- Nitropyrimidinones; synthetic equivalents of diformylamine and nitromalonaldehyde
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Reactions of two isomeric nitropyrimidinones with bidentate enolate anions were studied. When 3-methyl-5-nitropyrimidin-4(3H)-one (1) was employed, ring transformation proceeded to give pyridin-4(1H)-ones 3 functionalized at the 3- or 5-positions. This pyrimidin-4-one 1 behaved as an activated diformylamine HN(CHO)2. 1-Methyl-5-nitropyrimidin-2(1H)-one (2) afforded polyfunctionalized bicyclo[3.3.1]nonene derivatives 7 and 8 and/or p-nitrophenol derivatives 9. In this case, pyrimidin-2-one 2 acted as the synthetic equivalent of unstable O2NCH(CHO)2. These two nitropyrimidinones are valuable intermediates for the synthesis of polyfunctionalized compounds.
- Nishiwaki,Tohda,Ariga
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Read Online
- Method for preparing nitro compound by using graphene to catalyze nitric oxide
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The invention discloses a method for preparing a nitro compound by using graphene to catalyze nitric oxide. A graphene oxide carbon material is used for catalysis of a reaction of nitric oxide and a nitrification substrate such as an aromatic compound to prepare the nitro compound. The method is used for replacing a traditional nitric acid/sulfur acid method to prepare the nitro compound, so thatthe atom utilization rate of the reaction is increased, the energy is saved, and the emission is reduced; and the method has the characteristic of atom economy during industrial preparation of the nitro compound.
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Paragraph 0043; 0044
(2018/06/16)
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- Tailor-made synthesis of N,N,2,6-tetrasubstituted 4-nitroanilines by three-component ring transformation of dinitropyridone
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The ring transformation of dinitropyridone afforded various kinds of 2,6-disubstituted-4-nitroanilines upon treatment with aliphatic ketones in the presence of ammonium acetate as a nitrogen source, wherein dinitropyridone behaved as the synthetic equival
- Le, Song Thi,Asahara, Haruyasu,Nishiwaki, Nagatoshi
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supporting information
p. 1203 - 1206
(2015/03/04)
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- Nitrosation of aryl and heteroaryltrifluoroborates with nitrosonium tetrafluoroborate
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Organotrifluoroborates have emerged as an alternative to toxic and air- and moisture-sensitive organometallic species for the synthesis of functionalized aryl and heteroaryl compounds. It has been shown that the trifluoroborate moiety can be easily converted into a variety of different substituents in a late synthetic stage. In this paper, we disclose a mild, selective, and convenient method for the ipso-nitrosation of organotrifluoroborates using nitrosonium tetrafluoroborate (NOBF4). Aryl- and heteroaryltrifluoroborates were converted into the corresponding nitroso products in good to excellent yields. This method proved to be tolerant of a broad range of functional groups.
- Molander, Gary A.,Cavalcanti, Livia N.
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experimental part
p. 4402 - 4413
(2012/06/18)
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- Modification and optimization of the bis-picolylamide-based relay protection for carboxylic acids to be cleaved by unusual complexation with Cu2+ salts
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A simple modification of our recently published protection scheme for carboxylic acids as amides resulted in a new protecting group with significantly improved properties. It requires shorter reaction times for deprotection and allows us to replace Cu(OTf)2 by CuCl2, indicating at the same time the importance of the nature of the anion of the Cu2+ source. Since the new scheme fulfills all criteria required for an ideal protection group it should find widespread application in synthetic organic chemistry.
- Mundinger, Stephan,Jakob, Uwe,Bichovski, Plamen,Bannwarth, Willi
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p. 8968 - 8979,12
(2012/12/11)
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- Facile one-pot direct arylation and alkylation of nitropyridine N -oxides with grignard reagents
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Facile arylation and alkylation of nitropyridine N-oxides were developed through the reactions of Grignard reagents with nitropyridine N-oxides. For the same 4-nitropyridine N-oxide, arylation occurred at the 2- (or 6-) position, whereas alkylation occurred at the 3-position in an adjustably site-selective manner. The cooperative action of the two groups was discovered in the reactions of 3-nitropyridine N-oxides. This protocol can find wide applications in building various pyridine compounds as illustrated in total syntheses of Emoxipin and Caerulomycin A and E.
