Preparation, properties, and reductive alkylation of arylhydrazides

1998 ◽  
Vol 76 (8) ◽  
pp. 1180-1187 ◽  
Author(s):  
Giancarlo Verardo ◽  
Nicoletta Toniutti ◽  
Angelo G Giumanini
Keyword(s):  
Carboxylic Acid ◽  
Carboxylic Acids ◽  
Alkyl Group ◽  
Sodium Tetrahydroborate ◽  
Structural Features ◽  
High Yield ◽  
Reductive Alkylation ◽  
H Nmr ◽  
E And Z Isomers

1-Acyl-2-arylhydrazines (1), readily obtained in high yield from the condensation of arylhydrazines and the appropriate liquid carboxylic acid (2), underwent reductive alkylation with the same or different liquid carboxylic acids (2) and NaBH4 to give 1-acyl-2-alkyl-2-arylhydrazines (3) in good to moderate yields. The carboxylic acid has both the role of supplying the entering alkyl group and of acting as solvent. Most likely, it also modifies the BH4- anion to an active reducing agent under those conditions. The 1H NMR criteria for identifying the location of acylation of hydrazines and E and Z isomers are given. The MS spectra of the prepared hydrazides were analyzed in order to identify relevant structural features leading to specific fragmentations.Key words: 1-acyl-2-arylhydrazine, 1-acyl-2-alkyl-2-arylhydrazine, reductive alkylation, sodium tetrahydroborate, carboxylic acid.

scholarly journals Ligand-Controlled Regiodivergence in Nickel-Catalyzed Hydroarylation and Hydroalkenylation of Alkenyl Carboxylic Acids

2020 ◽  
Author(s):  
Zi-Qi Li ◽  
Yue Fu ◽  
Ruohan Deng ◽  
Van Tran ◽  
Yang Gao ◽  
...  
Keyword(s):  
Dft Calculations ◽  
Transition State ◽  
Carboxylic Acids ◽  
Alkyl Group ◽  
Steric Effects ◽  
High Yield ◽  
Mechanistic Studies ◽  
Ligand Environment ◽  
Ligand Free ◽  
Electronic And Steric Effects

<div>A nickel-catalyzed regiodivergent hydroarylation and hydroalkenylation of unactivated alkenyl carboxylic acids is reported, whereby the ligand environment around the metal center dictates the regiochemical outcome. Markovnikov hydrofunctionalization products are obtained under mild ligand-free conditions, with up to 99% yield and >20:1 selectivity. Alternatively, anti-Markovnikov products can be accessed with a novel 4,4-disubstituted Pyrox ligand in excellent yield and >20:1 selectivity. Both electronic and steric effects on the ligand contribute to the high yield and selectivity. Mechanistic studies suggest a change in the turnover-limiting and selectivity-determining step induced by the optimal ligand. DFT calculations reveal that in the anti-Markovnikov pathway, repulsion between the ligand and the alkyl group is minimized (by virtue of it being 1° versus 2°) in the rate- and regioselectivity-determining transmetalation transition state. <br></div>

scholarly journals Ligand-Controlled Regiodivergence in Nickel-Catalyzed Hydroarylation and Hydroalkenylation of Alkenyl Carboxylic Acids

2020 ◽  
Author(s):  
Zi-Qi Li ◽  
Yue Fu ◽  
Ruohan Deng ◽  
Van Tran ◽  
Yang Gao ◽  
...  
Keyword(s):  
Dft Calculations ◽  
Transition State ◽  
Carboxylic Acids ◽  
Alkyl Group ◽  
Steric Effects ◽  
High Yield ◽  
Mechanistic Studies ◽  
Ligand Environment ◽  
Ligand Free ◽  
Electronic And Steric Effects

<div>A nickel-catalyzed regiodivergent hydroarylation and hydroalkenylation of unactivated alkenyl carboxylic acids is reported, whereby the ligand environment around the metal center dictates the regiochemical outcome. Markovnikov hydrofunctionalization products are obtained under mild ligand-free conditions, with up to 99% yield and >20:1 selectivity. Alternatively, anti-Markovnikov products can be accessed with a novel 4,4-disubstituted Pyrox ligand in excellent yield and >20:1 selectivity. Both electronic and steric effects on the ligand contribute to the high yield and selectivity. Mechanistic studies suggest a change in the turnover-limiting and selectivity-determining step induced by the optimal ligand. DFT calculations reveal that in the anti-Markovnikov pathway, repulsion between the ligand and the alkyl group is minimized (by virtue of it being 1° versus 2°) in the rate- and regioselectivity-determining transmetalation transition state. <br></div>

Sulfur-Free Penicillin Derivatives. V. Preparation, Hydrolysis, and Oxidative Rearrangement Of Fused Oxazoline–Azetidinones

