Ethyl chloroacetate → Ethyl 3-amino-4,5,6,7-tetrahydrobenzo[2,1-d]selenophene-2-carboxylate

HRID 1097210

Reaktionsgleichung

Reaktionsgleichung von HRID 1097210
[Se-2:1].[Na+].[Na+].Cl[C:5]1[CH2:10][CH2:9][CH2:8][CH2:7][C:6]=1[C:11]#[N:12].Cl[CH2:14][C:15]([O:17][CH2:18][CH3:19])=[O:16].C[O-].[Na+]>CN(C=O)C.CO>[NH2:12][C:11]1[C:6]2[CH2:7][CH2:8][CH2:9][CH2:10][C:5]=2[Se:1][C:14]=1[C:15]([O:17][CH2:18][CH3:19])=[O:16]

Komponenten

7

Edukt 4

HCID 7751Ethyl chloroacetateHCID 73973Sodium selenideHCID 10942334Sodium MethoxideHCID 498409392-Chlorocyclohex-1-ene-1-carbonitrile

Produkt 1

HCID 87068721Ethyl 3-amino-4,5,6,7-tetrahydrobenzo[2,1-d]selenophene-2-carboxylate

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 887MethanolLösungsmittelHCID 6228DimethylformamideLösungsmittel2×

Reaktionsbedingungen

Temperatur
60 °C

Versuchsvorschrift

To a suspension of sodium selenide (4.7 g, 37.3 mmol, prepared from 3.0 g of selenium as described above) in DMF (37 mL) was added a solution of 2-chlorocyclohex-1-enecarbonitrile (5.24 g, 37.3 mmol) in DMF (18 mL) at rt for 5 min and stirred the mixture at 60° C. for 45 min. The reaction mixture was allowed to rt and added ethyl chloroacetate (3.16 mL, 37.3 mmol) dropwise for 5 min. The reaction mixture was stirred at 60° C. for 3 h. Then, a solution of sodium methoxide (2.0 g, 37.3 mmol) in methanol (37 mL) was added dropwise and stifling was continued for 2 h at the same temperature. The mixture was allowed to rt and poured into ice cold water and stirred for 15 min. The solution was extracted with chloroform (3×200 mL) and the combined chloroform layer was washed with water, brine and dried over sodium sulfate. The solution was filtered and evaporated the solvent. The residue was chromatographed over silica gel column using hexane-EtOAc (90:10) as eluents to give the product as a yellow color oil of a mixture of ethyl and methyl ester (2.4 g, 25%). 1H NMR (400 MHz, CDCl3): δ 5.54 (2H, s, —NH2), 4.24 (2H, q, J=7.1 Hz, —COOCH2CH3), 2.74-2.75 (2H, m, H-7), 2.27-2.28 (2H, m, H-4), 1.81-1.84 (4H, m, H-5,6), 1.31 (3H, t, J=7.1 Hz, —COOCH2CH3); LC-MS (positive ion mode): m/z 294, 296 (M+Na)+.

Aufarbeitung

  1. customwas allowed to rt
  2. stirringThe reaction mixture was stirred at 60° C. for 3 h
  3. waitstifling was continued for 2 h at the same temperature
  4. customwas allowed to rt
  5. additionpoured into ice cold water
  6. stirringstirred for 15 min
  7. extractionThe solution was extracted with chloroform (3×200 mL)
  8. washthe combined chloroform layer was washed with water, brine
  9. dry with materialdried over sodium sulfate
  10. filtrationThe solution was filtered
  11. customevaporated the solvent
  12. customThe residue was chromatographed over silica gel column
  13. customto give the product

Quellen und Nachweise

ORD-Eintrag
ord-74909cd9edce4fbc9fc2adf726745920
Quelldatensatz
uspto-grants-2012_03
Patentnummer
US08143237B2

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