(Z)-Methyl 3-(4-ethoxy­anilino)but-2-enoate

Zhang, L.-P.; Ni, C.-H.; Li, Z.-Y.; Zhang, W.

doi:10.1107/S160053680800891X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1051

doi:10.1107/S160053680800891X

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(Z)-Methyl 3-(4-ethoxyanilino)but-2-enoate

Li-Ping Zhang,^a ^* Cai-Hua Ni,^a Zhi-Yong Li ^a and Wei Zhang ^a

^aSchool of Chemical and Materials Engineering, Jiangnan University, 1800 Lihu Road, Wuxi 214122, Jiangsu, People's Republic of China
^*Correspondence e-mail: zhangliping76518@163.com.cn

(Received 3 March 2008; accepted 2 April 2008; online 10 May 2008)

The title compound, C₁₃H₁₇NO₃, was synthesized from methyl 3-oxobutanoate and 4-ethoxybenzenamine using a catalytic amount of InBr₃ under solvent-free conditions. The 3-aminobut-2-enoic acid methyl ester group is planar and forms a dihedral angle of 83.4 (1)° with the benzene ring. The ethoxy group is slightly twisted away from the benzene ring [dihedral angle = 13.8 (1)°]. An intramolecular N—H⋯O hydrogen bond generating an S(6) ring is observed. Molecules are linked into a chain along the b axis by intermolecular C—H⋯O hydrogen bonding.

Related literature

For general background on β-enamino esters, see: Bartoli et al. (1994 ); Cimarelli & Palmieri (1996 ); Cimarelli et al. (1994 ); Elassar & El-Khair (2003 ); Greenhill (1977 ); Lubell et al. (1991 ); Michael et al. (1999 ); Paola et al. (2000 ); Rybarczyk-Pirek & Grabowski (2002 ); Yunus et al. (2008 ).

Experimental

Crystal data

C₁₃H₁₇NO₃
M_r = 235.28
Monoclinic, P 2₁ /n
a = 12.421 (2) Å
b = 6.3372 (13) Å
c = 16.569 (3) Å
β = 96.519 (3)°
V = 1295.7 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 294 (2) K
0.30 × 0.26 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.942, T_max = 0.990
6917 measured reflections
2628 independent reflections
1629 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.136
S = 1.00
2628 reflections
158 parameters
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.11 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.86	2.08	2.741 (2)	133
C6—H6⋯O2ⁱ	0.93	2.57	3.362 (3)	143
Symmetry code: (i) x, y+1, z.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1999 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680800891X/ci2569sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680800891X/ci2569Isup2.hkl

checkCIF report

Comment top

β-Enamino esters are useful precursors for the preparation of biologically active compounds such as β-enamino acids, γ-enamino alcohols or β-enamino esters (Lubell et al., 1991; Bartoli et al., 1994; Cimarelli et al., 1994; Cimarelli & Palmieri, 1996). Therefore, many synthetic methods have been developed for the preparation of these compounds (Greenhill, 1977; Elassar et al., 2003; Michael et al., 1999). As part of our program on developing new environmental friendly methodologies for the preparation of β-enamino compounds, we have synthesized the title compound (Fig.1). We report here the crystal structure of it.

In the title molecule, the 3-amino-but-2-enoic acid methyl ester group is planar (r.m.s. deviation 0.045 Å) and it forms a dihedral angle of 83.4 (1)° with the benzene ring. The ethoxy group is slightly twisted away from the benzene ring [dihedral angle 13.8 (1)°]. An intramolecular N1—H1···O2 hydrogen bond generating an S(6) ring is observed. The N1—C9 bond length [1.341 (2) Å] is shorter than the N1—C1 [1.435 (2) Å] bond length, indicating electron delocalization.

The molecules are linked into a chain along the b axis by intermolecular C—H···O hydrogen bonds (Fig. 2).

Related literature top

For general background on β-enamino esters, see: Bartoli et al. (1994); Cimarelli & Palmieri (1996); Cimarelli et al. (1994); Elassar & El-Khair (2003); Greenhill (1977); Lubell et al. (1991); Michael et al. (1999); Paola et al. (2000); Rybarczyk-Pirek & Grabowski (2002); Yunus et al. (2008).

