CN116903505A - Method for synthesizing S-biaryl dithio carbamate compound - Google Patents
Method for synthesizing S-biaryl dithio carbamate compound Download PDFInfo
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Abstract
本发明公开了一种合成S‑联芳基二硫代氨基甲酸酯类化合物的方法，其包括以下步骤：将环状二芳基碘鎓盐、胺和二硫化碳分散在溶剂中进行反应，即得S‑联芳基二硫代氨基甲酸酯类化合物。本发明的合成S‑联芳基二硫代氨基甲酸酯类化合物的方法无需催化剂和碱的参与，具有反应条件温和、操作简便安全、原料易得、区域选择性好、官能团兼容性好等优点，适合进行大规模推广应用。
The invention discloses a method for synthesizing S-biaryldithiocarbamate compounds, which includes the following steps: dispersing cyclic diaryl iodonium salts, amines and carbon disulfide in a solvent for reaction, to obtain S‑biaryldithiocarbamates. The method for synthesizing S-biaryldithiocarbamate compounds of the present invention does not require the participation of catalysts and bases, and has the advantages of mild reaction conditions, simple and safe operation, easy availability of raw materials, good regional selectivity, and good functional group compatibility. , suitable for large-scale promotion and application.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for synthesizing S-biaryl dithio carbamate compounds.
Background
The dithiocarbamic acid ester compounds are widely existing bioactive compounds in the nature, and are of great interest in the fields of natural products, medicines, pesticides and the like, and the synthetic method of the compounds becomes a research hotspot. The traditional method for synthesizing the dithiocarbamic acid ester compound needs to use highly toxic thiophosgene, which not only has potential safety hazard, but also causes environmental pollution (H.Tilles, J.Am.Chem.Soc.,1959,81,714;W.Walter,K.Bode,Angew.Chem.Int.Ed.Engl, 1967,6,281). Therefore, it is of great importance to explore a more green and efficient synthesis method of dithiocarbamic acid ester compounds.
In recent years, there have been many reports on the synthesis of dithiocarbamates by reacting carbon disulfide and an amine with an electrophile, for example:
a) The method for synthesizing the S-alkyl dithio carbamate compound mainly comprises the following steps: 1) Salvatore et al in 2001 reported the co-promotion of halogenated hydrocarbon and amine, carbon disulfide synthesis of S-alkyl dithiocarbamates by base and TBAI (R.Salvatore, S.Sahab, K.Jung Tetrahedron Lett.,2001,42,2055); 2) In 2009 Yadav et al reported that metal-free and additive-mediated electron-deficient olefins reacted with amines, carbon disulfide to synthesize such compounds (L.Yadav, R.Patel, V.Srivastava, tetrahedron lett.,2009,50,1335); 3) Karskar et al reported that nano magnesium oxide catalyzes the reaction of Michael acceptors with amines and carbon disulfide to synthesize this class of compounds (B.Karmakar, J.Banerji, tetrahedron lett.,2011,52,6584); 4) The 2013 sand subject group reported that the base promoted hydrazone, amine and carbon disulfide to synthesize the compound and the like (Q.Sha, Y.Wei, org.Biomol.Chem.,2013,11,5615);
b) The method for synthesizing the S-aryl dithio carbamate compound mainly comprises the following steps: 1) The Bao Weiliang group of subjects reported the synthesis of S-aryl dithiocarbamates by copper-catalyzed reaction of iodo-arenes with sodium dithiocarbamates (y.liu, w.bao, tetrahedron lett.,2007,48,4785); 2) In 2008 Ranu et al reported that copper nanoparticles catalyzed the reaction of halogenated aromatic hydrocarbons with amines and carbon disulfide to synthesize S-aryl dithiocarbamates (b.sukalian; saha; ranu, green chem.,2008,10,1224); 3) The Zhang Bing group of problems in 2015 proposes the synthesis of S-aryl dithiocarbamates by the base-promoted reaction of pentafluorobenzonitrile with an amine, carbon disulfide (X.Yin, Y.Guo, B.Zhang, et al, tetrahedron lett, 2015,56,5135); 4) 2016, qi Chaorong et al developed a copper-mediated coupling reaction of arylboronic acids with amines, carbon disulphide to synthesize S-aryldithiocarbamates (C.Qi, T.Guo, W.Xiong, synlett,2016,27,2626); 5) 2021 Sushata et al reported the synthesis of S-aryl dithiocarbamates by reacting linear diaryliodonium salts with amines, carbon disulfide without metal or base participation (K.Sushanta, J.Sonal, M.Sandip, et al, org. Lett.,2021,23,6401).
In summary, although the research of the current method for synthesizing the dithiocarbamic acid ester compound has been greatly progressed, the methods still have the problems of low atom utilization rate, need of transition metal catalysis, narrow substrate application range, poor product modifier and the like, and are difficult to completely meet the practical application requirements. Furthermore, methods for synthesizing S-biaryl dithiocarbamates have not been reported so far.
Therefore, the development of the S-biaryl dithiocarbamic acid ester compound synthesis method has the advantages of no need of a catalyst, mild reaction conditions, simple and safe operation, easily available raw materials, good regioselectivity and good functional group compatibility, and has very important significance.
Disclosure of Invention
The invention aims to provide a method for synthesizing S-biaryl dithio carbamate compounds.
The technical scheme adopted by the invention is as follows:
the method for synthesizing the S-biaryl dithio carbamate compound comprises the following steps: dispersing cyclic diaryl iodonium salt, amine and carbon disulfide in a solvent for reaction to obtain an S-biaryl dithio carbamate compound; the structural formula of the cyclic diaryl iodonium salt is as follows:wherein R is 1 Is at least one of methyl, ethyl, tertiary butyl, fluorine, chlorine, methoxy and trifluoromethyl, R 2 Is at least one of methyl, ethyl, tertiary butyl, fluorine, chlorine, methoxy and trifluoromethyl. And (3) injection: r is R 1 And R is 2 Each may represent a plurality of substituents on the benzene ring, for example: r is R 1 Can be represented as containing a benzene ring2 methyl groups.
Preferably, the molar ratio of the cyclic diaryl iodonium salt, the amine and the carbon disulfide is 1:1-4:1-4.
Preferably, the amine has the formula:wherein R is 3 Is one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, cyclohexyl, benzyl and 2-naphthylmethyl, R 4 Is one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, cyclohexyl, benzyl and 2-naphthylmethyl.
Preferably, the amine is one of tetrahydropyrrole, piperidine, 4-phenylpiperidine, cyclohexylimine, morpholine, thiomorpholine, 1-phenylpiperazine, ethyl N-benzylglycinate, desloratadine, amoxapine, fluoxetine.
Preferably, the solvent is at least one of acetonitrile, dichloromethane and water.
Preferably, the reaction is carried out at 25-85 ℃ for 2-12 hours.
Preferably, the reaction is carried out at a stirring rate of 400rpm to 800 rpm.
Preferably, the reaction solution is further separated and purified after the completion of the reaction.
Preferably, the specific operation of the separation and purification is as follows: the reaction solution is washed with water, extracted with ethyl acetate, and then the organic layer is taken for drying, filtering and reduced pressure distillation, and then column chromatography purification is carried out.
Preferably, the eluent of the column chromatography consists of petroleum ether and ethyl acetate according to the volume ratio of 15-25:1.
The synthetic reaction formula of the S-biaryl dithio carbamate compound is as follows:
the beneficial effects of the invention are as follows: the method for synthesizing the S-biaryl dithiocarbamic acid ester compound does not need the participation of a catalyst and alkali, has the advantages of mild reaction conditions, simple and safe operation, easily available raw materials, good regioselectivity, good functional group compatibility and the like, and is suitable for large-scale popularization and application.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in example 1.
FIG. 2 is a nuclear magnetic resonance carbon spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in example 1.
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in example 8.
FIG. 4 is a nuclear magnetic resonance carbon spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in example 8.
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in example 9.
FIG. 6 is a nuclear magnetic resonance carbon spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in example 9.
FIG. 7 is a nuclear magnetic resonance hydrogen spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in example 10.
FIG. 8 is a nuclear magnetic resonance carbon spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in example 10.
FIG. 9 is a nuclear magnetic resonance hydrogen spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in example 11.
FIG. 10 is a nuclear magnetic resonance carbon spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in example 11.
FIG. 11 is a nuclear magnetic resonance hydrogen spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in example 12.
FIG. 12 is a nuclear magnetic resonance carbon spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in example 12.
FIG. 13 is a nuclear magnetic resonance hydrogen spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in example 13.
FIG. 14 is a nuclear magnetic resonance carbon spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in example 13.
FIG. 15 is a nuclear magnetic resonance hydrogen spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in example 14.
FIG. 16 is a nuclear magnetic resonance carbon spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in example 14.
FIG. 17 is a nuclear magnetic resonance hydrogen spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in example 15.
FIG. 18 is a nuclear magnetic resonance carbon spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in example 15.
FIG. 19 is a nuclear magnetic resonance fluorine spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in example 15.
FIG. 20 is a nuclear magnetic resonance hydrogen spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in example 16.
FIG. 21 is a nuclear magnetic resonance carbon spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in example 16.
FIG. 22 is a nuclear magnetic resonance hydrogen spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in example 17.
FIG. 23 is a nuclear magnetic resonance carbon spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in example 17.
FIG. 24 is a nuclear magnetic resonance hydrogen spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in example 18.
FIG. 25 is a nuclear magnetic resonance carbon spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in example 18.
Detailed Description
The invention is further illustrated and described below in connection with specific examples.
Example 1:
a method for synthesizing an S-biaryl dithiocarbamate compound, comprising the steps of:
adding 0.1mmol of 1, 9-dimethyl-dibenzo [ b, d ] iodonium triflate, 0.25mmol of diethylamine, 0.25mmol of carbon disulfide and 1.5mL of acetonitrile into a reaction vessel, stirring and reacting for 12 hours at 25 ℃ after the reaction vessel is closed, stirring at 600rpm, stopping heating and stirring, cooling to room temperature, adding 5mL of water for washing, extracting for 3 times by using ethyl acetate, combining organic phases, drying by using 0.5g of anhydrous sodium sulfate, filtering, distilling under reduced pressure, purifying by column chromatography, and obtaining the S-biaryl dithiocarbamic acid ester compound (yield: 40 percent) by volume ratio of petroleum ether and ethyl acetate.
The nuclear magnetic resonance hydrogen spectrogram of the S-biaryl dithiocarbamic acid ester compound synthesized in the embodiment is shown in fig. 1, the nuclear magnetic resonance carbon spectrogram is shown in fig. 2, and the resolution data are as follows:
1 H NMR(400MHz,CDCl 3 )：δ＝7.77(d,J＝7.8Hz,1H),7.66(dd,J＝7.4,1.7Hz,1H),7.48-7.40(m,2H),7.22(d,J＝7.5Hz,1H),6.94(t,J＝7.7Hz,1H),4.05-3.87(m,2H),3.70-3.49(m,2H),2.12(s,3H),2.01(s,3H),1.23(d,J＝7.2Hz,3H),1.10(d,J＝7.3Hz,3H)。
13 C NMR(100MHz,CDCl 3 )：δ＝194.51,148.02,144.02,139.04,137.38,136.58,136.18,131.70,130.89,129.89,128.83,128.04,102.01,21.95,20.18。
the infrared data and mass spectrum data of the S-biaryl dithio carbamate compound synthesized in the embodiment are as follows:
IR(KBr)ν max ：3041,2974,1555,1483,1447,1413,1350,1267,1204,1138,1079,982,913,862,826,757,672cm -1 。
HRMS(ESI)：Calcd for C 19 H 22 INS 2 [M+H] + :456.0311,Found 456.0312。
in summary, the structural formula of the S-biaryl dithio carbamate compound synthesized in this example is as follows:
example 2:
a method for synthesizing an S-biaryl dithiocarbamate compound, comprising the steps of:
0.1mmol of 1, 9-dimethyl-dibenzo [ b, d ] iodonium triflate, 0.25mmol of diethylamine, 0.25mmol of carbon disulfide and 1.5mL of acetonitrile are added into a reaction vessel, the reaction vessel is closed and stirred for 12 hours at 45 ℃, the stirring speed is 600rpm, heating and stirring are stopped, the reaction vessel is cooled to room temperature, 5mL of water is added for water washing, ethyl acetate is used for extraction for 3 times, the organic phases are combined, then the organic phases are dried by 0.5g of anhydrous sodium sulfate, filtration and reduced pressure distillation are carried out, column chromatography purification is carried out, and eluent of the column chromatography consists of petroleum ether and ethyl acetate according to the volume ratio of 20:1, thus obtaining the S-biaryl dithiocarbamate compound (the yield: 93 percent, the product is the same as example 1).
