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carbon of p-nitrocumyl chloride can be observed (unpublished work [27] M .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 [29] S. D . Darling, 0. N . Deogan, and R . E. Cosgroue, J. Am. Chem. Soc.
i s treated with a nucIeophile. However, with cumyl chlorides which 92, 696 (1970).
enter into radical anion reactions less readily than p-nitrocumyl chloride [30] G. Fmenkel, S. H. Ellis, and D. 7: Dix, J. Am. Chem. Soc. 87, 1406
competition from the SN2displacement at a tertiary carbon may occur ( 1965).
(see below). We are indebted to Dr. J. W Manthey and to Professor [31] B. N . Newton, Ph. D. Thesis, Purdue University, January 1972.
F . G. Bordwell for drawing our attention to the possibility of SN2 [32] N . Kornblum, S. D. Boyd, and F . W Stuchal, J. Am. Chem. Soc. 92,
displacements in cumylic systems. 5783 (1970).
[14] N . Kornblum, 7: M . Davies, G . W Earl, N . L. Holy, R. C. Kerber, [33] N . Kornblum and S. D. Boyd, J. Am. Chem. SOC. 92, 5784 (1970).
M . 7: Musser, and D. H. Snow, J. Am. Chem. Soc. 89, 725 (1967); [34] A. K . Hoffmann, W G. Hodgson, D. L. Maricle, and W: H. Jura, J.
N . Kornblum and M . M . Kestner, unpublished work. Am. Chem. SOC.86, 631 (1964); also see H. Sayo, Y: Tsukitani, and
[15] N . Kornblum and F. W Stuchal, J. Am. Chem. SOC. 92, 1804 (1970). M . Masui, Tetrahedron 24, 17 t 7 (1968).
[lh] N . Kornblum, 7: M . Dauics, G. W Earl, G. S. Greene, N . L. Holy, [35] N . Kornblum, M . M. Kestner, S. D. Boyd, and L. f.Canrun, J. Am.
R . C. Kerber, J. U! Manthey, M . 7: Musser, and D. H . Snow, J. Am. Chem. SOC.95, 3356 (1973).
Chem. SOC.89, 5714 (1967). 1361 G. A. Russell, R. K . Norris, and E. J. Panek, J. Am. Chem. SOC.93,
[17] Unpublished work by Drs. P. A. Wade and R. I: Swiger. 5839 (1971).
[18] N . Kornblum, G. W Earl, N . L. Holy, J . W Manthey, M . I: Musser, [37] L. W: Seigle and H . E. Nass, J. Org. Chem. 5, 100 (1940).
D. H. Snow, and R. I: Swiger, J. Am. Chem. SOC. 90, 6221 (1968). [38] E. E. Dun Tamelen and G. Van Z y l , J. Am. Chem. SOC.7f, 835 (1949).
[I91 R . 7: Swiger, Ph. D. Thesis, Purdue University, June 1970. [39] N . Kornblum, S . D. Boyd, H . H! Pinnick, and R. G. Smith, J. Am.
[20] J. W: Manthey, Ph. D. Thesis, Purdue University, August 1969. Chem. SOC.93,4316 (1971).
[21] Leung Cheng, unpublished work. [40] N . Kornblum, S. D. Boyd, and N . Ono, J. Am. Chem. Soc. 96, 2580
[22] , D. Boyd, and N. Ono, J. Am. Chem. SOC.96, 2580
N . K o r ~ l u m S. (1 974).
(1974), and references cited therein. (411 J. J . Zeilstra and J. B. F. N . Engberts, Rec. Trav. Chim. Pays-Bas.
[23] H. W Pinnick, Ph. D. Thesis, Purdue University. January 1972. 92, 954 (1973).
[24] The stable free radical galvinoxyl, an efficient scavenger of free radicals [42] J. K . Dory, H. Feuer, and N . Kornblum, unpublished work.
[ 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 1.131 N . K o r ~ b ~ S.
~ mC., Carlson, and R. G. Smith, unpublished work.
occurs in 30min; without galvinoxyl the reaction goes 57 % to comple- [@] J . K . Kim and J. F. Bunnett, J. Am. Chem. SOC. 92, 7643 (1970);
tion in this time (Dr. M . M . Kestner, unpublished). J. F. Bunnert and B. F . Gloor, J. Org. Chem. 39, 382 (1974); J. F.
[25] P. A. Wade, Ph. D. Thesis, Purdue University, May 1973. We are Bunnett, J. Chem. Educ. 51, 312 (1974).
indebted to Professor H. A. Morrison for valuable assistance in this [45] J. F. Wo,fe, J . C. Greene, and 7: Hudlicky, J. Org. Chem. 37, 3199
photochemical work. (1972); J. r! Hay, 7: Hudlicky, and J . F. Woye, J. Am. Chem. SOC.
[26] N . Kornbfum, R. 7: Swiger, G. W Earl, H . W Pinnick, and F . W 97, 374 (1975).
Stuchai, J. Am. Chem. SOC.92, 5513 (1970). 2461 J . A. Zoltewiez and 7: M . Oestrrich, J. Am. Chem. SOC.95, 6863 (1973).

