Pyrrolidones nitriles

N-(2-Cyan-athyl)-pyrrolidon —> 3-Pyrrolidino-propansdure-nitril 66% d.Th. 

A more highly substituted pyrrolidone, doxapram, shows activity as a respiratory stimulant. Preparation of this agent involves an interesting rearrangement, which in effect results in a ring exchange reaction. Alkylation of the anion from diphenylacetonitrile with the chloropyrrolidine 14 affords 15. Hydrolysis of the nitrile function leads to the... 

All nitrile-based coatings reported in this study we e applied to Bonderite 40 coated steel (B40) panels (150-300 mg/ft zinc phosphate pretreatment The Parker Company). A commercial high nitrile polymer (Barex 210) was employed as the base resin. N-vinyI pyrrolidone (Aldrich) and gamma-butyrolactone (Aldrich) were employed as reactive diluents. 

Because of the repulsion of the cyanide groups the polymer backbone assumes a rod-like conformation. The fibers derive their basic properties from this stiff structure of PAN where the nitrile groups are randomly distributed about the backbone rod. Because of strong bonding between the chains, they tend to form bundles. Most acrylic fibers actually contain small amounts of other monomers, such as methyl acrylate and methyl methacrylate. As they are difficult to dye, small amounts of ionic monomers, such as sodium styrene sulfonate, are often added to improve their dyeability. Other monomers are also employed to improve dyeability. These include small amounts (about 4%) of more hydrophilic monomers, such as -vinyl-2-pyrrolidone (Equation 6.69), methacrylic add, or 2-vinylpyridine (Equation 6.70). 

There remains a collection of syntheses from relatively uncommon precursors. One that has seen a modest amount of exploration involves the use of pyrrolidones as precursors. Thus the iV-tosyl-2-pyrrolidone 172 reacts with nitriles to give partially reduced pyrrolo[2,3-r/ pyrimidines 173 (Equation 64) <1996T7973>. 

An unusual rearrangement provides the key to the preparation of a highly substituted pyrrolidone, doxapram (26-7), that is used as a respiratory stimulant. The synthesis starts with the displacement of chlorine on pyrrolidine (26-1) by the carbanion from diphenylacetonitrile (26-2) to give (26-3) as the product. The quite hindered nitrile is then hydrolyzed to the corresponding carboxylic acid (26-4) by basic hydrolysis. The reaction of acid with thionyl chloride presumably proceeds initially to form the corresponding acid chloride. The close proximity of that group to basic... 

Stannic chloride has been attached to monomers 21 containing ester (21a), carbazole (21b), pyrrolidone (21c), nitrile (21d) and pyridine (21d) moieties. The polymeric ligands were prepared by copolymerization of styrene, divinylbenzene and functional monomers such as methyl methacrylate, A -vinylcarbazole, Af-vinylpyrrolidone, acrylonitrile and 4-vinylpyridine [33], These polymers were treated with stannic chloride in chloroform to afford the corresponding polymer-supported stannic chloride complexes (Eq. 8). These polymeric complexes have been used as catalysts for such organic reactions including esterification, acetalization, and ketal formation. These complexes had good catalytic activity in the reactions and could be reused many times without loss of activity. Their stability was much better than that of plain polystyrene-stannic chloride complex catalyst. 

By this method, 1-bromonaphthalene affords 1-naphthonitrile in 94% yield after refluxing for 4 hrs. with pyridine as solvent the reaction mixture is heated in an oil bath at 215-225° for 15 hrs., and the yield is 82-90%. Efficient procedures for liberating the nitrile from the cuprous halide complex involve pouring the brown reaction mixture into an aqueous solution of ferric chloride (oxidizes Cu+ to Cu ", which forms no complex), ethylenediamine (forms complexes with Cu+ and Cu " ), or sodium cyanide (forms soluble sodium cuprocyanide). The higher-boiling N-methyl-2-pyrrolidone (b.p, 202°) is also satisfactory, but is more expensive. 

