| Reference | [1]. J Nanosci Nanotechnol. 2019 Aug 1;19(8):4623-4631. doi: 10.1166/jnn.2019.16490.<br />
Nanocrystalline Cu-ZnO as an Green Catalyst for One Pot Synthesis of 4,4'-((phenyl)methylene)bis(3-methyl-1-phenyl-1H-pyrazol-5-ol) Derivatives.<br />
Shinde S(1), Karale B(1), Bankar D(2), Arbuj S(2), Moulavi M(2), Amalnerkar D(2), Kim T(1).<br />
Author information: (1)Post Graduate Department of Chemistry, Radhabai Kale Mahila Mahavidyalaya, Ahmednagar 414001, India. (2)Centre for Materials for Electronic Technology (C-MET), Off Pashan Road, Panchwati, Pune 411008, India.<br />
Synthesis of 4,4'-((phenyl)methylene)bis(3-methyl-1-phenyl-1H-pyrazol-5-ol) derivatives was successively carried out using Cu doped ZnO nanomaterials. The nanocrystalline Cu-ZnO was obtained by decomposing as-synthesized copper-zinc oxalate intermediate at 520 °C. The prepared Cu-ZnO nanostructured catalyst was characterized with FTIR, X-ray diffraction, field emission scanning electron microscope and electron diffraction techniques. XRD analysis indicates the formation of highly crystalline hexagonal phase of ZnO along with the presence of monoclinic CuO. FESEM photographs shows the existence of plate like structures made up of small spherical shaped particles having size in the range of 30-50 nm. As-synthesized Cu-ZnO was used as heterogeneous catalyst for one pot synthesis of 4,4'-((phenyl)methylene)bis(3-methyl-1-phenyl-1H-pyrazol-5-ol) derivatives using phenyl hydrazine, ethyl acetoacetate and aromatic aldehydes. The 3-methyl-1-phenyl-1H-pyrazol-5-ol was obtained as in-situ precursor to the series of bis-pyrazolone derivatives. The progress of reaction was monitored by thin layer chromatography. The obtained organic product was further characterized and confirmed by FT-IR, 1H-NMR, 13C-NMR and HRMS spectroscopic techniques. The Cu-ZnO catalyst confers upto 96% yield of pyrazolone derivatives in ethanol solvent at refluxing condition. The Cu-ZnO catalyst was used successfully up to 5 cycles without much loss of catalytic activity. Overall, the use of environmental friendly Cu-ZnO nano-structures as a heterogeneous catalyst shows higher yield and lower reaction time towards the synthesis of bispyrazolone derivatives by Tandem Knoevenagel/Michael reaction.<br />
DOI: 10.1166/jnn.2019.16490 PMID: 30913758<br />
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[2]. ACS Med Chem Lett. 2016 Aug 30;7(11):994-998. doi: 10.1021/acsmedchemlett.6b00253. eCollection 2016 Nov 10.<br />
Site-Specific Tandem Knoevenagel Condensation-Michael Addition To Generate Antibody-Drug Conjugates.<br />
Kudirka RA(1), Barfield RM(1), McFarland JM(1), Drake PM(1), Carlson A(1), Bañas S(1), Zmolek W(1), Garofalo AW(1), Rabuka D(1).<br />
Author information: (1)Catalent Biologics West , 5703 Hollis Street, Emeryville, California 94530, United States.<br />
Expanded ligation techniques are sorely needed to generate unique linkages for the growing field of functionally enhanced proteins. To address this need, we present a unique chemical ligation that involves the double addition of a pyrazolone moiety with an aldehyde-labeled protein. This ligation occurs via a tandem Knoevenagel condensation-Michael addition. A pyrazolone reacts with an aldehyde to generate an enone, which undergoes subsequent attack by a second pyrazolone to generate a bis-pyrazolone species. This rapid and facile ligation technique is performed under mild conditions in the absence of catalyst to generate new architectures that were previously inaccessible via conventional ligation reactions. Using this unique ligation, we generated three site-specifically labeled antibody-drug conjugates (ADCs) with an average of four drugs to one antibody. The in vitro and in vivo efficacies along with pharmacokinetic data of the site-specific ADCs are reported.<br />
DOI: 10.1021/acsmedchemlett.6b00253 PMCID: PMC5108035 PMID: 27882197<br />
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[3]. Inorg Chem. 2008 Aug 18;47(16):7396-404. doi: 10.1021/ic800615y. Epub 2008 Jul 24.<br />
1D molecular ladder of the ionic complex of terbium-4-sebacoylbis(1-phenyl-3-methyl-5-pyrazolonate) and sodium dibenzo-18-crown-6: synthesis, crystal structure, and photophysical properties.<br />
Remya PN(1), Biju S, Reddy ML, Cowley AH, Findlater M.<br />
Author information: (1)Chemical Sciences and Technology Division, National Institute for Interdisciplinary Science & Technology (NIIST), Thiruvananthapuram-695 019, India.<br />
