- 4-Phosphopyrazol-2-yl alanine: A non-hydrolysable analogue of phosphohistidine
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We report the synthesis of a stable analogue of τ-phosphohistidine: 4-phosphopyrazol-2-yl alanine (pPza). Polyclonal antibodies generated against the mimic show high reactivity and selectivity for τ-phosphohistidine, with minor or no cross-reactivity towards non-phosphorylated histidine or O-phosphoamino acids, including phosphotyrosine.
- Lilley, Matthew,Mambwe, Bezaleel,Thompson, Mark J.,Jackson, Richard F. W.,Muimo, Richmond
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Read Online
- Improved synthesis of 1H-pyrazole-4-carbaldehyde
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A simple and convenient two-step method for the synthesis of the title compound 1 was developed using N-protected 4-pyrazolilmagnesium bromide 9 as a key intermediate. Laborious procedures for purification or isolation of target compound are not required, therefore, up to 20g of 1 could be obtained in a single run.
- Taydakov, Ilya V.,Krasnoselskiy, Sergey S.,Dutova, Tatiana Y.
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Read Online
- Cytotoxic Ruthenium(II) Complexes of Pyrazolylbenzimidazole Ligands That Inhibit VEGFR2 Phosphorylation
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Eight new ruthenium(II) complexes of N,N-chelating pyrazolylbenzimidazole ligands of the general formula [RuII(p-cym)(L)X]+ [where the ligand L is 2-(1H-pyrazol-1-yl)-1H-benzo[d]imidazole (L1) substituted at the 4 position of the pyrazole ring by Cl (L2), Br (L3), or I (L4) and X = Cl- and I-] were synthesized and characterized using various analytical techniques. Complexes 1 and 3 were also characterized by single-crystal X-ray crystallography, and they crystallized as a monoclinic crystal system in space groups P21/n and P21/c, respectively. The complexes display good solution stability at physiological pH 7.4. The iodido-coordinated pyrazolylbenzimidazole ruthenium(II) p-cymene complexes (2, 4, 6, and 8) are more resistant toward hydrolysis and have less tendency to form monoaquated complexes in comparison to their chlorido analogues (1, 3, 5, and 7). The halido-substituted 2-(1H-pyrazol-1-yl)-1H-benzo[d]imidazole ligands, designed as organic-directing molecules, inhibit vascular endothelial growth factor receptor 2 (VEGFR2) phosphorylation. In addition, the ruthenium(II) complexes display a potential to bind to DNA bases. The cytotoxicity profile of the complexes (IC50 ca. 9-12 μM for 4-8) against the triple-negative breast cancer cells (MDA-MB-231) show that most of the complexes are efficient. The lipophilicity and cellular accumulation data of the complexes show a good correlation with the cytotoxicity profile of 1-8. The representative complexes 3 and 7 demonstrate the capability of arresting the cell cycle in the G2/M phase and induce apoptosis. The inhibition of VEGFR2 phosphorylation with the representative ligands L2 and L4 and the corresponding metal complexes 3 and 7 in vitro shows that the organic-directing ligands and their complexes inhibit VEGFR2 phosphorylation. Besides, L2, L4, 3, and 7 inhibit the phosphorylation of extracellular signal-regulated kinase 1/2 (ERK1/2) and proto-oncogene tyrosine-protein kinase (Src), capable of acting downstream of VEGFR2 as well as independently. Compounds L2, L4, 3, and 7 have a lesser effect on ERK1/2 and more prominently affect Src phosphorylation. We extended the study for L2 and 3 in the Tg(fli1:gfp) zebrafish model and found that L2 is more effective in vivo compared to 3 in inhibiting angiogenesis.
