Sodium Carbonate → (3-Bromobenzyl)-carbamic acid 9H-fluoren-9-ylmethyl ester

HRID 1925189Notes

Reaction equation

HRID 1925189 reaction equation
Cl.[Br:2][C:3]1[CH:4]=[C:5]([CH:8]=[CH:9][CH:10]=1)[CH2:6][NH2:7].C([O-])([O-])=O.[Na+].[Na+].[CH:17]1[C:29]2[CH:28]([CH2:30][O:31][C:32](C3CC(=O)N(O)C3=O)=[O:33])[C:27]3[C:22](=[CH:23][CH:24]=[CH:25][CH:26]=3)[C:21]=2[CH:20]=[CH:19][CH:18]=1>O1CCOCC1.C(Cl)Cl>[CH:17]1[C:29]2[CH:28]([CH2:30][O:31][C:32](=[O:33])[NH:7][CH2:6][C:5]3[CH:8]=[CH:9][CH:10]=[C:3]([Br:2])[CH:4]=3)[C:27]3[C:22](=[CH:23][CH:24]=[CH:25][CH:26]=3)[C:21]=2[CH:20]=[CH:19][CH:18]=1

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 27249803-Bromobenzylamine hydrochlorideHCID 21653429Fmoc-N-hydroxysuccinimide

Product 1

HCID 67519536(3-Bromobenzyl)-carbamic acid 9H-fluoren-9-ylmethyl esterYield 82.1%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 312751,4-DioxaneSolvent

Procedure

To 3-bromobenzylamine hydrochloride (16.0 g, 71.9 mmol) was added aqueous 9% Na2CO3 (211 mL) followed by 9-fluorenylmethyloxycarbonyl-N-hydroxysuccinimide (25.5 g, 75.5 mmol) in dioxane (211 mL). This was stirred 30 minutes, then diluted with CH2Cl2 (200 mL). The layers were separated and the aqueous layer was extracted with CH2Cl2. The combined organic layers were washed with 1 M HCl, brine, dried over magnesium sulfate, filtered, and concentrated in vacuo. The resulting solid was purified by recrystallization (ethyl acetate/hexanes) to obtain a fluffy, white solid (24 g, 59 mmol, 82%). 1H NMR (400 MHz, d6-DMSO): δ 7.90 (t, 1H, J=6.2 Hz), 7.88 (d, 2H, J=7.5 Hz), 7.68 (d, 2H, J=7.5 Hz), 7.43 (m, 4H), 7.32 (dd, 2H, J=7.5 Hz, 7.5 Hz), 7.26 (d, 1H, J=7.7 Hz), 7.20 (d, 1H, J=7.3 Hz), 4.35 (d, 2H, J=6.6 Hz), 4.22 (t, 1H, J=6.6 Hz), 4.17 (d, 2H, J=6.2 Hz). ESI/MS: 408 (M+H+).

Workup

  1. customThe layers were separated
  2. extractionthe aqueous layer was extracted with CH2Cl2
  3. washThe combined organic layers were washed with 1 M HCl, brine
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe resulting solid was purified by recrystallization (ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-275083d8f9e8400ea5e6b87df18f4937
Source dataset
uspto-grants-2012_05
Patent number
US08178579B2

Reaction notes

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