Vinyl ethers containing an epoxy group: XXII. Synthesis and base-catalyzed transformations of 1-(allyloxy)- and 1-[2-(vinyloxy)ethoxy]-3-(2-propynyloxy) propan-2-ols

Article abstract of DOI:10.1007/s11178-005-0362-0

Reactions of 2-(allyloxymethyl)- and 2-[2-(vinyloxy)ethoxy]methyloxiranes with 2-propynol (-3 wt % of t-BuOK, 75-85°C, 5-10 h) lead to formation of new 1-organyloxy-3-(2-propynyloxy)propan-2-ols (yield 65-95%). On heating to 45-100°C in the presence of bases (KOH, t-BuOK), 1-allyloxy- and 1-[2-(vinyloxy)ethoxy]-3-(2-propynyloxy)propan-2-ols are transformed into the corresponding 2-vinyl-1,3-dioxolane, 6-methyl-2,3-dihydro-1,4-dioxine, 6-methylene-1,4-dioxane, and 2,3-dihydro-5H-1,4-dioxepine derivatives, whose yield and ratio strongly depend on the solvent nature, catalyst, and substituent at the hydroxy group. 2-Vinyl-1,3-dioxolane and 6-methyl-2,3-dihydro-1,4- dioxine derivatives are formed as the major products (yield 70-99%) in the presence of t-BuOK in aprotic media (toluene, THF, DMSO) or in the absence of a solvent as a result of prototropic isomerization followed by intramolecular heterocyclization. Intramolecular nucleophilic cyclization of 3-(2-propynyloxy)propan-2-ols to 6-methylene-1,4-dioxane is the predominant process in water in the presence of KOH. In all cases, the fraction of 2,3-dihydro-5H-1,4-dioxepine derivatives among the cyclization products ranges from 0 to 5% (KOH) or to 14% (t-BuOK).

Full text of DOI:10.1007/s11178-005-0362-0

Russian Journal of Organic Chemistry, Vol. 41, No. 10, 2005, pp. 1430–1444. Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 10, 2005,
pp. 1462–1476.
Original Russian Text Copyright © 2005 by Dmitrieva, Nikitina, Albanov, Nedolya.
Vinyl Ethers Containing an Epoxy Group:
XXII.* Synthesis and Base-Catalyzed Transformations
of 1-(Allyloxy)- and 1-[2-(Vinyloxy)ethoxy]-3-(2-propynyl-
oxy)propan-2-ols
L. L. Dmitrieva, L. P. Nikitina, A. I. Albanov, and N. A. Nedolya
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: nina@irioch.irk.ru
Received October 29, 2003
Abstract—Reactions of 2-(allyloxymethyl)- and 2-[2-(vinyloxy)ethoxy]methyloxiranes with 2-propynol
(~3 wt % of t-BuOK, 75–85°C, 5–10 h) lead to formation of new 1-organyloxy-3-(2-propynyloxy)propan-2-ols
(yield 65–95%). On heating to 45–100°C in the presence of bases (KOH, t-BuOK), 1-allyloxy- and 1-[2-(vinyl-
oxy)ethoxy]-3-(2-propynyloxy)propan-2-ols are transformed into the corresponding 2-vinyl-1,3-dioxolane,
6-methyl-2,3-dihydro-1,4-dioxine, 6-methylene-1,4-dioxane, and 2,3-dihydro-5H-1,4-dioxepine derivatives,
whose yield and ratio strongly depend on the solvent nature, catalyst, and substituent at the hydroxy group.
2-Vinyl-1,3-dioxolane and 6-methyl-2,3-dihydro-1,4-dioxine derivatives are formed as the major products
(yield 70–99%) in the presence of t-BuOK in aprotic media (toluene, THF, DMSO) or in the absence of
a solvent as a result of prototropic isomerization followed by intramolecular heterocyclization. Intramolecular
nucleophilic cyclization of 3-(2-propynyloxy)propan-2-ols to 6-methylene-1,4-dioxane is the predominant
process in water in the presence of KOH. In all cases, the fraction of 2,3-dihydro-5H-1,4-dioxepine derivatives
among the cyclization products ranges from 0 to 5% (KOH) or to 14% (t-BuOK).
Base-catalyzed intramolecular cyclizations of
Ȧ-(2-propynyloxy)- [2–8], Ȧ-(2-propynylsulfanyl)- [9],
and Ȧ-(2-propynylamino)alkan-1-ols [10, 11], as well
as of their 2-haloallyl analogs [4, 5, 9], have been
studied in sufficient detail. Such cyclizations (which
involve intramolecular nucleophilic addition of func-
tional group at the acetylenic triple bond) are among
the most widespread reactions leading to five-, six-,
or seven-membered heterocycles containing one or
two heteroatoms (N, O, S) [8, 12, 13]. However, in
the series of Ȧ-(2-propynyloxy)alkan-1-ols, only
2-(2-propynyloxy)ethanol and its simplest derivatives
R1CŁCC(R2)(R3)OCH(R4)CH(R5)OH (R1 = R2 = R3 =
R4 = R5 = H [3, 4, 7]; R1 = R2 = R3 = R4 = H, R5 = Me,
Ph; R1 = R2 = R3 = R5 = H, R4 = Ph; R1 = R2 = R3 = H,
R4 = R5 = Me [3, 6]; R1 = R2 = R4 = R5 = H, R3 = Me
[7]; R1 = R4 = R5 = H, R2 = Me, R3 = Ph [8]; R1 = R2 =
R4 = H, R3 = R5 = Me [3, 6, 7]; R1 = Me, R2 = R3 =
R4 = R5 = H [7]), 3-(2-propynyloxy)propan-1-ol [5],
2-(2-propynyloxy)cyclopentanol [7], and 2-(2-propyn-
yloxy)cyclohexanol [3, 6, 7] were studied.
Obviously, introduction of additional reaction cen-
ters, e.g., olefinic fragments with qualitatively different
chemical natures of the double carbon–carbon bonds
(specifically vinyloxy and allyloxy groups), into
(2-propynyloxy)alkanol molecules should strongly
extend the synthetic potential of both initial alkanols
[1–8, 12] and their cyclization products [1, 8, 14], as
well as the range of their useful properties and the
scope of practical application. Known representatives
of this class of compounds are used in various fields
(see, e.g., references in [1]), including the synthesis of
dendrimers, dienes, Į-hydroxy and Į-oxo acids, Į-hy-
droxymethyl ketones, Į,Į'-dihydroxy ketones, poly-
cyclic compounds (via functionalization or transforma-
tions of 1,4-dioxines) [15], and enediyne antibiotics
(through key intermediates containing 2-vinyl-1,3-di-
oxolane fragments) [16]. In turn, the synthetic and
practical significance of vinyl and allyl ethers and
materials based thereon is so high that even the most
* For communication XXI, see [1].
1070-4280/05/4110-1430 © 2005 Pleiades Publishing, Inc.

VINYL ETHERS CONTAINING AN EPOXY GROUP: XXII.
1431
important fields of their application could not be listed
in the framework of the present article. Among these,
preparation of unique polymers and copolymers for
medicine and technics, pharmaceuticals, technically
important products, etc. [17–19].
catalyst. The reaction was carried out in the absence of
a solvent by heating a mixture of the reactants and
catalyst (~3 wt %). To attain high conversion and sup-
press side processes (in particular, stepwise oligomer-
ization via polyaddition), 2-propynol was taken in
a ~1.1–1.7 molar excess with respect to oxirane I. It is
known [22] that base-catalyzed reactions of oxiranes
with alcohols and phenols, apart from the correspond-
ing monoadducts, give considerable amounts of poly-
glycol ethers as a result of addition of initially formed
1,2-diol monoether to oxirane. Moreover, the process
may be accompanied by homopolymerization of
oxiranes I in the presence of alkaline initiators [22].
Obviously, the reaction outcome is determined by the
ratio of the rates of the main and side processes.
Hydroxy-containing alkynyl ethers (1,2-diol mono-
2-propynyl ethers) can be synthesized via opening of
oxirane ring by the action of acetylenic alcohols, in-
cluding accessible 2-propynol, in the presence of alkali
metal hydroxide (methyl-, phenyl-, or 1,2-dimethyl-
oxirane; NaOH or KOH; reflux, 1–3 h; yield 32–37%)
[3, 6], tertiary amines (oxirane or methyloxirane;
N,N-dimethylaniline; high-pressure reactor, 60–150°C,
7–8 h; yield 69–74%) [20] or acid catalysts [oxirane,
methyloxirane, 2-(chloromethyl)oxirane, 1-(3,3-di-
methyloxiran-2-yl)ethanone, 1,2-epoxycyclopentane,
1,2-epoxy-1-ethylcyclopentane, or 1,2-epoxycyclo-
hexane; boron trifluoride–ether complex; –5 to 20°C,
3–15 h; yield up to 85%] [21]. Usually, 2–5 equiv of
acetylenic alcohol (with respect to oxirane) is taken.
The reaction course was monitored by IR spec-
troscopy, following the intensity of the IR absorption
band at 3000 cm–1, which corresponds to stretching
vibrations of the C–H bond in the oxirane ring. The
disappearance of that band was accompanied by ap-
pearance of absorption bands due to vibrations of
hydroxy (3430–3450 cm–1) and 2-propynyloxy groups
(~2120 and ~3280 cm–1); the other absorption bands,
specifically those belonging to the allyloxy (840–850,
1270, 1340–1360, 1640, 3010, and 3080 cm–1) or
vinyloxy group (860, 1200, 1330, 1620–1640, 3050–
3070, and 3120 cm–1) remained essentially unchanged.
The conversion of initial oxiranes Ia and Ib was
estimated on the basis of the intensities of signals from
By reacting 2-propynol with functionally sub-
stituted oxiranes [18], e.g., 2-(allyloxymethyl)- and
2-[2-(vinyloxy)ethoxy]methyloxiranes Ia and Ib, we
succeeded in synthesizing in a simple way new re-
presentatives of polyfunctional 3-(2-propynyloxy)-
propan-2-ols, 1-allyloxy-3-(2-propynyloxy)propan-2-
ol (IIa) and 1-[2-(vinyloxy)ethoxy]-3-(2-propynyloxy)-
propan-2-ol (IIb) [1], which are promising as mono-
mers, synthons, and starting compounds for fine or-
ganic (including heterocyclic [1]) synthesis, as well as
convenient models for studying prototropic rearrange-
ments and intramolecular cyclizations.
1
protons in the oxirane ring in the H NMR spectra, į,
ppm: 3.08–3.10 m (1H, OCH), 2.73–2.74 d.d and
2.55–2.56 q (2H, OCH2). The conditions for reactions
of 2-(allyloxymethyl)oxirane (Ia) with 2-propynol and
the yields of 1-allyloxy-3-(2-propynyloxy)propan-2-ol
(IIa) are given in Table 1.
HO
+
O
RO
Ia, Ib
As might be expected, the reaction time and the
yield of 2-propanols II depended on the structure of
oxirane I and temperature. The maximal yield of
3-(2-propynyloxy)propan-2-ol (IIa, isolated product)
was 65–68% (yield of the crude product >80%) in
the reaction of oxirane Ia with 2-propynol (1.18–
1.25 equiv) at 75–85°C (reaction time 9.5–10 h;
Table 1, run nos. 5, 7, 8). 3-(2-Propynyloxy)propan-2-
ol (IIb) was synthesized in a similar way by heating
a mixture of oxirane Ib and 2-propynol at a ratio of
1:1.67 in the presence of ~3 wt % of t-BuOK (80–
85°C, 5 h; yield up to 95%); this reaction was con-
sidered in detail in the preceding communication [1].
O
t-BuOK
HO
OR
IIa, IIb
R = CH2=CHCH2 (a), CH2=CHOCH2CH2 (b).
Taking into account that molecules Ib and IIb
possess an additional reaction center (vinyloxy group)
which is sensitive to acid compounds [1, 18] (ex-
tremely high reactivity of the electron-rich double
bond toward electrophiles is the most general and well
known property of vinyl ethers [1, 18, 19]), the con-
densation of 2-propynol with oxiranes I was performed
in the presence of potassium tert-butoxide as base
When the reaction was performed with equimolar
amounts of oxirane Ia and 2-propynol, up to 45% of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 10 2005

