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Acta Cryst. (2009). E65, o751    [ doi:10.1107/S1600536809008496 ]

(5E)-Dimethyl 2-bromomethyl-5-cyclohexylimino-2-phenyl-2,5-dihydrofuran-3,4-dicarboxylate

A. Zonouzi, M. Biniaz, H. Rahmani and S. W. Ng

Abstract top

The molecule of the title compound, C21H24BrNO5, has a planar furan ring [maximum deviation = 0.025 (3) Å]. The carboxymethyl group in the 3-position is nearly coplanar with this ring [dihedral angle = 7.9 (1)°], whereas that in the 4-position is nearly perpendicular to it [dihedral angle = 78.9 (1) Å].

Related literature top

The iminolactone was synthesized by the one-pot, solvent-free reaction of dimethyl acetylenedicarboxylate, cyclohexyl isocyanide and α-bromoacetophenone under microwave irradiation; for other synthetic methods, see: Ma & Xie (2002, 2005); Nair et al. (2000); Villemin & Liao (2003).

Experimental top

To a mixture of 2-bromo-1-phenyl ethanone (α-bromo acetophenone, 0.398 g, 2 mmol) and dimethyl acetylenedicarboxylate (0.25 ml, 2 mmol), cyclohexyl isocyanide (0.25 ml, 2 mmol) was added. Irradiation of the mixture with microwave radiation (180 W) for 5 min produced the title iminolactone. The reaction was monitored by TLC (ethyl acetate n-hexane 4:1) until no α-bromoacetophenone was detectable. The product was recrystalized from methanol; yield 90%, m.p. 351 K.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C–H 0.95 to 0.99 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5Ueq(C).

The final difference Fourier map had a large peak/deep hole in the vicinity of the bromide atom. Attempts to model the bromide atom as being disordered over two positions did not lead to any improvement in the refinement.

