Boron illustration

The choice of tin to serve as the internal standard for boron illustrates the application of the criteria for internal standards as listed earlier. For example, tin is not a constituent of plant tissue, its ionization potential is 7.30 eV and that of boron is 8.29 eV, the boiling points are 2260°C for tin and 2550°C for boron, and the two spectral lines used are only 2.2 A apart. 

Here we will illustrate the method using a single example. The aldol reaction between an enol boronate and an aldehyde can lead to four possible stereoisomers (Figure 11.32). Many of these reactions proceed with a high degree of diastereoselectivity (i.e. syn anti) and/or enantioselectivity (syn-l syn-Tl and anti-l anti-lT). Bernardi, Capelli, Gennari,... 

The controlled thermal decomposition of dry aromatic diazonium fluoborates to yield an aromatic fluoride, boron trifluoride and nitrogen is known as the Schiemann reaction. Most diazonium fluoborates have definite decomposition temperatures and the rates of decomposition, with few exceptions, are easily controlled. Another procedure for preparing the diazonium fluoborate is to diazotise in the presence of the fluoborate ion. Fluoboric acid may be the only acid present, thus acting as acid and source of fluoborate ion. The insoluble fluoborate separates as it is formed side reactions, such as phenol formation and coupling, are held at a minimum temperature control is not usually critical and the temperature may rise to about 20° without ill effect efficient stirring is, however, necessary since a continuously thickening precipitate is formed as the reaction proceeds. The modified procedure is illustrated by the preparation of -fluoroanisole ... 

The 4 point group is that to which a regular icosahedron, illustrated in Figure 4.13(a), belongs. It contains 20 equilateral triangles arranged in a three-dimensional sttucture. This is the conformation of the anion, in which there is a boron atom, with a hydrogen atom... 

Diamond. Diamond [7782 0-3] is the hardest substance known (see Carbon, diamond, natural). It has a Knoop hardness of 78—80 kN/m (8000—8200 kgf/m ). The next hardest substance is cubic boron nitride with a Knoop value of 46 kN/m, and its inventor, Wentorf, beheves that no manufactured material will ever exceed diamond s hardness (17). In 1987 the world production of natural industrial diamonds (4) was about 110 t (1 g = 5 carats). It should be noted that whereas the United States was the leading consumer of industrial diamonds in 1987 (140 t) only 260 kg of natural industrial diamonds were consumed this is the lowest figure in 48 years (4), illustrating the impact that synthetic diamonds have made on the natural diamond abrasive market. 

Cationic polymerization of coal-tar fractions has been commercially achieved through the use of strong protic acids, as well as various Lewis acids. Sulfuric acid was the first polymerization catalyst (11). More recent technology has focused on the Friedel-Crafts polymerization of coal fractions to yield resins with higher softening points and better color. Typical Lewis acid catalysts used in these processes are aluminum chloride, boron trifluoride, and various boron trifluoride complexes (12). Cmde feedstocks typically contain 25—75% reactive components and may be refined prior to polymerization (eg, acid or alkali treatment) to remove sulfur and other undesired components. Table 1 illustrates the typical components found in coal-tar fractions and their corresponding properties. 

The most important reaction with Lewis acids such as boron trifluoride etherate is polymerization (Scheme 30) (72MI50601). Other Lewis acids have been used SnCL, Bu 2A1C1, Bu sAl, Et2Zn, SO3, PFs, TiCU, AICI3, Pd(II) and Pt(II) salts. Trialkylaluminum, dialkylzinc and other alkyl metal initiators may partially hydrolyze to catalyze the polymerization by an anionic mechanism rather than the cationic one illustrated in Scheme 30. Cyclic dimers and trimers are often products of cationic polymerization reactions, and desulfurization of the monomer may occur. Polymerization of optically active thiiranes yields optically active polymers (75MI50600). 

This is illustrated in Eig. 2.30 [2.167]. The surface was that of a fractured compact of SiC to which horon and carhon had been added to aid the sintering process. The aim of the analysis was to establish the uniformity of distribution of the additives and the presence or absence of impurities. The Auger maps show not only very non-uniform distribution of boron (Eig. 2.30a) but also strong correlation of boron with sodium (Eig. 2.30c), and weaker correlation of boron with potassium (Eig. 2.30b). Point analyses for points A and B marked on the images reveal the presence of sulfur and cal-... 

Most of the compounds in this class have been prepared from preexisting crown ether units. By far, the most common approach is to use a benzo-substituted crown and an electrophilic condensation polymerization. A patent issued to Takekoshi, Scotia and Webb (General Electric) in 1974 which covered the formation of glyoxal and chloral type copolymers with dibenzo-18-crown-6. The latter were prepared by stirring the crown with an equivalent of chloral in chloroform solution. Boron trifluoride was catalyst in this reaction. The polymer which resulted was obtained in about 95% yield. The reaction is illustrated in Eq. (6.22). 

As an illustration of the results of the measurements just described, the mechanical properties for four unidirectionally reinforced composite materials, glass-epoxy, boron-epoxy, graphite-epoxy, and Kevlar 49 -... 

