Solid forms comprising N-(5-tert-butyl-isoxazol-3-yl)-N'-{4-[7-(2-morpholin-4-yl-ethoxy)imidazo[2,1-b][1,3]benzothiazol-2-yl]phenyl}urea, compositions thereof, and uses therewith
A form, solid technology, applied in medical preparations containing active ingredients, drug combinations, anhydride/acid/halide active ingredients, etc., can solve problems such as polymorphism sensitivity
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Embodiment 1
[0412] 6.1 Example 1.N-(5-tert-butyl-isoxazol-3-yl)-N'-{4-[7-(2-morpholin-4-yl-ethoxy) Synthesis of imidazo[2,1-B][1,3]benzothiazol-2-yl]phenyl}urea ("Compound B1")
[0413] A. The intermediate 2-amino-1,3-benzothiazol-6-ol was prepared according to a slight modification of the literature method of Lau and Gompf: J. Org. Chem. 1970, 35, 4103-4108. To a stirred solution of thiourea (7.6 g, 0.10 mol) in a mixture of 200 mL ethanol and 9 mL concentrated hydrochloric acid was added a solution of 1,4-benzoquinone (21.6 g, 0.20 mol) in 400 mL hot ethanol. The reaction mixture was stirred at room temperature for 24 hours, then concentrated to dryness. The resulting residue was triturated with hot acetonitrile and the resulting solid was filtered and dried.
[0414] The free base was obtained by dissolving the hydrochloride in water, neutralizing with sodium acetate, and collecting the solid by filtration. Purification by LCMS (M+H=167) and NMR afforded the product (2-amino-1,3-...
Embodiment 2
[0419] 6.2 Example 2.N-(5-tert-butyl-isoxazol-3-yl)-N'-{4-[7-(2-morpholin-4-yl-ethoxy) Alternative Synthesis of Imidazo[2,1-B][1,3]Benzothiazol-2-yl]phenyl}urea ("Compound B1")
[0420] A. To intermediate 2-(4-nitrophenyl)imidazo[2,1-b][1,3]benzothiazol-7-ol (2.24 g, 7.2 mmol) from Example 1B in ethanol (40mL) was added to the suspension in SnCl 2 ·H 2 O (7.90 g, 35 mmol), and heated to reflux. Concentrated HCl was added to the reaction mixture and gradually the form precipitated. The reaction mixture was heated to reflux for 20 hours, then allowed to cool to room temperature. The solution was poured onto ice, neutralized with 10% NaOH, and adjusted to about pH 6. The organic phase was extracted three times with ethyl acetate (80ml x 3). via MgSO 4 The extract was dried and concentrated to give a yellow solid (1.621 g, 80%). The solid was recrystallized from methanol to give pure product (1.355 g, 67%).
[0421]B. To a suspension of the intermediate from Step 2A (0...
Embodiment 3
[0424] 6.3 Example 3.N-(5-tert-butyl-isoxazol-3-yl)-N'-{4-[7-(2-morpholin-4-yl-ethoxy) Extensive Synthesis of Imidazo[2,1-B][1,3]Benzothiazol-2-yl]phenyl}urea (“Compound B1”)
[0425] Figure 66a with Figure 66b A multistep reaction procedure for the preparation of large quantities of compound B1 is described in and further described below.
[0426] Step 1: Preparation of 2-amino-6-hydroxybenzothiazole (intermediate 1) . 2-Amino-6-methoxybenzimidazole was reacted with hot aqueous HBr for about 3 hours, then the clear solution was cooled to ambient temperature overnight. The precipitated solid was collected, dissolved in hot water, and adjusted to pH between 4.5-5.5. The resulting solid was collected, dried and recrystallized from isopropanol. The second crop material was collected. The solid was dried in vacuo to afford Intermediate 1.
[0427] Step 2: Preparation of 2-(4-nitrophenyl)imidazo[2,1-b]benzothiazol-7 alcohol (Intermediate 2). 2-Amino-6-hydroxybenzoth...
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