摘要
为了完善3,4-双(4'-硝基呋咱-3'-基)氧化呋咱(DNTF)的核磁表征,采用NMR实验与GIAO-NMR理论计算相结合的方法区分并归属13C和15N的化学位移。采用二甲基亚砜(DMSO-d6)、丙酮(Acetone-d6)和氯仿(CDCl3)为溶剂,进行了DNTF的一维13CNMR和15NNMR实验,并在DMSO-d6中获得DNTF的所有核磁信号。采用二维INADEQUATE实验完成了13CNMR的归属。采用高斯09程序,在DFT-B3LYP/6-311+G(2d,p)水平上优化了DNTF结构,用GIAO方法在不同基组上计算了13CNMR和15NNMR的化学位移,计算结果与实验值一致性较好。结果表明,受氧化呋咱环上氧原子O(22)吸电子作用的影响,C(9)与C(13)的化学位移出现较大的差别,与C(13)相比,C(9)出现在高场。
In order to optimize the NMR assignment of 3,4-dinitrofurazanfuroxan（DNTF）,a combination of experimental NMR and computational GIAO-NMR techniques was utilized to distinguish the chemical shifts of 13C and 15N. One dimensional（1D） 13 C and 15 N NMR analyses were performed using DMSO-d6 ,acetone-d6 and CDCl3 as solvent. All signals of DNTF were found in DMSO-d6 . In the 13 C NMR,the chemical shifts were assigned by 2D INADEQUATE NMR experiment. Based on the geometry of DNTF optimized at the DFT-B3LYP/6-311 ＋G（2d,p）level by using Guassian 09 program,the 13C and 15N NMR chemical shifts were calculated by GIAO method at different level,which agree with experimental data. Results show that the electro-withdrawing effect of the O（22）in furoxan cycle leads to large 13C chemical shift changes of C（9）and C（13）,and makes C（9）appear in higher field than C（13）.
出处
《含能材料》
EI
CAS
CSCD
北大核心
2013年第4期473-478,共6页
Chinese Journal of Energetic Materials
