4ꢀ-Aryl Aminimide Analogues of Clozapine
681
181–183◦C. (Found: C 60.5, H 4.8, N 13.6. C26H23ClF3N5O
requires C 60.8, H 4.5, N 13.6%.) νmax (KBr)/cm−1 3216, 1604,
1566. λmax/nm (ε/M−1 cm−1) 227 (27 500), 257 (11 700), 296
(5500). δH (CDCl3) 3.27 (2H, br m, H2ꢀa, H6ꢀa), 3.58 (3H, s,
CH3N+), 3.87 (4H, br m, H3ꢀ, H5ꢀ), 4.42 (2H, m, H2ꢀb, H6ꢀb),
4.97 (1H, s, H5), 6.62 (1H, d, J 8.5, H6), 6.82 (1H, d, J 8, H4),
6.87 (1H, dd, J 8.5, 2.5, H7), 7.02 (1H, app t, J 7.5, H2), 7.07
(1H, d, J 2.5, H9), 7.24 (1H, dd, J 7.5, 1, H1), 7.33 (1H, app td,
J 7.5, 1, H3), 7.44 (1H, app t, J 7.5, H5ꢀꢀ), 7.60 (1H, d, J 7.5,
H4ꢀꢀ), 8.18 (1H, d, J 7.5, H6ꢀꢀ), 8.29 (1H, br s, H2ꢀꢀ). δC (CDCl3)
42.6 (C3ꢀ, C5ꢀ), 53.3 (CH3N+), 62.0 (C2ꢀ, C6ꢀ), 120.48 (C4),
120.54 (C6), 122.7 (C11a), 123.6 (C2), 124.2 (C7), 124.5 (q, J
278, CF3), 124.6 (C2ꢀꢀ), 126.3 (C4ꢀꢀ), 127.1 (C9), 128.3 (C5ꢀꢀ),
129.4 (C8), 130.1 (C1), 130.5 (q, J 32, C3ꢀꢀ), 131.0 (C6ꢀꢀ), 132.8
(C3), 139.6 (C1ꢀꢀ), 140.7 (C5a), 141.2 (C9a), 153.3 (C4a), 162.3
(C11), 168.6 (CO). m/z (+ESI, 30V) 516 (35%, M[37Cl]H+),
514 (100%, MH+), 501 (28), 499 (70).
1-[4-(8-Chloro-5H-dibenzo[b,e][1,4]diazepin-11-yl)-
1-methylhexahydropyrazin-1-ium]-
1-(3-methoxy)benzimide 2r
Purifiedbyflashchromatography(9/1, chloroform/propan-2-
ol), yellow rosettes (CHCl3/hexane), yield 61%, mp 208–209◦C.
(Found: C 65.6, H 5.6, N 14.5, MH+ 476.1854. C26H26ClN5O2
requires C 65.6, H 5.5, N 14.7%, MH+ 476.1848.) νmax
(KBr)/cm−1 3296, 1602, 1564. λmax/nm (ε/M−1 cm−1) 230
(24 500), 262 (17 000), 299 (9500). δH (CDCl3, 500 MHz) 3.28
(2H, br m, H2ꢀa, H6ꢀa), 3.61 (3H, s, CH3N+), 3.84 (3H, s,
OCH3), 3.91 (4H, m, H3ꢀ, H5ꢀ), 4.48 (2H, m, H2ꢀb, H6ꢀb), 4.99
(1H, s, H5), 6.63 (1H, d, J 8.5, H6), 6.82 (1H, d, J 8, H4), 6.87
(1H, dd, J 8.5, 2.5, H7), 6.93 (1H, br dd, J 8, 2, H4ꢀꢀ), 7.01 (1H,
app t, J 7.5, H2), 7.07 (1H, d, J 2.5, H9), 7.23 (1H, d, J 7.5, H1),
7.34 (1H, br app t, J 8, H3), 7.43 (1H, app t, J 8, H5ꢀꢀ), 7.60 (1H,
br s, H2ꢀꢀ), 7.68 (1H, br d, J 7.5, H6ꢀꢀ). δC (CDCl3) 42.8 (C3ꢀ,
C5ꢀ), 53.6 (CH3N+), 55.7 (OCH3), 62.4 (C2ꢀ, C6ꢀ), 112.9 (C2ꢀꢀ),
116.5 (C4ꢀꢀ), 120.2 (C6ꢀꢀ), 120.6 (C4, C6), 123.1 (C11a), 123.7
(C2), 124.3 (C7), 127.3 (C9), 128.9 (C5ꢀꢀ), 129.4 (C8), 130.3
(C1), 132.9 (C3), 139.9 (C1ꢀꢀ), 140.7 (C5a), 141.6 (C9a), 153.4
(C4a), 159.7 (C3ꢀꢀ), 162.2 (C11), 170.6 (CO). m/z (+ESI, 30V)
498 (20%, MNa+), 478 (38%, M[37Cl]H+), 476 (100%, MH+).
