The Journal of Organic Chemistry
ARTICLE
to reflux and stirred. After 12 h, the reaction mixture was cooled and the
product crystallized from the solution. The crude product was washed
with cold (ꢀ10 °C) ethanol and placed under high vacuum to yield the
purified product as a yellow-orange crystalline solid.
138.1, 130.3, 129.4, 127.3 (q, J = 278.4 Hz), 123.7, 116.5, 40.8 (q, J =
27.4 Hz), 33.2, 25.1 (m), 25.0, 24.0 (m); IR (CHCl3) 3327, 3103, 3023,
2963, 1619, 1594 cmꢀ1; HRMS (ESI) m/z calcd for C13H13F3N4NaO4
(M + Na)+ 369.0787, found 369.0786. Anal. Calcd for C13H13F3N4O4:
C, 45.09; H, 3.78. Found: C, 45.14; H, 3.72.
4-Benzyloxycyclohexanone (2,4-Dinitrophenyl)hydrazone
(11). The standard hydrazone formation procedure was followed with
4-benzyloxycyclohexanone (19; 0.817 g, 4.0 mmol) followed by an
additional recrystallization from ethanol, to yield an orange solid (1.24 g,
80%): mp 125ꢀ126 °C (lit.77 mp 126ꢀ128 °C); 1H NMR (500 MHz,
CDCl3) δ 11.19 (s, 1H), 9.12 (d, J = 2.6 Hz, 1H), 8.29 (dd, J = 9.6, 2.4
Hz, 1H), 7.97 (d, J = 9.6 Hz, 1H), 7.40ꢀ7.28 (m, 5H), 4.61 (m, 2H),
3.81 (tt, J = 5.9, 3.1 Hz, 1H), 2.80ꢀ2.61 (m, 2H), 2.53ꢀ2.39 (m, 2H),
2.09ꢀ2.00 (m, 2H), 2.00ꢀ1.86 (m, 2H); 13C NMR (126 MHz, CDCl3)
δ 160.3, 145.5, 138.7, 137.8, 130.2, 129.1, 128.7, 127.9, 127.7, 123.8,
116.5, 73.1, 70.5, 31.2, 31.0, 30.0, 23.0; IR (CHCl3) 3327, 3102, 3022,
2954, 2864, 1619 cmꢀ1; HRMS (ESI) m/z calcd for C19H19N4O5 (M ꢀ
H)ꢀ 383.1356, found 383.1346. Anal. Calcd for C19H20N4O5: C, 59.37;
H, 5.24. Found: C, 59.46; H, 5.43.
4-Methoxycyclohexanone (2,4-Dinitrophenyl)hydrazone
(12). The standard hydrazone formation procedure was followed with
4-methoxycyclohexanone (21; 0.500 g, 3.90 mmol) to yield an orange
solid (0.979 g, 82%): mp 139ꢀ140 °C (lit.78 mp 150 °C); 1H NMR (500
MHz, CDCl3) δ 11.19 (s, 1H), 9.12 (d, J = 2.6 Hz, 1H), 8.29 (dd, J = 9.6,
2.5Hz, 1H), 7.96 (d, J = 9.6 Hz, 1H), 3.59 (tt, J = 5.8, 3.3 Hz, 1H), 3.40 (s,
3H), 2.71ꢀ2.57 (m, 2H), 2.50ꢀ2.38 (m, 2H), 2.02ꢀ1.85 (m, 4H); 13C
NMR (126 MHz, CDCl3) δ 160.2, 145.5, 137.8, 130.2, 129.1, 123.8,
116.5, 75.2, 56.3, 31.0, 30.4, 29.5, 22.9; IR (CHCl3) 3327, 3113, 3018,
2953, 2885, 1619 cmꢀ1; HRMS (ESI) m/z calcd for C13H16N4NaO5
(M + Na)+ 331.1018, found 331.1018.
4-(Methyoxycarbonyloxy)cyclohexanone(2,4-Dinitrophenyl)-
hydrazone (13). The standard hydrazone formation procedure was
followed with methyl 4-(methyoxycarbonyloxy)cyclohexanone (24;
2.10 g, 12.2 mmol) followed by an additional recrystallization from 1/1
ethanol/ethyl acetate, to yield a yellow solid (3.05 g, 71%): mp
160ꢀ162 °C; 1H NMR (500 MHz, CDCl3) δ 11.15 (s, 1H), 9.07 (d,
J = 2.6 Hz, 1H), 8.26 (dd, J = 9.6, 2.5 Hz, 1H), 7.93 (d, J = 9.6 Hz, 1H),
5.00 (m, 1H), 3.80 (s, 3H), 2.74ꢀ2.60 (m, 2H), 2.57ꢀ2.46 (m, 2H),
2.12ꢀ1.98 (m, 4H); 13C NMR (126 MHz, CDCl3) δ 158.3, 155.2,
145.4, 137.9, 130.2, 129.2, 123.7, 116.4, 73.2, 55.1, 31.0, 30.8, 29.6, 22.9;
IR (CHCl3) 3327, 3102, 3029, 2959, 1746, 1619 cmꢀ1; HRMS (ESI)
m/z calcd for C14H15N4O7 (M ꢀ H)ꢀ 351.0941, found 351.0947. Anal.
