US3138629A - Process for making an omicron-higher alkyl omicron-methyl methanephosphonate - Google Patents

Process for making an omicron-higher alkyl omicron-methyl methanephosphonate Download PDF

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US3138629A
US3138629A US83612A US8361261A US3138629A US 3138629 A US3138629 A US 3138629A US 83612 A US83612 A US 83612A US 8361261 A US8361261 A US 8361261A US 3138629 A US3138629 A US 3138629A
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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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric 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
    • C07F9/28—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
    • 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
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents

Definitions

  • This invention relates to new surface active compounds and to new processes for preparing such compounds. More particularly the new compounds to which this invention relates are certain new phosphonate and phosphate esters, which in turn are commonly classed as pentavalent organophosphorous esters.
  • a primary object of the invention is to make available new surface active compounds which can be prepared from available sources and which are especially useful in hard water because they are not precipitated by the mineral constituents thereof and because their efficiency is not impaired by hard Water.
  • the new compounds of this invention are of the general formula where R is an alkyl or alkoxy radical having from 1 to about 3 carbon atoms, R" is an alkyl radical having from 1 to about 3 carbon atoms, and R is an alkyl or alkenyl radical having from about 12 to about 18 carbon atoms. It will be noted that where R is an alkyl radical the compounds are phosphonate esters; whereas, where R is an alkoxy radical the compounds are phosphate esters.
  • this invention regards methyldodecyl methylphosphonate CHsO and dimethyldodecyl phosphate CHQO O Patented June 23, 1964 phate compounds will be as is illustrated in the preceding paragraph; that is, the appropriate nomenclature describing those alkyl or alkenyl radicals shown in the formulae as being attached directly to the phosphorus atom is Written as one word with the parent term "phosphonate, and the appropriate nomenclature describing those alkyl or allcenyl radicals shown as being attached to the phosphorus atom by an oxygen atom is written apart from and preceding the appropriate parent term.
  • the process for preparing the new phosphonate and phosphate esters comprises the steps of: reacting a compound of the general formula RIIO R!!! where R is an alkyl or alkoxy radical having from 1 to about 3 carbon atoms and R" and R" are alkyl radicals having from 1 to about 3 carbon atoms, with an alkylating agent of the general formula RX, where R is an alkyl or alkenyl radical having from about 12 to about 18 carbon atoms and X is a bromide, iodide or acetate radical; and separating the desired compound prepared, which compound is of the general formula R' ⁇ /O P/ RO ⁇ OR where R, R and R are as defined above, from the reac-, tion by-products.
  • R' ⁇ /O P/ RO ⁇ OR where R, R and R are as defined above
  • R, R, R and R are as defined above.
  • molar ratio of organophosphorus ester to alkylating agent employed in the process of this invention is preferably at least 1:1.
  • a higher molar ratio can be used if desired, because there is no criticality with respect to the top limit except for economic considerations.
  • the conditions of the general reaction comprise: heating the reactants at a temperature within the range of from about C. to about 250 C. and sufficient to initiate the reaction; at a pressure suflicient to maintain the reactants in a substantially liquid state; and for from about 10 to about 50 hours and sufficient to form the compounds of this invention.
  • reactants employed in this invention i.e., the particular phosphonates, phosphates and alkylating agents,
  • phosphates can be prepared by reacting phosphorus oxycholride and an alcohol in the presence of a tertiary amine;
  • the halide alkylating agents can be formed by radical initiated addition of hydrogen halide (HX) to l-olefins having the appropriate long carbon chain or by reacting an alcohol having the appropriate long carbon chain with hydrogen halide (HX);
  • the acetate alkylating agents can be obtained by reacting alcohols having the appropriate long carbon chain with an acetylating agent, such as acetyl chloride or acetic anhydride.
  • the aforementioned bromide, iodide or acetate alkylating agents are suitable for use in the process of the invention. However for various reasons the use of certain of these agents is preferred. Because the halide alkylating agents provide larger product yields and do not require the utilization of an autoclave or similar device to obtain a substantial yield, their use is preferable to that of the acetate alkylating agents. Furthermore, of the suitable halide alkylating agents, alkyl bromide is preferred because the unreacted alkyl bromide is easier to separate from the reaction products than is the unreacted alkyl iodide.
  • the reactants are heated at a temperature within the range of from about 160 C. to about 250 C. for from about to about 50 hours.
