Nucleophilic addition to acetylenes in superbasic catalytic systems: XI. Transformations of alkali metal hydroxides during vinylation of 1-heptanol with acetylene under elevated pressure

Article abstract of DOI:10.1023/A:1013847901532

Base-catalyzed addition of 1-heptanol to acetylene under elevated pressure of the latter is accompanied by side processes including formation of carboxylic acid salts (alkali metal heptanoates and acetates) with liberation of hydrogen and acetylene polyme

Full text of DOI:10.1023/A:1013847901532

Russian Journal of Organic Chemistry, Vol. 37, No. 11, 2001, pp. 1553 1558. Translated from Zhurnal Organicheskoi Khimii, Vol. 37, No. 11, 2001,
pp. 1629 1634.
Original Russian Text Copyright
2001 by Oparina, Parshina, Khil’ko, Gorelova, Preiss, Henkelmann, Trofimov.
Nucleophilic Addition to Acetylenes in Superbasic
Catalytic Systems: XI.* Transformations of Alkali Metal
Hydroxides during Vinylation of 1-Heptanol with Acetylene
under Elevated Pressure
L. A. Oparina1, L. N. Parshina1, M. Ya. Khil’ko1, O. V. Gorelova1, T. Preiss2,
J. Henkelmann2, and B. A. Trofimov1
1
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
fax: (3952)396046; e-mail: bat@irioch.irk.ru
2
Ammonia Laboratory, BASF Actiengesellschaft, Ludwigshafen, Germany
Received January 10, 2001
Abstract Base-catalyzed addition of 1-heptanol to acetylene under elevated pressure of the latter is accom-
panied by side processes including formation of carboxylic acid salts (alkali metal heptanoates and acetates)
with liberation of hydrogen and acetylene polymerization. The rate of acetylene absorption depends on the
alkali metal nature and falls down in the series CsOH H2O RbOH H2O > 2KOH H2O > NaOH > LiOH.
Approximately the same order is observed for variation of the rate of deactivation of the catalyst owing to
its transformation into metal carboxylate. Dehydration of the catalyst accelerates both vinylation and acetylene
polymerization.
In the preceding communication [1] we reported
the results of our study of the vinylation of 1-heptanol
The liquid parts of the reaction mixtures and
acetone washings (after removal of acetone) were
with acetylene under atmospheric pressure in the pres- subjected to fractional distillation, and fractions thus
ence of alkali metal hydroxides. We also estimated
the role of the alkali metal cation in the main and side
processes. It was reasonable to continue the work in
this line by studying vinylation of 1-heptanol with
acetylene under elevated pressure in the presence of
the same catalysts.
obtained were analyzed by GLC; the yield of 1-heptyl
vinyl ether and the conversion of 1-heptanol were
calculated. The still residues were analyzed by titra-
tion to determine the concentration of alkali metal
hydroxide and metal carboxylates.
Our results show (Table 1) that the conversion of
1-heptanol, the yield of 1-heptyl vinyl ether, and the
selectivity of vinylation (initial acetylene pressure
12 14 atm, 150 C, 5 h) depend on the nature and con-
centration of alkali metal hydroxide (LiOH, NaOH,
2KOH H2O, RbOH H2O, or CsOH H2O; initial
concentration 5 20 mol %). Lithium hydroxide turned
out to be a poor catalyst even at a concentration of
20 mol %; the reaction mixture contained only traces
of 1-heptyl vinyl ether. These data are consistent with
both published data [2] and our previous results. In
the presence of the other alkali metal hydroxides at
a concentration of 20 mol % the conversion of
1-heptanol attained 96 100%, and the yields of
1-heptyl vinyl ether were approximately similar but
not quantitative (61 68%; Table 1). This means that
The reactions were carried out in a 1-l rotating steel
high-pressure reactor. Acetylene was supplied into
the reactor at an initial pressure of 12 17 atm, and
the mixture was heated to a required temperature
(110 150 C). By the end of the process, the reaction
mixture was usually a two-phase system consisting of
a liquid and solid fractions. The amount of the latter
depended on the initial concentration of the catalyst.
The precipitate was washed with acetone to remove
adsorbed liquid products and with diethyl ether to
remove tars and was examined by spectral methods
1
(IR and H NMR), potentiometric titration in aqueous
medium, and elemental analysis.
____________
*
For communication X, see [1].
1070-4280/01/3711-1553$25.00 2001 MAIK Nauka/Interperiodica

