Preparation and X-ray crystal structure of (4ba ,6P ,9P ,9aa ,10a ,I%)- 4b,5,6,7,8,9,9a,10,11,12,13,14-dodecahydro-4b-pheny1-6,9: 10,13-

dimethanodicyclohepta[a,c]naphthalene

ALAN RICHARD HARRIS, KEITH MILLS. A N D MICHAEL MARTIN-SMITH Clrottistr~ Diciisio~r, GIu.ro Grorrp Rcsetrrc.11 Ltd.. Wnrc,, f f~r!fortlsl~irc~, SGlZ ODJ Et~gltrrrcl

A N D

PETER .MURRAY-RUST A N D JUDITH MURRAY-RUST Depcrrt~t~er~! o f Clrer~~is!ry, U~~iuersity o,f Stirli~lg. Stirling, FKY 4LA Scotlnrttl

Received Feb~uary 21. 1980 Tllis popcr is tlcdic~cr!ecl lo t l ~ c I I I C I I I ~ , : \ . o fDr . LPo Mario~l

ALAN RICHARD HARRIS. MILLS. MICHAI;L MAKFIN-SMITH. PETLR MURRAY-RUST-. and JunlT~H MURRAY-Rus.I.. Can. J . Chem. 58, 1847 (1980).

The novel hexacyclic title hydrocarbon, formed by an unusual oxidative dimerization of 3-phenylbicyclo[3,2,(]oct-2-ene. has been isolated and its structure elucidated by means of X-ray crystallography. The trivial name 4b-phenylmariontetraene is proposed for the hydrocarbon. Crystals are orthorhombic, PDco; a = 21.87(2), h = 10.57(2), c= 17.41(2) A from diffractometer measurements (Mo KC radiation). V = 4024.2 A', Z = 8 , D, = 1.21 Mg m-', F(000) = 1584. p = 0.34cm-I. The structure was solved by direct phasing methods with MULTAN 78 and was refined by weighted full-matrix least-squares procedures to R = 0.046 for 2287 observed reflexions.

ALAN RICHARD HARRIS, K E I T H MILLS, MICHAEL MARTIN-SMIT H. PETER MURRAY-RUST et JUDITH MURRAY-RUST. Can. J . Chem. 58, 1847 (1980).

On a isole le nouvel hydrocarbure hexacyclique mentionne dans le titre qui se forme par une dimerisation oxydante inhabituelle du phenyl-3 bicyclo[3.2.I]octene-2, et on a determine sa structure par diffraction de rayons-X. Pour cet hydrocarbure, on propose le nom vulgaire suivant phenyl-4b mariontetraene.

A partir des mesures de diffraction (radiation Mo KC), on a trouve que les cristaux son1 orthorhombiques Phccr; n = 21,87(2), b = 10.57(2), c = 17,41(2) A. V = 4024.2 A', Z = 8, L),. = 1,21 Mg m-I, F(000) = 1584, p = 0.34 cm-l. On a resolu la structure par la methode des moindres carres (matrice entiere) et on I'a affinee jusqu'i une valeur de R = 0,046 pour 2287 reflexions observees.

[Traduit par le journal]

The last twenty-five years have witnessed a fine honing of X-ray crystallographic technique to pro- vide an extremely sharp tool capable of giving rapid elucidation of the full molecular constitutions of crystalline organic compounds of high structural complexity. The economy of time inherent in the method is reflected in the present structural eluci- dation of an unexpected by-product, a report of- fered in tribute to Leo Marion's early appreciation (1-5) of the potential of the X-ray method. Reaction of the alkene 2 (6) with a mixture of silver cyanate and iodine, applying the conditions employed by Stoll et crl. (7) on the related alkene 1, gave not only the expected allylamine 3 but also two hy- drocarbons 4 and 5 shown by mass spectrometry and microanalysis to have the empirical formulae C,,H,, and C4,H4, respectively. Application of 13C and IH nmr spectroscopy to the lower molecular weight hydrocarbon 4 (isolated in 12% yield) did not permit unequivocal structural assignment. Ac- cordingly an X-ray crystallographic analysis was undertaken on the hydrocarbon 4, which can be formally viewed as representing a dimerization of 2 with concurrent loss of two hydrogen atoms. The

( i i) H30+ \ OoC

31% isolated 12% isolated (ca. 2: 1)

0008-4042/80/ I7 1847-04$0 1 .OO/O @I980 National Research Council of Canada/Conseil national de recherches du Canada

Can

. J. C

hem

. Dow

nloa

ded

from

ww

w.n

rcre

sear

chpr

ess.

com

by

193.

