Ammonium Chloride → 2-(3-Ethylureido)-7-(pyridin-2-yl)benzothiazol-5-ylboronic acid

HRID 712154Notes

Reaction equation

HRID 712154 reaction equation
[CH2:1]([NH:3][C:4]([NH:6][C:7]1[S:8][C:9]2[C:15]([C:16]3[CH:21]=[CH:20][CH:19]=[CH:18][N:17]=3)=[CH:14][C:13](OS(C(F)(F)F)(=O)=O)=[CH:12][C:10]=2[N:11]=1)=[O:5])[CH3:2].[B:30]1(B2OCC(C)(C)CO2)[O:35]CC(C)(C)C[O:31]1.C([O-])(=O)C.[K+].[NH4+].[Cl-]>CS(C)=O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(Cl)Cl>[CH2:1]([NH:3][C:4]([NH:6][C:7]1[S:8][C:9]2[C:15]([C:16]3[CH:21]=[CH:20][CH:19]=[CH:18][N:17]=3)=[CH:14][C:13]([B:30]([OH:35])[OH:31])=[CH:12][C:10]=2[N:11]=1)=[O:5])[CH3:2]

Participants

7

Reactant 4

HCID 25517Ammonium ChlorideHCID 517044Potassium AcetateHCID 2734316Bis(neopentyl glycolato)diboronHCID 72724619HCID 72724619, compound

Product 1

HCID 727244832-(3-Ethylureido)-7-(pyridin-2-yl)benzothiazol-5-ylboronic acidYield 88.6%

Reagents, catalysts & solvents 2

HCID 178418807HCID 178418807, compoundCatalystHCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
80 °C

Procedure

To a stirred solution of [2-(ethylcarbamoylamino)-7-(2-pyridyl)-1,3-benzothiazol-5-yl]trifluoromethanesulfonate (25 g, 56.1 mmol) in DMSO (250 mL) at rt was added bis(neopentylglycolato) diboron (25.20 g, 112.10 mmol) and potassium acetate (16.5 g, 168.2 mmol). The resulting reaction mixture was de-gassed by purging N2 for 15-20 min followed by addition of [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) DCM adduct (6.8 g, 8.4 mmol). The reaction mixture was again purged with N2for 15-20 min then heated to 80° C. for 90 min. After the completion of reaction (by TLC), the reaction mixture was poured onto saturated NH4Cl solution (1 L). The resulting precipitate was filtered and dried under vacuum. The solid cake was taken up in 2N NaOH (200 mL) and stirred for 45 min at rt. The solution was filtered and the filtrate acidified up to pH 5-6. The solid thus obtained was filtered and dried to obtain the desired product (17 g, 88%). 1H-NMR (DMSO-d6): δ 1.10 (t, J=7.20 Hz, 3H), 3.20 (m, 2H), 6.84 (br s, 1H), 7.41 (m, 1H), 8.01 (m, 1H), 8.12 (s, 1H), 8.25 (m, 3H), 8.40 (s, 1H), 8.79 (d, J=4.0 Hz, 1H) and 10.57 (br s, 1H). MS: 343.25 [M+H]+.

Workup

  1. customThe resulting reaction mixture
  2. customwas de-gassed
  3. customby purging N2 for 15-20 min
  4. customThe reaction mixture was again purged with N2for 15-20 min
  5. customAfter the completion of reaction (by TLC)
  6. filtrationThe resulting precipitate was filtered
  7. customdried under vacuum
  8. filtrationThe solution was filtered
  9. customThe solid thus obtained
  10. filtrationwas filtered
  11. customdried

Sources & evidence

ORD record
ord-fca422f74af14241b571973746bc3321
Source dataset
uspto-grants-2015_11
Patent number
US09181234B2

Reaction notes

Loading…