Special solvent. Newman - recommends N-methyl-2-pyrrolidone as solvent for the reaction of an aryl halide with cuprous cyanide to produce the corresponding nitrile. Dimethylformamide (b.p. 153°) has been suggested as a better solvent than originally used pyridine (b.p. 115°), but l-methyl-2-pyrrolidone has an even higher boiling point and seems still more satisfactory. An example is the synthesis of... 

The most general synthesis of substituted 6,7-dihydro-5/f-pyrrolo[l,2-a]imidazoles has been described in several patents. The starting materials are pyrrolidine derivatives such as the 2-iminopyrrolidine or 2-pyrrolidone (Scheme 8) <89EUP306300, 92MI 802-01 >. In the first case, the 2-iminopyrrolidine reacts with the chloroketone (57) at 40°C to give the dihydro pyrrolo[l,2-a]im-idazole (58). In the second case the 2-pyrrolidone was A -acylated by 4-picolyl chloride and the product (59) cyclocondensed with a nitrile to give the 2,3-diaryl-6,7-dihydro-5//-pyrrolo[l,2-a]im-idazole (60). 

Presumably the mesomeric 3a,5a-cyclo-cation (442) suffers nucleophilic attack by the nitrile hydrolysis of the resulting cation (443) gives the amide (444). The reaction provides a convenient route from cholesterol to 3)5-acetamido-cholest-5-ene. Use of 4-chlorobutyronitrile gives the corresponding chloro-amide, which is readily hydrolysed to the amine hydrochloride or cyclized by base to give the pyrrolidone (445). 

Nonoxynol-4 sulfate Octadecene nitrile Octoxynol-14 N-Octyl pyrrolidone Oleamine Oleth-15 Oleth-5 phosphate Oleyl imidazolinium hydrochloride Oleyl propylene diamine dioleate 4,4(5H)-Oxazoledimethanol,... 

Dicyclohexylamine Lauryl nitrile C12H23N HNO2 Dicyclohexylamine nitrite C12H23NO N-Octyl pyrrolidone (Ci2H23NO)n Nylon 12 C12H23O2 K Potassium laurate C12H23O2 Na Sodium laurate Ci2H2304Na... 

N-Condensed benzothiazoles. A soln. of N-(o-bromophenyl)-5-/ r/-butylthio-2-pyrrolidone and Bu3SnD in deaerated benzene containing a little azodiisobutyro-nitrile refluxed under N2 until reaction complete (4-18 h) 2,3-benzo-8-oxo-4-thia-l-azabicyclo[3.3.0]octane. Y 89%. F.e. incl. N-condensed 2//-l,3-benzothiazines from N-(o-bromobenzyl)-analogs s. A.L.J. Beckwith, D.R. Boate, J. Org. Chem. 53, 4339-48 (1988). 

Table 17.3 compares the solvency of a 60 vol% nitroethane and 40 vol% toluene blend for a nitrile-butyl rubber as compared to the solvents cyclohexanone and N-methyl 2-pyrrolidone. A Lotus 123 spreadsheet, DECITREE.WKl, was used to generate Table 17.3. This spreadsheet is included on the computer disk accompanying this book. The spreadsheet allows one to compare the solubility parameters of solvents with a selected resin. The values for the selected resin are supplied by the user while the solvent data is available from the lookup tables. The typical R values are calculated and the location of...

Figure 17.2 Hansen solvency on a polarity versus hydrogen bonding plot of a 60 vol% nitroethane and 40 vol% toluene blend for a nitrile-butyl rubber as compared to the solvents cyclohexanone and N-methyl 2-pyrrolidone. This plot comes from the solvency comparisons shown in Table 17.3.

