CN110117239A - Asymmetric trithio class compound and its synthetic method and application - Google Patents

Asymmetric trithio class compound and its synthetic method and application Download PDF

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CN110117239A
CN110117239A CN201810124062.1A CN201810124062A CN110117239A CN 110117239 A CN110117239 A CN 110117239A CN 201810124062 A CN201810124062 A CN 201810124062A CN 110117239 A CN110117239 A CN 110117239A
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reaction
compound
formula
trithio
amino acid
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姜雪峰
薛佳晖
肖霄
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East China Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
    • C07C319/24—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides by reactions involving the formation of sulfur-to-sulfur bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/56—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/57—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C323/58—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups with amino groups bound to the carbon skeleton
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    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/12—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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Abstract

The synthetic method of the invention discloses one kind asymmetry trithio class compound as shown in formula (3), with over cure reagent R shown in formula (1)1SSOMe is reaction raw materials with organic sulfur alcohol compound shown in formula (2), and under the action of catalyst, reaction obtains the asymmetric trithio class compound.Reaction condition of the present invention is mild, and raw material is cheap and easy to get, and operation is simple, yield is higher, metallic catalyst is not necessarily in reaction, environmentally friendly it is not necessary that additional oxidation or reducing agent is added；Reaction substrate is easy preparation；Reaction efficiency is high after reaction amplification.Organic mercaptan in formula (2) can be the polypeptide compounds containing mercaptan, and the present invention provides method for the sulfur modification of crossing of polypeptide.The present invention has wide application prospect and practical value.

Description

Asymmetric trithio class compound and its synthetic method and application
Technical field
The invention belongs to organic compound technique applied technical fields, and in particular to asymmetric trithio class compound and its conjunction At methods and applications.
Background technique
The organic compound of the structure containing trithio is a kind of very important compound, and trisulfide is widely present in Natural products, especially marine natural products, such as famous Epidithiodiketopiperazines (ETPs) class naturally produce In object (as follows).And trisulfide also has preferable application in terms of materials chemistry, and research finds trisulfide Cathode material as rechargeable lithium battery is shown compared with the higher efficiency of disulphide.Furthermore polysulfide or common Lube oil additive, mainly as gear oil.Therefore a kind of mild condition is found, easy to operate, the wide over cure examination of substrate spectrum Agent building trisulfide is particularly important.
In the prior art, the method for synthesizing asymmetric trisulfide at present is seldom, and most traditional construction method is with adjacent benzene Dicarboximide sets out, and synthesizes azepine sulfur vulcanization object by two-step reaction, azepine sulfur vulcanization object can then be synthesized with thiol reaction Trisulfide needs using the biggish phthalimide of molecular weight during synthesizing azepine sulfur vulcanization object, and need to make With unstable, boiling point low and strong corrosivity raw material sulfur dichloride, factors above reduces the practicability of the reagent.And it is big Under the conditions of majority this method synthesize trisulfides reagent efficiency it is lower.
Therefore, it finds a kind of with versatility, is participated in without metal, plant efficient, environmental-friendly, mild condition and warp The applicable synthesis trisulfide method of Ji, which just seems, to be even more important.
Summary of the invention
The present invention overcomes the shortcomings of conventional synthesis trisulfide, use is tasteless, the stable, over cure that easily prepares Reagent R1SSOMe, the reaction have the characteristics that reactivity is strong, is not necessarily to metal catalytic.In consideration of it, the present invention devise by using Lewis acid catalyst passes through a kind of organic sulfur alcohol compound and R1The necleophilic reaction of SSOMe prepares asymmetric trithio class The reaction method of compound.
The invention proposes a kind of asymmetric trithio class compounds, shown in structural formula such as formula (3):
Wherein, R1Selected from straight chained alkyl, substituted benzyl, sugar, containing sugar derivatives, amino acid derivativges etc.；
R2Selected from alkyl, aryl, substituted aryl, amino acid derivativges, oligopeptides compound etc.；
Preferably, R1Selected from decyl, to cyanobenzyls, pyranose sugar derivatives, furanose derivative, amino acid derivativges；
R2Selected from isopropyl, normal-butyl, isobutyl group, tert-butyl, cyclohexyl, n-octyl, dodecyl, allyl, ten Seven fluorine decyls, tri- ethoxy silicon substrate n-propyl of 1-, 1- ethoxy, adamantyl, to t-butylbenzyl, to methoxy-benzyl, 1- pyrrole Piperazine ethyl, p-methoxyphenyl, o-methyl-phenyl, 1,8- bis- replace octyl, ethylene glycol diethyl, dodecyl, amino acid to spread out Biology, oligopeptides compound.
Further, asymmetry trithio class compound shown in formula (3) includes:
The invention proposes a kind of synthetic methods of asymmetric trithio class compound, with over cure reagent shown in formula (1) R1Organic sulfur alcohol compound shown in SSOMe and formula (2) is reaction raw materials, under the action of catalyst, in organic solvent, instead It should obtain the asymmetry trithio class compound as shown in formula (3).Shown in the reaction process such as reaction equation (a)；
Wherein, R1Selected from straight chained alkyl, substituted benzyl, sugar, containing sugar derivatives, amino acid derivativges etc.；
R2Selected from alkyl, aryl, substituted aryl, amino acid derivativges, oligopeptides compound etc.；
Preferably, R1Selected from decyl, to cyanobenzyls, pyranose sugar derivatives, furanose derivative, amino acid derivativges；
R2Selected from isopropyl, normal-butyl, isobutyl group, tert-butyl, cyclohexyl, n-octyl, dodecyl, allyl, ten Seven fluorine decyls, tri- ethoxy silicon substrate n-propyl of 1-, 1- ethoxy, adamantyl, to t-butylbenzyl, to methoxy-benzyl, 1- pyrrole Piperazine ethyl, p-methoxyphenyl, o-methyl-phenyl, 1,8- bis- replace octyl, ethylene glycol diethyl, dodecyl, amino acid to spread out Biology, oligopeptides compound.
In the present invention, over cure reagent shown in organic sulfur alcohol compound shown in the formula (2) and formula (1) R1The molar ratio of SSOMe is 1.0:2.0-2.5:1.0；Preferably, the molar ratio of the two dosage is 1.1:1.0.
In the present invention, the catalyst is B (C6F5)3。
In the present invention, the mole dosage of the catalyst is over cure reagent R shown in formula (1)1The 0-5mol% of SSOMe； Preferably, the mole dosage of the catalyst is over cure reagent R shown in formula (1)1The 0mol% of SSOMe or 2.5mol%.
In the present invention, the organic solvent is methylene chloride.
In the present invention, the reaction is carried out at 0-40 DEG C；It preferably, is carried out at 10-40 DEG C；Further preferably Ground, the temperature of reaction are 25 DEG C.
