2,3-O-Isopropyl­idene-1-O-p-tolyl­sulfonylglycerol

Piotr Kuś; Marcin Rojkiewicz; Grzegorz Zięba; Peter G Jones

doi:10.1107/S1600536809015037

. 2009 May 7;65(Pt 6):o1191. doi: 10.1107/S1600536809015037

2,3-O-Isopropylidene-1-O-p-tolylsulfonylglycerol

Piotr Kuś ^a, Marcin Rojkiewicz ^a, Grzegorz Zięba ^a, Peter G Jones ^b,^*

PMCID: PMC2969609 PMID: 21583063

Abstract

In the title compound, C₁₃H₁₈O₅S, the five-membered ring has an envelope conformation. The packing involves four C—H⋯O interactions, three of which combine to form layers of molecules parallel to the bc plane.

Related literature

For related literature, see: Baer & Fischer (1948 ▶); Jones et al. (2003 ▶); Kazemi et al. (2007 ▶); Ouchi et al. (1990 ▶). The structure of a related derivative is presented in the following paper, see: Kuś et al. (2009 ▶).

Experimental

Crystal data

C₁₃H₁₈O₅S
M _r = 286.33
Monoclinic,
a = 15.143 (2) Å
b = 5.7297 (9) Å
c = 15.665 (2) Å
β = 90.385 (3)°
V = 1359.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 133 K
0.40 × 0.20 × 0.05 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: none
12509 measured reflections
3357 independent reflections
2339 reflections with I > 2σ(I)
R _int = 0.111

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.114
S = 1.05
3357 reflections
175 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP (Siemens, 1994 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809015037/bt2935sup1.cif

e-65-o1191-sup1.cif^{(18.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809015037/bt2935Isup2.hkl

e-65-o1191-Isup2.hkl^{(164.7KB, 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
C16—H16⋯O1ⁱ	0.95	2.60	3.212 (2)	122
C17—H17C⋯O1ⁱⁱ	0.98	2.65	3.369 (3)	131
C17—H17B⋯O1ⁱⁱⁱ	0.98	2.66	3.558 (3)	153
C5—H5A⋯O2^iv	0.98	2.64	3.509 (3)	148

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

Acknowledgments

Financial support by the Polish State Committee for Scientific Research (grant No. R 05 043 03) is gratefully acknowledged.

supplementary crystallographic information

Comment

Isopropylidene and tosyl groups are often used as protecting or activating units in polyhydroxyalkyl compounds used for synthesis of sugar-like derivatives. Recently we described the crystal structure of L-arabitol tosylate protected by two isopropylidene groups (Jones et al., 2003). D,L-Isopropylideneglycerol is an important substrate for the synthesis of many derivatives of glycerol; the isopropylidene protecting group is a convenient form of protection for the two vicinal hydroxyls in the molecule of glycerol. After the reaction at the third, free hydroxyl group, acid hydrolysis of the protecting group leads to 1-O-substituted glycerol derivatives. In our experiments we used commercial (Aldrich) solketal as precursor for the protecting group. Tosylation of this compound leads to compound 1 (Baer & Fischer, 1948; Ouchi et al. 1990; Kazemi et al. 2007).

The molecule is shown in Fig. 1. Bond lengths and angles may be regarded as normal. The five-membered ring displays an envelope conformation, with approximate local mirror symmetry about O5 and the midpoint of C2—O4. The chain of five atoms from S to C3 displays an extended conformation, with torsion angles close to ±180°.

There are four weak C—H···O interactions with H···O between 2.6 and 2.7 Å. Three of these combine to form layers of molecules parallel to the bc plane at x≈ 1/4 (Fig. 2) and 3/4.

The structure of a related derivative is presented in the following paper (Kuś et al., 2009).

Experimental

The compound 1 was obtained according to method described by Kazemi et al. (2007). The analytical and spectroscopic data are consistent with the literature. Single crystals suitable for X-ray analysis were obtained by slow evaporation from petroleum ether.

NMR data: ¹H NMR (CDCl₃, 400 MHz): δ 7.80 (d, 2H), 7.35 (d, 2H), 4.28 (q, 1H), 4.06–3.95 (m, 3H), 3.78–3.75 (dd, 1H), 2.45 (s, 3H), 1.34 (s, 3H), 1.31 (s, 3H). - ¹³C NMR (100 MHz): δ 145.21, 132.81, 130.06, 128.15, 110.20, 73.05, 69.62, 66.35, 26.77, 25.28, 21.80.

IR data: —S(O₂)—O— vibrations at 1177 (versus) and 1348 cm^-1 (s); 1,3-dioxalone ring at 971 cm^-1. There are no bands above 2990 cm^-1.