A new compound,
Heterocyclic compounds are used, for instance, as antifungal, herbicide, and growth accelerator for plants; the biological properties of heterocycles generally make them play a vital role in human life [
Due to the importance of 1,4-benzoxazine and its derivatives, several synthetic methods have been reported over the past few decades. Most of the reported methods were about the synthesis of specific benzoxazines by
All reagents were of analytical grade. The infrared (IR) spectra were recorded in KBr on a KJ-IN-27G infrared spectrophotometer. Melting points were determined on Beijing Taike melting point apparatus (X-4) and uncorrected. The 1H-NMR and 13C-NMR spectra were recorded on Bruker AVANCE 300 MHz, with CDCl3 as the solvent and TMS as the internal standard. MS was recorded on a Waters Xevo TQ mass spectrometer. Elemental analysis was taken on a FLASH EA1112 Elemental Analysis Instrument. The X-ray data were collected on a Bruker AXS II CCD area-detector diffractometer using graphite-monochromated Mo
The
Procedure of preparing the title compound.
The solution of compound
Dichloroacetyl chloride (17.6 nmol) was added slowly in the mixture containing compound
The crystal with dimensions of 0.33 mm × 0.30 mm × 0.22 mm was mounted on a Bruker AXS II CCD area-detector diffractometer equipped with a graphite-monochromator Mo
The structure was solved by direct methods using the
Crystal and structure refinement for the title compound.
Empirical formula | C11H10Cl3NO2 |
Formula weight | 294.55 |
Temperature (K) | 293(2) |
Crystal system | Monoclinic |
Space group |
|
Radiation |
0.71073 |
|
6.7619(14) |
|
24.866(5) |
|
9.737(3) |
|
90 |
|
130.982(18) |
|
90 |
|
1235.9(5) |
|
4 |
|
600 |
Density (calc.) (mg/m3) | 1.583 |
Crystal size (mm3) | 0.33 × 0.30 × 0.22 |
Absorption coefficient (mm−1) | 0.729 |
Theta range for data collection (°) | 3.13–27.45 |
Range/indices ( |
−8, 8; −32, 32; −12, 11 |
Reflections collected/unique | 11955/2840 ( |
Completeness to theta = 27.47 | 99.9% |
Absorption correction |
0.8585 and 0.7971 |
Data/restraints/parameters | 2840/0/155 |
Goodness-of-fit on |
1.106 |
|
0.0476, 0.1274 |
|
0.0613, 0.1330 |
|
0.953 |
|
−0.653 |
The synthesis of compound
Low temperature should be employed because of
In the infrared spectrum, a characteristic carbonyl band at around 1675 cm−1 was assigned to the presence of C=O. However, for the steric hindrance effect of 3-methyl, the
The structure of title compound is confirmed by X-ray crystallographic analysis. Selected bond lengths and angles are given in Table
Selected bond lengths (
Bond | Length ( |
Bond | Angles (°) | Bond | Angles (°) |
---|---|---|---|---|---|
Cl(1)-C(3) | 1.744(2) | C(6)-O(1)-C(7) | 115.78(16) | C(1)-C(6)-C(5) | 120.1(2) |
Cl(2)-C(11) | 1.756(2) | C(10)-N(1)-C(5) | 122.18(16) | O(1)-C(7)-C(8) | 111.18(18) |
