Organophosphorus Compounds. I. 2-Chloroalkylphosphonic Acids as Phosphorylating Agents

Maynard, JA; Swan, JM

doi:10.1071/ch9630596

Cited by 105 publications

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“…A number of groups have studied aspects of the breakdown of the acid (1, 4-6). Maynard and Swan (4) showed that the products are chloride ion, ethylene, and phosphate. The yield of ethylene was found to be quantitative (1,5), and according to Yang (6), the yield of phosphate is also quantitative.…”

mentioning

confidence: 99%

Kinetic Studies of the Thermal Decomposition of 2-Chloroethylphosphonic Acid in Aqueous Solution

Biddle

Kerfoot²,

Kho³

et al. 1976

Plant Physiol.

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The decomposition of 2-chloroethylphosphonic acid in aqueous solution has been studied at pH values from 6 to 9 and at temperatures in the 30 to 55 C range. The rate of decomposition is estimated from the rate of formation of ethylene. The rate is proportional to the concentration of the phosphonate dianion and is independent of the hydroxyl ion concentration. The rate constant at 40 C is 1.9 x 10-4 sec-I and the activation energy is 29.8 kcal mol-'. The rate of reaction is not affected significantly by the presence of potassium iodide or urea (substances which increase the rate of leaf abscission in trees sprayed by 2-chloroethylphosphonic add). The rate decreases sghtdy in the presence of low concentrations of magnesium and caldum ions.2-Chloroethylphosphonic acid is widely used in regulating plant development. Its plant growth activity is primarily associated with its ability to release ethylene to the plant tissues (2). A number of groups have studied aspects of the breakdown of the acid (1, 4-6). Maynard and Swan (4) showed that the products are chloride ion, ethylene, and phosphate. The yield of ethylene was found to be quantitative (1, 5), and according to Yang (6), the yield of phosphate is also quantitative. Maynard and Swan noted that the decomposition proceeds only at pH values above 4.5 and came to the tentative conclusion that a doubly ionized phosphonate group is required before fragmentation can occur. Edgerton and Blanpied (3) showed that the rate of formation of ethylene in buffered solutions increases rapidly with pH in the S to 7 region, and Warner and Leopold (5) claimed that ethylene evolution proceeds linearly with time for the first 7 hr, the rate increasing with increasing pH. The decomposition has been described as a base-catalyzed elimination reaction (1), and a second order reaction (5). Yang (6) suggests that the mechanism involves the nucleophilic attack of water on the phosphonate dianion and adds that OH-may also serve as a nucleophile in the reaction. Kinetic data for the decomposition under controlled conditions of both pH and temperature do not appear to be available. This note reports such data, together with some information on the effects of certain additives on the rate of decomposition. MATERIALS AND METHODSThe 2-chloroethylphosphonic acid, provided by Amchem Products, Amber, Pa., was of purity >99%; titration with NaOH indicated that it contained 99.8 + 0.4% acid. The material is hygroscopic and was exposed only to dry air. Buffer solutions were prepared by addition of NaOH solution to solutions of reagent grade sodium dihydrogen phosphate, boric acid, or sodium bicarbonate. Urea and KI were of reagent grade.The reaction vessel for the kinetic experiments consisted of a modified 125-ml conical flask with inner and outer compartments. Ten ml 0.1 M 2-chloroethylphosphonic acid solution, whose pH had been adjusted to 4.1 by addition of NaOH, was placed in the central compartment; 25 ml buffer solution was placed in the outer compartment, and the flask was immersed in ...

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mentioning

confidence: 99%

Kinetic Studies of the Thermal Decomposition of 2-Chloroethylphosphonic Acid in Aqueous Solution

Biddle

Kerfoot²,

Kho³

et al. 1976

Plant Physiol.

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“…LG:, just as C-P scission occurs only in the dianion, but not in the monoanion, of a 2-haloalkylphosphonic acid (Maynard and Swan, 1963). Similarly diazotization of -0 -P(O)(Ph) -CHz -CH2 -NH; , but not of Ph2P(0) -CH2 -CH2 -NH;, gave C-P scission (Mastalerz and Richtarski, 1971).…”

Section: Results and Dlscussionmentioning

confidence: 99%

“…Presumably departure of Nz from -H 0 3 P -CH2 -CH-(-N ' 2) -COOH is accompanied by scission of the P-C bond rather than attack of 01 on C2, the usual reaction when 2-amino acids are diazotized. The reaction is thus like the diazotization of aminoethylphosphonic acid studied by Mastalerz and Richtarski (1971), and closely analogous to the Conant-Swan breakdown in base of 2-haloalkylphosphonic acids (see Maynard and Swan, 1963); it is one of the reactions analysed by Clark et al (1964) as a P-XYZ system in which Z accommodates electrons and it is similar to the mechanism of natural splitting of the C-P bond (La Nauze et al, 1977;Olsen et al, 1988) and to the release of phosphate when 1-aminoalkylphosphonic acids react with ninhydrin (Warren, 1966). When, however, 2 mol/mol HBr was added, no phosphate was released (and bromo acid rather than hydroxy acid was the main product).…”

Section: Results and Dlscussionmentioning

confidence: 99%

The synthesis of 3‐phosphonoalanine, phosphonopyruvic acid and phosphonolactic acid

Sparkes¹,

Rogers²,

Dixon³

1990

European Journal of Biochemistry

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3‐Phosphonoalanine has been made by the Strecker synthesis from phosphonoacetaldehyde, which is easily prepared from vinyl acetate. It gives phosphonopyruvate by transamination when treated with glyoxylate. Phosphonolactate, an analogue of phosphoglycerate, is prepared by reducing phosphonopyruvate. Diazotization of phosphonoalanine was investigated as a route for making phosphonolactate: addition of NaNO2 to the isoelectric form of phosphonoalanine gave much scission of the C‐P bond with release of phosphate; addition of HBr prevented this release and gave largely the bromo acid. The supplement reports the synthesis of arsonolactate, a similar analogue, by treating chlorolactate with alkaline arsenite.

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“…The chemical mechanism of ethylene production from CEPA suggested by Maynard and Swan (5) involves the nucleophilic attack on -the phosphonate dianion by a water molecule and the concerted elimination of chlorine, leading to direct formation of phosphate and chloride as shown in equation (I). Probably the OH-ion may also serve as an nucleophile in the reaction.…”

mentioning

confidence: 99%

Ethylene Evolution From 2-Chloroethylphosphonic Acid

Yang

1969

Plant Physiol.

167

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Organophosphorus Compounds. I. 2-Chloroalkylphosphonic Acids as Phosphorylating Agents

Cited by 105 publications

References 0 publications

Kinetic Studies of the Thermal Decomposition of 2-Chloroethylphosphonic Acid in Aqueous Solution

Kinetic Studies of the Thermal Decomposition of 2-Chloroethylphosphonic Acid in Aqueous Solution

The synthesis of 3‐phosphonoalanine, phosphonopyruvic acid and phosphonolactic acid

Ethylene Evolution From 2-Chloroethylphosphonic Acid

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