carbon of p-nitrocumyl chloride can be observed (unpublished work [27] M . M . Kestner, Ph. D. Thesis, Purdue University, May 1973.
of Dr. P. A. Wade). But, ordinarily the S,2 displacement does not 1281 J . F. Garst, Accounts Chem. Res. 4,400 (1971).
compete with the radical anion process when p-nitrocumyl chloride
i s treated with a nucIeophile. However, with cumyl chlorides which
enter into radical anion reactions less readily than p-nitrocumyl chloride
competition from the SN2displacement at a tertiary carbon may occur
(see below). We are indebted to Dr. J. W Manthey and to Professor
F . G. Bordwell for drawing our attention to the possibility of SN2
displacements in cumylic systems.
[14] N . Kornblum, 7: M . Davies, G . W Earl, N . L. Holy, R. C. Kerber,
M . 7: Musser, and D. H. Snow, J. Am. Chem. Soc. 89, 725 (1967);
N . Kornblum and M . M . Kestner, unpublished work.
[15] N . Kornblum and F. W Stuchal, J. Am. Chem. SOC. 92, 1804 (1970).
[lh] N . Kornblum, 7: M . Dauics, G. W Earl, G. S. Greene, N . L. Holy,
R . C. Kerber, J. U! Manthey, M . 7: Musser, and D. H . Snow, J. Am.
Chem. SOC.89, 5714 (1967).
[17] Unpublished work by Drs. P. A. Wade and R. I: Swiger.
[18] N . Kornblum, G. W Earl, N . L. Holy, J . W Manthey, M . I: Musser,
D. H. Snow, and R. I: Swiger, J. Am. Chem. SOC. 90, 6221 (1968).
[I91 R . 7: Swiger, Ph. D. Thesis, Purdue University, June 1970.
[20] J. W: Manthey, Ph. D. Thesis, Purdue University, August 1969.
[21] Leung Cheng, unpublished work.
[22] , D. Boyd, and N. Ono, J. Am. Chem. SOC.96, 2580
N . K o r ~ l u m S.
(1974), and references cited therein.
[23] H. W Pinnick, Ph. D. Thesis, Purdue University. January 1972.
[24] The stable free radical galvinoxyl, an efficient scavenger of free radicals
[ P . D. Bartlett and 7: Funahashi, J. Am. Chem. SOC.84, 2600 (196211
also inhibits the reaction (12) -+ (20). If 5 mol % is added no reaction
occurs in 30min; without galvinoxyl the reaction goes 57 % to comple-
tion in this time (Dr. M . M . Kestner, unpublished).
[25] P. A. Wade, Ph. D. Thesis, Purdue University, May 1973. We are
indebted to Professor H. A. Morrison for valuable assistance in this
photochemical work.
[26] N . Kornbfum, R. 7: Swiger, G. W Earl, H . W Pinnick, and F . W
Stuchai, J. Am. Chem. SOC.92, 5513 (1970).
Mechanism of Ozonolysis
By Rudolf Criegee[*]
The formation of ozonides (1,2,4-trioxolanes) from alkenes and ozone can be described
as a succession of three [2 f 31 cycloadditions or cycloreversions involving primary ozonides
(1,3,3-trioxolanes)and aldehyde or ketone oxides as decisive intermediates, all of which have
finite lifetimes. There is no warranted experimental basis for assuming an alterna ive mechanism.
1. Introduction
The oxidative cleavage of unsaturated compounds with
ozone in solution, which was first studied in detail by Harries“]
at the turn of the century, is, in many respects an unusual
type of reaction. With very few exceptions, a double bond
is cleaved quantitatively under extremely mild conditions-
usually at or below -78°C in dilute solution in the absence
of acids or bases. The products of this cleavage are aldehydes
and/or ketones or their peroxidic derivatives, or-in the case
of aldehydes-their oxidation products, the carboxylic acids.
The product pattern obtained in individual cases depends
not only on the constitution of the starting compounds but
also on the reaction conditions, especially the solvent used
and the method of workup, which can be carried out purely
hydrolyti~lIy,reductively, or oxidatively.
[*] Prof. Dr. R. Criegee
Institut fur Organische Chemie der Universitat
75 Karlsruhe, Ric~ard-Willstatter-Allee(Germany)
Anyew. Chem. inrernal. Edit. / Val. 14 (1975) 1 No. 11
[29] S. D . Darling, 0. N . Deogan, and R . E. Cosgroue, J. Am. Chem. Soc.
92, 696 (1970).
[30] G. Fmenkel, S. H. Ellis, and D. 7: Dix, J. Am. Chem. Soc. 87, 1406
( 1965).
[31] B. N . Newton, Ph. D. Thesis, Purdue University, January 1972.
[32] N . Kornblum, S. D. Boyd, and F . W Stuchal, J. Am. Chem. Soc. 92,
5783 (1970).
[33] N . Kornblum and S. D. Boyd, J. Am. Chem. SOC. 92, 5784 (1970).
[34] A. K . Hoffmann, W G. Hodgson, D. L. Maricle, and W: H. Jura, J.
Am. Chem. SOC.86, 631 (1964); also see H. Sayo, Y: Tsukitani, and
M . Masui, Tetrahedron 24, 17 t 7 (1968).
[35] N . Kornblum, M . M. Kestner, S. D. Boyd, and L. f.Canrun, J. Am.
Chem. SOC.95, 3356 (1973).
1361 G. A. Russell, R. K . Norris, and E. J. Panek, J. Am. Chem. SOC.93,
5839 (1971).
[37] L. W: Seigle and H . E. Nass, J. Org. Chem. 5, 100 (1940).
[38] E. E. Dun Tamelen and G. Van Z y l , J. Am. Chem. SOC.7f, 835 (1949).
[39] N . Kornblum, S . D. Boyd, H . H! Pinnick, and R. G. Smith, J. Am.
Chem. SOC.93,4316 (1971).
[40] N . Kornblum, S. D. Boyd, and N . Ono, J. Am. Chem. Soc. 96, 2580
(1 974).
(411 J. J . Zeilstra and J. B. F. N . Engberts, Rec. Trav. Chim. Pays-Bas.
92, 954 (1973).
[42] J. K . Dory, H. Feuer, and N . Kornblum, unpublished work.
1.131 N . K o r ~ b ~ S.
~ mC., Carlson, and R. G. Smith, unpublished work.
[@] J . K . Kim and J. F. Bunnett, J. Am. Chem. SOC. 92, 7643 (1970);
J. F. Bunnert and B. F . Gloor, J. Org. Chem. 39, 382 (1974); J. F.
Bunnett, J. Chem. Educ. 51, 312 (1974).
[45] J. F. Wo,fe, J . C. Greene, and 7: Hudlicky, J. Org. Chem. 37, 3199
(1972); J. r! Hay, 7: Hudlicky, and J . F. Woye, J. Am. Chem. SOC.
97, 374 (1975).
