Oxidation of substituted 1,5-hexadien-3-ols with various oxidants

Article abstract of DOI:10.1023/A:1013843700623

Substituted 1,5-hexadien-3-ols were synthesized by the [2,3]-Wittig rearrangement of unsymmetrical bis-allyl ethers, as well as by reactions of 1-(2-alkenyl)-2-chloromethyloxiranes with Mg/THF. The products were oxidized with pyridinium chlorochromate (PCC), zinc chlorochromate (ZCC), tert-butyl hydroperoxide in the presence of OsO4, and tert-butyl hydroperoxide alone. The oxidation of substituted 1,5-hexadien-3-ols with PCC and ZCC gave the corresponding carbonyl compounds. In the reaction with tert-butyl hydroperoxide catalyzed by OsO4 the internal double bond in the substrate was regioselectively converted into epoxy group, whereas allylic oxidation was prevented.

Full text of DOI:10.1023/A:1013843700623

Russian Journal of Organic Chemistry, Vol. 37, No. 11, 2001, pp. 1542 1548. From Zhurnal Organicheskoi Khimii, Vol. 37, No. 11, 2001,
pp. 1618 1624.
Original English Text Copyright
2001 by Servi, Cansiz, Acar, Koparir.
Oxidation of Substituted 1,5-Hexadien-3-ols
*
with Various Oxidants
S. Servi, A. Cansiz, A. Acar, and M. Koparir
Fen-Edebiyat Faculty, Firat University, Elazig, 23169 Turkey
e-mail: syleymanselvi@hotmail.com
Received November 27, 2000
Abstract Substituted 1,5-hexadien-3-ols were synthesized by the [2,3]-Wittig rearrangement of unsym-
metrical bis-allyl ethers, as well as by reactions of 1-(2-alkenyl)-2-chloromethyloxiranes with Mg/THF.
The products were oxidized with pyridinium chlorochromate (PCC), zinc chlorochromate (ZCC), tert-butyl
hydroperoxide in the presence of OsO , and tert-butyl hydroperoxide alone. The oxidation of substituted
4
1
,5-hexadien-3-ols with PCC and ZCC gave the corresponding carbonyl compounds. In the reaction with tert-
butyl hydroperoxide catalyzed by OsO the internal double bond in the substrate was regioselectively con-
4
verted into epoxy group, whereas allylic oxidation was prevented.
Oxidation reactions are very important for organic
chemistry and biological systems. Organic molecules
having benzylic or allylic hydrogen atoms are oxidized
with atmospheric oxygen or hydroperoxides to give
various products. Substituted 1,5-hexadien-3-ols pos-
sess allylic hydrogen atoms in different positions,
which promote their ready autooxidation. Substituted
zinc chlorochromate are cheaper and easy to prepare,
and procedures utilizing these oxidants are fairly
simple. PCC becomes a moderately strong oxidant
provided that its hygroscopicity and weakly acidic
character are modified by addition of sodium acetate.
ZCC is a very potent oxidant with respect to com-
pounds having allylic and benzylic hydrogen atoms.
Osmium(VIII) oxide is a very expensive and toxic
reagent. A disadvantage of t-BuOOH as oxidant is
that it promotes radical processes which result in
formation of a number of products. The use of tert-
butyl hydroperoxide in combination with a catalytic
amount of metal oxide ensures selective oxidation of
hydroxy groups to carbonyl. Oxidation of allyl-like
alcohols with t-BuOOH in the presence of some
catalysts yields the corresponding , -epoxy alcohols
1
,5-hexadien-3-ols are used in the synthesis of phero-
mones and antibiotics [1 3]; they also exhibit a very
strong antimicrobial activity [4]. Three methods for
preparation of substituted 1,5-hexadien-3-ols are
known. The first of these is based on the Grignard
reaction of unsaturated carbonyl compounds with
allyl- or vinylmagnesium halides [5 9]. The second
procedure involves four sigmatropic rearrangements
initiated by the regioselective [2,3]-Wittig rearrange-
ment of unsymmetrical bisallyl ethers [10 14]. The
third method is reduction of 1-(2-alkenyl)-2-chloro-
methyloxiranes with metallic sodium in methanol or
their reaction with magnesium in THF [15 19].
