Preparation, Properties and Reactions of Polychloroamine Derivatives

Abstract

Highly chlorinated amine derivatives can be prepared by the high‐temperature chlorination of amines and amine derivatives. Essential for the success of this reaction is an adequate temperature control suited to the constitution of the amines. In many cases the chlorination products achieve stability by cleavage reactions with formation of the imidic acid chloride or isocyanide dichloride grouping. Cyclic compounds are formed under special conditions. The chlorination process described can be used to obtain e.g. polychloroaryl and polychloroalkyl isocyanide dichlorides, polychloroaryl and polychloroalkyl imidic acid chlorides, and polychloroheterocyclic compounds.

Polychloroheteroaromatic Compounds

“…Pentachloropyridine is formed together with other products on chlorination of piperidine with chlorine diluted with carbon tetrachloride at 580° [252]. N-Methylpiperidine [253] and piperidine-N-carbonyl chloride [69,71] similarly give pentachloropyridine, together with lower chlorinated pyridines. Photo chlorination of 2,6-dicyano-N-methylpiperidine in chloroform at 50-60° for 67 h followed by further treatment of the product with chlorine in an autoclave at 195° in the presence of charcoal or further chlorination of the initial product in the vapour phase is claimed [254] to give trichloro-2,6-dicyanopyridine.…”

“…Similar treatment of N-methylpyrrolidine initially gives the polychloropyrroline (48), which loses carbon tetrachloride on prolonged reaction to give pentachloro-2H-pyrrole (39) [701. N-Phenylpyrrolidine similarly gives (49) (60-70%) [70,711, whilst 2,4-dichloro-6-pyrrolidino-striazine yields compound (50) [70, 711. Compound (49) is also formed (38%), together with (51), when NN-diethylaniline is treated with chlorine at 200 0 [70, 711. Under similar conditions N-methylpyrrolid-2-one yields compound (52; R= CCI3 ) [70, 711. On being heated with phosphorus pentachloride under pressure, succinimide gives a small amount of dichloromaleimide (53; R = H), together with the pyrrolidone (52; R = H) and pentachloro-2Hpyrrole (39) [45,521. As expected, with phosphorus pentachloride under similar conditions, dichloromaleimide (53; R = H) gives compound (52; R = H) or compound (39), or a mixture of both, depending on the conditions [52-541. In addition to tetrachloro-Nphenylpyrrole (45; R = CI), the pyrrolidone (52; R = Ph) (cf. ref.…”

“…These highly chlorinated indoles are reported to be extremely sensitive to moisture; the nature of the products formed on hydrolysis has not been established, but they all contain a carbonyl group [100,101]. Heptachloro-31l-indole (65) may be prepared also by the action of heat on N-pentachlorophenyltrichloroacetimidoyl chloride (66) [70,102,103]. 2,4-Dichloro-6-trichloromethylphenyl isocyanide dichloride (67) similarly yields 2,3,3,5,7-pentachloro-3H-indole.…”

“…Tetrachloro-o-benzoquinone condenses with ethyl (i-aminocrotonate and its N-methyl derivative in the presence of acid to give unstable 1: l-adducts, which cyclize to give the polychloroindoles (69; R = H or Me) [105]. 4,5,7-and 4,6,7-Trichloroisatin may be prepared by treatment of the appropriately chlorinated aniline with a mixture of chloral hydrate, hydroxylamine hydrochloride, and sodium sulphate, followed by cyclization of the resulting isonitrosoacetanilide (70) with concentrated sulphuric acid [106]. When (2-carboxy-3,4,5,6tetrachlorophenyl)glycine is heated with a mixture of acetic anhydride and sodium acetate, it yields NO-diacetyl-4,5,6,7-tetrachloroindoxyl (71; R = OAc), which gives the mono acetyl compound (71; R = H) following hydrolysis and reacetylation under controlled conditions [106].…”

Aromatic and Alkaromatic Chlorocarbons

“…It has recently been reported [106] that perchloro-N-methyleneaniline (XV) obtained by chlorination from various anilines, at 400-700° is converted partly into perchlorobenzene.…”