- Carbon Atom Insertion into Pyrroles and Indoles Promoted by Chlorodiazirines
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Herein, we report a reaction that selectively generates 3-arylpyridine and quinoline motifs by inserting aryl carbynyl cation equivalents into pyrrole and indole cores, respectively. By employing α-chlorodiazirines as thermal precursors to the corresponding chlorocarbenes, the traditional haloform-based protocol central to the parent Ciamician-Dennstedt rearrangement can be modified to directly afford 3-(hetero)arylpyridines and quinolines. Chlorodiazirines are conveniently prepared in a single step by oxidation of commercially available amidinium salts. Selectivity as a function of pyrrole substitution pattern was examined, and a predictive model based on steric effects is put forward, with DFT calculations supporting a selectivity-determining cyclopropanation step. Computations surprisingly indicate that the stereochemistry of cyclopropanation is of little consequence to the subsequent electrocyclic ring opening that forges the pyridine core, due to a compensatory homoaromatic stabilization that counterbalances orbital-controlled torquoselectivity effects. The utility of this skeletal transform is further demonstrated through the preparation of quinolinophanes and the skeletal editing of pharmaceutically relevant pyrroles.
- Dherange, Balu D.,Kelly, Patrick Q.,Levin, Mark D.,Liles, Jordan P.,Sigman, Matthew S.
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supporting information
p. 11337 - 11344
(2021/08/16)
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- ZnMe2-Mediated, Direct Alkylation of Electron-Deficient N-Heteroarenes with 1,1-Diborylalkanes: Scope and Mechanism
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The regioselective, direct alkylation of electron-deficient N-heteroarenes is, in principle, a powerful and efficient way of accessing alkylated N-heteroarenes that are important core structures of many biologically active compounds and pharmaceutical agents. Herein, we report a ZnMe2-promoted, direct C2- or C4-selective primary and secondary alkylation of pyridines and quinolines using 1,1-diborylalkanes as alkylation sources. While substituted pyridines and quinolines exclusively afford C2-alkylated products, simple pyridine delivers C4-alkylated pyridine with excellent regioselectivity. The reaction scope is remarkably broad, and a range of C2- or C4-alkylated electron-deficient N-heteroarenes are obtained in good yields. Experimental and computational mechanistic studies imply that ZnMe2 serves not only as an activator of 1,1-diborylalkanes to generate (α-borylalkyl)methylalkoxy zincate, which acts as a Lewis acid to bind to the nitrogen atom of the heterocycles and controls the regioselectivity, but also as an oxidant for rearomatizing the dihydro-N-heteroarene intermediates to release the product.
- Jo, Woohyun,Baek, Seung-Yeol,Hwang, Chiwon,Heo, Joon,Baik, Mu-Hyun,Cho, Seung Hwan
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supporting information
p. 13235 - 13245
(2020/09/01)
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- Transition-Metal-Free Regioselective Alkylation of Pyridine N-Oxides Using 1,1-Diborylalkanes as Alkylating Reagents
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Reported herein is an unprecedented base-promoted deborylative alkylation of pyridine N-oxides using 1,1-diborylalkanes as alkyl sources. The reaction proceeds efficiently for a wide range of pyridine N-oxides and 1,1-diborylalkanes with excellent regioselectivity. The utility of the developed method is demonstrated by the sequential C?H arylation and methylation of pyridine N-oxides. The reaction also can be applied for the direct introduction of a methyl group to 9-O-methylquinine N-oxide, thus it can serve as a powerful method for late-stage functionalization.
