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3
(
1
(
d, 3JH,H = 8.6 Hz, 1 H, 2-H), 7.02 (dd, J = 8.6, 4JH,H = 1.1 Hz, 2 H,
730 (w), 721 (s), 709 (m), 651 (w), 622 (w), 558 (m), 541 (m), 485
H,H
2-H, 16-H) ppm. 13C NMR (75 MHz, CD Cl ): δ = 184.0 (C-10), 161.2 (m), 440 (m), 412 (w) cm . MS (APCI , CH OH): m/z (%) = 298.1
C-1), 159.9 (C-9), 147.8 (C-11), 139.9 (C-3), 135.7 (C-8a), 132.5 (C-6), (100). HRMS: calcd. for [C H12NO + H] 298.0863; found 298.0862.
–1
+
2
2
3
+
20 2
1
32.0 (C-7), 130.3 (C-13, C-15), 129.4 (C-8), 129.2 (C-4a, C-5a), 128.0
Oxazinone 8: 2-Aminoethanol (0.38 mL, 6.35 mmol) was added to a
suspension of 1,8-dihydroxy-9,9-dimethoxy-10-anthrone (18; 1.66 g,
(C-5), 126.1 (C-14), 124.6 (C-2), 120.9 (C-12, C-16), 119.9 (C-1a), 110.8
(C-4) ppm. IR (neat): ν = 1668 (m), 1603 (w), 1587 (m), 1556 (m),
˜
5.80 mmol) in toluene (50 mL) and the resulting reaction mixture
1
1
489 (m), 1477 (w), 1446 (m), 1333 (s), 1278 (m), 1255 (s), 1223 (s),
172 (w), 1149 (w), 1112 (m), 985 (w), 944 (m), 885 (w), 839 (w), 827
was heated at reflux for 18 h. n-Pentane was added and the precipi-
tate was filtered off, washed with n-pentane (2 × 20 mL), and dried
in vacuo. 8 was obtained as an orange solid (805 mg, 49 %). TLC
(
(
s), 809 (w), 784 (s), 752 (s), 707 (s), 691 (s), 678 (m), 654 (w), 632
–
w), 616 (w), 600 (m), 567 (w), 541 (m), 512 (w), 479 (m), 438 (w) cm
1
(
chloroform): R = 0.11. H NMR (300 MHz, CDCl ): δ = 13.04 (s, 1 H,
1
f
3
3
.
C H BrNO (378.22): calcd. C 63.51, H 3.20, N 3.70; calcd. C 63.67,
20 12 2
4
3
OH), 7.83 (dd, J = 7.7, J = 1.1 Hz, 1 H, 4-H), 7.78 (dd, J
=
H,H
H,H
H,H
H 3.23, N 3.90.
4
3
7
(
.8, J = 1.0 Hz, 1 H, 5-H), 7.57 (pt, J = 8.0 Hz, 1 H, 6-H), 7.53
H,H H,H
4
-Bromo-1-hydroxy-9-(2,6-diisopropylphenylimino)-10-
3
3
4
pt, J = 8.0 Hz, 1 H, 3-H) 7.24 (dd, J = 8.9, J = 1.1 Hz, 1
H,H H,H H,H
anthrone (6): 2,6-Diisopropylaniline (0.15 mL, 0.79 mmol) was
added to a suspension of 4-bromo-1-hydroxy-9,9-dimethoxy-10-
anthrone (23; 70 mg, 0.20 mmol) in toluene (10 mL) and the result-
ing mixture was heated at reflux for 24 h. The solvent of the red
reaction mixture was removed in vacuo and the raw product was
purified by column chromatography (silica gel; n-pentane/ethyl
acetate, 20:1). 6 was obtained as a red solid (88 mg, 95 %). TLC (n-
pentane/ethyl acetate, 20:1): R = 0.28. H NMR (300 MHz, CD Cl ):
δ = 15.64 (s, 1 H, OH), 8.25 (dd, J = 7.8, J = 1.0 Hz, 1 H, 5-H),
3
4
3
H, 2-H), 7.15 (dd, J = 8.2, J = 1.0 Hz, 1 H, 7-H), 6.04 (pt, J =
.3 Hz, 1 H, 11-H), 4.15 (d, J = 4.4 Hz, 2 H, 12-H), 2.12 (br. s, 1 H,
OH) ppm. C NMR (75 MHz, CDCl ): δ = 182.4 (C-10), 161.1 (C-1),
H,H
H,H
H,H
3
4
H,H
13
3
158.4 (C-8), 153.7 (C-9), 135.2 (C-6), 133.8 (C-3), 132.9 (C-4a), 130.5
(C-5a), 123.7 (C-2), 121.5 (C-7), 120.5 (C-5), 119.5 (C-4), 114.6 (C-1a),
1
2
13.9 (C-8a), 88.0 (C-11), 65.4 (C-12) ppm. IR (neat): ν˜ = 3483 (br w),
866 (br w), 1669 (w), 1627 (s), 1590 (m), 1488 (m), 1459 (m), 1358
1
f
2
2
(m), 1284 (s), 1260 (s), 1160 (w), 1113 (w), 1057 (m), 976 (w), 907
3
4
–1
+
H,H
H,H
(w), 867 (w), 836 (m), 770 (s), 736 (s) cm . MS (APCI , CH OH): m/z
3
3
7
.78 (d, J = 4.5 Hz, 1 H, 2-H), 7.62–7.58 (m, 1 H, 8-H), 7.31–7.20
+
H,H
(%) = 282.2 (100). HRMS: calcd. for 282.0761 [C16H11NO + H] ;
4
3
(m, 4 H, 6-H, 13-H, 14-H, 15-H), 7.17 (d, J = 8.9 Hz, 1 H, 3-H), 2.83
H,H
found 282.0758. C H NO (281.26): calcd. C 68.32, H 3.94, N 4.98;
16
11
4
3
3
(sept, J
= 6.8 Hz, 2 H, 17-H, 20-H), 1.14 (d, J
= 6.8 Hz, 6 H,
H,H
H,H
found C 68.24, H 3.98, N 4.94.
