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Green Chemistry
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1H NMR (300 MHz, CDCl3): δ 7.63-7.54 (m, 2H), 7.46-7.30 (m, 3H), (300 MHz, CDCl3): δ 7.38-7.27 (m, 5H), 3.92 (d, 1H, J =V1ie4w.4ArtHiczle),O3n.li7ne1
DOI: 10.1039/C6GC00408C
4.52 (s, 1H), 4.43 (d, 1H, J = 14.2 Hz), 4.36 (dd, 1H, J = 0.4, 14.2 Hz), (dd, 1H, J = 0.4, 14.4 Hz), 3.29 (d, 1H, J = 14.2 Hz), 3.00 (d, 1H, J =
1.12 (s, 9H). 13C NMR (75.5 MHz, CDCl3): δ 136.3, 128.6, 128.3, 14.2 Hz), 1.17 (s, 9H). 13C NMR (75.5 MHz, CDCl3): δ 134.1, 131.2,
126.4, 124.8 (q, JC,F = 285.6 Hz), 76.6 (q, JC,F = 28.7 Hz), 69.9, 68.7, 128.3, 127.3, 125.9 (q, JC,F = 297.2 Hz), 75.4 (q, JC,F = 27.0 Hz), 68.5,
26.4. 19F NMR (470.6 MHz, CDCl3): δ −78.01 (s, CF3). HRMS (ESI): m/z 68.3, 38.5, 26.4. 19F NMR (470.6 MHz, CDCl3): δ −78.64 (s, CF3).
calcd for C13H18F3N2O [M+H]+ 275.1366, found 275.1356.
HRMS (ESI): m/z calcd for C14H20F3N2O [M+H]+ 289.1522, found
289.1512.
3-(tert-Butyldiazenyl)-1,1,1-trifluoro-2-(p-tolyl)propan-2-ol (7b)
2-[(tert-Butyldiazenyl)methyl]-1,1,1-trifluoro-4-phenylbutan-2-ol
(7g)
Following the general procedure starting from 1b (0.91 mL, 6
mmol), diazene 7b was obtained as a pale yellow oil (1.73 g, 99%).
1H NMR (300 MHz, CDCl3): δ 7.46 (d, 2H, J = 8.2 Hz), 7.19 (d, 2H, J = Following the general procedure starting from 1g (1.01 mL, 6
8.2 Hz), 4.52 (s, 1H), 4.41 (d, 1H, J = 14.2 Hz), 4.32 (d, 1H, J = 14.2 mmol), diazene 7g was obtained as a pale yellow oil (1.81 g, 99%).
Hz), 2.35 (s, 3H), 1.13 (s, 9H). 13C NMR (75.5 MHz, CDCl3): δ 138.5, 1H NMR (300 MHz, CDCl3): δ 7.35-7.17 (m, 5H), 4.03 (d, 1H, J = 14.4
133.3, 129.0, 126.3, 124.8 (q, JC,F = 285.6 Hz), 76.5 (q, JC,F = 28.8 Hz), Hz), 3.97 (d, 1H, J = 14.4 Hz), 2.97-2.73 (m, 2H), 2.25-1.99 (m, 2H),
70.0, 68.8, 26.5, 21.1. 19F NMR (470.6 MHz, CDCl3): δ −78.07 (s, CF3). 1.23 (s, 9H). 13C NMR (75.5 MHz, CDCl3): δ 141.2, 128.7, 128.3,
HRMS (ESI): m/z calcd for C14H20F3N2O [M+H]+ 289.1522, found 126.2, 126.0 (q, JC,F = 286.8), 77.2, 75.1 (q, JC,F = 27.8 Hz), 68.7, 35.3,
28.9, 26.6. 19F NMR (470.6 MHz, CDCl3): δ −78.95 (s, CF3). HRMS
289.1521.
(ESI): m/z calcd for C15H22F3N2O [M+H]+ 303.1679, found 303.1679.
3-(tert-Butyldiazenyl)-2-(2,4-dimethoxyphenyl)-1,1,1-
trifluoropropan-2-ol (7c)
3-(tert-Butyldiazenyl)-1,1,1-trifluoro-2-methylpropan-2-ol (7h)
Following the general procedure starting from 1c (1.47 g, 6 mmol), Following the general procedure starting from 1h (0.52 mL, 6
diazene 7c was obtained as a pale yellow oil (2.01 g, 99%). 1H NMR mmol), diazene 7h was obtained as a pale yellow oil (1.27 g, 99%).
(300 MHz, CDCl3): δ 7.43 (d, 1H, J = 8.6 Hz), 6.53-6.48 (m, 2H), 5.68 1H NMR (300 MHz, CD2Cl2): δ 3.93 (d, 1H, J = 13.7 Hz), 3.81 (d, 1H, J
(d, 1H), 4.51 (d, 1H, J = 14.3 Hz), 4.38 (d, 1H, J = 14.3 Hz), 3.85 (s, = 13.7 Hz), 1.44 (s, 3H), 1.18 (s, 9H). 13C NMR (125 MHz, CD2Cl2): δ
3H), 3.81 (s, 3H), 1.11 (s, 9H). 13C NMR (75.5 MHz, CDCl3): δ 161.1, 125.9 (q, JC,F = 284.3 Hz), 73.4 (q, JC,F = 28.5 Hz), 70.7, 68.3, 26.3,
158.7, 131.2, 125.3 (q, JC,F = 287.3), 115.8, 104.8, 99.4, 77.5 (q, JC,F
=
20.0 (d, JC,F = 1.0 Hz). 19F NMR (470.6 MHz, CDCl3): δ −81.14 (s, CF3).
