CN109796383B

CN109796383B - 1-thiophenyl-N-acetyl-2-naphthylamine and its derivative and synthesis method

Info

Publication number: CN109796383B
Application number: CN201910078042.XA
Authority: CN
Inventors: 肖福红; 袁珊珊; 邓国军; 黄华文; 陈善平
Original assignee: Xiangtan University
Current assignee: Xiangtan University
Priority date: 2019-01-19
Filing date: 2019-01-19
Publication date: 2020-09-18
Anticipated expiration: 2039-01-19
Also published as: CN109796383A

Abstract

The invention mainly relates to 1-thiophenyl-N-acetyl-2-naphthylamine and derivatives thereof and a synthesis method thereof, in the combined action of a cheap and easily available iron-containing reagent and an iodine compound, the carbon-sulfur bond of a thioester compound is broken and the 2-naphthylamine is subjected to bifunctional recombination to generate a new C-N/C-S bond, and a one-pot multi-component reaction is carried out to generate the 1-thiophenyl-N-acetyl-2-naphthylamine and the derivatives thereof. The method overcomes the defects that the existing synthetic method of the 1-thiophenyl-N-acetyl-2-naphthylamine compound has complex synthetic steps and can be completed by adopting a multi-step synthetic process; the method of the invention keeps atom economy to the utmost extent; the compound has stable molecular structure and excellent chemical property, and the molecular cut block and the compound fragment contain rich contents of biological activity and pharmacological activity; the method also has the advantages of simple reaction system, mild reaction conditions, less reaction equipment, simple and convenient experimental operation, wide material sources, easy expansion of users and application, higher product utilization value and the like.

Description

1-thiophenyl-N-acetyl-2-naphthylamine and its derivative and synthesis method

Technical Field

The invention relates to 1-thiophenyl-N-acetyl-2-naphthylamine and derivatives thereof and a synthetic method, belonging to the field of organic synthesis.

Background

The 1-thiophenyl-N-acetyl-2-naphthylamine and the derivatives thereof are very important organic compounds, and the compounds have important biological activity and pharmacological activity and extremely high application value in the fields of pesticides, medicines and the like.

Disclosure of Invention

Therefore, the invention aims to provide a novel compound, namely 1-thiophenyl-N-acetyl-2-naphthylamine and derivatives thereof.

The invention also aims to provide a synthesis method of the 1-thiophenyl-N-acetyl-2-naphthylamine and the derivatives thereof, which has the advantage of simple process.

Thus, the present invention provides a 1-thiophenyl-N-acetyl-2-naphthylamine and its derivatives, which have the general formula of formula I:

wherein

R₁Selected from hydrogen atom, alkyl, alkoxy, halogen and aromatic radical;

R₂selected from straight chain, branched chain alkyl, cyclic alkyl, substituted or non-substituted aryl and alkenyl.

The invention relates to a method for preparing 1-thiophenyl-N-acetyl-2-naphthylamine and derivatives thereof, which is prepared by heating and stirring 2-naphthylamine compounds, thioester compounds, iron-containing reagents and iodine-containing reagents under the reaction condition of an organic solvent.

Preferably, in the method of the present invention, the iodine-containing reagent is selected from one or more of elemental iodine, potassium iodide, amine iodide, tetrabutylamine iodide, iodosuccinimide, iodine chloride, iodobenzene diacetic acid, iodine bromide, hydrogen iodide, 2-iodoylbenzoic acid, zinc iodide, and cuprous iodide.

Preferably, in the method of the present invention, the iron-containing reagent is selected from one or more of ferrous sulfate, ferrous chloride, iron powder, ferric sulfate, ferric fluoride, ferric trifluoromethanesulfonate, ferric oxide, ferric chloride, ferroferric oxide, ferric acetylacetonate, and ferric nitrate.

Preferably, in the method of the present invention, the organic solvent is selected from one or more of acetonitrile, tetrahydrofuran, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, 1, 4-dioxane, toluene, 1, 2-dichloroethane, 1, 2, 2-tetrachloroethane, chlorobenzene, o-xylene, p-xylene, benzyl alcohol, nitrobenzene, pyridine and quinoline.

Preferably, in the method, the molar ratio of the 2-naphthylamine compound to the thioester compound is 1: 1.0-5.0, and the reaction temperature is 80-140 ℃.

Preferably, in the method of the present invention, the structural formula of the 2-naphthylamine is as follows:

formula II

Preferably, in the method of the present invention, the thioester compound has the following formula:

formula III

Wherein

R₁Selected from hydrogen atom, alkyl, alkoxy, halogen and aromatic radical;

Preferably, the thioester compound is selected from the group consisting of S-phenylthioacetate, S- (4-methylphenyl) thioacetate, S- (4-bromophenyl) thioacetate, S- (4-chlorophenyl) thioacetate, S- (4-fluorophenyl) thioacetate, S- (4-methoxyphenyl) thioacetate, S- (3-methylphenyl) thioacetate, S- (3-methoxyphenyl) thioacetate, S- (3-bromophenyl) thioacetate, S- (3-chlorophenyl) thioacetate, S- (3-fluorophenyl) thioacetate, S- (2-methylphenyl), S- (2-bromophenyl) thioacetate, S- (2-chlorophenyl) thioacetate, S- (2-fluorophenyl) thioacetate, S- (2-methoxyphenyl) thioacetate, S- (2-ethylphenyl) thioacetate, S- (2, 3-dichlorophenyl) thioacetate, S- (2-naphthyl) thioacetate, S- (4-methylphenyl) thiopropionate, S- (4-methylphenyl) thiobutyrate, S- (4-methylphenyl) thiovalerate, S- (4-methylphenyl) thiohexanoate, S- (4-methylphenyl) thioheptanoate, S- (4-methylphenyl) thiooctanoate, S- (2-methoxyphenyl) thioacetate, S- (2-fluorophenyl) thioacetate, S- (2-methoxyphenyl) thioacetate, S- (4-methylphenyl) thiohexanoate, S- (4-methylphenyl) thioheptanoate, S- (4-methylphenyl) thiooctanoate, S- (, S- (4-methylphenyl) thiononanoate, S- (4-methylphenyl) thiodecanoate, S- (4-methylphenyl) thiobenzoate, S- (4-methylphenyl) thiophenylacetate, S- (4-methylphenyl) thiophenylpropionate, S- (4-methylphenyl) thio-benzene (4-fluoro) propionate, S- (4-methylphenyl) thio-cyclopentyl propionate, S- (4-methylphenyl) thio-butenoate, S- (4-methylphenyl) thio-cyclopropyl formate, S- (4-methylphenyl) thio-tert-butyrate, S- (4-methylphenyl) thio-isobutyrate, S- (4-methylphenyl) thio-isovalerate, S- (4-methylphenyl) thio-decanoate, S- (4-methylphenyl) thio-benzoate, S- (4-methylphenyl) thio-propionate, S- (4-methylphenyl), S- (4-methylphenyl) thiopivalate.