Example 3:
a method for synthesizing an S-biaryl dithiocarbamate compound, comprising the steps of:
0.1mmol of 1, 9-dimethyl-dibenzo [ b, d ] iodonium triflate, 0.25mmol of diethylamine, 0.25mmol of carbon disulfide and 1.5mL of acetonitrile are added into a reaction vessel, the reaction vessel is closed and stirred for 12 hours at 85 ℃, the stirring speed is 600rpm, heating and stirring are stopped, the reaction vessel is cooled to room temperature, 5mL of water is added for water washing, ethyl acetate is used for extraction for 3 times, the organic phases are combined, then the organic phases are dried by 0.5g of anhydrous sodium sulfate, filtration and reduced pressure distillation are carried out, column chromatography purification is carried out, and eluent of the column chromatography consists of petroleum ether and ethyl acetate according to the volume ratio of 20:1, thus obtaining the S-biaryl dithiocarbamate compound (the yield: 93 percent, the product is the same as example 1).
Example 4:
a method for synthesizing an S-biaryl dithiocarbamate compound, comprising the steps of:
0.1mmol of 1, 9-dimethyl-dibenzo [ b, d ] iodonium triflate, 0.25mmol of diethylamine, 0.25mmol of carbon disulfide and 1.5mL of acetonitrile are added into a reaction vessel, the reaction vessel is closed and stirred for 2 hours at 45 ℃, the stirring speed is 600rpm, heating and stirring are stopped, the reaction vessel is cooled to room temperature, 5mL of water is added for water washing, ethyl acetate is used for extraction for 3 times, the organic phases are combined, then the organic phases are dried by 0.5g of anhydrous sodium sulfate, filtration and reduced pressure distillation are carried out, column chromatography purification is carried out, and eluent of the column chromatography consists of petroleum ether and ethyl acetate according to the volume ratio of 20:1, thus obtaining the S-biaryl dithiocarbamate compound (the yield: 96 percent, the product is the same as example 1).
Example 5:
a method for synthesizing an S-biaryl dithiocarbamate compound, comprising the steps of:
0.1mmol of 1, 9-dimethyl-dibenzo [ b, d ] iodonium triflate, 0.1mmol of diethylamine, 0.1mmol of carbon disulfide and 1.5mL of acetonitrile are added into a reaction vessel, the reaction vessel is closed and stirred for 2 hours at 45 ℃, the stirring speed is 600rpm, heating and stirring are stopped, the reaction vessel is cooled to room temperature, 5mL of water is added for water washing, ethyl acetate is used for extraction for 3 times, the organic phases are combined, then the organic phases are dried by 0.5g of anhydrous sodium sulfate, filtration and reduced pressure distillation are carried out, column chromatography purification is carried out, and eluent of the column chromatography consists of petroleum ether and ethyl acetate according to the volume ratio of 20:1, thus obtaining the S-biaryl dithiocarbamate compound (yield: 41 percent, the product is the same as example 1).
Example 6:
a method for synthesizing an S-biaryl dithiocarbamate compound, comprising the steps of:
0.1mmol of 1, 9-dimethyl-dibenzo [ b, d ] iodonium triflate, 0.4mmol of diethylamine, 0.4mmol of carbon disulfide and 1.5mL of acetonitrile are added into a reaction vessel, the reaction vessel is closed and stirred for 2 hours at 45 ℃, the stirring speed is 600rpm, heating and stirring are stopped, the reaction vessel is cooled to room temperature, 5mL of water is added for water washing, ethyl acetate is used for extraction for 3 times, the organic phases are combined, then the organic phases are dried by 0.5g of anhydrous sodium sulfate, filtration and reduced pressure distillation are carried out, column chromatography purification is carried out, and eluent of the column chromatography consists of petroleum ether and ethyl acetate according to the volume ratio of 20:1, thus obtaining the S-biaryl dithiocarbamic acid ester compound (the yield: 95 percent, the product is the same as in example 1).
Example 7:
a method for synthesizing an S-biaryl dithiocarbamate compound, comprising the steps of:
adding 0.1mmol of 1, 9-dimethyl-dibenzo [ b, d ] iodonium triflate, 0.25mmol of diethylamine, 0.25mmol of carbon disulfide and 1.5mL of water into a reaction vessel, stirring and reacting for 2 hours at 45 ℃ after the reaction vessel is closed, stirring at 600rpm, stopping heating and stirring, cooling to room temperature, adding 5mL of water for washing, extracting with ethyl acetate for 3 times, combining organic phases, drying with 0.5g of anhydrous sodium sulfate, filtering, distilling under reduced pressure, and purifying by column chromatography, wherein eluent of the column chromatography consists of petroleum ether and ethyl acetate according to a volume ratio of 20:1, thus obtaining the S-biaryl dithiocarbamic acid ester compound (yield: 50%; product is the same as example 1).
