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United States Patent Office Patented Oct 2,957,931 United States Patent Office Patented Oct. 25, 1960 2 but only with organic substituents. Formula 5 represents hypophosphorous acid, whereas Formula 4 represents an 2,957,931 isomeric form known only in the organic series. The SYNTHESIS OF COMPOUNDS HAVING ACARBON. compound having Formula 7 is orthophosphorous acid, PHOSPHORUS LINKAGE but the isomeric form, Formula 6, is known only in the organic series. Lyle A. Hamilton and Robert H. Williams, Pitman, N.J., Esters of the inorganic acids, orthophosphorous acid assignors to Socony Mobil Oil Company, Inc., a corpo (7) and hypophosphorous acid (5), are named as phos ration of New York phites and hypophosphites, e.g., monoethyl phosphite, di No Drawing. Filed July 28, 1949, Ser. No. 107,376 10 ethyl phosphite, and ethyl hypophosphite. Organic phosphines having groups such as R, RO, RS, 11 Claims. (Cl. 260-403) etc., in place of the hydrogen atoms of phosphine, and the monosubstituted phosphine oxides are named in ac . cordance with the I.V.C. Rule 34a, c, and f (see C.A. 39, This invention relates, broadly, to organic phosphorus 5 5939-5940 (1945). compounds, and is more particularly concerned with When two hydrogen atoms of phosphine oxide are organic phosphorus compounds in which at least one or replaced with organic radicals, there are two possible ganic radical is joined to phosphorus by a direct carbon isomeric forms, in accordance with the equation, illus phosphorus linkage and with a process for producing trated by the ethyl derivative, them. 20 As is well known to those familiar with the art, there has been considerable confusion in the nomenclature of organic phosphorus compounds, particularly the acid and C.H. H. ester types. For example the names, "phosphonous acid' NM and "phosphinous acid,” have been suggested by the 25 Sn American Chemical Society. These terms, however, de cá, So note compounds which may exist in isomeric forms and (a) the terms do not distinguish these forms. Accordingly, for the sake of clarity and of complete understanding of the present invention, and in order to indicate actual Or structural forms, the following system of phosphorus 30 compound nomenclature has been selected, and adhered Cas to throughout the specification and claims: In general, P-OH all compounds are named as derivatives of phosphine or of phosphine oxide, except in the cases of esters of in Cs organic phosphorus acids and of phosphinic and phos 35 (b) phonic acids and their derivatives. In using this system, the name of an ester radical is written as a separate word from the name of the acid nucleus. The name of a radi To both of these isomers has been applied the apparently cal which is attached directly to phosphorus, thereby 40 forming part of the acid nucleus, is written as one word misleading term "phosphinous acid.” The "ester' of with the name of the acid. The possible inorganic phos form (b) also can exist in an isomeric form, phorus compounds are illustrated in the following for mulae and equations: 45 C5 O P-O CBI M H-p-H Ho-p-H H-p-H Obs BI H E. (c) (1) (2) (3) 50 Of Ho-p-H e Ho-p-r CH5 O O N2 55 (4) (5) CH CB (d) O 60 no-on to-- In order to avoid ambiguity, all of these compounds are E. E. named as derivatives of phosphine or of phosphine oxide. (6) (7) Accordingly, form (a) is diethylphosphine oxide; form (b), hydroxydiethylphosphine; form (c), propoxydiethyl 65 phosphine; and form (d), propyldiethylphosphine oxide. Formula 1 represents phosphine. Compounds having When only one of the hydrogen atoms attached to the Formulae 2 and 3 are not known in the inorganic series, phosphorus atom of hypophosphorous acid (5) is re r 2,957,981 3 4 placed with an organic radical two isomeric forms are tives of the unsaturated compound, utilizing the radical obtained, names set forth hereinbefore. For example, CBIs O CHsO O 2 P-CHO-C-CH Chio? O ho 2 - HQ P-CHC-O CH P-CH-COOE 10 Ho? H^ CH-C OOH O and CHs The single term, "phosphonous acid,” has been applied to both isomers. Likewise, the "esters' thereof have two Y-CHOH isomeric forms, 5 H are named (diethyl phosphono-)ethyl acetate, methyl OCE phosphonopropionate, phosphinosuccinic acid, and ethyl CEs-P phosphinopropanol, respectively. OH However, when two or more of the more complex un (g) saturated compounds are added to the same phosphorus O compound, nomenclature becomes more difficult. Ac C t o cordingly, the products produced are named as substi tuted derivatives of the phosphorus compound reactant, Dr O C3H 25 setting forth in parenthesis the name of the more com (h) plex compound component. For example, the products Accordingly, these compounds are all named as deriva of the following reactions: tives of phosphine and of phosphine oxide. Thus, form (e) is hydroxyethylphosphine