[MeC(OH)₂]⁺ClO₄ ^-: A New Efficient Organocatalyst for the Preparation of 1-Amido- and 1-Carbamato-alkyl Naphthols

Abstract

[MeC(OH)₂]⁺ClO₄ ^- as a super acidic ionic liquid is found to be a new and highly efficient catalyst in the synthesis of amidoalkyl naphthols via three-component condensation of β-naphthol and aldehydes with nitriles, amides, or carbamates.

multicomponent reactions - amidoalkyl naphthols - ionic liquids - super acids

References and Notes

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Tamaddon, F.; Tavakoli, F. manuscript submitted for publication.

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General Procedure for the [MeC(OH) ₂ ] ⁺ ClO ₄ ^- -Catalyzed Synthesis of Amidoalkyl Naphthols
A mixture of an aldehyde (1 mmol), β-naphthol (1 mmol) with amide, nitrile, urea, or carbamate (1 mmol) in the presence of [MeC(OH)₂]⁺ClO₄ ^- (1 mol%) was stirred in EtOAc (1 mL) at r.t. (or at 80 ˚C under solvent-free conditions) for the given times. After completion of the reaction (TLC monitoring), H₂O was added, and the precipitate was filtered off to give the corresponding amidoalkyl naphthols. Most of the products were known and characterized by comparison of their melting points and spectral data with those reported in the literature without further purification. In some cases the products were recrystallized from EtOH-H₂O (60:40).

