HCID 18707010, compound → HCID 18707007, compound

HRID 1422080Notes

Reaction equation

HRID 1422080 reaction equation
[CH2:1]([O:8][C:9]1[CH:10]=[CH:11][C:12]2[N:13]3[C:17]=1[C:16](C(O)=O)=[C:15]([C:21]([O:23][CH2:24][CH3:25])=[O:22])[C:14]3=[C:26]([C:30]1[CH:35]=[CH:34][C:33]([O:36][CH2:37][C:38]3[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=3)=[CH:32][CH:31]=1)[C:27]=2[CH2:28][CH3:29])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1>N1C2C(=CC=CC=2)C=CC=1.[Cu]>[CH2:1]([O:8][C:9]1[CH:10]=[CH:11][C:12]2[N:13]3[C:17]=1[CH:16]=[C:15]([C:21]([O:23][CH2:24][CH3:25])=[O:22])[C:14]3=[C:26]([C:30]1[CH:31]=[CH:32][C:33]([O:36][CH2:37][C:38]3[CH:39]=[CH:40][CH:41]=[CH:42][CH:43]=3)=[CH:34][CH:35]=1)[C:27]=2[CH2:28][CH3:29])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

4

Reactant 1

HCID 18707010HCID 18707010, compound

Product 1

HCID 18707007HCID 18707007, compound

Reagents, catalysts & solvents 2

HCID 23978CopperCatalystHCID 7047QuinolineSolvent

Conditions

Temperature
170 °C

Procedure

7-Benzyloxy-3-(4-benzyloxyphenyl)-2-ethoxycarbonyl-4-ethylpyrrolo[2,1,5-cd]indolizine-1-carboxylic acid (21.63 g, 38 mmol) was dissolved in 220 ml of quinoline under a nitrogen atmosphere. Copper powder (3.35 g, 50 mmol) was added and the mixture was heated to 170° C. for 21/2 hour. The reaction mixture was filtered when hot, and the filtrate was flash chromatographed over silica gel 60, using toluene: petroleum ether (1:1) as the eluent. Fractions containing the product were combined and added 300 ml of water was added and the pH was adjusted to 2 with 6N hydrochloric acid. The organic material was extracted into 3×300 ml of dichloromethane and the combined organic layers were washed with brine, dried over sodium sulfate and the solvent was evaporated. The crude product was purified by column chromatography over silica gel 60, using toluene:petroleum ether (1:1) as the eluent. The crude product was crystallised from hot toluene and petroleum ether. This gave 15.90 g (79%) of ethyl 7-benzyloxy-3-(4-benzyloxyphenyl)-4-ethylpyrrolo[2,1,5-cd]indolizine-2-carboxylate as yellow crystals. M.p. 114-116° C. MS(SP): m/z 529 (M+). 1H-NMR (DMSO-d6, 300 MHz) δ: 0.92 (t, 3H); 1.28 (t, 3H); 2.93 (q, 2H); 4.00 (q, 2H); 5.19 (s, 2H); 5.61 (s, 2H); 7.12 (d, 2H); 7.32-7.53 (m, 11H); 7.59 (d, 2H); 7.74 (s, 1H); 8.16 (d, 1H).

Workup

  1. filtrationThe reaction mixture was filtered when hot
  2. customchromatographed over silica gel 60
  3. additionFractions containing the product
  4. additionadded 300 ml of water
  5. additionwas added
  6. extractionThe organic material was extracted into 3×300 ml of dichloromethane
  7. washthe combined organic layers were washed with brine
  8. dry with materialdried over sodium sulfate
  9. customthe solvent was evaporated
  10. customThe crude product was purified by column chromatography over silica gel 60
  11. customThe crude product was crystallised from hot toluene and petroleum ether

Sources & evidence

ORD record
ord-1e68046c9c264fdc98791efaf36e27b3
Source dataset
uspto-grants-2000_06
Patent number
US06080754

Reaction notes

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