- Zhang, Fang,Duan, Xin-Fang
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supporting information; scheme or table
p. 6102 - 6105
(2012/01/06)
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- 2- [ (2-SUBSTITUTED) -IND0LIZIN-3-YL] -2-OXO-ACETAMIDE DERIVATIVES AS ANTIFUNGAL AGENTS
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The invention provides compounds of formula (I), and pharmaceutically acceptable salts thereof wherein: Rl, R2, R3, R4, R5, R6, R7, X and X1 are as defined herein. These compounds are useful in the manufacture of medicaments for use in the prevention or treatment of a fungal disease. Compounds of formula (I), and agriculturally acceptable salts thereof, may also be used as agricultural fungicides.
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Page/Page column 117
(2008/12/05)
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- Preparation of nitropyridines by nitration of pyridines with nitric acid
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Preparation of nitropyridines by nitration of pyridines with nitric acid was discussed. Trifluoroacetic anhydride was chilled in an ice bath and the pyridine or substituted pyridines were slowly added and stirred at chilled conditions for 2 h. Relative amounts of the reactants were required for the nitration of pyridine were characterized by 1H and Nuclear magnetic resonance (NMR) spectroscopy and elemental analysis. It was observed that the yields of β-nitropyridines obtained using the standard protocol were generally higher than those obtained using N2O3.
- Katritzky, Alan R.,Scriven, Eric F. V.,Majumder, Suman,Akhmedova, Rena G.,Vakulenko, Anatoliy V.,Akhmedov, Novraz G.,Murugan, Ramiah,Abboud, Khalil A.
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p. 538 - 541
(2007/10/03)
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- Nitropyridyl isocyanates
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We hereby report the first preparation of 3-nitro-4-pyridyl isocyanate 9 and 5-nitro-2-pyridyl isocyanate 18. They were formed by Curtius rearrangement of the corresponding acyl azides 8 and 17, prepared from methyl 3-nitro-4-pyridinecarboxylate 6 via the hydrazide 7 and 5-nitro-picolinic acid 16, respectively. The substrates 6 and 16 were generated by nitration of methyl 4-pyridinecarboxylate 5 and nitration and oxidation of 2-picoline 14. 3-Nitro-4-pyridyl isocyanate 9 can be stored in dry solution and is stable at room temperature for several weeks while 5-nitro-2-pyridyl isocyanate 18 was less stable and should be used for synthetic purposes immediately.
- Holt, Jarle,Andreassen, Trygve,Bakke, Jan M.,Fiksdahl, Anne
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p. 259 - 264
(2007/10/03)
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- Benzopiperidine derivatives
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Benzopiperidine derivatives represented by formula (I), salts thereof or hydrates thereof, processes for producing the same and drugs comprising the same: wherein the variables are as described in the specification. These compounds are useful as drugs efficacious in the prevention and treatment of these various inflammatory diseases and immunologic diseases, such as rheumatoid arthritis, atopic dermatitis, psoriasis, asthma, and rejection reaction accompanying organ transplantation.
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- Structure-Activity Relationships of the p38α MAP Kinase Inhibitor 1-(5-tert-Butyl-2-p-tolyl-2H-pyrazol-3-yl)-3-[4-(2-morpholin-4-yl-ethoxy) naphthalen-1-yl]urea (BIRB 796)
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We report on the structure-activity relationships (SAR) of 1-(5-tert-butyl-2-p-tolyl-2H-pyrazol-3-yl)-3-[4-(2-morpholin-4-yl-ethoxy) naphthalen-1-yl]urea (BIRB 796), an inhibitor of p38α MAP kinase which has advanced into human clinical trials for the treatment of autoimmune diseases. Thermal denaturation was used to establish molecular binding affinities for this class of p38α inhibitors. The tert-butyl group remains a critical binding element by occupying a lipophilic domain in the kinase which is exposed upon rearrangement of the activation loop. An aromatic ring attached to N-2 of the pyrazole nucleus provides important π-CH 2 interactions with the kinase. The role of groups attached through an ethoxy group to the 4-position of the naphthalene and directed into the ATP-binding domain is elucidated. Pharmacophores with good hydrogen bonding potential, such as morpholine, pyridine, and imidazole, shift the melting temperature of p38α by 16-17 °C translating into Kd values of 50-100 pM. Finally, we describe several compounds that potently inhibit TNF-α production when dosed orally in mice.
- Regan, John,Capolino, Alison,Cirillo, Pier F.,Gilmore, Thomas,Graham, Anne G.,Hickey, Eugene,Kroe, Rachel R.,Madwed, Jeffrey,Moriak, Monica,Nelson, Richard,Pargellis, Christopher A.,Swinamer, Alan,Torcellini, Carol,Tsang, Michele,Moss, Neil
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p. 4676 - 4686
(2007/10/03)
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- 1,4-Benzofused urea compounds useful in treating cytokine mediated diseases
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Disclosed are 1,4-disubstituted benzo-fused urea compounds of formula (I): wherein Ar, X, A, L, and Q of formula(I) are defined herein. The compounds inhibit production of cytokines involved in inflammatory processes and are thus useful for treating diseases and pathological conditions involving inflammation such as chronic inflammatory disease. Also disclosed are processes for preparing these compounds and pharmaceutical compositions comprising these compounds.
