CN112010794B - Method for synthesizing N-substituted sulfimide compound - Google Patents
Method for synthesizing N-substituted sulfimide compound Download PDFInfo
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Abstract
The invention discloses a method for synthesizing an N-substituted sulfimide compound, which comprises the following steps: in the air atmosphere, N- (hydrocarbon acyloxy) amide and disubstituted thioether are used as raw materials, a ruthenium complex is used as a catalyst, the reaction is carried out in a reaction solvent under the condition that a silver salt additive and a ligand exist, and after the reaction is finished, the N-substituted sulfimide compound is obtained through separation and purification. The invention has the beneficial effects that: (1) through comprehensive screening and cooperation of a proper substrate, temperature, a catalyst and a ligand, the substrate has a wide application range; (2) compared with the prior art, the method has the advantages of simple synthesis of raw materials, mild reaction conditions, no need of inert gas protection, simple and convenient operation and high reaction efficiency.
Description
Technical Field
The invention relates to a method for synthesizing N-substituted sulfimide compounds, belonging to the field of metal catalytic organic synthesis.
Background
Sulfimides are monoazal analogues of sulfoxides, and many derivatives have important biological activities and are of great significance in medicinal chemistry and crop protection. In the disclosed synthetic methods, it is generally necessary to use suitable nitrene precursors in combination with thioethers in order to obtain different sulfimide derivatives, such as:
D. swern (D.Swern) et al ("Tetracovalent Sulfur intermediates in organosilicon synthesis", Tetrahedron Lett.,1972,13, 2635-:
E.M. Karel (E.M. Carreir) et al ("N, O-bis (Trifluoroacetyl) hydroxyamine as a Useful electrophoretic Nitrogen Source: Catalytic Synthesis of N- (Trifluoroacetyl) sulfilimines", org.Lett.,1999,1, 149-152) disclose a copper triflate catalyzed reaction of a thioether with a lithium salt prepared from N, O-bis (Trifluoroacetyl) hydroxylamine to give the desired product, the formula:
allen Amstertron et al ("effective nitrogen transfer from derivative dN-acyloxyaziridines", Tetrahedron Letters,2003,44, 5335-:
kastein, Bohm (CartenBolm) et al ("Rhodium-Catalyzed activation of sulfoxides and sulfoxides: effective preparation of N-unreacted sulfoxides and sulfoxides", org.Lett.,2004,6, 1305-1307) disclose a Rhodium Catalyzed reaction of an iminoiodoalkane formed in situ from an amine and iodobenzene acetate with a thioether to form the desired product, according to the following equation:
kastitan Bomu et al ("Rhodium-Catalyzed immunization of Sulfoxides and Sulfoxides: effective Preparation of N-unreacted Sulfoximines and Sulfoximines", org.Lett.,2007,9, 3809-3811) disclose a method for the conversion of N-cyanosulfilimine to the desired product under trifluoroacetic anhydride without the participation of metals, according to the following reaction scheme:
branch aspiration (Chi-Ming Che) et al ("[ Fe ] III (F 20 -tpp)Cl]Is an Effective Catalyst for Nitrene Transfer Reactions and Amination of Saturated Hydrocarbons with Sulfonyl and Aryl Azides as Nitrogen Source under Thermal and Microwave-Assisted Conditions ", chem. -Eur.J., 2010,16, 10494-10501) discloses a reaction of thioethers with azide compounds under iron catalysis to produce a target product, the reaction formula is as follows:
kasten Bolm et al ("Light-Induced Ruthenium-Catalyzed Nitrene Transfer Reactions: A Photochemical applied towards N-Acyl sulfides and Sulfoximines", Angew. chem., int. Ed.,2014,53, 5639-:
lebeier (Lebei ne Lebel) et al (Rhodium-Catalyzed Stereoselective amplification of Thioethers with N-Melyxycarbamates, DMAP and Bis (DMAP) CH 2 Cl 2 as Key Additives, angel. chem. int.ed.2014,53, 7300-:
in the technical scheme, the conditions of complicated raw material synthesis steps, low reaction efficiency, complex reaction conditions and the like exist.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects of the prior art, the invention discloses a method for synthesizing an N-substituted sulfimide compound.
