N-alkyl-pyrrolidones

Tertiary phosphine oxides, alkylmethyl sulphoxides, and alkylhydroxyethyl sulphoxides produced in the same way from trialkyl phosphines and thioethers, as well as N-alkyl-pyrrolidones (III) [51] and some long-chain imidazoline derivatives (IV) [52] should be... 

Aryl and alkyl nitriles (7), in the presence of levulinic acid, hydrogen and a catalyst can be converted to N-alkyl pyrrolidones (Figure 2). Preferred catalysts for this reduction include Ir/Si02, Ru/AbOa and Pd/C. Excellent results are obtained with low cost nitriles such as 2-and 3-pentenenitrile which are intermediates or byproducts in the production of nylon intermediates (Invista) and should be available at very low cost. Aryl nitriles such as benzonitrile can also be used to prepare N-benzyl and N-cyclohexylmethyl pyrrolidones. 

Intercalates form readily between the n-alkyl pyrrolidones and yield interesting effects as a function of alkyl length and ratio of pyrrolidone to surface cation [6]. When utilizing n-dodecyl pyrrohdone (DDP) as a surface treatment, it was found that when DDP was mixed with the clay in a 1 1 ratio to the exchangeable cation, there was an interdigitated intercalate with a r/-spacing of 2.1 nm, which is quite similar to that observed for traditional quaternary amine treated clays. 

N-alkyl pyrrolidones are a class of amide surfactants made by reacting a primary amine with butyrolactone to give a amide alcohol, then cyclizing to the pyrrolidone (Fig. 17) [21]. 

Dirhodium(ll) tetrakis[methyl 2-pyrrolidone-5(R)-oarboxylate], Rh2(5R-MEPV)4, and its enantiomer, Rh2(5S-MEPY)4, which is prepared by the same procedure, are highly enantioselective catalysts for intramolecular cyclopropanation of allylic diazoacetates (65->94% ee) and homoallylic diazoacetates (71-90% ee),7 8 intermolecular carbon-hydrogen insertion reactions of 2-alkoxyethyl diazoacetates (57-91% ee)9 and N-alkyl-N-(tert-butyl)diazoacetamides (58-73% ee),10 Intermolecular cyclopropenation ot alkynes with ethyl diazoacetate (54-69% ee) or menthyl diazoacetates (77-98% diastereomeric excess, de),11 and intermolecular cyclopropanation of alkenes with menthyl diazoacetate (60-91% de for the cis isomer, 47-65% de for the trans isomer).12 Their use in <1.0 mol % in dichloromethane solvent effects complete reaction of the diazo ester and provides the carbenoid product in 43-88% yield. The same general method used for the preparation of Rh2(5R-MEPY)4 was employed for the synthesis of their isopropyl7 and neopentyl9 ester analogs. 

Consequently, as part of this study, we elected to combine the viscosifying effect of hydrophobic associations with the thermal stability of NVP and the high molecular weight capability of acrylamide. Sepcifically, we synthesized terpolymers of acrylamide, N-alkyl acrylamide, and N-vinyl pyrrolidone (NVP-RAM) and tetrapolymers of acrylamide, N-alkylacrylamide, sodium acrylate, and N-vinyl pyrrolidone... 

Manzer LE (2005) Production of 5-methyl-N-(methylaryl)-2-pyrrolidone, 5-methyl-N-(methylcycloalkyl)-2-pyrrolidone and 5-methyl-N-alkyl-2-pyrrolidone by reductive animation of levulinic acid with cyano compounds. WO 2,004,085,048 A3... 

The N-alkylallylamines which are readily accessible from allyl chloride and primary amines or from allylamine and alkyl chlorides [684] react to form N-alkyl-2-pyrrolidones. 

Carbonylation of N-alkylated p-methylallylamines yields l-alkyl-4-me-thyl-2-pyrrolidones. 

Some specific recent applications of the GC-MS technique to various types of polymers include the following PE [49,50], poly(l-octene) [51], poly(l-decene) [51], poly(l-dodecene) [51], 1-octene-l-decene-l-dodecene terpolymer [51], chlorinated polyethylene [52], polyolefins [53, 54], acrylic acid methacrylic acid copolymers [55], polyacrylates [56], styrene-butadiene and other rubbers [57-59], nitrile rubber [60], natural rubbers [61, 62], chlorinated natural rubber [63, 64], polychloroprene [65], PVC [66-68], silicones [69, 70], polycarbonates [71], styrene-isoprene copolymers [72], substituted PS [73], polypropylene carbonate [74], ethylene-vinyl acetate copolymers [75], Nylon [76], polyisopropenyl cyclohexane a-methyl styrene copolymers [77], m-cresol-novolac epoxy resins [78], polymeric flame retardants [79], poly(4-N-alkyl styrenes) [80], polyvinyl pyrrolidone [81], vinyl pyrrolidone-methyl acryloxysilicone copolymers [82], polybutylcyanoacrylate [83], polysulfide copolymers [84], poly(diethyl-2-methacryloxy)ethyl phosphate [85], ethane-carbon monoxide copolymers [86], polyetherimide [87], bisphenol A [88], ethyl styrene [89], styrene-isoprene block copolymer [89], polyvinyl alcohol-co-vinyl acetate [90], epoxide thiol [91], maleic acid-propylene copolymer [92], P-hydroxy butyrate-P-hydroxy valerate copolymer [93], polycaprolactams [39,94], PS [95,96], polypyrrole [95,96], polyhydroxy alkanoates [97], poly(p-chloromethyl) styrene [81], polybenzooxazines and siloxy substituted polyoxadisila-pentanylenes [98,99] poly benzyl methacrylates [100], polyolefin blends after ageing in soil [101] and polystyrene peroxide [43]. 

