Ethyl bromoacetate → 1,4,7-Tris-(benzyloxycarbonyl)-10-(ethoxycarbonylmethyl)-1,4,7,10-tetrazacyclododecane

HRID 1271804Notes

Reaction equation

HRID 1271804 reaction equation
[CH2:1]([O:8][C:9]([N:11]1[CH2:22][CH2:21][NH:20][CH2:19][CH2:18][N:17]([C:23]([O:25][CH2:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)=[O:24])[CH2:16][CH2:15][N:14]([C:33]([O:35][CH2:36][C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)=[O:34])[CH2:13][CH2:12]1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(=O)([O-])[O-].[Na+].[Na+].[CH2:49]([O:51][C:52](=[O:55])[CH2:53]Br)[CH3:50]>C(#N)C>[CH2:1]([O:8][C:9]([N:11]1[CH2:22][CH2:21][N:20]([CH2:53][C:52]([O:51][CH2:49][CH3:50])=[O:55])[CH2:19][CH2:18][N:17]([C:23]([O:25][CH2:26][C:27]2[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=2)=[O:24])[CH2:16][CH2:15][N:14]([C:33]([O:35][CH2:36][C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)=[O:34])[CH2:13][CH2:12]1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 7748Ethyl bromoacetateHCID 10340Sodium CarbonateHCID 151342581,4,7-Tris-(benzyloxycarbonyl)-1,4,7,10-tetrazacyclododecane

Product 1

HCID 184548871,4,7-Tris-(benzyloxycarbonyl)-10-(ethoxycarbonylmethyl)-1,4,7,10-tetrazacyclododecane

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

68.2 g (118.6 mmol) of 1,4,7-tris-(benzyloxycarbonyl)-1,4,7,10-tetrazacyclododecane (Delaney et al., J Chem. Soc. Perkin Trans. 1991, 3329) is dissolved in 700 ml of acetonitrile and mixed with 75.4 g (545.5 mmol) of sodium carbonate. Then, 39.6 g (355.5 mmol) of bromoacetic acid ethyl ester is added while being stirred vigorously, and it is heated for 20 hours to 40° C. Insoluble components are filtered out, evaporated to the dry state and chromatographed on silica gel (mobile solvent: ethyl acetate/hexane 20:1). The fractions that contain the product are combined and concentrated by evaporation.

Workup

  1. temperatureit is heated for 20 hours to 40° C
  2. filtrationInsoluble components are filtered out
  3. customevaporated to the dry state
  4. customchromatographed on silica gel (mobile solvent: ethyl acetate/hexane 20:1)
  5. concentrationconcentrated by evaporation

Sources & evidence

ORD record
ord-cf244fb2cd5641fc82b7b8d6b2dd053f
Source dataset
uspto-grants-2007_04
Patent number
US07208140B2

Reaction notes

Loading…