- Mild, General, and Regioselective Synthesis of 2-Aminopyridines from Pyridine N -Oxides via N -(2-Pyridyl)pyridinium Salts
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A synthesis of 2-aminopyridines from pyridine N-oxides via their corresponding N-(2-pyridyl)pyridinium salts has been demonstrated and investigated. The reaction sequence features a highly regioselective conversion of the N-oxide into its pyridinium salt
- Xiong, Hui,Hoye, Adam T.
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supporting information
p. 371 - 375
(2022/01/27)
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- Ligand compound for copper catalyzed aryl halide coupling reaction, catalytic system and coupling reaction
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The invention provides a ligand compound capable of being used for copper catalyzed aryl halide coupling reaction, the ligand compound is a three-class compound containing a 2-(substituted or non-substituted) aminopyridine nitrogen-oxygen group, and the invention also provides a catalytic system for the aryl halide coupling reaction. Thecatalytic system comprises a copper catalyst, a compound containing a 2-(substituted or non-substituted) aminopyridine nitrogen-oxygen group adopted as a ligand, alkali and a solvent, and meanwhile, the invention also provides a system for the aryl halide coupling reaction adopting the catalyst system. The compound containing the 2-(substituted or non-substituted) aminopyridine nitrogen oxygen group can be used as the ligand for the copper catalyzed aryl chloride coupling reaction, and the ligand is stable under a strong alkaline condition and can well maintain catalytic activity when being used for the copper-catalyzed aryl chloride coupling reaction. In addition, the copper catalyst adopting the compound as the ligand can particularly effectively promote coupling of copper catalyzed aryl chloride and various nucleophilic reagents which are difficult to generate under conventional conditions, C-N, C-O and C-S bonds are generated, and numerous useful small molecule compounds are synthesized. Therefore, the aryl halide coupling reaction has a very good large-scale application prospect by adopting the copper catalysis system of the ligand.
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Paragraph 0111-0118; 0121
(2021/05/29)
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- Ruthenium-Catalyzed Reductive Arylation of N-(2-Pyridinyl)amides with Isopropanol and Arylboronate Esters
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A new three-component reductive arylation of amides with stable reactants (iPrOH and arylboronate esters), making use of a 2-pyridinyl (Py) directing group, is described. The N-Py-amide substrates are readily prepared from carboxylic acids and PyNH2, and the resulting N-Py-1-arylalkanamine reaction products are easily transformed into the corresponding chlorides by substitution of the HN-Py group with HCl. The 1-aryl-1-chloroalkane products allow substitution and cross-coupling reactions. Therefore, a general protocol for the transformation of carboxylic acids into a variety of functionalities is obtained. The Py-NH2 by-product can be recycled.
- Ronson, Thomas O.,Renders, Evelien,Van Steijvoort, Ben F.,Wang, Xubin,Wybon, Clarence C. D.,Prokopcová, Hana,Meerpoel, Lieven,Maes, Bert U. W.
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supporting information
p. 482 - 487
(2019/01/04)
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- Synthetic method of 2-amino-5-methyl pyridine
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The invention provides a synthetic method of 2-amino-5-methyl pyridine and relates to the field of research and development of chemical synthesis of drugs. The synthetic method comprises the following steps: adding methyl groups to pyridine to prepare 5-methyl pyridine; preparing N-oxidative methyl pyridine by 5-methyl pyridine; preparing 2-nitro-5-methyl nitrogen-oxidative pyridine by nitrogen-oxidative pyridine; and preparing the 2-amino-5-methyl pyridine by the 2-nitro-5-methyl nitrogen-oxidative pyridine. The synthetic method provided by the invention has the advantages of high product yield and purity, low in production cost and good in environment-friendly effect.
