Alkylation nitrile

NITRILES, alkylation of, 55, 91 NITRILES, a-vinyl- [Nitriles a-ethenyl-],... 

Nickel, dichloro [ethylenebis(dimethyl-phosphine)], 58, 133 Nickel, dichloro[ethj lenebis(diphenyl-phosphine)], 58,133 [Ni (-)-diop Cl2 ], (-)-diop=2,3-0-iso-propylidene-2,3-dihydroxy-l,4-bis(di-phenylphosphino)butane, 58, 133 Nickel, dichloro [ trimethylenebis(diphenyl-phosphine)], 58,133 NITRILES, alkylation of, 55, 91 NITRILES FROM KETONES, 58, 101 NITRILES, a vinyl, 55, 99, 101 p-Nitrobenzenesulfonyl cyanide, 57, 89 p-Nitrobenzyl alcohol, 57, 72 p-NITROBENZYL FLUORIDE, 57, 72 Nitro compounds, 56, 36 Nitronates, 56, 36... 

Under these conditions esters, carboxylic acids, lactones, amides, nitriles, alkyl halides, and nilro compounds arc not reduced. Some of the groups are reduced, however, in refluxing 2-cthyHiexanol (I30 ). 

RCHO to a ketone RCOR (for other methods, see 10-71, 16-82, and 18-9). In this procedure the normal mode of reaction of a carbonyl carbon is reversed. The C atom of an aldehyde molecule is normally electrophilic and is attacked by nucleophiles (Chapter 16), but by conversion to the protected cyanohydrin this carbon atom has been induced to perform as a nucleophile. The German word Umpolung is used to describe this kind of reversal (another example is found in 10-71). Since the ion 166 serves as a substitute for the unavailable R— C=0 anion, it is often called a masked R( C=0) ion. This method fads for formaldehyde (R = H), but other masked formaldehydes have proved successful. In an interesting variation of nitrile alkylation, a quaternary bromide [PhC(Br)(Me)CN] reacted with allyl bromide, in the presence of a Grignard reagent, to give the alkylated product [PhC(CN)(Me)CH2CH=CH2]. ... 

Carboxylic Acid Derivatives generally have a acyl group(RC=O) attached to an electronegative atom, with the notable exception of nitriles (Alkyl group attached to a cyano group). Illustrated examples should be added at some later time. Please see John McMurry s Organic Chemistry 6th edition chapter 22 for further explanation on this topic... 

Dehydration of nitrogen compounds is a well-known route to nitriles. Alkyl, aralkyl, aryl, and heteroaryl amides are readily converted into the corresponding nitriles using trichloromethyl chloroformate as the dehydrating agent (Scheme 130) the work-up is... 

Alkyl cyanides. See Nitriles Alkyl fluorides, 625 Alkyl groups... 

Primary or secondary alkyl halides can be converted into nitriles (alkyl cyanide) by nucleophilic substitution. The nitriles formed can in turn be converted to carboxylic acids by hydrolysis. 

Reactions with Active Methylene Compounds. Enolates of ketones," esters," enediolates," 1,3-dicarbonyl compounds," amides and lactams," as well as nitrile-stabilized carbanions," can be alkylated with benzyl bromide. Cyclohexanone may be benzylated in 92% ee using a chiral amide base." Amide bases as well as alkoxides have been employed in the case of nitrile alkylations." Benzylation of metalloenamines may be achieved and enantioselective reactions are possible using a chiral imine (eq 3). However, reactions between benzyl bromide and enamines proceed in low yield. The benzylation of a ketone via its enol silyl ether, promoted by fluoride, has been observed. ... 

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