CN108689825A - 一种合成2-(三氟亚乙基/二氟乙基)-1,3-二酮化合物的方法 - Google Patents
一种合成2-(三氟亚乙基/二氟乙基)-1,3-二酮化合物的方法 Download PDFInfo
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- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
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Abstract
本发明公开了一种合成2‑(三氟亚乙基/二氟乙基)‑1,3‑二酮化合物的方法:以三氟乙酸酐/二氟乙酸酐为试剂,以1,3‑二酮衍生物为底物,以三乙基胺为碱,在溶剂中,加热80‑130度,搅拌1~24小时,反应结束后反应液后处理得到2‑(2,2,2‑三氟亚乙基)‑1,3‑二酮和2‑(2,2‑二氟乙基)‑1,3‑二酮化合物。本发明的合成方法具有产率普遍较高、原料易得,操作简便,底物广等优点,具有良好的工业应用前景。
Description
技术领域
本发明属于有机氟化学合成领域,具体涉及一种合成2-(三氟亚乙基/二氟乙基)-1,3-二酮化合物的方法。
背景技术
氟原子具有最强的电负性,较小的原子半径和较低的极化率,往有机物中引入氟元素可以显著提高其脂溶性、稳定性以及生物活性。例如在有机化合物上引入三氟甲基基团,能使目标分子的极性、偶极距、稳定性和亲脂性得到提高。因此,有机含氟化合物已广泛应用在医药、农药以及材料等领域。通过利用结构简单、廉价易得的氟化试剂,在有机分子上引入含氟基团,是合成有机含氟化合物的重要手段。
另一方面,1,3-二酮骨架广泛存在于天然产物,药物分子,以及生物相关的分子中,呈现出多样的生物活性,如抗氧化、抗肿瘤、抗菌、抗病毒和抗真菌活性等。在1,3-二酮骨架上引入三氟甲基基团、二氟甲基基团将赋予化合物新的生物活性。本发明利用一些简单易得的原料,一步合成2-(2,2,2-三氟亚乙基)-1,3-二酮和2-(2,2-二氟乙基)-1,3-二酮化合物,其有望在医药、农药以及先进材料上得到应用。
发明内容
本发明的目的在于提供一种合成2-(2,2,2-三氟亚乙基)-1,3-二酮和2-(2,2-二氟乙基)-1,3-二酮化合物的方法,其具有产率高、原料易得、操作简便、底物广等优点,具有良好的工业应用前景。
为实现上述目的,本发明采用如下技术方案:
一种合成2-(2,2,2-三氟亚乙基)-1,3-二酮的方法,其以三氟乙酸酐为试剂,以1,3-二酮衍生物为底物,以三乙基胺为碱,在溶剂中经加热反应得到所述2-(2,2,2-三氟亚乙基)-1,3-二酮化合物;其反应流程为:
。
一种合成2-(2,2-二氟乙基)-1,3-二酮化合物的方法,其以二氟乙酸酐为试剂,以1,3-二酮衍生物为底物,以三乙基胺为碱,在溶剂中经加热反应得到所述2-(2,2-二氟乙基)-1,3-二酮化合物;其反应流程为:
。
上述反应的具体反应步骤为:在氮气气氛中,向带有磁力搅拌装置的容器中加入1,3-二酮衍生物、三氟乙酸酐/二氟乙酸酐、三乙基胺和溶剂,混合均匀后关好塞子,将其加热至80-130℃,搅拌反应20 h后,用乙酸乙酯萃取三次,合并有机相,加饱和氯化钠溶液洗涤,经无水硫酸镁干燥后,旋蒸除去有机溶剂,得到的粗产物以正戊烷(正己烷)和二氯甲烷为洗脱剂,经硅胶柱层析分离得到2-(2,2,2-三氟亚乙基)-1,3-二酮和2-(2,2-二氟乙基)-1,3-二酮化合物。
其中,三氟乙酸酐/二氟乙酸酐、1,3-二酮衍生物、三乙基胺以及溶剂的摩尔比为0.05-2.00:0.10-4.00:0.10-6.000:5-25。
所述溶剂为甲苯、四氢呋喃、乙腈、N-甲基吡咯烷酮、乙二醇二甲醚、二氯乙烷中的一种。
所述1,3-二酮衍生物的结构式为,其具体为下述式1-式23中的任意一种:
。
所得2-(2,2,2-三氟亚乙基)-1,3-二酮的结构通式为:,其具体为下述式1-式23中的任意一种:
;
所得2-(2,2-二氟乙基)-1,3-二酮的结构通式为:,其具体为下述式1-式10中的任意一种:
。
本发明的有益效果在于:
本发明以廉价易得的三氟乙酸酐/二氟乙酸酐、1,3-二酮衍生物、三乙基胺等为原料,一步合成2-(2,2,2-三氟亚乙基)-1,3-二酮和2-(2,2-二氟乙基)-1,3-二酮化合物,其操作简便,普遍具有较高的产率,且底物范围广,具有很好的工业应用前景。
附图说明
图1为实施例6制得的1,3-二(4-甲氧基苯)-2-(2,2,2-三氟亚乙基)丙烷-1,3-二酮单晶结构示意图。
