Regio- and stereochemical control in substitution reactions of cyclophosphazenes

Allen, Christopher W.

doi:10.1021/cr00002a002

Cited by 382 publications

(254 citation statements)

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“…The values of these compounds are calculated and listed in Table 3. The δP(spiro)-shifts of the phosphazene bases (3a-3d) are considerably larger than that of the starting compound (2). However, when the Cl atoms exchanged with amine groups, the δP-shifts of the free bases were decreasing.…”

Section: Syntheses and Characterizations The Intermediate Schiff Basmentioning

confidence: 87%

“…Various cyclotriphosphazene derivatives have been prepared from the Cl replacement reactions of N3P3Cl6 with the different nucleophiles [2]. The condensation reactions of N3P3Cl6 with excess monodentate and bidentate ligands resulted in the formation of fully substituted cyclotriphosphazenes [3].…”

Section: Introductionmentioning

confidence: 99%

“…The present study is focused on the preparation of the partly substituted 4-fluorobenzylspirocyclotriphosphazene (2), and the fully substituted phosphazene ligands (3a-3d) for the goal of the preparation of the PILs (4a-4d) of the phosphazene ligands with gentisic acid. In addition, this paper also describes features of spectroscopic crystallographic properties, the evaluation of antimicrobial activity, and DNA interactions of all the compounds.…”

Section: Introductionmentioning

confidence: 99%

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The Syntheses and Structural Characterizations, Antimicrobial Activity and in Vitro Dna Binding of 4-Fluorobenzylspiro(n/O)cyclotriphosphazenes and Their Phosphazenium Salts

Elmas¹,

Okumuş²,

Kılıç³

et al. 2016

J. Turk. Chem. Soc., Sect. A: Chem.

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Abstract:In the present study, the condensation reaction of N3P3Cl6 (1) with sodium 3-(4-fluorobenzylamino)-1-propanoxide gave partly substituted 4-fluorobenzylspirocyclotriphosphazene (2). The Cl replacement reactions of 2 with excess benzylamine, n-hexylamine, n-butylamine and n-propylamine led to the formation of the corresponding 4-fluorobenzylspiro(N/O)tetrabenzylamino (3a), tetrahexylamino (3b), tetrabutylamino (3c) and tetrapropylamino (3d) cyclotriphosphazenes. With the protic ionic liquids (PILs), phosphazenium salts (4a-4d), were obtained from the reactions of the corresponding phosphazene bases (3a-3d) with gentisic acid in dry THF. The structures of all the isolated cyclotriphosphazene derivatives were determined by elemental analyses, FTIR and H} NMR techniques. The crystal structure of 4d was verified by X-ray diffraction analysis. All the compounds were screened for antibacterial and antifungal activities against bacteria and yeast strains. The interactions of the compounds with supercoiled pUC18 plasmid DNA were investigated.

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Section: Syntheses and Characterizations The Intermediate Schiff Basmentioning

confidence: 87%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The Syntheses and Structural Characterizations, Antimicrobial Activity and in Vitro Dna Binding of 4-Fluorobenzylspiro(n/O)cyclotriphosphazenes and Their Phosphazenium Salts

Elmas¹,

Okumuş²,

Kılıç³

et al. 2016

J. Turk. Chem. Soc., Sect. A: Chem.

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“…In the reactions of N 3 P 3 Cl 6 , (1), with mono-functional reagents, such as secondary amines, giving rise to non-geminally di-substituted derivatives, the yields of the trans-isomer are generally substantially larger than that of the cis-isomer and steric effects were invoked to rationalize these observations [39]. However, for the reaction of (9) with NaOR [13,40,41] the reverse behaviour was observed, producing a slight predominance of the cis over trans-isomer, which was rationalized in terms of the co-ordination of the sodium ion by the lone pairs of electrons of the oxygen atom in the P-OR group already present after monosubstitution. A similar sodium ion solvation was also postulated by Brandt and co-workers [27, 42] to account for the exclusive formation of cis-ansa macrocyclic-cyclophosphazene derivatives.…”

