Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105005676/hj1041sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105005676/hj1041IIsup2.hkl |
CCDC reference: 248251
(R)-(-)-[(2-methoxy-5-methyl)phenyl]-2-phenyl ethylamine (3 mmol) and 2-hydroxy-5-methyl acetophenone (3 mmol) (both purchased from J&K Chemical Ltd) were dissolved in me thanol (20 ml) and reacted at room temperature for 12 h. Solvent was removed and NaBH4 (15 mmol) was added to the solution in an THF/ethanol (20 ml, 1:1 v/v) mixture. The reaction was allowed to stand and was monitored by thin-layer chromatography and gel chromatography. After a variable period, the reaction was stopped at constant conversion of starting material. 6 M HCl was then added dropwise to the reaction mixture until hydrogen production ceased, and the mixture was then neutralized with Na2CO3. The aqueous solution was extracted with CHCl3. The organic layer was dried with anhydrous sodium sulfate and filtered. The solvent was removed under reduced pressure. Further purification was carried out by thin-layer silica gel chromatography [first time: chloroform/methanol (40:1 v/v); second time: chloroform/methanol (60:1, v/v)] to give chiral 2-{(R)-1-[(R)-1-(2-methoxy-5-methylphenyl)-2-phenylethyl- amino]ethyl}-4-methylphenol (canary oil, 89.2%, [a]D18= −19.5(c 1/2, CHCl3)). Since only the major diastereoisomer was obtained pure by thin-lay silica gel chromatography, the 1H NMR signals for the minor diastereoisomer was deduced from the spectra of the crude reaction mixture. Compound (I) and concentrated HCl were reacted at room temperature, and a white solid was precipitated. The solvent was removed and the solid residue was recrystallized from ethanol to yield compound (II) (m.p. 473.0–473.2 K).
H atoms were visible in difference maps and were subsequently treated as riding atoms, with C—H distances of 0.93 (aromatic H atoms), 0.96 (CH3), 0.97 (CH2) and 0.98 Å (CH).
Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1995); software used to prepare material for publication: SHELXTL.
C25H30NO2+·Cl− | Dx = 1.173 Mg m−3 |
Mr = 411.95 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 3690 reflections |
a = 9.227 (3) Å | θ = 2.5–22.3° |
b = 15.323 (6) Å | µ = 0.18 mm−1 |
c = 16.504 (6) Å | T = 298 K |
V = 2333.4 (15) Å3 | Block, colorless |
Z = 4 | 0.43 × 0.35 × 0.31 mm |
F(000) = 880 |
Bruker SMART CCD area-detector diffractometer | 4115 independent reflections |
Radiation source: fine-focus sealed tube | 3080 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→10 |
Tmin = 0.926, Tmax = 0.946 | k = −18→18 |
12327 measured reflections | l = −19→14 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.038 | Geom |
wR(F2) = 0.097 | w = 1/[σ2(Fo2) + (0.0695P)2 + 0.2951P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
