Sodium Dithionite → 6-Amino-2-iodo-3,4-dimethoxybenzonitrile

HRID 1795387Notes

Reaction equation

HRID 1795387 reaction equation
[N+:1]([C:4]1[C:9]([C:10]#[N:11])=[C:8]([I:12])[C:7]([O:13][CH3:14])=[C:6]([O:15][CH3:16])[CH:5]=1)([O-])=O.S(S([O-])=O)([O-])=O.[Na+].[Na+]>C(O)C.O>[NH2:1][C:4]1[C:9]([C:10]#[N:11])=[C:8]([I:12])[C:7]([O:13][CH3:14])=[C:6]([O:15][CH3:16])[CH:5]=1

Participants

5

Reactant 2

HCID 24489Sodium DithioniteHCID 155382832-Iodo-3,4-dimethoxy-6-nitrobenzonitrile

Product 1

HCID 155382846-Amino-2-iodo-3,4-dimethoxybenzonitrileYield 92%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent

Conditions

Temperature
85 °C

Procedure

In a reactor vessel, a suspension of 6-nitro-2-iodo-3,4-dimethoxybenzonitrile (see Example 1(d) of WO 98/30560, 10 kg) in ethanol (60 l) at room temperature was charged with a solution of sodium dithionite (15.6 kg of technical grade material) in water (67.5 l) over 45 mins maintaining the temperature below 35° C. The addition vessel was washed with water (10 l). The resulting mixture was warmed to reflux (ca. 85° C.) for ca. 90 mins and then the temperature adjusted to 65° C. A solution of 6M aqueous hydrochloric acid (12.5 l) was added over ca. 10 mins and the resulting mixture stirred at 65° C. for ca. 5 hours before being cooled to room temperature. The pH was adjusted to the range 7–8 using 40% sodium hydroxide (2 l), the resulting mixture left to stir for 3 hours, filtered and washed with water (50 l). The damp cake was slurried in water (90 l) overnight at room temperature, filtered, washed with water (100 l) and dried in vacuo to give 8.35 kg (92%) of the title compound.

Workup

  1. temperaturemaintaining the temperature below 35° C
  2. washThe addition vessel was washed with water (10 l)
  3. temperatureThe resulting mixture was warmed
  4. customadjusted to 65° C
  5. additionA solution of 6M aqueous hydrochloric acid (12.5 l) was added over ca. 10 mins
  6. temperaturebefore being cooled to room temperature
  7. waitthe resulting mixture left
  8. stirringto stir for 3 hours
  9. filtrationfiltered
  10. washwashed with water (50 l)
  11. waitThe damp cake was slurried in water (90 l) overnight at room temperature
  12. filtrationfiltered
  13. washwashed with water (100 l)
  14. customdried in vacuo

Sources & evidence

ORD record
ord-723ab16b65b34a42be1b843009256691
Source dataset
uspto-grants-2006_04
Patent number
US07026479B2

Reaction notes

Loading…