React. Kinet. Catal. Lett., Vol. 47, No.

i, 65-71 (1992)

RKCL 1098

CATALYTIC PREPARATION OF M E S I T Y L OXIDE FROM ACETONE

N. Si~ul, N. C i k o v i ~ x, N. W o l f and J. J e l e n ~ i ~

Faculty of T e c h n o l o g y , University of Zagreb, Savska cesta 16,

41000 Zagreb, Croatia
XFaculty of F o o d T e c h n o l o g y and B i o t e c h n o l o g y ,
Zagreb, Croatia
Received November 5, 1991
Accepted November 19, 1991

In the p r o c e s s of the a l d o l condensation of a c e t o n e the

preparation of m e s i t y l oxide has b e e n s t u d i e d w i t h re-
spect to the t e m p e r a t u r e and the n a t u r e of c a t a l y s t .
Strong basic ion e x c h a n g e r s Ionenaustauscher III (Merck
III) and L e w a t i t MP 500 w e r e used in the t e m p e r a t u r e
range from 0 to 50~ Better results are a c h i e v e d with
Merck III, as is e v i d e n t from DAA/MO yields, rate con-
stants and e n e r g y activation values. Empirical expres-
sions for D A A / M O production are given.

Hcc~efloBaaM B~M~HMe TeMnepaTypN M npMpo~N K~TSJIM3aTOp~ H~

npouecc anb~onbHoM KOH~eHCS/IMM ~eTOHa npM noayqeHHM OKMCM

Me3HTHna (OM). HCHOnB3OBSJIH CMnbH~e OCHOBH~e HOHOO6MeHHHKH

MapKH Ionenaustauscher Ill (Merck Ill) M Lewatit MP 500 B

MHTepBa~e TeMnepKTyp OT 0 ~0 500C. HCXO~ H3 B N X O B O B 7]AC/OM

(/IAC=~HaUeTOHOB~M CHHpT), BenHqHH KOHCTS/4T C K O p O C T e M H sHep-

FM~ aKTMBaUMM, ayqmMe pe3ynbTaT~ ~OCTMPH~rrN n p M MCnOnbSOBa-

HMM Merck III. ~pMBO~STC~ 3MnMpMHeCKMe BNpaxeHM~ npOMSBO~-

C T B a ~AC/OM.

Akad6miai Kiad6, Budapest

 v
SISUL et al.: MESITYL OXIDE

INTRODUCTION

In the aldol c o n d e n s a t i o n of acetone into d i a c e t o n e alcohol

(DAA) numerous by-products, such as mesityl oxide, isophorone
mesitylene, phorone and 3,5-xylenol are also obtained. Various
catalysts are used for this purpose, especially basic catalysts
like barium, c a l c i u m and m a g n e s i u m hydroxide or alumina [1-3].
The a p p l i c a t i o n of strongly basic anion exchange resins is also
known [4-6]. Mesityl oxide (MO) is one of the main b y - p r o d u c t s
in the process of DAA synthesis. It is p r e d o m i n a n t e l y formed
at higher temperatures according to the schematic equation:

CH 3 CH 3
2 C<3C=O ~C-CH-C-CH ~C-CH-C-CH + H20
/ ~ /I 2, 3 ~ / - II 3
c~3 cH3 oH o cH 3 o

acetone diacetone alcohol mesityl oxide

Thus in many studies of d i a c e t o n e alcohol condensation from

acetone the study of mesityl oxide formation is also included.

EXPERIMENTAL

In previous works the catalytic preparation of diacetone

alcohol was studied [7,83. Simultaneously the formation of me-
sityl oxide was also determined. In this work its p r o d u c t i o n
is studied w i t h respect to the t e m p e r a t u r e and the catalyst
nature. The e x p e r i m e n t s were carried out in the t e m p e r a t u r e
range from 0 to 50~ using strongly basic ion exchangers
L e w a t i t MP 500 and I o n e n a u s t a u s c h e r III (Merck III) as cata-
lysts. All the e x p e r i m e n t s were p e r f o r m e d in a l a b o r a t o r y set-
up for batch p r o d u c t i o n described earlier [73. Preparation of
c a t a l y s t was done by 24 h swelling in d i s t i l l e d water and 2 h
immersion in 1 M NaOH, then rinsed with water and ethanol. A
gas c h r o m a t o g r a p h y m e t h o d was used to identify reaction prod-
ucts.

