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ATTEMPTED SYNTHESIS OF BICYCLO[2.2.0]HEXAN-1-OLANDOTHER BICYCLO [2.2.0] HEXANE DERIVATIVESbyRONALD TERRY SLEETERB. A. in Chemistry, Millikin University, 1965A MASTER'S THESISsubmitted in partial fulfillment of therequirements for the degreeMASTER OF SCIENCEDepartmentofChemistryKANSAS STATE UNIVERSITYManhattan, Kansas1968Approvedby:"Major Professor

11TABLE OF CONTENTSivLIST OF TABLESvLIST OF SPECTRA1INTRODUCTION11OBJECTIVES OF THIS INVESTIGATIONDISCUSSION OF EXPERIMENTAL chlorobicyclo [2.2.l] hept-2-enel,4-Dichloro-7,7-dimethoxybicyclo [2.2.l].heptane38381,4-Dichlorobicyclo [2.2. l]heptan-7-one394-Chlorobicyclo [2.2.0] hexane-1-carboxylic Acid40Methyl 4-Chlorobicyclo [2.2.0] hexane-1-carboxylate41Attempted Dechlorination of 4-Chlorobicyclo [2.2. 0]hexane1-carboxylic AcidAttempted Dechlorination of Methyl 4-Chlorobicyclohexane-1-carboxylateThermal Decomposition of Methyl 4-Chlorobicyclohexane-1-carboxylate[2.[2. 2.oj42-432.0] -44454-Chlorobicyclo [2.2.0] hexane-1-methanolDechlorination of 4-Chlorobicyclo [2.2.0] hexane-1-methanol.46Bicyclo [2.2.0]hexane-l-methyl Tosylate48Oxidation of Bicyclo [2.2.0] hexane-1-methanol50A. Jones'B. BasicReagent OxidationPotassium Permanganate OxidationMethyl Bicyclo [2.2.0] hexane-1-carboxylate505051

IllMethyl Cyclohexyl Ketone via the Methyl Sulfinyl Carbanion.Attempted Synthesis of Methyl Bicyclo [2.2.0] hex-l-ylketone via the Methyl Sulfinyl Carbanion.5151Synthesis of Methyl Cyclohexyl Ketone via the Dimethyl54Cadmium ReactionSynthesis of Methyl Bicyclo [2. 2. 0] hex-l-yl Ketone viathe Dimethyl Cadmium Reaciont56Baeyer-Villiger Oxidation of the Ketone Mixture59Synthesis of Tert-Butyl Cyclohexanecarboxylate61Synthesis of Methyl Cyclohexanecarboxylate61cis -Cyclobutane-1 2-dicarboxylic Anhydride62cis -l,2-Bis(hydroxymethyl)cyclobutane62cis -l,2-Bis(bromomethyl)cyclobutane62cis -l,2-Bis(cyanomethyl)cyclobutane62cis -l,2-Cyclobutanediacetic Acid62Dimethyl Cyclobutane- cis -1 2-di-cC-bromoacetate62,,Reaction of Dimethyl Cyclobutane- cis -1 ,2-di-oC-bromoacetatewith Sodium Hydride62ACKNOWLEDGEMENTS64BIBLIOGRAPHY65VITA68

IVLIST OF TABLESTABLE1.Comparison of Reaction Runs of the Attempted Synthesisof Methyl Bicyclo [2.2.0] hexyl-1 Ketone fromMethyl Sulfinyl Carbanion54TABLE2.Comparison of Reaction Runs of the Baeyer-VilligerOxidation of the Ketone Mixture60

