Unsaturated ozonides from the ozonolysis of cyclodienes in the presence of carbonyl compounds

Article abstract of DOI:10.1002/1099-0690(200108)2001:16<3083::AID-EJOC3083>3.0.CO;2-K

Treatment of the conjugated C₅- to C₈-cyclodienes (5a-5b) with one molar equivalent of ozone in dichloromethane in the presence of added carbonyl compounds (3) resulted almost exclusively in monoozonolysis reactions to give the corre

Full text of DOI:10.1002/1099-0690(200108)2001:16<3083::AID-EJOC3083>3.0.CO;2-K

FULL PAPER
Ozonolysis / Alkenes / Isomerization / Carbonyl compounds
Treatment of the conjugated C5- to C8-cyclodienes (5a−5b)
with one molar equivalent of ozone in dichloromethane in
olefins 1,5-cyclooctadiene (6a) and 1,5-dimethyl-1,5-cyclo-
octadiene (6b) under similar conditions afforded both unsat-
the presence of added carbonyl compounds (3) resulted al- urated cross-ozonides (11 and 17, respectively) derived from
most exclusively in monoozonolysis reactions to give the cor- monoozonolysis and cross-ozonides (12 + 16 and 19, respect-
responding unsaturated cross-ozonides 8 and/or 10 as the ively) derived from diozonolysis.
major products. In contrast, ozonolysis of the nonconjugated
Ozonolysis reactions of conjugated cyclic dienes in non-
participating solvents have not been studied extensively.[1Ϫ4]
In previous work, Griesbaum et al. have shown that in
methanol ozone attacks the double bonds of conjugated
cyclodienes stepwise, in contrast to the reaction with non-
conjugated cyclodienes.[5Ϫ8] Ozonolysis of cycloalkenes in
anhydrous nonparticipating solvents results in the forma-
tion of polymeric ozonides because the intramolecular
We treated solutions of compounds Ϫ in dichlorome-
cycloaddition of carbonyl oxides with aldehydes is much
thane with about one equivalent of ozone in the presence
slower than intermolecular reactions. In order to avoid the
of carbonyl compounds
and . Ozonolysis of
in the
formation of polymeric ozonides, a good 1,3-dipolarophile
is needed to trap the carbonyl oxide intermediates. In previ-
ous work we have shown that the carbonyl oxide interme-
presence of carbonyl compounds afforded a product mix-
ture in which the ozonides (Z)- (32%), (14%) and (E)
(11%) were detected by 1H NMR spectroscopy. Of
diates , generated from the ozonolysis of cycloalkenes
,
these,
(11%) and (E)-
(7%), although not (Z)-
,
can be trapped by carbonyl compounds to form the cor-
could be isolated. In a similar manner, ozonolysis of
in
responding ozonides .[9Ϫ11]
the presence of
gave a mixture of (Z)-
(29%),
(14%) and (E)-
(11%), from which
(11%) and (E)-
(7%) could be isolated. The formation of ozonide
is in line with the known fact that five-membered cyclool-
efins give high yields of ozonides, i.e. the intramolecular
reaction of the carbonyl oxide moieties in and can com-
pete favorably with intermolecular reactions with external
carbonyl compounds.[12,13]
We have now extended this mode of reaction to the ozon-
olysis of the conjugated cyclodienes
conjugated cyclodienes and
Ϫ
and to the non-
in the presence of car-
bonyl compounds
unsaturated ozonides
and
ϩ
to obtain the corresponding
, and , respectively.
The ozonolysis of
pounds and afforded the corresponding unsaturated
ozonides (Z)- , (Z)-
in the presence of carbonyl com-
[a]
Department of Chemistry, The Catholic University of Korea,
Puchon 422-723, Korea
,
Z -
and (Z)-
, which
Eur. J. Org. Chem.
, 3083Ϫ3087
WILEY-VCH Verlag GmbH, 69451 Weinheim, 2001
1434Ϫ193X/01/0816Ϫ3083 $ 17.50ϩ.50/0 3083

S. H. Park, J. Y. Lee, T. s. Huh
FULL PAPER
were isolated in yields of 58, 21, 53 and 21%, respectively.
These results suggest that the formation of intermediate
is favored over that of . In contrast, in the ozonolysis of (Z)-
in the presence of , the formation of intermediate
Ozonolysis of
the corresponding ozonides (Z)-
(25%) ϩ (60%), respectively.
in the presence of
and
provided
(68%) and
(23%) ϩ
was obviously favored over that of , as evidenced by the
formation of 62% of the ozonide Z-
Z- . Finally, in the ozonolysis of
and only 10% of
in the presence of
and of
ponding ozonides Z-
(84%) derived from intermediates of type were obtained.
