CN109369356B - Method for preparing 1, 6-hexanedial by selectively oxidizing cyclohexene - Google Patents

Method for preparing 1, 6-hexanedial by selectively oxidizing cyclohexene Download PDF

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CN109369356B
CN109369356B CN201811632646.6A CN201811632646A CN109369356B CN 109369356 B CN109369356 B CN 109369356B CN 201811632646 A CN201811632646 A CN 201811632646A CN 109369356 B CN109369356 B CN 109369356B
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hexanedial
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CN109369356A (en
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李瑞军
冯冰冰
刑程翔
贾龙飞
李�杰
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Zhengzhou University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt

Abstract

The invention discloses a method for preparing 1, 6-hexanedial by selectively oxidizing cyclohexene, wherein a catalyst is a cobalt complex of an isosteryl alcohol derivative, and the method comprises the following steps: adding a solvent, cyclohexene, a catalyst and a cocatalyst into a reaction kettle, introducing oxygen, keeping the pressure of the reaction kettle at 0.2-0.6 MPa, the reaction temperature at 120-170 ℃, and the reaction time at 60-300 minutes to obtain the 1, 6-hexanedial. Compared with the prior art, the invention has the advantages that free radicals generated by the decomposition of tert-butyl peroxide serving as a cocatalyst react with oxygen to generate oxygen radicals, the cobalt complex serving as the catalyst of the isosteviol derivative reacts with double bonds in cyclohexene to enable the isosteviol derivative to have higher reaction activity, and the activated double bonds react with the oxygen radicals to generate 1, 6-hexanedial; the method is environment-friendly, and the 1, 6-hexanedial has good selectivity and high yield.

Description

Method for preparing 1, 6-hexanedial by selectively oxidizing cyclohexene
Technical Field
The invention belongs to the field of chemical material intermediates, and particularly relates to a method for preparing 1, 6-hexanedial by selectively oxidizing cyclohexene.
Background
1, 6-hexanedial is an important fine chemical product. The leather tanning function of the 1, 6-hexanedial is good, and the tanning agent is widely used in the leather industry; the 1, 6-hexanedial is also a quick-acting broad-spectrum chemical sterilizing agent, does not corrode metal instruments, glass and plastic products, and is used for sterilizing medical instruments, food appliances and the like. The 1, 6-hexanedial can be obtained by oxidizing cyclohexene with ozone and then reducing and hydrolyzing, or directly obtained by oxidizing with ozone in acetic acid in the presence of tetracyanoethylene. However, since a large amount of toxic substances are used in large-scale industrial production and the environment is seriously polluted, it is required to develop a new green oxidation process for preparing 1, 6-hexanedial from the viewpoints of economy, environmental protection and sustainable development.
Documents Hodgson, Gregory K et al, (ACS Catalysis, 8, 2914-.
The documents Schottenheim Julia et al (European Journal of organic Chemistry, 21, 3501-.
The documents Manikandan T.S. et al, (RSC Advances, 6, 97107-.
Documents Li G. et al (Journal of Molecular Catalysis A: Chemical, 194(1-2), 169-.
In recent years, the use of oxygen as a clean oxidant has become a focus of research, as oxygen is the most abundant, inexpensive and environmentally friendly oxidant available. In the field of selective oxidation of cyclohexene to 1, 6-hexanedial, it is of great importance to develop new efficient, highly selective direct oxygen oxidation systems.
Disclosure of Invention
The invention aims to provide a method for preparing 1, 6-hexanedial by selectively oxidizing cyclohexene.
