- Application of pfitzinger reaction in synthesis of hetero ring annelated quinoline carboxylic acid derivatives
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The diazotized 8-aminoquinoline (4) was reacted with 2-(hydroxymethylidine)cyclohexanone and N-benzyl 3-(hydroxymethylidine)-piperidine-4-one (5, 6) (generated from the reaction of cyclohexanone and N-benzyl-4-piperidone with ethyl formate in the presence of NaOEt) under the conditions of Japp-Klingemann reaction, followed by Fisher-indolization of the resulting hydrazones in acid, formed the quinolinooxocarbazole (7) and N-benzyl quinolinooxoazacarbazole (8), respectively. Pfitzinger reaction of compounds 7 and 8 with isatin in alkali afforded the corresponding quinoline carboxylic acid derivatives 10 and 11, respectively. In accord to generally accepted mechanism of Pfitzinger reaction, we suggest that the reaction of compounds 7 and 8 with isatin in alkali proceeds with the formation of isatoic acid which undergoes instantaneous cyclocondensation with carbonyl species 7 and 8 to generate compounds 10 and 11, respectively.
- Yadav, Taruna,Yadav, Neelam K.,Yadav, Manju,Singh, Bhawani,Kishore
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Read Online
- DYE COMPOUND AND PHOTOPOLYMER COMPOSITION
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The present invention relates to a novel structure compound, a photopolymer composition comprising the compound as a dye, a hologram recording medium produced by the photopolymer composition, an optical element including the hologram recording medium, and a holographic recording method using the hologram recording medium. The hologram recording medium has improved durability against temperature and humidity.COPYRIGHT KIPO 2019
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Paragraph 0196-0200
(2019/10/08)
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- Design and synthesis of spirocyclic ligands of glucocorticoid receptors
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Spirocyclic indazoles were designed as potential ligands for the glucocorticoid receptors (GRs). A short and efficient synthetic sequence was developed allowing the preparation of pure diastereomeric spirocyclic analogs of fluorocortivazol. Our studies also revealed a new application of Burgess reagent leading to a ring expansion. The structures and conformations of several key intermediates and products were confirmed by single crystal X-ray diffraction analysis. Conformational assignments were also supported by DFT calculations. As a proof of concept we tested the affinity of diastereomeric compounds 13b and 14b for the GRs. Rewardingly, it was found that 14b showed a promising IC50 of 27 nM.
- Badarau, Eduard,Robert, Frédéric,Massip, Stéphane,Jakob, Florian,Lucas, Simon,Frormann, Sven,Ghosez, Léon
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p. 5119 - 5128
(2018/03/07)
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- Stereospecific Construction of Contiguous Quaternary All-Carbon Centers by Oxidative Ring Contraction
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Oxidative ring contraction of cyclic α-formyl ketones was facilitated by the action of H2O2under operationally simple and environmentally benign reaction conditions. The process was highly regioselective and enables stereospecific construction of contiguous quaternary all-carbon centers from stereodefined all-substituted all-cyclic ketones. The asymmetric syntheses of (+)-cuparene and (+)-tochuinyl acetate were also successively achieved by taking advantage of this novel protocol.
- Yu, Xin,Hu, Jiadong,Shen, Zhigao,Zhang, Hui,Gao, Jin-Ming,Xie, Weiqing
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supporting information
p. 350 - 353
(2016/12/30)
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- GLUCOSYLCERAMIDE SYNTHASE INHIBITORS FOR THE TREATMENT OF DISEASES
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Described herein are compounds of Formula I, methods of making such compounds, pharmaceutical compositions and medicaments containing such compounds, and methods of using such compounds to treat or prevent diseases or conditions associated with the enzyme glucosylceramide synthase (GCS).
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Paragraph 000608
(2015/04/15)
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- Investigations into an anionic oxy-Cope/transannular conjugate addition approach to 7,20-diisocyanoadociane
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An anionic oxy-Cope/transannular conjugate addition approach to the potent antimalarial 7,20-diisocyanoadociane is presented. The unexpected formation of undesired diastereomers in the key reaction led to the structural reassignment of previous products of this type of cascade and a reevaluation of the reversibility of the transannular ring closure. During efforts to coax the reaction toward the desired product, a transannular ene reaction provided tricyclic compounds relevant to the kempane diterpenoids.
- Roosen, Philipp C.,Vanderwal, Christopher D.
