15916-99-1Relevant academic research and scientific papers
Two novel diorganotin phosphonic diamides: Syntheses, crystal structures, spectral properties and in vitro antibacterial studies
Gholivand, Khodayar,Farshadian, Sedigheh,Hosseini, Zahra,Khajeh, Khosro,Akbari, Neda
, p. 700 - 707 (2010)
Two diorganotin complexes with general formulae SnCl2(CH 3)2[C6H5P(O)(NHCH(CH 3)2)2]2 (1) and SnCl 2(CH3)2[C6Hs
Ultrasound-promoted, rapid and green synthesis of phosphonamide derivatives under catalyst and solvent-free conditions
Bouchareb, Fouzia,Berredjem, Malika,Bouzina, Abdeslem,Guerfi, Meriem
, p. 422 - 430 (2020/12/15)
We report a rapid, efficient, economic, environmentally benign, and easy to scale-up method for the synthesis of phosphonamide derivatives using ultrasound irradiation, under catalyst and solvent-free conditions starting from the corresponding amine and phenyl phosphonic dichloride. The reaction was achieved in excellent isolated yield in a short reaction time at room temperature. The structures of the synthesized compounds are confirmed by elemental analysis as well as by IR and 1H, 13C, 31P NMR spectroscopic data and mass spectrometry.
Synthesis, spectral characterization and crystal structures of organophosphonic diamides: Pyramidal nitrogen centers and hydrogen bonding in [PhP(O)(NHtBu)2], [PhP(O)(NHDipp)2] (Dipp = 2,6-iPr2C6H3) and [tBuP(O)(NHiPr)2]
Murugavel, Ramaswamy,Pothiraja, Ramasamy
, p. 968 - 974 (2007/10/03)
Organophosphonic diamides of general formula [R1P(O)(NHR2)2] (1-8; R1 = Ph, Cy or tBu and R2 = Cy, iPr, tBu or Dipp) have been prepared by the addition of P,P′-dichloro(alkyl/aryl)phosphine oxide, R1P(O)Cl2, to a solution of primary amine in toluene. The synthesis of PhP(O)(NHtBu)2 (1) in high yield was achieved by slow oxidation of PhP(NHtBu)2 in air over several days. All new compounds have been characterized by elemental analysis and by IR, EI mass and NMR (1H and 31P) spectroscopy. The molecular structures of [PhP(O)(NHtBu)2] (1), [PhPO(NHDipp)2] (2) and [tBuP(O)(NHiPr)2] (7) have been determined by single crystal X-ray diffraction studies. The amido nitrogen atoms in 1, 2 and 7 show considerable deviation from the expected trigonal-planar geometry. The observed dihedral angles and the orientation of the nitrogen lone pair (l.p.) in these compounds point to the role of l.p.(N) → σ*(P-X) type negative hyperconjugative interactions in P-N multiple bonding. Compounds 1 and 7 form interesting polymeric structures in the solid state with the aid of N-H...O=P hydrogen bonding interactions while the presence of the very bulky Dipp substituent on nitrogen in 2 prevents the participation of the N-H protons in hydrogen bonding with phosphoryl oxygen atoms.
Associative and Dissociative Mechanisms for the Rections of N-t-Butyl-P-phenylphosphonamidic Chloride with Isopropylamine and t-Butylamine: Competitive, Kinetic, and Stereochemical Studies
Freeman, Sally,Harger, Martin J. P.
, p. 81 - 90 (2007/10/02)
The substitution reactions of N-t-butyl-P-phenylphosphonamidic chloride (4a) with isopropylamine and t-butylamine (or t-pentylamine in stereochemical experiments) in MeCN at 0 deg C can apparently proceed by one associative and two dissociative mechanisms
Influence of ortho Methyl and Isopropyl Substituents on the Reactivity of N-t-Butyl P-Arylphosphonamidic Chlorides with Isopropylamine and t-Butylamine: Steric Acceleration of Metaphosphonimidate Formation by an Elimination-Addition Mechanism; Contrasting Behaviour of N,N-Dimethyl P-A...
