Conjugated Azoalkenesi Part III. Synthesis of Sone Phosphorous Azoalkenes

Recently, some of us reviewed the synthes is and chemical reactions of conjugated azoalkenes.¹ Emphasis was placed on the fact that these derivatives represent at the same time interesting products and useful intermediates in organic chemistry. In fact, conjugated azoolefins undergo a wide range of 1,4-additions, (3+2)- and (4+2)-cycloadditions allowing various functionalizations of the carbon atom adjacent to the carbonyl group, and the construction of many types of interesting five - and six-membered heterocycles, such as widely substituted pyrrole and pyridazine rings. These relevant synthetic objectives appear not to be smoothly obtained by other procedures. In addition, many of the compounds produced from conjugated azoalkenes can profitably be employed in the preparation of natural, pharmaceutical, and phytopharmaceutical products.¹     

Effect of metal ions in organic synthesis. Part XIII. Selective regeneration of hydroxyl and carboxyl groups from some derivatives by copper (II) ion-promoted hydrolysis

Acetyl derivatives of alcoholic and phenolic hydroxyl groups represent not only useful educts, intermediates and products in organic, bioorganic and pharmaceutical chemistry, but also interesting derivatives for isolation, purification and characterization of alcohols and phenols (especially for natural products). Furthermore, the acetylation reaction is frequently used for the protection of hydroxyl function. In general, however, acetoxy-groups may be highly resistent to hydrolysis so that their conversion into hydroxyl groups often requires strongly basic or acidic media, expensive and/or hardly available reagents, complicated procedures. These conditions may be incompatible with sensitive substrates or with other insufficiently stable groups present in the molecular residue.^1,2 Very similar arguments are sound for some hydrazide derivatives of carboxylic acids.^1,3,4     

Effect of Metal Ions in Organic Synthesis. part XVI. Knoevenagel Condensations of Aldehydes and Tosylhydrazones with 2,4-Pentanedione by Copper (II) Chloride-Catalyzed Reaction

Based on some of our previous findings on the activity of some metal ions in certain organic reactivities,¹ we have now studied the Knoevenagel condensations of aliphatic and aromatic aldehydes or their tosylhydrazone derivatives with 2,4-pentanedione. In the presence of catalytic amounts of anhydrous copper (II) chloride, these compounds react in tetrahydrofuran at room temperature, affording the corresponding alkylidene or arylidene compounds in 48–98% yields.