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Method for preparing 1,6-adipaldehyde through selective oxidation of cyclohexene

A technology of adipaldehyde and cyclohexene, applied in the field of selective oxidation of cyclohexene to prepare 1,6-adipaldehyde, which can solve the problems of poor selectivity and achieve the effects of environmental friendliness, high reactivity and good selectivity

Active Publication Date: 2019-02-22
ZHENGZHOU UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0006] Literature Li G. et al. (Journal of Molecular Catalysis A: Chemical, 194(1-2), 169-180; 2003), Jpn. Kokai Tokkyo Koho 2005170856 used oxygen as an oxidant to oxidize cyclohexene to obtain 1,6-hex Mixture of dialdehydes, epoxides of cyclohexene, 1,6-adipic acid, etc., poor selectivity

Method used

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  • Method for preparing 1,6-adipaldehyde through selective oxidation of cyclohexene

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Embodiment 1

[0022] Synthesis of isosterveol derivative amino alcohols: Isosterveol derivative amino alcohols were synthesized according to the literature (Lai Hongtao, Synthesis of novel diamine chiral ligands and their application in asymmetric organic catalysis Research, 2016, Master Thesis of Zhengzhou University).

[0023] Synthesis of isosterveol derivative aminoalcohol glyoxal condensate: Add 20mL methanol and 7.5g (0.02mol) isosterveol derivative aminoalcohol into a 100mL three-neck flask, stir and drop glyoxal 1.5 g (0.01 mol), stirred at room temperature for 8 hours, the precipitate was suction-filtered, washed with methanol, and dried in vacuum at 50°C to obtain 5.8 g of isosteviol derivative amino alcohol glyoxal condensate, yield 75.1%. Its structural formula is:

[0024] ;

[0025] 1H NMR (400 MHz, CDCl 3 , TMS): δ7.5 (d, 2H), 4.06–4.11 (m, 4H), 3.82 (d,2H),, 3.33 (m, 4H), 3.04 (d, 2H), 2.49 (s, 2H) , 2.15 (d, 2H), 1.42–1.83(m,18H), 1.83–1.09 (m, 14H) , 1.27 (s, 6H), 1....

Embodiment 2

[0031] Add 8.2 g (0.1 mol) cyclohexene, 0.95 g (0.001 mol) cobalt complex of isosteviol derivatives, 20 mL tetrahydrofuran, 12.9 g (0.1 mol) tert-butanol peroxide into the autoclave, and feed oxygen Until the pressure of the reactor is 0.4 MPa, the reaction temperature is 160° C., and the reaction time is 180 minutes. The specific reaction results are shown in Table 1.

[0032] 1,6-Hexanal (C 6 h 10 o 2 ): 1H NMR (400 MHz, CDCl 3 , TMS): δ9.7 (t,2H), 2.4 (m,4H), 1.6 (m, 4H); GC-MS: [M] + 114, [M-29] + 85.

Embodiment 3

[0034] Add 8.2 g (0.1 mol) of cyclohexene, 0.94 g (0.001 mol) of manganese complex of isosteviol derivatives, 20 mL of tetrahydrofuran, 12.9 g (0.1 mol) of tert-butanol peroxide into the autoclave, and feed oxygen The pressure of the reactor was 0.4MPa, the reaction temperature was 160°C, and the reaction time was 180 minutes. The specific reaction results are shown in Table 1.

[0035] 1,6-Hexanal (C 6 h 10 o 2 ): 1H NMR (400 MHz, CDCl 3 , TMS): δ9.7 (t,2H), 2.4 (m,4H), 1.6 (m, 4H); GC-MS: [M] + 114, [M-29] + 85.

[0036] 1,6-Hexanedioic acid (C 6 h 10 o 4 ): Mp 151.2~152.3℃; 1H NMR (400 MHz, CDCl3, TMS): δ2.2 (t, 4H), 1.6 (m, 4H).

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Abstract

The invention discloses a method for preparing 1,6-adipaldehyde through selective oxidation of cyclohexene. A catalyst is a cobalt complex of an isosteviol derivative. The method comprises the steps as follows: adding a solvent, cyclohexene, a catalyst and a cocatalyst to a reaction kettle, introducing oxygen, keeping the pressure of the reaction kettle at 0.2-0.6 MPa, and conducting a reaction atthe temperature of 120-170 DEG C for 60-300 min to obtain 1,6-adipaldehyde. Compared with existing methods, the method has the advantages that free radicals produced through decomposition of the cocatalyst tert-butyl hydroperoxide act with oxygen to produce oxygen radicals, the catalyst cobalt complex of the isosteviol derivative acts with double bonds in cyclohexene, so that the reaction activity is higher, and activated double bonds and free radicals react to produce 1,6-adipaldehyde. The method is environmentally friendly, and 1,6-adipaldehyde is good in selectivity and high in yield.

Description

technical field [0001] The invention belongs to the field of chemical material intermediates, and in particular relates to a method for preparing 1,6-hexanedial by selective oxidation of cyclohexene. Background technique [0002] 1,6-Adipaldehyde is an important fine chemical product. 1,6-Adipaldehyde has a good leather tanning effect and is widely used in the leather industry; 1,6-Adipaldehyde is also a quick-acting broad-spectrum chemical sterilizer, and does not corrode metal appliances, glass and plastic products, and is used in Disinfection and sterilization of medical equipment, food utensils, etc. 1,6-Hexandial can be obtained from cyclohexene by ozone oxidation followed by reductive hydrolysis, or directly obtained by ozone oxidation in acetic acid in the presence of tetracyanoethylene. However, a large amount of toxic substances are used in large-scale industrial production, which seriously pollutes the environment. Therefore, it is necessary to develop a new gree...

Claims

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Application Information

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IPC IPC(8): C07C45/34C07C47/12B01J31/22
CPCB01J31/2217B01J2531/845C07C45/34C07C47/12
Inventor 李瑞军冯冰冰刑程翔贾龙飞李杰
Owner ZHENGZHOU UNIV
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