Diisopropylamine → HCID 67604664, compound

HRID 1735850Notes

Reaction equation

HRID 1735850 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.CCCCCC.[O:19]1[CH2:24][CH2:23][CH2:22][CH2:21][CH:20]1[O:25][CH2:26]P(=O)(OCC)OCC.[CH2:35]([C:38]1([CH:53]=O)[C:44]2[CH:45]=[CH:46][CH:47]=[CH:48][C:43]=2[CH2:42][CH2:41][C:40]2[CH:49]=[CH:50][CH:51]=[CH:52][C:39]1=2)[CH:36]=[CH2:37].[NH4+].[Cl-]>C1COCC1>[CH2:35]([C:38]1([CH:53]=[CH:26][O:25][CH:20]2[CH2:21][CH2:22][CH2:23][CH2:24][O:19]2)[C:39]2[CH:52]=[CH:51][CH:50]=[CH:49][C:40]=2[CH2:41][CH2:42][C:43]2[CH:48]=[CH:47][CH:46]=[CH:45][C:44]1=2)[CH:36]=[CH2:37]

Participants

8

Reactant 6

HCID 7912DiisopropylamineHCID 8058HexaneHCID 25517Ammonium ChlorideHCID 11230495Diethyl {[(oxan-2-yl)oxy]methyl}phosphonateHCID 19079053HCID 19079053, compoundHCID 178418339Butyllithium

Product 1

HCID 67604664HCID 67604664, compoundYield 46%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
0 °C

Procedure

Dissolved diisopropylamine (9.2 g, 0.0910 mol) in 200 mL of dry THF. Cooled to 0° C. under a nitrogen atmosphere. Added 2.5M n-butyl lithium in hexane (35.2 mL, 0.0880 mol) via syringe. Stirred at 0° C. for 10 mins then cooled to -78° C. Added diethyl [(2-tetrahydropyranyloxy)methyl]phosphonate in 45 mL of dry THF via addition funnel. Stirred at -78° C. for 1 hour. Added 10,11-dihydro-5-(2-propenyl)-5H-dibenzo[a,d]cyclohepten-5-carboxaldehyde in 100 mL of dry THF via addition funnel. Warmed to room temperature then refluxed for 16 hours. Cooled to room temperature, and added 500 mL of saturated NH4Cl. Separated layers, and extracted aqueous solution with ether. Washed combined organic extracts with saturated NaHCO3, dried with MgSO4, filtered, and evaporated. Purified crude product by flash chromatography on silica gel eluting with 3% ether-hexane then 5% ether-hexane. Combined appropriate fractions and evaporated to give 12.7 g (46% yield) of 10,11-dihydro-5-(2-propenyl)-5H-dibenzo[a,d]cyclohepten-5-yl-(2-tetrahydropyranyloxy-ethene).

Workup

  1. temperaturethen cooled to -78° C
  2. stirringStirred at -78° C. for 1 hour
  3. temperatureWarmed to room temperature
  4. temperaturethen refluxed for 16 hours
  5. temperatureCooled to room temperature
  6. extractionSeparated layers, and extracted aqueous solution with ether
  7. washWashed
  8. dry with materialdried with MgSO4
  9. filtrationfiltered
  10. customevaporated
  11. customPurified crude product by flash chromatography on silica gel eluting with 3% ether-hexane
  12. customevaporated

Sources & evidence

ORD record
ord-07d0bd3c30fe4ad38739754e83cc2933
Source dataset
uspto-grants-1996_07
Patent number
US05538986

Reaction notes

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