Borane → HCID 18761444, compound

HRID 431713Notes

Reaction equation

HRID 431713 reaction equation
[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][C:12]([CH2:15][C:16](O)=[O:17])=[C:11]([N+:19]([O-:21])=[O:20])[CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.B.B.C1COCC1.CO.C(Cl)(Cl)Cl>O>[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][C:12]([CH2:15][CH2:16][OH:17])=[C:11]([N+:19]([O-:21])=[O:20])[CH:10]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 6331BoraneHCID 2723981Borane;tetrahydrofuranHCID 5311925HCID 5311925, compoundHCID 21584188Chloroform methanol

Product 1

HCID 18761444HCID 18761444, compoundYield 95%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

4-Benzyloxy-2-nitrophenylacetic acid (6.38 g, 22.2 mmol) was dissolved in freshly distilled and dry THF (60 mL) and stirred in an ice bath under N2. After 5 min, borane (55.6 mL, 55.5 mmol, 1M solution in THF) was transferred using a canula to a dropping funnel placed over the stirring solution. The BH3-THF solution was then slowly added to the solution, producing much effervescence. The red solution was left stirring in the ice bath for 10 min, and then allowed to stir at room temperature for 4 h. The reaction was checked by TLC (10% MeOH/CHCl3). Water (150 mL) was slowly added to the flask until effervescence no longer occurred. The organic layer was dried with anhydrous sodium sulfate and gravity filtered. The solution was then concentrated down producing a brown oil. Column chromatography (SiO2, 10-60% EtOAc/5% CHCl3 for solubility/hexane gradient elution) afforded 2-(4-benzyloxy-2-nitrophenyl)ethanol (5.72 g, 21.0 mmol, 95%) as a brownish solid. Mp 48-52° C.; TLC (10% MeOH/CHCl3) Rf=0.61; 1H-NMR (CDCl3, 500 MHz) 7.54 (d, 2.5, 1H), 7.42 (m, 5H), 7.31 (d, 8.5, 1H), 7.17 (dd, 2.5, 8.5, 1H), 5.10 (s, 2H), 3.91 (br q, 6.5, 2H), 3.65 (br t, 6.5, OH), 3.10 (t, 6.5, 2H); IR (neat) 3400, 3050, 2965, 2921, 2858, 1622, 1523, 1453, 1344, 1240, 1039, 804. EI-MS m/z (relative intensity) 273 (M+, 14). Accurate mass (EI-MS) for C15H15NO4: calcd. 273.1001, obsd. 273.0992.

Workup

  1. distillationin freshly distilled
  2. customproducing much effervescence
  3. waitThe red solution was left
  4. stirringto stir at room temperature for 4 h
  5. dry with materialThe organic layer was dried with anhydrous sodium sulfate and gravity
  6. filtrationfiltered
  7. concentrationThe solution was then concentrated
  8. customdown producing a brown oil
  9. washColumn chromatography (SiO2, 10-60% EtOAc/5% CHCl3 for solubility/hexane gradient elution)

Sources & evidence

ORD record
ord-c9df8b8e39a0438393d36d7ca1637d76
Source dataset
uspto-grants-2003_12
Patent number
US06660742B2

Reaction notes

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