2301-25-9 1-(4-硝基苯)-1H-咪唑

运输信息：常温运输。危险描述：非危险化学品（但GHS分类显示具有皮肤刺激（2级）、严重眼刺激（2级）、呼吸道刺激（单次暴露）的危险；WGK Germany:3；RTECS号:NI7962000；危险等级:IRRITANT；海关编码:2933299090）。防护措施：需遵循P261、P264等预防声明。

化学合成

化学合成

路线1：

• 步骤：向10mL圆底烧瓶中依次加入磁力搅拌子、咪唑（59mg，0.5mmol）、4-硝基苯基硼酸（1.0mmol）、硫化亚铜（4mg，0.025mmol）和甲醇（2mL），随后加入N,N,N′,N′-四甲基乙二胺（TMEDA，0.075mL，0.5mmol）。用橡胶隔膜密封烧瓶，通过隔膜插入18号针头确保反应体系与空气接触。将反应混合物以400-600rpm搅拌适当时间。反应完成后，用乙酸乙酯（2×15mL）萃取，合并有机相，用饱和乙二胺四乙酸二钠盐水溶液（15mL）洗涤，无水硫酸钠干燥，减压浓缩后经硅胶柱色谱（己烷-乙酸乙酯梯度）纯化，得到目标产物。
• 条件：20℃，48h；空气接触
• 收率：76%
• 参考文献：[1] ChemCatChem, 2016, vol. 8, #18, p.2953-2960；[2] Chemistry Letters, 2010, vol.39, #7, p.764-765；[3] Tetrahedron, 2018, vol.74, #5, p.606-617；[4] Bulletin of the Korean Chemical Society, 2017, vol.38, #10, p.1203-1208；[5] Synthetic Communications, 2015, vol.45, #2, p.245-252

路线2：

• 步骤：在25mL圆底烧瓶中，取苯酚/胺/苯硫酚（1.2mmol，0.112g）、4-硝基氯苯（1mmol，0.157g）、碱KOH（1.2mmol，0.08g）和催化剂（4.5mg，2.5mol%），加入DMSO（mL）。将反应混合物加热至110℃反应8h。反应完成后，离心分离催化剂，二氯甲烷洗涤，反应混合物用水稀释，二氯甲烷（3×10cm³）萃取，有机层无水硫酸钠干燥，减压蒸发，柱色谱（石油醚-乙酸乙酯）纯化。
• 条件：110℃，8h；空气氛围
• 收率：90%
• 参考文献：[1] Synthesis, 2008, #11, p.1707-1716；[2] Synthetic Communications, 2008, vol.38, #4, p.626-636；[3] Journal of Organic Chemistry, 2007, vol.72, #8, p.2737-2743；[4] Chinese Journal of Chemistry, 2012, vol.30, #10, p.2394-2400；[5] Journal of the American Chemical Society, 2007, vol.129, #45, p.13879-13886；[6] Tetrahedron, 2008, vol.64, #19, p.4254-4259；[7] RSC Advances, 2015, vol.5, #112, p.92121-92127；[8] Chemical Communications, 2004, #7, p.778-779；[9] Journal of Organic Chemistry, 2007, vol.72, #22, p.8535-8538；[10] Journal of Organic Chemistry, 2009, vol.74, #20, p.7951-7954；[11] Synthetic Communications, 2012, vol.42, #2, p.279-284；[12] Synthetic Communications, 2012, vol.42, #1, p.114-121；[13] Synlett, 2006, #14, p.2195-2198；[14] Tetrahedron, 2008, vol.64, #10, p.2471-2479；[15] Synlett, 2008, #19, p.3068-3072；[16] RSC Advances, 2016, vol.6, #93, p.90154-90164；[17] Journal of the American Chemical Society, 2005, vol.127, #28, p.9948-9949；[18] Synthesis, 2009, #15, p.2517-2522；[19] Tetrahedron Letters, 2011, vol.52, #41, p.5220-5223；[20] RSC Advances, 2014, vol.4, #14, p.7321-7329；[21] New Journal of Chemistry, 2016, vol.40, #2, p.1454-1459；[22] Journal of Organic Chemistry, 2011, vol.76, #9, p.3151-3159；[23] Polyhedron, 2012, vol.34, #1, p.143-148；[24] Chemistry Letters, 2016, vol.45, #2, p.223-225；[25] Advanced Synthesis and Catalysis, 2007, vol.349, #11-12, p.1938-1942；[26] Chinese Journal of Catalysis, 2014, vol.35, #11, p.1818-1824；[27] Tetrahedron, 2008, vol.64, #7, p.1383-1387；[28] Chinese Journal of Chemistry, 2012, vol.30, #10, p.2389-2393,5；[29] Research on Chemical Intermediates, 2016, vol.42, #10, p.7611-7624；[30] Synthesis, 2010, #9, p.1505-1511；[31] Journal of Organic Chemistry, 2006, vol.71, #21, p.8324-8327；[32] Patent: CN104447557, 2017, B. Location in patent: Paragraph 0141; 0142; 0143; 0144; 0145; 0146；[33] Monatshefte fur Chemie, 2004, vol.135, #4, p.419-423；[34] Green Chemistry, 2012, vol.14, #5, p.1268-1271；[35] Organic and Biomolecular Chemistry, 2015, vol.13, #13, p.4101-4114；[36] Bioorganic Chemistry, 2014, vol.57, p.65-82；[37] Journal of Organic Chemistry, 2007, vol.72, #23, p.8943-8946；[38] Chinese Journal of Chemistry, 2013, vol.31, #2, p.267-270；[39] Journal of the Chinese Chemical Society, 2013, vol.60, #8, p.1007-1013；[40] Chinese Chemical Letters, 2010, vol.21, #1, p.51-54；[41] Monatshefte fur Chemie, 2003, vol.134, #1, p.37-43；[42] European Journal of Organic Chemistry, 2011, #24, p.4523-4527；[43] Patent: US5965743, 1999, A；[44] Patent: EP1612204, 2006, A1. Location in patent: Page/Page column 19；[45] RSC Advances, 2014, vol.4, #29, p.15122-15130

路线3：

• 步骤：将9g（64.5mmol）碳酸钾和5g（3.75ml; 35.2mmol）1-氟-4-硝基苯加入到2g咪唑（29.4mmol）在14ml DMF中的溶液中。将反应混合物在110℃搅拌1.5小时。向培养基中加入乙酸乙酯（50ml），用50ml水洗涤3次。有机相用硫酸镁干燥并真空浓缩，得到4.4g澄清油形式的产物。
• 条件：110℃，1.5h；水-乙酸乙酯-DMF混合溶剂
• 收率：80%
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