Neophyl iodide

CsH5C(CHs)>CH>1. Neophyl iodide, prepared (59) from neophyl chloride (58) reacted with K3Co(CN).-> in the same way, except that 12 ml. of benzene were added to disperse the halide, and reaction time was 20 hours. The infrared spectrum of the light brown solid product isolated exhibited CN stretch bands at 2125 and 2089 cm." Acidification followed by alkali treatment yielded neophyl cyanide (infrared and PMR analysis). 

Neopentyl and Neophyl Iodides. The halides mentioned above formed the corresponding organocobalt complexes on reaction with pentacyanocobaltate(II). While neopentyl radical is stable to rearrangement, the neophyl radical undergoes aryl migration (56) as follows ... 

Even though photoinduction is the most commonly used initiation method, not many studies on the mechanism involved have been reported. This step can involve ET within an excited charge-transfer complex (CTC) formed between the nucleophile and the substrate. This type of initiation has been proposed for the reaction of CHjCOMe ions with iodobenzene and bromobenzene in DMSO, for nitrile carbanions with haloarenes such as 2-bromonaphthalene or p-bromobiphenyl in liquid ammonia, " and in the reaction of iodobenzene and PhSEt " with (EtO)2PO ions in DMSO and DMF, respectively. Acceleration by KI in the substitution of haloarenes with (EtO)2PO ions or with 2-naph-thoxide ions has been explained on the same basis. Initiation by a CTC has also been suggested for the photoinduced reaction of neophyl iodide with carbanions in DMSO. ... 

The quantum yield for substitution of neophyl iodide by CH2COPh ion was determined to be 0.127. The quantum yield of initiation, evaluated by suppressing the propagation steps with the presence of DTBN as radical trap, has a value of 10 ". Based on both quantum yields, the chain length or propagation obtained for the reaction is approximately 127. This is the first report of which is a direct... 

Displacements. Primary and secondary alkyl chlorides react rapidly and exother-mally with sodium cyanide in partial solution in dimethyl sulfoxide to give the corresponding nitriles in excellent yield. - The reactions are faster and the yields better than in the reactions of the corresponding bromides or iodides in aqueous alcohol. Neopentyl and neophyl halides can be converted by this method to... 

The mixed lithium neophyl(phenyl)cuprates react with high SN2-selectivity with chiral cyclic allylic acetates such as 37 providing chiral alkenyl iodides of type 38. In the presence of zinc bromide, a change of regioselectivity is observed and the reaction with the chiral acyclic pentafluorobenzoate 39 provides only SN2 -product 40 with 85% yield and 95% ee (Scheme 9.11) [22]. 

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