[25 33]. Martin et al. used tert-butyl hydroperoxide
together with VO(acac) to synthesize glycosidase
2
inhibitors. The same oxidizing system was also used
for the synthesis of (+)-KDO from furan precursors
[34 36]. Ho and Sapp [37] studied by mass spec-
trometry the mechanism of oxidation of the furan ring
with the system t-BuOOH VO(acac)2.
Analysis of published data shows that oxidation
reactions of substituted 1,5-hexadienes have not been
studied in sufficient detail. The oxidants used in the
present work were thoroughly selected, taking into
consideration the substrate structure. Initial 1,5-hexa-
dien-3-ols were prepared by two different methods
(Scheme 1).
Numerous oxidants are now available for organic
compounds, and their list is supplemented almost
dayly [20 24]. Among these, the main are pyridi-
nium chlorochromate (PCC), zinc chlorochromate
(
ZCC), OsO , and t-BuOOH, which are used in
4
combination with various catalysts. Depending on the
oxidant and substrate structure, various oxidation
products are formed. Pyridinium chlorochromate and
_
*
___________
The original article was submitted in English.
1
070-4280/01/3711-1542$25.00 2001 MAIK Nauka/Interperiodica

OXIDATION OF SUBSTITUTED 1,5-HEXADIEN-3-OLS
1543
Scheme 1.
1
2
3
1
3
2
1
2
3
1
2
3
R = R = H, R = CH (a); R = R = CH , R = H (b); R = CH , R = R = H (c); R = C H , R = R = H (d).
3
3
3
6
5
Unsymmetrical bisallyl ethers IIc and IId were
synthesized by reactions of trans-2-buten-1-ol (Ic) and
trans-3-phenyl-2-propen-1-ol (Id) with allyl bromide
IIIa, IIIb, IVa, and IVb were synthesized by the
procedures described in [15 19].
The oxidation of compounds IVa IVd with PCC
in the presence of potassium hydroxide and tetrabutyl- (method A) and ZCC (method B) gave the correspond-
ammonium hydrogen sulfate as phase-transfer catalyst.
Substituted 1,5-hexadien-3-ols were obtained in high
yield by the [2,3]-Wittig rearrangement of ethers IIc
and IId at 75 C under argon [10 14]. Compounds
ing carbonyl compounds Va and Vb. In the oxidation
of IVa with PCC product VIa was isolated in addition
to Va. Being a strong oxidant with respect to allylic
and benzylic hydrogen atoms, ZCC oxidized alcohol
Scheme 2.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 11 2001

1
544
SERVI et al.
Scheme 3.
IVa to 2-methyl-1,5-hexadiene-3,4-dione (VIa); the
latter was formed as a result of oxidation of both
allylic hydrogen atom and allylic hydroxy group in
IVa (Scheme 2). By oxidation of compound IVd with
PCC and ZCC we obtained benzaldehyde (VII), cin-
namaldehyde (VIII), and 1-phenyl-1,5-hexadien-3-one
benzaldehyde were obtained only by oxidation of
compound IVd according to method C. On the other
hand, allylic hydrogen atom or allylic hydroxy group
could be abstracted by t-BuO or t-BuOO radicals.
The oxygen oxygen bond in alkyl hydroperoxides is
very weak, and its dissociation produces radical
species which are capable of initiating the other chains
(Vd). The fraction of benzaldehyde was greater when
(Scheme 4).
the reaction was performed with ZCC as oxidant. It
should be noted that oxidation of IVd with both PCC
and ZCC gives products with smaller molecular
weights owing to decomposition of the initial mole-
cule (Scheme 2).
Scheme 4.
Presumably, the oxidation of olefins having allylic
hydrogen atoms follows two pathways: allylic oxida-
tion and direct attack on the double bond. In the pres-
ence of such oxygen carriers as t-BuOOH or H O ,
2
2
the metal can serve as a relay for transfer of oxygen
atom from the hydroperoxide to the olefin via an oxo-
metal intermediate. The dismutation of t-BuOOH to
t-BuOH and O in the presence of transition metals
2
The oxidation of compounds IVc and IVd with
has been well documented. tert-Butyl hydroperoxide
is known to oxidize olefins to epoxy derivatives and
allylic oxidation products in the presence of transition
metal catalysts.
