Triethylamine → HCID 23501331, compound

HRID 1770356Notes

Reaction equation

HRID 1770356 reaction equation
[H-].[H-].[H-].[H-].[Li+].[Al+3].C(N(CC)CC)C.[Si:14]([O:21][C:22]1[CH:23]=[C:24]([CH:29]=[CH:30][CH:31]=1)[C:25]([O:27][CH3:28])=O)([C:17]([CH3:20])([CH3:19])[CH3:18])([CH3:16])[CH3:15].[CH:32]12[CH2:41][CH:36]3[CH2:37][CH:38]([CH2:40][CH:34]([CH2:35]3)[C:33]1=O)[CH2:39]2>C1COCC1.CCOCC>[Si:14]([O:21][C:22]1[CH:23]=[C:24]([CH2:25][O:27][CH:28]=[C:33]2[CH:34]3[CH2:40][CH:38]4[CH2:37][CH:36]([CH2:41][CH:32]2[CH2:39]4)[CH2:35]3)[CH:29]=[CH:30][CH:31]=1)([C:17]([CH3:20])([CH3:19])[CH3:18])([CH3:16])[CH3:15]

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 64151AdamantanoneHCID 11715937Benzoic acid, 3-[[(1,1-dimethylethyl)dimethylsilyl]oxy]-, methyl esterHCID 21226445Aluminium lithium hydride

Product 1

HCID 23501331HCID 23501331, compoundYield 21%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

A 500 mL three-neck flask was fitted with a reflux condenser, 125 mL addition funnel, and nitrogen line. The apparatus was dried by means of a hot air gun and nitrogen purging. Dry THF (200 mL) was added and the flask cooled in an ice bath. TiCL3 (24 g, 156 mmol) was added rapidly followed by LAH (2.8 g, 75 mmol) in portions with stirring. The cooling bath was removed and the black mixture was allowed to warm to room temperature. Triethylamine (12 mL, 86 mmol) was added to the stirred suspension and refluxed for 1 hour. After this period a solution of methyl 3-tert-butyldimethylsilyloxybenzoate (4.40 g, 16.6 mmol) and 2-adamantanone (3.0 g, 20.4 mmol) in 50 mL of dry THF was added dropwise to the refluxing mixture over 5 hours. Refluxing was continued for an additional 4 hours after which the reaction was cooled to room temperature and diluted with 100 mL of ether. The organic solution was separated and concentrated. Chromatography over silica with 1% ethyl acetate/hexane gave 1.29 g (21%) of 7b as an oil: 1H NMR (CDCl3) delta 0.196 (s, 6H), 0.985 (s, 9H), 1.78-1.97 (m, 12H), 2.628 (s, 1H, 3.23 (s, 1H), 3.29 (s, 3H), 6.75-7.20 (m, 4H); 13C NMR (CDCl3) delta -4.50, 18.19, 25.67, 28.37, 30.16, 32.28, 37.25, 38.19, 39.01, 57.51, 119.29, 121.08, 122.32, 128.87, 131.11, 136.84, 143.47, 155.37. ##STR43##

Workup

  1. customA 500 mL three-neck flask was fitted with a reflux condenser, 125 mL addition funnel
  2. customThe apparatus was dried by means of a hot air gun and nitrogen purging
  3. additionDry THF (200 mL) was added
  4. temperaturethe flask cooled in an ice bath
  5. additionTiCL3 (24 g, 156 mmol) was added rapidly
  6. customThe cooling bath was removed
  7. temperaturerefluxed for 1 hour
  8. temperatureRefluxing
  9. temperatureafter which the reaction was cooled to room temperature
  10. customThe organic solution was separated
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-2a8d6d7f2da44232ac7b8291c2342845
Source dataset
uspto-grants-1995_01
Patent number
US05386017

Reaction notes

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