Nucleophilic addition to acetylenes in superbasic catalytic systems: XIV. Vinilation of diols in a system CsF-NaOH

Article abstract of DOI:10.1007/s11178-005-0223-x

A new catalytic system CsF-NaOH was developed for the synthesis of mono- and divinyl ethers of alkanediols exceeding in efficiency KOH. The nucleophilic addition of diols to acetylene in the presence of this system occurs both at enhance pressure (without solvent, 140-160°C) and atmospheric pressure (in DMSO medium, 100°C) of acetylene. Conditions were established of a selective preparation in a high yield of divinyl ethers from diols. 2005 Pleiades Publishing, Inc.

Full text of DOI:10.1007/s11178-005-0223-x

Russian Journal of Organic Chemistry, Vol. 41, No. 5, 2005, pp. 661-667. Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 5, 2005,
pp. 677-683.
Original Russian Text Copyright Ó 2005 by Oparina, Khil’ko, Chernyshova, Shaikhudinova, Parshina, Preiss, Henkelmann, Trofimov.
Nucleophilic Addition to Acetylenes in Superbasic Catalytic
Systems: XIV*. Vinilation of Diols in a System CsF-NaOH
L.A. Oparina1, M.Ya. Khil'ko1, N.A. Chernyshova1, S.I. Shaikhudinova1, L.N. Parshina1,
Th. Preiss2, J. Henkelmann2, and B.A. Trofimov1
1Faworsky Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk, 664033 Russia
e-mail: oparina@irioch.irk.ru
2BASF Aktiengesellschaft, Ammonia Laboratory ZAR/C, M 311, 67056 Ludwigshafen, Germany
Received February 11, 2004
Abstract—A new catalytic system CsF–NaOH was developed for the synthesis of mono- and divinyl ethers of
alkanediols exceeding in efficiency KOH. The nucleophilic addition of diols to acetylene in the presence of this
system occurs both at enhance pressure (without solvent, 140–160°C) and atmospheric pressure (in DMSO
medium, 100°C) of acetylene. Conditions were established of a selective preparation in a high yield of divinyl
ethers from diols.
products of these diols vinylation under acetylene pressure
in the presence of the catalytic system CsF–NaOH were
mono- IIa–IIg and divinyl IIIa–IIIg ethers formed in
an overall yield 60–85% (Tables 1 and 2).
Nucleophilic mono- and diaddition of diols to acetylene
occurs under effect of strong bases (alkali metal hy-
droxides and alcoholates, superbasic system KOH–
DMSO etc.) at enhanced or atmospheric pressure of
acetylene [2–10] and is accompanied as a rule by further
transformations of the target mono- and divinyl ethers
(acetalization, the rupture of C–O bonds, elimination of
a vinyl alcohol etc.) [2–13]. Therefore the search for
new catalysts for the efficient and selective synthesis of
mono- and divinyl ethers from diols remains an urgent
problem. With this goal we have for the first time studied
a reaction of acetylene with diols in the presence of
a new catalytic system CsF–NaOH [1, 14] whose
efficiency is due apparently mainly to the formation in
situ of anhydrous cesium hydroxide nanoparticles. The
an-hydrous cesium hydroxide is known to be more active
[15] but less available than KOH vinylation catalyst.
The effect of the vinylation conditions [reaction
temperature (136–158°C), heating time (1.5–3.0 h),
concentration of the catalytic system CsF–NaOH (5/5–
10/10 mol% of each component)] on the yield and relative
amount of final products II and III was investigated by
an example of 1,4-butanediol (Ie) (Table 1) that was
known to add to acetylene in the presence of potassium
hydroxide [2, 16] in a highly selective fashion with a
minimal formation of side products.