4115 reflections | Δρmax = 0.14 e Å−3 |
263 parameters | Δρmin = −0.13 e Å−3 |
18 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.03 (7) |
C25H30NO2+·Cl− | V = 2333.4 (15) Å3 |
Mr = 411.95 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 9.227 (3) Å | µ = 0.18 mm−1 |
b = 15.323 (6) Å | T = 298 K |
c = 16.504 (6) Å | 0.43 × 0.35 × 0.31 mm |
Bruker SMART CCD area-detector diffractometer | 4115 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3080 reflections with I > 2σ(I) |
Tmin = 0.926, Tmax = 0.946 | Rint = 0.031 |
12327 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | Geom |
wR(F2) = 0.097 | Δρmax = 0.14 e Å−3 |
S = 1.01 | Δρmin = −0.13 e Å−3 |
4115 reflections | Absolute structure: Flack (1983) |
263 parameters | Absolute structure parameter: −0.03 (7) |
18 restraints |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cl1 | 0.54726 (8) | 0.28032 (4) | 0.32748 (4) | 0.0603 (2) | |
N1 | 0.3272 (2) | −0.03250 (12) | 0.18827 (11) | 0.0386 (5) | |
H1A | 0.3999 | −0.0055 | 0.2146 | 0.046* | |
H1B | 0.3549 | −0.0880 | 0.1795 | 0.046* | |
O1 | −0.0697 (2) | 0.04598 (18) | 0.24767 (15) | 0.0941 (7) | |
O2 | 0.4320 (2) | 0.13496 (10) | 0.21243 (10) | 0.0540 (5) | |
H2 | 0.4595 | 0.1745 | 0.2422 | 0.081* | |
C1 | −0.0673 (3) | −0.0311 (2) | 0.20648 (19) | 0.0714 (9) | |
C2 | 0.0664 (3) | −0.07331 (18) | 0.20186 (15) | 0.0520 (7) | |
C3 | 0.0750 (3) | −0.15326 (19) | 0.16279 (18) | 0.0647 (8) | |
H3 | 0.1639 | −0.1818 | 0.1610 | 0.078* | |
C4 | −0.0439 (5) | −0.1925 (2) | 0.1261 (2) | 0.0829 (11) | |
C5 | −0.1739 (5) | −0.1497 (3) | 0.1314 (2) | 0.0980 (14) | |
H5 | −0.2555 | −0.1748 | 0.1080 | 0.118* | |
C6 | −0.1872 (4) | −0.0713 (3) | 0.1698 (2) | 0.0954 (13) | |
H6 | −0.2772 | −0.0441 | 0.1717 | 0.114* | |
C7 | −0.0299 (5) | −0.2790 (3) | 0.0838 (3) | 0.1263 (17) | |
H7A | 0.0689 | −0.2984 | 0.0864 | 0.152* | 0.50 |
H7B | −0.0583 | −0.2728 | 0.0281 | 0.152* | 0.50 |
H7C | −0.0914 | −0.3211 | 0.1098 | 0.152* | 0.50 |
H7D | −0.1228 | −0.2964 | 0.0632 | 0.152* | 0.50 |
H7E | 0.0044 | −0.3220 | 0.1215 | 0.152* | 0.50 |
H7F | 0.0375 | −0.2738 | 0.0398 | 0.152* | 0.50 |
C8 | −0.1921 (4) | 0.1014 (3) | 0.2371 (3) | 0.1235 (17) | |
H8A | −0.1803 | 0.1530 | 0.2693 | 0.148* | 0.50 |
H8B | −0.2782 | 0.0711 | 0.2537 | 0.148* | 0.50 |
H8C | −0.2003 | 0.1173 | 0.1810 | 0.148* | 0.50 |
H8D | −0.2589 | 0.0746 | 0.2000 | 0.148* | 0.50 |
H8E | −0.1610 | 0.1565 | 0.2156 | 0.148* | 0.50 |
H8F | −0.2389 | 0.1103 | 0.2884 | 0.148* | 0.50 |
C9 | 0.1955 (3) | −0.03336 (16) | 0.24276 (15) | 0.0452 (6) | |
H9 | 0.1714 | 0.0273 | 0.2559 | 0.054* | |
C10 | 0.2371 (3) | −0.07938 (16) | 0.32176 (15) | 0.0519 (7) | |
H10A | 0.1544 | −0.0790 | 0.3581 | 0.062* | |
H10B | 0.2607 | −0.1398 | 0.3100 | 0.062* | |
C11 | 0.3634 (3) | −0.03745 (16) | 0.36337 (14) | 0.0467 (6) | |