DMITRIEVA et al.
Table 1. Reaction of oxirane Ia with 2-propynol in the presence of ~3 wt % of t-BuOK
1432
Amounts of reactants, mol
Yields of products,a %
Run
no.
Temperature, Reaction
imitial
oxirane Ia
high-boiling undistillable
fraction
°C
time, h
oxirane Ia
2-propynol
0.05
crude IIa distilled IIa
residue
1b
0.04
60
1.5
9.0
100.0
–
60
c29c
54
–
–
05
–
–
5
–
–
70
5.5
005.0
070.0
019.0
33.0
–
2b
3b
4b
0.09
0.09
0.31
0.10
0.10
0.36
70
6.0
c30c
75–80
75–80
80–85
75–80
80–85
75–80
80–85
8.0
70
47.4
11
8.0
10.00
10.00
15.00
9.5
009.5
007.9
045.0
013.0
016.7
62
–
35.9
68.2
36.7
05
03
01
5
1
5d
6d
7d
8d
0.11
0.35
0.11
0.04
0.13
0.35
0.13
0.05
–
e84e
e67e
9.5
a
b
c
d
e
Calculated on the reacted oxirane Ia.
The reaction mixture was treated first with a ~15% aqueous solution of ammonium chloride and then with diethyl ether.
The yield was determined from the 1H NMR spectra by the intensity of signals from protons in residual epoxy groups.
The mixture was dissolved in diethyl ether, and the solution was passed through a layer of neutral aluminum oxide.
The products obtained in run nos. 7 and 8 were combined and distilled under reduced pressure to isolate 65.4% of compound IIa and 5%
of a high-boiling substance.
the initial reactants was recovered from the reaction
mixture, and the yield of IIa did not exceed 37% even
when the reaction time was 15 h (80–85°C; Table 1,
run no. 6). Lowering the temperature to 60–70°C also
considerably slows down the process (Table 1, run
nos. 1, 2). After heating for 9 h at 60°C or for 6 h
at 70°C, the concentration of 2-propanol IIa in the
reaction mixture did not exceed 30%. Under analogous
conditions, the yields of the target product in the
reaction of 2-propynol with oxirane Ib were 69–73%
[1]. It follows from the above data that oxirane Ib is
much more reactive than Ia in the base-catalyzed
reaction with 2-propynol. Probable factors responsible
for the higher reactivity of oxirane Ib were discussed
previously [1].
droxy group and triple bond [2–8, 12], which are
usually promoted by bases. A probable reason is the
low concentration of the catalyst (~0.05 mol per mole
of oxirane). In some cases, some of the above side
processes occurred (as a rule, to an insignificant ex-
tent) during isolation of 3-(2-propynyloxy)propan-2-ol
(IIb) from crude reaction mixtures, i.e., during distilla-
tion in the presence of base catalyst. These instances
were analyzed in detail in [1].
We did not examine the regioselectivity of oxirane
ring opening by the action of 2-propyn-1-ol in the
presence of potassium tert-butoxide specially. How-
ever, numerous published data [18, 22], including the
results of special studies [27], suggest that opening of
the oxirane ring in compounds I, as well as in other
monosubstituted oxiranes (e.g., in methyloxirane), by
nucleophilic attack in neutral and basic media is regio-
selective; it leads to formation of secondary hydroxyl
group, i.e., primary ethers. As a rule, the fraction of
secondary ether is negligible. As shown in [27], the
ratio of the rates of addition of methoxide ion (MeO–)
to CH2 and CH(Me) groups of methyloxirane is ~97:3,
i.e., the corresponding secondary alcohol is in fact the
only reaction product.
Under the examined conditions, the fraction of
high-boiling and undistillable products (probably poly-
ethers) is insignificant (2–11%, Table 1). These data
may be treated as an evidence for reduced reactivity of
initial oxirane Ia and resulting 1,2-diol monoether IIa
with respect to each other.
It should be noted that we observed no further
transformations of 3-(2-propynyloxy)propan-2-ols IIa
and IIb, such as prototropic rearrangements in the
2-propynyl or allyl (in IIa) fragments (e.g., acetylene–
allene [12, 23] and/or allyl–propenyl isomerization
[24–26]) or intramolecular cyclizations involving hy-
3-(2-Propynyloxy)propan-2-ols IIa and IIb are
colorless mobile liquids which can readily be purified
by vacuum distillation. Their structure was confirmed
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 10 2005

