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[18.104.22.168'.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   [2. 31 12. 81 Coupling Reactions of Vinylidenedicyclopropanes Doubly Halogenated in Allylic Positions-A Productive Synthesisof Trispiro[22.214.171.124.2.0]nonane (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[126.96.36.199]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.