WO2021031756A1 - Procédé de synthèse de composés d'acide carboxylique ou de cétone à partir d'alcool ou d'aldéhyde à l'aide d'oxygène ou d'oxygène dans l'air en tant qu'oxydant - Google Patents
Procédé de synthèse de composés d'acide carboxylique ou de cétone à partir d'alcool ou d'aldéhyde à l'aide d'oxygène ou d'oxygène dans l'air en tant qu'oxydant Download PDFInfo
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Definitions
- the present invention relates to a chemical synthesis method. Specifically, it is a new method for synthesizing carboxylic acid or ketone compounds from alcohols or aldehydes using oxygen or oxygen in the air as an oxidant. ,2,6,6-Tetramethylpiperidine oxide is used to oxidize alcohol or aldehyde to the corresponding carboxylic acid or ketone compound.
- Carboxylic acid is a kind of basic chemical raw material and has a pivotal and important position in the chemical industry. Oxidation reaction is the main synthesis route of carboxylic acid compounds.
- the environmental burden brought by traditional oxidation methods (heavy metal oxides) is often an insurmountable obstacle in industrial production. Therefore, air oxidation-based synthesis methods have attracted more and more attention. .
- people have carried out some work in the air oxidation reaction of alcohols catalyzed by cheap metals, and developed some air oxidation systems based on cheap metal catalysts to achieve one-step conversion from alcohol to carboxylic acid (Tetrahedron Lett., 1995, 36, 6923) -6926; Chem.
- the present invention has researched and developed a nitrate/4-hydroxy-2,2,6,6-tetramethylpiperidine oxide based on oxygen or oxygen in the air as the oxidant
- the purpose of the present invention is to provide a simple, efficient, fast and more economical synthesis novel based on nitrate/4-hydroxy-2,2,6,6-tetramethylpiperidine oxide catalytic oxidation carboxylic acid or ketone compound method.
- the present invention discloses a new method for synthesizing carboxylic acid or ketone compound from alcohol or corresponding aldehyde with oxygen or oxygen in the air as oxidant. It is used in nitrate/4-hydroxy-2,2,6,6-tetramethyl Under the catalysis of piperidine oxide and the action of additives, the reaction substrate alcohol or the corresponding aldehyde is oxidized to the corresponding carboxylic acid or ketone compound.
- the reaction formula is as follows:
- the method of the present invention specifically includes the following steps: adding nitrate, 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide and additives into a container, ventilating, and then removing the reaction substrate alcohol Or the corresponding aldehyde is added to the reaction system at a time or dropwise, and the reaction is stirred; concentrated, fast column chromatography or direct distillation and steaming to obtain carboxylic acid or ketone compound.
- the alcohol is primary alcohol RCH 2 OH or secondary alcohol R 1 CHOHR 2 .
- R is C3-C15 linear or branched alkanes, or unsaturated hydrocarbons containing benzene rings or alkenes or alkynes, and the substrate is compatible with functional groups such as alkoxy and halogen; the reaction substrate or the corresponding primary alcohol Of aldehydes.
- the primary alcohol is a primary monohydric alcohol or a primary dihydric alcohol
- the primary dihydric alcohol is a primary dihydric alcohol with a carbon number greater than 6.
- R 1 is C1-C15 linear or branched alkanes, or unsaturated hydrocarbons containing benzene rings or alkenes or alkynes
- R 2 is C1-C15 linear or branched alkanes, or containing benzene rings or Unsaturated hydrocarbons such as alkenes or alkynes.
- the secondary alcohol is a secondary fatty alcohol, benzyl alcohol, allyl alcohol or propargyl alcohol.
- the additives are 1,2-dichloroethane, 1,1-dichloroethane, 1,2-dichloropropane, 1,3-dichloropropane, dichloromethane, nitromethane
- 1,2-dichloroethane, 1,1-dichloroethane, 1,2-dichloropropane, 1,3-dichloropropane, dichloromethane, nitromethane One or more of benzene, toluene, acetonitrile, ethyl acetate, tetrahydrofuran, etc.; preferably, acetonitrile.
- the nitrate is one or a mixture of iron nitrate nonahydrate and copper nitrate trihydrate; preferably, it is iron nitrate nonahydrate.
- the molar ratio of the alcohol or the corresponding aldehyde, nitrate, 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide is 100: (1-10): (1 ⁇ 10); Preferably, it is 100:5:5.
- the molar ratio of the alcohol or the corresponding aldehyde and the additive is 1:(1-6); preferably, it is 1:3.
- the inorganic chloride includes one or more of lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, etc. ; Preferably, it is potassium chloride.
- the molar ratio of the alcohol or corresponding aldehyde and inorganic chloride is 100:(1-10); preferably, it is 100:5.
- the gas for pumping is pure oxygen or oxygen in the air.
- the reaction temperature is room temperature to 50°C; preferably, it is room temperature.
