Synthesis of vinyl phenyl ether and its use for ammetric titration of silver(I)

Article abstract of DOI:10.1023/A:1016123628083

Catalytic vinylation of phenol with acetylene at atmospheric pressure was studied. The yield of vinyl phenyl ether was determined as influenced by the solvent, reaction temperature, and catalyst amount. The mechanism of formation of vinyl phenyl ether was proposed. Ammetric titration of silver(I) with a solution of vinyl phenyl ether in nonaqueous acetic acid solutions was performed.

Full text of DOI:10.1023/A:1016123628083

Russian Journal of Applied Chemistry, Vol. 75, No. 3, 2002, pp. 480 482. Translated from Zhurnal Prikladnoi Khimii, Vol. 75, No. 3,
2002, pp. 491 493.
Original Russian Text Copyright
2002 by Nurmanov, Gevorgyan, Matmuratov, Kasimova, Sirlibaev, Kalyadin.
MACROMOLECULAR CHEMISTRY
AND POLYMERIC MATERIALS
Synthesis of Vinyl Phenyl Ether and Its Use
for Ammetric Titration of Silver(I)
S. E. Nurmanov, A. M. Gevorgyan, Sh. A. Matmuratov, O. Kasimova,
T. S. Sirlibaev, and V. G. Kalyadin
National University of Uzbekistan, Tashkent, Uzbekistan
Received August 16, 2001
Abstract Catalytic vinylation of phenol with acetylene at atmospheric pressure was studied. The yield of
vinyl phenyl ether was determined as influenced by the solvent, reaction temperature, and catalyst amount.
The mechanism of formation of vinyl phenyl ether was proposed. Ammetric titration of silver(I) with a solu-
tion of vinyl phenyl ether in nonaqueous acetic acid solutions was performed.
It is known [1, 2] that vinyl derivatives are widely
used as monomers, cross-linking agents, pharmaceu-
ticals, etc.. Among them vinyl ethers are the most
used, since are synthesized from readily available
reagents by simple procedures. Preparation of vinyl
ethers by vinylation at atmospheric pressure was
studied insufficiently.
_
+
K
HC HC
_
_
... ...
C6H5O H C
C6H5OK
C6H5O
CH
H
C6H5O
C
CH
C6H5 O CH =CH
_
C H OH
In this work we studied vinylation of phenol with
acetylene at atmospheric pressure and different tem-
peratures in different solvents in the presence of KOH
as catalyst. This reaction was performed in benzene,
water, and dimethyl sulfoxide (DMSO) (Table 1). In
benzene, no vinyl phenyl ether (VPE) was formed,
since this solvent is low-polar, has low boiling point,
and does not dissolve the catalyst. In water, the VPE
yield is low.
6
5
C6H5O CH=CH2 + C6H5O .
Thus, the VPE yield increases with increase in the
dielectric constant and basicity of the solvent.
Since the solubility of gases in liquids decreases
with increasing temperature, we studied the tempera-
ture dependence of the VPE yield in the presence
of various amounts of KOH (3 15 wt % relative to
phenol) (Table 2).
In DMSO, KOH DMSO separated ion pairs are
formed, which increases the basicity of the solvent.
Phenol transforms into readily dissociating potassium
phenolate, which promotes vinylation.
As seen from Table 2, no VPE is formed at tem-
peratures below 75 C. At 95 100 C the yield is 17
19%, and at 145 150 C it reaches a maximum of
25 32%.
+ CH3
H3C
CH3
_
The structure of VPE was confirmed by IR spec-
troscopy and by its physicochemical parameters which
coincided with the published values.
+
K+OH
+
S
K+
O
S
OH ,
_
CH3
O
Separated ion pair
Thus, synthesis of PVE at atmospheric pressure
CH3
_
Table 1. Yield of VPE as influenced by the solvent (KOH
catalyst : phenol weight ratio 0.1)
_
C6H5OH + K+
O
O
S
OH
+
CH3
CH3
Solvent
T,
C
VPE yield, %
Benzene
H2O
DMSO
76 79
95 100
95 100
C6H5OK +
S H2O,
CH3
Traces
17 19
1070-4272/02/7503-0480$27.00 2002 MAIK Nauka/Interperiodica

