2-Pyrrolidones acid esters

Narayanan, K.S., M. Singh, and R.K. Chaudhuri (1993). The reduction of herbicide leaching using vinyl pyrrolidone copolymers and methyl vinyl ether maleic acid ester copolymers. In P.D. Berger, B.N. Devisetty, and F.R. Hall, eds., Pesticide Formulations and Application Systems, Vol. 13. Philadelphia, PA American Society for Testing and Materials, pp. 57-75. 

Hydroxypropyl cellulose (HPC) Hydroxyethylcellulose (HEC) Methylcellulose (MC) Polvinyl alcohol (PVA) Polyacrylic acid (PAA) Poly (meth) acrylic acid ester (PMAA) Polyvinyl pyrrolidone (PVP) Polyethylene glycols (PEG) White wax... 

These stringent requirements are demonstrated by few chemicals other than water. It remains to be seen to what extent the limitations can be relaxed for a chemical promoter to be acceptable (to patients and to the regulatory authorities). Enhancers include a wide range of chemical entities that increase skin permeability (Figure 8.9), such as sulphoxides, alcohols, polyols, pyrrolidones, alkanes, fatty acids, esters, amines and amides, terpenes, surfactants, cyclodextrins, water, etc. 

Matsumura and his coworkers [38] have employed the 2-pyrrolidone anion, in DMF solution, to deprotonate arylacetic acid esters with subsequent oxidative dimerization of the corresponding carbanions. This study includes a useful comparison between the electrochemical and chemical generation of the 2-pyrrolidone anion (by fluoride anion displacement in A-trimethylsilyl-2-pyrrolidone). The advantage lies with the electrochemical route, which gave yields of final product of 80%, compared with the 30% obtained with the chemically generated base (Scheme 10). The overall process, formation of dimethyl 2,3-diphenylsuccinates, is not only efficient and convenient but also operates with high diastereoselectivity when under the control of an oxazolidinone chiral auxiliary (Scheme 10). 

A serious limitation of this powerful analytical technique is the inability to detect and quantify Gin and Asn m an amino acid mixture In the acid-catalyzed esterification reaction, the amides (Gin and Asn) are rapidly deaminated and converted to the same derivatives as those formed by Glu and Asp, respectively. Consequently, summations of both Glu and Gin concentrations and Asp and Asn concentrations are determined by this method. It has been shown that when Gin is heated to a temperature of about 100°C in an acidified alcoholic medium, rapid conversion to glutamic acid diester takes place. Pyrrolidone carboxylic acid ester has been shown by mass spectrometry to be a cyclized intermediate (Fig 2). This intermediate reaches its maximum concentrahon after heating at 100°C for 5-10 mm (Collins and Summer, 1978). 

Fig 2 Formation of Glu derivative from Gin via pyrrolidone carboxylic acid ester intermediate... 

Sucroglycerides Sucrose fatty acid esters solvent, commercial cleaners Methoxydiglycol Phenoxyethanol solvent, commercial cleaning Lauryl pyrrolidone... 

A soln. of startg. Rh(I) complex in methylene chloride treated with 3 eqs. ethereal HCl, left 1 h at —78°, 10 eqs. trimethyl phosphite added, warmed to 25° for 12 h, and treated with excess methanol and a further 5 eqs. trimethyl phosphite at 25° for 24 h 1-butyl-3-methyl-2-pyrrolidone. Y 86%. F.e. inch 2-piperidones, also f rr-amino-carboxylic acid esters from ethylene-r r/-amine-rhodium(I) complexes, s. M.E. Krafft et al., Tetrahedron Letters 29, 6421-4 (1988) 5y -selectivity with trisubsl. olefinic amine complexes s. ibid. 30, 539-42 (1989). 

Pyrrolidones from y-bromocarboxylic acid esters—Optically active compounds s. 19, 952... 

Reaction of oxalic acid esters with 2-pyrrolidones s. 16, 801... 

Styrene injected under anhydrous conditions from a syringe through a neoprene septum into a soln. of K-terf-butoxide in N-methyl-2-pyrrolidone, and the product isolated after 24 hrs. at room temp. N-methyl-3-phenethyl-2-pyrrolidone. Conversion ca. 100%. F. e., also in solvents, s. H. Pines, S. V. Kannan, and J. Simonik, J. Org. Chem. 36, 2311 (1971) Mikael addition with Li-diisopropyl-amide, a-alkylthiocarboxylic acid esters s. R. J. Cregge, J. L. Herrmann, and R. H. Sdilessinger, Tetrah. Let. 1973, 2603. 

