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

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Presentation on theme: "Phosphorus Containing Macrocycles and Macrobicycles W.D. Habicher and I. Bauer University of Technology Dresden Institute of Organic Chemistry."— Presentation transcript:

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

2 HAS-Phosphites as Antioxidants for Synthetic Polymers long term thermo stabilizer light and long term thermo stabilizer processing 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 Synthesis of Macrocycles with P(III) and P(V) Acid Derivatives X = Cl, NR 2 Y = lone pair, O, S P chloride methodP amidite method

7 Stereoisomerism of Tetracoordinated P(III)- and P(V)-Macrocycles 2 Phosphorus Centers 4 Phosphorus Centers 3 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 Dimers Dimers + Trimers Tetramer Different Ring Sizes of P-Macrocycles

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

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

19 Double-Capping Method for Macrobicycle Formation I

20 Oxidation of in,out-Phosphite Macrobicycle 31 P{ 1 H} NMR:  = (in), (out) 31 P{ 1 H} NMR:  = (in), (out) 31 P{ 1 H} NMR:  = (in), (out) k ox [s -1 ] (298 K) out-P2.74  in-P1 

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

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

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

24 Oxidation of Isomeric P-Macrobicycles

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

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

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

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

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

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

35 Complexation of Cu(I) with the in,in-P-Cryptand MALDI-TOF: Matrix: 1,8,9-trihydroxyanthracene m/z: 1254 [M-CL - ], (M calcd = ) 31 P NMR:  112 br. stabilized [Cu 2 Cl] + cation

36 Acknowledgement Dr. M. Gruner G. Theumer (TU Dresden) Prof. I. Antipin Dr. I. I. Stoikov Dr. S. Solovieva (Kazan State University) 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 Prof. E. Kazakova Dr. A. Prosvirkin Dr. A. Ziganshina (A.E. Arbuzov Institute Kazan)

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 et al.

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 Secotrinerviten- 2 ,3  -diol 3  -Acetoxy-15  - hydroxy-7,16-seco- trinervita-7,11-diene 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,

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

49 Synthesis of a Thiophosphate Macrobicycle

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

51 Reaction of Phosphorous Dichlorides with Bisphenols III

52 Phosphorous Amide Method II -Asymmetric P-Macrocycles as Unstable Intermediates- - Formation of Symmetric P-Macrocycles and Open Chain Products-


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