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Synlett 2011(13): 1841-1844  
DOI: 10.1055/s-0030-1260947
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Reaction of β-Vinyl-meso-tetraphenylporphyrin with o-Quinone Methides

José C. J. M. D. S. Menezesa, Ana T. P. C. Gomesa, Artur M. S. Silvaa, Maria A. F. Faustinoa, Maria G. P. M. S. Nevesa, Augusto C. Toméa, Fernando de C. da Silvab, Vitor F. Ferreirab, José A. S. Cavaleiro*a
a QOPNA, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal
Fax: +351(234)370084; e-Mail: jcavaleiro@ua.pt;
b Departamento de Química Orgânica, Universidade Federal Fluminense, 24020-141 Niterói, Rio de Janeiro, Brazil
Further Information

Publication History

Received 9 May 2011
Publication Date:
14 July 2011 (online)

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Abstract

The hetero-Diels-Alder reaction of β-vinyl-meso-­tetraphenylporphyrinatozinc(II) with quinone methides generated in situ from Knoevenagel reaction of 2-hydroxy-1,4-naphthoqui­none, 4-hydroxycoumarin, and 4-hydroxy-6-methylcoumarin with paraformaldehyde and directly from o-hydroxybenzyl alcohol derivatives is reported.

Key words

porphyrin - o-quinone methide - naphthoquinone - coumarin - o-hydroxybenzyl alcohol - hetero-Diels-Alder

    References and Notes

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10

General Procedure for Preparing Compounds 8, 9, and 10a,b
In a round-bottom flask, equipped with a magnetic stirring bar, a solution of 2-hydroxy-1,4-naphthoquinone (1, 6.2 mg, 35.5 µmol) [or 4-hydroxycoumarins (2a, 5.7 mg; 2b, 6.2 mg; 35.5 µmol)], 1,4-dioxane (5 mL), paraformaldehyde (8.5 mg, 284 µmol), and porphyrin 4 (25 mg, 35.5 µmol) was heated at reflux until consumption of the starting porphyrin 4 (1-48 h). Quinone methide precursors were added at regular intervals. Dioxane was then removed under reduced pressure, CHCl3 (50 mL) was added to the residue, and the mixture was washed with sat. aq NaHCO3 (2 × 20 mL). The organic phase was concentrated under vacuum, and the residual crude product was purified by column chromatog-raphy on silica gel and subsequently by preparative TLC using CHCl3 as the eluent.

