Q Cppyri hl 1967 b y Lhr Anntcon Ehmicol Socirly
VOLUME32, NUMBER11
NOVEMBER 15, 1967
The Chemistry of Nitrogen Radicals. V. The Free-Radical Addition of Dialkyl-N-chloramines to Olefinic and Acetylenic Hydrocarbons ROBERT S. NEALE Union Carbide Research Institute, Tarrytown, New York 10691
Received April 88,1967 The addition of dialkyl-N-chloramines to aliphatic 1,3-dienes1 1,2-dienea1terminal olefins, and acetylenes in sulfuric acid-acetic ?cid is described. These facile, free-radical chain reactions all involve the addition of an aminium radical &NH+ to a carbon-carbon multiple bond as the key step in the process, which affords 1: 1 adducts in 15438% yield. Since addition,not hydrogen abstraction, is characteristic of aminium radical reactions with these unsaturated hydrocarbons, chloramination provides a useful, direct route to pchloroalkyl-, pchloroalkenyl-, and &chloro&enylaminw in those casea in which nonradicd reactions or the Hofmann-Loeffler chloramine rearrangement do not compete successfully with the free-radical addition.
During a general study designed to define and utilize the potential of amino radicals as synthesis intermediates, we have explored a remarkable reaction whereby protonated aliphatic N-chlorodialkylamines add to unsaturated hydrocarbons in one step to produce chlorinated tertiary amines.’ I n the present paper we describe the application of this free-radical process to unsubstituted olefins, 1,3-dienes1 1,2dienes, and acetylenes in the solvent sulfuric acid-acetic acid; in the following paper we present our results using both substituted olefins and other acidic solvents. These papers together define the scope and limitations of the chloramination reaction, which provides ready access to a large number of previously unavailable compounds. As will be shown below, all these chloraminations are the consequence of a free-radical chain sequence of the type shown in eq 1 and 2, in which the key propagation &YH+ &NH
+-&-A.I I
+>C4
