154 Ali et al.
Calcad. for C18H21NO4S (347.12): C, 62.23; H, 6.09;
N, 4.03. Found: C, 61.94; H, 5.92; N, 3.89. MS: m/z
(FAB) 348 (M + H)+.
Found: C, 62.47; H, 5.87; N, 14.42.. MS: m/z (FAB)
310 (M + Na)+.
2-(2-Naphthyloxyacetamido)-4-(methylthio)bu-
tanoylhydrazine (15). From 11 (3.63 g). Yield: 2.98
Methyl 2-(2-naphthyloxyacetamido)-4-hydroxy-
propanoate (12). From L-serine acetate hydrochlo-
ride (1.55 g). Yield: method a, 2.30 g (72%); method
1
g (76%); mp 185–188◦C. H NMR (CDCl3): δ 8.37
(d, 1H, J = 8.0 Hz, NH); 7.92–7.80 (m, 3H, H-4,
H-5, H-8); 7.48 (t, 1H, J = 7.4 Hz, H-7); 7.40 (t, 1H,
J = 7.6 Hz, H-6); 7.30 (m, 2H, H-1, H-3); 4.70 (s, 2H,
CH2-10); 4.45 (m, 1H, H-13); 4.31 (br s, 2H, NH2);
2.58 (br s, 2H, CH2-16); 2.41 (m, 2H, CH2-15); 2.00
(s, 3H, SMe). Anal. Calcad for C17H21N3O3S (347.43):
C, 58.77; H, 6.09; N, 12.09. Found: C, 58.52; H, 5.93;
N, 11.84.. MS: m/z (FAB) 348 (M + H)+.
1
b, 0.170 g (65%); mp 145–147◦C. H NMR (CDCl3):
δ 7.73–7.61 (m, 4H, NH, H-4, H-5, H-8); 7.41 (ddd,
1H, J = 1.3 Hz, 8.0 Hz, H-7); 7.32 (ddd, 1H, J = 1.2
Hz, 8.0 Hz, H-6); 7.30 (dd, 1H, J = 2.5 Hz, 8.9 Hz,
H-3); 7.09 (d, 1H, J = 2.5 Hz, H-1); 4.73 (dt, 1H,
J = 3.8 Hz, 9.5 Hz, H-13); 4.60 (s, 2H, CH2-10);
3.96 (2 × dd, 2H, J 3.8 Hz, 11.3 Hz, CH2-15); 3.72
(br s, 3H, OAc, OH). 13C NMR (CDCl3): δ 172.9
(C-11); 169.1 (C-14); 150.7 (C-2); 132.9 (C-8a); 129.9
(C-4); 129.1 (C-4a); 127.7 (C-5); 127.0 (C-8); 126.7
(C-7); 124.4 (C-6); 118.2 (C-3); 107.9 (C-1); 67.4
(C-10); 62.9 (C-15); 52.7 (CO2Me); 17.1 (C-17). Anal.
Calcad. for C17H19NO5 (317.33): C, 64.34; H, 6.03;
N, 4.41. Found: C, 64.03; H, 5.89; N, 4.14. MS: m/z
(FAB) (C17H19NO5) 318 (M + H)+.
2-(2-Naphthyloxyacetamido)-3-hydroxypropano-
ylhydrazine (16). From 12 (3.19 g). Yield: 2.15 g
1
(71%); mp >250◦C. H NMR (CDCl3): 9.02 (s, 1H,
NH); 7.84 (d, 1H, J = 8.2 Hz, NH); 7.71–7.54 (m,
3H, H-4, H-5, H-8); 7.24 (t, 1H, J = 7.5 Hz, H-7);
7.13 (t, 1H, J = 7.5 Hz, H-6); 7.09 (d, 1H, J = 2.2
Hz, H-1); 7.03 (dd, 1H, J = 2.2 Hz, 8.9 Hz, H-3);
4.81 (8t, 1H, J = 5.6 Hz, OH); 4.45 (s, 2H, CH2-10);
4.14 (m., 1H, H-13); 4.02 (br s, 2H, NH2); 3.43 (m,
2H, CH2-15). Anal. Calcad for C15H17N3O4 (303.31):
C, 59.40; H, 5.65; N, 13.85. Found: C, 59.15; H, 7.73;
N, 12.85.. MS: m/z (FAB) 304 (M + H)+.
General Procedure of Preparation
of the Hydrazide Derivatives 13–16
To a solution of the ester derivatives 6 and
10–12 (10 mmol) in EtOH (20 mL) was added
N2H4·H2O (15 mmol), and the reaction mixture was
heated under reflux for 3 h. After cooling, the so-
lution was evaporated to dryness and the residue
was recrystallized from EtOH to give the desired hy-
drazide derivatives.
