1n-v— . n W.” i. 00 A R EAC’ 4 1.2 b n:....\:w.l....n ~....h.w3. 1,. aw n. .w.. (it: . ... .« . ‘4‘... 2.2 . . . . . _ , . . ‘ . . _ . . . A . . _ . r, . . ‘ < . . .V Z A. _ 5 t . . h‘ aegf? 2R3?» 4! VQRDY*V GS? N 2374 B a lat-IN W9.- he ‘KSWHEfi RH mm . ‘ M ‘wefia E6 1 ‘i , K c ' . .._....,..‘ _ 1.58— in.) 1:94”— :. W.a... .gfi?. This is to certify that the thesis entitled The Reaction of Substituted 5-Hydroxy -6-methylbicyclo[4.4.0.01’5]decan-9-ones presented by John David Yordy has been accepted towards fulfillment of the requirements for Ph.D. Janet, Organic Chemistry Major professor Date September 14. 1974 0-7639 . I, r * ’ammm av “DAG & 30'3" 800K BINDERY LIBRARY BINDERS ._ m iiiiiifiil. im 1 llll 5-HYDRO. The bic} lithium-armor; as illustrate hr" . synthetica 1 1y yield. (Cd ABSTRACT THE REACTIONS OF SUBSTITUTED 5-HYDROXY-62METHYLBICYCLO[4.4.0.01t5]DECAN—9-ONES BY John David Yordy The bicyclo[4.4.0.01I5]decan-9-ones were prepared by lithium-ammonia reduction of the corresponding enediones as illustrated in Equation (1). HO (1) 1) Li' NH“ THE, 0 o 2) (NH4)2C03 o Cyclopropanols, such as 2“ rearranged under the appro- priate conditions of acid- or base-catalysis to give the synthetically versatile intermediates Q, g” and Q’in good yield. ago 6 o 3 s (01 .3 '- a " _mwgflljl ‘ s :- I“: “ The forr icinvolve 1‘ propane ring: is then cleaw cyclo[4.4.0.03 hydrindandione dicne system b finch do under configuration sisof a bromo These resj John David Yordy The formation of a hydrindandione from Z'has been shown to involve interaction of the carbonyl group with the cyclo- propane ring, giving an isomeric cyclopropanol (g), which is then cleaved to g” Unexpectedly certain substituted bi- cyclo[4.4.0.01:5]decan-9-ones were found not to yield hydrindandiones. Moreover, only the EEEEET fused hydrindan— dione system has been obtained from those cycloprOpanols which do undergo this type of rearrangement. The trans configuration was unequivocally demonstrated by X-ray analy- sis of a bromo derivative of g; These results are explained by conformational differ- ences in the cycloprOpanol systems which affect the carbonyl- cyclopropyl interactions necessary for rearrangements to the hydrindandione to occur. A remarkable methyl substituent effect during the base- catalyzed rearrangement of 2 produced the twistane aldol Q as the major product (Equation 2). The unusual tricyclic methyl ethers 11 and 12 were formed during the acid treatment of 12 (Equation 3). John David Yordy ' HO . KOH <2) g. m 9. ° * M60 M80 5-HYDROXY in pc THE REACTIONS OF SUBSTITUTED 5-HYDROXY-6-METHYLBICYCID [4 .4 .o .o1 . 5 ] DECAN-9 -ONES BY John David Yordy A DISSERTATION Submitted to Michigan State University in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Department of Chemistry 1974 This work is d Winifred, whos good fit. and M Clar give fam: DEDICATION This work is dedicated to the following: Winifred, my wife, John, Eric, and Michael, our children, whose love and encouragement have made these years good and worthwhile; Mr. and Mrs. John W. Yordy, my parents, and Mr. and Mrs. Clarence Hostetler, my parents-in-law, who have given the rich heritage of close and wonderful families. ii Fl "' ‘\. Ll‘l‘ qm' The auth Reusch for hi the course of to ask probin @iidance has development . APPIeCia stimulating a] friendship anc Finally’l Science Found. MiChigan Stat? ACKNOWLEDGMENTS The author is deeply grateful to Professor William Reusch for his friendship, counsel, and encouragement during the course of this work. He was always willing to listen, to ask probing questions, and to make suggestions. His guidance has contributed immeasurably to my professional development. Appreciation is also extended to my colleagues for stimulating and informative discussions, and for their friendship and humor. Finally, the author would like to thank the National Science Foundation, National Institutes of Health, and Michigan State University for financial support. iii INTRODUCTION RESULTS AND 1 EXPERIMENTAL General l-Methyl Ethyl trans-l, dione 2 trans-1, dione Lithium-l [4.4; TABLE OF CONTENTS Page INTRODUCTION . . . . . . . . . . . . . . . . . . . . . 1 RESULTS AND DISCUSSION . . . . . . . . . . . . . . . . 13 EXPERIMENTAL . . . . . . . . . . . . . . . . . . . . . 50 General . . . . . . . . . . . . . . . . . . . . . 50 1-Methylbicyclo[4.4.0]dec-6-ene-2,8-dione 2- Ethylene Ketal 452) . . . . . . . . . . . . . 51 trans-1,9-Dimethylbicyclo[4.4.0]dec-6-ene-2,8- dione 2-Ethylene Ketal (22) . . . . . . . . . . 51 trans-1,9Dimethylbicyclo[4.4.0]dec-6-ene-2,8- dione (fsvgl) o o o o o o o o o o o o o o o o o o 52 Lithium-Ammonia Reduction of Substituted Bicyclo- [4.4.0]dec-6-ene-2,8-diones 2' 5,11, 5,4", 52’, and 52 53 (a) (13f,5a,6fi)-5-Hydroxy-6-methyltricyclo [4.4.0.01'51decan-9-one (2) . o . . . . . 54 (b) (13f,5a,66,10€)—5-Hydroxy-6,10-dimethyltri- cyclo[4.4.0.01o5]decan-9-one (£2) . . . . 55 (c) (13f,5a,65,8a)-5~Hydroxy-6,8-dimethy1tri- cyclo[4.4.0.01a5]decan-9-one (fig) . . . . 55 (d) (13f,5a,65,7a)-54Hydroxy-6,7-dimethyltri- cyclo[4.4.0.01r5]decan-9-one (52) . . . . 56 (e) (1§_,56.6a,7o)-5-Hydroxy-6,7-dimethyltri- cyclo[4.4.0.01:5]decan-9-one (fig) . . . . 57 8-Ethoxy-trans-1,10-dimethylbicyclo[4.4.0]dec- 5,7-diene-fi-One (58) o o o o o o o o o o o o o 57 Reduction and Hydrolysis of 8-Ethoxy-trans-1,10- dimethylbicyclo[4.4.0]dec-5,7-diene-§-one (52) 58 Lithium-Ammonia Reduction and Oxidation of (5a,65, 7a)-7-Hydroxy-5,6-dimethylbicyclo[4.4.0]dec-l- one (Q1) . .'. . . . . . . . . . . . . . . . . 59 (1a,6a,105)-1,10-Dimethylbicyclo[4.4.0]decan- 2,8-dione(§g)................ 61 iv TABLE OF CONTENTS (Cont.) Page (13,6a,9a)-1,9-Dimethylbicyclo[4.4.0]decan—2,8- dione (110) O O O O O O O O O O O O O O O O 61 Base-Catalyzed Reduction of Substituted Tricyclo- [4.4. 0.01 5]decan-9-ones . . . . . . . . . . 62 (a) trans-1,6-Dimethylbicyclo[4.3.0]nona-2,7— dione (46) . . . . . . . . . . . . . . 62 (b) Base-Catalyzed Reduction of (1R*, 5a,65, 10g )-5- -Hydroxy-6, ,10-dimethyltricyclo- [4.24. 0.0 5]decan-9-one (62) . . . . . 63 (c) Base-Treatment of (1R*,53,6a, 7a)—5-Hydroxy- 6 ,7-dimethyltricycloT4. 4.0.01 5]decan-9- one (63) . . . . . . . . . . . . . . . 64 (d) Base Treatment of (1R*, 5a66,7a)-5-Hydroxy- 6, 7-dimethyltricycloT4.4. 0.01 5]decan-9- one (50) . . . . . . . . . . . . . . . 65 (e) Base Treatment of (1R*, 5a,66,8a)-5-Hydroxy- 6, 8-dimethyltricycloT4. 4. 0.01 5]decan-9- one (£3) 0 O O O O O C O C O O O O O O 65 (1a,3a,66)-3-Bromo-1,6-dimethylbicyclo[4.3.0]nona- 2, 7-dione (Figure 1) . . . . . . . . . . . . 67 (1R*,3R*,6S*,8R*,10R*)-8~Hydroxy-1,10-dimethy1tri- cyclo[4 .4 0. T03. 8]decan-2-one (100) . . . . . 68 Preparation of trans-1,10-Dimethyl-8- (pfbromobenzene— sulfonoxy)-tricyclo[4 4. 0. O3 8]decan-2-one (Figure 2) . . . . . . . . . . . . . . . . . 69 Acid Treatment of Substituted Tricyclo[4.4.0.01o5]- decan-9-ones . . . . . . . . . . . . . . . . 69 (a) Acid Treatment of (1R*, 50,66)-5éHydroxy-6- methyltricyclo[4 .4 O. T0105]decan-9-one (4) 70 (b) Acid Treatment of (1R*, 5a,65,10¥)-5+Hydroxy- 6, 10-dimethyltricyclo[4 4. 0.01 5]decan-9- one (62) . . . . . . . . . . . . . . . 71 (c) Acid Treatment of (1R*, 55,6ai7a)-5+Hydroxy- 6 ,7-dimethyltricycloT4 4. 0. 15]decan-9- one (63) . . . . . . . . . . . . . . . 72 (d) Acid Treatment of (1R* 5a,65,7a)-5-Hydroxy- 6, 7-dimethyltricycloT4. 4. 0.01 5]decan-9- one (50) O O . . O C . C O O C O C O O 73 (e) Acid Treatment of (1R*, 5a6B,8a)-5-Hydroxy- 6, 8-dimethyltricycloT4. 4.0.01 5]decan-9- one (64 ) O O O O C C O O C C O O C O O 73 TABLE OF cor: synthesi Deriv (a) (b) Acid Tre Base Tre Reductio 6-met Preparat Base Tre tricy REFERENCES APPENDIX A: APPENDIX B: 1 TABLE OF CONTENTS (Cont.) Page Synthesis of Substituted SiMethoxy Twistane Derivatives . . . . . . . . . . . . . . . . 74 (a) (1R*, 3R*, 68*, 8R* ,10R*)-8-Methoxy-1, 10-di- methyltricyclo[4. 4. TO. 03 8]decan-2-one (101) O O C O O C O O O I O O O O C O 74 (b) (1R*, 3R*, 68*, 8R* ,9R*)-84Methoxy-1, 9-di- methyltricycloT4 4. TO. 03 8]decan-2-one (122) . . . . . . . . . . . . . . . . 75 Acid Treatment of Cyclopropanol 121 . . . . . . 75 Base Treatment of cyclopropanol 117 . . . . . . 76 Reduction and Cleavage of (18*, 3a,6a)—3—Methoxy 6-methy1tricyclo[4. 4 .0. 01 3]decan-7-one (91) 77 Preparation of Cyclopr0py1 Acetates 76 and 77 . 78 Base Treatment of (18*, 3a,6a)-3~Acetoxy-6-methy1- tricyclo[4. 4 .0. 01T3]decan-7-one (77) . . . . 80 REFERENCES . O O O O O O C O C O O O O O O O O O O O 8 1 APPENDIX A: SPECTRA . . . . . . . . . . . . . . . . 85 APPENDIX B: NOMENCLATURE . . . . . . . . . . . . . 184 vi TABLE II- III. IV. LIST OF TABLES Page The C-10 methyl and vinyl hydrogen shifts for ’6w7 and Q O O O O O O O C C O O O O O O O O O 1 8 The ultra violet spectra and halfawave potentials for bicyclo[4.4.0]dec-6-ene-2,8-diones and their corresponding derivatives . . . . . . . 21 Ratio of cyclopropyl acetates 12.and,11 . . . 27 Products derived from the base and acid cleavage of cyclopropanols 4, g2, and §§f§2,1n meOH O O O O O O O O O O O I O O O O O O O O 3 3 Conformational analysis of analogues of l—methyl- cis—bicyclo[4.4.0]decan-2,8-dione . . . . . . 43 vii T u-l..-.' .4. .L-fiemm‘ ..~.- ‘ Em. "'3 igure 10. 11. 12. 13. Ster of g; Sterc as de Infrz [4.4. (2‘2) Infra [4.4. Infra methy Infra 6,10~ (62) Infra] dimet} Infrar dimeth Infrar dimeth Infrar biCYCl IRfIar methyl Infrar dimeth Infra: imetk LIST OF FIGURES Figure Page 1. Stereodrawings illustrating the bromo-derivative of gg'as determined by X-ray analysis . . . . . 25 2. Stereodrawings illustrating the brosylate of 100 as determined by X-ray analysis . . . . . . . . 39 3. Infrared spectrum of trans-1,9-dimethylbicyclo- [4.4.0]dec-6-ene-2,8-dione 2-ethylene ketal (gov) O O O O O O I O O O O O O O O O O O I O O 85 4. Infrared spectrum of trans-1,9-dimethylbicyclo- [4.4.0]dec-6-ene-2,8-dione (£6) . . . . . . . . 86 5. Infrared spectrum of (1R*,5a,6B)-5-hydroxy-6- methyltricyclo[4.4.O.O175]decan-9-one (4) . . . 87 6. Infrared spectrum of (15f;5a,65,106)-5-hydroxy- 6,10-dimethyltricyclo[4.4.O.01v5]decan-9-one (rig!) o o o o o o o o o o o o O o o o o o o o o 88 7. Infrared spectrum of (1R*,5a,6B,8a)—5-hydroxy-6,8— dimethyltricyclo[4.4.0.51t5]decan-9-one (62) . 89 8. Infrared Spectrum of (13f,5a,65,7a)-5-hydroxy-6,7- dimethyltricyclo[4.4.O.O1v5 decan-9-one (52) . 9O 9. Infrared spectrum of (1R*,55,6a,7a)-5-hydroxy-6,7- dimethyltricyclo[4.4.0.U1'5]decan-9-one (62) . 91 10. Infrared spectrum of (15,6a, 7a)-1,7-dimethyl- bicyclo[4.4.0]decan-2,8-dione (62) . . . . . . 92 11. Infrared spectrum of 8-ethoxy-trans-1,10-di methylbicyclo[4.4.0]dec-5,7—dione-2-one (58) . 93 12. Infrared spectrum of (5a,65,7a)-7-hydroxy-5,6- dimethylbicyclo[4.4.0]dec-1-ene-3-one (67) . . 94 13. Infrared Spectrum of (55,6a,7a)-7-hydroxy-5,6- dimethylbicyclo[4.4.0]dec-1-ene-3-one (68) . . 95 viii figure 14. Inf bic 15. Isf- bic: 16. Inf: bio} 17. Infr [4.3 18. Infr cycL 19. Infra [4.3. 20. Infra hydro 2-one 21- Infra: bicyc; 22- Infra: Cyclo[ 23- Infrar methyl] 24° Infrare (2~bron [4.4.03 25° Infrare methylt 26- Infrare NEthylt 27' Infrarg, 1,181? (9,5,) 28' IDfrare mELhOXLF ‘8‘One IJST OF FIGURES (Cont.) Figure Page 14. Infrared spectrum of (18,6a,10a)-1,10-dimethy1- bicyclo[4.4.0]decan-2,8-dione (66) . . . . . . 96 15. Infrared spectrum of (1a,6a,10§)-1,10-dimethyl- bicyclo[4.4.0]decan-2,8—dione (6g) . . . . . . 97 16. Infrared spectrum of (18,6a,9a)-1,9-dimethyl- bicyclo[4.4.0]decan-2,8-dione (110) . . . . . . 98 17. Infrared spectrum of trans-1, 6-dimethylbicyclo- [4.3. 0]nona-2, 7-dione (46) . . . . . . . . . . 99 18. Infrared spectrum of (1a,6a,7 )-1,7-dimethylbi- cyclo[4.4.0]decan-2,8-dione (62 and 66) . . . . 100 19. Infrared spectrum of (1a,6fi,9a)-trimethylbicyclo- [4 .3001n0na-2,7-dione (97) o o o o o o o o o o 101 20. Infrared Spectrum of (1R*, 3R*, 68*, 8R*, 10R*)-8- hydroxy-l, 10-dimethyltricyclo[4. 4. 0. T03 8Tdecan- 2-one (100) C O C C C O C C C . C O O . C . . C 102 21. Infrared spectrum of (1a,68,8€)-1,6,8-trimethyl- bicyclo[4.3 .0]nona-2, 7-dione (102) . . . . . . 103 22. Infrared spectrum of (1a,6a,9 )-1,9-dimethylbi- cyclo[4.4.0]decan-2,8-dione ( 03—104) . . . . . 104 23. Infrared spectrum of (1a,3a,65)-3-bromo-1,6—di- methylbicyclo[4.3.0]nona-2,7-dione (Figure 1) . 105 24. Infrared Spectrum of (1R*,3R*,6S*,8R*,10R*)-8- (Efbromobenzenesulfonoxy)-1, T10-dimethyltricyclo- .4 03 8]decan—2-one (Figure 2) . . . . . . . 106 25. Infrared spectrum of (18*, 3a,6a)-3-methoxy-6- methyltricyclo[4. 4. 0. 01T 3]decan-7-one (91) . . 107 26. Infrared spectrum of (1R*, 5a,66)-5-methoxy-6- methyltricyclo[4. 4. 0. 01T5]decan-9-one (90) . . 108 27. Infrared Spectrum of (1R*, 28*, 6R* ,7R*)-2-methoxy- 1 ,7—dimethyltricyclo[4. 4 JO 7Tdecan-8-one (96) . . . . . . . . . . . . . . . . . . . . . 109 28. Infrared spectrum of (1R*, 28*, 4S*, 68*, 7R*)-2- methoxy-L 7—dimethyltricyclo[4. 4'.0 0.53:9Tdecan -8 "One (g) o o o o o o o o o o o o o o O o o o 1 1 0 ix LIST OF FIGURES (Cont.) Figure 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39. 40. 41. 42. Page Infrared spectrum of (18*, 3a,5a,6a)-3- -Methoxy- 5 ,6-dimethy1tricyclo[4. 4'.0. 0103]decan-7-one (99) 111 Infrared spectrum of (IR ,55,6a,7a)-59Methoxy- 6, 7-dimethyltricyclo[4. 4. 001 5]decan-9-one (98) 112 Infrared spectrum of (1R*,3R*,68*,8R*,10R*)-8- Methoxy-l, 10-dimethy1tricyclo[4. 4. 0. _0303]decan- Z‘One (101) o o o a o o o o o o o o o o o o o o 113 Infrared Spectrum of (18*, 3a,45,6a)-3A< 4 dioxane.H20 £5; 12 D OH _ O ‘\ C 5 /' OD 6 ( ) , \ dioxane .D20 + ,’ $1 \ q, H 5 molecule being studied. Base catalyzed cleavage of 2-phenyl- 1-methylcyclopropanol g'in heavy water proceeded with in- version Of configuration at the benzylic carbon (Equation 6).8 On the other hand, Wharton and Bair13 noted that both 2§27 and gnggf7-hydroxy-1,6-dimethylbicyclo[4.4.0]heptane 18' Opened with retention of configuration on treatment with potassium Efbutoxide in Efbutyl alcohol. However, the same system reacted with inversion of configuration, when an ethylene glycol solvent system was used (Equation 7). (CH3)3COH (CH3)COK 19 HO(CH2)20H NaO(CH2)20H \ ‘ CHO \‘CH3 20 These results are consistent with the Observations and inter- pretations reported by Cram and coworkers14 for electrophilic substitutions involving carbanion intermediates. Recent studies by Wharton and Fritzberg15 Of the ring Opening reactions of hemiketals derived from trans-2,3-dijg- butylcyCIOpropanone have disclosed that predominate retention Of configuration occurred in both methanol-O-d and ethylene glycol-O-dz (Equation 8). .- ._ . " ' "3'- 1”! 11 I hv—‘<~_ J" \ / (8 Grams prir latter Syst Of the Subs Stable anio occur. Anothe~ valved ring H ROD H OD -—i> >\ R 21 22 8 ( ) RONa Cram's principles would have predicted inversion for the latter system. However, it is possible that the geometry Of the substrate favors formation Of the conformationally stable anion 22 which is protonated before inversion can occur . 