A new compound, 2-dichloromethyl-2-
The 2-dichloromethyl-1,3-dioxacycloalkane compounds have received considerable attention due to safening activities against herbicidal injuries to crop plants [
Several synthetic procedures to obtain 1,3-dioxacycloalkanes have been reported [
All chemicals and solvents were of reagent grade and were used as purchased without further purification. The melting point was determined on a Beijing Taike melting point apparatus (X-4) and was uncorrected. The 1H NMR and 13C NMR spectra were run on a Bruker AVANCE 400 MHz spectrometer with CDCl3 as the solvent and TMS as the internal standard. The mass spectrum was recorded on a Waters Xevo TQ mass spectrometer. The infrared (IR) spectra were recorded in KBr disks on a Bruker ALPHA-T. The X-ray data were collected on a Rigaku RAXIS-RAPID rapid X-ray diffraction measurement using graphite monochromated Mo
The title compound was synthesized according to the route shown in Scheme
Synthesis of the title compound
A mixture of
To a vigorously stirred solution of acetal (
The cube-shaped single crystal of the title compound was grown by slow cooling from a hot saturated solution in ethanol. The crystal with dimensions of 0.27 × 0.10 × 0.07 mm was mounted on a Bruker AXSII CCD area-detector diffractometer with a graphite-monochromated Mo
Crystal and structure refinement for title compound.
Item | Value |
---|---|
CCDC | 928570 |
Empirical formula |
C11H11Cl2NO4 |
Formula weigh | 292.11 |
Temperature | 293(2) K |
Radiation |
0.71073 Å |
Crystal system, space group | Monoclinic, |
Unit cell dimensions |
|
Volume | 1260.3(4) Å3 |
|
4 |
Calculated density | 1.540 mg/m3 |
Absorption coefficient | 0.520 mm−1 |
|
600 |
Item | Value |
Crystal size | 0.27 |
Theta range for data collection | 3.32 to 27.47 deg. |
Range/indices ( |
−14, 14; −19, 19; −10, 9 |
Reflections collected/unique | 12162/2867 ( |
Completeness to theta = 27.47 | 99.1% |
Absorption correction |
0.9645 and 0.8736 |
Data/restraints/parameters | 2867/0/163 |
Goodness-of-fit on |
1.032 |
|
0.0508, 0.1072 |
|
0.1016, 0.1352 |
Largest diff. peak and hole (eÅ−3) | 0.268 and −0.232 |
Molecular diagram of compound
The packing view of compound
The synthesis of the compound
The selected bond lengths and bond angles are shown in Table
Selected bond lengths (Å) and angles (°) for the title compound.
Bond Length (Å) | Bond Angle (°) | ||
---|---|---|---|
C(1)–C(6) | 1.379(4) | C(6)–C(1)–C(2) | 120.20(3) |
C(1)–C(2) | 1.382(4) | C(6)–C(1)–C(7) | 119.80(2) |
C(1)–C(7) | 1.543(4) | C(2)–C(1)–C(7) | 119.90(3) |
C(2)–C(3) | 1.391(4) | C(1)–C(2)–C(3) | 120.50(3) |
C(3)–C(4) | 1.369(4) | C(4)–C(3)–C(2) | 117.90(3) |
C(4)–C(5) | 1.372(4) | C(3)–C(4)–C(5) | 123.30(3) |
C(4)–N(1) | 1.489(4) | C(3)–C(4)–N(1) | 118.20(3) |
C(5)–C(6) | 1.396(4) | C(5)–C(4)–N(1) | 118.50(3) |
C(7)–O(1) | 1.409(3) | C(4)–C(5)–C(6) | 118.00(3) |
C(7)–O(2) | 1.411(3) | C(1)–C(6)–C(5) | 120.10(3) |