1975 ◽  
Vol 53 (4) ◽  
pp. 497-512 ◽  
Author(s):  
Saul Wolfe ◽  
Shui-Lung Lee ◽  
Jean-Bernard Ducep ◽  
Gérard Kannengiesser ◽  
Wha Suk Lee
Keyword(s):  
Carboxylic Acid ◽  
Sulfonic Acid ◽  
Acyl Transfer ◽  
High Yield ◽  
Methyl Groups ◽  
Acyl Substituent ◽  
Oxidative Rearrangement ◽  
Alternative Routes ◽  
Hydrolysis Of

Chlorinolysis of an anhydropenicillin affords a 2-(2′-chloro-3′S-amino, -acylamino or -phthalimido-4′-oxo)azetidinyl-3-methyl-2-butenoyl chloride, as a mixture of 2′R (cis) and 2′S (trans) epimers in which the 2′R epimer usually predominates. Hydrolysis of the acid chloride and treatment of the carboxylic acid with aqueous bicarbonate causes cyclization, in the case of a 3′-acylamino substituent, to a 2R-6-(1′-carboxy-2′-methyl-prop-1-enyl)-1-oxa-3,6-diaza-4S,5R-bicyclo[3,2,0]hept-2-ene-7-one. The mechanisms of these transformations are discussed, and alternative routes to such fused oxazoline–azetidinones are also presented.The oxazolines undergo ready hydrolysis to sulfonic acid salts of 2-(2′R-acyloxy-3′S-amino-4′-oxo)azetidinyl-3-methyl-2-butenoates upon treatment with the hydrate of a sulfonic acid in acetone solvent. Neutralization of these salts proceeds without O → N acyl transfer, because acylation yields a diacylated azetidinone in which the new acyl substituent is attached to nitrogen. Monobromination of the allylic methyl groups of these salts, followed by treatment with 2 molar-equiv. of triethylamine, leads to a deep-seated rearrangement, in high yield, to an oxazinone. The mechanism of this rearrangement and, in particular, the role of acylimines in this and related reactions, including the biosynthesis of penicillin, are discussed.

Pteridines CI Synthesis and Properties of Lumazine-6- and -7-carboxylic Acids

Pteridines ◽  
1993 ◽  
Vol 4 (4) ◽  
pp. 178-186 ◽  
Author(s):  
Roland Eisele ◽  
Keiichi Aritomo ◽  
Wolfgang Pfleiderer
Keyword(s):  
Carboxylic Acid ◽  
Carboxylic Acids ◽  
Resonance Effect ◽  
Uv Spectra ◽  
High Yield ◽  
Methyl Group ◽  
Methyl Derivatives ◽  
Pyrimidine Moiety

Summary Lumazine-6-(8) and 7-carboxylic acid (23) and their N-methyl derivatives (12, 13, 21, 26, 28, 29) have been synthesized and characterized by the determination of their pK values and the UV spectra of the neutral, mono and dianion species. It was noticed that the acidities of the two N-H protons of the pyrimidine moiety are almost the same indicating that the dianions of 8 and 23, respectively, are I: 1 mixtures of the corresponding N-l and N-3 deprotonated forms. The lumazine-7-carboxylic acids (23, 26, 28, 29, 31, 33) are in comparison to their 6-carboxyJic acid counterparts (8, 12, 13, 21, 39) stronger acids by about I pK unit due to the resonance effect of the 4-oxo function on C-7 but not C-6. Alkaline KMn04 oxidation of 6.7-dimethyl-Iumazine (30) forms expectedly 6-methyl-Iumazine-7-carboxylic acid (31) in high yield according to the activation of the 7-methyl group by the electron-attracting 4-carbonyl residue.

scholarly journals Encapsulation of benzene carboxylic acids using cyclodextrins

2021 ◽  
Vol 12 (1) ◽  
pp. 40-51
Author(s):  
L. A. Belyakova ◽  
Keyword(s):  
Carboxylic Acid ◽  
Carboxylic Acids ◽  
Spectral Characteristics ◽  
Complexing Agents ◽  
X Ray ◽  
Medicinal Substances ◽  
Nonspecific Interactions ◽  
The Stability ◽  
Formation Of Complexes