C12 | 0.3491 (4) | 0.04298 (19) | 0.40086 (17) | 0.0645 (8) | |
H12 | 0.2592 | 0.0704 | 0.4017 | 0.077* | |
C13 | 0.4655 (5) | 0.0828 (2) | 0.43680 (19) | 0.0817 (11) | |
H13 | 0.4537 | 0.1366 | 0.4620 | 0.098* | |
C14 | 0.5989 (5) | 0.0439 (3) | 0.4358 (2) | 0.0869 (11) | |
H14 | 0.6780 | 0.0713 | 0.4598 | 0.104* | |
C15 | 0.6149 (4) | −0.0348 (3) | 0.3995 (2) | 0.0826 (10) | |
H15 | 0.7053 | −0.0616 | 0.3991 | 0.099* | |
C16 | 0.4983 (3) | −0.07581 (19) | 0.36311 (17) | 0.0607 (8) | |
H16 | 0.5112 | −0.1297 | 0.3383 | 0.073* | |
C17 | 0.3070 (3) | 0.01147 (14) | 0.10722 (14) | 0.0381 (6) | |
H17 | 0.2360 | −0.0225 | 0.0763 | 0.046* | |
C18 | 0.4506 (3) | 0.00799 (17) | 0.06186 (16) | 0.0542 (7) | |
H18A | 0.4375 | 0.0303 | 0.0080 | 0.065* | |
H18B | 0.4837 | −0.0513 | 0.0591 | 0.065* | |
H18C | 0.5211 | 0.0428 | 0.0899 | 0.065* | |
C19 | 0.3103 (3) | 0.16121 (14) | 0.17134 (15) | 0.0416 (6) | |
C20 | 0.2470 (3) | 0.10201 (14) | 0.11831 (14) | 0.0378 (5) | |
C21 | 0.1238 (3) | 0.12697 (16) | 0.07632 (15) | 0.0465 (6) | |
H21 | 0.0808 | 0.0872 | 0.0411 | 0.056* | |
C22 | 0.0621 (3) | 0.20900 (17) | 0.08478 (16) | 0.0571 (7) | |
C23 | 0.1256 (3) | 0.26526 (17) | 0.13990 (17) | 0.0600 (8) | |
H23 | 0.0844 | 0.3199 | 0.1483 | 0.072* | |
C24 | 0.2482 (3) | 0.24274 (15) | 0.18272 (17) | 0.0524 (7) | |
H24 | 0.2891 | 0.2820 | 0.2191 | 0.063* | |
C25 | −0.0707 (4) | 0.2348 (2) | 0.0372 (2) | 0.0946 (12) | |
H25A | −0.0988 | 0.1875 | 0.0024 | 0.114* | 0.50 |
H25B | −0.0493 | 0.2853 | 0.0050 | 0.114* | 0.50 |
H25C | −0.1484 | 0.2479 | 0.0739 | 0.114* | 0.50 |
H25D | −0.0989 | 0.2930 | 0.0518 | 0.114* | 0.50 |
H25E | −0.1484 | 0.1952 | 0.0492 | 0.114* | 0.50 |
H25F | −0.0492 | 0.2326 | −0.0197 | 0.114* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0633 (4) | 0.0449 (3) | 0.0726 (5) | −0.0110 (3) | −0.0108 (4) | −0.0020 (3) |
N1 | 0.0369 (11) | 0.0352 (10) | 0.0437 (12) | 0.0005 (8) | −0.0036 (9) | 0.0017 (9) |
O1 | 0.0617 (14) | 0.128 (2) | 0.0923 (17) | 0.0378 (15) | 0.0039 (14) | 0.0002 (16) |
O2 | 0.0532 (11) | 0.0449 (9) | 0.0639 (11) | −0.0038 (9) | −0.0171 (10) | −0.0082 (8) |
C1 | 0.0463 (19) | 0.108 (3) | 0.0599 (19) | 0.0007 (19) | 0.0017 (16) | 0.0267 (19) |
C2 | 0.0386 (15) | 0.0654 (17) | 0.0519 (16) | −0.0092 (14) | −0.0011 (13) | 0.0183 (13) |
C3 | 0.0518 (17) | 0.0684 (19) | 0.074 (2) | −0.0231 (15) | −0.0078 (16) | 0.0191 (17) |
C4 | 0.081 (3) | 0.094 (3) | 0.073 (2) | −0.050 (2) | −0.022 (2) | 0.0294 (19) |
C5 | 0.069 (3) | 0.144 (4) | 0.081 (3) | −0.057 (3) | −0.020 (2) | 0.041 (3) |
C6 | 0.0409 (19) | 0.164 (4) | 0.081 (3) | −0.007 (2) | −0.0077 (19) | 0.044 (3) |
C7 | 0.162 (4) | 0.097 (3) | 0.120 (3) | −0.073 (3) | −0.043 (3) | 0.013 (2) |
C8 | 0.083 (3) | 0.155 (4) | 0.132 (4) | 0.062 (3) | 0.020 (3) | 0.033 (3) |
C9 | 0.0426 (14) | 0.0461 (14) | 0.0470 (15) | 0.0000 (12) | 0.0038 (12) | 0.0056 (12) |
