CN109438384B - Polysubstituted 2, 4-diaryl thiazole and derivative and synthetic method thereof - Google Patents

Polysubstituted 2, 4-diaryl thiazole and derivative and synthetic method thereof Download PDF

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CN109438384B
CN109438384B CN201811449501.2A CN201811449501A CN109438384B CN 109438384 B CN109438384 B CN 109438384B CN 201811449501 A CN201811449501 A CN 201811449501A CN 109438384 B CN109438384 B CN 109438384B
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aromatic
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thiazole
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CN109438384A (en
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邓国军
蒋晶晶
黄华文
肖福红
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Xiangtan University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D277/24—Radicals substituted by oxygen atoms

Abstract

The invention relates to a method for synthesizing polysubstituted 2, 4-diaryl thiazole and derivatives thereof. The invention develops the technical scheme of converting aromatic ketone compounds, aromatic aldehyde compounds, ammonium salt and sulfur powder into 2, 4-diaryl thiazole and derivatives thereof for the first time, and prepares thiazole derivatives with stable molecular structure and excellent chemical properties; the technical scheme for converting the aromatic ketone compound, the aromatic aldehyde compound, the ammonium salt and the sulfur powder into the 2, 4-diaryl thiazole and the derivative has the advantages that reaction raw materials are cheap and easy to obtain, a metal catalyst is not needed, and only equivalent amount of water is needed to be added, so that the environmental pollution is reduced, the raw materials are saved, and the reaction cost is reduced; the whole reaction system is simple, the reaction condition is mild, the experimental operation is simple and safe, and a method for constructing the thiazole derivative through one-step reaction under the condition without metal catalysis is developed.

Description

Polysubstituted 2, 4-diaryl thiazole and derivative and synthetic method thereof
Technical Field
The invention relates to a method for synthesizing polysubstituted 2, 4-diaryl thiazole and derivatives thereof, belonging to the technical field of organic compound synthesis.
Background
The 2, 4-diaryl thiazole and the derivatives thereof are important aromatic heterocyclic compounds, have wide biological activity and have wide application prospect in the fields of chemistry, medicine, biological coloring agent, material science and the like. The existing method for synthesizing the compounds has the defects of complex synthesis steps, adoption of organic amine compounds as ammonium sources, addition of metal catalysts for catalysis and the like.
Disclosure of Invention
The invention provides polysubstituted 2, 4-diaryl thiazole and derivatives thereof with stable molecular structure and excellent chemical properties for the first time.
The invention also provides a method for synthesizing the polysubstituted 2, 4-diaryl thiazole and the derivatives thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: the invention provides polysubstituted 2, 4-diaryl thiazole and derivatives, which have a general formula I:
Figure BSA0000174925940000011
wherein
R1Selected from:
hydrogen atom, linear saturated or unsaturated alkyl of C1-C8, halogen, methane oxygen, benzene aryl and condensed ring; alkyl, alkoxy, fused rings with one or more halogen substituents;
R2selected from:
hydrogen atom, linear saturated or unsaturated alkyl of C1-C8, halogen, alkoxy, aromatic group and condensed ring; alkyl, alkoxy, fused rings with one or more halogen substituents;
the invention also provides a method for synthesizing the polysubstituted 2, 4-diaryl thiazole and the derivative thereof, which comprises the following steps:
adding aromatic ketone compound, aromatic aldehyde compound, ammonium salt, sulfur powder, water and organic solvent;
fully mixing the reactants, and heating for reaction;
purifying to obtain the product.
Preferably, in the synthesis method of the present invention, the aromatic ketone compound is selected from C8-C16 aromatic ketones, and the general formula thereof is formula II:
Figure BSA0000174925940000012
Figure BSA0000174925940000021
wherein
R1Selected from:
hydrogen atom, linear saturated or unsaturated alkyl of C1-C8, halogen, methane oxygen, benzene aryl and condensed ring; alkyl, alkoxy, fused rings with one or more halogen substituents;
preferably, in the synthesis method of the present invention, the aromatic ketone compound is selected from: acetophenone, 4-methylacetophenone, 4-fluoroacetophenone, 4-bromoacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-phenylacetylacetophenone, 4-phenylacetophenone, 4-chloroacetophenone, 3-chloroacetophenone, 4-methoxyacetophenone, 3-trifluoromethylacetophenone, 4-trifluoromethylacetophenone, 2-naphthylacetophenone.
