N-Vinylpyridine

N-Vinylpyridine N-Vinylpyrrolidone Vinylsulfonic acid Figure 12-1. N-Vinylpyridine, N-vinylpyrrolidone, vinylsulfonic acid. 

Nitrite salts inhibit the sometimes explosive spontaneous polymerisation of N-vinylpyridine derivatives . 

Heavy-duty (HD) additives keep solid combustion and oxidation products in suspension, thus avoiding deposits on metal surfaces, sludge formation and corrosive wear by neutralizing acidic decomposition products. Detergents, some of them RR-based, have sulfonate, hydroxy and/or carboxyl groups and usually contain metal ions or amine functions. More modem HD additives are based on methacrylates of fatty alcohols (Cn-ig), copolymerized with diethylaminoethyl methacrylate (9 1), vinylpyrollidone, N-vinylpyridine and hy-droxyethyl methacrylate. These ash-free dispersants may act also as VI improvers. Extreme-pressure (EP) additives ... 

Strauss and Williamst have studied coil dimensions of derivatives of poly(4-vinylpyridine) by light-scattering and viscosity measurements. The derivatives studied were poly(pyridinium) ions quaternized y% with n-dodecyl groups and (1 - y)% with ethyl groups. Experimental coil dimensions extrapolated to 0 conditions and expressed relative to the length of a freely rotating repeat unit are presented here for the molecules in two different environments ... 

Poly(4-vinylpyridine) [25232-41-1] M (105.1)n. Purified by repeated pptn from solns in EtOH and dioxane, and then EtOH and ethyl acetate. Finally, freeze-dried from rcrt-butanol. 

Reaction of 9-bromo-2-morphohno-4//-pyrido[l, 2-n]pyrimidin-4-ones with 4-vinylpyridine in DMF at 80 °C for 16 h in the presence of CS2CO3 and PdCbCdppf), and with amines and phenols in boiling THF for 20 h in the presence of KOr-Bu and PdCbCdppf) yielded 9-[2-(4-pyridyl)vinyl), 9-(substituted amino), and 9-aryloxy derivatives, respectively (01MIP9). 4-Hydroxyaniline gave a 9-(4-hydroxyphenyl)amino derivative. 

The polymers were prepared using MAA as functional monomer and EDMA as crosslinking monomer if not otherwise noted. VPY= 2- or 4-vinylpyridine TRIM = trimethylolpropane trimethacrylate DPGE = (R)-N,0-dimethacryloylphenylglycinol PYAA = 3-(4-pyridinyl)acrylic acid. 

In contrast to /3-PCPY, ICPY did not initiate copolymerization of MMA with styrene [39] and AN with styrene [40]. However, it accelerated radical polymerization by increasing the rate of initiation in the former case and decreasing the rate of termination in the latter case. The studies on photocopolymerization of MMA with styrene in the presence of ICPY has also been reported [41], /8-PCPY also initiated radical copolymerization of 4-vinylpyridine with methyl methacrylate [42]. However, the ylide retarded the polymerization of N-vinylpyrrolidone, initiated by AIBN at 60°C in benzene [44]. (See also Table 2.)... 

The pioneering work on amphiphilic polyelectrolytes goes back to 1951, when Strauss et al. [25] first synthesized amphiphilic polycations by quaternization of poly(2-vinylpyridine) with n-dodecyl bromide. They revealed that the long alkyl side chains attached to partially quaternized poly(vinylpyridine)s tended to aggregate in aqueous solution so that the polymers assumed a compact conformation when the mole fraction of the hydrophobic side chains exceeded a certain critical value. Thus, Strauss et al. became the first to show experimentally the intramolecular micellation of amphiphilic polymers and the existence of a critical content of hydrophobic residues which may be compared to the critical micelle concentration of ordinary surfactants. They called such amphiphilic polyelectrolytes polysoaps [25],... 

Recently, the quaternized poly-4-vinylpyridine, 50-54 (QPVP) was found to be an electron acceptor in the charge-transfer interactions 104 Ishiwatari et al.105) studied alkaline hydrolyses of p-nitrophenyl-3-indoleacetate 58 (p-NPIA) and N-(indole-3-acryloyl) imidazole 59 (IAI) (electron donor) in the presence of QPVP. The fcobs vs. polyelectrolyte concentration plots are shown in Fig. 12. As is seen in... 