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supporting information
p. 4368 - 4371
(2015/01/16)
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- A novel synthetic protocol for the heteroannulation of oxocarbazole and oxoazacarbazole derivatives through corresponding oxoketene dithioacetals
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An efficient novel strategy for the heteroannulation of 6,7-dihydropyrazolo[3,4-b]carbazol-8(1H,5H,9H)-one 4 and 5-N-benzyl-6,7- dihydropyrazolo[3,4-b]carbazol-8(1H,9H)-one 5 has been developed to allow the incorporation of pyrazole, isoxazole, pyrimidine, benzodiazepine, and benzothiazepine rings through their corresponding oxoketene dithioacetal derivatives 6 and 7, respectively.
- Tyagi, Ruchi,Kaur, Navjeet,Singh, Bhawani,Kishore, Dharma
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- Microwave assisted synthesis, characterization and biocidal activities of some new chelates of carbazole derived Schiff bases of cadmium and tin metals
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This study is planned to report the advancement of green microwave approach in the fabrication of a new series of biologically potent (N^X, where X = O/S) donor Schiff bases and their cadmium(II) and tin(II) complexes. The ligands and their metal complexes have been characterized in terms of elemental analysis, molar ionic conductance, magnetic moment and spectral (IR, UV-Vis, NMR ( 1H, 119Sn), FAB-mass, thermal and XRD) data. The data revealed that the ligands coordinated to the metal center via nitrogen and oxygen/sulfur atoms and form an octahedral arrangement of the ligands around central metal atom. All compounds were evaluated for their in vitro antimicrobial activities against two pathogenic bacteria Bacillus subtilis and Escherichia coli and two fungi Aspergillus niger and Aspergillus flavus by standard disc diffusion method. The discs were stored in an incubator at 37 °C. The compounds were dissolved in DMF at 500 and 1000 ppm concentrations for screening biocidal activity. The compounds were dissolved in DMF to get the 100 and 200 ppm concentration of test solutions for screening fungicidal activity. The inhibition zone around each disc was measured (in mm) after 24 h and 96 h for biocidal and fungicidal activities respectively.
- Yadav, Manju,Mishra, Neelima,Sharma, Nutan,Chandra, Sulekh,Kumar, Dinesh
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p. 733 - 742
(2014/07/07)
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- Synthesis and Oxidative Cleavage of Oxazinocarbazoles: Atropselective Access to Medium-Sized Rings
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Polycyclic systems can be converted into medium-sized-ring-containing compounds through the controlled oxidative cleavage of internal double bonds. This approach is particularly accessible in systems that contain a suitably substituted indole ring. Here, a robust approach to the synthesis of the understudied oxazinocarbazole system is reported. After regioselective incorporation of a carbonyl functional group, m-chloroperoxybenzoic acid (MCPBA) is used to cleave the indole 2,3-double bond that this system contains. This results in a competition between two processes, oxidative cleavage of the double bond and a pinacol-type rearrangement, both of which occur with very high diastereoselectivity. The balance between the two processes is studied as a function of the substrate structure. Extensive use of X-ray crystallographic analysis of the products enables detailed mechanistic conclusions to be drawn.
- Liu, Gu,Lancefield, Christopher S.,Lorion, Magali M.,Slawin, Alexandra M. Z.,Westwood, Nicholas J.
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supporting information
p. 2808 - 2814
(2015/02/19)
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- A novel necroptosis inhibitor - Necrostatin-21 and its SAR study
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An initial structure-activity relationship study of the novel necroptosis inhibitor Nec-21 was described. Any changes of the tetracyclic scaffold were detrimental for the activity. Introduction of a substituent to 7 or 8 position (e.g., cyano or methoxy group, respectively), would increase the activity. The 7 and 8-position disubstituted compound 17b was 35-fold as potent as the lead, while EC50 reached 14 nM.
- Wu, Zhijie,Li, Ying,Cai, Yu,Yuan, Junying,Yuan, Chengye
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supporting information
p. 4903 - 4906
(2013/09/02)
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- Noteworthy mechanistic precedence in the exclusive formation of one regioisomer in the Beckmann rearrangement of ketoximes of 4-piperidones annulated to pyrazolo-indole nucleus by organocatalyst derived from TCT and DMF
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Application of a very mild protocol to the Beckmann rearrangement of ketoximes of pyrazolo annulated oxocarbazole 5a and oxoazacarbazole 5b with the organocatalyst derived from 2,4,6-trichloro[1,3,5]triazine (TCT) and dimethylformamide (DMF) has been explored to provide a regioselective formation of the corresponding azepine 6a and 1,4-diazepine 6b respectively in good yield and purity. The mechanistic precedence for the exclusive formation of only one regioisomer has been discussed. Copyright Taylor & Francis Group, LLC.
