Page 3 of 15
Photochemical & Photobiological Sciences
Please do not adjust margins
Journal Name
ARTICLE
(3.63) 564 (4.12) 605 (3.73) nm. HRMS (ESI) m/z calcd for 2-[ethyl-1-(but-2-en-1-yl)-7-bromine-4-oxo-1,4-dihydVroiewquAirnticoleliOnnel-ine
C59H42N5O3Zn [M + H]+ 932.2579, found 932.2592.
3-carboxylate]-5,10,15,20-tetraphenylporphyrinatozinc(II)
DOI: 10.1039/C9PP00102F
1
Yield: (24 %). H NMR (300 MHz, CDCl3) δ 8.97 (s, 1H, H-3), 8.93-
8.91 (m, 3H, β-H), 8.89-8.87 (m, 2H, β-H), 8.77 (d, J = 4.7 Hz, 1H, β-
H), 8.44 (s, 1H, H-2’), 8.27 (d, J = 8.6 Hz, 1H, H-5’), 8.21-8.18 (m, 6H,
H-o-Ph-5,10,15), 8.10-8.08 (m, 2H, H-o-Ph-20), 7.77-7.72 (m, 10H,
H-m,p-Ph-5,10,15), 7.68-7.65 (m, 3H, H-m,p-Ph-20, H-8’), 7.53 (dd, J
= 8.6, 1.6 Hz, 1H, H-6’), 6.41-6.38 (m, 2H, H-α,H-β), 4.69 (d, J = 3.9
Hz, 2H, CH2), 4.38 (q, J = 7.1 Hz, 2H, OCH2CH3), 1.40 (t, J = 7.1 Hz, 3H,
OCH2CH3). 13C NMR (75 MHz, CDCl3) δ 174.0 (C-4’), 165.7 (CO2Et),
150.9, 150.9, 150.8, 150.7, 150.6, 150.4, 149.5 (C-2’), 148.0, 146.3,
143.2, 143.0, 142.8, 141.0, 140.2, 134.6, 134.1, 132.6, 132.4, 131.9,
131.2 (C-3), 129.7 (C-5’), 128.7, 128.3, 128.0, 127.8, 127.7, 126.9,
126.8, 126.7, 122.0, 121.7, 121.3, 120.9, 119.3, 111.7, 61.2
(OCH2CH3), 56.4 (CH2), 14.6 (OCH2CH3). UV-vis (DMF): λmax (log ɛ)
433 (5.67) 475 (3.74) 524 (3.58) 574 (4.29) 604 (3.86) nm. HRMS
(ESI) m/z calcd for C59H41BrN5O3Zn [M + H]+ 1010.1684, found
1010.1708.
2-[ethyl-1-(but-2-en-1-yl)-6-chloro-4-oxo-1,4-dihydroquinoline-3-
carboxylate]-5,10,15,20-tetraphenylporphyrinatozinc(II) (5b) Yield:
1
(42 %). H NMR (500 MHz, CDCl3) δ 8.79 (s, 1H, H-3), 8.78-8.75 (m,
3H, β-H), 8.73-8.71 (m, 2H, β-H), 8.61 (d, J = 4.6 Hz, 1H, β-H), 8.52 (s,
1H, H-2’), 8.42 (d, J = 2.6 Hz, 1H, H-5’), 8.13-8.09 (m, 6H, H-o-Ph-
5,10,15), 7.99-7.98 (m, 2H, H-o-Ph-20), 7.70-7.63 (m, 10H, H-m,p-
Ph-5,10,15 e H-p-Ph-20), 7.61 (dd, J = 9.1, 2.6 Hz, 1H, H-7’), 7.54 (t, J
= 7,6 Hz, 2H, H-m-Ph-20), 7.47 (d, J = 9.1 Hz, 1H, H-8’), 6.36-6.34 (m,
2H, H-α, H-β), 4.71 (d, J = 3.8 Hz, 2H, CH2), 4.39 (q, J = 7.1 Hz, 2H,
OCH2CH3), 1.37 (t, J = 7.1 Hz, 3H, OCH2CH3). 13C NMR (125 MHz,
CDCl3+MeOD) δ 174.2 (C-4’), 165.6 (CO2Et), 150.74, 150.67, 150.57,
150.4, 150.2, 149.6 (C-2’), 147.8, 146.1, 143.8, 143.5, 143.3, 140.5,
137.8, 134.6, 134.0, 133.2, 132.22 (C-α or C-β), 132.16, 131.98,
131.94, 131.5, 130.8 (C-3), 130.2, 127.9, 127.44, 127.39, 127.1 (C-
5’), 126.8, 126.6 (C-7’), 126.5, 121.3, 121.1 (C-α or C-β) 120.8, 120.4,
120.2, 118.7 (C-8’), 111.1, 61.3 (OCH2CH3), 56.3 (CH2), 14.4
(OCH2CH3). UV-vis (DMF): λmax (log ɛ) 433 (5.56) 476 (4.38) 516
(3.81) 564 (4.25) 604 (3.87) nm. HRMS (ESI) m/z calcd for
C59H41ClN5O3Zn [M + H]+ 966.2189, found 966.2207.
