Benzyl Bromide → HCID 57904839, compound

HRID 1093111Notes

Reaction equation

HRID 1093111 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[N:7]=[C:8]2[N:14]([C:15](=[O:18])[C:16]=1[OH:17])[CH2:13][CH:12]1[CH2:19][CH2:20][C:9]2([O:21][CH2:22][CH2:23][OH:24])[CH2:10][CH2:11]1)=[O:5])[CH3:2].C([O-])([O-])=O.[K+].[K+].Br[CH2:32][C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1>CN(C=O)C>[CH2:1]([O:3][C:4]([C:6]1[N:7]=[C:8]2[N:14]([C:15](=[O:18])[C:16]=1[O:17][CH2:32][C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)[CH2:13][CH:12]1[CH2:19][CH2:20][C:9]2([O:21][CH2:22][CH2:23][OH:24])[CH2:10][CH2:11]1)=[O:5])[CH3:2]

Participants

5

Reactant 3

HCID 7498Benzyl Bromide2×HCID 11430Potassium Carbonate2×HCID 57905239HCID 57905239, compound

Product 1

HCID 57904839HCID 57904839, compoundYield 55%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of 5-hydroxy-1-(2-hydroxyethoxy)-6-oxo-3,7-diazatricyclo[7.2.2.02,7]trideca-2,4-diene-4-carboxylic acid ethyl ester (203 mg, 0.600 mmol) in DMF (1 mL) was added K2CO3 (249 mg, 1.80 mmol) and (bromomethyl)benzene (103 mg, 0.600 mmol) and the mixture stirred at room temperature overnight under N2. Additional (bromomethyl)benzene (206 mg, 1.2 mmol, 2 eq.) and K2CO3 (166 mg, 1.2 mmol, 2 eq.) were added and the mixture stirred overnight. The mixture was concentrated in vacuo to remove most of DMF, and the residue was diluted with ethyl acetate (15 mL),washed with water followed by brine, then dried (Na2SO4) and concentrated to provide an amber oil which was purified by silica gel column chromatography (18 g SiO2, 45% ethyl acetate/CH2Cl2) to gave the title compound (141 mg, 0.329 mmol, 55% yield) as an amber oil; HPLC: retention time=2.18 min (area percent=92%); LCMS: m/z 429 (M+H); 1H NMR (500 MHz, CDCl3) δ ppm 1.28 (3H, t, J=7.2 Hz), 1.63 (2H, ddd, J=14.3, 7.5, 7.2 Hz), 1.83-1.94 (2H, m), 2.06 (4H, t, J=7.6 Hz), 2.42 (1H, brs), 3.59 (2H, t, J=4 Hz), 3.70 (2H, d, J=4 Hz), 4.05 (2H, d, J=4.0 Hz), 4.31 (2H, q, J=7.2 Hz), 5.22 (2H, s), 7.27 (1H, t, J=7.4 Hz), 7.32 (2H, t, J=7.2 Hz), 7.46 (2H, d, J=6.7 Hz); 13C NMR (126 MHz, CDCl3) δ ppm 14.1, 23.2, 27.6, 30.5, 53.6, 62.1, 62.2, 65.3, 74.5, 76.7, 128.3, 128.5, 128.6, 136.8, 140.0, 142.4, 159.2, 161.3, 163.9.

Workup

  1. stirringthe mixture stirred overnight
  2. concentrationThe mixture was concentrated in vacuo
  3. customto remove most of DMF
  4. additionthe residue was diluted with ethyl acetate (15 mL),washed with water
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated
  7. customto provide an amber oil which
  8. customwas purified by silica gel column chromatography (18 g SiO2, 45% ethyl acetate/CH2Cl2)

Sources & evidence

ORD record
ord-2dbe9e5e835343a59ab2b4b5d875a93f
Source dataset
uspto-grants-2012_03
Patent number
US08129398B2

Reaction notes

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