Benzyl 2,5-dioxopyrrolidin-1-yl carbonate

An-Fu Hu; Tao Ji; Yu-Xing Gao; Peng-Xiang Xu; Yu-Fen Zhao

doi:10.1107/S1600536808015948

. 2008 Jun 21;64(Pt 7):o1326. doi: 10.1107/S1600536808015948

Benzyl 2,5-dioxopyrrolidin-1-yl carbonate

An-Fu Hu ^a, Tao Ji ^a, Yu-Xing Gao ^a, Peng-Xiang Xu ^a,^*, Yu-Fen Zhao ^a

PMCID: PMC2961810 PMID: 21202950

Abstract

The asymmetric unit of the title compound, C₁₂H₁₁NO₅, contains two independent molecules with similar geometric parameters but different orientations of the phenyl rings. The molecular packing is stabilized by weak nonclassical C—H⋯O hydrogen-bonding interactions.

Related literature

For related literature, see: Alenka (1982 ▶); Wang et al. (2006 ▶).

Experimental

Crystal data

C₁₂H₁₁NO₅
M _r = 249.22
Monoclinic,
a = 12.9348 (6) Å
b = 6.0151 (3) Å
c = 16.5398 (9) Å
β = 106.170 (5)°
V = 1235.96 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 (2) K
0.60 × 0.50 × 0.37 mm

Data collection

Bruker APEX area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.939, T _max = 0.962
7601 measured reflections
2648 independent reflections
1646 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.113
S = 0.90
2648 reflections
325 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808015948/pv2076sup1.cif

e-64-o1326-sup1.cif^{(23.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808015948/pv2076Isup2.hkl

e-64-o1326-Isup2.hkl^{(130KB, 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
C10—H10B⋯O1ⁱ	0.97	2.56	3.251 (4)	128
C8A—H8AA⋯O4ⁱⁱ	0.93	2.47	3.398 (5)	172
C10—H10A⋯O1Aⁱⁱ	0.97	2.48	3.057 (5)	118
C2A—H2AA⋯O1ⁱⁱⁱ	0.97	2.49	3.417 (5)	161
C6A—H6AA⋯O5A^iv	0.93	2.60	3.354 (6)	139

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

Acknowledgments

The authors thank the Key Foundation of Science and Technology of Fujian Province, China (grant No. 2002H011), for supporting this work, and Mr R.-B. Huang for technical assistance.

supplementary crystallographic information

Comment

The title compound, (I), is a more convenient and mild reagent than benzyl carbonochloridate in protecting amino acids. It can also be used in the synthesis of a series of biologically active molecules (Alenka, 1982).

The asymmetric unit of (I) contains two independent molecules, the atoms of the second molecule have been identified by the letter A in their labels (Fig. 1). The two molecules adopt different orientations of the phenyl rings, as reflected by the torsion angles O2—C2—C3—C8 and O2—C2—C3—C4 with values -48.6 (4) and 134.7 (3)°, respectively, in the first molecule as compared with the values of the corresponding torsion angles in the second molecule being -88.5 (4) and 95.3 (5)°, respectively. Furthermore, the bond lengths and angles also have some slight differences. For example, the bond lengths O3—N1 and O3A—N1A are 1.391 (3) and 1.376 (4) Å, respectively. As to the bond angles, the values of the angles O1—C1—O3 and O1A—C1A—O3A are 124.9 (3) and 123.3 (3)°, respectively. Bond lengths and angles in (I) are in agreement with those reported for a similar compound (Wang et al., 2006). The structure contains rather weak non-classical hydrogen bonds of the type C—H···O involving the carbonyl groups (Table 1).

Experimental

To a stirred solution of benzyl chloroformate (3.41 g, 20 mmol) and N-hydroxysuccinimide (2.30 g, 20 mmol) in methylene chloride (20 ml) at room temperature was added dropwise triethylamine (2.90 ml, 20 mmol). After stirring for 10 h at room temperature, the mixture was concentrated under vacuum and the crude product was purified by column chromatography (petroleum ether-ethyl acetate, 4:1) to give the title compound as a white solid in 88% yield. Single crystals of (I) were obtained by slow evaporation of a petroleum ether-ethyl acetate solution (1:1 v/v).