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LETTER
minimum amount of CH2Cl2. Hexane was added to the solution till
a precipitate appeared, compound 3 was isolated as a red solid (24
mg, 64%); mp 251 °C. Rf = 0.95 (Al2O3, 3% MeOH in CH2Cl2). 1H
NMR (500 MHz, CDCl3): δ = 10.12–9.96 (m, 4 H), 8.29–8.29 (m,
2 H), 6.38–6.14 (m, 4 H), 4.39–4.34 (m, 2 H), 4.16–3.98 (m, 10 H),
3.86–3.84 (m, 1 H), 3.67–3.65 (m, 6 H), 3.58–3.54 (m, 6 H), 2.61
(pent, J = 2.5 Hz, 2 H), 2.49 (pent, J = 2.6 Hz, 2 H), 1.21 (t, J = 7.1
Hz, 12 H), –3.87 (br s, 2 H) ppm. 13C NMR (125 MHz, CDCl3):
δ = 130.4, 130.3, 120.7, 120.5, 97.8, 97.7, 97.2, 96.8, 96.7, 96.5,
67.6 (d, JCP = 5.9 Hz), 63.8 (d, JCP = 5.7 Hz), 62.1, 35.9, 33.4 (d,
JCP = 6.4 Hz), 31.9, 22.7, 22.1, 16.1 (d, JCP = 6.7 Hz), 12.7, 12.6,
11.7, 11.5 ppm. ESI-HRMS: m/z calcd for C38H47N4O5P [M + H]+:
671.3359; found: 671.3357. UV/vis (CH2Cl2) λmax (ε) = 669
(1.23·103), 629 (4.95·103), 574 (6.81·103), 540 (1.09·104), 505
(1.28·104), 406 (1.51·105) (L·mol–1·cm–1).
(25% acetone in toluene). It was then dissolved in the minimum
amount of CH2Cl2. Hexane was added to the solution till a precipi-
tate appeared, compound Zn6 was isolated as a red solid (36 mg,
88%). 1H NMR (400 MHz, CDCl3): δ = 10.18 (s, 1 H), 10.05 (s, 1
H), 9.57 (d, J = 4.5 Hz, 1 H), 9.45 (t, J = 4.4 Hz, 2 H), 9.34 (d,
J = 4.5 Hz, 1 H), 9.28 (d, J = 4.5 Hz, 1 H), 9.22 (d, J = 4.6 Hz, 1 H),
9.00 (t, J = 4.2 Hz, 2 H), 8.06 (d, J = 8.2 Hz, 2 H), 7.89 (d, J = 8.1
Hz, 2 H), 5.35 (s, 1 H), 3.05 (m, 6 H), 2.70 (m, 14 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 151.1, 149.8, 149.7, 149.7, 149.4, 148.9,
148.4, 147.1, 141.9, 135.9, 132.0, 131.8, 131.7, 129.7, 129.5, 121.9,
118.4, 117.7, 105.9, 105.4, 65.9, 65.9, 53.3, 53.3, 53.2, 41.6, 41.5,
37.9 ppm.
5-(4-Bromophenyl)-15-[1,5-bis(dimethoxyphosphoryloxy)pent-
3-yl]porphyrin (6)
Compound 6 was prepared from Zn6 (25 mg, 0.029 mmol) accord-
ing to the literature26 (21 mg, 93%). 1H NMR (400 MHz, CDCl3):
δ = 10.31 (d, J = 7.8 Hz, 2 H), 9.85 (d, J = 4.8 Hz, 1 H), 9.67 (d,
J = 4.7 Hz, 1 H), 9.50 (m, 2 H), 9.40 (m, 2 H), 9.11–8.98 (m, 2 H),
8.18–8.07 (m, 2 H), 8.02–7.89 (m, 2 H), 5.90–5.73 (m, 1 H), 4.13–
4.06 (m, 2 H), 4.00–3.85 (m, 2 H), 3.66–3.35 (m, 14 H), 3.28–3.17
(m, 2 H), –2.88 (d, J = 25.9 Hz, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 148.1, 147.8, 147.08, 146.3, 145.9, 144.5, 143.7, 143.6,
139.9, 136.1, 133.1, 132.6, 132.1, 131.8, 131.1, 130.3, 130.0, 128.6,
128.4, 122.6, 118.6, 117.3, 105.6, 105.0, 66.46, 66.4, 54.1, 54.0,
53.9, 41.8, 41.7, 37.8 ppm.
