Clarke, K.; Rothwell, K. published an article in 1960, the title of the article was A kinetic study of the effect of substituents on the rate of formation of alkylpyridinium halides in nitromethane solution.Product Details of 25813-24-5 And the article contains the following content:
Rates of reaction of substituted pyridines with CH2:CHCH2Br (I), MeI, PhCH2Br, and PrBr in MeNO2 were measured at several temperatures Substituents influenced both Arrhenius parameters, E and log PZ. In general, the logarithms of the rate constants varied linearly with the dissociation constants of the bases in H2O; however, the rates for the alkoxypyridines did not fit the linear relation, presumably due to a solvent effect, and those for the 2-substituted pyridines followed a different linear relation than those for the 3- and 4-substituted compounds Plots of log k against the Hammett substituent constants gave a somewhat scattered series of points, the 3- and 4-substituted compounds giving approx. linear relations with different slopes. The ortho effect influenced the activation energy, rather than the PZ factor. Primary steric hindrance was deemed important in the ortho effect. Changes in the free energy of ionization of pyridines and of activation for the Menschutkin reaction brought about by 2 substituents were algebraic sums of the changes brought about by the 2 groups individually, except in the case of 2,6- and 2,3-disubstituted compounds Rate constants (k × 104) at 60°, energies of activation (kcal./mole), and log PZ for reactions with I, and pK for ionization of the pyridine bases were (substituents shown): 2-Me, 7.53, 13.62, 5.83, 5.97; 3-Me, 71.4, 12.52, 6.06, 5.68; 4-Me, 81.7, 12.44, 6.07, 6.02; 2,3-Me2, 7.34, 13.86, 5.96, 6.60; 2,4-Me2, 14.6, 13.20, 5.82, 6.72; 2,5-Me2, 12.4, 13.31, 5.83, 6.47; 2,6-Me2, 0.18, -, -, 6.77; 3,4-Me2, 131.5, 12.20, 6.13, 6.52; 3,5-Me2 (II), 109.1, 12.37, 6.14, 6.14; 2-Et, 3.65, 13.94, 5.71, 5.99; 4-Et, 85.0, 12.46, 6.11, 6.02; 2,4,6-Me3, 0.31, -, -, 7.48; 2-OMe, -, -, – (no reaction), 3.40; 3-OMe, 41.3, 12.73, 5.96, 4.91; 4-OMe(III), 91.9, 12.38, 6.08, 6.55; 3-OEt, 45.7, -, -, -, 4-OEt, 104.0, 12.44, 6.18, 6.67; 3-Br, 5-OMe (IV), 5.56, 13.72, 5.75, -; 3-Br, 5-OEt (V), 6.38, 13.69, 5.78, -: 3-F, 5.69, 13.76, 5.77, 3.0; 3-Cl, 5.45, 13.72, 5.74, 2.84; 3-Br (VI), 5.87, 13.67, 5.13, 2.84; 3-CO2Et, 8.98, 13.58, 5.87, 3.35; 4-CO2Et, 10.0, 13.51, 5.87, 3.45; unsubstituted, 46.3, 12.73, 6.00, 5.17. The 2-F, 2-Cl, 3,5-Br2 (VII), 3,5-Br2 4-OMe, 3,5-Br2 4-Cl (VIII), 2-CO2Et, 4-OMe 5-NO2 (IX), and 4-OEt 5-NO2 (X) derivatives did not react with I at 60°. Kinetic measurements were made in 0.05M solution of the reactants, the extent of reaction being determined by Volhard titration of the bromide formed. VII (5 g.) in 75 ml. ether added to Me3CLi (from 1.3 g. Li) in ether at -35 to -40°, the mixture stirred 30 min., excess MeI in ether added, the ether removed, the residual paste acidified and steam-distilled, and the residue made alk. and steam-distilled gave II, b. 170.0-70.5°, m. -10°. The perbromide of pyridine hydrobromide treated by the method of Englert and McElvain (CA 23, 1901) gave, along with 3-bromo- and 3,5-dibromopyridine, a mixture of tribromopyridines from which 2,3,5-tribromopyridine, b. 160°, m. 45.0-5.5°, was isolated. VII (15 g.) refluxed 8 hrs. with MeOK (from 10 g. K) in 100 ml. MeOH, the solution filtered, acidified, and steam-distilled, the residue made alk. and steam distilled, the product extracted with ether, and HBr added gave 74% IV hydrobromide, m. 178.5-9.5°, from which IV, m. 33.5-4.0°, was liberated by addition of NaOH. V, b5 111°, m. 8.2-8.8°, was prepared similarly. VII and MeOK heated 5 min. at 140° and steam distilled gave 32% 3,5-dimethoxypyridine, isolated as the picrate; chloroplatinate m. 212-13° (decomposition) (alc. HCl). Chelidamic acid (20 g.) and 25 g. Br in H2O stirred 24 hrs., the product filtered off and decarboxylated 1 hr. at 200-240°, 15 g. PCl5 and 15 g. POCl3 added, the mixture heated 0.5 hr. at 125°, H2O added, and the mixture poured into iced aqueous KOH and steam-distilled gave 15.1 g. VIII, m. 98.0-8.5° (alc.). The latter (10 g.) added to MeOK (from 10 g. K) in 100 ml. MeOH and diluted with H2O gave 40% ether, m. 85-6° (alc.). Picolinic acid (20 g.) in 50 g. absolute EtOH and 50 g. H2SO4 refluxed 4 hrs., poured on ice, made alk. with NH3, and extracted with Et2O gave 20% Et picolinate, b47 153-4°. Et nicotinate, b21 116°, m. 9.6-10.0°, and Et isonicotinate, b21 111.5-12.0°, m. 7.0-7.5°, were similarly prepared in 80 and 40% yield, resp. Nitration of 4-hydroxypyridine (Koenigs and Freter, CA 19, 71) gave 15% 4-hydroxy-3,5-dinitropyridine, m. 315°, and no mononitro derivative The nitrate of III (2.5 g.), 10 g. fuming HNO3, and 10 g. fuming H2SO4 (containing 20% SO3) heated 24 hrs. on a steam bath gave 34% IX, m. 76.0-6.5°. X, m. 48.0-8.4°, was prepared similarly in 41% yield. The experimental process involved the reaction of 3,5-Dibromo-4-methoxypyridine(cas: 25813-24-5).Product Details of 25813-24-5
3,5-Dibromo-4-methoxypyridine(cas:25813-24-5) belongs to pyridine-derivatives. Several pyridine derivatives play important roles in biological systems. While its biosynthesis is not fully understood, nicotinic acid (vitamin B3) occurs in some bacteria, fungi, and mammals.Product Details of 25813-24-5