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Synlett 2017; 28(17): 2315-2319
DOI: 10.1055/s-0036-1589089
letter
© Georg Thieme Verlag Stuttgart · New York

Selective Oxidation of Secondary Amines to N,N-Disubstituted Hydroxylamines by Choline Peroxydisulfate

Alireza Banan
a   Department of Chemistry, Faculty of Sciences, Azarbaijan Shahid Madani University, 53714-161 Tabriz, Iran
,
Hassan Valizadeh
a   Department of Chemistry, Faculty of Sciences, Azarbaijan Shahid Madani University, 53714-161 Tabriz, Iran
,
Akbar Heydari*
b   Department of Chemistry, Tarbiat Modares University, 14155-4838 Tehran, Iran   Email: heydar_a@modares.ac.ir
,
Abolghasem Moghimi
c   Department of Chemistry, Faculty of Science, Islamic Azad University, North Tehran Branch, 191367-4711, Tehran, Iran
› Author AffiliationsPartial financial assistance from the Research Vice Chancellor of Azarbaijan Shahid Madani University is gratefully acknowledged
Further Information

Publication History

Received: 21 April 2017

Accepted after revision: 28 June 2017

Publication Date:
17 August 2017 (online)

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Abstract

N,N-Disubstituted hydroxylamines were prepared directly from secondary amines by a reliable method using an oxidizing task-specific ionic liquid, choline peroxydisulfate. The operational simplicity, high selectivity, and green reaction conditions, make this method efficient and practical.

Key words

hydroxylamines - ionic liquids - choline peroxydisulfate - oxidation - amines - green chemistry

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1589089.
  • Supporting Information
 

