cas 109-09-1, 2-Chloropyridine | Articles data

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Silver-catalyzed protodecarboxylation of heteroaromatic carboxylic acids
[Chemical Equation Presented] A simple and highly efficient protodecarboxylation procedure for a variety of heteroaromatic carboxylic acids catalyzed by Ag2CO3 and AcOH in DMSO is described. This methodology can also perform the selective monoprotodecarboxylation of several aromatic dicarboxylic acids.
Lu, Pengfel,Sanchez, Carolina,Cornella, Josep,Larrosa, Igor
p. 5710 - 5713
(2009)
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Preparation of 2-chloropyridine
Regiospecific chlorination of pyridine-N-oxide to give 2-chloropyridine was achieved in 90% yield with 99.2% selectivity by treatment with phosphorus oxychloride in the presence of a stoichiometric amount of triethylamine. Other chlorinating agents such as sulfuryl chloride, p-toluenesulfonyl chloride, trichloroacetyl chloride, benzenesulfonyl chloride and methanesulfonyl chloride produced 2-chloropyridine also under these conditions, albeit in moderate yield.
Jung,Jung,Park
p. 2507 - 2511
(2001)
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Facile and Selective Synthesis of Chloromethylpyridines and Chloropyridines Using Diphosgene/Triphosgene
Diphosgene and triphosgene in the presence of amines were found to be an excellent chlorinating agents with high selectivity for the preparation of chloromethylpyridines and chloropyridines from picoline-N-oxides and pyridine-N-oxides respectively.
Narendar,Gangadasu,Ramesh, Ch.,Raju, B. China,Rao, V. Jayathirtha
p. 1097 - 1103
(2004)
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Efficient Phosphorus-Free Chlorination of Hydroxy Aza-Arenes and Their Application in One-Pot Pharmaceutical Synthesis
The chlorination of hydroxy aza-arenes with bis(trichloromethyl) carbonate (BTC) and SOCl2 has been effectively performed by refluxing with 5 wt % 4-dimethylaminopyridine (DMAP) as a catalyst. Various substrates are chlorinated with high yields. The obtained chlorinated aza-arenes can be used directly with simple workup for succedent one-pot synthesis on a large scale.
Wang, Jian,Li, Yan-Hui,Pan, Song-Cheng,Li, Ming-Fang,Du, Wenting,Yin, Hong,Li, Jing-Hua
p. 146 - 153
(2020)
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A simple and highly effective oxidative chlorination protocol for the preparation of arenesulfonyl chlorides
2,4-Dichloro-5,5-dimethylhydantoin (DCDMH) was found to be a mild and efficient reagent for the direct oxidative conversion of sulfur compounds to the corresponding arenesulfonyl chlorides in good to excellent yields through oxidative chlorination. The method is suitable for many types of sulfur substrates (thiols, disulfides, and benzylic sulfides). The overall process is simple, practical, and it provides convenient access to a variety of aryl or heteroarylsulfonyl chlorides. The mild reaction conditions and the broad substrate scope render this method attractive and complementary to existing syntheses of aryl or heteroarylsulfonyl chlorides.
Pu, Yu-Ming,Christesen, Alan,Ku, Yi-Yin
p. 418 - 421
(2010)
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Solvent-free or low-solvent large-scale preparation of chloropyrimidine and analogues
Chloropyrimidine or other N-containing aromatic heterocyclic analogues can be efficiently prepared from the corresponding hydroxylated precursors under solvent-free or low-solvent conditions with equimolar or less chlorinating reagents. This high-yielding protocol allows successful preparations of multigram and kilogram batches of these important synthetic intermediates.
Sun, Zhihua,Wang, Han,Wen, Kun,Li, Ya,Fan, Erkang
p. 4149 - 4153
(2011)
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Clean protocol for deoxygenation of epoxides to alkenes: Via catalytic hydrogenation using gold
The epoxidation of olefin as a strategy to protect carbon-carbon double bonds is a well-known procedure in organic synthesis, however the reverse reaction, deprotection/deoxygenation of epoxides is much less developed, despite its potential utility for the synthesis of substituted olefins. Here, we disclose a clean protocol for the selective deprotection of epoxides, by combining commercially available organophosphorus ligands and gold nanoparticles (Au NP). Besides being successfully applied in the deoxygenation of epoxides, the discovered catalytic system also enables the selective reduction N-oxides and sulfoxides using molecular hydrogen as reductant. The Au NP catalyst combined with triethylphosphite P(OEt)3 is remarkably more reactive than solely Au NPs. The method is not only a complementary Au-catalyzed reductive reaction under mild conditions, but also an effective procedure for selective reductions of a wide range of valuable molecules that would be either synthetically inconvenient or even difficult to access by alternative synthetic protocols or by using classical transition metal catalysts. This journal is
Fiorio, Jhonatan L.,Rossi, Liane M.
p. 312 - 318
(2021/01/29)

