Boron trifluoride → HCID 20522869, compound

HRID 223240Notes

Reaction equation

HRID 223240 reaction equation
[C:1]([O:6][CH2:7][CH3:8])(=[O:5])[C:2]([CH3:4])=[O:3].[CH3:9][O:10][C:11]1[CH:12]=[C:13]([CH:19](O)C)[CH:14]=[CH:15][C:16]=1[O:17][CH3:18].B(F)(F)F.[N+]([CH3:29])([O-])=O>C(Cl)Cl>[CH3:18][O:17][C:16]1[CH:15]=[C:14]2[C:4](=[CH:12][C:11]=1[O:10][CH3:9])[C:2]([CH3:29])([C:1]([O:6][CH2:7][CH3:8])=[O:5])[O:3][CH2:19][CH2:13]2

Participants

6

Reactant 4

HCID 6356Boron trifluorideHCID 6375NitromethaneHCID 12041Ethyl pyruvateHCID 4364381-(3,4-dimethoxyphenyl)ethanol

Product 1

HCID 20522869HCID 20522869, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Ethyl pyruvate (1.00 g, 0.0086 m), 3,4-dimethoxyphenylethanol (1.57 g, 0.0086 m), and, 1 ml of BF3 etherate are stirred at 25° C. in 20 ml of nitromethane for 45 minutes. The mixture is dissolved in methylene chloride and extracted with aqueous sodium bicarbonate. The organic phase is dried (sodium sulfate), concentrated, and chromatographed on silica gel to give 1.4 g of 6,7-dimethoxy-1-methyl-1-carboethoxyisochroman. A 0.5 g sample of this is dissolved in ether and treated with 100 mg of LAH. After 10 minutes, the mixture is quenched with ethyl acetate and partitioned between 1 N aqueous sodium hydroxide and CH2Cl2. The organic phase yields 0.34 g of 6,7-dimethoxy-1-methyl-1-hydroxymethylisochroman. This is dissolved in THF and treated sequentially with sodium hydride and then o-tetrahydropyranyl chloroethanol. The adduct, upon treatment with acid and water, yields 2-[(7,8-dimethoxy-1-methyl-isochroman-1-yl)methoxy]ethanol. In the manner of Preparation 7, this can be converted to its benzenesulfonates ##STR21## Furthermore, 2-[(1-methylisochroman-1-yl)methoxy]ethanols, with various substituents on the isochroman ring, can be prepared by using the appropriate phenyl ethanols whose substituents, R1 -R5 (vide supra), are analogous to those substituents of the isochromans of Table 3.

Workup

  1. extractionextracted with aqueous sodium bicarbonate
  2. dry with materialThe organic phase is dried (sodium sulfate)
  3. concentrationconcentrated
  4. customchromatographed on silica gel

Sources & evidence

ORD record
ord-084b9e730e094b9fa8e953769e81f6ce
Source dataset
uspto-grants-1982_10
Patent number
US04352805

Reaction notes

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