CN112409144B - Method for synthesizing carboxylic acid or ketone compound from alcohol or aldehyde by using oxygen or oxygen in air as oxidant - Google Patents
Method for synthesizing carboxylic acid or ketone compound from alcohol or aldehyde by using oxygen or oxygen in air as oxidant Download PDFInfo
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Abstract
The invention discloses a novel method for synthesizing carboxylic acid or ketone compounds from alcohol or corresponding aldehyde by taking oxygen or oxygen in air as an oxidant, which is characterized in that the alcohol or corresponding aldehyde is oxidized into the corresponding carboxylic acid or ketone compounds under the catalysis of nitrate/4-hydroxy-2,2,6,6-tetramethylpiperidine oxide and the action of an additive. When an additional inorganic chloride is added, the reaction is accelerated. The method has the advantages of low catalyst price, easy operation, high yield, rich substrate diversity, mild reaction conditions, environmental friendliness and the like. The method is not only suitable for laboratory synthesis, but also suitable for industrial synthesis of carboxylic acid or ketone compounds.
Description
Technical Field
The invention relates to a chemical synthesis method, in particular to a novel method for synthesizing carboxylic acid or ketone compounds from alcohol or aldehyde by using oxygen or oxygen in air as an oxidant, namely, the alcohol or aldehyde is oxidized into corresponding carboxylic acid or ketone compounds in the presence of nitrate and 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide.
Background
Carboxylic acids are a basic class of chemical raw materials and have gained significant importance in the chemical industry. The oxidation reaction is a main synthetic route of carboxylic acid compounds, and the environmental burden of the conventional oxidation method (heavy metal oxide) is often an insurmountable obstacle in industrial production, so that the synthetic method based on air oxidation is receiving more and more attention. In recent years, work has been carried out in the field of air oxidation reactions of inexpensive metal-catalyzed alcohols, developing air oxidation systems based on inexpensive metal catalysts to achieve one-step conversion of alcohols to carboxylic acids (Tetrahedron lett.,1995,36,6923-6926, chem.commun.,2004,244-245, j.org.chem.,2007,72,7030-7033 applied catalysis a. The 2,2,6,6-tetramethylpiperidine oxide is expensive and its cost is too high on an industrial scale. In contrast, 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide is extremely inexpensive, but its catalytic activity is very low.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention researches and develops a catalytic oxidation system for synthesizing carboxylic acid or ketone compounds from alcohol or aldehyde based on nitrate/4-hydroxy-2,2,6,6-tetramethylpiperidine oxide by taking oxygen or oxygen in air as an oxidant.
The invention aims to provide a novel method for synthesizing carboxylic acid or ketone compounds based on nitrate/4-hydroxy-2,2,6,6-tetramethylpiperidine oxide catalytic oxidation, which is simple, efficient, rapid and more economical.
The invention is realized by the following technical scheme:
the invention discloses a new method for synthesizing carboxylic acid or ketone compound from alcohol or corresponding aldehyde by taking oxygen or oxygen in air as oxidant, which oxidizes reaction substrate alcohol or corresponding aldehyde into corresponding carboxylic acid or ketone compound under the catalysis of nitrate/4-hydroxy-2,2,6,6-tetramethylpiperidine oxide and the action of additive, and the reaction formula is as follows:
the method specifically comprises the following steps: adding nitrate, 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide and an additive into a container, pumping gas, then adding a reaction substrate alcohol or corresponding aldehyde into a reaction system at one time or dropwise, and stirring for reaction; concentrating, and performing flash column chromatography or distilling directly to obtain carboxylic acid or ketone compound.
In the present invention, the alcohol is a primary alcohol RCH 2 OH or a secondary alcohol R 1 CHOHR 2 。
Wherein R is C3-C15 straight-chain or branched alkane or unsaturated hydrocarbon containing benzene ring or alkene or alkyne, and the substrate is compatible with functional groups such as alkoxy, halogen and the like; the reaction substrate is an aldehyde corresponding to the above-mentioned primary alcohol.
Preferably, the primary alcohol is a primary monohydric alcohol or a primary dihydric alcohol having a carbon number greater than 6.
Wherein R is 1 Is C1-C15 straight chain or branched alkane, or unsaturated hydrocarbon containing benzene ring, alkene or alkyne, etc.; r 2 Is C1-C15 straight-chain or branched alkane, or unsaturated hydrocarbon containing benzene ring, alkene or alkyne, etc.
Preferably, the secondary alcohol is secondary aliphatic alcohol, benzyl alcohol, allyl alcohol or propargyl alcohol and the like.
In the invention, the additive is one or more of 1,2-dichloroethane, 1,1-dichloroethane, 1,2-dichloropropane, 1,3-dichloropropane, dichloromethane, nitromethane, benzene, toluene, acetonitrile, ethyl acetate, tetrahydrofuran and the like; preferably, it is acetonitrile.
