Reactions Of Hexachlorocyclotriphosphazatriene Research Articles

Design, synthesis and spectral characterization of cyclotriphosphazenes including heterocyclic rings

In this study, described the synthesis on a cyclotriphosphazene containing the spirocyclic 2,2′-dioxybiphenyl group and 2-mercapto-1-methylimidazole (methimazole) or 2-mercaptothiazoline (MTZ) moieties. These spiro(in difunctional ligands, both ends are bound to the same phosphorus) cyclotriphosphazene derivatives (6, 7a) were synthesized in two steps. In first step; mono substituted phosphazene compounds 2,4,4,6,6-pentachloro-2-(2-mercapto-1-methylimidazolyl) cyclo2λ5, 4λ5, 6λ5, triphosphazatriene; N4P3Cl5C3S2H5 (4), and 2,4,4,6,6-pentachloro-2-(2-mercapto-tiyazolinyl) cyclo2λ5, 4λ5, 6λ5, triphosphazatriene; N4P3Cl5C4S2H4 (5)] were prepared from the reaction of hexachlorocyclotriphosphazatriene (trimer, N3P3Cl6, 1), with methimazole (2) or MTZ (3) in tetrahydrofurane (THF) in the presence of metallic sodium under an argon atmosphere.In second step; monospiro2-mercaptothiazolinyl (7a) and dispiro2-mercapto-1-methylimidazolyl sübstituted (6) phosphazene derivatives were obtained from the reactions of 4 and 5 with 2,2′-dihydroxybiphenyl (8) in acetone in the presence of potassium carbonate (K2CO3). Structural characterizations of all obtained compounds were made using by elemental analysis, FT-IR, 1H, 13C and 31P NMR spectroscopies. Compounds 5–7a are reported for the first time in this study.

Synthesis, structural, and stereogenic characterizations of new trispirocyclotriphosphazenes

AbstractIn this study, trispirophosphazenes containing biphenyl‐2,2′‐dioxy and ferrocenyldiamino groups were synthesized to investigate their stereogenic and structural properties. For this purpose, monospiro (1) and trans/cis‐dispiro (2and3) cyclotriphosphazenes were obtained from the reactions of hexachlorocyclotriphosphazatriene (N3P3Cl6; trimer;HCCP) withN‐ethyl‐N′‐ferrocenylmethyl‐ethylenediamine. Subsequently, bis(biphenyl‐2,2′‐dioxy)‐substituted ferrocenylphosphazene (4) was prepared from the reaction of an equimolar amount of monoferroceylphosphazene (1) with two equimolar amounts of dipotassium biphenyl‐2,2′‐dioxide. Reactions of equimolar amounts of2and3with equimolar amounts of dipotassium biphenyl‐2,2′‐dioxide yielded trans‐(5) and cis‐(6) trispirophosphazenes, respectively. Characterizations of all trispiro compounds were made using1H,13C, and31P NMR spectra. In addition, trispirophosphazenes5and6have two equivalent stereogenic P‐centers.Trans‐5andcis‐6are expected to exist in racemate and meso forms. The molecular and crystal structures of the two phosphazenes (4and5) were clarified by single‐crystal X‐ray crystallography. Also, since the absolute configuration of one enantiomer of5is found to be RR, the other must be SS.

Reactions of cyclochlorotriphosphazatriene with 2-mercaptoethanol. Calorimetric and spectroscopic investigations of the derived products

