ChemInform Abstract: Catalysis Using Phosphorus Compounds in the Reaction of Benzoic Acid with Aniline.

Abstract

1993 amide formation, amide hydrolysis amide formation, amide hydrolysis O 0320 10 -142 Catalysis Using Phosphorus Compounds in the Reaction of Benzoic Acid with Aniline. -Phosphorus compounds of different nature catalyze the formatiom of benzanilide from benzoic acid and aniline (18 examples). P(III) compounds are found to be more active in comparison with P(V) compounds. Possible catalysis mechanisms are discussed of which an intermediary formation of acyl phosphites is most probable. -(SHTEINBERG, L. YA.; BOIKO, V. D.; KONDRATOV, S. A.; SHEIN, S. M.; SHTEINBERG, YA. B.; Zh. Org.

Catalytic amide formation from non-activated carboxylic acids and amines

“…Molecular sieves were used as a water scavenger at room temperature and the catalyst loading was reported to be 25 mg/mmol substrate. The results from the PEG reactions were 90 shown to be comparable to, and sometimes better than, results from reactions in ionic liquids or t-butanol. The authors showed that the immobilized enzyme could be reused up to 8 times with only 5% difference in yield between the first and the eighth run.…”

“…Sheldon and co-workers showed that racemic ibuprofen could 85 be kinetically resolved as its hydroxamic acid with Candida rugosa lipase (ChiroCLEC-CR) in 41% yield with >92% ee as the (S)-isomer (catalyst loading of 50 mg per mmol substrate). The racemic acid could also be resolved as its octanoylhydrazine derivative with the best result arising from the use of 90 Pseudomonas lipoprotein lipase in 50% yield with 82% ee as the (R)-enantiomer ( Figure 2). 49 The enzymatic dipeptide synthesis from protected amino acids on solid support, reported by Ulijn et al, was also shown to be 95 active in kinetic resolution.…”

“…The use of metal complexes as Lewis acidic mediators for the 90 formation of secondary and tertiary amides goes back to the 1970's, when Wilson and Weingardten used stoichiometric amounts of TiCl 4 to form carboxamides from non-activated carboxylic acids and amines. 84 In 1972, the first patent was filed for a catalytic process describing the production of amides from 95 different long chain fatty acids and amines.…”

“…22 After 24 hours at 55 ºC and a 1:1 molar ratio 85 of carbamate to acid, the amides were formed in near quantitative yields with a catalyst loading of 100 mg immobilized enzyme to 1 mmol substrate. The same methodology was also efficient for the direct amidation of 10-hydroxystearic acid and 10-ketostearic acid in 2-methyl-2-butanol to obtain the corresponding primary 90 amides in 94% and 92% yield respectively. 23 Furthermore, it was shown that multi-hydroxylated fatty acids were efficiently converted into the corresponding amides employing the same method.…”

“…32 Yields of up to 97% were obtained at 90 ºC with immobilized Candida Antarctica lipase B (Novozym® 435) after 50 hours of reaction time. The molar ratio of acid to amine was 1:1 in 2-methyl-2-butanol with a catalyst loading of 57 mg immobilized 90 enzyme to 1 mmol substrate. The authors reported that the amide coupling also worked well using decanoic acid or N-methylgalactamine as substrates (Scheme 8).…”