CN105669596B - 一种n,n‑二烷基胺基酚的制备方法 - Google Patents

一种n,n‑二烷基胺基酚的制备方法 Download PDF

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CN105669596B
CN105669596B CN201610129737.2A CN201610129737A CN105669596B CN 105669596 B CN105669596 B CN 105669596B CN 201610129737 A CN201610129737 A CN 201610129737A CN 105669596 B CN105669596 B CN 105669596B
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罗美明
贾磊
谢君瑶
高森
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Abstract

本发明公开了一种N,N‑二烷基胺基酚类化合物的制备方法。在有机溶剂中，在铁催化剂的作用下，以酚和O‑苯甲酰基‑N,N‑二烷基羟胺为原料，合成N,N‑二烷基胺基酚类化合物。本发明制备方法简单，反应条件非常温和，反应速度快，用少量铁盐或氧化物为催化剂，可大大降低成本。本发明方法可用于合成一系列N,N‑二烷基胺基酚类化合物，合成的产物可应用于合成染料、配体、医药等方面。

Description

一种N,N-二烷基胺基酚的制备方法
技术领域
本发明涉及一种N,N-二烷基胺基酚的制备方法，该方法在铁催化剂作用下以O-苯甲酰基-N,N-二烷基羟胺为胺化试剂与酚类化合物发生反应制备N,N-二烷基胺基酚。
背景技术
N,N-二烷基胺基酚是一类重要的化合物，广泛应用于合成染料、配体、医药等方面。传统制备N,N-二烷基胺基酚的方法包括卤代酚的胺解（J. Chem. Soc. B, 1970,1742; Russ. J. Org. Chem., 2007, 43, 1092），氨基酚的N-烷基化（Iran. J. Sci.Technol., 1978, 7, 153），偶氮化合物在醛类存在下的还原（J. Am. Chem. Soc., 1941,63, 751）等，这些方法需要先制备卤代酚、氨基酚等之后再转变为N,N-二烷基胺基酚，存在着反应步骤较多、条件苛刻、收率低、底物局限性高等缺陷。
直接从酚出发合成N,N-二烷基胺基酚的路线简捷、高效，但方法较少。
在三氟化硼的作用下，N-苯甲酰氧基哌啶与苯酚可以在较高的温度下邻位胺基化（J. Org. Chem. 1961, 26, 3013）。但是该反应在使用10倍当量的苯酚的情况下胺基化产物仍只有25%的收率，当苯酚的用量提高的20倍当量时，收率也仅仅达到32%。虽然该方法与本发明采用的胺化试剂相同，但采用的催化剂为三氟化硼至少需要等当量、反应温度高、苯酚用量大、收率低，并且底物仅局限于苯酚一例，不适合工业生产。
在奎宁类催化剂作用下，利用偶氮二羧酸酯可以实现2-萘酚的邻位胺基化（Angew. Chem. Int. Ed. 2006, 45, 1147），但该方法得到的产物为肼类产物，而且催化剂昂贵，底物局限性高。
N,N-二取代肼与2-萘酚反应可以生成N上未取代的1-氨基-2-萘酚，而不能得到N, N-二烷基胺基萘酚（J. Am. Chem. Soc., 2008, 130, 5840）。
在醋酸和异丙苯溶剂中，吩噻嗪、吩恶嗪等胺类底物与酚发生氧化偶联反应可以实现酚的邻位胺基化，但反应温度较高，胺类底物仅局限于吩噻嗪、吩恶嗪类化合物（Angew. Chem. Int. Ed., 2015, 54, 4102），不适合制备N,N-二烷基胺基酚。
发明内容
本发明提供了一种在铁催化剂的作用下，O-苯甲酰基-N,N-二烷基羟胺与酚直接反应合成N,N-二烷基胺基酚的方法。该方法反应速度快，条件温和，操作简单。
所述的N,N-二烷基胺基酚的结构如式（Ⅰ）所示：
（Ⅰ）
[所述的酚具有化学式（Ⅱ）的结构：
（Ⅱ）
[所述的O-苯甲酰基-N,N-二烷基羟胺具有化学式（Ⅲ）的结构：
（Ⅲ）
[化学式（Ⅰ）~（Ⅲ）中R1为H、烷基、烷氧基、卤素；或者为首尾各自连在芳环相邻碳原子上的烃基；O-苯甲酰基-N,N-二烷基羟胺（Ⅲ）中的R2R3N-为吗啉基、哌啶基、吡咯烷基、哌嗪基，或者R2、R3各自独立为碳原子数为1~12的烷基。
该制备方法用方程式表示如下：
[所述的催化剂为铁的盐或氧化物。
