Tri-o-tolylphosphine → HCID 59812013, compound

HRID 2114035Notes

Reaction equation

HRID 2114035 reaction equation
C([Si](C)(C)[N:6]1[C:10]2=[N:11][CH:12]=[C:13]([C:15]3[CH:20]=[CH:19][C:18]([N:21]([CH3:23])[CH3:22])=[CH:17][CH:16]=3)[CH:14]=[C:9]2[C:8]([Sn](CCCC)(CCCC)CCCC)=[CH:7]1)(C)(C)C.Br[C:40]1[C:44]([CH3:45])=[CH:43][S:42][CH:41]=1.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>C1(C)C=CC=CC=1.CCOC(C)=O.CC#N.CC#N.Cl[Pd]Cl>[CH3:23][N:21]([CH3:22])[C:18]1[CH:17]=[CH:16][C:15]([C:13]2[CH:14]=[C:9]3[C:8]([C:40]4[C:44]([CH3:45])=[CH:43][S:42][CH:41]=4)=[CH:7][NH:6][C:10]3=[N:11][CH:12]=2)=[CH:20][CH:19]=1

Participants

7

Reactant 3

HCID 80271Tri-o-tolylphosphineHCID 27349353-Bromo-4-methylthiopheneHCID 59811998HCID 59811998, compound

Product 1

HCID 59812013HCID 59812013, compoundYield 21%

Reagents, catalysts & solvents 3

HCID 6093782Bis(acetonitrile)dichloropalladiumCatalystHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
85 °C

Procedure

A mixture of 7 (129.7 mg, 0.186 mmol), 3-bromo-4-methylthiophene (30 μL, 0.30 mmol), PdCl2(MeCN)2 (4.8 mg, 18.6 μmol), tri-o-tolylphosphine (11.4 mg, 37.5 μmol) in toluene (1.7 mL) was stirred under N2 at 85° C. overnight. The reaction mixture was cooled to r.t., diluted with AcOEt (3 mL), and extracted with 10% aqueous HCl ((4×0.5 mL). combined aqueous solutions were washed with CH2Cl2 (2 mL), and basified with 10% aqueous NaOH (2.5 mL). The mixture was extracted with CH2Cl2:MeOH=19:1 (4×3 mL). Combined extracts were washed with brine, dried (MgSO4), and concentrated in vacuum. The residue was purified by preparative TLC using CH2Cl2:MeOH=19:1 as eluent to afford 8 (12.9 mg, 21%) as tan solid. 1H NMR (400 MHz, CDCl3) δ 2.34 (d, J=1.0 Hz, 3H), 3.01 (s, 6H), 6.85 (d, J=8.9 Hz, 2H), 7.10 (dq, J=3.3, 1.0 Hz, 1H), 7.36 (d, J=3.3 Hz, 1H), 7.41 (d, J=1.2 Hz, 1H), 7.53 (d, J=8.9 Hz, 2H), 8.14 (d, J=2.1 Hz, 1H), 8.59 (d, J=2.1 Hz, 1H), 10.00 (bs, 1H).

Workup

  1. temperatureThe reaction mixture was cooled to r.t.
  2. extractionextracted with 10% aqueous HCl ((4×0.5 mL)
  3. washcombined aqueous solutions were washed with CH2Cl2 (2 mL)
  4. extractionThe mixture was extracted with CH2Cl2
  5. washCombined extracts were washed with brine
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated in vacuum
  8. customThe residue was purified by preparative TLC

Sources & evidence

ORD record
ord-ca40b232186d4694a45341d23bbe13ed
Source dataset
uspto-grants-2008_10
Patent number
US07432375B2

Reaction notes

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