  • acetate alkylating agents employed in this invention tend to volatilize at temperatures approaching 250 C., it is necessary that the reaction be run under a pressure sufficient to keep the reactants substantially in a liquid state. A preferable procedure is to conduct the reaction in an autoclave to avoid the loss of volatile components. 7
  • the period of time during which the reactants are heated be within the range of from about to about 25 hours.
  • the iodide alkylating agents are more reactive than the other alkylating agents used in the reaction. Therefore, when the iodide alkylating agents are employed it is desirable for the purpose of reducing by-product formation to react the starting materials for from about 10 to about hours.
  • the acetate alkylating agents be employed the time during which the reactants are heated be within the range of from about 15 to about hours. 7
  • Example I Methyldodecyl methylphosphonate was prepared as follows. Equimolar amounts (0.1 mole) of dodecyl bromide and dimethyl methylphosphonate were placed in a 3-neck flask. The flask was fitted with a thermometer, a condenser and a nitrogen inlet. During the reaction a slight positive nitrogen pressure l-5 mm. Hg) was maintained. The flask containing the reactants was heated in an oil bath for 16 hours at 185 C. and then for 3 hours at 205 C.
  • the methyldodecyl methylphosphonate prepared was separated from the unreacted starting materials and from the didodecyl methylphosphonate which was formed as a by-product of the reaction by vacuum distillation.
  • the yield of methyldodecyl methylphosphonate was 38% of theoretical, based on the amount of dodecyl bromide employed.
  • Hexadecyl bromide can be substituted for dodecyl bromide in the above example to form methyl hexadecyl methylphosphonate, which ester has surface active properties.
  • Example II 0.25 mole of dodecyl bromide was reacted with 0.49 mole of diethyl ethylphosphonate according to the process described in Example I, with the exception that the reactants were heated for 20 hours at 200 C.
  • the yield of the ethyldodecyl ethylphosphonate formed after separation by vacuum distillation from the unreacted starting materials and from the didodecyl ethyl phosphonate which was formed as a by-product of the reaction was 58% of theoretical, based on the amount of dodecyl bromide employed.
  • the ethyl dodecyl ethylphosphonate was found to have surface active properties.
  • Hexadecyl bromide can be substituted for dodecyl bromide in the above example to form ethylhexadecyl ethylphosphonate, which ester has surface active properties.
  • Example Ill Equimolar amounts (0.2 mole) of dodecyl iodide and dimethyl methylphosphonate were reacted according to the process described in Example I, with the exception that the reactants were heated for 1 hour at C. and then for 19 hours at C.
  • the yield of the methyldodecyl methylphosphonate obtained after separation by vacuum distillation from the unreacted starting materials and from the didodecyl methylphosphonate which was formed as a by-product of the reaction was 34% of theoretical, based on the amount of dodecyl iodide'used.
  • the methyldodecyl methylphosphonate was found to have surface active properties.
  • Hexadecyl iodide or hexadecyl bromide can be substituted for dodecyl iodide in the above example to form methylhexadecyl methylphosphonate, which ester has surface active properties.
  • Dimethyldodecyl phosphate was prepared by reacting 0.25 mole of dodecyl bromide with 0.5 mole of trimethyl phosphate according to the process described in Example I, with the exception that the reactants were heated for 4 hours at 195 C. and then for 14 hours at 215 C.
  • the yield of dimethyldodecyl phosphate after separation by vacuum distillation from the unreacted starting materials and from the methyldidodecyl phosphate which was formed as a by-product of the reaction was 54% of theoretical, based on the amount of dodecyl bromide employed.
  • the dimethyldodecyl phosphate obtained was then tested for surface active properties by the Harkins and Jordan method described in Example I. The results of the test is shown in tabular form below; the readings being convertible into a dynes/ cm. figure by multiplying by 1.07:
  • Dimethylpropyl thosphate can be substituted for trimethyl phosphate in the above example to form an ester which has surface active properties.
  • Example V 0.25 mole of dodecyl bromide was heated with 0.5 mole of triethyl phosphate for 4 hours at 205 C. and then for 6 hours at 215 C. using the process described in Example I.
  • the yield of diethyldoceyl phosphate after separation by vacuum distillation from the unreacted starting materials and from the ethyldidodecyl phosphate which was formed as a by-product of the reaction was 63% of theoretical, based on the amount of dodecyl bromide employed.