This indicates that ozone cleavage of and of occurred
in the presence of
or of , only the corres-
(74%), Z-
(74%) and Z-
with high preference in one direction to give the interme-
diates rather than . This is surprising, since one would
have expected the zwitterion in to be resonance stabilized
by the double bond more than the zwitterion of .[10]
In the ozonolysis of
,
and
in the presence of car-
bonyl compounds , no evidence was found for the forma-
tion of the corresponding ozonides . This is in line with
the known fact that ozone attacks the double bonds of con-
jugated cyclodienes stepwise.
From the results of the ozonolysis of
and
it can be
The isomerization of the (Z)-ozonides
concluded that, in contrast to the conjugated cyclodienes ,
the two double bonds in nonconjugated cyclodienes are
attacked almost simultaneously by ozone to give approxim-
ately equal amounts of mono- and diozonolysis products.
It can be further concluded that ozone cleavage of the
and
in dichloromethane at room temper-
ature afforded, in each case, the corresponding (E)-ozonides
in yields of between 65% and 84%.
double bonds in
occurs predominantly in one direction
only, with the formation of higher substituted carbonyl ox-
ides.
All of the peroxidic products were isolated by column
chromatography on silica gel. The (Z)-and (E)-double bond
isomers were assigned by NOESY measurements. The
ozonides (Z)- , (Z)-
, (Z)-
and (Z)-
were ob-
tained as mixtures of two diastereoisomers at the ozonide
rings.[14,15]
Ozonolysis of
and
(30%),
in the presence of carbonyl compounds
provided the corresponding ozonides (Z)-
(15%), (25%), and (Z)- (25%),
The structures of all isolated ozonides were established
1
by H and 13C NMR spectroscopy, and by their reduction
(14%), with triphenylphosphane to give the expected dials and car-
(27%), respectively, along with 8% of dialdehyde
.
bonyl compounds .
The ozonide moieties of all ozonides could be recognized
by the appearance of 13C NMR signals for the carbon
atoms in the trioxolane rings in the typical range of δ ϭ
94.49Ϫ106.28.[10,11,16,17] The ozonide moieties of structures
(Z)- , (Z)- and (Z)- were additionally confirmed by the
1
appearance of H NMR signals for the CH groups in the
ozonide
rings
in
the
expected
range
and
multiplicities.[10,11,15Ϫ17]
The successful coozonolysis of the conjugated cyclodi-
enes in the presence of carbonyl compounds opens a con-
venient short-path synthesis for the hitherto unknown types
of ozonides
,
and
which bear double bonds and an
aldehyde group in the side chains.
Bruker AC-300. 1H NMR and 13C NMR spectra
were recorded in CDCl3 with TMS as internal reference. Chroma-
tographic separations: Flash chromatography on silica gel.
3084
Eur. J. Org. Chem.
, 3083Ϫ3087

Unsaturated Ozonides from the Ozonolysis of Cyclodienes
All ozonolyses were carried out in 50 mL of
FULL PAPER
H), 5.46 (dd, J ϭ 11.23 and 8.04 Hz, 1 H), 5.85 (d, J ϭ 6.24 Hz, 1
dichloromethane at Ϫ78 °C using one molar equivalent of ozone. H), 5.91 (dd, J ϭ 11.16 and 8.21 Hz, 1 H), 9.79 (s, 1 H). Ϫ 13C
Residual ozone was flushed out with nitrogen, the solvent was dis-
tilled off at room temperature under reduced pressure and the res-
idue was separated by flash chromatography. All chromatography
described below was carried out with dichloromethane/diethyl
ether in a ratio of 15:1. The formaldehyde ( ) used in the coozono-
lysis reactions was freshly prepared by pyrolysis of paraformal-
dehyde in each case.
NMR: δ ϭ 21.04, 43.60, 94.85, 98.73, 123.26, 138.93, 200.93. Ϫ
C7H10O4 (158.2): calcd. C 53.14, H 6.37; found C 53.47, H 6.15.
Reduction of (Z)-
with TPP gave 2-hexene-1,6-dial. [1H NMR:
δ ϭ 2.41 (m, 2 H) 2.81 (m, 2 H), 6.18 (dd, 1 H), 6.85 (dt, 1 H),
9.50 (d, 1 H), 9.79 (s, 1 H)].
Z
Colorless liquid. 1H
NMR: δ ϭ 1.95 (m, 2 H), 2.77 (m, 2 H), 5.07 (s, 1 H), 5.17 (s, 1
H), 5.24 (t, J ϭ 4.56 Hz, 3 H), 5.99 (dd, J ϭ 11.16 and 5.82 Hz, 1
H), 6.57 (dt, J ϭ 11.16 and 8.21 Hz, 1 H), 10.07 (d, J ϭ 7.34 Hz,
1 H). Ϫ 13C NMR: δ ϭ 22.71, 31.22, 94.54, 102.82, 150.61, 191.35.
Ϫ C7H10O4 (158.2): calcd. C 53.14, H 6.37; found C 53.56, H 6.22.
A solution of 20Ϫ40 mg of an ozonide and
an excess of triphenylphosphane in 0.6 mL of CDCl3 was kept at
room temperature for 24 hours. The products were analyzed by 1H
NMR spectroscopy.