- Acharya, Moulinath,Chakraborty, Ayan,Chakraborty, Manas Pratim,Das, Rahul,Koley, Tuhin Subhra,Mukherjee, Arindam,Purkait, Kallol,Roy, Shantanu Saha,Roy, Souryadip
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supporting information
p. 18379 - 18394
(2021/12/01)
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- Cui-catalyzed coupling reactions of 4-iodopyrazoles and alcohols: Application toward withasomnine and Homologs
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The direct 4-alkoxylation of 4-iodo-1H-pyrazoles with alcohols was achieved by a CuIcatalyzed coupling protocol. The optimal reaction conditions employed excess alcohol and potassium t-butoxide (2 equiv) in the presence of CuI (20 mol%) and 3,4,7,8-tetramethyl-1,10-phenanthroline (20 mol%) at 130 °C for 1 h under microwave irradiation. The present method was efficiently applied to the synthesis of withasomnine and its six- and seven-membered cyclic homologs.
- Harusawa, Shinya,Hayama, Noboru,Kubo, Yumika,Kuroiwa, Nao,Nakamizu, Ayaka,Nishikawa, Kohei,Ono, Jun,Takagaki, Toshiki,Tatsui, Yuya,Usami, Yoshihide,Yoneyama, Hiroki
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- Method for synthesizing 1 - methyl -4 -iodo pyrazole (by machine translation)
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The invention relates to the technical field 1 - methyl -4 - iodinol synthesis, in particular to a synthesis method of 1 - methyl -4 - iodo pyrazole. The synthesis method of 1 - methyl -4 - iodinol comprises the following steps: (1) mixing 1 - methylpyrazole with iodine, heating to 40 - 80 °C, dropwise adding an oxidizing agent aqueous solution to carry out iodination reaction, and (2) adding alkali liquor to 5 - 9 DEG C to obtain a light yellow crystal, namely 1 - methyl -4 - iodo pyrazole. To 1 - methyl -4 - iodinol synthesis method, 1 - methylpyrazole raw materials are used as the iodinating agent, and an oxidizing agent, an oxidizing agent and hydrogen iodide are added to generate iodine, so that iodine is fully utilized, the reaction rate and product yield are improved, and the synthesis cost 1 - methyl -4 -iodo pyrazole is greatly reduced. (by machine translation)
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Paragraph 0050-0053
(2020/06/16)
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- PROCESSES AND INTERMEDIATES FOR MAKING A JAK INHIBITOR
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This invention relates to processes and intermediates for making {1-{1-[3-fluoro-2-(trifluoromethyl)isonicotinoyl]piperidin-4-yl}-3-[4-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-1H-pyrazol-1-yl]azetidin-3-yl}acetonitrile, useful in the treatment of diseases related to the activity of Janus kinases (JAK) including inflammatory disorders, autoimmune disorders, cancer, and other diseases.
- -
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Paragraph 0116-0117
(2019/08/22)
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- Deprotonation of 4-ethynylpyrazolium salts
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4-Ethynyl-1,2-dimethylpyrazolium salts were prepared by methylation of the corresponding 4-ethynyl-1-methylpyrazoles with trimethyloxonium tetrafluoroborate and were deprotonated to give the corresponding pyrazolium-4acetylenides, which are mesomeric betaines. These can be represented as alkynyl- or mesoionic allenylidene-type resonance forms. Calculations and spectroscopic investigations were performed to determine the contribution of each canonical form to the overall structure. Ylides and N-heterocyclic carbenes are tautomers of the betaines. Their relative stabilities have been compared.
- Ahlburg, Nils Lennart,Doppleb, Olivia,Hillrichs, Kai,Namyslo, Jan C.,Hübner, Eike G.,Schmidt, Andreas
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p. 1203 - 1215
(2018/08/06)
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- Bivalent carbamates as novel control agents of the malaria mosquito, Anopheles gambiae
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Widespread pyrethroid resistance has caused an urgent need to develop new insecticides for control of the malaria mosquito, Anopheles gambiae. Insecticide discovery efforts were directed towards the construction of bivalent inhibitors that occupy both the peripheral and catalytic sites of the mosquito acetylcholinesterase (AChE). It was hypothesized that this approach would yield a selective, high potency inhibitor that would also circumvent known catalytic site mutations (e.g. G119S) causing target site resistance. Accordingly, a series of bivalent phthalimide-pyrazole carbamates were prepared having an alkyl chain linker of varying length, along with other modifications. The most active compound was (1-(3-(1,3-dioxoisoindolin-2-yl)propyl)-1H-pyrazol-4-yl methylcarbamate, 8a), which has a chain length of three carbons, good mosquito anticholinesterase activity, and ca. 5-fold selectivity compared to human AChE. Moreover, this compound was toxic to mosquitoes by topical application (LD50 = 63 ng/female) with only 6-fold cross resistance in the Akron strain of Anopheles gambiae that showed 50- to 60-fold resistance to conventional carbamate insecticides. However, contact lethality in the WHO paper assay was disappointing. The implications of these results for design of new mosquitocides are discussed.
