Ozonolyses of 1,4-disubstituted 1,3-cyclohexadienesand of related compounds in methanol

KARLGRIESBAUM,'
HENRIMERTENS,
A N D IN CHANJUNG
Engler-Bunte-Institut, Bereich Petrochemie, Universitat Karlsruhe (TH), 0-7500 Karlsruhe, Germany
Received November 10. 1989

KARLGRIESBAUM, HENRIMERTENS, and IN CHANJUNG. Can. J. Chem. 68, 1369 (1990).

Ozonolyses of 1,4-dimethyl- ( 5 a ) and of 1-methyl-4-isopropyl-1,3-cyclohexadiene ( 5 6 ) in methanol occur stepwise by
sequential cleavage of the two double bonds. Monoozonolysis products are the corresponding compounds 6 and 7, and
diozonolysis products are the corresponding cyclic peroxides 19,20, and 21. By contrast, ozonolysis of the non-conjugated diene
2,5-dimethyl-l,5-hexadiene(13) in methanol occurs by simultaneous mono- and diozonolysis to give 14, 16a, 18a, and 20a.
Key words: ozonolysis, 1,3-cyclohexadienes, 3-hydroperoxy-l,2-dioxanes, 2,5-bis-hydroperoxy-2,5-dimethoxyhexane, 3-
hydroxy-l,2-dioxanes, 3,6-dimethoxy-l,2-dioxanes.
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KARLGRIESBAUM, HENRIMERTENS et IN CHANJUNG.Can. J. Chem. 6 8 , 1369 (1990).

L'ozonolyse, dans le mkthanol, des 1,4-dimCthyl- (5a) et 1-mCthyl-4-isopropyl-cyclohexa-1,3-dikne ( 5 6 ) se produit par des
clivages par Ctape des deux doubles liaisons. Les produits de monoozonolyse sont les composCs 6 et 7 alors que les produits de
diozonolyse sont les peroxydes cycliques correspondants 19,20 et 21. Par opposition, l'ozonolyse dans le mCthanol d'un dikne
non-conjuguC, comme le 2,5-dimkthyl-hexa-l,5-dikne(13), provoque des mono- et des di-ozonolyses simultanCes qui
fournissent les produits 14, 16a, 18a et 20a.
Mots elks : ozonolyse, cyclohexa-1,3-diknes, 3-hydroperoxy-1,2-dioxanes,2,5-bis-hydroperoxy-23-dimCthoxyhexane,3-
hydroxy-l,2-dioxanes, 3,6-dimkthoxy-l,2-dioxanes.
[Traduit par la revue]

Introduction the cyclodienes 5a and 5b, and of the acyclic substrates 13 and
Can. J. Chem. 1990.68:1369-1375.

Ozonolysis reactions of conjugated cyclic diolefins in partici- in at ca. -750C.

pating solvents have not been studied extensively, and essential
details concerning the course of events are unknown. Ozonoly-
sis of 1,3-cyclohexadiene gave a mixture of oxalic acid and
succinic acid (1); ozonolysis of 1-methyl-4-isopropyl-1,3-cyclo-
hexadiene in methanol, followed by reduction with sodium
iodide in acetic acid, gave 2-methyl-3,6-dioxoheptane (2).
Ozonolysis of naphthalene ( l a ) and of the substituted naphtha-
lenes l b - d in methanol afforded in each case the hemiperacetal
2a, and Id gave, additionally, the peracetal 2d (3). Com-
pounds 3 and 4 have been postulated, yet not proven, as inter-
mediates for 2a and 2d, respectively. Similar results were reported
for the ozonolysis of 1-methylnaphthalene (4) and of substi-
tuted 2-methoxynaphthalenes (5) in methanol.
Results and discussion
Monoozonolyses of the dienes Sa, Sb, and 13
Treatment of 5a with 0.7 molar equivalents of ozone gave the
two monoozonolysis products 6 a and 7 a in a ratio of 3:2, as
shown by 'H nmr analysis of the fresh ozonolysis product.
Compound 7 a could be isolated and structurally assigned by
spectroscopic methods. At room temperature it decomposed
slowly to give a mixture of 8a and 9 a . Compound 6a was less
stable and decomposed when we tried to isolate it. Hence its
structural assignment is based only on its 'H nmr data, which
were obtained from the mixture of 6 a and 7 a in the crude
reaction product, and on the fact that reduction of this mixture
with dimethyl sulfide gave Z-8a and E-8a (ratio 1:2) as the sole

q g."' *OH OOH

The results of these ozonolysis reactions did not reveal (a)
whether ozone attack at the two double bonds of the diene
systems occurred simultaneously or consecutively, (b) the
direction of cleavage, and (c) the nature of the primary cleavage
products. In line with our continued interest in the ozonolysis of
conjugated dienes (6), we have now studied the ozonolysis of
'Author to whom correspondence may be addressed.
Pnnted In Canada / Impnm.5 au Canada
products.
Treatment of 5 b with ca. 0.8 molar equivalents of ozone
afforded a peroxidic product mixture from which ca. 3% of 7 b ,
5% of 7 c , 6% OF 8b (unknown stereochemistry),2% of E-8c, 2%
of Z-8c, 1% of l o b , and 0.1 % of 10c have been isolated. While
6 b and 6c could not be positively identified in the product
mixture, there is indirect evidence for their transient existence
from the results of the diozonolysis of 5 b as reported below. We
assume, by analogy with 6 a , that 6 b and 6c are labile and
undergo rapid decomposition, possibly in part by oxygen
transfer to the double bonds of 8 b and 8c to give epoxides l o b
and 10c, respectively.
The isolated hydroperoxides 7 b and 7 c decomposed sponta-
neously in CDC13, and within ca. 18 h as neat samples at room
temperature, to give 8 b and 8 c , respectively. In CDC13/pyri-
dine they were stable for several hours. Reductions of 7 b and 7 c
with dimethyl sulfide also afforded 8 b and 8c, respectively.
Compound 8 b of unknown geometry as well as Z-8c and E-8c
have been identified by comparison of their 'H nmr and mass
spectral data with those published in the literature (7). Epoxides
l o b and 10c have been tentatively identified based on their 'H
nmr data.
 1370 CAN. J. CHEM. VOL. 68, 1990
The relative proportions of the ozonolysis products in the
crude reaction mixture could not be determined by glc analysis
due to the thermal instability of 7 b and of 7 c , nor by 'H nmr
analysis due to overlap of diagnostic signals. Immediate
reduction of a fresh ozonolysis product mixture with dimethyl
sulfide afforded 8 b and 8c in relative amounts of 70 and 30%.
