Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C231/00—Preparation of carboxylic acid amides

Definitions

• the present invention relates to a method for producing carboxylic acid amide.
• Carbonic acid amides which are industrially useful substances, are:-reaction of carboxylic acid or its ester with amine as a killing process, or It is well known that it is produced by the hydrolysis reaction of the corresponding nitrile. Although the yield of each of these processes has reached almost satisfactory levels due to recent technological advances, the processes from petrochemical raw materials are long. In order to shorten the process, for example, a method of reacting carbon monoxide with dimethylamine in the production of N, -dimethylformamide, for example, as disclosed in British Patent No. 9 No. 255558 is a known force; it requires high pressure and requires complicated operations to treat guinea pigs as by-products. Therefore, there is an industrial need to develop a simpler and more economical method.
• the present invention relates to (a) a first-class alcohol, (b) an ammonia,
• WIPO At least one compound selected from the group consisting of primary amines and secondary amines, together with (c) a molecular oxygen-containing gas, (palladium or platinum
• a molecular oxygen-containing gas palladium or platinum
• Primary alcohols are, for example, methanol, ethanol, and isof. Mouth Pinolenoreco nole, n-Tinolenoreconore: 2-ethylinohexanol, ⁇ -octyl alcohol Unsaturated aliphatic primary alcohols such as ethyl alcohol; penzilan alcohol, and aromatic alcohols such as cinnamyl alcohol ⁇ -norethyl) There is a monovalent alcohol such as a non-reactive compound, a non-functional compound such as a heterocyclic alcohol, and the aromatic alcohol described above.
• OMPI Yo OMPI Yo
• polyvalent alcohols such as ethylen, alcohol, alcohol, alcohol, glycerin, etc. may be used.
• methyl alcohol, unsubstituted or substituted pen alcohol, unsubstituted or substituted pyridine A hydrogen atom at the carbon atom adjacent to the carbon atom having an alcoholic hydroxyl group, such as alkanol, unsubstituted or substituted furfuryl alcohol, Adjacent to a carbon atom with an alcoholic hydroxyl group, such as primary alcohol, aryl alcohol, or crotyl alcohol, which has no atoms attached.
• Primary alcohols having an unsaturated bond at the carbon atom of the present invention are used in the present invention. It is excellent in terms of mouth reaction, and it can be used in the following manners: technole, phenol, phenol, phenolic, phenolic, and phenolic. -Nore is most preferably used.
• the first-class amines include methylamine, ethylamine and fu. Mouth Pilamin, Isov. Aliphatic primary amines such as mouth pillamine and ptinoreamin; cyclopropylamine, sick mouth pentylamine, sick mouth hexyl Amin's lunar cyclic primary-amine; aromatic primary amines such as a-line, toluidine, and naphthylamine; and benzylamine Primary aromatic amines, such as aromatic and xylidene diamines; and those with heterocyclic skeletons such as ⁇ nicillin skeleton ⁇ cephalosporin skeleton A typical example is a first-class amine.
• Amine is a chlorine atom, a bromine atom, a fluorine atom, a halogen atom, a methyl atom, an ethyl atom, an isophylamine, a carbon atom constituting an amide compound.
• Alkyl groups such as Q-alkyl groups and alkoxy groups such as methoxy and ethoxy may be substituted.
• particularly preferred compounds are ammonia, the above-mentioned primary amines, dimethylamines, methylamine methylethylamines, pyridines, and pyridines.
• Pellagun is most suitable, for example, ammonia, methylamine, ethylamine, dimethylamine, and ethylamine.
• the amount ratio of the primary alcohol and the compound selected from ammonia, primary amine and secondary amine can be arbitrarily determined depending on the reaction. Although it is possible, the molar ratio of the former (ammonia or amimin) to the former (the first-class alcohol) is, in effect, the former (the first-class alcohol). ) For one mole, the latter (ammonia or ami)
• the range is from 0.02 mol to about 100 mol, with the former being approximately 1 mol and the latter being approximately 0.01 mol or more.
• the oxygen used in the present invention may be molecular oxygen, that is, oxygen gas itself or a mixed gas obtained by diluting oxygen gas with a reaction-inactive diluent gas, for example, nitrogen, carbon dioxide gas, or the like. Can also be used.
• the amount of oxygen present in the reaction system is more than the stoichiometric amount required for the reaction, and preferably about 1.5 times the stoichiometric amount.
