2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 136049191, compound

HRID 661806Notes

Reaction equation

HRID 661806 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([C:9]2[C:10]3[NH:14][C:13]([CH:15]=[C:16]4[N:40]=[C:19]([C:20]([C:32]5[CH:37]=[CH:36][CH:35]=[C:34]([O:38][CH3:39])[CH:33]=5)=[C:21]5[NH:31][C:24](=[CH:25][C:26]6[CH:27]=[CH:28][C:29]=2[N:30]=6)[CH:23]=[CH:22]5)[CH:18]=[CH:17]4)=[CH:12][CH:11]=3)[CH:6]=[CH:7][CH:8]=1.[C:41]([C:43]1[C:49](=O)[C:48](Cl)=[C:47](Cl)[C:45](=O)[C:44]=1[C:53]#N)#N.[CH2:55]1[CH2:59]OC[CH2:56]1>>[CH3:39][O:38][C:34]1[CH:33]=[C:32]([C:20]2[C:21]3[NH:31][C:24]([CH:25]=[C:26]4[N:30]=[C:29]([C:9]([C:5]5[CH:6]=[CH:7][CH:8]=[C:3]([O:2][CH3:1])[CH:4]=5)=[C:10]5[NH:14][C:13](=[C:15]([CH2:56][CH2:55][CH2:59][CH2:53][CH2:44][CH2:45][CH2:47][CH2:48][CH2:49][CH2:43][CH3:41])[C:16]6[CH:17]=[CH:18][C:19]=2[N:40]=6)[CH:12]=[CH:11]5)[CH:28]=[CH:27]4)=[CH:23][CH:22]=3)[CH:37]=[CH:36][CH:35]=1

Participants

4

Reactant 3

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 8028TetrahydrofuranHCID 135503060HCID 135503060, compound

Product 1

HCID 136049191HCID 136049191, compound

Procedure

5,15-bis-(3-Methoxy-phenyl)-porphyrin (100 mg, 0.19 mmol) is dissolved in anhydrous THF (30 mL at −50° C. under an argon atmosphere. The organolithium reagent described above (5 mL) is added dropwise to the mixture. After 5 min the cooling bath is removed and the mixture is warmed to room temperature. After stirring at room temperature for 15 min the reaction is quenched by slow addition of water (2 mL). After 15 min the mixture is oxidized by the addition of DDQ (4 mL, 0.4 mmol, 0.1 M in THF) and stirred for a further 15 min. The mixture is filtered through alumna (neutral, Brockman grade+) and purified by column chromatography on silica gel eluting with hexane:dichloromethane (4:1 by vol.) The first fraction is collected and crystallised from methanol:dichloromethane.

Workup

  1. additionis added dropwise to the mixture
  2. customAfter 5 min the cooling bath is removed
  3. customis quenched by slow addition of water (2 mL)
  4. stirringstirred for a further 15 min
  5. filtrationThe mixture is filtered through alumna (neutral, Brockman grade+)
  6. custompurified by column chromatography on silica gel eluting with hexane:dichloromethane (4:1 by vol.) The first fraction
  7. customis collected
  8. customcrystallised from methanol

Sources & evidence

ORD record
ord-4140583447d14607bda85e716ba458fd
Source dataset
uspto-grants-2011_12
Patent number
US08084602B2

Reaction notes

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