European Journal of Organic Chemistry
10.1002/ejoc.201700070
FULL PAPER
-
1
CH
2
), 6.28 (d, J = 5.2 Hz, 1H, CHth), 7.56 (d, J = 4.8 Hz, 1H, CHth), 8.22
, 25 °C): = 23.77, 25.54,
7.45, 51.56, 92.97, 103.58, 107.98, 122.10, 146.56, 151.91, 163.65,
65.76, 175.00 ppm. FT-IR (HATR): = 2923, 2854, 1672, 1493, 1372,
2856, 1632, 1470, 1411, 1248, 1155, 1084, 783 cm . HR-MALDI-MS
ppm (s, 1H, CH). 13C NMR (125 MHz, CDCl
δ
S [M+H] 418.21589; found 418.21567.
+
3
32 3
(DHB): calcd for C22H N O
3
2
1
1
ν
Chromophore 6b. Aldehyde 9b (222 mg) and N,N´-dibutylbarbituric acid
288 mg) were dissolved in 1,2-dichloroethane (20 mL) and Al (255 mg;
.5 mmol) was added. The reaction mixture was refluxed for 6 h,
-1
256, 1177, 1005, 929, 770 cm . HR-MALDI-MS (DHB): calcd for
(
2 3
O
+
C
16
H20NO
4
S [M+H] 322.11075; found 322.13881.
2
subsequently stirred at 25 °C for 16 h, filtered, and the solvent was
Chromophore 5b. The title compound was synthesized from aldehyde 9b
221 mg) and Meldrum´s acid (216 mg; 1.5 mmol) following the general
method (ii) in CH CN at 85 °C for 48 h. Yield: 153 mg (44 %); violet solid.
= 0.6 (SiO ; Hex/EtOAc 1:2); mp 213 °C. Found: C, 62.13; H, 6.15; N,
.01; S, 9.07; C18 S requires C, 62.23; H, 6.09; N, 4.03; S, 9.23 %.
, 25 °C): = 1.70-1.73 (m, 12H, CH +CH ), 3.42-
), 6.12 (d, J = 4.8 Hz, 1H, CHth), 7.27 (d, J = 4.8 Hz, 1H,
CHth), 7.38 (d, J = 14 Hz, 1H, CH), 7.58 (t, J = 13.2 Hz, 1H, CH), 8.00 ppm
evaporated in vacuo. The crude product was purified by column
(
chromatography (SiO
2
, CH
Cl
S requires C, 64.98; H, 7.50; N, 9.47; S, 7.23 %.
2
Cl
2
/acetone 60:1). Yield: 248 mg (56 %); black
3
solid. R = 0.4 (SiO ; CH
f
2
2
2
); mp 148 °C. Found: C, 64.70; H, 7.56; N,
R
4
1
f
2
9.21; S, 6.98; C24
H
33
N
3
O
3
1
H
21NO
4
H NMR (400 MHz, CDCl
), 1.56-1.61 (m, 4H, CH
), 3.88-3.92 (m, 4H, CH
3
, 25 °C):
δ
= 0.90-0.93 (m, 6H, CH
3
), 1.31-1.38
), 3.38-3.40
H NMR (400 MHz, CDCl
3
δ
2
3
(m, 4H, CH
2
2
), 1.63-1.70 (m, 6H, CH
2
3
.45 (m, 4H, CH
2
(m, 4H, CH
2
2
), 6.08 (d, J = 4.8 Hz, 1H, CHth), 7.22
(d, J = 4.4 Hz, 1H, CHth), 7.38 (d, J = 13.6 Hz, 1H, CH), 7.88 (t, J = 13.2
Hz, 1H, CH), 8.01 ppm (d, J = 12.8 Hz, 1H, CH). 13C NMR (125 MHz,
(
d, J = 12.8 Hz, 1H, CH). 13C NMR (100 MHz, CDCl
3
, 25 °C):
δ
= 23.72,
2
5.30, 27.53, 51.72, 100.88, 103.79, 106.92, 117.59, 125.48, 141.61,
CDCl
40.99, 41.50, 51.47, 106.25, 106.60, 118.06, 125.73, 140.89, 148.86,
151.59, 156.63, 162.49, 163.14, 168.19 ppm. FT-IR (HATR): = 2936,
2850, 1703, 1632, 1553, 1513, 1401, 1359, 1331, 1214, 1133, 1051, 993,
3
, 25 °C): δ = 13.87, 13.90, 20.24, 20.35, 23.53, 25.07, 30.32, 30.40,
149.09, 157.61, 162.69, 164.97, 168.87 ppm. FT-IR (HATR):
ν
= 2852,
-
2
.
358, 1673, 1514, 1469, 1410, 1349, 1210, 1138, 1112, 987, 927, 758 cm
ν
1
H21NO
4
S [M]+ 347.11858; found
HR-MALDI-MS (DHB): calcd for C18
-1
34 3 3
H N O
S [M+H]+
347.11969.
