US2900408A - Acid esters of acyl-phosphorous acids and method of making the same - Google Patents

Acid esters of acyl-phosphorous acids and method of making the same Download PDF

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Publication number
US2900408A
US2900408A US657496A US65749657A US2900408A US 2900408 A US2900408 A US 2900408A US 657496 A US657496 A US 657496A US 65749657 A US65749657 A US 65749657A US 2900408 A US2900408 A US 2900408A
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acid
phosphorous
acyl
phosphite
acid esters
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US657496A
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Blaser Bruno
Kaiser Wilhelm Jakob
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4062—Esters of acids containing the structure -C(=X)-P(=X)(XR)2 or NC-P(=X)(XR)2, (X = O, S, Se)
    • C07F9/4065—Esters of acids containing the structure -C(=X)-P(=X)(XR)2, (X = O, S, Se)

Definitions

  • This invention relates to acid esters of acyl-phosphorous acids and their salts and to a method of preparing the same from halides of monobasic or polybasic carboxylic acids and di-substituted phosphites.
  • the ethyl ester of acetyl-phosphorous acid or benZoyl-phosphorous acid may be obtained by a reaction between acetyl chloride or benzoyl chloride and triethyl phosphite.
  • the neutral esters thus obtained decompose upon saponification either into the corresponding carboxylic acid and phosphorous acid or into the corresponding aldehyde and phosphoric acid. It is therefore not possible to produce acid esters of acyl-phosphorous acids or their salts by this method.
  • acid esters of acyl-phosphorous acids may be produced in a very simple fashion by reacting halides of monobasic or polybasic carboxylic acids with di-substituted phosphites at elevated temate peratures.
  • a monocarboxylic acid halide is used,
  • reaction in accordance with the present invention probablyproceeds in accordance with the following general equation.
  • R and R represent identical or dilierent aliphatic or cycloaliphatic hydrocarbon radicals with preferably less than 8 carbon atoms
  • R" represents an aliphatic, cycloaliphatic or aromatic hydrocarbon radical.
  • the radicals R, R and R" may be straight-chain hydrocarbon radicals or also branched-chain hydrocarbon radicals. They may also be substituted, for example halogensubstituted.
  • the radical R may 'in addition be interrupted by heteroatoms; that is, by oxygen, sulfur or nitrogen atoms. If the halide of a dibasic or polybasic carboxylic acid is used as the starting material for the process in accordance with the invention, dibasic or polybasic acid esters are formed in analogous fashion, for example, in accordance with the following equation:
  • the halides preferably the chlorides or bromides, of aliphatic, cycloaliphatic or aromatic monocarboxylic, dicarboxylic or polycarboxylic acids, the hydrocarbon radicals of which carry various substit-uents or t 2 are also interrupted by heteroatoms or hetero atom groups, may be used as starting materials for the process according to the present invention; such acids are, for example, acetic acid, butyric acid, isobutyric acid, lauric acid and higher fatty acids, mono-, di-jand trichloroacetic acid, as well as other halogenated carboxylic acids, ether-carboxylic acids, thioether-carboxylic acids, aminocarboxylic acids, cyclohexane-carboxylic acid, benzoic acid and other substituted or unsubstituted.
  • acids are, for example, acetic acid, butyric acid, isobutyric acid, lauric acid and higher fatty acids, mono-, di
  • aromatic carboxylic acids as Well as diand poly-carboxylic acids, such as adipic acid, sebacic acid, tricarballylic acid, phthalic acid, tetrachlorophthalic acid, terephthalic acid, trlmesic acid, and the like.
  • Di substituted phosphites which may be reacted with the carboxylic acid halides in accordance with the invention are, for example, diethyl phosphite, di-isopropyl phosphite, dibutyl phosphite, dioctyl phosphite, di-(Z- chloroethyD-phosphite, and the like.
  • the two reaction components are preferably used in quantitative ratios such that about one mol of di-substituted phosphite is present for each CO-Hal group.
  • the reaction takes place at elevated temperatures, preferably between 50 and C.
  • elevated temperatures preferably between 50 and C.
  • an inert organic solvent or diluent such as carbon tetrachlorodie or benzene.
  • the reaction proceeds with the formation of an aliphatic or cycloaliphatic halide. If a low-molecular aliphatic alcohol is used for the production of the disubstituted phosphite, this hydrocarbon halide continuously distills out of the reaction mixture during the reaction. If a high-molecular aliphatic or cycloaliphatic alcohol is used to produce disubstituted phosphite, the hydrocarbon halide may be distilled off vacuo during or after the reaction.
  • the acid esters of acyl-phosphorous acids obtained by reaction in accordance with the invention are useful as capillary-active agents for various purposes, for example as cleaning agents or washing agents.
  • the acid ester of acy-l-phosphorous acid as described above may be transformed into their salts, for example their alkali metal salts in a very simple fashion.
  • These salts are likewise useful as capillary-active agents and may be used alone or with usual substances, for example phosphates, alka line carbonates and silicates as washing agents, cleaning agents or as textile-finishing agents.
