US3299123A - Substituted methylene diphosphonic acids and salts and esters thereof - Google Patents

Substituted methylene diphosphonic acids and salts and esters thereof Download PDF

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US3299123A
US3299123A US271607A US27160763A US3299123A US 3299123 A US3299123 A US 3299123A US 271607 A US271607 A US 271607A US 27160763 A US27160763 A US 27160763A US 3299123 A US3299123 A US 3299123A
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ester
methylene
esters
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diphosphonate
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Steven J Fitch
Riyad R Irani
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Monsanto Co
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Monsanto Co
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Priority to DE19641302929D priority patent/DE1302929B/de
Priority to FR970088A priority patent/FR1394386A/fr
Priority to US590449A priority patent/US3414393A/en
Priority to US578500A priority patent/US3518200A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3839—Polyphosphonic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/572—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/34—Derivatives of acids of phosphorus
    • C11D1/342—Phosphonates; Phosphinates or phosphonites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/02—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents
    • D06L1/04—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents combined with specific additives

Definitions

  • An object of this invention is to provide new and useful organic compounds of phosphorus containing a PC-P group in their molecules.
  • a further object of this invention is to provide new and useful organic compounds of phosphorus containing a I335 PCP group in their molecules with the C group being a hydrophobic and/ or lipophilic groups.
  • a further object of this invention is to provide new and useful organophosphonic acids, as well as their salts and esters.
  • a more specific object of this invention is to provide new and useful organo-methylene diphosphonic acids or the salts thereof which exhibit, among other things, combined surfactancy, sequestering and deflocculating properties.
  • a more specific object of this invention is to provide new and useful organo-met-hylene diphosphonate esters which exhibit, among other things, the unique ability of solubilizing water in water immiscible solvents.
  • Another object of this invention is to provide detergent compositions containing organo-methylene diphosphonic acids or the salts thereof.
  • Another object of this invention is to provide detergent compositions containing organo-methylene diphosphonic acids or the salts thereof which are suitable for use in aqueous systems.
  • Another object of this invention is to provide detergent compositions containing organo-methylene diphosphonate esters.
  • a still further object of this invention is to provide detergent compositions containing organo-methylene diphosphonate esters which are suitable for use as dry-cleaning detergents in organic solvents.
  • a still further object of this invention is to provide gasoline additive compositions containing organo-methylene diphosphonate esters.
  • This invention is directed to new and useful organomethylene diphosphonic acid compounds, as well as the salts and esters thereof, said compounds having the gen eral formula.
  • R is selected from the class consisting of aliphatic hydrocarbyl, alicyclic, aryl, alkaryl, aralkyl groups of from 5 to 30 carbon atoms and carbon containing heterocyclic groups and X is selected fro-m the class con sisting of cations selected from the group consisting of hydrogen ions, alkali metal cations, alkaline earth metal cations, aluminum cations, ammonium ions and amine ions, and aliphatic hydrocarbyl, aryl, alkaryl and aralkyl groups of from 1 to 30 carbon atoms.
  • R and X represent groups containing carbon chains, such as aliphatic hydrocarbyl groups, or groups containing alkyl moieties, i.e., aralkyl groups
  • carbon chains may be of a straight chain structure or branch chain structure.
  • R and X when the represent aliphatic hydrocarbyl groups, such groups may be saturated or unsaturated.
  • the compound of the instant invention should preferably contain not more than 25 carbon atoms associated with R and X (when X represents ester groups, and there are few, if any, end uses, in which'the foregoing groups contain more than a total of 50 carbon atoms.
  • organo-methylene diphosphonic acids the salts of organo-rnethylene diphosphonic acids, and the esters of organo-methylene diphosphonic acids.
  • the compounds of the invention can be prepared by various methods with the following methods presented as being representative of their preparation.
  • the ester of the organo-methylene diphosphonic acids can be prepared by first forming a mctallo-derivative of a methylene diphosphonate ester and reacting this metallO ester derivative with an organo-halide to produce the desired organo-methylene diphosphonate ester.
  • the reaction of the metallo-ester derivative with the organohalide is believed represented by the following equation:
  • R represents the same groups as in the foregoing general Formula 1.