oxide; form (f), ethyldihy PE-2C cc.NE - (H.CHNE,pH droxyphosphine; form (g), hydroxypropoxyethylphos 30 phine; and form (h), ethylpropoxyphosphine oxide. CHCHNH The acid resulting from replacing both of the hydrogen atoms attached to the phosphorus atom of hypophos phorous acid (5) with organic radicals is named as a CHCH-NH. phosphinic acid. The esters thereof are called phosphi 35 pH nates, e.g., propyl diethylphosphinate. CECHNE Organic compounds, in which the hydrogen atom at and: tached to the phosphorus atom of orthophosphorous acid (7) is replaced with an organic radical, are called phos - CH-c OOCs phonic acids. The nomenclature of phosphinic acids and 40 CH-COO C2H5 phosphonic acids has been described by the I.V.C. Rule CH-COO CH / (H-C OO CH 34b and c (C.A. 39, 5939 (1945)). PH-3 || Phosphorus compounds which contain more complex CE-COO CE5 -am- PCH-coo CHs substituent groups are named in accordance with the GH-cooch, nomenclature described hereinbefore. The substituent 45 CH-COO C2Es groups are designated by their usual radical names, such are named, respectively, bis-(ethylamine-) phosphine and as silicyl (HaSi-), stannyl (HSn-), amido (HN-), tris-(diethyl succinate-)phosphine. sulfo (HO(O)SO-), sulfino (HO(O)S-), phosphono It must be appreciated that the foregoing examples are (HO)2OP-), phosphino (HP-), phosphonico merely illustrative of the nomenclature system used (HOOP-), phospharseno (-P:AS-), phosphazo 50 herein. Methyl, ethyl, and propyl radicals have been used (-P:N-), phospho (OP-), phosphoro (-P:P-), for the purposes of illustration. When other radicals phosphoroso (OP-), phosphinous (HOP-), etc. The appear in a compound in place of the ethyl and/or pro phosphorus compounds which contain two or more phos pyl radicals, the standard name of the radical so appear phorus-containing groups attached to a hydrocarbon ing will be used in the compound name. The foregoing group or to a substituted hydrocarbon group are desig 55 system of nomenclature is believed to cover most phos nated as substituted derivatives thereof. For example, phorus compounds encountered. Whenever instances CEIs C2Es occur in which a compound cannot be named adequately by this system of nomenclature, the nomenclature there Ho-1-0 (CH-0-h-oh of will be explained when a name is assigned to the 60 compound. OCEI. OCH H. H. The compounds contemplated herein include phos phines, phosphine oxides, phosphonic acids, esters of C.H.0-h-CHCHCCH-h-och, CH-in--CH, phosphonic acids, phosphinic acids, esters of phosphinic 9 O &H, So acids, and various substituted derivatives of these com and 65 pounds. Some of the compounds which can be prepared CH-P-P-CE N by the present process are known, such as, for example, C2H. H. dibutyl esters of normal 1-alkanephosphonic acids. A are called, respectively, bis-(ethanephosphinicooxy-)pro large variety of compounds, however, are believed to be pane, bis-(diethyl phosphono-) 2-chloro-propane, (dieth new compositions of matter. The latter include esters ylstannyl-)propylphosphine oxide, and (diethylphos 70 of normal- and branched-chain alkanephosphonic acids phino-)propylphosphine. In a similar manner, com having the phosphorus attached to a carbon atom other pounds derived by the addition of a phosphorus com than a terminal carbon atom in the chain; derivatives of pound reactant to a more complex unsaturated com alkanephosphonic acids in which additional functional pound reactant, such as unsaturated acids, esters, alco groups are carried on the carbon structure, such as car hols, aldehydes, etc, are named as substituted deriva 75 boxylic acid groups, aldehyde groups, carbonyl groups, 2,957,981 5 6 hydroxyl groups, halogens, amino or amido groups, or The two types of phosphorus compounds are represented sulfide groups; olefinic and acetylenic phosphonic acids by the following formulae: and their derivatives; and telomers containing phospho rus. Many other new compositions contemplated herein Y Y XX xx will become apparent hereinafter. A x P OHA-P- A x P of A-P-H The prior art methods of preparing organic phospho O X O X rus compounds have been disadvantageous from one or XO B O B more standpoints. They have been relatively expensive, B and/or the reactions involved therein have been diffi Type I Type II cult to control, and/or they have given poor yields in O wherein A and B are monvalent atoms or radicals and many instances, and/or they have been rather complex Y is any atom or radical attached to phosphorus by co and involved. Furthermore, it has been impossible to ordinate covalence. Small x represents electrons con prepare many of the compounds contemplated herein, tributed by the phosphorus atom and small o represents by the use of known reactions. Insofar as is now known, electrons contributed by A, B, and H.
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