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 One group of possible reaction products includes the so-


called “ozonides”, which were shown more than three decades
The oxidative cleavage of unsaturated compounds with ago by RiecherZJto have the structure of the 1,2,4-trioxolanes
ozone in solution, which was first studied in detail by Harries“] (I). These are cyclic peroxides, a large number of which
at the turn of the century, is, in many respects an unusual are known today as distillable liquids or crystalline com-
type of reaction. With very few exceptions, a double bond pounds. The “exotic” nature of ozone cleavage or “ozonolysis”
is cleaved quantitatively under extremely mild conditions- is at once apparent when one considers the formation of
usually at or below -78°C in dilute solution in the absence these ozonides. Not only is the double bond of the alkene
of acids or bases. The products of this cleavage are aldehydes cleaved but also the ozone molecule itself, the two resulting
and/or ketones or their peroxidic derivatives, or-in the case fragments of which form an ether bridge and a peroxide
of aldehydes-their oxidation products, the carboxylic acids. bridge, respectively, between the two C atoms of the alkene.
The product pattern obtained in individual cases depends
not only on the constitution of the starting compounds but 0-0
R-CH=CW-R + 0, 4 RH<~)RH
also on the reaction conditions, especially the solvent used
and the method of workup, which can be carried out purely (1)
hydrolyti~lIy,reductively, or oxidatively.
Few other reactions have so compellingly warranted atten-
tion as regards the mechanism involved. We have been study-
[*] Prof. Dr. R. Criegee
Institut fur Organische Chemie der Universitat ing this question since 1949. Essential contributions have been
75 Karlsruhe, Ric~ard-Willstatter-Allee(Germany) made by other groups, too I3l.

Anyew. Chem. inrernal. Edit. / Val. 14 (1975) 1 No. 11 745


2. Three-Step Mechanism of Ozonolysis Of these, only the dioxetane derivative (7) and the 1,2,3-
trioxolane (8) are likely to favor formation of a 1,Zdiol
It is clear from the start that ozonolysis cannot proceed on reduction. Formula (7), which was first proposed almost
a s a one-step reaction. As we currently believe (and as we half a century ago by Stuuciingerr.61 for the then hypothetical
had already suggested in a lecture delivered at the IUPAC primary ozonides, was recently favored by S t ~ r y ~ How- '~.
Congress in New York in 1951),to our knowledge the reaction ever, according to Baiky[81the NMR spectrum of the primary
proceeds in three discrete steps, all of which, according to ozonideof (2)151ind~cates equivalence ofthe chemical environs
Huisgrn's terminology['], are 1,3-dipolar reactions ([2+ 31 at both C atoms, which would not be so in the case of
additions or reversions). Let us first of all look at these postu- (7). Story's apparent evidence for ( 7 ) . namely the reduction
lated steps and then, in the following and later Sections, ofa primary ozonide with pinacoline to give a 1,2-dioxetane'"],
we shall deal with illustrative examples and confirmatory was later recognized as being experimentally erroneous[Lo!
evidence of their participation in ozonolysis. Other instances of the detection of primary ozonides have
Reuction A : Formation of a "primary ozonide" 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
Reaction B: Decomposition of the primary ozonide into of formula ( 4 ) . Bailey was able to detect such complexes
carbonyl compound + "carbonyl oxide" 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,
Reuction C: Addition of the "carbonyl oxide" to the carbonyl however, whether they play any further part in the process
compound 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
3. Primary Ozonides oxygen molecule and thus give the epoxides. The addition
of ozone, which, in accordance with the principle resonance
Addition compounds of ozone and olefin have already been formulas
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
is a typical dipole" 5 ] , proceeds stereospecifically, as is evident
at - 78°C crystals are formed which decompose exothermally
from the configuration of the diols formed on reduction.
on warming to about -40°C and do not reappear on subse-
Since resonance stabilization of the ozone molecule is miss-
quent cooling. The constitution with still intact C-C single
ing in the primary ozonides (8) they are not only thermally
bond could be confirmed by low-temperature reduction with
much more labile but are also stronger oxidizing agents than
isopropylmagnesium chloride: the racemic diol (3) was
ozone towards some substrates. For example, tetracyanoethyl-
formed.
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
There are five conceivable ways in which we can formulate o"0 + ,c=c,
an olefin-ozone adduct, namely those depicted in (4)-(8). % 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
(4) (5) (6) (7) (8 1 is helpful for recognizing primary ozonides and estimating
rr-complex a-complex peroxy- oxy-1,Z- 1,2,3-tri- their stability, and on the other hand one can obtain
epoxide dioxetane oxolane carbonyl compounds as products by this "reductive ozoniza-

