2
80
MEKHAEV et al.
Scheme 2.
H (1 atm) / Ir
2
EtOH,
2
5oC, 5 h
~
1%
Results of alkenes hydrogenation
1
2
3
a
R
R
R
Reaction product
Dodecane
Succinic acid
Stearic acid
Propionitrile
1,4-butandiol
Ethylbenzene
Butyric acid
Methyl (3-phenyl)propionate
Yield , %
C
10
H
21
H
H
H
H
H
H
COOH
14COOH
H
100
100
100
100
80
98
98
COOH
C
8
H
17
C
7
H
CN
CH
Ph
2
OH
2
CH OH
H
H
H
H
Me
Ph
COOH
COOMe
52
a
Yield according to the data of GC of reaction mixtures.
adiponitrile does not undergo hydrogenation. The hyd-
rogenation products of cis-but-2-ene-1,4-diol along with
the main product, 1,4-butanediol, contained a small quan-
tity of 1-butanol (~5%). After styrene hydrogenation in
the reaction mixture beside ethylbenzene ethylcyclohexa-
ne was detected (~1.5%). The hydrogenation of the ben-
zene ring was also observed in the case of methyl
cinnamate with the formation of methyl 3-cyclohexylpro-
pionate (~3.5%). However, the aromatic ring of biphe-
nyl did not suffer hydrogenation, the overall content in
the mixture of hydrogenated products of phenylcyclo-
hexane and bicyclohexyl did not exceed 1% (Scheme 2).
2. Mekhaev, A.V., Pestov, A.V., Yatluk, Yu.G.,
Pervova, M.G., and Panyukova, A.A., Russ. J. Org.
Chem., 2013, vol. 49, p. 691.
3. Mekhaev, A.V., Butin, F.N., Pervova, M.G., Taran, O.P.,
Simakova, I.L., and Parmon, V.N., Russ. J. Org. Chem.,
2
014, vol. 50, p. 900.
4
5
6
. Andersson, Ph.G., Iridium Catalysis, New York:
Springer, 2011.
. Jiang, H.-Y., Sun, B., Zheng, X.-X., and Chen, H., Appl.
Catal. A, 2012, vol. 421, p. 86.
. Yang, C.F., Jiang, H.Y., Feng, J., Fu, H.Y., Li, R.X.,
Chen, H., and Li, H.J., J. Mol. Catal. A: Chem., 2009,
vol. 300, p. 98.
The attempts to intensify the process by raising the
temperature and prolonging the reaction time did not
significantly increase the biphenyl conversion. In cont-
rast to nano-size palladium catalysts [11, 12], the nano-size
powder of metal Ir is unfit for biphenyl hydrogenation.
7
. Jiang, H.-Y., Yang, C.-F., Li, C., Fu, H.-Y., Chen, H.,
Li, R.-X., and Li, X.-J., Angew. Chem., Int. Ed., 2008,
vol. 47, p. 9240.
8. Taubmann, S. and Alt, H.G., J. Mol. Catal. A: Chem.,
2008, vol. 287, p. 102.
9
. Huang, Z., Brookhart, M., Goldman, A.S., Kundu, S.,
Ray, A., Scott, S.L., and Vicente, B.C., Adv. Synth.
Catal., 2009, vol. 351, p. 188.
The attempt to reduce 1-dodecene using 2-propanol
as hydrogen source was unsuccessful.
Thus the nano-size metallic Ir powder exhibited a
high catalytic activity in hydrogenation of alkenes and
their derivatives under simple experimental conditions.
1
0. He, L., Wang, J.-Q., Gong, Ya., Liu, Y.-M., Cao, Y.,
He, H.-Y., and Fan, K.-N., Angew. Chem., Int. Ed.,
2
011, vol. 50, p. 10216.
The work was carried out under the financial
support of the Russian Science Foundation (grant
no. 14-13-00136).
11. Mekhaev, A.V., Chupakhin, O.N., Uimin, M.A.,
Ermakov, A.E., Pervova, M.G., Gorbunova, T.I.,
Mysik, A.A., Saloutin, V.I., and Yatluk, Yu.G., Russ.
Chem. Bull., 2009, vol. 58, p. 1321.
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. Beletskaya, I.P., Selivanova, A.V., Tyurin, V.S., Matve-
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 2 2015