Hydrochloric Acid → HCID 18407113, compound

HRID 370001Notes

Reaction equation

HRID 370001 reaction equation
[C:1]1([C:7]([CH2:13][O:14][CH2:15][CH2:16][Si:17]([CH3:20])([CH3:19])[CH3:18])([CH2:10][CH:11]=[CH2:12])[C:8]#N)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[H-].C([Al+]CC(C)C)C(C)C.C1(C)C=CC=CC=1.C(OCC)(=[O:40])C.Cl>C(OCC)C>[C:1]1([C:7]([CH2:13][O:14][CH2:15][CH2:16][Si:17]([CH3:20])([CH3:19])[CH3:18])([CH2:10][CH:11]=[CH2:12])[CH:8]=[O:40])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 1140TolueneHCID 8857Ethyl AcetateHCID 18407155HCID 18407155, compoundHCID 21225700Diisobutylaluminumhydride

Product 1

HCID 18407113HCID 18407113, compoundYield 39.2%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

A solution of 2-phenyl-2-(2-(trimethylsilyl)ethoxymethyl)-pent-4-enenitrile (354 mg, 1.23 mmol) in ethyl ether (1.0 mL) was cooled in an ice bath and a 1.5 M solution of diisobutylaluminum hydride in toluene (1.25 mL, 1.88 mmol) was added. After 2.5 h, ethyl acetate (0.30 mL, 270 mg, 3.1 mmol) was added and the mixture was transferred to a stirred mixture of 30 mL of ethyl ether and 10 mL of 2 N aqueous HCl at 0° C. After 10 min, the layers were separated and the aqueous layer was stirred for 0.5 h with another 30 mL of ethyl ether. The two organic layers were washed in succession with 10 mL each of 2 N aqueous HCl, saturated aqueous sodium bicarbonate, and brine. The combined organic layers were dried over sodium sulfate and evaporated. The residue was dissolved in 5.0 mL of THF and 0.7 mL of water was added followed by 1.0 g of silica gel. After stirring for 40 min at RT, the mixture was filtered and the silica gel was washed with additional THF. The filtrate was evaporated and the residue was purified by flash column chromatography on silica gel, eluting with 2% ethyl ether in hexane, to give 140 mg of the title compound as a colorless oil. 1H NMR (400 MHz, CDCl3): δ 9.56 (s, 1H), 7.35 (t, 2H, J=7 Hz), 7.26 (t, 1H, J=7 Hz), 7.16 (d, 2H, J=7 Hz), 5.47 (ddt, 1H, J=17, 10, 7 Hz), 5.06-4.96 (m, 2H), 3.98 (d, 1H, J=9 Hz), 3.80 (d, 1H, J=9 Hz), 3.58-3.47 (m, 2H), 2.73 (d, 2H, J=7 Hz), 0.88 (t, 2H, J=8 Hz), -0.03 (s, 9 H). Mass spectrum (CI): m/z=263 (M-27, 100%).

Workup

  1. waitAfter 10 min
  2. customthe layers were separated
  3. washThe two organic layers were washed in succession with 10 mL each of 2 N aqueous HCl, saturated aqueous sodium bicarbonate, and brine
  4. dry with materialThe combined organic layers were dried over sodium sulfate
  5. customevaporated
  6. dissolutionThe residue was dissolved in 5.0 mL of THF
  7. addition0.7 mL of water was added
  8. stirringAfter stirring for 40 min at RT
  9. filtrationthe mixture was filtered
  10. washthe silica gel was washed with additional THF
  11. customThe filtrate was evaporated
  12. customthe residue was purified by flash column chromatography on silica gel
  13. washeluting with 2% ethyl ether in hexane

Sources & evidence

ORD record
ord-f0da1f46a63645e383c611f755470d02
Source dataset
uspto-grants-2000_10
Patent number
US06140349

Reaction notes

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