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Prepared sodium monofluorophosphate in 1929.

3, 1953; granted July 5, 1955 1954 During 1954 to 1957, certain data was published -by the stannous fluoride research group at the University of Indiana- indicating the relative ineffectiveness of sodium monofluorophosphate in the inhibition of dental caries.

PhD thesis 1923 on the action of sulfuric acid on fluorspar and properties of fluosulfonic acid.

15, 1949 1947 (Procter & Gamble Company) and (now with , Clinton Laboratories, Oak Ridge, Tennessee) published the 13th report in a series of studies of fluorophosphoric acids: Preparation of anhydrous monofluorophosphoric acid (25b). "It has recently been shown that the esters of monofluorophosphoric acid which were previously known to be highly toxic, have a probable usefulness in the treatment of glaucoma and myasthenia gravis, the di-isopropyl ester being especially suited for this purpose.

thesis on the action of sulfuric acid on fluorspar.

by reacting the anhydrous acid with ethylene, forms diethyl monofluorophosphate in a reaction corresponding to that of monoethyl sulfuric acid which, when heated, forms diethyl sulfate" Possible uses of the (mono- and di-) fluorophosphoric acids include "as catalysts for polymerization, condensation and alkylation reactions especially for combining such compounds as isoalkanes, and olefines or isoolefines.

Anderson, of the Ozark Mahoning Company, filed a patent for the production of potassium and sodium monofluorophosphates from potassium/sodium fluorides (to avoid the use of HF) and potassium/sodium metaphosphates.

Hodge, fluoride expert at the University of Rochester.

The method consists of three steps: (a) selection of phosphorus trichloride for reaction with the hydroxy body or mercaptan by which the respective alkyl hydrogen phosphite is obtained; (b) treatment of the product obtained in step (a) with chlorine to produce the chloro-phosphoric ester; (c) preparation of highly toxic fluorine compounds by heating gently the chloro compound (step (b)) with excess metallic fluoride (e.g. sodium fluoride) and distilling the organic fluorine compound from the chlorine residue. 1944 and , assignors to Monsanto Chemical Company, patented the production of dialkyl fluorophosphates (such as DFP, diisopropyl fluorophosphate) "by a process which comprises reacting an aliphatic alcohol with phosphorus trichloride to form a dialkyl hydrogen phosphite, chlorinating the crude product and then fluorinating the dialkyl chlorophosphate formed by means of an alkali fluoride (e.g.

ANDERSON, assignor to Ozark Mahoning Company, Tulsa, Oklahoma: "Method of producing monofluorophosphates"; US Patent 2,481,807, filed September 28, 1947, patented Sept.

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Sodium monofluorophosphate is being used "

The product of our invention, to wit, anhydrous monofluorphosphoric acid is of value for the synthesis of various organic materials useful as insecticides, or as a catalyst and for other purposes in the arts, and it is therefore our belief that the acid which in consequence of our invention is now available will have numerous and important applications and that the invention marks a distinct and valuable contribution to industry"). In England, and of Cambridge, in cooperation with the Ministry of Supply filed patents on the preparation of esters of fluorophosphoric acid (e.g. DFP) via chlorophosphonic esters (a standard method for preparing organic fluoro compounds consists in treating a corresponding chloro-compound with inorganic fluoride, see also -> the ):

2-8, "Monofluorophosphate - Its Beginning"; (2) J. Dent.

In discussions with Lange the idea developed that there should be commercial applications for these new fluorine compounds, possibly as mothproofing agents, so he was retained as a consultant to help in a research and development program" (1) In the course of work supported by Ozark, the synthesis of monofluorophosphoric acid finally became possible. The preparation of fluorophosphoric acids became the subject of a dissertation by Ralph Livingston (May 1943). Livingston´s "Historical Review" attests to the fact that "a discussion of the fluorophosphoric acids resolves itself primarily into a discussion of a series of papers by W.

21 (1899) 43; (9a) Seifert 1932, cited in "Fluorine Chemistry", Vol.

29, 1949 "" announced a "New Baby in the Fluorine Family", another "milestone in the history of fluorine chemistry": the availability of salts of monofluorophosphoric and hexafluorophosphoric acids (generally designated FP salts by Ozark). Their history, the report says, "

Beiträge zur Kenntnis der Fluorsulfonsäure", Inaug.

1943 "" led, during World War II, to an association of Ozark Chemical Company (which possessed the raw material for fluorine compounds, fluorspar) with the Purdue Research Foundation (1) where research on some organic fluorine compounds was to be conducted for the National Defense Research Committee (25). "

(1948) 695; (24a) "New baby in the fluorine family", Ind.

Stability, storage and shipment were no longer big problems. Concerning toxicity, the report claims: "Toxicity of the FP compounds is not marked, although it may be more than that of simple fluorides. They do not possess the intense physiological action of the dialkyl esters of the mono- acid, such as DFP (diisopropyl fluorophosphate), which has become of importance in recent years in the treatment of glaucoma and has been described, (though conceivably) as composing the German "nerve" war gases known as ." - An early attempt of white-wash, apparently, for DFP is not Tabun nor Sarin, but one of the nerve agents nevertheless.

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