As seen from Table 1 under comparable conditions
the optimum amount of the catalytic system CsF–NaOH
is apparently 7 mol% of each component with respect to
butanediol Ie (Table 1, runs nos. 2–4): Using this con-
centration of the catalyst it is easy by varying the reaction
conditions and the ratio diol:acetylene to direct the process
to predominant formation of mono- (Table 1, runs nos. 2
and 3) or divinyl ether (run no. 4). At lower catalyst
concentration (Table 1, run no. 1) the conversion of the
initial diol within the same period decreases from 100 to
85% (Table 1, cf. runs nos. 1 and 3). Correspondingly,
the increase in the catalyst concentration to 10 mol% of
each component (Table 1, run no. 5) results in the
predominant formation of divinyl ether IIIe, however in
an insufficient yield (52%) apparently due to side
processes. Therewith the reaction mixture often suffers
self-heating (for instance, from 137 to 150°C, run no. 5,
By an example of a series of primary and secondary
diols Ia–Ig containing from 2 to 7 carbon atoms between
the hydroxy groups we demonstrated that the main
&V) 1D2+
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R = (CH2)2 (a), CH(CH3)CH(CH3) (b), (CH2)3 (c),
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(f), (CH2)7 (g).
* For communication XII see [1].
1070-4280/05/4105-0661Ó2005 Pleiades Publishing, Inc.

OPARINA et al.
662
Table 1. Vinylation of diols Id–Ig in the presence of CsF–NaOH at enhanced acetylene pressurea
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Table 2. Vinylation of 1,2- and 1,3-diols Ia–Id in the presence of CsF–NaOH at enhanced acetylene pressurea
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Initial pressure of acetylene 14 at, reactor of 1 liter capacity. KOH was used as catalyst.
of the carbon chain between the hydroxy groups. For
instance, in going from 1,3-propanediol (Ic) to 1,4-butane-
diol (Ie) and further to 1,7-heptanediol (Ig) the period of
reaction sufficient for complete vinylation (150–160°C,
CsF–NaOH concentration of 7 mol% of each component,
molar excess of acetylene with respect to diol) decreased
respectively 2 and 3-fold (Table 2, run no. 5; Table 1, run
no. 4, 10); therewith the yield of divinyl ethers IIIc, IIIe,
and IIIg was equal to 55, 76, and 85% respectively.
Table 1), i.e. at the reaction acceleration the possibility
of its control decreases.
In vinylation of 1,4-butanediol (Ie) the potassium
hydroxide proved to be under comparable conditions
a weaker catalyst than the system CsF–NaOH: With the
latter catalyst the complete conversion of diol Ie was
reached 1.5 times faster, and the yield of 1,4-butandiol
divinyl ether IIIe was 76% against 58% (Table 1, cf.
runs nos. 4 and 6). The lower catalytic activity of the
potassium hydroxide than that of the system CsF–NaOH
is also obvious from comparison of the rates of acetylene
consumption in the course of 1,4-butanediol vinylation in
the presence of these catalysts (Fig. 1).
The vinylation of the secondary hydroxy group is
known [2, 8] to occur more difficultly than the primary
one.Actually under optimum conditions for the synthesis
of 1,4-butanediol divinyl ether IIIe (150–158°C, 2 h,
7/7 mol% CsF–NaOH) the yield of 2,5-divinyloxy-hexane
(IIIf) was lower and attained 47% at the overall yield of
ethers IIf and IIIf 69% (Table 1, cf. runs nos. 4 and 7)
For diols with a linear structure (Ic, Ie, and Ig)
a certain trend was observed in increase of the rate and
efficiency of the reaction under study with growing length
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 5 2005

NUCLEOPHILIC ADDITION TO ACETYLENES IN SUPERBASIC CATALYTIC SYSTEMS: XIV.
663
but the conversion of 2,5-hexanediol (If) was complete.
Diol If and its monovinyl ether IIf were presumably
consumed in side reactions of Dumas–Stass type [17].
The increased to 10 mol% catalyst concentration favored
divinyl ether IIIf formation (Table 1, run no. 8), and the
use of excess 2,5-hexanediol (If) with respect to acetylene
and carrying out the vinylation reaction at a moderate
temperature (below 140°C) facilitated prevailing
preparation of monovinyl ether IIf (Table 1, run no. 9).
A well known feature of the base-catalyzed vinylation
of 1,2- and 1,3-diols is a side process consisting in
cyclization of their vinyl monoethers into the correspond-
ing cyclic acetals (1,3-dioxacyclanes) [2, 8, 9, 13]. The
use of the catalytic system CsF–NaOH instead of
potassium hydroxide does not prevent this cyclization
(Table 2). Moreover, cyclic acetal IVb is the main product
from 2,3-butanediol IIb (Table 2, run no. 4).
