1070-4272/02/7507-1101$27.00C2002 MAIK [Nauka/Interperiodica]
Russian Journal of Applied Chemistry, Vol. 75, No. 7, 2002, pp. 1101!1103. Translated from Zhurnal Prikladnoi Khimii, Vol. 75, No. 7,
2002, pp. 1118!1120.
Original Russian Text Copyright + 2002 by Zhaksibaev, Kartonozhkina, Abylkasova, Izdebskaya, Mambetkazieva, Pak.
Straight and Modified Copper Catalysts for Stereoselective
Hydrogenation of 5,17-Docosadiyne
M. Zh. Zhaksibaev, O. I. Kartonozhkina, G. E. Abylkasova, G. T. Izdebskaya,
R. A. Mambetkazieva, and A. M. Pak
Sokol’skii Institute of Organic Catalysis and Electrochemistry, Ministry of Education
and Science of Kazakhstan Republic, Almaty, Kazakhstan
Received February 12, 2001; in final form, March 2002
Abstract-Modified copper catalysts providing high rate of 5,17-docosadiyne hydrogenation with 100% yield
of cis,cis-5,17-docosadiene (gypsy moth attractant) were developed.
Stereoselective hydrogenation of high-molecular-
weight acetylene derivatives to corresponding cis-or
trans-olefins is the most complex and the finest stage
in the synthesis of attractants and pheromones.
gent requirements are placed upon hydrogenation prod-
ucts, since even 1% impurities of positional or geo-
metric isomers present in an attractant or pheromone
decrease or fully eliminate its biological activity.
It is known that, in hydrogenation of acetylene
derivatives, copper catalysts exhibit high selectivity
[2!4] and stereospecificity [5, 6] but low activity. The
goal of this study was to develop modified copper
catalysts for sufficiently fast and stereoselective hy-
drogenation of diacetylene hydrocarbon 5,17-docosa-
with the aim to ensure its complete conversion
and quantitative yield of cis,cis-diene and fairly high
Copper catalysts (10% Cu) modified with europi-
um and yttrium oxides were prepared by impregnating
a support with metal salt solutions . The europium
and yttrium content was varied from 1 to 10%.
The catalyst precursors were thermally treated in
air at 473 K for 2 h and then reduced in a hydrogen
flow in a tubular furnace at 623 K for 3 h.
Hydrogenation was performed in a high-pressure
kinetic device (HPKD) by a common procedure. The
Attractants and pheromones of harmful insects allows oppor-
tune and efficient use of insecticides, which substantially de-
creases contamination of the environment .
The hydrogenation product of this compound, cis,cis-5,17-do-
cosadiene is the hypsy moth attractant.
temperature was varied from 373 to 423 K, and pres-
sure, from 6 to 10 MPa. Hexane was used as a diluent.
Hydrogenation was performed until hydrogen uptake
ceased after complete conversion of diacetylene
derivative into the cis,cis-ethylene compound.
The products of 5,17-docosadiyne hydrogenation
were analyzed on a Tsvet-500 chromatograph equipped
with a 500000.25-mm capillary column coated with
OV-101 phase. Chromatograms were treated using an
The catalysts were studied by X-ray phase analy-
sis on a DRON-4 diffractometer with filtered CuK
radiation. The catalyst surface area was determined
on an Accusorb-2100 device by the BET method from
physical adsorption of nitrogen. Temperature-pro-
grammed desorption of hydrogen was also performed.
It was found that all catalysts contain metallic
copper lattice without any extrinsic atoms. At the
same time, no sharp diffraction maxima of the modi-
fier were observed. This may be due to the fact that
rare-earth compounds form thin surface films on alu-
minum and copper oxides, or X-ray amorphous com-
pounds are formed by a solid-phase reaction of the
modifier, copper oxide, and aluminum oxide on heat-
ing in an air flow. Both the above processes can
proceed simultaneously. These suggestions are in-
directly confirmed by a decrease in the surface area on
introduction of europium and yttrium oxides into the
catalyst. Introduction of 1 to 10% europium decreases
the catalyst surface area from 68 to 48 m
the catalyst 10% Cu/C-Al
, the surface area is
. With the yttrium content increasing
from 1 to 10%, the surface area decreases from 75 to
. The largest amount of hydrogen (2.2 cm
is desorbed from the catalyst modified with 5% Eu