Hydrochloric Acid → HCID 22257129, compound

HRID 1611454Notes

Reaction equation

HRID 1611454 reaction equation
[C:1]([O:4][C:5]1[C:10]2[O:11][C:12]([CH3:15])([CH3:14])[CH2:13][C:9]=2[CH:8]=[C:7](N)[CH:6]=1)(=[O:3])[CH3:2].N(OC(C)(C)C)=O.[I:24]I.Cl>C(#N)C>[C:1]([O:4][C:5]1[C:10]2[O:11][C:12]([CH3:15])([CH3:14])[CH2:13][C:9]=2[CH:8]=[C:7]([I:24])[CH:6]=1)(=[O:3])[CH3:2]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 807IodineHCID 10906Tert-Butyl nitriteHCID 22257136HCID 22257136, compound

Product 1

HCID 22257129HCID 22257129, compoundYield 52.2%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

A stirred solution of 1.0 gram (0.0045 mole) of 5-amino-2,2-dimethyl-2,3-dihydrobenzo[2,3-b]furan-7-yl acetate in 40 mL of acetonitrile was cooled in an ice-bath and 0.55 mL (0.0045 mole) of tert-butyl nitrite was added. Upon completion of addition, the reaction mixture was stirred for an additional 15 minutes with continued cooling. After this time 1.2 grams (0.0045 mole) of iodine was added in two portions during a five-minute period. Upon completion of addition, the reaction mixture was stirred for an additional one hour with continued cooling, allowed to warm to ambient temperature where it stirred for three hours, and then it was warmed to reflux where it stirred for 30 minutes. After this time the reaction mixture was cooled and poured into 50 mL of aqueous 10% hydrochloric acid and the mixture was extracted with two 25 mL portions of methylene chloride. The combined extracts were washed with one 25 mL portion of an aqueous solution saturated with sodium chloride, dried with sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure to a residue. The residue was purified with column chromatography on silica gel using methylene chloride as an eluant. The appropriate fractions were combined and concentrated under reduced pressure, yielding 0.78 gram of the subject compound. The NMR spectrum was consistent with the proposed structure. The reaction was repeated to obtain additional intermediate.

Workup

  1. additionUpon completion of addition
  2. additionUpon completion of addition
  3. stirringthe reaction mixture was stirred for an additional one hour with continued cooling
  4. stirringstirred for three hours
  5. temperatureit was warmed
  6. temperatureto reflux where it
  7. stirringstirred for 30 minutes
  8. temperatureAfter this time the reaction mixture was cooled
  9. extractionthe mixture was extracted with two 25 mL portions of methylene chloride
  10. washThe combined extracts were washed with one 25 mL portion of an aqueous solution saturated with sodium chloride
  11. dry with materialdried with sodium sulfate
  12. filtrationfiltered
  13. concentrationThe filtrate was concentrated under reduced pressure to a residue
  14. customThe residue was purified with column chromatography on silica gel
  15. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-87b355f04a2a498da07d6824e2e4efaa
Source dataset
uspto-grants-2006_01
Patent number
US06987194B2

Reaction notes

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