Nitric Acid → 2-(3-Methoxy-propyl)-4-nitro-phenoxy-acetic acid ethyl ester

HRID 1242279Notes

Reaction equation

HRID 1242279 reaction equation
[CH2:1]([O:3][C:4](=[O:18])[CH2:5][O:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=1[CH2:13][CH2:14][CH2:15][O:16][CH3:17])[CH3:2].[N+:19]([O-])([OH:21])=[O:20]>C(OC(C(F)(F)F)=O)(C(F)(F)F)=O>[CH2:1]([O:3][C:4](=[O:18])[CH2:5][O:6][C:7]1[CH:12]=[CH:11][C:10]([N+:19]([O-:21])=[O:20])=[CH:9][C:8]=1[CH2:13][CH2:14][CH2:15][O:16][CH3:17])[CH3:2]

Participants

4

Reactant 2

HCID 944Nitric AcidHCID 67072081HCID 67072081, compound

Product 1

HCID 670724332-(3-Methoxy-propyl)-4-nitro-phenoxy-acetic acid ethyl ester

Reagents, catalysts & solvents 1

HCID 9845Trifluoroacetic anhydrideSolvent2×

Procedure

4.00 g (15.9 mmol) of the above prepared [2-(3-methoxy-propyl)-phenoxy]-acetic acid ethyl ester was dissolved in 5.0 ml of TFAA and added slowly and carefully via dropping funnel to a mixture of 5 ml of TFAA and 4 ml of conc. HNO3 (65%) kept at −10° C.; the reaction was then allowed to proceed for additional 30 Min. Careful quenching with ice, twofold extraction with AcOEt, washing with NaHCO3 and brine, drying over magnesium sulfate, and evaporation of the solvents left a crude product which was purified by flash chromatography (SiO2, hexane/AcOEt=75/25) to deliver finally 3.00 g of the title compound as light brown oil, contaminated according to NMR with roughly 35% of the ortho-isomer which was separated after the next step.

Workup

  1. additionadded slowly
  2. customkept at −10° C.
  3. customCareful quenching with ice, twofold extraction with AcOEt
  4. washwashing with NaHCO3 and brine
  5. dry with materialdrying over magnesium sulfate, and evaporation of the solvents
  6. waitleft a crude product which
  7. customwas purified by flash chromatography (SiO2, hexane/AcOEt=75/25)
  8. customwas separated after the next step

Sources & evidence

ORD record
ord-7bb0b098c2b94abcb419ecdc53522f71
Source dataset
uspto-grants-2006_10
Patent number
US07115611B2

Reaction notes

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