- An improved method for the synthesis of phenylacetic acid derivatives via carbonylation
-
2,4-Dichlorophenylacetic acid is synthesized in high yield via the carbonylation of 2,4-dichlorobenzyl chloride, and various experimental conditions are evaluated. Xylene, bistriphenylphosphine palladium dichloride, tetraethylammonium chloride and sodium hydroxide in solution are added to the reaction system and held at 80 °C under a CO atmosphere. 2,4-Dichlorophenylacetic acid is obtained in a maximum yield of 95percent, and a mechanism for 2,4-dichlorobenzyl chloride carbonylation is proposed. The reaction system provides a mild, effective and novel means by which to prepare phenylacetic acid derivatives from their corresponding benzyl chloride derivatives.
- Li, He,Zhang, Yijun,Liu, Dinghua,Liu, Xiaoqin
-
-
Read Online
- Oxidation of Alkynyl Boronates to Carboxylic Acids, Esters, and Amides
-
A general efficient protocol was developed for the synthesis of carboxylic acids, esters, and amides through oxidation of alkynyl boronates, generated directly from terminal alkynes. This protocol represents the first example of C(sp)?B bond oxidation. This approach displays a broad substrate scope, including aryl and alkyl alkynes, and exhibits excellent functional group tolerance. Water, primary and secondary alcohols, and amines are suitable nucleophiles for this transformation. Notably, amino acids and peptides can be used as nucleophiles, providing an efficient method for the synthesis and modification of peptides. The practicability of this methodology was further highlighted by the preparation of pharmaceutical molecules.
- Li, Chenchen,Li, Ruoling,Zhang, Bing,Zhao, Pei,Zhao, Wanxiang
-
supporting information
p. 10913 - 10917
(2020/05/25)
-
- Preparation method of acid with different substituent groups
-
The invention discloses a preparation method of an acid with different substituent groups. A terminal alkyne is lithiated with n-butyllithium, and then reacts with isopropoxyboronic acid pinacol ester, hydrogen chloride is added to achieve quenching, then the obtained reaction product is oxidized by an oxidizing agent, and the oxidized reaction product is separated and purified to obtain the acid.The method of the invention has the advantages of simplicity in operation, one-pot process preparation, no metal catalysis, nontoxic reagents, greenness, environmental friendliness and high atomic utilization rate, and provides a novel and quick way for preparing the acid with different substituent groups; and the obtained acid is an important fine chemical product, and can be widely used in fields of medicines, pesticides, spices and other industries.
- -
-
Paragraph 0073-0077
(2019/10/23)
-
- Preparation method of phenylacetic acid type compound
-
The invention discloses a preparation method of a phenylacetic acid type compound. The preparation method of the phenylacetic acid type compound I comprises the following steps that in a solvent and aCO gas phase system, a benzyl halide type compound II, pyridine-2-cobalt carboxylate, palladium acetate and alkaline neutralizers take carbonylation reaction to obtain the phenylacetic acid type compound I. A mixed catalytic system has a synergistic effect; the whole use quantity of catalysts is greatly reduced. When the mixed catalyst is used, a better catalytic effect can be achieved; the characteristics of easily obtaining the catalyst, avoiding the production safety risk of toxic three wastes and the like, reducing the reaction pressure, realizing mild reaction conditions, reducing the production risk, facilitating the production and the like are realized. The formulas are shown in description.
- -
-
Paragraph 0083; 0084; 0085
(2019/02/21)
-
- The selenium-containing complexes in the phenylacetic acid and its derivatives or its application in the synthesis of (by machine translation)
-
The present invention provides a kind of structural formula (I) indicated by the 2 - (2 - carboxyl phenyl) benzothiazole of selenium-containing complexes of, this kind of selenium-containing complex can be applied to the catalytic benzyl chloride rigid synthetic phenylacetic acid or derivatives thereof in the reaction, in the reaction, the less the amount of catalyst, the catalytic activity is high, simple operation, conducive to such synthetic method in industry popularization and application. (by machine translation)
- -
-
Paragraph 0019; 0020; 0023; 0024
(2018/07/30)
-
- Ruthenium-catalyzed umpolung carboxylation of hydrazones with CO2
-
The first ruthenium-catalyzed umpolung carboxylation of hydrazones with CO2 to generate important aryl acetic acids is reported. Besides aldehyde hydrazones, a variety of ketone hydrazones, which have not been successfully applied in previous umpolung reactions with other reactive electrophiles, also show high reactivity and selectivity under mild conditions. Moreover, this operationally simple protocol features good functional group tolerance, is readily scalable, and offers easy derivation of important structures, including bioactive felbinac and adiphenine. Computational studies reveal that this umpolung reaction proceeds through the generation of a Ru-nitrenoid followed by concerted [4 + 2] cycloaddition with CO2.