0.65

.67

on 1

1/14

/14

For

pers

onal

use

onl

y.

CAN. J . CHEM. VOL. 58, 1980

FIG. 1. View of the molecule of the hydrocarbon C,,H,,, 4, employing the arbitrarily assigned crystallographic numbering. Tables of fractional atomic co-ordinates, bond distances, bond angles, and torsion angles employing this crystallographic numbering system together with lists of structure factors and thermal parameters have been deposited with the Depository of Unpublished Data, CISTI, National Research Council of Canada, Ottawa, Ont., Canada K I A 0S2 and with the Crystallographic Data Centre, Cambridge, England.

result, portrayed in accordance with the initially assigned (arbitrary) X-ray numbering, is shown in Fig. 1, permitting representation of the compound in accordance with Chemical Abstracts convention as 6, namely

(4bcl ,6P ,9P ,9acl, l k ,13cl)-4b,5,6,7,8,9,9a, 10,11,12, 13,14-dodecahydro-4b-phenyl-6,9: 10,13-dimethano- dicyclohepta[a,c]naphthalene. It is proposed that the trivial name, marionane, be given to the satu- rated hexacyclic ring system 7 in the stereochemistry shown, thus permitting 6 to be

termed 4b-phenylmarion-l,3,4a(l4b),9b(l4a)-tet- raene. The highly bridged ring system present in 6 has not been studied structurally before. The X-ray results as shown in Fig. 1 reveal the confor- mation of the rings in terms of the crystallographic numbering to be as follows. Rings D and Fa re both envelopes with flaps at C(21) and C(22) respec- tively. Ring C is a boat with prows at C(8) and C(21) but flattened and twisted at C(2), C(8). Ring B is an irregular half chair. Ring E is a sofa with almost perfect mirror symmetry and the E/F system has almost perfect local mirror symmetry, the plane

Can

. J. C

hem

. Dow

nloa

ded

from

ww

w.n

rcre

sear

chpr

ess.

com

by

193.

0.65

.67

on 1

1/14

/14

For

pers

onal

use

onl

y.

HARRIS ET AL. 1849

passing through C(15), C(22) and the mid-point of C(18)-C(19). Work directed towards the purifica- tion and structural elucidation of the second hy- drocarbon by-product, C4,H4, (corresponding to an oxidized trimer of 2) and on the mechanism of formation of both the hydrocarbons is in progress and will be reported elsewhere.

Experimental X-rcry Crystallogrcrphic Dota

On crystallization from toluene-ethanol the hydrocarbon 4 afforded large rhombs. A crystal with dimensions 0.5 x 0.65 x 0.65 mm was used for the study. Systematic absences (from Weissenberg photographs) hkO h odd, h01 I odd and Okl k odd indicated space group Pbco. Crystal data:

C ~ ~ H ~ ~ fw = 366 o = 21.87(2), b = 10.57(2), c = 17.41(2) A, from diffractometer measurements (Mo KC radiation) V = 4024.2 A', Z = 8, D, = 1.21 Mg m-', F(000) = 1584, p = 0.34~11-I.

Data were collected for hO-I I1 with Om, = 25" on a Stoe STADI-2 2-circle diffractometer (graphite monochromated Mo KC radiation). This gave 3348 data of which 2287 unique re- flexions with I > k(I) were used in subsequent calculations. Lorentz and polarization corrections (but none for extinction or absorption) were applied and the data scaled by a Wilson plot. The structure was solved by direct phasing methods with MULTAN 78(8) and the SHELX-76 system of programs (9) was used for refinement calculations. Complex neutral atomic scat- tering factors were taken from International Tables for X-ray Crystallography (10). Weighted full-matrix least-squares refinement (including isotropic hydrogen atoms) converged at R = 0.046 for 2287 observed reflexions (R = X(IF,I - 1F,II/ZIF,(); R,, = 0.047 (R,, = Z((jF,,I - I F , ( ( ~ I V " ~ ) / Z ( ( F , I ~ W ~ ' ~ ) , IV = 3.81/(0~(F~) + 4.6 x 10-4F,Z). (The weighting scheme parameters were ad- justed by the SHELX program (9).) In the final cycle all shifts in parameters were less than their standard deviations.