Preferably, the synthesis method of the present invention, the aromatic aldehyde compound has a general formula of formula III:
Figure BSA0000174925940000022
wherein
R2Selected from:
hydrogen atom, linear saturated or unsaturated alkyl of C1-C8, halogen, alkoxy, aromatic group and condensed ring; alkyl, alkoxy, fused rings with one or more halogen substituents;
preferably, in the synthesis method of the present invention, the aromatic aldehyde compound is selected from: benzaldehyde, 4-methylbenzaldehyde, 4-chlorobenzaldehyde, 3-chlorobenzaldehyde, 2-chlorobenzaldehyde, 4-methoxybenzaldehyde, 4-benzaldehyde, 4-trifluoromethylbenzaldehyde, 3, 4-dimethylbenzaldehyde, 4-fluorobenzaldehyde, 4-bromobenzaldehyde, 2-methylbenzaldehyde, 2-bromobenzaldehyde, 3-methylbenzaldehyde, 3-bromobenzaldehyde, 2-naphthaldehyde.
Preferably, in the synthesis method of the present invention, the ammonium salt is selected from: one or more of ammonium persulfate, ammonium chloride, ammonium iodide and ammonium hexafluorophosphate.
Preferably, the synthesis method of the present invention: the mol ratio of the aromatic ketone compound to the aromatic aldehyde compound to the ammonium salt to the sulfur powder to the water is 1.0: 3.0-4.0: 2.0-3.0: 2.0-4.0: 8.0-11.0; meanwhile, the reaction temperature is 130-150 ℃; the reaction time is 24-36 h; the organic solvent is: one or more of pyridine, quinoline and N, N-dimethylformamide.
Compared with the prior art, the invention has the following beneficial effects:
(I) according to the invention, the aromatic ketone compound, the aromatic aldehyde compound, the ammonium salt and the sulfur powder are firstly converted into the 2, 4-diaryl thiazole and the derivative, so that the product with stable molecular structure and excellent chemical property is prepared; (II) the technical scheme of converting aromatic ketone compounds, aromatic aldehyde compounds, ammonium salts and sulfur powder into 2, 4-diaryl thiazole and derivatives thereof is that the aryl thiazole is synthesized by the combined action of directly using the ammonium salts as a nitrogen source and the sulfur powder as a sulfur source for the first time by a one-pot method, the reaction raw materials are cheap and easy to obtain, and the reaction operation is simple, convenient and safe; (III) the aromatic ketone compound, the aromatic aldehyde compound, the ammonium salt and the sulfur powder are converted into the 2, 4-diaryl thiazole and the derivative, metal or other catalysts are not needed in the reaction, and only green and easily obtained water is needed to be used as an additive, so that the environmental pollution is reduced, and the reaction cost is reduced; (IV) the technical scheme for converting the aromatic ketone compound, the aromatic aldehyde compound, the ammonium salt and the sulfur powder into the 2, 4-diaryl thiazole and the derivative thereof has the characteristics of simple reaction system, mild reaction condition, higher product utilization value and the like. The 2, 4-diaryl thiazole derivative and the synthesis method thereof can be widely applied to a plurality of fields of chemistry, medicine, biological coloring agent, material science and the like; research and development of 2, 4-diaryl thiazole compounds efficiently and selectively synthesized by a multi-component one-pot method.
Drawings
In order to demonstrate the products of the invention, the invention provides nuclear magnetic hydrogen and carbon spectra of some of the examples.
FIGS. 1a and 1b nuclear magnetic spectra of the product of example 1;
FIGS. 2a and 2b nuclear magnetic spectra of the product of example 4;
FIGS. 3a and 3b nuclear magnetic spectra of the product of example 6;
FIGS. 4a and 4b nuclear magnetic spectra of the product of example 9;
FIGS. 5a and 5b nuclear magnetic spectra of the product of example 11;
FIGS. 6a and 6b nuclear magnetic spectra of the product of example 15;
FIGS. 7a and 7b nuclear magnetic spectra of the product of example 17;
FIGS. 8a and 8b nuclear magnetic spectra of the product of example 22;
FIGS. 9a and 9b nuclear magnetic spectra of the product of example 24;
FIGS. 10a and 10b nuclear magnetic spectra of the product of example 27;
wherein a is a hydrogen spectrum and b is a carbon spectrum.
