Cinnamonitriles, reaction with

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

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

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). 

Chloroperoxidase catalysis by, 58, 302 in chlorination of pyrazoles, 57, 337 Chlorophyll, thioaldehyde synthetic intermediate to, 55, 3 Chlorosulfonyl isocyanate, reaction with 2-arylhydrazono-3-oxobutanoate, 59, 148 Chromatography, of [l,2,4]triazolo[l,5-a]-pyrimidines, 57, 106 Chrom-3-enes, see 2//-l-Benzopyrans Chromium tricarbonyl complexes of 3,5-diphenyl-l-(alkyl- or oxido-)-thiabenzenes, 59, 206, 227 indoles, lithiation of, 56, 181, 184 of pyridine, 58, 160 pyridines, lithiation of, 56, 230, 239 of 2f/-thiopyrans, 59, 227 Chromones, see l-Benzopyran-4-ones Cinnamonitrile, a-cyano-, condensations with thio-, seleno-amides, 59, 184, 186 Cinnoline, nitration, MO calculation, 59, 302... 

Acrylonitrile can also be successfully used. The reaction with water-insoluble aryl iodides is carried out in HMPA-H2O mixture (9 1, v/v), giving high yields of the corresponding cinnamonitriles. Water-soluble aryl iodides like iodobenzoate and iodophenolate ions readily react in neat water. Palladium acetate (1 mol%) is usually used as the catalyst precursor. Unlike most other Heck reactions, which give almost exclusively ( ) isomers of the products, the reactions with acrylonitrile yield a mixture of E) and (Z) isomers with 3 1 to 4 1 ratio, close to that observed under conventional anhydrous conditions [94]. 

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>. 

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... 

The diazoacetonitrile-imine reaction may be considered complimentary to azide addition to cinnamonitriles because in the latter case only triazoline thermolysis products result.284 The reversed order of reactivity of the diazoacetonitrile to that of diazomethane implies an electrophilic attack on the imine and is explained in terms of a LUMOdi MC lonit[ile-HOMOin,int controlled interaction. Thus electron-rich enamines, which do not react with diazoalkanes, may be expected to react with electron-poor diazo compounds. 

The synthetically useful a,/J-unsaturated [nC]-labelled precursors, [nC]acrylonitrile (192) and [11C]cinnamonitrile (193), have been prepared189-191 with potassium [nC]cyanide (equation 101). The substitution reactions have been performed in MeCN, benzene, 1,2-dichlorobenzene, DMSO and THF solvents, but the highest radiochemical yields were obtained in acetonitrile. 192 was used in a model reaction (equation 102) to synthesize 2-cyano[nC]ethyldimethyl malonate 194 from sodium hydride/dimethyl malonate. 

A new efficient procedure has been proposed for the synthesis of 3-aryl-5-amino-l//-pyrazoles by reaction of a-chloro-/ -arylacrylonitriles with hydrazine hydrate <2004RJ01518>. Reaction of 2-(3,3-dicyano-2-propenylidene)-4,4,5,5-tetra-methyl-l,3-dioxolane 641 with hydrazine afforded 3-(2-hydroxy-l,l,2-trimethylpropoxy)pyrazole 642 (Equation 134) <2003RJ01016>. Treatment of ethyl 3,3-dicyano-2-methoxyacrylate with alkyl, aryl, heterocyclic, and sulfonyl hydrazines led to the synthesis of N-l-substituted 3-acyM-cyano-5-aminopyrazoles, which are versatile intermediates for the synthesis of many biologically active scaffolds <2006TL5797>. 2-Hydrazinothiazol-4(5//)-one reacted with a variety of cinnamonitrile derivatives and activated acrylonitriles to yield annelated pyrazolopyrano[2,3-rf thiazole <1998JCM730>. 

The Sn2 mechanism is ruled out for reaction between the tertiary halide, r-BuBr, and radical anions derived from the more easialy reduced compounds cinnamonitrile (9) ethyl cinnamate (12a), methyl styryl ketone (23a), and phenyl styryl ketone (20a). Reduction of the activated alkenes in the presence of an excess of r-BuBr leads to mixtures of products where a r-Bu group has been introduced in a- or j0-position or in the phenyl ring. For 9 and 12a small amounts of butylated hydrodimers were obtained in addition, and for the enone 23a formation of the unsaturated alcohol with introduction of the /-Bu group at C-1 was a major product [192]. In this case the mechanism is unambiguously reduction of the activated alkene followed by electron transfer to r-BuBr concerted with halide cleavage, in... 

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