Copolymerization of Chlorocyclotriphosphazene Derivatives Containing the Methacycloylbutenedioxy and N-(Ferrocenylmethyl)-N-Methylamino Substituents with Methylmethacrylate

Myer, Charles N.; Allen, Christopher W.

doi:10.1007/s10904-006-9086-z

Cited by 10 publications

(3 citation statements)

References 16 publications

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“…This has allowed for the use of phosphazenes related to 11 to serve as a monomers in radical initiated olefin polymerization. [31][32][33] The role of the ester carbonyl was examined by investigating the thermolysis of 12 where the methacrylate group is replaced by a methoxy group. Even under forcing conditions (111°, 48 hours), no rearrangement was observed.…”

Section: Dalton Transactions Papermentioning

confidence: 99%

The mechanism of a phosphazene–phosphazane rearrangement

Hayes

Allen

2016

Dalton Trans.

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The phosphazene-phosphazane rearrangement of N3P3Cl5O(CH2)2OC(=O)CMe=CH2 (8) has been examined in detail using one and two dimensional NMR ((31)P, (1)H) spectroscopy and mass spectrometry. The mixed phosphazene-phosphazane [NPCl2]2[N((CH2)2OC(=O)CMe=CH2)P(O)Cl] (14), [NPCl2]2[NHP(O)Cl] (13) and a two ring assembly [NPCl2]2[NP(O{(NPCl2)2(N((CH2)2OC(=O)CMe=CH2)P(O)}] (15) have all been detected in the product mixture. The rate of the rearrangement has been measured at five temperatures by (31)P and (1)H NMR. The reaction is first order in 8 (T1/2 at 111° is 4.65 hours). The activation enthalpy is positive and the activation entropy is negative. A mechanism involving competing intra and inter molecular processes which fits the product distribution and kinetic data has been proposed. Several other methyacrylphosphazenes were examined under the same thermolysis conditions. The rearrangement was observed and the rates obtained in cases where the (CH2)2 spacer unit of the methacrylate was replaced by linear and branched propyl units. The rearrangement was not observed when the methacrylate was appended to a spirocyclic unit, the spacer unit was extended to the n-butyl group and when the methacrylate unit was replaced by a methoxy group. These results are all consistent with the proposed mechanism. This investigation resolves conflicting results previous reported for the rearrangement.

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Section: Dalton Transactions Papermentioning

confidence: 99%

The mechanism of a phosphazene–phosphazane rearrangement

Hayes

Allen

2016

Dalton Trans.

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“…42−45 The nature of the substituents on the ring plays a dominant role in directing the course of the reaction. 32,42,46 We have previously shown that the reactions of the 3-amino-1-propanoxy spiro derivative (1e) of hexachlorocyclotriphos-phazene with pyrrolidine proceed with an overwhelming preference for the bis geminal product at the disubstitution stage. 47 While the predominant formation of non-geminal cis and trans isomers are the expected result from the reaction with a secondary amine, the exclusive formation of the bis geminal derivative at this relatively early stage of substitution indicated that additional factors become important as more of the chlorine atoms are replaced on the phosphazene ring.…”

Section: ■ Introductionmentioning

confidence: 99%

“…However, most secondary amines, with the exception of aziridine, follow a predominantly non-geminal path, and these reactions are generally stereo- and regioselective with the trans non-geminal isomer as the major product. Detailed kinetic analyses have shown that the trans preference arises from the entropy of activation. , Increased solvent polarity can also favor dissociative processes and hence geminal substitution in aminolysis reactions. − The nature of the substituents on the ring plays a dominant role in directing the course of the reaction. ,, …”

Section: Introductionmentioning

confidence: 99%

Regiochemical Control in the Substitution Reactions of Cyclotriphosphazene Derivatives with Secondary Amines

et al. 2018

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The substitution reactions of the monospiro and geminally disubstituted cyclotriphosphazene derivatives NPClR (R = OCH(CF)CHO (1a), SPh (1b), OCHCHCHO (1c), NHPh (1d), OCHCHCHNH (1e), NHBu (1f)) with two secondary amines (pyrrolidine and dimethylamine) were carried out to investigate geminal or non-geminal directing effects in mixed substituent cyclophosphazenes. The relative amounts of isomeric products, geminal and non-geminal trans or cis, was established quantitatively from the P NMR spectra of the reaction mixtures. Although secondary amines generally follow a non-geminal pathway in the reactions with hexachlorocyclotriphosphazene, in this work, the reactions of two different secondary amines with some NPClR (R = OCHCHCHNH, NHPh, NHBu) derivatives lead to the formation of geminal products. We have shown that this observation depends on the electron-donating properties of the PR groups. Isolated compounds were analyzed by standard techniques such as elemental analysis, mass spectrometry, and H andP NMR spectroscopy. The structures of compounds for which suitable crystals could be obtained were characterized by X-ray crystallography.

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From Rings to Polymers

Allen

2007

J Inorg Organomet Polym

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Copolymerization of Chlorocyclotriphosphazene Derivatives Containing the Methacycloylbutenedioxy and N-(Ferrocenylmethyl)-N-Methylamino Substituents with Methylmethacrylate

Cited by 10 publications

References 16 publications

The mechanism of a phosphazene–phosphazane rearrangement

The mechanism of a phosphazene–phosphazane rearrangement

Regiochemical Control in the Substitution Reactions of Cyclotriphosphazene Derivatives with Secondary Amines

From Rings to Polymers

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