  • metallo-derivatives of the tetraester methylene diphosphonate can be prepared in several ways.
  • Group IA (alkali metals) ester derivatives and particularly the sodioand potassioester derivatives it is usually only necessary to react the alkali metal directly with the ester. The reaction is often exothermic so that, in most cases, it maybe necessary to bring the reactants together while cooling, to dilute the mixture with an inert solvent such as xylene, benzene, toluene, ether, dioxane, hexane and the like, or to add the sodium or potassium slowly to the esters in the inert solvent.
  • an inert solvent such as xylene, benzene, toluene, ether, dioxane, hexane and the like, or to add the sodium or potassium slowly to the esters in the inert solvent.
  • Group l-B metal derivatives and in particular the silver-ester derivative and cuprous-ester derivative; the Group II-B metal derivatives, and in particular the zinc-ester derivatives; and Group IV-A metal derivatives, and in particular the leadand tin-ester derivatives by methods which are similar to the foregoing methods. Because of the relative inexpensiveness and the ready availability of sodium and potassium and because of their rather straight forward reaction with the ester it is gen erally advantageous to form the sodioand po-tassio-ester derivatives and, therefore, sodium and potassium are the preferred metals for use in forming these ester derivatives.
  • reaction of the metallo-ester derivatives with an organo halide is relatively straight forward. Oftentimes, however, it may be necessary to use temperatures above room temperature, i.e., about 25 C., in order to facilitate the reaction with temperatures of between about 70 C. to about 180 C. usually being sufficient. In most cases, depending on the temperature used, a definite precipitate forms, i.e., metal-halide, after a period of time of between about 10 minutes and about 4 hours.
  • the precipitate may be removed by several well known methods, such as, filtration, centrifugation and decantation, or by dissolution with water and phase separation, and, if desired, the filtrate can thereafter be distilled to improve the purity of the organo-methylene diphosphonate ester.
  • organo halides containing substituent groups such as, hydroxyl, carboxylic acid, and halides
  • substituent groups such as, hydroxyl, carboxylic acid, and halides
  • carboxylic acid groups can be protected by the well known method of esterification prior to the reaction and hydrolysis of the ester subsequent to the reaction.
  • hydroxyl group can usually be protected by the well known method of ether formation using such materials as dihydropyrane, benzyl chloride, tritychloride and the like to form the ethers followed by removal of the protective groups by such methods as hydrolysis with dilute mineral acids, catalytic hydrogenation, or chemical reduction.
  • the halide group of polyhalide compounds can usually be protected by conversion into an ether group, a common reactant being sodium alkoxide, and the ether group subsequently cleaved with a hydrogen halide to remove the protective ether groups.
  • the organo-methylene diphosphonic acid can be prepared by the hydrolysis of the corresponding esters with a concentrated mineral acid. Generally, by refluxing the ester and a concentrated mineral acid, such as HCl or HBr, at reflux temperatures for a period of usually about five hours is all that is necessary for the hydrolysis.
  • a concentrated mineral acid such as HCl or HBr
  • the salts of the organo-methylene diphosphonic acids can be prepared by neutralization of the acids with a stoichiometric amount of a base or a salt of a volatile acid that contains essentially the desired cation.
  • Bases or salts of volatile acids such as those containing an alkali metal, alkaline earth metal, aluminum, ammonia and amines are especially suited.
  • one of organo-methylene diphosphonic acids can he neutralized with a stoichiometric amount of a base containing the sodium cation, such as NaOH, Na CO and the like.
  • organo-methylene diphosphonic acid titrates using a pH meter as a tribasic acid can be prepared by neutralization of the acids with a stoichiometric amount of a base and evaporating to dryness.
  • the acids are titrated using a pH meter in the presence of a 10% NaCl solution they will titrate as tetra-basic acids.
  • Example 1 Into a suitable reaction vessel about 39.1 grams of potassium metal is added slowly to about 288 grams tetraethyl methylene diphosphonate in about 2.5 liters of xylene. The temperature of the reaction vessel is maintained at about 65 C. After all of the potassium is used up about 179 grams of n-heptyl bromide is added dropwise to the reaction mixture. To ensure a satisfactory degree of reaction the mixture is heated between about 100 C. and 140 C. for about 10 hours. After filtering the potassium bromide the reaction product is distilled yielding the ester as a colorless liquid.
