The nitrobenzene activation step in the carbonylation reaction using PdCl2/Fe/I2/Py catalytic system

Skupińska, Jadwiga; Karpińska, Monika; Ołówek, Maria

doi:10.1016/j.apcata.2005.01.030

Cited by 12 publications

(9 citation statements)

References 28 publications

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“…As we demonstrated previously, the process of carbonylation of NB contains a step of oxidative carbonylation of aniline (interme- Table 1 Parameters obtained for the carbonylation a of aniline by mixture of CO/O2, catalyzed by PdCl2(XnPy)2 complexes: conversion (C AN ) and yield (YEPC), of aniline, selectivity (SEPC) and turnover frequency (TOF) of PdCl2 ( [19,20,32]. PdCl 2 (X n Py) 2 complexes are effective catalysts for this process [19].…”

Section: Resultsmentioning

confidence: 98%

“…No substituent effects (in the aniline ring) on the yield of EPC or DPU in the presence of NB as an oxidizing agent was observed [32]. Surprisingly, significant substituent effects on the reaction yield were reported when molecular oxygen was employed [25].…”

Section: Introductionmentioning

confidence: 94%

“…In our laboratory was successfully applied the catalytic system PdCl 2 /Fe/I 2 /pyridine for carbonylation of aromatic amines in the presence of nitrobenzene (NB) or molecular oxygen as oxidizing agent to obtain ethyl N-phenylcarbamate (EPC) or N,Ndiphenylurea (DPU) [25,[30][31][32]. No substituent effects (in the aniline ring) on the yield of EPC or DPU in the presence of NB as an oxidizing agent was observed [32].…”

Section: Introductionmentioning

confidence: 97%

“…Mechanism of NB carbonylation proposed by Krogul and Skupinska [19,31,32] includes the formation of aniline (AN) as the first step with the electron transfer from palladium to nitro group of NB as a rate determining step. In general, carbonylation of NB can be considered as a carbonylation of AN with nitrobenzene being an oxidant [19] but mechanism of the carbonylation of AN catalyzed by PdCl 2 (X n Py) 2 complexes in the presence of oxidants other than NB still remains unsolved.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

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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Section: Resultsmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 94%

Section: Introductionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

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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“…In two recent papers [15,16] the authors have described the various transformations which have taken place during the carbonylation of nitrobenzene in the presence of the PdCl 2 /Fe/I 2 /Py catalyst system and have proposed intermediate palladium complexes formed in this reaction. Now the authors present preliminary results regarding the role of various catalyst system components.…”

Section: P Hn O 2 + 3co + Etoh → P Hn Hc(o)oetmentioning

confidence: 99%

The effect of the components of the PdCl2/Fe/I2/Py catalytic system on nitrobenzene carbonylation to ethyl N-phenylcarbamate

et al. 2005

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Abstract:The PdCl 2 /Fe/I 2 /Py catalytic system (Py -pyridine), reported to be highly active in the reaction of nitrobenzene carbonylation to ethyl phenylcarbamate was studied. The present paper describes the role of catalyst components and its effect on the activity and selectivity of the catalyst. The increase in the amount of PdCl 2 in the system while retaining a constant level of the other catalyst components, results in the increase of both carbamate and aniline yields. The increase in the amount of iron while retaining the other components constant, initially causes an increase in the carbamate yield; however, at Fe : Pd ratios higher than 36, the carbamate yield remains constant. The change in the amount of iron has no effect on the amount of aniline formed in the system. An increase in the amount of iodine in the system while retaining the other components constant, results in a decrease in carbamate yield and a considerable increase in the aniline yield of the reaction products.

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Biomass‐Derived, Target Specific, and Ecologically Safer Insecticide Active Ingredients

Goculdas,

Ramirez,

Crossley

et al. 2024

ChemSusChem

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With the continuous increase in food production to support the growing population, ensuring agricultural sustainability using crop‐protecting agents, such as pesticides, is vital. Conventional pesticides pose significant environmental risks, prompting the need for eco‐friendly alternatives. This study reports the synthesis of new amide‐based insecticidal active ingredients from biomass‐derived monomers, specifically furfural and vanillin. The process involves reductive amination followed by carbonylation. The synthesis of the furfural‐based carbamate yield reaches a cumulative 88%, with catalysts Rh/Al2O3 and La(OTf)3 being recyclable at each stage. Insecticidal activity assessments reveal that the furfural carbamate exhibits competitive performance, achieving an LC50 of 6.35 μg/cm², compared to 6.27 μg/cm² for carbofuran. Ecotoxicity predictions indicate significantly lower toxicity levels toward non‐target aquatic and terrestrial species. The importance of the low octanol‐water partition coefficient of the biobased carbamate, attributed to the oxygen heteroatom and electron density of the furan ring, is discussed in detail. Building on these promising results, the synthesis strategy was extended to six other biobased aldehydes, resulting in a diverse portfolio of biomass‐derived carbamates. A techno‐economic analysis reveals a minimum selling price of 11.1$/kg, only half that of comparable carbamates, demonstrating the economic viability of these new biobased insecticides.

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The nitrobenzene activation step in the carbonylation reaction using PdCl2/Fe/I2/Py catalytic system

Cited by 12 publications

References 28 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

The effect of the components of the PdCl2/Fe/I2/Py catalytic system on nitrobenzene carbonylation to ethyl N-phenylcarbamate

Biomass‐Derived, Target Specific, and Ecologically Safer Insecticide Active Ingredients

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