- Mutunga, James M.,Chen, Qiao-Hong,Wong, Dawn M.,Lam, Polo C.-H.,Li, Jianyong,Totrov, Maxim M.,Gross, Aaron D.,Carlier, Paul R.,Bloomquist, Jeffrey R.
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p. 704 - 708
(2016/10/30)
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- A 1-alkyl-pyrazol-4-boronic acid frequency method for the synthesis of ester
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The invention belongs to the field of organic chemical synthesis and provides a synthetic method of 1-alkylpyrazole-4-boronic acid pinacol ester. The synthetic method comprises the following three steps: 1. reacting pyrazole with iodine and hydrogen peroxide to generate 4-iodopyrazole A; 2. reacting the 4-iodopyrazole with alkyl halide to obtain an intermediate B; 3. preparing a Grignard reagent of the raw material by using 1-alkyl-4-iodopyrazole as a raw material and adopting an isopropyl Grignard reagent exchange method at 0-30 DEG C, with BE001 as a boron reagent, and reacting to obtain the final product. The technological method is accessible in raw materials, simple and convenient to operate and lower in cost and is a proper method for preparing 1-alkylpyrazole-4-boronic acid pinacol ester compounds.
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Paragraph 0021; 0025-0028
(2017/03/14)
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- Mild regioselective iodination of pyrazoles using n-butyltriphenylphosphonium peroxodisulfate
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A practical, efficient and inexpensive method of synthesis of iodopyrazoles by the reaction of pyrazoles with iodine using n-butyltriphenylphosphonium peroxodisulfate as an oxidant at room temperature is reported. The use of n-butyltriphenylphosphonium peroxodisulfate is feasible due to its easy preparation and handling, high stability and activity.
- Gorjizadeh,Afshari,Naseh
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p. 1931 - 1934
(2016/10/04)
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- Transition-Metal-Free N-Arylation of Pyrazoles with Diaryliodonium Salts
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A new synthetic method was developed for the N-arylation of pyrazoles using diaryliodonium salts. The transformation does not require any transition-metal catalyst and provides the desired N-arylpyrazoles rapidly under mild reaction condition in the presence of aqueous ammonia solution as a mild base without the use of inert atmosphere. The chemoselectivity of unsymmetric diaryliodonium salts was also explored with large number of examples.
- Gonda, Zsombor,Novák, Zoltán
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supporting information
p. 16801 - 16806
(2015/11/16)
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- Rapid and efficient copper-catalyzed finkelstein reaction of (hetero)aromatics under continuous-flow conditions
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A general, rapid, and efficient method for the copper-catalyzed Finkelstein reaction of (hetero)aromatics has been developed using continuous flow to generate a variety of aryl iodides. The described method can tolerate a broad spectrum of functional groups, including N-H and O-H groups. Additionally, in lieu of isolation, the aryl iodide solutions were used in two distinct multistep continuous-flow processes (amidation and Mg-I exchange/nucleophilic addition) to demonstrate the flexibility of this method.
- Chen, Mao,Ichikawa, Saki,Buchwald, Stephen L.
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supporting information
p. 263 - 266
(2015/02/05)
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- New approach to electrochemical iodination of arenes exemplified by the synthesis of 4-iodopyrazoles of different structures
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The two-stage electrosynthesis of 4-iodosubstituted pyrazole derivatives was performed. At the first stage, KIO3 was obtained at the Ni anode under the undivided galvanostatic conditions of electrolysis of an aqueous alkaline solution of KI (or I2) at the Ni anode. At the second stage, pyrazole and its derivatives were iodinated in the heterophase (H2O-CHCl3 (CCl4)) medium by the KIO3-KI (or KIO3-I2) system in the presence of H2SO4. The yields of iodopyrazoles were 74-92%. The electrochemical iodination of anisole, 2-methylpyrazole, and thiophene was carried out to form 4-iodoanisole (88% yield), 4,5-diiodo-2-methylimidazole (54% yield), and a mixture of 2-iodothiophene (60% yield) and 2,5-diiodothiophene (4% yield).