The above results show that ozone attack at the conjugated
diene systems of 5a and 5 b occurs stepwise and that, probably
for steric reasons, attack at the methyl substituted double bond
of 5b is approximately 2.3 times faster than attack at the
isopropyl substituted double bond. The direction of cleavage in
the monoozonolysis of 5a, which gave l l a and 12a in
approximately equal amounts as primary cleavage products, is
not in line with the experience that trialkyl substituted double
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bonds are almost exclusively cleaved to give the higher
substituted carbonyl oxide. We believe that the stepwise attack
of ozone at 5a and 5 b is due to the fact that the oxygenated
functional groups that are formed in allylic positions to the
remaining double bonds of the monoozonolysis products 6 and 7
deactivate these double bonds against further ozone attack.
Similarly, the relatively high proportion of 7 a formed in the
ozonolysis of 5a can be ascribed to resonance stabilization of
the positive centre of the carbonyl oxide moiety in 12a by the
neighbouring double bond.
Can. J. Chem. 1990.68:1369-1375.
To test the above hypotheses concerning the reasons for the
stepwise ozone attack and for the direction of cleavage, we
investigated the monoozonolysis of the non-conjugated diene
13. Treatment of 13 with 0.7 molar equivalents of ozone gave a
mixture of 14 (52%),2 16a (23%), 19a (7%), cis-20a (lo%),
and trans-20a (8%), as shown by 'H nmr analysis. Hydroper-
oxides 14 and 16a have been isolated and characterized by their
2~elativeproduct distribution. The products derived from the =CL2
moiety are not included in the material balance.
'H nmr spectra as well as by reduction with triphenyl phosphine
to give 15 and 17a, respectively. Monoozonolysis of 13
followed by immediate reduction with triphenyl phosphine
afforded 15 and 17a in a ratio of 54:46.
From these results it can be concluded that, in contrast to the
conjugated diene 5 a , the two double bonds in 13 are almost
simultaneously attacked by ozone to give approximately equal
amounts of mono- and diozonolysis products. This is ascribed to
the fact that the functional groups introduced by monoozonol-
ysis are so remote from the remaining double bond that they do
not decrease its reactivity towards ozone attack. It can be further
concluded that ozone cleavage of the double bonds in 13 occurs
predominantly in one direction only, with formation of the
higher substituted carbonyl oxides, since there was no indica-
tion for the presence of either 15 or 17a in the product mixture.
Diozonolyses of 5a, 5b, and 13 and ozonolysis of some model
compounds
Diozonolysis of 5a gave 70-80% of 16a along with small
amounts, each, of 19a, cis- and trans-20a, and cis- and trans-2la.
After warm-up to room temperature and evaporation of the sol-
vent, the contents of 19a (33%),3 cis-20a (12%), trans-20a
(19%), cis-2la (1 1%), and trans-2la (24%) had considerably
increased at the expense of that of 16a, which had virtually
disappeared.
Diozonolysis of 13 and oznonolysis of 14 gave similar
results: Immediately after completion of the reaction, 16a was
the major product in selectivities of 65% and 85%, respectively,
but after warm-up to room temperature 16a had again disap-
peared. Thus, the aged product mixture derived from the
ozonolysis of 13 contained 19a (12%), cis-20a (12%), trans-20a
(ll%), cis-2la (20%), and trans-2la (45%), yet none of
16a. From such mixtures, cis-20a (in admixture with 30% of
the trans isomer), trans-20a (in admixture with 10% of the
cis isomer), cis-2la, and trans-2la have been isolated.
Ozonolysis of 15 gave a mixture of 17a (27%)' and 19a
(73%), from which 19a has been isolated. There was no
indication for the presence of 18a.
Diozonolysis of 5 b and subsequent warm-up to room
temperature gave a product mixture from which 19b, 19c, and
21b, each of unknown stereochemistry, as well as cis-20b,
-
trans-20b, cis-20c, trans-20c, and a mixture of 17b and 22
3 ~ e l a t i v eproduct distribution. The products derived from the
=CH--CH= moiety are not included in the material balance.
 GRIESBAIJ M ET AL.
have been isolated. Due to overlap of diagnostic signals, the
relative amounts of these compounds in the product mixture
could not be determined by 'H nmr spectroscopy. Ozonolyses
of 8b and of 8c gave mixtures of 17b (58%), P9b (31%), 22
(1 1%), and of 17 b (4 1%), 19c (32%), 22 (27%), respectively.
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The hemiperacetals 19a, 19b, and 19c of unknown stereo-
chemisty have been characterized by their 'H and 13cnmr
Can. J. Chem. 1990.68:1369-1375.
spectra, by elemental analysis, and by reduction with dimethyl
sulfide to give the corresponding diketones of structure 17.
Their formation is explained by ozone cleavage of monoozonol-
ysis products 14 and 6 , 7 , 8 , respectively, to give y-keto
hydroperoxides of structure 18, which subsequently undergo
intramolecular acetalization. In the latter reaction, the equilib-
rium is apparently completely shifted towards the side of the
hemiperacetal, since 19a, 19b, and 19c showed no positive
hydroperoxide test with lead tetraacetate (8).
The hydroperoxyperoxides 20a, 20b, and 20c have been
characterized by their 'H and 13C nmr spectra, by positive
hydroperoxide tests with lead tetraacetate (8), and by reduction
with dimethyl sulfide to give the corresponding diketones of
structure 17 and dimethyl sulfoxide in molar ratios of 1:2. The
stereochemical assignments are based on the assumptions (a)
that in 20a the methyl group at the hydroperoxy substituted
carbon atom and in 206 and 20c the isopropyl groups assume
equatorial positions in the preferred conformations owing to the
relatively high A values (9a), and (b) that, by analogy with
results obtained for other substituted 6-membered rings (9b),
the signals of the CH30 groups in the equatorial position of
cis-20a (6 = 3.39), and of cis-20c (6 = 3.40) as well as the
signal of the axial CH3 group of cis-20b (6 = 1.50) appear
downfield from the corresponding signals of trans-20a (6 =
3.36) trans-20c (6 = 3.36) and trans-20b (6 = 1.37).
The formation of compounds 20b and 20b,c can be rational-
ized by further ozone cleavage of the monoozonolysis products
14 and 6 , respectively, to give intermediates of structure 23. In
the latter, the carbonyl oxide moiety can react either intramolec-
ularly with the hydroperoxide group of 23 to give 20 or
intermolecularly with methanol to give 16, which subsequently
forms 20 by intramolecular displacement of methanol. We
could not find experimental evidence for the first reaction path,
i.e., the intramolecular reaction of 23 to give 20, and to our
knowledge trapping of a carbonyl oxide by a hydroperoxide is
hitherto unknown. The second reaction path via a bis-hydro-
peroxide of structure 16 is obviously responsible for the
1371
formation of 20a following the diozonolysis of 5a and of 13
since, as reported above, 20a was in each case formed at the
expense of the precursor 16a upon warm-up of the fresh
ozonolysis mixture. In support of this reasoning, it was found
that authentic 16a in CDC13 was converted into a mixture
containing 30% of cis-20a, 30% of trans-20a, 22% of cis-2la,
and 18% of trans-21a when it was kept at room temperature
overnight.
