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R. L. Riggs et al. / Tetrahedron 61 (2005) 11230–11243
C, 56.7; H, 4.3; N, 4.6%). ymax 3120 (NH), 1710 (ester
C]O), 1630 (lactam C]O). dH (DMSO-d6) 0.84 (3H, t,
JZ7.2 Hz, CH2CH3), 2.10 (3H, s, AcOH), 3.31 (2H, q, JZ
7.2 Hz, OCH2) 3.67 (3H, s, OMe), 6.76 and 6.84 (each 2H,
AA0BB0, p-MeOC6H4), 7.44 (4H, s, Ar), 7.22 and 7.57 (each
2H, AA0BB0, Ar), 10.93 (1H, s, NH) and 11.92 (1H, s, NH).
dC 14.0 (CH3), 55.7 (OCH3), 60.2 (OCH2), 102.6 (quat),
107.3 (quat), 114.5 (2!CH), 125.9 (2!CH), 127.7 (2!
CH), 128.8 (4!CH), 129.8 (2!CH), 131.1 (2!quat),
132.1 (2!quat), 132.4 (quat), 133.4 (quat), 157.1 (quat),
157.4 (quat), 165.6 and 168.8 (2!CO).
5.1.17. 3-p-Bromophenyl-6-p-chlorophenyl-2-p-methoxy-
phenyl-5-methyl-DPP 16d. A mixture of DPP 13d
(100 mg, 0.2 mmol), methyl p-toluenesulfonate (75.1 mg,
0.404 mmol), potassium carbonate (70 mg, 0.51 mmol) and
DMF (10 cm3) was heated to 100 8C for 3 h, cooled to room
temperature, added to water and extracted with DCM.
Evaporation of the solvents followed by washing with water
then methanol gave the pyrrolopyrrole 16d as a red-orange
solid (81 mg, 79%), mp 262–264 8C. (Found: C, 59.5; H,
3.3; N, 5.3. C25H16BrClN2O3 requires C, 59.1; H, 3.3; N,
5.5%). ymax 1670 (C]O) and 1610; dH 3.31 (3H, s, NCH3),
3.75 (3H, s, OCH3), 6.83 and 7.01 (each 2H, AA0BB0,
NC6H4OMe), 7.37 and 7.47 (each 2H, AA0BB0, p-Ar), 7.41
and 7.80 (each 2H, AA0BB0, p-Ar). dC 30.1 (NCH3) 55.9
(OCH3) 114.9 (2!C, Ar-H), 126.2 (2!C, quat), 126.4
(quat), 126.8 (quat), 128.5 (2!C, quat), 129.3 (2!C, Ar),
129.6 (2!C, Ar), 130.9 (2!C, Ar) 131.4 (2!C, Ar), 132.1
(2!C, Ar), 138.1 (quat), 146.6 (quat), 148.1 (quat), 159.6
(2!C, quat) and 162.9 (quat). m/z (EI): 520/522/524 (27/
100/78%, MC) and 288/290 (60/61%).
5.1.14. 5-Methyl-2,3,6-triphenyl-DPP 16a. The triphenyl-
DPP 13a (500 mg, 1.37 mmol) was stirred with methyl
p-toluenesulfonate (383 mg, 2.06 mmol), potassium car-
bonate (380 mg, 2.75 mmol) and DMF (40 cm3) overnight.
Water was added, and the organic component extracted with
DCM. The solvent was evaporated and washing with water
then methanol gave the DPP 16a as an orange solid
(290 mg, 56%), mp 267–269 8C. (Found: C, 79.4; H, 5.0; N,
7.3. C25H18N2O2 requires C, 79.35; H, 4.8; N, 7.4%). dH
3.42 (3H, s, NCH3), 7.15–7.20 (2H, m, Ar) 7.28–7.41 (6H,
m, Ar), 7.51–7.56 (3H, m, Ar), 7.62–7.68 (2H, m, Ar), 7.91–
7.95 (2H, m, Ar). m/z (ESI Cve): 402 [28%, (MCNaC
1)C], 401 [100%, (MCNa)C] and 379 [14%, (MC1)C].
5.1.18. 5-Benzyl-2,3,6-triphenyl-DPP 17a. The triphenyl-
DPP 13a (500 mg, 1.37 mmol) was stirred with benzyl
bromide (352 mg, 245 ml, 2.06 mmol), potassium carbonate
(380 mg, 2.75 mmol) and DMF (40 cm3) overnight. Water
was added, and the organic component extracted with DCM.
The solvent was evaporated and washing with water and
then methanol gave the pyrrolopyrrole 17a as an orange
solid (548 mg, 93%), mp 262–264 8C. (Found: C, 81.9; H,
4.8; N, 6.2. C31H22N2O2 requires C, 81.9; H, 5.0; N, 6.2%).
ymax 1680 (CO), 1590; dH 5.05 (2H, s, PhCH2N), 7.16–7.24
(4H, m, Ar-H), 7.27–7.50 (12H, m, Ar-H), 7.66–7.70 (2H,
m, Ar-H) and 7.74–7.79 (2H, m, Ar-H). dC 46.1 (CH2),
127.1 (2!CH), 127.8 (CH), 128.0 (2!quat), 128.1 (quat),
128.2 (2!CH), 128.3 (CH), 128.7 (2!CH), 129.2 (4!
