Ozonolysis of (1R,cis)-4,7,7-trimethyl-3-oxabicyclo[4.1.0]hept-4-en-2-one

Article abstract of DOI:10.1023/A:1016543021664

The structure of peroxides forming in ozonolysis of enololactone and their further transformations are determined by the structure of the initial substrate and by effect of solvent used for ozonolysis.

Full text of DOI:10.1023/A:1016543021664

Russian Journal of Organic Chemistry, Vol. 38, No. 4, 2002, pp. 511 518. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 4, 2002,
pp. 536 543.
Original Russian Text Copyright
2002 by Kukovinets, Kasradze, Galin, Spirikhin, Zainullin, Kislitsyn, Abdullin, Kunakova, Tolstikov.
Ozonolysis
of (1R,cis)-4,7,7-Trimethyl-3-oxabicyclo[4.1.0]hept-4-en-2-one
O. S. Kukovinets, V. G. Kasradze, F. Z. Galin, L. V. Spirikhin,
R. A. Zainullin, M. I. Kislitsyn, M. I. Abdullin, R. V. Kunakova, and G. A. Tolstikov
Institute of Organic Chemistry, Ufa Scientific Center, Russian Academy of Sciences, Ufa, Bashkortostan, 450054 Russia
Bashkirskii State University, Institute of Service Technology of Ufa, Ufa, Bashkortostan, 450054 Russia
Received July 11, 2001
Abstract The structure of peroxides forming in ozonolysis of enololactone and their further transformations
are determined by the structure of the initial substrate and by effect of solvent used for ozonolysis.
The structure of peroxide ozonolysis products is
known to depend on the structure of initial substrate
and on the solvent for ozonolysis [1 3]. The investig-
ation of ozonolysis of (1R,cis)-4,7,7-trimethyl-3-
oxabicyclo[4.1.0]hept-4-en-2-one (I) originating from
lactonization of ketocaronic acid, potential synthon
for preparation of acid components from pyrethroid
series [4, 5], furnished an opportunity to establish the
structure of key peroxy compounds and to presume
the possible transformation routes thereof into the
final reaction products. The consideration of probable
reaction pathways allows a conclusion that the trans-
formation of zwitter-ions IIa, b arising from ozono-
lysis of compound I in various solvents (CH2Cl2,
ROH, CH3CN) depends on the structure of the initial
substrate (enololactone I), and on the character of
solvent used in the ozonolysis process.
reliably that in the reaction mixture dioxirane IIId is
not present.
At the isolation of peroxides obtained by ozono-
lysis of enololactone I in CH2Cl2 by means of solvent
evaporation in a vacuum at 0 C further transforma-
tions of bipolar ion IIIa, b also occur intramolecular-
ly without formation of IIIc dimer, for the molecular
weight of the products measured by the isopiestic
method corresponds to monomer.
The stability of zwitter-ion IIIa, b is uncommon
for carbonyl oxides, and it may be understood taking
into account the capability of halohydrocarbon
solvents to stabilize this structure by trimolecular
mechanism (see structure A) described by Swain and
Eddy [7].
The reduction of peroxides obtained by enolo-
lactone I ozonolysis in CH2Cl2 with zinc in acetic
acid or with hydrogen in the presence of Lindlar
catalyst affords formerly described [4] mixed
anhydride, and its yield is considerably higher when
the process is carried out without isolation of per-
oxides IIIa, b. Mixed anhydride IV is hydrolyzed
via intermediate formation of formylcarboxylic acid
(V) into 4 -hydroxy-6,6-dimethyl-3-oxabicyclo-
[3.1.0]hexan-2-one (VI) (Scheme 1).
In the peroxy product obtained by ozonolysis of
compound I in CD2Cl2 at 78 C the 1H and 13C NMR
spectra registered at 78 C revealed the presence of
an aldehyde group ( 9.64,
199.23 ppm). Besides
H
C
this in the 13C spectrum appeared a singlet at
164.40 ppm that we assigned to the carbonyl of the
acetoxy group, and a signal at 105.01 ppm character-
istic of a carbon linked to two oxygens.