Example 8:
a method for synthesizing an S-biaryl dithiocarbamate compound, comprising the steps of:
0.1mmol of 1, 9-dimethyl-dibenzo [ b, d ] iodonium triflate, 0.25mmol of di-n-propylamine, 0.25mmol of carbon disulfide and 1.5mL of acetonitrile are added into a reaction vessel, the reaction vessel is closed and stirred at 45 ℃ for 2 hours, the stirring speed is 600rpm, heating and stirring are stopped, cooling to room temperature is carried out, 5mL of water is added for water washing, ethyl acetate is used for extraction for 3 times, the organic phases are combined, then 0.5g of anhydrous sodium sulfate is used for drying, filtration and reduced pressure distillation are carried out, column chromatography purification is carried out, and eluent of the column chromatography consists of petroleum ether and ethyl acetate according to the volume ratio of 20:1, thus obtaining the S-biaryl dithiocarbamic acid ester compound (yield: 87%).
The nuclear magnetic resonance hydrogen spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in the embodiment is shown in fig. 3, the nuclear magnetic resonance carbon spectrum is shown in fig. 4, and the resolution data are as follows:
1 H NMR(400MHz,CDCl 3 )：δ＝7.77(d,J＝7.9Hz,1H),7.66(dd,J＝7.3,1.7Hz,1H),7.49-7.39(m,2H),7.22(dt,J＝7.5,1.0Hz,1H),6.94(t,J＝7.7Hz,1H),3.93-3.76(m,2H),3.58-3.37(m,2H),2.12(s,3H),2.02(s,3H),1.77-1.67(m,2H),1.61-1.40(m,2H),0.91(t,J＝7.4Hz,3H),0.80(t,J＝7.4Hz,3H)。
13 C NMR(100MHz,CDCl 3 )：δ＝195.14,148.11,144.06,139.05,137.53,136.56,136.18,131.73,130.86,129.92,128.75,128.04,102.06,56.84,54.72,21.96,20.98,20.20,19.68,11.21,11.10。
the infrared data and mass spectrum data of the S-biaryl dithio carbamate compound synthesized in the embodiment are as follows:
IR(KBr)ν max ：3052,2964,2926,2872,1552,1480,1444,1364,1303,1269,1237,1194,1144,1091,1033,987,919,891,861,829,770,743,672,618cm -1 。
HRMS(ESI)：Calcd for C 21 H 26 INS 2 [M+H] + :484.0624,Found 484.0627。
in summary, the structural formula of the S-biaryl dithio carbamate compound synthesized in this example is as follows:
example 9:
a method for synthesizing an S-biaryl dithiocarbamate compound, comprising the steps of:
0.1mmol of 1, 9-dimethyl-dibenzo [ b, d ] iodonium triflate, 0.25mmol of diisobutylamine, 0.25mmol of carbon disulfide and 1.5mL of acetonitrile are added into a reaction vessel, the reaction vessel is closed and stirred at 45 ℃ for 2 hours, the stirring speed is 600rpm, heating and stirring are stopped, cooling to room temperature is carried out, 5mL of water is added for water washing, ethyl acetate is used for extraction for 3 times, the organic phases are combined, then 0.5g of anhydrous sodium sulfate is used for drying, filtration and reduced pressure distillation are carried out, column chromatography purification is carried out, and eluent of the column chromatography consists of petroleum ether and ethyl acetate according to the volume ratio of 20:1, thus obtaining the S-biaryl dithiocarbamic acid ester compound (yield: 79%).
The nuclear magnetic resonance hydrogen spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in the embodiment is shown in fig. 5, the nuclear magnetic resonance carbon spectrum is shown in fig. 6, and the resolution data are as follows:
1 H NMR(400MHz,CDCl 3 )：δ＝7.77(d,J＝7.9Hz,1H),7.66(dd,J＝7.3,1.7Hz,1H),7.48-7.41(m,2H),7.20(d,J＝7.5Hz,1H),6.93(t,J＝7.7Hz,1H),4.00(d,J＝12.7Hz,1H),3.55(q,J＝12.4,7.1Hz,2H),3.31(d,J＝11.2Hz,1H),2.42(dt,J＝14.1,7.0Hz,1H),2.11(s,3H),2.02(s,3H),1.89(d,J＝11.0Hz,1H),0.94-0.72(m,12H)。
13 C NMR(100MHz,CDCl 3 )：δ＝196.21,148.31,144.09,139.06,137.86,136.59,136.19,131.82,130.70,129.91,128.67,128.00,102.08,61.30,21.96,20.22,20.19。
the infrared data and mass spectrum data of the S-biaryl dithio carbamate compound synthesized in the embodiment are as follows:
IR(KBr)ν max ：3052,2960,2926,2869,1553,1471,1443,1408,1357,1284,1240,1195,1147,1090,1036,996,943,904,862,826,770,740,673,631cm -1 。
HRMS(ESI)：Calcd for C 23 H 30 INS 2 [M+H] + :512.0937,Found 512.0941。
in summary, the structural formula of the S-biaryl dithio carbamate compound synthesized in this example is as follows:
example 10:
a method for synthesizing an S-biaryl dithiocarbamate compound, comprising the steps of:
adding 0.1mmol of 1, 9-dimethyl-dibenzo [ b, d ] iodonium triflate, 0.25mmol of N-ethyl N-propylamine, 0.25mmol of carbon disulfide and 1.5mL of acetonitrile into a reaction vessel, stirring and reacting for 2 hours at 45 ℃ after the reaction vessel is closed, stirring at 600rpm, stopping heating and stirring, cooling to room temperature, adding 5mL of water for water washing, extracting for 3 times by ethyl acetate, combining organic phases, drying by 0.5g of anhydrous sodium sulfate, filtering, distilling under reduced pressure, purifying by column chromatography, and obtaining the S-biaryl dithiocarbamic acid ester compound (yield: 98 percent) by volume ratio of eluent consisting of petroleum ether and ethyl acetate.
