Water → HCID 59180880, compound

HRID 1618868Notes

Reaction equation

HRID 1618868 reaction equation
[CH2:1]([O:3][C:4](=[O:22])[CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][O:10][C:11]1[CH:16]=[C:15]([CH:17]=[O:18])[CH:14]=[CH:13][C:12]=1[N+:19]([O-])=O)[CH3:2].O>C(O)C.Cl>[CH2:1]([O:3][C:4](=[O:22])[CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][O:10][C:11]1[CH:16]=[C:15]([CH:17]=[O:18])[CH:14]=[CH:13][C:12]=1[NH2:19])[CH3:2]

Participants

5

Reactant 2

HCID 962WaterHCID 59180879HCID 59180879, compound

Product 1

HCID 59180880HCID 59180880, compound

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 702EthanolSolvent

Conditions

Temperature
70 °C

Procedure

To a solution of 6-(5-formyl-2-nitro-phenoxy)-hexanoic acid ethyl ester (1.0 g, 3.23 mmol) in ethanol (20 ml) and concentrated HCl (5 ml) was added stannous chloride (2.17 g, 11.63 mmol). The mixture was stirred at 70° C. for 90 minutes while being monitored by thin layer chromatography. After cooling to room temperature, the mixture was poured into water (100 ml) and neutralized with a saturated solution of sodium bicarbonate resulting in the precipitation of tin salts and a dark brown oil. The salts were washed with ethyl acetate and the washings were combined with the original filtrate, the aqueous phase was separated and the remaining ethyl acetate phase was dried with magnesium sulfate, filtered and concentrated by rotary evaporation to a brown oil which was purified by column chromatography (45% CH2Cl2, 45% hexane, 10% Et3N). The product, 6-(2-amino-5-formyl-phenoxy)-hexanoic acid ethyl ester, was obtained as a red oil (0.33 g, 35%). An additional 0.32 g of red oil was obtained from the column but found to be a mixture of unidentified byproducts. 1H NMR (400 MHz, CDCl3) δ: 9.72 (s, 1H), 7.30 (m, 2H), 613 (d, 1H, J=8.4 Hz), 4.50 (s, 2H), 4.15 (q, 2H, J=7.2 Hz), 4.08 (t, 2H, J=6.8 Hz), 2.35 (t, 2H, J=8.8 Hz), 1.88 (m, 2H), 1.74 (m, 2H), 1.55 (m, 2H) 1.30 (t, 3H, J=6.8 Hz). 13C NMR (400 MHz, CDCl3) δ: 109.59, 173.60, 146.08, 143.31, 127.78, 127.55, 112.72, 109.11, 68.18, 60.35, 34.20, 28.83, 25.69, 24.61, 14.18. IR (neat): 3481, 3362, 2936, 2868, 2722, 2360, 2341, 2229, 2156, 1964, 1727, 1671, 1612, 1587, 1572, 1517, 1444, 1394, 1368, 1313, 1243, 1164, 1140, 1095, 1029, 864, 817, 789, 748.

Workup

  1. temperatureAfter cooling to room temperature
  2. customneutralized with a saturated solution of sodium bicarbonate resulting in the precipitation of tin salts
  3. washThe salts were washed with ethyl acetate
  4. customthe aqueous phase was separated
  5. dry with materialthe remaining ethyl acetate phase was dried with magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated by rotary evaporation to a brown oil which
  8. customwas purified by column chromatography (45% CH2Cl2, 45% hexane, 10% Et3N)

Sources & evidence

ORD record
ord-b713acd47c7948668b29f6028863af20
Source dataset
uspto-grants-2014_07
Patent number
US08772048B2

Reaction notes

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