We believe that during ozonation in CH2Cl2 of
enololactone I which is a cyclic vinyl ester the
primarily arising zwitter-ions IIa, b undergo an
intramolecular rearrangement into secondary bipolar
ions IIIa, b (Scheme 1). It is also presumable that
the peroxide IIIa, b is stabilized by formation of a
dimer IIIc or a dioxirane IIId. However the styrene
addition to the peroxides just after the ozonation did
not afford styrene epoxide in the reaction products. In
keeping with the published data [6] it shows fairly
The stabilization of intermediate zwitter-ion IIa, b
at enololactone I ozonolysis in alcohols occurs by
another route. Unexpectedly the peroxy product does
not contain alkoxy group that is usually regarded [1]
as taking part in ozonides stabilization in the form of
1
alkoxyhydroperoxides. It was demonstrated by H and
13C that two compounds arise with spectral character-
istics well consistent with structures VII and VIII.
They apparently result from the attack of zwitter-ions
1070-4280/01/3804-511$27.00 2002 MAIK Nauka/Interperiodica

512
KUKOVINETS et al.
Scheme 1.
IIa, b stabilized by alcohol on the C=O group of the
second fragment of the molecule (Scheme 2).
169.09 ppm, two peaks of carbon atoms attached to
two oxygens at 104.80 and 105.22 ppm, and a double
set of the signals from the other parts of the
molecules.
Since in the 13C NMR spectrum of compounds
VII and VIII after storage in the methanol solution
for 24 h alongside the other peaks appear signals at
174.93 and 174.78 ppm corresponding to free carb-
oxy groups it is possible that in the alcoholic solution
occur tautomeric transformations shown in Scheme 3.
The formation of monomeric peroxides VII and
VIII was confirmed by measuring their molecular
weight by isopiestic method (220) and by the content
1
of active oxygen therein (8.16%). In the H NMR
spectrum appear signals of two kinds of methyl
groups (2.19 and 2.20 ppm) from acetate fragments
with intensity ratio 1: 2 indicating that one of the
peroxides, presumable VIII, is present in double
amount. The protons linked to two oxygens give rise
to peaks at 4.88 and 5.05 respectively. In the
13C NMR spectrum of the ozonides are present four
carboxy group signals at 168.17, 168.31, 168.72 and
The reduction with dimethyl sulfide of the overall
peroxy product obtained by ozonolysis in alcohols in
every case afforded virtually a single product, 4 -alk-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 4 2002

OZONOLYSIS
513
Scheme 2.
R = Me, Et, i-Pr.
Scheme 3.
oxy-6,6-dimethyl-3-oxabicyclo[3.1.0]hexan-2-one
(XI XIII). Apparently the reduction starts with
alcohol attack on the atoms C2 or C5 in bicycle VII or
atoms C2, C4 in oxolane VIII (Scheme 4). The
reaction proceeds through acyclic forms IXa, IXb,
Xa, Xb, XIV XVI for in the IR and NMR spectra
after separation of crystalline alkoxylactone XI XIII
are observed signals corresponding to aldehyde, ester,
and carboxy groups that might appear only if in the
mixture are present nonlactone monocyclic forms
XIV, IXb, XVI. In the IR spectrum alongside the
absorption band of the carbonyl group from the five-
1
membered lactone (1780 cm ) are seen vibration
1
1
bands of aldehyde (1725 cm ), ester (1750 cm ),
1
and carboxy (1695 cm ) groups respectively. The
carbon atoms of the above carbonyl groups in the
13C NMR spectra appear as peaks at 173, 201, 180,
and 177 ppm.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 4 2002

514
KUKOVINETS et al.
Scheme 4.
The formation of alkoxy derivatives XI XIII is con-
the carbonyl carbon signal ( 173 ppm) virtually is not
affected by the change of alkyl in the alkoxy group.