The technical scheme is as follows: a method for synthesizing N-substituted thioimide compounds comprises the following steps:
in the air atmosphere, taking N- (hydrocarbon acyloxy) amide and disubstituted thioether as raw materials, taking a ruthenium complex as a catalyst, reacting in a reaction solvent in the presence of a silver salt additive and a ligand, and after the reaction is finished, separating and purifying to obtain an N-substituted sulfimide compound, wherein:
the structural formula of the N- (hydrocarbon acyloxy) amide is shown as
Wherein:
R 1 is C 1 ～C 10 Alkyl, aryl and aryl containing a substituent C 1 ～C 10 Alkyl, alkoxy, halogen;
R 2 is C 1 ～C 10 A hydrocarbon acyl group;
the structural formula of the disubstituted thioether is
Wherein R is 3 And R 4 Is C 1 ～C 12 Alkyl, phenyl, benzyl;
the mol ratio of the N- (hydrocarbon acyloxy) amide, the disubstituted thioether, the ruthenium complex, the silver salt additive and the ligand is 1: (1-2): (0.01-0.1): (0.04-0.4): (0.02-0.2);
the amount of the reaction solvent is 5-25 mL/g based on the weight of the N- (hydrocarbon acyloxy) amide.
Further, the ruthenium complex is one of ruthenium trichloride, ruthenium dichloride, triphenylphosphine ruthenium dichloride and p-cymene ruthenium dichloride dimer, and triphenylphosphine ruthenium dichloride is preferred.
Further, the silver salt additive is one of silver chloride, silver nitrate, silver acetate, silver hexafluoroantimonate and silver tetrafluoroborate, and preferably silver acetate.
Further, the ligand is one of triphenylphosphine, bipyridine, benzamide, benzoic acid and benzohydroxamic acid, and is preferably benzohydroxamic acid.
Further, the reaction solvent is one of methanol, ethanol, toluene, dichloromethane, dichloroethane, acetonitrile and ethyl acetate, preferably methanol.
Further, the reaction temperature is 0 to 100 ℃ and preferably 25 ℃.
Further, the reaction time is 5 to 300 minutes, preferably 10 minutes.
Furthermore, the molar ratio of the N- (hydrocarbon acyloxy) amide, the disubstituted thioether, the ruthenium complex, the silver salt additive and the ligand is 1:1.5:0.05:0.2: 0.1.
Further, the separation and purification is column chromatography separation or recrystallization.
Has the advantages that: the invention discloses a method for synthesizing N-substituted sulfimide compounds, which has the advantages that:
(1) through comprehensive screening and cooperation of a proper substrate, temperature, a catalyst and a ligand, the substrate has a wide application range;
(2) compared with the prior art, the method has the advantages of simple synthesis of raw materials, mild reaction conditions, no need of inert gas protection, simple and convenient operation and high reaction efficiency.
The specific implementation mode is as follows:
the present invention will be described specifically with reference to the following examples, but these examples should not be construed as limiting the scope of the present invention in any way.
Example 1:
a method for synthesizing an N-substituted thioimide compound, comprising the steps of:
in the air atmosphere, N- (hydrocarbon acyloxy) amide and disubstituted thioether are used as raw materials, a ruthenium complex is used as a catalyst, the reaction is carried out in a reaction solvent in the presence of a silver salt additive and a ligand, and after the reaction is finished, N-substituted sulfimide compounds are obtained through column chromatography separation, wherein:
the structural formula of the N- (hydrocarbon acyloxy) amide is shown as
Wherein:
R 1 is an aryl group;
R 2 is pivaloyl;
the structural formula of the disubstituted thioether is
Wherein:
R 3 is phenyl;
R 4 is a benzyl group;
the molar ratio of the N- (hydrocarbon acyloxy) amide, the disubstituted thioether, the ruthenium complex, the silver salt additive and the ligand is 1: 1: 0.01: 0.04: 0.02;
the reaction solvent was used in an amount of 5mL/g based on the weight of the N- (hydrocarbylacyloxy) amide.
Further, the ruthenium complex is triphenylphosphine ruthenium dichloride.
Further, the silver salt additive is silver acetate.
Further, the ligand is benzohydroxamic acid.
Further, the reaction solvent is methanol.
Further, the reaction temperature was 25 ℃.
Further, the reaction time was 10 minutes.
Further, after completion of the reaction, the reaction mixture was filtered, dried and separated by column chromatography (PE/EA: 2/1) to obtain the product.