Fig. 1. Change of acetylene pressure in the course of
1,4-butanediol (Ie) vinylation: 1, in the presence of KOH,
7 mol%, 2, in the presence of CsF–NaOH, 7/7 mol%
(reaction temperature 150–158°C).
vinylation of the diol (Table 2, runs nos. 1–3). The
assumption that the catalytic system totally deactivated
was not confirmed since the adding of acetylene into the
reaction mixture cooled to room temperature resulted in
reanimation of the reaction with a faire rate at the
repeated heating of the reactor. Presumably, in the
strongly basic medium generated by CsOH where crown-
like complexes besides may form with the ethylene-oxide
diol Ia moieties elimination of vinyl alcohol occurs from
ethanediol divinyl ether IIIa [6, 7, 12]. The arising volatile
divinyl ether conserves the pressure in the reactor. Apart
from the divinyl ether a hydrogen liberation may occur
along the Dumas–Stass reaction [17] and by the known
process of acetylene consumption affording acetates
[18–20]. However it should be mentioned that inasmuch
as both latter processes require alkali consumption, the
repeated start of diol Ia vinylation at the supply of the
fresh acetylene portion and insignificant decrease in the
vinylation rate indicate that the alkali consumption was
small in this case, and consequently, these processes do
not notably affect ethanediol (Ia) vinylation.
5
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n = 0, R = R' = H (a), R= R' = CH3 (b); n = 1, R = R' = H (c),
R = H, R' = CH3 (d).
The relative amount of arising cyclic acetals, mono-,
and divinyl ethers depends on the ratio diol:acetylene:
catalyst, on the temperatire and time of reaction. For
instance, acetylene deficit (Table 2, runs nos. 1–3, 6)
results in incomplete diol conversion and to predominant
formation of the monovinyl ethers, the raising of the
temperature and increased catalyst concentration, as we
have shown previously [13], accelerates both the vinyl-
ation and acetalization of monovinyl ethers and favors
the formation of divinyl ethers and cyclic acetals even at
the acetylene deficit (Table 2, runs nos. 2, 5, 7, 8).
The comparison with KOH (Table 2, runs nos. 9 and
11) demonstrated the higher activity of the catalytic
couple CsF–NaOH in vinylation of 1,2- and 1,3-diols, but
the selectivity of the process still remained insufficient.
The prevalence of one among the ethers like was attained
at vinylation, for instance, of 1,4-butanediol (Ie) (Table 1,
run no. 4) or1,7-heptanediol (Ig) (Table 1, run no. 10)
we failed to achieve.
Hence all the features of ethanediol (Ia) vinylation
under acetylene pressure in the presence of potassium
hydroxide described in the literature [2, 6–9] and
previously observed in our studies [11–13] were also
revealed at catalysis of the reaction by the system CsF–
NaOH; the use of the system did not permit us any
significant refinement of the process characteristics.
We showed formerly that vinylation of diols in a super-
basic catalytic system KOH–DMSO occurred under
atmospheric pressure of acetylene and at relatively mild
temperature conditions, and therewith the system KOH–
DMSO selectively catalyzed the synthesis of divinyl ethers
Attention should also be drawn to the fact, that
ethanediol vinylation stopped with retention of some
excessive pressure in the reactor even when the initial
acetylene amount was insufficient for the exhaustive
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 5 2005

OPARINA et al.
664
It turned out that the vinylation of diols in the
superbasic system CsF–NaOH–DMSO occurred less
efficiently than the vinylation of monohydric alcohols [1].
Thus, in the presence of catalyst CsF–NaOH (10 mol%
each, corresponding to the concentration of 5/5 mol% to
every hydroxy group) in the reaction mixture after heating
to 100°C for 5–6 h was identified alongside initial 1,4-
butanediol (Ie) predominantly monovinyl ether (yield
30%), and the yield of divinyl ether IIIe was no more
than 10% (Table 3, run no. 8; Fig. 2, curve 3). Under
comparable conditions [1] the yield of vinyl heptyl ether
obtained by vinylation of 1-heptanol was 87%.
