrometry data: MS (EI) 285.1 (M) + )。
Example 3:2, 2-dimethyl-3- ((phenylsulfanyl) methyl) -3- (p-tert-butylphenyl) oxirane
2-(4-(Tert-butyl)phenyl)-3,3-dimethyl-2-((phenythio)methyl)oxirane
2-methyl-3-p-tert-butylphenyl-3-en-2-ol (0.2 mmol,32.42 mg), 1- (phenylthio) succinimide (0.26 mmol,53.82 mg) and HFIP (2.0 mL) were added to a20 mL Schlenk tube equipped with a Teflon cap. Then, S isThe chlenk tube was reacted at room temperature for 2.5 hours. Thereafter, the mixture was concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 20/1) to give the desired product in 59% yield. Nuclear magnetic data: 1 H NMR(CDCl 3 ,400MHz):δ7.34–7.28(m,4H),7.24–7.22(m,2H),7.20–7.16(m,2H),7.14–7.09(m,1H),3.53(d,J＝12.9Hz,1H),3.41(d,J＝12.9Hz,1H),1.52(s,3H),1.32(s,9H),1.03(s,3H). 13 C NMR(CDCl 3 delta 150.1,136.8,135.7,129.5,128.6,126.7,125.9,124.8,68.1,64.8,40.7,34.5,31.3,22.3,20.8 mass spectral data: MS (EI) 327.1 (M) + )。
Example 4:2- ([ 1,1' -biphenyl ] -3-yl) -3, 3-dimethyl-2- ((phenylthio) methyl) oxirane
2-([1,1'-Biphenyl]-3-yl)-3,3-dimethyl-2-((phenylthio)methyl)oxirane
3- ([ 1,1' -biphenyl)]-3-yl) -2-methyl-3-en-2-ol (0.2 mmol,47.62 mg), 1- (phenylthio) succinimide (0.26 mmol,53.82 mg) and HFIP (2.0 mL) were added to a20 mL Schlenk tube equipped with a Teflon cap. Then, the Schlenk tube was reacted at room temperature for 2.5 hours. Thereafter, the mixture was concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 20/1) to give the desired product in 74% yield. Nuclear magnetic data: 1 H NMR(CDCl 3 ,300MHz):δ7.57–7.55(m,2H),7.52–7.50(m,2H),7.42–7.39(m,4H),7.33–7.29(m,1H),7.26–7.24(m,2H),7.19–7.15(m,2H),7.12–7.10(m,1H),3.57(d,J＝13.1Hz,1H),3.42(d,J＝13.04Hz,1H),1.51(s,3H),1.04(s,3H). 13 C NMR(CDCl 3 delta 140.7,140.1,137.9,136.6,129.7,128.7,127.5,127.2,127.0,126.6,126.1,68.1,64.9,40.6,22.3,20.8 mass spectral data: MS (EI) 347.1 (M) + )。
Example 5:2- (4-fluorophenyl) -3, 3-dimethyl-2- ((phenylthio) methyl) oxirane
2-(4-Fluorophenyl)-3,3-dimethyl-2-((phenylthio)methyl)oxirane
3- (4-fluorophenyl) -2-methyl-3-en-2-ol (0.2 mmol,36.02 mg), 1- (phenylthio) succinimide (0.26 mmol,53.82 mg) and HFIP (2.0 mL) were added to a20 mL Schlenk tube equipped with a Teflon cap. Then, the Schlenk tube was reacted at room temperature for 2.5 hours. Thereafter, the mixture was concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 20/1) to give the desired product in 95% yield. Nuclear magnetic data: 1 H NMR(CDCl 3 ,400MHz):δ7.36–7.32(m,2H),7.26–7.23(m,2H),7.22–7.18(m,2H),7.16–7.12(m,1H),7.01–6.97(m,2H),3.52(d,J＝13.1,1H),3.38(d,J＝13.2,1H),1.50(s,3H),1.00(s,3H). 13 C NMR(CDCl 3 ,101MHz):δ162.0( 1 J CF ＝246.9Hz),136.3,134.6( 4 J CF ＝3.2Hz),129.6,128.8,128.7,126.2,114.8( 2 J CF =21.6 Hz), 67.8,64.9,40.6,22.1,20.6, mass spectral data: MS (EI) 289.1 (M) + )。
