，， ，，，

(1.浙江工業(yè)大學(xué) 化學(xué)工程與材料學(xué)院，浙江 杭州 310032；2.杭州中美華東制藥有限公司，浙江 杭州 310011)

1 實(shí)驗(yàn)部分

1.1 實(shí)驗(yàn)試劑與儀器

試劑：溶劑使用前經(jīng)除水并重蒸后于500 mL的單口瓶中密封保存，N-甲基芳胺類化合物(Ⅰ)由相應(yīng)的取代苯胺制備得到[16]，α-重氮-β-酮酸對(duì)硝基芐酯類化合物(Ⅱ)由相應(yīng)的β-酮酸對(duì)硝基芐酯和對(duì)甲苯磺酰疊氮制備得到[17].所用催化劑、試劑和溶劑均為國內(nèi)商業(yè)購得.柱層析填料為SiO2(粒度為200—300目).

儀器：Waters 1525高效液相色譜儀，Bruker DRX 500核磁共振儀，Agilent 6210 LC/TOF 液質(zhì)聯(lián)用儀，BUCHI M-565熔點(diǎn)測定儀等.

產(chǎn)物表征如下：

2 結(jié)果與討論

2.1 反應(yīng)條件的優(yōu)化

為了探究反應(yīng)的最佳條件，我們以N-甲基苯胺(Ⅰa)和α-重氮乙酰乙酸對(duì)硝基芐酯(Ⅱa)反應(yīng)制備α-(N-甲基-N-苯基)氨基乙酰乙酸對(duì)硝基芐酯(Ⅲaa)為模型，即

表1 N-甲基苯胺和α-重氮乙酰乙酸對(duì)硝基芐酯的插入反應(yīng)條件的優(yōu)化1)

2.2 底物拓展

表2 Cu(TFA)2催化N-甲基芳胺和α-重氮-β-酮酸對(duì)硝基芐酯的插入反應(yīng)1)

續(xù)表2

3 結(jié) 論

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