3-[(E)-4-(3-oxoprop-1-en-1-yl]-5,10,15,20
tetraphenylporphyrinatozinc(II) (6) 1H NMR (500 MHz, CDCl3) δ
9.11 (s, 1H, H-3), 9.08 (d, J = 8.0 Hz, 1H, CHO), 8.91-8.89 (m, 6H, β-
H), 8.20-8.18 (m, 6H, H-o-Ph-5,10,15), 8.11-8.09 (m, 2H, H-o-Ph-20),
7.83-7.71 (m, 12H, H-m,p-Ph-5,10,15,20), 7.04 (d, J = 15.4 Hz, 1H, H-
α), 6.77 (dd, J = 15.4, 8.0 Hz, 1H, H-β). 13C NMR (125 MHz, CDCl3) δ
194.2 (CHO), 151.2, 151.16, 151.12, 151.1, 150.7, 150.1 (C-β), 149.8
(C-2’), 147.4, 146.4, 142.9, 142.5, 142.4, 138.9, 134.43, 134.41,
134.39, 134.1, 133.9, 132.8, 132.63, 132.61, 132.56, 132.51, 132.3,
132.0, 129.6 (C-α), 129.0, 128.5, 128.4, 128.2, 127.9, 127.6, 127.1,
126.6, 121.9, 121.4, 121.3, 120.8. HRMS (ESI) m/z calcd for
C47H31N4OZn [M + H]+ 731.1789, found 731.1770.
2-[ethyl-1-(but-2-en-1-yl)-7-chloro-4-oxo-1,4-dihydroquinoline-3-
carboxylate]-5,10,15,20-tetraphenylporphyrinatozinc(II) (5c) Yield:
1
(24 %). H NMR (300 MHz, CDCl3) δ 8.95 (s, 1H, H-3), 8.92-8.90 (m,
3H, β-H), 8.89-8.86 (m, 2H, β-H), 8.76 (d, J = 4.7 Hz, 1H, β-H), 8.38 (s,
1H, H-2’), 8.22- 8.16 (m, 6H, H-o-Ph-5,10,15), 8.13-8.08 (m, 3H, H-o-
Ph-20, H-5’), 7.76-7.70 (m, 10H, H-m,p-Ph-5,10,15, H-p-Ph-20), 7.68-
7.61 (m, 3H, H-m-Ph-20, H-8’), 7.49 (dd, J = 8.6, 1.5 Hz, 1H, H6’),
6.35 (s, 2H, H-α, H-β), 4.66 (d, J = 3.1 Hz, 2H, CH2), 4.29 (q, J = 7.1
Hz, 2H, OCH2CH3), 1.35 (t, J = 7.1 Hz, 3H, OCH2CH3). 13C NMR (75
MHz, CDCl3) δ 173.7 (C-4’), 165.4 (CO2Et), 150.9, 150.8, 150.8,
150.7, 150.6, 150.4, 149.4 (C-2’), 147.9, 146.2, 143.3, 143.0, 142.8,
140.8, 139.9, 139.1, 134.6, 134.0, 132.5, 132.4, 131.8, 131.0 (C-3),
129.5, 128.2, 127.7, 127.6, 127.4, 126.8, 126.8, 126.7, 125.7 (C-6’),
121.9, 121.2, 120.8, 120.8, 116.2 (C-8’), 111.5, 61.1 (OCH2CH3), 56.7
(CH2), 14.5 (OCH2CH3). UV-vis (DMF): λmax (log ɛ) 432 (5.45) 476
(4.50) 515 (3.88) 564 (4.18) 604 (3.86) nm. HRMS (ESI) m/z calcd for
C59H41ClN5O3Zn [M + H]+ 966.2189, found 966.2211.
