The Journal of Organic Chemistry
ARTICLE
(CH), 123.7 (C), 121.6 (C), 120.3 (CH), 113.0 (CH), 101.2 (C), 81.0
(C), 22.2 (CH3). IR (neat): 3056, 2923, 2200, 1670, 1598, 1504, 1442,
1363, 1253, 1155, 1072, 970, 758, 690 cmÀ1. MS (ESI, m/z): 257.11 [M +
Na]+. HRMS (ESI): calcd for C16H14N2Na 257.1055 [M + Na]+, found
257.1049. The spectral data were in agreement with those reported
previously for this compound.65
(Z)-1-(4-Phenylbut-3-yn-2-ylidene)-2-(4-(trifluoromethyl)phenyl)-
hydrazine (Z-22m). 4-Phenylbut-3-yn-2-one (125 mg, 0.87 mmol) and
(4-(trifluoromethyl)phenyl)hydrazine (153 mg, 0.87 mmol) were em-
ployed to afford 200 mg (76%) of the indicated product for condition B.
1H NMR (400 MHz, CDCl3): δ 8.31 (br s, 1H), 7.45 (d, J = 7.6 Hz, 2H),
7.39 (d, J = 8.5 Hz, 2H), 7.32 (m, 3H), 7.02 (d, J = 8.4 Hz, 2H), 2.16
(s, 3H). 13C NMR (100 MHz, CDCl3): δ 146.6 (C), 131.9 (CH), 129.7
(CH), 128.7 (CH), 126.6 (m, CH), 125.9 (C), 124.7 (d, J = 269.8 Hz,
C), 121.8 (q, J = 32.9 Hz, C), 121.2 (C), 112.5 (CH), 101.7 (C), 80.4
(C), 22.3 (CH3). IR (neat): 3313, 3082, 2989, 2918, 2360, 2177, 2162,
1612, 1527, 1488, 1325, 1311, 1267, 1153, 1099, 1062, 821, 748,
684 cmÀ1. MS (ESI, m/z): 303.11 [M + H]+. HRMS (ESI): calcd for
C17H14F3N2 303.1109 [M + Na]+, found 303.1104.
(Z)-1-(3-Chloro-4-fluorophenyl)-2-(4-phenylbut-3-yn-2-ylidene)-
hydrazine (Z-22n). 4-Phenylbut-3-yn-2-one (114 mg, 0.79 mmol) and
(3-chloro-4-fluorophenyl)hydrazine (127 mg, 0.79 mmol) were em-
ployed to afford 198 mg (87%) of the indicated product for condition B.
1H NMR (400 MHz, CDCl3): δ 8.18 (br s, 1H), 7.54 (m, 2H), 7.42 (m,
3H), 7.17 (dd, J = 6.3, 2.5 Hz, 1H), 7.03 (t, J = 8.7 Hz, 1H), 6.88 (m, 1H),
2.24 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 152.5 (d, J = 18.4 Hz, C),
141.0 (C), 131.8 (CH), 129.6 (CH), 128.7 (CH), 125.0 (C), 121.5
(d, J = 18.4 Hz, C), 121.3 (C), 116.8 (d, J = 21.8 Hz, CH), 114.5 (CH),
112.0 (d, J = 6.2 Hz, CH), 101.6 (C), 80.6(C), 22.2 (CH3). IR (neat):
3309, 3055, 2916, 2360, 2165, 1606, 1556, 1506, 1442, 1259, 1209, 1186,
1153, 862, 804, 746, 680 cmÀ1. MS (ESI, m/z): 309.06 [M + Na]+.
HRMS (ESI): calcd for C16H12ClFN2Na 309.0571 [M + Na]+, found
309.0565.
(Z)-1-(2,5-Difluorophenyl)-2-(4-phenylbut-3-yn-2-ylidene)hydrazine
(Z-22o). 4-Phenylbut-3-yn-2-one (151 mg, 1.05 mmol) and (2,5-difluor-
ophenyl)hydrazine (152 mg, 1.05 mmol) were employed to afford 245
mg (86%) the indicated product for condition B. 1H NMR (400 MHz,
CDCl3): δ 8.54 (br s, 1H), 7.57 (m, 2H), 7.44 (m, 3H), 7.25 (m, 1H),
6.98 (m, 1H), 6.47 (m, 1H), 2.28 (s, 1H). 13C NMR (100 MHz, CDCl3):
δ 159.8 (d, J = 239.8 Hz, C), 145.7 (d, J = 233.4 Hz, C), 133.7 (t, J = 12
Hz, C), 131.9 (CH), 129.7 (CH), 128.7 (CH), 127.2 (C), 121.2 (C),
115.3 (dd, J = 20, 9.7 Hz, CH), 105.0 (dd, J = 24.8, 7 Hz, CH), 102.2 (C),
101.6 (dd, J = 30.4, 2.5 Hz, CH), 80.4 (C), 22.1 (CH3). IR (neat): 3327,
3066, 3045, 2921, 2173, 1633, 1521, 1460, 1247, 1151, 1130, 977, 854,
808, 754, 732, 684 cmÀ1. MS (ESI, m/z): 293.09 [M + Na]+. HRMS
(ESI): calcd for C16H12F2N2Na 293.0868 [M + Na]+, found 293.0861.