Caution: All ozonolysis reactions, chromatographic separations,
and reductions of ozonides were carried out behind protective
safety-glass shields in a fumehood. Ozonides were transported, for
example to the analytical laboratory, in thick-walled steel con-
tainers. Safety glasses and gloves must be worn at all times.
Reduction of (Z)-
with TPP gave 2-hexene-1,6-dial.
Ozonolysis of
(0.24 g,
3.0 mmol) and
which (Z)-
(0.41 g, 6.0 mmol) gave a liquid residue, from
(0.31 g, 1.59 mmol, 53%) and (Z)- (0.12 g,
0.63 mmol, 21%) were isolated.
Ozonolysis of
(0.40 g,
6.0 mmol) and 1 mL of
(0.07 g, 0.61 mmol, 11%) and (E)-
gave a liquid residue, from which
Z
(0.06 g, 0.42 mmol, 7%)
Colorless liquid (a mixture of two diastereoisomers at the
ozonide ring). H NMR: δ ϭ 1.88 (s, 3 H), 2.50 (m, 2 H), 2.62 (m,
were isolated.
1
Colorless liquid. 1H NMR:
2 H), [5.53 (t, J ϭ 6.23 Hz), 5.56 (t, J ϭ 6.23 Hz)] (1 H), 6.01 (d,
J ϭ 6.41 Hz, 1 H), 6.08 (dd, J ϭ 11.12 and 8.21 Hz, 1 H), 6.37 (dt,
J ϭ 11.12 and 8.36 Hz, 1 H), 9.78(s, 1 H). Ϫ 13C NMR :δ ϭ 20.67,
21.21, 98.99, 100.93, 101.44, 117.00, 120.31, 124.90, 137.51.142.17,
200.66. Ϫ C9H11NO4 (197.2): calcd. C 54.81, H 5.62; found C
55.11, H 5.73.
δ ϭ 2.31 (dd, J ϭ 6.71 and 2.13 Hz, 1 H), 2.63 (dd, J ϭ 6.76 and
2.31 Hz, 1 H), 5.82 (d, J ϭ 7.83 Hz, 1 H), 5.87 (t, J ϭ 3.06 Hz, 1
H), 5.91Ϫ6.02 (m, 2 H). Ϫ 13C NMR: δ ϭ 34.00, 95.72, 100.30,
126.07, 127.39. Ϫ C5H6O3 (114.1): calcd. C 52.63, H 5.30; found
C52.37, H 5.16.
Reduction of
with TPP gave pentene-1,5-dial. [1H NMR: δ ϭ
Reduction of (Z)-
with TPP gave 2-hexene-1,6-dial and acetyl
2.93 (m, 2 H), 6.30 (dd, 1 H), 6.82 (dt, 1 H), 9.57 (d, 1 H), 9.78 (s,
1 H)].
cyanide.
Z
E
Colorless liquid. 1H
Colorless liquid (a mixture of two diastereoisomers at the
ozonide ring). 1H NMR: δ ϭ 1.87 (s, 3 H), 2.10 (m, 2 H), 2.85 (m,
2 H), [5.30 (t, J ϭ 4.72 Hz), 5.70 (t, J ϭ 4.72 Hz)](1 H), 6.03 (dd,
J ϭ 11.17 and 7.54 Hz, 1 H), 6.55 (dt, J ϭ 11.17 and 7.76 Hz, 1
H), 10.06 (d, J ϭ 7.52 Hz, 1 H). Ϫ 13C NMR: δ ϭ 21.24, 22.28,
22.68, 29.42, 33.52, 98.45, 98.91, 105.65, 116.87, 131.29, 149.55,
190.64. Ϫ C9H11NO4 (197.2): calcd. C 56.87, H 6.20; found C
56.11, H 6.29.
NMR: δ ϭ 2.79 (m, 2 H), 5.15 (s, 2 H), 5.16 (s, 1 H), 5.37 (t, J ϭ
4.52 Hz, 1 H), 6.25 (dd, J ϭ 15.81 and 7.08 Hz, 1 H), 6.79 (dt, J ϭ
15.81 and 6.11 Hz, 1 H), 9.55 (d, J ϭ 7.82 Hz, 1 H). Ϫ 13C NMR:
δ ϭ 18.29, 35.67, 94.67, 101.57, 136.45, 149.17, 193.67. Ϫ C6H8O4
(144.1): calcd. C 50.01, H 5.60; found C 50.38, H 5.34.
Reduction of (E)-
with TPP gave pentene-1,5-dial.
Ozonolysis of
(0.82 g, 12.0 mmol) gave a liquid residue, from
(0.08 g, 0.67 mmol, 11%) and (E)- (0.08 g,
(0.40 g,
Reduction of (Z)-
acetyl cyanide.
with TPP gave 2-hexene-1,6-dial and
6.0 mmol) and
which
0.42 mmol, 7%) were isolated.
