Aminomethyl phosphonate

Another GC/MS method that was validated as a food tolerance method involved the determination of glyphosate and (aminomethyl)phosphonic acid (AMPA) in crops. In this method, glyphosate and AMPA residues are extracted from crop commodities (corn grain) with water. The extracts are then partitioned with dichloromethane,... 

A major concern in H2O2 oxidation is the alcohol/olefin chemoselectivity (Rao, 1991). This biphasic oxidation was initially developed for olefin epoxidations but with an (aminomethyl)phosphonic acid additive for high selectivity (Rudolph et al., 1997). Now, the removal of this additive has been found to significantly increase the rate and selectivity of alcohol oxidation. 

A mixture of diethyl [(diphenylmethylene)aminomethyl]phosphonate (lmmol), Aliquat 336 (20mg, 0.05 mmol), the appropriate halide (1.5 mmol), and finely ground KOH (300 mg, 5 mmol) was stirred at rt, and the reaction progress was monitored by TLC (silica gel). The mixture was worked up by adding CH2C12 (10 mL) and slurrying with silica gel (50 mg). After filtration, the solvent was removed in vacuo, and the residue was purified by flash chromatography (silica gel). 

Flame retardants (qv) are incorporated into the formulations in amounts necessary to satisfy existing requirements. Reactive-type diols, such as IV,IV-bis(2-hydroxyethyl)aminomethyl phosphonate (Fyrol 6), are preferred, but nonreactive phosphates (Fyrol CEF, Fyrol PCF) are also used. Often, the necessary results are achieved using mineral fillers, such as alumina trihydrate or melamine. Melamine melts away from the flame and forms both a nonflammable gaseous environment and a molten barrier that helps to isolate the combustible polyurethane foam from the flame. Alumina trihydrate releases water of hydration to cool the flame, forming a noncombustible inorganic protective char at the flame front. Flame-resistant upholstery fabric or liners are also used (27). 

The M-diphenylmethylene derivative of diethyl (aminomethyl) phosphonate (172 R = H) can be alkylated (solvept systems not... 

In the case of tribenzyl and trimethyl amine, a-substitution products could be obtained using diethyl malonate or diethylphosphonate as nucleophiles, if 2,4,6-collidine was used as base in an acetonitrile electrolyte [20]. In this way, dialkyl aminomethyl phosphonates and malonates could be obtained in good yield. 

The mechanism of the cyclization step in the preparation of perhydro-1,4,2-oxazaphosphorin-5-ones (45) from halogenoacetyl halides and a-aminomethyl-phosphonate esters (see Organophosphorus Chemistry , Vol. 8, p. 112) has been investigated, using labelling of the two possible modes of cyclization, the correct one appears to involve the nucleophilicity of the phosphoryl group, as indicated in Scheme 12. ... 

The best known phosphorus polyol of significant commercial importance is diethyl-N,N-bis (2-hydroxyethyl) aminomethyl phosphonate, which is obtained by a Mannich reaction between diethylphosphite, formaldehyde and diethanolamine (reaction 18.11) [5, 34] ... 

In the soil glyphosate is broken down by microorganisms. The end-product of degradation is COj, with aminomethyl phosphonic acid formed as intermediate product (HjN—CHjPOfOH) ) (Torstenson and Aamisepp, 1977 Nomura and Hilton, 1977 Moshier, 1978). 

The alkylation of diethyl (aminomethyl)phosphonate Schiff bases e.g. (217 R =H or Ph, R =Ph), with (218 Y=C1, OAc, or 0C02Et) is catalyzed by Pd(0). The alkylation of the Schiff base (219) ( from diethyl (aminomethyl)phosphonate and either (IR,2R,5R)-(+)- or (IS,2S,5S)-(-)-2-hydroxy-3-pinanone) followed by separation of the diastereoisomeric products (220) and their subsequent acidolysis, afforded the resolved esters (221) Amongst the various compounds so prepared was the optically... 

In an attempt to obtain diastereoselectivity in the alkylation of derivatives of (aminomethyl)phosphonic acid and so prepare other (1-aminoaikyl)phosphonic acid derivatives in optically active forms, the alkylation (by Mel and PhCH2Br) of the chiral 1,3,2-dioxaphosphorinanes (325 Y=H, CHO C= CHPh or CPh2) as their anions, has been examined. The substrates were derived from 2,4-pentanediol (325 R=H) when the exocyclic P-C bond is oriented equatorialiy preferentially, and from 2-methyl-2,4-pentanediol (325 R=Me) in which the P-C bond prefers the axial position. Unfortunately, in spite of the... 

Hypophosphorous acid can also be aminoalkylated in the absence of mineral acid, (aminomethyl)phosphorous acids (12) are formed but in the presence of acid the second P-H group can also be substituted with formation of bis(aminomethyl)-phosphonic acids 323... 

The third procedure for the synthesis of phosphorylated diazoalkyl compounds is that of diazotization of the correspondingly substituted amino compounds, As a result of the ready availability of dimethyl and diethyl (aminomethyl)phosphonates, these form the most convenient starting materials for conversion into the dialkyl (diazomethyl)phospho-nate by the use of NaN02-acid . Latterly, the customary reagent combination has been that of propyl nitrite in acetic acid, and successful conversions have been described for 16 (Z = COOR CONHR and CN ). In the case of the last substrates, the diazo transfer procedure is said to be unsuitable, because of extensive side reactions which lead to phosphorylated 1,2,3-triazoles. Most reports have been concerned with the preparation of 1 -diazoalkyl compounds, and the syntheses of compounds in which the diazo group is sited elsewhere on the carbon skeleton are very rare ... 

Several studies have employed Escherichia coli, some strains of which appear to be particularly active in their ability to cause P—C bond fission, and through the use of one of these, a metabolite from ethylphosphonic acid was shown to be a-l-(ethylhydroxyphos-phinoyl)ribose (aminomethyl)phosphonic acid and its 7V-methyl, 7V,A -dimethyl and N-acetyl derivatives are converted into A -methylacetamide, A, A -dimethylacetamide, trimethylamine and 7V-methylacetamide, respectively. ... 

The range of phosphonic acids which can be utilized enzymically (at least by those enzymes present in Pseudomonas fluorescens) has recently been extended to include aminoalkyl-, hydroxyalkyl- and oxoalkyl-phosphonic acids, as well as phosphonodipep-tides only slight growth was seen with the herbicide glyphosate (A-phosphonomethyl-glycine (83), which is metabolized to (aminomethyl)phosphonic acid, and neither phos-phinothricin (84) nor its dialanyl tripeptide bialaphos supports growth in contrast to the behaviour of other bacterial extracts isolated from soil ". ... 

R = H), derived from (+)-oxopinic acid, and (aminomethyl)phosphonic acid diethyl ester, was alkylated in the usual way and the products hydrolysed to give the (S)-( 1-aminoalkyl)phosphonic diesters with 15. 62, 93, and 92% e.e. for R = Me, Et. Bn. and allyl. The reaction between (347 R = Li) and diethyl vinylphosphonate gave the (lS)-(347 R = CH2CH2P02Et2) which was acidolysed ( aqueous acetic acid) to... 

Fig. 4 Frequency of detection for selected pesticides (red bars) and their transformation products (blue bars) from 86 municipal wells sampled in Iowa during 2001 [48]. ESA -ethane sulfonic acid OXA - oxanUic acid AMPA - aminomethyl phosphonic acid...

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