Copolymers of vinyl pyrrolidone, crotonate, vinyl neodecanoic acid Copolymers of vinyl pyrrolidone and acrylic acid ester... 

Copolymers of vinyl pyrrolidone and acrylic acid ester... 

Hydroxy- from keto-carboxylic acid esters s. 72, 64 s. a. S. Dalby, G. W. Kenner, and R. C. Sheppard, Soc. 1960, 968 a-Hydroxy- from a-keto-carboxylic acid amides s. 13, 63 3-Hydroxy-2-pyrrolidones from 2,3-pyrrolidiones s. 13,64 Glyeitol — from carbohydrate phosphates G... 

Cltroflex citric acid esters provide a wide range of benefits when used as plasticizers with aqueous- and solvent-based polymers, including acrylic, methacrylic, ethyl cellulose, hydroxypropyl methyl cellulose, nitrocellulose, vinyl acetate, vinyl chloride, vinyl pyrrolidone, vinylidene chloride, axiA urethane polymer systems. 

The combination of ethanol/water/DME and N-methyl-2-pyrrolidone (NMP) was found to interact sufficiently strongly with microwave and generates the heat required to promote the Stille cross-couplings. Methyl acrylate was converted smoothly to the corresponding cinnamic acid esters in 3.8 min at 60 W in the presence of DMF (Patel et al., 1977). 

A/ -Methoxycarbonyl-2-pyrroline undergoes Vilsmeier formylation and Friedel-Crafts acylation in the 3-position (82TL1201). In an attempt to prepare a chloropyrroline by chlorination of 2-pyrrolidone, the product (234) was obtained in 62% yield (8UOC4076). At pH 7, two molecules of 2,3-dihydropyrrole add together to give (235), thus exemplifying the dual characteristics of 2,3-dihydropyrroles as imines and enamines. The ability of pyrrolines to react with nucleophiles is central to their biosynthetic role. For example, addition of acetoacetic acid (possibly as its coenzyme A ester) to pyrroline is a key step in the biosynthesis of the alkaloid hygrine (236). 

The 4-azidobutyrate ester is introduced via the acid chloride. Gleavage occurs by pyrrolidone formation after the azide is reduced by hydrogenation, H2S or Ph3P. ... 

The treatment of esters of aromatic acids with l-alkyl-2-pyrrolidones and l-alkyl-2-piperidones is an extremely useful method for the preparation of simple pyrrolines and piperideines, respectively. The l-alkyl-3-aroyl-2-... 

However, morpholine-4-carboxylic acid 2-hydroxy-1-methyl-ethyl ester is formed by the reaction of PC and the substrate morpholine in an undesired side reaction. By use of 1.4-dioxane or the pyrrolidones as mediator s3 about 30 to 45% of the morphoUne is consumed by this side reaction. The by-product is contained in the PC phase and can not be extracted to the non-polar product phase. The selectivity to the desired amines is lowered, because of the consiunption of the morphoUne. Thus, PC has to be substituted by another polar solvent (e.g. water, methanol or ethylene glycol) in future experiments. The lactates react with the morphoUne, too resulting in the corresponding amide. Overall, the hydroaminomethylation in the TMS systems PC/dodecane/lactate results in a conversion of 1-octene of about 80%, but in selectivities to the amines of only 50 to 60%. 

Nicotine Nicotine, l-methyl-2-(3-piridyl)pirrolidine (13.1.27), is an alkaloid that is isolated from the plant Nicotiana (Nicotiana tabacum, Nicotiam rustica, and others) and can be synthesized in varions ways [33-36]. In particular, it is proposed to proceed from nicotinic acid ethyl ester, which is condensed with iV-methylpyrrolidone, giving l-methyl-2-nicotinoyl pyrrolidone-2 (13.1.23). Acidic hydrolysis of this compound leads to an opening of the pyrrolidine ring giving the intermediate (13.1.24), which under the reaction conditions is decarboxylated to the /-aminoketone (13.1.25). The carbonyl group is reduced to an alcohol and the resnlting prodnct (13.1.26) undergoes dehydration to nicotine (13.1.27). 

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