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Modified mesoporous aluminophosphate as an efficient solid acid catalyst for the synthesis of novel O- and N-acetylated compounds: solvent free condition

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Abstract

Solid acids such as amorphous aluminophosphates (AlP) modified with different transition metals (Fe/Mo/W) were synthesized by either precipitation or co-precipitation methods. These solid acids were characterized by BET, NH3-TPD, PXRD and FT-IR techniques. The catalytic activity of these solid acids was evaluated in the synthesis of novel O- and N-acetylated compounds of various substituted alcohols, phenols, pyridine alcohols, furan alcohols, aryl alcohols and amines under solvent free conditions with acetic anhydride as an acetylating agent. The reaction conditions were optimized by varying the catalyst, molar ratio of the reactants, reaction temperature and amount of the solid acid catalyst. Among the solid acids, FeAlP consisting of 0.025 mol% Fe showed good catalytic activity in the acetylation reaction and produces high yield of acetylated products. In addition, the catalysts can also be reused in acetylation at least for 4 reaction cycles without significance loss of catalytic activity.

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Scheme 1
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Scheme 2

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Notes

  1. # Novel acetylated organic compounds

Abbreviations

AA:

Acetic anhydride

4-MPA:

4-Methoxy phenyl acetate

4-MP:

4-Methoxy phenol

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Acknowledgments

Authors are thankful to VGST, GoK (GRD-375), for funding, IISc, Bangalore for providing IR, PXRD, GC–MS data and IITM for NMR and BET analysis.

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Authors and Affiliations

  1. Chemistry Research Laboratory, HMS Institute of Technology, Tumkur, Karnataka, 572104, India

    K. Shyamprasad, S. Z. Mohamed Shamshuddin, M. Shyamsundar & N. Thimmaraju

  2. Research and Development Centre, Bharathiar University, Coimbatore, India

    K. Shyamprasad, S. Z. Mohamed Shamshuddin, M. Shyamsundar & N. Thimmaraju

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  1. K. Shyamprasad
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  2. S. Z. Mohamed Shamshuddin
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  3. M. Shyamsundar
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  4. N. Thimmaraju
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Corresponding author

Correspondence to S. Z. Mohamed Shamshuddin.

Appendix 1: Spectral data of O- and N-acetylated compounds

Appendix 1: Spectral data of O- and N-acetylated compounds

4-Methylphenyl acetate (Entry 1, Table 2 )

1H NMR (CDCl3, 300 MHz): δ 2.01 (s, 3H), 2.25 (s, 3H), 6.92 (d, 2H, 7.6 Hz), 7.04 (d, 2H, 8.8 Hz). IR (cm−1): 3027, 2953, 1738, 1160, 754. GC–MS m/z: 150 [M]+. Physical state: Clear liquid

4-Methoxyphenyl acetate (Entry 2, Table 2 )

IR (cm−1): 3019, 2960, 1758, 1506, 1217, 1193, 755; 1H NMR (CDCl3, 300 MHz): δ 2.27 (s, 3H), 3.79 (s, 3H), 6.88 (d, 2H, J = 8.8 Hz), 7.00 (d, 2H, J = 9.0 Hz); 13C (CDCl3, 300 MHz): δ 20.58, 55.12, 114.11, 122.03, 143.92, 156.95, 169.61; GC–MS (m/z) 166 (M+), 124 (100).

1-Acetoxy-1-phenyl propane (Entry 3, Table 2 )

IR (neat) 1737 cm−1; 1H NMR (CDCl3, 300 MHz): δ 0.87 (t, 3H, J = 7.38 Hz), 1.73–1.99 (m, 2H), 2.06 (s, 3H), 5.66 (t, 1H, J = 6.86 Hz), 7.28 (m, 5H); 13C (CDCl3, 300 MHz) δ 9.72, 20.99, 29.12, 77.13, 126.38, 127.63, 128.19, 140.39, 170.12; GC–MS (m/z) 178 (M+), 43(100).

4-Bromophenyl acetate (Entry 4, Table 2 )

IR (neat) 1760 cm−1; 1H NMR (CDCl3, 300 MHz) δ 2.29 (s, 3H), 6.97 (d, 2H, J = 8.7 Hz), 7.48 (d, J = 8.1 Hz, 2H); 13C (CDCl3, 300 MHz): δ 20.99, 118.82, 123.34, 132.39, 149.63, 169.02; GC–MS (m/z) 216(M+), 172(100).

2-Methoxy-4-(3-oxobutyl)phenyl acetate # (Entry 5, Table 2 )

BP: 318 0C; 1H NMR (CDCl3, 300 MHz): δ 2.12 (s, 3H), 2.32(s, 3H), 2.81 (t, 2H, 7.4 Hz), 2.88 (t, 2H, 2.4 Hz), 3.89 (s, 3H), 6.87 (d, 1H, J = 4.6 Hz), 6.93 (s, 1H), 7.34 (d, 1H, J = 12 Hz). 13C NMR (CDCl3, 300 MHz): δ 20.55, 30.23, 30.81, 43.53, 56.34, 112.65, 121.76, 124.89, 137.04, 139.40, 152.21, 170.41, 206.39. GC–MS m/z: 234.88 [M]+. Physical state: Liquid.

