Decomposition of vinyl ethers by alkalide K- K+ (15-crown-5)2 via organopotassium intermediates

Article abstract of DOI:10.1016/j.jorganchem.2004.02.004

The structure of vinyl ethers determines the direction of the C-O bond cleavage by alkalide K^-, K⁺(15-crown-5)₂ 1. Highly reactive organopotassium compounds are intermediate products formed in the system containing phenyl vinyl ether, butyl vinyl ether, ethylene glycol butyl vinyl ether or triethylene glycol methyl vinyl ether. Vinylpotassium and butylpotassium react with 15-crown-5. The oxacyclic ring of the latter is opened in this case. Organopotassium ethers possessing CH₂CH₂O units eliminate ethylene. It results in various potassium alkoxides. The reaction of 1 with butyl vinyl ether occurs very slow as compared to other vinyl ethers and most of other reagents used till now.

Full text of DOI:10.1016/j.jorganchem.2004.02.004

Journal of Organometallic Chemistry 689 (2004) 1580–1585
www.elsevier.com/locate/jorganchem
Decomposition of vinyl ethers by alkalide Kꢀ, Kþ(15-crown-5)2 via
organopotassium intermediates
a
a,
b
Zbigniew Grobelny , Andrzej Stolarzewicz *, Adalbert Maercker ,
c
d
Stanisław Krompiec , Janusz Kasperczyk , Jozef Rzepa
e
ꢀ
a
Institute of Materials Science, University of Silesia, Bankowa 12, 40-007 Katowice, Poland
b
Institut f€ur Organische Chemie, Universit€at Siegen, D-57068 Siegen, Germany
Department of Analytical and General Chemistry, Silesian University of Technology, 44-101 Gliwice, Poland
c
d
Chair of Molecular Biology, Biochemistry and Biopharmacy, Medical University of Silesia, 41-200 Sosnowiec, Poland
e
Institute of Chemistry, University of Silesia, 40-007 Katowice, Poland
Received 10 December 2003; accepted 6 February 2004
Abstract
The structure of vinyl ethers determines the direction of the C–O bond cleavage by alkalide Kꢀ, Kþ(15-crown-5)2 1. Highly
reactive organopotassium compounds are intermediate products formed in the system containing phenyl vinyl ether, butyl vinyl
ether, ethylene glycol butyl vinyl ether or triethylene glycol methyl vinyl ether. Vinylpotassium and butylpotassium react with 15-
crown-5. The oxacyclic ring of the latter is opened in this case. Organopotassium ethers possessing CH2CH2O units eliminate
ethylene. It results in various potassium alkoxides. The reaction of 1 with butyl vinyl ether occurs very slow as compared to other
vinyl ethers and most of other reagents used till now.
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: Vinyl ethers; Alkalide; Potassium anions; Organopotassium intermediates
1. Introduction
between the substituted carbon atom and oxygen or
between the CH2 group and oxygen, respectively. The
direction of the ether bond cleavage depended on the
kind of substituent. Unexpectedly, the scission of one of
the linear ether bonds was found in some oxiranes
possessing an oxygen atom in the substituent [7]. The
highly strained oxirane ring remained undisturbed. The
decomposition of cyclic ethers in a larger ring, e.g.,
18-crown-6 [13], 15-crown-5 [14], and their monocyclo-
hexano- and dicyclohexano-derivatives [15] was
observed under the influence of potassium anions in
tetrahydrofuran solution.
The use of alkalides for the ether bond cleavage
seemed to be an important area for organometallic
chemists. That led to the generation of new organopo-
tassium compounds being intermediate products in
those systems. They were generally unstable and un-
derwent various fast reactions, e.g., with crown ether or
with the substrate [16]. Some of them eliminate potas-
sium phenoxide [5] or unsaturated hydrocarbons, e.g.,
Alkalides, i.e. salts containing alkali metal anions and
complexed metal cations are excellent electron-transfer
reagents for the ether cleavage. Fish et al. [1] observed
the regioselectivity of the ether bond scission in aromatic
ethers using Kꢀ, Kþ(18-crown-6). Then, it was found
that the regioselective cleavage of the alkyl-oxygen bond
occurred also in methyl phenyl ether, ethyl phenyl ether
[2], and allyl phenyl ether [3] in their reactions with Kꢀ,
Kþ(15-crown-5)2 1. It was shown in further works that
various cyclic ethers as monosubstituted oxiranes [3–9],
oxetane [10–12] and tetrahydrofuran [13,14] can also be
opened by alkalides. The most interesting seemed to be
the reaction involving oxiranes. The oxacyclic ring was
opened in the a- [8,9] or in the b-position [3–6,9], i.e.