The product was a colorless oil in 91% yield, nuclear magnetic resonance as follows:
1 H NMR(400MHz,CDCl 3 )δ8.21-8.19(m,2H),7.58-7.38(m,8H),7.31-7.29(m,1H),7.23-7.19(m,2H),6.95(d,J＝7.2Hz,2H),4.63(d,J＝12.4Hz,1H),4.26(d,J＝12.4Hz,1H). 13 C NMR(125MHz,CDCl 3 )δ176.6,136.6,132.21,132.17,130.71,130.66,129.3,128.8,128.7,128.5,128.3,128.0,127.7,56.0.HRMS(ESI):[M+H] + Calcd.320.1104,Found320.1112.
example 2:
a method for synthesizing an N-substituted thioimide compound, comprising the steps of:
in the air atmosphere, taking N- (hydrocarbon acyloxy) amide and disubstituted thioether as raw materials, taking a ruthenium complex as a catalyst, reacting in a reaction solvent in the presence of a silver salt additive and a ligand, and recrystallizing after the reaction is finished to obtain the N-substituted sulfimide compound, wherein:
the structural formula of the N- (hydrocarbon acyloxy) amide is shown as
Wherein:
R 1 is aryl containing a substituent, and the substituent is chlorine;
R 2 is pivaloyl;
the structural formula of the disubstituted thioether is
R 3 Is phenyl;
R 4 is benzyl;
the mol ratio of the N- (hydrocarbon acyloxy) amide, the disubstituted thioether, the ruthenium complex, the silver salt additive and the ligand is 1: 2: 0.1: 0.4: 0.2;
the reaction solvent was used in an amount of 25mL/g based on the weight of the N- (hydrocarbyloxy) amide.
Further, the ruthenium complex is ruthenium trichloride.
Further, the silver salt additive is silver chloride.
Further, the ligand is triphenylphosphine.
Further, the reaction solvent is ethanol.
Further, the reaction temperature was 0 ℃.
Further, the reaction time was 300 minutes.
The product was a yellow oil in 60% yield, nuclear magnetic as follows:
1 H NMR(400MHz,CDCl 3 )δ7.72-7.69(m,1H),7.58-7.51(m,3H),7.45-7.38(m,3H),7.30-7.27(m,2H),7.25-7.21(m,3H),6.97(d,J＝7.2Hz,2H),4.67(d,J＝12.4Hz,1H),4.33(d,J＝12.4Hz,1H). 13 C NMR(125MHz,CDCl 3 )δ177.1,137.7,132.4,131.8,131.6,130.7,130.10,130.06,129.9,129.4,128.9,128.5,128.2,128.1,126.3,55.9.HRMS(ESI):[M+H] + Calcd.354.0714,Found 354.0724.
example 3:
a method for synthesizing an N-substituted thioimide compound, comprising the steps of:
in the air atmosphere, N- (hydrocarbon acyloxy) amide and disubstituted thioether are taken as raw materials, a ruthenium complex is taken as a catalyst, the reaction is carried out in a reaction solvent under the condition that a silver salt additive and a ligand exist, and after the reaction is finished, the N-substituted sulfimide compound is obtained through column chromatography separation, wherein:
the structural formula of the N- (hydrocarbon acyloxy) amide is shown as
Wherein:
R 1 is aryl containing a substituent, and the substituent is F;
R 2 is pivaloyl;
the structural formula of the disubstituted thioether is
Wherein:
R 3 is phenyl;
R 4 is a benzyl group;
the mol ratio of the N- (hydrocarbon acyloxy) amide, the disubstituted thioether, the ruthenium complex, the silver salt additive and the ligand is 1:1.5:0.05:0.2: 0.1;
the reaction solvent was used in an amount of 10mL/g based on the weight of the N- (hydrocarbyloxy) amide.
Further, the ruthenium complex is ruthenium dichloride.
Further, the silver salt additive is silver nitrate.
Further, the ligand is bipyridine.
Further, the reaction solvent is toluene.
Further, the reaction temperature was 100 ℃.
Further, the reaction time was 5 minutes.
Further, after completion of the reaction, the reaction mixture was filtered, dried and separated by column chromatography (PE/EA: 2/1) to obtain the product.
The product was a colorless oil, 88% yield, nuclear magnetism as follows:
1 H NMR(400MHz,CDCl 3 )δ8.22-8.18(m,2H),7.55-7.50(m,3H),7.44-7.40(m,2H),7.31-7.27(m,1H),7.23-7.19(m,2H),7.08-7.04(m,2H),6.94(d,J＝7.2Hz,2H),4.62(d,J＝12.4Hz,1H),4.26(d,J＝12.4Hz,1H). 13 C NMR(125MHz,CDCl 3 )δ175.6,164.6(d,J＝248.8Hz),132.9,132.3,132.2,130.9(d,J＝8.8Hz),130.7,129.3,128.7,128.5,128.3,128.0,114.5(d,J＝21.3Hz),56.0. 19 F NMR(400MHz,CDCl 3 )δ-110.2.HRMS(ESI):[M+H] + Calcd.338.1009,Found 338.1011.
