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MSU, Laboratory of Macrocyclic Receptors

MSU, Laboratory of Macrocyclic Receptors. Moscow State University Chemistry Department. Carboxylated Adamantylcalixarenes. V. Kovalev. MSU, Laboratory of Macrocyclic Receptors. MAIN TOPICS :. ADAMANTYLCALIX[4]ARENES CARBOXYLATED AT THE LOWER RIM

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MSU, Laboratory of Macrocyclic Receptors

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  1. MSU, Laboratory of Macrocyclic Receptors Moscow State University Chemistry Department Carboxylated Adamantylcalixarenes V. Kovalev

  2. MSU, Laboratory of Macrocyclic Receptors MAIN TOPICS: • ADAMANTYLCALIX[4]ARENES CARBOXYLATED AT THE LOWER RIM • ADAMANTYLCALIX[4,6]ARENES CARBOXYLATED AT THE UPPER RIM • CONJUGATES OF CARBOXYLATED ADAMANTYLCALIX[4,6]ARENES WITH AMINO ACIDS • ADAMANTYLTHIACALIX[4]ARENES CARBOXYLATED AT THE UPPER RIM

  3. MSU, Laboratory of Macrocyclic Receptors • ADAMANTYLCALIX[4]ARENES CARBOXYLATED AT THE LOWER RIM

  4. MSU, Laboratory of Macrocyclic Receptors 1.1. CALIX[4]ARENES CARBOXYLATED AT THE LOWER.

  5. MSU, Laboratory of Macrocyclic Receptors 1.2. COMMON STRATEGY OF THE LOWER RIM CARBOXYLATION OF CALIX[4]ARENES.

  6. MSU, Laboratory of Macrocyclic Receptors 1.3. ADAMANTYLCALIX[4]ARENES CARBOXYLATED AT THE LOWER RIM.

  7. MSU, Laboratory of Macrocyclic Receptors 1.4. p-(1-ADAMANTYL)CALIX[4]ARENE TETRACARBOXYLIC ACID AND ITS DERIVATIVES..

  8. MSU, Laboratory of Macrocyclic Receptors 1.5. COMPLEXATION OF TETRADIETHYLAMIDE OF AdC4A CARBOXILIC ACID WITH Sr(Pic)2.

  9. MSU, Laboratory of Macrocyclic Receptors 1.6. AdC4A SELECTIVELY CARBOXYLATED AT THE LOWER RIM.

  10. MSU, Laboratory of Macrocyclic Receptors 1.7. AdC4A SELECTIVELY CARBOXYLATED AT THE LOWER RIM

  11. MSU, Laboratory of Macrocyclic Receptors 1.8. THE ALKYLATION OF CALIXARENE NITRILES IN TRIFLUOROACETIC ACID (TFA).

  12. MSU, Laboratory of Macrocyclic Receptors 1.9. ADAMANTYLATION OF 1,3-DICYANOMETHOXY-p-H-CALIX[4]ARENE IN TFA

  13. MSU, Laboratory of Macrocyclic Receptors 1.10. X-RAY STRUCTURE OF 5,17-DI(1-Ad)-26,28-DI[N-(1‑Ad)­CARBOMOYLMETHOXY]CALIX[4]ARENE. Empirical formula C96 H116 N2 O6 Formula weight 1393.91 Temperature 110(2) K Crystal system, space group MONOCLINIC, C2/C Unit cell dimensions a = 60.018(8)A b = 10.9904(14)A c = 24.777(3) A Volume 15698(3) A3 Z, Calculated density 8, 1.180 Mg/m^3 Analysis of Potential Hydrogen Bonds: Donor – H… Acceptor distances angles N(1) – H(1A) … O(3) 3.024(3) 164.03 N(1) – H(1A) … O(4) 2.663(3) 110.84 O(3) – H(3A) … O(6) 2.715(3) 178(3) O(5) – H(5A) … O(4) 2.768(2) 173(3)

  14. MSU, Laboratory of Macrocyclic Receptors • ADAMANTYLCALIX[4,6]ARENES CARBOXYLATED AT THE UPPER RIM

  15. 2.1. FULL ADAMANTYLATION OF p-H-CALIX[4, 6]ARENES BY CARBOXYLATED ADAMANTANOLS MSU, Laboratory of Macrocyclic Receptors

  16. 2.2. SELECTIVE ADAMANTYLATION OF p-H-CALIX[4, 6]ARE-NES WITH CARBOXYLATED ADAMANTANOLS MSU, Laboratory of Macrocyclic Receptors

  17. 2.3. UPPER and LOWER RIM METHYLATION OF CARBOXY LATED DAMANTYLCALIX[6]ARENES MSU, Laboratory of Macrocyclic Receptors

  18. 2.4. UPPER RIM MODIFICATIONS OF CARBOXYLATED ADAMANTYLCALIX[6]ARENES. MSU, Laboratory of Macrocyclic Receptors

  19. 3-MeOOCCH2-1-Ad R 1-Adamantyl 3-MeSO2Ph-1-Ad n 4 4 4 SOLVENT Chloroform Chloroform Chloroform 53 TC, C 57 60 15.8 G*, KCAL/MOL 15.7 15.9 2.5. CONFORMATIONAL PROPERTIES OF ADAMANTYLCALIX[4]ARENES 3-HOOC-1-Ad 4 DMSO 30 - 3-HOOCCH2-1-Ad 4 Tetrachloroethane 95 17.5

  20. R n SOLVENT TC, C G*, KCAL/MOL 2.6. CONFORMATIONAL PROPERTIES OF ADAMANTYLCALIX[6]ARENES tert-Butyl 6 Chloroform 11 13.3 tert-Octyl 6 Chloroform 13 13.6 1-Adamantyl 6 Chloroform 12 - 3-MeSO2Ph-1-Ad 6 Chloroform 25 - 3-HOOCCH2-1-Ad 6 Chloroform 60 - MSU, Laboratory of Macrocyclic Receptors Coalescence Temperatures For The Conformational Inversion Of The Adamantylcalix[6]arenes.

