65039-08-9 1-乙基-3-甲基溴化咪唑

运输方式：冰袋运输。危险性质：非危险化学品。海关编码：29332900，存储类别：11 - 可燃固体，WGK Germany：3。危险性类别：眼部刺激 类别2，经皮刺激 类别2。危险性描述：H315（造成皮肤刺激）、H319（造成严重眼刺激）、H335（可能引起呼吸道刺激）。危险标志：GHS07，信号词：Warning。危险性防范说明：P261（避免吸入粉尘/烟雾）、P305 + P351 + P338（如进入眼睛，立即用大量水冲洗并就医）。

化学合成。

化学合成

合成路线 1（1. 合成：65039-08-9）

产率：98% 合成条件：at 40℃; for 24 h; Schlenk technique; Inert atmosphere 实验步骤：配体（3除外）均通过改进Starikova等人的方法合成。将N-单取代的唑（0.1mmol）和无水甲苯置于双颈烧瓶中并搅拌直至形成均匀的溶液；然后在连续搅拌下滴加烷基卤（0.3mmol）。加入烷基卤化物后，搅拌混合物，同时在40℃加热24小时。除去溶剂，将配体真空干燥。 产物表征：1-甲基-3-乙基咪唑溴化物（2）白色固体，产量（4.70g，98％）。IR（ATR cm -1）：3065,2975,1670,1571,1467,1172,1101,856,789,649,789,621,417；δH（400MHz，CDCl3）：1.47（3H，t，J 7.3Hz，CH3），3.97（3H，s，NCH3），4.32（2H，q，NCH2），7.54（2H，s，NCH）和10.07ppm（1H，s，CH）；δC（100MHz，CDCl3）：15.64（CH3），36.63（NCH3），45.18（NCH2），122.01（NCH），123.71（NCH）和136.73ppm；m/z（ESI）111.5（M + -Br-）；HRMS（ESI）计算值C6H11BrN2,111.09222（M + -Br-）；发现，111.09196（M + -Br-）。 参考文献：[1] Angewandte Chemie - International Edition, 2012, vol. 51, # 46, p. 11483 - 11486 [2] Angew. Chem., 2012, vol. 124, # 46, p. 11650 - 11654,5 [3] Organic and Biomolecular Chemistry, 2013, vol. 11, # 15, p. 2534 - 2542 [4] Journal of Chemical and Engineering Data, 2004, vol. 49, # 4, p. 760 - 764 [5] Patent: WO2006/63656, 2006, A1. Location in patent: Page/Page column 32 [6] Patent: WO2006/63654, 2006, A1. Location in patent: Page/Page column 25-26 [7] Organic and Biomolecular Chemistry, 2013, vol. 11, # 15, p. 2534 - 2542 [8] Journal of Chemical and Engineering Data, 2004, vol. 49, # 4, p. 760 - 764 [9] Patent: WO2006/63656, 2006, A1. Location in patent: Page/Page column 32 [10] Patent: WO2006/63654, 2006, A1. Location in patent: Page/Page column 25-26 [11] Organic and Biomolecular Chemistry, 2013, vol. 11, # 15, p. 2534 - 2542 [12] Journal of Chemical and Engineering Data, 2004, vol. 49, # 4, p. 760 - 764 [13] Patent: WO2006/63656, 2006, A1. Location in patent: Page/Page column 32 [14] Patent: WO2006/63654, 2006, A1. Location in patent: Page/Page column 25-26 [15] Organic and Biomolecular Chemistry, 2013, vol. 11, # 15, p. 2534 - 2542 [16] Journal of Chemical and Engineering Data, 2004, vol. 49, # 4, p. 760 - 764 [17] Patent: WO2006/63656, 2006, A1. 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合成路线 2（2. 合成：65039-08-9）

产率：86% 合成条件：at 20℃; for 2 h; Inert atmosphere 实验步骤：实施例3和4：亚甲基二乙酸酯50mL Schlenk烧瓶配备磁力搅拌棒，在室温下加入EMIM-乙酸酯（20.0g，117.0mmol）和0.5当量二氯甲烷（5.0g，58.7mmol）并进行反应 反应后，在80℃，减压下（85.0％）从反应混合物中蒸馏出纯产物。当二溴甲烷用作底物时，反应在室温下反应快，并且高度放热 。反应通过均相路径进行，纯化产物在80℃减压下从反应混合物中蒸馏出来（产率86.0％）。乙二醇二甲酯：1H NMR（CD3CN，400.13MHz）：δ= 2.04（s，6H， CH3），5.64（s，2H，CH2）; 13 C NMR：δ= 20.9（CH 3），79.7（CH 2），170.8（CO）; FTIR（ATR模式）：v = 2996（br），1758（s），1190（s），1009（s），978（s） 参考文献：

• [1] Patent: EP2532646, 2012, A1. Location in patent: Page/Page column 5-7

合成路线 3（3. 合成：65039-08-9）

产率：90% 合成条件：at 20℃; for 3 h; Inert atmosphere 实验步骤：实施例1和2：乙二醇二乙酸酯;在100mL Schlenk烧瓶上装配磁力搅拌棒，在室温下加入EMIM-乙酸酯（50.0g，0.293mol）和0.5当量的1,2-二氯乙烷（14.5g，0.146mol）并在70°C，3小时。反应后，得到两相，倾析上层，反应混合物用乙醚萃取3次，合并所有馏分，真空除去乙醚。得到最终的纯产物，为无色液体（90.0％收率）。当使用1,2-二溴乙烷作为底物时，即使在室温下反应也非常快并且是高度放热的。反应通过均相途径进行;在100℃减压下从反应混合物中蒸馏出纯产物（90.0％收率）。乙二醇二乙酸酯：1 H NMR（CDCl 3,400.13MHz）：δ= 2.02（s，6H，CH 3），4.2（s，4H，CH 2）; 13 C NMR：δ= 20.9（CH 3），62.3（CH 2），170.9（CO）; FTIR（ATR模式）：v = 2961（br），1735（s），1371（m），1213（s），1048（m）。 参考文献：

• [1] Patent: EP2532646, 2012, A1. Location in patent: Page/Page column 5-7