Metal-Free Deoxygenation of Amine N-Oxides: Synthetic and Mechanistic Studies
We report herein an unprecedented combination of light and P(III)/P(V) redox cycling for the efficient deoxygenation of aromatic amine N-oxides. Moreover, we discovered that a large variety of aliphatic amine N-oxides can easily be deoxygenated by using only phenylsilane. These practically simple approaches proceed well under metal-free conditions, tolerate many functionalities and are highly chemoselective. Combined experimental and computational studies enabled a deep understanding of factors controlling the reactivity of both aromatic and aliphatic amine N-oxides.
Lecroq, William,Schleinitz, Jules,Billoue, Mallaury,Perfetto, Anna,Gaumont, Annie-Claude,Lalevée, Jacques,Ciofini, Ilaria,Grimaud, Laurence,Lakhdar, Sami
p. 1237 - 1242
(2021/06/01)

Transition-metal-free decarboxylative halogenation of 2-picolinic acids with dihalomethane under oxygen conditions
A convenient and efficient method for the synthesis of 2-halogen-substituted pyridines is described. The decarboxylative halogenation of 2-picolinic acids with dihalomethane proceeded smoothly via N-chlorocarbene intermediates to afford 2-halogen-substituted pyridines in satisfactory to excellent yields under transition-metal-free conditions. This new type of decarboxylative halogenation is operationally simple and exhibits high functional-group tolerance.
Zhang, Xitao,Feng, Xiujuan,Zhang, Haixia,Yamamoto, Yoshinori,Bao, Ming
supporting information
p. 5565 - 5570
(2019/10/22)

Metal-Free Iodine-Catalyzed Oxidation of Ynamides and Diaryl Acetylenes into 1,2-Diketo Compounds
Metal-free oxidation of ynamides is described, employing pyridine-N-oxides as oxidants under molecular iodine catalysis. In stark contrast to Br?nsted acid catalysis, iodophilic activation of ynamides diverts the reaction manifold into a dioxygenation pathway. This oxidation is very rapid at room temperature with only 2.5 mol % I2. Furthermore, this protocol could be extended to nonactivated alkynes, such as diarylacetylenes, to deliver various benzil derivatives.
Kim, Seung Woo,Um, Tae-Woong,Shin, Seunghoon
supporting information
p. 4703 - 4711
(2018/04/26)

Preparation method of non-transition metal-catalyzed 2-halogenated pyridine compound
The invention provides a preparation method of a non-transition metal-catalyzed 2-halogenated pyridine compound. The 2-halogenated pyridine compound is an important component of many medicines and bioactive molecules and has important application in the fields of organic synthesis, medicinal chemistry and the like and wide market prospects. The invention relates to the preparation method of the non-transition metal-catalyzed 2-halogenated pyridine compound. According to the method, pyridine-2-carboxylic acid, derivatives of the pyridine-2-carboxylic acid, NaF, KF, CsF, TBAF, NaCl, KCl, CsCl, TBAC, NCS, NaBr, KBr, CsBr, Br2, TBAB, NBS, NaI, KI, CsI, I2 and NIS are used as raw materials, and under the presence of base and an accelerant and mild conditions, the 2-halogenated pyridine compoundis synthesized. The method has the advantages that the steps are simple, the raw materials are easy to obtain, the reaction conditions are mild and the like; the method has great use value and socialand economic benefits.
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Paragraph 0041-0043

(2018/10/11)

Deoxygenation of tertiary amine N-oxides under metal free condition using phenylboronic acid
A simple and efficient method for the deoxygenation of amine N-oxides to corresponding amines is reported using the green and economical reagent phenylboronic acid. Deoxygenation of N,N-dialkylaniline N-oxides, trialkylamine N-oxides and pyridine N-oxides were achieved in good to excellent yields. The reduction susceptible functional groups such as ketone, amide, ester and nitro groups are well tolerated with phenylboronic acid during the deoxygenation process even at high temperature. In addition, an indirect method for identification and quantification of tert-amine N-oxide is demonstrated using UV–Vis spectrometry which may be useful for drug metabolism studies.
Gupta, Surabhi,Sureshbabu, Popuri,Singh, Adesh Kumar,Sabiah, Shahulhameed,Kandasamy, Jeyakumar
supporting information
p. 909 - 913
(2017/02/15)

