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Synthesis and Selected Reactivity Studies of a Dissymmetric (Phosphinoylmethylpyridine N ‐Oxide) Methylamine Platform
Author(s) -
Ouizem Sabrina,
Pailloux Sylvie L.,
Ray Alisha D.,
Duesler Eileen N.,
Dickie Diane A.,
Paine Robert T.,
Hay Benjamin P.
Publication year - 2014
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201400120
Subject(s) - chemistry , methylamine , pyridine , reactivity (psychology) , medicinal chemistry , denticity , ligand (biochemistry) , stereochemistry , trifluoromethyl , reagent , substituent , crystal structure , crystallography , organic chemistry , medicine , biochemistry , alkyl , alternative medicine , receptor , pathology
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)CH 2 ]‐6‐[Ph 2 P(O)CH 2 ]C 5 H 3 NO}(NO 3 ) 3 (MeOH)} 2 , {Eu{2‐[(Me 2 N) 2 CN(H + )CH 2 ]‐6‐[Ph 2 P(O)CH 2 ]C 5 H 3 N(H) + }(NO 3 ) 4 (OMe)} and {Er{2‐[(C 8 H 4 O 2 )NCH 2 ]‐6‐[Ph 2 P(O)CH 2 ]C 5 H 3 N(O)}(NO 3 ) 3 (MeOH)} · (CH 3 ) 2 CO, 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.