The invention also claims the application of the 1-thiophenyl-N-acetyl-2-naphthylamine and the derivatives thereof in the synthesis of mechanical synthesis intermediates, bactericides and medicaments.

The technical scheme of the invention has the following advantages:

the invention relates to 1-thiophenyl-N-acetyl-2-naphthylamine and derivatives and a synthesis method thereof, in particular to a method for generating 1-thiophenyl-N-acetyl-2-naphthylamine and derivatives thereof by performing one-pot multi-component reaction under the combined action of a cheap and easily-obtained iron-containing reagent and an iodine compound and generating a new C-N/C-S bond through the carbon-sulfur bond breakage of a thioester compound and the bifunctional recombination of 2-naphthylamine. The method overcomes the defects that the existing synthetic method of the 1-thiophenyl-N-acetyl-2-naphthylamine compound has complex synthetic steps and can be completed by adopting a multi-step synthetic process; the method of the invention keeps atom economy to the utmost extent; the compound has stable molecular structure and excellent chemical property, and the molecular cut block and the compound fragment contain rich contents of biological activity and pharmacological activity; the method also has the advantages of simple reaction system, mild reaction conditions, less reaction equipment, simple and convenient experimental operation, wide material sources, easy expansion of users and application, higher product utilization value and the like.

Drawings

In order to demonstrate the products of the invention, the invention provides nuclear magnetic hydrogen and carbon spectra of some of the examples.

FIG. 1a nuclear magnetic hydrogen spectrum of the product of example 1.

FIG. 1b nuclear magnetic carbon spectrum of the product of example 1.

FIG. 2a nuclear magnetic hydrogen spectrum of the product of example 2.

FIG. 2b nuclear magnetic carbon spectrum of the product of example 2.

FIG. 3a nuclear magnetic hydrogen spectrum of the product of example 3.

FIG. 3b nuclear magnetic carbon spectrum of the product of example 3.

FIG. 4a nuclear magnetic hydrogen spectrum of the product of example 4.

FIG. 4b nuclear magnetic carbon spectrum of the product of example 4.

FIG. 5a nuclear magnetic hydrogen spectrum of the product of example 5.

FIG. 5b nuclear magnetic carbon spectrum of the product of example 5.

FIG. 6a nuclear magnetic hydrogen spectrum of the product of example 6.

FIG. 6b nuclear magnetic carbon spectrum of the product of example 6.

FIG. 7a nuclear magnetic hydrogen spectrum of the product of example 7.

FIG. 7b nuclear magnetic carbon spectrum of the product of example 7.

FIG. 8a nuclear magnetic hydrogen spectrum of the product of example 8.

FIG. 8b nuclear magnetic carbon spectrum of the product of example 8.

FIG. 9a is a nuclear magnetic hydrogen spectrum of the product of example 19.

FIG. 9b nuclear magnetic carbon spectrum of the product of example 19.

FIG. 10a is a nuclear magnetic hydrogen spectrum of the product of example 20.

FIG. 10b nuclear magnetic carbon spectrum of the product of example 20.

FIG. 11 is a general reaction system of the method for synthesizing 1-thiophenyl-N-acetyl-2-naphthylamine and its derivatives.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The technical features mentioned in the different embodiments of the invention described below can be combined with each other as long as they do not conflict with each other.

The synthesis method of the 1-thiophenyl-N-acetyl-2-naphthylamine and the derivative thereof is characterized in that a novel C-N/C-S bond is generated by performing bifunctional recombination on carbon-sulfur bond breakage of thioester compounds and 2-naphthylamine in a cheap and easily-obtained iron-containing reagent and iodine compounds, and 1-thiophenyl-N-acetyl-2-naphthylamine and the derivative thereof are generated in a one-pot multi-component manner. The method overcomes the defects that the existing synthesis method of the 1-thiophenyl-N-acetyl-2-naphthylamine compound has complex synthesis steps and can be completed by adopting a multi-step synthesis process; it maintains atom economy to the utmost extent; it has stable molecular structure, excellent chemical property, molecular blocks and compound segments containing rich contents of biological activity and pharmacological activity; the method also has the characteristics of simple reaction system, mild reaction conditions, less reaction equipment, simple and convenient experimental operation, wide material sources, easy expansion of users and application, higher product utilization value, predictable market commercialization prospect and the like.

1-thiophenyl-N-acetyl-2-naphthylamine and derivatives thereof, having the general formula I:

R₁selected from hydrogen atom, alkyl, alkoxy, halogen and aromatic radical;

The invention also provides a method for preparing the 1-thiophenyl-N-acetyl-2-naphthylamine and the derivatives thereof, which is obtained by heating and stirring the 2-naphthylamine compound and the thioester compound under the reaction condition of an organic solvent.

Preferably, in the method of the present invention, the solvent is selected from one or more of acetonitrile, tetrahydrofuran, N-dimethylacetamide, N-dimethylformamide, dimethylsulfoxide, 1, 4-dioxane, toluene, 1, 2-dichloroethane, 1, 2, 2-tetrachloroethane, chlorobenzene, o-xylene, p-xylene, benzyl alcohol, nitrobenzene, pyridine, and quinoline.

Preferably, in the method of the present invention, the molar ratio of the 2-naphthylamine compound to the thioester is 1: 1.0-5.0, and the reaction temperature is 80-140 ℃.

The structural formula of the 2-naphthylamine is as follows:

the general formula of the thioester compound is shown as formula III:

wherein

R₁Selected from hydrogen atom, alkyl, alkoxy, halogen and aromatic radical;

Preferably, in the method of the present invention, the thioester compound is selected from the group consisting of S-phenylthioacetate, S- (4-methylphenyl) thioacetate, S- (4-bromophenyl) thioacetate, S- (4-chlorophenyl) thioacetate, S- (4-fluorophenyl) thioacetate, S- (4-methoxyphenyl) thioacetate, S- (3-methylphenyl) thioacetate, S- (3-methoxyphenyl) thioacetate, S- (3-bromophenyl) thioacetate, S- (3-chlorophenyl) thioacetate, S- (3-fluorophenyl) thioacetate, S- (2-methylphenyl), S- (2-bromophenyl) thioacetate, S- (2-chlorophenyl) thioacetate, S- (2-fluorophenyl) thioacetate, S- (2-methoxyphenyl) thioacetate, S- (2-ethylphenyl) thioacetate, S- (2, 3-dichlorophenyl) thioacetate, S- (2-naphthyl) thioacetate, S- (4-methylphenyl) thiopropionate, S- (4-methylphenyl) thiobutyrate, S- (4-methylphenyl) thiovalerate, S- (4-methylphenyl) thiohexanoate, S- (4-methylphenyl) thioheptanoate, S- (4-methylphenyl) thiooctanoate, S- (2-methoxyphenyl) thioacetate, S- (2-fluorophenyl) thioacetate, S- (2-methoxyphenyl) thioacetate, S- (4-methylphenyl) thiohexanoate, S- (4-methylphenyl) thioheptanoate, S- (4-methylphenyl) thiooctanoate, S- (, S- (4-methylphenyl) thiononanoate, S- (4-methylphenyl) thiodecanoate, S- (4-methylphenyl) thiobenzoate, S- (4-methylphenyl) thiophenylacetate, S- (4-methylphenyl) thiophenylpropionate, S- (4-methylphenyl) thio-benzene (4-fluoro) propionate, S- (4-methylphenyl) thio-cyclopentyl propionate, S- (4-methylphenyl) thio-butenoate, S- (4-methylphenyl) thio-cyclopropyl formate, S- (4-methylphenyl) thio-tert-butyrate, S- (4-methylphenyl) thio-isobutyrate, S- (4-methylphenyl) thio-isovalerate, S- (4-methylphenyl) thio-decanoate, S- (4-methylphenyl) thio-benzoate, S- (4-methylphenyl) thio-propionate, S- (4-methylphenyl), S- (4-methylphenyl) thiopivalate.

