Triethylamine → HCID 21466649, compound

HRID 1940363Notes

Reaction equation

HRID 1940363 reaction equation
[H-].[H-].[H-].[H-].[Li+].[Al+3].C(N(CC)CC)C.[OH:14][C:15]1[CH:16]=[C:17]([CH:22]=[CH:23][CH:24]=1)[C:18]([O:20][CH3:21])=O.[CH:25]12[CH2:34][CH:29]3[CH2:30][CH:31]([CH2:33][CH:27]([CH2:28]3)[C:26]1=O)[CH2:32]2>C1COCC1.O>[OH:14][C:15]1[CH:16]=[C:17]([CH2:18][O:20][CH2:21][C:25]23[CH2:34][CH:29]4[CH2:30][CH:31]([CH2:33][CH:27]([CH2:28]4)[CH2:26]2)[CH2:32]3)[CH:22]=[CH:23][CH:24]=1

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 64151AdamantanoneHCID 88068Methyl 3-HydroxybenzoateHCID 21226445Aluminium lithium hydride

Product 1

HCID 21466649HCID 21466649, compoundYield 89%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

[(3-Hydroxyphenyl)methoxymethyl]adamantane (1a) was prepared as described in my previous application Ser. No. 224,681, filed Jul. 27, 1988. A 500-mL flask was fitted with a reflux condenser, a 125-mL addition funnel, and nitrogen line. The apparatus was dried by means of a hot air gun and nitrogen purging. Dry THF (40 mL) was added and the flask cooled in an ice bath. TiCl3 (1.5 g, 10 mmol) was added rapidly followed by LAH (0.19 g, 5 mmol) in portions with stirring. The cooling bath was removed and the black mixture was allowed to warm to room temperature. Triethylamine (0.7 mL, 5 mmol) was added to the stirred suspension and refluxed for 15 min. After this period, a solution of methyl 3-hydroxybenzoate (152 mg, 1 mmol) and 2-adamantanone (300 mg, 2 mmol) in 20 mL of dry THF was added dropwise to the refluxing mixture over 15 min. Refluxing was continued for an additional 15 min after which the reaction was cooled to room temperature and diluted with 100 mL of distilled water. The aqueous solution was extracted with 3×50 mL portions of ethyl acetate. The combined organic layer was washed with water, dried over MgSO4, and concentrated. Chromatography over silica with 15% ethyl acetate/hexane gave 240 mg (89%) of 1a as a white solid: mp 133°-4° C.; 1H NMR (CDCl3) δ1.64-1.96 (m, 12H), 2.65 (s, 1H), 3.24 (s, 1H), 3.32 (s, 3H), 5.25 (s, 1H, OH exchange with D2O), 6.70-7.30 (m, 4H); 13C NMR (CDCl3) δ28.45, 30.36, 32.36, 37.30, 39.18, 39.33, 57.82, 114.60, 116.16, 122.19, 129.24, 137.24, 155.62; MS m/e (rel intensity) 271 (20, M+1), 270 (100, M), 253 (7.3), 213 (35.1), 121 (41.7), 93 (9.4); Exact mass: calcd 270.1619, found 270.1616. ##STR21##

Workup

  1. custom[(3-Hydroxyphenyl)methoxymethyl]adamantane (1a) was prepared
  2. customA 500-mL flask was fitted with a reflux condenser, a 125-mL addition funnel
  3. customThe apparatus was dried by means of a hot air gun and nitrogen purging
  4. additionDry THF (40 mL) was added
  5. temperaturethe flask cooled in an ice bath
  6. customThe cooling bath was removed
  7. temperaturerefluxed for 15 min
  8. waitAfter this period
  9. temperatureRefluxing
  10. temperatureafter which the reaction was cooled to room temperature
  11. extractionThe aqueous solution was extracted with 3×50 mL portions of ethyl acetate
  12. washThe combined organic layer was washed with water
  13. dry with materialdried over MgSO4
  14. concentrationconcentrated

Sources & evidence

ORD record
ord-139807825e5c46c1957a75bdf4ddcb31
Source dataset
uspto-grants-1997_12
Patent number
US05698728

Reaction notes

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