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Effective acetylation of alcohols, phenols and amines over mesoporous aluminophosphate solid acids under solvent free conditions

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Abstract

Solid acids such as amorphous aluminophosphates (AlP) and iron aluminophosphates (FeAlP) were synthesized by either precipitation or co-precipitation methods. These solid acids were characterized by BET, NH3-TPD, PXRD, FT-IR and NMR techniques for their surface area, surface acidity, crystallinity and functionality. AlPs and FeAlPs were found to be mesoporous in nature. The catalytic activity of these solid acids was determined in acetylation of various alcohols, phenols and amines with acetic anhydride under solvent free conditions. The reaction conditions were optimized by varying the parameters such as 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. These solid acid catalysts can also be reused for acetylation at least for five reaction cycles without any appreciable loss of catalytic activity.

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Acknowledgments

Authors are thankful to Kuvempu University for IR analysis, IISc, Bangalore for providing PXRD, GC–MS data and IITM for NMR & BET analysis.

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Authors and Affiliations

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

    K. Shyamprasad, S. Z. Mohamed Shamshuddin & V. T. Vasantha

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

    K. Shyamprasad & S. Z. Mohamed Shamshuddin

Authors
  1. K. Shyamprasad
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  2. S. Z. Mohamed Shamshuddin
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  3. V. T. Vasantha
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Corresponding author

Correspondence to S. Z. Mohamed Shamshuddin.

Appendix

Appendix

Note: All the purified products were characterized by GC–MS, IR and 1H NMR studies and the data are in comparison with the authentic samples.

Amyl acetate (entry 1, Table 2): 1H-NMR (400 MHz; CDCl3; δ/ppm): 4.049(t, 2H, CH2), 2.040(s, 3H, CH3), 1.63(t, 2H, CH2), 1.52 to 1.14 (m, 4H, 2CH2), 0.91(t, 3H, CH3); GC–MS m/z: 130[M]+.

n-Decyl acetate (entry 2, Table 2): 1H-NMR (400 MHz; CDCl3; δ/ppm): 0.87 (t, 3J(H, H) = 6.8 Hz, 3H, CH2CH3), 1.30 (m, 14H, CH3(CH2)7), 1.61 (m, 2H, OCH2CH2), 2.04 (s, 3H, OAc), 4.04 (t, 3J(H, H) = 6.8 Hz, 2H, OCH2);IR (cm−1): 2,925, 2,854, 1,741, 1,239; GC–MS m/z: 200[M]+.

Triacetin (entry 3, Table 2): 1H NMR (400 MHz, CDCl3) δ 2.03 (d, 9 H, J 8 Hz), 4.1 (dd, 2H, J 4.0, 8.0 Hz), 4.2 (dd, 2H, J 8.0, 8.0 Hz), 5.2 (m, 1H), 4.2 (dd, 2H, J 8.0, 8.0 Hz), 5.2 (m, 1H); IR (cm−1): 1,747, 1,372, 1,225, 1,501; GC–MS m/z: 200[M]+.

Cyclohexyl acetate (entry 4, Table 2): 1H NMR (300 MHz, CDCl3) δ 1.25–1.85 (m, 10H), 2.00 (s, 3H), 4.65 (m, 2H); IR (cm−1): 3,020, 2,940, 1,721, 1,256, 1,215, 756; GC–MS m/z: 159 [M]+.

Phenyl acetate (entry 5, Table 2): 1H NMR (300 MHz, CDCl3) δ 2.21 (s, 3H), 7.0–7.4 (m, 5H); IR (cm−1): 1,763, 1,193, 748; GC–MS m/z: 136 [M]+.

4-Methylphenyl acetate (entry 6, Table 2): 1H NMR (300 MHz, CDCl3) δ 2.01 (s, 3H), 2.25 (s, 3H), 6.92 (d, 2H), 7.04 (d, 2H); IR (cm−1): 3,027, 2,953, 1,738, 1,160, 754; GC–MS m/z: 150 [M]+.

4-Chlorophenyl acetate (entry 7, Table 2): 1H NMR (300 MHz, CDCl3) δ 1.98 (s, 3H), 7.0 (d, 2H), 7.25 (d, 2H); IR (cm−1): 1,763, 1,216, 1,198, 756; GC–MS m/z: 170 [M]+.

Benzene-1,4-diyl diacetate (entry 8, Table 2): 1H NMR (CDCl3) δ 2.29 (s, 6H), 7.10 (s, 4H); IR (KBr): 1,762 cm−1; GC–MS m/z: 194 [M]+.

Benzene-1,2,3-triyl diacetate (entry 9, Table 2): 1H NMR (CDCl3) δ 2.27 (s, 9H), 7.11 (d, J = 8.03 Hz, 2H), 7.25 (t, J = 7.50 Hz, 1H); IR (KBr): 1,765, 1,608 cm−1; GC–MS m/z: 252 [M]+.

Benzyl acetate (entry 10, Table 2): 1H NMR (300 MHz, CDCl3) δ 2.07 (s, 3H), 5.05 (s, 2H), 7.26–7.36 (m, 5H); IR (cm−1): 3,020, 1,733, 1,216, 756; GC–MS m/z: 150 [M]+.