LIST OF SPECTRAINFRARED SPECTRA4-Chlorobicyclo [2.2.0] hexane-1-carboxy lie Acid.23.-Methyl 4-Chlorobicyclo [2.2.0] hexane-1-carboxylate23Methyl clo [2.2. 0] hexane-1-methanol25Bicyclo [2.2.0] hexane-1-methanol25Bicyclo [2.2.0] hexane-1-methyl Tosylate25271-Norbornyl TosylateBicyclo [2.2.0] hexane-1-carboxylic Acid.2727Methyl Bicyclo [2.2. 0] hexane-1-carboxylateN.M.R. SPECTRA4-Chlorobicyclo [2.2.0] hexane-1-carboxylic Acid29Methyl 4-Chlorobicyclo [2.2.0] hexane-1-carboxy late29Methyl yclo [2.2.0 hexane-1-methanol31Bicyclo [2.2.0] hexane-1-methanol,.31Bicyclo [2.2.0]hexane-l-methyl Tosylate311-Norbornyl Tosylate33Bicyclo [2.2. 0]hexane-l-carboxylic Acid33Methyl Bicyclo [2.2.0] hexane-1-carboxylate33MASS SPECTRABicyclo [2.2. Ojhexane-1-methanol, (70 ev.)35Bicyclo35[2.2.Ojhexane-1-methanol, (14 ev.)4-Chlorobicyclo [2.2. o]hexane-l-methanol, (70 ev.)374-Chlorobicyclo [2.2.0] hexane-1-methanol,37(14 ev.)

INTRODUCTIONResearch on the chemistry of the bicyclo[2.2.0]hexane system has beenrapidly expanding and a number of reviews either totally or partiallyconcerned with it are now in print on the subject.have reviewed the literature prior to mid-1967.Reineke36and Davis17A large, excellent reviewon the bicyclo[2.2.0]hexa-2,5-diene system (Dewar Benzene) appeared in 1967by Schafer and Hellman.were discussed fromaa41The modes of synthesis and reactions of the systemAnother review, concerned withhistorical viewpoint.complete compilation of all the intramolecular photochemical cycloadditionreactions of nonconjugated dienes through 1964 and most of 1965, was writtenby Dillingand included a number of reactions producing the bicyclo [2.2hexane system.[2.2.0].0]Finally another short review on derivatives of the bicyclo-hexane system by Criegee14appeared in 1965.The present review updates those by Reineke and Davis covering theliterature through February, 1968.Bicyclo[2erroneously reported by Zelinski and Nametkin.2.0] hexane (2),which was firstas the product of the Wurtzreaction between cis -1 ,4-dibromocyclohexane (1) and sodium, was the subjectof a new attempt which was almost identical.Connor and Wilson12attemptedto synthesize 2 using 1,4-dibromocyclobutane with lithium amalgam in ether.The intermediate, 2, was postulated as a route to 1,5-hexadiene (3), which "

.was the only product obtained.However, they did not rule out the possibilitythat 3 might arise by direct fragmentation of 1.7Srinivasan and Carlough produced 1-methylbicyclo[2 .2 .0]hexane (5) asthe minor product in the mercury sensitized dimerization of 2-methyl-l 5-hexa,diene (4)CH3 " CH,1itA structure of the following type( 7)was considered, but was ruled outin the following photosensitized internal addition of myrcene (6) by Liu and29Hammond. rfh67The preparation of bicyclo [2.2.0] hexane-1-methanol (8) and solvolysisof its p-nitrobenzoate (9) was discussed in a very recent paper by Dauben,The same independently discovered mode of prep-Chitwood, and Scherer.aration as was utilized is described in the present work.CH 2 OPNBCH 2 OH OPNB 10Solvolysis of the p-nitrobenzoatean 81% yield and 11 in0.43 x 10sec."a919% 99.511in 60% aqueous acetone yielded 10 inThe first order rate constant wasand was compared to a number of cis-fused bicyclic

neopentyl systems in an excellent discussion.Several attempts were madeby these authors to synthesize the tosylate ester, but were unsuccessful.A photolysis reaction on 2 was reported by Jones.of a pentacyclic compound of structureJL325Small amountswere isolated, the n.m.r.spectrum of which agreed with this structural formulation.»-f-12A series of derivativesreported by Sasse3914 were prepared in aphotolysis reactionin 1965.iyoj.PhRPh-CeC-Ph- -3-Chloro-2-f luorobicycloSchroder and Martini49'[2.—2.0] hexa-2,5-diene ( 15) was prepared byin a Diels-Alder reaction and was the precursortcseveral derivatives,j-Me-CSC-MeV ClCI15" Van Tamelin and Carty[2.2.0J48have studied the chemical behavior of bicyclo-hexa-2,5-diene (16) by allowing it to react with various electro-philic species.They found that the reactions do not involve aromatization,but characteristically provide nonbenzenoid transformation products.

