Reactions of lead tetraacetate. I. Formation of acylamines from primary carboxamides

1968 ◽  
Vol 21 (1) ◽  
pp. 185 ◽  
Author(s):  
B Acott ◽  
ALJ Beckwith ◽  
A Hassanali
Keyword(s):  
Acetic Acid ◽  
Reaction Mechanism ◽  
Benzoic Acid ◽  
Intermediate Formation ◽  
Lead Tetraacetate ◽  
Acid Mixture ◽  
Curtius Rearrangement ◽  
Alkyl Isocyanate

Pentanamide, when treated with lead tetraacetate in hot benzene, affords a mixture of N-butylacetamide and N,N?-dibutylurea. Examples of similar transformations of a number of primary carboxamides are described. The reaction, which may also be conducted in acetic acid or benzene-acetic acid mixture, is catalysed by pyridine. Cyclohexanecarboxamide, when oxidized by lead tetraacetate in the presence of propionic or benzoic acid, is converted into the appropriate acylcyclohexylamine. The reaction mechanism involves intermediate formation of alkyl isocyanate, possibly via Curtius rearrangement of acylnitrene.

The mechanism of lead tetraacetate decarboxylation. I. Tertiary carboxylic acids

1974 ◽  
Vol 27 (8) ◽  
pp. 1673 ◽  
Author(s):  
ALJ Beckwith ◽  
RT Cross ◽  
GE Gream
Keyword(s):  
Acetic Acid ◽  
Reaction Mechanism ◽  
Carboxylic Acid ◽  
Product Distribution ◽  
Lead Tetraacetate ◽  
Copper Salts ◽  
Elimination Process ◽  
Initial Generation ◽  
Cis And Trans ◽  
Lead Species

The reactions of cis- and trans-decalin-9-carboxylic acid, 2,2,3-trimethylbutanoic acid, and adamantane-1-carboxylic acid with lead tetraacetate in benzene and, in some cases, acetic acid have been studied. In each case the nature and distribution of the products is consistent with the hypothesis that the reaction mechanism involves the initial generation of tertiary radicals which are subsequently converted into the related cations either by one-electron oxidation by lead species, or via organolead intermediates which undergo heterolysis. The change in product distribution which occurs when the reactions are conducted in the presence of copper salts indicates that tertiary radicals react rapidly with cupric species to afford organocopper intermediates from which olefins are derived by a cis-elimination process, and acetates by SNi or heterolytic mechanisms.

Reactions of lead tetraacetate. II. Formation of carbamic acid esters from primary carboxamides

1968 ◽  
Vol 21 (1) ◽  
pp. 197 ◽  
Author(s):  
B Acott ◽  
ALJ Beckwith ◽  
A Hassanali
Keyword(s):  
Reaction Mechanism ◽  
Efficient Method ◽  
Intermediate Formation ◽  
Lead Tetraacetate ◽  
Carbamic Acid ◽  
Structural Types ◽  
Wide Range ◽  
Alcohol Mixtures ◽  
Acid Esters

Treatment of primary carboxamides with lead tetraacetate in benzene-alcohol mixtures or neat alcohol affords a convenient, flexible, and efficient method for the preparation of N-substituted carbamic acid esters. The reaction is applicable to amides and alcohols of a wide range of structural types including compounds containing oleflnic, ester, aromatic, and other reactive functions. The reaction mechanism appears to involve intermediate formation of isocyanates.

Theoretical study of the ketonization reaction mechanism of acetic acid over SiO2

2009 ◽  
Author(s):  
Mendel Fleisher ◽  
E. Lukevics ◽  
L. Leite ◽  
D. Jansone ◽  
K. Edolfa ◽  
...  
Keyword(s):  
Acetic Acid ◽  
Reaction Mechanism ◽  
Theoretical Study

Lead Tetraacetate Oxidations in the Sugar Group. V.1The Rates of Oxidation of Open-Chain Polyalcohols in Dry Acetic Acid Solution2