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- Palladium catalyzed cross-methylation of bromoheterocycles with intramolecularly stabilized dimethyl indium reagents
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Although the intramolecularly stabilized [(3- dimethylamino)propyl]dimethylaluminum (1a) fails to undergo palladium-catalyzed cross-coupling with bromopyridines and with bromofuran derivatives, the analogous gallium and indium reagent lb and 1c smoothly c
- Jaber, Nimer,Schumann, Herbert,Blum, Jochanan
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p. 565 - 567
(2007/10/03)
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- Preparation of novel heteroisoindoles from nitropyridines and nitropyridones
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The reaction of nitropyridine derivatives with ethyl isocyanoacetate in the presence of 1,8-diazabicyclo[5.4.0]undecene proceeded tandem cyclization to give polycyclic pyrrolopyridines or imidazopyridines. On the other hand, N-protected 3-nitro- and 5-nitropyridones and N,N-diprotected 5-nitrouracil gave corresponding bicyclic pyrroles in good yields under the similar conditions.
- Murashima, Takashi,Nishi, Keiji,Nakamoto, Ken-ichi,Kato, Atsushi,Tamai, Ryuji,Uno, Hidemitsu,Ono, Noboru
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p. 301 - 310
(2007/10/03)
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- The synthesis of β-nitropyridine compounds
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Pyridine and a number of substituted pyridines have been nitrated by reaction with N2O5 followed by reaction with an aqueous solution of SO2xH2O or NaHSO3. The dependence of the yields on the pH of the aqueous reaction medium, on the concentration of SO2xH2O-HSO3-, on addition of methanol to the aqueous phase, and on the reaction temperature were investigated. The yields obtained with NaHSO3 were: 3-nitropyridine 77%, 2-methyl-5-nitro-pyridine 36%, 3-methyl-5-nitropyridinc 24%, 3-acetyl-5-nitropyridine 18%, 5-nitropyridine-3-carboxylic acid 15%, 3-chloro-5-nitropyridine 11%, 4-methyl-3-nitropyridine 39%, 4-acetyl-3-nitropyridine 67%, 4-cyano-3-nitropyridine 45%, 4-phenyl-3-nitropyridine 68%, 4-formyl-3-nitropyridine 62% (from reaction in liquid SO2), 3-nitropyridine-4-carboxylic acid 48%, methyl 3-nitropyridine-4-carboxylate 75%, 2,3-dimethyl-5-nitropyridine 37%, 2,4-dimethyl-5-nitropyridine 64%, 3-nitroquinoline 10% and 4-nitroisoquinoline 42%.
- Bakke, Jan M.,Ranes, Eli,Riha, Jaroslav,Svensen, Harald
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p. 141 - 144
(2007/10/03)
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- A new efficient synthesis of 3-nitropyridine and substituted derivatives
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Pyridine and pyridine derivatives have been nitrated in the β-position by reaction with N2O5 or NO2·BF4 in MeNO2, THF or MeCN to form the N-nitropyridinium salt. This was then reacted with an aqueous solution of a nucleophile to give the β-nitro compound in moderate to good yield.
- Bakke, Jan M.,Ranes, Eli
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p. 281 - 283
(2007/10/03)
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- Quinolizinone type compounds
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Antibacterial compounds having the formula STR1 and the pharmaceutically acceptable salts, esters and amides thereof, preferred examples of which include those compounds wherein A is =CR6 --; R1 is cycloalkyl of from three to eight carbon atoms or substituted phenyl; R2 is selected from the group consisting of STR2 R3 is halogen; R4 is hydrogen, loweralkyl, a pharmaceutically acceptable cation, or a prodrug ester group; R5 is hydrogen, loweralkyl, halo(loweralkyl), or --NR13 R14 ; and R6 is halogen, loweralkyl, halo(loweralkyl), hydroxy-substituted loweralkyl, loweralkoxy(loweralkyl), loweralkoxy, or amino(loweralkyl), as well as pharmaceutical compositions containing such compounds and the use of the same in the treatment of bacterial infections.