  • Decease in water sruface tension Du Nouy Teusiometer caused by a Example VI Dirnethylhexadecyl phosphate was prepared by heating 0.2 mole of hexadecyl iodide with 0.8 mole of trimethyl phosphate for hours at 190 C., according to: the process described in Example I.
  • the yield of dimethylhexadecyl phosphate after separation by vacuum distillation from the unreacted starting materials and from the methyldihexadecyl phosphate which was formed as a by-product of the reaction was 55% of theoretical, based on the amount of hexadecyl iodide employed.
  • the dimethylhexadecyl phosphate was found to have surface active properties.
  • Dodecenyl bromide or hexadecenyl iodide can be substituted in the above example to form esters which have surface active properties.
  • Example VII Equimolar amounts (0.3 mole) of dodecyl acetate and dimethyl methylphosphonate were sealed in a glass lined autoclave. The reactants were then heated in the autoclave for 18 hours at a temperature of 250 C. The methyldodecyl methylphosphonate prepared was separated by vacuum distillation from the starting materials and from the didodecyl methylphosphonate which was formed as a by-product of the reaction. The yield of methyldodecyl methylphosphonate after separation by vacuum distillation from the unreacted starting materials and from the diodecyl methylphosphonate which was formed as a by-product of the reaction was 28% of theoretical, based on the amount of dodecyl acetate employed. The methyldodecyl methylphosphonate was: found to have surface active properties.
  • Example VIII Equimolar amounts (0.15 mole) of dodecyl acetate and dimethyl methylphosphonate were reacted according to the process described in Example VII, with the exception that the reactants were heated for 48 hours.
  • the yield of methyldodecyl methylphosphonate formed after separation by vacuum distillation from the unreacted starting materials and from the didodecyl methylphosphonate which was formed as a by-product of the reaction was 15% of theoretical, based on the amount of dodecyl acetate employed.
  • the methyldodecyl methylphosphonate was found to have surface active properties.
  • a process for preparing mono-higher alkyl phosphonate ester compound of the general formula where R and R are each methyl and R is alkyl having 12 carbon atoms consisting essentially of reacting an organophosphorous ester compound of the general formula where R and R" are each methyl, and R' is alkyl having from 1 to about 3 carbon atoms, with an alkylating agent of the general formula RX, where R is alkyl having 12 carbon atoms, and X is bromide the molar ratio of said organophosphorous ester reactant to said alkylating agent being from 1:1 to about 4:1, at a temperature within the range of from about 180 C. to about 220 C. for from about 15 to about 25 hours under substantially atmospheric pressure said reaction being a purely thermal reaction, and thereafter, recovering the mono-higher alkyl phosphonate ester reaction product.
  • a process for preparing mono-higher alkyl phos phonate ester compound of the general formula where R and R" are each methyl and R is alkyl having 12 carbon atoms consisting essentially of reacting an organophosphorous ester compound of the general formula i RI O RIII where R and R" are each methyl, and R is alkyl having from 1 to about 3 carbon atoms, with an alkylating agent of the general formula RX, where R is alkyl having 12 carbon atoms and X is iodide the molar ratio of said orgahophosphorous ester reactant to said alkylating agent being from 1:1 to about 4: 1, at a temperature within the range of about 160 C. to about 200 C., for from about 10 to about 20 hours under substantially atmospheric pressure said reaction being a purely thermal reaction, and, thereafter recovering the mono-higher alkyl phosphonate ester reaction product.

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Description

United States Patent 3,138,629 PROCESS FOR MAKING AN O-HIGHER ALKYL O-METHYL METHANEPHOSPHONATE Robert G. Laughlin, Cincinnati, Ohio, assignor to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio t No Drawing. Filed Jan. 19, 1961, Ser. No. 83,612
Claims. (Cl. 260-461) This invention relates to new surface active compounds and to new processes for preparing such compounds. More particularly the new compounds to which this invention relates are certain new phosphonate and phosphate esters, which in turn are commonly classed as pentavalent organophosphorous esters.
A primary object of the invention is to make available new surface active compounds which can be prepared from available sources and which are especially useful in hard water because they are not precipitated by the mineral constituents thereof and because their efficiency is not impaired by hard Water. Other objects will become apparent in the description which follows.
The new compounds of this invention are of the general formula where R is an alkyl or alkoxy radical having from 1 to about 3 carbon atoms, R" is an alkyl radical having from 1 to about 3 carbon atoms, and R is an alkyl or alkenyl radical having from about 12 to about 18 carbon atoms. It will be noted that where R is an alkyl radical the compounds are phosphonate esters; whereas, where R is an alkoxy radical the compounds are phosphate esters.
