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Hz), 118.6 , 117.9 (q, 3JCF = 3.7 Hz), 110.9 (q, 3JCF = 3.9 Hz). HRMS (ESI+): calcd for C7H8F3N2
[M–Сl]+: 177.0640; found 177.0638.
Phenylhydrazine hydrochloride31
Pale yellow solid (1.02 g, 71%), mp 256–258 °C (lit.31: 250– 252 °C); IR (KBr) ν (cm-1): 3210,
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3153−2774, 2682, 2000, 1920, 1848, 1765, 1609, 1587, 1523, 1494. H NMR (DMSO-d6, 400
MHz, ppm): δ 10.37 (s, 3H), 8.34 (s, 1H, br), 7.27–7.23 (m, 2H), 7.02 (d, J = 7.6 Hz, 2H), 6.92
(t, J = 7.3 Hz, 1H). 13C NMR (DMSO-d6, 101 MHz, ppm): δ 146.0, 129.4, 121.9, 115.0. HRMS
(ESI+): calcd for C6H9N2 [M–Сl]+: 109.0766; found 109.0761.
4-Methylphenylhydrazine hydrochloride8
Pale yellow solid (1.11 g, 70%), mp 220–222 °C (lit.8:222–235 °C ; IR (KBr) ν (cm-1): 3221,
)
3162−2761, 2690, 2008, 1880, 1587, 1519, 1494. 1H NMR (DMSO-d6+CCl4, 400 MHz, ppm): δ
10.28 (s, 3H), 7.02 (d, J = 8.3 Hz, 2H), 6.94 (d, J = 8.3 Hz, 2H), 2.27 (s, 3H). 13C NMR (DMSO-
d6, 101 MHz, ppm): δ 143.6, 130.9, 129.7, 115.4, 20.7. HRMS (ESI+): calcd for C7H11N2 [M–
Сl]+: 123.0922; found 123.0919.
3,4-Dimethylphenylhydrazine hydrochloride32
Pale brown solid (894 mg, 52%), mp 205−206 °C (lit.32:197 °C); IR (KBr) ν (cm-1): 3153−2217,
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2016, 1915, 1851, 1749, 1597, 1509, 1448. H NMR (DMSO-d6, 400 MHz, ppm): δ 10.22 (s,
3H), 7.00 (d, J = 8.1 Hz, 1H), 6.83 (s, 1H), 6.76 (dd, J = 8.1, 1.7 Hz, 1H), 2.15 (s, 3H), 2.12 (s,
3H). 13C NMR (DMSO-d6, 101 MHz, ppm): δ 143.9, 137.1, 130.2, 129.7, 116.7, 112.7, 20.1,
19.0. HRMS (ESI+): calcd for C8H13N2 [M–Сl]+: 137.1079; found 137.1076.
4-Ethylphenylhydrazine hydrochloride33
o
Pale brown solid (947 mg, 55%), mp 208−210 °C (lit.33: 200 C); IR (KBr) ν (cm-1): 3232,
3162−2747, 2686, 1947, 1889, 1591, 1568, 1535, 1513. 1H NMR (DMSO-d6, 400 MHz, ppm): δ
10.30 (s, 3H), 7.08 (d, J = 8.4 Hz, 2H), 6.95 (d, J = 8.4 Hz, 2H), 2.50 (q, J = 7.6 Hz, 2H), 1.11 (t,
J = 7.6 Hz, 3H). 13C NMR (DMSO-d6, 101 MHz, ppm): δ 143.8, 137.4, 128.6, 115.4, 27.9, 16.4.
HRMS (ESI+): calcd for C8H13N2 [M–Сl]+: 137.1079; found 137.1075.
4.7. Typical procedure for C–N coupling reaction of 4-bromotoluene and hydrazine on a
300 mmol scale. Preparative synthesis of 4-tolylhydrazine hydrochloride
CuBr (1.1 g, 7.5 mmol, 2.5 mol%), L3 (3.3 g, 12 mmol, 4 mol%), H2O (15 mL) and
K3PO4·7Н2О (12.2 g, 36 mmol) were mixed in a 250 mL flask. After СТАВ (3.3 g, 9 mmol) and
4-bromotoluene (51.3 g, 300 mmol) were added, the resulting mixture was stirred at 110 °C for
10 min. Then K3PO4·7Н2О (109.5 g, 324 mmol) and N2H4ꢀH2O (98%) (30 g, 600 mmol) were
added. The reaction mixture was stirred at 110 °C for 1 h until complete consumption of starting
material as monitored by TLC (eluent–hexane), then cooled to room temperature and diluted
with СH2Cl2 (300 mL). The resulting solution was filtered and washed with brine (2×100 mL).
НСl (37%) were added to the CH2Cl2 solution dropwise until pH 3−4. The formed precipitate
was filtered off, washed with СH2Cl2 and dried at room temperature (34.6 g, 73%).
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