Boric acid catalyst

Since previous papers (1, 2) describe details of the manufacturing process for secondary alcohols(SA) and their ethoxylates (SAE), only the outline of the process will be presented here. A mixture of secondary alcohols is obtained by liquid phase air-oxidation of normal paraffins in the presence of a boric acid catalyst(Figure 1). Although the existing commercial processes, as developed independently, comprise significantly different combinations of various unit processes, they are all based on this boric acid-modified oxidation of hydrocarbons(3). 

Pfizer has also been investigating catalytic direct amidation reactions. One of the most encouraging substrates is the synthesis of zamifenacin, which has been used for overactive bladder and irritable bowel syndrome. Only 2 mol% boric acid catalyst loading gave complete conversion of amide with Dean-Stark water removal in the direct amidation. Unfortunately, in 1990, zamifenacin was put on hold and replaced by darifenacin, so the synthesis of zemifenacin was never sealed up beyond laboratoiy scale. 

In the DSM proeess, ammoninm sulfate formation is redueed from about 5 kg for eaeh kilogram of eaprolactam to 1.8 kg. Boric acid catalysts can be used for the rearrangement of the oxime to the lactam at 330°C in fixed or fluidized beds, but have not been nsed eonnnercially. Strong acid exchange resins have... 

Boric acid itself was investigated as a possible catalyst for the formation of secondary and tertiary amines by Tang and co-workers in 2005. It was found that 4-phenylbutyric acid and benzylamine were able to be coupled together in the presence of 5 mol% boric acid in heptane at 100 °C. Less nucleophilic substrates were tolerated, however in these cases the catalyst loading was increased to 25 mol%. This reaction was also carried out on a large scale requiring only 1 mol% of the boric acid catalyst (Scheme 17.4). At lower temperatures, however, boric acids are less efficient. 

Boron trifluoride [7637-07-2] (trifluoroborane), BF, was first reported in 1809 by Gay-Lussac and Thenard (1) who prepared it by the reaction of boric acid and fluorspar at duU red heat. It is a colorless gas when dry, but fumes in the presence of moisture yielding a dense white smoke of irritating, pungent odor. It is widely used as an acid catalyst (2) for many types of organic reactions, especially for the production of polymer and petroleum (qv) products. The gas was first produced commercially in 1936 by the Harshaw Chemical Co. (see also Boron COMPOUNDS). 

The boric and sulfuric acids are recycled to a HBF solution by reaction with CaF2. As a strong acid, fluoroboric acid is frequently used as an acid catalyst, eg, in synthesizing mixed polyol esters (29). This process provides an inexpensive route to confectioner s hard-butter compositions which are substitutes for cocoa butter in chocolate candies (see Chocolate and cocoa). Epichlorohydrin is polymerized in the presence of HBF for eventual conversion to polyglycidyl ethers (30) (see Chlorohydrins). A more concentrated solution, 61—71% HBF, catalyzes the addition of CO and water to olefins under pressure to form neo acids (31) (see Carboxylic acids). 

Formaldehyde is readily reduced to methanol by hydrogen over many metal and metal oxide catalysts. It is oxidized to formic acid or carbon dioxide and water. The Cannizzaro reaction gives formic acid and methanol. Similarly, a vapor-phase Tischenko reaction is catalyzed by copper (34) and boric acid (38) to produce methyl formate ... 

Cyclohexane. The LPO of cyclohexane [110-82-7] suppUes much of the raw materials needed for nylon-6 and nylon-6,6 production. Cyclohexanol (A) and cyclohexanone (K) maybe produced selectively by using alow conversion process with multiple stages (228—232). The reasons for low conversion and multiple stages (an approach to plug-flow operation) are apparent from Eigure 2. Several catalysts have been reported. The selectivity to A as well as the overall process efficiency can be improved by using boric acid (2,232,233). K/A mixtures are usually oxidized by nitric acid in a second step to adipic acid (233) (see Cyclohexanol and cyclohexanone). 

Reactions. The most important commercial reaction of cyclohexane is its oxidation (ia Hquid phase) with air ia the presence of soluble cobalt catalyst or boric acid to produce cyclohexanol and cyclohexanone (see Hydrocarbon oxidation Cyclohexanoland cyclohexanone). Cyclohexanol is dehydrogenated with 2iac or copper catalysts to cyclohexanone which is used to manufacture caprolactam (qv). 

The tertiary metal phosphates are of the general formula MPO where M is B, Al, Ga, Fe, Mn, etc. The metal—oxygen bonds of these materials have considerable covalent character. The anhydrous salts are continuous three-dimensional networks analogous to the various polymorphic forms of siHca. Of limited commercial interest are the alurninum, boron, and iron phosphates. Boron phosphate [13308-51 -5] BPO, is produced by heating the reaction product of boric acid and phosphoric acid or by a dding H BO to H PO at room temperature, foUowed by crystallization from a solution containing >48% P205- Boron phosphate has limited use as a catalyst support, in ceramics, and in refractories. 

In this process, catalysts, such as boric acid, molybdenum oxide, zirconium, and titanium tetrachloride or ammonium molybdate, are used to accelerate the reaction. The synthesis is either carried out in a solvent (aUphatic hydrocarbon, trichlorobenzene, quinoline, pyridine, glycols, or alcohols) at approximately 200°C or without a solvent at 300°C (51,52). 