VINYL ETHERS CONTAINING AN EPOXY GROUP: XXII.
1433
1
by the data of elemental analysis and IR and H
and 13C NMR spectroscopy. To minimize undesirable
processes during vacuum distillation, the catalyst must
be removed from the reaction mixture, e.g., by treat-
ment with a ~15% aqueous solution of ammonium
chloride or by dissolution of the products in a minimal
amount of diethyl ether and subsequent passing of the
solution through a layer of neutral aluminum oxide.
The latter procedure is more advantageous, for it en-
sures considerably lesser loss of the target product than
in the aqueous treatment.
strongly on the solvent nature (in addition to the nature
of the heteroatom). In particular, the cyclization of
2-(2-propynyloxy)ethanol catalyzed by alkali metal
hydroxides was shown [4, 7] to produce four products:
2-vinyl-1,3-dioxolane, 2-methylene-1,4-dioxane,
2-methyl-2,3-dihydro-1,4-dioxine, and 2,3-dihydro-
5H-1,4-dioxepine whose ratio depended on the condi-
tions. In the reaction in water in the presence of NaOH
or KOH (70–100°C, 12 h), the major products were
2-methylene-1,4-dioxane (36–45%) and 2,3-dihydro-
5H-1,4-dioxepine (36–48%), while the fraction of
2-vinyl-1,3-dioxolane was smaller (7–24%) and only
traces of 2-methyl-2,3-dihydro-1,4-dioxine (less than
1–2%) were detected. 2-Vinyl-1,3-dioxolane was
formed as the major product in the reaction carried out
in tert-butyl alcohol in the presence of KOH (reflux,
12 h); its fraction in the mixture of cyclic products was
65% (overall yield 61%) [7]. Finally, the same reaction
in aprotic solvents such as decahydronaphthalene
(100–180°C), dimethyl sulfoxide (70–150°C, 0.7 h),
and triethylene glycol dimethyl ether (100–190°C)
afforded 2-methyl-2,3-dihydro-1,4-dioxine (41–86%)
and 2-vinyl-1,3-dioxolane (18–48%) as the major
products, while the two other heterocyclic compounds
were formed in small amounts (1–10%) [4, 7]. The
highest yield (58%) and regioselectivity of the process
(86% of 2-methyl-2,3-dihydro-1,4-dioxine) were ob-
served in the system KOH–triethylene glycol dimethyl
ether (180–190°C, 0.5 h) [7]. In the other cases, the
overall yield of heterocyclic products ranged from
21 to 33% [4, 7].
In the preceding communication [1] we showed for
the first time that 1-[Ȧ-(vinyloxy)alkoxy]-3-(2-propyn-
yloxy)propan-2-ols, in particular compound IIb and
its analog synthesized from 2-propynol and 2-{2-[2-
(vinyloxy)ethoxy]ethoxymethyl}oxirane according to
the above scheme, are smoothly converted into
2-methyl-4-(2-propynyloxymethyl)-1,3,6-trioxocane
and 2-methyl-4-(2-propynyloxymethyl)-1,3,6,9-tetra-
oxacycloundecane, respectively, in the presence of
a catalytic amount (~0.5 wt %) of trifluoroacetic acid
in anhydrous diethyl ether (via intramolecular electro-
philic addition of hydroxy group at the vinyloxy
group). This reaction opens a simple route to previous-
ly unknown but undoubtedly promising cyclic poly-
ether acetals possessing highly reactive 2-propynyloxy
groups in the side chain. Karaev et al. [28] previously
desribed an example of acid-catalyzed cyclization of
2-(1,1-dimethyl-2-propynyloxy)cyclohexanol with
participation of the hydroxy group and the triple bond
under hydration conditions (H2O, HgO–H2SO4, 50–
60°C, 2 h); the product of this reaction was 2,3,3-tri-
methyloctahydro-1,4-benzodioxin-2-ol (yield 50%).
On the other hand, the nature of the catalyst (as
follows from the data of [4, 7]) affects the overall yield
of the cyclization products but almost does not affect
their ratio. In going from NaOH to KOH, other con-
ditions being equal (water, 100°C, 12 h), the yield
increases from 54 to 72%, while the ratio 2-methylene-
1,4-dioxane–2,3-dihydro-5H-1,4-dioxepine (36:44)
changes only slightly in favor of the former (39:36)
[7]. When the cyclization in the presence of sodium
hydroxide was performed at lower temperature (70°C),
both the overall yield and the fraction of 2-vinyl-1,3-
dioxolane decreased (from 54 to 37% and from 20 to
7%, respectively) [4].
On the other hand, no data on reactions of (2-prop-
ynyloxy)alkanols II in the presence of bases have been
reported so far, primarily because these compounds
have been unknown prior to our studies (see above). In
order to elucidate the effect of the substituent on the
carbon atom attached to hydroxy group on the cycliza-
tion direction and synthesize new families of oxygen-
containing heterocycles having highly reactive centers
(allyloxy and vinyloxy groups), we examined base-
catalyzed intramolecular cyclization of 1-allyloxy- and
1-[2-(vinyloxy)ethoxy]-3-(2-propynyloxy)propan-2-ols
IIa and IIb. The reaction conditions and product yields
are collected in Tables 2 and 3.
However, introduction of even the simplest substit-
uents (Me, Ph) into the ethanol or propynyl moiety of
the 2-(2-propynyloxy)ethanol molecule [3, 4, 6–8]
often gives rise to an appreciably different (from that
considered above) pattern of the effect of the solvent
and other factors on the ratio and overall yield of
It was found previously [4, 7, 9, 11] that the direc-
tion of cyclization of alkynols containing a heteroatom
(N, O, S) between the hydroxy group and triple bond
and the yield of the resulting heterocycles depend most
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 10 2005

DMITRIEVA et al.
1434
Table 2. Isomerization and intramolecular cyclization of 3-(2-propynyloxy)propan-2-ols IIa and IIb in the presence of
potassium hydroxide (molar ratio II–KOH 0.01:0.004)
Product composition,a %
Initial
Run
no.
Solvent Temperature, Reaction Overall
compound
no.
(10 ml)
°C
time, h yield, %
II
III
IV
V
VI
VII
VIII
01
02
03b
04b
05
06
07
08
09
10
11
H2O
~100
~100
0~75
~100
0~75
0~65
0~75
0~65
0~65
0~65
~100
~100
0~65
0~65
04
07
70
80
70
80
90
90
80
90
70
80
80
90
80
80
50
63
60
07
–
–
–
–
~1
30
05
–
40
23
09
55
20
24
20
19
<1
14
05
14
10
09
10
02
~1
14
<1
04
~1
06
<1
05
05
04
10
–
–
–
IIa
IIb
IIa
IIb
IIa
IIb
IIa
IIb
IIa
IIb
IIa
IIb
IIa
IIb
H2O
09
–
02
–
H2O
0.16.5
07
–
H2O
~1
<1
–
17
40
37
40
41
05
07
37
23
10
02
02
40
35
40
34
10
9
DMSO
DMSO
DMSO
DMSO
THF
~1 min
~1 min
00.0.5
02
–
–
–
–
–
–
–
–
00.7.5
02
45
39
–
40
26
10
–
–
THF
–
Toluene
Toluene
–
02
–
43
59
–
12
13b
14c
01
–
–
12
50
80
20
08
–
–
02
–
<1
a
b
c
Here, as well as in Table 3, the yields were estimated on the basis of the 1H NMR spectra.
0.012 mol of KOH.
No solvent.
cyclization products [į, ppm: V: 4.24–4.43 s (CH2=);
VI: 4.62–4.77 d.d.t (exo-CH=), 6.24–6.35 d.d.d (exo-
OCH=); VII: 5.12–5.29 d (OCHO), 5.22–5.38 d
(CH2=), 5.41–5.43 d.d.d (CH=); VIII: 1.66 d (Me),
5.68–5.77 q (exo-OCH=)] with those of protons in the
vinyloxy [IIb, į, ppm: 4.01 d.d, 4.19 d.d (CH2=),
6.46 d.d (OCH=)] or allyloxy group [į, ppm: 5.17 d.d.t,
5.26 d.d.t (CH2=), 5.89 d.d.t (CH=)] or with the overall
intensity of signals from the allyloxy and 1-propenyl-
oxy groups [IIa, į, ppm: 1.55 d (Me), 4.41 d.q (CH=),
5.93 d.q (OCH=)]. The conversion of 2-propanols II
and the overall yield of products were estimated from
the residual intensity of the OH (į 2.95–3.01 ppm, d)
and ŁCH protons (į 2.48 ppm, t). The complete
absence of signals from acetylenic protons and carbon
atoms [įC 74.94–75.02 (ŁCH), 79.61–79.70 ppm (ŁC)]
the cyclization products, mainly for stereoelectronic
reasons.
We studied the cyclizations of 1-allyloxy- and
1-[2-(vinyloxy)ethoxy]-3-(2-propynyloxy)propan-2-ols
IIa and IIb in water, DMSO, THF, and toluene and
without a solvent. As catalyst we used KOH and
t-BuOK. The progress of reactions was monitored by
1
IR and H and 13C NMR spectroscopy; both reaction
mixtures and products isolated by distillation were
examined. In the IR spectra, we observed decrease in
the intensity of absorption bands due to vibrations of
the hydroxy group (3430–3450 cm–1) and terminal
triple bond [2120 (CŁC), 3280 (ŁC–H) cm–1] up to
their complete disappearance. Simultaneously, the
regions corresponding to stretching vibrations of allene
fragment (~1950 cm–1, C=C=C), internal triple bond
(2170 cm–1, –CŁC–), and double C=C bonds (1650–
1660 and 1680–1700 cm–1; in the spectrum of IIb, the
first band usually appears as a shoulder on the strong
absorption band at 1610–1640 cm–1 due to vinyloxy
group) were monitored. The yields were calculated
from the 1H NMR spectra by comparing the intensities
of characteristic signals from protons in the acetylene–
allene isomerization [į, ppm: III: 5.44 d (CH2=), 6.74 t
(CH=); IV: 1.40 s (Me–CŁC)] and intramolecular
1
in the H and 13C NMR spectra indicated 100% con-
version of 3-(2-propynyloxy)propan-2-ols IIa and IIb.
Scheme 1 shows possible reaction pahways (ac-
cording to our and published data [4, 6, 7]) and prod-
ucts. The reaction mechanisms (the main mechanism
including pathways 1–5 was proposed in [4], and alter-
native mechanism including pathways 6–10 was pro-
posed in [6, 7]) imply base-catalyzed prototropic re-
arrangement of 3-(2-propynyloxy)propan-2-ols II into
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 10 2005

