Hydrochloric Acid → HCID 58069908, compound

HRID 2174306Notes

Reaction equation

HRID 2174306 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.O>[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

8

Reactant 5

HCID 313Hydrochloric Acid2×HCID 807IodineHCID 7865Methyl formateHCID 4311764Sodium borohydrideHCID 15148292{[(8-Bromooctyl)oxy]methyl}benzene

Product 1

HCID 58069908HCID 58069908, compoundYield 48.5%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To freshly activated Mg turnings (24.08 g, 1.003 mol) was added 200 mL anhydrous THF was added 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 reaction was refluxed for 1 h and then cooled to room temperature. (60.24 g, 1.0033 mol) methyl formate was then added slowly and reaction was continued for 2 h. 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). Organic layer was taken in 5 lit 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. Resulting solution was stirred for an hour and then volatilites were stripped off under vacuum. Residue was taken in water (1 L) and acidified by 10% HCl solution (PH 4). Product was then extracted out with ethyl acetate (3×1 L). Organic phase was then dried and concentrated on rotary evaporator to get the desired compound 4 (57 g, 24%) as solid. H1 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. additionwas added
  2. customthe exothermic reaction
  3. additionAfter complete addition reaction
  4. temperaturewas refluxed for 1 h
  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. extractionProduct was then extracted out with ethyl acetate (3×1 L)
  11. customOrganic phase was then dried
  12. concentrationconcentrated on rotary evaporator

Sources & evidence

ORD record
ord-e62058c4852749e391169cfb2674298d
Source dataset
uspto-grants-2015_06
Patent number
US09061063B2

Reaction notes

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