Phenyl pyrrolidone

Wahrend 4-Hydroximino-4-pyridyl-(2)-butansaure-athylester liber Palladium/Ba-riumsulfat zum 5-Pyridyl-(2)-pyrrolidon-(2) hydriert wird2, bleibt die Hydroximino-Gruppe bei der RingschluBhydrierung des 2-Hydroximino-3-phenyl-3-cyan-propansau-re-athylesters zum 3-Hydroximino-4-phenyl-pyrrolidon-(2) liber Platin(IV)-oxid in Eis-essig selektiv erhalten3. 

This study involved the preparation and characterization of poly(N-phenyl 3,4-dimethylenepyrrolidine) and the subsequent oxidation and reduction of this polymer. The parent polymer was not very soluble, so it was difficult to characterize. However, after oxidizing in the presence of palladium on carbon in nitrobenzene, the resultant poly(N-phenyl 3,4-dimethylenepyrrole) was soluble in several organic solvents. Attempts to reduce the original polymer to the pyrrolidone were unsuccessful. 

For the addition of ethylene, EtOAc as solvent was particularly advantageous and gave 418 in 60% yield (Scheme 6.86). The monosubstituted ethylenes 1-hexene, vinylcyclohexane, allyltrimethylsilane, allyl alcohol, ethyl vinyl ether, vinyl acetate and N-vinyl-2-pyrrolidone furnished [2 + 2]-cycloadducts of the type 419 in yields of 54—100%. Mixtures of [2 + 2]-cycloadducts of the types 419 and 420 were formed with vinylcyclopropane, styrene and derivatives substituted at the phenyl group, acrylonitrile, methyl acrylate and phenyl vinyl thioether (yields of 56-76%), in which the diastereomers 419 predominated up to a ratio of 2.5 1 except in the case of the styrenes, where this ratio was 1 1. The Hammett p value for the addition of the styrenes to 417 turned out to be -0.54, suggesting that there is little charge separation in the transition state [155]. In the case of 6, the p value was determined as +0.79 (see Section 6.3.1) and indicates a slight polarization in the opposite direction. This astounding variety of substrates for 417 is contrasted by only a few monosubstituted ethylenes whose addition products with 417 could not be observed or were formed in only small amounts phenyl vinyl ether, vinyl bromide, (perfluorobutyl)-ethylene, phenyl vinyl sulfoxide and sulfone, methyl vinyl ketone and the vinylpyri-dines. 

The nature of alkyl halide and the environment of the phosphorus atom make a substantial contribution to the direction of the reaction. Thus, cyclic phosphites [108], like trialkyl phosphites [110], react with preservation of the coordination of the P(III) phosphorus atom (126-132 ppm). If the alkoxyl group is substituted by amide, alkyl, or aryl, the nucleophilicity of the phosphorus atom in the corresponding amidophosphite (phosphonite) increases in comparison with the trialkyl phosphite. This probably promotes attack by 1 -haloalkyl-2-pyrrolidone at the phosphorus atom and not the oxygen, and this was confirmed experimentally. As a result of the investigated reactions amidophosphonates or ethyl phenyl phosphinates llOa-c were isolated compounds with P(III) were not detected in these cases. 

When we attempted the analogous reaction with Ar-vinyl-2-pyrrolidones as the olefin components under similar conditions, we obtained surprisingly l-[4-methoxy-4-phenyl-3-oxo-l-butenyl]-2-pyrrolidones instead of the expected cyclopropane derivatives (82) ... 

How can one explain the origin of these products in which one finds, aside from the former carbene ligand and the pyrrolidone, just an additional carbonyl group It seems plausible that the carbene ligand first of all reacts with carbon monoxide to form methoxy (phenyl) ketene. This, in turn, forms with the polarized olefin a cyclobutanone derivative which by ring opening goes over to the observed product (Fig. 6). 

Fig. 6. Hypothesis concerning the course of the reaction during the treatment of pentacarbonyl[methoxy(phenyl)carbene]chromium(0) with JV-vinyl-2-pyrrolidones under a CO pressure of 150 atm.

Poly(methyl acetoxy silylene) [poly(MASi)] is also claimed [130] to initiate the polymerization of cyclohexyl methacrylate upon UV irradiation and to crosslink the resulting polymer by air exposure. Finally, the pyridinium salt of partially chloromethylated poly(methyl phenyl silylene) (Q-PMPSi) is reported [131] to initiate the polymerization, in aqueous solution, of hydrophilic vinyl monomers such as methacrylic acid, acrylamide, 2-hydroxyethyl methacrylate and 1 -vinyl-2-pyrrolidone. 