Calcd for C14H16N4O7: C, 47.73; H, 4.58. Found: C, 47.62; H, 4.52.
4-(Methyoxycarbonylamino)cyclohexanone (2,4-Dinitro-
phenyl)hydrazone (14). The standard hydrazone formation procedure
was followed with 4-(methyoxycarbonylamino)cyclohexanone (27;
0.170 g, 1.0 mmol) to yield a yellow solid (0.292 g, 84%): mp
216ꢀ217 °C; 1H NMR (500 MHz, CDCl3) δ 11.16 (s, 1H), 9.12 (d,
J = 2.6 Hz, 1H), 8.30 (dd, J = 9.6, 2.5 Hz, 1H), 7.95 (d, J = 9.6 Hz, 1H),
4.64 (s, 1H), 3.87 (br m, 1H), 3.69 (s, 3H), 2.82 (m, 1H), 2.67 (dtd, J =
14.8, 4.6, 1.8 Hz, 1H), 2.47 (ddd, J = 14.9, 12.0, 5.0 Hz, 1H), 2.34ꢀ2.18
(m, 3H), 1.62ꢀ1.47 (m, 2H); 13C NMR (101 MHz, CDCl3) δ 158.3,
156.4, 145.4, 138.0, 130.3, 129.3, 123.8, 116.5, 52.4, 48.8, 33.3, 32.8, 31.7,
24.8; IR (CH2Cl2) 3436, 3329, 3060, 2970, 2858, 1724 cmꢀ1; HRMS
(ESI) m/z calcd for C14H16N5O6 (M ꢀ H)ꢀ 350.1100, found 350.1108.
Anal. Calcd for C14H17N5O6: C, 47.86; H, 4.88. Found: C, 47.92; H, 4.71.
4-(Trifluoromethyl)cyclohexanone (2,4-Dinitrophenyl)-
hydrazone (15). The standard hydrazone formation procedure was
followed with 4(trifluoromethyl)cyclohexanone (29; 0.114 mg, 0.7 mmol).
Additional reaction time (3 days) was required. Flash chromatography
(5/95 methanol/toluene) gave a yellow solid (0.090 g, 38%): mp
147ꢀ148 °C; 1H NMR (500 MHz, CDCl3) δ 11.18 (s, 1H), 9.12 (d,
J = 2.54 Hz, 1H), 8.31 (dd, J = 9.6, 2.5 Hz, 1H), 7.96 (d, J = 9.6 Hz, 1H),
2.97 (m, 1H), 2.77 (m, 1H), 2.48ꢀ2.35 (m, 2H), 2.31ꢀ2.14 (m, 3H),
1.78ꢀ1.60 (m, 2H); 13C NMR (126 MHz, CDCl3) δ 157.5, 145.4,
Axial-4-benzyloxydecalone (2,4-Dinitrophenyl)hydrazone
(42). The standard hydrazone formation procedure was followed with
axial-4-benzyloxydecalone (34; 0.373 g, 1.4 mmol). Additional purifica-
tion by flash chromatography (1/9 ethyl acetate/hexanes) yielded a
1
yellow solid (0.252 g, 50%): mp 161ꢀ163 °C; H NMR (500 MHz,
CDCl3) δ 11.26 (s, 1H), 9.12 (d, J = 2.5 Hz, 1H), 8.28 (dd, J = 9.6, 2.4
Hz, 1H), 7.96 (d, J = 9.6 Hz, 1H), 7.43ꢀ7.28 (m, 5H), 4.70 (d, J = 11.8
Hz, 1H), 4.50 (d, J = 11.8 Hz, 1H), 3.58 (m, 1H), 2.70 (m, 1H), 2.55 (td,
J = 11.5, 3.1 Hz, 1H), 2.44 (td, J = 14.0 Hz, 5.1 Hz, 1H), 2.37 (m, 1H),
2.20 (m, 1H), 1.89ꢀ1.71 (m, 3H), 1.63ꢀ1.19 (m, 6H, overlap with H2O);
13C NMR (126 MHz, CDCl3) δ 162.1, 145.9, 138.9, 137.6, 130.1, 129.0,
128.6, 127.83, 127.75, 123.8, 116.6, 76.3, 71.5, 48.6, 43.1, 29.9, 28.9, 27.5, 26.2,
25.8, 22.1; IR (CH2Cl2) 3331, 3108, 3061, 2935, 2859, 1619 cmꢀ1; HRMS
(ESI) m/z calcd for C23H26N4NaO5 (M + Na)+ 461.1801, found 461.1800.
Anal. Calcd for C23H26N4O5: C, 63.00; H, 5.98. Found: C, 63.09; H, 6.09.
Equatorial-4-benzyloxydecalone (2,4-Dinitrophenyl)-
hydrazone (43). The standard hydrazone formation procedure was
followed with equatorial-4-benzyloxydecalone (38; 0.050 g, 0.2 mmol).