VINYL ETHERS CONTAINING AN EPOXY GROUP: XXII.
1435
Table 3. Isomerization and intramolecular cyclization of 3-(2-propynyloxy)propan-2-ols IIa and IIb in the presence of
potassium tert-butoxide (molar ratio II–t-BuOK 0.01:0.004)
Initial
Run no. compound
no.
Product composition, %
Solvent
(10 ml)
Temperature, Reaction
Overall
yield, %
°C
time, h
III
V
VI
VII
VIII
01
DMSO
DMSO
DMSOb
DMSO
THF
0~75
0~45
0~75
0~65
0~45
0~65
~100
~100
0~65
0~65
~5 min
~1 min
02
a90a
90
c90c
–
–
5
–
–
–
–
–
7
3
–
<5
<1
<5
~1
–
35
40
45
53
18
18
42
22
50
39
60
55
25
46
72
57
50
56
30
58
IIa
02
03
04
05
06
07
08
09f
10f
05
10
–
IIb
IIa
IIb
IIa
IIb
IIa
IIb
IIa
IIb
01
90
01
d90d
90
e80e
10
22
07
18
10
–
THF
02
<3
~1
<4
<3
–
Toluene
Toluene
–
0.000.75
10
90
,002.5
07
70
–
90
a
b
c
d
e
f
100% of 1-propenyloxy derivatives VIc–VIIIc.
5 ml.
The mixture contained 10% of initial alcohol IIa.
The mixture contained ~5% of 1-propenyloxy derivatives.
~25% of 1-propenyloxy derivatives.
Without a solvent.
the corresponding 3-(1,2-propadienyloxy)propan-2-ols
III and 3-(1-propynyloxy)propan-2-ols IV and their
cyclization to compounds V–IX, as well as prototropic
rearrangements of 6-methylene-1,4-dioxane V into
6-methyl-2,3-dihydro-1,4-dioxine VIII and of 2-ethyli-
dene-1,3-dioxolane IX into 2-vinyl-1,3-dioxolane VII.
is accompanied by migration of the exocyclic double
bond into the ring (pathway 6). Moreover, Faure and
Descotes [6] believed that this is the only pathway
leading to 1,4-dioxines. According to [4, 7], the con-
tribution of pathway 6 strongly depends on the struc-
ture of 2-(2-propynyloxy)ethanol and reaction condi-
tions. Such isomerization was shown in [7] to proceed
at a low rate and only in DMSO: when a mixture of
cyclic products in the presence of KOH was heated at
120°C, the concentration of 2-methylene-1,4-dioxane
decreased from 38 to 21% in 0.7 h and to 3% in 4.8 h;
simultaneously, the concentration of 2-methyl-2,3-di-
hydro-1,4-dioxine increased from 4 to 25 and 41%,
respectively. The isomerization can be accelerated by
raising the temperature: after heating for 0.7 h at
190°C in the KOH–DMSO system, the concentration
of 2-methyl-2,3-dihydro-1,4-dioxine increased from 3
to 38% [7]. As noted in [4], both thermal and hy-
droxide ion-induced isomerization of 2-methylene-1,4-
dioxane contribute very little to the formation of 2-meth-
yl-2,3-dihydro-1,4-dioxine in the reaction of 2-(2-pro-
pynyloxy)ethanol with NaOH in DMSO at 120°C.
In fact, the reaction outcome is determined prima-
rily by the ratio of rates of two concurrent processes,
base-catalyzed acetylene–allene isomerization of
3-(2-propynyloxy)propan-2-ol II (pathway 1) and its
cyclization via intramolecular nucleophilic addition of
the hydroxy group at the internal or terminal triple-
bonded carbon atom, leading to 6-methylene-1,4-di-
oxane V and/or 2,3-dihydro-5H-1,4-dioxepine VI
(pathway 2). In turn, the formation of 2-vinyl-1,3-di-
oxolane VII and 6-methyl-2,3-dihydro-1,4-dioxine
VIII is determined by the ratio of rates of two other
concurrent processes, prototropic rearrangement of
3-(1,2-propadienyloxy)propan-2-ol III (pathway 3)
and its cyclization via intramolecular nucleophilic
addition of the hydroxy group at the allene C1 atom
(pathway 4).
In keeping with published data [6, 7], apart from
intramolecular cyclization of 3-(1-propynyloxy)prop-
an-2-ol (IV) (pathway 5) [4], 6-methyl-2,3-dihydro-
1,4-dioxine (VIII) may be formed by base-catalyzed
rearrangement of 6-methylene-1,4-dioxane (V), which
It was also presumed [6] that 2-vinyl-1,3-dioxolane
can be formed in aprotic solvents via cyclization of
3-(1-propynyloxy)propan-2-ol IV (in our case) to
2-ethylidene-1,3-dioxolane IX (pathway 7), followed
by rearrangement involving migration of the double
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 10 2005

DMITRIEVA et al.
Scheme 1.
RO
1436
O
O
O
2
RO
RO
IIa, IIb
+
O
Va–Vc
VIa–VIc
10
O
O
4
HO
·
O
OR
6
IIIa–IIIc
VIIa–VIIc
9
8
O
O
O
RO
5
RO
HO
OR
O
O
IVa–IVc
VIIIa–VIIIc
IXa–IXc
7
R = CH2=CHCH2 (a), CH2=CHOCH2CH2 (b), MeCH=CH (c).
of 5-methylene-1,3-dioxanes into the corresponding
4H-1,3-dioxines was performed using a very large
excess of the base, though at room temperature in the
system t-BuOK–t-BuOH (6 equiv of t-BuOK, 5 equiv
of t-BuOH, THF, 12 h, yield 82–91%) [30]. Our
studies were performed with considerably more dilute
solutions of the reagent and catalyst [1 M solutions of
3-(2-propynyloxy)propan-2-ols II and ~0.4 M solu-
tions of base in appropriate solvent], the relative con-
centration of the base was appreciably lower (0.4 mol
of base per mole of II against equimolar ratio of the
reagent and base in [4, 7]), and the temperature was
also considerably lower (45–100°C). Therefore, we
succeeded in detecting formation of 1,2-propadienyl-
oxy (III) and 1-propynyloxy (IV) isomers of II as
intermediates in the synthesis of cyclic ethers and
hence obtained experimental proofs for the reaction
under study to follow pathways 1–5. Previously [4, 7],
this mechanism of cyclization of propynyloxyalkanols
was assumed on the basis of only indirect evidences.
bond from the oxygen atom to the terminal carbon
atom (pathway 8), though ketene acetals like IX
usually cannot be detected due to their instability under
the reaction conditions [29]. Also, there exists the pos-
sibility for formation (in addition to 1,3-dioxolane VII,
pathway 4) of some amounts of compounds V, VI, and
VIII by intramolecular cyclization of 3-(1,2-propadi-
enyloxy)-propan-2-ols III as a result of addition of the
hydroxy group at the central or terminal carbon atom
of the 1,2-propadienyloxy group (pathways 9, 10).
Proofs in support of the transformation of allenyloxy-
ethanols into 1,4-dioxines were given in [7].
However, analysis of our results showed that, even
though some of the above alternative reaction path-
ways are actually operative, their contribution to the
overall yield of compounds V–VIII is quite insignif-
icant. Although transformation of oxygen-containing
heterocycles with an exocyclic double bond into their
isomers with endocyclic double bond is possible, it
obviously requires more severe conditions. For ex-
ample, the base-catalyzed cyclizations reported in
[4, 7] were effected in a 2 M solution of 2-(2-prop-
ynyloxy)ethanol and base at 100–190°C, while the
isomerizations of 2-methylene-1,4-dioxanes into
6-methyl-2,3-dihydro-1,4-dioxines occurred at a base–
cyclic product molar ratio of (0.5–1):1 in DMSO at
100–190°C (0.7–12 h). By contrast, the isomerization
Thus we have shown that reactions of 1-allyloxy-
and 1-[2-(vinyloxy)ethoxy]-3-(2-propynyloxy)propan-
2-ols IIa and IIb with potassium hydroxide (Table 2)
or tert-butoxide (Table 3), depending on the condi-
tions, follow preferentially or exclusively pathways
1–5. By contrast, no reliable experimental proofs have
been obtained for pathways 6–10. These results will be
considered in more detail below.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 10 2005