The following reactions illustrate a part of their work. 'L L7/»m-ClC 6 H C0 H43/16 16BrBr.- / Br/Br"BrThe photolysis of 17 with a, R — methyl, and b,R- H, was done byWarrener and Bremnerwere discussed.They.7The products were analyzed and mechanistic pathwaysalso studied the photolysis of a number ofR*aJ- R0%b)R] V\,? r /Ria)40%b)0.1% oo22%—17a)10%RSR8 \uoRcyclohexadiene imidesti(1 8)in an effort to suppress aromatization yetretain the potential functionality of an anhydride group.the corresponding benzene derivative was produced.When R was H,However, when R wascyclohexyl or n-butyl, 19 and 20 were produced. I /o18.33Paquette and Cox,in studing the photochemistry of 2,3-homotropone,rationalized the following interconversion through 22 to explain theformation of one of the products 23.However, when 21 was subjected to

the reaction conditions only a polymeric solid formed.C .*\ & t — nn A small body of work on complexes of the bicyclo[2.2.0]hexa-2 ,5-dienesystem has appeared in the literature since the last review.reported the first preparation of suchDietl and Maitlesits role in the isomerization of the ligand.(hexamethylbicyclo[2.2.0]hexa-2,5 diene),aA paper bycomplex andDewar hexamethylbenzenewhen allowed to react withdichlorobis(benzonitrile)palladium in benzene, gives yellow platelets of thecomplex 24, dichloro(hexamethylbicyclo [2.2.0]hexa-2,5-diene)palladium.-j-(PhCN) 2 PdCl2-f-2PhCNReaction of triphenyl phosphine with 24 will regenerate the Dewar benzene,24-j-Booth, et al.,2Ph 3 P* IJ(PhP) 2 PdCl 2in studying the reaction of 24 with rhodium chloridetrihydrate in aqueous methanol at 60 , found 25 as a novel product.

4 24 -f RhCl '3H 234C125Volger and Hogeveen50reported the study of the thermal isomerizationof -dichlorodi(hexamethyl-Dewar-benzene) dirhodium (26) and compared itto the thermal isomerization of hexamethyl-Dewar-benzene,which they alsoinvestigated.CI Rh"RhCI26Fischer, et al.complex (27),22,reported the synthesis of the following chromiumtet racarbonyl(hexame thy lbicyclo [2.2.0] hexa-2,5-diene)chromium (0), in a 5% yield.More papers have appeared on larger ring systems incorporating thebicyclo [2.2.0] hexane framework.Rosenberg and Eimutisfacile synthesis of octamethyl- syn -tricyclo[4.4 .0.0 2375']reported theocta-3 ,7-diene(28) from anhydrous aluminum chloride and 2-butyne in cyclohexane,which very closely resembles the former work by Sch'afer.J.\CHoC CCHoMCI3 {1A1C1.28

. 15rwho has done much work on the bicyclo [2.2.0J hexane system,1Criegee,reported the synthesis and identification of the following isomers 29, 30,and 31 in the dechlorination with lithium or sodium amalgam of 3 4-dichloro,3,4-dimethylcyclobutene\3130" 29"*""»Eberback and Prinzbach, 21 who have also done much work on the bicyclo[2. 2.0]hexane system, have reported yet another synthesis including threederivatives (32, 33, and 34) in the following photolysis reaction.R\[kwR -R'l'"\' ;ii323334A question of whether or not free benzocyclobutadiene was liberatedfrom (benzocyclobutadiene)irontricarbonyl (35) under oxidative decompositionand the role of the silver ion in such decompositions prompted two papers byPettit.31 32Pettit found that free benzocyclobutadiene was released whenrr- 35 r Fe(CO).Fe(CO).36 37the proper oxidant was chosen and gave 37 when 35 and 36 were combined inthe presence of lead tetraacetate.He also learned that the silver ion inthe silver ion oxidation was implicated to be involved in other than mereoxidation.