On increasing the concentration of the catalyst CsF–
NaOH to 20/20 mol% the rate of 1,4-butanediol (Ie)
reaction with acetylene in DMSO (100°C) sharply
increased, and in 5.5 h the yield of divinyl ether IIIe
reached 86% (Table 3, run no. 9; Fig. 2, curve 2). How-
ever further concentration increase is not feasible under
these conditions for the vinylation of 1,4-butanediol (Ie)
in the presence of 30/30 mol% of catalytic couple CsF–
NaOH resulted already within 4.5 h not only in complete
conversion of the initial diol and its monovinyl ether IIe,
but also in decrease in the yield of the corresponding
divinyl ether IIIe to 70% (Table 3, run no. 10; Fig. 2,
curve 1). Apparently in the presence of large amounts of
the basic catalyst the side processes occurring alongside
the diol vinylation are also accelerated, for instance, the
formation of carboxylic acids salts [11, 15, 21] or vinyl
alcohol cleavage from the arising vinyl ethers IIe and
IIIe [12] etc.
Fig. 2. Vinylation of 1,4-butanediol (Ie) at atmospheric
pressure of acetylene in the presence of a superbasic
system CsF–NaOH–DMSO. (1) CsF–NaOH 30/30 mol%;
(2) CsF–NaOH 20/20 mol%; (3), CsF–NaOH 10/10 mol%.
[16]. On the other hand, the vinylation of 1-heptanol
effected by CsOH·H2O also was considerably faster in
DMSO than in the absence of solvent [21]. It was of
interest to study the effect on diol vinylation of a new
catalytic system CsF–NaOH–DMSO. This was
especially important for 1,2- and 1,3-diols whose vinylation
as was shown above did not afford satisfactory yields of
divinyl ethers in the absence of DMSO.
The optimization of the reaction conditions was
performed as before by an example of 1,4-butanediol (Ie)
whose vinylation in the presence of basic catalysts
occurred more smoothly than with 1,2- and 1,3-diols.
Table 3. Vinylation of diols Ia, Ic–Ie, and Ig in the presence of CsF–NaOH–DMSO at atmospheric acetylene pressurea
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ꢈꢅꢅꢀ
ꢍꢆꢀ
ꢈꢅꢅꢀ
ꢈꢅꢅꢀ
ꢍꢋꢀ
ꢅꢀ
ꢇꢍꢀ
ꢉꢅꢀ
ꢅꢀ
ꢀꢉꢀ
ꢀꢀꢀ
ꢀꢁꢀ
ꢅꢀ
ꢆꢊꢀ
ꢅꢀ
ꢆꢅꢄꢆꢅꢀ
ꢈꢅꢅꢀ
ꢀ
a 0.05 mol of diol, 50 ml of DMSO, 100°C, rate of acetylene flow ~2 l/h.
b Alcoholate obtained by distilling off water was used as catalyst. .
c KOH was used as catalyst.
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 5 2005

NUCLEOPHILIC ADDITION TO ACETYLENES IN SUPERBASIC CATALYTIC SYSTEMS: XIV.
665
The vinylation of 1,4-butanediol (Ie) with acetyl-
ene under comparable conditions in the presence of
the traditional superbasic system KOH (20 mol%)–
DMSO or of the new catalytic system CsF–NaOH
(20/20 mol%)–DMSO (Table 3, runs nos. 11 and 9
respectively) demonstrate the advantages of the latter:
the yield of divinyl ether IIIe was in the first case 10%,
in the second 86%. We succeeded to prepare divinyl ether
IIIe in a 86% yield in the system KOH–DMSO only at
the use at equimolar amount of KOH [i.e., in the presence
of 100 mol% KOH with respect to 1,4-butanediol
(Ie)] [16].
and cyclization of 1,3-butanediol monovinyl ether IId.
The reaction of ethanediol (Ia) with acetylene under
atmospheric pressure in the system CsF–NaOH–DMSO
with the use of the catalytic reagents in amounts from
10/10 to 40/40 mol% gave rise to formation of mono-IIa
and divinyl IIIa ethers in an overall yield not exceeding
49% (Table 3, runs nos. 1–5), although the initial diol Ia
conversion was 74–100%.
