Dimethylformamide → tert-butyl 4-(prop-1-yn-1-yl)-1H-pyrazole-1-carboxylate

HRID 1526613ノート

反応式

HRID 1526613 の反応式
Br[C:2]1[CH:3]=[N:4][N:5]([C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])[CH:6]=1.C(N([CH2:19][CH3:20])CC)C.[CH3:21]N(C=O)C>[Cu]I.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:21]([C:2]1[CH:3]=[N:4][N:5]([C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])[CH:6]=1)#[C:19][CH3:20]

参加物

6

反応物 3

HCID 6228DimethylformamideHCID 8471TriethylamineHCID 457897231-Boc-4-bromopyrazole

生成物 1

HCID 90391073tert-butyl 4-(prop-1-yn-1-yl)-1H-pyrazole-1-carboxylate

試薬・触媒・溶媒 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418397HCID 178418397、化合物触媒

反応条件

温度
70 °C

実験手順

A sealable vial was charged with a solution of tert-butyl 4-bromo-1H-pyrazole-1-carboxylate (1 g, 4.05 mmol) and triethylamine (2.81 mL, 20.24 mmol) in DMF (6.75 mL). The solution was purged with nitrogen for 10 minutes. Copper (I) iodide (0.077 g, 0.405 mmol) and tetrakis(triphenylphosphine)palladium (0.234 g, 0.202 mmol) were added and 1-propyne was bubbled through the solution for 2 min. The reaction mixture was heated at 70° C. overnight. The reaction was poured into a 9:1 mixture of aqueous saturated ammonium chloride/ammonium hydroxide and the mixture was extracted with EtOAc. The combined organic extracts were washed with a 9:1 mixture of aqueous saturated ammonium chloride/ammonium hydroxide, aqueous lithium bromide solution, brine, and dried over sodium sulfate. The filtrate was concentrated in vacuo and the residue was purified by silica gel chromatography, eluting with 1:9 EtOAc in heptane, to provide tert-butyl 4-(prop-1-yn-1-yl)-1H-pyrazole-1-carboxylate, which was taken up in MeOH and treated with excess solid K2CO3 for 15 minutes. The reaction mixture was filtered and the filtrate was concentrated under reduced pressure The crude material was partitioned between DCM and water. The layers were separated and the aqueous layer was extracted with DCM. The combined organic extracts were washed with brine and dried over sodium sulfate. The filtrate was concentrated in vacuo to afford 4-(prop-1-yn-1-yl)-1H-pyrazole. LC/MS (ESI−) m/z=107.0 (M+H).

後処理

  1. customThe solution was purged with nitrogen for 10 minutes
  2. custom1-propyne was bubbled through the solution for 2 min
  3. additionThe reaction was poured into a 9:1 mixture of aqueous saturated ammonium chloride/ammonium hydroxide
  4. extractionthe mixture was extracted with EtOAc
  5. washThe combined organic extracts were washed with a 9:1 mixture of aqueous saturated ammonium chloride/ammonium hydroxide, aqueous lithium bromide solution, brine
  6. dry with materialdried over sodium sulfate
  7. concentrationThe filtrate was concentrated in vacuo
  8. customthe residue was purified by silica gel chromatography
  9. washeluting with 1:9 EtOAc in heptane

出典と根拠

ORDレコード
ord-bee41b0bd24d4a25a0fa1dab11d267bc
出典データセット
uspto-grants-2015_07
特許番号
US09085576B2

反応ノート

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