The nuclear magnetic resonance hydrogen spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in the embodiment is shown in fig. 7, the nuclear magnetic resonance carbon spectrum is shown in fig. 8, and the resolution data are as follows:
1 H NMR(400MHz,CDCl 3 )：δ＝7.77(d,J＝7.9Hz,1H),7.66(dd,J＝7.4,1.7Hz,1H),7.48-7.40(m,2H),7.22(dt,J＝7.6,0.9Hz,1H),6.94(t,J＝7.7Hz,1H),4.06-3.79(m,2H),3.69-3.36(m,2H),2.12(s,3H),2.02(s,3H),1.72(q,J＝7.6Hz,1H),1.51(dt,J＝39.4,7.6Hz,1H),1.16(dt,J＝58.1,7.1Hz,3H),0.86(dt,J＝46.2,7.4Hz,3H)。
13 C NMR(100MHz,CDCl 3 )：δ＝194.83,148.07,144.04,139.05,137.47,136.57,136.18,131.72,130.87,129.91,128.80,128.04,102.04,56.39,54.12,50.05,47.91,21.97,21.04,20.20,19.78,12.54,11.54,11.22,11.10。
the infrared data and mass spectrum data of the S-biaryl dithio carbamate compound synthesized in the embodiment are as follows:
IR(KBr)ν max ：3052,2967,2927,2872,1552,1483,1445,1372,1351,1288,1250,1199,1142,1090,1037,993,940,888,861,827,771,672cm -1 。
HRMS(ESI)：Calcd for C 20 H 24 INS 2 [M+H] + :470.0468,Found 470.0471。
in summary, the structural formula of the S-biaryl dithio carbamate compound synthesized in this example is as follows:
example 11:
a method for synthesizing an S-biaryl dithiocarbamate compound, comprising the steps of:
adding 0.1mmol of 1, 9-dimethyl-dibenzo [ b, d ] iodonium triflate, 0.25mmol of N-methylcyclohexylamine, 0.25mmol of carbon disulfide and 1.5mL of acetonitrile into a reaction vessel, stirring and reacting for 2 hours at 35 ℃ after the reaction vessel is closed, stirring at 600rpm, stopping heating and stirring, cooling to room temperature, adding 5mL of water for water washing, extracting for 3 times by ethyl acetate, combining organic phases, drying by 0.5g of anhydrous sodium sulfate, filtering, distilling under reduced pressure, purifying by column chromatography, and obtaining the S-biaryl dithiocarbamic acid ester compound (yield: 80 percent) by using petroleum ether and ethyl acetate according to the volume ratio of 20:1.
The nuclear magnetic resonance hydrogen spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in the embodiment is shown in fig. 9, the nuclear magnetic resonance carbon spectrum is shown in fig. 10, and the resolution data are as follows:
1 H NMR(400MHz,CDCl 3 )：δ＝7.77(d,J＝7.9Hz,1H),7.65(dd,J＝11.6,7.3Hz,1H),7.48-7.38(m,2H),7.23(d,J＝7.5Hz,1H),6.95(q,J＝7.1Hz,1H),5.44-4.26(m,1H),3.20(d,J＝103.8Hz,3H),2.14(s,3H),2.01(s,3H),1.91-1.61(m,5H),1.51-1.05(m,6H)。
13 C NMR(100MHz,CDCl 3 )：δ＝139.05,137.38,136.83,136.59,136.17,131.66,131.51,129.91,128.88,128.80,128.05,102.01,62.82,62.39,37.46,34.91,30.51,30.18,29.45,29.24,25.45,25.20,21.99,20.20。
the infrared data and mass spectrum data of the S-biaryl dithio carbamate compound synthesized in the embodiment are as follows:
IR(KBr)ν max ：3049,2927,2854,1552,1443,1388,1365,1316,1254,1220,1176,1147,1082,1004,973,897,866,830,770,741,670,638.83cm -1 。
HRMS(ESI)：Calcd for C 22 H 26 INS 2 [M+H] + :496.0624,Found 496.0628。
in summary, the structural formula of the S-biaryl dithio carbamate compound synthesized in this example is as follows:
example 12:
a method for synthesizing an S-biaryl dithiocarbamate compound, comprising the steps of:
adding 0.1mmol of 1, 9-dimethyl-dibenzo [ b, d ] iodonium triflate, 0.25mmol of morpholine, 0.25mmol of carbon disulfide and 1.5mL of acetonitrile into a reaction vessel, stirring at 45 ℃ for 2 hours after the reaction vessel is closed, stirring at 600rpm, stopping heating and stirring, cooling to room temperature, adding 5mL of water for water washing, extracting 3 times by ethyl acetate, combining organic phases, drying by 0.5g of anhydrous sodium sulfate, filtering, distilling under reduced pressure, purifying by column chromatography, and obtaining the S-biaryl dithiocarbamic acid ester compound (yield: 75 percent) by volume ratio of eluent of petroleum ether and ethyl acetate.