Example 6:2- (4-chlorophenyl) -3, 3-dimethyl-2- ((phenylthio) methyl) oxirane
2-(4-Chlorophenyl)-3,3-dimethyl-2-((phenylthio)methyl)oxirane
3- (4-chlorophenyl) -2-methyl-3-en-2-ol (0.2 mmol,39.21 mg), 1- (phenylthio) succinimide (0.26 mmol,53.82 mg) and HFIP (2.0 mL) were added to a20 mL Schlenk tube equipped with a Teflon cap. Then, the Schlenk tube was reacted at room temperature for 2.5 hours. Thereafter, the mixture was concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 20/1) to give the desired product in 42% yield. Nuclear magnetic data: 1 H NMR(DMSO-d 6 ,400MHz):δ7.39–7.32(m,1H),7.29–7.28(m,3H),7.26–7.22(m,3H),7.21–7.19(m,1H),7.17–7.13(m,1H),3.52(d,J＝13.2Hz,1H),3.37(d,J＝13.2Hz,1H),1.50(s,3H),1.00(s,3H). 13 C NMR(DMSO-d 6 ,101MHz): 13 C NMR(CDCl 3 101MHz,) δ 137.4,136.2,133.2,129.8,128.8,128.5,128.1,126.2,67.8,64.9,40.4,22.1,20.7, mass spectral data: MS (EI) 305.1 (M) + )。
Example 7:2, 2-dimethyl-3- (naphthyl) -3- (phenylthio) methyl) oxirane
2,2-Dimethyl-3-(naphthalen-2-yl)-3-((phenylthio)methyl)oxriane
2-methyl-3-naphthalen-3-en-2-ol (0.2 mmol,42.42 mg), 1- (phenylthio) succinimide (0.26 mmol,53.82 mg) and HFIP (2.0 mL) were added to a20 mL Schlenk tube equipped with a Teflon cap. Then, the Schlenk tube was reacted at room temperature for 2.5 hours. Thereafter, the mixture was concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 20/1) to give the desired product in 79% yield. Nuclear magnetic data: 1 H NMR(CDCl 3 400MHz):δ7.84-7.77(m,4H),7.50–7.44(m,3H),7.26–7.23(m,2H),7.16–7.12(m,2H),7.09–7.05(m,1H),3.66(d,J＝13.1Hz,1H),3.47(d,J＝13.0Hz,1H),1.56(s,3H),1.02(s,3H). 13 C NMR(101MHz,CDCl 3 ) Delta 136.5,136.3,132.8,132.7,129.6,128.6,128.0,127.6 (2C), 126.2,126.1,126.0,125.9,124.8,68.4,65.0,40.6,22.2,20.7 mass spectrum data: MS (EI) 321.1 (M) + )。
Example 8: 2-benzyl-3, 3-dimethyl-2- ((phenylthio) methyl) oxirane
2-Benzyl-3,3-dimethyl-2-((phenylthio)methyl)oxirane
3-benzyl-2-methyl-3-en-2-ol (0.2 mmol,35.22 mg), 1- (phenylthio) succinimide (0.26 mmol,53.82 mg) and HFIP (2.0 mL) were added to a20 mL Schlenk tube equipped with a Teflon cap. Then, the Schlenk tube was reacted at room temperature for 2.5 hours. Thereafter, the mixture was concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 20/1)The desired product was obtained in 53% yield. Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 ):δ7.34–7.31(m,2H),7.26–7.24(m,3H),7.22–7.19(m,4H),7.19–7.16(m,1H),3.18(d,J＝14.7Hz,1H),3.08–3.07(m,1H),3.05–3.03(m,1H),2.85(d,J＝12.8Hz,1H),1.47(s,3H),1.27(m,3H). 13 C NMR(101MHz,CDCl 3 ) Delta 137.2,136.0,130.5,129.6,128.9,128.4,126.6,126.5,66.7,63.1,36.8,36.2,21.5,21.2 mass spectrometry data: MS (EI) 285.1 (M) + )。