Section: This Raises the Further Question To What Extent The Spiro Momentioning

confidence: 99%

Competitive formation of spiro and ansa derivatives in the reactions of tetrafluorobutane-1,4-diol with hexachlorocyclotriphosphazene: A comparison with butane-1,4-diol

et al. 2006

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Beşli, Serap; Coles, Simon J.; Davies, David B.; Eaton, Robert J.; Kılıç, Adem; Shaw, Robert A. (2006) Competitive formation of spiro and ansa derivatives in the reactions of tetrafluorobutane-1,4-diol with hexachlorocyclotriphosphazene: a comparison with butane-1,4-diol. Polyhedron 25 (4): [963][964][965][966][967][968][969][970][971][972][973][974] This is an author-produced version of a paper published in Polyhedron . This version has been peer-reviewed, but does not include the final publisher proof corrections, published layout, or pagination. All articles available through Birkbeck ePrints are protected by intellectual property law, including copyright law. Any use made of the contents should comply with the relevant law. AbstractReaction of hexachlorocyclotriphosphazene, N 3 P 3 Cl 6 (1), in two stoichiometries (1:1.2 and 1:3)with the sodium derivative of the fluorinated diol, 2,2,3,3-tetrafluorobutane-1,4-diol, (2), in THF solution at room temperature afforded six products, whose structures have been characterized by X-ray crystallography and 1 H, 19 F and 31 P NMR spectroscopy: the mono-spiro compound, N 3 P 3 Cl 4 (OCH 2 CF 2 CF 2 CH 2 O), (3), its ansa isomer, (4), a di-spiro derivative N 3 P 3 Cl 2 (OCH 2 CF 2 CF 2 CH 2 O) 2 , (5), its spiro-ansa (6) and non-gem cis bis-ansa (7) isomers and a tri-spiro compound N 3 P 3 (OCH 2 CF 2 CF 2 CH 2 O) 3 , (8). The tri-spiro derivative (8) was also formed in the reaction of the ansa compound (4) with diol (2) in a 1:3 ratio in THF at room temperature.The reactions of (1) with step-wise additions of (2) were also investigated at low temperature (-78 0 C) to give the same range of products as at room temperature. The results of all reactions are compared with previous work on the reactions of (1) with butane-1,4-diol/pyridine mixtures and with the reaction of hexafluorocyclotriphosphazene, N 3 P 3 F 6 (9), with the silyl derivative of the diol (2), (Me 3 SiOCH 2 CF 2 ) 2 , in a 1:0.4 mole ratio in the same solvent, THF.3

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“…The balance of o and IT effects is different from that in carbon-based molecules and is an important topic of this paper. Apart from their specific applications, the results obtained may also help in the elucidation of the directional effects found in the substitution reactions of phosphazenes (1).…”

Section: Introductionmentioning

confidence: 98%

The molecular and electronic structure of 1-pyrazolylphosphazenes

Gallicano¹,

Paddock²,

Rettig³

et al. 1992

Can. J. Chem.

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KEITH D. GALLICANO, NORMAN L. PADDOCK, STEVEN J. R E~G , and JAMES TROTIFR. Can. J. Chem. 70, 1855 (1992). The nature of the interactions between pyrazolyl and phosphazene rings has been investigated through the study of the structures of bis(1 -pyrazolyl)methane, CH2(H2pz),, 1, bis[l-(3,5-dimethylpyrazolyl)]methane, CH,(Me,pz),, 2, the pyrazolylphosphazenes N,p,(Me,p~)~, 3, N4P4(H2pz),, 4, and N,P,(Me2pz),, 5, and the partially substituted gem-N,P,ph,(Me,p~)~, 6. Crystal data are as follows: 1, orthorhombic, P2'2'2,, a = 7.997(2), b = 9.287(2), c = reflections. Interpretation of the structures through iterative extended Hiickel calculations shows that conjugative interactions lead to a quinonoid deformation of the pyrazole ring, similar to that in bis(1-pyrazoly1)carbonyl. a-Electron transfer to the phosphazene ring, facilitated by the use of acceptor d orbitals on phosphorus, is accompanied by a synergic a transfer to the pyrazole ring. The pyrazolyl group acts both as a strongly electronegative group and as a good potential donor. The calculations account satisfactorily for the bond lengths in the pyrazolyl group, the large bond angles at nitrogen in 4 and 5, the bond length inequalities in the phosphazene ring of 6, and the reactivity of the pyrazolylphosphazenes. [Traduit par la redaction]

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Regio- and stereochemical control in substitution reactions of cyclophosphazenes

Cited by 382 publications

References 58 publications

The Syntheses and Structural Characterizations, Antimicrobial Activity and in Vitro Dna Binding of 4-Fluorobenzylspiro(n/O)cyclotriphosphazenes and Their Phosphazenium Salts

The Syntheses and Structural Characterizations, Antimicrobial Activity and in Vitro Dna Binding of 4-Fluorobenzylspiro(n/O)cyclotriphosphazenes and Their Phosphazenium Salts

Competitive formation of spiro and ansa derivatives in the reactions of tetrafluorobutane-1,4-diol with hexachlorocyclotriphosphazene: A comparison with butane-1,4-diol

The molecular and electronic structure of 1-pyrazolylphosphazenes

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