A priori, one had also to consider a third mode of formation
for compounds 20, viz. hydrolysis of methoxy hydroperoxides
of types 6 , 14, 16, or 18 by trace amounts of water to give
hydrogen peroxide, which in turn reacts with hemiperacetals of
structure 19 to give 20. If this were truely an alternative, one
should also expect the formation of 20a in the ozonolysis of 15.
It should provide 18a as the primary product. This could
undergo partial hydrolysis to give H202, which in turn could
react with 19a to give 20a, whereas none of the intermediates
16a or 23a, required for the formation of 20a by the alternate
routes, can be derived from 15. As reported above, ozonolysis
of 15 gave 17a and 19a, yet not detectable amounts of 20a, thus
ruling out the third potential mode of formation for compounds
20.
The cyclic peroxides 21a and 21 b were characterized by their
'H and I3C nrnr spectra, by elemental analysis, and by reduction
with triphenyl phosphine to give the corresponding diketones of
structure 17. Both 21a and 21b are remarkably stable, as
evidenced by the fact that reduction with sodium iodide or with
triphenyl phosphine did not occur at room temperature but had
to be performed at ca. 60°C. The stereochemical assignments of
cis- and trans-21a are again based on the assumptions (a) that
due to the larger A value (9a), the methyl groups in trans-21a
assume equatorial positions in the preferred conformation, and
(b) that the signals of the resulting axial CH30 groups appear
upfield (9b) (6 = 3.34) from those of the axial and equatorial
CH30 groups (6 = 3.38) in cis-21a. The stereochemistry of
isolated 21b could not be assigned on the basis of the above
arguments, since only one isomer was obtained.
The formation of the cyclic peroxides 21 can be rationalized
by reaction of compounds 19 or 20 with methanol. This view is
supported by the fact that the yield of isolated 21b from the
diozonolysis of 5 b could be increased to 3 1% when the crude
product mixture was treated with p-toluenesulfonic acid for
20 h, i.e., when the acetalization of 19b and 20b was catalyzed
by acid.
The structure of ozonide 22 was proven through the indepen-
dent preparation of 22 by the ozonolysis of a mixture of 8b and
8c in pentane and by reduction of 22 with triphenyl phosphine to
give 17b. The formation of 22 from 5b is rationalized by
intramolecular cycloaddition of the carbonyl oxide moieties
with the carbonyl groups of intermediates 24b and 24c. The fact
that 22 is obtained even in methanol as a solvent indicates that
this cycloaddition competes favourably with the trapping of the
carbonyl oxide by methanol.
In summary, the work described in this paper has shown that
the course of the ozonolysis of conjugated dienes deviates
considerably from that of similarly structured non-conjugated
dienes both in the sequence of ozone attack and in the direction
of cleavage of the two double bonds. Furthermore, the previ-
ously postulated (4, 5) intermediacy of 1,4-bis-methoxyhydro-
peroxides like 4 has now been proven by the isolation of 16a,
and it was shown that they serve not only as precursors for
compounds like 2d or 21, but that they react also to give the
hitherto unknown class of compounds 20.
 1372 CAN. 1. CHEM. VOL. 68, 1990
Experimental
General methods
The 'H nmr and I3C nmr spectra were recorded on a Bruker WM 250
and, only where it is specifically mentioned, on a Bruker WP 60 or on a
Bruker WH 300; ir spectra on a Beckman Acculab 1; and gc/ms spectra
on a Hewlett-Packard 5985 B instrument. The glc analyses were
carried out on a Shimadzu model 6A using a glass column 0.3 X
300 cm, 5% Nitrilesiliconoil XE 60 on Chromosorb G.
Monoozonolysis of 5a
A solution of 0.3 g (2.8 mmol) of 5a (10) in 10 mL of methanol was
treated with 0.7 molar equivalents of ozone at -75OC. The mixture was
flushed with nitrogen and evaporated at room temperature with a water
aspirator to leave 0.5 1 g of a colourless liquid residue; 'H nmr analysis
(CDCI,, Me4%)showedthepresenceof6a (6: 1.36 (s, 3H), 2.00(s, 3H),
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3.34 (s, 3H), 5.91 (d, J = 7.7 Hz, lH), 7.88 (br s, lH), 9.94 (d, J =
7.7 Hz, 1H)) and of 7 a (data, see below) in a ratio of 3:2. From
0.5 g of the residue 72 mg (13% yield) of 7 a were isolated by flash
chromatography (1 1) (column 2.5 X 50 cm; 60 g Florisil; 1 L of pentane
and diethyl ether, 7:3; fractions of 50 mL) in fractions 7-9.
1-Hydroperoxy-I-methoxy-3-methyl-6-0x0-2-tee( 7 ~ )Colour- :~
less liquid; ir (film), v: 3400 (OOH), 1715 (C=O), 1680 (C=C)
cm-'; 'H nmr (CDC13, Me4Si), 6: 1.75 (d, J = 0.8 Hz, 3H), 2.19
(s, 3H), 2.26-2.65 (m, 4H), 3.52 (s, 3H), 5.27 (dd, J = 6.3 Hz and
0.8Hz, IH),5.44(d, J = 6 . 3 H z , 1H),9.28(s, 1H);'3Cnmr(CDC13,
Me4Si), 6: 22.88q, 26.78t, 29.98q, 41.52t, 55.12q, 104.67d,
120.88d, 142.51 s, 208.33 s.
Can. J. Chem. 1990.68:1369-1375.
Decomposition of 7a
A sample of 0.3 g of neat 7a was kept at room temperature for 16
days; 'H nmr analysis (CDC13, Me4Si) showed the presence of 8% of
Z-8a (6: 1.97 (d, J = 1.3 Hz, 3H), 2.19 (s, 3H), 5.88 (dd, J = 7.9 and
1.3 Hz, lH), 9.97 (d, J = 7.9 Hz, 1H)); of 4%of E-8a (6: 2.19 (s, 6H),
5.83 (d, J = 7.8 Hz, lH), 9.99 (d, J = 7.8 Hz, 1H)); 43% of Z-9a (6:
1.75 (s, 3H), 2.16 (s, 3H), 3.31 (s, 6H), 5.02 (d, J = 6.2Hz, lH),
5.30 (d, J = 6.2Hz, 1H)); and 43% of E-9a (6: 1.73 (s, 3H), 2.16
Monoozonolysis of 5a followed by reduction with dimethyl sulfide
A solution of 0.3g (2.8mmol) 5 a in lOmL of methanol was
ozonized with 0.7 molar equivalents of ozone at -75°C. The reaction
product was flushed with nitrogen, admixed with 0.16 g (2.6 mmol) of
dimethyl sulfide, kept at room temperature for 18 h, and then
evaporated at room temperature with a water aspirator to leave 0.7 g of
a colourless liquid residue. Gas-liquid chromatographic analysis
(60-180°C at 1O0C/min)with the help of authentic samples showed the
presence of Z-8a (tR = 20.46 min) and of E-8a (tR = 22.77 min) in a
ratio of 1:2.
Monoozonolysis of 5b
A solution of 1.07 g (7.9 mmol) of 5 b in 25 mL of methanol was
ozonized with 0.8 molar equivalents of ozone at -78'C. The reaction
product was flushed with nitrogen and evaporated, at room temperature
and 18Torr(l Torr = 133.3 Pa), to leave 1.81 g of aliquidresidue. By
flash chromatography (1 1) (column 2 x 100 cm; 100 g of Florisil; 2 L
of pentaneldiethyl ether, 7:3; fractions of 50 mL), 79 mg (3.3%) of 7b
(fractions 20-27) and 119 mg (5.0%) of 7 c (fractions 11-16) were
isolated. Flash chromatography of a second sample (column 2 x
100 cm; 123 g of silica gel; 2 L of pentaneldiethy] ether, 7:3, followed
by 1 L of diethyl ether: fractions of 50mL) provided 637 mg of a
mixture of 8 b (51%), 8 c (37%), l o b (I I%), and 10c (1%). Separation
of this mixture by the hplc method (column 1.6 X 25 cm; Lichrosorb Si
100; 10 bar (1 bar = 100 kPa); pentaneldiethy] ether, 3:7) gave 110 mg
(6%) of 8b, 34 mg (1.8%) of E-8c, 45 mg (2.4%) of Z-8c, 24 mg
(1.1%) of lob, and 1.8mg (0.1%) of 10c.
l-Hydroperoxy-l-methoxy-3-isopropyl-6-oxo-2-ptene (7b):4 Colour-
less, viscous liquid; ir (film), v: 3350 (OOH), 1710 (C=O), 1663
4 ~ u toe decomposition of the neat substance no elemental analysis
has been performed.
(C=C) cm-'; 'H nmr (CDC13/pyridine-d5, Me4Si), 6: 1.03 (dd, J =
6.8 and 0.7Hz, 6H), 2.16 (s, 3H), 2.21-2.63 (m, 5H), 3.51 (s, 3H),
5.27 (dd, J = 6.3 and 0.7Hz, lH), 5.42 (d, J = 6.3 Hz, IH).
l-Hydroperoxy-l-methoxy-3,7-dimethyl-6-oxo-2-octene ( 7 ~ )Colour-
:~
less, viscous liquid; ir (film), v: 3370 (OOH), 1710 (C=O), 1665
(C=C) cm-I; 'H nmr (CDC13/pyridine-d5, Me4Si), 6: 1.10 (d, J =
6.9Hz, 6H), 1.74(d, J = l . l H z , 3H), 2.15-2.72(m, 5H),3.51 (s,
3H), 5.28 (dd, J = 6.0and 1.2Hz, IH), 5.44 (d, J = 6.0Hz, 1H).
3-lsopropyl-6-o.ro-2-heptenal(8b; unknown stereochernistry): Colour-
less, viscous liquid; glc (60-160°C at 4"C/min), tR = 50.16 min; 'H
nmr (60 MHz, CDC13, Me4Si), 6: 1.1 l (d, J = 6.8 Hz, 6H), 2.19
(s, 3H), 2.29-2.76 (m, 5H), 5.89 (d, J = 7.7Hz, lH), 10.00 (d,
J = 7.7 Hz, 1H). The data are identical with those reported for 8 b in
the literature (7).
E-3.7-Dimethyl-6-0x0-2-octenal (E-8c): Colourless, viscous liquid;
glc (60- 160°C at 4"C/min), t~ = 55.23 min; 'H nmr (60 MHz, CDCI,,
Me4Si), 6: 1.11 (d, J = 6.8Hz, 6H), 2.19 (d, J = 1.3Hz, 3H),
2.41-2.80(m, 5H), 5.83 (dq, J = 8.0and 1.3 Hz, IH), 10.00 (d, J =
8.0 Hz, 1H). The data are identical with those reported for E-8c in the
literature (7).
E-3,7-Dimethyl-6-oxo-2-octenal (Z-8c): Colourless, viscous liquid;
glc (60-160°C at 4"C/min), tR = 47.33 min; 'H nmr (60 MHz,
CDC13, Me4Si), 6: 1.1 1 (d, J = 6.9 Hz, 6H), 1.97 (d, J = 1.5 Hz,
3H), 2.50-2.84 (m, 5H), 5.88 (dq, J = 8.0 and 1.5Hz, lH), 9.99
(d, J = 7.9 Hz, 1H). The data are identical with those reported for
Z-8c in the literature (7).
2-Isopropyl-2-(3-oxo)-butyl-3-jormyl-o.~ne (lob): Slightly yellow
liquid; 'H nmr (60 MHz, CDCI,, Me4Si), 6: 0.90 (d, J = 6.6 Hz, 3H),
1.01 (d, J = 6.6Hz, 3H), 2.17 (s, 3H), 1.56-2.83 (m, 5H), 3.35
(d, J = 4.6 Hz, lH), 9.54 (d, J = 4.6 Hz, 1H); ei-ms (rel. intensity, %),
mle: 1 8 4 ( 0 . 5 ) ( ~ ) +155(51)(M-CHO)',
, 141 ( ~ ~ ) ( M - C H ~ C O ) ' ,
71 (23) ((CH,), CHCO)+, 43 (100) (CH,CO)+; ci-ms (rel. intensity,
%), mle: 185 (27) (M + 1)'. Since the compound was not pure
(yellow), no elemental analysis was performed.
2-Methyl-2-(3-o.ro-4-methyl)-pentyl-3-formyl-oxirane ( 1 0 ~ ) 'H
:
nmr (60 MHz, CDC13, Me4Si), 6: 0.96 (d, J = 6.8 Hz, 6H), 1.73
(s, 3H), 3.93(d, J = 4.4Hz, lH), 9.44(d, J = 4.4Hz, 1H). Insuf-
ficient amount for elemental analysis.
Reduction of 7b
To a solution of 23 mg (0.1 mmol) of 76 inC6D6, 13 mg (0.21 mmol)
of dimethyl sulfide was added and the mixture was kept at room
temperature for 17 h; 'H nmranalysis (60 MHz, CDC13,Me4%) showed
the signals of E- and Z-8b, methanol (6 = 3.26), dimethyl sulfide (6 =
1.75), and dimethyl sulfoxide (6 = 1.79).
Reduction of 7c
In the same way, 17 mg (0.08 mmol) of 7 c was reduced with 5.6 mg
(0.09 mmol) of dimethyl sulfide to give E- and Z-8c, methanol, and
dimethyl sulfoxide.
Monoozonolysis of5b followed by reduction with dimethyl sulfide
A solution of 1.04 g (7.6 mmol) of 5 b in 20 mL of methanol was
ozonized with 0.7 molar equivalents of ozone at -78'C. The mixture
was flushed with nitrogen and admixed with 0.71 g (1 1.5 mmol) of
precooled (-20°C) dimethyl sulfide. The mixture was briefly agitated,
allowed to warm up to room temperature overnight, kept at room
temperature for 5 h, and then evaporated at 20°C and 18 Torr to leave
2.44g of a colourless liquid; glc analysis (60-160°C at 4'C/min)
showed the peaks of 8 b (tR = 50.13 min), E-8c (tR = 55.04 min), and
Z-8c (tR = 47.30 min). The relative peak areas of 8 b and of E-8c +
Z-8c were 70% and 30%, respectively. By flash chromatography
(column 2 x 10 cm; 8 g silica gel; 250 mL of pentaneldiethyl ether,
99:1, 250mL pentaneldiethyl ether, 3:2), 581 mg (3.46mmol) of a
mixture containing 86 and of 8 c was isolated.
Monoozonolysis of 13
A solution of 0.95 g (8.7 mmol) of 1 3 in 20 mL of methanol was
ozonized with 0.7 molar equivalents of ozone at -78'C.
A sample of the crude reaction product was immediately analyzed by
'H nmr (CDCl,, Me4Si), to show the presence of 14 (52%),' 16a
(23%), 19a (7%), cis-20a (lo%), and trans-20a (8%). Then triphenyl
 GRIESBAUM ET AL.
phosphine was added to the sample and the mixture was kept at room
temperature for 10 min; 'H nmr analysis showed the presence of 15 (6:
1.72 (s, 3H), 2.14 (s, 3H), 1.84-2.59 (m, 4H), 4.65 (s, lH), 4.73
(s, 1H)) and of 17a (6: 2.19 (s, 6H), 2.72 (s, 4H)) in a molar ratio of
54:46.
The remainder of the crude ozonolysis product was warmed up to
room temperature and evaporated at 18 Tom to leave 1.3 g of a
peroxidic liquid residue. By flash chromatography (column 2.5 x
50 cm; 80 g silica gel; 2 L of pentaneldiethy1 ether, 75:25; fractions of
50 mL), 560 mg (35%) of 14 (fractions 4 and 5) and 30 mg (1 '6%) of
16a (fractions 28-33) were isolated.
2-Methyl-5-hydroperoxy-5-methoxy-I-hexene(14):4 Colourless liquid;
ir (film), v: 3320 (OOH), 1645 (C=C) cm-'; 'H nmr(CDC13, Me4Si),
6: 1.36 (s, 3H), 1.75 (s, 3H), 1.80- 188 (m, 2H), 2.04-2.13 (m, 2H),
3.32 (s, 3H), 4.70 (s, 2H), 7.74 (s, 1H); I3C nmr (CDCl,, Me4Si), 6:
Downloaded from www.nrcresearchpress.com by 157.35.85.13 on 12/30/18. For personal use only.
18.97, 22.51, 32.04, 33.24, 48.92, 107.04, 109.84, 145.27.
2,5-Bis-hydroperoxy-2,5-dimethoxyhexane ( 1 6 ~probably
;~ a mix-
ture of meso- and rac-16a in nearly equal amounts): Colourless liquid;
'H nmr (CDCl,, Me4Si), 6: 1.29 and 1.32 (s, each, CH,) 1.50-2.05
(m, CH2CH2),3.34 (s, CH30), 8.54 and 8.82 (s, each, OOH); 13Cnmr
(CDC13, Me4Si), 6: 18.37, and 18.67, 29.72 and 29.84, 48.93 and
48.97, 106.70 and 106.75.
Reduction of 1 4
Triphenyl phosphine was added to a solution of one drop of 14 in
0.6 mL of CDC13and the mixture was kept at room temperature for 10
min; 'H nmr analysis (Me4Si) showed the presence of 15.
Reduction of Ida
Can. J. Chem. 1990.68:1369-1375.
16a was completely converted into 17a by the above method, as
shown by 'H nmr analysis.
Diozonolysis of 5a
A solution of 0.3 g (2.8 mmol) of 5 a in 10 mL of methanol was
ozonized at -78OC until it turned blue, and excess ozone was
removed by flushing with nitrogen. A sample of the crude reaction
product was immediately analyzed by 'H nmr (CDC13, Me4Si) which
showed the presence of ca. 75% of 16a (6 = 1.29, 1.32) and small
amounts, each, of 19a (6 = 1.40), cis-20a (6 = 1.51), trans-20a (6 =
1.46), cis-2la (6 = 1.41), and trans-2la (6 = 1.30).
The remainder of the crude reaction product was warmed up to room
temperature and evaporated at ca. 20 Torr to leave 0.49 g of a liquid
residue; 'H nmr analysis (CDC13, Me4Si) showed the presence of 19a
(33%), cis-2Oa (12%), trans-20a (19%), cis-2la (1 I%), and trans-2la
(24%), whereas the signals of 16a had disappeared.
Diozonolysis of 1 3
(a) Determination of the product distribution
A solution of 0.1 g (0.90 mmol) of 1 3 in 10 mL of methanol was
ozonized at -78OC until it turned blue. The excess of ozone was
removed by flushing with nitrogen and the solution was evaporated at
room temperature and 18 Tom to leave 1.39 g of a liquid residue.
Immediate 'H nmr analysis (CDC13, Me4Si) showed the presence of
16a (65%, 6 = 1.29, 1.32), 19a (12%, 6 = 1.40), cis-20a(10%, 6 =
1.51), trans-20a (8%, 6 = 1.46), and cis-2la (5%, 6 = 1.41); ' ~ n m r
analysis of a sample that was kept at room temperature overnight
showed the presence of 19a (12%), cis-20a (12%), trans-200 (1 I%),
cis-2la (20%), and trans-2la (45%, 6 = 1.30), whereas the signals of
16a had disappeared.
( b ) sola at ion of stereoisomers of 20a and 21a
A solution of 1.90 g (17.3 mmol) of 13 in 30 mL of methanol was
ozonized at -78OC until the solution turned blue, and excess ozone was
removed by flushing with nitrogen. The crude reaction product was
warmed up to room temperature and evaporated at 20°C and 18 Torr to
leave 2.43 g of a yellow liquid residue. Flash chromatography of the
residue (column 2 x 100 cm; 122 g of silica gel; 2 L of pentaneldiethy1
ether, 4: 1, and 0.5 L of diethyl ether; fractions of 50 mL) gave 830 mg
of a mixture of cis- and trans-21a in fractions 10 and 11 and 630 mg of
a mixture of cis- and trans-20a and cis-2la in fractions 12-20. From
fractions 10 and 11, 143 mg (5%) of cis-2la and 53 1 mg (17.5%) of
trans-2la were isolated by hplc separation (clurnn 3 X 10 cm;
1373
Lichrosorb Si 60; 10 bar; pentaneldiethy] ether, 9: 1). Fractions 12-20
were again submitted to flash chromatography under the same
conditions to give 473 mg of a 1: 1 mixture of cis- and trans-20a. From
the latter mixture, cis- and trans-20a could be enriched, yet not
completely separated from each other, by hplc separation (conditions
as above).
cis-3 -Hydroperoxy-6-methoxy -3,6-dimethyl-l,2-dioxane(cis-20a;
in admixture with 30% of trans-20a): Colourless liquid; ir (film), v:
3400 (OOH) cm-'; 'H nmr (60 MHz, CDCl,, Me4Si), 6: 1.44 (s, 3H),
1.51 (s, 3H), 1.60-2.16 (m, 4H), 3.39 (s, 3H), 8.59 (s, 1H); I3C nmr
(CDCl,, Me4Si), 6: 19.33, 19.60, 26.62, 29.75, 49.19, 102.64,
107.13. Anal. calcd. for C7HI4o5:C 47.18, H 7.92; found: C 47.10,
H 7.81. Addition of a drop of cis-20a to lead tetraacetate in benzene
resulted in the spontaneous development of gas bubbles.
trans-3-Hydroperoxy-6-methoxy-3,6-dimethyl-1,2-dioxane (trans-20a;
in admixture with 10% of cis-20a): Colourless solid; ir (film), v: 3400
(OOH) cm-'; 'H nmr (60 MHz, CDCl,, Me4Si), 6: 1.31 (s, 3H), 1.46
(s, 3H), 1.53-2.16 (m, 4H), 3.36 (s, 3H), 8.36 (s, 1H); I3C nmr
(CDCl,, Me4Si), 6: 19.71, 19.81, 28.23, 31.00, 49.98, 103.37,
107.58. Addition of trans-20a to lead tetraacetate in benzene resulted
in the spontaneous development of gas bubbles.
cis-3,6-Dimethyl-3,6-dimethoxy-l,2-dioxane (cis-2la): Colourless
liquid; 'H nmr (CDC13, Me4Si), 6: 1.41 (s, 6H), 1.60-210 (m, 4H),
3.38 (s, 6H); I3C nmr (CDC13, Me4Si), 6: 19.70 (q, J = 29.9Hz),
30.90 (t, J = 32.0 Hz), 49.71 (q, J = 44.0 Hz), 102.31 (s).
trans-3,6-Dimethyl-3,6-dimethoxy-1,2-dioxane (trans-2la): Colourless
liquid; 'H nmr (CDC13, Me4Si), 6: 1.30 (s, 6H), 1.50-2.10 (m, 4H),
3.34 (s, 6H); I3C nmr (CDC13, Me4Si), 6: 19.92, 29.69, 49.01,
101.72. Anal. calcd. for C6Hl6O4:C 54.53, H 9.15; found: C 54.52,
H 8.97.
Ozonolysis of 1 4
A solution of 0.1 g (0.63 mmol) of 14 in 10 mL of methanol was
ozonized at -78OC until it turned blue. Excess ozone was removed by
flushing with nitrogen and the solvent was evaporated at room
temperature and ca. 20 Torr to leave 0.13 g of a liquid residue.
Immediate 'H nmr analysis (CDC13, Me4Si) showed the presence of
16a (85%; 6 = 1.29, 1.32), 19a (5%; 6 = 1.40), cis-20a (7%;
6 = 1.51), and trans-20a (3%, 6 = 1.46).
Ozonolysis of 15 and isolation of 19a
A solution of 1.51 g (13.4mmol) of 15 in 25 mL of methanol was
ozonized at -74OC until it turned blue, and excess ozone was removed
by flushing with nitrogen. A small sample was immediately analyzed
by 'H nmr (CDC13, Me4Si) to show the presence of 17a (27%,' 6 =
2.19and2.72)andof19a(73%,6 = 1.32, 1,39,3,34).Theremainder
of the product mixture was evaporated at 20°C and 20 Tom to leave
1.8 g of a liquid residue. By flash chromatography (column 2 x
100 cm; 120 g of silica gel; 1 L of pentaneldiethy1 ether, 4: 1, fractions
of 50mL), 433 mg (20%) of 19a was isolated in fractions 14-23.
3-Hydroxy-6-methoxy-3,5-dimethyl-l,2-dioxane (19a, unknown stereo-
chemistry): Colourless solid, mp 68°C; ir (CCl,), v : 3620, 3480 cm-';
'H nmr (CDCl-,, Me4Si), 6: 1.32 (s, 3H), 1.40 (s, 3H), 1.60-2.10
(m, 4H), 3.03 (s, lH), 3.35 (s, 3H); I3C nmr (CDC13, Me4%), 6:
19.89, 25.13, 29.63, 29.95, 49.16, 99.43, 101.76. Anal. calcd. for
C7HI4o4:C 51.84, H 8.70; found: C 51.88, H 8.37.
Diozonolysis of 5 b
(a) Isolation of l9b, 19c, cis-20b, trans-20b, cis-20c, and trans-20c
A solution of 3.07 g (22.6 mmol) of 5 b in 50 mL of methanol was
ozonized at -75OC until it turned blue. Excess ozone was removed by
flushing with nitrogen and the reaction mixture was immediately
evaporated at 20°C and 18 Torr to leave 5.42 g of a liquid residue.
Immediate separation of the residue by flash chromatography (column
2 x 100 cm; 125 g of silica gel; 0.5 L of pentaneldiethy1 ether, 9:1,2 L
of pentaneldiethy1 ether, 4:1, 1 L of pentaneldiethy1 ether, 2: 1, 0.5 L
of diethyl ether; fractions of 50 mL) gave 45 mg of a 1:1 mixture of 21b
and 22 in fractions 7-9, 1.15 g of a 1.2 mixture of 20b (cis + trans),
+
and of 20c (cis trans) in fractions 16-40, and 1.84 g of a mixture of
17b, 19b, 19c, and formic acid in fractions 50-63. Fractions 16-40
were further separated by the hplc method (column 1.6 x 25 cm;
 1374 CAN. 1. CHEM.VOL. 68, 1990
Lichrosorb Si 100; 11 bar; pentaneldiethylether, 4: 1) to give 192 mg of
mixture A, containing cis- and trans-206 and trans-20c, 516 mg of
mixture B containing cis-206 and trans-20c and 402 mg of mixture C,
containing cis-206 and cis- and trans-20c. Further hplc separation
under the same conditions gave 42mg (0.9%) of trans-206 from
mixture A, 125 mg (2.7%) of cis-20c from mixture C, as well as 74 mg
(1.6%) of cis-206 and 573 mg (12.3%) of trans-20c from a combina-
tion of mixture B and the by-products obtained from the separation of
mixtures A and C. The hplc separation of fractions 50-63 from the
flash chromatography gave 42mg (1%) of 19b and 137 mg (3.2%) of
19c.
3-Hydroxy-3-methyl-6-methoxy-6-isopropyl-1 2-dioxane(196): Colour-
less solid, mp 31°C; 'H nmr (CDCI3, Me4Si), 6: 0.92 (d, J = 7.0Hz,
3H), 0.97 (d, J = 7.0 Hz, 3H), 1,39 (s, 3H), 1.45-2.30 (m, 5H), 3.30
(s, 3H); 13cnmr (CDC13, Me4%), 6: 16.50, 17.40, 21.15, 25.65,
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28.82, 29.89, 48.19, 99.00, 104.38.
3-Hydroxy-3-isopropyl-6-methyl-6-methoxy-1,2-dioxane(l9c): Colour-
less viscous liquid; 'H nmr (CDCI3, Me4Si), 6: 0.97 (d, J = 6.9 Hz,
3H), 0.98 (d, J = 6.9 Hz, 3H), 1.31 (s, 3H), 1.20-2.10 (m, 5H), 2.95
(s, lH), 3.34 (s, 3H); I3C nmr (CDCI3, Me4Si), 6: 15.94, 16.81,
20.22, 24.81, 29.52, 35.80, 49.05, 101.30, 101.51. Anal. (of a 1:l
mixture of 19b and 19c) calcd. for C9H1804:C 56.82, H 9.54; found:
C56.46, H9.31.
cis-3-Hydroperoxy-3-methyl-6-methoxy-6-isopropy1-1,2 -dioxane (cis-
206): Colourless solid, mp 77°C; ir (CCl,), v: 3460 (OOH) cm-'; 'H
nmr (300 MHz, CDCI3, Me4Si), 6: 0.94 (d, J = 6.8Hz, 3H), 0.95
(d,J=6.8Hz,3H), 1.50(s,3H), 1.67-2.16(m,4H),2.19(sept, J=
6.9 Hz, lH), 3.35 (s, 3H), 8.42 (s, 1H); I3cnmr (CDC13, Me4Si), 6:
Can. J. Chem. 1990.68:1369-1375.
16.19, 16.48, 19.48, 24.53, 27.69, 31.90, 49.61, 106.27, 108.13.
Addition of cis-206 to lead tetraacetate in benzene resulted in the
spontaneous development of gas bubbles.
trans-3-Hydroperoxy-3-methyl-6-methoxy-6-isopropyl-1,2 -dioxane
(trans-20b): Colourless solid, mp 68°C; ir (CCI,), v: 3500 (OOH)
cm-'; 'H nmr (CDC13, Me,Si), 6: 0.91 (d, J = 6.8Hz, 3H), 0.96
(d, J = 6.8 Hz, 3H), 1.37 (s, 3H), 1.53-2.02 (m, 4H), 2.03 (sept, J =
6.8 Hz, lH), 3.31 (s, 3H), 8.15 (s, 1H); I3C nmr (CDCI3, Me4Si),
6: 16.44, 17.40, 20.19, 21.83, 26.34,30.04,48.30, 104.98, 106.46.
Addition of trans-20b to lead tetraacetate in benzene resulted in the
spontaneous development of gas bubbles.
cis-3-Hydroperoxy-3-isopropyl-6-methyl-6-methoxy-1,2-dioxane(cis-
20c): Colourless, viscous liquid; ir (CCl,), v: 3380 (OOH) cm-I; 'H
nmr (CDCI3, Me4Si), 6: 0.98 (d, J = 7.0 Hz, 3H), 0.99 (d, J =
6.9 Hz, 3H), 1.44 (s, 3H), 1.65-2.20 (m, 4H), 2.36 (sept, J = 7.0 Hz,
lH), 3.40 (s, 3H), 8.43 (s, 1H); I3cnmr (CDC13, Me,Si), 6: 16.58,
16.81, 19.78, 23.23, 30.51, 31.53, 50.13, 103.83, 110.48. Addition
of cis-20c to lead tetraacetate in benzene resulted in the spontaneous
development of gas bubbles.
trans-3-Hydroperoxy-3-isopropy1-6-methyl-6-metho-12-dioxane
(trans-20c): Colourless, viscous liquid; ir (film), v: 35 10 ( 0 0 H ) cm- '; was flushed off with nitrogen, the mixture was warmed up to room
'H nmr (CDC13, Me4Si), 6: 0.97 (d, J = 6.8 Hz, 3H), 0.99 (d, J =
6.8 Hz, 3H), 1.29 (s, 3H), 1.34-2.10 (m, 4H), 2.39 (sept, J = 6.9 Hz,
lH), 3.36 (s, 3H), 7.92 (s, 1H); I3cnmr (CDCl3, Me4Si), 6: 16.62,
17.41, 19.15, 19.93, 29.41, 30.32, 49.03, 101.93, 109.75. Anal.
calcd. for CgH1805:C 52.41, H 8.80; found: 52.70, H 8.68. Addition
of trans-20c to lead tetraacetate in benzene resulted in the spontaneous
development of gas bubbles.
(b) isolation of 21b
Ozonolysis of 5 b was repeated as described above for (a), but the
crude reaction product was kept at room temperature for 27 h before it
was evaporated. By flash chromatography (column 2 X 100 cm; 119 g
of silica gel; pentaneldiethy1 ether, 9:1, fractions of 50 mL), 340mg
(7.3%) of 21b was obtained in fractions 6-9.
3-Methyl-6-isopropyl-3,6-dimethoxy-l,2-dioxane (21b): Colourless
liquid; 'H nmr(300MHz, CDC13,Me4Si), 6: 0.90(d, J = 6.8 Hz, 3H),
0.95 (d, J = 6.8 Hz, 3H), 1.28 (s, 3H), 1.35-2.17 (m, 5H), 3.29
(s, 31),3.33(s, 3H); 13Cnmr(C~C13, Me4Si), 6: 16.49, 17.42,20.43,
20.91, 29.03, 29.93,47.94, 48.78, 100.96, 104.08. Anal. calcd. for
C10HZ004:C 58.80, H 9.87; found: C 58.95, H 9.66.
