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(d, J = 7.8 Hz, 2H), 8.16 (d, J = 8.1 Hz, 2H), 8.30–8.35
(m, 3H), 13.60 (br s, 1H). 13C NMR (DMSO-d6); d
153.6, 140.0, 139.7, 131.3, 131.2, 130.1, 130.0, 128.8,
127.4, 127.3, 127.1, 125.5, 119.7, 118.4, 112.1, 104.0.
MS (m/z, rel. int.); 321 (M++1, 100), 283 (50), 229
(10). Anal. Calcd for C21H12N4: C, 78.73; H, 3.78.
Found: C, 78.41; H, 3.89.
13.09 (br s, 1H). 13C NMR (DMSO-d6); d 161.7, 158.4,
151.7, 151.5, 148.0, 141.6, 141.5, 139.2, 130.4, 129.6,
127.2, 127.0, 122.2, 121.2, 121.0, 114.2, 113.9. MS (m/z,
rel. int.); 405 (M++1, 70), 203 (100). Anal. Calcd for
C21H17FN6O2Æ0.8H2O: C, 60.17; H, 4.44. Found: C,
60.00; H, 4.37.
2.4.12. 2-(40-Amidino-30-fluorobiphenyl-4-yl)-1H-benzimid-
azole-5-amidine acetate salt (5c). The same procedure de-
scribed for 5a was used starting with 4c. Yield: 85%, mp:
2.4.7. 2-[30-(N-Hydroxyamidino)-biphenyl-4-yl]-1H-benz-
imidazole-5-N-hydroxyamidine (4b). The same procedure
described for 4a was used starting with 3b. Yield: 95%,
1
210–212 ꢁC. H NMR (D2O/DMSO-d6); d 1.78 (s, 3·
1
CH3), 7.61 (d, J = 8.4 Hz, 1H), 7.84–8.05 (m, 6H), 8.12
(s, 1H), 8.39 (d, J = 8.4 Hz, 2H). MS (m/z, rel. int.); 373
(M++1, 8), 357 (100), 340 (40). Anal. Calcd for
C21H17FN6Æ3.0AcOHÆ1.3H2O: C, 56.30; H, 5.52; N,
14.59. Found: C, 56.12; H, 5.18; N, 14.21.
mp 290–293 ꢁC. H NMR (DMSO-d6); d 5.89 (s, 2H),
5.99 (s, 2H), 7.48–7.53 (m, 4H), 7.73 (d, J = 8.1 Hz,
1H), 7.79 (d, J = 8.1 Hz, 1H), 7.94 (d, J = 8.1 Hz, 2H),
8.06 (s, 1H), 8.30 (d, J = 8.1 Hz, 2H), 9.60 (s, 1H),
9.71 (s, 1H), 13.07 (br s, 1H). 13C NMR (DMSO-d6);
d 151.7, 150.7, 141.2, 139.1, 134.0, 129.1, 128.8, 127.2,
127.1, 127.0, 124.9, 123.7. MS (m/z, rel. int.); 387
(M++1, 80), 194 (100). Anal. Calcd for C21H18N6O2Æ1.0-
H2O: C, 62.36; H, 4.98. Found: C, 62.40; H, 4.93.
2.4.13. 40-Formyl-2-methylbiphenyl-4-carbonitrile (2d).
The same procedure described for 2a was used employ-
ing 4-bromo-3-methylbenzonitrile, instead of 4-bro-
mobenzonitrile. Yield: 71%, mp: 130–130.5 ꢁC. 1H
NMR (DMSO-d6); d 2.28 (s, 3H), 7.46 (d, J = 7.8 Hz,
1H), 7.63 (d, J = 8.1 Hz, 2H), 7.77 (d, J = 7.8 Hz, 1H),
7.86 (s, 1H), 8.02 (d, J = 8.1 Hz, 2H), 10.08 (s, 1H).
13C NMR (DMSO-d6); d 192.7, 145.4, 144.9, 136.6,
135.3, 133.9, 130.3, 129.7, 129.6, 129.5, 118.6, 110.7,
19.6. MS (m/z, rel. int.); 221 (M+, 100), 203 (5), 192
(40), 177 (20), 165 (25). Anal. Calcd for C15H11NO: C,
81.42; H, 5.01. Found: C, 81.50; H, 5.13.
2.4.8.
2-(30-Amidinobiphenyl-4-yl)-1H-benzimidazole-5-
amidine acetate salt (5b). The same procedure described
for 5a was used starting with 4b. Yield: 77%, mp 211–
1
212.5 ꢁC. H NMR (D2O/DMSO-d6); d 1.89 (s, 3· CH3
of acetate), 7.62–7.75 (m, 4H), 7.80–8.15 (m, 4H), 8.20
(s, 1H), 8.38 (d, J = 8.1 Hz, 2H). MS (m/z, rel. int.); 355
(M++1, 20), 339 (60), 322 (100). Anal. Calcd for
C21H18N6Æ3.0AcOHÆ2.4H2O: C, 56.12; H, 6.07; N,
14.55. Found: C, 56.09; H, 5.81; N, 14.80.
2.4.14. 2-(40-Cyano-20-methylbiphenyl-4-yl)-1H-benzimid-
azole-5-carbonitrile (3d). The same procedure described
for 3a was used starting with 2d. Yield: 74%, mp: 269–
2.4.9. 3-Fluoro-40-formylbiphenyl-4-carbonitrile (2c). The
same procedure described for 2a was used employing
1
270 ꢁC. H NMR (DMSO-d6); d 2.34 (s, 3H), 7.49 (d,
4-bromo-2-fluorobenzonitrile,
instead
of
4-bro-
1
J = 7.8 Hz, 1H), 7.60–7.63 (m, 3H), 7.77 (d, J = 7.8 Hz,
2H), 7.85 (s, 1H), 8.16–8.32 (m, 3H), 13.57 (br s, 1H).
