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

HRID 1057068Notes

Reaction equation

HRID 1057068 reaction equation
[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]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 343679-Fluorenylmethyl chloroformateHCID 239041Propargylamine

Product 1

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

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 8058HexaneSolvent

Procedure

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).

Workup

  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

Sources & evidence

ORD record
ord-9cc1e302c8c94ad695142d7d98178116
Source dataset
uspto-grants-2016_07
Patent number
US09399073B2

Reaction notes

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