The general formula of the reaction system of the synthesis method of the 1-thiophenyl-N-acetyl-2-naphthylamine and the derivatives thereof is formed by the formulas I, II and III, as follows:

the method comprises the following steps:

(1) adding 2-naphthylamine, thioester, iron, iodine and organic solvent into a reaction vessel;

(2) fully mixing the reactants, and heating;

(3) purifying after the reaction to obtain a product;

the organic solvent is selected from one or more of acetonitrile, tetrahydrofuran, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, 1, 4-dioxane, toluene, 1, 2-dichloroethane, 1, 2, 2-tetrachloroethane, chlorobenzene, o-xylene, p-xylene, benzyl alcohol, nitrobenzene, pyridine and quinoline.

Preferably chlorobenzene;

for better synthesis, the molar ratio of the 2-naphthylamine compound to the thioester is preferably 1: 2,

the iron-containing reagent is selected from one or more of ferrous sulfate, ferrous chloride, iron powder, ferric sulfate, ferric fluoride, ferric trifluoromethanesulfonate, ferric oxide, ferric chloride, ferroferric oxide, ferric acetylacetonate and ferric nitrate;

preferably ferric oxide;

the iodine-containing reagent is selected from one or more of iodine, potassium iodide, amine iodide, tetrabutylamine iodide, iodosuccinimide, iodine chloride, iodobenzene diacetic acid, iodine bromide, hydrogen iodide, 2-iodosylbenzoic acid, zinc iodide, and copper iodide

Preferably iodo-succinimide;

the reaction temperature T is 80-140 ℃;

preferably 130 deg.c.

1-thiophenyl-N-acetyl-2-naphthylamine and derivatives thereof can be obtained from the process of the synthetic reaction system of the compound, under the combined action of a reagent containing iron and an iodine compound, the carbon-sulfur bond of the thioester compound is broken and the 2-naphthylamine is subjected to bifunctional recombination to generate a new C-N/C-S bond.

As an important molecular block, the compound of the formula III has stable molecular structure, excellent chemical property and certain physiological activity, can further synthesize a plurality of compound fragments containing 1-thiophenyl-N-acetyl-2-naphthylamine by converting functional groups, and has strong physiological activity and pharmacological activity; in a word, the compound has the characteristics that the reaction raw materials are cheap and easy to obtain, pretreatment is not needed, the reaction is directly synthesized in one pot, and the like; the method solves the problems of high cost and the like caused by the conventional multi-step synthesis method; the reaction condition is mild, and the temperature required by the reaction is greatly lower than the reaction temperature of the previous multi-step synthesis; the synthesized series of 1-thiophenyl-N-acetyl-2-naphthylamine compounds have quite high potential application value.

Table: reactants, reaction conditions and yields of examples 1-39

Nuclear magnetic and mass spectral data for the products of the examples are

The nuclear magnetic and mass spectral data of the product of example 1 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.75(s，1H)，8.71(d，J＝9.0Hz，1H)，8.38(d，J＝8.4Hz，1H)，7.96(d，J＝9.1Hz，1H)，7.83(d，J＝7.8Hz，1H)，7.51-7.46(m，1H)，7.45-7.40(m，1H)，7.19-7.13(m，2H)，7.12-7.06(m，1H)，6.98(m，2H)，2.14(s，3H).¹³C NMR(CDCl₃，100MHz，ppm)：168.6，140.4，135.6，135.2，131.5，131.0，129.2，128.4，127.7，126.3，125.9，125.8，125.1，119.8，113.2，25.0.HRMS calcd.for：C₁₈H₁₆NOS⁺[M+H]⁺294.0947，found 294.0948.

the nuclear magnetic and mass spectral data of the product of example 2 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.79(s，1H)，8.70(d，J＝9.0Hz，1H)，8.40(d，J＝8.5Hz，1H)，7.95(d，J＝9.1Hz，1H)，7.83(d，J＝7.9Hz，1H)，7.47-7.51(m，1H)，7.45-7.40(m，1H)，6.98(d，J＝8.1Hz，2H)，6.90(d，J＝8.3Hz，2H)，2.24(s，3H)，2.14(s，3H).¹³C NMR(CDCl₃，100MHz，ppm)168.6，140.3，135.9，135.0，132.0，131.4，131.0，130.0，128.4，127.7，126.5，125.8，125.1，119.7，113.8，25.1，20.8.HRMS calcd.for：C₁₉H₁₈NOS⁺[M+H]⁺308.1104，found 308.1105.

the nuclear magnetic and mass spectral data of the product of example 3 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.82(s，1H)，8.72(d，J＝9.0Hz，1H)，8.42(d，J＝8.5Hz，1H)，7.96(d，J＝9.1Hz，1H)，7.84(d，J＝8.0Hz，1H)，7.53-7.48(m，1H)，7.46-7.41(m，1H)，7.22-7.18(m，2H)，6.94-9.92(m，2H)，2.16(s，3H)，1.23(s，9H).¹³C NMR(CDCl₃，100MHz，ppm)168.6，149.1，140.3，135.1，132.0，131.3，131.0，128.4，127.7，126.3，126.2，125.9，125.0，119.7，113.7，34.3，31.2，25.0.HRMS calcd.for：C₂₂H₂₄NOS⁺[M+H]⁺350.1573，found 350.1576.

the nuclear magnetic and mass spectral data of the product of example 4 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.84(s，1H)，8.68(d，J＝9.0Hz，1H)，8.43(d，J＝8.5Hz，1H)，7.93(d，J＝9.1Hz，1H)，7.81(d，J＝8.0Hz，1H)，7.50(t，J＝7.6Hz，1H)，7.41(t，J＝7.4Hz，1H)，6.97(d，J＝8.7Hz，2H)，6.72(d，J＝8.7Hz，2H)，3.69(s，3H)，2.17(s，3H).¹³CNMR(CDCl₃，100MHz，ppm)168.7，158.4，140.1，135.0，131.2，131.1，128.6，128.5，127.7，126.1，125.9，125.1，119.8，115.0，114.8，55.3，25.1.HRMS calcd.for：C₁₉H₁₈NO₂S⁺[M+H]⁺324.1053，found 324.1054.