VINYL ETHERS CONTAINING AN EPOXY GROUP: XXII.
1437
Insofar as the rate of prototropic rearrangements in
water is known [12, 23] to be considerably lower than
in aprotic solvents [4, 6, 7, 11], the major products in
the reactions with aqueous solutions of alkali metal
hydroxides (as noted above) are 2-methylene-1,4-di-
oxanes and 2,3-dihydro-5H-1,4-dioxepines; they are
formed in approximately equal amounts, but the latter
always predominate [in the reactions with unsubstitut-
ed 2-(2-propynyloxy)alkanols]. This means that under
the above conditions the rate of intramolecular cy-
clization of 2-(2-propynyloxy)alkanol is considerably
higher than the rate of its isomerization. On the whole,
our results are consistent with such views on the
reaction mechanism, though in our case the yield of
1,4-dioxanes V strongly exceeds (by a factor of ~4
to 12) the yield of 1,4-dioxepines VI (Table 2, run
nos. 1–4). The corresponding difference for the re-
ported examples is usually smaller [7].
1-allyloxy-3-(1-propynyloxy)propan-2-ol (IVa), 9% of
6-methylene-1,4-dioxane Va, and ~1% of 2,3-dihydro-
5H-1,4-dioxepine VIa (Table 2, run no. 3). In the IR
spectrum of the reaction mixture we observed an ab-
sorption band at 2170 cm–1 due to stretching vibrations
of the internal triple CŁC bond, and the 1H NMR spec-
trum displayed a singlet at į 1.40 ppm from protons in
the MeCŁC group. Obviously, under these conditions
prototropic isomerization of IIa appreciably predomi-
nates over cyclization processes. This follows from
both large concentration of isomeric 2-propanol IVa in
the product mixture and reduction in the yields of
compounds Va and VIa (from 40 to 9% and from 10 to
~1%, respectively), as well as from the absence of
cyclization products VIIIa and VIIa which could be
formed from 3-(1-propynyloxy)propan-2-ol IVa or
its allene precursor IIIa, respectively.
Analogous increase in the amount of KOH in the
reaction with compound IIb, other conditions being
equal (Table 2; run nos. 2, 4), sharply raised the con-
version (from 37 to 93%) and appreciably increased
the concentration of 6-methylene-1,4-dioxane Vb
(from 23 to 54%). In addition to 2,3-dihydro-5H-1,4-
dioxepine VIb and 1,3-dioxolane VIIb (which were
also formed in run no. 2; only their concentration in-
creased from 2 to 14% and from 9 to 17%, respec-
tively), we identified products of prototropic isomer-
ization of compound IIb, 1-[2-(vinyloxy)ethoxy]-3-
(1,2-propadienyloxy)propan-2-ol (IIIb, ~1%) and
1-[2-(vinyloxy)ethoxy]-3-(1-propynyloxy)propan-2-ol
(IVb, ~5%).
As is seen from the data in Table 2, the only prod-
ucts of cyclization of 1-allyloxy-3-(2-propynyloxy)-
propan-2-ol (IIa) in water in the presence of KOH
(100°C, 4 h) were 2-(allyloxymethyl)-6-methylene-
1,4-dioxane (Va, 40%) and 2-(allyloxymethyl)-2,3-
dihydro-5H-1,4-dioxepine (VI, 10%). Here, up to 50%
of initial alcohol IIa was recovered from the reaction
mixture (Table 2, run no. 1). Replacement of the allyl
group by 2-(vinyloxy)ethyl appreciably affects the
reactivity. The conversion of 1-[2-(vinyloxy)ethoxy]-3-
(2-propynyloxy)propan-2-ol (IIb) in the reaction with
KOH in water (100°C) did not exceed 37% even when
the reaction time was prolonged to 7 h (Table 2, run
no. 2). Moreover, unlike the reaction with IIa, the
process was less selective, and 9% of 2-vinyl-4-[2-
(vinyloxy)ethoxymethyl]-1,3-dioxolane (VIIb) was
formed together with 6-methylene-2-[2-(vinyloxy)-
ethoxymethyl]-1,4-dioxane (Vb, 23%, the major prod-
uct). The concentrations of 2-[2-(vinyloxy)ethoxy-
methyl]-2,3-dihydro-5H-1,4-dioxepine (VIb) and
6-methyl-2-[2-(vinyloxy)ethoxymethyl]-2,3-dihydro-
1,4-dioxine (VIIIb) each did not exceed 2%. Presum-
ably, in contrast to compound IIa, 3-(2-propynyloxy)-
propan-2-ol IIb partially undergoes acetylene–allene
isomerization despite inhibitory effect of aqueous
medium.
In nonaqueous media (DMSO, toluene) in the pres-
ence of both KOH and t-BuOK, compounds II mainly
undergo intramolecular ring closure to 2-vinyl-1,3-di-
oxolanes VII and 6-methyl-2,3-dihydro-1,4-dioxines
VIII whose overall concentration in the product mix-
ture reaches 70–99% in DMSO and 78–92% in toluene
(Tables 2, 3). 6-Methylene-1,4-dioxanes V and 2,3-di-
hydro-5H-1,4-dioxepines VI are also formed, but the
concentration of VI does not exceed 6% (1–6%), and it
remains unchanged on prolonged reaction. Compound
V is formed in an amount of 5 to 24%; its concentra-
tion in the product mixture was the maximal (19–24%)
when the reaction was carried in DMSO in the pres-
ence of KOH (Table 2, run nos. 5–8). Presumably,
increased basicity of the medium favors not only
acetylene–allene isomerization of compound II but
also its cyclization. The ratio of the main products,
compounds V, VII, and VIII, obtained in DMSO in
the presence of KOH is ~1:2:2. The reaction occurs at
Lowering the temperature from 100 to 75°C with
simultaneous increase of the reaction time from 4 to
16.5 h and of the amount of KOH from 0.4 to 1.2 mol
per mole of IIa resulted in formation of a mixture of
linear and cyclic products containing 60% of initial
compound IIa, 30% of its isomerization product,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 10 2005

DMITRIEVA et al.
1438
moderate temperature and at a fairly high rate (~1 min
at 65–75°C, ) and is sometimes accompanied by strong
heat evolution. Increase of the reaction time to 0.5–2 h
almost does not affect the overall yield (80–90%) and
the product ratio (Table 2; run nos. 7, 8). This may be
regarded as an evidence for the absence of isomeriza-
tion of 6-methylene-1,4-dioxanes V into 1,4-dioxines
VIII (pathway 6 in Scheme 1) under the given con-
ditions. It is interesting that the reaction outcome in the
system KOH–DMSO does not depend on the substrate
structure. Unlike the reaction in water, the conversion
of compounds II both in DMSO and in toluene was
quantitative.
It should be emphasized that, under comparable
conditions, both in THF and in toluene in the presence
of both potassium hydroxide and potassium tert-but-
oxide the yield of Vb is greater by a factor of ~2–3
than the yield of Va. Presumably, these data indicate
both relatively higher rate of acetylene–allene isomer-
ization of compound IIa as compared to IIb and lower
rate of intramolecular cyclization with participation of
the terminal triple bond. The latter follows, e.g., from
the results of run no. 9 (Table 2) considered above:
After heating for 7.5 h at 65°C in the system KOH–
THF, the reaction mixture contained 45% of initial
propanol IIa and only traces (less than 1%) of its direct
cyclization products, compounds Va and VIa, while
the overall fraction of the isomerization products was
55%. A different pattern was observed with compound
IIb: the reaction mixture contained 19% of the direct
cyclization products (Vb and VIb) and 40% of the iso-
merization products (Table 2, run no. 10). These data
refer to 2 h elapsed from the reaction start, i.e., the
overall reactivity of compound IIb in THF and toluene
in the presence of KOH is appreciably higher than the
reactivity of IIa (Table 2, run nos. 9–12).
The effect of the structure of compounds II on the
ratio of cyclization products was observed most clearly
when the reaction was carried out in boiling toluene.
From alcohol IIa in the presence of potassium hydrox-
ide (toluene, 100°C, 2 h) we obtained compounds IIIa,
Va, VIIa, and VIIIa in 10, 5, 37, and 43% yield,
respectively (Table 2, run no. 11), while the major
cyclization product obtained from compound IIb under
analogous conditions (100°C, 1 h) was 2,3-dihydro-
1,4-dioxine VIIIb; its concentration exceeded that of
VIIb by a factor of ~2.5 (59 and 23%, respectively;
Table 2, run no. 12). On the other hand, the yield of Vb
was almost 3 times greater than the yield of Va (14 and
5%, respectively). Analogous results were obtained in
toluene in the presence of potassium tert-butoxide
(Table 3; run nos. 7, 8).
The main transformation products obtained from
compound IIa by the action of potassium tert-butoxide
in the absence of a solvent were 1,3-dioxolane VIIa
(50%) and 2,3-dihydro-1,4-dioxine VIIIa (30%)
(Table 3, run no. 9). The reaction mixture also con-
tained compounds IIIa, Va, and VIa (7, 10, and 3%,
respectively). Interestingly, analogous results were ob-
tained in the system t-BuOK–DMSO (Table 3, run
no. 3). The selectivity of cyclization of IIb under
solvent-free conditions was even higher: the overall
fraction of 1,3-dioxolane VIIb and 2,3-dihydro-1,4-
dioxine VIIIb was 97%, although their ratio was the
reverse (39 and 58%, respectively; Table 3, run
no. 10). The reaction catalyzed by KOH in the absence
of a solvent was very slow and nonselective (Table 2,
run nos. 13, 14). Here, the conversion of IIa was 50%
after heating for 12 h at 65°C, and of IIb, only 20%
(2 h). In addition to (1,2-propadienyloxy)propanol IIIa
(20%), compounds Va, VIa, and VIIa were formed
(10% each). No 2,3-dihydro-1,4-dioxine VIIIa was
detected. Among the transformation products of com-
pound IIb, we identified allenyl alcohol IIIb (8%),
small amounts of cyclic ethers Vb and VIIb (9 and
2%, respectively), and traces (<1%) of 2,3-dihydro-
1,4-dioxine VIIIb.
The rate of cyclization in other aprotic solvents,
e.g., tetrahydrofuran, was considerably lower than in
DMSO. In boiling THF in the presence of KOH, even
after 7.5 h the reaction mixture contained up to 45%
of initial compound IIa, and the major product was
1-allyloxy-3-(1,2-propadienyloxy)propan-2-ol (IIIa,
40%) (Table 2, run no. 9). The fraction of cyclic prod-
ucts was insignificant (15%), the main of these being
2,3-dihydro-1,4-dioxine VIIIa (10%) in a mixture with
5% of 1,3-dioxolane VIIa. Only traces of Va and VIa
were detected. Compound IIIa showed in the 1H NMR
spectrum a doublet signal at į 5.44 ppm (CH2=) and
a triplet at į 6.74 ppm (CH=) from protons in the
allene fragment. Obviously, under these conditions the
rates of isomerization of IIIa into IVa and its cycliza-
tion to 1,4-dioxine VIIIa clearly exceed the rate of
cyclization of IIIa to 1,3-dioxolane VIIa. On the other
hand, the reaction catalyzed by potassium tert-but-
oxide was fast and effective: the conversion of IIa
reached 90% on heating for 1 h at 45°C (Table 3,
no. 5). Moreover, the process is fairly selective: prod-
uct VIIIa is formed in 72% yield.
As we already noted, apart from the heterocycliza-
tions and acetylene–allene rearrangement considered
above, 1-allyloxy-3-(2-propynyloxy)propan-2-ol (IIa)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 10 2005

