A new route for the synthesis of phosphate esters: 2,2'-[benzene-1,2-diylbis(­oxy)]bis­(5,5-dimethyl-1,3,2-dioxaphosphinane) 2,2'-dioxide

M. A. Said, A. A.-S. Ali, David Hughes

Research output: Contribution to journalArticle

Abstract

Podand-type ligands are an inter­esting class of acyclic ligands which can form host-guest complexes with many transition metals and can undergo conformational changes. Organic phosphates are components of many biological mol­ecules. A new route for the synthesis of phosphate esters with a retained six-membered ring has been used to prepare 2,2'-[benzene-1,2-diylbis(­oxy)]bis­(5,5-dimethyl-1,3,2-dioxaphosphinane) 2,2'-dioxide, C6H4{O[cyclo-P(O)OCH2CMe2CH2O]}2 or C16H24O8P2, (1), 2-[(2'-hy­droxy­biphenyl-2-yl)­oxy]-5,5-di­methyl-1,3,2-dioxaphosphinane 2-oxide, [cyclo-P(O)OCH2CMe2CH2O](2,2'-OC6H4-C6H4OH), (2), and oxybis(5,5-dimethyl-1,3,2-dioxaphosphinane) 2,2'-dioxide, O[cyclo-P(O)OCH2CMe2CH2O]2, (3). Compound (1) is novel, whereas the results for compounds (2) and (3) have been reported previously, but we record here our results for compound (3), which we find are more precise and accurate than those currently reported in the literature. In (1), two cyclo-P(O)OCH2CMe2CH2O groups are linked through a catechol group. The conformations about the two catechol O atoms are quite different, viz. one C-C-O-P torsion angle is -169.11 (11)° and indicates a trans arrangement, whereas the other C-C-O-P torsion angle is 92.48 (16)°, showing a gauche conformation. Both six-membered POCCCO rings have good chair-shape conformations. In both the trans and gauche conformations, the catechol O atoms are in the axial sites and the short P=O bonds are equatorially bound.
Original languageEnglish
Pages (from-to)1037-1041
Number of pages5
JournalActa Crystallographica Section C
Volume71
DOIs
Publication statusPublished - 2015

Keywords

  • podand-type ligands
  • 1,3,2-dioxaphosphinane
  • phosphate ester
  • Crystal Structure
  • N-chloro­diiso­propyl­amine (NCDA)

Cite this