Ethanol → trans 5-hydroxy-3-nitro-6,7,8,9-tetrahydro [5H] benzocycloheptene-7-carbonitrile

HRID 1764724

Reaktionsgleichung

Reaktionsgleichung von HRID 1764724
[BH4-].[Na+].[N+:3]([C:6]1[CH:19]=[CH:18][C:9]2[CH2:10][CH2:11][CH:12]([C:16]#[N:17])[CH2:13][C:14](=[O:15])[C:8]=2[CH:7]=1)([O-:5])=[O:4].C(O)C>O>[OH:15][C@H:14]1[C:8]2[CH:7]=[C:6]([N+:3]([O-:5])=[O:4])[CH:19]=[CH:18][C:9]=2[CH2:10][CH2:11][C@H:12]([C:16]#[N:17])[CH2:13]1

Komponenten

5

Edukt 3

HCID 702EthanolHCID 4311764Sodium borohydrideHCID 545232963-nitro-5-oxo-6,7,8,9-tetrahydro [5H] benzocycloheptene-7-carbonitrile

Produkt 1

HCID 54445505trans 5-hydroxy-3-nitro-6,7,8,9-tetrahydro [5H] benzocycloheptene-7-carbonitrileAusbeute 22,3 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 962WaterLösungsmittel

Versuchsvorschrift

10 g of sodium borohydride were added over 5 minutes under nitrogen to a mixture of 20 g of 3-nitro-5-oxo-6,7,8,9-tetrahydro [5H] benzocycloheptene-7-carbonitrile, 200 ml of ethanol and 20 ml of water and the mixture was stirred for one hour at room temperature and then evaporated to dryness under reduced pressure. 400 ml of water were added to the residue and the mixture was extracted with methylene chloride. The organic phase was washed with water, dried and evaporated to dryness under reduced pressure to obtain 18 g of raw product which were chromatographed over silica gel. Elution with a 9-1 ethyl acetate-triethylamine mixture yielded 2 fractions. The first fraction of 6.5 g of trans product occured in the form of a yellow oil with an Rf = 0.65 which was crystallized from ethyl acetate to obtain 4.5 g of trans 5-hydroxy-3-nitro-6,7,8,9-tetrahydro [5H] benzocycloheptene-7-carbonitrile in the form of white crystals melting at 160° C. The second fraction of 7.9 g of cis product occured in the form of a yellow oil with a Rf = 0.55 which crystallized from ethyl acetate to obtain 6.5 g of cis 5-hydroxy-3-nitro-6,7,8,9-tetrahydro [5H] benzocycloheptene-7-carbonitrile in the form of white crystals melting at 142° C.

Aufarbeitung

  1. customevaporated to dryness under reduced pressure
  2. addition400 ml of water were added to the residue
  3. extractionthe mixture was extracted with methylene chloride
  4. washThe organic phase was washed with water
  5. customdried
  6. customevaporated to dryness under reduced pressure
  7. customto obtain 18 g of raw product which
  8. customwere chromatographed over silica gel
  9. washElution with a 9-1 ethyl acetate-triethylamine mixture
  10. customyielded 2 fractions
  11. customwas crystallized from ethyl acetate

Quellen und Nachweise

ORD-Eintrag
ord-535efd8246774adca3b04760d4f0a5e6
Quelldatensatz
uspto-grants-1978_09
Patentnummer
US04117164

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