Synthesis and selected reactivity studies of a dissymmetric (phosphinoylmethylpyridine N-oxide) methylamine platform

Sabrina Ouizem; Sylvie L. Pailloux; Alisha D. Ray; Eileen N. Duesler; Diane A. Dickie; Robert T. Paine; Benjamin P. Hay

doi:10.1002/ejoc.201400120

Synthesis and selected reactivity studies of a dissymmetric (phosphinoylmethylpyridine N-oxide) methylamine platform

Sabrina Ouizem, Sylvie L. Pailloux, Alisha D. Ray, Eileen N. Duesler, Diane A. Dickie, Robert T. Paine, Benjamin P. Hay

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

4 Scopus citations

Abstract

Efficient syntheses for the precursor molecules, 2-{6- [((diphenylphosphoryl)methyl)pyridin-2-yl]methyl}isoindoline-1,3-dione (2), 2-[(1,3-dioxoisoindolin-2-yl)methyl]-6-[(diphenylphosphoryl)methyl]pyridine 1-oxide (3), and their 6-[bis(2-(trifluoromethyl)phenyl)phosphoryl]methyl analogues are reported along with their transformations into the dissymmetric ligands, [(6-(aminomethyl)pyridin-2-yl)methyl]diphenylphosphine oxide (4), 2-(aminomethyl)-6-[(diphenylphosphoryl)methyl]pyridine 1-oxide (5) and 2-(aminomethyl)-6-{[bis(2-(trifluoromethyl)phenyl)phosphoryl]methyl}pyridine 1-oxide (5-F). Selected reactivity of the aminomethyl substituent of 4 and 5, as well as complexation reactions of several of the compounds with lanthanide(III) ions are described. Molecular structures of three uniquely different complexes, {Pr{2-[HC(O)N(H)CH₂]-6-[Ph₂P(O)CH₂]C ₅H₃NO}(NO₃)₃(MeOH)}₂, {Eu{2-[(Me₂N)₂CN(H⁺)CH₂]-6-[Ph ₂P(O)CH₂]C₅H₃N(H) ⁺}(NO₃)₄(OMe)} and {Er{2-[(C₈H ₄O₂)NCH₂]-6-[Ph₂P(O)CH ₂]C₅H₃N(O)}(NO₃)₃(MeOH)} ·(CH₃)₂CO, have been determined by single-crystal X-ray diffraction methods. The observed and computationally modeled structures that employ bidentate and tridentate ligand/metal interactions are compared. These results suggest further ligand modifications that should provide improved solvent extraction reagents.

Original language	English (US)
Pages (from-to)	3132-3148
Number of pages	17
Journal	European Journal of Organic Chemistry
Volume	2014
Issue number	15
DOIs	https://doi.org/10.1002/ejoc.201400120
State	Published - May 2014

Keywords

Chelates
Lanthanides
Ligand design
N ligands
Nitrogen oxides

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10.1002/ejoc.201400120

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title = "Synthesis and selected reactivity studies of a dissymmetric (phosphinoylmethylpyridine N-oxide) methylamine platform",

abstract = "Efficient syntheses for the precursor molecules, 2-{6- [((diphenylphosphoryl)methyl)pyridin-2-yl]methyl}isoindoline-1,3-dione (2), 2-[(1,3-dioxoisoindolin-2-yl)methyl]-6-[(diphenylphosphoryl)methyl]pyridine 1-oxide (3), and their 6-[bis(2-(trifluoromethyl)phenyl)phosphoryl]methyl analogues are reported along with their transformations into the dissymmetric ligands, [(6-(aminomethyl)pyridin-2-yl)methyl]diphenylphosphine oxide (4), 2-(aminomethyl)-6-[(diphenylphosphoryl)methyl]pyridine 1-oxide (5) and 2-(aminomethyl)-6-{[bis(2-(trifluoromethyl)phenyl)phosphoryl]methyl}pyridine 1-oxide (5-F). Selected reactivity of the aminomethyl substituent of 4 and 5, as well as complexation reactions of several of the compounds with lanthanide(III) ions are described. Molecular structures of three uniquely different complexes, {Pr{2-[HC(O)N(H)CH2]-6-[Ph2P(O)CH2]C 5H3NO}(NO3)3(MeOH)}2, {Eu{2-[(Me2N)2CN(H+)CH2]-6-[Ph 2P(O)CH2]C5H3N(H) +}(NO3)4(OMe)} and {Er{2-[(C8H 4O2)NCH2]-6-[Ph2P(O)CH 2]C5H3N(O)}(NO3)3(MeOH)} ·(CH3)2CO, have been determined by single-crystal X-ray diffraction methods. The observed and computationally modeled structures that employ bidentate and tridentate ligand/metal interactions are compared. These results suggest further ligand modifications that should provide improved solvent extraction reagents.",

keywords = "Chelates, Lanthanides, Ligand design, N ligands, Nitrogen oxides",

author = "Sabrina Ouizem and Pailloux, {Sylvie L.} and Ray, {Alisha D.} and Duesler, {Eileen N.} and Dickie, {Diane A.} and Paine, {Robert T.} and Hay, {Benjamin P.}",

year = "2014",

month = may,

doi = "10.1002/ejoc.201400120",

language = "English (US)",

volume = "2014",

pages = "3132--3148",

journal = "European Journal of Organic Chemistry",

issn = "1434-193X",

publisher = "Wiley-VCH Verlag",

number = "15",

}

TY - JOUR

T1 - Synthesis and selected reactivity studies of a dissymmetric (phosphinoylmethylpyridine N-oxide) methylamine platform

AU - Ouizem, Sabrina

AU - Pailloux, Sylvie L.