Methyl(2-Naphthyloxy)-3-O-(2,3,5,6-di-O-isopro-
pylidene-ꢀ-D-mannofuranos-1-yl) propanoate (19).
A solution of 12 (0.29 g, 0.90 mmol) and 18 (358
mg, 0.90 mmol) in dry CH2Cl2 (25 mL) was stirred
under nitrogen at room temperature for 5 min,
followed by the addition of TMSOTf (19.5 ꢁL, 0.09
mmol). After stirring for 2 h, a solid NaHCO3 was
added slowly, filtered, and the filtrate was washed
with water (30 mL), dried (Na2SO4), filtered and
evaporated to dryness. The residue was purified by
SiO2 column (20 g), using ethyl acetate/petroleum
ether as eluent to give 19 (0.36 g, 75%) as an oil.
1H NMR (CDCl3): δ 7.75–7.65 (m, 3H, H-4, H-5,
H-8); 7.42–7.28 (m, 3H, NH, H-6, H-7); 7.19 (dd,
1H, J = 2.3 Hz, 8.8 Hz, H-3); 7.11 (d, 1H, J = 2.3
Hz, H-1); 4.81 (br s, 2H, H-1ꢁ, H-13); 4.61 (s, 2H,
2-Naphthyloxyacetamidoacetohydrazide (13).
From 6 (2.73 g). Yield: 2.57 g (89%); mp 228–230◦C.
1H NMR (CDCl3): δ 9.13 (br s, 1H, NH); 8.39 (t, 1H,
J = 5.7 Hz, NH); 7.84–7.77 (m, 3H, H-4, H-5, H-8);
7.45 (ddd, 1H, J = 1.3 Hz, 6.9 Hz, H-7); 7.34 (ddd,
1H, J = 1.3 Hz, 6.9 Hz, H-6); 7.29 (dd, 1H, J = 2.6
Hz, H-3); 7.23 (d, 1H, J = 2.6 Hz, H-1); 4.64 (s, 2H,
CH2-10); 4.20 (br s, 2H, NH2); 3.78 (d, 2H, J = 5.9
Hz, CH2-13). Anal. Calcad for C14H15N3O3 (273.28):
C, 61.53; H, 5.53; N,15.38. Found: C, 61.21; H, 5.49;
N, 14.95. MS: m/z (FAB) 296 (M + Na)+.
ꢁ
ꢁ
ꢁ
ꢁ
CH2-10); 4.55 (dd, 1H, J4 ,5 = 3.5 Hz, J3 ,4 = 4.8 Hz,
H-4ꢁ); 4.31 (m, 2H, CH2-15); 4.03 (m, 1H, H-3ꢁ); 3.95
(dd, 1H, J5 ,6 = 4.2 Hz, J6 ,6 = 9.0 Hz, H-6ꢁ); 3.71 (s,
ꢁ
ꢁ
ꢁ
ꢁꢁ
ꢁ
ꢁꢁ
2-(2-Naphthyloxyacetamido)propanehydrazide
3H, OAc); 3.63 (dd, 1H, J5 ,6 = 3.3 Hz, H-6ꢁꢁ); 1.40
(2 × s, 6H, CMe2); 1.34, 1.21 (2 × s, 6H, CMe2). 13C
NMR (CDCl3): δ 169.7 (C-11); 168.0 (C-14); 154.9
(C-2); 134.1 (C-8a); 129.6 (C-4); 129.4 (C-4a); 127.5
(C-5); 126.8 (C-8); 126.5 (C-7); 124.2 (C-6); 118.0
(C-3); 112.5 (C-7ꢁ); 108.9 (C-7ꢁꢁ); 107.8 (C-1ꢁ); 105.9
(C-1); 84.6 (C-2ꢁ); 80.4 (C-4ꢁ), 79.1 (C-3ꢁ); 72.7 (C-5ꢁ),
67.3 (C-10); 66.6 (C-6ꢁ); 66.1 (C-15ꢁ); 62.6 (C-13);
(14). From 10 (2.87 g). Yield: 2.58 g (81%); mp
1
175–178◦C. H NMR (CDCl3): δ 8.05 (m, 1H, NH);
7.66–7.55 (m, 3H, H-4, H-5, H-8); 7.29–7.12 (m, 3H,
H-3, H-6, H-7); 7.06 (d, 1H, J = 2.5 Hz, H-1); 4.44
(s, 2H, CH2-10); 4.17 (m, 1H, H-13); 3.17 (br s, 2H,
NH2); 1.04 (t, 3H, J = 3.6 Hz, C13-Me). Anal. Calcad
for C15H17N3O3 (287.13): C, 62.71; H, 5.96; N, 14.63.