2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → Dimethyl 7-benzyloxy-3-(4-benzyloxyphenyl)-4-ethylpyrrolo[2,1,5-cd]indolizine-1,2-dicarboxylate

HRID 1422077Notes

Reaction equation

HRID 1422077 reaction equation
[CH2:1]([O:8][C:9]1[CH:17]=[CH:16][C:15]2[N:11]([CH:12]=[C:13]([C:20]3[CH:25]=[CH:24][C:23]([O:26][CH2:27][C:28]4[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=4)=[CH:22][CH:21]=3)[C:14]=2[CH2:18][CH3:19])[CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:34]([C:40]([O:42][CH3:43])=[O:41])#[C:35][C:36]([O:38][CH3:39])=[O:37].ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>C1(C)C=CC=CC=1>[CH2:1]([O:8][C:9]1[C:10]2[N:11]3[C:12]([C:13]([C:20]4[CH:21]=[CH:22][C:23]([O:26][CH2:27][C:28]5[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=5)=[CH:24][CH:25]=4)=[C:14]([CH2:18][CH3:19])[C:15]3=[CH:16][CH:17]=1)=[C:34]([C:40]([O:42][CH3:43])=[O:41])[C:35]=2[C:36]([O:38][CH3:39])=[O:37])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 12980Dimethyl acetylenedicarboxylateHCID 187070166-Benzyloxy-2-(4-benzyloxyphenyl)-1-ethylindolizine

Product 1

HCID 18707022Dimethyl 7-benzyloxy-3-(4-benzyloxyphenyl)-4-ethylpyrrolo[2,1,5-cd]indolizine-1,2-dicarboxylateYield 71.9%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

6-Benzyloxy-2-(4-benzyloxyphenyl)-1-ethylindolizine (50.0 g, 115 mmol) and dimethyl acetylene dicarboxylate (18.5 ml, 150 mmol) was dissolved in 1100 ml of dry toluene at 0° C. The reaction was slowly heated to room temperature and stirred for 3 hours. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (26 g, 115 mmol) was added and stirring was continued for 1/2 hour. The mixture was filtered through celite and the solvent removed. The crude product was crystallised from methanol to afford 47.4 g (71%) of dimethyl 7-benzyloxy-3-(4-benzyloxyphenyl)-4-ethylpyrrolo[2,1,5-cd]indolizine-1,2-dicarboxylate as yellow crystals. M.p. 115-120° C. 1H-NMR (DMSO-d6, 300 MHz) δ: 1.32 (t, 3H); 3.01 (q, 2H); 3.56 (s, 3H); 3.72 (s, 3H); 5.21 (s, 2H); 5.50 (s, 2H); 7.17 (d, 2H; 7.32-7.53 (m, 10H); 7.60 (d, 2H); 7.67 (d, 1H); 8.22 (d, 1H).

Workup

  1. stirringstirring
  2. waitwas continued for 1/2 hour
  3. filtrationThe mixture was filtered through celite
  4. customthe solvent removed
  5. customThe crude product was crystallised from methanol

Sources & evidence

ORD record
ord-7d32b438178749208c7919de96da1908
Source dataset
uspto-grants-2000_06
Patent number
US06080754

Reaction notes

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