118-48-9Relevant articles and documents
Tryptanthrin from indigo: Synthesis, excited state deactivation routes and efficient singlet oxygen sensitization
Pinheiro, Daniela,Pineiro, Marta,Pina, Jo?o,Brand?o, Pedro,Galv?o, Adelino M.,Seixas de Melo, J. Sérgio
, (2020)
The microwave-assisted synthesis of tryptanthrin from indigo in mild oxidation conditions, and a comprehensive study of the excited state properties of this compound in a variety of solvents with different polarity and viscosity values at room and low temperatures are reported. In contrast with indigo, emission of the triplet state of tryptanthrin is observed with a very efficient singlet oxygen sensitization quantum yield, indicating that the triplet state is efficiently populated. From time-resolved fluorescence and femtosecond transient absorption data, further supported with time-dependent density functional theory (TDDFT) calculations, two species, with S1 states with locally excited (LE) of π,π* nature and a charge transfer (CT) of n,π* characteristics, originated from an initially populated Frank-Condon S2 state (π,π*), are observed. The two electronically independent species are energetically nearly degenerate and inter-conversion is predicted (and rate constants determined) to occur between LE (S1) and CT (S1) species. Due to the low value of the fluorescence quantum yield (~10?3) and high triplet state yield (?T≥?Δ), the high stability of this compound is associated to the high efficiency of the radiationless deactivation processes which involve the formation of the CT state which efficiently converts, through S1 ~~> Tn intersystem crossing, to the T1 triplet state.
Is the 2,3-carbon-carbon bond of indole really inert to oxidative cleavage by Oxone?-Synthesis of isatoic anhydrides from indoles
Nelson, Amber C.,Kalinowski, Emily S.,Czerniecki, Nikolas J.,Jacobson, Taylor L.,Grundt, Peter
, p. 7455 - 7457 (2013)
A recent report has indicated that the oxidizing agent Oxone does not possess the ability to cleave the 2,3-carbon-carbon bond of indole. Work in our laboratory shows that this is not the case. Indole and a variety of aryl ring substituted derivatives readily react to form synthetically important isatoic anhydrides.
Synthesis, structure, and properties of N-(nitramino)phthalimide
Klenov,Churakov,Anikin,Strelenko,Fedyanin,Lyssenko,Tartakovsky
, p. 638 - 643 (2008)
N-(Nitramino)phthalimide R2N-NHNO2 (R2NH is phthalimide) was synthesized by nitration of N-aminophthalimide with nitronium tetrafluoroborate. The structure of this compound was established by X-ray diffraction and confirmed by 1H, 13C, and 14N NMR spectroscopy. The methylation of this compound with diazomethane affords a mixture of N-methyl (R2N-NMeNO2) and O-methyl (R2N-N=N(O)OMe) isomers. The latter compound contains the previously unknown high-nitrogen-oxygen fragment. The thermal decomposition of N-(nitramino)phthalimide in vacuo at 80-100 °C gives 2H-3,1-benzoxazine- 2,4(1H)-dione (isatoic anhydride) as the major product.
An unusual addition and ring-closure reaction of 1-(2-bromoethyl)-2,3-dihydro-3-propyl-1,3,2-benzo-diazaphosphorin-4(1H)-one 2-oxide with carbon disulfide for a new and convenient synthesis of the fused phosphorus heterocyclic compound
Huang, Jun-Min,Chen, Hui,Chen, Ru-Yu
, p. 2215 - 2225 (2002)
The reaction of 1-(2-bromoethyl)-2,3-dihydro-3-propyl-1,3,2- benzodiazaphosphorin-4(1H)-one 2-oxide with carbon disulfide takes an alternative pathway in the use of different bases. The sodium hydride mediated reaction leads to the formation of the tricyclic fused 1,2,3,4,4a,4b,5,6-octahydro-6-oxo-5-propyl-4-thia-3,4b,4a -thiazphosphaphenanthridine 4a-oxide via addition of H-P bond across the double bond of carbon disulfide followed by intramolecular cyclization. In the presence of triethylamine, refluxing a mixture of 1-(2-bromoethyl)-2,3-dihydro-3-propyl-1,3,2-benzodiazaphosphorin-4(1H)-one 2-oxide with carbon disulfide in benzene takes an unusual course with formation in excellent yield of the first example of fused phosphorus heterocyclic 4-[1′-(β-bromoethyl)-4′-oxo-3′-propyl-1′, 2′,3′,4′-tetrahydro-1,3,2-benzodiazaphosphorin-2′ -sulfide]-1,2,3,4,4a,4b,5,6-octahydro-6-oxo-5-propyl-3,4b, 4a- thiazphosphaphenanthridine 4a,2′-dioxide, which was confirmed by spectroscopic methods, microanalyses and single crystal X-ray structure determination.
Quinolines from the cyclocondensation of isatoic anhydride with ethyl acetoacetate: Preparation of ethyl 4-hydroxy-2-methylquinoline-3-carboxylate and derivatives
Jentsch, Nicholas G.,Hume, Jared D.,Crull, Emily B.,Beauti, Samer M.,Pham, Amy H.,Pigza, Julie A.,Kessl, Jacques J.,Donahue, Matthew G.