All of the compounds represented by the above general formula demonstrate surface active properties. However, it has been found that as the chain length of R and R increases, R remaining constant, surface activity decreases. Therefore it is desirable that the carbon chains represented by R and R contain not more than 3 carbon atoms. Preferred compounds are those in which R is an alkyl radical having 1 carbon atom, CH or an alkoxy radical having 1 carbon atom, CH O, and R is an alkyl radical having 1 carbon atom, CH Moreover, it has been discovered that optimum efiicacy of these compounds as surfactants in aqueous solution is obtained when R is a saturated alkyl radical having about 12 carbon atoms. In view of the aforementioned discoveries, this invention regards methyldodecyl methylphosphonate CHsO and dimethyldodecyl phosphate CHQO O Patented June 23, 1964 phate compounds will be as is ilustrated in the preceding paragraph; that is, the appropriate nomenclature describing those alkyl or alkenyl radicals shown in the formulae as being attached directly to the phosphorus atom is Written as one word with the parent term "phosphonate, and the appropriate nomenclature describing those alkyl or allcenyl radicals shown as being attached to the phosphorus atom by an oxygen atom is written apart from and preceding the appropriate parent term.
Briefly and broadly, the process for preparing the new phosphonate and phosphate esters comprises the steps of: reacting a compound of the general formula RIIO R!!! where R is an alkyl or alkoxy radical having from 1 to about 3 carbon atoms and R" and R" are alkyl radicals having from 1 to about 3 carbon atoms, with an alkylating agent of the general formula RX, where R is an alkyl or alkenyl radical having from about 12 to about 18 carbon atoms and X is a bromide, iodide or acetate radical; and separating the desired compound prepared, which compound is of the general formula R'\ /O P/ RO \OR where R, R and R are as defined above, from the reac-, tion by-products. These by-products are in the main of the general formulae ing made to draw a balance between reactants and reaction products:
where R, R, R and R are as defined above.
With regard to the molar ratio of organophosphorus ester to alkylating agent employed in the process of this invention such ratio is preferably at least 1:1. A higher molar ratio can be used if desired, because there is no criticality with respect to the top limit except for economic considerations.
The conditions of the general reaction comprise: heating the reactants at a temperature within the range of from about C. to about 250 C. and sufficient to initiate the reaction; at a pressure suflicient to maintain the reactants in a substantially liquid state; and for from about 10 to about 50 hours and sufficient to form the compounds of this invention.
The reactants employed in this invention, i.e., the particular phosphonates, phosphates and alkylating agents,
are readily obtained by various methods well known in the art. For example: the Michaelis-Arbuzov reaction forms phosphonates by reacting a phosphite with an alkyl halide, as described by G. M. Kosolapoff in Journal of the American Chemical Society, vol. 66, page 109 (1944); phosphates can be prepared by reacting phosphorus oxycholride and an alcohol in the presence of a tertiary amine; the halide alkylating agents can be formed by radical initiated addition of hydrogen halide (HX) to l-olefins having the appropriate long carbon chain or by reacting an alcohol having the appropriate long carbon chain with hydrogen halide (HX); and the acetate alkylating agents can be obtained by reacting alcohols having the appropriate long carbon chain with an acetylating agent, such as acetyl chloride or acetic anhydride.
It should be recognized that regardless of whether the new surfactant desired is to be a phosphonate ester or a phosphate ester the aforementioned bromide, iodide or acetate alkylating agents are suitable for use in the process of the invention. However for various reasons the use of certain of these agents is preferred. Because the halide alkylating agents provide larger product yields and do not require the utilization of an autoclave or similar device to obtain a substantial yield, their use is preferable to that of the acetate alkylating agents. Furthermore, of the suitable halide alkylating agents, alkyl bromide is preferred because the unreacted alkyl bromide is easier to separate from the reaction products than is the unreacted alkyl iodide.
As mentioned hereinbefore in connection with the conditions applicable to the general reaction of the invention, the reactants are heated at a temperature within the range of from about 160 C. to about 250 C. for from about to about 50 hours.
