Cleavage of different ether bonds in butyl glycidyl ether and allyl glycidyl ether by K-, K+ (15-crown-5)2

Article abstract of DOI:10.1016/S0022-328X(02)01801-6

The kind of substituent in alkyl glycidyl ethers affects the course of their reaction with K¹, K⁺ (15-crown-5)₂. The cyclic oxirane ring is exclusively cleaved in the case of butyl glycidyl ether whereas the presence of the unsaturated allyl group in the glycidyl ether molecule unexpectedly prefers the scission of the linear ether bond. In both the systems organometallic intermediates are formed. They react with crown ether causing its ring opening. Allylpotassium formed from allyl glycidyl ether reacts also with another glycidyl ether molecule; the oxirane ring is opened in this case.

Full text of DOI:10.1016/S0022-328X(02)01801-6

Journal of Organometallic Chemistry 660 (2002) 133Á138
/
www.elsevier.com/locate/jorganchem
Cleavage of different ether bonds in butyl glycidyl ether and allyl
glycidyl ether by Kꢀ, Kꢁ(15-crown-5)2
Zbigniew Grobelny a, Andrzej Stolarzewicz a,*, Adalbert Maercker b,
Stanis law Krompiec c, Tadeusz Bieg d
a Centre of Polymer Chemistry, Polish Academy of Sciences, 34, Marie Curie-Sklodowska Street, 41-819 Zabrze, Poland
b Institut fur Organische Chemie, Universitat Siegen, D-57068 Siegen, Germany
¨
¨
c Institute of Chemistry, Inorganic Technology and Electrochemistry, Silesian Technical University, 44-101 Gliwice, Poland
d Institute of Chemical Technology of Coal and Petroleum, Silesian Technical University, 44-101 Gliwice, Poland
Received 5 February 2002; received in revised form 29 July 2002; accepted 29 July 2002
Abstract
The kind of substituent in alkyl glycidyl ethers affects the course of their reaction with Kꢀ, Kꢁ(15-crown-5)2. The cyclic oxirane
ring is exclusively cleaved in the case of butyl glycidyl ether whereas the presence of the unsaturated allyl group in the glycidyl ether
molecule unexpectedly prefers the scission of the linear ether bond. In both the systems organometallic intermediates are formed.
They react with crown ether causing its ring opening. Allylpotassium formed from allyl glycidyl ether reacts also with another
glycidyl ether molecule; the oxirane ring is opened in this case.
# 2002 Published by Elsevier Science B.V.
Keywords: Potassium anions; Potassium alkalide; Glycidyl ethers
1. Introduction
propoxide and potassium phenoxide. Crown ether ring
opening occurred in a side reaction under the influence
of the organometallic intermediate. The process was
very fast at ambient temperature as it was already earlier
Glycidyl ethers,
, where R is an alkyl
or an aryl group, possess two kinds of ether bonds, i.e.
the cyclic and linear ones. Under basic conditions the
scission of the strained cyclic oxirane ring is preferred. A
nucleophile attacks its less hindered carbon atom and
the opening occurs in the b-position, i.e. between the
CH2 group and oxygen [1].
In our previous work [2] a system containing potas-
sium anions was used for the reaction with phenyl
glycidyl ether. Potassium alkalide Kꢀ, Kꢁ(15-crown-
5)2 (1) in tetrahydrofuran solution was selected for that
study. It was found that also in this case the cyclic ether
bond namely in the b-position was cleaved. An organo-
metallic intermediate was formed in this reaction. That
underwent g-elimination resulting in potassium cyclo-
observed using alkalide solutions [2Á4].
/
In the present work we describe results of further
investigations in this field. Glycidyl ethers possessing an
aliphatic substituent, i.e. butyl glycidyl ether and allyl
glycidyl ether were selected in this case. They were
model systems for our studies of the initiation step of
glycidyl ethers polymerization. The reaction conditions,
therefore, were the same as in the polymerization
process, i.e. glycidyl ethers were used in the excess in
relation to 1.
2. Results and discussion
The reaction of 1 with butyl glycidyl ether was
investigated in the first series of experiments. After
mixing of substrates the reaction mixture was treated
with benzyl bromide or methyl iodide to transform non-
volatile reaction products into volatile compounds. The
* Corresponding author. Tel.: ꢁ
/
48-32-271-6077; fax: ꢁ48-32-271-
/
2969
E-mail address: andrzej.stolarzewicz@cchp-pan.zabrze.pl (A.