Kitano S, Koyama Y, Kataoka K, Okano T, and Sakurai Y. A novel drug delivery system utilizing a glucose responsive polymer complex between poly(vinyl alcohol) and poly(N-vinyl-2-pyrrolidone) with a phenyl boronic acid moiety. Journal of Controlled Release 1992 19 162-170. 

Epoxy resins have been cured using a tris(ethyl acetoacetato) aluminium complex and tris (4-chloro-phenyl) (a-nitrobenzoy-loxy) silane.Resins produced by this catalyst mixture were found to have desirable electrical characteristics. N-vinyl-2-pyrrolidone is claimed to be a much superior resin than several acrylate diluents for photocured coatings... 

Wahrend in der Reihe der N-(2-Oxo-alkyl)-lactame sich die (2-Oxo-2-phenyl-athyl)-2-pyrrolidone noch mit Raney-Nickel aminieren lassen, werden die entsprechenden Ver-bindungen des 2-Piperidons, des s-Caprolactams und des 3-Oxo-morpholins unter glei-chen Bedingungen nur zu den entsprechenden Alkoholen reduziert12. 

The same Cr-carbene complex reacts with l-vinyl-2-pyrrolidone to give the metathesis product a-methoxystyrene and with 1-phenyl-1-piperidinoethylene to give both the cyclopropane derivative and a new carbene (the inorganic metathesis product) ... 

Studies in solution suggest specific association of chloroform with the benzo [b] thiophene molecule and interaction of acetone with the sulfur atom.67 Complexation constants of benzo [b]thiophene with polar solvents (e.g., DMF, 2-pyrrolidone) have been determined by an NMR method.77 In the complex of benzo [b] thiophene with Ag+, the metal ion is strongly associated with the lone pair of electrons on the sulfur atom78 in the 1,3,5-trinitrobenzene complex, NMR data suggest that the trinitro compound lies over the phenyl ring of the heterocycle.78,79 Likewise, in the chromium tricarbonyl complex, the Cr(CO)3 group is bonded to the benzenoid ring.80 Studies of the structure of benzo[b]thiophenium salts will be discussed in Section III,A,2. 

An interesting subsequent reaction has been observed for a series of 1,1 -dial ky 1- 3 - but e ny 1 phenyl ketones the resulting unsaturated carboxamides cyclize to pyrrolidone derivatives ... 

MMTS MsOH NBS NHMDS NMP NMR PPb Ph Pr PTC rt TBDMS Tf THF THP TLC TMEDA TMS TMSOTf Tol TOMAC Ts TsOH UDP methyl methylthiomethyl sulfoxide (=FAMSO) methanesulfonic acid N-bromosuccinimide sodium hexamethyldisililazide /V-methyl-2-pyrrolidone nuclear magnetic resonance parts per billion phenyl propyl Phase transfer catalysis room temperature t-butyldimethylsilyl triflatc (trifluoromethanesulfonate) tetrahydrofuran 2-tetrahydro-2//-pyran-2-yl thin-layer chromatography /V./V./V /V -tetramethylethylenediamine trimethylsilyl trimethylsilyl triflate p-tolyl trioctylmethylammonium chloride tosyl p-toluenesulfonic acid ultrasonically dispersed potassium... 

Allene recycled 24 hrs. at room temp, through a soln. of C-benzoyl-N-phenyl-methylenimine oxide in acetone 5-benzoyl-l-phenyl-3-pyrrolidone. Y 85%. F. e. under less mild conditions s. M. C. Aversa, G. Cum, and N. Uccella, Chem. Commun. 1971, 156. 

Figure 3.17 Poly(N-vinyl pyrrolidone] (PVP] and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM] structures.

MPSN. See Methyl phenyl sulfone MPT. See Methyl p-toluate MPTD. See Dimethyl diphenyl thiuram disulfide MPV. See Bis (4-vinylthiophenyl) sulfide M-Pyrol . See N-Methyl-2-pyrrolidone M-Qua1 40. See Polyquaternium-6 M-Quat 522. See Isostearamidopropyl ethyidimonium ethosulfate M-Quat 1033. See Soyethyidimonium ethosulfate... 

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