Hexachloroethane → HCID 86596367, compound

HRID 1272173Notes

Reaction equation

HRID 1272173 reaction equation
C(OC([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][CH:15]=[C:14]([F:22])[CH:13]=3)[CH2:9]1)=O)(C)(C)C.C([Li])(C)(C)C.[Cl:28]C(Cl)(Cl)C(Cl)(Cl)Cl>C1(C)C=CC=CC=1.CCCCC>[Cl:28][C:15]1[N:16]=[C:17]2[C:12](=[CH:13][C:14]=1[F:22])[CH2:11][C@H:10]1[N:18]2[C@H:19]([CH3:21])[CH2:20][NH:8][CH2:9]1

Participants

6

Reactant 3

HCID 6214HexachloroethaneHCID 69357759HCID 69357759, compound2×HCID 178418306HCID 178418306, compound

Product 1

HCID 86596367HCID 86596367, compoundYield 8.8%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8003PentaneSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of 0.23 g (4R,9aR)-7-fluoro-4-methyl-3,4,9,9a-tetrahydro-1H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester (intermediate h of examples 54–61) in 5 mL toluene was added dropwise at −78° C. 1.4 mL of a ca 1.3 M solution of t-butyllithium in pentane. The mixture was stirred at −78° C. for 30 min. To the resulting mixture was added 0.3 g hexachloroethane and the mixture was stirred at −78° C. for 30 min and then allowed to thaw to 0° C. over ca 30 min. The reaction was quenched with 10% citric acid and the organic phase was separated and evaporated and the residue purified by chromatography on silica gel with heptane:ethyl acetate (4:1). The product fractions containing the two isomers and some starting material were evaporated and the residue was taken up in 1 mL trifluoroacetic acid and kept at room temperature for 30 min. The solvent was evaporated and the residue was purified by chromatography on silica gel with dichloromethane:methanol:ammonia (9:1:0.1). The product fractions containing the more polar isomer were collected evaporated and dried under high vacuum to yield 0.016 g (4R,9aR)-6-chloro-7-fluoro-4-methyl-1,2,3,4,9,9a-hexahydro-2,4a,5-triaza-fluorene as light brown gum.

Workup

  1. stirringthe mixture was stirred at −78° C. for 30 min
  2. customthaw to 0° C.
  3. customover ca 30 min
  4. customThe reaction was quenched with 10% citric acid
  5. customthe organic phase was separated
  6. customevaporated
  7. customthe residue purified by chromatography on silica gel with heptane:ethyl acetate (4:1)
  8. additionThe product fractions containing the two isomers
  9. customsome starting material were evaporated
  10. waitkept at room temperature for 30 min
  11. customThe solvent was evaporated
  12. customthe residue was purified by chromatography on silica gel with dichloromethane:methanol:ammonia (9:1:0.1)
  13. additionThe product fractions containing the more polar isomer
  14. customwere collected
  15. customevaporated
  16. customdried under high vacuum

Sources & evidence

ORD record
ord-cec07f96980f4a9e813a0473c8f75685
Source dataset
uspto-grants-2007_04
Patent number
US07208494B2

Reaction notes

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