2-(Tributylstannyl)pyridine → 1-[5-Benzyloxy-7-(2-pyridyl)-1,3-benzothiazol-2-yl]-3-ethyl-urea

HRID 712152Notes

Reaction equation

HRID 712152 reaction equation
[CH2:1]([O:8][C:9]1[CH:10]=[C:11](Br)[C:12]2[S:16][C:15]([NH:17][C:18]([NH:20][CH2:21][CH3:22])=[O:19])=[N:14][C:13]=2[CH:23]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([Sn](CCCC)(CCCC)[C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][N:31]=1)CCC>CN(C=O)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:1]([O:8][C:9]1[CH:10]=[C:11]([C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][N:31]=2)[C:12]2[S:16][C:15]([NH:17][C:18]([NH:20][CH2:21][CH3:22])=[O:19])=[N:14][C:13]=2[CH:23]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 2

HCID 6077842-(Tributylstannyl)pyridineHCID 578136291-(5-Benzyloxy-7-bromo-benzothiazol-2-yl)-3-ethyl-urea

Product 1

HCID 727246171-[5-Benzyloxy-7-(2-pyridyl)-1,3-benzothiazol-2-yl]-3-ethyl-ureaYield 70%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

To a stirred of 1-(5-benzyloxy-7-bromo-1,3-benzothiazol-2-yl)-3-ethyl-urea (110 g, 0.27 mol) in DMF (1.1 L) was added 2-tributylstannyl pyridine (298 g, 0.81 mol). The resulting solution was purged with N2 for 15-20 min followed by addition of tetrakis(triphenylphosphine)palladium (0) (25.41 g, 0.022 mol). The resulting mixture was then heated to 100° C. under N2 atmosphere for 15-16 h. The reaction mass was cooled to 40-45° C. then filtered through celite. The celite bed was washed with DMF (500 mL) and hot EtOAc (1.50 L) and the combined filtrate concentrated at 60-70° C. under reduced pressure. The residue was purified through silica gel (20% EtOAc-Hexanes to 100% EtOAc) to obtain the desired product (76 g, 70%). 1H-NMR (DMSO-d6): δ 1.08 (t, J=7.20 Hz, 3H), 3.19 (q, J=6.80 Hz, 2H), 5.26 (s, 2H), 6.84 (br s, 1H), 7.32-7.43 (m, 5H), 7.51 (d, J=7.20 Hz, 2H), 7.69 (d, J=2.0 Hz, 1H), 7.95 (m, 1H), 8.25 (m, 1H), 8.78 (m, 1H) and 10.46 (br s, 1H). LCMS: 405.30 [M+H]+.

Workup

  1. customThe resulting solution was purged with N2 for 15-20 min
  2. temperatureThe reaction mass was cooled to 40-45° C.
  3. filtrationthen filtered through celite
  4. washThe celite bed was washed with DMF (500 mL) and hot EtOAc (1.50 L)
  5. concentrationthe combined filtrate concentrated at 60-70° C. under reduced pressure
  6. customThe residue was purified through silica gel (20% EtOAc-Hexanes to 100% EtOAc)

Sources & evidence

ORD record
ord-46baf13df9c54c8b924c2c45c70a330f
Source dataset
uspto-grants-2015_11
Patent number
US09181234B2

Reaction notes

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