Arkivoc 2017, v, 129‐140
Novosád, D. et al.
and concentrated under reduced pressure. The crude product was crystallized from a mixture of hexane/DCM.
NMR spectra of compounds 8 are given as a mixture of isomers; for integral intensity of protons see
Supplementary material. Due to dynamic equilibrium not all carbon atoms are apparent from CDCl3 spectra.
3‐Imino‐2‐(2‐phenylhydrazono)pentanenitrile (8i). Following the General procedure E, the reaction was
performed with 2.0 M solution of ethylmagnesium chloride (4.4 mL, 8.8 mmol) to afford 8i as a yellow solid
(225 mg, 77%); mp 108‐110 °C; 1H NMR (400 MHz, DMSO‐d6) δ 8.76 (brs, NH), 8.70 (s,NH), 8.33 (s, NH) 8.11 (s,
NH), 7.72 (d, J 7.3 Hz, arom), 7.50 (d, J 7.3 Hz, arom), 7.40 (t, J 7.8 Hz, arom), 7.23‐7.31 (m, arom), 2.86 (q, J 7.5
Hz, CH2), 2.50 (q, J 7.6 Hz, CH2), 1.26 (t, J 7.7 Hz, CH3), 1.22 (t, J 7.6 Hz, CH3); 13C NMR (100 MHz, DMSO‐d6) δ
173.0, 169.5, 152.8, 152.5, 129.0, 128.9, 128.1, 127.5, 121.6, 120.8, 117.7, 114.2, 103.0, 102.2, 26.5, 24.5,
13.4, 12.7; 1H NMR (400 MHz, CDCl3) δ 8 – 9 (brs, NH), 7.64 (d, J 8.5 Hz, arom), 7.41 (d, J 8.4 Hz, arom), 7.32 (t,
J 8.4 Hz, arom), 5.69 (brs, NH2), 3.03 (q, J 7.6 Hz, CH2), 2.70 (q, J 7.6 Hz, CH2), 1.37 (t, J 7.6 Hz, CH3), 1.37 (t, J 7.6
Hz, CH3); HRMS (HESI, m/z) calcd for C11H12N4 (200.11) [M+H]+ 201.1135, found 201.1136.
3‐Imino‐2‐(2‐phenylhydrazono)hexanenitrile (8j). Following the General procedure E, the reaction was
performed with 1.0 M solution of n‐propylmagnesium chloride (8.8 mL, 8.8 mmol) to afford 8j as a yellow solid
(212 mg, 68%); mp 56‐57 °C; 1H NMR (400 MHz, DMSO‐ d6) δ 8.76 (brs, NH), 8.69 (s,NH), 8.32 (s, NH) 8.11 (s,
NH), 7.72 (d, J 7.4 Hz, arom), 7.50 (d, J 7.3 Hz, arom), 7.41 (t, J 7.8 Hz, arom), 7.31‐7.23 (m, arom), 2.84 (q, J 7.4
13
Hz, CH2), 2.52 (q, J 7.5 Hz, CH2),1.73‐1.69 (m, 2 x CH2) 0.98 (t, J 7.7 Hz, CH3), 0.92 (t, J 7.6 Hz, CH3); C NMR
(100 MHz, DMSO‐d6) δ 171.5, 168.0, 152.8, 152.5, 129.1, 128.9, 128.1, 127.5, 121.7, 120.8, 115.8, 114.2,
1
103.6, 102.9, 35.2, 32.6, 22.0, 21.4, 13.6, 13.5; H NMR (400 MHz, CDCl3) δ 8 – 9 (brs, NH), 7.66 (d, J 8.5 Hz,
arom), 7.40 (d, J 8.4 Hz, arom), 7.32 (t, J 8.4 Hz, arom), 5.57 (brs, NH2), 2.98 (q, J 7.6 Hz, CH2), 2.65 (q, J 7.6 Hz,
CH2), 1.84‐1.78 (m, 2 x CH2), 1.09 (t, J 7.6 Hz, CH3), 1.05 (t, J 7.6 Hz, CH3); HRMS (HESI, m/z) calcd for C12H14N4
(214.12) [M+H]+ 215.1291, found 215.1293.
