BELYKH et al.
582
11.4 Hz), 6.35 d (1H, trans-32-H, J = 18.0 Hz),
8.09 d.d (1H, 3-CH, J = 18.0, 11.4 Hz), 8.84 s (1H,
20-H), 9.68 s (1H, 5-H), 9.70 s (1H, 10-H). Mass spec-
trum, m/z (Irel, %): 681 (38) [M + 2]+, 680 (49) [M + 1]+,
679 (100) [M]+, 608 (10) [M + 2H – CH2CO2CH3]+,
607 (25%) [M + H – CH2CO2CH3]+, 606 (45) [M –
CH2CO2CH3]+, 548 (42) [M + H – HN(C2H5)2 –
CO2CH3]+, 547 (15) [M – HN(C2H5)2 – CO2CH3]+, 520
(75) [M + H – HN(C2H5)2 – CH2CH2CO2CH3]+ or
[M + H – HN(C2H5)2 – CO – CO2CH3]+, 519 (11) [M –
HN(C2H5)2 – CH2CH2CO2CH3]+ or [M – HN(C2H5)2 –
CO – CO2CH3]+.
13-(Butylcarbamoyl)chlorin e6 152,173-dimethyl
ester (III). A solution of 100 mg of pheophorbide a
methyl ester (I) in a mixture of 0.5 ml of butylamine
and 10 ml of tetrahydrofuran was stirred for 20 min
and was then treated as described above for compound
II. The product was isolated by chromatography on
silica gel using carbon tetrachloride–acetone (40:1) as
eluent. Yield 68 mg (60%). 1H NMR spectrum, δ, ppm:
–1.83 br.s (III-NH), –1.62 br.s (I-NH), 1.72 t (3H,
8-CH2CH3, J = 7.6 Hz), 1.71 d (3H, 18-CH3, J =
8.0 Hz), 2.08–2.58 m (4H, 17-CH2CH2), 3.76–3.85 m
(2H, 8-CH2), 3.32 s (3H, 7-CH3), 3.49 s (3H, 1-CH3),
3.57 s (3H, 12-CH3), 3.61 s (3H, 172-CO2CH3), 3.81 s
(3H, 151-CO2CH3); 1.06 t (3H, J = 7.6 Hz), 1.74–
1.85 m (4H), 3.85–3.91 m (2H, 13-CONHC4H9);
4.35 br.d (1H, 17-H, J = 8.8 Hz), 4.46 q (1H, 18-H, J =
6.8 Hz), 5.26 d and 5.55 d (1H each, 15-CH2, J =
19.2 Hz), 6.38 m (1H, CONH), 6.14 d.d (1H, cis-32-H,
J = 11.2, 1.6 Hz), 6.36 d.d (1H, trans-32-H, J = 17.6,
1.6 Hz), 8.09 d.d (1H, 3-CH, J = 17.6, 11.2 Hz), 8.81 s
(1H, 20-H), 9.65 s (1H, 5-H), 9.70 s (1H, 10-H). Mass
spectrum, m/z (Irel, %): 681 (40) [M + H2]+, 680 (25)
[M + H]+, 679 (100) [M]+, 648 (5) [M – OCH3]+, 620
(10) [M – CO2CH3]+, 607 (28) [M + H – H2NC4H9]+,
606 (45) [M – H2NC4H9]+, 579 (10) [M + H –
H2NC4H9 – CO]+, 548 (13) [M – H – H2NC4H9 – CO –
OCH3]+ or [M + H – H2NC4H9 – CO2CH3]+, 547 (15)
[M + H – H2NC4H9 – CO – CH3OH]+, 520 (35) [M +
H – H2NC4H9 – CO – CO2CH3]+ or [M + H – H2NC4H9 –
CH2CH2CO2CH3]+.
