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M. Gonzalez-Lainez et al. / Dyes and Pigments 119 (2015) 30e40
38
Compound 6b was obtained as a yellow solid (164 mg,
4.1.10. (E)-1,3-Diethyl-5-((5-(4-((2-hydroxyethyl) (methyl)amino)
styryl)-2-thiophen-2-yl)methylen)-2-thiobarbituric acid (9)
To a solution of the 8 compound (67 mg, 0.12 mmol) in 2 mL
ethanol, NaOH was added (0.5 mL, 20%). The reaction mixture was
stirred at room temperature during 14 h with exclusion of light. The
residue was filtered and the solvent was removed. Chloroform
(200 mL) was added and the organic phase was washed several
times with both NH4Cl and water and dried. After concentration
under reduced pressure, a dark green solid was obtained (34 mg,
63%). Molecular weight (g/mol): 469.62.
0.63 mmol). Yield: 31%. Molecular weight (g/mol): 259.36.
m.p. (ꢁC) at 760 mmHg: 124. I.R. (Nujol) cmꢀ1: 1604 (C]C),
3250 (OeH). 1H NMR (400 MHz, CDCl3)
d: 3.01 (s, 3H), 3.51 (t,
J ¼ 5.6 Hz, 2H), 3.83 (t, J ¼ 5.6 Hz, 2H), 6.80 (d, J ¼ 8.6 Hz, 2H), 6.86
(d, J ¼ 16.1 Hz, 1H), 6.97e7.00 (m, 2H), 7.06 (d, J ¼ 16.1 Hz, 1H), 7.13
(d, J ¼ 5.0 Hz,1H), 7,36 (d, J ¼ 8.6 Hz, 2H).13C NMR (100 MHz, CDCl3)
d
: 39.0; 55.3; 60.1; 113.0; 118.1; 123.2; 124.7; 126.2; 127.4; 128.3;
143.7; 149.2. HRMS (HR-ESIþ) m/z 260,1105 [MþH]þ; molecular
formula C15H18NOS requires [MþH]þ: 260,1104. Elemental anal-
ysis found C 69.63, H 6.62, N 5.39, S 12.39%, molecular formula
m.p. (ꢁC) at 760 mmHg: 210. IR (Nujol) (cmꢀ1): 1377 (C]S),
C
15H17NOS requires C 69.46, H 6.61, N 5.40, S 12.36%.
1644 (C]O), 3497 (OeH).1H NMR (400 MHz, CDCl3)
d: 1.32 (t,
J ¼ 7.0 Hz, 3H), 1.36 (t, J ¼ 7.0 Hz, 3H), 3,09 (s, 3H), 3.58 (t, J ¼ 5.6 Hz,
2H), 3.87 (t, J ¼ 5.6 Hz, 2H), 4.56e4.67 (m, 4H), 6.79e6.86 (m, 2H),
7.09 (d, J ¼ 16.0 Hz, 1H), 7.21 (d, J ¼ 4.3 Hz, 1H), 7.38 (d, J ¼ 16.0 Hz,
1H), 7.45 (d, J ¼ 8.9 Hz, 2H), 7.78 (d, J ¼ 4.3 Hz, 1H), 8.60 (s, 1H).13C
4.1.8. 2-((4-(2-(5-formylthiophene-2-yl)vinyl)phenyl) (methyl)
amino)ethyl benzoate (Ald 4)
POCl3 (0.05 mL, 0.58 mmol) was added dropwise to (0.29 mL,
3.77 mmol) of freshly distilled DMF at 0 ꢁC in argon atmosphere. A
solution of (212 mg, 0.58 mmol) of compound 6a was added
dropwise to the POCl3/DMF complex at rt. The reaction mixture was
stirred at 80 ꢁC for 20 h. After the completion of the reaction
(monitored by TLC), the reaction mixture was cooled to rt and
poured into ice water. The crude product was extracted with
dichloromethane (3 ꢂ 100 mL) and the organic layer was washed
with sodium bicarbonate and water and dried over anhydrous so-
dium sulfate. After removing the solvent under reduced pressure,
the residue was purified by column chromatography (eluent:
hexane/dichloromethane, 1:1) on silica gel to afford an orange solid
(188 mg, 0.48 mmol), 83% yield as a mixture Z/E (46/54). Molecular
weight (g/mol): 391.48.
NMR (100 MHz, CDCl3) d: 12.4, 12.6, 29.7, 43.1, 44.0, 126.6, 129.0,
147.6, 149.0, 160.0, 161.2, 178.7. HRMS (ESIþ) m/z 470.1552 [MþH]þ;
[C24H28N3O3S2]þ requires 470.1567. UveVis data lmax(CH2Cl2)
(nm): 587, molar extinction coefficient εmax(mlꢀ1dm3 cmꢀ1): 41.
Elemental analysis found C 61.28, H 5.76, N 9.10, S 13.50%; mo-
lecular formula C24H27N3O3S2 requires C 61.38, H 5.80, N 8.95, S
13.65%.
4.1.11. (E)-5-((5-(4-((2-((terc-buthyldimethylsilyl)oxi)ethyl)
(methyl)amino)styryl)thiophen-2-yl)methylen)-1,3-dimethyl-2-
tioxodihydropyrimidine-4,6(1H,5H)-dione (10)
To a stirred solution of 1,3-diethyl-2-thiobarbituric acid, T
(50 mg, 0.250 mmol) in ethanol (6 mL), Ald 5 (100 mg, 0.250 mmol)
solved in ethanol (12 mL) was added. The reaction mixture was
heated at 70 ꢁC during 2 h with exclusion of light. The precipitated
was filtered and washed with cold ethanol. 0.120 g (0.205 mmol) of
a dark blue solid were obtained with a yield of 82%. Molecular
weight (g/mol): 583.88.
IR (KBr) cmꢀ1: 1262 (CeO), 1649 (C]O), 1714 (C]O). 1H NMR
(400 MHz, CDCl3)
d: 3.09e3.11 (m, 6H), 3.77e3.81 (m, 4H),
4.51e4.55 (m, 4H), 6.51 (d, J ¼ 12.0 Hz, 1H), 6.68 (d, J ¼ 12.0 Hz, 1H),
6.80 (m, 4H), 7.01 (d, J ¼ 16.0 Hz, 1H), 7.07e7.11 (m, 3H), 7.27 (d,
J ¼ 8.9 Hz, 2H), 7.39e7.44 (m, 6H), 7,54e7,56 (m, 3H), 7,64 (d,
J ¼ 3.9 Hz, 1H), 7.95e8.00 (m, 4H), 9.79 (s, 1H), 9.82 (s, 1H). HRMS
(HR-ESIþ) m/z 392,1321 [MþH]þ; molecular formula C23H22NO3S
requires [MþH]þ 392,1315. Elemental analysis found C 70.80, H
5.40, N 3.59, S 8.17%, molecular formula C22H21NO3S requires C
70.56, H 5.41, N 3.58, S 8.19%.
m.p. (oC) at 760 mmHg: 140 (d). IR (Nujol) (cmꢀ1): 1266 (CeO),
1382 (C]S), 1652 (C]O). 1H NMR (400 MHz, CDCl3)
d 0.02 (s, 6H),
0.88 (s, 9H), 1.31 (t, J ¼ 7.2 Hz, 3H), 1.36 (t, J ¼ 7.2 Hz, 3H), 3.07 (s,
3H), 3.53 (t, J ¼ 5.6 Hz, 2H), 3.80 (t, J ¼ 5.6 Hz, 2H), 4.58 (c, J ¼ 6.8 Hz
2H), 4.62 (c, J ¼ 6.8 Hz, 2H), 6.72 (d, J ¼ 8.8 Hz, 2H), 7.04 (d,
J ¼ 16 Hz, 1H), 7.19 (d, J ¼ 4.4 Hz, 1H), 7.37 (d, J ¼ 16 Hz, 1H), 7.42 (d,
J ¼ 8.8 Hz, 2H), 7.76 (d, J ¼ 4.4 Hz, 1H), 8.58 (s, 1H). 13C NMR
(100 MHz, CDCl3) ꢀ5.4, 12.4, 12.6, 25.8, 39.4, 43.1, 43.9, 54.7, 60.4,
108.4,112.2,116.0,126.0,129.1,136.2,147.9,148.8,150.2,161.3,162.8,
178.6. HRMS (ESIþ) m/z 584.2392 [MþH]þ; [C30H42N3O3S2Si]þ re-
quires 584.2431. UveVis data lmax(CH2Cl2) (nm): 599, molar
extinction coefficient εmax(mlꢀ1dm3 cmꢀ1): 50. Elemental analysis
found C 61.58, H 7.25, N 7.05, S 11.05%, molecular formula
4.1.9. (E)-2-((4-(2-(5-((1,3-diethylthiobarbituric)-5(2H)-ylidene)
methyl)thiophene-2-yl)vinyl)phenyl) (methyl)amino)ethyl benzoate
(8)
A solution of the aldehyde, Ald 4 (103 mg, 0.26 mmol) and 1,3-
diethyl-2-thiobarbituric acid, T (53 mg, 0.26 mmol) was prepared in
25 mL ethanol. The mixture was refluxed under argon atmosphere
with exclusion of light for 1 h. After cooling, the residue was filtered
and washed with cold ethanol. A dark blue solid was obtained
(83 mg, 55%). Molecular weight (g/mol): 573.73.
C30H41N3O3S2Si requires C 61.71, H 7.08, N 7.20, S 10.98%.
m.p. (ꢁC) at 760 mmHg: 175. IR (KBr) (cmꢀ1): 1264 (CeO), 1685
4.1.12. 5-(3-((E)-2-(5-((E)-4-((2-((terc-buthyldimethylsilyl)oxi)
ethyl) (methyl)amino)styryl)thiophen-2-yl)vinyl)-5,5-
dimethylcyclohex-2-en-1-yliden)-1,3-diethyl-2-
(C]O), 1717 (C]O).1H NMR (400 MHz, CDCl3)
d
: 1.32 (t, J ¼ 7.0 Hz,
3H), 1.37 (t, J ¼ 7.0, 3H), 3.13 (s, 3H), 3.82 (t, J ¼ 5.9 Hz, 2H), 4.53 (t,
J ¼ 5.9 Hz, 2H), 4.56e4.66 (m, 4H), 6.83 (d, J ¼ 8.8 Hz, 2H), 7.08 (d,
J ¼ 16.0 Hz, 1H), 7,22 (d, J ¼ 4.2 Hz, 1H), 7.38 (d, J ¼ 16.0 Hz, 1H),
7.40e7.43 (m, 2H), 7.44e7.47 (m, 2H), 7.54e7.58 (m, 1H), 7.79 (d,
J ¼ 4.2 Hz, 1H), 7.95e7.97 (m, 2H), 8.60 (s, 1H).13C NMR (100 MHz,
tioxodihydropyrimidine-4,6(1H,5H)-dione (11)
To a stirred solution of Ald 5 (150 mg, 0.373 mmol) in dry
acetonitrile (8 mL) piperidine (0.037 mL, 0.373 mmol) was added.
After 15 min, the acceptor IT (119.68 mg, 0.373 mmol) was also
added. The mixture was heated at 70 ꢁC during 1 h. The solvent was
removed and the residue was solved with dichloromethane
(200 mL) and washed with H2OeHCl (9:1) (2 ꢂ 70 mL) and twice
with water. The residue was dried and purified with two consec-
utive column chromatography hexane-ethyl acetate (8:1) on sili-
CDCl3) d: 12.4, 12.6, 39.1, 43.1, 43.9, 51.1, 61.9, 108.7, 112.5, 116.7,
126.3, 128.4, 129.1, 129.6, 129.7, 133.2, 135.4, 135.8, 147.8, 150.0,
160.0, 161.3, 162.3, 166.5, 178.7. HRMS (ESIþ) m/z 574.1809 [MþH]þ;
[C31H32N3O4S2]þ requires 574.1829. UveVis data lmax(CH2Cl2)
(nm): 584, molar extinction coefficient εmax(mlꢀ1dm3 cmꢀ1): 51.
Elemental analysis found C 65.01, H 5.56, N 7.11, S 11.25%; molec-
ular formula C31H31N3O4S2 requires C 64.90, H 5.45, N 7.32, S 11.18%.
cagel (40e60
mm). The desired product was obtained as a dark blue
solid with a yield of 6%. Molecular weight (g/mol): 704.07.