HOMOGENEOUS PROCESS FOR HYDRODEHALOGENATING HALOGENATED HETEROARYL COMPOUNDS
The present invention provides a homogeneous process for hydrodehalogenating a halo-substituted C3-C20 heteroaryl starting material to form a non-halogenated C3-C20 heteroaryl product and/or a halo- substituted C3-C20 heteroaryl product, wherein the halo-substituted C3-C20 heteroaryl product has at least one less halogen substituents than the halo-substituted C3-C20 heteroaryl starting material, the process comprising the step of hydrogenating the halo-substituted C3-C20 heteroaryl starting material in the presence of a rhodium or ruthenium complex, molecular hydrogen, a base and a solvent, wherein the process is carried out in a monophasic solvent system and the molar ratio of base to each halogen substituent to be removed is at least 1 :1.
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Page/Page column 12-13

(2017/07/11)

A Ruthenium Complex-Catalyzed Cyclotrimerization of Halodiynes with Nitriles. Synthesis of 2- and 3-Halopyridines
Monohalo- and dihalodiynes efficiently undergo [2+2+2] cyclotrimerization with nitriles in the presence of a catalytic amount of the ruthenium complex Cp*RuCl(cod) (10 mol%) to afford the corresponding halopyridines under ambient conditions in good isolated yields (up to 90%). The halopyridines are formed as two separable regioisomers. This is the first example of a direct synthesis of halopyridines from haloalkynes and nitriles. (Figure presented.) .
Bedná?ová, Eva,Colacino, Evelina,Lamaty, Frédéric,Kotora, Martin
supporting information
p. 1916 - 1923
(2016/07/06)

Method for synthesizing 2-chloropyridine
The invention discloses a method for synthesizing 2-chloropyridine. The method comprises the following steps: adding pyridine and a solvent into a 500mL container, controlling the pressure at normal pressure, stirring for 10-20 minutes, and dropwisely adding fluorine acetate, wherein the temperature is controlled to not exceed 30 DEG C; transferring the reaction mixture into a 500mL container, heating to 50-70 DEG C, and carrying out reduced pressure distillation under the vacuum degree of 0.07-0.09 MPa until no liquid is distilled out, thereby obtaining the residual material which is the 2-chloropyridine. The chlorination in the method does not need chlorine gas, phosphorus trichloride, phosphorous pentachloride, phosphorus oxychloride, phosgene or any other extremely toxic substance as a chlorination reagent, but uses dichloromethane as the chlorination reagent, and thus, the technique is safe and reliable for production. The reaction is carried out at normal temperature under normal pressure, and the yield of the 2-chloropyridine reaches 80%.
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Paragraph 0042; 0043

(2016/11/07)

2-chloropyridine synthetic method
The invention discloses a 2-chloropyridine synthetic method, which belongs to the technical field of fine chemical engineering. The method comprises the following steps: adding pyridine into a hypochloric acid salt solution, uniformly mixing the solution, slowly adding hydrochloric acid drop by drop at room temperature, stirring a mixture and reacting the mixture for 1-2 hours; then heating the material to the temperature of 60-80 DEG C, continuously reacting the material for 1-2 hours; and finally, adding a certain amount of a NaOH solution and neutralizing the solution to a pH value of 9-11, extracting a reactant by using trichloromethane and separating the reactant; distilling an extract phase and removing a trichloromethane solvent in order, recovering the unreacted pyridine to obtain the chloropyridine product. According to the invention, a GC/MS analysis on the chloropyridine product is carried out, selectivity of 2-chloropyridine can reach 83%. The hydrochloric acid and hypochlorite by-product with low cost in industrial production can substitute a chlorinating agent such as Cl2, reaction condition is mild, selectivity is good, process is simple, cost is low, and environment and safety problems during the production process of 2-chloropyridine can be solved.
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Paragraph 0021; 0022

(2016/12/16)

