CN109553515B - Method for preparing nonanal by selective oxidation of erucic acid or ester thereof - Google Patents

Method for preparing nonanal by selective oxidation of erucic acid or ester thereof Download PDF

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CN109553515B
CN109553515B CN201811632648.5A CN201811632648A CN109553515B CN 109553515 B CN109553515 B CN 109553515B CN 201811632648 A CN201811632648 A CN 201811632648A CN 109553515 B CN109553515 B CN 109553515B
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李瑞军
李怀珠
冯冰冰
刑程翔
贾龙飞
李�杰
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Abstract

A method for preparing nonanal by selective oxidation of erucic acid or esters thereof, wherein a catalyst is a manganese complex of a isosteviol derivative, comprises the following steps: adding a solvent, erucic acid or ester thereof, a catalyst and a cocatalyst into a reaction kettle, introducing oxygen, keeping the pressure of the reaction kettle at 0.2-0.7 MPa, the reaction temperature at 100-170 ℃, and the reaction time at 60-300 minutes to obtain the nonanal. Compared with the prior art, the method has the advantages that free radicals generated by decomposition of tert-butyl peroxide serving as a cocatalyst react with oxygen to generate oxygen radicals, the manganese complex serving as the catalyst of the isosteviol derivative reacts with double bonds in erucic acid or ester thereof to enable the isosteviol derivative to have higher reaction activity, and the activated double bonds react with the oxygen radicals to generate nonanal; the method has the advantages of mild reaction conditions, environmental friendliness, good selectivity of the nonanal and high yield.

Description

Method for preparing nonanal by selective oxidation of erucic acid or ester thereof
Technical Field
The invention belongs to the field of chemical material intermediates, and particularly relates to a method for preparing nonanal by selective oxidation of erucic acid or ester thereof.
Background
Selective oxidation of erucic acid or its ester to prepare nonanal is an important way to synthesize nonanal. Nonanal is used in large amounts in the synthesis of fine chemicals and organic intermediates. Nonanal exists in essential oil such as rose and neroli, is a natural perfume, has rose fragrance, and is widely applied to the fragrance blending industry. The oxidation of erucic acid or ester thereof to prepare nonanal traditionally adopts stoichiometric oxidant, and the oxidative epoxidation is carried out before ring opening oxidation, but in large-scale industrial production, the use of a large amount of heavy metal oxidant and heavy metal substances generated by the reaction seriously pollute the environment, so that a new green oxidation method needs to be developed for preparing nonanal through selective oxidation of erucic acid or ester thereof from the economic viewpoint, the environment protection viewpoint and the sustainable development viewpoint.
Documents CN102126953, CN101597221, WO 2014020281, WO 2011080297, WO 2007039481, and spring Peter et al (Catalysis Science & Technology,4, 708-.
Documents CN102351697, PCT int. appl.2014015290 and Bibi Haim et al (Bioorganic & Medicinal Chemistry Letters, 25, 342-346, 2015) use ozone, erucate is first formed into epoxide which is reduced to nonanal.
Rajabi, Mehdi et al, (Synthetic Communications, 44, 1149-. Amir Rubinstein et al (J. Am. chem. Soc. 2014, 136, 10941-10948) uses copper-tungsten-zinc composite catalyst to oxidize methyl erucate under the action of nitrogen dioxide and oxygen to obtain nonanal. Basavaraju, k.c. et al (angeltide Chemie, International Edition, 52, 6735-.
In recent years, because oxygen is the most abundant, cheap and environmentally friendly oxidant available, the use of oxygen as a clean oxidant has become a focus of research, and in the field of selective oxidation of erucic acid and its esters to nonanal, it is necessary to develop new efficient, mild, highly selective direct oxygen oxidation systems.
Disclosure of Invention
The invention aims to provide a method for preparing nonanal by selectively oxidizing erucic acid and esters thereof.