02R Another exceptional result, reported by Nickon,16 in- volved ring Opening of the nortricyclic system gg'with exclusive 1 {Equation 9 by Cram's r {9; H I could be ra favoring fl Cram17 as a means r. observed Wi‘ I‘ 10 7 exclusive inversion of configuration in Efbutanol solution (Equation 9), whereas retention would have been predicted by Cram's rules. Vflarton13 has suggested that this event (CH3)3COH k KOC (CH3 )3 25 26 could be rationalized by a general and pervasive effect favoring 252 attack in the norbornyl system. Cram17 has recently suggested a "rotation mechanism" as a means Of accounting for the inversion of configuration observed with cyclopropanols such as EEEQEfZ-phenyl-l-methyl cyclOprOpanOl (Equation 10). - \ b- I g..DOR o--D--OR 27 3E, (10) CD 6- ‘—’ W > D H 29 3O 8 During the past few years, cyc10propanols have been extensively used as synthetic intermediates. For example, compounds 31 and 34 undergo ring expansion to cyclobutanones on treatment with a variety of reagents (Equations 11 and 12).18 R H R + R H ___ x+ H—O x o x (11) R“_————‘> H R ---4> R 11, 1%. £22. a. X = R = H . X = H; R = H or CH3 c. X = OH; R = H or CH3 d. x = CH2N(CH2Ph)2; R = H Ho // (CH3)3COC1 (12) ~i> I'll 0 c1 3 ~53- 22. H A related expansion of carbinol amines or azides provides a new route to B-lactams (Equation 13).18 HO N3 H KH PO Q[::// 2 4 N 1 41> ( 3) NaOH 36 37 Cyc10propanol derivatives have also been used in the stereOSpecific introduction Of quarternary methyl groups, as illustrated by the syntheses of l-valverone (Equation 14)19 and trangfl,6-dimethylbicyclo[4.4.0]decalone (Equation 15).20 MeOH (14) HCl 5 1/ o f 33. 33 OH I OH I : ' s-Sm'th (15) Simon 1 Reagent ‘ l H3CO ‘ OCH3 MeOH 40 OH HCl 41 10 The cyclopropanol derivative 42 was effectively used by Corey and coworkersz1 in the preparation of the key intermediate 44 in the syntheses of prostaglandines E2 and - 1 an (Equat1on 16).2 H3CO H H3C0 H OH 1 ..._.. o d” CHO l a Cl I O5 i ’5 C O 43 44 45 CycloprOpanOl 4’ which is easily prepared by lithium- ammonia reduction of the Wieland Miescher ketone 3’ has been shown to be a versatile precursor Of many synthetically useful ring systems (Scheme 1).5'8'7 In particular, the formation of the perhydroindanedione 46 suggested an attractive approach, via 52 and 51, to the unique sesquiterpene perguisonegg’.21a 11 O O I 48 (80%) n 0 "W 46 (75%) HCl KOH Glyme MeOH. H20 HO 2, (88%) 1) TsCl 1) NaH, ¢H 2) HOAc, NaOAc 2) MeOH Li, NH3 0 lll’> lllllflllllL>o o g' 0 22, (64%) O 7 (75%) w Scheme 1 12 However, cycloprOpanOl §Qlfailed to give 51 under conditions which produced 46 from cyclopropanol 45; This unexpected result led to an extensive study of the factors controlling the ring Opening of substituted 5-hydroxytricyclo[4.4.O.O1I5]- decan-9—ones. The cyclopropanols used in this study were prepared by the lithium-ammonia reduction Of enediones g'and égfgg: (17) g'... R1 gg'... R1 E2.--° R2 gs ... R1 §§.°'- R1 Except for 52, RESULTS AND DISCUSSION = R2 = R3 = = R2 = R3 = = R3 = R4 = = R3 = R4 = = R2 = R4 = the syntheses Of these bicyclo[4.4.0]dec- (NH4)2C03 R4 = ........ H: R4 = CH: ... H; R1 = OH3 ... H; R2 = CHa ... H: R3 = CH3 ... é. g3 g2, §2. g2, 6-ene-2,8-diones are well documented.22'3'~"'1H enediones 54 and 55’ prepared in equal amounts by the an- nulation Of 2-methylcyclohexan-1,3-dione in the form of its monOpyrrOlidine enamine with 3-penten-2-one in form- amide,24b could not be separated satisfactorily. study or models we noted that reactions which changed 13 However, 14 either or both trigonal carbonyl centers to a tetrahedral configuration would introduce 1,3-diaxial interactions with the C-10 methyl Of 55, but not with 22; Such interactions would be expected to result in a rate retardation, thus per- mitting the selective derivatization of 52 in the presence of 52; The validity of this reasoning has been demonstrated by the selective formation of the dienol ether 21 from a mixture of gé'and 52; However, the conditions of this reac- tion proved extremely crucial and difficult to reproduce. oEt oEt 57 58 Thus failure to quench the reaction with triethyl amine at the optimum moment led to substantial amounts of 52; Hydrol- ysis of 51’ after separation from starting materials, gave pure 5,4,. The preparation of Qg'was accomplished as shown in Scheme 11. Ketal 52 was prepared in 86% yield by a modifica- tion of the transfer ketalization procedure reported by Bauduin and Pietrasanta.25 Formation of the kinetically favored conjugate base of gg'by the action of lithium di- isopropyl amide in tetrahydrofuran, followed by addition Of methyl iodide, led to q'—methyl epimersz.6 Equilibration 15 3L1N.6L)z MeI a» 3) KOH, MeOH 3 29, (86%) Ag Acetone “: 56 (66% from 59) Scheme II to the more stable isomer 62 was achieved by treatment with methanolic potassium hydroXide. This dimethyl ketal proved to be a crystalline solid (mp 109-110°) exhibiting a three proton singlet at 61.40, a three proton doublet at 61.12 (J = 6.0 Hz), and a one proton singlet at 65.83 in the pmr. Deketalization of 62 with aqueous hydrochloric acid in acetone gave a white solid (fig) having methyl and vinyl hydrogen signals in its pmr spectrum consistent with the proposed structure. The overall yield of 56 from 59 was 66%. Reductive cyclization Of the bicyclo[4.4.0]dec-6-ene- 2,8-diones to cycloprOpanols 4, 52, and 62764 was carried out in liquid ammonia solution at -78°, uSing equivalent amounts Of lithium metal. If no interaction between 16 non-adjacent functional groups had occurred, then the major products should have been the Egagsfdecalindiones, formed by reduction of the enone systems. While Eranggdecalin- diones have not been detected among the products from 3, 54, and 56, they are formed in the reduction Of 53 and 52; In the case of 53, the trans—decalindione 62 was detected in R2 = H! R4 CH3 $83 $3 .2” = H, R2 = CH3 the mother liquor remaining after crystallization of the cyclopropanol 62; The trgggffusion of the decalin rings in Qg'was suggeSted by the difference in the pmr line width at half-height of the angular methyl group and the TMS signal (Awh/2 = .61 cps),27 and a comparison of its melting point (73-750) with that given in the literature.28 The only crystalline material Obtained in early ap- plications of the dissolving metal reduction of 55 was a compound (mp 83-840), displaying unconjugated carbonyl absorptions in the infrared. This product had different spectral properties from those Of the isomeric gigfdecalin- dione 62 and was identified as the trans- isomer 66 by an independent synthesis, as illustrated in Scheme III. 55 17 (EtO)3CH 1) LiAlH4 2) H30+ ' ' HO . I 0 . + O o 67 (58%) 68 1) Li,NH3 2) Cr03 O 3 O : O. + O. I 0 O H 2s :52, 5 : 3 Scheme III 18 Eventually cyclopropanol 52 and the trans-decalindione 66 co-crystallized from the reduction of 52; The dienol ether gg'was Obtained (75%) as a crystalline solid by the reaction of Qé'with triethyl orthoformate.29 Lithium aluminum hydride reduction of 52” followed by acid hydrolysis, gave epimeric alcohols from‘which the axial alcohol Qz'crystallized in 58% yield. The equatorial alco- hol was Obtained from the mother liquor by preparative glpc. The stereochemical assignment of the hydroxyl group in these epimers was made by comparing the C-5) methyl and vinyl hydrogen chemical shifts in the pmr for each compound (Table I). Table I. The C-ES methyl and vinyl hydrogen shifts for 9,2. and s:- C-10 Vinyl Stereochemical Compound Methyl Hydrogen Assignment of TMS bTMS Hydroxyl Group 62' 1.16 6.06 axial 68' 1.05 5.83 equatorial The downfield shift of these protons in compound 21,15 con— Sistent with the axial hydroxyl assignment.30 Lithium-ammonia reduction of gz'followed by oxidation with Collins reagent31 gave isomeric decalindiones in a 38:62 ratio. The minor product, identical with the single 19 product Obtained from catalytic hydrogenation of 52” was the gi§_isomer 62; The major product was the trans isomer 66. This is one of a few cases in which a substantial amount of a gigfdecalin is formed during dissolving metal reductions of enones. Such systems usually give the trans configurations with high stereoselectivity.32'33 A similar result was expected for 67’since the structurally similar enone 22 (Equation 18) gaVe a trans/cis product ratio Of 7:124b and no cis-decalindione was detected in the reduction (18) L1, NH3 70 Zl'(trans, 71%) 2E (cis, 10%) of 52; However, enone 61 differs from 24 and 22,by virtue of the axial hydroxyl grOup at C-2. Stork34 has suggested that overlap of the orbital on the S-carbon with the p-orbitals of the enolate anion must be maintained during reduction. A comparison of the t£2§§_ and gig stereoelectronically allowed transition states 733’ and 232 derived from 61 indicates that the C-2 hydroxyl and C-10 methyl interactions in 132 are relieved in 132, Con- sequently the energies Of the transition states are more 20 73a 73b nearly equivalent and the trans/cis ratio much nearer unity than might otherwise be expected. Reduction of 68, the epimer having an equatorial hydroxyl at C—2, would be ex- pected to give a much larger trans/cis product ratio. Less circuitous routes to the t£22§_fused 62, involving the protection of the unconjugated carbonyl followed by dissolving metal reduction of the enone system and removal of the blocking group, proved unsuccessful or gave poor yields. The formation Of cyOIOprOpanols in these reductions indicates an interaction between the carbonyl and enone sys- tem at some stage in the course of the reaction. The exact nature Of this has not been established. Two mechanisms have been considered: an electrophilic attack by the carbon carbon atom at the S-carbon of the enone radical or dian- ion,35 and initial formation Of a transannular delocalized radical anion. Formation of the Erangfdecalindiones 65 and Qg'from 53 and 52 suggests that this interaction is sensi- tive to conformational changes induced by alkyl substituents. 21 Table II. The ultra violet spectra and half-wave potentials for bicyclo[4.4.0]dec-6-ene-2,8-diones and their corresponding derivatives. Half4Wave Potential xmax, in Volts Compound nm e Aceto- DMF nitrile O ’3' :1 I : 243.3 12,100 -1.96 -1.93 5’9, 63:! : 242.0 13,130 -2.12 -2.03 O o is, (I I 1 246.9 10,550 -1.95 -1.90 HQ 0 242.2 13,680 -2.13 Undet. (bk) 0 251 251.7 11,900 -2.03 -1 .95 O 22 Table II. Continued. HalféWave Potential k . in Volts Compound 23x 6 Aceto- DMF nitrile g‘fi 74 251.1 14,070 -2.17 -2.11 O 56 ,, 243.3 11,400 -2.00 -1.95 w 0 60 241.2 12,450 -2.15 -2.11 A comparison of the W,W* transitions of the enone sys- tems in bicyclo[4.4.0]dec-6—ene-2,8-diones with the corre- sponding systems lacking the unconjugated carbonyl function indicates that some interaction exists in the unreduced systems (Table II). The unconjugated carbonyl group acts to decrease the energy required for the v,v* transition of the enone systems. A comparison of the halfdwave potentials for the same compounds indicates a similar trend.36 The 23 unconjugated carbonyl group reduces the potential required for reduction. However, neither study permits an unambiguous prediction regarding the relative amounts of transfdecalin- diones and cyclopropanol which may be formed during the lithium-ammonia reduction of the bicyclo[4.4.0]dec-6-ene- 2,8-diones. The course of ring Opening reactions of these cyclo- propanols depends on the particular reacting systems (Scheme I). For example, base-catalyzed ring Opening of 4' with potassium hydroxide in a 1:1 methanol-water solution gives the trans-hydrindandione 42 in up to 75% yield, the Sigfdecalindione 4§'(~20%), and Only a trace of the Spiro diketone 21'(Equation 19). The cis-decalindione 48 and the H0 (19) ‘ KOH e O MeOH, H20 {A 48 («20%) 47 («1%) spiro diketone 41 were identified by comparison of their properties with those recorded for these compounds in the literature.29'37 24 Although both gig and £322§_ring fusions are possible for the perhydroindan system, gg'was assigned the trans configuration on the strength Of its conversion to the known 2-deoxy derivative.6 Confirmation of this configura- tional assignment was deemed essential because of the potential synthetic utility of this compound and because the stereospecificity Of the rearrangement to gg'posed intriguing mechanistic problems. The most unambiguous method of assigning the configura- tion Of’aurcomplex molecule is to effect a structural analysis with three-dimensional X-ray diffraction data. To this end a bromo—derivative was prepared (84%) by the re- action of gg'with 2-pyrroledionehydrotribromide, PHT.33:39 PHT selectiVely brominated the six-membered ring, suggesting that the a-methylene group in the five-membered ring is very hindered (such units can normally be brominated effi- ciently37). An axial configuration for the bromide was suggested by the Observed downfield methyl Shift3° (A .316) in the pmr for the angular methyl adjacent to the six- membered carbonyl. However, the six-membered ring carbonyl stretching frequency shift40 (Av = 20 cm-l) indicated a pseudo equatorial bromine, poSsibly resulting from a dis- tortion of the chair conformation Of this ring. Solution Of the X-ray data“1 provided a stereoscopic view of the molecule (Figure 1), demonstrating that the methyl groups (C-10 and C-11) are ££32§_and lie in a plane with C-8 and C-9. Another interesting structural feature 25 Figure 1. Stereodrawings illustrating the bromo-derivative Of gglas determined by X-ray analysis. [.14l .. ..,|.b.flm-§J— , \ 26 is found in the six-membered ring where C-5 is approximately coplanar with C-4, C-6, and C—8. This distortion of C-5, caused by the steric interaction Of the axial bromine with the methyl at C—9, is not the result Of crystal lattice forces, but is also present in solutions Of this compound as demonstrated by the coupling constants of H-5 with H-6 and H-7 (J5,6 = 4.0, J5’7 = 6.8 H3) in the pmr. These coupling constants are much larger than expected for an equatorial proton in a rigid six-membered ring, suggesting that the dihedral angles between the coupling hydrogens are considerably different from those expected in a chair con- formation. The trgggfhydrindandione gg'is probably formed by ring Opening of the isomeric cyclOprOpanol 75. This intermediate R0 0 0 \x H 0... 15‘ $0... R 7‘20... R=AC .... a has, in fact, been trapped as the acetate zz,along with the isomeric Zfi'by reacting one equivalent Of a dialkyl amide base26 in a solution of glyme or diglyme, hexamethylphos- phoramide, and tetramethylethylenediamine followed by quench- ing with acetic anhydride. The two isomers are readily distinguished by the presence of the cyclopropyl hydrogens 27 in 21, The ratio of ZZ,t° 26 increased with time, as shown in Table III. Table III. Ratio of cyclopropyl acetates 26 and 77. Reaction Time, Hr. Acetate IQ. Acetate 11 3/4 4 1 1 1/2 4 ' 3 The formation Of a hydrindandione isomer from é'appar- ently involves an interaction of the carbonyl group with the cycloprOpane ring, causing a shift of the C-1 —-C-5 bond to the C-5 -C-8 position, giving an isomeric cyclopropanol which is cleaved. The six-membered ring of 4 may assume one of two possible boat conformations relative to the three membered ring. As a result, two kinds of interactions, leading ultimately to isomeric hydrindandiones can be visu- alized (Scheme IV). Since only the trans product gg'has been Observed from these reactions, we may conclude either that the interaction leading to gi§_22'does not occur, or that zg'is somehow lost or destroyed during these Operations. ‘This Observation is consistent with other studies probing the spacial restric- tions on homoconjugative interaction of cyclopropyl and carbonyl chromophores.“2 For example, the uv spectra of exo-tricyclo[3.2.1.03'4]octane-8-One £2»(xmax 293 nm, e22) Scheme IV. is almost identical to that Of 7-norbornone (xmax 290, E14), whereas the absorption of the endo cyclopropyl ketone 81 o o 48 (xmax 276 nm, 644) is much different. 