1-Chloro-N,N-2-trimethylpropenylamine → HCID 89832292, compound

HRID 338115Notes

Reaction equation

HRID 338115 reaction equation
[C:1]([NH:9][C:10]([N:12]1[C:16]2([C:30]3[CH:35]=[CH:34][CH:33]=[C:32]([Br:36])[CH:31]=3)[CH2:17][N:18]([C:20]([O:22][CH2:23][C:24]3[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=3)=[O:21])[CH2:19][CH:15]2[CH2:14]O1)=[S:11])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.ClC(N(C)C)=C(C)C>C(O)(=O)C.[Zn]>[C:1]([NH:9][C:10]1[S:11][CH2:14][CH:15]2[CH2:19][N:18]([C:20]([O:22][CH2:23][C:24]3[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=3)=[O:21])[CH2:17][C:16]2([C:30]2[CH:35]=[CH:34][CH:33]=[C:32]([Br:36])[CH:31]=2)[N:12]=1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 2

HCID 6407921-Chloro-N,N-2-trimethylpropenylamineHCID 89823297HCID 89823297, compound

Product 1

HCID 89832292HCID 89832292, compoundYield 102.4%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 176Acetic AcidSolvent

Procedure

To a solution of benzyl 1-(benzoylcarbamothioyl)-6a-(3-bromophenyl)-3,3a,4,6-tetrahydropyrrolo[3,4-c]isoxazole-5-carboxylate (1.9 g, 3.3 mmol) in acetic acid (30 mL) is added powered zinc (2.0 g, 30 mmol). The resultant suspension is sonicated for 2 hours before being filtered through a pad of diatomaceous earth. The diatomaceous earth pad is washed with ethyl acetate. The combined filtrates are concentrated to dryness then diluted with ethyl acetate (100 mL) and washed with saturated sodium bicarbonate (100 mL). The aqueous layer is re-extracted with ethyl acetate (50 mL) and chloroform (50 mL). The combined organic layers are dried over magnesium sulfate, filtered, and concentrated. The residue is then dissolved in dichloromethane (30 mL) and treated with 1-chloro-N,N,2-trimethylpropenylamine (1.0 mL, 7.6 mmol). The resultant solution is stirred at ambient temperature for 3.3 hours and concentrated to dryness. The residue is purified by silica gel flash chromatography, eluting with gradient of ethyl acetate/dichloromethane (0 to 40%) to give the title compound (1.86 g, 100%). ES/MS (m/e): (79Br/81Br) 550/552 (M+H).

Workup

  1. filtrationbefore being filtered through a pad of diatomaceous earth
  2. washThe diatomaceous earth pad is washed with ethyl acetate
  3. concentrationThe combined filtrates are concentrated to dryness
  4. additionthen diluted with ethyl acetate (100 mL)
  5. washwashed with saturated sodium bicarbonate (100 mL)
  6. extractionThe aqueous layer is re-extracted with ethyl acetate (50 mL) and chloroform (50 mL)
  7. dry with materialThe combined organic layers are dried over magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated
  10. dissolutionThe residue is then dissolved in dichloromethane (30 mL)
  11. concentrationconcentrated to dryness
  12. customThe residue is purified by silica gel flash chromatography
  13. washeluting with gradient of ethyl acetate/dichloromethane (0 to 40%)

Sources & evidence

ORD record
ord-9838657ef968413cb72cf273b8280642
Source dataset
uspto-grants-2014_11
Patent number
US08889856B2

Reaction notes

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