Phosphoric acids synthesis with

Phosphitylation with Azolides of Phosphorous Acid Synthesis of Oligonucleotides... 

Similarly, reactive oxide mixtures are also used to synthesize aluminophosphate molecular sieves, usually starting from phosphoric acid along with the addition of alumina and silica sources analogous to those used in zeolite synthesis with a notable exception alkylammonium salts and amines were ultilized in structure-direchng and space filling to the exclusion of alkali hydroxide solutions and alkali metal salts. 

Control of the optical purity of 5 was deemed to be crucial at this point of the synthesis. Crystallization of 1 as its desired phosphoric acid salt with ee below the final desired specification did not upgrade its optical purity and we intended to process 5 to 1 in a through process with only a final isolation. 

In this chapter, mainly the ROP of cyclic P-containing monomers is discussed. The synthesis of P-containing polymers by the polyaddition is discussed only for the reaction of phosphoric acid derivatives with diepoxides. 

Synthesis. Hydroxyhydroquiaone is not produced on a large scale, but many uses for it are being developed. The most convenient preparation of hydroxyhydroquiaone is the reaction of -benzoquiaone with acetic anhydride ia the preseace of sulfuric acid or phosphoric acid. The resultant triacetate (29) can be hydrolyzed to hydroxyhydroquiaone (86). 

A Methylamino)phenol. This derivative (15) is easily soluble ia ethyl acetate, ethanol, diethyl ether, and benzene. It is also soluble ia hot water, but only spatingly soluble ia cold water. Industrial synthesis is by heating 3-(A/-methylamino)benzenesulfonic acid with sodium hydroxide at 200—220°C (179) or by the reaction of resorciaol with methylamiae ia the presence of aqueous phosphoric acid at 200°C (180). 

Acid-Gatalyzed Synthesis. The acid-catalysed reaction of alkenes with hydrogen sulfide to prepare thiols can be accompHshed using a strong acid (sulfuric or phosphoric acid) catalyst. Thiols can also be prepared continuously over a variety of soHd acid catalysts, such as seoHtes, sulfonic acid-containing resin catalysts, or aluminas (22). The continuous process is utilised commercially to manufacture the more important thiols (23,24). The acid-catalysed reaction is commonly classed as a Markownikoff addition. Examples of two important industrial processes are 2-methyl-2-propanethiol and 2-propanethiol, given in equations 1 and 2, respectively. 

The Grewe synthesis of /V-methylmorphinan [3882-38-0] (40), which paved the way for the preparation of dextromethorphan and numerous analogues, follows standard reactions to 2-meth5l-l-benzyl-l,2,3,4,5,6,7,8-octahydroisoquinoline. Cyclization of this compound with phosphoric acid gave a mixture of isomers from which /V-methylmorphinan was separated. 

On treatment of N-methylpapaverine, formed by the lithium aluminum hydride reduction of papaverine methiodide with phosphoric acid, N-methylpavine is formed which is identical with the racemic alkaloid argemonine. This reaction was used for the synthesis of the alkaloid (-h)-coreximine (268) (174) and similar compounds containing the proto-berberine grouping in the molecule (269,270). 

Tlie condensation of nitromalonic aldehyde (26) with 2,6-diaminopyridine (27) in the presence of phosphoric acid, affording 2-amino-6-nitro-l,8-naphthyridine (28,37%) (77TL2087), is another example of a successful application of a nitro aliphatic compound in the synthesis of nitronaphthy-ridines. 

The Arbuzov reaction,also called the Michaelis-Arbuzov reaction, allows for the synthesis of pentavalent alkyl phosphoric acid esters 4 from trivalent phosphoric acid esters 1 (Z,Z = R,OR) by treatment with alkyl halides 2. 

Phosphine(s), chirality of, 314 Phosphite, DNA synthesis and, 1115 oxidation of, 1116 Phospholipid, 1066-1067 classification of, 1066 Phosphopantetheine, coenzyme A from. 817 structure of, 1127 Phosphoramidite, DNA synthesis and, 1115 Phosphoranc, 720 Phosphoric acid, pKa of, 51 Phosphoric acid anhydride, 1127 Phosphorus, hybridization of, 20 Phosphorus oxychloride, alcohol dehydration with. 620-622 Phosphorus tribromide, reaction with alcohols. 344. 618 Photochemical reaction, 1181 Photolithography, 505-506 resists for, 505-506 Photon, 419 energy- of. 420 Photosynthesis, 973-974 Phthalic acid, structure of, 753 Phthalimide, Gabriel amine synthesis and, 929... 

