6
P. SAKTHIPRIYA AND N. ANANTHI
Fig. 2. (a) HPLC chromatogram of racemic 2-chloro phenyl oxirane. (b) HPLC chromatogram of (S)-2-chloro phenyl oxirane
+30.2° (c 1, CHCl3). FT IR: n, cm-1 3138 (-NH), 2872
EXPERIMENTAL
(-CH), 1073 (-CO). 1H NMR (500 MHz; CDCl3; Me4Si):
dH, ppm -2.51 (2H, s, pyrrole-NH), 1.27 (24H, s, -CH3),
General remarks
4.03; 3.77 (8H, m, -CH2), 4.58 (4H, t, -CH), 8.83 (8H, d,
pyrrole-CH). 13C NMR: dC, ppm 26.3, 68.6, 73.8, 75.2,
80.1, 110.4, 115.0, 115.2, 119.9, 123.2, 125.1, 125.18,
128.0, 128.09, 134.7, 151.2. HR MS: m/z 710.78 (calcd.
for [M + H]+ 710.82).
1H and 13C NMR spectra were recorded in CDCl3 with
a BRUKER AMX-400 MHz instrument using TMS as
an internal standard. Commercial Precoated Silica Gel
(Merck 60F-254) plates were used for TLC. 60–120 mesh
silica gel was used for column chromatography. Specific
rotations were recorded with a Rudolph autopol III
polarimeter. Enantiomeric excess was determined with a
Shimadzu Prominence HPLC 2010A instrument (Chiral
column: Chiralcel OD, Chiralcel OJ and Chiralpak OT,
Mobile phase: 95:5 hexane/i-PrOH, flow rate: 1 mL/
min, UV detector l = 210 nm). FT-IR spectra were
recorded with a Shimadzu Prestige 20 IR spectrometer.
All the chemicals were purchased from Merck. All the
solvents used were purchased from Merck and used after
purification.
Synthesis of 5,10,15,20-tetrakis[(2S)-1,4-dioxa-
spiro-5-decanyl]porphyrin 1b. Yield 0.523 g (42%).
[a]58925 +47.1° (c 1, CHCl3). FT IR: n, cm-1 3148 (-NH),
1
2870 (-CH), 1083 (-CO). H NMR (500 MHz; CDCl3;
Me4Si): dH, ppm -2.71 (2H, s, pyrrole-NH), 1.49; 1.47
(8H, m, -CH2), 1.58; 1.33 (16H, m, -CH2), 1.72; 1.62
(16H, m, -CH2), 4.03; 3.77 (8H, m, -CH2), 4.58 (4H, t,
-CH), 8.52 (8H, d, pyrrole-CH). 13C NMR: dC, ppm 23.5,
26.3, 35.6, 69.2, 74.4, 75.8, 80.7, 110.8, 115.0, 115.2,
119.9, 123.2, 125.1, 125.16, 128.01, 128.12, 134.7,
151.2. HR MS: m/z 871.04 (calcd. for [M + H]+ 871.07).
Synthesis of 5,10,15,20-tetrakis[(4R,5R)-4-yl-2-
oxo-hexahydro-2H-cyclopenta[b]furan-5-ylbenzoate]
porphyrin 1c. Yield 0.543 g (46%). [a]589 +50.0°
General procedure for the synthesis of meso
substituted chiral porphyrins 1(a–d)
25
(c 1, CHCl3). FT IR: n, cm-1 3138 (-NH), 2875 (-CH),
1
1710 (-C=O), 1086 (-CO). H NMR (500 MHz; CDCl3;
Chiral porphyrin ligands 1(a–d) were synthesized
from equimolar amount of pyrrole and different chiral
aldehydes according to Lindsey method using TFA and
p-chloranil (Scheme 1) [55]. The reaction was carried
out at room temperature in dry CH2Cl2 under nitrogen
atmosphere with trace acid (TFA) catalyst for 1 h. Then
stoichiometric amount of p-chloranil was added and the
solution was refluxed at 40°C for 1 h. Then the solvent
was evaporated and the crude was purified by column
chromatography using 85:15 hexane, ethyl acetate as an
eluent. The chiral porphyrins were obtained as purple
crystals in 40–50% yield.
Me4Si): dH, ppm -2.63 (2H, s, pyrrole-NH), 2.11 (4H, m,
-CH), 2.29 (8H, m, -CH2), 2.39 (8H, m, -CH2), 2.77 (4H,
t, -CH), 4.01 (4H, m, -CH), 4.28 (4H, m, -CH), 7.56 (8H,
m, -Ph), 7.65 (4H, m, -Ph), 8.07 (8H, m, -Ph), 8.869
(8H, d, pyrrole-CH). 13C NMR: dC, ppm 33.0, 33.3, 38.0,
38.8, 50.0, 79.0, 79.8, 119.9, 120, 120.2, 123.2, 125.11,
125.17, 128, 128.12, 128.6, 129.9, 130.1, 133.0, 134.6,
151.1, 165.9, 176.1. HR MS: m/z 1287.28 (calcd. for
[M + H]+ 1287.32).
Synthesis of 5,10,15,20-tetrakis[(S)-3-benzyl-2-
methyl-4-phenylbutyl]porphyrin 1d. Yield 0.610 g
(47%). [a]58925 +39.1° (c 1, CHCl3). FT IR: n, cm-1 3133
(-NH), 2870 (-CH). 1H NMR (500 MHz; CDCl3; Me4Si):
dH, ppm -2.62 (2H, s, pyrrole-NH), 1.20 (12H, d, -CH3),
3.48 (4H, m, -CH), 3.62 (16H, s, -CH2), 7.23 (16H, m,
Ph), 7.33 (16H, m, Ph), 7.26 (8H, m, Ph), 8.75 (8H, d,
Synthesis
Synthesis of 5,10,15,20-tetrakis [(R)-2,2-dimethyl-
1-oxolonyl]porphyrin 1a. Yield 0.545 g (40%). [a]589
25
Copyright © 2016 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2016; 20: 6–8