Acetic Acid → (+/-)-cis-6-(3,4-Dimethoxyphenyl)-cyclohex-3-enylamine

HRID 220106Notes

Reaction equation

HRID 220106 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([C@@H:9]2[CH2:14][CH:13]=[CH:12][CH2:11][C@@H:10]2[N+:15]([O-])=O)=[CH:5][C:4]=1[O:18][CH3:19].C(O)(=O)C>C(O)C.[Zn]>[CH3:19][O:18][C:4]1[CH:5]=[C:6]([C@@H:9]2[C@H:10]([NH2:15])[CH2:11][CH:12]=[CH:13][CH2:14]2)[CH:7]=[CH:8][C:3]=1[O:2][CH3:1]

Participants

5

Reactant 2

HCID 176Acetic AcidHCID 15389588(+/-)-cis-1 2-Dimethoxy-4-(2-nitrocyclohex-4-enyl)benzene

Product 1

HCID 86601281(+/-)-cis-6-(3,4-Dimethoxyphenyl)-cyclohex-3-enylamineYield 32.4%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 702EthanolSolvent

Procedure

40 g of (±)-cis-1,2-dimethoxy-4-(2-nitrocyclohex-4-enyl)benzene (compound H1) are dissolved in 400 ml of ethanol and 40 g of zinc powder are added. After heating to boiling temperature, 65 ml of glacial acetic acid are added dropwise. Afterwards, the reaction mixture is filtrated and concentrated. The residue is redissolved in diluted hydrochloric acid and extracted with toluene. The aqueous layer is alkalized using 6 N solution of sodium hydroxide and extracted several times with toluene. The combined organic phases of the alkalic extraction are dried using sodium sulfate and concentrated. The residue is chromatographed on silica gel using a mixture of petroleum ether/ethyl acetate/triethylamine in the ratio 6/3/1. 11.5 g of the title compound are obtained.

Workup

  1. temperatureAfter heating
  2. additionare added dropwise
  3. filtrationAfterwards, the reaction mixture is filtrated
  4. concentrationconcentrated
  5. dissolutionThe residue is redissolved in diluted hydrochloric acid
  6. extractionextracted with toluene
  7. extractionextracted several times with toluene
  8. extractionThe combined organic phases of the alkalic extraction
  9. customare dried
  10. concentrationconcentrated
  11. customThe residue is chromatographed on silica gel using
  12. additiona mixture of petroleum ether/ethyl acetate/triethylamine in the ratio 6/3/1

Sources & evidence

ORD record
ord-a9b5166980a2450c9bd2232f72f20e89
Source dataset
uspto-grants-2012_06
Patent number
US08202880B2

Reaction notes

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