具体实施方式
为了使本发明所述的内容更加便于理解,下面结合具体实施方式对本发明所述的技术方案做进一步的说明,但是本发明不仅限于此。
实施例1
在一个25 mL反应管中放入聚四氟乙烯磁石一粒,加入1.00 mmol 二苯甲酰甲烷,5mmol三氟乙酸酐,7 mmol三乙胺以及5 mL 甲苯,100℃密闭体系中搅拌反应20 h后,用乙酸乙酯萃取三次,合并有机相,加饱和氯化钠溶液洗涤,经无水硫酸镁干燥后,旋蒸除去有机溶剂;得到的粗产物以正戊烷(正己烷)和二氯甲烷为洗脱剂,通过硅胶柱层析分离得到1,3-二苯基-2-(2,2,2-三氟亚乙基)丙烷-1,3-二酮(产率85%)。1H NMR (400 MHz, CDCl3) δ8.02 (d, J = 7.3 Hz, 4H), 7.65 (dd, J = 14.2, 7.1 Hz, 2H), 7.53 (dd, J =12.4, 7.2 Hz, 4H), 6.35 (q, J = 7.5 Hz, 1H).13C NMR (101 MHz, CDCl3) δ 191.1(s), 190.9 (s), 148.9(q, J = 4.6 Hz), 135.2 (s), 134.8 (s), 134.6 (s), 134.5(s), 130.3 (s), 129.8 (s), 128.9 (s), 128.9 (s), 124.7 (q, J = 36.3 Hz),121.7 (q, J = 272.6 Hz). 19F NMR (376 MHz, CDCl3) δ -60.1 (d, J = 7.5 Hz, 3F)。
实施例2
在一个25 mL反应管中放入聚四氟乙烯磁石一粒,加入1.00 mmol 1,3-双(对-甲苯基)丙烷-1,3-二酮,5 mmol三氟乙酸酐,7 mmol三乙胺以及5 mL 四氢呋喃,100℃密闭体系中搅拌反应20 h后,用乙酸乙酯萃取三次,合并有机相,加饱和氯化钠溶液洗涤,经无水硫酸镁干燥后,旋蒸除去有机溶剂;得到的粗产物以正戊烷(正己烷)和二氯甲烷为洗脱剂,通过硅胶柱层析分离得到1,3-二-对-甲苯基-2-(2,2,2-三氟亚乙基)丙烷-1,3-二酮(产率52%)。1H NMR (400 MHz, CDCl3) δ 7.92 (t, J = 6.7 Hz, 4H), 7.38 – 7.30 (m, 4H),6.27 (q, J = 7.5 Hz, 1H), 2.45 (d, J = 4.5 Hz, 6H). 13C NMR (101 MHz, CDCl3) δ190.6 (s), 190.5 (s), 149.6 (q, J = 4.6 Hz), 145.8 (s), 145.7 (s), 132.9 (q,J = 0.9 Hz), 132.3 (s), 130.5 (s), 130.0 (s), 129.6 (s), 129.6 (s), 123.8 (q,J = 36.2 Hz), 121.7 (q, J = 272.5 Hz), 21.9 (s), 21.8 (s). 19F NMR (376 MHz,CDCl3) δ -60.1 (d, J = 7.6 Hz, 3F)。
实施例3
在一个25 mL反应管中放入聚四氟乙烯磁石一粒,加入1.00 mmol 1,3-双(间-甲苯基)丙烷-1,3-二酮,5 mmol三氟乙酸酐,7 mmol三乙胺以及5 mL 乙腈,100℃密闭体系中搅拌反应20 h后,用乙酸乙酯萃取三次,合并有机相,加饱和氯化钠溶液洗涤,经无水硫酸镁干燥后,旋蒸除去有机溶剂;得到的粗产物以正戊烷(正己烷)和二氯甲烷为洗脱剂,通过硅胶柱层析分离得到1,3-二间甲苯基-2-(2,2,2-三氟亚乙基)丙烷-1,3-二酮(产率58%)。1HNMR (400 MHz, CDCl3) δ 7.87 – 7.77 (m, 4H), 7.52 – 7.38 (m, 4H), 6.34 (q, J =7.5 Hz, 1H), 2.44 (d, J = 4.2 Hz, 6H). 13C NMR (101 MHz, CDCl3) δ 191.3 (s),191.1 (s), 149.2 (q, J = 4.5 Hz), 139.0 (s), 138.8 (s), 135.5 (s), 135.3 (s),135.2 (s), 135.0 (s), 130.5 (s), 129.9 (s), 128.7 (s), 127.6 (s), 127.4 (s),124.6 (q, J = 36.2 Hz), 121.7 (q, J = 272.5 Hz), 21.3 (s), 21.2 (s).19F NMR(376 MHz, CDCl3) δ -60.0 (d, J = 7.5 Hz, 3F). 19F NMR (376 MHz, CDCl3) δ -60.0(d, J = 7.5 Hz, 3F)。
