CN109438384A - Polysubstituted 2,4- diaryl thiazole and derivative and its synthetic method - Google Patents
Polysubstituted 2,4- diaryl thiazole and derivative and its synthetic method Download PDFInfo
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- CN109438384A CN109438384A CN201811449501.2A CN201811449501A CN109438384A CN 109438384 A CN109438384 A CN 109438384A CN 201811449501 A CN201811449501 A CN 201811449501A CN 109438384 A CN109438384 A CN 109438384A
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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
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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
- C07D277/24—Radicals substituted by oxygen atoms
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Abstract
The present invention relates to the synthetic methods of a kind of polysubstituted 2,4- diaryl thiazole and its derivative.The present invention has developed for the first time with aromatic ketone compounds, aromatic aldehyde compound, and ammonium salt and sulphur powder are converted into the technical solution of one kind 2,4- diaryl thiazole and its derivative, obtained molecular structure stabilized, the excellent thiazole derivative of chemical property；By aromatic ketone compounds, aromatic aldehyde compound, ammonium salt and sulphur powder are converted into the technical solution of one kind 2,4- diaryl thiazole and derivative, reaction raw materials are cheap and easy to get, without metallic catalyst, need to only add the water of equivalent, it reduces environmental pollution, saves material, reduce reaction cost；Entire reaction system is simple, and reaction condition is mild, experimental implementation handy and safe, has developed a kind of method for constructing thiazole derivative by single step reaction under conditions of no metal catalytic.
Description
Technical field
The present invention relates to the synthetic methods of a kind of polysubstituted 2,4- diaryl thiazole and its derivative, belong to organic compound
Synthesis technical field.
Background technique
2,4- diaryl thiazoles and its derivative are a kind of important heteroaromatic compounds, have extensive bioactivity,
It has broad application prospects chemistry, medicine, biological stain and material science etc. are multi-field.The existing such compound of synthesis
Method there are synthesis step complexity, mostly use organic amine compound as source of ammonium, and need to generally add metallic catalyst be catalyzed
The disadvantages of.
Summary of the invention
The present invention provide for the first time excellent polysubstituted 2, the 4- diaryl thiazole of a kind of molecular structure stabilized, chemical property and its
Derivative.
The present invention also provides the synthetic methods of a kind of polysubstituted 2,4- diaryl thiazole and its derivative.
The technical solution adopted by the present invention to solve the technical problems is: the present invention provides a kind of polysubstituted 2,4- diaryl
Thiazole and derivative, general formula are Formulas I:
Wherein
R1It is selected from:
Hydrogen atom, the linear saturation or unsaturated alkyl of C1-C8, halogen, methane oxygroup, benzene aromatic radical, condensed ring；With one
Alkyl, alkoxy, the condensed ring of a or multiple halogenic substituents；
R2It is selected from:
Hydrogen atom, the linear saturation or unsaturated alkyl of C1-C8, halogen, alkoxy, aromatic radical, condensed ring；With one or
Alkyl, alkoxy, the condensed ring of multiple halogenic substituents；
The present invention also provides the methods of a kind of polysubstituted 2, the 4- diaryl thiazole of synthesis and its derivative, including following step
It is rapid:
Aromatic ketone compounds, aromatic aldehyde compound, ammonium salt, sulphur powder, water and organic solvent is added；
Reactant is sufficiently mixed, heating reaction；
Purifying obtains product.
Preferably, synthetic method of the invention, the aromatic ketone compounds are led to selected from C8-C16 aromatics ketone
Formula is Formula II:
Wherein
R1It is selected from:
Hydrogen atom, the linear saturation or unsaturated alkyl of C1-C8, halogen, methane oxygroup, benzene aromatic radical, condensed ring；With one
Alkyl, alkoxy, the condensed ring of a or multiple halogenic substituents；
Preferably, synthetic method of the invention, the aromatic ketone compounds are selected from: acetophenone, 4- methyl acetophenone, 4-
Fluoro acetophenone, 4- bromoacetophenone, 3- methyl acetophenone, 2- methyl acetophenone, 4- phenylacetylene base acetophenone, 4- phenyl acetophenone,
4- chloro-acetophenone, 3- chloro-acetophenone, 4- methoxyacetophenone, 3- trifluoromethyl acetophenone, 4- trifluoromethoxy acetophenone, 2-
Acetonaphthone.
