REACTIONS

OF ACETONE
AND HYDROGEN
PEROXIDE 1283

Conductivity Results. Knowing the concentration vs. log mole % dioxane is also shown in Figure 5b.
of C(N02)a-from the optical absorption and also of its The plot yields a straight line. The intercept of 5
positive counterion which probably is a solvated proton, ohm-l cm2 equiv-' on the ordinate axis a t 100%
the equivalent conductivity of the ion pair can be cal- dioxane is taken as the equivalent conductivity of the
culated from the measured conductivity increase of the ion pair in this solvent. It may be pointed out that the
solutions. It turned out that the conductivity in- decomposition of NOz, produced by the reduction of
crease in pure dioxane is very low indicating a small / ~ (NO&
TNM, to form ions is too slow ( T ~ for NOZ- --+ +
equivalent conductivity of the ion pair in this solvent. NO,- = 700 pseclein water and ca. 10 sec in 2-propanole)
I n water-dioxane mixtures containing more than 35 to affect our results.
mole % water, the conductivity signals were large
Acknowledgment. The author wishes to express his
enough to be accurately measured. Figure 5a shows
thanks to Professor A. Henglein for many helpful dis-
a plot of the calculated equivalent conductivity vs.
cussions arid for his criticism of this work.
dioxane contents of the mixtures. The curve is similar
in shape to the curve giving the dependence of the di-
electric constant .I6 Extrapolation to 1 0 0 ~ odioxane (15) Calculated from the data in J E. Linde, Jr., and R. Fuoss,
J. Phys. Chem., 65, 999 (1961).
yields a very low value of the equivalent conductivity of (16) M. Gratsel, A. Henglein, J. Lilie, and G. Beck, Ber. Bunsenges.
less than 10 ohm-l em2equiv-'. A plot of A(c(No~)~-+H +) Phys. Chem., 73, 646 (1969).

The Reactions of Acetone and Hydrogen Peroxide. 11. Higher Adducts1

by M. C. V. Sauer and John 0. Edwards*

Metcalf Chemical Laboratory, Brown University, Providence, Rhode Island OR916 (Received August 2, 1971)
Publication costs assisted by U.8. A i r Force Ofice of Scientific Research

The formation of several peroxides derived from acetone and hydrogen peroxide has been investigated by proton
magnetic resonance spectroscopy. The kinetics of formation of 2,2-bis(hydroperoxy)propane have been in-
vestigated in detail. The slow step was found to exhibit general acid catalysis. Values of rate constants and
activation parameters are reported. A general mechanistic scheme for formation of the adducts is proposed.

Introduction H3C\ ,o-9 ,CH3

Organic peroxides derived from acetone and hydro-
gen peroxide have been extensively The
H3C-F VCH3
1 : 1 adduct (2-hydroxy-2-hydroperoxypropane,com- P ?
pound I) has recently been shown to be present in the
liquid mixtures. l p 4 The following three higher adducts
OOH
CHSCCH,
I lV,1,1,4,4,7,7-hexamethyl-1,4,7-cyclononatriperoxane

I
OOH
have been identified.2*3 Adduct I1 was isolated3 (in
about 12% yield) when 50% H202was reacted with
11, 2,2-bis(hydroperoxy) propane acetone a t 0" and a mole ratio of 1: 1 in the absence of
added hydrogen ion; in the presence of hydrogen ion,
CH3 CH,
I I
CHBCOOCCH~
(1) (a) Abstracted from part of the Ph.D. thesis of Maria C. V. Sauer
at Brown University, June 1970; (b) Paper I, M. C. V. Sauer and
I I J. 0. Edwards, J . Phys. Chem., 75, 3004 (1971).
0 0 (2) A. Rieohe, Angew. Chem., 70, 251 (1968).
I I
OH OH (3) N. A. Milas and A. Golubovic, J. Amer. Chem. Soc., 81, 6461
(1959).
(4) J. Kine and R . W. Redding, J. Org. Chem., 35, 2769 (1970),
111, a,a'-bis(hydroperoxy)diisopropyl peroxide and references listed therein.