In the invention, the nitrate is one or a mixture of ferric nitrate nonahydrate and copper nitrate trihydrate; preferably, it is ferric nitrate nonahydrate.
In the invention, the molar ratio of the alcohol or the corresponding aldehyde, the nitrate and the 4-hydroxy-2,2,6,6-tetramethyl piperidine oxide is 100: (1-10): (1-10); preferably, it is 100:5:5.
in the invention, the molar ratio of the alcohol or the corresponding aldehyde to the additive is 1: (1-6); preferably, 1:3.
in the invention, when an inorganic chloride is additionally added, the reaction is accelerated, wherein the inorganic chloride comprises one or more of lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride and the like; preferably, it is potassium chloride.
Wherein, the mol ratio of the alcohol or the corresponding aldehyde to the inorganic chloride is 100 (1-10); preferably, 100.
In the present invention, the gas to be pumped is pure oxygen or oxygen in the air.
In the invention, the reaction temperature is between room temperature and 50 ℃; preferably, room temperature.
The method has the advantages of mild reaction conditions, easy operation, high yield, rich substrate diversity, environmental friendliness and the like. In addition, compared with ferric nitrate nonahydrate, 2,2,6,6-tetramethyl oxynitride and a potassium chloride catalytic system (ephedrine Jiang Xingguo, a method for preparing acid by oxidizing alcohol or aldehyde with oxygen, application numbers: 201610141434.2, 2016.03.11), the invention has the following advantages: 1) The catalyst is cheap and the production cost is greatly reduced; 2) Additives such as acetonitrile have a remarkable promoting effect on the reaction; 3) The dosage of the solvent is greatly reduced; 4) The reaction can be carried out without adding chloride. The method is not only suitable for laboratory synthesis, but also suitable for industrial synthesis of carboxylic acid compounds.
Drawings
FIG. 1 is a graph showing the effect of the absence or addition of chloride on the oxidation reaction of isononyl alcohol.
Detailed Description
The method for synthesizing carboxylic acid or ketone compound is that alcohol or corresponding aldehyde can be oxidized into corresponding carboxylic acid or ketone compound under the catalysis of nitrate/4-hydroxy-2,2,6,6-tetramethyl piperidine oxide and in the presence of additive at room temperature, and the reaction formula is as follows:
wherein R can be alkyl, aryl, alkene, alkynyl, etc.; preferably, the alkyl group is a linear or branched alkane having 3 to 15 carbon atoms, and is compatible with functional groups such as alkoxy and halogen.
R 1 Is C1-C15 straight chain or branched alkane, or unsaturated hydrocarbon containing benzene ring, alkene or alkyne, etc.; r 2 Is C1-C15 straight chain or branched alkane or unsaturated hydrocarbon containing benzene ring or alkene or alkyne, etc.
The method comprises the following steps: adding nitrate, 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide and an additive into a three-necked bottle, pumping gas (pure oxygen or air), adding alcohol into a reaction system, and stirring and reacting for 10-72 hours at room temperature; concentrating, and performing flash column chromatography (or distilling directly) to obtain carboxylic acid compounds.
The technical solution of the present invention is further illustrated by the following specific examples:
example 1
Ferric nitrate nonahydrate (401.8mg, 1.0mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (172.4mg, 1.0mmol), potassium chloride (75.9mg, 1.0mmol), 1a (1.4381g, 10.0mmol) and 1,2-dichloroethane (2 mL) were charged into a three-necked flask, and purging (pure oxygen) was performed three times, and the mixture was stirred at room temperature (25 ℃) for 33 hours to obtain 49% of 2a (internal dibromomethane standard, nuclear magnetic yield) and 39% of 3a (internal dibromomethane standard, nuclear magnetic yield).
Example 2
Iron nitrate nonahydrate (405.8mg, 1.0mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (171.4mg, 1.0mmol), potassium chloride (75.7mg, 1.0mmol), 1a (1.4353g, 10.0mmol) and methylene chloride (2 mL) were charged into a three-necked flask, and stirred at room temperature (25 ℃ C.) for 33 hours with purging (pure oxygen) three times to obtain 41% of 2a (internal standard with dibromomethane, nuclear magnetic yield) and 27% of 3a (internal standard with dibromomethane, nuclear magnetic yield).
Example 3
Ferric nitrate nonahydrate (403.5mg, 1.0mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (171.6 mg, 1.0mmol), potassium chloride (75.0mg, 1.0mmol), 1a (1.4359g, 10.0mmol) and toluene (2 mL) were added to a three-necked flask, and the mixture was stirred at room temperature (25 ℃) for 24 hours under ventilation (pure oxygen) for three times to obtain 25% of 2a (internal standard with dibromomethane, nuclear magnetic yield) and 63% of 3a (internal standard with dibromomethane, nuclear magnetic yield).
