supplementary materials
2-(3-Methyl-2-nitrophenyl)-4,5-dihydro-1,3-oxazole
In the title compound, C10H10N2O3, an intermediate in the synthesis of anthranilamide insecticides, all the non-H atoms except the nitro-group O atom lie on a crystallographic mirror plane. The H atoms of the methyl group are disordered over two sets of sites with equal occupancies. In the crystal structure, C-H
N links lead to chains of molecules propagating in [100].
2-Bromoethanamine hydrobromide (10.25 g, 50 mmol) and 3-methyl-2-nitrobenzoyl
chloride (9.98 g, 50 mmol) were added into dichloromethane (200 ml), then
triethylamine (16.70 g, 165 mmol) was added. The mixture was heated to reflux
for 14 h and cooled down to room temperature, washed with water and brine,
dried by anhydrous sulfate magnesium, then evaporated to give the title
compound as a white solid.
The product was dissolved in dichloromethane and left to stand at room
temperature and colourless blocks of (I) were obtained.
Anal. Calcd for C10H10N2O3: C, 58.25; H, 4.89; N, 13.59; O, 23.28.
Found: C, 58.20; H, 4.90; N, 13.61; O, 23.25 1H NMR(CDCl3): 2.35 (s, 3H,
CH3), 4.06 (t, J=9.8 Hz, 2H, CH2), 4.40 (t, J=9.6 Hz, 2H, CH2),
7.41–7.43(m, 2H), 7.78–7.81 (m, 1H).
Although all H atoms were visible in difference maps, they were finally placed
in geometrically calculated positions, with C—H distances in the range
0.93–0.96 Å, and included in the final refinement in the riding model
approximation, with Uiso(H) = 1.2Ueq(C) for aromatic and
Uiso(H) = 1.5Ueq(C) for methyl H atoms.
Data collection: SMART (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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).
2-(3-Methyl-2-nitrophenyl)-4,5-dihydro-1,3-oxazole
top
Crystal data top
| C10H10N2O3 | F(000) = 216 |
| Mr = 206.20 | Dx = 1.407 Mg m−3 |
| Monoclinic, P21/m | Mo Kα radiation, λ = 0.71073 Å |
| a = 7.7767 (10) Å | Cell parameters from 1713 reflections |
| b = 7.337 (1) Å | θ = 2.7–27.9° |
| c = 8.6468 (12) Å | µ = 0.11 mm−1 |
| β = 99.414 (2)° | T = 296 K |
| V = 486.72 (11) Å3 | BLOCK, colourless |
| Z = 2 | 0.24 × 0.22 × 0.18 mm |
Data collection top
Bruker SMART CCD
diffractometer | 937 independent reflections |
| Radiation source: fine-focus sealed tube | 842 reflections with I > 2σ(I) |
| graphite | Rint = 0.011 |
| ω scans | θmax = 25.0°, θmin = 2.4° |
Absorption correction: multi-scan
(SADABS; Bruker, 2001) | h = −9→9 |
| Tmin = 0.834, Tmax = 1.000 | k = −6→8 |
| 2462 measured reflections | l = −10→9 |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.110 | H-atom parameters constrained |
| S = 1.07 | w = 1/[σ2(Fo2) + (0.0583P)2 + 0.1052P]
where P = (Fo2 + 2Fc2)/3 |
| 937 reflections | (Δ/σ)max < 0.001 |
| 90 parameters | Δρmax = 0.17 e Å−3 |
| 0 restraints | Δρmin = −0.15 e Å−3 |
Crystal data top
| C10H10N2O3 | V = 486.72 (11) Å3 |
| Mr = 206.20 | Z = 2 |
| Monoclinic, P21/m | Mo Kα radiation |
| a = 7.7767 (10) Å | µ = 0.11 mm−1 |
| b = 7.337 (1) Å | T = 296 K |
| c = 8.6468 (12) Å | 0.24 × 0.22 × 0.18 mm |
| β = 99.414 (2)° | |
Data collection top
Bruker SMART CCD
diffractometer | 937 independent reflections |
Absorption correction: multi-scan
(SADABS; Bruker, 2001) | 842 reflections with I > 2σ(I) |