Example 9: 1-cyclopentane-2-phenyl-2- ((phenylthio) methyl) oxirane
2-Phenyl-2-((phenylthio)methyl)-1-oxaspiro[2.4]heptane
1- (1-Phenylvinyl) cyclopentan-1-ol (0.2 mmol,37.622 mg), 1- (phenylthio) succinimide (0.26 mmol,53.82 mg) and HFIP (2.0 mL) were added to a20 mL Schlenk tube equipped with a Teflon cap. Then, the Schlenk tube was reacted at room temperature for 2.5 hours. Thereafter, the mixture was concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 20/1) to give the desired product in 95% yield. Nuclear magnetic data: 1 H NMR(CDCl 3 400MHz):δ7.41–7.39(m,2H),7.38–7.34(m,2H),7.32–7.30(m,3H),7.26–7.22(m,2H),7.19–7.15(m,1H),3.67(d,J＝13.1Hz,1H),3.35(d,J＝13.1Hz,1H),2.19–2.12(m,1H),1.94–1.70(m,4H),1.60–1.44(m,2H),1.38–1.32(m,1H). 13 C NMR(CDCl 3 delta 138.7,136.7,129.6,128.7,128.0,127.4,126.7,126.0,76.3,66.6,41.1,31.8,30.7,25.4,25.0 mass spectral data: MS (EI) 297.1 (M) + )。
Example 10: 2-isopropyl-2-methyl-3-phenyl-3- ((phenylthio) methyl) oxirane
2-Isopropy-2-methyl-3-phenyl-3-((phenylthio)methyl)oxirane
2, 3-dimethyl-4-phenyl-4-en-3-ol (0.2 mmol,38.03 mg), 1- (phenylthio) succinimide (0.26 mmol,53.82 mg) and HFIP (2.0 mL) were added to a20 mL Schlenk tube equipped with a Teflon cap. Then, the Schlenk tube was reacted at room temperature for 2.5 hours. Thereafter, the mixture was concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 20/1) to give the desired product in 81% yield. Nuclear magnetic data: 1 H NMR(CDCl 3 ,400MHz)mixture of diastereomers:δ7.44–7.43(m,2H),7.35–7.11(m,18H),3.63–3.59(m,2H),3.50–3.40(m,2H),2.01–1.94(m,1H),1.40(s,3H),1.15–1.10(m,7H),0.95(d,J＝6.7Hz,3H),0.87(s,3H),0.76(d,J＝6.8Hz,3H). 13 C NMR(101MHz,CDCl 3 ) Delta 139.3,138.7,136.8 (2C), 129.4 (2C), 128.6 (2C), 127.9,127.7,127.3,127.0,125.9 (2C), 71.2,70.8,69.6,69.3,40.8,39.8,31.4,31.3,19.1,17.9,17.7,17.3,13.7,12.5. Mass Spectrometry data: MS (EI) 299.1 (M) + )。
Example 11: 2-methyl-3-phenyl-3- ((phenylsulfanyl) methyl) -2-propane oxirane
2-Methyl-3-phenyl-3-((phenylthio)methyl)-2-propyloxirane
4-methyl-5-phenylhex-5-en-4-ol (0.2 mmol,38.03 mg), 1- (phenylsulfanyl) succinimide (0.26 mmol,53.82 mg) and HFIP (2.0 mL) were added to a20 mL Schlenk tube equipped with a Teflon cap. Then, the Schlenk tube was reacted at room temperature for 2.5 hours. Thereafter, the mixture was concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 20/1) to give the desired product in 95% yield. Nuclear magnetic data: 1 H NMR(CDCl 3, 400MHz)mixture of diastereomers:δ7.43–7.41(m,2H),7.38–7.31(m,6H),7.30–7.26(m,6H),7.24–7.19(m,4H),7.16–7.12(m,2H),3.62–3.59(m,2H),3.45–3.40(m,2H),1.85–1.80(m,1H),1.72–1.67(m,1H),1.62–1.57(m,2H),1.52(s,3H),1.42–1.32(m,2H),1.24–1.08(m,2H),1.03(t,J＝7.3Hz,3H),1.00(s,3H),0.73(t,J＝7.2Hz,3H). 13 C NMR(101MHz,CDCl 3 ) Delta 138.9,138.7,136.7 (2C), 129.5 (2C), 128.6 (2C), 127.9,127.8,127.3,127.0 (2C), 125.9,68.5,68.2,67.6,67.5,40.7,40.4,37.0,36.4,19.6,19.0,18.2,18.0,14.3,14.2. Mass Spectrometry data: MS (EI) 299.1 (M) + )。
