2,4-Dichloro-6-((1R)-1-{[(R)-(2-chloro­phen­yl)(cyclo­pent­yl)meth­yl]amino}eth­yl)phenol

Guang-You Zhang; Di-Juan Chen; Shu-Hong Wang; Ting Yang; Jian-Guo Chang

doi:10.1107/S1600536809041403

. 2009 Oct 17;65(Pt 11):o2759. doi: 10.1107/S1600536809041403

2,4-Dichloro-6-((1R)-1-{[(R)-(2-chlorophenyl)(cyclopentyl)methyl]amino}ethyl)phenol

Guang-You Zhang ^a, Di-Juan Chen ^a,^*, Shu-Hong Wang ^a, Ting Yang ^b, Jian-Guo Chang ^c

PMCID: PMC2971355 PMID: 21578353

Abstract

In the title compound, C₂₀H₂₂Cl₃NO, the five-membered ring adopts an envelope conformation, and the two benzene rings are oriented at a dihedral angle of 40.44 (9)°. Intramolecular O—H⋯N and N—H⋯Cl hydrogen bonding is present. In the crystal, the molecules are linked via weak intermolecular C—H⋯O hydrogen bonds.

Related literature

For aminophenols, see: Li et al. (2004 ▶); Puigjaner et al. (1999 ▶); Cimarelli et al. (2002 ▶); Joshi & Malhotra (2003 ▶); Zhang et al. (2003 ▶); Watts et al. (2005 ▶). For the synthesis, see: Yang et al. (2005 ▶).

Experimental

Crystal data

C₂₀H₂₂Cl₃NO
M _r = 398.74
Orthorhombic,
a = 8.4132 (7) Å
b = 13.6767 (10) Å
c = 17.0018 (14) Å
V = 1956.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.48 mm⁻¹
T = 298 K
0.21 × 0.16 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.907, T _max = 0.945
10361 measured reflections
3453 independent reflections
3005 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.096
S = 1.04
3453 reflections
227 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.18 e Å⁻³
Absolute structure: Flack (1983 ▶), 1464 Friedel pairs
Flack parameter: 0.00 (7)

Data collection: SMART (Bruker, 1999 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809041403/xu2619sup1.cif

e-65-o2759-sup1.cif^{(21.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809041403/xu2619Isup2.hkl

e-65-o2759-Isup2.hkl^{(172.8KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N1	0.96	1.74	2.622 (3)	151
N1—H1N⋯Cl3	0.84	2.68	3.260 (2)	127
C13—H13⋯O1ⁱ	0.93	2.56	3.422 (3)	154

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors are grateful to the Natural Science Foundation of Shandong Province, China (grant No. G0231) and the Foundation of the Education Ministry of China for Returned Students (grant No. G0220) for financial support. The X-ray data were collected at Taishan University, China.

supplementary crystallographic information

Comment

The chiral aminophenols containing some O and N atoms are of great interests due to their widespread application in asymmetric synthesis such as chiral bases, auxiliaries and ligands (Li et al., 2004; Puigjaner et al., 1999; Cimarelli et al., 2002). Recently, the synthesis of chiral aminophenols with a varity of functionalities has attracted increasing attention (Zhang et al., 2003; Watts et al., 2005). Herein, we present the molecular structure of the title aminophenol (I), which was initially prepared to test its catalytic activity. The aminophenol was prepared by conventional condensation of (R)-1-(2-chlorophenyl)-1-cyclopentylmethanamine with 1-(3,5-dichloro-2-hydroxyphenyl) ethanone in methanol.

The molecular structure of (I) is illustrated in Fig. 1. The title compoud has two chiral centers (C7/C9), which have configurations R, R, confirmed by the X-ray structural analysis. There are the intramolecular O—H···N and N—H···Cl hydrogen bonding which stablizes the conformation of the molecule (Table 1). In the crystal packing, the molecules are linked to each other via intermolecular C—H···O hydrogen bonds (Table 1).

Experimental

The title compound was prepared according to the procedure of Yang et al. (2005). (R)-1-(2-chlorophenyl)-1-cyclopentylmethanamine (0.9 mmol) and 1-(3,5-dichloro-2-hydroxyphenyl)ethanone (0.9 mmol) were dissolved in methanol (10 ml) and reacted at room temperature for 48 h. After removal of the solvent, NaBH₄ (4.5 mmol) was added to the solution in THF/ethanol (1:1 v/v, 20 ml) and stirred at 273 K until the solution became colourless. The solvent was then removed under reduced pressure. Water (10 ml) was added to the residue and 1 M HCl was added dropwise until hydrogen production ceased. The mixture was neutralized with aqueous solution of Na₂CO₃, then extracted with CHCl₃, and the organic layer was dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure. Further purification was carried out by thin-layer silica-gel chromatography (chloroform) to give a colorless solid (yield 82.7%). Single crystals of (I) were grown from the n-hexane solution.