0 it, w Circular dichroism characteristics of some n,w* car- bonyl transitions have been determined for the Optically active 5,7-cyclopropyl ketones Qg'and 82, The magnitude of the rotational strength was fOund to depend critically on the relative orientation of the cyclopropyl and carbonyl chromophores, the rotation Of 82,being much more intense 29 ) I. /l. O 82 83 "W than that of 88,44 A similar geometric dependence is seen in the ioniza- tion of B-functionalized cyclopropyl derivatives. A pre- liminary report on the solvolysis of 88782 has just appeared.42 Three of these molecules ionize in a fashion similar to I r I t _ :22, :32. £22, :31 other bicyclo[2.2.2]octyl derivatives.‘15 Only for isomer 88,18 long—range cyclopropyl participation prOposed. All Of these examples bear one similarity. The p- orbital of the carbonyl function, or that of the developing carbonium ion, is orthogonal to the participating bond of the cyclopropyl ring in each case (81, 88, and 8Z).4° This contrasts with the parallel orbital orientation preferred by the relatively stable cyclopropylcarbinyl cations.47 This difference is probably due to the increased distance 30 over which the orbitals must interact for homoconjugation. The orthogonal orientation increases the effectiveness Of orbital overlap. Two modes Of orthogonal orbital overlap, leading to homoconjugation of a p-Orbital and a cycloprOpane ring, have been observed. The most effective is a symmetrical edge approach, leading to overlap as illustrated in 883. However, it is clear that interaction with the corner of a three-membered ring can also be significant.48 Solvolysis Of the 2x2 brosylate 88,13 characterized by complete scrambling between C-8 and C-4, suggesting the corner inter- action intermediate 88, If edge interaction with the C-2 — C-3 bond were involved, deuterium scrambling between C-2 and C-3 should also have occurred. Absence of edge inter- action is presumably due to the unsymmetrical orientation of the p-orbital relative to the edge bond. These studies suggest that the gigfhydrindan 12 is not formed because the rate of corner interaction of £8 to give Z§,(Scheme IV) is greater than the distorted edge inter- action gg'leading to Z8, The corner interaction results in 31 inversion of configuration at C—1 of 48, since the carbonyl p-Orbital is interacting with the back lobe of the C-1 — C-5 bond. Substituents on 4'which favor conformation 43 rather than 48, or which cause subtle changes in the required cyclopropyl-carbonyl orientation and interaction are ex- pected to hinder formation Of the Eggggfhydrindandione. This hypothesis can be evaluated by examining the products resulting from the ring openings Of cyclOprOpanols substituted so as to favor either the six-membered ring conformation 48 or 48, Of the fOur cycloprOpanols with methyl substituents on the six-membered ring (88 and 88784), the steteochemical uncertainty of the secondary methyl Of Qg’makes it a poor model. Likewise, the a-methyl of 84, although initially favoring 848 because this conformation minimizes the C-9 methyl non-bonding interactions, could epimerize under reaction conditions before ring Opening occurs. The most appropriate models are 88'and 88, since there is little ambiguity regarding the conformations adopted by their respective six-membered rings and no pos- sibility of epimerization exists. Cyclopropanol 88 should favor 88b and yield substantial amounts of a Eggggfhydrindan- dione while no cyclopropyla-carbonyl interaction will occur for 88, existing primarily as 828, The rather severe non- bonded interactions for R1 in 882 and R2 in 888 makes these conformations thermodynamically less favored. 32 Ha R1 R2 R1 RS 3 R 3 R2 H2 H1 H OH OH 2 $3,... R1 = R2 = R3 = H .0. 22' 64a 00. R1 = R2 = H, R3 = CH3 64b 633 0.. R2 = R3 = H. R1 = CH8 63b 503 .00 R1 = R3 = H, R2 = CH3 50b Table IV tabulates the major products Obtained from the base-catalyzed ring Openings of cyclopropanols 4, 88, and 88784, These results support the proposed correlation between the conformation Of the six-membered ring and the appearance of a hydrindandione product. As predicted, 88' yields the Eggggfhydrindandione (81, 89%) as does 64 (488, 40%) although the product distribution from the latter suggests some epimerization may have occurred before ring cleavage. 0n the other hand, no bond rearrangement appears to have occurred for 88, but the stereochemical uncertainty of the secondary methyl makes a correlation Of these re- sults with conformation 42’Or 48'impossible. In the case of cyclopropanol 88, where the axial methyl at C-10 strongly favors 888, no hydrindandione is Observed. The major product Obtained from the base-catalyzed re- arrangment of 88 was the isomeric ketol 100 (Equation 20).49 33 Table IV. Products derived from the base and acid cleavage of cyclopropanols 4, 22, and nggg'in MeOH solution. Predicted % Cyc10propanol Configur- Products Yield ation H0 13 4’ 4a & 4b 46 a. - - - 75 O 5 47 NV 1 O 15 3,23. ~20 2.9. 20 91 44 34 Table IV. Continued. APredictedi _ $6 cyclopropanol Conf%9ur' PrOd“°ts Yield ation H0 21 52 4a 92 - o. - - 48 O ' O O 11 22, O 24 3 2:2, 6 O 95 31 35 Table IV. Continued. Predicted—i % Cyclopropanol Configur- ' Products . HO a 11 22o, \ 22, 22, to b 89% O MeO 2’1 0. a 27 O 22' C a 57 llli OMe HO ' e 4 100 9.. o a 34 a ”W . b 718 M60 Table IV. Continued. 36 Predicted’ % Cyclopropanol Configur- Products yield ation : 48G 69 O 5 64 4b 102 0 19d 103 rvvv 35d 0 O ’ 19d 104 ' Ivvy 35(1 105 32 37 Table IV. Continued. Predicted’ Cyclopropanol Configur- Products . ation Yleld aProduct from acid-catalysis. bProduct from base-catalysis. cAlthough this twistane methyl ether was not observed, it was the major product obtained from the treatment of epimers £23 and 124 in absolute methanol with dry hydro- chloric acid. See the Experimental Section. dCombined yield of 103 and 104. eThe yields of these products, obtained from the treatment of a mixture of 50 and 66, have been adjusted to reflect their conversion~Trom cycloprOpanol g2, 38 KOH (20) 50 + i; o + 'W MeOH, H20 122, (71%) —’ «:9, (29%) A pure sample of 122, obtained by glpc, proved to be a crystalline solid (mp 106—107°). This compound was sensi- tive to moisture and decomposed in part to gg'on silica gel chromatography. Treatment of 122 with a benzene solution of pftoluenesulfonic acid yielded 62, however, hot methanolic KOH transformed either pure lgg'or Qgiinto a 71:29 mixture of these isomers respectively. A pfbromobenzensulfonate derivative (mp 124-125°), analyzed by means of a Picker FACS-l four circle diffrac- tometer, established the twistane conformation of 122 as shown in Figure 2.50 Interestingly, the carbonyl bond angle (c-l -C-2 —-C-3) disclosed by this study is 108.9(4)°, indicating a degree of angle strain also reflected in the infrared stretching frequency of this function (1734 cm-l). Torsion angles for the six-membered rings of the twistane skeleton approximate the twist-boat conformation. Although several syntheses of twistane ring systems have been reported,51'54 one of the most interesting new methods for preparing such compounds involves the intramolecular aldol condensation of cis-bicyclo[4.4.0]dec-3,9-dione Pi Figure 2 . 39 Stereodrawings illustrating the brosylate of 100 as determined by x-ray analysis. F.” (21 pr 40 discovered by Deslongchamps.5“5a'b'C Here an unfavorable aldol equilibrium was displaced by derivatization of the aldol hydroxy function (Equation 21). Subsequent reactions 0 O BF3 HO Aczo AGO (21) +1 ————> o 1,91 12,9, 222, Eprovided a variety of other twistane derivatives. With the same alkaline conditions which induced conver- sion of 6,9“ to 122, gig-decalindiones 4’6, 9'2, 9’3, 122, and gggag, all having an equivalent arrangement of carbonyl func- tzjuons, yielded no detectable quantities of the corresponding aldol isomers. We conclude, therefore, that the aldol cyclo- :i::Eition of fig'and the unexpected stability of 122 are uniquely favored by the C-10 methyl substituent, probably because of extreme non-bonded interactions in at least one of the de G: a lin conformations : CH3 0 O I 3 CH3 0 I I ‘ “N 2. o +— _ 0 69a 69b 625' CO de ir. is E: 41 The gig-decalin epimers 6% and 66 (Table IV) were formed in a 2:1 product ratio from cyclopropanol 6,2". This same ratio was obtained from pure 62, the sole product from the catalytic reduction of 26,55 under the same alkaline conditions which induced conversion of 66 to (9‘2, and 66, Compounds 166 and £64, homogeneous by the glpc, were determined to be gig-fused by comparison of their properties, including the angular methyl widths at half-height, with the isomeric trans-decalindione 110, synthesized as shown in Equation (22 ) . o ” 1) Li,NH3.THF ” (22) 2) (NH4)2C03 ’ 3) H30+ 3 O H 60 1.1.9. The stereochemical assignments for the a-methyls of 103 and 122’ were accomplished by a conformational analysis of 1—methy1-_c_i_§_-bicyclo[4.4.0]decan-2,8-dione analogues. Since the 1-methyl-gg-decalindiones can exist in either of two Chair conformations, 462’ or 462, the position of this equi- librium will be determined by substituents which stabilize one conformer relative to the other. Each conformation Places the angular methyl in a unique environment which Should be reflected by the observed pmr chemical shift and Should be somewhat independent of other substituents if Chair conformations are maintained. .' c _ o - epj pm In Cd me me 42 O O --——O Q——-— 0 48a 48b In Table V the chemical shifts of the angular methyls are tabulated for a series of cis-decalindiones and the preferred conformation is indicated. It is evident from these data that conformation 3253. has a lower chemical shift value for the angular methyl (6 1.31-1.37) than does 466 (<5 1.43-1.51). The stereochemistry was determined by correlating the chemical shift of the angular methyls for epimers 3.953. and 164 to the preferred conformation. The products obtained from the acid treatment of cyclo- propanols 4, 66, and 62:64 are also tabulated in Table IV. In addition to those products also observed in the base- catalyzed ring opening of these cyclopropanols, a number of methyl ethers were trapped. The formation of cyclOpropyl methyl ethers 6’1, 62, and 166 from cyclOprOpanols 4, 66, and E2, is further support for a bond rearrangement occurring in only one conformation (46) of the six-membered ring, since 29. and 62 did not givethe corre3ponding methyl ethers. The stereochemistry of 61, and by analogy 66 and 166, was proven by a reaction sequence to be described later. 43 Table V. Conformation analysis of analogues of l-methyl- cis-bicyclo[4.4.0]decan-2,8-dione. 5. Compound Angular Preferred Methyl Conformation O 2.3 .. 1.37 O 2.9. 1.43 2.3 .. 1.33 o a to ' O m. Law Tab 103 104 w 44 Table V. Continued 6 Preferred Compound Angular . Methyl Conformation 1.31 0 103a 1.47 O O a v' ......104 .. O aCorrlformation and hence stereochemistry is suggested by the <311ntrast, the spiro diketone gz'is known to be formed from 2' with retention of configuration at C-6.37 However, 46 OH OH O 45 75 g 112 Scheme v. 47 Formation 2,9-Bond Formation Formation 114 116 Twistane Copane Tricyclo[4.4.0.02.9]- Methyl Ether Methyl Ether decane Methyl Ether Scheme VI. 48 it remains an open question whether the glgfdecalindione 46' is formed from cyclopropanol 4'with inversion of configura- tion at C-1 or from cyclopropanol Z6'by retention of con- figuration at the same carbon. One approach to answering this question is to determine the products obtained from similar ring Opening reactions Insing derivatives of cyclopropanols 4 and Z6 in which the <3arbony1 function has been protected or removed, thus pre— 'venting interconversion of one cyclopropanol to the other. To this end, reduction of 4'followed by acid treatment (of the crude diol lil’gave the known epimers 446 and 446,37 (axidation of which yielded 41, identical to an authentic :3ample37 (Equation 23). The stereospecificity of several HO N H + (23) g 413—4» “ i—o - 2932], OH 0 OH 117 W 118 = equatorial OH 119 = axial OH § reducing reagents in methanol at different temperatures can 13GB determined from the ratios of 1465146 which are obtained (Table VI). However, base cleavage of llz'followed by oxidation gaVe two products, the spiro diketone 41 and the _c_:_j_._s_- decalin- dicn'ie 46 in a 58:42 ratio respectively. This important ff! T2 a | p. (A (1‘ IL) a: 49 result demonstrates unequivocally that base catalyzed cleav- age to the spiro diketone 4Z'occurs with retention of con— figuration, whereas inversion of configuration was the "modus operandi" leading to the cis-decalindione 46'; StereosPecificity of reducing agents for the Table VI. reduction of cyclopropanol 4. Reagent Tempgéature Ratio of 118:119 NaBH3CN58'59 o 71:21 NaBH4 “'44 93: 6 In a similar manner, the carbonyl function of cyclo- propyl methyl ether 2}. was protected as the alcohol. Cleav- age with either boron tribromide in methylene chloride, or dry hydrogen chloride in absolute methanol, followed by oxidation, gave a single product, the trans-hydrindandione &. In the case of cyclopropyl acetate 17, protection of the carbonyl was not necessary. Thus saponification of 11 in methanolic potassium hydroxide gave 46, with no detect- able amounts of spiro diketone 41 or cis-decalindione 46 be ing formed . These results suggest that the cis-decalindione 46 originates only from the unrearranged cyclopropanol 4 by aCid- or base-catalyzed ring opening with inversion of con- figuration. EXPERIMENTAL General All reactions have been conducted under nitrogen or argon and stirred with magnetic devices unless otherwise :noted. Organic extracts were dried over anhydrous sodium or magnesium sulfate before they were concentrated or distilled. Infrared spectra were recorded on a Perkin-Elmer 237B grating spectrophotometer using sodium chloride cells. Proton magnetic resonance (pmr) spectra were obtained with either a Varian T-60 or a Varian HA-100 high resolution spectrometer; tetramethylsilane was used as an internal Standard in most cases. Ultraviolet spectra were obtained on a Unicam SP-800 or a Cary 17 spectrometer. Mass spectra were obtained with a Hitachi RMU—6 mass spectrometer or a 13KB gas chromatograph-mass spectrometer. Melting points were taken on either the Hoover-Thomas apparatus (capillary tubes) or on a hot-stage microsc0pe and are uncorrected. Gas-liquid partition chromatographic analyses (glpc) were conducted with either a Varian 1200 flame ionization gas chromatograph or an Aerograph A—90P3 thermal conductivity instrument . 5O 51 Micro-analyses were performed by Spang Microanalytical Laboratory, Ann Arbor, Michigan. leMethylbicycloL4.4.01dec-6-ene-2,8-dione 2-Ethylene Ketal (22.) A solution of 5.05 g (28.4 mmol) of W. M. ketone (6) in 200 ml of dry benzene and 2 ml of butan—Z-one 2-ethylene ketal was acidified with dry hydrogen chloride to a pH <1.“"5 The reaction was monitored by glpc. After 3 days, 3 ml more of butan-Z-one 2-ethylene ketal were added. This solution was stirred for an additional 3 days, and then washed sequentially with saturated sodium bicarbonate, 10% sodium hydroxide solution, and water. The organic phase was dried and the solvent removed at reduced pressure to yield 6.23 g of crude product. Crystallization from 3 ml of ether gave 4 -20 g of white crystals. Chromatography of the mother liquor on 20 g of neutral alumina (activity III) provided an additional 0.92 g for a total yield of 5.12 g (86%). An analytical sample had mp 69-70° (lit.57 66-670): ir 1668, 1622, 1328, 1170 cm-1; pmr (CDc13) Ol.36(s, an), 1.50-2.70 (m. 1011), 3.98(s, 4H). 