  • Example 2 The ester prepared according to Example 1 is hydrolyzed to the acid by refluxing about 386 grams with about 600 ml. concentrated HCl for about 5 hours. Evaporation to dryness yields the acid, octylidene diphosphonic acid, C H CH[PO(OH) The equivalent weight of this product, by tritration, is found to be about 98.0 which compares favorably with the calculated value of about 91.3. Elemental analysis yields the following results:
  • Trisodium octylidene diphosphonate C H CH[PO(ONa [PO(ONa) (OH)] is prepared by dissolving about 274 grams of free acid obtained as in Example 2 in about 1.2 liters of 10% NaOH solution and evaporating the aqueous solution to dryness at about 140 C. with the anhydrous form of the salt being formed.
  • Example 4 Into a suitable reaction vessel about 39.1 grams potassium metal is added slowly to about 288 grams tetraethyl methylene diphosphonate in about 2.5 liters of Xylene. The temperature of the reaction vessel is maintained at about C. After all of the potassium is used up about 247 grams of n-dodecylbromide is added dropwise to the reaction mixture. To ensure a satisfactory degree of reaction the mixture is heated at about C. for about 4 hours. After filtering the potassium bromide the reaction product is distilled yielding the ester as a colorless liquid. Analysis of the P NMR spectra of the ester indicated tetraethyl tridecylidene diphosphonate,
  • Example 5 Tetraethyl tridecylidene diphosphonate is hydrolyzed to the acid refluxing about 454 grams with about 600 ml. of concentrated HCl for about 2 to 3 hours. Evaporation to dryness yields the acid, tridecylidene diphosphonic acid, C H CH[PO(OH) which is analyzed with the following results:
  • Example 5 is prepared by dissolving about 334 grams of the free acid obtained as in Example 5 in about 1 /2 liters of 10% NH OH solution and evaporating the aqueous solution to dryness at about 120 C. with the anhydrous form of the salt being formed.
  • Example 7 2 5)2( 3) 4 9)2]2
  • Example 8 Dicalcium cyclohexyl methylene diphosphonate
  • C H CH[PO(OCaO)] J is prepared by dissolving about 322 grams of the free acid (cyclohexyl methylene diphosphonic acid), prepared generally by procedures used in Example 2, in about 1 liter of 20% Ca(OH) solution and evaporating the aqueous solu tion to dryness at about 120 C. with the anhydrous form of the salt being formed.
  • the free acid cyclohexyl methylene diphosphonic acid
  • Example 9 Tetraethyl benzyl methylene diphosphonate prepared generally by the procedures used in Example 1, is hydrolyzed to the acid by refluxing about 347 grams of the ester with about 800 ml. of concentrated HCl for about 4 hours. Evaporation to dryness yields the acid, benzyl methylene diphosphonic acid,
  • Example 12 Tetraethyl acetophenone methylene diphosphonate CH C(O)C H -CH[PO(OC H prepare-d generally by procedures used in Example 1, is hydrolyzed to the acid by refluxing about 405 grams of the ester with about 800 ml. of concentrated MCl for about 3 hours. *Evaporation to dryness yields the acid, acetophenone methylene diphosphonic acid, CH C(O)C H -CH[PO(OH)
  • Example 13 Into a suitable reaction vessel about 39.1 grams of potassium metal is added slowly to about 28 8 grams of tetraethyl methylene diphosphonate in about 2.5 liters of xylene. The temperature of the reaction vessel is maintained at about 70 C.