In order to achieve the purpose, the invention adopts the technical scheme that the method for preparing the 1, 6-hexanedial by selectively oxidizing cyclohexene comprises the following steps: adding a solvent, cyclohexene, a catalyst and a cocatalyst into a reaction kettle, introducing oxygen, keeping the pressure of the reaction kettle at 0.2-0.6 MPa, the reaction temperature at 120-170 ℃, and the reaction time at 60-300 minutes to obtain 1, 6-hexanedial; the catalyst is a cobalt complex of an isosterviol derivative, and the structural formula of the catalyst is as follows:
Figure 471096DEST_PATH_IMAGE001
。
preferably, the preparation method of the cobalt complex of the isostaviol derivative is as follows:
(1) adding 7.5g of isotretinoin derivative amino alcohol into a 100mL three-necked bottle, adding 20mL of methanol, stirring and dropwise adding 1.5g of glyoxal, stirring for 8 hours at room temperature, filtering the precipitate, washing with methanol, and drying in vacuum at 50 ℃ to obtain an intermediate product, namely, an isotretinoin derivative amino alcohol glyoxal condensation product; the structural formula of the isosteviol derivative aminoalcohol is:
Figure 201286DEST_PATH_IMAGE002
；
the structural formula of the isotretinol derivative amino alcohol glyoxal condensation product is:
Figure 981023DEST_PATH_IMAGE003
；
(2) and adding 40 mL of methanol, 11.6g of the intermediate product isosteviol derivative amino alcohol glyoxal condensation compound and 3.7g of cobalt acetate tetrahydrate into a 100mL three-necked bottle, carrying out reflux reaction for 10 hours under the protection of nitrogen, cooling, carrying out suction filtration, washing with methanol, and carrying out vacuum drying at 50 ℃ to obtain the cobalt complex of the isosteviol derivative.
Preferably, the cocatalyst is tert-butyl peroxide.
Preferably, the solvent is ethyl acetate or tetrahydrofuran.
Preferably, the molar ratio of the catalyst to the cyclohexene is 0.01-0.03: 1, and the molar ratio of the cocatalyst to the cyclohexene is 0.8-1.5: 1.
The invention has the following beneficial effects: the free radical generated by the decomposition of the tert-butyl peroxide as the cocatalyst reacts with oxygen to generate oxygen free radical, the cobalt complex of the isosteviol derivative as the catalyst reacts with the double bond in the cyclohexene to enable the isosteviol derivative to have higher reaction activity, and the activated double bond reacts with the oxygen free radical to generate 1, 6-hexanedial; the method for preparing the 1, 6-hexanedial by selectively oxidizing the cyclohexene is environment-friendly, and the 1, 6-hexanedial has good selectivity and high yield.
Detailed Description
The invention is further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1
Synthesis of isosteviol derivative aminoalcohol: the isosteviol derivative, aminoalcohol, was synthesized according to literature (seiko, synthesis of novel diamine chiral ligands and their use in asymmetric organocatalysis, 2016, master paper of zheng state university).
Synthesis of isosteviol derivative aminyl alcohol glyoxal condensate: 20mL of methanol and 7.5g (0.02mol) of an isosteviol derivative amino alcohol were added to a 100mL three-necked flask, 1.5g (0.01mol) of glyoxal was dropped under stirring, the mixture was stirred at room temperature for 8 hours, and the precipitate was filtered under suction, washed with methanol, and vacuum-dried at 50 ℃ to obtain 5.8g of an isosteviol derivative amino alcohol glyoxal condensate with a yield of 75.1%. The structural formula is as follows:
Figure 438549DEST_PATH_IMAGE004
；
1H NMR (400 MHz, CDCl3, 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), 1.16 (s, 6H), 0.91 (m, 6H), 0.79 (s, 6H)。
synthesis of cobalt complexes of isosteviol derivatives: 40 mL of methanol, 11.6g (0.015mol) of isotretinol derivative amino alcohol glyoxal condensate and 3.7g (0.015mol) of cobalt acetate tetrahydrate are added into a 100mL three-necked bottle, reflux reaction is carried out for 10 hours under the protection of nitrogen, cooling, suction filtration, methanol washing and vacuum drying at 50 ℃ are carried out, 9.9g of isotretinol derivative cobalt complex is obtained, and the yield is 69.3%. The structural formula is as follows:
Figure 252922DEST_PATH_IMAGE005
。
synthesis of manganese complexes of isosteviol derivatives: 40 mL of methanol, 7.7g (0.01mol) of isotretinol derivative amino alcohol glyoxal condensate and 2.7g (0.01mol) of manganese acetate dihydrate are added into a 100mL three-necked flask, reflux reaction is carried out for 10 hours under the protection of nitrogen, cooling, suction filtration and methanol washing are carried out, and the solid is dried in vacuum at 50 ℃ to obtain 7.1g of manganese complex of isotretinol derivative, wherein the yield is 74.7%. The structural formula is as follows:
Figure 75384DEST_PATH_IMAGE006
。
example 2
8.2 g (0.1 mol) of cyclohexene, 0.95 g (0.001 mol) of cobalt complex of isosbestol derivative, 20mL of tetrahydrofuran and 12.9 g (0.1 mol) of tert-butyl peroxide are added into an autoclave, oxygen is introduced until the pressure of the autoclave reaches 0.4MPa, the reaction temperature is 160 ℃, the reaction time is 180 minutes, and the specific reaction results are shown in the table I.