2-Phenethyl acetate (entry 11, Table 2): 1H NMR (CDCl3) δ 2.02 (s, 3H), 2.92 (t, J = 7.09 Hz, 2H), 4.27 (t, J = 7.09 Hz, 2H), 7.29 (m, 5H); IR (neat) 1,740 cm−1; GC–MS m/z: 164 [M]+.

p-Methoxybenzyl acetate (entry 12, Table 2): 1H NMR (400 MHz, CDCl3): δ 2.07 (s, 3H, –O–CO–CH3), 3.80 (s, 3H, O–CH3), 5.04 (s, 2H, –CH2–O–), 6.88(d, J = 8.40 Hz, 2H, –Ph), 7.30 (d, J = 8.40 Hz, 2H, –Ph); IR: 2,950, 1,736, 1,516, 1,245, 1,173, 1,040 cm−1; GC–MS m/z: 180 [M]+.

m-Methoxybenzylacetate (entry 13, Table 2): 1H NMR (CDCl3, δ, ppm): 7.22 (t, J = 8.5 Hz, 1H, ArH), 6.9‐6.8 (m, 3H, ArH), 5.03 (s, 2H, CH2), 3.75 (s, 3H, OCH3), 2.05 (s, 3H, OAc); GC–MS m/z: 180 [M]+.

p-Chlorobenzyl acetate (entry 14, Table 2): 1H NMR (60 MHz, CDCl3): δ 1.95 (s, 3H, –O–CO–CH3), 4.8 (s, 2H, –CH2–O–), 7.0 (m, 4H, ArH); IR: 2,960, 1,746, 1,495, 1,383, 1,234, 1,096, 1,014 cm−1; GC–MS m/z: 184[M]+.

2,4-Dichlorobenzylacetate (entry 15, Table 2): 1H NMR (CDCl3, δ, ppm): 7.66 (d, J = 2.3 Hz, 1H, ArH); 7.37 (dd, J = 8.8, 2.3 Hz, 1H, ArH), 6.77 (d, J = 8.8 Hz, 1H, ArH), 5.22 (s, 2H, CH2), 2.15 (s, 3H, OAc); GC–MS m/z:218 [M]+.

p-nitrobenzyl acetate (entry 16, Table 2): 1H NMR (CDCl3, 400 MHz): δ 2.17(s, 3H, COCH3), 5.22(s, 2H, PhCH2), 7.53 (2H, d, J = 8.8 Hz, ArH), 8.23(2H, d, J = 8.8 Hz, ArH) ppm; IR (KBr) cm−1: 1,235(C–O), 1,738(C=O); GC–MS m/z:195 [M]+.

1-Naphthyl acetate (entry 17, Table 2): 1H NMR (300 MHz, CDCl3) δ 2.4 (s, 3H), 7.2–7.9 (m, 7H); IR (cm−1): 3,061, 2,924, 1,767, 1,368, 1,200, 773; GC–MS m/z: 186 [M]+.

2-Naphthyl acetate (entry 18, Table 2): 1H NMR (300 MHz, CDCl3) δ 2.36 (s, 3H), 7.24 (d, J = 8.85 Hz, 1H), 7.47 (m, 2H), 7.56 (s, 1H), 7.78 (m, 3H); IR (KBr): 1,755 cm−1; GC–MS m/z: 186 [M]+.

Diphenylmethyl acetate (entry 19, Table 2): 1H NMR (CDCl3, δ, ppm): 7.38–7.27 (m, 10H, ArH), 7.00 (s, 1H, CH), 2.02 (s, 3H, OAc); GC–MS m/z:226 [M]+.

Benzoin acetate (entry 20, Table 2): 1H NMR (CDCl3, 400 MHz): 2.23 (s, 3H), 6.84 (s, 1H), 7.32–7.53 (m, 8H), 7.95 (d, J = 8.8 Hz, 2H); IR (neat): 1,738, 1,697 cm−1; GC–MS m/z: 269[M]+.

N-phenylacetamide (entry 21, Table 2): 1H NMR (300 MHz, CDCl3) δ 2.19 (s, 3H), 7.16–7.11 (m, 1H), 7.28 (broad s, 1H), 7.36–7.30 (m, 2H), 7.55–7.52 (m, 2H); IR (cm−1): 3,293, 1,662, 1,598, 1,557, 1,500, 1,431, 1,368, 1,325, 1,262, 1,040, 1,012, 962, 906, 750; GC–MS m/z: 135 [M]+.

N-(2-hydroxyphenyl) acetamide (entry 22, Table 2): 1H NMR (300 MHz, CDCl3) δ 2.24 (s, 3H), 6.90 (m, 1H), 7.02 (m, 2H), 7.42 (m, 1H), 8.80(s, 1H),9.11 (bs, 1H); IR (cm−1): 3,403, 3,150, 1,658, 1,587, 1,539, 1,446, 1,397, 1,287, 1,103, 1,037, 891, 767; GC–MS m/z: 151[M]+.

N-(4-hydroxyphenyl) acetamide (entry 23, Table 2): 1H NMR (300 MHz, CDCl3) δ 2.03 (s, 3H), 7.00 (d, 1H), 7.50 (d, 1H), 8.97(s, 1H), 9.40 (bs, 1H); IR (cm−1): 3,326, 3,164, 1,652, 1,611, 1,565, 1,507, 1,442, 1,372, 1,327, 1,259, 1,228, 1,173, 1,108, 969, 837, 808, 715, 687; GC–MS m/z: 151[M]+.

N-benzylacetamide (entry 24, Table 2): 1H NMR (300 MHz, CDCl3) δ 7.36–7.29 (m, 5H), 6.06 (bs, 1H), 4.43 (d, 2H), 2.03 (s, 3H); IR (cm−1): 3,294, 1,646, 1,548, 1,500, 1,283; GC–MS m/z: 149 [M]+.

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Shyamprasad, K., Mohamed Shamshuddin, S.Z. & Vasantha, V.T. Effective acetylation of alcohols, phenols and amines over mesoporous aluminophosphate solid acids under solvent free conditions. J Porous Mater 21, 1079–1090 (2014). https://doi.org/10.1007/s10934-014-9858-8

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