3-Bromophenyl isocyanate → HCID 178521749, compound

HRID 2111961Notes

Reaction equation

HRID 2111961 reaction equation
[Cl:1][C:2]1[CH:10]=[C:9]2[C:5]([C:6]([OH:11])=[N:7][NH:8]2)=[CH:4][CH:3]=1.Br[C:13]1[CH:18]=[CH:17][CH:16]=[C:15]([N:19]=[C:20]=[O:21])[CH:14]=1>N1C=CC=CC=1.CCOC(C)=O>[CH:14]1[C:13]2[C:18](=[CH:10][CH:2]=[CH:3][CH:4]=2)[CH:17]=[CH:16][C:15]=1[NH:19][C:20]([N:8]1[C:9]2[C:5](=[CH:4][CH:3]=[C:2]([Cl:1])[CH:10]=2)[C:6]([OH:11])=[N:7]1)=[O:21]

Participants

5

Reactant 2

HCID 1410013-Bromophenyl isocyanateHCID 178518960HCID 178518960, compound

Product 1

HCID 178521749HCID 178521749, compoundYield 157%

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 8857Ethyl AcetateSolvent

Procedure

2-Amino-4-chloro-benzoic acid (17.16 g, 100 mmol) was suspended in 90 ml of water and 20 ml of concentrated HCl. NaNO2 (6.9 g, 100 mmol) was dissolved in 15 ml water and added slowly at 0° C. The mixture was stirred at 0° C. for 30 minutes and Na2SO3 (34.0 g, 270 mmol) were added, dissolved in 150 ml water. The mixture was then stirred for 2 hours at room temperature. 30 ml of concentrated HCl were added and the mixture stirred overnight at room temperature and then at 80° C. for 2 hours. The solution is treated with aqueous NaOH until the pH is 5.5 and the precipitated was filtered and triturated with ethanol to yield 13.8 g (82%) of 6-chloro-1H-indazol-3-ol. 6-Chloro-1H-indazol-3-ol (700 mg, 4.15 mmol) was dissolved in 25 ml pyridine together with 1-bromo-3-isocyanato-benzene (990 mg, 5 mmol) and stirred at RT for 4 hours. The mixture was then diluted with EtOAc (100 ml) and washed 2× with 1 M HCl. The organic phase was dried with Na2SO4 and reduced under vacuum. The residue was now dissolved in 1 M NaOH and washed with EtOAc and then precipitated with HCl and the precipitate extracted into EtOAc, dried and reduced under vacuum. The product was then recrystallised from EtOAc and heptane to yield 1.1 g (79%) of crystalline solid (m.p. 223-225° C.).

Workup

  1. washwashed 2× with 1 M HCl
  2. dry with materialThe organic phase was dried with Na2SO4
  3. dissolutionThe residue was now dissolved in 1 M NaOH
  4. washwashed with EtOAc
  5. customprecipitated with HCl
  6. extractionthe precipitate extracted into EtOAc
  7. customdried
  8. customThe product was then recrystallised from EtOAc and heptane

Sources & evidence

ORD record
ord-c9d2c73a40964ac2b62ed2c0ae54b017
Source dataset
uspto-grants-2009_04
Patent number
US07521480B2

Reaction notes

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