The reactions of hexachlorocyclotriphosphazatriene, N3P3Cl6 (1) with 2-mercaptoethanol, 2-HS-CH2-CH2-OH (2), in (1:1, 1:2 and 1:3) mole ratios, in excess of NaH, in THF and diethylether solutions yield a total of 6 novel products: one mono spiro, N3P3Cl4[O-CH2-CH2-S] (3); one mono-substituted open chain, N3P3Cl5[S-CH2-CH2-OH] (4); one dispiro, N3P3Cl2[O-CH2-CH2-S]2 (5); one tri-substituted open chain, N3P3Cl3[S-CH2-CH2-OH]3 (6); one tris-spiro, N3P3[O-CH2-CH2-S]3 (7) and one disubstituted open chain, N3P3Cl4[S-CH2-CH2-OH]2 (8) derivatives. The spiro products (3, 5 and 7) are formed as the major products in this system and all of the synthesized compounds are found to be stable at room temperature. The structures of the derived compounds were elucidated by elemental analysis, TLC-MS, 31P and 1H NMR spectral data. For evaluation of melting behavior of derivatives (6) and (7), thermal transition peaks and their corresponding enthalpies were determined via DSC technique.

The reaction of hexachlorocyclotriphosphazatriene with P-aminophenol

GRAPHICAL ABSTRACT

Nucleophilic substitution reactions of adamantane derivatives with cyclophosphazenes

In the present work, the reactions of cyclophosphazenes with adamantane derivatives have been investigated. The geminal-bis- (3) and geminal-tetrakis- (4) compounds have been synthesized from the reaction of hexachloro-cyclotriphosphazatriene with 1-adamantanethiol. 2-(1′-Adamantylamino)-2,4,4,6,6-pentachlorocyclotriphosphazatriene (5) has been obtained from the reaction of hexachloro-cyclotriphosphazatriene with 1-adamantylamine. Furthermore, mono- (6) and non-geminal bis-substituted 1-adamantylamino cyclotetraphosphazene compounds 7 (2-trans-6) and 8 (2-cis-4) have been isolated from the reaction of octachlorocyclotetraphosphazatetraene with 1-adamantylamine. All compounds have been fully characterized by elemental analysis, mass, 1H and 31P NMR spectroscopies. Molecular and crystal structures of 3 and 5–7 have been determined by X-ray crystallography. Compounds 3 and 4 are reported as the first examples for adamantylthio derivatives of cyclophosphazene in the literature. Compounds 5–8 have been also reported for the first time.

Synthesis and the Spectral Investigations of Spiro, Ansa and Bridged Derivatives of Cyclochlorotriphosphazenes

The reactions of hexachlorocyclotriphosphazatriene, N3P3Cl6 (1) with 2,2-dimethylpropane-1,3-diol yield 9 new cyclophosphazene derivatives. One monospiro, N3P3Cl4[(OCH2)2-CMe2], dispiro, N3P3Cl2[(OCH2)2-CMe2]2 and tris-spiro N3P3[(OCH2)2-CMe2]3 derivatives. An ansa, N3P3Cl4[(OCH2)2-CMe2], and a spiro-ansa, N3P3Cl2[(OCH2)2-CMe2]2 isomers. One dangling, N3P3Cl5[(OCH2)2-CMe2OH], one singly-bridged, N3P3Cl5[(OCH2)2-CMe2] N3P3Cl5, one doubly-bridged, N3P3Cl4[(OCH2)2-CMe2]2N3P3Cl4, and one triple-bridged compounds, N3P3Cl3[(OCH2)2-CMe2]2N3P3Cl3 were also isolated. Product types and relative yields were compared with those arising from propane-1,3-diol. The yields of the spiro, ansa and the bridged products from the reactions of the dimethylpropane-diol system seem to be considerably enhanced relative to those of its unmethylated analogue. The structures of the compounds were determined by using the data obtained from 31P, 1H and 13C N.M.R.

Phosphorus−Nitrogen Compounds. 21. Syntheses, Structural Investigations, Biological Activities, and DNA Interactions of New N/O Spirocyclic Phosphazene Derivatives. The NMR Behaviors of Chiral Phosphazenes with Stereogenic Centers upon the Addition of Chiral Solvating Agents

