rac-Diethyl 9-hy­droxy-9-methyl-7-phenyl-1,4-diaza­spiro­[4.5]decane-6,8-dicarboxyl­ate

Abel M Maharramov; Arif I Ismiyev; Bahruz A Rashidov; Gunel M Rahimova; Mirza A Allahverdiyev

doi:10.1107/S1600536810054498

. 2011 Jan 8;67(Pt 2):o291. doi: 10.1107/S1600536810054498

rac-Diethyl 9-hydroxy-9-methyl-7-phenyl-1,4-diazaspiro[4.5]decane-6,8-dicarboxylate

Abel M Maharramov ^a, Arif I Ismiyev ^a, Bahruz A Rashidov ^a,^*, Gunel M Rahimova ^a, Mirza A Allahverdiyev ^a

PMCID: PMC3051672 PMID: 21522983

Abstract

The title molecule, C₂₁H₃₀N₂O₅, is chiral with four stereogenic centres. The crystal is a racemate and consists of enantiomeric pairs with the relative configuration rac-(6S*,7R*,8R*,9S*). The ethyl fragment of the ethoxycarbonyl group at position 6 is disordered in a 0.46 (3):0.54 (3) ratio. The crystal structure features intermolecular N—H⋯O. Intramolecular O—H⋯N and N—H⋯O hydrogen bonds also occur.

Related literature

For general background to the biological activity of β-cycloketoles and their nitrogenous derivatives, see: Krivenko et al. (2003 ▶).

Experimental

Crystal data

C₂₁H₃₀N₂O₅
M _r = 390.47
Triclinic,
a = 9.4140 (17) Å
b = 10.7606 (19) Å
c = 10.7874 (19) Å
α = 103.000 (4)°
β = 97.413 (4)°
γ = 97.736 (4)°
V = 1040.6 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.20 × 0.20 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.983, T _max = 0.987
8475 measured reflections
4252 independent reflections
2225 reflections with I > 2σ(I)
R _int = 0.065

Refinement

R[F ² > 2σ(F ²)] = 0.068
wR(F ²) = 0.175
S = 1.00
4252 reflections
288 parameters
45 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 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: SHELXL97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810054498/si2321sup1.cif

e-67-0o291-sup1.cif^{(24KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810054498/si2321Isup2.hkl

e-67-0o291-Isup2.hkl^{(208.3KB, 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
O5—H5O⋯N4	0.87 (3)	1.87 (3)	2.714 (4)	163 (3)
N4—H4N⋯O2	0.86 (4)	2.23 (4)	2.971 (4)	144 (4)
N1—H1N⋯O4ⁱ	0.93 (3)	2.32 (3)	3.113 (3)	143

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Symmetry code: (i) Inline graphic .

Acknowledgments

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

supplementary crystallographic information

Comment

Established that β-cycloketoles and their nitrogenous derivatives possess a wide spectrum of biological activity (Krivenko et al. 2003). The reactions of β-cycloketoles with ethilendiamine possibly leading to valuable compounds of practical use remain unexplored. Reaction β-cycloketoles with ethilendiamine has not been studied. Several reaction paths may be expected: one or two reactive centers of the substrate and reagent may be involved. Enamines or the products of heterocyclization or spirocyclization may be produced.

In the title compound, C₂₁H₃₀N₂O₅ (I), the cyclohexane ring adopts a chair conformation. The structure of (I) is reported here (Fig. 1). The crystal structure involves N—H···O intermolecular and O—H···N and N—H···O intramolecular hydrogen bonds. (Table 1 and Fig. 2).

The cyclohexane ring has a chair conformation. The phenyl ring is in a pseudo-equatorial position. Torsion angle between the ethoxycarbonyl group and the phenyl substituent is C14—C7—C8—C20 is 55.4 (3) ° and C11—C6—C7—C14 is -53.4 (3) °, which indicates the pseudo-axial location of hydrogen atoms at C6 C7 and C8.

THe imidazolidine ring has a envelope conformation. The fragment of a ring N1—C2—C3—N4 is almost planar - torsion angle is -6.9 (3) °.

The molecules (I) are diastereomers and possess three asymmetric centers at th C6, C7, C8 and C9 carbon atoms. The crystal of (I) is racemate and consists of enantiomeric pairs with the relative configuration of the centers of rac-6S*,7R*, 8R*, 9S*.The two [(C7(R),C8(R)] of four stereogenic centres of (I) are of the same chirality.

Experimental

(rac)-diethyl-4-hydroxy-4-methyl-6-oxo-2-phenyl-1,3-dicarboxylate (20 mmol), ethilendiamine (20 mmol) were dissolved in 20 ml e thanol. The mixture was stirred at 345–350 K within 10 h. After cooling to a room temperature obtained white crystals. The crystals were filtered and washed with ethanol and have been then dissolved in ethanol (50 ml) and recrystallized to yield colourless block-shaped crystals of the title compound.