Hydrochloric Acid → 2-[N-(tert-butoxycarbonylmethyl)amino]benzophenone

HRID 850205Notes

Reaction equation

HRID 850205 reaction equation
[NH2:1][C:2]1[CH:15]=[CH:14][CH:13]=[CH:12][C:3]=1[C:4]([C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)=[O:5].[I-].[K+].C(=O)([O-])[O-].[K+].[K+].Br[CH2:25][C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27].CN.Cl.C(=O)([O-])O.[Na+]>C(OCC)(=O)C.CN(C)C=O>[C:29]([O:28][C:26]([CH2:25][NH:1][C:2]1[CH:15]=[CH:14][CH:13]=[CH:12][C:3]=1[C:4]([C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)=[O:5])=[O:27])([CH3:32])([CH3:31])[CH3:30]

Participants

10

Reactant 7

HCID 313Hydrochloric AcidHCID 4875Potassium IodideHCID 6329MethylamineHCID 11430Potassium CarbonateHCID 760802-AminobenzophenoneHCID 79177tert-Butyl bromoacetate2×HCID 516892Sodium Bicarbonate

Product 1

HCID 109798502-[N-(tert-butoxycarbonylmethyl)amino]benzophenoneYield 87.2%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent2×

Procedure

A mixture of 2-aminobenzophenone (20.00 g, 0.101 mol), potassium iodide (8.42 g, 0.0507 mol), potassium carbonate (21.02 g, 0.152 mol), N,N-dimethylformamide (30 ml) and t-butyl bromoacetate (29.67 g, 0.152 mol) was stirred at room temperature, and allowed to react at 80° C. for 5.5 hr. The mixture was cooled to give slurry, to which 40% aqueous methylamine solution (11.81 g, 0.152mol) was added to decompose excess t-butyl bromoacetate. To the mixture were added ethyl acetate (60 ml) and 6.4% hydrochloric acid (147 g, 0.259 mol) for partition. The ethyl acetate layer was washed once with 2.1% sodium hydrogencarbonate (41 g, 0.010 mol) and condensed under reduced pressure to remove the solvent. The residue was crystallized from n-hexane (70 ml) to yield 2-[N-(tert-butoxycarbonylmethyl)amino]benzophenone (27.41 g, yield 86.8%) as a yellow crystal. (Reference value, mp: 88° C. (DSC).) 1H-NMR 200 MHz (CDCl3) δ: 1.50 (s, 9 H), 3.96 (d, J=5.3,2 H), 6.55-6.65 (m, 2H), 7.33-7.66 (m, 7H)), 8.90 (t, J=5.3,1 H) ##STR12##

Workup

  1. customto react at 80° C. for 5.5 hr
  2. temperatureThe mixture was cooled
  3. customto give slurry
  4. customfor partition
  5. customto remove the solvent
  6. customThe residue was crystallized from n-hexane (70 ml)

Sources & evidence

ORD record
ord-851576d505f2411eb89249e09b2879d4
Source dataset
uspto-grants-2000_01
Patent number
US06015921

Reaction notes

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