Methyl 2-[(4-chloro-2-meth­oxy-5-oxo-2,5-dihydro­furan-3-yl)amino]­acetate

Mo, Y.-Q.; Wang, Z.-Y.; Fu, J.-H.; Fang, H.-C.

doi:10.1107/S160053681002461X

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1857

doi:10.1107/S160053681002461X

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Methyl 2-[(4-chloro-2-methoxy-5-oxo-2,5-dihydrofuran-3-yl)amino]acetate

Yang-Qing Mo,^a Zhao-Yang Wang,^a ^* Jian-Hua Fu ^a and Hua-Cai Fang ^a

^aSchool of Chemistry and Environment, South China Normal University, Guangzhou 510006, People's Republic of China
^*Correspondence e-mail: wangwangzhaoyang@tom.com

(Received 17 June 2010; accepted 23 June 2010; online 30 June 2010)

The title compound, C₈H₁₀ClNO₅, was obtained via a tandem Michael addition–elimination reaction of 3,4-dichloro-5-methoxyfuran-2(5H)-one and glycine methyl ester in the presence of triethylamine. The molecular structure contains an approximately planar [maximum atomic deviation = 0.010 (2) Å] five-membered furanone ring. The crystal packing is stabilized by intermolecular N—H⋯O and weak C—H⋯O hydrogen bonding.

Related literature

For biologicallly active 4-amino-2(5H)-furanones, see: Kimura et al. (2000 ); Tanoury et al. (2008 ). For related furanone structures, see: Song et al. (2009b ); Li et al. (2009 ). For the synthesis, see: Song et al. (2009a ).

Experimental

Crystal data

C₈H₁₀ClNO₅
M_r = 235.62
Monoclinic, P 2₁ /c
a = 5.1366 (10) Å
b = 9.8316 (19) Å
c = 20.685 (4) Å
β = 102.532 (4)°
V = 1019.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 296 K
0.21 × 0.21 × 0.21 mm

Data collection

Bruker APEXII CCD diffractometer
3333 measured reflections
1714 independent reflections
1221 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.088
S = 1.05
1714 reflections
139 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.86	2.06	2.911 (3)	171
C6—H6B⋯O5ⁱⁱ	0.97	2.42	3.366 (3)	166
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) x-1, y, z.

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681002461X/xu2785sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681002461X/xu2785Isup2.hkl

checkCIF report

Comment top

2(5H)-Furanone is a simplest sub-unit of a large class of five membered heterocyclic carbonyl compounds. At the same time, 4-amino-2(5H)-furanone is an attractive moiety in chemical, pharmaceutical and agrochemical research. Many 4-amino-2(5H)-furanones have been patented as prodrugs or insecticides and herbicides (Kimura et al., 2000; Tanoury et al., 2008). Attracted by versatile 4-amino-2(5H)-furanones, we synthesized the title compound with 3,4-dichloro-5-methoxyfuran-2(5H)-one and glycine methylester in the presence of triethylamine via the tandem Michael addition-elimination reaction. With 2(5H)-furanone moiety and polyfunctional groups (carboxyl, amino, halo), the title compound is expected to be a biologically active product.

The structure of the title compound (I) is illustrated in Fig. 1. The title compound contains a five-membered furanone ring and a methoxy connected each other via C4—O3—C5 ether bond. The furanone ring is approximately planar, smilar to that found in a related compound (Song et al., 2009b). Additionally, the molecules are linked by intermolecular hydrogen bonds of N—H···O and C—H···O (Table 1).

Related literature top

For biologicallly active 4-amino-2(5H)-furanones, see: Kimura et al. (2000); Tanoury et al. (2008). For related furanone structures, see: Song et al. (2009b); Li et al. (2009).. For the synthesis, see: Song et al. (2009a).