In this regard it has been found that various portions of this temperature range provide the best results depending on the type of alkylating agent employed, roughly as follows: because of the relatively high reactivity of iodide alkylating agents, they function best when the temperature is maintained within the range of from about 160 C. to about 200 C.; the acetate alkylating agents function best when the temperature is maintained within the range of from about 220 C. to about 250 C.; and the bromide alkylating agents function best when the temperature is maintained within the range of from about 180 C. to about 220 C. Since the acetate alkylating agents employed in this invention tend to volatilize at temperatures approaching 250 C., it is necessary that the reaction be run under a pressure sufficient to keep the reactants substantially in a liquid state. A preferable procedure is to conduct the reaction in an autoclave to avoid the loss of volatile components. 7
Turning next to a consideration of the preferred period of time, in terms of hours, during which the reactants should be heated, it is to be noted that when the bromide alkylating agents are employed it is desirable that the period of time during which the reactants are heated be within the range of from about to about 25 hours. As noted above, the iodide alkylating agents are more reactive than the other alkylating agents used in the reaction. Therefore, when the iodide alkylating agents are employed it is desirable for the purpose of reducing by-product formation to react the starting materials for from about 10 to about hours. Moreover, it is preferable that when the acetate alkylating agents are employed the time during which the reactants are heated be within the range of from about 15 to about hours. 7
The following examples are illustrative of the invention. All materials were initially at room temperature; and the temperatures referred to in these examples are reaction temperatures. Also illustrated by the following examples is the preferred molar ratio of the organophosphorous ester reactant and the alkylating agent which is 1:1 to about'4zl.
Example I Methyldodecyl methylphosphonate was prepared as follows. Equimolar amounts (0.1 mole) of dodecyl bromide and dimethyl methylphosphonate were placed in a 3-neck flask. The flask was fitted with a thermometer, a condenser and a nitrogen inlet. During the reaction a slight positive nitrogen pressure l-5 mm. Hg) was maintained. The flask containing the reactants was heated in an oil bath for 16 hours at 185 C. and then for 3 hours at 205 C. The methyldodecyl methylphosphonate prepared was separated from the unreacted starting materials and from the didodecyl methylphosphonate which was formed as a by-product of the reaction by vacuum distillation. The yield of methyldodecyl methylphosphonate was 38% of theoretical, based on the amount of dodecyl bromide employed.
Employing the method of Harkins and Jordan as set forth in J. Am. Chem. Soc., vol. 52, p. 1751 (1930), which method utilizes a Du Nouy Surface Tensiometer, it was established that the methyldodecyl methylphosphonate prepared above possesses surface active properties. The result of this test is shown in tabular form below; the readings being convertible into a dynes/cm. figure by multiplying by 1.07:
Hexadecyl bromide can be substituted for dodecyl bromide in the above example to form methyl hexadecyl methylphosphonate, which ester has surface active properties.
Example II 0.25 mole of dodecyl bromide was reacted with 0.49 mole of diethyl ethylphosphonate according to the process described in Example I, with the exception that the reactants were heated for 20 hours at 200 C. The yield of the ethyldodecyl ethylphosphonate formed after separation by vacuum distillation from the unreacted starting materials and from the didodecyl ethyl phosphonate which was formed as a by-product of the reaction was 58% of theoretical, based on the amount of dodecyl bromide employed. The ethyl dodecyl ethylphosphonate was found to have surface active properties.
Hexadecyl bromide can be substituted for dodecyl bromide in the above example to form ethylhexadecyl ethylphosphonate, which ester has surface active properties.
Example Ill Equimolar amounts (0.2 mole) of dodecyl iodide and dimethyl methylphosphonate were reacted according to the process described in Example I, with the exception that the reactants were heated for 1 hour at C. and then for 19 hours at C. The yield of the methyldodecyl methylphosphonate obtained after separation by vacuum distillation from the unreacted starting materials and from the didodecyl methylphosphonate which was formed as a by-product of the reaction was 34% of theoretical, based on the amount of dodecyl iodide'used. The methyldodecyl methylphosphonate was found to have surface active properties.
Hexadecyl iodide or hexadecyl bromide can be substituted for dodecyl iodide in the above example to form methylhexadecyl methylphosphonate, which ester has surface active properties.
Dimethyldodecyl phosphate was prepared by reacting 0.25 mole of dodecyl bromide with 0.5 mole of trimethyl phosphate according to the process described in Example I, with the exception that the reactants were heated for 4 hours at 195 C. and then for 14 hours at 215 C. The yield of dimethyldodecyl phosphate after separation by vacuum distillation from the unreacted starting materials and from the methyldidodecyl phosphate which was formed as a by-product of the reaction was 54% of theoretical, based on the amount of dodecyl bromide employed.