Dehalogenation degradation method for halogenated pyridine compound
The invention provides a dehalogenation degradation method for a halogenated pyridine compound. The halogenated pyridine compound is adopted as a raw material, alcohol is adopted as a hydrogen source, water is adopted as a solvent, reacting is carried out for 3-10 h under normal pressure at the temperature of 20 DEG C to 120 DEG C under the action of a supported catalyst, and the halogenated pyridine compound is subjected to dehalogenation degradation in situ through water phase hydrogen production. A pyridine ring of the halogenated pyridine compound at least contains an F or Cl or Br or I substituent group. The supported catalyst is composed of an active component and a carrier, the active component is composed of a mixture of transition metal and other metal, the transition metal is one of Rh, Pd, Pt and Ni, and other metal is one of Se, Ca, Ba, La and Ce. The carrier is one of activated carbon, kieselguhr, zeolite, gamma-Al2O3, AlF3 and MgO. H2 is not directly used as a reduction agent, activated hydrogen is prepared through in-situ catalysis to directly participate in reacting, the advantages of being high in reaction activity, high in selectivity, high in safety, environmentally friendly and the like are achieved, and good application prospects are achieved.
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Paragraph 0023; 0024

(2016/12/16)

New (green) methodology for efficient hydrazine cleavage
An efficient method for removal of the hydrazine group from (hetero)aromatic substrates has been developed. It can be realized both on a solid support and in solution by synthesis employing a low concentration solution of trimethylsilanolate in tetrahydrofuran or N,N-dimethylformamide. For water-soluble substrates, the reaction can be performed in water, highlighting the eco-friendly attributes of this methodology.
Kubovi?ová, Lenka,Bürglová, Kristyna,Hlavá?, Jan
supporting information
p. 4824 - 4828
(2016/06/13)

A Novel Convenient Synthesis of Pyridinyl and Quinolinyl Triflates and Tosylates via One-Pot Diazotization of Aminopyridines and Aminoquinolines in Solution
The first effective and simple method for the direct one-pot transformation of 2-, 3-, and 4-aminopyridines, 2,6-diaminopyridines, and 2-aminoquinoline into the corresponding pyridinyl and quinolinyl trifluoromethanesulfonates and tosylates in solvents was developed. The procedure involves diazotization of the heterocyclic amines with sodium nitrite in mixed hexane-DMSO or hexane-DMF solutions in the presence of trifluoromethanesulfonic acid or p-toluenesulfonic acid.
Kassanova, Assiya Zh.,Krasnokutskaya, Elena A.,Beisembai, Perizat S.,Filimonov, Victor D.
p. 256 - 262
(2016/01/15)

One-step synthesis method of 2-chloropyridine from N-pyridine oxide
The invention discloses a one-step synthesis method of 2-chloropyridine from N-pyridine oxide. The method comprises the following steps: 1) chlorination: adding N-pyridine oxide into a flask, adding dichloromethane, oxalyl chloride and triethylamine, and stirring to react under appropriate conditions; and 2) distillation: transferring the reaction mixture into a 500mL container, heating to 50-70 DEG C, carrying out reduced pressure distillation under the vacuum degree of 0.07-0.09 MPa to remove the dichloromethane, oxalyl chloride, triethylamine, pyridine and other raw materials and other byproducts, continuing heating to 90-95 DEG C, distilling under the vacuum degree of 0.07-0.09 MPa to obtain 2-chloropyridine, wherein the residual high-boiling fraction is a small amount of unreacted N-pyridine oxide. The method can be implemented by two steps, thereby reducing the reaction process and enhancing the yield. The oxalyl chloride and triethylamine are used as reaction reagents to react at low temperature under atmospheric pressure, so that the final 2-chloropyridine yield reaches 90%.
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Paragraph 0039; 0040

(2016/10/10)

PhPOCl2as a potent catalyst for chlorination reaction of phenols with PCl5
Phenols are easily converted to the corresponding aryl chlorides by using phosphorus pentachloride (PCl5) and a catalytic amount of phenylphosphonic dichloride (PhPOCl2), which is a new efficient method for synthesis of aryl chloride in good yields.
Wu, Jiang,Zhou, Junpeng,Shi, Yalei,Zhu, Jintao
supporting information
p. 1619 - 1624
(2016/10/09)

