DE2015068C3 - - Google Patents

Description

the esters first with dilute aqueous hydrochloric acid while distilling off the liberated alcohol partially saponified and then the saponification is completed by adding concentrated hydrochloric acid.

The a-alkyl-phosphonosuccinic acids are behind dissolved in hydrochloric acid before saponification. After distilling off the hydrochloric acid in vacuo at temperatures up to The anhydrous α-alkyl-phosphonosuccinic acids are about 140 ° C that are viscous in the warmth and either crystallize in the cold or solidify glassy.

The α-substituted phosphonosuccinic acids according to the invention of formula I are characterized by an excellent ability to form complexes for alkaline earth metal ions the end. They are therefore excellent as sequestrants, e.g. B. in cleaning agents, suitable how they are used in the food industry for bottle washing. The ability to form complexes of the α-substituted phosphonosuccinic acids according to the invention is significantly higher than that of those previously used as sequestrants Phosphorus compounds. So the softening factor is which is a measure of the sequestering ability of a compound for:

Na-hexamethaphosphai has a softening factor of 100 when 10.0 ml of CaCl ₂ solution are used.

The -substituted phosphonosuccinic acids according to the invention also have the advantage that the saturation concentration of their sparingly soluble calcium salts is not achieved with the water hardness occurring in practice, d. H. no stone formation occurs; on the other hand, the saturation concentration of the poorly soluble calcium salts of the known phosphoric acid or phosphonic acid sequestering agent already achieved with the usual water hardness.

The table below shows the limit calcium concentrations (given in ° dH) for a number of Phosphoric and phosphonic acids compiled:

Compound calcium

Limit concentrations

link

Em-

hanging

factor

Hydroxyäthandäsphosphon- 10 ° i.e. was standing acid the Phosphonosuccinic acid 19 ° i.e. technology 25 nitrilotrismethylene phosphonic 24 ° i.e. acid Na hexametaphosphate 25 ° i.e.

0-phosphonobutyric acid 26

ß-phosphonopropionic acid 30

l-phosphonopropa.ii-23-di-58

carboxylic acid

Sodium hexametaphosphate 100
1,2-diphosphonosuccinic acid 100

Phosphonosuccinic acid 100

Hydroxyethane Diphosphonic Acid 280
Nitrilotrismethylene phosphonic 309
acid

was standing

the

technology

α-methylphosphonosuccinic acid

500 invention

40

The softening factor was determined as follows:

Reagents
1) soda solution

100 g CaIc. Soda p. A. are dissolved with distilled water and noticed on 1000 ml.

2) calcium chloride solution

37.92 g CaCl ₂ · H ₂ O are diluted with dist. Dissolved water and made up to 1000 ml SS

Performing the titration

100 ml of the 1% sample solution in dist. Water are adjusted to pH 13.0 with sodium hydroxide solution or HCl. 2 ml of soda solution are added. With constant stirring, the CaCl ₂ solution is allowed to drop in until a cloudiness can be seen which no longer dissolves within a minute. The calcium chloride solution was adjusted so that Na-nexametaphosphate resulted in a consumption of 10.0 ml of calcium chloride solution. The consumption of 0.1 ml CaCb solution corresponds to a softening factor of 1.

α-methylphosphono- 78 ° dH invention

succinic acid

The α-substituted phosphonosuccinic acids according to the invention can be used as free acids or in the form of their alkali or amine salts in cleaning agents, which also have the usual additives such as wetting agents, emulsifiers, defoamers, organic Builders, bleaches and disinfectants, may be used.

example 1

To the suspension of 23 g (1 mol) of sodium in 300 ml of toluene, with vigorous stirring and good Cooling at 20-25 ° C. 254 g (1 mol) of tetramethyl phosphonosuccinate added dropwise, a clear yellow solution of sodium phosphonosuccinic acid tetramethyl ester is formed in toluene.

126 g (1 mol) of dimethyl sulfate are added to this solution at 10-40 ° C. while stirring and cooling added dropwise over a period of about 25 minutes. The reaction mixture is then stirred for a further 1 hour. then the precipitated sodium monomethyl sulfate is filtered off and the filtrate by distillation in vacuo freed from the solvent up to a sump temperature of about 60 "C. The crude Ä-Methyl-phosphonosuccinic acid-tetramethyl ester fractionally distilled. Yield: 172 g (65% of Theory); B.p .: 127-130 ° C / l Torr.

