Silicon, condensation with formaldehyde

Maier and co-workers condensed formaldehyde and elemental silicon at 12 K in an argon matrix and photolyzed the mixture to form silaketene H2SiCO, which is similar in structure to the silylene-CO adduct mentioned above. The reactants first form siloxiranylidene 49 (which equilibrates with an unknown species postulated as the planar/linear silaketene 50 when exposed to 313-nm-wavelength light) and then forms complex 51 when photolyzed at 366 nm (Scheme 15). This species could also be formed by photolyzing diazidosilane 52 in the presence of CO, and complex 51 equilibrates with SiCO (53) and H2. The CO infrared shift for this bent structure was calculated at 2129 cm , which is shifted —80cm from the calculated value of free CO, at 2210 cm. The experimentally observed value was reported at 2038-2047 cm at 12 K. 

A number of routes are available for the synthesis of 2,2 -bipyridines where one of the pyridine rings is built up from simpler entities. For example, condensation of 2-(aminomethyl)pyridine (31) with acetaldehyde or acetylene over a silicon-alumina catalyst at 450°C gives 2,2 -bipyridine, ° whereas 2-cyanopyridine reacts with acetylene at 120°C in the presence of a cobalt catalyst to afford 2,2 -bipyridine in 95% yield.2-Acetylpyridine with acrolein and ammonia gives 2,2 -bipyridine in the presence of dehydrating and dehydrogenating catalysts, and related condensations afford substituted 2,2 -bipyridines. ° In a similar vein, condensation of benzaldehyde with 2 mol of 2-acetylpyridine in the presence of ammonia at 250°C affords 2,6-di(2-pyridyl)-4-phenylpyridine, ° and related syntheses of substituted 2,2 6, 2"-terpyridines have been described. Likewise, formaldehyde with two moles of ethyl picolinoylacetate and ammonia, followed by oxidation of the product and hydrolysis and decarboxylation, affords a good... 

Condensation polymers are classified as polyesters, polyamides, polyurethanes, and ether polymers, based on the internal functional group being ester (-COO-), amide (-CONH-), urethane (-OCONH-), or ether (-0-). Another group of condensation polymers derived by condensation reactions with formaldehyde is described under formaldehyde resins. Polymers with special properties have been classified into three groups heat-resistant polymers, silicones and other inorganic polymer, and functional polymers. Discussions in all cases are centered on important properties and main applications of polymers. 

The use of silicon-containing phenolic polymers with NDS compounds present as the photoactive polarity switch has been investigated. Formaldehyde condensation polymers with m-trimethyl-silylphenol (19) have been prepared. It is necessary to incorporate phenol as a comonomer in order to decrease the hydrophobicity of these resins so that they are soluble in aqueous base. The maximum silicon content obtainable is around 9% due to the acidolysis of the aromatic carbon-silicon bond during the acid-catalyzed polymerization process. Nevertheless, high resolution images with good oxygen etch resistance are obtained when these resins are formulated into resists with NDS derivatives present. 

This problem has been circumvented by utilizing the ipso-directing capability of a silicon substituent at the 2 position of the D ring to facilitate ring closure at this position. Benzylisoquinoline 26 condensed with formaldehyde to give predominantly product 28 when R = H. However, when R = SiMea, 27 was the only product observed and was isolated in excellent yield.Several members of the protoberberine family of natural products have been synthesized using this strategy. 

In some of these Nr reactions, such as in the case of self-condensations of sila-nols in silicone formation and of methylols in formaldehyde polymerizations, an end group may react with itself The number of such reactions in this subset will be defined as Nrj. 

Since alkyl-silicon bonds are known to be much more resistant to acidolysis than aromatic-silicon bonds, p-trimethylsilylmethylphenol has been condensed with formaldehyde (20), and terpolymers with m-cresol give good etch resistance and good images. Resorcinol-based novolac resins that contain silicon connected via an alkyl ether linkage (21) are also stable to the acidic polymerization conditions. These polymers are also reported to yield submicron images and to function in a bilayer mode. 

The effects of the composition and the methods of preparing V-Si-P ternary oxides on their catalytic performance in the vapor-phase aldol condensation of propionic acid with formaldehyde to form methacrylic acid were studied. The presence of both vanadyl pyrophosphate and large surface area was found to be required to achieve a good catalytic performance. Phosphorus serves to form and stabilize vanadyl pyrophosphate which is believed to be active sites and silicon serves to produce a large surface area and to modify the vanadyl pyo-phosphate. The presence of lactic acid is indispensable to produce a large surface area when the Si/V atomic ratio is in the range of 1 to 4. 

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