1
firmed by the signals of alkoxy groups in the H and
13C NMR spectra (3.60 and 56.30; 4.20 and 52.06;
3.92 and 71.93 ppm for OCH3, OCH2, and OCH
moieties respectively), and by the signals of carbon
atoms linked to two oxygen atoms (102.46, 105.14,
and 100.34 ppm respectively). The chemical shift of
The decrease in the yield of crystalline methoxy-
lactone XI at reduction with thiourea of peroxy
products obtained by ozonolysis of enololactone I in
methanol shows that the transformation (XIV) (XI)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 4 2002

OZONOLYSIS
(XI) is a
515
occurs faster, and the cyclization (XV)
H2NCS (181.27 ppm), C=O (173.65 ppm), NCO
(82.81 ppm) and to the other carbon atoms of the
molecular skeleton. Analysis of mass spectra revealed
the most characteristic for thioamides fragment ions
[11], namely those of m/z 167 [M SH]+ , 60
slower process. This fact is consistent with published
data on considerable, sometimes prevailing formation
of acetals at reduction of peroxides with thiourea [8],
especially as at standing from the mother liquor
additionally precipitate crystals of methoxylactone
XI. The hydrolysis of alkoxylactones obtained in the
presence of oxalic or sulfuric acid results in previous-
ly described [5] hydroxylactone VI.
+
[H2NCS] . Analytically determined content of sulfur
and nitrogen corresponds to the assumed structure
XVIIa.
All the reduced bicyclic products VI, XI XIII,
XVIIa possess -structure. This is confirmed by the
lack of coupling between protons attached to carbons
C4 and C5 that are situated at an angle close to 90 .
This is possible only at -position of the proton
attached to C4.
The primary peroxy product of enololactone I
ozonolysis in CH3CN is identical in its spectral
characteristics to compound IIIa, b. However it is
less stable in CH3CN than in CH2Cl2, and it under-
goes at storage spontaneous decomposition via labile
intermediate compounds to furnish acid V that in its
turn transforms into lactol VI. The latter process is
so slow that even in a long time the yield of com-
pound VI does not exceed 30%, although its forma-
tion is reliably confirmed by appearance in the overall
13C NMR spectrum of signals at 173.02 (C=O) and
105.75 ppm (O C O). Lactol VI was also isolated
from the reaction mixture as individual compound by
crystallization.
Since in the 1H NMR spectrum of the overall
product obtained by reduction of peroxides with
thiourea are present signals corresponding to
aldehyde (9.84 ppm) and carboxy (11.20 ppm) groups,
the formation of monocyclic compound V at reduc-
tion is possible, especially as at acid hydrolysis of the
overall product the yield of bicyclic lactol is fairly
high (82%).
Lower stability of peroxide IIIa, b in CH3CN than
in CH2Cl2 may be ascribed to less efficient complex-
ing of nitrile dipole with bipolar ion as compared
with CH2Cl2 [9].
Scheme 5.
The reduction of the peroxy ozonolysis product
obtained with CH3CN with thiourea just after finish
of ozonolysis afford a complex mixture of compounds.
From the mixture was isolated by column chromato-
graphy on SiO2 thiourea derivative XVIIa. Formation
1
of the latter is proved by the presence in the H NMR
spectrum alongside the signals of gem-dimethyl
groups at 1.10 and 1.17 ppm and doublets of the
protons from the cyclopropane ring ( , ppm: 1.90 d
and 1.97 d, J 6.1 Hz) also peaks corresponding to the
protons from NH2 group (5.25 and 7.6 ppm), NH
(9.86 ppm) and those attached to C4 carbon
(5.82 ppm) of bicyclic compound XVIIa. The un-
expected splitting of the signals of terminal protons
attached to thioamide nitrogen apparently is caused
by the contribution from XVIIb structure arising in
tautomeric transformations of compounds XVIIa and
XVIIb [10]. This assumption is additionally sup-
ported by changing intensity ratio of NH2 protons at
registering the NMR spectrum at 55 C. The down-
field shift of the proton linked to the other nitrogen
atom (9.86 ppm) is due presumably to the deshielding
effect of the neighboring strained bicyclic fragment
of the molecule. The 13C NMR spectrum of com-
pound XIIa contains signals corresponding to groups
Scheme 6.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 4 2002

516
KUKOVINETS et al.
