Cinnamamide

These Br nsted-type plots often seem to be scatter diagrams until the points are collated into groups related by specific structural features. Thus, p-nitrophenyl acetate gives four separate, but parallel, lines for reactions with pyridines, anilines, imidazoles, and oxygen nucleophiles.Figure 7-4 shows such a plot for the reaction of trans-cmmm c anhydride with primary and secondary aliphatic amines to give substituted cinnamamides.All of the primary amines without substituents on the a carbon (R-CHi-NHi) fall on a line of slope 0.62 cyclopentylamine also lies on this line. If this line is characteristic of normal behavior, most of the deviations become qualitatively explicable. The line drawn through the secondary amines (slope 1.98) connects amines with the structure R-CHi-NH-CHi-R. The different steric requirements in the acylation reaction and in the model process... 

The generality of this method for large-scale preparations was demonstrated for the syntheses of toluenesulfonyl aziridines from aminohydroxylation products of N-substituted cinnamamides (Table 12.9). The results of synthesis of other sulfo-nyl aziridines are summarized in Tables 12.10 and 12.11. 

The 1,3-dipolar cycloaddition of a variety of aromatic and aliphatic nitrile oxides to 2.5-/ra//.v-2.5-diphenylpyrrolidine-derived acrylamide and cinnamamide 399, efficiently affords the corresponding 4,5-dihydroisoxazole-5-carboxamides 400 in highly regio- and stereoselectivity (Scheme 1.47). Acid hydrolysis of these products affords enantiopure 4,5-dihydroisoxazole-5-carboxylic acids 401 (443). 

To a stirred suspension of 1.9 g orthocarbamoyl cinnamamide in 50 ml methanol add 26 ml 0.77 N NaOCl and heat in a distillation apparatus at 40° for 2 hours, or until no more indole is distilled off (can use the indole tests described earlier). Extract the distillate with CHCI3 and dry, evaporate in vacuum (or steam distill the solvent) to get about 45% indole. 

Four isobutylamide analogs of the natural products were synthesized in order to compare their insecticidal efficacy with that of the natural products. The synthetic scheme for the preparation of cis-fagaramide ( ) is shown in Figure 1. The syntheses of the cis (9) and trans (8) isomers of N -isobutyl-cinnamamide were accomplished by procedures similar to those utilized in the preparation of the cis (7) and trans (1 ) isomers of fagaramide, with the exception that benzaldehyde was used as starting material in the former case, piperonal in the latter. Isobutylbenzamide (10) was synthesized from benzoyl chloride and isobutylamine. 

Fio. 35. Effect of therm pr quUibratk>n of the mobile phase. Chromatograms of identical samples of 3 bromo- -ethyl cinnamamide run at (A) 58 ml/h, (B) 115 ml/h, and (Q 230 ml/h on a 5>fim S tisoib 01 with unheated precolumn. Reprinted with permission from Itrchalski and wilder (176), Anal. Chem. Copyri t 1979 by the American Chemical Society. 

Fio. 34. Effect of thermal pre-equilibratioii of the mcMIe phase. Chromatograms of identical samples, containing (A) 3-bromo-N-methyl cinnamamide and (B) clonazepam run at 40 ml/h (1), 80 ml/h (2), and 120 ml/h (3) with unheated (a) and heated (b) precolumns on a 5-/im Spherisorb ODS column. Reprinted with permission fiom Bsrchalski and Wilder (176), Anal. Chem. Copyright 1SI79 by the American Chemical Society. 

Keywords Viehe salt, acetophenone, solid-solid reaction, cinnamamide... 

Keywords cyanoacetamide, malodinitril, methyl cyanoacetate, aromatic aldehyde, Knoevenagel condensation, solid-solid reaction, base catalysis, melt reaction, uncatalyzed, cinnamamide, cinnamonitril, methyl cinnamate... 

Several types of unsaturated amides have produced gitonic superelectrophiles in superacidic media. For example, reaction of the cinnamamide (60) with benzene in CF3SO3H gives the addition product in quantitative yield (eq 20).27... 

Highly diastereoselective alkyl radical addition to Oppolzer s camphorsultam derivative (33) of oxime provides enantiomerically pure a-alkyl-a-amino acid derivative (34) at — 78 °C by the same method as shown in eq. 10.16. Moreover, enantioselective tandem radical 1,2-difunctionalization of cinnamamide (35) can be carried out with high stereoselectivity, using the chelation manner of the cinnamamide and a chiral bisoxazoline ligand on Mgl2, as shown in eq. 10.17. 

Z-Cinnamamide derivatives, (III), prepared by Bencherif (3) selectively bound to the a7 AChR receptor were used in the treatment of Alzheimer s disease. 

Other specific procedures for the synthesis of cinnamonitrile include the dehydration of cinnamamide with phosphorus... 

Cinnamamide-)6-CD (6-CiNH-/J-CD) is sparingly soluble in water. The solid state NMR studies CP/MAS NMR) show that the phenyl group is included in the /3-CD cavity. The X-ray powder pattern showed that 6-CiNH-P-CD forms a layer structure of the CD dimer. 

The fact that 6-CiNH-a-CD formed a supramolecular dimer in which cin-namoyl groups are included from the primary hydroxyl groups led us to use 3-cinnamamide-a-CD (3-CiNH-o -CD) as a building unit, because the phenyl group can be included in a-CD from the primary hydroxyl side successively to form supramolecular polymers. Actually, 3-CiNH-a-CD was found to form long supramolecular polymers with a molecular weight higher than 1.6 x 10 (Fig. 20). 

This method is highly selective for unsaturated ketones and aldehydes, whereas reduction of a,p-un-saturated carboxylic acid derivatives, such as esters, amides and nitriles, is very sluggish. Thus, benz-ylideneacetone was selectively and cleanly reduced in the presence of methyl cinnamate, cinnamonitrile or cinnamamide. ... 

C9H9NO cinnamamide, predominantly trans 621-79-4 489.83 42.908 2 16499 C9H9N303W triacetonitrile tungsten tricarbonyl 16800-47-8 307.15 25.714 1,2... 

Keywords franj-cinnamamide, dicarboxylic acid, cocrystals, [2+2]photodi-merization, cyclobutane... 

---