In the present invention, the time of the reaction is 5-8 hours；Preferably, it is 5 hours.
The invention also provides a kind of over cure reagents, shown in structure such as formula (1),
Wherein, R1Selected from straight chained alkyl, substituted benzyl, sugar, containing sugar derivatives, amino acid derivativges etc.；
Preferably, R1Selected from decyl, to cyanobenzyls, pyranose sugar derivatives, furanose derivative, amino acid derivativges.
In the present invention, R is used1SSOMe is over cure reagent, under Lewis acid catalyst, to thio-alcohol chemical combination Object carries out over cure reaction, is a kind of novelty, and efficient over cure reaction is the effective way for synthesizing asymmetric trithio class compound Diameter.
In a specific example, synthetic reaction of the present invention is added organic mercaptan (2) (X mmol) in reaction flask A, R1SSOMe (Y mmol), B (C6F5)3, (Z mmol), organic solvent (P mL), reaction system is at 25 DEG C, N2Stirring 5 is small under atmosphere When；After completion of the reaction, directly silica gel is added to be spin-dried for, obtains target product through column chromatography for separation.
The invention also provides the asymmetry trithio classes as shown in formula (3) being prepared according to the above-mentioned synthetic method of the present invention Compound.
The optimal conditions for the asymmetry trithio class compound as shown in formula (3) that synthetic method of the present invention is prepared is as follows Shown, wherein the yield of reaction equation (a) is 86%.
Wherein, R1Selected from straight chained alkyl, substituted benzyl, sugar, contain sugar derivatives, amino acid derivativges；
R2Selected from alkyl, aryl, substituted aryl, amino acid derivativges, oligopeptides compound；
Preferably, R1Selected from decyl, to cyanobenzyls, pyranose sugar derivatives, furanose derivative, amino acid derivativges；
R2Selected from isopropyl, normal-butyl, isobutyl group, tert-butyl, cyclohexyl, n-octyl, dodecyl, allyl, ten Seven fluorine decyls, tri- ethoxy silicon substrate n-propyl of 1-, 1- ethoxy, adamantyl, to t-butylbenzyl, to methoxy-benzyl, 1- pyrrole Piperazine ethyl, p-methoxyphenyl, o-methyl-phenyl, 1,8- bis- replace octyl, ethylene glycol diethyl, dodecyl, amino acid to spread out Biology, oligopeptides compound.
The invention has the following advantages that reaction is efficiently, high income, wherein 5,14,18,22,23,27 yield of embodiment is all 90% or more；The preparation of over cure reagent is simple, stablizes and has no irritating odor；It is more mild to react conditional；In reaction Use nontransition metal as catalyst, it is economical and practical, it is environmentally friendly；Reaction dissolvent is low boiling point organic solvent, green nothing Poison；The present invention is using the easy MeSSOMe of the mercaptan compound being commercially easy to get and preparation as reaction raw materials, in lewis acid catalyst Under the action of, react the asymmetric trithio class compound replaced；Operation is simple, and reaction condition is more mild, is suitble to Large-scale industrial production.
Specific embodiment
In conjunction with following specific embodiments, the present invention is described in further detail, and of the invention protects content not limit to In following embodiment.Without departing from the spirit and scope of the invention, those skilled in the art it is conceivable that variation and excellent Point is all included in the present invention, and using appended claims as protection scope.Implement process of the invention, condition, Reagent, experimental method etc. are among the general principles and common general knowledge in the art, this hair in addition to what is specifically mentioned below It is bright that there are no special restrictions to content.Data given by following embodiment include concrete operations and reaction condition and product.Product is pure Degree is identified by nuclear-magnetism.
The synthetic reaction of asymmetry trithio class compound of the invention, comprising the following steps:
Such as reaction equation (a), synthetic reaction of the present invention is addition organic mercaptan (2), R in reaction flask1SSOMe, B (C6F5)3, organic solvent, reaction system is at 25 DEG C, N2It is stirred 5 hours under atmosphere；After completion of the reaction, directly silica gel is added to be spin-dried for, Target product is obtained through column chromatography for separation.
Asymmetry trithio class compound as shown in Table 1, is the product synthesized by the method for the invention, there is not yet There is open source literature to disclose these compounds.
The new asymmetric trithio class compound of the invention of table 1
Embodiment 1
The synthesis of compound 3a:
Under nitrogen atmosphere, sequentially added into reaction tube 1a (42.3mg, 0.2mmol), isopropyl mercaptan 2a (20.5uL, 0.22mmol),B(C6F5)3(2.6mg, 0.005mmol), methylene chloride (2.0mL), reaction system stir 5 hours at normal temperature, After completion of the reaction, methylene chloride dilutes, and removes solvent, and column chromatographs to obtain colourless liquid compound 3a (40.9mg, 80%)1H NMR (400MHz,CDCl3) δ 7.62 (d, J=8.3Hz, 2H), 7.43 (d, J=8.3Hz, 2H), 4.07 (s, 2H), 3.15 (tt, J= 6.8Hz, J=6.8Hz, 1H), 1.33 (d, J=6.8Hz, 6H)；13C NMR(100MHz,CDCl3)δ142.3,132.3, 130.1,118.7,111.2,42.2,41.8,22.4；IR(film)2962,2922,2862,2228,1919,1606,1503, 1446,1235,1153,1047,875,842,741,652；HRMS(EI)Calcd for C11H13NS3255.0210,Found 255.0213.
Embodiment 2
The synthesis of compound 3a:
Under nitrogen atmosphere, sequentially added into reaction tube 1a (42.3mg, 0.2mmol), isopropyl mercaptan 2a (20.5uL, 0.22mmol),B(C6F5)3(2.6mg, 0.005mmol), methylene chloride (2.0mL), reaction system stir 5 hours at 0 DEG C, After completion of the reaction, methylene chloride dilutes, and removes solvent, and column chromatographs to obtain colourless liquid compound 3a (15.3mg, 30%)
Embodiment 3
The synthesis of compound 3b:
Under nitrogen atmosphere, sequentially added into reaction tube 1a (42.3mg, 0.2mmol), butyl mercaptan 2b (23.5uL, 0.22mmol),B(C6F5)3(2.6mg, 0.005mmol), methylene chloride (2.0mL), reaction system stir 5 hours at normal temperature, After completion of the reaction, methylene chloride dilutes, and removes solvent, and column chromatographs to obtain colourless liquid compound 3b (47.2mg, 88%)1H NMR (400MHz,CDCl3) δ 7.62 (d, J=8.1Hz, 2H), 7.43 (d, J=8.1Hz, 2H), 4.07 (s, 2H), 2.81 (t, J= 7.3Hz, 2H), 1.84-1.55 (m, 2H), 1.57-1.30 (m, 2H), 0.92 (t, J=7.4Hz, 3H)；13C NMR(100MHz, CDCl3)δ142.3,132.3,130.1,118.7,111.3,42.1,38.5,30.7,21.5,13.6.IR(film)2957, 2927,2867,2228,1919,1606,1504,1460,1380,1222,1101,1047,875,842,740,653.HRMS (EI)Calcd for C12H15NS3269.0367,Found 269.0371.