The radical reaction from a fluorine-containing compound
PROBLEM TO BE SOLVED: To provide a radical reaction substitute solvent for carbon tetrachloride which has been used heretofore as a radical reaction solvent. SOLUTION: A chain fluorine-containing hydrocarbon represented by formula (1): CmH2m+2-nFn(wherein m is an integer of 3-10 and n is an integer of 1 to 2m+1) or a cyclic fluorine-containing hydrocarbon represented by formula (2): CpH2p-qFq(wherein p is an integer of 3-10 and q is an integer of 1 to 2p-1) is used as a solvent for various radical reactions. COPYRIGHT: (C)2011,JPO&INPIT
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Paragraph 0033-0034

(2017/01/05)

Glycinatocopper(II) complex as an efficient heterogeneous catalyst for aromatic Finkelstein reaction of aryl and heteroaryl bromides to chlorides
Glycinatocopper(II) complex 1, readily synthesized from copper chloride and glycine was characterized by various techniques including FTIR, XRD, TGA and SEM analysis. The as-synthesized copper complex was found to be a simple and efficient catalyst for the synthesis of aryl and heteroaryl chlorides via aromatic Finkelstein reaction of aryl and heteroaryl bromides in high to excellent yields. The developed glycinatocopper(II) catalyst could easily be recovered from the reaction mixture and reused successfully for several runs without any loss in catalytic efficiency. The developed methodology represents the first example of the use of heterogeneous catalyst for the synthesis of aryl and heteroaryl chlorides via aromatic Finkelstein reaction.
Verma, Sanny,Saran, Sandeep,Jain, Suman L.
p. 178 - 183
(2014/02/14)

Selective and efficient deoxygenation of amine-n-oxides with CeCl 3 7H2O/zinc system
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Yoo, Byung Woo,Jung, Ha Il,Kim, Se Heon,Ahn, Young Sun,Choi, Ji Yong
p. 359 - 360
(2013/08/25)

Reduction of sulfoxides and pyridine-N-oxides over iron powder with water as hydrogen source promoted by carbon dioxide
A green process was developed for efficient reduction of sulfoxides and pyridine-N-oxides using the iron powder in the presence of H2O- CO2 to sulfides and pyridines, respectively. Notably, H2O is employed as the terminal hydrogen source, and CO2 could enhance hydrogen generation through in situ formation of carbonic acid. Thus carbonic acid offers simple neutralization by depressurizing CO2 and the system can eliminate unwanted byproducts. The high generality and chemo-selectivity of this protocol were demonstrated by the scope of substrates, in which chlorine, vinyl group and benzene ring can be tolerated.
Ma, Ran,Liu, An-Hua,Huang, Cheng-Bin,Li, Xue-Dong,He, Liang-Nian
supporting information
p. 1274 - 1279
(2013/06/05)

Rapid and selective in situ reduction of pyridine- N -oxides with tetrahydroxydiboron
Pyridine-N-oxides are often used as reactive precursors in the syntheses of substituted pyridines. Isolation and subsequent reduction of the associated pyridine-N-oxide intermediates can be challenging. We have discovered that tetrahydroxydiboron functions as a mild, versatile, and remarkably selective reducing agent for pyridine-N-oxides and may be used in an in situ fashion, thus obviating the isolation of N-oxide-containing intermediates. Georg Thieme Verlag Stuttgart New York.
Londregan, Allyn T.,Piotrowski, David W.,Xiao, Jun
supporting information
p. 2695 - 2700
(2014/01/06)

Efficient indium-mediated dehalogenation of aromatics in ionic liquid media
An efficient indium-mediated dehalogenation reaction of haloaromatics and haloheteroaromatics in ionic liquids has been studied. This method is simple and effective in the presence of [bmim]Br. Furthermore, this methodology is environmentally friendly compared with conventional ones.
Canete, Alvaro F.,Salas, Cristian O.,Zacconi, Flavia C.
p. 398 - 407
(2013/03/13)

Copper-catalyzed conversion of aryl and heteroaryl bromides into the corresponding chlorides
An efficient method for the synthesis of aryl and heteroaryl chlorides is described. The reactions of aryl and heteroaryl bromides with tetramethylammonium chloride proceeded smoothly in the presence of a copper catalyst under mild reaction conditions to produce the corresponding chlorides in satisfactory to excellent yields.
Feng, Xiujuan,Qu, Yiping,Han, Yanlei,Yu, Xiaoqiang,Bao, Ming,Yamamoto, Yoshinori
supporting information
p. 9468 - 9470
(2012/10/29)

