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Oxidation of Cyclopropyl Hydrocarbons with Ozone.

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main product. \r.hich undergoes stereoselective Diels-Alder
addition with 1 ,3-dienesll1. Elucidation of the mechanism of
this reaction required X-ray determination of the configuration
and conformation of ( I ).
Alder reaction of ( I ) and explains the stereoselectivity
found"'.
The spp"-sp2 type bond C-2-N-7 is unusually long at
1.54A. whereas the length of the C=N bond at 1.14x corresponds to expectations.
K L ' C C I \ C Soptcniher
~:
17. 1976 [L' 545h It.]
\cr\!oii: Alige\\. C'heni. SS. SO? 110761
(;eriiiiin
(AS Key\ir! numher:
/ I 1. (,06X(,4>3-7
Since ( I ) is very sensitive to light. it had to be handled
with extensive exclusion of light even during measurement
of the reflection intensities. Blue monoclinic crystals were
obtained from solutions in ri-hexane and petroleum etheri2I.
Space group: P3, 11 w i t h t i = 13.279. h= 15.0X5. c = Il.71.A.
;~=X4.XS0:D,,,=
1 . 2 X ~ . c m'::%=X(:!
inoleculesperasynimetric unit). D, = 1.29 g.cm .', With aid of an automatic single
crystal diffractonieter using Cu-Kr radiation ( N i filter) 4436
independent reflections were recorded in the range 0 I 0 I 70"
( 0 2 0 sciin. 5-point measurement): 1404 reflections were
unobserved ( I 5 2 0,).The structure was solved by direct
methods using the PHASDT
An E Fourier synthesis with the 300 greatest E values reproduced all the atoms
(except H ) to be expected from the constitutional formula.
In the course of least-squares refinement first with isotropic
and then anisotropic temperature parameters it could be
shown by a difference Fourier synthesis. which also revealed
all the H positions. that each molecule shows a second 0
position of the nitroso group ha\ ing different population parameters. The ratio of the population parameters of the two
0 positions was X : 7 for one molecule and 7 : 3 for the other.
Refinement converged at an R value of 5.9
Oxidation of Cyclopropyl Hydrocarbons with Ozone[**]
By I.;/ir./itrrtlr Prolisc/i and Arriiiii t k M r i i c w ~ I
Cyclopropylcarbonyl compounds are important intermediates i n preparative organic chemistry. We have found that
"dry ozonization""' is a method for directed functionalization
of cyclopropyl hydrocarbons in the 2-position to the cyclopropyl group. I t affords convenient entry even to those cyclopropylcarbonyl compounds for which precursors are as yet
unknown o r are only difficultly accessible.
I n the reaction ofcycloalkanes with ozone. which is adsorbed
on silim gel. the tertiary positions are preferably hydrouylatedl I I. Reaction of tricycle[ 3.3.7.O2.']decane (heuahydrobull\ alene) / I). howewr. predominantly affords tricycloA
"$,.
CL l - C Z - N 2
Oll-N2-C2
1012'
1181'
#"
H8
H10
[3.3.2.O2.*]decan-3-one ( 2 i [ 2 1(87",, of the mixture of products) along with smaller amounts of tricyclo[3.3.2.0'.8]decan5-01 ( 3 ) (in 9",, yield). This preference for the secondary
C-H bonds in the -*-position to the cyclopropyl group is
general.
Thus, the ri-alkylcyclopropanes ( 4 ) yield the ri-alkyl cyclopropyl ketones ( 5 ) as main products (see Table 1 ). The bicyclo[ri. 1 .O]alkan-2-ones i 7) are accessible in good yields from
Figure I shows the molecular structure of ( I ). The cyano
group on C-9 and the nitroso group on C-2 are cis configurated.
Steric interaction between these substituents leads to some
deformation of the trtrris-decalin system: the chair shaped
six-membered ring C-I to C-9 is noticeably flattened at C-1
and C-2. as shown by the internal angles of 113.6 and 114.4"
at these atoms. The N O and the G N groups are directed
away from each other, as seen from the nonparallel bonds
C-2-N-2 and C - 9 4 - 1 1 in Figure I .