Cl(3)-C(11) | 1.772(2) | C(10)-N(1)-C(8) | 124.35(16) | N(1)-C(8)-C(7) | 106.88(17) |
O(1)-C(6) | 1.368(3) | C(5)-N(1)-C(8) | 113.47(15) | N(1)-C(8)-C(9) | 111.50(18) |
O(1)-C(7) | 1.426(3) | C(2)-C(1)-C(6) | 121.2(2) | C(7)-C(8)-C(9) | 112.55(19) |
O(2)-C(10) | 1.212(3) | C(1)-C(2)-C(3) | 118.56(19) | O(2)-C(10)-N(1) | 124.12(18) |
N(1)-C(10) | 1.360(3) | C(2)-C(3)-C(4) | 122.0(2) | O(2)-C(10)-C(11) | 119.47(18) |
N(1)-C(5) | 1.431(2) | C(2)-C(3)-Cl(1) | 119.24(16) | N(1)-C(10)-C(11) | 116.40(17) |
N(1)-C(8) | 1.487(2) | C(4)-C(3)-Cl(1) | 118.80(17) | C(10)-C(11)-Cl(2) | 110.62(14) |
C(1)-C(6) | 1.389(3) | C(3)-C(4)-C(5) | 119.48(19) | C(10)-C(11)-Cl(3) | 108.41(15) |
C(1)-C(2) | 1.371(3) | C(4)-C(5)-C(6) | 118.64(18) | Cl(2)-C(11)-Cl(3) | 110.45(13) |
C(5)-C(6) | 1.404(3) | C(4)-C(5)-N(1) | 122.76(18) | ||
C(7)-C(8) | 1.514(3) | C(6)-C(5)-N(1) | 118.51(17) | ||
C(8)-C(9) | 1.522(3) | O(1)-C(6)-C(1) | 116.20(18) | ||
C(10)-C(11) | 1.546(3) | O(1)-C(6)-C(5) | 123.64(18) |
Atomic coordinates (×104) and equivalent isotropic displacement parameter (×103) for nonhydrogen atoms.
Atom |
|
|
|
|
---|---|---|---|---|
Cl(1) | −645(1) | −526(1) | −3480(1) | 54(1) |
Cl(2) | 2826(2) | −3055(1) | 2329(1) | 64(1) |
Cl(3) | 5737(2) | −2142(1) | 4698(1) | 78(1) |
O(1) | −3560(4) | −841(1) | 958(2) | 47(1) |
O(2) | 898(4) | −2134(1) | 13(2) | 53(1) |
N(1) | 95(3) | −1573(1) | 1441(2) | 31(1) |
C(1) | −3748(5) | −352(1) | −1179(3) | 40(1) |
C(2) | −3095(4) | −263(1) | −2227(3) | 38(1) |
C(3) | −1416(4) | −620(1) | −2102(3) | 35(1) |
C(4) | −352(4) | −1056(1) | −932(3) | 33(1) |
C(5) | −1032(4) | −1149(1) | 128(2) | 30(1) |
C(6) | −2780(4) | −793(1) | −26(3) | 35(1) |
C(7) | −2769(5) | −1322(1) | 2000(3) | 42(1) |
C(8) | 28(5) | −1468(1) | 2915(3) | 36(1) |
C(9) | 1973(5) | −1033(1) | 4209(3) | 48(1) |
C(10) | 1082(4) | −2026(1) | 1307(3) | 34(1) |
C(11) | 2579(4) | −2413(1) | 2954(3) | 37(1) |
Molecular structure for title compound at 30% probability level.
Packing view of the title compound.
According to the data from X-ray analysis of the structure, the bond lengths of C8-N1 and C7-O1 conformed to the value for normal single bond. The C10-O2 (1.212 Å) was similar for C=O double bond (1.19–1.23 Å) found in 1,4-benzoxazine ring. The title compound crystallized in the monoclinic, P21/
Hydrogen-bond distance (
D-H⋯A | D-H | H⋯A | D-A | <(DHA) |
---|---|---|---|---|
C(11)-H(11)⋯O(2)1 | 0.9797 | 2.2077 | 3.0940 | 149.82 |
C(8)-H(8)⋯Cl(2)2 | 0.9796 | 2.8721 | 3.5766 | 129.56 |
Symmetry codes:
Good quality single crystals of
The authors declare that there is no conflict of interests regarding the publication of this paper.
This work was supported by the National Nature Science Foundation of China (no. 31101473), the project funded by China Postdoctoral Science Foundation (2014M551208), and the Science and Technology Research Project of Heilongjiang Education Department (12531027).