Example 12: 2-methyl-2, 3-diphenyl-3- ((phenylthio) methyl) oxirane
2-Methyl-2,3-diphenyl-3-((phenylthio)methyl)oxirane
2, 3-Diphenyl-3-en-2-ol (0.2 mmol,44.82 mg), 1- (phenylsulfanyl) succinimide (0.26 mmol,53.82 mg) and HFIP (2.0 mL) were added to a20 mL Schlenk tube equipped with a Teflon cap. Then, the Schlenk tube was reacted at room temperature for 2.5 hours. Thereafter, the mixture was concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 20/1) to give the desired product in 21% yield. Nuclear magnetic data: 1 H NMR(CDCl 3 400MHz):δ7.47–7.45(m,2H),7.43–7.40(m,3H),7.38–7.36(m,3H),7.33–7.30(m,2H),7.16–7.08(m,5H),3.23(d,J＝13.5Hz,1H),2.86(d,J＝13.5Hz,1H),1.31(s,3H). 13 C NMR(101MHz,CDCl 3 ) Delta 140.1,137.8,136.4,130.1,128.5,128.4,128.1,127.6,127.5,127.2,126.2,126.0,70.2,69.2,40.7,22.1 mass spectrometry data: MS (EI) 333.1 (M) + )。
Example 13:2, 2-dimethyl-3-phenyl-3- ((s) -1- (phenylsulfanyl) ethyl) oxirane
2,2-Dimethyl-3-phenyl-3-((s)-1-(phenylthio)ethyl)oxirane
(E) -2-methyl-3-phenylpentan-3-en-2-ol (0.2 mmol,35.22 mg), 1- (phenylthio) succinimide (0.26 mmol,53.82 mg) and HFIP (2.0 mL) were added to a20 mL Schlenk tube equipped with a Teflon cap. Then, the Schlenk tube was reacted at room temperature for 2.5 hours. Thereafter, the mixture was concentrated under reduced pressure. The residue was taken up rapidly by means of silica gelPurification by chromatography (PE/EA 20/1) gave the desired product in 83% yield. Nuclear magnetic data: 1 H NMR(CDCl 3 400MHz):δ7.49–7.48(m,1H),7.47–7.46(m,1H),7.38–7.34(m,3H),7.30–7.26(m,3H),7.23–7.19(m,2H),3.52(q,J＝7.2Hz,1H),1.56(s,3H),1.48(d,J＝7.2Hz,3H),1.01(s,3H). 13 C NMR(101MHz,CDCl 3 ) Delta 136.5,135.8,131.7,128.7,127.6,126.6,71.5,64.5,49.8,23.5,20.0,19.5 mass spectrometry data: MS (EI) 285.1 (M) + )。
Example 14:2, 2-dimethyl-3-phenyl-3- ((p-methylphenylsulfanyl) methyl) oxirane
2,2-Dimethyl-3-phenyl-3-((p-tolylthio)methyl)oxirane
