Applications of prenyltransferases to the organic synthesis of some biologically active compounds are described. Trishomo-15, bishomo-16 and homo-farnesyl pyrophosphate 9, whose carbon skeletons are the same as those of the insect juvenile hormones, JH 0, JH I, and JH II, respectively, are synthesized by the action of farnesyl pyrophosphate synthetase of pig liver. The stereospecific C-C bond forming reaction of farnesyl pyrophosphate synthetase was efficiently utilized in the asymmetric synthesis of the stereoisomers of faranal, a trail pheromone of the Pharaoh ant, to establish the absolute configuration of the pheromone. The distribution of carbon chain length of polyprenyl pyrophosphates synthesized with solanesyl pyrophosphate synthetase of Micrococcus luteus can be controled artificially by changing the Mg++ concentration of the reaction mixture.
Recent advances in the synthesis of useful organic compounds by enzymatic method are described. Various L-amino acids were synthesized by multifunctional pyridoxal enzymes; D-amino acids, especiall D-phenylglycine derivatives, by dihydropyrimidinase, purine arabinosides by nucleoside phosphorylases, insulin by proteases, steroid hormons by oxygenases, semisynthetic penicillins by penicillin acylase, and coenzyme A through biosynthetic pathway with pantothenic acid and L-cysteine under the coupling with ATP-generating system. The described enzymatic methods are simple and the most economical processes to date for the industrial production of these useful compounds.
The present situation and the future development of the functional membrane are discussed. It is expected that the functional membrane play increasingly great roles in the chemical industry of the coming decade. These membranes are formed from polymer films, liquid membranes or bilayer membranes. The two, most important technologies based on the polymeric membrane are reverse osmosis and ion exchange. The liquid membrane is used for separation of ionic species : an extention of the solvent extraction process. By using appropriate ligands and ionophores, highly selective separations are realized. The active transport is made possible if the physical and chemical potentials are applied to the transport process. More advanced functional membranes may be designed on the basis of the synthetic bilayer membrane.
Industrial microorganisms have been improved mainly by mutation and selection for their productivity, but recent development of gene manipulation would offer more effective tool for microbial breedings. Since the primary gene products are polypeptides, the gene manipulation techniques have been mainly applied to produce human peptide hormones, interferons and enzymes. These polypeptides have been expected to be useful for therapy of human diseases in near future. The technique will be available also to improve biomass production including microorganisms and plants. Further application is planned in the field of chemical industry, such as the conversion of ethylene to ethylene oxide. In addition, this technique would be developed as tolls for breeding of industrial microorganisms, especially in Japan.
This report gives a short review about the progress of technological innovation in chemical uses of Biomass in the world. It has the four articles, (1) Chemicals from Renewable Resources (2) Oxygenated Aliphatic Chemical Feedstocks from Biomass (3) Oxygen containing Aromatic Compounds obtained from Lignin (4) About the Future Complemental Relation between the Three Carbon Resources-Oil·Coal·Biomass as Feedstocks for the Chemical Industry
An important role of C1 Chemistry is discussed generally from various situations. It is necessary for us to find out a new route of synthesis for basic chemical products from alternative raw materials which will be available in future by balance of costs between petroleum and other resources.
Synthetic methods of aromatic compounds from aliphatic compounds can be classified as follows : (A) Cyclohexene derivatives, obtained by Friedel-Crafts heaction from diene and dienophile are dehydrogenated to aromatic compounds. (B) Cyclotrimerization of acetylenic compounds. (C) Inter-and intra-molecular condensation of appropariate dicarbonyl-compounds and then the dehydrogenation of thus obtained cyclohexenone derivatives to the aromatic compounds. (D) Another various methods. This article concerns exclusively to the (C) method. The (C) method can be further divided into the following three sub-methods : C-1. Michael addition of active methylene and active methyl compounds to α, β-unsaturated carbonyl- compounds and then the adducts, i. e. the δ-dicarbonyl-compounds are cyclized intramolecularly to the cyclohexenone derivatives. The cyclization reactions are aldol-or ester condensation and thus obtained cyclohexenone derivatives are dehydrogenated to the corresponding aromatic compounds. C-2. Two molecules of active methylene compounds are joined by aldehydes (formaldehyde or acetaldehyde) or formic acid and thus obtained δ-dicarbonyl-compounds are then cyclized intramolecularly as in the case of C-1. C-3. Two molecules of dicarbonyl-compounds are intermolecularly cyclo-condensed directly to the substituted benzene-derivatives or at first to the cyclohexane-dione compounds and then dehydrogenated to the aromatic compounds. Many examples, according to the above-mentioned classifications, are given in this article.
The growing importance of energy, feedstock and environmental problems provide new opportunities for electroorganic industry. Some electroorganic processes are shown to be more economical and attractive for industrial production of fine chemicals, as compared with catalytic chemical routes. A detailed exploration of the process development for electroorganic reactions is provived. Factors for most effective process are the optimization of electrochemical reaction, the suitable design of cell and the proper choice of electrode. The electrochemical concept is not only possible for many commercial organic processes but also may actually be preferable from the technical, social and economic viewpoints, In renewal of an catalytic chemical process, it is worth due consideration to apply new electroorganic process.
Recent progress of industrially important isoprene chemicals is reviewed. Many various chemicals were synthesized by using isoprene as a starting material. Aroma chemicals, medicinal chemicals, agrochemicals, and their intermediates, for example, new type aroma chemicals having woody note, pheromones, drugs for ulcer, vitamines, and so on, and new synthesizing routes for those isoprene derived chemicals are briefly described.
Linear low density polyethylene (LLDPE) is attracting increasing attention lately in chemical industry. LLDPE was brought into commercial production for the first time in 1959 by Du Pont of Canada and, later in 1970, Mitsui Petrochemical Industries, Ltd. also set out on manufacturing its LLDPE product with the trade name of L-M Copolymer in Japan. LLDPE is manufactured by a process different from the conventional high-pressure process, such that its molecular and crystalline structures are uniquely distinct from those of high-pressure conventional LDPE. LLDPE offers salient characteristics, combining low swelling ratio and low melt strenght in its melt behavior, with high tensile strength, high elogation at break, high rigidity, high impact strength, and high environmental stress-crack resistance in respect of its solid properties. With these features used to the best advantage, LLDPE can afford a resin saving of 20 to 30 % and is expected to find its way largely into various fields of application currently served by LDPE.
Recent progress in functional organic materials for electronic industries was briefly reviewed. Avoiding the exhaustive descriptions, we will show how the organic and polymeric materials are used for electronic industries. The topics concerned profoundly with organic and polymer synthesis will be mentioned principally. For display materials, the topics on liquid crystals including the color display using guest-host effect, new mesomorphic state discotic mesophase and reentrant mesophase, polymeric liquid crystal will be shown. The electrochromic materials;viologen derivatives, alkalineearth diphthalocyanine complexes, polymeric electrochromic materials, will also be described. For recording materials, we will refer to the thermal recording materials, organic photoconductors for electrophotography and photochromic materials. Application of polyimide for passivation of semiconductor and new resist material for X ray and electron beam lithography will be explained. The new organic mateials which shows exotic characteristics; organic metals, template polymers, materials for chemical holeburning will be stated.