Experimental top

A mixture of the methyl-3-oxobutanoate (5 mmol), 4-ethoxybenzenamine (5 mmol) and InBr₃ (0.05 mmol) was stirred at room temperature for 1 h. After completion of the reaction, the reaction mixture was diluted with H₂O (10 ml) and extracted with EtOAc (210 ml). The combined organic layers were dried, concentrated, purified by column chromatography on SiO₂ with ethyl acetate-cyclohexane (2:8). Single crystals suitable for X-ray diffraction study were obtained from EtOAc-cyclohexane (1:10 v/v) by slow evaporation at room temperature.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (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 30% probability displacement ellipsoids.
	Fig. 2. A view of the molecular packing in the title compound. Hydrogen bonds are shown as dashed lines.

(Z)-Methyl 3-(4-ethoxyanilino)but-2-enoate top

Crystal data top

C₁₃H₁₇NO₃	F(000) = 504
M_r = 235.28	D_x = 1.206 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2289 reflections
a = 12.421 (2) Å	θ = 2.5–24.9°
b = 6.3372 (13) Å	µ = 0.09 mm⁻¹
c = 16.569 (3) Å	T = 294 K
β = 96.519 (3)°	Block, yellow
V = 1295.7 (4) Å³	0.30 × 0.26 × 0.20 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2628 independent reflections
Radiation source: fine-focus sealed tube	1629 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ϕ and ω scans	θ_max = 26.3°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→15
T_min = 0.942, T_max = 0.990	k = −7→6
6917 measured reflections	l = −20→20

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.042	H-atom parameters constrained
wR(F²) = 0.136	w = 1/[σ²(F_o²) + (0.0697P)² + 0.1223P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
2628 reflections	Δρ_max = 0.13 e Å⁻³
158 parameters	Δρ_min = −0.11 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.106 (7)

Crystal data top

C₁₃H₁₇NO₃	V = 1295.7 (4) Å³
M_r = 235.28	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.421 (2) Å	µ = 0.09 mm⁻¹
b = 6.3372 (13) Å	T = 294 K
c = 16.569 (3) Å	0.30 × 0.26 × 0.20 mm
β = 96.519 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2628 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1629 reflections with I > 2σ(I)
T_min = 0.942, T_max = 0.990	R_int = 0.031
6917 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.136	H-atom parameters constrained
S = 1.00	Δρ_max = 0.13 e Å⁻³
2628 reflections	Δρ_min = −0.11 e Å⁻³
158 parameters

