3-Bromo-4-dibenzyl­amino-5-methoxy­furan-2(5H)-one

Fu, J.-H.; Li, Z.-Y.; Wang, Z.-Y.; Ye, R.-R.

doi:10.1107/S1600536810008007

organic compounds

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Volume 66| Part 4| April 2010| Page o769

doi:10.1107/S1600536810008007

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3-Bromo-4-dibenzylamino-5-methoxyfuran-2(5H)-one

Jian-Hua Fu,^a Zhao-Yang Li,^a Zhao-Yang Wang ^a ^* and Rui-Rong Ye ^a

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

(Received 30 January 2010; accepted 2 March 2010; online 6 March 2010)

In the the title compound, C₁₉H₁₈BrNO₃, the furanone ring is almost planar [maximum atomic deviation = 0.019 (3) Å] and is nearly perpendicular to the two phenyl rings, making dihedral angles of 88.96 (17) and 87.71 (17)°. Intermolecular C—H⋯O hydrogen bonding is present in the crystal structure.

Related literature

2(5H)-Furanone is the simplest sub-unit of a large class of five-membered heterocyclic carbonyl compounds, see: Reva et al. (2008 ). The title compound is a derivative of 4-amino-2(5H)-furanone. For the biological activity of 4-amino-2(5H)-furanones, see: Kimura et al. (2000 ); Tanoury et al. (2008 ). For the synthesis, see: Toshiyuki & Yoshikazu (1955 ).

Experimental

Crystal data

C₁₉H₁₈BrNO₃
M_r = 388.25
Orthorhombic, P b c a
a = 15.756 (2) Å
b = 11.2475 (14) Å
c = 19.779 (3) Å
V = 3505.2 (8) Å³
Z = 8
Mo Kα radiation
μ = 2.36 mm⁻¹
T = 298 K
0.23 × 0.20 × 0.16 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.613, T_max = 0.704
18029 measured reflections
3429 independent reflections
2028 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.089
S = 1.00
3429 reflections
218 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C16—H16⋯O3ⁱ	0.98	2.49	3.396 (4)	154
Symmetry code: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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 global, I. DOI: 10.1107/S1600536810008007/xu2724sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810008007/xu2724Isup2.hkl

checkCIF report

Comment top

2(5H)-Furanone is a simplest sub-unit of a large class of five membered heterocyclic carbonyl compounds (Reva et al., 2008). 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-dibromo-5-methoxyfuran-2(5H)-one and dibenzylamine in the presence of potassium fluoride via the tandem asymmetric 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 two six-membered benzene rings. The furanone ring is approximately planar.

Related literature top

2(5H)-Furanone is the simplest sub-unit of a large class of five-membered heterocyclic carbonyl compounds, see: Reva et al. (2008). The title compound is a derivative of 4-amino-2(5H)-furanone; for the biological active of 4-amino-2(5H)-furanones, see: Kimura et al. (2000); Tanoury et al. (2008). For the synthesis, see: Toshiyuki & Yoshikazu (1955).

Experimental top

The precursor 3,4-dibromo-5-methoxyfuran-2(5H)-furanone was prepared according to the literature procedure (Toshiyuki & Yoshikazu, 1955).

After the mixture of dibenzylamine (2 mmol) and potassium fluoride (6 mmol) was dissolved in absolute tetrahydrofuran (2 ml) under nitrogen atmosphere, dichloromethane solution of 3,4-dibromo-5-methoxyfuran-2(5H)-furanone (2.0 mmol) was added. The residual liquid was dissolved in dichloromethane. The reaction was carried out under the stirring at room temperature for 48 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) 0.6224 g (80.2%).

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 50% probability level.

3-Bromo-4-dibenzylamino-5-methoxyfuran-2(5H)-one top

Crystal data top

C₁₉H₁₈BrNO₃	F(000) = 1584
M_r = 388.25	D_x = 1.471 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2798 reflections
a = 15.756 (2) Å	θ = 2.5–21.2°
b = 11.2475 (14) Å	µ = 2.36 mm⁻¹
c = 19.779 (3) Å	T = 298 K
V = 3505.2 (8) Å³	Block, colourless
Z = 8	0.23 × 0.20 × 0.16 mm

