Zinc(II) Porphyrin-Containing Dendrons
FULL PAPER
CH), 8.33 (d, J
7.97 (m, 2H; m-phenyl-H), 7.94 (m, 2H; Ar CH), 7.46 (m, 2H; m-
phenyl-H), 7.38 (m, 2H; o-phenyl-H), 7.31 (t, J(H,H)=7.6 Hz, 2H; Ar
CH), 7.05 (m, 2H; Ar CH), 4.74 (s, 4H; 2ꢄCH2N3), 3.35 (m, 8H; 4ꢄ
ethyl CH2), 2.35 (s, 12H; 4ꢄmethyl CH3), 2.28 (s, 6H; 2ꢄmethyl CH3),
G
COCH2CH2CO), 2.89 (m, 2H; CH2CH2CH2), 2.67 (t, JACTHNGUTER(NNUG H,H)=6.8 Hz,
2H; CH2CH2CH2), 2.64 (s, 9H; 3ꢄmethyl CH3), 2.36 (m, 2H;
CH2CH2CH2), 1.87 (s, 6H; 2ꢄmethyl CH3), 1.86 (s, 12H; 4ꢄmethyl
CH3), ꢀ2.54 ppm (brs, 2H; NH); MS (MALDI-TOF): m/z calcd for
C62H59N6O5: 967.45; found: 967.38 [M+H]+.
1.38 ppm (t, JACHTUNGTRENNUNG(H,H)=7.6 Hz, 12H; 4ꢄethyl CH3); UV/Vis (CH2Cl2): lmax
3-Trimethylsilylprop-2-ynylamine (15): Hydrazine hydrate (0.85 mL,
17.5 mmol) was added to a suspension of N-[3-(trimethylsilyl)-2-pro-
AHCTUNGERTGpNNUN ynyl]phthalimide (950 mg, 3.69 mmol) in dry ethanol (40 mL). The reac-
(eꢄ10ꢀ3)=396 (249), 541 (21.0), 578 nm (11.9 molꢀ1 Lcmꢀ1); MS
(MALDI-TOF): m/z calcd for C81H69N14OZn2: 1385.43; found: 1385.31
[M+H]+.
tion mixture was heated at reflux for 2 h. After cooling, the precipitate of
phthalic acid hydrazide was removed by filtration and washed with di-
chloromethane. The dichloromethane was removed under reduced pres-
sure, but product 15 could not be separated from the ethanol by distilla-
tion. Therefore, it was left in solution and used directly in the following
reaction steps. 1H NMR (300 MHz, CDCl3, 258C): d=4.82 (brs, 2H;
4,5-Bis[(2,8-diethyl-3,7-dimethyl-15-[4-(azidomethyl)phenyl]-5-porphyrin-
yl)-9,9-dimethylxanthene (9): Compound 8 (80.7 mg, 58.2 mmol) was dis-
solved in dichloromethane (10 mL), then HCl (6 n, 10 mL) was added
and the resulting mixture was stirred vigorously for 30 min. The organic
layer was separated, washed with saturated aqueous NaHCO3 (2ꢄ20 mL)
and water (2ꢄ20 mL), and then dried over MgSO4. The solvent was re-
moved under reduced pressure to afford the title compound as a purple
solid in quantitative yield (73.2 mg, 58.2 mmol). 1H NMR (300 MHz,
NH), 3.36 (s, 2H; CH2), 0.09 ppm (s, 9H; SiACTHNUTRGNEUNG
(CH3)3); 13C NMR
(75.5 MHz, CDCl3, 258C): d=106.9, 86.9, 32.2, ꢀ0.09 ppm; MS (ESI):
m/z calcd for C6H13NSi: 128.09; found:128.11 [M+H]+.