The Journal of Physical Chemistry, Vol. 76,No. 9, 1972

 1284 M. C. V. SAVERAND JOHN0. EDWARDS

all three adducts above have been isolated with the of equilibrium constants at different initial concentra-
cyclic trimer being the predominant product in con- tions of peroxide and acetone. Adduct I, which is the
centrated solutions. 1: 1 addition product, is formed very rapidly (albeit in
The mechanisms of formation of these different per- low concentration), and it has a known nmr spec-
oxides derived from acetone and hydrogen peroxide t r ~ m . ' ~The
,~~ spectra of freshly prepared solutions
have not been investigated. Further, little is known of acetone (from 3 to 10 AI) and hydrogen peroxide (5
about the equilibria between the several species. We to 13 M ) consist of two low-field signals a t 2.23 and
have studied the different stages of the hydrogen per- 1.43 6 ; the 2.23 6 resonance corresponds to the methyl
oxide-acetone interaction in (necessarily) concentrated protons of acetone and the 1.43 6 resonance has been
solution by means of nmr spectroscopy. The data on assigned'!* to adduct I.
primary adduct I are published elsewhere.lb The The spectra of these same solutions taken over the
mechanism of formation of the higher adducts (11, 111, course of an hour after mixing show a slow decrease in
and IV) must be differcnt, as in these three cases re- the intensity of the two signals mentioned above and
placement of OH by OOR obtains whereas formation the appearance of a new signal which has a resonance
of I occurs as an addition across the carbonyl double 1 cps upfield from that of I and which quickly becomes
bond. Data on the higher adducts are presented here. larger than that of I. The reaction under investigation
was found to be
Experimental Section
General. All reagents, buffers, and equipment were OH OOH
the same as those reported earlier.' The evaluation of I I
the equilibrium constants was also carried out as before. CH3CCHS + HzOz CH3CCHS + HzO (1)
Kinetics. The ltinctics of formation of I1 were in- I I
vestigated as follows. The pH of the peroxide solutions OOH OOH
was adjusted with HC1 (1 fW)in cases where buffers and the product can be identified (see below) as com-
were not employed. The pH values were corrected for pound I1 previously i s ~ l a t e d . ~ , ~
the influence of hydrogen peroxide on the glass electrode Over and above the fact that a compound of this na-
rcading.5 The ionic strength was adjusted in appro- ture having the appropriate properties and analysis has
priate cases with KC1. All kinetic runs were started been isolated and identified13 our assignment of the
by adding thc acetone to a known volume of peroxide nmr line to I1 is based on considerable evidence. First,
solution. This operation was carried out in a separate we observed the compound under the same conditions
tclst tube to facilitate mixing, and a small amount of the as it had been isolated by Milas and G o l u b o ~ i c . ~The
reaction mixture then wafi transferred to an nmr tube. position of the methyl proton nmr line is 0.80 6 lower
A pcviod of 10 min was allowcd for temperature equil- than that of acetone itself; this agrees with the result of
ibration before points were taken. Hine and Redding4 and with the general size of the
The rate of disappearance of acetone was measured methyl proton shift observed4 for all reactions of the
by nmr peak areas. The peak areas for both acetone
type
and product were evaluated by the automatic integra-
CHa CHs OR'
tor on the A-60A spectrometer. The concentration of \ \ /
acetone at any time, t , is given by the equation 'c +H O R ' Z C'
R/ No
[acetone], = (I*,I;" ,),
___ [acetonelo
'R O
'H
The equilibrium constants K H based on a stoichiometry
of one acetone and two hydrogen peroxides are con-
where is the integrated area of the acetone peak and
stant, and no reasonable alternative structure for this
I , is the area of the product peak. Brackets are used composition presents itself. The values of AH and A S
to denote concentrations, and the subscripts 0 and t
given below are consistent with a replacement process
refer to initial state and state at time of measurement, rather than an addition or elimination reaction. Fi-
respectively. Values of log [acetone], were plotted nally, the kinetic data (rates, acid catalysis, and activa-
against time; from the slopes of the resultant lines, val- tion parameters) are analogous to those observed for
ucs of observed rate constants k0b.d were found using acetal formation, and compound I1 may indeed be con-
the equation sidered as a modified ketal.
A(1og [acetone]) Compound I1 is the dominant product (as indicated
k o b s d = 2.303( At by the size of the nrnr signal) when the ratio [acetone]/
[H202]is equal to or less than 0.07. In those experi-
Results ments where this ratio is greater than 0.07, a third ad-
Stoichiometries. Each adduct exhibits a character-
istic line in the methyl proton region of the nrnr spectra, (5) J. R. Kolcainski, E. M. Roth, and E. 5.Shanley, J . Amer. Chem.
and identification of the lines was made by evaluation Soc., 7 9 , 531 (1957).