Catalytic epoxidation and allylic oxidation reac-
tions follow different paths. The first of these involves
oxygen transfer, while the second is a radical process
t-BuOOH in the absence of a catalyst (method D)
gives both epoxidation and allylic oxidation products.
We believe that the oxidation with tert-butyl hydro-
peroxide is a completely radical process which
involves formation of two different intermediates.
Compounds IVa IVd have allylic hydrogen atoms,
allylic hydroxy groups (IVa IVc), and benzylic
hydrogen atom (IVd) in different positions. tert-Butyl-
dioxy radical formed by decomposition of t-BuOOH
oxidizes the hydroxy group to carbonyl (intermediate
A); simultaneously, one or both double bonds are con-
verted into epoxy group. The t-BuOO radical behaves
(Scheme 3). The epoxidation could occur via activa-
tion of the peroxide oxygen atoms.
In the oxidation of substituted 1,5-hexadien-3-ols
with tert-butyl hydroperoxide catalyzed by OsO4
(method C), only the internal double bond was con-
verted into epoxy group while no allylic oxidation very selectively in the formation of intermediate
products were formed. , -Epoxy alcohols and
product of allylic oxidation. The methyl group in
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 11 2001

OXIDATION OF SUBSTITUTED 1,5-HEXADIEN-3-OLS
1545
IVc acts as electron donor through the hyperconjuga-
tion effect. -Conjugation of the phenyl group with
the double bond in compound IVd increases the
stability of intermediate A (Scheme 3), so that none
of the oxidation products is formed through inter-
mediate B.
through a dropping funnel. After 1 2 h, the reaction
completion was checked by TLC. The black mixture
was diluted with a fivefold volume of ether. The
precipitate was filtered off and washed with two
portions of ether. The ether solution was dried over
MgSO and evaporated under reduced pressure, and
4
the crude product was subjected to column chromato-
graphy on silica gel.
When the oxidation was effected with t-BuOOH
and a catalytic amount of OsO , only the internal
4
double bond of the substrate was converted into epoxy
group. No allylic oxidation products were obtained
following method C. Osmium(VIII) oxide prevents
both transformation of the terminal double bond into
Method B. Oxidation of compounds IVa IVd
with zinc chlorochromate. A solution of 8 mmol of
compound IVa IVd in 70 ml of CH Cl was prepared
in a 200-ml round-bottom flask equipped with
a magnetic stirrer. Zinc chlorochromate, 16 mmol,
was added to the solution in four portions over
a period of 15 min under vigorous stirring. The
mixture was stirred for 2 h, diluted with 120 ml of
2
2
epoxy group and allylic oxidation; OsO also provides
4
regioselective oxidation according to method C. In
method D, tert-butyldioxy radical selectively oxidizes
the allylic hydroxy group. The reaction with IVd is
also accompanied by formation of benzaldehyde as CH Cl , and filtered, and the filtrate was carefully
a result of benzylic oxidation.
2
2
evaporated on a rotary evaporator in a vacuum.
Thus, tert-butyl hydroperoxide in the presence of
Method C. Oxidation of compounds IVc and IVd
with tert-butyl hydroperoxide in the presence of OsO4.
A 50-mmol portion of compound IVc or IVd was
dissolved in 125 ml of t-BuOH, and 6.5 ml of a 20%
OsO as catalyst selectively oxidizes substituted
4
1
,5-hexadien-3-ols to , -epoxy alcohols. The use of
t-BuOOH alone results in oxidation of the allylic
hydroxy group to carbonyl with simultaneous trans-
formation of the double bond into epoxy group.
aqueous solution of NEt OH, 4 ml (103 mmol) of
4
t-BuOOH (a 3 M solution of isooctane), and 2.6 ml
(
0.2 mmol) of a 2.5% solution of OsO in t-BuOH
4
EXPERIMENTAL
were added. The mixture was kept for 12 h at room
temperature, 65 ml of a 5% solution of Na SO was
2
3
Chromium(VI) oxide, zinc(II) chloride, tetrabutyl-
ammonium hydrogen sulfate, butyllithium (as a 1.6 M
solution in hexane), tert-butyl hydroperoxide (as
a 3 M solution in isooctane), pyridine, trans-2-buten-
added, and the mixture was extracted with ether. The
extracts were washed with a saturated solution of
NaCl, dried over MgSO , and evaporated.