Stolarzewicz).
0022-328X/02/$ - see front matter # 2002 Published by Elsevier Science B.V.
PII: S 0 0 2 2 - 3 2 8 X ( 0 2 ) 0 1 8 0 1 - 6

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Z. Grobelny et al. / Journal of Organometallic Chemistry 660 (2002) 133Á138
/
samples were then analyzed using preliminarily the gas
chromatographyÁmass spectrometry (GCÁMS) techni-
que.
assumed that in the first step of the reaction one electron
is transferred from Kꢀ of 1 to the oxirane ring of butyl
glycidyl ether (Scheme 1). Then, the oxirane ring is
opened in the b-position giving radical anion 3. It
presumably recombines with K0 forming an organome-
tallic alkoxide 4. The latter reacts with crown ether
causing its destruction. The final products involve two
potassium alkoxides, 5 and 6, and after benzylation their
benzylated derivatives, 7 and 8, respectively. No pro-
ducts of g-elimination of 4, i.e. potassium cycloprop-
oxide and potassium butoxide, were found in the
reaction mixture. As mentioned, such reaction was
observed in the case of phenyl glycidyl ether when the
resonance stabilized phenoxide anion was formed [2].
It is worth noting that the reaction of butyl glycidyl
ether with 1 in tetrahydrofuran solution was presented
already in [6]. Methanol was used as the quenching
agent in that case. The oxirane ring opening was
described to occur in the system resulting in the
organometallic alkoxide 4. However, the latter was
assumed to react with methanol giving 1-butoxy-2-
propanol found in the mixture after protonation. A
possibility of the crown ring cleavage was not taken into
account on that stage of investigations. Thus, the use of
protonation as the only quenching method can lead to
the assumption of a wrong reaction mechanism.
/
/
Two main signals were observed in the chromatogram
of the benzylated sample. They were identified as of 1-
butoxy-2-benzyloxypropane (in 20% yield) and tetra-
ethylene glycol benzyl vinyl ether (18%). It means that
potassium 1-butoxy-2-propoxide and potassium tetra-
ethylene glycoxide vinyl ether were the real reaction
products. The former was obtained by the oxirane ring
opening. The latter is known as the product of crown
ring opening by organometallic intermediates [3,4]. In
order to analyze side reaction products the reaction
mixture was treated with methyl iodide instead of benzyl
bromide. Tri- and tetraethylene glycol dimethyl ethers in
4% total yield were found in this case additionally. They
were formed in the methylated sample as a result of the
reaction occurring between 1 and potassium tetraethy-
lene glycoxide vinyl ether leading to dipotassium tri- and
tetraethylene glycoxides [3,4].
Potassium anion is known as two electron transfer
species reacting in two steps [5]. In the first one K0 is
obtained from Kꢀ. Then, after the transfer of the
second electron Kꢁ is finally formed. The same
mechanism was supposed in the present work. It was
The reaction of 1 with allyl glycidyl ether was studied
in the second series of experiments. Signals of 6-allyloxy-
5-benzyloxy-1-hexene (17%), benzyl glycidyl ether (19%)
and tetraethylene glycol benzyl vinyl ether (12%) were
observed as the main ones in the chromatogram of the
benzylated sample. It means that potassium alkoxide
with two double bonds and potassium glycidoxide as
well as potassium tetraethylene glycoxide vinyl ether was
formed in this process. Propylene (6.5 cm3) was found in
the liquid phase and in the gas phase before and after
benzylation. Signals of low intensities of triethylene and
tetraethylene glycol dimethyl ether present in the
chromatogram of the methylated sample has shown
that also in this case the side reactions occurred.
Potassium glycidoxide and propylene were assumed
to be the products of the linear ether bond scission in the
allyl glycidyl ether molecule. The presence of potassium
tetraethylene glycoxide vinyl ether showed the crown
ring opening [3,4]. Potassium 6-allyloxy-1-hexene-5-
oxide seemed to be the product of the oxirane ring
opening.
Thus, introduction of the allyl group into the glycidyl
ether molecule instead of the saturated one fundamen-
tally changes the course of the reaction with 1. The
cleavage of the linear ether bond takes place in this case
whereas the oxirane ring remains undisturbed. It is
suggested that initially one electron transfer occurs from
Kꢀ to the double bond of allyl glycidyl ether (Scheme
2). The neighboring linear ether bond is opened and
potassium glycidoxide 10 and an allyl radical 11 are
Scheme 1.