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 SISUL et al.: MESITYL OXIDE

RESULTS AND DISCUSSION

Reaction courses of d i a c e t o n e alcohol synthesis and m e s i t y l

oxide formation with Lewatit MP 500 as c a t a l y s t are shown in
Figs 1 and 2, r e s p e c t i v e l y . It is e v i d e n t that the m e s i t y l oxide
yield increases with increasing temperature following the sim-
ultaneous decrease in d i a c e t o n e a!chol content. Concerning the
yield values of b o t h p r o d u c t s , it is a l s o c l e a r that the q u a n -
tities of o t h e r p o s s i b l e by p r o d u c t s s u c h as i s o p h o r o n e , mesity-
lene, phorone and 3,5-xylenol are n e g l i g i b l e . Similar results
are o b t a i n e d with both catalysts used, as is g i v e n in Fig. 3.
Better results are a c h i e v e d by Ionenaustauscher III (Merck III)
for b o t h p r o d u c t s . It is a l s o e v i d e n t that diacetone alcohol
and m e s i t y l oxide yields are e x p o n e n t i a l functions of the tem-
perature; When plotting logarithmic values of D A A / M O y i e l d vs.
inverse temperature, a linear dependence is o b t a i n e d as is seen
in Fig. 4. The slopes of s t r a i g h t lines for D A A and MO p r e p a r ~
t i o n are of the same m a g n i t u d e . A general empirical equation
is of the t y p e

in m = in m + A/T (I)
o

w h e r e mo is the h y p o t h e t i c yield at i n f i n i t e temperature and A

is the line slope. Calculating these individual constants from
the e x p e r i m e n t a l data the following specific equations are ob-
tained:

in m = 2.482 + 550.95/T for D A A - I (2)

in m = 2.182 + 550.95/T for D A A - 2 (3)
in m = 2 0 . 7 9 3 - 5 7 8 5 . 2 0 / T for MO- 1 (4)
in m = 2 0 . 2 9 3 - 5 7 8 5 . 2 0 / T for M O - 2 (5)

In T a b l e 1 the c a l c u l a t e d rate constants of b o t h r e a c t i o n s for

all the e x p e r i m e n t a l conditions are given. F r o m the t e m p e r a t u r e
dependence of the r a t e constant, i.e. f r o m the in k vs. I/T
dependence, an a p p r o x i m a t e activation energy is d e t e r m i n e d

67
SISUL et al.: MESITYL OXIDE

tO0

<
c3
8~i
< 60-
,_%
4O

1 2 3 4 5 6 7 8 9 10 11 12
Reaction time/h
temperature / ~

-o--0 9 10 -~-20 "-~ 30 --m- Z~O --e- 50

Fig. I. R e a c t i o n course of DAA synthesis. Catalyst:

Lewatil MP 500

14-
12

10
o 8
5

4-
2 ~A

O!
2 3 4 5 6 7 B 9 10 11 12
Reaction t i m e / h
te mperat ure / ~

-o-0 -,,--10 4 - 2 0 -c-30 -a,- 40 -n-50

Fig. 2. M e s i t y l oxide formation during the reaction.

Catalyst: Lewatit MP 500

68
 SI~UL et al.: MESITYL OXIDE

100

8O

6o

4O

2O

0
0 TO 20 3O 40 50
Temperoture/~

--o-- D A A "- DAA --I-- M O i MO

Fig. 3. E f f e c t of t e m p e r a t u r e on the y i e l d of D A A and

MO. Catalysts: 1-Merck III, 2 - L e w a t i t MP 500

1 ~, ~.__.___~_~______-----~
2

O - -

-1
3.096 3.196 3.296 3.396 3.496 3.663
l/Tx 103
-o-DAA -'- D A A -I--M0 -o- M 0

Fig. 4. L i n e a r dependence of D A A / M O y i e l d vs. I/T

Catalysts: 1-Merck III, 2-Lewatit MP 500

69
 v
SISUL et al.: MESITYL OXIDE

using the r e l a t l o n

E
(in k) a
(6)
(l/T) R

The c a l c u l a t e d values of E a are a l s o given in the Table.

Table 1

Rate c o n s t a n t and a p p r o x i m a t e activation energies of

DAA synthesis and MO formation

Rate constant, k/h -I

t/~ Ionenaustauscher III Lewatit MP 500
DAA MO DAA MO

i0 0.2495 0.0004 0.1575 0.0004

l0 0.2099 0.0010 0.1450 0.0010
20 0.1989 0.0018 0.1350 0.0018
30 0.1761 0.0051 0.1200 0.0042
40 0.1302 0.0117 0.0950 0.0110
50 0.1131 0.0231 0.0725 0.0200

E a / J m o l -I 11640 -59860 12080 -57030

CONCLUSION

In the p r o c e s s of the a l d o l condensation the q u a n t i t y of

mesityl oxide is n e g l i g i b l e at low t e m p e r a t u r e s , increasing
significantly above 30~ For e a c h d e c a d e of i n c r e a s i n g tem-
perature, the v e l o c i t y of the r e a c t i o n is a b o u t two t i m e s highe~
Simultaneously the D A A y i e l d increases because of the exothermic
character of the r e a c t i o n .
Better results achieved by M e r c k III c a t a l y s t in c o m p a r i s o n
with Lewatit MP 500, ensuring higher MO yields of a b o u t 20%.
Rate constants and E a v a l u e s confirm the r e s u l t s obtained.

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 SISUL et al. : MESITYL OXIDE

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