CN109796383A - 1- sulfur phenenyl-N- acetyl -2- naphthylamines and its derivative and synthetic method - Google Patents
1- sulfur phenenyl-N- acetyl -2- naphthylamines and its derivative and synthetic method Download PDFInfo
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Abstract
The invention mainly relates to a kind of 1- sulfur phenenyl-N- acetyl -2- naphthylamines and its derivative and synthetic methods, cheap and easy to get containing under ferron, iodine class compound collective effect, carbon-sulfur bond fracture and the 2- naphthylamines of sulfur ester occur Bifunctionalized recombination and generate new C-N/C-S key, carry out the method that one pot of multi-component reaction generates 1- sulfur phenenyl-N- acetyl -2- naphthylamines and its derivative.Method of the invention overcomes the synthetic method of existing 1- sulfur phenenyl-N- acetyl -2- naphthylamine compounds there are synthesis step complexity, needs the shortcomings that taking multi-step synthetic process that could complete；Method of the invention maintains Atom economy to the utmost；Excellent with molecular structure stabilized, chemical property, molecule stripping and slicing and compound segment include bioactivity abundant and pharmacological activity content；Also have many advantages, such as reaction system is simple, reaction condition is mild, consersion unit is less, experimental implementation is easy, materials are from a wealth of sources, user and application be easy to extend, product utilization value it is higher.
Description
Technical field
The present invention relates to 1- sulfur phenenyl-N- acetyl -2- naphthylamines and its derivative and synthetic methods, belong to organic synthesis neck
Domain.
Background technique
1- sulfur phenenyl-N- acetyl -2- naphthylamines and its derivative are a kind of very important organic compound, this kind of compound
It is important with good bioactivity and pharmacological activity, high application value is suffered from pesticide and medicine and other fields.
Summary of the invention
Therefore, the purpose of the present invention is to provide a new class of compound, that is, 1- sulfur phenenyl-N- acetyl -2- naphthylamines and its derivatives
Object.
It is yet another object of the invention to provide the synthetic method of a kind of 1- sulfur phenenyl-N- acetyl -2- naphthylamines and its derivative,
Has the advantages that simple process.
To which of the invention a kind of 1- sulfur phenenyl-N- acetyl -2- naphthylamines and its derivative, its general formula is Formulas I:
Wherein
R1Selected from hydrogen atom, alkyl, alkoxy, halogen, aromatic radical；
R2Selected from straight chain, branched alkyl, cyclic alkyl, substituted or non-substituted aryl, alkylene.
The method of 1- sulfur phenenyl-N- acetyl -2- naphthylamines and its derivative of the invention, by 2- naphthylamine compound, thioesters class
Compound is stirred to react to obtain containing ferron and containing iodine reagent is heated under organic solvent reaction condition.
Preferably, method of the invention, it is described to be selected from iodine, potassium iodide, iodate amine, tetrabutyl iodate containing iodine reagent
Amine, N-iodosuccinimide, lodine chloride, iodobenzene diacetate, Iodide Bromide, hydrogen iodide, 2- iodosobenzoic acid, zinc iodide, iodate
It is one of cuprous or several.
Preferably, method of the invention, it is described to be selected from ferrous sulfate, frerrous chloride, iron powder, ferric sulfate, fluorine containing ferron
Change one of iron, trifluoromethanesulfonic acid iron, di-iron trioxide, iron chloride, ferroso-ferric oxide, ferric acetyl acetonade, ferric nitrate or number
Kind.
Preferably, method of the invention, the organic solvent are selected from acetonitrile, tetrahydrofuran, n,N-dimethylacetamide, N,
Dinethylformamide, dimethyl sulfoxide, Isosorbide-5-Nitrae-dioxane, toluene, 1,2- dichloroethanes, 1,1,2,2- tetrachloroethanes, chlorine
One of benzene, ortho-xylene, paraxylene, benzyl alcohol, nitrobenzene, pyridine, quinoline are a variety of.
Preferably, the molar ratio of method of the invention, the 2- naphthylamine compound and sulfur ester is 1: 1.0-
5.0, reaction temperature is 80 DEG C -140 DEG C.