* Corresponding author. Tel.: +48-32-359-14-21; fax: +48-32-259-69-
29.
E-mail address: astolarzewicz@silesianet.pl (A. Stolarzewicz).
0022-328X/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.02.004

Z. Grobelny et al. / Journal of Organometallic Chemistry 689 (2004) 1580–1585
1581
ethylene [12,14] or cyclohexene [15]. Most of the reac-
tions mentioned above had been previously not
described in the literature.
However, there was a lack of information on the
behaviour of vinyl ethers under the influence of alkalide.
In this work, we present for the first time the results
concerning this problem. Phenyl vinyl ether, butyl vinyl
ether, ethylene glycol butyl vinyl ether, and triethylene
glycol methyl vinyl ether as well as 1 in tetrahydrofuran
solution were selected for the study.
vinylpotassium 3. It reacts with 15-crown-5 being in the
complex with potassium cation of 2. Potassium tetra-
ethylene glycoxide vinyl ether 5 is the product of the
reaction. A likely mechanism is that the vinylpotassium
species is behaving as a base and effecting an E2-like
elimination on the crown compound to provide the
alkoxide precursor 5 to benzyl ether 7. The cleavage of
the ether bond of phenyl vinyl ether in the a-position
was preferred probably due to the high resonance sta-
bility of the phenoxide anion. The same direction of the
C–O bond scission was described for that ether in the
presence of an excess of lithium powder and a catalytic
amount of 4,40-di-tert-butylbiphenylide (DTBB) in tet-
rahydrofuran at room temperature [17]. The reaction led
to the vinyllithium intermediate.
If the aromatic substituent in the vinyl ether molecule
has been replaced by an aliphatic one then Kꢀ transfers
one electron to the vinyl group giving K° and the cor-
responding radical anion. In this case, the ether bond
cleavage occurred in the b-position, i.e. between the
substituent and oxygen. Such a scission was observed in
butyl vinyl ether (R: Bu). Tetraethylene glycol benzyl
vinyl ether 7 (8%) and benzyl vinyl ether 11 (5%) were
found in the reaction mixture after treatment with
benzyl bromide. Butane was evolved during the reac-
tion. The proposed course of the process is presented in
Scheme 2. The b-scission in butyl vinyl ether is probably
due to the resonance stability of enolate anion of 8. It is
worth noting that potassium enolate of acetaldehyde 80
underwent exclusively O-benzylation giving benzyl vinyl
ether 11. The product of C-benzylation, i.e. 3-phenyl-
propionaldehyde was not detected. The formation of O-
alkylated product is not surprising when one considers
the hard nature of this metal enolate. Sodium enolates
are commonly employed to effect O-alkylation of eno-
lates and presumably potassium enolates will be equally
2. Results and discussion
The reaction of 1 with phenyl vinyl ether was con-
ducted in the first series of experiments. Two liquid
products, i.e. benzyl phenyl ether 6 (in 5% yield) and
tetraethylene glycol benzyl vinyl ether 7 (9%) were found
in the reaction mixture after treatment with benzyl
bromide as the quenching agent. Ethylene was evolved
during the reaction.
It was taken into account that the C–O bond in vinyl
ethers can be opened in two ways, called in this paper as
the a- or the b-opening:
CH2=CH__O__R
ð1Þ
α
β
The results showed that the ether bond in phenyl vi-
nyl ether (R: Ph) was cleaved exclusively in the a-posi-
tion, i.e. between the vinyl group and oxygen (Scheme
1). It was assumed that in the first step of the process Kꢀ
of 1 transfers one electron to the phenyl group giving K°
and a radical anion. The latter is unstable and decom-
poses by the homolytic cleavage to potassium phenoxide
2 and vinyl radical. Then, K° transfers the second elec-
tron to the radical, which results in the formation of
-
K-, K+
α-opening
K+
+
K˚
+
,
O
K
Ph
-
O
Ph
K-, K+
K˚
+
1
β-opening
,
Bu
K+
+
O
O
Bu
1
+ PhO-, K+
K˚
+
+
PhO-, K+
O-, K+
3
2
K˚
+
Bu +
O-, K+
BuK
+
2
8
9
8
O
, K+
-
O
O
O
+
PhO-, K+
2'
+
O-, K+
5
O
+
+
BuH
10
O-, K+
4
O
O
8'
O
O
BnBr
BnBr
5
BnBr
BnBr
O
O
PhOBn
OBn
O
6
7
OBn
OBn
O
O
O
11
7
K+
denotes K+(15-crown-5); the second crown ether molecule was omitted.
