2152 CANADIAN JOURNAL OF CHEMISTRY. VOL.

50, 1972

On the Extent of Transannular Rearrangement in the Formolysis of

1,5-CyclooctadieneMonoepoxide
JOHNM. MCINTOSH
Department of Chemistry, University of Windsor, Windsor. Ontario
Received January 13, 1972
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Formolysis of 1,5-cyclooctadiene monoepoxide (1) has been shown to give only ca. 25% of products of
transannular reactions. The difference between this result and those from the solvolyses of cyclooctene oxide
and 4-cyclooctenyl brosylate is attributed to conformational and ring-strain effects.

La formolyse du monokpoxyde (1) du cyclooctadiene-1,5 conduit a 25% seulement de produits resultant

de reactions trans-annulaire. La diffkrence entre ce rksultat et ceux issus de la solvolyse de l'kpoxyde du
cyclooct6ne et du brosylate du cyclooctknyl-4 est attribute a des effets conformationnels et de tension du cycle.
Canadian Journal of Chemistry, 50,2152 (1972)

Transannular reactions involving hydride
migrations and n-electron participation in
medium-sized ring solvolyses are well-docu-
mented (1). Perhaps the most thoroughly
Can. J. Chem. 1972.50:2152-2155.
components (Scheme 1). The yields are sum-
marized in Table 1.
The alcohol fraction contained 50% of 3,5-
cyclooctadienol (3) (9) which was distinguished

investigated case is the formolysis of cyclo-
octene oxide (2) where the competing reactions
of 1,3- and 1,5-hydride migrations have been
separated and shown to be in the ratio of 2: 3
(3). Attempts to extend the reaction to the
migration of other groups have met with limited
success (4, 5).
The preparation of 5-cyclooctene-l,2-diol(2)
in 73% yield by the acid-catalyzed hydroxylation
of 1,5-cyclooctadiene has been reported in the
patent literature (6). The presumed intermediate
in this reaction is 1,5-cyclooctadiene mono-
epoxide (1). The amount of normal epoxide
opening reported in this case is surprising when
compared with that of cyclooctene oxide (2)
since the presence of the double bond might be
expected to facilitate 1,3-hydride migrations
by stabilization of the developing positive
charge. Moreover, transannular n-electron par-
ticipation might be expected to provide an
energetically favorable pathway to bicyclic
products. It should be noted that the acetolysis
of 4-cyclooctenyl brosylate has been reported
(7) to give 74% of rearranged products. There-
fore we have reinvestigated the formolysis of
1,5-cyclooctadienemonoepoxide.
When 1,5-cyclooctadiene monoepoxide (1)
(8) was solvolyzed in either 85 or 98% formic
acid, a mixture of hydroxyformates was ob-
tained. Saponification and distillation of the
mixture afforded an alcohol fraction and a
higher-boiling diol fraction as the only volatile
from its isomer 4 (10) by its U.V.spectrum. The
remainder of the fraction was composed of a
mixture of bicyclooctenols as was shown by
elemental analysis, mass spectrometry, and by
integration of the n.m.r. spectrum.
The diol fraction was treated with acetone
and the isopropylidene ketal of 5-cyclooctene-
1,2-diol (5) was separated from the mixture by
distillation. The yields are summarized in
Table 1. That the residual diol mixture consisted
only of saturated bicyclooctanediols was shown
by (a) the absence of n.m.r. absorptions below
6 = 5.2, (b) the lack of reaction with dilute
bromine solution, and (c) the lack of hydrogen
absorption in the presence of a palladium
catalyst. Acetylation of the mixture gave a
mixture of diacetates which contained at least
eight components, many of which were incom-
pletely resolved under all v.p.c. conditions
utilized. Two of the components were separated
and the diols obtained by hydride reduction
were identified as bis-endo-bicyclo[3.3.O]octan-
2,6-diol (6) and a mixture of 2,5- and 2,6-
epoxycyclooctanol(7).
The comparison of the amount of trans-
annular reaction in this case and those of
cyclooctene oxide and 4-cyclooctenyl brosylate
is shown in Table 2. Clearly the introduction of
the n-bond into this cyclooctane ring effectively
negates the proclivity for transannular hydride
shift reactions found in cyclooctene oxide. The
only product isolated compatible with such a
 NOTES

0 0
(I) HCOOH
(2) NaOH,H20 O / O H
"OH
+ - OoH
+ others
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TABLE1. Product distribution in the solvolysis of 1

Alcohol (%) Diol8$ (%) Other diols (A)

Can. J. Chem. 1972.50:2152-2155.