Detailed Description
The present invention will now be described in further detail with reference to the accompanying drawings. These drawings are simplified schematic views illustrating only the basic structure of the present invention in a schematic manner, and thus show only the constitution related to the present invention.
The reaction equation is: "N" is an ammonium salt.
Figure BSA0000174925940000031
Examples 1 to 51
Step 1: adding aromatic ketone compounds (specific substances are shown in table 1), aromatic aldehyde compounds (specific substances are shown in table 1), ammonium salts (specific substances are shown in table 1), sulfur powder, water and organic solvents (specific substances are shown in table 1) into a reaction vessel;
step 2: uniformly heating (such as heating in an oil bath) the reaction vessel to the temperature described in table 1, and reacting the aromatic ketone compound, the aromatic aldehyde compound, the ammonium salt, the sulfur powder and the water in the solvent for the time described in table 1;
and step 3: purification step
Table 1: aromatic ketones, aromatic aldehydes, ammonium salts ("N"), solvents, reaction temperatures and reaction times in examples 1-29.
Figure BSA0000174925940000041
Figure BSA0000174925940000051
Wherein the molar ratio is the molar ratio of the aromatic ketone compound to the aromatic aldehyde compound to the ammonium salt to the sulfur powder to the water.
In the reaction of the above example, the aromatic ketone compound and the aromatic aldehyde compound, the ammonium salt and the sulfur powder act together to finally produce the target compound.
And (3) detecting the conversion rate of the substances in the reaction vessel after the step (3) and performing nuclear magnetic resonance, wherein the results of some examples are as follows:
the nuclear magnetic data of the product of example 1 are as follows:
1H NMR(400MHz，CDCl3)δ7.94(dd，J＝7.8，2.5Hz，2H)，7.75-7.67(m，2H)，7.48-7.30(m，8H)，7.25(t，J＝7.5Hz，3H)，4.30(s，2H).13C NMR(100MHz，CDCl3)δ165.2，152.5，140.0，134.9，133.6，133.0， 129.8，128.8，128.7，128.5，128.3，127.9，126.8，126.3，33.2.
the nuclear magnetic data of the product of example 2 are as follows:
1H NMR(400MHz，CDCl3)δ7.95(dd，J＝7.9，2.6Hz，2H)，7.61(d，J＝8.1Hz，2H)，7.46-7.37(m， 3H)，7.33(t，J＝7.2Hz，2H)，7.29-7.22(m，5H)，4.30(s，2H)，2.40(s，3H).13C NMR(100MHz，CDCl3)δ 164.9，159.4，152.3，140.1，133.8，131.8，130.0，129.7，128.8，128.7，128.3，127.6，126.7，126.3，113.9，55.3， 33.2.
the nuclear magnetic data of the product of example 3 are as follows:
1H NMR(400MHz，CDCl3)δ7.94(dd，J＝7.6，4.0Hz，2H)，7.71-7.65(m，2H)，7.43-7.37(m，3H)， 7.34(t，J＝7.3Hz，2H)，7.29-7.22(m，3H)，7.14(t，J＝8.7Hz，2H)，4.27(s，2H).13C NMR(100MHz， CDCl3)δ165.3，162.5(d，J＝246.0Hz)，151.5，139.8，133.5，132.8，131.0(d，J＝3.2Hz)，130.6，130.5， 129.9，128.8(d，J＝2.7Hz)，128.3，126.9，126.3，115.4(d，J＝21.4Hz)，33.2.
the nuclear magnetic data of the product of example 4 are as follows:
1H NMR(400MHz，CDCl3)δ7.92(dd，J＝7.6，4.0Hz，2H)，7.63-7.53(m，4H)，7.45-7.37(m，3H)， 7.33(t，J＝7.3Hz，2H)，7.29-7.20(m，3H)，4.26(s，2H).13C NMR(100MHz，CDCl3)δ165.4，151.2，139.7， 133.9，133.5，133.3，131.6，130.3，129.9，128.8，128.8，128.3，126.9，126.3，122.0，33.2.
the nuclear magnetic data of the product of example 5 are as follows:
1H NMR(400MHz，CDCl3)δ7.94(dd，J＝7.4，2.0Hz，2H)，7.56(s，1H)，7.47(d，J＝7.7Hz，1H)，7.42 -7.37(m，3H)，7.33(t，J＝7.2Hz，3H)，7.26(t，J＝5.6Hz，3H)，7.19(d，J＝7.6Hz，1H)，4.29(s，2H)，2.41 (s，3H).13C NMR(100MHz，CDCl3)δ165.1，152.7，140.2，138.1，134.9，133.8，133.0，129.7，129.6，128.8， 128.7，128.7，128.4，128.3，126.8，126.4，125.8，33.3，21.5.