Cl3CCN/PPh3 and CBr4/PPh3: Two efficient reagent systems for the preparation of N-heteroaromatic halides
Cl3CCN/PPh3 and CBr4/PPh3 are two highly reactive reagent systems for the conversion of N-heteroaromatic hydroxy compounds into N-heteroaromatic chlorides or bromides in moderate to excellent yields under mild and acid-free conditions.
Kijrungphaiboon, Woranun,Chantarasriwong, Oraphin,Chavasiri, Wainthorn
scheme or table
p. 674 - 677
(2012/02/15)

Synthesis of polyhalogenated 4,4′-bipyridines via a simple dimerization procedure
Polyhalogenated 4,4′-bipyridines were conveniently synthesized in a single step starting from dihalopyridines. A mechanism was proposed on the basis of experiments performed with 2-chloro-5-bromopyridine 1a. 2-Chloro-4-lithio-5- bromopyridine A1 was produced via ortholithiation of 1a by using either LDA or t-BuLi bases. When LDA was used, dimer 3a containing two chlorines and two bromine atoms was formed predominantly accompanied by several byproducts whose structure and mechanism of formation are discussed. In the case of t-BuLi, although the major product was 2-chloropyridine 7, a new pyridone product 8 was formed that is probably the result of the dihydropyridine intermediate hydrolysis. The dimerization procedure involving LDA was employed to prepare a large number of halogenated 4,4′-bipyridines in moderate to good yields. In some specific cases, halogenated 3,4′ and 2,4′-bipyridines were obtained in lower yields and their structures were unambiguously assigned by X-ray diffraction analysis.
Abboud, Mohamed,Mamane, Victor,Aubert, Emmanuel,Lecomte, Claude,Fort, Yves
supporting information; experimental part
p. 3224 - 3231
(2010/08/19)

METHOD FOR PURIFICATION OF PYRIDINE, AND METHOD FOR PRODUCTION OF CHLORINATED PYRIDINE
A method of purifying crude pyridine on an industrial scale at low cost and in a simple manner is provided. More specifically, a pyridine purification method including subjecting crude pyridine to an alkali treatment and then to distillation, or a pyridine purification method including adding an acid or water to crude pyridine, and subjecting the resulting mixture to an alkali treatment and then to distillation is provided. According to the purification method of the present invention, crude pyridine can be purified on an industrial scale at low cost and in a simple manner. Moreover, the pyridine purified by this method is useful as a starting material for various organic syntheses because of its high purity. For example, the pyridine can be reacted with chlorine to produce a chlorinated pyridine in a high yield.
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(2010/12/31)

Mild and efficient deoxygenation of amine-N-oxides with BiCl3/Indium system
The BiCl3/indium system was found to be a new reagent for deoxygenation of various amine-N-oxides to the corresponding amines in good to excellent yields under mild conditions.
Yoo, Byung Woo,Choi, Jin Woo
experimental part
p. 3550 - 3554
(2009/12/03)

Mild and efficient deoxygenation of amine-N-oxides with MoCl5/NaI system
The MoCl5/NaI system was found to be a new reagent for deoxygenation of various amine-N-oxides to the corresponding amines in good to excellent yields under mild conditions. Copyright Taylor & Francis Group, LLC.
Yoo, Byung Woo,Park, Min Chol
p. 1646 - 1650
(2008/09/20)

From haloquinolines and halopyridines to quinoline- and pyridinesulfonyl chlorides and sulfonamides
The action of sodium methanethiolate (in boiling DMF) towards haloazines (i.e. chloro- or bromo-pyridines and quinolines) (1) (with halogen substituent in non-aza-activated position) causes sequentially halogen ipso-substitution to methylthioazines (2) and then S-demethylation to azinethiolates (3A), which were: i) subjected to S-methylation, ii) oxidized to diazinyl disulfides (4) and iii) oxidatively chlorinated to azinesulfonyl chlorides (5). α- and γ-pyridine- and quinolinesulfonyl chlorides (5a, 5c, 5d and 5f) were prepared by oxidative chlorination of respective disulfides (4) performed in conc. hydrochloric acid and characterized by 1H and 13C NMR spectra. All azinesulfonyl chlorides (5) were effectively converted to corresponding azinesulfonamides (6).
Maslankiewicz, Andrzej,Marciniec, Krzysztof,Pawlowski, Maciej,Zajdel, Pawel
p. 1975 - 1990
(2008/09/16)