(Z)-1-(1,3-Diphenylprop-2-yn-1-ylidene)-2-phenylhydrazine (Z-
22p). 1,3-Diphenylprop-2-yn-1-one (206 mg, 1.0 mmol) and phenylhy-
drazine (115 mg, 1.0 mmol) were employed to afford 80 mg (27%) of
the indicated product for condition B. 1H NMR (400 MHz, CDCl3): δ
8.79 (br s, 1H), 8.06 (d, J = 7.9 Hz, 2H), 7.69 (m, 2H), 7.49 (m, 5H),
7.39 (m, 3H), 7.30 (d, J = 7.9 Hz, 2H), 7.0 (t, J = 7.0 Hz, 1H). 13C NMR
(100 MHz, CDCl3): δ 143.6 (C), 135.9 (C), 132.0 (CH), 129.7 (CH),
129.4 (CH), 128.8 (CH), 128.5 (CH), 128.2 (CH), 125.7 (C), 125.6
(CH), 121.6 (CH), 121.1 (C), 113.6 (CH), 103.8 (C), 78.9 (C). IR
(neat): 3298, 2928, 2360, 2160, 1600, 1517, 1490, 1442, 1259, 1168,
1072, 885, 748, 686 cmÀ1. MS (ESI, m/z): 319.12 [M + Na]+. HRMS
(ESI): calcd for C21H16N2Na 319.1211 [M + Na]+, found 319.1206.
(Z)-1-(1,3-Diphenylprop-2-yn-1-ylidene)-2-(4-(trifluoromethyl)-
phenyl)hydrazine (Z-22q). 1,3-Diphenyl-prop-2-yn-1-one (206 mg, 1.0
mmol) and (4-(trifluoromethyl)phenyl)hydrazine (176 mg, 1.0 mmol)
was employed to afford 189 mg (52%) of the indicated product
for condition B. 1H NMR (400 MHz, CDCl3): δ 8.83 (br s, 1H), 8.02
(d, J = 7.5 Hz, 2H), 7.67 (d, J = 7.6 Hz, 2H), 7.58 (d, J = 8.4 Hz, 2H), 7.49
(m, 5H), 7.39 (d, J = 7.3 Hz, 1H), 7.29 (d, J = 8.4 Hz, 2H). 13C NMR
(100 MHz, CDCl3): δ 146.8 (C) 135.4 (C), 132.0 (CH), 129. (CH),
128.8 (CH), 128.5 (CH), 127.9 (C), 126.7 (m, CH), 125.9 (CH), 125.8
(CH), 123.8 (d, J = 175 Hz, (C), 122.6 (q, J = 32.2 Hz, C), 121.2 (C),
113.1 (CH), 104.2 (C), 78.5 (C). IR (neat): 3303, 3064, 3029, 2360,
2187, 1612, 1533, 1488, 1419, 1321, 1267, 1551, 1095, 1060, 829, 752,
682 cmÀ1. MS (ESI, m/z): 387.11 [M + Na]+. HRMS (ESI): calcd for
C22H15F3N2Na 387.1085 [M + Na]+, found 387.1080.
(Z)-1-(2,5-Difluorophenyl)-2-(1,3-diphenylprop-2-yn-1-ylidene)-
hydrazine (Z-22r). 1,3-Diphenylprop-2-yn-1-one (220 mg, 1.06 mmol)
and (2,5-difluorophenyl)hydrazine (154 mg, 1.06 mmol) were em-
ployed to afford 139 mg (36%) of the indicated product for condition
B. 1H NMR (400 MHz, CDCl3): δ 8.93 (br s, 1H), 8.01 (d, J = 7.5 Hz,
2H), 7.65 (m, 2H), 7.45 (m, 5H), 7.40 (m, 2H), 7.02 (m, 1H), 6.52
(m, 1H). 13C NMR (100 MHz, CDCl3): δ 159.4 (d, J = 239 Hz, C),
145.7 (d, J = 235.5 Hz, C), 134.7 (C), 132.8 (t, J = 11.5 Hz, C), 131.6
(CH), 129.4 (CH), 128.6 (C),128.4 (CH), 128.3 (CH), 128.0 (CH),
125.3 (CH), 120.7 (C), 115.0 (dd, J = 20, 9.4 Hz, CH), 105.3 (dd, J =
24.6, 7.5 Hz, CH), 104.3 (C), 101.6 (d, J = 29.1 Hz, CH), 78.0 (C). IR
(neat): 3317, 3056, 2920, 2360, 2185, 1633, 1529, 1496, 1461, 1436,
1346, 1288 1247, 1182, 1157, 839, 785, 752, 729, 686 cmÀ1. MS (ESI,
m/z): 355.10 [M + Na]+. HRMS (ESI): calcd for C21H14F2N2Na
355.1023 [M + Na]+, found 355.1017.