Ethyl 2,2-difluoro-4-iodo-4-(trimethylsilyl)butanolate reacts with primary amines to afford the products of intramolecular cycliza-tion, N-alkyl-3,3-difluoro-5-trimethylsilyl-2-pyrrolidones 210—217 as (Scheme 24.24) (146). 

Scheme 24.24 Synthesis of N-alkyl-3,3-difluoro-5-tritnethylsilyl-2-pyrrolidones.

The importance of ring size holds also for tautomerism of -pyrrol-5-ones and. d -dihydro-6-pyridones. While the former compounds behave as cyclic 1-methyl-2-alkyl-2-hydroxy-5-pyrrolidones 179) (76) [or, on distillation, as the dehydrated l-methyl-2-alkyl-J -pyrrolones (77)], the latter compounds exist as acyclic N-methylamides of 8-oxo-acids (78) [as shown by infrared spectroscopy (/80)j. The dehydration of 78 during distillation to form l-methyl-2-alkyl-. -dihydro-6-pyridones (79) is achieved only with difficulty. 

Alkyl halides can be hydrolyzed to alcohols. Hydroxide ion is usually required, except that especially active substrates such as allylic or benzylic types can be hydrolyzed by water. Ordinary halides can also be hydrolyzed by water,442 if the solvent is HMPA or N-methyl-2-pyrrolidone.443 In contrast to most nucleophilic substitutions at saturated carbons, this reaction can be performed on tertiary substrates without significant interference from elimination side reactions. The reaction is not frequently used for synthetic purposes, because alkyl halides are usually obtained from alcohols. 

The apparently simple procedures of partial dehydrogenation of pyrrolidines and partial hydrogenation of pyrroles afford Zl1-pyr-rolines. However, the reaction is complex and is of little preparative value.97-98 A 1-Pyrrolines may be obtained by isomerization of A 3-pyrrolines.100 From the preparative point of view, partial hydrogenation of quaternary pyridine salts in strongly alkaline media to give 1-alkyl-id 2-piperideines is more important.101 Formation of heterocyclic enamines was observed in the reduction of i -methyl-pyrrolidone with lithium aluminum hydride,102 -alkylpiperidones with sodium in ethanol,103,104 and in the electrolytic reduction of N-methylglutarimide.106... 

The solubility of rare earth hydrides in organic solvents is increased by appropriate additives, too. For this purpose the hydrides are reacted with electron-donor ligands such as alkyl benzoates, alkyl propionates, alkyl tolu-ates, dialkylethers, cyclic ethers, alkylated amines, N,N -dimclhylacelamide, AT-methyl-2-pyrrolidone, trialkyl and triaryl phosphines, trialkyl phosphates and triaryl phosphates, trialkyl phosphates, hexamethylphosphoric triamide, dimethyl sulfoxide, etc. Prior to use as a polymerization catalyst the prereacted mixture of the rare earth hydride plus the additive is prereacted with Al-alkyl-based Lewis acids in the temperature range of 60-100 °C for 10 min to 24 h [351,352]. 

Treatment of esters of aromatic acids with l-alkyl-2-pyrrolidones and l-methyl-2-piperidones is an useful method for the preparation of simple pyrrolines and piperidines, respectively. The l-alkyl-3-aroyl-2-pyrrolidones (110, n = 1) and l-alkyl-3-aroyl-2-piperidones (110, n = 2) thus formed are cleaved by the action of concentrated hydrochloric acid to give l-methyl-2-aryl-2-pyrrolines453 (111, n = 1) and l-alkyl-2-aryl-2-piperidines454 (111, n = 2), respectively. After blocking the secondary nitrogen atom in a lactam by means of acylation, one can prepare 2-aryl-1-pyrrolines (112, n = 1) and 2-aryl-1 -piperidines4 55-457 (112, n = 2). 

Further examples for electron acceptor monomers are acrylonitrile [37], diethyl fumarate [39], fumaronitrile [29,30, 38], maleonitrile [38], N-carbethoxymaleimide [29], N,N-diethylaminoethyl methacrylate [39], nitroethylene [10] and iV-ethyl-maleimide [40], As electron donor monomem also are used vinyl alkyl ethers [38, 40], alkyl methacrylate [40], JV-vinyl pyrrolidone [40] and cyclohexene oxide [10]. 

In method (a), an alkyl halide (or tosylate) reacts with [Fe(CO)4] " in N-melhyl-2-pyrrolidone to give an anionic iron alkyl (1), some of which have been isolated and characterized. Further reaction with another alkyl halide gives a complex tentatively formulated as (2), which may decompose to the ketone via the complex (3) formed by solvent-assisted migratory insertion. No alkyl coupling products are detected. 

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