- Lyalin,Petrosyan
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p. 360 - 367
(2015/02/05)
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- PROCESSES AND INTERMEDIATES FOR MAKING A JAK INHIBITOR
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This invention relates to processes and intermediates for making {1-{1-[3-fluoro-2-(trifluoromethyl)isonicotinoyl]piperidin-4-yl}-3-[4-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-1H-pyrazol-1-yl]azetidin-3-yl}acetonitrile, useful in the treatment of diseases related to the activity of Janus kinases (JAK) including inflammatory disorders, autoimmune disorders, cancer, and other diseases.
- -
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Paragraph 0159
(2014/09/29)
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- PYRROLOPYRIDINEAMINO DERIVATIVES AS MPS1 INHIBITORS
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The present invention relates to the use of certain pyrrolopyridineamino derivatives (hereinafter referred to as “PPA derivatives”), particularly 1H-pyrrolo[3,2-c]pyridine-6-amino derivatives, to inhibit the spindle checkpoint function of Monospindle 1 (Mps1—also known as TTK) kinases either directly or indirectly via interaction with the Mps kinase itself. In particular, the present invention relates to PPA derivatives for use as therapeutic agents for the treatment and/or prevention of proliferative diseases, such as cancer. The present invention also relates to processes for the preparation of the PPA derivatives, and pharmaceutical compositions comprising them. Formula (I)
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Paragraph 0621-0622
(2014/02/15)
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- Highly hydrophobic isoreticular porous metal-organic frameworks for the capture of harmful volatile organic compounds
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Tunable hydrophobicity: Efficient air filters for the protection against chemical warfare agents might be achieved by surface functionalization of the pores in robust metal-organic frameworks (MOFs) with fluoroalkyl residues and the precise control of their pore size (see picture). These MOFs capture harmful volatile organic compounds even under extremely moist conditions (80 % relative humidity). Copyright
- Padial, Natalia M.,Quartapelle Procopio, Elsa,Montoro, Carmen,Lopez, Elena,Oltra, J. Enrique,Colombo, Valentina,Maspero, Angelo,Masciocchi, Norberto,Galli, Simona,Senkovska, Irena,Kaskel, Stefan,Barea, Elisa,Navarro, Jorge A. R.
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supporting information
p. 8290 - 8294
(2013/09/02)
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- Fast halogenation of some N-heterocycles by means of N,N'-dihalo-5,5- dimethylhydantoin
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An instantaneous, selective and high-yielding halogenation process is reported. The method operates with imidazoles, pyrazoles, and indoles under benign reaction conditions. The developed process involves the use of N,N'-dihalo-5,5-dimethylhydantoins (halo=chlorine, bromine, iodine) as halogenation reagents that are activated by catalytic quantities of a strong Bronsted acid. Moreover, the halogenation process is switchable to produce either the mono- or di-halogenated products. Issues related to the reaction mechanism are investigated and a proposal for a reaction mechanism is disclosed.
- Sandtorv, Alexander H.,Bjorsvik, Hans-Rene
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p. 499 - 507
(2013/05/08)
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- Efficient iodination of structurally varying pyrazoles in heterophase medium
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A synthesis of 4-iodo-substituted pyrazoles by iodination of pyrazole and its derivatives in the heterophase (H2O/CHCl3 (CCl 4)) medium with the system KI-KIO3 in the presence of H2SO4 additives was accomplished. The yields of 4-iodo-substituted pyrazoles in the iodination of pyrazole, 3,5- dimethylpyrazole, pyrazole-3(5)-carboxylic acid, 1-methylpyrazole-3-carboxylic acid, 1-methylpyrazole-5-carboxylic acid, 3-nitropyrazole, 1-methyl-3- nitropyrazole, 1-methylpyrazole, 1-ethylpyrazole, and 1-isopropylpyrazole were within 80-97%, whereas in the case of 3-nitropyrazole-5-carboxylic acid it was 32%.