所述的O-苯甲酰基-N,N-二烷基羟胺与所述的酚的摩尔比为1:1~3:1，所述的催化剂与所述的酚的摩尔比为0.01:1~0.2:1。
所述的反应温度为25~100℃，更优选为25~40℃；所述的反应时间为0.2~6.0 h，优选为0.5~2.0 h，能够充分反应，以提高收率。
所述的有机溶剂为甲苯、氯苯、对二甲苯、1,4-二氧六环、1,2-二氯乙烷、甲醇、乙醇、二氯甲烷、乙腈、N,N-二甲基甲酰胺等，优选为甲苯，可以更好的提高收率。
所述的有机溶剂的用量无特别严格的要求，能将原料充分分散溶解即可，一般2.0mmol的酚原料溶剂用量为4.0 mL左右。
本发明的产品后处理包括：加入三乙胺调节pH, 减压蒸出溶剂，然后使用柱色谱进行分离。
与现有技术相比，本发明具有以下优点：
[本发明方法以铁的盐或氧化物为催化剂，反应条件温和，速度快，可大大降低成本。
本发明方法可用于合成一系列N,N-二烷基胺基酚化合物，合成的产物可应用于合成染料、配体、医药等方面。
实施例
下面结合实施详细说明本发明，但本发明并不仅限于此。
实施例 1
在氩气保护下，将N-苯甲酰氧基哌啶 (2.6 mmol) 的甲苯 (4.0 mL) 溶液加入到2-萘酚 (2.0 mmol) 与FeCl3 (0.2 mmol) 的混合物中，在常温下搅拌15 min，反应结束(TLC监测) 后，向体系中加入0.5 mL三乙胺，继续搅拌5 min，硅胶柱层析纯化，洗脱剂是石油醚:乙酸乙酯=20:1，得到白色固体1- (N-哌啶基) -2-萘酚，收率89%。1H NMR (400 MHz,CDCl3) δ (ppm): 8.30 (br s, 1H), 7.97 (d, J = 8.5 Hz, 1H), 7.77 (d, J = 8.2Hz, 1H), 7.61 (d, J = 8.8 Hz, 1H), 7.41 (t, J = 7.1 Hz, 1H), 7.23-7.28 (m,2H), 3.58 (td, J = 11.7, 1.9 Hz, 2H), 2.99 (d, J = 11.2 Hz, 2H), 1.42-1.82(m, 6H); 13C NMR (100 MHz, CDCl3) δ (ppm): 151.6, 132.2, 129.9, 129.5, 129.4,128.1, 125.8, 122.4, 122.3, 116.0, 52.3, 27.8, 24.2。
实施例 2：比较例
在氩气保护下，将N-苯甲酰氧基哌啶 (2.6 mmol) 的甲苯 (4.0 mL) 溶液加入到2-萘酚 (2.0 mmol) 与BF3·Et2O (2.0 mmol) 的混合物中，在常温下搅拌30 h，TLC监测无预期产物1- (N-哌啶基) -2-萘酚生成。
实施例 3
在氩气保护下，将N-苯甲酰氧基哌啶 (2.6 mmol) 的氯苯 (4.0 mL) 溶液加入到2-萘酚 (2.0 mmol) 与Fe2O3 (0.2 mmol) 的混合物中，在常温下搅拌15 h，反应结束 (TLC监测) 后，向体系中加入0.5 ml三乙胺，继续搅拌5 min，硅胶柱层析纯化，洗脱剂是石油醚:乙酸乙酯=20:1，得到白色固体1- (N-哌啶基) -2-萘酚，收率79%。
实施例 4
在氩气保护下，将N-苯甲酰氧基哌啶 (2.6 mmol) 的二氯甲烷 (4.0 mL) 溶液加入到6-甲基-2-萘酚 (2.0 mmol) 与FeCl2 (0.2 mmol) 的混合物中，在常温下搅拌，反应结束 (TLC监测) 后，反应结束后按实施例1处理，1- (N-哌啶基) -6-甲基-2-萘酚收率89%。1H NMR (400 MHz, CDCl3) δ (ppm): 8.23 (br s, 1H), 7.89 (d, J = 8.6 Hz,1H), 7.52-7.55 (m, 2H), 7.20-7.27 (m, 2H), 3.58 (t, J = 10.6 Hz, 2H), 2.99(d, J = 10.9 Hz, 2H), 2.45 (s, 3H), 1.43-1.82 (m, 6H); 13C NMR (100 MHz,CDCl3) δ (ppm): 150.8, 131.7, 130.2, 129.8, 128.4, 128.0, 127.4, 122.2,115.9, 52.3, 27.8, 24.2, 21.3。
实施例 5
