OKay, I know that I should stop posting bizarre chemistry, but I just can't help myself. (Probably only Rev drone and Rhodium will apreiciate this topic
)
This is the general route to which I propose: where Ar can be any* substituted phenyl ring
[ArCH2CH2CO2]2 + Cu(I) + hv --> ArCH2CH2CO2Cu(II) + CO2 + ArCH2CH2*
ArCH2CH2* + NH3 + Cu(II) -{hv}-> ArCH2CH2NH2 + H(+) + Cu(I)
Here the article...
"Mechanism of Electron transfer Oxidation of
Alkyl Radicals by Copper(II) Complexes", in The Journal of the
American Chemical Society, Vol 90, yr 1968, page 4616-4625. Also there
is another article in the same volume on page 4038-4050, it is also a
good one.
The article use Cu(II) species to decompose peroxides (!) to alkyl
radicals that either form alkenes or nucluephilic substituted alkanes
(!).
Page 4616
"Oxidative elimination
>CH-C<* --> >C=C, + H(+) + e
Oxidative substitution
>CH-C<* --> >CH-C<-N(+) + e
N = necleophile = HOAc, HOR, CH3CN, ArH, etc. ..."
Page 4618
"Kinetics of Oxidation of [Beta]-Arylethyl Radicals. [Beta]-Arylethyl
radicals (substituted on the ring) were derived from the catalyzed
decomposition of substituted hydro-cinnamoyl peroxides [1]. Oxidation
of these [Beta]-arylethyl
[ArCH2CH2CO2]2 + Cu(I) --> ArCH2CH2CO2Cu(II) + CO2 + ArCH2CH2*___(15)
radicals with Cu(II) gave a mixture of elimination
(styrenes) and substitution ([beta]-arylethyl acetates)
products. The relative amounts of aceate and
styrene derivetives represented the relative rates of
oxidative substitution, Ks, and elimination, Ke, respectively. ...
ArCH2CH2* + HOAc + Cu(II) -{Ks}-> ArCH2CH2OAc + H(+) + Cu(I)___(16)
ArCH2CH2* + Cu(II) -{Ke}-> ArCH=CH2 + H(+) + Cu(I)___(17)"
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Hopefully I didn't include any mistakes, typos or whatnots....
This post is for informational purposes only an is not intended to facilitate illegal activity.
