(4S,5S)-4,5-双(胺甲酰基)-2-(2-溴苯基)-1,3-二氧戊环的合成、谱学表征及其晶体结构

Synthesis,Spectrum Characterization and Crystal Structure of (4S,5S)-4,5-dicarboxamide-2-(2-bromophenyl)-1,3-dioxolane

（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）nm^3,Dx=1.714 g/cm^3,Z=4,F（000）=632,μ=3.38 mm^-1,S=1.00,R=0.063,wR=0.181。

（4S,5S）-4,5-dicarboxamide-2-（2-bromophenyl）-1,3-dioxolane is the key intermediate which can be synthesized for anticancer drugs.The title compound was synthesized from 2-bromobenzaldehyde and D-ethyl tartrate as starting materials,which can be prepared by the condensation reaction and ammonolyzed by ammonia.The effects of ratio of substances,amount of catalyst and reaction time on yield were discussed.The most favorite technological conditions of title compound（Ⅰ） were determined as follows：n（D-ethyl tartrate）∶n（2-bromobenzaldehyde）=1.3∶1,catalyst dosage=4.5% of mass of the reactants,cyclohexane 10 mL,reaction time 6 h;pumped ammonia 4 h at room temperature,recrystallized from ethanol to obtain final product,the yield was 67.1%,m.p.113～114 ℃.The single crystal was obtained by dissolving product in ethanol and evaporating at room temperature.The structure of the product was characterized by melting point,elementary analysis,MS,^1HNMR and X-ray single crystal diffraction.The crystal belongs to monoclinic system with space group P21 and crystallographic data of the compound are：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）nm^3,Dx=1.714 g/cm^3,Z=4,F（000）=632,μ=3.38 mm^-1,S=1.00,R=0.063,wR=0.181.