- Yan, Si-Shun,Zhu, Lei,Ye, Jian-Heng,Zhang, Zhen,Huang, He,Zeng, Huiying,Li, Chao-Jun,Lan, Yu,Yu, Da-Gang
-
p. 4873 - 4878
(2018/06/07)
-
- A phenylacetic acid compound preparation method (by machine translation)
-
The invention relates to the field of chemical synthesis, in particular relates to a preparation method of the compound of phenylacetic acid. The present invention provides a preparation method of the compound of phenylacetic acid, the acid compounds of the structural formula states the benzene second grade shown in formula I, the preparation method comprises the following steps: (1) diazo addition reaction: formula II compound containing vinylidene chloride, acid, diazotization reagent, phase transfer catalyst and a copper catalyst in the system of the formula III compound: (2) hydrolysis reaction: the compound of formula III in the presence of acid hydrolysis of formula I compounds. The present invention provides a preparation method of and is simple, easy operation, low cost of raw materials, mild reaction conditions, low risk, does not need to use expensive noble metal catalyst and complex industrial operation means, the product quality is stable, therefore easy achievement of large-scale industrial production. (by machine translation)
- -
-
Paragraph 0112
(2018/03/01)
-
- Regio- and Stereoselective Oxidation of Styrene Derivatives to Arylalkanoic Acids via One-Pot Cascade Biotransformations
-
Green and selective oxidation methods are highly desired in chemical synthesis and manufacturing. In this work, we have developed a biocatalytic method for the regio- and stereoselective oxidation of styrene derivatives into arylacetic and (S)-2-arylpropionic acids via a one-pot epoxidation–isomerization–oxidation sequence. This was done via the engineering of Escherichia coli (StyABC-EcALDH) coexpressing styrene monooxygenase (SMO), styrene oxide isomerase (SOI) and aldehyde dehydrogenase (EcALDH) as an active and easily available whole-cell catalyst. Regioselective oxidation of styrene and 11 substituted styrenes using the E. coli cells was performed in a one-pot set-up, producing 12 phenylacetic acids in both high conversion and high yield. Engineering of E. coli (StyABC-ADH9v1) coexpressing SMO, SOI and ADH9v1 (a mutated alcohol dehydrogenase) led to biocatalysts capable of regio- and stereoselective oxidation of α-methylstyrene derivatives to the corresponding chiral acids. One-pot asymmetric synthesis of 4 (S)-2-arylpropionic acids was achieved in good conversion and excellent ee with the E. coli cells. This is a new type of asymmetric alkene oxidation to give chiral acids with no chemical counterpart thus far. The cascade bio-oxidation operates under mild conditions, uses molecular oxygen, exhibits very high regio- and enantioselectivity, and gives high conversion, thus providing a green and efficient method for the synthesis of arylacetic acids and (S)-2-arylpropionic acids directly from easily available styrenes. (Figure presented.).
- Wu, Shuke,Zhou, Yi,Seet, Daniel,Li, Zhi
-
p. 2132 - 2141
(2017/06/23)
-
- An efficient one pot method for synthesis of carboxylic acids from nitriles using recyclable ionic liquid [bmim]HSO4 Dedicated to my mentor Professor (Mrs.) Krishna Misra on her 76th birthday
-
Environmentally benign ionic liquid [bmim]HSO4 was found suitable for conversion of nitriles into carboxylic acids under mild conditions with excellent purity.
