Cinnamoyl azides

In a related type of reaction, the styryl isocyanates, readily available by Curtius rearrangement of cinnamoyl azides, undergo thermal cyclization to l-isoquinolones in good yield (equation 34) the reaction can also be carrried out using Friedel-Crafts catalysts. 2,3-Dihydro-4( 1//)- isoquinolones are obtained by Dieckmann cyclization of N- (o- carbalkoxy-benzyl)glycine ester derivatives (equation 35). The same reaction has been used for the synthesis of a range of non-aromatic heterocycles (equations 36 and 37). 

Styryl isocyanates 183, readily available by Curtius rearrangement of cinnamoyl azides, undergo thermal or Friedel Crafts cyclization to 1-isoquinolones 184 (Scheme 110). 

The Curtius rearrangements of some franr-cinnamoyl azides (13), obtained by treatment of the corresponding chlorides with sodium azide, smoothly give franr-3-styryl isocyanates (14), which are efficiently isomerized in an inert solvent at 250 °C to produce 1-isoquinolone derivatives (15 equation 9). The isomerization proceeds more conveniently at 140 °C in the presence of iodine. 

Also, aromatic poljdsocyanates are obtained in the copolymerization of styrene with cinnamoyl azide (21). Blocked pol5dsocyanates (14) are obtained from p-nitrostyrene and carbon monoxide in methanol, using a nithenimn catalyst (22). 

Its expl props were not detd m-Nitrocinnamoyl Azide, col rhmb crysts (from ether), mp 117-18° (dec) puffs off at higher temp in sol in cold w or ale, sol in chlf or ether was prepd by treating m-nitro cinnamoyl hydrazide with Na nitrite + HC1 in water covered with ether (Refs 1 2)... 

Attempts to apply the azide-tetrazole isomerism to the synthesis of tetrazolo[l,5-a][l,3,5]triazines were published <88IZV491>. This equilibrium was found to be shifted generally to the ring opened azides (31), and the maximum amount of the tetrazole (32) of 15% was detected in DMSO-de at 20 °C in the case of = H, R = morpholino group. The same tetrazolo ring system was, however, found to be stable with 5-styryl and 7-thio substitution <87LA65> aminotetrazole (33) when reacted with cinnamoyl isothiocyanate alTorded the tetrazolotriazine-thione (34) most likely formed via cyclization of the intermediate thiourea. 

The preparations and properties of many polymers containing pendant aryl azide groups were described by Delzenne and London. There were attempts made to combine azide groups with cinnamoyl groups in one pendant substituent on polymers" ... 

Addition of the azide groups, however, does little to increase bond activity. Also, marked wavelength dependence on and transitions occurs in both functional groups, the azide and the cinnamoyl. 

Unsaturated Acids. The formation of olefinic acid azides by the sodium azide procedure appears to be limited only by the availability of the acid chloride. Examples of a,/3-olefinic acid azides prepared by this method are crotonyl, cinnamoyl, and methacrylyl azides. The hydrazide route to the azide is sometimes complicated by ride reactions. The esters of oleic acid and elaidic acid give the respective hydra-zides in good yield under the usual conditions, but severe treatment causes reduction of the unsaturated hydrazides to stearoyl hydrazide. ... 

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