884, 748 cm . HR-MALDI-MS (DHB): calcd for C24
44.23154; found 444.23174.
4
Chromophore 5c. The title compound was synthesized from aldehyde 9c
222 mg) and Meldrum´s acid (360 mg) following the general method (iii)
in CH Cl at 25 °C. Yield: 180 mg (38 %); red-violet solid. R = 0.75 (SiO
EtOAc/CH Cl 1:10); mp 199 °C. Found: C, 57.02; H, 5.04; N, 2.72; S,
.91; C23
400 MHz, CDCl
(
Chromophore 6c. The title compound was synthesized from aldehyde 9c
(222 mg) and N,N´-dibutylbarbituric acid (600 mg) following the general
2
2
f
2
;
2
2
method (iii) at 25 °C for 3 h. Yield: 448 mg (67 %); dark red solid. R
(SiO ; CH Cl ); mp 127 °C. Found: C, 63.19; H, 7.62; N, 10.20; S, 4.61;
S requires C, 62.94; H, 7.40; N, 10.49; S, 4.80 %. H NMR (400
, 25 °C): = 0.93-0.99 (m, 12H, CH ), 1.34-1.43 (m, 8H, CH ),
), 1.76-1.86 (m, 6H, CH ), 3.66-3.68 (m, 4H, CH ),
), 8.26 (s, 1H, CH), 8.46 (s, 1H, CH), 8.62 ppm (s,
, 25 °C): = 13.93, 13.98, 20.29,
f
= 0.3
1
5
(
H
25NO
8
S requires C, 58.09; H, 5.30; N, 2.95; S, 5,74 %. H NMR
, 25 °C): = 1.73 (s, 6H, CH ), 1.75 (s, 8H, CH +CH ),
.84-1.86 (m, 4H, CH ), 3.67-3.69 (m, 4H, CH ), 8.23 (s, 1H, CH), 8.35 (s,
H, CH), 8.41 ppm (s, 1H, CH). 13C NMR (125 MHz, CDCl
, 25 °C):
2
2
2
1
3
δ
3
2
3
35 49 5 6
C H N O
1
1
δ
2
2
MHz, CDCl
3
δ
3
2
3
1.58-1.62 (m, 8H, CH
2
2
2
= 23.66, 25.99, 27.60, 27.85, 56.85, 102.19, 104.59, 104.62, 107.03,
16.75, 122.44, 147.41, 149.57, 151.53, 160.90, 162.44, 163.99, 179.62
3.91-3.97 (m, 8H, CH
2
1
1H, CH). 13C NMR (125 MHz, CDCl
3
δ
ppm. FT-IR (HATR):
ν
= 2921, 2852, 2364, 1690, 1490, 1356, 1271, 1154,
20.32, 20.35, 20.37, 23.70, 26.09, 30.27, 30.31, 41.31, 41.78, 42.03, 42.35,
56.68, 106.50, 111.33, 118.06, 122.51, 147.09, 149.40, 151.00, 151.25,
-1
S [M]+
1020, 920, 787 cm . HR-MALDI-MS (DHB): calcd for C23
H25NO
8
4
75.12954; found 475.13067.
152.37, 160.90, 162.28, 162.79, 162.89, 180.13 ppm. FT-IR (HATR):
ν
=
-
1
2
954, 2870, 1654, 1535, 1389, 1365, 1287, 1149, 1100, 950, 787 cm .
50 5 6
H N O
S [M+H]+ 668.34763; found
HR-MALDI-MS (DHB): calcd for C35
68.34758.
Chromophore 5d. The title compound was synthesized from dialdehyde
d (276 mg) and Meldrum´s acid (360 mg) following the general method
ii). Yield: 460 mg (87 %); black solid. R = 0.8 (SiO ; EtOAc/CH Cl 1:20).
S requires C, 61.47;
, 25 °C): = 1.73-
), 3.39-3.42 (m, 4H, CH ),
.27 (d, J = 15.6 Hz, 1H, CH), 7.38 (d, J = 14.8 Hz, 1H, CH), 7.49 (s, 1H,
6
9
(
f
2
2
2
Found: C, 61.21; H, 5.64; N, 2.64; S, 5.91; C27
H
29NO
8
Chromophore 6d. The title compound was synthesized from dialdehyde
9d (276 mg) and N,N´-dibutylbarbituric acid (600 mg) following the general
1
H, 5.54; N, 2.65; S, 6.08 %. H NMR (400 MHz, CDCl
3
δ
1.74 (m, 14H, CH
2 3
+CH ), 1.80-1.85 (m, 4H, CH
2
2
method (ii). Yield: 634 mg (88 %); black solid. R
f
= 0.55 (SiO
S requires C, 65.06;
, 25 °C): = 0.94-
), 1.58-1.64 (m, 8H, CH ), 1.71-
), 3.90-3.95 (m, 8H, CH ), 7.27
(d, J = 13.6 Hz, 1H, CH), 7.32-7.39 (m, 1H, CH), 7.52 (s, 1H, CHth), 8.06-
8.12 (m, 3H, CH), 8.22 ppm (dd, J = 12.4 Hz, J = 14.8 Hz, 1H, CH).
