Molecules 2018, 23, 127
4 of 11
Product
3
(0.585 g, 1 mmol) and 0.18 mL of 3-aminopropylmethoxyldimethylsilane were dissolved
◦
in tetrahydrofuran (60 mL). Then, the solution was warmed to 30 C and stirred for 0.5 h. The course of
the reaction was confirmed by thin-layer chromatography (toluene:acetone, 6:1; R = 0.75). The purple
f
solid was collected by filtration and dried to obtain 0.411 g of purple dye DP (yield 59%).
1
DP1 purification was done by column chromatography (dichloromethane:ethyl acetate, 10:1; v/v).
The synthesis of red dye DP2 (yield 58%) and DP3 (yield 57%) was similar to the method used in
the preparation of DP1 (3-aminopropylmethyldimethoxylsilane and 3-aminopropyltrimethoxylsilane
instead of 3-aminopropylmethoxyldimethylsilane were used, respectively).
2
.1.4. Characterization
The UV-Vis absorption spectra of the corresponding dyes were measured by an Agilent 8453
1
UV-Vis spectrophotometer (Agilent, Santa Clara, CA, USA). H-NMR Spectra were recorded with a
Varian INOVA 400 NMR spectrometer (Varian, Palo Alto, CA, USA). Infra-red spectra (20Dxb) were
measured with Necolet (Madison, WI, USA). Mass spectra were recorded on CID (Collision-Induced
Dissociation) = 50 V to 200 V with an HP 1100 high pressure liquid chromatography/mass spectrometry
(HPLC/MS) system (1100 HPLC, Hewlett Packard, Palo Alto, CA, USA).
2
.1.5. Structure Characterization Results of Reactive Disperse Silicon-Containing Dyes (Please see in
Supplementary Materials)
+
1
Red dye DR1: C H ClN O Si: MS (API-ES) [M + H] : 572. H-NMR data (ppm): (CDCl , 400 MHz) δ:
25
34
9
3
3
0
.07 (s, 6H), 0.56 (t, J = 6.6 Hz, 2H), 1.26 (t, J = 6.4 Hz, 6H), 1.85–1.86 (m, 2H), 3.01–3.02 (m, 2H), 3.49–3.50
(
m, 4H), 3.44–3.45 (m, 3H), 5.32–5.33 (m, 2H), 6.39–6.41 (m, 1H), 7.75–7.86 (m, 3H), 8.16–8.29 (m, 3H).
−
1
FT-IR (KBr, cm ): 3407, 3273 (N-H); 1587, 1564, 1473 (benzene ring or cyanide ring); 1520, 1327 (NO );
1
2
2
− −1
1
261 (Si-Me); 1178, 1101, 1078 (Si-OMe). UV-Vis (nm): 512.1; molar absorptivity (L
.40 × 10 .
·
mol
·
cm ):
4
+
1
Red dye DR2: C H ClN O Si: MS (API-ES) [M + H] : 588. H-NMR data (ppm): (CDCl , 400 MHz)
25
34
9
4
3
δ
: 0.15 (s, 3H), 0.70 (t, J = 8.0 Hz, 2H), 1.30 (t, J = 6.8 Hz, 6H), 1.85–1.86 (m, 2H), 3.50–3.54 (m, 12H),
.48–6.49 (m, 1H), 7.76–7.89 (m, 3H), 8.15–8.31 (m, 3H). FT-IR (KBr, cm ): 3398, 3356, 3265 (N-H);
−
1
6
1
562, 1473 (benzene ring or cyanide ring); 1516, 1325 (NO ); 1259 (Si-Me); 1176, 1101, 1076 (Si-OMe).
2
UV-Vis (nm): 511.9; molar absorptivity (L·mol− ·cm ): 2.41 × 10 .
1
−1
4
+
1
Red dye DR3: C H ClN O Si: MS (API-ES) [M + H] : 604. H-NMR data (ppm): (CDCl , 400 MHz
)
25
34
9
5
3
δ
: 0.72 (t, J = 8.0 Hz, 2H), 1.30 (t, J = 6.8 Hz, 6H), 1.77–1.78 (m, 2H), 3.51–3.60 (m, 15H), 6.44–6.46
−
1
(m, 1H), 7.76–7.87 (m, 3H), 8.15–8.29 (m, 3H). FT-IR (KBr, cm ): 3396, 3373, 3267 (N-H); 1585,
1
1
562, 1475 (benzene ring or cyanide ring); 1518, 1327 (NO ); 1178, 1101, 1078 (Si-OMe); 1176, 1101,
2
076 (Si-OMe). UV-Vis (nm): 512.0; molar absorptivity (L·mol ·cm ): 2.40 × 10 .
−
1
−1
4
+
1
Purple dye DP1: C H BrClN O Si: MS (API-ES) [M + H] : 697. H-NMR data (ppm): (CDCl3,
25
32
10
5
6
3
8
00 MHz)
δ: 0.14 (s, 6H), 0.68 (t, J = 6.6 Hz, 2H), 1.35 (t, J = 6.4 Hz, 6H), 1.68–1.70 (m, 2H), 3.47 (s,
H), 3.47–3.48 (m, 2H), 3.57–3.60 (m, 4H), 6.51–6.53 (m, 2H), 6.99–6.70 (m, 1H), 8.39–8.39 (m, 1H),
.66–8.66 (m, 1H). FT-IR (KBr, cm ): 3417, 3361, 3269 (N-H); 1579, 1566, 1473 (benzene ring or cyanide
−
1
ring); 1527, 1319 (NO ); 1259 (Si-Me); 1196, 1072 (Si-OMe). UV-Vis (nm): 553.5; molar absorptivity
2
−
1
−1
4
(
L·mol ·cm ): 1.66 × 10 .
+
1
Purple dye DP2: C H BrClN O Si: MS (API-ES) [M + H] : 713. H-NMR data (ppm): (DMSO-d ,
25
32
10
6
6
400 MHz)
δ: 0.11 (s, 3H), 0.66 (t, J = 8.0 Hz, 2H), 1.30 (t, J = 6.8 Hz, 6H), 1.62–1.74 (m, 2H), 3.22 (s, 6H),
3
.46–3.49 (m, 2H), 3.50–3.67 (m, 4H), 6.83–6.85 (m, 1H), 7.59–7.60 (m, 1H), 8.21–8.22 (m, 1H), 8.54 (s,
−
1
1
H), 8.74–8.75 (m, 1H). FT-IR (KBr, cm ): 3417, 3361, 3269 (N-H); 1566, 1473 (benzene ring or cyanide
ring); 1527, 1319 (NO ); 1259 (Si-Me); 1196, 1072 (Si-OMe). UV-Vis (nm): 553.4; molar absorptivity
2
−
1
−1
4
(
L·mol ·cm ): 1.66 × 10 .