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Acta Cryst. (2013). E69, o1136    [ doi:10.1107/S1600536813016887 ]

1-Benzyl-5-ethyl-5-hydroxy-1H-pyrrol-2(5H)-one

Y.-J. Gao, Y.-H. Wang and J.-L. Ye

Abstract top

The title compound, C13H15NO2, was obtained as a by-product in the Grignard reaction of malimide. The dihedral angle between the five-memebred ring (r.m.s. deviation = 0.005 Å) and the benzene ring is 67.20 (14)°. The benzene ring and the ethyl chain lie to the same side of the five-membered ring. In the crystal, molecules are linked by O-H...O hydrogen bonds, generating C(6) chains propagating in [010].

Comment top

Using Grignard reagents as the nucleophiles allows a flexible introduction of diverse side chains at the C-2 carbonyl of malimides (Huang, 2006). In addition, Grignard reagents are essentially strong bases, so the addition of a Grignard reagent to a malimide provided an unexpected 3-alkoxy group elimination product rac-1-benzyl-5-methyl-1H-pyrrol-2(5H)-one (He et al., 2003). Recently a new addition-elimination product, rac-1-benzyl-5-ethyl-5-hydroxy-1H-pyrrol-2(5H)-one, was found in the Grignard addition reaction. Here we report the structure of the title compound.

In γ-lactam ring the vinyl carbon atoms remain almost coplanar with the amide moiety [r.m.s. 0.0006 Å], which are agreement with the similar compounds (Goh et al., 2007; Ma & Xie, 2002). In the crystal, the molecules are linked by O—H···O hydrogen bonds between the hydroxyl group and the oxygen atom of the carbonyl group.

Related literature top

For background to Grignard reagents, see: Huang (2006); He et al. (2003). For related structures, see: Goh et al. (2007); Ma & Xie (2002).

Experimental top

To a stirred solution of (S)-N,O-benzyl-malimide ((S)-1-benzyl-3-(benzyloxy)pyrrolidine-2,5-dione) (2 mmol) in anhydrous CH2Cl2 (20 ml) was added dropwise EtMgBr (4 mmol) in diethyl ether at -20 °C under nitrogen atmosphere. The mixture was stirred at -20 °C for 1 h and then quenched by adding a saturated aqueous solution of NH4Cl. The mixture was extracted with CH2Cl2 (4 × 10 ml). The combined extracts were washed with brine, dried over Na2SO4, concentrated under reduced pressure. The residue was purified by flash chromatography (eluent: EtOAc/PE = 1: 2; then 2: 1), provided a mixture of diastereomers (4S)-1-benzyl-4-(benzyloxy)-5-ethyl-5-hydroxypyrrolidin-2-one as major products (white crystals, yield 85%) and the title compound as minor product (colourless crystals, yield 10%). Colourless pillars of the tiltle compound were obtained by slow evaporation of a mixture of n-hexane/ethyl acetate solution.

