The Mechanism of Aminations of Halobenzenes¹

Abstract

Mechanism of Amination of Halobenzenes 601 1.3855, was used as solvent. Sodium iodide, reagent grade, was dried overnight at 105°before use. The nitrate esters, prepared by nitration of the bromohydrins, were kindly furnished by Dr. Boris Franzus.Reaction Rate Studies.-The reactions were run and the rates calculated substantially as described by Young.20 No salt corrections20 were made, nor did any appear necessary.In runs below 90°, the solutions were prepared at the reaction temperature in volumetric flasks and run in ground-glass stoppered volumetric flasks. At higher temperatures sealed tubes were used; as well as in some runs at 88°. The principal advantage of the use of «-propyl alcohol over methyl alcohol resides in its lower volatility.The order of the reactions may be noted from tire constancy of the rate constants with variation of reagent concentration (Table I).Reaction of Iodine with Solvents.-An acetone solution, 0.005 M in iodine and 0.21 M in sodium iodide, lost about 50% of its iodine in 70 hours at 62.4°. A solution (in 99% aq. methanol), 0.025 M in iodine and 0.265 M in sodium iodide lost less than 2% of its iodine in 200 hours at 62.4°. A solution (in «-propyl alcohol), 0.065 M in iodine and 0.26 M in sodium iodide, lost less than 1% of its iodine in 200 hours at 62.4°.

A STUDY ON THE STRUCTURE OF THE CYCLOPENTADIENYL ANION WITH C14 AS TRACER

“…The Schmidt Reaction on Glutaric Acid-3-C14 This was carried out according to procedures already described in the literature (29,30). From 198 mg (1.5 mmoles) of X I I I , the yield of barium carbonate from the carbon dioxide absorbed in carbonate-free sodium hydroxide solution was 300 mg (52%), while the yield of trimethylene-1,3-diamii1e-2-C~~ dihydrogen bromide was 49.5 mg (14%).…”

Facile one-pot synthesis of 10-aryl derivatives of 9-aminoanthracenes and 9,10-dihydroanthracen-9-imines

“…3 However, 3,6-dimethylbenzyne 3a reacts with lithiated arylacetonitriles 4 to give 1,4,5,8-tetramethyl-9,10-dihydroanthracen-9-imines 8 (Scheme 1). protons of the acetyl group at δ 2.5 and δ ~1.7, two sets of doublets for the peri protons at δ ~ 7.9 and δ ~ 9.1, and a considerably broadened amide proton signal as well as a broadened signal in the range of δ 5.5 -6.0 due to 5-H of the imino tautomers.…”

Investigation of Reaction Mechanisms by Product Studies

“…Some of the most surprising (but also 20 The Investigation of Organic Reactions and Their Mechanisms convincing) mechanistic evidence has arisen from mechanistic studies involving isotopic labelling (e.g. evidence for benzyne intermediates) and the use of isotopic labels provides ways to identify which bonds are broken or formed during a reaction (Section 2.3.2).…”