the nuclear magnetic data of the product of example 6 are as follows:
1H NMR(400MHz，CDCl3)δ7.92(d，J＝5.5Hz，2H)，7.38(d，J＝5.3Hz，3H)，735-7.19(m，7H)， 7.14(d，J＝7.4Hz，2H)，4.02(s，2H)，2.28(s，3H).13C NMR(100MHz，CDCl3)δ165.0，152.9，140.0，137.8， 134.3，134.2，133.7，130.5，130.2，129.7，128.8，128.6，128.5，128.3，126.6，126.3，125.6，32.9，20.1.
the nuclear magnetic data of the product of example 7 are as follows:
1H NMR(400MHz，CDCl3)δ7.94(dd，J＝7.8，2.8Hz，2H)，7.73(d，J＝8.2Hz，2H)，7.61(d，J＝8.1 Hz，2H)，7.55(dd，J＝7.8，2.4Hz，2H)，7.43-7.38(m，3H)，7.38-7.32(m，5H)，7.30-7.24(m，3H)，4.32 (s，2H).13C NMR(100MHz，CDCl3)δ165.3，151.6，139.8，134.7，133.6，133.5，131.7，131.6，129.9，128.8， 128.8，128.6，128.3，128.3，126.9，126.3，123.2，122.7，90.2，89.3，33.3.
the nuclear magnetic data of the product of example 8 are as follows:
1H NMR(400MHz，CDCl3)δ7.96(dd，J＝7.9，2.0Hz，2H)，7.80(d，J＝8.2Hz，2H)，7.66(dd，J＝ 16.5，8.2Hz，4H)，7.48-7.31(m，8H)，7.27(d，J＝6.9Hz，3H)，4.35(s，2H).13C NMR(100MHz，CDCl3)δ 165.2，152.2，140.7，140.6，140.0，134.0，133.7，133.1，129.8，129.1，128.8，128.8，128.4，127.4，127.2，127.1， 126.8，126.3，33.3.
the nuclear magnetic data of the product of example 9 are as follows:
1H NMR(400MHz，CDCl3)δ7.92(dd，J＝7.7，4.1Hz，2H)，7.65(d，J＝8.5Hz，2H)，7.44-7.37(m， 5H)，7.33(t，J＝7.2Hz，2H)，7.29-7.21(m，3H)，4.27(s，2H).13C NMR(100MHz，CDCl3)δ165.4，151.3，139.7，133.8，133.5，133.4，133.3，130.0，129.9，128.8，128.8，128.7，128.3，126.9，126.3，33.2.
the nuclear magnetic data of the product of example 10 are as follows:
1H NMR(400MHz，CDCl3)δ7.96-7.90(m，2H)，7.75(s，1H)，7.58-7.53(m，1H)，7.42-7.38(m， 3H)，7.36-7.30(m，4H)，7.29-7.22(m，3H)，4.28(s，2H).13C NMR(100MHz，CDCl3)δ165.4，150.8， 139.6，136.6，134.4，134.0，133.4，130.0，129.7，128.9，128.8，128.8，128.3，128.0，126.9，126.7，126.3，33.2.
the nuclear magnetic data of the product of example 11 are as follows:
1H NMR(400MHz，CDCl3)δ7.93(dd，J＝7.8，2.2Hz，2H)，7.64(d，J＝8.6Hz，2H)，7.42-7.35(m， 3H)，7.35-7.29(m，2H)，7.25(t，J＝6.6Hz，3H)，7.01-6.94(m，2H)，4.27(s，2H)，3.83(s，3H).13C NMR (100MHz，CDCl3)δ164.9，159.4，152.3，140.1，133.8，131.8，130.0，129.7，128.8，128.7，128.3，127.6，126.7， 126.3，113.9，55.3，33.2.