实施例4
在一个25 mL反应管中放入聚四氟乙烯磁石一粒,加入1.00 mmol 1,3-双(邻-甲苯基)丙烷-1,3-二酮,5 mmol三氟乙酸酐,7 mmol三乙胺以及5 mL N-甲基吡咯烷酮,100℃密闭体系中搅拌反应20 h后,用乙酸乙酯萃取三次,合并有机相,加饱和氯化钠溶液洗涤,经无水硫酸镁干燥后,旋蒸除去有机溶剂;得到的粗产物以正戊烷(正己烷)和二氯甲烷为洗脱剂,通过硅胶柱层析分离分离得到1,3-二邻甲苯基-2-(2,2,2-三氟亚乙基)丙烷-1,3-二酮(产率23%)。1H NMR (400 MHz, CDCl3) δ 7.71 (d, J = 7.7 Hz, 1H), 7.59 (d, J = 7.6Hz, 1H), 7.45 (dt, J = 11.5, 7.5 Hz, 2H), 7.31 (dt, J = 15.0, 7.9 Hz, 4H),6.37 (q, J = 7.7 Hz, 1H), 2.58 (s, 3H), 2.40 (s, 3H). 13C NMR (101 MHz, CDCl3)δ 194.4 (s), 193.0 (s), 150.1 (q, J = 4.5 Hz), 140.9 (s), 138.3 (s), 135.4(s), 134.3 (s), 133.2 (s), 132.4(s), 132.2 (s), 132.1 (s), 131.7 (s), 129.6(s), 126.7 (q, J = 36.3 Hz), 125.9 (s), 125.6 (s), 121.9 (q, 272.5 Hz), 21.5(s), 20.1 (s). 19F NMR (376 MHz, CDCl3) δ -60.1 (d, J = 7.8 Hz, 3F)。
实施例5
在一个25 mL反应管中放入聚四氟乙烯磁石一粒,加入1.00 mmol 1,3-双(4-(叔丁基)苯基)丙烷-1,3-二酮,5 mmol三氟乙酸酐,7 mmol三乙胺以及5 mL 乙二醇二甲醚,100℃密闭体系中搅拌反应20 h后,用乙酸乙酯萃取三次,合并有机相,加饱和氯化钠溶液洗涤,经无水硫酸镁干燥后,旋蒸除去有机溶剂;得到的粗产物以正戊烷(正己烷)和二氯甲烷为洗脱剂,通过硅胶柱层析分离得到1,3-双(4-(叔丁基)苯基)-2-(2,2,2-三氟亚乙基)丙烷-1,3-二酮(产率72%)。1H NMR (400 MHz, CDCl3) δ 8.00 (t, J = 9.0 Hz, 4H), 7.56 (t, J= 8.2 Hz, 4H), 6.30 (q, J = 7.4 Hz, 1H), 1.37 (d, J = 4.5 Hz, 18H). 13C NMR(101 MHz, CDCl3). 13C NMR (101 MHz, CDCl3) δ 190.6 (s), 190.4 (s), 158.6 (s),158.5 (s), 149.7 (q, J = 4.6 Hz), 132.7 (s), 132.3 (s), 130.4 (s), 129.9 (s),126.0 (s), 125.9 (s), 123.7 (q, J = 36.2 Hz),121.5 (q, J = 272.6 Hz), 35.3(s), 31.0 (s). 19F NMR (376 MHz, CDCl3) δ -60.1 (d, J = 7.5 Hz, 3F)。
实施例6
在一个25 mL反应管中放入聚四氟乙烯磁石一粒,加入1.00 mmol 1,3-双(4-甲氧基苯基)丙烷-1,3-二酮,5 mmol三氟乙酸酐,7 mmol三乙胺以及5 mL 二氯乙烷,100℃密闭体系中搅拌反应20 h后,用乙酸乙酯萃取三次,合并有机相,加饱和氯化钠溶液洗涤,经无水硫酸镁干燥后,旋蒸除去有机溶剂;得到的粗产物以正戊烷(正己烷)和二氯甲烷为洗脱剂,通过硅胶柱层析分离层析分离得到1,3-双(4-甲氧基苯基)-2-(2,2,2-三氟亚乙基)丙烷-1,3-二酮(产率65%)。