Hydrochloric Acid → HCID 71571793, compound

HRID 532180Notes

Reaction equation

HRID 532180 reaction equation
[OH:1][B:2]1[C:6]2[CH:7]=[CH:8][C:9](/[CH:11]=[N:12]/[OH:13])=[CH:10][C:5]=2[C:4]([CH3:15])([CH3:14])[O:3]1.C1C(=O)N(Cl)C(=O)C1.[Cl:24][C:25]1[CH:30]=[C:29]([C:31]([CH2:33][F:34])=[CH2:32])[CH:28]=[C:27]([Cl:35])[C:26]=1[Cl:36].Cl>CN(C=O)C.CC(=O)OCC.O>[F:34][CH2:33][C:31]1([C:29]2[CH:28]=[C:27]([Cl:35])[C:26]([Cl:36])=[C:25]([Cl:24])[CH:30]=2)[O:13][N:12]=[C:11]([C:9]2[CH:8]=[CH:7][C:6]3[B:2]([OH:1])[O:3][C:4]([CH3:15])([CH3:14])[C:5]=3[CH:10]=2)[CH2:32]1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 31398ChlorosuccinimideHCID 86685062HCID 86685062, compoundHCID 89572652HCID 89572652, compound

Product 1

HCID 71571793HCID 71571793, compoundYield 41.1%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
45 °C

Procedure

To a solution of (E)-1-hydroxy-3,3-dimethyl-1,3-dihydrobenzo[c][1,2]oxaborole-5-carbaldehyde oxime (225.5 mg, 1.1 mmol) in DMF (10 mL) at rt was added NCS (177 mg, 1.32 mmol). The reaction mixture was warmed to 45° C., stirred for 2.5 h and cooled to rt. To a solution of 1,2,3-trichloro-5-(3-fluoroprop-1-en-2-yl)benzene (260 mg, 1.1 mmol) and TEA (122.2 mg, 1.21 mmol) in DMF (20 mL) was added the above mixture dropwise at 0° C. The mixture was stirred at this temperature for 1 h and then at rt overnight. The mixture was acidified with HCl (3 N) to pH of 2 and then poured into water followed by extraction with EA (100 ml×2). The combined organic layers were washed with brine, dried over Na2SO4, filtered and concentrated under reduced pressure. The residue was purified by prep-TLC eluted with PE:EA (2:1) to give the final title compound (200 mg, yield 41%) as a white solid: 1H NMR (300 MHz, DMSO-d6): δ 9.14 (s, 1H), 7.77 (s, 2H), 7.69-7.68 (m, 3H), 4.91 (s, 1H), 4.75 (s, 1H), 3.80 (s, 2H), 1.45 (s, 6H). MS: m/z=443 [M+H]+.

Workup

  1. temperaturecooled to rt
  2. stirringThe mixture was stirred at this temperature for 1 h
  3. customat rt
  4. customovernight
  5. extractionfollowed by extraction with EA (100 ml×2)
  6. washThe combined organic layers were washed with brine
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. customThe residue was purified
  11. washby prep-TLC eluted with PE

Sources & evidence

ORD record
ord-dc11a393f59f4b65ba29b0c7b32b33eb
Source dataset
uspto-grants-2014_10
Patent number
US08853186B2

Reaction notes

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