Solvolysis Temperature
medium ("c) * t * t * t
85% HCOOHS 95 7 4 72.5 45.0 20.0 15.1
95% HCOOHS 60 - - 74.5 50.7 20.2 13.7

'Based on the total volatile components of the solvolysis.

+Based on 1.
:As ketal.
§Average of three runs.

TABLE
2. Comparison of products from cyclooctane compounds

Normal reaction Hydride shift Bicyclics

Compound Medium a)* products (%)* (%)*
1 85% HCOOH 72.5 7 20.0
98% HCOOH 74.5 - 20.2
Cyclooctene
oxide 85% HCOOH 13 86 < 1.
4-Cyclooctenyl
brosylate HOAc/NaOAc 26t - 74

'Based on the total volatile components of the solvolysis.

+Elimination product.

mechanism is dienol 3 (Scheme 2). However,

the data do not allow the assignment of this
difference to the presence of a preferred pathway
involving n-electron participation. Two argu-
ments can be advanced to rationalize these
results. Models suggest that (a) in a suitable also required the eclipsing of the C,--C, and
transition state for 1,3-hydride migration, the the C,-C, protons. These energetically un-
protons on C-3 and -7 are in very close proximity favorable situations may be responsible for the
and (b) the conformation required for n-electron observed increase in the amount of "normal"
participation in the opening of the epoxide ring epoxide opening. Alternately, it has been
 2154 CANADlAN JOURNAL OF
pointed out that the introduction of one double
bond into the cyclooctane ring reduces the ring
strain. The experimental evidence on this point
has been summarized (7). Although precise
thermochemical data are not available. it has
been suggested (7) that the ring strain' in the
bicyclo[3.3.0]octanes and the bicyclo[4.2.0]-
octanes (which should be reflected in the
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transition state leading to them) may be large
enough to make their formation from an
incipient cyclooctenyl carbonium ion slow rela-
tive to the usual epoxide-opening reaction.
If the products from 1 arise by attack of
formate directly on the protonated epoxide, the
difference in the products from 1 and 4-cyclo-
octenyl brosylate is understandable since the
latter is thought to proceed via a more car-
bonium ion-like transition state which allows
greater flexibility of the ring and thus more
n-participation in the product-forming step.
Can. J. Chem. 1972.50:2152-2155.
Experimental
Melting points and boiling points are uncorrected;
v.p.c. analyses were performed on an F and M Model 720
instrument; i.r. spectra were recorded in chloroform solu-
tion; and n.m.r. spectra in deuteriochloroform unless other-
wise noted. Microanalyses were performed by Dr. S. M.
Nagy and Associates (M.I.T.) and by A. B. Gygli, Micro-
analysis Laboratory (Toronto).
Solvolysis of 1.5-CyclooctadieneMonoepoxide (1)
(A) With 85% Formic Acid
To 500 ml of hot (95") formic acid was added 60 g
(0.48 mol) of 1 dropwise with stirring. An exothermic
reaction ensued. The temperature was maintained at 95"
for 1 h after the final addition and then most of the acid
was removed by distillation at 80 mm. The residual brown
oil was treated with 150 ml of cold 50% aqueous sodium
hydroxide and stirred at room temperature overnight. The
thick mass was extracted with four 200 ml portions of
chloroform and the extracts were dried, evaporated, and
carefully distilled to give an alcohol fraction (2.6 g, 4.3%
as dienol), b.p. 45-59" (0.25 mm), a main fraction (48.5 g,
70.1% as cyclooctene diols), b.p. 83-98" (0.23 mm), and a
non-distillable residue which was discarded.
(B) With 98% Formic Acid
The reaction was carried out in the same manner except
the temperature was maintained at 60". Fractionation of
