Hexane → HCID 18922484, compound

HRID 1289984Notes

Reaction equation

HRID 1289984 reaction equation
[Li][CH2:2][CH2:3][CH2:4][CH3:5].CCCCCC.C([O:14][CH:15](OCC)[C:16]1[CH:21]=[C:20](Br)[CH:19]=[CH:18][C:17]=1[O:23][CH3:24])C.COB(OC)OC>C1COCC1>[CH2:2]([C:20]1[CH:19]=[CH:18][C:17]([O:23][CH3:24])=[C:16]([CH:21]=1)[CH:15]=[O:14])[CH2:3][CH2:4][CH3:5]

Participants

6

Reactant 4

HCID 8058HexaneHCID 8470Trimethyl borateHCID 12433391HCID 12433391, compoundHCID 178418339Butyllithium

Product 1

HCID 18922484HCID 18922484, compoundYield 43%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

n-BuLi in hexane (1.6M, 15.4 mL, 24.6 mmol) was added dropwise over 15 min to a -70° C. solution of 5-bromo-2-methoxybenzaldehyde diethylacetal in 50 mL of THF. Once the addition was complete, the mixture was stirred and allowed to warm up to 0° C. over 1.5 h. The mixture was then cooled to -70° C. and a solution of trimethylborate (5.4 mL, 48 mmol) in 25 mL of THF was added rapidly through a double-ended needle. The reaction was kept at -70° C. for 4 h and was then allowed to warm to 0° C. slowly before being quenched by the addition of 70 mL of 2.0N aqueous hydrochloric acid. After the mixture had been stirred for 1 h, the layers were separated and the aqueous layer was extracted with 3×100 mL of ethyl acetate. The combined organic layers were dried (sodium sulfate), decanted, and evaporated. The residue was then dissolved in ethyl acetate (100 mL) and extracted with 4×44 mL of 2.0N sodium hydroxide. The ethyl acetate layer was dried (sodium sulfate), decanted, and evaporated. The crude material was purified by flash column chromatography on silica gel, eluting with 10-20% dichloromethane in hexane to yield 5-butyl-2-methoxybenzaldehyde (1.87 g, 43% yield) as an amber liquid.

Workup

  1. additionOnce the addition
  2. temperatureThe mixture was then cooled to -70° C.
  3. temperatureto warm to 0° C. slowly
  4. custombefore being quenched by the addition of 70 mL of 2.0N aqueous hydrochloric acid
  5. stirringAfter the mixture had been stirred for 1 h
  6. customthe layers were separated
  7. extractionthe aqueous layer was extracted with 3×100 mL of ethyl acetate
  8. dry with materialThe combined organic layers were dried (sodium sulfate)
  9. customdecanted
  10. customevaporated
  11. dissolutionThe residue was then dissolved in ethyl acetate (100 mL)
  12. extractionextracted with 4×44 mL of 2.0N sodium hydroxide
  13. dry with materialThe ethyl acetate layer was dried (sodium sulfate)
  14. customdecanted
  15. customevaporated
  16. customThe crude material was purified by flash column chromatography on silica gel
  17. washeluting with 10-20% dichloromethane in hexane

Sources & evidence

ORD record
ord-3f090462cf5e4477b7194cdadec812a6
Source dataset
uspto-grants-1998_05
Patent number
US05750549

Reaction notes

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