Borate reactions

Homologation oj is recommended as tf( acyclic ketones withoit usually slow reaction borate). 

Duliere (271) reported that human serum protdns treated with ninhydrin in slightly alkaline solution for 2 days at 37°C. no longer reacted with formaldehyde and vice versa. E erth (272), in a fairly complete study, found that optimal conditions were 37 C., pH 7.0-7.5, 1% ninhydrin, and two days or more for reaction. Borate buffers should be avoided. 

Alkyl borates. By heating boric acid with excess of the alcohol the water formed in the reaction is removed by fractional distillation as an azeo tropic mixture with the alcohoi, for example ... 

Treatment of the borates with iodine leads to boron- C2 migration of an alkyl group[9]. This reaction has not been widely applied synthetically but it might be more applicable for introduction of branched alkyl groups than direct alkylation of an indol-2-yllithium intermediate. 

Vinylation can also be done by Pd-catalysed cross-coupling in which one component is used as a halide or triflate and the other as a stannane (Stille reaction) or boronic acid (Suzuki reaction). Entry 9, Table 11.3, is an example of the use of a vinylstannane with a haloindole. lndole-3-boronic acids, which can be prepared by mcrcuration/boration, undergo coupling with vinyl triflates (Entry 10). 

Catalysts. Iodine and its compounds ate very active catalysts for many reactions (133). The principal use is in the production of synthetic mbber via Ziegler-Natta catalysts systems. Also, iodine and certain iodides, eg, titanium tetraiodide [7720-83-4], are employed for producing stereospecific polymers, such as polybutadiene mbber (134) about 75% of the iodine consumed in catalysts is assumed to be used for polybutadiene and polyisoprene polymeri2a tion (66) (see RUBBER CHEMICALS). Hydrogen iodide is used as a catalyst in the manufacture of acetic acid from methanol (66). A 99% yield as acetic acid has been reported. In the heat stabiH2ation of nylon suitable for tire cordage, iodine is used in a system involving copper acetate or borate, and potassium iodide (66) (see Tire cords). 

Lithium Borates. Lithium metaborate [13453-69-5], LLBO2 2H20, is prepared from reaction of lithium hydroxide and boric acid. It is used as the fluxing agent for the matrix for x-ray fluorescence analytical techniques and in specialty glasses and enamels. The anhydrous salt melts at 847°C. 

Hexafluoro-2,5-dihydrofuran [24849-02-3] is distilled into sulfur trioxide [7446-11-9] at 25°C. Addition of trimethyl borate [121-43-7] initiates a reaction which upon heating and distillation leads to a 53% yield of difluoromaleic anhydride. Dichloromaleic anhydride [1122-17-4] can be prepared with 92% selectivity by oxidation of hexachloro-1,3-butadiene with SO in the presence of iodine-containing molecules (65). Passing vaporized... 

The products resulting from such reactions should, therefore, have analogous names. If KBO2 is a borate, KBS2 is a thioborate and KBF is a fluoroborate. Similarly, the replacement of an oxygen atom by a sulfur atom or two fluorine atoms is understandable. However, the relationship of K2BN2 is less obvious, until one considers the dehydration and deammoniation schemes ... 

The cmde phthaUc anhydride is subjected to a thermal pretreatment or heat soak at atmospheric pressure to complete dehydration of traces of phthahc acid and to convert color bodies to higher boiling compounds that can be removed by distillation. The addition of chemicals during the heat soak promotes condensation reactions and shortens the time required for them. Use of potassium hydroxide and sodium nitrate, carbonate, bicarbonate, sulfate, or borate has been patented (30). Purification is by continuous vacuum distillation, as shown by two columns in Figure 1. The most troublesome impurity is phthahde (l(3)-isobenzofuranone), which is stmcturaHy similar to phthahc anhydride. Reactor and recovery conditions must be carefully chosen to minimize phthahde contamination (31). Phthahde [87-41-2] is also reduced by adding potassium hydroxide during the heat soak (30). 

Single-electron transfer from a borate anion particle to the excited polymethine cation generates a dye radical and an aLkylphenylbotanyl radical. The aLkylphenylbotanyl radical fragments to form an active alkyl radical. It is the alkyl radical particles that initiate the polymerization reactions (101). 

Properties of zinc salts of inorganic and organic salts are Hsted in Table 1 with other commercially important zinc chemicals. In the dithiocarbamates, 2-mercaptobenzothiazole, and formaldehyde sulfoxylate, zinc is covalendy bound to sulfur. In compounds such as the oxide, borate, and sihcate, the covalent bonds with oxygen are very stable. Zinc—carbon bonds occur in diorganozinc compounds, eg, diethjizinc [557-20-0]. Such compounds were much used in organic synthesis prior to the development of the more convenient Grignard route (see Grignard reactions). 

Boric oxide is an excellent Lewis acid. It coordinates even weak bases to form four-coordinate borate species. Reaction with sulfuric acid produces H[B(HSO 4] (18). At high (>1000° C) temperatures molten boric oxide dissolves most metal oxides and is thus very corrosive to metals in the presence of oxygen. 

A value of Ai/298 —199.2 8.4 kJ/mol (—47.61 2.0 kcal/mol) has been calculated for this reaction, which is of considerable economic importance to glass manufacturers because 2 3 during glass (qv) processing are gready increased by the presence of water. For this reason anhydrous borates or... 

