Principles of Synthesis

R. Szostak, Molecular Sieves Principles of Synthesis and Identification, Van Nostrand Reinhold, New York, 1989. ISBN 0442280238. 

The synthetic chemist is more than a logician and strategist he is an explorer strongly influenced to speculate, imagine, and even to create. These added elements provide the touch of artistry which can hardly be included in a cataloguing of the basic principles of synthesis, but they are very real and extremely important."... 

Figure 1 Principle of synthesis of block copolymer by the use of macro-initiator. = azo or peroxy group O A = monomer B = oligomer A.

FI3. W. L. Jolly, The Synthesis and Characterisation of Inorganic Compounds. Prentice-Hall, Englewood Cliffs, New Jersey, 1970. A very useful text, covering the principles of synthesis of inorganic compounds, many of which can be extrapolated to organometallics. Contains chapters on synthetic principles, synthetic techniques, compound characterisation, synthesis. 

Szostak, R. (1998) Molecular Sieves, Principles of Synthesis and Identification, 2nd edn, Blackie Academic Professional, London, pp. 208-244. 

However, care must be exercised in using molecular sieves for drying organic liquids. Appreciable amounts of impurities were formed when samples of acetone, 1,1,1-trichloroethane and methyl-r-butyl ether were dried in the liquid phase by contact with molecular sieves 4A (Connett Lab.Practice 21 545 1972). Other, less reactive types of sieves may be more suitable but, in general, it seems desirable to make a preliminary test to establish that no unwanted reaction takes place. For the principles of synthesis and identification see R. Szostak Molecular Sieves, Chapman Hall, London 1988, and for structure, synthesis and properties see R.Szostak Handbook of Molecular Sieves, Chapman Hall 1992. 

Other important methods of synthesis of coordination compounds are discussed in detail [1,3,10,11,53,201,202,206,207,316,318,322,690]. In this respect, we emphasize the synthesis of metal-polymers [690,691] and preparation of complexes in the solid phase (mechano- or tribosynthesis) [10,201,202,206]. Additionally to the above-described techniques, the general methods and principles of synthesis of coordination compounds are used to obtain metal-polymers (immediate interaction of polymer ligands and metal salts, template electrosynthesis, polymer-analogous transformations). The last method consists of the polymerization of metal-monomers (metal-containing monomers) and fixation of metal complexes on the polymer... 

Szostak, R. Molecular Sieves Principle of Synthesis and Identification Van Nostrand Reinhold New York, 1989. 

Donor-Acceptor-Substituted Cyclopropanes — Principles of Synthesis and Ring... 

Generation of a bernyne intermediate. A general principle of synthesis devised by Bunnett involves creation of an intermediate benzyne having a nucleophilic center so located that it can add intramolecularly to the triple bond. An example is the synthesis of 3-acetyloxindole from o-chloroacetoacetanilide (Union Carbide Chem. Co.) with potassium amide in liquid ammonia. In another synthesis o- and m-halo isomers gave the same product. 

An important principle of synthesis is to avoid mixtures of isomers wherever possible minimizing separations increases recovery of products. Bimolecular dehydration is a random process. Heating a mixture of ethanol and methanol with acid will produce all possible combinations dimethyl ether, ethyl methyl ether, and diethyl ether. This mixture would be troublesome to separate. 

The results obtained show that immobilization of metal complexes in polymer gels allows to prepare physically heterogeneous and chemically homogeneous catalysts and leads to an important increase in their activity, selectivity and stability in the reactions of dimerization of lower olefins. The immobilization of the complexes opens new possibilities of macromolecular design of the catalysts with desired structural organization and will contribute to the development of general principles of synthesis of highly efficient and environmentally friendly catalytic systems for liquid phase processes. 

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