在氩气保护下，将N-苯甲酰氧基哌啶 (2.6 mmol) 的二甲苯 (4.0 mL) 溶液加入到6-甲氧基-2-萘酚 (2.0 mmol) 与FeSO4(0.2 mmol) 的混合物中，在常温下搅拌，反应结束 (TLC监测) 后，反应结束后按实施例1处理，1- (N-哌啶基) -6-甲氧基-2-萘酚收率87%。1H NMR (400 MHz, CDCl3) δ (ppm): 8.15 (br s, 1H), 7.92 (d, J = 7.5 Hz,1H), 7.55 (d, J = 8.8 Hz, 1H), 7.25 (d, J = 8.8 Hz, 1H), 7.13-7.16 (m, 2H),3.91 (s, 3H), 3.57 (td, J = 11.6, 2.4 Hz, 2H), 3.02 (d, J = 11.5 Hz, 2H),1.45-1.94 (m, 6H); 13C NMR (100 MHz, CDCl3) δ (ppm): 155.0, 149.8, 130.4,130.3, 127.6, 126.6, 123.8, 118.4, 116.3, 107.5, 55.3, 52.4, 27.8, 24.2。
实施例 6
在氩气保护下，将N-苯甲酰氧基哌啶 (2.6 mmol) 的二氯乙烷 (4.0 mL) 溶液加入到7-甲氧基-2-萘酚 (2.0 mmol) 与Fe2(SO4)3 (0.2 mmol) 的混合物中，在常温下搅拌，反应结束 (TLC监测) 后，反应结束后按实施例1处理，1- (N-哌啶基) -7-甲氧基-2-萘酚收率84%。1H NMR (400 MHz, CDCl3) δ (ppm): 8.35 (br s, 1H), 7.70 (d, J = 8.9 Hz,1H), 7.57 (d, J = 8.7 Hz, 1H), 7.28 (s, 1H), 7.12 (d, J = 8.7 Hz, 1H), 6.98(dd, J = 8.9, 2.4 Hz, 1H), 3.96 (s, 3H), 3.60(td, J = 11.7, 2.5 Hz, 2H), 3.04(d, J = 12.1 Hz, 2H), 1.43-1.86 (m, 6H); 13C NMR (100 MHz, CDCl3) δ (ppm):157.6, 152.1, 133.3, 130.9, 129.1, 127.9, 124.8, 114.2, 113.4, 101.9, 55.3,51.9, 27.8, 24.3。
实施例 7
在氩气保护下，将N-苯甲酰氧基哌啶 (2.6 mmol) 的甲苯 (4.0 mL) 溶液加入到6-溴-2-萘酚 (2.0 mmol) 与Fe(OAc)3 (0.2 mmol) 的混合物中，在常温下搅拌，反应结束(TLC监测) 后，反应结束后按实施例1处理，1- (N-哌啶基) -6-溴-2-萘酚收率88%。1H NMR(400 MHz, CDCl3) δ (ppm): 8.30 (br s, 1H), 7.95 (d, J = 2.0 Hz, 1H), 7.87 (d,J = 9.1 Hz, 1H), 7.56 (d, J = 8.8 Hz, 1H), 7.50 (dd, J = 9.0, 2.1 Hz, 1H),7.28-7.30 (m, 1H), 3.54 (td, J = 11.7, 2.6 Hz, 2H), 3.00 (d, J = 12.2 Hz,2H), 1.45-1.98 (m, 6H); 13C NMR (100 MHz, CDCl3) δ (ppm): 151.9, 131.2, 130.6,130.1, 129.0, 127.2, 124.0, 117.1, 115.9, 52.3, 27.8, 24.1。
实施例8
实验操作按实施例1处理，6-羟基-5- (N-哌啶基) -2-萘甲酸乙酯收率87%。1HNMR (400 MHz, CDCl3) δ (ppm): 8.55 (s, 1H), 8.52 (br s, 1H), 8.00-8.05 (m,2H), 7.77 (d, J = 8.8 Hz, 1H), 7.32 (d, J = 8.8 Hz, 1H), 4.35 (q, J = 7.2 Hz,2H), 3.59 (td, J = 11.7, 2.5 Hz, 2H), 3.00 (d, J = 11.1 Hz, 2H), 1.49-1.95(m, 6H), 1.46 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ (ppm): 166.8,153.8, 134.4, 132.4, 130.1, 129.8, 128.4, 125.4, 124.3, 122.3, 116.7, 60.9,52.2, 27.8, 24.1, 14.4。
实施例 9