The encapsulation of medicinal substances in various polymers is a common way to increase their thermal, hydrolytic, and chemical stability. However, the bioavailability of the encapsulated drugs decreases. The solution to this important problem can be the preparation of nanocapsules of medicinal substances using complexing agents, for example, cyclodextrins. The purpose of this work is to study the possibility of encapsulation of benzoic, salicylic, and β-resorcylic acids using α- and β-cyclodextrins. The interaction of benzene carboxylic acids with cyclodextrins in aqueous solutions at 20–30 оС has been studied by spectrophotometry. The formation of complexes with a composition of 1:1 in the cyclodextrin – benzene carboxylic acid systems has been proven. The stability constants of the complexes and the main thermodynamic parameters of complex formation have been calculated. It has been shown that the nature of changes in the spectral characteristics of benzene carboxylic acids in the presence of cyclodextrins can be used to predict the possibility of aromatic organic compounds encapsulation. The determining role of the complementarity of geometric parameters of cyclodextrins and benzene carboxylic acids in the preparation of inclusion complexes with features of nanocapsules has been found. The prospects of using β-cyclodextrin for encapsulation of benzene carboxylic acids have been demonstrated. The complexes of β-cyclodextrin with benzene carboxylic acids were synthesized and studied by IR spectroscopy, X-ray analysis and derivatography. The formation of two types of complexes in the β-cyclodextrin – benzene carboxylic acid system was established. The first type of complexes is formed due to nonspecific interactions between the hydrophobic cavity of β-cyclodextrin and the benzene carboxylic acid molecule, the second type is due to specific interactions between the functional groups of molecules. Benzoic and salicylic acids form nanocapsules with β-cyclodextrin, and their hydrolytic and thermal stability increases. Complexes of the second type acquire the properties of a new compound: β-resorcylic acid loses its individuality, forming strong supramolecular structures with β-cyclodextrin.

Fibrinolytic Activity of Cerebro-Spinal Fluid and the Development of Artificial Cerebral Haematomas in Dogs

1969 ◽  
Vol 21 (02) ◽  
pp. 294-303 ◽  
Author(s):  
H Mihara ◽  
T Fujii ◽  
S Okamoto
Keyword(s):  
Cerebrospinal Fluid ◽  
Carboxylic Acid ◽  
Fibrinolytic Activity ◽  
Clinical Implications ◽  
Trans Form ◽  
Plate Method ◽  
Blood Samples ◽  
Fibrin Plate ◽  
The Brain

SummaryBlood was injected into the brains of dogs to produce artificial haematomas, and paraffin injected to produce intracerebral paraffin masses. Cerebrospinal fluid (CSF) and peripheral blood samples were withdrawn at regular intervals and their fibrinolytic activities estimated by the fibrin plate method. Trans-form aminomethylcyclohexane-carboxylic acid (t-AMCHA) was administered to some individuals. Genera] relationships were found between changes in CSF fibrinolytic activity, area of tissue damage and survival time. t-AMCHA was clearly beneficial to those animals given a programme of administration. Tissue activator was extracted from the brain tissue after death or sacrifice for haematoma examination. The possible role of tissue activator in relation to haematoma development, and clinical implications of the results, are discussed.

Metal-Metal Cooperative Bond Activation by Heterobimetallic Alkyl, Aryl, and Acetylide PtII/CuI Complexes

2020 ◽  
Author(s):  
Shubham Deolka ◽  
Orestes Rivada Wheelaghan ◽  
Sandra Aristizábal ◽  
Robert Fayzullin ◽  
Shrinwantu Pal ◽  
...  
Keyword(s):  
Alkyl Group ◽  
Bond Activation ◽  
Bond Cleavage ◽  
Terminal Alkyne ◽  
Alkyl Aryl ◽  
Metal Metal ◽  
The Stability ◽  
Selective Formation ◽  
Organoplatinum Compounds

We report selective formation of heterobimetallic PtII/CuI complexes that demonstrate how facile bond activation processes can be achieved by altering reactivity of common organoplatinum compounds through their interaction with another metal center. The interaction of the Cu center with Pt center and with a Pt-bound alkyl group increases the stability of PtMe2 towards undesired rollover cyclometalation. The presence of the CuI center also enables facile transmetalation from electron-deficient tetraarylborate [B(ArF)4]- anion and mild C-H bond cleavage of a terminal alkyne, which was not observed in the absence of an electrophilic Cu center. The DFT study indicates that the role of Cu center acts as a binding site for alkyne substrate, while activating its terminal C-H bond.

The Role of Archpriest Eugene Popov in Enhancing of the Anglican-Orthodox Dialog

2020 ◽  
pp. 71-84
Author(s):  
Ярослав Очканов
Keyword(s):  
State Level ◽  
Structural Features ◽  
Russian Orthodox ◽  
Church Community ◽  
Anglican Church ◽  
Current State ◽  
The Church

