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

HRID 65624

반응식

HRID 65624 반응식
[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

참가 물질

8

반응물 4

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

생성물 1

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

시약·촉매·용매 3

HCID 241Benzene용매HCID 702Ethanol용매HCID 962Water용매

반응 조건

온도
150 °C

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-65e06d5b58864482b9abc9d1ed3e7ecb
출처 데이터셋
uspto-grants-1978_12
특허 번호
US04128560

연결된 노트

불러오는 중…