The nuclear magnetic resonance hydrogen spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in the embodiment is shown in fig. 11, the nuclear magnetic resonance carbon spectrum is shown in fig. 12, and the resolution data are as follows:
1 H NMR(400MHz,CDCl 3 )：δ＝7.77(d,J＝7.9Hz,1H),7.66-7.59(m,1H),7.48-7.40(m,2H),7.25(d,J＝7.5Hz,1H),6.97(t,J＝7.7Hz,1H),3.69(s,8H),2.13(s,3H),2.01(s,3H)。
13 C NMR(100MHz,CDCl 3 )：δ＝196.67,147.77,143.83,138.94,136.82,136.75,136.30,131.80,130.52,130.02,129.05,128.23,101.87,51.49,21.95,20.19。
the infrared data and mass spectrum data of the S-biaryl dithio carbamate compound synthesized in the embodiment are as follows:
IR(KBr)ν max ：3051,2967,2919,2855,1552,1456,1417,1300,1266,1224,1180,1113,1063,1030,990,906,864,825,772,738,702,672,634cm -1 。
HRMS(ESI)：Calcd for C 19 H 20 INOS 2 [M+H] + :470.0104,Found 470.0108。
in summary, the structural formula of the S-biaryl dithio carbamate compound synthesized in this example is as follows:
example 13:
a method for synthesizing an S-biaryl dithiocarbamate compound, comprising the steps of:
adding 0.1mmol of 1, 9-dimethyl-dibenzo [ b, d ] iodonium triflate, 0.25mmol of N-benzyl glycine ethyl ester, 0.25mmol of carbon disulfide and 1.5mL of acetonitrile into a reaction vessel, sealing the reaction vessel, stirring at 45 ℃ for 2h, stopping heating and stirring, cooling to room temperature, adding 5mL of water for water washing, extracting 3 times by ethyl acetate, combining organic phases, drying by 0.5g of anhydrous sodium sulfate, filtering, distilling under reduced pressure, purifying by column chromatography, wherein eluent of the column chromatography consists of petroleum ether and ethyl acetate according to a volume ratio of 20:1, and thus the S-biaryl dithiocarbamate compound (yield: 94%) is obtained.
The nuclear magnetic resonance hydrogen spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in the embodiment is shown in fig. 13, the nuclear magnetic resonance carbon spectrum is shown in fig. 14, and the resolution data are as follows:
1 H NMR(400MHz,CDCl 3 )：δ＝7.77(d,J＝7.9Hz,1H),7.72(dd,J＝7.3,1.9Hz,1H),7.52-7.43(m,2H),7.43-7.10(m,5H),7.07-6.99(m,2H),5.36-4.12(m,6H),2.14(s,3H),2.04(s,3H),1.26(t,J＝7.1Hz,3H)。
13 C NMR(100MHz,CDCl 3 )：δ＝198.94,167.55,139.04,137.38,136.80,136.32,134.51,132.05,130.56,130.02,128.95,128.86,128.29,128.17,127.93,101.96,61.33,57.16,54.69,21.94,20.24,14.18。
the infrared data and mass spectrum data of the S-biaryl dithio carbamate compound synthesized in the embodiment are as follows:
IR(KBr)ν max ：3056,2980,2925,1744,1552,1493,1457,1431,1387,1348,1268,1216,1195,1166,1089,1027,978,903,856,828,773,737,700,673,638cm -1 。
HRMS(ESI)：Calcd for C 26 H 26 INO 2 S 2 [M+H] + :576.0522,Found 576.0527。
in summary, the structural formula of the S-biaryl dithio carbamate compound synthesized in this example is as follows:
example 14:
a method for synthesizing an S-biaryl dithiocarbamate compound, comprising the steps of:
0.1mmol of 1, 9-dimethyl-dibenzo [ b, d ] iodonium triflate, 0.25mmol of benzylamine, 0.25mmol of carbon disulfide and 1.5mL of acetonitrile are added into a reaction vessel, the reaction vessel is closed and then stirred for 2 hours at 35 ℃, the stirring speed is 600rpm, heating and stirring are stopped, cooling to room temperature is carried out, 5mL of water is added for water washing, ethyl acetate is used for extraction for 3 times, the organic phases are combined, 0.5g of anhydrous sodium sulfate is used for drying, filtration and reduced pressure distillation are carried out, column chromatography purification is carried out, and eluent of the column chromatography consists of petroleum ether and ethyl acetate according to the volume ratio of 20:1, thus obtaining the S-biaryl dithiocarbamic acid ester compound (yield: 34%).
The nuclear magnetic resonance hydrogen spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in the embodiment is shown in fig. 15, the nuclear magnetic resonance carbon spectrum is shown in fig. 16, and the resolution data are as follows:
1 H NMR(400MHz,CDCl 3 )：δ＝7.74(d,J＝7.9Hz,1H),7.58(dd,J＝6.8,2.3Hz,1H),7.43-7.39(m,2H),7.31(dt,J＝6.6,2.0Hz,3H),7.28-7.21(m,3H),7.00(t,J＝7.8Hz,1H),5.00(dd,J＝14.9,6.0Hz,1H),4.73(dd,J＝15.0,4.8Hz,1H),2.00(s,3H),1.93(s,3H)。
13 C NMR(100MHz,CDCl 3 )：δ＝194.37,147.77,142.76,138.95,137.74,136.77,135.70,134.05,133.00,130.19,129.71,129.34,128.81,128.45,128.05,128.03,100.05,50.28,21.59,20.38。
the infrared data and mass spectrum data of the S-biaryl dithio carbamate compound synthesized in the embodiment are as follows:
IR(KBr)ν max ：3350,3056,2922,1553,1498,1447,1379,1327,1266,1175,1080,998,927,859,828,748,699,669,605cm -1 。
HRMS(ESI)：Calcd for C 22 H 20 INS 2 [M+H] + :490.0155,Found 490.0158。
in summary, the structural formula of the S-biaryl dithio carbamate compound synthesized in this example is as follows:
example 15:
a method for synthesizing an S-biaryl dithiocarbamate compound, comprising the steps of:
adding 0.1mmol of 1, 4-dimethyl-9-trifluoromethyl-dibenzo [ b, d ] iodonium triflate, 0.25mmol of diethylamine, 0.25mmol of carbon disulfide and 1.5mL of acetonitrile into a reaction vessel, stirring and reacting for 2 hours at 45 ℃ after the reaction vessel is closed, stirring at 600rpm, stopping heating and stirring, cooling to room temperature, adding 5mL of water for washing, extracting for 3 times by ethyl acetate, combining organic phases, drying by 0.5g of anhydrous sodium sulfate, filtering, distilling under reduced pressure, purifying by column chromatography, and obtaining the S-biaryl dithiocarbamic acid ester compound (yield: 88 percent) by volume ratio of petroleum ether to ethyl acetate.