Experimental top

The precursor 3,4-dichloro-5-methoxyfuran-2(5H)-furanone was prepared according to the literature procedure (Song et al., 2009a). After the mixture of glycine methylester (3.0 mmol) and triethylamine (2.8 ml) was dissolved in absolute tetrahydrofuran under nitrogen atmosphere, dichloromethane solution of 3,4-chloro-5-methoxyfuran-2(5H)-furanone (2.0 mmol) was added. The reaction was carried out under the stirring at room temperature for 55 h. Once the reaction was complete, the solvents were removed under reduced pressure. The residual solid was dissolved in dichloromethane. Then the combined organic layers from extraction were concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography with the gradient mixture of petroleum ether and ethyl acetate to give the product yielding (I) 0.2372 g (50.6%).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. View of the title compound showing the atom-labelling scheme. Ellipsoids are drawn at the 30% probability level.
	Fig. 2. Perspective view of the packing of (I). Dashed lines stand for hydrogen bonds.

Methyl 2-[(4-chloro-2-methoxy-5-oxo-2,5-dihydrofuran-3-yl)amino]acetate top

Crystal data top

C₈H₁₀ClNO₅	F(000) = 488
M_r = 235.62	D_x = 1.535 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 826 reflections
a = 5.1366 (10) Å	θ = 2.3–25.2°
b = 9.8316 (19) Å	µ = 0.38 mm⁻¹
c = 20.685 (4) Å	T = 296 K
β = 102.532 (4)°	Cubic, colorless
V = 1019.7 (3) Å³	0.21 × 0.21 × 0.21 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1221 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.019
Graphite monochromator	θ_max = 25.2°, θ_min = 2.0°
ϕ and ω scans	h = −5→6
3333 measured reflections	k = −5→11
1714 independent reflections	l = −24→24

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.088	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0339P)² + 0.3573P] where P = (F_o² + 2F_c²)/3
1714 reflections	(Δ/σ)_max < 0.001
139 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₈H₁₀ClNO₅	V = 1019.7 (3) Å³
M_r = 235.62	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.1366 (10) Å	µ = 0.38 mm⁻¹
b = 9.8316 (19) Å	T = 296 K
c = 20.685 (4) Å	0.21 × 0.21 × 0.21 mm
β = 102.532 (4)°

Data collection top

Bruker APEXII CCD diffractometer	1221 reflections with I > 2σ(I)
3333 measured reflections	R_int = 0.019
1714 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.088	H-atom parameters constrained
S = 1.05	Δρ_max = 0.18 e Å⁻³
1714 reflections	Δρ_min = −0.18 e Å⁻³
139 parameters

Special details top

Experimental. ¹H NMR (400 MHz, CDCl₃, TMS): 3.52 (3H, s, CH, CH₃), 3.82 (3H, s, CH, CH₃), 4.29 (2H, s, CH, CH₂), 5.75 (1H, s, CH).

