Aromatic phosphorus acid

Plasticizers include the esters of a few aliphatic and aromatic mono and dicarboxylic acids, aliphatic and aromatic phosphorus acid esters, ethers, alcohols, ketones, amines, amides, and non-polar and chlorinated hydrocarbons. These additives are used in various mixtures. For their separation and qualitative detection, thin-layer chromatography (TLC) is preferred. Usually Kieselgur plates, 0.25 mm thick, activated at 110°C for 30 min, in the saturated vapor are used. Methylene chloride and mixtures of diisopropyl ether/petether at temperatures between 40 to 60°C have been successfully used as the mobile phase. Refer to Table 1. 

A powerful and efficient method for the preparation of poly(ketone)s is the direct polycondensation of dicarboxylic acids with aromatic compounds or of aromatic carboxylic acids using phosphorus pentoxide/methanesulfonic acid (PPMA)16 or polyphosphoric acid (PPA)17 as the condensing agent and solvent. By applying both of these reagents to the synthesis of hexafluoroisopropylidene-unit-containing aromatic poly(ketone)s, various types of poly(ketone)s such as poly(ether ketone) (11), poly(ketone) (12), poly(sulfide ketone) (13), and poly-... 

Sulfonic acids are prone to reduction with iodine [7553-56-2] in the presence of triphenylphosphine [603-35-0] to produce the corresponding iodides. This type of reduction is also facile with alkyl sulfonates (16). Aromatic sulfonic acids may also be reduced electrochemicaUy to give the parent arene. However, sulfonic acids, when reduced with iodine and phosphorus [7723-14-0]y produce thiols (qv). Amination of sulfonates has also been reported, in which the carbon—sulfur bond is cleaved (17). Ortho-lithiation of sulfonic acid lithium salts has proven to be a useful technique for organic syntheses, but has litde commercial importance. Optically active sulfonates have been used in asymmetric syntheses to selectively O-alkylate alcohols and phenols, typically on a laboratory scale. Aromatic sulfonates are cleaved, ie, desulfonated, by uv radiation to give the parent aromatic compound and a coupling product of the aromatic compound, as shown, where Ar represents an aryl group (18). 

Phosphorus trichloride and phosphorus pentachloride are also suitable reagents for acid chloride formation, but their use is largely restricted to aromatic carboxylic acids. (Section 6.14.1, p. 1073). 

As a general rule, ylides with allylic or benzylic functionality do not proceed with a high degree of stereoselectivity. There have been recent examples of arachidonic acid derivatives in which the coupling of an allylic phosphonium salt with an unsaturated aldehyde resulted in (Z)-selective alkenation. As in the case of nonstabilized ylides, replacing aromatic phosphorus substituents with allylic (113 equation 25) or alkyl (115 equation 26) groups dramaticaUy increases the production of the (, -al-kene. ... 

We have used organo-phosphorus acids [25] as promoters of the reaction of aromatic amines with dimethylcarbonate (DMC) or diphenylcarbonate (DPC) in the presence of carbon dioxide to generate N-alkyl- or aryl-carbamates. We have applied this methodology to the carbamation of aniline, naphtylamine, toluen-diamine, 4,4 -diaminophenyl-methane, among others. 

Synthesis of Phosphoric Acids and Their Derivatives. - A series of monoalkyl and dialkyl phosphorus acid chiral esters have been synthesised for use as carriers for the transport of aromatic amino acids through supported liquid membranes. The compounds acted as effective carriers but enantio-separation was at best moderate. A range of phosphono- and phosphoro-fluoridates have been prepared by treatment of the corresponding thio- or seleno- phosphorus acids with aqueous silver fluoride at room temperature (Scheme 1). In some cases oxidation rather than fluorination occurred. Stereospecifically deuterium-labelled allylic isoprenoid diphosphates, e.g. (1), have been synthesised from the corresponding deuterium-labelled aldehyde by asymmetric reduction, phosphorylation and Sn2 displacement with pyrophosphate (Scheme 2). ... 