The dimethyldodecyl phosphate obtained was then tested for surface active properties by the Harkins and Jordan method described in Example I. The results of the test is shown in tabular form below; the readings being convertible into a dynes/ cm. figure by multiplying by 1.07:
Dimethylpropyl thosphate can be substituted for trimethyl phosphate in the above example to form an ester which has surface active properties.
Example V 0.25 mole of dodecyl bromide was heated with 0.5 mole of triethyl phosphate for 4 hours at 205 C. and then for 6 hours at 215 C. using the process described in Example I. The yield of diethyldoceyl phosphate after separation by vacuum distillation from the unreacted starting materials and from the ethyldidodecyl phosphate which was formed as a by-product of the reaction was 63% of theoretical, based on the amount of dodecyl bromide employed.
Employing the Harkins and Jordan method, described in Example I, showed the diethyldodecyl phosphate produced by this example to be a surface active agent. The result of this test is shown in tabular form below; the readings being convertible into a dynes/cm. figure by multiplying by 1.07:
Decease in water sruface tension Du Nouy Teusiometer caused by a Example VI Dirnethylhexadecyl phosphate was prepared by heating 0.2 mole of hexadecyl iodide with 0.8 mole of trimethyl phosphate for hours at 190 C., according to: the process described in Example I. The yield of dimethylhexadecyl phosphate after separation by vacuum distillation from the unreacted starting materials and from the methyldihexadecyl phosphate which was formed as a by-product of the reaction was 55% of theoretical, based on the amount of hexadecyl iodide employed. The dimethylhexadecyl phosphate was found to have surface active properties.
Dodecenyl bromide or hexadecenyl iodide can be substituted in the above example to form esters which have surface active properties.
6 Example VII Equimolar amounts (0.3 mole) of dodecyl acetate and dimethyl methylphosphonate were sealed in a glass lined autoclave. The reactants were then heated in the autoclave for 18 hours at a temperature of 250 C. The methyldodecyl methylphosphonate prepared was separated by vacuum distillation from the starting materials and from the didodecyl methylphosphonate which was formed as a by-product of the reaction. The yield of methyldodecyl methylphosphonate after separation by vacuum distillation from the unreacted starting materials and from the diodecyl methylphosphonate which was formed as a by-product of the reaction was 28% of theoretical, based on the amount of dodecyl acetate employed. The methyldodecyl methylphosphonate was: found to have surface active properties.
Example VIII Equimolar amounts (0.15 mole) of dodecyl acetate and dimethyl methylphosphonate were reacted according to the process described in Example VII, with the exception that the reactants were heated for 48 hours. The yield of methyldodecyl methylphosphonate formed after separation by vacuum distillation from the unreacted starting materials and from the didodecyl methylphosphonate which was formed as a by-product of the reaction was 15% of theoretical, based on the amount of dodecyl acetate employed. The methyldodecyl methylphosphonate was found to have surface active properties.
What is claimed is: V
1. A process for preparing mono-higher alkyl phosphonate ester compound of the general formula where R and R are each methyl and R is alkyl having 12 carbon atoms, consisting essentially of reacting an organophosphorous ester compound of the general formula where R and R" are each methyl, and R' is alkyl having from 1 to about 3 carbon atoms, with an alkylating agent of the general formula RX, where R is alkyl having 12 carbon atoms, and X is bromide the molar ratio of said organophosphorous ester reactant to said alkylating agent being from 1:1 to about 4:1, at a temperature within the range of from about 180 C. to about 220 C. for from about 15 to about 25 hours under substantially atmospheric pressure said reaction being a purely thermal reaction, and thereafter, recovering the mono-higher alkyl phosphonate ester reaction product.
2. A process for preparing mono-higher alkyl phos phonate ester compound of the general formula where R and R" are each methyl and R is alkyl having 12 carbon atoms consisting essentially of reacting an organophosphorous ester compound of the general formula i RI O RIII where R and R" are each methyl, and R is alkyl having from 1 to about 3 carbon atoms, with an alkylating agent of the general formula RX, where R is alkyl having 12 carbon atoms and X is iodide the molar ratio of said orgahophosphorous ester reactant to said alkylating agent being from 1:1 to about 4: 1, at a temperature within the range of about 160 C. to about 200 C., for from about 10 to about 20 hours under substantially atmospheric pressure said reaction being a purely thermal reaction, and, thereafter recovering the mono-higher alkyl phosphonate ester reaction product.
