(2SR,3RS)-Methyl 2-(adamantan-1-yl)-3-phenyl­sulfonyl-3-(pyridin-2-ylsulfan­yl)propano­ate dichloro­methane hemisolvate

Rosa-Luisa Meza-León; Sylvain Bernès; Elsie Ramírez Domínguez; Martha Sosa-Rivadeneyra; Leticia Quintero-Cortés

doi:10.1107/S1600536811010312

. 2011 Mar 26;67(Pt 4):o981–o982. doi: 10.1107/S1600536811010312

(2SR,3RS)-Methyl 2-(adamantan-1-yl)-3-phenylsulfonyl-3-(pyridin-2-ylsulfanyl)propanoate dichloromethane hemisolvate

Rosa-Luisa Meza-León ^a, Sylvain Bernès ^b, Elsie Ramírez Domínguez ^a, Martha Sosa-Rivadeneyra ^a, Leticia Quintero-Cortés ^a,^*

PMCID: PMC3099796 PMID: 21754240

Abstract

The title compound, C₂₅H₂₉NO₄S₂ 0.5CH₂Cl₂, was obtained as a racemate. The pyridine and phenyl rings are arranged face-to-face, giving a weak intramolecular π–π interaction [centroid–centroid separation = 3.759 (3) Å]. These interactions are extended intermolecularly, forming chains of stacked rings along [001] with separations of 3.859 (3) and 3.916 (3) Å. The solvent used for crystallization, CH₂Cl₂, is located in voids between the chains of molecules, with a site occupancy of 0.5.

Related literature

For chemical, polymer and pharmaceutical applications of adamantane and its derivatives, see: Beller et al. (2002 ▶); Mathias et al. (1995 ▶, 2001 ▶); Stotskaya et al. (1995 ▶); Spasov et al. (2000 ▶); Enomoto et al. (2010 ▶). For catalyst reactions, see: Taoufik et al. (1999 ▶). For poly(p-phenylenevinylene) (PPV) derivatives, see: Jeong et al. (2002 ▶). For their antiviral and disease-related activity, see: Kadi et al. (2010 ▶); Papanastasiou et al. (2010 ▶) and for their use in the treatment of influenza A, leukemia and deafness, see: Zarubaev et al. (2010 ▶); Spasov et al. (2000 ▶). For the Barton decarboxylation reaction, see: Togo (2004 ▶).

Experimental

Crystal data

C₂₅H₂₉NO₄S₂·0.5CH₂Cl₂
M _r = 514.08
Monoclinic,
a = 12.709 (4) Å
b = 27.820 (6) Å
c = 14.448 (3) Å
β = 101.254 (19)°
V = 5010 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 298 K
0.40 × 0.40 × 0.40 mm

Data collection

Siemens P4 diffractometer
6603 measured reflections
4434 independent reflections
2936 reflections with I > 2σ(I)
R _int = 0.026
3 standard reflections every 97 reflections intensity decay: 40%

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.154
S = 1.03
4434 reflections
316 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: XSCANS (Siemens, 1996 ▶); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811010312/jj2070sup1.cif

e-67-0o981-sup1.cif^{(33.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811010312/jj2070Isup2.hkl

e-67-0o981-Isup2.hkl^{(217.3KB, hkl)}

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

Acknowledgments

We gratefully acknowledge financial support of the Facultad de Ciencias Químicas, Benemérita Universidad Autónoma de Puebla.

supplementary crystallographic information

Comment

Adamantane and its derivatives have a broad range of chemical (Taoufik et al., 1999; Beller et al., 2002), polymer (Mathias et al., 1995, 2001), and pharmaceutical (Stotskaya et al., 1995; Spasov et al., 2000; Enomoto et al., 2010) applications. Compounds containing adamantyl radicals are useful catalysts for many chemical reactions, such as the refining of halogen atoms and preparation of heterogeneous bimetallic catalysts (Taoufik et al., 1999). The rigid, spherical shape of adamantane reduces interchain interactions in polymers and may help with the synthesis of poly(p-phenylenevinylene) (PPV) derivatives (Jeong et al., 2002). Adamantane-containing molecules have also been found to have antiviral activity (Kadi et al., 2010; Papanastasiou et al., 2010) and have been used in the treatment of influenza A (Zarubaev et al., 2010), HIV-1, leukemia and deafness (Spasov et al., 2000).

Alkyl radicals derived from O-acyl esters of N-hydroxy-2-thiopyridone (a.k.a. Barton esters) are nucleophilic, so treatment with electron-deficient olefins such as vinyl sulfones generates the corresponding addition products (alkyl 2-pyridyl sulfides) effectively. Derivatives generated from adamantylcarboxylic acid using the Barton method (Togo, 2004) have potential biological activity. Crystallization of the racemate in the title compound is similar to an anti addition of the Barton ester to the olefin.

The title compound, is a racemic mixture of enantiomers (Fig. 2). The CH₂Cl₂ solvent molecule is placed close to a 2-fold axis with a site occupancy of 1/2. The dihedral angle between the mean planes of the phenyl and pyridine rings is 20.24 (12)° [centroid to centroid separation = 3.759 (3)Å]. This π–π intramolecular interaction is extended along the c axis, with intermolecular pyridine-pyridine and phenyl-phenyl interactions related by 2-fold symmetry. Distances separating rings are 3.859 (3)Å and 3.916 (3)Å, respectively, while angles between aromatic mean planes are 25.28 (13)° and 19.84 (7)° (Fig. 3). CH₂Cl₂ molecules are placed between the chains of molecules stacked through these π–π contacts.

Experimental

To a solution of 1,3-dicyclohexylcarbodiimide (DCC, 2 mmol) in CH₂Cl₂ (8 ml) was added N-hydroxy-2-thiopyridone (2.2 mmol) under an argon atmosphere. The solution was protected from light with aluminium foil and kept at 273 K in an ice bath. Adamantylcarboxylic acid (2 mmol) dissolved in CH₂Cl₂ was added dropwise to the solution. After the addition, the mixture was allowed to reach room temperature and further stirred for a period of 1.5 h. The resulting yellow solid was filtered on a bed of silica gel and washed with dry CH₂Cl₂ (all in dark). The filtrate was concentrated under reduced pressure, to give a crystalline solid. m.p. 164–166°C (compound 1 in Fig. 1). O-acyl ester 1 (1 mmol) was dissolved in CH₂Cl₂ (5 ml) under an argon atmosphere and (E)-methyl-3-(phenylsulfonyl)acrylate 2 (1.1 mmol) was added to the yellowish solution. The mixture was irradiated with a tungsten lamp (150 W), following the reaction by TLC. The products were purified by chromatography on silica gel (eluent: hexane:ethyl-acetate, 7:3). A white crystalline solid was obtained with a yield of 88%. m.p. 145–146 °C (compound 3).This compound was crystallized by slow evaporation of a CH₂Cl₂ solution, affording the title hemisolvate.