Example 4
Ferric nitrate nonahydrate (405.0mg, 1.0mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (172.2mg, 1.0mmol), potassium chloride (75.0mg, 1.0mmol), 1a (1.4442g, 10.0mmol) and acetonitrile (2 mL) were added to a three-necked flask, and ventilation (pure oxygen) was performed three times, and stirring was performed at room temperature (25 ℃) for 12 hours, and flash column chromatography (petroleum ether/ethyl acetate = 10/1) was performed to obtain 2a (1.4387 g, yield: 83%, purity: 91%).
Example 5
Iron nitrate nonahydrate (404.7mg, 1.0mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (171.6mg, 1.0mmol), potassium chloride (74.8mg, 1.0mmol), 1a (1.4438g, 10.0mmol), acetonitrile (413.8mg, 10.0mmol) and 1,2-dichloroethane (2 mL) were charged into a three-necked flask, and the mixture was purged (pure oxygen) three times and stirred at room temperature (25 ℃ C.) for 24 hours to obtain 58% of 2a (using dibromomethane as an internal standard, nuclear magnetic yield) and 26% of 3a (using dibromomethane as an internal standard, nuclear magnetic yield).
Example 6
Ferric nitrate nonahydrate (404.4mg, 1.0mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (172.8mg, 1.0mmol), potassium chloride (75.8mg, 1.0mmol), 1a (1.4550g, 10.0mmol), acetonitrile (409.6mg, 10.0mmol) and toluene (2 mL) were charged into a three-necked flask, and the mixture was stirred at room temperature (25 ℃) for 24 hours under ventilation (pure oxygen) three times to obtain 44% of 2a (using dibromomethane as an internal standard, nuclear magnetic yield) and 46% of 3a (using dibromomethane as an internal standard, nuclear magnetic yield).
Example 7
Ferric nitrate nonahydrate (403.7mg, 1.0mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (172.0mg, 1.0mmol), potassium chloride (75.1mg, 1.0mmol), 1a (1.4357g, 10.0mmol) and acetonitrile (1.228057g, 30mmol) were added to a three-necked flask, and ventilation (pure oxygen) was performed three times, followed by stirring at room temperature (25 ℃) for 10 hours and flash column chromatography (petroleum ether/ethyl acetate = 10/1) to obtain 2a (1.3316g, 85%).
Example 8
To a three-necked flask, ferric nitrate nonahydrate (404.4mg, 1.0mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (172.6mg, 1.0mmol), potassium chloride (74.8mg, 1.0mmol), 1a (1.4338g, 10.0mmol) and acetonitrile (0.8320g, 20mmol) were charged, and the mixture was purged (pure oxygen) three times, stirred at room temperature (25 ℃) for 24 hours, and flash column chromatography (petroleum ether/ethyl acetate = 10/1) was performed to obtain 2a (1.2883g, 82%).
Example 9
To a three-necked flask, ferric nitrate nonahydrate (403.0mg, 1.0mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (172.4mg, 1.0mmol), potassium chloride (75.4mg, 1.0mmol), 1a (1.4442g, 10.0mmol) and acetonitrile (0.4060g, 10 mmol) were added, and the mixture was purged (pure oxygen) three times, stirred at room temperature (25 ℃) for 24 hours, and flash column chromatography (petroleum ether/ethyl acetate = 10/1) was performed to obtain 2a (1.1226g, 71%).
Example 10
Ferric nitrate nonahydrate (402.9mg, 1.0mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (171.2mg, 1.0mmol), potassium chloride (74.8mg, 1.0mmol), 1a (1.4403g, 10.0mmol) and acetonitrile (0.2113g, 5 mmol) were charged into a three-necked flask, and the mixture was stirred at room temperature (25 ℃) for 24 hours with purging (pure oxygen) three times to obtain 49% of 2a (internal standard with dibromomethane, nuclear magnetic yield) and 26% of 3a (internal standard with dibromomethane, nuclear magnetic yield).
Example 11
Ferric nitrate nonahydrate (201.5mg, 0.5mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (85.8mg, 0.5mmol), potassium chloride (37.2mg, 0.5mmol), 1a (1.4389g, 10.0mmol), acetonitrile (1.2408g, 30mmol) were charged into a three-necked flask, and the mixture was stirred three times with ventilation (pure oxygen) at room temperature (25 ℃ C.) for 24 hours, passed through a short silica gel column (dichloromethane: 20 mL. Times.3), concentrated, and subjected to flash column chromatography (petroleum ether/ethyl acetate =50/1 to 5/1) to obtain a product 2a (1.245g, 79%) as a liquid.
Example 12
Ferric nitrate nonahydrate (202.6mg, 0.5mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (86.6mg, 0.5mmol), potassium chloride (37.2mg, 0.5mmol) and acetonitrile (1.2321g, 30mmol) are added into a three-necked flask, air exchange (pure oxygen) is carried out for three times, 1a (1.3806 g,9.6 mmol) is dropwise added under stirring at room temperature (25 ℃) (dropwise completed within 5 hours), stirring is continuously carried out at room temperature for reaction for 19 hours, a short silica gel column (dichloromethane: 20mL multiplied by 3) is used, concentration and flash column chromatography (petroleum ether/ethyl acetate = 50/1-5/1) are carried out, and a product 2a (1.2899g, 85%) is obtained and is liquid.