1
The reduction with dimethyl sulfide of enolo-
IR spectrum (cm ): 1775 s, 1740 s, 1115 s, 940 m.
1H NMR spectrum ( , ppm): 1.22 s, 1.23 s, 1.30 s,
1.31 s (6H, CH3), 1.72 1.78 m (2H, H1, H3), 2.19 s
and 2.20 s (3H, CH3CO), 4.88 and 5.05 m (1H,
OCHO). 13C NMR spectrum ( , ppm): 15.13 q and
20.83 q (CH3), 26.32 s and 26.96 s (C2), 32.90 d,
32.99 d, 33.49 d and 34.17 d (C1 and C3), 104.80 d
and 105.22 d (O C O), 168.17 s, 168.31 s, 168.72 s,
169.09 s (O=C). Found, %: Oact 8.16. C9H12O5.
Calculated, %: Oact 8.00.
lactone I ozonolysis products obtained in CH3CN also
affords a mixture of compounds. From this mixture
by column chromatography alongside the expected
hydroxylactone VI was isolated in 9% yield 3-oxa-
bicyclo[3.1.0]hexane-2,4-dione (XVIII).
EXPERIMENTAL
IR spectra were recorded on spectrophotometer
1
UR-20 from thin films or mulls in mineral oil. H and
2-Acetoxycarbonylcyclopropanecarboxaldehyde
IV (mixed anhydride of acetic and caronic acids). (a)
To peroxide IIIa, b prepared as above without separ-
ation thereof from solution in CH2Cl2 was added
20 ml of glacial acetic acid, and then by portions
activated zinc powder (11.9 g, 0.18 mol). The mix-
ture was stirred for 2 h at room temperature, the pre-
cipitate was filtered off, the solvent was removed in a
vacuum of a water-jet pump, and the residue was sub-
jected to chromatography on SiO2, eluent pentane
ether, 2: 1. We obtained 5.3 g (88%) of anhydride
IV, mp 112 113 C, identical to compound described
in [4]. (b) From peroxide IIIa, b prepared as above
was distilled off CH2Cl2 under reduced pressure.
The residue was dissolved in a mixture of glacial
acetic acid (24 ml) and anhydrous ethyl ether
(106 ml). To the solution was added by portions the
activated zinc powder (11.9 g, 0.18 mol) maintaining
the temperature at 20 C. Then the reaction mixture
was stirred for 2 h at the same temperature. The mix-
ture was filtered, the filtrate was evaporated in a
vacuum. We obtained 3.28 g of compound IV. The
precipitate that was filtered off was washed with ethyl
ether to isolate additionally 0.09 g of anhydride IV,
overall yield attained 56%.
13C NMR spectra were registered on spectrometer
Bruker AM-300 at operating frequencies 300.13 and
75.25 MHz respectively, solvent CDCl3, internal
reference TMS. GLC analyses were performed on
chromatograph Chrom-5 equipped with glass columns
1200 3 mm, stationary phase 5% SE-30 on Chroma-
ton N-AW-DMCS (0.16 0.20 mm), oven tempera-
1
ture 50 300 C programmed at a rate 12 deg min ,
carrier gas helium. Mass spectra were measured on
MKh-1303 instrument, ionization temperature 200 C,
ionizing electrons energy 80 eV. The optical rotation
was registered on polarimeter Perkin Elmer-141.