746
tion” even in cases where otherwise rearrangements to anoma- 4.3. Rearrangements
lous ozonization products occur (see Section 4.3).
There are a series of cases in which ozonization leads not
4. Carbonyl Oxides only to oxidative rupture of the double bond but also of
an adjacent C--C single bond. This “anomalous ozoniza-
Primary ozonides are stable at or above -78°C only in tion”[221can be explained in terms of a peroxide rearrangement
exceptional cases. In order to explain the diversity of decom- of the carbonyl oxide. Whether this proceeds via a dioxirane
position products it was assumed at a very early stage[’” (13) as intermediatei231is undecided. The products in these
that decomposition into a carbonyl compound (aldehyde or cases are esters, lactones, or (in the case of a,P-unsaturated
ketone) and a carbonyl oxide (aldehyde oxide or ketone oxide) ketones) also acid anhydrides.
(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 u -Hydroxyacetone is sometimes observed as by-product
of the carbonyl oxides are analogous to those of the amine in the ozonolysis of olefins bearing an isopropylidene group.
%=OF rH .\@,c-o\oQ This can also be explained in terms of an-albeit different
type-rearrangement of a carbonyl oxide, here of acetone
OQ
“I oxide.The two-step rearrangement ought to involve formation
of a very unstable vinyl hydroperoxide (14) as interme-
oxides, nitrile oxides or sulfoxides, but only the nitrile oxides diate124. 251.
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.
4.4, Reaction with Aldehydes or Ketones
4.1. Dimerization
The most important and most frequent reaction of the
Primarily with olefins bearing four substituents at the double
carbonyl oxides is their combination with an aldehyde or
bond, but also in other cases, one obtains as ozonization
a ketone to give an “ozonide”. This could be a monomeric
products the “dimeric keto- (or aldehyde-) peroxides” ( I 1 j ozonide having the l,2,4-trioxoIane structure, formed accord-
They are most readily rationalized as
(1,2,4,5-tetrao~anes)~~’~.
ing to Reaction C in Section 2 by cycloaddition, or also
dimers of the carbonyl oxides.
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.
4.2. Reactions with Proton-Active Substances
5. Formation of Monomeric Ozonides
Ozonization of olefins in the presence of alcohols[”* “I,
ammonia[”I, hydrocyanic acid[201,hydrogen peroxidec2‘I, etc. 5.1. Scope of Formation of Monomeric Ozonides
leads to products, which arise formally-and in our opinion
also in reality-by addition of the respective reagent to the Monomeric ozonides are obtained from alkenes only if
carbonyl oxide. A typical’exampleis the ozonization in metha- at least one H atom is present at the double bond[271, whereas
nol as solvent, in which the geminal methoxyhydroperoxides tetraalkyl-substituted ethylenes afford only oligomers, dimeric
( I 2 ) are formed. 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
Ozonolysis in methanol is also of preparative importance, reactions.
since in this case not only is the formation of dimeric peroxides One can, of course, also “force” keto groups to add to
avoided but also that of oligomeric ozonides, which can some- carbonyl oxides. One possible way ofdoing this is by increasing
times considerably interfere with the ozonization in inert sol- the reactivity of a keto group by neighboring substituents.
vents. If the carbonyl oxides were not zwitterions, but singlet Suitable substituents for this purpose are eIectron-with#rawing
diradicals as proposed by G ~ d d u r d [ ~then
~ I , methanol should groups such as halogen atoms or ester groups. Thus mono-
not add as H-OCH3 but as H--CH20H; this however, meric ozonides could be obtained both from 1,4-dibromo-2,3-
has never been observed. dimethyl-2-butene (15) as well as from 2,3-dimethylcrotonate

