Hydrochloric Acid → HCID 11644468, compound

HRID 1831878Notes

Reaction equation

HRID 1831878 reaction equation
CN(C1CCCCC1)[CH:3]1CCCC[CH2:4]1.Br[C:16]1[S:20][C:19]([C:21]([CH2:23][C:24]([C:26]([F:29])([F:28])[F:27])=[O:25])=[O:22])=[CH:18][CH:17]=1.C=C.Cl>O.CCOCC.C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.O1CCOCC1>[CH:3]([C:16]1[S:20][C:19]([C:21]([CH2:23][C:24]([C:26]([F:29])([F:28])[F:27])=[O:25])=[O:22])=[CH:18][CH:17]=1)=[CH2:4]

Participants

9

Reactant 4

HCID 313Hydrochloric AcidHCID 6325EthyleneHCID 24210N-Methyl dicyclohexylamineHCID 2551251-(5-Bromothiophen-2-yl)-4,4,4-trifluorobutane-1,3-dione

Product 1

HCID 11644468HCID 11644468, compoundYield 32.2%

Reagents, catalysts & solvents 4

HCID 83681Tris(1,1-dimethylethyl)phosphineCatalystHCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 312751,4-DioxaneSolvent

Procedure

1,4-Dioxane (40 mL), tri-t-butylphosphine (0.182 g, 0.9 mmol), and methyldicyclohexylamine (19.5 g, 100 mmol) were placed into a Schlenk flask and transferred by syringe to a PPI LC series 300 mL reactor containing dipalladium tris(dibenzylidenelacetone) (0.420 g, 0.45 mmol) and 5-bromothenoyltrifluoroacetone (9 g, 30 mmol) The reactor was charged to 300 psi with ethylene and the reaction was allowed to stir for 48 hours at room temperature. Upon completion of the reaction the contents taken up in water (50 mL) and ether (50 mL), the aqueous phase acidified by addition of concentrated hydrochloric acid, and extracted with ether (2×50 mL). The combined organic phase was rinsed with saturated sodium chloride solution, and the organic phase was dried over magnesium sulfate overnight. The solution was filtered, the solvent was removed by vacuum, and the residue dissolved in chloroform (3 mL). The product was isolated by column chromatography from silica gel (Selecto, mesh size 63-200) with 10% ether in chloroform as eluent. The solvent was removed to give a light green solid (2.4 g, 32% yield). The solid was reacted with cupric chloride dehydrate in methanol, precipitated by addition of water, and recrystallized from THF/hexanes to give (VTTFA)2Cu.1.5THF. 1H-NMR (90 MHz, 25° C., CDCl3): δ 14.25 (s, 1H), 7.63 (d, 1H), 7.12 (d, 1H), 6.94 (dd, 1H), 6.36 (s, 1H), 5.86 (s, 1H). Anal.: (found/calc for C26H24CuF6O5.5S2) 81.71 (81.58), H 5.65 (5.59).

Workup

  1. customtransferred by syringe to a PPI LC series 300 mL reactor
  2. customUpon completion of the reaction the contents
  3. extractionextracted with ether (2×50 mL)
  4. washThe combined organic phase was rinsed with saturated sodium chloride solution
  5. dry with materialthe organic phase was dried over magnesium sulfate overnight
  6. filtrationThe solution was filtered
  7. customthe solvent was removed by vacuum
  8. dissolutionthe residue dissolved in chloroform (3 mL)
  9. customThe product was isolated by column chromatography from silica gel (Selecto, mesh size 63-200) with 10% ether in chloroform as eluent
  10. customThe solvent was removed

Sources & evidence

ORD record
ord-ac692ffc25224608a32456068c42eb69
Source dataset
uspto-grants-2006_06
Patent number
US07067702B2

Reaction notes

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