| Tmin = 0.834, Tmax = 1.000 | Rint = 0.011 |
| 2462 measured reflections | θmax = 25.0° |
Refinement top
| R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
| wR(F2) = 0.110 | Δρmax = 0.17 e Å−3 |
| S = 1.07 | Δρmin = −0.15 e Å−3 |
| 937 reflections | Absolute structure: ? |
| 90 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | Uiso*/Ueq | Occ. (<1) |
| O1 | 0.2190 (2) | 0.2500 | 1.12373 (17) | 0.0794 (6) | |
| O2 | 0.33918 (12) | 0.10351 (17) | 0.61731 (13) | 0.0628 (4) | |
| N1 | 0.4057 (2) | 0.2500 | 0.95534 (19) | 0.0617 (6) | |
| N2 | 0.27535 (19) | 0.2500 | 0.64083 (17) | 0.0428 (4) | |
| C1 | −0.0249 (3) | 0.2500 | 0.4054 (2) | 0.0520 (5) | |
| H1A | 0.0705 | 0.3268 | 0.3893 | 0.078* | 0.50 |
| H1B | −0.1309 | 0.2952 | 0.3449 | 0.078* | 0.50 |
| H1C | −0.0041 | 0.1280 | 0.3728 | 0.078* | 0.50 |
| C2 | −0.0410 (2) | 0.2500 | 0.5759 (2) | 0.0430 (5) | |
| C3 | −0.2030 (3) | 0.2500 | 0.6245 (3) | 0.0533 (5) | |
| H3 | −0.3034 | 0.2500 | 0.5495 | 0.064* | |
| C4 | −0.2181 (3) | 0.2500 | 0.7801 (3) | 0.0630 (6) | |
| H4 | −0.3281 | 0.2500 | 0.8092 | 0.076* | |
| C5 | −0.0709 (3) | 0.2500 | 0.8946 (3) | 0.0589 (6) | |
| H5 | −0.0828 | 0.2500 | 0.9998 | 0.071* | |
| C6 | 0.0946 (2) | 0.2500 | 0.8531 (2) | 0.0434 (5) | |
| C7 | 0.1040 (2) | 0.2500 | 0.6938 (2) | 0.0381 (4) | |
| C8 | 0.2508 (2) | 0.2500 | 0.9762 (2) | 0.0428 (5) | |
| C9 | 0.3878 (3) | 0.2500 | 1.2242 (3) | 0.0671 (7) | |
| H9 | 0.4021 | 0.1424 | 1.2902 | 0.081* | |
| C10 | 0.5156 (3) | 0.2500 | 1.1111 (2) | 0.0580 (6) | |
| H10 | 0.5890 | 0.3576 | 1.1251 | 0.070* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| O1 | 0.0487 (9) | 0.1510 (17) | 0.0384 (8) | 0.000 | 0.0066 (7) | 0.000 |
| O2 | 0.0475 (6) | 0.0714 (8) | 0.0701 (8) | 0.0137 (5) | 0.0117 (5) | −0.0128 (5) |
| N1 | 0.0353 (9) | 0.1100 (16) | 0.0376 (9) | 0.000 | −0.0005 (7) | 0.000 |
| N2 | 0.0323 (8) | 0.0582 (10) | 0.0363 (8) | 0.000 | 0.0013 (6) | 0.000 |
| C1 | 0.0451 (11) | 0.0637 (13) | 0.0437 (11) | 0.000 | −0.0033 (8) | 0.000 |
| C2 | 0.0358 (10) | 0.0443 (10) | 0.0463 (10) | 0.000 | −0.0010 (8) | 0.000 |
| C3 | 0.0316 (9) | 0.0658 (13) | 0.0594 (13) | 0.000 | −0.0020 (8) | 0.000 |
| C4 | 0.0322 (10) | 0.0932 (17) | 0.0649 (14) | 0.000 | 0.0114 (9) | 0.000 |
| C5 | 0.0397 (11) | 0.0885 (16) | 0.0505 (12) | 0.000 | 0.0130 (9) | 0.000 |
| C6 | 0.0347 (10) | 0.0516 (11) | 0.0434 (10) | 0.000 | 0.0046 (8) | 0.000 |
| C7 | 0.0290 (8) | 0.0422 (10) | 0.0428 (10) | 0.000 | 0.0047 (7) | 0.000 |
| C8 | 0.0408 (10) | 0.0521 (11) | 0.0352 (9) | 0.000 | 0.0057 (7) | 0.000 |
| C9 | 0.0550 (13) | 0.1013 (19) | 0.0413 (11) | 0.000 | −0.0030 (10) | 0.000 |
| C10 | 0.0445 (11) | 0.0834 (16) | 0.0418 (11) | 0.000 | −0.0058 (8) | 0.000 |
Geometric parameters (Å, °) top
| O1—C8 | 1.339 (2) | C3—C4 | 1.370 (3) |
| O1—C9 | 1.451 (3) | C3—H3 | 0.9300 |
| O2—N2 | 1.2149 (13) | C4—C5 | 1.385 (3) |
| N1—C8 | 1.247 (2) | C4—H4 | 0.9300 |
| N1—C10 | 1.472 (2) | C5—C6 | 1.391 (3) |
| N2—O2i | 1.2149 (13) | C5—H5 | 0.9300 |
| N2—C7 | 1.478 (2) | C6—C7 | 1.391 (3) |
| C1—C2 | 1.501 (3) | C6—C8 | 1.478 (3) |
| C1—H1A | 0.9600 | C9—C10 | 1.504 (3) |
| C1—H1B | 0.9600 | C9—H9 | 0.9700 |
| C1—H1C | 0.9600 | C9—H9i | 0.9700 |
