Amides II. Acylation of amides to diacylimines

Abstract

Three acylating mechanisms are involved in the reaction between amides and anhydrides. In the aliphatic series all mechanisms are governed by the indilctive effects operating in the reactants.Amides act as acids towards anhydrides. Diacylimines and the corresponding anhydrides acylate alcohols by the same mechanism.A new compound, propionylchloroacetarnide, has been prepared. Properties of some diacylimines have been established. Uses for diacylimines are suggested.

On the Reactivity of α-(Triphenylphosphoranylidene)-benzylphenylketene with Nitrogen Compounds: Synthetic and Mechanistic Implications

“…To provide insight into the behavior of α-TPBPK toward nitrogen compounds without transferable hydrogen, 2 was treated with azobenzene and N-(p-methoxyphenyl)benzaldimine, but only complex mixtures were formed. However, with diethyl azodicarboxylate 16 a clean reaction took place, wherein the N-acyl carbamate (17) was formed in excellent yield. This is a very interesting result since densely substituted N-acyl carbamates are versatile intermediates in the synthesis of nucleoside analogues and their preparation is not a trivial task.…”

“…A solution of 105.0 mg (0.5 mmol) of diphenylcyclopropenone (1) and 134.3 mg (0.5 mmol) of triphenylphosphine in 8.0 cm 3 of benzene in a two-necked roundbottom flask was left at room temperature with stirring for 2 h. To the orange solution was added 83.2 mg (0.5 mmol) of N-benzoylacetamidine (5). The solution turned yellow and was left stirring for 24 h. After this time the solvent was removed under reduced pressure and the residue was purified by column chromatography (Florisil  ) affording 15.7 mg (12%) of 14 (benzene/ethyl acetate 5%), 28.1 mg (13.5%) of 15 17 (benzene/ethyl acetate 5%) and 76.5 mg (67%) of α-phenylcinnamamide (13) 18 (benzene/ethyl acetate 10%). 14: IR (KBr): ν max /cm -1 3274, 1706, 1690, 1610.…”

Photochemical reactivity of keto imino ethers. VI. Type I rearrangement and (2 + 2) photocycloaddition to the carbon-nitrogen double bond of 2-oxazolin-4-ones

“…7V-(Chloroacetyl)benzamide was prepared according to the procedure described by Polya and Spots word. 21 The product was obtained in 76% yield with mp 159-159.5°( lit. mp 157°) and gave the following spectral data: NMR (CDCb, 60 MHz) 5 4,77 (2 H, s), 7.75 (5 H, m), and 9.0 ppm (1 H, broad); ir (CHCI3) 2.96, 5.78, and 5.87 µ; mass spectrum m/e 197 (M+, 7), 162 (22), 105 (base), 77 (87), and 51 (38).…”

“…The solid was recrystallized from chloroform, yielding 11 g (73%) of a white solid with mp 131-132°with the following spectral data: NMR (CDCI3, 60 MHz) 3.92 (3 H, s), 4.80 (2 H, s), 7. 1-7.6 ppm (4 H, m); ir (CDCI3) 2.96, 5.78, 5.85, and 6.79 µ; mass spectrum m/e 221 (M+, 24), 135 (base), 107 (25), and 77 (21).…”

The Fundamental Basis for Cyclopolymerization. III. A Spectroscopic Study of Dimethacrylamides

“…In some reactions the yield of methacrylonitrile was 5060% based upon the amount of methacrylamide used. It has been reported that acid chlorides catalyze the acylation of amides by anhydrides [6] but can in some cases lead to . When methacrylamide, methacrylic anhydride, and a trace of methacryloyl chloride were heated together, no dimethacrylamide was isolated and a 65% yield of methacrylonitrile was obtained.…”