Data collection top

Bruker APEXII area-detector diffractometer	3429 independent reflections
Radiation source: fine-focus sealed tube	2028 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
ϕ and ω scan	θ_max = 26.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −19→18
T_min = 0.613, T_max = 0.704	k = −13→13
18029 measured reflections	l = −10→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) = 0.089	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0297P)² + 1.9449P] where P = (F_o² + 2F_c²)/3
3429 reflections	(Δ/σ)_max = 0.002
218 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₉H₁₈BrNO₃	V = 3505.2 (8) Å³
M_r = 388.25	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 15.756 (2) Å	µ = 2.36 mm⁻¹
b = 11.2475 (14) Å	T = 298 K
c = 19.779 (3) Å	0.23 × 0.20 × 0.16 mm

Data collection top

Bruker APEXII area-detector diffractometer	3429 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2028 reflections with I > 2σ(I)
T_min = 0.613, T_max = 0.704	R_int = 0.054
18029 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 1.00	Δρ_max = 0.30 e Å⁻³
3429 reflections	Δρ_min = −0.27 e Å⁻³
218 parameters

Special details top

Experimental. ¹H NMR (400 MHz, CDCl₃, TMS): 3.52 (3H, s, CH, CH₃), 4.53 (2H, d, CH, CH₂), 4.90 (2H, d, CH, CH₂), 5.74 (1H, s, CH), 7.21-7.42 (10H, m, CH, Ar-H);

