The features of electrochemical method in the oxidation of organic compound are described from practical standpoints as compared with those of oxidizing agent method and catalytic method. Oxidation products are usually formed by direct electron release of organic compounds to anode or indirect path through inorganic reagent to anode, followed by various chemical reactions, but can be partly formed by cathodic reaction of dissolved oxygen in electrolytic solution with organic compounds. Electro-oxidation method which was developed since 1830 ages is recently much attentioned as an improved method of organic syntheses because of emphasis on its advantages, especially specific and harmlessly environmental process. Several kinds of characterized reactions in electro-oxidation synthesis such as Kolbe-type dimerization, anodic substitution and oxygenation via inorganic mediators are mentioned. Dehydrodimerization of active hydrogen compounds and regiospecific anodic halogenation to aromatic nucleous using cyclodextrin modified carbon electrodes are discussed in fairly details.
This review is organized under the following headings with 440 references. 1. Generation and reactions of reactive intermediates. 1.1. Carbon species. 1.2. Nitrogen species. 1.3. Oxygen species. 1.4. Others. 2. Reactions of organic hetero atoms. 2.1. Nitrogen. 2.2. Sulfur. 2.3. Phosphorus and others. 3. Formation and reactions of organometallic compounds. 3.1. Formation of metallic compounds employing electrodes as a metal source. 3.2. Conversion of metallic compounds to other metallic compounds. 3.3. Formation of nonmetallic compounds from metallic compounds. 4. Bimolecular reactions. 4.1. Dimerization. 4.2. Cyclization. 4.3. Ring expansion and contraction. 5. Stereochemistry. 5.1. Stereoselective and stereospecific reactions. 5.2. Asymmetric reactions and asymmetric syntheses. 6. New type reactions.
Progress in the synthesis of long-lived carbocations has been reviewed with selected 180 references published for one and half decade through 1978. On the basis of the structural features ten major types of the carbocations are included and their synthetic routes, especially the final steps, are described and discussed briefly. The types are follows : 1) dienyl and allyl cations, 2) vinyl and phenyl cations, 3) Hückel cations, 4) carbocations stabilized with the homoaromaticity and with the bicycloaromaticity, 5) carbocations with the coordination number 4, 5, or 6, 6) dipositive carbocations and carbodications, 7) hydrocarbon radical cations, 8) carbocations with intramolecular through-space stabilization, 9) carbocations stabilized by heteroatoms, 10) carbocations coordinated with metal and carbocations stabilized by organometallic complexes
Recent progress of the synthetic entries and the utilities of fluorinated sulfur (IV) and (VI) compounds including new routes to the stable sulfuranes and stereochemical problems on sulfur (IV) and (VI) compounds is reviewed. Synthesis and synthetic reactions of R2S (OCH2CF3) developed by these authors are also summarized.
A survey is given of recent progress of additives which can be effectively used for photographic materials and processing. A number of organic compounds are employed for extensive purposes, i. e., physical-ripening retarders, stabilizers and chemical sensitizers advantageous for photographic characteristies; coating aids, hardeners and antistatic agents to improve physical properties of films; UV absorbers and antioxidants effective for image stability. Studies on the additives is still in progress, associated with advancement of synthetic organic chemistry.
It has been so far reported that the reaction of carbon monoxide with aryl or vinyl halides in the presence of alcohol or amine smoothly proceeded under atmospheric pressure by use of a catalytic amount of PbII and PPh3 to give esters or amines in good yields. This reaction was extended by us to the synthesis of heterocyclic compounds. The aryl halide having the internal amino, hydroxy and amido groups gave the benzolactams, benzolactones and imido derivatives. A variety of heterocyclic compounds including sendaverine (alkaloid) and anthramycine derivatives (antibiotics) were synthesized by this intramolecular cyclization.