Angew. Chrm. interim. Edit. / Vr,l. 1 4 ( I Y 7 5 ) / N o . I / 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


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
c: 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
ary ozonide ought to lead to the ketocarbonyl oxide (27)
in equal amounts. As regards cycloaddition the acetyl group
as wcll as the diketone (26). The carbonyl oxide group now
proved to be 1.7 times more reactive than the benzoyl group.
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) 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. A detailed discussion is unnecessary however, since
ozonide ( 3 5 ) . The result was surprising: the cyclobutene deri- another explanation developed by Bui/ey[""~ 471 requires no

vative was formed exclusively, although it should be thermo- fundamentally new mechanism.
dynamically more labile because of greater ring strain. The According to Bailey, carbonyl oxides having two unlike
reaction must therefore be kinetically controlled. substituents (e.g. H and tert-butyl) should be able to exist
in syn;mri isomeric forms, similar to those of oximes. This
5.7. Ozonides from Diazo Compounds hypothesis states that cisltruns isomeric primary ozonides hav-
ing a bulky substituent at each of the two carbon atoms
In all experiments described so far the carbonyl oxide was should afford unequal amounts of syn and anti carbonyl oxide
formed by spontaneous decomposition of a primary ozonide. and, moreover, that these stereoisomeric carbonyl oxides
On photo-oxidation of diphcnyldiazomethane, Murru!.[''I was add in unequal amounts to aldehydes to form ci.s and rrons
able to detect a short-li\ed product which in the presence of ozonide.
benzaldehyde affords the oronide of triphenylethylene. This I1
short-livcd intermediate can only be benzophenone oxide (36). Ii\ /
,c' C\
11 It

J " "
It-Cli 0
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 Prerequisite for this hypothesis is that the primary ozonides
to its representing the sole route from olefins to ozonides. are nonplanar immediately prior to decomposition and that
The principal objections come from the stereoselectivity of the preferred conformations of the five-membered ring depend
ozonization and the incorporation of labeled oxygen into upon the position and size of the substituents. Likewise. the
the trioxolane ring of ozonides. oronides should be formed in preferred nonplanar confor-
mations.
6.1. Stereoselectivity of Ozonolysis
6.2. Incorporation of Labeled Oxygen into the Ozonide Ring
The mechanism developed in Sections 1 to 5 requires, inter
uliu, that the primary ozonide decomposes entirely into two Ozonization ofan olefin in the presence of an [0"]aldehyde
fragments in the second reaction step. A cis olcfin should should afford an ozonide having a labeled oxygen atom. The
then give the same fragments as the isomeric Irut1.s olefin. three-step mechanism would require, in accord with Reac-
These fragments are transformed by cycloaddition into the tion C (Section 2) also in the modified form of Bailey. that
ozonidcs which can likewise exist in cis/rruns isomeric forms. the labcled 0 atom is always incorporated exclusively as
The mechanism developed is incapab!e of predicting whether the ether bridge of the ozonide.
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. In principle, it is possible to deduce the site of the heavy
However, as first established by . S ~ h r ~ d e rand [ ~ ~later
~ , by oxygen atom from the fragments observed in the mass spectra
S ~ o r j and
. M ~ ~ r r u y I " and
~ ' ~ , other workers["'. 3''1, this is not of ozonides. Stor). and were the first to perform
always the case. The geometry of the olefin can indeed exert such studies. They came to the surprising conclusion that
ii considerable influence on the composition of the ozonide a considerable proportion of the label was located in the
mixture, especially when bulky groups such as rrrt-butyl or peroxide bridgeand not in theether bridge.This would indicate
isopropyl are attached to the double bond of the olefin. This that part of the 0--0 bridge is generated from the aldehydic
applies not only to the composition of the "normal" ozonides oxygen atom with formation of a new 0-0 bond. The
but in the same way to that of "crossed ozonides". mechanism due to Story and Murru!. mentioned in Section
In order to interpret these findings, Storj* and Murra!.["' 6.1 would account for these findings.
developed an alternative mechanism of ozonolysis. Although Independent studies performed in recent years, first by Flis-
it explains the stereochemical results. their proposal contains rdrl'"] and later by Kuczkowskil""', have shown that the heavy
ii number of improbable ud hoc. assumptions, c.8. insertion ozonides prepared in the above manner from ethylene, propy-
of an aldehyde group into an 0-0 bond of the primary Icne, 1-butene, 2,5-dimethyI-3-hexene, and stilbene all contain