C10 | 0.0558 (17) | 0.0551 (15) | 0.0450 (15) | −0.0053 (13) | 0.0031 (14) | 0.0097 (13) |
C11 | 0.0620 (18) | 0.0433 (14) | 0.0348 (14) | −0.0007 (13) | −0.0002 (12) | 0.0087 (11) |
C12 | 0.090 (2) | 0.0535 (17) | 0.0507 (18) | 0.0096 (17) | −0.0023 (17) | 0.0027 (14) |
C13 | 0.134 (4) | 0.0563 (19) | 0.055 (2) | −0.021 (2) | −0.010 (2) | −0.0042 (15) |
C14 | 0.099 (3) | 0.100 (3) | 0.062 (2) | −0.041 (2) | −0.014 (2) | −0.004 (2) |
C15 | 0.068 (2) | 0.109 (3) | 0.071 (2) | −0.004 (2) | −0.0105 (18) | −0.007 (2) |
C16 | 0.066 (2) | 0.0612 (17) | 0.0547 (18) | 0.0054 (15) | −0.0047 (14) | −0.0078 (14) |
C17 | 0.0431 (14) | 0.0352 (12) | 0.0361 (14) | −0.0007 (11) | −0.0062 (11) | 0.0005 (10) |
C18 | 0.0598 (17) | 0.0543 (15) | 0.0485 (15) | 0.0052 (14) | 0.0049 (15) | 0.0041 (12) |
C19 | 0.0407 (14) | 0.0394 (13) | 0.0446 (14) | −0.0020 (10) | −0.0032 (13) | 0.0031 (12) |
C20 | 0.0452 (15) | 0.0329 (12) | 0.0353 (13) | −0.0010 (11) | 0.0017 (12) | 0.0021 (10) |
C21 | 0.0514 (15) | 0.0450 (14) | 0.0432 (14) | 0.0056 (12) | −0.0095 (13) | 0.0006 (12) |
C22 | 0.0638 (18) | 0.0530 (16) | 0.0544 (16) | 0.0178 (15) | −0.0064 (15) | 0.0009 (13) |
C23 | 0.069 (2) | 0.0445 (16) | 0.0668 (19) | 0.0164 (14) | 0.0035 (16) | −0.0040 (14) |
C24 | 0.0637 (18) | 0.0387 (13) | 0.0548 (16) | −0.0014 (12) | 0.0030 (15) | −0.0079 (12) |
C25 | 0.103 (3) | 0.079 (2) | 0.102 (3) | 0.046 (2) | −0.040 (2) | −0.0132 (19) |
N1—C17 | 1.509 (3) | C10—H10B | 0.9700 |
N1—C9 | 1.512 (3) | C11—C16 | 1.377 (4) |
N1—H1A | 0.9000 | C11—C12 | 1.385 (4) |
N1—H1B | 0.9000 | C12—C13 | 1.370 (5) |
O1—C1 | 1.363 (4) | C12—H12 | 0.9300 |
O1—C8 | 1.423 (4) | C13—C14 | 1.368 (5) |
O2—C19 | 1.372 (3) | C13—H13 | 0.9300 |
O2—H2 | 0.8200 | C14—C15 | 1.354 (5) |
C1—C2 | 1.395 (4) | C14—H14 | 0.9300 |
C1—C6 | 1.404 (5) | C15—C16 | 1.383 (4) |
C2—C3 | 1.387 (4) | C15—H15 | 0.9300 |
C2—C9 | 1.500 (3) | C16—H16 | 0.9300 |
C3—C4 | 1.389 (4) | C17—C20 | 1.505 (3) |
C3—H3 | 0.9300 | C17—C18 | 1.523 (4) |
C4—C5 | 1.369 (6) | C17—H17 | 0.9800 |
C4—C7 | 1.505 (5) | C18—H18A | 0.9600 |
C5—C6 | 1.363 (6) | C18—H18B | 0.9600 |
C5—H5 | 0.9300 | C18—H18C | 0.9600 |
C6—H6 | 0.9300 | C19—C24 | 1.387 (3) |
C7—H7A | 0.9600 | C19—C20 | 1.389 (3) |
C7—H7B | 0.9600 | C20—C21 | 1.385 (3) |
C7—H7C | 0.9600 | C21—C22 | 1.387 (3) |
C7—H7D | 0.9600 | C21—H21 | 0.9300 |
C7—H7E | 0.9600 | C22—C23 | 1.384 (4) |
C7—H7F | 0.9600 | C22—C25 | 1.508 (4) |
C8—H8A | 0.9600 | C23—C24 | 1.377 (4) |
C8—H8B | 0.9600 | C23—H23 | 0.9300 |
C8—H8C | 0.9600 | C24—H24 | 0.9300 |
C8—H8D | 0.9600 | C25—H25A | 0.9600 |
C8—H8E | 0.9600 | C25—H25B | 0.9600 |
C8—H8F | 0.9600 | C25—H25C | 0.9600 |
C9—C10 | 1.531 (3) | C25—H25D | 0.9600 |
C9—H9 | 0.9800 | C25—H25E | 0.9600 |
C10—C11 | 1.497 (4) | C25—H25F | 0.9600 |
C10—H10A | 0.9700 | ||
