Dimethylformamide → HCID 131727477, compound

HRID 1985710Notes

Reaction equation

HRID 1985710 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:20][C@@H:19]([CH3:21])[N:18]2[C@H:10]([CH2:11][C:12]3[C:17]2=[N:16][C:15]([CH:22]([C:27]([CH3:32])([CH3:31])[CH:28]([CH3:30])[CH3:29])[O:23][SiH:24]([CH3:26])[CH3:25])=[C:14](Br)[CH:13]=3)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C([Li])(C)(C)C.CN(C)[CH:41]=[O:42]>C1(C)C=CC=CC=1.CCCCC>[C:1]([O:5][C:6]([N:8]1[CH2:20][C@@H:19]([CH3:21])[N:18]2[C@H:10]([CH2:11][C:12]3[C:17]2=[N:16][C:15]([CH:22]([C:27]([CH3:32])([CH3:31])[CH:28]([CH3:30])[CH3:29])[O:23][SiH:24]([CH3:26])[CH3:25])=[C:14]([CH:41]=[O:42])[CH:13]=3)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 3

HCID 6228DimethylformamideHCID 131727478HCID 131727478, compoundHCID 178418306HCID 178418306, compound

Product 1

HCID 131727477HCID 131727477, compoundYield 94.6%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8003PentaneSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of 26.5 g (0.049 mol) (4R,9aR)-7-bromo-6-[dimethyl-(1,1,2-trimethyl-propyl)-silanyloxymethyl]-4-methyl-3,4,9,9a-tetrahydro-1H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester in 800 ml toluene was added at −78° C. during 10 minutes 50 ml of a 1.5 M solution of tert. butyllithium in pentane. The reaction mixture was stirred at −78° C. for 30 minutes. To the resulting orange solution was added 30 ml dimethylformamide during 3 minutes. The reaction mixture was stirred at −78° C. for 30 minutes and the cooling bath was then removed and the mixture was stirred for 30 min at ambient temperature. The reaction was quenched by addition of 300 ml of a 10% aqueous solution of citric acid and extracted with ethyl acetate. The organic phase was washed with a 10% aqueous solution of sodium bicarbonate and brine, dried over sodium sulfate, evaporated under aspirator vacuum and purified by chromatography on silica gel with heptane:ethyl acetate=4:1 to 3:1. to yield 22.70 g (94.6%) of the title compound as yellow foam (MS: 490 (M+H+)).

Workup

  1. stirringThe reaction mixture was stirred at −78° C. for 30 minutes
  2. customthe cooling bath was then removed
  3. stirringthe mixture was stirred for 30 min at ambient temperature
  4. customThe reaction was quenched by addition of 300 ml of a 10% aqueous solution of citric acid
  5. extractionextracted with ethyl acetate
  6. washThe organic phase was washed with a 10% aqueous solution of sodium bicarbonate and brine
  7. dry with materialdried over sodium sulfate
  8. customevaporated under aspirator vacuum
  9. custompurified by chromatography on silica gel with heptane

Sources & evidence

ORD record
ord-86954ee8c8124fa4aea3eb7e42d5b7e0
Source dataset
uspto-grants-2009_06
Patent number
US07547699B2

Reaction notes

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