The Journal of Physical Chemistru, Vol. 76, -Vo. 0, 197g

 PEROXIDE
OF ACETONEAND HYDROGEN
REACTIONS 1285

duct which is apparently the reaction product derived

Table 11: Thermodynamic Parameters" for the Formation of
from condensation of adducts I and I1 is formed. 2,2-Bis(hydroperoxy)propane and
OH OOH CH3 CH3 cr,a'-Bis(hydroperoxy)diisopropyl Peroxide at 25"

I I I I Adduot AHa ASo AGO TAP

CH3CCH3 + CHaCCH3 HOOCOOCOOH (2) 2,2-Bis(hydroperoxy )propane 3.2 21 -3.0 6.2
I I / I a,or'-Bis(hydroperoxy)diisopropyl
peroxide
2.9 18 - 2.4 5.3
OOH OOH CH3 CH3
a The units for AH', AGO, and TAS" are kcal mol-' and for
This product, denoted 111, is cy, a'-bis(hydroper0xy)di- A S o are cal mol-' deg-l. The standard deviations are estimated
isopropyl peroxide and is observed in the nmr spectra to be about 0.3 for AH", AGO, and TAS' and about 1for AS".
as a signal at 3 cps lower field from that of 11.
On further increasing the acetone concentration,
([acetone]/ [HzOz])> '/e, a fourth resonance which we I1 shows the thcrmodynamic parameters obtained for
assign to cyclic adduct IV is observed after several days. each reaction.
In solutions where the ratio [acetone]/[HzO2] is about Kinetics of Adduct XI Formation. To explain the
unity, the spectra takcn 24 hr after the mixing of the formation of the 2,2-bis(hydroperoxy)propane1the fol-
reactants indicate the presence of all four products with lowing mechanism was initially hypothesized.
the 2-hydroxy-2-hydroperoxypropane resonance as a
shoulder on the 2,2-bis (hydroper0xy)propane resonance. 0 OH
Equilibrium Constants. T o prove the stoichiometry /I KI I
of the reactions that lead to the formation of 2,2-bis(hy- CH3CCH3 + HOOH CH3CCHa
droperoxy)propane and a,cy '-bis(hydroperoxy)diisopro- I
pyl peroxide, the spectra of several solutions were taken OOH
a t equilibrium over a range of acetone concentrations OH
from 0.5 to 6 M , of hydrogen peroxide concentration I k2
from 9 to 15 M , and of water concentration from 20 to CH3CCH3 + HX CH36CH3 + HzO + X-
40 M . The resonances were integrable by planimeter I lL2 I
or, in some cases of very good resolution, with the auto- OOH OOH
matic integrator of the spectrometer. The equilib- OOH
rium constants K I I and K I I were
~ calculated using the I
relationships CH3CCH3 + HOOH )r CH3CCH3k3