Example 13
Ferric nitrate nonahydrate (201.2mg, 0.5mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (86.4mg, 0.5mmol), 1a (1.4546g, 10.0mmol) and acetonitrile (1.2237g, 30mmol) were added to a three-necked flask, and 2a (1.1226 g, 70%) was obtained by purging (pure oxygen) three times, stirring at room temperature (25 ℃) for 24 hours, and flash column chromatography (petroleum ether/ethyl acetate =50/1 to 10/1).
1 H NMR(300MHz,CDCl 3 ):δ＝10.86(br d,1H),2.37(dd,J 1 ＝14.7Hz,J 2 ＝6.0Hz,1H),2.18(dd,J 1 ＝14.7Hz,J 2 ＝8.1Hz,1H),2.11-1.98(m,1H),1.27(dd,J 1 ＝14.1Hz,J 2 ＝4.2Hz,1H),1.18(dd,J 1 ＝14.1Hz,J 2 ＝6.0Hz,1H),1.01(d,J＝6.3Hz,3H),0.91(s,3H)； 13 C NMR(75MHz,CDCl 3 ):δ＝179.9,50.5,43.7,31.0,29.9,26.8,22.6；IR(neat,cm -1 )＝2958,1713,1469,1411,1366,1286,1247,1219,1171,1079；MS(EI):m/z(％)143[M-H,5.37],57(100).
Example 14
Adding copper nitrate trihydrate (121.2mg, 0.5mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (85.3mg, 0.5mmol) and acetonitrile (1.2300g, 30mmol) into a three-neck flask, ventilating (pure oxygen) for three times, dropwise adding 1a (1.4055g, 9.7mmol) under stirring at room temperature (25 ℃) (dropwise adding the pure oxygen within 5 hours), continuously stirring at room temperature for reaction for 67 hours, passing through a short silica gel column (dichloromethane: 20 mL. Times.3), using dibromomethane as an internal standard to obtain 3a 47% (nuclear magnetic yield), and performing flash column chromatography (petroleum ether/ethyl acetate = 50/1-5/1) to obtain 2a (0.6677g, 43%).
Example 15
Ferric nitrate nonahydrate (40.1mg, 0.1mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (17.4mg, 0.1mmol), 1a (1.4345g, 10.0mmol) and acetonitrile (1.2500g, 30mmol) were added to a three-necked flask, and ventilation (pure oxygen) was carried out three times, and stirring was carried out at room temperature (25 ℃) for 72 hours, and a short silica gel column (dichloromethane: 20 mL. Times.3) was used with dibromomethane as an internal standard to give 3a12% (nuclear magnetic yield), and 59% was recovered from the raw material 1 a.
Example 16
Ferric nitrate nonahydrate (202.7mg, 0.5mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (84.8mg, 0.5mmol), 1a (1.4434g, 10.0mmol) and acetonitrile (1.2309g, 30mmol) were added to a three-necked flask, and 2a (1.1539g, 73%) was obtained by purging (pure oxygen) three times, stirring at 50 ℃ for 18 hours, and flash column chromatography (petroleum ether/ethyl acetate = 50/1-5/1).
Example 17
Ferric nitrate nonahydrate (199.6 mg, 0.5mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (85.0mg, 0.5mmol), lauryl alcohol 1b (1.8620g, 10.0mmol) and acetonitrile (1.2431g, 30mmol) were charged into a three-necked flask, and the mixture was purged with air (pure oxygen) three times, stirred at room temperature (25 ℃) for 48 hours, passed through a short silica gel column (dichloromethane: 20 mL. Times.3), and dibromomethane was used as an internal standard to obtain 2b 70% (nuclear magnetic yield).
Example 18
Ferric nitrate nonahydrate (202.4 mg,0.5 mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (85.7 mg,0.5 mmol), potassium chloride (37.7 mg,0.5 mmol), lauryl alcohol 1b (1.8583g, 10.0 mmol) and acetonitrile (1.6404g, 40mmol) were added to a three-necked flask, purged with air (pure oxygen) three times, stirred at room temperature (25 ℃) for 24 hours, short silica gel column (dichloromethane: 20mL × 3; ethyl acetate: 60 mL), concentrated, and flash column chromatographed (petroleum ether/ethyl acetate = 50/1-5/1) to obtain product 2b (1.7469g, 87%) as a solid (n-hexane/ethyl acetate = 4/1).