2461 J . A. Zoltewiez and 7: M . Oestrrich, J. Am. Chem. SOC.95, 6863 (1973).
One group of possible reaction products includes the so-
called “ozonides”, which were shown more than three decades
ago by RiecherZJto have the structure of the 1,2,4-trioxolanes
(I). These are cyclic peroxides, a large number of which
are known today as distillable liquids or crystalline com-
pounds. The “exotic” nature of ozone cleavage or “ozonolysis”
is at once apparent when one considers the formation of
these ozonides. Not only is the double bond of the alkene
cleaved but also the ozone molecule itself, the two resulting
fragments of which form an ether bridge and a peroxide
bridge, respectively, between the two C atoms of the alkene.
0-0
R-CH=CW-R + 0, 4 RH<~)RH
(1)
Few other reactions have so compellingly warranted atten-
tion as regards the mechanism involved. We have been study-
ing this question since 1949. Essential contributions have been
made by other groups, too I3l.
745
2. Three-Step Mechanism of Ozonolysis
It is clear from the start that ozonolysis cannot proceed
a s a one-step reaction. As we currently believe (and as we
had already suggested in a lecture delivered at the IUPAC
Congress in New York in 1951),to our knowledge the reaction
proceeds in three discrete steps, all of which, according to
Huisgrn's terminology['], are 1,3-dipolar reactions ([2+ 31
additions or reversions). Let us first of all look at these postu-
lated steps and then, in the following and later Sections,
we shall deal with illustrative examples and confirmatory
evidence of their participation in ozonolysis.
Reuction A : Formation of a "primary ozonide"
Reaction B: Decomposition of the primary ozonide into
carbonyl compound + "carbonyl oxide"
Reuction C: Addition of the "carbonyl oxide" to the carbonyl
compound
3. Primary Ozonides
Addition compounds of ozone and olefin have already been
postulated on numerous occasions as the primary intermediate
products of ozonolysis, but it was not until 1958 before
S c h r i i d ~ dsucceeded
~~ in detecting such a compound. On ozoni-
zation of trans-2,2,5,5-tetramethyl-3-hexene (2) in pentane
at - 78°C crystals are formed which decompose exothermally
on warming to about -40°C and do not reappear on subse-
quent cooling. The constitution with still intact C-C single
bond could be confirmed by low-temperature reduction with
isopropylmagnesium chloride: the racemic diol (3) was
formed.
There are five conceivable ways in which we can formulate
an olefin-ozone adduct, namely those depicted in (4)-(8).
(4) (5) (6) (7) (8 1
rr-complex a-complex peroxy- oxy-1,Z- 1,2,3-tri-
epoxide dioxetane oxolane
746
Of these, only the dioxetane derivative (7) and the 1,2,3-
trioxolane (8) are likely to favor formation of a 1,Zdiol
on reduction. Formula (7), which was first proposed almost
half a century ago by Stuuciingerr.61 for the then hypothetical
primary ozonides, was recently favored by S t ~ r y ~ How- '~.
ever, according to Baiky[81the NMR spectrum of the primary
ozonideof (2)151ind~cates equivalence ofthe chemical environs
at both C atoms, which would not be so in the case of
(7). Story's apparent evidence for ( 7 ) . namely the reduction
ofa primary ozonide with pinacoline to give a 1,2-dioxetane'"],
was later recognized as being experimentally erroneous[Lo!
Other instances of the detection of primary ozonides have
been reported; those derived from aliphatic trans-olefins are
stable only below - 1I O T , those from corresponding cis-ole-
fins only below - 130"C1' 'I.
While the primary ozonides are, in general, 1,2,3-trioxolanes
( 8 ) there are also indications for the existence of T[ complexes
of formula ( 4 ) . Bailey was able to detect such complexes
in the reaction of ozone with electron-rich arenes at
-150"C1'21. They absorb visible light, but in contrast to the
deep-blue of ozone they are violet, red, or yellow. At higher
temperatures they decompose into their components. It is
possible that they are also formed from olefins and ozone
if sufficiently low temperatures are used. It is still questionable,
however, whether they play any further part in the process
of ozonization.
o-Complexes ( 5 ) or peroxy-epoxides ( 6 ) must be assumed
as primary products in the few ozonizations in which the
double bond is not completely cleaved but epoxides or their
secondary products are formed. This is the case in sterically
very strongly hindered olefins, K. g. in I-mesityl-I -phenylethyl-
eneIL3]or in adamantylideneadamantaner.'41. Probably the
intermediates ( 5 ) or (6) in these cases immediately lose an
oxygen molecule and thus give the epoxides. The addition
of ozone, which, in accordance with the principle resonance
formulas
is a typical dipole" 5 ] , proceeds stereospecifically, as is evident
from the configuration of the diols formed on reduction.
Since resonance stabilization of the ozone molecule is miss-
ing in the primary ozonides (8) they are not only thermally
much more labile but are also stronger oxidizing agents than
ozone towards some substrates. For example, tetracyanoethyl-
ene (TCNE) is stable toward ozone at - 78 "C but, according
to Giintlzer['61,is oxidized by primary ozonides to the (pre-
viously unknown) TCNE epoxide ( 9 ) . The primary ozonide
is converted smoothly into the carbonyl compound.
0 NC, /CN
o"0 + ,c=c,
% NC CN NC
Isolation of the primary ozonide is unnecessary, ozonization