The reactions of hexachlorocyclotriphosphazatriene, N(3)P(3)Cl(6), with N/O-donor-type N-alkyl (or aryl)-o-hydroxybenzylamines (1a-1e) produce mono- (2a-2e), di- (3a-3d), and tri- (4a and 4b) spirocyclic phosphazenes. The tetrapyrrolidino monospirocyclic phosphazenes (2f-2i) are prepared from the reactions of partly substituted compounds (2a-2d) with excess pyrrolidine. The dispirodipyrrolidinophosphazenes (3e-3h) and trispirophosphazenes (3i-3k) are obtained from the reactions of trans-dispirophosphazenes with excess pyrrolidine and sodium (3-amino-1-propanoxide), respectively. Compounds 3a-3d have cis and trans geometric isomers. Only the trans isomers of these compounds are isolated. Compounds 3a-3h have two stereogenic P atoms. They are expected to be in cis (meso) and trans (racemic) geometric isomers. In the trans trispiro compounds (3i-3k), there are three stereogenic P atoms. They are expected to be in racemic mixtures. The stereogenic properties of 3a-3k are confirmed by (31)P NMR spectroscopy upon the addition of the chiral solvating agent; (S)-(+)-2,2,2-trifluoro-1-(9'-anthryl)ethanol. The molecular structures of 3i-3k, 4a, and 4b look similar to a propeller, where the chemical environment of one P atom is different from that of others. Additionally, 4a and 4b are also expected to exist as cis-trans-trans and cis-cis-cis geometric isomers, but both of them are found to be in cis-trans-trans geometries. The solid-state structures of 2a, 2e, 2f, 3e, and 3f are determined by X-ray crystallography. The compounds 2f-2i, 3e-3i, and 3k are screened for antibacterial activity against gram-positive and gram-negative bacteria and for antifungal activity against yeast strains. These compounds (except 3f) have shown a strong affinity against most of the bacteria. Minimum inhibitory concentrations (MIC) are determined for 2f-2i, 3e-3i, and 3k. DNA binding and the nature of interaction with pUC18 plasmid DNA are studied. The compounds 2f-2i, 3e-3i, and 3k induce changes on the DNA mobility. The prevention of BamHI and HindIII digestion (except 2g) with compounds indicates that the compounds bind with nucleotides in DNA.

The investigation of structural and thermosensitive properties of new phosphazene derivative bearing glycol and aminoalcohol

Three isomers (nongeminal cis-2,4,6 ( 2); nongeminal trans-2,4,6 ( 3); geminal 2,2,4 ( 4)) were isolated from the reaction of hexachlorocyclotriphosphazatriene (trimer) ( 1) with diethylene glycol monobutyl ether (DEGBE). The substitution reactions of cis-tris isomer ( 2) with 3-amino-1-propanol were investigated under different solutions conditions to provide amphiphilic phosphazene ( 5). All of compounds were characterized by using elemental analysis, 31P NMR and mass spectroscopies. Thermosensitive properties of compound 5 were studied. The compound 5 is soluble in both water and organic media. This indicates that compound 5 is an amphiphilic molecule. Concentration-dependent LCST (Lower Critical Solution Temperature) behavior of 5 was measured in water. Compound 5 exhibited a reversible and thermosensitive phase transition in aqueous medium, from soluble to insoluble states. Compound 5 showed LCST at 37 °C (for 7 wt.% concentration) which is near to body temperature.

The investigation of structural and thermosensitive properties of new phosphazene derivatives bearing glycol and amino acid

In this study, hexachlorocyclotriphosphazene, N(3)P(3)Cl(6) (cylotriphosphazene), was reacted with hydrophilic and hydrophobic groups to synthesize amphiphilic phosphazene derivatives (4-12). Cylotriphosphazene was reacted triethylene glycol monomethyl ether (TEGME), dipropylene glycol monomethyl ether (DPGME), diethylene glycol monobutyl ether (DEGBE), (1 : 3 mole proportion) in the presence of sodium hydride and using tetrahydrofuran (THF) as solvent at -60 °C. Three isomers (nongeminal cis-2,4,6 (1a-3a); nongeminal trans-2,4,6 (1b-3b); geminal 2,2,4 (1c-3c)) were isolated from the reaction of hexachlorocyclotriphosphazatriene (trimer) (1) with TEGME, DPGME and DEGBE. The substitution reactions of cis-tris isomers (1a-3a) with 4-amino butyric acid, 5-amino valeric acid and 6-amino hexanoic acid were separately done to provide amphiphilic phosphazenes (4-12). All compounds were characterized by using elemental analysis, (31)P NMR and mass spectroscopy. Thermosensitive properties of compounds were studied. The compounds (4-12) were soluble in both water and organic media that shows they are amphiphilic molecules. Concentration-dependent LCST (Lower Critical Solution Temperature) behaviours of new compounds (4-12) were measured in water. Compounds 7, 9, 11 and 12 exhibited a reversible and thermosensitive phase transition in aqueous medium, from soluble to insoluble states.

Phosphorus−Nitrogen Compounds. 18. Syntheses, Stereogenic Properties, Structural and Electrochemical Investigations, Biological Activities, and DNA Interactions of New Spirocyclic Mono- and Bisferrocenylphosphazene Derivatives

The reactions of hexachlorocyclotriphosphazatriene, N(3)P(3)Cl(6), with mono- (1 and 2) and bisferrocenyldiamines (3-5), FcCH(2)NH(CH(2))(n)NHR(1) (R(1) = H or FcCH(2)-), produce mono- (6 and 7) and spirocyclic bisferrocenylphosphazenes (8-10). The fully substituted phosphazenes (11-15 and 18-21) are obtained from the reactions of corresponding partly substituted phosphazenes (6-10) with excess pyrrolidine and NH(2)(CH(2))(3)ONa, respectively. The reactions of 6 with 1-aza-12-crown-4 afford geminal (16) and tris (17) crown ether-substituted phosphazenes. The structural investigations of the compounds have been verified by elemental analyses, mass spectrometry, Fourier transform IR, (1)H, (13)C, and (31)P NMR, and DEPT, COSY, HETCOR, and HMBC techniques. The crystal structures of 7, 10, 11, and 15 have been determined by X-ray crystallography. In 16 and 17, there are one and two stereogenic P atoms, respectively, and they are expected to be in enantiomeric mixtures. The structures of 18-21 look similar to a propeller. In 20 and 21, there are two stereogenic P atoms, and they exist as cis (meso; 20a and 21a) and trans (racemic; 20b and 21b) geometric isomers, according to the chiral solvating agent (S)-(+)-2,2,2-trifluoro-1-(9'-anthryl)ethanol experiments. Moreover, the compounds 18 and 19 have three stereogenic P atoms, and they exist as enantiomeric mixtures. Cyclic voltammetric investigations of compounds 6-21a reveal that ferrocene redox centers undergo oxidation concurrently at the same potential with basically reversible peaks, and these compounds appear to be quite robust electrochemically. The compounds 11-15 have been screened for antibacterial activity against gram positive and gram negative bacteria and for antifungal activity against yeast strains.The compounds 11, 12, 14, and 15 are evaluated for antituberculosis activity against reference strain Mycobacterium tuberculosis H37Rv (ATCC 27294). Interactions between compounds 11-15 and pBR322 plasmid DNA are studied by agarose gel electrophoresis. These compounds induce conformational changes in the DNA helix.

Structural and fluorescence properties of phenolphthalein bridged cyclotriphosphazatrienes

This study dealt with the reactions of hexachlorocyclotriphosphazatriene, N 3P 3Cl 6 (trimer) ( 1) with phenolphthalein ( 2) to give the phenolphthalein bridged compounds 3, 4 and 5. The phenolphthalein bridged cyclotriphosphazatriene derivatives are reported for the first time. The new compounds ( 3– 5) are characterized by elemental analysis, mass spectrometry, UV–vis, FT-IR, 1H, 31P NMR and fluorescence spectroscopy. The more bridged phenolphthalein groups show the higher intensity of the absorption bands in the UV–vis spectra. Fluorescence spectrum of compound 3 shows a small band in the lower spectral range, while the spectra of compounds 4 and 5 show more intense and a band in higher spectral range.

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.

Phosphorus−Nitrogen Compounds. 14. Synthesis, Stereogenism, and Structural Investigations of Novel N/O Spirocyclic Phosphazene Derivatives

The reactions of hexachlorocyclotriphosphazatriene, N3P3Cl6, with N/O donor-type N-alkyl-o-hydroxybenzyl- and o-hydroxynaphthylamines result in novel mono- (3a, 4a and 4b), di- (5a and 5b), and tri- (3b, 6a, and 6b) spirocyclic phosphazene derivatives. The tetrakis-pyrrolidinophosphazene, 3b, has been obtained from the reaction of partly substituted compound 3a with the excess pyrrolidine in tetrahydrofuran. The relationship between the endocyclic NPN (alpha) and exocyclic NPO (alpha') bond angles of the analogous spirocyclic phosphazenes with the deltaP shifts of NPO phosphorus atoms have been presented. It was observed that there is a linearity between alpha angles and deltaP shifts, while no linear relationship has been observed for alpha' angles. In addition, we have found the correlation between Delta(P-N) and deltaNPO shifts, which implies a linear relationship. Delta(P-N)=(a-b), where a and b are the average lengths of two adjacent P-N bonds. The structural investigations of all of the compounds have been made by elemental analyses; mass spectrometry; Fourier transform infrared spectroscopy; one-dimensional 1H, 13C, and 31P NMR; distortionless enhancement by polarization transfer; and two-dimensional correlation spectroscopy, heteronuclear shift correlation, and heteronuclear multiple-bond correlation homo- and heteronuclear correlation techniques. The solid-state structures of 3a, 4a, 4b, and 5a have been determined by X-ray crystallographic techniques. The asymmetric units of compounds 3a and 4a contain two independent molecules, and 3a has strong intermolecular N-H...N hydrogen bonds linking three phosphazene rings. The molecular structure of 6a looks like a propeller where the chemical environment of P1 is different from that of P2 and P3. On the other hand, compounds 5a and 5b are expected to exist as cis- or trans-geometric isomers and to be in cis (meso) or trans (racemic) configurations. The crystallographic and preliminary chiral solvating agents results show that both of them are trans (racemic). In addition, 6a and 6b are also expected to exist as cis-trans-trans- and cis-cis-cis-geometric isomers; both of them are found to be in cis-trans-trans geometries. According to the two-dimensional spectroscopic data, the possible conformations of 3a and 4a in CDCl3 are the same with the solid-state structures.

Novel phosphazene derivatives: Synthesis, anisochronism and structural investigations of mono- and ditopic spiro-crypta phosphazenes

The reactions of hexachlorocyclotriphosphazatriene, N 3P 3Cl 6, with N 2O 2-donor type coronands (diaza-crown ethers) 1– 3 afford novel monotopic 4– 7 and ditopic 8– 10 spiro-crypta phosphazenes, respectively. It has been observed that the reactions of N 3P 3Cl 6 with 1 equivalent amount of coronands 1– 3 yield only monotopic spiro-derivatives, while three equivalent amount of coronands 2 and 3 give dominantly ditopic dispiro-crypta-phosphazene skeletons. On the other hand, the 31P NMR spectrum of 8 indicates that the ditopic spiro-ansa phosphazene 10 is present besides the ditopic dispiro derivative 8. Unexpectedly, the reaction of 6 with excess amount of pyrrolidine leads to the formation of geminal product 7. The 31P NMR spectra of 4, 5, 6 and 10 indicate that all of these compounds have anisochronism. The structures of 5, 8 and 9 have been determined by X-ray crystallography. The relative radii of macrocyclic hole sizes of 5, 8 and 9 are calculated from the crystallographic results. The relationships between the exocyclic NPN and endocyclic NPN bond angles of the analogous compounds with δP-shifts of NPN phosphorus atoms have been discussed. Thus, sums of the bond angles around the nitrogen atoms are in the range of [342.7(2)°–354.4(2)°], showing that the nitrogen atoms have pyramidal configurations. The pyramidal configuration gives rise to stereogenic properties. The salient spectroscopic features [FTIR, 1H, 13C, 31P NMR, HETCOR (for 5 and 7) and MS] of all the compounds are presented.

The Reactions of Hexachlorocyclotriphosphazatriene with Ligands Including Mercapto Groups

In this work, the reactions of hexachlorocyclotriphosphazatriene (trimer), N 3 P 3 Cl 6 1, with 2-mercapto-1-methylimidazole (methimazole) 2, 2-mercaptopyrimidine 3, and 2-mercaptopyridine 4 were discussed. Mono- (5) and pentasubstituted (6) phosphazenes were obtained from the reaction of 1 with 2-mercapto-1-methylimidazole. Both mono- (7) and disubstituted geminal (8) phosphazenes were obtained from the reaction of 1 with 2-mercaptopyrimidine. But phoshazene or any phosphorus compound could not be isolated from the reaction of 1 with 2-mercaptopyridine.

The reactions of hexachlorocyclotriphosphazatriene with pyridine derivatives

AbstractThe reactions of hexachlorocyclotripho‐sphazatriene, N3P3Cl6 (1), with 2‐hydroxypyridine (2), 2‐aminopyridine (3), 2‐amino‐6‐methyl‐pyridine (4), and 2‐hydroxy‐4‐methylquinoline (5) have been investigated. The products were identified by elemental analyses, IR, 1H, 13C, and 31P NMR spectroscopy. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:57–60, 2006; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20185

Synthesis of 2-Aminomethylpyridine Derivatives of Phosphazenes

Novel cyclophosphazenes (5-8) with pyridine side groups have been synthesized by the reactions of hexachlorocyclotriphosphazatriene, N 3 P 3 Cl 6 (1), with 2-amino-3-methylpyridine (2), 2-amino-4-methylpyridine (3) and 2-amino-5-methylpyridine (4). Di- and monosubstituted products (5, 6) were obtained from the reaction of 1 with 2 and 3, respectively. Both di- and monosubstituted products (7, 8) were obtained from 2-amino-5-methylpyridine with 1. The structures of the compounds (5-8) were defined by IR, 1 H, 13 C and 31 P NMR spectroscopy and elemental analyses.

ChemInform Abstract: Unusual Products in the Reactions of Hexachlorocyclotriphosphazatriene with Sodium Aryloxides.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Unusual products in the reactions of hexachlorocyclotriphosphazatriene with sodium aryloxides

Reactions of hexachlorocyclotriphosphazatriene, N3P3Cl6 1, with sodium aryloxides have been studied. Compound 1 was found to react by the nucleophilic substitution pathway to yield monocyclophosphazenes [N3P3Cl6(OC6H2Bu13-2,4,6) 5 and N3P3Cl4(OC6H2Me-4-Bu12-2,6)2 6] and bi(cyclophosphazenes) ([Cl5N3P3-P3N3Cl4(OC6H3Bu12-2,6)] 7 and [N3P3(OC6H3Bu12-2,6)5]2 8). The unusual bi(cyclophosphazenes) 7 and 8 are the first examples of two cyclotriphosphazene rings linked by a P(SINGLE BOND)P bond [2.193 (2) Å], which have been obtained by reacting 1 with ArONa. The structures of compounds 5–8 are ascertained by elemental analyses, 1H-, 31P-13C-NMR, IR, and MS spectra. The molecular structure of monocyclic-phosphazene 5 was determined by X-ray diffraction techniques for further structural assignment. It crystallizes in the monoclinic space group P21/m with a = 6.144(2), b = 17.079(9), c = 13.181(9) Å, β = 92.79(7), and Z = 2, R = 0.074. Compound 5 is on a crystallographic mirror plane, and there is only a half molecule in the asymmetric unit. © 1996 John Wiley & Sons, Inc.

ChemInform Abstract: Reaction of Hexachlorocyclotriphosphazatriene with Benzoic Acid in the Presence of Triethylamine.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.