- Kumar, Satyanand,Dixit, Sandeep Kumar,Awasthi, Satish Kumar
-
supporting information
p. 3802 - 3804
(2014/07/07)
-
- Palladium-catalyzed silver-mediated α-arylation of acetic acid: A new approach for the α-arylation of carbonyl compounds
-
A new approach for the α-arylation of acetic acid through Pd-catalyzed silver-mediated direct C-H arylation of acetic acid with aryl iodides was developed. This protocol provided a straightforward method for the synthesis of a diverse set of α-phenylacetic acids. Palladium served on a silver platter: A new approach for the α-arylation of acetic acid through Pd-catalyzed silver-mediated direct C-H arylation of acetic acid with aryl iodides is presented. This protocol provides a straightforward method for the synthesis of a diverse set of α-phenylacetic acids. Deuteration experiments are performed to help elucidate the reaction mechanism.
- Wu, Guo-Jie,Guan, Jing,Han, Fu-She,Zhao, Yu-Long
-
p. 1589 - 1593
(2014/06/24)
-
- PROCESS FOR SYNTHESIZING PHENYLACETIC ACID BY CARBONYLATION OF TOLUENE
-
A production process for substituted phenylacetic acids or ester analogues thereof is disclosed. In this process toluene or toluene substituted with various substituents, an alcohol, an oxidant and carbon monoxide are used as raw materials to obtain compounds comprising structure of phenylacetic acid ester or analogues thereof by catalysis of the complex catalyst formed from transition metal and ligand, and such compounds are hydrolyzed to obtain various substituted phenylacetic acid based compounds. This type of compounds and their derivatives serve as important fine chemicals used widely in the industries of pharmaceuticals, pesticides, perfume and the like.
- -
-
Paragraph 0018; 0068; 0069
(2013/11/19)
-
- An efficiently cobalt-catalyzed carbonylative approach to phenylacetic acid derivatives
-
A highly efficient cobalt-catalyzed carbonylative approach to phenylacetic acid derivatives under one atmosphere pressure is reported. This methodology represents a useful extension of benzimidazole used as ligand in metal catalysis, and the catalytic mechanism has been proved by computer simulation. Notably, this new cobalt precatalyst, which promotes the carbonylation reaction dramatically and has already been used for scale-up experiment of phenylacetic acid derivatives.
- She, Meng-Yao,Xiao, Da-Wei,Yin, Bing,Yang, Zheng,Liu, Ping,Li, Jian-Li,Shi, Zhen
-
p. 7264 - 7268
(2013/08/23)
-
- Nitrile biotransformation by whole cells of Aspergillus sp. PTCC 5266
-
Aspergillus sp. PTCC 5266 exhibited nitrile-hydrating activity over a broad pH range from 6.0 to 10.0 at 26°C. It hydrated 4-nitrophenylacetonitrile, 2-chlorobenzonitrile and 3-chlorobenzonitrile to their corresponding carboxylic acids and amides, while benzyl cyanide, benzonitrile, 4-tolunitrile, cyclohexanecarbonitrile, 4-chlorobutyronitrile and isobutyronitrile gave carboxylic acids as the sole products. The maximum whole-cell nitrile-hydrating activity was observed at pH 7.0.
- Yousefi,Mohammadi,Habibi,Cheraghi
-
body text
p. 54 - 59
(2012/03/10)
-
- Exceptionally simple catalytic system for the carbonylation of benzyl halides
-
A ligand-less catalytic system, Pd(OAc)2 immobilized in NBu4Hal melt is suggested for the synthesis of arylacetic acids by the carbonylation of benzyl bromides.
- Lapidus, Albert L.,Eliseev, Oleg L.,Bondarenko, Tatyana N.,Chau, Nguen H.,Kazantsev, Ruslan V.
-
scheme or table
p. 256 - 257
(2010/01/18)
-
- Induced thermolysis of tert-butyl phenylperacetates by thiophenol: Simultaneous occurrence of homolysis and single electron transfer
-
Thermolysis of tert-butyl phenylperacetates in the presence of thiophenol takes place via dual mechanism. The two-bond homolysis indicates ρH+ = -1.16, testifying to polar transition states. The single electron transfer yields a radical anion intermediate which undergoes fragmentation with ρET = 1.01.