- Jo, Woohyun,Kim, Junghoon,Choi, Seoyoung,Cho, Seung Hwan
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supporting information
p. 9690 - 9694
(2016/08/10)
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- Pd-Catalyzed Ligand-Free Synthesis of Arylated Heteroaromatics by Coupling of N-Heteroaromatic Bromides with Iodobenzene Diacetate, Iodosobenzene, or Diphenyliodonium Salts
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An efficient method for synthesizing arylated heteroaromatics has been reported via Pd-catalyzed ligand-free cross-coupling of N-heteroaromatic bromides with iodine(III) reagents under mild conditions. Iodobenzene diacetate, iodosobenzene, and diphenyliod
- Wang, Xiajun,He, Yongqin,Ren, Mengdan,Liu, Shengkang,Liu, He,Huang, Guosheng
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p. 7958 - 7962
(2016/09/09)
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- Newly-generated Al(OH)3-supported Pd nanoparticles-catalyzed Stille and Kumada coupling reactions of diazonium salts, (Het)aryl chlorides
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A ligand-free Pd/Al(OH)3 nano-catalyst which is prepared by one-pot three-component method using Pd(PPh3)4, tetra (ethylene glycol), and aluminum tri-sec-butoxide exhibits excellent catalytic activity in Stille cross-couplings of (Het)aryl chlorides, arenediazonium tetrafluoroborate salts with phenyltributylstannane, respectively, and Kumada couplings of (Het)aryl chlorides with various Grignard reagents. More importantly, these two processes show excellent functional group compatibility with moderate to good yields and they are also versatile with respect to not only (Het)aryl chlorides, but also diazonium salts, and heteroaryl Grignard reagents. The nano-catalyst could also be recycled and reused 5 times without loss of activity and decrease of yield.
- Li, Xing,Zhu, Tingting,Shao, Zhongqi,Li, Yingjun,Chang, Honghong,Gao, Wenchao,Zhang, Yongli,Wei, Wenlong
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supporting information
p. 69 - 75
(2015/12/23)
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- Nickel- and Palladium-Catalyzed Coupling of Aryl Fluorosulfonates with Aryl Boronic Acids Enabled by Sulfuryl Fluoride
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Herein are reported examples of the nickel- and palladium-catalyzed cross-coupling of aryl fluorosulfonates and aryl boronic acids. These reactions occur in good to excellent yields under mild conditions with excellent functional group compatibility employing either Pd(OAc)2 and inexpensive PPh3 or the inexpensive and readily available NiCl2(PCy3)2. Importantly, the in situ conversion of phenol derivatives to the corresponding aryl fluorosulfonate by reaction with sulfuryl fluoride and a base and subsequent cross-coupling to form biaryls in a single pot are described. The combination of inexpensive sulfuryl fluoride and efficient catalysts reported in these methodologies will enable economical Suzuki coupling of phenols in pharmaceutical and agrochemical processes.
- Hanley, Patrick S.,Krasovskiy, Arkady L.,Ober, Matthias S.,Whiteker, Gregory T.,Kruper, William J.
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p. 5041 - 5046
(2015/09/15)
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- METHOD FOR COUPLING A FIRST AROMATIC COMPOUND TO A SECOND AROMATIC COMPOUND
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In one aspect, there is provided a method of coupling a first aromatic compound having a fluorosulfonate substituent to a second aromatic compound having a boron-containing substituent. In another aspect, there is provided a method of coupling a first aromatic compound having a hydroxyl substituent to a second aromatic compound having a boron-containing substituent in a one-pot reaction.
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Paragraph 00142-00144
(2015/11/24)
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- Visible-light-promoted and one-pot synthesis of phenanthridines and quinolines from aldehydes and o -Acyl hydroxylamine
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A one-pot synthesis of phenanthridines and quinolines from commercially available or easily prepared aldehydes has been reported. O-(4-Cyanobenzoyl)hydroxylamine was utilized as the nitrogen source to generate O-acyl oximes in situ with aldehydes catalyzed by Bronsted acid. O-Acyl oximes were then subjected to visible light photoredox catalyzed cyclization via iminyl radicals to furnish aza-arenes. A variety of phenanthridines and quinolines have been prepared assisted by Bronsted acid and photocatalyst under visible light at room temperature with satisfactory yields.
