Nucleophilic addition to acetylenes in superbasic catalytic systems: XIII. Fluoride cesium containing systems, efficient catalysts for alkanols vinylation

Article abstract of DOI:10.1007/s11178-005-0222-y

New catalytic systems CsF-MOH (M = Li, Na) were developed for the synthesis of alkyl vinyl ethers comparable in efficiency to cesium alcoholates. The addition of primary and secondary alcohols to acetylene occurs in the presence of these systems at the atmospheric (DMSO, 100°C) or at enhanced (without solvent, 135-140°C) acetylene pressure and affords alkyl vinyl ethers in up to 93% yield. 2005 Pleiades Publishing, Inc.

Full text of DOI:10.1007/s11178-005-0222-y

Russian Journal of Organic Chemistry, Vol. 41, No. 5, 2005, pp. 656-660. Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 5, 2005,
pp. 672-676.
Original Russian Text Copyright Ó 2005 by Oparina, Shaikhudinova, Parshina1, Vysotskaya, Preiss, Henkelmann, Trofimov.
Nucleophilic Addition to Acetylenes in Superbasic Catalytic
Systems: XIII.* Fluoride Cesium Containing
Systems, Efficient Catalysts forAlkanols Vinylation
1
1
1
1
L.A. Oparina , S.I. Shaikhudinova , L.N. Parshina , O.V. Vysotskaya ,
2
2
1
Th. Preiss , J. Henkelmann , and B.A. Trofimov
1Faworsky Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk, 664033 Russia
e-mail: oparina@irioch.irk.ru
2
BASF Aktiengesellschaft, Ammonia Laboratory ZAR/C, M 311, 67056 Ludwigshafen, Germany
Received February 11, 2004
Abstract—New catalytic systems CsF–MOH (M = Li, Na) were developed for the synthesis of alkyl vinyl ethers
comparable in efficiency to cesium alcoholates. The addition of primary and secondary alcohols to acetylene
occurs in the presence of these systems at the atmospheric (DMSO, 100°C) or at enhanced (without solvent, 135–
140°C) acetylene pressure and affords alkyl vinyl ethers in up to 93% yield.
The systematic investigation of alcohols vinylation with
acetylenes discovered by A.E. Faworsky [2] and further
developed by W. Reppe [3] and M.F.Shostakovskii [4]
rious process. Usually azeotropic removal of water is used
with an appropriate high-boiling solvent (octane, toluene).
The present article contains findings evidencing the pos-
provide deeper theoretical insight into the nucleophilic sibility of a successful application to the vinyl ethers syn-
additions to the triple bond [5] and constant refining of thesis of a catalytic system CsF–MOH (M = Li, Na)
the synthesis of vinyl ethers of versatile structures [3–
2]. Here the main trend in stimulating vinilation reaction
where the anhydrous CsOH is formed directly in the
course of vinylation. This system possesses significant
advantages compared to traditional vinylation catalysts
like sodium and potassium hydroxides.
1
is the application of superbasic systems, like alkali metal
hydroxide–polar solvent lacking hydroxy groups (DMSO,
N-methylpyrrolidone, HMPA) [5, 7–12], or alkali metal
alcoholate–Lewis base (Crown ether)–solvent lacking
hydroxy groups (hydrocarbon) [13, 14].
The high catalytic efficiency of the system developed
is apparently due predominantly to the exchange between
the lithium or sodium hydroxides and cesium fluoride re-
sulting in cesium hydroxide and sparingly soluble lithium
or sodium fluorides.
We report here on the application of highly basic sys-
tems CsF–MOH and CsF–MOH–DMS (M = Li, Na) as
efficient catalysts to alcohols vinylation.
02+ꢀꢀꢀꢀꢀ&V)
&V2+ꢀꢀꢀꢁꢁ0)
In [15, 16] it was shown by an example of 1-heptanol
vinylation under enhanced and atmospheric acetylene
pressure in the presence of alkali metal hydroxides that
the catalysts under investigation fit to the following series
The nature of the alkali metal cation in the MOH
where M = Li, Na) used in the catalytic couple CsF–
(
MOH did not virtually affect the rate of vinylation in keep-
ing with the preliminary occurrence of the exchange re-
action and with the actual catalysis of alcohol vinylation
by the arising cesium hydroxide. The formation of spar-
ingly soluble lithium and sodium fluorides shifts the ex-
change equilibrium to the right. Therewith the better solu-
bility in alcohols of NaOH compared to LiOH ensures
the faster and more complete preparation of an active
catalyst in the system CsF–NaOH. Therefore the most
results reported here were obtained with the use of just
this catalytic couple.
according to the decreasing efficiency: CsOH·H O ³
2
RbOH·H O > 2KOH·H O > NaOH > KOH·H O > LiOH.