1554
OPARINA et al.
1-heptanol remaining unchanged (Table 1). Further
reduction of the catalyst concentration (down to
5 mol %) is favorable only in the case of potassium
hydroxide: the yield of 1-heptyl vinyl ether increases
to 70%, and the selectivity, to 78%. With the other
alkali metal hydroxides taken at the same concentra-
tion, the yield of the target product was lower, while
the selectivity of its formation almost did not change
(Table 1).
The rate of vinylation of 1-heptanol was estimated
by the rate of acetylene absorption, i.e., by the reduc-
tion of the overall pressure in the reactor under the
assumption that the absorbed acetylene is primarily
consumed for the formation of 1-heptyl vinyl ether.
The reactor was charged with 1-heptanol, alkali metal
hydroxide as catalyst (10 mol % with respect to the
substrate), and acetylene was supplied at an initial
pressure of 17 atm. As the temperature rose, the
pressure increased and attained the maximal value
(23 24 atm) at about 110 C. During a certain period,
the pressure remained constant and began to fall down
3 5 min before a required temperature was reached
(150 C). This moment was assumed to be the initial
one, and the pressure was then measured every 10 min
(Fig. 1). As follows from the acetylene absorption
curves shown in Fig. 1, the rates of vinylation of
1-heptanol in the presence of RbOH H2O and CsOH
H2O are approximately similar: the initial rates are
Fig. 1. Kinetic curves for acetylene absorption in the
vinylation of 1-heptanol (substrate amount 0.4 mol, initial
acetylene pressure 17 atm at room temperature, 150 C) in
the presence of 10 mol % of (1) RbOH H2O, (2) CsOH
H2O, (3) 2KOH H2O, and (4) NaOH.
the vinylation process is accompanied by side reac-
tions involving either the initial reactants or final
products, or both.
Reduction of the concentration of NaOH and
2KOH H2O to 10 mol % did not change the yield of
the product and reaction selectivity to an appreciable
extent; both these parameters remained in the range
from 61 to 69%. In the presence of the same amount
of RbOH H2O or CsOH H2O the yield of 1-heptyl
vinyl ether increases by 7 18%, and the selectivity
of its formation attains 76 81%, the conversion of
1
0.25 and 0.30 mol l min , respectively. An analogous
pattern is observed for 2KOH H2O and NaOH: the
1
initial rates are equal to 0.18 mol l min (Fig. 1,
curves 3 and 4). However, the curves for the first pair
come to a plateau in less than 1 h, whereas the corre-
sponding period for 2KOH H2O and NaOH is longer
by a factor of 1.5.
Table 1. Base-catalyzed vinylation of 1-heptanol with
acetylene (substrate amount 0.15 mol, initial acetylene
pressure 12 14 atm at room temperature, 150 C, 5 h)
Table 2 summarizes the yields of 1-heptyl vinyl
ether, substrate conversions, and reaction selectivities
for vinylation of 1-heptanol with acetylene at 150 C
in the presence of various alkali metal hydroxides.
Comparison of the yields of the target product shows
that cesium and rubidium hydroxides are clearly
superior to the other catalysts: 81 86% against 70%
for sodium and potassium hydroxides. However, their
advantage becomes less obvious when the activity of
alkali metal hydroxides is estimated by the selectivity
of formation of 1-heptyl vinyl ether. The data in
Tables 1 and 2 indicate that, after intense acetylene
absorption has ceased, heating of the reaction mixture
leads to decrease of the yield of 1-heptyl vinyl ether
and hence of the reaction selectivity. This means that
the target product undergoes further transformations.
Substrate
conversion, 1-heptyl vinyl
Yield of
Selec-
tivity,
%
Catalyst,
mol %
%
ether, %
LiOH, 20
NaOH, 20
NaOH, 10
NaOH, 5
2KOH H2O, 20
2KOH H2O, 10
2KOH H2O, 5
RbOH H2O, 20
RbOH H2O, 10
RbOH H2O, 5
CsOH H2O, 20
CsOH H2O, 10
CsOH H2O, 5
20
96
89
76
100
96
90
100
99
73
100
99
<2
64
61
50
61
63
70
68
75
57
64
80
73
<10
67
69
66
61
66
78
68
76
78
64
81
81
90
The vinylation of 1-heptanol at 100 115 C was
found to proceed at a relatively low rate, regardless
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 11 2001