- Lyalin,Petrosyan
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p. 1044 - 1051
(2014/03/21)
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- PYRROLOPYRIDINEAMINO DERIVATIVES AS MPS1 INHIBITORS
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The present invention relates to the use of certain pyrrolopyridineamino derivatives (hereinafter referred to as "PPA derivatives"), particularly 1H-pyrrolo[3,2-c]pyridine-6- amino derivatives, to inhibit the spindle checkpoint function of Monospindle 1 (Mps1 – also known as TTK) kinases either directly or indirectly via interaction with the Mps kinase itself. In particular, the present invention relates to PPA derivatives for use as therapeutic agents for the treatment and/or prevention of proliferative diseases, such as cancer. The present invention also relates to processes for the preparation of the PPA derivatives, and pharmaceutical compositions comprising them. Formula (I)
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Page/Page column 63
(2012/10/07)
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- A simple method for iodination of heterocyclic compounds using HIO 4/NaCl/silica gel/H2SO4 in water
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A fast and simple method for iodination of some heterocycles is reported. The reactions were carried out in water, using HIO4/H 2SO4/NaCl/silica gel at moderate temperatures of 25-50 °C. Springer-Verlag 2011.
- Hosseini, Abolfazl,Khalilzadeh, Mohammad A.,Hosseinzadeh, Masoumeh,Tajbakhsh, Mahmoud
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experimental part
p. 619 - 623
(2012/07/14)
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- Synthesis, structural, and biological evaluation of the arene-linked pyrazolyl methane ligands and their d9/d10 metal complexes
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A series of the p-bis[(1-pyrazolyl)methyl] benzene ligands (L 1-L6) in the DMSO system were synthesized. In the mean time, by using the ligands as a linker, a new family of transition metal coordination polymers, namely, [Cu2(L1)2Cl 4] (1), [Cu2(L2)2Cl4] (2), [Ag(L2)(NO3)] (3), [Zn2(L 2)2(SCN)4] (4) and [Cd2(L 2)(SCN)4] (5) [L1 = 1,4-bis((1H-pyrazol-1-yl) methyl)benzene; L2 = 1,4-bis(3,5-dimethyl-1H-pyrazol-1-yl)methyl) benzene] have been constructed by the reaction of the p-bis[(1-pyrazolyl)methyl] benzene and corresponding to the transition metal compounds in a mixed solution of CH3OH/C2H5OH at mild temperature condition. All the coordination polymers and p-bis[(1-pyrazolyl)methyl]benzene ligands were characterized by elemental analysis, IR spectroscopy, 1H NMR and 13C NMR, and some of them were characterized by UV spectroscopy, thermogravimetric analysis, X-ray powder and X-ray single-crystal diffraction. Structural analyses reveal that the ligands L3-L5 (L 3 = 1,4-bis((4-iodo-1H-pyrazol-1-yl)methyl)benzene, L4 = 1,4-bis((4-iodo-3,5-dimethyl-1H-pyrazol-1-yl)methyl)benzene, L5 = 1,4-bis((4-nitro-1H-pyrazol-1-yl)methyl)benzene,L6 = 1,4-bis((4-nitro-3,5-dimethyl-1H-pyrazol-1-yl) methyl) benzene) are discrete organic compound molecules and the complexes 1-5 are 1D M-L-M coordination polymers, which are further interlinked via hydrogen bonds resulting in 2D or even 3D supermolecular networks. The luminescent properties of the coordination polymers 3, 4 and 5 were examined by luminescence spectra. The analytic results indicate that different metal complexes with the same ligand have different influence on the characteristic photoluminescence. Furthermore, the cytotoxicity of the ligands L1-L6 and complexes 1-5 were evaluated against hepG2 cells. For the ligands of L1-L6, the different substituents of the pyrazole ring slightly influenced the cytotoxicity of the cell. It is found that nitro-compounds have shown the highest cytotoxicity under the same concentration condition. The cytotoxic activity of the complexes 1-5 are strongly increased by the introduction of the transition metals.