4
Method D. Oxidation of compounds IVc and IVd
with tert-butyl hydroperoxide. The procedure was the
same as in method C with the difference that OsO4
was not added.
1
-ol, trans-3-phenyl-2-propen-1-ol, and tert-butyl
alcohol were commercial products. All solvents were
used without additional purification.
The progress of reactions was monitored by thin-
layer chromatography on silica gel 60 F254 applied
to aluminum plates; and the products were purified
by column chromatography. The IR spectra were
(
2E)-1-Allyloxy-2-butene (IIc). Yield 69%.
1
bp 48 49 C (50 mm). IR spectrum (NaCl), , cm :
080, 1650, 1130, 960, 936. H NMR spectrum
1
3
1
(CDCl , 90 MHz), , ppm: 1.57 1.71 d (3H, J =
recorded on a Wattson FT-IR spectrometer. The H
3
and 13C NMR spectra were measured on Jeol FX-90Q
7 Hz), 3.88 m (4H), 5.02 5.22 m (2H), 5.22 6.15 m
(
3H). 13C NMR spectrum, C, ppm: 17.6, 71.0, 116.3,
and Bruker AC-200 instruments relative to tetra-
methylsilane. The GC MS and elemental analyses
were performed at the Center of Science and Techno-
logy Research of Turkey (TUBITAK).
1
28.4, 128.7, 135.5. Found, %: C 74.6; H 10.4.
C H O. Calculated, %: C 75.0; H 10.7.
7
12
3-(Allyloxy)-1-phenylpropene (IId). Yield 71%.
1
bp 118 120 C (10 mm). IR spectrum (NaCl), , cm :
Oxidation of substituted 1,5-hexadien-3-ols
1
(method A; oxidation of compounds IVa IVd with
3080, 3040, 1657, 1140, 965, 750 700. H NMR
pyridinium chlorochromate). Pyridinium chloro-
chromate, 1.5 mmol, was dissolved in 2 ml of
CH Cl , 0.03 mmol of sodium acetate was added to
spectrum (CDCl , 90 MHz), , ppm: 3.95 m (4H),
3
4.84 5.35 m (2H), 5.54 6.66 m (3H), 6.94 7.53 m
1
3
(5H). C NMR spectrum, C, ppm: 70.6, 116.2,
124.9, 127.0, 128.5, 130.9, 131.5, 134.3. Found, %:
2
2
the solution, and a solution of 1 mmol of substituted
,5-hexadien-3-ol in 1.5 ml of CH Cl was added
1
C 83.1; H 8.3. C H O. Calculated, %: C 82.8; H 8.0.
2
2
12 14
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 11 2001

1
546
SERVI et al.
5-Methyl-1,5-hexadien-3-one (Va). IR spectrum
6
-Chloro-4,5-epoxy-2-methyl-1-hexene (IIIa).
1
1
Yield 76%. bp 70 72 C (20 mm). IR spectrum
(NaCl), , cm : 3080, 1680, 1625, 935. H NMR
spectrum (CDCl , 90 MHz), , ppm: 2.2 s (3H),
1
1
(NaCl), , cm : 3080, 1640, 1250, 720. H NMR
3
4
.47 s (2H), 4.75 s (2H), 6.27 6.31 m (3H). GC MS
spectrum (CDCl , 90 MHz), , ppm: 1.75 s (3H), 2.2
2
4
3
+
data: M , m/z 110; base peak, m/z 55; retention time
.378 min. Yield 67.5%. Found, %: C 77.1; H 9.5.
.3 m (2H), 2.97 3.00 m (2H), 3.36 3.57 m (2H),
.82 m (2H). Found, %: C 57.1; H 7.3; Cl 23.8.
9
C H O. Calculated, %: C 77.4; H 9.7.
C H ClO. Calculated, %: C 57.3; H 7.5; Cl 24.2.
8
12
7
11
(
5E)-2-Methyl-1,5-heptadien-4-one (Vb). IR spe-
6
-Chloro-2-methyl-4,5-epoxy-1-heptene (IIIb).
1
ctrum (NaCl), , cm : 3040, 1680, 1625, 990, 935.
H NMR spectrum (CDCl , 90 MHz), , ppm: 2.2 s
3H), 4.47 s (2H), 4.75 s (2H), 6.0 6.8 m (2H).