1.74 m (6H, 18-CH3, 8-CH2CH3), 2.07–2.59 m (4H,
17-CH2CH2), 3.32 s (3H, 7-CH3), 3.49 s (3H, 1-CH3),
3.56 s (3H, 12-CH3), 3.60 s (3H, 172-CO2CH3) 3.80 s
(3H, 151-CO2CH3) 3.76–3.85 m (2H, 8-CH2); 0.94 t
(3H), 1.36–1.45 m (6H), 1.74–1.86 m (4H), and 3.85–
3.91 m (2H, J = 6.8 Hz) (NC6H13); 4.35 br.d (1H,
17-H, J = 9.2 Hz), 4.47 q (1H, 18-H, J = 6.8 Hz),
5.26 d and 5.55 d (1H each, 15-CH2, J = 19.0 Hz),
6.38 m (1H, CONH), 6.14 d.d (1H, cis-32-H, J =
11.0 Hz), 6.35 d (1H, trans-32-H, J = 18.0 Hz), 8.08 d.d
(1H, 3-CH, J = 18.0, 11.0 Hz), 8.82 s (1H, 20-H), 9.65 s
(1H, 5-H), 9.70 s (1H, 10-H). Mass spectrum, m/z
(Irel, %): 709 (44) [M + H2]+, 708 (90) [M + H]+, 707
(100) [M]+, 649 (10) [M + H – CO2CH3]+, 648 (24)
[M – CO2CH3]+, 636 (28), 635 (63), 634 (56), 607 (24)
[M + H – HNC6H13]+, 606 (20) [M – HNC6H13]+,
549 (58) [M + H2 – HNC6H13 – CO2CH3]+, 548 (66)
[M + H – HNC6H13 – CO2CH3]+, 547 (35) [M –
HNC6H13 – CO2CH3]+, 520 (16) [M + H – H2NC6H13 –
CO – CO2CH3]+.
13-(Octylcarbamoyl)chlorin e6 152,173-dimethyl
ester (V). A solution of 50 mg of pheophorbide a
methyl ester (I) in a mixture of 0.5 ml of octylamine
and 10 ml of tetrahydrofuran was stirred for 20 min.
The mixture was then treated as described above for
compound II. The product was isolated by chromatog-
raphy on silica gel using carbon tetrachloride–acetone
1
(40:1) as eluent. Yield 20 mg (32%). H NMR spec-
trum, δ, ppm: –1.84 br.s (III-NH), –1.65 br.s (I-NH),
1.71 t (3H, 8-CH2CH3, J = 7.6 Hz), 1.71 d (3H,
18-CH3, J = 6.8 Hz), 2.08–2.61 m (4H, 17-CH2CH2),
3.31 s (3H, 7-CH3), 3.49 s (3H, 1-CH3), 3.76–3.85 m
(2H, 8-CH2), 3.56 s (3H, 12-CH3), 3.61 s (3H,
172-CO2CH3), 3.80 s (3H, 151-CO2CH3); 0.91 t (3H,
J = 7.2 Hz), 1.23–1.76 m (8H), 1.74–1.85 m (4H), and
3.85–3.91 m (2H) (NC8H17); 4.35 br.d (1H, 17-H, J =
7.6 Hz), 4.47 q (1H, 18-H, J = 7.6 Hz), 5.26 d and
5.55 d (1H each, 15-CH2, J = 18.8 Hz), 6.38 br.t (1H,
CONH, J = 4.0 Hz), 6.14 d.d (1H, cis-32-H, J = 11.6,
1.2 Hz), 6.36 d.d (1H, trans-32-H, J = 18.2, 1.2 Hz),
8.08 d.d (1H, 3-CH, J = 18.2, 11.6 Hz), 8.82 s (1H,
20-H), 9.65 s (1H, 5-H), 9.70 s (1H, 10-H). Mass spec-
trum, m/z (Irel, %): 737 (60) [M + H2]+, 736 (35) [M +
H]+, 735 [M]+ (100), 677 (10) [M + H – CO2CH3]+,
676 (15) [M – CO2CH3]+, 664 (29) [M + H2 –
CH2CO2CH3]+, 663 (42) [M + H – CH2CO2CH3]+, 662
(46) [M – CH2CO2CH3]+, 648 (21) [M + H – CH2CH2-
CO2CH3]+, 607 (12) [M + H – H2NC8H17]+, 606 (18)
13-(Hexylcarbamoyl)chlorin e6 152,173-dimethyl
ester (IV). A solution of 50 mg of pheophorbide a
methyl ester (I) in a mixture of 0.5 ml of hexylamine
and 10 ml of tetrahydrofuran was left to stand for 24 h
and was then treated as described above for diethyl-
amide II. The product was isolated by chromatography
on silica gel using carbon tetrachloride–acetone (40:1)
[M – H2NC8H17]+, 580 (16) [M + H2 – H2NC8H17
–
1
as eluent. Yield 20 mg (34%). H NMR spectrum, δ,
CO]+, 577 (30) [M + H – H2NC8H17 – OCH3]+, 576
(33%) [M + H – CH2CO2CH3 – CH2CH2CO2CH3]+ or
ppm: –1.84 br.s (III-NH), –1.67 br.s (I-NH), 1.68–
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 4 2010