C. Kieffer et al. / Tetrahedron 69 (2013) 2987e2995
2993
(CH), 128.7 (2CH), 129.6 (CH), 129.9 (CH), 130.6 (CH), 132.7 (2CH),
135.2 (CH), 149.5 (C), 154.1 (C), 161.1 (C). LC/MS (ESIþ) tR 5.10 min,
m/z [MþH]þ 347.19/349.10/351.11. HRMS (ESIþ) m/z 346.9903
[MþH]þ, calcd for C17H9Cl3N2þH: 346.9904.
8.17e8.21 (m, 1H). 13C NMR (CDCl3, 50 MHz):
d
22.2 (CH3), 70.6
(CH), 121.4 (C), 125.6 (CH), 128.1 (CH), 132.3 (CH), 147.6 (C), 151.1 (C),
160.1 (C), 163.5 (C). LC/MS (ESIþ) tR 3.89 min, m/z [MþH]þ261.13/
263.24/265.05. HRMS (ESIþ) m/z 282.9570 [MþNa]þ, calcd for
C10H7Cl3N2þNa: 282.9567.
4.4.2. 1,4-Diphenylbuta-1,3-diyne (10). C16H10. MW: 202.25 g/mol.
yellow solid (35%). Mp 85 ꢀC (lit. 85e87 ꢀC).32 1H NMR (CDCl3,
4.4.10. 1,1,2,2-Tetrachloro-1,2-bis(4-chloro-7-methylquinazolin-2-yl)
200 MHz):
50 MHz):
d
7.31e7.37 (m, 6H), 7.52e7.56 (m, 4H). 13C NMR (CDCl3,
ethane (22). MW: 521.05 g/mol. Beige solid (25%). Mp 289 ꢀC. 1H
d
73.9 (2C), 81.5 (2C), 121.8 (2C), 128.4 (4CH), 129.2 (2CH),
NMR (CDCl3, 200 MHz):
d
2.58 (s, 6H), 7.59e7.63 (m, 2H), 7.74 (s,
22.1 (2CH3),
132.5 (4CH).
2H), 8.11e8.31 (m, 2H). 13C NMR (CDCl3, 50 MHz):
d
95.3 (2C), 120.8 (2C), 125.3 (2CH), 128.4 (2CH), 132.4 (2CH), 146.8
(2C), 150.5 (2C), 158.4 (2C), 161.1 (2C). LC/MS (ESIþ) tR 5.56 min, m/z
[MþH]þ518.56/520.53/522.49/524.82. Anal. Calcd for C20H12Cl6N4:
C, 46.10; H, 2.32; N, 10.75%. Found: C, 46.51; H, 2.30; N, 10.69%.
4.4.3. 4-Chloro-2-dichloromethylquinazoline (11). C9H5Cl3N2. MW:
247.51 g/mol. White solid (6%). Mp 140 ꢀC (lit. 135e137 ꢀC).33 1H
NMR (CDCl3, 200 MHz):
d
6.86 (s, 1H), 7.77e7.85 (m, 1H), 7.99e8.14
70.5
(m, 2H), 8.30e8.35 (m, 1H). 13C NMR (CDCl3, 50 MHz):
d
(CHCl2), 123.3 (CH), 126.0 (CH), 129.2 (CH), 130.1 (CH), 135.7 (CH),
150.7 (C), 160.1 (C), 164.1 (C).
4.4.11. 4-(Cyclopentylethynyl)-2-trichloromethylquinazoline
(23). MW: 339.65 g/mol. Pale brown solid (11%). Mp 117 ꢀC. 1H
NMR (CDCl3, 200 MHz):
7.73e7.80 (m, 1H), 7.94e8.02 (m, 1H), 8.12e8.17 (m, 1H), 8.35e8.38
(m, 1H). 13C NMR (CDCl3, 50 MHz):
25.3 (2CH2), 31.1 (CH), 33.5
d 1.66e2.22 (m, 8H), 2.99e3.14 (m, 1H),
4.4.4. 1,1,2,2-Tetrachloro-1,2-bis(4-chloroquinazolin-2-yl)ethane
(12). MW: 493.00 g/mol. Beige solid (48%). Mp 238 ꢀC. 1H NMR
d
(CDCl3, 200 MHz):
d
7.75e7.83 (m, 2H), 7.93e7.98 (m, 4H),
95.2 (2C), 122.6
(2CH2), 76.7 (C), 97.0 (C), 108.1 (CH), 124.3 (CH), 126.7 (CH), 129.4
(CH), 129.7 (CH), 135.0 (CH), 149.3 (C), 154.8 (C), 161.0 (C). LC/MS
(ESIþ) tR 5.33 min, m/z [MþH]þ 339.07/341.06/343.10. HRMS (ESIþ)
m/z 339.0220 [MþH]þ, calcd for C16H13Cl3N2þH: 339.0217.