  • Example 14 Into a suitable reaction vessel about 39.1 grams of potassium metal is added slowly to about 288 grams of tetraethyl methylene diphosphonate in about 2.5 liters of xylene. The temperature of the reaction vessel is maintained at about 70 C. After all of the potassium is used up about grams of (x-ClllOlOPYlIOl is added slowly to the reaction mixture. To ensure a satisfactory degree reaction the mixture is heated at about C. to about C. for about 6 hours. After filtering the potassium bromide the reaction product is distilled yielding the ester, tetraethyl pyrryl-l-methylene diphosphonate,
  • esters which can be reacted with metallic sources to form the metallo-ester derivatives, such as the potassio-ester derivatives, according to the procedures as illustrated by the foregoing examples include the following esters: tetramethyl methyl ene diphosphonate, tetra-n-hexyl methylene diphosphonate, tetra-isopropyl methylene diphosphonate, tetradodecyl methylene diphosphonate, tetra-hexadecyl methylene diphosphonate, tetra-toluyl methylene diphosphonate, tetra-xylyl methylene diphosphonate, and the like, as well as mixed esters, such as, diethyl-dibutyl methylene diphosphonate, diethyl-di-n-hexyl methylene diphosphonate, dimethyl-diethyl methylene diphosphonate and the following esters: te
  • Alicyclic halide compounds include cyclopentyl bromide, cyclohexyl chloride, cycloheptanyl chloride, cycloheptanyl bromide, cyclopentadiene dibromide, cyclohexane carboxylic acid chloride, 1-chloro-1-methyl cyclohexane, 3-bromo-cyclohexene, 3-chloro-cyclohexene, 2- chloro-cyclopentadiene, 2-bromo-cycloheptanone, 1-2-dibromo cycloheptane, 1bromo-4tert-butyl-cyclohexane, 1- chloro-l-met-hyl cyclohexane, 1-2-dibromo cycloheptane, 1-chloro-3 methyl cyclohexane, and the like.
  • Aryl halide compounds include the mono-cyclic arylhalide compounds, such as ch lorobenzene, 2-chloroaniline, 2-amino-4, 6-dichloro phenyl br-omobenzene, 4-bromo aniline and the like, as well as the polycyclic aryl halide compounds, such as, 3-chlo-robiphenyl, 4-amino-4-chloro biphenyl, 2-chloro-1-naphthal, 2-chloro-anthraquinone, 1- chl oro-naphthalene, l-bromo-naphthalene, 2 bromo biphenyl, and the like.
  • Alkaryl halide compounds include benzyl chloride, ⁇ 3- phenyl ethyl chloride, 4-methyl benzyl chloride, 3-rnethyl benzyl chloride, Z-methyl benzyl chloride, 2-chlorobenzyl chloride, 4-chlorobenzyl chloride, 3-chlorobenzyl chloride, 4-isopropy1 benzyl chloride, m-xylene dichloride, a-chl-oro acetophenone, benzyl chloroformate, benzyl bromide, B-phenyl ethyl bromide, Z-bromo benzyl bromide, 3-nitro benzyl bromide and the like.
  • Aralkyl halide compounds include 2-chlorotoluene, 3- chlorotoluene, 4-chlorotoluene, l-chloro-Z-ethyl benzene, 2-ch loro-2-vinyl benzene, 1-chloro-2-isopropyl benzene, 2-chloro-4-isop1'opyl-l-methyl benzene, p-chloro benzoic acid, 2-chloro-4-octyl phenol, 2-chloro-4-nonyl phenol, 2-chloro-4-dodecy1 phenol, 2-benzyl-4-chlorophenol, 2- bromotoluene, 1-bromo-4-ethyl benzene, 4-bromoacetanilide, 4-bromoacetophenone, phenaryl bromide, 4- bromobenzoic acid and the like.
  • Heterocyclic halide compounds include N-chlorosuccinimide, N-bromo succinimide, 2-chloropyridine, 2- chloroquinaline, 2bromo-5- nitro furan, 2-bromo-5-methyl furan, S-bromo indole, 5-bromo-2-methyl indole, 4-bromo-2-picoline, 3-chloropyridine, 4-chloropyridine, 3-bro- D mo-thiophene, 2-bromo-3,4-dinitro thiophene, 2-chloro thiophene, 2-bromofuran, 3,4-dichloro-tetrahydrofuran, 3,4-dichloro-2,S-diphenyl furan, S-bromoindole, 4chloroindole, 7-chloro-2,3-dimethyl indole, 2-chloro-1,4,6-trimethyl indole and the like.