- Wang, Xin-Yu,Liu, Shu-Qing,Zhang, Chun-Yan,Song, Ge,Bai, Feng-Ying,Xing, Yong-Heng,Shi, Zhan
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p. 151 - 164
(2013/01/15)
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- HETEROCYCLIC COMPOUNDS AS JANUS KINASE INHIBITORS
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The invention provides compounds of formula (I) or a salt thereof as described herein. The invention also provides pharmaceutical compositions comprising a compound of formula (I), processes for preparing compounds of formula (I), intermediates useful for preparing compounds of formula I and therapeutic methods for suppressing an immune response or treating cancer or a hematologic malignancy using compounds of formula (I).
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Page/Page column 148
(2011/04/18)
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- New pyrazolyl and thienyl aminohydantoins as potent BACE1 inhibitors: Exploring the S2′ region
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The proteolytic enzyme β-secretase (BACE1) plays a central role in the synthesis of the pathogenic β-amyloid in Alzheimer's disease. SAR studies of the S2′ region of the BACE1 ligand binding pocket with pyrazolyl and thienyl P2′ side chains are reported. These analogs exhibit low nanomolar potency for BACE1, and demonstrate >50- to 100-fold selectivity for the structurally related aspartyl proteases BACE2 and cathepsin D. Small groups attached at the nitrogen of the P2′ pyrazolyl moiety, together with the P3 pyrimidine nucleus projecting into the S3 region of the binding pocket, are critical components to ligand's potency and selectivity. P2′ thiophene side chain analogs are highly potent BACE1 inhibitors with excellent selectivity against cathepsin D, but only modest selectivity against BACE2. The cell-based activity of these new analogs tracked well with their increased molecular binding with EC50 values of 0.07-0.2 μM in the ELISA assay for the most potent analogs.
- Malamas, Michael S.,Erdei, Jim,Gunawan, Iwan,Barnes, Keith,Hui, Yu,Johnson, Matthew,Robichaud, Albert,Zhou, Ping,Yan, Yinfa,Solvibile, William,Turner, Jim,Fan, Kristi Yi,Chopra, Rajiv,Bard, Jonathan,Pangalos, Menelas N.
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scheme or table
p. 5164 - 5170
(2011/10/09)
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- PROCESSES FOR PREPARING JAK INHIBITORS AND RELATED INTERMEDIATE COMPOUNDS
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The present invention is related to processes for preparing chiral substituted pyrazolyl pyrrolo[2,3-d]pyrimidines of Formula III, and related synthetic intermediate compounds. The chiral substituted pyrazolyl pyrrolo[2,3-d]pyrimidines are useful as inhibitors of the Janus Kinase family of protein tyrosine kinases (JAKs) for treatment of inflammatory diseases, myeloproliferative disorders, and other diseases.
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Page/Page column 102-103
(2010/08/07)
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- Electrosynthesis of 4-iodopyrazole and its derivatives
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Electrosynthesis of 4-iodo-substituted pyrazoles has been accomplished by iodination of the corresponding precursors on a Pt-anode in aqueous solutions of KI under conditions of the diaphragm galvanostatic electrolysis. Efficiency of the process depends on the donor-acceptor properties of substituents and their positions in the pyrazole ring. Thus, iodination of pyrazole, 3,5-dimethylpyrazole, 3-nitropyrazole, 1-methylpyrazole, 1,3-dimethylpyrazole, pyrazole-3(5)-carboxylic acid or methyl esters furnished 4-iodo derivatives in 57, 86, 2, 5, 35, 30, and 40% yields, respectively.
- Lyalin,Petrosyan,Ugrak
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experimental part
p. 1549 - 1555
(2011/05/04)
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- Green iodination of pyrazoles with iodine/hydrogen peroxide in water
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In this Letter, we describe a practical, green iodination of pyrazoles to form the corresponding 4-iodopyrazole derivatives. The reaction takes place in water, using only 0.5 equiv of iodine and 0.6 equiv of hydrogen peroxide, a system that generates water as the only reaction by-product.