GC MS data: M , m/z 124; base peak, m/z 109; reten-
tion time 9.492 min. Yield 58.3%. Found, %: C 77.1;
H 9.5. C H O. Calculated, %: C 77.4; H 9.7.
Yield 79%. bp 92 93 C (4 mm). IR spectrum (NaCl),
cm : 3081, 1641, 1250, 732. H NMR spectrum
CDCl , 200 MHz), , ppm: 1.55 (3H, J = 7 Hz),
.8 s (3H), 2.22 d.d (1H, J = 15, 6 Hz), 2.33 d.d (1H,
J = 15, 6 Hz), 2.93 d.d (1H, J = 7, 2 Hz), 3.85 quint
1H, J = 7 Hz), 3.93 t.d (1H, J = 6, 2 Hz), 4.82 s
1H), 4.85 s (1H). Found, %: C 59.7; H 7.8; Cl 22.3.
1
1
1
,
3
(
(
1
3
+
(
(
8
12
(
5E)-1,5-Heptadien-4-one (Vc). IR spectrum
1
1
C H ClO. Calculated, %: C 59.8; H 8.1; Cl 22.1.
(NaCl), , cm : 3040, 1680, 1625, 990. H NMR
8
13
spectrum (CDCl , 90 MHz), , ppm: 2.1 m (3H),
5
-Methyl-1,5-hexadien-3-ol (IVa). IR spectrum
3
1
3
1
1
4.37 m (2H), 5.0 5.7 m (3H), 6.02 6.76 m (2H).
C
(
NaCl), , cm : 3380, 3050, 1645, 935. H NMR
spectrum (CDCl , 90 MHz), , ppm: 1.61 s (3H),
.2 d (4H), 3.04 s (1H), 3.94 4.40 m (1H), 4.57
.45 m (2H), 5.56 6.12 m (1H). C NMR spectrum,
C, ppm: 22.7, 46.2, 70.8, 113.7, 114.5, 141.1. Found,
NMR spectrum, C, ppm: 17, 37, 124, 128, 130, 137,
3
1
97. Found, %: C 76.8; H 8.9. C H O. Calculated,
7 10
2
5
1
3
%: C 76.4; H 9.1.
(1E)-1-Phenyl-1,5-hexadien-3-one (Vd). IR spec-
1
%
: C 74.6; H 10.9. C H O. Calculated, %: C 75.0;
H 10.7.
trum (NaCl), , cm : 3040, 1680, 1625, 1080, 990,
7
12
1
760. H NMR spectrum (CDCl3, 90 MHz), , ppm:
4
.35 m (2H), 5.0 5.7 m (3H), 6.25 7.91 m (2H), 7.2
5
-Methyl-1,5-heptadien-4-ol (IVb). Yield 74%.
1
3
1
7.6 m (5H). C NMR spectrum, , ppm: 37, 123,
127, 128, 129, 131, 137, 197. GC MS data: M , m/z
C
bp 55 56 C (10 mm). IR spectrum (NaCl), , cm :
370, 3060, 1640, 935. H NMR spectrum (CDCl ,
00 MHz), , ppm: 1.67 d (3H, J = 7 Hz), 1.78 s
3H), 2.22 d (2H, J = 6 Hz), 4.2 t.d (1H, J = 7, 5 Hz),
.78 s (1H), 4.86 s (1H), 5.35 5.76 m (2H). C NMR
spectrum, C, ppm: 18.1, 22.9, 46.7, 114.0, 127.4,
34.0, 142.8. Found, %: C 75.9; H 11.6. C H O.
Calculated, %: C 75.0; H 10.7.
+
1
3
2
(
3
172; base peak, m/z 171; retention time 18.376 min.
Yield 48.2% (A), 36.1% (B). Found, %: C 83.2; H 7.3.
1
3
C H O. Calculated, %: C 83.7; H 7.0.
1
2
12
4
2
-Methyl-1,5-hexadiene-3,4-dione (VIa). GC MS
+
data: M , m/z 124; base peak, m/z 109; retention time
1
8 14
9
.492 min. Yield 3%. Found, %: C 67.3; H 6.8.
C H O . Calculated, %: C 67.7; H 6.5.