The most probable side processes in vinylation of
ethanediol (Ia) are apparently the Dumas–Stass reaction
and the base-catalyzed elimination of the vinyl alcohol
from the arising vinyl ethers IIa and IIIa [12], since we
have not observed formation in a significant amount of
dioxolane IVa (may be due to a stringent mode of the
GLC analysis of the reaction mixtures caused by the
presence of DMSO and hampering a reliable identification
of volatile impurities).
The conditions we found for selective and efficient
synthesis of divinyl ether IIIe from 1,4-butanediol (Ie)
and acetylene in the system CsF–NaOH–DMSO (Table
3, run no. 9) proved to be plausible also for the exhaustive
vinylation of 1,7-heptane-diol (Ig) (Table 3, run no. 12)
confirming the general character of the reaction, at least
for diols with a normal backbone and no less than four
CH2 groups in the molecule. At heating (100°C, 2.5 h)
1,7-heptanediol (Ig) in the system CsF (20 mol%)–NaOH
(20 mol%)–DMSO in an acetylene flow 1,7-
divinyloxyheptane (IIIg) was obtained in a 87% yield at
the complete conversion of the initial diol.
It should be especially mentioned that although the
ethanediol (Ia) vinylation took a long time (4.5–6 h)
monovinyl ether IIa remained in the reaction mixture, and
the complete conversion of initial diol Ia reached 100%
only at the use of large amount of the catalyst (30/30 and
more mol% of CsF–NaOH). Obviously the catalyst is
consumed in the side processes, first of all, in the formation
of carboxylic acids salts by Dumas–Stass reaction.
Surprisingly this process of a general character [15, 21]
was the most apparent in the vinylation of 1,2- and
1,3-diols presumably due to the formation of crown-like
complexes of alkali metal cations both with the initial diols
and their vinylation products.
In the system KOH–DMSO a similar result was
obtained applying 100 mol% of KOH with respect to
initial 1,7-heptanediol (Ig) [16].
Inasmuch as the secondary alcohols add to acetylene
slower than primary [2, 8] it was presumable that under
comparable conditions the yield of the divinyl ether from
1,3-butanediol IIId would be lower than the yield of the
divinyl ether from 1,4-butanediol IIIe. The vinylation at
100°C within 5 h of 1,3-butanediol (Id) in the system
CsF (20 mol%)–NaOH (20 mol%)–DMSO actually
afforded divinyl ether IIId in a low yield (21%), and in
the reaction mixture was present a significant amount of
monovinyl ether IId (yield 57%) (Table 3, run no. 7).
But 2,4-dimethyl-1,3-dioxane (IVd) was virtually lacking
in the product, meaning that no cyclization of the
monovinyl ether occurred that commonly accompanied
the vinylation of 1,2- and 1,3-diols. Taking into account
that the yield of divinyl ether from 1,3-butanediol IIId in
vinylation effected by the system KOH–DMSO at the
use of equimolar amount of KOH attained 60% [16] and
that according to our data [13] the cyclization of
monovinyl ethers was also catalyzed by alkali, apparently,
the applied amount of the alkaline catalyst, namely, 20/
20 mol% of the system CsF–NaOH, was insufficient for
an efficient catalysis of competing reactions of vinylation
Thus the new catalytic systems CsF–NaOH and CsF–
NaOH–DMSO are more efficient than the traditional
catalysts KOH and KOH–DMSO in the vinylation of
alkanediols with a long chain, but are second to the latter
in vinylation of 1,2- and 1,3-diols due to the high activity
in catalyzing side processes.
EXPERIMENTAL
IR spectra of compounds synthesized were recorded
from thin films on a spectrometer Bruker JFS-25 in the
–1
region 400–4000 cm . 1H NMR spectra were registered
at room temperature on spectrometer Bruker DPX-400
at operating frequency 400.13 MHz, solvent CDCl3,
internal reference HMDS. The reaction mixtures were
analyzed by GLC on LKhM-80 instrument equipped with
a katharometer, column 3000´3 mm, stationary phase
poly(ethylene glycol) 20000, 1% on NaCl, carrier gas
helium.
