Transformations of acids in the course of ozonolysis of oxygen-containing derivatives of cycloparaffins

Article abstract of DOI:10.1023/B:RJAC.0000008316.31725.9f

Transformations of monocarboxylic, dicarboxylic, and keto acids in the course of low-temperature ozonolysis were studied using the corresponding ¹⁴C-labeled compounds.

Full text of DOI:10.1023/B:RJAC.0000008316.31725.9f

Russian Journal of Applied Chemistry, Vol. 76, No. 8, 2003, pp. 1348 1350. Translated from Zhurnal Prikladnoi Khimii, Vol. 76, No. 8, 2003,
pp. 1386 1388.
Original Russian Text Copyright
2003 by Syroezhko, Begak.
CHEMISTRY
OF FOSSIL FUEL
Transformations of Acids in the Course of Ozonolysis
of Oxygen-containing Derivatives of Cycloparaffins
A. M. Syroezhko and O. Yu. Begak
St. Petersburg State Technological Institute, St. Petersburg, Russia
Mendeleev Russian Research Institute of Metrology,
Federal State Unitary Enterprise, St. Petersburg, Russia
Received March 20, 2003
Abstract Transformations of monocarboxylic, dicarboxylic, and keto acids in the course of low-temperature
ozonolysis were studied using the corresponding 14C-labeled compounds.
Deep oxidation of cyclohexane [1], methylcyclo-
hexane [2], and their oxygen-containing derivatives
(alcohols, ketones, esters, lactones) [2] results in
accumulation of monocarboxylic, dicarboxylic, and
keto acids, which are actively oxidized by ozone
oxygen mixtures.
that, under these conditions, the hydroxy peroxy radi-
cal derived from 2-methylcyclohexanol does not react
with the C H bonds of the acids in hand and of
2-methylcyclohexanol. However, alkyl and alkoxyl
radicals and ozone abstract the most labile hydrogen
atoms from 2-methylcyclohexanol, labeled acids under
consideration, and intermediate oxidation products,
including radicals. The radioactive products of ozonol-
ysis of [2,3-14C]succinic acid are [2,3-14C]propionic
acid, [2-14C]acetic acid, and 14CO2.
[2,3-14C]Succinic acid is 21.5% decarboxylated in
3 h at 32.5% overall conversion. Ozone attacks the
acid at both the methylene chain and the functional
group:
In this study, we analyzed transformations of [2,3-
14C]succinic, [2,4-14C]glutaric, [1,2-14C]- -ketoglutar-
ic, and [1-14C]caproic acids in 2-methylcyclohexanol
under conditions of its oxidation at 80 C ([O3] =
4 vol %).
Procedures for radiochromatographic analysis of
the acids are described in [3, 4]. Calculations [2] show
CH3
CH3
CH3
CH3
COOH
COOH
CH3
CH3
OH
OO
OH
OO
OH
OH
OH
O2
ROH, O3, O2
O3
.
.
.
.
O
2
.
+
HO O2
O2
,
CH3
CH3
COOH
CH3
COOH
CH3
OH
OO
O2
O3
.
COOH
COOH
.
.
.
HO O2
,
CH2
CH2OO
O3
.
HOOC 14CH2 14CH2 COOH
HOOC 14CH2 14CH2 COO
HOOC 14CH2 14CH3
O2
.
HO O2
,
ROH
.
.
HOOC 14CH2 14CH2
CO2
ROH
.
.
HOOC 14CH2 14CH2 COOH + O3
HOOC 14CH 14CH2 COOH
HOOC 14CH(OO) 14CH2 COOH
.
HO O2
,
1070-4272/03/7608-1348 $25.00 2003 MAIK Nauka/Interperiodica