2-methyl-3-phenyl-3-en-2-ol (0.2 mmol,32.42 mg), 1- (p-methylphenylsulfanyl) succinimide (0.26 mmol,57.47 mg) and HFIP (2.0 mL) were added to a20 mL Schlenk tube equipped with a Teflon cap. Then, the Schlenk tube was reacted at room temperature for 2.5 hours. Thereafter, the mixture was concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 20/1) to give the desired product in 89% yield. Nuclear magnetic data: 1 H NMR(CDCl 3 ,400MHz):δ7.41–7.39(m,2H),7.36–7.32(m,2H),7.30–7.27(m,1H),7.20–7.18(m,2H),7.05–7.03(m,2H),3.54(d,J＝13.0Hz,1H),3.38(d,J＝13.0Hz,1H),2.30(s,3H),1.51(s,3H),1.02(s,3H). 13 C NMR(CDCl 3 delta 138.9,136.2,132.9,130.4,129.5,127.9,127.3,127.1,68.3,64.7,41.4,22.2,20.9,20.7 mass spectral data: MS (EI) 285.1 (M) + )。
Example 15:2, 2-dimethyl-3-phenyl-3- ((p-methoxyphenylthio) methyl) oxirane
2-(((4-Methoxyphenyl)thio)methyl)-3,3-dimethyl-2-phenyloxirane
2-methyl-3-phenyl-3-en-2-ol (0.2 mmol,32.42 mg), 1- (p-methoxyphenylthio) succinimide (0.26 mmol,61.63 mg) and HFIP (2.0 mL) were added to a20 mL Schlenk tube equipped with a Teflon cap. Then, the Schlenk tube was reacted at room temperature for 2.5 hours. Thereafter, the mixture was concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 20/1) to give the desired product in 96% yield. Nuclear magnetic data: 1 H NMR(CDCl 3 ,300MHz):δ7.40–7.36(m,2H),7.33–7.30(m,2H),7.28–7.26(m,1H),7.24–7.22(m,2H),6.83–6.73(m,2H),3.74(s,3H),3.48(d,J＝13.2Hz,1H),3.29(d,J＝13.2Hz,1H),1.45(s,3H),0.98(s,3H). 13 C NMR(CDCl 3 delta 158.8,139.0,133.3,132.6,127.8,127.3,127.1,126.8,114.5,114.3,68.4,64.6,55.2,42.6,22.2,20.7 mass spectral data: MS (EI) 301.1 (M) + )。
Example 16:2, 2-dimethyl-3-phenyl-3- ((p-fluorophenylthio) methyl) oxirane
2-(((4-Fluorophenyl)thio)methyl)-3,3-dimethyl-2-phenyloxirane
2-methyl-3-phenyl-3-en-2-ol (0.2 mmol,32.42 mg), 1- (p-fluorobenzenesulfide) succinimide (0.26 mmol,58.51 mg) and HFIP (2.0 mL) were added to a20 mL Schlenk tube equipped with a Teflon cap. Then, the Schlenk tube was reacted at room temperature for 2.5 hours. Thereafter, the mixture was concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 20/1) to give the desired product in 69% yield. Nuclear magnetic data: 1 H NMR(CDCl 3 ,300MHz):δ7.34–7.27(m,4H),7.26–7.24(m,1H),7.23–7.20(m,2H),6.89–6.85(m,2H),3.51(d,J＝13.3Hz,1H),3.32(d,J＝13.3Hz,1H),1.47(s,3H),0.98(s,3H). 13 C NMR(CDCl 3 ,75MHz):δ161.7( 1 J CF ＝247.2Hz),138.7,132.7( 3 J CF ＝8.1Hz),131.4( 4 J CF ＝3.5Hz),127.9,127.4,127.1,115.7( 1 J CF =21.8 Hz), 68.4,64.8,41.8,22.2,20.7, mass spectral data: MS (EI) 289.1 (M) + )。
Example 17:3, 3-dimethyl-2- ((2, 4-dimethylbenzenesulfide) methyl) -2-phenyl-oxirane
2-(((2,4-Dimethylphenyl)thio)methyl)-3,3-dimethyl-2-phenyloxirane
