Acetic Acid → HCID 66849502, compound

HRID 1191317Notes

Reaction equation

HRID 1191317 reaction equation
[NH2:1][C:2]1[CH:11]=[CH:10][C:9]([Br:12])=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].[CH:13](=O)[C:14]1[CH:19]=[CH:18][C:17]([O:20][CH3:21])=[CH:16][CH:15]=1.C(O)(=O)C.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].C(=O)(O)[O-].[Na+]>ClCCl>[Br:12][C:9]1[CH:10]=[CH:11][C:2]([NH:1][CH2:13][C:14]2[CH:19]=[CH:18][C:17]([O:20][CH3:21])=[CH:16][CH:15]=2)=[C:3]([CH:8]=1)[C:4]([O:6][CH3:7])=[O:5]

Participants

7

Reactant 5

HCID 176Acetic AcidHCID 312444-MethoxybenzaldehydeHCID 516892Sodium BicarbonateHCID 736224Methyl 2-amino-5-bromobenzoateHCID 5049666Sodium triacetoxyborohydride

Product 1

HCID 66849502HCID 66849502, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of methyl 2-amino-5-bromobenzoate (10.0 g, 43.5 mmol) in dichloromethane (0.5 M, 90 mL) at 0° C. were added p-anisaldehyde (7.9 mL, 65 mmol) and acetic acid (1.2 mL, 22 mmol). Sodium triacetoxyborohydride (18.4 g, 87.0 mmol) was added portion-wise to the solution mixture. The reaction was allowed to warm to room temp and stirred overnight. Upon completion, the reaction was poured into saturated sodium bicarbonate (200 mL). The product was extracted with dichloromethane (3×75 mL). The combined organic extractions were dried over magnesium sulfate, filtered, and concentrated in vacuo. The crude material was purified via flash chromatography (silica, 1:1 hexanes/dichloromethane) to yield methyl 5-bromo-2-[(4-methoxybenzyl)amino]benzoate. HRMS (M+H)=350.0381. 1H NMR (400 MHz, CDCl3) 8.08 (b, 1H), 8.10 (d, 1H), 7.36 (dd, 1H), 7.24 (d, 2H), 6.88 (d, 2H), 6.54 (d, 1H), 4.35 (s, 2H), 3.86 (s, 3H), 3.80 (s, 3H).

Workup

  1. extractionThe product was extracted with dichloromethane (3×75 mL)
  2. extractionThe combined organic extractions
  3. dry with materialwere dried over magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe crude material was purified via flash chromatography (silica, 1:1 hexanes/dichloromethane)

Sources & evidence

ORD record
ord-28e1352e64ea40b48dfc1e79197fb513
Source dataset
uspto-grants-2014_03
Patent number
US08680116B2

Reaction notes

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