4786-24-7Relevant academic research and scientific papers
5, 7-SUBSTITUTED-IMIDAZO [1, 2-C] PYRIMIDINES AS INHIBITORS OF JAK KINASES
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Page/Page column 78, (2011/11/01)
Compounds of Formula I: (Formula should be inserted here) and stereoisomers and pharmaceutically acceptable salts and solvates thereof in which R1, R2, R3, R4, R5, R6, R7, X1 and X2 have the meanings given in the specification, are inhibitors of one or more JAK kinases and are useful in the treatment of autoimmune diseases, inflammatory diseases, rejection of transplanted organs, tissues and cells, as well as hematologic disorders and malignancies and their co-morbidities.
Synthesis of aryliminoacetonitriles under FVT conditions or by dehydrogenation of arylaminoacetonitriles: an NMR and UV-photoelectron spectroscopy study
Le?niak, Stanis?aw,Chrostowska, Anna,Kuc, Dawid,Maciejczyk, Ma?gorzata,Khayar, Sa?d,Nazarski, Ryszard B.,Urbaniak, ?ukasz
body text, p. 10581 - 10589 (2010/02/28)
The synthesis of [(E)-arylimino]-acetonitriles 3 has been described. It was found that the title compounds can be obtained on the three ways, namely by: (i) dehydrogenation of arylaminoacetonitriles 1, (ii) thermal fragmentation of 1-aryl-4-cyano-β-lactams 4 and (iii) retro-ene reaction of (allyl-p-methoxyphenyl-amino)-acetonitrile (7a) under FVT conditions. 1H and 13C NMR spectra of compounds 3, 5 and 6, and all their precursors 1 and 4, were recorded and analysed in detail using chemical shifts δH and δC [from GIAO DFT B3LYP/6-31(d) calculations] and J-couplings predicted at the DFT B3LYP/IGLO-II level. Also, UV-photoelectron spectra of 4a,d and 3a,d were measured and analysed considering the theoretical evaluation of their ionisation potentials.
Elimination kinetics of β-hydroxynitriles in the gas phase
Chuchani, Gabriel,Dominguez, Rosa M.,Rotinov, Alexandra,Quijano, Jairo,Valencia, Cristina,Vicente, Bernardo,Franco, Dimas
, p. 19 - 23 (2007/10/03)
The gas-phase elimination kinetics of primary, secondary and tertiary β-hydroxynitriles were examined in static seasoned vessels over the temperature range 360-450 °C and pressure range 47-167 Torr (1 Torr = 133.3 Pa). These reactions are homogeneous, unimolecular and follow a first-order rate law. The rate coefficients are given by the Arrhenius equation: for 3-hydroxypropionitrile log k1 = (14.29 ± 0.47) - (234.9 ± 6.3) kJ mol-1 (2.303 RT)-1; for 3-hydroxybutyronitrile log k1 = (13.76 ± 0.10) - (222.6 ± 0.7) kJ mol-1 (2.303RT)-1; and for 3-hydroxy-3-methylbutyronitrile log k1 (s-1) = (13.68 ± 0.68) - (212.5 ± 8.7) kJ mol-1 (2.303RT)-1. The decomposition rates of the β-hydroxynitriles increase from primary to tertiary carbon containing the OH group. The rates for the β-hydroxynitriles are found to be slower than those for the corresponding β-hydroxyacetylene analogs. The value of log A from 13.7 to 14.4 and the small positive ΔS≠ indicate a mechanism different from a six-centered cyclic transition state. These data appear to indicate that a four-membered cyclic transition state or a quasi-heterolytic mechanism is conceivable. Copyright
The Cyanation of Vinyl Halides with Alkali Cyanides Catalyzed by Nickel(0)-Phosphine Complexes Generated In Situ: Synthetic and Stereochemical Aspects
Sakakibara, Yasumasa,Enami, Hiroji,Ogawa, Hiroshi,Fujimoto, Shinpei,Kato, Hiroyuki,et al.
, p. 3137 - 3144 (2007/10/03)
The cyanation of β-bromostyrenes catalyzed by Ni(PPh3)n, which was generated in situ from NiBr2(PPh3)2-Zn-PPh3 (Ni:Zn:P=1:3:2 molar ratio), was at first examined with various MCN (M=K, Na)-dipolar aprotic solvent systems by several procedures.The presence of excess cyanide ion inhibited the reaction.However, when the KCN-DMF system with some intermediate cyanide solubility was used, the nitriles were obtained in high yields and high stereoselectivity at 50 deg C by almost all of the procedures attempted.On the contrary, the KCN-HMPA and KCN-MeCN systems with cyanide solubilities accelerated the coupling of the halides to inhibit the cyanation, and in general the NaCN-DMF and NaCN-HMPA systems with high cyanide solubilities needed to reduce Ni(II) before adding MCN in order to make the catalytic reaction start.Vinyl halides such as 1- and 2-halo (Cl, Br)-1-alkenes, 2-bromo-2-butenes, 3-bromo-3-hexenes, and 1-chlorocyclohexene were also cyanated using suitable procedures and MCN-solvent systems to give the corresponding nitriles in high yields and fair-to-good stereoselectivities.However, with (Z)-2-ethoxy-1-bromoethene the (E)-nitrile, though its selectivity markedly varied with the reaction temperature, was obtained as the main product.The cyanation of ethyl (Z)-β-bromoacrylate and ethyl α-bromoacrylate was unsuccessful due to polymerization.