The results of osmotic pressure measurements are shown in Fig. 145 for poly-(4-vinyl-N-butylpyridinium bromide) in alcohol, and for the parent uncharged polymer, poly-(4-vinylpyridine), likewise in alcohol. The value of /c for the former (note difference in scales) is much larger than for the latter, and it increases with dilution. The... 

Fig. 145.—Osmotic pressure-concentration ratios ( in g./cm and c in g./lOO ml.) for poly-(4-vinylpyridine) in alcohol, O, coordinates left and below poly-(N-butyl-4-vinylpyridinium bromide) in alcohol, coordinates right and above and the same polymer in alcoholic 0.61 N lithium bromide, 3 coordinates left and below. °> ...

If 0.6 N lithium bromide is added to the solution of the polyelectrolyte and also to the solvent on the opposite side of the osmometer membrane, the lowermost set of points in Fig. 145 (lower and left scales) is observed. The anion concentration inside and outside the coil is now so similar that there is little tendency for the bromide ions belonging to the polymer to migrate outside the coil. Hence the osmotic pressure behaves normally in the sense that each poly electrolyte molecule contributes essentially only one osmotic unit. The izjc intercept is lower than that for the parent poly-(vinylpyridine) owing to the increase in molecular weight through addition of a molecule of butyl bromide to each unit. 

Combining the nucleophilicity of the indole 3-position just illustrated and the well-known tendency of C-2 and C-4 vinyl pyridines to add nucleophiles, a convenient synthesis of the tranquilizer benzindopyrine (19) was devised.6 Reaction of N-benzylindole (17) with 4-vinylpyridine (18) in acetic acid produced 19 directly. 

Tricyclic antihistamines as a rule carry aliphatic nitrogen as a substituent on a side chain attached to the central ring the side chain nitrogen may be part of a heteroaromatic ring. Conjugate addition of p-chloroaniline (49) to the substituted vinylpyridine 50 gives the alkylated aniline 51. Treatment of that intermediate with nitrous acid leads to N-nitroso intermediate 52 which is then reduced to the hydrazine (53). Reaction of 53 with N-methyl-4-piperidone... 

If the more activated alkene 2-vinylpyridine is used in place of styrene with the same catalysts and the same range of substrates, anti-Markovnikoff hydroamination is also found. Thus, N-[2-(2 -pyridyl)ethyl]piperidine was isolated in 53% yield from reaction of 2-vinylpyridine with piperidine in the presence of [Rh(COD)2]+/2PPh3 under reflux. N H addition was observed with other amines, the remaining product in all cases being primarily that from oxidative amination (Table 12). When the catalytic reaction was run in the absence of phosphine, the yield of hydroamination product increased dramatically.171... 

Copolymers of styrene with 4-vinylpyridine (II) and N-viny1imizado1e (III) were obtained by copolymerization for one day at 60°C in 25 wt% comonomer solutions in toluene, using AIBN as initiator. In all cases the degrees of substitution, a, of the functionalized polymers with ligand groups were derived from the nitrogen contents found by elemental analyses. 

Ernst H, Rittinghausen S, Bartsch W, Creutzenberg O, Dasenbrock C, Gorlitz BD, Hecht M, Kairies U, Muhle H, Muller M, Heinrich U, Pott F (2002) Pulmonary inflammation in rats after intratracheal instillation of quartz, amorphousSiO(2),carbon black, and coal dust and the influence of poly-2-vinylpyridine-N-oxide (PVNO). Experimental and Toxicologic Pathology 54 109-126. 

PVP-Os Osmium-bipyridyl-modified quaternized poly 4-vinylpyridine) [102,206,207] PAH-Fc Ferrocene-modified polyallylamine [77, 101, 208] P(CM-FcJ Poly(vynil ferrocene) copolymer [224] PVn Polyalkylviologens (PVn, n number of methylene groups) [67, 104,... 

H. B. Friedrich, N. Singh, A Study of Poly (4-vinylpyridine)-Supported Ruthenate in the Oxidation of Alcohols, Catal. Lett. 110 (2006) 61—70. 

The total yield of 2-vinylpyridine formed from 2-methylpyridine can be as high as 90%. 2-Vinylpyridine may also be obtained in almost quantitative yields by heating 2-alkylaminopyridine derivatives (which are directly available by cobalt catalysis) with a supported (e.g., AI2O3) alkali metal hydroxide [Eq.(8) R = R = alkyl, cyloalkyl, etc., RR N = heterocycle] (76SZP14399 78MI1). 

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