CuI/2,2'-联吡啶/2,2,6,6-四甲基哌啶氧化物催化氧化醇生成腈的工艺

doi:10.11944/j.issn.1000-0518.2018.11.170446

摘要/Abstract

摘要：

以高压反应釜为反应装置,采用CuI/Bipy(2,2'-联吡啶)/TEMPO(2,2,6,6-四甲基哌啶氧化物)催化体系,以氨水作氮源,分子氧作氧化剂,对醇催化氧化生成相应腈的方法进行了优化。以苯甲醇的催化氧化反应为模型反应,考察了催化剂及其用量、溶剂、反应温度以及时间对催化性能的影响。实验表明:在高压釜中,120 ℃、40×10⁵ Pa的氮氧混合气(φ(O₂)=8%)条件下,将催化剂摩尔分数降低至1%(脂肪醇催化剂摩尔分数为5%),反应时间缩短至8 h时,催化效果最佳。同时,该反应系统对于不同的芳香醇和脂肪醇的氧化均取得了90%以上的转化率和90%以上的产品收率。

关键词: 醇, 腈, 催化氧化, 高压反应釜

Abstract:

CuI/Bipy(2,2'-bipyridine)/TEMPO(2,2,6,6-Tetramethylpiperidinooxy) catalytic oxidation process was optimized for nitriles synthesis using alcohols as starting material with aqueous ammonia as nitrogen source and molecular oxygen as the oxidant in a pressurized reactor. The effect of copper salts, catalyst loading, solvent, reaction temperature and reaction time were studied using benzyl alcohol as a model substrate. It is shown that low catalyst loading(1% molar fraction for aromatic alcohols, 5% molar fraction for aliphatic alcohols) and short reaction time(8 hours) are required for oxidizing both aromatic and aliphatic alcohols to their corresponding nitriles over 90% conversion rate and 90% yield under 40×10⁵ Pa presure of O₂(8% volume fraction)-N₂ gas mixture at 120 ℃.

Key words: alcohols, nitriles, catalytic oxidation, high pressure reactor

徐坤仑,曹祖宾,乔海燕,韩冬云,石薇薇. CuI/2,2'-联吡啶/2,2,6,6-四甲基哌啶氧化物催化氧化醇生成腈的工艺[J]. 应用化学, 2018, 35(11): 1335-1341.

XU Kunlun,CAO Zubin,QIAO Haiyan,HAN Dongyun,SHI Weiwei. CuI/2,2'-Bipyridine/2,2,6,6-Tetramethylpiperidinooxy Catalytic Oxidation Process of Alcohol to Nitrile[J]. Chinese Journal of Applied Chemistry, 2018, 35(11): 1335-1341.