C(7)–C(11) | 1.541(4) | O(1)–C(7)–O(2) | 111.50(2) |
C(8)–O(1) | 1.454(3) | O(1)–C(7)–C(11) | 103.60(2) |
C(8)–C(9) | 1.511(5) | O(2)–C(7)–C(11) | 103.10(2) |
C(9)–C(10) | 1.498(5) | O(1)–C(7)–C(1) | 111.90(2) |
C(10)–O(2) | 1.450(4) | O(2)–C(7)–C(1) | 112.20(2) |
C(11)–Cl(2) | 1.764(3) | C(11)–C(7)–C(1) | 113.90(2) |
C(11)–Cl(1) | 1.772(3) | O(1)–C(8)–C(9) | 109.60(3) |
N(1)–O(3) | 1.204(4) | C(10)–C(9)–C(8) | 109.50(3) |
N(1)–O(4) | 1.207(4) | O(2)–C(10)–C(9) | 111.10(3) |
C(7)–C(11)–Cl(2) | 112.10(2) | ||
C(7)–C(11)–Cl(1) | 111.30(2) | ||
Cl(2)–C(11)–Cl(1) | 109.30(16) | ||
O(3)–N(1)–O(4) | 123.80(3) | ||
O(4)–N(1)–C(4) | 117.90(3) | ||
C(7)–O(1)–C(8) | 113.40(2) | ||
C(7)–O(2)–C(10) | 113.70(2) |
Atomic coordinates (
|
|
|
| |
---|---|---|---|---|
C(1) | 7449(3) | 5587(2) | 2026(3) | 39(1) |
C(2) | 7093(3) | 5514(2) | 286(4) | 43(1) |
C(3) | 7860(3) | 5811(2) | −879(4) | 45(1) |
C(4) | 8963(3) | 6185(2) | −242(4) | 46(1) |
C(5) | 9336(3) | 6287(3) | 1476(4) | 56(1) |
C(6) | 8561(3) | 5974(3) | 2626(4) | 53(1) |
C(7) | 6584(3) | 5263(2) | 3305(3) | 41(1) |
C(8) | 6429(3) | 3703(2) | 2402(4) | 52(1) |
C(9) | 7107(3) | 3407(3) | 4099(5) | 62(1) |
C(10) | 7912(3) | 4169(3) | 4840(5) | 65(1) |
C(11) | 5699(3) | 6005(2) | 3794(4) | 44(1) |
Cl(1) | 4673(1) | 6351(1) | 1997(1) | 56(1) |
Cl(2) | 6481(1) | 6970(1) | 4717(1) | 69(1) |
N(1) | 9794(3) | 6497(2) | −1481(4) | 62(1) |
O(1) | 5800(2) | 4560(1) | 2618(2) | 43(1) |
O(2) | 7226(2) | 5011(2) | 4898(2) | 50(1) |
O(3) | 9484(3) | 6373(3) | −2984(3) | 93(1) |
O(4) | 10734(3) | 6871(3) | −917(4) | 98(1) |
According to X-ray analysis, the structure, the title compound, C11H11Cl2NO4, contained a 1,3-dioxane and a benzene ring. The phenyl ring is almost vertical with the 1,3-dioxane ring, with the dihedral angles of 100.4°. The torsion angle of C(7)–O(1)–C(8)–C(9) was 56.6(3)°. The torsion angle of C(7)–O(2)–C(10)–C(9) was −54.0°, which made the 1,3-dioxane similar to chair conformation.
Generally, the average bond lengths and bond angles of ring system (phenyl and 1,3-dioxane) are normal. The bond lengths of C–N and C–O were close to the typical bond length. In the plane benzene ring, the C–C bond lengths range from 1.369(4) Å to 1.396(4) Å, almost equal to the values of typical bonds of aromatic structure. And the bond angles of the benzene ring change from 117.9(3)° to 123.3(3)°, also with the average of 120°. The bond angles of 1,3-dioxane are between 109.50(3) and 113.70(2), close to 109.5, which also confirm the chair conformation of 1,3-dioxane.
This work was supported by the National Nature Science Foundation of China (no. 31101473), the Natural Science Foundation of Heilongjiang Province (B201212), the Science and Technology Research Project of Heilongjiang Education Department (no. 12521002), and the Research Science Foundation in Technology Innovation of Harbin (2012RFXXN002).