The a-methyl-phosphonosuccinic acid tetramethyl ester obtained in this way is with 100 ml of dilute hydrochloric acid (2 mol HCl / liter) for 18 hours while distilling off of the methanol formed during the saponification is heated to boiling temperature. Then the saponification mixture is used 150 ml of concentrated hydrochloric acid (12 mol HCl / liter) are added and the mixture is added for a further 18 hours Heated to reflux temperature. The reaction solution is then evaporated to dryness in vacuo (maximum Sump temperature: 120 ° C) and diluted with water to a 50% solution.

Example 2

254 g (l mol) of phosphonosuccinic acid-tetramethylester be at 20-25 ⁰ C under stirring with a solution of 54 g (1 mol) of sodium methylate in 330 ml of methanol were added 5 After adding 300 ml of toluene is the solvent mixture in vacuo at 15 -25 ^C C distilled off so far that the sodium phosphonosuccinic acid tetramethyl ester just remains in solution. After adding 300 ml of toluene again and again distilling off the solvent mixture in vacuo, the sodium salt is in a virtually methanol-free toluene solution.

The solution of the thus obtained sodium-phosphonobemsteinsäure-tetramethylesters is added dropwise with stirring and cooling within 30 minutes at 20-30 ⁰ C and 140 g (l MolJTrimethylphosphat added. The reaction mixture is stirred for a further 2 hours then the precipitated sodium dimethyl phosphate is. . filtered and the filtrate by distillation in vacuo until a bottom temperature of 6O ⁰ C the solvent bef-ince Subsequently, the crude product is purified by distillation yield: 195 g; b.p. 126-131 ° C / 1 Torr..

According to the gas chromatogram, the distillate consists to 86% of methyl phosphonosuccinic acid tetramethyl ester and 10% tetramethyl phosphonosuccinate.

The distillate was heated with 400 ml of concentrated hydrochloric acid (12 mol / liter) for 24 hours at reflux, the weak acidic reaction solution is then evaporated to dryness in vacuo to diluted to a sump temperature of 120 ⁰ C and then with water to give a 50% solution .

Example 3

35

To the solution of 1 mol of sodium phosphonosuccinic acid tetramethyl ester in 200 ml of toluene, which was prepared as described in Example 1, 121 g (1 mol) of allyl bromide are added dropwise with stirring and cooling at 20-25 ° C. in the course of about 20 minutes. After the addition of allyl bromide is complete, the mixture is stirred for a further 3 hours. The precipitated sodium bromide is filtered off and the Fiitrat up to a bottom temperature of 60-7O ⁰ C door freed from the solvent by distillation in vacuo. The crude product is then distilled. Yield: 246 g (84% of theory); boiling point: 133-140 ° C./1 Torr.

According to the gas chromatogram, the product contains tetramethyl ester of 92% «-allylphosnhonosuccinic acid.

The ester is saponified in the manner indicated in Example 1

Example 4

55

To 254 g (1 mol) of tetramethyl phosphonosuccinate the solution of 27 g (0.5 Mol) sodium methylate dissolved in 180 ml of methanol added dropwise. The evaporating methanol is distilled off. After the addition of methylate has ended, the reaction mixture is stirred at 100 ° C. for 30 minutes. The reaction product is then allowed to cool to 50 ° C. and 42 ml of concentrated product are added dropwise with stirring Hydrochloric acid (12 mol HCl / liter). The sodium chloride which separates out is then filtered off. The filtrate is saponified in the manner described in Example 1. 360 g of a 50% strength aqueous solution of a are obtained 1: 1 mixture of phosphono succinic acid and α-methyl-phosphonosuccinic acid.