Special details top

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	0.11751 (9)	1.2475 (2)	1.03170 (8)	0.0714 (4)
O2	0.55147 (10)	0.4131 (2)	0.90568 (7)	0.0697 (4)
O3	0.60606 (12)	0.2866 (2)	0.79053 (8)	0.0872 (5)
N1	0.39962 (11)	0.7279 (2)	0.88382 (9)	0.0654 (4)
H1	0.4403	0.6528	0.9181	0.078*
C1	0.32646 (13)	0.8715 (3)	0.91658 (9)	0.0578 (4)
C2	0.21953 (14)	0.8158 (3)	0.92064 (10)	0.0660 (5)
H2	0.1934	0.6891	0.8979	0.079*
C3	0.15124 (13)	0.9455 (3)	0.95793 (11)	0.0642 (5)
H3	0.0794	0.9067	0.9600	0.077*
C4	0.18978 (13)	1.1339 (3)	0.99243 (10)	0.0562 (4)
C5	0.29584 (13)	1.1948 (3)	0.98654 (11)	0.0621 (5)
H5	0.3216	1.3232	1.0079	0.074*
C6	0.36297 (13)	1.0624 (3)	0.94847 (10)	0.0622 (5)
H6	0.4341	1.1032	0.9444	0.075*
C7	0.15753 (16)	1.4153 (3)	1.08352 (12)	0.0747 (6)
H7A	0.1915	1.5212	1.0526	0.090*
H7B	0.2113	1.3624	1.1257	0.090*
C8	0.06476 (18)	1.5100 (4)	1.12071 (12)	0.0860 (6)
H8A	0.0129	1.5654	1.0787	0.129*
H8B	0.0908	1.6218	1.1569	0.129*
H8C	0.0309	1.4036	1.1505	0.129*
C9	0.41069 (14)	0.6995 (3)	0.80498 (10)	0.0606 (5)
C10	0.34385 (18)	0.8388 (4)	0.74539 (12)	0.0856 (6)
H10A	0.2687	0.8250	0.7530	0.128*
H10B	0.3542	0.7976	0.6911	0.128*
H10C	0.3660	0.9830	0.7541	0.128*
C11	0.48003 (16)	0.5549 (3)	0.77912 (11)	0.0682 (5)
H11	0.4847	0.5450	0.7236	0.082*
C12	0.54568 (14)	0.4182 (3)	0.83178 (11)	0.0603 (5)
C13	0.66598 (19)	0.1247 (4)	0.83608 (13)	0.0913 (7)
H13A	0.7034	0.1842	0.8847	0.137*
H13B	0.7176	0.0641	0.8038	0.137*
H13C	0.6171	0.0170	0.8503	0.137*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0558 (7)	0.0803 (9)	0.0782 (8)	0.0017 (6)	0.0075 (6)	−0.0156 (7)
O2	0.0708 (8)	0.0769 (9)	0.0602 (8)	0.0030 (6)	0.0030 (6)	−0.0031 (6)
O3	0.1112 (11)	0.0823 (10)	0.0680 (8)	0.0315 (8)	0.0100 (7)	−0.0054 (7)
N1	0.0600 (9)	0.0757 (10)	0.0604 (9)	0.0114 (7)	0.0069 (7)	0.0021 (7)
C1	0.0526 (10)	0.0670 (11)	0.0537 (9)	−0.0002 (8)	0.0050 (7)	0.0037 (8)
C2	0.0572 (11)	0.0703 (12)	0.0701 (11)	−0.0124 (9)	0.0062 (8)	−0.0107 (9)
C3	0.0465 (9)	0.0752 (13)	0.0709 (11)	−0.0097 (8)	0.0067 (8)	−0.0097 (9)
C4	0.0497 (9)	0.0632 (10)	0.0546 (9)	0.0017 (8)	0.0015 (7)	0.0024 (8)
C5	0.0540 (10)	0.0603 (11)	0.0710 (11)	−0.0080 (8)	0.0030 (8)	−0.0018 (9)
C6	0.0481 (10)	0.0686 (12)	0.0698 (11)	−0.0075 (8)	0.0063 (8)	0.0057 (9)
C7	0.0787 (13)	0.0724 (13)	0.0724 (12)	0.0010 (10)	0.0071 (9)	−0.0102 (10)
C8	0.0949 (15)	0.0886 (15)	0.0745 (12)	0.0188 (12)	0.0097 (11)	−0.0090 (11)
C9	0.0589 (10)	0.0621 (11)	0.0613 (10)	−0.0050 (8)	0.0087 (8)	0.0037 (8)
C10	0.0966 (15)	0.0921 (15)	0.0697 (12)	0.0227 (12)	0.0170 (11)	0.0152 (11)
C11	0.0787 (13)	0.0715 (12)	0.0552 (10)	0.0040 (10)	0.0118 (9)	0.0015 (9)
C12	0.0607 (11)	0.0566 (10)	0.0642 (11)	−0.0066 (8)	0.0088 (8)	−0.0060 (9)
C13	0.1021 (16)	0.0811 (15)	0.0877 (15)	0.0275 (12)	−0.0022 (12)	−0.0071 (12)

Geometric parameters (Å, º) top

O1—C4	1.371 (2)	C6—H6	0.93
O1—C7	1.420 (2)	C7—C8	1.493 (3)
O2—C12	1.2187 (19)	C7—H7A	0.97
O3—C12	1.357 (2)	C7—H7B	0.97
O3—C13	1.431 (2)	C8—H8A	0.96
N1—C9	1.341 (2)	C8—H8B	0.96
N1—C1	1.435 (2)	C8—H8C	0.96
N1—H1	0.86	C9—C11	1.360 (3)
C1—C6	1.376 (2)	C9—C10	1.503 (3)
C1—C2	1.383 (2)	C10—H10A	0.96
C2—C3	1.377 (3)	C10—H10B	0.96
C2—H2	0.93	C10—H10C	0.96
C3—C4	1.385 (2)	C11—C12	1.420 (3)
C3—H3	0.93	C11—H11	0.93
C4—C5	1.387 (2)	C13—H13A	0.96
C5—C6	1.384 (2)	C13—H13B	0.96
C5—H5	0.93	C13—H13C	0.96