1H NMR (400 MHz, CDCl3) δ 8.11 – 7.86 (m, 4H), 7.05 – 6.92 (m,4H), δ 6.75 (s, 0.3H), 6.20 (q, J = 7.5 Hz, 0.7H), 3.87 (t, J = 4.3 Hz, 6H).13C NMR (101 MHz, CDCl3) δ 189.3 (s), 189.2 (s), 184.6 (s), 164.8 (s), 164.7(s), 163.1 (s), 150.4 (q, J = 4.7 Hz), 133.0 (s), 132.5 (s), 129.1 (s), 128.4(s), 128.2 (s), 127.6 (s), 122.5 (q, J = 36.0 Hz), 121.8 (q, J = 272.5 Hz),91.5 (s), 55.6 (s), 55.6 (s), 55.5 (s), 55.4 (s). 19F NMR (376 MHz, CDCl3) δ -60.1 (d, J = 7.5 Hz, 3F)。
实施例7
在一个25 mL反应管中放入聚四氟乙烯磁石一粒,加入1.00 mmol 1,3-双(3-甲氧基苯基)丙烷-1,3-二酮,5 mmol三氟乙酸酐,7 mmol三乙胺以及5 mL 甲苯,100℃密闭体系中搅拌反应20 h后,用乙酸乙酯萃取三次,合并有机相,加饱和氯化钠溶液洗涤,经无水硫酸镁干燥后,旋蒸除去有机溶剂;得到的粗产物以正戊烷(正己烷)和二氯甲烷为洗脱剂,通过硅胶柱层析分离层析分离得到3-双(3-甲氧基苯基)-2-(2,2,2-三氟亚乙基)丙烷-1,3-二酮(产率79%)。1H NMR (400 MHz, CDCl3) δ 7.64 – 7.51 (m, 3H), 7.42 (td, J = 16.1,8.7 Hz, 3H), 7.15 (dd, J = 32.2, 8.1 Hz, 2H), 6.85 (s, 0.17H), 6.37 (q, J =7.5 Hz, 0.83H), 3.89 (s, 1H), 3.85 (s, 5H). 13C NMR (101 MHz, CDCl3) δ 190.8(s), 190.6 (s), 185.5(s), 160.0 (s, 2C), 159.9 (s), 149.0 (q, J = 4.6 Hz),136.9 (s), 136.5 (s), 136.1 (s), 129.9 (s), 129.7 (s), 125.0 (q, J = 36.3Hz), 123.1 (s), 123.0 (s),121.6 (s), 121.1 (s), 121.2 (q, J = 273.0 Hz),119.6 (s), 118.6 (s), 113.9 (s), 112.9 (s), 112.0 (s), 93.5 (s), 55.5 (s),55.4 (s). 19F NMR (376 MHz, CDCl3) δ -60.1 (d, J = 7.5 Hz, 3F)。
实施例8
在一个25 mL反应管中放入聚四氟乙烯磁石一粒,加入1.00 mmol 4,4'-丙二酰基苄腈,5 mmol三氟乙酸酐,7 mmol三乙胺以及5 mL 甲苯,100℃密闭体系中搅拌反应20 h后,用乙酸乙酯萃取三次,合并有机相,加饱和氯化钠溶液洗涤,经无水硫酸镁干燥后,旋蒸除去有机溶剂;得到的粗产物以正戊烷(正己烷)和二氯甲烷为洗脱剂,通过硅胶柱层析分离层析分离得到4,4' - (2-(2,2,2-三氟亚乙基)丙二酰)苄腈(产率50%)。1H NMR (400 MHz,CDCl3) δ 8.08 (d, J = 8.2 Hz, 4H), 7.87 (dd, J = 8.1, 6.5 Hz, 4H), 6.40 (q, J= 7.3 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 189.8 (s), 189.5 (s), 146.8 (q, J =4.5 Hz), 137.7 (s), 137.6 (s), 132.9 (s), 132.8 (s), 130.5 (s), 130.0 (s),126.3 (q, J = 36.7 Hz), 121.2 (q, J = 273.0 Hz), 118.1 (s), 118.0 (s), 117.5(s), 117.4 (s). 19F NMR (376 MHz, CDCl3) δ -60.1 (d, J = 7.3 Hz, 3F)。
实施例9