Embodiment 4
The synthesis of compound 3c:
Under air atmosphere, sequentially added into reaction tube 1a (42.3mg, 0.2mmol), iso-butyl mercaptan 2c (24.0uL, 0.22mmol),B(C6F5)3(2.6mg, 0.005mmol), methylene chloride (2.0mL), reaction system stir 5 hours at normal temperature, After completion of the reaction, methylene chloride dilutes, and removes solvent, and column chromatographs to obtain colourless liquid compound 3c (47.5mg, 88%)1H NMR (400MHz,CDCl3) δ 7.62 (d, J=8.3Hz, 2H), 7.44 (d, J=8.3Hz, 2H), 4.07 (s, 2H), 2.94-2.89 (m, 1H), 1.82-1.66 (m, 1H), 1.63-1.50 (m, 1H), 1.33 (d, J=6.8Hz, 3H), 0.96 (t, J=7.4Hz, 3H).13C NMR(100MHz,CDCl3)δ142.4,132.3,130.2,118.7,111.3,48.8,42.2,28.7,20.0, 11.4.IR(film)2963,2924,2871,2229,1606,1499,1454,1415,1288,1180,1080,962,842, 741,651.HRMS(EI)Calcd for C12H15NS3269.0365,Found 269.0365.
Embodiment 5
The synthesis of compound 3d:
Under nitrogen atmosphere, sequentially added into reaction tube 1a (42.3mg, 0.2mmol), tert-butyl mercaptan 2d (19.9mg, 0.22mmol),B(C6F5)3(2.6mg, 0.005mmol), methylene chloride (2.0mL), reaction system stir 5 hours at normal temperature, After completion of the reaction, methylene chloride dilutes, and removes solvent, and column chromatographs to obtain compound as white solid 3d (50.8mg, 94%)1H NMR (400MHz,CDCl3) δ 7.61 (d, J=8.1Hz, 2H), 7.42 (d, J=8.2Hz, 2H), 4.07 (s, 2H), 1.36 (s, 9H) ；13C NMR(100MHz,CDCl3)δ142.4,132.2,130.1,118.7,111.2,49.1,42.3,29.8.IR(film) 2965,2918,2227,1607,1507,1455,1419,1391,1161,871,851,651.HRMS(EI)Calcd for C12H15NS3 269.0367,Found 269.0368.
Embodiment 6
The synthesis of compound 3e:
Under nitrogen atmosphere, sequentially added into reaction tube 1a (42.3mg, 0.2mmol), cyclohexanethiol 2e (27uL, 0.22mmol),B(C6F5)3(2.6mg, 0.005mmol), methylene chloride (2.0mL), reaction system stir 5 hours at normal temperature, After completion of the reaction, methylene chloride dilutes, and removes solvent, and column chromatographs to obtain colourless liquid compound 3e (49.2mg, 87%)1H NMR (400MHz,CDCl3) δ 7.62 (d, J=8.2Hz, 2H), 7.43 (d, J=8.2Hz, 2H), 4.07 (s, 2H), 2.90 (tt, J= 10.6,3.7Hz,1H),2.13–1.90(m,2H),1.89–1.67(m,2H),1.63-1.60(m,1H),1.49–0.98(m, 5H)；13C NMR(100MHz,CDCl3)δ142.4,132.3,130.2,118.7,111.3,50.1,42.2,32.5,25.9, 25.5.IR(film)2924,2852,2229,1605,1497,1447,1262,1183,1080,965,827,739, 648.HRMS(EI)Calcd for C14H17NS3295.0523,Found 295.0525.
Embodiment 7
The synthesis of compound 3f:
Under nitrogen atmosphere, sequentially added into reaction tube 1a (42.3mg, 0.2mmol), n octylmercaptan 2f (38uL, 0.22mmol),B(C6F5)3(2.6mg, 0.005mmol), methylene chloride (2.0mL), reaction system stir 5 hours at normal temperature, After completion of the reaction, methylene chloride dilutes, and removes solvent, and column chromatographs to obtain colourless liquid compound 3f (55.2mg, 85%)1H NMR (400MHz,CDCl3) δ 7.62 (d, J=8.2Hz, 2H), 7.43 (d, J=8.2Hz, 2H), 4.07 (s, 2H), 2.90 (tt, J= 10.6,3.7Hz,1H),2.13–1.90(m,2H),1.89–1.67(m,2H),1.63-1.60(m,1H),1.49–0.98(m, 5H)；13C NMR(100MHz,CDCl3)δ142.3,132.3,130.1,118.7,111.3,42.1,38.8,31.7,29.1, 29.0,28.7,28.4,22.6,14.1.IR(film)3063,2925,2853,2229,1726,1606,1503,1461, 1289,1196,1020,965,842,740,652.HRMS(EI)Calcd for C16H23NS3325.0993,Found 325.0989.
Embodiment 8
The synthesis of compound 3g:
Under nitrogen atmosphere, 1a (42.3mg, 0.2mmol), n-dodecyl mercaptan 2g are sequentially added into reaction tube (38uL, 0.22mmol), methylene chloride (2.0mL), reaction system stir 8 hours, after completion of the reaction, methylene chloride at normal temperature Dilution, removes solvent, and column chromatographs to obtain colourless liquid compound 3g (68mg, 89%)1H NMR(400MHz,CDCl3)δ7.62(d, J=8.3Hz, 2H), 7.43 (d, J=8.3Hz, 2H), 4.07 (s, 2H), 2.85-2.71 (m, 2H), 1.80-1.63 (m, 2H), 1.40-1.25 (m, 18H), 0.88 (t, J=6.8Hz, 3H)；13C NMR(100MHz,CDCl3)δ142.3,132.3,130.1, 118.6,111.4,42.2,38.9,31.9,29.6,29.6,29.5,29.4,29.3,29.1,28.7,28.4,22.7, 14.1.IR(film)2922,2852,2229,1606,1504,1461,1414,1234,1079,963,842,742, 652.HRMS(EI)Calcd for C20H31NS3381.1619,Found 381.1626.