- Tyagi, Ruchi,Kaur, Navjeet,Singh, Bhawani,Kishore
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- Synthesis of novel precursors of Pfitzinger reaction: A facile one-pot strategy to the synthesis of quinoline carboxylic acid derivatives of pyrazolo-carbazoles and azacarbazoles
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Interaction of 5-indazolyldiazonium chloride 2 with 2-hydroxymethylidene cyclohexanone 5 and N-benzyl-3-hydroxymethylidene-4-piperidone 6 under the conditions of Japp-Klingemann reaction, followed by Fischer-indolization of the resulting hydrazones, formed the 5,7,8,9-tetrahydropyrazolo[4,3-b]carbazol-6(1H) -one 9 and 9-benzyl-5,7,8,9-tetrahydropyrido[2′,3′:4,5]pyrrolo[2,3- f]indazol-6(1H)-one 10, respectively. Pfitzinger reaction of 9 and 10 with isatin in alkali afforded the corresponding quinoline carboxylic acid derivatives 12 and 13, respectively. [Figure not available: see fulltext.]
- Tyagi, Ruchi,Singh, Bhawani,Kishore
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scheme or table
p. 431 - 435
(2012/08/07)
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- Asymmetric synthesis and in vivo biological inactivity of the right-hand terpenoid fragment of terpendole e
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Synthesis of the DEF-ring terpenoid fragment of terpendole E, an Eg5 inhibitor, is described. The DE-ring was constructed by a modification of Barrero's radical cyclization. The F-ring tetrahydropyran was then constructed by acid-induced cyclization of an epoxy alcohol, which was prepared by cross-metathesis followed by Shi's epoxidation. Cell-based assays indicated that the DEF-ring fragment is not capable of inhibiting cell growth and cell cycle progression of human cancer cell lines, indicating that the DEF-ring fragment alone is not sufficient for the biological activity. The DEF-ring terpenoid fragment of terpendole E, has been synthesized in 15 steps starting from farnesyl acetate, employing radical cyclization (DE-ring formation) and stereoselective cyclization of an epoxyalcohol (F-ring formation). Cell-based assays showed that the right-hand DEF-ring fragment is inactive in cell growth and cell cycle progression of human cancer cell lines.
- Oikawa, Masato,Hashimoto, Ryo,Sasaki, Makoto
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supporting information; experimental part
p. 538 - 546
(2011/04/17)
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- NOVEL HETEROCYCLIC COMPOUNDS, PHARMACEUTICAL COMPOSITIONS CONTAINING THEM AND PROCESSES FOR THEIR PREPARATION
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The present invention relates to novel heterocyclic compounds of general formula (I) that are phosphodiesterase inhibitors (PDEs), in particular phosphodiesterase type 4 inhibitors. These novel PDEs are useful in the treatment of inflammatory diseases (such as asthma, COPD, allergic rhinitis, allergic conjunctivitis, respiratory distress syndrome, chronic bronchitis, nephritis, rheumatoid spondylitis, osteoarthritis, atopic dermatitis, eosinophilic granuloma, psoriasis, rheumatoid septic shock, ulcerative colitis, multiple sclerosis, chronic inflammation, Crohn's syndrome and central nervous system(CNS) disorders) as well as disorders or conditions generally characterized by or associated with an excessive secretion of TNF-α and Phosphodiesterase 4 (PDE IV).
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Page/Page column 30
(2009/10/22)
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- Synthesis of substituted benzenes from α-methylene ketones
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A new general method for the synthesis of substituted benzenes from cyclic ketones having active methylene groups via the corresponding hydroxymethylene ketones and enamino-ketones has been developed. Formylation of these ketones with ethyl formate followed by enamination with pyrrolidine produces enamino-ketones which on reaction with threefold excess of malononitrile in boiling benzene in the presence of ammonium acetate in acetic acid gives the substituted benzenes in good yield. The reaction has been extended to aliphatic and aromatic ketones having active methylene groups to give substituted benzenes and biphenyls, respectively.
- Khaidem, Ibomacha Singh,Singh, Sagolsem Lokhol,Singh, Laishram Ramananda,Khan, Mohd Ziaur Rahman
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p. 911 - 914
(2007/10/03)
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- Tetracyclic compounds from tetrahydrocarbazolones. Part 1. Synthesis from 2,3,4,9-tetrahydrocarbazol-1-ones
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Reaction of several 2,3,4,9-tetrahydrocarbazol-1-ones 1 was used to synthesise new thieno, furo and selenadiazolo annelated carbazoles.