1-[4-(8-Chloro-5H-dibenzo[b,e][1,4]diazepin-11-yl)-
1-methylhexahydropyrazin-1-ium]-
1-(4-trifluoromethyl)benzimide 2p
Purifiedbyflashchromatography(85/15, chloroform/propan-
2-ol), yellow/orange rosettes (CHCl3/hexane), yield 45%, mp
159–161◦C. (Found: C 58.5, H 4.6, N 13.1, MH+ 514.1613.
C26H23ClF3N5O·H2O requires C 58.7, H 4.7, N 13.2%,
MH+ 514.1616.) νmax (KBr)/cm−1 3288, 1604, 1552. λmax/nm
(ε/M−1 cm−1) 228 (28 800), 260 (20 400), 299 (9100). δH
(CDCl3) 3.27 (2H, br m, H2ꢀa, H6ꢀa), 3.57 (3H, s, CH3N+),
3.87 (4H, br m, H3ꢀ, H5ꢀ), 4.41 (2H, m, H2ꢀb, H6ꢀb), 5.00 (1H,
s, H5), 6.63 (1H, d, J 8.5, H6), 6.82 (1H, d, J 8, H4), 6.87 (1H,
dd, J 8.5, 2.5, H7), 7.01 (1H, app t, J 7.5, H2), 7.07 (1H, d, J 2.5,
H9), 7.23 (1H, d, J 8, H1), 7.31 (1H, app td, J 7.5, 1.5, H3), 7.58
(2H, d, J 8, H3ꢀꢀ, H5ꢀꢀ), 8.11 (2H, d, J 8, H2ꢀꢀ, H6ꢀꢀ). δC (CDCl3)
42.7 (C3ꢀ, C5ꢀ), 53.4 (CH3N+), 62.1 (C2ꢀ, C6ꢀ), 120.5 (C4, C6),
122.9 (C11a), 123.6 (C2), 124.3 (C7), 124.6 (q, J 274, CF3),
124.8 (C3ꢀꢀ, C5ꢀꢀ), 127.2 (C9), 128.1 (C2ꢀꢀ, C6ꢀꢀ), 129.5 (C8),
130.1 (C1), 131.4 (q, J 32, C4ꢀꢀ), 132.8 (C3), 140.6 (C5a), 141.3
(C9a), 142.5 (C1ꢀꢀ), 153.3 (C4a), 162.3 (C11), 168.9 (CO). m/z
(+ESI, 30V) 516 (35%, M[37Cl]H+), 514 (100%, MH+).
1-[4-(8-Chloro-5H-dibenzo[b,e][1,4]diazepin-11-yl)-
1-methylhexahydropyrazin-1-ium]-
1-(4-methoxy)benzimide 2s
Purifiedbyflashchromatography(4/1, chloroform/propan-2-
ol), yellow needles (CHCl3/hexane), yield 45%, mp 159–160◦C.
(Found: C 64.0, H 5.4, N 14.3, MH+ 476.1848. C26H26ClN5O2
requires C 64.4, H 5.6, N 14.4%, MH+ 476.1848.) νmax
(KBr)/cm−1 3224, 1606, 1566. λmax/nm (ε/M−1 cm−1) 231
(20 400), 258 (19 100), 297 (7100). δH (CDCl3) 3.23 (2H, br
m, H2ꢀa, H6ꢀa), 3.58 (3H, s, CH3N+), 3.90 (3H, s, OCH3), 3.90
(4H, br m, H3ꢀ, H5ꢀ), 4.43 (2H, m, H2ꢀb, H6ꢀb), 4.92 (1H, s, H5),
6.62 (1H, d, J 8.5, H6), 6.82 (1H, br d, J 8, H4), 6.84 (2H, d, J 9,
H3ꢀꢀ, H5ꢀꢀ), 6.87 (1H, dd, J 8.5, 2.5, H7), 7.01 (1H, app td, J 8, 1,
H2), 7.07 (1H, d, J 2.5, H9), 7.23 (1H, dd, J 8, 1.5, H1), 7.31 (1H,
app td, J 8, 1.5, H3), 7.96 (2H, d, J 9, H2ꢀꢀ, H6ꢀꢀ). δC (CDCl3)
42.3 (C3ꢀ, C5ꢀ), 53.2 (CH3N+), 55.2 (OCH3), 61.7 (C2ꢀ, C6ꢀ),
112.9 (C3ꢀꢀ, C5ꢀꢀ), 120.2 (C4, C6), 122.5 (C11a), 123.3 (C2),
123.9 (C7), 126.8 (C9), 128.9 (C2ꢀꢀ, C6ꢀꢀ), 129.1 (C8), 129.9
(C1), 131.1 (C1ꢀꢀ), 132.5 (C3), 140.3 (C5a), 141.0 (C9a), 152.9
(C4a), 160.7 (C4ꢀꢀ), 162.0 (C11), 169.8 (CO). m/z (+ESI, 30V)
478 (35%, M[37Cl]H+), 476 (100%, MH+).
