rac-Diethyl 6-hy­droxy-4-[(2-hy­droxy­eth­yl)amino]-6-methyl-2-phenyl­cyclo­hex-3-ene-1,3-dicarboxyl­ate

Abel M Maharramov; Arif I Ismiyev; Bahruz A Rashidov

doi:10.1107/S1600536810052669

. 2010 Dec 18;67(Pt 1):o187. doi: 10.1107/S1600536810052669

rac-Diethyl 6-hydroxy-4-[(2-hydroxyethyl)amino]-6-methyl-2-phenylcyclohex-3-ene-1,3-dicarboxylate

Abel M Maharramov ^a,^*, Arif I Ismiyev ^a, Bahruz A Rashidov ^a

PMCID: PMC3050247 PMID: 21522691

Abstract

The title compound, C₂₁H₂₉NO₆, is chiral with three stereogenic centres. The crystal is a racemate and consists of enantiomeric pairs with the relative configuration rac-(2R*,3S*,4R*). The ethyl fragment of the ethoxycarbonyl group at position 1 is disordered in a 0.60:0.40 ratio. The crystal packing displays intermolecular O—H⋯O hydrogen bonding. An intramolecular N—H⋯O hydrogen bond also occurs.

Related literature

β-Cycloketoles and their nitrogenous derivatives possess a wide spectrum of biological activity, see: Krivenko et al. (2003 ▶).

Experimental

Crystal data

C₂₁H₂₉NO₆
M _r = 391.45
Monoclinic,
a = 41.078 (14) Å
b = 5.940 (2) Å
c = 18.683 (6) Å
β = 113.581 (13)°
V = 4178 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.30 × 0.30 × 0.30 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1998 ▶) T _min = 0.973, T _max = 0.973
18275 measured reflections
4530 independent reflections
3052 reflections with I > 2σ(I)
R _int = 0.060

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.143
S = 1.00
4530 reflections
263 parameters
8 restraints
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; 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 global, I. DOI: 10.1107/S1600536810052669/kp2299sup1.cif

e-67-0o187-sup1.cif^{(23.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810052669/kp2299Isup2.hkl

e-67-0o187-Isup2.hkl^{(222KB, 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—H1O⋯O6ⁱ	0.94	1.92	2.802 (2)	157
O6—H6O⋯O1ⁱⁱ	0.95	1.78	2.727 (2)	172
N1—H1N⋯O2	0.91	1.91	2.650 (2)	137

Open in a new tab

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

Acknowledgments

We thank Professor Victor N. Khrustalev for fruitful discussions and help with this work.

supplementary crystallographic information

Comment

β-Cycloketoles and their nitrogenous derivatives possess a wide spectrum of biological activity (Krivenko et al. 2003). The reactions of β-cycloketoles with ethanolamine possibly lead to valuable compounds of practical use but remain unexplored. Reaction β-cycloketoles with ethanolamine has not been studied. Several reaction paths may be expected: one or two reactive centres of the substrate and reagent may be involved. Enamines or the products of heterocyclisation or spirocyclisation may be produced.

The cyclohexene ring has a distorted half-chair conformation. Phenyl ring is in a pseudo-equatorial position (Fig. 1). Torsion angle between the ethoxycarbonyl group and the phenyl substituent, C12—C2—C3—C18 is 59,04 (18) °, indicating the pseudo-axial location of hydrogen atoms at C2 and C3. The crystal structure involves O—H···O intermolecular and O—H···O and N—H···O intramolecular hydrogen bonds (Table 1 and Fig. 2).

Experimental

(rac)-Diethyl-4-hydroxy-4-methyl-6-oxo-2-phenyl-1,3-dicarboxylate (20 mmol), monoethanolamine (20 mmol) were dissolved in 20 mL ethanol. The mixture was stirred at 345–350 K within 10 h. After cooling to a room temperature white crystals were obtained. The crystals were filtered and washed with ethanol. Then the crystals obtained were recrystallised from 50 mL ethanol to yield colourless block-shaped crystals of the title compound.