1284 Russian Chemical Bulletin, VoL 47, No.

7, July, I998

The ratio of the rate constants for H atom abstraction and 13-cleavage
for bis-oxyisopropylidene biradicai
S. A. Grabovsky, N. N. Kabai'na~a, S. L Khursan, and ;I. V. Shereshopets*

Institute of Organic Chemistry, Ufa Research Center of the Russian Academy of Sciences,
71 prosp. Ok,tyabrya, 450054 Ufa, Russian Federation.
Fax: + 7 (347 2) 35 6066

The relative reactivity of bis-oxyisopropylidene biradicai "OCMe20" generated upon

horaolysis of the O--O bond of diraethyldioxirane was characterized by the ratio of the rate
constants for H atom abstraction and It-cleavage: ka/k2 -- 0.23+0.06 L tool -I (314 K).

Key words: kinetics, dioxiranes; free radicals.

C o n v i n c i n g e v i d e n c e was obtained that the reaction Results and Discussion

o f d i m e t h y l d i o x i r a n e ( D M D O ) with saturated organic
c o m p o u n d s occurs by a radical m e c h a n i s m 1-8 involving Formal kinetics. The kinetics o f the thermolysis o f
bis-oxyisopropylidene biradical as the key intermediate. c o m p o u n d 1 were studied in an o x y g e n a t m o s p h e r e as a
This biradical, like o t h e r oxyl radicals, ~ tends to undergo function o f the [MeyCOI : [CCI4] ratio. A decrease in
13-cleavage attd hydrogen a t o m abstraction. 7,g In this the c o n c e n t r a t i o n o f a c e t o n e retards the therrnolysis,
work, we d e t e r m i n e d the ratio o f the rate constants for indicating the i n v o l v e m e n t o f a c e t o n e in the reaction.
these reactions. U n d e r these conditions, the c o n s u m p t i o n o f dioxirane
obeys first-order kinetics o v e r t h e w h o l e c o n c e n t r a t i o n
Experimental range studied. F r o m the kinetic curves, we calculated
the effective rate constants (keff/s - I ) o f d e c o m p o s i t i o n
Acetone and tetrachlororaehane were purified by a known o f 1 as a function of the c o n c e n t r a t i o n o f a c e t o n e
procedure, t~ Diraethyldioxirane I was synthesized in a spe- (tool L - I ) :
cially designed reactor that consisted of a 250-raL three-
[MeyCO ] 13.66 8.69 6.21 1.04 0.55
necked flask equipped with a mechanical stirrer and an air
/%~-- I ~ 2.7+0.3 2.07+0.05 1.58+0.06 0.82+0.01 0.68+0.05
condenser. The condenser was connected to a trap cooled with
an n-octane--liquid nitrogen mixture ( - 5 6 *C). Acetone It was found that kcfr does not d e p e n d on the initial
(15 raL), NaHCO 3 (12 g), and water (20 mL) were placed in concentration o f c o m p o u n d 1.
the reactor, and then oxone (KHSO4"2KHSO 5" K2SO4) Decomposition mechanism. T h e kinetic features o f
(25 g) was added. The reaction was conducted for 25 rain
the c o n s u m p t i o n of dioxirane can be e x p l a i n e d in terms
(Tmact = 10 ~ under argon with intense stirring under
vacuum (~150 Tort). The yellowish solution collected in the o f the m e c h a n i s m proposed previously. 7 T h e steps de-
cooled trap was dried with magnesium sulfate for 4 h at termining the reaction rate are t h e following: reversible
- 5 6 *C. The solution was distilled in vacuo (~45 Torr) at homolysis o f dioxirane at the O - - O bond, 13-cleavage of
- 1 0 *C into a trap cooled with liquid nitrogen. Diraethyl- bis-oxyisopropylidene biradical, a n d abstraction o f t~ae
dioxirane was identified and analyzed according to the proce- H atom:
dure reported previously. It The kinetics of decomposition of
compound t were monitored by spectrophotometry (Speeord
M40) measuring the decrease in the optical density (X. = 335
nra) at 41.0+0.5 *C in a 2.6-raL quartz cetl (optical path t cm)
maintained at a constant temperature. The initial concentra-
xo.- XOo: ,,>
tion of compound I varied in the (0.72--4.32)" 10-2 raol L -I
range. Mixtures of acetone and tetrachlororaethane in various
ratios were used as the solvent. The experiments were carded
out in an oxygen atraospl',ere, which was maintained by con-
~ O"
O"
~ MeCOO" + Me"
(2)
tinuous introduction of oxygen to the solution. The concentra-
tion of oxygen, calculated flora published data, iz ranged from
6.8- 10 -3 (acetone) to 1.4.10 -2 tool L -I (tetrachlororaethane).
It was shown in preliminary experiments that during purging,
o)= " O" + "CH2C(O)Me (3)
the content of diraethytdioxirane remained virtually constant. Xo + ~ X ~