1 H NMR(300MHz,CDCl 3 )δ11.45(brs,1H,COOH),2.35(t,J＝7.5Hz,2H,CH 2 ),1.63(quint,J＝7.1Hz,2H,CH 2 ),1.40-1.18(m,16H,8×CH 2 ),0.88(t,J＝6.6Hz,3H,CH 3 )； 13 CNMR(75MHz,CDCl 3 )δ180.7,34.1,31.9,29.6,29.4,29.3,29.2,29.0,24.7,22.7,14.1；IR(KBr,cm -1 ):2917,2849,1694,1470,1430,1411,1351,1328,1303,1249,1220,1193,1084；MS(EI)m/z(％):200(M + ,9.43),73(100).
Example 19
Ferric nitrate nonahydrate (202.1mg, 0.5 mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (86.1mg, 0.5 mmol) and acetonitrile (1.2302g, 30mmol) are added into a three-necked flask, air (pure oxygen) is ventilated for three times, hexanol 1C (0.9821g, 10.0 mmol) is dropwise added under stirring at room temperature (25 ℃) (dropwise is finished within 5 hours), the reaction is continuously stirred at room temperature for 10 hours, a short silica gel column (dichloromethane: 20 mL. Times.3) is used, concentration and flash column chromatography (petroleum ether/ethyl acetate = 10/1-5/1) is carried out, and a product 2C (0.8786g, 79%) is obtained and is liquid.
1 H NMR(300MHz,CDCl 3 )δ10.85(brs,1H,COOH),2.35(t,J＝7.5Hz,2H,CH 2 ),1.63(quint,J＝7.2Hz,2H,CH 2 ),1.40-1.28(m,4H,2×CH 2 ),0.90(t,J＝6.6Hz,3H,CH 3 )； 13 C NMR(75MHz,CDCl 3 )δ180.4,34.0,31.2,24.3,22.3,13.8；IR(neat,cm -1 ):2960,2934,2875,1712,1463,1414,1293,1247,1213,1107；MS(EI)m/z(％):117(M+H,100),99(100).
Example 20
Ferric nitrate nonahydrate (202.0mg, 0.5mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (85.7mg, 0.5mmol), potassium chloride (37.2mg, 0.5mmol) and acetonitrile (1.2328g, 30mmol) were added to a three-necked flask, air (pure oxygen) was exchanged three times, n-butanol 1d (0.7358g, 10.0mmol) was added dropwise with stirring at room temperature (25 ℃) (dropwise addition completed within 5 hours), the reaction was continued with stirring at room temperature for 17 hours, a short silica gel column (dichloromethane: 20 mL. Times.3) was passed through, concentration and flash column chromatography (petroleum ether/ethyl acetate =10/1 to 3/1) to obtain product 2d (yield: 80%; isolated yield: 55%) as a liquid.
Example 21
Ferric nitrate nonahydrate (202.0mg, 0.5mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (86.5mg, 0.5mmol), n-butyraldehyde 3d (0.721g, 10.0mmol) and acetonitrile (1.2249g, 30mmol) were added to a three-necked flask, and the reaction was stirred at room temperature for 22 hours with ventilation (pure oxygen), so that the starting material 3d was completely converted.
1 H NMR(300MHz,CDCl 3 )δ2.34(t,J＝7.5Hz,2H,CH 2 ),1.70-1.60(m,2H,CH 2 ),0.98(t,J＝7.5Hz,3H,CH 3 )； 13 C NMR(75MHz,CDCl 3 )δ180.4,35.9,18.1,13.5；IR(neat,cm -1 ):2969,2879,2666,1713,1461,1414,1283,1220,1096；MS(EI)m/z(％):88(M + ,2.75),60(100).
Example 22
Ferric nitrate nonahydrate (201.6mg, 0.5mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (85.5mg, 0.5mmol) and acetonitrile (1.2524g, 30mmol) were added to a three-necked flask, and ventilation (pure oxygen) was carried out three times, 6-chlorohexanol 1e (1.2999g, 9.5mmol) was added dropwise with stirring at room temperature (25 ℃) within 5 hours, stirring was continued for 19 hours at room temperature, and a silica gel column (dichloromethane: 20 mL. Times.3) was shortened to obtain a product 2e 83% (nuclear magnetic yield) using dibromomethane as an internal standard.
Example 23
Ferric nitrate nonahydrate (201.0mg, 0.5mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (86.0mg, 0.5mmol), potassium chloride (37.0mg, 0.5mmol), 6-chlorohexanol 1e (1.3747g, 10.0mmol) and acetonitrile (1.2693g, 30mmol) were added to a three-necked flask, and air (pure oxygen) was ventilated three times, stirred at room temperature (25 ℃) for 12 hours, passed through a short silica gel column (dichloromethane: 20 mL. Times.3), concentrated, and flash column chromatographed (petroleum ether/ethyl acetate =10/1 to 3/1) to obtain 2e (1.1037g, 73%) as a product as a liquid.
