4771-80-6Relevant articles and documents
Asymmetric Synthesis of Optically Active 3-Cyclohexene-1-carboxylic Acid Utilizing Lactic Ester as a Chiral Auxiliary in the Diastereoselective Diels–Alder Reaction
Ochiai, Hidenori,Hayashi, Wakana,Nishiyama, Akira,Fujita, Ryunosuke,Kubota, Shunichi,Sasagawa, Miwa,Nishi, Tatsuya
supporting information, p. 1002 - 1009 (2022/02/09)
The optically active 3-cyclohexene-1-carboxylic acid was synthesized through a TiCl4-catalyzed diastereoselective Diels–Alder reaction utilizing lactic acid ester as a chiral auxiliary, which can be removed by washing with H2O. The (S)- and (R)-isomers were both derived from easily available ethyl l-lactate.
Selective α,δ-hydrocarboxylation of conjugated dienes utilizing CO2and electrosynthesis
Buckley, Benjamin R.,Elmorsy, Saad S.,Malkov, Andrei V.,Mashaly, Mohammad A.,Said, Samy B.,Sheta, Ahmed M.
, p. 9109 - 9114 (2020/09/17)
To date the majority of diene carboxylation processes afford the α,δ-dicarboxylated product, the selective mono-carboxylation of dienes is a significant challenge and the major product reported under transition metal catalysis arises from carboxylation at the α-carbon. Herein we report a new electrosynthetic approach, that does not rely on a sacrificial electrode, the reported method allows unprecedented direct access to carboxylic acids derived from dienes at the δ-position. In addition, the α,δ-dicarboxylic acid or the α,δ-reduced alkene can be easily accessed by simple modification of the reaction conditions. This journal is
Organocatalyzed Aerobic Oxidation of Aldehydes to Acids
Dai, Peng-Fei,Qu, Jian-Ping,Kang, Yan-Biao
supporting information, p. 1393 - 1396 (2019/02/26)
The first example organocatalyzed aerobic oxidation of aldehydes to carboxylic acids in both organic solvent and water under mild conditions is developed. As low as 5 mol % N-hydroxyphthalimide was used as the organocatalyst, and molecular O2 was used as the sole oxidant. No transition metals or hazardous oxidants or cocatalysts were involved. A wide range of carboxylic acids bearing diverse functional groups were obtained from aldehydes, even from alcohols, in high yields.
Zinc Oxide-Catalyzed Dehydrogenation of Primary Alcohols into Carboxylic Acids
Monda, Fabrizio,Madsen, Robert
supporting information, p. 17832 - 17837 (2018/11/23)
Zinc oxide has been developed as a catalyst for the dehydrogenation of primary alcohols into carboxylic acids and hydrogen gas. The reaction is performed in mesitylene solution in the presence of potassium hydroxide, followed by workup with hydrochloric acid. The transformation can be applied to both benzylic and aliphatic primary alcohols and the catalytically active species was shown to be a homogeneous compound by a hot filtration test. Dialkylzinc and strongly basic zinc salts also catalyze the dehydrogenation with similar results. The mechanism is believed to involve the formation of a zinc alkoxide which degrades into the aldehyde and a zinc hydride. The latter reacts with the alcohol to form hydrogen gas and regenerate the zinc alkoxide. The degradation of a zinc alkoxide into the aldehyde upon heating was confirmed experimentally. The aldehyde can then undergo a Cannizzaro reaction or a Tishchenko reaction, which in the presence of hydroxide leads to the carboxylic acid.
Preparation method of cycloalkene carboxylic acid
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Paragraph 0017; 0018; 0019; 0020, (2018/05/16)
The invention discloses a preparation method of cycloalkene carboxylic acid. The preparation method of cycloalkene carboxylic acid represented as the molecular formula I comprises steps as follows: unsaturated fatty acid represented as the molecular formula II and 1,3-butadiene are subjected to polymerization reaction for 1-3 h in a pressure vessel at the temperature of 120-300 DEG C with aqueousphase serving as a solvent in an inert environment with nitrogen pressurized gauge pressure being 1.0-5.0 MPa, then a synthesis liquid is transferred into a distillation kettle for distillation underthe negative-pressure condition, and cycloalkene carboxylic acid represented as the molecular formula I is obtained. Overall, the preparation method has the advantages as follows: reaction speed is high, reaction period is short, the reaction is performed in the aqueous phase, purification of cycloalkene carboxylic acid is facilitated, operation is simple and convenient, continuous production canbe executed, product quality is effectively improved, and use value is quite high.
An Efficient Aerobic Oxidation Protocol of Aldehydes to Carboxylic Acids in Water Catalyzed by an Inorganic-Ligand-Supported Copper Catalyst
Yu, Han,Ru, Shi,Zhai, Yongyan,Dai, Guoyong,Han, Sheng,Wei, Yongge
, p. 1253 - 1257 (2018/02/16)
A method for the aerobic oxidation of aldehydes to carboxylic acids in water by using an inorganic-ligand-supported copper catalyst was developed. This method was performed with the use of atmospheric oxygen as the sole oxidant under extremely mild aqueous conditions, and furthermore, a wide range of aldehydes with various functional groups were tolerated. The copper catalyst could be recycled and used in successive reactions at least six times without any appreciable degradation in performance. This method is operationally simple and avoids the use of high-costing, toxic, air/moisture-sensitive, and commercially unavailable organic ligands. The generality of this method gives it potential to be used on the industrial scale.
Method for preparing acid through oxidating alcohols or aldehydes by oxygen
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Paragraph 0051; 0052; 0053; 0054; 0094; 0095; 0096, (2017/09/29)
The invention provides a method for preparing acid through oxidating alcohols or aldehydes by using oxygen or oxygen in air as an oxidant. The method comprises the steps: oxidating the alcohols or aldehydes to produce the acid at room temperature in an organic solvent in a manner of taking ferric nitrate (Fe(NO3)3.9H2O), 2,2,6,6-tetramethylpiperidyl nitrogen oxide (TEMPO) and an inorganic halide as catalysts and taking the oxygen or air as an oxidant, and oxidating diols to produce lactone; or, carrying out a reaction on the aldehydes, which serve as a raw material, under neutral conditions by taking ferric nitrate as a catalyst, and oxidating the aldehydes to produce the acid and peroxy acid. The method has the advantages that the method is environmentally friendly, the cost is low, the yield is high, the atomic economical efficiency is high, the compatibility of substrate functional groups is good, the reaction conditions are mild, a reaction scale can be enlarged, and the like, so that the method is suitable for being applied to industrial production.
Silver-Catalyzed Dehydrogenative Synthesis of Carboxylic Acids from Primary Alcohols
Ghalehshahi, Hajar Golshadi,Madsen, Robert
, p. 11920 - 11926 (2017/09/07)
A simple silver-catalyzed protocol has been developed for the acceptorless dehydrogenation of primary alcohols into carboxylic acids and hydrogen gas. The procedure uses 2.5 % Ag2CO3 and 2.5–3 equiv of KOH in refluxing mesitylene to afford the potassium carboxylate which is then converted into the acid with HCl. The reaction can be applied to a variety of benzylic and aliphatic primary alcohols with alkyl and ether substituents, and in some cases halide, olefin, and ester functionalities are also compatible with the reaction conditions. The dehydrogenation is believed to be catalyzed by silver nanoparticles that are formed in situ under the reaction conditions.
BORON-BASED CYCLOADDITION CATALYSTS AND METHODS FOR THE PRODUCTION OF BIO-BASED TEREPHTHALIC ACID, ISOPHTHALIC ACID AND POLY (ETHYLENE TEREPHTHALATE)
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Paragraph 00171; 00187, (2017/04/11)
Methods for producing cycloaddition products comprising: reacting a diene with a dienophile in the presence of one or more boron-based catalysts of Formula I or Formula II are provided. In particular, the methods can be used to prepare 4-methyl-3-cyclohexene- 1-carboxylic acid and 3-methyl-3-cyclohexene-l-carboxylic acid, including bio-based versions thereof. The cycloaddition products can be advantageously used in the production of terephthalic acid and isophthalic acid, and ultimately, poly(ethylene terephthalate), and bio-based versions thereof. Formula I Formula II
An Efficient Iron(III)-Catalyzed Aerobic Oxidation of Aldehydes in Water for the Green Preparation of Carboxylic Acids
Yu, Han,Ru, Shi,Dai, Guoyong,Zhai, Yongyan,Lin, Hualin,Han, Sheng,Wei, Yongge
, p. 3867 - 3871 (2017/03/27)
The first example of a heterogeneous iron(III)-catalyzed aerobic oxidation of aldehydes in water was developed. This method utilizes 1 atmosphere of oxygen as the sole oxidant, proceeds under extremely mild aqueous conditions, and covers a wide range of various functionalized aldehydes. Chromatography is generally not necessary for product purification. Its operational simplicity, gram-scale oxidation, and the ability to successively reuse the catalyst, make this new methodology environmentally benign and cost effective. The generality of this methodology gives it the potential to be used on an industrial scale.