Freeman, Sally,Harger, Martin J.
, p. 1399 - 1406 (2007/10/02)
The two types of phosphonamidic chloride ArP(O)(Cl)NMe2, (5) and ArP(O)(Cl)NHBut (7) have been prepared with Ar=Ph, o-MeC6H4, 2,4,6-Me3C6H2, and 2,4,6-Pri3C6H2.Both types give the expected phosphonic diamide substitution products with PriNH2 and ButNH2 in MeCN, but the two types display contrasting reactivity.With ButNH2 the NMe2 substrates (5) become progressively less reactive as the degree of steric crowding increases, and although the decrease is quite small (70-fold overall) it seems consistent with an associative N2(P)> mechanism.These substrates react >=100 times faster with PriNH2, than with ButNH2 and in PriNH2-ButNH2 competitive experiments they give almost exclusively (>=99percent) the product derived from the less hindered PriNH2.For the NHBut substrates (7) with ButNH2, there is little difference in reactivity between the Ph and o-MeC6H4 compounds, and between the 2,4,6-Me3C6H2 and 2,4,6-Pri3C6H2 compounds, but remarkably the more crowded pair of substrates is the more reactive, by a factor of ca. 100.Also, in competitive experiments these substrates display relatively little preference for reaction with PriNH2.Here a dissociative elimination-addition mechanism, with a metaphosphonimidate intermediate, is seen to be important.A possible explanation of the steric acceleration is advanced.The ability of (7; Ar=Ph) to undergo substitution by elimination-addition makes possible the phosphonylation of unreactive nucleophiles such as ButOH and Pri2NH under mild conditions.
Three-membered Heterocycles,10. - Phosphonohydrazidic Esters by Alkoxide-induced Rearrangement of N-Chlorophosphonic Diamides
Quast, Helmut,Heuschmann, Manfred,Abdel-Rahman, Mohamed O.
, p. 943 - 966 (2007/10/02)
Phosphoric and phosphonic amides 8 are formed from phosphoric and phosphonic chlorides 6 and primary amines 7 in high yields. 2,5-Dimethyl-2,5-hexanediamine (7e) reacts with phenylphosphonic dichloride (6c) to give the perhydro-1,3,2-diazaphosphepine 8h.The amides 8 are converted almost quantitatively into the N-chlorophosphoric and N-chlorophosphonic amides 9 by means of tert-butyl hypochlorite.The N,N'-di-tert-alkyl-N-chlorophosphonic diamides 9 derived from methyl-, tert-butyl-, or phenylphosphonic acid react with methoxide or tertiary alkoxides to afford the phosphonohydrazidic esters 10-13.The methyl ester 10d is also formed from 1,2,3-tri-tert-butyldiazaphosphiridine 3-oxide (14) and methanol. 1H-, 13C-, and 31P-NMR spectra prove that the sharply melting phosphonohydrazidic esters 10-13 exist in solution as two diastereomers with ratios ranging from 9:1 to 6:4.The hydrazidic methyl ester 10d which was investigated as a representative example exhibits a temperature dependent 1H-NMR spectrum.Due to the presence of the tert-alkyl groups, inversion at the tertiary nitrogen atom is slow on each NMR time scale. The independence of the IR spectrum on the concentration shows that the predominant diastereomer of 10d is stabilized by an intramolecular hydrogen bond.The electron impact induced decomposition of the amides 8, N-chloroamides 9, and phosphonohydrazidic esters 10-13 ultimately produces cations which are derived from monomeric metaphosphoric or metaphosphonic acid. 6 N hydrochloric acid first splits off the P-N-tert-butyl group of the methyl ester 10d to give the intermediate 15 which can be isolated or which undergoes further hydrolysis to tert-butylphosphonic acid (17) and tert-butylhydrazine(19).The tert-butyl ester 11d yields the same final products in hot hydrochloric acid.At low temperatures and short reaction times, however, di-tert-butylhydrazine (18) is formed.