O
O
where
Scheme 1.
Scheme 2.

1582
Z. Grobelny et al. / Journal of Organometallic Chemistry 689 (2004) 1580–1585
good, if not better, at achieving this regioselectivity.
Unexpectedly, the reaction of 1 with butyl vinyl ether
studied in the present work was rather slow. It occurred
in about two hours whereas that with phenyl vinyl ether
was found to be instantaneously. The end of the reaction
was correlated with the discoloration of the reaction
mixture indicating the absence of Kꢀ.
OMe
O
O
O
K-, K+
+
1
-
-
,
OMe
O
O
O
OMe
O
O
O
K+
K+
K˚
+
,
K˚
+
Introduction of the CH2CH2O group or groups into
the vinyl ether molecule makes the process more com-
plex. Tetraethylene glycol benzyl vinyl ether 7 (6%),
benzyl vinyl ether 11 (2%), ethylene glycol benzyl butyl
ether 13 (4%), and benzyl butyl ether 16 (3%) are iden-
tified in the mixture benzylated after the reaction of 1
with ethylene glycol butyl vinyl ether (R: CH2CH2OBu).
On the other hand, 7 (5%), 11 (2%), triethylene glycol
benzyl methyl ether 18 (5%), and diethylene glycol
benzyl methyl ether 21 (4%) are found when triethylene
glycol methyl vinyl ether is used (R: (CH2CH2O)2-
CH2CH2OMe). Ethylene is evolved in both the cases.
These results suggest that the cleavage of the ether bond
occurs under the influence of metal anions in the b-
position and, rather unexpectedly, also in the a-position
in both the ethers (Schemes 3 and 4). The b-cleavage can
be connected with the resonance stability of the enolate
anion 8 as well as with the stabilisation of alkylpotas-
sium intermediates 14 and 19 by the oxygen atom or
α-opening
β-opening
OMe
O
OMe
O
O
K˚
+
+
K˚
+
+
-
+
O-, K+
, K
O
O
8
17
OMe
O
OMe
O
O-, K+
BnBr
+
+
19
K
K
8
O
O
O-, K+
3
17
-
O
OMe
O
O
O-, K+
OBn
O
+
+
OMe
O
O-, K+
11
4
5
O-, K+
O
O
20
17'
BnBr
BnBr
O
BnBr
OMe
OMe
OBn
18
O
O
OBn
O
7
O
21
OBn
O
O
Scheme 4.
OBu
K-, K+
+
atoms. The reason why the a-cleavage also takes place is
not clear. One possible explanation bases on the differ-
ence in the number of oxygen atoms in vinyl ether
molecules with and without CH2CH2O units. Some in-
teraction between two or more oxygen atoms and the
potassium cation, similar to those observed in glymes
[18], might be responsible for such phenomenon. For
example the presence of an additional oxygen atom in
the vicinity of the alkoxide group changes the activity of
lithium, sodium and potassium alkoxides in the poly-
merization of methyl methacrylate [19]. A similar effect
was found in the polymerization of styrene by
H(OCH2CH2)nOꢀ, Kþ, where n ¼ 1–5 [20]. The reac-
tion rate, and the molecular weight of polymers were
controlled by the number of oxygen atoms in the initi-
ator molecule.
1
O
-
,
OBu
O
-
,
OBu
O
K+
K+
K˚
+
K˚
+
α-opening
OBu
β-opening
K˚
+
+
K˚
+
O-, K+
+
OBu
O-, K+
8
12
OBu
OBu
-
+
-
12
+
, K
O
+
14
8
K
+
K
3
, K
O
BnBr
-
It is worth noting that in the case of ethylene glycol
butyl vinyl ether and triethylene glycol methyl vinyl
ether only the ether bonds neighbouring with the vinyl
group are opened by potassium anions. The remaining
ether bonds, i.e. CH2–O–CH2 and CH2–O–Bu or CH2–
O–Me are stable.