Embodiment 9
The synthesis of compound 3h:
Under nitrogen atmosphere, sequentially added into reaction tube 1a (42.3mg, 0.2mmol), allyl sulfhydrate 2h (27uL, 0.22mmol),B(C6F5)3(2.6mg, 0.005mmol), methylene chloride (2.0mL), reaction system stir 5 hours at normal temperature, After completion of the reaction, methylene chloride dilutes, and removes solvent, and column chromatographs to obtain colourless liquid compound 3h (41.3mg, 86%)1H NMR (400MHz,CDCl3) δ 7.62 (d, J=8.2Hz, 2H), 7.43 (d, J=8.2Hz, 2H), 5.89-5.79 (m, 1H), 5.28- 5.14 (m, 2H), 4.07 (s, 2H), 3.45 (d, J=7.3Hz, 2H)；13C NMR(100MHz,CDCl3)δ142.2,132.4, 132.3,130.1,119.3,118.6,111.3,42.3,41.5.IR(film)2979,2913,2229,1923,1632, 1606,1505,1414,1223,1103,1073,916,844,724,649.HRMS(EI)Calcd for C11H11NS3253.0544,Found 253.0049.
Embodiment 10
The synthesis of compound 3i:
Under nitrogen atmosphere, sequentially added into reaction tube 1a (42.3mg, 0.2mmol), mercaptan 2i (105.8mg, 0.22mmol), methylene chloride (2.0mL), reaction system stir 8 hours at normal temperature, and after completion of the reaction, methylene chloride dilutes, Solvent is removed, column chromatographs to obtain compound as white solid 3i (103.1mg, 78%)1H NMR(400MHz,CDCl3)δ7.64(d,J =8.0Hz, 2H), 7.44 (d, J=7.9Hz, 2H), 4.09 (s, 2H), 3.29-2.86 (m, 2H), 2.62-2.49 (m, 2H)；19F NMR(377MHz,CDCl3) -80.8 (3F, t, J=9.9Hz),-[113.8 (6)–113.9(3)](2F,m.CF2),‐[121.7‐ 121.8](2F,m.CF2),-122.0(4F,s,2×CF2),-122.8(2F,s,CF2),-123.3(2F,s,CF2),-126.17 (2F,m.CF2)；13C NMR(100MHz,CDCl3)δ141.8,132.4,130.2,118.6,111.6,42.1,31.3(t,2JC-F =22.2Hz), 28.8.IR (film) 2952,2920,2230,1332,1147,1116,953,844,703,647.HRMS (EI) Calcd for C18H10F17NS3658.9704,Found 658.9711.
Embodiment 11
The synthesis of compound 3j:
Under nitrogen atmosphere, sequentially added into reaction tube 1a (42.3mg, 0.2mmol), mercaptan 2j (53uL, 0.22mmol),B(C6F5)3(2.6mg, 0.005mmol), methylene chloride (2.0mL), reaction system stir 5 hours at normal temperature, After completion of the reaction, methylene chloride dilutes, and removes solvent, and column chromatographs to obtain colourless liquid compound 3j (43.6mg, 52%)1H NMR (400MHz,CDCl3) δ 7.61 (d, J=7.9Hz, 2H), 7.43 (d, J=8.1Hz, 2H), 4.06 (s, 2H), 3.81 (q, J= 7.0Hz, 6H), 2.84 (t, J=7.2Hz, 2H), 1.87-1.80 (m, 2H), 1.21 (t, J=7.0Hz, 9H), 0.90-0.41 (m,2H)；13C NMR(100MHz,CDCl3)δ142.3,132.3,130.1,118.7,111.2,58.4,42.0,41.5, 22.3,18.3,9.5.IR(film)2974,2888,2229,1606,1390,1242,1165,1075,957,785.HRMS (EI)Calcd for C17H27NO3S3 417.0922,Found417.0914.
Embodiment 12
The synthesis of compound 3k:
It under nitrogen atmosphere, is sequentially added into reaction tube 1a (42.3mg, 0.2mmol), 2- hydroxyethyl mercaptan 2k (15.5uL,0.22mmol),B(C6F5)3(2.6mg, 0.005mmol), methylene chloride (2.0mL), reaction system is stirred at normal temperature It mixes 5 hours, after completion of the reaction, methylene chloride dilution removes solvent, and column chromatographs to obtain compound as white solid 3k (46mg, 89%) .1H NMR(400MHz,CDCl3) δ 7.62 (d, J=8.2Hz, 2H), 7.43 (d, J=8.0Hz, 2H), 4.09 (s, 2H), 3.90 (t, J=5.6Hz, 2H), 2.98 (t, J=5.8Hz, 2H), 2.17 (s, 1H)；13C NMR(100MHz,CDCl3)δ141.9, 132.3,130.1,118.6,111.4,59.6,42.1,41.4.IR(film)3381,2927,2232,1607,1504,1415, 1182,1104,1040,1101,842,783,650.HRMS(EI)Calcd for C10H11NOS3257.0003,Found 257.0008.
Embodiment 13
The synthesis of compound 3l:
It under nitrogen atmosphere, is sequentially added into reaction tube 1a (42.3mg, 0.2mmol), 1- Buddha's warrior attendant alkanethiol 2l (37.0mg,0.22mmol),B(C6F5)3(2.6mg, 0.005mmol), methylene chloride (2.0mL), reaction system is stirred at normal temperature Mix 5 hours, after completion of the reaction, methylene chloride dilution removes solvent, column chromatograph compound as white solid 3l (62.2mg, 89%)1H NMR(400MHz,CDCl3) δ 7.61 (d, J=8.2Hz, 2H), 7.43 (d, J=8.2Hz, 2H), 4.06 (s, 2H), 2.08(s,3H),1.88(m,6H),1.74–1.63(m,6H)；13C NMR(100MHz,CDCl3)δ142.4,132.2,130.1, 118.7,111.1,50.8,42.4,42.3,35.9,29.8.IR(film)3381,2927,2232,1607,1504,1415, 1182,1104,1040,1101,842,783,650.HRMS(EI)Calcd for C10H11NOS3257.0003,Found 257.0008.
Embodiment 14
The synthesis of compound 3m:
Under nitrogen atmosphere, 1a (42.3mg, 0.2mmol) is sequentially added into reaction tube, to tert-butyl benzyl mercaptan 2m (39.8mg, 0.22mmol), methylene chloride (2.0mL), reaction system stir 8 hours, after completion of the reaction, dichloromethane at normal temperature Alkane dilution, removes solvent, and column chromatographs to obtain colourless liquid compound 3m (66.4mg, 92%)1H NMR(400MHz,CDCl3)δ 7.61 (d, J=8.3Hz, 2H), 7.39 (d, J=8.3Hz, 2H), 7.36 (d, J=8.3Hz, 2H), 7.24 (d, J=8.3Hz, 2H),4.04(s,2H),3.98(s,2H),1.31(s,9H)；13C NMR(100MHz,CDCl3)δ150.8,142.2,133.1, 132.3,130.1,129.1,125.6,118.6,111.4,42.9,42.3,34.5,31.3.IR(film)3055,2956, 2228,1606,1508,1362,1293,1200,970,836,657.HRMS(EI)Calcd for C19H21NS3359.0836, Found 359.0838.
