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

investigated case is the formolysis of cyclo- from its isomer 4 (10) by its U.V.spectrum. The
octene oxide (2) where the competing reactions remainder of the fraction was composed of a
of 1,3- and 1,5-hydride migrations have been mixture of bicyclooctenols as was shown by
separated and shown to be in the ratio of 2: 3 elemental analysis, mass spectrometry, and by
(3). Attempts to extend the reaction to the integration of the n.m.r. spectrum.
migration of other groups have met with limited The diol fraction was treated with acetone
success (4, 5). and the isopropylidene ketal of 5-cyclooctene-
The preparation of 5-cyclooctene-l,2-diol(2) 1,2-diol (5) was separated from the mixture by
in 73% yield by the acid-catalyzed hydroxylation distillation. The yields are summarized in
of 1,5-cyclooctadiene has been reported in the Table 1. That the residual diol mixture consisted
patent literature (6). The presumed intermediate only of saturated bicyclooctanediols was shown
in this reaction is 1,5-cyclooctadiene mono- by (a) the absence of n.m.r. absorptions below
epoxide (1). The amount of normal epoxide 6 = 5.2, (b) the lack of reaction with dilute
opening reported in this case is surprising when bromine solution, and (c) the lack of hydrogen
compared with that of cyclooctene oxide (2) absorption in the presence of a palladium
since the presence of the double bond might be catalyst. Acetylation of the mixture gave a
expected to facilitate 1,3-hydride migrations mixture of diacetates which contained at least
by stabilization of the developing positive eight components, many of which were incom-
charge. Moreover, transannular n-electron par- pletely resolved under all v.p.c. conditions
ticipation might be expected to provide an utilized. Two of the components were separated
energetically favorable pathway to bicyclic and the diols obtained by hydride reduction
products. It should be noted that the acetolysis were identified as bis-endo-bicyclo[3.3.O]octan-
of 4-cyclooctenyl brosylate has been reported 2,6-diol (6) and a mixture of 2,5- and 2,6-
(7) to give 74% of rearranged products. There- epoxycyclooctanol(7).
fore we have reinvestigated the formolysis of The comparison of the amount of trans-
1,5-cyclooctadienemonoepoxide. annular reaction in this case and those of
When 1,5-cyclooctadiene monoepoxide (1) cyclooctene oxide and 4-cyclooctenyl brosylate
(8) was solvolyzed in either 85 or 98% formic is shown in Table 2. Clearly the introduction of
acid, a mixture of hydroxyformates was ob- the n-bond into this cyclooctane ring effectively
tained. Saponification and distillation of the negates the proclivity for transannular hydride
mixture afforded an alcohol fraction and a shift reactions found in cyclooctene oxide. The
higher-boiling diol fraction as the only volatile 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 CHEMISTRY. VOL. 50, 1972

pointed out that the introduction of one double Catalytic reduction over 10% palladium-on-charcoal
bond into the cyclooctane ring reduces the ring resulted in a hydrogen absorption of 2 equiv and furnished
cyclooctanol, identical in all respects with an authentic
strain. The experimental evidence on this point sample.
has been summarized (7). Although precise The n.m.r. spectrum of the remainder of the fraction
thermochemical data are not available. it has showed an integrated intensity of 1.4 for the vinyl protons
been suggested (7) that the ring strain' in the (total of 12) but was otherwise uninformative. Catalytic
reduction resulted in a hydrogen absorption of 95% of
bicyclo[3.3.0]octanes and the bicyclo[4.2.0]- 1 equiv. Analysis of the product on several v.p.c. columns
octanes (which should be reflected in the showed one very broad peak. The n.m.r. spectrum was
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transition state leading to them) may be large blank below 6 5.15 and a test with bromine in carbon
enough to make their formation from an tetrachloride was negative.
Anal. Calcd. for C,H,,O: C, 77.38; H, 9.74. Found:
incipient cyclooctenyl carbonium ion slow rela- C, 77.37; H, 9.61.
tive to the usual epoxide-opening reaction. A solution of 40.0 g (0.282 mol) of the fraction of b.p.
If the products from 1 arise by attack of 83-98" (0.23 mm) in 500 ml of acetone was shaken with
formate directly on the protonated epoxide, the 60 g of anhydrous cupric sulfate for 22 h at room tem-
difference in the products from 1 and 4-cyclo- perature. The solution was filtered, the residue washed
with acetone and the solvent removed by distillation.
octenyl brosylate is understandable since the Fractionation of the residue afforded 5.8 g (21.2%) of a
latter is thought to proceed via a more car- viscous glycol mixture, b.p. 96-124" (0.4 mm) and 39.4 g
bonium ion-like transition state which allows (77%) of 5-cyclooctene-trans-1,2-diol isopropylidene ketal
greater flexibility of the ring and thus more (5), b.p. 66-68' (2.0 mm); ng 1.4699; i.r. 3020, 2985, 2940,
n-participation in the product-forming step. 2860 1100 cm-'; n.m.r. 5.64 (2H, mult), 3.90 (2H, mult),
Can. J. Chem. 1972.50:2152-2155.

2.24 (8H, mult), 1.33 (6H, sing).