Z. Grobelny et al. / Journal of Organometallic Chemistry 660 (2002) 133Á
/138
135
Scheme 4.
Various results of allyl ethers cleavage were presented
till now in the literature. Angelo [7] found that the
reaction of sodium naphthalenide, i.e. one-electron-
transfer reagent, with allyl ethyl ether resulted in biallyl
(in 30% yield) as the main product. Ethanol was not
isolated. Biallyl (40%) and phenol (60%) were found in
the case of allyl phenyl ether. It was suggested that the
cleavage of the ether bond between the allyl carbon and
the oxygen atom took place in the first step of the
process and then allyl radicals formed underwent
dimerization giving biallyl. Biallyl was also obtained
by Weber [8] in the reaction of allyl methyl ether with
sodium, being another one-electron-transfer reagent [9],
in the presence of trimethylchlorsilane. The mechanism
of this reaction was not proposed. On the other hand,
Eisch [10] obtained allyllithium from allyl phenyl ether
Scheme 2.
formed. Then, 11 recombines with K0 giving allylpotas-
sium 12. It reacts with crown ether of 10 which results in
propylene 13 and potassium tetraethylene glycoxide
vinyl ether 6 with one crown ether in the complex
(Scheme 3). Allylpotassium reacts also with another allyl
glycidyl ether molecule (Scheme 4). The oxirane ring is
opened in this case in the b-position. It leads to
potassium alkoxide with two double bonds 15 and after
benzylation to its benzyl derivative 16. It should be
mentioned that potassium anions do not take part in
such a process. An expected product of the oxirane ring
opening by 1, i.e. potassium 1-allyloxy-2-propoxide, was
not observed in the reaction mixture.
using the excess of lithium in tetrahydrofuran at ꢀ
/
10 8C. However, Crandall [11] reported that allyl benzyl
ether under the influence of lithium in tetrahydrofuran
was cleaved to benzyllithium and lithium allyloxide.
Allyllithium was not observed in the reaction mixture.
In such a situation we decided to check the reaction of
1 with allyl phenyl ether selected as a model compound
and to confirm this way the reaction mechanism
suggested for allyl glycidyl ether. Propylene, benzyl
phenyl ether, and tetraethylene glycol benzyl vinyl ether
were found in this case in the benzylated reaction
mixture. Biallyl was not observed. It indicated that allyl
radicals formed initially did not dimerize but rather
recombined with K0 giving allylpotassium which then
reacted with crown ether (Scheme 5). It seems that the
rate of recombination is much faster then the rate of
dimerization. Therefore, the latter can not occur in the
presence of 1.
The reactions of organometallic compounds were very
fast, as it had been described already in our earlier
Scheme 3.
works [2Á4]. Their volatile derivatives were not observed
/

136
Z. Grobelny et al. / Journal of Organometallic Chemistry 660 (2002) 133Á138
/
case of saturated butyl substituent the oxirane ring is
exclusively opened in the glycidyl ether molecule. The
presence of the allyl group prefers the cleavage of the
linear ether bond. It results in the formation of
potassium alkoxide containing undisturbed oxirane
ring, i.e. potassium glycidoxide. The selective linear
ether bond scission in allyl glycidyl ether by 1 may be
explained by a greater tendency to receive the electron
by the unsaturated group rather than by the oxirane
ring.
15-Crown-5 plays a dual role in the studied systems. It
takes part in the occurring processes both as the
complexing agent and as the reagent. Its oxacyclic ring
is opened easily in the reactions with organometallic
intermediates. Potassium tetraethylene glycoxide vinyl
ether is the product of this reaction.
A mixture of potassium alkoxides is formed in both
series of experiments. It can be assumed that these
alkoxides can be the real initiators in the polymerization
of selected glycidyl ethers by potassium alkalide.
4. Experimental
GCÁMS analyses were run on a 30 m long DB 1701
/
fused silica capillary column, using a Varian 3300 gas
chromatograph equipped with a Finnigan MAT 800 AT
ion trap detector. Diethylene glycol dimethyl ether was
used as the internal standard for the yield measurement.
Gaseous products were searched for by gas chromato-
graphy (GC) with a 2.4 m long stainless steel column
packed with Al2O3, 0.2Á0.3 mm, deactivated with 5%
/
Scheme 5.
