Precursor synthetic methods

The IF structures and nanotubes for WS2 were first observed during hydrodesulfurization using thin films of tungsten [50]. Tenne and coworkers [59-62] developed a precursor synthetic method for obtaining both IF-MS2 (M = Mo, W) and nanotubes. The method is based on a gas-phase reaction between partially reduced metal oxides and hydrogen sulfide. The synthesis consists of three steps. First is the formation of the oxide MO3. For M = W, this step involves the preparation of WO3 by heating a mngsten filament in the presence of wate vapor. The second step is the partial reduction of the oxide to an amorphous suboxide MO3 c. For W, the reduction of WO3 produces in the form of needle-... 

Silicon oxynitride exhibits better resistance to thermal downshock and oxidation than silicon nitride, although it decomposes under similar conditions with loss of N2 . Thus, it represents a practical target for precursor synthetic methods. Unfortunately, it is difficult to achieve the exact 2Si 1012N stoichiometry in a processable precursor and retain this ratio during pyrolysis. Hence, very little work has been directed toward developing Si20N2 precursors . Furthermore, the approaches used to date rely on processing with NH3 to achieve the correct stoichiometry. 

Alkynes with EWGs are poor substrates for the coupling with halides. Therefore, instead of the inactive propynoate, triethyl orthopropynoate (350) is used for the coupling with aryl halides to prepare the arylpropynoate 351. The coupling product 353 of 3,3-dicthoxy-l-propyne (352) with an aryl halide is the precursor of an alkynal[260]. The coupling of ethoxy) tributylstan-nyl)acetylene (354) with aryl halides is a good synthetic method for the aryl-acetate 355[261]. 

Literature articles, which report the formation and evaluation of difunctional cyanoacrylate monomers, have been published. The preparation of the difunctional monomers required an alternative synthetic method than the standard Knoevenagel reaction for the monofunctional monomers, because the crosslinked polymer thermally decomposes before it can revert back to the free monomer. The earliest report for the preparation of a difunctional cyanoacrylate monomer involved a reverse Diels-Alder reaction of a dicyanoacrylate precursor [16,17]. Later reports described a transesterification with a dicyanoacrylic acid [18] or their formation from the oxidation of a diphenylselenide precursor, seen in Eq. 3 for the dicyanoacrylate ester of butanediol, 7 [6]. 

The first type of polycarbosilane synthesized by using ADMET methodology was a poly[carbo(dimethyl)silane].14c Linear poly(carbosilanes) are an important class of silicon-containing polymers due to their thermal, electronic, and optical properties.41 They are also ceramic precursors to silicon carbide after pyrolysis. ADMET opens up a new route to synthesize poly(carbosilanes), one that avoids many of the limitations found in earlier synthetic methods.41... 

The following is a comprehensive smwey of the chemistry of macrocycles comprised entirely of phenyl and acetylenic moieties. Although over fom" decades old, this area of research has come into its own just in the last few years. Widespread interest in the field has been spurred by recent discoveries utilizing these compoimds as ligands for organometallic chemistry, hosts for binding guest molecules, models of synthetic carbon allotropes, and precursors to fullerenes and other carbon-rich materials. This review will discuss the preparation of a tremendous variety of novel structm-es and detail the development of versatile synthetic methods for macro cycle construction. 

Figure 13 shows the irreversible conversion of a nonconjugated poly (p-phenylene pentadienylene) to a lithiun-doped conjugated derivative which has a semiconducting level of conductivity (0.1 to 1.0 S/cm) (29). Obviously, the neutral conjugated derivative of poly (p-phenylene pentadienylene) can then be reversibly generated from the n-type doped material by electrochemical undoping or by p-type compensation. A very similar synthetic method for the conversion of poly(acetylene-co-1,3-butadiene) to polyacetylene has been reported (30), Figure 14. This synthesis of polyacetylene from a nonconjugated precursor polymer containing isolated CH2 units in an otherwise conjugated chain is to be contrasted with the early approach of Marvel et al (6) in which an all-sp3 carbon chain was employed.