- Sung Soo Kim,Tuchkin,Chun Soo Kim
-
p. 7738 - 7740
(2007/10/03)
-
- Quinolones as gonadotropin releasing hormone (GnRH) antagonists: Simultaneous optimization of the C(3)-aryl and C(6)-substituents
-
A series of 3-arylquinolones was prepared and evaluated for their ability to act as gonadotropin releasing hormone (GnRH) antagonists. A variety of substitution patterns of the 3-aryl substituent are described. The 3,4,5-trimethylphenyl substituent (23h) was found to be optimal. (C) 2000 Elsevier Science Ltd. All rights reserved.
- Young, Jonathan R.,Huang, Song X.,Chen, Irene,Walsh, Thomas F.,DeVita, Robert J.,Wyvratt Jr., Matthew J.,Goulet, Mark T.,Ren, Ning,Lo, Jane,Yang, Yi Tien,Yudkovitz, Joel B.,Cheng, Kang,Smith, Roy G.
-
p. 1723 - 1727
(2007/10/03)
-
- Study of interactive free-energy relationships on ruthenium(III) catalyzed oxidation of phenyl styryl ketone and its substituted analogues by V(V) in acid medium
-
Kinetics of Ru(III) catalyzed oxidation of phenyl styryl ketone (PSK) and its substituted analogues by V(V) has been investigated in aqueous acetic acid-sulphuric acid medium in the temperature range 298-313 K. First-order dependence each on [V(V)], [PSK], and [Ru(III)] was observed. Inverse first-order dependence was observed for [V(IV)]. The rate decreased with the increase in dielectric constant (D) of the medium. The rates were enhanced by electron-donating substituents in both the phenyl rings and decreased by electron-with-drawing substituents. Linear Hammett's plots were obtained for various substituents in benzaldehyde moiety of PSK for a given substituent in acetophenone moiety and vice versa. The mechanism proposed envisages formation of Ru(IV) from V(V)+Ru(III) reaction followed by the attack on C double bond O by Ru(IV). Applicability of interactive free-energy relationship has been tested. The cross-interaction constants qx and qy have been determined at different temperatures and possible interpretations discussed.
- Annapoorna,Prasad Rao,Sethuram
-
p. 581 - 588
(2007/10/03)
-
- Pyrrolidinyl hydroxamic acid compounds and their production process
-
A compound of formula (I) STR1 and its pharmaceutically acceptable salt, wherein A is hydrogen or OY, wherein Y is a hydroxy protecting group; Ar is phenyl optionally substituted with one or more substituents selected from halo, hydroxy, C1 -C4 alkyl, C1 -C4 alkoxy, CF3, C1 -C4 alkoxy-C1 -C4 alkyloxy and carboxy-C1 -C4 alkyloxy; X is phenyl, naphthyl, biphenyl, indanyl, benzofuranyl, benzothiophenyl, 1-tetralone-6-yl,C1 -C4 alkylenedioxy, pyridyl, furyl and thienyl these groups optionally being substituted with up to three substituents selected from halo, C1 -C4 alkyl, C1 -C4 alkoxy, hydroxy, NO2, CF3 and SO2 CH3 ; and R is hydrogen, C1 -C4 alkyl or a hydroxy protecting group. These compounds and pharmaceutical compositions containing them are useful as analgesic, anti-inflammatory, diuretic, anesthetic or neuroprotective agents, or an agent for stroke or treatment of functional bowel diseases such as abdominal pain, for the treatment of a mammalian subject, especially a human subject. Further, the present invention provides processes for producing the hydroxamic compounds of formula (I) and their intermediate compounds of the formula. STR2
- -
-
-
- Rat hepatic microsomal aldehyde dehydrogenase. Identification of 3- and 4-substituted aromatic aldehydes as substrates of the enzyme
-
The rat hepatic microsomal aldehyde dehydrogenase (mALDH) metabolizes aliphatic and aromatic aldehydes to the corresponding acids with NAD as the optimal cofactor. However, dehydrogenation of the aliphatic compounds is substantially more efficient. In the present study, a series of aromatic aldehydes was evaluated as substrates of the purified mALDH so that the physicochemical factors that contribute to substrate affinity could be evaluated. Substitution of the aromatic system in the 3- and 4-positions produced relatively good substrates, but 2-substituted congeners did not undergo dehydrogenation. However, aldehydes with hydrophilic substituents in the 