The bicyclo[2.2.0]hexane system has also been utilized to explainK. Wei,routes to various al.,52observed long chainconjugated dialdehydes in the photooxidation of pure liquid benzene andproposed the following mechanisms to explain their products.A *.0 o 0o—HC-(CH CH)5-CHCHOCHOCHO.28Krebs and Byrdpostulated bicyclic intermediates to explain thedimerization product 38 fromRaciszewski351,2-dehydrocyclooctatetrene also discussed the theoretical mechanistic pathways andexcited states involved in the 2r irradiation of maleic anhydride in benzeneand included the bicyclo[2.2.0] hexane system in his discussion.A small amount of work including the prismane structure as a proposedintermediate is reported.Seyferth, et al.,observedanovel isomerizationin the Diels-Alder reaction of cG-pyrone and bis(trimethylsilyl)acetyleneyielding the meta isomer 39 ina53% yield instead of the expected orthoisomer, which was found along with the para isomer in onlyThe following mechanism was one of four proposed.atrace amount.

SiMe 36.*SiMeV?3SiMe,- " III9SiMe,SiMe3 SiMe„39Much the same type of intermediate was proposed by Burgstahler,10in the following photochemical !., fA number of cage type derivatives containing the bicyclo[2.2.0j hexanestructure have been synthesized.producedaSmith, Kline, and French Labs.46havenumber of derivatives (40 and 41) where R 1 NH 2 and R 2 COOH or NH 2R,er4041Paquette and Wise.34 synthesized 42 following the method of Pettit.Irradiation of 42 gave 43, which was then compared to other compoundshaving S-C co transannular interactions by studying the dipole moment andultraviolet and infrared spectra. /Fe(00) 34243,

10Octaphenyl cubane (44) was prepared by fhrondsen and Zeiss 49 andanother derivative 45 explaining the n.m.r. spectral data wasproposed. -»»(Ph),44Finally Russell, et al.,45have prepared the semidione 46 and studiedits e.s.r. spectrum.46

11OBJECTIVES OF THIS INVESTIGATIONThe objectives of this investigation were to synthesize bicyclohexan-1-ol and certain of its precursors.[2.2.0]

12DISCUSSION OF EXPERIMENTAL RESULTSSeveral highly successful techniques for generating compounds ofbicyclo [2.2.0]hexane parentage had been developed by the time this workwas undertaken.One of the most intriguing appeared in a paper by Scherer.MeO OMeCI CI V'tY C11Cl'42MeO oMeMeO OMeXI?iCl ? Cl- C1- 47Using hexachlorocyclopentadiene as the readily available starting material,he was able to prepare the 4-chlorobicyclo [2.2.0]hexane-l-carboxylic acid(47) in a high overall yield.Acid 47 was felt to be an elegant precursorto many other derivatives by applying carefully thought out conversions.As Reineke[2.2.0]and Davishad prepared the exo - (48) and endo -bicyclohexan-2-o Is (49), respectively, bicyclofirst derivative desired.[2.2.0]hexan-l-ol (50) was theThe preparation of it would complete the seriesOHOH484950and provide valuable information on the stability and the nature of theproducts of the bridgehead carbonium ion generated through solvolysis ofthe tosylate ester.The solvolysis of the exo -bicyclobeen completed by Reineke,[2.2.0]hexan-2-ol hadand the preparation for the solvolysis of theendo xsomer was already in progress by Davis. 17The following reaction

13sequence was proposed as the most plausible for entry into the bicycloOne of the strongest arguments for the sequence[2.2.o]hexan-l-ol (50)./C0 2 MeCOCH SOMeyCOgMe47Cl5251COMe* L-CJ—532 -Q54OHCMe 55was the fact that it was the same used successfully by Davisinto a mixture of alcohols 48 and 49for entry.Many difficulties were encountered in this synthesis.on the dechlorination of the ester175 1.The first aroseEven though mild conditions were used(i.e., reaction temperature of 73* for one hour, using lithium and tert -butylalcohol), the major product from the reaction was the ester of cyclohexanecarboxylic acid.To complicate things even further the methyl ester haspartly transesterif ied to the tert -butyl ester giving a mixture of the two.In an effort to clear this up,the dechlorination was run under milderconditions (i.e., 35-40 for eight hours) on the acid 47.The acid was notused initially as it was felt that a greater solubility problem would beencountered in the reaction mixture over that of the methyl ester.Afterthe reaction was felt to be complete, the methyl ester of the productswas made using diazomethane in ether.Work-up gave methyl cyclohexane-carboxylate as the major product in a 41.3% yield of the product mixture.Rearranged chloroesters made up 32.3% of the product, while 26.4% wasdechlorinated, but contained double bonds.mixture was done using a6'The g.c. analysis of the productx J", 20% Carbowax column on 60/80 Chromosorb W

