Crystal form of cyclohexane derivative maleate
A maleate and derivative technology, applied in the field of medicinal chemistry, can solve the problems of the preparation process and the drug-forming process, chemical stability, poor crystal stability, etc., and achieve the effects of good hygroscopicity and good crystal stability.
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Embodiment 1
[0063] Example 1: N'-[trans-4-[2-[7-(benzo[b]thiophene)-4-yl-1-piperazine]ethyl]cyclohexyl]-N,N-dimethyl Preparation of urea (compound of formula I)
[0064] The preparation of the free base refers to Example 5 of CN106518841A.
[0065] Preparation of 1-benzo[b]thiophene-4-piperazine hydrochloride
[0066]
[0067] 7.20g 7-bromobenzo[b]thiophene, 19.9g piperazine, 4.70g sodium tert-butoxide, 0.32g (R)-(+)-2,2'-bis(diphenylphosphino)-1 , a mixture of 1′-binaphthalene (BINAP), 0.63 g of dipalladium tris(dibenzylideneacetone) and 150 ml of toluene was refluxed for 1 hour under a nitrogen atmosphere. Pour 150ml of water into the reaction solution, then extract with 100ml×3 ethyl acetate, wash with water, dry over anhydrous magnesium sulfate, and evaporate the solvent under reduced pressure (0.01MPa, 45°C). The residue was purified by silica gel column chromatography (dichloromethane:methanol:25% aqueous ammonia=100:10:1) to obtain 4.60 g of 1-benzo[b]thiophen-4-yl-piperazine...
Embodiment 2
[0075] Example 2: N'-[trans-4-[2-[7-(benzo[b]thiophene)-4-yl-1-piperazine]ethyl]cyclohexyl]-N,N-dimethyl Preparation of urea (formula I compound) maleate
[0076] 200 mg of the product from Example 1 and maleic acid in a molar ratio of 1.05 were stirred in 5 ml of acetone (Acetone) to precipitate a solid, and the maleate salt was isolated.
Embodiment 3
[0077] Example 3: N'-[trans-4-[2-[7-(benzo[b]thiophene)-4-yl-1-piperazine]ethyl]cyclohexyl]-N,N-dimethyl Preparation of urea (formula I compound) maleate crystal form I
[0078] According to the salt 200mg obtained in Example 2 in 5 milliliters of H 2 After being suspended and stirred in O at room temperature for 3 days, the crystal form I of the maleate salt of the compound of formula I was obtained by centrifugation at room temperature.
[0079] Figure 1A Powder X-ray Diffraction Pattern (XRPD) is shown and corresponding spacing values at 2θ are provided in Table 1 characteristic peaks. Figure 1B The DSC results show that the sample has two endothermic peaks at 110.5°C and 192.8°C; Figure 1B The TGA showed that the sample had a weight loss of 5.64% when the sample was heated to 150 °C. 1 H-NMR conforms to 1:1 stoichiometry (base: maleic acid), see the results Figure 1C .
[0080] Regarding the maleate salt crystal form I of the compound of formula I, the solubil...
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