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The Journal of Organic Chemistry
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8.28ꢀ8.22 (m, 2H), 7.23ꢀ7.13 (m, 4H). 13C NMR (75 MHz,
(EIꢀTOF): m/z calculated for C16H14N2O3 [M]+, 282.1004. Found,
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CDCl3, 24 oC, δ): 165.1 (d, J = 147.4 Hz, C), 161.8 (d, J = 147.0
Hz, C), 144.2 (C), 140.3 (C), 128.0 (CH), 127.9 (CH), 124.5
(CH), 124.4 (CH), 115.8 (CH), 115.7 (CH), 115.5 (CH), 115.4
(CH). HRMS (EIꢀTOF): m/z calculated for C12H8F2N2O [M]+,
234.0605. Found, 234.0610.
282.1010.
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1,2ꢀbis(4ꢀ(ethoxycarbonyl)phenyl)diazene oxide 1p (9 mg, 92%,
pale yellow solid, mp = 112.6~114.6 oC): Rf = 0.28(EtOAc : nꢀ
hexane = 1:10); 1H NMR (300 MHz, CDCl3, 24 oC, δ): 8.39 (d, J
= 8.8 Hz, 2H), 8.22ꢀ8.15 (m, 6H), 4.44 (q, J = 7.2 Hz, 2H), 4.41
(q, J = 7.2 Hz, 3H), 1.44(t, J = 7.1 Hz, 3H), 1.42 (t, J = 7.1 Hz,
3H). 13C NMR (100 MHz, CDCl3, 24 oC, δ): 165.7 (C), 165.2 (C),
150.8 (C), 146.9 (C), 133.6 (C), 131.0 (C), 130.3 (CH×2), 130.1
(CH×2), 125.2 (CH×2), 122.4 (CH×2), 61.6 (CH2), 61.2 (CH2),
14.3 (CH3×2). HRMS (EIꢀTOF): m/z calculated for C18H18N2O5
[M]+, 342.1216. Found, 342.1216.
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1,2ꢀbis(4ꢀnitrophenyl)diazene oxide 1l (9 mg, 92%, yellow solid,
mp = 189.6~190.8 oC): Rf = 0.21(EtOAc : nꢀhexane = 1:8); 1H
NMR (400 MHz, CDCl3, 24 oC, δ):8.55 (d, J = 9.2 Hz, 2H), 8.44
(d, J = 9.2 Hz, 2H), 8.39 (d, J = 9.2 Hz, 2H), 8.31 (d, J = 9.2 Hz,
2H). 13C NMR (100 MHz, CDCl3, 24 oC, δ): 151.3 (C), 149.9 (C),
147.7 (C), 1.47.4 (C), 126.3 (CH×2), 124.5 (CH×2), 124.3
(CH×2), 123.8 (CH×2). HRMS (EIꢀTOF): m/z calculated for
C12H8N4O5 [M]+, 288.0495. Found, 288.0492.
1,2ꢀbis(3ꢀ(methoxycarbonyl)phenyl)diazene oxide 1q (52 mg,
90%, pale yellow solid, mp = 76.1~77.5 oC): Rf = 0.25(EtOAc : nꢀ
hexane = 1:15); 1H NMR (400 MHz, CDCl3, 24 oC, δ): 8.97 (s,
1H), 8.75 (s, 1H), 8.52 (dd, J = 8.1, 1.1 Hz, 1H), 8.44 (d, J = 8.0
Hz, 1H), 8.27 (d, J = 7.7 Hz, 1H), 8.09 (d, J = 7.7 Hz, 1H), 7.62
(t, J = 7.9 Hz, 1H), 7.58 (t, J = 7.9 Hz, 1H), 4.45 (q, J = 7.1 Hz,
2H), 4.42 (q, J = 7.1 Hz, 2H), 1.44 (t, J = 7.0 Hz, 3H), 1.43 (t, J =
6.9 Hz, 3H). 13C NMR (75 MHz, CDCl3, 24 oC, δ): 165.8 (C),
165.1 (C), 148.2 (C), 143.7 (C), 132.6 (CH), 131.6 (C), 131.2 (C),
130.5 (CH), 129.1 (CH), 128.9 (CH), 128.7 (CH), 127.0 (CH),
126.3 (CH), 123.4 (CH), 61.5 (CH2), 61.2 (CH2), 14.2 (CH3×2).
HRMS (EIꢀTOF): m/z calculated for C18H18N2O5 [M]+, 342.1216.
Found, 342.1216.
