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product was puried by ltration and washed with cold MeOH NMR (100 MHz, DMSO-d
6
) d 188.3 (1C), 183.9 (1C), 178.3 (1C),
(
2 mL) or by column chromatography when necessary. Yields 170.5 (1C), 153.2 (1C), 134.1 (1C), 133.6 (1C), 132.3 (1C), 131.5
are reported below and pure compounds were obtained as (1C), 129.7 (1C), 128.0 (1C), 127.9 (1C), 127.9 (1C), 126.6 (1C),
stable solids. 126.4 (1C), 126.1 (1C), 125.7 (1C), 125.3 (1C), 124.0 (1C), 123.6
,4 -([1,1 -Biphenyl]-4,4 -diylbis(azanediyl))bis(3-methoxy- (1C), 122.5 (1C), 118.4 (1C), 113.7 (1C), 60.1 (1C). IR (KBr lm)
0
0
0
4
ꢁ1
cyclobut-3-ene-1,2-dione) (1). Following the general procedure, (cm ) n 2924, 2854, 1800, 1711, 1604, 1574, 1463, 1377, 814,
compound 1 was obtained aer 64 h of reaction at room 434. MS (ESI+) 396.3 [M + H]. HRMS (ESI+) calcd for
ꢃ
temperature as a yellow solid in 75% yield (61 mg). M.p. > 260 C
C
25
H17NNaO
4
418.1050; found 418.1046 [M + Na].
1
ꢃ
decomp. H NMR (300 MHz, DMSO-d , 60 C) d 10.84 (s, 2H),
6
3-(Chrysen-6-ylamino)-4-methoxycyclobut-3-ene-1,2-dione (5).
1
3
7
.67 (d, J ¼ 8.6 Hz, 4H), 7.44 (d, J ¼ 7.6 Hz, 4H), 4.41 (s, 6H). C- Following the general procedure using 1 mL of MeOH and Et N
3
ꢃ
APT NMR (75 MHz, DMSO-d , 60 C) d 136.9 (2C), 134.7 (2C), (0.2 mmol), compound 5 was obtained aer 60 h of reaction at
6
ꢁ
1
1
3
1
26.5 (4C), 119.7 (4C), 60.2 (2C). IR (KBr lm) (cm ) n 3250, room temperature as a yellow paled solid in 76% yield (53.7 mg).
ꢃ
1
192, 3095, 2923, 2853, 1797, 1706, 1616, 1569, 1514, 1456, M.p. > 260 C decomp. H NMR (400 MHz, DMSO-d
392, 1377, 1080, 926, 846, 733, 457. MS (ESI+) 405.2 [M + H]. s, 1H), 9.00 (d, J ¼ 8.0 Hz, 1H), 8.92 (d, J ¼ 8.1 Hz, 1H), 8.86 (d, J ¼
NaO
427.0901; found 427.0896 9.1 Hz, 1H), 8.69 (br s, 1H), 8.32 (d, J ¼ 7.6 Hz, 1H), 8.10 (d, J ¼ 8.5
6
) d 11.20 (br
HRMS (ESI+) calcd for C22
M + Na].
-Methoxy-4-(phenanthren-9-ylamino)cyclobut-3-ene-1,2-dione DMSO-d
H
16
N
2
6
1
3
[
Hz, 2H), 7.88–7.59 (m, 4H), 4.34 (s, 3H). C-APT NMR (100 MHz,
) d 188.7 (1C), 184.9 (1C), 178.9 (1C), 170.8 (1C), 131.8
3
6
(2). Following the general procedure, compound 2 was obtained (1C), 131.7 (1C), 130.4 (1C), 129.8 (1C), 128.3 (1C), 127.4 (1C),
aer 64 h of reaction at room temperature as a white solid in 58% 127.3 (1C), 127.1 (1C), 126.9 (1C), 126.8 (1C), 126.7 (1C), 126.5
ꢃ
1
yield (35.5 mg). M.p. 188–190 C. H NMR (400 MHz, DMSO-d ) (1C), 126.0 (1C), 123.7 (1C), 123.6 (1C), 123.4 (1C), 121.1 (1C),
6
ꢁ
1
d 11.03 (s, 1H), 8.93–8.88 (m, 1H), 8.86–8.81 (m, 1H), 8.18 (dd, J ¼ 116.0 (1C), 60.3 (1C). IR (KBr lm) (cm ) n 3225, 2923, 2853,
8
.0, 1.4 Hz, 1H), 7.95 (dd, J ¼ 7.6, 1.7 Hz, 1H), 7.82–7.63 (m, 5H), 1797, 1720, 1592, 1509, 1486, 1403, 809, 748, 447. MS (ESI+) 354.2
13
4
6 3
.30 (s, 3H). C-APT NMR (100 MHz, DMSO-d ) d 188.6 (1C), 184.7 [M + H]. HRMS (ESI+) calcd for C23H15NNaO 376.0944; found
(
(
(
1C), 178.8 (1C), 171.2 (1C), 131.1 (1C), 130.9 (1C), 130.3 (1C), 128.5 376.0934 [M + Na].
