127.2, 126.0, 125.0, 121.0, 118.4, 113.0, 82.4, 28.2; FT-IR (CHCl3)
3336, 3057, 2977, 1699, 1602, 1496 cm-1; HRMS (FAB) m/z
(M + 1)+ calcd for C21H23N2O2 335.1760, found 335.1760.
3314, 3057, 2979, 1716, 1600, 1367, 1311, 1153 cm-1; HRMS
(FAB) m/z (M + 1)+ calcd for C23H25N2O3 377.1865, found
377.1865.
N-(4-Cya n op h en yl)-N-n a p h th a len -2-ylh yd r a zin eca r box-
ylic Acid ter t-Bu tyl Ester (3j, solid ). 1H NMR (400 MHz,
CDCl3) δ 7.95 (d, J ) 1.6 Hz, 1H), 7.82-7.77 (m, 4H), 7.69 (dd,
J ) 2.0, 2.4 Hz, 1H), 7.55-7.52 (m, 2H), 7.49-7.42 (m, 2H),
6.92-6.88 (m, 2H), 1.43 (s, 9H); 13C NMR (100 MHz, CDCl3) δ
153.3, 151.5, 139.3, 133.5, 133.2, 130.8, 128.2, 127.6, 127.3, 126.3,
125.4, 121.0, 119.4, 118.8, 112.6, 103.1, 84.0, 28.1; FT-IR (CHCl3)
3316, 3065, 2978, 2220, 1718, 1608 cm-1; HRMS decomposition.
N′-(4-Ben zoylp h en yl)-N-n a p h t h a len -2-ylh yd r a zin eca r -
boxylic Acid ter t-Bu tyl Ester (3k , solid ). 1H NMR (400 MHz,
CDCl3) δ 8.00 (s, 1H), 7.85-7.72 (m, 8H), 7.56-7.52 (m, 1H),
7.48-7.37 (m, 4H), 6.90 (d, J ) 8.4 Hz, 2H), 6.85 (s, 1H), 1.45
(s, 9H); 13C NMR (100 MHz, CDCl3) δ 195.1, 153.5, 151.9, 139.6,
138.2, 133.2, 132.4, 131.5, 130.7, 129.8, 128.1, 128.0, 127.6, 127.3,
126.2, 125.3, 121.2, 118.7, 111.7, 82.8, 28.2; FT-IR (CHCl3) 3313,
N-Na p h th a len -2-yl-N′-p-tolylh yd r a zin eca r boxylic Acid
ter t-Bu tyl Ester (3b, solid ). 1H NMR (400 MHz, CDCl3) δ 8.02
(s, 1H), 7.79-7.74 (m, 4H), 7.43-7.35 (m, 2H), 7.02 (d, J ) 8.0
Hz, 2H), 6.70 (d, J ) 8.4 Hz, 2H), 6.40 (s, 1H), 2.26 (s, 3H), 1.38
(s, 9H); 13C NMR (100 MHz, CDCl3) δ 153.9, 145.7, 140.3, 133.4,
130.6, 130.3, 129.6, 127.9, 127.7, 127.2, 126.0, 125.0, 121.3, 118.4,
113.1, 82.3, 28.2, 20.7; FT-IR (CHCl3) 3337, 2975, 1713, 1513
cm-1; HRMS (FAB) m/z (M + 1)+ calcd for C22H25N2O2 339.1916,
found 349.1903.
N′-(4-Meth oxyp h en yl)-N-n a p h th a len -2-ylh yd r a zin eca r -
boxylic Acid ter t-Bu tyl Ester (3c, solid ). The same method
as for 3a was used. 1H NMR (400 MHz, CDCl3) δ 8.02 (s, 1H),
7.78-7.74 (m, 4H), 7.43-7.35 (m, 2H), 6.78 (s, 4H), 6.35 (s, 1H),
3.73 (s, 3H), 1.40 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 154.2,
153.9, 145.7, 141.8, 140.3, 133.3, 130.6, 127.9, 127.6, 127.2, 126.0,
125.0, 121.3, 118.5, 114.5, 82.3, 55.6, 28.2; FT-IR (CHCl3) 3327,
2978, 1711, 1510, 1312, 1239, 1153 cm-1; HRMS (FAB) m/z (M
+ 1)+ calcd for C22H25N2O3 365.1865, found 365.1873.
3058, 2979, 2932, 1716, 1650, 1598, 1368, 1315, 1150 cm-1
;
HRMS (FAB) m/z (M + 1)+ calcd for C28H27N2O3 439.2022, found
439.2021.
Gen er a l P r oced u r e for th e P r ep a r a tion of 1-(2-Am in o-
p h en yl)n a p h th a len -2-yla m in e (4a ). A mixture of 3a (50 mg,
0.15 mmol), 3 mL of ethanol, and three drops of concentrated
HCl (35%) was heated under reflux for 1 h. Upon being cooledg
and neutralized with NaHCO3, the reaction mixture was filtered,
concentrated, and chromatographed (2:1 hexanes:CH2Cl2 to 9:1
EtOAc:MeOH) to afford 27 mg (77% yield) of 4a as a solid. 1H
NMR (400 MHz, CDCl3) δ 7.72-7.67 (m, 2H), 7.27-7.19 (m, 4H),
7.10 (dd, J ) 1.6, 1.2 Hz, 1H), 7.03 (d, J ) 8.8 Hz, 1H), 6.90-
6.84 (m, 2H), 3.64 (br s, 4H); 13C NMR (100 MHz, CDCl3) δ 144.8,
141.7, 133.3, 131.7, 130.7, 129.0, 128.9, 128.0, 127.9, 126.5, 123.8,
122.2, 121.2, 118.9, 118.1, 115.6, 115.3; FT-IR (CHCl3) 3381,
3052, 1620, 1497, 1392, 1291, 1150 cm-1; HRMS (FAB) m/z
(M + 1)+ calcd for C16H15N2 235.1235, found 235.1227.
1-(2-Am in o-5-m eth ylp h en yl)n a p h th a len -2-yla m in e (4b,
solid ). 1H NMR (400 MHz, CDCl3) δ 7.70 (d, J ) 7.6 Hz, 1H),
7.66 (d, J ) 8.88 Hz, 1H), 7.29-7.17 (m, 3H), 7.04 (dd, J ) 2.0,
2.4 Hz, 1H), 7.00 (d, J ) 8.4 Hz, 1H), 6.91 (d, J ) 2.0 Hz, 1H),
6.76 (d, J ) 8.0 Hz, 1H), 3.57 (br s, 4H); 13C NMR (100 MHz,
CDCl3) δ 142.3, 141.7, 133.3, 132.0, 129.5, 128.8, 128.1, 128.0,
127.8, 126.4, 123.8, 122.1, 121.3, 118.1, 115.8, 115.5, 20.6; FT-
IR (CHCl3) 3453, 3361, 3050, 2861, 1621, 1504, 1351, 1281, 1147
cm-1; HRMS (FAB) m/z (M + 1)+ calcd for C17H17N2 249.1392,
found 249.1397.
N′-(2-Meth oxyp h en yl)-N-n a p h th a len -2-ylh yd r a zin eca r -
boxylic Acid ter t-Bu tyl Ester (3d , solid ). 1H NMR (400 MHz,
CDCl3) δ 8.06 (d, J ) 1.6 Hz, 1H), 7.82 (dd, J ) 2.0, 2.4 Hz, 1H),
7.77-7.75 (m, 3H), 7.04 (s, 1H), 6.86-6.80 (m, 4H), 3.89 (s, 3H),
1.36 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 153.5, 146.8, 140.4,
137.6, 133.4, 130.5, 127.9, 127.6, 127.2, 126.0, 124.9, 121.2, 120.9,
120.5, 118.2, 112.1, 109.9, 82.0, 55.5, 28.1; FT-IR (CHCl3) 3356,
3056, 2976, 1714, 1600, 1504, 1368, 1310, 1249, 1153 cm-1
;
HRMS (FAB) m/z (M + 1)+ calcd for C22H25N2O3 365.1865, found
365.1873.
N′-(4-ter t-Bu tylp h en yl)-N-n a p h th a len -2-ylh yd r a zin eca r -
boxylic Acid ter t-Bu tyl Ester (3e, solid ). 1H NMR (400 MHz,
CDCl3) δ 8.02 (s, 1H), 7.78-7.23 (m, 4H), 7.42-7.34 (m, 2H),
7.23-7.18 (m, 2H), 6.78-6.74 (m, 2H), 6.43 (s, 1H), 1.39 (s, 9H),
1.26 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 153.9, 145.6, 143.7,
140.3, 133.3, 130.6, 127.8, 127.6, 127.2, 126.0, 125.8, 125.0, 121.4,
118.6, 112.8, 82.3, 34.1, 31.6, 28.2; FT-IR (CHCl3) 3341, 1964,
1714, 1515 cm-1; HRMS (FAB) m/z (M + 1)+ calcd for C25H31N2O2
391.2386, found 391.2373.
N′-Bip h en yl-4-yl-N-n a p h t h a len -2-ylh yd r a zin eca r b oxy-
lic Acid ter t-Bu tyl Ester (3f, solid ). 1H NMR (400 MHz,
CDCl3) δ 8.04 (s, 1H), 7.80-7.74 (m, 4H), 7.52-7.34 (m, 8H),
7.24 (t, J ) 7.6 Hz, 1H), 6.88 (d, J ) 8.4 Hz, 2H), 6.52 (s, 1H),
1.41 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 153.8, 147.5, 140.7,
140.1, 133.9, 133.3, 130.6, 128.5, 128.0, 127.8, 127.6, 127.3, 126.4,
126.1, 125.1, 121.2, 118.5, 113.3, 82.5, 28.2; FT-IR (CHCl3) 3344,
2978, 1713, 1612, 1488, 1308, 1152 cm-1; HRMS (FAB) m/z (M
+ 1)+ calcd for C27H27N2O2 411.2073, found 411.2074.
N-Na p h th a len -2-yl-N′-(4-n itr op h en yl)h yd r a zin eca r box-
ylic Acid ter t-Bu tyl Ester (3g, solid ). 1H NMR (400 MHz,
CDCl3) δ 8.16-8.12 (m, 2H), 7.93 (d, J ) 2.4 Hz, 1H), 7.81-
7.75 (m, 3H), 7.66 (dd, J ) 2.4, 2.0 Hz, 1H), 7.48-7.40 (m, 2H),
6.89-6.86 (m, 2H), 1.44 (s, 9H); 13C NMR (100 MHz, CDCl3) δ
153.4, 153.3, 140.8, 139.1, 133.2, 130.9, 128.3, 127.6, 127.3, 126.4,
125.8, 125.5, 121.0, 118.9, 111.6, 83.2, 28.1; FT-IR (CHCl3) 3323,
3062, 2978, 1716, 1598 cm-1; HRMS (FAB) m/z (M + 1)+ calcd
for C21H22N3O4 380.1610, found 380.1607.
4-(N′-ter t-Bu toxycar bon yl-N′-n aph th alen -2-ylh ydr azin o)-
ben zoic Acid Meth yl Ester (3h , solid ). 1H NMR (400 MHz,
CDCl3) δ 7.99-7.72 (m, 4H), 7.47-7.40 (m, 2H), 6.88-6.85 (m,
2H), 6.70 (s, 1H), 3.87 (s, 3H), 1.40 (s, 9H); 13C NMR (100 MHz,
CDCl3) δ 166.7, 153.4, 152.0, 139.6, 133.3, 131.3, 130.7, 128.2,
127.6, 127.3, 126.2, 125.3, 122.5, 121.0, 118.6, 112.0, 82.8, 51.9,
28.2; FT-IR (CHCl3) 3323, 2979, 1715, 1608 cm-1; HRMS (FAB)
m/z (M + 1)+ calcd for C23H25N2O4 393.1814, found 393.1809.