The product was an orange solid (0.077 g, 92%): mp 174ꢀ175 °C; 1H
NMR (500 MHz, CDCl3) δ 11.20 (s, 1H), 9.12 (d, J = 2.4 Hz, 1H), 8.29
(dd, J = 9.6, 2.2 Hz, 1H), 7.96 (d, J = 9.6 Hz, 1H), 7.39ꢀ7.27 (m, 5H),
4.67 (d, J = 11.6 Hz, 1H), 4.51 (d, J = 11.6 Hz, 1H), 3.35 (td, J = 9.5, 4.4 Hz,
1H), 2.91 (dt, J = 15.0, 4.0 Hz), 2.42ꢀ2.32 (m, 2H), 2.21 (m, 1H), 2.14ꢀ
1.99 (m, 2H), 1.92ꢀ1.76 (m, 2H), 1.64ꢀ1.53 (m, 1H, overlap with
H2O), 1.51ꢀ1.39 (m, 2H), 1.32ꢀ1.18 (m, 2H), 1.05 (m, 1H); 13C NMR
(126 MHz, CDCl3) δ 160.9, 145.8, 138.6, 137.8, 130.2, 129.2, 128.7,
127.99, 127.96, 123.8, 116.7, 80.4, 71.5, 48.9, 46.5, 30.8, 29.5, 27.2, 25.8,
25.7, 24.3; IR (CH2Cl2) 3330, 3103, 3054, 2932, 2858, 1619 cmꢀ1; HRMS
(ESI) m/zcalcd for C23H26N4NaO5 (M+Na)+ 461.1801, found 461.1798.
Axial-4-methoxydecalone (2,4-Dinitrophenyl)hydrazone
(44). The standard hydrazone formation procedure was followed with
axial-4-methoxydecalone (35; 0.202 g, 1.1 mmol). Additional purifica-
tion by flash chromatography (1/9 ethyl acetate/hexanes) yielded an
1
orange solid (0.340 g, 85%): mp 172ꢀ173 °C; H NMR (500 MHz,
CDCl3) δ 11.26 (s, 1H), 9.13, (d, J = 2.5 Hz, 1H), 8.28 (dd, J = 9.6, 2.5
Hz, 1H), 7.96 (d, J = 9.6 Hz, 1H), 3.41 (s, 3H), 3.32 (m, 1H), 2.68 (m,
1H), 2.44 (td, J = 11.5, 3.2 Hz, 1H), 2.40ꢀ2.30 (m, 2H), 2.19 (m, 1H),
1.88ꢀ1.75 (m, 2H), 1.73ꢀ1.58 (m, 2H), 1.54ꢀ1.34 (m, 3H),
1.34ꢀ1.18 (m, 2H); 13C NMR (126 MHz, CDCl3) δ 162.9, 146.0,
137.6, 130.2, 129.0, 123.9, 116.6, 78.4, 57.4, 48.6, 43.1, 29.8, 28.2, 27.5,
26.2, 25.8, 21.9; IR (CH2Cl2) 3331, 3108, 3056, 2934, 2859, 1619 cmꢀ1
;
HRMS (ESI) m/z calcd for C17H22N4NaO5 (M + Na)+ 385.1488, found
385.1483. Anal. Calcd for C17H22N4O5: C, 56.34; H, 6.12. Found: C,
56.59; H, 6.16.
Equatorial-4-methoxydecalone (2,4-Dinitrophenyl)hydrazone
(45). The standard hydrazone formation procedure was followed with
equatorial-4-methoxydecalone (39; 0.035 g, 0.2 mmol). The reaction
time was 3 days. Crystallization from the reaction mixture gave an orange
solid (0.046 g, 67%): mp 152ꢀ153 °C; 1H NMR (500 MHz, CDCl3) δ
11.19 (s, 1H), 9.12, (d, J = 2.6 Hz, 1H), 8.29 (dd, J = 9.6, 2.5 Hz, 1H),
7.96 (d, J = 9.6 Hz, 1H), 3.40 (s, 3H), 3.12 (td, J = 9.4, 4.1 Hz, 1H), 2.89
(dt, J = 15.1, 4.5 Hz, 1H), 2.35 (dq, J = 13.3, 4.5 Hz, 1H), 2.30ꢀ2.15 (m,
2H), 2.15ꢀ1.99 (m, 2H), 1.93ꢀ1.75 (m, 2H), 1.55ꢀ1.38 (m, 2H),
1.39ꢀ1.17 (m, 3H), 1.07 (m, 1H); 13C NMR (126 MHz, CDCl3) δ
161.0, 145.8, 137.8, 130.2, 129.1, 123.8, 116.7, 82.3, 57.2, 48.8, 46.4, 30.8,
28.7, 27.3, 25.8, 25.7, 24.2; IR (CH2Cl2) 3330, 3107, 3057, 2933, 2858,
1619 cmꢀ1; HRMS (ESI) m/z calcd for C17H21N4O5 (M ꢀ H)ꢀ
361.1512, found 361.1505. Anal. Calcd for C17H22N4O5: C, 56.34; H,
6.12. Found: C, 56.51; H, 6.22.
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dx.doi.org/10.1021/jo200950s |J. Org. Chem. 2011, 76, 7706–7719