5.79(s, 1H). tr ans -1 , 9-Dimethylbicyclo[4 .4 .0] dec-6-ene -2 , 8-dione 2 -Ethylene 1% ($29.5 To a solution of 0.65 ml (4.96 mmol) of diiSOprOpyl anline in 5 ml of THF at 0° was added 2.08 ml (5.00 mmol) of 2-4M n—butyl lithium. After the solution was stirred for 52 10 min, 1.00 g (4.51 mmol) of 1—methylbicyclo[4.4.0]dec-6- ene-2,8-dione 2-ethylene ketal (66) in 3 ml of THF was added. This enolate anion solution was warmed to room temperature and stirred for 15 min, following which 0.314 ml (5.00 mmol) of methyl iodide was added and this solution was stirred an additional 1 1/2 hr. The reaction mixture was diluted with benzene and washed with water and saturated sodium chloride solution. Evaporation of the organic phase gave an oil which was shown by glpc analysis (20% SE 30, 185°) to con- sist of two products. The oil was dissolved in a 30:1 methanoldwater solution, 1.0 g of KOH was added, and the solution stirred overnight. After dilution with water and extraction with benzene, the combined organic phases were washed with water, saturated sodium chloride solution, and then dried and evaporated. The resulting oil was diluted with ether and cooled to give 0.795 g (75%) of crystalline ketal (66). An analytical sample, obtained by recrystal- lization from ether-ethyl acetate, had mp 109-110°: ir(cc1,) 1673, 1622, 1369, 1112, 1053 cm-1; pmr (cvc13) 61.12(d, J = 6.0 hz, 3H), 1.40(s, 3H), 1.52-2.95(m, 9H), 4.00(s, 4H), 5.83(s, 1H); mass spectrum (70 eV) m/e (rel intensity) 236(4), 99(100), 55(10). 5321, Calcd. for C14H2003: C, 71.16; H, 8.53 Found: C, 71.02; H, 8.65. trans-1,9-Dimethylbicyclo[4.4.0]dec-6-ene-2,8-dione (66) A crude sample of ketal 66, prepared as previously 53 described from 6.20 g (23.6 mmol) of ketal 52’ was dis- solved in 250 ml of acetone which contained 2 m1 of water and 5 ml of concentrated hydrochloric acid solution. After stirring the solution for several days, most of the acetone was removed at reduced pressure, and the residue was diluted with water and extracted with benzene. The organic phase was washed sequentially with water, saturated sodium bicarbonate solution, and saturated sodium chloride solution. Evaporation of the solvent left an oil residue which was dissolved in ether and cooled to induce crystal- lization (first crOp 1.90 g, second crop of 1.62 g) for a combined yield of 3.52 g (66%) 52; An analytical sample, obtained by recrystallization from ether, had mp 98-1000: ir(ccl4) 1715, 1672, 1624, 1452, 872 cm‘l; pmr(CDC13) 61.17 (d, J = 6.5 Hz, 3H), 1.52(s, 3H), 1.58-3.10(m, 9H), 6.84(s, 1H): mass spectrum (70 ev) m/e (rel intensity) 192(27), 177(11), 174(40), 164(10), 150(17), 137(100), 121(45), 108(40), 93(51), 55(77). Anal. calcd. for C12H1302: c, 74.97; H, 8.39 Found: C. 75.01; H, 8.42. LithiumeAmmonia Reduction of Substituted Bicycloifi.4.0]dec- 6-ene-2,8-diones 3, 53, 54, 55, and 56 The general method for the preparation of cycloprOpanols from their corresponding enediones is illustrated by the reduction of Wieland Miescher ketone 3; 54 (a) ilR*05a165)‘5‘HydrOXy-G-methyltricygloi4,4.0.01o5]— decan—9-one Ci) A solution of 1.34 g (193 mmol) of lithium in 500 ml of liquid ammonia, freshly distilled from sodium, and 25 ml of tetrahydrofuran was prepared in a three-necked flask equipped with an overhead stirrer and a dry-ice condenser. To this solution was added dropwise (80 min) 17.1 g (96 mmol) of Wieland Miescher ketone (2)22a,b in 125 ml of tetrahydro- furan. After addition the mixture was stirred for 20 min at —78°, following which it was decomposed by the addition of a large excess of anhydrous ammonium carbonate. The liquid ammonia was evaporated by placing the flask, through which a stream of nitrogen flowed, in a water bath. The slurry which remained was treated with water and ether, transferred to a separatory funnel, extracted with ether, and finally the organic extracts were washed with water and dried. Removal of the solvent at reduced pressure left an oil which crystallized to give 16.0 g of a white solid. Recrystallization from ether gave 15.1 g (87%) of pure cyclo- propanol 4; Cyclopropanol g'can be sublimed at 92° and 0.05 torr without decomposition. An analytical sample, obtained by several recrystallizations from ether, had mp 98-1000: ir(cc1,) 1710, 1150 cm-1; pmr(CDCl3) 51.08(s, 3H), 1.60-2.48(m, 12H), 3.12(bs, 1H); mass spectrum (70 eV) m/e (rel intensity) 180(100), 165(47), 152(15), 137(73), 124(57), 109(43), 97(46), 31(49), 67(37), 55(90). 1 55 Anal. Calcd. for C11H1502: C, 73.33; H, 8.88 Found: C, 73.21; H, 8.78. (b) (13f,5a,65,10 )-5-Hydroxyl-6,10-dimethyltricyclo- [4 .4 .0 .01 '5] decan-9-one (62‘) Lithium-ammonia reduction of 7.00 g (36.4 mmol) of 1,7—dimethylbicyclo[4.4.0]dec-6-ene-2,8-dione 52, conducted as previously described, yielded 8.30 g of an oil containing some THF. Crystallization from ether gave 3.20 g (46%) of white crystals. Several recrystallizations from ether- hexane gave an analytical sample, mp 115-1180 (lit.37 96-1020): ir(CCl,) 3570, 1695 cm'l. In addition to cyclOpropanol 62’ the mother liquor contained.~28% of the Ergngfdecalindione 65 which could be readily separated from 62 by preparative glpc (4% 03-1, 180°). An analytical sample had mp 73-750: ir(ccl,) 1710, 1450 cm‘l; pmr(CDCl3) 50.62(d,J = 7H3, an), 0.94 [s, an; Awh/z ‘ 0.61 cps (sweep width 50 Hz)], 1.05-2.40(m, 12H); mass spectrum (70 eV) m/e (rel intensity) 194(53, 127(100), 68(95). (c) (13f,5a,65,8a)-5-Hydroxy-6,8-dimethyltricyclo- [4.4.0.0105Tdecan-9-one egg) Lithium-ammonia reduction of 1.50 g (7.82 mmol) of trans-1,9-dimethylbicyclo[4.4.0]decan-2,8-dione 56 yielded 1.53 g of an oil which did not crystallize under various conditions. The pmr spectrum indicated only one product, 56 although glpc analysis indicated a trace of enedione igwas also present. Cyc10propanol 64 had the following properties: ir(film) 3350, 1705 cm-1: pmr(CDC13) 60.99(d, J = 6.5H3, 3H). 1.10(s, 3H), 1.15-2.90(m, 11H), 3.96(bs, 1H); mass Spectrum (70 eV) m/e (rel intensity) 194(84, 179(59), 174(31), 166(25), 151(96), 137(70), 124(80), 123(80), 109(65), 95(100), 81(65), 69(75), 55(85), (d) (13* .5a, 6(3 , 7a ) -5 -Hydroxy-6, 7-dimethyltricyclo- [4.4.0.01'5]decan-9-one2g Lithium-ammonia reduction of 10.0 g (52.1 mmol) of trans-1,10-dimethylbicyclo[4.4.0] dec-6-ene-2,8-dione 5,5,, conducted as previously described, yielded 10.4 g of an oil. Crystallization at -780 yielded 6.4 g of crystalline material consisting of a 3:1 mixture of 5,0 and (13,6a,10a)-1,10-di- methylbicyclo [4 .4 .0] decan-2 , 8-dione 6'6.Recrysta11izations did not alter this ratio: however, a careful Kugelwéihr distillation substantially increased the purity of fig: iz:(ccl,) 3475, 1706 cm-1: pmr(CDC13) 61.06(s, 3H), 1.15(d, J = 6.5 Hz, 3H), 1.40-2.75(m, 11H), 3.52 (bs,1H): mass Spectrum (70 eV) m/e (rel intensity) 194(32), 179(18), 176(22), 161(27), 151(26), 135(60), 123(42), 109(42), 95(40), 69 (72), 55(70), 41(100). An analytical sample of the minor product 6,6, prepared by recrystallization from ether, had mp 82.5-83.5° and SPectral properties identical to those recorded for the I“ajor product obtained from the dissolving metal reduction 57 and subsequent oxidation of (5a,68,7a)-7-hydroxy-5,6-di- methylbicyclo[4.4.0]dec-1-ene-3-one 61. (e) (13f,58,6cn7d)-5-Hydroxy-6,7-dimethyltricyclo- [4.4.0.0105]decan-9-one (ngfi' Lithium-ammonia reduction of 258 mg (1.34 mmol) of gig- 1,10-dimethylbicyclo[4.4.0]dec-6-ene-2,8-dione 54 gave 292 mg of an oil which did not crystallize under various condi- tions even though the pmr spectrum suggested a single pro- duct predominated. This oil had the following prOperties: ir(film) 3450, 1700 cm'l; pmr(CDC13) 60.91(s, 3H), 1.01(d, J = 6.5 Hz, 3H), 1.12-2.80(m, 11H), 3.47(bs, 1H); mass spectrum (70 ev) m/e (rel intensity 194(23), 179(25), 176(32), 160(27), 151(31), 145(40), 133(46), 124(49), 74(75), 59(100). 8-Ethoxy-trans~1,10-Dimethylbicyclo[4.4.0]dec-5,7-diene- 2-one (58) To a solution of 1.00 g (5.20 mmol) of trans-1,10- dimethylbicyclo[4.4.0]d e C-6-ene-2,8-dione Efi'in 40 m1 of benzene were added 0.2 ml of ethanol and 2 ml of redistilled ethyl orthoformate. Dry hydrogen chloride was then intro- duced until a pH <1 was obtained. The reaction mixture was stirred for 2 hr at room temperature, and then sequentially washed with saturated sodium bicarbonate, water, and satu- rated sodium chloride solution. Evaporation of the solvent gave 1.170 g of crude product which slowly solidified to a yellow solid on cooling. Crystallization from an ether—hexane 58 solution gave 0.792 g of white crystals. The mother liquors were chromatographed on 20 g of Woelm neutral alumina (activity III). Elution with 10-30% ethyl acetate in hexane gave an additional 0.128 g of the dienolether 58 for a com- bined yield of 0.857 g (75%). Recrystallization from ether— pentane gave an analytical sample: mp 95-960; ir(CCl4) 1710, 1650, 1625, 1380, 1355, and 1170 cm-1; pmr(CDC13) 60.97(d, 3H, J = 7.0 Hz), 1.17(s, 3H), 1.31(t, 3H, J = 7.0 Hz), 1.42-2.95(m, 7H), 3.79(1, 2H, J = 7.0 Hz), 5.24 (s, 1H), 5.66(dd, 1H, J = 3.0 Hz, J' = 3.0 Hz): mass spec- trum (70 eV) m/e (rel intensity) 220(100), 205(9), 192(41), 177(58), 163(44), 149(30), 135(58), 121(17), 91(30), 77(20). Anal. Calcd. for C12H2002: C, 76.32: H, 9.15 Found: C, 76,34: H, 9.14. Reduction and Hydrolysis of 8-Ethoxy-trans-1,10-dimethy1- bicyclo[4.4.0] dec -5,7-diene-2Fone (5E) A solution of 500 mg (2.27 mmol) of dienol ether 58 in 10 ml of dry THF was added to a suspension of 200 mg of lithium aluminum hydride in 50 ml of dry THF and the mixture was refluxed under a nitrogen atmosphere overnight. The reaction mixture was then cautiously decomposed with water and the solvent was removed at reduced pressure. The resi— due was dissolved in 100 m1 of acetone and 3 ml of water, acidified to pH <1 with hydrochloric acid, and stirred at room temperature for 1/2 hr. Most of the acetone was evapor- ated at reduced pressure, ether was added and the organic phase was washed with water and saturated sodium bicarbonate 59 solution, then dried over magnesium sulfate. Evaporation at reduced pressure gave a semi-crystalline solid. Careful crystallization from ether yielded 250 mg (58%) of (5a,63, 7a)-7-hydroxy-5,6-dimethylbicyclo[4.4.0]dec-1-ene-3-one E1; mp 122-1230: ir col, 3600, 3380, 1572, 1620, 1040 cm-1; pmr(CDC13) 01.16(d, 3H, J = 7.0 Hz), 1.21(s, 3H), 1.45-3.20 (m, 9H), 4.14(m, 1H), 6.06(S, 1H): mass spectrum (70 eV) m/e (rel intensity) 194(48), 176(16), 161(100), 138(41), 123(61). Found: C, 74.18; H, 9.41. Glpc analysis (4% QF—l, 190°) indicated that, in addi- tion to 61’ the mother liquor contained ~'50% of the (5B,6a,7a)-7-hydroxy-5,6-dimethylbicyclo[4.4.0]dec-l-ene- 3-one (68), which was isolated by preparative glpc as a crystalline solid, mp 117-119°: ir(cc1,) 3600, 3390, 1668, 1612, 1036 cm-1; pmr(CDC13) 5 1.05(d, 3H, J = 7.0 Hz), 1.29 (s, 3H), 1.41-3.01(m, 9H), 3.85(m, 1H), 5.83(s, 1H); mass spectrum (70 ev) m/e (rel intensity) 194(33), 176(23), 161(100), 138(36), 123(51), 91(51), 41(64). Angl.Calcd. for C12H1302: C, 74.19: H, 9.34 Found: C. 74.01; H, 9.34. Lithium-Ammonia Reduction and Oxidation of (5a,65,7a)-7- Hydroxy35,6-dimethylbicyclo[4.4.0] doc -1-—ene-3-one (W67) To a solution of 130 mg (0.67 mmol) of §Z,in 75 ml of liquid ammonia and 25 ml of dry THF at -33° was added small amounts of lithium metal until a blue color persisted. The 60 reaction mixture was then stirred for 15 min, quenched with ammonium chloride, and the ammonia was evaporated to give a residue which was dissolved in water and extracted with ether. The ether extract was dried and the solvent was evaporated to give an oil, which was dissolved in 2 ml of methylene chloride and oxidized by freshly prepared Collins reagent.31 A black, tarry deposit separated immediately. The reaction was stirred for an additional 15 minutes at room temperature. The solution was then decanted from the residue which was washed with 40 ml of ether. The combined organic solutions were washed with three portions of 5% sodium hydroxide solution, 5% aqueous hydrochloric acid, water, and saturated sodium bicarbonate solution. Evapora— tion of the solvent gave 105 mg of an oil consisting of two components in a 62:38 ratio. These were isolated with difficulty by the repeated passage of impure fractions through a 4% QF-l column at 170°. The major component was the traggfdecalin 62, mp 82.5-83.5: ir(CCl4) 1710, 1440, 1410 cm-1: pmr(CDC13) 5 0.92(d, 3H, J =7.0 Hz), 1.36(s, 3H), 1.46-3.00(m, 12H); mass spectrum (70 eV) m/e (rel intensity) 194(54), 179(13), 161(33), 123(53), 111(49), 95(39), 69(100), 55(61), 41(81). ' Anal, Calcd. for C12H1803: C, 74.19: H, 9.34 Found: c, 74.10: H, 9.44. The minor component was the gigfdecalin 62, recovered as an oil and shown by glpc and ir analysis to be identical 61 to the single product obtained from catalytic hydrogenation of trans-1,10-dimethylbicyclo[4.4.0] dec -6-ene-2,8-dione 55, (1a,6a,106)-1,10-Dimethylbicyclo[4.4.0]decan-2,8-dione (62) A solution of 100 mg (0.52 mmol) of trans-1,10-dimethyl- bicyclo[4.4.0] dec -6-ene-2,8-dione Qégin 1 ml of ethanol was added to a pre-hydrogenated suspension of 10 mg of 10% palladium on charcoal in 5 ml of ethanol, and the resulting mixture was shaken in a Parr hydrogenator (50 psi, room temperature). Hydrogen uptake ceased after 25 min: the suspension was then filtered and the catalyst washed with hot ethanol.29 Chromatography of the crude organic product on silica gel gave 95 mg (94%) of (1a,6a,105)-1,10-dimethyl— bicyclo[4.4.0]decan-2,8-dione §2 as an oil: ir(ccl,) 1720, 1705, 1085 cm_1: nmr (CDC13) 0 1.23(d, J = 6.0 Hz, an), 1.43(S, 3H), 1.52-3.20(m, 12H); mass spectrum (70 eV) m/e (rel intensity) 194(35), 179(3), 161(10), 123(20), 110(91), 95(28), 81(29), 69(75), 55(47), 41(100). Anal. Calcd for C12H1303: C, 74.19; H, 9.34 Found: C, 74.11; H, 9.20. (18,6a,9o)-1,9-Dimethylbicyclo[4.4.0]decan-2,8-dione (110) Lithium was added in small pieces to a solution of 150 mg (0.64 mmol) of Ergggel,9-dimethylbicyclo[4.4.0]dec- 6-ene-2,8-dione 2-ethylene ketal gg'in 20 ml of THF and 75 ml of liquid ammonia until a blue color persisted. This solution was then stirred at reflux for 1 hr, following 62 which the reaction was quenched with excess ammonium chloride. The ammonia was evaporated by placing the flask in a cold water bath, and the residue was taken up in ether and washed with water. Several drOps of concentrated H2SO4 were added to the etherial solution which was then stirred overnight. The solution was sequentially washed with water and saturated sodium bicarbonate solution, then dried and evaporated. An analytical sampleswas crystallized from ether, mp 58-610: ir(ccl,) 1708, 1445, 1165 cm-1: pmr(CDC13) 6 1.07(d, J = 6.5 Hz, 3H), 1.40[s, 3H; d, J = 0.59 cps (sweep width 50 Hz) and AWh/2 - 0.95 cps], 1.50-3.92(m, 12H); mass spectrum (70 eV) m/e (rel intensity) 194(100), 179(10), 166(15), 161(13), 95(65), 41(95). A331. Calcd. for C12H1803: C, 74.19: H, 9.34 Found: C, 74.32; H, 9.16. Base-Catalyzed Reactions of Substituted TricycloL4.4.0.01:5]- decan-9-ones The general method for effecting base-catalyzed rear- rangements of tricyclo[4.4.0.01I5]decan-9-ones is illustrated by the reaction of cyclOpropanol g'with KOH in aqueous methanol. (a) trans-1,6-Dimethylbicyclo[4.3.0]nona-2,7-dione (if) To 8 ml of a deoxygenated 50:50 methanoldwater mixture at 0° was added 1.02 g (5.67 mmol) of (1Rf,5a,65)-5-hydroxy- 6-methyltricyclo[4.4.0.01 5]decan-9-one 4'and an excess of 63 potassium hydroxide. This solution was stirred for 4 hr at 0° and then overnight at room temperature. Following dilu- tion with water and extraction with benzene, the organic phase was washed with water and dried. Evaporation at reduced pressure gave a white crystalline product, which on recrystallization from ether yielded 0.62 g (62%) of hydrindanedione 46, In some preparations yields as high as 75% have been realized by extensive chromatography of the mother liquors on silica gel. It was recently discovered58 that 48 forms a bisulfite addition,thus making separation of 46 and 48 much easier. An analytical sample had mp 167-168°: ir (KBr) 1705, 1735 cm-1: pmr (c0013) 6 0.92(s, an), 1.17 (s, 3H), 1.32-2.89(m, 10H): mass spectrum (70 eV) m/e (rel intensity) 180(59), 165(55), 152(4), 136(24), 124(45), 109(100), 94(57), 82(51), 67(50), 55(50), 41(65). ‘Aggl. Calcd. for C11H1502: C, 73.33: H, 8.88 Found: C, 73.05: H, 8.91. The mother liquor also contained a trace of 10—methyl- spiro[4,5]decan-1,7-dione gz'and and ~o50% of 1-methyl-cis- bicyclo[4.4.0]decan-2,7-dione 48 (19% yield from 4). (b) Base Catalyzed Reaction of (13f,5a,68,10E)-5- Hydroxy-6,10-dimethyltricyclo[4.4.0.0173]decan- 9-one (6 ) Base treatment of 100 mg (0.52 mmol) of cyclopropanol 62 gave 95 mg of an oil which glpc analysis (4% QF-l, 160°) showed to consist of spiro diketone 92 (6%) and the epimers 22 and 92 (72% in a 2:1 ratio) as well as other minor products. 