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B. Stefane et al. / Tetrahedron Letters 42 (2001) 6659–6662
6662
References
methanol giving 2b in 50% yields. Mp 130–132°C (acetone/
methanol); IR (KBr): 3105, 2933, 1712, 1608, 1524, 1345,
1231, 1124, 1013, 972, 859 cm−1 1H NMR (300 MHz,
CDCl3): l 4.46 (s, 2H), 7.32–7.41 (m, 7H), 7.56–7.61 (m,
2H), 8.28–8.40 (m, 4H); 13C NMR (75 MHz, CDCl3): l
42.3, 123.4, 125.0, 125.3, 128.0, 129.4, 129.5, 130.6, 133.9,
141.2, 148.5, 148.6, 152.7, 173.4; MS (FAB) m/z (rel.
intensity) 406 (MH+, 40), 107 (23), 91 (26). Anal. calcd for
C20H15N5O5: C, 59.26; H, 3.73; N, 17.28. Found: C, 59.53;
H, 3.56; N, 17.45.
1. For a general review on the amino protective groups, see:
(a) Greene, T. W. In Protective Groups in Organic Synthe-
sis; John Wiley & Sons: New York, 1991; p. 494; (b) Kunz,
H.; Waldmann, H. In Comprehensive Organic Synthesis;
Trost, B. M.; Fleming, I.; Winterfeldt, E., Eds.; Pergamon
Press: New York, 1991; Vol. 6, p. 631; (c) Kocienski, P.
J. In Protecting Groups; Thieme: New York, 1994; p. 185.
For recent reviews see: (a) Theodoridis, G. Tetrahedron
2000, 56, 2339; (b) Jarowicki, K.; Kocienski, P. J. J. Chem.
Soc., Perkin Trans. 1 2000, 2495.
;
10. Compound 2c: methyl chloroformate (0.1 mol, 9.45 g) was
slowly added at rt to a stirred suspension of 1,3-bis(4-nitro-
fenil) triazene (10 mmol, 2.86 g) and potassium carbonate
(0.092 mol, 12.82 g) in acetone (60 mL). The reaction
mixture was stirred at rt for 20 h, the solid material was
filtered off, suspended in water (50 mL) and the insoluble
material separated by filtration and crystallized from
toluene giving 2c in 35% yields. Mp 127–129°C (toluene);
IR (KBr): 3113, 3081, 1734, 1609, 1522, 1476, 1447, 1217,
1107, 961, 860, 760 cm−1; 1H NMR (300 MHz, DMSO-d6):
l 3.92 (s, 3H), 7.63–7.74 (M, 4H), 8.30–8.40 (m, 4H); 13C
NMR (75 MHz, CDCl3): l 55.2, 123.5, 125.1, 125.2, 130.6,
141.8, 148.4, 148.5, 152.6, 153.6; MS (EI) m/z (rel. inten-
sity) 317 (M+−28, 30), 196 (92), 166 (20), 150 (62), 122
(1000). Anal. calcd for C14H11N5O6: C, 48.70; H, 3.21; N,
20.28. Found: C, 48.91; H, 3.20; N, 20.01.
&
2. Stefane, B.; Kocˇevar, M.; Polanc, S. J. Org. Chem. 1997,
62, 7165.
3. Hill, D. T.; Stanley, K. G.; Williams, J. E. K.; Love, B.;
Fowler, P. J.; McCafferty, J. P.; Macko, E.; Ladd, C. B.
J. Med. Chem. 1983, 26, 865.
4. (a) Wirschun, W.; Jochims, J. C. Synthesis 1997, 233; (b)
Wirschun, W.; Maier, G.-M.; Jochims, J. C. Tetrahedron
1997, 53, 5755.
5. (a) Smith, R. H.; Mehl, A. F.; Hicks, A.; Denlinger, C. L.;
Kratz, L.; Wesley, A. A.; Michejda, J. C. J. Org. Chem.
1986, 51, 3751; (b) Iley, J.; Ruecroft, G.; Carvalho, E.;
Rosa, E. J. Chem. Res. (S) 1989, 162; (c) Smith, H. R.;
Scudiero, D. A.; Michejda, C. J. J. Med. Chem. 1990, 33,
2579; (d) Smith, H. R.; Wladkowski, D. B.; Herling, J. A.;
Pfaltzgraff, B. P.; Klose, J.; Michejda, C. J. J. Org. Chem.
1992, 57, 654; (e) Carvalho, E.; Iley, J.; Rosa, E. J. Chem.
Soc., Perkin Trans. 2 1993, 865.
11. (a) Waldmann, H. Tetrahedron Lett. 1988, 29, 1131; (b)
Waldmann, H.; Sebastian, D. Chem. Rev. 1994, 94, 911.
12. Reaction of 3-acyl-1,3-diaryltriazenes 1a and 1b and 2a–c
with amines. A selected amine (1 mmol) was added to the
solution of 3-acyl-1,3-diaryltriazene (1.1 mmol) in acetoni-
trile, methanol or chloroform (8 mL). The reaction mixture
was stirred at room temperature for 2–84 h (see Table 2).