141under the same conditions as employed be Davis7for the purification ofhis methyl bicyclo [2.2.o]hexa-2,5-diene-2-carboxylate.It was felt at thetime that the product would be stable under those conditions (detectortemperature 300 100 ,,injection port temperature 305 , column temperatureand helium gas flow rate of 60 ml. /minute).that it was not.Later analysis provedTherefore, the unsaturated, dechlorinated product mayComparison of its n.m.r. spectrum with that ofhave been the desired one.the actual rearranged product was somewhat difficult, because it had beencollected as a mixture of two products with the other product dominatingthe mixture.Since the methyl cyclohexanecarboxylate was the major product,rearrangement during the reaction occurred.Itwas felt that the carboxylgroup might be increasing the lability of the zero bridge to rupture underthe reaction conditions.The following mechanism was postulated.COoMeC0 o MeItC0 2 MeCO?Mewas felt that the lithium had bonded to the organic substratefollowed, then, by anchimerically assisted zero bridge rupture.assistance was provided by the carbonyl group in the 1-position.TheLaterwork showed that whenever a carbonyl group was in the 1-position, be itacid, ester, or ketone, the compound was not likely to be stable to thermalconditions above 100 .Davis17had no trouble with thermal stability whenthe carbonyl group was in the 2-position.Whenever a saturated functionwas in the 1-position, such as in the bicyclo[2.the compound was found to be thermally stable.2.0] hexane-1-methanol (57)

15Since the dechlorination of the chloroacid failedwas proposed to synthesize the alcoholCH2 OHch — -»sClA—P .2*157852new sequenceCH 2 H56 aThis is outlined below.50. 5354 .55 50Initially lithium aluminum hydride was used to reduce the ester, 51;however, a mixture of products was obtained.Scherer43*had suggestedthe use of diborane reduction on the acid after having the same problem.This reduction gave only one product, 6.A mass spectrum was run at bothhigh and low ionization energy (70 and 14 ev.).M/e 93 was the base peakfor the low ionization energy and 95% of the base for the high ionizationenergy.This was easily explained by Iobs of water and chlorine from theparent.The parent was not present under high ionization energy, but didshow up under the low energy.Lithium and tert -butyl alcohol were used in one attempt to dechlorinatethe chloromethanolreactive.GassmanJ5623without success.The lithium seemed to be toofound the same difficulty when he reduced 1,2,3,4-tetrachloro-7 7-dimethoxybicyclo [2.2.1] hept-2-ene to,[2.2.l]hept-2-ene.7,7-dimethoxybicyclo-Using lithium he found partial reduction of the doublebond to the completely saturated compound.Sodium gave him the desiredproduct only with no reduction of the double bond.Many difficulties were encountered by this author using sodium.small reactions using 3 g.On(23 mmoles) or less of the chloromethanol 56,the product was relatively pure, but the yields were low (24%).On large

16reactions using7g.(48 mmoles) or more,the sodium balled togetherreacting slowly, causing the reaction length to run in some cases overaweek.The yields were higher (50%); however, there werenumber of impurities which could be separated by g.c.columns tried,a6'x %",Of the4% Carbowax on 60/80 Chromosorb G column workedbest and gave some separation ofthe major product.largeraonly.aminor shoulder component (12.3%) fromA mass spectrum was run at both high and low ionizationenergy (70 and 14 ev.).The base peak on both was at m/e 83.This wasreadily explainable by loss of the hydroxyl hydrogen and ethylene from theparent compound.aAnother large peak at m/e 85 might be explained byrearrangement of the parent to hexa-2 ,5-diene-2-methanol, followed byloss of two carbons and three hydrogens by breaking the bond betweencarbons four and five.No parent ion, m/e 112, was observed at high energy,but it was present at low ionization energy as expected for alcohols.An attempt was made at this point to prepare the tosylate ester 58followingaA 93% yield was obtained ofprocedure given by Reineke.fairly pure product as indicated from its n.m.r. spectrum.An attempt topurify it on an alumina column of activity three resulted in completeconversion to 1-norbornyl tosylate (59).Dauben, Chitwood, and SchererCH 2OTslOTs J5859independently had attempted to synthesize the same tosylate ester 58 byseveral methods without success.They were able to make the p-nitrobenzoateand study the solvolysis of this ester in 60% aqueous acetone.uted their fast rate constant of 0.43 x 10"sec."They attrib-at 99.5 to relief of

