Potassium periodate → HCID 86736813, compound
Reaction equation
[C@@H:1]12[CH2:22][CH2:21][C@@H:2]1[C:3]([OH:20])=[C:4]([OH:19])[C:5]1[CH:6]=[CH:7][C:8]3[CH:9]=[C:10]4[C:15](=[CH:16][C:17]=3[C:18]=12)[CH:14]=[CH:13][CH:12]=[CH:11]4.[Na].I([O-])(=O)(=O)=O.[K+]>>[CH:5]1([CH:4]=[O:19])[C:6]2[C:7]3[CH:16]=[C:15]4[C:10]([CH:11]=[CH:12][CH:13]=[CH:14]4)=[CH:9][C:8]=3[CH:17]=[CH:18][C:1]=2[CH:22]=[CH:21][CH:2]1[CH:3]=[O:20]Participants
Procedure
The dihydrobenzanthracene derivatives of the present invention may be readily prepared as set forth in the following reaction scheme: ##STR6## wherein A and B are as hereinbefore defined. In accordance with the above reaction scheme, the benzanthracene (VII) is heated with excess vinylene carbonate at reflux temperature under nitrogen for about 10-24 hours. Excess vinylene carbonate is removed by vacuum distillation. The residue is taken up in methylene chloride, clarified with charcoal, and precipitated with methanol to provide both the syn and anti forms of the cis-dihydro-ethanobenzanthracene cyclic carbonate (XII). Hydrolysis of the cyclic carbonate (XII) with aqueous-ethanolic potassium hydroxide at 70°-75° C. for about 1-4 hours produces both the syn and anti forms of the cis-dihydro-ethanobenzanthracene-diol (XIII) which in turn is treated with lead tetraacetate in glacial acetic acid at 20°-35° C. for about 10-30 minutes to give the dihydrobenzanthracene-dicarboxaldehyde (XIV). Alternatively, the diol (XIII) may be suspended in an aqueous solution of either sodium or potassium periodate and stirred at room temperature for 24 hours to provide the dicarboxaldehyde (XIV). Either procedure provides the cis-isomer of the dicarboxaldehyde (XIV) which may be readily converted to the trans form by standard procedures. Oxidation of the dihydrobenzanthracene-dicarboxaldehyde (XIV) with either ferric chloride in methanol or lead tetraacetate in glacial acetic acid, both at 20°-35° C. for 1-5 hours, then provides the benzanthracene-dicarboxaldehyde (XI). Treatment of XI and XIV with a hydrazine derivative of the formula H2N--NH--B then provides the novel compounds (I, II, III and IV) of the present invention. This reaction is best carried out in ethanol or n-propanol at the reflux temperature for 1-4 hours in the presence of an acid such as hydrochloric acid or acetic acid.
Sources & evidence
- ORD record
- ord-6b1269dcc3a34af7888c8c8e13b71655
- Source dataset
- uspto-grants-1980_02
- Patent number
- US04187373
Reaction notes
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