- Kim, Mary M.,Ruck, Rebecca T.,Zhao, Dalian,Huffman, Mark A.
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p. 4026 - 4028
(2008/09/20)
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- Amino-5-(5-membered)hetero-arylimidazolone compounds and the use thereof for beta-secretase modulation
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The present invention provides a 2-amino-5-heteroaryl-5-phenylimidazolone compound of formula I The present invention also provides methods for the use thereof to inhibit β-secretase (BACE) and treat β-amyloid deposits and neurofibrillary tangles
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Page/Page column 13-14
(2008/06/13)
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- A comparison of microwave-accelerated and conventionally heated iodination reactions of some arenes and heteroarenes, using ortho-periodic acid as the oxidant
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A fast and simple method for the oxidative iodination of some activated arenes and heteroarenes, either under microwave irradiation or by conventional heating, is reported, using diiodine and ortho-periodic acid as the oxidant. The reactions were carried out in hot 95% ethanol under a reflux condenser. For the microwave assisted reactions, the reaction times were always notably shortened, but the yields were nearly the same as those afforded by the conventional method.
- Sosnowski, Maciej,Skulski, Lech
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p. 401 - 406
(2007/10/03)
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- A multifunctional high-spin biradical pyrazolylbipyridine- bisnitronylnitroxide
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(Chemical Equation Presented) Synthesis and UV-vis, IR, and EPR spectroscopic characterizations, together with X-ray structural analysis, of functional nitronyl- and iminonitroxides attached to pyrazolylbipyridine are described. The exchange interactions between the nitronylnitroxides are found to be stronger than for the iminonitroxides. Although the substitution of a pyridine with the pyrazole ring leads to shorter distances and larger dipolar couplings, the exchange interaction is diminished. While compound 1 forms dimers in the solid state, the terpyridine 3 leads to supramolecular π-stacking.
- Zoppellaro, Giorgio,Enkelmann, Volker,Geies, Ahmed,Baumgarten, Martin
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p. 4929 - 4932
(2007/10/03)
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- Specifically targeted catalytic antagonists and uses thereof
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This invention provides chimeric molecules that are catalytic antagonists of a target molecule. The catalytic antagonists of this invention preferably comprise a targeting moiety attached to an enzyme that degrades the molecule specifically bound by the targeting moiety. The catalytic antagonists of this invention thus bind to a target recognized by the targeting moiety (e.g., a receptor) the enzyme component of the chimera then degrades all or part of the target. This typically results in a reduction or loss of activity of the target and release of the chimeric molecule. The chimeric molecule is then free to attack and degrade another target molecule.
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- Ethyl vinyl ether - An agent for protection of the pyrazole NH-fragment. A convenient method for the preparation of N-unsubstituted 4-alkynylpyrazoles
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N-Unsubstituted 4-iodopyrazole (1) is easily converted into 4-alkynyl derivatives (5) in moderate to good overall yields by using intermediate protection of the nitrogen atom of the pyrazole ring by ethyl vinyl ether.
- Vasilevsky, Sergei F.,Klyatskaya, Svetlana V.,Tretyakov, Eugene V.,Elguero, José
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p. 879 - 886
(2007/10/03)
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- Synthesis of a tritium-labeled, fipronil-based, highly potent, photoaffinity probe for the GABA receptor
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3-{4-[1-(2,6-Dichloro-4-trifluoromethylphenyl)pyrazolo]} -3-(trifluoromethyl)diazirine is a fipronil-based (i.e. fiprole), high-affinity probe for the GABA receptor. For synthesis of the tritium-labeled version of this trifluoromethyldiazirinylfiprole ([3H]TDF) the required intermediate, 3-{4-[1-(2,6-dichloro-3-iodo-4-trifluoromethylphenyl)-5-iodopyrazolo]} -3-(trifluoromethyl)diazirine, was prepared in 10 steps from pyrazole and 3,5-dichloro-4-fluorobenzotrifluoride. One of the key transformations was lithiation and subsequent iodination of the 4-(2,2,2-trifluoro-1-hydroxyethyl)pyrazole intermediate. The last step involved reduction of the diiodofiprole with tritium, Pd/C, and triethylamine in ethyl acetate and afforded [3H]TDF with a specific activity of 15 Ci/mmol and 99% radiopurity.