17ring strain in going to 1-norbornyl p-nitrobenzoate.As the synthesis of the bicyclo [2.2.0] hexan-1-ol was still the majorobject, further study on the methanol 8 was tabled.Oxidation ofacid 57 was then tried with Jones' reagent resulting inproduct.a8 to the32% yield ofBetter yields, as high as 63%, were obtained by basic permanganateoxidation usingThe methyl ester 52 wasmethod of Kenyon and Piatt.athen synthesized by reaction with diazomethane and brought the work backto the point where an attempt could be made to make the ketone 54.Reaction of methyl ester 52 with methylsulf inyl carbanion was chosen,as Davishad previously found success with it except for isomerizationproblems.His endo-ketone 62 isomerized under the reaction conditions tothe exo-isomer 63.No such problem was involved in the present work. h"* O0 2 Me60\GOCH 2 SOMe 62 COMeThe n.m.r. spectrum run on the adduct 49 suggested the presence of severalcompounds.The adduct was reduced with aluminum amalgam, and upon work-upthe n.m.r. spectrum showed the possibility of several ketones, none ofwhich appeared to be the desired product, as the bulk of the n.m.r. spectralabsorption was too high, from T7.7to 9.35.G.c. separation and collectionof products only gave ketones with the wrong structure.This method was dropped in favor of the dimethyl cadmium reactionF ClC0 2 H5764- »Me54

18outlined above.Again the n.m.r. spectrum of the product indicatedmixture of several early as in the preparation of the acyl halide.decrease this by altering reaction conditions.conditions was gained.aA noticeable amount of decomposition occurredAttempts were made toAn indication of optimumNothing could be done to improve the yield of theacyl haiide, but a trap-to- trap distillation of it at 35 and 0.10 mm. didimprove the purityTo optimize the yield, the dimethyl cadmium for the next step must bemade underadeoxygenated nitrogen atmosphere to minimize the amount of theunidentified ester formed.An injection of the product mixture from reactionof acid chloride 64 and dimethyl cadmium on the g.c.ment of some of the product mixture.resulted in rearrange-It was felt that the best method ofseparation and identification of the product would be to proceed to theBaeyer-Villiger reaction with the mixture as it was.This, if successful,would give the acetate, which was anticipated to be stable to g.c. conditions.The oxidation was performed and four products were obtained by g.c.collection, two of which were acetates.The n.m.r. spectrum of one of theacetates gave precisely what one would expect for the product, bicyclo[2.2.0]hex-l-yl acetate.The amount of product varied from 59% to 17% ofthe mixture for the two runs made as analyzed by g.c. integration.singlet absorption at T8.06 andaArelatively large multiplet at T7.52-7.64 and a small continuous absorption at T7. 25-8. 98 was found in then.m.r. spectrum.No further work was done.Before the above work was undertaken, an attempt to couple theoG-carbons in dimethyl cyclobutane- cis -1 ,2-di-c&bromoacetate (65) wastried.The precursor was prepared according to the following sequence.

19JC0 2 MeC0 H2C0 d Me/-j-BrC0 2 H-CN " /CH-OHCH 2 CN - " CH OH2CH 2CN CH Br2,CHBrC0 2 MeCH 2 C0 H2(oHO,CH Br22- C0 2 MeC02Me v CHBrC0 2 MeCH 2 C0 2 H65Blanchard and Cairncrossfound the following coupling reaction withsodium hydride to give a 92% yield of bicycloMe[l.1.0]but-l-yl nitrile.Me- I CNNCIt was felt that thereaction outlined below might afford a cheap,relatively high yield method of attaining a bicyclo[2.2.0jhexene derivative.H BrBrC0 2 Me65 VC 2 MeBr \7 CO-MeHC0 2 MeBrC0 2 Me& VnC0 Me2i\C0 2 MeUpon reaction of 65 with sodium hydride in tetrahydrof uran, employing themethod of Blanchard and Cairncross, a tar was recovered which did notchromatograph on an alumina column.The project was subsequently dropped.

