Bromoacetic Acid → 9-Fluorenylmethyl bromoacetate

HRID 589414Notes

Reaction equation

HRID 589414 reaction equation
[CH:1]1[C:13]2[CH:12]([CH2:14][OH:15])[C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]=2[CH:4]=[CH:3][CH:2]=1.[Br:16][CH2:17][C:18](O)=[O:19].C1(C)C=CC(S([O-])(=O)=O)=CC=1.CN(C)C1C=C[NH+]=CC=1.C1CCC(N=C=NC2CCCCC2)CC1>ClCCl>[Br:16][CH2:17][C:18]([O:15][CH2:14][CH:12]1[C:13]2[CH:1]=[CH:2][CH:3]=[CH:4][C:5]=2[C:6]2[C:11]1=[CH:10][CH:9]=[CH:8][CH:7]=2)=[O:19]

Participants

6

Reactant 4

HCID 6227Bromoacetic AcidHCID 10868DicyclohexylcarbodiimideHCID 904669H-Fluorene-9-methanolHCID 111854944-(Dimethylamino)pyridinium 4-toluenesulfonate

Product 1

HCID 860598919-Fluorenylmethyl bromoacetate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

Under ice-cooling, 9-fluorenemethanol (99%, 0.694 g, 3.5 mmol), bromoacetic acid (99%, 0.406 g, 2.9 mmol), DPTS (0.130 g, 0.44 mmol) and DCC (99%, 0.729 g, 3.5 mmol) were combined in dichloromethane (9 mL), stirred at 0° C. for 1 h, and the precipitate of dicyclohexylurea was filtered off from the cold mixture. The filtrate was diluted with cold ethyl acetate (30 mL), washed twice with cold 5% aqueous solution of NaH2PO4 (60 mL, acidified with H3PO4 to pH=3), freed of water droplets, and the solvents were distilled off in vacuo. The residue was extracted with cold pentane to remove the excess of DCC, and purified by flash chromatography (silica-gel, hexane-CHCl3, 5:1 to 1:1) followed by crystallization from cold hexane. Yield of 8: 0.795 g (87%). The purity was confirmed by TLC (SiO2, heptane-ethyl acetate, 9:1).

Workup

  1. temperatureUnder ice-cooling
  2. filtrationthe precipitate of dicyclohexylurea was filtered off from the cold mixture
  3. additionThe filtrate was diluted with cold ethyl acetate (30 mL)
  4. washwashed twice with cold 5% aqueous solution of NaH2PO4 (60 mL, acidified with H3PO4 to pH=3)
  5. distillationthe solvents were distilled off in vacuo
  6. extractionThe residue was extracted with cold pentane
  7. customto remove the excess of DCC
  8. custompurified by flash chromatography (silica-gel, hexane-CHCl3, 5:1 to 1:1)
  9. customfollowed by crystallization from cold hexane

Sources & evidence

ORD record
ord-e1dcc0a8182940eb8e5481cfdc672df2
Source dataset
uspto-grants-2016_01
Patent number
US09233163B2

Reaction notes

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