Potassium vinyltrifluoroborate → methyl 4-(4-(difluoromethyl)-5-vinylthiazol-2-yl)-1-methyl-1H-pyrazole-5-carboxylate

HRID 60143

反応式

HRID 60143 の反応式
F[C:2](OB([O-])[O-])=[C:3]([F:5])[F:4].[K+].[K+].Br[C:13]1[S:17][C:16]([C:18]2[CH:19]=[N:20][N:21]([CH3:27])[C:22]=2[C:23]([O:25][CH3:26])=[O:24])=[N:15][C:14]=1[CH:28](F)F.[B-](F)(F)(F)C=C.[K+]>[Pd](Cl)Cl.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].C(OCC)(=O)C.C(N(CC)CC)C.C(O)C>[F:4][CH:3]([F:5])[C:2]1[N:15]=[C:16]([C:18]2[CH:19]=[N:20][N:21]([CH3:27])[C:22]=2[C:23]([O:25][CH3:26])=[O:24])[S:17][C:13]=1[CH:14]=[CH2:28]

参加物

8

反応物 3

HCID 23679353Potassium vinyltrifluoroborateHCID 86620274Potassium trifluorovinylborateHCID 90383233methyl 4-(5-bromo-4-(difluoromethyl)thiazol-2-yl)-1-methyl-1H-pyrazole-5-carboxylate

生成物 1

HCID 117761094methyl 4-(4-(difluoromethyl)-5-vinylthiazol-2-yl)-1-methyl-1H-pyrazole-5-carboxylate収率 58%

試薬・触媒・溶媒 4

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒2 回HCID 702Ethanol溶媒HCID 8471Triethylamine溶媒2 回HCID 8857Ethyl Acetate溶媒

反応条件

温度
100 °C

実験手順

Potassium trifluorovinylborate (172 mg), 1,1′-bis(diphenylphosphino)ferrocene-palladium(II) dichloride (31 mg), and triethylamine (59.4 μl) were added to an ethanol (2.1 ml) solution of the methyl 4-(5-bromo-4-(difluoromethyl)thiazol-2-yl)-1-methyl-1H-pyrazole-5-carboxylate (150 mg) obtained in (Example 1.4) <Step 1>, and the obtained mixture was then stirred in a nitrogen atmosphere at 100° C. for 17 hours. Thereafter, potassium trifluoro(vinyl)borate (342 mg), 1,1′-bis(diphenylphosphino)ferrocene-palladium(II) dichloride (62 mg), and triethylamine (59.4 μl) were added to the reaction solution, and the obtained mixture was stirred again in a nitrogen atmosphere at 100° C. for 2 hours 40 minutes. Thereafter, ethyl acetate (100 ml) and a saturated saline (50 ml) were added to the reaction solution. An organic layer was extracted, and was then dried over anhydrous sodium sulfate. The solvent was distilled away under reduced pressure, and the obtained residue was then purified by silica gel column chromatography (silica gel:eluent; heptane:ethyl acetate=95:5-50:50), so as to obtain the title compound (74 mg) in the form of a colorless solid.

後処理

  1. customobtained in (Example 1.4) <Step 1>
  2. stirringthe obtained mixture was stirred again in a nitrogen atmosphere at 100° C. for 2 hours 40 minutes
  3. extractionAn organic layer was extracted
  4. dry with materialwas then dried over anhydrous sodium sulfate
  5. distillationThe solvent was distilled away under reduced pressure
  6. customthe obtained residue was then purified by silica gel column chromatography (silica gel:eluent; heptane:ethyl acetate=95:5-50:50)

出典と根拠

ORDレコード
ord-f7e2c1a181be472c8a441820e6365940
出典データセット
uspto-grants-2016_09
特許番号
US09440970B2

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