CONCERNING THE REACTIVITY AND CONJUGATION OF THE -OLEFINES

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP80T00246A007100690002-6
• Release Decision: RIPPUB
• Original Classification: K
• Document Page Count: 10
• Document Creation Date: December 22, 2016
• Document Release Date: July 15, 2009
• Sequence Number: 2
• Publication Date: August 7, 1959
• Content Type: REPORT

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 Approved For Release 2009/07/15: CIA-RDP80T00246AO07100690002-6
QONCERNING THE REACTIVITY AND CONJUGATION OF 'THE It -OLFFINW
.. I. L. Knunyants
The specific properties of the f -olefins reflected most
1trikingly in their reactions with nucleophilic reagents have
ow ceased to astonish chemists, since these properties are
recounted for by the electronic exhaustion of the y -bond.
lcoording to their speed of interaction with nucleophilio
bompounds, the `f-olefines may be arranged in a row, with ?
agent forming the radical. Noteworthy in this respect are
r-ethylene the least reactive.
The reverse holds true in reactions with electrophilio
ompounds. The same relationships are valid in radical reactions,
prhich proceed the more readily, the weaker the bond of the
e reactions of the If-olefineswith nitrogen dioxide, in which,
from the dinitrocompounds reported by Cofman in 1949 &M
:Citroperfluor paraffin alcohols and 0-nitroperfluornitrose----fIn@
aeldine in.1953, exceedingly interesting nitrites of ox
gold be formed.
Ibvestigation has shown that in these reactions, which
e of a radical nature, the reactivity of the u-olifines, as
4L
ght be expected, falls drastically from f -ethylene via l-propylene
.d 'f-oyclobutene to 'f-isobutylene. Thus, whereas tetrafluorethylene
eactl with N204 explosively and a controlled reaction can be
btained only in the medium of an inert solvent (CC14; OHIO 1-01201,
f -isobutylene can be drawn into the reaction only at
$360 - 180?C. without the use of a solvent. In every case, along
with dinitro- 'f-paraffins there do indeed appear nitrites of a' -nitro-
i`f-paraffin alcohols, whose formation earlier investigators eoasehow
failed to notice. When f -ethylene, %f-propylene, and `P.-iso-butylene
are nitrated, 'the ratios of the dinitroparaffine and the nitrites
foraedare 1:1 1: ?
4, and 'l:1 respectively.
r,
4 Approved For Release 2009/07/15: CIA-RDP80T00246AO07100690002-6
rfessor Knunyants, Moscow Academy of Science, Prospect Lenin,
., Institute of Elementary Organic Compounds.
 Approved For Release 2009/07/15: CIA-RDP80T00246AO07100690002-6
-2-
The reaction ,begins with the *-olifine ,be pg,. attacked by t%e
radioal-like electrophilic particle NO2 and leads to a radical
tabiliaed by the interaction of the odd electron with C-F bonds,
ioh Hasseldine rightly compares in stability with tertiary
'dioals. The further recombination of these radicals gives
Vise to nitrites and nitrosocompounds:
(GF3)F