Hydrochloric Acid → 4-Hydroxymethylbenzyl 5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-naphthyl ether

HRID 483715Notes

Reaction equation

HRID 483715 reaction equation
ClC(OCC)=O.[CH3:7][C:8]1([CH3:31])[CH2:17][CH2:16][C:15]([CH3:19])([CH3:18])[C:14]2[CH:13]=[C:12]([O:20][CH2:21][C:22]3[CH:27]=[CH:26][C:25]([C:28](O)=[O:29])=[CH:24][CH:23]=3)[CH:11]=[CH:10][C:9]1=2.C(N(CC)CC)C.[BH4-].[Na+].Cl>O1CCCC1.O>[CH3:7][C:8]1([CH3:31])[CH2:17][CH2:16][C:15]([CH3:18])([CH3:19])[C:14]2[CH:13]=[C:12]([O:20][CH2:21][C:22]3[CH:27]=[CH:26][C:25]([CH2:28][OH:29])=[CH:24][CH:23]=3)[CH:11]=[CH:10][C:9]1=2

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 8471TriethylamineHCID 10928Ethyl chloroformateHCID 4311764Sodium borohydrideHCID 148505784-Carboxybenzyl 5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-naphthyl ether

Product 1

HCID 148505824-Hydroxymethylbenzyl 5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-naphthyl etherYield 37.7%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
0 °C

Procedure

A solution of 0.97 g (9 mmol) of ethyl chloroformate in 5 ml of tetrahydrofuran was added dropwise to a solution of 3 g (9 mmol) of 4-carboxybenzyl 5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-naphthyl ether and 0.9 g (9 mmol) of triethylamine in 20 ml of dry tetrahydrofuran at 0° C. The mixture was stirred at 0° C. for 30 min, the solid was filtered off, and the filtrate was added dropwise to a solution of 0.83 g (22 mmol) of sodium borohydride in 8 ml of tetrahydrofuran and 8 ml of water. The reaction mixture was then allowed to reach room temperature within 1 h and was then acidified with 1N hydrochloric acid. Most of the tetrahydrofuran was removed in a rotary evaporator, and the remaining aqueous phase was extracted with chloroform. The organic phase was dried over Na2SO4 and concentrated. Fractional crystallization from ethyl acetate, discarding the first fraction, resulted in 1.1 g of the title compound of melting point 108°-109° C.

Workup

  1. filtrationthe solid was filtered off
  2. waitto reach room temperature within 1 h
  3. customMost of the tetrahydrofuran was removed in a rotary evaporator
  4. extractionthe remaining aqueous phase was extracted with chloroform
  5. dry with materialThe organic phase was dried over Na2SO4
  6. concentrationconcentrated
  7. customFractional crystallization from ethyl acetate

Sources & evidence

ORD record
ord-0062eef9eab544bb84889a0e0be78fff
Source dataset
uspto-grants-1993_07
Patent number
US05225601

Reaction notes

Loading…