Gas-phase vinylation of N-methylacetamide

Article abstract of DOI:10.1023/A:1026361003797

Catalysts for selective gas-phase vinylation of N-methylacetamide with acetylene were studied. These catalysts were obtained by applying to wide-pore silica gel of the CdO-K₂O-ZnO system or applying to commercial Al₂O₃ of the CdO-K₂O and CdO-K₂O-ZnO systems.

Full text of DOI:10.1023/A:1026361003797

Russian Journal of General Chemistry, Vol. 73, No. 6, 2003, pp. 940 946. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 6, 2003,
pp. 993 1000.
Original Russian Text Copyright
2003 by Deryagina, Sukhomazova, Levanova, Arndt, Henkelman, Trofimov.
Gas-Phase Vinylation of N-Methylacetamide
E. N. Deryagina, E. N. Sukhomazova, E. P. Levanova,
I. -D. Arndt, I. Henkelmann, and B. A. Trofimov
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk, Russia
BASF Joint-Stock Company, Ludwigshafen, Germany
Received July 9, 2001
Abstract Catalysts for selective gas-phase vinylation of N-methylacetamide with acetylene were studied.
These catalysts were obtained by applying to wide-pore silica gel of the CdO K2O ZnO system or applying
to commercial Al2O3 of the CdO K2O and CdO K2O ZnO systems.
N-methyl-N-vinylacetamide, a perspective mono-
mer for preparing such a highly basic polymer as poly- these conditions: At 350 360 C (catalyst K4ZrO4 S),
95%). Amide I is less effectively vinylated under
vinylamine, as well as other polymers and copolymers, the conversion is 6%, and the yields of N-methyl-N-
is still hardly available because of the lack of eco-
nomical methods of its synthesis. Known methods of
direct liquid-phase vinylation of amides with ace-
tylene in the presence of their potassium derivatives
or cadmium acetate [1, 2] proved ineffective with the
simplest amides, such as N-methylacetamide (I).
vinylacetamide (II) are 6% per taken and 40 50% per
consumed amide.
The direct synthesis of N-vinylphthalimide via gas-
phase reaction of acetylene with phthalimide proved
to be the most effectively catalyzed by zinc and
cadmium oxides applied to charcoal separately or
together [14]. On the best catalyst at 270 280 C, the
yield of N-vinylphthalimide was 83% (the conversion
of phthalimide was not given).
Gas-phase vinylation with acetylene suggests its
thermal or catalytic activation. Pyrolysis of acetylene
commences at temperatures above 500 C and is ef-
fectively catalyzed by such metals as V, W, Ni, Zr,
Nb, and Ta. At 580 680 C, acetylene converts pri-
marily into benzene and toluene [3]. Aromatic hydro-
carbons formed by pyrolysis of acetylene are pre-
cursors of polyaromatic polymers, pyrolized coke, or
soot [4 12]. These processes should be taken into
account in conducting thermal and heterogeneous
catalytic reactions of acetylene with various reagents.
The aim of the present work was searching for
more active catalysts for gas-phase vinylation of
amide I with acetylene. To this end, we checked
combinations of potassium, zinc, and cadmium oxides,
as well as cesium fluoride and lanthanum triflate on
various supports.
Thermally, amide I does not react with acetylene
up to 500 C (acetylene begins to convert into aro-
matic hydrocarbons after 300 C).
Gas-phase vinylation of acetamides have scarcely
been documented. The patent [13] describes the
heterogeneous catalytic gas-phase vinylation with
acetylene of 2-pyrrolidone, 2-piperidone, and amide I.
The catalysts used were potassium (sodium, lithium)
aluminates, stannates, zincates, vanadates, titanates,
beryllates, bismuthates, and lanthanates, as well as
mixtures of metal oxides, applied to charcoal. The
reactions were performed at 290 360 C in a flow
system.