- Joseph, Delphine,Martarello, Laurent,Kirsch, Gilbert
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p. 2001 - 2014
(2007/10/03)
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- Dipolar cyclization reactions in heterocyclic synthesis: A novel route to furanophanes
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The multistep transformation of 2,3-bridged butenynyl oxiranes 8 into furanophanes 12 involving bridgehead olefins 11 as key intermediates is described. The two lower members of 12 undergo rapid air oxidation resulting in the formation of the dienediones 14a,b. 14b is converted by base into the bicyclo[6.3.0]undecadienone 15.
- Eberbach,Laber
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- Oxidative Seco Rearrangement. A Novel Carbon-Carbon Bond Cleavage
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Cycloalkanones can be converted to 2,2-(trimethylenedithio)cycloalkanones and, by reduction or addition of an organometallic reagent, to the corresponding alcohols.These hydroxydithianes undergo a novel ring cleavage with concomitant rearrangement of the oxidation pattern to produce 3-(ω-oxoalkyl)-1,4-dithiacycloheptan-2-ones upon treatment with lead tetraacetate.In this way the oxidation level of C(1), C(2), and C(3) of the original cycloalkanone has been adjusted.Six-, nine-, and twelve-membered rings have been cleaved in 65-95percent yields.The regiocontrol of the method was illustrated with a 2- and a 3-substituted cyclohexanone in which only the oxidation pattern of C(5), C(6), and C(1) were adjusted.The 1,4-dithiacycloheptan-2-ones are simultaneously a β-keto sulfide and a thioester.The β-keto sulfide was subjected to oxidation-elimination to illustrate the versatility of these substances, giving (after methanolysis) pure (E)-α,β-unsaturated methyl esters.This process extended the adjustment of the oxidation level to C(4) of the original cycloalkanone.Application of this sequence to cyclononanone allowed a synthesis of the queen's substance that is found in several species of insects.The utility of the thioester unit was illustrated by a ketone synthesis upon treatment with organocuprates.The resultant α-thioketones were subjected to oxidation-elimination to give (E)-α,β-unsaturated enones.Possible mechanistic pathways for this unusual oxidative rearrangement are discussed.In this connection, it was found that treatment of a ketene thioacetal with lead tetraacetate at 55 deg C smoothly effected acetoxylation.
- Trost, Barry M.,Hiroi, Kunio,Jungheim, Louis N.
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p. 1839 - 1847
(2007/10/02)
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- 5,6-Benzo analogues or prostaglandin E
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Disclosed are prostaglandin analogues having the structural formula, STR1 in which: T is selected from the group consisting of carboxyl, alkoxycarbonyl or cyano; M is selected from the group consisting of carbonyl, R-hydroxymethylene or S-hydroxymethylene; L is selected from the group consisting of methylene or methine, provided L is methine only if J is methine; J is selected from the group consisting of methylene, ethylene, R-hydroxymethylene, S-hydroxymethylene or methine, provided J is methine only if L is methine; W is selected from the group consisting of --CH2 --CH-- or trans --CH=C--; T1 and T2 are attached to adjacent carbon atoms; T1 is selected from the group consisting of hydrogen or phenyl, provided T1 is phenyl only if T2 is lower alkyl; T2 is selected from the group consisting of n-pentyl or lower alkyl, provided T2 is lower alkyl only if T1 is phenyl; Or T1 and T2 are joined together to form an alkylene group of 4 or 6 carbon atoms. Also disclosed are methods for preparing such prostaglandin analogues.
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- 5,6-Benzo analogues of prostaglandin E
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Disclosed are prostaglandin analogues having the structural formula, STR1 in which: T is selected from the group consisting of carboxyl, alkoxycarbonyl or cyano; M is selected from the group consisting of carbonyl, R-hydroxymethylene or S-hydroxymethylene; L is selected from the group consisting of methylene or methine, provided L is methine only if J is methine; J is selected from the group consisting of methylene, ethylene, R-hydroxymethylene, S-hydroxymethylene or methine, provided J is methine only if L is methine; W is selected from the group consisting of --CH2 --CH-- or trans --CH=C--; T1 and T2 are attached to adjacent carbon atoms; T1 is selected from the group consisting of hydrogen or phenyl, provided T1 is phenyl only if T2 is lower alkyl; T2 is selected from the group consisting of n-pentyl or lower alkyl, provided T2 is lower alkyl only if T1 is phenyl; Or T1 and T2 are joined together to form an alkylene group of 4 or 6 carbon atoms. Also disclosed are methods for preparing such prostaglandin analogues.
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