20SUMMARYThe synthesis of 4-chlorobicyflo [2.2.0] hexane-1-carboxylic acid(47) has been reported,42and it was felt that 47 should be a practicalprecursor to the desired bicycloconverted to the methyl ester.[2.The acid 47 was2.0] hexan-1-ol (50).Dechlorination of the ester with lithiumand tert-butyl alcohol gave tert -butyl cyclohexanecarboxylate as the majorSixteen other products were obtained and wereproduct.and tert -butyl esters.were dechlorinated,amixture of methylSome were attributed to starting material; othersbut contained double bonds.This was cleared up bydechlorinating the acid 47 and then analyzing the products after conversionto the methyl esters.41.3% yield.Methyl cyclohexanecarboxylate was recovered in aRearranged chloroesters made up 32.3% of the product; while26.4% was dechlorinated, but contained double bonds.The chloro acid47 was then reduced with diborane to give 4-chlorobicyclo[2.2.0jhexane-1-methanol (52), which was then successfully dechlorinated to givebicyclo [2.2.0] hexane-1-methanol (8) in a 50% yield.A successful preparationof the bicyclo [2.2.0] hexane-1-methyl tosylate was carried out and totalrearrangement to 1-norbornyl tosylate was effected in an attempt to purifyit bychromatography on an activity three alumina column.alcohol8with Jones' reagent gave a 32% yield of bicyclo1-carboxylic acid (53).Oxidation of the[2.2.0] hexane-Better yields, as high as 63%, were obtained withbasic permanganate.The corresponding ester, methyl bicyclo [2.2. 0] hexane-1-carboxy late(48), was synthesized and an unsuccessful attempt was made to make theketone, methyl bicyclo [2.2. 0]hexyl ketone (54), in a reaction with methyl-sulfinyl carbanion in tetrahydrof uran.None of the desired ketone was

21obtained.The dimethyl cadmium reaction was then carried out on bicyclo-[2.2.0] hexane-1-carbonyl chloride (60),with thionyl chloride.prepared by reaction of the acid 48A more promising mixture of ketones was obtained.ABaeyer-Villiger reaction was run and the products were isolated by g.c.collection.One is believed to be the desiredTwo acetates were isolated.bicyclo [2.2.0]hex-l-yl acetate produced in a low yield.One of the major accomplishments of this work was the discovery ofanchimerically assisted decomposition of the bridge bond under thermalconditions whenever a carbonyl group was in the 1-position.Decompositionwas followed by n.m.r. analysis of products before and after g.c. collection.The bicyclo [2.2.0] hexane system was found to be fairly stahle whenever asaturated function was in the 1-position.This observation included theacetate, which was found to be stable to the conditions used for g.c.purification.Before the above work was done, research was done on a coupling reactioninvolving sodium hydride and dimethyl cyclobutane-cis-l,2-di-oC -t)romo acetate(65) in an attempt to synthesize 1,2-dicarbomethoxybicyclo [2.2.0] hex-2-ene.The method of Blanchard and Cairncrossintractable tar was the only product.was employed without success.An

INFRARED SPECTRA4-Chlorobicyclo [2.2.0] hexane-1-carboxylic Acid(in Nujol mull)Methyl 4-Chlorobicyclo [2.2.0]hexane-l-carboxylate(neat)Methyl 5-Chlorohexa-l 5-diene-2-carboxy late,(neat)

-;J3II4II5LJ6II7Il l8I9micronsII10IIIIII12'13'14'15

INFRARED SPECTRA4-Chlorobicyclo [2.2.0]hexane-l-methanol(in Nujol mull)Bicyclo [2.2.o] hexane-1-methanol(neat)Bicyclo [2.2.0]hexane-l-methyl Tosylate(neat)


INFRARED SPECTRA1-Norbornyl Tosylate(neat)Bicyclo [2.2.0]hexane-l-carboxylic Acid(neat)Methyl Bicyclo [2.2.o] hexane-1-carboxylate(neat)

27iiiiiiiTiiiiri.i13 i14L15

N.M.R. SPECTRA4-Chlorobicyclo(in[2. 2.0]CC1 CC1dthexane-1-carboxylic Acidwith TMS internal standard)dtMethyl 4-Chlorobicyclo [2.2.0] hexane-1-carboxylate(in CC1. with TMS internal standard)Methyl 5-chlorohexa-l 5-diene-2-carboxy late,(in CC1. with TMS internal standard)


