2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → 5-(2-Chloro-5-fluoropyrimidin-4-yl)-N-methyl-N-phenylthiazol-2-amine

HRID 2267384Notes

Reaction equation

[Li]C(C)(C)C.CCCCCCC.[CH3:13][N:14]([C:21]1[S:22][CH:23]=[CH:24][N:25]=1)[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.[Cl:26][C:27]1[N:32]=[CH:31][C:30]([F:33])=[CH:29][N:28]=1.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl.O=C1O[C@H]([C@H](CO)O)C([O-])=C1O.[Na+]>C1COCC1.O>[Cl:26][C:27]1[N:32]=[C:31]([C:23]2[S:22][C:21]([N:14]([CH3:13])[C:15]3[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=3)=[N:25][CH:24]=2)[C:30]([F:33])=[CH:29][N:28]=1

Participants

Conditions

Temperature: -78 °C

Procedure

A 1.6 M solution of tBuLi in heptane (1.6 mL, 2.6 mmol) was added to a stirred solution of 0.44 g (2.3 mmol) of 2-(N-Methyl-N-phenylamino)thiazole in 8 mL of THF at −78° C. The solution was stirred for 15 min at −78° C. before 0.24 mL (2.6 mmol) of 2-chloro-5-fluoropyrimidine and 2 mL of THF were added. The reaction solution was stirred for 10 min at −78° C., then quenched by addition of 1 mL of AcOH in 1 mL of MeOH. Solid 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (1.1 g, 4.6 mmol) was added and the reaction solution was warmed to 0° C. and stirred for 30 min, poured into 50 mL of a 0.5 M solution of sodium ascorbate, diluted with 200 mL of water and the crude product removed by filtration and washed repeatedly with water. The residue was dried by toluene co-evaporation to deliver the title compound. MS (M+H)+ 321.

Workup

additionwere added
customquenched by addition of 1 mL of AcOH in 1 mL of MeOH
temperaturethe reaction solution was warmed to 0° C.
stirringstirred for 30 min
customthe crude product removed by filtration
washwashed repeatedly with water
dry with materialThe residue was dried by toluene co-evaporation

Sources & evidence

ORD record: ord-6ec377d3b5244a8ab07789cd8dffcf68
Source dataset: uspto-grants-2010_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07858785B2

Reaction notes

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