VACUOLAR-TYPE (H+)-ATPase-INHIBITING COMPOUNDS, COMPOSITIONS, AND USES THEREOF
a technology of vacuolar-type (h+)-atpase inhibitors and compounds, applied in the field of vacuolar-type (h +)-atpase inhibitors, compositions, can solve the problems of rare h+)-atpase inhibitors, agents available for exploiting therapeutic opportunities, and purely synthetic approaches to identify novel vacuolar-type (h+)-atpase inhibitors
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example 1
[0105]This example illustrates a procedure for obtaining certain compounds of the present invention from marine sponges and tunicates.
[0106]The particular extract of a Haliclona sp. sponge selected from the NCI Natural Products Repository, Frederick, Md., for investigation in the present example showed an NCI 60-cell screening mean-graph (TGI) fingerprint that was highly correlated (TGI-COMPARE Pearson correlation coefficient greater than or equal to 0.7) to that of either salicylihalamide A or lobatamide A. The extract also showed proton NMR (500 MHz) resonances at chemical shift values (and multiplicities) recorded in CD3OD and referenced to residual methanol of: 6.65(d), 7.12(t), 6.72(d), 6.80(d), 5.68(d), and 6.87(dt). The selected extract was from a Haliclona sp. sponge that had been collected by P. Murphy in Southwestern Australia, 0.7 nautical miles off Rottnest Island, in March, 1989, at a depth of 15 meters. The sponge reportedly occurred as a green mass with amorphous lobe...
example 2
[0118]This example illustrates the structure proofs of particular compounds of the present invention.
[0119]Salicylihalamide A, such as obtained and characterized spectroanalytically in Example 1, was an amorphous solid with a molecular formula established by HREIMS as C26H33NO5. The 13C and DEPT NMR spectra (Table 2) showed 26 unique resonances: 5 quaternary, 14 methine, 5 methylene, and 2 methyl carbons. Chemical shift values further characterized two ester or amide carbonyls, 14 olefinic or aromatic carbons, and two oxygenated methines. Three exchangeable protons completed the proton count. The IR spectrum confirmed OH and / or NH (3288 cm−1) functionalities and suggested the presence of both an amide (1651 cm−1) and an intramolecularly hydrogen-bonded conjugated ester (1697 cm−1). The 13C (125 MHz) and 1H (500 MHz) NMR data for salicylihalamide A in C6D6 and CD3OD are illustrated below in Table 2.
TABLE 2HMBC (1H Correlation,HMBC (1H correlation,C#δc (C6D6)δH (multiplicity, Hz)(C6D6...
example 3
[0135]This example illustrates the isolation and structure of particular compounds of the present invention, Lobatamides C—F.
[0136]Lobatamides C—F were isolated from Aplidium lobatum, and the structures elucidated, according to procedures analogous to those described in Examples 1 and 2 for lobatamides A and B. Lobatamide C, was shown by HRFABMS to be isomeric with lobatamides A and B, namely C27H32N2O8. As with the latter compounds, the presence of three exchangeable protons was indicated by a CIMS deuterium exchange experiment using ND3 as the ionizing agent. The structural similarities among the three compounds were clearly evident from both the 13C and 1H NMR spectra (Tables 4-6). The 13C NMR spectrum of lobatamide C contained signals for all 27 carbons, including two ester carbonyls (δ 171.7, 169.9); an amide carbonyl (δ 164.1); 15 sp2 carbons, fourteen of which were accounted for a phenyl ring and four olefins; three oxygenated methine carbons (δ 73.7, 73.2, 72.9); three methy...
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