Ozonolysis of
(0.28 g,
3.0 mmol) and 1 mL of
(0.05 g, 0.31 mmol, 10.1%) and (Z)
62%) were isolated.
gave a liquid residue, from which (Z)-
E
Colorless liquid. 1H NMR: δ ϭ 1.87 (s, 3 H), 2.94 (m, 2
H), 5.41 (t, J ϭ 4.26 Hz, 1 H), 6.27 (dd, J ϭ 15.81 and 7.06 Hz, 1
H), 6.78 (dt, J ϭ 15.81 and 6.02 Hz, 1 H), 9.53 (d, J ϭ 7.82 Hz, 1
H). Ϫ 13C NMR: δ ϭ 21.14, 33.18, 98.24, 104.26, 137.20, 146.56,
193.31. Ϫ C8H9NO4 (183.2): calcd. C 52.45, H 4.95; found C 52.14,
H 4.77.
(0.32 g, 1.86 mmol,
Z
Colorless liquid. 1H
NMR: δ ϭ 1.76 (m, 2 H), 2.24 (m, 2 H), 2.45 (t, J ϭ 6.26 Hz, 2
H), 5.10 (s, 1 H), 5.26 (s, 1 H), 5.46 (dd, J ϭ 11.13 and 8.21 Hz, 1
H), 5.56 (d, J ϭ 4.52 Hz, 1 H), 5.86 (dt, J ϭ 11.12 and 6.23 Hz, 1
H), 9.78 (s, 1 H). Ϫ 13C NMR: δ ϭ 21.84, 27.55, 43.22, 94.85,
98.79, 122.85, 140.29, 201.78. Ϫ C8H12O4 (172.2): calcd. C 55.80,
H 7.02; found C 55.78, H 7.17.
Reduction of (E)-
cyanide.
with TPP gave pentene-1,5-dial and acetyl
Ozonolysis of
(0.24 g,
Reduction of (Z)-
with TPP gave 2-heptene-1,7-dial. [1H NMR:
3.0 mmol) and 1 mL of
gave a liquid residue, from which (Z)-
δ ϭ 1.85 (m, 2 H), 2.37 (m, 2 H), 2.50 (m, 2 H), 6.11 (dd, 1 H),
6.83 (dt, 1 H), 9.49 (d, 1 H), 9.76 (s, 1 H)].
(0.27 g, 1.74 mmol, 58%) and (E)-
were isolated.
(0.11 g, 0.69 mmol, 23%)
Z 5
Colorless liquid 1H
Z
Colorless liquid. 1H
NMR: δ ϭ 2.52 (m, 2 H), 2.58 (m, 4 H), 5.11 (t, 2 H), 5.27 (s, 1 NMR: δ ϭ 1.70 (m, 2 H), 1.81 (m, 2 H), 2.68 (m, 2 H), 5.06 (s, 1
Eur. J. Org. Chem. , 3083Ϫ3087 3085

S. H. Park, J. Y. Lee, T. s. Huh
FULL PAPER
H), 5.17 (t, J ϭ 5.16 Hz, 1 H), 5.19 (s, 1 H), 6.00 (dd, J ϭ 11.23 J ϭ 7.82 Hz, 1 H). Ϫ 13C NMR: δ ϭ 22.73, 32.95, 94.57, 102.80,
and 6.41 Hz, 1 H), 6.59 (dt, J ϭ 11.23 and 7.36 Hz, 1 H), 10.06 (d, 133.67, 157.25, 194.64. Ϫ C7H10O4 (158.2): calcd. C 53.14, H 6.37;
J ϭ 7.72 Hz, 1 H). Ϫ 13C NMR: δ ϭ 23.65, 27.96, 30.92, 94.49,
103.58, 131.08, 152.13, 191.13. Ϫ C8H12O4 (172.2): calcd. C 55.80,
H 7.02; found C 55.63, H 6.93.
found C 53.36, H 6.32. Reduction with TPP gave 2-hexenedial.
E
Colorless liquid. Yield
74%. 1H NMR: δ ϭ 1.79 (m, 4 H), 2.40 (m, 2 H), 5.06 (s, 1 H),
5.16 (t, J ϭ 4.08 Hz, 1 H), 5.19 (s, 1 H), 6.15 (dd, J ϭ 10.84 and
7.83 Hz, 1 H), 6.82 (dt, J ϭ 10.84 and 4.58 Hz, 1 H), 9.51 (d, J ϭ
7.78 Hz, 1 H). Ϫ 13C NMR: δ ϭ 22.33, 30.99, 32.55, 94.47, 103.56,
133.82, 157.58, 194.28. Ϫ C8H12NO4 (172.2): calcd. C 55.80, H
7.02; found C 55.96, H 6.94. Reduction with TPP gave 2-heptene-
1,6-dial.
Reduction of (Z)-
with TPP gave 2-heptene-1,7-dial.
