Cinnamaldehyde 2-nitro

The monoanions of primary nitroalkanes, phenylnitromethane, and a-nitro esters are all preferentially C-alkylated by cinnamyl acetate and 2-butenyl acetate in 50-89% yield in the presence of Pd catalyst (Eq. 5.51).75 The a-nitro ester gives the C-alkylate in 89% yield, but 2-nitropropane gives the C-alkylate in only 29% yield. The main product is cinnamaldehyde, which is derived from 0-alkylation.75a... 

Pseudonitrosites can sometime be isolated and converted into furoxans by heating in alcohol or water. In some cases the reaction is carried out with a mixture of nitrogen oxides for example, 4-nitro-3-phenylfuroxan is obtained by the action on cinnamaldehyde of nitrogen oxides generated by a mixture of nitric and arsenious oxides [9],... 

Wittig olefination of 2-nitro-Z-cinnamaldehyde (1300) with the phosphonium bromide 1301 led to the diene 1302. The Diels-Alder cycloaddition of 1302 with maleimide (1303), followed by dehydrogenation with DDQ, afforded the phthali-mide 1304. Double deoxygenation of 1304 with triphenylphosphine (PPhs) in collidine gave O-methylarcyiiaflavin B (1305). Finally, heating of 1305 with molten pyridine hydrochloride led to arcyriaflavin B (346) (759) (Scheme 5.215). 

The significant synthetic advantage of this approach is the isolation of regio-and stereo-defined enol silyl ethers of optically active y-nitro aldehydes (Table 4.2). For example, after the reaction of 16a with trans-cinnamaldehyde, the resulting mixture can be directly purified by silica gel column chromatography to produce the optically active enol silyl ether 20a in 90% yield (Table 4.2, entry 1). High... 

Sometimes nitrofuroxans are produced. The explosive 3-methyl-4-nitro compound (52) is formed from propene and dinitrogen trioxide or tetroxide when no oxygen is added to the reaction,286,287 and also by the action of nitrous acid on methacrylic acid.127 4-Nitro-3-phenylfuroxan is a by-product of the reaction of nitrogen oxides (from nitric acid and arsenious oxide) and cinnamaldehyde.288... 

Nitrile, azo, and nitroso groups, and even the oxygen molecule, take part in such reactions, and acetylenic triple bonds in particular confer reactivity as philodiene. As for dienes, so for philodienes the reactivity depends on the constitution. Activating groups particularly favor addition. The most reactive components include <%,/ -unsaturated carbonyl compounds such as acrolein, acrylic acid, maleic acid and its anhydride, acetylenedicarboxylic acid, p-benzo-quinone and cinnamaldehyde, as well as saturated nitriles and <%,/ -unsaturated nitro compounds. Tetracyanoethylene also reacts with dienes.41,42 Conjugation of the double bond to an active group is not absolutely essential for a philodiene, for dienes add under certain conditions also to philodienes with isolated double bonds examples of the latter type are vinyl esters and vinyl-acetic acid. Ketenes do not undergo the Diels-Alder reaction with dienes, but instead yield cyclobutanone derivatives 43,44... 

The acyloin (benzoin) condensation is applicable, not merely to benzaldehyde itself, but also to its homologs, to its alkoxy derivatives, and to furfur-aldehyde. It fails, however, with free hydroxybenzaldehydes and with halo-genated nitro and amino benzaldehydes and cinnamaldehyde gives diminutive yields. 

A soln. of cinnamaldehyde thiosemicarbazone in dry tetrahydrofuran stirred at room temp, with 1.4 equivalents of NaHCOg, a soln. of an equimolar quantity of 5-nitro-2-furoyl chloride in the same solvent added, stirred 2 hrs., and refluxed 30 min. cinnamaldehyde S-(5-nitro-2-furoyl)thiosemicarbazone. Y 87%. F. e. s. W. S. Sherman and A. A. Alter, J. Org. Chem. 21, 2237 (1962). 

The most relevant structural features of this new class of SPS co-crystals is that suitable guests are not only small molecules (both essentially apolar, like DCE[55] and highly polar, like 4-nitro-aniline [53]) but also long molecules like 4-(dimethyl-amino)-cinnamaldehyde, which exhibit a molecular volume too large to be enclosed as a guest into the 8 phase. 

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