51164-42-2Relevant articles and documents
Oxidation of tertiary benzamides by 5,10,15,20-tetraphenyl- porphyrinatoironIII chloride-tert-butylhydroperoxide
Constantino, Luis,Iley, Jim
, p. 1894 - 1900 (2007/10/03)
Tertiary benzamides are oxidized by the 5,10,15,20- tetraphenylporphyrinatoiron(III) chloride-ButOOH system at the α-position of the N-alkyl groups. The major products are N-acylamides, although small amounts of secondary amides, the products of dealkylation, are also formed. Plots of initial rate versus initial substrate concentration for these reactions are curved, suggesting formation of an oxidant-substrate complex. The reaction rates are almost insensitive to the substituent in the benzamide moiety, but there is a kinetic deuterium isotope effect of 5.6 for the reaction of the N,N-(CH3)2 and N,N-(CD3) 2 compounds. Comparison of the reaction products from N-alkyl-N-methylbenzamides reveals that, for all compounds studied except N-cyclopropyl-N-methylbenzamide, oxidation of the alkyl group is preferred, strongly so (by a factor of ca. 8) for N-allyl-N-methylbenzamide. In contrast to microsomal oxidation, there is no steric hindrance to oxidation of an isopropyl group. Thus, we propose that these reactions proceed via hydrogen atom abstraction to form an α-carbon-centred radical and we attribute the observed diminished reactivity of the N-cyclopropyl group to its known reluctance to form a cyclopropyl radical. Oxidation of N-methyl-N-(2,2,3,3- tetramethylcyclopropyl)methylbenzamide provides preliminary evidence for rearrangement of an intermediate radical. While it remains unclear how these reactions proceed directly to the N-acyl products, we have established that N-hydroxymethyl, N-alkoxymethyl and N-alkylperoxymethyl intermediates are not involved.
A simple, convenient and general method for the synthesis of N-acylalkylaminomethyl- and N-acylalkylamino(alkyl, aryl, heteroaryl)methylphosphonates and -phosphine oxides
Couture,Deniau,Grandclaudon
, p. 953 - 956 (2007/10/02)
A variety of N-acylalkylaminomethyl- and alkylamino(alkyl, aryl, heteroaryl)methylphosphonates and -phosphine oxides has been efficiently prepared by acylation of suitable Schiff bases and subsequent treatment of the chloromethylcarboxamide intermediates with the appropriate phosphorylating agent.
A New Direct Synthesis of Tertiary N-Acyloxymethylamide Prodrugs of Carboxylic Acid Drugs
Moreira, Rui,Mendes, Eduarda,Calheiros, Teresa,Bacelo, Maria J.,Iley, Jim
, p. 7107 - 7110 (2007/10/02)
N-Alkyl-N-chloromethylamides 2, prepared from secondary amides, paraformaldehyde and chlorotrimethylsilane, react readily with carboxylate anions to generate the corresponding tertiary N-acyloxymethylamides 3 in good yield; the latter give rise to the parent carboxylic acids in aqueous media at pH 7.4 and 37 deg C with half-lives between ca. 1 min and 42 h.
A convenient synthesis of enamides and dienamides by Horner-Wittig and Wadsworth-Emmons reactions
Couture, Axel,Deniau, Eric,Grandclaudon, Pierre
, p. 1479 - 1482 (2007/10/02)
Various N-acyl-N-alkyl-l-amino-alkenes and -1,3-dienes have been efficiently prepared by reacting aldehydes or ketones 3 with N-alkyl-N-(diphenylphosphinoyl)methyl and -N-(diethoxyphosphoryl)methyl carboxamides 1, 2.
Synthesis and reactivity of aliphatic and (hetero) aromatic N-alkyl-N-(diphenyloxophosphinyl)methyl carboxamides and lactams
Couture,Deniau,Grandclaudon
, p. 2381 - 2392 (2007/10/02)
A variety of aliphatic, aromatic and heteroaromatic N-alkyl-N-(diphenyloxophosphinyl)methyl carboxamides and lactams have been prepared by preliminar chloromethylation of the appropriate secondary amides and subsequent treatment with ethyl diphenylphosphinite.
Acyl Halide Induced Cleavage of N-Acylated Aminals
Boehme, Horst,Raude, Edgar
, p. 3421 - 3429 (2007/10/02)
Acyl halides attack N-acylated aminals 6 at the amine nitrogen as well as at the carboxamide group to form either N-halomethyl carboxamides 5 besides N,N-dialkyl carboxamides 11, or diacylamines 12 besides N,N-dialkylmethaneiminium halides 4.Depending on the variation of the substituents on both heteroatoms the cleavage may be directed to follow only one or the other pathway.Of highly synthetic interest is the broadly applicable preparation of methaneiminium salts 4 having bulky substituents on nitrogen by means of cleavage of the corresponding N,N-dialkyl-N'-formyl-N'-methylmethanediamines 6.
