Imides cyano

As part of an effort to develop high-performance, high-temperature-resistant polymers for microelectronics applications, we also recently described a series of both partially fluorinated and nonfluorinated poly(aryl ether ketone)s containing amide, amide-imide, cyano oxadizole, or pyridazine groups and characterized their thermal and electrical properties.11... 

The above is an example of the Guareschi reaction. It is applicable to most dialkyl ketones and to alicyclic ketones (e.g., cyclohexanone, cyc/opentanone, etc.). The condensation product (I) is probably formed by a simple Knoe-venagel reaction of the ketone and ethyl cyanoacetate to yield ethyl a-cyano-pp dimethylacrylate (CH3)2C=C(CN)COOCjHj, followed by a Michael ad tion of a second molecule of ethyl cyanoacetate finally, the carbethoxyl groups are converted to the cyclic imide structure by the action of ammonia. 

The synthetic potential of alkenylzirconium complexes is partially due to the fact that the hydrozirconation of alkynes can be carried out in the presence of some synthetically useful functional groups such as halide [80,153, 211, 212], acetals, amides, imides, carbamates, sulfides [186], ester, cyano [95, 213] and chiral propargyl amino functionalities [214]. 

Attack on Halogen. Predictably, the 3-bromo-3-cyano-imides (56) and (57) form quasiphosphonium salts (58) with aryl phosphites, phosphonites, and phosphinites.47 In the case of (56) these salts cyclize to the oxazaphosphorane (59), which is in equilibrium with the iminophosphorane (60), depending on the phosphorus ester used. 

The apparently quite broad structural requirements for anticonvulsant activity, noted earlier in this chapter, extend to yet another class of five-membered heterocycles that include an imide function. Imidazo-2,4-diones, better known as hydan-toins, have comprised some of the most widely used drugs for treating severe motor and psychomotor epileptic seizures. The general reaction used to prepare this heterocyclic system involves the treatment of a carbonyl compound with ammonium carbonate and potassium cyanide. The first step in the complex sequence can be visualized as the addition of the elements of ammonia and hydrogen cyanide to give an a-aminonitrile (88-2). Addition of ammonia to the cyano group would then lead to an amidine (88-3). Carbon dioxide or carbonate ion present in the reaction... 

The unstable dibenz[c,/][l,2]oxazepines (312 R = CN, Cl) have been isolated as the major products of the UV irradiation of 9-cyano- and 9-chloro-acridine 10-oxides (310) in benzene (c/. the analogous Af-imide to 1,2-diazepine conversion on p. 598). Although none of the oxaziridine tautomer (311) was detectable by UV spectroscopy, the subsequent deoxygenation of (312) to acridine suggests the existence of a thermal equilibrium between (311) and (312) (79T1273). These dibenzo compounds (312) are the only fully unsaturated oxazepines yet isolated but the 2,3-benzoxazepin-l-one system (314) has recently been prepared by the reaction of benzonitrile oxide with the benzopyranone (313) (80JCS(Pl)846). 

Phthalimides have often been used in the double role of electron acceptor sensitizers and radical traps, and are in fact benzylated by irradiation in the presence of toluene and several other precursors. 4,5-Dicyanophthalimide undergoes substitution of a benzyl for a cyano group when irradiated with toluene, but mainly attack at the imide carbon occurs with diphenylmethane. With various donors the competition between the two modes of reaction has been found to depend on the cage vs. out of cage radical cation cleavage, in the first case with the assistance of the radical anion [223] (Sch. 18). 

Chloro-3-cyano-4,6-diphcnylpyridinc reacted with sodium hydrogen telluride in ethanol under an argon atmosphere to produce a cyclic telluronocarboxylic amide (tellurolocar-boxylic imide)1. 

Similar to thiol addition to imines, imidic esters,69,70 and cyano compounds possessing an a-proton (35), such as cyanic acid,71 cyanamide,71 monosubstituted cyanimides,72 and a-substituted acetonitriles,69,70,73,74 react smoothly with a-mercaptoacetic acids (26) to generate an unstable acyclic intermediate 36, which cyclizes to give 37 (Y = O, NH, NR, and CHR, respectively) [Eq. (10)]. 

The cyclization of formamidincs (24) has been extended to similar reactions of amidrazones (29), which give 1,5-diaminoimidazoles when treated with bases (Scheme 2.2.10). Again, depending on the basic strength, the 4-substituent is cyano or cyanoformimidoyl. The amidrazones are available in almost quantitative yield by treatment of the imidate (27) with hydrazine hydrate at room temperature [35]. 

Cyano-l, 2-benzoquinone, 732 4-Cyanocatecho, 732 3a-Cyanocholestane, 696 Ia-Cyano-Sa-cholestane-3-one, 5 Cyanocholestane-3-one, Sa- and 55-, 1197 o-Cyanocycloheptanone imide, 1047 N-Cyano-1,1-dimethylaziridine, 174 2-Cyano-3,6-dlmcthyl-l,4-benzoquinone,... 

The tandem Homer-Wadsworth-Emmons and Michael reactions have been applied to lactols, providing tetrahydropyranyl or tetrahydrofuranyl derivatives to the hemiaminal derived from A-Boc-protected pyroglutamic esters, providing 5-substituted prolinates and to imidate anion, providing oxazolidine. On reaction with lactols, replacement of the cyanomethylphosphonate by the 1-cyano-1-dimethylaminomethylphosphonate leads to the formation of a-cyano enamines as a... 

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