For gas-phase vinylation of amide I we developed
several types of catalysts on the basis of available
supports: silica gel, - and -aluminas, as well as
natural and synthetic zeolites. First we ranked the
supports by moisture capacity. This value allows
estimation of the amount of catalyst solution fully
absorbed by the support. The moisture capacities
(Table 1) are directly related to the porosity of the
supports: the higher the moisture capacity, the larger
the pore size. Some supports with low moisture
capacities were not used.
The easiest vinylated are 2-pyrrolidone and 2-pi-
peridone. On the best catalysts, such as KAlO2,
K2AlO3, K4ZrO4, K2ZnO2, and K2O CdO on charcoal,
their conversions at 290 310 C attain 30 40%, and
the selectivity of the reactions is very high (the yields
of N-vinyl derivatives per consumed amide are 90
The conditions and results of the reactions of
amide I with acetylene are listed in Table 2 (hori-
zontal reactor) and Table 3 (vertical reactor).
1070-3632/03/7306-0940$25.00 2003 MAIK Nauka/Interperiodica

GAS-PHASE VINYLATION OF N-METHYLACETAMIDE
941
As seen from Tables 2 and 3, the catalyst
Table 1. Catalysts of vinylation of amide Ia
11.2%CdO + 2.8%ZnO on an AB-17 ferrosilicate
support catalyzes vinylation of amide I with acetylene
at 300 400 C. As the amount of the catalyst is in-
creased from 3 to 10 g, the conversion of amide I at
300 C increases from 0.7 to 4%, and the yield of
vinylation product II increases from 0.3 to 3.2% at a
selectivity of 96% [Table 2, run nos. 1 (1), 1 (2), 1 (3),
1 (4), 2 (1), 2 (2), 2 (3), and 3]. The conversion is
increased if a 9-fold molar excess of acetylene is used.
Above 400 C, acetylene strongly pyrolyzes and cokes
the catalyst. The AB-17 support is intrinsically in-
active in this reaction at 300 C.
Applied catalytic
Moisture
capacity,
%
systems
Support
CdO, ZnO, CdO ZnO,
10% 10% 11.2: 2.8%
AB-17
60
+
ferrosilicate
Clinoptilolite
(natural zeolite)
TsVM
Ti(IV)O2(20%)
synthetic zeolite
TsVM synthetic
zeolite
Al2O3(10%)
Zeolite 65%
TsVM
35%Al2O3
Zeolite Na,
K-erionite
14.0
27.4
+
+
+
+
+
+
The catalysts on the basis of a TsVM Ti(IV)O2
(20%) commercial synthetic zeolite with applied CdO
(10%), ZnO (10%), or their mixture [CdO (11.2%)
and ZnO (2.8%)] proved inactive in the reaction
studied at 300 C (Table 2, run no. 4 and Table 4, run
nos. 7 and 8). The catalysts 11.2%CdO + 2.8%ZnO
on a natural zeolite (clinoptilolite), as well as TsVM-
Al2O3(10%) and TsVM-Al2O3 (35%) zeolites, proved
almost inactive. In this case, the conversion of
compound I is no higher than 2.4% at 300 350 C
[Table 2, run no. 5 and Table 3, run nos. 6 (1) and
6 (2)].
45
52
+
+
+
+
48
72
OPP-2 support
(Al2O3)
+
+
+
+
Silicagel-1, fineb 113
+
+
+
+
Silica gel-2,
coarse
Zeolite
-Al2O3 (50%)
Granulated syn-
tetic zeolite, NaX
37.5
The support -Al2O3 (OPP-2) was found to be more
perspective. An active catalyst is formed by applying
10% of CdO to this support. The conversion of amide
I on it at 300 C is 4%, and the yield of vinylation
product II, 3.2% (selectivity 91%). The conversion of
substrate I on the catalyst prepared by applying 10%
of ZnO to this support is 1.6%, the yield of product II
is 1.8%, and the selectivity is 92%. Better results were
obtained with the catalyst prepared by applying to this
support a mixture of CdO and ZnO in a 4:1 weight
ratio (11.2 and 2.8%, respectively). The conversion
of amide I is 5.3%, and the yield of vinyl derivative
II is 4.8% at a selectivity of 91% (Table 3, run nos.