- the invention has the advantages of mild reaction conditions, easy operation, high yield, rich substrate diversity, environmental friendliness and the like.
- nonahydrate ferric nitrate, 2,2,6,6-tetramethyl nitroxide, potassium chloride catalytic system (Aso Ming Jiang Xingguo, a method of oxygen oxidation of alcohol or aldehyde to produce acid, Application number: 201610141434.2, 2016.03.11)
- it has the following advantages: 1) The price of the catalyst is extremely low, and the production cost is greatly reduced; 2) Additives such as acetonitrile can significantly promote the reaction; 3) The amount of solvent is greatly reduced ; 4)
- the reaction can be carried out without adding chloride.
- the invention is not only suitable for laboratory synthesis but also suitable for industrial synthesis of carboxylic acid compounds.
- Figure 1 is a graph showing the effect of chloride addition on the oxidation reaction of isononanol.
- the method for synthesizing carboxylic acid or ketone compound of the present invention is catalyzed by nitrate/4-hydroxy-2,2,6,6-tetramethylpiperidine oxide, in the presence of additives, at room temperature Alcohol or corresponding aldehyde is oxidized to corresponding carboxylic acid or ketone compound, the reaction formula is as follows:
- R can be an alkyl group, an aryl group, an alkene group, an alkynyl group, etc.; preferably, the alkyl group is a straight or branched chain alkane with 3 to 15 carbons, which is compatible with functional groups such as alkoxy and halogen.
- R 1 is a C1-C15 linear or branched alkane, or an unsaturated hydrocarbon containing a benzene ring or alkene or alkyne
- R 2 is a C1-C15 linear or branched alkane or a benzene ring or alkene or alkyne Unsaturated hydrocarbons such as hydrocarbons.
- the steps are: adding nitrate, 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide and additives into a three-necked flask, pumping air (pure oxygen or air), and then adding alcohol to In the reaction system, the reaction is stirred at room temperature for 10-72 hours; concentrated, flash column chromatography (or direct distillation and steaming) to obtain carboxylic acid compounds.
- ferric 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 dichloromethane (2mL), ventilate (pure oxygen) three times, stir at room temperature (25°C) for 33 hours, and obtain 41% of 2a (with dibromomethane as internal Standard, nuclear magnetic yield), 27% of 3a (using dibromomethane as internal standard, nuclear magnetic yield).
- the solvent has a significant influence on the reaction: 3,5,5-trimethyl-1-hexanol (isononyl alcohol, 1a) is used as the reaction substrate, and the yields in different solvents are significantly different (No. 1-4, The above examples 1-4); using acetonitrile as a solvent, the target compound (2a) can be obtained with a yield of 83% in only 12 hours; adding one equivalent of acetonitrile to 1,2-dichloroethane and toluene produces The rate is significantly increased, showing that acetonitrile has a promoting effect on the reaction (Sequence No. 5 and 6, Examples 5 and 6 above).
- the reaction process of the present invention is: the primary alcohol is first oxidized to the corresponding aldehyde under the catalysis of nonahydrate ferric nitrate/4-hydroxy-2,2,6,6-tetramethylpiperidine oxide/potassium chloride (3 ), accompanied by the formation of esters (4) and acetals (5) (stage 1); as the reaction proceeds, aldehydes and acetals are gradually converted into corresponding carboxylic acids (2) (stage 2)
- the solvent involved in the present invention can be acetonitrile, 1,2-dichloroethane, 1,1-dichloroethane, 1,2-dichloropropane, 1,3-dichloropropane, dichloromethane, nitro One or a mixture of methane, benzene, toluene, ethyl acetate, and tetrahydrofuran.
- acetonitrile is used as the solvent (additive) to achieve the best effect.
- the molar ratio of alcohol or corresponding aldehyde/acetonitrile is 1:1 to 6; preferably, the molar ratio of alcohol or corresponding aldehyde/acetonitrile is 1:3 .
Abstract
L'invention concerne un nouveau procédé de synthèse de composés d'acide carboxylique ou de cétone à partir d'un alcool ou d'un aldéhyde correspondant à l'aide d'oxygène ou d'oxygène dans l'air en tant qu'oxydant. Sous la catalyse par un nitrate/oxyde de 4-hydroxy-2,2,6,6-tétraméthylpipéridine et sous l'action d'additifs, un alcool ou un aldéhyde correspondant est oxydé en un composé d'acide carboxylique ou de cétone correspondant. Lorsqu'un chlorure inorganique supplémentaire est ajouté, la réaction est accélérée. L'invention présente des avantages tels qu'un faible prix de catalyseur, un fonctionnement facile, un rendement élevé, une diversité riche en substrats, des conditions de réaction modérées et le fait d'être écologique. L'invention est non seulement appropriée pour la synthèse en laboratoire mais également appropriée pour la synthèse industrielle de composés d'acide carboxylique ou de cétone.
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