Bromoacetyl bromide → N-(5-(4-cyanobenzyloxy)-2-(bromoacetyl)aminobenzoyl)-beta-alanine ethyl ester

HRID 861938Notes

Reaction equation

HRID 861938 reaction equation
[Br:1][CH2:2][C:3](Br)=[O:4].[CH2:6]([O:8][C:9](=[O:32])[CH2:10][CH2:11][NH:12][C:13](=[O:31])[C:14]1[CH:19]=[C:18]([O:20][CH2:21][C:22]2[CH:27]=[CH:26][C:25]([C:28]#[N:29])=[CH:24][CH:23]=2)[CH:17]=[CH:16][C:15]=1[NH2:30])[CH3:7]>C(Cl)Cl.O>[CH2:6]([O:8][C:9](=[O:32])[CH2:10][CH2:11][NH:12][C:13](=[O:31])[C:14]1[CH:19]=[C:18]([O:20][CH2:21][C:22]2[CH:23]=[CH:24][C:25]([C:28]#[N:29])=[CH:26][CH:27]=2)[CH:17]=[CH:16][C:15]=1[NH:30][C:3](=[O:4])[CH2:2][Br:1])[CH3:7]

Participants

5

Reactant 2

HCID 61147Bromoacetyl bromideHCID 19700602HCID 19700602, compound

Product 1

HCID 19700600N-(5-(4-cyanobenzyloxy)-2-(bromoacetyl)aminobenzoyl)-beta-alanine ethyl ester

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Procedure

A solution of 1.44 g (7.15 mmol, 1.1 eq.) bromoacetyl bromide in 10 mL of methylene chloride was added over 10 mins. to a stirred biphasic solution of 2.38 g (6.5 mmol, 1.0 eq.) of N-(5-(4-cyanobenzyloxy)-2-aminobenzoyl)-β-alanine ethyl ester in 100 ml of methylene chloride and 30 mL of water cooled to 0° C. The reaction was complete in 1/2 hr. (TLC, 96 CH2Cl2 :4 MeOH, product Rf =0.71) and was partitioned between dilute aqueous sodium bicarbonate and methylene chloride. The organic phase was dried over sodium sulfate, filtered and concentrated to give 3.11 g (98%) of off white crystals of N-(5-(4-cyanobenzyloxy)-2-(bromoacetyl)aminobenzoyl)-β-alanine ethyl ester which was used unpurified but may be recrystallized from ethyl acetate/hexane. 1H NMR (CDCl3, δTMS) 8.41(1H,d,ArH), 7.60 (4H,abq,ArH), 7.02(2H,d,ArH), 6.98(1H,t,NH), 5.12 (2H,s,ArCH2O),4.16 (2H,q,COOCH2), 3.97 (2H,s,CH2Br), 3.68 (2H,q,NCH2), 2.61 (2H,t,CH2COO), 1.25 (3H,t,CH3). IR (KBr): 3389(NH), 3355(NH), 2226(CN), 1735(ester), 1675,1642(amides), 1609,1523,1423,1244,1184,819. MS (FAB, M+H+) cald for C22H22N3O5Br 488.3, found (M+H+) 489.

Workup

  1. custom(TLC, 96 CH2Cl2 :4 MeOH, product Rf =0.71) and was partitioned between dilute aqueous sodium bicarbonate and methylene chloride
  2. dry with materialThe organic phase was dried over sodium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated

Sources & evidence

ORD record
ord-c85e8133363844c3ab2de939e8d3053b
Source dataset
uspto-grants-1998_02
Patent number
US05716951

Reaction notes

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