Journal of Materials Chemistry A
Paper
ꢁ
(
Yield 1 g, 75%) m.p. 175–179 C. d
H
(400 MHz, MeOD) 8.11
d
H
(400 MHz, THF) 8.04–8.02 (doublet and singlet over-
(
1H, d, J 8.4), 7.89–7.80 (3H, m), 7.53–7.41 (2H, m), 7.32 (1H, t, J lapping 3H), 7.10 (1H, d, J 8.2), 5.58 (1H, s), 4.92 (2H, q, J 7.1),
.4), 4.25 (2H, bs), 3.24 (6H, q, J 7.3), 2.80 (2H, t, J 6.4), 1.93 (6H, 3.98 (2H, t, J 7.4), 3.65 (1H, s), 1.71 (6H, s), 1.56 (3H, t, J 7.1), 1.48
s), 1.33 (9H, t, J 7.3). (4H, m), 1.35 (14H, s), 0.95 (3H, t, J 6.6).
(101 MHz, MeOD) 191.78, 191.28, 185.69, 181.53, 173.25, (101 MHz, THF) 189.65, 187.42, 185.97, 171.22, 164.78,
7
d
C
d
C
1
1
2
38.03, 130.69, 130.12, 129.36, 128.99, 128.65, 127.93, 126.43, 164.58, 144.90, 138.61, 128.58, 122.74, 121.28, 105.69, 80.66,
25.99, 122.82, 122.40, 121.73, 112.87, 109.97, 38.39, 30.99, 67.84, 45.19, 40.59, 30.02, 27.73, 27.67, 27.62, 27.45, 27.44,
6.07, 7.93.
24.93, 24.51, 24.29, 20.71, 13.33, 11.61.
+
+
ꢀ
ꢀ
MS (FTMS+) M calculated ¼ 424, M observed ¼ 424, m/z
MS (FTMSꢀ) [M ꢀ H] calculated ¼ 494, [M ꢀ H] observed
+
ꢀ
accurate mass (FTMS+), reference compound: NH OAc, M
¼ 494. m/z accurate mass (FTMSꢀ), [M ꢀ H] calculated ¼
4
+
ꢀ
calculated ¼ 424.1292, M observed ¼ 424.1294. FT-IR (ATR) n/ 494.2912, [M ꢀ H] observed ¼ 494.2919.
ꢀ
1
ꢀ1
cm 3141 (s), 2982 (s), 2685 (s), 2515 (s), 2197 (s), 2178 (s), 1732
FT-IR (ATR) n/cm 3065 (b), 2925 (s), 2856 (s), 2530 (b), 1773
(
(
s), 1626 (s), 1595 (s), 1537 (s), 1517 (s). UV-visible lmax 467 nm (s), 1716 (s), 1678 (s), 1603 (s), 1539 (s). UV-visible lmax 428 nm
ꢀ
1
ꢀ1
ꢀ1
ꢀ1
ꢀ1
ꢀ1
ꢀ1
ꢀ1
47 000 M cm ꢂ 500 M cm ) in ethanol.
(78 000 M cm ꢂ 700 M cm ) in ethanol.
Preparation of 4-[(1-carboxy-1,3-dihydro-3,3-dimethyl-2H-
benzo[e]indol-2-ylidene)methyl]-3-cyclobutene-1,2-dione (5)
Preparation of 2-((2-ethoxy)methylene)-3,3-dimethyl-1-
dodecylindoline-3-(dicyanomethylidene)-5-carboxylic acid (8)
3
-Ethoxy-[(1-carboxyethyl)-1,1,2-trimethyl-1H-benzo[e]indolium
Synthetic procedures followed to (4).
ꢁ
iodide-2-ylidene)methyl]-3-cyclobutene-1,2-dione (1.07 g, 2.7
mmol) was dissolved in ethanol (10 ml) and heated under
Yield 0.8 g (70%) m.p. 170–175 C.
d (400 MHz, MeOD) 7.98 (1H, d, J 8.3), 7.90 (1H, s), 6.99 (1H,
H
reux. Tetrabutyl ammonium hydroxide (1 ml, 40%) was added d, J 8.3), 6.14 (1H, s), 3.86 (2H, t, J 7.0), 3.24 (6H, m), 1.75 (2H, d,
and the solution was reuxed for 10 min. The mixture was J 6.6), 1.68 (6H, s), 1.32 (24H, m), 0.91 (3H, t, J 6.3).
concentrated and 15 ml of cold ethanol was added. The yellow
dC (101 MHz, MeOD) 192.35, 185.79, 178.53, 168.78, 167.78,
product crystallized and was washed with ethanol three times. 163.87, 147.41, 140.60, 130.48, 123.27, 122.81, 118.66, 117.84,
ꢁ
Yield 0.5 g (50%) m.p. 185–191 C.
