897671-69-1 N-[1,1'-联苯-4-基]-9,9-二甲基-9H-芴-2-胺

运输信息：常温运输。危险描述：非危险化学品，海关编码2921490090

N-[1,1'-联苯-4-基]-9,9-二甲基-9H-芴-2-胺为联苯胺的N取代衍生物，在医药、化工中间体的制备中广泛应用，也用于化学合成。

医药; 化工中间体

合成路线 1（1. 合成：897671-69-1）

产率：91% 合成条件：With palladium diacetate; caesium carbonate In toluene for 24 h; Reflux 实验步骤：反应器中的2L 50.0g联苯-4-胺（330mmol），2-溴-9,9-二甲基-9H-芴43.2g（276mmol），乙酸钯，1.2g（5.6mmol），膦胺，6.4g（11.02mmol），126g（386mmol）碳酸铯加入1000mL甲苯中，在回流下搅拌24小时。通过冷却至室温完成反应后，过滤并用甲苯在减压下浓缩。用柱色谱法分离，得到57g（收率91％） 参考文献：[1] Patent: KR2015/130797, 2015, A. Location in patent: Paragraph 0453-0458 [2] Patent: KR2015/114636, 2015, A. Location in patent: Paragraph 0546-0551 [3] Patent: CN107686484, 2018, A. Location in patent: Paragraph 0085-0088 [4] Patent: KR2016/78765, 2016, A. Location in patent: Paragraph 0187; 0190; 0195; 0196 [5] Patent: US2017/125688, 2017, A1. Location in patent: Paragraph 0314-0316 [6] Patent: KR2017/90390, 2017, A. Location in patent: Paragraph 0125; 0179-0182 [7] Patent: KR101763838, 2017, B1. Location in patent: Paragraph 0107; 0151-0154 [8] Patent: KR101531614, 2015, B1. Location in patent: Paragraph 0822-0825 [9] Patent: KR101486562, 2015, B1. Location in patent: Paragraph 0829-0833 [10] Patent: US2017/125677, 2017, A1. Location in patent: Paragraph 0113-0116 [11] Patent: US2017/125678, 2017, A1. Location in patent: Paragraph 0088; 0089; 0090; 0091 [12] Patent: KR101653337, 2016, B1. Location in patent: Paragraph 0194-0196 [13] Patent: KR2018/14985, 2018, A. Location in patent: Paragraph 0614; 0631-0637 [14] Patent: KR2015/100825, 2015, A. Location in patent: Paragraph 0191-0193 [15] Patent: KR2016/27985, 2016, A. Location in patent: Paragraph 0153-0155 [16] Patent: US2018/282295, 2018, A1. Location in patent: Paragraph 0149; 0150 [17] Patent: CN106928237, 2017, A. Location in patent: Paragraph 0152; 0153-01551; 0260-0262 [18] Patent: CN106588674, 2017, A. Location in patent: Paragraph 0056; 0057; 0058 [19] Patent: WO2012/15265, 2012, A1. Location in patent: Page/Page column 14 [20] Patent: CN105153031, 2018, B. Location in patent: Paragraph 0083; 0084; 0085 [21] Patent: KR2018/47313, 2018, A. Location in patent: Paragraph 0172-0175 [22] Patent: KR2018/60582, 2018, A. Location in patent: Paragraph 0215-0217 [23] Patent: KR2018/60089, 2018, A. Location in patent: Paragraph 0165-0168 [24] Patent: KR2018/74172, 2018, A. Location in patent: Paragraph 0245-0248 [25] Patent: CN105111143, 2018, B. Location in patent: Paragraph 0084; 0085; 0086

合成路线 2（2. 合成：897671-69-1）

产率：92% 合成条件：With [Pd(N,N'-bis(2,6-bis(di-p-tolylmethyl)-4-methylphenyl)-imidazol-2-ylidene)(acetylacetonate)Cl]; lithium hexamethyldisilazane In 1,4-dioxane at 110℃; for 3 h; Inert atmosphere; Sealed tube 实验步骤：一般步骤：向玻璃瓶中加入[Pd（IPr * me）（acac）Cl]，纯胺（1.1mmol）和芳基卤化物（1mmol）的无水1,4-二恶烷（1mL），在大气压下，氩气并用装有隔膜的螺帽密封。随后在室温下在氩气下注入LiHMDS（1.1mmol），然后将反应混合物在110℃回流3小时。此后，蒸发二恶烷，将粗产物溶解在CH₂Cl₂中。在覆盖有硅藻土的二氧化硅垫上过滤溶液，并用CH₂Cl₂洗脱垫。在硅胶上进行色谱分离后，得到纯的络合物。 参考文献：[1] Journal of Organometallic Chemistry, 2018, vol. 861, p. 125 - 130 [2] Advanced Synthesis and Catalysis, 2016, vol. 358, # 10, p. 1589 - 1594 [3] Patent: CN106632219, 2017, A. Location in patent: Paragraph 0077; 0078; 0079; 0080

合成路线 3（3. 合成：897671-69-1）

实验步骤：4-氨基联苯在20℃下，以(冰醋酸)：(水)=1：4为溶剂，加入重铬酸钾进行反应，分离提纯后，再加入18-冠-6相转移催化剂，以邻二氯苯为溶剂在氮气保护下与9，9-二甲基-2-溴芴进行反应，在回流下反应20h，产物经柱层析和重结晶提纯N-[1，1'-联苯-4-基]-9，9-二甲基-9H-芴-2-胺。其合成反应式如下图：图 N-[1，1'-联苯-4-基]-9，9-二甲基-9H-芴-2-胺的合成反应式