2
2
2
The comparison of the catalytic activity of KOH hydrates
(
2KOH·H O and KOH·H O) confirmed the known [4,
2 2
7
] negative effect of water on the vinylation process.
Consequently, the use of anhydrous alkali metal hydrox-
ides, first of all of CsOH would considerably accelerate
the vinylation of the hydroxy compounds. However the
preparation of anhydrous cesium and rubidium is a labo-
*
For communication XII see [1].
1070-4280/05/4105-0656Ó2005 Pleiades Publishing, Inc.

NUCLEOPHILIC ADDITION TO ACETYLENES IN SUPERBASIC CATALYTIC SYSTEMS: XIII.
657
&
V) 1D2+
high vinylation rate of the higher alcohols permitted the
reduction of the catalyst concentration to 5 and even
3 mol% (Table 1, cf. runs nos. 10–12, 14), whereas with
the lower (Table 1, runs nos. 3 and 4) and especially
secondary (Table 1, runs nos. 2 and 6 cf. with runs
nos. 1 and 4) alcohols the use of 10 mol% of the catalyst
is more feasible.
5
2+ꢀꢀꢀ +& &+
52&+ &+
R = Pr, i-Pr, Bu, i-Bu, s-Bu, Et CHCH , cyclo-C H ,
2
2
6
11
n.-C H , n.-C H , n.-C H .
7
15
9
19
12 25
The reaction of acetylene with primary and second-
ary aliphatic alcohols in the presence of the catalytic sys-
tem CsF–NaOH at 135–140°C (1–3 h) and enhanced
acetylene pressure afforded alkyl vinyl ethers in a 73–
The potassium hydroxide turned out to be less active
than the new superbasic system: When instead of CsF–
NaOH was used KOH (at catalyst concentration 5 mol%)
the conversion of 1-heptanol into the vinyl heptyl ether
decreased from 88 to 61% (Table 1, cf. runs nos. 12 and
8
9% yield (Table 1).
It was demonstrated by an example of 1-heptanol [16]
that as large as this vinyl ether yield was obtained under
similar conditions only in reaction in the presence of ce-
sium heptylate.
1
3). The vinyl ethers (R = cyclo-C H , n.-C H ) were
6 11 9 19
obtained in lower yields even at the longer reaction pe-
riod (Table 1, cf. runs nos. 8 and 9, 15 and 16).
The higher primary alcohols (R = Et CHCH ,
2
2
n.-C H , n.-C H , n.-C H ) possess a similar reactivity
7
15
9
19
12 25
It is known that the application of superbasic catalytic
media of the type alkali metal hydroxide–polar solvent
lacking hydroxy groups (DMSO, HMPA, N-methyl-
pyrrolidone etc.) results in considerable acceleration of
the nucleophilic addition to the acetylene [5, 7–12]. The
higher vinylation rate permits performing the reaction
under milder conditions, often under atmospheric pres-
sure of the acetylene.
and afford vinyl ethers in fairly equal yields and with a
high selectivity (Table 1, runs nos. 7, 10–12, 14, 15, 17).
The conversion of alcohol suggests that the reactivity tends
to grow in the series C < C » C < C » C , whereas
4
6
7
9
12
the selectivity of the reaction is virtually unchanged. The
Table 1. Vinylation of alcohols ROH with acetylene in the
presence of CsF–NaOH at enhanced acetylene pressure
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systems at atmospheric pressure of acetylene
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a
5
0 mmol of alcohol, 50 ml of DMSO, 100°C, acetylene flow rate
a
ꢀ
3
00 mmol of alcohol, 135–140°C, initial acetylene pressure 10–
4 at, reactor of 1 liter capacity.
The yield is calculated with respect to the reacted alcohol.
Vinylation catalyst KOH.