VINYL ETHERS CONTAINING AN EPOXY GROUP: XXII.
1439
and its derivatives IIIa–VIIIa can be involved in
another base-catalyzed prototropic isomerization,
namely allyl–propenyl rearrangement [24–26] which
implies migration of the double C=C. Insofar as pre-
parative version of that rearrangement was not the aim
of the present study, we did not optimize its conditions
but only analyzed the NMR spectra of the products
obtained under the conditions summarized in Tables 2
and 3, as well as in other experiments.
VIIa failed to undergo rearrangement into 1-propenyl
isomer VIIc under the same conditions.
No allyl–propenyl isomerization occurred in the
absence of a solvent (Table 4; run nos. 10, 11) even
under catalysis by t-BuOK. The most probable reason
is relatively low temperature (60°C) and insufficient
reaction time (3 h). As shown in [26], prototropic
rearrangement of allyl ethers under solvent-free con-
ditions requires heating to 150–175°C over a period
of 3–163 h in the presence of 2–15 wt % of base
catalyst (t-BuOK, MeONa) in a nitrogen atmosphere
(yield 35–99%).
KOR2, DMSO
O
R1
O
R1
IIa–VIIIa
IIc–VIIIc
The structure of the cyclization and isomerization
R2 = H, t-Bu.
1
products was confirmed by the H and 13C NMR and
1
IR spectra. In the H NMR spectra of the 1-propenyl
As in the acetylene–allene rearrangement, the ease
of allyl–propenyl isomerization is determined by
the solvent nature, temperature, and reaction time
(Table 4). In most cases, e.g., in toluene (100°C, 2 h)
and THF (65°C, 7.5 h) in the presence of potassium
hydroxide, no allyl–propenyl isomerization occurred
(Table 4; run nos. 1, 4). Replacement of KOH by
t-BuOK displaced the equilibrium toward the 1-prop-
enyl isomer to an insignificant extent (25% in toluene
and 5% in THF; Table 4, run nos. 3 and 5). This is
consistent with the data of [25], according to which the
reaction rate attains its maximal value in polar aprotic
solvents like DMSO: at 25°C, the half-conversion
period of allyl phenyl ether in a 0.68 M solution in
DMSO by the action of 0.05 M t-BuOK was 1.5 min.
In 1,2-dimethoxyethane, the half-conversion period
was 160 min, though the concentration of t-BuOK was
0.66 M. In fact, in the superbasic system t-BuOK–
DMSO, the rate of allyl–propenyl rearrangement of
compound IIa was the highest (Table 4, run no. 8), and
the substrate conversion was quantitative within a few
minutes. However, twofold reduction of the volume of
DMSO completely inhibited the allyl–propenyl iso-
merization (Table 4, run no. 9). The isomerization
showed an unexpectedly strong dependence on the
substrate structure. By heating compound IIa in the
system KOH–DMSO for 7 h at 70°C (Table 4, run
no. 7) we obtained a mixture of 4-allyloxymethyl-2-
vinyl-1,3-dioxolane (VIIa), 2-allyloxymethyl-6-meth-
yl-2,3-dihydro-1,4-dioxine (VIIIa), and 2-(1-propenyl-
oxymethyl)-6-methyl-2,3-dihydro-1,4-dioxine (VIIIc)
which were isolated by column chromatography and
isomers, the doublet signal from the methyl protons is
located at į 1.55 ppm, and multiplets at į 4.42 and
5.95 ppm belong to protons at the double bond in the
MeCH=CH–O fragment. The isomeric composition of
the cyclic products was not examined specially; how-
ever, it should be noted that cyclization of compounds
II gives mixtures of diastereoisomeric 2-vinyl-1,3-di-
oxolanes VIIa–VIIc due to the presence in their mole-
cules of two asymmetric carbon atoms (C2 and C4) in
the OCHO and OCHCH2OR fragments.
H
4
*
5
RO
3O
H
O1
*
2
VIIa–VIIc
R = CH2=CHCH2 (a), CH2=CHOCH2CH2 (b), MeCH=CH (c).
The existence of two diastereoisomers follows from
1
13
doubling of all signals in the H and C NMR spectra
of compounds VII. Differences in the position of reso-
nance signals from diastereotopic carbon atoms in the
13C NMR spectra are insignificant: the ǻįC range is
0.06 to 0.55 ppm. The largest difference is observed
in the 13C signals from the acetal (OCHO) and vinyl
groups (CH2=): ǻįC = is 0.51–0.55 and 0.59–
0.68 ppm, respectively. The =CH signals are the least
sensitive: ǻįC = 0.06–0.12 ppm. The maximal differ-
ence in the chemical shifts of protons (ǻį) does not
exceed 0.13 ppm (OCHO), and the minimal ǻį value
(0.01–0.02 ppm) is observed for the CH2= protons.
1
identified by the H and 13C NMR spectra. The con-
version of allyloxymethyl-1,4-dioxine VIIIa into the
corresponding 1-propenyloxymethyl derivative VIIIc
was only 40%, while allyloxymethyl-1,3-dioxolane
Cyclization products derived from 3-(2-propynyl-
oxy)propan-2-ols II are colorless mobile liquids which
are distilled under reduced pressure as azeotropic mix-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 10 2005

DMITRIEVA et al.
1440
Table 4. Allyl–propenyl isomerization of 1-allyloxy-3-(2-propynyloxy)propan-2-ol (IIa) and its derivatives IIIa–VIIIa
Product composition,a %
Temperature, Reaction
Run no. Base catalyst Solvent (10 ml)
°C
time, h
allyloxy derivatives
1-propenyloxy derivatives
01
02
03
04
05
06
07
08
09
10
11
KOH
Toluene
Toluene
Toluene
THF
~100
0~65
~100
0~65
0~45
0~75
0~75
0~75
0~75
0~65
0~65
02.00
05.00
00.75
07.50
01.00
00.16
07.00
00.10
02.00
12.00
03.00
100
100
075
100
095
100
080
–
–
–
t-BuOK
t-BuOK
KOH
025
–
t-BuOK
KOH
THF
005
–
DMSO
DMSO
DMSO
DMSOb
No solvent
No solvent
KOH
020
100
–
t-BuOK
t-BuOK
KOH
100
100
100
–
t-BuOK
–
a
The degree of isomerization was determined from the intensity ratio of signals at į 1.55 (Me), 4.40 (MeCH=), and 5.25/5.15 ppm (CH2=)
in the 1H NMR spectra of mixtures IIa–VIIIa.
b
5 ml.
tures boiling in a narrow temperature range (~3°C).
Pure compounds VIIa and VIIIa were isolated by
column chromatography.
each, CH2=), 4.00 m (2H, OCH2), 3.66 d.d and 3.36 q
(1H each, OCH2), 3.08 m (1H, CH), 2.73 d.d and
2.55 q (1H each, CH2). 13C NMR spectrum (CCl4–
CDCl3), įC, ppm: 134.30 (CH=), 116.68 (CH2=), 71.81
(OCH2), 70.47 (OCH2), 50.32 (CH), 43.69 (CH2).
EXPERIMENTAL
2-[2-(Vinyloxy)ethoxy]methyloxirane (Ib). IR
spectrum, Ȟ, cm–1: 760, 830 sh, 840, 860 sh, 880 sh,
920, 970, 1040, 1130, 1160 sh, 1200, 1250, 1330,
1370, 1460, 1620, 1640 sh, 2870, 2930, 3000, 3050,
3120. 1H NMR spectrum (CDCl3), į, ppm: 6.44 q (1H,
OCH=), 4.15 d.d and 3.97 d.d (1H each, CH2=), 3.82–
3.66 m [4H, (CH2)2], 3.41 q (2H, OCH2), 3.10 m (1H,
CH), 2.74 d.d and 2.56 q (1H each, CH2). 13C NMR
spectrum (CDCl3), įC, ppm: 155.56 (OCH=), 86.55
(CH2=), 71.86 (OCH2), 69.54 (OCH2), 67.08 (OCH2),
50.48 (CH), 43.74 (CH2).
The IR spectra were recorded on a Specord 75IR
spectrometer from samples prepared as thin films. The
1H and 13C NMR spectra were measured on a Bruker
DPX-400 instrument at 400 and 100 MHz, respec-
tively, from ~5–10% solutions in CDCl3 or CCl4–
CDCl3 using HMDS as internal reference and on
a Bruker DPX-250 spectrometer at 250 and 62.9 MHz,
respectively, from ~5–10% solutions in CDCl3 using
TMS as internal reference. Toluene was purified by the
known procedure [31]. Dimethyl sulfoxide was heated
with KOH for a short time to 120°C, left to stand
for 10–12 h at room temperature, and distilled under
reduced pressure over t-BuOK. Tetrahydrofuran was
kept over KOH and was then distilled over calcium
hydride in the presence of benzophenone. 2-[2-(Vinyl-
oxy)ethoxy]methyloxirane (Ib) was synthesized by the
procedure reported in [32]. Commercial 2-(allyloxy-
methyl)oxirane (Ia) and 2-propynol were purified by
distillation. The purity of the initial compounds was
checked by NMR spectroscopy.
1-Allyloxy-3-(2-propynyloxy)propan-2-ol (IIa).
a. A mixture of 5.6 g (100 mmol) of 2-propynol, 10 g
(87.7 mmol) of oxirane Ia, and 0.47 g (~3 wt %) of
t-BuOK was stirred for 8 h at 75–80°C (Table 1, run
no. 3). It was then cooled to 20°C and poured into
60 ml of aqueous ammonium chloride, the organic
layer was separated, and the aqueous layer was treated
with diethyl ether (3×50 ml). The extracts were com-
bined with the organic phase, washed with water, dried
over MgSO4, and evaporated on a rotary evaporator.
The residue was 10.44 g (70%) of IIa; vacuum distilla-
tion gave 7.03 g (47.2%) of the product.
2-(Allyloxymethyl)oxirane (Ia). IR spectrum, Ȟ,
cm–1: 770, 800, 840 sh, 850, 920, 990, 1100, 1140 sh,
1160 sh, 1270, 1340, 1410, 1450, 1640, 2850, 2900,
1
2930, 3000, 3050, 3070. H NMR spectrum (CDCl3),
b. The reaction mixture obtained under the condi-
į, ppm: 5.88 m (1H, CH=), 5.25 d.m and 5.15 d.m (1H
tions of run no. 5 (Table 1) was cooled to room tem-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 10 2005

