p-Toluenesulfonic acid → HCID 19774812, compound

HRID 1614097Notes

Reaction equation

HRID 1614097 reaction equation
[CH3:1][C:2]1([CH3:16])[CH2:11][CH2:10][C:9]([CH3:13])([CH3:12])[C:8]2[CH:7]=[C:6]([CH:14]=[O:15])[CH:5]=[CH:4][C:3]1=2.C([O-])([O-])O[CH2:19][CH3:20].C1(C)C=CC(S(O)(=O)=O)=CC=1.C(=O)([O-])[O-].[Na+].[Na+].[P:40]([O:47]CC)([O:44][CH2:45][CH3:46])[O:41][CH2:42][CH3:43].B(F)(F)F.CCOCC>C(O)C.C(Cl)Cl.O>[CH2:19]([O:15][CH:14]([P:40](=[O:47])([O:44][CH2:45][CH3:46])[O:41][CH2:42][CH3:43])[C:6]1[CH:5]=[CH:4][C:3]2[C:2]([CH3:16])([CH3:1])[CH2:11][CH2:10][C:9]([CH3:12])([CH3:13])[C:8]=2[CH:7]=1)[CH3:20]

Participants

10

Reactant 6

HCID 6101p-Toluenesulfonic acidHCID 8000Boron trifluoride etherateHCID 10340Sodium CarbonateHCID 31215Triethyl phosphiteHCID 104208875,5,8,8-Tetramethyl-5,6,7,8-tetrahydro-2-naphthalenecarbaldehydeHCID 53630039Ethylorthoformate

Product 1

HCID 19774812HCID 19774812, compound

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

65.4 g (0.3 mol) of 5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-naphthaldehyde, 56 g (0.38 mol) of ethyl orthoformate and 0.3 g of 4-toluenesulfonic acid in 75 ml of absolute ethanol were stirred at room temperature for 16 h. Then 7.6 g of anhydrous sodium carbonate were added, the mixture was stirred for about 15 min, the solids were filtered off, and the filtrate was concentrated. 92 g of diethyl acetal remained. 73.5 g (0.25 mol) of this diethyl acetal and 42.2 g (0.25 mol) of triethyl phosphite were dissolved in 240 ml of dry methylene chloride and, at -20° C. under nitrogen, 38 g (0.265 mol) of boron trifluoride diethyl etherate were added dropwise. The mixture was allowed to reach room temperature overnight, then 80 ml of water were added, the phases were separated, and the organic phase was dried over sodium sulfate and concentrated. Purification by column chromatography (silica gel; n-heptane/ethyl acetate 1:0→1) resulted in 33.3 g of slightly impure diethyl 1-ethoxy-1-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-naphthyl)methylphosphonate as an oil whose structure was confirmed by H and 13C NMR.

Workup

  1. filtrationthe solids were filtered off
  2. concentrationthe filtrate was concentrated
  3. waitto reach room temperature overnight
  4. customthe phases were separated
  5. dry with materialthe organic phase was dried over sodium sulfate
  6. concentrationconcentrated
  7. customPurification by column chromatography (silica gel; n-heptane/ethyl acetate 1:0→1)

Sources & evidence

ORD record
ord-9bdbace0cb784ae4a6e6af204ff2d958
Source dataset
uspto-grants-1993_03
Patent number
US05194664

Reaction notes

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