TRANSFORMATIONS OF ACIDS IN THE COURSE OF OZONOLYSIS
1349
CH3
CH3
OH
OH
OO
.
.
.
.
+ HOOC 14CH(OO) 14CH2COOH
+ HOOC 14CH(O) 14CH2COOH
O
O2
.
.
.
O3
HOOC 14CH(O) 14CH2COOH
OOC 14CH(O) 14CH2COOH
14CHO 14CH2COOH
.
HO O2
CO2
,
O
O
O
.
O3
O3
HOOC 14CH2 14C H
HOOC 14CH2 14COOH
OOC 14CH2 14COOH
.
O2
HO O2
,
O
.
ROH
HOOC 14CH2
HOOC 14CH3
.
14CO2
ROH
.
OO
.
O3, O2
ROH
.
HOOC 14CH(O) 14CH2COOH
HOOC 14CH(OH) 14CH2COOH
.
HOOC 14C 14CH2COOH + HO2
.
HO
ROH
OH
OOH
HOOC 14C 14CH2COOH
OH
O3, O2, ROH
HOOC 14C 14CH2COOH
O
HOOC 14COOH + 14CH3COOH
H2O2
.
At 32.5% conversion of [2,3-14C]succinic acid,
the total activity of acetic and propionic acids is
10.1%. Hence, the major amount of 14CO2 is formed in
further ozonolysis of [14C]oxalic acid:
O3
HOO14C 14CH2COOH
HOO14C 14CH COOH
.
HO O2
,
.
O2
HOO14C 14CH(OO) COOH
.
.
O3
2O3
OO CH COOH
CO2
.
.
.
O3
.
O3
.
HOO14CCOOH
14CO2 + HCO2
CO2
HO O2, CO2
2HO O2
,
,
HO O2
HO O2
,
,
[2,4-14C]Glutaric acid transforms with 30.2% con-
version into 14CO2 and [2,4-14C]butyric (1.2%), [1,3-
14C]succinic (13%), [1-14C]oxalic (0.41%), [1-14C]ace-
tic (0.8%), and [1-14C]propionic (0.45%) acids with-
in 180 min. The composition and activity ratio of
the acids show that all the methylene groups of glu-
taric acid are attacked by ozone. However, the -meth-
ylene groups are attacked predominantly. Note that
CH and OH acids can also be attacked by alkoxyl
radical.
The probability of recombination of the alkoxyl
and hydroxy radicals to form intermediate hydroper-
oxide is low. However, 2-methylcyclohexanol reacts
with ozone to form unstable 1-hydroxy-1-hydrotrioxy-
2-methylcyclohexane whose thermolysis generates
.
hydroperoxy radical HO2 [5, 6]. Recombination of the
hydroperoxy and peroxy radicals yields -hydroper-
oxysuccinic acid. Its decomposition generates the
corresponding -oxyl radical:
Under the ozonolysis conditions, [1,2-14C]- -keto-
glutaric acid is 42.5% consumed in 180 min; 14CO2
and 14CO are formed in 18.1 and 2.1% yields, respec-
tively. The liquid radioactive products are [1-14C]ace-
tic (0.3%), [1-14C]propionic (1.8%), [1-14C]succinic
(13.0%), and [1-14C]oxalic (7.1%) acids. Ozone at-
tacks -ketoglutaric acid at the -positions to the
carbonyl and carboxy groups and also directly at the
O H bond of the carboxy group. Detection of 14CO
shows that ozonolysis involves cleavage of C C
bonds throughout the carbon chain of the keto acid.
Experiments with [1-14C]caproic acid showed that
it transforms in 180 min with 30.5% conversion into
HOOC 14CH(OOH) 14CH2COOH
.
HOOC 14CH(O) 14CH2COOH
.
HO
The probability of reaction of this radical with the
ozone molecule via O H bond in the carboxy group is
low, since this radical reacts with a high rate constant
[7] with alcohol molecules present in excess. How-
ever, occurrence of the reaction of the radical with
ozone to even a small extent will result in formation
of CO2 by oxidation of the intermediately formed
malonic acid:
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 76 No. 8 2003