of the olefin in the presence of one equivalent ofTCNE suffices.
The reaction has twofold significance: On the one hand it
is helpful for recognizing primary ozonides and estimating
their stability, and on the other hand one can obtain
carbonyl compounds as products by this "reductive ozoniza-
tion” even in cases where otherwise rearrangements to anoma-
lous ozonization products occur (see Section 4.3).
4. Carbonyl Oxides
Primary ozonides are stable at or above -78°C only in
exceptional cases. In order to explain the diversity of decom-
position products it was assumed at a very early stage[’”
that decomposition into a carbonyl compound (aldehyde or
ketone) and a carbonyl oxide (aldehyde oxide or ketone oxide)
(10) takes place in accordance with the Reaction B given
in Section 2. In this d~ompositionan 0-0 and a C<
bond cleave, while the (stronger) C-0 bonds remain intact.
Of the decomposition products the aldehydes and ketones
are stable compounds, whereas the carbonyl oxides ( I O ) ,
thus far unknown in substance, are energy-rich species but
have the possibility of resonance stabilization. The structures
of the carbonyl oxides are analogous to those of the amine
%=OF rH .\@,c-o\oQ
OQ
“I
oxides, nitrile oxides or sulfoxides, but only the nitrile oxides
have comparable resonance possibilities.
Which type of reactions can the carbonyl oxides (earlier
also called peroxidic zwitterions) undergo that will lead to
their final stabilization? These reactions will be described in
the following.
4.1. Dimerization
Primarily with olefins bearing four substituents at the double
bond, but also in other cases, one obtains as ozonization
products the “dimeric keto- (or aldehyde-) peroxides” ( I 1 j
They are most readily rationalized as
(1,2,4,5-tetrao~anes)~~’~.
dimers of the carbonyl oxides.
4.2. Reactions with Proton-Active Substances
Ozonization of olefins in the presence of alcohols[”* “I,
ammonia[”I, hydrocyanic acid[201,hydrogen peroxidec2‘I, etc.
leads to products, which arise formally-and in our opinion
also in reality-by addition of the respective reagent to the
carbonyl oxide. A typical’exampleis the ozonization in metha-
nol as solvent, in which the geminal methoxyhydroperoxides
( I 2 ) are formed.
Ozonolysis in methanol is also of preparative importance,
since in this case not only is the formation of dimeric peroxides
avoided but also that of oligomeric ozonides, which can some-
times considerably interfere with the ozonization in inert sol-
vents. If the carbonyl oxides were not zwitterions, but singlet
diradicals as proposed by G ~ d d u r d [ ~then
~ I , methanol should
not add as H-OCH3 but as H--CH20H; this however,
has never been observed.
Angew. Chrm. interim. Edit. / Vr,l. 1 4 ( I Y 7 5 ) / N o . I /
4.3. Rearrangements
There are a series of cases in which ozonization leads not
only to oxidative rupture of the double bond but also of
an adjacent C--C single bond. This “anomalous ozoniza-
tion”[221can be explained in terms of a peroxide rearrangement
of the carbonyl oxide. Whether this proceeds via a dioxirane
(13) as intermediatei231is undecided. The products in these
cases are esters, lactones, or (in the case of a,P-unsaturated
ketones) also acid anhydrides.
u -Hydroxyacetone is sometimes observed as by-product
in the ozonolysis of olefins bearing an isopropylidene group.
This can also be explained in terms of an-albeit different
type-rearrangement of a carbonyl oxide, here of acetone
oxide.The two-step rearrangement ought to involve formation
of a very unstable vinyl hydroperoxide (14) as interme-
diate124. 251.
4.4, Reaction with Aldehydes or Ketones
The most important and most frequent reaction of the
carbonyl oxides is their combination with an aldehyde or
a ketone to give an “ozonide”. This could be a monomeric
ozonide having the l,2,4-trioxoIane structure, formed accord-
ing to Reaction C in Section 2 by cycloaddition, or also
an (in inert solvents usually insoluble) oligomeric ozonide.
Very little is known about the constitution[2h1of the latter, so
they will not be considered any further here. In section 5 we
shall review the arguments that favor formation of the mono-
meric ozonides according to Reaction C.
5. Formation of Monomeric Ozonides
5.1. Scope of Formation of Monomeric Ozonides
Monomeric ozonides are obtained from alkenes only if
at least one H atom is present at the double bond[271, whereas
tetraalkyl-substituted ethylenes afford only oligomers, dimeric
peroxides, and/or rearrangement products[lxl.This is under-
standable,since in the last mentioned cases the carbonyl oxides
must be accompanied by ketones, whose activity in a cycload-
dition is certainly much smaller than that of the aldehydes.
Hence the zwitterion (carbonyl oxide) has time for alternative
reactions.
One can, of course, also “force” keto groups to add to
carbonyl oxides. One possible way ofdoing this is by increasing
the reactivity of a keto group by neighboring substituents.
Suitable substituents for this purpose are eIectron-with#rawing
groups such as halogen atoms or ester groups. Thus mono-
meric ozonides could be obtained both from 1,4-dibromo-2,3-
dimethyl-2-butene (15) as well as from 2,3-dimethylcrotonate
747
 (16), although both starting compounds carry four substi-
tuents at the double Bromoacetone and pyruvate,
respectively, must be assumed as intermediates.