example 4:
a method for synthesizing an N-substituted thioimide compound, comprising the steps of:
in the air atmosphere, N- (hydrocarbon acyloxy) amide and disubstituted thioether are used as raw materials, a ruthenium complex is used as a catalyst, the reaction is carried out in a reaction solvent in the presence of a silver salt additive and a ligand, and after the reaction is finished, the N-substituted sulfimide compound is obtained through recrystallization, wherein:
the structural formula of the N- (hydrocarbon acyloxy) amide is shown as
Wherein:
R 1 is thienyl;
R 2 is pivaloyl;
the structural formula of the disubstituted thioether is
Wherein:
R 3 is phenyl;
R 4 is benzyl;
the molar ratio of the N- (hydrocarbon acyloxy) amide, the disubstituted thioether, the ruthenium complex, the silver salt additive and the ligand is 1: 1: 0.1: 0.4: 0.1;
the reaction solvent was used in an amount of 10mL/g based on the weight of the N- (hydrocarbyloxy) amide.
Further, the ruthenium complex is triphenylphosphine ruthenium dichloride.
Further, the silver salt additive is silver hexafluoroantimonate.
Further, the ligand is benzamide.
Further, the reaction solvent is dichloromethane.
Further, the reaction temperature was room temperature.
Further, the reaction time was 10 minutes.
And further filtering, spin-drying and recrystallizing after the reaction is finished to obtain the product.
The product was an orange solid in 81% yield, nuclear magnetic as follows:
1 H NMR(400MHz,CDCl 3 )δ7.76-7.75(m,1H),7.55-7.50(m,3H),7.44-7.38(m,3H),7.31-7.27(m,1H),7.24-7.20(m,2H),7.06(dd,J＝4.8,3.6Hz,1H),6.97(d,J＝7.2Hz,2H),4.62(d,J＝12.4Hz,1H),4.23(d,J＝12.4Hz,1H). 13 C NMR(125MHz,CDCl 3 )δ171.9,141.7,132.3,132.1,130.8,129.9,129.32,129.28,128.9,128.5,128.2,127.9,127.1,56.3.HRMS(ESI):[M+Na] + Calcd.348.0487,Found 348.0480.
example 5:
a method for synthesizing an N-substituted thioimide compound, comprising the steps of:
in the air atmosphere, N- (hydrocarbon acyloxy) amide and disubstituted thioether are taken as raw materials, a ruthenium complex is taken as a catalyst, the reaction is carried out in a reaction solvent under the condition that a silver salt additive and a ligand exist, and after the reaction is finished, the N-substituted sulfimide compound is obtained through column chromatography separation, wherein:
the structural formula of the N- (hydrocarbon acyloxy) amide is shown as
Wherein:
R 1 is aryl;
R 2 is pivaloyl;
the structural formula of the disubstituted thioether is
Wherein:
R 3 is phenyl;
R 4 is benzyl;
the mol ratio of the N- (hydrocarbon acyloxy) amide, the disubstituted thioether, the ruthenium complex, the silver salt additive and the ligand is 1: 2: 0.05:0.2: 0.1;
the reaction solvent was used in an amount of 20mL/g based on the weight of the N- (hydrocarbyloxy) amide.
Further, the ruthenium complex is p-cymene ruthenium dichloride dimer.
Further, the silver salt additive is silver hexafluoroantimonate.
Further, the ligand is benzoic acid.
Further, the reaction solvent is dichloroethane.
Further, the reaction temperature was 90 ℃.
Further, the reaction time was 8 minutes.
Further, after the reaction, the product was obtained by filtration, spin-drying and column chromatography (PE/EA: 2/1).
The product was a colorless oil, 81% yield, nuclear magnetic resonance as follows:
1 H NMR(400MHz,DMSO)δ8.52(s,1H),7.10(s,2H),6.63(s,1H),2.26(s,6H). 13 C NMR(100MHz,DMSO)δ152.8(s),140.0(s),138.2(s),123.8(s),116.3(s),21.6(s).HRMS(ESI):[M+H] + Calcd.370.1260,Found 370.1256.
example 6:
a method for synthesizing N-substituted thioimide compounds comprises the following steps:
in the air atmosphere, N- (hydrocarbon acyloxy) amide and disubstituted thioether are used as raw materials, a ruthenium complex is used as a catalyst, the reaction is carried out in a reaction solvent in the presence of a silver salt additive and a ligand, and after the reaction is finished, the N-substituted sulfimide compound is obtained through recrystallization, wherein:
the structural formula of the N- (hydrocarbon acyloxy) amide is shown as
Wherein:
R 1 is a substituted alkyl group;
R 2 is pivaloyl;
the structural formula of the disubstituted thioether is
Wherein:
R 3 is phenyl;
R 4 is a benzyl group;
the molar ratio of the N- (hydrocarbon acyloxy) amide, the disubstituted thioether, the ruthenium complex, the silver salt additive and the ligand is 1: 1.2: 0.05: 0.1: 0.1;
the reaction solvent was used in an amount of 10mL/g based on the weight of the N- (hydrocarbyloxy) amide.
