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Method for preparing 5-substituted-2-thiazolidinone

A technology of thiazolidinone and alkyl, applied in the field of preparation of 5-substituted 2-thiazolidinone

Active Publication Date: 2013-10-16
BEIJING UNIV OF CHEM TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, there is no general method for the synthesis of 5-substituted 2-thiazolidinones, therefore, it is of great significance to develop a method for the synthesis of 5-substituted 2-thiazolidinones

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0051] Preparation of methyl 3-(2-thiazolidinon-5-yl)propionate 3a

[0052] Add dithiocarbonic acid to a 50 mL three-neck flask O -Ethyl- S -(2-oxo-2-methoxyethyl) ester (388.3 mg, 2 mmol), tert-butyl N-allylcarbamate (345.8 mg, 2.2 mmol) and 2 mL of 1,2-dichloro Ethane (DCE), evacuated, N 2 under protection at 90 o Add lauroyl peroxide (DLP) (21 mg, 2.5 mol%) after reflux in C oil bath for 5 minutes, TLC detects the reaction, add DLP (11.5-84 mg, 1.25-10 mol%) every 45 minutes until the raw material is yellow The ortho ester completely disappeared and the reaction was stopped. After the reaction solution was spinned to remove the solvent, it was separated on a silica gel column (eluent petroleum ether: ethyl acetate = 15:1 to 3:1) to obtain dithiocarbonic acid O -Ethyl- S -(5-methoxy-1-tert-butoxycarbonylamino-5-oxopent-2-yl)ester.

[0053] Add the above addition product (351.5 mg, 1 mmol), 5 mL of acetonitrile and 88% formic acid (690 mg, 15 mmol) into a 25 mL round-b...

Embodiment 2

[0055] Preparation of Diethyl 2-[(2-thiazolidinon-5-yl)methyl]malonate 3b

[0056] According to the method described in Example 1, with dithiocarbonic acid O -Ethyl- S -(1,3-diethoxy-1,3-dioxopropan-2-yl] ester and tert-butyl N-allylcarbamate as raw materials to obtain 2-[(2-thiazolidinone-5 -yl)methyl]diethyl malonate, colorless solid 201 mg, yield 31%, melting point: 68-69 o c. 1 H NMR (CDCl 3 , 400 MHz) ( δ , ppm) 1.28 (t, J = 7.1 Hz, 3H, CH 3 ), 1.29 (t, J = 7.1 Hz, 3H, CH 3 ), 2.32 (ddd, J = 14.2, 9.2, 8.0 Hz, 1H in CH 2 ), 2.40 (ddd, J = 14.2, 9.2, 5.6 Hz, 1H in CH 2 ), 3.34 (ddd, J = 10.1, 5.6, 0.9 Hz, 1H in CH 2 ), 3.50 (dd, J = 9.2, 5.6 Hz, 1H, CH), 3.76 (dd, J = 10.1, 7.2 Hz, 1H in CH 2 ), 3.86 (dddd, J = 9.2, 8.0, 5.6, 5.6 Hz, 1H, CH), 4.17-4.26 (m, 4H, 2CH 2 ), 6.23 (s, 1H, NH). 13 C NMR (CDCl 3 , 101 MHz) ( δ , ppm) 13.9, 14.0, 34.4, 44.4, 48.7, 49.8, 61.8, 61.9, 168.4, 168.5, 174.7.

Embodiment 3

[0058] Preparation of 5-(3-oxobutyl)thiazolidin-2-one 3c

[0059] According to the method described in Example 1, with dithiocarbonic acid O -Ethyl- S -(2-oxopropyl) ester and tert-butyl N-allyl carbamate were used as raw materials to obtain 5-(3-oxobutyl)thiazolidin-2-one, colorless oily liquid 125 mg, yield 54%. 1 H NMR (CDCl 3 , 400 MHz) ( δ , ppm) 1.98 (dddd, J = 14.4, 7.6, 7.6, 6.0 Hz, 1H in CH 2 ), 2.11 (dddd, J = 14.4, 9.6, 7.6, 6.0 Hz, 1H in CH 2 ), 2.17 (s, 3H, CH 3 ), 2.56 (ddd, J = 16.4, 7.6, 6.0 Hz, 1H in CH 2 ), 2.63 (ddd, J = 16.4, 7.6, 6.0 Hz, 1H in CH 2 ), 3.31 (ddd, J = 10.1, 5.2, 1.2 Hz, 1H, CH), 3.73 (ddd, J = 10.1, 5.2, 0.8 Hz, 1H in CH 2 ), 3.88 (dddd, J = 9.6, 7.6, 5.2, 5.2 Hz, 1H, CH), 6.16 (s, 1H, NH). 13C NMR (CDCl 3 , 101 MHz) ( δ , ppm) 29.1, 30.0, 40.7, 46.1, 48.8, 175.0, 207.1.

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Abstract

The invention provides a method for preparing 5-substituted-2-thiazolidinone. The method comprises the steps of carrying out a free radical addition reaction between O,S-dialkyl dithiocarbonate and N-allyl carbamic acid tert-butyl ester to obtain xanthogenate that contains urethane groups and preparing the 5-substituted-2-thiazolidinone through acid-catalyzed cyclization. The preparation method has the advantages of easily available raw materials and convenient operation, thereby being suitable for mass production. The obtained compounds may be used as important organic and medicament synthesis intermediates and the like.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a preparation method of 5-substituted 2-thiazolidinone. Background technique [0002] Thiazolidinone structures exist in many natural products and play an important role in medicine as well as modern organic synthetic chemistry. Compounds containing thiazolidinone structure have anticancer properties (Sonnenschein, R. N.; Johnson, T. A.; Tenney, K.; Valeriote, F. A.; Crews, P. J. Nat. Prod. 2006, 69 , 145; Amagata, T.; Johnson, T. A.; Cichewicz, R. H.; Tenney, K.; Mooberry, S. L.; Media, J.; Edelstein, M.; Valeriote, F. A.; Crews, P. J. Med. Chem. 2008, 51 , 7234.) and anti-HIV activity (Oiry, J.; Puy, J-Y.; Mialocq, P.; Clayette, P.; Fretier, P.; Jaccard, P.; Dereuddre-Bosquet, N.; Dormont, D. ; Imbach, J. L. J. Med. Chem. 1999, 42 , 4733.). It also has bactericidal, insecticidal, anti-inflammatory, anti-convulsant, and anti-thyroid effects (Singh...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D277/14
Inventor 许家喜黄忠衍
Owner BEIJING UNIV OF CHEM TECH