Preferably, synthetic method of the invention, the aromatic aldehyde compound, general formula are formula III:
Wherein
R2It is selected from:
Hydrogen atom, the linear saturation or unsaturated alkyl of C1-C8, halogen, alkoxy, aromatic radical, condensed ring；With one or
Alkyl, alkoxy, the condensed ring of multiple halogenic substituents；
Preferably, synthetic method of the invention, the aromatic aldehyde compound are selected from: benzaldehyde, 4- tolyl aldehyde, 4-
Chlorobenzaldehyde, 3- chlorobenzaldehyde, 2- chlorobenzaldehyde, 4-methoxybenzaldehyde, 4- phenyl benzaldehyde, 4- trifluoromethylated benzaldehyde,
3,4- dimethylbenzaldehydes, 4- fluorobenzaldehyde, 4- bromobenzaldehyde, 2- tolyl aldehyde, 2- bromobenzaldehyde, 3- tolyl aldehyde,
3- bromobenzaldehyde, 2- naphthaldehyde.
Preferably, synthetic method of the invention, the ammonium salt are selected from: ammonium persulfate, ammonium chloride, ammonium iodide, hexafluorophosphoric acid
Ammonium it is one or more.
Preferably, synthetic method of the invention: aromatic ketone compounds and aromatic aldehyde compound and ammonium salt and sulphur powder with
The molar ratio of water is 1.0: 3.0-4.0: 2.0-3.0: 2.0-4.0: 8.0-11.0；Meanwhile reaction temperature is 130-150 DEG C；Instead
Seasonable a length of 24-36h；The organic solvent are as follows: pyridine, quinoline, n,N-Dimethylformamide it is one or more.
The present invention compared with prior art caused by the utility model has the advantages that
(I) present invention converts one kind 2,4- for aromatic ketone compounds, aromatic aldehyde compound, ammonium salt and sulphur powder for the first time
Molecular structure stabilized, the excellent product of chemical property is made in the technical solution of diaryl thiazole and derivative；(II) by aromatic ketone
Class compound, aromatic aldehyde compound, ammonium salt and sulphur powder are converted into the technical solution of one kind 2,4- diaryl thiazole and derivative,
It is for the first time directly using ammonium salt as nitrogen source, sulphur powder is as sulphur source, one kettle way collective effect synthesizing aryl thiazole, and reaction raw materials are honest and clean
Valence is easy to get, operation handy and safe；(III) it converts aromatic ketone compounds, aromatic aldehyde compound, ammonium salt and sulphur powder to
The technical solution of one kind 2,4- diaryl thiazole and derivative, reaction are not needed using metal or other catalyst, it is only necessary to be made
The water for using green to be easy to get reduces environmental pollution as additive, reduces reaction cost；(IV) by aromatic ketone compounds, fragrance
Aldehyde compound, ammonium salt and sulphur powder are converted into the technical solution of one kind 2,4- diaryl thiazole and its derivative, it has reaction
The features such as system is simple, and reaction condition is mild, and product utilization value is higher.The present invention 2,4- Diarylthiazole derivatives and its conjunction
At method, it can be widely applied to the multiple fields such as chemistry, medicine, biological stain and material science；Multicomponent one kettle way is efficient
Selectivity synthesis 2, the research and development of 4- diaryl thiazole compound.
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 nuclear magnetic spectrogram of 1 product of Fig. 1 a and 1b embodiment；
The nuclear magnetic spectrogram of 4 product of Fig. 2 a and 2b embodiment；
The nuclear magnetic spectrogram of 6 product of Fig. 3 a and 3b embodiment；
The nuclear magnetic spectrogram of 9 product of Fig. 4 a and 4b embodiment；
The nuclear magnetic spectrogram of 11 product of Fig. 5 a and 5b embodiment；
The nuclear magnetic spectrogram of 15 product of Fig. 6 a and 6b embodiment；
The nuclear magnetic spectrogram of 17 product of Fig. 7 a and 7b embodiment；
The nuclear magnetic spectrogram of 22 product of Fig. 8 a and 8b embodiment；
The nuclear magnetic spectrogram of 24 product of Fig. 9 a and 9b embodiment；
The nuclear magnetic spectrogram of 27 product of Figure 10 a and 10b embodiment；
Wherein a is hydrogen spectrogram, and b is carbon spectrogram.
Specific embodiment
In conjunction with the accompanying drawings, the present invention is further explained in detail.These attached drawings are simplified schematic diagram, only with
Illustration illustrates basic structure of the invention, therefore it only shows the composition relevant to the invention.
Reaction equation are as follows: " N " is ammonium salt.
Embodiment 1-51
Step 1: by aromatic ketone compounds (specific substance is shown in Table 1), aromatic aldehyde compound (specific substance is shown in Table 1),
Ammonium salt (specific substance is shown in Table 1), sulphur powder, water and organic solvent (specific substance is shown in Table 1) are added in reaction vessel；
Step 2: reaction vessel is evenly heated (such as oil bath heating) to temperature described in table 1, aromatic ketone compounds,
Aromatic aldehyde compound, ammonium salt, sulphur powder and water are reacted in a solvent, and continue the time described in table 1；
Step 3: purification step
Table 1: aromatic ketone compounds, aromatic aldehyde compound, ammonium salt (" N "), solvent, reaction temperature in embodiment 1-29
And the reaction time.
