A new and simple route for the synthesis of α,β-unsaturated ketones via cleavage of the C-C(O)C single bond of monoalkylated β-diketone has been described. The reaction was catalyzed by copper, a cheap transition m...A new and simple route for the synthesis of α,β-unsaturated ketones via cleavage of the C-C(O)C single bond of monoalkylated β-diketone has been described. The reaction was catalyzed by copper, a cheap transition metal in a weakly basic medium (K<sub>3</sub>PO<sub>4</sub>) at room temperature. To carry out this study, we first had to synthesize the monoalkylated β-diketones 1. Afterwards, α,β-unsaturated ketones 2 were obtained with high yields around 80%. Finally, all the products were characterized by 1H NMR, 13C NMR, and HRMS spectra. .展开更多
The title compound (C17H16O2, Mr = 252.30) crystallizes in the monoclinic system, space group P21/c with a = 11.5763(14), b = 11.0321(11), c = 11.5094(13) ?, β = 114.581(3)o, V = 1336.7(3) ?3 , Z = 4, Dc = 1.254 g/...The title compound (C17H16O2, Mr = 252.30) crystallizes in the monoclinic system, space group P21/c with a = 11.5763(14), b = 11.0321(11), c = 11.5094(13) ?, β = 114.581(3)o, V = 1336.7(3) ?3 , Z = 4, Dc = 1.254 g/cm3, μ(MoKa) = 0.081 cm-1 and F(000) = 536.00. The final R and wR are 0.0527 and 0.1285, respectively for 3058 observed reflections (I > 2σ(I)). In the title molecule, two phenyl rings are rotated oppositely with respect to the central part C(1)–C(2)=C(3)– C(4) (plane 3) and the dihedral angle between them is 14.8o. The phenone O(1) atom deviates from plane 3 by 0.291 ?. In the crystal the molecules form H-bond chains of R2 (6) and R2 (5) types 1 1 along [001]. The molecule chains interacted through three cooperative C–H…O H-bonds (R3 (11)) 1 in the ‘bay area’ (Fig. 3), extending along [010] and forming layer (100). Between the layers, there exist C–H/π interactions along [101]. Studies on the cooperative C–H…O H-bonds R3 (11) in the 1 similar crystals are also presented.展开更多
采用量子化学计算和分子动力学(MD)模拟,研究了溶剂化物环四亚甲基四硝胺(HMX)/N,N-二甲基甲酰胺(DMF)的结构和分子间相互作用。对浸渍在DMF溶剂中的β-HMX分子的MD模拟表明,HMX的分子构象已经从β转变为α相。在M P2/6-31G*水平上的理...采用量子化学计算和分子动力学(MD)模拟,研究了溶剂化物环四亚甲基四硝胺(HMX)/N,N-二甲基甲酰胺(DMF)的结构和分子间相互作用。对浸渍在DMF溶剂中的β-HMX分子的MD模拟表明,HMX的分子构象已经从β转变为α相。在M P2/6-31G*水平上的理论计算也说明,在D M F溶剂中,α-HM X比β-HM X更稳定。这解释了在HM X/D M F溶剂化物的多晶型中,所有的HMX分子均呈α构象的原因。采用MP2/6-31G*方法,对α-HMX和DMF分子间可能的同型和异型二聚体进行结构优化。结果表明,组分间存在C—H…O氢键相互作用,并且α-HMX/DMF的稳定化能非常接近α-HMX/α-HMX,并远远大于D M F二聚体的。这意味着异型分子间力可和同型分子间力竞争。从热力学的观点来看,共结晶过程可能发生。对α-HM X在D M F中的过饱和溶液的M D模拟表明,分子间相互作用对共结晶有利。这些理论研究对理解在HM X的D M F溶液中为什么发生的是共结晶而不是重结晶提供了有价值的信息。展开更多
文摘A new and simple route for the synthesis of α,β-unsaturated ketones via cleavage of the C-C(O)C single bond of monoalkylated β-diketone has been described. The reaction was catalyzed by copper, a cheap transition metal in a weakly basic medium (K<sub>3</sub>PO<sub>4</sub>) at room temperature. To carry out this study, we first had to synthesize the monoalkylated β-diketones 1. Afterwards, α,β-unsaturated ketones 2 were obtained with high yields around 80%. Finally, all the products were characterized by 1H NMR, 13C NMR, and HRMS spectra. .
基金This research was supported by the Key Subject Foundation of Jiangsu Province(S1109001)
文摘The title compound (C17H16O2, Mr = 252.30) crystallizes in the monoclinic system, space group P21/c with a = 11.5763(14), b = 11.0321(11), c = 11.5094(13) ?, β = 114.581(3)o, V = 1336.7(3) ?3 , Z = 4, Dc = 1.254 g/cm3, μ(MoKa) = 0.081 cm-1 and F(000) = 536.00. The final R and wR are 0.0527 and 0.1285, respectively for 3058 observed reflections (I > 2σ(I)). In the title molecule, two phenyl rings are rotated oppositely with respect to the central part C(1)–C(2)=C(3)– C(4) (plane 3) and the dihedral angle between them is 14.8o. The phenone O(1) atom deviates from plane 3 by 0.291 ?. In the crystal the molecules form H-bond chains of R2 (6) and R2 (5) types 1 1 along [001]. The molecule chains interacted through three cooperative C–H…O H-bonds (R3 (11)) 1 in the ‘bay area’ (Fig. 3), extending along [010] and forming layer (100). Between the layers, there exist C–H/π interactions along [101]. Studies on the cooperative C–H…O H-bonds R3 (11) in the 1 similar crystals are also presented.
基金National Natural Science Foundation of C hina(NSAF,No.11176029)the Key Research Project of Education Department of SichuanProvince(No.10zd1106)
文摘采用量子化学计算和分子动力学(MD)模拟,研究了溶剂化物环四亚甲基四硝胺(HMX)/N,N-二甲基甲酰胺(DMF)的结构和分子间相互作用。对浸渍在DMF溶剂中的β-HMX分子的MD模拟表明,HMX的分子构象已经从β转变为α相。在M P2/6-31G*水平上的理论计算也说明,在D M F溶剂中,α-HM X比β-HM X更稳定。这解释了在HM X/D M F溶剂化物的多晶型中,所有的HMX分子均呈α构象的原因。采用MP2/6-31G*方法,对α-HMX和DMF分子间可能的同型和异型二聚体进行结构优化。结果表明,组分间存在C—H…O氢键相互作用,并且α-HMX/DMF的稳定化能非常接近α-HMX/α-HMX,并远远大于D M F二聚体的。这意味着异型分子间力可和同型分子间力竞争。从热力学的观点来看,共结晶过程可能发生。对α-HM X在D M F中的过饱和溶液的M D模拟表明,分子间相互作用对共结晶有利。这些理论研究对理解在HM X的D M F溶液中为什么发生的是共结晶而不是重结晶提供了有价值的信息。
