Stannous Chloride → 4-Bromo-2-hydrazinylbenzoic acid hydrochloride

HRID 661890Notes

Reaction equation

HRID 661890 reaction equation
[N:1]([O-])=O.[Na+].[NH2:5][C:6]1[CH:14]=[C:13]([Br:15])[CH:12]=[CH:11][C:7]=1[C:8]([OH:10])=[O:9].[Sn](Cl)[Cl:17]>O.Cl>[ClH:17].[Br:15][C:13]1[CH:12]=[CH:11][C:7]([C:8]([OH:10])=[O:9])=[C:6]([NH:5][NH2:1])[CH:14]=1

Participants

6

Reactant 3

HCID 24479Stannous ChlorideHCID 886912-Amino-4-bromobenzoic acidHCID 23668193Sodium Nitrite

Product 1

HCID 666056644-Bromo-2-hydrazinylbenzoic acid hydrochlorideYield 86.2%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolvent2×HCID 962WaterSolvent

Conditions

Temperature
-5 °C

Procedure

Step 1 A solution of sodium nitrite (2.448 g, 35.5 mmol) in water (12 mL) was added dropwise to a suspension of 2-amino-4-bromobenzoic acid (7.30 g, 33.8 mmol) in concentrated hydrochloric acid (34 mL) at −5° C., at such rate that the temperature did not exceed 0° C. The resulting suspension was stirred at −5° C. for 10 min and was then added dropwise to a rapidly stirred solution of tin (II) chloride (13.46 g, 71.0 mmol) in concentrated hydrochloric acid (10 mL) at −5° C., at such a rate that the temperature did not exceed 0° C. The resulting suspension was warmed to rt and stirred for 1 h. The precipitate was collected by filtration, washed with water, and dried to provide 4-bromo-2-hydrazinylbenzoic acid hydrochloric acid salt as a pale tan solid (7.79 g, 86%). 1H NMR (400 MHz, DMSO-d6) δ 9.14 (br. s., 1H) 7.79 (d, J=8.35 Hz, 1H) 7.34 (d, J=1.76 Hz, 1H) 7.13 (dd, J=8.35, 1.76 Hz, 1H). Mass spectrum m/z 231, 233 (M+H)+.

Workup

  1. customdid not exceed 0° C
  2. customdid not exceed 0° C
  3. temperatureThe resulting suspension was warmed to rt
  4. stirringstirred for 1 h
  5. filtrationThe precipitate was collected by filtration
  6. washwashed with water
  7. customdried

Sources & evidence

ORD record
ord-e3b6cede3b0143e9bfb17d1f47df81dd
Source dataset
uspto-grants-2011_12
Patent number
US08084620B2

Reaction notes

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