CN103044352B - Thiazolidinone derivatives and preparation method thereof - Google Patents
Thiazolidinone derivatives and preparation method thereof Download PDFInfo
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- CN103044352B CN103044352B CN201110308986.5A CN201110308986A CN103044352B CN 103044352 B CN103044352 B CN 103044352B CN 201110308986 A CN201110308986 A CN 201110308986A CN 103044352 B CN103044352 B CN 103044352B
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- under reduced
- reduced pressure
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- thiazolinone derivative
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229960001701 chloroform Drugs 0.000 claims description 10
- PQJJJMRNHATNKG-UHFFFAOYSA-N ethyl bromoacetate Chemical compound CCOC(=O)CBr PQJJJMRNHATNKG-UHFFFAOYSA-N 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 235000017281 sodium acetate Nutrition 0.000 claims description 10
- 239000001632 sodium acetate Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 230000000844 anti-bacterial effect Effects 0.000 claims description 5
- 229940088710 antibiotic agent Drugs 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229960004756 ethanol Drugs 0.000 claims description 5
- QKFJKGMPGYROCL-UHFFFAOYSA-N phenyl isothiocyanate Chemical compound S=C=NC1=CC=CC=C1 QKFJKGMPGYROCL-UHFFFAOYSA-N 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 4
- WNRGWPVJGDABME-UHFFFAOYSA-N 3,5-Dimethoxyaniline Chemical compound COC1=CC(N)=CC(OC)=C1 WNRGWPVJGDABME-UHFFFAOYSA-N 0.000 claims description 3
- KRZCOLNOCZKSDF-UHFFFAOYSA-N 4-fluoroaniline Chemical compound NC1=CC=C(F)C=C1 KRZCOLNOCZKSDF-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- FEKSQPIVDJSVJJ-UHFFFAOYSA-N n-chloro-2-fluoroaniline Chemical compound FC1=CC=CC=C1NCl FEKSQPIVDJSVJJ-UHFFFAOYSA-N 0.000 claims description 3
- NCBZRJODKRCREW-UHFFFAOYSA-N m-anisidine Chemical compound COC1=CC=CC(N)=C1 NCBZRJODKRCREW-UHFFFAOYSA-N 0.000 claims description 2
- 229940124350 antibacterial drug Drugs 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000003814 drug Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000001207 fluorophenyl group Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- -1 thiazoline ketone Chemical class 0.000 description 2
- 206010011409 Cross infection Diseases 0.000 description 1
- 101100391174 Dictyostelium discoideum forC gene Proteins 0.000 description 1
- 241000713772 Human immunodeficiency virus 1 Species 0.000 description 1
- 206010034133 Pathogen resistance Diseases 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000002082 anti-convulsion Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 206010025482 malaise Diseases 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 201000008827 tuberculosis Diseases 0.000 description 1
- 230000036642 wellbeing Effects 0.000 description 1
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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Thiazole And Isothizaole Compounds (AREA)
Abstract
The invention relates to thiazolidinone derivatives which are characterized by having the following general formula, wherein R is shown in the specification. The thiazolidinone derivatives can be applied to prepare antibacterial drugs. A preparation method of the thiazolidinone derivatives is disclosed by the invention.
Description
Technical field
The present invention relates to class thiazolinone derivative and preparation method thereof.
Background technology.
Antibacterials be current clinical application the most extensively and a most important class medicine, along with the continuous listing of new variety and the increase of bacterial resistance bacterial strain and the increase of resistance, the sickness rate of hospital infection disease rises gradually, brings very large difficulty to the aspect such as clinical conditions and prevention.In recent years, antibacterials had had and had developed on a large scale very much, but the resistance phenomenon of new antimicrobial agent also accompanies row thereupon, and the reasonable application of antibacterials is day by day complicated.
Thiazolinone and derivative thereof are owing to having pharmacology and the biological activity of wide spectrum, as sterilization, anticonvulsion, antitumor, tuberculosis, pain relieving, anticancer and anti HIV-1 virus etc., simultaneously in organic synthesis, it or the good intermediate of a class, can be used for synthesis and many there is bioactive compound, can also for the synthesis of fuel, liquid crystal material etc., and the concern of extremely chemist and medicine scholar.Therefore, the present invention is by preparation one class thiazolinone derivative.