The nuclear magnetic resonance hydrogen spectrogram of the S-biaryl dithiocarbamate compound synthesized in the embodiment is shown in fig. 17, the nuclear magnetic resonance carbon spectrogram is shown in fig. 18, the nuclear magnetic resonance fluorine spectrogram is shown in fig. 19, and the resolution data are as follows:
1 H NMR(400MHz,CDCl 3 )：δ＝8.07(dd,J＝8.0,1.3Hz,1H),7.90(dd,J＝7.9,1.3Hz,1H),7.65(td,J＝7.9,1.0Hz,1H),7.18-7.09(m,2H),3.97(dd,J＝14.9,7.7Hz,2H),3.69-3.49(m,2H),2.50(s,3H),2.06(s,3H),1.26(t,J＝7.1Hz,3H),1.09(t,J＝7.2Hz,3H)。
13 C NMR(100MHz,CDCl 3 )：δ＝192.90,147.16,143.64,141.86,138.84,136.60,134.16,129.42,128.93,128.05,128.00,127.90,109.19,49.87,47.45,29.39,21.79,12.61,11.53。
19 F NMR(376MHz,CDCl 3 )：δ＝-60.39。
the infrared data and mass spectrum data of the S-biaryl dithio carbamate compound synthesized in the embodiment are as follows:
IR(KBr)ν max ：2978,2931,1486,1448,1417,1378,1353,1308,1268,1203,1171,1135,1094,1073,1006,979,914,810,751,705,659cm -1 。
HRMS(ESI)：Calcd for C 20 H 21 F 3 INS 2 [M+H] + :524.0185,Found 524.0190。
in summary, the structural formula of the S-biaryl dithio carbamate compound synthesized in this example is as follows:
example 16:
a method for synthesizing an S-biaryl dithiocarbamate compound, comprising the steps of:
0.1mmol of 1,4, 9-trimethyl-dibenzo [ b, d ] iodonium triflate, 0.25mmol of diethylamine, 0.25mmol of carbon disulfide and 1.5mL of acetonitrile are added into a reaction vessel, the reaction vessel is closed and stirred at 45 ℃ for 2 hours, the stirring speed is 600rpm, heating and stirring are stopped, cooling to room temperature is carried out, 5mL of water is added for water washing, ethyl acetate is used for extraction for 3 times, the organic phases are combined, then 0.5g of anhydrous sodium sulfate is used for drying, filtration and reduced pressure distillation are carried out, column chromatography purification is carried out, and eluent of column chromatography consists of petroleum ether and ethyl acetate according to the volume ratio of 20:1, thus obtaining the S-biaryl dithiocarbamic acid ester compound (yield: 84%).
The nuclear magnetic resonance hydrogen spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in the embodiment is shown in fig. 20, the nuclear magnetic resonance carbon spectrum is shown in fig. 21, and the resolution data are as follows:
1 H NMR(400MHz,CDCl 3 )：δ＝7.67(dd,J＝7.5,1.6Hz,1H),7.47-7.39(m,2H),7.12(s,2H),4.05-3.87(m,2H),3.64-3.53(m,2H),2.50(s,3H),2.09(s,3H),1.99(s,3H),1.24(t,J＝7.0Hz,3H),1.08(t,J＝7.0Hz,3H)。
13 C NMR(100MHz,CDCl 3 )：δ＝194.51,148.94,144.54,139.24,137.32,136.56,135.76,131.65,130.91,129.67,128.29,127.84,108.77,29.47,21.61,20.19。
the infrared data and mass spectrum data of the S-biaryl dithio carbamate compound synthesized in the embodiment are as follows:
IR(KBr)ν max ：3046,2975,2927,2869,1555,1483,1448,1377,1352,1299,1267,1205,1140,1086,1071,1007,981,917,860,818,774,748,722,679cm -1 。
HRMS(ESI)：Calcd for C 20 H 24 INS 2 [M+H] + :470.0468,Found 470.0472。
in summary, the structural formula of the S-biaryl dithio carbamate compound synthesized in this example is as follows:
example 17:
a method for synthesizing an S-biaryl dithiocarbamate compound, comprising the steps of:
adding 0.1mmol of 1,3,4, 9-trimethyl-dibenzo [ b, d ] iodonium triflate, 0.25mmol of diethylamine, 0.25mmol of carbon disulfide and 1.5mL of acetonitrile into a reaction vessel, sealing the reaction vessel, stirring at 45 ℃ for 2 hours, stopping heating and stirring, cooling to room temperature, adding 5mL of water for water washing, extracting 3 times by ethyl acetate, combining organic phases, drying by 0.5g of anhydrous sodium sulfate, filtering, distilling under reduced pressure, purifying by column chromatography, wherein eluent of the column chromatography consists of petroleum ether and ethyl acetate according to a volume ratio of 20:1, and thus the S-biaryl dithiocarbamate compound (yield: 75%) is obtained.