  • the acid esters may also be transformed into other acid esters by ester-radical exchange or into neutral esters by heating them, preferably with high-molecular alcohols and, necessary, in the presence of suitable esterification catalysts.
  • polybasic esters of acyl-phosphorous acids produced from the halides of diand polycarboxylic acids in accordance with the present invention may also be reacted with polyvalent alcohols to form acid or also neutral polyesters of varying molecular size.
  • Example vI 29.2 gm. of the residue were stirred with a solution of to s. s daei asa a 7 3 4 gm. sodium hydroxide in 1.4 liters water. foaming, turbid solution, similar to a soap solution, was formed. From this solution the pure sodium salt of the monoethyl ester of lauroyl phosphorous acid was obtained in a solid form by salt-ing out with sodium chloride.
  • Example II A mixture of 61 gm. adipic acid dichloride and 92 gm. diethyl-phosphite was stirred for 8 hours at 90-95 C.; 40 gm. ethyl chloride distilled ofi during that time. The reaction product, the di-monoethyl ester of adipoyl phosphorous acid, was a colorless, viscous: liquid which dissolved in water to form a clear solution having an acid reaction.
  • Example III A mixture of 55.2 gm. diethyl-phosphite and 56.2 gm. benzoyl chloride was heated for 20 hours at a temperature between 85 and 95 C., accompanied by stirring; 25 gm.
  • Example IV A mixture of 19 gm. capric acid chloride and 14.5 gm. diethyl-phosphite was stirred for 8 hours at a temperature between 85 and 95 C.; 6 gm. ethyl chloride distilled'off during that time. The residue, the monoethyl ester of caproyl phosphorous acid, was a clear, colorless, moderately viscous oil which was readily soluble in dilute sodium hydroxide.
  • Example V A mixture of 81, gm. 2-ethylhexanoic acid chloride and 69 gm. diethyl phosphite was stirred for about6 hours at a temperature between 90 and 95 C. until no more ethyl chloride distilled oflf. 102 gm. of the moderately viscous residue formed thereby were heated in admixture with 112 gm. Z-ethylhexanol at 100 C. while passing a slow stream of nitrogen therethrough until a reduction in weight of 17 gm. occurred. Thereafter, the excess Z-ethylhexanol was distilled oil at a vacuum of 2.5 mm. Hg.
  • the residue had an acid number of 142 and a saponification value of 273 (calculated values for C7H15cO-PO(OH)OC3H17Z143 and 286, respectively).
  • the acid ester dissolved in dilute sodium hydroxide. The solution foamed and exhibited excellent wetting properties.
  • Example VI A mixture of 109.3 gm. lauroyl chloride and 97 gm. dibutyl phosphite was heated to 95 C. while passing nitrogen therethrough; the butyl chloride formed thereby was trapped in a condenser. After about 20 hours no more butyl chloride split E. The reduction in weight of the reaction mixture was 43.5 gm. The residue was a viscous, almost colorless oil. The phosphorus and carbon content of the reaction product corresponded to the formula The chlorine content was smaller than 0.1%. The acid number was 182l86 (calculated 175) and the saponification value was 355-363 (calculated 350).
  • Example VII For the cleaning of foodstuff containers, preferably of metal there is excellently suited a product of the following composition: V V 30% by weight trisodium phosphate (12 H 0).
  • Example VIII 50 parts trisodium phosphate 20 parts sodium tripolyphosphate 10 parts sodium sulfate 20 parts acid ester, obtained as described in Example I, paragraph 1 are mixed. The product obtained in this manner after dissolving in water (about 10 grams per liter) is an excellent dishwashing composition.
  • Example IX A cleaning agent of similar quality is obtained, if in the above (Example VIII) indicated combination, the acid ester is replaced by 20 parts of the sodium salt of the acid ester, which is described inExample I, paragraph 2.
  • Example X An excellent metal cleaning agent is obtained by preparing a 2% aqueous solution of a mixture of the fol lowing composition:
  • Example II obtained as described in Example II 50 parts sodium sulfate 24 parts sodium pyrophosphate (Na H P O 1 part 2-mercaptobenzthiazol.
  • the process of producing acid esters of acyl-phosphorous acid which comprises heating a mixture of an organic carboxylic acid halide and a di-lower alkyl phosphite in a ratio of 1 mol di-lower alkyl phosphite per -CO-halide group in the carboxylic acid halide to a temperature between 50 and 150 C., and removing the lower alkyl halide from the reaction mixture.
  • the process of producing the monoethyl ester of caproyl phosphorous acid which comprises heating a mixture of equimolar amounts of capn'c acid chloride and diethyl-phosphite to a temperature between 85 and 95 C., and removing the ethyl chloride formed thereby from the reaction mixture.
  • the process of producing the monoethyl ester of Z-ethylhexanoyl phosphorous acid which comprises heating a mixture of equimolar amounts of Z-ethylhexanoic acid chloride and diethyl-phosphite to a temperature between 90 and 95 C., and removing the ethyl chloride formed thereby from the reaction mixture.
  • R is an alkyl radical
  • R" is selected from the group consisting of monoand di-valent saturated aliphatic and aromatic hydrocarbon radicals containing 1 to 7 carbon atoms and the radicals of saturated monovalent higher fatty acids, and the alkali metal salts thereof.
  • Acid esters of acyl-phosphorous acids having a structural formula selected from the group consisting of and A OR