2-methyl-3-phenyl-3-en-2-ol (0.2 mmol,32.42 mg), 1- (2, 4-dimethylbenzenesulfide) succinimide (0.26 mmol,61.12 mg) and HFIP (2.0 mL) were added to a20 mL Schlenk tube equipped with a Teflon cap. Then, the Schlenk tube was reacted at room temperature for 2.5 hours. Thereafter, the mixture was concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 20/1) to give the desired product in 51% yield. Nuclear magnetic data: 1 H NMR(CDCl 3 400MHz):δ7.41–7.38(m,2H),7.34–7.30(m,2H),7.28–7.24(m,1H),7.14-7.12(m,1H),6.34–6.88(m,2H),3.44(d,J＝12.7Hz,1H),3.30(d,J＝12.7Hz,1H),2.28(s,3H),2.25(s,3H),1.49(s,3H),1.00(s,3H). 13 C NMR(101MHz,CDCl 3 ) Delta 139.0,138.4,136.3,132.1,130.9,130.4,127.9,127.3,127.1,127.0,68.2,64.7,40.7,22.2,20.8 (2C), 20.4. Mass spectrometry data: MS (EI) 299.1 (M) + )。
Example 18:2, 2-dimethyl-3- ((naphthyl-2-thio) methyl) -3-phenyloxirane
2,2-Dimethyl-3-((naphthalen-2-ylthio)methyl)-3-phenyloxirane
1- (1-Phenylvinyl) cyclohexane-1-ol (0.2 mmol,40.43 mg), 1- (naphthyl-2-thio) succinimide (0.26 mmol,66.83 mg) and HFIP (2.0 mL) were added to a20 mL Schlenk tube equipped with a Teflon cap. Then, the Schlenk tube was reacted at room temperature for 2.5 hours. Thereafter, the mixture was concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 20/1) to give the desired product in 76% yield. Nuclear magnetic data: 1 H NMR(CDCl 3 ,400MHz):δ7.81–7.73(m,2H),7.70–7.65(m,3H),7.46–7.43(m,3H),7.37–7.32(m,3H),7.30–7.26(m,1H),3.67(d,J＝13.0Hz,1H),3.54(d,J＝13.0Hz,1H),1.58(m,3H),1.06(m,3H). 13 C NMR(101MHz,CDCl 3 ) Delta 138.8,134.1,133.6,131.6,128.1,127.9,127.6,127.5,127.4,127.3,127.1,127.0,126.4,125.6,68.2,64.9,40.5,22.2,20.8 mass spectrometry data: MS (EI) 321.1 (M) + )。
Example 19:2- ((benzylthio) methyl) -3, 3-dimethyl-2-phenyloxirane
2-((Benzylthio)methyl)-3,3-dimethyl-2-phenyloxirane
2-methyl-3-phenyl-3-en-2-ol (0.2 mmol,32.42 mg), 1- (benzylthio) succinimide (0.26 mmol,57.47 mg) and HFIP (2.0 mL) were added to a20 mL Schlenk tube equipped with a Teflon cap. Then, the Schlenk tube was reacted at room temperature for 2.5 hours. Thereafter, the mixture was concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 20/1) to give the desired product in 42% yield. Nuclear magnetic data: 1 H NMR(CDCl 3 ,400MHz):δ7.39–7.36(m,4H),7.34–7.30(m,2H),7.28–7.26(m,2H),7.23–7.22(m,2H),3.62(d,J＝13.3Hz,1H),3.50(d,J＝13.3Hz,1H),2.96–2.86(m,2H),1.44(s,3H),1.00(s,3H). 13 C NMR(101MHz,CDCl 3 ) Delta 139.3,138.0,129.0,128.3,127.9,127.3,127.1,126.9,64.1,36.6,35.8,29.7,22.3,20.5 mass spectrometry data: MS (EI) 285.1 (M) + )。
Example 20:2- ((butylsulfanyl) methyl) -3, 3-dimethyl-2-phenyloxirane
2-((Butylthio)methyl)-3,3-dimethyl-2-phenyloxirane