AU - Ray, Alisha D.

AU - Duesler, Eileen N.

AU - Dickie, Diane A.

AU - Paine, Robert T.

AU - Hay, Benjamin P.

PY - 2014/5

Y1 - 2014/5

N2 - Efficient syntheses for the precursor molecules, 2-{6- [((diphenylphosphoryl)methyl)pyridin-2-yl]methyl}isoindoline-1,3-dione (2), 2-[(1,3-dioxoisoindolin-2-yl)methyl]-6-[(diphenylphosphoryl)methyl]pyridine 1-oxide (3), and their 6-[bis(2-(trifluoromethyl)phenyl)phosphoryl]methyl analogues are reported along with their transformations into the dissymmetric ligands, [(6-(aminomethyl)pyridin-2-yl)methyl]diphenylphosphine oxide (4), 2-(aminomethyl)-6-[(diphenylphosphoryl)methyl]pyridine 1-oxide (5) and 2-(aminomethyl)-6-{[bis(2-(trifluoromethyl)phenyl)phosphoryl]methyl}pyridine 1-oxide (5-F). Selected reactivity of the aminomethyl substituent of 4 and 5, as well as complexation reactions of several of the compounds with lanthanide(III) ions are described. Molecular structures of three uniquely different complexes, {Pr{2-[HC(O)N(H)CH2]-6-[Ph2P(O)CH2]C 5H3NO}(NO3)3(MeOH)}2, {Eu{2-[(Me2N)2CN(H+)CH2]-6-[Ph 2P(O)CH2]C5H3N(H) +}(NO3)4(OMe)} and {Er{2-[(C8H 4O2)NCH2]-6-[Ph2P(O)CH 2]C5H3N(O)}(NO3)3(MeOH)} ·(CH3)2CO, have been determined by single-crystal X-ray diffraction methods. The observed and computationally modeled structures that employ bidentate and tridentate ligand/metal interactions are compared. These results suggest further ligand modifications that should provide improved solvent extraction reagents.

AB - Efficient syntheses for the precursor molecules, 2-{6- [((diphenylphosphoryl)methyl)pyridin-2-yl]methyl}isoindoline-1,3-dione (2), 2-[(1,3-dioxoisoindolin-2-yl)methyl]-6-[(diphenylphosphoryl)methyl]pyridine 1-oxide (3), and their 6-[bis(2-(trifluoromethyl)phenyl)phosphoryl]methyl analogues are reported along with their transformations into the dissymmetric ligands, [(6-(aminomethyl)pyridin-2-yl)methyl]diphenylphosphine oxide (4), 2-(aminomethyl)-6-[(diphenylphosphoryl)methyl]pyridine 1-oxide (5) and 2-(aminomethyl)-6-{[bis(2-(trifluoromethyl)phenyl)phosphoryl]methyl}pyridine 1-oxide (5-F). Selected reactivity of the aminomethyl substituent of 4 and 5, as well as complexation reactions of several of the compounds with lanthanide(III) ions are described. Molecular structures of three uniquely different complexes, {Pr{2-[HC(O)N(H)CH2]-6-[Ph2P(O)CH2]C 5H3NO}(NO3)3(MeOH)}2, {Eu{2-[(Me2N)2CN(H+)CH2]-6-[Ph 2P(O)CH2]C5H3N(H) +}(NO3)4(OMe)} and {Er{2-[(C8H 4O2)NCH2]-6-[Ph2P(O)CH 2]C5H3N(O)}(NO3)3(MeOH)} ·(CH3)2CO, have been determined by single-crystal X-ray diffraction methods. The observed and computationally modeled structures that employ bidentate and tridentate ligand/metal interactions are compared. These results suggest further ligand modifications that should provide improved solvent extraction reagents.

KW - Chelates

KW - Lanthanides

KW - Ligand design

KW - N ligands

KW - Nitrogen oxides

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U2 - 10.1002/ejoc.201400120

DO - 10.1002/ejoc.201400120

M3 - Article

AN - SCOPUS:84900872159

SN - 1434-193X

VL - 2014

SP - 3132

EP - 3148

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

IS - 15

ER -

Synthesis and selected reactivity studies of a dissymmetric (phosphinoylmethylpyridine N-oxide) methylamine platform

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