64 (1) 6,10-Dimethylspiro[4,5]dican—2,7-dione 94 had properties consistent with those previously recordedr"7 ix(cc1,) 1735, 1705 cm-1. (2) (1a,6a.7fi)-1,7-Dimethylbicyclo[4.4.0]decan- 2 ,8-dione 23. had properties identical to those previously reported: ir (001,) 1708 cm-1; pmr(CDCl3) 6 0.98(d, J = (5.5 Hz, 3H), 1.33(s, 3H), 1.56-2.95(m, 12H): mass Spectrum (70 eV) m/e (rel intensity) 194(51), 127(100), 68(98). Treatment of pure 2% in aqueous methanollat room temperature with either KOH or HCl gave a 2:1 product ratio of 9,2, to 93. (3) (1a,6a,7a)-1,7-Dimethylbicyclo[4.4.0]decan- 2 ,8—dione 23’ had the following properties: ir(CCl4) 1708 cal—1; pmr(CDC13) 6 1.01(d, J =- 7.0 Hz, 3H), 1.51(s, 3H). (c) Base treatment of (1R*,5B,6a,7a)-5-Hydroxy-6,7- dimethyltricyclo[4.4.0.0!'5]decan-9-one (63) Base-catalysis of 128 mg (0.66mmol) of cycloprOpanol 6'3. gave 128 mg of crystalline material, shown by glpc analysis to consist of 89% of the m—hydroindanedione ’91. Prepara- tiVe glcp gave an analytical sample, mp 95-100°: ir(CCl4) 1710, 1739, 1458, 1378, 1092, 1020 cm-1: nmr(CDC13) 6 0.98 (S . 3H), 1.12(s, 3H), 1.10(d, J = 6.0 Hz, 3H), 2.25-3.05(m, SH) : mass spectrum (70 ev) m/e (rel intensity) 194(27), 179(9), 153(9), 137(13), 124(100), 109(28), 96(51)- 65 (d) Base Treatment of (lgf,5a,68,7a)-5-Hydroxy-6,7- dimethyltricyclo[4.4.0.01'5]decan-9—one (66) Base treatment of 200 mg of a mixture of cyclOpropanol 66 and the trans-decalindione 66, prepared from the dissolving metal reduction of enedione 66, gave a quantitative yield of an oil from which three components were separated by prepara- tive glcp (4% QF-l, 195°): (1) (13f,3§f,6§f,83f,10§f)-8-Hydroxy-1,10- dimethyltricyclo[4.4.0.0303]decan-Z—one 666 (57%) had properties identical to the ketol derived from the base treatment of gigfdecalindione 665 ir(CCl4) 3590, 3400, 1725 cm-1; (2) (1a,6a,103)-1,10-Dimethy1bicyclo[4.4.0]decan- 2,8-dione 66 (16%) had prOperties identical to those of the single product obtained from the catalytic reduction of enedione 66; ir(film) 1720, 1705, 1085 cm-1: (3) (15,6a,10a)-1,10-Dimethylbicyclo[4.4.0]decan- 2,8—dione 66'(26%) had properties identical to the trans- decalindione obtained as in Scheme III: ir(CC14) 1710, 1440, 1410 cm-1. (e) Base Treatment of (1R*,5a,6fi,8a)-5-Hydroxy-6,8— dimethyltricycIoT4f4.0.0105]décan-9-one (64) Base treatment of 200 mg (1.04 mmol) of the oily cyclo- propanol 62 gave an oil. Preparative glpc (4% QF—l, 185°) separated the two major components: 66 (1) (15,6a,8g)-1,6,8-Trimethylbicyclo[4.3.0]nona— 2,7-dione 166'(80 mg, 40%), mp 90-950 was homogeneous by glpc and tlc: ir(ccl,) 1739, 1713, 1455, 1375 cm-1: pmr (60 MC, CDC13) indicated two sets of two singlets each (6 0.86, 1.16 and 0.96, 1.11) and a doublet (6 1.24, J = 7.0 Hz) which separated into a pair of doublets (J' I 7.0 Hz, J" = 7.2 Hz) when the spectrum was taken in C3D6 at 100 MC and a sweep width of 250 Hz: mass spectrum (70 ev) m/e (rel intensity) 194(59), 179(48), 151(44), 137(38), 125(59), 124(57), 110(98), 95(100). éflil' Calcd. for C12H1803: C, 74.19: H, 9.34 Found: C, 73.99; H, 9.30. (2) Oa,6a,9§)-1,9-Dimethylbicyclo[4.4.0]decan- 2,8-diones $66 and 162 (70 mg, 35%) was homogeneous by glpc and tlc: ir(film) 1708, 1450, 1423, 1375, 1152, and 1095 cm-1; pmr (60 MC, CDC13) indicated two singlets (6 1.31 and 1.47) and a pair of doublets (6 0.95, J = 6.0 Hz and 6 1.01, J - 6.7 Hz) whose coupling constants did not change when the spectrum was taken at 100 MC with a sweep width of 250 Hz: mass spectrum (70 ev) m/e (rel intensity) 194(51), 124(59), 111(100), 95(44), 81(32), 69(56). 522$: Calcd for C12H1303: C, 74.19: H, 9.34 Found: C, 74.25: H, 9.35. 67 (1a,3a,6fi)33-Bromo-1,6-dimethylbicyclo[4.3.0]nona-2,7- dione Fig. 1 To a solution of 1.42 g (7.90 mmol) of 2332271,6—di— methylbicyclo[4.3.0]nona—2,7-dione (26) in 50 ml of dry carbon tetrachloride was added 4.40 g (9.59 mmol) of 2-pyrrolidonehydrobribromide, PHT.3°o59 This solution was stirred in the dark at room temperature for 20 hr, during which time a white crystalline solid [bix-(2-pyrolidone) hydrobromide] precipitated. The precipitate and the un- reacted PHT were removed by filtration, 100 ml of ether was added to the filtrate and the organic solution was washed with saturated sodium bicarbonate, water and satur- ated sodium chloride solution. The solvent was evaporated from the dried solution and the residue (2.47 g) was crys- tallized from ether to give a first crop of 1.10 g and a second crop of 0.60 g for a combined yield of 84%. An analytical sample had mp 144-147°: ir(KBr) 1720, 1740 cm-1: pmr(CDC13) 6 0.95(s, 3H), 1.49(s, 3H), 3.04-1.60(m, 8H). 4.43(dd, 1H, J = 4.0 Hz, J' = 6.8 Hz): mass spectrum (70 eV) m/e (rel intensity) 260(4), 258(4), 245(3), 243(3), 190(3), 188(3), 179(18), 165(23), 151(13), 137(18), 123(25), 110(47), 95(88), 82(75), 67(74), 55(59), 41(100). 533;, Calcd. for C11Hi5033r: .C, 51.01: H, 5.79 Found: C, 51.09: H, 5.90. 68 (13f,33f,6§:,83f,103f)—8-Hydroxy-1,10-dimethyltricyclo- [4.4.0.03081decan—2-one (100) To 2 ml of methanoldwater (50:50) which contained one pellet of potassium hydroxide was added 20 mg (0.10 mmol) of (1a,6a,105)-1,10-dimethylbicyclo[4.4.0]decan-2,8-dione 66; This solution was stirred overnight at room temperature and then diluted with water and extracted with benzene. I The organic extract was washed with water and evaporated at reduced pressure. It gave a quantitative recovery of an oil. Glpc analysis (4%TQF-1, 195°) of this oil indicated it was a mixture of ketol 166'(71%) and unreacted starting material (29%). Preparative glpc gave an analytical sample (mp 106-107°) which rapidly lost its crystalline properties on exposure to the air and which could not be recrystallized. The spectroscopic prOperties of 166'were observed to be: ir(CCl4) 3590, 3400, 1725, 1455, 1378, 1315, and 1070 cm_1: nmr(d3-DMSO) 6 0.67(d, J = 6.5 Hz, 3H), 0.81(s, 3H), 0.85- 2.40(m, 11H), 4.96(s, 1H): mass Spectrum (70 ev) m/e (rel intensity) 194(35), 110(91), 95(28), 81(29), 69(75), 55(47), 41(100). ’ 523$, Calcd. for C12H1802: C, 74.19: H, 9.34 Found: C, 74.14: H, 9.51. 69 Preparation of trans-1,10-Dimethyl-8(6:bromobenzenesu1fonoxy)— tricyclo[4.4.0.0§'°]decan-2eone (Fig 2) A solution of 90 mg (0.22 mmol) of ketol 166 in 2 ml of dry pyridine was treated at 0° with a large excess of pfbromobenzenesulfonyl chloride. After complete dissolution the resulting solution was stirred at room temperature for three days, and then poured into water at 0°, stirred, and extracted with ether. The organic phase was washed sequentially with dilute hydrochloric acid, water, and saturated Sdoium bicarbonate solution and dried over anhy- drous sodium sulfate. Careful evaporation gave 133 mg (70%) of white crystals. A portion of these were dissolved in ether and placed in a closed vial from which very Slow evaporation of the solvent gave excellent Single crystals appropriate for collecting three dimensional X-ray data. An analytical sample had mp 124-125°: ir(CCl‘) 1734, 1325- 1380, 1178, 920, 868 cm_1: nmr (CDC13) 6 0.88(d, J a 6.5 Hz, 3H), 0.92(s, 3H), 1.20-2.86(m, 11H), 7.78(S, 4H): mass Spectrum (70 ev) m/e (rel intensity) 414(3), 412(3), 221(6), 219(6), 193(45), 176(24), 157(14), 155(14), 148(28), 133(12), 120(12), 110(100), 93(17), 81(14), 69(21), 55(21). 5231, Calcd. for 018H218r0,: c, 52.31; H, 5.12 Found: C, 52.29: H, 5.21. Acid Treatment of Substituted Trigyc1914.4.0.01'91decanf9-ones The general method for acid-catalyzed ring opening of tricyclo[4.4.0.01:5]decan-9-ones is illustrated by the 7O reaction of cyclopropanol 6 with hydrogen chloride in aqueous methanol. (a) Acid Treatment of (13f,5a,66)-5-Hydroxy-6-methyl— tricyclo[4.4.0.01I5]decan-9-one (22_ A solution of 200 mg (1.11 mmol) of cycloprOpanolJQ in 10 ml of a 50:50 MeOH-Hzo solution was treated with concentrated hydrochloric acid until a pH < 1 was obtained. After the mixture was stirred at room temperature for 2 days, the solution was diluted with water and extracted with benzene. The organic phase was washed with water and saturated sodium chloride solution. Evaporation of the solvent gave an oil which was separated by preparative glpc into five components. Three minor products (66, 13%; 21, 5%; and g6, 15%) were identical to those obtained from the base- catalysis of 2, The two major products were oils, cyclo- prOpyl methyl ethers 61 and 66, which have the following constitution: (1) (lgf,3a,6a)-32Methoxy-6-methyltricyclo- [4.4.0.01c316ecan-9-one 2}.(44%)= ir(Film) 1705, 1439, 1234, 1045; pmr(CDC13) 6 0.34(d, J = 5.5 Hz, 1H), 0.74(d, J = 5.5 Hz, 1H), 1.32(s, 3H), 1.36—2.80(m, 10H), 3.37(s, 3H); mass spectrum (70 ev) m/e (rel intensity) 194(14), 179(100), 151(26), 138(27), 123(80), 110(35), 91(36): 4 533;. Calcd. for C13H1802: c, 74.19; H, 9.34. Found: C, 73.92: H, 9.45. 71 (2) (13f,5a,6B)-5zMethoxy~6-methyltricyclo- [4.4.0.01'°]decan-9-one 66'(20%): ir(film) 1710 cm-1: pmr(CDC13) 1.12(s, 3H), 1.20-2.80(m, 12H), 3.37(s, 3H): mass spectrum (70 ev) m/e(rel intensity) 194(12), 179(100), 151(15), 137(88), 123(31), 105(34), 93(38), 91(50), 79(47). gggl, Calcd. for C12H1303: C, 74.19: H, 9.34 Found: C, 74.00; H, 9.41. (b) Acid Treatment of (15f,5a,6B,10£)-5-Hydroxy-6,10- dimethyltricyclo[4.4.0.0‘15]decan-9-one 66‘ Acid-catalyzed ring opening of 250 mg (1.29 mmol) of cyclopropanol 66'yielded 248 mg of an oil. Preparative glpc (4% QF—l, 170°) gave three products [66'(21%); 66'(11%); and 66'(3%)], identical to those obtained from the base- catalysis of 66, and two methoxy ethers which had the fol- lowing properties: (1) (13f,2§f,6§f,73f)-2-Methoxy-1,7-dimethyl- tricyclo[4.4.0.09'7]decan—8-one (66, 31% yield): ir(film) 1708, 1318, 1231, 1065, 1042 cm-1: pmr(CDC13) 6 0.94 (s, 3H), 1.30(s, 3H), 1.32—2.85(m, 11H). 3.28(s, 3H); mass spectrum (79 ev) m/e (rel intensity) 208(22), 193(100), 175(18), 165(20), 161(16), 151(23), 137(52), 124(38), 105(53), 91(44), 79(44). ' éggi, Calcd. for C13H2002: C, 74.96: H, 9.68 Found: C, 74.94: H, 9.62. 72 (2) (13f,2§f,4§f,6§,7§f)-2-Methoxy-1,7-dimethyl- tricyclo[4.4.0.02:9]decan-8-one (66, 6% yield): ir(film) 1710, 1450, 1150, 1014 cm-1: pmr(CDC13) 6 1.04(s, 3H), 1.05 (a, 7.0 Hz, 3H), 1.20-2.70(m, 11H), 3.26(s, 3H); mass Spectrum (70 ev) m/e (rel intensity) 208(18), 151(100), 137(32), 121(26), 105(26), 91(33), 79(31). 523;, Calcd. for 013H200,: c, 74.96; H, 9.68 Found: C, 74.69: H, 9.62. (c) Acid Treatment of (15f,55,6a,7d)-5-Hydroxy-6,7- dimethyltricyclo[4.4.0.01o5]decan-9-one (63) Acid treatment of 130 mg (0.67 mmol) of cyclopropanol 66'yielded 124 mg of an oily residue. The Eggggfhydrindan- dione 6Z,(11%), identical to the major product obtained from the base catalysis of 66, and two methoxy ethers were separated by preparative glpc (4% QF-l, 180°): (1) (1§f,3a,5a,6a)-32Methoxy-5,6-dimethyltricyclo— [4.4.0.01:8]decan—9-one gg,(57%): ir(film) 1708, 1325, 1234, 1050 cm"; pmr(CDC13) 6 0.32(d, J = 5.5 Hz, 1H), 0.80-0.99 [m, 4H, simplifying to a doublet (J = 6.0 Hz, 3H) upon spin decoupling at 0.32], 1.23(s, 3H), 1.32-2.79(m, 11H), 3.30(s, 3H): mass spectrum (70 ev) m/e (rel intensity) 208(16), 193(54), 165(80), 137(70), 123(100), 105(36), 91(40), 79(38). ' (2) (13*o55.5.0.7a)-5-Methoxytricyclo[4.4.0.01:5] dec-9-one 66 (27%): ir(film) 1708 cm-1: pmr(CDCl3) 73 6 0.92(s, 3H), 1.06(d, J = 6.5 Hz, 3H), 1.20-2.81(m, 13H), 3.32(s, 3H): mass Spectrum (70 ev) m/e (rel intenSity) 208(19), 193(26), 177(17), 165(35), 151(41), 138(100), 123(39), 105(28), 93(44), 91(37). ‘ ‘ (d) Acid Treatment of (13f,5a,6B,7a)—5-Hydroxy-6,7— dimethyltricyclo[4.4.0.0105]dgcan-9-one (50) Acid treatment of 230 mg (1.18 mmol) of a mixture of cyclopropanol 66 and the Eggggfdecalindione 66, prepared by the dissolving metal reduction of enedione 66, gave a quanti- tative yield of an oil from which four components were separated by preparative glpc. In addition to 66 (23%), two of these products [166 (26%), 66 (36%)] were identical to those obtained from base-catalyzed reaction of 66, A minor product, 166'(5%), which had properties identical to the methyl ether obtained from the treatment of gigfdecalindione 66’in methanol with HCl, was also isolated. (e) Acid Treatment of (13f,5a,6B,8a)-5-Hydroxy-6,8- dimethyltricyclo[4.4.0.01 5]decan-9-one (6g) Acid treatment of 300 mg (1.54 mmol) of 62 yielded 237 mg of crude product, from which three compounds were separated by preparative glpc (4% QF-l, 185°). Two of these products [the empimeric Sigfdecalindiones 166 and 162'(com- bined yield 19%) and the epimeric Eggggfhydrindanes 666' (5%)] were identical to those obtained from the base- catalyzed ring opening of 62, A rearranged cyclopropyl 74 methyl ether, O§f,3a,4B,6a)-3-methoxy-4,6—dimethyltricyclo- [4.4.0.01:3]decan-7—one 166 (oil, 32%) was also isolated: ir(film) 1708, 1445, 1232, 1050, 1018 cm-1: pmr(CDC13) 6 0.24(d, J = 5.5 Hz, 1H), 0.73(a, J = 5.5 Hz, 1H), 0.98(d, J = 6.5 Hz, 3H), 1.32(s, 3H), 1.41-2.78(m, 9H), 3.33(s, 3H): mass Spectrum (70 ev) m/e (rel intensity) 208(10), 193(100), 176(8), 165(30), 152(18), 137(57), 123(54), 105(33), 91(33), 72(42). I ' ' 3 Synthesis of Substituted 8HMethoxy Twistane Derivatives The general procedure for the preparation of 8-methoxy- twistane derivatives from their corresponding Sigfdecalin- diones is illustrated by the reaction of 69 in anhydrous MeOH with dry HCl. (3) (13f,3§f,6§f,8§f,10§f)-8-Methoxy-1,10-dim3thyl: tricyclo[4.4.0.03o3]decan-2-one (101) A solution of 22.5 mg (0.108 mmol) of (1a,6a,106)-1,10- dimethylbicyclo[4.4.0]decan-2,8-dione 62'in 4 ml of absolute methanol was maintained at 0° while anhydrous hydrogen chloride was added over a 2 minute period. The reaction was then allowed to warm to room temperature and Stirred for 1 hour, following which the solvent was removed at reduced pressure. The residue was dissolved in ether, washed sequentially with saturated sodium chloride solution and saturated sodium bicarbonate solution and dried. Re- moval of the solvent gave an oil which was purified by 75 passing through a Short silica gel column. Removal of the solvent gave 23.8 mg (98%) of 66; as an oil with the fol- lowing physical prOperties: ir(neat) 1726, 1451, 1135, 1110, 1090, and 1074 cm"1; pmr(CDC13) 6 0.80(d, H, J = 6.0 Hz), 0.91(s, 3H), 1.00-2.42(m, 11H), 3.23(s, 3H): mass Spectrum (70 ev) m/e (rel intensity) 208(13), 193(4), 176(8), 110(100), 99(63). A236, Calcd. for C13H2002: C, 74.96: H, 9.68 Found: C, 74.96; H, 9.72. The oil thus obtained could be crystallized from wet ether (mp 45-460): however, ir absorption at 3410 cm-1 suggested water was incorporated in the crystal lattice. The carbonyl absorption appeared unchanged. (b) (1;f,3§f,6§f,8§f,9§f)-8-Methoxy-1,9-dimethyl- tricyclo[4.4.0.03:3]decan-Z-one (196) Acid treatment of 41 mg (0.21 mmol) of 166 yielded a single product (166, 44%), separated as an oil from unre- acted starting material by preparative glpc (4% QF-l, 180°): ir(film) 1728, 1450, 1192, 1167, 1082, 1047, 995 cm-1; pmr (cc14) 6 0.90(s, 3H), 0.91(d, J = 7.0 Hz, 3H), 1.09-3.68 (m, 11H), 3.15(S, 3H): mass spectrum (70 eV) m/e (rel intensity) 208(16), 110(100). Acid Treatment of Cyclopropanol 117 To 50 mg (0.28 mmol) of cyclopropanol g'in 9 ml of absolute MeOH was added 32.6 mg (16 meg) of solid NaBH4. 