In order to realize the aim, the invention adopts the technical scheme that the method for preparing the nonanal by selectively oxidizing the erucic acid or the ester thereof comprises the following steps: adding a solvent, erucic acid or ester thereof, a catalyst and a cocatalyst into a reaction kettle, introducing oxygen, keeping the pressure of the reaction kettle at 0.2-0.7 MPa, the reaction temperature at 100-170 ℃, and the reaction time at 60-300 minutes to obtain nonanal; the catalyst is a manganese complex of isosterviol derivatives, and the structural formula of the manganese complex is as follows:
Figure 978283DEST_PATH_IMAGE001
。
preferably, the preparation method of the manganese complex of the isostaviol derivative is as follows:
(1) adding 9.4g of isotretinoin derivative amino alcohol into a 100mL three-necked bottle, adding 20mL of methanol, stirring, dropwise adding 1.9g 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 condensate;
the structural formula of the isosteviol derivative aminoalcohol is:
Figure 583839DEST_PATH_IMAGE002
；
the structural formula of the isotretinol derivative amino alcohol glyoxal condensation product is:
Figure 363576DEST_PATH_IMAGE003
；
(2) and adding 40 mL of methanol into a 100mL three-necked bottle, carrying out reflux reaction on 7.7g of the intermediate isosteviol derivative amino alcohol glyoxal condensation compound and 2.7g of manganese acetate dihydrate under the protection of nitrogen for 10 hours, cooling, carrying out suction filtration, washing with dichloromethane, and carrying out vacuum drying at 50 ℃ to obtain the manganese complex of the isosteviol derivative.
Preferably, the cocatalyst is tert-butyl peroxide.
Preferably, the solvent is 1, 4-dioxane or tetrahydrofuran.
Preferably, the erucic acid ester is any one or more of erucic acid ethyl ester, erucic acid methyl ester or erucic acid phenyl ester.
Preferably, the molar ratio of the catalyst to the erucic acid or the ester thereof is 0.01-0.05: 1, and the molar amount of the cocatalyst added is 80-120% of the molar amount of the erucic acid or the ester thereof.
Preferably, the mass of the solvent is 300-1000% of the mass of the erucic acid or the ester thereof.
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 manganese complex of the isosteviol derivative reacts with the double bond in the erucic acid or the ester thereof to enable the isosteviol derivative to have higher reaction activity, and the activated double bond reacts with the oxygen free radical to generate nonanal; the method has the advantages of mild reaction conditions, environmental friendliness, good selectivity of the nonanal 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 9.4g (0.025mol) of the isotretinoin derivative amino alcohol were added to a 100mL three-necked flask, and 1.9g (0.013mol) of glyoxal was added dropwise with stirring, and stirred at room temperature for 8 hours, and the precipitate was filtered, washed with methanol, and vacuum-dried at 50 ℃ to obtain 8.1g of an isotretinoin derivative amino alcohol glyoxal condensate in a yield of 80.2%. The structural formula is as follows:
Figure 696469DEST_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 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 were put into a 100mL three-necked flask, and subjected to reflux reaction for 10 hours under the protection of nitrogen, cooling, suction filtration, washing with dichloromethane, and vacuum drying at 50 ℃ to obtain 7.1g of a manganese complex of an isotretinol derivative, with a yield of 74.7%. The structural formula is as follows:
Figure 510841DEST_PATH_IMAGE005
。
synthesis of cobalt complexes of isosteviol derivatives: 40 mL of methanol, 7.7g (0.01mol) of isotretinol derivative amino alcohol glyoxal condensate and 2.5g (0.01mol) of cobalt acetate tetrahydrate are added into a 100mL three-necked flask, and the mixture is refluxed and reacted for 12 hours under the protection of nitrogen, cooled, filtered, washed by dichloromethane, and dried in vacuum at the solid temperature of 50 ℃ to obtain 6.7g of cobalt complex of isotretinol derivative, wherein the yield is 70.1%. The structural formula is as follows:
Figure 333303DEST_PATH_IMAGE006
。
example 2
3.5 g (0.01mol) of methyl erucate, 0.083 g (0.0001 mol) of manganese complex of isosbestol derivative, 10.5 g of 1, 4-dioxane and 1.0 g (0.008 mol) of tert-butyl peroxide are added into an autoclave, oxygen is introduced until the pressure of the autoclave is 0.2MPa, the reaction temperature is 100 ℃, the reaction time is 60 minutes, and the specific reaction result is shown in the table I.