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: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. Thermal ellisoid plot (Barbour, 2001) of C21H24BrNO5; probability levels are set at 70% and H-atoms are drawn as spheres of arbitrary radius.
(5E)-Dimethyl 2-bromomethyl-5-cyclohexylimino-2-phenyl-2,5-dihydrofuran-3,4-dicarboxylate top
Crystal data top
C21H24BrNO5F(000) = 928
Mr = 450.32Dx = 1.410 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3661 reflections
a = 16.8599 (3) Åθ = 2.7–28.3°
b = 7.2871 (1) ŵ = 1.97 mm−1
c = 17.4145 (3) ÅT = 123 K
β = 97.330 (1)°Prism, colorless
V = 2122.06 (6) Å30.30 × 0.15 × 0.10 mm
Z = 4
Data collection top
Bruker SMART APEX
diffractometer		4873 independent reflections
Radiation source: fine-focus sealed tube4034 reflections with I > 2σ(I)
graphiteRint = 0.046
ω scansθmax = 27.5°, θmin = 1.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −21→21
Tmin = 0.590, Tmax = 0.828k = −9→9
19142 measured reflectionsl = −22→22
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)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.156H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0837P)2 + 3.6326P]
where P = (Fo2 + 2Fc2)/3
4873 reflections(Δ/σ)max = 0.001
255 parametersΔρmax = 2.31 e Å−3
0 restraintsΔρmin = −0.67 e Å−3
Crystal data top
C21H24BrNO5V = 2122.06 (6) Å3
Mr = 450.32Z = 4
Monoclinic, P21/cMo Kα radiation
a = 16.8599 (3) ŵ = 1.97 mm−1
b = 7.2871 (1) ÅT = 123 K
c = 17.4145 (3) Å0.30 × 0.15 × 0.10 mm
β = 97.330 (1)°
Data collection top
Bruker SMART APEX
diffractometer		4873 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		4034 reflections with I > 2σ(I)
Tmin = 0.590, Tmax = 0.828Rint = 0.046
19142 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.156Δρmax = 2.31 e Å−3
S = 1.08Δρmin = −0.67 e Å−3
4873 reflectionsAbsolute structure: ?
255 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.25611 (3)1.02341 (5)0.45239 (2)0.03930 (16)
O10.29800 (12)0.6088 (3)0.49013 (12)0.0216 (4)
O20.09230 (13)0.3244 (3)0.36320 (12)0.0240 (5)
O30.11434 (15)0.5554 (4)0.28251 (13)0.0297 (5)
O40.06942 (14)0.8094 (3)0.54175 (13)0.0289 (5)
O50.02390 (13)0.6629 (3)0.43103 (13)0.0259 (5)
N10.30562 (15)0.4537 (4)0.37308 (15)0.0207 (5)
C10.23476 (17)0.6816 (4)0.53027 (16)0.0186 (6)
C20.16009 (17)0.6470 (4)0.47364 (16)0.0185 (6)
C30.17954 (17)0.5531 (4)0.41267 (16)0.0183 (6)
C40.26637 (18)0.5307 (4)0.42102 (16)0.0185 (6)
C50.25368 (19)0.8840 (4)0.54633 (17)0.0240 (6)
H5A0.30620.89430.57870.029*
H5B0.21280.93690.57590.029*
C60.23270 (17)0.5743 (4)0.60559 (16)0.0190 (6)
C70.25969 (18)0.3940 (4)0.61047 (17)0.0219 (6)
H70.27900.33820.56720.026*
C80.25852 (19)0.2952 (4)0.67858 (19)0.0251 (6)
H80.27710.17200.68150.030*
C90.2307 (2)0.3741 (5)0.74210 (19)0.0281 (7)
H90.23050.30600.78860.034*
C100.2030 (2)0.5530 (5)0.73749 (19)0.0308 (7)
H100.18360.60800.78090.037*
C110.20363 (19)0.6531 (5)0.66923 (18)0.0252 (6)
H110.18410.77550.66620.030*
C120.08049 (18)0.7155 (4)0.48724 (17)0.0212 (6)
C13−0.05632 (18)0.7330 (5)0.4356 (2)0.0291 (7)
H13A−0.09420.67410.39570.044*
H13B−0.05710.86600.42730.044*
H13C−0.07170.70590.48680.044*
C140.12496 (18)0.4812 (4)0.34460 (17)0.0194 (6)
C150.0330 (2)0.2459 (5)0.3044 (2)0.0329 (8)
H15A0.01360.12940.32320.049*
H15B0.05720.22400.25700.049*
H15C−0.01200.33120.29340.049*
C160.39323 (18)0.4490 (5)0.38899 (18)0.0236 (6)
