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329
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sealed capillary); lit. data: [8e] m.p. 178ꢀ
/
179 8C dec.
TLC (PE:E, 1:2): Rf 0.39. H-NMR (200 MHz, CDCl3,
TMS): d 2.37 (2H, d, HCÅ, Jꢄ1.0), 3.91 (2H, d, CH),
6.74 (4H, d, aromatic H, Jꢄ 6.6), 7.13 (4H, d, aromatic
1
(b) S.S. Rai, J. Wolff, Proc. Natl. Acad. USA 95 (1998) 4253.
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/
/
/
H). MS DIP: m/z 262 (9%), 131 (100%). HR-MS/CI-
NH3: Calc. for C18H15O2 MHꢁ 263.107 205. Found:
263.107 290. Anal. Found: C, 82.78; H, 5.21. C18H14O2
requires: C, 82.44; H, 5.34%.
(c) G.G. Kuiper, B. Carlsson, K. Grandien, E. Enmark, J.
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¨
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3.8.
D,L-3,4-Di(4-hydroxyphenyl)hexane (D,L-1)
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Under an atmosphere of hydrogen, a solution of
D,L-9
(42 mg, 0.16 mmol) in ethyl acetate (8 ml) was stirred
over 5% Pd/C (28 mg) for 48 h at 20 8C. The reaction
mixture was filtered off on a short bed of celite,
evaporated to dryness, then fractionated on a Florisil
(g) K.E. Bergmann, S.W. Landvatter, P.G. Rocque, K.E.
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(i) H. Ohishi, M. Ogawa, Chem. Pharm. Bull. (Tokyo) 41 (1993)
1157;
column (P, P:E, 2:1, 1:1) to yield
a white solid. M.p. 124ꢀ124.5 8C (sealed capillary); lit.
data: m.p. 126ꢀ128 8C [8a]; 123ꢀ124 8C [8c]. TLC
(PE:E, 1:2): Rf 0.52. H-NMR (200 MHz, [d6]acetone,
TMS): d 0.69 (6H, t, CH3, Jꢄ7.3), 1.38ꢀ1.58 (2H, m,
CH2), 1.73ꢀ1.92 (2H, m, CH2), 2.63 (2H, m, CH), 6.57ꢀ
D,L-1 (37 mg, 86.0%) as
/
(j) F. Martinez-Azorin, J.A. Teruel, F. Fernandez-Belda, J.C.
Gomez-Fernandez, J. Biol. Chem. 267 (1992) 11923;
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2045;
/
/
1
/
/
/
/
(l) J.E. Hart, Toxicology 61 (1990) 185.
[7] (a) Y. Sato, T. Murai, T. Oda, H. Saito, M. Kodama, A. Hirata,
J. Biochem. 101 (1987) 1247;
6.75 (8H, m, aromatic H), 7.93 (2H, s, OH). MS DIP: m/
z 270 (3%), 135 (100%). HR-MS/CI-NH3: Calc. for
C18H26NO2 MNH4ꢁ 288.196 354. Found: 288.195 968.
(b) Y. Sakakibara, K. Hasegawa, T. Oda, H. Saito, M. Kodama,
A. Hirata, M. Matsuhashi, Y. Sato, Biochem. Pharmacol. 39
(1990) 167;
(c) T. Oda, M. Watanuki, Y. Sakakibara, Y. Sato, Biol. Pharm.
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[8] For nonstereoselective synthesis of D,L-1 see:
4. Supplementary material
(a) E. Schwenk, D. Papa, B. Whitman, H.F. Ginsberg, J. Org.
Chem. 9 (1944) 175;
Tables of crystallographic details, bond distances and
angles, atomic coordinates and equivalent isotropic
displacement parameters, as well as torsion angles for
(b) N.P. Buu-Hoi, N. Noan, J. Org. Chem. 14 (1949) 1023;
(c) D.J. Collins, J.J. Hobbs, Aust. J. Chem. 23 (1970) 1605;
(d) H.H. Inhoffen, D. Kopp, S. Maric, J. Bekurdts, R. Selimoglu,
Tetrahedron Lett. (1970) 999;
D,L-6; data are also available as files in CIF format.
For the adaptation of the synthetic method previously developed
by us, see:
Acknowledgements
(e) M.J. Meyers, J. Sun, K.E. Carlson, G.A. Marriner, B.S.
Katzenellenbogen, J.A. Katzenellenbogen, J. Med. Chem. 44
(2001) 4230.
Acknowledgment is made to the donors of the
American Chemical Society Petroleum Research Fund
for support of this research (Grant #39104ꢀB1). The
authors are greatly indebted to Hewlett Packard and
Office of Graduate Studies, Research and International
Programs, College of Science and Mathematics and
University Corporation, California State University
Northridge for generous support.
[9] G.G. Melikyan, A. Deravakian, S. Myer, S. Yadegar, K.I.
Hardcastle, J. Ciurash, P. Toure, J. Organomet. Chem. 578
(1999) 68.
/
[10] H. Greenfield, H.W. Sternberg, R.A. Friedel, J.H. Wotiz, R.
Markby, I. Wender, J. Am. Chem. Soc. 78 (1956) 120.
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143 (1995) 331;
(b) G.G. Melikyan, K.M. Nicholas, in: P.J. Stang, F. Diederich
(Eds.), Modern Acetylene Chemistry, VCH, Weinheim, 1995, p.
99;
(c) H.E. Amouri, M. Gruselle, Chem. Rev. 96 (1996) 1077.
[12] (a) G.G. Melikyan, S. Bright, T. Monroe, K.M. Hardcastle, J.
Ciurash, Angew.Chem. 110 (1998) 170;
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