the nuclear magnetic and mass spectral data of the product of example 5 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.75(s，1H)，8.70(d，J＝9.0Hz，1H)，8.36(d，J＝8.5Hz，1H)，7.96(d，J＝9.1Hz，1H)，7.83(d，J＝7.9Hz，1H)，7.53-7.48(m，1H)，7.46-7.41(m，1H)，6.99-6.93(m，2H)，6.91-6.85(m，2H)，2.18(s，3H).¹³C NMR(CDCl₃，100MHz，ppm)168.6，161.3(d，J＝244.5Hz)，140.3，134.8，131.6，131.1，130.6(d，J＝3.2Hz)，128.5，128.1(d，J＝7.9Hz)，127.8，125.6，125.2，119.8，116.4(d，J＝22.1Hz)113.5，25.0.HRMScalcd.for：C₁₈H₁₅FNOS⁺[M+H]⁺312.0853，found 312.0857.

the nuclear magnetic and mass spectral data of the product of example 6 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.71(d，J＝8.0Hz，2H)，8.32(d，J＝8.4Hz，1H)，7.98(d，J＝9.1Hz，1H)，7.84(d，J＝8.0Hz，1H)，7.50(t，J＝7.6Hz，1H)，7.44(t，J＝7.3Hz，1H)，7.13(d，J＝8.5Hz，2H)，6.89(d，J＝8.5Hz，2H)，2.18(s，3H).¹³C NMR(CDCl₃，100MHz，ppm)168.6，140.5，134.8，134.1，131.8，131.7，131.1，129.4，128.5，127.9，127.4，125.5，125.2，119.8，112.6，25.1.HRMS calcd.for：C₁₈H₁₅ClNOS⁺[M+H]⁺328.0557，found328.0557.

the nuclear magnetic and mass spectral data of the product of example 7 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.72(s，1H)，8.70(d，J＝9.0Hz，1H)，8.31(d，J＝8.4Hz，1H)，7.99(d，J＝9.1Hz，1H)，7.85(d，J＝8.0Hz，1H)，7.51(t，J＝7.5Hz，1H)，7.45(t，J＝7.3Hz，1H)，7.28(d，J＝8.5Hz，2H)，6.82(d，J＝8.5Hz，2H)，2.18(s，3H).¹³C NMR(CDCl₃，100MHz，ppm)168.6，140.5，134.8，134.7，132.3，131.9，131.1，128.5，128.0，127.7，125.5，125.3，119.8，119.5，112.4，25.1.HRMS calcd for：C₁₈H₁₅BrNOS⁺[M+H]⁺372.0052，found 372.0056.

the nuclear magnetic and mass spectral data of the product of example 8 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.79-8.61(m，2H)，8.29(d，J＝8.4Hz，1H)，7.97(d，J＝9.1Hz，1H)，7.87-7.82(m，1H)，7.50-7.45(m，1H)，7.45-7.40(m，1H)，7.25-7.20(m，1H)，7.08-7.02(m，1H)，6.87-6.81(m，1H)，6.36-6.28(m，1H)，3.03-2.95(m，2H)，2.13(s，3H)，1.43(t，J＝7.5Hz，3H).¹³C NMR(CDCl₃，100MHz，ppm)168.6，140.9，140.6，135.1，133.9，131.4，131.1，128.6，128.4，127.7，126.9，125.7，125.3，125.1，119.8，112.9，26.8，25.0，14.4.HRMS calcd.for：C₂₀H₂₀NOS⁺[M+H]⁺322.1260，found 322.1262.

the nuclear magnetic and mass spectral data of the product of example 9 are as follows:

the nuclear magnetic and mass spectral data of the product of example 10 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.87(s，1H)，8.71(d，J＝9.0Hz，1H)，8.40(d，J＝8.4Hz，1H)，7.95(d，J＝9.1Hz，1H)，7.82(d，J＝7.9Hz，1H)，7.51-7.45(m，1H)，7.44-7.39(m，1H)，7.13-7.06(m，1H)，6.88(d，J＝8.2Hz，1H)，6.69-6.62(m，1H)，6.49-6.42(m，1H)，3.97(s，3H)，2.16(s，3H).¹³C NMR(CDCl₃，100MHz，ppm)168.7，156.2，140.6，135.3，131.2，131.0，128.4，127.6，127.5，127.0，125.9，125.0，123.6，121.6，119.8，112.9，110.6，56.0，25.0.HRMS calcd.for：C₁₉H₁₈NO₂S⁺[M+H]⁺324.1053，found 324.1056.

the nuclear magnetic and mass spectral data of the product of example 11 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.79(s，1H)，8.71(d，J＝9.0Hz，1H)，8.43(d，J＝8.5Hz，1H)，7.98(d，J＝9.1Hz，1H)，7.85(d，J＝8.0Hz，1H)，7.57-7.51(m，1H)，7.48-7.42(m，1H)，7.16-7.06(m，2H)，6.88-6.82(m，1H)，6.62-6.55(m，1H)，2.21(s，3H).¹³C NMR(CDCl₃，100MHz，ppm)168.7，159.9(d，J＝242.8Hz)，140.7，135.1，131.7，131.1，128.9，128.5，127.8(d，J＝10.5Hz)，125.6，125.2，125.0(d，J＝3.3Hz)，122.5(d，J＝16.9Hz)，119.9，115.6(d，J＝21.2Hz)，25.0.HRMS calcd for：C₁₈H₁₅FNOS⁺[M+H]⁺312.0853，found312.0856.

the nuclear magnetic and mass spectral data of the product of example 12 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.73(d，J＝9.1Hz，1H)，8.67(s，1H)，8.32(d，J＝8.5Hz，1H)，8.00(d，J＝9.1Hz，1H)，7.86(d，J＝7.7Hz，1H)，7.54-7.49(m，1H)，7.48-7.43(m，1H)，7.42-7.35(m，1H)，7.07-7.01(m，1H)，6.92-6.86(m，1H)，6.37-6.29(m，1H)，2.17(s，3H).¹³C NMR(CDCl₃，100MHz，ppm)168.7，140.8，135.0，134.7，131.9，131.5，131.1，129.6，128.5，128.0，127.5，126.9，126.7，125.6，125.3，119.9，112.2，25.1.HRMScalcd.for：C₁₈H₁₅ClNOS⁺[M+H]⁺328.0557，found 328.0557.

the nuclear magnetic and mass spectral data of the product of example 13 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.73(d，J＝9.1Hz，1H)，8.65(s，1H)，8.32(d，J＝8.5Hz，1H)，8.01(d，J＝9.1Hz，1H)，7.87(d，J＝7.5Hz，1H)，7.62-7.55(m，1H)，7.55-7.50(m，1H)，7.49-7.43(m，1H)，7.00-6.92(m，2H)，6.35-6.27(m，1H)，2.18(s，3H).¹³C NMR(CDCl₃，100MHz，ppm)168.7，140.7，136.6，134.9，132.9，131.9，131.0，128.5，128.1，128.0，126.9，126.8，125.5，125.2，121.1，119.8，112.8，25.1.HRMS calcd.for：C₁₈H₁₅BrNOS⁺[M+H]⁺372.0052，found 372.0053.