6,7-Bis[3-(diethoxyphosphoryloxy)propyl]-1,3,5,8-tetramethyl-
2,4-divinylporphyrin (4)
Compound 4 was prepared from diol 1 (30 mg, 0.056 mmol) ac-
cording to the general procedure. The crude product was purified by
DCVC (25% acetone in toluene). It was then dissolved in the mini-
mum amount of CH2Cl2. Hexane was added to the solution till a pre-
cipitate appeared, compound 4 was isolated as a red solid (42 mg,
1
97%); mp 128 °C. Rf = 0.85 (Al2O3, 3% MeOH in CH2Cl2). H
NMR (500 MHz, CDCl3): δ = 10.00 (s, 1 H), 9.96 (s, 1 H), 9.87 (s,
1 H), 9.85 (s, 1 H), 8.19–8.08 (m, 2 H), 6.32–6.26 (dd, J = 17.7,
12.2 Hz, 2 H), 6.14–6.10 (dd, J = 11.4, 10.7 Hz, 2 H), 4.34–4.31 (m,
4 H), 4.16–4.10 (m, 12 H), 3.58–3.54 (m, 12 H), 2.66–2.61 (m, 4 H),
1.30 (t, J = 7.1 Hz, 12 H), –3.99 (br s, 2 H) ppm. 13C NMR (125
MHz, CDCl3): δ = 130.2, 130.2, 120.6, 97.9, 97.2, 96.9, 96.9, 95.8,
67.0 (d, JCP = 6.3 Hz), 63.7 (d, JCP = 4.8 Hz), 33.4, 33.3, 22.2, 16.1
(d, JCP = 6.3 Hz), 12.6, 11.7, 11.6 ppm. ESI-HRMS: m/z calcd for
C42H56N4O8P2 [M + Na]+: 829.3470; found: 829.3466. UV/vis
(CH2Cl2) λmax (ε) = 821 (4.63·102), 775 (2.60·102), 669 (1.72·103),
629 (4.8·103), 575 (6.34·103), 540 (1.03·104), 505 (1.22·104), 406
(1.49·105) (L·mol–1·cm–1). Anal. Calcd for C42H56N4O8P2: C, 62.52;
H, 7.00; N, 6.94. Found: C, 62.41; H, 7.03; N, 7.04.
5,10,15,20-Tetrakis(4-dimethoxyphosphonoxyphenyl)porphy-
rin (7)
Compound 7 was prepared from 5,10,15,20-tetrakis(4-hydroxyphe-
nyl)porphyrin23b (25 mg, 0.037 mmol) according to the general pro-
cedure, the reaction was performed with 24 equiv of both dimethyl
chlorophosphate and DABCO. Chromatography (2% MeOH in
CH2Cl2) of the crude product and subsequent recrystallization from
hexane–CH2Cl2 yielded a red solid (35 mg, 85%); mp dec >280 °C.
Rf = 0.70 (Al2O3, 2% MeOH in CH2Cl2). 1H NMR (400 MHz,
CDCl3): δ = 8.86 (s, 8 H), 8.19 (d, J = 8.2 Hz, 8 H), 7.73 (dd, J = 8.6
Hz, JCP = 1.0 Hz, 8 H), 4.08 (d, JCP = 11.3 Hz, 24 H), –2.84 (br s, 2
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 150.7 (d, JCP = 6.7 Hz),
138.9, 135.6, 119.1, 118.2 (d, JCP = 5 Hz), 55.2 (d, JCP = 6,2) ppm.
UV/vis (CH2Cl2): λmax (ε) = 645 (5.32·103), 590 (6.88·103), 549
(1.00·104), 514 (2.32·104), 447 (1.40·104), 418 (5.97·105), 292
(1.87·104), 253 (1.89·104) (L·mol–1·cm–1). ESI-HRMS: m/z calcd for
C52H50N4O16P4 [M + Na]+: 1133.2041; found: 1133.2065. Anal.
Calcd for C52H50N4O16P4 + H2O: C, 55.33; H, 4.64; N, 4.96. Found:
C, 55.33; H, 4.76; N, 5.14.
6,7-Bis[3-(dimethoxyphosphoryloxy)propyl]-1,3, 5,8-tetra-
methyl-2,4-divinylporphyrin (5)
Compound 5 was prepared from diol 1 (30 mg, 0.056 mmol) ac-
cording to the general procedure using dimethyl chlorophosphate.
The crude product was purified by DCVC (25% acetone in toluene).
It was then dissolved in the minimum amount of CH2Cl2. Hexane
was added to the solution till a precipitate appeared, compound 5
was isolated as a red solid (39 mg, 92%); mp 243 °C. Rf = 0.80
(Al2O3, 3% MeOH in CH2Cl2). 1H NMR (500 MHz, CDCl3):
δ = 10.18 (s, 1 H), 10.15 (s, 1 H), 10.05 (s, 1 H), 9.95 (s, 1 H), 8.31–
8.23 (m, 2 H), 6.37 (dd, J = 17.8, 1.4 Hz, 2 H), 6.18 (dd, J = 11.5,
1.3 Hz, 2 H), 4.38–4.33 (m, 4 H), 4.19 (t, J = 7.4 Hz, 4 H), 3.8 (d,
General Procedure for the Phosphorylation of Alcohols
To a solution of an alcohol (0.65 mmol) and DABCO (1.5 equiv,
0.98 mmol) in anhyd THF (2 mL), at r.t., dialkyl chlorophosphate
(1.5 equiv, 0.98 mmol) was added dropwise via syringe. The result-
ing mixture was stirred for 4 h at r.t. It was then poured into CH2Cl2
and washed with aq HCl (5%), sat. aq NaHCO3 and brine. The or-
ganic layer was dried over Na2SO4, filtered, and concentrated. The
residue was purified by silica gel chromatography.
J
HP = 11.1 Hz, 12 H), 3.70 (s, 3 H), 3.69 (s, 3 H), 3.62 (s, 3 H), 3.61
(s, 3 H), 2.66 (tt, J = 6.6, 6.9 Hz, 4 H), –3,77 (br s, 2 H) ppm. 13
C
NMR (125 MHz, CDCl3): δ = 130.2, 120.8, 98.1, 97.4, 97.1, 95.8,
67.3 (d, JCP = 5.8 Hz), 53.3 (d, JCP = 5.9 Hz), 33.4, 33.3, 22.1, 12.6,
11.7 ppm. ESI-HRMS: m/z calcd for C38H48N4O8P2 [M + Na]+:
773.2839; found: 773.2875. UV/vis (CH2Cl2): λmax (ε) = 669
(5.22·102), 630 (4.78·103), 576 (6.82·103), 541 (1.10·104), 506
(1.22·104), 408 (1.50·105) (L·mol–1·cm–1). Anal. Calcd for
C38H48N4O8P2 + H2O: C, 59.37; H, 6.56; N, 7.29. Found: C, 59.64;
H, 6.54; N, 7.50.
Diethyl[2-(4-methylphenylsulfonamido)propyl]phosphate (9)
Compound 9 was prepared from N-tosyl alaninol (150 mg, 0.65
mmol) according to the general procedure using diethyl chlorophos-
phate (2). The crude product was chromatographed (10% EtOAc in
hexanes) to afford phosphate 9 (225 mg, 94%) as a colorless oil.
Rf = 0.6 (SiO2, 3% MeOH in CH2Cl2). 1H NMR (500 MHz, CDCl3):
δ = 7.77 (d, J = 8.3 Hz, 2 H), 7.30 (dd, J = 8.5, 0.6 Hz, 2 H), 5.28
(d, J = 7.7 Hz, 1 H), 4.09 (q, J = 7.1 Hz, 4 H), 3.91–3.88 (m, 2 H),
3.61–3.31 (m, 1 H), 2.42 (s, 3 H), 1.35–1.31 (m, 6 H), 1.13 (d,
J = 6.8 Hz, 3 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 143.4,
137.9, 129.7, 127.1, 127.0, 70.1 (d, JCP = 5.8 Hz), 64.1 (d, JCP = 5.7
Hz), 64.0 (d, JCP = 5.7 Hz), 49.5, 49.4, 21.5, 17.9, 16.1, 16.0 ppm.
ESI-HRMS: m/z calcd for C14H24NO6PS [M + Na]+: 388.0954;
Zn(II) 5-(4-Bromophenyl)-15-[1,5-bis(dimethoxyphosphory-
loxy)pent-3-yl]porphyrin (Zn6)
Compound Zn6 was prepared from Zn(II) 5-(4-bromophenyl)-15-
(1,5-dihydroxypent-3-yl)porphyrin26 (30 mg, 0.048 mmol) accord-
ing to the general procedure, the reaction was performed with 12
equiv of both dimethyl chlorophosphate and DABCO. After reac-
tion a partial demetalation was observed, so to the reaction mixture
Zn(OAc)2 dihydrate (0.053, 0.24 mmol) was added and stirred at r.t.
for an additional 2 h. The crude product was purified by DCVC
Synlett 2012, 23, 2667–2671
© Georg Thieme Verlag Stuttgart · New York