C4—O1—C7	118.48 (14)	H7A—C7—H7B	108.4
C12—O3—C13	117.32 (15)	C7—C8—H8A	109.5
C9—N1—C1	126.37 (15)	C7—C8—H8B	109.5
C9—N1—H1	116.8	H8A—C8—H8B	109.5
C1—N1—H1	116.8	C7—C8—H8C	109.5
C6—C1—C2	118.81 (16)	H8A—C8—H8C	109.5
C6—C1—N1	120.47 (15)	H8B—C8—H8C	109.5
C2—C1—N1	120.63 (16)	N1—C9—C11	122.43 (16)
C3—C2—C1	120.90 (17)	N1—C9—C10	116.80 (16)
C3—C2—H2	119.6	C11—C9—C10	120.76 (16)
C1—C2—H2	119.6	C9—C10—H10A	109.5
C2—C3—C4	119.86 (16)	C9—C10—H10B	109.5
C2—C3—H3	120.1	H10A—C10—H10B	109.5
C4—C3—H3	120.1	C9—C10—H10C	109.5
O1—C4—C3	115.74 (15)	H10A—C10—H10C	109.5
O1—C4—C5	124.43 (16)	H10B—C10—H10C	109.5
C3—C4—C5	119.83 (16)	C9—C11—C12	123.90 (16)
C6—C5—C4	119.30 (17)	C9—C11—H11	118.0
C6—C5—H5	120.4	C12—C11—H11	118.0
C4—C5—H5	120.4	O2—C12—O3	121.13 (16)
C1—C6—C5	121.23 (16)	O2—C12—C11	126.71 (16)
C1—C6—H6	119.4	O3—C12—C11	112.16 (16)
C5—C6—H6	119.4	O3—C13—H13A	109.5
O1—C7—C8	108.47 (16)	O3—C13—H13B	109.5
O1—C7—H7A	110.0	H13A—C13—H13B	109.5
C8—C7—H7A	110.0	O3—C13—H13C	109.5
O1—C7—H7B	110.0	H13A—C13—H13C	109.5
C8—C7—H7B	110.0	H13B—C13—H13C	109.5

C9—N1—C1—C6	−100.4 (2)	N1—C1—C6—C5	−174.42 (15)
C9—N1—C1—C2	83.0 (2)	C4—C5—C6—C1	−0.1 (3)
C6—C1—C2—C3	−1.9 (3)	C4—O1—C7—C8	−178.42 (16)
N1—C1—C2—C3	174.69 (16)	C1—N1—C9—C11	−177.96 (17)
C1—C2—C3—C4	−0.4 (3)	C1—N1—C9—C10	3.2 (3)
C7—O1—C4—C3	165.99 (15)	N1—C9—C11—C12	1.1 (3)
C7—O1—C4—C5	−13.3 (2)	C10—C9—C11—C12	179.97 (18)
C2—C3—C4—O1	−176.87 (16)	C13—O3—C12—O2	7.7 (3)
C2—C3—C4—C5	2.5 (3)	C13—O3—C12—C11	−172.85 (18)
O1—C4—C5—C6	177.09 (16)	C9—C11—C12—O2	−1.7 (3)
C3—C4—C5—C6	−2.2 (2)	C9—C11—C12—O3	178.90 (18)
C2—C1—C6—C5	2.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	2.08	2.741 (2)	133
C6—H6···O2ⁱ	0.93	2.57	3.362 (3)	143

Symmetry code: (i) x, y+1, z.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₇NO₃
M_r	235.28
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	294
a, b, c (Å)	12.421 (2), 6.3372 (13), 16.569 (3)
β (°)	96.519 (3)
V (Å³)	1295.7 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.26 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.942, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	6917, 2628, 1629
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.624

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.136, 1.00
No. of reflections	2628
No. of parameters	158
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.11

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	2.08	2.741 (2)	133
C6—H6···O2ⁱ	0.93	2.57	3.362 (3)	143

Symmetry code: (i) x, y+1, z.

Acknowledgements

The authors acknowledge financial support from the Southern Yangtze University.

References

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