the nuclear magnetic and mass spectral data of the product of example 14 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.76(s，1H)，8.71(d，J＝9.0Hz，1H)，8.38(d，J＝8.5Hz，1H)，7.96(d，J＝9.1Hz，1H)，7.83(d，J＝7.6Hz，1H)，7.52-7.46(m，1H)，7.45-7.39(m，1H)，7.04(t，J＝7.7Hz，1H)，6.91(d，J＝7.6Hz，1H)，6.85(s，1H)，6.73(d，J＝7.9Hz，1H)，2.20(s，3H)，2.15(s，3H).¹³C NMR(CDCl₃，100MHz，ppm)168.6，140.4，139.2，135.3，135.0，131.4，131.0，129.1，128.4，127.7，126.8，126.8，125.8，125.1，123.3，119.7，113.3，25.0，21.3.HRMS calcd.for：C₁₉H₁₈NOS⁺[M+H]⁺308.1104，found 308.1106.

the nuclear magnetic and mass spectral data of the product of example 15 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.76(s，1H)，8.71(d，J＝9.0Hz，1H)，8.38(d，J＝8.5Hz，1H)，7.96(d，J＝9.1Hz，1H)，7.83(d，J＝7.6Hz，1H)，7.52-7.46(m，1H)，7.45-7.39(m，1H)，7.04(t，J＝7.7Hz，1H)，6.91(d，J＝7.6Hz，1H)，6.85(s，1H)，6.73(d，J＝7.9Hz，1H)，2.20(s，3H)，2.15(s，3H).¹³C NMR(CDCl₃，100MHz，ppm)168.6，140.3，139.1，135.3，135.0，131.4，131.0，129.1，128.4，127.7，126.8，126.7，125.8，125.1，123.3，119.7，113.3，25.0，21.3.HRMS calcd.for：C₁₉H₁₈NO₂S⁺[M+H]⁺324.1053，found 324.1055.

the nuclear magnetic and mass spectral data of the product of example 16 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.82-8.63(m，2H)，8.32(d，J＝8.5Hz，1H)，7.99(d，J＝9.1Hz，1H)，7.85(d，J＝8.1Hz，1H)，7.54-7.48(m，1H)，7.48-7.40(m，1H)，7.18-7.10(m，1H)，6.83-6.73(m，2H)，6.71-6.59(m，1H)，2.18(s，3H).¹³C NMR(CDCl₃，100MHz，ppm)168.6，163.1(d，J＝247.5Hz)140.6，138.0(d，J＝7.5Hz)，134.9，132.0，131.1，130.5(d，J＝8.2Hz)，128.5，127.9，125.4(d，J＝23.8Hz)，121.7(d，J＝7.9Hz)，119.8，113.3，113.0(d，J＝3.3Hz)，112.8，112.1，25.0.HRMS calcd.for：C₁₈H₁₅FNOS⁺[M+H]⁺312.0853，found312.0856.

the nuclear magnetic and mass spectral data of the product of example 17 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.75(s，1H)，8.71(d，J＝12.7Hz，1H)，8.37-8.29(m，1H)，8.01(d，J＝9.1Hz，1H)，7.89-7.84(m，1H)，7.56-7.50(m，1H)，7.49-7.44(m，1H)，7.11-7.05(m，2H)，7.05-6.99(m，1H)，6.81-6.75(m，1H)，2.20(s，3H).¹³C NMR(CDCl₃，400MHz，ppm)168.6，140.6，137.7，135.1，134.8，132.0，131.0，130.3，128.5，128.0，126.1，125.9，125.5，125.3，124.1，119.8，112.0，25.0.HRMS calcd.for：C₁₈H₁₅ClNOS⁺[M+H]⁺328.0557，found 328.0561.

the nuclear magnetic and mass spectral data of the product of example 18 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.73(d，J＝9.0Hz，1H)，8.68(s，1H)，8.32(d，J＝8.4Hz，1H)，8.00(d，J＝9.1Hz，1H)，7.86(d，J＝7.6Hz，1H)，7.55-7.49(m，1H)，7.48-7.43(m，1H)，7.26-7.18(m，2H)，7.01(t，J＝7.9Hz，1H)，6.81-6.75(m，1H)，2.19(s，3H).¹³C NMR(CDCl₃，100MHz，ppm)168.6，140.6，138.0，134.8，132.0，131.0，130.6，129.0，128.7，128.6，128.0，125.3，125.3，124.5，123.2，119.7，111.9，25.1.HRMS calcd.for：C₁₈H₁₅BrNOS⁺[M+H]⁺372.0052，found 372.0053.

the nuclear magnetic and mass spectral data of the product of example 19 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.82(s，1H)，8.76(d，J＝9.0Hz，1H)，8.41(d，J＝8.3Hz，1H)，8.01(d，J＝9.1Hz，1H)，7.89-7.84(m，1H)，7.75-7.70(m，1H)，7.66(d，J＝8.7Hz，1H)，7.57-7.53(m，1H)，7.50-7.35(m，5H)，7.16-7.11(m，1H)，2.13(s，3H).¹³C NMR(CDCl₃，100MHz，ppm)168.7，140.6，135.1，133.7，133.0，131.7，131.6，131.1，129.0，128.5，127.8，127.7，127.0，126.7，125.8，125.7，125.2，124.5，124.2，119.8，113.0，25.1.HRMS calcd.for：C₂₂H₁₈NOS⁺[M+H]⁺344.1104，found 344.1105.

the nuclear magnetic and mass spectral data of the product of example 20 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.74(d，J＝9.1Hz，1H)，8.61(s，1H)，8.27(d，J＝8.4Hz，1H)，8.03(d，J＝9.1Hz，1H)，7.87(d，J＝7.5Hz，1H)，7.55-7.50(m，1H)，7.49-7.45(m，1H)，7.23-7.18(m，1H)，6.83(t，J＝8.0Hz，1H)，6.21-6.15(m，1H)，2.19(s，3H).¹³C NMR(CDCl₃，100MHz，ppm)168.8，140.9，137.3，134.7，133.5，132.3，131.1，129.2，128.6，128.2，127.7，127.3，125.4，125.3，124.5，119.9，111.6，25.1.HRMS calcd.for：C₁₈H₁₄Cl₂NOS⁺[M+H]⁺362.0168，found 362.0173.

the nuclear magnetic and mass spectral data of the product of example 21 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.84(s，1H)，8.75(d，J＝9.1Hz，1H)，8.41(d，J＝8.5Hz，1H)，7.96(d，J＝9.1Hz，1H)，7.84(d，J＝8.0Hz，1H)，7.54-7.47(m，1H)，7.46-7.40(m，1H)，6.98(d，J＝8.1Hz，2H)，6.90(d，J＝8.3Hz，2H)，2.43-2.36(m.2H)，2.24(s，3H)，1.18(t，J＝7.6Hz，3H).¹³C NMR(CDCl₃，100MHz，ppm)172.2，140.3，135.8，135.1，131.9，131.2，130.9，130.0，128.3，127.6，126.4，125.8，125.0，119.8，113.8，31.2，20.9，9.4.HRMS calcd for：C₂₀H₂₀NOS⁺[M+H]⁺322.1260，found 322.1263.