The nitroso group can adopt two conformations which
interconvert by rotation about C-2-N-2. In the principal
oxygen site (0-I I ) the bonds N=O and C-2-C-3 are almost
eclipsed, and in the secondary oxygen position (0-1
2) this
applies to the bonds N = O and C-2-CI-1. The main conformation found in the crystalline state of the nitroso group
permits a steric description of the transition state of the Diels-
'x
p
76 1
the bicyclo[n. 1 .O]alkanes (6); bicyclo[n.l .O]alkan-3-ones ( 9 )
are formed as byproducts along with traces of the diketones
(10).
Exceptions are the bicyclo[2.1 .O]pentane ( 6 ) , I I = 1, which
yields, ititer a h , cyclopropylacetic acid['], and compound ( 6 e )
(see Table 1). The apparent difference in the reactions of
( 6 d ) and ( 6 e ) is consistent with the observation that energetically different carbenium ions occur as intermediates in the
solvolysis of 3,5-dinitrobenzoates of the cis- and trans-bicyclo[6.1.0]nonan-2-ols~to~.
Obviously, the actual radical attack
of ozone at a C-H bond1"] will be determined by a polar
effect["] favoring attack at such positions at which a partial
(/Oc,),
60582-67-4: ( 1 1 ). 185-65-9: (I?), 2205-98-3: f 13). 60582-68-5; (14).
24518.94-3: ( 1 5 j . 60582-69-6: ( 1 6 ) . 60582-70-9: f 17). 36262-35-8: (/No),
50895-58-4: (lXhJ.50695-42-6: (IYu). 60582-71-0: f 1Yh). 60619-15-0: ozone,
I 0028- 15-6
~
. . ~
~
Z. Cdirri, E. K u i i i ~ ,>!M a x i . . and T: li.
Vcrr!,aii!.. J. Orp. Chem.
411. 2141 (1975).
The structures of the new compounds were determined on the basis
of their mass. IR and 'H-NMR spectra. For all known compounds
these spectra were in accord with published data [3-61 or with those
of authentic samples.
Houben-Weyl: Methoden der Organischen Chemie. 4th edit. Vol. 413.
Thieme. Stuttgart 1971, and literature cited therein.
M . H~iri[i~l\and H. M . E i i d i i i . Justus Liebigs Ann. Chem. hY7. 100
11966).
L. D. H a , u and J . N . P i t r jr.. J. Am. Chem. Soc, XY. 1973 (1967).
A . C. Cope, S . Mooii, and C . H . Prirk, J. Am. Chem. Soc. 84, 4848
1 1962).
K . 5.Wiberq and A. de M ~ , i j ~ rTetrahedron
r,
Lett. IY6Y. 59.
7: h j i , S. N i s h i h . and H . Tsiihoinuro. J. Chem. SOC.Chem. Commun.
/ Y 77.284.
The central C-C bond which is known to be reactive towards electrophiles is apparently attacked in this case. Investigations on the
mechanism of this reaction are currently in progress.
K . 5. Wihenq and 7: Ncrkrihirir. J. Am. Chem. SOC. 93, 51 93 (1971).
F. E . S i o r ~ . D.
. E. EmqcJ, and R. W Miirror. J. Am. Chem. SOC.YN.
I 880 (I976).
Cf. C. RiiiIrordr. Angew. Chem. N2, 845 (1970): Angew. Chem. Int.
Ed. Engl. Y, 830 (1970).
M . Eli<jr//i~iI"/fand W. Lurrke. Angew. Chem. X4, 346 (1972): Angew.
Chem. lnt. Ed. Engl. I / . 310 11972).
Table I . Cornnosition of nroduct mixtiires obtained oil "dry ozonization"
Ref
[31
[41
1011)
0
/Oh)
I
/Or)
2
/Od)
IIJi,)
4
I
[3. 51
[2. 31
13. 61
[7]
[7]
[2. 31
12. 81
Coupling Reactions of Vinylidenedicyclopropanes Doubly Halogenated in Allylic Positions-A Productive
Synthesisof Trispiro[2.0.2.0.2.0]nonane
([3]Rotane)[**l
By Lurz Fifjer[*l
Vinylidenedicyclopropanes ( 1 ) which are doubly halogenated and metalated in the allylic positions were formerly
unknown. They contain a tricyclopropyl synthon and as 1,3difunctional molecules should possess considerable potential
for the formation of cyclic systems. It therefore appeared
particularly rewarding to examine their utility in the synthesis
of the otherwise difficultly accessible [rt]rotanes ( 2 ) , ti= 3,
4. 5 . . .
