O-Cyano-N-oxides

Potassium hexacyanoferrate(III)/potassium cyanide o-Cyano-N-oxides from cyclic N-oxides... 

Potassium hexacyanoferrate(lll)/potassium cyanide o-Cyano-N-oxides from cyclic N-oxides s. 26, 776 s. a. J. Org. Chem. 37, 3588 (1972)... 

G. Pilcher, W. E. Acree Jr., J. R. Powell. Enthalpies of Combustion of the Pyridine N-oxide Derivatives 4-Methyl-, 3-Cyano-, 4-Cyano-, 3-Hydroxy-, 2-Carboxy-, 4-Carboxy-, and 3-Methyl-4-Nitro, and of the Pyridine Derivatives 2-Carboxy- and 4-Carboxy-. The Dissociation Enthalpies of the N-O Bonds. J. Chem. Thermodynamics 1998, 30, 869-878. (b) M. D. M. C. Ribeiro da Silva, personal communication. 

Buchardt, O., Lohse, C., Duffield, A.M. and Djerassi, C. (1967) The photolysis of 1-phenyl and 1-cyano substituted isoquinoline N-oxides to benz[f]-l,3-oxazepines. Tetrahedron Letters, 8 (29), 2741-2745. 

N-oxides of this type are accessible from o-nitroaniline-based syntheses (see earlier section). l,2-Dihydro-2-oxoquinoxaline 4-oxide (64) and its N-methyl derivative (65) condense with compoimds containing an active methylene group in the presence of piperidine, yielding 3-alkylated quinoxalinones (66). The oxide 64, when warmed with aqueous potassium cyanide, affords 3-cyano-l,2-dihydro-2-oxoquinoxaline, whereas oxide 65 gives l,2-dihydro-3-hydroxy-2-oxo-l-methylquinoxaline. ... 

Diethyl cyanophosphonate converts quinoline and isoquinoline A -oxides into the 1- and 2-cyano heterocycles in high yields in a process which must have O-phosphorylation as a first step, and in which the elimination of diethylphosphate may proceed via a cyclic transition state trimethylsilyl cyanide and diazabicyclounde-cene effect the same transformation. Chloroformates and an alcohol convert the N-oxides into ethers, as illustrated below for isoquinoline A -oxide. ... 

Cyclization of 3-cyano-2-[(3-hydroxypropyl)amino]-5-(4-pyridyl)pyri-dine-l -oxide (298) in POCl3 yielded 9 - c y a n o - 7 - (4 - pyrid yl)-.3,4-dihydro- 2//-pyrido[l,2-a]-pyrimidine l -oxide (299) (94EJM175). After heating 3-cyano-4-trifluoromethyl-6-phenyl-2-[(3-hydroxypropyl- and 3-hydroxybutyl)-amino] pyridines in boiling POCl3 for 1 h, the product was treated with aqueous NH4OH to yield 6-phenyl-8-trifluoromethyl-9-cyano-3,4-dihydro-2/7-pyr-ido-[l,2-a]pyrimidine and its 4-methyl derivative (01CHE329). 

Draw the structural formula (one repeating unit) for each of the following polymers (a) poly(4-methylpent-l-ene) (b) poly(chlorotri uoroethylene) (c) poly(vinyl ethyl ether) (d) poly(vinylidene chloride) (e) polyethyleneimine (f) poly(methyl-2-cyano-acrylate) (g) polychloroprene (h) poly(buty-leneterephthalate) (i) poly(l,2-propylene oxalate) (j) poly(dihydroxymethylcyclohexyl terephthalate) (k) poly-caprolactam (nylon-6) (1) polyformaldehyde (m) poly-oxymethylene (n) poly(propylene oxide) (o) poly (propylene glycol) (p) poly(p-phenylene sulfone) (q) poly(dimethyl siloxane) (r) poly (vinyl butyral) (s) poly (p-phenylene) (t) poly(p-xylylene) (u) polycaprolactone... 

The carbon atom of the carbonyl group has two bonds with oxygen, and it also has one more bond with some heteroatom, Z (O, N, Cl, etc.). That gives a total of three bonds to heteroatoms. The carbon atom of a cyano group also has three bonds to a heteroatom. So, nitriles are at the same oxidation level as the other carboxylic acid derivatives. 

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