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
US657496A 1956-05-08 1957-05-07 Acid esters of acyl-phosphorous acids and method of making the same Expired - Lifetime US2900408A (en)

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Application Number Priority Date Filing Date Title
DEH26995A DE1010965B (de) 1956-05-08 1956-05-08 Verfahren zur Herstellung von sauren Estern der Acylphosphonsaeuren bzw. ihrer Salze

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3012054A (en) * 1960-03-18 1961-12-05 Dow Chemical Co Tetraalkyl esters of diphosphonates
US3118876A (en) * 1958-07-26 1964-01-21 Takeda Pharmaceutical Process for preparing glycoside phosphates
US3214454A (en) * 1958-09-06 1965-10-26 Henkel & Compagnie G M B H Process of forming metal ion complexes
US3324202A (en) * 1963-07-09 1967-06-06 Fmc Corp Phosphorus-containing polyols
US3378610A (en) * 1964-11-18 1968-04-16 Chemagro Corp Phenoxyacetyl phosphonates
US3400148A (en) * 1965-09-23 1968-09-03 Procter & Gamble Phosphonate compounds
US3676532A (en) * 1969-11-21 1972-07-11 Olin Corp Alpha-(dialkoxyphosphinyl)aryl methyl dialkyl phosphates
US3899496A (en) * 1970-10-06 1975-08-12 Henkel & Cie Gmbh Production of 1-aminoalkane-1,1-diphosphonic acids
US3940436A (en) * 1970-04-13 1976-02-24 Monsanto Company Substituted ethane diphosphonic acids and salts and esters thereof
US3944599A (en) * 1970-04-13 1976-03-16 Monsanto Company Substituted ethane diphosphonic acids and salts
US3957858A (en) * 1970-04-13 1976-05-18 Monsanto Company Substituted ethane diphosphonic acids and salts and esters thereof
US4339443A (en) * 1978-09-22 1982-07-13 Fbc Limited Compounds and compositions
US4348332A (en) * 1980-10-23 1982-09-07 Bayer Aktiengesellschaft Phosphonoformaldehyde, a process for its preparation and its use as an intermediate product for the preparation of medicaments
US4911887A (en) * 1988-11-09 1990-03-27 W. R. Grace & Co.-Conn. Phosphonic acid compounds and the preparation and use thereof
US4981648A (en) * 1988-11-09 1991-01-01 W. R. Grace & Co.-Conn. Inhibiting corrosion in aqueous systems
US5017306A (en) * 1988-11-09 1991-05-21 W. R. Grace & Co.-Conn. Corrosion inhibitor
US5266722A (en) * 1988-11-09 1993-11-30 W. R. Grace & Co.-Conn. Polyether bis-phosphonic acid compounds
US5410060A (en) * 1992-12-05 1995-04-25 Basf Aktiengesellschaft Process for preparation of arenebisphosphine oxides