1-[4-(8-Chloro-5H-dibenzo[b,e][1,4]diazepin-11-yl)-
1-methylhexahydropyrazin-1-ium]-
1-(2-methoxy)benzimide 2q
Purified by flash chromatography (4/1, chloroform/propan-
2-ol), yellow needles (CHCl3/hexane), yield 48%, mp 163.5–
165◦C. (Found: C 65.8, H 5.5, N 14.5. C26H26ClN5O2 requires
C 65.6, H 5.6, N 14.7%.) νmax (KBr)/cm−1 3262, 1614, 1587,
1563. λmax/nm (ε/M−1 cm−1) 226 (24 500), 260 (13 500), 299
(7400). δH (CDCl3) 3.16 (2H, br m, H2ꢀa, H6ꢀa), 3.59 (3H, s,
CH3N+), 3.85 (3H, s, OCH3), 4.03 (4H, m, H3ꢀ, H5ꢀ), 4.46 (2H,
m, H2ꢀb, H6ꢀb), 4.95 (1H, s, H5), 6.63 (1H, d, J 8.5, H6), 6.82
(1H, d, J 8, H4), 6.85 (1H, dd, J 8.5, 2.5, H7), 6.86 (1H, d, J 8,
H3ꢀꢀ), 6.89 (1H, app t, J 8, H5ꢀꢀ), 7.03 (1H, app t, J 7.5, H2), 7.07
(1H, d, J 2.5, H9), 7.23 (1H, app td, J 8, 1.5, H4ꢀꢀ), 7.25 (1H, br d,
J 8, H1), 7.32 (1H, app td, J 8, 1.5, H3), 7.43 (1H, dd, J 7.5, 1.5,
H6ꢀꢀ). δC (CDCl3) 42.8 (C3ꢀ, C5ꢀ), 53.5 (CH3N+), 56.1 (OCH3),
61.9 (C2ꢀ, C6ꢀ), 111.8 (C3ꢀꢀ), 120.6 (C4, C6, C1ꢀꢀ, C5ꢀꢀ), 123.1
(C11a), 123.7 (C2), 124.2 (C7), 127.3 (C9), 129.3 (C6ꢀꢀ), 129.5
(C8, C4ꢀꢀ), 130.3 (C1), 132.8 (C3), 140.7 (C5a), 141.5 (C9a),
153.4 (C4a), 157.2 (C2ꢀꢀ), 162.3 (C11), 170 (CO). m/z (+ESI,
30V) 478 (35%, M[37Cl]H+), 476 (100%, MH+).
1-[4-(8-Chloro-5H-dibenzo[b,e][1,4]diazepin-11-yl)-
1-methylhexahydropyrazin-1-ium]-
1-(2-acetyl)benzimide 2t
Purifiedbyflashchromatography(85/15, chloroform/propan-
2-ol), pale yellow needles (CHCl3/hexane), yield 43%, mp
221–222◦C. (Found: C 66.4, H 5.3, N 14.2. C27H26ClN5O2
requires C 66.5, H 5.4, N 14.4%.) νmax (KBr)/cm−1 3364, 1680,
1604, 1552. λmax/nm (ε/M−1 cm−1) 229 (30 200), 261 (17 800),
299 (9100). δH (CDCl3, 500 MHz) 2.56 (3H, s, COCH3), 3.25
(2H, br m, H2ꢀa, H6ꢀa), 3.57 (3H, s, CH3N+), 3.88 (4H, m, H3ꢀ,
H5ꢀ), 4.36 (2H, m, H2ꢀb, H6ꢀb), 4.94 (1H, s, H5), 6.65 (1H, d,
J 8.5, H6), 6.84 (1H, br d, J 7.5, H4), 6.88 (1H, dd, J 8.5, 2.5,
H7), 7.04 (1H, app td, J 7.5, 1, H2), 7.07 (1H, d, J 2.5, H9), 7.26
(1H, dd, J 7.5, 1, H1), 7.33 (1H, app td, J 7.5, 1, H3), 7.35–7.39
(2H, m, H4ꢀꢀ, H6ꢀꢀ), 7.41 (1H, app td, J 7, 2, H5ꢀꢀ), 7.80 (1H,