Reductions of hemiperacetals of structure 19
(a) Reduction of 19a: A solution of 23 mg (0.14 mmol) of 19a and
19mg (0.30mmol) of dimethyl sulfide in CDC13 was kept at room
temperature for 5 days; 'H nmr analysis (Me4Si) showed the presence
of 17a and of dimethyl sulfoxide (6 = 2.64) in a ratio of 1.1.
(b) Reduction of 19b and 19c: A solution containing 31 mg
(0.16 mmol) of a 1: 1 mixture of 19b and 19c and 32 mg (0.5 mmol) of
dimethyl sulfide in CDC13 was kept at room temperature for 6 days;
'H nmr analysis (Me4Si) showed the presence of 176 (6 = 1.11, 2.19,
2.72) and of dimethyl sulfoxide (6 = 2.63) in a ratio of 1:l.
Reductions of hydroperoxyperoxides of structure 20
(a) Reduction of 20a: A solution containing 15 mg (0.08 mmol) of a
1:1 mixture of cis- and trans-20a, and 25 mg (0.4 mmol) of dimethyl
sulfide in 0.5 mL of CDCI3 was kept at room temperature for 2 weeks;
'H nmr analysis (Me,Si) showed the presence of 17a (6 = 2.19,2.7 1)
and of dimethyl sulfoxide (6 = 2.63) in a ratio of 1:2.
(b) Reduction of20b and20c: Solutions containing dimethyl sulfide
and cis-206, trans-206, cis-20c, and trans-20c, respectively, in
CDC13 were kept at room temperature for ca. 1 week, each; 'H nmr
analysis (Me4Si) showed in each case the presence of 176 and of
dimethyl sulfoxide (6 = 2.62) in a ratio of 1.2.
Reductions of the cyclic peracetals of structure 2 1
(a) Reduction of cis- and trans-21a: A solution of 21a (cis:trans =
1:l) and triphenyl phosphine in CDCI3 was heated to 60°C for 6 days;
'H nmr analysis (Me4Si) showed the presence of 17a (6 = 2.19 and
2.71).
(b) Reduction of2lb: A solution of 18.5 mg (0.09 mmol) of 21b and
47.5 mg (0.18 mmol) of triphenyl phosphine in 0.6 rnL of CDCI3 was
kept at room temperature for 3 days; 'H nmr analysis (Me4Si) showed
no change in the composition. The solution was heated to 60°C for 4
days; 'H nmr analysis showed the presence of 17b and of the remaining
21b in a ratio of 2: 1.
Ozonolysis of 5b followed by acid catalysis
A solution of 1.95 g (13.6 mmol) of 5 b in 50 mL of methanol was
ozonized at -74OC until it turned blue. Excess ozone was removed by
flushing with nitrogen, the mixture was warmed up to room tempera-
ture, admixed with 50 mg of p-toluenesulfonic acid monohydrate, and
stirred at room temperature for 20 h. Then lOmg of potassium
carbonate was added, stirring was continued for 1 h, and the solvent
was evaporated at 20°C and 18 Tom. From the residue, 861 mg (3 1%)
of 21b was isolated by flash chromatography in fractions 8- 12 (column
2 x 100 cm; 120 g of silica gel; 1 L of pentaneldiethy] ether, 9:1,
fractions of 50 mL).
Preparation of 22 by ozonolysis of 8b and 8c in pentane
A solution of 58 1 mg (3.46 mmol) of a mixture of 8 6 and 8 c in 50 mL
of pentane was ozonized at -60°C until it turned blue. Excess ozone
temperature, pentane was largely evaporated, and the residue was
submitted to flash chromatography (column 2 X 100 cm; 60 g of silica
gel; 2 L of pentaneldiethy] ether, 49:l; fractions of 50mL) to give
93 mg (17%) of 22 in fractions 8- 16.
1-Methyl-4-isopropyl-2,3,7-~ioxabicyclo[2.2. I]heptane (22): Colour-
less liquid; 'H nmr (CDC13, Me4Si), 6: 1.06 (d, J = 6.9 Hz, 3H), 1.09
(d, J = 7.OHz, 3H), 1.67 (s, 3H), 1.76-2.41 (m, 5H); 13cnmr
(CDCI3, Me4Si), 6: 14.96, 17.35, 17.76, 28.99, 30.83, 34.92,
110.66, 115.37. Anal. calcd. for C8HI4o3:C 60.74, H 8.92; found:
C 60.46, H 8.74.
Reduction of 22
A solution of 31 mg (0.20 mmol) of 22 and 154 mg (0.59 mmol) of
triphenyl phosphine in 0.3 mL of CDC13 was kept at room temperature
for 3 days; 'H nrnr analysis (Me4Si) showed the presence of 176.
1. A. T. MENYAILO, I. E. PROKROVSKAYA, and A. K. YKOLEVA.
Neftekhimiya, 7, 70 (1967).
2. W. I. FANTAand W. F. EIUIIAN.J. Org. Chem. 33, 1656 (1968).
 GRIESBAUM ET AL. 1375

3. P. S. BAILEY,S. S. BATH,F. DOBINSON, F. J. GARCIA-SHARP, 7. G. RUCKER and U. MOLLS.Liebigs Ann. Chem. 5, 608 (1979).
and C. D. JOHNSON. J. Org. Chem. 29, 697 (1964). 8. R. CRIEGEE, H. PILZ,and H. FLYGARE. Ber. Dtsch. Chem. Ges.
4 . R. H . CALLIGHAN and M. H. WILT. J. Org. Chem. 26, 5212 72, 1799 (1939).
(1961). 9. H. GUNTHER. NMR-Spektroskopie. Georg Thieme Verlag, Stutt-
5. J. J. PAPPAS, W. P. KEAVENEY, M. BERGER, and R. V. RUSH.J. part. 1973. (a) p. 264; ( b ) p. 77.
Org. Chem. 33, 787 (1968). 10. W. T. BRADY, S. J. NORTON,and J. KO. Synthesis, 7 , 7 0 4 (1985).
6. K. GRIESBAUM and G. ZWICK.Chem. Ber. 119, 229 (1986), and 11. W. C. STILL,M. KAHN,and A. MITRA.J. Org. Chem. 43,2923
references cited therein. (1978).
Downloaded from www.nrcresearchpress.com by 157.35.85.13 on 12/30/18. For personal use only.
Can. J. Chem. 1990.68:1369-1375.