The bis-phosphines, 1,1’-[1,2-phenylenebis(methylene)]bis-3,5-diaza-1-azonia-7-phosphatricyclo[3.3.1.1]decane dibromide (1), 1,1’-[1,3-arenebis(methylene)]bis-[3,5-diaza-1-azonia-7-phosphatricyclo [3.3.1.1]decane dibromide (arene = phenyl (2), tolyl (3), anisolyl (4)), and 1,1’-[1,4-phenylenebis(methylene)]bis-3,5-diaza-1-azonia-7-phosphatricyclo[3.3.1.1]decane dibromide (5) were prepared in over 90% yield by refluxing 1,2-bis(bromomethyl)benzene, 1,3-bis(bromomethyl)benzene, 1,3-bis(bromomethyl)-5-methyl-benzene, 1,3-bis(bromomethyl)-5-methoxy-benzene, and 1,4-bis(bromomethyl)benzene with 1,3,5-triaza-7-phosphaadamantane (PTA) in acetone or chloroform. Compounds 1-5 are the first phosphines reported that contain two PTA moieties. All five compounds were characterized by ESI-MS, elemental analysis, 1H, 13C, and 31P NMR spectroscopy, while 3 and 4 were additionally analyzed via single crystal X-ray diffraction. The relative positions of the PTA units on the aromatic ring as well as the substituents of the ring had a pronounced effect on the water-solubilities of the systems. The ortho compound (1, 2000 mg/mL ) was more than two orders of magnitude more soluble than the para compound (5, 12.5 mg/mL). The meta substituted phenyl (2) and tolyl (3) compounds had solubilities (810 mg/mL) that were more than triple that of PTA (235 mg/mL) while the anisolyl analog (4) was half as soluble (121 mg/mL).
Preparation, Spectroscopy, X-ray Analysis, and Water-Solubility Studies of the First Bis-PTA (PTA=1,3,5-Triaza-7-phosphaadamantane) derivatives.
BERGAMINI, Paola;MARVELLI, Lorenza;
2009
Abstract
The bis-phosphines, 1,1’-[1,2-phenylenebis(methylene)]bis-3,5-diaza-1-azonia-7-phosphatricyclo[3.3.1.1]decane dibromide (1), 1,1’-[1,3-arenebis(methylene)]bis-[3,5-diaza-1-azonia-7-phosphatricyclo [3.3.1.1]decane dibromide (arene = phenyl (2), tolyl (3), anisolyl (4)), and 1,1’-[1,4-phenylenebis(methylene)]bis-3,5-diaza-1-azonia-7-phosphatricyclo[3.3.1.1]decane dibromide (5) were prepared in over 90% yield by refluxing 1,2-bis(bromomethyl)benzene, 1,3-bis(bromomethyl)benzene, 1,3-bis(bromomethyl)-5-methyl-benzene, 1,3-bis(bromomethyl)-5-methoxy-benzene, and 1,4-bis(bromomethyl)benzene with 1,3,5-triaza-7-phosphaadamantane (PTA) in acetone or chloroform. Compounds 1-5 are the first phosphines reported that contain two PTA moieties. All five compounds were characterized by ESI-MS, elemental analysis, 1H, 13C, and 31P NMR spectroscopy, while 3 and 4 were additionally analyzed via single crystal X-ray diffraction. The relative positions of the PTA units on the aromatic ring as well as the substituents of the ring had a pronounced effect on the water-solubilities of the systems. The ortho compound (1, 2000 mg/mL ) was more than two orders of magnitude more soluble than the para compound (5, 12.5 mg/mL). The meta substituted phenyl (2) and tolyl (3) compounds had solubilities (810 mg/mL) that were more than triple that of PTA (235 mg/mL) while the anisolyl analog (4) was half as soluble (121 mg/mL).I documenti in SFERA sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