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- Formation of anilines from 5-nitro-2-phenylpyrimidine, amines, and acetone
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The reaction of 5-nitro-2-phenylpyrimidine with aliphatic amines and acetone gave N-substituted 4-nitroanilines.In addition, 2-methyl-5-nitropyridine was also obtained from ethylamine. - Key words: pyrimidine; transformation of cyclic intermediates; anilines; pyridine.
- Gromov, S. P.
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p. 1041 - 1043
(2007/10/02)
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- Nitration of Aromatic and Heteroaromatic Compounds by Dinitrogen Pentaoxide
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Nitration of benzene and monosubstituted benzenes in liquid SO2 by dinitrogen pentaoxide at - 11 deg C gave the corresponding nitroarenes with substitution patterns similar to those obtained by nitrations with HNO3-H2SO4.For acetophenone an o/m ratio of 0.94 was obtained.The yields were dependent on the substituents.With a 1:1 ratio of arene: N2O5 the yields varied from 73percent for toluene to 0.4percent for nitrobenzene as substrates.From competition experiments and the nitration of bibenzyl it was concluded that the reaction was faster than the macroscopic rate of mixing.The qualitative order of reactivity for PhX was X = OCH3>CH3>H>Cl>CH3CO>NO2.Nitration with N2O5 in liquid CO2 gave similar results.Nitration of pyrimidine, pyrrole, imidazole and indole with N2O5-SO2 gave no nitrated products.With thiophene, 2- (34percent) and 3-nitrothiophene (5percent) together with 2,4-(16percent) and 2,5-dinitrothiophene (8percent) were obtained.With pyridine, mono- and di-methylpyridines, quinoline, isoquinoline and 4-phenylpyridine nitration of the pyridine ring was obtained.The yields varied from ca. 70percent to 16percent, except for 3,5-, 2,5- and 2,6-dimethylpyridine for which only traces of nitro-dimethylpyridines were obtained.The reaction with the pyridines appears to be intramolecular both in the SO2 phase and in the water phase used for quenching the reaction.The reaction was proposed to proceed by a complex formed in liquid SO2:
- Bakke, Jan M.,Hegbom, Ingrid,Oevreeide, Elin,Aaby, Kjersti
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p. 1001 - 1006
(2007/10/02)
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- Synthesis and Properties of 3-, 4-, and 5-Nitro-2-pyridinecarbaldehyde 2-pyridylhydrazones and Characterization of Their Metal Complexes
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Three hydrazones, 3-, 4-, and 5-nitro-2-pyridinecarbaldehyde 2-pyridylhydrazones, were synthesized.Their properties and reactivities with metal ions and the extraction and characteristics of the resultant complexes have been investigated and compared with one another.As a result, useful information on the molecular design of highly sensitive hydrazone reagents has been obtained.
- Odashima, Tsugikatsu,Sakakura, Kei,Kohata, Katsunori,Ishii, Hajime
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p. 797 - 803
(2007/10/02)
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- A One-pot Synthesis of 3-Nitro- and 3,5-Dinitro-2-picolines
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3-Nitro- and 3,5-dinitro-2-picoline were each prepared in a one-pot synthesis in high yield by treatment of the respective 2-chloro-3-nitro- and 2-chloro-3,5-dinitropyridines with diethyl sodiomalonate, followed by hydrolysis and decarboxylation with 50percent sulfuric acid.
- Liu, Mao-Chin,Lin, Tai-Shun,Sartorelli, Alan C.
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p. 2965 - 2970
(2007/10/02)
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- 5-Aminopyridine compounds
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R2 represents hydrogen or halogen, R3 represents hydrogen or, together with R2, represents =0, R4 represents hydrogen or alkyl, R5 represents hydrogen, alkyl, halogenoalkyl or aryl, R7 represents alkyl, R8 represents alkyl, cyloalkyl, aralkyl, aryl or heterocyclyl, which can optionally be substituted, R9 represents acyl or hydrogen and Hal represents halogen. Compounds III are new. Compounds I are known as yield-promoting agents in animal feeds.
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- PYRIMIDINE SIGMA-COMPLEXES. 7. THE RECYCLIZATION OF 5-NITROPYRIMIDINE AND ITS METHOXY DERIVATIVES UPON REACTION WITH THE ACETYLACETONE CARBANION
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A study was carried out on the reaction of 5-nitro and 5-nitromethoxypyrimidines with the acetylacetone carbanion.Benzene and pyridine derivatives are formed as a result of recyclization.The direction of the reaction depends on the position of the substituents in the pyrimidine ring and the nature of the bases.
- Remennikov, G. Ya.,Kurilenko, L. K.,Boldyrev, I. V.,Cherkasov, V. M.
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p. 422 - 425
(2007/10/02)
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