在一个25 mL反应管中放入聚四氟乙烯磁石一粒,加入1.00 mmol 1,3-双(4-氟苯基)丙烷-1,3-二酮,5 mmol三氟乙酸酐,7 mmol三乙胺以及5 mL 甲苯,100℃密闭体系中搅拌反应20 h后,用乙酸乙酯萃取三次,合并有机相,加饱和氯化钠溶液洗涤,经无水硫酸镁干燥后,旋蒸除去有机溶剂;得到的粗产物以正戊烷(正己烷)和二氯甲烷为洗脱剂,通过硅胶柱层析分离胶柱层析分离得到1,3-双(4-氟苯基)-2-(2,2,2-三氟亚乙基)丙烷-1,3-二酮(产率79%)。 1H NMR (400 MHz, CDCl3) δ 8.05 (dt, J = 8.7, 6.9 Hz, 4H), 7.17 (dd,J = 18.2, 9.7 Hz, 4H), 6.29 (q, J = 7.4 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ189.3 (s), 189.2 (s), 167.9 (d, J = 4.4 Hz), 165.4 (d, J = 4.6 Hz), 148.9 (q,J = 4.6 Hz), 133.2 (d, J = 9.8 Hz), 132.7 (d, J = 9.9 Hz), 131.6 (s), 131.1(d, J = 2.9 Hz), 123.9 (q, J = 36.4 Hz), 121.5 (q, J = 272.6 Hz), 116.4 (d, J= 6.0 Hz), 116.1 (d, J = 6.1 Hz). 19F NMR (376 MHz, CDCl3) δ -60.2 (d, J = 7.5Hz, 3F), -101.6 (tt, J = 8.3, 5.4 Hz, 1F), -101.8 (tt, J = 8.3, 5.4 Hz, 1F)。
实施例10
在一个25 mL反应管中放入聚四氟乙烯磁石一粒,加入1.00 mmol 1,3-双(4-氯苯基)丙烷-1,3-二酮,5 mmol三氟乙酸酐,7 mmol三乙胺以及5 mL 甲苯,100℃密闭体系中搅拌反应20 h后,用乙酸乙酯萃取三次,合并有机相,加饱和氯化钠溶液洗涤,经无水硫酸镁干燥后,旋蒸除去有机溶剂;得到的粗产物以正戊烷(正己烷)和二氯甲烷为洗脱剂,通过硅胶柱层析分离胶柱层析分离得到1,3-双(4-氯苯基)-2-(2,2,2-三氟亚乙基)丙烷-1,3-二酮(产率72%)。1H NMR (400 MHz, CDCl3) δ 7.94 (dd, J = 8.4, 4.8 Hz, 4H), 7.50 (dd,J = 8.4, 3.9 Hz, 4H), 6.31 (q, J = 7.4 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ189.7 (s), 189.6 (s), 148.4 (q, J = 4.6 Hz), 141.6 (s), 141.5 (s), 133.5 (s),133.0(s), 131.7 (s), 131.2 (s), 129.4 (s), 129.3 (s), 124.5 (q, J = 36.4 Hz),121.5 (q, J = 272.7 Hz). 19F NMR (376 MHz, CDCl3) δ -60.1 (d, J = 7.4 Hz, 3F)。
实施例11
在一个25 mL反应管中放入聚四氟乙烯磁石一粒,加入二苯甲酰甲烷,5 mmol二氟乙酸酐,7 mmol三乙胺以及5 mL 甲苯,130℃密闭体系中搅拌反应20 h后,用乙酸乙酯萃取三次,合并有机相,加饱和氯化钠溶液洗涤,经无水硫酸镁干燥后,旋蒸除去有机溶剂;得到的粗产物以正戊烷(正己烷)和二氯甲烷为洗脱剂,通过硅胶柱层析分离得到2-(2,2-二氟乙基)-1,3-二苯基丙烷-1,3-二酮(产率30%)。1H NMR (400 MHz, CDCl3) δ 8.01 (d, J =7.7 Hz, 4H), 7.62 (t, J = 7.3 Hz, 2H), 7.50 (t, J = 7.4 Hz, 4H), 6.06 (t, J =56.7 Hz, 1H), 5.58 (t, J = 6.4 Hz, 1H), 2.70 (ddd, J = 16.7, 10.9, 4.3 Hz,2H). 13C NMR (101 MHz, CDCl3) δ 194.7 (s), 135.2 (s), 134.0 (s), 129.1 (s),128.7 (s), 115.7 (t, J = 239.6 Hz), 50.1 (t, J = 4.3 Hz), 33.4 (t, J = 22.4Hz). 19F NMR (376 MHz, CDCl3) δ -115.9 (dt, J = 56.7, 17.0 Hz, 2F)。
实施例12
