6959-47-3Relevant articles and documents
Synthesis method of 2-chloromethylpyridine hydrochloride
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Paragraph 0018-0024, (2020/05/05)
The invention belongs to the field of organic synthesis, and specifically relates to a synthesis method of 2-chloromethylpyridine hydrochloride. The synthesis method comprises the following steps: (1)taking 2-methylpyridine as a raw material and reacting 2-methylpyridine with hydrogen peroxide in the presence of acetic acid to generate oxynitride-2-methylpyridine, wherein the molar ratio of 2-methylpyridine: acetic acid: hydrogen peroxide is 1: (1-1.1): (1.3-1.5), the oxidation reaction temperature is 70-80 DEG C, and the reaction time is 10-14 h; (2) carrying out reactions between oxynitride-2-methylpyridine and glacial acetic acid to generate methyl 2-pyridylacetate; (3) hydrolyzing methyl 2-pyridylacetate to obtain 2-pyridylcarbinol; and (4) reacting 2-pyridylcarbinol with thionyl chloride to obtain the target product namely 2-chloromethylpyridine hydrochloride, wherein the molar ratio of 2-pyridylcarbinol to the thionyl chloride is 1: (1.1-1.3). The preparation method provided bythe invention is high in yield, low in cost, mild in reaction conditions and easy for industrial production.
Synthesis of Co(II) NNN-pyridine based complexes and their activity in the partial oxidation of n-octane
Chanerika, Revana,Friedrich, Holger B.,Shozi, Mzamo L.
, (2019/07/12)
A series of four NNN-pyridine based ligands of the general form: pyCH2N(R)CH2py {R = propyl, tert-butyl, cyclohexyl and phenyl; py = pyridine} were synthesised and characterised. Complexation of each ligand to CoCl2?6H2O afforded new Co(II) complexes [Co{pyCH2N(R)CH2py}Cl2] (R = C3H7 (1), C(CH3)3 (2), C6H11 (3) and C6H5 (4)). Single crystal X-ray diffraction data confirmed that complex 1 crystallised as a mononuclear unit and was characterised by a distorted trigonal bipyramidal arrangement of ligands around Co. As catalysts in the oxidation of n-octane using t-BuOOH as oxidant, 2 (10% product yield) was found to be most efficient and the selectivity over 1–4 was predominantly towards 2-octanol, after reduction of alkylhydroperoxides by PPh3. All catalysts were significantly more active in the activation of n-octane using hydrogen peroxide, with a yield of 45% observed over catalyst 3. Furthermore, with H2O2, all catalysts produced a high concentration of alkylhydroperoxides, with catalyst 4 giving up to 91% alcohols after workup. TONs of up to 1100 were achieved over the Co/H2O2 systems.
Synthesis method of 2-chloromethylpyridine hydrochloride
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Paragraph 0018-0024, (2019/05/28)
The invention belongs to the field of organic synthesis, and particularly relates to a synthesis method of 2-chloromethylpyridine hydrochloride. The synthesis method includes following steps: (1), taking 2-methylpyridine as a raw material, reacting with hydrogen peroxide in an acetic acid condition to generate nitrogen oxide-2-methylpyridine, wherein a molar ratio of 2-methylpyridine, acetic acidand hydrogen peroxide is 1:1-1.1:1.3-1.5, temperature of oxidizing reaction is 70-80 DEG C, and reaction time is 10-14h; (2), allowing nitrogen oxide 2-methylpyridine to react with glacial acetic acid to generate 2-methyl pyridylacetate; (3), hydrolyzing 2-methyl pyridylacetate into 2-pyridinemethanol; (4), allowing 2-pyridylacetate to react with thionyl chloride to obtain a target product-2-chloromethylpyridine hydrochloride, wherein a molar ratio of 2-pyridinemethanol to thionyl chloride is 1:1.1-1.3. The preparation method is high in yield, low in cost, mild in reaction condition and easyin industrial production.
Tetrazolylhydrazides as selective fragment-like inhibitors of the JumonjiC-domain-containing histone demethylase KDM4A
Rüger, Nicole,Roatsch, Martin,Emmrich, Thomas,Franz, Henriette,Schüle, Roland,Jung, Manfred,Link, Andreas
supporting information, p. 1875 - 1883 (2015/11/10)
The JumonjiC-domain-containing histone demethylase 2A (JMJD2A, KDM4A) is a key player in the epigenetic regulation of gene expression. Previous publications have shown that both elevated and lowered enzyme levels are associated with certain types of cancer, and therefore the definite role of KDM4A in oncogenesis remains elusive. To identify a novel molecular starting point with favorable physicochemical properties for the investigation of the physiological role of KDM4A, we screened a number of molecules bearing an iron-chelating moiety by using two independent assays. In this way, we were able to identify 2-(1H-tetrazol-5-yl)acetohydrazide as a novel fragment-like lead structure with low relative molecular mass (Mr=142 Da), low complexity, and an IC50 value of 46.6 μm in a formaldehyde dehydrogenase (FDH)-coupled assay and 2.4 μm in an antibody-based assay. Despite its small size, relative selectivity against two other demethylases could be demonstrated for this compound. This is the first example of a tetrazole group as a warhead in JMJD demethylases. Anchor fragment: To develop non-promiscuous metalloenzyme inhibitors, a metal-complexing acetohydrazide group was integrated in a tetrazolyl fragment, which can be matured into a scaffold to promote further selectivity at the ligand backbone binding site of these emerging drug targets.
