Hydrochloric Acid → HCID 58069908, compound

HRID 1472295Notes

Reaction equation

HRID 1472295 reaction equation
II.Br[CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][O:12][CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.[CH:20]([O:22][CH3:23])=O.[BH4-].[Na+].Cl>C1COCC1>[CH2:13]([O:12][CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][CH2:6][CH2:5][CH2:4][CH:11]([OH:12])[CH2:10][CH2:9][CH2:8][CH2:7][CH2:6][CH2:5][CH2:4][CH2:20][O:22][CH2:23][C:19]1[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 807IodineHCID 7865Methyl formateHCID 4311764Sodium borohydrideHCID 15148292{[(8-Bromooctyl)oxy]methyl}benzene

Product 1

HCID 58069908HCID 58069908, compoundYield 48.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To freshly activated Mg turnings (24.08 g, 1.003 mol) was added 200 mL anhydrous THF, followed by the addition of pinch of iodine into the mixture under inert atmosphere. After initiation of the Grignard formation a solution of Compound 3 (150 g, 0.5016 mol) in 1 L of dry THF was added slowly controlling the exothermic reaction. After complete addition, the reaction was heated to reflux for 1 hour, then cooled to room temperature. Methyl formate (60.24 g, 1.0033 mol) was then added slowly and reaction was continued for 2 hours. After completion, the reaction was quenched by slow addition of 10% HCl followed by water (1 L) and extracted with ethyl acetate (3×1 L). The organic layer was taken in 5 liter beaker, diluted with 500 mL of methanol and cooled to 0° C. To this solution excess of NaBH4 (˜5 eq) was added in portions to ensure the hydrolysis of formate ester which was not cleaved by addition of HCl. The resulting solution was stirred for an hour and then volatilites were removed under vacuum. The residue was taken in water (1 L) and acidified by 10% HCl solution (PH 4). The product was then extracted with ethyl acetate (3×1 L). The organic phase was then dried and concentrated on rotary evaporator to afford compound 4 (57 g, 24%) as solid. 1H NMR (400 MHz, CDCl3): δ=7.35-7.32 (m, 8H), 7.29-7.24 (m, 2H), 4.49 (s, 4H), 3.56 (m, 1H), 3.46-3.43 (m, 4H), 1.63-1.56 (m, 4H), 1.44-1.34 (m, 28H). C13 NMR (100 MHz, CDCl3): δ=138.56, 128.21, 127.49, 127.34, 72.72, 71.76, 70.37, 37.37, 29.64, 29.56, 29.47, 29.33, 26.07, 25.54.

Workup

  1. customthe exothermic reaction
  2. additionAfter complete addition
  3. temperaturethe reaction was heated
  4. temperatureto reflux for 1 hour
  5. customreaction
  6. customAfter completion, the reaction was quenched by slow addition of 10% HCl
  7. extractionextracted with ethyl acetate (3×1 L)
  8. additiondiluted with 500 mL of methanol
  9. temperaturecooled to 0° C
  10. customvolatilites were removed under vacuum
  11. extractionThe product was then extracted with ethyl acetate (3×1 L)
  12. customThe organic phase was then dried
  13. concentrationconcentrated on rotary evaporator

Sources & evidence

ORD record
ord-8d40f55ac9f94e1d9c490cb5d101c620
Source dataset
uspto-grants-2015_04
Patent number
US09012498B2

Reaction notes

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