NUCLEOPHILIC ADDITION TO ACETYLENES . . . : XI.
1555
Table 2. Vinylation of 1-heptanol (0.4 mol) with acetylene (initial pressure 17 atm at room temperature) at 150 C in
the presence of 10 mol % of alkali metal hydroxide
Yield of 1-heptyl vinyl
ether, %
Conversion of
1-heptanol, %
Catalyst
NaOH
2KOH H2O
RbOH H2O
CsOH H2O
Time, h
Selectivity, %
1.5
1.5
1.0
1.0
72
69
81
86
84
85
97
98
86
81
83
88
of the catalyst nature. The rate of vinylation in the
metal alkoxides are more efficient catalysts than the
presence of sodium hydroxide sharply decreases (the corresponding hydroxides in nucleophilic addition of
pressure in the reactor fell down by only 1 atm in
2 h), and it was necessary to heat the reaction mixture
at 130 C for an additional 2 h in order to attain the
same acetylene conversion as in experiments with
2KOH H2O and RbOH H2O as catalyst (Table 3).
The best conversion of 1-heptanol, as well as the yield
of 1-heptyl vinyl ether, was obtained with the use of
cesium hydroxide monohydrate as catalyst (Table 3).
On the other hand, even under so mild temperature
conditions deactivation of the catalyst was observed.
Potentiometric titration of the precipitates and still
residues obtained after fractional distillation of the
reactions mixtures showed that in 4 h (reaction time)
25% of sodium or potassium hydroxide and up to
50% of rubidium or cesium hydroxide was converted
into the corresponding carboxylic acid salts, alkali
metal heptanoates [3] or acetates [4 6] (Table 3).
The basicity of the medium and the activity of
reacting anions can be enhanced by binding of alkali
metal cations with polyethers containing OCH2CH2O
fragments, e.g., crown ethers or polyethylene glycols
[6, 7]. Figure 2 shows the effect of addition of
1 mol % of polyethylene glycol (PEG, molecular
weight 400) on the vinylation of 1-heptanol catalyzed
by potassium hydroxide (curve 1). This curve is
steeper that the curve for acetylene absorption ob-
tained under analogous conditions but in the absence
of PEG-400 (Fig. 2, curve 2). However, in both cases
the yields of 1-heptyl vinyl ether were almost similar
(60% and 61%); therefore, increased acetylene absorp-
tion in the presence of PEG is likely to result from
vinylation of polyethylene glycol itself; it is known
[6] that PEG reacts with acetylene more readily than
do aliphatic alcohols. Nevertheless, we presume that
addition of larger amounts of polyethylene glycol or
other crown ether-like activating species will inrease
the rate of vinylation of 1-heptanol.
alcohols to acetylene [8]. Taking the above into
account, we made an attempt to increase the selec-
tivity and efficiency of vinylation by carrying out
the reaction in anhydrous medium.
We failed to remove crystallization water from
cesium hydroxide as an azeotropic mixture with
octane or toluene (without 1-heptanol). By heating
a mixture of CsOH H2O with 1-heptanol and excess
octane under stirring at 130 140 C with a Dean Stark
trap we succeeded in removing about 70% of water
(calculated on the hydrate water and that released
in the formation of cesium 1-heptanolate) as an azeo-
tropic mixture with octane. The resulting suspension
was heated under acetylene pressure. The reaction
was accompanied by fast absorption of acetylene and
evolution of heat; the mixture spontaneously warmed
up from 125 to 150 C in several minutes. In this case
the amount of absorbed acetylene was greater by
a factor of 1.8 than that required for complete vinyla-
tion of the alcohol; this is explained by anionic
polymerization of acetylene. Despite the relatively
short reaction time ( 10 min) and active acetylene
Table 3. Base-catalyzed vinylation of 1-heptanol with
acetylene at 110 115 C (initial acetylene pressure 12
13 atm at room temperature, 4 h) in the presence of alkali
metal hydroxides (10 mol %)
Yield of
Conversion
Conversion
Catalyst
1-heptyl vinyl of 1-heptanol, of catalyst,
ether, %
%
%
NaOHa
33
27
22
31
45
37
32
44
25
25
45
50
2KOH H2O
RbOH H2O
CsOH H2O
a
Water is known to inhibit vinylation thus reducing
the yield of vinyl ethers [6]. On the other hand, alkali
The reaction mixture was heated first for 2 h at 110 115 C
and then for 2 h at 130 C.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 11 2001

