10.1002/cplu.202000026
ChemPlusChem
FULL PAPER
MHz, Pyridine-d5, 278 K): δ(ppm, J(Hz)): 4.35 (s, 28H), 3.69 (s, 24H), 3.18
(s, 42H), 2.66 (br s, 4H), 2.11 (br s, 4H). 13C NMR (126 MHz, Pyridine-d5,
278 K): δ(ppm, J(Hz)): 151.7, 142.7, 71.2, 71.0, 58.4, 51.3, 49.1, 37.5, 36.0,
24.3; IR (ATR): ν˜= 2979, 2933, 1560, 1425, 1113 cm−1; HR MS (ESI):
(m/z): 1601.7394 [M+H]+ (teor.: 1601.7426). Q39-1Zn UV/Vis (DMF): λmax
(ε)= 659 (171030), 600 (33870), 523 (35110), 383 nm (121350
mol−1dm3cm−1).
143.2, 143.1, 142.9, 142.8, 135.5, 135.3, 123.5, 123.3, 71.2, 71.1, 59.7,
58.5, 49.2, 49.1, 49.0, 48.1, 47.8, 40.5, 35.4, 33.9, 33.5, 33.0, 32.3; IR
(ATR): ν˜= 2926, 2095 (N3), 1420, 1112 cm−1; HR MS (ESI): (m/z):
1650.8181 [M+H]+ (teor.: 1650.8219), 826.4205 [M+2H]2+ (teor.:
826.4183); UV/Vis (DMF): λmax (ε)= 659 (180160), 601 (35060), 514
(33380), 382 nm (123140 mol−1dm3cm−1).
9,10,16,17,23,24-hexakis[bis(2-methoxyethyl)amino]-3-diethylamino-
2-[4-(2-azidoethyl)piperidin-1-yl]-1,4,8,11,15,18,22,25-
9,10,16,17,23,24-hexakis[bis(2-methoxyethyl)amino]-3-[4-(2-
azidoethyl)piperidin-1-yl]-2-(3-carboxypropyl-methylamino)-
1,4,8,11,15,18,22,25-octaazaphthalocyaninato zinc(II) (2): Prepared
according to general method described above using TPyzPz 2H (90 mg,
octaazaphthalocyaninato zinc(II) (4): Prepared according to general
method described above using TPyzPz 4H (285 mg, 0.19 mmol), zinc (II)
acetate (205 mg, 1.12 mmol); eluent: dichloromethane/MeOH 20:1
(Rf=0.42). Yield: dark blue solid (213 mg, 72 %). 1H NMR (500 MHz,
Pyridine-d5, 278 K): δ(ppm, J(Hz)): 4.58 (d, J = 12.4 Hz, 2H), 4.43 – 4.32
(m, 24H), 4.04 (q, J = 7.1 Hz, 4H), 3.76 – 3.70 (m, 20H), 3.67 (t, J = 5.4
Hz, 4H), 3.33 (t, J = 7.0 Hz, 2H), 3.22 (s, 30H), 3.20 (s, 6H), 3.03 (t, J =
11.9 Hz, 2H), 1.82 (d, J = 12.1 Hz, 2H), 1.63 – 1.56 (m, 1H), 1.56 – 1.45
(m, 4H), 1.27 (t, J = 7.0 Hz, 6H); 13C NMR (126 MHz, Pyridine-d5, 278 K):
δ(ppm, J(Hz)): 151.47, 151.44, 151.40, 151.32, 151.27, 151.14, 151.05,
150.95, 143.60, 142.90, 142.87, 142.85, 142.82, 142.56, 71.23, 71.20,
71.17, 71.13, 58.47, 58.44, 49.21, 49.16, 49.11, 48.99, 48.04, 42.55, 35.40,
33.89, 32.19, 13.17; IR (ATR): ν˜= 2927, 2096 (N3), 1460, 1420, 1112
cm−1; HR MS (ESI): (m/z): 1594.7903 [M+H]+ (teor.: 1594.7957). Q41-1Zn
UV/Vis (DMF): λmax (ε)= 659 (199740), 602 (38700), 522 (36520), 382 nm
(137670 mol−1dm3cm−1).
