Phosphoric acid ester amides, reaction with

Phosphoramidous fluorides, 13 383-389 Phosphoranes, 16 47 cage compounds, 30 246 as propellanes, 33 268 Phosphorescence, 19 68 Phosphoric acid ester amides, reaction with hexafluoroacetone, 30 237 Phosphoric acids, condensed, properties of, 5 220... 

Surfactants are prepared which contain carboxylic acid ester or amide chains and terminal acid groups selected from phosphoric acid, carboxymethyl, sulfuric acid, sulfonic acid, and phosphonic acid. These surfactants can be obtained by reaction of phosphoric acid or phosphorus pentoxide with polyhydroxystearic acid or polycaprolactone at 180-190°C under an inert gas. They are useful as polymerization catalysts and as dispersing agents for fuel, diesel, and paraffin oils [69]. 

Nitrogen- or Fluorine-Containing Phosphonates In N-containing phosphoric acid esters an >NH or >NR group is used instead of the bivalent >0. A typical reaction is the transformation of POCl3 with primary or secondary amines to the corresponding amides see Eq. (73) ... 

The lubrication system is extremely complex. The mechanism of lubrication is partly dictated by the nature of interactions between the lubricant and the solid surface. Additives blended into lubricating oil formulations either adsorb onto the sliding surfaces, eg., fatty alcohols, fatty amines, amides, phosphoric acid esters (friction modifiers), or react with the surface, eg., ZDDP, MoDTC, MoDDP organic phosphates (extreme pressure). Some interactions affecting the surfaces of metals include adsorption, chemisorption, and tribochemical reactions-these form new compounds on the surface and lubrication by reaction products (Bhushan and Gupta, 1991 Briscoe et al., 1973 Briscoe and Evens, 1982 Heinicke, 1984 Hsu and Klaus, 1978 and 1979 Klaus and Tewksbury, 1987 Lansdown, 1990 Liston, 1993 McFadden et al., 1998 Studt, 1989). 

For example, EtCl reacts with the alloy to give tetraethyllead in 85 % yield [9]. This method is such that only one quarter of the lead is converted to lead alkyl and the remainder has to be recycled. Unfortunately, sodium-rich alloys such as Na4Pb do not react satisfactorily. Ketones, aldehydes, acetals, acid anhydrides, esters, amides, phosphoric acid esters, organosilicons, organoaluminum compounds, etc. as reaction accelerators of the alloy process have been reported [9]. For example, the reaction of EtCl at 100-120 °C in the presence of 0.1 % acetone gives tetraethyllead in 98% yield [10]. 

Acryhc esters dimerize to give the 2-methylene glutaric acid esters catalyzed by tertiary organic phosphines (37) or organic phosphorous triamides, phosphonous diamides, or phosphinous amides (38). Yields of 75—80% dimer, together with 15—20% trimer, are obtained. Reaction conditions can be varied to obtain high yields of trimer, tetramer, and other polymers. 

The complex thioamide lolrestat (8) is an inhibitor of aldose reductase. This enzyme catalyzes the reduction of glucose to sorbitol. The enzyme is not very active, but in diabetic individuals where blood glucose levels can. spike to quite high levels in tissues where insulin is not required for glucose uptake (nerve, kidney, retina and lens) sorbitol is formed by the action of aldose reductase and contributes to diabetic complications very prominent among which are eye problems (diabetic retinopathy). Tolrestat is intended for oral administration to prevent this. One of its syntheses proceeds by conversion of 6-methoxy-5-(trifluoroniethyl)naphthalene-l-carboxyl-ic acid (6) to its acid chloride followed by carboxamide formation (7) with methyl N-methyl sarcosinate. Reaction of amide 7 with phosphorous pentasulfide produces the methyl ester thioamide which, on treatment with KOH, hydrolyzes to tolrestat (8) 2[. 

The results of these studies and others reported previously demonstrate that the 1-oxypyridinyl group is an effective catalyst for the transacylation reactions of derivatives of carboxylic and phosphoric acids when incorporated in small molecules and polymers. Furthermore, this catalytic site exhibits high selectivity for acid chlorides in the presence of acid anhydrides, amides, and esters. Therefore, catalysts bearing this group as the catalytic site can be used successfully in synthetic applications that require such specificity. The results of this work suggest that functionalized polysiloxanes should be excellent candidates as catalysts for a wide variety of chemical reactions, because they combine the unique collection of chemical, physical, and dynamic-mechanical properties of siloxanes with the chemical properties of the functional group. Finally, functionalized siloxanes appear to mimic effectively enzyme-lipophilic substrate associations that contribute to the widely acknowledged selectivity and efficiency observed in enzymic catalysis. 

Abramov, V.S., Savintseva, R.N., and Ermakova, V.E., Reaction of epihalohydrins with phosphorus(III) compounds. Part 2. Reactions of epiiodohydrin with esters, esteramides, and amides of phosphorous acid, Zh. Obshch. Khim., 38, 2281, 1968 7. Gen. Chem. USSR (Engl. Transl.), 38, 2207, 1968. 

In these reactions, hydrolysis of diphenyl and triaryl phosphites to monoaryl phosphites and phenol was coupled by dehydration between carboxylic acids and amines or alcohols to the corresponding amides and esters. Therefore, the reaction can be generalized as a hydrolysis-dehydration reaction (Scheme 2). The concept of the hydrolysis-dehydration reaction using phosphites has been drown to be applicable also to reactions with other phosphorus compounds such as phosphinites, phos-phonites and phosphorates s Aryl esters of these phosphorus compounds are effective as condensing agents in the production of carboxylic amides and esters (from carboxylic acids and amines or alcohols, respectively) whereas alkyl esters are ineffective (Eqs. (1-3)) ... 

Related anchored l,l,3,3-tetraphenyl-2-oxa-l,3-diphospholanium bis-triflate (39) has been prepared by reaction of brominated poly(styrene-co-divinylbenzene) resin 38 with the phosphorous anion generated from l,2-bis(diphenylphosphino)ethane and sodium naphthalenide followed by further oxidation and reaction with triflic anhydride (Scheme 7.13) [55]. This supported reagent has also been employed, to a lesser extent than 37, for the formation of esters and amides by reaction of carboxylic acids with primary alcohols and amines, respectively. 

Stereochemical data exist for a large number of displacement reactions on neutral phosphoric acid and thiophosphoric acid esters and amides (64). Many of these occur with retention of configuration, especially when the displacement reactions occur on five-membered ring compounds, and this stereochemical course is explained by pseudorotation of a pentacoordinate intermediate. In contrast, only one stereochemical study has been performed on an anionic phosphate ester with the intention of detecting the participation of a phosphorane intermediate. 

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