1, 6-hexanedial (C)6H10O2）：1H NMR (400 MHz, CDCl3, TMS): δ9.7 (t,2H), 2.4 (m, 4H), 1.6 (m, 4H)；GC-MS: [M]+ 114, [M-29]+ 85。
Example 3
8.2 g (0.1 mol) of cyclohexene, 0.94 g (0.001 mol) of manganese complex of isoversol derivative, 20mL of tetrahydrofuran and 12.9 g (0.1 mol) of tert-butyl peroxide are added into an autoclave, oxygen is introduced until the pressure of the autoclave reaches 0.4MPa, the reaction temperature is 160 ℃, the reaction time is 180 minutes, and the specific reaction results are shown in the table I.
1, 6-hexaneDialdehyde (C)6H10O2）：1H NMR (400 MHz, CDCl3, TMS): δ9.7 (t,2H), 2.4 (m, 4H), 1.6 (m, 4H)；GC-MS: [M]+ 114, [M-29]+ 85。
1, 6-adipic acid (C)6H10O4）：Mp 151.2~152.3℃；1H NMR (400 MHz, CDCl3, TMS): δ2.2 (t, 4H), 1.6 (m, 4H)。
Example 4
8.2 g (0.1 mol) of cyclohexene, 0.25 g (0.001 mol) of cobalt acetate tetrahydrate, 20mL of tetrahydrofuran and 12.9 g (0.1 mol) of tert-butyl peroxide are added into the autoclave, oxygen is introduced until the pressure of the autoclave reaches 0.4MPa, the reaction temperature is 160 ℃, the reaction time is 180 minutes, and the specific reaction result is shown in Table I.
1, 6-hexanedial (C)6H10O2）：1H NMR (400 MHz, CDCl3, TMS): δ9.7 (t,2H), 2.4 (m, 4H), 1.6 (m, 4H)；GC-MS: [M]+ 114, [M-29]+ 85。
1, 6-adipic acid (C)6H10O4）：Mp 151.2~152.3℃；1H NMR (400 MHz, CDCl3, TMS): δ2.2 (t, 4H), 1.6 (m, 4H)。
Example 5
8.2 g (0.1 mol) of cyclohexene, 0.95 g (0.001 mol) of cobalt complex of isosbestol derivative, 20mL of tetrahydrofuran and 12.9 g (0.1 mol) of tert-butyl peroxide are added into an autoclave, oxygen is introduced until the pressure of the autoclave reaches 0.5MPa, the reaction temperature is 120 ℃, the reaction time is 240 minutes, and the specific reaction results are shown in Table I.
1, 6-hexanedial (C)6H10O2）：1H NMR (400 MHz, CDCl3, TMS): δ9.7 (t,2H), 2.4 (m, 4H), 1.6 (m, 4H)；GC-MS: [M]+ 114, [M-29]+ 85。
Example 6
12.3 g (0.15 mol) of cyclohexene, 1.4 g (0.0015 mol) of cobalt complex of isosbestol derivative, 20mL of tetrahydrofuran and 19.3 g (0.15 mol) of tert-butyl peroxide are added into an autoclave, oxygen is introduced until the pressure of the autoclave reaches 0.5MPa, the reaction temperature is 140 ℃, the reaction time is 240 minutes, and the specific reaction results are shown in Table I.
