The Preparation and Crystal Structures of Octaoxoketocalix[8]arene Derivatives: The Ketocalixarene Counterparts of the Largest “Major” Calixarene
Abstract
:1. Introduction
2. Results
2.1. General Considerations
2.2. Oxidation of Octamethylether of Calix[8]arene
2.3. Crystal Structure of Ketocalix[8]arene 6b
2.4. Demethylation of 6b with Iodocyclohexane/DMF
2.5. Oxidation of Octaacetoxy p-tert-Butyl-calix[8]arene 3c
2.6. Crystal Structure of Octaacetoxy Ketocalix[8]arene 6c
2.7. Preparation and Crystal Structure of Octahydroxyketocalix[8]arene 6a
2.8. Low-Temperature 1H NMR Spectra of 6a
3. Experimental Methods
3.1. General Information
3.2. Crystal Data
- Crystal data for 6a: empirical formula: C98.5H108O21.25, formula weight: 1631.84, temperature: 150.0(1) K, crystal system: monoclinic, space group: I2/a, a: 18.4709(5) Å, b: 22.0612(6) Å, c: 23.7204(7) Å, β: 90.484(3)°, V: 9665.5(5) Å3, Z: 4, ρcalc: 1.121 g/cm3, μ: 0.078 mm−1, F(000): 3476.0, crystal size: 0.24 × 0.09 × 0.08 mm3, radiation: Mo Kα (λ = 0.71073), 2θ range for data collection: 4.41 to 64.572°, index ranges: −23 ≤ h ≤ 27, −32 ≤ k ≤ 28, −33 ≤ l ≤ 35, reflections collected: 44,192, independent reflections: 14328 [Rint =0.0435, Rsigma =0.0584], data/restraints/parameters: 14,328/0/606, goodness-of-fit on F2: 1.028, final R indexes [I ≥ 2σ (I)]: R1: 0.0916, wR2: 0. 0.2518, final R indexes [all data]: R1: 0.1404, wR2: 0.2827, largest diff. peak/hole/e Å−3 0.80/−0.34.
- Crystal data for 6b: empirical formula: C97.67H113.33Cl5O16, formula weight: 1720.50, temperature: 200.0(1) K, crystal system: triclinic, space group: P-1, a: 12.4386(1)Å, b: 13.4767(2) Å, c: 14.6784(1) Å, α: 97.887(1)°, β: 93.365(1)°, γ: 96.941(1)°, V: 2412.32(4) Å3, Z: 1, ρcalc: 1.184 g/cm3, μ: 0.212 mm−1, F(000): 912.0, crystal size: 0.43 × 0.11 × 0.07 mm3, radiation: Mo Kα (λ = 0.71073), 2θ range for data collection: 4.174 to 64.604°, index ranges: −17 ≤ h ≤ 18, −19 ≤ k ≤ 19, −21 ≤ l ≤ 21, reflections collected: 104,881, independent reflections: 15145 [Rint = 0.0309, Rsigma = 0.0221], data/restraints/parameters: 15,145/0/631, goodness-of-fit on F2: 1.031, final R indexes [I ≥ 2σ (I)]: R1: 0.0695, wR2: 0.2071, final R indexes [all data]: R1: 0.0871, wR2: 0.2205, largest diff. peak/hole/e Å−3 0.84/−0.66.
- Crystal data for 6c: empirical formula: C116H112Cl2O24, formula weight: 1960.95, temperature: 150.0(1) K, crystal system: triclinic, space group: P-1, a: 10.0905(1) Å, b: 15.8706(2) Å, c: 17.1177(2) Å, α: 84.812(1)°, β: 76.830(1)°, γ: 82.254(1)°, V: 2639.74(5) Å3, Z: 1, ρcalc: 1.234 g/cm3, μ: 0.134 mm−1, F(000): 1034.0, crystal size: 0.26 × 0.19 × 0.09 mm3, radiation: Mo Kα (λ = 0.71073), 2θ range for data collection: 4.174 to 64.798°, index ranges: −14 ≤ h ≤ 14, −22 ≤ k ≤ 23, −23 ≤ l ≤ 24, reflections collected: 94,717, independent reflections: 16,346 [Rint = 0.0412, Rsigma = 0.0312], data/restraints/parameters: 16,346/0/778, goodness-of-fit on F2: 1.027, final R indexes [I ≥ 2σ (I)]: R1: 0.0737, wR2: 0.1987, final R indexes [all data]: R1: 0.0918, wR2: 0.2101, largest diff. peak/hole/e Å−3 0.57/−0.68.
3.3. Synthesis of Compounds 6a–6c
3.3.1. Preparation of 5,11,17,23,29,35,41,47-Octa-tert-butyl-49,50,51,52,53,54,55,56-octahydroxy-2,8,14,20,26,32,38,44-octaoxo-calix[8]arene (6a)
3.3.2. Preparation of 5,11,17,23,29,35,41,47-Octa-tert-butyl-49,50,51,52,53,54,55,56-octamethoxy-2,8,14,20,26,32,38,44-octaoxocalix[8]arene (6b)
3.3.3. Preparation of 5,11,17,23,29,35,41,47-Octa-tert-butyl-49,50,51,52,53,54,55,56-octaacetoxy-2,8,14,20,26,32,38,44-octaoxo-calix[8]arene (6c)
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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Kogan, K.; Omar, S.; Bogoslavsky, B.; Biali, S.E. The Preparation and Crystal Structures of Octaoxoketocalix[8]arene Derivatives: The Ketocalixarene Counterparts of the Largest “Major” Calixarene. Molecules 2024, 29, 4094. https://doi.org/10.3390/molecules29174094
Kogan K, Omar S, Bogoslavsky B, Biali SE. The Preparation and Crystal Structures of Octaoxoketocalix[8]arene Derivatives: The Ketocalixarene Counterparts of the Largest “Major” Calixarene. Molecules. 2024; 29(17):4094. https://doi.org/10.3390/molecules29174094
Chicago/Turabian StyleKogan, Katerina, Suheir Omar, Benny Bogoslavsky, and Silvio E. Biali. 2024. "The Preparation and Crystal Structures of Octaoxoketocalix[8]arene Derivatives: The Ketocalixarene Counterparts of the Largest “Major” Calixarene" Molecules 29, no. 17: 4094. https://doi.org/10.3390/molecules29174094