The synthesis of key intermediate 12, in optically active form, commences with the resolution of racemic trans-2,3-epoxybutyric acid (27), a substance readily obtained by epoxidation of crotonic acid (26) (see Scheme 5). Treatment of racemic 27 with enantio-merically pure (S)-(-)-1 -a-napthylethylamine affords a 1 1 mixture of diastereomeric ammonium salts which can be resolved by recrystallization from absolute ethanol. Acidification of the resolved diastereomeric ammonium salts with methanesulfonic acid and extraction furnishes both epoxy acid enantiomers in eantiomerically pure form. Because the optical rotation and absolute configuration of one of the antipodes was known, the identity of enantiomerically pure epoxy acid, (+)-27, with the absolute configuration required for a synthesis of erythronolide B, could be confirmed. Sequential treatment of (+)-27 with ethyl chloroformate, excess sodium boro-hydride, and 2-methoxypropene with a trace of phosphorous oxychloride affords protected intermediate 28 in an overall yield of 76%. The action of ethyl chloroformate on carboxylic acid (+)-27 affords a mixed carbonic anhydride which is subsequently reduced by sodium borohydride to a primary alcohol. Protection of the primary hydroxyl group in the form of a mixed ketal is achieved easily with 2-methoxypropene and a catalytic amount of phosphorous oxychloride. 

The acidic catalysts used for these reactions include formic acid, HX (X = F, Cl, Br), oxalic acid, phosphoric acid, sulfuric acid, sulfamic acid, and p-toluenesulfonic acid.4 Oxalic acid is preferred since resins with low color can be obtained. Oxalic acid also decomposes at high temperatures (>180°C) to C02, CO, and water, which facilitates the removal of this catalyst thermally. Typically, 1-6 wt % catalyst is used. Hydrochloric acid results in corrosive materials and reportedly releases carcinogenic chloromethyl ether by-products during resin synthesis.2... 

In 1950 the Fischer-Tropsch synthesis was banned in Germany by the allied forces. Sinarol, a high paraffinic kerosene fraction sold by Shell, was used as a substitute. This ban coincided with the rapid development of the European petrochemical industry, and in due time Fischer-Tropsch synthesis applied to the production of paraffins became uneconomic anyway. After the war there was a steady worldwide increase in the demand for surfactants. In order to continually meet the demand for synthetic detergents, the industry was compelled to find a substitute for /z-paraffin. This was achieved by the oligomerization of the propene part of raffinate gases with phosphoric acid catalyst at 200°C and about 20 bars pressure to produce tetrapropene. Tetrapropene was inexpensive, comprising a defined C cut and an olefinic double bond. Instead of the Lewis acid, aluminum chloride, hydrofluoric acid could now be used as a considerably milder, more economical, and easier-to-handle alkylation catalyst [4],... 

There are some means for synthesis of defined primary or secondary esters. Monoester salts of phosphoric acid, for instance, are prepared by addition of alcohol or ethoxylated alcohol, alkali fluoride, and pyrophosphoryl chloride (C12P0)20 in a molar ratio of 0.9-1.5 0.05-1 1.0 at -50 to +10°C and hydrolysis of the Cl-containing intermediates with base. Thus, 32.3 g (C12P0)20 was treated at -50°C with 23.9 g lauryl alcohol in the presence of 0.7 g KF and the mixture was slowly warmed to room temperature and hydrolyzed with H20 and 40% NaOH to give 83% sodium monolauryl phosphate. The monoester salts showed comparable or better washing and foaming efficiency than a commercial product [12]. 

There are several schemes for the synthesis of cellulose formates (slow) reaction of the polymer with formic acid faster reaction in the presence of a mineral acid catalyst, e.g., sulfuric or phosphoric acid. The latter route is usually associated with extensive degradation of the polymer chain. Reaction of SOCI2 with DMF produces the Vilsmeier-Haack adduct (HC(Cl) = N (CH3)2C1 ) [145]. In the presence of base, cellulose reacts with this adduct to form the unstable intermediate (Cell - O - CH = N" (CH3)2C1 ) from which cellulose formate is obtained by hydrolysis. The DS ranges from 1.2 to 2.5 and the order of reactivity is 5 > C2 > C3 [140-143,146]. 