- An, Xiao-De,Yu, Shouyun
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supporting information
p. 2692 - 2695
(2015/06/16)
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- Iridium-catalyzed C-H borylation of pyridines
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The iridium-catalysed C-H borylation is a valuable and attractive method for the preparation of aryl and heteroaryl boronates. However, application of this methodology for the preparation of pyridyl and related azinyl boronates can be challenged by low reactivity and propensity for rapid protodeborylation, particularly for a boronate ester ortho to the azinyl nitrogen. Competition experiments have revealed that the low reactivity is due to inhibition of the active catalyst through coordination of the azinyl nitrogen lone pair at the vacant site on the iridium. This effect can be overcome through the incorporation of a substituent at C-2. Moreover, when this is sufficiently electron-withdrawing protodeborylation is sufficiently slowed to permit isolation and purification of the C-6 boronate ester. Following functionalization, reduction of the directing C-2 substituent provides the product arising from formal ortho borylation of an unhindered pyridine ring. This journal is the Partner Organisations 2014.
- Sadler, Scott A.,Tajuddin, Hazmi,Mkhalid, Ibraheem A. I.,Batsanov, Andrei S.,Albesa-Jove, David,Cheung, Man Sing,Maxwell, Aoife C.,Shukla, Lena,Roberts, Bryan,Blakemore, David C.,Lin, Zhenyang,Marder, Todd B.,Steel, Patrick G.
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supporting information
p. 7318 - 7327
(2014/11/07)
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- Synthesis of pinacol arylboronates from aromatic amines: A metal-free transformation
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A metal-free borylation process based on Sandmeyer-type transformation using arylamines derivatives as the substrates has been developed. Through optimization of the reaction conditions, this novel conversion can be successfully applied to a wide range of aromatic amines, affording borylation products in moderate to good yields. Various functionalized arylboronates, which are difficult to access by other methods, can be easily obtained with this metal-free transformation. Moreover, this transformation can be followed by Suzuki-Miyaura cross-coupling without purification of the borylation products, which enhances the practical usefulness of this method. A possible reaction mechanism involving radical species has been proposed.
- Qiu, Di,Jin, Liang,Zheng, Zhitong,Meng, He,Mo, Fanyang,Wang, Xi,Zhang, Yan,Wang, Jianbo
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p. 1923 - 1933
(2013/03/29)
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- Cyclometallated Pd(II) thiosemicarbazone complexes: New catalyst precursors for Suzuki-coupling reactions
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Four tridentate [C,N,S] thiosemicarbazone Pd(II) complexes were applied as catalyst precursors for the Suzuki-Miyaura coupling of a variety of aryl halides and aryl boronic acids. After screening various catalytic conditions, it was found that one dinuclear complex IV containing the bis(diphenylphosphino) ferrocene spacer was able to efficiently catalyze these reactions with yields up to 99% irrespective of the type of aryl substituent on the substrate.
- Yan, Hong,Chellan, Prinessa,Li, Tingyi,Mao, Jincheng,Chibale, Kelly,Smith, Gregory S.