Alcohols react with boric acid with elimination of water to form borate esters, B(OR)3. A wide variety of borate salts and complexes have been prepared by the reaction of boric acid and inorganic bases, amines, and heavy-metal cations or oxyanions (44,45). Fusion with metal oxides yields... 

Manufacture. The majority of boric acid is produced by the reaction of inorganic borates with sulfuric acid in an aqueous medium. Sodium borates are the principal raw material in the United States. European manufacturers have generally used partially refined calcium borates, mainly colemanite from Turkey. Turkey uses both colemanite and tincal to make boric acid. 

Production of borax from the reaction of colemanite and sodium carbonate is carried out in Spain, Italy, and Poland. Turkish production from colemanite has been discontinued in favor of direct production from tincal ore. Sodium borates are produced in Russia from datoHte and in Kazakhstan from szaibelyite. 

A number of reviews have appeared covering the various aspects of borate glasses. The stmcture, physical properties, thermochemistry, reactions, phase equihbria, and electrical properties of alkah borate melts and glasses have been presented (73). The apphcation of x-ray diffraction, nmr, Raman scattering, in spectroscopy, and esr to stmctural analysis is available (26). Phase-equihbrium diagrams for a large number of anhydrous borate systems are included in a compilation (145), and thermochemical data on the anhydrous alkah metal borates have been compiled (17). 

Borate salts or complexes of virtually every metal have been prepared. For most metals, a series of hydrated and anhydrous compounds maybe obtained by varying the starting materials and/or reaction conditions. Some have achieved commercial importance. 

From Boric Oxide and Alcohol. To avoid removing water, boric oxide, B2O3, can be used in place of boric acid. The water of reaction (eq. 4) is consumed by the oxide (eq. 5). Because boric acid reacts with borates at high temperatures, it is necessary to filter the reaction mixture prior to distillation of the product. Only 50% of the boron can be converted to ester by this method. In cases where this loss can be tolerated, the boric oxide method is convenient. This is particularly tme for methyl borate and ethyl borate preparation because formation of the undesirable azeotrope is avoided. 

Transesterification. Transesterification is another method that does not require the removal of water. If a borate of lower molecular weight is available, higher molecular weight esters may be prepared by reaction of the appropriate higher molecular weight alcohol. 

Steric factors are important ia transesterification reactions. With a given alcohol, primary alkyl borates react at a rate too fast to measure, secondary alkyl borates react at measurable rates, and tert-huty borate reacts very slowly. 

U.S. Borax Research Corp., Anaheim, California, markets several borate esters under the trademark BORESTER. These include triethanolamine borate (BORESTER 20), tricresyl borate (m- and p-isomers) (BORESTER 8), and the biborate (4) (BORESTER 7). Whereas the chemical name for (4) is given in Table 1, it is commonly referred to as trihexylene glycol biborate [26545-48-2] and is prepared by the reaction of two moles of boric acid and three moles of hexylene glycol. 

Processes to produce boric acid esters are based on the azeotropic removal of water from a mixture of the appropriate alcohol, phenol, or glycol, and boric acid. A suitable hydrocarbon azeotroping agent is used to help remove the water. The water is removed continuously by using a condenser that allows continuous return of the solvent to the reaction vessel. Eor some borate esters, such as the glycol borates, distillation can result in decomposition. 

Hydrocarbon Oxidation. The oxidation of hydrocarbons (qv) and hydrocarbon derivatives can be significantly altered by boron compounds. Several large-scale commercial processes, such as the oxidation of cyclohexane to a cyclohexanol—cyclohexanone mixture in nylon manufacture, are based on boron compounds (see Cylcohexanoland cyclohexanone Eibers, polyamide). A number of patents have been issued on the use of borate esters and boroxines in hydrocarbon oxidation reactions, but commercial processes apparently use boric acid as the preferred boron source. The Hterature in this field has been covered through 1967 (47). Since that time the Hterature consists of foreign patents, but no significant appHcations have been reported for borate esters. 

The fluoroalkyl hypochlorites readily react with GO and SO2 to form the corresponding chloroformates and chlorosulfates in near quantitative yields (270). They add to olefins giving a-chloroethers (271). Borate esters are obtained by reaction of perfluoroalkyl hypochlorites with BGl (272). 

Pyrazoles, and some indazoles, substituted on the nitrogen by B, Al, Ga, In, Si, Ge, Sn, P and Hg are known. Poly(pyrazol-1 -yl)borates have been studied by Trofimenko (72CRV497) who found that they were excellent ligands (Section 4.04.2.1.3(vi)). The parent ligands (282), (283) and (284) are available by the reaction of an alkali metal borohydride with pyrazole, the extent of substitution depending on the reaction temperature (Scheme 22). 

Borate esters are hydrolyzed with aqueous acid or base. More sterically hindered borates such as pinanediol derivatives are quite stable to hydrolysis. Borates are stable to anhydrous acid and base, HBr/BzOOBz, NaH, and Wittig reactions. ... 

Control of the nuclear chain reaction in a reactor is maintained by the insertion of rods containing neutron absorbing materials such as boron, boron carbide, or borated steel. In state-of-the-art high temperature reactor designs, such as the Gas... 

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