Ozonolysis of (1R,cis)-4,7,7-trimethyl-3-oxabi-
cyclo[4.1.0]hept-4-en-2-one (I). Through a solution
of enololactone I (5 g, 0.033 mol) in anhydrous
CH2Cl2, MeOH, or CH3CN (50, 36, or 40 ml re-
spectively) was passed at 78 C a flow of O3 O2
mixture till complete disappearance of compound I
from the solvent (TLC monitoring). The ozone
1
consumption was 46.5 mmol h , ozonation time
43.5 min. After the end of reaction the solution was
flushed with argon, and the peroxides were isolated
by cautious evaporation of the solvent under reduced
pressure. As a result were separated respectively
peroxides III (5.6 g, 92%), a mixture of VII and
VIII (5.7 g, 87%), and IIIa, b (5.9 g, 90%).
4 -Alkoxy-6,6-dimethyl-3-oxabicyclo[4.1.0]-
hept-4-en-2-ones (XI XIII). (a) Through a solution
of enololactone I (5 g, 0.033 mol) in anhydrous
methanol, ethanol, or 2-propanol (36 ml) was passed
a flow of O3 O2 mixture till compound I completely
disappeared from the solution (TLC monitoring).
Then the reaction mixture was flushed with nitrogen,
and 2.9 ml of dimethyl sulfide was added thereto at
stirring. The stirring was continued till complete
disappearance of peroxides ( 12 h) (test with acid
solution of KI). Methanol was evaporated in a
vacuum, to the residue was added 20 ml of CHCl3,
and the solution obtained was washed with saturated
NaCl solution (2 10 ml), dried with MgSO4,
filtered, the solvent was evaporated in a vacuum of
water-jet pump. As a residue was obtained 3.9 g
1-(Acetoxyperoxydehydromethyl)-2,2-dimethyl-
1
3-formylcyclopropane (IIIa, b). IR spectrum (cm ):
1
2760 m, 1745 s, 1725 s, 1120 s, 960 m H NMR
spectrum( , ppm): 1.01s and 1.40s (6H, CH3), 1.98d
(1H, H1, J 6.2 Hz) 2.03 m (1H, H3), 2.15 s (3H,
CH3CO), 9.64 br.s (CHO). 13C NMR spectrum ( ,
ppm): 14.84 q and 27.95 q (CH3), 17.46 (CH3CO),
22.40 s (C2), 29.94 d (C1), 36.58 d (C3), 105.01 s
(O C O), 166.40 s (C=O), 199.23 d (CHO). Found,
%: Oact 7.30. C9H12O5. Calculated, %: Oact 8.00.
Mixture of 5-acetoxy-7,7-dimethyl-3,4-dioxabi-
cyclo[4.1.0]heptan-2-one (VII) and 7,7-dimethyl-
4-peracetoxy-3-oxabicyclo[3.1.0]hexan-2-one (VIII).
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OZONOLYSIS
517
(76%) of compound XI, or 4.1 g (73%) of compound
XII, or 4.1 g (68%) of compound XIII.
reaction mixture was flushed with argon, to the
solvent obtained was added 0.5 g of Lindlar catalyst,
and the mixture was stirred under argon till negative
test for peroxides (with acid solution of KI). The
catalyst was filtered off, the solvent was evaporated
in a vacuum of water-jet pump, and as residue was
obtained 5.4 g (89%) of anhydride IV with char-
acteristics identical to those reported in [5].
(b) Enololactone I (5 g, 0.033 mol) was ozonized
as above in 36 ml of anhydrous methanol, and to the
solution obtained was added thiourea (1.35 g,
0.0177 mol). The reaction mixture thus obtained was
stirred for 10 min, the separated precipitate was
filtered off, the solvent was removed, and from the
residue was isolated by chromatography on SiO2
(eluent pentane ether, 3: 1)1.6 g (31%) of methoxy-
lactone XI identical to that obtained by procedure a.