-.)

CHzBr H3C
C H3-C H=C H-C 2Hs

A keto group can also be reactive, however, if for steric

reasons there is a particularly great tendency for its C atom
to change from sp2- into sp3-hybridization. This is so, e. y.
in the case of adamantanone, which has proved to be a good
dipolarophile toward several carbonyl oxides[’41.
The third possibility for the addition of a keto group to Primary ozonides of u n s ~ m e t r i colefins ( 2 4 ) can funda-
a carbonyl oxide group is when both groups are in one mole- mentally decompose in two different ways, so that two alde-
cule, so that the cycloaddition will be an intramolecular reac- hydes or ketones and two carbonyl oxides are formed. These
tion, which is far more preferred than an intermolecular reac- can afford by cycloaddition three ozonides, namely the unsym-
tion. Here, it is necessary to usea cyclic olefin with a tetrasubsti- metrical ozonide corresponding to the starting olefin in addi-
tuted double bond as starting material. Indeed, cyclopentenes tion to two symmetrical ozonides.
such as (17)r291andcyclobutenes such as (18)[301give mono-
meric ozonides in excellent yields.

If, on the other hand, the double bond is present in a Since the time it became possible to separate similar
six- or higher-membered ring no monomeric but only oligo- ozonides by thin layer chromatography or the lower members
meric ozonides are obtained[“’. Apparently, in these cases by gas chromatography1331,the expected “crossed-ozonides”
the cycloaddition is not favored since the monomeric ozonide have been detected and isolated from the “normal” ozonides
would then contain, inter alia, an eight- or higher-membered in many ~ a s e s [ ~ ~ - ~ ~ ] .
ring and such rings are generally formed only with difficulty.
5.4. cislirans Isomeric Ozonides
5.2. Ozonization in the Presence of “Foreign” Aldehydes or
Ketones In a 1,2,4-trioxolane ring, substituents can be present in
the cis or trans positions. Using the above mentioned methods
If the carbonyl oxides have a finite lifetime they must also
of separation it has been possible to isolate numerous pairs
be able to add to an aldehyde or reactive ketone admixed
of cis/trans isomeric o ~ o n i d e s [361.
~ ~In, some of these cases the
prior to the ozonization, for the latter ought to be able to
configuration could be unequivocally assigned. SymmetricalIy
compete for the carbonyl oxide with any aldehyde (or ketone)
disubstituted trioxolanes are rneso-forms in the cis-ozonide,
formed during ozonization. This is especially so when an
racemates in the trans-ozonide. Optically active ozonides can
aldehyde is added and a ketone is formed from the olefin.
be obtained only from the latter. Murrayr371achieved this
Furthermore, admixed aldehydes or ketones can be added
by partial destruction of the one enantiomer with brucine,
in larger concentration, and in the extreme case they can be
used as solvent. Examples of such intermolecular com-
peting reactions are those which lead to the ozonides
(19j--(2*3)l3‘.’2’251,
In these and other cases ozonides of olefins not employed cis -0zonide trans -0zonide
in the experiment are obtained. meso -form racem -form

748 Anyew. Chern. iaternar. Edit. / W1. 14 ( 1 9 7 5 ) / , N o . I 1

and Korher"" by chromatography of the racemates on opti- be differentiated NMR-spectroscopically. Both ozon-
cally active ceII~lose-2'/~
acetate ides-(SO) and (3l)-are formed in exactly equal amounts.
The cis-ozonides have longer retention times than the truns-
ozonides in column- and gas-chromatography, so a less
tedious albeit not as well founded determination of con-
figuration can be carried out in this

5.5. Competition between Inter- and Intramolecular Ozonide

Formation

When olefins bearing keto groups are ozonized there is

the possibility that such keto groups interfere in the ozonide
formation. As long ago as the fifties L o h u ~ ~ . s [ozonized
~"l the
unsaturated diketone ( 2 5 ) . Here, decomposition of the prim- 130) 1 : l 131)