N.M.R. SPECTRA4-Chlorobicyclo(in CC1[2.2.0]hexane-l-methanolwith TMS internal standard)4Bicyclo [2.2.0] hexane-1-methanol(in CC1. with TMS internal standard)Bicyclo [2.2.0] hexane-1-methyl Tosylate(in CC1„ with TMS internal standard)4

21CH.OHdj1- i-.i.i.i.i.i.ii,,,,,,,,,imCH-OT.Jxi.i.- Jii. A

N.M.R. SPECTRA1-Norbornyl Tosylate(in CC1, with TMS internal standard)4Bicyclo [2.2.0] hexane-1-carboxylic Acid(in CC1. with TMS internal standard)Methyl Bicyclo(in CC14[2. 2.0]hexane-1-carboxylatewith TMS internal standard)


MASS SPECTRABicyclo [2.2.0] hexane-1-methanol(70 ev.)Bicyclo [2.2.0J hexane-1-methanol(14 ev.)

55100-100100-83CH o 0Hdj'IIlullI,lllI11[1114]50m/ellpllllt -t100

MASS SPECTRA4-Chlorobicyc lo[2 . 2 . 0]hexane-1-methanol(70 ev.)4-Chlorobicyclo [2.2.o] hexane-1-methanol(14 ev.)

;:100-39CH 2 0HCIiil,S4LJilmT-kLl450100100-m/e100

ntiadiene.The method of McBee, et al.30was used to synthesize the title compound in a 90% yield, b,p. 64 /0. 6 mm.,n26D'3 1.5385.(lit.3 62% yield, b.p. 82 -84 /2 mm.,n 1.5250).Theinfrared and n.m.r. spectral data were consistent with the product expected.The infrared spectrum displayed absorptions at 3.32 (m), 3.42 (m),5.65 (m),6.16 (s), 6.90 (w)10.37 (s),11.94 (s),,8.35 (w)9.05 (w),13.05 (s), and 13.36 (m)w9.25 (w),.,9.55 (w)The n.m.r. spectrumdisplayed a sharp singlet atT6.64.7,7-Dimethoxy-l,2,3,4-tetrachlorobicylo [2.2. lJhept-2-eneof Gassman and Papein a 70.3% yield, b.p.b.p. 72-81 /0.10 mm.).68 /0.15 mm., nD3.46 (s), 3.58 (m),*1.5265 (lit.2378.5% yield,The infrared spectrum exhibited absorptions6.22 (s),6.89 (s), 7.80 (s), 7.91 (s), 8.22 (w)8.48 (w), 9.20 (w), 9.50 (s), 9/90 (s),11.98 (s),The methodThe infrared and n.m.r. spectra were consistentwith the expected used for the preparation of the title compound12.69 (s), and 13.83(m)ju.10.12 (s),10.91 (s), 11.50 (s)The n.m.r. spectrum gave adoublet centering atT6.45(6H) and a symmetric multiplet centering atl-7.95(4H).1,4-Dichloro-7 7-dimethoxybicyc lo [2.2.1] heptane,.The title compoundwas prepared by a modification of the procedure given by Scherer 42To 25 g.(86 mmoles) of 7 ,7-dimethoxy-l 2, 3 ,4-tetrachlorobicyclo-[2.2.1] hept-2-ene,,placed in a 150 ml. capacity Magna Dash autoclavewas added 50 ml. of triethylamine (over threefold excess) twospatula tips full of 5% palladium on carbon, and enough ethanol (90%)

39to bring the volume to 100 ml.Hydrogen was pressured into the auto-clave from 1000 to 2000 lbs./ in.2and heated at 82ofor 24 h

cis-Cyclobutane-1,2-dicarboxylicAnhydride 62 cis-l,2-Bis(hydroxymethyl)cyclobutane 62 cis-l,2-Bis(bromomethyl)cyclobutane 62 cis-l,2-Bis(cyanomethyl)cyclobutane 62 cis-l,2-CyclobutanediaceticAcid 62 DimethylCyclobutane-cis-1,2-di-cC-bromoacetate 62 cetate withSodiumHydride 62

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