the nuclear magnetic and mass spectral data of the product of example 22 are as follows:

¹H NMR(CDCl₃，100MHz，ppm)8.82(s，1H)，8.75(d，J＝9.1Hz，1H)，8.41(d，J＝8.5Hz，1H)，7.96(d，J＝9.1Hz，1H)，7.84(d，J＝7.9Hz，1H)，7.53-7.48(m，1H)，7.45-7.40(m，1H)，6.98(d，J＝8.1Hz，2H)，6.92-6.87(m，2H)，2.34(t，J＝7.5Hz，2H)，2.24(s，3H)，1.68(q，J＝7.4Hz，2H)，0.93(t，J＝7.4Hz，3H).¹³C NMR(CDCl₃，100MHz，ppm)171.6，140.3，135.8，135.2，132.0，131.4，131.0，130.0，128.4，127.7，126.5，125.8，125.0，119.8，113.8，40.1，20.8，18.9，13.6.HRMS calcd for：C₂₁H₂₂NOS⁺[M+H]⁺336.1417，found336.1420.

the nuclear magnetic and mass spectral data of the product of example 23 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.83(s，1H)，8.75(d，J＝9.1Hz，1H)，8.43(d，J＝8.5Hz，1H)，7.97(d，J＝9.1Hz，1H)，7.87-7.83(m，1H)，7.54-7.49(m，1H)，7.47-7.42(m，1H)，6.99(d，J＝8.0Hz，2H)，6.94-6.88(m，2H)，2.37(t，J＝7.5Hz，2H)，2.25(s，3H)，1.66-1.59(m，2H)，1.35-1.29(m，2H)，0.88(t，J＝7.3Hz，3H).¹³C NMR(CDCl₃，100MHz，ppm)171.7，140.3，135.8，135.1，131.9，131.3，130.9，130.0，128.3，127.6，126.4，125.8，125.0，119.8，113.7，37.9，27.5，22.2，20.8，13.7.HRMS calcd for：C₂₂H₂₄NOS⁺[M+H]⁺350.1573，found 350.1577.

the nuclear magnetic and mass spectral data of the product of example 24 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.84(s，1H)，8.76(d，J＝9.0Hz，1H)，8.47-8.39(m，1H)，7.98(d，J＝9.1Hz，1H)，7.87-7.83(m，1H)，7.54-7.49(m，1H)，7.47-7.42(m，1H)，6.99(d，J＝8.2Hz，1H)，6.93-6.88(m，2H)，2.36(t，J＝7.5Hz，2H)，2.25(s，3H).1.66-1.61(m，2H)，1.32-1.24(m，4H)，0.90-0.83(m，3H).¹³C NMR(CDCl₃，100MHz，ppm)171.8，140.3，135.8，135.2，132.0，131.4，130.9，130.0，128.4，127.6，126.4，125.8，125.0，119.7，113.7，38.2，31.2，25.2.，22.3，20.8，13.8.HRMS calcd.for：C₂₃H₂₆NOS⁺[M+H]⁺364.1730，found 364.1733.

the nuclear magnetic and mass spectral data of the product of example 25 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.84(s，1H)，8.77(d，J＝8.8Hz，1H)，8.44(d，J＝8.0Hz，1H)，7.99(d，J＝9.2Hz，1H)，7.86-7.84(d，J＝8.0Hz，1H)，7.48-7.43(m，1H)，7.44-7.42(m，1H)，7.00(d，J＝1.9Hz，2H)，6.91(d，J＝2.1Hz，2H)，2.38(t，J＝7.5Hz，2H)，2.25(s，3H)，1.66(d，J＝7.2Hz，2H)，1.35-1.25(m，6H)，0.92-0.87(m，3H).¹³C NMR(CDCl₃，100MHz，ppm)171.7，140.3，135.8，135.1，131.9，131.4，130.9，130.0，128.4，127.6，126.3，125.8，125.0，119.7，113.6，38.3，31.5，28.7，25.4，22.4，20.8，14.0.HRMScalcd.for：C₂₄H₂₈NOS⁺[M+H]⁺378.1886，found 378.1891.

the nuclear magnetic and mass spectral data of the product of example 26 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.83(s，1H)，8.74(d，J＝9.1Hz，1H)，8.45-8.38(m，1H)，7.96(d，J＝9.1Hz，1H)，7.86-7.81(m，1H)，7.52-7.47(m，1H)，7.45-7.40(m，1H)，6.98(d，J＝8.2Hz，2H)，6.92-6.86(m，2H)，2.35(t，J＝7.5Hz，2H)，2.24(s，3H)，1.61(d，J＝8.4Hz，2H)，1.31-1.19(m，8H)，0.87(t，J＝6.9Hz，3H).¹³C NMR(CDCl₃，100MHz，ppm)171.7，140.4，135.8，135.2，132.0，131.4，131.0，130.0，128.4，127.7，126.4，125.8，125.0，119.8，113.7，38.3，31.6，29.1，29.0，25.5，22.6，20.8，14.0.HRMS calcd.for：C₂₅H₃₀NOS⁺[M+H]⁺392.2043，found 392.2044.

the nuclear magnetic and mass spectral data of the product of example 27 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.82(s，1H)，8.74(d，J＝9.1Hz，1H)，8.44-8.38(m，1H)，7.96(d，J＝9.1Hz，1H)，7.85-7.81(m，1H)，7.52-7.47(m，1H)，7.45-7.40(m，1H)，6.98(d，J＝8.2Hz，2H)，6.91-6.87(m，2H)，2.35(t，J＝7.5Hz，2H)，2.24(s，3H)，1.66-1.59(m，2H)，1.31-1.21(m，10H)，0.87(t，J＝6.9Hz，3H).¹³C NMR(CDCl₃，100MHz，ppm)171.8，140.3，135.8，135.1，131.9，131.4，131.0，130.1，128.4，127.7，126.4，125.8，125.0，119.8，113.6，38.3，31.8，29.3，29.1，29.0，25.5，22.6，20.8，14.0.HRMS calcd.for：C₂₆H₃₂NOS⁺[M+H]⁺406.2199，found 406.2203.

the nuclear magnetic and mass spectral data of the product of example 28 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.82(s，1H)，8.74(d，J＝9.1Hz，1H)，8.45-8.38(m，1H)，7.96(d，J＝9.1Hz，1H)，7.86-7.82(m，1H)，7.53-7.48(m，1H)，7.45-7.40(m，1H)，6.98(d，J＝8.2Hz，2H)，6.92-6.87(m，2H)，2.35(t，J＝7.6Hz，2H)，2.24(s，3H)，1.66-1.58(m，2H)，1.32-1.20(m，12H)，0.88(t，J＝6.9Hz，3H).¹³C NMR(CDCl₃，100MHz，ppm)171.8，140.4，135.8，135.2，132.0，131.4，131.0，130.0，128.4，127.7，126.4，125.8，125.0，119.8，113.7，38.3，31.8，29.4，29.3，29.2，29.1，25.5，22.6，20.8，14.1.HRMS calcd.for：C₂₇H₃₄NOS⁺[M+H]⁺420.2356，found 420.2359.