Embodiment 15
The synthesis of compound 3n:
Under nitrogen atmosphere, 1a (42.3mg, 0.2mmol) is sequentially added into reaction tube, to methoxybenzyl mercaptan 2n (34mg, 0.22mmol), methylene chloride (2.0mL), reaction system stir 8 hours, after completion of the reaction, methylene chloride at normal temperature Dilution, removes solvent, and column chromatographs to obtain colourless liquid compound 3n (58.2mg, 87%)1H NMR(400MHz,CDCl3)δ7.61 (d, J=8.2Hz, 2H), 7.40 (d, J=8.2Hz, 2H), 7.21 (d, J=8.6Hz, 2H), 6.86 (d, J=8.7Hz, 2H), 4.01(s,4H),3.80(s,3H)；13C NMR(100MHz,CDCl3)δ159.2,142.3,132.3,132.3,130.5, 130.1,128.1,118.6,114.1,114.0,111.3,55.3,42.6,42.2.IR(film)3065,2929,2838, 2229,1607,1509,1300,1250,1174,1032,825,741,649.HRMS(EI)Calcd for C16H15NOS3333.0316,Found 333.0323.
Embodiment 16
The synthesis of compound 3o:
Under nitrogen atmosphere, 1a (42.3mg, 0.2mmol), 2 pyrazinyl ethyl mercaptan 2o are sequentially added into reaction tube (34mg, 0.22mmol), methylene chloride (2.0mL), reaction system stir 8 hours, after completion of the reaction, methylene chloride at normal temperature Dilution, removes solvent, and column chromatographs to obtain compound as white solid 3o (53.8mg, 84%)1H NMR(400MHz,CDCl3)δ8.54– 8.40 (m, 3H), 7.60 (d, J=8.3Hz, 2H), 7.41 (d, J=8.2Hz, 2H), 4.06 (s, 2H), 3.25 (s, 4H)；13C NMR(100MHz,CDCl3)δ154.8,145.0,144.3,142.7,142.0,132.3,130.1,118.6,111.4,42.2, 37.3,34.2.IR(film)2974,2229,1720,1517,1476,1403,1212,1160,1058,1017,768.HRMS (ESI)Calcd for C14H13N3S3(M+H+)320.0344,Found 320.0311.
Embodiment 17
The synthesis of compound 3p:
Under nitrogen atmosphere, 1a (42.3mg, 0.2mmol) is sequentially added into reaction tube, to methoxybenzenethiol 2p (30.9mg,0.22mmol),B(C6F5)3(2.6mg, 0.005mmol), methylene chloride (2.0mL), reaction system is stirred at normal temperature Mix 5 hours, after completion of the reaction, methylene chloride dilution removes solvent, column chromatograph colourless liquid compound 3p (55.4mg, 86%)1H NMR(400MHz,CDCl3) δ 7.58 (d, J=8.1Hz, 2H), 7.53 (d, J=8.7Hz, 2H), 7.30 (d, J= 8.1Hz, 2H), 6.89 (d, J=8.7Hz, 2H), 3.99 (s, 2H), 3.82 (s, 3H)；13C NMR(100MHz,CDCl3)δ 160.7,142.1,134.3,132.2,130.1,127.2,118.6,114.8,111.2,55.4,42.2.IR(film)3056, 2974,2226,1587,1490,1459,1291,1245,1174,1024,822,634.HRMS(EI)Calcd for C15H13NOS3319.0159,Found 319.0154.
Embodiment 18
The synthesis of compound 3q:
It under nitrogen atmosphere, is sequentially added into reaction tube 1a (42.3mg, 0.2mmol), 2- methylbenzene phenyl-sulfhydrate 2q (27.4mg,0.22mmol),B(C6F5)3(2.6mg, 0.005mmol), methylene chloride (2.0mL), reaction system is stirred at normal temperature Mix 5 hours, after completion of the reaction, methylene chloride dilution removes solvent, column chromatograph colourless liquid compound 3q (58.8mg, 95%)1H NMR(400MHz,CDCl3) δ 7.72-7.65 (m, 1H), 7.59 (d, J=8.3Hz, 2H), 7.31-7.19 (m, 5H),3.99(s,2H),2.46(s,3H)；13C NMR(100MHz,CDCl3)δ142.1,139.8,135.2,132.7,132.3, 130.7,130.1,129.2,126.7,118.6,111.4,42.2,20.7.IR(film)2970,2228,1918,1605, 1503,1463,1413,1045,842,749,707,649.HRMS(EI)Calcd for C15H13NS3303.0210,Found 303.0211.
Embodiment 19
The synthesis of compound 3r:
Under nitrogen atmosphere, 1a (42.3mg, 0.2mmol), n-acetyl-L-cysteine first are sequentially added into reaction tube Ester 2r (39mg, 0.22mmol), B (C6F5)3(2.6mg, 0.005mmol), methylene chloride (2.0mL), reaction system is at normal temperature Stirring 8 hours, after completion of the reaction, methylene chloride dilution, remove solvent, column chromatograph compound as white solid 3r (46.6mg, 65%)1H NMR(400MHz,CDCl3)δ17.62 (d, J=7.9Hz, 2H), 7.42 (d, J=8.0Hz, 2H), 6.38 (s, 1H),4.94(s,1H),4.08(s,2H),3.76(s,3H),3.38-3.29(m,2H),2.03(s,3H)；13C NMR (100MHz,CDCl3)δ170.6,141.8,132.4,130.2,118.6,111.5,77.3,77.0,76.7,52.8,51.6, 42.2,40.8,23.2.IR(film)3330,2920,2851,2230,1711,1609,1533,1416,1373,1209, 1123,969,826,730,648.HRMS(ESI)Calcd for C14H16N2O3S3(M+Na+)379.0215,Found 379.0208.
Embodiment 20
The synthesis of compound 3s:
It under nitrogen atmosphere, is sequentially added into reaction tube 1a (42.3mg, 0.2mmol), 1,8- pungent two mercaptan 2s (19.6mg,0.11mmol),B(C6F5)3(2.6mg, 0.005mmol), methylene chloride (2.0mL), reaction system is stirred at normal temperature Mix 5 hours, after completion of the reaction, methylene chloride dilution removes solvent, column chromatograph colourless liquid compound 3s (46.1mg, 85%)1H NMR(400MHz,CDCl3) δ 7.62 (d, J=8.2Hz, 4H), 7.43 (d, J=8.1Hz, 4H), 4.07 (s, 4H), 2.80 (t, J=7.3Hz, 4H), 1.69 (dt, J=14.7,7.3Hz, 4H), 1.37-1.30 (m, 8H)；13C NMR(100MHz, CDCl3)δ142.3,132.3,130.1,118.7,111.3,42.1,38.7,28.9,28.6,28.2.IR(film)2924, 2853,2227,1606,1503,1413,1291,1233,1051,843,721,650.HRMS(ESI)Calcd for C22H24N2O2S6(M+Na+)559.0469,Found 559.0462.
