(R)-2,2′-Bis(meth­oxy­meth­oxy)-1,1′-binaphth­yl

Liang Zhou; Wumanjiang Eli

doi:10.1107/S1600536812014699

. 2012 Apr 13;68(Pt 5):o1361. doi: 10.1107/S1600536812014699

(R)-2,2′-Bis(methoxymethoxy)-1,1′-binaphthyl

Liang Zhou ^a, Wumanjiang Eli ^a,^*

PMCID: PMC3344493 PMID: 22590255

Abstract

The asymmetric unit of the title compound, C₂₄H₂₂O₄, contains two independent molecules in both of which the naphthalene ring systems adopts a transoid arrangement. The dihedral angles between the naphthalene ring system in the two molecules are 83.0 (1) and 89.0 (1)°. There are slight differences in the C(H₃)—O—C(H₂)—O– torsion angles of the eqivalent methoxymethoxy groups. In the crystal, weak C—H⋯O hydrogen bonds are present.

Related literature

For general background to the application of 1,1′-binaphthol (BINOL) derivatives in asymmetric synthesis, see: Brunel et al. (2006 ▶). For the synthesis, see: Shi & Wang (2002 ▶). For related structures, see: Tachi et al. (1999 ▶); Zong et al. (2011 ▶).

Experimental

Crystal data

C₂₄H₂₂O₄
M _r = 374.42
Orthorhombic,
a = 10.8608 (13) Å
b = 12.6158 (14) Å
c = 29.419 (3) Å
V = 4030.9 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.20 × 0.20 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.984, T _max = 0.985
19981 measured reflections
5112 independent reflections
3899 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.061
wR(F ²) = 0.149
S = 1.01
5112 reflections
509 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812014699/lh5447sup1.cif

e-68-o1361-sup1.cif^{(43KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812014699/lh5447Isup2.hkl

e-68-o1361-Isup2.hkl^{(250.4KB, hkl)}

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

Table 1. Selected torsion angles (°).

C1—O1—C2—O2	−68.1 (6)
C24—O4—C23—O3	64.4 (7)
C25—O5—C26—O6	−73.6 (5)
C48—O8—C47—O7	65.8 (7)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C34—H34A⋯O8ⁱ	0.93	2.40	3.251 (5)	152
C39—H39A⋯O5ⁱⁱ	0.93	2.52	3.417 (5)	161

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors are grateful to the Key Laboratory of Applied Catalysis of Xinjiang Technical Institute of Physics and Chemistry for financial support, and also acknowledge the Analysis and Testing Center of Xinjiang Technical Institute of Physics and Chemistry for their technical and instrumental support.

supplementary crystallographic information

Comment

Optically active 1,1'-binaphthol(BINOL) and its derivatives are one of the most important chiral ligands, and have been widely used for in asymmetric synthesis for many years (Brunel et al. 2006). Although 2,2'-bis(methoxymethoxy)-1,1'-binaphthyl is a very important intermediate to many chiral ligands for various metal complex catalysis, none of its structural properties have been explored. Within our ongoing project of synthesizing BINOL derivatives, we have synthesized the title compound determined its crystal structure. Examples of similar structures have been published (Tachi et al., 1999; Zong et al., 2011).

The asymmetric unit of the title compound is shown in Fig. 1. There are two crystallographically independent molecules in which the two naphthalene ring systems in each, adopt a transoid arrangement. There are only slight differences in the torsion angles of the eqivalent methoxymethoxy groups (Table 1). In the crystal, Fig. 2, molecules are linked by weak C—H···O hydrogen bonds.

Experimental

The title compound (I) was synthesized from (R)-BINOL according to the literature method (Shi & Wang, 2002). Under a nitrogen atmosphere, (R)-BINOL (5.72 g, 20 mmol) was added to a suspension of NaH (2.40 g, 100 mmol) in anhydrous THF (40 ml) at 273K with stirring. The resulting solution was further stirred at 273K for 10 min, and then methoxymethyl chloride (3.65 ml, 48 mmol) was slowly added. The mixture was allowed to warm to room temperature and stirred for 4 h. After the standard procedures of quenching, washing and drying the organic layers, the solvent was removed. A crystal suitable for X-ray analysis was grown from a solution of (I) in ethyl acetate and petroleum ether by slow evaporation at room temperature.