HCID 19261315, compound → HCID 18762168, compound

HRID 650853Notes

Reaction equation

HRID 650853 reaction equation
[CH3:1]C(C)([O-])C.[K+].[C:7]([O:11][C:12]([O:14][C:15]1[CH:16]=[C:17]([CH:20]=[CH:21][CH:22]=1)[CH:18]=O)=[O:13])([CH3:10])([CH3:9])[CH3:8]>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1>[C:7]([O:11][C:12]([O:14][C:15]1[CH:16]=[C:17]([CH:20]=[CH:21][CH:22]=1)[CH:18]=[CH2:1])=[O:13])([CH3:10])([CH3:9])[CH3:8]

Participants

5

Reactant 2

HCID 19261315HCID 19261315, compoundHCID 23665647Potassium tert-butoxide

Product 1

HCID 18762168HCID 18762168, compoundYield 48.7%

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

m-Hydroxybenzaldehyde (819 mmol, 100.0 g) was placed in a 5 L 3-necked round bottom flask equipped with a mechanical stirrer and an argon gas inlet, to which was added THF (4.5 L). Potassium t-butoxide (834 mmol, 93.7 g) was slowly added to the solution over 3 min. After 15 min, di-t-butyl dicarbonate (834 mmol, 182.3 g) was added over 15 min. After 2.5 hr at room temperature the reaction mixture was poured into 4 L of water and the product was extracted with 2 L of a mixture of hexanes and ether (1:1). The organic layers were combined, washed with saturated NaCl (2 L), saturated NaHCO3 (1 L), and H2O (2 L), and dried over MgSO4 (ca. 100 g). The organic phase was filtered and condensed to give m-(t-butoxycarbonyloxy)benzaldehyde (792 mmol, 176 g) in 97% crude yield. Methyl(triphenyl)phosphonium bromide (848 mmol, 303 g) was placed in a 2 L 3-necked round bottom flask containing 1.5 L of THF. The mixture was cooled to 0° C. under nitrogen and potassium t-butoxide (830 mmol, 93.1 g) was added slowly to the mixture over 10 min. m-(t-Butoxycarbonyloxy)benzaldehyde (792 mmol, 176 g) was added and the mixture was stirred for another 6 h, upon which the solvent was removed on a rotary evaporator and hexanes (1.5 L) added. The mixture was stirred for 2 h and filtered through a small bed of silica. The hexane layer was concentrated to give 120 g of the crude product. Purification by column chromatography gave 85 g of pure m-(t-butoxycarbonyloxy)styrene (47% yield based on m-hydroxybenzaldehyde).

Workup

  1. additionwas added
  2. customwas removed on a rotary evaporator and hexanes (1.5 L)
  3. additionadded
  4. stirringThe mixture was stirred for 2 h
  5. filtrationfiltered through a small bed of silica
  6. concentrationThe hexane layer was concentrated
  7. customto give 120 g of the crude product
  8. customPurification by column chromatography

Sources & evidence

ORD record
ord-c6ef5023fc46439d97367dcd4e5b651d
Source dataset
uspto-grants-2001_08
Patent number
US06277546B1

Reaction notes

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