, p. 2529 - 2536 (2018)
A convenient two-step synthesis of ethyl 4-hydroxy-2-methylquinoline-3-carboxylate derivatives has been developed starting from commercially available 2-aminobenzoic acids. In step 1, the anthranilic acids are smoothly converted to isatoic anhydrides using solid triphosgene in THF. In step 2, the anhydride electrophiles are reacted with the sodium enolate of ethyl acetoacetate, generated from sodium hydroxide, in warm N,N-dimethylacetamide resulting in the formation of substituted quinolines. A degradation–buildup strategy of the ethyl ester at the 3-position allowed for the construction of the α-hydroxyacetic acid residue required for the synthesis of key arylquinolines involved in an HIV integrase project.
Switchable Access to 3-Carboxylate-4-quinolones and 1-Vinyl-3-carboxylate-4-quinolones via Oxidative Cyclization of Isatins and Alkynes
Jiang, Shi-Fen,Xu, Cheng,Zhou, Zhi-Wen,Zhang, Qin,Wen, Xiao-Hui,Jia, Feng-Cheng,Wu, An-Xin
, p. 4231 - 4234 (2018)
An efficient transition-metal-free oxidative cyclization reaction using isatins and alkynes for the facile synthesis of structurally diverse 4-quinolones has been developed. Intriguingly, switchable access to substituted 3-carboxylate-4-quinolones and 1-vinyl-3-carboxylate-4-quinolones could be achieved by choosing a different base in the reaction. The obtained products could undergo further transformations, increasing the application potential of the method in organic synthesis.
Green synthesis of novel phosphonate derivatives using ultrasonic irradiation
Sharafian, Shirin,Hossaini, Zinatossadat,Rostami-Charati, Faramarz,Khalilzadeh, Mohammad A.
, p. 1283 - 1291 (2020)
[Figure not available: see fulltext.] A novel and efficient procedure for the generation of quinazolinone phosphonate derivatives employing the reaction of euparin, isatin or its derivatives, primary amines, dialkyl acetylenedicarboxylates, trimethyl phosphite or triphenyl phosphite, and acidic solution of hydrogen peroxide in aqueous media at ambient temperature under ultrasonic irradiation was developed. Without ultrasonic irradiation, the reaction does not proceed and agitation of the reaction mixture is difficult. Some advantages of this procedure are: short time of reaction, high yields of products, easy isolation of products.
Facile synthesis of fluoroalkylated quinolones using fluoroalk-2-ynoates as fluorinated building blocks
Wu, Jun,Zhang, Hui,Ding, Xiao,Tan, Xuefei,Shen, Hong C.,Chen, Jie,He, Weimin,Deng, Hongmei,Song, Liping,Cao, Weiguo
, p. 54 - 60 (2019)
In the presence of Na2CO3, a variety of fluoroalkylated quinolones were efficiently synthesized from isatins and fluoroalk-2-ynoates in good to excellent yields at room temperature. The reaction can proceed via two different ways with Michael adduct or isatoic anhydride as the key intermediate.
TBHP-Mediated Oxidative Decarboxylative Cyclization in Water: Direct and Sustainable Access to Anti-malarial Polycyclic Fused Quinazolinones and Rutaecarpine
Chen, Xingyu,Xia, Fei,Zhao, Yifan,Ma, Ji,Ma, Yue,Zhang, Dong,Yang, Lan,Sun, Peng
, p. 1239 - 1244 (2020)
Polycyclic fused quinazolinones with anti-malarial activity were synthesized through tert-butyl hydroperoxide (TBHP)-mediated oxidative decarboxylative cyclization between commercially available isatins and cyclic amines in one step. The reaction proceeds smoothly in water without additional transition-metal catalyst, acid and base. The newly synthesized products were evaluated to exhibit moderate to good anti-malarial activity against chloroquine drug-sensitive Plasmodium falciparum 3D7 strain. Additionally, this method also provides direct approach to Rutaecarpine in good yield.
Recyclable (PhSe)2-catalyzed selective oxidation of isatin by H2O2: a practical and waste-free access to isatoic anhydride under mild and neutral conditions
Yu, Lei,Ye, Jianqing,Zhang, Xu,Ding, Yuanhua,Xu, Qing
, p. 4830 - 4838 (2015)
After a series of careful conditional optimizations and catalyst screenings, a methodology to prepare isatoic anhydrides through organoselenium-catalyzed selective oxidation of isatins by H2O2 under mild and neutral conditions was developed. The reactions were very practical because of the recyclability of the catalyst and solvent and the convenient isolation procedures of the products. This work reports the organoselenium-catalyzed oxidation of heterocycles that greatly expands the application scopes of organoselenium catalysis. It also indicates that the organoselenium catalysts are robust enough to be recycled in industrial production if suitable isolation procedures are developed.
