Tetrapropylphosphocavitands: Synthesis, Structure, and Properties

Maslennikova, V. I.; Shkarina, Elena V.; Vasyanina, L. K.; Лысенко, К. А.; Sinicina, Tatyana K.; Merkulov, Roman V.; Nifantyev, E. E.

doi:10.1080/10426509808035686

Cited by 23 publications

(19 citation statements)

References 6 publications

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“…Substituents in the calixarene template are responsible only for solubility of the compound. The alkylation of phosphoramidite cavitands with alkyl halides takes place only under heating and in the presence of a large excess of the reactant, 152,154 whereas the reactions of hydrotetrafluoroboric acid derivatives proceed under milder conditions. 155 The protonation of phosphoramidite cavitands with hydrotetrafluoroboric acid in chloroform at room temperature at different reactant rations gives rise to a inseparable mixture R 1 = n-CnH2n+1 (n = 1 ± 6); R 2 = Me, Et; Ar = Ph, 4-MeC6H4, 2-Pr i C6H4, 2,6-Bu t 2 -4-MeC6H2, of products resulting from several competitive reactions.…”

Section: Design Of Phosphocavitandsmentioning

confidence: 99%

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Phosphorus-containing macrocyclic compounds: synthesis and properties

Knyazeva¹,

Бурилов²,

Пудовик³

et al. 2013

Russ. Chem. Rev.

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Main trends in the development of methods for Main trends in the development of methods for the synthesis of phosphorus-containing macrocyclic com-the synthesis of phosphorus-containing macrocyclic compounds in the past 15 years are considered. Emphasis is pounds in the past 15 years are considered. Emphasis is given to reactions producing macrocyclic structures with the given to reactions producing macrocyclic structures with the participation of a phosphorus atom and other functional participation of a phosphorus atom and other functional groups involved in organophosphorus molecules and to groups involved in organophosphorus molecules and to modifications of macrocycles by phosphorus compounds modifications of macrocycles by phosphorus compounds in different valence states. Possibilities of the practical in different valence states. Possibilities of the practical application of phosphorus-containing macrocyclic com-application of phosphorus-containing macrocyclic compounds in difference areas of science and engineering are pounds in difference areas of science and engineering are discussed. The bibliography includes 205 references discussed. The bibliography includes 205 references. .

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Section: Design Of Phosphocavitandsmentioning

confidence: 99%

“…Generally, it was performed by the attachment of sulfur to trivalent phosphorus atoms of calix [4]resorcinols or cavitands pre-phosphorylated at the upper rim. 82,140,145,151,152,161 …”

Section: Scheme 82mentioning

confidence: 99%

Phosphorus-containing macrocyclic compounds: synthesis and properties

Knyazeva¹,

Бурилов²,

Пудовик³

et al. 2013

Russ. Chem. Rev.

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“…2a,b). A narrow singlet in the 31 P NMR spectrum and a set of signals for the protons of the resorcinarene matrix in the 1 H NMR spectrum are typical for rigid phosphocyclic calixarene structures 18,19 . The averaging of signals for the protons of the macrocyclic skeleton in phosphocavitands is due to the symmetry of their molecules.…”

Section: Methodsmentioning

confidence: 99%

New aspects in the chemistry of perphosphorylated calix[4]resorcinarenes

Nifantyev¹,

Maslennikova²,

Habicher³

et al. 2004

Arkivoc

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Interaction between calix[4]resorcinarenes 1 and 2-amino-1,3,2-diheterophosphorinanes 2 resulted in sterically pure polyphosphocyclic conjugates 3. The structure of which was supported by NMR spectroscopy and X-ray diffraction analysis. The possibility of further modification of perphosphorylated resorcinarenes 3 was studied. It was shown that compounds 3a,b containing tBu-N groups at the phosphorus atoms do not enter into reactions increasing the coordination number of phosphorus because of steric hindrance. Sterically less hindered phosphoresorcinarenes 3c-i readily add sulfur, oxygen, and form octanuclear and chelate complexes with transition metals (Mo and Pd, respectively).