Example 24
Ferric nitrate nonahydrate (202.1mg, 0.5mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (86.3mg, 0.5mmol), potassium chloride (37.6mg, 0.5mmol) and acetonitrile (1.2524g, 30mmol) were added to a three-necked flask, and 6-chlorohexanol 1e (1.2855g, 10.0mmol) was added dropwise with stirring at room temperature (25 ℃) for three times with aeration (pure oxygen) (dropwise addition was completed within 5 hours), stirring was continued at room temperature for 13 hours, short silica gel column (dichloromethane: 20 mL. Times.3) was passed through, concentration and flash column chromatography (petroleum ether/ethyl acetate =10/1 to 3/1) was carried out to obtain 2e (1.0895g, 77%) as a liquid product.
1 H NMR(300MHz,CDCl 3 )δ3.54(t,J＝6.6Hz,2H,CH 2 ),2.38(t,J＝7.2Hz,2H,CH 2 ),1.80(quint,J＝7.2Hz,2H,CH 2 ),1.67(quint,J＝8.1Hz,2H,CH 2 ),1.58-1.48(m,2H,CH 2 )； 13 CNMR(75MHz,CDCl 3 )δ180.0,44.7,33.8,32.1,26.2,23.9；IR(neat,cm -1 ):2943,2869,2676,1713,1541,1414,1277,1238,1133,1056；MS(EI)m/z(％):153(M( 37 Cl)+H,3.34),151(M( 35 Cl)+H,9.76),73(100).
Example 25
Ferric nitrate nonahydrate (201.6mg, 0.5 mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (85.9mg, 0.5 mmol) and acetonitrile (1.2254g, 30mmol) are added into a three-necked flask, air (pure oxygen) is ventilated for three times, 5-hexynol 1f (0.9745g, 10.0mmol) is dropwise added under stirring at room temperature (25 ℃) (dropwise completed within 5 hours), the reaction is continued for 27 hours at room temperature, a silica gel column (dichloromethane: 20 mL. Times.3) is too short, dibromomethane is used as an internal standard, and a product 2f71% (nuclear magnetic yield) is obtained.
Example 26
Ferric nitrate nonahydrate (202.2mg, 0.5mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (86.2mg, 0.5mmol), potassium chloride (36.8mg, 0.5mmol), 5-hexynol 1f (0.9799g, 10.0mmol) and acetonitrile (1.2323g, 30mmol) were added to a three-necked flask, and the mixture was stirred at room temperature (25 ℃) for 16 hours with aeration (pure oxygen) three times, passed through a short silica gel column (dichloromethane: 20 mL. Times.3), concentrated, and subjected to flash column chromatography (petroleum ether/ethyl acetate =5/1 to 3/1) to obtain product 2f (0.7204g, 64%): the product was a liquid.
Example 27
Ferric nitrate nonahydrate (202.4mg, 0.5mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (86.4mg, 0.5mmol), potassium chloride (36.8mg, 0.5mmol) and acetonitrile (1.2263g, 30mmol) were added to a three-necked flask, air (pure oxygen) was exchanged three times, 5-hexynol 1f (0.9570g, 9.7mmol) was added dropwise with stirring at room temperature (25 ℃) within 5 hours, the reaction was continued at room temperature for 15 hours, a short silica gel column (dichloromethane: 20 mL. Times.3) was passed through, concentration and flash column chromatography (petroleum ether/ethyl acetate =5/1 to 3/1) was carried out to obtain product 2f (0.7987g, 73%): product was liquid.
1 H NMR(300MHz,CDCl 3 ):δ2.52(t,J＝7.5Hz,2H,CH 2 ),2.29(td,J＝6.9,2.4Hz,2H,CH 2 ),1.99(t,J＝2.7Hz,1H,CH),1.86(quant,J＝7.2Hz,2H,CH 2 )； 13 C NMR(75MHz,CDCl 3 )δ179.7,83.0,69.3,32.5,23.2,17.7；IR(neat,cm -1 )＝3297,2946,2118,1714,1434,1245,1206,1158,1052；MS(EI):m/z(％)111[M-H,4.72],70(100).
Example 28
Ferric nitrate nonahydrate (202.5mg, 0.5mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (85.7mg, 0.5mmol), 3,4-dimethoxyphenethyl alcohol 1g (1.8209g, 10.0 mmol) and acetonitrile (1.2270g, 30mmol) were added to a three-necked flask, and the mixture was purged with air (pure oxygen) three times, stirred at room temperature (25 ℃) for 24 hours, passed through a short silica gel column (ethyl acetate: 20 mL. Times.3), concentrated, and flash column chromatographed (petroleum ether/ethyl acetate =5/1 to 1/1) to obtain 2g (1.1g, 63%) of a product as a solid (95.0 to 96.3 ℃ n-hexane/ethyl acetate = 4/1).
1 H NMR(300MHz,CDCl 3 )δ6.85-6.79(m,3H,Ar-H),3.88(s,3H,CH 3 ),3.87(s,3H,CH 3 ),3.60(s,2H,CH 2 )； 13 C NMR(75MHz,CDCl 3 )δ177.9,149.0,148.4,125.7,121.6,112.5,111.3,55.9,40.6；IR(KBr,cm -1 ):3005,2963,2942,2839,2650,1717,1646,1608,1593,1515,1468,1447,1423,1396,1340,1263,1242,1190,1149,1037,1018；MS(EI)m/z(％):196(M + ,93.46),151(100).