I
OOH SOOH

H
OOH OOH
I I
CH3CCHg CH3CCHS + H+
Values for the equilibrium constants K I I and KIII at I I
+OOH OOH
several temperatures are given in Table I. Every con-
stant therein reported represents an average of a t least I
four determinations; a t 40°, each K I Ivalue represents
H
an average of five runs in the absence of compound 111 Different rate laws were derived assuming first step 4
and five runs in the presence of compound 111. Table and then step 5 to be the rate-determining step of the
reaction. When step 4 is rate determining, the rate
law should be
Table I: Equilibrium Constants" for the Formation of
2,2-Bis(hydroperoxy)propaneand
- d[acetone] -
- ~ K[acetonel
I [H~OZ
[HX]
]
or,or'-Bis(hydroperoxy )diisopropyl Peroxide dt 1 + KI[HzOzl (7)

with the denominator having a value near to unity.

Temp, OC KII KIII
When step 5 is rate determining, the rate law should be
5 114 i 8 44 i4
25 170 f. 8 62 f. 8 -d [acetone] -
32 180 f. 8 67 i6 dt
40 218 i 12 78 f6
For the definitions of K I I and &I, see text.

The Journal of Physical Chemistry, Vol. 76, No. 9,1979

 1286 M. C. V. SAUER 0. EDWARDS
AND JOHN

I I I I
? . ” “ ” . . *

*.O
.8
.6.
t 26
24.
I

.4.

.2 . 20.
1.0
cu
‘
r
.8.
-m
O .6.

d *4.
.2.
0.0- ‘*. 28O
.8 .
.6.
L I
3
PH
I
5 6.
Figure 1. Dependence of rate constant kz‘ (as defined in
text) on pH at three temperatures.
0 10 20 30 40 5 0 60 7 0 80 90

A significant difference lies in the nature of catalysis by

CH+J to6
acid: for the first mechanism general acid catalysis is Figure 2. Separation of rate constant kz’ into ko and k ~terms
:
(see eq 9)at three temperatures.
predicted, whereas for the second specific acid catalysis
is predicted.
The dependence of the reaction on hydrogen peroxide
The slope of the Iine is equal to kH, and the constant ko
concentration was studied at 24”, at constant pH and
is obtained from the intercept by extrapolation to [H+]
in the absence of any other acid. It was found that the
= 0. VaIues of k~ and 1c0 a t three different tempera-
rate law followed by the reaction is the same as the law
tures are listed in Table 111.
derived assuming step 4 as the rate-determining step,
that is
kobsd(1 + KI[H~OZ]) ~ ’ K[HzO,]
I Table I11 : Proton-Catalyzed and Spontaneous Rate
Constants of Formation of 2,2-Bis(hydroperoxy)propane a t
where kobsd is the first-order-pseudo constant for de-
Three Temperatures
crease in acetone concentration. The reaction was
found to be catalyzed by both H + and undissociated Temp, OC kH, M - 1 sec-1 lzo X IO‘, sec-1
acids, and eq 9 shows the observed dependence
28 4.25 0.30
k,’ = ko + ~ H [ H ++] Ica[HX] (9) 41
54
10.5
27.6
0.85
2.70
Dependence of the rate constant kz‘ on pH at three dif-
ferent temperatures is shown in Figure 1.
At low pH and in the absence of any molecular acid
the reaction proceeds largely via the path involving Table IV: Acid Catalytic R a t e Constants at 40” and p = 1
catalysis by the solvated proton. Thus, for these data, for the Formation of 2,2-Bis(hydroperoxy)propane
kz’ = k~ [H+], and the slope of - 1 is observed as ex- Acid Pa qa PKU ka, M-1 ~m-1
pected at pH values lower than 5 . A “spontaneous”
HsO + 3 1 -1.74 10.5
reaction was observed in the region where the amount +0.66 2.00
ClaCCOOH 1 2
of proton catalysis becomes unimportant (pH > 5 ) . ClzCHCOOH 1 2 +1.31 4.5 x lo-’
This spontaneous reaction can be attributed to catal- HSOd- 1 2 +l.52 35 x 10-2
ysis by hydrogen peroxide and water. The rate con- HJ’Oa 3 2 +1.78 13.9 X
stants IcH and lco can be obtained by plotting lcz’ against ClCH&OOH 1 2 +2.76 2.1 x 10-2
[H+] (Figure 2) according to the equation a These are the statistical corrections in the Bronsted equation