在一个25 mL反应管中放入聚四氟乙烯磁石一粒,加入1.00 mmol 1,3-双(4-(叔丁基)苯基)丙烷-1,3-二酮,5 mmol二氟乙酸酐,7 mmol三乙胺以及5 mL 甲苯,130℃密闭体系中搅拌反应20 h后,用乙酸乙酯萃取三次,合并有机相,加饱和氯化钠溶液洗涤,经无水硫酸镁干燥后,旋蒸除去有机溶剂;得到的粗产物以正戊烷(正己烷)和二氯甲烷为洗脱剂,通过硅胶柱层析分离得到(4-(叔丁基)苯基)-2-(2,2-二氟乙基)丙烷-1,3-二酮(产率22%)。1HNMR (400 MHz, CDCl3) δ 7.97 (d, J = 7.6 Hz, 4H), 7.52 (d, J = 7.5 Hz, 4H),6.03 (t, J = 56.6 Hz, 1H), 5.53 (t, J = 6.4 Hz, 1H), 2.77 – 2.58 (m, 2H),1.36 (s, 18H). 13C NMR (101 MHz, CDCl3) δ 194.3 (s), 157.9 (s), 132.6 (s),128.7 (s), 126.08 (s), 115.9 (t, J = 239.5 Hz), 50.0 (t, J = 4.4 Hz), 35.2(s), 33.5 (t, J = 22.5 Hz), 31.0 (s). 19F NMR (376 MHz, CDCl3) δ -116.0 (dt, J= 56.9, 16.8 Hz, 2F)。
实施例13
在一个25 mL反应管中放入聚四氟乙烯磁石一粒,加入1.00 mmol 1,3-双(4-氟苯基)丙烷-1,3-二酮,5 mmol二氟乙酸酐,7 mmol三乙胺以及5 mL 甲苯,130℃密闭体系中搅拌反应20 h后,用乙酸乙酯萃取三次,合并有机相,加饱和氯化钠溶液洗涤,经无水硫酸镁干燥后,旋蒸除去有机溶剂;得到的粗产物以正戊烷(正己烷)和二氯甲烷为洗脱剂,通过硅胶柱层析分离得到(4-氟苯基)-2-(2,2-二氟乙基)丙烷-1,3-二酮(产率20%)。1H NMR (400MHz, CDCl3) δ 8.01 (dd, J = 7.6, 5.4 Hz, 4H), 7.16 (t, J = 8.1 Hz, 4H), 6.03(tt, J = 56.6, 3.8 Hz, 1H), 5.44 (t, J = 6.5 Hz, 1H), 2.76 – 2.61 (m, 2H). 13CNMR (101 MHz, CDCl3) δ 192.9 (s), 167.5 (s), 165.0 (s), 131.4 (d, J = 9.6Hz), 116.4 (d, J = 22.1 Hz), 115.6 (t, J = 239.7 Hz), 50.1 (t, J = 4.2 Hz),33.4 (t, J = 22.3 Hz). 19F NMR (376 MHz, CDCl3) δ -102.9 – -103.0 (m, 1F), -116.1 (dt, J = 56.6, 17.2 Hz, 2F)。
实施例14
在一个25 mL反应管中放入聚四氟乙烯磁石一粒,加入1.00 mmol 1,3-双(4-氯苯基)丙烷-1,3-二酮,5 mmol二氟乙酸酐,7 mmol三乙胺以及5 mL 甲苯,130℃密闭体系中搅拌反应20 h后,用乙酸乙酯萃取三次,合并有机相,加饱和氯化钠溶液洗涤,经无水硫酸镁干燥后,旋蒸除去有机溶剂;得到的粗产物以正戊烷(正己烷)和二氯甲烷为洗脱剂,通过硅胶柱层析分离得到(4-氯苯基)-2-(2,2-二氟乙基)丙烷-1,3-二酮(产率21%)。1H NMR (400MHz, CDCl3) δ 8.01 (dd, J = 7.6, 5.4 Hz, 4H), 7.16 (t, J = 8.1 Hz, 4H), 6.03(tt, J = 56.6, 3.8 Hz, 1H), 5.44 (t, J = 6.5 Hz, 1H), 2.76 – 2.61 (m, 2H). 13CNMR (101 MHz, CDCl3) δ 192.9 (s), 167.5 (s), 165.0 (s), 131.4 (d, J = 9.6Hz), 116.4 (d, J = 22.1 Hz), 115.6 (t, J = 239.7 Hz), 50.1 (t, J = 4.2 Hz),33.4 (t, J = 22.3 Hz). 19F NMR (376 MHz, CDCl3) δ -116.1 (dt, J = 56.6, 17.2Hz, 2F)。
实施例15