Accordingly, both keto groups react equally rapidly with

c:
ary ozonide ought to lead to the ketocarbonyl oxide (27)
as wcll as the diketone (26). The carbonyl oxide group now
has the choicc of forming an ozonidc ring intermolecularly
with a kcto group of the diketone or intramolecularly with
thc keto group in its own molcculc. The intramolecular reac-
tion predominates; the same o7onide as is formed from
1,2-dimethylcyclopenteneis obtained in good yield.
Later, Grieshuim""'l was able to obtain the ozonidc of
1,2-dimethylcyclobutene from the unsaturated diketone (28)
the carbonyl oxide. Hence there is no preference for the keto
group which is formed along with the carbonyl oxide group
on cleavage of the primary ozonide. Reaction of these two
groups with one another in a partial solvent cage is therefore
ruled out, as is also a direct intramolecular rearrangement
of the primary ozonide into the ozonide. Rather, the interme-
diate (291 must have a finite lifctimc so that the carbonyl oxidc
has time to choose between the two alternative possibilities.
The starting compound can be varied in many different
ways so as to obtain further information about the possible
choices open to the carbonyl oxide group. Only two further
examples will be mentioned here. One concerns the ozonolysis
of the phenacyl derivative corresponding to the acetonyl com-
pound. An acetyl and a benzoyl group compete in the interme-
diate. Here also there are two-in this case separable-reac-
tion products (32) and (331, which, however, are not formed
in equal amounts. As regards cycloaddition the acetyl group
proved to be 1.7 times more reactive than the benzoyl group.
c H3 c gH5

having onc less methylene group in each of the two chains

(scc also Section 5.1).

132j 1.7 1.0 (33)

c H, In the second example 4-acetyl- 1,2-dimethylcyclopentene

was ozonized. In this case two acetyl groups situated in differ-
ent positions to the carbonyl group compete with each other
5.6. Intramolecular Competing Reactions in the intermediate. In one case a cyclopentene ozonide ( 3 4 )

When H cyclic olefin having a sidechain containing ;I kcto

group is o~onized one expects intermediary formation of
a molecule having one carbonyl oxide and two keto groups, cr' H3
both of which can cycloadd to the carbonyl oxide group.
Mrs. Bunciu has carried out experiments of this type['"]. The
1
first example was (3,4-dimethyl-3-cyclopentenyl)acetone.In CH3 (34J
this citse t h e intermediate product to be expected on oroniza-
tion is symmetrical with respect to the Twitterion group. In
orderto bcablc todistinguish bctwcen the two keto groups the
) I atoms adjacent to the keto group of the starting material
were deuterated. The two possible reaction products can now
?WH3
0 CI1, (35)