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- Method for preparing 2-amino-5-methylpyridine through ammoniation of 3-methylpyridine
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The invention discloses a method for preparing 2-amino-5-methylpyridine through ammoniation of 3-methylpyridine. The method comprises the following steps: placing a solvent, metallic sodium, a catalyst, an additive and the raw material 3-methylpyridine in a high-pressure reaction container, carrying out heating to 50 to 80 DEG C, then slowly adding liquefied ammonia and carrying out pressurization for a reaction; continuing pressurization to 3 to 6 MPa and heating to 150 to 190 DEG C and continuing the reaction; and terminating the reaction until no obvious pressure increase occurs during the reaction. According to the invention, a one-pot process is employed, and hydrolysis, liquid separation and rectification are successively carried out so as to produce 2-amino-5-methylpyridine and byproduce 2-amino-3-methylpyridine, wherein a ratio of 2-amino-5-methylpyridine to 2-amino-3-methylpyridine is in a range of (9-20): 1. The method has a high 3-methylpyridine conversion rate; the selectivity of the obtained 2-amino-5-methylpyridine can reach 90% or above; and the yield of 2-amino-5-methylpyridine can be increased to 84.5% or above.
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Paragraph 0024; 0025; 0026; 0027; 0028; 0029; 0030-0035
(2017/08/28)
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- PROCESS FOR THE CATALYTIC DIRECTED CLEAVAGE OF AMIDE-CONTAINING COMPOUNDS
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The present invention relates to a catalytic method for the conversion of amide-containing compouds by means of a build-in directing group and upon the action of a heteronucleophilic compound (in se an amine (RNH2 or RNHR') or an alcohol (ROH) or a thiol (RSH)) in the presence of a metal catalyst to respectively esters, thioesters, carbonates, thiocarbonates and to what is defined as amide-containing compounds (such as carboxamides, urea, carbamates, thiocarbamates). The present invention also relates to these amide-containing compounds having a build-in directing group (DG), as well as the use of such directing groups in the catalytic directed cleavage of N-DG amides with the use of heteronucleophiles (in se an amine (RNH2 or RNHR') or an alcohol (ROH) or thiol (RSH)).
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Page/Page column 51; 54
(2017/04/11)
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- Synthetic method of 4-(chloromethyl)-2-(3-(trifluoromethyl)phenoxy)pyridine
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The invention relates to a synthetic method of 4-(chloromethyl)-2-(3-(trifluoromethyl)phenoxy)pyridine and belongs to the field of chemical synthesis.A traditional technology for producing 4-(chloromethyl)-2-(3-(trifluoromethyl)phenoxy)pyridine is backward, long in process, low in yield and large in three-waste amount and treatment is difficult.The synthetic method of the 4-(chloromethyl)-2-(3-(trifluoromethyl)phenoxy)pyridine is mild in reaction condition and high in yield.
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Paragraph 0007
(2016/10/09)
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- Tertiary formylated amines by microwave irradiation of N,N-dimethyl- N′-(2-pyridyl) formamidines with methyl vinyl ketone
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Treatment of N,N-dimethyl-N′-(2-pyridyl)formamidine with methyl vinyl ketone under microwave irradiation yields N-formyl-N-(3-oxobutyl)-2- pyridylamine without decomposition or polymerization of methyl vinyl ketone. The result is an alternative non-oxidat
- Gomez-Garcia, Omar,Salgado-Zamora, Hector,Campos-Aldrete, Elena
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- Mild and highly selective palladium-catalyzed monoarylation of ammonia enabled by the use of bulky biarylphosphine ligands and palladacycle precatalysts
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A method for the Pd-catalyzed arylation of ammonia with a wide range of aryl and heteroaryl halides, including challenging five-membered heterocyclic substrates, is described. Excellent selectivity for monoarylation of ammonia to primary arylamines was achieved under mild conditions or at rt by the use of bulky biarylphosphine ligands (L6, L7, and L4) as well as their corresponding aminobiphenyl palladacycle precatalysts (3a, 3b, and 3c). As this process requires neither the use of a glovebox nor high pressures of ammonia, it should be widely applicable.
- Cheung, Chi Wai,Surry, David S.,Buchwald, Stephen L.
