1-Isocyanatoadamantane → HCID 57147682, compound

HRID 1459400Notes

Reaction equation

HRID 1459400 reaction equation
[CH3:1][O:2][C:3](=[O:19])[CH:4]([CH2:12][C:13]1[CH:18]=[CH:17][N:16]=[CH:15][CH:14]=1)[CH2:5][C:6]1[CH:11]=[CH:10][N:9]=[CH:8][CH:7]=1.C([N-]C(C)C)(C)C.[Li+].[C:28]12([N:38]=[C:39]=[O:40])[CH2:37][CH:32]3[CH2:33][CH:34]([CH2:36][CH:30]([CH2:31]3)[CH2:29]1)[CH2:35]2>O1CCCC1.C1CCCCC1>[CH3:1][O:2][C:3](=[O:19])[C:4]([CH2:5][C:6]1[CH:7]=[CH:8][N:9]=[CH:10][CH:11]=1)([CH2:12][C:13]1[CH:14]=[CH:15][N:16]=[CH:17][CH:18]=1)[C:39]([NH:38][C:28]12[CH2:37][CH:32]3[CH2:31][CH:30]([CH2:36][CH:34]([CH2:33]3)[CH2:35]1)[CH2:29]2)=[O:40]

Participants

6

Reactant 3

HCID 20599951-IsocyanatoadamantaneHCID 2724682Lithium diisopropylamide2×HCID 18770380HCID 18770380, compound

Product 1

HCID 57147682HCID 57147682, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8078CyclohexaneSolvent

Procedure

To a stirred solution of 3-pyridin4-yl-2-pyridin4-ylmethyl-propionic acid methyl ester (24.44 g, 95 mmol) in tetrahydrofuran (300 ml) chilled with a dry ice/acetone bath, lithium diisopropylamide (70 ml of a 1.5M solution in cyclohexane, 105 mmol of lithium diisopropylamide) was added dropwise over 15 minutes. After stirring for 20 minutes, the solution temperature was elevated to -40° C. After 30 minutes of stirring at -40° C., a solution of adamantyl isocyanate (16.92 g, 95 mmol) in tetrahydrofuran (100 ml) was added dropwise over 10 minutes. After 15 minutes stirring, the cooling bath was removed and the reaction was then stirred for 3 hours at ambient temperature. The reaction was then chilled in an ice water bath and glacial acetic acid (14 ml) was added dropwise over 10 minutes. After stirring for 20 minutes at ambient temperature, the solvent was removed in vacuo, and the residue was extracted into water/methylene chloride (300 ml of each). The aqueous phase was extracted three times with 200 ml portions of fresh methylene chloride. The combined organic extracts were dried (anhydrous sodium sulfate), and concentrated in vacuo to an oil (49.6 g).

Workup

  1. customwas elevated to -40° C
  2. stirringAfter 30 minutes of stirring at -40° C.
  3. stirringAfter 15 minutes stirring
  4. customthe cooling bath was removed
  5. stirringthe reaction was then stirred for 3 hours at ambient temperature
  6. temperatureThe reaction was then chilled in an ice water bath
  7. additionglacial acetic acid (14 ml) was added dropwise over 10 minutes
  8. stirringAfter stirring for 20 minutes at ambient temperature
  9. customthe solvent was removed in vacuo
  10. extractionthe residue was extracted into water/methylene chloride (300 ml of each)
  11. extractionThe aqueous phase was extracted three times with 200 ml portions of fresh methylene chloride
  12. dry with materialThe combined organic extracts were dried (anhydrous sodium sulfate)
  13. concentrationconcentrated in vacuo to an oil (49.6 g)

Sources & evidence

ORD record
ord-8395f7ea29eb4bf08e5b62db69a38d4f
Source dataset
uspto-grants-1998_12
Patent number
US05854232

Reaction notes

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