Further, the ruthenium complex is triphenylphosphine ruthenium dichloride.
Further, the silver salt additive is silver acetate.
Further, the ligand is benzohydroxamic acid.
Further, the reaction solvent is methanol.
Further, the reaction temperature was 25 ℃.
Further, the reaction time was 10 minutes.
And further filtering, spin-drying and recrystallizing after the reaction is finished to obtain the product.
The product was a colorless oil with a yield of 95% and a nuclear magnetic resonance as follows:
1 HNMR(400MHz,DMSO)δ7.58-7.45(m,5H),7.28-7.27(m,1H),7.25-7.17(m,7H),7.05(d,J＝6.8Hz,2H),4.49(d,J＝12.4Hz,1H),4.42(d,J＝12.8Hz,1H),2.85(t,J＝7.6Hz,2H),2.52(t,J＝7.6Hz,2H). 13 C NMR(125MHz,DMSO)δ181.6,141.8,133.0,131.8,130.7,129.4,129.2,128.4,128.2,128.10,128.06,127.4,125.6,53.0,32.0.HRMS(ESI):[M+H] + Calcd.348.1417,Found 348.1410.
example 7:
a method for synthesizing an N-substituted thioimide compound, comprising the steps of:
in the air atmosphere, N- (hydrocarbon acyloxy) amide and disubstituted thioether are taken as raw materials, a ruthenium complex is taken as a catalyst, the reaction is carried out in a reaction solvent under the condition that a silver salt additive and a ligand exist, and after the reaction is finished, the N-substituted sulfimide compound is obtained through column chromatography separation, wherein:
the structural formula of the N- (hydrocarbon acyloxy) amide is shown as
Wherein:
R 1 is phenyl;
R 2 is pivaloyl;
the structural formula of the disubstituted thioether is
Wherein
R 3 Is phenyl;
R 4 is methyl;
the mol ratio of the N- (hydrocarbon acyloxy) amide, the disubstituted thioether, the ruthenium complex, the silver salt additive and the ligand is 1: 1: 0.05:0.2: 0.1;
the reaction solvent was used in an amount of 20mL/g based on the weight of the N- (hydrocarbyloxy) amide.
Further, the ruthenium complex is ruthenium trichloride.
Further, the silver salt additive is silver acetate.
Further, the ligand is benzohydroxamic acid.
Further, the reaction solvent is methanol.
Further, the reaction temperature was 70 ℃.
Further, the reaction time was 20 minutes.
Further, after completion of the reaction, the reaction mixture was filtered, dried and separated by column chromatography (PE/EA: 1/2) to obtain the product. The product was a white solid with a yield of 94% and a nuclear magnetic resonance as follows:
1 H NMR(400MHz,CDCl 3 )δ8.18-8.16(m,2H),7.86-7.84(m,2H),7.57-7.37(m,6H),2.93(s,3H).
example 8:
a method for synthesizing an N-substituted thioimide compound, comprising the steps of:
in the air atmosphere, taking N- (hydrocarbon acyloxy) amide and disubstituted thioether as raw materials, taking a ruthenium complex as a catalyst, reacting in a reaction solvent in the presence of a silver salt additive and a ligand, and recrystallizing after the reaction is finished to obtain the N-substituted sulfimide compound, wherein:
the structural formula of the N- (hydrocarbon acyloxy) amide is shown as
Wherein:
R 1 is phenyl;
R 2 is pivaloyl;
the structural formula of the disubstituted thioether is
Wherein R is 3 And R 4 Is benzyl;
the molar ratio of the N- (hydrocarbon acyloxy) amide, the disubstituted thioether, the ruthenium complex, the silver salt additive and the ligand is 1:1.5:0.05: 0.1: 0.2;
the reaction solvent was used in an amount of 15mL/g based on the weight of the N- (hydrocarbyloxy) amide.
Further, the ruthenium complex is ruthenium dichloride.
Further, the silver salt additive is silver nitrate.
Further, the ligand is bipyridine.
Further, the reaction solvent is ethanol.
Further, the reaction temperature was room temperature.
Further, the reaction time was 20 minutes.
