Ammonium Chloride → HCID 58474459, compound

HRID 1400856Notes

Reaction equation

HRID 1400856 reaction equation
[Cl:1][C:2]1[C:7]2[S:8][CH:9]=[CH:10][C:6]=2[N:5]=[CH:4][CH:3]=1.C([Li])CCC.Br[C:17]1[N:22]=[CH:21][C:20]([CH2:23][CH2:24][N:25]2[CH2:30][CH2:29][O:28][CH2:27][CH2:26]2)=[CH:19][CH:18]=1.[Cl-].[NH4+]>C1COCC1.[Cl-].[Zn+2].[Cl-].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Cl:1][C:2]1[CH:3]=[CH:4][N:5]=[C:6]2[CH:10]=[C:9]([C:17]3[N:22]=[CH:21][C:20]([CH2:23][CH2:24][N:25]4[CH2:30][CH2:29][O:28][CH2:27][CH2:26]4)=[CH:19][CH:18]=3)[S:8][C:7]=12

Participants

8

Reactant 4

HCID 25517Ammonium ChlorideHCID 112752517-Chlorothieno[3,2-b]pyridineHCID 58474653HCID 58474653, compoundHCID 178418339Butyllithium

Product 1

HCID 58474459HCID 58474459, compoundYield 101.4%

Reagents, catalysts & solvents 3

HCID 3007855ZincchlorideCatalystHCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To 7-chlorothienopyridine (0.81 g, 4.8 mmol) in THF (100 mL) at −78° C. was added n-butyllithium (2.5 M in hexanes, 2.1 mL, 5.1 mmol), dropwise. The mixture was allowed to warm to 0° C. then zinc chloride (1.0 M in diethyl ether, 4.8 mL, 4.8 mmol) was added. The mixture was stirred and warmed to room temperature. Bromide 175 (1.0 g, 3.7 mmol) and tetrakis(triphenylphosphine)palladium (0.85 g, 0.74 mmol) in THF (75 mL) were added dropwise, and the resultant mixture was heated to reflux for 2 h. It was then cooled and ammonium chloride (2.0 mL) was added, and the mixture was concentrated. The residue was partitioned between water and ethyl acetate, resulting in a thick precipitate. This was isolated by suction filtration and triturated with ethyl acetate, to provide title compound 176 (1.35 g, 100% yield, crude) as a yellow solid. LRMS (M+H): 360.4

Workup

  1. temperaturewarmed to room temperature
  2. temperatureto reflux for 2 h
  3. temperatureIt was then cooled
  4. concentrationthe mixture was concentrated
  5. customThe residue was partitioned between water and ethyl acetate
  6. customresulting in a thick precipitate
  7. customThis was isolated by suction filtration
  8. customtriturated with ethyl acetate

Sources & evidence

ORD record
ord-e98609967e11415d94695f8bc8dec976
Source dataset
uspto-grants-2014_12
Patent number
US08906852B2

Reaction notes

Loading…