750
the " 0 label exclusively, or at least to an extent far in excess tive field for further research! I consider this statement to
of 90 x, in the ether bridge. No explanation for the different have lost none of its validity.
results of Story and Murray has yet become available. At any Received: Fcbruary 28. 1975 [ A 76 IE]
rate, there is no definite experimental evidence requiring an German version: Angew. Chem 87. 765 (19751
alternative mechanism.
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).
7. Concluding Remarks 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.
In conclusion, let us recapitulate how the action of ozone Edit. 2. 565 (1963).
R . C r i e g r e and G. Schriilm.. Chem. Ber. 93, 689 (1960).
on olefins leads to complete oxidative cleavage of the double H . Sruudiiiger, Ber. Deut. Chem. Ges. 58, 108X (1925).
bond and furthermore to cleavage of the ozone molecule P. R . Srorj,. J. A. Alfotd. J . R . Biayrrs, and W C. R ~ J J. . Amer.
Chem. Soc. 93. 3042, 3044 ( 197 I ).
into an ether and a peroxide fragment. P. S. Buile!. J. A. 7'hoiiipson, and B. A . Shoiilders, J. Amcr. Chem.
Even the initial step, addition of ozone to the double bond, Soc. 88, 4098 ( 1966).
amounts to an oxidation of the olefin to the oxidation state P. R . Srorr. E. A . W h i r r d , and J . A. A//ord. J. Amer. Chem. Soc.
94, 2143 (1972).
ofa 1,2-diol. At the same time, the -04-0- unit, which K . R Kopeck!,, R . A . L o c k i ~ o o d ,J . E. Filhr, and R. W: Reid. Can.
is still able to perform oxidation, is anchored to the organic J. Chem. 51, 468 (1973): P. S. Builey. T. P. Crrrrrr, C. M . F i s c k r .
molecule. Since the three 0 atoms are bonded relatively loosely and J 4. Thonipson, ihid. 51. 1278 (1973).
F . L. Greeiircood. J. Org. Chem. 30, 3108 (1965): 1.. J Durliani and
to each other in the primary ozonide owing to lack of F . L. G r e e r i ~ o o d ,ihid. 33. 1629 (1968): F . L. Gret~rinoodand L. J.
resonance, one ofthe 0-0 bonds is easily ruptured. However, Diirhuin. ihid. 34, 3363 (1969).
P S. Bnilej.. J. W W(ir.d. 7: P. Curter. Jr.. E. Nieh, C. M . Fischrr,
stable or stabilized molecules (and not energy-rich radicals
and A , - / . Y Khuslioh. J. Amer. Chem. Soc. Y6, 6136 (1974).
or ions) can only arise if the C--C bond is broken simul- P. S . Builn- and 4. G. Lniie. J. Amer Chem. Soc. XY. 4473 (1967).
taneously. As a result of this cleavage, the two C atoms which H . KPIII. Chem. Ber. / O X , 1207 (1975).
Cf. however: P. J. Hor. 7: H . Dirririiny, and CV A . Goddard. Accounts
were originally double bonded attain the oxidation state of Chcm. Res. 6. 368 (1973).
ketones or aldehydes while the ozone molecule is reduced R . Ci-iryrt, and P. Giiiirhrr, Chern. Ber. 96. 1546 (1963).
to a derivative of hydrogen peroxide. The ozonide is finally 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).
decomposed by water. The overall reaction is described by M . J. F r e i w r i . and E . K . Fir/[/.\,J. Org. Chcm. 2Y. 2240 11964).
the equation 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).
.
'C=C< + O3 + H20 + 2 :C=O + HzOz 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).
Of course, many details still remain open. Let us mention R . Criegrr. S . S. Burh. and R. rot1 Borriliuupr, Chem. Ber. 93. 2891