PI
~~
.
~.
~
.~
[Y],,
PI
[a] As a rule. 200 500 nig of the hydroc;irbon was ozonized. I n an experiment
with 500mg ( h h ) the yield of cliromatographically isolated ( 7 h 1 w s 60".,.
In other isolations using larger quantities the yields arc 20 30",, higher.
positive charge can be stabilized by the cyclopropyl neighboring group. Accordingly. the selectivity of the ketonization
is greater in the case of spiro[2S]octane ( 1 1 ) than in (6):
r-oxidation to the spiro[2.5]octan-4-one (22) and the dione
(13) takes place exclusively. The dispiro[2.2.2.2]decane ( 2 4 )
affords about equal amounts of the monoketone ( 1 5 ) and
the isomeric diketones (16) and (17).
Starting from the r r m s - and cis-tricyclo[5.1 .0.02.4]octanes
( 1 8 ~ and
)
( 1 8 b ) this method affords the first entry to the
tricyclo[5.1 .0.02~4]octan-6-ones( 1 9 a ) and ( 2 9 h ) . which are
of importance as precursors for the t r n t i ~ -31[ ~and the previously
unknown cis-tris-o-homobenzene.
Rcceived: September I . 1976 [Z 549 IE]
German \ ersioii : Anget\. Chem. SX X02 II9761
C'AS Registry numbers:
( I ). 283-4943: ( 2 ) . 1746-95-8: (3).60582-63-0: 1401, I191-96-4:(4b).930-574: ( 5 ~ ) 765-43-5:
.
( 5 h ) . 6705-46-0; ( 6 ~ 1 )285-58-5:
.
f h h ) , 186-08-8: 1 6 ).
~
2x6-43-1: /hi/). 13757-43-2: f h L'), 39 174-79-3: ( 7 r l ) . 41 60-49-0: f 7 h ) . 577 I-584: ( 7 1.~ 16335-43-6: f 7 d ) . 16739-31-0: 1 7 ~ ) 16739-33-2:
.
( N a J . 1755-04-0:
/ N h ). 60582-64- I : f X e ) . 22562-45-4: ( 9 c,). 49565-06-2: f Y d ) . 22562-46-5:
(Ye). 22562-47-6: / / O h ) . 60582-65-2: ( I O c ) , 37621-43-5: / I1Jd). 60582-66-3:
762
(I/,X
=
Halogen, M e t a l
1 2 ~ !.I = 3 , 4 , 5,
We now report the first synthesis of two vinylidenedicyclopropanes (6) and ( 8 ) which are doubly halogenated in their
allylic positions; their intramolecular coupling to give the
dispiroheptanes (7)[11 and (9) provides an entry to the entire
[nlrotane series
We obtained (6)f31and (8)l3]by double ring opening of
dicyclopropyl ketone (3/14] with bromine in chloroform, recyclization of the resulting tileso/( )-I ,3,5,7-tetrabromoheptan4-one (4)r3l with sodium hydroxide in diethylene glycol to
give I , I '-dibromodicyclopropyl ketone (5)l'. 'I, and subsequent methylenation and cyclopropylidenation, respectively,
in the presence of potassium tert-butoxide.
Metalation and intramolecular coupling of ( 6 ) and ( 8 )
to form 7-methylenedispiro[2.0.2. Ilheptane f 7)"Iand 7-cyclopropylidenedispiro[2.0.2.l]heptane ( 9 ) l 3 ] was accomplished
-
[*I
Dr. L. Fitjer
Oreanisch-Cheinisches Jnstitut der Universitiit
Tamnianiistrasse 2. D-3400 Gottingen (Germany)
[**I
This work was supported by the Deutsche Forschungsgemeinschaft.
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