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Phosphorus Containing Macrocycles and Macrobicycles

W.D. Habicher and I. Bauer University of Technology Dresden Institute of Organic Chemistry. Phosphorus Containing Macrocycles and Macrobicycles. HAS-Phosphites as Antioxidants for Synthetic Polymers. processing stabilizer. light and long term thermo stabilizer.

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Phosphorus Containing Macrocycles and Macrobicycles

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  1. W.D. Habicher and I. Bauer University of Technology Dresden Institute of Organic Chemistry Phosphorus Containing Macrocyclesand Macrobicycles

  2. HAS-Phosphites as Antioxidants for Synthetic Polymers processing stabilizer light and long term thermo stabilizer long term thermo stabilizer

  3. Oligomeric Hindered Amine Phosphites as Polymer Stabilizers-Phosphorous Chloride Method- Unexpected Result: Formation of Macrocyclic Byproducts !!!

  4. Phosphorus Containing Macrocycles in Synthetic Organic and Supramolecular Chemistry • Tricoordinated phosphorus containing macrocycles • can function as ligands for transition metal catalyzed reactions • (Heck reaction, hydroformylation, homogenous catalytic hydration, • Suzuki coupling, Sonogashira coupling etc.) • Pentavalent phosphoryl macrocycles • can be used for metal complexation and for molecular recognition of • H donating substrates also of biologically interesting compounds • such as amino acids

  5. Principles of Macrocycle Formation B. Dietrich, P. Viout, J.-M. Lehn, "Macrocyclic Chemistry: Aspects of Organic and Inorganic Supramolecular Chemistry", VCH, Weinheim, New York, Basel, Cambridge, 1992.

  6. X = Cl, NR Y = lone pair, O, S P chloride method P amidite method 2 Synthesis of Macrocycles with P(III) and P(V) Acid Derivatives

  7. Stereoisomerism of Tetracoordinated P(III)- and P(V)-Macrocycles 2 Phosphorus Centers 3 Phosphorus Centers 4 Phosphorus Centers X = lone pair, O

  8. Reaction of Phosphorous Dichlorides with Bisphenols I

  9. Oxidation of Phosphorus Macrocycles

  10. Reaction of Phosphorous Dichlorides with Bisphenols II

  11. Reaction of Phosphorous Dichlorides with Bisphenols IV

  12. Reaction of Phosphorous Dichlorides with Bisphenols V

  13. Different Ring Sizes of P-Macrocycles Dimers + Trimers Dimers Tetramer

  14. Phosphorous Amide Method I-Asymmetric P-Macrocycles as Unstable Intermediates-- Formation of Symmetric P-Macrocycles and Open Chain Products-

  15. X-Ray Structure of trans-4

  16. P-Containing Macrobicycles - Principles of Formation I - B. Dietrich, P. Viout, J.-M. Lehn, "Macrocyclic Chemistry: Aspects of Organic and Inorganic Supramolecular Chemistry", VCH, Weinheim, New York, Basel, Cambridge, 1992.

  17. flexible arms In,Out-Isomerism diastereomers relatively rigid arms diastereomers R.W. Alder, S.P. East, Chem. Rev.1996, 96, 2097-2111

  18. „In-ness“ and “Out-ness“- of Bridgehead Substituents in-CR 0° £ q£ 90° out-CR 90°£ q £ 180° R.W. Alder, S.P. East, Chem. Rev.1996, 96, 2097-2111

  19. Double-CappingMethod for Macrobicycle Formation I

  20. Oxidation of in,out-PhosphiteMacrobicycle 1 2 3 31P{1H} NMR:  = 147.2 (in), 128.0 (out) 31P{1H} NMR:  = 147.9 (in), -21.6 (out) 31P{1H} NMR:  = -11.2 (in), -21.8 (out) 1 2 3

  21. Double-CappingMethod for Macrobicycle Formation II in,in 31P NMR after rough chroma- tography out,out macropolycycles in,out

  22. X-Ray Structure of out,out-p,p,p-Phenylene Bridged Phosphite-Macrobicycle q = 130° 10.5 Å q = 132° view into the cavity view along the P-P-axis

  23. X-Ray Structure of in,in-p,p,p-Phenylene Bridged Phosphite-Macrobicycle q = 7.8° 8.5 Å Conformer A q = 2.6° view into the cavity q = 2.0° 8.3 Å view along P-P-axis Conformer B q = 17.3°

  24. Oxidation of Isomeric P-Macrobicycles

  25. Double-CappingMethod for the Formation of p,m,p-Phenylene Bridged Phosphorus Brigdehead Macrobicycles III 31P NMR of the crude product out,out in,in in,out

  26. X-Ray Structure of out,out-p,m,p-Phenylene Bridged Phosphite-Macrobicycle view along P-P-axis view into the cavity

  27. X-Ray Structure of in,in-p,m,p-Phenylene Bridged Phosphite-Macrobicycle Conformer A view into the cavity Conformer B view along P-P-axis