And further filtering, spin-drying and recrystallizing after the reaction is finished to obtain the product. The product was a white solid, 88% yield, nuclear magnetism as follows:
1 H NMR(400MHz,CDCl 3 )δ8.11-8.08(m,2H),7.44-7.32(m,13H),4.34(d,J＝12.8Hz,2H),4.15(d,J＝13.2Hz,2H). 13 C NMR(125MHz,CDCl 3 )δ177.4,136.7,130.6,130.4,129.1,128.9,128.8,128.5,127.7,48.5.HRMS(ESI):[M+H] + Calcd.334.1260,Found 334.1260.
example 9:
a method for synthesizing an N-substituted thioimide compound, comprising the steps of:
in the air atmosphere, N- (hydrocarbon acyloxy) amide and disubstituted thioether are taken as raw materials, a ruthenium complex is taken as a catalyst, the reaction is carried out in a reaction solvent under the condition that a silver salt additive and a ligand exist, and after the reaction is finished, the N-substituted sulfimide compound is obtained through column chromatography separation, wherein:
the structural formula of the N- (hydrocarbon acyloxy) amide is shown as
Wherein:
R 1 is phenyl;
R 2 is pivaloyl;
the structural formula of the disubstituted thioether is
Wherein:
R 3 is 4-fluorophenyl;
R 4 is methyl;
the mol ratio of the N- (hydrocarbon acyloxy) amide, the disubstituted thioether, the ruthenium complex, the silver salt additive and the ligand is 1: 2: 0.1: 0.1: 0.1;
the reaction solvent was used in an amount of 10mL/g based on the weight of the N- (hydrocarbyloxy) amide.
Further, the ruthenium complex is triphenylphosphine ruthenium dichloride.
Further, the silver salt additive is silver tetrafluoroborate.
Further, the ligand is triphenylphosphine.
Further, the reaction solvent is methanol.
Further, the reaction temperature was room temperature.
Further, the reaction time was 10 minutes.
Further, after the reaction was completed, the product was obtained by filtration, spin-drying and column chromatography (PE/EA-1/2). The product was a white solid in 85% yield with the following nuclear magnetization:
1 H NMR(400MHz,CDCl 3 )δ8.19-8.14(m,2H),7.86-7.83(m,2H),7.47-7.36(m,3H),7.25-7.21(m,2H),2.90(s,3H). 13 C NMR(125MHz,CDCl 3 )δ176.7,164.8(d,J＝251.3Hz),136.1,130.8,129.1(d,J＝8.8Hz),128.6,127.8,117.2(d,J＝22.5Hz),35.1. 19 F NMR(400MHz,CDCl 3 )δ-106.2.HRMS(ESI):[M+H] + Calcd.262.0696,Found262.0700.
example 10:
a method for synthesizing an N-substituted thioimide compound, comprising the steps of:
in the air atmosphere, N- (hydrocarbon acyloxy) amide and disubstituted thioether are used as raw materials, a ruthenium complex is used as a catalyst, the reaction is carried out in a reaction solvent in the presence of a silver salt additive and a ligand, and after the reaction is finished, the N-substituted sulfimide compound is obtained through recrystallization, wherein:
the structural formula of the N- (hydrocarbon acyloxy) amide is shown as
Wherein:
R 1 is phenyl;
R 2 is pivaloyl;
the structural formula of the disubstituted thioether is
Wherein the content of the first and second substances,
R 3 is m-methoxyphenyl;
R 4 is methyl;
the mol ratio of the N- (hydrocarbon acyloxy) amide, the disubstituted thioether, the ruthenium complex, the silver salt additive and the ligand is 1: 1: 0.1: 0.04: 0.2;
the reaction solvent was used in an amount of 10mL/g based on the weight of the N- (hydrocarbyloxy) amide.
Further, the ruthenium complex is triphenylphosphine ruthenium dichloride.
Further, the silver salt additive is silver acetate.
Further, the ligand is benzohydroxamic acid.
Further, the reaction solvent is methanol.
Further, the reaction temperature was room temperature.
Further, the reaction time was 20 minutes.
And further filtering, spin-drying and recrystallizing after the reaction is finished to obtain the product. The product was a colorless oil, 96% yield, nuclear magnetic resonance as follows:
1 H NMR(400MHz,CDCl 3 )δ8.18-8.15(m,2H),7.46-7.36(m,6H),7.08-7.05(m,1H),3.84(s,3H),2.91(s,3H). 13 C NMR(125MHz,CDCl 3 )δ176.7,160.5,137.1,136.3,128.6,127.7,118.6,118.0,111.6,55.5,35.1.HRMS(ESI):[M+H] + Calcd.274.0896,Found 274.0899.
