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New Catalyst Systems for the Dimerization of Ethylene and Propene.

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New Catalyst Systems for the Dimerization of
Ethylene and Propene
Synthesis of Alkynylamines from a-Halogeno
Iminium Salts and Ketene S,N-Acetals
By Dr. J. Ewers
By Dr. R. Buijle, Dr. A. Halleux, and Dr. H. G. Viehe
Scholven Chemie AG, Gelsenkirchen-Buer (Germany)
According to W i k e and Bogdanovic "1, allylnickel halide
systems catalyse the dimerization of ethylene and propene.
These catalysts are particularly active if the halogen is bound
in a complex by addition of Lewis acids, e.g. AIC13, and if
phosphines are added to them.
We have found catalysts for the dimerization of ethylene and
propene that are probably x-complexes of Ni(0) and substantially exceed the system named above in activity (based
on nickel content).
The catalyst is formed when a nickel salt (e.g. bisacetylacetonatonickel) is reduced with a chlorine-containing organoaluminium compound in toluene. The most suitable reducing
agent is A I ~ ( C Z H ~ ) ~Catalytic
C I ~ . activity appears only when
at least one mole of Al2(C2H&C13 is added per mole of
nickel salt. A yellow to orange solution is formed, which
absorbs propene greedily. The activity of the catalyst is increased by electron-donors, e.g. triphenylphosphine.
The catalyst can be used over a wide temperature range and
has a high activity even at -30 "C. A catalyst prepared from
1 mole of bisacetylacetonatonickel, 45 moles of Al~(CzH5)3C13,
and 16 moles of triphenylphosphine converts 5.7 x 105 moles
of propene in 2 hours at 6OoC and 10 atm. 91 % of the product consists of:
Union Carbide European Research Associates,
Brussels (Belgium)
Ynamines react with an excess of anhydrous hydrogen
halide with formation of a-halogenoiminium salts [21. The
ynamines are regenerated therefrom by lithium dialkylamides. Ketene N,N-acetals, which can be separated by
distillation, are also formed in this reaction, so that the total
yields range between 50 and 75 %. An ethereal solution of
the amide is dropped during 30 min into a n ethereal solution
of the iminium salt at OOC; the solution is then decanted
from the precipitated salts and distilled.
a-Halogenoiminium salts are readily obtained from carboxamides and phosgene 131, so that this synthesis of ynamines has
preparative interest. Pure N,N-diethyl-1-butynylamine is
obtained from crude N,N-diethyl-1-chlorobutylideneiminium
chloride in 77 % yield. A summary of the results is given in
Table 1.
Table 1 . Ynamines from a-halogenoiininium salts.
0
LiNRl
[R1-CH2-CC1=NR:] C1'
R'-C-C-NRi
5.p.
Base
Ynamine
i " C h m Hgl
60-62/90
2-Methyl-I-pentenc 17 4
72-73/15
2-Methyl-2-pentene 26 5 O 0
4-MethqI-2-pentene 37 0
50-51/30
4-Methyl-I-pentenc 1 6 O , )
77-78/15
2,3-Dimethyl-l-butene 6.0
2,3-Dimethyl-2-butene 0 5
Yield
[%I
33
58
12
39
0
46
38
77
29
[a1
[a] Obtained only in solution and identified by infrared spectroscopy.
2-Hexene 5 6 ",,
3-Hexene 5 3
Ynamines can also be prepared from ketene S,N-acetals 141.
"4,
4-Phenylethynylmorpholineis obtained by slow addition of
P-methylthio-P-morpholinostyrene
under nitrogen to lithium
Ethylene is dimerized even faster and with a higher conversion. A catalyst prepared from 1 mole of bisacetylacetonatonickel, 32 moles of A12(CzH5)3C13, and 8 moles of triphenylphosphine converts 8.3 x l o 5 moles of ethylene in 15 minutes
and is still fully active at the end of this time. 94% of the
product consists of butenes, of which 95 % is 2-butene.
diethylamide in tetrahydrofuran at 20 "C or t o sodium amide
in boiling piperidine. After 3 hr the mixtures are fractionally
distilled. The same ynamines arise when the ketene S,Nacetal is led over solid sodium amide at 150-165 "C and 1 mm.
Table 2. Ynamines from ketene S,N-acetals.
Catalysts for the dimerization of propene can also be obtained from :
1 Mole of di-(x-allyl)nickel+ 32 moles of A12(C2H5)3C13
1 Mole of x-allylnickel chloride
+ 32 moles of
R'-CH=C(SR)-NR;
~
Ynamine
AIZ(C~H&CI~
+
1 Mole of di-(x-ally1)nickelt 32 moles of A I ~ ( C Z H ~ ) ~ C I ~
R1
I
R2
C~HS
Morpholino
H
Morpholino
8 moles of triphenylphosphine
1 Mole of ;c-allylnickel chloride+ 32 moles of Alz(CzH5)3C13+
I
Base
LiN(C2Hs)r
NaNHz
NaNH2/CsHI ,N
NaNH2/C5HIIN
R'-C-C-NR;
I
Yield
?&m
Hgl
99- 100/0.01
i%1
40
50
50
[a 1
8 moles of triphenylphosphine
1 Mole of di-(x-ally1)nickelf 32 moles of AICI,
+ 8 moles
of triphenylphosphine
These systems are, however, less active than those without
the ally1 group.
Received: April 5th. 1966
[ Z 203 IE]
German version: Angew. Chem. 78, 593 (1966)
[l] G . Wilke et a/., Angew. Chem. 78, 157 (1966); Angew. Chem.
internat. Edit. 5, 151 (1966).
584
[ l ] Part XI1 of Heterosubstituted Acetylenes. - Part XI: H. C .
Viehe, R . Merenyi, and J . F. Oth, Angew. Chem. 76, 922 (1964);
Angew. Chem. internat. Edit. 3, 755 (1964).
[2] H. G . Viehe, Lecture on June 5th, 1964, in Paris.
[3] H. Eilingsfeld, M . Seefelder, and H. Weidinger, Chem. Ber.
96, 2671 (1963).
141 R . Gompper and W. Elser, Tetrahedron Letters 1964, 1971.
Angew. Chem. internat. Edit.
1 VoI. 5 (1966) / No. 6
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