Статья посвящена исследованию малоизученной стороны деятельности видного русского священнослужителя протоиерея Евгения Попова, бывшего с 1842 по 1875 гг. настоятелем русской посольской церкви в Лондоне. Его служение на Английской земле совпало с углублением диалога между Русской Православной и Англиканской церквами, явившегося следствием религиозных преобразований в Англии в 1830 - 1840-е гг. Отец Евгений в рассматриваемый период фактически стал связующим звеном между русским церковноначалием и англиканами - инициаторами единения двух Церквей. Он проделал огромную работу по популяризации православия в Англии и много сделал для ознакомления русской церковной общественности с вероучением и структурными особенностями англиканства. Материалом для исследования послужили, прежде всего, письма протоиерея Евгения Попова обер-прокурорам Святейшего Синода Н. А. Протасову и А. П. Толстому. Эти документы являются своеобразными отчётами о современном состоянии Англиканской Церкви, о религиозных течениях в ней и усилиях, предпринимаемых определёнными церковными кругами в Англии по сближению с православием. Результаты его деятельности имели важное значение в последующие десятилетия, когда англикано-православный диалог вышел на церковно-государственный уровень. The article is devoted to the insufficiently studied aspects of Russian prominent cleric Archpriest Eugene Popov, rector of Russian Embassy Church in London from 1842 to 1875. His Ministry on the English soil coincided with the deepening of the dialogue between the Russian Orthodox and Anglican Churches, which was the result of religious transformations in England in the 1830s and 1840s. Father Eugene in the period under consideration actually became a connecting link between the Russian Church authorities and the anglicans-initiators of the union of the two Churches. He had done a great job by popularizing Orthodoxy in England and by familiarizing the Russian Church community with the doctrine and structural features of Anglicanism. The study, first of all, is based the letters of Archpriest Yevgeny Popov to the chief prosecutors of the Holy Synod N. A. Protasov and A. P. Tolstoy, which were original reports on the current state of the Anglican Church, it’s religious trends, and the efforts made by certain Church circles in England to get closer to Orthodoxy. The fruits of his activities were important in the following decades, when the Anglican-Orthodox dialogue reached the Church-state level.

THE USE OF THE TRANSLATION METHOD IN MASTERING THE TERMS

2019 ◽  
pp. 87-95
Keyword(s):  
International Relations ◽  
English Language ◽  
Structural Features ◽  
Point Of View ◽  
General Classification ◽  
Optimal Methods ◽  
Foreign Companies ◽  
The Social ◽  
Problems Of Translation

The article is devoted to the role of Tourism terminology in linguistics and the issue of general classification, peculiarities in the expression and translation of terms related to tourism in English into Uzbek and Russian, as well as the choice of the most optimal methods for translating terms in accordance with the requirements of this professional sphere. The terminology of the English language tourism is distinguished by its brightness, versatility. Tourism terms are formed under the influence of a generalized lexical layer of language and perform a specific functional function.Tourism terms are formed through the affixation method (prefixation, suffixation, circumphixation) and get rich through the process.The terminology of English Tourism is distinguished by its content and structural features, forming a part of the language vocabulary from the linguistic point of view. Texts in the field of Tourism take into their composition concepts of Tourism and interpret them in their content. They will be mainly in the form of advertising, as well as enlighten information about a particular region or place, create informational precedents and ensure their manifestation in the social cultural presence. The relevance of the study of the problems of translation of terms in the field of tourism has been investigated, mainly due to the development of international relations, expansion of cooperation between local and foreign companies, as well as the increase in this area of communication.

Synthesis of 3-(Cyclohexylamino)-2-arylimidazo[1,2-a]pyridine-8- carboxylic Acids Via an Efficient Three-component Condensation Reaction between Cyclohexylisocyanide and 2-Aminopyridine-3-carboxylic Acid in the Presence of Aromatic Aldehyde

2018 ◽  
Vol 21 (4) ◽  
pp. 298-301 ◽  
Author(s):  
Ghasem Marandi
Keyword(s):  
Biological Sciences ◽  
Carboxylic Acid ◽  
Carboxylic Acids ◽  
High Performance ◽  
Condensation Reaction ◽  
Aromatic Aldehydes ◽  
New Materials ◽  
One Pot ◽  
High Yields ◽  
Benzaldehyde Derivatives

Aim and Objective: The reaction of cyclohexylisocyanide and 2-aminopyridine-3- carboxylic acid in the presence of benzaldehyde derivatives in ethanol led to 3-(cyclohexylamino)-2- arylimidazo[1,2-a]pyridine-8-carboxylic acids in high yields. In a three component condensation reaction, isocyanide reacts with 2-aminopyridine-3-carboxylic acid and aromatic aldehydes without any prior activation. Material and Methods: The synthesized products have stable structures which have been characterized by IR, 1H, 13C and Mass spectroscopy as well as CHN-O analysis. Results: In continuation of our attempts to develop simple one-pot routes for the synthesis of 3- (cyclohexylamino)-2-arylimidazo[1,2-a]pyridine-8-carboxylic acids, aromatic aldehydes with divers substituted show a high performance. Conclusion: In conclusion, this study introduces the art of combinatorial chemistry using a simple one-pot procedure for the synthesis of new materials which are interesting compounds in medicinal and biological sciences.

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