kz’ = ko + ~H[H+] (10)

k a l p = Ga((q/p)K*)a.

The Journal of Physical Chemistry, Vol. 76, No. 9,1972

 OF ACETONE
REACTIONS AND HYDROGEN
PEROXIDE 1287

3Table V : Activation Parameters" a t 25" for the Formation

of 2,2-Bis(hydroperoxy)propane

AS* -
E& AH* AS* AS~O

0 "Spontaneous" reaction 17.5 16.9 - 22 6

6 H +-catalyzed reaction 13.8 13.2 - 10 18
Units for E , and A H * are kcal mol-', and for AIS* and
AS* - A&" are cal mol-' deg-1 The standard deviations for
E , and AH* are estimated as 0.3, whereas for AS* and AS* -
A& they are 1.

Both reactions involve the replacement of an OH group

by an OOR group with concurrent formation of water.
For adduct 11, HOOR represents hydrogen peroxide;
for adduct 111, HOOR represents adduct I1 itself. The
similarity in the chemistry of these two reactions is re-
flected in the similarity of the thermodynamic param-
eters.
All of the products from the reaction of acetone and
hydrogen peroxide can be formed by the steps of eq 1,
2, 3 plus the following
0 OOH OH OH
PKa + log P
II
CH3CCH3
I e
+ CH3CCH3 I 1
CH3COOCCH3 (12)
Figure 3. Varia,tion of acid-catalyzed rate constant IC. with I
OH
I I
CH3 CH,
p K , of the corresponding general acid. This Bronsted plot
has data for (1) ClCHzCOOH, (2)H3PO4, (3)HSOa-, (4)
C12CHCOOH, ( 5 ) ClsCCOOH, and (6) H30+.

At constant pH and working with increasing concen- CH3 CH3 OOH

(CH3)Z 7/O-o\ 7(CH3)2
trations of XEI, it is possible to obtain the corresponding I I
CH~COOCCH3 +
I
CHSCCH, -=-t
P P
acid catalytic constant IC, by use of eq 9. Values of IC,
for five different acids are listed in Table IV. A Bron- I I
OH OH
I O\CP (13)

sted plot of the system is shown in Figure 3.

OOH I
Activation parameters of the reaction were calculated
for both types of reactions and are listed in Table V. 0 OOH OOH
/ (CH3)z + 2Hz0

In this case the overall entropies of activation are equal II

CH,CCH3 + I /
CH&OOCCH3
to I I
AX1* = AX1" + ASH' (H+-catalyzed reaction) 6H36H3

and Only two general types of stoichiometry are neces-

A&* = A&" + so*(spontaneous reaction) sary for the description of products from the reactions
of hydroperoxides ROOH and carbonyl compounds
where AX1" is the change in entropy of the rapid equi- R'C(=O)"'. These two types are addition of ROOH
librium step (eq 3) prior to the rate step. across the double bond (such as in eq 3) and conversion
Discussion of COR"' to COOR as in eq 11. Although the details
vary from adduct to adduct, the general pathways
General Pathway. The formation reactions of ad-
should be related.
duct I1 and adduct I11 are similar to each other as may
Stage 12 was not observed by the nmr technique.
be visualized from the general equation
The product of this reaction should be present in smaller
0H OOR quantity than adduct I as the acetone concentration is
I I small. The equilibrium constants obtained for forma-
CH3CCH3 + HOOR CH3CCHs + HzO (11) tion of adduct I would have shown deviations from con-
I I stancy if the process were important; no such devia-
OOH OOH tions were observed.