9 11). These results (in terms of the yield of com-
pound II) are close to those in the patent [13] but
obtained at a lower temperature (300 C).
48
49
a
b
Sign + denotes supports used for preparing catalysts. With
addition of (CF SO ) La (1%) and CsF (10%).
3
3 3
(4:1) to silica gel-1. It begins to work already at
250 C. At this temperature, the conversion of amide I
is 5.4%, and the yield of vinyl derivative is II is 3.8%,
and the selectivity is 87%. At 300 C, the conversion
of substrate I increases to 13.7%, and the yield of
vinyl derivative II attains 7.4%. However, the selec-
tivity of the process decreases (53%). Apparently,
product II decomposes under the action of zinc oxide.
These results surpass patent data, and they were
further improved by varying the ratio of cadmium and
zinc oxides and introducing into the catalytic system
potassium oxide or other active components.
Silica gel-1 with a high moisture capacity (113%)
proved a prospective support. With On the catalyst
obtained by applying 10% of CdO to this support, the
conversion of amide I at 300 C is 6.2%, and the yield
of target product II is 5.5% at a selectivity of 91%
(Table 3, run no. 12). The catalyst 10%ZnO + silica
gel-1 proved too active. With this catalyst, an exo-
Absolutely inactive in the reaction at 300 C proved
lanthanum triflate (1%) or cesium fluoride (10%) on
thermic effect is observed already at 260 C. Therewith, silica gel-1 (Table 2, run nos. 17 and 18). Cesium
substrate I decomposes completely (Table 3, run
no. 13). Thermal polymerization of acetylene and
catalyst coking also enhance. The most active catalyst
was prepared by applying a mixture of CdO and ZnO
fluoride even inhibited acetylene pyrolysis: The
catalyst underwent no coking in the course of the re-
action, and one may probably make use of this pro-
perty in designing more stable catalytic systems.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 6 2003

942
DERYAGINA et al.
Table 2. Vinylation of amide I with acetylene (horizontal reactor, rate of amide I 1 ml/h)
Con-
densate
Conver- Yield of
sion com-
weight, of amide pound
C2H2 Contact Reaction
Run
no.
Catalyst;
weight, g
T,
C
Amide I, Amide
g (mmol) I:C2H2
time,
time,
time,
a
l/h
s
s
g
I, %
0.0
1.2
2.4
0.7
1.6
2.6
3.5
3.8
0.0
II,b
%
1 (1) AB-17+CdO(11.2%)+
ZnO(2.8%); 3
1 (2) AB-17+CdO(11.2%)+
ZnO(2.8%); 3
1 (3) AB-17+CdO(11.2%)+
ZnO(2.8%); 3
1 (4) AB-17+CdO(11.2%)+
ZnO(2.8%); 3
2 (1) AB-17+CdO(11.2%)+
ZnO(2.8%); 6
2 (2) AB-17+CdO(11.2%)+
ZnO(2.8%); 6
2 (3) AB-17+CdO(11.2%)+
ZnO(2.8%); 6
300 0.25 (3.5)
350 0.15 (2.1)
400 0.5 (6.8)
400 0.23 (3.1)
300 0.25 (3.4)
300 0.27 (3.6)
300 0.20 (2.7)
300 0.29 (4.0)
1:6
1:6
1:6
1:10
1:2
1:6
1:9
1:9
1:8
1.8
1.8
1.8
3.0
0.6
1.8
2.8
2.8
2.4
11
10.5
10
6
1000
600
0.31
0.25
0.5
0.0
0.9 (93.9)
1.8 (94.1)
0.3 (96.8)
0.9 (95.1)
1.8 (91.4)
3.0 (90.0)
3.2 (96.0)
0.0
2000
900
0.23
0.25
0.27
0.20
0.37
0.64
24
10
7
900
1000
700
3
AB-17+CdO(11.2%)+
ZnO(2.8%); 10
5
1100
2300
4
TsVM-Ti(IV)O2 (20%)+ 300 0.65 (8.9)
CdO(11.2%)+
8
ZnO(2.8%); 6
5
Clinoptilolite-
CdO(11.2%)+
ZnO(2.8%); 6
300 0.57 (7.8)
1:10
3.0
7
2000
0.48
0.5
0.21
a
b
Molar ratio.