( 1960).
a few.
Example: R. Cri<,gee and G. Lohurrs. Chem. Ber. 86. I (1952).
For instance, what is the structure of the oligomeric ozonides Example: R . Crirgrr and K . N o / / , Liebigs Ann. Chem. 62.5, I (1959).
and how are they formed'! Do they really contain 0 - 0 4 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.
units alongside ether and peroxide groups, as proposed by
87. 3025 (1965).
Greenwood I26! G. Sdiriirlrr. Chem. Ber. 9
With suitably substituted cyclobutenes, endolexu isomeric , 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).
ozonides have been found on numerous occasions15 411. How '3
L. D Louri, R . M: Mrirru!,, and P. R . S r o r j , J . Amer. Chem. Soc.
can their configuration be established and what determines 87, 737 (1965).
their relative proportions? 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.
Will it become possible to at least detect a carbonyl oxide SOC.8H. 3655 (1966).
spectroscopically, or even to isolate one? 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).
The products of ozonolysis are strongly solvent dependent. K . Grieshouni, Chem. Ber. 101. 463 (1968).
Can this dependence be correlated with any solvent parame- R . Criryee and A. B~IICILI,Chem -Ztg. 9H. 161 (1974): R , Crrrgrr. 4.
ters? 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):
What is the course of gas phase ozonolysis of olefins[2-s 2 , 531? R . W Murrrr! and D. P. H i q / q , ibirl. 95, 7886 (1973).
Are primary ozonides again formed initially? If so, do they 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.
also decompose to aldehyde and carbonyl oxide, or is a diradi- Soc. 88. 3 143 (1966).
F. L. Grrriii%oot/and B. J. I I u i k e . Tetrahedron Lett. 1965. 631.
cal >c-06 formed instead? P. R . Story. R . M.: M i r r r u r , and R. D. Yorisst.f\.eh, J. Amer. Chem.
Can the view recently expressed by G o d d ~ r d [that~ ~ ' the Soc. 88. 3 144 ( I 966); R . U: M r i r r q ~ .R . D. Yori.s.sufl~~li.and P R . Storj..
so called cdrbonyl oxides are singlet diradicals also in solution ihid. 89, 4473 (1967).
N . L. Bauld, J. A . Thoirip.soii, C. E. Hiidson. and P. S. Bui/rJ,,J. Amer.
be confirmed or disproved? Solution of this problem will Chem. Soc. 90, I822 ( I 96X).
be of crucial importance for our understanding of the events R . P. Luirrtwr. R. L. Kiic:I\~~cski.and C. U: Grili.5. J. Amer. Chem.
SOC.96, 348 (1974).
occurring during the ozonolysis of olefins. P. R . Sror.!,. C. W. Bishop, J . R . Birryrss. R . M.: .k4urr[i)~. and R . D.
In 1844, that is 131 years ago, and four years after the Yoi~.rsef~~eh. J. Amer. Chem. Soc. Y(J. 1907 (196x1: P. R . Stor,.. C. E.
discovery of ozone by Schiinbein, no less than six pages were 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).
devoted to ozone by Otto in his "Lehrbuch der Chemie"[54]. S. F/i.\:dr. J . CorIes, and J. R r i i ~ r d ,J. Amer. Chem. Soc. 90. 1364
He closed this section with the exclamation: A highly produc- (1968).

Chrnr. irirrrriot Edrr. ! RA. I 4 ( 1 9 7 5 )


41ig~w ' No. / I 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-


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

752