Racemic and Optically Active 1,1ꢀ-Binaphthyl-2,2ꢀ-diyl Sulfite 569
solid (32 mg) obtained was analyzed by NMR
spectroscopy.
was added. A part of this solution (1 mL) was placed
in a polarimetric tube, and the optical rotation was
measured. The content of the tube and the vial was
combined and evaporated under reduced pressure
(including a few hour drying under high vacuum
(0.5 mmHg)) yielding 21 mg of a white solid as a
crude product.
1H NMR (CDCl3, 200.16 MHz) δ 7.82–7.85 (d,
JHH = 7.02 Hz, 4HAr), 7.13–7.41 (m, 8HAr), 5.75 (bs,
2H, OH), 2.88–2.94 (bs, 2 × 2H, NCH ), 1.00 (bs,
2 × 12H, H C).
3
1H NMR (CDCl3, 200.16 MHz) δ 7.95–7.84 (m,
4HAr), 7.39–7.12 (m, 8HAr), 4.62 (bs, 2H), 2.50 (q,
J = 7.2 Hz, 6H,CH2CH3), 1.00 (t, J = 7.2 Hz, 9 H,
CH2CH3).
An Ionic Salt or a Complex with a Hydrogen
Bond of (R)-(+)-2,2ꢀ-Dihydroxy-1,1ꢀ-binaphthyl
and Diisopropylamine (Compound 8)
(R)-(+)-2,2ꢀ-Dihydroxy-1,1ꢀ-binaphthyl
(17
mg,
0.06 mmol) was charged to a small vial and dis-
solved in dichloromethane (2 mL). To a clear
solution, diisopropylamine (12 mg, 0.12 mmol, 2
equiv.) was added. A part of this solution (1 mL)
was placed in a polarimetric tube, and the optical
rotation was measured. The content of the tube
and the vial was combined and evaporated under
reduced pressure (including a few hours of drying
under high vacuum (0.5 mmHg)), yielding 20 mg of
a white solid as a crude product.
Crystallographic Data for 2a
C13H12O3S, M = 332.36, orthorhombic, P212121
space group, a = 5.9244(4), b = 16.1977(7), and
˚
c = 16.8640(7) A, Z = 4 molecules per unit cell,
Dc = 1.364 g/cm3, F(000) = 688, crystal size 0.20
× 0.08 × 0.05 mm. Diffraction data were collected
at 293(2) K, using an Oxford Diffraction Xcalibur
3TM diffractometer (Abingdon, UK) (Cu Kα radiation,
CCD detector). The structure was solved by direct
methods and refined by full-matrix least-squares on
F2 with SHELXL-97 [23]. The disorder on S1, O1,
O2, and O3 atoms was resolved by finding alterna-
tive positions from the difference Fourier map and
was subsequently refined over two positions with the
occupancy of 0.666(5) for the major component. To
assist in the refinement process, the anisotropic dis-
placement parameters of O and S atoms of the mi-
nor components were constrained to be the same as
those of the major components. Apart from the H2
atom, all hydrogen atoms were positioned geometri-
cally and constrained to ride on their parent atoms,
with C H distances of 0.93 and with Uiso(H) values
of 1.2Ueq(C). The (R) configuration was established
by means of the Flack x parameter [10] of −0.12 (4)
and the Hooft y parameter [11] of −0.06 (2), calcu-
lated for 1184 Bijvoet pairs (100% coverage). R[F2
> 2σ (F2)] = 0.051, wR(F2) = 0.139, S = 1.01 for
2872 independent reflections [2270 reflections with
I > 2σ (I)] and 235 parameters.
1H NMR (CDCl3, 200.16 MHz) δ 7.86–7.98 (m,
4HAr), 7.29–7.40 (m, 6HAr), 7.13–7.17 (m, 2HAr), 3.53
(bs, 2H, OH), 2.78–2.94 (m, 2H, NCH ), 0.99 (d,
JHH = 6.23 Hz, 12H, H C). Elem. Anal. Calcd for
3
comp. 8: C, 80.59; H,7,54; N, 3,61, found: C, 79.98;
H, 7.48; N, 3.59;
Compound 9
Twenty milligrams of (R)-(–)-1,1ꢀ-Binaphthyl-2,2ꢀ-
diyl-sulfite 2 (0.06 mmol) was charged to a small vial
and dissolved in dichloromethane (2 mL). To a clear
solution, triethylethylamine (0.030 g., 0.3 mmol, 5
equiv) was added. A part of this solution (1 mL) was
placed in a polarimetric tube, and the optical rota-
tion was measured. After that, the content of the tube
and the vial was combined and evaporated under re-
duced pressure followed by a few hours of drying un-
der high vacuum (0.5 mmHg). A white solid (28 mg)
obtained was analyzed by NMR spectroscopy.
1H NMR (CDCl3, 200.16 MHz) δ 7.83–7.78 (m,
4HAr), 7.45–7.40 (m, 2HAr),7.30–7.08 (m, 6HAr), 2.67
(q, J = 7.2 Hz, 12H, CH2Me), 1.05 (t, J = 7.2 Hz, 18
H, CH2Me).
Crystallographic Data for 2b
C13H12O3S, M = 332.36, monoclinic, P21, a =
˚
˚
˚
11.0443(13) A, b = 7.9384(8) A, c = 17.599(3) A
and β = 92.423(12)◦, Z = 4 molecules per unit cell,
Dc = 1.432 g/cm3, F(000) = 688, crystal size 0.37 ×
0.30 × 0.06 mm. Diffraction data were collected at
293(2) K, using an Oxford Diffraction Xcalibur 3TM
diffractometer (Cu Kα radiation, CCD detector). The
structure of 2b was also solved by direct methods
and refined by full-matrix least-squares on F2 with
SHELXL-97 [23], and the disorder on O01 and O02
An Ionic Salt or a Complex with a Hydrogen
Bond of (R)-(+)-2,2ꢀ-Dihydroxy-1,1ꢀ-binaphthyl
and Triethylamine (Compound 10)
(R)-(+)-2,2ꢀ-Dihydroxy-1,1ꢀ-binaphthyl
(17
mg,
0.06 mmol) was charged to a small vial and dis-
solved in dichloromethane (2 mL). To a clear
solution, triethylamine (30 mg, 0.30 mmol, 5 equiv.)
Heteroatom Chemistry DOI 10.1002/hc