Refinement top

The hydrogen atoms were positioned geometrically, with C—H = 0.93, 0.98, 0.97 and 0.96 Å for phenyl, methine, methylene and methyl H atoms, respectively, and were included in the refinement in the riding model approximation. The displacement parameters of methyl H atoms were set to 1.5Ueq(C), while those of other H atoms were set to 1.2Ueq(C). In the absence of significant anomalous scattering effects the absolute structure of the chosen crystal was indeterminate.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound showing 50% probability displacement ellipsoids.
[Figure 2] Fig. 2. The packing of the molecules, viewed down the a axis. O—H···O hydrogen bond interactions are shown as dashed lines.
1-Benzyl-5-ethyl-5-hydroxy-1H-pyrrol-2(5H)-one top
Crystal data top
C13H15NO2F(000) = 230
Mr = 215.27Dx = 1.227 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
a = 7.0399 (14) ÅCell parameters from 2119 reflections
b = 7.1795 (14) Åθ = 3.0–27.0°
c = 11.817 (2) ŵ = 0.08 mm1
β = 102.72 (3)°T = 173 K
V = 582.6 (2) Å3Pillar, colourless
Z = 20.3 × 0.2 × 0.2 mm
Data collection top
Oxford Diffraction Xcalibur (Sapphire3, Gemini ultra)
diffractometer
1947 independent reflections
Radiation source: Enhance (Mo) X-ray Source1811 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.054
Detector resolution: 16.1903 pixels mm-1θmax = 27.0°, θmin = 3.0°
phi and ω scansh = 88
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2010)
k = 99
Tmin = 0.980, Tmax = 0.983l = 1415
3363 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.145H-atom parameters constrained
S = 1.13 w = 1/[σ2(Fo2) + (0.0893P)2 + 0.0423P]
where P = (Fo2 + 2Fc2)/3
1947 reflections(Δ/σ)max < 0.001
145 parametersΔρmax = 0.25 e Å3
1 restraintΔρmin = 0.32 e Å3
Crystal data top
C13H15NO2V = 582.6 (2) Å3
Mr = 215.27Z = 2
Monoclinic, P21Mo Kα radiation
a = 7.0399 (14) ŵ = 0.08 mm1
b = 7.1795 (14) ÅT = 173 K
c = 11.817 (2) Å0.3 × 0.2 × 0.2 mm
β = 102.72 (3)°
Data collection top
Oxford Diffraction Xcalibur (Sapphire3, Gemini ultra)
diffractometer
1947 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2010)
1811 reflections with I > 2σ(I)
Tmin = 0.980, Tmax = 0.983Rint = 0.054
3363 measured reflectionsθmax = 27.0°
Refinement top
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.145Δρmax = 0.25 e Å3
S = 1.13Δρmin = 0.32 e Å3
1947 reflectionsAbsolute structure: ?
145 parametersAbsolute structure parameter: ?
1 restraintRogers parameter: ?
Special details top

Experimental. Absorption correction: CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.2177 (3)0.6481 (3)0.96950 (15)0.0294 (4)
N10.0106 (3)0.7331 (3)0.85306 (15)0.0214 (4)
C10.2478 (4)0.4825 (5)0.4747 (2)0.0383 (7)
H1A0.23590.49240.39810.046*
O20.2472 (3)0.9389 (2)0.83792 (15)0.0294 (4)
H2A0.23971.00490.89340.044*
C20.3230 (4)0.3208 (5)0.5114 (2)0.0403 (7)
H2B0.360.22220.46020.048*
C30.3426 (4)0.3079 (5)0.6254 (2)0.0352 (6)
H3A0.39270.20.65110.042*
C40.2774 (4)0.6967 (4)0.9869 (2)0.0291 (6)
H4A0.40860.69371.02350.035*
C50.1894 (4)0.6312 (4)0.5507 (2)0.0325 (6)
H5A0.13620.7380.52550.039*
C60.1548 (4)0.7814 (4)0.74846 (19)0.0254 (5)
H6A0.10330.88080.70840.03*
H6B0.27070.82810.77060.03*
C70.2009 (4)0.7521 (3)0.8611 (2)0.0241 (5)
C80.2875 (4)0.4557 (4)0.7009 (2)0.0283 (6)
H8A0.30160.44590.77710.034*
C90.0541 (3)0.6758 (3)0.95313 (19)0.0225 (5)
C100.2118 (3)0.6177 (4)0.66498 (19)0.0252 (5)
C110.1357 (4)0.6535 (4)1.0372 (2)0.0300 (6)
H11A0.1510.61491.11380.036*
C120.2726 (4)0.6284 (4)0.7756 (2)0.0286 (6)
H12A0.41040.6520.78260.034*
H12B0.20610.66430.69780.034*
C130.2442 (4)0.4196 (4)0.7893 (2)0.0335 (6)
H13A0.29310.35350.73110.05*
H13B0.10810.39320.78070.05*
H13C0.31360.38060.86490.05*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0328 (9)0.0290 (11)0.0303 (9)0.0023 (8)0.0153 (7)0.0011 (8)
N10.0209 (9)0.0227 (10)0.0203 (8)0.0000 (8)0.0035 (7)0.0002 (8)
C10.0360 (14)0.053 (2)0.0254 (12)0.0033 (15)0.0061 (10)0.0087 (13)
O20.0358 (10)0.0214 (10)0.0325 (9)0.0076 (8)0.0104 (7)0.0009 (7)
C20.0317 (14)0.052 (2)0.0370 (14)0.0020 (14)0.0067 (11)0.0215 (14)
C30.0295 (14)0.0360 (16)0.0398 (14)0.0060 (12)0.0068 (11)0.0067 (12)
C40.0289 (12)0.0263 (14)0.0283 (11)0.0024 (11)0.0020 (9)0.0022 (10)
C50.0311 (13)0.0398 (16)0.0260 (12)0.0042 (12)0.0049 (10)0.0011 (12)
C60.0249 (12)0.0254 (13)0.0242 (11)0.0054 (10)0.0017 (9)0.0016 (10)
C70.0224 (11)0.0218 (13)0.0274 (11)0.0005 (10)0.0039 (8)0.0017 (10)
C80.0237 (11)0.0339 (16)0.0268 (11)0.0028 (11)0.0047 (8)0.0044 (11)
C90.0300 (12)0.0150 (11)0.0230 (10)0.0016 (10)0.0069 (8)0.0021 (9)
C100.0196 (10)0.0320 (14)0.0222 (10)0.0058 (11)0.0004 (8)0.0033 (10)
C110.0363 (13)0.0278 (14)0.0225 (11)0.0053 (12)0.0008 (9)0.0013 (10)
C120.0244 (12)0.0275 (14)0.0362 (13)0.0000 (10)0.0118 (9)0.0008 (11)
C130.0310 (14)0.0260 (13)0.0449 (14)0.0059 (12)0.0114 (11)0.0022 (12)
Geometric parameters (Å, º) top
O1—C91.225 (3)C5—C101.397 (3)
N1—C91.349 (3)C5—H5A0.93
N1—C61.458 (3)C6—C101.530 (3)
N1—C71.477 (3)C6—H6A0.97
C1—C21.385 (5)C6—H6B0.97
C1—C51.397 (4)C7—C121.513 (4)
C1—H1A0.93C8—C101.384 (4)
O2—C71.421 (3)C8—H8A0.93
O2—H2A0.82C9—C111.488 (3)
C2—C31.387 (4)C11—H11A0.93
C2—H2B0.93C12—C131.526 (4)
C3—C81.386 (4)C12—H12A0.97
C3—H3A0.93C12—H12B0.97
C4—C111.306 (4)C13—H13A0.96
C4—C71.518 (3)C13—H13B0.96
C4—H4A0.93C13—H13C0.96
C9—N1—C6124.4 (2)O2—C7—C4112.9 (2)
C9—N1—C7113.05 (18)N1—C7—C4100.05 (19)
C6—N1—C7122.47 (19)C12—C7—C4113.7 (2)
C2—C1—C5121.2 (2)C10—C8—C3121.2 (2)
C2—C1—H1A119.4C10—C8—H8A119.4
C5—C1—H1A119.4C3—C8—H8A119.4
C7—O2—H2A109.5O1—C9—N1126.2 (2)
C1—C2—C3119.1 (3)O1—C9—C11127.9 (2)
C1—C2—H2B120.4N1—C9—C11105.9 (2)
C3—C2—H2B120.4C8—C10—C5119.2 (2)
C8—C3—C2120.0 (3)C8—C10—C6120.7 (2)
C8—C3—H3A120C5—C10—C6120.0 (2)
C2—C3—H3A120C4—C11—C9109.5 (2)
C11—C4—C7111.5 (2)C4—C11—H11A125.3
C11—C4—H4A124.3C9—C11—H11A125.3
C7—C4—H4A124.3C7—C12—C13115.8 (2)
C10—C5—C1119.2 (3)C7—C12—H12A108.3
C10—C5—H5A120.4C13—C12—H12A108.3
C1—C5—H5A120.4C7—C12—H12B108.3
N1—C6—C10113.5 (2)C13—C12—H12B108.3
N1—C6—H6A108.9H12A—C12—H12B107.4
C10—C6—H6A108.9C12—C13—H13A109.5
N1—C6—H6B108.9C12—C13—H13B109.5
C10—C6—H6B108.9H13A—C13—H13B109.5
H6A—C6—H6B107.7C12—C13—H13C109.5
O2—C7—N1110.21 (19)H13A—C13—H13C109.5
O2—C7—C12107.48 (19)H13B—C13—H13C109.5
N1—C7—C12112.5 (2)
C5—C1—C2—C30.8 (4)C7—N1—C9—O1179.5 (2)
C1—C2—C3—C80.1 (4)C6—N1—C9—C11176.7 (2)
C2—C1—C5—C101.5 (4)C7—N1—C9—C110.3 (3)
C9—N1—C6—C1092.1 (3)C3—C8—C10—C50.5 (4)
C7—N1—C6—C1091.2 (3)C3—C8—C10—C6178.9 (2)
C9—N1—C7—O2119.7 (2)C1—C5—C10—C81.4 (4)
C6—N1—C7—O257.4 (3)C1—C5—C10—C6178.0 (2)
C9—N1—C7—C12120.4 (2)N1—C6—C10—C857.8 (3)
C6—N1—C7—C1262.5 (3)N1—C6—C10—C5122.8 (2)
C9—N1—C7—C40.6 (3)C7—C4—C11—C90.6 (3)
C6—N1—C7—C4176.5 (2)O1—C9—C11—C4180.0 (3)
C11—C4—C7—O2117.8 (3)N1—C9—C11—C40.2 (3)
C11—C4—C7—N10.7 (3)O2—C7—C12—C13177.5 (2)
C11—C4—C7—C12119.4 (3)N1—C7—C12—C1361.0 (3)
C2—C3—C8—C100.2 (4)C4—C7—C12—C1351.8 (3)
C6—N1—C9—O13.5 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2A···O1i0.821.952.772 (3)176
Symmetry code: (i) x, y+1/2, z+2.