实验操作按实施例1处理，1- (N-哌啶基) -6-氰基-2-萘酚收率81%。1H NMR (400MHz, CDCl3) δ (ppm): 8.44 (br s, 1H), 8.08 (s, 1H), 7.95 (d, J = 8.8 Hz, 1H),7.61 (d, J = 8.8 Hz, 1H), 7.47 (d, J = 8.7 Hz, 1H), 7.28 (d, J = 8.8 Hz, 1H),3.44 (t, J = 11.5 Hz, 2H), 2.90 (d, J =11.3 Hz, 2H), 1.40-1.81 (m, 6H); 13CNMR (100 MHz, CDCl3) δ (ppm): 154.5, 135.5, 130.3, 129.4, 128.9, 128.4,126.4, 123.3, 119.6, 117.9, 105.6, 52.3, 27.7, 24.0。
实施例 10
实验操作按实施例1处理，1- (N-哌啶基)- 2,7-二萘酚收率71%。1H NMR (400MHz, CDCl3) δ (ppm): 7.67 (d, J = 8.8 Hz, 1H), 7.53 (d, J = 8.8 Hz, 1H), 7.30(d, J = 1.8 Hz, 1H), 7.08 (d, J = 8.8 Hz, 1H), 6.88 (dd, J = 8.8, 2.2 Hz,1H), 3.54 (td, J = 11.7, 2.2 Hz, 2H), 2.95 (d, J = 11.5 Hz, 2H), 1.38-1.83(m, 6H); 13C NMR (100 MHz, CDCl3) δ (ppm):153.6, 152.1, 133.3, 131.3, 128.8,128.0, 124.9, 114.1, 113.4, 104.9, 51.8, 27.8, 24.1。
实施例 11
实验操作按实施例1处理，5- (N-哌啶基)- 6-羟基喹啉收率77%。1H NMR (400MHz, CDCl3) δ (ppm): 8.72 (d, J = 3.3 Hz, 1H), 8.39 (d, J = 8.6 Hz, 1H), 8.21(br s, 1H), 7.97 (d, J = 9.0 Hz, 1H), 7.50 (d, J = 9.2 Hz, 1H), 7.35 (dd, J =8.4, 4.3 Hz, 1H), 3.50 (t, J = 11.4 Hz, 2H), 3.03 (d, J = 11.0 Hz, 2H), 1.47-1.85 (m, 6H); 13C NMR (100 MHz, CDCl3) δ (ppm): 151.8, 146.7, 144.2, 130.6,129.5, 129.2, 127.3, 120.4, 119.4, 52.6, 27.7, 24.1。
实施例 12
实验操作按实施例4处理，2- (N-哌啶基) -4-甲基苯酚收率40%。1H NMR (400MHz, CDCl3) δ (ppm): 6.95 (s, 1H), 6.85 (t, J = 2.0 Hz, 2H), 2.79 (t, J = 5.6Hz, 2H), 2.27 (s, 3H), 1.69-1.75 (m, 4H), 1.58-1.59 (m, 2H); 13C NMR (100 MHz,CDCl3) δ (ppm): 149.0, 140.1, 129.0, 126.3, 121.8, 113.3, 54.1, 26.8, 24.0,20.8。
实施例 13
实验操作按实施例1处理，2- (N-哌啶基) -4-甲基苯酚收率62%。1H NMR (400MHz, CDCl3) δ (ppm): 6.85 (d, J = 8.8 Hz, 1H), 6.73 (d, J = 2.8 Hz, 1H), 6.61(dd, J = 8.8, 2.8 Hz, 1H), 3.75 (s, 3H), 2.78 (t, J = 8.8 Hz, 4H), 1.70-1.74(m, 4H), 1.58-1.59 (m, 2H); 13C NMR (100 MHz, CDCl3) δ (ppm): 153.0, 145.4,140.9, 113.7, 110.1, 108.1, 55.8, 53.9, 26.8, 23.9。
实施例 14
实验操作按实施例1处理，6- (N-哌啶基) -2,4-二甲基苯酚收率62%。1H NMR(400 MHz, CDCl3) δ (ppm): 6.80 (s, 1H), 6.75 (s, 1H), 2.77 (t, J = 4.8 Hz,4H), 2.23 (s, 6H), 1.69-1.75 (m, 4H), 1.55-1.60 (m, 2H); 13C NMR (100 MHz,CDCl3) δ (ppm): 147.2, 139.6, 128.1, 127.8, 122.6, 119.0, 54.1, 26.9, 24.0,20.8, 15.8。
实施例 15
在氩气保护下，将N-苯甲酰氧基哌啶(4.0 mmol) 的甲苯 (4.0 mL) 溶液加入到3,5-二甲基苯酚 (2.0 mmol) 与FeCl3 (0.8 mmol) 的混合物中，在常温下搅拌，反应结束(TLC监测) 后，反应结束后按实施例1处理，2- (N-哌啶基) -3,5-二甲基苯酚收率65%。1HNMR (400 MHz, CDCl3) δ (ppm): 6.63 (s, 1H), 6.39 (s, 1H), 3.14-3.20 (m, 2H),2.83-2.86 (m, 2H), 2.34 (s, 3H), 2.24 (s, 3H), 1.84-1.87 (m, 1H), 1.69-1.75(m, 2H); 1.62-1.69 (m, 2H); 13C NMR (100 MHz, CDCl3) δ (ppm): 147.2, 139.6,128.1, 127.8, 122.6, 119.0, 54.1, 26.9, 24.0, 20.8, 15.8。
实施例 16
实验操作按实施例15处理，6-(N-哌啶基) -2-氯-4-甲氧基苯酚收率46%。1H NMR(400 MHz, CDCl3) δ (ppm): 6.66 (s, 1H), 6.63 (s, 1H), 3.74 (s, 3H), 2.78 (t,J = 5.2 Hz, 4H), 1.70-1.75 (m, 4H), 1.56-1.60 (m, 2H); 13C NMR (100 MHz,CDCl3) δ (ppm): 152.7, 141.9, 118.6, 110.3, 107.1, 100.0, 55.8, 53.8, 26.6,23.8。
实施例 17
实验操作按实施例1处理，1-二乙胺基- 2-萘酚收率83%。1H NMR (400 MHz,CDCl3) δ (ppm): 8.15 (br s, 1H), 7.72 (t, J = 8.0 Hz, 2H), 7.56 (d, J = 8.8Hz, 1H), 7.33 (t, J = 7.4 Hz, 1H), 7.16-7.21 (m, 2H), 3.20- 3.36 (m, 4H),0.93 (t, J = 7.2 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ (ppm): 153.8, 132.0,129.7, 129.6, 128.2, 125.8, 125.6, 122.4, 121.9, 115.7, 49.3, 14.6。
实施例 18
实验操作按实施例1处理，1-（N-吗啉基）- 2-萘酚收率87%。1H NMR (400 MHz,CDCl3) δ (ppm): 8.11 (br s, 1H), 8.04 (d, J = 8.5 Hz, 1H), 7.83 (d, J = 8.1Hz, 1H), 7.70 (d, J = 8.8 Hz, 1H), 7.49 (t, J = 7.0 Hz, 1H), 7.33 (t, J = 7.9Hz, 1H), 7.27-7.29 (m, 1H), 4.09 (d, J = 11.7 Hz, 2H), 3.95 (td, J = 11.4,2.8 Hz, 2H), 3.85 (td, J = 11.0, 2.0 Hz, 2H), 2.86 (d, J = 11.8 Hz, 2H); 13CNMR (100 MHz, CDCl3) δ (ppm): 151.6, 131.8, 129.6, 129.5, 128.8, 127.9,126.2, 122.7, 121.9, 116.1, 68.5, 50.9。
实施例 19
实验操作按实施例1处理，1-（N-吡咯烷基）- 2-萘酚收率76%。1H NMR (400 MHz,CDCl3) δ (ppm): 7.85 (d, J = 8.2 Hz, 1H), 7.73 (d, J = 8.5 Hz, 1H), 7.67 (d,J = 8.8 Hz, 1H), 7.46 (d, J = 8.0 Hz, 1H), 7.27-7.33 (m, 3H), 3.41 (s, 4H),2.23 (s, 4H); 13C NMR (100 MHz, CDCl3) δ (ppm): 153.3, 130.6, 129.8, 128.1,126.1, 125.9, 122.4, 121.3, 115.8, 51.7, 26.5。
