Classifications

• • 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
  • C07F9/386—Polyphosphonic acids containing hydroxy substituents in the hydrocarbon radicals
• • 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
  • C07F9/4025—Esters of poly(thio)phosphonic acids
  • C07F9/404—Esters of poly(thio)phosphonic acids containing hydroxy substituents in the hydrocarbon radicals

Definitions

• the present invention relates to a new process for the production of derivatives of hydroxy methylene diphosphonic acid from the corresponding carboxylic acid. It relates more particularly to the production of said derivative from carboxylic acid which is not very soluble in water, that is to say of carboxylic acid whose number of carbons is greater than 13.
• This new process is more particularly suited to carboxylic acids whose number of carbons is greater than 15.
• one of the aims of the present invention is to provide a process making it possible to produce hydroxy-diphosphonated compounds with a clearly higher yield, in particular with respect to phosphorus III reagents, than the techniques described previously.
• Another object of the present invention is to provide a process of the above type, the by-products of which are easily recyclable.
• Another object of the present invention is to provide a process of the above type which makes it possible to obtain either the diphosphoni tetracide as corresponding, or its esters whose average composition corresponds to a diacid diester.
• a further object of the present invention is to provide a technique for purifying tetracide.
• dant comprising: a) mixing of said corresponding carboxylic acid with a reagent P III chosen from the group consisting of phosphorus tri-halides, phosphorous acid and their mixtures, the reaction mixture being kept protected from humidity; characterized by the fact that the molecular ratio (P III / RCOOH) between the reagent P III and said corresponding carboxylic acid is in the range between 13 / 12th and 18 / 12th and by the fact that it also comprises the etane: b) heating the reaction medium to a temperature between 80 and 110 ° C for a period between 3 and 20 hours approximately.
• a reagent P III chosen from the group consisting of phosphorus tri-halides, phosphorous acid and their mixtures, the reaction mixture being kept protected from humidity; characterized by the fact that the molecular ratio (P III / RCOOH) between the reagent P III and said corresponding carboxylic acid is in the range between 13 / 12th and 18 / 12th and by the fact that it also
• step a With regard to the temperature of step a), it should be noted that the reaction is exothermic at the start, probably due to the dehydration reactions which leads to the elimination of the humidity from the reaction medium and to the dehydration of the carboxyl group. This explanation is not, however, limiting. It is desirable to maintain a temperature below 110 ° C and preferably above 80 ° C. However, when no diluent is used, as will be explained later, it is difficult to obtain such temperatures as soon as the melting temperature of the corresponding carboxylic acid is higher than the above values. It is desirable for the reactions which are supposed to take place at the start of mixing to take place that the carboxylic acid is melted. Tempé Rature is preferably chosen between the melting point of the corresponding carboxylic acid and 110oC.
• a good way to achieve temperature regulation is the rate of addition of the phosphorus tri-halide.
• the speed of addition of the phosphorus tri-halide is chosen so that the temperature of the reaction mixture does not exceed 110 ° C.
• An optimal value of the ratio between the reagent P III and the carboxylic acid is around 15 / 12th ( ⁇ 10%).
• the preferred phosphorus tri-halide is phosphorus tri-chloride.
• the best are linear, branched and cyclic ethers whose boiling temperature is between 80 and 150oC, which allows a good regulation of the temperature of the reaction mixture, and preferably the sulfones, the best diluents being the substituted or unsubstituted sulfolanes.
• step b) generally takes place from half an hour to one hour after said corresponding carboxylic acid has been mixed with reagent P III, during this period the temperature of said reaction mixture being that determined either by exothermic tee of the reaction, either by the melting point of the carboxylic acid.
• the preferred heating time depends on the heating temperature chosen, which depends, as explained above, on the melting temperature of the carboxylic acid. The higher the heating temperature, the shorter the heating time and vice versa the lower the heating temperature, the longer the heating time.
• Those skilled in the art can be guided on the one hand by the conventional consideration that an increase of 10 ° C corresponds to a doubling of the kinetics and on the other hand by the fact that at 90oC a satisfactory duration is around 10 to 12 hours.
• the reaction mixture obtained as a result of the heating contains hydroxy-di-phosphonic acid only in small proportion but it also contains a certain number of condensation compounds which it is advisable to solvolyze to release the hydroxy-diphosphonic acid possibly contained.
