2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 18707014, compound

HRID 1422124Notes

Reaction equation

HRID 1422124 reaction equation
[C:1]([NH:4][C:5]1[CH:13]=[CH:12][C:11]2[N:7]([CH:8]=[C:9]([C:16]3[CH:21]=[CH:20][C:19]([O:22][CH2:23][C:24]4[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=4)=[CH:18][CH:17]=3)[C:10]=2[CH2:14][CH3:15])[CH:6]=1)(=[O:3])[CH3:2].[C:30]([O:34][CH3:35])(=[O:33])[C:31]#[CH:32].ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>C1(C)C=CC=CC=1>[C:1]([NH:4][C:5]1[CH:13]=[CH:12][C:11]2[N:7]3[C:6]=1[C:31]([C:30]([O:34][CH3:35])=[O:33])=[CH:32][C:8]3=[C:9]([C:16]1[CH:21]=[CH:20][C:19]([O:22][CH2:23][C:24]3[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=3)=[CH:18][CH:17]=1)[C:10]=2[CH2:14][CH3:15])(=[O:3])[CH3:2]

Participants

5

Reactant 3

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 13536Methyl propiolateHCID 18706907HCID 18706907, compound

Product 1

HCID 18707014HCID 18707014, compoundYield 83%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
90 °C

Procedure

A solution of 6-acetylamino-2-(4-benzyloxyphenyl)-1-ethylindolizine (38.5 g, 0.1 mol) in 3000 ml of toluene was stirred in a nitrogen atmosphere at 50° C. while methyl propiolate (10.2 ml, 0.115 mol) was added dropwise. The mixture was heated to 90° C. and stirring was continued for 3 hours. The mixture was cooled to 4° C. and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (22.6 g, 0.1 mol) was added in portions. The cooling source was removed and stirring was continued for 16 hours. The mixture was filtered through celite and the celite pad was washed several times with toluene. The combined filtrates were evaporated to app. 500 ml and 1000 ml of petroleum ether was added. The precipitate was filtered off and dried to yield 38.7 g (83%) of the title compound. M.p. 210-13° C. 1H-NMR (DMSO-d6, 200 Hz) δ: 1.38 (t, 3H), 2.27 (s, 3H), 3.15 (q, 2H), 3.96 (s, 3H), 5.18 (s, 2H), 7.20 (d, 2H), 7.35-7.55 (m, 5H), 7.75 (d, 2H), 7.90 (s, 1H), 8.13 (d, 1H), 8.95 (d, 1H), 11.78 (s, 1H).

Workup

  1. additionwas added dropwise
  2. temperatureThe mixture was cooled to 4° C.
  3. customThe cooling source was removed
  4. stirringstirring
  5. waitwas continued for 16 hours
  6. filtrationThe mixture was filtered through celite
  7. washthe celite pad was washed several times with toluene
  8. customThe combined filtrates were evaporated
  9. addition500 ml and 1000 ml of petroleum ether was added
  10. filtrationThe precipitate was filtered off
  11. customdried

Sources & evidence

ORD record
ord-2ba8015b823a4405b7696e8f5f0ffb11
Source dataset
uspto-grants-2000_06
Patent number
US06080754

Reaction notes

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