Page 214 - 《精细化工》2022年第7期
P. 214
·1500· 精细化工 FINE CHEMICALS 第 39 卷
green oxidation system of catalytic oxidation synthesis of phenylacetone
by ethylene benzene[J]. Gansu Science and Technology (甘肃科技),
2011, 27(22): 51-54.
[4] LI J Q (李家其), GUO J (郭军),YIN D L (尹笃林). Progress on
ethylbenzene catalytic oxidation to synthesize acetophenone[J]. Fine
Chemical Intermediates (精细化工中间体), 2005, 35(4): 1-3.
[5] LI G X (李贵贤), LI Y Z (李亚珍), XU Y D (徐彦铎), et al.
Advances in development of catalysts for liquid-phase oxidation of
ethylbenzene to acetophenone[J]. Applied Chemical Industry (应用
化工), 2012, 41(8): 1412-1416.
[6] XU Y, HU X B, SHAO J, et al. Hydration of alkynes at room
temperature catalyzed by gold (Ⅰ) isocyanide compounds[J]. Green
Chemistry, 2015, 17(1): 532-537.
[7] LIU W L (刘文杰), LI J H (李金恒). Cerium(Ⅳ) sulfate-catalyzed
hydration[J]. Chinese Journal of Organic Chemistry (有机化学), 2006,
26(8): 1073-1078.
[8] HINTERMANN L, LABONNE A. Catalytic hydration of alkynes
and its application in synthesis[J]. Synthesis, 2007, (8): 1121-1150.
图 6 反应机理 [9] BUDDE W L, DESSY R E. The homogeneously catalyzed hydration
Fig. 6 Reaction mechanism of acetylenes by mercuric perchlorate-perchloric acid: Evidence for a
bis-(acetylene)-mercuric ion complex as an intermediate[J]. Journal
由图 6 可见,炔烃首先扩散到 HBeta 的外表面, of the American Chemical Society, 1963, 85(24): 3964-3970.
[10] GOODWIN J A, APONICK A. Regioselectivity in the Au-catalyzed
随后吸附到布朗斯特酸性位点(BAS,弱酸和中强 hydration and hydroalkoxylation of alkynes[J]. Chemical Communications,
酸位点)上,形成 ArC≡≡C-BAS 加合物Ⅰ(1)。 2015, 51(42): 8730-8741.
[11] XU C X, DU W Y, ZENG Y, et al. Reactivity switch enabled by
水分子和被 BAS 活化后的三键通过加成反应生成
counterion: Highly chemoselective dimerization and hydration of
不稳定的烯醇中间体Ⅱ(2)。随后,烯醇在 BAS terminal alkynes [J]. Organic Letters, 2014, 16(3): 948-951.
上经过两个平行的单电子转移过程,形成稳定的水 [12] HIRONOBU K, KEIJI U, SHUNICHI F, et al. Isolation and crystal
structures of both enol and keto tautomer intermediates in a hydration
合产物芳香酮Ⅲ(3)。最后,芳香酮从催化剂的 of an alkyne-carboxylic acid ester catalyzed by iridium complexes in
BAS 脱附,形成最终产物芳香酮,同时催化剂得到 water[J]. Journal of American Chemical Society, 2008, 130(50):
循环使用(4)。 17141-17147.
[13] FRANCESCO T, ANDREW M C, ALESSANDRO S, et al. Platinum
(Ⅱ) diphosphinamine complexes for the efficient hydration of alkynes
3 结论 in micellar media[J]. Advanced Synthesis and Catalysis, 2012, 354(16):
1095-1104.
本文以廉价易得的酸性沸石 HBeta 为催化剂, [14] JIN X J, OISHI T, YAMAGUCHI K, et al. Heterogeneously catalyzed
efficient hydration of alkynes to ketones by tin-tungsten mixed oxides[J].
在温和的条件下,实现了多种芳基酮的绿色合成。
Chemistry A European Journal, 2011, 17(4): 1261-1267.
该体系避免了有机配体、高毒性催化剂和贵金属盐 [15] ÖTVÖS S B, SZÉCSÉNYI Z, FÜLӦP F, et al. Bismuth(Ⅲ)-
催化剂的使用,因此,该催化体系更加清洁,产物 catalyzed hydration of terminal alkynes: Sustainable synthesis of
methyl ketones in batch and flow[J]. American Chemical Society
提纯更加简便,大大降低了该工艺的能源消耗。同 Sustainable Chemistry and Engineering, 2019, 7(15): 13286-13293.
时 HBeta 催化剂在催化芳基炔烃水合体系中循环使 [16] PARK J, YEON J, LEE P H, et al. Iron-catalyzed indirect hydration
of alkynes in presence of methanesulfonic acid[J]. Tetrahedron Letters,
用 4 次依然有较好的活性(第 5 次使用后产率仍可
2013, 54(33): 4414-4417.
达 99%),表现出了优异的可重复使用性能。经过 [17] HASSAM M, LI W S. Copper-catalyzed markovnikov hydration of
对反应条件的优化和底物适用范围的考察发现:该 alkynes[J]. Tetrahedron, 2015, 71(18): 2719-2723.
[18] GAO L F, ZHUGE W Y, FENG X, et al. Co/rGO synthesized via the
催化体系在相对温和的条件下(120 ℃,6 h)对大 Alcohol-thermal method as a heterogeneous catalyst for the highly
量的芳基炔烃表现出了良好的兼容性,产物的产率 efficient oxidation of ethylbenzene with oxygen[J]. New Journal of
均高于 90%。 Chemistry, 2019, 43(21): 8189-8194.
[19] YU X Y (于心玉), GAO S (高珊), LIU C H (刘彩华), et al.
Preparation of 2-t-butyl-p-cresol catalyzed by Hβ zeolite[J]. Fine
参考文献:
Chemicals (精细化工), 2006, 23(6): 598-600.
[1] YANG X (杨晰), LONG H T (龙海涛). Research progress on [20] TAO T Y (陶庭雨), FU W Q (傅雯倩). Preparation of a Ni 2P/HZSM-5
catalytic oxidation of ethylbenzene to acetophenone by oxygen[J]. catalyst and its catalytic performance for phenylacetylene selective
Industrial Catalysts (工业催化), 2021, 29(8): 19-25. hydrogenation[J]. Fine Chemicals (精细化工), 2019, 34(5): 929-934.
[2] SUN Y (孙宇), SHI W W (石薇薇), SHEN J (沈健). Synthesis of [21] MU M M (穆曼曼), CHEN L G (陈立功). Progress of Friedel-Crafts
acetophenone by catalytic oxidation of ethylbenzene over V-SBA-15[J]. acylation of arenes over solid acid catalysts[J]. Fine Chemicals (精细
Gas Chemical Industry (天然气化工), 2016, 41(6): 44-48. 化工), 2017, 34(4): 361-367.
[3] MA J J (马建军), LI L (李莉), MAO Z H (毛志红), et al. Progress in (下转第 1512 页)