Triphenylarsine → 3-(2,6-Dichloropyridin-3-yl)-4-(2-ethylaminopyridin-3-yl)thiophene

HRID 580818Notes

Reaction equation

Br[C:2]1[C:6]([C:7]2[C:8]([NH:13][CH2:14][CH3:15])=[N:9][CH:10]=[CH:11][CH:12]=2)=[CH:5][S:4][CH:3]=1.[Cl:16][C:17]1[C:22]([Sn](CCCC)(CCCC)CCCC)=[CH:21][CH:20]=[C:19]([Cl:36])[N:18]=1.C1([As](C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[F-].C([N+](CCCC)(CCCC)CCCC)CCC>CN1CCCC1=O.C(OCC)(=O)C>[Cl:16][C:17]1[C:22]([C:2]2[C:6]([C:7]3[C:8]([NH:13][CH2:14][CH3:15])=[N:9][CH:10]=[CH:11][CH:12]=3)=[CH:5][S:4][CH:3]=2)=[CH:21][CH:20]=[C:19]([Cl:36])[N:18]=1

Participants

Conditions

Temperature: 100 °C

Procedure

A mixture of 3-bromo-4-(2-ethylaminopyridin-3-yl)thiophene [synthesis described above] (0.757 g), 2, 6-dichloro-3-tributylstannylpyridine (1.331 g), triphenylarsine (0.261 g), and trisdibenzylideneacetone dipalladium (0.092 g) in N-methylpyrrolidinone (3 mL) was heated at 100° C. for 48 hours. Tetrabutylammonium fluoride (1M in tetrahydrofuran, 3 mL) was added . After 2 hours, the mixture was diluted with ethyl acetate, washed with water, dried, filtered and evaporated. The residue was fractionated by chromatography to give 3-(2,6-dichloropyridin-3-yl)-4-(2-ethylaminopyridin-3-yl)thiophene (0.059 g) which was used directly in the next step. To a solution of 3-(2,6-dichloropyridin-3-yl)-4-(2-ethylaminopyridin-3-yl)thiophene (0.059 g) in tetrahydrofuran (2 mL) was added sodium hexamethyldisilazide (1 molar in tetrahydrofuran, 1 mL). After 20 minutes, the reaction was quenched with methanol, diluted with ethyl acetate, washed with water, dried, filtered and evaporated. The residue was fractionated by chromatography to give 6-chloro-8-ethyl-thienyl[3',4':6,5]dipyrido[2,3-b:3',2'-f]azepine (0.024 g) mp 139-141° C.

Workup

washwashed with water
customdried
filtrationfiltered
customevaporated

Sources & evidence

ORD record: ord-1ec6d79167184507bd6f9063ecf1f0b3
Source dataset: uspto-grants-1999_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05919779

Reaction notes

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