Anhydride IV (5.2 g, 0.03 mol) was stirred in 1%
water solution of oxalic acid (50 ml) for 3 h, then the
product was extracted into ethyl acetate, and the
extract was dried on MgSO4. The solvent was distill-
ed off, and the residue was subjected to column
chromatography on SiO2 (eluent pentane ether, 3: 1).
We obtained 3.4 g (87%) of lactol VI, mp 116.5
117 C, [ ]2D8 101.5 (c 1.0, EtOH), spectral char-
acteristics were the same as published in [5].
1
Compound (XI). IR spectrum (cm ): 1760 s,
1220 s, 1190 s, 1140 s, 1010 m, 940 s, 860 w
1HNMR spectrum ( , ppm): 1.16s, 1.18 s (6H, CH3),
2.01 d (1H, H5, 1J 6.7 Hz), 2.04 d (1H, H1, 5J
6.7 Hz), 3.60 s (3H, OCH3), 5.05 s (1H, OCHO).
13C NMR spectrum ( , ppm): 15.06q, 25.40q (CH3),
24.47 s (C6), 29.93 d (C5), 35.22 d (C1), 56.30 q
(OCH3), 102.46 d (OCHO), 173.39 s (C=O). Mass
spectrum [m/z (I, %)]: 156 [M]+ (0.1), 155 [M 1]+
(b) Enololactone I (5g, 0.033mol) was ozonized
as above in 36 ml of anhydrous methanol, and to the
solution obtained was added at stirring 2.9 ml of
(CH3)2S. In 12 min MeOH was distilled off, to the
residue was added 1% water solution of oxalic acid
(50 ml), and the suspension obtained was stirred for
3 h; and the suspension got homogenous. Then the
hydrolysis product was extracted into ethyl acetate,
the extract was dried on MgSO4, filtered, two thirds
of the solvent was evaporated at 20 mm Hg, and the
separated crystals were filtered off. We obtained
3.83 g (82%) of compound VI identical to the above
described. From the mother liquor after evaporation
was additionally isolated 0.47 g (10%) of compound
VI. (c) Compound XVIIa (2 g, 0.01 mol) was stirred
with 18 ml of 1% water solution of oxalic acid.
Lactol VI resulting from hydrolysis was isolated as
described above in amount 1.23 g (87%).
(18.1), 124 [M CH3OH]+ (37.6), 31 [OCH3] (100).
+
Found, %: C 61.62; H 7.81. C8H12O3. Calculated,
%: C 61.52; H 7.74.
1
Compound (XII). IR spectrum (cm ): 1755 s,
1225 s, 1205 s, 1140 s, 1015 m, 935 s 860 m.
1HNMR spectrum ( , ppm): 1.16s, 1.19s (6H, CH3),
1
1.25 t (3H, C_H_3CH2, J 7.0 Hz), 2.00 d (1H, H5, J
3
6.3 Hz), 2.05 d (1H, H1, J 6.3 Hz), 4.20 q (2H,
CH2O, J 7.0 Hz), 5.12 s (1H, OCHO). 13C NMR
spectrum ( , ppm): 15.06 q, 25.40 q (CH3), 20.94 q
(C_H_3CH2), 24.51 s (C6), 29.81 d (C5), 35.28 d (C1),
52.06 t (OCH2), 105.14 d (OCHO), 174.42 s (C=O).
Found, %: C 63.24; H8.40. C9H14O3. Calculated, %:
C 63.50; H 8.31.