8.24e8.29 (m, 2H). 13C NMR (CDCl3, 50 MHz):
d
(2CH), 125.7 (2CH), 129.4 (2CH), 130.2 (2CH), 135.3 (2CH), 150.3
(2C), 158.4 (2C), 161.6 (2C). LC/MS (ESIþ) tR 5.22 min, m/z [MþH]þ
490.66/492.70/494.72/496.70/498.46. HRMS (ESIþ) m/z 492.8920
[MþH]þ, calcd for C18H8Cl6N4þH: 492.8924. Typical fragment
M¼163 Da, [C8H4ClN2]þ, was identified in ESIþ at ꢁ30 V.
4.4.12. 4-(4-Tolylethynyl)-2-trichloromethylquinazoline (24). MW:
361.65 g/mol. Yellow solid (21%). Mp 177 ꢀC (isopropanol). 1H NMR
(CDCl3, 200 MHz):
J¼8.1 Hz, 2H), 7.78e7.86 (m, 1H), 7.97e8.03 (m, 1H), 8.18e8.22 (m,
1H), 8.46e8.51 (m, 1H). 13C NMR (CDCl3, 50 MHz):
21.8 (CH3), 84.7
d
2.44 (s, 3H), 7.28 (d, J¼8.1 Hz, 2H), 7.68 (d,
4.4.5. 4-(Cyclopropylethynyl)-2-trichloromethylquinazoline
(13). MW: 311.59 g/mol. White solid (19%). Mp 180 ꢀC. 1H NMR
d
(CDCl3, 200 MHz):
(m, 1H), 7.94e8.02 (m, 1H), 8.13e8.17 (m, 1H), 8.28e8.32 (m, 1H).
13C NMR (CDCl3, 50 MHz):
0.8 (CH), 9.8 (2CH2), 72.7 (C), 97.5 (C),
107.4 (C), 124.3 (C), 126.7 (CH), 129.5 (CH), 129.6 (CH), 135.0 (CH),
149.3 (C), 154.6 (C), 161.0 (C). LC/MS (ESIþ) tR 4.58 min, m/z [MþH]þ
311.05/313.07/314.95. HRMS (ESIþ) m/z 332.9720 [MþNa]þ, calcd
for C14H9Cl3N2þNa: 332.9724.
d
1.10e1.13 (m, 4H), 1.62e1.74 (m, 1H), 7.72e7.79
(C), 97.0 (C), 101.1 (C), 117.8 (C), 124.2 (C), 126.6 (C), 129.4 (2CH),
129.5 (CH), 129.8 (CH), 132.7 (2CH), 135.2 (CH), 141.2 (C), 149.5 (C),
154.3 (C), 161.1 (C). LC/MS (ESIþ) tR 5.48 min, m/z [MþH]þ 361.13/
363.16/365.19. Anal. Calcd for C18H11Cl3N2: C, 59.78; H, 3.07; N,
7.75%. Found: C, 59.71; H, 3.01; N, 7.69%.
d
4.4.13. 4-(3-Tolylethynyl)-2-trichloromethylquinazoline (25). MW:
361.65 g/mol. Pale yellow solid (20%). Mp 175 ꢀC (isopropanol). 1H
4.4.6. 1,4-Dicyclopropylbuta-1,3-diyne (14). C10H10. MW: 130.19 g/
NMR (CDCl3, 200 MHz):
J¼6.5 Hz, 2H), 7.77e7.82 (m, 1H), 7.99e8.06 (m, 1H), 8.18e8.23 (m,
1H), 8.46e8.51 (m, 1H). 13C NMR (CDCl3, 50 MHz):
21.2 (CH3), 84.7
d
2.42 (s, 3H), 7.34 (d, J¼6.5 Hz, 2H), 7.60 (d,
mol. Colorless oil (24%).34 1H NMR (CDCl3, 200 MHz):
d
0.71e0.88
(m, 8H), 1.21e1.32 (m, 2H). 13C NMR (CDCl3, 50 MHz):
d
0.01 (2CH),
d
8.7 (2CH2), 60.8 (2C), 80.0 (2C).
(C), 97.0 (C), 100.8 (C), 120.6 (C), 124.2 (C), 126.6 (CH), 128.6 (CH),
129.6 (CH), 129.9 (2CH), 131.5 (CH), 133.2 (CH), 135.2 (CH), 138.5 (C),
149.5 (C), 154.3 (C), 161.1 (C). LC/MS (ESIþ) tR 5.44 min, m/z [MþH]þ
361.15/363.16/365.15. Anal. Calcd for C18H11Cl3N2: C, 59.78; H, 3.07;
N, 7.75%. Found: C, 59.80; H, 2.98; N, 7.70%.