A continuous process has been described (14) which can produce either the amide or the nitrile by adjusting the reaction conditions. Boric acid has been used as a catalyst in the amidation of fatty acid (15). Other catalysts employed include alumina (16), titanium, and 2inc alkoxides (17). The difficulty of complete reaction during synthesis has been explained by the formation of RCOOH NH RCOO , a stable intermediate acid ammonium salt (18). 

Diphenylamine can also be produced by passing the vapors of aniline over a catalyst such as alumina, or alumina impregnated with ammonium fluoride (17). The reaction is carried out at 480°C and about 700 kPa (7 atm). Conversion per pass, expressed as parts diphenylamine per 100 parts of reactor effluent, is low (18—22%), and the unconverted aniline must be recycled. Other catalysts disclosed for the vapor-phase process are alumina modified with boron trifluoride (18), and alumina activated with boric acid or boric anhydride (19). 

Tetraalkyl titanates react with organic borates, B(OR )2, to give complexes of the general formula Ti(OR)4 B(OR )2, which are useful as catalysts and cross-linking agents (562). Mixtures of chelated organic titanates such as TYZOR TE and TYZOR LA with alkaU metal borates, such as borax, or boric acid can be used to produce shear-stable fracturing fluids (563). 

The uses of boric oxide relate to its behavior as a flux, an acid catalyst, or a chemical iatermediate. The fluxing action of B2O2 is important ia preparing many types of glass, gla2es, frits, ceramic coatings, and porcelain enamels (qv). 

Three commercial processes that use these various hot carbonate flow arrangements are the promoted Benfield process, the Catacarb process, and the Giammarco-Vetrocoke process (26—29). Each uses an additive described as a promoter, activator, or catalyst, which increases the rates of absorption and desorption, improves removal efficiency, and reduces the energy requirement. The processes also use corrosion inhibitors, which aHow use of carbon—steel equipment. The Benfield and Catacarb processes do not specify additives. Vetrocoke uses boric acid, glycine, or arsenic trioxide, which is the most effective. 

The oxidation of cyclohexane to a mixture of cyclohexanol and cyclohexanone, known as KA-od (ketone—alcohol, cyclohexanone—cyclohexanol cmde mixture), is used for most production (1). The earlier technology that used an oxidation catalyst such as cobalt naphthenate at 180—250°C at low conversions (2) has been improved. Cyclohexanol can be obtained through a boric acid-catalyzed cyclohexane oxidation at 140—180°C with up to 10% conversion (3). Unreacted cyclohexane is recycled and the product mixture is separated by vacuum distillation. The hydrogenation of phenol to a mixture of cyclohexanol and cyclohexanone is usually carried out at elevated temperatures and pressure ia either the Hquid (4) or ia the vapor phase (5) catalyzed by nickel. 

Alkylamines react with leucoquinizarin in a stepwise manner to give l-alh anaino-4-hydroxyanthraquinone, and 1,4-diaLkylamino derivatives after air oxidation. Aromatic amines react similarly in the presence of boric acid as a catalyst. The complex formed (129) causes the less nucleophilic aromatic amines to attack at the 1-, and 4-positions. 

A number of basic materials such as hydroxides, hydrides and amides of alkaline and alkaline earth metals and metal oxides such as zinc oxide and antimony oxide are useful catalysts for the reaction. Acid ester-exchange catalysts such as boric acid, p-toluene sulphonic acid and zinc chloride are less... 

By selection of conditions and catalyst, the intermediate hydroxyimine (11) can be directed to either (he hydroxy ketone (10) or amino alcohol (12), Over platinum oxide in methanol-acetic acid-water the amino alcohol forms, whereas over alkali-free Ra-Ni in methanol-water or over 10% Pd-on-C in methanol-water containing boric acid, the hydroxy ketones form in excellent yield. Nitrile oxide cycloadditions have been applied to five-membered ring syntheses (.50). 

In one approach cyclohexane is autoxidized to a mixture of cyclohexanol and cyclohexanone in the presence of a Co or Mn naphthenate catalyst. This mixture is subsequently oxidized to adipic acid using nitric acid as the oxidant in the presence of a Cu Vv catalyst. An alternative method using dioxygen in combination with Co or Mn in HOAc gives lower selectivities to adipic acid (70% vs 95%). Alternatively, autoxidation in the presence of stoichiometric amounts of boric acid produces cyclohexanol as the major product, which is subsequently oxidized to adipic acid using HNO3 in the presence of Cu Vv. The latter step produces substantial amounts of N2O as a waste product. 

An important route to 1,4-diaminoanthraquinones, represented by structure 78, is illustrated in Scheme 4.6. Quinizarin (75) is first reduced to leucoquinizarin, which has been shown to exist as the diketo structure 77. Condensation of compound 77 with two moles of an amine, followed by oxidation leads to the diaminoanthraquinone 78. Boric acid is a useful catalyst for this reaction, particularly when less basic amines are used. 

An acidic-cure catalyst is added to the urea-formaldehyde resin before it is used as an adhesive. Ammonium chloride and ammonium sulfate are the most widely used catalysts for resins in the forest products industry. A variety of other chemicals can be used as a catalyst, including formic acid, boric acid, phosphoric acid, oxalic acid, and acid salts of hexamethylenetetramine. 

Imino derivatives 61 were obtained directly from 3-formylchromone [36] 59 and creatinine [37] 60, with DM SO as solvent and boric acid as catalyst, and with micro-wave irradiation and classical heating (Tab. 8.4). The authors have also investigated the preparation of the 2-thioxo-5-imidazolidin-4-ones 63 from thiohydantoin 62 in... 

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