12

Unequivocal proton and carbon assignments for all compounds were based on two-dimensional COSY, HSQC, and HMBC experiments.
Data for {2-(5,10-Dioxo-3,4,5,10-tetrahydro-2 H -benzo[ g ]chromen-2-yl)-5,10,15,20-tetraphenylporphyrinato}zinc(II) (8)
¹H NMR (300 MHz, CDCl3): δ = 2.12-2.32 (m, 2 H, H-3′ and H-4′), 2.54-2.79 (m, 2 H, H-3′ and H-4′), 4.95 (d, J = 8.3 Hz, 1 H, H-2′), 7.49-7.54 (m, 1 H, Hp-Ph), 7.65-7.76 (m, 13 H, Hm,p-Ph, H-7′ and H-8′), 8.07-8.11 (m, 2 H, H-6′ and H-9′), 8.14-8.23 (m, 8 H, Ho-Ph), 8.73 (d, J = 4.8 Hz, 1 H, H-β), 8.89 (d, J = 4.8 Hz, 1 H, H-β), 8.92 (d, J = 4.8 Hz, 1 H, H-β), 8.93 (s, 2 H, H-12 and H-13), 8.95 (d, J = 4.8 Hz, 1 H, H-β), 9.12 (s, 1 H, H-3). ¹³C NMR (75 MHz, CDCl3): δ = 20.2 (C-4′), 29.4 (C-3′), 75.8 (C-2′), 120.4, 121.1, 121.2, 121.5, 121.7 (C-4′a and 2 C-quat), 126.0, 126.2, 126.3, 126.4, 126.6, 126.65, 126.7, 127.5, 128.3 (Co-Ph, Cm,p-Ph, C-6′, C-9′), 131.1; 131.6, 132.0, 132.2, 132.2, 132.5 (C-β), 132.9 (Co-Ph, C-3), 133.0, 133.3, 133.8, 134.4, 134.42, 134.7 (C-7′, C-8′, Co-Ph, Cm,p-Ph), 142.5, 142.6, 142.7,143.3 (C-1), 145.8, 147.9, 150.3, 150.4, 150.5, 150.6, 150.9, 156.2 (C-10a′), 179.5 (C-5′), 184.5 (C-10′); UV/vis (CHCl3): λmax (log ε) = 424 (4.94), 554 (4.57), 597 (3.96) nm. HRMS (ESI+): m/z [M + H]+ calcd for C57H37N4O3Zn: 889.2152; found: 889.2143.
Data for {2-(5,6-Dioxo-3,4,5,6-tetrahydro-2 H -benzo[ h ]chromen-2-yl)-5,10,15,20-tetraphenylporphyrinato}zinc(II) (9)
¹H NMR (500 MHz, CDCl3): δ = 2.16-2.24 (m, 2 H, H-3′ and H-4′), 2.58-2.61 (m, 1 H, H-3′), 2.71-2.75 (m, 1 H, H-4′), 5.08 (d, J = 10.2 Hz, 1 H, H-2′), 7.47-7.51 (m, 2 H, H-8′, 1 Hp-Ph), 7.55 (dt, J = 7.6, 1.6 Hz, 1 H, H-9′), 7.71-7.81 (m, 12 H, Hm,p-Ph, H-10′), 8.09 (dd, J = 7.6, 1.3 Hz, 1 H, H-7′), 8.16-8.24 (m, 8 H, Ho-Ph), 8.76 (d, J = 4.6 Hz, 1 H, H-β), 8.91 (d, J = 4.6 Hz, 1 H, H-β), 8.95 (s, 2 H, H-12 and H-13), 8.96 (d, J = 4.6 Hz, 1 H, H-β), 8.97 (d, J = 4.6 Hz, 1 H, H-β), 9.14 (d, J = 0.7 Hz, 1 H, H-3). ¹³C NMR (125 MHz, CDCl3): δ = 19.8 (C-4′), 29.8 (C-3′), 76.9 (C-2′), 114.2 (C-4′a), 120.4, 121.1, 121.4, 121.7, 124.2 (C-10′), 126.4, 126.5, 126.6, 126.7, 127.6, 127.7 (Cm,p-Ph), 128.6, 128.7 (Cm,p-Ph, C-7′), 129.9 (C-6′a), 130.6 (C-8′), 131.8, 132.27, 132.30, 132.33, 132.4, 132.43 (C-β), 132.6 (C-3, C-10′a), 133.4, 133.5, 134.36, 134.4, 134.42; 134.5 (C-o), 134.75 (C-9′), 142.3, 142.5, 142.7, 143.2 (C-1), 145.5, 147.7, 150.21, 150.4, 150.57, 150.6, 150.7, 150.8, 163.6 (C-10b′), 178.7 (C-5′), 179.7 (C-6′); UV/vis (CHCl3): λmax (log ε): 424 (4.85), 552 (4.52), 596 (3.96) nm. HRMS (ESI+): m/z [M + H]+ calcd for C57H37N4O3Zn: 889.2152; found: 889.2122.

13

Data for {2-(5-Oxo-2,3,4,5-tetrahydro-2 H -pyrano[3,2- c ]chromen-2-yl)-5,10,15,20-tetraphenylporphyrinato}zinc(II) (10a)
¹H NMR (500 MHz, CDCl3): δ = 2.25-2.29 (m, 2 H, H-3′ and H-4′), 2.61-2.67 (m, 2 H, H-3′ and H-4′), 5.04 (d, J = 8.5 Hz, 1 H, H-2′), 7.19 (ddd, J = 8.1, 7.2, 1.0 Hz, 1 H, H-9′), 7.34 (dd, J = 8.5, 1.0 Hz, 1 H, H-7′), 7.40-7.45 (m, 1 H, Hp-Ph), 7.49 (ddd, J = 8.5, 7.2, 1.4 Hz, 1 H, H-8′), 7.71-7.81 (m, 12 H, Hm,p-Ph, H-10′), 8.16-8.23 (m, 8 H, Ho-Ph), 8.75 (d, J = 4.6 Hz, 1 H, H-β), 8.90 (d, J = 4.6 Hz, 1 H, H-β), 8.94 (s, 2 H, H-12 and H-13), 8.95 (d, J = 4.6 Hz, 1 H, H-β), 8.97 (d, J = 4.6 Hz, 1 H, H-β), 9.15 (d, J = 0.5 Hz, 1 H, H-3). ¹³C NMR (125 MHz, CDCl3): δ = 20.9 (C-3′), 30.0 (C-4′), 75.9 (C-2′), 101.2 (C-4′a), 115.9 (C-10′a), 116.5 (C-7′), 120.5, 121.1, 121.3, 121.6, 122.5 (C-10′), 123.7 (C-9′), 126.4, 126.5, 126.6, 126.7, 127.6, 127.7, 128.5 (Cm,p-Ph), 131.2 (C-8′), 131.7, 132.3, 132.35, 132.6 (C-β), 133.4, 133.5, 134.37, 134.4, 134.42, 134.47, 134.5 (Co-Ph), 142.3, 142.4, 142.5, 142.7, 143.5 (C-1), 145.6, 147.8, 150.2, 150.4, 150.5, 150.6, 150.9, 152.4 (C-6′a), 160.7 (C-10′b), 163.4 (C-5′). UV/vis (CHCl3): λmax (log ε): 425 (4.94), 555 (4.54), 596 (4.00) nm. HRMS (ESI+): m/z [M + H]+ calcd for C56H37N4O3Zn: 877.2152; found: 877.2116.

15

General Procedure for Preparing 11a-c
A mixture of porphyrin 4 (10 mg, 14.2 µmol) and appropriate benzyl alcohol (3a, 1.7 mg; 3b, 2.2 mg; 14.2 µmol) was refluxed in o-dichlorobenzene (3 mL) in a sealed tube until consumption of starting porphyrin 4 (monitored by TLC) with addition of quinone methide precursors at regular intervals. After completion of reaction (6-26 h) the mixture was loaded on a silica column or preparative TLC plate and eluted with PE. Further elution with CHCl3 gave the corresponding adducts.

16

Data for [2-(Chroman-2-yl)-5,10,15,20-tetraphenylporphyrinato]zinc(II) (11a)
¹H NMR (300 MHz, CDCl3): δ = 2.14-2.26 (m, 1 H, H-3′), 2.43-2.55 (m, 1 H, H-3′), 2.56-2.74 (m, 2 H, H-4′), 4.95 (d, J = 9.6 Hz, 1 H, H-2′), 6.85-6.94 (m,2 H, H-6′ and H-8′), 7.07-7.21 (m, 2 H, H-5′ and H-7′), 7.53-7.59 (m, 1 H, Hp-Ph), 7.68-7.80 (m, 11 H, Hm,p-Ph), 8.15-8.23 (m, 8 H, Ho-Ph), 8.73 (d, J = 4.7 Hz, 1 H, H-β), 8.89 (d, J = 4.7 Hz, 1 H, H-β), 8.91 (d, J = 4.7 Hz, 1 H, H-β), 8.92 (s, 2 H, H-12 and H-13), 8.95 (d, J = 4.7 Hz, 1 H, H-β), 9.16 (s, 1 H, H-3). ¹³C NMR (75 MHz, CDCl3): δ = 26.2 (C-4′), 31.7 (C-3′), 74.2 (C-2′), 117.1 (C-8′), 120.0 (C-6′), 120.6, 120.9, 121.1, 121.5, 122.1 (C-4′a), 126.1, 126.5, 126.55, 127.0, 127.5, 128.1 (C-7′, Cm,p-Ph), 129.5 (C-5′), 131.5, 131.9, 132.0, 132.1, 132.4, 132.5 (C-β), 133.3, 133.7, 134.3, 134.4, 134.42, 134.6 (Co-Ph), 142.6, 142.7, 142.8, 145.9, 146.5 (C-1), 148.4, 150.0, 150.2, 150.3, 150.5, 150.9, 155.6 (C-8′a). UV/vis (CHCl3): λmax (log ε): 420 (4.98), 548 (4.59) nm. HRMS (ESI+): m/z [M + H]+ calcd for C53H37N4Ozn: 809.2253; found: 809.2273.

17

Data for {2-[8-(2-Hydroxybenzyl)chroman-2-yl)]-5,10,15,20-tetraphenylporphyrinato}zinc(II) (11c)
¹H NMR (300 MHz, CDCl3): δ = 2.17-2.75 (m, 4 H, H-3′and H-4′), 3.79 (d, J = 14.4 Hz, 1 H, CH2), 3.92 (d, J = 14.4 Hz, 1 H, CH2), 4.97 (dd, J = 10.4, 1.1 Hz, 1 H, H-2′), 6.47 (dd, J = 8.0, 1.1 Hz, 1 H, H-3′′), 6.75 (dt, J = 7.5, 1.1 Hz, 1 H, H-5′′), 6.84 (t, J = 7.4 Hz, 1 H, H-6′), 6.87 (s, 1 H, OH), 6.93-6.97 (m, 2 H, H-5′ and H-4′′), 7.12 (dd, J = 7.4, 1.4 Hz, 1 H, H-7′), 7.20 (dd, J = 7.5, 1.6 Hz, 1 H, H-6′′), 7.52-7.55 (m, 1 H, Hp-Ph), 7.66-7.76 (m, 11 H, Hm,p-Ph), 8.17-8.33 (m, 8 H, Ho-Ph), 8.77 (d, J = 4.7 Hz, 1 H, H-β), 8.89 (d, J = 4.7 Hz, 1 H, H-β), 8.93 (s, 2 H, H-β), 8.95 (s, 2 H, H-β), 9.26 (s, 1 H, H-3). ¹³C NMR (75 MHz, CDCl3): δ = 26.3 (C-4′), 30.5 (CH2), 31.2 (C-3′), 75.3 (C-2′), 116.4 (C-3′′), 120.3 (C-5′′), 120.6, 120.8 (C-6′), 121.07, 121.13, 121.4, 122.2 (C-4′a), 126.2, 126.4, 126.5 (Cm,p-Ph), 127.0 (Cm,p-Ph, C-1′′), 127.5, 127.6, 127.8 (C-8′), 128.1 (C-4′′,
C-7′, C-5′, Cm,p-Ph), 128.2, 130.4 (C-6′′), 130.5; 131.5, 132.06, 132.1, 132.2, 132.4 (C-β), 132.8 (C-3), 133.4, 133.6, 134.4, 134.5, 134.9 (Co-Ph), 142.8, 142.9, 144.9, 145.8, 148.1, 150.2, 150.2, 150.4, 150.4, 150.5, 150.8, 151.6 (C-8′a), 154.0 (C-2′′). UV/vis (CHCl3): λmax (log ε): 420 (5.72), 547 (4.59) nm. HRMS (ESI+): m/z [M]+ calcd for C60H42N4O2Zn: 914.2594; found: 914.2583.