Room temperature ionic liquid promoted synthesis of 1,5-benzodiazepine derivatives under ambient conditions

Jarikote, Dilip V.; Siddiqui, Shafi A.; Rajagopal, R.; Daniel, Thomas; Lahoti, R. J.; Srinivasan, Kumar

doi:10.1016/s0040-4039(03)00096-0

Cited by 162 publications

(67 citation statements)

References 25 publications

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“…Although the rearranged intermediates have not been directly detected in the EDTA decomposition, some potential fragments can still be proposed. It is reported that compound 1 could be prepared by condensation of o-PDA with 4-methyl-3-penten-2-one, 25 acetone, [26][27][28][29][30][31] acetonedicarboxylic acid, 32 or 2, 4, 4-trichloro-2-metylpentane 33 under different conditions ( Figure 5). These facts suggest that the rearranged intermediates might be one or some of these reactants.…”

Section: Resultsmentioning

confidence: 99%

“…[38][39][40][41][42] Several methods for preparing these compounds have been reported in the literature. [25][26][27][28][29][30][31][32] To our knowledge, the formation of the 1,5-benzodiazepine skeleton by the reaction of EDTA with o-PDA in strong acidic medium has not been reported so far. Although this reaction may not be an economic route for the preparation of compound 1, it helps us to sketch a new potential thermal decomposition mechanism for EDTA.…”

Section: Resultsmentioning

confidence: 99%

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Thermal decomposition of ethylenediaminetetraacetic acid in the presence of 1,2-phenylenediamine and hydrochloric acid

Chen¹,

Gao²,

Wang³

2006

J. Braz. Chem. Soc.

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Considerando os produtos de reação do ácido etilenodiaminotetraacético (EDTA) com 1,2-fenilenodiamina (o-PDA), um novo processo para a decomposição térmica do EDTA é proposto. O meio ácido forte e a presença de o-PDA facilitam a decomposição de EDTA, como evidenciado pela temperatura relativamente baixa de reação. Em adição aos passos descritos na literatura, um processo de rearranjo está presente na reação de decomposição. Os intermediários rearranjados condensam com o-PDA, formando um inesperado composto biologicamente ativo 2,2,4-trimetil-3H-5-hidro-1,5-benzodiazepina, proporcionando a possibilidade de explorar um mecanismo de decomposição alternativo para este quelante amplamente utilizado.Based on the reaction products of ethylenediaminetetraacetic acid (EDTA) with 1,2-phenylenediamine (o-PDA), a novel thermal decomposition pathway of EDTA is proposed. The strong acidic medium and the presence of o-PDA facilitate the decomposition of EDTA as evidenced by the relatively lower reaction temperature. In addition to the steps described in literatures, rearrangement process is involved in the decomposition reaction. The rearranged intermediates condense with o-PDA, forming an unexpected biologically active compound 2,2,4-trimethyl-3H-5-hydro-1,5-benzodiazepine, thus provides the possibility to explore an alternative decomposition mechanism for this widely used chelator.Keywords: ethylenediaminetetraacetic acid, heterocycle, reaction mechanism, thermal decomposition, thermochemistry IntroductionEthylenediaminetetraacetic acid (EDTA) is one of the most extensively used chelating agents in chemistry, biochemistry, medicine, environmental sciences, and paper industry.1-6 As a scavenger for metal oxides or a stabilizer for metal ions, EDTA is also used at elevated temperatures to prevent scale deposits in high-pressure boilers or nuclear reactors owing to its thermal stability. Nevertheless, the behaviour of EDTA in waste water effluents 8,9 and natural aquatic systems 10 has incurred lots of threats to the natural environment. EDTA not only increases the total nitrogen contents, but also remobilizes most toxic heavy metals from solid matter into water solution and thus extends their biological life cycles. 11Hence, great attention has been paid to the study on decomposition mechanism 12-17 and treatment technique 18 for this aminopolycarboxylic acid complexing agent. Both EDTA and its disodium salt are stable to heat even at 423 K.19 EDTA begins to decompose at about 463 K and nearly 50% breaks down at 483 K in the presence of metal ions. 12 Stepwise decarboxylations and hydrolysis procedures of the ethylene C-N link of EDTA have been suggested by earlier researchers. 13,14 As shown in Figure 1, the decomposition mode may differ greatly with temperature changes. 14,15 Other factors such as acidity and reaction medium can also influence the decomposition of EDTA. For example, Vol. 17, No. 5, 2006 when ammonia was used as a reaction medium and reactant in a high pH system, both ammonolysis and hydrolysis of EDTA oc...

