Iodine → HCID 178507413, compound

HRID 2203272Notes

Reaction equation

HRID 2203272 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]([CH2:11][NH2:12])[CH2:9][NH2:10])=[CH:4][CH:3]=1.C([O-])([O-])=O.[K+].[K+].C([O:23][C:24](=O)[NH:25][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][C:27]=1[CH:32]=O)(C)(C)C.II>CC(O)(C)C>[NH2:1][C:2]1[CH:3]=[CH:4][C:5]([CH:8]2[CH2:11][N:12]3[C:24](=[O:23])[NH:25][C:26]4[CH:31]=[CH:30][CH:29]=[CH:28][C:27]=4[C:32]3=[N:10][CH2:9]2)=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 807IodineHCID 11430Potassium CarbonateHCID 11287472tert-Butyl (2-formylphenyl)carbamate2×HCID 86702442HCID 86702442, compound

Product 1

HCID 178507413HCID 178507413, compoundYield 39%

Reagents, catalysts & solvents 1

HCID 6386tert-ButanolSolvent

Procedure

A mixture of 2-(4-aminophenyl)propane-1,3-diamine.3HCl (632 mg, 2.30 mmol) and powdered K2CO3 (3.18 g, 23.0 mmol) in 30 mL t-BuOH was heated at 83° C. for 45 min, then tert-butyl(2-formylphenyl)carbamate (560 mg, 2.53 mmol) was added. At 6.5 hours the reaction was allowed to partially cool, approximately 25 mg tert-butyl(2-formylphenyl)carbamate was added, then iodine (48 mg, 0.188 mmol) added, stirred 5 min at rt, and the heating resumed at 83° C. After 1.5 hours the temperature was lowered to 75° C. and the reaction continued an additional 15 hours. The reaction was partitioned between EtOAc and aqueous Na2CO3 solution plus Na2S2O3, the EtOAc layer washed with brine, dried with Na2SO4, and evaporated. The resulting solid was chromatographed eluting with CHCl3/MeOH to give the title compound as a yellow-tan solid (262 mg, 39%). 1H NMR (DMSO-d6) δ: 10.65 (br. s, 1H), 7.97 (dd, J=7.9, 1.5 Hz, 1H), 7.39-7.45 (m, 1H), 6.98-7.08 (m, 2H), 6.93-6.98 (m, 2H), 6.51-6.57 (m, 2H), 4.96 (br. s, 2H), 4.12-4.20 (m, 1H), 3.61-3.70 (m, 1H), 3.36-3.53 (m, 2H), 2.73-2.85 (m, 1H).

Workup

  1. temperatureto partially cool
  2. customresumed at 83° C
  3. waitAfter 1.5 hours the temperature was lowered to 75° C.
  4. waitthe reaction continued an additional 15 hours
  5. customThe reaction was partitioned between EtOAc and aqueous Na2CO3 solution plus Na2S2O3
  6. washthe EtOAc layer washed with brine
  7. dry with materialdried with Na2SO4
  8. customevaporated
  9. customThe resulting solid was chromatographed
  10. washeluting with CHCl3/MeOH

Sources & evidence

ORD record
ord-381a0d1b8733480697cef3ff2d64a255
Source dataset
uspto-grants-2016_06
Patent number
US09365575B2

Reaction notes

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