Reactivity phosphoric

In the reaction of the very reactive phosphoric triimidazolide (for preparation see Section 2.2), which is also called phosphoryltriimidazole in analogy to the carbonyldii-midazole CDI, with an excess of methanol, as products trimethyiphosphate, dimethyl-phosphate, and O-methylphosphoric imidazolide were detected after one hour, and after two days the imidazolium salt of dimethylphos-phate was obtained in high yield [13]... 

In this procedure a diacylglyceryl phosphate is first converted with CDI into a reactive phosphoric imidazolide, which is then treated with a labeled alcohol to give a labeled phosphoric acid diester 123... 

Concentrations of dissolved reactive phosphorous (DRP) (Fig. 4) in glacier streams, and the two small streams Calancasca and Versegeres, fell in the range of a few... 

Sulfines. Sulfines are generally prepared by oxidation of thiocarbonyl compounds with peracids. Two other methods have been reported recently. One is the reaction of SO2 with sulBciently reactive phosphorous ylides. One example is shown in equation (I). The second, more general method is based on the Peterson... 

Reactive flame retardants can be integrated in plastics by way of reactions. For instance, tetrabromobisphenol A (TBBA) and reactive phosphoric flameproofing agents with P-OH or PH groups can be integrated into epoxy resins. HET acid and tetrabromophthalic acid anhydride in combination with antimony trioxide are used... 

For polyester and blends with cotton, phosphorous-based FRs are often used. The use of finishes based on reactive phosphorous FRs can result in wash-resistant polyester/cotton fabrics. 

Flow-based arrangements have been extensively investigated and widely adopted for the determination of soluble reactive phosphorous (SRP) in environmental samples. Flow-based systems for SRP have been successfully used in shipboard determinations [69,73,76,94,95], in situ analysis of streams [107], in field monitoring and control of phosphorus removal in wastewater treatment plants [71,90,100,108,109] and also in other bioprocesses control and land-based laboratory applications. 

In peptide syntheses, where partial racemization of the chiral a-carbon centers is a serious problem, the application of 1-hydroxy-1 H-benzotriazole ( HBT") and DCC has been very successful in increasing yields and decreasing racemization (W. Kdnig, 1970 G.C. Windridge, 1971 H.R. Bosshard, 1973), l-(Acyloxy)-lif-benzotriazoles or l-acyl-17f-benzo-triazole 3-oxides are formed as reactive intermediates. If carboxylic or phosphoric esters are to be formed from the acids and alcohols using DCC, 4-(pyrrolidin-l -yl)pyridine ( PPY A. Hassner, 1978 K.M. Patel, 1979) and HBT are efficient catalysts even with tert-alkyl, choles-teryl, aryl, and other unreactive alcohols as well as with highly bulky or labile acids. 

See also phosphorous acid.) [PHOSPHORUS COMPOUNDS] (Vol 18) Phosphomc acid reactive dyes... 

Figure 2 illustrates the three-step MIBK process employed by Hibernia Scholven (83). This process is designed to permit the intermediate recovery of refined diacetone alcohol and mesityl oxide. In the first step acetone and dilute sodium hydroxide are fed continuously to a reactor at low temperature and with a reactor residence time of approximately one hour. The product is then stabilized with phosphoric acid and stripped of unreacted acetone to yield a cmde diacetone alcohol stream. More phosphoric acid is then added, and the diacetone alcohol dehydrated to mesityl oxide in a distillation column. Mesityl oxide is recovered overhead in this column and fed to a further distillation column where residual acetone is removed and recycled to yield a tails stream containing 98—99% mesityl oxide. The mesityl oxide is then hydrogenated to MIBK in a reactive distillation conducted at atmospheric pressure and 110°C. Simultaneous hydrogenation and rectification are achieved in a column fitted with a palladium catalyst bed, and yields of mesityl oxide to MIBK exceeding 96% are obtained. 

Suitable catalysts include the hydroxides of sodium (119), potassium (76,120), calcium (121—125), and barium (126—130). Many of these catalysts are susceptible to alkali dissolution by both acetone and DAA and yield a cmde product that contains acetone, DAA, and traces of catalyst. To stabilize DAA the solution is first neutralized with phosphoric acid (131) or dibasic acid (132). Recycled acetone can then be stripped overhead under vacuum conditions, and DAA further purified by vacuum topping and tailing. Commercial catalysts generally have a life of about one year and can be reactivated by washing with hot water and acetone (133). It is reported (134) that the addition of 0.2—2 wt % methanol, ethanol, or 2-propanol to a calcium hydroxide catalyst helps prevent catalyst aging. Research has reported the use of more mechanically stable anion-exchange resins as catalysts (135—137). The addition of trace methanol to the acetone feed is beneficial for the reaction over anion-exchange resins (138). 

Ghloromethylation. The reactive intermediate, 1-chloromethylnaphthalene [86-52-2] has been produced by the reaction of naphthalene in glacial acetic acid and phosphoric acid with formaldehyde and hydrochloric acid. Heating of these ingredients at 80—85°C at 101.3 kPa (1 atm) with stirring for ca 6 h is required. The potential ha2ard of such chloromethylation reactions, which results from the possible production of small amounts of the powerhil carcinogen methyl chloromethyl ether [107-30-2J, has been reported (21). 