13C NMR (125 MHz, CDCl
, 25 °C): = 13.99, 14.03, 20.37, 20.47, 23.75,
2 2 2
; CH Cl ).
7
Found: C, 65.15; H, 7.54; N, 9.69; S, 4.38; C39
H, 7.42; N, 9.73; S, 4.45 %. H NMR (400 MHz, CDCl
H
53
N
5
O
6
1
CHth), 7.77 (dd, J
1
= 12 Hz, J
2
= 14.8 Hz, 1H, CH), 7.93 (dd, J
= 12 Hz, J = 16 Hz, 2H, CH).
= 23.68, 25.63, 27.79, 56.11, 104.65,
1
= 12 Hz,
3
δ
J
2
= 14.8 Hz, 1H, CH), 8.08 ppm (dd, J
1
2
0.97 (m, 12H, CH
3
), 1.32-1.43 (m, 8H, CH
2
2
1
3C NMR (125 MHz, CDCl
3
, 25 °C):
δ
1.81 (m, 6H, CH
2
), 3.37-3.40 (m, 4H, CH
2
2
1
1
04.75, 108.20, 108.39, 122.24, 122.68, 128.69, 135.42, 145.75, 146.45,
57.37, 158.49, 161.45, 161.54, 163.60, 163.76, 170.30 ppm. FT-IR
1
2
(HATR):
ν
= 2931, 2358, 1703, 1556, 1453, 1354, 1277, 1141, 1106, 991,
3
δ
-1
S [M]+
926, 787, 715 cm . HR-MALDI-MS (DHB): calcd for C27
H
29NO
8
25.68, 30.39, 30.46, 41.53, 41.56, 42.06, 56.12, 112.23, 112.51, 122.80,
122.91, 123.24, 129.26, 134.57, 145.35, 146.26, 151.26, 151.30, 156.57,
527.16084; found 527.16244.
1
ν
57.56, 162.00, 162.09, 162.55, 162.70, 169.66 ppm. FT-IR (HATR):
= 2954, 2864, 2360, 1654, 1558, 1496, 1402, 1370, 1152, 1102, 987,
Chromophore 6a. The title compound was synthesized from aldehyde 9a
195 mg) and N,N´-dibutylbarbituric acid (288 mg) following the general
method (iii) in CH Cl at 25 °C. Yield: 260 mg (62 %); orange solid. R = 0.8
SiO ; CH Cl /acetone 100:5); mp 172 °C. Found: C, 63.32; H, 7.52; N,
0.04; S, 7.61; C22 S requires C, 63.28; H, 7.48; N, 10.06; S,
.68 %. H NMR (500 MHz, CDCl , 25 °C): = 0.93 (t, J = 7.5 Hz, 6H, CH ),
.34-1.38 (m, 4H, CH ), 1.60-1.72 (m, 10H, CH ), 3.56-3.57 (m, 4H, CH ),
.91-3.94 (m, 4H, CH ), 6.31 (d, J = 5 Hz, 1H, CHth), 7.60 (s, 1H, CHth),
.30 ppm (s, 1H, CH). 13C NMR (125 MHz, CDCl
, 25 °C): = 14.09, 20.46,
3.75, 25.55, 30.54, 41.03, 41.77, 51.37, 99.65, 108.25, 122.67, 146.42,
51.92, 151.96, 162.85, 163.90, 174.74 ppm. FT-IR (HATR): = 2923,
-1
[M+H]+
7
7
89 cm . HR-MALDI-MS (DHB): calcd for
20.37893; found 720.37825.
39 54 5
C H N O
6
S
(
2
2
f
(
2
2
2
1
7
1
3
8
2
1
H
31
3
N O
3
Chromophore 7a. The title compound was synthesized from aldehyde 9a
(196 mg) and N,N´-dibutyl-2-thiobarbituric acid (308 mg) following the
general method (iii) at 25 °C. Yield: 252 mg (58 %); pink-red solid.
1
3
δ
3
2
2
2
2
R
f
= 0.65 (SiO
2
; CH
2
Cl
requires C, 60.94; H, 7.21; N, 9.69; S, 14.79 %.
, 25 °C): = 0.93-0.96 (m, 6H, CH ), 1.36-1.42
), 1.69-1.75 (m, 10H, CH ), 3.61-3.62 (m, 4H, CH ), 4.45-4.50
2
), 6.39 (d, J = 5 Hz, 1H, CHth), 7.63 (d, J = 5 Hz, 1H, CHth),
2
); mp 216 °C. Found: C, 61.21; H, 7.33; N, 9.54; S,
3
δ
14.51; C22
H NMR (500 MHz, CDCl
H
31
N
3
O
2
S
2
1
3
δ
3
ν
(m, 4H, CH
2
2
2
(m, 4H, CH
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