Wherein molar ratio * is the molar ratio of aromatic ketone compounds and aromatic aldehyde compound and ammonium salt and sulphur powder and water.
In the reaction of above-described embodiment, aromatic ketone compounds and aromatic aldehyde compound, ammonium salt and sulphur powder collective effect,
Ultimately generate target compound.
Substance in reaction vessel after step 3 is subjected to conversion ratio detection and carries out nuclear magnetic resonance, the knot of section Example
Fruit is as follows:
The nuclear magnetic data of 1 product of embodiment is as follows:
1H NMR (400MHz, CDCl3) δ 7.94 (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) δ 165.2,152.5,
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 2 product of embodiment is as follows:
1H NMR (400MHz, CDCl3) δ 7.95 (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 3 product of embodiment is as follows:
1H NMR (400MHz, CDCl3) δ 7.94 (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) δ 165.3,162.5 (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 4 product of embodiment is as follows:
1H NMR (400MHz, CDCl3) δ 7.92 (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) δ 165.4,151.2,139.7,133.9,133.5,133.3,131.6,130.3,129.9,128.8,128.8,
128.3,126.9,126.3,122.0,33.2.
The nuclear magnetic data of 5 product of embodiment is as follows:
1H NMR (400MHz, CDCl3) δ 7.94 (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) δ 165.1,152.7,140.2,
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 6 product of embodiment is as follows:
1H NMR (400MHz, CDCl3) δ 7.92 (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) δ 165.0,
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 7 product of embodiment is as follows:
1H NMR (400MHz, CDCl3) δ 7.94 (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) δ 165.3,151.6,139.8,134.7,
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 8 product of embodiment is as follows:
1H NMR (400MHz, CDCl3) δ 7.96 (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 9 product of embodiment is as follows:
1H NMR (400MHz, CDCl3) δ 7.92 (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) δ 165.4,151.3,139.7,133.8,133.5,133.4,133.3,130.0,129.9,128.8,
128.8,128.7,128.3,126.9,126.3,33.2.
The nuclear magnetic data of 10 product of embodiment is as follows:
1H NMR (400MHz, CDCl3) δ 7.96-7.90 (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)δ
165.4,150.8,139.6,136.6,134.4,134.0,133.4,130.0,129.7,128.9,128.8,128.8,
128.3,128.0,126.9,126.7,126.3,33.2.
The nuclear magnetic data of 11 product of embodiment is as follows:
1H NMR (400MHz, CDCl3) δ 7.93 (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) 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 14 product of embodiment is as follows:
1H NMR (400MHz, CDCl3) δ 8.12 (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) δ 165.2,152.4,140.0,133.7,133.4,133.2,132.8,132.3,
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 15 product of embodiment is as follows:
1H NMR (400MHz, CDCl3) δ 7.83 (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) δ 165.3,152.1,140.0,137.1,136.4,135.0,
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 16 product of embodiment is as follows:
1H NMR (400MHz, CDCl3) δ 7.87 (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) δ 164.0,152.8,138.3,135.8,134.5,132.7,132.7,132.0,
129.7,129.1,128.9,128.7,128.6,128.2,127.5,32.6.
The nuclear magnetic data of 17 product of embodiment is as follows:
1H NMR (400MHz, CDCl3) δ 7.98 (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) δ 163.7,153.1,141.7,135.2,134.9,134.6,134.5,
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 18 product of embodiment is as follows:
1H NMR (400MHz, CDCl3) δ 8.38-8.29 (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) δ 160.6,151.8,137.5,134.8,
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 19 product of embodiment is as follows:
1H NMR (400MHz, CDCl3) δ 7.88 (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) δ 165.0,
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 21 product of embodiment is as follows:
1H NMR (400MHz, CDCl3) δ 8.05 (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) δ 163.6,153.7,143.7,
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 22 product of embodiment is as follows:
1H NMR (400MHz, CDCl3) δ 7.75-7.69 (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) δ 165.4,152.1,138.6,137.6,137.0,136.9,135.2,135.0,133.0,131.5,130.0,
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 23 product of embodiment is as follows:
1H NMR (400MHz, CDCl3) δ 7.96-7.90 (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) δ 164.1,164.0 (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 24 product of embodiment is as follows:
1H NMR (400MHz, CDCl3) δ 7.84-7.78 (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) δ 164.0,
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 25 product of embodiment is as follows:
1H NMR (400MHz, CDCl3) δ 7.76-7.68 (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) δ 164.9,151.4,138.5,136.5,136.1,135.1,133.3,132.9,131.4,130.4,129.7,
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 26 product of embodiment is as follows:
1H NMR (400MHz, CDCl3) δ 8.16 (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) δ 162.2,152.0,139.2,139.2,134.7,134.1,134.0,133.0,132.8,131.4,130.3,
130.1,128.6,128.5,128.0,127.8,127.4,124.3,121.5,33.6.
