Bicarbonate Ion → Methyl 4-(7-cyano-3-hydroxymethylheptyl)benzoate

HRID 1672680Notes

Reaction equation

HRID 1672680 reaction equation
[C:1]([CH:4]([CH2:17][CH2:18][CH2:19][CH2:20][C:21]#[N:22])[CH2:5][CH2:6][C:7]1[CH:16]=[CH:15][C:10]([C:11]([O:13][CH3:14])=[O:12])=[CH:9][CH:8]=1)(O)=[O:2].C(=O)(O)[O-]>C1COCC1>[C:21]([CH2:20][CH2:19][CH2:18][CH2:17][CH:4]([CH2:1][OH:2])[CH2:5][CH2:6][C:7]1[CH:16]=[CH:15][C:10]([C:11]([O:13][CH3:14])=[O:12])=[CH:9][CH:8]=1)#[N:22]

Participants

4

Reactant 2

HCID 769Bicarbonate IonHCID 57831399Methyl 4-(3-carboxy-7-cyanoheptyl)benzoate

Product 1

HCID 57831355Methyl 4-(7-cyano-3-hydroxymethylheptyl)benzoateYield 47%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

33 ml of a 1 M borane-THF complex solution (33 mmol) are added dropwise to a solution of 5 g (16.48 mmol) of methyl 4-(3-carboxy-7-cyanoheptyl)benzoate from Example 92A in 62 ml of THF at −15° C., and the solution is stirred at this temperature for 2 hours. Then a further 16 ml of 1 M borane-THF complex solution are added dropwise, and stirring is continued for 45 minutes. The reaction mixture is then warmed to 0° C. and stirred at this temperature for 1 hour. After reaction is complete, 100 ml of saturated bicarbonate solution are added to the reaction mixture, and the solvent is concentrated to dryness. The residue is taken up in ethyl acetate and water, and the aqueous phase is extracted with ethyl acetate. The combined organic phases are dried over sodium sulfate and again freed of solvent. The resulting crude product is purified by flash chromatography on silica gel (mobile phase: cyclohexane/ethyl acetate 2:1→1:3→100% ethyl acetate). 2.4 g (93% purity, 47% yield) of a colorless solid are obtained.

Workup

  1. additionThen a further 16 ml of 1 M borane-THF complex solution are added dropwise
  2. stirringstirring
  3. waitis continued for 45 minutes
  4. stirringstirred at this temperature for 1 hour
  5. customAfter reaction
  6. concentrationthe solvent is concentrated to dryness
  7. extractionwater, and the aqueous phase is extracted with ethyl acetate
  8. dry with materialThe combined organic phases are dried over sodium sulfate
  9. customThe resulting crude product is purified by flash chromatography on silica gel (mobile phase: cyclohexane/ethyl acetate 2:1→1:3→100% ethyl acetate)
  10. custom2.4 g (93% purity, 47% yield) of a colorless solid are obtained

Sources & evidence

ORD record
ord-665bf748e4a441d59a665c3e36ef7e06
Source dataset
uspto-grants-2011_08
Patent number
US07998988B2

Reaction notes

Loading…