The mechanistic study indicated that in radical anions
of vinyl ethers containing the CH2CH2O unit or units
the cleavage of the ether bond occurring between the
vinyl group and oxygen is heterolytic and not homolytic
O
OBu
-
, K+
OBn
O
BuO-, K+
+
15
O
+
5
11
O-, K+
12'
4
O
O
BnBr
BnBr
BnBr
O
BuOBn
OBu
16
OBn
O
7
OBn
O
O
13
Scheme 3.

Z. Grobelny et al. / Journal of Organometallic Chemistry 689 (2004) 1580–1585
1583
whereas in phenyl vinyl ether the homolytic a-cleavage is
observed.
The organopotassium compounds formed as inter-
mediates, i.e. 3, 9, 14, and 19 underwent further fast
reactions. None of their benzylated derivatives were
detected in any of the systems studied. The compounds 3
and 9 reacted exclusively with the crown ether whereas
14 and 19, i.e. containing CH2CH2O sequences, de-
composed to appropriate potassium alkoxides with the
liberation of ethylene.
4. Experimental
Gaseous products were searched for by gas-chroma-
tography (GC) with a 2.4 m long stainless steel column
packed with Al2O3, 0.2–0.3 mm, deactivated with 5%
K2CO3, in an INCO 505 gas chromatograph equipped
with a flame ionization detector.
GC–MS analysis of liquids was performed on a 30-m
MDN 5S capillary column in a GC Trace 2000 gas
chromatograph equipped with a Finnigan Trace MS
detector. Diethylene glycol was used as an internal
standard for the yield measurements. The gaseous
compounds were determined with a Chromatron GCHF
chromatograph at ambient temperature on a 2-m metal
column filled with modified alumina. NMR spectra were
recorded in CDCl3 with a Varian Unity Inova spec-
The yields of reaction products were low, below 10%,
because the process was conducted using an excess of
vinyl ethers. That allowed us to avoid side reactions
between alkalide and primary reaction products. At the
excess of 1 further reactions take place with the partic-
ipation of potassium anions. It was reported [7] that in
such case some initial products were destroyed and
various new compounds were observed in the reaction
mixture. Therefore, that method of substrate delivery
might lead to erroneous conclusions concerning the re-
action mechanism.
In all the processes studied till now, the discoloration
of the blue alkalide solution was instantaneous after
mixing with the excess of the reagent. The reaction of
potassium anions was very fast at ambient temperature.
The exception to this rule was observed only by the
self-decomposition of potassium solutions. In that case
a slow reaction of potassium anions occurred with a
ligand, e.g. 18-crown-6 [13], 15-crown-5 [14], or their
cyclohexano derivatives [15], and with tetrahydrofuran
used as the solvent [13,14]. The next exception was
found in the present work for the reaction of Kꢀ,
Kþ(15-crown-5)2 with butyl vinyl ether. The question
why that reaction occurred during about 2 h whereas
the others were usually instantaneous remains
unanswered.
trometer (300 MHz for H and 75 MHz for 13C) at 20
1
°C. Chemical shifts are expressed in ppm downfield from
TMS. 2D-NMR spectroscopy heteronuclear chemical
shift correlation (HETCOR) and absolute value COSY
were used in correlation of the lines in NMR spectra.
HRMS were recorded on a Finnigan MAT 95 mass
spectrometer (Finnigan MAT GmbH, Bremen,
Germany).
Butyl vinyl ether, ethylene glycol butyl vinyl ether
and triethylene glycol methyl vinyl ether (all Aldrich)
were distilled over CaH2. The fractions boiling at 94, 70
°C/20 mm Hg, and 112 °C/10 mm Hg were collected,
respectively. A 0.1 M Kꢀ, Kþ(15-crown-5)2 tetrahy-
drofuran solution was prepared as described in [21].
The reaction was carried out in an apparatus de-
scribed in [4] under dry argon atmosphere at 20 °C. 0.1
M Kꢀ, Kþ(15-crown-5)2 dark blue tetrahydrofuran so-
lution (10 mL) was introduced into 0.5 M solution of
vinyl ether (10 mL) in tetrahydrofuran while mixing.
After discoloration the reaction mixture was treated
with benzyl bromide to transform non-volatile reaction
products into the volatile compounds. The latter were
then identified matching their retention times, mass
spectra, and NMR spectra with those of authentic
compounds.