K2CO3, in an INCO 505 gas chromatograph equipped
with a flame ionization detector. 1H- and 13C-NMR
spectra were recorded at 20 8C on a Varian VXR-300
in benzylated or methylated samples in spite of the fact
that the reaction mixture was treated with benzyl
bromide or methyl iodide immediately after mixing of
reagents.
1
multinuclear pulsed spectrometer operating at the H
resonance frequency of 300 MHz, and the 13C resonance
frequency of 75 MHz. Chemical shifts were referenced
to tetramethylsilane serving as an internal standard for
1H and 13C measurements. Deuterated chloroform was
used as the solvent. Proton signals assignment was done
using a MestRe-C 2.3a spectrum simulator. Signals
assignment in the 13C spectra was done using a DEPT
and HETCOR correlation technique.
It is necessary to emphasize that in all experiments the
blue potassium alkalide solution was dropped into the
excess of glycidyl ethers. That resulted in low reaction
yields, however, only under such conditions the original
reaction products could be detected. In other cases, i.e.
at the excess of 1 or even at the molar ratio of reagents
close to 1:1, further reactions are expected to occur with
the participation of potassium anions [12]. A mixture of
various compounds can be finally formed and some-
times without the original reaction product or products.
Therefore, one may draw misleading conclusions con-
cerning the reaction mechanism.
Butyl glycidyl ether (Aldrich) and allyl glycidyl ether
(Aldrich) were heated over CaH2 for 6 h and then
distilled under dry argon atmosphere; the fractions
boiling at 165 and 154 8C were collected, respectively.
Allyl phenyl ether (Aldrich) was distilled at 192 8C and
used as a model compound. Tetrahydrofuran (POCH)
was boiled over CuCl to decompose peroxides, then over
CaH2 for 10 h, and finally it was distilled at 66 8C. This
fraction was dried over metallic potassium for 20 h and
redistilled prior to use. 15-Crown-5 (Aldrich) was dried
under vacuum at 50 8C for 8 h. Potassium (Fluka) was
purified in boiling tetrahydrofuran and then distilled
3. Conclusions
The course of the reaction of 1 with selected alkyl
glycidyl ethers depends on the kind of substituent. In the

Z. Grobelny et al. / Journal of Organometallic Chemistry 660 (2002) 133Á
/138
137
under high vacuum into a reactor described in [13]. Blue
solution (0.1 M) of Kꢀ, Kꢁ(15-crown-5)2 was obtained
by dissolution of the potassium mirror in 0.2 M 15-
crown-5 tetrahydrofuran solution at 25 8C as in [14].
The metalÁsolvent contact time was equal to 25 min.
/
The reaction of glycidyl ether with potassium anions
was conducted under dry argon atmosphere at 25 8C.
Ten cubic centimeter of 0.1 M Kꢀ, Kꢁ(15-crown-5)2
blue solution was dropped into 10 cm3 of 0.5 M butyl or
allyl glycidyl ether in tetrahydrofuran solution while
mixing, i.e. glycidyl ether was still at the excess. The
reaction was very fast. Potassium anions vanished
instantaneously in the system after mixing of reagents.
It was easy to observe during experiments because the
blue potassium solution becomes colorless at the same
time [13]. Then, the reaction mixture was immediately
treated with benzyl bromide or methyl iodide as the
quenching agent. The obtained compounds were identi-
fied by matching their mass spectra, retention times, and
NMR spectra with those of authentic compounds. The
reaction of allyl phenyl ether with Kꢀ, Kꢁ(15-crown-
5)2 and the analysis of its products were conducted at
the same conditions as for glycidyl ethers.
1H-NMR CDCl3 d 7.38Á
2H, PhÃCH2Ã); 3.669 (ddd, 1H, CH3Ã
Hz, Jꢂ6.2 Hz, Jꢂ4.8 Hz); 3.466 (dd, 1H, CH3Ã
CH2ÃOÃ, Jgem 9.9 Hz, Jꢂ6.2 Hz); 3.406 (t, 2H, Ã
OÃCH2ÃCH2ÃCH2ÃCH3, Jꢂ6.6 Hz); 3.337 (dd, 1H,
CH3ÃCHÃCH2ÃOÃ, Jgem 9.9 Hz, Jꢂ4.8 Hz); 1.544
(tt, 2H, ÃOÃCH2ÃCH2ÃCH2ÃCH3, Jꢂ7.0 Hz, Jꢂ
Hz); 1.367 (qt, 2H, ÃOÃCH2ÃCH2ÃCH2ÃCH3, Jꢂ
Hz, Jꢂ7.0 Hz); 1.160 (d, 3H, CH3ÃCHÃCH2ÃOÃ
/
7.17 (m, 5H, PhÃ
/
); 4.572 (s,
/
/
/
CH Ã
/
, Jꢂ
CHÃ
/
/
6.2
/
/
/
/
/
/
ꢂ
/
ꢀ
/
/
/
/
/
/
/
/
/
/
/
ꢂ
/
/
/
/
/
/
/
/
/6.6
/
/
/
/
/
/7.3
/
/
/
/
/
, Jꢂ
/
6.2 Hz); 0.906 (t, 3H, Ã
/
OÃ
/
CH2Ã
/
CH2Ã
/
CH2Ã
/
CH3, Jꢂ
/
7.3 Hz). MS m/z (%) 222 [Mꢁ, 6], 148 (40), 135 (12), 107
(30), 91 (100), 87 (10), 65 (15), 57 (78), 41 (17).
