12H-dibenzo[d,g][1,3,2]dioxaphosphocins: Synthesis, structures and “through-space” spin-spin coupling in their NMR spectra

doi:10.1002/JHET.5570250241

Paper

12H-dibenzo[d,g][1,3,2]dioxaphosphocins: Synthesis, structures and “through-space” spin-spin coupling in their NMR spectra

Published Mar 1, 1988 · J. D. Goddard, Alan W. Payne, N. Cook

Journal of Heterocyclic Chemistry

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35

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Abstract

A series of 12H-dibenzo[d,g][1,3,2]dioxaphosphocins has been prepared by the reactions of bisphenols with either ethyl phosphorodichloridate or phosphorus pentasulfide. The structures of a pair of cis and trans isomers in this series were elucidated by X-ray crystallography. Both isomers adopt the boat-chair conformation in the solid state with the bulky group at C-12 in the pseudo-equatorial position. Some flattening of the heterocyclic ring due to the pseudo-axial ethoxy group was observed in the cis isomer. A novel transannular cyclisation reaction was observed in the mass spectra of the cis isomers and this has allowed us to assign the configurations of all the isomers in the series. The pmr spectra of the compounds have been explained in terms of the rigid boat-chair conformation; however, as bulky groups were introduced at C-12, signs of mobility were observed for the cis isomers and an equilibrium was established with mobile boat forms. A stereospecific long-range coupling between P and the proton at C-12 could be transmitted “through space” by the antiperiplanar lone-pair electrons on the ring oxygen atoms.

Study Snapshot

12H-dibenzo[d,g][1,3,2]dioxaphosphocins show rigid boat-chair conformation and mobility, with a unique "through-space" spin-spin coupling in their NMR spectra.

PopulationOlder adults (50-71 years)

Sample size24

MethodsObservational

OutcomesBody Mass Index projections

ResultsSocial networks mitigate obesity in older groups.

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Paper

12H-dibenzo[d,g][1,3,2]dioxaphosphocins: Synthesis, structures and “through-space” spin-spin coupling in their NMR spectra

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References

INHIBITION OF PSEUDOROTATION IN SOME MONOCYCLIC PENTAOXYPHOSPHORANES

Some monocyclic pentaoxyphosphoranes exhibit significant barriers to intramolecular ligand reorganization, suggesting steric inhibition of pseudorotation.

13C NMR Study of 3,9‐di(alkylphenoxy) ‐2,4,8,10‐tetraoxa‐3,9‐diphosphaspiro[5.5]undecanes

The 13,9-dioxo derivatives of 3,9-di(alkylphenoxy)2,4,8,10tetraoxa3,9-diphosphaspiro[5.5]undecanes show a chair conformation with cis alkylphenoxy groups

REACTION OF SEVEN‐ AND EIGHT‐MEMBERED CYCLIC PHOSPHOROCHLORIDITES WITH 3,5‐DI‐TERT‐BUTYL‐4‐HYDROXYBENZYL ALCOHOL: FACILE PHOSPHORUS‐CARBON BOND FORMATION

This study demonstrates that facile phosphorus-carbon bond formation can occur when seven- and eight-membered cyclic phosphorophholoridite reactions with 3,5-di-t-butyl-4-hydroxybenzyl alcohol.

The Reaction of Seven- and Eight- Membered Cyclic Phosphorochloridites with Polyols

Novel bridged dibenzo[d,f][1,3,2]dioxaphosphepin and dibenzo[d,g][1,3,2]dioxaphosphocin ring systems were synthesized, with potential for applications in organic synthesis and drug discovery.

REACTION OF SEVEN- AND EIGHT-MEMBERED CYCLIC PHOSPHOROCHLORIDITES WITH ALKANOLAMINES

Substituted 6-chloro-12H-dibenzo[d,g][1,3,2]dioxaphosphocins and 6-chlorodibenzo[d,f][1,3,2]dioxaphosphepins react with alkano

Citations

Investigations on the Enantiomerization Mechanism of an Organophosphorus Cages – DFT Study

The enantiomerization pathways of organophosphorus cages Bz3XPO4 show a decreasing twist angle order, with steric factors mainly affecting activation energy and structural data.

Exocyclic Diastereotopic Protons as a Probe for Conformational Bias in Eight-Membered Rings Containing Phosphorus and Titanium

In addition to steric effects, electronic effects from ring oxygen atoms also influence the preferred conformation in solution of eight-membered rings containing phosphorus and titanium.