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL132418C (de) * 1962-04-13
DE2965566D1 (en) * 1978-07-14 1983-07-07 Basf Ag Acylphosphinoxide compounds, their preparation and their use
FR2489711A1 (fr) * 1980-04-21 1982-03-12 Minemet Rech Sa Compositions echangeuses de cations metalliques
IL91362A0 (en) * 1989-08-20 1990-03-19 Yissum Res Dev Co Bisphosphonates,process for preparing them and pharmaceutical compositions containing them
US5196409A (en) * 1989-08-20 1993-03-23 Yissum, Research Development Company Of The Hebrew University Of Jerusalem Bisphosphonates, pharmaceutical compositions, and process for the treatment of irregularities in calcium metabolism
DE4033215A1 (de) * 1990-10-19 1992-04-23 Hoechst Ag Acyl-(2'-hydroxybiphenyl-2-yl)-phosphinsaeuresalze, ihre herstellung und verwendung

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2491920A (en) * 1946-05-16 1949-12-20 Du Pont Diesters of 1-ketophosphonic acids
US2629731A (en) * 1951-03-07 1953-02-24 Shell Dev Esters of phosphonoformic acids and polyhydric alcohols
US2719167A (en) * 1953-04-13 1955-09-27 Ciba Ltd Compounds containing phosphorus and process therefor

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2491920A (en) * 1946-05-16 1949-12-20 Du Pont Diesters of 1-ketophosphonic acids
US2629731A (en) * 1951-03-07 1953-02-24 Shell Dev Esters of phosphonoformic acids and polyhydric alcohols
US2719167A (en) * 1953-04-13 1955-09-27 Ciba Ltd Compounds containing phosphorus and process therefor

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3118876A (en) * 1958-07-26 1964-01-21 Takeda Pharmaceutical Process for preparing glycoside phosphates
US3214454A (en) * 1958-09-06 1965-10-26 Henkel & Compagnie G M B H Process of forming metal ion complexes
US3012054A (en) * 1960-03-18 1961-12-05 Dow Chemical Co Tetraalkyl esters of diphosphonates
US3324202A (en) * 1963-07-09 1967-06-06 Fmc Corp Phosphorus-containing polyols
US3378610A (en) * 1964-11-18 1968-04-16 Chemagro Corp Phenoxyacetyl phosphonates
US3400148A (en) * 1965-09-23 1968-09-03 Procter & Gamble Phosphonate compounds
US3676532A (en) * 1969-11-21 1972-07-11 Olin Corp Alpha-(dialkoxyphosphinyl)aryl methyl dialkyl phosphates
US3940436A (en) * 1970-04-13 1976-02-24 Monsanto Company Substituted ethane diphosphonic acids and salts and esters thereof
US3944599A (en) * 1970-04-13 1976-03-16 Monsanto Company Substituted ethane diphosphonic acids and salts
US3957858A (en) * 1970-04-13 1976-05-18 Monsanto Company Substituted ethane diphosphonic acids and salts and esters thereof
US3899496A (en) * 1970-10-06 1975-08-12 Henkel & Cie Gmbh Production of 1-aminoalkane-1,1-diphosphonic acids
US4339443A (en) * 1978-09-22 1982-07-13 Fbc Limited Compounds and compositions
US4348332A (en) * 1980-10-23 1982-09-07 Bayer Aktiengesellschaft Phosphonoformaldehyde, a process for its preparation and its use as an intermediate product for the preparation of medicaments
US4911887A (en) * 1988-11-09 1990-03-27 W. R. Grace & Co.-Conn. Phosphonic acid compounds and the preparation and use thereof
US4981648A (en) * 1988-11-09 1991-01-01 W. R. Grace & Co.-Conn. Inhibiting corrosion in aqueous systems
US5017306A (en) * 1988-11-09 1991-05-21 W. R. Grace & Co.-Conn. Corrosion inhibitor
US5266722A (en) * 1988-11-09 1993-11-30 W. R. Grace & Co.-Conn. Polyether bis-phosphonic acid compounds
US5312953A (en) * 1988-11-09 1994-05-17 W. R. Grace & Co.-Conn. Polyether bis-phosphonic acid compounds
US5410060A (en) * 1992-12-05 1995-04-25 Basf Aktiengesellschaft Process for preparation of arenebisphosphine oxides

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DE1010965B (de) 1957-06-27

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