2, 6, Di-tert-butyl-4-methyl phenyl acetate (Entry 6, Table 2 )

mp 70–74 °C; IR (KBr) 1763 cm−1; 1H NMR (CDCl3, 300 MHz) δ 1.33 (s, 18H), 2.31 (s, 3H), 2.33 (s, 3H), 7.11 (s, 2H); 13C (CDCl3, 300 MHz): δ 21.56, 22.72, 31.49, 35.25, 127.11, 134.60, 141.93, 171.41; GC–MS (m/z) 262 (M+), 43 (100).

O-chlorobenzyl acetate (Entry 7, Table 2 )

1H NMR (CDCl3, 300 MHz): δ 7.38–7.32 (m, 2H), 7.28–7.2 (m, 2H), 5.21 (s, 2H), 2.10 (s, 3H). GC–MS m/z: 184 [M]+.

1-Acetoxy-1-ethynyl cyclohexane (Entry 8, Table 2 )

IR (neat) 1744 cm−1; 1H NMR (CDCl3, 300 MHz) δ 1.63 (m, 6H), 1.81–1.89 (m, 2H), 2.05 (s, 3H), 2.12 (m, 2H), 2.60 (s, 1H); 13C (CDCl3, 300 MHz): δ 21.87, 22.38, 25.03, 36.84, 74.19, 75.04, 83.58, 169.24; GC–MS (m/z) 123 (M-43+), 43(100).

(E)-3-Phenylprop-2-enyl acetate (Entry 9, Table 2 )

1H NMR (CDCl3, 300 MHz): δ 1.98 (s, 3H), 4.60 (t, J = 6.2 Hz, 2H), 6.20–6.22 (m, 1H), 6.54 (d, J = 1.7 Hz, 1H), 7.17–7.30 (m, 5 H). 13C NMR (CDCl3, 300 MHz): δ 20.95, 64.97, 123.77, 126.42, 127.88, 128.42, 133.99, 136.01, 170.55. GC–MS m/z: 175.43 [M]+.

2-Methoxy-4-(prop-2-en-1-yl) phenyl acetate # (Entry 10, Table 2 )

BP: 282 °C; 1H NMR (CDCl3, 300 MHz): δ 2.37 (s, 3H), 3.23 (d, 2H, 7.8 Hz), 3.97 (s, 3H), 5.12–5.5.64(d, 2H, 16 Hz), 5.98 (m, 1H, 8.8 Hz), 6.78 (d, 1H, 7.6 Hz), 6.98 (s, 1H), 7.12 (d, 1H, 12.6 Hz). 13C NMR (CDCl3, 300 MHz): δ 20.33, 39.04, 55.68, 113.76, 115.13, 121.73, 122.51, 136.52, 137.67, 138.90, 151.39, 169.04. GC–MS m/z: 205.53 [M]+. Physical state: Oily Liquid.

Cyclopropyl (phenyl) methyl acetate (Entry 11, Table 2 )

1H NMR (CDCl3, 300 MHz): δ 0.37–0.40 (m, 2H), 0.53–0.59 (m, 2H), 1.32 (m, 1H), 2.08 (s, 3H), 5.22 (d, J = 4 Hz), 7.27–7.39 (m, 5H). 13C NMR (CDCl3, 100 MHz): δ 2.97, 4.04, 16.48, 21.19, 79.57, 126.51, 127.75, 128.27, 140.28, 170.28. GC–MS m/z: 177.53 [M]+.

Pyridine-2-methyl acetate (Entry 12, Table 2 )

1H NMR (CDCl3, 300 MHz): δ 2.13, (s, 3H), 5.19 (s, 2H), 7.20 (d, 1H, J = 1.6 Hz,), 7.31 (d, 1H, J = 1.7 Hz,), 8.56 (d, 1H, J = 4.8 Hz,). 13C NMR (CDCl3, 300 MHz): δ 20.95, 64.97, 123.00, 126.43, 127.88, 128.42, 133.99, 136.01, 170.55. GC–MS m/z: 150.53 [M]+.

Furan-2-ylmethyl acetate (Entry 13, Table 2 )

1H NMR (CDCl3, 300 MHz): δ 2.06 (s, 3H), 5.04 (s, 2H), 6.35 (d, J = 10 Hz, 2H), 7.41 (s, 1H). 13C NMR (CDCl3, 300 MHz): δ 20.73, 57.99, 97.29, 110.50, 143.19, 150.53, 175.95. GC–MS m/z: 139.24 [M]+.

