Hydrochloric Acid → 2-Methylpentane

HRID 2181355Notes

Reaction equation

HRID 2181355 reaction equation
[CH:1]1([CH2:4][N:5]2[C:10]3[S:11][CH:12]=[C:13]([C:14]([OH:16])=[O:15])[C:9]=3[C:8](=[O:17])[N:7]([CH3:18])[C:6]2=[O:19])[CH2:3][CH2:2]1.C([N-]C(C)C)(C)C.[Li+].[F:28][C:29]([F:39])([F:38])[C:30]1[CH:37]=[CH:36][CH:35]=[CH:34][C:31]=1[CH:32]=O.Cl>O1CCCC1>[CH3:36][CH2:37][CH2:30][CH:31]([CH3:34])[CH3:32].[CH:1]1([CH2:4][N:5]2[C:10]3[S:11][C:12]([CH2:32][C:31]4[CH:34]=[CH:35][CH:36]=[CH:37][C:30]=4[C:29]([F:28])([F:38])[F:39])=[C:13]([C:14]([OH:16])=[O:15])[C:9]=3[C:8](=[O:17])[N:7]([CH3:18])[C:6]2=[O:19])[CH2:3][CH2:2]1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 123067o-(Trifluoromethyl)benzaldehydeHCID 2724682Lithium diisopropylamideHCID 22484123HCID 22484123, compound

Product 2

HCID 78922-MethylpentaneHCID 22484116HCID 22484116, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

1-(Cyclopropylmethyl)-1,2,3,4-tetrahydro-3-methyl-2,4-dioxo-thieno[2,3-d]pyrimidine-5-carboxylic acid (6.8 g) was suspended in tetrahydrofuran (100 ml) and cooled to −78° C. to which lithium diisopropylamide (63 ml, 1M) was added. After complete addition the solution was left for 30 min before 2-(trifluoromethyl)-benzaldehyde, (7.4 mls) was added neat. After 1 h HCl(2M in water) was added and the reaction allowed to warm to room temperature. The reaction was concentrated in vacuo and partitioned between ethyl acetate and HCl (2M in water). The organic phase was collected, dried over magnesium sulfate, filtered and concentrated in vacuo and redissolved in diethyl ether, then washed with half saturated sodium hydrogen bicarbonate. The aqueous phase was collected and the diethyl ethyl was washed a seconded time with half saturated sodium hydrogen bicarbonate. The aqueous extracts were combined, acidified with HCl (conc.) and extracted with ethyl acetate. The organic phase was collected, dried over magnesium sulfate, filtered and concentrated in vacuo to brown gum. The gum was redissolved in trifluoroacetic acid (10 mls) and triethyl silane(5 mls) and stirred at room temperature for 72 hrs. The reaction was then concentrated in vacuo, and partioned between dichloromethane and water. The organics were collected, dried over magnesium sulfate, filtered and concentrated in vacuo before being purified by chromatography eluting with 20:1 dichloromethane:acetic acid and recrstallisation from ethyl acetate and isohexane, to yield 3.63 g of the subtitle compound.

Workup

  1. additionwas added
  2. additionAfter complete addition the solution
  3. additionwas added neat
  4. concentrationThe reaction was concentrated in vacuo
  5. custompartitioned between ethyl acetate and HCl (2M in water)
  6. customThe organic phase was collected
  7. dry with materialdried over magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. dissolutionredissolved in diethyl ether
  11. washwashed with half saturated sodium hydrogen bicarbonate
  12. customThe aqueous phase was collected
  13. washthe diethyl ethyl was washed a seconded time with half saturated sodium hydrogen bicarbonate
  14. extractionextracted with ethyl acetate
  15. customThe organic phase was collected
  16. dry with materialdried over magnesium sulfate
  17. filtrationfiltered
  18. concentrationconcentrated in vacuo to brown gum
  19. dissolutionThe gum was redissolved in trifluoroacetic acid (10 mls)
  20. concentrationThe reaction was then concentrated in vacuo
  21. customThe organics were collected
  22. dry with materialdried over magnesium sulfate
  23. filtrationfiltered
  24. concentrationconcentrated in vacuo
  25. custombefore being purified by chromatography
  26. washeluting with 20:1 dichloromethane

Sources & evidence

ORD record
ord-27c37ac74ad2490294c33ab17584b22d
Source dataset
uspto-grants-2005_05
Patent number
US06890923B2

Reaction notes

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