The Journal of Physical Chemistry, Vol. 76, N o . 9, 1972

1288 AND JOHX0. EDWARDS
M. C. V. SAUER

Cyclic adduct IV could result from either of the two

steps proposed (eq 13 and 13’) or from some related
process. The complexity of the stoichiometry coupled
with the fact that adduct IV can under some circum-
stances be the predominant product (90%) strongly
suggests that the other adducts are intermediates in These activation entropies, although most certainly
thc formation of this stable cyclic peroxide. complicated as to contributing i n f l ~ e n c e s ,seem
~ , ~ to be
Mechanism of Formation of S,f?-Bis(hydroperoxy)pro- dominated by the entropy increase resulting from the
pane. According to the results obtained for (a) depen- increase in number of particles.
dence of rate on pcroxide concentration, (b) pH depen- The reaction of eq 1 is analogous to the formation of
dencc. of the rate, (c) general acid catalysis of the rate, an acetal from a hemiacetal, which process is known to
and (d) aclivation parameters, it can be concluded that be catalyzed by acid. Both general acid catalysis and
thc mcchanism of formation of 2,2-bis(hydroperoxy)- specific acid c a t a l y ~ i s ~ -have
’ ~ been reported. There-
propane is indced that described in the Results section. fore, the general acid catalysis found here is unusual,
The probable steps arc (3)) (4), ( 5 ) , and (6) with (4) albeit unexcep t ion a1.
being the rate-determining step.
The Bronsted law applied to our system is represented Acknowledgments. This study was supported by the
in Figurc 3. Thc slopc of the line is 0.8, with a nega- U. S. Air Force Office of Scientific Research under
tivc deviation for &0+. The observcd spontancous Grant No. 70-1839; their continuing support is appre-
rcactiori is mainly attributcd to catalysis by hydrogen ciated. RIiss Kathleen Edwards is acknowledged for
peroxide (pK, = 11.4)6which is prcscnt in a consider- her assistance in calculations and graphing of the ki-
able concentration; this cannot, hon.cver, be considcred netic data.
as proved.
Thc activation parameters reflect thc changcs from (6) W. G . Evans and N.Uri, Trans. Faradail Soc,, 45,224 (1949).
ground statc to transition state. The cntropy of ad- (7) F. A. Long, J. G. Prit)chard, and F. E. Stafford, J . Amer. Chem.
duct I formation is -28 cal mol-’ dcg-’, and thc ob- Soc., 79,2362 (1957).
served activation entropies AX *obsd must be corrected (8) M. M . Kreevoy, “Rates and Mechanism of Reactions,” part 11,
A . Weissberger, Ed., Wiley-Interscience, New York, N. Y . , 1963,
for this contribution. The remnant values ASH’ and Chapter X X I I I .
ASo* arc +18 and + 6 cal mol-’ deg-l, respectively. (9) A. Kanbaanpera and L. Markker, Acta Chem. Scand., 23, 2465
These arc for the processes (1969).
(10) M. M. Kreevoy and R. W. Taft, J . Amer. Chem. SOC.,77, 3146
(1955), and references therein.
I + H 3 0 +--+ CHsCCH3+ 2Hz0 (11) J. Koskikallio and E. Whalley, Trans. Faraday SOC.,5 5 , 809
(1959).
I (12) P. M. Heininger and W. J. Kilpatrick, J . Anter. Chom. ASOC.,61,
OOH 2510 (1939).
(13) C. Armour, C. A. Bunton, S. Patai, L. Selman, and C. A.
arid Vernon, J . Chem. Soc., 412 (1961).

The Joumal of Physical Chemistry, Vol. 76, No. 9, 1972