512
STEPOVIK et al.
No phenol and tert-butyl hydroperoxide were found.
PhCH(Me)OOH (0.08 g) was determined by iodo-
metric titration. For identification of the latter, re-
sidual hydrolysis products were dissolved in benzene,
and the solution was heated at 60 C for 3 h with a
catalytic amount of p-toluenesulfonic acid [4]. Phenol,
0.03 g, was determined by chromatography, and acetal-
dehyde was identified as 2,4-dinitrophenylhydrazone.
The formation of these products is evidence for the
presence of PhCH(Me)OOH.
diethyl ether. Methyl acetate was identified after
treatment of the hydrolyzate with diazomethane.
Peroxide compounds, 0.07 g, were determined by
iodometric titration in the presence of Fe3+. The
presence of tert-butyl perbenzoate among the hydro-
lysis products was proved by the reaction with
aluminum isopropoxide [26].
REFERENCES
Experiments with the other hydrocarbons were
performed in a similar way.
1. Dodonov, V.A., Stepovik, L.P., Soskova, A.S., and
Zaburdaeva E.A., Zh. Obshch. Khim., 1994, vol. 64,
no. 10, p. 1715.
Reaction of 1-hydroperoxy-1,1-diphenylethane
with alkoxide I. To a solution of 0.75 g of
Ph2C(Me)OOH in 12 ml of benzene, 1.19 g of
Ti(OBu-t)4 was added. In a minute the reaction got
stramineous and in 20 min, dark brown. The con-
densate contained 0.39 g of t-BuOH and 0.03 g of
PhC(O)Me (identified by TLC as 2,4-dinitrophenyl-
hydrazone).
2. Stepovik, L.P., Dodonov, V.A., and Zaburdaeva, E.A.,
Zh. Obshch. Khim., 1997, vol. 67, no. 1, p. 116.
3. Stepovik, L.P., Zaburdaeva, E.A., and Dodonov, V.A.,
Zh. Obshch. Khim., 1997, vol. 67, no. 2, p. 282.
4. Stepovik, L.P., Martynova, I.M., and Dodonov, V.A.,
Zh. Obshch. Khim., 1999, vol. 69, no. 2, p. 267.
5. Zaburdaeva, E.A., Stepovik, L.P., Dodonov, V.A.,
and Martynova, I.M., Zh. Obshch. Khim., 1997,
vol. 67, no. 12, p. 2015.
The residue was a dark brown mobile substance. It
was hydrolyzed by the above procedure. The ethereal
extract contained (by chromatographic data) 0.43 g of
t-BuOH, 0.28 g of Ph2C(OH)Me, 0.15 g of
Ph2C=CH2, 0.01 g of Ph2C=O, and 0.02 g of PhOH.
In hydrolyzate, 0.03 g of Ph2C(Me)OOH was found
by iodometric titration. 1-Hydroperoxy-1,1-diphenyl-
ethane was identified as described above.
6. Stepovik, L.P., Martynova, I.M., Dodonov, V.A., and
Cherkasov, V.K., Izv. Ross. Akad. Nauk, Ser. Khim.,
2002, no. 4, p. 590.
7. Stepovik, L.P., Martynova, I.M., and Dodonov, V.A.,
Zh. Obshch. Khim., 2000, vol. 70, no. 8, p. 1399.
8. Stepovik, L.P., Dodonov, V.A., Gulenova, M.V., Mar-
tynova, I.M., and Cherkasov, V.K., Abstracts of
Papers, XI Mezhdunarodnaya konferentsiya po khimii
organicheskikh i elementorganicheskikh peroksidov
(XI Int. Conf. on Chemistry of Organic and Organo-
element Peroxides), Moscow, 2003, p. 25.
Reaction of benzyl ethyl ether with the
Ti(OBu-t)4 t-BuOOH system (1:1:2). A mixture of
0.27 g of PhCH2OEt, 0.68 g of Ti(OBu-t)4, and 0.18 g
t-BuOOH in 7 ml of benzene was allowed to stand
for 1 day. The reaction solution got reddish orange. It
was concentrated and analyzed by chromatography to
find 0.50 g of t-BuOH, 0.01 g of PhCHO, 0.02 g of
PhCH2OH, 0.03 g of PhC(O)OEt, and 0.08 g of the
starting benzyl ethyl ether. Acetaldehyde and benzal-
dehyde were identified by TLC as 2,4-dinitrophenyl-
hydrazones.
9. Moiseeva, N.I., Gekhman, A.E., Minin, V.V., La-
rin, G.M., Bashtanov, M.E., Krasnovskii, A.A., and
Moiseev, I.I., Kinet. Katal., 2000, vol. 41, no. 2,
p. 191.
10. Russell, G.A., J. Am. Chem. Soc., 1957, vol. 79,
no. 14, p. 3871.
The residue was a yellow tarry substance. It was
hydrolyzed with 10% H2SO4 and extracted with
small portions of diethyl ether. The ethereal extracts
contained 0.28 g of t-BuOH, 0.06 g of PhC(O)OEt,
0.01 g of PhCO2H (as methyl ester after treatment
with diazomethane), and 0.35 g of the starting benzyl
ethyl ether.
11. Howard, J.A. and Ingold, K.U., Can. J. Chem., 1967,
vol. 45, no. 16, p. 793.
12. Rakhimov, A.I., Khimiya i tekhnologiya organiches-
kikh perekisnykh soedinenii (Chemistry and Techno-
logy of Organic Peroxide Compounds), Moscow:
Khimiya, 1979, p. 11.
13. Adam, W., Braun, M., Griesbeck, A., Lucchini, V.,
Staab, E., and Will, B., J. Am. Chem. Soc., 1989,
vol. 111, no. 1, p. 203.
The residue from a parallel run was analyzed for
acetic acid (found 0.02 g of MeCO2H) [19]. After
titration with alkali, the xylene solution was separated,
and the alkaline solution was concentrated. The re-
sidue was acidified with H2SO4 and extracted with
14. Dodonov, V.A., Stepovik, L.P., Sofronova, S.M., and
Mukhina, T.V., Zh. Obshch. Khim., 1988, vol. 58,
no. 7, p. 1578.
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