References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Arbuzov et al.: Bull. Acad. Sci. U.S.S.R., Div. Chem. Sci., (English Trans.), pp. 787-795, 1952.
Burger: U.S. Atomic Energy Comm. HW-44888, Janu- 15 ary 3, 1957, pp. 1-25.

Claims (1)

1. A PROCESS FOR PREPARING MONO-HIGHER ALKYL PHOSPHONATE ESTER COMPOUND OF THE GENERAL FORMULA
US83612A 1961-01-19 1961-01-19 Process for making an omicron-higher alkyl omicron-methyl methanephosphonate Expired - Lifetime US3138629A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1230801B (en) * 1965-03-20 1966-12-22 Bayer Ag Process for the production of mixed phosphonic acid esters
US3391083A (en) * 1966-06-29 1968-07-02 Monsanto Co Surface active agents
US3887654A (en) * 1971-07-05 1975-06-03 Ciba Geigy Corp Phosphorus containing reaction products
US10066186B2 (en) 2013-04-22 2018-09-04 Basf Se Lubricating oil compositions containing a halide seal compatibility additive and a second seal compatibility additive
US10106759B2 (en) 2013-04-22 2018-10-23 Basf Se Seal compatibility additive to improve fluoropolymer seal compatibility of lubricant compositions

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2436141A (en) * 1946-03-07 1948-02-17 Du Pont Dialkyl esters of long-chain alkylphosphonates
US2552325A (en) * 1947-02-24 1951-05-08 Monsanto Chemicals Diethyl octyl phosphates
US2589326A (en) * 1949-12-21 1952-03-18 Socony Vacuum Oil Co Inc Organic phosphorus ester-p2s5 reaction products and oil compositions containing the same
US2612514A (en) * 1947-06-04 1952-09-30 Fmc Corp Production of esters of relatively strong organic and inorganic acids with aliphatic compounds having more than one carbon atom
US2875229A (en) * 1956-02-14 1959-02-24 Eastman Kodak Co Preparation of neutral mixed phosphates from trialkyl phosphates and carboxylic acid esters
US2875230A (en) * 1956-02-14 1959-02-24 Eastman Kodak Co Preparation of neutral mixed phosphates from trialkyl phosphates and alcohols
US2957931A (en) * 1949-07-28 1960-10-25 Socony Mobil Oil Co Inc Synthesis of compounds having a carbonphosphorus linkage

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2436141A (en) * 1946-03-07 1948-02-17 Du Pont Dialkyl esters of long-chain alkylphosphonates
US2552325A (en) * 1947-02-24 1951-05-08 Monsanto Chemicals Diethyl octyl phosphates
US2612514A (en) * 1947-06-04 1952-09-30 Fmc Corp Production of esters of relatively strong organic and inorganic acids with aliphatic compounds having more than one carbon atom
US2957931A (en) * 1949-07-28 1960-10-25 Socony Mobil Oil Co Inc Synthesis of compounds having a carbonphosphorus linkage
US2589326A (en) * 1949-12-21 1952-03-18 Socony Vacuum Oil Co Inc Organic phosphorus ester-p2s5 reaction products and oil compositions containing the same
US2875229A (en) * 1956-02-14 1959-02-24 Eastman Kodak Co Preparation of neutral mixed phosphates from trialkyl phosphates and carboxylic acid esters
US2875230A (en) * 1956-02-14 1959-02-24 Eastman Kodak Co Preparation of neutral mixed phosphates from trialkyl phosphates and alcohols

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1230801B (en) * 1965-03-20 1966-12-22 Bayer Ag Process for the production of mixed phosphonic acid esters
US3480701A (en) * 1965-03-20 1969-11-25 Bayer Ag Process for the production of mixed phosphonic acid esters
US3391083A (en) * 1966-06-29 1968-07-02 Monsanto Co Surface active agents
US3887654A (en) * 1971-07-05 1975-06-03 Ciba Geigy Corp Phosphorus containing reaction products
US10066186B2 (en) 2013-04-22 2018-09-04 Basf Se Lubricating oil compositions containing a halide seal compatibility additive and a second seal compatibility additive
US10106759B2 (en) 2013-04-22 2018-10-23 Basf Se Seal compatibility additive to improve fluoropolymer seal compatibility of lubricant compositions

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