Nitrosation with Sodium Hexanitrocobaltate(III)
J . Org. Chem., Vol. 62, No. 21, 1997 7169
Gen er a l P r oced u r e for th e Syn th esis of 3-Meth yl-1,3-
d ia r yltr ia zen es. Powdered NaOH (1 mmol, 40 mg) and MeI
(0.2 mL, 456 mg, 3.19 mmol) were added to the solution of 1
mmol of a triazene 4 in MeOH (8 mL) and heated under reflux
for 1 h. Then, another portion of MeI (0.2 mL, 456 mg, 3.19
mmol) was added at rt and the reaction mixture was stirred,
until the starting triazene disappeared as followed by TLC
(0.5-12 h). The reaction mixture was kept at -15 °C for 1-2
h. The product 5 was filtered off and washed with MeOH (2
× 5 mL), precooled to -15 °C.
(rel intensity) 415 (M+, 0.6), 207 (41), 179 (100); HRMS calcd
for C15H9Cl2F6N3 415.0078, found 415.0088. Anal. Calcd for
C15H9Cl2F6N3: C, 43.29; H, 2.18; N, 10.10. Found: C, 43.07;
H, 2.00; N, 10.20.
3-Meth yl-1,3-bis(4-cya n op h en yl)tr ia zen e (5l) was pre-
pared as described in the general procedure, expect using
MeONa (54 mg, 1 mmol) instead of NaOH. The reaction
mixture was stirred after the first addition of MeI at rt for 3
h and after the second addition of the same reagent for 23 h:
240 mg of 5l was isolated, yield 92%; mp 211-212 °C
(methanol); IR (KBr) 2230, 1605, 1510, 1450, 1400, 1353, 1317,
1215, 1205, 1160, 1100, 985, 850, 835 cm-1; 1H NMR (300 MHz,
DMSO-d6) δ 3.70 (s, 3H), 7.73 (m, 1H), 7.76 (m, 2H), 7.79 (m,
1H), 7.90 (m, 4H); 13C NMR (75 MHz, DMSO-d6) δ 32.3, 105.9,
109.3, 117.3 (2C), 118.8 (2C), 122.2 (4C), 133.5 (2C), 147.3,
152.3; MS m/ z (rel intensity) 261 (M+, 2.1), 130 (50), 102 (100);
HRMS calcd for C15H11N5 261.1014, found 261.1012. Anal.
Calcd for C15H11N5: C, 68.95; H, 4.24; N, 26.80. Found: C,
68.81; H, 4.27; N, 27.07.
3-Meth yl-1,3-bis(2-iod op h en yl)tr ia zen e (5d ): 410 mg,
yield 89%; mp 77-78 °C (methanol); IR (KBr) 1580, 1480,
1455, 1427, 1397, 1263, 1230, 1205, 1128, 1023, 755 cm-1; 1H
NMR (300 MHz, DMSO-d6) δ 3.57 (s, 3H), 7.00 (ddd, 1H, J 1
)
7.8 Hz, J 2 ) 7.2 Hz, J 3 ) 1.7 Hz), 7.17 (ddd, 1H, J 1 ) 7.9 Hz,
J 2 ) 7.2 Hz, J 3 ) 1.8 Hz), 7.37 (ddd, 1H, J 1 ) 8.5 Hz, J 2 ) 7.2
Hz, J 3 ) 1.3 Hz), 7.46 (dd, 2H, J 1 ) 7.9 Hz, J 2 ) 1.4 Hz), 7.53
(ddd, 1H, J 1 ) 7.9 Hz, J 2 ) 7.3 Hz, J 3 ) 1.4 Hz), 7.93 (d, 1H,
J ) 7.5 Hz), 8.02 (dd, 1H, J 1 ) 7.8 Hz, J 2 ) 1.3 Hz); 13C NMR
(75 MHz, DMSO-d6) δ 38.3, 95.8, 97.3, 117.8, 127.5, 128.2,
128.9, 129.3, 129.4, 139.0, 139.8, 147.0, 148.9; MS m/ z (rel
intensity) 463 (M+, 1.4), 231 (97), 203 (100), 76 (55); HRMS
calcd for C13H11I2N3 462.9043, found 462.9056. Anal. Calcd
for C13H11I2N3: C, 33.72; H, 2.39; N, 9.07. Found: C, 33.53;
H, 2.30; N, 9.13.
1,2,3-Ben zotr iazin -4(3H)-on e (6) was prepared from 2-ami-
nobenzamide and SHNC as described above for the synthesis
of 1,3-diaryltriazenes: reaction time, 41 h; 111 mg, yield 76%;
mp 219-220 °C (methanol); lit.42 mp 220 °C (dec).