N4-(Prop-2-ynyl)-N1,N7-bis(trifluoroacetyl)-1,7-diamino-4-azaheptane
CDCl3, 258C): d=8.93 (d, J
(H,H)=4.1 Hz, 4H; b-pyrrole CH), 8.32 (s, 4H; meso-H), 8.26 (d, J-
(H,H)=4.1 Hz, 4H; b-pyrrole CH), 7.96 (m, 4H; m-phenyl-H+Ar CH),
7.56 (d, J(H,H)=7.4 Hz, 2H; m-phenyl-H), 7.47 (d, J(H,H)=7.0 Hz, 2H;
o-phenyl-H), 7.34 (t, J(H,H)=6.9 Hz, 2H; Ar CH), 7.12 (d, J(H,H)=
ACHTUNGTRENUN(NG H,H)=6.3 Hz, 2H; o-phenyl-H), 8.55 (d, J-
ACHTUNGTRENNUNG
(17):
A solution of propargyl bromide in toluene (80%, 3.8 mL,
35.3 mmol) was slowly added to a solution of N1,N7-bis(trifluoroacetyl)-
1,7-diamino-4-azaheptane (16; 8.53 g, 26.4 mmol) and triethylamine
(5.50 mL, 39.6 mmol) in dry THF (100 mL). The mixture was stirred at
RT for 3 d. The reaction mixture was poured into saturated aqueous
NaHCO3 (100 mL) and extracted with CHCl3 (3ꢄ100 mL). The com-
bined organic layers were washed with brine, dried over MgSO4, and
evaporated under reduced pressure to give 17 as a red oil (5.25 g,
14.5 mmol, 55%). 1H NMR (300 MHz, CDCl3, 258C): d=7.73 (s, 2H;
ACHTUNGTRENNUNG
G
ACHTUNGTRENNUNG
G
ACHTUNGTRENNUNG
6.5 Hz, 2H; Ar CH), 4.81 (s, 4H; 2ꢄCH2N3), 3.46 (m, 8H; 4ꢄethyl
CH2), 2.36 (s, 12H; 4ꢄmethyl CH3), 2.28 (s, 6H; 2ꢄmethyl CH3),
1.39 ppm (t, JACHTUNGTRENNUNG(H,H)=7.2 Hz, 12H; 4ꢄethyl CH3), NH (4H) not ob-
served; UV/Vis (CH2Cl2): lmax (eꢄ10ꢀ3)=391 (882), 511 (42.5), 546
(21.9), 580 (21.3), 634 nm (8.0 molꢀ1 Lcmꢀ1); MS (MALDI-TOF): m/z
calcd for C81H73N14O: 1257.61; found: 1257.62 [M+H]+.
NH), 3.44 (dt, J
(d, (H,H)=2.3 Hz, 2H; NCH2CCH), 2.60 (t,
CH2CH2N), 2.21 (t, (H,H)=2.3 Hz, 1H; CCH), 1.72 ppm (m, 4H;
CH2CH2CH2); 13C NMR (75.5 MHz, CDCl3, 258C): d=157.5 (q, J
(C,F)=
37 Hz, COCF3), 116.1 (q, J(C,F)=288 Hz, CF3), 77.2 (CH2CCH), 73.9
ACHUTGTNREN(NUG H,H)=6.2 Hz, JACHTNUGTRENNUNG
J
N
JACHTUNGTRENNUNG
4,5-Bis
ACHTUNGTRENNUNG
JACHTUNGTRENNUNG
porphyrinyl)-9,9-dimethylxanthene (10): A solution of CuAHCTUNGTRENNUNG
ACHTUNGTRENNUNG
(29.0 mg) and sodium acetate (35.0 mg) in methanol (2 mL) was added to
a solution of 8 (6.6 mg, 5.25 mmol) in chloroform (20 mL). The resulting
solution was heated at reflux for 4 h, then the solvent was removed by
rotary evaporation. The crude material was purified by column chroma-
tography to give compound 10 (7.0 mg, 5.07 mmol, 98%). UV/Vis
AHCTUNGTRENNUNG
(CCH), 51.8 (CH2CH2N), 41.1 (NCH2CCH), 38.9 (NHCH2CH2),
25.7 ppm (CH2CH2CH2); HRMS (ESI): m/z calcd for C13H18F6N3O2:
362.1298; found: 362.1290 [M+H]+.