(Z)-1-Phenyl-2-(3-ferrocenylprop-2-yn-1-ylidene)hydrazine (Z-23a).
3-Ferrocenylpropynal (200 mg, 0.84 mmol) and phenylhydrazine (91
mg, 0.84 mmol) were employed to afford 132 mg (48%) and 149 mg
(54%) of the indicated product for conditions A and B, respectively. 1H
NMR (400 MHz, CDCl3): δ 8.64 (br s, 1H, NH), 7.32 (t, J = 7.3 Hz,
2H), 7.13 (d, J = 7.6 Hz, 2H), 6.94 (t, J = 7.3 Hz, 1H), 6.55 (s, 1H), 4.57
(s, 2H), 4.35 (s, 2H), 4.29 (s, 5H). 13C NMR (100 MHz, CDCl3): δ
143.7 (C), 129.4 (CH), 120.4 (CH), 115.7 (CH), 113.2 (CH), 102.4
(C), 76.5 (C), 71.8 (CH), 70.3 (CH), 69.7 (CH), 62.9 (C). IR (neat):
3303, 2360, 2204, 2160, 1602, 1560, 1519, 1488, 1259, 1147, 1105, 1018,
999, 875, 810, 750, 692 cmÀ1. MS (ESI, m/z): 351.06 [M + Na]+.
HRMS (ESI): calcd for C19H16FeN2Na 351.0559 [M + Na]+, found
351.0555.
(E)-1-Phenyl-2-(3-ferrocenylprop-2-yn-1-ylidene)hydrazine (E-23a).
3-Ferrocenylpropynal (200 mg, 0.84 mmol) and phenylhydrazine (91
mg, 0.84 mmol) were employed to afford 124 mg (45%) and 99 mg
(36%) of the indicated product for conditions A and B, respectively. 1H
NMR (400 MHz, CDCl3): δ 7.95 (br s, 1H, NH), 7.27 (t, J = 7.9 Hz,
2H), 7.08 (d, J = 7.9 Hz, 2H), 7.03 (s, 1H), 6.90 (t, J = 7.3 Hz, 1H), 4.51
(s, 2H), 4.27 (s, 2H), 4.25 (s, 5H). 13C NMR (100 MHz, CDCl3): δ
143.7 (C), 129.3 (CH), 120.8 (CH), 120.4 (C), 113.12 (CH), 92.2 (C),
82.0 (C), 71.6 (CH), 70.1 (CH), 69.2 (CH), 64.3 (C). IR (neat): 3305,
2204, 2160, 1602, 1560, 1519, 1490, 1348, 1261, 1147, 1105, 1018, 999,
875, 810, 750, 692 cmÀ1. MS (ESI, m/z): 351.06 [M + Na]+. HRMS
(ESI): calcd for C19H16FeN2Na 351.0559 [M + Na]+, found 351.0555.
(Z)-1-(3-(Ferrocenyl)prop-2-yn-1-ylidene)-
2-(4-(trifluoromethyl)phenyl) hydrazine (Z-23b). 3-Ferrocenylpropy-
nal (200 mg, 0.84 mmol) and (4-(trifluoromethyl)phenyl)hydrazine
(148 mg, 0.84 mmol) were employed to afford 150 mg (45%) and 143
mg (43%) of the indicated product for conditions A and B, respectively.
1H NMR (400 MHz, CDCl3): δ 8.72 (br s, 1H, NH), 7.54 (d, J = 7.5 Hz,
2H), 7.16 (d, J = 7.6 Hz, 2H), 6.60 (s, 1H), 4.57 (s, 2H), 4.37 (s, 2H),
4.28 (s, 5H). 13C NMR (100 MHz, CDCl3): δ 146.2 (C), 126.7 (m,
CH), 124.6 (d, J = 269.5 Hz, C), 122.5 (q, J = 32.3 Hz, C), 117.8 (CH),
112.8 (CH), 103.2 (C), 76.0 (C), 71.9 (CH), 70.4 (CH), 69.9 (CH),
62.4 (C). IR (neat): 3325, 2187, 1614, 1542, 1523, 1323, 1263, 1091,
1058, 1001, 821 cmÀ1. MS (ESI, m/z): 419.04 [M + Na]+. HRMS
(ESI): calcd for C20H15F3FeN2Na 419.0433 [M + Na]+, found
419.0429.
(E)-1-(3-(Ferrocenyl)prop-2-yn-1-ylidene)-2-(4-(trifluoromethyl)-
phenyl) hydrazine (E-23b). 3-Ferrocenylpropynal (200 mg, 0.84 mmol)
6736
dx.doi.org/10.1021/jo201119e |J. Org. Chem. 2011, 76, 6726–6742