Embodiment 21
The synthesis of compound 3t:
It under nitrogen atmosphere, is sequentially added into reaction tube 1a (42.3mg, 0.2mmol), pungent two sulphur of 3,6- dioxas -1,8- Alcohol 2t (20.1mg, 0.11mmol), B (C6F5)3(2.6mg, 0.005mmol), methylene chloride (2.0mL), reaction system is in room temperature It is lower stirring 5 hours, after completion of the reaction, methylene chloride dilution, remove solvent, column chromatograph colourless liquid compound 3t (42.9mg, 79%)1H NMR(400MHz,CDCl3) δ 7.62 (d, J=8.2Hz, 4H), 7.43 (d, J=8.2Hz, 4H), 4.07 (s, 4H), 3.76 (t, J=6.6Hz, 4H), 3.63 (s, 4H), 3.01 (t, J=6.6Hz, 4H)；13C NMR(100MHz,CDCl3)δ 142.1,132.3,130.1,118.6,111.3,70.4,69.1,42.0,38.0.IR(film)3063,2854,2227, 1605,1503,1417,1325,1290,1196,1103,1068,845,737,650.HRMS(ESI)Calcd for C22H24N2O2S6(M+NH4 +)558.0500,Found 558.0449.
Embodiment 22
The synthesis of compound 3u:
Under nitrogen atmosphere, 1b (46.3mg, 0.2mmol), n-dodecyl mercaptan 2g are sequentially added into reaction tube (38uL, 0.22mmol), methylene chloride (2.0mL), reaction system stir 8 hours, after completion of the reaction, methylene chloride at normal temperature Dilution, removes solvent, and column chromatographs to obtain colourless liquid compound 3u (79.4mg, 99%)1H NMR(400MHz,CDCl3)δ8.19 (d, J=8.7Hz, 2H), 7.49 (d, J=8.7Hz, 2H), 4.11 (s, 2H), 2.81 (t, J=7.2Hz, 2H), 1.76-1.63 (m, 2H), 1.40-1.23 (m, 18H), 0.87 (t, J=6.8Hz, 3H)13C NMR(100MHz,CDCl3)δ147.2,144.4, 130.2,123.7,41.6,38.8,31.9,29.6,29.5(8),29.5,29.4,29.3,29.1,28.7,28.4,22.6, 14.1.IR(film)2925,2849,1601,1521,1344,1178,962,800,705.HRMS(EI)Calcd for C19H31NO2S3401.1517,Found 401.1519.
Embodiment 23
The synthesis of compound 3v:
Under nitrogen atmosphere, 1c (32.7mg, 0.2mmol), n-dodecyl mercaptan 2g are sequentially added into reaction tube (38uL, 0.22mmol), methylene chloride (2.0mL), reaction system stir 8 hours, after completion of the reaction, methylene chloride at normal temperature Dilution, removes solvent, and column chromatographs to obtain colourless liquid compound 3v (60.7mg, 99%)1H NMR(400MHz,CDCl3)δ2.97 (t, J=6.7Hz, 2H), 2.86 (t, J=7.2Hz, 2H), 2.54 (t, J=7.0Hz, 2H), 2.19-2.12 (m, 2H), 1.76- 1.69 (m, 2H), 1.41-1.21 (m, 18H), 0.87 (t, J=6.8Hz, 3H)13C NMR(100MHz,CDCl3)δ118.9, 38.8,36.4,31.8,29.6,29.6,29.5,29.4,29.3,29.1,28.6,28.4,24.0,22.6,15.7,14.1.IR (film)2924,2849,2248,1462,1296,971,806,723.HRMS(EI)Calcd for C16H31NS3333.1619, Found 333.1619.
Embodiment 24
The synthesis of compound 3w:
Under air atmosphere, 1d (84.9mg, 0.2mmol), n-acetyl-L-cysteine are sequentially added into reaction tube Methyl esters 2r (39mg, 0.22mmol), B (C6F5)3(2.6mg, 0.005mmol), methylene chloride (0.5mL), reaction system is in room temperature It is lower stirring 5 hours, after completion of the reaction, methylene chloride dilution, remove solvent, column chromatograph colourless liquid compound 3w (68.3mg, 60%)1H NMR(400MHz,CDCl3) δ 6.48 (d, J=7.1Hz, 1H), 5.85 (d, J=3.6Hz, 1H), 5.25 (s, 1H), 4.92 (dt, J=7.7,4.9Hz, 1H), 4.46 (d, J=3.6Hz, 1H), 4.16 (s, 2H), 4.09-4.04 (m, 1H), 4.01- 3.94 (m, 1H), 3.75 (s, 3H), 3.45-3.27 (m, 2H), 2.90 (t, J=7.0Hz, 2H), 2.48 (t, J=7.1Hz, 2H),2.14–2.01(m,5H),1.48(s,3H),1.37(s,3H),1.28(s,3H),1.27(s,3H).13C NMR (100MHz,CDCl3)δ171.3,170.6,169.8,112.2,109.3,105.0,83.3,79.8,76.1,72.4,67.3, 52.7,51.6,40.6,37.4,32.4,26.8,26.6,26.1,25.2,23.6,23.0.IR(film)3304,2986, 2939,1743,1660,1528,1375,1213,1162,1073,1021,846,732,642.HRMS(ESI)Calcd for C22H35NO10S3(M+Na+)592.1315,Found 592.1344.
Embodiment 25
The synthesis of compound 3x:
It under air atmosphere, is sequentially added into reaction tube 1e (134.2mg, 0.2mmol), half Guang ammonia of N- acetyl group-L- Sour methyl esters 2r (39mg, 0.22mmol), B (C6F5)3(2.6mg, 0.005mmol), methylene chloride (0.5mL), reaction system is normal Temperature lower stirring 5 hours, after completion of the reaction, methylene chloride dilution removed solvent, and column chromatographs to obtain compound as white solid 3x (65.2mg, 40%)1H NMR(400MHz,CDCl3) δ 8.02 (d, J=7.3Hz, 2H), 7.99 (d, J=7.4Hz, 2H), 7.88 (d, J=7.3Hz, 2H), 7.59-7.48 (m, 3H), 7.44 (t, J=7.7Hz, 2H), 7.40-7.34 (m, 4H), 6.52 (d, J=7.5Hz, 1H), 5.91-5.77 (m, 2H), 5.60 (d ofABq, J=10.6,3.6Hz, 1H), 5.22 (d, J= 3.5Hz, 1H), 4.93 (dt, J=7.6,5.0Hz, 1H), 4.53-4.48 (m, 2H), 4.39-4.33 (m, 1H), 3.75 (s, 3H), 3.47 (s, 3H), 3.37-3.36 (m, 2H), 2.89-2.74 (m, 2H), 2.62 (t, J=7.2Hz, 2H), 2.09-1.99 (m,5H).13C NMR(100MHz,CDCl3)δ171.8,170.7,169.8,166.1,166.0,165.4,133.4,133.3 (1),133.3(0),129.8,129.7,129.5,129.4,129.2,129.1,128.5,128.4,97.6,68.9,68.6, 68.4,66.5,62.3,55.7,52.7,51.6,40.7,37.5,32.1,23.5,23.1.IR(film)3376,2976, 2904,1723,1678,1375,1262,1066,710.HRMS(ESI)Calcd for C38H41NO13S3(M+Na+) 838.1632,Found 838.1664.