76 The resulting solution was stirred for 3 1/2 hr at —44°, and then quenched with HOAc. After it was warmed to room tempera— ture, 4 ml of water and 1/2 ml of concentrated hydrochloric acid was added and the resulting solution was stirred over- night. Following the addition of more water and extraction with benzene, the organic phase was washed sequentially with water and saturated NaHC03 solution. Glpc analysis (4% QF—l, 185°) indicated the formation of the isomeric Spiro ketols 166 and 166 in a 93:6 product ratio. Jones oxidation gave the spiro diketone gl'in 94% yield: ir(CC14) 1710, 1739 cm . The amount of trans—hydrinandione 26 or cis-decalin- dione g6’produced was less than 1%. Base Treatment of CycloprOpanol 117 Cyclopropanol 161, prepared as previously described by the reduction of 300 mg (1.66 mmol) of cyclOprOpanol 2'with 160 mg (4.21 mmol) of NaBH4 in 15 ml of absolute MeOH, was treated i2_§1£2 with KOH until a pH > 13 was achieved. The resulting solution was stirred overnight and then diluted with water and thoroughly extracted with benzene. The benzene extracts were washed with water, dried, and evapor- ated to give an oil. Glpc analysis (4% QF-1, 185°) indi- cated two components, spiro diketone 26 and Sigfdecalindione 66, in a 58:42 product ratio. Each product displayed Spectral properties identical to those of the compound and melting points (21, 59-610: 26, 64-66°) which remained un— changed when each was mixed with an authentic sample. 77 Reduction and Cleavage of (18*,3a,6a)—3-Methoxy-6—methyl- tricyclo[4.4.0.01:3]decan—7-one GEE) (a) Cleavage with Boron Tribromide To 130 mg (0.67 mmol) of cyclopropyl methyl ether 6; in 5 ml of absolute EtOH at 0° was added 25 mg (0.66 mmol) of NaBH4. The reaction was stirred for 1 hr, quenched with HOAc, the solvent was evaporated at reduced pressure, and the residue was dissolved in water and thoroughly extracted with ether. The organic phase was washed with water and dried. Evaporation of the solvent gave an oil, which was dissolved in 5 ml of dry CH2C12 and cooled to a -78°. This solution was treated with 0.20 ml (2.11 mmol) of BBrs, and stirred for 1 hr.°° The reaction mixture was then poured into cold water, extracted with benzene, and the organic phase washed with water and dried. Evaporation of the sol- vent followed by Jones oxidation61 of the residue gave a Single product, the Eggggfhydrindandione 26, and some start- ing material (cyclOpropyl methyl ether 66) in a 72:28 ratio respectively. Spectra of the Eggggfhydrindandione were identical to those obtained for the major product (26) ob- tained from the base treatment of cyclopropanol g'and the melting point (167-1680) was undepressed when miXed with an authentic sample. (b) CyclOprOpyl methyl ether 6l'(98 mg, 0.50 mmol) was reduced with 50 mg (1.31 mmol) of NaBH4 in absolute EtOH 78 as previously described. The product obtained was dissolved in absolute MeOH, cooled to 0°, and saturated with dry HCl. After it was stirred overnight, the solution was diluted with water, thoroughly extracted with benzene, and the organic phase was washed with water and saturated NaHC03 solution. Evaporation of the solvent followed by Jones oxidation of the residue yielded the E£§E§fhydrindandione $§.(72%)’ None of the spiro diketone 61 or the gig- decalindione 26 were detected. Preparation of CycloprOpyl Acetates Z6 and 11 A solution of 0.18 ml (1.22 mmol) of diisopropyl amine in 0.6 ml HMPA at 0° was treated with 0.70 ml (1.33 mmol) of 1.9M nguLi, and Stirred for 15 min. To the resulting lithium amide was added 200 mg (1.11 mmol) of cyclopropanol g'in 1.2 m1 DME followed by the addition of 0.7 ml of TMEDA. After it was stirred for 1 1/2 hr, during which period the solution gradually warmed to room temperature, the reaction was quenched with 6 ml of Aczo and stirred for an additional 15 min. This mixture was poured into ice water saturated with NaHC03, stirred for 1 hr, and then thoroughly extracted with ether. The organic extracts were washed with water and dried over Na2504. Evaporation of the solvent gave an oil, best analyzed by a combination of 4% QF-l and 4% SE-30 columns, and thereby shown to consist of four components: 79 (1) (1§f,3a,6a)-3-Acetoxy-6-methyltricyclo[4.4.0.01:3]- decan-7-one (11, 30%): ir(film) 1750, 1708, 1213 cm-1: pmr(CDC13) 6 0.37(d, J = 5.5 Hz, 1H), 0.95(d, J = 5.5 Hz, 1H): 1.03-2.90[m, 16H including one Singlet at 6 1.45(3H) and another Singlet at 6 2.07(3H)]: mass Spectrum (70 ev) m/e (rel intensity) 222(1), 180(22), 147(62), 43(100). Aggl. Calcd. for CH02: C, 70.24: H. 8.16 Found: C, 70.22: H, 8.21. (2) trans-1,6-Dimethylbicyclo[4.3.0]nona-2,7- dione (26, 16%): The pmr Spectrum was identical to that of an authentic sample. (3) (13f,5a,6§)-5sAcetoxy-6-methyltricyclo[4.4.0.01:5]- decan-7-one (11, 40% yield): ir(film) 1745, 1715, 1265, 1215 cm"; pmr(CDC13) 6 1.17(s, 3H), 1.21-2.70(n, 15H, in- cluding a singlet at 6 2.05); mass spectrum (70 ev) m/e (rel intensity) 222(2), 180(31), 162(48), 137(49), 43(100). 523;, Calcd. for C12H1303: c, 70.24; H, 8.16 3 Found: C, 70.17; H, 8.03. (4) An enol acetate, isolated in 11% yield, was identi- fied as 6-acetoxy-Eggggfdimethylbicyclo[4.4.0]non-6-ene-2-one on the strength of its pmr and mass spectra: pmr(CDC13‘ 3 singlets at 6 1.11, 1.38, and 2.15 are superimposed on a multiplet, 5.29(m, 1H): mass spectrum (70 eV) m/e (rel intensity) 222(1), 180(86), 165(54), 162(41), 40(100). 80 Base Treatment of (16f,3a,6a)-3—Acetoxy-6-methyltricyclo— [4.4.0.0103]decan-7-one (ZZ) To 1 mg of cyclopropyl acetate ZZ.in 8 drops of MeOH was added 2 drOpS of 0.43M methanolic KOH, and the reaction was monitored by glcp with a 4% SE-30 analytical column. 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A complete description of the crystal structure of this bromo derivative has recently been published: J. D. Yordy and M. A. Newman, J. Crys. Mol. Struc., 4, 121 (1974) . "' J. Haywood-Farmer, Chem. Rev., 22, 315 (1974). R. E. Pincock and J. Haywood-Farmer, Tetrahedron Lett., 4759 (1967). D. A. Lightner and w. A. Beavers, J. Amer. Chem. Soc., 66, 2677 (1971). L. A. Spuriock and R. J. Schultz, JiyAmer. Chem. Soc., 66, 6302 (1970). P. G. Gassman, J. Seter, and F. J. Williams, J. Amer. Chem. Soc., 66, 1673 (1971). B. R. Ree and J. C. Martin, J. Amer. Chem. Soc., 66, 1660 (1970). P. K. Freeman, D. M. Balls, and J. N. Blazevich, g, Amer. Chem. Soc., 66, 2051 (1970). A communication regarding 101 has been submitted to Tetrahedron Letterg, 50. 51. 52. 53. 54. 55. 56. 57. 58. 59. 60. 61. 84 This appears to be the first reported X-ray structure determination of a twistane derivative. Full details of this work (with Dr. B. L. Barnett) have been sub- mitted to the Journal of Crystal and Molecular Structure. a) H. W; Whitlock, J. Amer. Chem. Soc., 84, 3412 (1962): b H. w. Whitlock, ibid., 22, 4929 (196877' K. Adachi, K. Naeman, and M. Nakazaki, Tetrahedron Lett., 5467 (1968). a) M. Tichy and J. Sicher, ibid., 4609 (1969); b M. Tichy, ibid., 2001 (1972). H. Greuter and H. Schmid, Helv. Chim. Acta, 66, 2382 (1972). a) J. Gautheir and P. Deslongchamps, Can. J. Chem., 45, 297 (1967). A. Belanger, J. Poupart and P. Deslongchamps, Tetrahedron Lett., 2127 (1968). c)* A. Belanger, Y. Lambert, and P. Deslongchamps, Can. J. Chem., 61, 795 (1969). Pure 66'had been previously prepared by P. S. Venkatar- amani in this laboratory. E. J. Corey, M. Ohno, R. Mitra, and P. Vatakencherry, J. Amer. Chem. Soc., 66, 478 (1964). W. Reusch and J. Martin, Unpublished work. W. E. Daniels, M. E. Chiddix, and S. A. Glickman, J. Org;_Chem., 66, 573 (1963). J. F. W. McOmie, M. L. Watts, and D. E. West, Tetra- hedron, 22, 2289 (1968). G. Buchi and B. Egger, J. Org, Chem., 66, 2021 (1971). APPENDIX A S PECTRA 85 TRANSMITTANCE (%) 3500 3000 2500 2000 1500 "200!ch [CM '1 } .1 r ‘ ‘00 6 g ' ‘ TRANSMITYANCEWS) JCS 1800 1600 I400 1200 1000 800 "IMNCV 'CM '1 Figure 3. Infrared spectrum of trans-1,9—dimethylbicyclo- [4.4.0]dec-6-ene-2,8-dione 2-ethylene ketal (66). 86 I'llrflnifllhl.l.hhlcw 1500 Arm 2K” tcw. 101' I'II'I ..l. . ". 4'4 (M111 ”W ii 7 4 54.11’JXL .., . ..w: ... . . » pl _ 1 _ q i u . _. . _ 1 I} b .171) V .I '1. #1111 (A 30MB 3500 3%-.-- .-:..- i... ....-- .. ..... , ... :... L... “l. . , i . .u . n . .u m... m . .111?) r w i _ i I--. . . h _ . n .1 ._ .. +1 ..--.1: 1.11.1111 a w _ ..-1 :1... -- L1. . ..:; H . u . ..... _ :ngz ... . .. _ :.:. m- . _ . l . 1 _ i; . .w: ...-. 1 . ..w. -:. a.) 2.6;. .mmmn m - L M .. I a. 01"}."10‘ . V 5.----. -..... .....- v 1 o 1111.. 11.0.1115 i .m .. . _ 19115 ! p 100 .M. 0 8 0 0 6 4 1...: muzfiezmzée . , . ¢.- .__._. “—- I 1 1 0 4000 "(QUENCY ,1)..r..../..~n7g ' -.'. .-.-3- '2" 'f) 240 40 <( 0: 2O O 3 . :‘ . . . ; . . _ _ , _ . : _ . , 4000 3500 ' 3000 2500 2000 1500 "EQUENCY (CM 80 b O TRANSMITTANCE(%) 1'0 0 2000 1 800 1 600 1 400 1 200 1000 800 IIIOUCNIV KM) Figure 8. Infrared Spectrum of (1Rf,5a,6fi,7a)-5-hydroxy-6,7- dimethyltricyclo[4.4.0.01'5]decan-9-one (66). 91 YRANSMITTANCEHS) 1600 1400 1200 1000 800 'IEOUENCV {M ‘u 100 100 80 80 E 5' 2 6° 60 < E 2 4° 40 ( CZ .— 0 _- _. 4000 3500 3000 2500 2000 1 500 lullnn urv I’DI' Figure 9. Infrared spectrum of (13f,5B,6a,7a)-5-hydroxy-6,7- dimethyltricyclo[4.4.0.01o5]decan-9-one (66). 92 TRANSMITTANCE (7:1) 3500 3000 2500 2000 1500 moumcv (on I; 100 80 g? L U 260 < p— E ‘2 :40 1 ..... 2 - 1 ' H . . -~ — »---— —-—~—— , , , , -_-._.____, 20 : _ . ( .,,_ a. -1 _‘ a, ((l__ % 1;-..1. -1 --: _ ~. ' ; H 1 E i ; r 1 1 E t 0 V _ U 3:: .3 1800 1600 1400 I200 1000 800 Ffl’OUENCV ICM 1 Figure 10. Infrared spectrum of (16,6a,7 a)-1,7-dimethyl- bicyclo[4.4.0]decan—2,8-dione (66). 93 -~-;-100 i l l 1 1 - ’a- — -.‘w -ud . 14L 1 liiL_L LLL' 1 .... i _L 0 . . . .- .—.-~..-—.— ——1—.——’. -.——— ...-... -..—- 1 l 0 I . . , ‘ . A - . . --—’ cs- O“-~--- .~.—>-0- . . . 1 ‘ I u . 2000 2500 unoumcv '(M n 3000 100 Z<:=2./.Z<~.:. 20 1500 3500 4000 O 8 1.00.;I1VIIIIif’sO-OIIH1-‘1‘. )0. nl I . 1200 1800 '330 100 O 8 6 3932525; 800 1000 1400 1600 ‘.\ .-.ENC'1 . rc- Infrared spectrum of 8-ethoxy-trans-1,10-dimethyl- 7-diene-2-one ( 8). bicyclo[4.4.0]dec-5, Figure 11. . ...-5.--. - .L. 0 .¢ 1 ..-! 100 ' i — .- u..- .v ----0-0-7 0 80 0 O o—-—.-n.—o--o—o—._—-.a .-. .. . ...- I ,A.. I I I a. O TRANSMITTANCE 7‘.. .J-J—gL. KM? 80 4o I -- ....-- r -7 LB- 20‘ — ~ - —-~—«: - : _~--- ! , - ~ ;~ ~¢ 20 ' ... .. i E I ; “—”" ' _’ _"‘"*'”T' "”""""”—"T‘" "7"" " ' " 3" ’7' i f ' + - I - . 'r ,.‘_ . ; 2 I I . L ' 4000 3500 3000 2500 2000 1500 REQUENCV CM' -- ...... - ...“ __.___ -- - "'1'": ' ' - - , i T | '1‘] ‘ 00 _ .n- ' a 3 2 r ’u; - :-- ...- -... -_; I _ _ __ _;._ I I - 5 I ‘ _ : 3 . r' " "j I ‘ ‘ “ :"fl ——~-:-——-——-~ ; ——- - —~- 7— - —— ...- --— i so I i-.. i..I , I! ‘ .._-_ _- T"? I - .. I I . I - -- ; .1? I40 . g.- , :.: I i ' :--I I 1 I I I I ' E i i ‘ I ~— . i - ; .'... E... ? -...‘I {)0 . . . ‘ I I E - I . I r I I - I . 2 I I I : ~ I .. 0 i -- ‘ 4é . . .I ... . l . ..:... I I I .. -4 I I : . I . : I I ' I I - . ' I I I ' I I I I I . I I i J ,, . . ....l...._...._...1. ...... -.--.-_--..I.__.- --.. ..L..__.__..:.._._. ..I... _-.__J.. -... ._.;_.. .-.—L. I ...; IL) 3300 I800 1600 I400 I200 1000 800 MM, ,--.' v -u, Infrared spectrum of (5a,66,7a)-7-hydroxy-5,6- dimethylbicyclo[4.4.0]dec-l—ene-3-one (£1). Figure 12. 95 ..--?a-:_T..~,-p..“.-P*-~w——.—Jq—.J~. --Jqp.d—.lo—‘n-TL--L--M~q.c—-1 sh-rl—fiLcch—A;J—A TL IOOI»"I"I '. . .4.... - I I 0' ‘ I I I ' ‘ I t F I . ’ I I ' 1' t i I' I I E '7 I ' ' .' I 80 ; ‘7 ' ‘ I “J . ‘-) 60 0 z ; 4 . ..- , . c .. t C: 1:40 - *'r -— . < ': (X I— : *f‘ 'fi' "‘ .MJHWIUE ' . i . , 2o—~--M~—-~—~:~— -em:-~I~¢—~«~—~ - I I . i I '“M j—‘E'H'w‘m—‘H 0“ ' I I"'I . . 1.- .. “r“‘I-."f“""" .... - r. . 3500 2000 3000 2500 "(QUINCY CM 1 007 +- it” -, — 2;.-.- Tm“ — - --- r, -, — - - -~- g I“T““I"!*fif7. F I ‘7““"I";"s‘ : 2 ; I L.-- ._......L....._ _ -L... L__ --- .'.- __I___.__w.._ __ .--- 7. ' J - ‘ ---... ' I I I" I ‘ I ' ' - ' ' . ‘ . . . I I “ I" : i g ’ I " ' ” *‘ “ ’ no? ~f— j I .— g- —-L~——*.m——«—;—— —.“- -.,_n___“_ ——. ~ 4 a» i .I. 1- L g- -I E - _- - I- I é I ; I ‘ i 50 .- “- r 7 "- -' ‘m‘ f“ ‘ " ' "4 I : ' 2 t i I f 8 I- - ~- ' 'r I - -3 I "-.— -.— - I °' " - ~ : " T" 1 I I . . ; E I ' - I 9 I I ; , I- .. -. .“ H--. I I I I..- .3--- -.I ..--...-- -. . . .7 ~\ 10 ‘II’ I. . , ,' :k - i 0:, . ' I I " ”It“ -' -° ' ' I” ‘ ..-..-“ I' ‘ ' ' 1 I It I I I I I ' I I I 20““ ' I " f "‘I'“ 5 I 'I‘ ' ‘I‘m 1‘ 20 I I .i I I I I I I = 3 I . 5 . _ : ' : z I ' I . , . .l i J - o u f. o z - E . f - ...: :.. 1 . . . : ; ‘ ’. 2 I f , r . . I g ‘0. .....-_.I._-.,L-.-.-.I__-.,... 3.. . . 3.. - . - L.-- --- I ..-.Lm----..._. v.4. -..- u.---..0 2000 I800 1600 I400 1200 1000 800 Figure 13. A Infrared spectrum of (56,6a,7a)-7-hydroxy-5,6- dimethylbicyclo[4.4.0]dec-1-ene-3-one (fig). 0 b. . .o n .I.-..ICI OO’I'OIV.IIIIIQ. ...l... I. II-|’| ‘CI‘IIV‘IIOI..II .ulo .ITIOIJ 96 .................. ICM" 2 23X) "(QUINCY . MI- - . ... I . . _ . L :1] ..I n W .* , . . . ... u L I.c.o..ur|cll..v _ . U . ,r I. ........ < _ .. ... . . . L .. . .. o . ‘iil‘no‘ui II .I.- t . 6..- _ . . . — u . g .0 fl . u. _ v I» P m voll. . . . u o, w h It. 0 LTIIIO uuuuuuuuuuuu m u , l o . . . o .I. .. r a . viii cigil AT‘IL’OO. . . . , .. I u - . . .._. ‘ . ‘ o . . o . . . _ .. . II. I II 1!. L! .L. p . . a - . Isooo' _ , . » oil... .0 ._oo .0 I. r . w w v o ...... . _. b . . .4 .. I..- 1.-.“; .. « m . _ .. F .. .. M 4 r . _ . a . . . , . . _ r -.TIL. - I" _ L _ . _ I Oloitt; n.iIIOII!II.‘IIIIIO. 0 '0 I-J'cble! 0.. ..I . - . lilo--.‘ IIIIIIaoIZ L. . I!" I '33:! 1‘01.-.‘ ..I O . .c ”*”T' I I i In 3500 ¢ | I+II_ 800 1000 1200 \1 Hn'l‘flll N! \ .. 1400 1600 -IfiIIIéI.II sq! . h v. I'OII+' 4..-. -..-It... .oll '1... A 1800 -—.——T- -——§—-—-——o ._—_;___i--..1__'-.§... 100 4 fl: muz rfllo. . . H _ _ . . fl .. . h . .. ....4 .. . .. .. . ...* - o ..o.+ ........... m...¢6|o,fiuotoocc.vu. I 016 . .... .. ... .. ... ..* o . . . . ‘ ... u .L a: a a“ W . .;. :f » . _ . M r w i i . H _ . m a . J. ........ .. ... . .... f . . H ._ : . _ . , . . _ . L , 100“"? w 4 Q; muz——- -O . 1 I , I . . I I 3 l - n I . . H w _ . p . ._ m m _ , . c . a W . o 5 . +. If: . :M . _ . . . . 19., h : _:;;v;.. . w . 1%.. M: . 1. - :--...._1:. . . 1| m m L . . _ . _ - I; .1 II I ......... . . - :-:.-- .....-I-..w..1 2mm FIEOUENCV CM ' . mxm 0 0 6 4 33 8555.25: . I- L _ . a . i M W .— . .1; . . . . I.~ I "I _ . I . O I o I . I.I. t.. o A . . . . lc ..~. . " ..:. . . v ..I. .. ... . . 1 . .1 . I . o. On. . ....o.... ...-‘0..A.n...u. no... ... ...fi..o.....oo LI...” . .... .. . I .rl . . . 0 0 2 «xm mxm 3500 moo ‘ 1 I I -—-—.—_. -. o -:>O p..- .— - ‘ 1 ‘ bxk 180C. _ : 3° 5025:3325: 2000 w -methoxy- -one (96). n:8 I4§* :6§_* I 7R*) '2 .09'9ldeca .2§_* .0 Infrared spectrum (13f 1,7-dimethy1tricyclo[4.4 Figure 28. 111 100 80 80 60 60 40 40 TRANSMITTANCE(%) M O 20 0 ; 4000 3500 3000 2500 2000 1 500 ”(QUINCY KM '| 1 00 E'; I.