The Introduction of Nitrile-Groups into Heterocycles and Concversion of Carboxylic Groups into their Corresponding Nitriles with Clorosulfonylisocyanate and Triethylamine
Vorbrueggen, Helmut,Krolikiewicz, Konrad
, p. 6549 - 6558 (2007/10/02)
Addition of chlorosulfonylisocyanate (CSI) to heterocycles such as thiophene (4) or indole (15) and unsaturated systems such as dihydropyran (7) gives N-chlorosulfonylamides RCONHSO2Cl, which can be converted by equivalent amounts of triethylamine to their corresponding nitriles.Since carboxylic acids react with CSI to N-chlorosulfonylamides, subsequent treatment with triethylamine affords the corresponding nitriles, but no isocyanates as claimed by other authors.The mechanisms of the conversion of the intermediate N-chlorosulfonylamides into the corresponding nitriles are discussed.
Dehydrobromination of γ-Bromo-β-oxonitriles. Formation of α,β-Unsaturated Nitriles by Decarbonylation of Cyanocyclopropanone Intermediates
Herter, Rolf,Foehlisch, Baldur
, p. 381 - 384 (2007/10/02)
The title reaction was observed with the 4-bromo-3-oxopentanenitriles 1a and b which react with silver oxide to form the 2-butenenitriles 3a and b.A further product of the bromide 1b, bis(3-cyano-2,2-dimethylbutanoic) anhydride (5b), can also be derived from a cyanocyclopropanone intermediate by nucleophilic cleavage.Ring contractions may be performed by boiling the cyclic γ-bromo-β-oxonitriles 6a - d in toluene with silver oxide to yield the 1-cycloalkene-1-carbonitriles 8a - d.
Stereoselective Cyanation of Vinyl Halides Catalyzed by Tetracyanocobaltate(I)
Funabiki, Takuzo,Hosomi, Hiroaki,Yoshida, Satohiro,Tarama, Kimio
, p. 1560 - 1568 (2007/10/02)
Tetracyanocobaltate(I), 3-, which is formed in an aqueous alkaline solution under a hydrogen atmosphere, catalyzes the cyanation of vinyl halides to form 2-alkenenitriles.The reaction is stereoselective, forming nitriles with retention of configuration, except for (Z)-2-bromobut-2-ene, which forms a mixture of nearly equimolar isomeric nitriles.Reactivity is dependent on the CN:Co ratio and is highest when the ratio is slightly lower than 5:1.Presence of excess cyanide ion inhibits the reaction, but a dropwise addition of the KCN solution to maintain CN:Co3-, were detected as intermediates by 1H and 13C NMR spectroscopy, indicating that the reaction proceeds stepwise.In the first step, the ? complex is formed by the oxidative addition of a vinyl halide to 3- via a radical nonchain process; in this step stereoselectivity is determined.In the second step, which is rate determining, a 2-alkenenitrile is formed by the reductive coupling of the vinyl and cyano ligands, regenerating 3-.Clear NMR evidence has been obtained for the formation of 3-, where the olefin is (E)- or (Z)-cinnamonitrile.A high degree of electron transfer from 3- to olefin was indicated by the large upfield shifts of the olefinic carbon atom resonances by coordination.
Production of Acrylonitrile and Other Unsaturated Nitriles from Alkenes and Alkynes
Henis, Neil B.,Miller, Larry L.
, p. 2526 - 2529 (2007/10/02)
Passage of unsaturated organic molecules trough a 13.56-MHz radio-frequency discharge, in the presence of cyanogen, results in the formation of unsaturated nitriles.Acrylonitrile was the major product from ethylene, propylene, acrolein, methyl vinyl ketone, or 1,1,1-trifluoropropylene. 1-Butene, 2-butene, and isobutylene gave mixtures of nitrile products with the CN situated at vinylic or allylic positions. 2-Butyne gave 1-cyanopropyne.Other compounds gave only low yields of nitriles and considerable polymer.The effects of power, pressure, flow rate, and ratios of reactants on the yields of acrylonitrile from propylene and cyanogen were studied.A typical power yield of acrylonitrile was 30 g kW-1 h-1.Maximum material yields of nitrile products were obtained at intermediate powers and pressures.The products are consistent with a reaction scheme involving attack of initially formed cyano radicals on the organic substrate.This step forms activated radical intermediates, which decay through elimination of an atom or group.The atom or group which is most weakly bound is preferentially lost.
