Lawesson's reagent → 2,3,4,5-Tetrahydro-4-methyl-5-thioxopyrido[3,2-f][1,4]oxazepin-2-propanenitrile

HRID 236160

Reaktionsgleichung

Reaktionsgleichung von HRID 236160
[CH3:1][N:2]1[C:8](=O)[C:7]2[CH:10]=[CH:11][CH:12]=[N:13][C:6]=2[O:5][CH:4]([CH2:14][CH2:15][C:16]#[N:17])[CH2:3]1.COC1C=CC(P2(=S)SP(=S)(C3C=CC(OC)=CC=3)[S:27]2)=CC=1>C1(C)C=CC=CC=1>[CH3:1][N:2]1[C:8](=[S:27])[C:7]2[CH:10]=[CH:11][CH:12]=[N:13][C:6]=2[O:5][CH:4]([CH2:14][CH2:15][C:16]#[N:17])[CH2:3]1

Komponenten

4

Edukt 2

HCID 87949Lawesson's reagent2×HCID 137264592,3,4,5-Tetrahydro-4-methyl-5-oxopyrido[3,2-f][1,4]-oxazepine-2-propanenitrile

Produkt 1

HCID 137264602,3,4,5-Tetrahydro-4-methyl-5-thioxopyrido[3,2-f][1,4]oxazepin-2-propanenitrileAusbeute 24,9 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 1140TolueneLösungsmittel

Versuchsvorschrift

To a solution of 11.0 g (0.04 mole) of 2,3,4,5-tetrahydro-4-methyl-5-oxopyrido[3,2-f][1,4]-oxazepine-2-propanenitrile in 175 ml toluene was added 10.5 g (0.026 mole) of 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide. The reaction mixture was heated to reflux for 2 hr with vigorous mechanical stirring. Another 3.0 g (0.007 mole) of 2,4 bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane 2,4-disulfide was added and heating continued for 1 hr additional. The reaction mixture was allowed to cool and stand overnight at room temperature. Toluene was removed by rotary evaporation (90° C., water aspirator) and the residue taken up in 200 ml chloroform. This was washed with 2×50 ml 2M aqueous potassium hydroxide and concentrated by rotary evaporator (90° C., water aspirator). Crystallization ensued upon cooling. Recrystallization from isopropyl alcohol afforded 1.60 g (13.8%) product, m.p. 155°-56° C.

Aufarbeitung

  1. temperatureThe reaction mixture was heated
  2. temperatureto reflux for 2 hr with vigorous mechanical stirring
  3. temperatureheating
  4. temperatureto cool
  5. waitstand overnight at room temperature
  6. customToluene was removed by rotary evaporation (90° C., water aspirator)
  7. washThis was washed with 2×50 ml 2M aqueous potassium hydroxide
  8. concentrationconcentrated by rotary evaporator (90° C., water aspirator)
  9. customCrystallization
  10. temperatureupon cooling
  11. customRecrystallization from isopropyl alcohol

Quellen und Nachweise

ORD-Eintrag
ord-9a105e94488f46d3b6f6a124c8389264
Quelldatensatz
uspto-grants-1987_02
Patentnummer
US04642343

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