Spectrophysics and photochemistry of the formaldehyde molecule. Part II

Buck, HM Henk

doi:10.1002/recl.19821010701

Cited by 1 publication

(2 citation statements)

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“…Alternatively, since oxidation of hydrazine by molecular oxygen must proceed via the radical cation, [H2NNH2] +- [6], which would also be electrophilic, the same arguments as were made for [4] could be applied. It is conceivable, but less likely, that I6] could also deliver two hydrogen atoms stereoselectively in a concerted and competitive process to an alkene.…”

Section: Methodsmentioning

confidence: 99%

“…The use of hydrazine for the reduction of ethylenic (olefinic) bonds has been known for almost eighty years and is believed to involve the intermediacy of diimide (HN=NH, [1 ]), a reactive species that first excited considerable attention some twenty years ago (1,2). A range of papers describing calculations on (3)(4)(5)(6)(7), or properties of (8)(9)(10), diimide is evidence of a continuing interest in unravelling the chemistry of this species. The hydrazine reduction reaction has found favor for reductions of unsaturated fatty acids (11)(12)(13) because no apparent cistrans isomerism or ethylenic bond positional shifts occur, in strong contrast to the results from the use of catalytic hydrogenation (14).…”

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confidence: 99%

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Studies on the mechanism of the hydrazine reduction reaction: Applications to selected monoethylenic, diethylenic and triethylenic fatty acids ofcis configurations

Ratnayake

Grossert

Ackman

1990

J Americ Oil Chem Soc

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The hydrazine reduction of cis ethylenic bonds has been studied using a number of Cle, Cls, and C20 monoethylenic, Cls diethylenic, and Cls plus C20 triethylenic fatty acids. Relative reduction rates were determined and correlated with the positions of the ethylenic bonds in the fatty acids. The terminal ethylenic bond was the most reactive and among the others, reactivity was greater nearer the ends of the chain than in the center. Also, the ethylenic bonds closer to the carboxyl group showed greater reactivity than those closer to the methyl end of the chain. Differences in reactivity among the centrally located double bonds were not significant. These reactivity trends are consistent with a mechanism involving protonated diimide as an intermediate in the reduction process. In diethylenic fatty acids, the non-methylene-interrupted dienes showed slightly lower reactivity than the methylene-interrupted counterparts, which indicated that both the position of ethylenic bonds and the relative distance between two ethylenic bonds in the diene influence the rate of reaction. The information obtained from the rate studies should be useful for predicting the product distribution from partial hydrazine reductions of long-chain polyethylenic compounds.KEY WORDS: Diimide reductions, fatty acids, hydrazine reduction, reduction of unsaturated fatty acids, structure determinations.

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Section: Methodsmentioning

confidence: 99%