Facile Synthesis of o- and p-(1-Trifluoromethyl)-alkylated Phenols via Generation and Reaction of Quinone Methides

Yuefa Gong; Katsuya Kato

doi:10.1055/s-2002-20458

LETTER

Facile Synthesis of o- and p-(1-Trifluoromethyl)-alkylated Phenols via Generation and Reaction of Quinone Methides

Yuefa Gong, Katsuya Kato*
National Institute of Advanced Industrial Science and Technology (AIST), 2266-98 Anagahora, Shimoshidami, Moriyama-ku, Nagoya 463-8560, Japan
e-Mail: katsuya-kato@aist.go.jp;

Abstract

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Abstract

Several ortho- and para-(1-chloro-2,2,2-trifluoroethyl)phenols were prepared from the corresponding alcohols and thionyl chloride in the presence of pyridine. They reacted smoothly with sodium borohydride and Grignard reagents under mild conditions, forming 2,2,2-trifluoroethyl- or 1-trifluoromethylalkylphenols in high yields.

Key words

trifluoroalkyl - phenol - sodium borohydride - Grignard reagent - quinone methide

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Referenzen

References

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9

1b: A colorless oil. ¹H NMR (CDCl₃): δ = 7.09 (2 H, s), 4.98 (1 H, q, J = 6.8 Hz), 4.52 (1 H, br, s), 2.25 (6 H, s). ¹⁹F NMR (CDCl₃): δ = 88.68 (3 F, d, J = 6.8 Hz). MS: m/z (%) = 238(32) [M⁺], 203(100), 169(41), 153(67). HRMS: Calcd: 238.0372; found: 238.0373. 2b: A colorless oil. ¹H NMR (CDCl₃): δ = 7.37 (2 H, d, J = 8.4 Hz), 6.85 (2 H, d, J = 8.4 Hz), 5.76 (1 H, br, s), 5.06 (1 H, q, J = 6.8 Hz). ¹⁹F NMR (CDCl₃): δ = 88.39 (3 F, d, J = 6.8 Hz). MS: m/z (%) = 210(39) [M⁺], 175(100), 141(42), 125(67), 96(24). HRMS: Calcd: 210.0059; found: 210.0059. 3b: A colorless oil. ¹H NMR (CDCl₃): δ = 7.59 (1 H, d, J = 7.5 Hz), 7.20 (1 H, m), 7.02 (1 H, m), 6.82 (1 H, d, J = 8.1 Hz), 6.17 (1 H, br, s), 5.82 (1 H, q, J = 7.0 Hz). ¹⁹F NMR (CDCl₃): δ = 88.80 (3 F, d, J = 7.0 Hz). MS: m/z (%) = 210(68) [M⁺], 175(60), 155(30), 145(60), 141(74), 127(100), 96(39). HRMS: Calcd: 210.0059; found: 210.0061. 1c: Colorless needles, mp 86-87 °C. ¹H NMR (CDCl₃): δ = 6.89 (2 H, s), 4.62 (1 H, s), 3.21 (2 H, q, J = 10.8 Hz), 2.23 (6 H, s). ¹⁹F NMR (CDCl₃): δ = 95.53 (3 F, t, J = 10.8 Hz). MS. m/z (%) = 204(57) [M⁺], 135(100), 109(7), 91(25). Anal. Calcd for C₁₀H₁₁F₃O: C, 58.82; H, 5.43. Found: C, 58.72; H, 5.42. 2c: Colorless needles, mp 56-58 °C. ¹H NMR (CDCl₃): δ = 7.15 (2 H, d, J = 8.2 Hz), 6.81 (2 H, d, J = 8.2 Hz), 5.95 (1 H, br, s), 3.27 (2 H, q, J = 11.0 Hz). ¹⁹F NMR (CDCl₃): δ = 95.48 (3 F, t, J = 11.0 Hz). MS: m/z (%) = 176(40) [M⁺], 157(3), 107(100). Anal. Calcd for C₈H₇F₃O: C, 54.55; H, 4.01. Found: C, 54.50; H, 4.02. 3c: A colorless oil. ¹H NMR (CDCl₃): δ =7.25 (1 H, d, J = 7.5 Hz), 6.92-7.22 (2 H, m), 6.79 (1 H, d, J = 7.9 Hz), 5.12 (1 H, br, s), 3.46 (2 H, q, J = 10.8 Hz). ¹⁹F NMR (CDCl₃): δ = 96.33 (3 F, t, J = 10.8 Hz). MS: m/z (%) = 176(72) [M⁺], 156(42), 107(100). Anal. Calcd for C₈H₇F₃O: C, 54.55; H, 4.01. Found: C, 54.47; H, 4.00. 1d: Colorless needles, mp 109-110 °C. ¹H NMR (CDCl₃): δ = 6.87 (2 H, s), 5.60 (1 H, m), 5.00 (1 H, d, J = 18.0 Hz), 4.96 (1 H, d, J = 9.2 Hz), 4.67 (1 H, s), 3.14 (1 H, m), 2.66 (2 H, m), 2.21 (6 H, s). ¹⁹F NMR (CDCl₃): δ = 91.99 (3 F, d, J = 9.4 Hz). MS: m/z (%) = 244(10) [M⁺], 203(100), 153(27), 91(12). Anal. Calcd for C₁₃H₁₅F₃O: C, 63.93; H, 6.19. Found: C, 63.73; H, 6.16. 11: Colorless plates, mp 57-58 °C. ¹H NMR (CDCl₃): δ = 6.51 (1 H, s), 5.97 (1 H, s), 5.20 (1 H, q, J = 8.1 Hz), 1.97 (3 H, s), 1.95 (3 H, s). ¹⁹F NMR (CDCl₃): δ = 106.96 (3 F, d, J = 8.1 Hz). MS: m/z (%) = 203(100) [M⁺], 153(26). Anal. Calcd for C₁₀H₉F₃O: C, 59.41; H, 4.49. Found: C, 59.60; H, 4.50. 2d: A colorless oil. ¹H NMR (CDCl₃): δ = 7.15 (2 H, d, J = 8.4 Hz), 6.81 (2 H, d, J = 8.4 Hz), 5.60 (1 H, m), 5.21 (1 H, s), 5.00 (1 H, d, J = 16.9 Hz), 4.96 (1 H, d, J = 10.3 Hz), 3.23 (1 H, m), 2.67 (2 H, m). ¹⁹F NMR (CDCl₃): δ = 91.67 (3 F, d, J = 9.4 Hz). MS: m/z (%) = 216(15) [M⁺], 175(100), 127(6), 125(51). Anal. Calcd for C₁₁H₁₁F₃O: C, 61.11; H, 5.13. Found: C, 61.03; H, 5.11. 3d: A colorless oil. ¹H NMR (CDCl₃): δ = 7.31 (1 H, d, J = 8.3 Hz), 6.94-7.18 (2 H, m), 6.87 (1 H, d, J = 7.7 Hz), 5.60 (1 H, m), 5.07 (1 H, s), 4.99 (1 H, d, J = 15.4 Hz), 4.95 (1 H, d, J = 9.01 Hz), 4.10 (1 H, m), 2.70 (2 H, m). ¹⁹F NMR (CDCl₃): δ = 92.49 (3 F, d, J = 9.2 Hz). MS: m/z (%) = 216(39) [M⁺], 215(44), 195(17), 175(62), 155(61), 127(100), 115(28), 107(31). Anal. Calcd for C₁₁H₁₁F₃O: C, 61.11; H, 5.13. Found: C, 61.09; H, 5.10.