The reaction of N,N-spiro bridged octachlorobis(cyclotriphosphazene) with 1,3-propanediol: Comparison with 1,2-ethanediol (original) (raw)
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The first substitution reactions of N,N-spiro bridged octachlorobiscyclotriphosphazene
Polyhedron, 2015
The reaction of the N,N-spiro bridged octachlorobiscyclotriphosphazene {N 3 P 3 Cl 4 [br-N(CH 2) 5 CH 3 ] 2 N 3 P 3 Cl 4 } (1), in three (1:1 stoichiometries, 1:2 and 1:3.5), with the sodium derivative of 1,2-ethanediol in THF solution at room temperature produced five products, the mono-spiro derivative {N 3 P 3 Cl 2 [O(CH 2) 2 O] [br-N(CH 2) 5 CH 3 ] 2 N 3 P 3 Cl 4 } (2), cis and trans di-spiro derivatives {N 3 P 3 Cl 2 [O(CH 2) 2 O][br-N(CH 2) 5 CH 3 ] 2 [O(CH 2) 2 O]N 3 P 3 Cl 2 } (3, 5), the ipsilateral di-spiro isomer {N 3 P 3 [O(CH 2) 2 O] 2 [br-N(CH 2) 5 CH 3 ] 2 N 3 P 3 Cl 4 } (4) and the tetra-spiro derivative {N 3 P 3 [O(CH 2) 2 O] 2 [br-N(CH 2) 5 CH 3 ] 2 [O(CH 2) 2 O] 2 N 3 P 3 }, (6), whose structures have been characterized by elemental analysis, mass spectrometry, 1 H and 31 P NMR spectroscopy and X-ray crystallography. The nucleophilic substitution reactions of the N,N-spiro bridged octachlorobiscyclotriphosphazene were investigated for the first time and X-ray crystallographic studies of all the structures (2-6) have been reported as the first examples of derivatives of this new class of ring system in the literature.
Polyhedron, 2009
Reaction of hexachlorocyclotriphosphazene, N 3 P 3 Cl 6 (1), with the sodium derivative of the fluorinated diol, 2,2,3,3,4,4,5,5-octafluorohexane-1,6-diol, (2), in THF solution at room temperature afforded five products, whose structures have been characterised by 1 (6). X-ray crystallographic studies confirmed the structures of the ansa compound , the double-bridged compound (5-anti) and the first example of a triple-bridged cyclotriphosphazene derivative (6). The results were also compared with those for reactions of (1) with analogous fluorinated shorter diols (1,4-butane-and 1,5-pentane-diols). It is found that on increasing the chain length of the diol, there is a decrease in the relative proportion of intramolecular reactions giving spiro and ansa derivatives and an increase in the amount of bridged cyclophosphazene derivatives via intermolecular reactions.
Inorganica Chimica Acta, 2008
Reactions of dilithiated diols [HO(CH 2 CH 2 O) n+1 H, n = 1, 2 and 3] with 3,5-bis(N,N-dimethylamino)-1,1-dichlorodicarbaphosphazene (1) in THF have been carried out to afford the first examples of lariat ether type cyclocarbaphosphazene derivatives (C 4 H 8 O 3 PN) (Me 2 NCN) 2 (2), (C 6 H 12 O 4 PN)(Me 2 NCN) 2 (3) and (C 8 H 16 O 5 PN)(Me 2 NCN) 2 (4). Reaction of the tetrasodium salt of pentaerythritol with 1 and bis(morpholino)dichlorodicarbaphosphazene (1a) yielded the first examples of pentaerythritoxy-bridged cyclodicarbaphosphatriazenes [(Me 2 NCN) 2 PN(OCH 2) 2 ] 2 C (5) and [(OC 4 H 8 NCN) 2 PN(OCH 2) 2 ] 2 C (6). The spectral and structural properties of these compounds are determined and compared with spirocyclic 1,3-propanedioxy derivative of 1 (7) and analogous compounds of cyclophosphazenes. The crystal structures of the compounds 4, 5 and 7 are reported. In addition, complexation studies of compounds 3 and 4 with Na I , K I , Ag I and Cu II ions were carried out by conductance measurements. The studies indicate mostly 1:1 complex formation between the metal ions and lariat ether type cyclocarbaphosphazene derivatives.
Sakarya University Journal of Science, 2019
In this study, the reactions of 2-(2-hydroxyethyl) thiophene (2) and benzyl alcohol (3) with pentanedioxycyclochlorotriphosphazene (1) and pentanedioxy triple-bridged cylochlorotriphosphazene (6) were studied. The novel cyclotriphosphazene compounds: two di-substituted spiro-ansa, N3P3[O(CH2)5O]-(C6H7OS)]2 (4) and N3P3[O(CH2)5O-(C6H5CH2O)]2 (5); and two fully substituted triple-bridged, N3P3[O(CH2)5O]3-(C6H7OS)6N3P3 (7) and N3P3[O(CH2)5O]3-(C6H5CH2O)6N3P3 (8) derivatives were formed in THF solvent by using NaH base at ambient conditions. Because of their variety of applications, there is a great deal of interest in the preparation of aromatic macrocyclic derivatives of cyclophosphazenes. The main purpose of these studies is to develop bioactive cyclophosphazene derivatives in the search for new effective drug candidates for the treatment of various diseases, in particular, anticancer and antimicrobials. The synthesized compounds (4, 5, 7, 8) were defined using analytical techniques namely Element analysis, TLC/MS system, and NMR spectroscopy. Thermal stabilities, crystal purity, and recrystallization properties and corresponding enthalpies of synthesized derivatives were analyzed in the course of heating and cooling cycles of DSC.
