DE3232997A1 - Diphosphonic acids - Google Patents

Abstract

Compounds of the formula (I) <IMAGE> in which R denotes the alkylene radical -(CH2)n- and n = 2 to 10 or a phenylene radical and Me denotes a hydrogen atom or a cation forming a water-soluble salt. The products are excellent sequestering agents for polyvalent metal ions, such as copper ions and iron ions and also calcium ions. The products are used as corrosion and scale prevention agents and as an additive for delaying the setting of plaster and slip liquefaction agents. They can furthermore be used for tartar prevention.

Description

"Dinhosphonic Acids"

The invention relates to new diphosphonic acids which have a thiazine dioxide group contained in the molecule.

US Pat. No. 4,264,767 discloses the conversion of alpha-aminoalkanemonophosphonic acids known with divinyl sulfone in aqueous alkaline solutions. This gives monophosphonic acids, that contain a thiazine group in the molecule. These connections are among others proposed for use as stone deposits and anti-corrosion agents.

It has now been found that the new, one described below 1,4-thiazine group in the molecule contained diphosphonic acids a substantial improvement the properties, especially with regard to -the complexation-like ability have the known compounds.

The new compounds correspond to the following formula (I) where R = the alkylene radical - (CH2) n - and n = 2 to 10 or a phenylene radical and Me a hydrogen atom or a cation which forms a water-soluble salt.

The new compounds are obtained by reacting divinyl sulfone with omega-amino-hydroxyalkane-1,1 diphosphonic acids. Implementation is expedient carried out in an alkaline medium. The starting components mentioned used in molar amounts.

When the divinyl sulfone is added, an exothermic reaction takes place. The reaction is carried out at temperatures of about 25 to 500 C, and the reaction mixture leave it at this temperature for a while.

The reaction product can then be treated with ion exchangers (Acid form) can be converted into the diphosphonic acid. The yields are there over 90%.

Unless the water-soluble salts directly, such as Sodium salts, incurred, the new Dir phosphonic acids can partially or complete neutralization with inorganic compounds such as NaOH, KOH, alkali carbonates or also alkanolamines, such as monoethanolamine, diethanolamine or triethanolamine, be converted into the corresponding water-soluble salts.

The new diphosphonic acids of formula I are excellent sequestering agents for polyvalent metal ions, especially for divalent and trivalent metal ions, such as Copper and iron. They are also suitable as complexing agents for alkaline earth metal ions, in particular calcium ions, so that they are used for numerous technical applications, such as used for example in detergents and cleaning agents as well as in water treatment can be; they have a stabilizing effect on per compounds.

The new compounds are also used as a corrosion and stone build-up preventive for cooling water, especially in combination with additives known per se, such as zinc salts, orthophosphates, chromates or hydrazine hydrates, good suitable.

They are also suitable as additives to retard the setting of Gypsum and as a slip liquefier. Besides the free Acids also the sodium, potassium or ammonium salts are used.

They can also be used in oral and dental care products, to avoid the formation of tartar. to prevent tartar can besides the free phosphonic acids in these agents also include the pharmacologically harmless ones Salts; such as sodium, potassium, ammonium and substituted ammonium salts such as mono-, Find di- or triethanolammonium salts use. Both the partial salts, in which only a part of the acidic protons is replaced by other cations than the full salts can also be used.

The subject of the application is illustrated by the following examples explained without being limited to this.

Example 1 0.1 mol of the tetrasodium salt of 3-amino-1-hydroxypropane-1,1-diphosphonic acid, dissolved in 100 ml of water, were reacted at 50 ° C. with 0.1 mol of divinyl sulfone. Included the divinyl sulfone was added slowly. The implementation was exothermic and brought a temperature increase of 8 0C. The reaction mixture was another 1 hour stirred at 500C. The clear solution was used to isolate the reaction product Adjusted to pH 1 with concentrated hydrochloric acid. The diphosphonic acid which precipitates out was separated.