Per taken and reacted (in parentheses) amide I.
Table 3. Vinylation of amide I with acetylene [vertical reactor, rate of amide I 1 l/h, amide I: C2H2 molar ratio 1:6;
C2H2 rate 1.8 l/h, contact time 7 s]
Weight
of con-
desate, g amide I, %
Conver-
sion of
Yield of
Run
no.
Amide I,
g (mmol)
Reaction
time, s
Catalyst; weight, g
T,
C
compound
II,a
%
6 (1) TsVM-Al2O3(10%)+CdO(11.2%)+
ZnO(2.8%); 6
6 (2) TsVM-Al2O3(10%)+CdO(11.2%)+
ZnO(2.8%); 6
300
0.5 (6.8)
0.5 (6.8)
2.2 (30.1)
2.0 (27.4)
1.9 (26)
1800
1800
9200
8200
680
0.5
0.6
0.3
0.0
0.0
5.3
0.4
350
300
300
300
0.57
2.02
1.9
0.2
0.0
0.0
7
8
9
TsVM-Ti(IV)O2 (20%)+
CdO(10%); 6
TsVM-Ti(IV)O2 (20%)+
ZnO(10%); 6
Al2O3 (OPP-2)+CdO (11.2%)+
ZnO(2.8%); 8.8
1.92
4.8 (91.1)
10
11
12
13
Al2O3 (OPP-2)+ZnO(10%); 8.65
Al2O3 (OPP-2)+CdO (10%); 8.3
Silica gel-1+CdO (10%); 6.5
Silica gel-1+ZnO (10%); 7.4
300
300
300
1.9 (25)
6700
6300
6400
1800
1.76
1.79
1.87
0.47
1.6
4.0
6.2
1.8 (92.2)
3.2 (91.0)
5.5 (90.6)
0.0
1.8 (23.9)
1.8 (24.5)
260b 0.5 (6.8)
100
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 6 2003

GAS-PHASE VINYLATION OF N-METHYLACETAMIDE
943
Table 3. (Contd.)
Weight
of con-
desate, g amide I, %
Conver-
sion of
Yield of
compound
II,a
Run
no.
Amide I,
g (mmol)
Reaction
time, s
Catalyst; weight, g
T,
C
%
14
TsVM-Al2O3 (35%)+CdO(11.2%)+
ZnO (2.8%); 9.42
Silica gel-1+CdO (11.2%)+
ZnO(2.8%); 7.1
Silica gel-1+CdO (11.2%)+
ZnO(2.8%); 7.4
300
300
1.3 (17.0)
4500
4200
4700
1.26
1.36
1.29
2.4
13.7
5.4
1.2 (94.2)
7.4 (53.4)
3.8 (87.5)
15
16
1.16 (16.0)
250 260 1.3 (18.0)
17
18
Silica gel-1+(CF3SO3)3La; 5.6
Silica gel-1+CsF (10%);5.9
300
300
1.4 (18.0)
1.2 (16.0)
4900
4200
1.31
1.29
0.0
0.0
0.0
0.0
a
b
Per taken and reacted (in parentheses) amide I. At this temperature, exothermic effect and complete decomposition of amide I
are observed.
