Nitrogen → Tert-butyl {1-[3,5-bis(trifluoromethyl)phenyl]-1-hydroxybut-3-en-2-yl}carbamate

HRID 529698

反応式

HRID 529698 の反応式
[C:1]([NH:8][CH2:9][CH:10]=[CH2:11])([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].C([Li])(CC)C.N#N.[F:19][C:20]([F:34])([F:33])[C:21]1[CH:22]=[C:23]([CH:26]=[C:27]([C:29]([F:32])([F:31])[F:30])[CH:28]=1)[CH:24]=[O:25]>C1COCC1.[Cl-].[Cl-].[Zn+2]>[F:19][C:20]([F:33])([F:34])[C:21]1[CH:22]=[C:23]([CH:24]([OH:25])[CH:9]([NH:8][C:1](=[O:2])[O:3][C:4]([CH3:7])([CH3:6])[CH3:5])[CH:10]=[CH2:11])[CH:26]=[C:27]([C:29]([F:32])([F:30])[F:31])[CH:28]=1

参加物

7

反応物 4

HCID 947NitrogenHCID 1362473,5-Bis(trifluoromethyl)benzaldehydeHCID 4067274tert-butyl N-(prop-2-en-1-yl)carbamateHCID 178418400CID 53628100

生成物 1

HCID 86682261Tert-butyl {1-[3,5-bis(trifluoromethyl)phenyl]-1-hydroxybut-3-en-2-yl}carbamate収率 44.9%

試薬・触媒・溶媒 2

HCID 3007855Zincchloride触媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-78 °C

実験手順

To N-Boc-allylamine (50.0 g, 0.318 mol) in anhydrous THF (800 mL) at −78° C. was added sec-butyllithium (1.30 M in cyclohexane, 538.0 mL, 0.7 mol) dropwise under a stream of N2 gas. The resulting yellow solution was stirred at −78° C. for an additional 2 hours, after which time ZnCl2 (1.1 M in Et2O, 349.8 mL, 0.35 mol) was added. The solution was stirred for 1 hour before 3,5-bis-trifluoromethylbenzaldehyde (169.3 g, 0.700 mol) was added to the clear solution. The mixture was stirred at −78° C. for 1 hour before quenching with acetic acid (227 mL). The reaction was poured into ice water (2 L) and the organic layer was washed with aqueous saturated NaHCO3 (2 L×2) and brine (1 L), was dried (MgSO4), and concentrated. The crude material was recrystallized from petroleum ether (300 mL) to yield tert-butyl {1-[3,5-bis(trifluoromethyl)phenyl]-1-hydroxybut-3-en-2-yl}carbamate (57 g) as a white powder. In total this process yielded 2.8 kg of material. MS ESI calc'd. for C17H20F6NO3 [M+H]+ 400.1, found 400.0.

後処理

  1. additionwas added to the clear solution
  2. stirringThe mixture was stirred at −78° C. for 1 hour
  3. custombefore quenching with acetic acid (227 mL)
  4. additionThe reaction was poured into ice water (2 L)
  5. washthe organic layer was washed with aqueous saturated NaHCO3 (2 L×2) and brine (1 L)
  6. dry with materialwas dried (MgSO4)
  7. concentrationconcentrated
  8. customThe crude material was recrystallized from petroleum ether (300 mL)

出典と根拠

ORDレコード
ord-5a9112b2b6c9444eb0a49ea20a3379fe
出典データセット
uspto-grants-2016_05
特許番号
US09346825B2

関連ノート

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