H160.40970.45440.44620.028*
C170.4273 (2)0.6150 (5)0.3507 (2)0.0330 (8)
H17A0.40510.61890.29530.040*
H17B0.41090.72880.37550.040*
C180.5186 (2)0.6070 (6)0.3579 (2)0.0382 (9)
H18A0.53850.71190.32970.046*
H18B0.54100.61760.41300.046*
C190.5467 (2)0.4285 (7)0.3250 (2)0.0402 (9)
H19A0.52800.42260.26880.048*
H19B0.60590.42490.33210.048*
C200.5149 (2)0.2658 (6)0.3648 (2)0.0405 (9)
H20A0.53700.26630.42020.049*
H20B0.53230.15120.34140.049*
C210.4232 (2)0.2705 (5)0.3573 (2)0.0338 (8)
H21A0.40100.25750.30220.041*
H21B0.40400.16560.38600.041*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0740 (3)0.0243 (2)0.0196 (2)−0.01265 (16)0.00615 (16)0.00297 (13)
O10.0240 (10)0.0273 (12)0.0134 (10)−0.0023 (8)0.0023 (8)−0.0049 (8)
O20.0316 (11)0.0228 (11)0.0167 (10)−0.0060 (9)−0.0010 (8)−0.0029 (8)
O30.0384 (13)0.0344 (13)0.0146 (11)−0.0051 (10)−0.0029 (9)0.0058 (9)
O40.0321 (12)0.0330 (13)0.0214 (11)0.0071 (10)0.0022 (9)−0.0057 (10)
O50.0228 (10)0.0296 (12)0.0245 (11)0.0021 (9)0.0007 (8)−0.0072 (9)
N10.0246 (13)0.0224 (13)0.0157 (12)−0.0007 (10)0.0047 (9)−0.0015 (10)
C10.0241 (14)0.0189 (14)0.0129 (13)−0.0010 (10)0.0033 (10)−0.0019 (10)
C20.0261 (14)0.0156 (13)0.0132 (12)−0.0013 (11)0.0006 (10)0.0021 (10)
C30.0244 (14)0.0189 (14)0.0115 (13)−0.0008 (11)0.0015 (10)0.0005 (10)
C40.0260 (14)0.0190 (14)0.0100 (13)−0.0037 (11)0.0007 (10)−0.0002 (10)
C50.0340 (16)0.0218 (15)0.0161 (14)−0.0043 (12)0.0027 (12)−0.0008 (11)
C60.0209 (13)0.0217 (14)0.0139 (13)−0.0006 (11)0.0004 (10)−0.0009 (11)
C70.0258 (14)0.0210 (15)0.0184 (14)−0.0001 (11)0.0007 (11)−0.0031 (11)
C80.0304 (16)0.0195 (14)0.0241 (15)0.0003 (12)−0.0013 (12)0.0023 (12)
C90.0359 (17)0.0299 (17)0.0178 (14)−0.0010 (13)0.0009 (12)0.0061 (13)
C100.045 (2)0.0323 (18)0.0158 (15)0.0074 (15)0.0073 (13)0.0037 (13)
C110.0366 (17)0.0228 (15)0.0167 (14)0.0068 (13)0.0046 (12)0.0001 (12)
C120.0279 (15)0.0191 (14)0.0164 (13)0.0015 (11)0.0025 (11)0.0027 (11)
C130.0236 (15)0.0311 (17)0.0322 (17)0.0024 (13)0.0016 (12)0.0002 (14)
C140.0225 (14)0.0216 (14)0.0141 (13)0.0012 (11)0.0026 (10)−0.0018 (11)
C150.0348 (18)0.0362 (19)0.0265 (17)−0.0122 (15)−0.0015 (13)−0.0112 (14)
C160.0241 (15)0.0324 (17)0.0141 (14)−0.0019 (12)0.0021 (11)−0.0023 (12)
C170.0313 (17)0.036 (2)0.0314 (18)−0.0065 (14)0.0037 (13)0.0027 (15)
C180.0310 (18)0.048 (2)0.036 (2)−0.0099 (16)0.0038 (14)0.0017 (17)
C190.0253 (16)0.063 (3)0.0332 (19)−0.0053 (17)0.0070 (14)−0.0088 (19)
C200.0305 (18)0.046 (2)0.044 (2)0.0075 (16)0.0026 (15)−0.0067 (18)
C210.0279 (17)0.0329 (19)0.041 (2)0.0002 (14)0.0073 (14)−0.0066 (16)
Geometric parameters (Å, °) top
Br1—C51.930 (3)C9—H90.9500
O1—C41.376 (3)C10—C111.396 (4)
O1—C11.448 (3)C10—H100.9500
O2—C141.326 (4)C11—H110.9500
O2—C151.454 (4)C13—H13A0.9800
O3—C141.202 (4)C13—H13B0.9800
O4—C121.204 (4)C13—H13C0.9800
O5—C121.333 (4)C15—H15A0.9800
O5—C131.457 (4)C15—H15B0.9800
N1—C41.261 (4)C15—H15C0.9800
N1—C161.468 (4)C16—C211.524 (5)
C1—C21.518 (4)C16—C171.528 (5)
C1—C51.528 (4)C16—H161.0000
C1—C61.531 (4)C17—C181.529 (5)
C2—C31.339 (4)C17—H17A0.9900
C2—C121.479 (4)C17—H17B0.9900
C3—C41.462 (4)C18—C191.521 (6)
C3—C141.499 (4)C18—H18A0.9900
C5—H5A0.9900C18—H18B0.9900
C5—H5B0.9900C19—C201.506 (6)
C6—C111.392 (4)C19—H19A0.9900
C6—C71.389 (4)C19—H19B0.9900
C7—C81.390 (4)C20—C211.535 (5)
C7—H70.9500C20—H20A0.9900
C8—C91.381 (5)C20—H20B0.9900
C8—H80.9500C21—H21A0.9900