On the basis of the novel heterocyclic beta-diketone, 4-sebacoylbis(1-phenyl-3-methyl-5-pyrazolone (H 2SbBP), three new lanthanide complexes Tb 2(SbBP) 3(H 2O) 2 ( 1), Gd 2(SbBP) 3(H 2O) 2 ( 2), and [Tb(SbBP) 2] [Na(DB18C6)H 2O] ( 3) have been synthesized and characterized by various spectroscopic techniques. The single-crystal X-ray diffraction analysis of 3 reveals that the complex crystallizes in the monoclinic space group C2/ c with a = 25.300(6) A, b = 19.204(7) A, c = 15.391(3) A, beta = 93.17(3) degrees , and V = 7466(4) A (3). The crystal structure of 3 is heterodinuclear and features a Tb (3+) center surrounded by two tetradentate bispyrazolone ligands in a somewhat distorted square-antiprismatic geometry. The Na (+) coordination environment is distorted hexagonal pyramidal and involves six oxygen atoms furnished by DB18C6 and one oxygen atom from a water molecule. The X-ray diffraction study of 3 also revealed an interesting 1D molecular ladder structure based on C-H/pi, intra- and intermolecular hydrogen-bonding interactions. The photophysical properties of 1 and 3 in solid state have been investigated, and the quantum yields and (5)D 4 lifetimes were found to be 4.82 +/- 0.01% and 18.13 +/- 0.82% and 1.11 +/- 0.01 and 2.82 +/- 0.02 ms, respectively.<br />
DOI: 10.1021/ic800615y PMID: 18651731<br />
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[4]. Anal Chem. 2011 Dec 1;83(23):9060-7. doi: 10.1021/ac2019848. Epub 2011 Nov 1.<br />
A versatile method for analysis of serine/threonine posttranslational modifications by β-elimination in the presence of pyrazolone analogues.<br />
Furukawa J(1), Fujitani N, Araki K, Takegawa Y, Kodama K, Shinohara Y.<br />
Author information: (1)Laboratory of Medical and Functional Glycomics, Graduate School of Advanced Life Science, Hokkaido University, Sapporo 001-0021, Japan.<br />
Post-translational modifications (PTMs) of serine and threonine occur by diverse mechanisms, including phosphorylation, sulfation, and various types of sugar chain modifications, making characterization of the resulting structures very labor-intensive. Moreover, to fully understand the biological functions of PTMs, both the sites of modification and the modified structures must be analyzed. The present work describes a novel, versatile strategy in which the released O-glycan and the formerly glycosylated/phosphorylated peptide are labeled and thus amenable to further study. In this approach, glycopeptides/phosphopeptides are subjected to β-elimination in the presence of pyrazolone derivatives (BEP), which in the same reaction labels the formerly glycosylated/phosphorylated peptide. The reaction is essentially a β-elimination/Michael addition in which a carbon-carbon bond-forming Michael donor rather than a heteroatomic Michael donor is used. The O-glycans released upon BEP are recovered as bis-pyrazolone derivatives, without any detectable side reaction (peeling). Using this technique, the O-glycan profiles of model mucin-type glycoproteins were successfully analyzed. The BEP strategy discriminates between phosphorylated and GlcNAcylated peptides, since cleaved GlcNAc is detectable. In addition, both the released O-glycan and the formerly glycosylated peptide can be selectively labeled by different reagents via a β-elimination reaction performed in the presence of pyrazolone and the thiol Michael donor.<br />
DOI: 10.1021/ac2019848 PMID: 21995958 [Indexed for MEDLINE]<br />
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[5]. J Fluoresc. 2018 Sep;28(5):1181-1193. doi: 10.1007/s10895-018-2282-8. Epub 2018 Sep 7.<br />
Synthesis of Symmetric Bridged Bis-Pyrazolone Based Metal Complex Acid Dyes and their Applications on Leather.<br />
Ayaz M(1), Ayaz M(1), Ali F(2), Saeed A(3), Khurshid A(4), Shabir G(5)(6), Ahmad T(7), Kazmi SAR(7), Khan HA(7).<br />
Author information: (1)Department of Chemistry, Hazara University, KPK, Mansehra, 21300, Pakistan. (2)Department of Chemistry, Hazara University, KPK, Mansehra, 21300, Pakistan. [email protected]. (3)Department of Chemistry, Quaid-I-Azam University, Islamabad, 45320, Pakistan. (4)Department of Metallurgy and Material Engineering, PIEAS, PO Nilore, Islamabad, 45650, Pakistan. (5)Department of Chemistry, Quaid-I-Azam University, Islamabad, 45320, Pakistan. [email protected]. (6)Department of Chemistry, Govt. Gordon College Rawalpindi, Punjab, Pakistan. [email protected]. (7)Department of Chemistry, Govt. Gordon College Rawalpindi, Punjab, Pakistan.<br />
Our present investigation aims at the synthesis and application of new, symmetric bridged bis-pyrazolone based acid dyes. The bis-pyrazolone compounds were accomplished from bis- hydrazine of 4,4'-Diaminostilbene-2,2'-disulfonic acid and ethyl acetoacetate. The bis-pyrazolones have been coupled with diazonium salts of o-hydroxyl aromatic amines which resulted in ligand dyes. The intermediate ligand dyes were treated with 3d transition metals to achieve the targeted metal complex acid dyes. The structures of investigated compounds were confirmed with the help of spectroscopic techniques. Dyes were applied on leather and their application parameters including their light fastness, wash fastness and rubbing fastness were determined. Graphical Abstract Symmetric brymmetric Bridged bis-Pyrazolone based Metal Complex Acid.<br />
DOI: 10.1007/s10895-018-2282-8 PMID: 30191355
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