2-(Naphthalen-1-yl­amino)­cyclo­hexa­nol

Rachid Outouch; Brahim Boualy; Mustapha Ait Ali; Larbi El Firdoussi; Corrado Rizzoli

doi:10.1107/S1600536811021714

. 2011 Jun 11;67(Pt 7):o1628. doi: 10.1107/S1600536811021714

2-(Naphthalen-1-ylamino)cyclohexanol

Rachid Outouch ^a, Brahim Boualy ^a, Mustapha Ait Ali ^a, Larbi El Firdoussi ^a, Corrado Rizzoli ^b,^*

PMCID: PMC3152018 PMID: 21837034

Abstract

The title compound, C₁₆H₁₉NO, was synthesized under solvent-free conditions by reaction of 7-oxa-bicyclo[4.1.0]heptane and naphthalen-1-amine in the presence of Ca(CF₃COO)₂ as catalyst. The cyclohexane ring adopts a chair conformation. In the crystal, molecules are linked by intermolecular N—H⋯O hydrogen bonds and C—H⋯π interactions into chains parallel to the c axis.

Related literature

For background to applications of β-aminoalcohols in organic synthesis, see: Rogers et al. (1989 ▶); O’Brien (1999 ▶); Ager et al. (1996 ▶). For the synthesis of β-aminoalcohols, see: Deyrup & Moyer (1969 ▶); Kamal, Ramu et al. (2005 ▶); Yarapathy et al. (2006 ▶); Yadav et al. (2003 ▶); Rafiee et al. (2004 ▶); Robin et al. (2007 ▶); Das et al. (2000 ▶); Kamal, Adil & Arifuddin (2005 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₁₆H₁₉NO
M _r = 241.32
Orthorhombic,
a = 12.0278 (4) Å
b = 11.5910 (3) Å
c = 9.5566 (3) Å
V = 1332.33 (7) Å³
Z = 4
Cu Kα radiation
μ = 0.58 mm⁻¹
T = 294 K
0.18 × 0.15 × 0.10 mm

Data collection

Siemens AED diffractometer
4933 measured reflections
1353 independent reflections
1326 reflections with I > 2σ(I)
R _int = 0.034
3 standard reflections every 100 reflections intensity decay: 0.0%

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.087
S = 1.08
1353 reflections
169 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Data collection: AED (Belletti et al., 1993 ▶); cell refinement: AED; data reduction: AED; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and SCHAKAL97 (Keller, 1997 ▶); software used to prepare material for publication: SHELXL97 and PARST95 (Nardelli, 1995 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811021714/zl2377sup1.cif

e-67-o1628-sup1.cif^{(16.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811021714/zl2377Isup2.hkl

e-67-o1628-Isup2.hkl^{(66.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811021714/zl2377Isup3.cml

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

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

Cg1 is the centroid of the C7–C11/C16 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.83 (3)	2.30 (3)	3.125 (2)	171 (2)
C14—H14⋯Cg1ⁱ	0.93	2.71	3.530 (3)	148

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Symmetry code: (i) Inline graphic .

Acknowledgments

Financial support from the Universitá degli Studi di Parma is gratefully acknowledged.

supplementary crystallographic information

Comment

β-Amino alcohols are useful organic intermediates owing to their versatility as building blocks in the synthesis of several biologically active natural products (Rogers et al., 1989), unnatural amino acids (O'Brien, 1999) and chiral auxiliaries (Ager et al., 1996). These compounds are traditionally synthesized by direct treatment of epoxides with excessive amounts of amines at elevated temperatures (Deyrup & Moyer, 1969). Under such conditions, less reactive epoxides and sluggish amines react slowly and sensitive functional groups undergo undesirable side reactions. Many alterations were made in recent years to enhance the synthetic scope of this reaction by the use of Lewis acid catalysis (Kamal, Ramu et al., 2005), solid phase synthesis (Yarapathy et al., 2006), ionic liquids (Yadav et al., 2003), heteropolyacids (Rafiee et al., 2004), microwave irradiation (Robin et al., 2007), fluorinated solvents (Das et al., 2000), and ultrasound mediation (Kamal, Adil & Arifuddin, 2005). As a contribution to this widespread area, we describe here the synthesis and crystal structure of the title amino alcohol.

In the molecule of the title compound (Fig. 1), the cyclohexane ring adopts a chair conformation with puckering parameters (Cremer & Pople, 1975) Q = 0.5765 (19) Å, θ = 2.6 (2)° and φ = 31 (5)°. The hydroxy and amine substituent to the ring are equatorially oriented. In the crystal structure (Fig. 2), intermolecular N—H···O hydrogen bonds and C—H···π interactions (Table 1) link the molecules into chains running parallel to the c axis.

Experimental

In a screw capped vial equipped with a magnetic stirrer, Ca(CF₃CO₂)₂ (0.03 g, 0.11 mmol) was added to naphthalen-1-amine (0.293 g, 2.04 mmol) and 7-oxa-bicyclo[4.1.0]heptane (0.481 g, 2.00 mmol), and the resulting mixture was left under vigorous stirring at 313 K (40°C) for 31 h. The mixture was extracted with AcOEt (3 × 10 ml), and the combined organic layers were dried over anhydrous Na₂SO₄. The combined filtrates were concentrated under vacuum to afford the title product (276 mg, yield 56%). Crystals suitable for X-ray analysis were obtained by slow evaporation of a diethyl ether solution. M.p. 366–367 K.