1556
OPARINA et al.
major components: water, 1-heptyl vinyl ether, and
1-heptanol; also, traces of a volatile substance were
detected, assumingly of 1-heptene or heptane. When
the reaction was performed with dehydrated cesium
hydroxide, an additional high-boiling fraction,
bp 104 120 C (2 mm), was isolated. Its amount was
5 wt % of the total amount of products; according to
the GLC data, it contained 4 main components and
6 components in trace amounts. Among these, we
unambiguously identified expected 1,1-di(heptyloxy)-
ethane CH3CH(OC7H15-n)2, whose yield was 1.2%
on the 1-heptanol taken. The other components were
characterized by IR spectra. The presence of the
1
following absorption bands, , cm : 1197, 1607 w,
Fig. 2. Kinetic curves for acetylene absorption in the
1634 sh, and 1644 v.s (stretching vibrations of the
C O and C C bonds in vinyloxy group), suggests
that one of the high-boiling components is vinyl ether
formed as a result of initial condensation of 1-heptanol
according to Guerbet [9] (Scheme 1).
vinylation of 1-heptanol (0.3 mol) with acetylene (initial
acetylene pressure 16 atm at room temperature, 130 C)
(1) in the presence of 10 mol % of 2KOH H2O and (2) in
the presence of 10 mol % of 2KOH H2O and 1 mol %
of polyethylene glycol (molecular weight 400).
Scheme 1.
polymerization, the yield of 1-heptyl vinyl ether was
85%, and the conversion of 1-heptanol attained 98%;
these results are comparable with those obtained in
the vinylation of 1-heptanol at 150 C in 1 h in the
presence of cesium hydroxide (Table 2).
Chromatographic analysis of the liquid part of
the reaction mixture showed the presence of three
Table 4. Transformations of alkali metal hydroxides
during vinylation of 1-heptanol with acetylene (initial
pressure 14 17 atm at room temperature, 150 C, 5 h)
2-Pentylnonyl vinyl ether is likely to be formed
in the reactions performed under different conditions,
for the IR spectra of the extracts of the still residues
contained similar absorption bands; however, its
amounts were even smaller. No hydroxy compounds
were found in the above mixture of high-boiling
components: the IR spectra lacked the corresponding
absorption bands.
The amount of the solid fraction of the reaction
mixture depends on the nature and concentration of
alkali metal hydroxide. In the reactions with NaOH,
the solid fraction was a light yellow powder whose
weight was 15, 7, or 3% of the total weight of the
reaction mixture with an initial NaOH concentration
of 20, 10, and 5 mol %, respectively. With rubidium
and cesium hydroxide monohydrates at concentrations
of 20 and 10 mol % the dark brown powders consti-
tuted 15 25 wt % of the mixture. Approximately the
same amount of the solid fraction was obtained in
experiments with 20 mol % of 2KOH H2O; reduction
of the concentration of the latter to 10 mol % leads
to a more than twofold decrease of the amount of
the solid fraction which becomes light brown. In
Hydroxide Carboxylate fraction, %
Catalyst,
conversion,
mol %
%
heptanoate
acetate
LiOH, 20
NaOH, 20
NaOH, 10
NaOH, 5
50
88
94
91
99
95
94
72
99
95
92
51
99
98
96
Traces
48
80
79
50
56
48
100
35
40
40
100
26
43
37
100
52
20
21
50
44
52
Traces
65
60
60
Traces
74
57
63
2KOH H2O, 20
2KOH H2O, 10
2KOH H2O, 5
2KOH H2O, 20a
RbOH H2O, 20
RbOH H2O, 10
RbOH H2O, 5
RbOH H2O, 20a
CsOH H2O, 20
CsOH H2O, 10
CsOH H2O, 5
a
Without acetylene.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 11 2001

