以六硝基联卞(HNBB)为原料,4-羟基-2,2,6,6-四甲基哌啶-N-氧自由基(4-OH-TEMPO)和氯化亚铁(FeCl2)为催化剂,在二甲亚砜(DMSO)中通过氧气氧化HNBB脱氢制备了六硝基茋(HNS),收率为81%。确定了最佳反应条件:溶剂为DMSO,催化剂组合及其比例...以六硝基联卞(HNBB)为原料,4-羟基-2,2,6,6-四甲基哌啶-N-氧自由基(4-OH-TEMPO)和氯化亚铁(FeCl2)为催化剂,在二甲亚砜(DMSO)中通过氧气氧化HNBB脱氢制备了六硝基茋(HNS),收率为81%。确定了最佳反应条件:溶剂为DMSO,催化剂组合及其比例为n(4-OH-TEMPO)∶n(FeCl2)=4∶6时,在55℃下以25 m L·h-1的速率通入氧气反应8 h。推测了可能的反应机理:亚铁离子结合氧气直接氧化底物HNBB脱氢得到HNS,4-OH-TEMPO在这个过程中起到一个促进FeCl2循环加速氧化脱氢的助催化作用。展开更多
Potential energy surface of HNS 2 is investigated by means of second order Moller Plesset perturbation theory (MP2) and QCISD(T) (single point) methods. At final QCISD (T)/6 311++G(3df,2p)//MP2/6 311++G(d,p...Potential energy surface of HNS 2 is investigated by means of second order Moller Plesset perturbation theory (MP2) and QCISD(T) (single point) methods. At final QCISD (T)/6 311++G(3df,2p)//MP2/6 311++G(d,p) level with zero point vibrational energies included, cis HNSS is found to be global minimum on the potential energy surface, followed by low lying trans HNSS, HN(S)S( C 2v ), cis HSNS, cis HSSN, trans HSNS, trans HSSN, and HN(S)S( C s ) by 13 46, 66 92, 78 25, 80 38, 81 22, 81 38 and 86 40 kJ/mol, respectively. A new high lying HS(N)S isomer with C s symmetry is located on the potential energy surface. The kinetic stabilities of all isomers are predicted. Comparisons are made for HNS 2 with its analogues, HNO 2, HPS 2 and HPO 2. The causes that lead to the differences between HNS 2 and its analogues are hypervalent capacity of phosphorus and distinct electronegativities of hydrogen, nitrogen and phosphorus.展开更多
文摘以六硝基联卞(HNBB)为原料,4-羟基-2,2,6,6-四甲基哌啶-N-氧自由基(4-OH-TEMPO)和氯化亚铁(FeCl2)为催化剂,在二甲亚砜(DMSO)中通过氧气氧化HNBB脱氢制备了六硝基茋(HNS),收率为81%。确定了最佳反应条件:溶剂为DMSO,催化剂组合及其比例为n(4-OH-TEMPO)∶n(FeCl2)=4∶6时,在55℃下以25 m L·h-1的速率通入氧气反应8 h。推测了可能的反应机理:亚铁离子结合氧气直接氧化底物HNBB脱氢得到HNS,4-OH-TEMPO在这个过程中起到一个促进FeCl2循环加速氧化脱氢的助催化作用。
文摘Potential energy surface of HNS 2 is investigated by means of second order Moller Plesset perturbation theory (MP2) and QCISD(T) (single point) methods. At final QCISD (T)/6 311++G(3df,2p)//MP2/6 311++G(d,p) level with zero point vibrational energies included, cis HNSS is found to be global minimum on the potential energy surface, followed by low lying trans HNSS, HN(S)S( C 2v ), cis HSNS, cis HSSN, trans HSNS, trans HSSN, and HN(S)S( C s ) by 13 46, 66 92, 78 25, 80 38, 81 22, 81 38 and 86 40 kJ/mol, respectively. A new high lying HS(N)S isomer with C s symmetry is located on the potential energy surface. The kinetic stabilities of all isomers are predicted. Comparisons are made for HNS 2 with its analogues, HNO 2, HPS 2 and HPO 2. The causes that lead to the differences between HNS 2 and its analogues are hypervalent capacity of phosphorus and distinct electronegativities of hydrogen, nitrogen and phosphorus.