Stable and reusable nanoscale Fe2O3-catalyzed aerobic oxidation process for the selective synthesis of nitriles and primary amides

Stable and reusable nanoscale Fe2O3-catalyzed aerobic oxidation process for the selective synthesis of nitriles and primary amides

Green Chem., 2018, Advance Article
DOI: 10.1039/C7GC02627G, Paper

Kathiravan Murugesan, Thirusangumurugan Senthamarai, Manzar Sohail, Muhammad Sharif, Narayana V. Kalevaru, Rajenahally V. Jagadeesh
Nanoscale Fe₂O₃-catalyzed environmentally benign synthesis of nitriles and amides has been performed from easily accessible aldehydes and ammonia using O₂.

http://pubs.rsc.org/en/Content/ArticleLanding/2018/GC/C7GC02627G?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

Stable and reusable nanoscale Fe₂O₃-catalyzed aerobic oxidation process for the selective synthesis of nitriles and primary amides

 

Kathiravan Murugesan,^a  Thirusangumurugan Senthamarai,^a  Manzar Sohail,^b  Muhammad Sharif,^b  Narayana V. Kalevaru^a  and  Rajenahally V. Jagadeesh*^a 

Author affiliations

* Corresponding authors

^a Leibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, Germany
E-mail:Jagadeesh.Rajenahally@catalysis.de

^b The Center of Research Excellence in Nanotechnology (CENT) and Department of Chemistry, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia

Abstract

The sustainable introduction of nitrogen moieties in the form of nitrile or amide groups in functionalized molecules is of fundamental interest because nitrogen-containing motifs are found in a large number of life science molecules, natural products and materials. Hence, the synthesis and functionalization of nitriles and amides from easily available starting materials using cost-effective catalysts and green reagents is highly desired. In this regard, herein we report the nanoscale iron oxide-catalyzed environmentally benign synthesis of nitriles and primary amides from aldehydes and aqueous ammonia in the presence of 1 bar O₂ or air. Under mild reaction conditions, this iron-catalyzed aerobic oxidation process proceeds to synthesise functionalized and structurally diverse aromatic, aliphatic and heterocyclic nitriles. Additionally, applying this iron-based protocol, primary amides have also been prepared in a water medium.

1H NMR (300 MHz, Chloroform-d) δ 7.17 – 6.96 (m, 2H), 6.93 – 6.70 (m, 1H), 4.33 – 4.11 (m, 4H). 13C NMR (75 MHz, Chloroform-d) δ 147.75 , 143.80 , 125.87 , 121.21 , 118.91 , 118.25 , 104.38 , 64.59 , 64.12 . Off white solid

  

cas 19102-07-9

• 1,4-Benzodioxan-6-carbonitrile (8CI)
• 2,3-Dihydro-1,4-benzodioxin-6-carbonitrile
• 1-(2,3-Dihydrobenzo[b][1,4]dioxin-6-yl)nitrile

MP

Melting Point, °C
105 - 106 Tetrahedron, 2015, vol. 71,  29, p. 4883 - 4887

NMR PREDICTS

1H NMR

13C NMR PREDICT

More................

Journal of the American Chemical Society, 2001, vol. 123, 49, p. 12202 - 12206

More.............

RSC Advances, 2013, vol. 3, 44, p. 22389 - 22396

http://www.rsc.org/suppdata/ra/c3/c3ra44386h/c3ra44386h.pdf

  

MORE........

Organic Letters, 2017, vol. 19,  12, p. 3095 - 3098

http://pubs.acs.org/doi/suppl/10.1021/acs.orglett.7b01199/suppl_file/ol7b01199_si_001.pdf

2,3-Dihydrobenzo[b][1,4]dioxine-6-carbonitrile (Scheme 1, 2n) According to the general procedure A, the reaction of 1n (0.20 mmol), zinc cyanide (2.0 equiv), PCyPh2 (0.20 equiv) and Pd(OAc)2 (0.05 equiv) in dioxane (0.25 M) for 16 h at 150 °C, afforded after work-up and chromatography the title compound in 75% yield (24.2 mg). White solid. 1H NMR (500 MHz, CDCl3) δ 7.17-7.11 (m, 2H), 6.91 (d, J = 8.1 Hz, 1H), 4.32-4.31 (m, 2H), 4.30- 4.26 (m, 2H). 13C NMR (125 MHz, CDCl3) δ 147.84, 143.91, 126.04, 121.37, 119.01, 118.37, 104.62, 64.71, 64.24.

 

//////////////