749
should have been formed, and in the other a cyclobutene
ozonide ( 3 5 ) . The result was surprising: the cyclobutene deri-
vative was formed exclusively, although it should be thermo-
dynamically more labile because of greater ring strain. The
reaction must therefore be kinetically controlled.
5.7. Ozonides from Diazo Compounds
In all experiments described so far the carbonyl oxide was
formed by spontaneous decomposition of a primary ozonide.
On photo-oxidation of diphcnyldiazomethane, Murru!.[''I was
able to detect a short-li\ed product which in the presence of
benzaldehyde affords the oronide of triphenylethylene. This
short-livcd intermediate can only be benzophenone oxide (36).
Mtrrrtcv's experiments provide evidence, which is indepen-
dent of all ozonolysis results, that ozonides can arise by addi-
tion of a carbonyl compound to a carbonyl oxide.
6. Objections to the "Three-Step Mechanism"
Having dealt with the arguments supporting the validity
oft he proposed ozonolysis mechanism, we should not overlook
a number of serious objections to this mechanism or at least
to its representing the sole route from olefins to ozonides.
The principal objections come from the stereoselectivity of
ozonization and the incorporation of labeled oxygen into
the trioxolane ring of ozonides.
6.1. Stereoselectivity of Ozonolysis
The mechanism developed in Sections 1 to 5 requires, inter
uliu, that the primary ozonide decomposes entirely into two
fragments in the second reaction step. A cis olcfin should
then give the same fragments as the isomeric Irut1.s olefin.
These fragments are transformed by cycloaddition into the
ozonidcs which can likewise exist in cis/rruns isomeric forms.
The mechanism developed is incapab!e of predicting whether
the reunification of the fragments leads to a cis or a rruns
ozonide or to a mixture of the two.
In any case the ozonidc composition should be independent
of whether the c.i\ or truns olefin is used as starting material.
However, as first established by . S ~ h r ~ d e rand [ ~ ~later
~ , by
S ~ o r j and
. M ~ ~ r r u y I " and
~ ' ~ , other workers["'. 3''1, this is not
always the case. The geometry of the olefin can indeed exert
ii considerable influence on the composition of the ozonide
mixture, especially when bulky groups such as rrrt-butyl or
isopropyl are attached to the double bond of the olefin. This
applies not only to the composition of the "normal" ozonides
but in the same way to that of "crossed ozonides".
In order to interpret these findings, Storj* and Murra!.["'
developed an alternative mechanism of ozonolysis. Although
it explains the stereochemical results. their proposal contains
ii number of improbable ud hoc. assumptions, c.8. insertion
of an aldehyde group into an 0-0 bond of the primary
750
ozonide. A detailed discussion is unnecessary however, since
another explanation developed by Bui/ey[""~ 471 requires no
fundamentally new mechanism.
According to Bailey, carbonyl oxides having two unlike
substituents (e.g. H and tert-butyl) should be able to exist
in syn;mri isomeric forms, similar to those of oximes. This
hypothesis states that cisltruns isomeric primary ozonides hav-
ing a bulky substituent at each of the two carbon atoms
should afford unequal amounts of syn and anti carbonyl oxide
and, moreover, that these stereoisomeric carbonyl oxides
add in unequal amounts to aldehydes to form ci.s and rrons
ozonide.
I1
Ii\ /
,c' C\
11 It
J " "
It-Cli 0
Prerequisite for this hypothesis is that the primary ozonides
are nonplanar immediately prior to decomposition and that
the preferred conformations of the five-membered ring depend
upon the position and size of the substituents. Likewise. the
oronides should be formed in preferred nonplanar confor-
mations.
6.2. Incorporation of Labeled Oxygen into the Ozonide Ring
Ozonization ofan olefin in the presence of an [0"]aldehyde
should afford an ozonide having a labeled oxygen atom. The
three-step mechanism would require, in accord with Reac-
tion C (Section 2) also in the modified form of Bailey. that
the labcled 0 atom is always incorporated exclusively as
the ether bridge of the ozonide.
In principle, it is possible to deduce the site of the heavy
oxygen atom from the fragments observed in the mass spectra
of ozonides. Stor). and were the first to perform
such studies. They came to the surprising conclusion that
a considerable proportion of the label was located in the
peroxide bridgeand not in theether bridge.This would indicate
that part of the 0--0 bridge is generated from the aldehydic
oxygen atom with formation of a new 0-0 bond. The
mechanism due to Story and Murru!. mentioned in Section
6.1 would account for these findings.
Independent studies performed in recent years, first by Flis-
rdrl'"] and later by Kuczkowskil""', have shown that the heavy
ozonides prepared in the above manner from ethylene, propy-
Icne, 1-butene, 2,5-dimethyI-3-hexene, and stilbene all contain
the " 0 label exclusively, or at least to an extent far in excess
of 90 x, in the ether bridge. No explanation for the different
results of Story and Murray has yet become available. At any
rate, there is no definite experimental evidence requiring an
alternative mechanism.
7. Concluding Remarks
In conclusion, let us recapitulate how the action of ozone
on olefins leads to complete oxidative cleavage of the double
bond and furthermore to cleavage of the ozone molecule
into an ether and a peroxide fragment.
Even the initial step, addition of ozone to the double bond,
amounts to an oxidation of the olefin to the oxidation state
ofa 1,2-diol. At the same time, the -04-0- unit, which
is still able to perform oxidation, is anchored to the organic
molecule. Since the three 0 atoms are bonded relatively loosely
to each other in the primary ozonide owing to lack of
resonance, one ofthe 0-0 bonds is easily ruptured. However,
stable or stabilized molecules (and not energy-rich radicals
or ions) can only arise if the C--C bond is broken simul-
taneously. As a result of this cleavage, the two C atoms which
were originally double bonded attain the oxidation state of
ketones or aldehydes while the ozone molecule is reduced
to a derivative of hydrogen peroxide. The ozonide is finally
decomposed by water. The overall reaction is described by
the equation
.
'C=C< + O3 + H20 + 2 :C=O + HzOz
Of course, many details still remain open. Let us mention
a few.
For instance, what is the structure of the oligomeric ozonides
and how are they formed'! Do they really contain 0 - 0 4
units alongside ether and peroxide groups, as proposed by
Greenwood I26!
