N-alkyl-hydroxamic acid-isoindolyl compounds and their pharmaceutical uses
A compound and alkyl technology, applied in the field of N-alkyl-hydroxamic acid-isoindolyl compounds and their pharmaceutical applications, can solve problems such as limitations, effectiveness and side effects
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[0132] 4.1. Preparation of compounds
[0133] The compounds can be prepared using known methods generally used for the preparation of imides and 2,3-dihydro-1H-isoindolinones. However, the present invention also relates to improvements in the formation of the final compounds, which are described in more detail below.
[0134] Reaction of N-alkoxycarbonyldiimides with amines in the presence of a base such as sodium carbonate or sodium bicarbonate yields N-substituted imides essentially as described in: Shealy et al., Chem . & Ind., (1965) 1030-1031 and Shealy et al., J. Pharm. Sci. 57, 757-764 (1968). Alternatively, cyclic anhydrides can be reacted with appropriate amines to form imides. Cyclic imides can also be formed by refluxing an anhydrous tetrahydrofuran solution of a suitably substituted dicarboxylic acid monoamide with N,N'-carbonyldiimidazole. Alternatively, 2-bromomethyl-benzoate esters can be reacted with appropriate amines to give 2,3-dihydro-1H-isoindolinones a...
Embodiment 2
[0226] (1R)-2-[1-(3-ethoxy-4-methoxy-phenyl)-3-hydroxy-propyl]-7-nitro-2,3-dihydro-isoindole- 1-keto
[0227]
[0228] According to the method of Example 1, from (3R)-3-amino-3-(3-ethoxy-4-methoxy-phenyl)-propan-1-ol (3.0g, 13mmol), 2-bromo Preparation of methyl-6-nitro-benzoate (3.6g, 13mmol) and triethylamine (2ml, 14mmol) in DMF (40ml) (1R)-2-[1-(3-ethoxy-4 -methoxy-phenyl)-3-hydroxy-propyl]-7-nitro-2,3-dihydro-isoindol-1-one to give a yellow solid (4.1 g, yield 81%):
[0229] 1 H NMR (CDCl 3 )δ1.44(t, J=7Hz, 3H, CH 3 ), 2.13-2.31 (m, 2H, CH 2 ), 3.54-3.59(m, 1H, CHH), 3.71-3.77(m, 1H, NCHH), 3.87(s, 3H, CHH 3 ), 3.94(d, J=16Hz, 1H, NCHH), 4.06(q, J=7Hz, 2H, CH 2 ), 4.26 (d, J=16Hz, 1H, NCHH), 5.70 (dd, J=4, 11Hz, 1H, NCH), 6.85-6.99 (m, 3H, Ar), 7.55-7.77 (m, 3H, Ar ); 13 C NMR (CDCl 3 )δ14.76, 33.92, 45.80, 51.30, 55.98, 58.65, 64.63, 65.84, 111.39, 113.22, 119.75, 122.91, 124.13, 126.74, 130.66, 132.11, 143.84, 146.63, 2.468.682
Embodiment 3
[0231] (3R)-(tert-butoxy)-N-{3-(3-ethoxy-4-methoxyphenyl)-3-[7-nitro-1-oxodihydroisoindole- 2-yl]-propyl}carbonylamino(tert-butoxy)formate
[0232]
[0233] At room temperature, to (1R)-2-[1-(3-ethoxy-4-methoxy-phenyl)-3-hydroxy-propyl]-7-nitro-2,3-dihydro - Isoindol-1-one (4.1g, 11mmol), (tert-butoxy) carbonylamino (tert-butoxy) formate (3.0g, 13mmol) and triphenylphosphine in THF (40ml) solution, Diisopropyl azodicarboxylate (2.6ml, 13mmol) was added. After 30 min, the solvent was removed in vacuo. The residue was purified by chromatography (silica gel) to give (3R)-(tert-butoxy)-N-{3-(3-ethoxy-4-methoxyphenyl)-3-[7-nitro -1-Oxodihydroisoindol-2-yl]-propyl}carbonylamino(tert-butoxy) formate (5 g, yield 78%):
[0234] 1 H NMR (CDCl 3 )δ1.41(s, 9H, 3CH 3 ), 1.42(t, J=7Hz, 3H, CH 3 ), 1.51(s, 9H, 3CH 3 ), 2.39-2.52 (m, 2H, CH 2 ), 3.59-3.69 (m, 2H, CH 2 ), 3.84 (s, 3H, CH 3 ), 4.06 (q, J=7Hz, 2H, CH 2 ), 4.11 (d, J = 16Hz, 1H, NCHH), 4.43 (d, J = 16Hz, 1H, NCHH)...
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