the nuclear magnetic data of the product of example 14 are as follows:
1H NMR(400MHz，CDCl3)δ8.12(s，1H)，7.97(dd，J＝8.0，2.1Hz，2H)，7.91-7.81(m，4H)，7.50- 7.45(m，2H)，7.43-7.36(m，3H)，7.35-7.29(m，2H)，7.28-7.22(m，3H)，4.34(s，2H).13C NMR(100 MHz，CDCl3)δ165.2，152.4，140.0，133.7，133.4，133.2，132.8，132.3，129.8，128.8，128.8，128.4，128.2， 128.1，127.7，127.6，126.8，126.8，126.3，126.2，33.3.
the nuclear magnetic data of the product of example 15 are as follows:
1H NMR(400MHz，CDCl3)δ7.83(d，J＝8.2Hz，2H)，7.73-7.69(m，2H)，7.44(t，J＝7.4Hz，2H)， 7.37(t，J＝7.3Hz，1H)，7.20(d，J＝8.0Hz，2H)，7.14(s，4H)，4.25(s，2H)，2.37(s，3H)，2.34(s，3H).13C NMR(100MHz，CDCl3)δ165.3，152.1，140.0，137.1，136.4，135.0，133.0，131.1，129.5，129.4，128.8，128.4， 128.2，127.8，126.3，32.9，21.4，21.0.
the nuclear magnetic data of the product of example 16 are as follows:
1H NMR(400MHz，CDCl3)δ7.87(d，J＝8.5Hz，2H)，7.69-7.63(m，2H)，7.45(t，J＝7.4Hz，2H)， 7.39(t，J＝8.5Hz，3H)，7.29(d，J＝8.4Hz，2H)，7.15(d，J＝8.3Hz，2H)，4.26(s，2H).13C NMR(100MHz， CDCl3)δ164.0，152.8，138.3，135.8，134.5，132.7，132.7，132.0，129.7，129.1，128.9，128.7，128.6，128.2， 127.5，32.6.
the nuclear magnetic data of the product of example 17 are as follows:
1H NMR(400MHz，CDCl3)δ7.98(s，1H)，7.78(d，J＝7.1Hz，1H)，7.67(d，J＝7.4Hz，2H)，7.46(t，J ＝7.4Hz，2H)，7.42-7.30(m，3H)，7.28-7.19(m，3H)，7.10(t，J＝6.2Hz，1H)，4.27(s，2H).13C NMR(100 MHz，CDCl3)δ163.7，153.1，141.7，135.2，134.9，134.6，134.5，132.6，130.1，130.0，129.8，128.7，128.6， 128.5，128.2，127.1，126.5，126.2，124.5，32.9.
the nuclear magnetic data of the product of example 18 are as follows:
1H NMR(400MHz，CDCl3)δ8.38-8.29(m，1H)，7.69(d，J＝7.3Hz，2H)，7.47-7.27(m，7H)，7.23- 7.15(m，3H)，4.43(s，2H).13C NMR(100MHz，CDCl3)δ160.6，151.8，137.5，134.8，133.8，132.7，132.0， 131.8，130.6，130.5，130.1，130.0，129.6，128.6，128.5，128.3，127.9，127.1，126.9，30.8.
the nuclear magnetic data of the product of example 19 are as follows:
1H NMR(400MHz，CDCl3)δ7.88(d，J＝8.8Hz，2H)，7.73-7.68(m，2H)，7.44(t，J＝7.4Hz，2H)， 7.36(t，J＝7.3Hz，1H)，7.16(d，J＝8.6Hz，2H)，6.91(d，J＝8.8Hz，2H)，6.86(d，J＝8.7Hz，2H)，4.22(s， 2H)，3.83(s，3H)，3.79(s，3H).13C NMR(100MHz，CDCl3)δ165.0，161.0，158.4，151.8，135.0，132.8， 132.3，129.4，128.8，128.4，127.8，126.7，114.1，114.1，55.3，55.2，32.4.
the nuclear magnetic data of the product of example 21 are as follows:
1H NMR(400MHz，CDCl3)δ8.05(d，J＝8.2Hz，2H)，7.71-7.64(m，4H)，7.59(d，J＝8.1Hz，2H)， 7.50-7.32(m，5H)，4.37(s，2H).13C NMR(100MHz，CDCl3)δ163.6，153.7，143.7，136.7，134.4，132.8， 131.6(q，J＝32.4Hz)，129.4(q，J＝32.4Hz)，128.7，128.7，128.4，126.6，126.0，125.9(q，J＝4.0Hz)，125.8， 124.1(q，J＝270.4Hz)，123.9(q，J＝270.5Hz)，33.1.
