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A kind of preparation method of 7,8-dihydroquinoline-2,5(1h,6h)-dione derivatives

A technology for dihydroquinoline and derivatives, applied in 7 fields, can solve the problems of expensive catalyst, harsh reaction conditions, low reaction yield, etc., and achieve the effects of large implementation value, easy availability of raw materials, and simple post-processing

Inactive Publication Date: 2011-12-21
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

There are certain limitations in the above-mentioned several methods, which are mainly reflected in the low reaction yield, relatively harsh reaction conditions, expensive catalysts, and relatively large environmental pollution.

Method used

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  • A kind of preparation method of 7,8-dihydroquinoline-2,5(1h,6h)-dione derivatives
  • A kind of preparation method of 7,8-dihydroquinoline-2,5(1h,6h)-dione derivatives
  • A kind of preparation method of 7,8-dihydroquinoline-2,5(1h,6h)-dione derivatives

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Example 1 1-phenyl-7,7-dimethyl-3-(3-nitrophenyl)-7,8-dihydroquinoline-2,5(1H,6H)-dione (compound a ) preparation

[0026] In a 250mL three-necked flask equipped with a thermometer, a reflux condenser, and mechanical stirring, add 11.16g (40mmol) of 2-(acetoxy-(3-nitrophenyl))methyl methacrylate, 5,5-di Methyl-1,3-cyclohexanedione 5.60g (40mmol), potassium carbonate 2.76g (20mmol), acetone 33.48g, stirred at 56°C for 4h, then added aniline 3.72g (40mmol), continued the reaction for 2h. The solvent was recovered under reduced pressure, and the resulting crude product was recrystallized from 95% ethanol to obtain 7.20 g of 1-phenyl-7,7-dimethyl-3-(3-nitrophenyl)-7,8-dihydroquinoline- 2,5(1H,6H)-diketone, off-white crystal, the yield is 44.8%, the melting point is 175.0-177.3°C, and the HPLC purity is 98.6%. 1 H NMR (500MHz, CDCl 3 ): δ=1.01(s, 6H, CH 3 ), 2.29 (s, 2H, CH 2 ), 2.38(s, 2H, CH 2 ), 3.94 (s, 2H, CH 2 ), 7.16(t, J=7.5Hz, 2H, ArH), 7.44(t, J=8.0Hz, 1H, A...

Embodiment 2

[0027] Example 2 1-phenyl-7,7-dimethyl-3-(3-nitrophenyl)-7,8-dihydroquinoline-2,5(1H,6H)-dione (compound a ) preparation

[0028]The feed ratio is Baylis-Hillman adduct: 5,5-dimethyl-1,3-cyclohexanedione: base catalyst: aniline=1:1:1:2, wherein Baylis-Hillman adduct is 2- (Acetoxy-(3-nitrophenyl))methyl methacrylate 11.16g (40mmol), the base is potassium carbonate, the solvent is acetone, the amount is 4 times the amount of the Baylis-Hillman adduct, at 56 ° C Under the first stage of reaction for 8h, the second stage of reaction for 3h.

[0029] Others are the same as Example 1, and the product is 1-phenyl-7,7-dimethyl-3-(3-nitrophenyl)-7,8-dihydroquinoline-2,5(1H,6H)- 13.20 g of diketone, off-white crystals, the yield is 82.1%, the melting point is 175.6-177.5°C, and the HPLC purity is 98.4%.

Embodiment 3

[0030] Example 3 1-phenyl-7,7-dimethyl-3-(3-nitrophenyl)-7,8-dihydroquinoline-2,5(1H,6H)-dione (compound a ) preparation

[0031] The feed ratio is Baylis-Hillman adduct: 5,5-dimethyl-1,3-cyclohexanedione: base catalyst: aniline=1: 1.2: 1.2: 3, wherein Baylis-Hillman adduct is 2- (Acetoxy group-(3-nitrophenyl)) methyl methacrylate 11.16g (40mmol), base is triethylenediamine, solvent is acetonitrile, consumption is 8 times of Baylis-Hillman adduct quality, in At 80°C, the first stage was reacted for 5 hours, and the second stage was reacted for 2 hours.

[0032] Others are the same as Example 1, and the product is 1-phenyl-7,7-dimethyl-3-(3-nitrophenyl)-7,8-dihydroquinoline-2,5(1H,6H)- Diketone 13.44g, off-white crystal, yield 83.6%, melting point 175.3-177.0°C, HPLC purity 98.9%.

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Abstract

The invention discloses a preparation method of a 7,8-dihydroquinoline-2,5(1H,6H)-dione derivative represented by formula (I), the preparation method comprising the following steps: as shown in formula (I) The Baylis-Hillman adduct represented by (II) reacts with 1,3-cyclohexanedione represented by formula (III) or 1,3-cyclohexanedione represented by formula (III) under the action of a base catalyst at 0~100°C in an organic solvent or under solvent-free conditions. The derivative is reacted for 1-12 hours, then primary amine is added to react at 0-100° C. for 1-8 hours, and the compound of formula (I) can be obtained after post-treatment. Compared with the prior art, the present invention is mainly embodied in easy availability of raw materials, simple and convenient operation, mild reaction conditions, high reaction yield, good atom economy, and low environmental pollution, so it has greater practical value and potential social and economic benefits.

Description

(1) Technical field [0001] The invention relates to a preparation method of 7,8-dihydroquinoline-2,5(1H,6H)-dione derivatives. (2) Background technology [0002] 7,8-Dihydroquinoline-2,5(1H,6H)-dione derivatives are an important class of heterocyclic compounds that widely exist in natural products and show good physiological activities, such as anticancer , antibacterial, cardiotonic, etc., are widely used in medicine and pesticides. [0003] Before the present invention was made, the methods for synthesizing 7,8-dihydroquinoline-2,5(1H,6H)-diketone derivatives in the prior art were: (1) methyl propiolate or ethyl ester Cyclization with 3-aminocyclohex-2-enone derivatives [(a) Ruda, M.C. et al., Heterocycl. Commun. 2003, 9, 571. (b) Pettit, G R. et al., J.Org.Chem.1968, 33, 1089. (c) Aigars, J.R.et al., US 2006004001.]; (2) 2-phenylmalonate derivatives and 3-aminocyclohex-2-ene Ketone derivatives were obtained by cyclization under microwave irradiation at 250°C [Rivkin, A...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D215/227
Inventor 钟为慧苏为科林福亮
Owner ZHEJIANG UNIV OF TECH
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