3- or 4-positions and those with extremely bulky substituents at both positions (e.g., 3,4-dibenzyloxy) were also poor substrates for the enzyme and dehydrogenation was undetectable. A quantitative structure-activity relationship was determined that related the logarithm of the Michaelis constants for 27 substituted aromatic aldehydes with the zero-order connectivity function of the molecule (0χ), the shapes of the 3-and 4-substituents (κ), and the electronic nature of the 4-substituent (σ). In this equation, 81% of the data variance was explained. From a consideration of the dimensions of 3-phenoxybenzaldehyde, which was a relatively good substrate, the mALDH possesses a narrow cleft within the active site that is at least 7.5 A wide and extends at least 12 A from the the catalytic residue (probably cysteine). Previously established relationships between connectivity functions and molecular polarizability suggest that dipolar interactions within the active site, as well as dispersion forces, may play a role in substrate specificity. Although optimal shapes for carbocyclic substituents were not provided by the analysis, the unfavorable effect on dehydrogenation from hydrophilic and large substituents suggests that the active site of the mALDH is relatively rigid and that the orientation of the substrate in relation to the catalytic cysteine and the cofactor binding site is critical.
- Martini, Robert,Murray, Michael
-
p. 268 - 276
(2007/10/03)
-
- Esters of α-Arylalkanoic Acids from 'Masked' α-Halogenoalkyl Aryl Ketones and Silver Salts: Synthetic, Kinetic, and Mechanistic Aspects
-
A method for the synthesis of alkyl esters of α-arylalkanoic acids is given based on silver-ion-assisted (AgBF4, AgOSO2CF3, AgSbF6, AgNO3) solvolysis of alkyl acetals of primary and secondary α-halogenoalkyl aryl ketones (Hal = I, Br, Cl) in an alcoholic medium (methanol, ethanol).The reaction is quite selective and alkyl esters are the only reaction products; ethers, which are possible substitution products, are not found.The importance of masking the carbonyl as the acetal is emphasised.The reaction is found to be first-order in AgBF4 and in the primary α-halogeno acetal.A three-point Hammett correlation (ρ = -3.29) between ?+ and the rate constants suggests a large cationic contribution as well as strong aryl participation in the transition state.The role payed by the oxygen of the acetal group in the specificity of the reaction is discussed in comparison with the reactivity of analogous compounds with saturated skeletons and of α-halogenoalkyl aryl ketones.
- Giordano, Claudio,Castaldi, Graziano,Casagrande, Francesco,Belli, Aldo
-
p. 2575 - 2582
(2007/10/02)
-
- An Efficient and Remarkably Regioselective Synthesis of Benzocyclobutenones from Benzynes and 1,1-Dimethoxyethylene
-
New efficient methodology for the synthesis of substituted benzocyclobutenones is presented that involves the cycloaddition of various substituted benzynes to 1,1-dimethoxyethylene followed by hydrolysis to the corresponding ketone.In most cases studied a high degree of regioselectivity was observed.These observations are consistent with a nonsynchronous mechanism wherein steric and inductive considerations can be used to account for the products observed.
- Stevens, Robert V.,Bisacchi, Gregory S.
-
p. 2393 - 2396
(2007/10/02)
-
- Micellar Catalysis of the Basic Hydrolysis of Anilides. III α-Substituted N-Methyl-N-p-nitrophenylacetamides
-
The basic hydrolysis of a number of α-substituted N-methyl-N-p-nitrophenylacetamides has been studied both in the presence and absence of micelles of cetyltrimethylammonium bromide (ctab).Unlike the related p-nitrophenyl esters of α-substituted acetic acids, no evidence for the operation of the E1cb mechanism in the basic hydrolysis has been detected.Reasons for the differences between the amides and esters are discussed.Substituent effects on the hydrolysis of the amides have been studied both by single-parameter and dual-parameter analysis.
- Broxton, Trevor J.,Duddy, Neil W.
-
p. 1771 - 1781
(2007/10/02)
-