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p. 154 - 157
(2013/02/21)
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- Synthesis of biaryls through a one-pot tandem borylation/Suzuki-Miyaura cross-coupling reaction catalyzed by a palladacycle
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The tricyclohexylphosphane adduct of cyclopalladated ferrocenylimine I exhibited high catalytic activity in the one-pot borylation/Suzuki-Miyaura coupling (BSC) reaction with low catalyst loading (2 mol-%). Various biaryls were obtained in good to excellent yields for 37 examples. This process was applied to aryl and heteroaryl halides (Br and Cl) containing a variety of functional groups and did not require an excess amount of phosphane ligand and the addition of the palladium catalyst in the second step. Cyclopalladated ferrocenylimine I exhibited high catalytic activity in the borylation/Suzuki- Miyaura coupling (BSC) reaction with low catalyst loading. Various unsymmetrical biaryls were obtained ingood to excellent yields in one pot. This protocol was applied to aryl and heteroaryl halides (Br and Cl) containing a variety of functional groups without adding catalyst in the second step. Copyright
- Wang, Lianhui,Cui, Xiuling,Li, Jingya,Wu, Yusheng,Zhu, Zhiwu,Wu, Yangjie
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p. 595 - 603
(2012/03/09)
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- OXADIAZOLE DERIVATIVE HAVING ENDOTHELIAL LIPASE INHIBITORY ACTIVITY
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Disclosed is a compound which is useful as an endothelial lipase inhibitor. A compound represented by the formula: its pharmaceutically acceptable salt, or a solvate thereof, wherein Ring A is aromatic carbocycle or aromatic heterocycle,Z is —NR5—, —O— or —S—,R5 is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl or the like,R1 is hydrogen, halogen, hydroxy, cyano, nitro, carboxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl or the like,R2 and R3 are each independently hydrogen, halogen, hydroxy or the like,R4 is a group represented by the formula: —(CR6R7)n-R8, wherein R6 and R7 are each independently hydrogen, halogen, hydroxy or the like, n is an integer of 0 to 3, R8 is carboxy, cyano, substituted or unsubstituted alkyl or the like, Rx is halogen, hydroxy, cyano, nitro, carboxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl or the like,m is an integer of 0 to 3.
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Page/Page column 29-30
(2012/10/08)
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- Compositions and methods for modulating a kinase cascade
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The invention relates to compounds and methods for modulating one or more components of a kinase cascade.
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Page/Page column 151
(2009/06/27)
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- Phosphine-free cross-coupling reaction of halopyridines with arylboronic acids in an ionic liquid: Water mixture
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Palladium acetate-catalysed Suzuki reaction of halopyridines and arylboronic acids has been investigated in roomtemperature ionic liquids in the absence of the phosphine ligand. A significant effect of water on the efficiency of the Suzuki reaction in ionic liquids was observed. The mixture of ionic liquid and water significantly enhanced the rate of the coupling reaction. The separation of the product was easily performed by extraction with diethyl ether and the Pd(OAc)2-[bmim][PF6] (1-butyl-3-methylimidazolium hexafluorophosphate) can be reused six times with only a small loss of reactivity.
- Xin, Bingwei
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experimental part
p. 412 - 415
(2009/06/30)
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- Compositions and methods of treating cell proliferation disorders
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The invention relates to compounds and methods for treating cell proliferation disorders.
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Page/Page column 82-83
(2008/06/13)
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- 5-MEMBERED N-HETEROCYCLIC COMPOUNDS WITH HYPOGLYCEMIC AND HYPOLIPIDEMIC ACTIVITY
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Use of a compound of the formula: wherein R represents a hydrocarbon group which may be substituted or a heterocyclic group which may be substituted; X represents a bond, an oxygen atom, a sulfur atom, or a group of the formula: -CO-, -CS-, -CR(OR)- or -NR- wherein each of R and R represents a hydrogen atom or a hydrocarbon group which may be substituted, R represents a hydrogen atom or a protective group for a hydroxyl group; m represents an integer of 0 to 3; Y represents an oxygen atom, a sulfur atom, or a group of the formula: -SO-, -SO2-, -NR-, -CONR- or -NRCO- wherein R represents a hydrogen atom or a hydrocarbon group which may be substituted; ring A represents an aromatic ring which may further have 1 to 3 substituents; n represents an integer of 1 to 8; ring B represents a nitrogen-containing 5-membered hetero ring which may further be substituted by an alkyl group; X represents a bond, an oxygen atom, a sulfur atom, or a group of the formula: -SO-, -SO2-, -O-SO2- or -NR- wherein R represents a hydrogen atom or a hydrocarbon group which may be substituted; R represents a hydrogen atom, a hydrocarbon group which may be substituted or a heterocyclic group which may be substituted; W represents a bond or a divalent hydrocarbon residue having 1 to 20 carbon atoms; R represents a group of the formula: -OR (R represents a hydrogen atom or a hydrocarbon group which may be substituted) or -NRR (each of R and R, whether identical or not, represents a hydrogen atom, a hydrocarbon group which may be substituted, a heterocyclic group which may be substituted, or an acyl group which may be substituted; R and R may bind together to form a ring); or a salt thereof, for the manufacture of a pharmaceutical preparation for preventing or treating syndrome X.
