Nitrogen reaction with magnesium

Of the many organometallic compounds, only Grignard reagents are used for formation of C-N bonds. Alkyl- and aryl-magnesium halides undergo various types of reaction with nitrogen compounds,1216 but few of these have major importance. 

The combustion of magnesium is a bit easier to talk about than the combustion of a hydrocarbon fuel, so I shall deal with magnesium first and then move on to the more familiar reaction of the combustion of hydrocarbons. I ll pretend that in its combustion, magnesium combines only with oxygen its additional reaction with nitrogen when it bums in air doesn t add much new and complicates the discussion. 

The purity of commercial-grade calcium depends to a large extent on the purity of the calcium oxide used in its production. Impurities such as magnesium oxide, or other alkaline-earth or alkaH metal compounds are reduced along with the calcium oxide, and these metals can contaminate the calcium. In addition, small amounts of aluminum may distill with the calcium vapor, and small amounts of calcium nitride may be produced by reaction with atmospheric nitrogen. 

Precursors for this task were obtained by addition of /-butylmagnesium bromide to the central bond of [1.1.1 ]propellane 40a followed by conversion of the 3-f-butylbicyclo[ 1.1.1 Jpentyl-1 -y 1-magnesium bromide (88) into the ketones 89 by standard methods.27 Reaction of ketones 89 with tosyl hydrazide afforded the hydrazones 90, which gave the corresponding lithium salts 91 by reaction with MeLi in ether. These salts were dried under high vacuum and then pyrolized at 4 x 10 5 torr in the temperature range of 100-130°C and the volatile products condensed in a liquid nitrogen-cooled trap. 

Amines such as diethylamine, morpholine, pyridine, and /V, /V, /V, /V -tetramethylethylene-diamine are used to solubilize the metal salt and increase the pH of the reaction system so as to lower the oxidation potential of the phenol reactant. The polymerization does not proceed if one uses an amine that forms an insoluble metal complex. Some copper-amine catalysts are inactivated by hydrolysis via the water formed as a by-product of polymerization. The presence of a desiccant such as anhydrous magnesium sulfate or 4-A molecular sieve in the reaction mixture prevents this inactivation. Polymerization is terminated by sweeping the reaction system with nitrogen and the catalyst is inactivated and removed by using an aqueous chelating agent. 

B. 2-Naphthalenethiol. In a 250-ml. flask, fitted with a diffusion tube2 and swept with nitrogen, is placed 23.1 g. (0.10 mole) of O-2-naphthyldimethylthiocarbamate (Note 4). The flask is heated at 270-275° for 45 minutes in a salt bath (Note 5). After cooling, a solution of 8.4 g. (0.15 mole) of potassium hydroxide in 10 ml. of water and 75 ml. of ethylene glycol is added to the flask. The diffusion tube is replaced by a condenser, and the mixture is heated at reflux for 1 hour (Note 6). The cooled reaction mixture is poured onto 150 g. of ice. After the ice has melted, the mixture is shaken two times with 150-ml. portions of chloroform. The chloroform layers are discarded, and the aqueous layer is cautiously acidified with concentrated hydrochloric acid (Note 7) and shaken three times with 75-ml. portions of chloroform. The organic layers are combined and dried by filtration through anhydrous magnesium sulfate. The solvent is removed by distillation to yield 13-15 g. of crude product. Distillation yields 10.3-12.8 g. (71-80%) of pure 2-naphthalenethiol, b.p. 92-94° (0.4 mm.), m.p. 80-81° (Note 8). 

Carbenoids have both a nucleophilic and an electrophilic nature. This is one of the most striking characteristics of carbenoids. Especially, electrophilic reaction of magnesium carbenoids with carbon and nitrogen nucleophiles has recently received much attention and various new interesting synthetic methods have appeared. 

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