1944 ◽  
Vol 66 (3) ◽  
pp. 467-468 ◽  
Author(s):  
Robert C. Hockett ◽  
Margaret T. Dienes ◽  
Hewitt G. Fletcher ◽  
Hugh E. Ramsden
Keyword(s):  
Acetic Acid ◽  
Lead Tetraacetate ◽  
Open Chain ◽  
Group V

scholarly journals Synthesis of spiro[dihydropyridine-oxindoles] via three-component reaction of arylamine, isatin and cyclopentane-1,3-dione

2013 ◽  
Vol 9 ◽  
pp. 8-14 ◽  
Author(s):  
Yan Sun ◽  
Jing Sun ◽  
Chao-Guo Yan
Keyword(s):  
Acetic Acid ◽  
Reaction Mechanism ◽  
Room Temperature ◽  
The Other ◽  
Other Hand ◽  
Three Component Reaction ◽  
High Yields

A fast and convenient protocol for the synthesis of novel spiro[dihydropyridine-oxindole] derivatives in satisfactory yields was developed by the three-component reactions of arylamine, isatin and cyclopentane-1,3-dione in acetic acid at room temperature. On the other hand the condensation of isatin with two equivalents of cyclopentane-1,3-dione gave 3,3-bis(2-hydroxy-5-oxo-cyclopent-1-enyl)oxindole in high yields. The reaction mechanism and substrate scope of this novel reaction is briefly discussed.

Improved synthesis of anti-sesquinorbornene

1984 ◽  
Vol 62 (9) ◽  
pp. 1840-1844 ◽  
Author(s):  
Karl R. Kopecky ◽  
Alan J. Miller
Keyword(s):  
Acetic Acid ◽  
Sulfuric Acid ◽  
Carboxylic Acid ◽  
Lead Tetraacetate ◽  
Carboxyl Group ◽  
Silver Acetate ◽  
Benzenesulfonyl Chloride ◽  
Methoxide Ion ◽  
Hydrolysis Of ◽  
Monomethyl Ester

Treatment of methyl hydrogen decahydro-1,4:5,8-exo,endo-dimethanonaphthalene-4a,8a-dicarboxylate with lead tetraacetate in benzene – acetic acid replaces the carboxyl group by an acetoxy group. Hydrolysis of this product with 25% sulfuric acid at 130 °C forms 8a-hydroxydecahydro-1,4:5,8-exo,endo-dimethanonaphthalene-4a-carboxylic acid 10. The reaction between 10 and benzenesulfonyl chloride in pyridine containing triethylamine at 95 °C produces anti-sesquinorbornene 1 in 34% yield. In the absence of triethylamine 1 is converted to the hydrochloride. The iodohydroperoxide of 1 is converted by silver acetate at 0 °C to the diketone in a luminescent reaction. The 1,2-dioxetane could not be isolated. Decahydro-1,4:5,8-exo,exo-dimethanonaphthalene-4a,8a-dicarboxylic anhydride is converted slowly by methoxide ion in methanol at 150 °C to the monomethyl ester which then undergoes demethylation. The isomeric exo,endo anhydride undergoes reaction readily with methoxide ion at 80 °C.

scholarly journals Oxidative Study of Benzaldehyde by Isoqauinolinium Bromo Chromate

2019 ◽  
Vol 16 ◽  
pp. 5354-5359
Author(s):  
Arun Kumar Dwivedi ◽  
K. N. Sharma ◽  
Arvind Prasad Dwivedi
Keyword(s):  
Dielectric Constant ◽  
Acetic Acid ◽  
Complex Formation ◽  
Benzoic Acid ◽  
Neutral Salt ◽  
Kinetics Analysis ◽  
Keto Form ◽  
Acetic Acid Medium ◽  
Oxidative Reaction ◽  
Rate Of Reaction

The kinetics analysis of the oxidative reaction between benzaldehyde and oxidant is quinolinium Bromo chromate was reported in aqueous 40% acetic acid medium at 313 K. The rate of reaction varies first-power of [IQBC] and [H2SO4], whereas fractional-order kinetics was observed for benzaldehyde. The rate constant gradually increases with decrease in dielectric constant of the medium. The neutral salt does not alter the rate. The metal cations (Cu++) slightly accelerate the rate of oxidation when added to reaction mixture. The study rules out the participation of keto form of substrate in complex formation. Benzoic acid was identified as the end-product in stoichiometrically 1:1 based mechanism. The rate law was derived in accordance with the kinetic results.

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