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Br1	0.09981 (2)	1.14889 (3)	0.35209 (2)	0.07708 (16)
C9	0.24254 (19)	0.8956 (3)	0.36299 (14)	0.0447 (7)
C5	0.29710 (17)	0.8590 (3)	0.16073 (14)	0.0440 (7)
C8	0.25104 (19)	0.9658 (3)	0.29832 (14)	0.0506 (8)
H8A	0.2423	1.0493	0.3083	0.061*
H8B	0.3085	0.9570	0.2815	0.061*
C6	0.3624 (2)	0.7779 (3)	0.15594 (17)	0.0689 (10)
H6	0.3598	0.7075	0.1805	0.083*
C7	0.22153 (18)	0.8294 (2)	0.20442 (15)	0.0495 (8)
H7A	0.1754	0.8027	0.1757	0.059*
H7B	0.2365	0.7644	0.2344	0.059*
C10	0.1799 (2)	0.8127 (3)	0.37322 (17)	0.0618 (9)
H10	0.1395	0.7997	0.3398	0.074*
C4	0.3031 (2)	0.9608 (3)	0.12329 (18)	0.0674 (10)
H4	0.2598	1.0168	0.1252	0.081*
C14	0.3011 (2)	0.9133 (3)	0.41324 (17)	0.0625 (9)
H14	0.3436	0.9696	0.4072	0.075*
C11	0.1764 (2)	0.7486 (3)	0.43241 (19)	0.0750 (11)
H11	0.1335	0.6928	0.4388	0.090*
C13	0.2981 (3)	0.8493 (4)	0.47231 (18)	0.0828 (12)
H13	0.3385	0.8623	0.5058	0.099*
C12	0.2358 (3)	0.7666 (4)	0.48199 (18)	0.0806 (11)
H12	0.2337	0.7230	0.5219	0.097*
C2	0.4371 (3)	0.9017 (4)	0.0793 (2)	0.0818 (12)
H2	0.4844	0.9168	0.0525	0.098*
C1	0.4314 (2)	0.7997 (4)	0.1153 (2)	0.0858 (12)
H1	0.4747	0.7438	0.1125	0.103*
C3	0.3730 (3)	0.9814 (4)	0.0826 (2)	0.0840 (12)
H3	0.3760	1.0509	0.0573	0.101*
N1	0.19202 (15)	0.9304 (2)	0.24524 (12)	0.0448 (6)
O1	0.08872 (13)	0.95812 (19)	0.12416 (10)	0.0558 (6)
O3	−0.06901 (14)	1.1434 (2)	0.26344 (12)	0.0691 (6)
O2	−0.02363 (12)	0.99727 (18)	0.19541 (10)	0.0532 (5)
C16	0.05326 (18)	0.9313 (3)	0.18643 (14)	0.0434 (7)
H16	0.0426	0.8457	0.1904	0.052*
C18	0.11283 (18)	0.9735 (2)	0.24190 (14)	0.0400 (7)
C20	−0.0134 (2)	1.0746 (3)	0.24854 (16)	0.0497 (8)
C19	0.06917 (18)	1.0562 (2)	0.27812 (14)	0.0446 (7)
C15	0.0499 (3)	0.8984 (4)	0.07008 (18)	0.0898 (13)
H15A	0.0518	0.8142	0.0780	0.135*
H15B	0.0794	0.9166	0.0289	0.135*
H15C	−0.0082	0.9235	0.0663	0.135*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0724 (3)	0.0756 (3)	0.0833 (3)	0.0017 (2)	−0.0117 (2)	−0.0326 (2)
C9	0.0377 (17)	0.0467 (16)	0.0498 (19)	0.0101 (14)	−0.0009 (15)	−0.0007 (14)
C5	0.0398 (17)	0.0478 (17)	0.0445 (18)	0.0011 (15)	−0.0038 (13)	0.0051 (15)
C8	0.0364 (17)	0.0554 (19)	0.060 (2)	−0.0035 (15)	−0.0035 (15)	0.0059 (16)
C6	0.059 (2)	0.074 (2)	0.073 (2)	0.0192 (19)	0.0072 (19)	0.026 (2)
C7	0.0452 (18)	0.0435 (18)	0.060 (2)	0.0056 (14)	0.0007 (15)	0.0084 (15)
C10	0.053 (2)	0.075 (2)	0.057 (2)	−0.0080 (18)	−0.0030 (16)	0.0139 (18)
C4	0.060 (2)	0.057 (2)	0.085 (3)	0.0059 (17)	0.0155 (19)	0.020 (2)
C14	0.061 (2)	0.068 (2)	0.059 (2)	0.0024 (18)	−0.0100 (18)	−0.0032 (19)
C11	0.079 (3)	0.081 (3)	0.066 (2)	−0.006 (2)	0.005 (2)	0.017 (2)
C13	0.088 (3)	0.102 (3)	0.058 (3)	0.008 (3)	−0.022 (2)	−0.005 (2)
C12	0.097 (3)	0.091 (3)	0.054 (2)	0.015 (3)	0.002 (2)	0.019 (2)
C2	0.059 (2)	0.103 (3)	0.083 (3)	−0.005 (2)	0.023 (2)	0.006 (3)
C1	0.060 (2)	0.102 (3)	0.095 (3)	0.026 (2)	0.024 (2)	0.017 (3)
C3	0.080 (3)	0.075 (3)	0.098 (3)	−0.007 (2)	0.026 (2)	0.030 (2)
N1	0.0362 (14)	0.0476 (14)	0.0506 (15)	−0.0009 (12)	−0.0020 (11)	0.0026 (12)
O1	0.0549 (13)	0.0668 (14)	0.0457 (13)	−0.0002 (11)	0.0038 (11)	0.0049 (11)
O3	0.0516 (13)	0.0647 (14)	0.0909 (18)	0.0162 (12)	0.0008 (12)	−0.0133 (13)
O2	0.0393 (12)	0.0610 (13)	0.0594 (14)	0.0064 (10)	−0.0041 (10)	−0.0071 (11)
C16	0.0411 (17)	0.0447 (17)	0.0442 (18)	−0.0011 (14)	0.0014 (14)	0.0013 (14)
C18	0.0381 (17)	0.0366 (16)	0.0452 (17)	−0.0082 (13)	0.0016 (13)	0.0085 (13)
C20	0.048 (2)	0.0440 (18)	0.057 (2)	−0.0009 (16)	0.0058 (16)	0.0004 (16)
C19	0.0427 (17)	0.0406 (16)	0.0506 (18)	−0.0044 (14)	−0.0017 (14)	−0.0012 (14)
C15	0.086 (3)	0.133 (4)	0.050 (2)	−0.001 (3)	0.004 (2)	−0.015 (2)

