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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

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Front Chem Sci Eng    2013, Vol. 7 Issue (2) : 226-232    https://doi.org/10.1007/s11705-013-1321-x
RESEARCH ARTICLE
Facile synthesis of isoindoline-1,3-diones by palladium-catalyzed carbonylative cyclization of o-bromobenzoic acid and primary amines
Mayur V. KHEDKAR, Bhalchandra M. BHANAGE()
Department of Chemistry, Institute of Chemical Technology, Matunga, Mumbai 400019, India
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Abstract

A facile method for the carbonylative cyclization of o-bromobenzoic acid with primary amine using Pd(OAC)2 as a metal precursor and 1,1'-bis(diphenylphosphino)ferrocene (dppf) as a ligand has been developed. The effect of various reaction parameters such as ligand, solvent, base, time and temperature on this cyclization was studied. The optimized protocol was used for a wide variety of substituted aryl amines with different steric and electronic properties, affording the corresponding isoindoline-1,3-diones in good to excellent yields under atmospheric pressure of carbon monoxide at 100°C within 10 h using 1,4-diazabicyclo[2.2.2]octane (DABCO) as a base. The reaction system finds attractive alternative to the conventional multistep synthetic process and thus represents an effective utilization of carbonylative protocol for synthesis of valuable chemicals.
Keywords carbonylative cyclization reactions      isoindole-1,3-dinones      homogeneous catalysis      dppf     
Corresponding Author(s): BHANAGE Bhalchandra M.,Email:bm.bhanage@gmail.com, bm.bhanage@ictmumbai.edu.in   
Issue Date: 05 June 2013
 Cite this article:   
Mayur V. KHEDKAR,Bhalchandra M. BHANAGE. Facile synthesis of isoindoline-1,3-diones by palladium-catalyzed carbonylative cyclization of o-bromobenzoic acid and primary amines[J]. Front Chem Sci Eng, 2013, 7(2): 226-232.
 URL:  
https://academic.hep.com.cn/fcse/EN/10.1007/s11705-013-1321-x
https://academic.hep.com.cn/fcse/EN/Y2013/V7/I2/226
Fig.1  Carbonylative cyclization of -bromobenzoic acid
Fig.2  Structures of the phosphine ligands -
EntryLigandSolventBaseTemperatur/°CYield /%b)
Effect of ligand
1-TolueneDABCO1000
2L1TolueneDABCO10020
3L2TolueneDABCO10010
4L3TolueneDABCO1005
5L4TolueneDABCO10015
6L5TolueneDABCO10010
7L6TolueneDABCO10085
8c)L6TolueneDABCO10060
Effect of solvent
9L6DMFDABCO10040
10L6CH3CNDABCO1005
11L6WaterDABCO1000
Effect of base
12L6TolueneEt3N10060
13L6TolueneK2CO310010
14L6TolueneCs2CO310015
Effect of temperature
15L6TolueneDABCO9070
16L6TolueneDABCO11087
17d)L6TolueneDABCO10075
a) Reaction conditions: 2-bromobenzoic acid (1 mmol), aniline (1.5 mmol), Pd(OAc)2 (5 mol-%), ligand (10 mol%), base (2 mmol), solvent (10 mL), 1 atm CO, and 10 h.b) GC Yield. c) Pd(OAc)2 (2.5 mol%). d) Reaction time 8 h.
Tab.1  Optimization of carbonylative cyclization of -bromobenzoic acid
Entryo-bromobenzoic acidAmineProductYield/%b)
183
22a79
31a85
41a86
51a79
61a90
71a89
81a76
91a70
101a89
111a91
121a90
a) Reaction conditions: o-bromobenzoic acid (1 mmol), amine (1.5 mmol), Pd(OAc)2 (5 mol-%), dppf (10 mol-%), DABCO (2 mmol), toluene (10 mL), CO (1 atm), 100°C, 10 h;b) Isolated yield
Tab.2  Reaction of -bromobenzoic acid with different aromatic and aliphatic amines
Fig.3  Plausible reaction mechanism of carbonylative cyclization of -bromobenzoic acid
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