Table 4. Moisture capacities of catalytic systemsa
Applied components, %
Moisture
Support
capacity, %
K2O, 10 CdO K2O, 10-5 CdO K2O, 15-10 CdO K2O CsF, 10-5-1
Silica gel-1
OPP-3 (Al2O3)
A-64 (Al2O3)
Charcoal
113
94
82
+
+
+
+
+
+
+
+
+
+
+
173
a
Sign
+
denotes supports used for preparing catalysts.
Table 5. Vinylation of amide I with acetylene [vertical reactor, support silica gel-1, amide I rate 1 ml/h, C2H2 rate
1.8 l/h, I :C2H2 molar ratio amide 1: 6, 300 C]
Catalyst
(% of applied components);
weight, g
Weight
of con-
dencate, g amide I, %
Conver-
sion of of compound
II,a
Yield
Run
no.
Amide I, g Contact
Reaction
time, s
(mmol)
time, s
%
19b
CdO+K2O (10 5); 7.0
1.3 (18)
1.3 (18)
1.5 (21)
0.9 (12)
1.4 (19)
1.2 (16)
1.5 (21)
1.4 (19)
1.3 (18)
1.1 (15)
1.6 (22)
7
7
7
7
7
9
9
9
9
9
9
4600
4800
5600
3200
5200
4400
5300
5100
4800
4100
5700
1.30
1.35
1.60
0.90
1.50
1.30
1.57
1.50
1.40
1.20
1.70
14.1
5.5
15.0
2.2
11.2 (96.2)
3.3 (91.0)
5.2 (63.3)
1.3 (88.9)
0 (0)
13.6 (78.6)
12.8 (73.8)
10.0 (83.6)
11.1 (67.5)
9.0 (47.7)
16.0 (90.0)
20b,c CdO+K2O (10 5); 6.7
21b
CdO+ZnO (12.5 1.5); 7.2
22b,d CdO+ZnO (12.5 1.5); 7.1
23b
24e
25e
K2O (10); 7.1
CdO+K2O (10 5); 10.4
CdO+K2O+CsF (10 5 1); 10.1
0
17.5
16.8
13.8
18.7
19.3
18.0
26e,f CdO K2O (10 5); 10.3
27e,f CdO+K2O CsF (10 5 1); 10.1
28e
29e
CdO+K2O (15 10); 10.3
CdO+K2O+ZnO (10 5 1); 10.3
a
b
Per taken and reacted (in parentheses) amide I. Reactor with an internal diameter of 12 mm and a reaction zone length of
c
d
e
120 mm. The support was impregnated with KOH. Reaction temperature 250 C. Reactor with an internal diameter of 15 mm
and a reaction zone length of 150 mm. The support was impregnated with aqueous solutions of reagent mixtures.
f
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 6 2003

944
DERYAGINA et al.
Table 6. Vinylation of amide I with acetylene (vertical reactor)
Weight
of
condensate, g
Conversion
of amide
I, %
Yiels of
compound II,b
%
Run
no.
Catalyst (% of applied
components); weight, g
Amide I, g
Reaction
time, s
(mmol)a
30c K2O (10); 8.3
1.55 (0.20)
1.28 (18)
1.15 (16)
1.29 (18)e
1.06 (14.4)
1.47 (20)
0.95 (13)
1.1 (15)
5600
4600
4100
4600
3800
5300
3400
3975
5662
1.06
1.29
1.21
1.29
1.1
1.5
1.0
1.2
1.65
0
2.7
77.8
1.6
12.3
4.1
13.2
15.5
16.0
0.0
31d CdO+K2O (10 5); 11.7
32d CdO+K2O (15 10); 13.0
33d CdO+K2O (15 5); 13.0
34f CdO+K2O (10 5); 11.93
35f CdO+K2O (15 10); 14.05
36f CdO+K2O+CsF (10 5 1); 13.93
37f CdO K2O (15 5); 14.4
38f CdO K2O ZnO (15 5 1); 14.4
2.0 (92.3)
24.1 (31.0)
1.0 (93.2)
9.0 (80.9)
3.5 (84.9)
7.7 (76.3)
13.2 (91.0)
13.8 (90.0)
1.57 (21)
a
b
f
Amide I rate 1 ml/h, C H rate 1.8 l/h, amide I:C H molar ratio 1:6, contact time 11 s, reaction temperature 300 C.