Embodiment 26
The synthesis of compound 3y:
Under nitrogen atmosphere, 1f (85.3mg, 0.2mmol), n-dodecyl mercaptan 2g are sequentially added into reaction tube (44.5uL,0.22mmol),B(C6F5)3(2.6mg, 0.005mmol), methylene chloride (0.5mL), reaction system is stirred at normal temperature Mix 5 hours, after completion of the reaction, methylene chloride dilution removes solvent, column chromatograph compound as white solid 3y (60.7mg, 88%)1H NMR(400MHz,CDCl3) δ 5.24-5.21 (m, 1H), 5.17-5.02 (m, 2H), 4.65 (d, J=9.8Hz, 1H), 4.26 (d ofABq, J=12.5,4.6Hz, 1H), 4.12 (d ofABq, J=12.4,1.8Hz, 1H), 3.76 (ddd, J =9.8,4.3,2.0Hz, 1H), 2.85 (t, J=6.9Hz, 2H), 2.05 (s, 3H), 2.00 (s, 3H), 1.99 (s, 3H), 1.97 (s, 3H), 1.71-1.63 (m, 2H), 1.42-1.16 (m, 18H), 0.84 (t, J=6.7Hz, 3H)13C NMR(100MHz, CDCl3)δ170.4,170.0,169.2,169.0,87.6,76.3,73.7,69.6,67.9,61.8,39.2,31.8,29.5, 29.4(5),29.3,29.2,29.1,28.6,28.3,22.6,20.6(4),20.6(3),20.5(7),20.5(6),20.4 (5),14.0.IR(film)2978,2904,1745,1403,1227,1005,892.HRMS(ESI)Calcd for C26H44O9S3(M+Na+)619.2039,Found 619.2040.
Embodiment 27
The synthesis of compound 3z:
Under nitrogen atmosphere, 1g (59.5mg, 0.2mmol), n-acetyl-L-cysteine first are sequentially added into reaction tube Ester 2r (39mg, 0.22mmol), B (C6F5)3(2.6mg, 0.005mmol), methylene chloride (0.5mL), reaction system is at normal temperature Stirring 8 hours, after completion of the reaction, methylene chloride dilution, remove solvent, column chromatograph compound as white solid 3z (86.7mg, 98%)1H NMR(400MHz,CDCl3)δ6.69(brs,1H),5.49(brs,1H),4.86(s,1H),4.61(s,1H), 3.72(s,3H),3.72(s,3H),3.35-3.31(m,4H),2.01(s,3H),1.39(s,9H).13C NMR(125MHz, CDCl3)δ170.8,170.6,170.0,154.9,80.2,52.7,52.7,52.6,51.5,41.3,40.6,28.1, 22.9.IR(film)3337,2973,1743,1712,1664,1517,1369,1216,1163,1050,782.HRMS(EI) Calcd for C15H26N2O7S3442.0902,Found442.0907.
Embodiment 28
The synthesis of compound 3aa:
It under nitrogen atmosphere, is sequentially added into reaction tube 1g (59.5mg, 0.2mmol), 2s (91.2mg, 0.22mmol), B (C6F5)3(2.6mg, 0.005mmol), methylene chloride (0.5mL), reaction system stir 8 hours at normal temperature, after completion of the reaction, Methylene chloride dilution, removes solvent, and column chromatographs to obtain colourless liquid compound 3aa (59.5mg, 52%)1H NMR(400MHz, DMSO-d6) δ 8.53 (t, J=5.6Hz, 1H), 7.89 (d, J=7.5Hz, 2H), 7.78 (d, J=8.5Hz, 1H), 7.73 (d, J =7.4Hz, 2H), 7.42 (t, J=7.5Hz, 3H), 7.33 (t, J=7.4Hz, 2H), 4.55-4.30 (m, 3H), 4.29-4.20 (m, 2H), 3.96-3.76 (m, 2H), 3.65 (s, 3H), 3.63 (s, 3H), 3.34-3.22 (m, 2H), 3.12 (td, J=14.0, 10.1Hz,2H),1.38(s,9H).13C NMR(100MHz,DMSO-d6)δ170.6,169.9,169.4,155.4,154.8, 143.3,140.2,127.1,126.5,124.8,119.6,78.1,65.3,53.1,52.1,51.7,51.2,46.1,40.6, 39.7,38.5,27.6.IR(film)3330,2977,2903,1691,1519,1403,1223,1163,1049,866, 739.HRMS(EI)Calcd for C30H37N3O9S3(M+Na+)702.1584,Found 702.1598.
Embodiment 29
The synthesis of compound 3ab:
It under nitrogen atmosphere, is sequentially added into reaction tube 1h (47.3mg, 0.2mmol), 2s (91.2mg, 0.22mmol), B (C6F5)3(2.6mg, 0.005mmol), methylene chloride (0.5mL), reaction system stir 8 hours at normal temperature, after completion of the reaction, Methylene chloride dilution, removes solvent, and column chromatographs to obtain colourless liquid compound 3ab (74.3mg, 60%)1H NMR(400MHz, CDCl3) δ 7.76 (d, J=7.5Hz, 2H), 7.60 (d, J=7.3Hz, 2H), 7.40 (t, J=7.4Hz, 2H), 7.33-7.29 (m, 2H), 6.90 (s, 1H), 5.80 (s, 1H), 4.65 (s, 1H), 4.47-4.45 (d, J=6.7Hz, 2H), 4.23 (t, J= 6.8Hz,1H),4.12-3.99(m,2H),3.75(s,3H),3.44-3.35(m,1H),3.27-3.22(m,1H),2.87(t,J =7.3Hz, 2H), 1.75-1.68 (m, 2H), 1.39-1.34 (m, 2H), 1.30-1.22 (m, 12H), 0.88 (t, J=6.8Hz, 3H).13C NMR(100MHz,CDCl3)δ170.1,169.8,156.1,143.7,141.3,127.8,127.1,125.1, 120.0,67.4,53.8,52.5,47.2,41.4,41.2,38.9,31.9,29.5,29.4(9),29.3,29.2,28.8, 28.5,22.7,14.1.IR(film)3293,2976,2908,1741,1692,1651,1533,1403,1255,1051,893, 734,663.HRMS(ESI)Calcd for C31H42N2O5S3(M+H+)619.2329,Found 619.2326.