1, 6-hexanedial (C)6H10O2）：1H NMR (400 MHz, CDCl3, TMS): δ9.7 (t,2H), 2.4 (m, 4H), 1.6 (m, 4H)；GC-MS: [M]+ 114, [M-29]+ 85。
Example 7
12.3 g (0.15 mol) of cyclohexene, 1.4 g (0.0015 mol) of cobalt complex of isosbestol derivative, 20mL of tetrahydrofuran and 19.3 g (0.15 mol) of tert-butyl peroxide are added into an autoclave, oxygen is introduced until the pressure of the autoclave reaches 0.5MPa, the reaction temperature is 170 ℃, the reaction time is 240 minutes, and the specific reaction results are shown in Table I.
1, 6-hexanedial (C)6H10O2）：1H NMR (400 MHz, CDCl3, TMS): δ9.7 (t,2H), 2.4 (m, 4H), 1.6 (m, 4H)；GC-MS: [M]+ 114, [M-29]+ 85。
1, 6-adipic acid (C)6H10O4）：Mp 151.2~152.3℃；1H NMR (400 MHz, CDCl3, TMS): δ2.2 (t, 4H), 1.6 (m, 4H)。
Example 8
12.3 g (0.15 mol) of cyclohexene, 1.4 g (0.0015 mol) of cobalt complex of isosbestol derivative, 20mL of tetrahydrofuran and 19.3 g (0.15 mol) of tert-butyl peroxide are added into an autoclave, oxygen is introduced until the pressure of the autoclave reaches 0.4MPa, the reaction temperature is 160 ℃, the reaction time is 60 minutes, and the specific reaction results are shown in Table I.
1, 6-hexanedial (C)6H10O2）：1H NMR (400 MHz, CDCl3, TMS): δ9.7 (t,2H), 2.4 (m, 4H), 1.6 (m, 4H)；GC-MS: [M]+ 114, [M-29]+ 85。
Example 9
12.3 g (0.15 mol) of cyclohexene, 1.4 g (0.0015 mol) of cobalt complex of isosbestol derivative, 20mL of tetrahydrofuran and 19.3 g (0.15 mol) of tert-butyl peroxide are added into an autoclave, oxygen is introduced until the pressure of the autoclave reaches 0.4MPa, the reaction temperature is 160 ℃, the reaction time is 120 minutes, and the specific reaction results are shown in Table I.
1, 6-hexanedial (C)6H10O2）：1H NMR (400 MHz, CDCl3, TMS): δ9.7 (t,2H), 2.4 (m, 4H), 1.6 (m, 4H)；GC-MS: [M]+ 114, [M-29]+ 85。
Example 10
12.3 g (0.15 mol) of cyclohexene, 1.4 g (0.0015 mol) of cobalt complex of isosbestol derivative, 20mL of tetrahydrofuran and 19.3 g (0.15 mol) of tert-butyl peroxide are added into an autoclave, oxygen is introduced until the pressure of the autoclave reaches 0.4MPa, the reaction temperature is 160 ℃, the reaction time is 300 minutes, and the specific reaction results are shown in Table I.
1, 6-hexanedial (C)6H10O2）：1H NMR (400 MHz, CDCl3, TMS): δ9.7 (t,2H), 2.4 (m, 4H), 1.6 (m, 4H)；GC-MS: [M]+ 114, [M-29]+ 85。
Example 11
16.4 g (0.2 mol) of cyclohexene, 3.8 g (0.004 mol) of cobalt complex of isosbestol derivative, 50mL of tetrahydrofuran and 25.7 g (0.2 mol) of tert-butyl peroxide are added into an autoclave, oxygen is introduced until the pressure of the autoclave reaches 0.6MPa, the reaction temperature is 160 ℃, the reaction time is 240 minutes, and the specific reaction result is shown in Table I.