  28. Double-CappingMethod for the Formation of p,m,p-Phenylene Bridged Phosphorus Brigdehead Macrobicycles III 31P NMR of the crude product out,out in,in ??? in,out

  29. Intertwined out,out-conformer ??? Novel Dioxaphospha[3.1.1.]p,m,p-Cyclophanes

  30. X-Ray Structure of a Novel Bisdioxaphospha[3.1.1.]p,m,p-Cyclophane

  31. Podand Precursors for the Synthesis of Macrobicycles

  32. Single-Capping Method for Macrobicycle Formation

  33. ( C H ) z 2 ( C H ) y 2 ( C H ) x 2 Reaction of in,in-P-Macrobicycle with a Bisazide Topological analogue to propellane structure

  34. 1,2 3 4 5 Extraction of Metal Cations from Aqueous Solution with Macrocyclic P(III)- and P(V) compounds 1 Extractability [%] 2 3 X = lone pair 4 X = S 5 X = O

  35. Complexation of Cu(I) with the in,in-P-Cryptand stabilized [Cu2Cl]+ cation MALDI-TOF: Matrix: 1,8,9-trihydroxyanthracene m/z: 1254 [M-CL-], (Mcalcd = 1293.24) 31P NMR: d 112 br.

  36. Acknowledgement Dr. M. Gruner G. Theumer (TU Dresden) Prof. I. Antipin Dr. I. I. Stoikov Dr. S. Solovieva (Kazan State University) Prof. E. Kazakova Dr. A. Prosvirkin Dr. A. Ziganshina (A.E. Arbuzov Institute Kazan) Prof. R. Schmutzler, Prof. P.G. Jones, Dr. H. Thönnessen (TU Braunschweig) Dr. R. Fröhlich (University Münster) Financial support DFG: Graduiertenkolleg ”Struktur-Eigenschafts-Beziehungen bei Heterocyclen” DFG + RFFI: Projekt 2133/3-1: „Synthese neuer phosphorhaltiger Makrocyclen und Kryptanden“ Fonds der Chemischen Industrie

  37. Oligomeric Hindered Amine Phosphites as Polymer Stabilizers-Phosphorous Amide Method-

  38. Synthesis of Macrocycles with P(III) and P(V) Acid Derivatives

  39. P-Containing Macrocycles from Bisphenols and Naphthols by Phosphorous Amide Method – Literature examples Y. I. Blokhin, D. V. Gusev, V. K. Belsky, A. I. Stash, E. E. Nifantev, Phosphorus, Sulfur and Silicon 1995, 102, 143. Y. I. Blokhin, F. M. Galiaskarova, D. V. Gusev, M. Y. Ergashov, V. K. Belsky and E. E. Nifantev, Phosphorus, Sulfur and Silicon 1996,111, 170.

  40. „Pyrocatechol phosphites“ P.A. Kirpichnikov etal.

  41. Selective Oxidation of a P-Macrocycle II

  42. Selective Oxidation of a Tetrameric Phosphorus Macrocycle

  43. Oxidation of Isomeric Phosphite Cryptands out,out-isomer in,out-isomer in,in-isomer

  44. Natural Products Showing in,out-Isomerism 3a-Acetoxy-15b- hydroxy-7,16-seco- trinervita-7,11-diene Secotrinerviten- 2b,3a-diol Ingenol

  45. P-Containing Macrobicycles - Principles of Formation II - B. Dietrich, P. Viout, J.-M. Lehn, "Macrocyclic Chemistry: Aspects of Organic and Inorganic Supramolecular Chemistry", VCH, Weinheim, New York, Basel, Cambridge, 1992.

  46. P-Containing Macrobicycles - Principles of Formation III - B. Dietrich, P. Viout, J.-M. Lehn, "Macrocyclic Chemistry: Aspects of Organic and Inorganic Supramolecular Chemistry", VCH, Weinheim, New York, Basel, Cambridge, 1992.

  47. Phosphorus Bridgehead Macrobicycles in Literature B.P. Friedrichsen, R.P. Powell, H.W. Whitlock, J. Am. Chem. Soc. 1990, 112, 8931-8941.

  48. Phosphorus Bridgehead Macrobicycles in Literature J. Mitjaville, A.-M. Caminade, J.-P. Majoral, J. Chem. Soc.Chem. Commun.1994, 112, 2161. Ch.B. Allen, L.O. Spreer, J. Org. Chem.1994, 59, 7695-7700. A.A. Chaikovskaja, T.N. Kudrya, R.I. Yurchenko, O.M. Voitsekhovskaya, A.M. Pinchuk, Zh. Obshch. Khim.1988, 58, 1925-1926.

  49. Synthesis of a Thiophosphate Macrobicycle

  50. Complexation of p-Nitrophenol with the in,in-Phosphate

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