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supporting information
p. 3734 - 3737
(2013/08/23)
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- Homogenous bimetallic catalysis on amination of ArX and ArX2 in aqueous medium-synergistic effect of dicopper complexes
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A dicopper complex [Cu2(bpnp)(OH)(CF3COO) 3] (1) (bpnp = 2,7-bis(pyridin-2-yl)-l,8-naphthyridine) was found to be an excellent catalyst on amination of aryl halides and aryl dihalides with ammonia in aqueous solutions leading to the corresponding anilines and aryldiamines, respectively. Catalytic activity of 1 toward amination appears to be superior to those of other mono nuclear copper complexes. Furthermore, the bimetallic catalyst 1 gave exclusively diamination product in the reaction of ArX2 with ammonia, but other copper complexes showed poor selectivity. Kinetic product distribution study suggests that the dicopper metal ions in this catalysis promote the second amination efficiently.
- Liao, Bei-Sih,Liu, Shiuh-Tzung
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- Pyrido-annulated 1,3-azaphospholes: Synthesis of 1,3-azaphospholo[5,4-b] pyridines and preliminary reactivity studies
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Pyrido-annulated σ2-phosphorus heterocycles, 1,3-azaphospholo[5,4-b]pyridines 4 and 5, were synthesized by reduction of diethyl 2-aminopyridme-3-phosphonates 1 with LiAlH4 and cyclocondensation of the resulting 2-amino-3-phosphanylpyridines 2 with dimethylformamide and dimethylacetamide dimethyl acetal, respectively, via intermediate phosphaalkenes 3. The P=C-N heterocycles are stable in the presence of OH and NH compounds but add tBuLi at the P=C bond. Reaction with one equivalent of M(CO)5(thf) leads to η1-P-coordinated (azaphospholo[5,4-b]pyridine)M(CO)5 complexes (M = Cr, Mo, W). Spectroscopic data are in accordance with the dominance of π-acceptor properties. X-ray crystal structure analyses reveal "base-pairing" of 2-amino3-phosphanylpyridine (2a) and NH-functional azaphospholopyridine 5a by N-H...N hydrogen bonds, and the competing formation of 1,3-diphosphetane 6c from the phosphaalkene intermediate.
- Adam, Mohamed Shaker S.,Jones, Peter G.,Heinicke, Joachim W.
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experimental part
p. 3307 - 3316
(2011/01/05)
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- An efficient copper-catalyzed amination of aryl halides by aqueous ammonia
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The copper(I) bromide/1-(5,6,7,8-tetrahydroquinolin-8-yl)-2-methylpropan-l- one (CuBr-LS) combination catalyzed the cross-coupling reactions between aryl or heteroaryl halides and aqueous ammonia with high yields to produce primary aromatic or heteroaromatic amines at room temperature or under mild conditions.
- Wang, Deping,Cai, Qian,Ding, Ke
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supporting information; experimental part
p. 1722 - 1726
(2011/02/25)
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- Efficient palladium-catalyzed synthesis of aminopyridyl phosphonates from bromopyridines and diethyl phosphite
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A general method for coupling aminopyridyl bromides with diethyl phosphite is reported. This efficient route is realized through the use of a palladium catalyst and triethylamine as base. Georg Thieme Verlag Stuttgart.
- Bessmertnykh, Alla,Douaihy, Christiane Morkos,Muniappan, Sankar,Guilard, Roger
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experimental part
p. 1575 - 1579
(2009/04/03)
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- A general and efficient 2-amination of pyridines and quinolines
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(Chemical Equation Presented) Pyridine N-oxides were converted to 2-aminopyridines in a one-pot fashion using Ts2O-t-BuNH2 followed by in situ deprotection with TFA. The amination proceeded in high yields, excellent 2-/4-selectivity, and with good functional group compatibility. 2-Amino (iso)quinolines were also obtained in the same manner. Combined with the simple oxidation of pyridines to pyridine N-oxides, this method provides a general and efficient way for amination of 2-unsubstituted pyridines.