3. Conclusions
The structure of vinyl ethers determines the direction
of the ether bond cleavage by alkalide Kꢀ, Kþ(15-
crown-5)2. Vinylpotassium and butylpotassium as in-
termediate products open the crown ether ring being in
the complex with the potassium cation. Organopotas-
sium compounds containing the CH2CH2O groups
eliminate ethylene forming potassium alkoxides. Po-
tassium enolate of acetaldehyde is one of the final
products in most of the studied systems. It undergoes
exclusively O-benzylation after treating with benzyl
bromide, i.e. it behaves rather as an alkoxide than as an
organopotassium compound. Surprisingly, the reaction
of alkalide with butyl vinyl ether is rather slow in
comparison to most reactions of potassium anions
known until now.
4.1. Phenyl vinyl ether
A mixture of 0.01 mol 2-bromoethyl phenyl ether,
0.01 mol 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and
tetrahydrofuran (10 mL) was vigorously stirred at 60 °C
for 6 h. After cooling pentane (10 mL) was added and
the mixture was left overnight at 0 °C. The salt precip-
itate was filtered off and washed with 10 mL of tetra-
hydrofuran and pentane mixture (1:1). Volatile fractions
were removed by distillation and phenyl vinyl ether was
obtained in practically quantitative yield (purity > 99%;
1
GC). B.p. ¼ 48–49 °C/12 mm Hg. Its MS data and H
and 13C NMR spectra (CDCl3) are presented in [22,23],
respectively.

1584
Z. Grobelny et al. / Journal of Organometallic Chemistry 689 (2004) 1580–1585
4.2. Benzyl vinyl ether (11)
hexane and benzene on a rotatory evaporator the resi-
due was distilled under reduced pressure. Triethylene
glycol benzyl methyl ether has been finally obtained in
70% yield as a novel compound (purity > 97%; GC).
B.p. ¼ 191 °C/2 mm Hg.
A mixture of 0.01 mol 2-bromoethyl benzyl ether,
0.01 mol 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and
tetrahydrofuran (10 mL) was vigorously stirred at 60 °C
for 8 h. After cooling pentane (10 mL) was added and
the mixture was left overnight at 0 °C. The salt precip-
itate was filtered off and washed with 10 mL of tetra-
hydrofuran and pentane mixture (1:1). Volatile fractions
were removed by distillation and benzyl vinyl ether was
obtained in practically quantitative yield (purity > 99%;
GC). B.p. ¼ 50–51 °C/16 mm Hg. MS; m/z (%): 134
(Mþ, 4), 116 (7), 105 (11), 91 (100), 77 (7), 65 (30), 51 (9),
39 (11). MS data were also presented in [24], and 1H and
13C NMR (CDCl3) spectra in [25].
1
2
3
4
5
6
7
PhCH2-O-CH2CH2-O-CH2CH2-O-CH2CH2-O-CH3
1H NMR (CDCl3): 7.40–7.20 (m, 5H, Ph), 4.56 (s,
2H, CH2-1), 3.70–3.60 (m, 10H, CH2-2,3,4,5,6), 3.48–
3.56 (m, 2H, CH2-7), 3.36 (s, 3H, CH3). 13C NMR:
138.14 (C-1, Ph), 128.25 (Cmeta, Ph), 127.58 (Cortho, Ph),
127.47 (Cpara, Ph), 78.06 (CH2-1), 71.79 (CH2-7), 70.49
(CH2-2,3,4), 70.39 (CH2-5), 69.27 (CH2-6), 58.88 (CH3).
MS, m/z (%): 254 (Mþ, 2), 195 (2), 148 (14), 133 (14),
120 (6), 105 (12), 92 (100), 77 (10), 72 (7), 65 (24), 59
(92), 45 (25), 39 (7). HRMS (EI, 70 eV) calcd. for
C14H22O4 [Mþ] 254, 1518. Found 254, 1515.
4.3. Ethylene glycol benzyl butyl ether (13)
A mixture of 0.1 mol ethylene glycol monobutyl
ether, 0.11 mol benzyl chloride, 50% NaOH (60 mL),
0.005 mol tetrabutylammonium hydrogensulfate, and
benzene (50 mL) was vigorously stirred in 70–80 °C on a
water bath for 3 h. After cooling, water (100 mL) and
hexane (100 mL) were added. The layers were separated,
the organic layer has been washed with water (3 ꢁ 50
mL) and dried with anhydrous MgSO4. Having re-
moved hexane and benzene on a rotatory evaporator the
residue has been distilled under reduced pressure. Eth-
ylene glycol benzyl butyl ether was finally obtained in
88% yield as a novel compound (purity > 97%; GC).
