Hydrochloric Acid → HCID 86665280, compound

HRID 1970842Notes

Reaction equation

HRID 1970842 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([C:8]([F:20])([C:16]([F:19])([F:18])[F:17])[C:9]([F:15])([F:14])[C:10]([F:13])([F:12])[F:11])[CH:5]=[C:4]([S:21][CH3:22])[C:3]=1[NH:23][C:24](=[O:36])[C:25]1[CH:30]=[CH:29][C:28]([C:31]#[N:32])=[C:27]([N+:33]([O-])=O)[CH:26]=1.[Sn](Cl)(Cl)(Cl)Cl.Cl>C(O)(C)C>[NH2:33][C:27]1[CH:26]=[C:25]([CH:30]=[CH:29][C:28]=1[C:31]#[N:32])[C:24]([NH:23][C:3]1[C:4]([S:21][CH3:22])=[CH:5][C:6]([C:8]([F:20])([C:16]([F:17])([F:18])[F:19])[C:9]([F:14])([F:15])[C:10]([F:11])([F:12])[F:13])=[CH:7][C:2]=1[Cl:1])=[O:36]

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 24287Tin tetrachlorideHCID 86665281HCID 86665281, compound

Product 1

HCID 86665280HCID 86665280, compoundYield 45.8%

Reagents, catalysts & solvents 1

HCID 3776IsopropanolSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of N-[2-chloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methylthiophenyl]-4-cyano-3-nitrobenzamide (Example 1.4) (13.0 g, 23 mmol) in isopropanol (110 ml) was added tin chloride (15.69 g, 82.8 mmol). The mixture was cooled to 0° C. and aqueous hydrochloric acid (37% w/v) (22 ml) was added slowly. The mixture was stirred at 80° C. for 1 hours. About one third of the total volume of isopropanol was evaporated. Water (100 ml) was added to the mixture followed by aqueous sodium hydroxide (4N) to adjust the pH to 8 to 9. The aqueous phase was extracted three times with ethyl acetate (20 ml). The combined organic extracts were dried over sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel (eluent: ethyl acetate/cyclohexane 1:2 to 1:1) to give 3-amino-N-[2-chloro-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methylthiophenyl]-4-cyanobenzamide (5.65 g, 45.8% yield). LC-MS (Method 1): RT=2.03, [M−H]−=536.

Workup

  1. customAbout one third of the total volume of isopropanol was evaporated
  2. additionWater (100 ml) was added to the mixture
  3. extractionThe aqueous phase was extracted three times with ethyl acetate (20 ml)
  4. dry with materialThe combined organic extracts were dried over sodium sulfate
  5. concentrationconcentrated
  6. customThe residue was purified by column chromatography on silica gel (eluent: ethyl acetate/cyclohexane 1:2 to 1:1)

Sources & evidence

ORD record
ord-b4e9326f69924859a946b62b793408cb
Source dataset
uspto-grants-2013_04
Patent number
US08431514B2

Reaction notes

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