28.3 Hz), 70.0, 68.1, 55.8, 55.3, 26.5. 19F NMR (470.6 MHz, CDCl3): δ HRMS (ESI): m/z calcd for C8H15F3N2O [M+H]+ 213.1209, found
−79.29 (s, CF3). HRMS (ESI): m/z calcd for C15H21F3N2O3Na [M+Na]+
213.1206.
357.1396, found 357.1388.
2-[(tert-Butyldiazenyl)methyl]-1,1,1-trifluorononan-2-ol (7i)
3-(tert-Butyldiazenyl)-1,1,1-trifluoro-2-(4-fluorophenyl)propan-2-ol
(7d)
Following the general procedure starting from 1i (1.14 mL, 6 mmol),
diazene 7i was obtained as a pale yellow oil (1.78 g, 99%). 1H NMR
(300 MHz, CDCl3): δ 3.95 (d, 1H, J = 14.2 Hz), 3.89 (d, 1H, J = 14.2
Hz), 3.69 (s, 1H), 1.89-1.68 (m, 2H), 1.63-1.38 (m, 2H), 1.37-1.23 (m,
8H), 1.21 (s, 9H), 0.88 (t, 3H, J = 7.0 Hz). 13C NMR (75.5 MHz, CDCl3):
δ 126.0 (q, JC,F = 286.7 Hz), 75.3 (q, JC,F = 27.7 Hz), 68.7, 68.5, 33.3,
31.7, 29.9, 29.0, 26.5, 22.6, 22.4, 14.0. 19F NMR (470.6 MHz, CDCl3):
δ −78.98 (s, CF3). HRMS (ESI): m/z calcd for C14H28F3N2O [M+H]+
297.2148, found 297.2145.
Following the general procedure starting from 1d (0.85 mL, 6
mmol), diazene 7d was obtained as a pale yellow oil (1.75 g, 99%).
1H NMR (300 MHz, CDCl3): δ 7.62-7.51 (m, 2H), 7.13-7.02 (m, 2H),
4.41 (d, 1H, J = 14.1 Hz), 4.35 (d, 1H, J = 14.1 Hz), 1.12 (s, 9H). 13C
NMR (75.5 MHz, CDCl3): δ 162.8 (d, JC,F = 247.7 Hz), 132.1 (d, JC,F
=
3.1 Hz), 128.5 (dd, JC,F = 8.2, 1.1 Hz), 124.6 (q, JC,F = 286.0 Hz), 115.2
(d, J = 21.5 Hz), 76.3 (q, JC,F = 28.6 Hz), 69.7, 68.9, 26.4. 19F NMR
(470.6 MHz, CDCl3): δ −78.32 (s, CF3), [(−113.35)-(−113.44) m, 1F].
HRMS (ESI): m/z calcd for C13H17F4N2O [M+H]+ 293.1272, found
293.1261.
Ethyl
2-[(tert-butyldiazenyl)methyl]-3,3,3-trifluoro-2-
hydroxypropanoate (7j)
Following the general procedure starting from 1j (0.77 mL, 6 mmol),
1
diazene 7j was obtained as a colorless oil (1.62 g, 99%). H NMR
3-(tert-Butyldiazenyl)-1,1,1-trifluoro-2-(thiophen-2-yl)propan-2-ol
(7e)
(300 MHz, CDCl3): δ 4.40 (d, 1H, J = 13.9 Hz), 4.38 (q, 1H, J = 7.1 Hz),
4.37 (q, 1H, J = 7.1 Hz), 4.03 (d, 1H, J = 13.9 Hz), 1.34 (t, 3H, J = 7.15
Following the general procedure starting from 1e (0.76 mL, 6
mmol), diazene 7e was obtained as a pale yellow oil (1.68 g, 99%).
1H NMR (300 MHz, CDCl3): δ 7.33 (dd, 1H, J = 1.17, 5.13 Hz), 7.13-
7.07 (m, 1H), 7.01 (dd, 1H, J = 3.82, 5.09 Hz), 4.82 (s, 1H), 4.40 (d,
1H, J = 14.3 Hz), 4.35 (d, 1H, J = 14.3 Hz), 1.13 (s, 9H). 13C NMR (75.5
MHz, CDCl3): δ 140.2, 127.1, 126.3, 125.8, 124.1 (q, JC,F = 285.8 Hz),
70.0 (q, JC,F = 28.5 Hz), 68.9, 26.4. 19F NMR (470.6 MHz, CDCl3): δ
−79.25 (s, CF3). HRMS (ESI): m/z calcd for C11H16F3N2OS [M+H]+
281.0930, found 281.0920.
Hz), 1.17 (s, 9H). 13C NMR (75.5 MHz, CDCl3): δ 168.6, 122.9 (q, JC,F
=
286.2 Hz), 76.7 (q, JC,F = 29.2 Hz), 68.5, 68.0, 63.8, 26.7, 14.0. 19F
NMR (470.6 MHz, CDCl3): δ −77.49 (s, CF3). HRMS (ESI): m/z calcd
for C10H17F3N2O3Na [M+Na]+ 293.1083, found 293.1081.
General procedure for the 'one-pot' synthesis of α-hydroxy α-
trifluoromethyl hydrazones 8
Freshly distilled formaldehyde tert-butylhydrazone 4 (0.13 mL, 1
mmol) was added to trifluoromethyl ketone 1 (1 mmol) at room
temperature. The mixture was stirred for the time specified (Table
2, tlc monitoring) to afford pure diazene 7. Subsequently, a solution
of TFA (0.1 mmol) in CH2Cl2 (10 mL) was added to a solution of
2-Benzyl-3-(tert-butyldiazenyl)-1,1,1-trifluoropropan-2-ol (7f)
Following the general procedure starting from 1f (0.91 mL, 6 mmol),
diazene 7f was obtained as a pale yellow oil (1.73 g, 99%). 1H NMR
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