Ozonolysis of
(0.28 g,
3.0 mmol) and
which (Z)-
(0.41 g, 6.0 mmol) gave a liquid residue, from
(0.47 g, 2.22 mmol, 74%) was isolated.
Z
Colorless liquid (a mixture of two diastereoisomers at the
ozonide ring). 1H NMR: δ ϭ 1.75 (m, 2 H), 1.87 (s, 3 H), 1.95 (m.
2 H), 2.72 (m, 2 H), [5.28 (t, J ϭ 4.43 Hz), 5.64 (t, J ϭ 4.43 Hz)]
(1 H), 6.02 (dd, J ϭ 11.26 and 6.17 Hz, 1 H), 6.59 (dt, J ϭ 11.26
and 5.34 Hz, 1 H), 10.06 (d, J ϭ 7.82 Hz, 1 H). Ϫ 13C NMR: δ ϭ
21.28, 23.01 23.47, 27.69, 27.89, 29.24, 33.45, 98.81, 106.28, 106.33,
116.42, 116.98, 131.11, 151.71, 191.10. Ϫ C10H13NO4 (211.2):
calcd. C 56.87, H 6.20; found C 56.64, H 6.27.
E
Colorless liquid.
1
Yield 85%. H NMR: δ ϭ 1.55 (m, 4 H), 1.76 (m, 2 H), 2.37 (m,
2 H), 5.05 (s, 1 H), 5.14 (t, J ϭ 4.78 Hz, 1 H), 5.18 (s, 1 H), 6.11
(dd, J ϭ 13.75 and 7.83 Hz, 1 H), 6.82 (dt, J ϭ 13.75 and 7.28 Hz,
1 H), 9.50 (d, J ϭ 7.28 Hz, 1 H). Ϫ 13C NMR: δ ϭ 23.68, 27.95,
31.28, 32.80, 94.42, 103.81, 133.63, 158.19, 194.27. Ϫ C9H14O4
(186.2): calcd. C 58.05, H 7.58; found C 58.24, H 7.47. Reduction
with TPP gave 2-octen-1,8-dial.
Reduction of (Z)-
acetyl cyanide.
with TPP gave 2-heptene-1,7-dial and
E
1
Colorless liquid. Yield 73%. H NMR: δ ϭ 2.14 (m, 2 H),
2.16 (s, 3 H), 2.58 (m, 4 H), 5.39 (t, J ϭ 6.24 Hz, 1 H), 6.19 (dd,
J ϭ 11.13 and 5.82 Hz, 1 H), 6.82 (dt, J ϭ 11.13 and 8.07 Hz, 1
H), 9.53 (d, J ϭ 7.58 Hz, 1 H). Ϫ 13C NMR: δ ϭ 27.92, 30.85,
94.23, 106.11, 116.72, 134.46, 154.10, 194.46. Ϫ C9H11NO4 (197.2):
calcd. C 56.87, H 6.20; found C 56.11, H 6.29. Reduction with TPP
gave 2-hexene-dial and acetyl cyanide.
Ozonolysis of
gave a liquid residue, from which (Z)-
(0.41 g, 2.3 mmol, 74.1%) was isolated.
(0.32 g,
3.0 mmol) and 1 mL of
Z
Colorless liquid. 1H
NMR: δ ϭ 1.56 (m, 4 H), 1.78 (m, 2 H), 2.64 (t, J ϭ 7.36 Hz, 2
H), 5.03 (s, 1 H), 5.14 (t, J ϭ 4.73 Hz, 3 H), 5.17 (s, 1 H), 5.97 (dd,
J ϭ 15.86 and 8.12 Hz, 1 H), 6.62 (dt, J ϭ 15.86 and 6.94 Hz, 1
H), 10.07 (d, J ϭ 8.12 Hz, 1 H). Ϫ 13C NMR: δ ϭ 23.59, 28.09,
31.20, 94.36, 103.74, 130.67, 152.93, 191.13. Ϫ C9H14O4 (186.2):
calcd. C 58.05, H 7.58; found C 58.26, H 7.44.
E
Colorless liquid (a mixture of diastereoisomers at the ozon-
1
ide ring). Yield 65%. H NMR: δ ϭ 1.75 (m, 2 H), 1.86 (s, 3 H),
1.95 (m, 2 H), [5.28 (t, J ϭ 4.46 Hz), 5.64(t, J ϭ 4.46 Hz)] (1 H),
6.16 (dd, J ϭ 6.28 and 3.04 Hz, 1 H), 6.82 (dt, J ϭ 6.28 and
3.20 Hz, 1 H), 9.51 (d, J ϭ 7.82 Hz, 1 H). Ϫ 13C NMR: δ ϭ 21.29,
21.79, 27.91, 29.27, 32.45, 98.87, 106.32, 116.72, 117.08, 131.17,
151.43, 194.26. Ϫ C10H13NO4 (211.2): calcd. C 56.87, H 6.20;
found C 57.04, H 6.14. Reduction with TPP gave 2-heptene-dial
and acetyl cyanide.