4.3. Tetraethylene glycol benzyl vinyl ether (8)
The method of its preparation as well as its H-, 13C-
NMR and mass spectra were described in [3].
1
4.1. 1-Butoxy-2-propanol
A mixture of 0.5 mol 1,2-propanediol, 0.1 mol 1-
bromobutane, 150 cm3 50% aqueous (aq.) NaOH, and
0.01 mol tetrabutylammonium hydrogensulfate has been
4.4. Benzyl glycidyl ether (12)
1
Its H- and 13C-NMR spectra were described in [15].
stirred and heated on a water bath for 3 h at 80Á90 8C.
/
MS m/z (%) 164 [Mꢁ, 25], 107 (86), 91 (100), 79 (64), 65
(43), 57 (18), 51 (18), 39 (18).
After cooling 100 cm3 hexane and 500 cm3 water has
been added. The layers have been separated, the organic
layer has been washed three times with 20 cm3 water and
dried with anhydrous MgSO4. The product has been
distilled and 1-butoxy-2-propanol was obtained in 80%
yield (purity 93%; contained 7% of 2-butoxy-1-propa-
4.5. 1-Allyloxy-5-hexen-2-ol
A mixture of 0.1mol 1,2-epoxy-5-hexene, 0.6 mol allyl
alcohol, 0.3 mol powdered NaOH and 0.01 mol tetra-
butylammonium hydrogensulfate has been intensively
nol). Boiling point (b.p.)ꢂ
/
169Á172 8C per 760 mmHg.
/
stirred in 50Á60 8C on a water bath for 3 h. After
/
cooling, 200 cm3 water and 100 cm3 hexane have been
added. The layers have been separated, the organic layer
has been washed three times with 20 cm3 of water and
dried with anhydrous MgSO4. Volatile constituents
(mostly hexane) have been removed by distillation on
a rotatory evaporator. The residue has been distilled
under reduced pressure. 1-Allyloxy-5-hexen-2-ol has
4.2. 1-Butoxy-2-benzyloxypropane (7)
A mixture of 0.1 mol 1-butoxy-2-propanol, 0.11 mol
benzyl chloride, 0.4 mol powdered NaOH, 0.01 mol
tetrabutylammonium hydrogensulfate, and 60 cm3 tol-
uene has been intensively stirred in 50Á60 8C on a water
/
bath for 3 h. After cooling 100 cm3 water and 100 cm3
hexane has been added. The layers have been separated,
the organic layer has been washed three times with 20
cm3 water and dried with anhydrous MgSO4. Having
removed hexane and toluene on a rotatory evaporator
the residue has been distilled under reduced pressure. 1-
Butoxy-2-benzyloxypropane has been finally obtained
in 75% yield (purity 95%; contained 5% 2-butoxy-1-
been obtained in 60% yield. B.p.ꢂ
/
59Á60 8C per 1
/
mmHg.
4.6. 6-Allyloxy-5-benzyloxy-1-hexene (16)
A mixture of 0.05 mol 1-allyloxy-5-hexen-2-ol, 0.55
mol benzyl chloride, 0.17 mol powdered NaOH, 0.005
mol tetrabutylammonium hydrogensulfate and 40 cm3
benzyloxypropane). B.p.ꢂ
/
106Á107 8C per 1 mmHg.
/
13C-NMR CDCl3 d:
toluene has been stirred intensively in 50Á60 8C on a
/

138
Z. Grobelny et al. / Journal of Organometallic Chemistry 660 (2002) 133Á138
/
water bath for 3 h. After cooling 100 cm3 water and 100
cm3 hexane have been added. The layers have been
separated, the organic layer has been washed three times
with 20 cm3 water and dried with anhydrous MgSO4.