This analog derivative has obvious restraining effect to bacterial growth, and therefore, thiazolinone derivative extremely merits attention as the prospect of very potential anti-bacterial drug.Along with deepening continuously of thiazoline ketone drug research, basis that its anti-microbial effect mechanism is constantly understood is carried out effective structure of modification and modification and molecular designing, being used for clinical by having increasing thiazoline ketone antibacterials that are efficient, low toxicity, promoting the well-being of mankind.
Summary of the invention
The object of the present invention is to provide a class thiazolinone derivative and their preparation method.
Technical scheme of the present invention is as follows:
One class thiazolinone derivative, is characterized in that it has following general formula:
In formula, R is:
Prepare a method for an above-mentioned class thiazolinone derivative, it is characterized in that it is made up of the following step:
Step 1. is by 0.01mol thiocarbanil, and 0.01mol para-fluoroaniline or the chloro-2-fluoroaniline of 3-or 3,5-dimethoxyaniline, 20mL trichloromethane is placed in the round-bottomed flask with reflux, and oil bath is heated, back flow reaction 4h at 55 DEG C.
Step 2., by solvent trichloromethane evaporated under reduced pressure, adds water and is extracted with ethyl acetate twice, organic over anhydrous Na
2sO
4evaporated under reduced pressure after dry, obtains solid.
The solid that step 2 obtains by step 3. is dissolved in ethanol, then adds ethyl bromoacetate and sodium acetate, back flow reaction 8h at 60 DEG C.Wherein the mol ratio of step 2 gained reactant and ethyl bromoacetate is 1: 3, is 1: 1.5 with the mol ratio of sodium acetate.
After step 4. reacts completely, add water after etoh solvent evaporate to dryness, be extracted with ethyl acetate, organic over anhydrous Na
2sO
4drying, solvent under reduced pressure evaporate to dryness, the crude product dehydrated alcohol recrystallization obtained obtains a class thiazolinone derivative of the present invention.
Embodiment
Further describe the present invention by following examples, but scope of the present invention is not by any restriction of these embodiments.
The preparation of embodiment one: 3-(the fluoro-phenyl of 4-)-2-phenyl imido-thiazol-4-one (compound 1).
By 0.01mol thiocarbanil, 0.01mol para-fluoroaniline, 20mL trichloromethane is placed in the round-bottomed flask with reflux, and oil bath is heated, back flow reaction 4h at 55 DEG C.By solvent trichloromethane evaporated under reduced pressure, add water and be extracted with ethyl acetate twice, organic over anhydrous Na
2sO
4evaporated under reduced pressure after dry, obtains solid.The solid obtained is dissolved in ethanol, then adds ethyl bromoacetate and sodium acetate, back flow reaction 8h at 60 DEG C.Wherein the mol ratio of gained solid and ethyl bromoacetate is 1: 3, is 1: 1.5 with the mol ratio of sodium acetate.After reacting completely, add water after etoh solvent evaporate to dryness, be extracted with ethyl acetate, organic over anhydrous Na
2sO
4drying, solvent under reduced pressure evaporate to dryness, the crude product dehydrated alcohol recrystallization obtained obtains a class thiazolinone derivative of the present invention.Buff powder, productive rate 60%, m.p.120-123 DEG C; 1H NMR (300MHz, CDCl3): 4.17 (s, 2H); 6.86-6.92 (m, 2H); (7.13-7.19 dd, J=8.4Hz, 2H); 7.31-7.52 (m, 5H) .MS (ESI): 287.06 (C
15h
11fN
2oS, [M+H]+) .Anal.Calcd for C
15h
11fN
2oS:C, 62.92; H, 3.87; N, 9.78%.Found:C, 62.61; H, 3.73; N, 9.92%.
The preparation of embodiment two: 3-(the fluoro-phenyl of the chloro-2-of 3-)-2-phenyl imido-thiazol-4-one (compound 2).