Reduction of (Z)-
with TPP gave 2-octene-1,8-dial [1H NMR:
δ ϭ 1.69 (m, 4 H), 2.35 (m, 2 H), 2.49 (m, 2 H), 6.12 (dd, 1 H),
6.83 (dt, 1 H), 9.52 (d, 1 H), 9.78 (s, 1 H)].
Ozonolysis of
(0.41 g, 6.0 mmol) gave a liquid residue, from
(0.57 g, 2.53 mmol, 84%) was isolated.
(0.32 g,
3.0 mmol) and
which (Z)-
E
1
Colorless liquid. Yield 81%. H NMR: δ ϭ 1.51 (m, 4 H),
Z
1.78 (s, 3 H), 1.83 (m, 2 H), 2.18 (m, 2 H), 5.19 (t, J ϭ 4.64 Hz, 1
H), 6.05 (dd, J ϭ 10.63 and 6.42 Hz, 1 H), 6.76 (dt, J ϭ 10.63 and
3.28 Hz, 1 H), 9.44 (d, J ϭ 7.82 Hz, 1 H). Ϫ 13C NMR: δ ϭ 21.31,
23.21, 27.93, 29.79, 32.69, 98.64, 106.62, 116.74, 133.73, 157.83,
194.24. Ϫ C11H15NO4 (225.2): calcd. C 58.66, H 6.71; found C
58.42, H 6.84. Reduction with TPP gave 2-octene-1,8-dial and
acetyl cyanide.
Colorless liquid (a mixture of two diastereoisomers at the
ozonide ring). H NMR: δ ϭ 1.46 (m, 4 H), 1.76 (s, 3 H), 2.54 (t,
1
J ϭ 6.23 Hz, 2 H), [5.16 (t, J ϭ 4.61 Hz), 5.53 (t, J ϭ 4.61 Hz) (1
H), 5.84 (dd, J ϭ 9.68 and 7.23 Hz, 1 H), 6.50 (dt, J ϭ 9.68 and
3.18 Hz, 1 H), 9.96 (d, J ϭ 8.08 Hz, 1 H). Ϫ 13C NMR: δ ϭ 21.17,
23.13, 23.36 28.01, 28.84, 29.09, 29.64, 33.75, 98.24, 98.67, 106.52,
116.42, 117.04, 130.69, 152.8, 191.16. Ϫ C11H15NO4 (225.2): calcd.
C 58.66, H 6.71; found C 58.46, H 6.65.
Ozonolysis of
(0.32 g,
3.0 mmol) and 1 mL of gave a liquid residue, from which (Z)-
Reduction of (Z)-
cyanide.
with TPP gave 2-octene-1,8-dial and acetyl
(0.17 g, 0.91 mmol, 30%),
0.45 mmol, 15%) and
(0.1 g, 0.75 mmol, 25%),
(0.02 g, 0.24 mmol, 8%) were isolated.
(0.08 g,
Z
Z
Colorless liquid. 1H
Solutions of 3.0 mL of an ozonide in 10 mL of dichloromethane
were kept at room temperature for several weeks. The solvent was
evaporated at room temperature and reduced pressure and the
formed (E)-ozonides were isolated by flash chromatography.
NMR: δ ϭ 1.68 (m, 2 H), 2.12 (m, 2 H), 2.27 (m, 2 H), 2.40 (m, 2
H), 4.95 (s, 1 H), 5.04 (t, J ϭ 5.11 Hz, 1 H), 5.08 (s, 1 H), 5.31 (m,
2 H), 9.67 (t, J ϭ 1.51 Hz, 1 H). Ϫ 13C NMR: δ ϭ 20.28, 21.98,
31.36, 43.87, 94.34, 103.45, 129.01, 129.67, 202.24. Ϫ C9H14O4
(186.2): calcd. C 58.05, H 7.58; found C 59.97, H 7.46.
E
Colorless liquid.
Yield 71%. H NMR: δ ϭ 1.97 (m, 2 H), 2.52 (m, 2 H), 5.08 (s, 1
H), 5.23 (s, 1 H), 5.25 (t, J ϭ 4.54 Hz, 1 H), 6.01 (dd, J ϭ 8.16 Reduction of (Z)-
1
with TPP gave 4-octene-1,8-dial. [1H NMR:
δ ϭ 2.27 (m, 4 H), 2.40 (m, 4 H), 5.31 (t, 2 H), 9.67 (s, 2 H)].
and 3.14 Hz, 1 H), 6.83 (dt, J ϭ 8.16 and 3.02 Hz, 1 H), 9.50 (d,
3086
Eur. J. Org. Chem.
