Triethylamine → 6-(4-Hydroxymethyl-2-methoxy-5-nitrophenoxy)hexyl acetate

HRID 987394Notes

Reaction equation

HRID 987394 reaction equation
[C:1]([O:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][O:11][C:12]1[CH:17]=[C:16]([N+:18]([O-:20])=[O:19])[C:15]([CH:21]=[O:22])=[CH:14][C:13]=1[O:23][CH3:24])(=[O:3])[CH3:2].[BH4-].[Na+].[Cl-].[NH4+].C(N(CC)CC)C>C(O)C.ClCCl>[C:1]([O:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][O:11][C:12]1[CH:17]=[C:16]([N+:18]([O-:20])=[O:19])[C:15]([CH2:21][OH:22])=[CH:14][C:13]=1[O:23][CH3:24])(=[O:3])[CH3:2]

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 25517Ammonium ChlorideHCID 4311764Sodium borohydrideHCID 180087936-(4-Formyl-2-methoxy-5-nitrophenoxy)hexyl acetate

Product 1

HCID 180087906-(4-Hydroxymethyl-2-methoxy-5-nitrophenoxy)hexyl acetate

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

A flame-dried, 250 mL round bottom flask was charged, under argon, with 4 (8 g, 23.6 mmol) and this was suspended in 35 mL of anhydrous ethanol. The flask was protected from light and then placed in an ice bath. Sodium borohydride (2.06 g, 54.3 mmol) was added in small portions and the reaction was allowed to stir at 0° C. for 180 minutes. At this time, saturated ammonium chloride (30 mL) was added slowly to the reaction mixture over a period of 20 minutes to minimize the gas evolution. Ethanol was evaporated in vacuo and the mixture was diluted with water (100 ml) and extracted with dichloromethane (3×100 mL). The combined organic layers were dried with magnesium sulfate, filtered, and the solvent was evaporated in vacuo to give orange oil. This oil was subjected to column chromatography (SiO2, 75×200 mm, 1% triethylamine in dichloromethane) to give, following solvent evaporation, 7.25 g (90%) of 5 as a yellow solid. Rf=0.30 (33% ethyl acetate/hexane). Mp >220° C. 1H NMR (400 MHz, DMSO-d6): δ7.67 (s, 1), 7.38 (s, 1), 5.55 (t, J=6.4 Hz, 1), 4.81 (d, J=6.4 Hz, 2), 4.04 (t, J=7.2 Hz, 2), 4.00 (t, J=7.6 Hz, 2), 3.91 (s, 3), 1.99 (s, 3), 1.76-1.72 (m, 2), 1.61-1.57 (m, 2), 1.45-1.37 (m, 4) ppm.

Workup

  1. customplaced in an ice bath
  2. customEthanol was evaporated in vacuo
  3. additionthe mixture was diluted with water (100 ml)
  4. extractionextracted with dichloromethane (3×100 mL)
  5. dry with materialThe combined organic layers were dried with magnesium sulfate
  6. filtrationfiltered
  7. customthe solvent was evaporated in vacuo
  8. customto give orange oil
  9. customto give
  10. customsolvent evaporation, 7.25 g (90%) of 5 as a yellow solid

Sources & evidence

ORD record
ord-fa3fd1c378ed4818ab6545cb6c6e043c
Source dataset
uspto-grants-2003_10
Patent number
US06632641B1

Reaction notes

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