-
1
8
3
.0 (d, J=9.5 Hz, 1H) , 7.4 (t, J=7.9 Hz, 2H), 7.0 (d, J=7.9 Hz,
H), 4.8 (m, 1H), 4.6 (s, 2H), 4.4 (m, 1H), 4.1 (m, 4H), 3.95 (d,
4H), 1.3 (m, 4H), 1.1 (m, 9H), 0.85 (t, J= 7.4 Hz, 6H). Ir (cm ) v
3285 (NH), 2918 (CH), 1642 (C=O), 1521 (NO ). CIMS m/z
) , 15) ; Anal. Calcd for
11S: C, 52.00; H, 6.48; N, 10.46. Found: C, 51.99; H,
6.52; N, 10.37.
2
+
+
J=5.5 Hz, 2H), 3.6 (m, 2H), 2.3 (t, J=7.3 Hz, 2H), 2.1-1.95 (m,
670.6 ((M + H) , 100), 687.6 ((M + NH
4
C H N O
29 43 5
-1
2
(
(
H), 1.7 (m, 4H), 1.4 (m, 4H), 1.0 (m, 6H). Ir (cm ) v 3284
NH), 2960 (CH), 1643 (C=O), 1531 (NO ). LSIMS m/z 720.2
(M + H) , 43), 742.2 ((M + Na) , 27); HRLSIMS: Calc for
2
+
+
4.1.2.16.
N-(tert-Butoxycarbonyl)-S-(2,4-dinitrophenyl)
glutathione di-n-butyl ester (16) was prepared according to
Method B using di-tert-butyl dicarbonate (1eq). Purification by
/MeOH : 9/1) gave the expected product as yellow
crystals. Yield 51%; mp 108-110C; H NMR (D MSO) 9.0 (s,
1H), 8.8 (m, 1H), 8.5 (m, 2H), 8.1 (d, J=8.7 Hz, 1H), 7.4 (d,
J=8.7 Hz, 1H), 4.8 (m, 1H), 4.2-3.9 (m, 7H), 3.6 (m, 2H), 2.3
(m, 2H), 2.0-1.8 (m, 2H), 1.6 (t, J=7.8 Hz, 4H), 1.4 (m, 13H), 1.0
C
C
5
32
H
H
45
N
4
O
12S: 737.2816, Found: 737.2811 ; Anal. Calcd for
12S: C, 53.39 ; H, 5.75; N, 9.73. Found: C, 53.28; H,
32
41
N
5
O
.40; N, 9.63.
.
PTLC (CHCl
3
1
4
.1.2.11.
N-(3-Phenylpropionyl)-S-(2,4-dinitrophenyl)
6
glutathione di-n-butyl ester (11) was prepared according to
Method A using 3-phenylpropionyl chloride. Trituration with
Et O gave the product as yellow crystals. Yield 70%; mp 143-
2
1
-1
1
2
5
2
2
1
1
7
9
46C; H NMR (D
6
MSO) 9.0 (s, 1H), 8.7 (m, 1H), 8.5 (m,
(t, J=7.8 Hz, 6H). Ir (cm ) v 3285 (NH), 2918 (CH), 1642
). LSIMS m/z 686.3 ((M + H) , 100), 708.3
43 5
((M + Na) , 85) ; Anal. Calcd for C29H N O12S: C, 50.78; H,
+
H), 8.4 (d, J= 7.0 Hz, 1H), 8.1 (d, J=8.7 Hz, 1H), 7.4-7.2 (m,
H), 4.8 (m, 1H), 4.3 (m, 1H), 4.1(m, 4H), 4.0 (d, J=7.0 Hz,
H), 3.6 (m, 2H), 2.9 (t, J= 7.8 Hz, 2H), 2.4 (t, J= 7.0 Hz, 2H),
.2 (t, J= 7.8 Hz, 2H), 2.0-1.8 (m, 2H), 1.6 (m, 4H), 1.4 (m, 4H),
(C=O), 1521 (NO
2
+
6.32 ; N, 10.22. Found: C, 50.40; H, 6.28 ; N, 9.82.
-1
4.1.2.17. N-(tert-Butylacetyl)-S-(2,4-dinitrophenyl)glutathione
di-n-butyl ester (17) was prepared according to Method B using
tert-butylacetyl chloride. Purification by PTLC (CHCl /MeOH :
3
/1) gave the product as yellow crystals. Yield 45%; mp 118-
MSO) 9.0 (s, 1H), 8.8 (m, 1H), 8.5 (m,
2H), 8.2 (d, J=8.7 Hz, 1H), 8.1 (d, J=9.6 Hz, 1H), 4.8 (m, 1H),
.0 (m, 6H). Ir (cm ) v 3294 (NH), 3058 (CH), 1644 (C=O),
541 (NO ). HRLISMS calc for C33 11S 717.2679, Found
17.2669; Anal. Calcd for C33 11S: C, 55.21; H, 6.04; N,
.76. Found: C, 55.20; H, 6.24; N, 9.83. .
2
43 5
H N O
43 5
H N O
9
1
1
20C; H NMR (D
6
4
.1.2.12. N-(trans-Cinnamoyl)-S-(2,4-dinitrophenyl)
glutathione di-n-butyl ester (12) was prepared according to
Method A using trans-cinnamoyl chloride. Trituration with Et
gave the product as yellow crystals. Yield 82%; mp 150-155C;
4.3 (m, HN-CH-CH
2H), 2.3 (m, 2H), 2.2 (s, 2H), 2.0-1.8 (m, 2H), 1.6 (t, 4H), 1.4 (m,
13H), 1.0 (t, 6H). Ir (cm ) v 3280 (NH), 2959 (CH), 1642
(C=O), 1531 (NO ). HRLSIMS: Calc for C30
683.2836. Found 683.2841; Anal. Calcd for C30
52.70; H, 6.63; N, 10.24. Found: C, 52.41; H, 7.23, N; 10.34.
2
), 4.1 (m, 4H), 4.0 (d, J=7.0 Hz, 2H), 3.6 (m,
2
O
-1
1
H NMR (D
d, J= 9.7 Hz, 1H), 7.6 (d, J= 8.0 Hz, 2H), 7.5 (m, 4H), 6.8 (d,
J=14.5 Hz, 1H), 4.8 (m, 1H), 4.4 (m, 1H), 4.2 (m, 4H), 4.0 (d,
6
MSO) 9.0 (s, 1H), 8.7 (m, 1H), 8.6 (m, 3H), 8.1
2
H
45
N
5
O
11S:
(
45 5
H N O11S: C,
2
4
H), 3.6 (m, 2H), 2.3 (t, J=7.0 Hz, 2H), 2.1-1.9 (m, 2H), 1.6 (m,
-1
4.1.2.18.
N-(Adamantyloxycarbonyl)-S-(2,4-dinitrophenyl)
H), 1.4 (m, 4H), 1.0 (m, 6H). Ir (cm ) v 3241 (NH), 2943
+
glutathione di-n-butyl ester (18) was prepared according to
Method using 1-adamantyl fluoroformate (1eq 3).
Purification by PTLC (CHCl /AcOH : 25/1) gave the product as
yellow crystals. Yield 51%; mp 72-74C; H NMR (D
.0 (s, 1H), 8.75 (m, 1H), 8.5 (d, J= 8.1 Hz, 2H), 8.05 (d, J=8.7
(CH), 1656 (C=O), 1577 (NO
2
). LISMS m/z 716.3 ((M + H) ,
5), 738.3 ((M + Na) , 100); HRLISMS: Calc for C33
16.2601, Found: 716.2593 ; Anal. Calcd for C33
5.37; H, 5.78 ; N, 9.79. Found: C, 55.03; H, 6.04; N, 9.71.
+
B
x
2
7
5
H
42
N
O
5
O
11S:
3
H
41
N
5
11S: C,
1
6
MSO)
9
4
.1.2.13. N-(Benzyloxycarbonyl)-S-(2,4-dinitrophenyl)
Hz, 1H), 7.35 (d, J=8.1 Hz, 1H), 4.75 (m, 1H), 4.15 (t, J= . Hz,
4H), 3.9 (d, J= 5.9 Hz, 3H), 3.6 (dd, J= 14.4, 5.9 Hz, 2H), 2.3
(bs, 3H), 2.1 (s, 2H), 2.0 (bs, 8H), 1.65 (bs, 10H), 1.4 (m, 4H),
glutathione di-n-butyl ester (13) was prepared according to the
previously described procedure .
2
4
-
1
0
1
H
2
9
.95 (t, J= 8.0 Hz, 6H). Ir (cm ) v 3284 (NH), 2912 (CH),
641 (C=O), 1514 (NO ). Anal. Calcd for C35
O: C, 54.43; H, 6.47; N, 9.06. Found: C, 54.39; H, 6.43 ; N,
.1.