Preferably, the structural formula of method of the invention, the 2- naphthylamines is as follows:
Formula II
Preferably, the general formula of method of the invention, the sulfur ester is as follows:
Formula III
Wherein
R1Selected from hydrogen atom, alkyl, alkoxy, halogen, aromatic radical；
R2Selected from straight chain, branched alkyl, cyclic alkyl, substituted or non-substituted aryl, alkylene.
Preferably, method of the invention, the sulfur ester select S- phenyl acetic acid esters, S- (4- aminomethyl phenyl)
Thiacetate, S- (4- bromophenyl) thiacetate, S- (4- chlorphenyl) thiacetate, S- (4- fluorophenyl) thioacetic acid
Ester, S- (4- methoxyphenyl) thiacetate, S- (3- methoxyphenyl) thiacetate, S- (3- aminomethyl phenyl) thio second
Acid esters, S- (3- methoxyphenyl) thiacetate, S- (3- bromophenyl) thiacetate, S- (3- chlorphenyl) thioacetic acid
Ester, S- (3- fluorophenyl) thiacetate, S- (2- aminomethyl phenyl), S- (2- bromophenyl) thiacetate, S- (2- chlorphenyl)
Thiacetate, S- (2- fluorophenyl) thiacetate, S- (2- methoxyphenyl) thiacetate, S- (2- ethylphenyl) sulphur
For acetic acid esters, S- (2,3- dichlorophenyl) thiacetate, S- (2- naphthalene) thiacetate, S- (4- aminomethyl phenyl) thio third
Acid esters, S- (4- aminomethyl phenyl) Thiobutyric acid ester, the thio valerate of S- (4- aminomethyl phenyl), S- (4- aminomethyl phenyl) thio caproic acid
Ester, S- (4- aminomethyl phenyl) thiaheptanoic acid ester, S- (4- aminomethyl phenyl) thio-octanoic acid ester, S- (4- aminomethyl phenyl) thio n-nonanoic acid
Ester, the thio decylate of S- (4- aminomethyl phenyl), S- (4- aminomethyl phenyl) Thiobenzoate, S- (4- aminomethyl phenyl) thio phenyl second
Acid esters, the thio Phenpropionate of S- (4- aminomethyl phenyl), S- (4- aminomethyl phenyl) thio-benzene (4- fluorine) propionic ester, S- (4- methylbenzene
Base) thio cyclopentanepropanoiacid acid ester, the thio butenoate of S- (4- aminomethyl phenyl), S- (4- aminomethyl phenyl) thiacyclopropyl's formic acid
Ester, the thio tertiary butyrate of S- (4- aminomethyl phenyl), S- (4- aminomethyl phenyl) thio isobutyrate ester, S- (4- aminomethyl phenyl) are thio different
Valerate, S- (4- aminomethyl phenyl) thio pivalate.
1- sulfur phenenyl-N- acetyl -2- naphthylamines and its derivative is also claimed in the present invention, in machine synthetic intermediate, sterilization
Application in terms of agent, pharmaceutical synthesis.
Technical solution of the present invention has the advantages that
1- sulfur phenenyl-N- acetyl -2- naphthylamines of the invention and its derivative and synthetic method are tried in iron content cheap and easy to get
Under agent, iodine class compound collective effect, carbon-sulfur bond fracture and the 2- naphthylamines of sulfur ester occur Bifunctionalized recombination and generate
New C-N/C-S key carries out the method that one pot of multi-component reaction generates 1- sulfur phenenyl-N- acetyl -2- naphthylamines and its derivative.This
The method of invention overcomes the synthetic methods of existing 1- sulfur phenenyl-N- acetyl -2- naphthylamine compounds there are synthesis step complexity,
Need the shortcomings that taking multi-step synthetic process that could complete；Method of the invention maintains Atom economy to the utmost；Tool
There are molecular structure stabilized, chemical property excellent, molecule stripping and slicing and compound segment include bioactivity abundant and pharmacological activity
Content；Also have reaction system is simple, reaction condition is mild, consersion unit is less, experimental implementation is easy, materials are from a wealth of sources,
The advantages that user and application are easy to extend, product utilization value is higher.