1,2ꢀbis(3ꢀnitrophenyl)diazene oxide 1m (68 mg, 91%, white solid,
mp = 145.3~146.4 oC): Rf = 0.15(EtOAc : nꢀhexane = 1:6); 1H
NMR (400 MHz, CDCl3, 24 oC, δ): 9.22 (t, J = 2.0 Hz, 1 H), 9.13
(t, J = 2.0 Hz, 1 H), 8.71 (ddd, J = 8.2, 2.1, 0.9 Hz, 1 H), 8.49
(tdd, J = 8.2, 2.1, 0.9 Hz, 2 H), 8.31 (ddd, J = 8.2, 2.1, 0.9 Hz, 1
H), 7.79 (t, J = 8.2 Hz, 1 H), 7.71 (t, J = 8.2 Hz, 1 H). 13C NMR
(100 MHz, CDCl3, 24 oC, δ): 148.4 (C), 148.3 (C×2) , 143.8 (C),
131.5 (CH), 130.2 (CH), 129.7 (CH), 128.0 (CH), 126.7 (CH),
124.5 (CH), 120.4 (CH), 118.0 (CH). HRMS (EIꢀTOF): m/z
calculated for C12H8N4O5 [M]+, 288.0495. Found, 288.0494.
1,2ꢀbis(4ꢀacetylphenyl)diazene oxide 1n (9 mg, 94%, pale yellow
solid, mp = 186.2~189.4 oC): Rf = 0.13(EtOAc : nꢀhexane = 1:5);
1H NMR (400 MHz, CDCl3, 24 oC, δ): 8.44 (d, J = 8.6 Hz, 2H),
8.23 (d, J = 8.7 Hz, 2H), 8.13 (d, J = 8.9 Hz, 2H), 8.10 (d, J = 8.7
Hz, 2H), 2.70 (s, 3H), 2.67 (s, 3H). 13C NMR (100 MHz, CDCl3,
24 oC, δ): 197.0 (C), 196.7 (C), 150.7 (C),147.0 (C), 140.0 (C),
137.3 (C), 129.0 (CH×2), 128.9 (CH×2), 126.0 (CH×2), 122.8
(CH×2), 26.9 (CH3), 26.7 (CH3). HRMS (EIꢀTOF): m/z calculated
for C16H14N2O3 [M]+, 282.1004. Found, 282.1009.
1,2ꢀbis(4ꢀethylphenyl)diazene oxide 1r (31 mg, 88%, yellowish
oil): Rf = 0.16(EtOAc : nꢀhexane = 1:120); 1H NMR (300 MHz,
CDCl3, 24 oC, δ): 8.20 (d, J = 8.5 Hz, 2H), 8.13 (d, J = 8.4 Hz,
2H), 7.35ꢀ7.29 (m, 4H), 2.78ꢀ2.68 (m, 4H), 1.28 (t, J = 7.6 Hz,
3H), 1.27 (d, J = 7.5 Hz, 3H). 13C NMR (100 MHz, CDCl3, 24 oC,
δ): 148.1 (C), 146.3 (C), 146.1 (C), 141.9 (C), 128.0 (CH×4),
125.6 (CH×2), 122.2 (CH×2), 28.8 (CH2), 28.5 (CH2), 15.2
(CH3×2). HRMS (EIꢀTOF): m/z calculated for C16H18N2O [M]+,
254.1419. Found, 254.1425.
1,2ꢀbis(3ꢀacetylphenyl)diazene oxide 1o (48 mg, 85%, yellow
solid, mp = 135.8~137.2 oC): Rf = 0.18(EtOAc : nꢀhexane = 1:5);
1H NMR (400 MHz, CDCl3, 24 oC, δ): 8.89 (d, J = 1.8 Hz, 1H),
8.72 (d, J = 1.6 Hz, 1H), 8.54 (dd, J = 8.2, 1.1 Hz, 1H), 8.42 (dd,
J = 8.2, 1.1 Hz, 1H), 8.19 (d, J = 7.7 Hz, 1H), 8.02 (d, J = 7.7 Hz,
1H), 7.66 (t, J = 7.9 Hz, 1H), 7.61 (t, J = 7.9 Hz, 1H), 2.71 (s,
3H), 2.68 (s, 3H). 13C NMR (100 MHz, CDCl3, 24 oC, δ): 197.2
(C), 196.3 (C), 148.3 (C), 143.8 (C), 137.8 (C), 137.6 (C), 131.2
(CH), 129.5 (CH), 129.3 (CH), 129.1 (CH), 129.0 (CH), 126.4
(CH), 125.7 (CH), 122.1 (CH), 26.7 (CH3), 26.6 (CH3). HRMS
1,2ꢀbis(4ꢀmethoxyphenyl)diazene oxide 1s (8 mg, 69%, yellowish
solid, mp = 114.5~117.5 oC): Rf = 0.3(EtOAc : nꢀhexane = 1:5);
1H NMR (400 MHz, CDCl3, 24 oC, δ): 8.26 (t, J = 9.2 Hz, 4H),
6.99ꢀ6.94 (m, 4H), 3.89 (s, 3H), 3.88 (s, 3H). 13C NMR (100
MHz, CDCl3, 24 oC, δ): 161.8 (C), 160.1 (C), 141.6 (C), 137.9
(C), 127.7 (CH×2), 123.7 (CH×2), 113.6 (CH×2), 113.5 (CH×2),
55.6 (CH3), 55.4 (CH3). HRMS (EIꢀTOF): m/z calculated for
C14H14N2O3 [M]+, 258.1004. Found, 258.1002.
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