• the method according to the present invention also comprises a following solvolysis step: c) solvolysis of said reaction mixture by heating with a solvent having a hydroxyl function.
• Solvolysis can be carried out either by alcohols, in which case an ester is obtained, or a mixture of esters, or by water, in which case the hydroxy-di-phosphonic tetracide is obtained.
• the heating is carried out by reflux in the presence of a hydrohalic acid for one to 6 hours, the concentration of hydrohalic acid being between 2 and 6 N.
• the volume ratio between said reaction mixture obtained after step b) and said aqueous halohydric acid is between 1 and 4 N.
• the solvolysis is carried out at a temperature between 110 and 120oC, preferably between 120 and 140oC.
• Solvolysis can also be carried out in a diluent. It then suffices to choose an inert diluent both with respect to the reaction mixture resulting from step b) and with respect to the alcohol used. We can use for example heavy ethers or even alcohol itself.
• the amount of alcohol used with the reaction mixture resulting from step b) is an amount greater than the stoichiometric amount necessary for the esterification of the two acid functions of the potential hydroxy-diphosphonic compound produced during the reaction, advantageously an amount greater than the sum of the stoichiometric amount necessary for the ester ification of the two acid functions of the potential hydroxy-diphosphonic compound produced during the reaction and the stoichiometric amount necessary for the ester ification of the residual carboxylic acid, preferably an amount greater than twice the sum of the stoichiometric amount necessary for the ester ification of the two acid functions of the potential hydroxy-diphosphonic compound produced during the reaction and the stoichiometric amount necessary for the esterification of the residual carboxylic acid.
• Example 1 Comparative example This example consists in reproducing the teaching of Belgian patent no 619,600, corresponding to US patent no 4,060,546, by applying the technique used by BLASER for lauric acid to stearic acid (example 5 of the patent Belgian and example 7 of the US patent). The entire technique has been repeated and there is no need to repeat it here, the only difference consisting in the replacement of lauric acid by stearic acid and the total amount of reaction mixture, since the reaction was carried out in laboratory conditions on quantities 100 times smaller, 17.06 grams of stearic acid, 5.49 grams of phosphorus trichloride and 1.08 g of water.
• nuclear magnetic resonance spectra relating to phosphorus 31 demonstrate that this sodium salt corresponds not to pure hydroxy-diphosphonic acid but to a mixture of complexes in which the pure hydroxy-disphosphonic acid is only low proportion and has some similarities with the spectra obtained on the reaction mixtures from step b), that is to say before solvolysis.
• This salt was therefore subjected to hydrolysis according to the techniques described below.
• the reaction mixture After adding 4N concentrated hydrochloric acid in an amount equal to twice the mass of the sodium salt, the heating taking place under reflux at a temperature in the region of 120-130oC, the reaction mixture is refluxed for approximately 8 hours then allowed to cool. After cooling, the phase is subjected to extraction with ether. The ethereal solution and the residual aqueous phase are recovered, then these two ptiases are subjected to an NMR examination of phosphorus 31.
• the ether phase contains essentially hydroxy-diphosphonic acid, while the aqueous phase contains only phosphorous acid. We dose the amount of phosphorus in the two phases and we see that only 0.36 g of phosphorus are involved in the form of hydroxydiphosphonic acid for an initial amount of 1.23 g, so a lower yield at 30%.
• Example 2 Comparative Example This example repeats as far as possible the conditions described in Example 1 of US Pat. No. 4,316,877 (M. A. TUNICK, columns 5 and 6) using stearic acid as the initial carboxylic acid.
• stearic acid is used to be insoluble in water but soluble in carbon tetra chloride, chloroform, ether and THF, while hydroxy diphosphonic acid originating from carboxylic acids heavy is insoluble in chloroform and soluble in THF.
• reaction mixture as described above is subjected to evaporation under vacuum to remove the last volatile materials. It is then redissolved in excess n-heptyl alcohol (200 cc of n-heptyl alcohol per 100 grams of reaction mixture after disappearance of the volatiles). The mixture is heated to reflux (120 o C) and gives an ester of hydroxy-di phosphoni acid which analysis of phosphorus and carbon corresponds to a diester however that the NMR spectrum of phosphorus 31 resembles the product obtained by esterification of purissime stearic acid and ethyl orthoformate.

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• 1983
  • 1983-08-24 CA CA000435225A patent/CA1197520A/fr not_active Expired
  • 1983-08-24 DE DE8383401701T patent/DE3370156D1/de not_active Expired
  • 1983-08-24 AT AT83401701T patent/ATE25848T1/de not_active IP Right Cessation
  • 1983-08-24 EP EP83401701A patent/EP0104974B1/fr not_active Expired
  • 1983-08-25 WO PCT/FR1983/000175 patent/WO1984000966A1/fr not_active Ceased
  • 1983-08-25 JP JP58502805A patent/JPS59501713A/ja active Granted

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