Detailed description of the invention
In order to prove product of the invention, the present invention provides the nucleus magnetic hydrogen spectrum figure and nuclear-magnetism carbon spectrogram of section Example.
The nucleus magnetic hydrogen spectrum figure of 1 product of Fig. 1 a embodiment.
The nuclear-magnetism carbon spectrogram of 1 product of Fig. 1 b embodiment.
The nucleus magnetic hydrogen spectrum figure of 2 product of Fig. 2 a embodiment.
The nuclear-magnetism carbon spectrogram of 2 product of Fig. 2 b embodiment.
The nucleus magnetic hydrogen spectrum figure of 3 product of Fig. 3 a embodiment.
The nuclear-magnetism carbon spectrogram of 3 product of Fig. 3 b embodiment.
The nucleus magnetic hydrogen spectrum figure of 4 product of Fig. 4 a embodiment.
The nuclear-magnetism carbon spectrogram of 4 product of Fig. 4 b embodiment.
The nucleus magnetic hydrogen spectrum figure of 5 product of Fig. 5 a embodiment.
The nuclear-magnetism carbon spectrogram of 5 product of Fig. 5 b embodiment.
The nucleus magnetic hydrogen spectrum figure of 6 product of Fig. 6 a embodiment.
The nuclear-magnetism carbon spectrogram of 6 product of Fig. 6 b embodiment.
The nucleus magnetic hydrogen spectrum figure of 7 product of Fig. 7 a embodiment.
The nuclear-magnetism carbon spectrogram of 7 product of Fig. 7 b embodiment.
The nucleus magnetic hydrogen spectrum figure of 8 product of Fig. 8 a embodiment.
The nuclear-magnetism carbon spectrogram of 8 product of Fig. 8 b embodiment.
The nucleus magnetic hydrogen spectrum figure of 19 product of Fig. 9 a embodiment.
The nuclear-magnetism carbon spectrogram of 19 product of Fig. 9 b embodiment.
The nucleus magnetic hydrogen spectrum figure of 20 product of Figure 10 a embodiment.
The nuclear-magnetism carbon spectrogram of 20 product of Figure 10 b embodiment.
Figure 11 is the reaction system general formula of 1- sulfur phenenyl-N- acetyl -2- naphthylamines and its derivative synthesizing process of the invention.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with attached drawing, it is clear that described implementation
Example is a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill
Personnel's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
As long as technical characteristic involved in invention described below different embodiments does not constitute punching each other
It is prominent to be combined with each other.
In conjunction with the synthetic route of the compounds of this invention, the synthetic method of 1- sulfur phenenyl-N- acetyl -2- naphthylamines and its derivative
It is cheap and easy to get containing ferron, iodine class compound, difunctionality occurs for carbon-sulfur bond fracture and the 2- naphthylamines of sulfur ester
Change recombination and generates new C-N/C-S key, one pot of multi-component generation 1- sulfur phenenyl-N- acetyl -2- naphthylamines and its derivative.It gram
The synthetic method of existing 1- sulfur phenenyl-N- acetyl -2- naphthylamine compounds has been taken there are synthesis step complexity, has needed to take multistep
Synthesis technology could be completed；It maintains Atom economy to the utmost；It has molecular structure stabilized, chemically of fine quality
Good, molecule stripping and slicing and compound segment include bioactivity abundant and pharmacological activity content；It also have reaction system it is simple,
Reaction condition is mild, consersion unit is less, experimental implementation is easy, materials are from a wealth of sources, user and application are easy to extension, product benefit
Be worth it is higher, market business prospect is expected the features such as.
1- sulfur phenenyl-N- acetyl -2- naphthylamines and its derivative, its general formula is Formulas I:
R1Selected from hydrogen atom, alkyl, alkoxy, halogen, aromatic radical；
R2Selected from straight chain, branched alkyl, cyclic alkyl, substituted or non-substituted aryl, alkylene.