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Thermal decomposition of ethylenediaminetetraacetic acid in the presence of 1,2-phenylenediamine and hydrochloric acid

Chen¹,

Gao²,

Wang³

2006

J. Braz. Chem. Soc.

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“…These includes, (i) BF 3 24 (v) 1,3-di-n-butylimidazolium bromide without any catalyst. 25 Literature survey also reveals the method of Shrinivasan and co-workers, a multicomponent reaction for the synthesis of 3-Hbenzo[b]-1,4-diazepines. 26 Recently, Jiang and co-workers reveals [4+2+1] cycloaddition of o-phenylenediamine and ethyl propionate to synthesize 3, 4-disubstituted 1,5-benzodiazepines in good yield.…”

Section: Introductionmentioning

confidence: 99%

Solvent Free Oxalic Acid Catalyzed Synthesis of 1,5-Benzodiazepines

Sarkate

Sangshetti

Dharbale

et al. 2013

J. Chil. Chem. Soc.

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In the present study 1, 5-benzodiazepines were synthesized from a range of α, β-unsaturated ketones and o-phenylendiamine using oxalic acid 10 mol% as a catalyst under solvent free conditions. The yields of the present method are better than the reported method which explains effectiveness of oxalic acid catalyst. The cost effective, resourceful, undemanding and environment friendly are the advantageous aspects of this method.

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“…Owing to their versatile applications various methods for the synthesis of benzodiazepines have been reported. One of the commonly reported methods for the synthesis of benzodiazepines is the condensation reaction between o-phenylenediamines and ketones [5], enones [6] or β-haloketones [7], using ionic liquids [8], under microwave irradiation [9] [16]. The reported methods of the synthesis of benzodiazepine suffers from one or other limitations such as harsh reaction conditions, expensive reagents, low yields, relatively long reaction time and formations of side products [17][18][19][20][21][22][23][24][25].…”

Section: Introductionmentioning

confidence: 99%

Biopolymer-supported iron oxide nanocomposite: Preparation and catalytic application in the synthesis of benzodiazepine derivatives

Maleki

Kamalzare

2013

Proceedings of the 17th International Electronic Conference on Synthetic Organic Chemistry

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Abstract:In this work, cellulose-based nanocomposite containing high contents of Fe 3 O 4 nanoparticles used as a catalyst in the condensation reaction between o-phenylenediamines and ketones for synthesis of benzodiazepines in good to excellent yields under mild conditions. A good correlation between the amount of surface acid sites as well as the surface morphology of the catalysts and the catalytic activity has been observed. This method has been found to be ecofriendly, simple and economical. The solid supported nanocatalyst could be recycled and reused without significant loss of its catalytic activity.

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Room temperature ionic liquid promoted synthesis of 1,5-benzodiazepine derivatives under ambient conditions

Cited by 162 publications

References 25 publications

Thermal decomposition of ethylenediaminetetraacetic acid in the presence of 1,2-phenylenediamine and hydrochloric acid

Thermal decomposition of ethylenediaminetetraacetic acid in the presence of 1,2-phenylenediamine and hydrochloric acid

Solvent Free Oxalic Acid Catalyzed Synthesis of 1,5-Benzodiazepines

Biopolymer-supported iron oxide nanocomposite: Preparation and catalytic application in the synthesis of benzodiazepine derivatives

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