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

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

doi:10.1107/S1600536813016887

organic compounds

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ISSN: 2056-9890

Volume 69| Part 7| July 2013| Page o1136

https://doi.org/10.1107/S1600536813016887

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

Yan-Jiao Gao,^a Yu-Huang Wang ^a and Jian-Liang Ye ^a ^*

^aThe Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, People's Republic of China
^*Correspondence e-mail: yejl@xmu.edu.cn

(Received 17 June 2013; accepted 18 June 2013; online 22 June 2013)

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].

Related literature

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

Experimental

Crystal data

C₁₃H₁₅NO₂
M_r = 215.27
Monoclinic, P 2₁
a = 7.0399 (14) Å
b = 7.1795 (14) Å
c = 11.817 (2) Å
β = 102.72 (3)°
V = 582.6 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 173 K
0.3 × 0.2 × 0.2 mm

Data collection

Oxford Diffraction Xcalibur (Sapphire3, Gemini ultra) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ) T_min = 0.980, T_max = 0.983
3363 measured reflections
1947 independent reflections
1811 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.145
S = 1.13
1947 reflections
145 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯O1ⁱ	0.82	1.95	2.772 (3)	176
Symmetry code: (i) $[-x, y+{\script{1\over 2}}, -z+2]$ .

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813016887/hb7096sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813016887/hb7096Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813016887/hb7096Isup3.cml

checkCIF report

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.

Structure description top

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

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

	Fig. 1. The molecular structure of the title compound showing 50% probability displacement ellipsoids.
	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

C₁₃H₁₅NO₂	F(000) = 230
M_r = 215.27	D_x = 1.227 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 7.0399 (14) Å	Cell parameters from 2119 reflections
b = 7.1795 (14) Å	θ = 3.0–27.0°
c = 11.817 (2) Å	µ = 0.08 mm⁻¹
β = 102.72 (3)°	T = 173 K
V = 582.6 (2) Å³	Pillar, colourless
Z = 2	0.3 × 0.2 × 0.2 mm

Data collection top

Oxford Diffraction Xcalibur (Sapphire3, Gemini ultra) diffractometer	1947 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1811 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
Detector resolution: 16.1903 pixels mm^-1	θ_max = 27.0°, θ_min = 3.0°
phi and ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −9→9
T_min = 0.980, T_max = 0.983	l = −14→15
3363 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.145	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.0893P)² + 0.0423P] where P = (F_o² + 2F_c²)/3
1947 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.25 e Å⁻³
1 restraint	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₁₃H₁₅NO₂	V = 582.6 (2) Å³
M_r = 215.27	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 7.0399 (14) Å	µ = 0.08 mm⁻¹
b = 7.1795 (14) Å	T = 173 K
c = 11.817 (2) Å	0.3 × 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)
T_min = 0.980, T_max = 0.983	R_int = 0.054
3363 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	1 restraint
wR(F²) = 0.145	H-atom parameters constrained
S = 1.13	Δρ_max = 0.25 e Å⁻³
1947 reflections	Δρ_min = −0.32 e Å⁻³
145 parameters

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

	x	y	z	U_iso*/U_eq
O1	−0.2177 (3)	0.6481 (3)	0.96950 (15)	0.0294 (4)
N1	−0.0106 (3)	0.7331 (3)	0.85306 (15)	0.0214 (4)
C1	−0.2478 (4)	0.4825 (5)	0.4747 (2)	0.0383 (7)
H1A	−0.2359	0.4924	0.3981	0.046*
O2	0.2472 (3)	0.9389 (2)	0.83792 (15)	0.0294 (4)
H2A	0.2397	1.0049	0.8934	0.044*
C2	−0.3230 (4)	0.3208 (5)	0.5114 (2)	0.0403 (7)
H2B	−0.36	0.2222	0.4602	0.048*
C3	−0.3426 (4)	0.3079 (5)	0.6254 (2)	0.0352 (6)
H3A	−0.3927	0.2	0.6511	0.042*
C4	0.2774 (4)	0.6967 (4)	0.9869 (2)	0.0291 (6)
H4A	0.4086	0.6937	1.0235	0.035*
C5	−0.1894 (4)	0.6312 (4)	0.5507 (2)	0.0325 (6)
H5A	−0.1362	0.738	0.5255	0.039*
C6	−0.1548 (4)	0.7814 (4)	0.74846 (19)	0.0254 (5)
H6A	−0.1033	0.8808	0.7084	0.03*
H6B	−0.2707	0.8281	0.7706	0.03*
C7	0.2009 (4)	0.7521 (3)	0.8611 (2)	0.0241 (5)
C8	−0.2875 (4)	0.4557 (4)	0.7009 (2)	0.0283 (6)
H8A	−0.3016	0.4459	0.7771	0.034*
C9	−0.0541 (3)	0.6758 (3)	0.95313 (19)	0.0225 (5)
C10	−0.2118 (3)	0.6177 (4)	0.66498 (19)	0.0252 (5)
C11	0.1357 (4)	0.6535 (4)	1.0372 (2)	0.0300 (6)
H11A	0.151	0.6149	1.1138	0.036*
C12	0.2726 (4)	0.6284 (4)	0.7756 (2)	0.0286 (6)
H12A	0.4104	0.652	0.7826	0.034*
H12B	0.2061	0.6643	0.6978	0.034*
C13	0.2442 (4)	0.4196 (4)	0.7893 (2)	0.0335 (6)
H13A	0.2931	0.3535	0.7311	0.05*
H13B	0.1081	0.3932	0.7807	0.05*
H13C	0.3136	0.3806	0.8649	0.05*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0328 (9)	0.0290 (11)	0.0303 (9)	−0.0023 (8)	0.0153 (7)	−0.0011 (8)
N1	0.0209 (9)	0.0227 (10)	0.0203 (8)	0.0000 (8)	0.0035 (7)	−0.0002 (8)
C1	0.0360 (14)	0.053 (2)	0.0254 (12)	0.0033 (15)	0.0061 (10)	−0.0087 (13)
O2	0.0358 (10)	0.0214 (10)	0.0325 (9)	−0.0076 (8)	0.0104 (7)	0.0009 (7)
C2	0.0317 (14)	0.052 (2)	0.0370 (14)	−0.0020 (14)	0.0067 (11)	−0.0215 (14)
C3	0.0295 (14)	0.0360 (16)	0.0398 (14)	−0.0060 (12)	0.0068 (11)	−0.0067 (12)
C4	0.0289 (12)	0.0263 (14)	0.0283 (11)	−0.0024 (11)	−0.0020 (9)	0.0022 (10)
C5	0.0311 (13)	0.0398 (16)	0.0260 (12)	0.0042 (12)	0.0049 (10)	0.0011 (12)
C6	0.0249 (12)	0.0254 (13)	0.0242 (11)	0.0054 (10)	0.0017 (9)	0.0016 (10)
C7	0.0224 (11)	0.0218 (13)	0.0274 (11)	−0.0005 (10)	0.0039 (8)	0.0017 (10)
C8	0.0237 (11)	0.0339 (16)	0.0268 (11)	0.0028 (11)	0.0047 (8)	−0.0044 (11)
C9	0.0300 (12)	0.0150 (11)	0.0230 (10)	−0.0016 (10)	0.0069 (8)	−0.0021 (9)
C10	0.0196 (10)	0.0320 (14)	0.0222 (10)	0.0058 (11)	0.0004 (8)	−0.0033 (10)
C11	0.0363 (13)	0.0278 (14)	0.0225 (11)	−0.0053 (12)	−0.0008 (9)	0.0013 (10)
C12	0.0244 (12)	0.0275 (14)	0.0362 (13)	0.0000 (10)	0.0118 (9)	0.0008 (11)
C13	0.0310 (14)	0.0260 (13)	0.0449 (14)	0.0059 (12)	0.0114 (11)	−0.0022 (12)

Geometric parameters (Å, º) top

O1—C9	1.225 (3)	C5—C10	1.397 (3)
N1—C9	1.349 (3)	C5—H5A	0.93
N1—C6	1.458 (3)	C6—C10	1.530 (3)
N1—C7	1.477 (3)	C6—H6A	0.97
C1—C2	1.385 (5)	C6—H6B	0.97
C1—C5	1.397 (4)	C7—C12	1.513 (4)
C1—H1A	0.93	C8—C10	1.384 (4)
O2—C7	1.421 (3)	C8—H8A	0.93
O2—H2A	0.82	C9—C11	1.488 (3)
C2—C3	1.387 (4)	C11—H11A	0.93
C2—H2B	0.93	C12—C13	1.526 (4)
C3—C8	1.386 (4)	C12—H12A	0.97
C3—H3A	0.93	C12—H12B	0.97
C4—C11	1.306 (4)	C13—H13A	0.96
C4—C7	1.518 (3)	C13—H13B	0.96
C4—H4A	0.93	C13—H13C	0.96