Anal. Calcd. for Cl,Hl,O,: C, 72.46; H, 9.95. Found:
Experimental C, 72.50; H, 9.87.
Melting points and boiling points are uncorrected;
5-Cycloocrene-trans-I,2-diol(2)
v.p.c. analyses were performed on an F and M Model 720
Five grams (0.027 mol) of ketal 5 were hydrolyzed with
instrument; i.r. spectra were recorded in chloroform solu-
85% formic acid at reflux for 2 h. After saponification of
tion; and n.m.r. spectra in deuteriochloroform unless other-
the product with aqueous sodium hydroxide, distillation
wise noted. Microanalyses were performed by Dr. S. M.
gave 3.12 g (80%) of 2, b.p. 88-89" (0.12 mm); ng 1.5110;
Nagy and Associates (M.I.T.) and by A. B. Gygli, Micro-
i.r. 3320 cm-' ;n.m.r. 5.59 (2H, trip J = 4), 4.38 (2H, broad),
analysis Laboratory (Toronto).
3.53 (2H, mult), 1.1-2.75 (8H, mult).
Solvolysis of 1.5-CyclooctadieneMonoepoxide (1) Anal. Calcd. for C,H,,O,: C, 67.57; H, 9.92. Found:
(A) With 85% Formic Acid C, 67.72; H, 10.11.
To 500 ml of hot (95") formic acid was added 60 g Acetylation of the remainder of the diol in the usual
(0.48 mol) of 1 dropwise with stirring. An exothermic manner afforded a mixture of diacetates. We were unable
reaction ensued. The temperature was maintained at 95" to completely resolve the mixture under any v.p.c. con-
for 1 h after the final addition and then most of the acid ditions. There were at least eight components present, none
was removed by distillation at 80 mm. The residual brown of which corresponded to diol2. The lack of reaction of this
oil was treated with 150 ml of cold 50% aqueous sodium mixture with dilute bromine solution, the absence of n.m.r.
hydroxide and stirred at room temperature overnight. The absorptions below 6 5.4 and the absence of a significant
thick mass was extracted with four 200 ml portions of peak at m/e 224 showed that the mixture was composed
chloroform and the extracts were dried, evaporated, and of saturated materials only. Two components were isolated,
carefully distilled to give an alcohol fraction (2.6 g, 4.3% reduced with lithium aluminum hydride, and the products
as dienol), b.p. 45-59" (0.25 mm), a main fraction (48.5 g, shown to be bis-endo-bicyclo[3.3.0]octan-2,6-diol(6) identi-
70.1% as cyclooctene diols), b.p. 83-98" (0.23 mm), and a cal with an authentic sample (see below) and a mixture of
non-distillable residue which was discarded. 2,5- and 2,6-epoxycyclooctano1, also identical with an
authentic sample (1 1).
(B) With 98% Formic Acid
The reaction was carried out in the same manner except Bis-endo-bicyclo[3.3.0]octan-2.6-diol (6)
the temperature was maintained at 60". Fractionation of Bicyclo[3.3.0]octan-2,6-dione(12) (3.53 g, 0.026 mol) was
the saponified mixture gave no alcohol fraction, 47.2 $ reduced over prereduced platinum oxide in 75 ml of
(68% as cyclooctene diols) of a viscous oil, b.p. 85-100 methanol at 80" and 1450-1300 p.s.i. for 12 h. Filtration
(0.25 mm), and some residue which was discarded. and evaporation of the solvent gave residue which was
The alcohol fraction was separated into two components distilled to give 6 (3.36 g, 9379, b.p. 102-103" (0.38 mm);
by preparative v.p.c. (8 ft x 0.25 in. 20% SE30, 150°), one n g 1.5095. I(

of which was identified as 3,s-cyclooctadienol(3) (9) which Anal. Calcd. for C,H1402 : C, 67.57; H, 9.92. Found :
was distinguished from 2,4-cyclooctadienol (4) (10) by its C, 67.42; H, 9.72.
U.V.spectrum: I,,, (EtOH) 230 nm ( E 4070). The bis-phenylurethane had m.p. 196-197".
Anal. Calcd. for C,H,,O: C, 77.38; H, 9.74. Found: Anal. Calcd. for C,,H,,O4N2 : C, 69.45; H, 6.63; N, 7.37.
C, 77.13; H, 9.63. 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 work (2, 3) has shown that the susceptibilities
authors attempted to relate the contribution of of salts are not very different depending on
oxygen atoms to the molar diamagnetic suscepti- whether they are crystals or in solution, at least
bility with the type of bonding of the oxygen. for uni-univalent salts; typically the suscepti-
The compounds then considered contained bility of the salt in solution is 4 to 5% higher.
oxygen linked to nitrogen and phosphorus, and The susceptibility varies very little with con-
these were considered with special reference to centration (4), so it was thought to be justifiable
the bond orders of the bonds to oxygen. The to compare salt solutions of different concentra-
present note deals with compounds containing tions.
oxygen linked to chlorine or bromine, partic-
Experimental
ularly in the sodium salts of oxyhalide ions.
Chemicals
Since some of the compounds in question are
Sodium Hypochlorite
difficult to obtain as pure crystals (e.g., sodium A stock solution (about 1.2 M) was purified by filtration
hypobromite), the measurements of suscepti- through sintered glass, and then adding a 5% solution of
bility were made on aqueous solutions. Earlier barium chloride dropwise with stirring, until no more