Example 5

A solution of 40.5 g (0.75 mol) of sodium methylate dissolved in 270 ml of methanol is added dropwise to 254 g (1 mol) of tetramethyl phosphonosuccinate at 135 ° C. with stirring and heating over the course of 30 minutes. The evaporating methanol is distilled off in a water jet vacuum during the dropwise addition. The reaction mixture is achgeriihrt for 30 minutes at 135 ⁰ C under atmospheric pressure i <. After cooling to about 50 ^° C., 63 ml (0.75 mol) of concentrated hydrochloric acid are added to the reaction product and the precipitated sodium chloride is filtered off. The filtrate is saponified in the manner described in Example 1

After concentrating the saponification solution in vacuo, 150 g of a 1: 3 mixture are obtained Phosphonosuccinic acid and v-methyl-phosphonosuccinic acid.

Example 6

In 254 g (1 mol), heated to 100 ⁰ C-phosphonosuccinic tetramethylcster be entered solid within 30 minutes at 100 ° C 27 g (0.5 mole) of sodium methoxide with stirring and cooling in portions to g per 3.5. Before each addition, it is waited until the temperature of the mixture has fallen back to 100.degree. C. After the addition has ended, the reaction mixture is stirred for a further 1 hour

The reaction mixture is worked up in the manner described in Example 5. One receives a l: l mixture of phosphonosuccinic acid and Λ-methyl-phosphonosuccinic acid.

Example! 7th

11.5 g (0.5 mol) of sodium are added in portions over the course of 1 hour to the boiling mixture of 254 g (1 mol) of tetramethyl phosphonosuccinate and 16 g of methanol. The sodium melts and reacts with your mixture. After the last addition of sodium, the mixture is stirred at 120 ^° C. for a further 1 hour.

The reaction mixture is in -1er in Example 5 Worked up described manner A 1: 1 mixture of phosphonosuccinic acid and Λ-methyl phosphonosuccinic acid.

Example 8

The conversion of tetramethyl phosphonosuccinate with sodium methylate can also be carried out continuously - and methanol vapor is used, the heating mantle is charged by a thermostat with a circulation pump with oil of 280 -310 ⁰ C with jwei metering pumps are Pho5phonobemsteinsiure-ti tr * methylester (41, l mol / h, corresp 10.46 kg / h.) and Methylate solution containing 2.8 mol of sodium diethylate / liter of methanol (20.5 mol / h -7.2 liters of solution / h) was added with vigorous stirring. The evaporating methanol is condensed in a product cooler ^{. The reaction temperature in the stainless steel reactor is 115-12O 0} C. the reaction product, a mixture of phosphonobern-

methyl stinate or its sodium salt and methyl phosphonosuccinic acid methyl ester or its sodium salt and methyl Λ-methyl phosphonosuccinate or its sodium salt is reheated at 120 ° C. in a 4 liter flask.

The reaction mixture to be obtained is worked up in the manner described in Example 5 performed. It becomes a 1: 1 mixture of phosphonosuccinic acid and Λ-methylphosphonosuccinic acid obtain.

Example 9

To 310 g (1 mol) phosphono-tetraäthylester added dropwise at 15O ⁰ C with stirring and heating period of 2 hours the solution of 34 g (0.5 mol) of sodium ethylate in 185 ml of ethanol. The evaporating ethanol is distilled off. After the addition of ethylate has ended, the reaction mixture is stirred for 10 minutes.

The reaction mixture is worked up in the manner described in Example 5. 375 g are obtained a 50% aqueous solution of a 1:! mixture of phosphono-succinic acid and a-ethyl-phosphono-succinic acid.

Example 10

To the solution of 1 mole of sodium phosphonobemsteinsäure-tetramethylester in 200 ml of toluene, which was prepared in Example as .beschrieben!, Is added dropwise with stirring at 30-40 ⁰ C, 126 g (1 mol) of benzyl chloride. The reaction mixture is stirred at the stated temperature for 4 hours. The reaction mixture is then treated with a solution of 1 mol of hydrogen chloride in 250 ml of dry ether. The precipitated sodium chloride is filtered off and the filtrate was freed by distillation under vacuum up to a bottom temperature of 8O ⁰ C from all volatile compounds. The crude product consists essentially of methyl benzyl phosphonosuccinate which is contaminated by methyl phosphono succinate and methyl methyl phosphonosuccinate.

The crude product is in the example 1 saponified manner described.