Nonanal (C)9H18O）：1H NMR (400 MHz, CDCl3, TMS): δ9.7 (s, 1H), 2.4 (d, 2H), 1.6 (d, 2H), 1.28–1.33(m, 10H), 0.91 (d, 3H)；GC-MS: [M]+ 142, [M-27]+ 115。
2, 4-dinitrononanal phenylhydrazone (C)15H22N4O4）：1H NMR (400 MHz, CDCl3, TMS): δ8.8 (s, 1H), 8.3 (d, 1H), 7.5 (s, 1H), 7.0 (s, 1H), 6.8(d, 1H), 1.29-1.33 (m, 14H),0.9 (t, 3H)。
Example 3
3.7 g (0.01mol) of ethyl erucate, 0.25 g (0.0003 mol) of manganese complex of isoviol derivative, 14.8 g of 1, 4-dioxane and 1.3 g (0.01mol) 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 140 ℃, the reaction time is 120 minutes, and the specific reaction results are shown in Table I.
Nonanal (C)9H18O）：1H NMR (400 MHz, CDCl3, TMS): δ9.7 (s, 1H), 2.4 (d, 2H), 1.6 (d, 2H), 1.28–1.33(m, 10H), 0.91 (d, 3H)；GC-MS: [M]+ 142, [M-27]+ 115。
2, 4-dinitrononanal phenylhydrazone (C)15H22N4O4）：1H NMR (400 MHz, CDCl3, TMS): δ8.8 (s, 1H), 8.3 (d, 1H), 7.5 (s, 1H), 7.0 (s, 1H), 6.8(d, 1H), 1.29-1.33 (m, 14H),0.9 (t, 3H)。
Example 4
4.2 g (0.01mol) of erucic acid phenyl ester, 0.42 g (0.0005 mol) of manganese complex of isoviol derivative, 21.0 g of 1, 4-dioxane and 1.6 g (0.012 mol) of tert-butyl peroxide are added into an autoclave, oxygen is introduced until the pressure of the autoclave is 0.7MPa, the reaction temperature is 170 ℃, the reaction time is 180 minutes, and the specific reaction result is shown in Table I.
Nonanal (C)9H18O）：1H NMR (400 MHz, CDCl3, TMS): δ9.7 (s, 1H), 2.4 (d, 2H), 1.6 (d, 2H), 1.28–1.33(m, 10H), 0.91 (d, 3H)；GC-MS: [M]+ 142, [M-27]+ 115。
2, 4-dinitrononanal phenylhydrazone (C)15H22N4O4）：1H NMR (400 MHz, CDCl3, TMS): δ8.8 (s, 1H), 8.3 (d, 1H), 7.5 (s, 1H), 7.0 (s, 1H), 6.8(d, 1H), 1.29-1.33 (m, 14H),0.9 (t, 3H)。
Example 5
3.5 g (0.01mol) of methyl erucate, 0.42 g (0.0005 mol) of manganese complex of isoversol derivative, 21.0 g of 1, 4-dioxane and 1.3 g (0.01mol) of tert-butyl peroxide are added into an autoclave, oxygen is introduced until the pressure of the autoclave is 0.2MPa, the reaction temperature is 140 ℃, the reaction time is 240 minutes, and the specific reaction result is shown in Table I.
Nonanal (C)9H18O）：1H NMR (400 MHz, CDCl3, TMS): δ9.7 (s, 1H), 2.4 (d, 2H), 1.6 (d, 2H), 1.28–1.33(m, 10H), 0.91 (d, 3H)；GC-MS: [M]+ 142, [M-27]+ 115。
2, 4-dinitrononanal phenylhydrazone (C)15H22N4O4）：1H NMR (400 MHz, CDCl3, TMS): δ8.8 (s, 1H), 8.3 (d, 1H), 7.5 (s, 1H), 7.0 (s, 1H), 6.8(d, 1H), 1.29-1.33 (m, 14H),0.9 (t, 3H)。
Example 6:
3.7 g (0.01mol) of ethyl erucate, 0.083 g (0.0001 mol) of manganese complex of isosbestol derivative, 25.9 g of 1, 4-dioxane and 1.3 g (0.01mol) 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 170 ℃, the reaction time is 300 minutes, and the specific reaction result is shown in the table I.
