Carboxyl radical-assisted 1,5-aryl migration through Smiles rearrangement

2016 ◽  
Vol 14 (41) ◽  
pp. 9768-9779 ◽  
Author(s):  
Asik Hossian ◽  
Ranjan Jana
Keyword(s):  
Benzoic Acids ◽  
Smiles Rearrangement ◽  
Carboxylate Oxygen ◽  
Carboxyl Radical

A silver(i)-catalyzed Smiles rearrangement of 2-aryloxy- or 2-(arylthio)benzoic acids to provide aryl-2-hydroxybenzoate or aryl-2-mercaptobenzoate dimer, respectively, through 1,5-aryl migration from oxygen or sulfur to carboxylate oxygen is reported.

scholarly journals X-ray structures of organic salts between diethanolamine and ortho- and para-isomers of aminobenzoic acid: A specific synthon responsible for an association of the components

2018 ◽  
Vol 9 (2) ◽  
pp. 121-125 ◽  
Author(s):  
Aziz Bakhtiyarovich Ibragimov ◽  
Bakhtiyar Sabirkhanovich Zakirov ◽  
Bakhtiyar Tulyaganovich Ibragimov ◽  
Jamshid Mengnorovich Ashurov
Keyword(s):  
Single Crystal ◽  
Benzoic Acids ◽  
Aminobenzoic Acid ◽  
Organic Salts ◽  
X Ray ◽  
Single Crystal Structures ◽  
Carboxylate Oxygen ◽  
3D Network ◽  
Graph Set ◽  
Oxygen Atoms

Two organic salts between diethanolamine (DEA) and ortho- and para-isomers (OABA and PABA) of aminobenzoic acid (ABA) have been obtained and their X-ray single crystal structures determined. In both salts, cationic and anionic components are incorporated into dimers by the two H-bonds formed between ABA carboxylate oxygen atoms and nitrogen and one of oxygen atoms of DEA which close a cycle with the graph-set notation of R22(9). Further dimers are associated by intricate systems of the H-bonds into 1D- and 3D-network structures in crystals of DEA·OABA and DEA·PABA, respectively. H-bonding which generates these dimers may be considered as a synthon specific for yielding of salts between DEA and mono-substituted aromatic benzoic acids.

Several Species of Nucleophiles in the Smiles Rearrangement

2017 ◽  
Vol 21 (16) ◽  
Author(s):  
Ali Ramazani ◽  
Farzaneh Moradnia ◽  
Hamideh Aghahosseini ◽  
Ilnaz Abdolmaleki
Keyword(s):  
Smiles Rearrangement

Substituted N,N-Dimethyl-3-(phenylthio)- and -4-(phenylthio)benzylamines

1992 ◽  
Vol 57 (1) ◽  
pp. 194-203 ◽  
Author(s):  
Karel Šindelář ◽  
Vojtěch Kmoníček ◽  
Marta Hrubantová ◽  
Zdeněk Polívka
Keyword(s):  
Serotonin Receptors ◽  
Hydrobromic Acid ◽  
Antidepressant Activity ◽  
Benzoic Acids ◽  
Lithium Aluminium Hydride ◽  
Acid Chlorides ◽  
Activity Inhibition ◽  
Lithium Aluminium ◽  
The Brain

(Arylthio)benzoic acids IIa - IIe and VIb - VId were transformed via the acid chlorides to the N,N-dimethylamides which were reduced either with diborane "in situ" or with lithium aluminium hydride to N,N-dimethyl-(arylthio)benzylamines Ia - Ie and Vb - Vd. Leuckart reaction of the aldehydes IX and X with dimethylformamide and formic acid afforded directly the amines Va and Ve. Demethylation of the methoxy compounds Ia and Ve with hydrobromic acid resulted in the phenolic amines If and Vf. The most interesting N,N-dimethyl-4-(phenylthio)benzylamine (Va) hydrochloride showed affinity to cholinergic and 5-HT2 serotonin receptors in the rat brain and some properties considered indicative of antidepressant activity (inhibition of serotonin re-uptake in the brain and potentiation of yohimbine toxicity in mice).

Kinetics and Mechanism of Decomposition of 1,3-Bis(4-methylphenyl)triazene Catalyzed with Substituted Benzoic Acids in 25% Aqueous Methanol-General or Specific Catalysis?

1994 ◽  
Vol 59 (9) ◽  
pp. 2029-2041
Author(s):  
Oldřich Pytela ◽  
Taťjana Nevěčná
Keyword(s):  
Benzoic Acids ◽  
Hammett Equation ◽  
Aqueous Methanol ◽  
Mechanism Of Decomposition ◽  
Kinetics Of Decomposition ◽  
Independent Variable ◽  
Amino Derivatives ◽  
Substituted Benzoic Acids ◽  
The Individual ◽  
Kinetics Of

The kinetics of decomposition of 1,3-bis(4-methylphenyl)triazene catalyzed with 13 substituted benzoic acids of various concentrations have been measured in 25 vol.% aqueous methanol at 25.0 °C. The rate constants observed (297 data) have be used as values of independent variable in a series of models of the catalyzed decomposition. For the catalytic particles were considered the undissociated acid, its conjugated base, and the proton in both the specific and general catalyses. Some models presumed formation of reactive or nonreactive complexes of the individual reactants. The substituent effect is described by the Hammett equation. The statistically best model in which the observed rate constant is a superposition of a term describing the dependence on proton concentration and a term describing the dependence on the product of concentrations of proton and conjugated base is valid with the presumption of complete proton transfer from the catalyst acid to substrate, which has been proved. The behaviour of 4-dimethylamino, 4-amino, and 3-amino derivatives is anomalous (lower catalytic activity as compared with benzoic acid). This supports the presumed participation of conjugated base in the title process.