By 0.01mol thiocarbanil, chloro-2 fluoroanilines of 0.01mol 3-, 20mL trichloromethane is placed in the round-bottomed flask with reflux, and oil bath is heated, back flow reaction 4h at 55 DEG C.By solvent trichloromethane evaporated under reduced pressure, add water and be extracted with ethyl acetate twice, organic over anhydrous Na
2sO
4evaporated under reduced pressure after dry, obtains solid.The solid obtained is dissolved in ethanol, then adds ethyl bromoacetate and sodium acetate, back flow reaction 8h at 60 DEG C.Wherein the mol ratio of step 2 gained reactant and ethyl bromoacetate is 1: 3, is 1: 1.5 with the mol ratio of sodium acetate.After reacting completely, add water after etoh solvent evaporate to dryness, be extracted with ethyl acetate, organic over anhydrous Na
2sO
4drying, solvent under reduced pressure evaporate to dryness, the crude product dehydrated alcohol recrystallization obtained obtains a class thiazolinone derivative of the present invention.Pale yellow powder, productive rate 65%, m.p.129-130 DEG C; 1HNMR (300MHz, CDCl3): 4.31 (s, 2H); (6.86-6.89 d, J=3.6Hz, 1H); (6.97-6.99 d, J=3.6Hz, 1H); 7.07-7.18 (m, 1H); (7.28-7.32 t, J=3.3Hz, 1H); 7.34-7.47 (m, 2H); 7.51-7.61 (m, 2H) .MS (ESI): 321.02 (C
15h
10clFN
2oS, [M+H]+) .Anal.Calcd forC
15h
11fN
2oS:C, 56.17; H, 3.14; N, 8.73%.Found:C, 56.23; H, 3.11; N, 8.63%.
The preparation of embodiment three: 3-(3,5-3,5-dimethylphenyl)-2-phenyl imido-thiazol-4-one (compound 3).
By 0.01mol thiocarbanil, 0.01mol 3,5-dimethoxyaniline, 20mL trichloromethane is placed in the round-bottomed flask with reflux, and oil bath is heated, back flow reaction 4h at 55 DEG C.By solvent trichloromethane evaporated under reduced pressure, add water and be extracted with ethyl acetate twice, organic over anhydrous Na
2sO
4evaporated under reduced pressure after dry, obtains solid.The solid obtained is dissolved in ethanol, then adds ethyl bromoacetate and sodium acetate, back flow reaction 8h at 60 DEG C.Wherein the mol ratio of step 2 gained reactant and ethyl bromoacetate is 1: 3, is 1: 1.5 with the mol ratio of sodium acetate.After reacting completely, add water after etoh solvent evaporate to dryness, be extracted with ethyl acetate, organic over anhydrous Na
2sO
4drying, solvent under reduced pressure evaporate to dryness, the crude product dehydrated alcohol recrystallization obtained obtains a class thiazolinone derivative of the present invention.White powder, productive rate 60%, m.p.195-196 DEG C;
1hNMR (300MHz, CDCl
3): 2.32 (s, 6H); 4.14 (s, 2H); 6.86 (s, 1H); 6.88-6.89 (m, 1H); 6.99 (s, 2H); (7.08-7.12 dd, J=6.3Hz, 2H); 7.31-7.36 (m, 2H) .MS (ESI): 329.09 (C
17h
16n
2o
3s, [M+H]+) .Anal.Calcd for C
17h
16n
2o
3s:C, 62.18; H, 4.91; N, 8.53%.Found:C, 61.99; H, 4.93; N, 8.63%.