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1- (1-Phenylvinyl) cycloheptan-1-ol (0.2 mmol,43.23 mg), 1- (butylsulfanyl) succinimide (0.26 mmol,48.64 mg) and HFIP (2.0 mL) were added toA20 mL Schlenk tube was fitted with a Teflon cap. Then, the Schlenk tube was reacted at room temperature for 2.5 hours. Thereafter, the mixture was concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA 20/1) to give the desired product in 79% yield. Nuclear magnetic data: 1 H NMR(CDCl 3 400MHz):δ7.38–7.36(m,2H),7.34–7.30(m,2H),7.28–7.24(m,1H),3.10(d,J＝13.5Hz,1H),2.96(d,J＝13.5Hz,1H),2.41–2.34(m,2H),1.51(s,3H),1.47-1.41(m,2H),1.34–1.29(m,2H),0.98(s,3H),0.86–0.82(m,3H). 13 C NMR(101MHz,CDCl 3 ) Delta 139.3,127.8,127.2,127.0,68.9,64.1,37.3,32.6,31.4,22.2,21.8,20.6,13.5 mass spectrometry data: MS (EI) 251.1 (M) + )。
TABLE 1
Absorption and emission datea
a In DCM(10 -5 M)
The highly fused thiooxiranes have unique photoelectric properties, as shown in fig. 1, which were tested by UV-Vis diffuse reflectance and Photoluminescence (PL) spectroscopy, with products of different substituents having higher absorption peaks in the UV range and higher emission peaks in the visible range. As shown in Table 1, the fluorescence Stokes shift (Stokes shift) is the difference between the strongest wavelengths of the same electron transition in the absorption and emission spectra, and the product may produce a larger red shift.

Claims (3)

1. A process for preparing 3- ((arylmercapto/alkylmercapto) methyl) oxirane, characterized by: the method comprises the following steps: allyl alcohol and N- (arylmercapto/alkylmercapto) succinimide are used as raw materials, alcohol is used as a solvent, and the reaction is carried out at room temperature to obtain a product;
the structural formula of the allyl alcohol is as follows:
wherein: r is R 1 Is one of phenyl, naphthyl and benzyl; when R is 1 When the phenyl is phenyl, the substituent on the phenyl is one of hydrogen, methyl, tertiary butyl, phenyl, fluorine and chlorine; r is R 2 ，R 3 Is one of aryl, alkyl and cycloalkyl;
the structural formula of the N- (arylmercapto/alkylmercapto) succinimide is as follows:
wherein: r is one of aryl, naphthyl, heteroaryl and alkyl;
the 3- ((arylmercapto/alkylmercapto) methyl) oxirane has the structural formula:
wherein: r is R 1 Is one of phenyl, naphthyl and benzyl; when R is 1 When the phenyl is phenyl, the substituent on the phenyl is one of hydrogen, methyl, tertiary butyl, phenyl, fluorine and chlorine; r is R 2 ，R 3 Is one of aryl, alkyl and cycloalkyl;
r is one of aryl, naphthyl, heteroaryl and alkyl;
the alcohol is hexafluoroisopropanol.
2. The method for producing 3- ((arylmercapto/alkylmercapto) methyl) oxirane of claim 1, wherein: the mol ratio of the allyl alcohol to the N- (arylmercapto/alkylmercapto) succinimide is 1:1.3-2.0.
3. The method for producing 3- ((arylmercapto/alkylmercapto) methyl) oxirane of claim 1, wherein: the reaction time was 2.5 hours.
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