2- Pyrrolidones anhydrides

In a more recent study using dedicated multimode microwave reactors for chemical synthesis, which enable temperature and power control, it was demonstrated that microwave irradiation could be effectively employed to couple aromatic carboxylic acids to polystyrene Wang resin [25], if the symmetrical anhydride procedure was used, and not the three-component O-acylisourea activation method [19]. Almost quantitative loading was achieved in l-methyl-2-pyrrolidone (NMP) at 200 °C within 10 min under... 

Pyrrolidone is a lactone used for the production of nylon-4. This reactant may be produced by the reduction ammoniation of maleic anhydride. s-Caprolactam, used in the production of nylon-6, may be produced by the Beckman rearrangement of cyclohexanone oxime (structure 17.11). The oxime may be produced by the catalytic hydrogenation of nitrobenzene, the photolytic nitrosylation of cyclohexane (structure 17.9), or the reaction of cyclohexanone and hydroxylamine (structure 17.10). Nearly one-half of the production of caprolactam is derived from phenol. 

D-Glutamic acid-g-(t-butyl)ester N-carboxy anhydride was previously polymerized by Fujimoto et al. (1) in a l,2-dichloroethane/l,4-dioxane mixture using sodium 4-methyl-2-pyrrolidone as initiator. Additional derivatives were... 

NMO NMP Nu PPA PCC PDC phen Phth PPE PPTS Red-Al SEM Sia2BH TAS TBAF TBDMS TBDMS-C1 TBHP TCE TCNE TES Tf TFA TFAA THF THP TIPBS-C1 TIPS-C1 TMEDA TMS TMS-C1 TMS-CN Tol TosMIC TPP Tr Ts TTFA TTN N-methylmorpholine N-oxide jV-methyl-2-pyrrolidone nucleophile polyphosphoric acid pyridinium chlorochromate pyridinium dichromate 1,10-phenanthroline phthaloyl polyphosphate ester pyridinium p-toluenesulfonate sodium bis(methoxyethoxy)aluminum dihydride (3-trimethylsilylethoxy methyl disiamylborane tris(diethylamino)sulfonium tetra-n-butylammonium fluoride f-butyldimethylsilyl f-butyldimethylsilyl chloride f-butyl hydroperoxide 2,2,2-trichloroethanol tetracyanoethylene triethylsilyl triflyl (trifluoromethanesulfonyl) trifluoroacetic acid trifluoroacetic anhydride tetrahydrofuran tetrahydropyranyl 2,4,6-triisopropylbenzenesulfonyl chloride 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane tetramethylethylenediamine [ 1,2-bis(dimethylamino)ethane] trimethylsilyl trimethylsilyl chloride trimethylsilyl cyanide tolyl tosylmethyl isocyanide meso-tetraphenylporphyrin trityl (triphenylmethyl) tosyl (p-toluenesulfonyl) thallium trifluoroacetate thallium(III) nitrate... 

The tricyclic intermediate 58 was subsequently used to construct the pentacyclic nucleus of lycorine (1) by base-catalyzed Michael addition and aldol condensation. The key intermediate (58) was obtained from 3-pyrrolidone ethylene ketal with one equivalent of 4,5-methylenedioxyphtalic anhydride followed by LiAlH4 reduction,... 

Fig. 11.1 Structures of polysuccinic acid-maleic acid anhydride (A), polyvinyl pyrrolidone (B), and polyethyleneglycol (C).

Aspartic acid Fumaric acid 2-Amino-1,4-butanediol, 3-aminotetrahydrofuran, amino-2-pyrrolidone, aspartic anhydride Werpy and Petersen 2004... 

Soluble carriers include antibodies and soluble synthetic polymers such as poly(hydroxypropyl methacrylate), poly(lysine), poly(aspartic acid), polyvinylpyrrolidone), poly(N-vinyl-2-pyrrolidone-co-vinylamide) and poly (styrene co-maleic acid/anhydride). 

Reaction of succinylhydrazide derived from (A)-amino-2-methoymethylpyrrolidine (SAMP) with benzylmagne-sium chlorides allows us to prepare a number of enantiopure 5-arylmethyl-pyrrolidones and -pyrrolidines.265 An enantioselective desymmetrization of anhydrides was reported by Fu. Arylmagnesium chlorides react in toluene in the presence of 1 equiv. of (—)-sparteine with 3-substituted glutaric anhydrides, giving aryl ketones with 87-92% ee (Scheme 90).266... 