  • bases or salts of volatile acids which can be reacted with the free acids to produce salt compounds of the instant invention according to the procedures as illustrated by the foregoing examples include the inorganic alkali metal, alkaline earth metal and aluminum salts, oxides and hydroxides, such as, NaCl, NaNO Na O, Na CO KOH, K 0, KCl, K CO KNO LiOH, LiCl, LlNO3, Ll2CO CSOH, CsCl, CSNO3, CS2CO3, CaCl CaO, CaCO MgCl MgO, MgCO BaCO BaCl Ba(OH) Ba(NO SrCA SrCl Sr(OH) Al(OH A1 Al(NO and amines, such as, ethyl amine, diethylamine, propyl amine, propylene diamine, diethylene triamine, hexyl amine, 2-ethylhexyl amine and the like.
  • oxides and hydroxides such as, NaCl, NaNO
  • organo-methylene diphosphonic acids or the salts thereof were found to exhibit not only good deflocculating or dispersing properties and sequestration properties but also good surfactancy properties. It is highly unusual for all of these properties to be effectively exhibited by the same compound. As can be appreciated, such compounds can advantageously be utilized in applications which can use the foregoing properties, such as, detergent compositions.
  • R is selected from the class consisting of saturated and ethylenically unsaturated aliphatic hydrocarbyl radicals containing from 5 to 20 carbon atoms and Z is a cation selected from the group consisting of hydrogen in conventional amounts such as is normally used with detergent compositions and which is generally about 5% concentration or below.
  • esters of organo-methylene diphosphonic acids were found not only to be substantially miscible with water but also highly soluble in organic solvents, such as hydrocarbon solvent, i.e. hexane and pentane, carbon tetra chloride, haloethylene solvents (perchloroethylene), ethers, alcohols, and the like.
  • organic solvents such as hydrocarbon solvent, i.e. hexane and pentane, carbon tetra chloride, haloethylene solvents (perchloroethylene), ethers, alcohols, and the like.
  • the esters were found to impart a solubilizing. action to water in water-immiscible solvents, such as many of the previously mentioned solvents. This totally unexpected property renders them highly useful as gasoline de-icer additives and along with their surfactancy properties renders them useful as dry cleaning detergents.
  • the unique ability to impart a solubilizing action to water in water-immiscible solvents can be utilized in many and
  • esters of higher alkylidene diphosphonic acids are preferred in applications which use the combined surfactancy and/or water solubilizing properties. These compounds are of the following formula:
  • R is selected from the class consisting of saturated and ethylenically unsaturated aliphatic hydrocarbyl radicals containing from to carbon atoms and R R R and R are selected from the class consisting of alkyl groups of from 1 to 20 carbon atoms, aryl hydrocarbyl groups and alkaryl groups with the lower alkyl groups being especially preferred.
  • ester compounds of the instant invention are useful in gasoline as de-icer additives and are preferably used in amounts of from .005 to 5% by weight.
  • An advantageous feature of these deicer additives is their ability to function either wholly as the primary additive for surface ignition control or in conjunction with other known phosphorus additives for surface ignition control.
  • ester compounds of the instant invention can be used as either the primary surfactant or in conjunction with other surfactants.
  • the primary surfactant When used as substantially the primary surfactant with many of the common organic solvents, such as, Stoddards solvent and perchloroethylene, amounts within the range of .05% to 10% by weight are usually sufficient with amounts about 2% by weight being preferred.
  • ester compounds of the instant invention may also be used as extractants for metals in an aqueous-organic solvent system.
  • R is selected from the class consisting of aliphatic hydrocarbyl groups of from 7 to 30 carbon atoms and alicyclic, aryl, alkaryl, aralkyl groups of from 5 to 30 carbon atoms and
  • X is selected from the class consisting of cations selected from the group consisting of hydrogen ions, alkali metal cations, alkaline earth metal cations, aluminum cations, ammonium ions and amine ions, and aliphatic hydrocarbyl, aryl, alkaryl and aralkyl groups of from 1 to 30 carbon atoms.