1
Compound (XIII). IR spectrum (cm ): 1760 s,
( )-N-(6,6-Dimethyl-4-oxo-3-oxabicyclo[3.1.0]-
hexan-2 -yl)thiourea (XVIIa). To peroxide obtained
by ozonolysis of enololactone (5 g, 0.033 mol) in
40 ml of CH3CN was added at cooling to 0 C in
several portions 1.35 g (0.0177 mol) of thiourea. On
completion of addition the mixture was stirred for
10 min, the separated precipitate was filtered off, the
solvent was evaporated, and the residue was subjected
to column chromatography on SiO2, eluent hexane
ethyl acetate, 4: 1. We obtained 3.16 g (48%) of
compound XVII, [ ]D20 33.44 (c 0.01, CHCl3). IR
1225 s, 1200 s, 1135 s, 1010 m, 940 s, 860 m
1H NMR spectrum ( , ppm): 1.11 s, 1.34 s (6H,
CH3C6), 1.15 d and 1.22 d (6H, CH3, J 6.0 Hz),
1.98 br.s (2H, H1 and H5), 3.93 d (1H, CHO, J
6.0 Hz), 5.20 s (1H, OCHO). 13C NMR spectrum
( , ppm): 15.06 q and 25.42 q (C_H_3C6), 21.83 q
and 23.38 q (C_H_3CH), 24.25 s (C6), 30.37 d (C5),
35.74 d (C1), 71.93 d (CHO), 100.34 d (C4),
173.31 s (C=O).
4 -Hydroxy-6,6-dimethyl-3-oxabicyclo[4.1.0]-
hept-4-en-2-one (VI). (a) Through a solution of
enololactone I (5 g, 0.033 mol) in anhydrous di-
chloromethane (50 ml) was passed a flow of O3 O2
mixture till compound I completely disappeared from
the solution (TLC monitoring) (ozone consumption
1
spectrum (cm ): 3380 s, 3300 s, 1765 s, 1610 m,
1
1520 m, 1290 s, 920 s, 870 m. H NMR spectrum ( ,
5
ppm): 1.10 s, 1.17 s (6H, CH3), 1.90 d (1H, H1, J
1
6.1 Hz), 1.97 d (1H, H5, J 6.1 Hz), 5.82 s (1H,
H2, J 2.7 Hz), 9.86 s (NH), 5.25 br.s and 7.6 br.s
1
(2H, NH2). 13C NMR spectrum ( , ppm): 14.55 q
44.2 mmol h , ozonolysis time 45 min). Then the
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KUKOVINETS et al.
and 26.11 q (CH3), 26.51 s (C6), 30.47 d and 33.95 d
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181.27 s (C=S). Mass spectrum [m/z (I, %)]: 200
[M]+ (0.6), 185 [M CH3] (26.1), 183 [M OH]+
+
(18.6), 172 [M CO]+ (37.2), 167 [M CH3 H2O]
+
(6.9), 41 (100). Found, %: C 48.15; H 6.2; N 13.2;
S 15.24. C8H12N2O2S. Calculated, %: C 48.00; H
5.99; N 14.00; S 16.01.
3-Oxabicyclo[3.1.0]hexane-2,4-dione (XVIII).
To peroxide obtained by ozonolysis of enololactone
(5 g, 0.033 mol) in 40 ml of CH3CN was added at
cooling to 0 C 2.9 ml of dimethyl sulfide, and stir-
ring was continued till complete disappearance of
peroxides (test with acid solution of KI). The solvent
was distilled off, the residue was subjected to
chromatography on SiO2 (eluent pentane ether, 3: 1).
We obtained 1.49 g (32%) of lactol VI identical to
that described above, and 0.37 g (9%) of dione
XVIII.
Compound (XVIII). [ ]2D0 12.90 (c 0.01,
1
CHCl3). IR spectrum (cm ): 1840 s, 1788 s, 1210 s,
840 m. 1H NMR spectrum ( , ppm): 1.31 s and
1.40 s (6H, CH3), 2.6 s (2H, H1 and H5). 13C NMR
spectrum ( , ppm): 16.84 q (CH3), 34.73 s (C6),
34.92 d (C1 and C5), 167.21 s (C=O). Mass spec-
trum [m/z (I, %)]: 140 [M]+ (0.06), 125 [M CH3]+
(1.8), 122 [M H2O]+ (6.91), 112 [M CO]+ (28.3),
96 (100). Found, %: C 59.89; H 5.83. C7H8O3.
Calculated, %: C 60.00; H 5.75.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 4 2002