TRPV1 antagonists including dihydroxy substituent and uses thereof
A technology of methyl and fumaric acid, applied in medical preparations containing active ingredients, anti-inflammatory agents, non-central analgesics, etc.
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[1011] The preparation of solvates is known in the art. For example "Preparation and Crystal Characterization of a Polymorph, a Monohydrate, and an EthylAcetate Solvate of the Antifungal Fluconazole," by Caira et al., J.Pharmaceut.Sci., 93(3) : 601-611 (2004) describes the preparation of solvates of fluconazole and ethyl acetate and with water. Similar preparations of solvates, hemisolvates, hydrates, etc. are described in "Preparation and Physical Chemical Characterization of 5 Niclosamide Solvates and 1 Hemisolvate," by Van Tonder et al. 5 (1): Article 12 (2004) and "Over one hundred solvates of sulfatethiazole," by Bingham et al., Chem. Comm., pp. 603-604 (2001). In one embodiment, a non-limiting process involves dissolving a compound of formula (I) in a desired amount of the desired solvent (organic solvent, water or a mixture thereof) at a temperature of about 20°C to about 25°C, cooling the solution The rate is sufficient to form crystals, which are isolated by known m...
Embodiment 1
[1238] 5.1 Example 1: Preparation of Compound C126(r)
[1239]
[1240] tert-butyl 4-(5-bromo-3-fluoropyridin-2-yl)-piperazine-1-carboxylate (103)
[1241] 5-Bromo-2-chloro-3-fluoropyridine (101, 8.0 g, 38.0 mmol, Oakwood Products, Inc., West Columbia, SC) in DMSO (32 mL) was mixed with tert-butylpiperazine-1-carboxylate The reaction mixture of butyl ester (102, 7.08 g, 38.02 mmol, Sigma-Aldrich) was heated at 100°C for 16 hours. The mixture was cooled to a temperature of about 25 °C, poured on cold 10% aqueous sodium carbonate and extracted with EtOAc. The organic layer was washed with water, washed with brine, dried over sodium sulfate and concentrated to afford 15.5 g of semi-solid. The semisolid was washed with hexane and filtered. The filtrate was concentrated to provide 7.5 g of residue. The residue was chromatographed on a silica gel column eluting with a gradient from 100% hexanes to 10:90 EtOAc:hexanes to afford 103 as a solid (24% yield).
[1242] (E) tert-bu...
Embodiment 2
[1254] 5.2 Example 2: Compounds B122(j), B122(k), B122(o), B122(p), B125(j), B125(k), B125(o), B125(p), B155(h) , B155(j), B155(o), B158(j), B158(o), C4(r), C123(r), C125(r) and C170(r)
[1255] The following compounds of formula (I) were prepared using procedures similar to those described in Example 1 above.
[1256] B122(j): (R)-N-(benzo[d]thiazol-2-yl)-4-{5-[(1S,2S)-1,2-dihydroxypropyl]-3-fluoropyridine -2-yl}-3-methylpiperazine-1-carboxamide.
[1257] 1 HNMR (DMSO-d 6 )δ: 0.87 (3H, d, J = 6.1Hz), 1.07 (3H, d, J = 6.4Hz), 3.08-3.45 (3H, m), 3.75-3.54 (2H, m), 3.94-4.30 (3H , m), 4.35(1H, t, J=5.0Hz), 4.66(1H, d, J=4.6Hz), 5.28(1H, d, J=4.4Hz), 7.20(1H, t, J=7.4Hz ), 7.70-7.28 (3H, m), 7.72-7.91 (1H, m), 7.96 (1H, s), 11.33 (1H, brs). LC / MS (M+1): m / z=447.
[1258] B122(k): (S)-N-(benzo[d]thiazol-2-yl)-4-{5-[(1S,2S)-1,2-dihydroxypropyl]-3-fluoropyridine -2-yl}-3-methylpiperazine-1-carboxamide.
[1259] 1 HNMR (DMSO-d 6 )δ: 0.87 (3H, d, J = 6.4Hz), 1.07 (3H, d, J =...
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