Some specific recent applications of the chromatography-mass spectrometry technique to various types of polymers include the following PE [130, 131], poly(l-octene), poly(l-decene), poly(l-dodecene) and 1-octene-l-decene-l-dodecene terpolymer [132], chlorinated polyethylene [133], polyolefins [134,135], acrylic acid, methacrylic acid copolymers [136, 137], polyacrylate [138], styrene-butadiene and other rubbers [139-141], nitrile rubber [142], natural rubbers [143,144], chlorinated natural rubber [145,146], polychloroprene [147], PVC [148-150], silicones [151,152], polycarbonates (PC) [153], styrene-isoprene copolymers [154], substituted PS [155], polypropylene carbonate [156], ethylene-vinyl acetate copolymer [157], Nylon 6,6 [158], polyisopropenyl cyclohexane-a-methylstyrene copolymers [195], cresol-novolac epoxy resins [160], polymeric flame retardants [161], poly(4-N-alkylstyrenes) [162], pol)winyl pyrrolidone [31,163], vinyl pyrrolidone-methacryloxysilicone copolymers [164], polybutylcyanoacrylate [165], polysulfide copolymers [1669], poly(diethyl-2-methacryloxy) ethyl phosphate [167, 168], ethane-carbon monoxide copolymers [169], polyetherimide [170], and bisphenol-A [171]. 

DMA has been applied to the determination of Tg in neoprene, styrene-butadiene, polyisoprene, polybutadiene, polychloroprene, nitrile ethylene-propylene-diene, and butyl rubbers [4], polybutadiene [10], glass-filled low-density polyethylene [11], PU, PMMA, polyimides, acrylonitrile-butadiene-styrene terpolymer, PET, and Nylon 6 [2], bisphenol-A epoxy diacrylate, N-vinyl pyrrolidone copolymer, and trimetholpropane triacrylate [5]. 

Hetbyl-l.m.tolyl.pyrrolidon.(5). arbon> e6aie.(2).nitril 22, 290. 

FTIR spectroscopy has been applied in the study of polymer blends including Neoprene rubber, chlorosulfonated PE, nitrile rubber, polyvinyl chloride (PVC) containing carbon black and other fillers [86], Nylon 6 inorganic [87], polyhydroxyether sulfone/poly(N-vinyl pyrrolidone) [88], graphite-based low-density polyethylene [89], caprolactone/Nafion blends [90], polybutylene terephthalate/polyamide [91], polyphenylene sulfide/acrylonitrile - butadiene - styrene [92], PMMA/polypyrrol [93], and lower or high performance liquid chromatography (LDPE/HDPE) [94]. 

Other applications of AFM to the characterisation of polymers include polythiophene [9], nitrile rubbers [10], perfluoro copolymers of cyclic polyisocyanurates of hexamethylene diisocyanate and isophorone diisocyanate [11], perfluorosulfonate [12], vinyl polymers [13], polyhydroxybutyrate [14], polyacrylic acid nanogels [15], acrylic copolymers [16, 17], polyurethanes [18, 19], ethylene methacrylate copolymer [4, 20], polyamides [21], polyvinyl pyrrolidone [22], and polyethyl methacrylate dispersions [23], acryloyl chloride [13], aniline-4-sulfonic acid [24], ethylene propylene 5-ethylidene-2-norbornene terpolymer [25] and butylene adipate - butylene terephthalae [26]. 

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. 

Through the years other monomers have been investigated. The diene commonly employed is 1,3-butadiene, although isoprene, 2-ethyl butadiene, 2,3-dimethyl butadiene, piperylene, and other substituted dienes have been investigated. The nitrile commonly employed is acrylonitrile. It has been reported that when part of the acrylonitrile is replaced by methacrylo-nitrile or ethacrylonitrile, the cement-making properties of the rubber are improved. Small proportions of a third monomer may also be used in conjunction with the two principal components. Hycar 1072, which employs methacrylic acid as the third monomer, is occasionally used in adhesive applications. Other monomers including ethyl acrylate, methyl methacrylate, styrene, vinylidene chloride, acrylic acid, N-vinyl-2-pyrrolidone, and vinyl acetate have been employed in varying amounts to adjust the adhesive and elastomeric properties. 

Heating can also increase the degree of conversion, either conventionally or through use of microwave irradiation. Cohen and coworkers showed that [Zrg04(0H)4(bdc-Br)g] (UiO-66-Br) reacts with CuCN in DMF at 140 °C with 43% of the bromides converted to nitriles after 24 h. In contrast, microwave irradiation in A-methyl-2-pyrrolidone increased the conversion to 90% after only 10 min. Ranocchiari and coworkers reported that vapor-phase PSM could be used to enhance the degree of modification while also decreasing reaction time. In this process, the... 

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