The present invention also provides a kind of methods of 1- sulfur phenenyl-N- acetyl -2- naphthylamines and its derivative, by 2- naphthylamine compound
With sulfur ester is heated under reaction condition under organic solvent stirs to get.
Preferably, method of the invention, it is described to be selected from iodine, potassium iodide, iodate amine, tetrabutyl iodate containing iodine reagent
Amine, N-iodosuccinimide, lodine chloride, iodobenzene diacetate, Iodide Bromide, hydrogen iodide, 2- iodosobenzoic acid, zinc iodide, iodate
It is one of cuprous or several.
Preferably, method of the invention, it is described to be selected from ferrous sulfate, frerrous chloride, iron powder, ferric sulfate, fluorine containing ferron
Change one of iron, trifluoromethanesulfonic acid iron, di-iron trioxide, iron chloride, ferroso-ferric oxide, ferric acetyl acetonade, ferric nitrate or number
Kind.
Preferably, method of the invention, the solvent are selected from acetonitrile, tetrahydrofuran, n,N-dimethylacetamide, N, N- bis-
Methylformamide, dimethyl sulfoxide, Isosorbide-5-Nitrae-dioxane, toluene, 1,2- dichloroethanes, 1,1,2,2- tetrachloroethanes, chlorobenzene, neighbour
One of dimethylbenzene, paraxylene, benzyl alcohol, nitrobenzene, pyridine, quinoline are a variety of.
Preferably, the molar ratio of method of the invention, the 2- naphthylamine compound and thioesters is 1: 1.0-5.0 reaction temperature
It is 80 DEG C -140 DEG C.
Described its structural formula of 2- naphthylamines is as follows:
The general formula of the sulfur ester is formula III:
Wherein
R1Selected from hydrogen atom, alkyl, alkoxy, halogen, aromatic radical；
R2Selected from straight chain, branched alkyl, cyclic alkyl, substituted or non-substituted aryl, alkylene.
Preferably, method of the invention, the sulfur ester are selected from S- phenyl acetic acid esters, S- (4- methylbenzene
Base) thiacetate, S- (4- bromophenyl) thiacetate, S- (4- chlorphenyl) thiacetate, S- (4- fluorophenyl) be thio
Acetic acid esters, S- (4- methoxyphenyl) thiacetate, S- (3- methoxyphenyl) thiacetate, S- (3- aminomethyl phenyl) sulphur
For acetic acid esters, S- (3- methoxyphenyl) thiacetate, S- (3- bromophenyl) thiacetate, S- (3- chlorphenyl) thio second
Acid esters, S- (3- fluorophenyl) thiacetate, S- (2- aminomethyl phenyl), S- (2- bromophenyl) thiacetate, S- (2- chlorobenzene
Base) thiacetate, S- (2- fluorophenyl) thiacetate, S- (2- methoxyphenyl) thiacetate, S- (2- ethylo benzene
Base) thiacetate, S- (2,3- dichlorophenyl) thiacetate, S- (2- naphthalene) thiacetate, S- (4- aminomethyl phenyl)
Thiopropionate, S- (4- aminomethyl phenyl) Thiobutyric acid ester, the thio valerate of S- (4- aminomethyl phenyl), S- (4- aminomethyl phenyl) sulphur
It is thio for capronate, S- (4- aminomethyl phenyl) thiaheptanoic acid ester, S- (4- aminomethyl phenyl) thio-octanoic acid ester, S- (4- aminomethyl phenyl)
Pelargonate, the thio decylate of S- (4- aminomethyl phenyl), S- (4- aminomethyl phenyl) Thiobenzoate, S- (4- aminomethyl phenyl) are thio
Phenylacetate, the thio Phenpropionate of S- (4- aminomethyl phenyl), S- (4- aminomethyl phenyl) thio-benzene (4- fluorine) propionic ester, S- (4- first
Base phenyl) thio cyclopentanepropanoiacid acid ester, the thio butenoate of S- (4- aminomethyl phenyl), S- (4- aminomethyl phenyl) thiacyclopropyl's first
Acid esters, the thio tertiary butyrate of S- (4- aminomethyl phenyl), S- (4- aminomethyl phenyl) thio isobutyrate ester, S- (4- aminomethyl phenyl) are thio
Isovalerate, S- (4- aminomethyl phenyl) thio pivalate.