Facial triad modelling using ferrous pyridinyl prolinate complexes: Synthesis and catalytic applications
Moelands, Marcel A. H.,Schamhart, Daniel J.,Folkertsma, Emma,Lutz, Martin,Spek, Anthony L.,Klein Gebbink, Robertus J. M.
, p. 6769 - 6785 (2014/05/06)
A series of new chiral pyridinyl prolinate (RPyProR) ligands and their corresponding Fe(ii) triflate and chloride complexes are reported. The ligands possess an NN′O coordination motif, as found in the active site of non-heme iron enzymes with the so-called 2-His-1-carboxylate facial triad. The coordination behaviour of these ligands towards iron turned out to be dependent on the counter ion (chloride or triflate), the crystallization conditions (coordinating or non-coordinating solvents) and the presence of substituents on the ligand. In combination with Fe(ii)(OTf)2, coordinatively saturated complexes of the type [Fe(L)2](OTf)2 are formed, in which the ligands adopt a meridional coordination mode. The use of FeCl 2 in a non-coordinating solvent leads to 5-coordinated complexes [Fe(L)(Cl)2] with a meridional N,N′,O ligand. Crystallization of these complexes from a coordinating solvent leads to 6-coordinated [Fe(L)(solv)(Cl)2] complexes (solv = methanol or acetonitrile), in which the N,N′,O ligand is coordinated in a facial manner. For RPyProR ligands bearing a 6-Me substituent on the pyridine ring, solvent coordination and, accordingly, ligand rearrangement are prevented by steric constraints. The complexes were tested as oxidation catalysts in the epoxidation of alkene substrates in acetonitrile with hydrogen peroxide as the oxidant under oxidant limiting conditions. The complexes were shown to be especially active in the epoxidation of styrene type substrates (styrene and trans-beta-methylstyrene). In the best case, complex [Fe(6-Me-PyProNH2)Cl2] (15) allowed for 65% productive consumption of hydrogen peroxide toward epoxide and benzaldehyde products. This journal is the Partner Organisations 2014.
Monocyclopentadienyl binuclear complexes, ligands used in their preparaion, catalyst systems comprising them and olefin polymerisation process
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Page/Page column, (2013/07/19)
A complex of formula (I) wherein R1 is a hydrogen atom or C1-C40 hydrocarbon radical Ra and Rb equal to or different from each other, are hydrogen atoms or C1-C40 hydrocarbon radical or Ra and Rb can be joined to form a from 4 to 7 membered ring, M is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten; X, equal to or different from each other, are a hydrogen atom, a halogen atom, a R, OR, OSO2CF3, OCOR, SR, NR2 or PR2 group where R is as defined in the claims; Z is a divalent bridging group; T2 is a radical comprising at least one uncharged donor containing at least one atom of group 15 or 16 of the Periodic Table; L is a divalent bridging group. The invention also relates to a catalyst system comprising complex (I), an alumoxane or a compound capable of forming an alkyl metallocene cation, and optionally an oranoaluminium compound. The catalyst system is employed in the polymerisation of one or more α-olefins. The ligands making up the complex (I) are also claimed.
Investigating the oxidation of alkenes by non-heme iron enzyme mimics
Barry, Sarah M.,Mueller-Bunz, Helge,Rutledge, Peter J.
scheme or table, p. 7372 - 7381 (2012/10/08)
Iron is emerging as a key player in the search for efficient and environmentally benign methods for the functionalisation of C-H bonds. Non-heme iron enzymes catalyse a diverse array of oxidative chemistry in nature, and small-molecule complexes designed to mimic the non-heme iron active site have great potential as C-H activation catalysts. Herein we report the synthesis of a series of organic ligands that incorporate key features of the non-heme iron active site. Iron(ii) complexes of these ligands have been generated in situ and their ability to promote hydrocarbon oxidation has been investigated. Several of these systems promote the biomimetic dihydroxylation of cyclohexene at low levels, when hydrogen peroxide is used as the oxidant; allylic oxidation products are also observed. An investigation of ligand stability reveals formation of several breakdown products under the conditions of the oxidative turnover reactions. These products arise via oxidative decarboxylation, dehydration and deamination reactions. Taken together these results indicate that competing mechanisms are at play with these systems: biomimetic hydroxylation involving high-valent iron species, and allylic oxidation via Fenton chemistry and Haber-Weiss radical pathways.
(2-Alkyl-3-pyridyl)methylpiperazine derivatives as PAF antagonists
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, (2008/06/13)
The present invention relates to new (2-alkyl-3-pyridyl) methylpiperazine derivatives of general formula I: wherein R1, R2 and Z are as defined in Claim 1. The invention also relates to processes for their preparation and to pharmaceutical compositions containing them. These compounds are potent, orally active PAF antagonists and, consequently, they are useful in the treatment of the diseases in which this substance is involved.
Side chain chlorination process of heterocycles
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, (2008/06/13)
A novel method of chlorinating the alkyl side chains of a nitrogen containing heterocyclic comprising reacting an alkyl substituted heterocycle with trichloroisocyanuric acid at temperatures of 20° to 200° C. to obtain the same in high yields.
Side Chain Chlorinations of N-Heterocyclic Compounds by Trichloroisocyanuric Acid (TCC)
Jeromin, Guenter E.,Orth, Winfried,Rapp, Bernd,Weiss, Wolfgang
, p. 649 - 652 (2007/10/02)
N-Heterocyclic compounds such as 2-methylpyridines, 2-methylquinoline, and 2-methylquinoxaline react with trichloroisocyanuric acid (TCC) without the addition of an initiator to provide the corresponding chloromethyl derivatives in good yields.