C21-0082. Calcium dihydrogen phosphate is a common phosphoras fertilizer that is made by treating fluoroapatite with phosphoric acid. Hydrogen fluoride is a by-product of the synthesis. Write a balanced equation for the production of this fertilizer and calculate the mass percent of phosphorus in the fertilizer. 

When AMP is heated under reflux in DMF, the 2, 3 -cyclic phosphate is formed, and cyclic phosphates can also be obtained from nucleosides and ortho-, pyro-, or poly-phosphoric acids under the same conditions. Promotion of phosphorylation by DMF is well known and the reaction with AMP is probably intermolecular as no 3, 5 -cyclic AMP can be detected. Minor products in the latter reaction are the 2, 3 -cyclic 5 -diphosphate and the 2 (30,5 -diphosphate. The synthesis of adenosine 2 (3 )-phosphate 5 -pyrophosphate has been achieved by the phosphoromorpholidate method used in a synthesis of Co A. ... 

Cochineal pigments are extracted from dried bodies of female insects with water or with ethanol the result is a red solution that is concentrated in order to obtain the 2 to 5% carminic acid concentration customary for commercial cochineal. For carmine lakes, the minimum content of carminic acid is 50%. An industrial procedure applied in Spain uses ammonium hydroxide as the extracting agent and phosphoric acid as the acidifying agent. For analytical purposes the extraction is carried out with 2 N HCl at 100°C. The chemical synthesis of carminic acid has also been reported and is the subject of European and United States patents. ... 

Smith, M., Moffatt, J.G., Khorana, H.G. (1958) Carbodumides. VIII. Observations on the Reactions of Carbodiimides with Acids and Some New Applications in the Synthesis of Phosphoric Acid Esters. Journal of the American Chemical Society, 80, 6204-6212. 

The presence of triethylenetetramine in the hydrothermal synthesis of open-framework zinc phosphates results in a number of frameworks with one- to three-dimensional structures. The structures include one-dimensional ladders, two-dimensional layer structures, and one structure where the tetramine is bound to the zinc center. The structural type was highly sensitive to the relative concentration of the amine and phosphoric acid.411 Piperazine and 2-methylpiperazine can be used as templating molecules in solvothermal syntheses of zinc phosphates. The crystallization processes of the zinc compounds were investigated by real time in situ measurements of synchrotron X-ray powder diffraction patterns.412... 

Benzyl esters of phosphoric acid have been employed also with success in organic synthesis. Usually palladium catalysts are used to remove the benzyl protecting group (Scheme 4.50). 

Thiotraamidophosphoric acids (35) are isoelectronic with phosphoric acids and were initially reported from the reaction of phosphorus pentasulfide with primary amines at high temperatures.62 Subsequently, an improved synthesis for 35 with increased yields and milder conditions has been reported involving the room temperature reaction of thiophosphoryl chloride and primary amines (Equation 50).63 The most convenient route to the analogous selenium derivatives SeP(NHPh)3 is from the oxidation of P(NHPh)3 with elemental selenium (Equation 51).63 Also isoelectronic with phosphoric acids are dithio wamido-phosphoric acids (36), which can be prepared from the reaction of phosphorus pentasulfide with an excess of primary amine at 30°C in toluene (Equation 52).62 The selenium derivatives of 36 can be prepared in a similar reaction from phosphorus (V) selenide, although due to their increased acidity... 

Synthesis of glycosyl phosphates by reaction of hemiacetals with activated phosphoric acid derivatives... 

Ordered mesoporous materials of compositions other than silica or silica-alumina are also accessible. Employing the micelle templating route, several oxidic mesostructures have been made. Unfortunately, the pores of many such materials collapse upon template removal by calcination. The oxides in the pore walls are often not very well condensed or suffer from reciystallization of the oxides. In some cases, even changes of the oxidation state of the metals may play a role. Stabilization of the pore walls in post-synthesis results in a material that is rather stable toward calcination. By post-synthetic treatment with phosphoric acid, stable alumina, titania, and zirconia mesophases were obtained (see [27] and references therein). The phosphoric acid results in further condensation of the pore walls and the materials can be calcined with preservation of the pore system. Not only mesoporous oxidic materials but also phosphates, sulfides, and selenides can be obtained by surfactant templating. These materials have pore systems similar to OMS materials. 

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