107.01, 86.06, 42.47, 41.36, 37.18, 35.58, 31.67, 29.32, 29.08,
d
H
(400 MHz, MeOD) 8.12 (1H, d, J 8.6), 7.83 (2H, dd, J 11.4, 29.04, 28.97, 27.91, 26.47, 26.21, 26.14, 23.01, 22.33, 17.98,
8
.6), 7.51–7.43 (2H, m), 7.28 (1H, t, J 7.5), 5.77 (1H, s), 4.29–4.21 13.06, 8.46, 7.85.
ꢀ
ꢀ
(
(
2H, m), 3.29–3.19 (10H, m), 2.68–2.60 (2H, m), 1.95 (6H, s), 1.67
10H, dt, J 15.9, 7.9), 1.50–1.35 (8H, m), 1.03 (8H, t, J 7.3).
MS (FTMSꢀ) [M] calculated ¼ 514, [M] observed ¼ 514 m/z
accurate mass (FTMSꢀ), [M] calculated ¼ 514.2711, [M]ꢀ
ꢀ
dC (101 MHz, MeOD) 204.15, 196.50, 179.97, 177.48, 164.56, observed ¼ 514.2699.
ꢀ
1
1
1
1
40.82, 130.72, 130.34, 129.33, 128.88, 126.09, 122.19, 121.66,
FT-IR (ATR) n/cm 3158 (bs), 2925 (s), 2854 (s), 2639 (bs),
09.93, 82.58, 58.13, 58.11, 58.08, 39.72, 34.14, 26.23, 23.39, 2201 (s), 2182 (s), 1749 (s), 1705 (s), 1666 (s), 1618 (m), 1604 (m),
ꢀ
1
ꢀ1
ꢀ1
9.32, 19.30, 12.55.
1533 (s). UV-visible lmax 466 nm (55 000 M cm ꢂ 600 M
+
+
ꢀ1
MS (FTMS+) M calculated ¼ 270, M observed ¼ 270, m/z cm ) in ethanol.
+
accurate mass (FTMS+), reference compound: NH
calculated ¼ 270.1125, M observed ¼ 270.1126.
4
OAc, M
+
Preparation of 5-carboxy-2,3,3-trimethyl-1-carboxyethyl-3H-
ꢀ
1
FT-IR (ATR) n/cm 3512 (w), 2960 (s), 2937 (s), 2876 (s), 1751 indolium iodide (9)
(
l
m), 1666 (w), 1623 (m), 1592 (s), 1548 (s), 1516 (s). UV-visible
A mixture of 5-carboxy-2,3,3-trimethyl-3H-indolium iodide (2 g,
mmol) and 3-iodopropionic acid (2 g, 7.5 mmol) was heated
ꢀ1
ꢀ1
ꢀ1
ꢀ1
443 nm (18 400 M cm ꢂ 200 M cm ) in ethanol.
max
6
under reux overnight under nitrogen in anhydrous 1,2
dichlorobenzene (30 ml). Aer cooling, the solvent was removed
in vacuo and the product was re-crystallized from methanol to
Preparation of 5-carboxy-2,3,3-trimethyl-1-dodecyl-3H-
indolium iodide (6)
A mixture of 5-carboxy-2,3,3-trimethyl-3H-indolium iodide (2 g, give a yellow solid. (Yield 1.67 g, 70%).
+
+
6
mmol) and iodododecane (4.1 g, 24 mmol) was heated under
MS (FTMS+) M calculated ¼ 276, M observed ¼ 276, m/z
+
reux overnight under nitrogen in anhydrous acetonitrile (80 accurate mass (FTMS+), reference compound: NH
ml). Aer cooling, the solvent was removed in vacuo and the calculated ¼ 276.1230, M observed ¼ 276.1227.
4
OAc, M
+
product was re-crystallized from methanol to give a yellow solid.
(
Yield 2.42 g, 72%).
Preparation of 2-((2-ethoxy-3,4-dioxocyclobut-1-enyl)
+
+
MS (FTMS+) M calculated ¼ 372, M observed ¼ 372. m/z methylene)-3,3-dimethyl-1-carboxyethylindoline-5-carboxylic
+
accurate mass (FTMS+), reference compound: NH OAc, M
calculated ¼ 372.2897, M observed ¼ 372.887.
acid (10)
4
+
Synthetic procedures followed (3).
ꢁ
Yield 0.5 g (80%) m.p. 180–185 C.
(400 MHz, MeOD) 8.04–7.97 (doublet and singlet over-
Preparation of 2-((2-ethoxy-3,4-dioxocyclobut-1-enyl)methylene)-
3
d
H
,3-dimethyl-1-dodecylindoline-5-carboxylic acid (7)
lapping 3H), 7.20 (1H, d, J 8.3), 6.02 (1H, s), 4.44 (3H, t, J 6.7),
4.27–4.20 (two overlapping triplets 4H), 4.17 (3H, t, J 7.4), 3.20
(2H, q, J 7.3), 1.66 (6H, s).
Synthetic procedures followed to (3).
ꢁ
(2 g, 65%) m.p. 180–184 C.
J. Mater. Chem. A
This journal is © The Royal Society of Chemistry 2015