实施例 20
实验操作按实施例1处理，1-(N-(N′-叔丁氧羰基哌嗪基))- 2-萘酚收率72%。1HNMR (400 MHz, CDCl3) δ (ppm): 8.10 (br s, 1H), 7.94 (d, J = 8.5 Hz, 1H), 7.82(d, J = 8.1 Hz, 1H), 7.69 (d, J = 8.8 Hz, 1H), 7.47 (t, J = 7.4 Hz, 7.27-7.34(m, 2H), 4.25 (s, 2H), 3.75 (t, J = 11.0 Hz, 2H), 2.95-3.16 (m, 4H), 1.55 (s,9H); 13C NMR (100 MHz, CDCl3) δ (ppm): 154.8, 151.4, 131.9, 129.5, 129.4,128.8, 128.2, 126.2, 122.7, 121.9, 116.2, 80.2, 50.7, 28.5。
实施例 21
实验操作按实施例1处理，1-(N-(N′-叔丁氧羰基哌嗪基))- 6-甲基-2-萘酚收率68%。1H NMR (400 MHz, CDCl3) δ (ppm): 7.93 (br s, 1H), 7.84 (d, J = 8.7 Hz,1H), 7.59-7.61 (m, 2H), 7.28-7.31 (m, 1H), 7.24 (d, J = 8.8 Hz, 1H), 4.23 (s,2H), 3.71 (t, J = 11.6 Hz, 2H), 2.92-3.12 (m, 4H), 2.48 (s, 3H), 1.55 (s,9H); 13C NMR (100 MHz, CDCl3) δ (ppm): 154.8, 150.7, 132.1, 130.0, 129.8,128.4, 128.2, 128.0, 121.8, 116.1, 80.1, 50.7, 28.5, 28.4, 21.2。
实施例 22
实验操作按实施例1处理，1-( N -(N′-叔丁氧羰基哌嗪基))- 6-溴-2-萘酚收率68%。1H NMR (400 MHz, CDCl3) δ (ppm): 7.94-7,97 (m, 2H), 7.80 (d, J =9.1 Hz,1H), 7.57 (d, J = 9.2 Hz, 1H), 7.50 (dd, J = 6.8, 2.6 Hz, 1H), 7.28-7.30 (m,2H), 2.23 (s, 2H), 3.65 (td, J = 11.6, 2.9 Hz, 2H), 2.92-3.14 (m,4H), 1.55(s, 9H); 13C NMR (100 MHz, CDCl3) δ (ppm): 155.0, 151.8, 131.3, 129.7, 129.4,128.5, 127.9, 123.6, 119.2, 117.4, 116.3, 80.6, 50.7, 28.5。

Claims (6)

1.一种N,N-二烷基胺基酚的制备方法，其特征在于，包括：在有机溶剂中，在铁催化剂的作用下，酚与O-苯甲酰基-N,N-二烷基羟胺进行反应，反应完成后经后处理得到具有下列化学式(I)的N,N-二烷基胺基酚：
(I)
所述的酚具有化学式（Ⅱ）的结构：
(II)
所述的O-苯甲酰基-N,N-二烷基羟胺具有化学式（Ⅲ）的结构：
(III)
化学式（Ⅰ）和（Ⅱ）中R1为H、甲基、甲氧基、卤素；或者R1首尾各自连在芳环相邻碳原子上形成取代的萘环、喹啉环，其中取代基是H、羟基、甲基、甲氧基、卤素、氰基、酯基；O-苯甲酰基-N,N-二烷基羟胺（Ⅲ）中的R2R3N-为吗啉基、哌啶基、吡咯烷基、哌嗪基，或者R2、R3各自独立为碳原子数为1~12的烷基。
2.根据权利要求1所述的方法，其特征在于，所述的铁催化剂为铁的盐或氧化物。
3.根据权利要求1所述的方法，其特征在于，所述的催化剂与所述的酚的摩尔比为0.01:1~0.2:1。
4.根据权利要求1所述的方法，其特征在于，所述的O-苯甲酰基-N,N-二烷基羟胺与所述的酚的摩尔比为1:1~3:1。
5.根据权利要求1所述的方法，其特征在于，所述的反应温度为25~100 ℃；所述的反应时间为0.2~6.0 h。
6.根据权利要求1所述的方法，其特征在于，所述的有机溶剂为甲苯、氯苯、二甲苯、1,4-二氧六环、1,2-二氯乙烷、甲醇、乙醇、二氯甲烷、乙腈、N,N-二甲基甲酰胺。
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