C9—N1—C6	124.4 (2)	O2—C7—C4	112.9 (2)
C9—N1—C7	113.05 (18)	N1—C7—C4	100.05 (19)
C6—N1—C7	122.47 (19)	C12—C7—C4	113.7 (2)
C2—C1—C5	121.2 (2)	C10—C8—C3	121.2 (2)
C2—C1—H1A	119.4	C10—C8—H8A	119.4
C5—C1—H1A	119.4	C3—C8—H8A	119.4
C7—O2—H2A	109.5	O1—C9—N1	126.2 (2)
C1—C2—C3	119.1 (3)	O1—C9—C11	127.9 (2)
C1—C2—H2B	120.4	N1—C9—C11	105.9 (2)
C3—C2—H2B	120.4	C8—C10—C5	119.2 (2)
C8—C3—C2	120.0 (3)	C8—C10—C6	120.7 (2)
C8—C3—H3A	120	C5—C10—C6	120.0 (2)
C2—C3—H3A	120	C4—C11—C9	109.5 (2)
C11—C4—C7	111.5 (2)	C4—C11—H11A	125.3
C11—C4—H4A	124.3	C9—C11—H11A	125.3
C7—C4—H4A	124.3	C7—C12—C13	115.8 (2)
C10—C5—C1	119.2 (3)	C7—C12—H12A	108.3
C10—C5—H5A	120.4	C13—C12—H12A	108.3
C1—C5—H5A	120.4	C7—C12—H12B	108.3
N1—C6—C10	113.5 (2)	C13—C12—H12B	108.3
N1—C6—H6A	108.9	H12A—C12—H12B	107.4
C10—C6—H6A	108.9	C12—C13—H13A	109.5
N1—C6—H6B	108.9	C12—C13—H13B	109.5
C10—C6—H6B	108.9	H13A—C13—H13B	109.5
H6A—C6—H6B	107.7	C12—C13—H13C	109.5
O2—C7—N1	110.21 (19)	H13A—C13—H13C	109.5
O2—C7—C12	107.48 (19)	H13B—C13—H13C	109.5
N1—C7—C12	112.5 (2)

C5—C1—C2—C3	0.8 (4)	C7—N1—C9—O1	−179.5 (2)
C1—C2—C3—C8	0.1 (4)	C6—N1—C9—C11	−176.7 (2)
C2—C1—C5—C10	−1.5 (4)	C7—N1—C9—C11	0.3 (3)
C9—N1—C6—C10	−92.1 (3)	C3—C8—C10—C5	−0.5 (4)
C7—N1—C6—C10	91.2 (3)	C3—C8—C10—C6	178.9 (2)
C9—N1—C7—O2	−119.7 (2)	C1—C5—C10—C8	1.4 (4)
C6—N1—C7—O2	57.4 (3)	C1—C5—C10—C6	−178.0 (2)
C9—N1—C7—C12	120.4 (2)	N1—C6—C10—C8	57.8 (3)
C6—N1—C7—C12	−62.5 (3)	N1—C6—C10—C5	−122.8 (2)
C9—N1—C7—C4	−0.6 (3)	C7—C4—C11—C9	−0.6 (3)
C6—N1—C7—C4	176.5 (2)	O1—C9—C11—C4	180.0 (3)
C11—C4—C7—O2	117.8 (3)	N1—C9—C11—C4	0.2 (3)
C11—C4—C7—N1	0.7 (3)	O2—C7—C12—C13	177.5 (2)
C11—C4—C7—C12	−119.4 (3)	N1—C7—C12—C13	−61.0 (3)
C2—C3—C8—C10	−0.2 (4)	C4—C7—C12—C13	51.8 (3)
C6—N1—C9—O1	3.5 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1ⁱ	0.82	1.95	2.772 (3)	176

Symmetry code: (i) −x, y+1/2, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₅NO₂
M_r	215.27
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	173
a, b, c (Å)	7.0399 (14), 7.1795 (14), 11.817 (2)
β (°)	102.72 (3)
V (Å³)	582.6 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.3 × 0.2 × 0.2

Data collection
Diffractometer	Oxford Diffraction Xcalibur (Sapphire3, Gemini ultra)
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.980, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	3363, 1947, 1811
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.145, 1.13
No. of reflections	1947
No. of parameters	145
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.32

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1ⁱ	0.82	1.95	2.772 (3)	176

Symmetry code: (i) −x, y+1/2, −z+2.

Acknowledgements

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

References

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