the nuclear magnetic and mass spectral data of the product of example 29 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.91(s，1H)，8.76(d，J＝9.1Hz，1H)，8.43(d，J＝8.5Hz，1H)，7.97(d，J＝9.1Hz，1H)，7.86-7.82(m，1H)，7.53-7.48(m，1H)，7.46-7.40(m，1H)，6.98(d，J＝8.1Hz，2H)，6.92-6.87(m，2H)，2.58-2.47(m，1H)，2.24(s，3H)，1.17(d，J＝6.9Hz，6H).¹³C NMR(CDCl₃，100MHz，ppm)175.4，140.3，135.8，135.2，131.8，131.6，131.3，130.9，128.4，127.6，126.3，125.7，125.0，119.7，113.8，37.1，20.8，19.4.HRMScalcd.for：C₂₁H₂₂NOS⁺[M+H]⁺336.1417，found 336.1420.

the nuclear magnetic and mass spectral data of the product of example 30 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)9.22(s，1H)，8.78(d，J＝9.1Hz，1H)，8.49-8.42(m，1H)，7.98(d，J＝9.1Hz，1H)，7.87-7.84(m，1H)，7.54-7.50(m，1H)，7.46-7.42(m，1H)，6.99(d，J＝8.2Hz，2H)，6.92-6.87(m，2H)，2.24(s，3H)，1.23(s，9H).¹³C NMR(CDCl₃，100MHz，ppm)177.0，140.5，135.7，135.4，131.8，131.4，131.0，130.0，128.4，127.7，126.2，125.7，125.0，119.7，114.0，40.3，27.4，20.8.HRMS calcd.for：C₂₂H₂₄NOS⁺[M+H]⁺350.1573，found350.1578.

the nuclear magnetic and mass spectral data of the product of example 31 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)9.02(s，1H)，8.69(d，J＝9.1Hz，1H)，8.36-8.29(m，1H)，7.89(d，J＝9.1Hz，1H)，7.79-7.74(m，1H)，7.46-7.40(m，1H)，7.39-7.33(m，1H)，6.93(d，J＝8.0Hz，2H)，6.89-6.83(m，2H)，2.19(s，3H)，1.51-1.45(m，1H)，1.04-0.98(m，2H)，0.82-0.75(m，2H).¹³C NMR(CDCl₃，100MHz，ppm)172.2，140.6，135.8，135.1，132.1，131.4，130.9，130.0，128.4，127.7，126.6，125.8，124.9，119.7，113.2，20.8，16.3，8.3.HRMScalcd.for：C₂₁H₂₀NOS⁺[M+H]⁺334.1260，found 334.1263.

the nuclear magnetic and mass spectral data of the product of example 32 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.81(s，1H)，8.76(d，J＝9.0Hz，1H)，8.46-8.39(m，1H)，7.98(d，J＝9.1Hz，1H)，7.88-7.83(m，1H)，7.54-7.48(m，1H)，7.47-7.42(m，1H)，6.99(d，J＝8.3Hz，2H)，6.93-6.87(m，2H)，2.24(d，J＝10.0Hz，5H)，2.17-2.08(m，1H)，0.94(d，J＝6.6Hz，6H).¹³C NMR(CDCl₃，100MHz，ppm)171.1，140.3，135.8，135.1，132.0，131.3，131.0，130.0，128.4，127.6，126.4，125.8，125.0，119.8，113.7，47.5，26.2，22.3，20.8.HRMS calcd.for：C₂₂H₂₄NOS⁺[M+H]⁺350.1573，found 350.1577.

the nuclear magnetic and mass spectral data of the product of example 33 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.79(d，J＝9.0Hz，2H)，8.41(d，J＝8.5Hz，1H)，7.98(d，J＝9.1Hz，1H)，7.87-7.83(m，1H)，7.53-7.48(m，1H)，7.46-7.41(m，1H)，6.98(d，J＝8.1Hz，2H)，6.93-6.85(m，2H)，2.24(d，J＝2.8Hz，5H)，1.03(s，9H).¹³C NMR(CDCl₃，100MHz，ppm)170.4，140.4，135.7，135.2，132.0，131.4，130.9，130.0，128.3，127.6，126.3，125.8，125.0，119.6，113.4，52.3，31.2，29.7，20.8.HRMS calcd.for：C₂₃H₂₆NOS⁺[M+H]⁺364.1730，found 364.1733.

the nuclear magnetic and mass spectral data of the product of example 34 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.83(s，1H)，8.76(d，J＝9.1Hz，1H)，8.48-8.40(m，1H)，7.98(d，J＝9.1Hz，1H)，7.87-7.83(m，1H)，7.54-7.49(m，1H)，7.47-7.42(m，1H)，7.00(d，J＝8.2Hz，2H)，6.93-6.88(m，2H)，2.40-2.35(m，2H)，2.25(s，3H)，1.76-1.44(m，9H)，1.11-1.01(m，2H).¹³C NMR(CDCl₃，100MHz，ppm)171.8，140.3，135.8，135.2，132.0，131.3，130.9，130.0，128.4，127.6，126.3，125.8，125.0，119.8，113.6，39.5，37.6，32.4，31.7，25.1，20.8.HRMS calcd.for：C₂₅H₂₈NOS⁺[M+H]⁺390.1886，found 390.1889.

the nuclear magnetic and mass spectral data of the product of example 35 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)9.76(s，1H)，8.98(d，J＝9.1Hz，1H)，8.50-8.44(m，1H)，8.05(d，J＝9.1Hz，1H)，7.91-7.87(m，1H)，7.86-7.82(m，2H)，7.58-7.52(m，2H)，7.50-7.44(m，3H)，7.02-6.95(m，4H)，2.24(s，3H).¹³C NMR(CDCl₃，100MHz，ppm)165.4，140.4，136.0，135.2，134.8，132.0，131.8，131.5，131.1，130.0，128.8，128.5，127.8，127.1，126.6，125.9，125.1，119.5，114.4，20.8.HRMS calcd.for：C₂₄H₂₀NOS⁺[M+H]⁺370.1260.found 370.1260.

the nuclear magnetic and mass spectral data of the product of example 36 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.91(s，1H)，8.77(d，J＝9.1Hz，1H)，8.40-8.33(m，1H)，7.96(d，J＝9.1Hz，1H)，7.85-7.81(m，1H)，7.50-7.46(m，1H)，7.45-7.40(m，1H)，7.30-7.26(m，3H)，7.23-7.16(m，2H)，6.94(d，J＝8.1Hz，2H)，6.72-6.62(m，2H)，3.74(s，2H)，2.26(s，3H).¹³C NMR(CDCl₃，100MHz，ppm)169.5，140.3，135.5，135.3，133.9，131.8，131.4，131.1，129.8，129.6，129.1，128.3，127.7，127.6，126.1，125.8，125.1，119.4，113.9，45.5，20.9.HRMS calcd.for：C₂₅H₂₂NOS⁺[M+H]⁺384.1417，found 384.1421.

