471-25-0Relevant articles and documents
Synthetic method of propiolic acid
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Paragraph 0020-0029, (2020/07/24)
The invention discloses a synthetic method of propiolic acid. The method comprises the following steps of: putting calcium carbide, a hydrogen donor, a solvent, a catalyst and an auxiliary agent intoa reaction kettle, introducing carbon dioxide into the reaction kettle, and heating and pressurizing to react, wherein the reaction temperature is 30-80 DEG C, the reaction pressure is 1-6 MPa, and the reaction time is 12-24 hours; separating a liquid and a hydrogen donor from the mixture after the reaction, and acidifying the liquid mixture to obtain a product. The propiolic acid synthesis methoddisclosed by the invention is relatively environment-friendly and low in production cost.
Environment-friendly preparation method of propiolic acid derivatives
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Paragraph 0027-0030, (2020/02/14)
The invention discloses an environment-friendly preparation method of propiolic acid derivatives. The preparation method comprises the following steps: (1) with 2,3-dibromosuccinic acid as a raw material, generating a butynedioic acid salt under alkaline conditions; (2) under an acidic condition, carrying out high-temperature decarboxylation to obtain propiolic acid; and (3) adding corresponding methanol or ethanol into propiolic acid in an extraction solvent, and preparing high-yield propiolate under acidic catalytic conditions under the condition that trimethyl orthoformate or triethyl orthoformate participates in dehydration. In the invention, the propiolic acid preparation method is friendly to environment and high in safety coefficient; and the method provided by the invention can beused for preparing methyl propiolate and ethyl propiolate, and has the advantages of small alcohol consumption, thorough reaction, high yield and easiness in separation.
Synthetic method for flavonoid glycoside drug intermediate propiolic acid
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Paragraph 0017-0020; 0022-0024; 0025-0028, (2018/07/30)
The invention discloses a synthetic method for the flavonoid glycoside drug intermediate propiolic acid. The synthetic method comprises the following steps: adding 3-aminopropyne and a sodium nitratesolution into a reaction vessel, controlling a stirring speed, controlling the temperature of the obtained solution, carrying out a reaction, adding an ethyl tert-butyl ether solution, raising solution temperature and carrying out a reaction; and adding antimony pentachloride powder and a diglycol diacetate solution, raising solution temperature, carrying out a reaction, then carrying out extraction with the ethyl t-butyl ether solution a plurality of times, carrying out standing for laying of the obtained solution so as to separate an oil layer, washing the oil layer with a potassium chloridesolution a plurality of times, washing the oil layer with a 3-methyl-2-pentanone solution a plurality of times, then washing the oil layer with a dipropylene glycol solution a plurality of times, carrying out recrystallization in a 1,3-dimethylcyclohexane solution and then carrying out dehydration with a dehydrating agent so as to obtain the finished propiolic acid.
Gold-catalyzed formal [4π+2π]-cycloadditions of tert-butyl propiolates with aldehydes and ketones to form 4H-1,3-dioxine derivatives
Karad, Somnath Narayan,Chung, Wei-Kang,Liu, Rai-Shung
supporting information, p. 13004 - 13007 (2015/08/06)
Gold-catalyzed formal hetero-[4π+2π] cycloadditions of tert-butyl propiolates with carbonyl compounds proceeded efficiently to yield 4H-1,3-dioxine derivatives over a wide scope of substrates. With acetone as a promoter, gold-catalyzed cycloadditions of these propiolate derivatives with enol ethers led to the formation of atypical [4+2]-cycloadducts with skeletal rearrangement.
CuCl catalyzed selective oxidation of primary alcohols to carboxylic acids with tert-butyl hydroperoxide at room temperature
Mannam, Sreedevi,Sekar
, p. 2457 - 2460 (2008/09/20)
Direct oxidation of primary alcohols to the corresponding carboxylic acids is performed highly efficiently at room temperature with anhydrous tert-butyl hydroperoxide in the presence of a catalytic amount of easily available CuCl under ligand free conditions in acetonitrile. Benzylic alcohols are more reactive than aliphatic alcohols, and these benzylic alcohols are selectively oxidized to the corresponding acids in the presence of aliphatic alcohols such as 1-octanol and 1-decanol.
Process for preparing alkynecarboxylic acids by oxidation of alkyne alcohols
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Page 7-8, (2008/06/13)
A process for preparing alkynecarboxylic acids includes the oxidation of an alkyne alcohol with a hypohalite in the presence of a nitroxyl compound at a pH of greater than 7 with continual addition of the alkyne alcohol and of the hypohalite to the reaction mixture.
Partial oxidation of alcohols to aldehydes and ketones under mild conditions
Qian, Guang,Zhao, Rui,Lu, Gaomeng,Qi, Yanxing,Suo, Jishuan
, p. 1753 - 1758 (2007/10/03)
A number of aldehydes and ketones were prepared by partial oxidation of alcohols in air catalyzed by RuO2/ZSM-5 which can be easily prepared with the industrial grade ZSM-5 and RuCl3·xH2O.
Preparation of alkynecarboxylic acids and alkyne alcohol esters of alkynecarboxylic acids by oxidation of alkyne alcohols
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, (2008/06/13)
A process for preparing alkynecarboxylic acids and alkyne alcohol esters of alkynecarboxylic acids, includes an oxidation reaction of an alkyne alcohol with from 1 to 10 molar equivalents of a hypohalite based on the number of functional groups to be oxidized in the presence of a nitroxyl compound at a pH of less than 7. There is also a partial oxidation reaction of the alkyne alcohol with from 0.5 to 5 molar equivalents of a hypohalite based on the number of functional groups to be oxidized in the presence of a nitroxyl compound at a pH of less than 7.
Spectroscopy of hydrothermal reactions 20: Experimental and DFT computational comparison of decarboxylation of dicarboxylic acids connected by single, double, and triple bonds
Li, Jun,Brill, Thomas B.
, p. 9491 - 9498 (2007/10/03)
The kinetics and pathways of decarboxylation of aqueous acetylenedicarboxylic acid at pH = 0.97 - 8.02 were studied in situ at 80-160°C and 275 bar by using an FT-IR spectroscopy flow reactor with sapphire windows. The first-order (or pseudo first-order) rate constants and corresponding Arrhenius parameters were obtained for the neutral acid, monoanion, and dianion. The decarboxylation rates are in the order: HO2CC≡CCO2- > HO2CC≡CCO2H > -O2CC≡CCO2-. The decarboxylation mechanisms of these reactants and the propiolic acid product were analyzed by B3LYP/6-31+G(d) density functional theory. The transition state structures were found for the neutral acids and monoanions. In gas phase the transition state structure is a four-member ring involving C-C(O)-O-H. In aqueous solution a cyclic structure incorporating at least one water molecule forms. A comparison of transition state structures for the decarboxylation of β-saturated (succinic) and β-unsaturated (maleic, fumaric, and acetylenedicarboxylic) aliphatic diacids was made with and without incorporating a water molecule. Consistent with experiment, the calculated activation energy for H-atom transfer to the α carbon atom in the decarboxylation step follows the order C≡C C=C C-C.
Permanganate oxidation of unsaturated alcohols in alkaline media
Jaky, Miklos,Simon-Trompler, Edit
, p. 561 - 567 (2007/10/03)
A study was made on permanganate oxidation of olefinic and acetylenic alcohols in aqueous alkali media. Deprotonation constants of alcohols can be calculated from the kinetic data. The rate constant of alkoxide group oxidation exceeded that of the unsaturated bond. For oxidation of the alcoholic group a mechanism based on hydride ion transfer is proposed.