The reaction system that 1- sulfur phenenyl-N- acetyl -2- naphthylamines and its derivative synthesizing process are made of Formulas I, II, III is led to
Formula, such as:
The following steps are included:
(1) 2- naphthylamines, thioesters, iron, iodine, organic solvent are added in the reaction vessel；
(2) it after being sufficiently mixed reactant, is heated；
(3) it is purified to obtain product after reacting；
It is sub- that organic solvent is selected from acetonitrile, tetrahydrofuran, n,N-dimethylacetamide, n,N-Dimethylformamide, dimethyl
Sulfone, Isosorbide-5-Nitrae-dioxane, toluene, 1,2- dichloroethanes, 1,1,2,2- tetrachloroethanes, chlorobenzene, ortho-xylene, paraxylene, benzene
One of methanol, nitrobenzene, pyridine, quinoline are a variety of.
Preferably chlorobenzene；
In order to reach better synthetic effect, the preferably molar ratio of 2- naphthylamine compound and thioesters is 1: 2,
It is described to be selected from ferrous sulfate, frerrous chloride, iron powder, ferric sulfate, ferric flouride, trifluoromethanesulfonic acid iron, three containing ferron
Aoxidize one of two iron, iron chloride, ferroso-ferric oxide, ferric acetyl acetonade, ferric nitrate or several；
Preferably di-iron trioxide；
Containing iodine reagent be selected from iodine, potassium iodide, iodate amine, tetrabutyl iodate amine, N-iodosuccinimide, lodine chloride,
One of iodobenzene diacetate, Iodide Bromide, hydrogen iodide, 2- iodosobenzoic acid, zinc iodide, cupric iodide are several
Preferably N-iodosuccinimide；
The temperature T of reaction is 80 DEG C -140 DEG C；
Preferably 130 DEG C.
From the synthetic reaction plant process of aforementioned present invention compound it can be concluded that, 1- sulfur phenenyl-N- acetyl -2- naphthylamines
And its derivative, under containing ferron, iodine class compound collective effect, carbon-sulfur bond fracture and the 2- naphthylamines of sulfur ester are sent out
Raw Bifunctionalized recombination generates new C-N/C-S key.
For above-mentioned formula III compound as a kind of important molecule stripping and slicing, its molecular structure stabilized, chemical property are excellent,
Itself has certain physiological activity, can also further be synthesized by the conversion to functional group and much contain 1- sulfur phenenyl-N- second
The compound segment of acyl -2- naphthylamines, contains very strong physiological activity and pharmacological activity；In short, the compounds of this invention has reaction
Raw material is cheap and easy to get and does not need to be pre-processed, and reacts the features such as directly synthesizing for one pot；It solves existing using multistep
The problems such as synthetic method bring higher cost；Its reaction condition is mild, and reaction required temperature is significantly less than previous multistep synthesis
Reaction temperature；A series of 1- sulfur phenenyl-N- acetyl -2- naphthylamine compounds of synthesis have quite high potential application valence
Value.
Table: reactant, reaction condition and the yield of embodiment 1-39
The nuclear-magnetism and mass spectrometric data of the product of embodiment be
The nuclear-magnetism and mass spectrometric data of 1 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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): δ 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-magnetism and mass spectrometric data of 2 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ 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-magnetism and mass spectrometric data of 3 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) δ 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-magnetism and mass spectrometric data of 4 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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)13C
NMR(CDCl3, 100MHz, ppm) and δ 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-magnetism and mass spectrometric data of 5 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ
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.HRMS
Calcd.for:C18H15FNOS+[M+H]+312.0853 found 312.0857.
The nuclear-magnetism and mass spectrometric data of 6 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ
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, found
328.0557.