4.1.2.14. N-(Indolepropionyl)-S-(2,4-dinitrophenyl)
2
49 5
H N O11S. 0.5
glutathione di-n-butyl ester (14) was prepared according to the
58
method described by Cabre et al
1eq), N,N-bis[2-oxo-3-oxazolidinyl]phosphonic chloride (BOP-
Cl) (1eq) as activator, Et (1eq) and (1eq) in a
dichloromethane solution (~20ml). Purification by PTLC
CHCl /MeOH : 9 / 1) gave the product as orange crystals. Yield
using indolepropionic acid
(
3
N
2
4.1.2.19. N,S-(2,4-Dinitrophenyl)glutathione di-n-butyl ester
(19) was prepared by thionyl chloride esterification of N, S-(2,4-
24
(
3
dinitrophenyl)glutathione in butanol (Method A). Trituration
with Et O gave the product as yellow crystals. Yield 85%; mp
130-135C; H NMR (D
1
6
1
2%; mp 145-150C; H NMR (D
6
MSO) 10.9 (m, 1H), 9.0 (s,
2
1
H), 8.8 (m, 1H), 8.7 (d, J= 9.0 Hz, 1H), 8.5 (d, 9.0 Hz, 1H), 8.4
6
MSO) 9.0 (m, 3H), 8.7 (t, J= 6.7 Hz,
(d, 9.0 Hz, 1H), 8.1 (d, 9.0 Hz, 1H), 7.6 (d, 9.0 Hz, 1H), 7.4 (d,
1H), 8.6 (d, J= 8.3 Hz, 1H), 8.5 (m, 1H), 8.3 (m, 1H), 8.0 (d, J=
8.3 Hz, 1H), 7.2 (d, J= 8.3 Hz, 1H), 5.0 (m, 1H), 4.8 (m, 1H),
4.2 (m, 2H), 4.1 (m, 2H), 3.9 (t, J= 6.7 Hz, 2H), 3.6 (m, 2H),
9.0 Hz, 1H), 7.0-7.2 (m, 3H), 4.7 (m, 1H), 4.3 (m, 1H), 4.1(m,
4
H), 4.0 (m, 2H), 3.6 (m, 2H), 3.0 (m, 2H), 2.3 (m, 2H), 2.0-1.8
-1
-1
(
3
m, 2H), 1.6 (m, 6H), 1.4 (m, 4H), 1.0 (m, 12H). Ir (cm ) v
285 (NH), 2958 (CH), 1643 (C=O), 1531 (NO ). ESIMS
m/z 757 ((M + H) , 20), 779 ((M + Na) , 100), 755 ((M - H) , 80),
2.3-2.2 (m, 4H), 1.7 (m, 4H), 1.4 (m, 4H), 1.0 (m, 6H). Ir (cm )
2
v 3283 (NH), 2959 (CH), 1642 (C=O), 1526 (NO
2
). LSIMS m/z
752.3 ((M + H) , 67), 774.2 ((M + Na) , 70); Anal. Calcd for
O: C, 46.80; H, 5.11; N, 12.74. Found: C, 47.24;
H, 4.89; N, 12.77.
+
+
-
+
+
-
7
5
91 ((M + Cl) , 85); Anal. Calcd for C35
0.72; H, 5.32; N, 10.14. Found: C, 50.69; H, 5.26; N, 10.32. .
H
44
N
6
O
11S.4H
2
O: C,
30 37 7 2
C H N O14S.H
4.1.2.15. N-(Trimethylacetyl)-S-(2,4-dinitrophenyl)
4.1.2.20.
N-(4-amino-6-chloro-1,3,5-triazin-2-yl)-S-(2,4-
glutathione di-n-butyl ester (15) was prepared according to
dinitrophenyl)glutathione di-n-butyl ester (20) was prepared
Method B using trimethylacetyl chloride (1.1eq). Trituration with
3
according to Method B using cyanuric chloride and CH CN
Et
2
O/ pet ether (40-60) gave the product as yellow crystals. Yield
replacing MeOH as the reaction solvent. After reaction for 4hr a
saturated solution of ammonia in MeOH (20 ml) was added to
the reaction and the solution stirred for a further 1 hr. The
solution was then evaporated and the residue dissolved in AcOEt
and filtered to remove insoluble material. The organic layer was
1
50%; mp 88-90C; H NMR (D MSO) 8.9 (s, 1H), 8.6 (t, J=5.6
6
Hz, 1H), 8.5 (d, J= 7.9 Hz, 2H), 8.0 (d, J= 9.0 Hz, 1H), 7.75 (d,
J= 7.9 Hz, 1H), 4.65 (m, 1H), 4.2 (m, 1H), 4.0 (m, 4H), 3.95 (d,
J=5.1 Hz, 2H), 3.6 (m, 2H), 2.3 (m, 2H), 2.0-1.8 (m, 2H), 1.5 (m,