Example 29
To a three-necked flask were added ferric nitrate nonahydrate (202.4 mg,0.5 mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (86.6 mg,0.5 mmol), potassium chloride (37.5 mg,0.5 mmol), nonanediol 1h (1.5997g, 10.0 mmol) and acetonitrile (1.2545g, 30mmol), purged with air (pure oxygen) three times, stirred at room temperature (25 ℃) for 48 hours, the reaction solution was basified with sodium hydroxide solution, ethyl acetate extracted (20ml x 3), the aqueous phase was acidified with concentrated hydrochloric acid, allowed to stand, filtered, and washed with water to give the product 2h (1.3233g, 70%): the product was solid, n-hexane/ethyl acetate =4/1 ℃. (105.1-106.9 ℃).
1 H NMR(300MHz,DMSO-d 6 ):δ＝11.98(br d,2H),2.18(d,J＝7.5Hz,4H),1.53-1.40(m,4H),1.30-1.18(m,6H)； 13 C NMR(75MHz,DMSO-d 6 ):δ＝175.5,34.6,29.43,29.39,25.4；IR(KBr,cm -1 )＝3028,2934,2849,1701,1467,1437,1410,1344,1309,1268,1252,1230,1208,1196,1129,10978,1051,930；MS(EI):m/z(％)189[M+H,35.43],171(100).
Example 30
Ferric nitrate nonahydrate (201.9mg, 0.5mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (86.5mg, 0.5mmol), phenethyl alcohol 1i (1.2249g, 10.0mmol) and acetonitrile (1.2348g, 30mmol) were charged into a three-necked flask, and the mixture was purged with air (pure oxygen) three times, stirred at room temperature for 15 hours, passed through a short silica gel column (ethyl acetate: 20 mL. Times.3), concentrated, and subjected to flash column chromatography (petroleum ether/ethyl acetate = 10) to obtain 2i (1.0705g, 89%) as a product as a liquid.
1 H NMR(300MHz,CDCl 3 )δ7.96(d,J＝7.2Hz,2H,Ar-H),7.55(t,J＝7.2Hz,1H,Ar-H),7.44(t,J＝7.5Hz,2H,Ar-H),2.59(s,3H,CH 3 )； 13 C NMR(75MHz,CDCl 3 )δ198.0,137.1,133.0,128.5,128.2,26.5.
Example 31
Ferric nitrate nonahydrate (201.9mg, 0.5mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (85.9mg, 0.5mmol), 1-octen-3-ol 1j (1.2789g, 10.0mmol) and acetonitrile (1.2507g, 30mmol) were added to a three-necked flask, and the mixture was purged with air (pure oxygen) three times, stirred at room temperature for 11 hours, passed through a short silica gel column (ethyl acetate: 20 mL. Times.3), concentrated, and subjected to flash column chromatography (petroleum ether/ethyl acetate = 10) to give product 2j (0.7349g, 58%) as a liquid.
1 H NMR(300MHz,CDCl 3 ):δ＝6.38(dd,J 1 ＝17.7Hz,J 2 ＝10.2Hz,1H),6.21(d,J＝17.4Hz,1H),5.80(d,J＝10.2Hz,1H),2.57(t,J＝7.5Hz,2H),1.70-1.56(m,2H),1.40-1.22(m,4H),0.90(t,J＝6.6Hz,3H)； 13 C NMR(75MHz,CDCl 3 ):δ＝201.0,136.6,127.7,39.6,31.4,23.7,22.4,13.8.
Example 32 Synthesis of 1mol Scale Isononanoic acid (2 a) based on pure oxygen
Ferric nitrate nonahydrate (40.4612g, 0.1mol), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (17.2267g, 0.1mol), potassium chloride (7.5055g, 0.1mol), isononyl alcohol 1a (175mL, 1.0mol) and acetonitrile (156mL, 3.0mol) were charged into a three-necked flask, and air (pure oxygen) was purged three times, stirred at room temperature for 23 hours (temperature controlled not higher than 45 ℃ C.), acetonitrile was recovered by atmospheric distillation, and the product 2a (118.5825g, YIeld 75%, purity: 93%) was obtained by distillation under reduced pressure (106 ℃/3.5 mmHg) as a liquid.
Example 33 Synthesis of Isononanoic acid (2 a) on a 1mol Scale based on air flow
Ferric nitrate nonahydrate (40.4190g, 0.1mol%), 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (17.2080g, 0.1mol), potassium chloride (7.4590g, 0.1mol), isononyl alcohol 1a (175mL, 1.0mol), and acetonitrile (156mL, 3.0mol) were charged into a three-necked flask, and the mixture was purged with air (pure oxygen) three times, stirred at room temperature for 72 hours (temperature controlled not higher than 50 ℃ C.), acetonitrile was recovered by atmospheric distillation, and distilled under reduced pressure (110 ℃/7.0 mmHg) to obtain a product 2a (134.3592g, YIELD 82%; purity: 98%) as a liquid.
