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Irradiation of Cis ,Cis-L ,S.Cyclooctadiene in the Presence

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Irradiation of Cis ,Cis-L ,S.Cyclooctadiene in the Presence ) v- {Reprioted froo the Journal ol the Aoericen Cbeoiccl Society,91,20Og (1g0g).1 Copyrigbt 1969 by tbe Aoericra Cbcrnicel Socicty ead reprioted by pernissioo of tbe copyright orocr. Irradiation of cis,cis-l ,S.Cyclooctadiene in the Presenceof copper(I) chloride GeorgeM. Whitesides,Gerald L. Goe,and Arthur C. Cope Irradiationof cls,cis-l,5-Cyclooctadiene in the Presenceof Copper(I)Chloride' George NI. \l'hitesides, Gerald L. Goe,:" and Arthur C. Cope2b Contributiott J'rorn the Departntent oJ'Cltenti.strt', ilIassac'husetts Itrstirure of' Technologl', Canrhridge, Llassacltusetts 02139. Receivetl Septembar t0. 1968 Abstract: Irradiation of an oxygen-frcepent:.tne suspcnsion of di-tt-chloro-bis(crs.crs-1,5-cycloocradiene)dicopper- (l) (4) at 254-msyields, in addition to tricyclo[].1.0.0:'t,loctlnc(t). sigrrificilnrquantitics of insolublecopper(l) comple.resof cis,tratrs-and tratts,trons-1.5-cyclooctldienes.Exumination of the photocfternicalbehavior of these dienes,and of their yieldsrelative to the yield of I during thc irradiation ol {. indicatesthat a rlajor part of the I formed hlts cls,trarrs-1,5-cyclooctadieneas x prccursor. These data furrher suggestthat a significant part of the photoconversionof cis,tratrs-1,5-cyclooctadicneto I may take placc lrcr the intermedilrcy'of tratts,trytrrs-1,5- cyclooctadiene. -rr I ransition metals catalyze the thermal and photo- /r---.' I chemicaldimerization of a widevariety of olefins.3-8 r--x// | One of the most interestingof the metal-catalyzedphoto- /-Jx--' chemicalreactions is the conversionof crs,cls-1,S-cyclo- 2a 2b octadieneto tricyclo[3.3.0.02'6]octane(l) by irradiation in the presenceof copper(l)chloride, or by photosensiti- servea varietyof functions: r'i:., as a photosensitizer,as zationwith mercury(3P,) atoms.s'a Althoughthe basic a "template" controlling the stereochemistryof reaction mechanismof the gas-phase,mercury-photosensitized of coordinatedexcited olefinic ligands,or as a catalysr reactionhas beenestablished,a neither the mechanism(s) facilitatingcarbon-carbon bond formation through mix- of the condensed-phase,copper-catalyzed photochemical ing of appropriatemetal orbitalswith olefinicmolecular reaction nor the nature of any intermediatesin this orbitals.t On the basisof quantumyield measurements. reactionhave yet beenclearly defined. Srinivasanhas su_egested that the primary photochemical The copper ion in the latter reaction might a priori step under the homogeneousreaction conditions of his experimentsinvolves absorption of light by uncomplexed (l) Supportedin part by the U. S. Army ResearchOffice (Durham), Grant ARO(D)-31-12.1-.135,and by the National ScienceFoundation, cis,cis-I,5-cyclooctadiene.He further proposedthat thc Crants GP-6222and CP-7266. copper(l)atom exertedits influencein the reactionin the (2) (a) National ScienceFoundation Predoctoral Fellow, 196l-1966: subsequentstabilization National Institutes of Health Predoctoral Fellow, 1966-1967. (b) of the initially tormed excited DeceasedJune 4, 1966. state of the olefin by formation of a complex of un- (3) R. Srinivasan,J. Arner.Chem. Soc., 86, 33lS (1964). specifiedstructure (representedschematically by 3).l (4) I. Haller and R. Srinivasan,ibid.,88,5084 (1966). (5) F. D. Mango and J. H. Schachtschneider,ibid., 89, 2485(1967). However, the appealinggeometrical relation betweenI (6) J. J. ivlrowcaand T. J. Katz, ibid.,88,4012(1966), and references and the racemic conformation of trans,trans-1,5-cyclo- therein. octadiene(2a), and the complicatedand quite different (7) W. Merk and R. Pettir,ibid.,89,4787,11-BB (1967). (8) D.J. Trecker, R. S. Foote, J. P. Henry, and J. E. McKeon, ibid., mechanismsuggested for the superficiallysimilar copper- 88, 302r 0966). catalyzedphotochemical dimerization of norbornene.s Journal of the American Chemical Society I 9l:10 I Ntay 7, 1969 26()9 actually consists of a mixture of severalspecies. 3fltl * "CuCl" -> probably containsappreciable quantities of both com- plexedand uncomplexedcrs,crs- 1,5-cyclooctadiene ; horr'- /.\ol tf-\/"Cvcl" ever, accurate estimates of the relativequantities of n-'/) -_) t complexedand uncomplexeddiene cannot be obtained from the availabledata. 3 In a typical experiment,a stirred, degassedpentanc suspensionof complex.l was irradiatedfor ca.24 hr at room temperature using low-pressuremercury lanrps, have led us to examine in detail severalaspects of the and the solid material presentat the end of the reacrion photochemistry of crs,crs-1,5-cyclooctadienein the pres- was separatedby filtration. The filtered solution was ence of copper(I) chloride, under reaction conditions shown by glpc to contain cls,crs-1,5-cyclooc'adienetnd somewhat different from those describedby Srinivasan. tricyclooctaneI as major components,and cls,crs-l.