0.06 mmol),
zinc
(II)
acetate
(63 mg,
0.34 mmol);
eluent:
dichloromethane/MeOH 14:1 (Rf=0.45). Yield: dark blue solid (63 mg,
67 %). 1H NMR (500 MHz, Pyridine-d5, 278 K): δ(ppm, J(Hz)): 4.49 (d, J =
12.3 Hz, 2H), 4.45 – 4.33 (m, 24H), 4.22 (t, J = 7.2 Hz, 2H), 3.77 – 3.70
(m, 20H), 3.69 (t, J = 5.4 Hz, 4H), 3.48 (s, 3H), 3.29 (t, J = 7.0 Hz, 2H),
3.22 (s, 24H), 3.21 (s, 6H), 3.20 (s, 6H), 3.01 (t, J = 11.5 Hz, 2H), 2.68 (t,
J = 7.1 Hz, 2H), 2.29 (p, J = 7.1 Hz, 2H), 1.79 (d, J = 10.1 Hz, 2H), 1.57 –
1.45 (m, 5H); 13C NMR (126 MHz, Pyridine-d5, 278 K): δ(ppm, J(Hz)):
175.5, 151.5, 151.4, 151.3, 151.22, 151.16, 151.02, 150.93, 143.8, 142.89,
142.86, 142.8, 142.3, 71.22, 71.20, 71.18, 71.14, 58.5, 58.4, 50.3, 49.2,
49.1, 49.0, 48.1, 37.7, 35.4, 33.8, 32.6, 32.1, 23.4.; IR (ATR): ν˜= 2927,
2096 (N3), 1463, 1418, 1112 cm−1; HR MS (ESI): (m/z): 1638.7856[M+H]+
(teor.: 1638.7855). UV/Vis (DMF): λmax (ε)= 660 (182780), 601 (36320),
522 (34720), 383 nm (125810 mol−1dm3cm−1).
9,10,16,17,23,24-hexakis(diethylamino)-2,3-bis(3-carboxypropyl-
methylamino)-1,4,8,11,15,18,22,25-octaazaphthalocyaninato zinc(II)
(5): Prepared according to general method described above using TPyzPz
5H (170 mg, 0.14 mmol), zinc (II) acetate (154 mg, 0.84 mmol); eluent:
dichloromethane/MeOH/acetic acid 100:5:2 (Rf=0.39). Yield: 135 mg
(75 %) of dark blue solid. 1H NMR (500 MHz, Pyridine-d5, 278 K): δ(ppm,
J(Hz)): 4.03 (t, J = 7.2 Hz, 4H), 3.94 – 3.84 (m, 24H), 3.31 (s, 6H), 2.66 (t,
J = 7.3 Hz, 4H), 2.25 (q, J = 7.4 Hz, 4H), 1.23 – 1.14 (m, 36H); 13C NMR
(126 MHz, Pyridine-d5, 278 K): δ(ppm, J(Hz)): 175.7, 151.5, 151.4, 150.8,
143.0, 142.9, 50.7, 43.0, 37.4, 32.7, 23.4, 13.2, 13.1; IR (ATR): ν˜= 2967,
1423, 1254, 1160 cm−1; HR MS (ESI): (m/z): 1241.6151 [M+H]+ (teor.:
1241.6159). UV/Vis (DMF): λmax (ε)= 659 (191640), 599 (38940), 514
(37490), 382 nm (137970 mol−1dm3cm−1).
2-[4-(2-azidoethyl)piperidin-1-yl]-3-[4-(2-dimethoxytrityloxyethyl)-
piperidin-1-yl]-9,10,16,17,23,24-hexakis[bis(2-methoxyethyl)amino]-
1,4,8,11,15,18,22,25-octaazaphthalocyaninato
zinc(II)
(3-DMTr):
Prepared according to general method described above using TPyzPz 3H-
DMTr (290 mg, 0.15 mmol), zinc (II) acetate (169 mg, 0.92 mmol), eluent:
dichloromethane/MeOH 22:1 (Rf=0.37). Yield: dark blue crystals (150 mg,
50 %). 1H NMR (500 MHz, Pyridine-d5, 278 K): δ(ppm, J(Hz)): 7.86 – 7.81
(m, 2H), 7.71 – 7.67 (m, 4H), 7.52 (t, J = 7.8 Hz, 2H), 7.40 – 7.35 (m, 1H),
7.14 – 7.09 (m, 4H), 4.75 (dd, J = 23.6, 12.3 Hz, 4H), 4.42 (t, J = 5.4 Hz,
16H), 4.38 (t, J = 5.6 Hz, 8H), 3.78 (s, 6H), 3.77 – 3.72 (m, 16H), 3.70 (t, J
= 5.2, 3.5 Hz, 8H), 3.44 (t, J = 6.4 Hz, 2H), 3.37 – 3.32 (m, 2H), 3.23 (s,
24H), 3.21 (s, 6H), 3.20 (s, 6H), 3.14 – 3.03 (m, 4H), 1.97 – 1.78 (m, 8H),
1.58 – 1.42 (m, 6H); 13C NMR (126 MHz, Pyridine-d5, 278 K): δ(ppm,
J(Hz)): 159.12, 151.52, 151.43, 151.29, 151.27, 151.02, 150.88, 150.85,
146.4, 143.12, 143.09, 142.9, 142.83, 142.79, 137.3, 130.7, 128.8, 128.3,
127.2, 113.7, 86.4, 71.22, 71.19, 71.1, 61.5, 58.5, 58.4, 55.3, 49.21, 49.16,
49.1, 49.0, 48.0, 47.7, 37.1, 35.4, 33.9, 33.7, 32.8, 32.3; IR (ATR): ν˜=
2924, 2096 (N3), 1509, 1418, 1112 cm−1; HR MS (ESI): (m/z): 1952.9515
[M+H]+ (teor.: 1952.9526). UV/Vis (DMF): λmax (ε)= 659 (199740), 602
(38700), 522 (36520), 382 nm (137670 mol−1dm3cm−1).