VINYL ETHERS CONTAINING AN EPOXY GROUP: XXII.
1441
perature and immediately dissolved in ~20–30 ml of
diethyl ether. The solution was passed through a small
(2.5–3.0 cm) layer of Al2O3, the solvent was removed
on a rotary evaporator, and the residue was distilled
under reduced pressure. Yield 11.9 g (68.2%), color-
less liquid, bp 81–82°C (1 mm), nD20 = 1.4630. IR spec-
trum, Ȟ, cm–1: 560, 630, 680, 840, 920, 950, 1000,
1100, 1205, 1270, 1330, 1360, 1400 sh, 1405, 1440,
1640 (C=C), 2120 (CŁC), 2850, 2900, 3010, 3080,
3280 (H–CŁ), 3430 (OH). 1H NMR spectrum, į, ppm:
Transformations of compounds IIa and IIb in
the presence of bases (general procedure). A mixture
of 10 mmol of 3-(2-propynyloxy)propan-2-ol IIa or
IIb and 4 mmol of t-BuOK or KOH in 10 ml of
appropriate solvent was stirred under the conditions
specified in Tables 2 and 3. The mixture was cooled to
20°C and poured into 50–60 ml of an aqueous solution
of ammonium chloride (with t-BuOK as base) or 50–
60 ml of water acidified with 1–2 ml of hydrochloric
acid (with KOH). The organic phase was separated,
the aqueous phase was extracted with diethyl ether
(2×50 ml), the extracts were combined with the
organic phase, washed with water, dried over MgSO4,
and evaporated under reduced pressure, and the residue
was subjected to vacuum distillation to isolate frac-
tions boiling in the temperature range from 48 to 51°C
(1 mm) (mixture of compounds Va–VIIIa) or from
85 to 88°C (1 mm) (Vb–VIIIb).
4
3
2.48 t (1H, HCŁ, J = 2.35 Hz), 3.01 d (1H, OH, J =
4.0 Hz), 3.46 and 3.50 (2H, CH2CCH2, AB quartet,
each component of which was split into a doublet due
3
3
to coupling with CHOH, JAB = 9.88, J = 6.36, J =
4.06 Hz), 3.54 and 3.60 (2H, CH2CHCH2, AB quartet
split into doublets due to coupling with CHOH, JAB
=
3
3
9.78, J = 6.26, J = 4.50 Hz), 3.96 m (1H, CHOH),
3
4
4.00 d.t (2H, =CHCH2O, J = 5.67, J = 1.47 Hz),
3
4.17 d (2H, CH2CŁ, J = 2.35 Hz), 5.17 d.d.t (1H,
2-Allyloxymethyl-6-methylene-1,4-dioxane (Va).
1H NMR spectrum of the cyclic fragment, į, ppm:
3.60–4.00 m (4H, CH2OCH2), 4.24 s (2H, exo-
C=CH2). 13C NMR spectrum, įC, ppm: 66.14
(CHCH2O), 66.68 (OCH2C=), 73.80 (OCH), 91.73
(C=CH2), 154.26 (C=CH2). The other 1H and 13C reso-
nance signals were obscured by signals of isomeric
cyclic compounds.
2
4
CH2=, Jcis = 10.37, J = J = 1.57 Hz), 5.26 d.d.t (1H,
CH2=, Jtrans = 17.31, 2J = 4J = 1.66 Hz), 5.89 d.d.t [1H,
CH=, Jtrans = 17.3, Jcis = 10.37, 3J(CH2CH) = 5.67 Hz].
13C NMR spectrum, įC, ppm: 58.62 (OCH2CŁ), 69.38
(CHOH), 71.35 and 71.38 (OCH2CHCH2O), 72.35
(=CHCH2), 74.94 (HCŁ), 79.61 (CŁ), 117.24 (CH2=),
134.64 (CH=). Found, %: C 63.83; H 8.36. C9H14O3.
Calculated, %: C 63.51; H 8.29.
6-Methylene-2-[2-(vinyloxy)ethoxymethyl]-1,4-
1
3-(2-Propynyloxy)-1-[2-(vinyloxy)ethoxy]-
propan-2-ol (IIb) was synthesized in a similar way
from 2-propynol and oxirane Ib [1]. Yield 95.3%,
bp 122–123°C (1 mm), nD20 = 1.4680. IR spectrum, Ȟ,
cm–1: 860, 1200, 1330, 1620, 1640 sh (C=C), 2120
(CŁC), 2860, 2930, 3050, 3120, 3280 split (H–CŁ),
dioxane (Vb). H NMR spectrum of the cyclic frag-
ment, į, ppm: 3.60–4.00 m (4H, CH2OCH2), 4.43 s
13
(2H, exo-C=CH2). C NMR spectrum, įC, ppm: 65.64
and 66.16 (CH2OCH2), 75.19 (OCH), 91.32 (C=CH2),
154.45 (C=CH2). Signals from the other fragments in
the spectra of mixtures of isomeric products were dif-
ficult to assign.
1
3450 (OH). H NMR spectrum, į, ppm: 2.48 t [1H,
4
HCŁ, J(CH2CŁCH) = 1.2 Hz], 2.95 d [1H, OH,
3J(HOCH) = 5.6 Hz], 3.51 d.d and 3.57 d.d (1H each,
CH2CHCH2, AB quartet split into doublets due to
2-Allyloxymethyl-2,3-dihydro-5H-1,4-dioxepine
1
(VIa). H NMR spectrum of the cyclic fragment, į,
3
3
ppm: 3.60–4.00 m (4H, CH2OCH2), 4.62 d.d.d (1H,
coupling with CHOH, JAB = 9.39, J = 6.48, J =
4.40 Hz), 3.54 d.d and 3.60 d.d (1H each, CH2CHCH2,
AB quartet split into doublets due to coupling with
CHOH, JAB = 9.39, 3J = 6.42, 3J = 4.52 Hz), 3.72 t (2H,
OCH2CH2O, J = 5.2 Hz), 3.82 t (2H, OCH2CH2O, J =
5.2 Hz), 3.99 m (1H, CHOH), 4.01 d.d (1H, CH2=,
3
3
6-H, J6,7 = 7.58, J = 4.89, J = 3.67 Hz), 6.24 d.d.d
4
4
(1H, 7-H, J6, 7 = 7.58, J = 2.08, J = 0.98 Hz).
13C NMR spectrum, įC, ppm: 66.13 and 67.50
(CH2OCH2), 72.80 (OCH), 105.55 (C6), 145.09 (C7).
13
The other 1H and C resonance signals were obscured
2
4
by signals of isomeric cyclic compounds.
Jcis = 8.0, J = 2.0 Hz), 4.18 d (2H, CH2CŁ, J =
1.2 Hz), 4.19 d.d (1H, CH2=, Jtrans = 16.0, 2J = 2.0 Hz),
6.46 d.d (1H, OCH=, Jtrans = 16.0, Jcis = 8.0 Hz).
13C NMR spectrum, įC, ppm: 58.68 (CH2CŁ), 67.39
and 69.94 (OCH2CH2O), 69.41 (CHOH), 71.19 and
72.66 (OCH2CHCH2O), 75.02 (HCŁ), 79.70 (CŁ),
86.95 (CH2=), 151.77 (OCH=). Found, %: C 59.49;
H 8.27. C10N16O4. Calculated, %: C 59.98; H 8.05.
2-[2-(Vinyloxy)ethoxymethyl]-2,3-dihydro-5H-
1
1,4-dioxepine (VIb). H NMR spectrum, į, ppm:
3.60–4.00 m (4H, CH2OCH2), 4.77 d.d.d (1H, 6-H,
3
3
J6,7 = 7.60, J = 4.91, J = 3.63 Hz), 6.35 d.d.d (1H,
7-H, J6,7 = 7.60, J = 2.09, J = 1.00 Hz). 13C NMR
spectrum, įC, ppm: 67.65 and 69.08 (CH2OCH2), 74.46
(OCH), 105.89 (C6), 145.33 (C7). The other 1H and 13C
4
4
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 10 2005

