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A branched 1,4-dienamide derivative and its synthesis method

A technology of dienamide and synthesis method, applied in the directions of organic chemistry method, organic chemistry, etc., can solve the problems such as no report of the method, and achieve the effects of simple operation, mild reaction conditions and wide application range

Active Publication Date: 2021-01-26
HANGZHOU NORMAL UNIVERSITY
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] These literatures have synthesized a series of stereospecific 1,3- and 1,4-diene compounds, but they are limited to conjugated alkenyl amides and electron-deficient alkenes as substrates, and can only activate the ortho-position of the amide group. Alkenyl carbon-hydrogen bonds, resulting in linear coupling products
The alkenylation coupling reaction of non-conjugated alkenyl amides, the method of synthesizing amide-substituted branched conjugated diene derivatives has not been reported

Method used

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  • A branched 1,4-dienamide derivative and its synthesis method
  • A branched 1,4-dienamide derivative and its synthesis method
  • A branched 1,4-dienamide derivative and its synthesis method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0042] Preparation of (E)-4-benzylidene-N-(quinolin-8-yl)hept-6-enamide

[0043] A screw cap vial was charged with palladium acetate (4.5 mg, 0.02 mmol), dimethylsulfoxide (0.35 mL) and methanol (0.7 mL). Then, pivalic acid (20.4mg, 0.2mmol), (Z)-5-phenyl-N-(quinolin-8-yl)pent-4-enamide (30.2mg, 0.1mmol) and Allyl methyl carbonate (46.4 mg, 0.4 mmol). The vial was sealed under argon and heated to 40°C and stirred for 16 hours. After cooling, the mixture was directly applied to flash column chromatography (PE / EA=4 / 1), and the reaction solution was separated by direct column chromatography to obtain the target product as a white liquid (25.3 mg, yield 74%). The reaction formula is as follows:

[0044]

[0045] The nuclear magnetic spectrum characterization result of this reaction product is as follows: 1 H NMR (500MHz, CDCl 3 ): δ9.77(s,1H), 8.77–8.74(m,2H), 8.11(dd,J=8.5,2.0Hz,1H),7.52–7.45(m,2H),7.41(dd,J=8.5 ,4.0Hz,1H),7.30–7.24(m,4H),7.18–7.15(m,1H),6.39(s,1H),5.96–5...

Embodiment 2

[0048] Preparation of (E)-4-(4-fluorobenzylidene)-N-(quinolin-8-yl)hept-6-enamide

[0049] A screw cap vial was charged with palladium acetate (4.5 mg, 0.02 mmol), dimethylsulfoxide (0.35 mL) and methanol (0.7 mL). Then, pivalic acid (20.4 mg, 0.2 mmol), (Z)-5-(4-fluorophenyl)-N-(quinolin-8-yl)pent-4-enamide (32.0 mg , 0.1 mmol) and allyl methcarbonate (46.4 mg, 0.4 mmol). The vial was sealed under argon and heated to 40°C and stirred for 16 hours. After cooling, the mixture was directly applied to flash column chromatography (PE / EA=4 / 1), and the reaction solution was separated by direct column chromatography to obtain the target product yellow liquid (33.4 mg, yield 93%). The reaction formula is as follows:

[0050]

[0051] The nuclear magnetic spectrum characterization result of this reaction product is as follows: 1 H NMR (500MHz, CDCl 3 )δ9.76(s,1H),8.77–8.74(m,2H),8.13(dd,J=8.0,1.5Hz,1H),7.53–7.47(m,2H),7.43(dd,J=8.0, 4.0Hz, 1H), 7.20(q, J=5.5Hz, 2H), 6.96(t, J=9...

Embodiment 3

[0053] Preparation of (E)-4-(4-methoxybenzylidene)-N-(quinolin-8-yl)hept-6-enamide

[0054] A screw cap vial was charged with palladium acetate (4.5 mg, 0.02 mmol), dimethylsulfoxide (0.35 mL) and methanol (0.7 mL). Then, pivalic acid (20.4 mg, 0.2 mmol), (Z)-5-(4-methoxyphenyl)-N-(quinolin-8-yl)pent-4-enamide ( 33.2 mg, 0.1 mmol) and allyl methcarbonate (46.4 mg, 0.4 mmol). The vial was sealed under argon and heated to 40°C and stirred for 16 hours. After cooling, the mixture was directly applied to flash column chromatography (PE / EA=4 / 1). The reaction solution was separated by direct column chromatography to obtain a yellow liquid (28.0mg, yield 76%), the reaction formula is as follows:

[0055]

[0056] The nuclear magnetic spectrum characterization result of this reaction product is as follows:. 1 H NMR (500MHz, CDCl 3)δ9.79(s,1H),8.79–8.75(m,2H),8.15(dd,J=8.5,1.5Hz,1H),7.54–7.48(m,2H),7.44(dd,J=8.5, 4.5Hz, 1H), 7.20(d, J=9.0Hz, 2H), 6.84–6.82(m, 2H), 6.33(s, 1H),...

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Abstract

The invention discloses a branched 1,4-dienamide derivative as shown in formula (1) and a synthesis method thereof. The specific synthesis method is as follows: alkenyl quinoline amide compound, allyl methyl carbonate Derivatives, transition metal salt catalysts and additives are placed in an organic solvent, heated and reacted in an argon atmosphere, and after the reaction is completed, the reaction liquid is post-treated to obtain the branched 1,4-dienamide derivative. Under mild conditions, the present invention utilizes 8-aminoquinoline amide as the N,N-bicoordinated directing group, and uses allyl methyl carbonate as the alkenylation agent to efficiently realize the carbon at the same carbon position of the alkenyl group. Hydroalkenylation reaction, the products obtained are all brand-new compounds, the reaction substrates are widely applicable, the raw materials are economical and easy to obtain, no need for exogenous oxidants, the operation is simple, the highest yield can reach 93%, and it has broad application prospects and economical value.

Description

technical field [0001] The invention relates to the technical field of synthesis of non-conjugated diene compounds, in particular to a branched 1,4-dienamide derivative and a synthesis method thereof. Background technique [0002] As we all know, the diene structure is a common chemical structure, which widely exists in natural products and pharmaceutical bioactive molecules, such as risstatin, biserin and bilolide, etc. 1,4-Dienes are also widely used as ligands in transition metal-catalyzed reactions. A variety of methods for the preparation of 1,4-diene compounds have been reported, including: catalytic coupling reaction, ene reaction, alkenylation reaction and Morita–Baylis–Hillman (Morita-Baylis-Hillman) reaction, etc. With the depletion of energy and the increasingly severe environmental problems, it is particularly urgent to develop efficient and highly selective synthesis methods of 1,4-diene compounds. [0003] The direct hydrocarbon allylation reaction of alkenes...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D215/40C07D405/12C07D409/12C07D401/12C07B37/00
CPCC07B37/00C07D215/40C07D401/12C07D405/12C07D409/12
Inventor 钟国富张坚沈聪卢秀男丁丽媛
Owner HANGZHOU NORMAL UNIVERSITY
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