Deuteration and dimerization of acetylene with a nieuwland catalyst in deuterium oxide

Article abstract of DOI:10.1246/cl.2008.38

Efficient deuteration and dimerization of acetylene have been readily attained in deuterium oxide with a Nieuwland catalyst which is practically used for dimerization of acetylene. Copyright

Full text of DOI:10.1246/cl.2008.38

38
Chemistry Letters Vol.37, No.1 (2008)
Deuteration and Dimerization of Acetylene with a Nieuwland Catalyst in Deuterium Oxide
Takashi Tachiyama,1 Makoto Yoshida,1 Tatsuhiro Aoyagi,1 and Shunichi Fukuzumiꢀ2
1Denki-Kagaku Kogyo Co., Ltd., Itoigawa 949-0393
2Department of Material and Life Science, Graduate School of Engineering, Osaka University,
SORST, Japan Science and Technology Agency (JST), Suita, Osaka 565-0871
(Received September 14, 2007; CL-071015; E-mail: fukuzumi@chem.eng.osaka-u.ac.jp)
Efficient deuteration and dimerization of acetylene have
been readily attained in deuterium oxide with a Nieuwland
catalyst which is practically used for dimerization of acetylene.
(a)
HC CH
26
Deuterated alkynes and alkenes are an important class of
compounds, which have frequently been utilized for biological
and physicochemical research, and the elucidation of reaction
mechanisms. There have been a number of reports on the devel-
opment of the reduction of alkynes into 1,2-deuterioalkenes with
deuterium oxide (D2O), which is undoubtedly the most inexpen-
sive and easy to handle deuterium source.1–5 With regard to ace-
tylene, the deuterized compound DCꢁCD is obtained by the re-
action of calcium carbide with D2O.6 However, there has been
no report on partial deuteration of acetylene with D2O to afford
HCꢁCD rather than fully deuterized compound DCꢁCD.7
We report herein partial and full deuteration of acetylene
and monovinylacetylene using D2O with a Nieuwland catalyst,
which is composed of CuCl and KCl or NH4Cl. The Nieuwland
catalyst has long been used as the representative catalyst for ace-
tylene dimerization on an industrial scale.8–12 The catalytic reac-
tion is carried out in aqueous solutions containing high concen-
trations of the Cuþ and Kþ (or NH4þ). Such an aqueous reaction
is environmentally more benign than a number of synthetic or-
ganic reactions with transition metal complexes used for dimeri-
zation of monosubstituted acetylenes in organic solvents.13
A mixture of CuCl (34.65 g, 0.350 mol) and KCl (24.80 g,
0.333 mol) was dissolved in 29.9 mL of distilled water (or
D2O) at 343 K under nitrogen stream and stirred for 30 min.
An aqueous solution of [CuCl] = 7.0 M of the Nieuwland
catalyst was obtained (50 mL). 150 mL of the catalyst solution
added into the three necked flask passed acetylene (the flow rate,
0.1 L/min.) for 15 min. As soon as acetylene supply was stop-
ped, the gas phase was substituted to nitrogen and the flask
was sealed. The gas phase was analyzed every 30 min by GC-MS
(a Shimadzu GCMS-QP 5000 equipped with a DS-1 chromatog-
raphy column).
20
25
HC CD
30
35
40
45
50
(b)
DC CD
28
26
HC CH
27
20
25
30
HC CH
35
40
45
50
(c)
26
DC CD
28
20
25
30
35
40
45
50
m/z
Figure 1. MS spectra of acetylene detected in the gas phase af-
ter introduction of (a) C2H2 into an H2O solution, (b) C2H2 into a
D2O solution, and (c) C2D2 into an H2O solution in the presence
of a Nieuwland catalyst.
–H+
+ [CuI]
Cu–C
–D+
HC CH
CH
+
+
H
+
+
D
–H+
Figure 1a shows a GC-MS spectrum of HCꢁCH at
m=z ¼ 26 detected in the gas phase of an H2O solution of acety-
lene/Nieuwland catalyst. When H2O is replaced by D2O, how-
ever, an H/D exchange of acetylene with D2O occurs to afford
HCꢁCD (m=z ¼ 27) and DCꢁCD (m=z ¼ 28) as shown in
Figure 1b. When HCꢁCH is replaced by DCꢁCD in an H2O so-
lution of acetylene/Nieuwland catalyst, DCꢁCD is converted to
HCꢁCD and HCꢁCH (Figure 1c). These results clearly indicate
that the Nieuwland catalyst is responsible for the H/D exchange
between acetylene and water.14
+ [CuI]
HC CD
Cu–C CD
+
+
H
+
+
D
+ [CuI]
DC CD
Scheme 1. A plausible mechanism of H/D exchange between
acetylene and proton in the presence of a Nieuwland catalyst
via formation of a ꢀ-complex of deprotonated acetylene with
CuI species.
The occurrence of H/D exchange between acetylene and
proton in water suggests that deprotonation of acetylene is in-
volved in the Nieuwland catalysis to produce a ꢀ-complex of de-
protonated acetylene with CuI species that is in equilibrium with
acetylene as shown in Scheme 1.15 In D2O HCꢁCH is converted
to HCꢁCD and then to DCꢁCD via a ꢀ-complex of deprotonat-
Copyright Ó 2008 The Chemical Society of Japan