Prc>parrrtiotl of Cotnpout~ds Melting points were determined on a Townson and Mercer

melting point apparatus and are uncorrected. Proton magnetic resonance spectra were recorded on a Varian Associates EM390 90 MHz spectrometer and "C spectra were recorded on a Var- ian Associates XL 100 spectrometer. Signal positions are quoted in 6 units with TMS or DSS as the internal standard. Gas-liquid chromatography was carried out on a Perkin-Elmer F30 machine. Mass spectra were recorded on a Kratos-AEI MS30 spectrometer. Ultraviolet spectra were recorded on a Perkin- Elmer 402 spectrometer and infrared spectra were recorded on a Perkin-Elmer 357 grating spectrometer.

3-Pheny/bicyclo[3,2, Iloct-2-me 2 This compound was prepared by a nickel(I1) acetylacetonate

catalysed coupling reaction (1 1) between phenyl magnesium bromide and 3-bromo- or 3-chlorobicyclo[3,2, Iloct-2-ene. This method gives a 6-8-fold increase in yield over the literature procedure (6). A solution of phenyl magnesium bromide (pre- pared from magnesium (9.6g; 0.4 mol) and bromobenzene (42 mL; 62 g; 0.4 mol)) in ether (150 mL) was added dropwise, with cooling (0°C) under nitrogen, to a stirred mixture of nickel acetylacetonate (0.3 g) and 3-bromobicyclo[3,2,1]oct-2-ene (50g, 0.267 mol) (12). The mixture was stirred at room tempera- ture for 20 h and then hydrochloric acid (200mL; 2M) was added dropwise at 0°C. The organic phase was separated and the aqueous phase was extracted with ether (2 x 200mL). The combined organic solutions were dried (MgS0,) and evaporated

it1 uocito. The residual yellow oil (50g) was distilled to give the title compound as a colourless oil (45g; 91%), bp 109- 113"C/1.5 Torr (lit. (6) bp 8WC10.5 Torr); uv h,,,(EtOH): 220 (e 9 200), 253 (12 000). 292 (sh, 500) nm; irv,,,(CHBr,): 1630cm-I (m, C=C); 'H nmr (CDCI,): 7.70-7.00 (5H, m, aromatic), 6.40 ( IH, d, J = 7Hz,-CH=CPh-). 2.80-1.00(10H, m. aliphatic); I'C nmr6 (ppm): 141.3, s(C3); 133.1, s(C9); 131.1, d(C2); 128.1, d and 124.6, d(C10 and C11); 126.5, d(C12); 38.9, t(C4); 35.7, d(C1); 35.3, t(C7 and C8); 33.5, d(C5); 30.5, t(C6).

Rerrctiotl of Alkene 2 \cjith a Mixtrrre of Iodine rrnd Silver Cyanate

A solution of the alkene 2 (43 g; 0.23 mol) in dichloromethane (400 mL) at 0°C under nitrogen atmosphere was treated with silver cyanate (13) (43 g; 0.22 mol) and then with iodine (57 g; 0.22 mol) in portions (-5 g) over 1 h. The mixture was stirred at P C for 4 h and kept at 0-5'C overnight, filtered, and the filtrate washed with aqueous sodium thiosulphate solution (8%; 250 mL). The solution was dried (MgSO,) and evaporated in uacuo. The residual pale yellow oil (45g) was dissolved in a mixture of acetone (600 mL) and concentrated hydrochloric acid (100 mL), kept at room temperature overnight, and then evapor- ated b~ cacuo. The residue was partitioned between water (300 mL) and ethyl acetate (400 mL) and some insoluble material (A) was filtered off (see below). The aqueous layer was sepa- rated, washed with ethyl acetate (300mL). and then basified with aqueous sodium hydroxide (2 M). The crude basic material was extracted into ethyl acetate (3 x 200mL). The combined extracts were dried (MgSO,) and evaporated to ca. 200 mL in crrcrro. The solution was treated with ethereal hydrogen chloride (8%) until no more precipitate formed and the salt was filtered off and crystallized from a mixture of methanol and ethyl acetate to give 3-phenylbicyclo[3,2,I]oct-3-en-exo-2-amine hydro- ch1oride.l 3 (14.4g; 31%) as a white powder mp 249-251°C (dec). Ultraviolet (EtOH)h,,,: 244 nm (e l l 100); 'H nmr (D20): 7.65 (5H, br s , aromatic), 6.60 ( IH, d , J = 7Hz. -CH=

(8H, m, remaining aliphatic). Ancrl. calcd. for C14H17N.HCI: C 71.33, H7.69, N5.95,CI 15.04;found: C71.41,H7.78,N6.19, C1 15.23%.

