Sodium Bicarbonate → Methyl 2-[(3,5-diaminophenyl)methoxy]acetate

HRID 1421096Notes

Reaction equation

HRID 1421096 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([CH:14]=[C:15]([N+:17]([O-])=O)[CH:16]=1)[CH2:7][O:8][CH2:9][C:10]([O:12][CH3:13])=[O:11])([O-])=O.C([O-])(O)=O.[Na+]>CO>[NH2:1][C:4]1[CH:5]=[C:6]([CH:14]=[C:15]([NH2:17])[CH:16]=1)[CH2:7][O:8][CH2:9][C:10]([O:12][CH3:13])=[O:11]

Participants

4

Reactant 2

HCID 516892Sodium BicarbonateHCID 15907745HCID 15907745, compound

Product 1

HCID 15907746Methyl 2-[(3,5-diaminophenyl)methoxy]acetateYield 64.3%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A mixture of 2.1 (5.0 g, 18.5 mmol), SnCl2 dihydrate (48.0 g, 212.7 mmol) in 60 mL of methanol was refluxed for 40 minutes. The resulting dark solution was cooled (ice bath) and cautiously neutralized by adding saturated NaHCO3. The solid precipitate was filtered off and washed with methanol and CH2Cl2 until no product was found (by TLC) in the washings. The filtrate and washings were combined and evaporated in vacuo to give crude diamine 2.2. Chromatography on a silica gel column (4.5×20 cm) eluting with ethyl acetate afforded the title compound as a yellow oil (2.5 g, 64%), which slowly crystallized upon drying in vacuo: 1H NMR (CDCl3) δ 6.11 (d, J=2 Hz, 1H, C4 --H), 5.96 (t, J=2 Hz, 2H, C2 --H), 4.44 (s, 2H, CH2), 4.07 (s, 2H, CH2), 3.75 (s, 3H, CH3), 3.59 (br s, 4H, NH2); 13C NMR (CDCl3) δ 170.96, 147.78, 139.33, 105.51, 101.41, 73.31, 66.85, 51.89.

Workup

  1. temperaturewas refluxed for 40 minutes
  2. temperatureThe resulting dark solution was cooled (ice bath)
  3. filtrationThe solid precipitate was filtered off
  4. washwashed with methanol and CH2Cl2 until no product
  5. customevaporated in vacuo
  6. customto give crude diamine 2.2
  7. washChromatography on a silica gel column (4.5×20 cm) eluting with ethyl acetate

Sources & evidence

ORD record
ord-79bf03a9c57f48a3b63326bf04ef5b53
Source dataset
uspto-grants-2000_06
Patent number
US06072046

Reaction notes

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