the nuclear magnetic data of the product of example 22 are as follows:
1H NMR(400MHz，CDCl3)δ7.75-7.69(m，3H)，7.65(d，J＝7.8Hz，1H)，7.45(t，J＝7.5Hz，2H)， 7.37(t，J＝7.3Hz，1H)，7.15(d，J＝7.8Hz，1H)，7.09(d，J＝7.6Hz，1H)，7.03-6.96(m，2H)，4.22(s，2H)， 2.28(d，J＝5.5Hz，6H)，2.24(d，J＝3.4Hz，6H).13C NMR(100MHz，CDCl3)δ165.4，152.1，138.6，137.6， 137.0，136.9，135.2，135.0，133.0，131.5，130.0，129.9，129.7，128.8，128.4，127.8，127.3，125.7，123.9，32.8， 19.8，19.7，19.7，19.4.
the nuclear magnetic data of the product of example 23 are as follows:
1H NMR(400MHz，CDCl3)δ7.96-7.90(m，2H)，7.68(d，J＝7.2Hz，2H)，7.45(t，J＝7.4Hz，2H)， 7.41-7.36(m，1H)，7.22-7.16(m，2H)，7.12-7.06(m，2H)，7.04-6.98(m，2H)，4.26(s，2H).13C NMR (100MHz，CDCl3)δ164.1，164.0(d，J＝206.2Hz)，161.5(d，J＝201.4Hz)，152.5，135.6(d，J＝3.1Hz)，134.6，132.9，129.9，129.9，129.8，128.7，128.5，128.3，128.2，128.1，115.9(d，J＝21.9Hz)，115.6(d，J＝ 21.3Hz)，32.4.
the nuclear magnetic data of the product of example 24 are as follows:
1H NMR(400MHz，CDCl3)δ7.84-7.78(m，2H)，7.70-7.65(m，2H)，7.56-7.52(m，2H)，7.48- 7.37(m，5H)，7.10(d，J＝8.3Hz，2H)，4.24(s，2H).13C NMR(100MHz，CDCl3)δ164.0，152.9，138.8， 133.4，132.6，132.6，132.0，131.9，130.0，128.7，128.6，128.2，127.8，124.1，120.8，32.7.
the nuclear magnetic data of the product of example 25 are as follows:
1H NMR(400MHz，CDCl3)δ7.76-7.68(m，3H)，7.44(t，J＝7.4Hz，2H)，7.36(t，J＝7.3Hz，1H)， 7.28-7.17(m，7H)，4.28(s，2H)，2.64(s，3H)，2.22(s，3H).13C NMR(100MHz，CDCl3)δ164.9，151.4， 138.5，136.5，136.1，135.1，133.3，132.9，131.4，130.4，129.7，129.1，128.7，128.6，128.4，127.8，127.1，126.3， 125.9，31.3，21.7，19.4.
the nuclear magnetic data of the product of example 26 are as follows:
1H NMR(400MHz，CDCl3)δ8.16(dd，J＝7.9，1.7Hz，1H)，7.78-7.64(m，3H)，7.60(dd，J＝8.0，1.0 Hz，1H)，7.50-7.34(m，4H)，7.31-7.10(m，4H)，4.44(s，2H).13C NMR(100MHz，CDCl3)δ162.2，152.0， 139.2，139.2，134.7，134.1，134.0，133.0，132.8，131.4，130.3，130.1，128.6，128.5，128.0，127.8，127.4，124.3， 121.5，33.6.
the nuclear magnetic data of the product of example 27 are as follows:
1H NMR(400MHz，CDCl3)δ7.80(s，1H)，7.75-7.69(m，3H)，7.45(t，J＝7.4Hz，2H)，7.37(t，J＝7.3 Hz，1H)，7.29(t，J＝7.6Hz，1H)，7.25-7.18(m，2H)，7.06(t，J＝8.3Hz，3H)，4.26(s，2H)，2.39(s，3H)， 2.33(s，3H).13C NMR(100MHz，CDCl3)δ165.4，152.3，140.0，138.5，138.4，135.0，133.6，133.1，130.6， 129.1，128.8，128.7，128.6，128.5127.9，127.5，126.9，125.4，123.6，33.2，21.4，21.3.
the nuclear magnetic data of the product of example 28 are as follows:
1H NMR(400MHz，CDCl3)δ8.14(s，1H)，7.83(d，J＝7.8Hz，1H)，7.66(d，J＝7.2Hz，2H)，7.53- 7.36(m，6H)，7.27(t，J＝8.1Hz，1H)，7.21-7.12(m，2H)，4.26(s，2H).13C NMR(100MHz，CDCl3)δ 163.6，153.2，142.1，135.5，134.5，132.7，132.6，131.4，130.3，130.1，129.1，128.7，128.6，128.2，128.0，127.0， 125.0，123.0，122.9，32.8.
the nuclear magnetic data of the product of example 29 are as follows:
1H NMR(400MHz，CDCl3)δ8.41(d，J＝0.8Hz，1H)，8.07(dd，J＝8.6，1.7Hz，1H)，7.88-7.77(m， 8H)，7.70(s，1H)，7.50-7.44(m，6H)，7.41-7.22(m，2H)，4.48(s，2H).13C NMR(100MHz，CDCl3)δ 165.4，152.8，137.6，134.9，134.0，133.6，133.3，133.2，132.4，131.1，128.8，128.6，128.5，128.0，127.8，127.7， 127.7，126.8，126.7，126.6，126.3，125.8，125.7，123.9，33.5.
table 2: examples 1-29 conversion and products
Figure BSA0000174925940000091
Figure BSA0000174925940000101
Figure BSA0000174925940000111
Figure BSA0000174925940000121
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims (4)

1. A method for synthesizing polysubstituted 2, 4-diaryl thiazole and derivatives thereof,
the general formula of the polysubstituted 2, 4-diaryl thiazole and the derivative thereof is shown as a formula I:
Figure FSB0000195593650000011
wherein R1 is selected from: hydrogen atom, straight-chain alkyl of C1-C8, halogen, methoxy, phenyl, phenylethynyl, trifluoromethyl and trifluoromethoxy;
r2 is selected from: hydrogen atom, straight-chain alkyl of C1-C8, halogen, methoxy, phenyl, trifluoromethyl;
characterized in that the method comprises the following steps:
(I) adding aromatic ketone compound, aromatic aldehyde compound, ammonium salt, sulfur powder, water and organic solvent;
(II) fully mixing the reactants, and heating for reaction;
(III) purifying to obtain a product;
the aromatic ketone compound is selected from C8-C16 aromatic ketones, and the general formula of the aromatic ketone compound is shown as a formula II:
Figure FSB0000195593650000012
wherein R1 is selected from: hydrogen atom, straight-chain alkyl of C1-C8, halogen, methoxy, phenyl, phenylethynyl, trifluoromethyl and trifluoromethoxy;
the general formula of the aromatic aldehyde compound is shown as formula III:
Figure FSB0000195593650000021
wherein R2 is selected from: hydrogen atom, straight-chain alkyl of C1-C8, halogen, methoxy, phenyl, trifluoromethyl;
the ammonium salt is selected from: one or more of ammonium persulfate, ammonium chloride, ammonium iodide and ammonium hexafluorophosphate;
the organic solvent is: one or more of pyridine, quinoline and N, N-dimethylformamide.
2. The process according to claim 1, characterized in that the aromatic aldehyde compounds are selected from: benzaldehyde, 4-methylbenzaldehyde, 4-chlorobenzaldehyde, 3-chlorobenzaldehyde, 2-chlorobenzaldehyde, 4-methoxybenzaldehyde, 4-benzaldehyde, 4-trifluoromethylbenzaldehyde, 4-fluorobenzaldehyde, 4-bromobenzaldehyde, 2-methylbenzaldehyde, 2-bromobenzaldehyde, 3-methylbenzaldehyde, 3-bromobenzaldehyde.
3. The method according to claim 1, wherein the aromatic ketone compound is selected from the group consisting of: acetophenone, 4-methylacetophenone, 4-fluoroacetophenone, 4-bromoacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-phenylacetylacetophenone, 4-phenylacetophenone, 4-chloroacetophenone, 3-chloroacetophenone, 4-methoxyacetophenone, 3-trifluoromethylacetophenone, 4-trifluoromethylacetophenone.
4. A method according to any one of claims 1-3, characterized in that: the mol ratio of the aromatic ketone compound to the aromatic aldehyde compound to the ammonium salt to the sulfur powder to the water is 1.0: 3.0-4.0: 2.0-3.0: 2.0-4.0: 8.0-11.0; meanwhile, the reaction temperature is 130-150 ℃; the reaction time is 24-36 h.
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