“ U 2 ( .... ’: i (D Z < K .— 20 1800 1600 1400 1200 1000 800 5030"!va TM . Figure 29. Infrared spectrum of (18*,3a,5a,6a)-3-methoxy-5,6- dimethyltricyclo[4.4.O.0T:3]decan—7—one (22). D O TRANSMITTANCEUS) TRANSMITTANCE(%) 8 b 0 go 112 3500 3000 2500 2000 i 500 ‘IIOUNKV «M '1 1800 1600 I400 1200 1000 800 "(QUINCY (M '1 Figure 30. Infrared spectrum of (1R*,5B,6q,7a)-5-methoxy-6,7- dimethyltricyclo[4.4.0.0T'5[decan-Q-one (2g). 100 (D O o O TRANSMITTANCE (7.4) 5 O 20- llkOUlNCV ( M' ’5 9.. LU U 2 < )— : am.“ 5 __ 1. 1 . <40~~~~ .-. ~ 1 1 11 40 g 1. p- »- Mn 20-——+-~-~1~ ‘ :20 “r; .4 mg o———~--—— 1 1, 1, - o 2000 12m. 1 1, 3.13 Figure 31. Infrared spectrum of (15f,3§f,65*,8R*,10R*)-8- methoxy-1,10-dimethyltricyclo[4.I.0.03r3]decan-2-. one (101). 114 100 N O 80 2‘; M] U 2 60 60 < .— t 5 Z 40 40 < I! y. N O 20 4000 3500 3000 2500 2000 1 500 IIEOUINCV KM '1 TRANSMITTANCE(%) 1800 1600 1400 1200 1000 800 Ill QUINCY ICM Figure 32. Infrared spectrum of (18*,3a,45,6a)-3-methoxy—4,6- dimethyltricyclo[4.4.0.0T:3]decan-7-one (105). 115 100 m 80 0 8 .$.muz<:.zmz<fi 20 1500 2000 2500 ”[011me (M - 3000 00 35 .0. 16\ 1"; ..6 .4 33muz<53mz<fi 1 1r». 1 . _ s . r 1 .1 \s . . 1 1 h 1 - 1. 13V. 1 m . h. .1 1 1+. . u l' 1. . .. . .11., -. I. 1 1. - - .... 1.1.111lllll1..1u.l _ _ u . . mm . . H u ..H .1 L w m. .1. 1 . . _- 1F 11 h: .. --1. I 1 .NHHU. _ .1 :;_.-- J- -1 . r 1. u _ _ . _ 1. . ... r... ... _ . w. I. m .... 0.. . _ 1 . 1 . . - . _ . . -- . 2 -. 1. 1.11.11 .. --. . p. H . _ a n _ . . . 1 . 1P1 h 1 L r 1 o O O o 0 0 8 2 1| Figure 33. . n4 _. 8 n . a \I C * e Szu 9] 08 * I Rt. so. * 0 S.. 6.9 E4 [ ago .1 * c Rrx 1.c (.1 I sit 01. mm. r.e 1t m c:i m... soy d1; e . r a m. v.0 crh nrt tie m one (106). 100 a O 0 O TRANSMITTANCE 17;») ‘ o " ' ' 1 ; : ' . . . L ; . g l 20 y————-—.—— -.-.-¢—<-.——-—-—<~— —- “-—~ -- -» -Q- <- A --- - - - - - . - . . . - .—»—-—’—.‘ ' . 1 ’1 . ‘ 1' ‘ . I 1 a 1 E ' 1 . : i - i 1 - 1 1 : r ' ‘ t . . . ‘ 1 2 ..-...” 1. ...... . 1 . -1..- .11. -. . 1--.. . . 1 . .. 51. , . _ . 1 1--.- . . ..-_____ I ‘ I 1 1 ' a 1 1.1 1 5 1 i ‘ - 1 3 : ‘ i -' 100 80 60 4O 2O 49300 3500 3000 2500 2000 1500 "I! QLENCV (M' A. ‘4 #“g - ”---—n . . -- 5 o 1 1 1 I 1 o TRANSMITTANCE (7'5) ~_---‘. ...—out -‘ u‘F o. 1' . '1 1 ;:' VJ! : 1 1 1 1 1 :1 1. : 1.. . .1 p 1. 1 . 1 L 1 ' 1 O :u a . : I _...._.-.- 1.... . 1 1 ‘00 —. .11-- - . . . 1 1 _ 1 _ .---1---.---...__1 .. .--. - . 1 1 1 1 : . n . _; . . 1 r . . . . . . - I! _ ‘ “ _ >________+ 80 -11“ : r _ ..1 1 T 1 ' “ " 1 1 j _— O — . 1 9 1 i .1 1 2000 1800 1600 1400 1200 1000 800 moumcv 1m '\ Figure 34. Infrared spectrum of (13f,5a,65)-5-acetoxy-6- methyltricyclo[4.4.0.01I51decan-9-one (22). 100 80 60 40 ‘20 80 0 O A O TRANSMITTANCE (‘N 20 c L __ -._-._. _._.11 r 1 . _-_—__— 4000 3500 3000 2500 2000 1500 O VIEOUE'KV t .u TRANSMITTANCE (fly) 1800 1600 I400 1200 1000 800 'IEOUINCV lCM") Figure 35. Infrared spectrum of (15*,3a,6a)-3-acetoxy-6- methyltricyclo[4.4.0.01 '3'] decan-7—one (21) . 118 .239: 32% ~33 mcoamfiwum mcoflcuw.mnmcwtmlomuno.v.v_oHo>oHnH>£umEacla.Hlmcmuu mo Eduuowmm Ham .mm musmflm \ 119 . 23an 3.19 mcoflvnmrmuwcwuouomvnHo.v.vaoHomoflnamnumaflnlm.Hnmcmnu mo Esnuow m Hem .bm wusmfim 3L _ 3 3" 3 E at 3 q. 3 3 d ‘-;-‘-AAAg—og‘-“ 120 .Aaaoauv «we mconm namumw_n.”o.o.v.v_oaomofluuamnumenm-axoucmsum-Amo.am.[Mae «0 sauuummm Ham .mm «Human W. 1.! Jq 1‘ 11— q 1“ ‘ ‘ - 4 ‘ ‘ ‘ - 1‘ 1“ ‘ _ ‘ 1. 121 ’LrlaalrlL .2258 Q8 oaoanucmomEoJo.o.v.$ -oHomoflHuflmsumeflouoH,oumxounmnunuAwofium.cm~*mflv mo asnuommm Hem .mm musmflm w. 'm- p. —-—v- r—vv—w-Vf‘vvv— 122 . A389 any maonmlcmomv -an.Ho.o.v.e.oHomoHHuamnuwaficnm.oumxouoasumuAcm.mw.cn.«may mo asuuommm Hem .ov musmflm o 3 a.» 3 Ext 3 e6 3 3 1.3»‘4. ‘1.1_41J._‘.+4411+144“41_‘«‘4_H r‘q‘J a J ‘ 123 (A) u 73 0.0 35.. ...... ... — ---+--+ ~za~ ~~ ' 11_ .1 z ..’iiii‘ E;:-1' x ”f' ._L - ..L— ——oo~ no. ~~ . v . ..I. 2‘7: '..'11. :'. - :' r “ ..... :37" :7 £3335 '1' x '''''''' .1' 3* '° ..' :41. 1'.- V’- % ........ 13.1; -.11. 11.11i1 . f g 11:31 . 1.... 323‘" . 1. .3' 3:11. * "ff; .1 1:2”: .. .3. :-'*“~" 2:?"- t'1'T":1'-~:7t-t':*"r7"'r.7 17r‘r'“:"‘"'.t '1 H H 3” ~3ii"iii§';3‘i733“5= [sf-73 ..‘ . .' 33:; . 1. .. ......‘t'tt'3 I; i- 3 -.-.-l- 7531*: H. . .'1:1L.1,. ..:;th :1. x .; :§.‘ 3. :3'33'1' .:;..:‘;.;‘ ::.11‘ 35.15:..‘11'? l gritglfiwnsravw-‘hww 7‘1 ~::“‘-“-?‘§i‘?zt' 5?'-1&::r-?‘?1.1 .. " “E31" - 31.11": 31' ' s15“ . 11“ ‘1 ‘ 273i: :92» ‘51 v, i1 : 7,441 - . . 4L l.1:1 .3' .L LL' .. L“ LLA ‘.. A AA A 1A ‘ AA 1 A A A A l ‘4‘ A l A4 LA I AA.‘ A l LAAAl u u u up an '9' u u u ‘o 0 Figure 41. (A) Pmr spectrum of a mixture of (1R*,5a,66,7a)- 5-hydroxy-6,7-dimethy1tricyclo[4.4.0.01'5]decan4§Fone (50) and (1fi,6a,10a)-1,10-dimethylbicyclo[4.4.0]decan-2,8-dione 733) (CDC13). (B) Pmr spectrum of (50) after Kugelwbhr distiTla- tion of a mixture of (Q9) and (£7 (cuc13). 124 I 4388 i ocoum ucmumofim.“o.o.v.vHH>numeflnun.oumxoucmgumuAd>.dm.mm.*mfiv mo asupommm Hem — \1334—11141—11111—13J1—1 1+—11‘< 1 ‘ q 1‘ ‘3~ I A.-.- _‘,1., O :-u-_- - - “3'. I ...: .Nv wnsmflm 125 u . . . £3098 Que 0203 w mucmomgo v EoHomoEHEuoaS- u .73 b 8de no 233QO Ham .3 353m ‘ ... A“.“‘ ‘1... p—w- - ”..-—popu-nowvo n '0. . __u42'-oc o AAA-.L‘ILLA qggcvn —— y- 126 .AnHUQUV «my maelmlmcmfin ->.m-omu_o.v.v.0HomoHnflmnumeflunoH.Humcmuunmxonumum mo asuuowmm gem _- -—_”-""“— ._-- ...... um .vv musmflm 127 4389 98 maoumumcmufi -omn_o.v.v.0HomoflpHmnumEHouo.mtmxouwmsuu-Ace.mm.cmv mo asuuummm Hem .mv musmflm o q. ...—u 9n ...—q 17 .at ‘1 ‘ ‘ ‘ 3‘” J3 ‘3‘ war. 128 . A I 89 Away «co. m- we? H -omo_o.v.¢_oHomUflnHmsumeflonm.mumxouumgueuAou.cm.ume mo asuuommm Hem .ov musmflm F. q. 3 3.. 3 2. at o.- 3 3 o.- 1 11 4 J ‘ W ‘ I ‘ I — ‘ ‘ ‘ 4 — ‘ ‘ d. ‘ _ ‘ ‘ 1 1% A_1 ‘ ‘ ‘ ‘ q 34 ‘ ‘ ‘ - q ‘ 1 1‘3 _ d 129 . . Away 39.6 um mucmomo.o.¢.v_oao»oflnflmzumeficuofi.a-AooH.cm.m~V mo asuuommm Hem .bv musmflm p o p 04. ad of 2? It 06 9.. 3. o.- ‘3 ‘ d J 3‘ d ‘ ‘ ‘1 ‘ — ‘ J 1 T .— 1 ‘ ‘ ‘ - 4 ‘ ‘ ‘ — ‘ ‘ + J ‘ ‘ ¢ 4 q - ‘ d ‘ ‘ .— ‘w—F . --JZ 130 1« Ed! HIDE H..— .Ame 98% ..m.«-58384.3205312323..on8289c: mo 5:30QO 25 .3 833m _—4_- 1.. g--- 131 . .Anaunov Ao V mcoa um mucmomcHo.v.«Hoflomoflnflmnumefiwum.H-Acm.co.mfiv mo enuuwwmm Heme .mv wusmflm 132 3 rail! «..‘; 22 . 2438 onv wcoflcnh.mlmcocHo.m.vHoHumownaazquHvtm.Hlmcmuu mo Esuuommm Hem .om musmflm o.— o.« ad ad .8 It 0.. 0.. 0.5 o.- _ ‘ W‘J ‘3‘ ‘ ‘ 1 . + d 1 ‘ 133 (A) [J's—‘..‘- _____ 7?: l . . . . I . - - . J u m u an i t E .- ‘.--A .L A— _‘_ .— .‘ .4 A -...A AA_. 77w. ‘v r vv —- vr—vvw v‘ r w I A A A4. 1 A A A A l A A J A l A A4 A l A A A A_l A u u u n W‘!’ 4.0 u ' - ' lbi- F1 ure 51. (A) Pmr spectrum of (1a.6a.7B) 1,7-dimethy g cyclo[4.4.0]decan-2,8-dione (92) (CDC13). (B) Pmr Spectrum of a mixture of ~n’and g§I(CDC13). 134 Ammv wcoflcus.mumcocHo.m.v_oaom0flnamsumefluuuAom.mo.ofiv mo ennuo ._ w . o . _ iw:_ .Amauouv mam Hem .Nm mnsmfim ‘ 3‘ 3‘3 A— 3‘ 135 (A) H i l Iv‘v‘v- —~-v‘— ‘hv—w‘iv—‘fl v he‘s-:2“ wwfifi IWM g--.- . .l ..J .. 1- 1+-- l-.-4114.irl u u so u mm u so 20 ml 0 (B) ’l H ..’-d / -1..-L1-.-LJ.J--1...L 4..-Li---l---.l u m In 51'".be u so 20 L0 Figure 53. (A) Pmr Spectrum of (1R*,3R*,68*,8R*,10R*)-8- hydroxy-1,10-dimethyltricycTc[4T4.Ojb3osTHecan-Z- one (100) (CDC13). (B) Same Spectrum taken with de-DMSO as the solvent. 136 ‘ 1‘ .Amaonov Amofiv «some us.m-mcocHo.m.viodosofluuamgumefiuu1m.m.Hu”ww.um.cfiv mo asuuommm Ham .vn mnsmwm 137 .Amaoooc Ave” can moflv macaw -m.uucmomo_o.¢.vHoHomoflnHSsuoanum.fluflmm.uo.cfiv mo asuuommm Hem .mm ousmflm 138 52... .Anauouv Ag wusmflmv cacao 50am ~ ~ 0 H . ab.mlmcoc.o.m.vHoHomUHnH>£umEchm.HIOEounlmnAmm on any «0 Ecuuoomm Ham on m . mf‘n". "" -~‘o- o -“~I.-‘l“|\u ..L‘Ui'l— '. :'.': ——l.~..o.oo.§-' .Jl 3-1M? .‘ 139 .1488 8 853.5 mcoumémwmu.mhm.o...o.whiowomoflugfimficuofi.H IAmxocomasmmamucmnoeountmvImlA*moH.*mm.*mm.*mm.*mHv mo Esuuommm Hem .hm wusmflm — “5‘ b —M"§ r,‘ .. 7;- 140 u H III! f~0 Icmow UH”. «o.o. v.v_o Homoa .uuam sum I E mlmxozum E lmul AU ®.c .Am m. HUG *mfiv mo wruwwmv mco 0mm In Hem mm madman 141 A J U G we awe 0 G OI ml- Cmum v m5 H U a U H .H u % g“ 0 E w '%x o m E m A d m m Hv m E d H wm m H E m m m m H 5 m om k; ..I. lllluuug. I 1". 1 lllllll...]\ 142 ll okaWv'mCOH-Iw'cmuwmvmh. NOOOO¢O¢H 'OHUWUHHUthumEHG'F~H'%*O£“0EINIA*mh~*mm~*m-*mfiv Ho Engummm Ham .om mndmflm ‘.AAA“ 143 I I .kwwvlmcohmucmomof.$664; IoHomoHuuaxnumEHUIh.HImxosumEINIA*mh.*mm.*mw.*mm.*mfiv mo Esuuommm uEm .Hm onsmflm co 3 en 3 — a... E 3.: 3 ed 3. Q. 1 4 d I q I 1 — + 1 T 1 — 1 1 1 1 _ 1 1 d A A. ‘A “--: ..- . .--... w o- - . ._ .-.-.- AWL; ‘ - .- .-- . .. . ---_.. -..... .-. doc-- .d l.‘b‘h—'-'-\'_Jt..'—'- all. ‘..'.- 0.. \ IO... 144 .189: “me mc?b..:mom3n;o.o.v.i IoHomofluuamnumeflcIo.mImxosumEIMIAdm.cm.dm.LWHV mo Enuuummm Hem .No musmfim 3 3 3 E st 3 o. 3. q. . 1-. ... .. ....q.4 .441...I.q.I.1. .I. ... («I l1IIIII IIIIII II I II I IIIIII I I LJIII #3 I1 I ...- _-_--* L. - 145 ‘1 I3 I !.§‘LI "r r . “:88 «my mconmucmomflc. 364.1 IoHomoHHuamzumEflth.mlmxosumEImIAdb.dw.mm.*mflv mo Eduuommm Hem .mw mnsmflm ..-..— *fl-w -..—.— -——.._J--C.¢&---.a — ..'—...;- ——__§.—-..‘. _-~l 146 #30an CoCIwcohmémomn I. no.9 w. 1 IoHosoHuuascumeflwuoH.Humxonumeumufi*mofi.*mm.*mo.*mm.*mflv mo Sauuuomm Hem .vm musmflm 147 m“-.§aw.u” ' .Anaoaoc Amofic manusIcmomc_a.Ho.o.v.v_ IoHomofiHuHmnquHcIm.vaxonuoEIMIAcm.uv.dm.*mfiv mo Esuuommm Hem .mm wnsmflm 148 . 6.3V mcouuucmomgmgoééé. IoHumoHuuawcumEflva.fiwaozumEIwI:.wm. ».mw.*mm.*.mm.*m31 m0 Esuuowmm Hem .mm musmflm -- ‘.V' -..}.- *. 3 E at o.- 3 3 o.- ‘ q ‘ ‘ 4 ‘ _ ‘ ‘ ‘ C - ‘ ‘ 1 3‘ ~ 1‘ ‘ ‘ 149 I...- . £E.. I. 389 $8 28$ Icmomcflm.Ho.o.v.vioHomoHHuHmsumEImImxoumomInIAmm.cm.*mav mo Esnuommm Ham .bm musmflm o 3 ow 3.. o... 3 at o.- 3 3 . I J o.- . «Ia 111 . . . . I .. _ . ..11 a ..1. 1 _.,1 . -... I I... . _ . _ ‘ J“,II“'—‘J~O*- ' ' O n- s&.—.:—‘— ’ ’ ‘ J! m 1... v“ .\ 150 . 23mg 3.8 mcouuucmomu Ian.Ho.o.v.vfi0H0>0wHuamnumEImumxoumomumIAco.dm.*mav mo Esuuowmm Hem .wm musmflm u< o m musm o rm 0 H H H m N or 3 on - 3. - 2a 2. .... - I U\ n. 92 .: cm. I o I. b S o2 one 2.; - o - . a”. I 02. or - Ed I ~ ’ ’ 0rd om - . .__~«. .1. O. on. or 151 xeea asea % 3 3 cm 92 .Img macavlm.NumcwlmlomoHo.v.vuoaomoflnam£meHvtm.Hlmcmuu mo Eduuommm mmmz .on musmwm AK! com or. 152 cu. ow. o3 on. or. on. 92 .0: a2 0? on or o. on or _ . a¢ ...w,r;.:.Im;.-I _-I . . _ H ..m -....:...I.... f2..- ...-w“ , . . ...II II M- _ I... .1 H . . .al IIII'HQIIIIFI|IHPI|I'.III!IMII.O.II . . “w .I LI 111'”? [.1 I'll-Ill ..‘.0— III Inn-ion»: I. .Q I 0‘ .. I. --.-.. “If _ I a . ., I H . “ ML- q .u I - ..I. I .w- I. I. ..IJIII .I. {till-1-..! - m I_ I i IIIT... .- Is. :I 3 ¢ — p . a I o - . I . . _ . H _ h - . . I . w _ .I- I: I. WI.1 __ ..... A.“ .I. . . I, .- I. I. . , I I ...-I _ I .. I; I -.I.- T m . a . I .. . _ . h a n a w . _ . _ a . u x . . fl ” u. .. I”: .u . . ..c . ..u . . . . .I:;:IIIIII-IIL II-.IIII+.-. . I“ III, Iz-r-.- -I; _ .I I” I .M I“ m I w; fin . a H mm _ w I I I I . .. . . . . . - . . . . _ . I. VJII51;.HV*uII. . . *- I;W_...I ".44; :e M. I W _ .-.-II! III-.-- III-IIIIIIIIIII- I III I-.. 3 . - p. I w, .:.. : .... r" _ _ . ._ - H I _ . H _ . q I _ H ._ _ _ I . - . Q ..I --.- I- _ - I - .II I...--- I-...I.-III-I-.- I I I I I ”I I... .._ I _, I _ . ..IIIIIII III? II N _ - _ H I w w . .I.-II I L on. .- m - _ .. w H j I _ m . .-I“- ...-...-tIkiI. -I.”:t «...-.... . . n . m _ . . . . H _ . H. h I-I-IIIIII. 1|TI I _ 1p. . II!!- 0% .J ' h _ - . --HIIVIILII --IIL. I..- .. I-..‘ . I I n L_ - ...--.._ o—-——<..-- - .-- . _ 0-.-... 4. “lb—...— J l ‘ ...-nu...— .—-.. . ... -32 need asea % 153 g ‘1.“ .«wv mfimImIcmomn_a.Io.o.¢.¢. Ioaomofiuuaasumfilmlzx0uvm:|nnAmm.dm.*mav mo Eduuommm mmmz m<:\ \ 3‘ g 6‘ 02 0.: 0: 00s 9% on 2. 3 .Hp musmflm x935 9523 g 154 f"- IoflomofluuflmnumeHonfi.mImxoucmnImIAwe“ con ow. on. u. 4- 9: 03 on. 0! Q - I; ....I.l:.-a. :...JI-Ivollollllfullluu. - . . 7 _ o — . . . . -T- .. _ I I. I c . . . .. -. to. v .l. | If I .YIIoIIOII 9'. . . IL - . II I . b I - p . . _ . . . . - . . . . . . . u . '....I n . - . . . - o . . I Ola-fall. .o.L..I .I'II‘. — I ~ . _ . . . o o .I. .I. O I -.-II n I - -a ll‘.|ou I .II-1III.(. I III".I .I. I. a . .- . . o . I a u . I .mmmv mcoumIcmuwn_n.Ho.o.v.v_ .u\:\ .mm.dm.xmfiv mo EDHuowmm mmmz .Nh musmwm o$ 1‘ , a? 9.2 o: co cw _ V -— —~--o-u—— .. . I u v u m Ll ll clul' 1'! .ol T '91 I ”I .. n ...... ~ e w_ &u IV 2 0“ ea or om ow ....- 00‘ need 9328 % 155 .Awmv mcMumucmomEnJo6é4. IoHomoflHuHmnqulew.olhxouvmnlmlAdw.um.dm.*mmv mo Eduuummm mmmz dr‘ no... or .2 at o: o! 0t on. 9: o: 2: or an £ 3 on or H k. . o . _ :.-: - -.- I l u 0‘ g m . ‘ . .i¢-:-v- .. - -§ 91 M w “ ~ H . _ . . u . . . .. .T- 0* on ow 0m 4:0m aw I‘ll-.0. n2 ......— —..—m.¢---.-o . ... .mh musmfim xead aseH % 156 . 3Q mcmumucmooo_o;o.o.v.fi IoHomoflnuaxsquaUIb~mlwxouvmsumlAdh.mo.dm.*muv mo Eduuuwmm mmmz .v> madman .u>§ eon oo. .5 of 3x on. a! a? on. o: om! a...» mm on o» 0M o» ’ _ . V ... . -H -. t . . -.I. i i! t . ..- - Os . . _ . a . H . 4 . u a . . I. 1| ID a J.I.-Iluo|o|. .1 0 -II.’ .. -0. I. :H,: a J . w h w H . . . _ . . . . _ ~ * . w h 9” II C ..... LAID I] d I ...III- ..IIII‘II O ,0. ...... I _ _ M V n. p L _ p n “ xeaa asea % g I. a w l . . ,m V _ u H . . V ~ . - ..I 6-4M--|!-o..ml-n..ll.4.l..’l”|-s . L. fill. . . 7 . .. 0b: . -. m . .M .... Vm .n _ . ” m 0 ~ _ H H _r.. I rlL T-l..|.Tzh I .1 : :vw. I.-. I 0% V .w _ _ h . V . . _ hi'll - . I 11,115.:“r. ..':t'dlltllllllv VI.‘ ‘1. 11.0.140V.,|I.I .- . . . H . . V . a ‘ , . . o . . . . ... _ . _ d . a a . . . . . . . ..-Ylor.all’t ll.‘ vi:-|-¢01t ..I- ..- |.Aa6| . Vv‘ .ilh' ’ffo:1.—Io ‘.....r' O|c|.lw.',0lli . I, ..Uu-..i ....tUIl O. I t .I. ... A ... . u . om - . . . . fl . . V a. . _ . n _ H _ K _ . ...—9 V . m m a. . - m .... . .w. . ~ . A n . ‘ . _ . . . . . . 7 ..-..II -. ..--r ...s! .. :.-. .- . . - Iiflller‘rlfioo! VII.;!.T.%1.I. :.-:Ifi..- ” . . . . . . om .. V , a p 0 . . _ H . . . . h.. . . w . a .V. _ . . . _ . n . . . . . u u . r W V V w . ;::+gw:ws:4fli+;ws-:m-+:%£;!4.V _ w.<-;sflsw:+ti.a:. . . . V. V . V .. _ _ V m . ‘_ II in: “.I..” ..‘... :OHUmUHHuahnumEfioub.oumxouvmnsmlAdb.dm.mm.*m~v mo Eunuommm mmmz .01 or. . 'lOnltt 157 ni'l.a|l"ll‘4ll .‘0. tn- 9 I.V-rl-v.l?4. r _ m P! IIIII it I'll Ityl ‘ - -- ...... u . . . u . I I..- h! .IVtol, o,. . _ . . . m . _ . “ _ u: ..I 9.04 u 10' Obs . “me mamumucmoofln.uo.o.¢.$ .nh musmwm on. 2.. 0n; 0.: o: 09‘ 0? ob on o¢ 9.... o? 0‘ .:-..v ox. on need 9393 % 0¢ cm 03 . . c _ m..-...-._..--,.. _ a . . . . H. II V l I-.-.!I!..! . _ . a . P _ . . u . _._ .... .- . “V . ” .-. .. . .. ; V H . .. 158 um.«-5888.1330332523- u .735 0.4.. Jam or. up: 9‘; OJ. 0.! or. an. . «my 98% .dm.aav Mo Esuuommm mmmz n§ 2: or on on. 3. a: or. on. ‘0os on. On 02 03. w mnsmflm .H or 'J M 295 3928 % X Oh 0» om om 0% 00\ 164 -m.m-cmowoHo.v.v_oaomofinamnumeHunm.H-AomVoo.mHV .UQ-s numb. wow” u 0 n.. 0q\ 3%.. '.. r r b L. I . . ..... O V . V . I I I I I I vI II II ... I I ll ..-. . V . . . . .n . V J n V, - .. . , . m . V . . . . V _ IIIIIIIIITII . I .-I. I II V II IV . . V . p I - > v u . . m . . . . . I . I... . _ V . u u . . . . . . V V“ -.'. t. '.qu - V" I A. ..I ...lI 4 I ‘.. I- u! . --I. 'I-t‘| h . p D u . . . . u . . .V m II IQI . I ...... I0. I. _ . _ ¢ — O . . .. . . . . 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Q8 986-». «-98: 8. m. anomoflflmfimfiwé 2.. 0: OP. 3‘ ans .3 ifi on. 6.0. s Hlmcmuu Ho 0: $2 or Esnuommm mmmz Qs go On or .mw musmflm on 0‘. 0h o¢ Or on or need 9398 % 166 .— b ..I .Amm vcmemv macaw -m.mucmooono.w.¢HoHo»oflnHmnumeflouu.Hufiw>.oo.cfiv mo asuuummm mmmz on‘ or. L o! On. or. dfit 0? In I -_.--_ . I V Ad I u _ ..'. . .V p.. .—-.. | . 4 n . a- .'--...L..—¢-—I ‘ . ..— 4.. I . ‘ . V I I -o -1y——- —--'-—49~o I.