During extensive studies on π-allylpalladium chemistry, we have developed classical β-keto ester and malonate chemistry to a new generation by discovering a variety of palladium-catalyzed reactions of their allylic esters. Palladium enolates are generated from allyl β-keto esters after decarboxylation and undergo the following transformations; a) reductive elimination to provide α-allyl ketones, b) elimination of β-hydrogen to give α, β-unsaturated ketones, c) formation of α-methylene ketones, d) hydrogenolysis to give ketones, e) aldol condensation, and f) Michael addition. Allyl malonates and cyanoacetes undergo similar reactions. Results of these studies, including several applications carried out by other researchers are summarized.
The palladium-catalyzed cross-coupling reaction between different types of organoboron compounds with sp2-, sp3-, and sp-hybridized carbon-boron compounds and various organic electrophiles in the presence of base provides a powerful and useful synthetic methodology for the formation of carbon-carbon bonds. The coupling reaction offers several advantages: (1) Availability of reactants (2) Mild reaction conditions (3) Water stability (4) Easy use of the reaction both in aqueous and heterogeneous conditions (5) Tolerance of a broad range of functional groups (6) High regio- and stereoselectivity (7) Insignificant effect toward steric hindrance (8) Use of very small amounts of catalysts (9) Utilization as one-pot synthesis (10) Non-toxic reaction
The simplified method of analysis to assess liquefaction potential of a given sand deposit is briefly introduced in the first part of this paper. Then, recent advances in the laboratory testing for evaluating liquefaction resistance are described with a particular emphasis on the sand partly saturated with water. As a means to identify the degree of saturation which is applicable for both field deposits and laboratory samples, the use of the longitudinal wave (P-wave) is proposed based on a suite of data obtained from the triaxial tests in the laboratory. It is recommended that the non-destructive P-wave measurements be carried out first to determine the degree of saturation, and then the cyclic triaxial tests involving large destructive strains should be performed to determine the cyclic strength on the same sample of the sand. In order to demonstrate usefulness of the proposed approach, two sets of undisturbed samples were secured from two sites; one is located in Sakai-minato city which has suffered severe liquefaction at the time of the 2000 Tottoriken-Seibu earthquake and the other site is located in Koshigaya city, Saitama, where likelihood of liquefaction to occur in a future earthquake is of major concern. Penetration tests and in-situ velocity logging were also conducted at these two sites. By adjusting the P-wave velocity of the undisturbed samples in the laboratory so as to have the same velocity in the field, the in-situ state of saturation was reproduced in the laboratory samples. Then, the cyclic loading tests were conducted to determine the cyclic strength of intact samples. The results of the laboratory tests as above were incorporated into the simple method of liquefaction analysis described in the first section of this paper. The analysis seems to yield results which are in reasonably good agreement with what was observed at the time of the earthquake.
An optimization model, fit for practical use, to allocate COD (Chemical Oxygen Demand)-based wasteload into a river system among outfalls is developed within the framework of robust optimization (RO). Nonpoint source COD loading, estimated based on the unit loading factor to be assumed known, is treated as uncontrollable one. The total amount of expected allowable COD load from point sources is then, under all possible scenarios of uncertain input information, maximized while satisfying the constraints on in-stream COD and DO (Dissolved Oxygen) transport, effluent standards and river water quality standards. Advantage of the ε-RO model using the ε-constraint method for optimization practice is brought to light from theoretical and practical aspects, in comparison with the conventional RO model resorting to the Lagrangian method. Solving a simple hypothetical example problem, it is demonstrated that the model developed is competent for successfully generating noninferior and robust solutions on optimal COD load allocation.
Realities of in-stream water quality and its control in Yasu River, Japan are diagnosed by use of an epsilon robust optimization (ε-RO) model with the aid of a Geographic Information System (GIS). The GIS helps delineate catchment boundaries associated with a diagnosed section of the river, find outfalls of wastewater, and estimate both discharge and uncontrollable COD (Chemical Oxygen Demand) load from nonpoint sources. Twelve hydro-environmental scenarios assumed to stochastically occur in a year are generated based on historical data. Calibration of a finite element model for COD and dissolved oxygen transport is conducted to identify some scenario components. The ε-RO model determines the optimal wasteload quotas at point sources (PSs) through allocation of the maximized total COD load, which lead to ameliorating water quality in the river. The diagnostic results show that there is every possibility that the in-stream water quality is upgraded even if total COD loading is increased so long as it is appropriately allocated to PSs.