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第 35 卷第 10 期                            精   细   化   工                                 Vol.35, No.10
             2018 年 10 月                             FINE CHEMICALS                                Oct.   2018


              精细化工中间体
                   [(4-(N,N-二甲氨基)苯基]二叔丁基磷的合成工艺



                                               *
                            屈凤波,陈   辉 ,赵顺伟,张银龙,杨振强,杨瑞娜
                                    (河南省科学院化学研究所有限公司,河南  郑州  450002)


                 摘要:以 N,N-二甲基苯胺为原料,经与 PCl 3 和吡啶反应生成[(4-(N,N-二甲氨基)苯基)二氯化磷(Ⅰ),然后在
                 CuI 和 LiBr 的催化作用下与叔丁基氯化镁反应制得[(4-(N,N-二甲氨基)苯基)二叔丁基磷(Ⅱ)。产物的结构经
                 31 PNMR、HNMR 和 HRMS 表征。通过考察各步反应条件,得出最佳工艺条件为:n(N,N-二甲基苯胺)∶n(PCl 3 )∶
                        1
                 n(吡啶)=1∶3∶3,110 ℃反应 24 h,Ⅰ的收率为 85.3%;n(Ⅰ)∶n(CuI)∶n(LiBr)∶n(叔丁基氯化镁)
                 =1∶0.1∶0.2∶3,40 ℃反应 12 h,Ⅱ的收率为 83.4%。
                 关键词:[(4-(N,N-二甲氨基)苯基)二叔丁基磷;[(4-(N,N-二甲氨基)苯基)二氯化磷;N,N-二甲基苯胺;催化;精
                 细化工中间体
                 中图分类号:TQ231      文献标识码:A     文章编号:1003-5214 (2018) 10-1791-04


                    Synthetic Process of 4-(Di-tert-butylphosphino)-N,N-dimethylaniline


                                                      *
                                QU Feng-bo, CHEN Hui , ZHAO Shun-wei, ZHANG Yin-long,
                                             YANG Zhen-qiang, YANG Rui-na
                            (Institute of Chemistry Henan Academy of Sciences, Zhengzhou 450002, Henan, China)

                 Abstract: Dichloro-4-(N,N-dimethylamino)phenylphosphane (Ⅰ) was synthesized from N,N-dimethylaniline
                 with PCl 3 in the presence of pyridine. A coupling reaction between compound I and tert-butylmagnesium
                 chloride using mixture of CuI and LiBr as catalyst led to 4-(di-tert-butylphosphino)-N,N-dimethylaniline
                                                                  1
                                                          31
                 (Ⅱ). These compounds were characterized by  PNMR,  HNMR and HRMS. The optimum reaction
                 conditions for the synthesis of compound I were determined as follows: n (N,N-dimethylaniline) : n (PCl 3) :
                 n  (pyridine) = 1∶3∶3, reaction  temperature 110 ℃, reaction time 24  h. Under the above-mentioned
                 conditions, the yield of compound Ⅰ was 85.3%. When  n  ( Ⅰ ) ∶ n (CuI) ∶ n (LiBr) ∶ n (tert-
                 butylmagnesium chloride) was 1∶0.1∶0.2∶3, reaction temperature was 40 ℃,and reaction time was 12
                 h, the yield of compound  Ⅱ reached 83.4%.
                 Key words: 4-(di-tert-butylphosphino)-N,N-dimethylaniline; dichloro-4-(N,N-dimethylamino) phenylphosphane;
                 N,N-dimethylaniline; catalyst; fine chemical intermediates
                 Foundation items:  National Natural  Science  Foundation  of China (21502045); Outstanding Youth
                 Scientific and Technological Innovation Fund of Henan Province (174100510018); Science and Technology
                 Open Cooperation Project of Henan Province (182106000015 and 17210600063)


                 [(4-(N,N-二甲氨基)苯基)二叔丁基磷作为一类                    成 OLED 功能材料、液晶分子等领域也有广泛的
            重要的有机磷类配体,与过渡金属络合后可以作为                             用途  [5-9] 。
            Suzuki-Miyaura 偶联反应的催化剂,在合成有机杂                         目前,关于[(4-(N,N-二甲氨基)苯基]二叔丁基磷
            环生物活性化合物方面效果显著                 [1-4] ,此外,在合        的合成方法主要包括:(1)二叔丁基磷与 N,N-二甲



                 收稿日期:2018-01-24;  定用日期:2018-04-13; DOI: 10.13550/j.jxhg.20180069
                 基金项目:国家自然科学基金(21502045);河南省科技创新杰出青年基金(174100510018);河南省科技开放合作项目(182106000015,
                 17210600063)
                 作者简介:屈凤波(1972—),女,高级工程师,硕士。联系人:陈辉(1984—),男,副研究员,博士,电话:0371-65511007,E-mail:
                 office@kingorgchem.com。
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