313. 1,3,5-Triazines. Part III. Arbuzov reactions of chlorotriazines

Preparation of 2,4,6-trisphosphinyl-1,3,5-triazine (1,3,5-triazinetriphosphonic acid)

“…In our case drop-wise addition of excess (Me 3 SiO) 3 P, containing the inert towards cyanuric chloride (Me 3 SiO) 2 P(O)H, to warmed at 110 • C solid cyanuric chloride should result in the production of 3b having intact ring [9] and probably free of side reactions [6]. However, only ∼20% of the expected Me 3 SiCl distilled off at 20 • C/760 mm Hg.…”

“…The Michaelis-Arbuzov reaction of cyanuric chloride with phosphites can be done in solvents or in the absence of a solvent [6]. In our case drop-wise addition of excess (Me 3 SiO) 3 P, containing the inert towards cyanuric chloride (Me 3 SiO) 2 P(O)H, to warmed at 110 • C solid cyanuric chloride should result in the production of 3b having intact ring [9] and probably free of side reactions [6].…”

“…In the Michaelis-Arbuzov reaction the triazine ring in 3a was intact and the products had some tendency to hydrolyze on the -OR group(s) in moist air but boiling them with water gave impure 4 [9]. A more detailed study of the reaction of cyanuric chloride with phosphites [6] revealed, among other findings, that competitive side reactions did not take place in the absence and in the presence of solvents (at 100-150 • C), some liquid esters 3a (R = n-Bu, PhCH 2 ) decomposed on the triazine ring when P.V. Ioannou / 2,4,6-trisphosphinyl-1,3,5-triazine kept in air and the -P(O)(OR) 2 group withdraws electrons from the ring thus favouring the nucleophilic displacement of -Cl by (RO) 3 P although the ease of -Cl displacement progressively decreases [10].…”

An efficient microwave-assisted synthesis and biological properties of polysubstituted pyrimidinyl- and 1,3,5-triazinylphosphonic acids

“…NMR spectra were recorded on Bruker AVANCE II 500 and/or Bruker AVANCE II 600 spectrometers in CDCl 3 , D 2 O or DMSO-d 6 ( 1 H at 500.0 or 600.1 MHz and 13 C at 125.7 or 150.9 MHz, chemical shifts are given in parts per million, coupling constants, J, in herz). Melting points were determined on a B€ uchi (Switzerland) melting point apparatus.…”

“…5 Later it was shown that reactivity of various phosphorous esters in the MeA reaction decreases in the order of increasing electron-withdrawing effect of the substituents on the phosphorus atom. 6 Furthermore, a replacement of the chlorine atom in 4,6-disubstituted 2-chlorotriazines was studied, 7 and the MeA reaction was used to prepare a series of N,N 0 -bis [(dialkylphosphono)-1,3,5-triazin-2-yl]diamines in high to moderate yields.…”