Synthesis and Characterization of P-tert-Butyl-calix[9, 10, 11 and 12]arenes.

Abstract

The p-tert-butylcalix[n]arenes (n = 9, 10, 11, 12) have been co-synthesized in significant amounts from cyclocondensation reaction mixture of linear phenolic oligomers in basic conditions. They have been isolated and fully characterized.

Notes

Melting points (°C, uncorrected) were determinated on a Electrothermal 9100 Capillary apparatus. ¹H- and ¹³C-NMR spectra were recorded on a Bruker AC 200 (200 and 50.32 MHz, CDCl₃, TMS, δ in ppm). Mass spectra were obtained by electrospray technique, negative mode (HP 5989/MS engine, S. C. A., CNRS, Solaize). IR was performed on a Perkin-Elmer 1310 apparatus (ν in cm⁻¹) and UV spectra were recorded on a Perkin-Elmer Lambda 2 UV/VIS apparatus (λ max in nm, ε in dm³ mol⁻¹ cm⁻¹). Elemental analyses were done by S. C. A., CNRS, Solaize. Macherey-Nagel plates were used for TLC analyses (SiO₂, Polygram SIL G/UV 254, ref. 805021; Al₂O₃ Polygram ALOX N/UV 254, ref. 802021) and a Touzart & Matignon column for RPHPLC (Spherisorb ODS1, 250×4.6 mm). 1: M.p. 295–296°C. ¹H NMR: δ 9.77 (s, 9H, Ar-OH), 7.17 (s, 18H, Ar-H), 3.91 (br s, 18H, Ar-CH ₂-Ar), 1.25 (s, 81H, C(CH ₃)₃). ¹³C NMR: δ 147.03, 144.35, 127.78, 125.74 (Ar C), 33.98 (C(CH₃)₃), 32.42 (Ar-CH₂-Ar), 31.48 (C(CH₃)₃). I.R. (KBr): 3260 (OH stretch), 2950 (CH₃ stretch), 2860 (CH₂ stretch), 1480 (CH₃ deformation), 1390–1360 (OH deformation), 1290–1250-1200 (CO stretch). U. V. (CHCl₃): 283 (s, 23154), 289.6 (27114). ES-MS: 1457.8 [M-H+]⁻, 728.4 [(M-2H⁺)]^2-/2. Elem. Anal. Calc. for C₉₉H₁₂₆O₉, CH₃CN (1501.15): C 80.81, H 8.66, O 9.59; found: C 80.68, H 8.80, O 9.49. 2: M.p. 300–301 °C. ¹H NMR: δ 9.23 (s, 10H, Ar-OH), 7.14 (s, 20H, Ar-H), 3.91 (s, 20H, Ar-CH ₂-Ar), 1.24 (s, 90H, C(CH ₃)₃). ¹³C NMR: δ 147.00, 144.30, 127.87, 125.63 (Ar C), 33.96 (C(CH₃)₃), 32.21 (Ar-CH₂-Ar), 31.46 (C(CH₃)₃). I.R. (KBr): 3300 (OH stretch), 2960 (CH₃ stretch), 2870 (CH₂ stretch), 1480 (CH₃ deformation), 1390–1360 (OH deformation), 1300–1250-1210 (CO stretch). U.V. (CHCl₃): 281 (s, 36984), 288.7 (40556). ES-MS: 1621.0 [M-H⁺]⁻, 810.0 [(M-2H⁺)]^2-/2. Elem. Anal. Calc. for C₁₁₀H₁₄₀O₁₀, 0.5 H₂O (1631.32): C 80.99, H 8.71, O 10.29; found: C 80.98, H 8.77, O 10.00. 3: M.p. 383–384°C. ¹H NMR: δ 9.53 (s, 11H, Ar-OH), 7.15 (s, 22H, Ar-H), 3.91 (s. 22H, Ar-CH ₂-Ar), 1.24 (s, 99H, C(CH ₃)₃). ¹³C NMR: δ 147.22, 144.20, 127.60, 125.72 (Ar C), 33.97 (C(CH₃)₃), 32.31 (Ar-CH₂-Ar), 31.50 (C(CH₃)₃). I. R. (KBr): 3200 (OH stretch), 2960 (CH₃ stretch), 2870 (CH₂ stretch), 1480 (CH₃ deformation), 1390–1360 (OH deformation), 1300-1250-1200 (CO stretch). U. V. (CHCl₃): 284 (s, 28934), 298 (31922). ES-MS: 1783.6 [M-H⁺]⁻, 891.1 [(M-2H⁺)]^2-/2. Elem. Anal. Calc. for C₁₂₁H₁₅₄O₁₁, 2 CH₃CN (1866.66): C 80.43, H 8.64, O 9.42; found: C 80.39, H 8.66. O 9.68. 4: M.p. > 400°C (dec.). ¹H NMR: δ 9.51 (s, 12H, Ar-OH), 7.08 (s, 24H, Ar-H), 3.82 (br s, 24H, Ar-CH ₂-Ar), 1.23 (s, 108H, C(CH ₃)₃). ¹³C NMR: δ 147.19, 144.22, 127.66, 125.81 (Ar C), 34.01 (C(CH₃)₃), 32.39 (Ar-CH₂-Ar), 31.54 (C(CH₃)₃). I. R. (KBr): 3200 (OH stretch), 2960 (CH₃ stretch), 2870 (CH₂ stretch), 1480 (CH₃ deformation), 1390–1360 (OH deformation), 1300-1250-1200 (CO stretch). U. V. (CHCl₃): 281 (s, 35536), 288.5 (38500). ES-MS: 1944.7 [M-H⁺]⁻, 972.0 [(M-2H⁺)]^2-/2. Elem. Anal. Calc. for C₁₃₂H₁₆₈O₁₂, 0.5 H₂O (1955.80): C 81.07, H 8.71, O 10.22; found: C 81.16, H 9.09, O 10.30.