9,10,16,17,23,24-hexakis(diethylamino)-3-[4-(2-azidoethyl)piperidin-
1-yl]-2-(3-carboxypropyl-methylamino)-1,4,8,11,15,18,22,25-
octaazaphthalocyaninato zinc(II) (6): Prepared according to general
method described above using TPyzPz 6H (160 mg, 0.13 mol), zinc (II)
acetate (145 mg, 0.79 mmol); eluent: dichloromethane/MeOH 18:1
(Rf=0.46). Yield: dark blue solid (126 mg, 75 %). 1H NMR (500 MHz,
Pyridine-d5, 278 K): δ(ppm, J(Hz)): 4.45 (d, J = 12.4 Hz, 2H), 4.19 (t, J =
7.3 Hz, 2H), 3.97 – 3.84 (m, 24H), 3.45 (s, 3H), 3.29 (t, J = 7.0 Hz, 2H),
2.99 (t, J = 12.0 Hz, 2H), 2.70 (t, J = 7.1 Hz, 2H), 2.30 (p, J = 7.3 Hz, 2H),
2-[4-(2-azidoethyl)piperidin-1-yl]-3-[4-(2-hydroxyethyl)-piperidin-1-
yl]-9,10,16,17,23,24-hexakis[bis(2-methoxyethyl)amino]-
1.77 (d, J = 10.7 Hz, 2H), 1.54 – 1.46 (m, 5H), 1.25 – 1.12 (m, 36H); 13
C
1,4,8,11,15,18,22,25-octaazaphthalocyaninato zinc(II) (3): TPyzPz 3-
DMTr (50 mg, 0.03 mmol) was dissolved in dichloromethane and
trichloroacetic acid (8 mg, 0.05 mmol) was added. Reaction mixture was
stirred for 2 hours at rt. Then, it was diluted with dichloromethane and
washed by 5% NaHCO3 (3×20 mL). Organic phase was dried with
anhydrous Na2SO4, filtered and evaporated to dryness. Final compound
NMR (126 MHz, Pyridine-d5, 278 K): δ(ppm, J(Hz)): 175.6, 151.61, 151.56,
151.52, 151.49, 151.41, 151.37, 151.16, 150.99, 143.8, 143.1, 143.00,
142.96, 142.4, 50.5, 49.2, 48.1, 42.99, 42.97, 42.77, 37.6, 35.4, 33.8, 32.7,
32.1, 23.4, 13.2, 13.1, 13.1; IR (ATR): ν˜= 2968, 2931, 2872, 2095 (N3),
1423, 1255, 1160 cm−1; HR MS (ESI): (m/z): 1278.6575 [M+H]+ (teor.:
1278.6587). UV/Vis (DMF): λmax (ε)= 659 (171030), 600 (33870), 523
(35110), 383 nm (121350 mol−1dm3cm−1).
was
purified
by
column
chromatography
on
silica
with
dichloromethane/MeOH 15:1 as a mobile phase (Rf=0.31). Yield: dark blue
crystals (37 mg, 88 %); 1H NMR (500 MHz, Pyridine-d5, 278 K): δ(ppm,
J(Hz)): 4.78 (br s, 4H), 4.41 (s, 16H), 4.36 (t, J = 5.1 Hz, 8H), 4.04 (t, J =
6.6 Hz, 2H), 3.74 (q, J = 5.1 Hz, 16H), 3.70 – 3.66 (m, 8H), 3.34 (p, J = 7.1
Hz, 2H), 3.23 (s, 24H), 3.21 (s, 6H), 3.20 (s, 6H), 3.15-3.03 (m, 4H), 2.07
(d, J = 11.4 Hz, 2H), 2.06-1.79 (m, 6H), 1.67-1.44 (m, 6H). 13C NMR (126
MHz, Pyridine-d5, 278 K): δ(ppm, J(Hz)): 151.5, 151.4, 151.3, 150.9, 149.7,
3,9,10,16,17,23,24-heptakis(diethylamino)-2-(4-(2-(4-(4-(bis(2-
hydroxyethyl)amino)phenyl)-1H-1,2,3-triazol-1-yl)ethyl)piperidin-1-
yl)-1,4,8,11,15,18,22,25-octaazaphthalocyaninato
zinc
(II)
(8):
Prepared according to general method described above using TPyzPz 8H
(25 mg, 0.02 mmol), zinc (II) acetate (20 mg, 0.11 mmol); eluent
dichloromethane/MeOH 13:1 (Rf=0.30). Yield: 18 mg (70%) of dark blue
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