Solvent-free synthesis of novel 2,10-dichoro-12-trichloromethyl-6-substituted xanthato-12H-dibenzo[d,g] [1,3,2] dioxaphosphocin-6-sulfides

This study presents a novel solvent-free method for synthesizing novel 2,10-dichloro-12-trichloromethyl-6-substituted xanthato-12H-dibenzo[d,g] [1,3,2] dioxaphosphocin-6-sul

Through‐Space J(P,P) and J(P,F) Spin–Spin Coupling in C1‐Symmetric Biaryl Diphosphanes

C1-symmetric biaryl diphosphanes show simultaneous 31P,31P and 31P,19F solution-phase through-space nuclear spin-spin coupling, with coupling constants ranging from 5.3-28.7 to 2.3-5.1 Hz.

A Macrobicyclic Calix[6]arene Phosphocine: Conformational Studies Involving High-Resolution NMR Analysis and Molecular Modeling

The racemate phosphorylated hexa(tert-butyl)calix[6]arene 1a is a macrocyclic dibenzo[1,3,2]dioxaphosphocine with a racemic nature, exhibiting a macrocyclic dibenzo[1,3,

12H-dibenzo[d,g][1,3,2]dioxaphosphocins: Synthesis, structures and “through-space” spin-spin coupling in their NMR spectra

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References

INHIBITION OF PSEUDOROTATION IN SOME MONOCYCLIC PENTAOXYPHOSPHORANES

Some monocyclic pentaoxyphosphoranes exhibit significant barriers to intramolecular ligand reorganization, suggesting steric inhibition of pseudorotation.

13C NMR Study of 3,9‐di(alkylphenoxy) ‐2,4,8,10‐tetraoxa‐3,9‐diphosphaspiro[5.5]undecanes

The 13,9-dioxo derivatives of 3,9-di(alkylphenoxy)2,4,8,10tetraoxa3,9-diphosphaspiro[5.5]undecanes show a chair conformation with cis alkylphenoxy groups

REACTION OF SEVEN‐ AND EIGHT‐MEMBERED CYCLIC PHOSPHOROCHLORIDITES WITH 3,5‐DI‐TERT‐BUTYL‐4‐HYDROXYBENZYL ALCOHOL: FACILE PHOSPHORUS‐CARBON BOND FORMATION

This study demonstrates that facile phosphorus-carbon bond formation can occur when seven- and eight-membered cyclic phosphorophholoridite reactions with 3,5-di-t-butyl-4-hydroxybenzyl alcohol.

The Reaction of Seven- and Eight- Membered Cyclic Phosphorochloridites with Polyols

Novel bridged dibenzo[d,f][1,3,2]dioxaphosphepin and dibenzo[d,g][1,3,2]dioxaphosphocin ring systems were synthesized, with potential for applications in organic synthesis and drug discovery.

REACTION OF SEVEN- AND EIGHT-MEMBERED CYCLIC PHOSPHOROCHLORIDITES WITH ALKANOLAMINES

Substituted 6-chloro-12H-dibenzo[d,g][1,3,2]dioxaphosphocins and 6-chlorodibenzo[d,f][1,3,2]dioxaphosphepins react with alkano

Citations

Investigations on the Enantiomerization Mechanism of an ­Organophosphorus Cages – DFT Study

The enantiomerization pathways of organophosphorus cages Bz3XPO4 show a decreasing twist angle order, with steric factors mainly affecting activation energy and structural data.

Exocyclic Diastereotopic Protons as a Probe for Conformational Bias in Eight-Membered Rings Containing Phosphorus and Titanium

In addition to steric effects, electronic effects from ring oxygen atoms also influence the preferred conformation in solution of eight-membered rings containing phosphorus and titanium.

Solvent-free synthesis of novel 2,10-dichoro-12-trichloromethyl-6-substituted xanthato-12H-dibenzo[d,g] [1,3,2] dioxaphosphocin-6-sulfides

This study presents a novel solvent-free method for synthesizing novel 2,10-dichloro-12-trichloromethyl-6-substituted xanthato-12H-dibenzo[d,g] [1,3,2] dioxaphosphocin-6-sul

Through‐Space J(P,P) and J(P,F) Spin–Spin Coupling in C1‐Symmetric Biaryl Diphosphanes

C1-symmetric biaryl diphosphanes show simultaneous 31P,31P and 31P,19F solution-phase through-space nuclear spin-spin coupling, with coupling constants ranging from 5.3-28.7 to 2.3-5.1 Hz.

A Macrobicyclic Calix[6]arene Phosphocine: Conformational Studies Involving High-Resolution NMR Analysis and Molecular Modeling

The racemate phosphorylated hexa(tert-butyl)calix[6]arene 1a is a macrocyclic dibenzo[1,3,2]dioxaphosphocine with a racemic nature, exhibiting a macrocyclic dibenzo[1,3,

Investigations on the Enantiomerization Mechanism of an Organophosphorus Cages – DFT Study