Chemistry Letters Vol.37, No.1 (2008)
39
In conclusion, we have demonstrated that partial and full
deuteration of acetylene as well as deuteration of monovinyl-
acetylene and divinylacetylene is readily achieved using a
Nieuwland catalyst in D2O. Such an efficient H/D exchange
of acetylene with proton in water also provides valuable insight
into the mechanism of the Nieuwland catalysis for dimerization
of acetylene.
This work was partially supported by Grants-in-Aid
(No. 19205019) from the Ministry of Education, Culture, Sports,
Science and Technology, Japan.
References and Notes
1
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2
3
4
5
6
7
Figure 2. MS spectra of monovinylacetylene detected in the
gas phase at 60 min after introduction of (a) C2H2 into an H2O
solution, (b) C2H2 into a D2O solution, and (c) C2D2 into an
H2O solution in the presence of a Nieuwland catalyst.
ed acetylene with CuI species in Scheme 1 where the catalytical-
ly active species is shown in the parenthesis: [Cu–CꢁCH(orD)].
Similarly when the reaction is started from DCꢁCD in H2O,
DCꢁCD is converted to HCꢁCD and then to HCꢁCH.
At 60 min after introduction of acetylene into an H2O solu-
tion of the Nieuwland catalyst, the dimerization of acetylene pro-
ceeds to afford monovinylacetylene (CH2=CHCꢁCH: m=z ¼
52) as shown in Figure 2a. In D2O, deuterized monovinylacety-
lene (CD2=CDCꢁCD: m=z ¼ 56) was produced under other-
wise the same conditions (Figure 2b).16 When the dimerization
of DCꢁCD was carried out in an H2O solution of the Nieuwland
catalyst, CH2=CHCꢁCH was produced without formation of
deuterized monovinylacetylene (Figure 2c).
8
9
10 a) W. H. Carothers, I. Williams, A. M. Collins, J. E. Kirby,
J. Am. Chem. Soc. 1931, 53, 4203. b) W. H. Carothers, G. J.
Berchet, A. M. Collins, J. Am. Chem. Soc. 1932, 54, 4066.
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Osakada, J. Mol. Catal. A: Chem. 2001, 175, 73.
12 Y. Tokita, A. Okamoto, K. Nishiwaki, M. Kobayashi, E.
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Reaction, ed. by W. R. Moser, D. W. Slocum, American
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New York, 1995, Vol. 12.
14 Partial H/D exchange between acetylene and water was
observed without the catalyst. However, the H/D exchange
was significantly enhanced by the presence of a Nieuwland
catalyst.
15 For CuI acetylides, see: P. Siemsen, R. C. Livingston, F.
Diederich, Angew. Chem., Int. Ed. 2000, 39, 2632.
16 At prolonged reaction time, HCꢁCH was completely con-
verted to DCꢁCD. However, the dimerization of DCꢁCD
also proceeds as shown in Figure 2b.
At prolonged reaction time, the reaction of HCꢁCH in D2O
with the Nieuwland catalyst affords the fully deuterized monovi-
nylacetylene and divinylacetylene. Thus, the Nieuwland catalyst
provides a convenient way to obtain the fully deuterized mono-
vinylacetylene and divinylacetylene.
It should be noted that a significant kinetic deuterium iso-
tope effect is observed because the dimerization rate of acetylene
is slowed down when HCꢁCH in H2O is replaced by HCꢁCH in
D2O as shown in Figure 2b where DCꢁCD (m=e ¼ 28) still re-
mains in contrast with the result in Figure 2a. The slower dime-
rization rate of HCꢁCH in D2O than that of HCꢁCH in H2O
was confirmed by the time profile of the formation rate of the
products in the gas phase. Such a kinetic deuterium effect sug-
gests that the deprotonation of acetylene to form the ꢀ-complex
of deprotonated acetylene with CuI species in the Nieuwland
catalyst may be involved in the catalytic cycle. However, the
detailed mechanisms of the catalytic dimerization of acetylene
has yet to be clarified by taking into account the fact that the
deuteration rate is much faster than the dimerization rate (see
Figure 1).
Published on the web (Advance View) December 1, 2007; doi:10.1246/cl.2008.38