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

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

3 MSU, Laboratory of Macrocyclic Receptors ADAMANTYLCALIX[4]ARENES CARBOXYLATED AT THE LOWER RIM 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 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 Temperature 110(2) K Crystal system, space group MONOCLINIC, C2/C Unit cell dimensions a = (8)A b = (14)A c = (3) A Volume 15698(3) A 3 Z, Calculated density 8, Mg/m^3 Analysis of Potential Hydrogen Bonds: Donor – H … Acceptor distances angles N(1) – H(1A) … O(3) 3.024(3)  N(1) – H(1A) … O(4) 2.663(3)  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 ADAMANTYLCALIX[4,6]ARENES CARBOXYLATED AT THE UPPER RIM

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

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

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

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

CONFORMATIONAL PROPERTIES OF ADAMANTYLCALIX[4]ARENES RnSOLVENT T C,  C  G *, KCAL/MOL 1-Adamantyl4Chloroform MeSO 2 Ph-1-Ad4 Chloroform HOOCCH 2 -1-Ad4Tetrachloroethane MeOOCCH 2 -1-Ad4Chloroform HOOC-1-Ad4DMSO30-

20 MSU, Laboratory of Macrocyclic Receptors 2.6. CONFORMATIONAL PROPERTIES OF ADAMANTYLCALIX[6]ARENES Coalescence Temperatures For The Conformational Inversion Of The Adamantylcalix[6]arenes. RnSOLVENT T C,  C  G *, KCAL/MOL tert-Butyl6Chloroform tert-Octyl6Chloroform Adamantyl6 Chloroform MeSO 2 Ph-1-Ad6 Chloroform HOOCCH 2 -1-Ad6Chloroform60-

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

22 MSU, Laboratory of Macrocyclic Receptors 2.8. METHYLENE PARTS OF 1 H NMR SPECTRA of MONBENZYLATED P-TERT-BUTYL- (A) and ADAMANTYL- (B) CALIX[6]ARENE IN CDCl 3

23 MSU, Laboratory of Macrocyclic Receptors 2.9. METYLENE PARTS OF 1 H NMR SPECTRA OF CARBOXYLATED CALIX[6]ARENES 1a, 2a, 2f, 4a and 6a (RT, CDCl 3 ) 1a 2f 4a6a 2a

24 MSU, Laboratory of Macrocyclic Receptors CONJUGATES OF CARBOXYLATED ADAMANTYLCALIX[4,6]ARENES WITH AMINO ACIDS 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. For linear section of the calibration curves Slope (mV decade -1 ) 43±5 (Phe) 57±2 (Phe) 46±1 (Ile) 59±1 (Tyr) Membrane composition for carrier-based ISEs in wt %. Membrane 1Membrane 2 Sensor agent, calixarene 111 Polymer matrix, PVC Plastizer, o-NPOE Ionoc additive, NaTPB-0.4

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

30 MSU, Laboratory of Macrocyclic Receptors ADAMANTYLTHIACALIX[4]ARENES CARBOXYLATED AT THE UPPER RIM 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 CHCl 3 molecules, one of which 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 MSU, Laboratory of Macrocyclic Receptors 4.6. ADAMANTYLATION OF p-H-TC[4]A.

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 Participants: E. Shokova, A. Motornay, I. Vatsuoro, A. Matveev, I. Podolsky, M. Kashapov FUNDS: RFBR, Grant , RFBR, Grant , RFBR, Grant ACKNOWLEDGEMENTS