1-(2-Am in o-5-m eth oxyp h en yl)n a p h th a len -2-yla m in e (4c,
1
solid ). H NMR (400 MHz, CDCl3) δ 7.73-7.68 (m, 2H), 7.31-
7.28 (m, 2H), 7.24-7.20 (m, 1H), 7.04 (d, J ) 8.4 Hz, 1H), 6.88-
6.82 (m, 2H), 6.71 (d, J ) 2.4 Hz, 1H), 3.81-3.76 (br s, 2H),
3.74 (s, 3H), 3.28 (br s, 2H); 13C NMR (100 MHz, CDCl3) δ 152.8,
141.6, 138.5, 133.2, 129.1, 128.0, 127.9, 126.6, 123.8, 122.4, 122.2,
118.1, 117.1, 116.2, 115.3, 55.7; FT-IR (CHCl3) 3444, 3360, 3208,
3049, 1620, 1501, 1420, 1278, 1204, 1038 cm-1; HRMS (FAB)
m/z (M + 1)+ calcd for C17H17N2O 265.1241, found 265.1347.
1-(2-Am in o-3-m eth oxyph en yl)n aph th alen -2-ylam in e (4d,
solid ). 1H NMR (400 MHz, CDCl3) δ 7.73 (d, J ) 8.0 Hz, 1H),
7.70 (d, J ) 8.8 Hz, 1H), 7.32-7.28 (m, 1H), 7.26-7.20 (m, 2H),
7.05 (d, J ) 8.8 Hz, 1H), 6.91-6.84 (m, 2H), 6.77 (dd, J ) 2.4,
1.6 Hz, 1H), 3.93 (s, 3H), 3.80 (br s, 2H), 3.70 (br s, 2H); 13C
NMR (100 MHz, CDCl3) δ 147.4, 141.7, 134.8, 133.2, 128.9, 128.0,
127.8,126.4, 123.9, 123.5, 122.1, 121.2, 118.1, 118.0, 115.2, 109.4,
55.6; FT-IR (CHCl3) 3465, 3372, 3053, 2934, 2836, 1602, 1473,
1279, 1198, 1052 cm-1; HRMS (FAB) m/z (M + 1)+ calcd for
C
17H17N2O 265.1241, found 265.1321.
6-ter t-Bu tyl-[1,1′]bin a p h th a len yl-2,2′-d ia m in e (4e, solid ).
1H NMR (400 MHz, CDCl3) δ 7.71 (d, J ) 7.6 Hz, 1H), 7.69 (d,
J ) 8.8 Hz, 1H), 7.30-7.19 (m, 4H), 6.81 (d, J ) 8.4 Hz, 1H),
3.62 (br s, 4H); 13C NMR (100 MHz, CDCl3) δ 142.1, 141.8, 141.7,
133.4, 128.9, 128.5, 128.0, 127.9, 126.4, 125.7, 124.0, 122.1, 120.9,
118.1, 116.0, 115.4, 34.2, 31.7; FT-IR (CHCl3) 3489, 3369, 3203,
3052, 2961, 2868, 1620, 1501, 1285, 1258, 1210 cm-1; HRMS
(FAB) m/z (M + 1)+ calcd for C20H23N2 291.1861, found 291.1857.
6-P h en yl-[1,1′]bin a p h th a len yl-2,2′-d ia m in e (4f, solid ). 1H
NMR (400 MHz, CDCl3) δ 7.74-7.70 (m, 2H), 7.56-7.52 (m, 3H),
N-(4-Acetylp h en yl)-N-n a p h th a len -2-ylh yd r a zin eca r box-
ylic Acid ter t-Bu tyl Ester (3i, solid ). 1H NMR (400 MHz,
CDCl3) δ 7.95 (d, J ) 1.6 Hz, 1H), 7.85-7.83 (m, 4H), 7.77-
7.67 (m, 4H), 7.44-7.37 (m, 2H), 6.87 (s, 1H), 6.84-6.81 (m, 2H),
2.50 (1s, 3H), 1.40 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 196.3,
153.4, 152.1, 139.5, 133.2, 130.7, 130.3, 130.1, 128.1, 127.6, 127.3,
126.2, 125.3, 121.0, 118.6, 111.8, 82.8, 28.1, 26.3; FT-IR (CHCl3)
5780 J . Org. Chem., Vol. 69, No. 17, 2004