7
8
2
(5E)-1,5-Heptadien-4-ol (IVc). Yield 62%. bp 72
+
1
Benzaldehyde (VII). GC MS data: M , m/z 106;
base peak, m/z 77; retention time 7.457 min. Yield
7.5% (A), 37.2% (B), 21.2% (C), 6.3% (D).
-Phenylpropenal (VIII). GC MS data: M ,
7
3
4 C (35 mm). IR spectrum (NaCl), , cm : 3600
200, 3040, 1651, 1260, 1065, 935. H NMR spec-
trum (CDCl , 90 MHz), , ppm: 0.94 1.02 d (3H,
J = 4 Hz), 2.23 m (2H), 3.94 q (1H, J = 6 Hz), 5.14 m
2H), 5.82 m (3H). C NMR spectrum, C, ppm:
6.0, 38.6, 76.7, 116.2, 139.3, 140.8. Found, %:
C 75.4; H 10.9. C H O. Calculated, %: C 75.0;
1
2
3
+
3
1
3
m/z 132; base peak, m/z 131; retention time 13.576.
Yield 5.53%.
(
1
1
-(3-Methyloxiranyl)-3-buten-1-ol (IXc). IR
7
12
1
H 10.7.
1E)-1-Phenyl-1,5-hexadien-3-ol (IVd). Yield
2%. bp 130 132 C (2 mm). IR spectrum (NaCl), ,
spectrum (NaCl), , cm : 3450 3340, 3060, 1642,
250, 965. H NMR spectrum (CDCl , 90 MHz), ,
1
1
(
3
ppm: 1.32 d (3H, J = 7 Hz), 3.41 m (2H), 4.2 m (1H),
7
+
1
1
4.3 4.9 m (2H), 5.0 5.7 m (3H). GC MS data: M ,
cm : 3600 3200, 3040, 1651, 1260, 740. H NMR
m/z 128; base peak, m/z 55; retention time 10.821 min.
spectrum (CDCl , 90 MHz), , ppm: 3.78 4.25 m
3H), 4.95 5.46 m (2H), 5.60 6.72 m (3H), 7.1 7.8 m
5H). C NMR spectrum, C, ppm: 71.8, 117.0,
27.3, 129.4, 133.0, 135.8, 137.7. Found, %: C 82.1;
H 7.9. C H O. Calculated, %: C 82.8; H 8.1.
3
Yield 48.8%. Found, %: C 65.7; H 9.6. C H O .
(
(
1
7
12
2
1
3
Calculated, %: C 65.6; H 9.4.
1
-(3-Phenyloxiranyl)-3-buten-1-ol (IXd). IR
1
spectrum (NaCl), , cm : 3550 3480, 1641, 1245,
1
2
14
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 11 2001

OXIDATION OF SUBSTITUTED 1,5-HEXADIEN-3-OLS
1547
1
9
70, 740. H NMR spectrum (CDCl , 90 MHz), ,
4. Servi, S., Digrak, M., Cansiz, A., and Ahmet-
3
ppm: 3.41 m (3H), 4.23 m (1H), 4.4 5.0 m (2H),
zade, M., Indian J. Chem. Sec. B, in press.
+
5
.10 5.67 m (3H), 7.2 7.3 m (5H). GC MS data: M ,
m/z 190; base peak, m/z 91; retention time 16.524 min.
Yield 32.2%. Found, %: C 75.1; H 6.7. C H O .
5. Kiun-Hono, O., Ann. Chem., 1940, vol. 13, p. 175.
6
7
8
.
.
.
Violo, A. and Levasseur, L.A., J. Am. Chem. Soc.,
1965, vol. 87, p. 1150.
1
2
14
2
Calculated, %: C 75.8; H 6.3.
Fujita, Y., Onishi, T., and Nishida, T., Synthesis,
1978, p. 612.
1
-(3-Methyloxiranyl)-3-buten-1-one (Xc). IR
1
Fujita, Y., Amiya, S., Onishi, T., and Nishida, T.,
Bull. Chem. Soc. Jpn., 1978, vol. 52, p. 1983.
spectrum (NaCl), , cm : 3040, 1715, 1640, 1245,
080, 970, 760. H NMR spectrum (CDCl , 90 MHz),
1
1
3
,
ppm: 3.95 m (2H), 4.27 5.42 m (2H), 5.10 5.67 m
9. Zair, T., Rouvier, C.S., and Santelli, M., Tetra-
hedron, 1993, vol. 49, p. 3313.