The nuclear magnetic data of 27 product of embodiment is as follows:
1H NMR (400MHz, CDCl3) δ 7.80 (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) δ 165.4,152.3,140.0,
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 28 product of embodiment is as follows:
1H NMR (400MHz, CDCl3) δ 8.14 (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 29 product of embodiment is as follows:
1H NMR (400MHz, CDCl3) δ 8.41 (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: the conversion ratio and product of embodiment 1-29 reaction
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (8)
1. a kind of polysubstituted 2,4- diaryl thiazole and its derivative, which is characterized in that its general formula is Formulas I:
Wherein
R1It is selected from:
Hydrogen atom, the linear saturation or unsaturated alkyl of C1-C8, halogen, methane oxygroup, benzene aromatic radical, condensed ring；With one or
Alkyl, alkoxy, the condensed ring of multiple halogenic substituents；
R2It is selected from:
Hydrogen atom, the linear saturation or unsaturated alkyl of C1-C8, halogen, alkoxy, aromatic radical, condensed ring；With one or more
Alkyl, alkoxy, the condensed ring of halogenic substituent.
2. a kind of method for synthesizing polysubstituted 2,4- diaryl thiazole and its derivative described in claim 1, including following step
It is rapid:
(I) aromatic ketone compounds, aromatic aldehyde compound, ammonium salt, sulphur powder, water and organic solvent is added；
(II) reactant is sufficiently mixed, heating reaction；
(III) purifying obtains product.
3. synthetic method according to claim 2, which is characterized in that the aromatic ketone compounds are selected from C8-C16
Aromatics ketone, general formula are Formula II:
Wherein
R1It is selected from:
Hydrogen atom, the linear saturation or unsaturated alkyl of C1-C8, halogen, methane oxygroup, benzene aromatic radical, condensed ring；With one or
Alkyl, alkoxy, the condensed ring of multiple halogenic substituents.
4. synthetic method according to claim 3, which is characterized in that the aromatic ketone compounds are selected from: acetophenone, 4-
Methyl acetophenone, 4- fluoro acetophenone, 4- bromoacetophenone, 3- methyl acetophenone, 2- methyl acetophenone, 4- phenylacetylene base acetophenone,
4- phenyl acetophenone, 4- chloro-acetophenone, 3- chloro-acetophenone, 4- methoxyacetophenone, 3- trifluoromethyl acetophenone, 4- trifluoro methoxy
Benzoylformaldoxime, 2- acetonaphthone.
5. synthetic method according to claim 2 or 3, which is characterized in that the aromatic aldehyde compound, general formula are formula
III:
Wherein
R2It is selected from:
Hydrogen atom, the linear saturation or unsaturated alkyl of C1-C8, halogen, alkoxy, aromatic radical, condensed ring；With one or more
Alkyl, alkoxy, the condensed ring of halogenic substituent.
6. synthetic method according to claim 5, which is characterized in that the aromatic aldehyde compound is selected from: benzaldehyde, 4-
Tolyl aldehyde, 4- chlorobenzaldehyde, 3- chlorobenzaldehyde, 2- chlorobenzaldehyde, 4-methoxybenzaldehyde, 4- phenyl benzaldehyde, 4- tri-
Methyl fluoride benzaldehyde, 3,4- dimethylbenzaldehydes, 4- fluorobenzaldehyde, 4- bromobenzaldehyde, 2- tolyl aldehyde, 2- bromobenzaldehyde,
3- tolyl aldehyde, 3- bromobenzaldehyde, 2- naphthaldehyde.
7. according to the described in any item synthetic methods of claim 2-6, which is characterized in that the ammonium salt is selected from: ammonium persulfate, chlorine
Change ammonium, ammonium iodide, ammonium hexafluorophosphate it is one or more.
8. according to the described in any item synthetic methods of claim 2-7, it is characterised in that: aromatic ketone compounds and aromatic aldehydes
Compound and ammonium salt and sulphur powder and the molar ratio of water are 1.0: 3.0-4.0: 2.0-3.0: 2.0-4.0: 8.0-11.0；Meanwhile instead
Answering temperature is 130 DEG C -150 DEG C；A length of 24-36h when reaction；The organic solvent are as follows: pyridine, quinoline, N, N- dimethyl formyl
Amine it is one or more.
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