Among the compounds evaluated for their ability to reverse electroconvulsive shock-induced amnesia in mice, perhydropyrrolo[2,l-/j][l, 3]thiazin-4,6-dione (454) was synthesized. A mixture of 5-ethoxy-pyrrolidone (452) and 3-mercaptopropanoic acid was heated at 60 C for 16 hr to give 453, which ring closed to 454 on heating with acetic anhydride in acetic acid (87JMC498). 

The electron richness of vinylferrocene as a monomer has been demonstrated in its copolymerization with maleic anhydride, in which 1 1 copolymers were obtained over a wide range of feed ratios and ri r2 = 0.003 [13]. Subsequent copolymerization of vinylferrocene with classic organic monomers, such as styrene [13], Ai-vinyl-2-pyrrolidone [15], methyl methacrylate [13] and acrylonitrile [13] were carried out and the Alfrey-Price Q and e parameters [16] determined. The value of e is a semiempirical measure of the electron richness of the vinyl group. The best value of e for vinylferrocene is about —2.1, which, when compared with the e values of maleic anhydride (-H 2.25), p-nitrostyrene (-1-0.39), styrene (—0.80), p-Ai,Ai -dimethyl-aminostyrene ( — 1.37) and l,T-dianisylethylene ( — 1.96), again emphasizes the electron rich nature of the vinyl group in vinylferrocene. 

Neutral or negatively charged polymeric resins are commonly employed to provide styling benefits in products such as mousses, gels, hairsprays, and setting lotions. Typical examples in use today are the copolymer of vinyl acetate and cro-tonic acid, the copolymer of polyvinyl pyrrolidone and vinyl acetate (PVP/VA), the ethyl ester of the copolymer of polyvinyl methyl ether and maleic anhydride (PVM/MA), and the copolymer of octylacrylamide/acrylates/butylaminoethyl methacrylate (Amphomer). 

Some commonly used graft monomers are acrylates, such as methacrylic acid (to enhance adhesion), acrylic esters and hydroxy functional acrylates (that can couple with polar materials, as wood). Maleic anhydride and n-vinyl pyrrolidone are also used, but with care taken to avoid potential volatilization during processing. The former is used as an adhesion promoter, the latter to enhance bio-compatibility. Specific properties depend both on the backbone or base material that is being grafted and on the graft monomer (Fig. 1). 

As an alternative to the differential procedure a measured amount of excess amine has been used to determine acid anhydrides, unused amine then being back-titrated. Aniline and nitro- or halogeno-substituted anilines have been used, but only two examples could be found of application to sulphonyl halides Terent ev and coworkers used hexamethy-leneimine in methanol, then back-titrated with HCl/methanol262 and Allan and Sobodacha263 used 3-chloroaniline in l-methyl-2-pyrrolidone and back-titrated with standard NaN02. 

Gamma-Butyrolactone (GBL) is an intermediate for the manufacture of Pyrrolidones which have a wide range of uses such as speciality solvents, functional monomers and pharmaceutical intermediates. GBL can be made by the vapour phase dehydrogenation of 1,4-butanediol over a copper/pumice catalyst at 200°C. It is also available as a by-product with THF in the Davy McKee two step butane diol process starting from maleic anhydride (MAN) via diethylmaleate [27]. 

Neutral and acidic polymers such as polyvinyl pyrrolidone, copolymers of polyvinyl pyrrolidone with vinyl acetate, and copolymers of methyl vinyl ether with half esters of maleic anhydride, are all used in hair styling and hair setting products. 

The resins of styling or setting products are usually cationic (e.g., polyquatemium-11, a copolymer of vinyl pyrrolidone and dimethy-laminoethyl methacrylate quaternized with dimethyl sulfate, similar to the quatemized copolymer of PVP depicted in Table 7-2), anionic (e.g., butyl ester of polyvinyhnethyl ether and maleic anhydride), neutral (e.g., copolymer of polyvinyl pyrrolidone, vinyl acetate), or even polyvinyl pyrrolidone itself with polyacrylate thickeners. 

---