  • a diphosphonic acid having the formula wherein R is selected from the class consisting of aliphatic hydrocarbyl groups of from 7 to 30 carbon atoms and alicyclic, aryl, alkaryl, aralkyl groups of from 5 to 30 carbon atoms and X is hydrogen.
  • a salt of a diphosphonic acid said salt having the formula wherein R is selected from the class consisting of aliphatic hydrocarbyl groups of from 7 to 30 carbon atoms and alicyclic, aryl, alkaryl, aralkyl groups of from 5 to 30 carbon atoms and X is selected from the class consisting of alkali metal cations, alkaline earth metal cations, aluminum cations, ammonium ions, and amine ions. 4.
  • An ester of a diphosphonic acid said ester having the formula X0 0 R 0 0X ⁇ ll 1 ll/ PC-P XO/ r I oX wherein R is selected from the class consisting of aliphatic hydrocarbyl groups of from 7 to 30 carbon atoms and alicyclic, aryl, alkaryl, aralkyl groups of from 5 to 30 carbon atoms and X is selected from the class consisting of aliphatic hydrocarbyl, aryl, alkaryl and aralkyl groups of from 1 to 30 carbon atoms.
  • a diphosphonic compound having the formula ZO H OZ wherein R is selected from the class consisting of saturated and ethylenically unsaturated aliphatic hydrocarbyl groups containing from 7 to 20 carbon atoms and Z is a cation selected from the group consisting of hydrogen ion, alkali metal cations, alkaline earth metal cations, aluminum cations, ammonium ions and amine ions.
  • a salt of a diphosphonic acid said salt having the formula ZO ⁇ O R 1+1 ZO Z wherein R is selected from the class consisting of saturated and ethylenically unsaturated aliphatic hydrocarbyl groups containing from 7 to 20 carbon atoms and Z is a cation selected from the class consisting of alkali metal cations, alkaline earth metal cations, aluminum cations, ammonium ions, and amine ions.

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US271607A 1963-04-09 1963-04-09 Substituted methylene diphosphonic acids and salts and esters thereof Expired - Lifetime US3299123A (en)

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Application Number Priority Date Filing Date Title
DENDAT1302557D DE1302557B (xx) 1963-04-09
US271607A US3299123A (en) 1963-04-09 1963-04-09 Substituted methylene diphosphonic acids and salts and esters thereof
DE19641302929D DE1302929B (xx) 1963-04-09 1964-04-08
FR970088A FR1394386A (fr) 1963-04-09 1964-04-08 Nouveaux acides organo-méthylène diphosphoniques, leurs sels et esters
US590449A US3414393A (en) 1963-04-09 1966-08-29 Gasoline compositions containing diphosphonates
US578500A US3518200A (en) 1963-04-09 1966-09-12 Organic phosphorus compounds,compositions containing same,and uses thereof

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US271607A US3299123A (en) 1963-04-09 1963-04-09 Substituted methylene diphosphonic acids and salts and esters thereof
US590449A US3414393A (en) 1963-04-09 1966-08-29 Gasoline compositions containing diphosphonates
US57850066A 1966-09-12 1966-09-12

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Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3400176A (en) * 1965-11-15 1968-09-03 Procter & Gamble Propanepolyphosphonate compounds
US3463835A (en) * 1965-10-05 1969-08-26 Plains Chem Dev Co Aromatic polyphosphonic acids,salts and esters
US3475486A (en) * 1966-09-12 1969-10-28 Monsanto Co Process for preparing phosphonic acids
US3475293A (en) * 1964-09-22 1969-10-28 Monsanto Co Electrodeposition of metals
US3488419A (en) * 1965-12-08 1970-01-06 Procter & Gamble Oral compositions for calculus retardation
US3518200A (en) * 1963-04-09 1970-06-30 Monsanto Co Organic phosphorus compounds,compositions containing same,and uses thereof