1, 6-hexanedial (C)6H10O2）：1H NMR (400 MHz, CDCl3, TMS): δ9.7 (t,2H), 2.4 (m, 4H), 1.6 (m, 4H)；GC-MS: [M]+ 114, [M-29]+ 85。
Example 12
16.4 g (0.2 mol) of cyclohexene, 5.7 g (0.006 mol) of cobalt complex of isosbestol derivative, 50mL of tetrahydrofuran and 25.7 g (0.2 mol) of tert-butyl peroxide are added into an autoclave, oxygen is introduced to the autoclave until the pressure is 0.6MPa, the reaction temperature is 160 ℃, the reaction time is 240 minutes, and the specific reaction results are shown in the table I.
1, 6-hexanedial (C)6H10O2）：1H NMR (400 MHz, CDCl3, TMS): δ9.7 (t,2H), 2.4 (m, 4H), 1.6 (m, 4H)；GC-MS: [M]+ 114, [M-29]+ 85。
Example 13
8.2 g (0.1 mol) of cyclohexene, 0.95 g (0.001 mol) of cobalt complex of isosbestol derivative, 20mL of tetrahydrofuran and 10.3 g (0.08 mol) of tert-butyl peroxide are added into an autoclave, oxygen is introduced until the pressure of the autoclave reaches 0.4MPa, the reaction temperature is 160 ℃, the reaction time is 240 minutes, and the specific reaction results are shown in Table I.
1, 6-hexanedial (C)6H10O2）：1H NMR (400 MHz, CDCl3, TMS): δ9.7 (t,2H), 2.4 (m, 4H), 1.6 (m, 4H)；GC-MS: [M]+ 114, [M-29]+ 85。
Example 14
8.2 g (0.1 mol) of cyclohexene, 0.95 g (0.001 mol) of cobalt complex of isosbestol derivative, 20mL of tetrahydrofuran and 19.4 g (0.15 mol) of tert-butyl peroxide are added into an autoclave, oxygen is introduced until the pressure of the autoclave reaches 0.4MPa, the reaction temperature is 160 ℃, the reaction time is 240 minutes, and the specific reaction results are shown in Table I.
1, 6-hexanedial (C)6H10O2）：1H NMR (400 MHz, CDCl3, TMS): δ9.7 (t,2H), 2.4 (m, 4H), 1.6 (m, 4H)；GC-MS: [M]+ 114, [M-29]+ 85。
1, 6-adipic acid (C)6H10O4）：Mp 151.2~152.3℃；1H NMR (400 MHz, CDCl3, TMS): δ2.2 (t, 4H), 1.6 (m, 4H)。
Example 15
16.4 g (0.2 mol) of cyclohexene, 1.9 g (0.002 mol) of cobalt complex of isosbestol derivative, 50mL of ethyl acetate and 25.7 g (0.2 mol) of tert-butyl peroxide are added into an autoclave, oxygen is introduced until the pressure of the autoclave reaches 0.5MPa, the reaction temperature is 160 ℃, the reaction time is 240 minutes, and the specific reaction result is shown in the table I.
1, 6-hexanedial (C)6H10O2）：1H NMR (400 MHz, CDCl3, TMS): δ9.7 (t,2H), 2.4 (m, 4H), 1.6 (m, 4H)；GC-MS: [M]+ 114, [M-29]+ 85。
Example 16
16.4 g (0.2 mol) of cyclohexene, 1.9 g (0.002 mol) of cobalt complex of isoversol derivative, 50mL of methyl tert-butyl ether and 25.7 g (0.2 mol) of tert-butyl peroxide are added into an autoclave, oxygen is introduced until the pressure of the autoclave reaches 0.5MPa, the reaction temperature is 160 ℃, the reaction time is 240 minutes, and the specific reaction results are shown in the table I.
1, 6-hexanedial (C)6H10O2）：1H NMR (400 MHz, CDCl3, TMS): δ9.7 (t,2H), 2.4 (m, 4H), 1.6 (m, 4H)；GC-MS: [M]+ 114, [M-29]+ 85。
1, 6-adipic acid (C)6H10O4）：Mp 151.2~152.3℃；1H NMR (400 MHz, CDCl3, TMS): δ2.2 (t, 4H), 1.6 (m, 4H)。
Example 17
16.4 g (0.2 mol) of cyclohexene, 1.9 g (0.002 mol) of cobalt complex of isosbestol derivative, 50mL of 1, 4-dioxane and 25.7 g (0.2 mol) of tert-butyl peroxide are added into an autoclave, oxygen is introduced until the pressure of the autoclave is 0.5MPa, the reaction temperature is 160 ℃, the reaction time is 240 minutes, and the specific reaction result is shown in Table I.