3‐Imino‐4‐methyl‐2‐(2‐phenylhydrazono)pentanenitrile (8k). Following the General procedure E, the reaction
was performed with 2.0 M solution of isopropylmagnesium chloride (4.4 mL, 8.8 mmol) to afford 8k as a
yellow solid (150 mg, 48%); mp 102‐104 °C; 1H NMR (400 MHz, DMSO‐d6) δ 8.74 (brs, NH), 8.41 (s,NH), 8.12 (s,
NH) 8.01 (s, NH), 7.49 (d, J 8.4 Hz, arom), 7.45‐7.38 (m, arom), 7.29 (t, J 7.6 Hz, arom), 7.25 (t, J 7.6 Hz, arom),
4.00 (heptaplet, J 7.2 Hz, CH), 3.07 (heptaplet, J 7.2 Hz, CH), 1.29 (d, J 6.8 Hz, CH3), 1.23 (d, J 6.8 Hz, CH3); 13C
NMR (100 MHz, DMSO‐d6) δ 175.9, 172.8, 152.7, 152.5, 129.0, 128.9, 128.1, 127.5, 121.7, 120.8, 115.5, 114.2,
103.1, 101.8, 32.1, 28.7, 20.0, 19.9; HRMS (HESI, m/z) calcd for C12H14N4 (214.12) [M+H]+ 215.1291, found
215.1292.
3‐Imino‐2‐(2‐phenylhydrazono)heptanenitrile (8l). Following the General procedure E, the reaction was
performed with 2.0 M solution of n‐butylmagnesium chloride (4.4 mL, 8.8 mmol) to afford 8l as a yellow solid
(223 mg, 67%); mp 78‐80 °C; 1H NMR (400 MHz, DMSO‐d6) δ 8.75 (brs, NH), 8.68 (s,NH), 8.31 (s, NH) 8.01 (s,
NH), 7.73 (d, J 8.4 Hz, arom), 7.50 (d, J 7.8 Hz, arom), 7.41 (t, J 8.2 Hz, arom), 7.28 (t, J 7.6 Hz, arom), 7.28 (t, J
7.6 Hz, arom), 2.86 (t, J 7.6 Hz, CH2), 2.56 (t, J 7.6 Hz, CH2), 1.71‐1.61 (m, 2 x CH2), 1.43‐1.31 (m, 2 x CH2), 0.92
13
(t, J 7.6 Hz, CH3), 0.89 (t, J 6.8 Hz, CH3); C NMR (100 MHz, DMSO‐d6) δ 171.8, 168.3, 152.7, 152.5, 129.0,
128.9, 128.1, 127.5, 121.6, 120.8, 115.7, 114.1, 103.6, 102.7, 32.6, 30.6, 30.4, 30.1, 21.7, 14.5; HRMS (HESI,
m/z) calcd for C13H16N4 (228.14) [M+H]+ 229.1448, found 229.1449.
3‐Cyclopentyl‐3‐imino‐2‐(2‐phenylhydrazono)propanenitrile (8m). Following the General procedure E, the
reaction was performed with 2.0 M solution of cyclopentylmagnesium chloride (4.4 mL, 8.8 mmol) to afford
8m as a yellow solid (266 mg, 76%); mp 202‐206 °C; 1H NMR (400 MHz, CDCl3) δ 8 – 9 (brs, NH), 7.66 (d, J 8.5
Hz, arom), 7.40 (d, J 8.4 Hz, arom), 7.31 (t, J 8.4 Hz, arom), 5.54 (brs, NH2), 4.16 (quintet, J 9.2 Hz, CH), 3.30
(quintet, J 9.2 Hz, CH), 2.20‐2.16 (m, CH2), 1.85‐1.78 (m, CH2) ; 13C NMR (100 MHz, CDCl3) δ 171.2, 167.8, 167.6,
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