5-(6-Am in o-1,3-b e n zod ioxol-5-yl)a zo-1,3-b e n zod iox-
ole (10) was prepared from aromatic amine 7 and SHNC,
following the above procedure for the synthesis of 1,3-diaryl-
triazenes: reaction time, 3 h; 98 mg; yield 69% (after column
chromatography on silica gel; petroleum ether-ethyl acetate
5:3); mp 216-218 °C (acetonitrile); IR (KBr) 3290, 1614, 1495,
1470, 1255, 1225, 1033, 933 cm-1; 1H NMR (300 MHz, DMSO-
d6) δ 5.95 (s, 2H), 6.10 (s, 2H), 6.41 (s, 1H), 6.43 (s, 2H), 7.02
(d, 1H, J ) 8.2 Hz), 7.07 (s, 1H), 7.38 (dd, 1H, J 1 ) 8.2 Hz, J 2
) 1.8 Hz), 7.52 (d, 1H, J ) 1.8 Hz); 13C NMR (75 MHz, DMSO-
d6) δ 95.8, 96.9, 98.3, 101.0, 101.6, 107.9, 121.3, 129.5, 139.7,
145.6, 148.0, 148.4, 148.5, 151.6; MS m/ z (rel intensity) 285
(M+, 100), 136 (79), 121 (57), 65 (40); HRMS calcd for
C14H11N3O4 285.0750, found 285.0751. Anal. Calcd for
C14H11N3O4: C, 58.95; H, 3.89; N, 14.73. Found: C, 59.12; H,
4.07; N, 15.06.
P r ep a r a tion of 5-(1-Meth ylp yr r ol-2-yl)a zo-1,3-ben zo-
d ioxole (11). A solution of SHNC (3 mmol, 1.212 g) in H2O
(4 mL) was added at room temperature to a solution of
aromatic amine 7 (4 mmol, 548 mg) and N-methylpyrrole (4
mmol, 324 mg) in MeOH (16 mL). The reaction mixture was
stirred for 18 h and then evaporated to dryness. The residue
was treated with H2O (15 mL) and the solid material was
filtered off and washed with H2O (3 × 5 mL). Separation by
column chromatography (silica gel, petroleum ether-ethyl
acetate 5:3) gave 307 mg (yield 34%) of 11 and 45 mg (yield
8%) of 10.
3-Me t h yl-1,3-b is(3-ch lor o-4-flu or op h e n yl)t r ia ze n e
(5e): 274 mg, yield 87%; mp 128-128.5 °C (methanol); IR
(KBr) 1597, 1495, 1455, 1387, 1260, 1235, 1187, 1117, 1055,
1
830, 760 cm-1; H NMR (300 MHz, DMSO-d6) δ 3.60 (s, 3H),
7.45 (dd, 1H, J 1 ) J 2 ) 8.9 Hz), 7.46 (dd, 1H, J 1 ) J 2 ) 8.9
Hz), 7.56 (m, 2H), 7.70 (dd, 1H, J 1 ) 7.6 Hz, J 2 ) 2.4 Hz), 7.74
(dd, 1H, J 1 ) 6.8 Hz, J 2 ) 2.7 Hz); 13C NMR (75 MHz, DMSO-
d6) δ 32.8, 117.1 (d, J ) 1.6 Hz), 117.4 (d, J ) 1.6 Hz), 117.6
(d, J ) 7.0 Hz), 118.9, 120.1 (d, J ) 18.6 Hz), 120.2 (d, J )
18.8 Hz), 122.0 (d, J ) 7.4 Hz), 122.1, 141.5 (d, J ) 2.8 Hz),
146.7 (d, J ) 3.2 Hz), 154.0 (d, J ) 242 Hz), 155.9 (d, J )
244.8 Hz); MS m/ z (rel intensity) 315 (M+, 10), 157 (76), 129
(100); HRMS calcd for C13H9Cl2F2N3 315.0142, found 315.0146.
Anal. Calcd for C13H9Cl2F2N3: C, 49.39; H, 2.87; N, 13.29.
Found: C, 49.24; H, 2.77; N, 13.40.
3-Meth yl-1,3-bis(3,4-d ich lor op h en yl)tr ia zen e (5f): 312
mg, yield 89%; mp 88-88.5 °C (methanol); IR (KBr) 1593,
1485, 1450, 1395, 1375, 1350, 1240, 1125, 1110, 1027, 995
1
cm-1; H NMR (300 MHz, DMSO-d6) δ 3.60 (s, 3H), 7.51 (dd,
1H, J 1 ) 8.7 Hz, J 2 ) 2.3 Hz), 7.56 (dd, 1H, J 1 ) 8.9 Hz, J 2
)
2.5 Hz), 7.63 (dd, 1H, J 1 ) 8.9 Hz, J 2 ) 0.2 Hz), 7.64 (d, 1H,
J ) 8.6 Hz), 7.72 (d, 1H, J ) 2.3 Hz), 7.76 (d, 1H, J ) 2.5 Hz);
13C NMR (75 MHz, DMSO-d6) δ 32.5, 117.1, 118.4, 121.5, 122.4,
125.9, 129.0, 130.8, 131.0, 131.8, 131.8, 143.9, 149.0; MS m/ z
(rel intensity) 347 (M+, 2.3), 173 (62), 145 (100); HRMS calcd
for C13H9Cl4N3 346.9551, found 346.9561. Anal. Calcd for
C13H9Cl4N3: C, 44.73; H, 2.60; N, 12.04. Found: C, 44.63; H,
2.57; N, 12.12.