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 5 2005

OPARINA et al.
666
The diols used in the study were distilled, NaOH was
REFERENCES
of “chemically pure” grade, CsF (Sigma-Aldrich) and
DMSO (Merck) were commercial reagents.
1. Oparina, L.A., Shaikhudinova, S.I., Parshina, L.N.,
Vysotskaya, O.V., Preiss, Th., Henkelmann, J., and Trofimov,
B.A., Zh. Org. Khim., 2005, vol. 41, p. 512.
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Novye monomery, reagenty i poluprodukty (Heteroatomic
Derivatives of Acetylene. New Monomers, Reagents, and
Intermediates), Moscow: Nauka, 1981, 319 p.
3. Trofimov, B.A., Usp. Khim., 1981, vol. 50, p. 248.
4. Trofimov, B.A., Z. Chem., 1986, vol. 26, p. 41.
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8. Shostakovskii, M.F., Prostye vinilovye efiry (Vinyl Ethers),
Moscow: Izd.Akad. Nauk SSSR, 1952, 280 p.
9. Reppe, W., Lieb. Ann., 1956, vol. 601, p. 81.
10. Steinborn, D., Mosinski, H., and Rosenstock, T.,
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1986, vol. 22, p. 1583.
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and Lavrov, V.I., Izv. Akad. Nauk SSSR, Ser. Khim., 1989,
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rina, L.A., Izv. Akad. Nauk SSSR, Ser. Khim., 1984, p. 1670.
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Preiss, Th., Henkelmann, J., and Trofimov, B.A., Zh. Org.
Khim., 2001, vol. 37, p. 1629.
16. Trofimov, B.A., Kudyakova, R.N., Oparina, L.A., Parshina,
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17. Ustanovlenie struktury organicheskikh soedinenii fizi-
cheskimi i khimicheskimi metodami (Recognition of
Organic Compounds Structure with Physical and Chemical
Methods), Moscow: Khimiya, 1967.
General procedure for vinylation of diols at
enhanced acetylene pressure. Into a rotating steel
reactor of 1 liter capacity was charged 0.2–0.6 mols of
diol Ia–Ig, NaOH and CsF in amounts indicated in
Tables 1 and 2 (0.006–0.04 mol of each component), and
acetylene was supplied to the initial pressure of 10–
14 at. The reaction was carried out at stirring and heating
to 135–140°C for 1–5 h as indicated in Tables 1 and 2.
The reaction products were distilled at atmospheric or
reduced pressure depending on the boiling point of the
monovinyl and divinyl ethers and were analyzed by GLC.
Diol conversions and vinyl ethers yields are given in Tables
1 and 2, the physical constants and spectral characteristics
of compounds obtained are consistent with those
published in [2, 8, 9, 16].
General procedure for vinylation of diols at
atmospheric pressure of acetylene. Into a reaction
flask of 100 ml capacity, equipped with an efficient reflux
condenser, thermometer, magnetic stirrer, and a bubbler
for supplying acetylene was charged 0.05 mol of diol I,
NaOH and CsF in amounts indicated in Table 3 (0.005–
0.02 mol of each component), and 50 ml of DMSO, the
content of the flask was heated to 100°C, and acetylene
was passed through the mixture at a rate of 2 liter per
hour. The process was monitored by GLC. The vinilation
reaction time is given in Table 3. From the mixture obtained
the reaction products were extracted with petroleum ether
(4´50 ml), the extract was washed with water (3´20–
30 ml), and dried with calcined potassium carbonate. On
removing the petroleum ether the residue was distilled.
Diol conversions and vinyl ethers yields are given in
Table 3.
18. Strosacker, C.J. and Stephenson, W.T., US Patent 1866328,
1932; Chem. Abstr., 1932, vol. 26, p. 4345.
19. Strosacker, C.J., Kennedy, C.C., and Pelton, E.L., US Patent
The study was carried out by the financial support of
the President of the Russian Federation to the leading
scientific schools (grant RF no. NSh-2241.2003.3).
1866329, 1932; Chem. Abstr., 1932, vol. 26, p. 4345.
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 5 2005