The nuclear-magnetism and mass spectrometric data of 7 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) δ 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-magnetism and mass spectrometric data of 8 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ 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-magnetism and mass spectrometric data of 9 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ 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-magnetism and mass spectrometric data of 10 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ 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-magnetism and mass spectrometric data of 11 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ 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, found
312.0856.
The nuclear-magnetism and mass spectrometric data of 12 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ 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.HRMS
Calcd.for:C18H15ClNOS+[M+H]+328.0557 found 328.0557.
The nuclear-magnetism and mass spectrometric data of 13 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ 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-magnetism and mass spectrometric data of 14 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ 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-magnetism and mass spectrometric data of 15 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ 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-magnetism and mass spectrometric data of 16 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ
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, found
312.0856.
The nuclear-magnetism and mass spectrometric data of 17 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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 δ, 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-magnetism and mass spectrometric data of 18 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ 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-magnetism and mass spectrometric data of 19 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ 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-magnetism and mass spectrometric data of 20 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ 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-magnetism and mass spectrometric data of 21 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ 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-magnetism and mass spectrometric data of 22 product of embodiment are as follows:
1H NMR(CDCl3, 100MHz, ppm) and δ 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) and δ 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, found
336.1420.
The nuclear-magnetism and mass spectrometric data of 23 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ
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-magnetism and mass spectrometric data of 24 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ 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-magnetism and mass spectrometric data of 25 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) δ 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.HRMS
Calcd.for:C24H28NOS+[M+H]+378.1886 found 378.1891.
The nuclear-magnetism and mass spectrometric data of 26 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ 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-magnetism and mass spectrometric data of 27 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ 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-magnetism and mass spectrometric data of 28 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ 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-magnetism and mass spectrometric data of 29 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ 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.HRMS
Calcd.for:C21H22NOS+[M+H]+336.1417 found 336.1420.
The nuclear-magnetism and mass spectrometric data of 30 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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 δ, 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, found
350.1578.
The nuclear-magnetism and mass spectrometric data of 31 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ 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.HRMS
Calcd.for:C21H20NOS+[M+H]+334.1260 found 334.1263.
The nuclear-magnetism and mass spectrometric data of 32 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ 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-magnetism and mass spectrometric data of 33 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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 δ, 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-magnetism and mass spectrometric data of 34 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ 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-magnetism and mass spectrometric data of 35 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ 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-magnetism and mass spectrometric data of 36 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ 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-magnetism and mass spectrometric data of 37 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ 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, found
398.1573.
The nuclear-magnetism and mass spectrometric data of 38 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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 δ, 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-magnetism and mass spectrometric data of 39 product of embodiment are as follows:
1H NMR(CDCl3, 400MHz, ppm) and δ 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) and δ 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.for
C25H21FNoS+[M+H]+402.1322 found 402.1328.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes within still in the protection scope of the invention.
Claims (9)
1. a kind of 1- sulfur phenenyl-N- acetyl -2- naphthylamines and its derivative, its general formula is Formulas I:
Wherein
R1Selected from hydrogen atom, alkyl, alkoxy, halogen, aromatic radical；
R2Selected from straight chain, branched alkyl, cyclic alkyl, substituted or non-substituted aryl, alkylene.
2. a kind of method for synthesizing 1- sulfur phenenyl-N- acetyl -2- naphthylamines and its derivative described in claim 1, feature exist
In being stirred by 2- naphthylamine compound, sulfur ester, containing ferron and containing iodine reagent is heated under organic solvent reaction condition
Reaction is mixed to obtain.
3. according to the method described in claim 2, it is characterized in that, described be selected from iodine, potassium iodide, iodate containing iodine reagent
Amine, tetrabutyl iodate amine, N-iodosuccinimide, lodine chloride, iodobenzene diacetate, Iodide Bromide, hydrogen iodide, 2- iodoxy benzene first
One of acid, zinc iodide, cuprous iodide are several.
4. according to the method described in claim 2, it is characterized in that, described be selected from ferrous sulfate, frerrous chloride, iron containing ferron
Powder, ferric sulfate, ferric flouride, trifluoromethanesulfonic acid iron, di-iron trioxide, iron chloride, ferroso-ferric oxide, ferric acetyl acetonade, ferric nitrate
One of or it is several.