Per taken and reacted (in parentheses) amide I. Support OPP-2 alumina. Support OPP-3 alumina. Reaction temperature 250 C.
Support commercial A-64 alumina.
2
2
2 2
c
d
e
As seen from Tables 2 and 3, the activity of the
wide-pore supports (silica gel and alumina) by im-
pregnating with aqueous potassium nitrate followed
by heat treatment. Pure potassium oxide is catalytical-
lly inactive (run no. 23).
catalyst correlates with the moisture capacity of the
support, i.e. with its pore size. Supports with a high
moisture capacity are wide-pore. The catalyst is the
more active the larger is the pore size of the support.
Moreover, the activity of the catalyst coorelates wuth
the nature of the support whose surface forms che-
mical bonds with applied components. Thus, Zinc
oxide on alumina is more active than cadmium oxide
on the same support. At the same time, the opposite
situation occurs with cadmium and zinc oxides on
silica gel-1 (run nos. 10 13). Mixed catalysts
(CdO:ZnO = 4:1) applied to alumina and silica gel-1,
too, differ in activity (run nos. 9 and 14). It is these
supports which we consider perspective for develop-
ment of catalysts for gas-phase vinylation of amides.
The catalytic system 10%CdO + 5%K2O was
formed on the wide-pore silica gel-1 surface by
applying, successively or simultaneously, aqueous
solutions of cadmium acetate and potassium nitrate
with subsequent heat treatment. The catalyst obtained
by applying first cadmium oxide and then potassium
oxide exhibited enhanced activity. At 300 C, the
conversion of amide I attains 14.1%, and the yield of
compound II is 11.2% at a selectivity of 96.2% (re-
actor 12 120 mm). With increased catalyst volume
(reactor 15 150 mm), the reagent contact time in-
creases from 7 to 9 s, which intensifies the reaction:
At 300 C, the conversion of amide I is 17.5%, and
the yield of vinyl derivative II is 13.6% at a selec-
tivity of 78.6% (run nos. 19 and 24, respectively).
The dependence of the reaction result of the ca-
talyst pore size suggests that the vinylation of amides
is diffusion-controlled. Therefore, the pore size of
narrow-pore supports is expedient to increase, for
example, by treatment with water vapor or by
crushing. It is expedient to use wide-pore supports and
to enlarge the area of contact of reagents with catalyst
active centers. To this end, more active components
may be applied and increase their amounts, thus
increasing the length and width of the reaction zone.
The catalytic system 10%CdO + 5%K2O +
1%CsF on silica gel-1 is slightly less active. At
300 C, the conversion of amide I is 16.8%, and the
yield of product II is 12.8% at a selectivity of 73.8%
(run no. 25). The catalysts obtained by simultaneously
impregnating supports with active components, too,
proved active in the reaction studied (run no. 27).
With increased amounts of active components on
silica gel-1, a less selective catalyst was obtained. At
a high conversion of amide I (19.3%), the yield of its
vinylation product II and the reaction selectivity are
low (9.0 and 47.7%, respectively) (run no. 28). The
most effective and selective catalyst was obtained by
applying to silica gel-1 a ternary catalytic system
(10%CdO + 5%K2O + 1%ZnO). In this case, the
Table 4 lists the characteristics of the catalytic
system developed with account for the revealed
regularities.
Tables 5 and 6 present the results of vinylation of
amide I with acetylene on improved catalysts on the
basis of potassium oxide.