1C), 128.4 (1C), 127.4 (1C), 127.4 (1C), 127.1 (1C), 127.0 (1C), 126.8 3-([9H-Fluoren-2-yl]amino)-4-methoxycyclobut-3-ene-1,2-dione
1C), 123.6 (1C), 123.3 (1C), 122.9 (1C), 121.1 (1C), 60.4 (1C). IR (6). Following the general procedure using 2 mL of MeOH,
ꢁ
1
(KBr lm) (cm ) n 3214, 2953, 2924, 2853, 1812, 1694, 1621, 1454, compound 6 was obtained aer 90 min of reaction at room
ꢃ
1
362, 1231, 936, 766, 749, 727, 420. MS (ESI+) 326.1 [M + Na]. temperature as a yellow solid in 77% yield (45 mg). M.p. > 250 C
1
HRMS (ESI+) calcd for C19
H
13NNaO
3
326.0788; found 326.0778 decomp. H NMR (400 MHz, DMSO-d
6
) d 10.86 (br s, 1H), 7.89–
[
M + Na].
7.83 (m, 2H), 7.61–7.54 (m, 2H), 7.42–7.34 (m, 2H), 7.32–7.26 (m,
13
3-(Fluoranthen-3-ylamino)-4-methoxycyclobut-3-ene-1,2-dione 1H), 4.40 (s, 3H), 3.92 (s, 2H). C-APT NMR (75 MHz, DMSO-d
6
)
(3). Following the general procedure, compound 3 was obtained d 183.8 (1C), 144.0 (1C), 142.7 (1C), 140.5 (1C), 137.2 (1C), 136.8
aer 93 h of reaction at room temperature and puried by (1C), 126.9 (1C), 126.3 (1C), 124.9 (1C), 120.3 (1C), 119.6 (1C),
ꢁ1
column chromatography, as a red solid in 49% yield (32.2 mg). 118.4 (1C), 116.3 (1C), 60.5 (1C), 36.4 (1C). IR (KBr lm) (cm ) n
ꢃ
1
M.p. > 260 C decomp. H NMR (400 MHz, DMSO-d ) d 11.24 (s, 3245, 3198, 2923, 2853, 1795, 1709, 1606, 1584, 1522, 1519, 1467,
6
1
2
7
d
1
H), 8.16 (d, J ¼ 8.1 Hz, 2H), 8.11 (d, J ¼ 7.5 Hz, 1H), 8.06–8.01 (m, 1389, 1077, 1016, 764, 730. MS (ESI+) 314.0 [M + Na]. HRMS (ESI+)
H), 7.74 (dd, J ¼ 8.2 Hz, J ¼ 7.1 Hz, 1H), 7.45 (d, J ¼ 7.5 Hz, 1H), calcd for C18 13NNaO 314.0788; found 314.0781 [M + Na].
