Triethylamine → HCID 19064092, compound

HRID 2392971Notes

Reaction equation

HRID 2392971 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].C(N(CC)CC)C.[Si:14]([O:21][C:22]1[CH:23]=[C:24]([CH:32]=[CH:33][CH:34]=1)[C:25]([O:27][CH2:28][CH2:29][CH2:30][Cl:31])=O)([C:17]([CH3:20])([CH3:19])[CH3:18])([CH3:16])[CH3:15].[CH:35]12[CH2:44][CH:39]3[CH2:40][CH:41]([CH2:43][CH:37]([CH2:38]3)[C:36]1=O)[CH2:42]2>C1COCC1.O.[Cl-].[Cl-].[Cl-].[Ti+3]>[Si:14]([O:21][C:22]1[CH:23]=[C:24]([C:25](=[C:36]2[CH:37]3[CH2:43][CH:41]4[CH2:40][CH:39]([CH2:44][CH:35]2[CH2:42]4)[CH2:38]3)[O:27][CH2:28][CH2:29][CH2:30][Cl:31])[CH:32]=[CH:33][CH:34]=1)([C:17]([CH3:20])([CH3:19])[CH3:18])([CH3:16])[CH3:15]

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 64151AdamantanoneHCID 21226445Aluminium lithium hydrideHCID 53950341HCID 53950341, compound

Product 1

HCID 19064092HCID 19064092, compound

Reagents, catalysts & solvents 3

HCID 10313229titanium(III) trichlorideCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

Titanium trichloride (25.8 g, 0.167 mol) was added to dry THF (500 mL) in a dried 3 L three-necked flask under a head of Ar at 0° C. Lithium aluminum hydride (3.01 g, 0.084 mol) was added in small portions with vigorous stirring. The reaction mixture was warmed to room temperature and 23.3 mL of triethylamine was added dropwise. After the addition was completed, the reaction mixture was refluxed for 2 h. Heating was stopped and a solution of 3-chloropropyl 3-(tert-butyldimethylsilyloxy)benzoate (5.28 g, 0.016 mol) and adamantanone (7.23 g, 0.048 mol) in 100 mL of dry THF was added dropwise to the refluxing mixture over a 45 min period. The reaction mixture was stirred over night at room temperature. The black mixture was diluted with water and extracted with 3×300 mL of hexane. The combined organic solutions were filtered, dried over sodium sulfate and concentrated under reduced pressure. The residue was partially purified by flash chromatography (2% ethyl acetate/hexane) to give the product as a viscous oil which was taken on to the next step. 1H NMR (CDCl3) δ0.200 (S, 6H), 0.988 (S, 9H), 1.66-2.01 (m, 14H), 2.63 (br s, 1H), 3.23 (br s, 1H), 3.538 (t, 2H, J=5.7 Hz), 3.640 (t, 2H, J=6.6 Hz), 6.75-7.22 (m, 4H). ##STR23##

Workup

  1. additionAfter the addition
  2. temperaturethe reaction mixture was refluxed for 2 h
  3. temperatureHeating
  4. extractionextracted with 3×300 mL of hexane
  5. filtrationThe combined organic solutions were filtered
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customThe residue was partially purified by flash chromatography (2% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-5be64b5f39004efa92ea2a1f0e918767
Source dataset
uspto-grants-1998_09
Patent number
US05804103

Reaction notes

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