Embodiment 30
The synthesis of compound 3ac:
It under nitrogen atmosphere, is sequentially added into reaction tube 1h (47.3mg, 0.2mmol), 2t (103.8mg, 0.22mmol), B(C6F5)3(2.6mg, 0.005mmol), methylene chloride (0.5mL), reaction system stir 8 hours at normal temperature, end of reaction Afterwards, methylene chloride dilutes, and removes solvent, and column chromatographs to obtain colourless liquid compound 3ac (67.5mg, 50%)1H NMR (400MHz,CDCl3) δ 7.75 (d, J=7.5Hz, 2H), 7.59 (d, J=7.3Hz, 2H), 7.39 (t, J=7.4Hz, 2H), 7.30 (t, J=7.4Hz, 2H), 7.21 (brs, 1H), 6.98 (brs, 1H), 5.94 (brs, 1H), 4.57 (s, 1H), 4.44 (m, 2H), 4.21 (t, J=6.8Hz, 1H), 4.16-3.84 (m, 4H), 3.69 (s, 3H), 3.31 (d, J=4.7Hz, 2H), 2.85 (t, J=7.3Hz, 2H), 1.70 (m, 2H), 1.40-1.21 (m, 14H), 0.88 (t, J=6.8Hz, 3H)13C NMR (100MHz,CDCl3)δ170.5,170.1,168.8,156.3,143.6,141.3,127.8,127.1,125.0,120.0, 67.4,54.1,52.3,47.1,43.1,41.1,40.6,38.8,31.8,29.5,29.4(5),29.2,29.1,28.7, 28.5,22.6,14.1.IR(film)3292,2970,2921,1742,1689,1644,1529,1404,1257,1068,802, 736,668.HRMS(ESI)Calcd for C33H45N3O6S3(M+Na+)698.2363,Found 698.2362.
Protection content of the invention is not limited to above embodiments.Without departing from the spirit and scope of the invention, originally Field technical staff it is conceivable that variation and advantage be all included in the present invention, and with appended claims be protect Protect range.

Claims (9)

1. a kind of asymmetry trithio class compound, which is characterized in that shown in its structural formula such as formula (3):
Wherein, R1Selected from straight chained alkyl, substituted benzyl, sugar, contain sugar derivatives, amino acid derivativges；
R2Selected from alkyl, aryl, substituted aryl, amino acid derivativges, oligopeptides compound.
2. asymmetry trithio class compound as described in claim 1, which is characterized in that the R1Selected from decyl, to cyano benzyl Base, contains sugar derivatives, amino acid derivativges at sugar；R2Selected from isopropyl, normal-butyl, isobutyl group, tert-butyl, cyclohexyl, just pungent Base, dodecyl, allyl, 17 fluorine decyls, tri- ethoxy silicon substrate n-propyl of 1-, 1- ethoxy, adamantyl, to tert-butyl Benzyl replaces octyl, ethylene glycol two to methoxy-benzyl, 1- pyrazine ethyl, p-methoxyphenyl, o-methyl-phenyl, 1,8- bis- Ethyl, dodecyl, amino acid derivativges, oligopeptides compound.
3. such as described in any item asymmetric trithio class compounds of claim 1-2, which is characterized in that the asymmetry trithio Class compound includes:
4. a kind of synthetic method of asymmetry trithio class compound, which is characterized in that with over cure reagent shown in formula (1) R1Organic sulfur alcohol compound shown in SSOMe and formula (2) is reaction raw materials, under the action of catalyst, in organic solvent, instead The asymmetry trithio class compound as shown in formula (3) should be obtained, shown in the reaction process such as reaction equation (a)；
Wherein, R1Selected from straight chained alkyl, substituted benzyl, sugar, contain sugar derivatives, amino acid derivativges；
R2Selected from alkyl, aryl, substituted aryl, amino acid derivativges, oligopeptides compound.
5. synthetic method as claimed in claim 4, which is characterized in that the catalyst is B (C6F5)3；The catalyst rubs Your dosage is over cure reagent R shown in formula (1)1The 0-5mol% of SSOMe.
6. synthetic method as claimed in claim 4, which is characterized in that the organic solvent is methylene chloride.
7. synthetic method as claimed in claim 4, which is characterized in that the reaction carries out at 0-40 DEG C.
8. synthetic method as claimed in claim 4, which is characterized in that organic sulfur alcohol compound shown in the formula (2) with Over cure reagent R shown in formula (1)1The molar ratio of SSOMe is 1.0:2.0-2.5:1.0.
9. a kind of over cure reagent, which is characterized in that shown in its structure such as formula (1),
Wherein, R1Selected from straight chained alkyl, substituted benzyl, sugar, contain sugar derivatives, amino acid derivativges.
CN201810124062.1A 2018-02-07 2018-02-07 Asymmetric trithio class compound and its synthetic method and application Pending CN110117239A (en)

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CN113004177A (en) * 2021-03-16 2021-06-22 靳浩田 Continuous production method of 3-mercaptopropionic acid alkyl ester and 3, 3' -trithiodipropionic acid dialkyl ester
CN113471529A (en) * 2021-06-29 2021-10-01 江西瑞马新能源材料技术有限公司 Preparation method of solid-state silicon lithium battery with long service life
CN113527022A (en) * 2020-04-21 2021-10-22 华东师范大学 Asymmetric polysulfide compound and its synthesis method and use

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Publication number Priority date Publication date Assignee Title
CN113527022A (en) * 2020-04-21 2021-10-22 华东师范大学 Asymmetric polysulfide compound and its synthesis method and use
CN113527022B (en) * 2020-04-21 2022-12-06 华东师范大学 Asymmetric polysulfide compound and its synthesis method and use
CN113004177A (en) * 2021-03-16 2021-06-22 靳浩田 Continuous production method of 3-mercaptopropionic acid alkyl ester and 3, 3' -trithiodipropionic acid dialkyl ester
CN113004177B (en) * 2021-03-16 2023-12-01 靳浩田 Continuous production method of 3-mercaptopropionic acid alkyl ester and 3,3' -dithiodipropionic acid dialkyl ester
CN113471529A (en) * 2021-06-29 2021-10-01 江西瑞马新能源材料技术有限公司 Preparation method of solid-state silicon lithium battery with long service life
CN113471529B (en) * 2021-06-29 2022-10-14 江西瑞马新能源材料技术有限公司 Preparation method of solid-state silicon lithium battery with long service life

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