, 3083Ϫ3087

Unsaturated Ozonides from the Ozonolysis of Cyclodienes
FULL PAPER
Colorless li-
quid. H NMR: δ ϭ 1.84 (s, 4 H), 5.07 (s, 2 H), 5.17 (s, 2 H), 5.29
Colorless liquid. 1H
1
NMR: δ ϭ 1.45 (s, 3 H), 2.14 (m, 2 H), 2.58 (t, J ϭ 6.92 Hz, 2 H),
(t, J ϭ 4.82 Hz, 2 H). Ϫ 13C NMR: δ ϭ 25.96, 94.54, 103.10. Ϫ 5.06 (s, 1 H), 5.11 (s, 1 H), 9.75 (s, 1 H). Ϫ 13C NMR: δ ϭ 22.94,
C6H10O6 (178.1): calcd. C 40.45, H 5.66; found C 40.32, H 5.68.
30.07, 38.51, 94.46, 109.15, 201.43. Ϫ C6H10O4 (146.1): calcd. C
49.33, H 6.90; found C 49.63, H 6.67.
Colorless liquid. 1H NMR:
δ ϭ 2.02 (m, 2 H), 2.49 (t, J ϭ 6.10 Hz, 2 H), 4.96 (s, 1 H), 5.06
(s, 1 H), 5.16 (t, J ϭ 5.23 Hz, 1 H), 9.67 (s, 1 H). Ϫ 13C NMR:
δ ϭ 21.95, 37.80, 94.47, 102.52, 200.96. Ϫ C5H8O4 (132.1): calcd.
C 45.46, H 6.10; found C 45.57, H 5.83.
Ozonolysis of
(0.41 g, 6.0 mmol) gave a liquid residue, from
(0.19 g, 0.75 mmol, 25%) and (0.31 g,
(0.41 g,
3.0 mmol) and
which (Z)-
1.81 mmol, 60%) were isolated.
Colorless liquid. 1H NMR: δ ϭ 2.81 (s, 4 H),
9.77 (s, 2 H). Ϫ 13C NMR: δ ϭ 36.34, 200.32.
Z
Colorless liquid (a mixture of diastereoisomers at
1
the ozonide ring). H NMR: δ ϭ 1.48 (s, 3 H), 1.69 (s, 3 H), 1.83
Ozonolysis of
(0.41 g, 6.0 mmol) gave a liquid residue, from
(0.32 g,
(s, 3 H), 1.94 (m, 2 H), 2.36 (m, 2 H), 2.76 (m, 2 H), [5.19 (m),
5.33 (m)] (1 H), 9.78 (s, 1 H). Ϫ 13C NMR: δ ϭ 21.95, 21.43, 22.86,
23.46, 24.51, 24.59, 24.88, 26.08, 26.69, 36.06, 42.50, 98.71, 113.98,
114.04, 117.29, 124.94, 134.94, 202.51. Ϫ C13H19NO4 (253.3):
calcd. C 61.64, H 7.56; found C 61.45, H 7.66.
3.0 mmol) and
which (Z)-
(0.17 g, 0.75 mmol, 25%),
(0.14 g, 0.82 mmol,
27%),
(0.11 g, 0.43 mmol, 14%) and
(0.02 g, 0.24 mmol, 8%)
were isolated.
Z
Reduction of (Z)-
acyl cyanide.
with TPP gave 4-methyl-8-oxo-4-nonenal and
Colorless liquid (a mixture of two diastereoisomers at the
1
ozonide ring). H NMR: δ ϭ 1.86 (s, 3 H), [1.71 (m), 1.95 (m)] (2
H), [2.15 (m), 2.27 (m)] (2 H), 2.39 (m, 2 H), 2.51 (t, J ϭ 5.42 Hz,
2 H), [5.25 (t, J ϭ 5.23 Hz), 5.62 (t, J ϭ 5.23 Hz)] (1 H), 5.42 (m,
2 H), 9.77 (s, 1 H). Ϫ 13C NMR: δ ϭ 20.32, 21.30, 21.43, 21.64,
29.91, 33.74, 43.85, 98.35, 98.68, 106.24, 106.38, 116.26, 117.04,
128.97, 129.62, 202.16. Ϫ C11H15NO4 (225.2): calcd. C 58.66, H
6.71; found C 58.42, H 6.53.
Colorless liquid (a mixture of diastereoisomers at the ozonide ring).
1H NMR: δ ϭ 1.49 (s, 3 H), 1.86 (s, 3 H), [2.08 (m), 2.29 (m)] (2
H), [2.58 (m), 2.77 (m)] (2 H), [9.77 (s), 9.82 (s)] (1 H). Ϫ 13C
NMR: δ ϭ 20.92, 21.92, 25.38, 27.50, 31.37, 37.75, 38.75, 98.60,
99.06, 113.47, 113.57, 116.96, 117.20, 200.57. Ϫ C8H11NO4 (185.2):
calcd. C 51.88, H 5.99; found C 52.07, H 5.74.
Reduction of (Z)-
with TPP gave 4-octene-1,8-dial and acyl
cyanide.
[1]
W. I. Fata, W. F. Erman, J. Org. Chem.
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P. S. Bailey, S. S. Bath, F. Dobinson, F. J. Garcia-Sharp, C. D.