-- ...4 . n . . .. V. i I. I -..-§_.JL.-J.;.-::._.i_.V-J I __..;.-. - TI. i :...-- VVI .. ‘.; I o——-~-dh¢-fL-¢-II' V_ N . w .1 . V. m . M _ 0 .I.. n ”I! 1%.! . Vi? o . . 0.3 M- q -4-—..‘...- -I~V-——+— l —. l‘.. +~_V;..-.;..:_.;..., I.. «v: 00. :_V;_ V,; ' t I . I V 3 -rV- I. i '..... ,.V V... I or v .-.;.,.V . V" .-V .VV I I ; ' . . I -.‘—-r—r. 4». --f-_-4-—.~.—.._... - . . . . . . . . .. . V . , . . . O l I IIIIOI. chap .....1. ..-._.. .--..-. -.- g. .. 0» --. . 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I I ...—...... .— ---—1 I I ..-- ' q.- I 168 new ow‘ om. Qh‘ u HOHUHUHH v mGOImlcmommmw mm. wswuwmmm mmmz .AooHl mH a: mIA*moH *mm *mm *mm * Ihxouc I IoH H IHmzumEHU 0! om‘ ar‘ on. 0?‘ 3 H 0: 62 or on or o¢ 0“ or .ow ousmHm 0‘ on on or on o¢ om oo\ xeea aseq % 169 30 N F 0P. «.2 93 02 on. or‘ _d o? \t a 0‘ _ I H 00‘ NO OHUI .N HV ma . b I O U H n A l I o“ Dmmm 85H“ mam: M . Hv m ..m d O W” . .H A V HGE H“ m w I %Odfl H o o H HO m MCOQ m 2v mm 3. co an Sm 0H5 .5 or 2 on on a. on .3 or 02 ea asea % x2 170 I‘d .AfioH can mch mGOHo Iw.mnemomvno.$.VHOH0m0HQHmsquHUIm.HIAwm.dm.de mo Ednuowmm mmmz .mw wuamHm :2 on 3 on 0.. F - H . fl . . « 4 - . ' W p .0 I ' u - I n p . m m . u 0 LI! I I 1'. '..-..I‘OIII'VII- IL I O 0 '.. I1 inllM'- | 0 o. .— I I o I...- ~I—i-~-- I _ . «-.. .-V 7 I I I I I I I ... .- “Ln—-... IV I . .‘_| —. h—o-c— I I .... ...! . I .I : b ' I _._'l.-..-*_..;..L.'. l l I , . '..... , ‘ . 2 . l *— ‘I- . I I . . - -...— -—..-- ...-.0. I —I-—-#-~ -... ..‘...“H..- I.— xeaa asefl.% . W . . . --.TII_.-.;4I.II. . : . . . ....HIIII. D V .H . ,. . 47.-LII...- H. .V ...; .. 0W ........ . H .0 o .. .- I . . . . . m w .M , .- ITI- . . : . 1. u n _ . . . . u . .- ~.... . 0 ‘.. n W . . , u _ n . . InfoI-IIu I: 01.. . ”III II . I I .“V I o hwm . . _ H _ J . _ ~ .. .V. n . .. _ u I. _ M 4...... a- O 0‘ -. . . _ -III4-4--I52IILI;II-- oo\ _ . . —. . . . _ . . . . . .. . . I.I.-II I. . . .I.. _ ~ .-..—-———.--_ - I o .. u . -—-‘— -__———.——....— I . , . I .. .o O I . I- I _-.+__... I ...—T:- I... .. .I.. -v----1r"—°'-’ -I Mfl_—.——4L —-+ ‘1 171 F‘J .AH musmfimv macaw-u.m Imcocao.m.vHoHo>UHQHmnumEHvIo.HIOEOHQIMIflaw.dm.de mo Eduuowmm mmmz 0? 3w 8a 2a. Su 33 2d 03 at 0: 2: o! 92 9: 3‘ 9.: o: 8‘ 3 .mm mnsmHm O. on 3 xeaa asefl % 0» on 3. 2: 172 oi. 9:. 3... 3n 9% an. on. o3 8... or. 3. 2; 3. IAmeCOMHsmmcmNchOEOHQLNVIwIA*moH.*mm.*mm.*mm.*mHv mo Esuuummm mmmz I .Am musmfimv ocoumJMmommho.pp.onw.wymHomoHuuHmsumefiuuoH.H ’ I d§§ on. o... 3. I ’ In? ‘1 2 _ # 3. o: 8. ur on 2. o-a 3 2 or on on ch 09\ .om mnsmflm need 9928 % 173 I . Amy mcoublcmomo Ian.Ho.o.w.w“oHumoHuuHmaumEImIaxosumEI«IAdm.dm.*mHV mo Esnuowmm mmmz .Hm musmHm .{t t on 0‘ 2.x qu oh 9h 0» oh or I! xeaa aseg % . I V H w _ . . _ _ q .4 u . . m ..... rut . I aw . ..I III. . u. 0‘ . u u m _ U m . m W _ If IoI II. .tLIIIT' ITI I LIII .. ..II+II . . . . _ . . H m w m . _ " IMI u w w . 9“ I... . o . I -. ... u o .I..- ..wIHI... . . u - - : . w LI- -..II- . . - on . .. H V b V . . . . « u u . _. m . . . I“ .... ,. . . ”I; I... _ .. 3* I. .IW. . IIMII ..-._. . n _ H m . . H . _ . . V 4 4 _ . . . . a . U . 4 a " ... V . m V . . m u u . n V b .. _ , w . “ Iu-I‘ '-.” I+ . .... I... —II..OIIINIIZI..IaI.. .Imtnlflflll _ . uqudIII _ .. q o? Ill IIIJ'I. ll .wl I ..ICHI I‘d . .- °* _ - . . ~ . ‘ _ . — ~ . u — ~ . _ . ¢ . m M . . M w u . . ... ... ..pr . w u H ." w . . . _ _ m . M _ _ u _ h . 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V. . . . _ v _ I; IIIIIIV I. I I . . . . .- . . . . . . — . IVII III «..II I’ III-III?! , . V . .Ammv mcoumlcmumNHa «o. o. v. vHoHomoanu Iflmsumaanuu HumxosuoeIuIA*mu *mm *mv *mm *mHV mo asuuoomm mum: ...... . c H _ h V V . _ LII .. IVILIVVI I V..- . 1 Ir. _ u . V V V m p N . . . a . V _ . a . V *1 _ . . . . - D V IL III IJIIII. l0 IIII II>IIJI L .I . 1 . _ _ . a _ . I ..I. I... ..I. w. h . h. w . _ _ . V. . I1 III I IIILIIII III I III! I I L__ I I T _ I I d>§ ’ I. ’ q < « H . .. .”V .m . ~ . p _ . v u . -Il'c -.‘... 9. .I.. I IIIII . . . n . h u C u, t O I . _ IYII III . .... _ .V a o . . . . . . .V m . - _ _ . . I. I'm ‘- .. O 'l‘IcO' - . V r _ . . I u H a. o 4, V +.. --¢:+II. V _ . I H V VI .. -w r V _V . . . e. _ h .V V w . M . L "lco u. H;-V+WTV .vm munmflm xeaa asea % 9» or f..2312< 177 «my maméucmomo_néo.o.v.$ IoHomofiuuaanquava~vlmxonumEIMIAdm.om.dm.*mnv mo Esauummm mmmz .nm madman 0:: as 8&2... c: at 3 92 ..: 5 ..: $ 5 .m 8 a a ... a. h 1 . . VJ. . I V .V 11 4 . V m . o . . 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H _ V . h . * M u _ .n _ m . _ .. m IIIII “I In 1 . 0 . . . . . . . ’ V . V _ . . _ V. V V H a“ m . . _ a _ . V V V ..... a _ V . . . V.. V U V .H. H V. M . w . .m ... II- VIIIVII . -VV p . p v _ _ N V m m . ..Vw m _ . .V -. ... fl ”1.. V . a _ . _ h n V II I II «I I I .. I. oV.V .V II . I I II I .9 I I III .I. I III II I . 9* L _ T 7 V _V I ~ . ..I I” ..I Q.\ x235 9828 g 178 ‘ uh. :...("III- I in. : I d M A Huwwmm mmmz .wa musmfim 0 ~ nv—ESH wxonumfi m A b. oAmm *mHV m anumfiw m IoHomOfiuuH filb a c o 3. o 9 oh 0» . h I 96. o u u c 0». gs un~ s t c. {s 0? 0“ u A rs need 9828 % A..A -. Vfi F. VII. m a- A . A. _ V_ I A A VV .A III. I4 A A A m 9‘ . .. . . . m P .A u . H . . . .:e - A A . V .V A a A A.. A :21. I V V A 1L. A A p A . _ A I .II- A . I. A _ . — L I . . m IL}! A . * -IVLIII.II_-I I A ..A. A t” . .A V _ A + . I A V . V. . 0% II A V b I ... A VV . . .. . ..n . . n .V .... A V . V A A V IVA-III V .V V A . A A ..V. ..V n. V . V m A u ‘.I III—II IIMI 0LT m m w on .AAI .v m I H V “III-..I: VIII .. . . . V A V AIIIIIIIII: _ AV: :4 VA.A AVV . -t A A VVA“ A -IIIAI . A AV _AV IA , V V Ir-AIIII+.V A A A «~-V;-. V V.A V A A -.V 3* A . . VI. . ...AVII1- .1 A A. A. - -- A.. A.. V ...-..I...- -- .A A A A . AA - V.A.-VIV AVVV.A...VA V - V w III. .A A “V. A. A. V II. .I. A . .... w -I.. .a _ V . A I . .. . A A u V on . A ..A.. A A V . A V I V A V . A . A. A. A .3. .V . . A -V A A V A r I A A A A . -I A V . A A VAVVVV IA _ V rI I.- II V A . AVA IV.-- VA A V. - 1 VA A II A A m A LIA VII-gm A g .. A A I.” -I. A A A _ m A A . .V.V -..V ...V 09 m . . .V . V I. 4. will-Jill: _ . . ... I.~.. ._ . .vll .I....uII . I oV . AIIAVA...VAVAVV....V.A V ., u I II IIITVI A V _ _ A. ~II . m Av ... .V A A . n V _ V m ..I AI A A A A- Vm .... A A m A IA. II AIM A H A VVV VVAV A A CW A . . A V A. A V. IVA V A .II .-. . . .- It. . . _ . . . .I.-lb % . a A A A _ w _ A. I . .m _ . w ...: .I....I . _V .I I JV A IIAIIII- .AA F-A A -A _ A no A . A1 V A A I14. -I ... M m A V w A . A- . A« A ..I .IIIJIIO A A * u A. a . . I. A VA V A A A V... . A V-A a A V A A A A I- A- V I AAIIIVAJ .A .A I III-II A. A A. . . u ” . . I... A- . . ...-..I A, ..V... . V , .- . A . .-VV-VVAAAAA i - _ V IIJfiI-IJ .. m .- .v V». I II V. _ . .-I*. W V I A n g V “ III—III ” I6.|.I|A . V III-II V A H A ILIIII . A . . . I._ AI.IrAr+IrAV A A. A _ . A I A ..I-I . . A I .I- A A - A u .. "VI. . A _ I! I V A A; A A p I . V II +-I4 - A %II. A F. A 1 . u _ u 179 .Anoflv mcoum-Mmomm_o «o. o. ¢. wuoaomoauu IamnumanuoH HumxosumEIwIA*mon *mw *mm *mm *mHv mo Eduuommm mum: .bm musmwm is 03. 00d or. o». o: oi om. of Om. 3.2 o: 02,0wu O.” Om. 0U ‘0.“ Q. + . _. _ _ _ _ _ 3 3 at Up a, m S a 8 d . a 1‘ gm m or or ca 180 Eiwafl .Amoflv mfiwwuucmumn_n.ao.o.¢.¢a IoHomofluuamnumEflvuo.vlaxonuwelmu“do.mv.dm.*mav mo Esuuommm mam: .mm unamfim 0>< 0?. com or fix Rx 0.3 on.‘ at on: _ . ‘ . a . q . a . . w . . . . . _ . _. ... u-..._T. W..—.:+ ....im. ..-... . TAM... 9Q 9. s 03 .. . pm a mm.u pn.§ . . w . M .. fi . m M -w . ,. IT.-- -_.z;..--- ......o. -livl 3+3.L_..T.13.hl-z w- 3 . Q. L ._ _ . . . m . . : m .. .. _ :.. 2”. ...fl _ u xxxxx :.....rlqlLT . -4 u . p ._ _ ,|f .. m . 1. . . _ . .717 ..n _ . m h .. h , _ ..:. .:.“: H 11.11 ...“! rim..- if... . L.I - w L - _ . . _ .4 . . ., . a a - . ... .- .. . . H ..- - dp . », .4 _ u . . -.- t“ m . . a . b . . H . _ . . , H n h .34 U . 3.?an w Mr V U V V . m # A. .r . _ . :1--+2.! ,3 .. .1. or m . . . . . _ . ., . n m. . r .... x .. -1- - r TI. .53....» . - El. .... z" r . .. a a . _ .... g W a . z. _ ., , fi .- _ .I. w H .. . aw. . ..-. . - on d . * . m u _ _ ~ . . _ ....- n w a M . . . w m M v w . .. x . W. ..w.:.,1-...-..-.---... . . H . , , a. e, . .. . .x ; .. . _ . . . .. _ . -1-+. . - u- .... .. .- . .. ., . - .- ...-.- - .- :.:-.. .-.--.. --:--..... . 9. ”-...“ w -.. -_. ..V.” 4 .,.r w- uw .I- .. . w . . . m . _ _ _ .. .5. . I+€l l-.ril.vl._.-!.l:!wf. «J9 .. fir ......rwilwl . In: ._ a -.H . m . -v:- _:m ..:? w .9. Lm+ _ u u N . m . m . u. . ‘ ... —1 F - . p _ IDI iw... I .I.... 1*.rtoiu: o.o|l-I"0vu-l WIWIAIII. .V.VIIFII L .10 . . v-.c'l lo I i-o. V.- ....-.T...._.‘.. . ..T.....& .... . . -.. . .. . ... . . .5 I .... .:.. I 00!. ‘ . .. .. . u m n m . u m w , . _ m . - Ly . U m. . m . w m . _ 141++¢+iw4j +4 . w . .4.? w .m . W . -...-. -..-.- .... m 13 . . . . . .. . H x . _ . . . . .. L. 2. . h. w ..-. m . .....L.... .. ...T- . ...; .-m -..”: --- 1 I. .x . . z” . . .. _, . w n. _ . _ H fl * r .._ . . ._. :.+ .._. _ h . . . n -... p. u . n . _: .. -:.—,1. .I.» _ . n q . _ .. . ... . , . .. _.. ._ _ . ...... 4... . _.. ll-._... biwl :7. w . .u. . . ...... . 181 .konH muonuummoowHo no. c. v. «HoHOHOHHu ungumaHvum HumxosumaumuH*ma *mm *mm *mm *mHH mo asuuommm mum: .mm «Human .u a H w . 1, Hw H. ...I. .....H; . ... H. .... .H - .H- . - .r __ ... 9+ H . H .HH.HJ . . ..Iu . .M .u l .HH-Inc.*llll no u al! I. .1 Hal .-q I.!. ....u-. ..... : . 1.... ....... .— . - 2!; H H H. -.. . H H H . H . H H, H _ _ H “E . J! a . . . 1.0.... o H. . _ H H . H. H H _. H . “. .. u .H ._ u . I. . w- . ..V: ......- .. T . .... . . . H H m . .H .. H u u . {Lu -.. - ..--L..- IITII.--1|I. I HE H w 1T l. H .HiellHI ....... -H H . . . _ H . H H H m H _ H . -,:._.. .-.. ... - -. . ..2 .. . H . . H _ . n . . . . . H u _ H +1!9+2.l::1 IL I -_-IL!!. I: E x _ .. H 1. .... H .. H . .m L H H H . H H . H H . . lTuIlTlTLW L w ...I. -1_l 3.1.1.... ... -H H H H . H H _ H H . . H. H H . .H-¢. H- :...¢ -sH. H H . . . H . - . . . ll... d1...+1‘a.’.l LT iri! It (OHI‘...“1II..6|¢Lr"O.I.AoIIILn o ..IAo II“! 0 m . . H H . . H H H A H H H m: u H d: I..... m.. . ..H. 0“ o u ..u u “ -Li- .:H..- :L . H. H. . . H H . +1-. ..- ..fi . H H u .. . .. u . _ .. . !H :-..H. I..- .m .H .H. .H .H . H . .. . ... H _ . . . . H. H . H . 1 _ .H H H .H H . . . t I..- all bib . . ..:...I O. A H H . H, H H . . . H . . t . -. _ E .- ..-.I ..o. 2 .. .3 2-.. ...w... ..H, H . H H .. . H . . A H. Hr+ . H. H H . H . - ...I.: ..I. I.-2H-I._T.I....l-l. :4 -... . - . L . . ”0 Ll +1-11IIIIH 1 ¢ ... . .H: H . H H.- .. . .H. H. H H . H . . . L .. . . . . - Lil-TIT... IL 1. EL... L .... . . ... H . W . . H H. H. .H e .. Hi .H. . . H . . . .. _ . , . H H . . .-::1 H Hw A-¢;!14: . V. .. ._ . w-.44- . . . H . . .n H . _ H , . ._ . .. ... . H . . . ML H +_ H . .+ 1+2“ - m. --.-”J iii... 1 .41 ..I+.I.H -. M .r H... H .. H . _ H . M . . . _ H . H . . _ . LlH . . H . . . _ 101. . H.. ....I. H _ fl. H H _ H H ”H H H . fl: H H n H. . H . H y .H H H. .H . . .. H. .. .. ..L. .:H:L 3.31:-.. m; H- . H. ...H- H . H; H .H_ H H L. H. H H - . . H H H 4... ‘IIQI. Oclll‘ I .1. .IIOIIIY-§O. 1. -.I. H H . . . . .. H . _ WV} ..‘--Il . . LC: H H ._l H H H H u. H. H . . H . H .fi H I H H H H H .. . H _ m ..H .HH. ._ .. _. .H H. H H . . cm 2.9: x295 9323 g 182 O Ova CO \ o cmom©_n H v m o. H 0c 0 Am” 3m mus .coH mm»: mam uuo Ed I H mo Hmm.dn.*ma .IW' mom Imxou Elm anum pa hoflu soda or o... 0n on 3 2. 3. o: o! o». I ‘ 02 o 0‘ of a». or. 00M SN 0.: OnN 0% 9% Q» 2: ed 3523 % x9 183 . . H usmam . .0 ¢ v . m o hicmomcmwmmw mmmz Hofl ..(MV flm I o SSH» Adwwdm.*mfiv m .Im' uwxoumom Elm pamsum noaumoflu o: a; 8 2. on or ‘ o: on a. on. oa‘ on. or. o: . 2% 0m 2; o: o; o m N 0. on a: ah xead asea % 0» 9w om ocx APPENDIX B NOMENCLATURE VT 184 & v Chemical Abstracts Service A DIVISION OF THE OHIO STATE UNIVERSITY THE AMERICAN CHEMICAL SOCIETY COLUMBUS“ °”'° “21° Phone 614-421-6940 Kurt L. LoenIng Nomenclature Director April 17, 1974 Dr. John D. Yordy Chemistry Department Michigan State University East Lansing, Michigan 8824 Dear Dr. Yordy: Please excuse the delay in replying to your letter of March 26. It arrived while I was at the ACS meeting in Los Angeles, and I am still trying to catch up with my correspondence. In answer to your query, Chemical Abstracts names most of the ring systems involved in your Compounds as ortho- and ortho- peri-fused systems rather than as von Baeyer rings. The IUPAC rules of organic nomenclature allow both methods. Thus, listing both methods, the fundamental ring systems involved in your six compoundslare named, numbered, and oriented as shown below. A: Naphthalene or H2 H H2 H20— C— C— 0— CH2 '9 10 1 2 a, 7 I. s . H209— c— C— c_ CH2 H2 H H2 Bicyclo[h.h.0]decane 185 Dr. Yordy - 2 - April 17, 197’; l§50yc10penta[l,3]cyC10pr0pa[l,2]benzene or :12 n2 HgC— c -— C — C...CH2 .. '\ H2C—C—‘C— CH—CHZ 112 Tricyclo[4.4.0.0$s]decane l§}CyclOpr0p[g]indene 01‘ H2 /C H2 1\ HZCq—- 9°— C, 3CI’I ‘7 I: 7 ...,l ch— C— C_C—CH2 H2 H H2 Tricyclo[4.h.0.0%9]decane 186 IDr. Yordy - 3 - April 17, l97h Hz H H Hac-— C—— C.__:_C ....CH 2 'q/IM' H08 0 C5... Ci—‘fCHg m Z__ H2 H H2 Tricyclo[h.h.0.0§8]decane Thus f disregarding stereochemistry for the moment, your compounds are named as follows: (1): 3,#,8,8apTetrahydro-8,8apdimethyl-1,6(2§,Z§)-naphthalenedione or 1,10-Dimethy1bicyclo[4.H.O]dec-6—ene-2,8-dione (l) (2): Octahydro-5—hydroxyz4,4apdimethy1~2(l§)-naphthalenone or 7-Hydroxye5,6-dimethylbicyclo[4.4.0]decan-3-one (g) (3): Hexahydro-Baphydroxy-3b,4-dimethylplg-cyclopenta[1,3]cyclo: prOpa[1,2]benzen-6(7§)-one or 5-Hydroxy-6,7-dimethyltricyclo[n.4,0.035]decan-9-one (Q) (4): Hexahydro—la—hydroxy- ,Ba-dimethylrlg-cycloprOp[g]inden~ ll (Egg-one 01' 3- Hydroxy— 5 , 6- dimethyltricyclo [1+ . ll . o. 01:3 ]decan- 7— one (3;) (5): same as 4 except for stereochemistry (Q) (6): 8—Hydroxy-l,lO—dimethyltricyclo[lI.lI.0.03:9]decan-2-one (Q) As for stereochemistry, I enclosez a COpy of the IUPAC tentative rules for fundamental stereochemistry. According to these rules, if the absolute configurations of your compounds are known, the Cahn-Ingold-Prelog sequence-rule symbols are used for the chiral 187 Dr. Yordy - h - April 17, 1974 centers. For the designation of relative configuration the R*,S* system.(rule E—5.lO) is suggested. —"— On the other hand, Chemical Abstracts, for the present collective- index period, has devele d its own syStem of stereodescriptors to “be prefixed to the non-stereospecific names of compounds. This system is a combination of the R,S system and the a,fi system and is summarized in 5203 of the Volume 76 (1972) introduction to the CA Index Guide (Cpr enclosed). Applying this system, the stereo: 'HESignations for the relative configurations of your compounds are (l): trans (for both the naphthalene and von Baeyer names) (2): (ha,haB,5o,8aa) or (la,5a,66,7a) for the von Baeyer name ( \N )3 (3&0,3b5,ua,7q3*) or (l§*,5a,6B,7a) for the von Baeyer name (*1): (1w.35,3w,7a§*) or (l§*,3a,5fi,6a) for the von Baeyer name (5): (1w,3a,3af3,7a_s_*) or (l§*,3a,5a,65) for the von Baeyer name (6): (13*,33*.6§*.8_13*,103*) If the absolute configurations of your compounds are known, then the absolute configuration of the reference center for each of your compounds should be cited in front of the corresponding relative description. I hope you find this information helpful. Please do not hesitate to let me know if I can be of further assistance. Sincerely, KM: L. Lm- ' Kurt L. Loening Director of Nomenclature KLD/bc Enclosures 1188 1These compounds are the following: 2Biochimica et Biophysica Acta, gQQ. I (1970). 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