3370 J . Org. Chem., Vol. 66, No. 10, 2001
Adcock et al.
bromo chloride as colorless crystals: mp 127-128.5 °C; 1H
NMR (CDCl3) δ 1.79 (2H, d), 1.91 (2H, s), 2.07 (1H, m), 2.16
(C3,5), 59.13 (C4), 29.78 (C6,10), 31.54 (C7), 49.35 (C8); MS
m/z (M+ - Br) calcd for C10H14Br2 213.02785, 215.02585, found
213.0244, 215.0221.
(2H, d), 2.26 (2H, s), 2.34 (2H, s) 2.86 (2H, d), 4.28 (1H, s); 13
C
NMR (CDCl3, relative to Me4Si) δ 63.14 (C1), 36.0 (C2,9), 39.80
(C3,5), 64.38 (C4), 42.34 (C6,10), 30.76 (C7), 49.09 (C8); MS
m/z (M+) calcd for C10H14BrCl 169.0784, 171.05694, found
169.0813, 171.0840.
(Z)-1,4-Dibr om oa d a m a n ta n e (5; X ) Y ) Br ). Following
procedures indicated above for the preparation of the E-isomer,
(Z)-4-bromoadamantane-1-carboxylic acid (5, X ) Br and Y )
COOH; 1.0 g, 3.86 mmol) was converted to the title compound.
Sublimation gave a white solid (850 mg, 75%) that was
recrystallized from methanol to afford the (Z)-dibromide as
colorless crystals: mp 106-108 °C; 1H NMR (CDCl3) δ 1.86
(2H, d), 1.96 (2H, d), 2.12 (1H, s), 2.22 (2H, d), 2.34 (2H, d),
2.36 (2H, s), 2.94 (2H, d), 4.54 (1H, s); 13C NMR (CDCl3,
relative to Me4Si) δ 63.13 (C1), 42.98 (C2,9), 40.35 (C3,5), 58.91
(C4), 36.59 (C6,10), 30.79 (C7), 49.24 (C8); MS m/z (M+ - Br)
calcd for C10H14Br2 213.02785, 215.02585, found 213.0255,
215.0256.
(E)-2-Ch lor o-5-iod oa d a m a n ta n e (4; X ) Cl a n d Y ) I).
Following procedures recently described for the preparation
of 1-chloro-3-iodoadamantane (3, X ) Cl and Y ) I) from
3-chloroadamantane-1-carboxylic acid (3, X ) Cl, Y ) COOH)9
(E)-4-chloroadamantane-1-carboxylic acid (4, X ) Cl and Y )
COOH; 1.0 g, 4.66 mmol) was converted into the title com-
pound. Sublimation gave a white solid (980 mg, 84%) that was
recrystallized from methanol to afford the (E)-chloro iodide as
1
colorless crystals: mp 115-116.5 °C; H NMR (CDCl3) δ 1.63
(2H, d), 1.93 (1H, s), 2.07 (2H, s), 2.36 (2H, d), 2.66 (6H, m),
4.40 (1H, s); 13C NMR (CDCl3, relative to Me4Si) δ 39.80 (C1,3),
64.93 (C2), 52.10 (C4,9), 44.42 (C5), 52.24 (C6), 31.91 (C7),
29.11 (C8,10); MS m/z (M+ - I) calcd for C10H14ClI 169.0784,
171.05694, found 169.0759, 171.0869.
(E)-2-Br om o-5-iod oa d a m a n ta n e (4, X ) Br a n d Y ) I).
Following procedures indicated above for the preparation of
(E)-2-chloro-5-iodoadamantane (4; X ) Cl and Y ) I), (E)-4-
bromoadamantane-1-carboxylic acid (4, X ) Br and Y )
COOH; 1.0 g, 3.86 mmol) was converted into the title com-
pound. Sublimation gave a white solid (750 mg, 63%) that was
recrystallized from methanol to afford the E-bromo iodide as
colorless crystals: mp 127-129 °C; 1H NMR (CDCl3) δ 1.68
(2H, d), 1.94 (1H, s), 2.14 (2H, s), 2.44 (2H, d), 2.63 (2H, s),
2.73 (4H, s); 13C NMR (CDCl3, relative to Me4Si) δ 40.38 (C1,3),
59.50 (C2), 52.64 (C4,9), 44.34 (C5), 52.44 (C6), 32.01 (C7),
29.85 (C8,10); MS m/z (M+ - I) calcd for C10H14BrI 213.02785,
found 213.02785.
(Z)-2-Ch lor o-5-iod oa d a m a n ta n e (5; X ) Cl a n d Y ) I).
Following procedures indicated above for the preparation of
the E-isomer, (Z)-4-chloroadamantane-1-carboxylic acid (5, X
) Cl and Y ) COOH; 1.0 g, 4.66 mmol) was converted into
the title compound. Sublimation gave a white solid (950 mg,
82%) that was recrystallized from methanol to afford the (Z)-
1
chloro iodide as colorless crystals: mp 71-72.5 °C; H NMR
(CDCl3) δ 1.88 (2H, d), 1.90 (1H, s), 2.00 (2H, d), 2.11 (2H, s),
2.42 (2H, d), 2.61 (2H, s), 3.10 (2H, d), 4.38 (1H, s); 13C NMR
(CDCl3, relative to Me4Si) δ 40.00 (C1,3), 64.51 (C2), 45.30
(C4,9), 45.85 (C5), 52.18 (C6), 31.16 (C7), 36.02 (C8,10); MS
m/z (M - I+) calcd for C10H14ClI 169.0784, 171.05694, found
169.0795, 171.0757.
(Z)-2-Br om o-5-iod oa d a m a n ta n e (5, X ) Br a n d Y ) I).
Following thprocedures indicated above for the preparation
of the E-isomer, (Z)-4-bromoadamantane-1-carboxylic acid (5,
X ) Br and Y ) COOH; 1.0 g, 3.86 mmol) was converted to
the title compound. Sublimation gave a white solid (880 mg,
89%) that was recrystallized from methanol to afford the
Z-bromo iodide as colorless crystals: mp 86-87.5 °C; 1H NMR
(CDCl3) δ 1.99 (5H, m), 2.17 (2H, s), 2.46 (2H, d), 2.62 (2H, s),
3.18 (2H, d), 4.63 (1H, s); 13C NMR (CDCl3, relative to Me4Si)
δ 40.52 (C1,3), 59.13 (C2), 45.92 (C4,9), 45.82 (C5), 52.34 (C6),
(E)- a n d (Z)-1,4-Dibr om oa d a m a n ta n e (4 a n d 5; X ) Y
) Br ) a n d (E)- a n d (Z)-2-Br om o-5-iod oa d a m a n ta n e (4
a n d 5; X ) Br a n d Y ) I, r esp ectively). By use of the
procedure of Lantvoev,42 a solution of tetrabromomethane (3.42
g, 7.32 mmol) in dry THF (10 mL) was added dropwise to a
solution of the E/Z epimeric alcohols (4 and 5; X ) OH and Y
) COOCH3; 1.44 g, 6.9 mmol) and triphenylphosphine (1.92
g, 7.32 mmol) in dry THF (20 mL). The reaction mixture was
refluxed for 72 h and then worked up as described above for
the corresponding chloro esters. Separation of the epimeric
bromo-ester mixture (4 and 5; X ) Br and Y ) COOCH3; E/Z
) 35/65) was effected by HPLC (prepacked silica gel column)
with 1.5% ethyl acetate/hexane as the eluent. The compounds
were obtained as colorless oils (1.11 g (combined yield), 59%).
E isomer (4, X ) Br and Y ) COOCH3): 13C NMR (CDCl3,
relative to Me4Si) δ 35.67 (C1,3), 61.15 (C2), 39.74 (C4,9), 39.64
(C5), 39.12 (C6), 27.15 (C7), 30.52 (C8,10), 51.75 (CH3), 176.69
(CO). Z isomer (5, X ) Br, Y ) COOCH3): 13C NMR (CDCl3,
relative to Me4Si) δ 35.53 (C1,3), 60.64 (C2), 32.53 (C4,9), 39.79
(C5), 38.81 (C6), 26.25 (C7), 37.12 (C8,10), 51.28 (CH3), 176.54
(CO). Hydrolysis of both esters by a standard procedure (KOH/
C2H5OH/H2O) afforded the corresponding 4-bromoadaman-
tane-1-carboxylic acids as white solids upon sublimation. E
isomer (4, X ) Br and Y ) COOH): mp 174-176 °C (lit.42 mp
195-197 °C); 13C NMR (CDCl3, relative to Me4Si) δ 35.54
(C1,3), 60.86 (C2), 39.47 (C4,9), 39.53 (C5), 38.87 (C6), 27.05
(C7), 30.46 (C8,10), 183.41 (CO). Z isomer (5, X ) Br and Y )
COOH): mp 186-188 °C (lit.42 mp 198-199 °C); 13C NMR
(CDCl3, relative to Me4Si) δ 36.10 (C1,3), 60.76 (C2), 32.62
(C4,9), 40.06 (C5), 38.92 (C6), 26.48 (C7), 37.43 (C8,10), 183.50
(CO).