Cu(I)-mediated deoxygenation of N-oxides to amines
A mild and highly efficient deoxygenation of variety of N-oxides using an inexpensive CuX, or a CuX-Zn or CuX-Al couple is described.
Singh, Sunil Kumar,Srinivasa Reddy,Mangle, Mangesh,Ravi Ganesh
p. 126 - 130
(2007/10/03)

A facile and efficient deoxygenation of amine-N-oxides with Mo(CO) 6
A variety of amine-N-oxides have been found to be selectively deoxygenated to the corresponding amines in high yields with Mo(CO)6 in ethanol under mild conditions.
Yoo, Byung Woo,Choi, Jin Woo,Yoon, Cheol Min
p. 125 - 126
(2007/10/03)

Deoxygenation of N-oxides with triphenylphosphine, catalyzed by dichlorodioxomolybdenum(VI)
Chemoselective deoxygenation of N-oxides was carried out under mild conditions with common phosphines in the presence of dichlorodioxomolybdenum(VI) . Georg Thieme Verlag Stuttgart.
Sanz, Roberto,Escribano, Jaime,Fernández, Yolanda,Aguado, Rafael,Pedrosa, María R.,Arnáiz, Francisco J.
p. 1389 - 1392
(2007/10/03)

Deoxygenation of sulfoxide and aza-aromatic N-oxide using a protocol of indium and acyl chloride
Sulfoxides and aza-aromatic N-oxides were deoxygenated using a system of indium and pivaloyl chloride at room temperature to give the corresponding sulfides and aza-aromatics in high yields. Georg Thieme Verlag Stuttgart.
Park, Eun Soo,Lee, Seung Hwan,Lee, Ji Hee,Rhee, Hak June,Yoon, Cheol Min
p. 3499 - 3501
(2007/10/03)

Hiyama cross-coupling of chloro-, fluoro-, and methoxypyridyltrimethylsilanes: Room-temperature novel access to functional bi(het)aryl
(Chemical Equation Presented) The incorporation of chloro, fluoro, or methoxy substituents on the pyridine ring of pyridyltrimethylsilanes allowed us to perform efficient Hiyama cross-coupling with various (het)aryl halides. The reactions proceeded smoothly at room temperature leading to the corresponding functional bis(het)aryl in fair to excellent yields. The presence of pyridine nitrogen α to the trimethylsilyl group was requisite to achieve the cross-coupling.
Pierrat, Philippe,Gros, Philippe,Fort, Yves
p. 697 - 700
(2007/10/03)

Reaction of N-fluoropyridinium fluoride with isonitriles: A convenient route to picolinamides
Reaction of N-fluoropyridinium fluoride generated in situ with a series of isonitriles led to the formation of the corresponding picolinamides in good yields. A similar reaction sequence for quinoline yielded the respective derivatives of 2-quinoline carboxylic acid. The proposed reaction mechanism involves the intermediate formation of a highly reactive carbene species.
Kiselyov, Alexander S.
p. 2279 - 2282
(2007/10/03)

8-substituted-6-trifluoromethyl-9-pyrido[3,2-g]quinoline compounds as androgen receptor modulators
Non-steroidal compounds and compositions which are agonists, partial agonists, and antagonists for androgen receptors and methods of preparation for the non-steroidal compounds and compositions.
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(2008/06/13)

Aminopyrimidine and aminopyridine anti-inflammation agents
Aminopyrimidine and aminopyridine (I) compounds, compositions and methods useful in the treatment of inflammatory, metabolic or malignant conditions, are provided herein.
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(2008/06/13)

Mild and Efficient Deoxygenation of Amine-N-oxides with Titanium Tetrachloride-Indium System
TiCl4/In system was found to be a new reagent for deoxygenation of various amine-N-oxides to the corresponding amines in good to excellent yields under mild conditions.
Yoo, Byung Woo,Choi, Kwang Hyun,Choi, Kyung Il,Kim, Joong Hyup
p. 4185 - 4189
(2007/10/03)

Process for preparation of 2-chloropyridine
Described are processes for producing 2-chloropyridine by reacting pyridine with molecular chlorine in the vapor phase in the presence of a catalyst which includes an organic compound which generates free radicals under the conditions of the reaction.
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(2010/01/31)

