Tetrachloro amines

An extensive study of the amination of halopyridines has been carried out by den Hertog and co-workers.A comparison of their results with studies in inert solvents using primary and tertiary amines should permit some evaluation of the postulated factors. 2,4-Dichloropyridine in concentrated aqueous ammonia (180°, 5 hr) resulted in the formation of 4-amino- (60% yield) and 2-amino-chloropyridines (20% yield). Under similar conditions, only 4-substitution of 3,4,6-trichloro- and of 2,3,4,5-tetrabromo- and -tetrachloro-pyridines was observed. However, in these and the other polyhalo pyridines, the appreciable and unequal mutual activation by the halogen substituents needs to be emphasized. 

Bis(substituted amino)-4,8-bisethylthio (or carboxymethylthio)-pyrimido[5,4-d]pyrimidines (464) are aminated first at the 4-position with primary or secondary amines at 180° (2 hr) and then at the 8-position (200°, 4 hr). The 4,8-bisthioxo derivative of 464 is 4,8-diaminated with ethanolamine (170°, 1 hr). 2,6-Dianilino-4,8-dioxo(or diethoxy or dibenzyloxy) derivatives of 464 react at the 4-and 8-positions with primary or secondary amines at 180°. The 2,4,6,8-tetrachloro derivative is claimed to goto the tetrakis(triethylammonio) compound. ... 

The reactions 33 between tetrachloro-A-n-butylphthalimide (113) and n-butylamine275 in aprotic and apolar media (cyclohexane, benzene, toluene, xylenes) show a third experimental reaction order in the amines explained by the formation of a complex (n-jr-like) between the electron acceptor substrate (the derivative of the phthalimide) and the electron donor nucleophile (the amine). In mixed solvents (such as the mixtures cyclohexane/aromatic solvents) the kinetic investigation reveals the presence of a competition between the electron donor solvent and the amine in complexing the substrate. 

Aliquat (0.2 g, 0.5 mmol) is added to the amine (l 4.5 mmol) in H20 (25 ml) and 1,2,3,4-tetrachloro-5,6-dinitrobenzene (2.0 g, 6.5 mmol) in PhMe (25 ml). The two-phase system is stirred under reflux for ca. 1 h and then cooled. The organic phase is separated, dried (MgS04), and evaporated. Chromatography of the residue from silica gives the aniline. 

Reacts with amines and alkali metals forming the corresponding water-soluble salts (Sanborn et al, 1977). Reacts with nitric acid forming a mixture of tetrachloro-o and p quinones (Monsanto, 1963). 

Other work (I) has shown that the reaction of titanium(IV) chloride and trimethylamine yielded a mixture which was 90% tetrachloro( trimethylamine)-titanium(IV) and 10% trichlorobis (trimethylamine) titanium (III). The oxidation product of the reaction was not identified. However, the authors suggested that the oxidation products could be amine polymers or chloroamine derivatives. 

Bis[2,2 -bis(diphenylphosphine)-l,l -binaphthyl] (tetrachloro) (triethyl-amine) diruthenium, 36 Bis( 1,5-cyclooctadiene)nickel(0)-Di-ethylaluminum chloride-Threophos, 298... 

Bis[2,2 -bis(diphenylphosphine)-l, 1 -binaphthyl](tetrachloro)(triethyl-amine)diruthenium, 36 [2,2 -Bis(diphenylphosphine) -1, T-binaphthyl](dimethanol)rhodium(I) perchlorate, 36... 

P3rrimidines with ethereal ammonia (20°, 30 min, 36% yield) or dimethylamine (0°, 1 hr, 62% yield) and alcoholic hydrazine hydrate (25°, 62% yield). It should be pointed out that the mono-snbstitution products from 2,4,6-trichloro-, 2,4,6,6-tetrachloro-, and 5-chloro-2,4,6-trifluoro-pyrimidines with tertiary amines in hydrocarbons were assumed by Kober and Raetz to be 2-derivatives. 

The reactions of aliphatic and aromatic amines with the trimeric chloride have been studied by Schenk (70) and by Bode, et al. (14), who give details of the preparation of the dichlorotetraanilide, the hexa-p-toluidide, the hexapiperidide, the tetrachloro-bis-dimethylamide and the corresponding compound with ethylenediamine. The tetrachloro-... 

Miscellaneous Reactions of Phosphines. Procedures for the resolution of benzylcyclohexylphenylphosphine have been developed, involving adduct formation with cyclopalladated chiral amine complexes. A similar approach has also been used for the resolution of P-chiral secondary phosphines, e.g. (193). Treatment of t-butyl(di-o-tolyl)phosphine with potassium tetrachloro-palladate(ii) yields a cyclopalladated complex (194), involving chiral phos-... 

Condensation of 2,3,5,6-tetrachloro-2,5-cyclohexadiene [118-75-2], C6C1402, with 9-ethyl-91T-carbazol-3-amine [132-32-1], C14H14N2, (11) leads fkst to (22) [6358-30-1]. Treatment with IV-methylol-a-chloroacetamide [2832-19-1] and sulfuric acid produces (23) [87564-36-1], which forms the pyridinium... 

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