Boron tribromide → HCID 10504178, compound

HRID 1421394Notes

Reaction equation

HRID 1421394 reaction equation
Cl.C[O:3][C:4]1[CH:9]=[CH:8][C:7]([C:10]2[S:14][C:13]3[CH:15]=[C:16]([O:19]C)[CH:17]=[CH:18][C:12]=3[C:11]=2[NH:21][C:22]2[CH:27]=[CH:26][C:25]([O:28][CH2:29][CH2:30][N:31]3[CH2:36][CH2:35][CH2:34][CH2:33][CH2:32]3)=[CH:24][CH:23]=2)=[CH:6][CH:5]=1.B(Br)(Br)Br>C(Cl)Cl>[OH:3][C:4]1[CH:9]=[CH:8][C:7]([C:10]2[S:14][C:13]3[CH:15]=[C:16]([OH:19])[CH:17]=[CH:18][C:12]=3[C:11]=2[NH:21][C:22]2[CH:27]=[CH:26][C:25]([O:28][CH2:29][CH2:30][N:31]3[CH2:36][CH2:35][CH2:34][CH2:33][CH2:32]3)=[CH:24][CH:23]=2)=[CH:6][CH:5]=1

Participants

4

Reactant 2

HCID 25134Boron tribromideHCID 18781549HCID 18781549, compound

Product 1

HCID 10504178HCID 10504178, compoundYield 56.4%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of 2-(4-methoxyphenyl)-3-[N-[4-[2-(1-piperidinyl)ethoxy]phenyl]amino]-6-methoxybenzo[b]thiophene hydrochloride (0.70 g, 1.25 mmol) in 40 mL of anhydrous CH2Cl2 under N2 10° C. was added BBr3 (0.36 mL, 3.80 mmmol). The solution was allowed to gradually warm to room temperature and stirred for a total of 6 h. The reaction was quenched by pouring the mixture into an excess of sat. NaHCO3 solution. The aqueous was then extracted several times with 5% EtOH/EtOAc. The organic was combined and dried (Na2SO4) and then concentrated in vacuo to a foam. The crude product was chromatographed (1-6% CH3OH/CHCl3) to provide 325 mg (49%) of 2-(4-hydroxyphenyl)-3-[N-[4-[2-(1-piperidinyl)ethoxy]phenyl]amino]-6-hydroxybenzo[b]thiophene as an oil. This material was converted to the hydrochloride salt by treatment with Et2O.HCl in EtOAc, and isolated as a white solid by filtration. Data for 2-(4-Hydroxyphenyl)-3-[N-[4-[2-(1-piperidinyl)ethoxy]phenyl]amino]-6-hydroxybenzo[b]thiophene Hydrochloride: mp 140-150° C. 1H NMR (DMSO-d6) δ9.57 (s, 2H), 7.40 (d, J=8.6 Hz, 2H), 7.19 (d, J=10.1 Hz, 1H), 7.16 (d, J=2.0 Hz, 1H), 6.75 (dd, J=10.1, 2.0 Hz, 1H), 6.70 (d, J=8.6 Hz, 2H), 6.64 (d, J=8.8 Hz, 2H), 6.46 (d, J=8.8 Hz, 2H), 4.21 (m, 2H), 3.50-3.30 (m, 4H), 3.01-2.95 (m, 2H), 1.81-1.63 (m, 5H), 1.38 (m, 1H). FD mass spec: 461. Anal. Calcd. for C27H28N2O3S.1.5 HCl: C, 62.94; H, 5.77; N, 5.44. Found: C, 62.99; H, 5.88; N, 5.27.

Workup

  1. customThe reaction was quenched
  2. additionby pouring the mixture into an excess of sat. NaHCO3 solution
  3. extractionThe aqueous was then extracted several times with 5% EtOH/EtOAc
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated in vacuo to a foam
  6. customThe crude product was chromatographed (1-6% CH3OH/CHCl3)

Sources & evidence

ORD record
ord-f1b81cd63be74da8b8a2c93e2706564f
Source dataset
uspto-grants-2000_06
Patent number
US06075151

Reaction notes

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