B.p. ¼ 161–162 °C/2 mm Hg.
4.5. Diethylene glycol benzyl methyl ether (21)
A mixture of 0.1 mol diethylene glycol monomethyl
ether, 0.11 mol benzyl chloride, 50% NaOH (60 mL),
0.005 mol tetrabutylammonium hydrogensulfate, and
benzene (50 mL) was vigorously stirred at 70–80 °C on a
water bath for 3 h. After cooling, water (100 mL) and
hexane (100 mL) were added. The layers were separated,
the organic layer was washed with water (3 ꢁ 50 mL)
and dried with anhydrous MgSO4. Having removed
hexane and benzene on a rotatory evaporator the resi-
due was distilled under reduced pressure. Diethylene
glycol benzyl methyl ether was finally obtained in 80%
1
2
3
4
5
6
7
PhCH2-O-CH2CH2-O-CH2CH2CH2CH3
1H NMR (CDCl3): 7.40–7.20 (m, 5H, Ph), 4.57 (s,
2H, CH2-1), 3.60–3.62 (m, 4H, CH2-2,3), 3.47 (t, J ¼
6.7 Hz, 2H, CH2-4), 1.62–1.52 (m, 2H, CH2-5), 1.43–
1.30 (m, 2H, CH2-6), 0.92 (t, J ¼ 7.2 Hz, 3H, CH3). 13
C
NMR: 138.26 (C-1, Ph), 128.25 (Cmeta, Ph), 127.64
(Cortho, Ph), 127.46 (Cpara, Ph), 73.14 (CH2-1), 71.14
(CH2-4), 70.07 (CH2-3), 69.35 (CH2-2), 31.66 (CH2-5),
19.21 (CH2-6), 13.86 (CH3). MS, m/z (%): 208 (Mþ, 25),
151 (3), 134 (4), 117 (6), 107 (19), 91 (100), 73 (17), 55
(14), 57 (43), 41 (15). HRMS (EI, 70 eV) calcd. for
C13H20O2 [Mþ] 208, 1463. Found 208, 1464.
4.4. Triethylene glycol benzyl methyl ether (18)
A mixture of 0.1 mol ethylene glycol monobutyl
ether, 0.11 mol benzyl chloride, 50% NaOH (60 mL),
0.006 mol tetrabutylammonium hydrogensulfate, and
benzene (50 mL) was vigorously stirred at 70–80 °C on a
water bath for 3 h. After cooling, water (100 mL) and
hexane (100 mL) were added. The layers were separated,
the organic layer was washed with water (3 ꢁ 50 mL)
and dried with anhydrous MgSO4. Having removed
Fig. 1. 2D-NMR HETCOR (H, C) spectrum of diethylene glycol
benzyl methyl ether (21) – methylene region.

Z. Grobelny et al. / Journal of Organometallic Chemistry 689 (2004) 1580–1585
1585
[3] Z. Grobelny, A. Stolarzewicz, A. Maercker, S. Krompiec, T. Bieg,
J. Organomet. Chem. 660 (2002) 133.
yield as
B.p. ¼ 163 °C/2 mm Hg.
a novel compound (purity > 97%; GC).
[4] Z. Grobelny, A. Stolarzewicz, M. Czaja, W. Demuth, A.
Maercker, J. Org. Chem. 64 (1999) 8990.
1
2
3
4
5
PhCH2-O-CH2CH2-O-CH2CH2-O-CH3
[5] Z. Grobelny, A. Stolarzewicz, A. Maercker, W. Demuth, J.
Organomet. Chem. 590 (1999) 153.
1H NMR (CDCl3): 7.40–7.20 (m, 5H, Ph), 4.56 (s,
2H, CH2-1), 3.60–3.65 (m, 6H, CH2-2,3,4), 3.52–3.57
(m, 2H, CH2-5), 3.37 (s, 3H, CH3). 13C NMR: 138.13
(C-1, Ph), 128.21 (Cmeta, Ph), 127.60 (Cortho, Ph), 127.43
(Cpara, Ph), 73.09 (CH2-1), 71.81 (CH2-5), 70.53 (CH2-
2), 70.42 (CH2-3), 69.28 (CH2-4), 58.90 (CH3) (Fig. 1).