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- COMPOUNDS AND METHODS
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This invention relates to substituted heteroanilide compounds which are modulators, agonists or antagonists, of the CCR5 receptior. In addition, this invention relates to the treatment and prevention of disease states mediatd by CCR5.
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- DIELS-ALDER REACTION OF 1,2,3-TRIAZINE WITH ALDEHYDE ENAMINE
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The Diels-Alder reaction of 4-methyl-1,2,3-triazine with several aldehyde enamines was carried out to afford 2,5-disubstituted pyridines.As an application of this method, we accomplished the synthesis of alkaloid, fusaric acid.
- Koyama, Junko,Ogura, Tamaki,Tagahara, Kiyoshi
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p. 1595 - 1600
(2007/10/02)
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- ARYL THIOPYRANO[2,3,4-C,D]INDOLES AS INHIBITORS OF LEUKOTRIENE BIOSYNTHESIS
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Compounds having the formula I: are inhibitors of 5-lipoxygenase and inhibitors of leukotriene biosynthesis. These compounds are useful as anti-asthmatic, anti-allergic, anti-inflammatory, and cyto-protective agents. They are also useful in treating angina, cerebral spasm, glomerular nephritis, hepatitis, endotoxemia, psoriasis, uveitis, and allograft rejection and in preventing the formation of atherosclerotic plaques.
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- Thiopyrano[2,3,4-c,d]indoles as inhibitors of leukotriene biosynthesis
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Compounds having the formula I: STR1 are inhibitors of leukotriene biosynthesis. These compounds are useful as anti-asthmatic, anti-allergic, anti-inflammatory, and cytoprotective agents. They are also useful in treating angina, cerebral spasm, glomerular nephritis, hepatitis, endotoxemia, psoriasis, uveitis and allograft rejection and in preventing the formation of atherosclerotic plaques.
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- Pyridyl styrene dialkanoic acids as anti-leukotriene agents
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Compounds having the formula: STR1 are leukotriene antagonists and inhibitors of leukotriene biosynthesis. These compounds are useful as anti-asthmatic, anti-allergic, anti-inflammatory, and cytoprotective agents.
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- Pyridyl dialkanoic acids and their use as medicaments
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Compounds having the formula. are leukotriene antagonists and inhibitors of leukotriene biosynthesis. These compounds are useful as anti-asthmatic, anti-allergic, anti-inflammatory, and cytoprotective agents.
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- Pyridine Derivatives in Peppermint Oil
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Five kinds of pyridine derivatives (1-5), including a novel compound, 5-phenyl-2-propylpyridine (4), were newly identified in peppermint oil.
- Sakurai, Kazutoshi,Takahashi, Katsuhiro,Yoshida, Toshio
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p. 2307 - 2312
(2007/10/02)
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- SYNTHESIS OF 3-AZAFLUORENE AND 2H-2-METHYLINDENOPYRIDINE
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4-Methyl-3-phenylpyridine was isolated from the mixture of four isomeric methylphenylpyridines formed in the condensation of crotonaldehyde with phenylacetaldehyde (β-phenylethanol or phenylacetylene) with ammonia in the presence of a cadmium-calcium phosphate catalyst. 4-Methyl-3-phenylpyridine was converted to 3-azafluorene by catalytic dehydrocyclization.A representative of a new series of pseudoazulenes, viz., 2H-2-methylindeno-pyridine, was obtained by treatment of 3-azafluorene methiodide with sodium hydroxide solution; the product was a crystalline black substance that remained unchanged during storage in air for 1 month.
- Prostakov, N. S.,Radzhan, P. K.,Soldatenkov, A. T.
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p. 1153 - 1156
(2007/10/02)
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