4.4.7. 1,1,2,2-Tetrachloro-1,2-bis[4-(cyclopropylethynyl)-quinazolin-
2-yl]ethane (15). MW: 552.28 g/mol. Yellow solid (4%). Mp 185 ꢀC.
1H NMR (CDCl3, 200 MHz):
d
0.91e1.03 (m, 8H), 1.46e1.57 (m, 2H),
7.63e7.71 (m, 2H), 7.80e7.85 (m, 4H), 8.18e8.22 (m, 2H). 13C NMR
(CDCl3, 50 MHz): 0.6 (2CH), 9.5 (4CH2), 72.5 (2C), 96.2 (2C), 105.6
d
4.4.14. 4-(2-Tolylethynyl)-2-trichloromethylquinazoline (26). MW:
(2C), 123.9 (2C), 126.2 (2CH), 129.0 (2CH), 129.2 (2CH), 134.1 (2CH),
149.2 (2C), 152.2 (2C), 159.3 (2C). LC/MS (ESIþ) tR 5.01 min, m/z
[MþH]þ 551.90/553.90/555.91/557.51/558.93. HRMS (ESIþ) m/z
551.0355 [MþH]þ, calcd for C28H18Cl4N4þH: 551.0358.
361.65 g/mol. Yellow solid (41%). Mp 179 ꢀC. 1H NMR (CDCl3,
200 MHz):
7.98e8.07 (m, 1H), 8.18e8.23 (m, 1H), 8.47e8.51 (m, 1H). 13C NMR
(CDCl3, 50 MHz): 21.1 (CH3), 88.7 (C), 97.0 (C), 99.4 (C), 120.7 (C),
d 2.68 (s, 3H), 7.31e7.44 (m, 3H), 7.73e7.86 (m, 2H),
d
124.2 (C),126.0 (CH),126.5 (CH),129.6 (CH),129.9 (2CH),130.6 (CH),
133.3 (CH), 135.1 (CH), 141.5 (C), 149.6 (C), 154.3 (C), 161.2 (C). LC/MS
(ESIþESIþ) tR 5.70 min, m/z [MþH]þ 361.13/363.15/365.27. HRMS
(ESIþ) m/z 361.0059 [MþH]þ, calcd for C18H11Cl3N2þH: 361.0060.
4.4.8. 7-Methyl-4-(phenylethynyl)-2-trichloromethyl-quinazoline
(20). MW: 361.65 g/mol. Beige solid (15%). Mp 174 ꢀC. 1H NMR
(CDCl3, 200 MHz):
1H), 7.75e7.80 (m, 2H), 7.99 (s, 1H), 8.33e8.37 (m, 1H). 13C NMR
(CDCl3, 50 MHz): 22.3 (CH3), 29.7 (C), 85.0 (C), 99.8 (C), 120.9 (C),
d 2.65 (s, 3H), 7.43e7.51 (m, 3H), 7.61e7.66 (m,
d
4.4.15. 2-Trichloromethyl-4-[2(2,4,5-trimethylphenyl)-ethynyl]-qui-
122.5 (C), 126.2 (CH), 128.5 (CH), 128.7 (2CH), 130.5 (CH), 132.1 (CH),
132.7 (2CH), 146.8 (C), 149.8 (C), 153.5 (C), 161.2 (C). LC/MS (ESIþ) tR
5.37 min, m/z [MþH]þ561.07/363.02/365.06. HRMS (ESIþ) m/z
382.9877 [MþNa]þ, calcd for C18H11Cl3N2þNa: 382.9880.
nazoline (27). MW: 389.71 g/mol. Pale yellow solid (70%). Mp
234 ꢀC. 1H NMR (CDCl3, 200 MHz):
d 2.27 (s, 3H), 2.30 (s, 3H), 2.61
(s, 3H), 7.09 (s, 1H), 7.53 (s, 1H), 7.76e7.85 (m, 1H), 7.97e8.05 (m,
1H), 8.17e8.21 (m, 1H), 8.47e8.51 (m, 1H). 13C NMR (CDCl3,
50 MHz):
d 19.0 (CH3), 20.0 (CH3), 20.5 (CH3), 88.3 (C), 97.0 (C),
4.4.9. 4-Chloro-2-dichloromethyl-7-methylquinazoline (21). MW:
100.4 (C), 117.8 (C), 124.2 (C), 126.6 (CH), 129.5 (CH), 129.8 (CH),
131.3 (CH), 134.2 (CH), 134.4 (C), 135.0 (CH), 139.0 (C), 140.0 (C),
149.5 (C), 154.5 (C), 161.2 (C). LC/MS (ESIþ) tR 5.70 min, m/z [MþH]þ
261.53 g/mol. Beige solid (14%). Mp 182 ꢀC. 1H NMR (CDCl3,
200 MHz): d 2.63 (s, 3H), 6.83 (s, 1H), 7.60e7.64 (m, 1H), 7.88 (s, 1H),