1, 6-hexanedial (C)6H10O2）：1H NMR (400 MHz, CDCl3, TMS): δ9.7 (t,2H), 2.4 (m, 4H), 1.6 (m, 4H)；GC-MS: [M]+ 114, [M-29]+ 85。
1, 6-adipic acid (C)6H10O4）：Mp 151.2~152.3℃；1H NMR (400 MHz, CDCl3, TMS): δ2.2 (t, 4H), 1.6 (m, 4H)。
Example 18
16.4 g (0.2 mol) of cyclohexene, 1.9 g (0.002 mol) of cobalt complex of isosbestol derivative, 50mL of acetic acid and 25.7 g (0.2 mol) of tert-butyl peroxide are added into an autoclave, oxygen is introduced until the pressure of the autoclave is 0.5MPa, the reaction temperature is 160 ℃, the reaction time is 240 minutes, and the specific reaction result is shown in the table I.
1, 6-hexanedial (C)6H10O2）：1H NMR (400 MHz, CDCl3, TMS): δ9.7 (t,2H), 2.4 (m, 4H), 1.6 (m, 4H)；GC-MS: [M]+ 114, [M-29]+ 85。
TABLE-reaction results
Figure 155467DEST_PATH_IMAGE008
Note: the conversion and product distribution were determined by high pressure liquid chromatography, area normalization (calibration of standard curve).

Claims (4)

1. A method for preparing 1, 6-hexanedial by selectively oxidizing cyclohexene is characterized by comprising the following steps: adding a solvent, cyclohexene, a catalyst and a cocatalyst into a reaction kettle, introducing oxygen, keeping the pressure of the reaction kettle at 0.2-0.6 MPa, the reaction temperature at 120-170 ℃, and the reaction time at 60-300 minutes to obtain 1, 6-hexanedial; the cocatalyst is tert-butyl peroxide; the catalyst is a cobalt complex of an isosterviol derivative, and the structural formula of the catalyst is as follows:
Figure 585156DEST_PATH_IMAGE001
。
2. the process for the selective oxidation of cyclohexene to 1, 6-hexanedial as claimed in claim 1, wherein the cobalt complex of the isosterviol derivative is prepared as follows:
(1) adding 7.5g of isotretinoin derivative amino alcohol into a 100mL three-necked bottle, adding 20mL of methanol, stirring and dropwise adding 1.5g of glyoxal, stirring for 8 hours at room temperature, filtering the precipitate, washing with methanol, and drying in vacuum at 50 ℃ to obtain an intermediate product, namely, an isotretinoin derivative amino alcohol glyoxal condensation product; the structural formula of the isotretinol derivative amino alcohol glyoxal condensation product is:
Figure 439979DEST_PATH_IMAGE002
；
(2) adding 40 mL of methanol, 11.6g of isotretinoin derivative amino alcohol glyoxal condensation compound and 3.7g of cobalt acetate tetrahydrate into a 100mL three-necked bottle, carrying out reflux reaction for 10 hours under the protection of nitrogen, cooling, carrying out suction filtration, washing with methanol, and carrying out vacuum drying at 50 ℃ to obtain the cobalt complex of the isotretinoin derivative.
3. The process for selective oxidation of cyclohexene to produce 1, 6-hexanedial as claimed in claim 1 wherein the solvent is ethyl acetate or tetrahydrofuran.
4. The method for preparing 1, 6-hexanedial by selective oxidation of cyclohexene of claim 1, wherein the molar ratio of the catalyst to cyclohexene is 0.01-0.03: 1, and the molar ratio of the cocatalyst to cyclohexene is 0.8-1.5: 1.
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