example 11:
a method for synthesizing an N-substituted thioimide compound, comprising the steps of:
in the air atmosphere, N- (hydrocarbon acyloxy) amide and disubstituted thioether are taken as raw materials, a ruthenium complex is taken as a catalyst, the reaction is carried out in a reaction solvent under the condition that a silver salt additive and a ligand exist, and after the reaction is finished, the N-substituted sulfimide compound is obtained through column chromatography separation, wherein:
the structural formula of the N- (hydrocarbon acyloxy) amide is shown as
Wherein:
R 1 is phenyl;
R 2 is pivaloyl; (ii) a
The structural formula of the disubstituted thioether is
Wherein
R 3 Is 4-methoxyphenyl;
R 4 is 4-methoxyphenyl;
the molar ratio of the N- (hydrocarbon acyloxy) amide, the disubstituted thioether, the ruthenium complex, the silver salt additive and the ligand is 1: 2: 0.05: 0.08: 0.1;
the reaction solvent was used in an amount of 20mL/g based on the weight of the N- (hydrocarbyloxy) amide.
Further, the ruthenium complex is triphenylphosphine ruthenium dichloride.
Further, the silver salt additive is silver acetate.
Further, the ligand is benzohydroxamic acid.
Further, the reaction solvent is methanol.
Further, the reaction temperature was room temperature.
Further, the reaction time was 10 minutes.
Further, after completion of the reaction, the reaction mixture was filtered, dried and separated by column chromatography (PE/EA: 1/2) to obtain the product. The product was a colorless oil, 82% yield, nuclear magnetism as follows:
1 H NMR(400MHz,CDCl 3 )δ8.24-8.23(m,2H),7.72(d,J＝9.2Hz,4H),7.43-7.36(m,3H),6.96(d,J＝9.2Hz,4H),3.79(s,3H). 13 C NMR(125MHz,CDCl 3 )δ176.2,162.3,136.7,130.6,129.5,128.8,128.4,127.6,127.40,127.38,115.2,55.5.HRMS(ESI):[M+H] + Calcd.366.1158,Found 366.1160.
example 12:
a method for synthesizing an N-substituted thioimide compound, comprising the steps of:
in the air atmosphere, N- (hydrocarbon acyloxy) amide and disubstituted thioether are used as raw materials, a ruthenium complex is used as a catalyst, the reaction is carried out in a reaction solvent in the presence of a silver salt additive and a ligand, and after the reaction is finished, the N-substituted sulfimide compound is obtained through recrystallization, wherein:
the structural formula of the N- (hydrocarbon acyloxy) amide is shown as
Wherein:
R 1 is phenyl;
R 2 is an alkanoyl group;
the structural formula of the disubstituted thioether is
Wherein R is 3 And R 4 Is n-hexyl;
the molar ratio of the N- (hydrocarbon acyloxy) amide, the disubstituted thioether, the ruthenium complex, the silver salt additive and the ligand is 1: 2: 0.1: 0.2: 0.1;
the reaction solvent was used in an amount of 10mL/g based on the weight of the N- (hydrocarbyloxy) amide.
Further, the ruthenium complex is triphenylphosphine ruthenium dichloride.
Further, the silver salt additive is silver acetate.
Further, the ligand is benzohydroxamic acid.
Further, the reaction solvent is methanol.
Further, the reaction temperature was 25 ℃.
Further, the reaction time was 10 minutes.
And further filtering, spin-drying and recrystallizing after the reaction is finished to obtain the product. The product was a yellow oil in 88% yield, nuclear magnetic resonance as follows:
1 H NMR(400MHz,CDCl 3 )δ8.10-8.08(m,2H),7.43-7.34(m,3H),3.12-3.05(m,2H),2.96-2.89(m,2H),1.82-1.74(m,4H),1.47-1.30(m,12H),0.89(t,J＝6.8Hz,6H). 13 C NMR(125MHz,CDCl 3 )δ177.2,136.9,130.4,128.5,127.6,44.9,31.1,28.2,23.2,22.2,13.8.HRMS(ESI):[M+H] + Calcd.322.2199,Found 322.2207.