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“…These compounds include resorcinarenes and their modified analogs. Due to the conformational lability of these molecules and presence of hydroxy groups and the ortho position of benzene rings at the macrocycle whose reactivity can be controlled, the resorcinarenes form a convenient basis for the design of complex compounds with polyfunctionalized cavity systems [5-10].Our goal was to synthesize derivatives of the new heterofunctional resorcinarenes and consider the ways to modify the free reaction sites of phosphoresorcinolarenes of various types.To implement this task we used a common scheme: the resorcinarenes were phosphorylated with phosphorous amides, the phospho(IV)resorcinarenes formed were transformed in the phosphorus(IV) resorcinollarenes, and various functional groups were introduced into the latter molecules.Depending on the required regioselectivity of the process, we selected as the basic compounds the resorcinollarenes I with certain substituents in methylidene bridges and ortho position of benzene rings of the macro-cyclic framework.As a platform for the synthesis of new orthofunctionalized phosphocavitands served ortho-bromotetra(phenylethyl)resorcinarene Ia, due to its boat conformation, that is convenient for the phosphocyclization [9,11], and to the presence of easily replaceable bromine atoms in the ortho positions of benzene rings of the macrocyclic skeleton [12][13][14][15] (Scheme 1).The cyclophosphorylation of Ia with tripiperidylphosphite was performed by the standard method [16,17] in dioxane at room temperature. To the formed phosphorus(III)cavitand was added sulfur without its isolation from the reaction mixture (Scheme 1).…”

mentioning

confidence: 99%

“…The cyclophosphorylation of Ia with tripiperidylphosphite was performed by the standard method [16,17] in dioxane at room temperature. To the formed phosphorus(III)cavitand was added sulfur without its isolation from the reaction mixture (Scheme 1).…”

mentioning

confidence: 99%

Synthesis of new heterofunctionalized resorcinarene derivatives

et al. 2012

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New derivatives of heterofunctionalized resorcinarenes differing by the nature, number, ratio, and orientation of functional groups were obtained by modification of free reactive centers in the phosphoresorcinarenes of different types.Currently great attention is paid to the design of the receptor systems that can act as chemosensors or extractants. The most common matrices for their creation are macrocyclic molecules containing free cavities and a large number of reaction centers located in a certain mode relative to each other [1][2][3][4]. These compounds include resorcinarenes and their modified analogs. Due to the conformational lability of these molecules and presence of hydroxy groups and the ortho position of benzene rings at the macrocycle whose reactivity can be controlled, the resorcinarenes form a convenient basis for the design of complex compounds with polyfunctionalized cavity systems [5-10].Our goal was to synthesize derivatives of the new heterofunctional resorcinarenes and consider the ways to modify the free reaction sites of phosphoresorcinolarenes of various types.To implement this task we used a common scheme: the resorcinarenes were phosphorylated with phosphorous amides, the phospho(IV)resorcinarenes formed were transformed in the phosphorus(IV) resorcinollarenes, and various functional groups were introduced into the latter molecules.Depending on the required regioselectivity of the process, we selected as the basic compounds the resorcinollarenes I with certain substituents in methylidene bridges and ortho position of benzene rings of the macro-cyclic framework.As a platform for the synthesis of new orthofunctionalized phosphocavitands served ortho-bromotetra(phenylethyl)resorcinarene Ia, due to its boat conformation, that is convenient for the phosphocyclization [9,11], and to the presence of easily replaceable bromine atoms in the ortho positions of benzene rings of the macrocyclic skeleton [12][13][14][15] (Scheme 1).The cyclophosphorylation of Ia with tripiperidylphosphite was performed by the standard method [16,17] in dioxane at room temperature. To the formed phosphorus(III)cavitand was added sulfur without its isolation from the reaction mixture (Scheme 1). Two singlet signals with equal integral intensities appeared in the 31 P NMR spectrum of the isolated tionamidophosphatocavitand II and the doubling of signals of the the benzene rings meta-protons of the framework in the 1 H NMR spectrum indicated the implementation of the kite conformation [17,18].The phosphorus(IV)cavitand II was brpoght into the reaction of electrophilic substitution. Compound II was treated with BuLi, then to it was added either methylchloroformate, which led to ortho-methoxycarbonyl derivative III (Scheme 1, a), or sequentially trimethylborate and hydrogen peroxide with sodium hydroxide solution, which completed by the formation of the ortho-hydroxylated cavitands IV (Scheme 1, b). Further, in the interaction of IV with acetic anhydride ortho-acetylated cavitand V was obtained (Scheme 1, c).Compounds III...

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Tetrapropylphosphocavitands: Synthesis, Structure, and Properties

Cited by 23 publications

References 6 publications

Phosphorus-containing macrocyclic compounds: synthesis and properties

Phosphorus-containing macrocyclic compounds: synthesis and properties

New aspects in the chemistry of perphosphorylated calix[4]resorcinarenes

Synthesis of new heterofunctionalized resorcinarene derivatives

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