Translated from Izvestiya Akademii Nauk. Seriya KhimicheskaviJ. No. 7, pp. 1321--1323, July, 1998.
1066-5285/98/4707-1284 $20.00 9 1998 Plenum Publishing Corporation
The rate constants for bis-oxyisopropylidene biradical
T h e subsequent reactions result in the formation of
c a r b o n - c e n t e r e d radicals, which are rapidly converted
into peroxy radicals in the oxygen atmosphere:
MeCOO" ,. M e " + CO z,
~ OH
O"
=
Me + MeCOOH,
O" + O ' .,~OH
X ~ OH + "CH2C(O)Me'
R" + O z ) ROO" (R = CH2C(O)Me, Me).
U n d e r the c o n d i t i o n s chosen, peroxy radicals are
inactive in the chain propagation reaction; they do not
react with c o m p o u n d I s but, instead, undergo r e c o m b i -
nation and t e r m i n a t e the oxidation chain.
Steps (4)--(7) have no effect on the rate o f c o n -
s u m p t i o n o f dioxirane. A c c o r d i n g to the a b o v e - p r e -
sented m e c h a n i s m , the rate o f the process is
a[DMDO l = k§ 2 +kj -[M~COI) -[DMOOI
dt k_ I + k:l + k 3 9[MezCOI " radical as shown by the increased k 2 value and, corre-
Apparently, the rate o f closure o f the dioxirane ring
( 14/_I ) is substantially higher than the rate of destruction
(W'2) and the rate o f hydrogen abstraction by the biradical
intermediate (kl"3). in this case, the d e p e n d e n c e o f the
effective rate c o n s t a n t for the c o n s u m p t i o n o f c o m -
p o u n d I on the c o n c e n t r a t i o n o f a c e t o n e can be trans-
formed in the linear form:
kerr = Kt - k 2 + K I ' k 3"[Me2CO ].
Equation (9) holds with a high correlation coefficient
( r = 0.995) (Fig. I, plot 1). F r o m the d e p e n d e n c e of k~rr
on the COl~centration of acetone, the parameters of this
e q u a t i o n were calculated:
KI "k 3 = (1.5+0.2)" 10-6 L tool -I s -I,
Kl - k~ = (6.4+1.5)" 10 -6 s -I,
k3/k 2 = 0.23+0.06 L tool -I.
It is of interest that the corresponding ka,/k d ratio for
the t e r t - b u t o x y radical, c a l c u l a t e d from published
data, 13-14 is 5 k mol -~, T h e lower k3/k 2 ratio found for
bis-oxyisopropylidene biradicals, c o m p a r e d to the corre-
sponding ratio of the rate constants for reactions of tert-
butoxy radicals, is apparently due to more effective
[)-cleavage of the biradical. Apparently, the biradical
intermediate is more destabilized than the /ert-butoxy
Russ.Chem.BulL, VoL 47, No. 7, July, 1998 1285
/c,~r 9 lO~ts - I
7 ,,
(4)
6 2
(5)
5 ,..,
4 Zx
3
(6)
(7)
0 ) i .... I J
2 4 6 8 [Me2COl/moi L -I
Fig. 1. Dependence of the effective rate constant (/%ff) of the
thermolysis of ! on the concentration of acetone: freshly
prepared solution of ! (1); after storage for 7 days (2).
(8)
spondingly, the decreased k3/k2 ratio.
N o t e that when dioxirane was stored for 7 days at
- 5 6 ~ (with short thaws needed to take aliquot samples),
its concentration decreased from 0.1 to 0.09 tool L - l .
The pattern o f d e p e n d e n c e o f keg on the c o n c e n t r a t i o n
o f acetone changed accordingly (see Fig. !, plot 2). T h e
increase in keff is obviously due to the fact that products
of decomposition o f c o m p o u n d 1 with more flexible H
atoms appear in the a c e t o n e solution. In our o p i n i o n ,
(9) this accounts for the increase in the rate o f c o n s u m p t i o n
of 1 in the presence o f products o f its d e c o m p o s i t i o n ,
which has been observed earlier, ts
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