在一个25 mL反应管中放入聚四氟乙烯磁石一粒,加入1.00 mmol 1,3-双(4-溴苯基)丙烷-1,3-二酮,5 mmol二氟乙酸酐,7 mmol三乙胺以及5 mL 甲苯,130℃密闭体系中搅拌反应20 h后,用乙酸乙酯萃取三次,合并有机相,加饱和氯化钠溶液洗涤,经无水硫酸镁干燥后,旋蒸除去有机溶剂;得到的粗产物以正戊烷(正己烷)和二氯甲烷为洗脱剂,通过硅胶柱层析分离得到1,3-双(4-溴苯基)-2-(2,2-二氟乙基)丙烷-1,3-二酮 (产率20%)。1H NMR(400 MHz, CDCl3) δ 7.82 (d, J = 7.9 Hz, 4H), 7.63 (d, J = 7.9 Hz, 4H), 6.03(tt, J = 56.6, 3.6 Hz, 1H), 5.41 (t, J = 6.5 Hz, 1H), 2.77 – 2.57 (m, 2H). 13CNMR (101 MHz, CDCl3) δ 193.4 (s), 133.8 (s), 132.5 (s), 130.1 (s), 129.6 (s),115.5 (t, J = 239.8 Hz), 50.0 (t, J = 4.1 Hz), 33.3 (t, J = 22.2 Hz). 19F NMR(376 MHz, CDCl3) δ -116.0 (dt, J = 56.6, 17.3 Hz, 2F)。
实施例16
在一个25 mL反应管中放入聚四氟乙烯磁石一粒,加入1.00 mmol 1-(4-溴苯基)-3-(对甲苯基)丙烷-1,3-二酮,5 mmol二氟乙酸酐,7 mmol三乙胺以及5 mL 甲苯,130℃密闭体系中搅拌反应20 h后,用乙酸乙酯萃取三次,合并有机相,加饱和氯化钠溶液洗涤,经无水硫酸镁干燥后,旋蒸除去有机溶剂;得到的粗产物以正戊烷(正己烷)和二氯甲烷为洗脱剂,通过硅胶柱层析分离得到1,3-双(4-氯苯基)-2-(2,2-二氟乙基)丙烷-1,3-二酮 (产率32%)。1H NMR (400 MHz, CDCl3) δ 7.89 (d, J = 7.5 Hz, 2H), 7.82 (d, J = 7.6 Hz,2H), 7.61 (d, J = 7.7 Hz, 2H), 7.30 (d, J = 7.8 Hz, 2H), 6.03 (tt, J = 56.7,3.8 Hz, 1H), 5.45 (t, J = 6.5 Hz, 1H), 2.82 – 2.52 (m, 2H), 2.44 (s, 3H). 13CNMR (101 MHz, CDCl3) δ 194.1 (s), 193.7 (s), 145.4 (s), 134.1 (s), 132.5 (s),132.4 (s), 130.1 (s), 129.9 (s), 129.2 (s), 128.9 (s), 115.7 (t, J = 239.6Hz), 50.0 (t, J = 4.2 Hz), 33.4 (t, J = 22.3 Hz), 21.7 (s). 19F NMR (376 MHz,CDCl3) δ -115.1 (dt, J = 56.6, 16.8 Hz, 2F), -115.9 (dt, J = 55.4, 16.2 Hz,2F), -116.1 (dt, J = 34.7, 16.5 Hz, 2F), -116.9 (dt, J = 56.7, 17.3 Hz, 2F)。
实施例17
在一个25 mL反应管中放入聚四氟乙烯磁石一粒,加入1.00 mmol 1-(4-溴苯基)-3-(4-氟苯基),5 mmol二氟乙酸酐,7 mmol三乙胺以及5 mL 甲苯,130℃密闭体系中搅拌反应20 h后,用乙酸乙酯萃取三次,合并有机相,加饱和氯化钠溶液洗涤,经无水硫酸镁干燥后,旋蒸除去有机溶剂;得到的粗产物以正戊烷(正己烷)和二氯甲烷为洗脱剂,通过硅胶柱层析分离得到1-(4-bromophenyl)-2-(2,2-difluoroethyl)-3-(4-fluorophenyl)propane-1,3-dione(产率21%)。1H NMR (400 MHz, CDCl3) δ 8.01 (dd, J = 7.3, 5.4 Hz, 2H),7.83 (d, J = 7.5 Hz, 2H), 7.64 (d, J = 7.5 Hz, 2H), 7.18 (t, J = 8.0 Hz, 2H),6.03 (tt, J = 56.7, 3.5 Hz, 1H), 5.42 (t, J = 6.4 Hz, 1H), 2.79 – 2.60 (m,2H). 13C NMR (101 MHz, CDCl3) δ 193.5 (s), 192.8 (s), 166.3 (d, J = 257.2 Hz),133.9 (s), 132.5 (s), 131.5 (s), 131.4 (s), 130.1 (s), 129.5 (s), 116.4 (d, J= 22.1 Hz), 115.5 (t, J = 239.7 Hz), 50.1 (t, J = 4.2 Hz), 33.3 (t, J = 22.2Hz). 19F NMR (376 MHz, CDCl3) δ -102.7 – -102.9 (m, 1F), -116.1 (dtd, J =56.7, 17.2, 3.3 Hz, 2F)。