~
2 l/h.
1
b
c
The yield is calculated with respect to the reacted alcohol.
30 ml of DMSO
Vinilation catalyst KOH.
b
c
d
d
e
Catalytic system CsF–LiOH.
Vinilation catalyst NaOH.
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 5 2005

658
OPARINA et al.
These observations proved to be valid alsofor the newly
reaction, the alcohol concentration in DMSO should be
~1 mol l- , the rate of acetylene flow ~2 liter per hour.
1
developed systems CsF–MOH (M = Li, Na). The use of
DMSO as a complexing solvent resulted in even more
active superbasic catalytic systems CsF–MOH (M = Li,
Na)–DMSO, considerably increased the vinylation effi-
ciency in the presence of the system CsF–NaOH–
DMSO. The latter system catalyzed the vinylation of
alcohols at the atmospheric pressure and temperature
The catalytic couple CsF–NaOH functions efficiently
even at concentration 5/5 mol%, but the complete
conversion of the alcohol is reached in a longer period,
approximately 1.5 times longer (Table 2, cf. runs nos. 10
and 11). Unlike this in the system NaOH–DMSO the
complete conversion of n.-C H OH is not attained even
7
15
1
00°C in 76–93% yields (Table 2). The optimum catalyst
at increasing the sodium hydroxide concentration to
20 mol% and at twice longer the process (Table 2, run
no. 12, cf. with runs nos. 10, 11).
concentration is 10 mol% of each catalyst component
