Sulfuric Acid → HCID 178424156, compound

HRID 1380387Notes

Reaction equation

HRID 1380387 reaction equation
[C:1]1([CH3:9])[CH:6]=[CH:5][C:4]([Mg]Br)=[CH:3][CH:2]=1.[C:10]1([P:16]([O-])[O:17]CC)[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1.S(=O)(=O)(O)O>CCOCC>[C:1]1([CH3:9])[CH:6]=[CH:5][CH:4]=[CH:3][C:2]=1[C:13]1[CH:14]=[CH:15][C:10]([PH2:16]=[O:17])=[CH:11][CH:12]=1

Participants

5

Reactant 3

HCID 1118Sulfuric AcidHCID 18981701ethoxy(phenyl)phosphiniteHCID 178418370HCID 178418370, compound

Product 1

HCID 178424156HCID 178424156, compoundYield 80.9%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

A solution of p-tolylmagnesium bromide [prepared from p-bromotolueme (29.1 g, 0.16 mol) and magnesium (4.38 g, 0.18 g-atom)] in ether (100 mL) was treated with a solution of ethyl phenylphosphonite (13,6 g, 0.08 mol) in ether (50 mL) with vigorous mechanical stirring. The mixture was heated at reflux for 1/2 hr., then 100 mL of 25% sulfuric acid was added cautiously. Three layers formed; the bottom (aqueous) layer was extracted with toluene. Addition of NaHCO3, to the combined upper layers produced a vigorous reaction and a single organic phase. The organic phase was washed with water and with saturated NaCl, dried and evaporated to give an oil (14 g). Kugelrohr distillation at 120°-160° C. (0.1 mmHg) followed by chromatography on silica gel (CHCl3), then 10% MeOH-CHCl3) gave 7.1 g of an oil. This was distilled in the Kugelrohr again (150° C., 0.1 mmHg) to give 6.2 g of product which appears to be pure by NMR and crystallized on standing. 1H NMR (CDCl3) δ 8.0-7.2 (m, 9 H), 8.08 (d, J=480 Hz, 1 H), 2.42 (s, 3 H).

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux for 1/2 hr
  3. customThree layers formed
  4. extractionthe bottom (aqueous) layer was extracted with toluene
  5. additionAddition of NaHCO3
  6. customto the combined upper layers produced
  7. customa vigorous reaction
  8. washThe organic phase was washed with water and with saturated NaCl
  9. customdried
  10. customevaporated

Sources & evidence

ORD record
ord-1bcd099c7776454aa1dbb4475dfea199
Source dataset
uspto-grants-1986_04
Patent number
US04581415

Reaction notes

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