examples 13 to 25
Is essentially the same as example 1, except that the substituent R of the N- (Hydroxyacyloxy) amide 1 And R 2 The following table specifically shows the differences:
examples 26 to 37
Substantially the same as example 1, except that R is a substituent in the disubstituted thioether 3 And R 4 The following table specifically shows the differences:
| R 3 | R 4 | yield of | |
| Example 26 | Methyl radical | Phenyl radical | 92％ |
| Example 27 | Ethyl radical | Methyl radical | 80％ |
| Example 28 | Isopropyl group | Ethyl radical | 85％ |
| Example 29 | Isobutyl radical | Isopropyl group | 85％ |
| Example 30 | Isoamyl radical | Isobutyl radical | 82％ |
| Example 31 | N-heptyl radical | Isoamyl radical | 90％ |
| Example 32 | N-octyl radical | N-heptyl radical | 95％ |
| Example 33 | N-nonyl radical | N-octyl radical | 88％ |
| Example 34 | N-decyl radical | N-nonyl radical | 88％ |
| Example 35 | N-undecyl radical | N-decyl radical | 86％ |
| Example 36 | Dodecyl radical | N-undecyl radical | 85％ |
| Example 37 | Benzyl radical | Dodecyl radical | 86％ |
The embodiments of the present invention have been described in detail. However, the present invention is not limited to the above-described embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (12)
1. A method for synthesizing N-substituted sulfimide compounds is characterized by comprising the following steps:
in the air atmosphere, N- (hydrocarbon acyloxy) amide and disubstituted thioether are used as raw materials, a ruthenium complex is used as a catalyst, the reaction is carried out in a reaction solvent in the presence of a silver salt additive and a ligand, and after the reaction is finished, an N-substituted sulfimide compound is obtained through separation and purification, wherein the structural formula of the N-substituted sulfimide compound is as follows:
wherein:
the structural formula of the N- (hydrocarbon acyloxy) amide is shown as
Wherein:
R 1 is C 1 ～C 10 Alkyl, aryl and aryl containing a substituent C 1 ～C 10 Alkyl, alkoxy, halogen;
R 2 is C 1 ～C 10 A hydrocarbon acyl group;
the structural formula of the disubstituted thioether is
Wherein R is 3 And R 4 Is C 1 ～C 12 Alkyl, phenyl, benzyl;
the mol ratio of the N- (hydrocarbon acyloxy) amide, the disubstituted thioether, the ruthenium complex, the silver salt additive and the ligand is 1: (1-2): (0.01-0.1): (0.04-0.4): (0.02-0.2);
the amount of the reaction solvent is 5-25 mL/g based on the weight of the N- (hydrocarbon acyloxy) amide, wherein:
the ruthenium complex is one of ruthenium trichloride, ruthenium dichloride, triphenylphosphine ruthenium dichloride and p-cymene ruthenium dichloride dimer;
the silver salt additive is one of silver chloride, silver nitrate, silver acetate, silver hexafluoroantimonate and silver tetrafluoroborate;
the ligand is one of triphenylphosphine, bipyridine, benzamide, benzoic acid and benzohydroxamic acid.
2. The method for synthesizing an N-substituted sulfimide compound as claimed in claim 1 wherein said ruthenium complex is triphenylphosphine ruthenium dichloride.
3. The method of claim 1, wherein the silver salt additive is silver acetate.
4. The method of claim 1, wherein the ligand is benzohydroxamic acid.
5. The method of claim 1, wherein the reaction solvent is one of methanol, ethanol, toluene, dichloromethane, dichloroethane, acetonitrile, and ethyl acetate.
6. The method of claim 5, wherein the reaction solvent is methanol.
7. The process for the synthesis of N-substituted thioimides according to claim 1, wherein the reaction temperature is in the range of 0 to 100 ℃.
8. The method of claim 7, wherein the reaction temperature is 25 ℃.
9. The method for synthesizing N-substituted sulfimide compound as claimed in claim 1, wherein the reaction time is 5 to 300 minutes.
10. The method of claim 9, wherein the reaction time is 10 minutes.
11. The method of claim 1, wherein the molar ratio of the N- (hydrocarbon acyloxy) amide, the disubstituted thioether, the ruthenium complex, the silver salt additive and the ligand is 1:1.5:0.05:0.2: 0.1.
12. The method for synthesizing an N-substituted thioimide compound as claimed in claim 1 wherein the separation purification is column chromatography or recrystallization.
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| JP2004277398A (en) * | 2003-02-25 | 2004-10-07 | Kyushu Univ | Method for producing optically active sulfimide compound |
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| CN108640869A (en) * | 2018-05-29 | 2018-10-12 | 四川大学 | Transition metal-catalyzed C-H couplings efficiently prepare mebenil aryl-heterocyclic analog derivative |
| CN109574890A (en) * | 2018-12-11 | 2019-04-05 | 温州大学 | A kind of N- sulfenyl-N- allyl substituted amide class compound and preparation method thereof |
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| JP2004277398A (en) * | 2003-02-25 | 2004-10-07 | Kyushu Univ | Method for producing optically active sulfimide compound |
| CN103936537A (en) * | 2014-04-24 | 2014-07-23 | 华东师范大学 | Method for performing gold-catalyzed selective C-H bond functionalization on phenol and aniline |
| CN108380245A (en) * | 2018-02-06 | 2018-08-10 | 中山大学 | A kind of novel bidentate phosphorus-azepine Cabbeen p-cymene type catalyzed by ruthenium complexes agent and preparation method thereof and synthesis application |
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