Kinetic study of hydrolysis of benzoates. part xxvii. ortho substituent effect in alkaline hydrolysis of phenyl esters of substituted benzoic acids in aqueous Bu4NBr

2009 ◽  
Vol 74 (1) ◽  
pp. 29-42 ◽  
Author(s):  
Vilve Nummert ◽  
Mare Piirsalu ◽  
Signe Vahur ◽  
Oksana Travnikova ◽  
Ilmar A. Koppel
Keyword(s):  
Alkaline Hydrolysis ◽  
Rate Constants ◽  
Pure Water ◽  
Substituent Effects ◽  
Benzoic Acids ◽  
Resonance Effects ◽  
The Media ◽  
Substituted Benzoic Acids ◽  
Hydrolysis Of ◽  
Ortho Substituent

The second-order rate constants k (in dm3 mol–1 s–1) for alkaline hydrolysis of phenyl esters of meta-, para- and ortho-substituted benzoic acids, X-C6H4CO2C6H5, have been measured spectrophotometrically in aqueous 0.5 and 2.25 M Bu4NBr at 25 °C. The substituent effects for para and meta derivatives were described using the Hammett relationship. For the ortho derivatives the Charton equation was used. For ortho-substituted esters two steric scales were involved: the EsB and the Charton steric (υ) constants. When going from pure water to aqueous 0.5 and 2.25 M Bu4NBr, the meta and para polar effects, the ortho inductive and resonance effects in alkaline hydrolysis of phenyl esters of substituted benzoic acids, became stronger nearly to the same extent as found for alkaline hydrolysis of C6H5CO2C6H4-X. The steric term of ortho-substituted esters was almost independent of the media considered. The rate constants of alkaline hydrolysis of ortho-, meta- and para-substituted phenyl benzoates (X-C6H4CO2C6H5, C6H5CO2C6H4-X) and alkyl benzoates, C6H5CO2R, in water, 0.5 and 2.25 M Bu4NBr were correlated with the corresponding IR stretching frequencies of carbonyl group, (ΔνCO)X.

2,2′-Biaryldicarboxylate Synthesis via Electrocatalytic Dehydrogenative C–H/C–H Coupling of Benzoic Acids

ACS Catalysis ◽  
2021 ◽  
pp. 6626-6632
Author(s):  
Zhongyi Zeng ◽  
Jonas F. Goebel ◽  
Xianming Liu ◽  
Lukas J. Gooßen
Keyword(s):  
Benzoic Acids

scholarly journals Hydrogenation of benzoic acid derivatives over Pt/TiO2 under mild conditions

2021 ◽  
Vol 4 (1) ◽  
Author(s):  
Miao Guo ◽  
Xiangtao Kong ◽  
Chunzhi Li ◽  
Qihua Yang
Keyword(s):  
Electron Transfer ◽  
Benzoic Acid ◽  
High Efficiency ◽  
Carboxyl Groups ◽  
Carboxyl Group ◽  
Benzoic Acids ◽  
Catalyst Poisoning ◽  
Benzoic Acid Derivatives ◽  
Mild Conditions ◽  
Transfer Direction

AbstractHydrogenation of benzoic acid (BA) to cyclohexanecarboxylic acid (CCA) has important industrial and academic significance, however, the electron deficient aromatic ring and catalyst poisoning by carboxyl groups make BA hydrogenation a challenging transformation. Herein, we report that Pt/TiO2 is very effective for BA hydrogenation with, to our knowledge, a record TOF of 4490 h−1 at 80 °C and 50 bar H2, one order higher than previously reported results. Pt/TiO2 catalysts with electron-deficient and electron-enriched Pt sites are obtained by modifying the electron transfer direction between Pt and TiO2. Electron-deficient Pt sites interact with BA more strongly than electron-rich Pt sites, helping the dissociated H of the carboxyl group to participate in BA hydrogenation, thus enhancing its activity. The wide substrate scope, including bi- and tri-benzoic acids, further demonstrates the high efficiency of Pt/TiO2 for hydrogenation of BA derivatives.

Optimizing the structure of (salicylideneamino)benzoic acids: Towards selective antifungal and anti-staphylococcal agents

2021 ◽  
Vol 159 ◽  
pp. 105732
Author(s):  
Martin Krátký ◽  
Klára Konečná ◽  
Kateřina Brokešová ◽  
Jana Maixnerová ◽  
František Trejtnar ◽  
...  
Keyword(s):  
Benzoic Acids
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