第一节用硅对碳进行等电排置换设计更加安全的化学品教程方案.ppt

Chapter 4 Application of Designing Safer Chemicals 4.1 Isosteric Replacement of Carbon with Silicon (用硅对碳进 行等电排置换) in the Design of Safer Chemicals 4.2 Designing Biodegradable Chemicals 4.3 Designing Aquatically Safer Chemicals References 4.1 Isosteric Replacement of Carbon with Silicon in the Design of Safer Chemicals 4.1.1 Silicon is an Isosteric atom of Carbon Common Features of Silicon and Carbon grouped in column 4A of the Periodic Table having many chemical similarities ： tetravalent, tetrahedral, and form stable bonds with carbon. Silicon is an Isosteric atom of Carbon Organic derivatives of silicon generally have no intrinsic toxicity, in contrast with the other Group 4A elements germanium (Ge), tin (Sn), and lead (Pd). Examples: Acetylcholine (乙酰胆碱) Urethane (尿烷) Muscarinic Antagonistis（蝇覃碱拮抗剂） Silicon is the element most similar to carbon, however it is not a generic replacement for all carbon atoms and certain strict limitations apply. Double bonds to silicon, and three-membered rings containing silicon, are unstable to air and moisture. Single bonds from silicon to heteroatoms such as nitrogen and oxygen are strong but can hydrolyze readily. Abiotic Degradation Currently the major environmental source of organosilane is silicone polymer (聚硅酮)(siloxanes硅氧烷), primarily polymers of 1,1-dimethyl silanediol. Siloxanes were once thought to be environmentally stable, but are now known to be depolymerized in the presence of water and soil. Example 1： Silane Analogs of DDT Example 2：Organosilane Fungicides (杀真菌剂) Silane Analogs of DDT In an early effort to design a more benign version of DDT, a number of silane analogs such as the DDD analog were prepared with the anticipation that these would be less environmentally persistent. Silane Analogs of DDT The presence of the readily oxidized silicon-hydrogen bond would have been one source of instability, both in