  • References and Notes

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  • 54 N,N-Dibenzylhydroxylamine (1a) White powder; isolated yield: 970 mg (91%); mp 122–124 °C. 1H NMR (DMSO-d 6): δ = 4.18 (s, 4 H, CH2–), 7.47–7.63 (m, 10 H, C6H5–), 9.93 (br s, 1 H, N-OH). 13C NMR (DMSO-d 6): δ = 50.07 (–CH2–), 129.01 (C-4), 129.29 (C-3), 130.57 (C-2), 132.33 (C-1, C–CH2–N–). N-Benzyl-N-(tert-butyl)hydroxylamine (1b) White powder; isolated yield: 788 mg (88%); mp 70–72 °C. 1H NMR (DMSO-d 6): δ = 1.46 (s, 9 H), 4.13 (s, 2 H), 9.29 (br s, 1 H, N-OH, exchangeable with D2O). 13C NMR (DMSO-d 6): δ = 25.30, 53.39, 56.95, 128.76, 129.94, 130.47, 133.10. N,N-Diethylhydroxylamine (1c) Brown liquid; isolated yield: 418 mg (94%). 1H NMR (CDCl3): δ = 1.43 (t, J = 6.75 Hz, 6 H, CH3), 3.04 (q, J = 6.75 Hz, 4 H, CH2), 9.25 (br s, 1 H, NOH). 13C NMR (CDCl3): δ = 10.80 (CH3), 41.93 (CH2). N,N-Diisobutylhydroxylamine (1d) Light-brown powder; isolated yield: 675 mg (93%); mp 57–59 °C. 1H NMR (CDCl3): δ = 1.10 (d, J = 6.75 Hz, 12 H, CH3), 2.28 (m, 2 H, –CH–), 2.80 (q, 1 J = 12.25 Hz, 2 J = 6.50, 4 H, –CH2–), 9.26 (br s, 1 H, NOH). 13C NMR (CDCl3): δ = 20.72 (CH3), 25.24 (=CH–), 54.92 (–CH2 –). N,N-Diallylhydroxylamine (1e) Brown liquid; isolated yield: 503 mg (89%). 1H NMR (CDCl3): δ = 3.56 (d, J = 6.50 Hz, 4 H, –CH2–N), 5.45 (t, 1 J = 2 J = 9.25 Hz, 4 H, =CH2), 6.03 (m, 2 H, =CH–), 9.76 (br s, 1 H, NOH). 13C NMR (CDCl3): δ = 48.02 (–CH2–), 123.98 (=CH2), 128.75 (–CH=). Morpholin-4-ol (1f) Brown oily liquid; isolated yield: 329 mg (64%). 1H NMR (DMSO-d 6): δ = 3.19 (t, J = 4.75 Hz, 4 H, –CH2–N), 3.66 (t, J = 4.75 Hz, 4 H, –CH2–O), 10.11 (br s, 1 H, NOH). 13C NMR (CDCl3): δ = 58.7 (–CH2–N), 65.9 (–CH2–O).Piperidin-1-ol (1g) Brown solid; isolated yield: 460 mg (91%); mp 32–34 °C. 1H NMR (CDCl3): δ = 1.66 (br s, 2 H, CH2), 1.88 (br s, 4 H, CH2), 3.16 (br s, 4 H, CH2–N), 9.33 (br s, 1 H, NOH). 13C NMR (CDCl3): δ = 22.34, 22.37, 44.37. Pyrrolidin-1-ol (1h) Brown oily liquid; isolated yield: 313 mg (72%). 1H NMR (CDCl3): δ = 2.01 (br s, 4 H, CH2), 3.31 (br s, 4 H, CH2–N), 9.58 (br s, 1 H, NOH). 13C NMR (CDCl3): δ = 24.31 (–CH2–), 44.96 (–CH2–N). 1H-Imidazol-1-ol (1i) Light-yellow liquid; isolated yield: 310 mg (74%). 1H NMR (CDCl3): δ = 7.13 (br s, 2 H, CH–N), 7.27 (br s, 1 H, N–CH–N), 7.76 (br s, 1 H, NOH). 13C NMR (CDCl3): δ = 121.62, 135.02. 1H-Indol-1-ol (1j) Brown oily liquid; isolated yield: 638 mg (96%). 1H NMR (CDCl3): δ = 6.54 (br s, 1 H, CH-3), 7.12 (t, J = 6.75 Hz, 1 H, CH-5), 7.15 (br s, 1 H, CH-2), 7.19 (t, J = 6.75 Hz, 1 H, CH-6), 7.37 (d, J = 7.75 Hz, 1 H, CH-7), 7.65 (d, J = 7.75 Hz, 1 H, CH-4), 8.18 (br s, 1 H, NOH). 13C NMR (CDCl3): δ = 102.4 (C-3), 111.0 (C-7), 119.7 (C-6), 120.7 (C-4), 121.9 (C-5), 124.2 (C-2), 127.7 (C-9) 135.7 (C-8). 6-Amino-9H-purin-9-ol (1k) Plum powder; isolated yield: 664 mg (88%); mp 210–212 °C. 1H NMR (DMSO-d 6): δ = 7.88 (br s, 2 H, NH2), 8.25 (s, 2 H, –CH–) 4.55 (br s, 1 H, –OH). 13C NMR (CDCl3): δ = 112.56 (C-5), 140.96 (C-8), 149.87 (C-4), 150.72 (C-2), 153.80 (C-6). 4-[1-(2,3-Dimethylphenyl)ethyl]-1H-imidazol-1-ol (1l) Yellow solid; isolated yield: 897 mg (83%); mp 188–190 °C. 1H NMR (CDCl3): δ = 1.68 (d, J = 7.00 Hz, 3 H, CH3), 2.22 (s, 3 H, CH3), 2.29 (s, 3 H, CH3), 4.58 (q, J = 7.00 Hz, 1 H, CH), 6.70 (s, 1 H, CH), 7.01–7.08 (m, 3 H), 8.77 (s, 1 H), 14.41 (br s, 1 H, NOH). 13C NMR (CDCl3): δ = 14.9 (CH3), 20.52 (CH3), 20.94 (CH3), 32.18 (CH), 115.14 (CH), 123.91 (CH), 125.89 (CH), 128.94 (CH), 132.90 (quat C), 134.21 (quat C), 137.31 (CH), 138.57 (quat C), 139.49 (quat C). 2-(2-Chlorophenyl)-2-[hydroxy(methyl)amino]cyclohexanone (1m) Light-yellow powder; isolated yield: 1176 mg (91%); mp 206–208 °C. 1H NMR (CDCl3): δ = 1.55–2.00 (m, 6 H), 2.44–2.63 (m, 5 H), 7.46–7.52 (m, 3 H), 8.14 (d, J = 0.75 Hz, 1 H), 9.53 (br s, 1 H, –OH), 10.57 (br s, 1 H, –OH). 13C NMR (CDCl3): δ = 21.60 (CH2), 28.29 (CH2), 29.41 (CH3), 38.26 (CH2), 40.19 (CH2), 72.60 (quat C), 128.50 (CH), 128.67 (CH), 131.76 (CH), 131.89 (CH), 131.96 (quat C), 135.27 (quat C), 205.28 (quat C, C=O).