(CH2Cl2):
lmax
(eꢄ10ꢀ3)=393
(447),
534
(14.6),
573 nm
N-(Prop-2-ynyl)-1,7-diamino-4-azaheptane (18): N-(Prop-2-ynyl)-N,N-
bis(trifluoroacetyl)-1,7-diamino-4-azaheptane (17; 696 mg, 1.61 mmol)
was treated with a mixture of MeOH and NH4OH (25%, 18 mL, 1:2)
and heated at reflux for 20 h. The residue was dried under high vacuum
to give product 18 as a colorless oil (272 mg, quantitative). 1H NMR
(5.4 molꢀ1 Lcmꢀ1); MS (MALDI-TOF): m/z calcd for C81H69Cu2N14O:
1381.44; found: 1381.39 [M+H]+.
4-[4-(10,15,20-Trimesityl-porphyrin-5-yl)-phenylcarbamoyl]-butyric acid
(13): Glutaric anhydride (302 mg, 2.51 mmol) was added to a solution of
5-(4-aminophenyl)-10,15,20-trimesitylporphyrin (12; 978 mg, 1.29 mmol)
in dry CH2Cl2 (90 mL). The mixture was stirred at RT for 20 h, then con-
centrated under reduced pressure. The product was purified by column
chromatography (silica gel, ethyl acetate) to afford the corresponding
acid in quantitative yield (1.11 g, 1.28 mmol, >99%). 1H NMR
(300 MHz, MeOD, 258C): d=3.46 (d, J
3.35 (s, 4H; NH), 2.99 (t, J(H,H)=7.5 Hz, 4H; CH2CH2N), 2.64 (t, J-
AHCTUNGTREN(NGUN H,H)=6.8 Hz, 4H; CH2CH2N), 2.63 (s, 1H; CCH), 1.82 ppm (tt, J-
ACHTUNGTREN(NNUG H,H)=2.4 Hz, 2H; NCH2CCH),
AHCTUNGTRENNUNG
AHCTUNGTRE(GNNNU H,H)=6.8, 7.5 Hz, 4H; CH2CH2CH2); HRMS (ESI): m/z calcd for
C9H20N3: 170.1652; found: 170.1649 [M+H]+.
(300 MHz, CDCl3, 258C): d=8.80 (d, J
CH), 8.70 (d, J(H,H)=4.8 Hz, 2H; b-pyrrole CH), 8.65 (s, 4H; b-pyrrole
CH), 8.15 (d, J(H,H)=8.1 Hz, 2H; phenyl-H), 7.86 (d, J(H,H)=8.1 Hz,
2H; phenyl-H), 7.79 (s, 1H; NHCO), 7.29 (s, 6H; mesityl CH), 2.63–2.55
(m, 13H; 3ꢄmethyl CH3 +CH2CH2CH2), 2.18 (m, 2H; CH2CH2CH2),
1.88 (s, 6H; 2ꢄmethyl CH3), 1.86 (s, 12H; 4ꢄmethyl CH3), ꢀ2.54 ppm
(brs, 2H; NH); MS (MALDI-TOF): m/z calcd for C58H56N5O3: 870.44;
found: 870.41 [M+H]+.