Nonanal (C)9H18O）：1H NMR (400 MHz, CDCl3, TMS): δ9.7 (s, 1H), 2.4 (d, 2H), 1.6 (d, 2H), 1.28–1.33(m, 10H), 0.91 (d, 3H)；GC-MS: [M]+ 142, [M-27]+ 115。
2, 4-dinitrononanal phenylhydrazone (C)15H22N4O4）：1H NMR (400 MHz, CDCl3, TMS): δ8.8 (s, 1H), 8.3 (d, 1H), 7.5 (s, 1H), 7.0 (s, 1H), 6.8(d, 1H), 1.29-1.33 (m, 14H),0.9 (t, 3H)。
Example 7
3.4 g (0.01mol) of erucic acid, 0.25 g (0.0003 mol) of manganese complex of isoviol derivative, 27.2 g of tetrahydrofuran and 1.3 g (0.01mol) of tert-butyl peroxide are added into an autoclave, oxygen is introduced until the pressure of the autoclave is 0.7MPa, the reaction temperature is 100 ℃, the reaction time is 240 minutes, and the specific reaction result is shown in Table I.
Nonanal (C)9H18O）：1H NMR (400 MHz, CDCl3, TMS): δ9.7 (s, 1H), 2.4 (d, 2H), 1.6 (d, 2H), 1.28–1.33(m, 10H), 0.91 (d, 3H)；GC-MS: [M]+ 142, [M-27]+ 115。
2, 4-dinitrononanal phenylhydrazone (C)15H22N4O4）：1H NMR (400 MHz, CDCl3, TMS): δ8.8 (s, 1H), 8.3 (d, 1H), 7.5 (s, 1H), 7.0 (s, 1H), 6.8(d, 1H), 1.29-1.33 (m, 14H),0.9 (t, 3H)。
Example 8
3.4 g (0.01mol) of erucic acid, 0.25 g (0.0003 mol) of manganese complex of isoviol derivative, 30.6 g of tetrahydrofuran and 1.6 g (0.012 mol) of tert-butyl peroxide are added into an autoclave, oxygen is introduced until the pressure of the autoclave is 0.2MPa, the reaction temperature is 140 ℃, the reaction time is 240 minutes, and the specific reaction result is shown in Table I.
Nonanal (C)9H18O）：1H NMR (400 MHz, CDCl3, TMS): δ9.7 (s, 1H), 2.4 (d, 2H), 1.6 (d, 2H), 1.28–1.33(m, 10H), 0.91 (d, 3H)；GC-MS: [M]+ 142, [M-27]+ 115。
2, 4-dinitrononanal phenylhydrazone (C)15H22N4O4）：1H NMR (400 MHz, CDCl3, TMS): δ8.8 (s, 1H), 8.3 (d, 1H), 7.5 (s, 1H), 7.0 (s, 1H), 6.8(d, 1H), 1.29-1.33 (m, 14H),0.9 (t, 3H)。
Example 9
3.4 g (0.01mol) of erucic acid, 0.42 g (0.0005 mol) of manganese complex of isoviol derivative, 34.0 g of tetrahydrofuran and 1.6 g (0.012 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 100 ℃, the reaction time is 180 minutes, and the specific reaction result is shown in Table I.
Nonanal (C)9H18O）：1H NMR (400 MHz, CDCl3, TMS): δ9.7 (s, 1H), 2.4 (d, 2H), 1.6 (d, 2H), 1.28–1.33(m, 10H), 0.91 (d, 3H)；GC-MS: [M]+ 142, [M-27]+ 115。
2, 4-dinitrononanal phenylhydrazone (C)15H22N4O4）：1H NMR (400 MHz, CDCl3, TMS): δ8.8 (s, 1H), 8.3 (d, 1H), 7.5 (s, 1H), 7.0 (s, 1H), 6.8(d, 1H), 1.29-1.33 (m, 14H),0.9 (t, 3H)。
Example 10
3.4 g (0.01mol) of erucic acid, 0.083 g (0.0001 mol) of manganese complex of isosteryl alcohol derivative, 34.0 g of tetrahydrofuran and 1.6 g (0.012 mol) of tert-butyl peroxide are added into an autoclave, oxygen is introduced until the pressure of the autoclave is 0.7MPa, the reaction temperature is 140 ℃, the reaction time is 300 minutes, and the specific reaction result is shown in Table I.