实施例18
在一个25 mL反应管中放入聚四氟乙烯磁石一粒,加入1.00 mmol 1-(4-溴苯基)-3-(4-甲氧基苯基)丙烷-1,3-二酮,5 mmol二氟乙酸酐,7 mmol三乙胺以及5 mL 甲苯,130℃密闭体系中搅拌反应20 h后,用乙酸乙酯萃取三次,合并有机相,加饱和氯化钠溶液洗涤,经无水硫酸镁干燥后,旋蒸除去有机溶剂;得到的粗产物以正戊烷(正己烷)和二氯甲烷为洗脱剂,通过硅胶柱层析分离得到1-(4-溴苯基)-2-(2,2-二氟乙基)-3-(4-甲氧基苯基)丙烷-1,3-二酮(产率30%)。1H NMR (400 MHz, CDCl3) δ 7.98 (d, J = 7.8 Hz, 2H), 7.82(d, J = 7.6 Hz, 2H), 7.61 (d, J = 7.7 Hz, 2H), 6.98 (d, J = 7.8 Hz, 2H), 6.02(t, J = 56.6 Hz, 1H), 5.40 (t, J = 6.0 Hz, 1H), 3.90 (s, 3H), 2.86 – 2.50 (m,2H). 13C NMR (101 MHz, CDCl3) δ 193.7 (s), 192.8 (s), 164.4 (s), 134.2 (s),132.3 (s), 131.2 (s), 130.0 (s), 129.2 (s), 127.8 (s), 115.7 (t, J = 239.6Hz), 114.4 (s), 55.6 (s), 50.0 (t, J = 4.0 Hz), 33.5 (t, J = 22.3 Hz). 19F NMR(376 MHz, CDCl3) δ -115.1 (dt, J = 56.7, 16.7 Hz, 2F), -115.8 (dt, J = 56.6,16.7 Hz, 2F), -116.2 (dt, J = 56.8, 17.4 Hz, 2F), -117.0 (dt, J = 56.9, 17.4Hz, 2F)。
Claims (9)
1.一种合成2-(2,2,2-三氟亚乙基)-1,3-二酮化合物的方法,其特征在于:以三氟乙酸酐为反应试剂,以1,3-二酮衍生物为反应底物,以三乙基胺为碱,在溶剂中经加热反应制得2-(2,2,2-三氟亚乙基)-1,3-二酮化合物;所述的2-(2,2,2-三氟亚乙基)-1,3-二酮的结构式为:。
2.一种合成2-(2,2-二氟乙基)-1,3-二酮化合物的方法,其特征在于:以二氟乙酸酐为反应试剂,以1,3-二酮衍生物为反应底物,以三乙基胺为碱,在溶剂中经加热反应制得2-(2,2-二氟乙基)-1,3-二酮化合物;所述的2-(2,2-二氟乙基)-1,3-二酮化合物的结构式为: 。
3.根据权利要求1或2所述的合成方法,其特征在于:所述的溶剂为甲苯、四氢呋喃、乙腈、N-甲基吡咯烷酮、乙二醇二甲醚、二氯乙烷中的一种。
4.根据权利要求1所述的合成方法,其特征在于:所述的三氟乙酸酐、1,3-二酮衍生物、三乙基胺以及溶剂的摩尔比为0.05-2.00:0.10-4.00:0.10-6.000:5-25。
5.根据权利要求2所述的合成方法,其特征在于:所述的二氟乙酸酐、1,3-二酮衍生物、三乙基胺以及溶剂的摩尔比为0.05-2.00:0.10-4.00:0.10-6.000:5-25。
6.根据权利要求1或2所述的合成方法,其特征在于:所述1,3-二酮衍生物的结构式为;其具体为下述式1-式23中的任意一种:
。
7.根据权利要求1所述的合成方法,其特征在于:所得2-(2,2,2-三氟亚乙基)-1,3-二酮的结构通式为:,其具体为下述式1-式23中的任意一种:
。
8.根据权利要求2所述的合成方法,其特征在于:所得2-(2,2-二氟乙基)-1,3-二酮的结构通式为:,其具体为下述式1-式10中的任意一种:
。
9.根据权利要求1或2所述的合成方法,其特征在于:所述加热反应的温度为80-130℃,反应时间为20 h。
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