1,3-Cyclohexanedione → HCID 70421324, compound

HRID 247384Notes

Reaction equation

HRID 247384 reaction equation
[C:1]1(=O)[CH2:5][CH2:4][CH2:3][C:2]1=[N:6]O.[C:9]1(=O)[CH2:14][CH2:13][CH2:12][C:11](=[O:15])[CH2:10]1>C(O)(=O)C.[Zn]>[CH2:5]1[C:1]2[CH:2]([NH:6][CH:13]3[C:12]=2[C:11](=[O:15])[CH:10]=[CH:9][CH2:14]3)[CH2:3][CH2:4]1

Participants

5

Reactant 2

HCID 104341,3-CyclohexanedioneHCID 73664614HCID 73664614, compound

Product 1

HCID 70421324HCID 70421324, compound

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 176Acetic AcidSolvent

Procedure

To a mechanically stirred solution of 1,2-cyclopentanedione-2-oxime (25.0 g, 0.22 mol) and 1,3-cyclohexanedione (25.0 g, 0.22 mol) in 70% acetic acid (250 mL) was added zinc dust (43.0 g, 0.66 g-atom) in about 5-g portions (moderately exothermic) over a 30 minute period. After the addition, the mixture was heated to reflux for 2 hours and was then cooled to room temperature. The solution was decanted from excess zinc and poured into ice water (250 mL). The mixture was extracted with dichloromethane (1×200 mL, 2×100 mL) and the combined extracts were washed with saturated sodium bicarbonate to neutrality, then washed with brine, and dried (Na2SO4). The solution was concentrated to about 1/4 the original volume, whereupon the title cyclopent[b]indolone (8.3 g) separated as a light tan solid: mp 236°-238° C. (recrystallized from ethyl acetate); IR (KBr) 3210 (NH), 1620 cm-1 (C=O); NMR (CDCl3) δ 2.07 (m, 2, CH2), 2.30-2.90 (m, 10, CH2), 10.17 (br s, 1, NH); MS m/e 175 (M+). Anal. Calcd for C11H13NO: C, 75.40; H, 7.48; N, 7.99. Found: C, 75.36; H, 7.38; N, 7.84.

Workup

  1. additionAfter the addition
  2. temperaturethe mixture was heated
  3. temperatureto reflux for 2 hours
  4. customThe solution was decanted from excess zinc
  5. additionpoured into ice water (250 mL)
  6. extractionThe mixture was extracted with dichloromethane (1×200 mL, 2×100 mL)
  7. washthe combined extracts were washed with saturated sodium bicarbonate to neutrality
  8. washwashed with brine
  9. dry with materialdried (Na2SO4)
  10. concentrationThe solution was concentrated to about 1/4 the original volume
  11. customwhereupon the title cyclopent[b]indolone (8.3 g) separated as a light tan solid
  12. custommp 236°-238° C. (recrystallized from ethyl acetate)

Sources & evidence

ORD record
ord-bd6d97fea14f45ffa1de11c20ac154b6
Source dataset
uspto-grants-1987_11
Patent number
US04707484

Reaction notes

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