• the catalyst used is palladium or platinum, which may be a metal itself, but it is preferable to use the metal supported on a carrier.
• the carrier to be used may be an ordinary one such as activated carbon, diaper, and alumina.
• the amount of metal supported on such a carrier may be a force that can be used in a range of about 0.1 to about 20 weight by weight, preferably a force in a range of about 0.5 to about 10 weight.
• organic acid salts include salts of gum, acetic acid, lopionic acid, stearic acid, malonic acid, succinic acid, glutaric acid, maleic acid, benzoic acid, and phthalic acid. Is used.
• the amount of lead, thallium, or mercury added to palladium or platinum is about ⁇ .01 in atomic ratio.
• the preparation of these catalysts may be carried out by a commonly used method, but one example is to immerse the carrier in an aqueous solution of nora, couma or a platinum salt, and after drying, subject to hydrogen, hydra Can be converted to metallic form and used for the reaction.
• the above-mentioned method for preparing a catalyst containing lead, thallium or mercury is carried out by a usual method, for example, adding a carrier to an aqueous solution of acetic acid, stirring for several hours, adsorbing lead acetate, Bake to 500 ° C to about 700 ° C. Further, this was added to an aqueous solution of palladium chloride, and after stirring for several hours, palladium chloride was adsorbed, and then reduced by holmaline, hydrazine, and hydrogen. To reduce.
• the carrier can be obtained by adding a platinum-supported carrier to an aqueous solution of a lead salt, stirring, and then drying.
• the carrier is supported when lead, thallium, or mercury is added, and the preferable amount of palladium or platinum supported on the carrier is about 0. It is in the range from 1 to about 20 weight, particularly preferably in the range from about 0.5 to about 10 weight. If you compare paradium with platinum,
• the reaction temperature in the present invention is preferably about 0 to about 200 ° C, and can be carried out at a relatively low temperature of about 15 to about 150 ° C. Having oxidizing activity near normal temperature is a wonder. Further, in order to solubilize the reaction raw materials, a solvent inert to the reaction, for example, dimethylformamide, dioxane, etc. can be used. The pressure can be reduced, atmospheric, or increased. Furthermore, the reaction can be carried out in a batch system or a continuous system.
• Di main Chi le ⁇ Mi emissions (4 0 wt) aqueous solution of 1 0 cc, commercially available as a METHANOL 1 OO cc and a catalyst 5% Nono 0 La di U beam - Ka turbo emissions (e emissions del Ha (Manufactured by Rude Co., Ltd.) was placed in a flask equipped with a gas inlet, convection cooler, stirrer, and thermometer, and the temperature inside the flask was adjusted to 40 ° C. While the solution was sufficiently stirred, air was passed through the gas inlet at a rate of 15 1 for 2 hours to react.
• a catalyst such as a catalyst was added to 50 cc of an aqueous solution containing 5 ⁇ -pyridyl alcohol, a kind of pyryl alcohol, containing 5 ⁇ . 5 ha.
• Radium-capo, 2 (from Angelhard) 2 ⁇ is inserted, the temperature is brought to 50 ° 0, ammonia gas is reduced to 0.3 / Hr, and air is removed.
• the reaction was carried out by passing air through the gas inlet at a speed of 10 ° C for 2 hours while stirring the reaction solution sufficiently.
• Aqueous solution of methane, 40% by weight of methinoreamin (40% by weight), dioxane 20 as a solvent, and activated carbon-supported catalyst [palladium 5% Supported, Pd: P 1: 3 (atomic ratio) Pb is supported as acetic acid) in the same apparatus as in Example 1 at a reaction temperature of 40 ° C and a rate of 5 Hr of oxygen. The reaction was carried out for 2 hours at, and the following result was obtained.
• Circular alcohol 2 methylamine (40 °) aqueous solution 30, dioxane as a solvent 30 ⁇ and activity
• a carboxylic acid amide can be obtained in good yield from alcohol and amiso under mild conditions, and can be synthesized in one step. Very economically advantageous.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Catalysts (AREA)
• Pyridine Compounds (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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• 1978
  • 1978-08-03 JP JP9413578A patent/JPS5522611A/ja active Granted
• 1979
  • 1979-08-01 US US06/195,740 patent/US4329462A/en not_active Expired - Lifetime
  • 1979-08-01 WO PCT/JP1979/000201 patent/WO1982003623A1/ja not_active Ceased

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