Darstellung von 2-Amino-1.3.2λ³(λ⁵)-dioxaphospholanen / Synthesis of 2-Amino-1,3,2λ³ (λ⁵)-dioxaphospholanes

Abstract

<jats:title>Abstract</jats:title><jats:p>The 2-amino-4,4,5,5-tetrakis(trifluoromethyl)-1,3,2λ<jats:sup>3</jats:sup>-dioxaphospholanes 1 a - c are synthesized by reacting halogenoaminophosphines with dilithiumperfluoropinacolate, whereas 1 d-f are obtained from 2-chloro-4,4,5,5-tetrakis(trifluoromethy 1) -1,3, 2λ<jats:sup>3</jats:sup>-dioxaphospholane and the aminosilanes RNH(SiMe<jats:sub>3</jats:sub>) (R = t-Bu, SiMe<jats:sub>3</jats:sub>) or the amide (Me<jats:sub>3</jats:sub>Si)<jats:sub>2</jats:sub>NLi, respectively. Addition of chlorine to 1 a-f yields the covalent 2,2-dichloro-1,3,2 λ<jats:sup>5</jats:sup>-dioxaphospholanes 2 a-f which furnish the spirophosphoranes 3 a-f upon reaction with dilithiumperfluoropinacolate. The X-ray structure analysis of 3 a exhibits an almost ideal trigonal bipyramid having a very short P-N bond distance (1.590 Å) and H ··· O distance (2.34 Å).</jats:p>

Monocyclische 1,3,2λ 5 ‐Oxazaphosphetane

“….065 (1) .051 (1) .079 (1) .137 (1) .033 (1) .040 (1) .035 (1) .060 (1) .066 (1) .042 (1) .067 (1) .099 (1) .136 (1) .030 (1) .108 (1) .040(1) .044 (1) .083 (1) .126 (1) .153 (1) .152 (1) .107 (1) .072 (1) .P83(1) .190 (1) .0366 (5) .0039(4) .0319 (9) .0063(9) .045 (1) .003 (1) .036 (1) .001 (1) .045 (1) -.011(1) .077 (1) .006(1) .075 (1) -.020 (1) .096 (1) -.028(1) .046 (1) .004(1) .OBl(l) -.006(1)…”

“…-.008(1) .099 (1) .029(1) .044 (1) .0089 (9) .051 (1) .012 (1) .062 (1) .011 (1) .093 (1) -.029(1) .093 (1) .035(1) .091 (1) .023(1) .115 (1) .009(1) .162 (1) .010(1) .134 (1) -.OOl(l) .181(1) -.003 (1) .040 (1) -.0018(9) .044 (1) -.008(1) .060 (1) .000(1) .105 (1) .021(1) .056 (1) .003 (1) .116 (1) -.003(1) .072 (1) -.006(11 .147ii j .004ii j .073(1) -.007(1) .146 (1) -.030(1) .048 (1) .M)64 (9) .066 (1) .030(1) .059 (1) .044(1) .120(1)…”

“….050 (1) .050(1) .0156 (9) .0203(9) .021 (1) .023 (11 .oosii j .ozaii j .028(1) .002 (1) .008 (1) .040 (1) .037 (1) .081(1) .019 (1) .019 (1) .…”

Ein methylimidoverbrücktes Diphosphoran, in dem Stickstoff nicht Glied eines Ringes ist / A Methylimido-bridged Diphosphorane in which Nitrogen is not Member of a Ring

“…(1)), entstanden durch oxidative Addition von elementarem Chlor an beide Phosphorzentren (zur Cl2-Addition siehe Lit. [6]) neben dem Trichlorphosphoran 4 [7] und dem Diazadiphosphetidin 5 das Diphosphoran 3, das seinerseits bei Raumtemperatur langsam (Schema, Gl. (2) und (3)) in 4 und 5 zerfällt.…”