ACHTUNGTNER(NUNG H,H)=4.8 Hz, 2H; b-pyrrole
N-Tetra-alkylation of compound 20 by N-(3-bromopropyl)phthalimide
(21): A suspension of N4-(tert-butoxycarbonyl)-1,7-diamino-4-azaheptane
(20; 1.52 g, 6.58 mmol) and K2CO3 (4.56, 33.0 mmol) in acetonitrile
(275 mL) was heated at reflux for 2 h. N-(3-Bromopropyl)phthalimide
(8.84 g, 33.0 mmol) was added and the reaction mixture was stirred for
2 d. After cooling to RT, the solid was filtered and the solvent was evapo-
rated. The remaining oil was extracted with CH2Cl2/water and washed
with water. The organic layer was dried over MgSO4. The crude product
was purified by column chromatography (silica gel, CHCl3!5% MeOH/
95% CHCl3) to give 21 (4.47 g, 4.52 mmol, 69%). 1H NMR (300 MHz,
ACHTUNGTRENNUNG
G
ACHTUNGTRENNUNG
4-[4-(10,15,20-Trimesityl-porphyrin-5-yl)-phenylcarbamoyl]-butyric acid
2,5-dioxopyrrolidin-1-yl-ester (14): 4-[4-(10,15,20-Trimesityl-porphyrin-5-
yl)-phenylcarbamoyl]-butyric acid (13; 1.84 g, 2.11 mmol) was dissolved
in anhydrous CH2Cl2 (56 mL) under argon, then cooled to 08C. Dicyclo-
hexylcarbodiimide (480 mg, 2.33 mmol) and N-hydroxysuccinimide
(240 mg, 2.09 mmol) were added. The reaction mixture was warmed to
RT and stirred for 2 d. The solvent was evaporated and replaced with
ethyl acetate to precipitate the dicyclohexylurea formed during the reac-
tion. The organic layer was filtered and concentrated, then the crude
product was purified by column chromatography (silica gel, CHCl3) to
give 14 as a violet solid (1.23 mg, 1.28 mmol, 60%). 1H NMR (300 MHz,
CDCl3, 258C): d=7.73–7.59 (m, 16H; Pht), 3.64 (t, J
CH2NPht), 3.13 (m, 4H; NCH2CH2), 2.43 (t, (H,H)=6.6 Hz, 8H;
NCH2CH2), 2.36 (t, (H,H)=7.0 Hz, 4H; CH2CH2N), 1.73 (m, 8H;
ACHTUNGTREN(NGNU H,H)=7.2 Hz, 8H;
JACHTUNGTRENNUNG
JACHTUNGTRENNUNG
CH2CH2 CH2), 1.60 (m, 4H; CH2CH2CH2), 1.36 ppm (s, 9H; tBu-CH3);
13C NMR (75.5 MHz, CDCl3, 258C): d=168.2, 155.4, 133.7, 132.1, 123.0,
78.9, 51.3, 51.2, 45.6, 36.3, 28.4, 26.1, 25.8 ppm; HRMS (ESI): m/z calcd
for C55H62N7O10: 980.4553; found: 980.4586 [M+H]+.
Compound 22: Compound 21 (2.25 g, 2.30 mmol) was dissolved in CHCl3
(6.8 mL), then TFA (18.2 mL) was slowly added at 08C. After stirring for
5 h, the solvent and the TFA were removed under vacuum. The resulting
residue was dissolved in water and adjusted to pH>8 by addition of satu-
rated aqueous NaHCO3. The resulting solution was extracted with CHCl3
(5ꢄ20 mL) and the combined organic layers were dried over MgSO4, fil-
CDCl3, 258C): d=8.82 (d, J
(H,H)=4.8 Hz, 2H; b-pyrrole CH), 8.64 (s, 4H; b-pyrrole CH), 8.41 (s,
1H; NHCO), 8.15 (d, J(H,H)=8.4 Hz, 2H; phenyl-H), 7.94 (d, J(H,H)=
8.3 Hz, 2H; phenyl-H), 7.29 (s, 6H; mesityl CH), 2.94 (brs, 4H;
ACHTUNGTRENN(UNG H,H)=4.8 Hz, 2H; b-pyrrole CH), 8.69 (d,
JACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
Chem. Eur. J. 2011, 17, 14643 – 14662
ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
14659