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
Cl1	0.60822 (13)	0.63332 (7)	0.79402 (3)	0.0553 (3)
O1	−0.0366 (3)	0.45788 (17)	0.69305 (7)	0.0483 (5)
O2	0.1905 (4)	0.39330 (18)	0.79393 (8)	0.0539 (5)
O3	−0.0115 (3)	0.51417 (18)	0.58504 (7)	0.0514 (5)
O4	0.1774 (4)	0.86029 (19)	0.48157 (8)	0.0584 (5)
O5	0.5179 (4)	0.7421 (2)	0.54029 (8)	0.0643 (6)
N1	0.3070 (4)	0.7560 (2)	0.65232 (9)	0.0422 (5)
H1	0.4557	0.7914	0.6723	0.051*
C1	0.1684 (5)	0.4711 (3)	0.74761 (11)	0.0430 (6)
C2	0.3270 (5)	0.5858 (2)	0.73770 (10)	0.0391 (6)
C3	0.2222 (4)	0.6466 (2)	0.67961 (10)	0.0370 (6)
C4	−0.0206 (5)	0.5655 (3)	0.64653 (11)	0.0431 (6)
H4	−0.1788	0.6234	0.6422	0.052*
C5	0.2212 (6)	0.4363 (3)	0.58209 (12)	0.0557 (7)
H5A	0.2345	0.3603	0.6118	0.084*
H5B	0.3767	0.4925	0.5948	0.084*
H5C	0.2083	0.4039	0.5377	0.084*
C6	0.1683 (5)	0.8198 (3)	0.59157 (11)	0.0437 (6)
H6A	0.1498	0.9162	0.5993	0.052*
H6B	−0.0092	0.7813	0.5785	0.052*
C7	0.3126 (5)	0.8008 (2)	0.53614 (11)	0.0406 (6)
C8	0.2996 (7)	0.8523 (3)	0.42456 (13)	0.0732 (9)
H8A	0.2823	0.7614	0.4072	0.110*
H8B	0.4851	0.8755	0.4378	0.110*
H8C	0.2122	0.9146	0.3911	0.110*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0510 (4)	0.0741 (5)	0.0358 (3)	−0.0075 (3)	−0.0018 (3)	−0.0010 (3)
O1	0.0403 (11)	0.0567 (11)	0.0465 (9)	−0.0055 (8)	0.0062 (7)	0.0025 (9)
O2	0.0549 (12)	0.0595 (12)	0.0498 (10)	0.0069 (9)	0.0166 (8)	0.0126 (9)
O3	0.0497 (12)	0.0609 (12)	0.0378 (9)	0.0078 (9)	−0.0033 (7)	−0.0068 (8)
O4	0.0615 (13)	0.0742 (13)	0.0422 (9)	0.0274 (10)	0.0172 (8)	0.0172 (9)
O5	0.0448 (12)	0.0992 (16)	0.0502 (10)	0.0270 (11)	0.0129 (8)	0.0102 (10)
N1	0.0366 (12)	0.0530 (13)	0.0352 (10)	−0.0009 (10)	0.0041 (8)	0.0014 (10)
C1	0.0370 (15)	0.0543 (16)	0.0393 (13)	0.0080 (12)	0.0119 (10)	−0.0011 (13)
C2	0.0365 (14)	0.0498 (15)	0.0305 (12)	0.0000 (11)	0.0061 (9)	−0.0013 (11)
C3	0.0323 (14)	0.0465 (14)	0.0332 (12)	0.0073 (11)	0.0094 (9)	−0.0029 (11)
C4	0.0369 (15)	0.0519 (16)	0.0389 (13)	0.0040 (11)	0.0045 (10)	0.0006 (12)
C5	0.0641 (19)	0.0567 (17)	0.0443 (14)	0.0112 (14)	0.0074 (12)	−0.0074 (13)
C6	0.0427 (16)	0.0466 (15)	0.0422 (13)	0.0086 (12)	0.0099 (11)	0.0054 (11)
C7	0.0382 (16)	0.0427 (14)	0.0400 (13)	0.0001 (12)	0.0067 (11)	−0.0007 (11)
C8	0.087 (2)	0.093 (2)	0.0451 (15)	0.0227 (19)	0.0262 (15)	0.0180 (16)

Geometric parameters (Å, º) top

Cl1—C2	1.712 (2)	C2—C3	1.345 (3)
O1—C1	1.372 (3)	C3—C4	1.513 (3)
O1—C4	1.444 (3)	C4—H4	0.9800
O2—C1	1.212 (3)	C5—H5A	0.9600
O3—C4	1.378 (3)	C5—H5B	0.9600
O3—C5	1.432 (3)	C5—H5C	0.9600
O4—C7	1.326 (3)	C6—C7	1.506 (3)
O4—C8	1.453 (3)	C6—H6A	0.9700
O5—C7	1.189 (3)	C6—H6B	0.9700
N1—C3	1.331 (3)	C8—H8A	0.9600
N1—C6	1.446 (3)	C8—H8B	0.9600
N1—H1	0.8600	C8—H8C	0.9600
C1—C2	1.432 (4)

