A kind of synthetic method of 2-iminothiazolidin-4-ketone and its derivatives

A technology of imino thiazolidine and a synthesis method, which is applied in the field of thiazole compound synthesis, can solve the problems of inability to be further modified, cumbersome post-processing, high toxicity of reagents, etc., and achieves the effects of ingenious design idea, avoidance of corrosion effect and simple operation.

Inactive Publication Date: 2011-12-14
XI AN JIAOTONG UNIV
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  • Abstract
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  • Application Information

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Problems solved by technology

[0020] Thiourea and N-substituted maleamide are obtained thiazolidinone derivatives through Michael-type addition under solvent-free conditions, and the yield is higher, which belongs to a green method (Shimo, T.; Matsuda, Y.; Iwanaga, T.; etal., Heterocycles, 2007, 71 (5), 1053-1058), but there is a substituent at the 5-position in the structure of the product obtained by this method, which is not an unsubstituted active methylene group, and cannot be further processed by condensation reaction Structural modification
[0021] The above-mentioned synthetic method has more or less various defects, thereby limiting its large-scale industrialized clean production, such as the toxicity of the reagent used is relatively large, the post-treatment is loaded down with trivial details, the product does not contain methylene, and cannot be further modified, etc. (Nekrasov, D.D.; Obukhova , A.S.Chem.Heterocylclic Compd., 2006, 42, 1109)

Method used

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  • A kind of synthetic method of 2-iminothiazolidin-4-ketone and its derivatives
  • A kind of synthetic method of 2-iminothiazolidin-4-ketone and its derivatives
  • A kind of synthetic method of 2-iminothiazolidin-4-ketone and its derivatives

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0051] Embodiment 1: Synthesis of 2-iminothiazolidin-4-one hydrochloride (1)

[0052]

[0053] Chloroacetic acid (9.46g, 100mmol), thiourea (7.61g, 100mmol) and water (10mL) were added successively in the reaction kettle. Stir the reaction in a water bath at 40°C, the reaction is exothermic, the reaction system becomes clear quickly, and then the temperature of the system rises, and the highest temperature reaches 72°C. After that, the temperature of the system gradually decreases, and the white solid increases. After 1 hour of reaction, the reaction temperature is constant to 40°C, and TLC is used. (Developer: chloroform-methanol 10:1) to monitor the reaction progress, iodine cylinder staining, showing that the reaction was complete, after the system was naturally cooled to room temperature, filtered with suction, the precipitate was collected and washed with a small amount of ice water, dried to obtain white crystals (9.15g) , which is 2-iminothiazolidin-4-one hydrochlori...

Embodiment 2

[0054] Example 2: Synthesis of 2-(ethylimino)-3-ethyl-thiazolidin-4-one (2)

[0055]

[0056] Add chloroacetic acid (2.35g, 25.0mmol), 1,3-diethylthiourea (3.05g, 23.0mmol) and water (10mL) successively in the flask, stir in an oil bath to dissolve completely, and heat to 100°C, reflux reaction for 5 hours, monitor the reaction progress with TLC (developing solvent: chloroform-methanol 20:1); after the reaction is completed, cool the reaction system to room temperature, add aqueous sodium hydroxide solution (2mol / L) to adjust the pH of the system to 12, extracted with ethyl acetate, and the obtained organic phase was washed with saturated sodium chloride and dried over anhydrous sodium sulfate. Filtrate and recover the organic solvent to obtain a yellow oily liquid, which gradually condenses into needle-like crystals (3.43g) after standing at room temperature, which is 2-(ethylimino)-3-ethyl-thiazolidin-4-one , and the yield was 86.4% (calculated as chloroacetic acid). Th...

Embodiment 3

[0057] Example 3: Synthesis of 3-n-butyl-2-(n-butylimino)thiazolidin-4-one (3)

[0058]

[0059] Chloroacetic acid (2.35g, 25.0mmol), 1,3-di-n-butylthiourea (4.7g, 25.0mmol) and water (15mL) were added successively in the flask, heated to 100°C, refluxed for 7.5 hours, TLC ( Developing agent: petroleum ether-ethyl acetate 5:1) to monitor the reaction progress, after the reaction was completed, when the system was cooled to room temperature, an oily substance was precipitated in the system, extracted with ethyl acetate, washed with saturated sodium chloride, and dried over anhydrous sodium sulfate. After filtration, the organic solvent was distilled off to obtain a yellow oily liquid (3.7 g), with a yield of 64.9% (based on chloroacetic acid). MS: 228.1(25)[M] + ; 1 H NMR (400MHz, CDCl 3 )δ: 3.92(s, 1H, HO-CH=), 3.76(s, 2H, R 1 R 2 NCH 2 CH 2 CH 2 CH 3 ), 3.69(t, 2H, R 1 R 2 NCH 2 CH2 CH 2 CH 3 ), 3.59(t, 2H, R 1 R 2 NCH 2 CH 2 CH 2 CH 3 ), 3.25(t, 2H, CH...

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Abstract

The invention discloses a method for synthesizing 2-iminothiazolidine-4-one and derivatives thereof. The method comprises the following steps of: reacting water or ethanol serving as a solvent and 1 molar part of thiourea or N,N'-disubstituted thiourea and 1 to 1.5 molar parts of chloroacetic acid which are taken as reaction raw materials at the temperature of between 40 and 100 DEG C for 1 to 10hours; and thus obtaining the 2-iminothiazolidine-4-one or the derivatives thereof after reaction. In the method, the water or the ethanol is taken as the solvent, and the chloroacetic acid is a reaction substrate and also a reaction catalyst; and the acidity of the chloroacetic acid is smartly utilized to self-catalyze the reaction, thiazole heterocycles can be formed through cyclization at higher reaction yield (32.5 to 86.4 percent) under the condition that additional catalysts are not used, and the process that a fussy esterification or amidation reaction is used for derivatization of thechloroacetic acid and the aftertreatment process of waste acid obtained after reaction are avoided. The method for synthesizing the 2-iminothiazolidine-4-one and the derivatives thereof is an environment-friendly synthetic process, is easy to operate, and is particularly suitable for industrialized clean production, and design thought is ingenious.

Description

technical field [0001] The invention belongs to the technical field of thiazole compound synthesis, in particular to a synthesis method of 2-iminothiazolidin-4-one and derivatives thereof. Background technique [0002] Most clinical drugs are chemically synthesized compounds containing heterocyclic structures. Some natural heterocyclic compounds are also commonly used clinical drugs. Many compounds related to life activities contain heterocyclic rings. In short, the activity of drugs often depends on the structure. heterocycle in . This may be due to the fact that heterocyclic compounds are less likely to be metabolized and decomposed in the body than alicyclic or aromatic ring compounds, and have better biocompatibility with the body. [0003] Heterocyclic compounds containing N and S atoms widely exist in nature and have a wide range of biological activities, especially in anti-tumor, anti-virus, anti-bacterial, anti-inflammatory, anti-diabetic, anti-psychotic, anti-hista...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D277/54
Inventor 孟歌郑美林许彦红董梦舒唐荣华高扬师建华
Owner XI AN JIAOTONG UNIV
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