Volatile constituents (mostly hexane and toluene) have
been removed by distillation on a rotatory evaporator.
The residue has been distilled under reduced pressure.
Finally, 6-allyloxy-5-benzyloxy-1-hexene has been ob-
4.7. Benzyl phenyl ether (19)
Its 1H-, 13C-NMR and mass spectra were described in
[2].
Tri- and tetraethylene glycol dimethyl ethers. Their
1H-, 13C-NMR and mass spectra were described in [3].
To the best of our knowledge two of these com-
pounds, i.e. 1-butoxy-2-benzyloxypropane (7) and 6-
allyloxy-5-benzyloxy-1-hexene (16) were till now not
described in the literature.
tained in 70% yield. B.p.ꢂ
/
118 8C per 1 mmHg. 13C-
NMR CDCl3 d:
Acknowledgements
The authors are indebted to Dr. G. Adamus and Dr.
K. Skutil for GC analysis of liquid and gaseous reaction
products. This work was supported by the Committee of
Scientific Research in Poland (project No. 3 TO9A 097
18).
1H-NMR CDCl3 d 7.38Á
1H, ÃOÃCH2ÃCH ÄCH2, Jꢂ
5.5 Hz); 5.771 (ddt, 1H, CH2Ä
16.8 Hz, Jꢂ10.2 Hz, Jꢂ6.6 Hz); 5.254 (dtd, 1H, Ã
OÃCH2ÃCHÄCH2-cis, Jꢂ17.2 Hz, Jꢂ1.4 Hz, Jꢂ
1.3 Hz); 5.142 (dtd, 1H, ÃOÃCH2ÃCHÄCH2-trans,
Jꢂ10.6 Hz, Jꢂ1.8 Hz, 1.3 Hz); 4.983 (dtd, 1H, cis-
CH2ÄCHÃCH2ÃCH2Ã, Jꢂ16.8 Hz, Jꢂ1.8 Hz, Jꢂ1.4
Hz); 4.931 (dtd, 1H, trans-CH2ÄCHÃCH2ÃCH2Ã, Jꢂ
10.2 Hz, Jꢂ1.8 Hz, 1.3 Hz); 4.664, 4.521 (qAB, 2H,
PhÃCH2Ã, JAB 11.7 Hz); 3.956 (ddd, 2H, ÃOÃCH2Ã
CHÄCH2, Jꢂ5.5 Hz, Jꢂ1.8 Hz, Jꢂ1.4 Hz); 3.557
(dddd, 1H, CH2ÄCHÃCH2ÃCH2ÃCH Ã, Jꢂ7.6 Hz,
Jꢂ5.8 Hz, Jꢂ4.5 Hz, Jꢂ4.3 Hz); 3.493 (dd, 1H, Ã
CHÃCH2ÃOÃ, Jgem 10.1 Hz, Jꢂ5.8 Hz); 3.438
(dd, 1H, ÃCHÃCH2ÃOÃ, Jgem 10.1 Hz, Jꢂ4.3
Hz); 2.183 (ddddd, 1H, CH2ÄCHÃCH2ÃCH2Ã
Jgem 14.7 Hz, Jꢂ6.8 Hz, Jꢂ6.6 Hz, Jꢂ1.8 Hz,
Jꢂ1.4 Hz); 2.100 (ddddd, 1H, CH2ÄCHÃCH2ÃCH2Ã
Jgem 14.7 Hz, Jꢂ7.3 Hz, Jꢂ6.6 Hz, Jꢂ1.8 Hz,
Jꢂ1.4 Hz); 1.634 (ddd, 1H, CH2ÄCHÃCH2ÃCH2Ã
Jgem 13.6 Hz, Jꢂ7.6 Hz, Jꢂ7.3 Hz); 1.611 (ddd,
1H, CH2ÄCHÃCH2ÃCH2Ã, Jgem 13.6 Hz, Jꢂ6.8
Hz, Jꢂ
4.5 Hz). MS m/z (%) 246 [Mꢁ, 2], 188 (2), 175
/
7.18 (m, 5H, PhÃ
17.2 Hz, Jꢂ
CH ÃCH2Ã
/
); 5.873 (ddt,
10.6 Hz, Jꢂ
CH2Ã, Jꢂ
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
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