CH), 129.4 (2!CH), 129.5 (2!CH), 130.2 (2!CH), 131.6
(CH), 131.9 (CH), 136.1 (quat), 137.8 (quat), 147.9 (quat),
149.7 (quat), 162.3 and 163.3 (2!CO).
5.1.15. 2-(p-Methoxyphenyl)-5-methyl-3,6-diphenyl-
DPP 16b. The triaryl-DPP 13b (1.23 g, 3.12 mmol), methyl
p-toluenesulfonate (1.13 g, 6.08 mmol) and potassium
carbonate (0.841 g, 6.08 mmol) were heated to 120 8C in
DMF (40 cm3) for 2 h. The mixture was cooled to room
temperature, water was added and the organic component
extracted with DCM. Evaporation of the solvent and
recrystallisation from toluene gave the methylated com-
pound 16b (0.99 g, 80%), mp 252–254 8C. (Found: C,
76.15; H, 4.9; N, 6.9. C26H20N2O3 requires C, 76.45; H, 4.9;
N, 6.9%). dH 3.53 (3H, s, NCH3), 3.93 (3H, s, OCH3), 7.00
and 7.21 (each 2H, AA0BB0, p-MeOC6H4), 7.41–7.50 (3H, m,
Ar-H), 7.61–7.67 (3H, m, Ar-H), 7.77–7.82 (2H, m, Ar-H),
and 8.02–8.07 (2H, m, Ar-H). dC 30.0 (NCH3), 55.9
(OCH3), 114.7 (2!CH), 128.1 (2!C quat), 128.2 (2!
quat), 128.7 (2!CH), 129.0 (2!quat), 129.2 (2!CH),
129.4 (2!CH), 129.6 (2!CH), 130.1 (2!CH), 131.4
(CH), 131.8 (CH), 147.6 (quat), 149.2 (quat), 159.3 and
162.6 (2!C]O)‡ and 163.2 (quat). m/z (ESI Cve): 447
[10%, MCKCH)C], 446 (27%, MCK), 431 [100%, (MC
Na)C] and 409 [35%, (MC1)C].
5.1.19. 5-Benzyl-2-p-methoxyphenyl-3,6-diphenyl-DPP
17b. The triaryl-DPP 13b (100 mg, 0.254 mmol), benzyl
bromide (118 mg, 83 ml, 0.66 mmol) and potassium car-
bonate (100 mg, 0.71 mmol) were heated to 120 8C in DMF
(10 cm3) for 2 h. The mixture was cooled to room
temperature, water was added and the organic component
extracted with DCM. Evaporation of the solvent from the
dried extract gave the benzylated compound 17b (108 mg,
88%), mp 263–264 8C (from AcOH). [Found: C, 76.2; H,
4.8; N, 5.6. C32H24N2O3 (3:2 ratio with AcOH) requires C,
76.3; H, 5.1; N, 5.3%]. dH 2.10 (3H, s, AcOH), 3.74 (3H, s,
OCH3), 4.97 (2H, s, NCH2), 6.82 and 7.04 (each 2H,
AA0BB0, p-MeOC6H4), 7.11–7.41 (6H, m, Ar-H), and 7.61–
7.71 (4H, m, Ar-H). dC 46.1 (CH2), 55.9 (OCH3), 114.8
(CH), 127.0 (CH), 127.8 (CH), 128.0 (quat), 128.1 (2!
quat), 128.7 (CH), 129.2 (2!CH), 129.4 (CH), 129.5 (CH),
130.2 (CH), 131.5 (CH), 131.8 (CH), 137.8 (quat), 148.0
(quat), 149.4 (quat), 159.4 (2!C]O),‡ 162.6 (quat) and
163.3 (quat). m/z (ESI Cve): 508 [34%, (MCNaC1)C],
507 [100, (MCNa)C] and 485 [8, (MC1)C].
5.1.16. 5-Methyl-3,6-diphenyl-2-p-trifluoromethylphe-
nyl-DPP 16c. A mixture of the DPP 13c (200 mg,
0.463 mmol), methyl p-toluenesulfonate (129 mg,
0.695 mmol), potassium carbonate (128 mg, 0.93 mmol)
and DMF (10 cm3) was stirred at room temperature
overnight, added to water and extracted with DCM.
Evaporation of the solvents followed by washing with
water then methanol gave the pyrrolopyrrole 16c as an
orange solid (184 mg, 89%), mp 237.5–238.5 8C. (Found:
C, 69.9; H, 3.7; N, 6.1. C26H17F3N2O2 requires C, 69.95; H,
3.8; N, 6.3%). dH 7.94–7.87 (2H, m, Ph-H), 7.67–7.51 (7H, m,
Ph-H), 7.45–7.27 (5H, m, Ar-H) and 3.42 (3H, s, N–CH3).
5.1.20. 5-Benzyl-3,6-diphenyl-2-(p-trifluoromethylphe-
nyl)-DPP 17c. A mixture of the triaryl-DPP 13c (200 mg,
0.46 mmol), benzyl bromide (119 mg, 83 ml, 0.695 mmol),
‡ Provisional assignment.