Claims (3)
1. a class thiazolinone derivative, is characterized in that it has following general formula:
In formula, R is:
2. prepare a method for a class thiazolinone derivative according to claim 1, it is characterized in that it is made up of the following step:
Step 1. by 0.01mol thiocarbanil, 0.01mol para-fluoroaniline or the chloro-2-fluoroaniline of 3-or 3,5-dimethoxyaniline, 20mL trichloromethane is placed in the round-bottomed flask with reflux, and oil bath is heated, back flow reaction 4h at 55 DEG C;
Step 2., by solvent trichloromethane evaporated under reduced pressure, adds water and is extracted with ethyl acetate twice, organic over anhydrous Na
2sO
4evaporated under reduced pressure after dry, obtains solid;
The solid that step 2 obtains by step 3. is dissolved in ethanol, then adds ethyl bromoacetate and sodium acetate, back flow reaction 8h at 60 DEG C, and wherein the mol ratio of step 2 gained reactant and ethyl bromoacetate is 1: 3, is 1: 1.5 with the mol ratio of sodium acetate;
After step 4. reacts completely, add water after etoh solvent evaporate to dryness, be extracted with ethyl acetate, organic over anhydrous Na
2sO
4drying, solvent under reduced pressure evaporate to dryness, the crude product dehydrated alcohol recrystallization obtained obtains a class thiazolinone derivative of the present invention.
3. the application of a class thiazolinone derivative according to claim 1 in preparation antibacterials.
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|---|---|---|---|
| CN201110308986.5A CN103044352B (en) | 2011-10-13 | 2011-10-13 | Thiazolidinone derivatives and preparation method thereof |
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|---|---|---|---|
| CN201110308986.5A CN103044352B (en) | 2011-10-13 | 2011-10-13 | Thiazolidinone derivatives and preparation method thereof |
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|---|---|
| CN103044352A CN103044352A (en) | 2013-04-17 |
| CN103044352B true CN103044352B (en) | 2015-04-29 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2949457A (en) * | 1958-11-28 | 1960-08-16 | Ciba Pharm Prod Inc | Certain 2-phenyl-imino-3-phenyl-thiazolidine-4-ones |
| CN1055180A (en) * | 1990-03-27 | 1991-10-09 | 沃纳-兰伯特公司 | 3 of thiazolinone, azoles quinoline ketone and the imidazolone type that 2-replaces, the preparation method of 5-di-tert-butyl-hydroxy phenyl methylene derivatives |
| WO2009137133A2 (en) * | 2008-02-14 | 2009-11-12 | University Of Washington | 5-substituted-2-imino-thiazolidinone compounds and their use as inhibitors of bacterial infection |
-
2011
- 2011-10-13 CN CN201110308986.5A patent/CN103044352B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2949457A (en) * | 1958-11-28 | 1960-08-16 | Ciba Pharm Prod Inc | Certain 2-phenyl-imino-3-phenyl-thiazolidine-4-ones |
| CN1055180A (en) * | 1990-03-27 | 1991-10-09 | 沃纳-兰伯特公司 | 3 of thiazolinone, azoles quinoline ketone and the imidazolone type that 2-replaces, the preparation method of 5-di-tert-butyl-hydroxy phenyl methylene derivatives |
| WO2009137133A2 (en) * | 2008-02-14 | 2009-11-12 | University Of Washington | 5-substituted-2-imino-thiazolidinone compounds and their use as inhibitors of bacterial infection |
Non-Patent Citations (1)
| Title |
|---|
| Potential Fungicides: Studies of 2-Arylimino-3-aryl-4-thiazolidinones, Their 1,1-Dioxides and 5-Phenylazo Derivatives;Ram Lakhan;《Agric. Biol. Chem.》;19821231;第46卷(第2期);第557-560页 * |
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Inventor after: Zhu Hailiang Inventor after: Sun Juan Inventor after: Zhang Yanbin Inventor after: Xiao Yu Inventor after: Yang Yushun Inventor after: Wang Xiaoliang Inventor after: Zhang Fei Inventor before: Zhu Hailiang Inventor before: Sun Juan Inventor before: Zhang Yanbin Inventor before: Yang Yushun Inventor before: Wang Xiaoliang Inventor before: Zhang Fei |
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Free format text: CORRECT: INVENTOR; FROM: ZHU HAILIANG SUN JUAN ZHANG YANBIN YANG YUSHUN WANG XIAOLIANG ZHANG FEI TO: ZHU HAILIANG SUN JUAN ZHANG YANBIN XIAO YU YANG YUSHUN WANG XIAOLIANG ZHANG FEI |
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