3
13
1
8-H, 21-H), 0.92 (d, JH,H = 6.9 Hz, 6 H, 19-H, 22-H) ppm. C NMR
1
-(2-Hydroxy-3,5-di-tert-butylphenylamino)-9,10-anthraquin-
(75 MHz, CD Cl ): δ = 183.2 (C-10), 162.5 (C-1), 160. 5 (C-9), 143.3
2 2
one (9): A suspension of 1-amino-9,10-anthraquinone (24; 343 mg,
.54 mmol), 3,5-di-tert-butyl-o-quinone (175 mg, 0.794 mmol), and
(C-11), 140.3 (C-2), 136.5 (C-12, C-16), 134.6 (C-8a), 132.9, 132.8 (C-
1
6
1
1
2
1
1
6
, C-8), 130.5 (C-1a), 130.1 (C-5a), 128.5 (C-5), 128.1 (C-7), 126.4 (C-
4), 125.1 (C-3), 124.8 (C-13, C-15), 119.1 (C-4a), 110.9 (C-4), 29.2 (C-
7, C-20), 24.1 (C-18, C-21), 22.6 (C-19, C-22) ppm. IR (neat): ν˜ =
961 (w), 1670 (w), 1600 (w), 1587 (w), 1568 (w), 1549 (w), 1477 (w),
439 (w), 1416 (w), 1341 (w), 1256 (s), 1217 (w), 1165 (w), 1084 (m),
013 (s), 868 (w), 838 (w), 793 (s), 783 (s), 708 (m), 662 (w), 634 (w),
p-toluenesulfonic acid (10 mg, 0.058 mmol) in toluene (20 mL) was
heated at reflux for 24 h. The solvent of the orange-red reaction
mixture was removed in vacuo and the raw product was purified
by column chromatography (silica gel; n-pentane/acetyl acetate,
2
0:1). 9 was obtained as an orange-red solid (34 mg, 10 %). TLC (n-
1
–
1
+
pentane/acetyl acetate, 20:1): R = 0.22. H NMR (300 MHz, CD Cl ;
00 (w), 562 (w), 545 (w), 492 (w), 466 (w) cm . MS (ESI , CH OH):
f
2
2
3
3
+
pt = pseudo-triplet): δ = 10.64 (s, 1 H, OH), 8.29 (dd, JH,H = 7.1,
m/z (%) = 462.4 (100). HRMS: calcd. for [C26H24BrNO2 + H]
62.1063; found 462.1062.