N-(2,3-dimethylphenyl) acetamide # (Entry 14, Table 2 )

M.P: 134 °C; 1H NMR (CDCl3, 300 MHz): δ 2.13, (s, 3H), 2.29 (s, 3H), 2.45(s, 3H), 7.12 (d, 1H, J = 4.7 Hz,), 7.26 (d, 1H, J = 6.8 Hz), 7.32 (dd, 1H, J = 14.2 and 8.6 Hz), 9.45(bs, 1H). 13C NMR (CDCl3, 300 MHz): δ 14.95, 22.81, 24.68, 112.8, 126.18, 126.92, 130.03, 138.92, 139.25, 170.29. GC–MS m/z: 161.2 [M]+. Physical state: solid

N-[3-(trifluoromethyl) phenyl] acetamide # (Entry 15, Table 2 )

M.P: 104 °C; 1H NMR (CDCl3, 300 MHz): δ 2.01 (s, 3H), 7.13 (d, 1H, J = 12 Hz), 7.32 (dd, 1H, J = 14 and 8.8 Hz), 7.63 (d, 1H, J = 6.8 Hz), 8.32(s, 1H). 13C NMR (CDCl3, 300 MHz): δ 24.02, 120.42, 124.09, 124.93, 126.17, 129.03, 132.36, 138.87, 168.78. GC–MS m/z: 202.15 [M]+. Physical state: solid.

N-(4-cyano-3-methylphenyl) acetamide # (Entry 16, Table 2 )

MP: 160 °C; 1H NMR (CDCl3, 300 MHz): δ 2.11 (s, 3H), 2.56 (s, 3H), 7.65 (bs, 1H), 7.43 (d, 1H, J = 8.7 Hz), 7.88 (d, 1H, J = 4.8 Hz), 7.98(s, 1H). 13C NMR (CDCl3, 300 MHz): δ 20.63, 24.82, 110.12, 115.91, 122.15, 122.87, 132.76, 141.53, 142.70, 170.93. GC–MS m/z: 173.49[M]+. Physical state: solid.

N-(4-ethynylphenyl) acetamide # (Entry 17, Table 2 )

MP: 90 °C; 1H NMR (CDCl3, 300 MHz) δ 2.14 (s, 3H), 4.10 (s, 1H), 7.22 (bs, 1H), 7.32 (dd, 1H, J = 8.4 and 1.8 Hz), 7.45(d, 1H, J = 4.8 Hz), 7.63 (d, 1H, J = 1.2 Hz). 13C NMR (CDCl3, 300 MHz): δ 24.12, 80.91, 83.23, 121.9, 122.8, 125.9, 128.1, 129.3, 138.8, 167.8. GC–MS m/z: 156.2 [M]+. Physical state: solid.

N-[4-(bromoacetyl) phenyl] acetamide # (Entry 18, Table 2 )

BP: 429 °C; 1H NMR (CDCl3, 300 MHz): δ 2.08 (s, 3H), 4.87 (s, 2H), 7.32 (bs, 1H), 2.81 (t, 2H, 7.4 Hz), 7.88 (d, 2H, 8 Hz), 7.95 (d, 2H, 7.6 Hz). 13C NMR (CDCl3, 300 MHz): δ 24.15, 31.45, 121.56, 129.83, 131.09, 142.92, 168.09, 191.80. GC–MS m/z: 255.13 [M]+. Physical state: Liquid.

N-(5-bromo-3-nitropyridin-2-yl) acetamide # (Entry 19, Table 2 )

B.P: 418 °C; 1H NMR (CDCl3, 300 MHz): δ 2.01 (s, 3H), 8.75 (s, 1H), 9.30 (bs, 1H), 9.43 (s, 1H). 13C NMR (CDCl3, 300 MHz): δ 24.61, 111.89, 137.12, 137.88, 141.65, 158.09, 169.12. GC–MS m/z: 376.21 [M]+. Physical state: Liquid.

N-(5-nitro-1, 3-thiazol-2-yl) acetamide # (Entry 20, Table 2 )

MP: 202 °C; 1H NMR (CDCl3, 300 MHz): δ 2.01, (s, 3H), 8.22 (s, 1H), 9.76 (bs, 1H). 13C NMR (CDCl3, 300 MHz): δ 24.15, 132.35, 149.58, 163.82, 170.01. GC–MS m/z: 140.7[M]+. Physical state: solid.

N-(9-oxo-9H-fluoren-4-yl) acetamide # (Entry 21, Table 2 )

M.P: 228 °C; 1H NMR (CDCl3, 300 MHz): δ 2.05 (s, 3H), 7.32 (bs, 1H) 7.42 (dd, 1H, J = 8.2 and 2.4 Hz), 7.51 (d, 2H, J = 8 Hz), 7.68 (d, 1H, J = 4.8 Hz), 8.56 (d, 2H, J = 8 Hz). 13C NMR (CDCl3, 300 MHz): δ 24.07, 119.83, 120.13, 122.91, 126.78, 127.86, 130.67, 131.21, 133.13, 134.98, 139.12, 139.78, 145.64, 169.19, 193.43. GC–MS m/z: 236.76 [M]+. Physical state: solid.Footnote 1

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Shyamprasad, K., Mohamed Shamshuddin, S.Z., Shyamsundar, M. et al. Modified mesoporous aluminophosphate as an efficient solid acid catalyst for the synthesis of novel O- and N-acetylated compounds: solvent free condition. J Porous Mater 23, 1095–1105 (2016). https://doi.org/10.1007/s10934-016-0167-2

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