With suitably substituted cyclobutenes, endolexu isomeric
ozonides have been found on numerous occasions15 411. How
can their configuration be established and what determines
their relative proportions?
Will it become possible to at least detect a carbonyl oxide
spectroscopically, or even to isolate one?
The products of ozonolysis are strongly solvent dependent.
Can this dependence be correlated with any solvent parame-
ters?
What is the course of gas phase ozonolysis of olefins[2-s 2 , 531?
Are primary ozonides again formed initially? If so, do they
also decompose to aldehyde and carbonyl oxide, or is a diradi-
cal >c-06 formed instead?
Can the view recently expressed by G o d d ~ r d [that~ ~ ' the
so called cdrbonyl oxides are singlet diradicals also in solution
be confirmed or disproved? Solution of this problem will
be of crucial importance for our understanding of the events
occurring during the ozonolysis of olefins.
In 1844, that is 131 years ago, and four years after the
discovery of ozone by Schiinbein, no less than six pages were
devoted to ozone by Otto in his "Lehrbuch der Chemie"[54].
He closed this section with the exclamation: A highly produc-
Chrnr. irirrrriot Edrr. ! RA. I 4 ( 1 9 7 5 )
41ig~w ' No. / I
tive field for further research! I consider this statement to
have lost none of its validity.
Received: Fcbruary 28. 1975 [ A 76 IE]
German version: Angew. Chem 87. 765 (19751
C . Hurries, Liebigs Ann. Chem. 343, 311 (1905).
A . R i d i e , R . Mri\rer. and If. Saurhoff, Liebigs Ann. Chem. 553. 246
i1942).
Older summaries: a ) P. S. Bui/c,i,, Chem. Rev. 58. 925 (1958): b) R .
W: M u r r u y . Accounts Chem. Res. I , 313 (1968).
R . Hiri.vqeii. Angew. Chem. 75, 604 (1963); Angcws. Chem internat.
Edit. 2. 565 (1963).
R . C r i e g r e and G. Schriilm.. Chem. Ber. 93, 689 (1960).
H . Sruudiiiger, Ber. Deut. Chem. Ges. 58, 108X (1925).
P. R . Srorj,. J. A. Alfotd. J . R . Biayrrs, and W C. R ~ J J. . Amer.
Chem. Soc. 93. 3042, 3044 ( 197 I ).
P. S. Buile!. J. A. 7'hoiiipson, and B. A . Shoiilders, J. Amcr. Chem.
Soc. 88, 4098 ( 1966).
P. R . Srorr. E. A . W h i r r d , and J . A. A//ord. J. Amer. Chem. Soc.
94, 2143 (1972).
K . R Kopeck!,, R . A . L o c k i ~ o o d ,J . E. Filhr, and R. W: Reid. Can.
J. Chem. 51, 468 (1973): P. S. Builey. T. P. Crrrrrr, C. M . F i s c k r .
and J 4. Thonipson, ihid. 51. 1278 (1973).
F . L. Greeiircood. J. Org. Chem. 30, 3108 (1965): 1.. J Durliani and
F . L. G r e e r i ~ o o d ,ihid. 33. 1629 (1968): F . L. Gret~rinoodand L. J.
Diirhuin. ihid. 34, 3363 (1969).
P S. Bnilej.. J. W W(ir.d. 7: P. Curter. Jr.. E. Nieh, C. M . Fischrr,
and A , - / . Y Khuslioh. J. Amer. Chem. Soc. Y6, 6136 (1974).
P. S . Builn- and 4. G. Lniie. J. Amer Chem. Soc. XY. 4473 (1967).
H . KPIII. Chem. Ber. / O X , 1207 (1975).
Cf. however: P. J. Hor. 7: H . Dirririiny, and CV A . Goddard. Accounts
Chcm. Res. 6. 368 (1973).
R . Ci-iryrt, and P. Giiiirhrr, Chern. Ber. 96. 1546 (1963).
R . C r i q w and G Wwin.. 1 irhigs Ann. Chem. 564. 9 (1949).
gr" and G. Lohotis, Liehrgs Ann. Chem. 583, 6 (1953).
M . J. F r e i w r i . and E . K . Fir/[/.\,J. Org. Chcm. 2Y. 2240 11964).
E. K . F I L N S Advan.
, Chem. Scr. 51. 99 (1965).
J . C. Roherrwii and W J . Kv5iio. J. Org. Chem. 35. 545 (1970).
See [3a], Page 947ff.
W R . Utird and M! A. Gor/dor.d. J. Aincr. Chem Soc. 97, 2x19 (1975).
P. R . S t o r ! . and J R . Burgc,ss, J. Amer. Chem. Soc. XY, 5726 (1967):
90, 1094 (1968).
R . C r i r q r e a n d H . K o r h t v . Chem. Ber. 1 0 4 , 1812 (1971).
F. L. Grr.rincoorl and H . Kirhriisrriri. .I.Org. Chem 32
R . Crieyee, A . Krrckoir., and H . Z r ~ i k r Chem. , Ber. S X , 1x78 (1955).
R . Criegrr. S . S. Burh. and R. rot1 Borriliuupr, Chem. Ber. 93. 2891
( 1960).
Example: R. Cri<,gee and G. Lohurrs. Chem. Ber. 86. I (1952).
Example: R . Crirgrr and K . N o / / , Liebigs Ann. Chem. 62.5, I (1959).
R. Crirgee, G. Bliisr. and IJ. Ziiihc. Chem. Ber. 87, 766 11954).
R . M! Miirru!., P . 8. Sior!.. and L. D. Looii. J. Amer. Chem. Soc.
87. 3025 (1965).
G. Sdiriirlrr. Chem. Ber. 9
, i r . D. A . I'NII
C . Rirzebos. J . C. G r i i r r i i i ~ , / i h / i i ~ ~ . \ ~and Dori~. Rec. Trav.
Chim. Pays-Bas 82, 1234 (1963).
'3
L. D Louri, R . M: Mrirru!,, and P. R . S r o r j , J . Amer. Chem. Soc.
87, 737 (1965).
0. Lorrnz and C. R r Purks, J. Org. Chem. 30. 1976 (1965).
R . M! Murrur. R . D. Ri,ursdi'eh, and P. R . Storr, J . Amer. Chem.
SOC.8H. 3655 (1966).
R C r k g e c and H . Korher. Chem. Ber. 104, I807 (1971).
G. L o l i a u ~Chem. Ber. 87. 1708 (1954).
K . Grieshouni, Chem. Ber. 101. 463 (1968).
R . Criryee and A. B~IICILI,Chem -Ztg. 9H. 161 (1974): R , Crrrgrr. 4.
Baririii. and H. Krui. Chem. Ber. I(J8. I642 ( I 975).
R . W! M i r r r a ~and A. Sir:ur, J. Amer. Chem. SOC 95, 3343 (1973):
R . W Murrrr! and D. P. H i q / q , ibirl. 95, 7886 (1973).
R . U: M i i r r a i . , R . D. Y o u s w f ~ d i .and P R . S l o r i . J. Amer. Chem.
Soc. 88. 3 143 (1966).
F. L. Grrriii%oot/and B. J. I I u i k e . Tetrahedron Lett. 1965. 631.
P. R . Story. R . M.: M i r r r u r , and R. D. Yorisst.f\.eh, J. Amer. Chem.
Soc. 88. 3 144 ( I 966); R . U: M r i r r q ~ .R . D. Yori.s.sufl~~li.and P R . Storj..
ihid. 89, 4473 (1967).
N . L. Bauld, J. A . Thoirip.soii, C. E. Hiidson. and P. S. Bui/rJ,,J. Amer.
Chem. Soc. 90, I822 ( I 96X).
R . P. Luirrtwr. R. L. Kiic:I\~~cski.and C. U: Grili.5. J. Amer. Chem.
SOC.96, 348 (1974).
P. R . Sror.!,. C. W. Bishop, J . R . Birryrss. R . M.: .k4urr[i)~. and R . D.
Yoi~.rsef~~eh. J. Amer. Chem. Soc. Y(J. 1907 (196x1: P. R . Stor,.. C. E.
Bishop, J. R . Burgess,and J. B. Olson, Advan. Chem. Ser. 77, 46 (1968):
R M: Murr-01 and R . Hugrii. J. Org. Chem. 36, 1103 (197 I).
S. F/i.\:dr. J . CorIes, and J. R r i i ~ r d ,J. Amer. Chem. Soc. 90. 1364
(1968).
751
[SO] C. M! G i / / i r , > and R 1.. K i r d o \ i s k i . J. Amcr. Chem. Soc. 94, 7609 [ 5 3 ] R . .AiAiii.wii. B. J . F i i i / ~ i r s o i i .and !V. J . Prric, J. Amer Chem. Soc.
(1972): C. l i : Gi//ie\. R . 1'. Loftiiiir~r.and R . L. K ~ i i : k r n ~ . ~ Arhrrl.
i , 96. 95, 7592 (1973). B. J . Fiir/~ri~.~oii, N . .I. P i r l s , and R. A r L i i ~ w i ~ihirl.
,
1536 (1974): K . P. L ~ r i r i i ~ i eand
r R. L. KircAoa.sLi. ihrrl. 94. 6205 (1974). 96. 5356 (1974): N . .I. Plir.5 and B. J . F i i ~ l o ~ s o rAnsew. x Chem. X7.
1511 R Crieyee and R . R~i.s~/,fii.\c/~/, Chcm. Ber. / 0 3 . 50 (1970). I X (1975); An_eea. Chem. internat. Edit. 14, I (1975).
[5?] L. A . H i d / . 1. C. Hi~aisiiii~~.. and J f i ~ m A / m Can.
, J. Chem. S/. 1504 [54] F . J . Otro: Lchrbuch der Chemle. 2nd edit., Vol. 2. 1st half. Vieweg.
I 1 973). Braunschweig 1844, p. 653.

