Hanife İbişoğlu

Structural investigations of phosphorus–nitrogen compounds. 7. Relationships between physical properties, electron densities, reaction mechanisms and hydrogen-bonding motifs of N3P3Cl(6 − n)(NHBut)n derivatives

A series of compounds of the N3P3Cl(6 - n)(NHBu(t))n family (where n = 0, 1, 2, 4 and 6) are presented, and their molecular parameters are related to trends in physical properties, which provides insight into a potential reaction mechanism for nucleophilic substitution. The crystal structures of N3P3Cl5(NHBu(t)) and N3P3Cl2(NHBu(t))4 have been determined at 120 K, and those of N3P3Cl6 and N3P3Cl4(NHBu(t))2 have been redetermined at 120 K. These are compared with the known structure of N3P3(NHBu(t))6 studied at 150 K. Trends in molecular parameters [phosphazene ring, P-Cl and P-N(HBu(t)) distances, PCl2 angles, and endo- and exocyclic phosphazene ring parameters] across the series are observed. Hydrogen-bonding motifs are identified, characterized and compared. Both the molecular and the hydrogen-bonding parameters are related to the electron distribution in bonds and the derived basicities of the cyclophosphazene series of compounds. These findings provide evidence for a proposed mechanism for nucleophilic substitution at a phosphorus site bearing a PCl(NHBu(t)) group.

Synthesis of a new class of fused cyclotetraphosphazene ring systems.

Octachlorocyclotetraphosphazene (1) was reacted with butylamines [n-butyl, i-butyl, sec-butyl, and t-butyl] in a 1:0.8 mol ratio in THF to obtain cyclotetraphosphazenes bearing a P-NH group, N4P4Cl7(NHR) [R = n-butyl (2a), i-butyl (2b), sec-butyl (2c), t-butyl (2d)](2a-d). The cyclotetraphosphazene derivatives 2a, 2b, and 2c were treated with sodium hydride giving rise to a new type of cyclophosphazene compounds (P8N8 ring) consisting of three fused tetramer rings (3a-c). Whereas reaction of sodium hydride with the t-butylaminocyclophosphazene derivative (2d) gave a P-O-P bridged compound (4) presumably as a result of hydrolysis reaction associated with moisture in the solvent. It is likely that the 16-membered cyclooctaphosphazene derivatives (3a-c) are formed by a proton abstraction/chloride ion elimination, intramolecular nucleophilic attack, ring opening and intermolecular condensation processes, respectively.

Dimorphism in 4,4,6,6-tetrachloro-2,2-(2,2-dimethylpropane-1,3-dioxy)cyclotriphosphazene and 6,6-dichloro-2,2:4,4-bis(2,2-dimethylpropane-1,3-dioxy)cyclotriphosphazene.

A second, polymorphic, form of the previously reported compound 4,4,6,6-tetrachloro-2,2-(2,2-dimethylpropane-1,3-dioxy)cyclotriphosphazene, C(5)H(10)Cl(4)N(3)O(2)P(3), is now reported. The molecular structures of these two compounds are similar, aside from minor conformational differences. However, the compounds crystallize in two different space groups and exhibit quite different crystal structure assemblies. Additionally, 6,6-dichloro-2,2:4,4-bis(2,2-dimethylpropane-1,3-dioxy)cyclotriphosphazene, C(10)H(20)Cl(2)N(3)O(4)P(3), is shown to exhibit two different conformational polymorphs when crystallized from different solvent mixtures. The alpha form crystallizes in the space group Pnma with the molecular structure lying on a mirror plane (symmetry code: x, -y + {1/2}, z), whilst the beta form is in the space group C2/c with the molecular structure lying on a twofold axis (symmetry code: -x, y, -z + {3/2}). The difference between the two molecular structures is in the conformation of the spiro-ring substituents with respect to the phosphazene ring. The resulting crystal structures give rise to differing packing motifs.

The reaction of hexachlorocyclotriphosphazatriene with bromoneopentyl glycol

- In the present work, novel phosphazene derivatives, monospiro- (1), dispiro- (2), and trispiro-2,2-bis(bromomethyl)-1,3-propandioxy (3) substituted cyclotriphosphazatrienes were synthesized with the reaction of bromoneopentyl glycol(2,2-bis(bromomethyl)-1,3 -propandiol) with hexachlorocyclotriphosphazatriene, N 3 P 3 Cl 6 . The structures of the compounds were determined by elemental analysis, mass spectrometry, 1 H and 31 P NMR spectroscopy. The thermal properties of the compounds (1), (2) and (3) were investigated by DSC and TGA.

4,4,6,6‐Tetrachloro‐2‐[(2,4‐dimethylphenyl)sulfanyl]‐N‐[4‐(2,2,4,4‐tetrachloro‐1,3,5,7,11‐pentaaza‐2λ5,4λ5,6λ5‐triphosphaspiro[5.5]undeca‐1,3,5‐trien‐7‐yl)butyl]‐1,3,5,2λ5,4λ5,6λ5‐triazatriphosphinin‐2‐amine

Reaction of the spermidine-bridged cyclophosphazene compound (N3P3Cl5)spd(N3P3Cl4) (spd = spermidine residue) with 2,4-dimethylthiophenol results in substitution of the P-Cl bond at the bridgehead >P(NHR)Cl group to give the title compound, C15H25Cl8N9P6S. An N-H...N hydrogen bond helps to establish the packing.

Conformational polymorphism in a chiral spiro-cis-ansa-bridged cyclo­triphosphazene derivative

The reaction of spermidine with 2,2,4,4-tetrachloro-6,6-diphenylcyclotriphosphazene produces a mixture of products of which one of the fractions is a spiro-cis-ansa derivative, namely 12-chloro-14,14-diphenyl-2,6,11,13,15,16-hexaaza-1,12-diphosphatricyclo[10.3.1.0(1,6)]hexadeca-12,14-diene, C19H26ClN6P3. Recrystallization of this fraction from different solvents results in the formation of two different crystalline forms. The rod morphology formed in dichloromethane-n-hexane (1:1) produces a triclinic structure with three molecules in the asymmetric unit. These three molecules adopt different conformations as a result of two NH groups flipping in an ansa-bridged ring system. The plate morphology crystals, grown in dichloromethane-n-hexane-ethyl acetate (1:1:1), produce a C-centred monoclinic structure that adopts a conformation that is essentially the same as one of the forms in the triclinic structure.

The diverse behaviour of the P-Cl bonds in the spiro-cis-ansa spermidine derivative cyclotriphosphazene towards mono-functional nucleophilic reagents

A number of new spiro-ansa spermidine derivative cyclotriphosphazenes (2-10) is synthesized in order to provide insight into the reaction mechanism for nucleophilic substitution. The structures of the compounds were determined by elemental analysis, mass (MS), (1)H, (19)F (for 9) and (31)P NMR spectroscopies. Compounds (2-8) and 9, 10 can be formed by a proton abstraction-chloride elimination and both the S(N)(1) and S(N)(2) reaction mechanisms, respectively.

The reaction of hexachlorocyclotriphosphazatriene with P-aminophenol

GRAPHICAL ABSTRACT ABSTRACT The reaction of hexachlorocyclotriphosphazatriene (1) with p-aminophenol (2) produced two new products: the open chain compound N3P3Cl5(NHC6H4OH) (3), and the bridged compound N3P3Cl5(NHC6H4O)N3P3Cl5(4). The compounds 3 and 4 were separated and characterized by elemental analysis, massspectrometry and NMR spectroscopy. The molecular structures of compounds 3 and 4 were determined by X-ray crystallography. Compound 3 is the first example of cyclotriphosphazene including (p-hydroxyphenyl) amino group and compound 4 was the first example of the N-substituted p-aminophenoxy group with cyclotriphosphazene.