  21. MSU, Laboratory of Macrocyclic Receptors 2.7. 1H NMR SPECTRUM of p-(3-CARBOXYMETHYL-1-ADAMANTYL)CALIX[6]ARENE in CDCl3 at 298 K.

  22. MSU, Laboratory of Macrocyclic Receptors 2.8. METHYLENE PARTS OF 1H NMR SPECTRA of MONBENZYLATED P-TERT-BUTYL- (A) and ADAMANTYL- (B) CALIX[6]ARENE IN CDCl3

  23. 2.9. METYLENE PARTS OF 1H NMR SPECTRA OF CARBOXYLATED CALIX[6]ARENES 1a, 2a, 2f, 4a and6a (RT, CDCl3) MSU, Laboratory of Macrocyclic Receptors 1a 2a 2f 4a 6a

  24. MSU, Laboratory of Macrocyclic Receptors • CONJUGATES OF CARBOXYLATED ADAMANTYLCALIX[4,6]ARENES WITH AMINO ACIDS

  25. MSU, Laboratory of Macrocyclic Receptors 3.1. PRINCIPAL STRATEGIES OF PEPTIDOCALIX[N]ARENE SYNTHESES. UPPER AND LOWER RIM DERIVATIVES.

  26. MSU, Laboratory of Macrocyclic Receptors 3.2. CONJUGATES OF CALIX[4,6]ARENES WITH AMINO ACIDS.

  27. MSU, Laboratory of Macrocyclic Receptors 3.4. CONJUGATES OF ADAMANTYLCALIX[4,6]ARENES WITH AMINO ACIDS. SYNTHESIS

  28. MSU, Laboratory of Macrocyclic Receptors 3.5. CONJUGATES OF AdC[4,6]A WITH AMINO ACIDS. POTENTIOMETRIC MEASUREMENTS. Membrane composition for carrier-based ISEs in wt %.Membrane 1Membrane 2Sensor agent, calixarene 1 1 1Polymer matrix, PVC 66.0 65.7Plastizer, o-NPOE 33.0 32.9Ionoc additive, NaTPB - 0.4 For linear section of the calibration curvesSlope (mV decade-1) 43±5 (Phe) 57±2 (Phe) 46±1 (Ile) 59±1 (Tyr)

  29. MSU, Laboratory of Macrocyclic Receptors 3.6. CONJUGATES OF AdC[4,6]A WITH AMINO ACIDS. WORKING CHARACTERISTICS OF THE MEMBRANE 2. Potentiometric selectivity coefficients (log KPot) of the ISE 2 for ME Phe and Ile in the presence of various interfering ions Effect of pH of the test solution on the potential response of the ME Phe.H+ ion-selective electrode

  30. MSU, Laboratory of Macrocyclic Receptors • ADAMANTYLTHIACALIX[4]ARENES CARBOXYLATED AT THE UPPER RIM

  31. MSU, Laboratory of Macrocyclic Receptors 4.1. THE WAYS OF TC4A TRANSFORMATIONS.

  32. MSU, Laboratory of Macrocyclic Receptors 4.2. TC[4]A MODIFIED AT THE UPPER RIM. LIT. DATA

  33. MSU, Laboratory of Macrocyclic Receptors 4.3. THE BROMINATION 0F 1,3-DIPROPYLOXY-TC[4]A. LIT. DATA

  34. MSU, Laboratory of Macrocyclic Receptors 4.4. FIRST SYNTHESIS OF ADAMANTYLATED TC[4]A

  35. MSU, Laboratory of Macrocyclic Receptors 4.5. X-RAY STRUCTURE OF p-(1-ADAMANTYL)-TC4A. i)AdTC4A crystallized in the orthorhombic crystal system. ii) the unit cell contained both AdTC4A and four CHCl3 molecules, one ofwhich was localized within the cavity of the host molecule; iii) AdTC4A adopted a cone conformation; iv) the average distance between two adjacent oxygen atoms was 2.77 Ǻ as and in the case of t-BuTC4A.

  36. 4.6. ADAMANTYLATION OF p-H-TC[4]A . MSU, Laboratory of Macrocyclic Receptors

  37. MSU, Laboratory of Macrocyclic Receptors 4.7. SYNTHESIS OF THE AdTC[4]A CARBOXYLATED AT THE UPPER RIM .

  38. MSU, Laboratory of Macrocyclic Receptors ACKNOWLEDGEMENTS Participants: E. Shokova, A. Motornay, I. Vatsuoro, A. Matveev, I. Podolsky, M. Kashapov FUNDS: RFBR, Grant - 03-02-33353, RFBR, Grant - 03-02-06254, RFBR, Grant - 03-02-06252

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