US3609075A (en) * 1968-06-25 1971-09-28 Procter & Gamble Cleaning and softening detergent compositions
US3617576A (en) * 1970-04-13 1971-11-02 Monsanto Co Methods of scale inhibition
US3624188A (en) * 1968-10-25 1971-11-30 Procter & Gamble Hypohalogenation of tetramethyl and tetraethyl methylenediphosphonates and trihydrocarbyl phosphonoacetates
US3678154A (en) * 1968-07-01 1972-07-18 Procter & Gamble Oral compositions for calculus retardation
US3683080A (en) * 1970-08-28 1972-08-08 Procter & Gamble Compositions for inhibiting anomalous deposition and mobilization of calcium phosphate in animal tissue
US3846483A (en) * 1970-04-13 1974-11-05 Monsanto Co Substituted ethane diphosphonic acids and salts and esters thereof
US3846420A (en) * 1969-11-19 1974-11-05 Henkel & Cie Gmbh Process for the preparation of 1-aminoalkane-1,-diphosphonic acids and their salts
US3925456A (en) * 1973-08-27 1975-12-09 Henkel & Cie Gmbh Cyclic aminophosphonic acids
US3940436A (en) * 1970-04-13 1976-02-24 Monsanto Company Substituted ethane diphosphonic acids and salts and esters thereof
US3992332A (en) * 1974-08-22 1976-11-16 Hemson Joseph Zenon Liquid composition for fabric treatment
USRE29182E (en) * 1965-12-08 1977-04-12 The Procter & Gamble Company Oral composition for calculus retardation
US4020091A (en) * 1965-10-28 1977-04-26 Plains Chemical Development Co. Chelation
US4116990A (en) * 1970-04-30 1978-09-26 Plains Chemical Development Co. Chelation
US4138431A (en) * 1978-06-29 1979-02-06 Nalco Chemical Company Reaction of α-phosphorus containing carboxylic acids with phosphorous acid to prepare scale and corrosion inhibitors
US4157364A (en) * 1977-10-25 1979-06-05 Buckman Laboratories, Inc. Process for preparing dimethylaminomethylenebis(phosphonic acid)
US4309364A (en) * 1979-02-13 1982-01-05 Symphar S.A. Diphosphonates
US4416877A (en) * 1979-02-13 1983-11-22 Symphar S.A. Anti-atherosclerotic pharmaceutical compositions containing diphosphonate compounds
US4719203A (en) * 1985-11-13 1988-01-12 Boehringer Mannheim Gmbh Diphosphonic acid derivatives, processes for the preparation thereof and pharmaceutical compositions containing them
US4746654A (en) * 1982-07-29 1988-05-24 Sanofi Anti-inflammatory products derived from methylene-diphosphonic acid, and process for their preparation
US4818774A (en) * 1986-03-10 1989-04-04 Occidental Chemical Corporation Organophosphorus compounds
US5043330A (en) * 1988-03-31 1991-08-27 Symphar S.A. Phenol substituted gem-diphosphonate derivatives, process for their preparation and pharmaceutical compositions containing them
US5157027A (en) * 1991-05-13 1992-10-20 E. R. Squibb & Sons, Inc. Bisphosphonate squalene synthetase inhibitors and method
US5449804A (en) * 1989-11-06 1995-09-12 Zaosheng; Xiao Diphosphonate compounds, their preparation and application

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US5332728A (en) * 1992-11-23 1994-07-26 Bristol-Myers Squibb Company Method for treating a fungal infection
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Cited By (34)

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Publication number Priority date Publication date Assignee Title
US3518200A (en) * 1963-04-09 1970-06-30 Monsanto Co Organic phosphorus compounds,compositions containing same,and uses thereof
US3475293A (en) * 1964-09-22 1969-10-28 Monsanto Co Electrodeposition of metals
US3463835A (en) * 1965-10-05 1969-08-26 Plains Chem Dev Co Aromatic polyphosphonic acids,salts and esters
US4020091A (en) * 1965-10-28 1977-04-26 Plains Chemical Development Co. Chelation
US3502585A (en) * 1965-11-15 1970-03-24 Procter & Gamble Detergent compositions containing propanepolyphosphonate compounds
US3400176A (en) * 1965-11-15 1968-09-03 Procter & Gamble Propanepolyphosphonate compounds