3-([9H-Fluoren-2-yl]amino)-4-propoxycyclobut-3-ene-1,2-dione
) d 188.2 (1C), 184.8 (1C), 179.0 (1C), 170.3 (1C), 138.5 (1C), (7). Firstly, 3,4-dipropoxycyclobut-3-ene-1,2-dione was prepared
38.1 (1C), 136.0 (1C), 133.5 (1C), 133.3 (1C), 131.8 (1C), 128.1 with 3,4-dimethoxy-3-cyclobutene-1,2-dione at reux in 1-prop-
1C), 127.9 (1C), 127.3 (1C), 123.8 (1C), 123.0 (1C), 121.9 (1C), anol during 24 h. Following the general procedure and using
H
3
1
3
.44–7.39 (m, 2H), 4.35 (s, 3H). C-APT NMR (100 MHz, DMSO-
6
(
1
21.6 (1C), 121.5 (1C), 121.1 (1C), 120.9 (1C), 60.4 (1C). IR (KBr the resulting squarate 3,4-dipropoxycyclobut-3-ene-1,2-dione,
lm) (cm ) n 3322, 3285, 2923, 2853, 1801, 1711, 1583, 1453, compound 7 was obtained aer 72 h of reaction at room
ꢁ
1
1
+
3
362, 1282, 1257, 940, 849, 778, 756, 750, 456. MS (ESI+) 350.1 [M temperature as a yellow solid in 68% yield (43.7 mg). M.p. > 250
ꢃ
1
Na]. HRMS (ESI+) calcd for C21
H
13NNaO
3
350.0788; found
6
C decomp. H NMR (400 MHz, DMSO-d ) d 10.85 (br s, 1H), 7.89–
50.0780 [M + Na].
7.82 (m, 2H), 7.62–7.54 (m, 2H), 7.42–7.25 (m, 3H), 4.75–4.68 (m,
0
0
13
3-([(R)-2 -Hydroxy-{1,1 -binaphthalen}-2-yl]amino)-4-methoxy- 2H), 3.92 (br s, 2H), 1.89–1.74 (m, 2H), 1.08–0.94 (m, 3H). C-APT
cyclobut-3-ene-1,2-dione (4). Following the general procedure, NMR (75 MHz, DMSO-d ) d 183.7 (1C), 169.2 (1C), 143.9 (1C),
6
compound 4 was obtained aer 120 h of reaction at room 142.7 (1C), 137.2 (1C), 136.8 (1C), 126.7 (1C), 126.3 (1C), 125.0
temperature and puried by column chromatography (1C), 120.3 (1C), 119.6 (1C), 118.5 (1C), 116.4 (1C), 74.6 (1C), 36.4
ꢁ
1
(
Hex : EtOAc 7 : 3 to 3 : 7), as a yellow solid in 76% yield (60 mg). (1C), 22.8 (1C), 9.7 (1C). IR (KBr lm) (cm ) n 3233, 3122, 3067,
ꢃ
24
1
M.p. 142–144 C. [a]D ¼ +152.7 (c 0.27, CHCl ). H NMR (400 2923, 2853, 1806, 1710, 1587, 1495, 1458, 1414, 1364, 828, 764,
3
MHz, DMSO-d
6
) d 9.97 (br s, 1H), 9.66 (br s, 1H), 8.04 (d, J ¼ 9.2 727. MS (ESI+) 342.1 [M + Na]. HRMS (ESI+) calcd for
Hz, 1H), 8.01 (d, J ¼ 9.7 Hz, 1H), 7.93 (d, J ¼ 8.9 Hz, 1H), 7.88 (d,
J ¼ 8.1 Hz, 1H), 7.59 (d, J ¼ 8.7 Hz, 1H), 7.50–7.44 (m, 1H), 7.35
20
C H17NNaO
3
342.1101; found 342.1090 [M + Na].
3,4-Bis([9H-uoren-2-yl]amino)cyclobut-3-ene-1,2-dione (8).
(
d, J ¼ 8.9 Hz, 1H), 7.33–7.23 (m, 2H), 7.19–7.14 (m, 1H), 7.06 (d, Following the general procedure using 2 mL of MeOH and Et
3
N
1
3
J ¼ 8.5 Hz, 1H), 6.84 (d, J ¼ 8.3 Hz, 1H), 4.23 (s, 3H). C-APT (0.2 mmol), compound 8 was obtained aer 72 h of reaction at
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RSC Adv., 2016, 6, 14171–14177 | 14175