Synthesis of oxime bearing cyclophosphazenes and their reactions with alkyl and acyl halides
Heteroatom Chemistry, 2006
Two novel cyclophosphazenes containing oxime groups were prepared from the hexakis(4formylphenoxy)cyclotriphosphazene (2) and hexakis-(4-acetylphenoxy)cyclotriphosphazene (7). The reactions of these oximes with acetyl chloride, chloroacetyl chloride, methyl iodide, propyl chloride, monochloroacetone, and 1,4-dichlorobutane were studied. Hexasubstituted compounds were obtained from the reactions of hexakis(4-[(hydroxyimino)methyl]phenoxy)cyclotriphosphazene (3) with acetyl chloride (4) and chloroacetyl chloride (5); however, tetrasubstituted product was obtained from methyl iodide (6). Tetra-and trisubstituted products were obtained from the reactions of hexakis(4-[(1)-Nhydroxyethaneimidoyl]phenoxy)cyclotriphosphazene (8) with acetyl chloride (9) and chloroacetyl chloride (10), respectively. All products were obtained in high yields. Pure and defined product could not be obtained from the reaction of 8 with methyl iodide, and could not be also obtained from the reactions of 3 and 8 with propyl chloride, monochloroacetone, and 1,4dichlorobuthane. The structures of the compounds were defined by elemental analysis, IR, 1 H, 13 C, and 31 P NMR spectroscopy.
Spiro, ansa-derivatives of cyclotetraphosphazenes with a tetrafluorobutane-1,4-diol
Polyhedron, 2010
The reaction of the octachlorocyclotetraphosphazene, N 4 P 4 Cl 8 (1), in three stoichiometries (1:1, 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 produced seven products, whose structures have been characterized by elemental analysis, mass spectrometry, 1 H, 19 F, 31 P NMR spectroscopy and by X-ray crystallography, where suitable single crystals were obtained: the mono-spiro compound, N 4 P 4 Cl 6 (OCH 2 CF 2 CF 2 CH 2 O) (3), its ansa isomer (4), cis-and trans-bis-spiro derivatives N 4 P 4 Cl 4 (OCH 2 CF 2 CF 2 CH 2 O) 2 (5 and 6), trisspiro compound N 4 P 4 Cl 2 (OCH 2 CF 2 CF 2 CH 2 O) 3 (7), its mono-spiro-bis-ansa isomer (8) and tetrakis-spiro compound N 4 P 4 (OCH 2 CF 2 CF 2 CH 2 O) 4 , (9). X-ray crystallographic studies confirmed that the structure of the mono-spiro-bis-ansa isomer (8) has been reported as a first example in the literature. The results of all reactions were compared with previous work on the reaction of hexachlorocyclotriphosphazene, N 3 P 3 Cl 6 with the sodium derivative of the diol (2), in a 1:1.2 mole ratio in the in the same solvent, THF, and with the reaction of octafluorocyclotetraphosphazene, N 4 P 4 F 8 , with the silyl derivative of the diol (2), (Me 3 SiOCH 2 CF 2) 2 , in a 1:0.4 mole ratio in THF.
Journal of Molecular Structure, 2005
The condensation reactions of {N-[(2-hydroxyphenylmethyl)amino]-methylpyridines (5-8) with trimer, N 3 P 3 Cl 6 , have been afforded partially substituted novel spiro-cyclic phosphazene derivatives (9-12) (Scheme 1). Compounds (9-12) have been characterized by elemental analyses, FTIR, 1 H-, 13 C-, 31 P-NMR, HETCOR, and MS. The structure of the spiro-cyclic phosphazene (9) has been examined crystallographically. It crystallizes in the P2 1 /n space group with aZ10.7906(10) Å , bZ8.5625(17) Å , cZ21.187(5) Å , bZ91.298(12)8, VZ 1957.1(6) Å 3 , ZZ4 and D x Z1.660 g cm K3. The structure consists of a non-planar phosphazene ring with a bulky methylpyridinyl and a benzo-fused spiro-cyclic side group. The six-membered spiro-cyclic ring has a twist-boat conformation.
Inorganic Chemistry, 2007
The reactions of hexachlorocyclotriphosphazatriene, N 3 P 3 Cl 6 , 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 (R) and exocyclic NPO (R′) bond angles of the analogous spirocyclic phosphazenes with the δP shifts of NPO phosphorus atoms have been presented. It was observed that there is a linearity between R angles and δP shifts, while no linear relationship has been observed for R′ angles. In addition, we have found the correlation between ∆(P−N) and δ NPO shifts, which implies a linear relationship. ∆(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 1 H, 13 C, and 31 P 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 CDCl 3 are the same with the solid-state structures.