Nonanal (C)9H18O）：1H NMR (400 MHz, CDCl3, TMS): δ9.7 (s, 1H), 2.4 (d, 2H), 1.6 (d, 2H), 1.28–1.33(m, 10H), 0.91 (d, 3H)；GC-MS: [M]+ 142, [M-27]+ 115。
2, 4-dinitrononanal phenylhydrazone (C)15H22N4O4）：1H NMR (400 MHz, CDCl3, TMS): δ8.8 (s, 1H), 8.3 (d, 1H), 7.5 (s, 1H), 7.0 (s, 1H), 6.8(d, 1H), 1.29-1.33 (m, 14H),0.9 (t, 3H)。
Example 11
3.4 g (0.01mol) of erucic acid, 0.095 g (0.0001 mol) of cobalt complex of isosteryl alcohol derivative, 34.0 g of tetrahydrofuran and 1.6 g (0.012 mol) of tert-butyl peroxide are added into the autoclave, oxygen is introduced until the pressure of the autoclave is 0.7MPa, the reaction temperature is 140 ℃, the reaction time is 300 minutes, and the specific reaction result is shown in Table I.
Nonanal (C)9H18O）：1H NMR (400 MHz, CDCl3, TMS): δ9.7 (s, 1H), 2.4 (d, 2H), 1.6 (d, 2H), 1.28–1.33(m, 10H), 0.91 (d, 3H)；GC-MS: [M]+ 142, [M-27]+ 115。
2, 4-dinitrononanal phenylhydrazone (C)15H22N4O4）：1H NMR (400 MHz, CDCl3, TMS): δ8.8 (s, 1H), 8.3 (d, 1H), 7.5 (s, 1H), 7.0 (s, 1H), 6.8(d, 1H), 1.29-1.33 (m, 14H),0.9 (t, 3H)。
TABLE reaction results of one or more examples
Figure 787287DEST_PATH_IMAGE007
Note: the conversion and product distribution were determined by high pressure liquid chromatography, area normalization (calibration of standard curve).

Claims (6)

1. A method for preparing nonanal by selective oxidation of erucic acid or an ester thereof is characterized by comprising the following steps: adding a solvent, erucic acid or ester thereof, a catalyst and a cocatalyst into a reaction kettle, introducing oxygen, keeping the pressure of the reaction kettle at 0.2-0.7 MPa, the reaction temperature at 100-170 ℃, and the reaction time at 60-300 minutes to obtain nonanal; the cocatalyst is tert-butyl peroxide; the catalyst is a manganese complex of isosterviol derivatives, and the structural formula of the manganese complex is as follows:
Figure 378003DEST_PATH_IMAGE001
。
2. the method for producing nonanal according to claim 1, wherein the manganese complex of the isosteviol derivative is produced by the following method:
(1) adding 9.4g of isotretinoin derivative amino alcohol into a 100mL three-necked bottle, adding 20mL of methanol, stirring and dropwise adding 1.9g 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 578040DEST_PATH_IMAGE002
；
(2) and adding 40 mL of methanol, 7.7g of the intermediate product isosteviol derivative amino alcohol glyoxal condensation compound and 2.7g of manganese acetate dihydrate into a 100mL three-necked bottle, refluxing for 10 hours under the protection of nitrogen, cooling, carrying out suction filtration, washing by using dichloromethane, and carrying out vacuum drying at 50 ℃ to obtain the manganese complex of the isosteviol derivative.
3. The method for producing nonanal according to claim 1, wherein the solvent is 1, 4-dioxane or tetrahydrofuran.
4. The method for preparing nonanal according to claim 1, wherein the erucic acid ester is one or more of ethyl erucate, methyl erucate and phenyl erucate.
5. The method for preparing nonanal according to claim 1, wherein the molar ratio of the catalyst to the erucic acid or the ester thereof is 0.01-0.05: 1, and the molar amount of the cocatalyst is 80-120% of the molar amount of the erucic acid or the ester thereof.
6. The method for preparing nonanal according to claim 1, wherein the amount of the solvent is 300 to 1000% by mass based on the mass of the erucic acid or the ester thereof.
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Synthesis, cytotoxic activity evaluation and HQSAR study of novel isosteviol derivatives as potential anticancer agents;Cong-Jun Liu;《European Journal of Medicinal Chemistry》;20160304;第115卷;26-40 *
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