Page 229 - 《精细化工》2020年第7期

第 7 期 黄天宇，等: 可见光促进对称型芳香偶氮类化合物的合成 ·1511·

邻位带有卤素对位带有甲基的芳基胺为底物时（序 前，关于光促进对称型芳香偶氮类化合物的形成机
号 19~22），反应均能以较理想的收率（38%~ 81%） 理尚不明确，有待进一步的深入研究。
获得目标产物Ⅱs~v，并且产物 2,2-二碘-4,4-二甲
参考文献：
基偶氮苯（Ⅱs）可以继续作为原料进行下一步的转
[1] NGUYEN H T, COULEMBIER O, GHEVSEN K, et al.
[37]
化应用 。以上芳环带有卤素的芳香胺为底物的反 Copper-catalyzed dehydrogenative polycondensation of a bis-aniline
应中均能检测到原料剩余，由此确定并未发生乌尔 hexylthiophene-based monomer: A kinetically controlled air-tolerant
process[J]. Macromolecules, 2012, 45(23): 9547-9550.
曼-胺化反应。
[2] HUNGER K. Industrial dyes: chemistry, properties, applications[M].

①
表 3 室温下可见光催化合成芳香偶氮化合物 Wiley-VCH, Weinheim, 2003;
[3] JAUMANN E A, STEINWAND S, KLENIK S, et al. A combined
Table 3 Synthesis of aromatic azo compounds catalyzed by optical and EPR spectroscopy study: Azobenzene-based biradicals as
visible light at room temperature ① reversible molecular photoswitches[J]. Physical Chemistry Chemical
Physics, 2017, 19(26): 17263-17269.
序号 芳香胺 产物 收率 /%
②
[4] MARKIEWICZ G, PAKULSKI D, GALANTI A, et al.
1 Ⅰa Ⅱa 71 Photoisomerisation and light-induced morphological switching of a
2 Ⅰb Ⅱb 92 polyoxometalate- azobenzene hybrid[J]. Chemical Communications,
3 Ⅰc Ⅱc 90 2017, 53(53): 7278-7281.
[5] LI S W, FENG Y Y, LONG P, et al. The light-switching conductance
4 Ⅰd Ⅱd 53
of an anisotropic azobenzene-based polymer close-packed on
5 Ⅰe Ⅱe 77 horizontally aligned carbon nanotubes[J]. Journal of Materials
6 Ⅰf Ⅱf 60 Chemistry C, 2017, 5(21): 5068-5075.
7 Ⅰg Ⅱg 44 [6] SUZUKI T, MORIYA T, ENDO R, et al. A photo-responsive
polymeric azopyridine ligand with metal-complexation sensitivity:
8 Ⅰh Ⅱh 88
Application to coordination equilibrium studies on the polymer
9 Ⅰi Ⅱi 78 complexes of a cobalt(Ⅱ) Schiff base[J]. Polymer Chemistry, 2017,
10 Ⅰj Ⅱj 58 8(4): 761-768.
11 Ⅰk Ⅱk 68 [7] BARBERO M, DEGANI I, DUGHERA S, et al. Preparation of
diazenes by electrophilic C-coupling reactions of dry arenediazonium
12 Ⅰl Ⅱl 98
o-benzenedisulfonimides with Grignard reagents[J]. Synthesis-
13 Ⅰm Ⅱm 90 Stuttgart, 1998, (9): 1235-1237.
14 Ⅰn Ⅱn 80 [8] TSAI W J, SHIAO Y J, LIN S J, et al. Selective COX-2 inhibitors.
③
15 Ⅰo Ⅱo — Part 1: Synthesis and biological evaluation of phenylazobenzenesul-
fonamides[J]. Bioorganic & Medicinal Chemistry Letters, 2006,
③
16 Ⅰp Ⅱp —
16(17): 4440-4443.
17 Ⅰq Ⅱq 痕量 [9] LIU X, LI H Q, YE S, et al. Gold-catalyzed direct hydrogenative
18 Ⅰr Ⅱr 12 coupling of nitroarenes to synthesize aromatic azo compounds[J].
Angewandte Chemie International Edition, 2014, 53(29): 7624-7628.
19 Ⅰs Ⅱs 81
[10] ZHU H Y, KE X B, YANG X Z, et al. Reduction of nitroaromatic
20 Ⅰt Ⅱt 42
compounds on supported gold nanoparticles by visible and ultraviolet
21 Ⅰu Ⅱu 38 light[J]. Angewandte Chemie International Edition, 2010, 49(50):
22 Ⅰv Ⅱv 72 9657-9661.
[11] NOZAWA-KUMADA K, ABE E, ITO S, et al. Super electron
①反应条件：4-甲基苯胺（0.4 mmol），三（2,2-联吡啶）
donor-mediated reductive transformation of nitrobenzenes: A novel
二氯化钌（1%），碘化亚铜（15%），吡啶（0.6 mmol）和乙腈 strategy to synthesize azobenzenes and phenazines[J]. Organic &
（4 mL） 空气氛围下密闭，室温下 36 W 蓝光灯光照 12 h； Biomolecular Chemistry, 2018, 16(17): 3095-3098.
②分离收率；③不发生反应。 [12] SAKAI N, ASAMA S, ANAI S, et al. One-pot preparation of
azobenzenes from nitrobenzenes by the combination of an
3 结论 indium-catalyzed reductive coupling and a subsequent oxidation[J].
Tetrahedron, 2014, 70(11): 2027-2033.
[13] KIM S S B, HOMMER R B, CANNONT R D. The oxidation of
在室温下，以[(bpy) 3 Ru]Cl 2 （1%）为光敏剂， hydrazobenzene catalyzed by cobalt complexes in nonaqueous
CuI （15%）为催化剂，吡啶（0.6 mmol）为添加 solvents[J]. Bulletin of the Korean Chemical Society, 2006, 27(2):
255-265.
剂，乙腈为溶剂，36 W 蓝光灯光照 12 h 催化芳香 [14] SAHOO M K, SARAVANAKUMAR K, JAISWAL G, et al.
胺合成了 19 种对称型芳香偶氮类化合物，最高收率 Photocatalysis enabling acceptorless dehydrogenation of diaryl
hydrazines at room temperature[J]. ACS Catalysis, 2018, 8(8): 7727-7733.
可达 98%。考察了不同光敏剂、催化剂、添加剂、 [15] LV H, LAISHRAM R D, LI J, et al. Photocatalyzed oxidative
溶剂、反应时间以及光敏剂、催化剂和添加剂的用 dehydrogenation of hydrazobenzenes to azobenzenes[J]. Green
Chemistry, 2019, 21(15): 4055-4061.
量对反应的影响，确定了最优反应条件，通过底物
[16] DU K-S, HUANG J-M. Electrochemical dehydrogenation of hydrazines
拓展验证了该反应的底物适用性。该方法具有利用 to azo compounds[J]. Green Chemistry, 2019, 21(7): 1680-1685.
可见光促进反应，高效清洁且在室温下以空气中氧 [17] GOLDSTEIN S L, MCNELIS E. Migrations in oxidations of
trisubstituted anilines[J]. Journal of Organic Chemistry, 1973, 38(1):
气为氧化剂，无需外加氧化剂等优点，在合成对称 183-185.
型芳香偶氮类化合物方面具有广阔的应用前景。目 [18] FIROUZABADI H, MOSTAFAVIPOOR Z. Barium manganate-A