C17—N1—C9 | 115.59 (18) | C11—C10—H10A | 109.0 |
C17—N1—H1A | 108.4 | C9—C10—H10A | 109.0 |
C9—N1—H1A | 108.4 | C11—C10—H10B | 109.0 |
C17—N1—H1B | 108.4 | C9—C10—H10B | 109.0 |
C9—N1—H1B | 108.4 | H10A—C10—H10B | 107.8 |
H1A—N1—H1B | 107.4 | C16—C11—C12 | 117.8 (3) |
C1—O1—C8 | 117.9 (3) | C16—C11—C10 | 121.3 (2) |
C19—O2—H2 | 109.5 | C12—C11—C10 | 120.9 (3) |
O1—C1—C2 | 116.3 (3) | C13—C12—C11 | 121.0 (3) |
O1—C1—C6 | 125.7 (3) | C13—C12—H12 | 119.5 |
C2—C1—C6 | 118.0 (4) | C11—C12—H12 | 119.5 |
C3—C2—C1 | 119.1 (3) | C14—C13—C12 | 120.4 (3) |
C3—C2—C9 | 121.6 (2) | C14—C13—H13 | 119.8 |
C1—C2—C9 | 119.3 (3) | C12—C13—H13 | 119.8 |
C2—C3—C4 | 122.6 (3) | C15—C14—C13 | 119.4 (3) |
C2—C3—H3 | 118.7 | C15—C14—H14 | 120.3 |
C4—C3—H3 | 118.7 | C13—C14—H14 | 120.3 |
C5—C4—C3 | 117.2 (4) | C14—C15—C16 | 120.8 (3) |
C5—C4—C7 | 121.8 (4) | C14—C15—H15 | 119.6 |
C3—C4—C7 | 121.0 (4) | C16—C15—H15 | 119.6 |
C6—C5—C4 | 122.0 (4) | C11—C16—C15 | 120.5 (3) |
C6—C5—H5 | 119.0 | C11—C16—H16 | 119.7 |
C4—C5—H5 | 119.0 | C15—C16—H16 | 119.7 |
C5—C6—C1 | 121.1 (4) | C20—C17—N1 | 110.44 (19) |
C5—C6—H6 | 119.5 | C20—C17—C18 | 114.34 (19) |
C1—C6—H6 | 119.5 | N1—C17—C18 | 108.22 (19) |
C4—C7—H7A | 109.5 | C20—C17—H17 | 107.9 |
C4—C7—H7B | 109.5 | N1—C17—H17 | 107.9 |
H7A—C7—H7B | 109.5 | C18—C17—H17 | 107.9 |
C4—C7—H7C | 109.5 | C17—C18—H18A | 109.5 |
H7A—C7—H7C | 109.5 | C17—C18—H18B | 109.5 |
H7B—C7—H7C | 109.5 | H18A—C18—H18B | 109.5 |
C4—C7—H7D | 109.5 | C17—C18—H18C | 109.5 |
H7A—C7—H7D | 141.1 | H18A—C18—H18C | 109.5 |
H7B—C7—H7D | 56.3 | H18B—C18—H18C | 109.5 |
H7C—C7—H7D | 56.3 | O2—C19—C24 | 122.4 (2) |
C4—C7—H7E | 109.5 | O2—C19—C20 | 117.7 (2) |
H7A—C7—H7E | 56.3 | C24—C19—C20 | 120.0 (2) |
H7B—C7—H7E | 141.1 | C21—C20—C19 | 118.7 (2) |
H7C—C7—H7E | 56.3 | C21—C20—C17 | 119.7 (2) |
H7D—C7—H7E | 109.5 | C19—C20—C17 | 121.6 (2) |
C4—C7—H7F | 109.5 | C20—C21—C22 | 122.5 (2) |
H7A—C7—H7F | 56.3 | C20—C21—H21 | 118.8 |
H7B—C7—H7F | 56.3 | C22—C21—H21 | 118.8 |
H7C—C7—H7F | 141.1 | C23—C22—C21 | 117.2 (3) |
H7D—C7—H7F | 109.5 | C23—C22—C25 | 121.6 (3) |
H7E—C7—H7F | 109.5 | C21—C22—C25 | 121.2 (3) |
O1—C8—H8A | 109.5 | C24—C23—C22 | 122.0 (2) |
O1—C8—H8B | 109.5 | C24—C23—H23 | 119.0 |
H8A—C8—H8B | 109.5 | C22—C23—H23 | 119.0 |
O1—C8—H8C | 109.5 | C23—C24—C19 | 119.7 (2) |
H8A—C8—H8C | 109.5 | C23—C24—H24 | 120.2 |
H8B—C8—H8C | 109.5 | C19—C24—H24 | 120.2 |
O1—C8—H8D | 109.5 | C22—C25—H25A | 109.5 |
H8A—C8—H8D | 141.1 | C22—C25—H25B | 109.5 |
H8B—C8—H8D | 56.3 | H25A—C25—H25B | 109.5 |
H8C—C8—H8D | 56.3 | C22—C25—H25C | 109.5 |
O1—C8—H8E | 109.5 | H25A—C25—H25C | 109.5 |
H8A—C8—H8E | 56.3 | H25B—C25—H25C | 109.5 |
H8B—C8—H8E | 141.1 | C22—C25—H25D | 109.5 |
H8C—C8—H8E | 56.3 | H25A—C25—H25D | 141.1 |
H8D—C8—H8E | 109.5 | H25B—C25—H25D | 56.3 |
O1—C8—H8F | 109.5 | H25C—C25—H25D | 56.3 |
