Ethylene derivatives nitriles

Acetonitrile added dropwise with stirring at 3-8 to 92%-H.2SO y then 3-methyl-3-buten-l-oI added slowly at 8-10°, and stirred ca. 25 min. while allowed to warm to room temp. 2,4,4-trimethyl-5,6-dihydro-4H-l,3-oxazine. Y 48%. F. e. s. S. P. McManus and J. T. Carroll, Org. Prep. Procedures 2, 71 (1970) from nitriles, ethylene derivs., and formaldehyde cf. C. Giordano, G. Ribaldone, and G. Borsotti, Synthesis 1971, 92. 

In Chart 7 we included a short series of benzylidenemalononitriles as well as a-nitrostilbenes.116 Note that the most common functionalities associated with the chemistry of the nucleophilic addition to the C=C bond, namely aldehydes, ketones, esters, anhydrides and nitriles, are EW substituents present in dienophiles and dipolarophiles used in NED DA and 1,3 dipolar cycloadditions, and they are included in Table l.121 In Table 14, we summarize the global properties and local electrophilicity values for the series of benzylidenemalononitriles and a-nitrostilbenes. Both series present ethylene derivatives with large electrophilicity values, to > 2.3 eV, they being classified as strong electrophiles within the theoretical electrophilicity scale.39... 

Subst. carboxylic acid amides from nitriles and ethylene derivatives Ethylene derivatives from, snbst. carboxylic acid amides... 

Unhindered acrylic compounds afford high yields of Baylis-Hillman adducts at ambient pressure whereas substituted acrylic nitriles and esters require high pressure to lead to functionalized ethylenic derivatives in fair to excellent yields (Table 10.14). 

Nitriles from terminal ethylene derivs. Regiospecific hydrocyanation via hydroboration... 

Ethylene derivatives from nitriles. Hydrogen cyanide, 1,6-elimination) 18, 986 —, thermal 17, 972 Dehydrocyclization s. 

Oxidations by hydrogen peroxide and nitriles Oxido compounds from ethylene derivatives s. 16,199... 

Nitryl fluoroborate 1,2-Nitroacylamines from ethylene derivs. and nitriles Extended Ritter reaction... 

Sodium hydride Sym. ethylene derivs. from 2 nitrile molecules... 

Aldehydes of different types can be conveniently prepared from the next lower halides through carbinols which are split by dia-zotized sulfanilic acid Aliphatic aldehydes in particular can be easily obtained from carboxylic acids through N-acylethylenimi-es Aldehydes, in turn, can be converted directly into nitriles with hydroxylamine hydrochloride Ketones can be efficiently prepared from ethylene derivatives via boranes and, in high purity, from labile alcohols by oxidation in an aq.-ethereal two-phase medium Heating aliphatic acids with reduced iron powder proved to be an excellent method for the prepn. of sym. straight-chain ketones /5-Aminoketones unobtainable by Mannich reaction may be prepared via halogenomagnesium enolates... 

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