Geometric parameters (Å, º) top

Br1—C19	1.860 (3)	C11—H11	0.9300
C9—C14	1.371 (4)	C13—C12	1.366 (5)
C9—C10	1.372 (4)	C13—H13	0.9300
C9—C8	1.509 (4)	C12—H12	0.9300
C5—C4	1.367 (4)	C2—C3	1.351 (5)
C5—C6	1.378 (4)	C2—C1	1.353 (5)
C5—C7	1.508 (4)	C2—H2	0.9300
C8—N1	1.458 (3)	C1—H1	0.9300
C8—H8A	0.9700	C3—H3	0.9300
C8—H8B	0.9700	N1—C18	1.340 (3)
C6—C1	1.374 (5)	O1—C16	1.386 (3)
C6—H6	0.9300	O1—C15	1.404 (4)
C7—N1	1.469 (3)	O3—C20	1.206 (3)
C7—H7A	0.9700	O2—C20	1.374 (3)
C7—H7B	0.9700	O2—C16	1.432 (3)
C10—C11	1.376 (4)	C16—C18	1.520 (4)
C10—H10	0.9300	C16—H16	0.9800
C4—C3	1.383 (5)	C18—C19	1.361 (4)
C4—H4	0.9300	C20—C19	1.441 (4)
C14—C13	1.373 (5)	C15—H15A	0.9600
C14—H14	0.9300	C15—H15B	0.9600
C11—C12	1.371 (5)	C15—H15C	0.9600

C14—C9—C10	118.4 (3)	C13—C12—H12	120.3
C14—C9—C8	118.6 (3)	C11—C12—H12	120.3
C10—C9—C8	123.0 (3)	C3—C2—C1	119.1 (4)
C4—C5—C6	117.7 (3)	C3—C2—H2	120.4
C4—C5—C7	123.4 (3)	C1—C2—H2	120.4
C6—C5—C7	118.9 (3)	C2—C1—C6	120.8 (4)
N1—C8—C9	114.3 (2)	C2—C1—H1	119.6
N1—C8—H8A	108.7	C6—C1—H1	119.6
C9—C8—H8A	108.7	C2—C3—C4	120.8 (4)
N1—C8—H8B	108.7	C2—C3—H3	119.6
C9—C8—H8B	108.7	C4—C3—H3	119.6
H8A—C8—H8B	107.6	C18—N1—C8	122.1 (2)
C1—C6—C5	120.8 (3)	C18—N1—C7	123.2 (2)
C1—C6—H6	119.6	C8—N1—C7	113.9 (2)
C5—C6—H6	119.6	C16—O1—C15	113.4 (2)
N1—C7—C5	113.2 (2)	C20—O2—C16	108.9 (2)
N1—C7—H7A	108.9	O1—C16—O2	109.8 (2)
C5—C7—H7A	108.9	O1—C16—C18	108.9 (2)
N1—C7—H7B	108.9	O2—C16—C18	105.7 (2)
C5—C7—H7B	108.9	O1—C16—H16	110.7
H7A—C7—H7B	107.7	O2—C16—H16	110.7
C9—C10—C11	120.7 (3)	C18—C16—H16	110.7
C9—C10—H10	119.6	N1—C18—C19	133.8 (3)
C11—C10—H10	119.6	N1—C18—C16	119.9 (2)
C5—C4—C3	120.7 (3)	C19—C18—C16	106.3 (2)
C5—C4—H4	119.7	O3—C20—O2	120.5 (3)
C3—C4—H4	119.7	O3—C20—C19	130.5 (3)
C9—C14—C13	121.2 (3)	O2—C20—C19	109.0 (3)
C9—C14—H14	119.4	C18—C19—C20	109.9 (3)
C13—C14—H14	119.4	C18—C19—Br1	131.8 (2)
C12—C11—C10	120.2 (4)	C20—C19—Br1	118.2 (2)
C12—C11—H11	119.9	O1—C15—H15A	109.5
C10—C11—H11	119.9	O1—C15—H15B	109.5
C12—C13—C14	120.0 (4)	H15A—C15—H15B	109.5
C12—C13—H13	120.0	O1—C15—H15C	109.5
C14—C13—H13	120.0	H15A—C15—H15C	109.5
C13—C12—C11	119.4 (4)	H15B—C15—H15C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···O3ⁱ	0.98	2.49	3.396 (4)	154

Symmetry code: (i) −x, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₉H₁₈BrNO₃
M_r	388.25
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	15.756 (2), 11.2475 (14), 19.779 (3)
V (Å³)	3505.2 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	2.36
Crystal size (mm)	0.23 × 0.20 × 0.16

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.613, 0.704
No. of measured, independent and observed [I > 2σ(I)] reflections	18029, 3429, 2028
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.089, 1.00
No. of reflections	3429
No. of parameters	218
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.27

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
C16—H16···O3ⁱ	0.98	2.49	3.396 (4)	154

Symmetry code: (i) −x, y−1/2, −z+1/2.

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).

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