Thermal Process. In the manufacture of phosphoric acid from elemental phosphoms, white (yellow) phosphoms is burned in excess air, the resulting phosphoms pentoxide is hydrated, heats of combustion and hydration are removed, and the phosphoric acid mist collected. Within limits, the concentration of the product acid is controlled by the quantity of water added and the cooling capabiUties. Various process schemes deal with the problems of high combustion-zone temperatures, the reactivity of hot phosphoms pentoxide, the corrosive nature of hot phosphoric acid, and the difficulty of collecting fine phosphoric acid mist. The principal process types (Fig. 3) include the wetted-waH, water-cooled, or air-cooled combustion chamber, depending on the method used to protect the combustion chamber wall. 

The second major route to diarylamiaes is the condensation of an aromatic amine with a phenol. Aniline [62-53-3] phenol [108-95-2] and 3.5% phosphoric acid at 325°C gives a 50% yield of DPA (23). Apparently, this reaction iavolves the addition of aniline to the keto form of the phenol. Thus, naphthols and hydroquiaone are more reactive and give higher yields of product. This is the preferred route to A/-phenyi-2-naphthyiamiQe, 4-hydroxydiphenyiamiQe, and diphenyl- -phenylenediamine (24). 

Chemical Reactivity - Reactivity with Water Reacts with water to generate heat and form phosphoric acid. The reaction is not violent Reactivity with Common Materials Reacts with metals to liberate flammable hydrogen gas Stability During Transport Stable Neutralizing Agents for Acids and Caustics Flush with water, neutralize acid with lime or soda ash Polymerization Not pertinent Inhibitor of Polymerization Not pertinent. 

The corresponding phosphoryl and thiophos-phoryl pseudohalides are also known, i.e. P0(NC0)3, PS(NC0)3, etc. Preparations are by standard procedures such as those on the diagram for PCI3 (p. 497). As indicated there, P(CN)3 has also been made it is a highly reactive white crystalline solid mp 203° which reacts violently with water to give mainly phosphorous acid and HCN. 

Substituents in the 6-position (cf. 267) show appreciable reactivity. 6-Bromo-as-triazine-3,5(2j, 4j )-dione (316) undergoes 6-substitution with secondary amines or hydrazine, with mercaptide anions or thiourea (78°, 16 hr), with molten ammonium acetate (170°, 24 hr, 53% yield), and with chloride ion during phosphorous oxychloride treatment to form 3,5,6-trichloro-as-triazine. The latter was characterized as the chloro analog of 316 by treatment with methanol (20°, heat evolution) and hydrolysis (neutral or acid) to the dioxo compound. The mercapto substituent in 6-mercapto-as-triazine-3,5(2iI,4if)-dione is displaced by secondary... 

It is not possible to plate rhodium directly on to reactive metals of the type mentioned above, in view of the acid nature of the electrolyte, but copper and its alloys, e.g. nickel-silver, brass, phosphor-bronze, beryllium-copper, which are of special importance in the electrical contact field, may be plated directly. Even in this case, however, an undercoat is generally desirable. 

Like all anhydrides (Section 21.5), the mixed carboxylic-phosphoric anhydride is a reactive substrate in nucleophilic acyl (or phosphoryl) substitution reactions. Reaction of 1,3-bisphosphoglycerate with ADR occurs in step 7 by substitution on phosphorus, resulting in transfer of a phosphate group to ADP and giving ATP plus 3-phosphoglycerate. The process is catalyzed by phospho-gjvcerate kinase and requires Mg2+ as cofactor. Together, steps 6 and 7 accomplish the oxidation of an aldehyde to a carboxylic acid. 

Intermediates 18 and 19 are comparable in complexity and complementary in reactivity. Treatment of a solution of phosphonium iodide 19 in DMSO at 25 °C with several equivalents of sodium hydride produces a deep red phosphorous ylide which couples smoothly with aldehyde 18 to give cis alkene 17 accompanied by 20 % of the undesired trans olefin (see Scheme 6a). This reaction is an example of the familiar Wittig reaction,17 a most powerful carbon-carbon bond forming process in organic synthesis. 

As sulfonic acid cannot be vaporized, its determination by the direct gas chromatography (GC) method is not possible. To enable determination by GC, the reactivity of the S03H group is used the esterification of the S03H group with diazomethane via acid chloride is one way to transfer the sulfonic acid to volatile compounds. By conversion of the sulfonic acid with phosphoric acid at 200-210°C, the S03H group is cleaved and the hydrocarbons are obtained [184-186]. 

Diesters of phosphorous acid are in general neutral because the phosphorous acid exists mostly in the phosphonate form with one hydrogen directly attached to the phosphorus. But with alkali metals the H can be changed against the alkali and reactive intermediates formed. Such alkali metal derivatives of dialkyl phosphites react with alkyl halides to give dialkyl alkanephosphonates, according to Eqs. (45) and (46). 

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