the saponified mixture gave no alcohol fraction, 47.2 $
(68% as cyclooctene diols) of a viscous oil, b.p. 85-100
(0.25 mm), and some residue which was discarded.
The alcohol fraction was separated into two components
by preparative v.p.c. (8 ft x 0.25 in. 20% SE30, 150°), one
of which was identified as 3,s-cyclooctadienol(3) (9) which
was distinguished from 2,4-cyclooctadienol (4) (10) by its
U.V.spectrum: I,,, (EtOH) 230 nm ( E 4070).
Anal. Calcd. for C,H,,O: C, 77.38; H, 9.74. Found:
C, 77.13; H, 9.63.
CHEMISTRY. VOL. 50, 1972
Catalytic reduction over 10% palladium-on-charcoal
resulted in a hydrogen absorption of 2 equiv and furnished
cyclooctanol, identical in all respects with an authentic
sample.
The n.m.r. spectrum of the remainder of the fraction
showed an integrated intensity of 1.4 for the vinyl protons
(total of 12) but was otherwise uninformative. Catalytic
reduction resulted in a hydrogen absorption of 95% of
1 equiv. Analysis of the product on several v.p.c. columns
showed one very broad peak. The n.m.r. spectrum was
blank below 6 5.15 and a test with bromine in carbon
tetrachloride was negative.
Anal. Calcd. for C,H,,O: C, 77.38; H, 9.74. Found:
C, 77.37; H, 9.61.
A solution of 40.0 g (0.282 mol) of the fraction of b.p.
83-98" (0.23 mm) in 500 ml of acetone was shaken with
60 g of anhydrous cupric sulfate for 22 h at room tem-
perature. The solution was filtered, the residue washed
with acetone and the solvent removed by distillation.
Fractionation of the residue afforded 5.8 g (21.2%) of a
viscous glycol mixture, b.p. 96-124" (0.4 mm) and 39.4 g
(77%) of 5-cyclooctene-trans-1,2-diol isopropylidene ketal
(5), b.p. 66-68' (2.0 mm); ng 1.4699; i.r. 3020, 2985, 2940,
2860 1100 cm-'; n.m.r. 5.64 (2H, mult), 3.90 (2H, mult),
2.24 (8H, mult), 1.33 (6H, sing).
Anal. Calcd. for Cl,Hl,O,: C, 72.46; H, 9.95. Found:
C, 72.50; H, 9.87.
5-Cycloocrene-trans-I,2-diol(2)
Five grams (0.027 mol) of ketal 5 were hydrolyzed with
85% formic acid at reflux for 2 h. After saponification of
the product with aqueous sodium hydroxide, distillation
gave 3.12 g (80%) of 2, b.p. 88-89" (0.12 mm); ng 1.5110;
i.r. 3320 cm-' ;n.m.r. 5.59 (2H, trip J = 4), 4.38 (2H, broad),
3.53 (2H, mult), 1.1-2.75 (8H, mult).
Anal. Calcd. for C,H,,O,: C, 67.57; H, 9.92. Found:
C, 67.72; H, 10.11.
Acetylation of the remainder of the diol in the usual
manner afforded a mixture of diacetates. We were unable
to completely resolve the mixture under any v.p.c. con-
ditions. There were at least eight components present, none
of which corresponded to diol2. The lack of reaction of this
mixture with dilute bromine solution, the absence of n.m.r.
absorptions below 6 5.4 and the absence of a significant
peak at m/e 224 showed that the mixture was composed
of saturated materials only. Two components were isolated,
reduced with lithium aluminum hydride, and the products
shown to be bis-endo-bicyclo[3.3.0]octan-2,6-diol(6) identi-
cal with an authentic sample (see below) and a mixture of
2,5- and 2,6-epoxycyclooctano1, also identical with an
authentic sample (1 1).
Bis-endo-bicyclo[3.3.0]octan-2.6-diol (6)
Bicyclo[3.3.0]octan-2,6-dione(12) (3.53 g, 0.026 mol) was
reduced over prereduced platinum oxide in 75 ml of
methanol at 80" and 1450-1300 p.s.i. for 12 h. Filtration
and evaporation of the solvent gave residue which was
distilled to give 6 (3.36 g, 9379, b.p. 102-103" (0.38 mm);
n g 1.5095. I(
Anal. Calcd. for C,H1402 : C, 67.57; H, 9.92. Found :
C, 67.42; H, 9.72.
The bis-phenylurethane had m.p. 196-197".
Anal. Calcd. for C,,H,,O4N2 : C, 69.45; H, 6.63; N, 7.37.
Found:C,69.63; H,6.39;N,7.12.
 NOTES 2155