the nuclear magnetic and mass spectral data of the product of example 37 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.85-8.67(m，2H)，8.47-8.38(m，1H)，7.98(d，J＝9.1Hz，1H)，7.88-7.83(m，1H)，7.54-7.49(m，1H)，7.47-7.42(m，1H)，7.30-7.25(m，2H)，7.24-7.17(m，3H)，6.99(d，J＝8.1Hz，2H)，6.92-6.84(m，2H)，3.04-2.95(m，2H)，2.72-2.64(m，2H)，2.26(s，3H).¹³C NMR(CDCl₃，100MHz，ppm)170.6，140.4，140.1，135.8，135.1，132.0，131.3，131.0，130.1，128.5，128.4，128.2，127.7，126.5，126.3，125.8，125.1，119.8，113.9，39.7，31.3，20.8.HRMS calcd.for：C₂₆H₂₄NoS⁺[M+H]⁺398.1573，found398.1573.

the nuclear magnetic and mass spectral data of the product of example 38 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.92(s，1H)，8.86(d，J＝9.1Hz，1H)，8.43-8.37(m，1H)，7.98(d，J＝9.1Hz，1H)，7.87-7.83(m，1H)，7.53-7.48(m，1H)，7.46-7.41(m，1H)，7.02-6.89(m，5H)，6.02-5.93(m，1H)，2.25(s，3H)，1.97-1.84(m，3H).¹³C NMR(CDCl₃，100MHz，ppm)164.1，141.8，140.6，135.8，135.1，132.0，131.4，131.0，130.0，128.4，127.7，126.5，125.9，125.8，125.0，119.7，113.8，20.8，17.8.HRMS calcd.for：C₂₁H₂₀NOS⁺[M+H]⁺334.1260，found 334.1261.

the nuclear magnetic and mass spectral data of the product of example 39 are as follows:

¹H NMR(CDCl₃，400MHz，ppm)8.86(s，1H)，8.77(d，J＝9.1Hz，1H)，8.36(d，J＝8.4Hz，1H)，7.97(d，J＝9.1Hz，1H)，7.84(d，J＝8.0Hz，1H)，7.51-7.46(m，1H)，7.46-7.40(m，1H)，7.18-7.11(m，2H)，7.00-6.87(m，4H)，6.65(d，J＝8.0Hz，2H)，3.71(s，2H)，2.27(s，3H).¹³C NMR(CDCl₃，100MHz，ppm)169.3，162.2(d，J＝245.0Hz)，140.2，135.5，135.2，131.6(d，J＝7.7Hz)，131.2，131.1(d，J＝3.1Hz)，129.7(d，J＝23.9Hz)，129.6，128.4，127.7，125.8，125.7，125.2，119.2，116.1，115.9，113.5，44.5，20.8.HRMS calcd.forC₂₅H₂₁FNoS⁺[M+H]⁺402.1322，found 402.1328.

it should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are intended to be within the scope of the invention.

Claims

1. A method for synthesizing 1-thiophenyl-N-acetyl-2-naphthylamine and its derivant is characterized in that 2-naphthylamine compound, thioester compound, iron-containing reagent and iodine-containing reagent are heated and stirred to react under the reaction condition of organic solvent;

the iodine-containing reagent is selected from one or more of elementary iodine, potassium iodide, amine iodide, tetrabutylamine iodide, iodosuccinimide, iodine chloride, iodobenzene diacetic acid, iodine bromide, hydrogen iodide, 2-iodosylbenzoic acid, zinc iodide and cuprous iodide;

the organic solvent is selected from one or more of acetonitrile, tetrahydrofuran, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, 1, 4-dioxane, toluene, 1, 2-dichloroethane, 1, 2, 2-tetrachloroethane, chlorobenzene, o-xylene, p-xylene, benzyl alcohol, nitrobenzene, pyridine and quinoline; the structural formula of the 2-naphthylamine is as follows:

the thioester compound has the following general formula:

formula III

The general formula of the 1-thiophenyl-N-acetyl-2-naphthylamine and the derivatives thereof is shown as formula I:

wherein R in formula III and formula I₁Selected from hydrogen atom, alkyl, alkoxy, halogen and aromatic radical; r₂Selected from straight chain, branched chain alkyl, cyclic alkyl, substituted or non-substituted aryl and alkenyl.

2. The method according to claim 1, wherein the molar ratio of the 2-naphthylamine compound to the thioester compound is 1: 1.0-5.0, and the reaction temperature is 80-140 ℃.

3. The method according to claim 1 or 2, wherein the thioester compound is selected from the group consisting of S-phenylthioacetate, S- (4-methylphenyl) thioacetate, S- (4-bromophenyl) thioacetate, S- (4-chlorophenyl) thioacetate, S- (4-fluorophenyl) thioacetate, S- (4-methoxyphenyl) thioacetate, S- (3-methylphenyl) thioacetate, S- (3-bromophenyl) thioacetate, S- (3-chlorophenyl) thioacetate, S- (3-fluorophenyl) thioacetate, S- (2-methylphenyl), S- (2-bromophenyl) thioacetate, S- (4-chlorophenyl) thioacetate, S- (3-fluorophenyl) thioacetate, S- (2-methylphenyl) thioacetate, S- (2-bromophenyl) thioacetate, and S- (4-chlorophenyl) thioa, S- (2-chlorophenyl) thioacetate, S- (2-fluorophenyl) thioacetate, S- (2-methoxyphenyl) thioacetate, S- (2-ethylphenyl) thioacetate, S- (2, 3-dichlorophenyl) thioacetate, S- (2-naphthyl) thioacetate, S- (4-methylphenyl) thiopropionate, S- (4-methylphenyl) thiohexanoate, S- (4-methylphenyl) thioheptanoate, S- (4-methylphenyl) thiooctanoate, S- (4-methylphenyl) thiononanoate, S- (4-methylphenyl) thiodecanoate, S- (4-methylphenyl) thiobenzoate, S- (2-fluorophenyl) thioacetate, S- (2-methoxyphenyl) thioacetate, S- (4-methylphenyl) thiohexanoate, S- (4-methylphenyl) thioheptanoate, S- (4-methylphenyl) thiooctanoate, S- (4-methylphenyl) thiononanoate, S- (, S- (4-methylphenyl) thiophenylacetate, S- (4-methylphenyl) thiophenylpropionate, S- (4-methylphenyl) thio-benzene (4-fluoro) propionate, S- (4-methylphenyl) thio-cyclopentyl propionate, S- (4-methylphenyl) thio-butenoate, S- (4-methylphenyl) thio-cyclopropyl formate, S- (4-methylphenyl) thio-tert-butyrate, S- (4-methylphenyl) thio-isobutyrate, S- (4-methylphenyl) thio-isovalerate, S- (4-methylphenyl) thio-pivalate.