Johnson, J. Org. Chem. , 26, 694Ϫ702.
J. J. Pappas, W. P. Keaveney, M. Berger, R. V. Rush, J. Org.
Chem. , 33, 787Ϫ792.
Col-
[2]
[3]
[4]
[5]
1
orless liquid. H NMR: δ ϭ 1.87 (s, 3 H), 1.68 (s, 3 H), [2.03 (m),
2.23 (m)] (1 H), [2.61 (t, J ϭ 7.21 Hz), 2.73 (t, J ϭ 7.21 Hz)] (1 H),
[5.32 (t, J ϭ 5.42 Hz), 5.75 (t, J ϭ 5.42 Hz)] (1 H), [9.83 (s), 10.08
(s)] (1 H). Ϫ 13C NMR: δ ϭ 20.87, 21.07, 22.04, 26.70. 37.05, 37.75,
98.40, 98.99, 105.47, 105.86, 116.93, 200.28, 200.57. Ϫ C7H9NO4
(171.2): calcd. C 49.14, H 5.30; found C 48.97, H 5.37.
R. H. Callighan, M. H. Wilt, J. Org. Chem.
5212Ϫ5216.
K. Griesbaum, H. Keul, S. Agarwal, G. Zwick, Chem. Ber.
, 116, 409Ϫ415.
K. Griesbaum, G. Zwick, Chem. Ber.
K. Griesbaum, H. Mertens, I.-Ch. Jung, Can. J. Chem.
68, 1369Ϫ1375.
K. Griesbaum, I.-Ch. Jung, H. Mertens, J. Org. Chem.
55, 6024Ϫ6027.
H. S. Shin, T. S. Huh, Bull. Korean Chem. Soc.
775Ϫ776.
H. S. Shin, C. W. Lee, J. Y. Lee, T. S. Huh, Eur. J. Org. Chem.
, 335Ϫ348.
K. R. Lee, C. W. Lee, T. S. Huh, Bull. Korean Chem. Soc.
20, 1437Ϫ1440.
, 26,
[6]
[7]
, 118, 3041Ϫ3057.
,
,
Colorless liquid (a mixture of diastereo-
isomers at the ozonide ring). 1H NMR: δ ϭ 1.86 (s, 6 H), 1.75 (m,
4 H), [5.31 (m), 5.72 (m)] (2 H). Ϫ 13C NMR: δ ϭ 21.11, 23.22,
23.96, 27.84, 28.39, 98.47, 99.00, 105.43, 116.21, 116.84. Ϫ
C10H12N2O6 (256.2): calcd. C 46.88, H 4.72; found C 46.64, H 4.69.
[8]
[9]
, 20,
[10]
[11]
Ozonolysis of
(0.41 g,
3.0 mmol) and 1 mL of
(0.15 g, 0.70 mmol, 23%) and
were isolated.
gave a liquid residue, from which (Z)-
,
(0.31 g, 2.0 mmol, 68%)
[12]
[13]
R. Criegee, Chem. Ber.
, 108, 743Ϫ748.
R. Criegee, G. Blust, G. Lohaus, Justus Liebigs Ann. Chem.
, 583, 1Ϫ36.
R. W. Murray, R. D. Youssefyeh, P. R. Story, J. Am. Chem.
Z
Col-
1
orless liquid. H NMR: δ ϭ 1.46 (s, 3 H), 1.68 (s, 3 H), 1.77 (m, 2
H), 2.12 (m, 2 H), 2.38 (m, 2 H), 2.50 (m, 2 H), 5.03 (s, 1 H), 5.13
(m, 1 H), 5.18 (s,1 H), 9.77 (s, 1 H). Ϫ 13C NMR: δ ϭ 22.68, 23.04,
23.42, 24.59, 37.71, 42.55, 94.41, 109.74, 125.85, 134.20, 202.49. Ϫ
C11H18O4 (214.3): calcd. C 61.66, H 8.47; found C 61.54, H 8.33.
[14]
Soc.
, 89, 2429Ϫ2434.
[15]
[16]
T. S. Huh, Bull. Kor. Chem. Soc.
, 19, 1152Ϫ1153.
K. Griesbaum, B. Ovez, T. S. Huh, Y. Dong, Liebigs Ann.
, 1571Ϫ1574.
K. Griesbaum, X. Liu, A. Kassiaris, M.Scherer, Liebigs
[17]
Reduction of (Z)-
with TPP gave 4-methyl-8-oxo-4-nonenal. [1H
NMR: δ ϭ 1.68 (s, 3 H), 2.12 (s, 3 H), 2.38 (m, 4 H), 2.50 (m, 4
Ann./Recueil
, 1381Ϫ1390.
Received December 12, 2000
[O00636]
H), 5.30 (m, 1 H), 9.77 (s, 1 H)].
Eur. J. Org. Chem.
, 3083Ϫ3087
3087