Acetic Acid → ethyl N-(3-amino4-chloro-6-fluoro-2-methoxyphenyl)carbamate

HRID 275657

Reaction equation

HRID 275657 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([F:8])[C:5]([NH:9][C:10](=[O:14])[O:11][CH2:12][CH3:13])=[C:4]([O:15][CH3:16])[C:3]=1[N+:17]([O-])=O.C(O)(=O)C.C(O)C.Cl>C(Cl)Cl.[Fe]>[NH2:17][C:3]1[C:4]([O:15][CH3:16])=[C:5]([NH:9][C:10](=[O:14])[O:11][CH2:12][CH3:13])[C:6]([F:8])=[CH:7][C:2]=1[Cl:1]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 313Hydrochloric AcidHCID 702EthanolHCID 18315060ethyl N-(4-chloro-6-fluoro-2-methoxy-3-nitrophenyl)carbamate

Product 1

HCID 18315064ethyl N-(3-amino4-chloro-6-fluoro-2-methoxyphenyl)carbamateYield 79.3%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 6344DichloromethaneSolvent

Procedure

Under a nitrogen atmosphere, a stirred solution of 21.3 grams (0.072 mole) of ethyl N-(4-chloro-6-fluoro-2-methoxy-3-nitrophenyl)-carbamate, 18.3 grams (0.328 mole) of iron powder, 50 mL of acetic acid, and 250 mL of ethanol was heated to 65° C. where it stirred for two hours. At the conclusion of this time, 3 mL (0.036 mole) of 12M hydrochloric acid was added. Upon completion of addition, the reaction mixture was stirred for an additional two hours. After this time, the reaction mixture was concentrated under reduced pressure to yield a brown oil. The oil was then taken up in methylene chloride. The mixture was filtered through diatomaceous earth, and the filter cake was washed with water and an aqueous saturated sodium bicarbonate solution. The filtrate was stored over sodium sulfate for about 18 hours and then filtered. The solvent was removed under reduced pressure to yield a black oil. This oil was filtered through a silica gel pad, yielding 15.0 grams of ethyl N-(3-amino4-chloro-6-fluoro-2-methoxyphenyl)carbamate. The NMR spectrum was consistent with the proposed structure.

Workup

  1. additionUpon completion of addition
  2. stirringthe reaction mixture was stirred for an additional two hours
  3. concentrationAfter this time, the reaction mixture was concentrated under reduced pressure
  4. customto yield a brown oil
  5. filtrationThe mixture was filtered through diatomaceous earth
  6. washthe filter cake was washed with water
  7. waitThe filtrate was stored over sodium sulfate for about 18 hours
  8. filtrationfiltered
  9. customThe solvent was removed under reduced pressure
  10. customto yield a black oil
  11. filtrationThis oil was filtered through a silica gel pad

Sources & evidence

ORD record
ord-29d7527beb7c4926a4e181cb9afc1961
Source dataset
uspto-grants-2002_03
Patent number
US06352958B1

Linked notes

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