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

HRID 1764724

反応式

HRID 1764724 の反応式
[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

参加物

5

反応物 3

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

生成物 1

HCID 54445505trans 5-hydroxy-3-nitro-6,7,8,9-tetrahydro [5H] benzocycloheptene-7-carbonitrile収率 22.3%

試薬・触媒・溶媒 1

HCID 962Water溶媒

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-535efd8246774adca3b04760d4f0a5e6
出典データセット
uspto-grants-1978_09
特許番号
US04117164

関連ノート

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