Aminal nitrogens, halogenation

Unlike many other type of radical addition reactions, the product is most often an alkyl-cobalt(III) species capable of further manipulation. These product Co—C bonds have been converted in good yields to carbon-oxygen (alcohol, acetate), carbon-nitrogen (oxime, amine), carbon-halogen, carbon-sulfur (sulfide, sulfinic acid) and carbon-selenium bonds (equations 179 and 180)354. Exceptions to this rule are the intermolecular additions to electron-deficient olefins, in which the putative organocobalt(III) species eliminates to form an a,/ -unsaturated carbonyl compound or styrene353 or is reduced (under electrochemical conditions) to the alkane (equation 181)355. 

The first two derivatives in the series, monuron and metobromuron, are related to the 4-haloanilines. Their primary photochemistry has been studied by Boulkamh and Richard by means of nanosecond absorption spectroscopy [80]. The transients detected from both compounds in aqueous solution could be assigned to the N-substituted 4-iminocarbene, imino-p-benzoquinone-O-oxide and anilino radical from a complete analogy of their spectral and reactive behavior with that of the species obtained from 4-chloroaniline [55,57]. The quantum yields of carbene formation were determined to be = 0.051 for monuron and

halogen-substituted phenylurea derivatives underwent the same heterolytic dehalogenation process as the 4-haloanilines, which could be understood with reference to the protonability of the amine nitrogen, as in the case of 4-chloro-N,N-dimethylanilinc [55]. 

JV-Iodo amides are prepared exclusively by reaction of JV-silver salts with iodine. Occasionally the nitrogen-halogen bond has been created by trans-halogenation from, e.g., dichlorourea396 or JV-bromo amides.397 JV-Chloro-succinimide has been recommended for halogenation of sensitive amines in the steroid series.398... 

Advantages Can be used for capillary chromatography. Selectivity can be chosen for halogens, amines, nitrogen and sulfur. High sensitivity at high selectivity. Can be used for halogen detection without a source of radioactivity, therefore no authorization necessary. Simple calibration, as the response is directly proportional to the number of heteroatoms in the analyte, for example, the proportion of Cl in the molecule. 

Although acetonitrile is one of the more stable nitriles, it undergoes typical nitrile reactions and is used to produce many types of nitrogen-containing compounds, eg, amides (15), amines (16,17) higher molecular weight mono- and dinitriles (18,19) halogenated nitriles (20) ketones (21) isocyanates (22) heterocycles, eg, pyridines (23), and imidazolines (24). It can be trimerized to. f-trimethyltriazine (25) and has been telomerized with ethylene (26) and copolymerized with a-epoxides (27). 

Amine—borane adducts have the general formula R3N BX where R = H, alkyl, etc, and X = alkyl, H, halogen, etc. These compounds, characterized by a coordinate covalent bond between boron and nitrogen, form a class of reducing agents having a broad spectmm of reduction potentials (5). 

For alkylbenzenes, nitrobenzenes, halogenated benzenes and for secondary or tertiary amines where at least one aromatic group is connected to an amino nitrogen, add the following corrections for each aromatic nuclei is. If N < 16, increase AN by 0.60 if N > 16, increase AN by 3.055 — 0.161N for each aromatic group. For any N, increase AB by (—140.04 + 13.869 ). 

It has been proposed (89JOC4808) that the first step of a reaction between an amine and an N-(l-chloroalkyl)pyridinium chloride 33 is a simple substitution of the halogen atom yielding a mixed bisonium salt 55 (pathway a in Scheme 19). Tliis is the final product when various nitrogen het-... 

A phenyl ethanol amine in which the nitrogen is alkylated by a long chain alphatic group departs in activity from the prototypes. This agent, suloctidil (43) is described as a peripheral vasodilator endowed with platelet antiaggregatory activity. As with the more classical compounds, preparation proceeds through bromination of the substituted propiophen-one ( ) and displacement of halogen with octyl amine. Reduction, in this case by means of sodium borohydride affords suloctidil (43). ... 

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