Potassium oxide was formed on the surfaces of two
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 6 2003

GAS-PHASE VINYLATION OF N-METHYLACETAMIDE
945
convesion of amide I is 18.0%, and the yield of vinyl
derivative II attains 16.0% at a selectivity of 90%
(run no. 29).
A-64 commercial alumina are the best supports. The
ternary system 10%CdO + 5%K2O + 1%ZnO is best
applied to silica gel-1. The A-64 alumina support is
best suited for catalytic systems with increased
contents of cadmium oxide. The results reported in
the patent [13] were overridden in run nos. 15 (Table
3), 19, 24 27, and 29 (Table 5), and 32, 34, and 36
(Table 6).
The catalytic system 12.5%CdO + 1.5%ZnO on
silica gel-1 is much less active. At 300 C, the con-
version of amide I is 15.0%, the yield of vinyl deriva-
tive II is 5.2%, but the selectivity is low (63%) (run
no. 21, reactor 12 120 mm). As the reaction tempera-
ture is decreased to 250 C, the conversion of amide I
and the yield of its vinylation product II fall.
EXPERIMENTAL
The catalytic systems formed by successively ap-
plying aqueous solutions of cadmium acetate and
potassium acetate to an OPP-3 wide-pore alumina and
an A-64 commercial alumina. The resulting data pri-
vedeny are listed in Table 6. The catalyst on the basis
of potassium oxide and OPP-3 is inactive (run no. 30).
The catalyst 10%CdO + 5%K2O on OPP-3 exhibits
a low activity (run no. 31). The conversion of amide I
is 2.7%, and the yield of vinyl derivative II is 2.0%
(at a high selectivity of 92.3%). As the amount of the
catalytic system 15%CdO + 10%K2O on the OPP-3
support is increased, the reaction is sharply intensified.
The conversion of amide I attains 77.8%, and the
yield of vinyl derivative II is 24%. However, the
selectivity of the reaction falls, probably, on account
of thermolysis of substrate I. At 250 C, the conver-
sion of amide I and the yield of its vinylation product
fall (to 1.6 and 1.0%, respectively), whereas the
reaction selectivity is high (93.2%) (run nos. 32 and
33). By applying CdO + K2O = 15 10% to charcoal
we failed to obtain an active catalyst for vinylation of
amide I.
The IR spectra were obtained on an IF.S.25,
Sample Scant:250 instrument in thin films for liquids
and in KBr pellets for solids. The NMR spectra were
registered on
a Bruker DPX-400 spectrometer
(400 MHz) in CDCl3, internal reference HMDS.
Pilot lots of specially prepared wide-pore silica gel
and alumina, as well as commercial A-64 alumina and
zeolites were used for preparing catalysts.
Wide-pore supports were prepared by heat treat-
ment of normal supports under steam and air. The
steam and air rates were 100 kg/h and 225 m3/h,
respectively. Steaming was began at 400 500 C.
After steam heat treatment was, the oven was cooled
in air.
The main stages of preparation of OPP-2 and
OPP-3 wide-pore aluminas after steam heat treatment
of A-64 alumina were as follows: drying at 110
120 C (4 h), heating to 700 750 C (6 h), keeping at
700 750 C (6 8 h), and cooling.
The steam heat treatment increases the pore size of
the supports but decreases their specific surface area
by beaking narrow pores.
The catalyst 10%CdO + 5%K2O on A-64 alumina
proved active (Table 6). The conversion of amide and
the yield of vinyl derivative II at 300 C are 12.3 and
9.0%, respectively (selectivity 80.9%). With increased
amounts of active components (15%CdO + 10%K2O),
the effectiveness of the vinylation reaction decreases.