SYNTHESIS OF VINYL PHENYL ETHER AND ITS USE
481
should be performed in DMSO at 145 150 C and the
catalyst (KOH) : phenol weight ratio of 0.15.
Table 2. Yield of vinyl phenyl ether in DMSO as in-
fluenced by temperature and catalyst amount
Vinyl ethers are widely used as biologically active
compounds in various branches of science, medicine,
and agriculture [3]. However, no data are reported on
analytical application of VPE. Its analogs are used as
analytical reagents [4]; in this connection, we tested
VPE as a titrating agent for determining various metal
ions in nonaqueous and mixed solvents. For this pur-
pose, we determined electrochemical properties of
VPE.
cKOH, wt % relative
T,
C
VPE yield, %
to phenol
10
10
10
10
10
3
75 80
95 100
Traces
17 19
23
31
26
9
25
32
120 125
145 150
155 160
145 150
145 150
145 150
5
15
Previously we found [5] that metal cations can be
selectively titrated with VPE solutions in glacial
acetic acid and its mixtures with various inert non-
aqueous solvents (chloroform, tetrachloromethane,
hexane, benzene, dioxane, methyl ethyl ketone, hep-
tane, etc.). The equivalence point (EP) was determined
ammetrically with a platinum working electrode.
-naphthylamide) were added. The resulting solution
was stirred for 10 min and then silver(I) was extracted
for 1 2 min with two 5-ml portions of chloroform [9].
To the combined extract placed in a titration vessel,
glacial acetic acid (5 ml) was added. The solution was
heated to boil and Thionalidate silver complex was
decomposed by adding a saturated solution (30
40 drops) of potassium permanganate or chromium
trioxide in glacial acetic acid until the solution be-
came yellow brown. Then 0.2 M solution (5 ml) of
lithium chloride or lithium perchlorate in glacial
acetic acid was added. The mixture was heated for
several minutes to reduce completely colloidal man-
ganese dioxide to Mn(II) [or Cr(IV) to Cr(III)] and
Ag(I) to Ag(0), which was judged by decolorization
of the solution. The solution was cooled to room tem-
perature and was ammetrically titrated by the proce-
dure in [6] with a standard (c = 0.0001 0.002 M)
VPE solution using two platinum working electrodes.
This procedures can be used for determining metal
ions in extracts formed in analysis of multicomponent
inorganic materials and in organic materials readily
soluble in nonaqueous and mixed solvents.
Preliminary experiments on titration of silver(I),
mercury(II), palladium(II), platinum(IV), and other
metals with VPE solutions in glacial acetic acid and
its mixtures with inert solvents [6, 7] confirmed our
assumptions about the shape of the titration curves
and the accuracy of the analysis. Complexes of these
metals with VPE are sufficiently soluble in nonaque-
ous and mixed solvents. In all cases the EP deter-
mined by extrapolation of the straight line sections of
the titration curves to their intersection corresponds to
formation of 1 : 1 and 2 : 1 complexes of the titrating
agent with monovalent and bivalent metal cations, re-
spectively. This was also confirmed by electro-
chemical and optical methods and by NMR spec-
troscopy [8].
The results of silver(I) determination in five dif-
ferent artificial mixtures simulating natural and in-
dustrial objects are presented in Table 3. Statistical
treatment of these data [10] shows that the procedure
proposed allows reliable and selective determination
of silver with a high accuracy.
+
To determine Ag in the presence of large amounts
of elements interfering with its determination and
usually present in tested minerals, jewelries, alloys,
and other objects, we proposed a procedure based on
CONCLUSIONS
+
extractive separation of Ag ions with subsequent
ammetric titration of these anions in the extract with
VPE.
(1) The best conditions (15% KOH, DMSO, 145
150 C) for preparing vinyl phenyl ether by reaction of
phenol with acetylene at atmospheric pressure were
determined.
An aliquot of a test solution containing no more
than 200 mmol of Ag(I) was placed in a separatory
funnel and acidified with HClO and HCl to the con-
centration of about 0.2 M. A 0.1 M solution of ethyl-
(2) A procedure was developed for determining
Ag in systems simulating real objects by ammetric
4
+
enediaminetetraacetic acid disodium salt (5 ml) titration with a solution of vinyl phenyl ether in non-
and 1% solution of Thionalide (thioglycolic acid aqueous and mixed solvents.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 75 No. 3 2002

482
NURMANOV et al.
Table 3. Results of ammetic titration of silver(I) extracted from model systems
Found Ag+, mg
(P = 0.95, x X)
Mixture composition, mg
n
S
Sr 102
Ag, 0.15 + Au, 0.56 + Co, 20.3 + Pt, 1.39
Ag, 0.15 + Rh, 1.04 + Pd, 5.42 + Os, 3.47
Ag, 0.15 + Ru, 2.56 + Ni, 40.5 + Bi, 30.6
Ag, 0.15 + Fe, 50.7 + Ir, 0.78 + Ni, 20.9
Ag, 0.15 + Co, 40.6 + Fe, 25.3 + Pt, 2.78
0.16 0.01
0.15 0.02
0.15 0.02
0.16 0.001
0.15 0.02
3
4
4
4
5
0.008
0.101
0.009
0.012
0.007
5.1
6.7
5.9
8.0
4.5
* P is the confidence probability, x is the average value, X is the confidence interval, n is the number of parallel measurements,
S is the standard deviation, and S is the relative standard deviation.
r
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RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 75 No. 3 2002