Triazene was filtered off and washed with methanol (2×5
mL). The solution was then evaporated to dryness and the
solid material purified on chromatotron using
EtOAc:hexane=1:5 (4n), EtOAc:hexane=3:5 (4i and 4l),
MeOH:CHCl3=1:25 (4m) and MeOH:CHCl3=1:10 (for
others). Compound 4g: mp 134–136°C (diethyl ether/
petroleum ether); IR (KBr): 3420, 3360, 2810, 1650, 1520,
6. Compound 1a: mp 123–126°C (ethanol); IR (KBr): 3100,
1740, 1525, 1475, 1380, 1350, 1200 cm−1; H NMR (300
1
MHz, CDCl3): l 2.77 (3H, s), 7.43 (1H, d, J=8.6 Hz), 7.61
(1H, d, J=8.6 Hz), 8.19 (1H, dd, J1=8.6 Hz, J2=2.3 Hz),
8.27 (1H, dd, J1=8.6 Hz, J2=2.5 Hz), 8.33 (1H, d, J=2.3
Hz), 8.43 (1H, d, J=2.5 Hz); 13C NMR (75 MHz,
DMSO-d6): l 22.2, 120.7, 123.3, 123.6, 124.7, 125.6, 130.8,
132.4, 133.1, 139.5, 147.5, 148.6, 148.9, 171.9. Anal. calcd
for C14H9Cl2N5O5: C, 42.32; H, 2.27; N, 17.63. Found: C,
42.35; H, 2.37; N, 17.34.
7. Compound 1b: mp 106–108°C (toluene); IR (KBr): 3120,
1735, 1535, 1480, 1360, 1240, 1150, 1130, 1060, 990, 910,
1450, 1420, 1285, 1235, 1165, 1045, 835, 750 cm−1 1H
;
1
810, 760, 740 cm−1; H NMR (300 MHz, CDCl3): l 4.45
NMR (300 MHz, DMSO-d6): l 2.76–2.84 (4H, m), 3.57–
3.60 (4H, m), 3.75 (2H, s), 4.60 (2H, bs), 6.46–6.51 (2H,
m), 6.65–6.70 (2H, m), 7.19–7.34 (5H, m); MS (EI) m/z (rel.
intensity) 295 (M+, 100), 176 (27), 147 (65), 120 (43), 91
(35). Anal. calcd for C18H21N3O: C, 73.19; H, 7.17; N,
14.23. Found: C, 73.57; H, 7.35; N, 14.09. Compound 4h:
mp 114–116°C (diethyl ether/petroleum ether); IR (KBr):
(2H, s), 7.34–7.45 (7H, m), 8.18 (1H, dd, J1=8.9 Hz,
J2=2.4 Hz), 8.27 (1H, dd, J1=8.9 Hz, J2=2.4 Hz), 8.33
(1H, d, J=2.4 Hz), 8.42 (1H, d, J=2.4 Hz); 13C NMR (75
MHz, DMSO-d6): l 40.6, 120.6, 123.3, 123.5, 124.7, 125.6,
126.9, 128.4, 129.6, 131.1, 132.4, 133.2, 133.8, 139.4, 147.6,
148.6, 148.7, 172.4; MS (FAB) m/z (rel. intensity) 474
(MH+, 2), 184 (40), 91 (44), 71 (39). Anal. calcd for
C20H13Cl2N5O5: C, 50.65; H, 2.76; N, 14.77. Found: C,
50.96; H, 2.77; N, 14.66.
3210, 3060, 1600, 1505, 1430, 1320, 1215, 820, 715 cm−1
;
1H NMR (300 MHz, CDCl3): l 1.58 (3H, s), 2.64 (2H, t,
J=6.8 Hz), 3.42 (2H, dt, J1=J2=6.8 Hz), 3.53 (2H, s), 5.33
(2H, bs), 6.68–6.72 (2H, m), 6.85–6.89 (2H, m), 7.15–7.18
(2H, m), 7.28–7.33 (3H, m); 13C NMR (75 MHz, DMSO-
d6): l 34.6, 40.9, 43.9, 115.5, 127.4, 129.1, 129.5, 129.7,
129.8, 130.3, 134.6, 154.6, 171.2; MS (EI) m/z (rel. inten-
sity) 256 (MH+, 4), 136 (35), 120 (100), 107 (32), 91 (52),
77 (21). Anal. calcd for C16H17NO2: C, 75.27; H, 6.71; N,
5.95. Found: C, 75.45; H, 6.53; N, 5.88.
8. Pytela, O.; Pilny, M.; Vecera, M. Collect. Czech. Chem.
Commun. 1984, 49, 1173, (Chem. Abstr. 1984, 101:
109982b).
9. Compound 2b: 1,3-bis(4-nitrophenil)triazene (22 mmol,
6.314 g) was added at rt to the stirred solution of
phenylacetyl chloride (24.2 mmol, 3.742 g) in acetone (80
mL) and then triethylamine (24.2 mmol, 2.444 g, 3.39 mL)
was slowly added. After stirring the reaction mixture at rt
for 24 h, the solid material was filtered off and filtrate
evaporated to dryness, treated with water (50 mL), filtered
off, washed with water and crystallized from acetone/
13. (a) Katritzky, A. R.; Chang, H.; Yang, B. Synthesis 1995,
503; (b) Katritzky, A. R.; Yang, B.; Semenzin, D. J. Org.
Chem. 1997, 62, 726; (c) Katritzky, A. R.; He, H.-Y.;
Suzuki, K. J. Org. Chem. 2000, 65, 8210.