31.19 (C7), 36.82 (C8,10); MS m/z (M+ - I) calcd for C10H14
BrI 213.02785, found 213.0295.
-
9-Br om o-10-iod otr ip tycen e (7; X ) Br a n d Y ) I). By
use of the lithiation procedure of Kawada and Iwamura,43
a
solution of 9,10-dibromotriptycene (7, X ) Y ) Br; 5.0 g, 0.012
mol) in benzene/diethyl ether (100 mL; 1:2 v/v) was treated
with ca. 2.2 molar equiv of n-butyllithium (25 mL of 1 M
solution in hexane; 0.026 mol) at 0 °C under an atmosphere
of dry nitrogen. The reaction mixture was stirred at this
temperature for 30 min and then allowed to stand undisturbed
for 1 h after removal of the cold bath. The supernatant liquid
was carefully removed by syringe under nitrogen before freshly
distilled iodobenzene (9.9 g, 0.05 mol) was added to the
9-bromo-10-triptycyllithium (7; X ) Br and Y ) Li) and the
reaction mixture refluxed overnight. After cooling the reaction
mixture was quenched with saturated aqueous NH4Cl and
worked up in the standard manner. Recrystallization from a
hexane/ethanol mixture (1:1 v/v) afforded the title compound
1
as leaflets (3.5 g, 64%): mp 303-305 °C; H NMR (CDCl3) δ
7.03-7.26 (6H, m, Ar), 7.83-8.06 (6H, m, Ar); 13C NMR
(CDCl3, relative to Me4Si) δ 123.26 (C1,8,13), 126.68 (C2,7,-
14), 126.59 (C3,6,15), 127.81 (C4,5,16), 142.28 (C4a,10a,11),
143.63 (C8a,9a,12), 71.73 (C9), 59.59 (C10); MS m/z (M+) calcd
for C20H12BrI 457.91695, 459.91498, found 457.9196, 459.9165.
Con ver sion of 6 (X ) COOH, Y ) O) to 6 (X ) Br , Y )
O). Following procedures recently described for the prepara-
tion of 1-bromo-3-chloroadamantane (3; X ) Br and Y ) Cl)
from 3-chloroadamantane-1-carboxylic acid (3, X ) COOH and
Y ) Cl),9 6 (X ) COOH, Y ) O; 0.5 g, 2.58 mmol) was converted
to 6 (X ) Br, Y ) O). A vpc and GC/MS analysis of the crude
product revealed the complete absence of the fragmentation
product (11). Sublimation of the crude product gave 6 (X )
(E)-1,4-Dibr om oa d a m a n ta n e (4; X ) Y ) Br ). Following
procedures indicated above for the preparation of (E)-1-bromo-
4-chloroadamantane (4; X ) Cl and Y ) Br), (E)-4-bromoada-
mantane-1-carboxylic acid (4, X ) Br and Y ) COOH; 1.0 g,
3.86 mmol) was converted into the title compound. Sublimation
gave a white solid (900 mg, 87%) that was recrystallized from
methanol to afford the (E)-dibromide as colorless crystals: mp
1
143-144.5 °C; H NMR (CDCl3) δ 1.62 (2H, d), 2.11 (1H, s),
2.31 (2H, d), 2.39 (4H, s), 2.49 (4H, s), 4.59 (1H, s); 13C NMR
(43) (a) Kawada, Y.; Iwamura, H. J . Org. Chem. 1981, 46, 3357. (b)
Kawada, Y.; Iwamura, H. J . Am. Chem. Soc. 1983, 105, 1449.
(CDCl3, relative to Me4Si) δ 61.86 (C1), 49.43 (C2,9), 39.72