- Sammelsont, Robert E.,Casida, John E.
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p. 8075 - 8079
(2007/10/03)
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- Solvent-Free Iodination of Arenes at Room Temperature
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Silica supported bismuth(III)nitrate pentahydrate [BNP-SiO2] was prepared under simple co-grinding condition. The iodination of aromatic compounds using BNP-SiO2 and molecular iodine under solvent-free conditions is described. The reaction occurred in the solid state at room temperature, yielding the corresponding mono-iodo derivative in good yields. However, less activated aromatics required longer reaction time with comparatively less yield.
- Alexander, Varughese M.,Khandekar, Amit C.,Samant, Shriniwas D.
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p. 1895 - 1897
(2007/10/03)
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- A mild and efficient method for the regioselective iodination of pyrazoles
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The iodination of N-H or N-benzylpyrazoles using elemental iodine in the presence of CAN as the in situ oxidant is a mild and efficient method to prepare 4-iodopyrazoles containing even electron-withdrawing substituents. The reaction is regioselective since the iodine atom preferred pyrazole instead of the benzyl group, and the 4-pyrazolic position instead of other possible positions in the heterocycle.
- Rodríguez-Franco, María Isabel,Dorronsoro, Isabel,Hernández-Higueras, Ana I,Antequera, Gema
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p. 863 - 865
(2007/10/03)
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- Aromatic iodination in aqueous solution. A new lease of life for aqueous potassium dichloroiodate
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A re-investigation of the use of aqueous potassium dichloroiodate (KICl2) as an iodinating agent for aromatic compounds has found the reagent to be more generally applicable than previously known. The reagent has been found to give excellent yields of iodinated heterocyclic compounds, such as isatin, imidazole and pyrazole.
- Garden, Simon J.,Torres, José C.,De Souza Melo, Simone C.,Lima, Alexandre S.,Pinto, Angelo C.,Lima, Edson L.S.
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p. 2089 - 2092
(2007/10/03)
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- Aromatic iodination of activated arenes and heterocycles with lead tetraacetate as the oxidant
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An easy, cheap and fairly quick laboratory method is presented for aromatic iodination of some highly activated arenes and heterocycles with molecular iodine in the presence of either pure lead tetraacetate dissolved in glacial acetic acid, or with the same oxidant but prepared in situ from Pb3O4 dissolved in hot AcOH/Ac2O prior to the iodination. 4-Bromo- and 2,4-dibromoanisoles are obtained from anisole by the respective oxidative bromination.
- Krassowska-Swiebocka,Lulinski,Skulski
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p. 926 - 928
(2007/10/02)
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- Micelle Activated Reactions I. Micelle Activated Iodination and Partial Dehalogenation of Pyrazoles and 1,2,4-Triazoles
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A method is described to iodinate pyrazole, substituted pyrazoles or 1,2,4-triazole with iodine or iodine chloride in aqueous alkaline in the presence of an anionic surfactant. 4-Iodo- (2a), 4-iodo-3(5)-methyl- (2b), 3(5),4-diiodo- (3a), 3(5),4-diiodo-5(3)-methyl- (3b), and 3,4,5-triiodo-pyrazole (3d) as soon as 4-iodo-pyrazole-3(5)-carboxylic acid (2c), and 3(5)-iodo-1,2,4-triazole (5) were prepared.Anhydrous hydrogen fluoride or triethylamine trishydrofluoride were found to be a suitable agent to effect a regioselective partial dehalogenation of 3b, 3d and 3,5-dibromo-1,2,4-triazole (7).We prepared 3(5)-iodo-5(3)-methyl-pyrazole (6b), 3,5-diiodo-pyrazole (6d) and 3(5)-bromo-1,2,4-triazole (8) on this way.
- Miethchen, R.,Randow, R.,Listemann, R.,Hildebrandt, J.,Kohlheim, K.
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p. 799 - 805
(2007/10/02)
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