C1—O1—C4	109.53 (18)	O3—C5—H5A	109.5
C4—O3—C5	115.52 (18)	O3—C5—H5B	109.5
C7—O4—C8	115.4 (2)	H5A—C5—H5B	109.5
C3—N1—C6	125.0 (2)	O3—C5—H5C	109.5
C3—N1—H1	117.5	H5A—C5—H5C	109.5
C6—N1—H1	117.5	H5B—C5—H5C	109.5
O2—C1—O1	121.0 (2)	N1—C6—C7	112.1 (2)
O2—C1—C2	130.7 (2)	N1—C6—H6A	109.2
O1—C1—C2	108.4 (2)	C7—C6—H6A	109.2
C3—C2—C1	110.4 (2)	N1—C6—H6B	109.2
C3—C2—Cl1	127.0 (2)	C7—C6—H6B	109.2
C1—C2—Cl1	122.65 (18)	H6A—C6—H6B	107.9
N1—C3—C2	129.3 (2)	O5—C7—O4	124.6 (2)
N1—C3—C4	123.20 (19)	O5—C7—C6	125.5 (2)
C2—C3—C4	107.5 (2)	O4—C7—C6	109.9 (2)
O3—C4—O1	111.4 (2)	O4—C8—H8A	109.5
O3—C4—C3	114.9 (2)	O4—C8—H8B	109.5
O1—C4—C3	104.20 (17)	H8A—C8—H8B	109.5
O3—C4—H4	108.7	O4—C8—H8C	109.5
O1—C4—H4	108.7	H8A—C8—H8C	109.5
C3—C4—H4	108.7	H8B—C8—H8C	109.5

C4—O1—C1—O2	178.2 (2)	C5—O3—C4—C3	52.9 (3)
C4—O1—C1—C2	−1.2 (2)	C1—O1—C4—O3	124.6 (2)
O2—C1—C2—C3	−177.5 (2)	C1—O1—C4—C3	0.2 (2)
O1—C1—C2—C3	1.9 (3)	N1—C3—C4—O3	57.7 (3)
O2—C1—C2—Cl1	2.5 (4)	C2—C3—C4—O3	−121.2 (2)
O1—C1—C2—Cl1	−178.19 (16)	N1—C3—C4—O1	179.8 (2)
C6—N1—C3—C2	−175.1 (2)	C2—C3—C4—O1	1.0 (2)
C6—N1—C3—C4	6.3 (3)	C3—N1—C6—C7	−110.6 (3)
C1—C2—C3—N1	179.5 (2)	C8—O4—C7—O5	−1.1 (4)
Cl1—C2—C3—N1	−0.4 (4)	C8—O4—C7—C6	178.5 (2)
C1—C2—C3—C4	−1.7 (3)	N1—C6—C7—O5	−0.7 (4)
Cl1—C2—C3—C4	178.33 (18)	N1—C6—C7—O4	179.7 (2)
C5—O3—C4—O1	−65.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.86	2.06	2.911 (3)	171
C6—H6B···O5ⁱⁱ	0.97	2.42	3.366 (3)	166

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₈H₁₀ClNO₅
M_r	235.62
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	5.1366 (10), 9.8316 (19), 20.685 (4)
β (°)	102.532 (4)
V (Å³)	1019.7 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.38
Crystal size (mm)	0.21 × 0.21 × 0.21

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3333, 1714, 1221
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.088, 1.05
No. of reflections	1714
No. of parameters	139
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.18

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.86	2.06	2.911 (3)	171
C6—H6B···O5ⁱⁱ	0.97	2.42	3.366 (3)	166

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x−1, y, z.

Acknowledgements

The work was supported by the National Natural Science Foundation of China (grant No. 20772035) and the Natural Science Foundation of Guangdong Province, China (grant No. 5300082).

References

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