-1- ln this paper we report the isolationof significantquan- cyclooctadiene,.l-vinylcyclohexene, and three unidenti- tities of cis,trans-and trans,trans-1,5-cyclooctadiene from fied componentsas minor constituents.t2The solid this reaction, and presentevidence pertinent to an under- materialwas composed of a mixtureof copper(l)chloridc standing of the role of thesecompounds in the conversion and copper(l) olefin complexes. Trearmentof this mix- of crs,cls- 1,5-cyclooctadieneto l.e ture with aqueoussodium cyanide solution liberated the olefinic components. E.xtractionand glpc analysis ot' Results the freed olefins indicated the presenceof both crs.cis- Isolation and Structure Proof of trans.trans-L,S-Cyclo- and cis,trans-I.5-cyclooctadiene,t3as well as a small octadiene. The starringmaterial tbr the majority of our quantityof anothercomponent, to whichwe haveassigned experimentshas been the crystallineand well-charac- the trans.trans-I,5-cyclooctadienestructure 2 on the basis -cyclooctadiene)di- terized di-pr-chloro-bis(crs,crs-1.5 of the chemicaland spectrcscopicevidence which follow's. copper(l)(.1).to Penranerather than diethylether was Compound 2 could be isolatedin pure form by glpc usedas themedium for our irradiations.in orderto avoid under ctrefully controlledconditions. This compt>und the complicatingfree-radical side reactionsencountered proved to be very sensitiveto tracesof oxygenor aciti. and slorvlypolymerized thermally even in the absencct)i' thcseagcnts. It was indc-finirelystable while tiozen rr -g\-..J'', 7ql - 78" under an inert atmosphere,and reasonablystablc I L___r- \.,/ in dilute solutionin degassedaprotic solvents. It polv- merizedexplosively on the additionof solventthat hati 4 not been deoxvgenated. It was characterizedby un odor similar to thoseof cis,trarrs-1,5-cyclooctadieneand trans-cyclooctene. by other worker_sduring the irracjiationof copper(l) I The infrared spectrum of 2 showed bands at l6t5 chloridein ether.r"r'r rhe useo[4 asstarting material - (C-C stretchingvibration) and 985cm L (trans-olelin and pentaneas mediumtbr the irradiationuntbrrunately bending vibrarion). No bands appearedin the 650- tntroducesseveral points of uncertaintyin our experi- 750-cm-t region.ra The observeddouble-bond stretch- ments. In particular,it hasnot beenpossible to measure ing frequency is lower than that of cis,trans-1,5-cvclo- rhesolubility of { in pentane,since a suspensionof 4 in -t octadiene(1630 cnt in their spectrum;peaks of equal this solvent dissociatesin part to tiee crs,cls-1,5-cyclo- intensityat 1622and 1635cm-t in the Raman spec- octadieneand a solid nonstoichiometric1,5-cycloocta- trumr3;, which in turn is lorverthan that of crs,crs-1,5- diene copper(t) complex. Further, we do not know cyclooctadiene(1655 cm-r in the ir spectrum,and l66J exactly what fraction of the total cls,cls-1.5-cycloocta-cm-r in the Ramanspectrumrr). dienepresent in the reactionmixture remainscomplexed The mass spectra of the I,3-, 1,4-, and 1,5-cyclo- with copper(l),either in solutionor as suspendedsolici. octadienesare strikingly similar in theregions corresoond- washing 4 with moderatequantities of pentaneresults in ing to fra*qmentscontaining three, five, six, and seven essentiallyquantitative extraction of cyclooctadienefrom carbon atoms (Figure l). However,while the 1,3-and the complex(see the E.rperimentalSection), and suggests 1,4-cyclooctadienesshow only small peaksin the region that 4 should be appreciably dissociatedunder the of m e 50-55, the base peak of the 1,5-cyclooctadienes conditionsof theseirradiations. Converserythe obser- occurs at mle ,s4 (butadienemolecular ion). The oc- vation (t,ideifia) that ca. 10,)(of the starting crs,cls-1,5- currenceof IVI* a,tmle 108for 2 demonstratesthat this cyclooctadienecan be recovered from the suspended compound has the same molecular formula as cls.cis- pentane-insolublecopper containing solids at the con- and cis,trans-I,5-cyclooctadienes.The observation ot' clusion of a typical irradiation, while ca. 50',,ois foun<tin solution, indicatesthat at least209.i of the crs,crs-diene remainsassociated rvith solid copper(l). Thus,it appears ( l2 ) One of the unidentifiedside products is probably tricl,clo- likely that a suspension 11.3.0.02'r;octane:cl. J. lvleinwaldand B. E. Kaplan, ibid.,89, i6l I of rvhatis nominaily4 in pentane ( I 967). (13) A. C. Cope, C. F. Howell. J. Bowers,R. C. Lord, and G. IL Whitesides. ibid., 89, .1024 ( 1967). This photochemical reacrion (9) Part of this work has been communicated: C. M. Whitesides, providesa pracricalsynthesis for small quantities(50 mg or less)ot' C. L. Goe, and A. C. Cope,ibid.,89,7136 (1967). ci s.t ra ns-1,5-cyclooctadiene. (10) H. L. Haight. J. R. Doyte,N. C. Baenziger,and G. F. Richards, (l"l) Bellamy reports the
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