The conversion of amide I and the yield of vinyl
derivative II fall to 4.1 and 3.5%, respectively, at a
selectivity of 84.9%. The catalytic system 10%CdO +
5%K2O + 1%CsF on the same support is of mo-
derate activity (Table 6). The most active catalysts
were obtained by applying to A-64 the catalytic sys-
tems 15%CdO + 5%K2O and 15%CdO + 5%K2O +
1%ZnO. In the first case, the conversion of amide I
and the yield of vinyl derivative II at 300 C are 15.5
and 13.2%, respectively (selectivity 91.0%). In the
second case, the results are slightly better, 16.0 and
13.8%, respectively (selectivity 90.0%).
Determination of moisture capacity of supports.
Support (zeolite, alumina, or silica gel), 10 g, pre-
calcined (200 250 C) in a drying oven to constant
weight, was placed into a porcelain dish, poured over
with water, and left to stand for 1 h. The water was
then decanted, the support was dried on a filter paper,
and weighed. The difference in weights between wet
and dried supports was used to measure the amount of
absorbed water.
Preparation of catalytic systems by applying
catalysts from solution to support. A mixture of
support dried to constant weight and catalyst in
distilled water whose amount was estimated from
moisture capacity was vigorously shaken for 30 min.
The catalyst was separated and dried first in air and
then in a drying oven to constant weight. The oxides
CdO and K2O were successively applied by the above
procedure by impregnating supports first with aqueous
Thus, we developed more effective catalysts for
gas-phase vinylation of amide I than those described
in the patent [13]. The wide-pore silica gel-1 and
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946
DERYAGINA et al.
1
cadmium acetate and then (after drying and calcina-
tion) with aqueous potassium nitrate. After drying and
calcination in a drying oven, the resulting catalytic
system was calcined again. The catalysts 10%CdO +
5%K2O + 1%CsF + silica gel 1, 10%CdO + 5%K2O +
Al2O3, and 10%CdO + 5%K2O + 1%CsF + Al2O3
were prepared in a similar way.
and GC MS. IR spectrum, , cm : 1623 (CH=CH2),
1
1655 (C=O), 2964, 2993, 3020, 3080 (CH). H NMR
spectrum, , ppm: 2.2 s (CH3C=O), 3.05 s (CH3 N),
4.36, 4.45 d.d (=CH2), 6.85 q (=CH). The mass
spectrum contains a molecular ion peak at m/z 99.
REFERENCES
Gas-phase vinylation of amide I with acetylene
was performed in a quartz tubular reactor 12 mm in
internal diameter and 180 270 mm in reaction zone
length, mounted in a horizontal electric oven. Amide
I was fed using a syringe autosampler in acetylene.
Acetylene was obtained in a Kipp apparatus, passed
through a calcined calcium chloride, and fed into the
reactor at a rate ensuring required reagent ratio. The
temperature in the reactor was controlled using a
thermocouple placed in the middle of hot zone, on the
outside of the reactor in a quartz pocket. The reaction
mixture was condensed into receivers and cooled traps
and then analyzed by GLC [Tsvet-500 chromatograph,
linear temperature programming at 12 deg/min (from
35 to 230 C), 2000 3-mm stainless-steel column,
liquid phase XE-60, 5% on Chromaton N-AW-HMDS
and DC-550, 5% on Chromaton N-AW-HMDS,
carrier gas helium]. An authentic sample of compound
II was used as reference.
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The reaction of amide I with acetylene in the
vertical mode was performed in a quartz tubular reactor
12 mm in internal diameter and 120 mm in reaction
zone length (or 15 150 mm), mounted in a vertical
electric oven. The temperature in the reactor was
controlled with a thermocouple placed in a qurtz
pocket solded inside the reaction tube. The reactor
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heating at 400 C for 4 h in argon. Then the reactor
was cooled to 300 C, and amide I was fed into it at a
rate of 1 ml/h in acetylene (1.8 l/h).
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Vinyl derivative II was isolated by vacuum distilla-
tion of the reaction mixtures, bp 83 87 C (19 mm)
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Jpn., Ind. Chem., 1953, vol 56, no. 3, p. 440.
1
and characterized by IR and H NMR spectroscopy
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