with respect to the alcohol brought into the vinylation
Table 3. Some physical constants and spectral characteristics of ethers ROCH=CH2
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ꢅꢁꢈꢇꢀPꢀꢐꢏ+ꢑꢃꢀ
ꢅꢁꢇꢍꢀPꢀꢐꢌ+ꢑꢀ
>
ꢅꢏꢉꢀ
ꢅꢁꢏꢊꢏꢆꢀ
ꢅꢁꢏꢊꢏꢋꢀ
ꢋꢁꢇꢅꢀ ꢏꢁꢌꢋꢀꢐ-ꢀꢅꢏꢁꢌꢃꢀ ꢇꢁꢍꢋꢀꢐ-ꢀꢋꢁꢋꢃꢀ ꢇꢁꢈꢌꢀꢐꢅ+ꢑꢀ
ꢅꢁꢏꢑꢀ ꢅꢁꢏꢑꢀ
ꢀ
F\FORꢂ&+ ꢀ
>ꢌꢇ@ꢀ
ꢋꢆꢀꢐꢅꢌꢑꢀ
Qꢁꢎ&+ ꢀ ꢅꢋꢋꢀ>ꢌꢇ@ꢀ
ꢅꢁꢏꢌꢌꢋꢀ
ꢅꢁꢏꢌꢌꢆꢀ
ꢋꢁꢏꢏꢀ ꢏꢁꢅꢊꢀꢐ-ꢀꢅꢏꢁꢏꢃꢀ ꢇꢁꢍꢌꢀꢐ-ꢀꢋꢁꢉꢃꢀ ꢇꢁꢋꢊꢀWꢀꢐꢌ+ꢃꢀꢀ ꢅꢁꢋꢇꢀTꢀꢐꢌ+ꢃꢀꢀ ꢆꢁꢉꢈꢀꢐꢇ+ꢃꢀ-ꢀꢋꢁꢉꢑꢀ
ꢅꢁꢉꢑꢀ
ꢅꢁꢉꢑꢀ
-ꢀꢋꢁꢋꢑꢀ
-ꢀꢋꢁꢋꢑꢃꢀꢅꢁꢌꢈ±
>ꢌꢇ@ꢀ
ꢅꢁꢇꢈꢀPꢀꢐꢉ+ꢑꢀ
ꢍꢈꢀꢐꢅꢇꢑꢀ
ꢅꢁꢏꢇꢌꢇꢀ
ꢋꢁꢏꢏꢀ ꢏꢁꢅꢊꢀꢐ-ꢀꢅꢏꢁꢇꢃꢀ ꢇꢁꢍꢏꢀꢐ-ꢀꢋꢁꢉꢃꢀ ꢇꢁꢋꢊꢀWꢀꢐꢌ+ꢃꢀꢀ ꢅꢁꢋꢏꢀTꢀꢐꢌ+ꢃꢀꢀ ꢆꢁꢉꢈꢀWꢀꢐꢇ+ꢃꢀ-ꢀꢋꢁꢋꢑꢀ
Qꢁꢎ&+ ꢀ ꢌꢆꢋ±ꢌꢆꢈꢀ>ꢌꢇ@ꢅꢁꢏꢇꢅꢆꢀ
ꢌꢇ@ꢀ
ꢅꢁꢉꢑꢀ
ꢅꢁꢉꢑꢀ
-ꢀꢋꢁꢋꢑꢀ
-ꢀꢋꢁꢍꢑꢃꢀꢅꢁꢇꢌ±
ꢅꢁꢇꢈꢀPꢀꢐꢌ+ꢑꢃꢀ
ꢅꢁꢌꢅ±ꢅꢁꢇꢌꢀPꢀ
ꢐꢅꢆ+ꢑꢀ
>
ꢅꢆꢌꢀꢐꢌꢑꢀ
ꢅꢁꢏꢏꢅꢌꢀ
ꢋꢁꢏꢇꢀ ꢏꢁꢅꢏꢀꢐ-ꢀꢅꢏꢁꢇꢃꢀ ꢇꢁꢍꢏꢀꢐ-ꢀꢋꢁꢈꢃꢀ ꢇꢁꢋꢏꢀWꢀꢐꢌ+ꢃꢀꢀ ꢅꢁꢋꢇꢀTꢀꢐꢌ+ꢃꢀꢀ ꢆꢁꢉꢋꢀWꢀꢐꢇ+ꢃꢀ-ꢀꢋꢁꢋꢑꢀ
Qꢁꢎ& + ꢀ ꢅꢌꢋꢀꢐꢇꢑꢀ>ꢌꢅ@ꢀ
ꢅꢁꢉꢑꢀ
ꢅꢁꢉꢑꢀ
-ꢀꢋꢁꢊꢑꢀ
-ꢀꢋꢁꢋꢑꢃꢀꢅꢁꢌꢋ±
ꢅꢁꢏꢊꢀPꢀꢐꢅꢉ+ꢑꢀ
ꢀ
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 5 2005

NUCLEOPHILIC ADDITION TO ACETYLENES IN SUPERBASIC CATALYTIC SYSTEMS: XIII.
Table 3. (Contd.)
659
5ꢀ
,5ꢀVSHFWUXPꢃꢀFP ꢀ
3
Uꢀ
Lꢎ3Uꢀ
Xꢀ
ꢏꢋꢈꢃꢀꢊꢍꢈꢃꢀꢈꢆꢆꢃꢀꢈꢋꢇꢃꢀꢉꢅꢇꢃꢀꢍꢆꢋꢃꢀꢍꢌꢈꢃꢀꢍꢊꢆꢃꢀꢍꢋꢊꢃꢀꢍꢉꢋꢃꢀꢅꢆꢆꢋꢃꢀꢅꢆꢅꢊꢃꢀꢅꢆꢏꢏꢃꢀꢅꢆꢈꢈꢃꢀꢅꢅꢌꢌꢃꢀꢅꢅꢏꢍꢃꢀꢅꢌꢆꢊꢃꢀꢅꢇꢌꢅꢃꢀꢅꢇꢉꢇꢃꢀ
ꢅꢏꢊꢋꢃꢀꢅꢏꢋꢋꢃꢀꢅꢋꢅꢌꢃꢀꢅꢋꢇꢋꢃꢀꢅꢋꢊꢆꢀVKꢃꢀꢌꢉꢋꢍꢃꢀꢌꢍꢇꢉꢃꢀꢌꢍꢈꢋꢃꢀꢇꢆꢏꢈꢃꢀꢇꢆꢈꢍꢃꢀꢇꢅꢅꢍꢀ
ꢏꢋꢈꢃꢀꢋꢆꢅꢃꢀꢋꢍꢈꢃꢀꢉꢅꢍꢃꢀꢉꢍꢉꢃꢀꢍꢏꢍꢃꢀꢍꢋꢉꢃꢀꢍꢉꢆꢃꢀꢅꢆꢅꢋꢃꢀꢅꢅꢌꢇꢃꢀꢅꢅꢉꢌꢃꢀꢅꢌꢆꢌꢃꢀꢅꢇꢌꢆꢃꢀꢅꢇꢏꢅꢃꢀꢅꢇꢈꢇꢃꢀꢅꢇꢉꢏꢃꢀꢅꢏꢊꢇꢃꢀꢅꢏꢋꢉꢃꢀꢅꢋꢅꢈꢃꢀ
