Peri and Regioselective Synthesis of New Heterocyclic Compounds from 1,5-Benzodiazepines

Elhazazi, S.; Baouid, A.; Hasnaoui, A.; Compain, Philippe

doi:10.1081/scc-120015555

Cited by 10 publications

(6 citation statements)

References 12 publications

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“…may have taken place, it was subsequently followed by a thermal decomposition of the so-formed unstable spirocompound j′ (Scheme 5). 24 The study of the HMBC map established of a whole set of linkages and a complete assignment of the 1 H and 13 C spectra supported the structures we have proposed (see experimental section). Thus the condensation of 3b with DPDM performed under the same experimental conditions gave the 2-benzhydrylthioether of 4-(2-hydroxyphenyl)-3H-1,5-benzodiazepine (7) as the exclusive product.…”

Section: Resultssupporting

confidence: 80%

Chemoselectivity of the 1,3-Dipolar Cycloaddition of Some Diazoalkanes with 1,5-Benzodiazepine Derivatives

Nsira

Karoui²,

Gharbi³

et al. 2012

Journal of Chemical Research

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Benzodiazepines are pharmaceutically important synthetic materials. Reaction of the 4-(2-hydroxyphenyl)-1,5-benzodiazepin-2-one with 2-diazopropane (DAP) gave a mixture of the 2-isopropylether of 4-(2-hydroxyphenyl)-3H-1,5-benzodiazepine and 1-isopropyl-4-(2-hydroxyphenyl)-3H-1,5-benzodiazepin-2-one. Whilst diphenyldiazomethane (DPDM) gave 1-benzhydryl-4-(2-hydroxyphenyl)-3H-1,5-benzodiazepin-2-one. Reaction of the corresponding thione with DAP led to the 2-isopropylthioether of 4-(2-hydroxyphenyl)-3H-1,5-benzodiazepine and 1-isopropyl-4-(2-hydroxyphenyl)-1,5-benzodiazepine-2-thione while the reaction with DPDM gave the 2-benzhydrylthioether of 4-(2-hydroxyphenyl)-3H-1,5-benzodiazepine. The characterisation of these prepared - N, - O and - S alkylated benzodiazepines involved 1D and 2D-NMR techniques, mass spectrometry and elemental analysis.

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Section: Resultssupporting

confidence: 80%

Chemoselectivity of the 1,3-Dipolar Cycloaddition of Some Diazoalkanes with 1,5-Benzodiazepine Derivatives

Nsira

Karoui²,

Gharbi³

et al. 2012

Journal of Chemical Research

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“…[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.…”

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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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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“…For background to benzodiazepine derivatives, see: Barltrop et al (1959);El Hazazi et al (2003); Sharp & Hamilton (1946). For related structures, see: Chiaroni et al (1995); El Hazazi et al (2000).…”

Section: Related Literaturementioning

confidence: 99%

“…Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1989); cell refinement: CAD-4 EXPRESS; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999). In order to develop work carried out before in our laboratory we were interested in the synthesis of new derivatives benzodiazepinic (El Hazazi et al, 2003). These reactions are either of the reactions of cycloadditions [2 + 1] realising generated carbenes in situ or reactions of transfer of methelyne.…”

Section: Data Collectionmentioning

confidence: 99%

Ethyl 5,5-dichloro-3-(4-chlorophenyl)-3a-methyl-4a-phenyl-3a,4,4a,5-tetrahydro-3H-aziridino[2,1-d][1,2,4]triazolo[4,3-a][1,5]benzodiazepine-1-carboxylate

et al. 2011

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Peri and Regioselective Synthesis of New Heterocyclic Compounds from 1,5-Benzodiazepines

Cited by 10 publications

References 12 publications

Chemoselectivity of the 1,3-Dipolar Cycloaddition of Some Diazoalkanes with 1,5-Benzodiazepine Derivatives

Chemoselectivity of the 1,3-Dipolar Cycloaddition of Some Diazoalkanes with 1,5-Benzodiazepine Derivatives

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

Ethyl 5,5-dichloro-3-(4-chlorophenyl)-3a-methyl-4a-phenyl-3a,4,4a,5-tetrahydro-3H-aziridino[2,1-d][1,2,4]triazolo[4,3-a][1,5]benzodiazepine-1-carboxylate

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