+
(
3H), 7.2 7.3 m (5H). GC MS data: M , m/z 126;
base peak, m/z 59. Retention time 10.702 min. Yield
10. Takanashi, O., Maeda, T., Mikami, K., and Na-
1
0.8%. Found, %: C 66.9; H 7.9. C H O . Calcu-
kai, T., Chem. Lett., 1986, p. 1355.
7
10
2
lated, %: C 66.7; H 7.4.
11. Greves, N. and Vines, K.J., Tetrahedron Lett., 1994,
vol. 35, p. 7077.
1
-(3-Phenyloxiranyl)-3-buten-1-one (Xd). IR
1
1
2. Mikami, K., Kishi, N., and Nakai, T., Chem. Lett.,
994, vol. 35, p. 7077.
spectrum (NaCl), , cm : 3040, 1715, 1640, 1245,
080, 970, 765. H NMR spectrum (CDCl , 90 MHz),
ppm: 3.95 m (2H), 4.2 5.3 m (2H), 5.1 5.7 m
3H), 7.2 7.3 m (5H). GC MS data: M , m/z 188;
1
1
1
,
(
3
13. Nakai, T. and Mikami, K., Chem. Rev., 1986,
+
vol. 86, p. 885.
base peak, m/z 118; retention time 16.368 min. Yield
14. Mikami, K. and Nakai, T., Synthesis, 1991, p. 594.
1
6.4%. Found, %: C 76.2; H 6.9. C H O . Calcu-
12 12 2
15. Ahmedov, M.A., Vladimirov, I.I., and Kosti-
lated, %: C 76.6; H 6.4.
kov, R.R., Russ. J. Org. Chem., 1987.
1
-(3-Methyloxiranyl)-2-oxiranylethanone (XIc).
16. Sadikzade, S.I., Ahmedov, M.A., and Mehme-
1
1
dov, G.H., USSR Patents, 1973, vol. 40, p. 25.
IR spectrum (NaCl), , cm : 1720, 1250, 1100. H
NMR spectrum (CDCl , 90 MHz), , ppm: 1.34 s
17. Servi, S., Coskun, M., and Ahmetzade, M., J. Firat
Univ. Sci. Eng., 1995, vol. 8, p. 143.
3
(
3H), 3.42 m (2H), 3.81 4.69 m (3H), 4.57 5.41 m
+
(2H). GC MS data: M , m/z 142; base peak, m/z 71;
18. Servi, S., PhD Thesis, Firat University, Graduate
School of Natural and Applied Sciences, Elazig,
Turkey, 1995.
retention time 10.051 min. Yield 33.2%. Found, %:
C 59.9; H 7.4. C H O . Calculated, %: C 59.2; H 7.0.
7
10
3
1
9. Servi, S., Ahmetzade, M., Coskun, M., and Can-
2
-Oxiranyl-1-(3-phenyloxiranyl)ethanone (XId).
1
siz, A., S. Afr. J. Chem., in press.
IR spectrum (NaCl), , cm : 3040, 1715, 1250, 1100.
H NMR spectrum (CDCl , 90 MHz), , ppm: 3.42 m
2H), 3.81 4.69 m (3H), 4.63 5.52 m (2H), 7.2 7.3 m
5H). GC MS data: M , m/z 204; base peak, m/z 130;
retention time 17.257 min. Yield 13.4%. Found, %:
C 70.2; H 5.6. C H O . Calculated, %: C 70.6;
1
20. Ozgun, B. and Degirmencibasi, N., Synth. Commun.,
999, vol. 29, p. 763.
3
1
(
(
+
21. Sener, S. and Cetinkaya, E., Abstracts of Papers,
Xth National Chemistry Congress, Bursa, Turkey,
1994.
1
2
12
3
H 5.9.
22. Servi, S. and Acar, A., Abstracts of Papers,
XIIIth National Chemistry Congress, Samsun,
Turkey, 1999.
The authors are indebted to the Firat University
Research Foundation (FUNAF) for financial support
of this work (project no. 295).
2
2
2
3. Corey, E.J. and Suggs, J.W., Tetrahedron Lett.,
975, no. 31, p. 2647.
1
4. Firouzabad, H. and Sharifi, A., Synthesis, 1992,
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