MS, m/z (%): 210 (Mþ, 6), 134 (25), 107 (15), 91 (100),
76 (39), 59 (83), 45 (41). HRMS (EI, 70 eV) calcd. for
C12H18O3 [Mþ] 210, 1256. Found 210,1252.
_
[6] Z. Grobelny, A. Stolarzewicz, B. Morejko-Buz, G. Buika,
ꢁ
ꢁ
J.V. Grazulevicius, A. Maercker, Eur. Polym. J. 38 (2002)
2359.
_
[7] Z. Grobelny, A. Stolarzewicz, B. Morejko-Buz, A. Maercker, J.
Organomet. Chem. 660 (2002) 6.
[8] Z. Grobelny, A. Stolarzewicz, B. Morejko-Buz_, A. Maercker, S.
Krompiec, T. Bieg, J. Organomet. Chem. 672 (2003) 43.
_
[9] Z. Grobelny, A. Stolarzewicz, B. Morejko-Buz, A. Maercker, Eur.
Polym. J. 40 (2004) 409.
ꢀ
[10] Z. Jedlinski, A. Misiołek, A. Jankowski, H. Janeczek, J. Chem.
Soc., Chem. Commun. (1991) 1513.
ꢀ
[11] Z. Jedlinski, A. Misiołek, A. Jankowski, H. Janeczek, J. Organo-
met. Chem. 433 (1992) 231.
4.6. Benzyl butyl ether (16), benzyl phenyl ether (6), and
tetraethylene glycol benzyl vinyl ether (7)
[12] Z. Grobelny, A. Stolarzewicz, A. Maercker, J. Organomet. Chem.
604 (2000) 283.
ꢀ
[13] Z. Jedlinski, A. Stolarzewicz, Z. Grobelny, Makromol. Chem. 187
(1986) 795.
Their GC–MS and NMR spectra have been reported
in [6,7,14], respectively.
[14] Z. Grobelny, A. Stolarzewicz, A. Maercker, J. Organomet. Chem.
628 (2001) 65.
_
[15] Z. Grobelny, A. Stolarzewicz, B. Morejko-Buz, R.A. Bartsch, K.
Yamato, F.A. Fernandez, A. Maercker, J. Org. Chem. 67 (2002)
7807.
Acknowledgements
[16] Z. Grobelny, J. Organomet. Chem. 677 (2003) 188.
[17] A. Bachki, F. Foubelo, M. Yus, Tetrahedron Lett. 39 (1998)
7759.
The authors are gratefully indebted to Dr. Marek
Sochacki, Mass Spectrometry Facility, Centre of Mo-
lecular and Macromolecular Studies, Polish Academy of
[18] M. Szwarc (Ed.), Ions and Ion Pairs in Organic Reactions, vols. 1
and 2, Wiley-Interscience, New York, 1972, 1974.
[19] M. Tomoi, K. Sekiya, H. Kakiuchi, Polym. J. 6 (1974) 438.
[20] A. Stolarzewicz, M. Czaja, D. Neugebauer, Polymer 41 (2000)
7865.
ꢀ ꢀ
Sciences, Łodz, Poland, for the HRMS measurements,
and to Dr. Krzysztof Skutil, Faculty of Chemistry,
Silesian University of Technology, for GC analysis of
gaseous products.
ꢀ
[21] Z. Grobelny, A. Stolarzewicz, M. Sokoł, J. Grobelny, H.
Janeczek, J. Phys. Chem. 96 (1992) 5193.
[22] E. Ellison, R. Kotsonis, J. Org. Chem. 38 (1973) 4192.
[23] R.A. Aitken, P.K.G. Hodgson, J.J. Morrison, A.O. Oyewale, J.
Chem. Soc. Perkin Trans. 1 (2002) 402.
References
[24] J.M. Dickinson, J.A. Murphy, C.W. Patterson, N.F. Wooster, J.
Chem. Soc. Perkin Trans. 1 (1990) 1179.
[1] R.H. Fish, J.W. Dupon, J. Org. Chem. 53 (1988) 5230.
[2] A. Stolarzewicz, Z. Grobelny, M. Kowalczuk, J. Organomet.
Chem. 492 (1995) 111.
~
[25] M.A. Sierra, J.C. del Amo, M.J. Mancheno, M. Gomez-Gallego,
ꢀ
J. Am. Chem. Soc. 123 (2001) 581.