Methyl c-1-cyano-t-2-methyl­sulfonyl-3-phenyl­cyclo­propane­carboxyl­ate

Victor A Vasin; Irina Yu Bolusheva; Vyacheslav A Neverov; Nikolai V Somov

doi:10.1107/S1600536811016370

. 2011 May 25;67(Pt 6):o1504. doi: 10.1107/S1600536811016370

Methyl c-1-cyano-t-2-methylsulfonyl-3-phenylcyclopropanecarboxylate

Victor A Vasin ^a,^*, Irina Yu Bolusheva ^a, Vyacheslav A Neverov ^b, Nikolai V Somov ^c

PMCID: PMC3120552 PMID: 21754871

Abstract

The title compound, C₁₃H₁₃NO₄S, is a racemic mixture of enantiomers. Short intramolecular contacts between sulfonyl O and ester carbonyl C atoms are observed [C⋯O = 2.881 (1), 2.882 (1) and 2.686 (1) Å], indicating the possibility of donor—acceptor interactions between these groups. The dihedral angle between the phenyl and cyclopropyl rings is 79.3 (1)°.

Related literature

Some α-bromovinyl sulfones react with primary amines in DMSO to give the products of aza-Michael ring closure reactions (MIRCR), viz. 2-sulfonyl-substituted aziridines, see: Galliot et al. (1979 ▶). Similarly, MIRCR of phenyl-(Z)-(2-phenyl-2-chloroethenyl)sulfone with diethyl sodium malonate leads to the formation of a sulfonyl-substituted cyclopropane, see: Yamamoto et al. (1985 ▶). For related structures, see: Vasin et al. (2008 ▶, 2010 ▶); Zefirov & Zorkii (1989 ▶).

Experimental

Crystal data

C₁₃H₁₃NO₄S
M _r = 279.3
Orthorhombic,
a = 10.7323 (4) Å
b = 20.0790 (6) Å
c = 6.2663 (2) Å
V = 1350.35 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 293 K
0.20 × 0.15 × 0.12 mm

Data collection

Xcalibur, Sapphire3, Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.964, T _max = 1
21704 measured reflections
3353 independent reflections
3044 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.078
S = 0.98
3353 reflections
172 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.14 e Å⁻³
Absolute structure: Flack (1983 ▶), 1523 Friedel pairs
Flack parameter: 0.05 (5)

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: publCIF (Westrip 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811016370/aa2006sup1.cif

e-67-o1504-sup1.cif^{(15.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811016370/aa2006Isup2.hkl

e-67-o1504-Isup2.hkl^{(164.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811016370/aa2006Isup3.cml

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

supplementary crystallographic information

Comment

It is know, that some alpha-bromovinyl sulfones react with primary amines in DMSO to give the products of aza-Michael Ring Closure reaction (MIRCR) - 2-sulfonylsubstituted aziridines (Galliot et al., 1979). Similarly MIRCR of phenyl-(Z)-(2-phenyl-2-chloroethenyl)sulfone with diethyl sodium malonate leads to formation of a sulfonylsubstituted cyclopropane (Yamamoto et al., 1985). We have carried out MIRCR between compound (1) (see Fig. 2) and monosodium salt of methyl cyanoacetate in THF at 20 °C and a cyclopropane derivative, (2), was obtained. The product, (2), was isolated by chromatography, crystallized and studied by X-ray diffraction.

In compound (2) three short intramolecular contacts C···O, which appreciable less sum of the van der Vaals radii given atoms = 3.000Å (Zefirov et al., 1989), are found out. The first of them takes place between atoms O2 of sulfonyl and C5 of methoxycarbonyl groups (2.881 Å). The second contact length 2.882Å is observed between atoms O4 of methoxycarbonyl and C10 of cyclopropane fragment. The third is shorted (2.686 Å). It arises between atoms O1 of methoxycarbonyl group and C2 of cyano group. Given contacts are evidence of possible donor-acceptor interaction between cys-located sulfonyl and methoxycarbonyl groups, and also between methoxycarbonyl on the one hand,cyano group and cyclopropene fragment - with another.

We shall note, that strong interaction between drawing together sulfonyl and methoxycarbonyl groups in structure of cyclobutane fragment, hardly fixed in space by trimethylene bridge, where free rotation of given groups was revealed earlier; interatomic distance C···O in this case is 2.489Å (Vasin et al., 2010). At the same time, in analogue of compound (2) - dimethyl 3-phenyl-2-(t)-phenylsulfonyl-1,1-cyclopropanecarboxylate, as it has been established by X-ray analysis, mutual, close to parallel, an arrangement of sulfonyl and ethoxycarbonyl groups the dipole-dipole interaction between them does not promote (Yamamoto et al., 1985).

The values of valent angles at atom C5 in compound (2), most likely, are consequence of noted donor-acceptor interaction: a little overestimated for C4—C5—O4 (124.35°) and O4—C5—O1 (126.02°), essentially underestimated for O1—C5—C4 (109.62°), and also value of angle C5—C4—C2 (114.35°).

The structure of compound (2) consists of separate molecules between which only van der Vaals interaction is carried out.

Experimental

Compound (2) was obtained by the reaction between the previously reported compound (1) (Vasin et al., 2008) and monosodium salt of methyl cyanoacetate (see Fig. 2). Sodium hydride (0.23 g 60% suspension in mineral oil) was freed of mineral oil by washing with hexane and was added dry THF (5 ml). Methyl cyanoacetate (4.2 g) in THF (10 ml) was added drop wise for 10 min at stirring. The stirring was continued for 1.5 h at 20 °C. After drop wise addition of compound (1) (1.0 g) in THF (10 ml), stirring was continued at 20° C for 20 h. The mixture was diluted with water (250 ml), neutralized with aqueous (1: 1) HCl, extracted with CHCl₃ (3 x 15 ml), washed with water, and dried over MgSO₄. Evaporation of solvent in vacuo gave 0.7 g semisolid product. Compound (2) was isolated by column chromatography on silicagel and crystallized from an acetone - hexane (1: 3) mixture [yield 0.21 g (20%); m. p. 417–418 K].