Efficient and chemoselective deoxygenation of amine N-oxides using polymethylhydrosiloxane
Deoxygenation of aromatic and aliphatic amine N-oxides to the corresponding amines is achieved under mild conditions. The reagent combination employed for this transformation is polymethylhydrosiloxane (PMHS) in the presence of either tetrakis (triphenylphosphine) palladium (0) [Pd(PPh3)4], titanium (IV) isopropoxide [Ti(i-PrO)4] or palladium on carbon (Pd/C).
Chandrasekhar,Reddy, Ch. Raji,Rao, R. Jagadeeshwar,Rao, J. Madhusudana
p. 349 - 351
(2007/10/03)

Application of phosphonium salts to the reactions of various kinds of amides
The phosphonium salts 1 and 2 prepared from triphenylphosphine and N-halogenosuccinimide proved to be applicable to the conversion of amide compounds. Especially, halogenation of electron-deficient heteroaromatic alcohols with these reagents seems to be a convenient method compared to the halogenation with phosphorus oxyhalides.
Sugimoto, Osamu,Mori, Miho,Moriya, Keisuke,Tanji, Ken-Ichi
p. 1112 - 1118
(2007/10/03)

2-Pyrimidineamine derivatives and processes for their preparation
Compounds of general formula (1) are described wherein: Ar is an optionally substituted aromatic group; R2 is a hydrogen or halogen atom or a group -X1-R2a where X1 is a direct bond or a linker atom or group, and R2a is an optionally substituted straight or branched chain alkyl, alkenyl or alkynyl group; R3 is an optionally substituted heterocycloalkyl group; and the salts, solvates, hydrates and N-oxides thereof. The compounds are selective protein tyrosine kinase inhibitors, particularly the kinases ZAP-70 and syk and are of use in the prophylaxis and treatment of immune or allergic diseases and diseases involving inappropriate platelet activation.
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(2008/06/13)

Ring-Centered Heterocyclic Cations and the Direct Heteroarylation of Aromatic and Heterocyclic Compounds
(matrix presented) The protonation of heterocyclic diazotates (attachment adjacent to a nitrogen atom) yields ring-centered heterocyclic carbocations that are highly reactive. The carbocations were found to alkylate aromatic and heterocyclic compounds, such as benzene, N-methylpyrrole, and 2-aminopyridine, in reactions that are synthetically useful. This carbocation involvement may serve as a paradigm for the cross-linking of DNA by nitrous acid and the anticancer activity of heterocyclic diazotates.
Song, Fenhong,St. Hilaire, Valentine R.,White, Emil H.
p. 1957 - 1959
(2008/02/11)

A facile halogenation of some hydroxyheterocycles using triphenylphosphine and N-halosuccinimide
Some hydroxyheterocycles were halogenated to give the corresponding haloheterocycles using triphenylphosphine and N-halosuccinimide. In comparison with the usual method using phosphorus oxyhalide, the haloheterocycles were easily isolated.
Sugimoto, Osamu,Mori, Miho,Tanji, Ken-ichi
p. 7477 - 7478
(2007/10/03)

Novel base-initiated reactions of N-substituted pyridinium salts
Reaction of N-fluoropyridinium triflate with a base in dichloromethane gave 2-chloropyridine as the major product along with 2-pyridyl triflate and 2-fluoropyridine, regardless of the nature of the base. This base-initiated reaction was also shown to take place similarly in other halogenated alkanes, ethers, a nitrile, aromatics, a ketone, vinyl ethers, alcohols and trimethylsilyl acetate as solvents to give pyridine derivatives substituted with a solvent molecule (s) at the 2-position. N-(Trifluoromethanesulfonyloxy)-and (benzenesulfonyloxy) pyridinium salts were found to undergo the same base-initiated reaction. These reactions may be explained by a postulated singlet carbene (canonical formula 11b) produced through proton abstraction of N-substituted pyridinium salts. A similar carbene reaction may thus likely occur in the thermal decomposition of thiatriazole 10. Ab initio MO calculations revealed the structure and properties of the labile deprotonated N-fluoropyridinium cation and supported the carbene intermediate reaction mechanism rather than a pyridynium or pyridyl cation mechanism. Quarroz's reports on the reactions of picolinic acid N-oxide and the reported reactions of pyridines with F2, CH3COOF or CsSO4F in solvents may be explained by this carbene mechanism.
Umemoto, Teruo,Tomizawa, Ginjiro,Hachisuka, Hitoharu,Kitano, Masakatsu
p. 161 - 168
(2007/10/03)