Sulfuric Acid → 6-Methyl-5,6,7,8,9,10-hexahydrocyclohept[b]indole-6-acetic acid methyl ester

HRID 65624

Reaktionsgleichung

Reaktionsgleichung von HRID 65624
[CH3:1][O:2][C:3](=[O:14])[CH2:4][C:5]1([CH3:13])[CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][C:6]1=O.Cl.[C:16]1([NH:22]N)[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.C1(NN)C=CC=CC=1.S(=O)(=O)(O)O>C1C=CC=CC=1.O.C(O)C>[CH3:1][O:2][C:3](=[O:14])[CH2:4][C:5]1([CH3:13])[C:6]2[NH:22][C:16]3[C:21]([C:7]=2[CH2:8][CH2:9][CH2:10][CH2:11]1)=[CH:20][CH:19]=[CH:18][CH:17]=3

Komponenten

8

Edukt 4

HCID 1118Sulfuric AcidHCID 7516PhenylhydrazineHCID 60962Phenylhydrazine hydrochlorideHCID 122919321-Methyl-2-oxocycloheptaneacetic acid methyl ester

Produkt 1

HCID 543070966-Methyl-5,6,7,8,9,10-hexahydrocyclohept[b]indole-6-acetic acid methyl ester

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 241BenzeneLösungsmittelHCID 702EthanolLösungsmittelHCID 962WaterLösungsmittel

Reaktionsbedingungen

Temperatur
150 °C

Versuchsvorschrift

A mixture of the compound of formula 3, 1-methyl-2-oxocycloheptaneacetic acid methyl ester (16 g, 0.08 mole), described in Example 10, phenylhydrazine hydrochloride (12 g, 0.08 mole), phenylhydrazine (8 g, 0.07 mole) and anhydrous ethanol (100 ml) is heated at reflux for 20 hr. After cooling, water is added and the reaction mixture is extracted with benzene (2X). Evaporation to dryness of the organic layer affords a residue. The residue is heated with a 20% sulfuric acid solution (230 ml) at reflux (oil bath at 150° C.) for 1 hr. The reaction mixture is poured on ice and extracted with benzene and ether. Evaporation to dryness affords a residue which is subjected to chromatography on silica gel (500 g) using benzene as eluant. The title compound, νmaxCHCl3 1736 cm-1 is eluted first, followed by 2,2a,3,4,5,6-hexahydro-2a-methyl-1H-10b-azabenzo[a]cyclopent[d]azulen-1-one (6, R1 = CH3, R2 and R3 = H, m = 4 and n = 1), nmr (CDCl3) δ 1.42 (s, 3H), 2.90 (s, 2H), 7.0-7.7 (m, 3H), 7.9-8.2 (m, 1H), followed by 2,4,4a,5,6,7,8,9-octahydro-4a-methyl-2-phenyl-3H-cyclohepta[c]pyridazin-3-one (14, R1 = CH3, R2 and R3 = H and m = 4), nmr (CDCl3) δ 1.18 (s, 3H), 2.18 (d, J = 16.5, 2H), 7.1-7.7 (m, 5H).

Aufarbeitung

  1. temperatureis heated
  2. temperatureat reflux for 20 hr
  3. temperatureAfter cooling
  4. extractionthe reaction mixture is extracted with benzene (2X)
  5. customEvaporation to dryness of the organic layer
  6. customaffords a residue
  7. additionThe reaction mixture is poured on ice
  8. extractionextracted with benzene and ether
  9. customEvaporation to dryness
  10. customaffords a residue which
  11. washThe title compound, νmaxCHCl3 1736 cm-1 is eluted first

Quellen und Nachweise

ORD-Eintrag
ord-65e06d5b58864482b9abc9d1ed3e7ecb
Quelldatensatz
uspto-grants-1978_12
Patentnummer
US04128560

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