Boron trifluoride etherate → Methyl 4-(1-aminocyclopropyl)benzoate

HRID 1694375

反応式

HRID 1694375 の反応式
[C:1]([C:3]1[CH:12]=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[CH:5][CH:4]=1)#[N:2].[CH3:13][CH2:14][Mg+].[Br-].B(F)(F)F.CCOCC>C1(C)C=CC=CC=1.C1COCC1>[NH2:2][C:1]1([C:3]2[CH:12]=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[CH:5][CH:4]=2)[CH2:14][CH2:13]1

参加物

6

反応物 3

HCID 8000Boron trifluoride etherateHCID 70791Methyl 4-cyanobenzoateHCID 178461630HCID 178461630、化合物

生成物 1

HCID 45140209Methyl 4-(1-aminocyclopropyl)benzoate収率 43%

試薬・触媒・溶媒 2

HCID 1140Toluene溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

Methyl 4-cyanobenzoate (2.6 kg, 16.1 mol) was dissolved in 40 L of toluene at −25° C. and Ti(Oi-Pr)4 (4.73 L, 16.1 mol) was added over 5 min, followed by EtMgBr (10.5 L of a 3.07M solution in THF, 32.3 mol) over 2 hr. After aging for 30 min, BF3.OEt2 (4.1 L, 32 mol) was added over 40 min and the mixture was aged for another 40 min. The reaction was quenched by the addition of 40 L of 3N HCl. The layers were separated and the aqueous layer was washed with 13 L toluene. The aqueous layer was then extracted with 2-MeTHF (2×26 L and 2×13 L). The combined 2-MeTHF layers were washed with 3N NaOH and the pH of the NaOH layer adjusted to 9 before separation of the layers. The organic layer was washed with 13 L of brine. Yield=43%. 1H NMR (500 MHz, CDCl3): δ 8.00 (d, 2H), 7.35 (d, 2H), 3.95 (s, 3H), 1.25 (t, 2H), 1.10 (t, 2H).

後処理

  1. customover 2 hr
  2. waitthe mixture was aged for another 40 min
  3. customThe reaction was quenched by the addition of 40 L of 3N HCl
  4. customThe layers were separated
  5. washthe aqueous layer was washed with 13 L toluene
  6. extractionThe aqueous layer was then extracted with 2-MeTHF (2×26 L and 2×13 L)
  7. washThe combined 2-MeTHF layers were washed with 3N NaOH
  8. customthe pH of the NaOH layer adjusted to 9 before separation of the layers
  9. washThe organic layer was washed with 13 L of brine

出典と根拠

ORDレコード
ord-2b4be886d5c54c15811377e8cb9bff9f
出典データセット
uspto-grants-2012_04
特許番号
US08158671B2

関連ノート

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