H8A—C8—H8F | 56.3 | C22—C25—H25E | 109.5 |
H8B—C8—H8F | 56.3 | H25A—C25—H25E | 56.3 |
H8C—C8—H8F | 141.1 | H25B—C25—H25E | 141.1 |
H8D—C8—H8F | 109.5 | H25C—C25—H25E | 56.3 |
H8E—C8—H8F | 109.5 | H25D—C25—H25E | 109.5 |
C2—C9—N1 | 112.0 (2) | C22—C25—H25F | 109.5 |
C2—C9—C10 | 113.2 (2) | H25A—C25—H25F | 56.3 |
N1—C9—C10 | 108.01 (19) | H25B—C25—H25F | 56.3 |
C2—C9—H9 | 107.8 | H25C—C25—H25F | 141.1 |
N1—C9—H9 | 107.8 | H25D—C25—H25F | 109.5 |
C10—C9—H9 | 107.8 | H25E—C25—H25F | 109.5 |
C11—C10—C9 | 112.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2 | 0.90 | 2.18 | 2.771 (3) | 123 |
N1—H1B···Cl1i | 0.90 | 2.21 | 3.104 (2) | 170 |
O2—H2···Cl1 | 0.82 | 2.29 | 3.114 (2) | 177 |
Symmetry code: (i) −x+1, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C25H30NO2+·Cl− |
Mr | 411.95 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 298 |
a, b, c (Å) | 9.227 (3), 15.323 (6), 16.504 (6) |
V (Å3) | 2333.4 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.18 |
Crystal size (mm) | 0.43 × 0.35 × 0.31 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.926, 0.946 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12327, 4115, 3080 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.097, 1.01 |
No. of reflections | 4115 |
No. of parameters | 263 |
No. of restraints | 18 |
H-atom treatment | GEOM |
Δρmax, Δρmin (e Å−3) | 0.14, −0.13 |
Absolute structure | Flack (1983) |
Absolute structure parameter | −0.03 (7) |
Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1995), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2 | 0.90 | 2.18 | 2.771 (3) | 123 |
N1—H1B···Cl1i | 0.90 | 2.21 | 3.104 (2) | 170 |
O2—H2···Cl1 | 0.82 | 2.29 | 3.114 (2) | 177 |
Symmetry code: (i) −x+1, y−1/2, −z+1/2. |
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The synthesis of enantiopure amines is an important subject of research because this class of compounds has found widespread application in biological systems showing pharmacological activity, and these compounds are used as resolving agents, chiral bases and auxiliaries in asymmetric synthesis (Juraristi, 1997; Clifton et al., 1982; Palmieri, 1999, 2000; Cimarelli & Palmieri, 1998, 2000). Most of them have been derived from a few readily available natural products (Soai & Niwa, 1992; Ager et al., 1996). To increase the understanding of asymmetric reactions, the design and synthesis of chiral ligands from non-natural resources is an essential research area in the field of synthetic organic chemistry (Vidal-Ferran et al., 1997; Bolm et al., 1998; Reddy et al., 1999; Paleo et al., 2000; Nugent, 2002) and chiral aminoalkylphenols are gaining increasing importance (Palmieri, 2000; Vyskocil et al., 1998; Cardellicchio et al., 1998, 1999; Bernardinelli et al., 2000; Liu et al., 2001; Cimarelli et al., 2001; Zhang et al., 2003).
