Cinnamonitrile

The reaction time depends on the quality of the potassium hydroxide employed. An induction period is often observed when older potassium hydroxide samples are used, possibly because surface formation of carbonates reduces the solubility of the salt in acetonitrile. An attempt was made to monitor the cinnamonitrile reaction by GLC, following loss of starting... 

The method described is a modification of the procedure used by Ghosez to synthesize cinnamonitrile. 3-(2-Furyl)acrylo-nitrile has been prepared by catalytic condensation of furfural with acetonitrile in the vapor phase at 320°, by dehydration of the corresponding amide over phosphorus pentachloride, and by decarboxylation of 3-(2-furyl)-2-cyanoacrylic acid. ... 

Cyclocondensation of pyridine-2-thione 100 with cinnamonitriles 101 in the presence of a catalytic amount of NEts afforded 4,6-dihydropyrido[2,l-Z)][l,3]thiazine-6-ones 102 (98MI10, 99MI26). 

Preparation of the analogue metioprim involves an alternate approach. Aldol condensation of aldehyde 59 with propionitrile gives the cinnamonitrile Reaction of... 

Wagner and co-workers explored the different selectivity of 1,3-dipolar cyclo additions of nitrones 140 and cinnamonitrile 139 leading to oxadia-zolines 141 derived from an exclusive CN attack instead of a C = C attack (Scheme 50). This behavior was observed when cinnamonitrile was coordinated to a transition metal like Ft or Pd [89]. A similar approach to platimun-promoted nitrile-nitrone cyclo additions was reported using cychc nitrones. In this case, the authors reported a higher stereoselectivity of cychc nitrones with respect to the acyclic nitrones, due to a rigid E conformation adopted by cyclic nitrones [90]. 

Other substituted olefins such as acrylonitrile, fumaronitrile, crotono-nitrile, cinnamonitrile, and diethylfumarate also formed adducts with Co (DMG)2 complexes containing py, H2O, or PBuj and, in one case, with [Co (DMG-BF2)2py]. Second-order rate constants were reported for the formation of several Tr-olefin-Co(I) complexes from organocobalt(III) complexes containing, for example, NCCH2CH2- with DMG, DPG, DMG-BF, py, H2O, and PBuj. 

Thiazolopyranopyrazoles such as 438 were obtained from condensation of hydrazinothiazoles 436 with activated cinnamonitriles 437 followed by further reaction with hydrazine (Equation 118) <1998JRM3207>. 

Van Bladeren PJ, Delbressine LP, Hoogeterp J J, et al. 1981. Formation of mercapturic acids from acrylonitrile, crotononitrile, and cinnamonitrile by direct conjugation and via an intermediate oxidation process. Drug Metab Dispos 9 246-249. 

A remarkable switch in selectivity was observed by Wagner and coworkers in the cycloaddition of nitrones to free and coordinated ( )-cinnamonitrile (Scheme 6.208)... 

It is interesting to note that reduction of cinnamonitrile, related to aromatic nitriles, gives dimers. Electrochemical dimerization of acrylonitrile is a well-known industrial process of the... 

Cinnamaldehyde, by reduction of cinna-monitrile with Raney nickel alloy in formic acid, 51,25 from the ester-mesylate, 51,76 Cinnamic acid, 50,18 CINNAMONITRILE, 50,18 Condensation, of p-acetylbenzenediazo-nium bromide with acrylic acid, 51,1... 

Elnagdi et al. (88AP851) found that the reaction of 86 with tetracya-noethylene does not afford the expected structure 101 (X = Y = CN). Instead the hydrazones (88) (X = R = CN R = Ph) were isolated. Similarly, compounds 88 were formed upon treatment of 86 with cinnamonitrile derivatives. It was thus postulated that the reaction of these electron-poor double bonds with 86 proceeded via formation of an acyclic intermediate (e.g. 102) by reaction with 103, which then decomposes into isolable 101 by the elimination of water. In support, compounds 86 were recovered unreacted when treated with cinnamonitriles or with tetracyanoethylene in the absence of water (88AP851). 

Closely related are the routes that start from / -oxodiazenes. Pyridazin-4(l//)-ones and thio and imino analogs 274 for instance have been synthesized from diazenylacetates 273 and active methylene compounds (Equation 69). In the same paper reactions of 273 with a-substituted cinnamonitriles were studied which gave access to substituted pyridazin-4(17/)-ones <2004HAC300>. 

In this paper we will report on using a series of modifiers to enhance selectivity during 1-phenyl-1-propyne over a Pd/alumina catalyst. The modifiers, trans-cinnamaldehyde, trans-cinnamonitrile, 3-phenylpropionitrile, and 3-phenylpropylamine, were chosen to have a functionality that potentially could adsorb more strongly than an alkene and to be unreactive under the reaction conditions. 

The reaction of 1-phenyl-l-propyne (IPP) was then studied after modilying the catalyst with trans-cinnamaldehyde (TCA), trans-cinnamonitrile (TCN), 3-phenylpropionitrile (3PPN), and 3-phenylpropylamine (3PPA). The first-order rate constant calculated for the loss of 1-phenyl-l-propyne in each of the systems is reported in Table 1. All the modifiers were unreactive under the conditions used. 

Nitro compounds can be cyclized to give quinolines in two non-reductive processes. In the first, an o-nitro-cinnamate or -cinnamonitrile is cyclized by treatment with cyanide ions, via the cyanide addition product as generalized in equation (29). The reaction has been... 

Cinnamonitrile can be prepared by one of the common routes to nitriles, e.g., by dehydration of cinnamaldoxime. It is stable to alkali and is used for perfuming soap and detergents. 

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