3-Chloro-4-[[(1,1-dimethylethyl)dimethylsilyl]oxy]benzaldehyde → 2-Chloro-4-ethenylphenol

HRID 2053646

Reaction equation

HRID 2053646 reaction equation
[CH2:1]([Li])CCC.[Cl:6][C:7]1[CH:8]=[C:9]([CH:12]=[CH:13][C:14]=1[O:15][Si](C(C)(C)C)(C)C)[CH:10]=O>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1>[Cl:6][C:7]1[CH:8]=[C:9]([CH:10]=[CH2:1])[CH:12]=[CH:13][C:14]=1[OH:15]

Participants

5

Reactant 2

HCID 220169343-Chloro-4-[[(1,1-dimethylethyl)dimethylsilyl]oxy]benzaldehydeHCID 178418339Butyllithium

Product 1

HCID 208726142-Chloro-4-ethenylphenol

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To a slurry of methyltriphenylphosphonium bromide (0.23 g) in dry THF (5 ml) under nitrogen at −78° C., n-butyl lithium (1.6M in hexanes, 0.37 ml) was added dropwise over 2 min. The mixture was allowed to warm to 0° C., stirred for 20 min, cooled to −78° C. and a solution of 3-chloro-4-[[(1,1-dimethylethyl)dimethylsilyl]oxy]benzaldehyde* (0.134 g) in dry THF (5 ml) added. The reaction mixture was allowed to reach room temperature overnight and quenched with saturated aqueous ammonium chloride. The resultant mixture was extracted with diethyl ether and the combined organic extracts were concentrated under reduced pressure. The residue was purified using SPE (silica, eluting with cyclohexane, followed by 5% to 25% ethyl acetate:cyclohexane) to give the title compound (0.049 g) as an oil. *Boukouvalas, J; Maltais, F; Lachance, N., Tetrahedron Lett. (1994), 35(43), 7897-900.

Workup

  1. temperaturecooled to −78° C.
  2. waitto reach room temperature overnight
  3. customquenched with saturated aqueous ammonium chloride
  4. extractionThe resultant mixture was extracted with diethyl ether
  5. concentrationthe combined organic extracts were concentrated under reduced pressure
  6. customThe residue was purified
  7. washSPE (silica, eluting with cyclohexane, followed by 5% to 25% ethyl acetate:cyclohexane)

Sources & evidence

ORD record
ord-e340b12d247f4b3cbf22d2973f6d1ba5
Source dataset
uspto-grants-2008_02
Patent number
US07326785B2

Linked notes

Loading…