- Yin, Jingjun,Xiang, Bangping,Huffman, Mark A.,Raab, Conrad E.,Davies, Ian W.
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p. 4554 - 4557
(2008/02/04)
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- HETEROAROMATIC AMIDES AS INHIBITOR OF FACTOR XA
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This application relates to heteroaromatic amides (or a pharmaceutically acceptable salt thereof) as defined herein, pharmaceutical compositions thereof, and its use as an inhibitor of factor Xa, as well as a process for its preparation and intermediates therefor.
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- Substituted 2-aminopyridines as inhibitors of nitric oxide synthases.
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A series of substituted 2-aminopyridines was prepared and evaluated as inhibitors of human nitric oxide synthases (NOS). 4,6-Disubstitution enhanced both potency and specificity for the inducible NOS with the most potent compound having an IC50 of 28 nM.
- Hagmann,Caldwell,Chen,Durette,Esser,Lanza,Kopka,Guthikonda,Shah,MacCoss,Chabin,Fletcher,Grant,Green,Humes,Kelly,Luell,Meurer,Moore,Pacholok,Pavia,Williams,Wong
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p. 1975 - 1978
(2007/10/03)
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- Process for the preparation of 2-substituted 5-alkyl-pyridines
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The title compounds of the formula STR1 can be prepared by cyclization of aminomethylenated 2-pentenoic acid derivatives of the formula STR2 where R, X, R1, R2 and Z have the meaning given in the description, in the presence of acids or ammonia. Preferably, aminomethylenated pentenoic acid derivatives are employed which can be prepared from pentenoic acid derivatives of the formula or with ortho-amides of the formula STR3 The meanings of A and B are also given in the description.
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- Process for the preparation of 2-amino-5-methyl-pyridine
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The invention relates to a novel process and novel intermediates for the preparation of 2-amino-5-methylpyridine (I) STR1 The process is characterized in that in a first step 3-methyl-pyridine 1-oxide of the formula (II) STR2 is reacted with a trialkylamine of the general formula (III) in which R represents alkyl, and with an electrophilic compound, in the presence or absence of a diluent, to give the ammonium salt of the general formula (IV) STR3 in which R has the abovementioned meaning and Z? represents an anion formed from an electrophilic compound, the compound (IV) is, possibly, isolated as a crude intermediate and, possibly, further purified and then in a second step the ammonium salt of the formula (IV) is reacted with hydrogen bromide, in the presence or absence of a diluent, at temperatures between 150° C. and 300° C. The compound (I) is an intermediate for the preparation of agrochemicals, for example of herbicides.
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- REGIOSPECIFIC AMINATION OF 3-SUBSTITUTED PYRIDINES USING IMIDOYL CHLORIDE FUNCTIONALIZED POLYSTYRENE
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New imidoyl chloride functionalized polystyrenes have been prepared and reacted with pyridine 1-oxides; regiospecific acylamination of 3-substituted pyridines at the 6-position has been achieved, the corresponding aminopyridine obtained by hydrolysis and, the polymer reagent recycled.
- Abramovitch, Rudolph A.,You-Xiong, Wang
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p. 2065 - 2068
(2007/10/02)
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- Studies on 1,3-Benzoxazines. I. Synthesis of Primary 2-Amino-pyridines via the Reaction of Imidoyl Chlorides of 1,3-Benzoxazines with Pyridine N-Oxides
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A new synthetic method for primary 2-aminopyridine derivatives is described.Treatment of the imidoyl chlorides of 1,3-benzoxazines (1a-i) with pyridine N-oxides resulted in the introduction of an oxazine moiety into the α-position of the pyridine ring through rearrangement of the initially formed reaction adduct.Acid hydrolysis of the rearrangement products afforded 2-aminopyridine derivatives in excellent yields.When methoxypyridine N-oxides were used, products of a different type (10 and 14) were obtained.
- Wachi, Kazuyuki,Terada, Atsusuke
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p. 465 - 472
(2007/10/02)
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