Triethylamine → HCID 58063622, compound

HRID 2035682Notes

Reaction equation

HRID 2035682 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][N:11]=[CH:10][CH:9]=2)=[CH:4][C:3]=1[F:14].[Si]([C:19]#[CH:20])(C)(C)C.CCN(CC)CC.C([O-])([O-])=O.[K+].[K+]>CO.CCOC(C)=O.[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O.C1COCC1>[C:19]([C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][N:11]=[CH:10][CH:9]=2)=[CH:4][C:3]=1[F:14])#[CH:20]

Participants

11

Reactant 4

HCID 8471TriethylamineHCID 11430Potassium CarbonateHCID 66111TrimethylsilylacetyleneHCID 666841274-(4-Bromo-3-fluorophenyl)pyridine

Product 1

HCID 58063622HCID 58063622, compoundYield 67%

Reagents, catalysts & solvents 6

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 887MethanolSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
100 °C

Procedure

4-(4-bromo-3-fluorophenyl)pyridine (55 mg, 0.218 mmol), CuI (5.8 mg, 0.031 mmol), PdCl2(PPh3)2 (23 mg, 0.033 mmol) were placed in a μwave tube under an atmosphere of N2. TMS acetylene (46 μL, 0.327 mmol), Et3N (121 μL, 0.873 mmol) and THF (1.1 mL) were added and the mixture was heated to 100° C. for 20 min and then cooled to ambient temperature. The mixture was filtered through a silica gel pack and washed with EtOAc. Combined eluents were evaporated under reduced pressure to give crude TMS acetylenic product as a solid. The crude material from step 1 was dissolved in MeOH (in some cases 20% EtOAc was added to increase solubility) and 3 eq of K2CO3 added and the mixture stirred for 30 min. To the mixture was added water and extracted with EtOAc. The combined organic layers were dried, filtered and evaporated. The residue was purified by column chromatography on silica to afford the title compound 29 mg (0.146 mmol).

Workup

  1. temperaturecooled to ambient temperature
  2. filtrationThe mixture was filtered through a silica gel pack
  3. washwashed with EtOAc
  4. customCombined eluents were evaporated under reduced pressure
  5. customto give crude TMS acetylenic product as a solid
  6. additionwas added
  7. additionadded
  8. extractionextracted with EtOAc
  9. customThe combined organic layers were dried
  10. filtrationfiltered
  11. customevaporated
  12. customThe residue was purified by column chromatography on silica

Sources & evidence

ORD record
ord-dcb6acce118d44049e9ef32fcc6cb35a
Source dataset
uspto-grants-2013_11
Patent number
US08575150B2

Reaction notes

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