2-(4-Methyl­cyclo­hex-3-en­yl)propan-2-yl N-phenyl­carbamate

Raza Murad Ghalib; Othman Sulaiman; Sayed Hasan Mehdi; Jia Hao Goh; Hoong-Kun Fun

doi:10.1107/S1600536810025080

. 2010 Jul 3;66(Pt 8):o1889–o1890. doi: 10.1107/S1600536810025080

2-(4-Methylcyclohex-3-enyl)propan-2-yl N-phenylcarbamate

Raza Murad Ghalib ^a, Othman Sulaiman ^a, Sayed Hasan Mehdi ^a, Jia Hao Goh ^b,^‡, Hoong-Kun Fun ^b,^*,^§

PMCID: PMC3007260 PMID: 21588225

Abstract

In the title carbamate compound, C₁₇H₂₃NO₂, one of the Csp ³ atoms of the cyclohexene ring is disordered over two sites with refined occupancies of 0.55 (2) and 0.45 (2), both disorder components resulting in half-boat conformations. The mean plane through the carbamate unit is inclined at interplanar angles of 14.80 (13), 18.30 (17) and 24.0 (2)°, respectively, with respect to the phenyl ring, and the major and minor disorder component cyclohexene rings. In the crystal structure, adjacent molecules are linked into chains along [001] via intermolecular N—H⋯O hydrogen bonds. The crystal structure is further stabilized by weak intermolecular C—H⋯π interactions.

Related literature

For general background to and applications of the title compound, see: Banerjee et al. (1978 ▶); Graia et al. (2009 ▶); Ibuka et al. (1985 ▶); Lapidus et al. (1987 ▶); Loev & Kormendy (1963 ▶); Muradov et al. (1986 ▶); Niu et al. (2007 ▶); Ibuka et al. (1985 ▶). For related carbamate structures, see: Garden et al. (2007 ▶); Graia et al. (2009 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₁₇H₂₃NO₂
M _r = 273.36
Monoclinic,
a = 19.3067 (19) Å
b = 9.0058 (9) Å
c = 8.9521 (9) Å
β = 100.964 (3)°
V = 1528.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100 K
0.58 × 0.20 × 0.10 mm

Data collection

Bruker APEXII DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.957, T _max = 0.992
8744 measured reflections
2205 independent reflections
2053 reflections with I > 2σ(I)
R _int = 0.049

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.154
S = 1.15
2205 reflections
187 parameters
4 restraints
H-atom parameters constrained
Δρ_max = 0.68 e Å⁻³
Δρ_min = −0.76 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810025080/hb5524sup1.cif

e-66-o1889-sup1.cif^{(21.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810025080/hb5524Isup2.hkl

e-66-o1889-Isup2.hkl^{(108.4KB, hkl)}

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

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

Cg1 is the centroid of the C1–C6 phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O2ⁱ	0.86	2.12	2.969 (3)	170
C13—H13A⋯Cg1ⁱⁱ	0.97	2.62	3.566 (3)	166

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

Acknowledgments

The authors would like to acknowledge Universiti Sains Malaysia (USM) for the University Grant (No. 1001/PTEKIND/8140152). HKF and JHG thank USM for the Research University Golden Goose Grant (No. 1001/PFIZIK/811012). JHG also thanks USM for the award of a USM fellowship.

supplementary crystallographic information

Comment

Carbamates are well-known class of compounds with biological activity (Muradov et al., 1986). They can be prepared by different methods, for example by nickel-catalyzed coupling of CO₂ and amines (Niu et al., 2007), by stirring of alcohols including steroids as well as primary and secondary alcohols, polyols, phenols with sodium cynate, and trifluoroacetic acid (Loev & Kormendy, 1963), by carbonylation of aromatic nitro compounds (Lapidus et al., 1987), by the reaction of isocynates with alcohols (Ibuka et al., 1985) in the presence of lewis acid and by the reaction of an amine and an alcohol with phosgene. Phytosterol, β-Sitosterol, stigmasterol and cholesterol react with phenyl isocyanate to give carbamate (Banerjee et al., 1978; Graia et al., 2009). In this study the title compound has been synthesized by the reaction of α-terpineol with phenylisocyanate in the presence of catalytic amount of HCl in chloroform solvent.

In the title carbamate compound (Fig. 1), atom C10 of the cyclohexene ring (C9-C14) is disordered over two sites with a refined occupancy ratio of 0.55 (2):0.45 (2). The major (C9/C10A/C11-C14) and minor (C9/C10B/C11-C14) disordered cyclohexene rings adopt the same conformation, that is the half-boat conformation; puckering parameters Q = 0.427 (4) Å, θ = 57.4 (5)°, φ = 335.9 (7)° for major disordered component and Q = 0.651 (6) Å, θ = 131.6 (4)° and φ = 161.7 (7)° for minor disordered component. The mean plane through the carbamate moiety (N1/C7/O1/O2) is inclined at interplanar angles of 14.80 (13), 18.30 (17) and 24.0 (2)°, respectively, with respect to the C1-C6 phenyl ring, major and minor disordered cyclohexene rings. The bond lengths and angles are comparable to those related carbamate structures (Garden et al., 2007; Graia et al., 2009).

In the crystal structure, intermolecular N1—H1N1···O2 hydrogen bonds (Table 1) link adjacent molecules into one-dimensional chains running along the [001] direction (Fig. 2). Further stabilization of the crystal structure is provided by weak intermolecular C13—H13A···Cg1 interactions (Table 1) involving the centroid of the C1-C6 phenyl ring.

Experimental

A mixture of α-terpineol (1.640 ml) and phenylisocyanate (1.087 ml) in 1:1 molar ratio were stirred in chloroform for 30 minutes in the presence of catalytic amount of HCl. The reaction mixture was dried on rota vapor at low pressure and then chromatographed over silica gel column loaded in light petroleum ether. The column was eluted only with light petroleum ether to give five fractions of the title compound. These fractions were mixed together on the basis of same TLC results and crystallized with chloroform:alcohol (1:1) to give the colourless needles of (I) (1.93 g, M.p. 378 K). The melting point was taken on Thermo Fisher digital melting point apparatus of IA9000 series and is uncorrected. Open column chromatography was performed on silica gel 60 (Merck, 0.040–0.063 mm, 230–400 mesh ASTM) and Sephadex LH-20 (Pharmacia). TLCs were taken on silica gel plates (silica gel 60 F₂₅₄ on aluminum foil, Merck).