Hydrochloric Acid → 5-(Benzyloxy)benzo[d]thiazol-7-ol

HRID 2209177Notes

Reaction equation

HRID 2209177 reaction equation
[CH2:1]([O:8][C:9]1[CH:10]=[C:11](Br)[C:12]2[S:16][CH:15]=[N:14][C:13]=2[CH:17]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(P(C(C)(C)C)C1C=CC=CC=1C1C(C(C)C)=CC(C(C)C)=CC=1C(C)C)(C)(C)C.[OH-:49].[K+].Cl>O1CCOCC1.CCOC(C)=O.O.[Cl-].[Na+].O.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH2:1]([O:8][C:9]1[CH:10]=[C:11]([OH:49])[C:12]2[S:16][CH:15]=[N:14][C:13]=2[CH:17]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

10

Reactant 4

HCID 313Hydrochloric AcidHCID 14797Potassium HydroxideHCID 11618717Di-tert-butyl(2',4',6'-tris(propan-2-yl)-(1,1'-biphenyl)-2-yl)phosphaneHCID 1178436335-(Benzyloxy)-7-bromobenzo[d]thiazole

Product 1

HCID 1178430995-(Benzyloxy)benzo[d]thiazol-7-ol

Reagents, catalysts & solvents 5

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolventHCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
90 °C

Procedure

5-(benzyloxy)-7-bromobenzo[d]thiazole (0.65 g, 2.0 mmol), Pd2(dba)3 (95 mg, 0.10 mmol), and 2-Di-tert-butylphosphino-2′,4′,6′-triisopropylbiphenyl (180 mg, 0.42 mmol) were taken up in 1,4-dioxane (7.2 mL) under Ar. Aqueous 2 M KOH (3 mL, 6 mmol) was added and the mixture was heated to 90° C. After 35 min, the mixture was cooled to r.t. and was diluted with EtOAc (20 mL), water (15 mL), and brine (15 mL). The aqueous phase was and acidified with 3 M aqueous HCl (3 mL, 9 mmol). The phases were separated, and the organic phase was dried over Na2SO4, filtered, and concentrated to afford a crude residue that was purified by silica gel chromatography (10-60% EtOAc in hexanes) to provide 5-(benzyloxy)benzo[d]thiazol-7-ol 4.03B. LCMS-ESI+ (m/z): [M+H]+ calcd for C14H12NO2S: 258.1; found 257.8.

Workup

  1. temperaturethe mixture was cooled to r.t.
  2. customThe phases were separated
  3. dry with materialthe organic phase was dried over Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customto afford a crude residue that
  7. customwas purified by silica gel chromatography (10-60% EtOAc in hexanes)

Sources & evidence

ORD record
ord-2ead5dbb99284aafb5c447ee16a61f11
Source dataset
uspto-grants-2016_06
Patent number
US09376441B2

Reaction notes

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