US3488419A (en) * 1965-12-08 1970-01-06 Procter & Gamble Oral compositions for calculus retardation
USRE29182E (en) * 1965-12-08 1977-04-12 The Procter & Gamble Company Oral composition for calculus retardation
US3475486A (en) * 1966-09-12 1969-10-28 Monsanto Co Process for preparing phosphonic acids
US3609075A (en) * 1968-06-25 1971-09-28 Procter & Gamble Cleaning and softening detergent compositions
US3678154A (en) * 1968-07-01 1972-07-18 Procter & Gamble Oral compositions for calculus retardation
US3624188A (en) * 1968-10-25 1971-11-30 Procter & Gamble Hypohalogenation of tetramethyl and tetraethyl methylenediphosphonates and trihydrocarbyl phosphonoacetates
US3846420A (en) * 1969-11-19 1974-11-05 Henkel & Cie Gmbh Process for the preparation of 1-aminoalkane-1,-diphosphonic acids and their salts
US3617576A (en) * 1970-04-13 1971-11-02 Monsanto Co Methods of scale inhibition
US3940436A (en) * 1970-04-13 1976-02-24 Monsanto Company Substituted ethane diphosphonic acids and salts and esters thereof
US3846483A (en) * 1970-04-13 1974-11-05 Monsanto Co Substituted ethane diphosphonic acids and salts and esters thereof
US4116990A (en) * 1970-04-30 1978-09-26 Plains Chemical Development Co. Chelation
US3683080A (en) * 1970-08-28 1972-08-08 Procter & Gamble Compositions for inhibiting anomalous deposition and mobilization of calcium phosphate in animal tissue
US3925456A (en) * 1973-08-27 1975-12-09 Henkel & Cie Gmbh Cyclic aminophosphonic acids
US3992332A (en) * 1974-08-22 1976-11-16 Hemson Joseph Zenon Liquid composition for fabric treatment
US4157364A (en) * 1977-10-25 1979-06-05 Buckman Laboratories, Inc. Process for preparing dimethylaminomethylenebis(phosphonic acid)
US4138431A (en) * 1978-06-29 1979-02-06 Nalco Chemical Company Reaction of α-phosphorus containing carboxylic acids with phosphorous acid to prepare scale and corrosion inhibitors
US4309364A (en) * 1979-02-13 1982-01-05 Symphar S.A. Diphosphonates
US4371527A (en) * 1979-02-13 1983-02-01 Symphar S.A. Therapeutic process with diphosphonate compounds
US4416877A (en) * 1979-02-13 1983-11-22 Symphar S.A. Anti-atherosclerotic pharmaceutical compositions containing diphosphonate compounds
US4746654A (en) * 1982-07-29 1988-05-24 Sanofi Anti-inflammatory products derived from methylene-diphosphonic acid, and process for their preparation
US4876248A (en) * 1982-07-29 1989-10-24 Sanofi Anti-inflammatory products derived from methylene-diphosphonic acid, and process for their preparation
US4719203A (en) * 1985-11-13 1988-01-12 Boehringer Mannheim Gmbh Diphosphonic acid derivatives, processes for the preparation thereof and pharmaceutical compositions containing them
AU584759B2 (en) * 1985-11-13 1989-06-01 Boehringer Mannheim Gmbh New diphosphonic acid derivatives, processes for the preparation thereof and pharmaceutical compositions containing them
US4818774A (en) * 1986-03-10 1989-04-04 Occidental Chemical Corporation Organophosphorus compounds
US5043330A (en) * 1988-03-31 1991-08-27 Symphar S.A. Phenol substituted gem-diphosphonate derivatives, process for their preparation and pharmaceutical compositions containing them
US5128331A (en) * 1988-03-31 1992-07-07 Symphar S.A. Method for lowering plasma lipid levels or blood pressure
US5449804A (en) * 1989-11-06 1995-09-12 Zaosheng; Xiao Diphosphonate compounds, their preparation and application
US5157027A (en) * 1991-05-13 1992-10-20 E. R. Squibb & Sons, Inc. Bisphosphonate squalene synthetase inhibitors and method

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DE1302929B (xx) 1971-12-30
US3414393A (en) 1968-12-03
DE1302557B (xx) 1971-08-26
US3518200A (en) 1970-06-30

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