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Selected Characterization Data N -[(2-Hydroxynaphthalen-1-yl)(phenyl)methyl]-benzamide (Table 2, Entry 1) ^9,¹8 White solid; mp 235-237 ˚C. IR (KBr): ν_max = 1625, 3065, 3418 cm^-¹. ^¹H NMR (300 MHz, DMSO-d ₆): δ = 7.20-7.90 (m, 16 H), 8.10-8.13 (d, 1 H, J = 8.4 Hz), 9.02 (d, 1 H, J = 8.4 Hz), 10.33 (s, 1 H, NH) ppm. ^¹³C NMR (75 MHz, DMSO-d ₆): δ = 50.0, 119.1, 119.4, 123.4, 127.1, 127.2, 127.5, 127.8, 128.9, 129.1, 129.2, 129.3, 130.1, 132.1, 133.0, 135.0, 142.7, 147.0, 153.9, 166.4 ppm.
N -[(2-Hydroxynaphthalen-1-yl)(4-nitrophenyl)methyl]-benzamide (Table 2, Entry 2) ^²9,8 Yellow solid; mp 247-249 ˚C. IR (KBr): ν_max = 1641, 3234, 3410 cm^-¹. ^¹H NMR (300 MHz, DMSO-d ₆): δ = 7.22-7.56 (m, 9 H), 7.82-7.91 (m, 4 H), 8.06 (d, 1 H, J = 8.4 Hz), 8.14 (d, 2 H, J = 8.4 Hz), 9.04 (d, 1 H, J = 8.1 Hz), 10.35 (s, 1 H, NH) ppm. ^¹³C NMR (75 MHz, DMSO-d ₆): δ = 49.1, 117.4, 118.6, 122.6, 122.8, 123.4, 127.0, 127.4, 127.5, 128.4, 128.7, 130.0, 131.6, 132.2, 134.0, 146.2, 150.2, 153.4, 166.3 ppm.
N -[(2-Hydroxynaphthalen-1-yl)( p -tolyl)methyl]-benzamide (Table 2, Entry 3) ^8,9 White solid; mp 223-225 ˚C. IR (KBr): ν_max = 1627, 3043, 3413 cm^-¹. ^¹H NMR (300 MHz, DMSO-d ₆): δ = 1.97 (s, 3 H, CH₃), 2.23 (s, 3 H, CH₃), 7.05-7.38 (m, 8 H), 7.74-7.81 (m, 2 H), 7.85 (d, 1 H, J = 8.4 Hz), 8.38 (d, 1 H, J = 8.4 Hz), 9.94 (s, 1 H, NH) ppm. ^¹³C NMR (75 MHz, DMSO-d ₆): δ = 20.5, 22.6, 47.6, 118.4, 119.0, 122.3, 126.0, 126.2, 128.5, 129.0, 132.3, 135.0, 139.5, 153.0, 169.0 ppm.
N -[1-(2-Hydroxynaphthalen-1-yl)butyl]benzamide (Table 2, Entry 6) ^³0 White solid; mp 240-242 ˚C. IR (KBr): ν_max = 3415, 3222, 3204, 1633, 1575, 1528, 1342, 1074, 815, 747, 716 cm^-¹. ^¹H NMR (300 MHz, DMSO-d ₆): δ = 10.09 (s, 1 H), 8.60 (d, 1 H, J = 6.3 Hz), 8.23 (d, 1 H, J = 7.6 Hz), 7.81 (t, 3 H, J = 7.2 Hz), 7.71 (d, 1 H, J = 8.8 Hz), 7.53-7.44 (m, 4 H), 7.31 (t, 1 H, J = 7.3 Hz), 7.20 (d, 1 H, J = 8.8 Hz), 6.04 (q, 1 H, J = 7.1 Hz), 2.15-2.10 (m, 1 H), 1.90-1.80 (m, 1 H), 1.51-1.42 (m, 1 H), 1.30-1.20 (m, 1 H), 0.95 (t, 3 H, J = 7.3 Hz) ppm. ^¹³C NMR (75 MHz, DMSO-d ₆): δ = 165.2, 152.8, 134.7, 132.1, 131.1, 128.5, 128.4, 128.3, 128.2, 126.9, 126.3, 122.3, 119.8, 118.6, 118.5, 46.6, 36.0, 19.6, 13.8 ppm.
N -[Phenyl-(2-hydroxy-naphthalen-1-yl)-methyl]-acetamide (Table 2, Entry 7) ^¹¹,²8 White solid; mp 232-233 ˚C. IR (KBr): ν_max = 3390, 3246, 3062, 1640, 1582, 1514, 1372, 1337, 1060, 808, 742, 696, 623 cm^-¹. ^¹H NMR (300 MHz, CDCl₃): δ = 1.95 (s, 3 H), 7.10 (m, 1 H), 7.12 (m, 1 H), 7.15 (m, 1 H), 7.17 (m, 1 H), 7.20 (m, 2 H), 7.21 (m, 1 H), 7.25 (m, 1 H), 7.35 (t, 1 H, J = 7.5 Hz), 7.70 (d, 1 H, J = 9.1 Hz) ppm. ^¹³C NMR (75 MHz, DMSO-d ₆): δ = 23.2, 40.3, 119.2, 122.9, 123.8, 126.6, 126.8, 128.5, 128.8, 128.9, 129.1, 129.8, 132.8, 143.1, 153.7, 169.0 ppm.
4-Bromo- N -[(2-hydroxynaphthalen-1-yl)(phenyl)-methyl]benzamide (Table 2, Entry 10) Yellow solid; mp 239-242 ˚C. IR (KBr): ν_max = 3408, 3246, 3146, 1626 cm^-¹. ^¹H NMR (400 MHz, DMSO-d ₆): δ = 7.22 (m, 7 H), 7.41 (t, 2 H, J = 8.0 Hz), 7.66 (t, 2 H, J = 4.4 Hz), 7.78 (m, 4 H), 8.02 (d, 1 H, J = 8.0 Hz), 7.20 (m, 2 H), 9.08 (d, J = 4.0 Hz, 1 H), 10.26 (s, 1 H) ppm. ^¹³C NMR (100 MHz, DMSO-d ₆): δ = 49.7, 115.5, 118.2, 122.6, 126.8, 128.3, 128.8, 128.9, 133.1, 142.8, 153.6, 167.8 ppm. Anal. Calcd for C₂₄H₁₈BrNO₂: C, 66.68; H, 4.20; Br, 18.48; N, 3.24; O, 7.40. Found: C, 66.75; H, 4.11; N, 3.15.