参考文献

[1]	Lee G A,Freedman H H.Phase Transfer Catalyzed Oxidations of Alcohols and Amines by Aqueous Hypochlorite[J]. Tetrahedron Lett,1976,17(20):1641-1644.
[2]	Miller J S,Manson J L.Designer Magnets Containing Cyanides and Nitriles[J]. Acc Chem Res,2001,34(7):563-570.
[3]	Smith M B,March J.March's Advanced Organic Chemistry:Reactions, Mechanisms, and Structure, Sixth Edition[J]. Molecules,2006,6(12):1064-1065.
[4]	Fleming F F,Yao L,Ravikumar P C,et al. Nitrile-containing Pharmaceuticals:Efficacious Roles of the Nitrile Pharmacophore[J]. J Med Chem,2010,53(22):7902-7917.
[5]	Trumm S,Wipff G,Geist A,et al. Optimising BTP Ligands by Tuning Their Basicity[J]. Radiochim Acta,2011,99(1):13-16.
[6]	Tamilselvan P,Basavaraju Y B,Sampathkumar E,et al. Cobalt(II) Catalyzed Dehydration of Aldoximes:A Highly Efficient Practical Procedure for the Synthesis of Nitriles[J]. Catal Commun,2009,10(5):716-719.
[7]	Ghorbani-Vaghei R,Shiri L,Ghorbani-Choghamarani A. An Efficient, Rapid and Facile Procedure for Conversion of Aldoximes to Nitriles Using Triphenylphosphine and N-Halo Sulfonamides[J]. Chinese Chem Lett,2013,24(12):1123-1126.
[8]	Tang X,An J,Denton R M.A Procedure for Appel Halogenations and Dehydrations Using a Polystyrene Supported Phosphine Oxide[J]. Tetrahedron Lett,2014,55(4):799-802.
[9]	Shu Z,Ye Y,Deng Y,et al. Palladium(Ⅱ)-Catalyzed Direct Conversion of Methyl Arenes into Aromatic Nitriles[J]. Angew Chem Int Ed,2013,52(40):10573-10576.
[10]	Jasem Y A,Barkhad M,Khazali M A,et al. Two Ways of Preparing Benzonitriles Using BrCCl3-PPh3 as the Reagent[J]. J Chem Res,2014,38(2):80-84.
[11]	Biondini D,Brinchi L,Germani R,et al. Dehydrogenation of Amines to Nitriles in Aqueous Micelles[J]. Eur J Org Chem,2005,2005(14):3060-3063.
[12]	Kim J,Chang S.A New Combined Source of “CN” from N,N-Dimethylformamide and Ammonia in the Palladium-Catalyzed Cyanation of Aryl C—H Bonds[J]. J Am Chem Soc,2010,132(30):10272-10274.
[13]	Lamani M,Prabhu K R.An Efficient Oxidation of Primary Azides Catalyzed by Copper Iodide:A Convenient Method for the Synthesis of Nitriles[J]. Angew Chem Int Ed,2010,49(37):6622-6625.
[14]	Rokade B V,Malekar S K,Prabhu K R.A Novel Oxidative Transformation of Alcohols to Nitriles:An Efficient Utility of Azides as a Nitrogen Source[J]. Chem Commun,2012,48(44):5506-5508.
[15]	Oishi T,Yamaguchi K,Mizuno N.Catalytic Oxidative Synthesis of Nitriles Directly from Primary Alcohols and Ammonia[J]. Angew Chem Int Ed,2009,48(34):6286-6288.
[16]	Yamaguchi K,He J,Oishi T,et al. The “Borrowing Hydrogen Strategy” by Supported Ruthenium Hydroxide Catalysts:Synthetic Scope of Symmetrically and Unsymmetrically Substituted Amines[J]. Chem-Eur J,2010,16(24):7199-7207.
[17]	Nie R,Shi J,Xia S,et al. MnO2/Graphene Oxide:A Highly Active Catalyst for Amide Synthesis from Alcohols and Ammonia in Aqueous Media[J]. J Mater Chem,2012,22(35):18115-18118.
[18]	Ishida T,Watanabe H,Takei T,et al. Metal Oxide-catalyzed Ammoxidation of Alcohols to Nitriles and Promotion Effect of Gold Nanoparticles for One-Pot Amide Synthesis[J]. Appl Catal,A,2012,425:85-90.
[19]	Dornan L M,Cao Q,Flanagan J C A,et al. Copper/TEMPO Catalysed Synthesis of Nitriles from Aldehydes or Alcohols Using Aqueous Ammonia and with Air as the Oxidant[J]. Chem Commun,2013,49(54):6030-6032.
[20]	Tao C,Liu F,Zhu Y,et al. Copper-catalyzed Aerobic Oxidative Synthesis of Aryl Nitriles from Benzylic Alcohols and Aqueous Ammonia[J]. Org Biomol Chem,2013,11(20):3349-3354.
[21]	Dighe S U,Chowdhury D,Batra S.Iron Nitrate/TEMPO:A Superior Homogeneous Catalyst for Oxidation of Primary Alcohols to Nitriles in Air[J]. Adv Synth Catal,2014,356(18):3892-3896.
[22]	Yin W,Wang C,Huang Y.Highly Practical Synthesis of Nitriles and Heterocycles from Alcohols Under Mild Conditions by Aerobic Double Dehydrogenative Catalysis[J]. Org Lett,2013,15(8):1850-1853.
[23]	Zhang Y,Huang R,Gao B,et al. Solvent-Free Aerobic Oxidation of Alcohols to Nitriles Catalyzed by Copper Iodide in Combination with a Quaternary Ammonium Modified TEMPO[J]. Catal Lett,2016,146(1):220-228.
[24]	Jagadeesh R V,Junge H,Beller M.Green Synthesis of Nitriles Using Non-Noble Metal Oxides-based Nanocatalysts[J]. Nat Commun,2014,5:4123-4130.
[25]	Osterberg P M,Niemeier J K,Welch C J,et al. Experimental Limiting Oxygen Concentrations for Nine Organic Solvents at Temperatures and Pressures Relevant to Aerobic Oxidations in the Pharmaceutical Industry[J]. Org Process Res Dev,2014,19(11):1537-1543.
[26]	Rogan L,Hughes N L,Cao Q,et al. Copper(Ⅰ)/ketoABNO Catalysed Aerobic Alcohol Oxidation[J]. Catal Sci Technol,2014,4(6):1720-1725.
[27]	Hoover J M,Ryland B L,Stahl S S.Copper/TEMPO-Catalyzed Aerobic Alcohol Oxidation:Mechanistic Assessment of Different Catalyst Systems[J]. ACS Catal,2013,3(11):2599-2605.
[28]	Zhang G,Zhang G,Lei J,et al. Aerobic Alcohol Ammoxidation Catalyzed by Copper(Ⅰ)/Amino Acid:A Scalable Protocol to Nitriles[J]. Chem Res Chinese Univ,2016,32(4):586-593.