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1-halogenated-1, 4-diene nitrile and synthetic method thereof

A kind of diene nitrile and olefin technology, applied in the field of 1-halogenated-1,4-diene nitrile and its synthesis

Inactive Publication Date: 2018-07-27
HUAZHONG AGRICULTURAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] However, the synthesis method for 1-halo-1,4-dienenitriles with high selectivity Z / E stereoselectivity still needs to be studied and improved.

Method used

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  • 1-halogenated-1, 4-diene nitrile and synthetic method thereof
  • 1-halogenated-1, 4-diene nitrile and synthetic method thereof
  • 1-halogenated-1, 4-diene nitrile and synthetic method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] With phenylacetylene nitrile (1a) and 3-chloroprop-1-alkene (2a) as reactants, palladium compound (palladium acetate, palladium chloride) as catalyst, dichloroethane, acetic acid, acetic anhydride or dimethyl 1-halogeno-1,4-dienenitrile was obtained by addition reaction at a reaction temperature of 70°C using methyl formamide as a solvent; among them, aromatic cyanoalkyne, 3-chloroprop-1-alkene The reaction ratio of palladium compound and solvent is 0.25mmoL: 0.5mmoL: 0.0125mmoL: 2mL; the specific reaction chemical formula is as shown in formula 1, under the constant situation of reactant, change solvent kind and catalyst kind, obtain different chromatographic products The experimental data of the rate and the highly selective Z / E structure are shown in Table 1.

[0023]

[0024] The productive rate of table 1. embodiment 1 same reactant different solvent different catalysts and high selectivity Z / E formula structural data

[0025]

[0026] a Reaction conditions...

Embodiment 2

[0028] With aryl alkyne (1) and 3-chloroprop-1-alkene (2a) as reactant, add lithium chloride, take palladium compound (palladium acetate, palladium chloride) as catalyst, take acetic acid as solvent, in the reaction A highly selective Z-stereostructure 1-chloro-1,4-dienenitrile compound is obtained through an addition reaction at a temperature of 35°C; among them, alkylcyanoalkynes, 3-chloroprop-1-alkenes, The reaction ratio of lithium chloride, palladium compound and acetic acid is 0.5mmoL: 1.0mmoL: 1.0mmoL: 0.025mmoL: 2mL; the specific reaction chemical formula is shown in formula 2, and different kinds of alkylcyanoalkynes obtain different chromatographic yields. For the experimental data, see Table 2 for details.

Embodiment 3

[0030] With aryl alkyne (1) and 3-chloroprop-1-alkene (2a) as reactant, with palladium compound (palladium acetate, palladium chloride) as catalyst, with dichloroethane as solvent, at the reaction temperature of 1-Chloro-1,4-dienenitrile compounds with highly selective E-stereostructure are obtained by addition reaction at 70°C; among them, alkylcyanoalkynes, 3-chloroprop-1-alkenes, chlorinated The reaction ratio of lithium, palladium compound and acetic acid is 0.5mmoL: 1.0mmoL: 0.025mmoL: 2mL; the specific reaction chemical formula is shown in formula 2, different kinds of alkylcyanoalkynes get different chromatographic yield experimental data, see table for details 2.

[0031]

[0032] Table 2. The productive rate and highly selective Z / E formula structural data of embodiment 2 and implementation 3 different alkyl cyanoalkyne species

[0033]

[0034] Method A: formation of Z. Reaction conditions: 1(0.5mmol), 2a(1.0mmol), LiCl(1.0mmol) and [Pd](0.025mmol) in 2mL of H...

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Abstract

The invention discloses a 1-halogenated-1, 4-diene nitrile and a synthetic method thereof, and relates to the technical field of organic synthesis. The 1-halogenated-1, 4-diene nitrile is obtained bytaking cyan alkynes and allyl halides as reactants, taking palladium compounds as catalysts, taking the dichloroethane, acid substances or dimethyl formamide as solvents, and performing addition reaction at the reaction temperature of 35-70 DEG C. The 1-halogenated-1, 4-diene nitrile and the synthetic method thereof have the advantages through screening comparison between the two reactants, solvent comparison, catalyst comparison and reaction temperature comparison, synthetic conditions, such as the reactants, the catalysts, the solvents and the reaction temperatures, for high chromatography yield are determined; the synthetic conditions of the 1-halogenated-1, 4-diene nitrile with a high-selectivity Z / E formula structure are screened and determined through comparison; the chromatography yield is 65-95%, and can reach 85-95% optimally.

Description

technical field [0001] The invention relates to the technical field of organic synthesis, in particular to 1-halo-1,4-dienenitrile and a synthesis method thereof. Background technique [0002] Transition metal-catalyzed carbon-carbon or carbon-heteroatom bond formation is an important part of organic chemistry. In this regard, palladium-catalyzed reactions have been one of the hottest topics for decades. For example, a large number of palladium-catalyzed addition reactions have been reported in the prior art, including alkynol ethers, alkynyl halides, propargyl groups, thioalkynes, etc. In particular, Pd-catalyzed reactions with cyanoalkynes have also been reported. [0003] However, the synthesis method of 1-halo-1,4-dienenitrile with high selectivity Z / E stereoselectivity still needs to be studied and improved. Contents of the invention [0004] In view of this, the embodiment of the present invention provides a 1-halo-1,4-dienenitrile and its synthesis method, the ma...

Claims

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Application Information

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IPC IPC(8): C07C255/35C07C253/30
CPCC07C255/35C07C253/30
Inventor 石炜关志朋唐嘉浩陈浩
Owner HUAZHONG AGRICULTURAL UNIVERSITY
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