Reductive carbonylation of 2,4-dinitrotoluene to 2,4-toluendiurethane with palladium(1,10-phenanthroline)2(hexafluorophosphate)2, as catalyst, and 1,10-phenanthrolinium hexafluorophosphate, as cocatalyst.

Santi, R.; Romano, Antonino Davide; Panella, F.; Mestroni, G.; Santi, A. Sessanti O.

doi:10.1016/s1381-1169(98)00379-3

Cited by 33 publications

(22 citation statements)

References 15 publications

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“…2-methylquinoline is probably formed during condensation of aniline with croton aldehyde (Eqs. (5) and (6)) [9,39], in agreement with our previous reports [31,32].…”

Section: Resultssupporting

confidence: 92%

“…Carbonylation of nitrocompounds [1][2][3][4][5] and amines [6][7][8][9][10] is particularly important in polymer industry -during production of carbamates, isocyanates and ureas. Carbonylation of amines is efficiently catalyzed by square planar palladium(II) complexes with nitrogen donor ligands [11][12][13][14][15][16][17][18][19][20][21] and two directions of this process are possible -the process carried out in alcohols leads to carbamates (Eq.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

One pot synthesis of ureas and carbamates via oxidative carbonylation of aniline-type substrates by CO/O2 mixture catalyzed by Pd-complexes

Krogul

Litwinienko

2015

Journal of Molecular Catalysis A: Chemical

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“…2-methylquinoline is probably formed during condensation of aniline with croton aldehyde (Eqs. (5) and (6)) [9,39], in agreement with our previous reports [31,32].…”

Section: Resultssupporting

confidence: 92%

Section: Introductionmentioning

confidence: 99%

One pot synthesis of ureas and carbamates via oxidative carbonylation of aniline-type substrates by CO/O2 mixture catalyzed by Pd-complexes

Krogul

Litwinienko

2015

Journal of Molecular Catalysis A: Chemical

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“…The reason is not known for sure, but it may be contrasted with the positive effect that acids have on the carbonylation of nitroarenes to methyl arylcarbamates. [37,[64][65][66][70][71][72] In the latter case, contrary to the reactions described in this review, the reaction proceed through the intermediate formation of anilines [51] and the role of the acidic promoter appears to play at least two different roles. One is to act as a bifunctional promoter, accelerating a proton transfer in the rate-determining carbonylation of aniline, and is well understood.…”

Section: Additivesmentioning

confidence: 55%

Transition Metal Catalyzed Reductive Cyclization Reactions of Nitroarenes and Nitroalkenes

2019

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Nitroarenes are the entry point for the production of most nitrogen‐containing aromatic compounds. Thus, any transformation that leads directly from them to the final product allows saving one or more synthetic steps. This review deals with homogeneously catalyzed reactions leading to the formation of N‐heterocyclic compounds from nitroarenes or nitroalkenes in one pot. Reactions that lead to the intermediate formation of amines are not considered. Carbon monoxide is the most often employed reductant because it allows selective reactions, is cheap, and only produces CO2 as stoichiometric byproduct. However, the difficulty in handling pressurized CO has stimulated in recent years the development of CO‐surrogates, that is molecules able to liberate CO during the reaction. The use of phosphines and diols has also been developed in conjunction with molybdenum catalysts. The review focusses in more detail on the literature in the period 2006–2018, but reference to earlier work is made when necessary to put recent results in a more general context.

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“…The highest ratio previously reported (at least in the free literature) is 500. [24] Catalyst Deactivation…”

Section: Full Papersmentioning

confidence: 99%

Carbonylation of Dinitrotoluene to Dimethyl Toluenedicarbamate; High Efficiency of Phosphorus Acids as Promoters for the Palladium-Phenanthroline Catalytic System

Gasperini

Ragaini

Cazzaniga

et al. 2005

Advanced Synthesis & Catalysis

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Phosphorus acids are excellent promoters for the palladium-phenanthroline catalyzed carbonylation of 2,4-dinitrotoluene to 2,4-toluenedicarbamate. For the first time, all intermediate nitrocarbamates and aminocarbamates have been independently synthesized and their amount after every catalytic reaction precisely quantified. An extensive optimization of all experimental variables has been carried out. The best acids are phenylphosphonic and 4-tolylphosphonic acids. The addition of 2,2-dimethoxypropane as an internal drying agent is highly beneficial. The addition of an amine derived from the starting dinitroarene increases both rate and selectivity of the carbonylation reaction. have been prepared for the first time. The latter displays a markedly higher solubility than all other [Pd(Phen) 2 ] 2 þ complexes. The effect of several possible promoters has also been investigated. Under the optimized experimental conditions, a 77.6% selectivity in dicarbamate was obtained when working at a molar ratio dinitrotoluene/Pd ¼ 2920. At the end of the reaction, the dicarbamate spontaneously precipitates out of the solution in high yields upon cooling, with no inclusion of the acid promoter or of phenanthroline. 2,6-Dinitrotoluene can also be efficiently carbonylated to the corresponding dicarbamate.

show abstract

Reductive carbonylation of 2,4-dinitrotoluene to 2,4-toluendiurethane with palladium(1,10-phenanthroline)2(hexafluorophosphate)2, as catalyst, and 1,10-phenanthrolinium hexafluorophosphate, as cocatalyst.

Cited by 33 publications

References 15 publications

One pot synthesis of ureas and carbamates via oxidative carbonylation of aniline-type substrates by CO/O2 mixture catalyzed by Pd-complexes

One pot synthesis of ureas and carbamates via oxidative carbonylation of aniline-type substrates by CO/O2 mixture catalyzed by Pd-complexes

Transition Metal Catalyzed Reductive Cyclization Reactions of Nitroarenes and Nitroalkenes

Carbonylation of Dinitrotoluene to Dimethyl Toluenedicarbamate; High Efficiency of Phosphorus Acids as Promoters for the Palladium-Phenanthroline Catalytic System

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