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A kind of preparation method of 2-carbamoyl-1,3-dicarbonyl derivative

A technology of carbamoyl and derivatives, which is applied in the field of preparation of organic compounds, can solve the problems of difficult to obtain raw materials, easy to react with water, and high toxicity of acid chlorides, and achieve short reaction time, simple post-treatment, and waste reduction. the effect produced

Active Publication Date: 2017-10-10
KUNSHAN KAIZHOU ENVIRONMENTAL PROTECTION MACHINERY CO LTD
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  • Abstract
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  • Claims
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AI Technical Summary

Problems solved by technology

[0008] The reported method requires three steps to obtain the key intermediate 2-carbamoyl-1,3-dicarbonyl derivatives for the synthesis of natural indolone alkaloids, and some raw materials are difficult to obtain, such as 3-chloro-3-oxo Ethyl propionate; the reaction conditions are relatively harsh, and two kinds of acid chlorides are needed. The acid chlorides are highly toxic and easy to react with water, so they are prone to smoke (hydrolysis) when exposed to the air, and NaH needs to be used as a base during the reaction, so Solvents and reactants must be anhydrous

Method used

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  • A kind of preparation method of 2-carbamoyl-1,3-dicarbonyl derivative
  • A kind of preparation method of 2-carbamoyl-1,3-dicarbonyl derivative
  • A kind of preparation method of 2-carbamoyl-1,3-dicarbonyl derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037] Example 1: Synthesis of 2-N,N-dimethylcarbamoyl-1,3-diphenyl-1,3-propanedione

[0038] Using 1,3-diphenyl-1,3-propanedione and N,N-dimethylformamide as raw materials, the reaction steps are as follows:

[0039] Add 1,3-diphenyl-1,3-propanedione (0.224 g, 1 mmol), N,N-dimethylformamide (2 mL), cuprous chloride (0.010 g, 0.1 mmol) and tert-butyl hydroperoxide (0.180 g, 2 mmol), react at 100°C;

[0040] TLC tracking reaction until complete completion;

[0041] The crude product obtained after the reaction was separated by column chromatography (petroleum ether: ethyl acetate = 4:1) to obtain the target product (yield 93%). The analytical data of the product are as follows: 1 H NMR (400 MHz, CDCl 3 ): δ 8.00 – 7.90 (m, 2H),7.74 – 7.66 (m, 2H), 7.56 – 7.48 (m, 1H), 7.47 – 7.38 (m, 5H), 7.15 (s, 1H),3.08 (s, 3H), 2.98 (s, 3H).

Embodiment 2

[0042] Example 2: Synthesis of 2-N,N-dimethylcarbamoyl-1-(4-methylphenyl)-3-phenyl-1,3-propanedione

[0043] Using 1-(4-methylphenyl)-3-phenyl-1,3-propanedione and N,N-dimethylformamide as raw materials, the reaction steps are as follows:

[0044] Add 1-(4-methylphenyl)-3-phenyl-1,3-propanedione (0.238 g, 1 mmol), N,N-dimethylformamide (2 ml), Copper chloride (0.013 g, 0.1 mmol) and tert-butyl hydroperoxide (0.180 g, 2 mmol) were reacted at 110°C;

[0045] TLC tracking reaction until complete completion;

[0046] The crude product obtained after the reaction was separated by column chromatography (petroleum ether: ethyl acetate = 4:1) to obtain the target product (yield 87%). The analytical data of the product are as follows: 1 H NMR (400 MHz, CDCl 3 ): δ 8.03 – 7.94 (m, 1H), 7.92 – 7.88 (m, 1H), 7.77 – 7.69 (m, 1H), 7.66 – 7.55 (m, 1H), 7.55 – 7.35 (m, 3H), 7.33 – 7.20 (m , 2H), 7.16 – 7.10 (m, 1H), 3.17 – 3.08 (m, 3H),3.04 – 2.98 (m, 3H), 2.43 – 2.32 (m, 3H).

Embodiment 3

[0047] Example 3: Synthesis of 2-N,N-dimethylcarbamoyl-1-(2-methylphenyl)-3-phenyl-1,3-propanedione

[0048] Using 1-(2-methylphenyl)-3-phenyl-1,3-propanedione and N,N-dimethylformamide as raw materials, the reaction steps are as follows:

[0049] Add 1-(2-methylphenyl)-3-phenyl-1,3-propanedione (0.238 g, 1 mmol), N,N-dimethylformamide (2 ml), Copper bromide (0.011 g, 0.05 mmol) and tert-butyl hydroperoxide (0.180 g, 2 mmol) were reacted at 120°C;

[0050] TLC tracking reaction until complete completion;

[0051] The crude product obtained after the reaction was separated by column chromatography (petroleum ether: ethyl acetate = 4:1) to obtain the target product (yield 77%). The analytical data of the product are as follows: 1 H NMR (400 MHz, CDCl 3 ): δ 8.05 – 7.92 (m, 1H), 7.77 – 7.63 (m, 1H), 7.59 – 7.22 (m, 7H), 6.83 – 6.56 (m, 1H), 3.21 – 2.80 (m, 6H), 2.60 – 2.51 (m , 3H).

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Abstract

The invention discloses a preparation method for a 2-amidoformyl-1,3-dicarbonyl derivative. A 1,3-dicarbonyl derivative is used as an initiator, and raw materials are easy to obtain and have multiple kinds. Products obtained through the method have multiple types, can be used directly and can also be used in other further reactions. Besides, the method includes a small number of steps, so that material consumption is reduced, unit operation is reduced, pollution is reduced, and production cost is lowered; moreover, reaction conditions are mild, reaction time is short, yield is high, reaction operation and aftertreatment processes are simple, and the method is suitable for industrial production.

Description

technical field [0001] The invention belongs to the technical field of preparation of organic compounds, and in particular relates to a preparation method of 2-carbamoyl-1,3-dicarbonyl derivatives. Background technique [0002] Indolinone alkaloids are an important class of natural products with important physiological activities. Coerulescine, horsfiline, CRTH2 (DP2) and CPC-1 are four important compounds in this family, which can be used as drug intermediates, starting materials for pesticide synthesis, etc. (see: Galliford, C. V.; Scheidt, K. A. Angew. Chem. Int. Ed. 2007, 46, 8748-8758; Zhou, F.; Liu, Y.-L.; Zhou, J. Adv. Synth. Catal.2010, 352, 1381-1407); its structure is as follows: [0003] [0004] It has been reported in the literature that these four natural products can be synthesized from 2-carbamoyl-1,3-dicarbonyl derivatives. The routes of compounds Coerulescine and horsfiline are as follows (see: Lv, J.-L.; Zhang-Negrerie, D.; Deng, J.; Du, Y.-F.; Zhao, ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C231/10C07C235/80C07C235/82C07D333/24C07D295/192
CPCC07C231/10C07D295/192C07D333/24C07C235/80C07C235/82
Inventor 邹建平周少方张令张沛之
Owner KUNSHAN KAIZHOU ENVIRONMENTAL PROTECTION MACHINERY CO LTD
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