C9—C101.384 (5)C21—H21B0.9900
C4—O1—C1110.3 (2)O5—C13—H13C109.5
C14—O2—C15115.9 (3)H13A—C13—H13C109.5
C12—O5—C13116.2 (2)H13B—C13—H13C109.5
C4—N1—C16119.1 (3)O3—C14—O2126.0 (3)
O1—C1—C2103.1 (2)O3—C14—C3124.1 (3)
O1—C1—C5107.0 (2)O2—C14—C3109.9 (2)
C2—C1—C5114.6 (2)O2—C15—H15A109.5
O1—C1—C6109.0 (2)O2—C15—H15B109.5
C2—C1—C6111.4 (2)H15A—C15—H15B109.5
C5—C1—C6111.3 (2)O2—C15—H15C109.5
C3—C2—C12128.2 (3)H15A—C15—H15C109.5
C3—C2—C1109.5 (3)H15B—C15—H15C109.5
C12—C2—C1122.3 (3)N1—C16—C21108.9 (3)
C2—C3—C4108.8 (2)N1—C16—C17108.9 (3)
C2—C3—C14128.2 (3)C21—C16—C17111.0 (3)
C4—C3—C14123.1 (3)N1—C16—H16109.3
N1—C4—O1125.8 (3)C21—C16—H16109.3
N1—C4—C3126.0 (3)C17—C16—H16109.3
O1—C4—C3108.2 (2)C18—C17—C16111.4 (3)
C1—C5—Br1112.3 (2)C18—C17—H17A109.3
C1—C5—H5A109.1C16—C17—H17A109.3
Br1—C5—H5A109.1C18—C17—H17B109.3
C1—C5—H5B109.1C16—C17—H17B109.3
Br1—C5—H5B109.1H17A—C17—H17B108.0
H5A—C5—H5B107.9C19—C18—C17111.2 (3)
C11—C6—C7119.2 (3)C19—C18—H18A109.4
C11—C6—C1121.3 (3)C17—C18—H18A109.4
C7—C6—C1119.5 (3)C19—C18—H18B109.4
C6—C7—C8120.1 (3)C17—C18—H18B109.4
C6—C7—H7119.9H18A—C18—H18B108.0
C8—C7—H7119.9C20—C19—C18110.8 (3)
C9—C8—C7120.7 (3)C20—C19—H19A109.5
C9—C8—H8119.6C18—C19—H19A109.5
C7—C8—H8119.6C20—C19—H19B109.5
C8—C9—C10119.5 (3)C18—C19—H19B109.5
C8—C9—H9120.3H19A—C19—H19B108.1
C10—C9—H9120.3C19—C20—C21110.9 (3)
C9—C10—C11120.2 (3)C19—C20—H20A109.5
C9—C10—H10119.9C21—C20—H20A109.5
C11—C10—H10119.9C19—C20—H20B109.5
C6—C11—C10120.3 (3)C21—C20—H20B109.5
C6—C11—H11119.9H20A—C20—H20B108.0
C10—C11—H11119.9C16—C21—C20111.4 (3)
O4—C12—O5125.0 (3)C16—C21—H21A109.3
O4—C12—C2123.6 (3)C20—C21—H21A109.3
O5—C12—C2111.4 (3)C16—C21—H21B109.3
O5—C13—H13A109.5C20—C21—H21B109.3
O5—C13—H13B109.5H21A—C21—H21B108.0
H13A—C13—H13B109.5
C4—O1—C1—C2−3.2 (3)C11—C6—C7—C8−0.8 (4)
C4—O1—C1—C5−124.4 (2)C1—C6—C7—C8179.7 (3)
C4—O1—C1—C6115.1 (2)C6—C7—C8—C90.0 (5)
O1—C1—C2—C34.5 (3)C7—C8—C9—C100.6 (5)
C5—C1—C2—C3120.4 (3)C8—C9—C10—C11−0.3 (5)
C6—C1—C2—C3−112.2 (3)C7—C6—C11—C101.1 (5)
O1—C1—C2—C12−174.1 (2)C1—C6—C11—C10−179.4 (3)
C5—C1—C2—C12−58.2 (4)C9—C10—C11—C6−0.6 (5)
C6—C1—C2—C1269.2 (3)C13—O5—C12—O42.8 (5)
C12—C2—C3—C4174.5 (3)C13—O5—C12—C2−176.0 (3)
C1—C2—C3—C4−4.0 (3)C3—C2—C12—O4−175.0 (3)
C12—C2—C3—C14−4.6 (5)C1—C2—C12—O43.3 (5)
C1—C2—C3—C14176.9 (3)C3—C2—C12—O53.8 (4)
C16—N1—C4—O1−2.1 (5)C1—C2—C12—O5−177.9 (3)
C16—N1—C4—C3177.6 (3)C15—O2—C14—O3−5.8 (4)
C1—O1—C4—N1−179.2 (3)C15—O2—C14—C3175.4 (3)
C1—O1—C4—C31.1 (3)C2—C3—C14—O3100.1 (4)
C2—C3—C4—N1−177.8 (3)C4—C3—C14—O3−78.9 (4)
C14—C3—C4—N11.4 (5)C2—C3—C14—O2−81.1 (4)
C2—C3—C4—O12.0 (3)C4—C3—C14—O299.9 (3)
C14—C3—C4—O1−178.9 (3)C4—N1—C16—C21146.3 (3)
O1—C1—C5—Br161.4 (3)C4—N1—C16—C17−92.6 (3)
C2—C1—C5—Br1−52.2 (3)N1—C16—C17—C18−173.9 (3)
C6—C1—C5—Br1−179.67 (19)C21—C16—C17—C18−54.1 (4)
O1—C1—C6—C11153.4 (3)C16—C17—C18—C1955.4 (4)
C2—C1—C6—C11−93.6 (3)C17—C18—C19—C20−57.0 (4)
C5—C1—C6—C1135.6 (4)C18—C19—C20—C2157.2 (4)
O1—C1—C6—C7−27.2 (3)N1—C16—C21—C20174.2 (3)
C2—C1—C6—C785.9 (3)C17—C16—C21—C2054.4 (4)
C5—C1—C6—C7−145.0 (3)C19—C20—C21—C16−56.3 (4)
Acknowledgements top

We thank the Research Council of Tehran University and the University of Malaya for supporting this study.

references
References top

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Villemin, D. & Liao, L. (2003). Synth. Commun. 33, 1575–1585.

Westrip, S. P. (2009). publCIF. In preparation.