The insoluble material (A) described above was filtered off and crystallized froma mixture of toluene and ethanol togive the hydrocarbon 4 (5g; 12%) a s off-white crystals mp 167-170°C (X-ray sample had mp 167.5-170°C); glc 4 M 2% OV-17 column at 280°C. retention time 11.4min. 98.8% purity. Ultraviolet (cyclohexane) h,,,: 221 (e 21 000). 227(21000), 233(17 500), 283 (9 100) nm; 'H nmr (CDCI,): 7.30-6.80 (9H, m, aromatic), 2.87-0.88 (21H. m, aliphatic); "C nmr 6(ppm): 150.6, s(C14a); 143.2, sand 142.2. s(C14band C9b); 134.8, s(C4a); 127.3, d and 126.9, d , (C18, C19, C21, andC22); 126.3, d , 125.9, d , 125.6, d, 125.2, d , and 122.4, d(Cl, C2. C3, C4, and C20); 121.8, s(C17); 58.1, d(C9a); 42.7, d and 42.1, d(C9and C10); 42.4, s(C4b); 39.2, d(C6); 36.7, t, 35.9, t, 35.5, t, 34. I, t, 33.6, t, and 32.6, t(C5, C7, C8, C11, C14, CIS, and (216); 32.4, d(C13); 31.3, t(C12) (num- bering as in6); msttlle: 366(100%; Mt), 297(28%; M - C,H,), 286 (91%; M - C6H8), 217 (33%; M - Cl IHl7 ) . Anal. calcd. for C,,H,,: C 91.80, H 8.20; found: C 91.79, H 8.32%.

Acknowledgments We thank Dr. J. Hunt and his staff of the Analyti-

cal Research Department, Glaxo Group Research

'The exo configuration of the amine function is apparent from the coupling constant of the etldo-2 proton in the nmr spectrum (12, 14, 15).

Can

. J. C

hem

. Dow

nloa

ded

from

ww

w.n

rcre

sear

chpr

ess.

com

by

193.

0.65

.67

on 1

1/14

/14

For

pers

onal

use

onl

y.

1850 CAN. J . CHEM. VOL. 5 8 . 1980

(Ware), for the provision of spectral and mic- roanalytical data. We also thank Dr. D. D. Mac- Nicol for providing I3C nmr spectra and Dr. T. J . Cholerton for interpretation. Grateful acknowl- edgement is made to Dr. D. R. Wilson for helpful discussions. One of us (JM-R) thanks G.G.R. (Ware) Ltd. for financial support.

I. M. PRZYBYLSKA and L . MARION. Can. J. Chem. 34, 185 (1956).

2. M. PRZYBYLSKA and L . MARION. Can. J . Chem. 35. 1075 (1957).

3. M. PRZYBYLSKA and L . MARION. Can. J . Chem. 37, 1 1 16 (1959).

4. M. PRZYBYLSKA and L . MARION. Can. J . Chem. 37, 1848 (1959).

5. M. PRZYBYLSKA and L . MARION. Can. J . Chem. 39, 2124 (1961).

6. C. W. J E F F O R D ~ ~ ~ E. HUANG-YEN. Tetrahedron, 23.4549 (1967).

7. A . P. STOLL. H. R. LOOSLI, P. NIKLAUS, and T . ZARDIN- TARTAGLIA. Helv. Chim. Acta, 61,648(1978).

8. P. MAIN. M U L T A N 78 program for crystal structure solu- tion. University of York, England. 1978.

9. G. M. SHELDRICK. SHELX-76 program for crystal struc- ture determination. University of Cambridge, England. 1976.

10. [nternational tables for X-ray crystallography. Vol. LV. Kynoch Press, Birmingham. 1974. p. 99.

1 1 . R. J . P. C ~ R R I U and J . P. MASSI:. Chem. Commun. 144 (1972).

12. W. R. MOORE. W. R. MOSER, and J . E . LAPRADL. J . Org. Chem. 28.2200(1963).

13. C. H. HLIA.IHCOCK and A. HASSNER. Org. Synth. 51, 112 (1971).

14. C. W. JEFFORD. S . MAHAJAN. J . WASLYN. and B. WAEGELL. J . Am. Chem. Soc. 87,2183 (1965).

15. C. W. JEFFORD. B. WAEGELL, and K. R A ~ I C Y . J . Am. Chem. Soc. 87,2191 (1965).

Can

. J. C

hem

. Dow

nloa

ded

from

ww

w.n

rcre

sear

chpr

ess.

com

by

193.

0.65

.67

on 1

1/14

/14

For

pers

onal

use

onl

y.