The nuclear magnetic resonance hydrogen spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in the embodiment is shown in fig. 22, the nuclear magnetic resonance carbon spectrum is shown in fig. 23, and the resolution data are as follows:
1 H NMR(400MHz,CDCl 3 )：δ＝7.65(dd,J＝7.4,1.7Hz,1H),7.45-7.38(m,2H),7.00(s,1H),3.97(d,J＝7.5Hz,2H),3.70-3.50(m,2H),2.49(s,3H),2.39(s,3H),2.05(s,3H),1.99(s,3H),1.24(t,J＝7.1Hz,3H),1.09(t,J＝6.9Hz,3H)。
13 C NMR(100MHz,CDCl 3 )：δ＝194.68,149.34,142.34,137.12,137.07,136.72,135.74,135.51,131.69,131.51,131.24,127.71,110.25,26.21,21.83,21.49,20.27。
the infrared data and mass spectrum data of the S-biaryl dithio carbamate compound synthesized in the embodiment are as follows:
IR(KBr)ν max ：3052,2975,2927,2867,1532,1483,1448,1379,1352,1299,1267,1203,1140,1071,1008,981,917,865,826,777,744,709cm -1 。
HRMS(ESI)：Calcd for C 21 H 26 INS 2 [M+H] + :484.0624,Found 484.0628。
in summary, the structural formula of the S-biaryl dithio carbamate compound synthesized in this example is as follows:
example 18:
a method for synthesizing an S-biaryl dithiocarbamate compound, comprising the steps of:
0.1mmol of 1, 9-dichloro-dibenzo [ b, d ] iodonium triflate, 0.25mmol of diethylamine, 0.25mmol of carbon disulfide and 1.5mL of acetonitrile are added into a reaction vessel, the reaction vessel is closed and stirred at 45 ℃ for 2 hours, the stirring speed is 600rpm, heating and stirring are stopped, cooling to room temperature is carried out, 5mL of water is added for water washing, ethyl acetate is used for extraction for 3 times, the organic phases are combined, 0.5g of anhydrous sodium sulfate is used for drying, filtration and reduced pressure distillation are carried out, column chromatography purification is carried out, and eluent of the column chromatography consists of petroleum ether and ethyl acetate according to the volume ratio of 20:1, thus obtaining the S-biaryl dithiocarbamate compound (yield: 61%).
The nuclear magnetic resonance hydrogen spectrum of the S-biaryl dithiocarbamic acid ester compound synthesized in the embodiment is shown in fig. 24, the nuclear magnetic resonance carbon spectrum is shown in fig. 25, and the resolution data are as follows:
1 H NMR(400MHz,CDCl 3 )：δ＝7.86(dd,J＝8.0,1.1Hz,1H),7.79(dd,J＝7.8,1.2Hz,1H),7.63(dd,J＝8.1,1.2Hz,1H),7.55-7.45(m,2H),7.02(t,J＝8.0Hz,1H),4.06-3.86(m,2H),3.60(s,2H),1.26(t,J＝7.2Hz,3H),1.11(t,J＝7.2Hz,3H)。
13 C NMR(100MHz,CDCl 3 )：δ＝192.20,145.07,141.72,138.35,137.35,134.49,133.81,133.25,130.92,130.28,129.43,129.23,101.22。
the infrared data and mass spectrum data of the S-biaryl dithio carbamate compound synthesized in the embodiment are as follows:
IR(KBr)ν max ：3064,2977,2929,1549,1485,1454,1418,1378,1351,1298,1268,1199,1142,1113,1068,1007,976,914,824,776,725cm -1 。
HRMS(ESI)：Calcd for C 17 H 16 Cl 2 INS 2 [M+H] + :495.9219,Found 495.9223。
in summary, the structural formula of the S-biaryl dithio carbamate compound synthesized in this example is as follows:
the above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. A method for synthesizing an S-biaryl dithiocarbamate compound, comprising the steps of: dispersing cyclic diaryl iodonium salt, amine and carbon disulfide in a solvent for reaction to obtain an S-biaryl dithio carbamate compound; the structural formula of the cyclic diaryl iodonium salt is as follows:wherein R is 1 Is at least one of methyl, ethyl, tertiary butyl, fluorine, chlorine, methoxy and trifluoromethyl, R 2 Is at least one of methyl, ethyl, tertiary butyl, fluorine, chlorine, methoxy and trifluoromethyl.
2. The method for synthesizing an S-biaryl dithiocarbamate according to claim 1, wherein: the molar ratio of the cyclic diaryl iodonium salt to the amine to the carbon disulfide is 1:1-4:1-4.
3. The method for synthesizing an S-biaryl dithiocarbamate according to claim 1 or 2, wherein: the structural formula of the amine is as follows:wherein R is 3 Is one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, cyclohexyl, benzyl and 2-naphthylmethyl, R 4 Is one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, cyclohexyl, benzyl and 2-naphthylmethyl.
4. The method for synthesizing an S-biaryl dithiocarbamate according to claim 1 or 2, wherein: the amine is one of tetrahydropyrrole, piperidine, 4-phenylpiperidine, cyclohexylimine, morpholine, thiomorpholine, 1-phenylpiperazine, N-benzyl glycine ethyl ester, desloratadine, amoxapine and fluoxetine.
5. The method for synthesizing an S-biaryl dithiocarbamate according to claim 1 or 2, wherein: the solvent is at least one of acetonitrile, dichloromethane and water.
6. The method for synthesizing an S-biaryl dithiocarbamate according to claim 1 or 2, wherein: the reaction is carried out at 25-85 ℃ for 2-12 h.
7. The method for synthesizing an S-biaryl dithiocarbamate according to claim 1 or 2, wherein: the reaction is carried out at a stirring rate of 400rpm to 800 rpm.
8. The method for synthesizing an S-biaryl dithiocarbamate according to claim 1 or 2, wherein: after the reaction is finished, the reaction solution is separated and purified.
9. The method for synthesizing S-biaryl dithiocarbamates of claim 8, wherein: the specific operation of separation and purification is as follows: the reaction solution is washed with water, extracted with ethyl acetate, and then the organic layer is taken for drying, filtering and reduced pressure distillation, and then column chromatography purification is carried out.
10. The method for synthesizing S-biaryl dithiocarbamates according to claim 9, wherein: the eluent of the column chromatography consists of petroleum ether and ethyl acetate according to the volume ratio of 15-25:1.
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| 黄洁诚: "以环状二芳基碘鎓盐合成（二硫代）氨基甲酸芳香酯的研究", 中国优秀硕士学位论文全文数据库工程科技Ⅰ辑, 15 April 2025 (2025-04-15) * |
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