| C2—C7 | 1.391 (2) | C10—H10 | 0.9700 |
| C2—C3 | 1.391 (3) | C10—H10i | 0.9700 |
| | | |
| C8—O1—C9 | 106.31 (16) | C6—C5—H5 | 119.8 |
| C8—N1—C10 | 107.34 (17) | C7—C6—C5 | 117.07 (18) |
| O2i—N2—O2 | 124.43 (16) | C7—C6—C8 | 122.89 (17) |
| O2i—N2—C7 | 117.75 (8) | C5—C6—C8 | 120.04 (18) |
| O2—N2—C7 | 117.75 (8) | C2—C7—C6 | 123.93 (17) |
| C2—C1—H1A | 109.5 | C2—C7—N2 | 115.90 (16) |
| C2—C1—H1B | 109.5 | C6—C7—N2 | 120.18 (15) |
| H1A—C1—H1B | 109.5 | N1—C8—O1 | 118.10 (17) |
| C2—C1—H1C | 109.5 | N1—C8—C6 | 126.55 (17) |
| H1A—C1—H1C | 109.5 | O1—C8—C6 | 115.35 (16) |
| H1B—C1—H1C | 109.5 | O1—C9—C10 | 103.87 (16) |
| C7—C2—C3 | 116.38 (18) | O1—C9—H9 | 111.0 |
| C7—C2—C1 | 122.16 (17) | C10—C9—H9i | 111.0 |
| C3—C2—C1 | 121.46 (17) | O1—C9—H9i | 111.0 |
| C4—C3—C2 | 121.60 (18) | C10—C9—H9i | 111.0 |
| C4—C3—H3 | 119.2 | H9—C9—H9i | 109.0 |
| C2—C3—H3 | 119.2 | N1—C10—C9 | 104.38 (16) |
| C3—C4—C5 | 120.52 (19) | N1—C10—H10 | 110.9 |
| C3—C4—H4 | 119.7 | C9—C10—H10 | 110.9 |
| C5—C4—H4 | 119.7 | N1—C10—H10i | 110.9 |
| C4—C5—C6 | 120.5 (2) | C9—C10—H10i | 110.9 |
| C4—C5—H5 | 119.8 | H10—C10—H10i | 108.9 |
| | | |
| C7—C2—C3—C4 | 0.0 | O2—N2—C7—C2 | −88.46 (13) |
| C1—C2—C3—C4 | 180.0 | O2i—N2—C7—C6 | −91.54 (13) |
| C2—C3—C4—C5 | 0.0 | O2—N2—C7—C6 | 91.54 (13) |
| C3—C4—C5—C6 | 0.0 | C10—N1—C8—O1 | 0.0 |
| C4—C5—C6—C7 | 0.0 | C10—N1—C8—C6 | 180.0 |
| C4—C5—C6—C8 | 180.0 | C9—O1—C8—N1 | 0.0 |
| C3—C2—C7—C6 | 0.0 | C9—O1—C8—C6 | 180.0 |
| C1—C2—C7—C6 | 180.0 | C7—C6—C8—N1 | 0.0 |
| C3—C2—C7—N2 | 180.0 | C5—C6—C8—N1 | 180.0 |
| C1—C2—C7—N2 | 0.0 | C7—C6—C8—O1 | 180.0 |
| C5—C6—C7—C2 | 0.0 | C5—C6—C8—O1 | 0.0 |
| C8—C6—C7—C2 | 180.0 | C8—O1—C9—C10 | 0.0 |
| C5—C6—C7—N2 | 180.0 | C8—N1—C10—C9 | 0.0 |
| C8—C6—C7—N2 | 0.0 | O1—C9—C10—N1 | 0.0 |
| O2i—N2—C7—C2 | 88.46 (13) | | |
| Symmetry codes: (i) x, −y+1/2, z. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C4—H4···N1ii | 0.93 | 2.60 | 3.508 (3) | 167 |
| Symmetry codes: (ii) x−1, y, z. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C4—H4···N1i | 0.93 | 2.60 | 3.508 (3) | 167 |
| Symmetry codes: (i) x−1, y, z. |
Bruker (2005). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Lahm, G. P., Selby, T. P., Freudenberger, J. H., Stevenson, T. M., Myers, B. J., Seburyamo, G., Smith, B. K., Flexner, L., Clark, C. E. & Cordova, D. (2005). Bioorg. Med. Chem. Lett. 15, 4898–4906.
Lahm, G. P., Selby, T. P. & Stevenson, T. M. (2003). International Patent WO 03/015 519.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
![[Figure 1]](./hb2868fig1thm.gif)
Anthranilamide compounds as a new class of inseticides are characterized by their high levels of insecticidal activity, no-cross resistance to existing insecticides, safety to off-target animal and low toxicity to mammals (Lahm et al. 2003, 2005)
The title compound (I) as an intermediate for preparing Chlorantraniliprole analogs plays an important role in identifying the configuration of two possible products.
In the molecular structure of (I), (Fig. 1) all the non-hydrogen atoms except the nitro-group O atom lie on a crystallographic mirror plane. In the crystal, C—H···N links lead to chains of molecules propagating in [100].