West (p. 6), Miller (p. 43), Zeigler (10), and Sawan (p. 112) outline the synthesis of a wide variety of soluble, processable polydiorganosilanes, a class of polymers which not long ago was thought to be intractable. Matyjaszewski (p. 78) has found significant improvements in the synthetic method for polydiorganosilane synthesis as well as new synthetic routes to unusual substituted polydiorganosilanes. Seyferth (p. 21, 143) reports synthetic routes to a number of new polycarbosilanes and polysilazanes which may be used as precursors to ceramic materials. 

Obviously, the advantages of this new synthetic method are i) valence isomerization can be performed under very mild conditions and ii) due to the fairly strong acidity of the bridgehead hydrogens of a bicyclobutane moiety, some substituents can be introduced regioselectively. Nevertheless, one serious disadvantage of this synthesis is the limitation of its applicability Thus, the formation of the precursor bicyclobutane derivatives is limited only to 46 and 56, and many attempts to prepare bicyclobutane precursors from other thiapyran derivatives have been unsuccessful so far. 

Although the merits of the synthetic method described in the preceding section are apparent, the limited applicability of this method prompted the search for alternative synthetic routes. During our work in this field we have found that a well known ring expansion via a carbene intermediate 45) does indeed proceed remarkably well with a variety of precursors. 

As described in this chapter, the sonochemical reduction technique appears to be a promising method for the preparation of various types of metal nanoparticles in an aqueous solution. By choosing more efficient organic additives, easily-reducible metal precursors, supports and templates with an appropriate role, more advanced functional nanoparticles could be synthesized successfully using the sonochemical reduction technique. In future, it is also possible to develop effective synthetic methods by combining the sonochemical method with other chemical methods. 

The decomposition of metal precursors in its zerovalent state constitutes a supplementary synthetic method to produce stable and well-dispersed NPs in ILs. As an... 

Macrocycles containing isoxazoline or isoxazole ring systems, potential receptors in host—guest chemistry, have been prepared by multiple (double, triple or quadruple) 1,3-dipolar cycloadditions of nitrile oxides, (prepared in situ from hydroxamoyl chlorides) to bifunctional calixarenes, ethylene glycols, or silanes containing unsaturated ester or alkene moieties (453). This one-pot synthetic method has been readily extended to the preparation of different types of macrocycles such as cyclophanes, bis-calix[4]arenes and sila-macrocycles. The ring size of macrocycles can be controlled by appropriate choices of the nitrile oxide precursors and the bifunctional dipolarophiles. Multiple cycloadditive macrocy-clization is a potentially useful method for the synthesis of macrocycles. 

This chapter has discussed the transition metal-catalyzed synthesis of allenes. Because allenes have attracted considerable attention as useful synthons for synthetic organic chemistry, effective synthetic methods for their preparation are desirable. Some recent reports have demonstrated the potential usefulness of optically active axially chiral allenes as chiral synthons however, methods for supplying the enantiomerically enriched allenes are still limited. Apparently, transition metal-catalyzed reactions can provide solutions to these problems. From the economics point of view, the enantioselective synthesis of axially chiral allenes from achiral precursors using catalytic amounts of chiral transition metal catalysts is especially attractive. Considering these facts, further novel metal-catalyzed reactions for the preparation of allenes will certainly be developed in the future. 

The olefm ring-closing metathesis (RCM) has been developed into an important synthetic method which is frequently employed in many synthetic endeavors. In many applications the popular Grubbs compound 204 or advanced complexes such as 205 and 206 were used as catalysts [117]. Rutjes and co-workers [118] and Okuro and Alper [119] elegantly used oxygen-substituted allenes to prepare precursors for the... 

The "principle of microscopic reversibility", which indicates that the forward and the reverse reactions must proceed through the same pathway, assures us that we can use the same reaction mechanism for generating the intermediate precursors of the "synthesis tree", that we use for the synthesis in the laboratory. In other words, according to the "principle of microscopic reversibility", [26] two reciprocal reactions from the point of view of stoichiometry are also such from the point of view of their mechanism, provided that the reaction conditions are the same or at least very similar. A corollary is that the knowledge of synthetic methods and reaction mechanisms itself -according to the electronic theory of valence and the theory of frontier molecular orbitals- must be applied in order to generate the intermediate precursors of the "synthesis tree" and which will determine the correctness of a synthesis design and, ultimately, the success of it. 

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