The corresponding beneficial effects of the invention are analyzed by specific embodiments:
1) The solvent has a remarkable influence on the reaction: the 3,5,5-trimethyl-1-hexanol (isononyl alcohol, 1 a) was used as a reaction substrate, and the yield difference among different solvents was significant (numbers 1-4, above examples 1-4); the target compound (2 a) can be obtained in 83% yield only in 12 hours by using acetonitrile as a solvent; one equivalent of acetonitrile was added to 1,2-dichloroethane and toluene, resulting in a significant increase in yield, indicating that acetonitrile has a promoting effect on this reaction (nos. 5 and 6, example 5,6 above).
2) Influence of acetonitrile addition on the reaction: adding 0.5-4 equivalent of acetonitrile, and carrying out reaction; preferably, the addition of 2-4 equivalents gives 82-85% yield of the corresponding isononanoic acid (example 4,7-10 above).
3) Influence of the mode of addition on the reaction: different modes of addition can affect the formation of the reaction by-product (ester, 4 a), with the formation of by-product 4a being significantly reduced when dosed in a dropwise manner (example 11,12 above).
4) Influence of chloride on the reaction: when chloride is added, the reaction can be accelerated to some extent (especially the oxidation process from alcohol to aldehyde) (see fig. 1). After the chloride is added, the generation of aldehyde can reach a peak value after 4 hours; in contrast, the formation of aldehyde without chloride peaked at 8 hours (example 13 above).
The reaction process of the invention is as follows: primary alcohols are first oxidized to the corresponding aldehyde (3) with catalysis of ferric nitrate nonahydrate/4-hydroxy-2,2,6,6-tetramethylpiperidine oxide/potassium chloride, with concomitant formation of the ester (4) and acetal (5) (stage 1); as the reaction proceeds, the aldehyde and acetal are gradually converted into the corresponding carboxylic acid (2) (stage 2)
Thus, naturally, starting from aldehyde (3), the synthesis of carboxylic acid (2) can also be achieved under catalysis of ferric nitrate nonahydrate/4-hydroxy-2,2,6,6-tetramethylpiperidine oxide (example 17 above).
In addition to this, the process is also applicable to polyhydroxy systems (example 29 above):
the solvent related to the invention can be one or a mixture of acetonitrile, 1,2-dichloroethane, 1,1-dichloroethane, 1,2-dichloropropane, 1,3-dichloropropane, dichloromethane, nitromethane, benzene, toluene, ethyl acetate and tetrahydrofuran. Preferably, the best results are obtained with acetonitrile as solvent (additive), the molar ratio of alcohol or corresponding aldehyde/acetonitrile being: 1:1-6; preferably, the molar ratio of alcohol or corresponding aldehyde/acetonitrile is 1:3.
Finally, it is also noted that the above-mentioned list is only a few specific embodiments of the present invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by the person skilled in the art from the present disclosure are to be considered within the scope of the present invention.
Claims (5)
1. A method for synthesizing carboxylic acid compounds from alcohol or corresponding aldehyde by taking oxygen or oxygen in the air as an oxidant is characterized in that a reaction substrate alcohol or corresponding aldehyde is oxidized into the corresponding carboxylic acid compounds under the catalysis of nitrate/4-hydroxy-2,2,6,6-tetramethylpiperidine oxide and the action of an additive;
the method specifically comprises the following steps: adding nitrate, 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide and an additive into a container, pumping gas, then adding a reaction substrate alcohol or corresponding aldehyde into a reaction system at one time or dropwise, and stirring for reaction; concentrating, performing flash column chromatography or distilling directly to obtain carboxylic acid compounds; when the inorganic chloride potassium chloride is additionally added, the reaction is accelerated;
the molar ratio of the alcohol or the corresponding aldehyde to the additive is 1: (2-4); the molar ratio of the alcohol or the corresponding aldehyde to the nitrate to the 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide to the inorganic chloride is 100: (5-10): (5-10) and (5-10);
the additive is acetonitrile;
the nitrate is ferric nitrate nonahydrate.
2. According to claim1, wherein the alcohol is a primary alcohol, RCH 2 OH; wherein R is C3-C15 straight chain or branched chain alkyl, unsaturated alkyl containing benzene ring, alkenyl or alkynyl; the R is substituted by alkoxy and halogen.
3. A process according to claim 2, characterised in that the primary alcohol is a primary monohydric alcohol or a primary dihydric alcohol; wherein the binary primary alcohol is a binary primary alcohol with a carbon number greater than 6.
4. The method of claim 1, wherein the temperature of the reaction is between room temperature and 50 ℃.
5. The method of claim 1, wherein the gas of the pumped gas is pure oxygen or oxygen in air.
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