Triethylamine → (9H-fluoren-9-yl)methyl prop-2-yn-1-ylcarbamate

HRID 1057068ノート

反応式

HRID 1057068 の反応式
[C:1](Cl)([O:3][CH2:4][CH:5]1[C:17]2[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=2)[C:11]2[C:6]1=[CH:7][CH:8]=[CH:9][CH:10]=2)=[O:2].[CH2:19]([NH2:22])[C:20]#[CH:21].C(N(CC)CC)C>C(Cl)Cl.CCCCCC>[CH2:19]([NH:22][C:1](=[O:2])[O:3][CH2:4][CH:5]1[C:17]2[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=2[C:11]2[C:6]1=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:20]#[CH:21]

参加物

6

反応物 3

HCID 8471TriethylamineHCID 343679-Fluorenylmethyl chloroformateHCID 239041Propargylamine

生成物 1

HCID 10084877(9H-fluoren-9-yl)methyl prop-2-yn-1-ylcarbamate収率 95.3%

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒2 回HCID 8058Hexane溶媒

実験手順

A solution of Fmoc chloride (25.00 g, 96.64 mmol, 1.05 eq.) in DCM (150 mL) was added dropwise to a solution of propargylamine 8 (5.89 mL, 92.04 mmol, 1.0 eq.) and triethylamine (15.4 mL, 110.4 mmol, 1.2 eq.) in DCM (200 mL) at −78° C. The reaction mixture was allowed to stir at room temperature, and after 16 hours the solution was washed with water (300 mL), 0.1 N aqueous citric acid (300 mL), saturated aqueous NaHCO3 (300 mL) and brine (200 mL). The organic phase was dried over magnesium sulphate, filtered and concentrated under reduced pressure to provide an amorphous white powder. Sonication in cold hexane (200 mL) followed by filtration afforded the product as a white solid (24.316 g, 95%). LC/MS (2.758 min (ES+)). m/z: 300.0 [M+Na]+. 1H NMR (400 MHz, CDCl3) δ 7.74 (d, 2H, J=7.6 Hz), 7.57 (d, 2H, J=7.4 Hz), 7.41-7.37 (m, 2H), 7.30 (dt, 2H, J=7.5, 1.2 Hz), 4.93 (br s, 1H), 4.41 (d, 2H, J=6.9 Hz), 4.21 (t, 1H, J=6.4 Hz), 3.99 (d, 2H, J=3.3 Hz), 2.24 (t, 1H, J=2.5 Hz).

後処理

  1. washafter 16 hours the solution was washed with water (300 mL), 0.1 N aqueous citric acid (300 mL), saturated aqueous NaHCO3 (300 mL) and brine (200 mL)
  2. dry with materialThe organic phase was dried over magnesium sulphate
  3. filtrationfiltered
  4. concentrationconcentrated under reduced pressure
  5. customto provide an amorphous white powder
  6. filtrationfollowed by filtration

出典と根拠

ORDレコード
ord-9cc1e302c8c94ad695142d7d98178116
出典データセット
uspto-grants-2016_07
特許番号
US09399073B2

反応ノート

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