The author wishes to express his appreciation to the late 4. A. C. COPE,P. E. BURTON, and M. L. CASPAR.J. Am.
Prof. A. C. Cope who initiated these investigations, and to Chem. Soc. 84,4855 (1962).
Dr. B. S. Fisher who obtained some of the preliminary 5. J. M. MCINTOSH, M. H. MISKOW, and G. WOOD. Can.
results while a student at M.I.T. The technical assistance J. Chem. 49, 3243 (1971).
of Mr. D. Hill and the financial assistance of the National 6. P. LAFONTand H. MENAND.Fr. Pat. 1 294 313
Research Council of Canada is also greatly appreciated. (1962); Chem. Abstr. 57, 16437 (1962).
7. A. C. COPEand P. E. PETERSON.J. Am. Chem. Soc.
1. For review see, (a) A. C. COPE,M. M. MARTIN,and 81, 1643 (1959).
M. A. MCKERVEY.Quart. Rev. 20, 119 (1966); (b) 8. A. C. COPE,B. S. FISHER, W. FUNKE, J. M. MCINTOSH,
A. C. COPE. Proc. Robert Welch Foundation Con- and M. A. MCKERVEY.J. Org. Chem. 34,2231 (1969).
Downloaded from www.nrcresearchpress.com by 157.36.27.72 on 03/21/19. For personal use only.

ferences on Chem. Res. 4, 11 (1960); (c) V. PRELOGand 9. J. K. CRANDALL and L. H. CHANG. J. Org. Chem. 32,
J. G. TRAYNHAM. In Molecular rearrangements. Vol. 1. 532 (1967).
Edited by P. de Mayo. Interscience. New York, N.Y. 10. A. C. COPE,S. MOON,C. H. PARK,and G. L. Woe.
1963. p. 593. J. Am. Chem. Soc. 84,4865 (1962).
2. A. C. COPE,S. W. FENTON, and C. F. SPENCER.J. Am. 11. A. C. COPE,M. A. MCKERVEY, and N. M. WEINSHEN-
Chem. Soc. 74,5884 (1952). KER. J. Org. Chem. 34,2229 (1969).
3. A. C. COPE,G. A. BERCHTOLD, P. E. PETERSON, and 12. C. T. BLOODand R. P. LINSTEAD.J. Chem. Soc.
S. H. SHARMAN.J. Am. Chem. Soc. 82,6366 (1960). 2255 (1952).

The Magnetic Susceptibilities of Some Oxyhalide Ions

Can. J. Chem. 1972.50:2152-2155.

M. B. KENNEDY
AND M. W. LISTER
Department of Chemistry. University of Toronto, Toronto 181. Ontario
Received March 3, 1972

Diamagnetic susceptibilities are reported for aqueous sodium hypochlorite, chlorite, hypobromite, and
bromite. The results, combined with data from the literature for compounds of general formula NaXO,, show a
small increase for n = 0 to 2, and a much larger increase thereafter. The interpretation of these results in terms
of bond orders is discussed, and comparisons are made with the enthalpies of formation, distances, and
force constants of these compounds.
Les susceptibilitts diamagnetiques des solutions aqueuses d'hypochlorite, de chlorite, d'hypobromite et
de bromite de sodium sont decrites. Les rtsultats, combines aux donntes de la litterature concernant les
wmposts de formule gintrale NaXO,, montrent un faible accroissement de n = 0 a 2 et une croissance plus
marquee au-delh. L'interprktation de ces rtsultats en fonction de I'ordre de liaison est discutke et les w m -
paraisons sont faites avec les enthalpies de formation, les distances et les constantes de force de ces composts.
Canadian Journal o f Chemistry, 50,2155 (1972)

In an earlier paper (l), one of the present
authors attempted to relate the contribution of
oxygen atoms to the molar diamagnetic suscepti-
bility with the type of bonding of the oxygen.
The compounds then considered contained
oxygen linked to nitrogen and phosphorus, and
these were considered with special reference to
the bond orders of the bonds to oxygen. The
present note deals with compounds containing
oxygen linked to chlorine or bromine, partic-
ularly in the sodium salts of oxyhalide ions.
Since some of the compounds in question are
difficult to obtain as pure crystals (e.g., sodium
hypobromite), the measurements of suscepti-
bility were made on aqueous solutions. Earlier
work (2, 3) has shown that the susceptibilities
of salts are not very different depending on
whether they are crystals or in solution, at least
for uni-univalent salts; typically the suscepti-
bility of the salt in solution is 4 to 5% higher.
The susceptibility varies very little with con-
centration (4), so it was thought to be justifiable
to compare salt solutions of different concentra-
tions.
Experimental
Chemicals
Sodium Hypochlorite
A stock solution (about 1.2 M) was purified by filtration
through sintered glass, and then adding a 5% solution of
barium chloride dropwise with stirring, until no more