11: mp 70-72 °C (from diethyl ether-petroleum ether); IR
(KBr) 1603, 1500, 1475, 1453, 1417, 1260, 1250, 1190, 1040,
1
817, 736 cm-1; H NMR (300 MHz, DMSO-d6) δ 3.91 (s, 3H),
3-Meth yl-1,3-bis(3,4,5-tr ich lor oph en yl)tr iazen e (5h ) was
prepared as described in the general procedure, except using
MeONa (54 mg, 1 mmol) instead of NaOH. The reaction
mixture was stirred after the first addition of MeI at rt for 3
h and after the second addition of the same reagent for 12 h;
386 mg of 5h was isolated: yield 92%; mp 206-207 °C (dec)
(chloroform); IR (KBr) 1585, 1555, 1455, 1427, 1400, 1378,
6.12 (s, 2H), 6.25 (dd, 1H, J 1 ) 4.1 Hz, J 2 ) 2.6 Hz), 6.52 (dd,
1H, J 1 ) 4.1 Hz, J 2 ) 1.7 Hz), 7.05 (d, 1H, J ) 8.2 Hz), 7.21
(m, 1H), 7.32 (d, 1H, J ) 1.9 Hz), 7.36 (dd, 1H, J 1 ) 8.2 Hz, J 2
) 1.9 Hz); 13C NMR (75 MHz, DMSO-d6) δ 32.9, 98.0, 99.0,
101.9, 108.1, 109.8, 121.1, 127.3, 145.5, 148.5, 148.6, 148.9;
MS m/ z (rel intensity) 229 (M+, 100), 80 (48); HRMS calcd
for C12H11N3O2 229.0851, found 229.0802. Anal. Calcd for
C12H11N3O2: C, 62.87; H, 4.84; N, 18.33. Found: C, 62.84; H,
5.05; N, 18.32.
1340, 1245, 1225, 1190, 1143, 1013, 884, 870, 815 cm-1 1H
;
NMR (300 MHz, CDCl3) δ 3.61 (s, 3H), 7.48 (s, 2H), 7.60 (s,
2H); 13C NMR (75 MHz, CDCl3) δ 32.6, 117.0, 121.7, 126.6,
129.7, 134.6, 134.9, 143.5, 148.3; MS m/ z (rel intensity) 415
(M+, 0.6), 207 (51), 179 (100); HRMS calcd for C13H7Cl6N3
414.8771, found 414.8788. Anal. Calcd for C13H7Cl6N3: C,
37.36; H, 1.69. Found: C, 37.47; H, 1.68.
Ack n ow led gm en t. The Ministry of Science and
Technology of Slovenia and the Slovenian Science
Foundation are gratefully acknowledged for financial
support. We would like to thank Dr. Bogdan Kralj and
Dr. Dusˇan Zˇigon (Mass Spectrometry Center, J ozˇef
Stefan Institute, Ljubljana, Slovenia) for mass
measurements.
3-Met h yl-1,3-b is(4-ch lor o-3-(t r iflu or om et h yl)p h en yl-
)tr ia zen e (5j): 391 mg, yield 94%; mp 113-113.5 °C (metha-
nol); IR (KBr) 1605, 1577, 1490, 1475, 1455, 1402, 1355, 1312,
1296, 1228, 1165, 1125, 1105, 1030, 1000 cm-1; 1H NMR (300
MHz, DMSO-d6) δ 3.69 (s, 3H), 7.76 (m, 2H), 7.87 (m, 4H); 13
C
J O9703820
NMR (75 MHz, DMSO-d6) δ 32.7, 116.0 (q, J ) 5.4 Hz), 120.5
(q, J ) 5.4 Hz), 122.2, 122.6 (q, 2C, J ) 273.2 Hz), 125.3 (q, J
) 1.8 Hz), 125.7, 127.3 (q, J ) 30.9 Hz), 127.4 (q, J ) 30.9
Hz), 128.4 (q, J ) 2.2 Hz), 132.5, 132.7, 143.2, 148.2; MS m/ z
(42) El-Shafei, A. K.; Ghattas, A. A. G. J . Indian Chem. Soc. 1984,
61, 65-67.