ꢅꢋꢇꢋꢃꢀꢅꢋꢏꢆꢀVKꢃꢀꢌꢉꢉꢌꢃꢀꢌꢍꢇꢊꢃꢀꢌꢍꢈꢈꢃꢀꢇꢆꢅꢉꢃꢀꢇꢆꢏꢇꢃꢀꢇꢆꢈꢋꢃꢀꢇꢅꢅꢉꢀ
ꢏꢇꢇꢃꢀꢊꢆꢌꢃꢀꢋꢆꢌꢃꢀꢈꢆꢆꢃꢀꢈꢏꢆꢃꢀꢈꢊꢉꢃꢀꢉꢅꢅꢃꢀꢉꢉꢉꢃꢀꢍꢏꢈꢃꢀꢍꢋꢇꢃꢀꢍꢈꢍꢃꢀꢅꢆꢆꢍꢃꢀꢅꢆꢌꢏꢃꢀꢅꢆꢇꢋꢃꢀꢅꢆꢋꢊꢃꢀꢅꢆꢈꢉꢃꢀꢅꢅꢌꢏꢃꢀꢅꢌꢆꢏꢃꢀꢅꢇꢌꢆꢃꢀꢅꢇꢈꢉꢃꢀ
ꢅꢏꢋꢋꢃꢀꢅꢋꢅꢅꢃꢀꢅꢋꢇꢉꢃꢀꢅꢋꢊꢆꢀVKꢃꢀꢌꢉꢈꢏꢃꢀꢌꢍꢇꢋꢃꢀꢌꢍꢋꢅꢃꢀꢇꢆꢅꢍꢃꢀꢇꢆꢏꢉꢃꢀꢇꢆꢈꢍꢃꢀꢇꢅꢅꢍꢀ
%
Lꢎ%Xꢀ
Vꢎ%Xꢀ
ꢏꢊꢌꢃꢀꢊꢍꢏꢃꢀꢈꢆꢆꢃꢀꢈꢇꢋꢃꢀꢉꢅꢌꢃꢀꢉꢋꢊꢃꢀꢍꢅꢌꢃꢀꢍꢏꢊꢃꢀꢍꢋꢇꢃꢀꢅꢆꢅꢌꢃꢀꢅꢆꢏꢅꢃꢀꢅꢆꢈꢋꢃꢀꢅꢅꢅꢏꢃꢀꢅꢅꢇꢊꢃꢀꢅꢌꢆꢈꢃꢀꢅꢇꢆꢆꢃꢀꢅꢇꢌꢅꢃꢀꢅꢇꢋꢍꢃꢀꢅꢇꢉꢍꢃꢀ
ꢅꢏꢅꢌꢃꢀꢅꢏꢈꢅꢃꢀꢅꢋꢅꢌꢃꢀꢅꢋꢇꢋꢃꢀꢅꢋꢊꢏꢃꢀꢌꢉꢈꢊꢃꢀꢌꢍꢅꢌꢃꢀꢌꢍꢇꢆꢃꢀꢌꢍꢊꢍꢃꢀꢇꢆꢅꢍꢃꢀꢇꢆꢏꢈꢃꢀꢇꢆꢉꢆꢃꢀꢇꢅꢅꢍꢀ
ꢏꢋꢏꢃꢀꢋꢍꢋꢃꢀꢈꢊꢆꢃꢀꢉꢌꢌꢃꢀꢉꢈꢆꢃꢀꢍꢅꢇꢃꢀꢍꢊꢆꢃꢀꢍꢋꢊꢃꢀꢍꢍꢌꢃꢀꢅꢆꢌꢇꢃꢀꢅꢆꢌꢍꢃꢀꢅꢆꢏꢅꢃꢀꢅꢅꢆꢍꢃꢀꢅꢅꢌꢋꢃꢀꢅꢅꢋꢌꢃꢀꢅꢅꢉꢆꢃꢀꢅꢌꢆꢆꢃꢀꢅꢇꢌꢌꢃꢀꢅꢇꢏꢋꢃꢀ
ꢅꢇꢈꢉꢃꢀꢅꢏꢆꢈꢃꢀꢅꢏꢊꢈꢃꢀꢅꢋꢅꢆꢃꢀꢅꢋꢇꢏꢃꢀꢌꢉꢉꢆꢃꢀꢌꢍꢇꢊꢃꢀꢌꢍꢈꢌꢃꢀꢇꢆꢅꢉꢃꢀꢇꢆꢏꢇꢃꢀꢇꢆꢈꢋꢃꢀꢇꢅꢅꢉꢀ
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W&+&+ꢀ ꢏꢌꢆꢃꢀꢋꢆꢊꢃꢀꢋꢋꢉꢃꢀꢈꢆꢆꢃꢀꢈꢌꢏꢃꢀꢉꢅꢅꢃꢀꢍꢌꢊꢃꢀꢍꢏꢊꢃꢀꢍꢋꢇꢃꢀꢍꢈꢉꢃꢀꢍꢍꢈꢃꢀꢅꢆꢈꢈꢃꢀꢅꢆꢍꢍꢃꢀꢅꢅꢇꢊꢃꢀꢅꢌꢆꢊꢃꢀꢅꢇꢌꢆꢃꢀꢅꢇꢏꢅꢃꢀꢅꢇꢈꢉꢃꢀꢅꢏꢋꢈꢃꢀꢅꢋꢅꢆꢃꢀ
ꢅꢋꢇꢋꢃꢀꢅꢋꢏꢉꢃꢀꢌꢉꢊꢉꢃꢀꢌꢉꢈꢆꢃꢀꢌꢍꢇꢅꢃꢀꢌꢍꢊꢉꢃꢀꢇꢆꢏꢋꢃꢀꢇꢆꢈꢉꢃꢀꢇꢅꢅꢉꢀ
F\FORꢎ&+ ꢀ ꢏꢈꢏꢃꢀꢋꢆꢉꢃꢀꢋꢍꢈꢃꢀꢉꢌꢌꢃꢀꢉꢋꢇꢃꢀꢉꢍꢆꢃꢀꢍꢆꢈꢃꢀꢍꢌꢈꢃꢀꢍꢏꢈꢃꢀꢍꢋꢏꢃꢀꢍꢉꢋꢃꢀꢅꢆꢌꢏꢃꢀꢅꢆꢇꢍꢃꢀꢅꢆꢊꢏꢃꢀꢅꢆꢈꢈꢃꢀꢅꢆꢍꢊꢃꢀꢅꢅꢌꢍꢃꢀꢅꢅꢏꢇꢃꢀꢅꢅꢈꢏꢃꢀꢅꢌꢆꢆꢃꢀ
ꢅꢌꢏꢍꢃꢀꢅꢌꢋꢆꢃꢀꢅꢇꢌꢈꢃꢀꢅꢇꢏꢅꢃꢀꢅꢇꢋꢈꢃꢀꢅꢏꢊꢆꢃꢀꢅꢋꢅꢌꢃꢀꢅꢋꢇꢇꢃꢀꢌꢉꢊꢉꢃꢀꢌꢉꢇꢏꢃꢀꢌꢍꢉꢌꢃꢀꢇꢆꢅꢊꢃꢀꢇꢆꢇꢍꢃꢀꢇꢆꢈꢇꢃꢀꢇꢅꢅꢋꢀ
Qꢁꢎ&+ ꢀ
Qꢁꢎ&+ ꢀ
Qꢁꢎ& + ꢀ
ꢀ
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ꢌꢍꢌꢅꢃꢀꢌꢍꢇꢏꢃꢀꢌꢍꢋꢇꢃꢀꢇꢆꢏꢉꢃꢀꢇꢆꢈꢍꢃꢀꢇꢅꢅꢍꢀꢀ
ꢋꢆꢊꢃꢀꢋꢍꢍꢃꢀꢈꢌꢌꢃꢀꢉꢅꢆꢃꢀꢉꢍꢋꢃꢀꢍꢏꢊꢃꢀꢍꢋꢇꢃꢀꢍꢈꢉꢃꢀꢅꢆꢈꢉꢃꢀꢅꢅꢇꢌꢃꢀꢅꢌꢆꢏꢃꢀꢅꢇꢌꢆꢃꢀꢅꢇꢈꢍꢃꢀꢅꢏꢅꢇꢃꢀꢅꢏꢋꢈꢃꢀꢅꢋꢅꢆꢃꢀꢅꢋꢇꢊꢃꢀꢅꢋꢏꢍꢃꢀꢌꢉꢊꢊꢃꢀ
ꢌꢍꢌꢋꢃꢀꢌꢍꢊꢊꢃꢀꢇꢆꢅꢊꢀVKꢃꢀꢇꢆꢏꢋꢃꢀꢇꢆꢈꢋꢃꢀꢇꢅꢅꢉꢀꢀ