Analysis found: C 23.2 H 5.66 N 3.75 P 17.3 S 9.12 calcd: 23.80 4.82 3.97 17 # S6 9.07 This was also possible by adding alcohol to the reaction mixture Na4 salt of the compound can be obtained in pure form.

Analysis found: C 19.2 H 3.12 N 3.01 P 13.9 S 7.34 Na 20.5 calculated: 19.05 2.95 3.17 14.06 7.26 20.86 Example 2 Analogously to Example 1, 0.1 mol of des Tetrapotassium salt of omega-amino-alpha-hydroxyhexane-alpha, alnha-diphosphonic acid implemented.

Analysis found: C 29.8 H 6.77 N 2.97 P 15.1 S 7.98 calcd: 30.38 5.82 3.54 15.70 8.10 The compound described can also be used directly as the potassium salt can be isolated by adding a lot of it after the reaction with divinyl sulfone Acetone is precipitated.

Analysis found: C 22.1 H 3.71 N 2.30 P 11.0 S 5.70 K 28.9 calculated: 21.92 3.47 2.56 11.33 5.85 28.57 Example 3 In the usual way, analogous to Beisniel 1 0.1 mol of the tetrasodium salt of the omega-amino # -alpha-hydroxyundecanalpha, alpha-diphosphonic acid reacted in 200 ml of water and isolated in the manner described i # Example 1 Analysis found: C 38.7 H 7.22 N 3.02 P 13.5 S 6.65 Calculated: 38.71 7.10 3.01 13.33 6.88 Example 4 The basic formulations for toothpastes are as follows Suitable formulations: a.) Glycerin 60.0 parts by weight water 13.5 parts by weight sodium carboxymethyl cellulose 0.6 parts by weight of silica exerogel, 20.0 parts by weight of sodium lauryl sulfate, 2.0 parts by weight Essential oils 1.0 part by weight sweetener 0> 4 parts by weight 3- [1,4-thiazine dioxide] -N-1-hydroxypropane-1 , 1-diphosphonic acid 2.5 parts by weight b.) Glycerin 30.0 parts by weight water 18.5 parts by weight Sodium arboxymethyl cellulose 1.0 part by weight aluminum hydroxide 44.0 parts by weight sodium lauryl sulfate 1.0 part by weight of pyrogenic silica 1.5 parts by weight of essential oils 1.5 parts by weight of sweet to ff 0.5 part by weight of 3- (1,4-thiazine dioxide) -N-1-hydroxypropane-1> 1-diphosphonic acid 2.0 parts by weight The following combination is the basic recipe for mouthwashes suitable: ethyl alcohol 19.5 parts by weight glycerol 7.5 parts by weight water 70.0 parts by weight Essential oils 0.2 part by weight sodium lauryl sulfate 0.1 part by weight antiseptic (chlorothymol) 0.1 part by weight sweetener 0.1 part by weight 3- (1,4-thiazine dioxide) -N-1-hydroxypropane-1,1-diphosphonic acid 2.5 C # ew.-parts instead of the diphosphonic acids used in Example 5 (see compositions a.), b.) and c.)) can also p- (1, 4-thiazine dioxide) -N-phenylene hydroxymethanediphosphonic acid, 6- (1,4-thiazine dioxide) -N-1-hydroxyhexane-1, 1-diphosphonic acid or 11- (1,4-thiazine dioxide) -N-1-hydroxyundecane-1,1-diphosphonic acid can be used.

By regularly using the mouthwashes and / or toothpastes with A content of the above-mentioned diphosphonic acids can prevent the formation of tartar reduce significantly. The formation of hard, compact plaque is largely prevented.

Claims (3)

Claims for compounds of formula (I) where R = the alkylene radical - (CEl2) n- and n = 2 to 10 or a phenylene radical and Me = a hydrogen atom or a cation which forms a water-soluble salt. 2. Compounds of the formula (I), where Me = sodium or potassium. 3. Compounds of the formula (I), where R = an alkylene radical with 2 to 5 carbon atoms.