(R P)-Menthyl (1-hydroxy­cyclo­hexyl)phenyl­phosphinate

Baoci Fu; Chang-Qiu Zhao

doi:10.1107/S1600536810009219

. 2010 Mar 17;66(Pt 4):o859. doi: 10.1107/S1600536810009219

(R _P)-Menthyl (1-hydroxycyclohexyl)phenylphosphinate

Baoci Fu ^a, Chang-Qiu Zhao ^a,^*

PMCID: PMC2983758 PMID: 21580682

Abstract

The title compound, C₂₂H₃₅O₃P, features a tetrahedral P atom bonded to a phenyl ring, a hydroxycyclohexyl unit and the O atom of a menthyl group. The axial chirality at phosphorus is R _P. In the crystal, molecules are connected through O—H⋯O hydrogen bonds involving the hydroxy and P=O groups, forming chains along the 2₁ screw axis. The methyl groups of the isopropyl fragment in the menthyl unit are disordered over two sites of equal occupancy.

Related literature

For general background to α-hydroxy alkylphosphonates, see: Kim & Wiemer (2003 ▶). For the structures of related phenylphosphinates, see: Sheldrick et al. (1981 ▶); Chaloner et al. (1991 ▶); Grice et al. (2004 ▶).

Experimental

Crystal data

C₂₂H₃₅O₃P
M _r = 378.47
Monoclinic,
a = 10.1808 (11) Å
b = 11.0611 (13) Å
c = 10.4207 (12) Å
β = 106.201 (1)°
V = 1126.9 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 298 K
0.42 × 0.32 × 0.26 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.944, T _max = 0.965
5667 measured reflections
3787 independent reflections
3248 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.096
S = 1.06
3787 reflections
263 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.24 e Å⁻³
Absolute structure: Flack (1983 ▶), 1685 Friedel pairs
Flack parameter: 0.14 (10)

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810009219/bh2267sup1.cif

e-66-0o859-sup1.cif^{(20.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810009219/bh2267Isup2.hkl

e-66-0o859-Isup2.hkl^{(185.6KB, 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
O3—H3⋯O2ⁱ	0.76 (3)	1.94 (3)	2.695 (3)	170 (3)

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Symmetry code: (i) Inline graphic .

Acknowledgments

We acknowledge the financial support of the Natural Science Foundation of China (No. 20772055).

supplementary crystallographic information

Comment

α-Hydroxy alkylphosphonates have received attention both as substrates for the preparation of other α-substituted phosphonates, and because of their potential biological activity. For example, representatives of this class act as inhibitors of farnesyl protein transferase (FPTase), renin, and HIV protease (Kim & Wiemer, 2003).

The P-chiral title compound, which can be synthesized by addition of (R_P)-menthyl-phenylphosphinate to cyclohexanone (see Experimental), is comprised of fully extended substituents: phenyl, menthyl and α-hydroxycyclohexyl. The configuration of the central P atom is R and the four groups around the P atom form an irregular tetrahedron as found in tert-butyl diphenylphosphinate (Grice et al., 2004). The bond angles are C1—P—C17 = 107.13 (11)°, O1—P—C1 = 107.06 (10)°, O1—P—C17 = 102.87 (9)°, O2—P—O1 = 113.87 (9)°, O2—P—C17 = 113.18 (11)° and O2—P—C1 = 112.05 (11)°, which compare with angles observed in related phenylphosphinate derivatives bearing a menthyl group (Chaloner et al., 1991; Sheldrick et al., 1981). Part of methyl groups (C14 and C15) were found to be disordered over two sites with equal occupancies.

Intramolecular O3—H3···O2 hydrogen bonds are found in the crystal structure. The crystal packing is further stabilized by van der Waals interactions.

Experimental

Cyclohexanone was added to a stirred DMF solution of (R_P)-menthyl-phenylphosphinate in a flask and the mixture was stirred for 48 h at room temperature. After washing with water, the resulting solid was dried, and recrystallized from diethyl ether, to afford the pure title product.