A Serendipitous Synthesis of 11a-Hydroxy-11,11a-dihydrobenzo[<i>e</i>]indeno[2,1-<i>b</i>][1,4]diazepine-10,12-dione Derivatives by Condensation of 2-Aminobenzamides with Ninhydrin in Water

Devi, Rajkumari Vijilata; Garande, Ashok M.; Maity, Dilip Kumar; Bhate, Prakash M.

doi:10.1021/acs.joc.5b02327

Cited by 19 publications

(11 citation statements)

References 53 publications

(59 reference statements)

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“…We used the same DFT method (B3LYP 6–31G(d,p)) as Bhate et al . on ninhydrin and indanetrione (calculating the partial atomic (Mulliken) charges), but we performed all calculations using a polarizable continuum model for water instead of the gas phase . Structure optimization was performed (supporting information section 9) and the corresponding frequencies were calculated for the different ninhydrin derivatives, intermediates and products.…”

Section: Resultsmentioning

confidence: 99%

“…Ninhydrin is a powerful electrophile that reacts not only with amines, enamines, ammonia and amino acids, but also with weak nucleophiles such as anilines, alcohols, ureas and even amides . Many studies have corroborated that upon dehydration of ninhydrin the central carbonyl of the resulting indanetrione is the most reactive towards amines.…”

Section: Introductionmentioning

confidence: 99%

“…have recently reported on the reaction of ninhydrin with an aniline containing an amide functionality. They calculated, using Density Functional Theory at the B3LYP 6–31G(d,p) level, that the central carbon is the least reactive when hydrated compared to the adjacent carbonyls, but becomes the most electron deficient and therefore the most reactive upon elimination of water, explaining that indanetrione reacts with the amide rather than ninhydrin itself . In 1999 Bowden et al .…”

Section: Introductionmentioning

confidence: 99%

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Effect of Substituents on the Reactivity of Ninhydrin with Urea

et al. 2018

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Ninhydrin, i. e. the stable hydrate of the reactive species indanetrione, is a well-known compound used for the quantification of ammonia and amino acids. However, substituent effects on the reactivity of ninhydrin with nucleophiles are not described. In this work, the kinetics of the reaction of C4-and C5-substituted ninhydrins with urea was studied and monitored by 13 C-NMR. Surprisingly, the obtained results show that electron donating groups (EDGs) as well as electron withdrawing groups (EWGs) decrease the rate of the reaction. EDGs decrease the electrophilicity of indanetrione, resulting in slower overall kinetics than unsubstituted ninhydrin. The calculated Gibbs free energy differences for the dehydration of unsubstituted and substituted ninhydrins and the subsequent reaction with urea showed that the dehydration of the compounds is more sensitive to electronic effects than the subsequent reaction with urea. Therefore, although EWGs increase the electrophilicity of indanetrione, this is more than counterbalanced by an adverse shift of the hydration equilibrium towards the unreactive hydrate (i. e. ninhydrin), resulting in slower kinetics as well.[a] J. Scheme 1. The mechanism of reaction of ninhydrin with amino acids. R.d.s. = rate-determining step. 1 e = ninhydrin, Table 1 entry e.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Effect of Substituents on the Reactivity of Ninhydrin with Urea

et al. 2018

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“…Using water as a solvent for organic conversion not only provides several green chemistry benefits, but also speeds up the reaction and increases the selectivity of the reaction. [15] 2.1. Coupling of C sp3 À H with C sp3 À H Bond…”

Section: Cdc Reactions For Cà C Bond Formation In Aqueous Mediamentioning

confidence: 99%

Recent Advances in Cross‐Dehydrogenative Couplings (CDC) of C−H Bond in Aqueous Media

Peng

Dong

2021

Adv Synth Catal

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To develop highly efficient synthetic reactions is quite important in organic chemistry. Cross dehydrogenative couplings (CDC) utilize C−H bonds of substrates to construct new C−X (X=C, S, O, N, P) bonds. For CDC, the pre‐functionalization of reaction substrates can be avoided and the C−X (X=C, S, O, N, P) bonds can be newly formed by simple and efficient synthesis routes. Meanwhile, water is increasingly used as a substitute for organic solvents in cross‐dehydrogenative coupling because of its rich content, non‐toxicity, and non‐ flammability. In recent years, organic chemists are devoted their efforts to explore the cross dehydrogenative couplings (CDC) in aqueous phase which feature high atom utilization rate and environmental friendliness. Herein, we summarized the recent advances in the construction of C−C, C−S, C−O, C−N, and C−P bonds through CDC reactions of C−H bonds in water.

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“…In 2016, Bhate group studied an unprecedented condensation reaction of ninhydrin with 2‐aminobenzamide derivatives in aqueous medium . They observed that, 2‐amino‐ N ‐phenylbenzamide derivatives 115 with substituents (Me, ‐OMe, ‐Et, ‐COOH, ‐COOMe) at the ortho position of the N ‐phenyl moiety 3′‐phenyl‐1′ H‐ spiro[indene‐2,2′‐quinazoline]‐1,3,4′(3′ H )‐trione derivatives 116 were obtained as the exclusive product (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

Ninhydrin Adducts as Valid Synthon in Organic Synthesis: A Review

Das¹,

Dutta

2020

ChemistrySelect

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Ninhydrin (1,2,3‐indanetrione hydrate) is a powerful electrophile having enormousapplications in organic and bio‐organic sciences. In the last few years, reactivity of various ninhydrin adducts have been exploited extensively for the development of diverse organic scaffolds. The present review focuses on the applications of readily accessible ninhydrin adducts as building block towards the synthesis of a variety of compounds including N‐inserted compounds, spiro‐heterocycles, medium ring compounds, polycyclic molecules, propellanes, cycloadducts, allylic anions, axially chiral molecules etc. Interestingly, some of the compounds have profound biological activities and a few display important photophysical properties. Most of the reactions described here are simple and carried out with easily available starting materials under green conditions.

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A Serendipitous Synthesis of 11a-Hydroxy-11,11a-dihydrobenzo[e]indeno[2,1-b][1,4]diazepine-10,12-dione Derivatives by Condensation of 2-Aminobenzamides with Ninhydrin in Water

Cited by 19 publications

References 53 publications

Effect of Substituents on the Reactivity of Ninhydrin with Urea

Effect of Substituents on the Reactivity of Ninhydrin with Urea

Recent Advances in Cross‐Dehydrogenative Couplings (CDC) of C−H Bond in Aqueous Media

Ninhydrin Adducts as Valid Synthon in Organic Synthesis: A Review

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