DMITRIEVA et al.
1442
resonance signals were obscured by signals of isomeric
cyclic compounds.
MeCH=, 3J = 6.85, Jcis = 6.60 Hz), 5.22 d (1H, OCHO,
3
3J = 6.11 Hz), 5.33 d (1H, OCHO, J = 5.33 Hz),
5.32 d.d.d (1H, CH2=CH, Jcis = 10.27 Hz), 5.34 d.d.d
2-Vinyl-1,3-dioxolane VIIa and 2,3-dihydro-1,4-
dioxine VIIIa were isolated as individual substances
by column chromatography on Silica gel 60 (0.063–
0.200 mm) using benzene as eluent.
2
4
(1H, CH2=CH, Jcis = 10.30, J = 1.22, J = 0.61 Hz),
5.46 d.d.d (1H, CH2=CH, Jtrans = 17.24, 2J = 1.22, 4J =
0.73 Hz), 5.47 d.d.d (1H, CH2=CH, Jtrans = 17.24, 2J =
1.22, 4J = 0.73 Hz), 5.95 m (1H, OCH=). Signals from
the =CHOCH2 fragment were overlapped by signals
from the OCH2 groups of dioxine derivative VIII.
13C NMR spectrum, į, ppm: 9.22 (Me), 67.11 and
67.22 (C5), 71.88 and 72.18 (4-CH2), 74.48 and 74.91
(C4), 103.58 and 104.13 (C2), 119.43 and 120.11
(CH2=), 134.37 and 134.46 (CH=C), 134.40 and
134.51 (MeCH=), 145.57 and 145.58 (OCH=).
(d,l/meso)-4-Allyloxymethyl-2-vinyl-1,3-dioxo-
1
lane (VIIa). H NMR spectrum, į, ppm: 3.38 d.d and
3.48 d.d (1H each, d/l-C5H2, AB part of ABX spin sys-
2
tem, JAB = 10.00, 3JAX = 3JBX = 5.00 Hz), 3.44 d.d and
3.50 d.d (1H each, meso-C5H2, AB part of ABX spin
2
3
3
system, JAB = 10.00, JAX = JBX = 5.50 Hz), 3.66 d.d
and 4.06 d.d (1H each, d,l-4-CH2, AB part of ABX spin
2
3
3
system, JAB = 9.00, J = 6.50, J = 7.50 Hz), 3.76 d.d
and 3.90 d.d (1H each, meso-4-CH2, AB part of ABX
2-Allyloxymethyl-6-methyl-2,3-dihydro-1,4-di-
oxine (VIIIa). 1H NMR spectrum, į, ppm: 1.66 d (3H,
2
3
3
spin system, JAB = 9.50, J = 5.50, J = 5.00 Hz),
3.96 m (2H, OCH2CH=), 4.20 m (1H, d/l-4-H), 4.24 m
(1H, meso-4-H), 5.12 d (2H, CH2=CHCH2), 5.21 d
(2H, CH2=CHCH2, Jtrans = 17.00 Hz), 5.16 d (1H,
4
Me, J = 1.22 Hz), 3.53 d.d (1H, OCH2CH, A part
2
3
of AB quartet, JAB = 10.27, J = 5.75 Hz), 3.60 d.d
3
(1H, OCH2CH, B part of AB quartet, JAB = 10.27, J =
3
3
5.14 Hz), 3.75 d.d (1H, 3-H, A part of AB quartet, JAB
=
d/l-2-H, J = 6.00 Hz), 5.29 d (1H, meso-2-H, J =
5.38 Hz), 5.26 d (2H, d/l-CH2=CHC2, Jcis = 10.50 Hz),
5.29 d (2H, meso-CH2=CHC2, Jcis = 10.50 Hz),
3
11.00, J = 6.97 Hz), 4.06 d.d (1H, 3-H, B part of AB
3
quartet, JAB = 11.00, J = 2.32 Hz), 4.06 d.t (2H,
3
4
5.41 d.d.d (2H, d/l-CH2=CHC2, Jtrans = 17.36, J =
2
=CHCH2O, J = 5.75, J = 1.34 Hz), 4.12 m (1H,
CHO), 5.18 d.d.t (1H, CH2=CH, Jcis = 10.39, 2J = 4J =
1.10, J = 0.98 Hz), 5.43 d.d.d (2H, meso-CH2=CHC2,
4
2
2
4
1.34 Hz), 5.26 d.d.t (1H, CH2=CH, Jtr4ans = 17.24, J =
Jtrans = 17.36, J = 1.10, J = 0.86 Hz), 5.70–5.90 d.d.t
(1H, CH2=CHCH2), 5.70–5.90 d.d.d (1H, CH2=CHC2).
13C NMR spectrum, įC, ppm: 67.14 and 67.38 (C5),
70.23 and 70.64 (=CHCH2O), 72.25 (4-CH2), 74.54
and 74.98 (C4), 103.67 and 104.21 (C2), 117.04 and
117.06 (CH2=CHCH2), 119.53 and 120.21 (CH2=CHC2),
134.35 (CH2=CHCH2), 134.42 and 134.52 (2-CH=).
4J = 1.47 Hz), 5.77 q (1H, 5-H, J = 1.22 Hz),
5.88 d.d.t (1H, CH=CH2, Jtrans = 17.24, Jcis = 10.39,
3J = 5.75 Hz). 13C NMR spectrum, įC, ppm: 15.65
(Me), 64.86 (C3), 68.64 (OCH2CH=), 72.03 and 72.33
(2-CH2), 74.58 and 75.02 (C2), 117.16 (CH2=), 121.10
(C5), 133.21 (C6), 134.36 (CH=CH2).
6-Methyl-2-[2-(vinyloxy)ethoxymethyl]-2,3-dihy-
(d,l/meso)-2-Vinyl-4-[2-(vinyloxy)ethoxymethyl]-
1
1
dro-1,4-dioxine (VIIIb). H NMR spectrum, į, ppm:
1,3-dioxolane (VIIb). H NMR spectrum, į, ppm:
4
5.12 d (1H, OCHO, 3J = 7.00 Hz), 5.25 d (1H, OCHO,
1.66 d (3H, Me, J = 1.2 Hz), 3.90 d.d (1H, CH2=,
Jcis = 8.00, 2J = 2.40 Hz), 4.00 m (1H, CHO), 4.08 d.d
3J = 7.00 Hz), 5.22 d (1H, CH2=CHC2, Jcis = 8.00, 2J =
2
4
1.22, J = 0.61 Hz), 5.24 d (1H, CH2=CHC2, Jcis
=
(1H, CH2=, Jtrans = 16.00, J = 2.40 Hz), 5.68 q (1H,
4
8.00 Hz), 5.36 d (1H, CH2=CHC2, Jtrans = 16.00 Hz),
5.38 d (1H, CH2=CHC2, Jtrans = 16.00 Hz). The other
1H resonance signals of compound VIIb were ob-
scured by signals of the other isomeric cyclic ethers.
13C NMR spectrum, į, ppm: 67.06 and 67.39 (C5),
74.60 and 74.88 (C4), 104.08 and 104.59 (C2), 120.06
and 120.65 (CH2=), 134.40 and 134.52 (CH=C).
5-H, J = 1.2 Hz), 6.37 d.d (1H, OCH=, Jtrans = 16.00,
Jcis = 8.00 Hz). 13C NMR spectrum of the cyclic
fragment, įC, ppm: 15.53 (Me), 64.63 (C3), 74.91 (C2),
1
121.04 (C5), 133.02 (C6). The other H and 13C reso-
nance signals were obscured by signals of isomeric
compounds.
6-Methyl-2-(1-propenyloxymethyl)-2,3-dihydro-
1
1,4-dioxine (VIIIc). H NMR spectrum, į, ppm:
(d,l/meso)-4-(1-Propenyloxymethyl)-2-vinyl-1,3-
dioxolane (VIIc). 1H NMR spectrum, į, ppm: 1.55 d.d
1.55 d.d (3H, MeCH=, 3J = 6.83, 4J = 1.71 Hz), 1.65 d
3
4
4
(3H, Me, J = 6.85, J = 1.59 Hz), 1.56 d.d (3H, Me,
(3H, 6-Me, J = 1.22 Hz), 3.87 d.d (1H, 2-CH2, A part
3J = 6.85, J = 2.08 Hz), 3.88 d.d (1H, CHCH2O, A
part of AB quartet, JAB = 8.19, J = 5.14 Hz), 3.96 d.d
(1H, CHCH2O, B part of AB quartet, JAB = 8.19, J =
of AB quartet, JAB = 10.88, 3J = 5.14 Hz), 4.03 d.d (1H,
4
3
3
3-H, A part of AB quartet, JAB = 11.00, J = 2.32 Hz),
3
3.67–3.82 (2H, 2-CH, 3-H, B parts of overlapping
AB quartets from OCH2 groups), 4.28 m (1H, OCH),
6.72 Hz), 4.13 m (1H, OCHCH2), 4.39 d.q (1H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 10 2005

VINYL ETHERS CONTAINING AN EPOXY GROUP: XXII.
1443
3
Jong, R.L.P., Verkruijsse, H.D., and Brandsma, L.,
Perspectives in the Organic Chemistry of Sulfur,
Zwanenburg, B. and Klunder, A.J.H., Eds., Amsterdam:
Elsevier, 1987, p. 105.
4.41 d.q (1H, MeCH=, Jcis = 6.7, J = 6.6 Hz), 5.77 q
(1H, 5-H, 4J = 1.22 Hz), 5.93 d.q (1H, OCH=CH, Jcis
=
6.7, J = 1.71 Hz). 13C NMR spectrum, į, ppm: 9.20
(MeCH=), 15.80 (6-Me), 64.67 (C3), 70.81 (2-CH2),
72.95 (C2), 121.32 (C5), 133.40 (C6), 134.50 (MeCH=),
145.60 (OCH=).
4
14. Potthoff, B. and Breitmaier, E., Chem. Ber., 1986,
vol. 119, p. 3204; Fetizon, M., Goulaouic, P., and
Hanna, I., J. Org. Chem., 1988, vol. 53, p. 5672;
Fetizon, M., Goulaouic, P., and Hanna, I., Heterocycles,
1989, vol. 28, p. 521; Blanchot, V. and Hanna, I., Synth.
Commun., 1991, vol. 21, p. 563; Hanna, I., Tetrahedron
Lett., 1995, vol. 36, p. 889; Fujioka, H., Kitagawa, H.,
Nagotimi, Y., and Kita, Y., J. Org. Chem., 1996, vol. 61,
p. 7309; Teng, X., Takayama, Y., Okamoto, S., and
Sato, F., J. Am. Chem. Soc., 1999, vol. 121, p. 11916;
O’Leary, D.J., Blackwell, H.E., Washenfelder, R.A.,
Miura, K., and Grubbs, R.H., Tetrahedron Lett., 1999,
vol. 40, p. 1091.
15. Yamamoto, M., Itoh, M., Ishiko, T., Kishikawa, K., and
Kohmoto, Sh., Abstracts of 17th Int. Congress of
Heterocyclic Chemistry, Vienna, August 1–6, 1999,
PO-32; Friesen, R.W., J. Chem. Soc., Perkin Trans. 1,
2001, p. 1969.
16. Nicolaou, K.C. and Smith, A.L., The Enediyne Anti-
biotics. Modern Acetylene Chemistry, Stang, P.J. and
Diederich, F., Eds., Weinheim: VCH, 1995, p. 203.
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