Experimental details

Crystal data
Chemical formulaC13H15NO2
Mr215.27
Crystal system, space groupMonoclinic, P21
Temperature (K)173
a, b, c (Å)7.0399 (14), 7.1795 (14), 11.817 (2)
β (°) 102.72 (3)
V3)582.6 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.3 × 0.2 × 0.2
Data collection
DiffractometerOxford Diffraction Xcalibur (Sapphire3, Gemini ultra)
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Oxford Diffraction, 2010)
Tmin, Tmax0.980, 0.983
No. of measured, independent and
observed [I > 2σ(I)] reflections
3363, 1947, 1811
Rint0.054
(sin θ/λ)max1)0.638
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.145, 1.13
No. of reflections1947
No. of parameters145
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.25, 0.32

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2A···O1i0.821.952.772 (3)176
Symmetry code: (i) x, y+1/2, z+2.
Acknowledgements top

The authors thank the NSF of Fujian Province of China (2011 J01056) for financial support.

references
References top

Goh, W. K., Iskander, G., Black, D. S. & Kumar, N. (2007). Tetrahedron Lett. 48, 2287–2290.

He, B. Y., Wu, T. J., Yu, X. Y. & Huang, P. Q. (2003). Tetrahedron Asymmetry, 14, 2101–2108.

Huang, P.-Q. (2006). Synlett pp. 1133–1149.

Ma, S. & Xie, H. (2002). J. Org. Chem. 67, 6575–6578.

Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.