13C NMR (DMSO-d6); 145.1, 141.6, 136.7, 133.8, 130.4,
129.7, 129.5, 128.5, 126.8, 119.9, 118.7, 110.3, 104.0,
19.7. MS (m/z, rel. int.); 335 (M++1, 100), 306 (5), 176
(35). Anal. Calcd for C22H14N4: C, 79.02; H, 4.22.
Found: C, 78.67; H, 4.39.
mobenzonitrile. Yield: 78%, mp 186–187 ꢁC. H NMR
(DMSO-d6); d 7.83–7.87 (m, 1H), 7.99–8.09 (m, 6H),
10.09 (s, 1H). 13C NMR (DMSO-d6); d 192.7, 164.5,
161.1, 146.2, 146.1, 142.4, 136.3, 134.4, 130.1, 128.0,
124.1, 115.1, 114.8, 113.9, 99.8, 99.6 (fluorine splitting).
MS (m/z, rel. int.); 225 (M+, 75), 224 (100), 195 (25), 169
(20). Anal. Calcd for C14H8FNO: C, 74.66; H, 3.58.
Found: C, 74.63; H, 3.55.
2.4.15. 2-[40-(N-Hydroxyamidino)-20-methylbiphenyl-4-yl]-
1H-benzimidazole-5-N-hydroxyamidine (4d). The same
proceduredescribedfor4awasusedstartingwith3d. Yield:
93%, mp: 300–302 ꢁC. 1H NMR (DMSO-d6); 2.33 (s, 3H),
5.84 (s, 4H), 7.29 (d, J = 7.8 Hz, 1H), 7.53–7.66 (m, 5H),
7.82 (s, 1H), 7.99 (s, 1H), 8.26 (d, J = 7.8 Hz, 2H), 9.59
(s, 1H), 9.66 (s, 1H), 13.02 (br s, 1H). MS (m/z, rel. int.);
401 (M++1, 100), 163 (25). Anal. Calcd for
C22H20N6O2Æ2.0H2O: C, 60.49; H, 5.50. Found: C, 60.82;
H, 5.54.
2.4.10. 2-(40-Cyano-30-fluorobiphenyl-4-yl)-1H-benzimid-
azole-5-carbonitrile (3c). The same procedure described
for 3a was used starting with 2c. Yield: 84%, mp: 302–
305 ꢁC. 1H NMR (DMSO-d6); d 7.62 (d, J = 8.1 Hz,
1H), 7.78 (d, J = 8.1 Hz, 1H), 7.88 (d, J = 8.1 Hz, 1H),
8.00–8.07 (m, 4H), 8.17 (s, 1H), 8.33 (d, J = 8.1 Hz,
2H), 13.60 (br s, 1H). 13C NMR (DMSO-d6); d 164.5,
161.2, 146.5, 146.4, 138.7, 134.3, 129.8, 127.9, 127.5,
123.5, 119.9, 115.5, 114.5, 114.3, 114.0, 104.1, 99.2,
99.0 (fluorine splitting). EI-MS (m/z, rel. int.); 338
(M+, 100), 222 (5), 195 (5), 169 (10). High resolution
mass calcd for C21H11FN4: 338.09677. Obsd: 338.09778.
2.4.16. 2-(40-Amidino-20-methylbiphenyl-4-yl)-1H-benzimid-
azole-5-amidine acetate salt (5d). The same procedure de-
scribed for 5a was used starting with 4d. Yield: 82%,
1
2.4.11. 2-[30-Fluoro-40-(N-hydroxyamidino)-biphenyl-4-yl]-
1H-benzimidazole-5-N-hydroxyamidine (4c). The same
procedure described for 4a was used starting with 3c.
mp: 193–195 ꢁC. H NMR (D2O/DMSO-d6); d 1.82 (s,
3· CH3), 2.40 (s, 3H), 7.60–8.00 (m, 7H), 8.20 (s, 1H),
8.25–8.38 (m, 2H). MS (m/z, rel. int.); 369 (M++1, 10),
353 (100), 336 (30). Anal. Calcd for C22H20N6Æ3.0AcO-
HÆ0.25H2O: C, 60.80; H, 5.92; N, 15.19. Found: C,
60.57; H, 5.73; N, 15.33.
1
Yield: 96%, mp: 281–283 ꢁC. H NMR (DMSO-d6); d
5.86 (s, 4H), 7.60–7.74 (m, 6H), 7.98 (d, J = 8.4 Hz,
2H), 8.32 (d, J = 8.4 Hz, 2H), 9.60 (s, 1H), 9.74 (s, 1H),