4-(Bromomethyl)-1,2-difluorobenzene → HCID 53258398, compound

HRID 1260179Notes

Reaction equation

HRID 1260179 reaction equation
[CH3:1][S:2][C:3]1[N:4]=[CH:5][C:6]2[C:7]3[N:8]([N:18]=[N:19][N:20]=3)[C:9]3[CH:17]=[CH:16][CH:15]=[CH:14][C:10]=3[NH:11][C:12]=2[N:13]=1.CC([O-])(C)C.[K+].[F:27][C:28]1[CH:29]=[C:30]([CH:33]=[CH:34][C:35]=1[F:36])[CH2:31]Br>CN(C=O)C.CC(O)(C)C>[F:27][C:28]1[CH:29]=[C:30]([CH:33]=[CH:34][C:35]=1[F:36])[CH2:31][N:11]1[C:12]2[N:13]=[C:3]([S:2][CH3:1])[N:4]=[CH:5][C:6]=2[C:7]2=[N:20][N:19]=[N:18][N:8]2[C:9]2[CH:17]=[CH:16][CH:15]=[CH:14][C:10]1=2

Participants

6

Reactant 3

HCID 5814364-(Bromomethyl)-1,2-difluorobenzeneHCID 23665647Potassium tert-butoxideHCID 135998025HCID 135998025, compound

Product 1

HCID 53258398HCID 53258398, compound

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 6386tert-ButanolSolvent

Procedure

The 11-(methylthio)-9H-benzo[b]pyrimido[5,4-f]tetrazolo[1,5-d][1,4]diazepine (5) (1.03 g) in DMF (20 mL) was treated with 1.1 eq. of 1M t-BuOK in t-BuOH (4 mL). The mixture was stirred at R.T. for 10 minutes then the 3,4-difluorobenzyl bromide (0.6 mL) was added. The mixture was stirred at R.T. for one hour. The reaction mixture was quenched with the addition of saturated aqueous ammonium chloride solution (20 mL). The mixture was extracted with ethyl acetate (3×50 mL) and the combined organic extracts were dried over sodium sulfate. Concentration in vacuo provided the titled product as a yellow solid (6) (1.3 g). M.p.=281-283° C.; 400 MHz 1H NMR (DMSO-d6) δ: 8.91 (s, 1H), 7.79 (dd, J=8.4, 1.6 Hz, 1H), 7.61 (dd, J=8.4, 1.2 Hz, 1H), 7.54 (ddd, J=8.8, 7.2, 1.6 Hz, 1H), 7.45-7.34 (m, 2H), 7.32-7.25 (m, 1H), 7.17-7.13 (m, 1H), 5.24 (s, 2H), 2.56 (s, 3H); LCMS [M+H]: 410; Calc. for C19H13F2N7S: C, 55.74; H, 3.20; N, 23.95; found C, 55.65; H, 2.96; N, 23.67.

Workup

  1. stirringThe mixture was stirred at R.T. for one hour
  2. customThe reaction mixture was quenched with the addition of saturated aqueous ammonium chloride solution (20 mL)
  3. extractionThe mixture was extracted with ethyl acetate (3×50 mL)
  4. dry with materialthe combined organic extracts were dried over sodium sulfate
  5. concentrationConcentration in vacuo

Sources & evidence

ORD record
ord-5c64ce56d013482abdcd40349becb550
Source dataset
uspto-grants-2013_06
Patent number
US08470812B2

Reaction notes

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