Solid forms of 1-ethyl-3-(5-(5-fluoropyridin-3-yl)-7-(pyrimidin-2-yl)-1h-benzo[d]imidazol-2-yl)urea
A fluoropyridine, 137.5ppm technology, used in medical preparations containing active ingredients, antibacterial drugs, drug combinations, etc., can solve problems such as inability to treat and bacterial infections that are difficult to treat with antibiotics
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[0226] Form IA is prepared by precipitating compound 1 from an aqueous solution, for example by adjusting the acidic solution to pH 7. In some embodiments, the resulting solid can be triturated with a protic solvent such as methanol (eg, hot methanol). In some embodiments, the aqueous solution of Compound 1 is the product of a chemical synthesis of Compound 1, such as provided in Example 1.
[0227] Form IA is a triclinic P-I system, as observed by single crystal structural data at room temperature, with the following unit cell sizes:
[0228]
[0229] α=82.700(14)°, β=83.793(14)°, γ=72.628(13)°
[0230]
[0231] The single crystal structure of type IA is shown in Fig. 1a and 1b.
[0232] A representative XRPD of Form IA is atfigure 2 available in . Representative peaks observed in XRPD are provided in Table 1 below:
[0233] Table 1: Representative XRPD peaks for Form IA
[0234] horn
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d value
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Embodiment 1
[0320] Example 1: Synthesis of Compound 6, Form IA
[0321] Compound 6, Form IA was prepared using the synthetic scheme and experiments provided below. Form IA was provided by precipitating the synthesized product from an aqueous solution (ie, neutralizing the aqueous solution) as in the experiments provided following the synthetic scheme.
[0322] Analytical methods used throughout the experiments below include:
[0323] (A) HPLC on a Waters XBridge Phenyl column, 4.6x75mm, 3.5 microns. Mobile phase A was water / 1M ammonium formate, pH 7.0 (99:1). Mobile phase B was ACN / water / 1M ammonium formate, pH 7.0 (90:9:1). Gradient of 10-100% B in 10-12 min. Flow rate 1.2 mL / min. Detection at UV 245nm. T = 30°C.
[0324] (B) LC on Agilent RP18, 4.6x250mm column. mobile phaseACN / H 2 O / TFA (60:40:0.1). Detection at 265nm. Flow rate 1.0 mL / min. Runtime 22 minutes.
[0325] (C) GC on a HP-5 column. Use H 2 As a carrier gas, the temperature gradient is 8-2-10-240. Flow rate 1...
Embodiment 3
[0454] Example 3: Physical Characteristics of Type IIA
[0455] Form IIA is prepared by the following two crystallization methods.
[0456] Method I: EtOH / CH to compound 1 free base (173.5 mg) 2 Cl 2 (1:1, 20 mL) to the suspension was added ethanesulfonic acid (95%, from Aldrich, 1.0 equiv, 38 μL). The mixture was stirred at ~45°C until dissolved. The solution was then filtered, concentrated in vacuo, and the resulting oily residue was redissolved in CH 2 Cl 2 (10 mL), this solution was added dropwise to a stirred solution of diethyl ether (~100 mL). The resulting off-white precipitate was filtered, washed with diethyl ether under nitrogen, and the solid was dried under high vacuum at -40-45°C overnight to afford Form IIA (174.6 mg) as a brown powder: HPLC: Rt = 4.92 min. (Method: solvent B: 0.1% TFA / 1% MeCN / water, solvent D: 0.1% TFA / MeCN. Gradient 10% D to 90% D in 8 min. Flow rate 1 mL / min. Method duration 12 min. Column 1 (YMC 3x150).
[0457] 1 H NMR (CD 3 OD, 5...
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