A kind of salt form, crystal form and preparation method of EGFR inhibitor
A technology of crystal form and solvent addition, which is applied in the application field of drugs for the treatment of non-small cell lung cancer, and can solve problems such as diarrhea and rash
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Embodiment 1
[0097] Preparation of compounds of formula (I): Example 1
[0098]
[0099] step 1:
[0100] N 2 Protected, pyridine (1.74Kg, 22.01mol, 1.10 eq.) In dichloromethane (20L) was cooled to -20 deg.] C, was slowly added dropwise trifluoromethanesulfonic anhydride (5.87Kg, 20.81mol, 1.04 equiv) was added dropwise completion of the reaction system at -20 ℃ and stirred for 0.5 hours and was slowly added dropwise 2-bromoethanol (2.50Kg, 20.01mol, 1.0 eq), and stir the reaction temperature was maintained below 0 ℃ 1.0 h, TLC (petroleum ether: acetic acid ethyl ester = 5: 1) showed the reaction was complete. After the reaction was filtered directly into the reaction system, and the filtrate was concentrated and then petroleum ether (15L), the precipitated solid was filtered and the filtrate was concentrated to give compound b (4.80Kg, 93.33% yield) as a dark yellow oil. 1 HNMR (400MHz, CDCL 3 ): 4.77 (t, J = 6.40Hz, 2H), 3.63 (t, J = 6.40Hz, 2H).
[0101] Step 2:
[0102] Compound b (8.5Kg...
Embodiment 2
[0122] Compounds of formula (II): Example 2
[0123] 8L of acetone was added to the 50L reaction vessel at room temperature was added the formula (I) compound (1.10Kg, 1.97mol, 1.0 eq.) In the reactor, stirred to dissolution clarification, thiourea resin (220.44g, 20% mass ratio ) was added to the reaction solution, stirred overnight at 25 deg.] C, vacuum filtration, the filter cake was washed with acetone 3L. The combined acetone solution is transferred to a 50L reactor, heated to 65 ℃, pressure-equalizing dropping funnel was slowly added dropwise methanesulfonic acid (185.34g, 1.93mol, 0.98 eq.), Dropwise addition, the solution was clear. After 30min, the solution to precipitate an off-white solid. Incubated for 2 hours, cooled to 25 ℃. N 2 Protection under reduced pressure suction, the filter cake was vacuum oven dried to constant weight to give of formula (II) compound as a brown solid (965G, 73% yield). 1 H NMR (400MHz, CD 3 OD): δ, 8.37 (s, 1H), 8.34 (d, J = 3.07Hz, 1H), 7.8...
Embodiment 3
[0124] Preparation of Compound A crystalline form of formula (II): Example 3
[0125] The compounds of formula (I) to take 120mg, 0.5mL was added dissolved in tetrahydrofuran, then added slowly with stirring 0.14mL methanesulfonic acid - tetrahydrofuran solution (V / V, 1: 9). After stirring overnight centrifugation, the residual solid sample placed in a vacuum oven (30 ℃) was dried overnight at 25 ℃, of formula (II) A crystalline form of the compound.
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