ꢋꢋꢉꢃꢀꢈꢌꢅꢃꢀꢉꢅꢆꢃꢀꢍꢏꢊꢃꢀꢍꢋꢇꢃꢀꢍꢍꢉꢃꢀꢅꢆꢋꢆꢃꢀꢅꢆꢈꢋꢃꢀꢅꢅꢇꢅꢃꢀꢅꢌꢆꢏꢃꢀꢅꢇꢌꢆꢃꢀꢅꢇꢈꢉꢃꢀꢅꢏꢋꢋꢃꢀꢅꢋꢆꢍꢃꢀꢅꢋꢇꢊꢃꢀꢅꢋꢏꢉꢃꢀꢌꢉꢊꢏꢃꢀꢌꢍꢌꢊꢃꢀꢌꢍꢋꢆꢀ
VKꢃꢀꢇꢆꢏꢋꢃꢀꢇꢆꢈꢍꢃꢀꢇꢅꢅꢉꢀ
Likewise, good results were obtained with cyclo-
of CsF–NaOH 20/20 mol%, 100°C, 5 h, initial pressure
16 at) gave rise to tert-butyl vinyl ether in a 8% yield at
25% conversion of t-BuOH. Alongside the tert-butyl
vinyl ether we found in the reaction mixture 2-vinyloxy-
hexanol as an example of secondary alcohols in reaction
carried out in DMSO at moderate temperature (100°C,
4–6 h) using the new catalyst CsF–NaOH in a quantity
1,3-butadiene arising by hydration trimerization of acety-
of 10–20 mol% (Table 2, run no. 8), whereas a compa-
rable preparative yield of vinyl cyclohexyl ether was at-
tained in the system KOH–DMSO under similar condi-
tions only at KOH concentration increased to 100 mol%
lene [8, 12].
EXPERIMENTAL
IR spectra of compounds synthesized were recorded
from thin films on a spectrometer Bruker JFS-25 in the
(Table 2, run no. 9).
When t-BuOH was subjected to vinylation in the sys-
tem CsF–NaOH–DMSO (atmospheric pressure, 10 mol%
of catalyst with respect to the alcohol, 100°C, 5 h) even
traces of tert-butyl vinyl ether were not detected. The
initial alcohol was recovered from the reaction mixture to
–1 1
region 400–4000 cm . H NMR spectra were registered
at room temperature on spectrometer Bruker DPX-400
at operating frequency 400.13 MHz, solvent CDCl , in-
3
ternal reference HMDS. The reaction mixtures were
analyzed by GLC on LKhM-80 instrument equipped with
katharometer, column 3000´3 mm, stationary phase
poly(ethylene glycol) 20000, 1% on NaCl, carrier gas
helium.
80%. The potentiometric titration revealed that no active
alkali remained in the reaction mixture, and the amount
of acetates formed corresponded to 81% conversion of
the initial sodium hydroxide. We believe that this pattern
of the process is due both to the hindrances to the forma-
tion of t-BuOCs (the tertiary alcohols because of their
low acidity difficultly react with alkali metals hydroxides
The alcohols used in the study were distilled, NaOH
was of “chemically pure” grade, CsF (Sigma-Aldrich)
and DMSO (Merck) were commercial reagents.
General procedure for vinylation of alcohols at
enhanced acetylene pressure. Into a rotating steel
reactor of 1 liter capacity was charged 300 mmol of
alcohol, NaOH and CsF in amounts indicated in Table 1,
and acetylene was supplied to the initial pressure of 10–
[17]) and to the basicity of medium getting higher than
the optimum value [18].As a result other processes domi-
nate, e.g., dehydration of the initial alcohol [19] and di-
rect synthesis of acetates from acetylene, water, and al-
kali metal hydroxides [20].
14 at. The reaction was carried out at stirring and heating
The vinylation of t-BuOH in the system CsF–NaOH–
DMSO under higher acetylene pressure (concentration
to 135–140°C for 1–3 h. The reaction products were dis-
tilled at atmospheric or reduced pressure depending on
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 5 2005

660
OPARINA et al.
the boiling point of the vinyl ether and were analyzed by
Other Natural Resources, New York, 1982, p. 140.
7. Trofimov, B.A., Geteroatomnye proizvodnye atsetilena.
Novye monomery reagenty i poluprodukty (Heteroatomic
Derivatives ofAcetylene), Moscw: Nauka, 1981, 319 p.
GLC. The yields of vinyl ethers ROCH=CH are given
2
in Table 1, their physicochemical and spectral character-
istics are presented in Table 3.
8
. Trofimov, B.A., Usp. Khim., 1981, vol. 50, p. 248.
. Trofimov, B.A., Z. Chem., 1986, vol. 26, p. 41.
0. Trofimov, B.A., Zh. Org. Khim., 1986, vol. 22, p. 1991.
1. Trofimov, B.A., Zh. Org. Khim., 1995, vol. 31, p. 1368.
General procedure for vinylation of alcohols at
atmospheric pressure of acetylene. Into a reaction
flask of 100 ml capacity, equipped with an efficient re-
flux condenser connected to a trap cooled to –60°C, ther-
mometer, magnetic stirrer, and a bubbler for supplying
acetylene was charged 50 ml of DMSO, 50 mmol of al-
cohol, NaOH and CsF in amounts indicated in Table 2,
9
1
1
1
2. Mikhaleva, A.I. and Gusarova, N.K., Atsetilen: reaktsii i
proizvodnye. Bibliografiya nauchnykh trudov B.A. Tro-
fimova (Acetylene: Reactions and Derivatives. Bibliogra-
phy of Scientific Publications of B.A. Trofimov) Novosibirsk:
Izd. Ros.Akad. Nauk, 1999, 231 p.
O
the content of the flask was heated to 100 C, and acety-
lene was flown through the mixture at a rate of 2 liter per
hour. The process was monitored by GLC. On comple-
tion of the synthesis the reaction mixture was diluted with
water (200 ml), the reaction product was extracted into
the ethyl ether (4´50 ml), the extract was washed with
water (3´20–30 ml), dried on K CO , combined with the
substance condensed in the trap (in case of low boiling
vinyl ethers), the solvent was removed on the rotary
evaporator, and the residue was distilled. The details of
experiments and the yields of vinyl ethers obtained are
compiled in Table 2.
1
3. Steinborn, D., Mosinski, H., Taube, R., Marschner, H., and
Bauer, J., German Patent 298775, 1990; Ref. Zh. Khim., 1993,
13N10P.
14. Steinborn, D., Mosinski, H., and Rosenstock, T.,
J. Organometal. Chem., 1991, vol. 414, p. 45.
15. Parshina, L.N., Oparina, L.A., Gorelova, O.V., Preiss, Th.,
Henkelmann, J., and Trofimov, B.A., Zh. Org. Khim., 2001,
vol. 37, p. 993.
2
3
16. Oparina, L.A., Parshina, L.N., Khil’ko, M.Ya., Gorelova, O.V.,
Preiss, Th., Henkelmann, J., and Trofimov, B.A., Zh. Org.
Khim., 2001, 37, p. 1629.
17. Holly, E.D., J. Org. Chem., 1959, vol. 24, p. 1752.
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).
18. Vasil’tsov, A.M., Trofimov, B.A., and Amosova, S.V., Izv.
Akad. Nauk SSSR, Ser. Khim., 1987, p. 1785.
1
9. Ustanovlenie struktury organicheskikh soedinenii
fizicheskimi i khimicheskimi metodami (Recognition of Or-
ganic Compounds Structure with Physical and Chemical
Methods). Moscow: Khimiya, 1967.
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21. Miller, S.A., Acetylene. Its Properties, Manufacture and
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RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 5 2005