5. according to the method described in claim 2, it is characterized in that, the organic solvent is selected from acetonitrile, tetrahydrofuran, N, N- bis-
Methylacetamide, n,N-Dimethylformamide, dimethyl sulfoxide, Isosorbide-5-Nitrae-dioxane, toluene, 1,2- dichloroethanes, 1,1,2,
One of 2- tetrachloroethanes, chlorobenzene, ortho-xylene, paraxylene, benzyl alcohol, nitrobenzene, pyridine, quinoline are a variety of.
6. according to method described in Claims 2 or 3 or 4 or 5, which is characterized in that the 2- naphthylamine compound and thioesters class
The molar ratio for closing object is 1: 1.0-5.0, and reaction temperature is 80 DEG C -140 DEG C.
7. according to the method described in claim 2, it is characterized in that, the structural formula of the 2- naphthylamines is as follows:
Formula II
8. according to the method described in claim 2, it is characterized in that, the general formula of the sulfur ester is as follows:
Formula III
Wherein
R1Selected from hydrogen atom, alkyl, alkoxy, halogen, aromatic radical；
R2Selected from straight chain, branched alkyl, cyclic alkyl, substituted or non-substituted aryl, alkylene.
9. according to the method described in claim 8, it is characterized in that, the sulfur ester is selected from S- phenyl acetic acid
Ester, S- (4- aminomethyl phenyl) thiacetate, S- (4- bromophenyl) thiacetate, S- (4- chlorphenyl) thiacetate, S-
(4- fluorophenyl) thiacetate, S- (4- methoxyphenyl) thiacetate, S- (3- methoxyphenyl) thiacetate, S-
(3- aminomethyl phenyl) thiacetate, S- (3- methoxyphenyl) thiacetate, S- (3- bromophenyl) thiacetate, S-
(3- chlorphenyl) thiacetate, S- (3- fluorophenyl) thiacetate, S- (2- aminomethyl phenyl), S- (2- bromophenyl) thio second
Acid esters, S- (2- chlorphenyl) thiacetate, S- (2- fluorophenyl) thiacetate, S- (2- methoxyphenyl) thioacetic acid
Ester, S- (2- ethylphenyl) thiacetate, S- (2,3- dichlorophenyl) thiacetate, S- (2- naphthalene) thiacetate,
S- (4- aminomethyl phenyl) thiopropionate, S- (4- aminomethyl phenyl) Thiobutyric acid ester, the thio valerate of S- (4- aminomethyl phenyl), S-
(4- aminomethyl phenyl) thio capronate, S- (4- aminomethyl phenyl) thiaheptanoic acid ester, S- (4- aminomethyl phenyl) thio-octanoic acid ester, S-
(4- aminomethyl phenyl) thio pelargonate, the thio decylate of S- (4- aminomethyl phenyl), S- (4- aminomethyl phenyl) Thiobenzoate, S-
(4- aminomethyl phenyl) thio phenylacetate, the thio Phenpropionate of S- (4- aminomethyl phenyl), S- (4- aminomethyl phenyl) be thio-benzene (4-
Fluorine) propionic ester, the thio cyclopentanepropanoiacid acid ester of S- (4- aminomethyl phenyl), the thio butenoate of S- (4- aminomethyl phenyl), S- (4- methyl
Phenyl) thiacyclopropyl's formic acid esters, the thio tertiary butyrate of S- (4- aminomethyl phenyl), S- (4- aminomethyl phenyl) thio isobutyrate ester,
The thio isovalerate of S- (4- aminomethyl phenyl), S- (4- aminomethyl phenyl) thio pivalate.
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| CN108440417A (en) * | 2018-04-16 | 2018-08-24 | 湘潭大学 | 1- methyl thio phenyls benzimidazole and its derivative synthesizing process |
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| CN108440417A (en) * | 2018-04-16 | 2018-08-24 | 湘潭大学 | 1- methyl thio phenyls benzimidazole and its derivative synthesizing process |
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