We report here the molecular structure of one example of this class of aminoalkylphenols, namely 2-{(R)-1-[(R)-1-(2-methoxy-5-methylphenyl)-2-phenylethylamino]ethyl}-4- methylphenol, (I). The aminoalkylphenol was prepared by conventional condensation of (R)-(-)-[(2-methoxy-5-methyl)-phenyl]-2- phenyl ethylamine with 2-hydroxy-5-methyl acetophenone (both purchased from J&K Chemical Ltd), andthen reduction using sodium borohydride in a tetrahydrofuran (THF)/ethanol (1:1, v/v) mixture. The (R,R)-diastereoisomer is obtained as the main product; the chemical yield of purified and isolated (R,R)-(I) and the diastereoisomeric excess, d.e. (determined by 1HMR of the crude reaction mixture), are 89.2 and 99.0%, respectively. Generally, the reduction should take place after the boron coordinates the imine N atom, activating the C═ N double bond, which assumes predominantly an E configuration, to nucleophilic attack. Subsequently, an intramolecular hydride transfer from NaBH4 to the C atom both on the si or re face of the C═N double bond takes place. Calculations were performed to find the energies of the transition states (R,R)–(I)—Ts and (S,R)–(I)–Ts, minimized at the PM3 semiempirical level, corresponding to the two different situations. Transition state (R,R)–(I)–Ts was more stable, with a difference of 1.35 kcal mol−1, and this value is in satisfactory accordance with experimental d.e., which shows (R,R)–(I) as major product. This is in agreement with the fact that for si attack, the hydride enters on the less hindered side, on the same side of the H atom of the chiral auxiliary (R)-(2-methoxy-5-methyl)phenyl benzyl group. At the same time the N-atom lone pair is gauche between the (2-hydroxy-5-methyl)phenyl and the methyl group of the same chiral group, in a very favourable position. On the other hand, the attack on the re face is on the more hindered side (Me) and with the N-atom lone pair in a less convenient position between (2-hydroxy-5-methyl)phenyl and hydrogen.
It is noteworthy that a novel chiral aminoalkylphenol, (I), was synthesized. To confirm the structure of (I), an X-ray study of the title compound, (II), was carried out (Fig. 1).
The molecular structure of Despite the large number of hydrogen bonds within the asymmetric unit, t(II) is shown in Fig. 1. Thes C1–C6 and C11–C16 aromatic ring are approximately parallel (Fig. 2), the dihedral angle between their planes being 4.5°. The dihehral angle between the planes of the C1–C6 and C19–C24 aromatic rings is 20.0°, while the dihedral angle between the C11–C16 and C19–C24 planes is 14.0°.
Selected bond lengths and angles, including those of the new stereogenic carbon center (C17), are reported in Table 1. The absolute configuration of (I) and (II) is (R,R), as shown in Fig. 1.
N—H···O hydrogen bonds are present within the asymmetric unit; atom N1 act as a hydrogen-bond donor to phenolyl atom O2 (Fig. 2 and Table 2). The molecular structure depends on two further pairs of N—H···Cl and O—H···Cl hydrogen bonds, from atoms N1 and O2 in the cation to atom Cl1 (Fig. 2 and Table 2).