C 0 M M U N I CAT1 0 N S

The novel compound ( 1 ) displays a slight electrical conducti-

vity in tetrahydrofuran, apparently due to partial dissociation.
On the other hand, ( I ) is also readily soluble in nonpolar
solvents such as pentane or benzene. Molecular-weight deter-

mination in benzene gives the value expected for (1) (exp.

455, calc. 466). This finding contraindicates a largely ionic
structure, such as is characteristic of alkali metal-transition
metal carbonyl compounds, which are composed of alkali
metal cations and carbonylmetalate anions.
The 'H-NMR spectrum of ( 1 ) in [D8]-THF at -2O'C con-
Dilithium-Nickel-Olefin Complexes. tains two singlets at s=7.77 and 7.9 for the protons of the
Novel Bimetal Complexes Containing a Transition amine. Three groups of signals of approximately equal intensity
Metal and a Main Group Metal occur at K = 8.2,9.33, and 9.72 for the protons of the cyclodode-
catriene bound to the nickel. All the protons of the CDT
By Kluus Jonas"] ligand in complex (1) are more strongly shielded than in
CDT . Ni", whose spectrum consists of only two signals at
During investigations on the reactions between nickel(0) com-
r=5.7 (=CH) and 7.7 (-CH2).
plexes and organometallic compounds of Group I B to IIIB
elements, which have already been reported in part".'], it The two most likely structures of ( 1 ) are shbwn as ( I u )
was found that binary olefin complexes such as all-trans-l.5,9- and ( I h ) .
cyclododecatrienenickel(~)[~~ [CDT. Nil or bis( I S-cycloocta-
diene)nickel(~)[~]
[(COD),Ni] can also undergo reaction with
elemental lithium to form crystalline adducts.
The deep red solution formed by CDT'Ni in a mixture of
tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine Ni
gradually becomes lighter in color, e. g., on stirring with lithium
sand. If the excess of lithium sand is removed by filtration
and diethyl ether added to the reaction mixture, the yellow
adduct (2) crystallizes out on cooling to -40°C.

In both cases adduct formation can be attributed to the ten-

The CDT ligand in complex (1) is present as unchanged
all-trans-l,5,9-~yclododecatriene,as is evident from the reac-
tion of (1) both with cyclooctatetraene (COT) and with COT
and an excess of 1,5-cyclooctadiene. In the former case
CDT' Ni is regenerated alongside Li2(COT)while in the second
the excess of C O D quantitatively displaces the cyclododeca-
triene from the nickel.
[*] Dr. K. Jonas
Max-Planck-Institut fur Kohlenforschung
433 Mii1heim:Ruhr. Kaiser-Willielm-Platr 1 (Germany)
dency of the coordinatively unsaturated CDT. Ni" (16 electron
shell) to achieve a noble gas configuration in which the two
additional electrons come from the two lithium atoms. With
regard to the hybridization of the nickel, structure ( l u )
appears more likely than ( I h). In ( I a ) the ligands are
arranged tetrahedrally around the Ni atom. The two Li atoms
jointly occupy a coordination site of the nickel. This kind
of tetrahedral arrangement around the central atom is also
suspected in [CDT. Ni(C0)][3Jand the corresponding mono-
phosphane adducts [CDT. Ni(PR3)][3*41.However, considera-
tion of models permits better correlation of the 'H-NMR
spectrum of ( I ) with / Z / J / [ ~ ] .
On reaction of lithium sand with coordinatively saturated
bis( 1,5-cyclooctadiene)nickel(o) ( 18 electron shell), the

752