NUCLEOPHILIC ADDITION TO ACETYLENES . . . : XI.
1557
experiments with 5 mol % of the catalyst, almost no
solid products were formed. In these cases, the trans-
formations of alkali metal hydroxides were deduced
from analysis of the still residues which remained
after distillation of liquid products. A homogeneous
reaction mixture was also obtained in experiments
with lithium hydroxide as catalyst.
The results of titration of the solid fractions and
still residues showed that the activity of alkali metal
hydroxides during the process increases in the series
NMR signal intensities (solvent D2O). In the reactions
catalyzed by NaOH, i.e., when the system contains
a little of water, sodium heptanoate is preferentially
formed. In the presence of 2KOH H2O approximately
equal amounts of CH3COOK and C6H15COOK are
obtained. Rubidium and cesium hydroxides mono-
hydrates are converted mainly into the corresponding
acetates.
Apart from metal hydroxides and carboxylates, the
solid fractions contained a small amount (less than
10 wt %) of tars (the corresponding part of the solid
fraction is soluble in ether) and a colored insoluble
polymer. The latter can be isolated by dissolution in
water of the precipitate preliminarily washed with
acetone and ether. Especially large amounts of the
polymeric product were obtained in reactions with
20 mol % of potassium, rubidium, and cesium hy-
droxides (35 40 wt % of the overall amount of the
solid fraction). The polymer contains up to 80% of
carbon, 10% of hydrogen, oxygen, and ash;
obviously, it is polyacetylene. Insignificant poly-
merization of acetylene is known [6] to accompany
vinylation in all cases. The contribution of acetylene
polymerization increases by the moment of complete
transformation of 1-heptanol which, as follows from
Fig. 1 and Table 2, comes very soon when cesium or
rubidium hydroxide is used as catalyst. Therefore,
these catalysts, as well as potassium hydroxide at
a concentration of 20 mol %, promote formation of
polyacetylene in considerable amounts.
LiOH < NaOH < 2KOH H2O
RbOH H2O
CsOH H2O (Table 4). Rubidium and cesium
hydroxides are almost completely converted into
carboxylic acid salts. In the IR spectra of the solid
fractions, as well as of the still residues obtained
after vacuum distillation of 1-heptyl vinyl ether and
1-heptanol, we observed characteristic absorption
1
bands of COO group at about 1400 and 1560 cm
[10] and a set of bands in the region 2800 2900 cm
1
( C H). Their intensity and resolution change from
one experiment to another, but the general pattern
was the same for all alkali metal hydroxides used.
Primary and secondary alcohols are known [9] to
lose hydrogen on heating above 200 C in the presence
of sodium or potassium hydroxide; as a result, car-
boxylic acid salts are formed (Dumas Stas reaction).
We have found that all alkali metal hydroxides, except
for LiOH, react with 1-heptanol under the vinylation
conditions, yielding alkali metal heptanoates:
EXPERIMENTAL
In fact, heptanoic acid was isolated by acidification
of aqueous solutions of the solid fractions. Dehydro-
genation of 1-heptanol with potassium and rubidium
hydroxides in the absence of acetylene (see Tabl. 4,
The IR spectra were recorded in the range from
400 to 4000 cm on a Specord 75IR spectrometer
1
from samples prepared as thin films or KBr pellets.
1
a
The H NMR spectra were obtained on a Jeol FX-90Q
note ) also occurs. Here, potassium hydroxide is
instrument (90 MHz) at room temperature using D2O
as solvent and DSS as internal reference or CDCl3 as
solvent and HMDS as internal reference. The reaction
mixtures were analyzed by GLC on an LKhM-80
chromatograph equipped with a thermal conductivity
detector; carrier gas helium (flow rate 2 l/h); 3000
3-mm column packed with 1% of polyethylene glycol
20000 on NaCl (0.16 0.25 mm).
more active than RbOH (according to the tritration
data, the ratio hydroxide heptanoate was 1:3 and
1:1, respectively. Moreover, the vinylation process
is accompanied by known formation of acetates from
acetylene, alkali metal hydroxide, and water [11 13]:
The concentrations of alkali metal hydroxides,
heptanoates, and acetates in the reaction mixtures
were determined by potentiometric titration of dilute
aqueous solutions at 20 C using a universal EV-74
ionometer equipped with glass and silver chloride
electrodes; the titrant was 0.1 N HClO4.
The presence of alkali metal acetates in the solid
fraction was confirmed by the H NMR spectra which
1
contain a signal at 1.90 ppm (CH3COO ). Insofar as
the acidity constants of the resulting carboxylic acids
are very similar, it was possible to determine only
the overall concentration of salts by potentiometric
titration. An approximate ratio of alkali metal acetates
and heptanoates can be estimated on the basis of the
1-Heptanol, RbOH H2O, and CsOH H2O were
of pure grade, LiOH and NaOH were of chemically
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 11 2001

1558
OPARINA et al.
pure grade, and KOH was of analytical grade (accord-
ing to the titration data); commercial potassium
hydroxide of analytical grade contained 14% of water,
which exactly corresponds to the formula 2KOH
H2O; 1-heptanol was distilled prior to use.
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1
1.4226. H NMR spectrum (CDCl3), , ppm: 6.41 d.d
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1
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 11 2001