1350
SYROEZHKO, BEGAK
14CO2, [1-14C]acetic acid (7%), [1-14C]proionic acid
(3.5%), [1-14C]butyric acid (3.4%), and small amounts
of formic acid:
CH3(CH2)3 CH(OOH) 14CO2H
T, O3 , ROH
H14COOH + CH3(CH2)3COOH
.
O3
CH3(CH2)4 14CO2H
CH3(CH2)414COO
.
CONCLUSIONS
HO O2
,
.
ROH
(1) In ozonolysis (80 C) of [2,3-14C]succinic, [2,4-
14C]glutaric, [1,2-14C]- -ketoglutaric, and [1-14C]-
caproic acids, ozone attacks the O H bond of the car-
boxy groups and all the methylene groups of the
aliphatic chain, predominantly those in the -position
relative to functional groups.
CH3(CH2)3CH2
.
CH3(CH2)3CH3
14CO2
ROH
.
O3
CH3(CH2)3CH214CO2H
CH3(CH2)3CH 14CO2H
.
HO O2
,
CH3
OH
OO
(2) Under the conditions examined, peroxy radicals
are inactive in cleavage of the C H and O H bonds.
The reactions involve ozone, oxygen, and alkyl, al-
koxyl, hydroxy, and hyroperoxy radicals.
.
O2
CH3(CH2)3 CH 14CO2H +
.
OO
CH3
OH
.
CH3(CH2)3 CH 14CO2H +
O
REFERENCES
O2
.
O
O
1. Korotkova, N.P., Syroezhko, A.M., and Proskurya-
kov, V.A., Okislenie tsiklogeksana i ego promezhutoch-
nykh kislorodsoderzhashchikh soedinenii ozonovoz-
dushnymi smesyami (Oxidation of Cyclohexane and Its
Intermediate Oxygen-Containing Derivatives with
Ozone Air Mixtures), Available from ONIITEKhIM,
Moscow, June 23, 1978, no. 1805-78.
2. Syroezhko, A.M., Liquid-Phase Oxidation of Alkanes,
Cycloalkanes, and Their Oxygen-Containing Deriva-
tives with Oxygen and Ozone in the Presence of s- and
d-Element Compounds, Doctoral Dissertation, Lenin-
grad, 1985.
O
O
O3
O3
CH3(CH2)3CHO
CH3(CH2)3 C H
O
.
HO O2, 14CO2
,
CH3(CH2)3CO2H
O2
By a similar scheme, ozone attacks the remote
( , , and relative to the carboxy group) methylene
groups of caproic acid.
The ratio of the amounts of pentane and valeric
acid shows that the probability of ozone attack at
the -position to the carboxy group is 3.6 times
higher compared to the attack at the O H bond of
[1-14C]caproic acid. [14C]Formic acid and 14CO2 can
be formed from the intermediate hydroperoxide by
the scheme
3. Syroezhko, A.M., Selivanov, N.T., Potekhin, V.M., and
Proskuryakov, V.A., Radiokhimiya, 1970, vol. 12,
no. 4, pp. 677 680.
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1973, vol. 46, no. 9, pp. 2066 2070.
5. Vikhorev, A.A., Syroezhko, A.M., and Proskurya-
kov, V.A., Zh. Prikl. Khim., 1977, vol. 50, no. 6,
pp. 1310 1314.
.
.
CH3(CH2)3CH(OO) 14CO2H + HO2
CH3(CH2)3 CH(OOH) 14CO2H
6. Vikhorev, A.A., Syroezhko, A.M., and Yakovlev, A.S.,
in Issledovaniya v oblasti khimii i tekhnologii produk-
tov pererabotki goryuchikh iskopaemykh (Studies in
the Field of Chemistry and Technology of Products of
Fossil Fuel Processing), Leningrad: Leningrad. Tekh-
nol. Inst. im. Lensoveta, 1975, issue 2, pp. 39 43.
7. Denisov, E.T., Mechanism of Homolytic Cleavage
of Molecules in the Liquid Phase, Itogi Nauki Tekh.,
Ser.: Kinet. Katal., 1981, vol. 9.
O2
CH3(CH2)3 CH 14CO2H
.
OH
.
O
O
O
O
O3
O3
CH3(CH2)3 CHO
CH3(CH2)3 C H
O
.
HO, O2, 14CO2
CH3(CH2)3 CO2H
O2
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 76 No. 8 2003