If you look carefully at Figure 6.15, you will note a few exceptions to the general trends referred to above and illustrated in Example 6.11. For example, the ionization energy of B (801 kj/mol) is less than that of Be (900 kj/mol). This happens because the electron removed from the boron atom comes from the 2p as opposed to the 2s sublevel for beryllium. Because 2p is higher in energy than 2s, it is not too surprising that less energy is required to remove an electron from that sublevel. 

The only preparative limitation to this method is the occasional coproduction of alkenyl-boronates that presumably arise via a-elimination pathways of the ate complex generated upon addition of the organometallic reagent to the a-haloalkylboronate4,29-30. This problem is illustrated in the synthesis of 5-(rm-butyldimethylsilyloxy)-2-pentenyl-substituted dioxaborolane30. 

An extremely attractive feature of the route outlined at the beginning of this section for the transformation of boronates 3 or 4 to a-substituted allylboron compounds 5 is that reagents with very high enantiomeric purity (> 90% ee) may be prepared when precursors such as 3 and 4, and therefore also ate complex 1, contain a suitable diol chiral auxiliary17. The following syntheses of (S)-68, lib9, and 1310 illustrate this feature. 

A demonstration of the feasibility of a reaction is illustrated in the following example regarding the formation of titanium diboride using either diborane or boron trichloride as a boron source, as shown in the following reactions ... 

Although superficially this reaction resembles 10-94 it is likely that the mechanism is quite different, involving migration of an R group from boron to carbon (see also 18-23-18-26). The mechanism is not known with certainty, it may be tentatively shown as (illustrated for an a-halo ketone) ... 

The materials for solid solutions of transition elements in j3-rh boron are prepared by arc melting the component elements or by solid-state diffusion of the metal into /3-rhombohedral (/3-rh) boron. Compositions as determined by erystal structure and electron microprobe analyses together with the unit cell dimensions are given in Table 1. The volume of the unit cell (V ) increases when the solid solution is formed. As illustrated in Fig. 1, V increases nearly linearly with metal content for the solid solution of Cu in /3-rh boron. In addition to the elements listed in Table 1, the expansion of the unit cell exceeds 7.0 X 10 pm for saturated solid solutions " of Ti, V, (2o, Ni, As, Se and Hf in /3-rh boron, whereas the increase is smaller for the remaining elements. The solubility of these elements does not exceed a few tenths at %. The microhardness of the solid solution increases with V . Boron is a brittle material, indicating the accommodation of transition-element atoms in the -rh boron structure is associated with an increase in the cohesion energy of the solid. 

The second synthetic route consists of the coupling of hexa(4-iodophenyl)ben-zene (34) with an alkylated oligophenylboronic acid to produce a hexa(oligo-phenyl)benzene by extending the aromatic chain [52]. This route is illustrated by the reaction of hexa(4-iodophenyl)benzene (34) with an alkylated terphenyl boronic acid with formation of the hexa(quaterphenyl)benzene derivative 33. Once again, the aliphatic substituents serve to guarantee sufficient solubility. 

Reaction conditions that involve other enolate derivatives as nucleophiles have been developed, including boron enolates and enolates with titanium, tin, or zirconium as the metal. These systems are discussed in detail in the sections that follow, and in Section 2.1.2.5, we discuss reactions that involve covalent enolate equivalents, particularly silyl enol ethers. Scheme 2.1 illustrates some of the procedures that have been developed. A variety of carbon nucleophiles are represented in Scheme 2.1, including lithium and boron enolates, as well as titanium and tin derivatives, but in... 

These examples and those in Scheme 2.6 illustrate the key variables that determine the stereochemical outcome of aldol addition reactions using chiral auxiliaries. The first element that has to be taken into account is the configuration of the ring system that is used to establish steric differentiation. Then the nature of the TS, whether it is acyclic, cyclic, or chelated must be considered. Generally for boron enolates, reaction proceeds through a cyclic but nonchelated TS. With boron enolates, excess Lewis acid can favor an acyclic TS by coordination with the carbonyl electrophile. Titanium enolates appear to be somewhat variable but can be shifted to chelated TSs by use of excess reagent and by auxiliaries such as oxazolidine-2-thiones that enhance the tendency to chelation. Ultimately, all of the factors play a role in determining which TS is favored. 

Several factors affect the reactivity of the boron and aluminum hydrides, including the metal cation present and the ligands, in addition to hydride, in the complex hydride. Some of these effects can be illustrated by considering the reactivity of ketones and aldehydes toward various hydride transfer reagents. Comparison of LiAlH4 and NaAlH4 has shown the former to be more reactive,63 which is attributed to the greater... 

Scheme 9.1 shows several examples of one-carbon homologations involving boron to carbon migration. Entry 1 illustrates the synthesis of a symmetrical tertiary alcohol. Entry 2 involves interception of the intermediate after the first migration by reduction. Acid then induces a second migration. This sequence affords secondary alcohols. 

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