3-[4-(2-(carboxyamino)vinyl]-5,10,15,20-
tetraphenylporphyrinatozinc(II) (7) 1H NMR (500 MHz, CDCl3) δ
8.95 (s, 1H, H-3), 8.93-8.90 (m, 3H, β-H), 8.89-8.87 (m, 2H, β-H),
8.83 (d, J = 4.7 Hz, 1H, β-H), 8.21-8.18 (m, 6H, H-o-Ph-5,10,15), 8.08-
8.05 (m, 2H, H-o-Ph-20), 7.77-7.70 (m, 12H, H-m,p-Ph-5,10,15,20),
6.36-6.33 (m, 2H, H-α, H-β), 4.53 (d, J = 5.0 Hz, 1H, CH2). 13C NMR
(125 MHz, CDCl3) δ 171.1 (NHCO2H), 156.5, 153.4, 150.9, 150.7,
150.5, 150.4, 150.4, 150.3, 148.5, 146.9, 143.1, 143.0, 142.9, 142.7,
137.8, 134.5, 134.1, 132.5, 132.3, 132.2, 132.1, 131.7, 131.2 (C-α or
C-β), 131.0, 130.8, 128.1, 127.6, 127.6, 126.9, 127.7, 124.4 (C-α or
C-β), 121.6, 121.2, 121.1, 120.6, 118.8, 65.7 (CH2). HRMS (ESI) m/z
calcd for C48H33N5O2Zn· M+• 775.1926, found 775.2043.
2-[ethyl-1-(but-2-en-1-yl)-6-bromine-4-oxo-1,4-dihydroquinoline-
3-carboxylate)-5,10,15,20-tetraphenylporphyrinatozinc(II)
(5d)
1
Yield: (46 %). H NMR (300 MHz, CDCl3) δ 8.83 (s, 1H, H-3), 8.80-
8.77 (m, 3H, β-H), 8.75-8.73 (m, 2H, β-H), 8.62 (d, J = 4.7, 1H, β-H),
8.59 (d, J = 2.4 Hz, 1H, H-5’), 8.51 (s, 1H, H-2’), 8.13-8.10 (m, 6H, H-
o-Ph-5,10,15), 8.00-7.98 (m, 2H, H-o-Ph-20), 7.74 (dd, J = 9.0, 2.4
Hz, 1H, H-7’), 7.70-7.62 (m, 10H, H-m,p-Ph-5,10,15, H-p-Ph-20),
7.57-7.52 (m, 2H, H-m-Ph-20), 7.39 (d, J = 9.1 Hz, 1H, H-8’), 6.35 (s,
2H, H-α, H-β), 4.69 (d, J = 2.6 Hz, 2H, CH2), 4.39 (q, J = 7.1 Hz, 2H,
OCH2CH3), 1.38 (t, J = 7.1 Hz, 3H, OCH2CH3). 13C NMR (75 MHz,
CDCl3) δ 173.4 (C-4’), 165.8 (CO2Et), 150.8, 150.8, 150.6, 150.5,
150.3, 149.4 (C-2’), 147.9, 146.2, 143.5, 143.2, 143.0, 140.8, 138.2,
135.6, 134.6, 134.1, 132.4, 132.2, 132.2, 132.0, 131.7, 131.0 (C-3),
130.7, 130.6, 128.2, 127.6, 127.6, 126.7, 126.6, 121.7, 121.4, 121.1,
120.6, 119.3, 118.5 (C-8’), 111.6, 61.3 (OCH2CH3), 56.6 (CH2), 14.6
(OCH2CH3). UV-vis (DMF): λmax (log ɛ) 431 (5.53) 475 (3.68) 523
(3.55) 564 (4.22) 604 (3.82) nm. HRMS (ESI) m/z calcd for
C59H41BrN5O3Zn [M + H]+ 1010.1684, found 1010.1697.
Hydrolysis and demetallation of conjugates 5a-e. General
Procedure
Into a flask with reflux condenser were added the conjugates 5a-e
(10 mg), NaOH (160 mg, 4000 mmol), EtOH (4 mL). The reaction was
kept under stirring and reflux for 2 hours. After that time the
mixture was neutralized with 50 mL of dilute citric acid solution and
extracted with 100 mL of CH2Cl2. The organic phase was dried with
anhydrous Na2SO4 and the solvent was evaporated. To the obtained
residue was added CH2Cl2 (4 mL) and TFA (0.5 mL). The mixture was
vigorously stirred at room temperature for 30 minutes, after which
it was neutralized with 100 mL of saturated aqueous solution of
NaHCO3. The organic extracts were dried over anhydrous Na2SO4.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins