Diisopropylamine → HCID 70416297, compound

HRID 569508Notes

Reaction equation

HRID 569508 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[CH3:13][N:14]1[CH2:23][CH2:22][C@H:21]2[C@@H:16]([C:17](=[O:30])[C:18]3[C:26]4[CH2:27][CH2:28][CH2:29][C:25]=4[NH:24][C:19]=3[CH2:20]2)[CH2:15]1.[CH3:31][C:32]([CH3:50])([CH2:36][CH2:37][O:38][C:39](=[O:49])[CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][CH2:47][CH3:48])[C:33](Cl)=[O:34]>O1CCCC1.CCCCCC>[CH3:50][C:32]([CH3:31])([CH2:36][CH2:37][O:38][C:39](=[O:49])[CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][CH2:47][CH3:48])[C:33]([N:24]1[C:19]2[CH2:20][C@@H:21]3[C@@H:16]([C:17](=[O:30])[C:18]=2[C:26]2[CH2:27][CH2:28][CH2:29][C:25]1=2)[CH2:15][N:14]([CH3:13])[CH2:23][CH2:22]3)=[O:34]

Participants

7

Reactant 4

HCID 7912DiisopropylamineHCID 12855939HCID 12855939, compoundHCID 14152318HCID 14152318, compoundHCID 178418339Butyllithium

Product 1

HCID 70416297HCID 70416297, compoundYield 47%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Procedure

To a solution of diisopropylamine (0.15 g) in tetrahydrofuran (15 mL) was added n-butyllithium in hexane (0.75 mL, 2M solution) at -20° to -30° and the solution was stirred at -20° to -30° C. for 30 minutes. To the solution was added at -20° to -30° C. (in one portion) trans-1,3,4,4a,5,7,8,9,10,10a-decahydro-2-methyl-6H-cyclopenta[4,5]pyrrolo[2,3-g]isoquinolin-10(2H)-one (0.244 g) and the mixture was stirred at -20° C. for 2 hours. To the solution was added the crude 2,2-dimethyl-4-[(1-oxodecyl)oxy]butanoyl chloride (0.45 g) in tetrahydrofuran at -20° to -30° and the mixture was stirred at this temperature for an additional 1 hour. The mixture was poured onto ice water and extracted in the dichloromethane. The combined dichloromethane extracts were washed with brine dried sodium sulfate and evaporated. The crude product was chromatographed on silica gel eluting with 5% methanol in dichloromethane to give 0.24 g of oily material (47%), trans-1,3,4,4a,5,6,7,8,9,10a-Decahydro-6-[2,2-dimethyl-1-oxo-4-[(1-oxodecyl)oxy]butyl]-2-methylcyclopenta[4,5]pyrrolo[2,3-g]isoquinolin-10(2H)-one IR (CHCl3), 1778 (C=O) and 1657 (C=O); NMR (CDCl3), δ0.88 (t, 3, CH3); 1.2-1.4 (m, 20, CH2 and CH3) 2.41 (5, 3, CH3); 3.04 (br.d, 1, CH); 3.56 (br.d, 1, CH); 4.14 (t, 2, CH2); MS m/e 512 (M+).

Workup

  1. stirringthe mixture was stirred at -20° C. for 2 hours
  2. stirringthe mixture was stirred at this temperature for an additional 1 hour
  3. additionThe mixture was poured onto ice water
  4. extractionextracted in the dichloromethane
  5. washThe combined dichloromethane extracts were washed with brine dried sodium sulfate
  6. customevaporated
  7. customThe crude product was chromatographed on silica gel eluting with 5% methanol in dichloromethane

Sources & evidence

ORD record
ord-51b9a46b8c9f45f6a9d796c0b09d72aa
Source dataset
uspto-grants-1988_03
Patent number
US04732902

Reaction notes

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