Phosphorus–nitrogen compounds. Part XXXI. Reactions of hexachlorocyclotriphosphazatriene with aniline

Abstract

Hexachlorocyclotriphosphazatriene reacts with aniline to give mono, 2,2-bis-, 2,4-bis-, 2,2,4-tris-, 2,2,4,4-tetrakis-. and hexakis-anilino-derivatives, N3P3C16-n(NHPh), (n = 1, 2, 2, 3,4, or 6). The predominantly geminal reaction pattern was established by basicity measurements. and by the preparation of anilinodimethylaminocyclotriphosphazatrienes, and measurements of their l H n.m.r. spectra. HEXACHLOROCYCLOTRIPHOSPHAZATRIENE (I) reacts withamines in organic solvents to give aminocyclotriphosphazatrienes and amine hydrochlorides.2 It is shown here that reactions with aniline take place by a predominantly geminal pattern, to give derivatives of composition N,P,Cl,-,(NHPh),A mixture containing all six derivatives in addition to oily decomposition products is usually obtained. Relatively weak nucleophiles, e.g., phenoxide and aniline, are less selective than stronger nucleophiles, e.g., aliphatic a m i n e ~, ~~~ which give rise to more powerful electron-supplying substituents.The monoanilinopentachloro-derivative ( 11) is isolated comparatively easily by column adsorption chromatography. The nongeminal-bisanilinotetrachloro-(IV) and geminal-trisanilinotrichloro-(V) derivatives are obtained in particularly low yields. A small-scale reaction of the monoanilinopentachloro-derivative ( 11) with 2 moles of aniline was shown by t.1.c. to give a mixture of all the higher derivatives ( 111)-(VII). Similar reactions of the geminal-bisanilinotetrachloroderivative (111) give only the geminal-tetrakisanilinodichloro-(VI) and hexakisanilino-(VII) derivatives. The nongeminal-bisanilinotetrachloro-derivative (IV) gives also the geminal-trisanilinotrichloro-derivative.The anilinochloro-derivatives react with an excess of dimethylamine in benzene or chloroform when heated in a sealed tube, to give anilinodimethylamino-derivatives. The reactions of hexachlorocyclotriphosphazatriene (I) with dimethylamine have been investigated extensively, and the structures of the chlorodimethylaminocyclotriphosphazatrienes have been establi~hed.~., Their reactions with aniline to give anilinodimethylamino-derivatives are also reported here.

Synthesis and Theoretical Studies of 1,3,3,5,5-Pentachloro- 1-mono-(2-amidopyridin)cyclotriphosphazene

“…This result implies that the products formed are presumably the non-geminal bis-(amino) derivatives. In contrast to the previous report of a predominantly geminal mode of substitution established for aniline in benzene 20,21 .…”

Studies of phosphazenes. Part 30. Reactions of hexachlorocyclotriphosphazene with aromatic primary amines: interplay of geminal and non-geminal modes of chlorine replacement

“…data for dimethylamino and methoxy derivatives of (p-anisidino)cyclotriphosphazenes are summarized in Figure 2; for the corresponding anilino and p-toluidino derivatives similar trends are observed both in the chemical shifts (deviation k 0.08 6 unit) and coupling constants (deviation & 1 Hz). The assignment of the chemical shifts to protons in different environments can be made unambiguously for compounds (21) , trans-(22), trans-(24), (25), (27), trans-(28), (30), trans-(31), (33), and trans-(34) from a consideration of the relative intensities and also on the basis of the presence or absence of 'virtual coupling'.' The assignments for other compounds are made on the basis of the shielding effect of the triethylamine is used as the hydrogen halide acceptor instead of the reacting amine itself in the above solvents, the geminal bis(amino) product is formed exclusively.…”

Bridged cyclophosphazenes resulting from deprotonation reactions of cyclotriphophazenes bearing a P–NH group

“…The first compound eluted from the column was the product 4b (0.82 g, 49%, mp 288 Reaction of 3c with NaH to give compound 4c and 5c. Compound 3c 43 (2.02 g, 5 mmol) was dissolved in 50 mL of dry THF in a 100 mL three-necked round-bottomed flask. The reaction mixture was cooled in an ice-bath and NaH (60% oil suspension, 0.2 g, 5 mmol) in 10 mL of dry THF was quickly added to a stirred solution under an argon atmosphere.…”