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(4S,5S)-4,5-双(胺甲酰基)-2-(2-溴苯基)-1,3-二氧戊环是合成铂类抗癌药的关键中间体。以邻溴苯甲醛为原料,与D-酒石酸二乙酯进行缩合反应,再经胺解得到标题化合物。通过探讨反应物摩尔比、催化剂用量、反应时间对反应结果的影响,得到最佳反应条件:n(D-酒石酸二乙酯)∶n(邻溴苯甲醛)=1.3∶1,催化剂用量为反应物总质量的4.5%,10 mL环己烷,回流反应6 h;常温导入氨气反应4 h,粗产物Ⅰ经乙醇重结晶,收率67.1%,熔点113~114℃。以无水乙醇为溶剂,经溶剂挥发得到目标产物单晶,并通过熔点、元素分析、MS、1HNMR和X射线单晶衍射仪确定了产物结构。对产物进行了谱学表征和晶体结构分析。该晶体属于单斜晶系,P21空间群,晶胞参数:a=94.150(19)nm,b=144.58(3)nm,c=96.170(19)nm,α=90.00°,β=111.14(3)°,γ=90.00°,V=1.2210(5)nm3,Dx=1.714 g/cm3,Z=4,F(000)=632,μ=3.38 mm-1,S=1.00,R=0.063,wR=0.181。
(4S, 5S) -4,5-bis (carbamoyl) -2- (2-bromophenyl) -1,3-dioxolane is a key intermediate in the synthesis of platinum anticancer drugs. O-bromobenzaldehyde as raw material, and D-diethyl tartrate condensation reaction, and then aminated to give the title compound. The optimal reaction conditions were obtained by discussing the effects of molar ratio of reactants, amount of catalyst and reaction time on the reaction results. The optimal reaction conditions were as follows: n (D-diethyl tartarate): n (o-bromobenzaldehyde) = 1.3:1 4.5% of total mass and 10 mL of cyclohexane were refluxed for 6 h. Ammonia was introduced into the reaction at room temperature for 4 h. The crude product I was recrystallized from ethanol with a yield of 67.1% and a melting point of 113-114 ° C. The target product single crystal was obtained by evaporation of solvent in anhydrous ethanol. The product structure was confirmed by melting point, elemental analysis, MS, 1HNMR and X-ray single crystal diffractometer. The products were characterized by spectroscopy and crystal structure analysis. The crystal belongs to monoclinic space group P21 with unit cell parameters of a = 94.150 (19) nm, b = 144.58 nm, c = 96.170 nm, α = 90.00 °, β = ) = Γ = 90.00 ° V = 1.2210 (5) nm3 Dx = 1.714 g / cm3 Z = 4 F (000) = 632 μ = 3.38 mm-1 S = 1.00 R = = 0.181.