4
3
4
JH,H = 1.6 Hz, 1 H, 8-H), 8.23 (dd, J = 7.2, J = 1.8 Hz, 1 H, 5-
4
H,H
H,H
3
4
H), 7.81–7.74 (m, 2 H, 6-H, 7-H), 7.64 (dd, J = 7.3, J = 1.1 Hz,
1
H,H
H,H
Benzoacridinone 7: A solution of 1-hydroxy-9-(phenylimino)-10-
anthrone (1; 507 mg, 1.69 mmol) in dichloromethane (400 mL) and
boron trifluoride diethyl etherate (3.20 mL, 25.4 mmol) were added
to a quartz photochamber fitted with a 125 W Heraeus Noblelight
HPK mercury arc lamp. A flow of argon was maintained throughout
the reaction and the mixture was photolyzed for 14 h. The resulting
brown solution was washed with hydrogen carbonate (3 × 100 mL)
and brine (2 × 100 mL), dried with sodium sulfate, and the
solvent was removed in vacuo. The raw product was purified by
column chromatography (silica gel; n-pentane/ethyl acetate,
3
4
H, 4-H), 7.40 (pt, J = 8.0 Hz, 1 H, 3-H), 7.33 (d, J = 2.4 Hz,
H,H
H,H
3
4
1
H, 14-H), 7.1 (d, J
= 2.1 Hz, 1 H, 16-H), 6.83 (dd, J
= 8.5,
H,H
H,H
4
JH,H = 1.1 Hz, 1 H, 2-H), 6.23 (s, 1 H, NH), 1.48 (s, 9 H, 22-H, 23-H,
2
4-H), 1.29 (s, 9 H, 18-H, 19-H, 20-H) ppm. 13C NMR (75 MHz, CD Cl ):
2
2
δ = 186.2 (C-9), 183.5 (C-10), 151.7 (C-1), 149.4 (C-12), 143.2 (C-13),
36.5 (C-15), 135.6 (C-3), 135.0 (C-8a), 134.8 (C-4a), 134.5 (C-7), 133.9
C-6), 133.5 (C-5a), 127.2, 127.1 (C-5, C-8), 125.7 (C-11), 123.4 (C-14),
22.9 (C-16), 120.9 (C-2), 118.2 (C-4), 115.2 (C-1a), 35.5 (C-19), 34.7
C-17), 31.7 (C-18, C-19, C-20), 29.7 (C-22, C-23, C-24) ppm. IR (neat):
ν˜ = 3447 (br w), 3360 (br w), 3238 (br w), 2957 (br w), 2866 (br w),
659 (w), 1632 (m), 1588 (m), 1571 (m), 1494 (m), 1475 (m), 1463
m), 1444 (w), 1419 (w), 1390 (w), 1361 (m), 1335 (w), 1298 (m),
1
(
1
(
2
7
0:1 → 10:1 → 1:1). 7 was obtained as an orange solid (372 mg,
1
(
1
4 %). TLC (n-pentane/ethyl acetate, 20:1): R = 0.11. H NMR
f
(300 MHz, CD Cl ; pt = pseudo-triplet): δ = 15.43 (s, 1 H, OH), 9.00
2 2
1
1
268 (s), 1236 (m), 1215 (m), 118 (m), 1165 (m), 1150 (m), 1076 (w),
045 (w), 1018 (w), 958 (m), 910 (w), 889 (w), 869 (w), 831 (w), 822
3
4
3
4
(dd, J = 8.4, J = 0.9 Hz, 1 H, 7-H), 8.71 (dd, J = 7.4, J
=
H,H
H,H
H,H
H,H
3
4
1
.2 Hz, 1 H, 5-H), 8.68 (dd, J = 8.1, J = 1.5 Hz, 1 H, 13-H), 8.22
H,H H,H
(
(
4
4
w), 803 (w), 770 (w), 734 (m), 710 (s), 652 (w), 637 (w), 617 (m), 589
3
4
3
(dd, J = 8.2, J = 1.4 Hz, 1 H, 16-H), 8.15 (dd, J = 8.3, 7.5 Hz,
H,H
H,H
H,H
–1
+
w), 538 (m), 473 (w), 415 (m) cm . MS (APCI , CH OH): m/z (%) =
3
4
3
1
H, 6-H), 7.96 (dd, J
= 7.6, J
= 1.3 Hz, 1 H, 3-H), 7.88–7.78
H,H
H,H
+
28.3 (100). HRMS: calcd. for [C H NO + H] 428.2220; found
3
28 29
3
(
m, 2 H, 15-H, 14-H), 7.60 (pt, JH,H = 8.0 Hz, 1 H, 2-H), 7.39 (dd,
JH,H = 8.2, J = 1.3 Hz, 1 H, 4-H) ppm. C NMR (75 MHz, CD Cl ):
28.2211.
3
4
13
H,H
2
2
δ = 183.3 (C-10), 161.8 (C-1), 152.6 (C-9), 141.8 (C-11), 133.4 (C-1a), Phenoxazine 10: A solution of 3,5-di-tert-butylcyclohexa-3,5-diene-
32.9 (C-2), 132.5 (C-8), 132.3 (C-6), 130.7 (C-5a), 130.4 (C-15), 129.1 1,2-dione (2.07 g, 9.40 mmol) and 1-amino-9,10-anthraquinone (24;
1
(C-5), 129.1 (C-16), 128.7 (C-14), 128.6 (C-7), 124.0 (C-4), 123.8 (C-12),
2.12 g, 9.49 mmol) in toluene (100 mL) was heated at reflux for
1
23.0 (C-13), 122.0 (C-8a), 119.2 (C-3), 117.8 (C-4a) ppm. IR (neat):
24 h. Then a further 1 equiv. of 3,5-di-tert-butylcyclohexa-3,5-diene-
ν˜ = 1661 (s), 1606 (m), 1594 (m), 1581 (m), 1563 (m), 1507 (w), 1476 1,2-dione (2.07 g, 9.40 mmol) was added and the resulting mixture
(
(
w), 1461 (s), 1363 (w), 1327 (w), 1291 (s), 1278 (m), 1236 (w), 1178
w), 1159 (s), 1016 (w), 882 (m), 867 (m), 842 (w), 780 (m), 758 (s),
was heated at reflux for 72 h. The solvent of the blue-violet reaction
mixture was removed in vacuo and the raw product was purified
Eur. J. Org. Chem. 2016, 756–767
www.eurjoc.org
766
© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim