4-Methoxy-alpha-toluenethiol → HCID 71076731, compound

HRID 1774506Notes

Reaction equation

HRID 1774506 reaction equation
[CH2:1]([O:3][C:4](=[O:12])[CH2:5][N:6]1[CH:10]=[C:9](I)[CH:8]=[N:7]1)[CH3:2].[CH3:13][O:14][C:15]1[CH:22]=[CH:21][C:18]([CH2:19][SH:20])=[CH:17][CH:16]=1.CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.CCN(C(C)C)C(C)C>O1CCOCC1.CCOC(C)=O.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH2:1]([O:3][C:4](=[O:12])[CH2:5][N:6]1[CH:10]=[C:9]([S:20][CH2:19][C:18]2[CH:21]=[CH:22][C:15]([O:14][CH3:13])=[CH:16][CH:17]=2)[CH:8]=[N:7]1)[CH3:2]

Participants

8

Reactant 4

HCID 804074-Methoxy-alpha-toluenethiolHCID 81531DiisopropylethylamineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 46738002Ethyl 4-iodo-1H-pyrazole-1-acetate

Product 1

HCID 71076731HCID 71076731, compound

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
90 °C

Procedure

(4-Iodo-pyrazol-1-yl)-acetic acid ethyl ester (1.8 g, 10.3 mmol), 4-methoxybenzyl mercaptan (1.43 mL, 10.3 mmol), Xantphos (0.298 g, 0.515 mmol) and then Hünig's base (3.7 mL, 21.2 mmol) were dissolved in dioxane (100 mL). The reaction was purged with N2 (g) for 10 minutes and then tris(dibenzylideneacetone)dipalladium(0) (0.235 g, 0.258 mmol) was added. The reaction was heated to 90° C. for 2 hours then cooled and diluted with EtOAc. The organic portion was washed with H2O and brine, with back-extraction, then dried and concentrated. The crude material was purified on silica gel (0-20% EtOAc in hexanes) to afford the title compound.

Workup

  1. customThe reaction was purged with N2 (g) for 10 minutes
  2. temperaturethen cooled
  3. washThe organic portion was washed with H2O and brine, with back-extraction
  4. customdried
  5. concentrationconcentrated
  6. customThe crude material was purified on silica gel (0-20% EtOAc in hexanes)

Sources & evidence

ORD record
ord-5da80e79d64f4117be5f2581fb772d97
Source dataset
uspto-grants-2016_02
Patent number
US09260416B2

Reaction notes

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