p-Toluenesulfonic acid → HCID 19774812, compound

HRID 1728469Notes

Reaction equation

HRID 1728469 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]>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 10340Sodium CarbonateHCID 31215Triethyl phosphiteHCID 5462311BoronHCID 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 trifhoride 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-l-(5,6,7,8-tetrahydro-5,5,8, 8-tetramethyl-2-naphthyl)methylphosphonate as an oil whose structure was confirmed by H and C 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-fa5fcaaf562e4636a28d4f7c00921d3b
Source dataset
uspto-grants-1994_07
Patent number
US05326900

Reaction notes

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