Acid Chlorides. Acid chlorides can be made from the corresponding fatty acids by treatment with phosphorus halides. When liquid carboxylic acids are reacted, the phosphorus halide, PCU or POCU, may be added gradually. If the acid does not react energetically, as in the case of the higher members of the acetic acid series or with aromatic carboxylic acids, phosphorus pentachloride is used. The reactions may be represented as follows ... 

Within the last two decades, a number of chemical structures have been proposed as metal deactivators for polyolefins. These include carboxylic acid amides of aromatic mono- and di-carboxylic acids and N-substituted derivatives such as N,N -diphenyloxamide, cyclic amides such as barbituric acid, hydrazones and bishydrazones of aromatic aldehydes such as benzaldehyde and salicylaldehyde or of o-hydroxy-arylketones, hydrazides of aliphatic and aromatic mono- and di-carboxylic acids as well as N-acylated derivatives thereof, bisacylated hydrazine derivatives, polyhydrazides, and phosphorus acid ester of a thiobisphenol. An index of trade names and suppliers of a few commercial metal deactivators is given in Appendix A4. 

Imidoyl chlorides of aromatic carboxylic acids ( ). An equimolar mixture of the N-monosubstituted amide and phosphorus pentachloride is heated for 15-180 min at 60-140 C. After completion of the reaction, which is indicated by the cessation of hydrogen chloride evolution, the phosphoryl chloride is removed under reduced pressure, and the remaining imidoyl chloride is distilled under vacuum. The reported yield ranges from 41-96%, but generally yields of 80-90% are obtained. 

Synonyms Cresyl phosphate Phosphoric acid, tris (methylphenyl) ester Phosphoric acid, tritolyl ester TCP Tricresyl phosphate, with > 3% ortho isomer Tris (methylphenyl) phosphate Tris (tolyloxy) phosphine oxide Tritolyl phosphate Classification Aromatic phosphorus compd. 

Classification Aromatic phosphorus compd. Empirical C12H10CIO3P Formula (C6Hs0)2P(0)CI Properties Liq. sol. in inert org. soivs. hydrolyzes with water m.w. 268.64 dens. 1.296 b.p. 145-148 C flash pt. 113 C ref. index 1.5500 Toxicology Harmful causes burns TSCA listed Precaution Corrosive hydrolyzes on contact with water to form HCI and diphenyl acid... 

In the preparation of the linear analogues, solvents such as nitrobenzene [478] and methylene chloride [479] were used. A new method capable of creating poly(ether ketone) and polyfthioether ketone) was recently disclosed by Ueda et al. [480-482]. Here, the dehydrating power of a mixture of phosphorus pentoxide and methanesulfonic acid (MSA) is the driving force for the direct polycondensation of aromatic dicarboxylic acids with aryl compounds contain-... 

By the action of phosphorus pentachlorido upon the aromatic acid, for example ... 

Aromatic thioamides can be prepared as described in the literature by different ways, either by S -> O exchange between the corresponding benzamides and phosphorus pentasulfide in pyridine solution in the presence of triethylamine (65, 646) as strong base, or by action of H2S on the appropriate nitrile with pyridine and triethylamine solvents using the method of Fairfull et al. (34, 374, 503). In this reaction, thioacetamide in acidic medium can also be used as a H2S generator with dimethylform-amide as the solvent (485). 

Because of the structural requirements of the bielectrophile, fully aromatized heterocycles are usually not readily available by this procedure. The dithiocarbamate (159) reacted with oxalyl chloride to give the substituted thiazolidine-4,5-dione (160) (see Chapter 4.19), and the same reagent reacted with iV-alkylbenzamidine (161) at 100-140 °C to give the 1 -alkyl-2-phenylimidazole-4,5-dione (162) (see Chapter 4.08). Iminochlorides of oxalic acid also react with iV,iV-disubstituted thioureas in this case the 2-dialkylaminothiazolidine-2,4-dione bis-imides are obtained. Thiobenzamide generally forms linear adducts, but 2-thiazolines will form under suitable conditions (70TL3781). Phenyliminooxalic acid dichloride, prepared from oxalic acid, phosphorus pentachloride and aniline in benzene, likewise yielded thiazolidine derivatives on reaction with thioureas (71KGS471). 

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