2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → 2-Chloro-4-(5-iodothiophen-2-yl)pyrimidine

HRID 2267347Notes

Reaction equation

[Li]CCCC.[I:6][C:7]1[S:8][C:9](I)=[CH:10][CH:11]=1.[Cl:13][C:14]1[N:19]=[CH:18][CH:17]=[CH:16][N:15]=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.C([O-])([O-])=O.[Na+].[Na+]>[Cl:13][C:14]1[N:19]=[C:18]([C:9]2[S:8][C:7]([I:6])=[CH:11][CH:10]=2)[CH:17]=[CH:16][N:15]=1

Participants

Conditions

Temperature: -20 °C

Procedure

nBuLi (16 mL, 1.6 M solution in hexane, 25 mmol) was added to a stirred solution of 2,5-diiodothiophene (7.0 g, 21 mmol) in THF (80 mL) at −50° C. The solution was stirred for 10 min at −50° C. before 2.9 g (25 mmol) of 2-chloropyrimidine was added. The reaction solution was stirred for 1 h at −20° C., then cooled to −50° C. and quenched by addition of 2 mL of AcOH in 10 mL of MeOH. Solid 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (10.4 g, 46 mmol) was added and the reaction solution was warmed to 0° C. and stirred for 1 h. The reaction mixture was then poured into 100 mL of a 0.5 M solution of sodium ascorbate, diluted with 250 mL of 1 M aqueous Na2CO3 and the crude product removed by filtration and washed repeatedly with water. The residue was azeotroped with toluene to give the product. MS (M+H)+ 323.

Workup

additionwas added
temperaturecooled to −50° C.
customquenched by addition of 2 mL of AcOH in 10 mL of MeOH
temperaturethe reaction solution was warmed to 0° C.
stirringstirred for 1 h
customthe crude product removed by filtration
washwashed repeatedly with water
customThe residue was azeotroped with toluene
customto give the product

Sources & evidence

ORD record: ord-56e8335d6bd44d089447e9ff1da52e3c
Source dataset: uspto-grants-2010_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07858785B2

Reaction notes

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