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Method of synthesizing hexa-2,4-dienedinitrile from 1,4-dihalogen-1,3-butadiene and cuprous cyanide

A technology of hexadiene dinitrile and cuprous cyanide, which is applied in cyanide reaction preparation, organic chemistry and other directions, can solve the problem of low reaction selectivity, achieve high separation yield, easy availability of raw materials, experimental equipment and operation Simple and easy effects

Inactive Publication Date: 2009-06-24
厦门康奥克科技有限公司
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Problems solved by technology

[0002] 2,4-Hexadiene dinitrile derivatives with various substituents are important organic synthesis intermediates, which can be used to construct carbocycles, heterocycles, and functionalized nitriles through conjugate addition reactions. It is also the precursor compound of very useful nylon monomers. The existing literature and patents can only synthesize several hexadiene dinitrile products with specific substituents, including obtaining such as compound (1 ) of adiene dinitrile (Tetrahedron Letters, 44 (7), 1333-1337; 2003.), obtained compound (2) and compound (3) (Ger.Offen., 19543862, 28 May.) by ring opening of toluenediamine 1997), obtain compound (4) (PCT Int.Appl., 9701531, 16 Jan 1997; Jpn.KokaiTokkyo Koho, 06279387, 04 Oct 1994, Heisei) etc. by ethylene nitrile, but the type of compound synthesized by these methods has great limitation and the reaction selectivity is not high, and other by-products are generated, so there is no general synthetic method for 2,4-hexadiene dinitrile derivatives with various substituents

Method used

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  • Method of synthesizing hexa-2,4-dienedinitrile from 1,4-dihalogen-1,3-butadiene and cuprous cyanide
  • Method of synthesizing hexa-2,4-dienedinitrile from 1,4-dihalogen-1,3-butadiene and cuprous cyanide
  • Method of synthesizing hexa-2,4-dienedinitrile from 1,4-dihalogen-1,3-butadiene and cuprous cyanide

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] One of the compounds of class I in the structural formula (R 1 =R 2 =R 3 =R 4 =n-Pr): Synthesis of 2,3,4,5-tetrapropyl-2,4-hexadienedionitrile:

[0026] To a 20mL round-bottomed flask, add 1mmol of 5,6-dipropyl-4,7-diiodo-4,6-decadiene and 2.5mmol of cuprous cyanide, add 5mL of DMF solvent, heat to reflux, and magnetically stir the reaction six hours. After the reaction, it was concentrated, decolorized and separated on a silica gel column, and the mixed solvent of petroleum ether:diethyl ether=10:1 was used as the eluent to obtain the pure product 2,3,4,5-tetrapropyl-2,4-hexadienedionitrile 0.248 g (purity >98%, colorless liquid), isolated yield 91%. The NMR and high-resolution mass spectrometry data of this compound are as follows: 1 H NMR (300MHz, CDCl 3 ): δ 0.96-1.03(m, 12H), 1.42-1.49(m, 4H), 1.61-1.73(m, 4H), 2.28-2.33(m, 8H). 13 C NMR (75MHz, CDCl 3 ): delta 13.02, 13.85, 20.59, 20.9231.47, 32.51, 114.27, 118.09, 155.70. HRMS: calcd for C 18 H 28 N 2...

Embodiment 2

[0028] The second compound of class I in the structural formula (R 1 =R 2 =n-Et, R 3 =R 4 =Ph): Synthesis of 2,3-diethyl-4,5-diphenyl-2,4-hexadienedionitrile

[0029] The synthetic route is basically the same as above. The starting material dihalogen compound of this synthesis is 3-ethyl-1,2-diphenyl-1,4-diiodo-1,3-hexadiene. 0.300 g of pure product (purity >98%, colorless solid, melting point: 105-106° C.) was obtained in 96% isolated yield. The NMR, high-resolution mass spectrometry and elemental analysis data of this compound are as follows: 1 H NMR (300MHz, CDCl 3 ): δ 1.09(t, J=7.5Hz, 3H), 1.34(t, J=7.5Hz, 3H), 2.26(br, 2H), 2.50(q, J=7.5Hz, 2H), 7.06-7.31( m, 10H). 13 C NMR (75MHz, CDCl 3 ): delta 12.06, 12.52, 23.65, 24.28, 115.88, 117.28, 118.38, 118.53, 128.64, 128.78, 129.03, 129.38, 129.65, 129.80, 133.15, 134.42, 154.83, 156.72 22 H 20 N 2 312.1627, found 312.1617.Anal.Calcd for C 22 H 20 N 2 : C, 84.64; H, 6.54, N, 8.97. Found: C, 84.58; H, 6.45, N...

Embodiment 3

[0031] The third compound of class I in the structural formula (R 1 =R 4 =n-Bu,R 2 =R 3 =H): Synthesis of 2,5-dibutyl-2,4-hexadienedionitrile

[0032] The synthetic route is basically the same as above. The starting material dihalogen compound of this synthesis is 5,8-dibromo-5,7-dodecadiene. The pure product 0.182 g (purity >98%, colorless liquid) was obtained in 84% isolated yield. The NMR and high-resolution mass spectrometry data of this compound are as follows: 1 HNMR (300MHz, CDCl 3 ): δ 0.95(t, J=7.5Hz, 6H), 1.31-1.44(m, 4H), 1.54-1.64(m, 4H), 2.36(t, J=7.5Hz, 4H), 6.97(s, 2H) ). 13 C NMR (75MHz, CDCl 3 ): δ 13.68, 21.92, 30.06, 34.37, 116.74, 120.60, 138.42. HRMS: calcd for C 14 H 20 N 2 216.1627, found 216.1625.

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Abstract

The invention provides a general method for synthesizing 2,4-hexadiene dinitrile derivatives with various substituents: first, 1,4-dihalo-1,3-butadiene derivatives and cyanide Copper is mixed, and N, N-dimethylformamide solvent is added to reflux, and the reaction product is concentrated and purified to obtain 2,4-hexadiene dinitrile derivatives. The synthesis method of the present invention adopts the oxidation addition / reduction elimination reaction of a continuous organohalogen reagent to cuprous cyanide, which is scientific and reasonable, the raw materials are easy to obtain, the application range is wide, the separation yield is high, the experimental equipment and operation are simple and easy, Easy to industrialize.

Description

technical field [0001] The invention relates to a general method for synthesizing 2,4-hexadienedionitrile derivatives with various substituents, and belongs to the field of organic synthesis intermediates and new functional material synthesis. Background technique [0002] 2,4-hexadiene dinitrile derivatives with various substituents are important intermediates in organic synthesis, which can be used to construct carbocycles, heterocycles, and functionalized nitrile by conjugated addition reactions. It is also a very useful precursor compound of nylon monomers. The existing literature and patents can only synthesize several hexadiene dinitrile products with specific substituents, including compounds such as compounds (1 ) of hexadiene dinitrile (Tetrahedron Letters, 44(7), 1333-1337; 2003.), compound (2) and compound (3) were obtained by ring-opening of toluene diamine (Ger. Offen., 19543862, 28 May 1997), obtained compound (4) from vinyl nitrile (PCT Int.Appl., 9701531, 16...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C253/14C07C255/00
Inventor 席振峰王从洋
Owner 厦门康奥克科技有限公司
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