Example 11

45

To the suspension of 23 g (1 mol) of sodium in 300 ml of toluene, with vigorous stirring and good Cooling at 20-30 ° C 422g (I mol) of tetrabutyl phosphonosuccinate dripped. A clear solution of tetrabutyl sodium phosphonosuccinate is formed in toluene.

184 g (1 mole) butyl iodide are added dropwise under stirring within 1 hour at 8O ⁰ C to this solution. The reaction mixture is then stirred at 80 ° C. for 2 hours. Then the precipitated sodium iodide is filtered off and the filtrate is freed from the volatile compounds by distillation in vacuo up to a bottom temperature of 100 ° C. The crude product that remains is a 1: 9 mixture of butyl phosphonosuccinate and butyl butyl ester according to the NMR spectrum .

The mixture is saponified in the manner described in Example I.

Example 12

To the solution of 1 mole of sodium-phosphono-tetraäthylester in 200 ml of toluene dropwise mar within 30 minutes at 60-70 ⁰ C, 154 g (1 mole] of diethyl sulphate. The reaction mixture is stirred for I hour. The precipitated Natriummonoäthylsulfat is filtered off. The The filtrate is freed from toluene by distillation in vacuo up to a bottom temperature of 70 ° C. The crude a-ethyl-phosphonosuccinic acid tetraethyl ester obtained is saponified in the manner described in Example 1.

Example 13

In a lemonade factory, bottles with a lye containing 2% caustic soda and an addition of Contains 0.1% of the following active ingredient concentrate, cleaned:

10% o-phosphoric acid,

10% Λ-methyl-phosphonosuccinic acid,

10% defoamer,

70% water.

The carbonate hardness of the water was 15 ° dH. The bottles were in perfect condition after being ejected cleaned and showed no limescale, and there were no limescale deposits on the cleaning machine.

Example 14

In a brewery, the bottle was also cleaned a lye from:

1.00% caustic soda,

0.03% orthophosphate,

0.04% mixture of phosphonosuccinic acid and

Λ-methyl-phosphonosuccinic acid 1: 1,
u, u / ° / o tntscnaumer.

The total hardness was 85 ° dH. The bottles were perfectly clean, free of limescale, and good wetted. In contrast to the use of cleaning agents containing polyphosphate, there was no formation observed from stone deposits on the machine parts.

Example 15

In a mineral water plant, 10 ppm of a 1: 1 mixture of phosphonosuccinic acid and methylphosphonosuccinic acid were added to the 45 ° C. post-spray water. The fossilization of the post-injection zone could thus be completely prevented, and the percentage of bottles that bubbled over due to the release of CO ₂ fell to zero, as no lime crystals - the cause of the undesired release of CO ₂ - had deposited in the bottles.

909 684/59

Claims (5)

Patent claims: 1. α-Substituted phosphonosuccinic acids of formula OR (HO) ₁ PC-COOH CH ₂ -COOH in which R stands for an alkyl radical with 1-4 carbon atoms or stands for the allyl or methallyl radical 2. A process for the preparation of substituted phosphonosuccinic acids of the formula according to Claim I _1, characterized in that tetraalkyl phosphonosuccinic acid esters of the formula are used (RO) ₂ P - CH - COOP-, CH ₂ - COOR ₁ in which Ri is a lower alkyl radical, metalized, the metal atom is replaced by an aliphatic radical and then acid saponified L 3. The method according to claim 2, characterized in that the aliphatic radical with the help of dimethyl sulfate, diethyl sulfate, trimethyl phosphate or triethyl phosphate. 4. The method according to claim 2, characterized in that the alkylating agent used is phosphonosuccinic acid tetra-Ci- to Q-alkyl esters. 5. Use of substituted phosphonosuccinic acid esters according to claim 1 as sequestering agents. The invention relates to -substituted phosphonosuccinic acids of the formula O R il I (HO) ₂ PC-COOH CH ₂ -COOH (I) in which R stands for an alkyl radical with 1-4 carbon atoms or for the allyl or methallyl radical. The invention also relates to a process for the preparation of -substituted phosphonic acids Formula I, which consists in using tetraalkyl phosphonosuccinic acid esters of the formula (R ₁ O) ₁ P CH COOR, CH ₂ COOR ₁ in which Ri is a lower alkyl radical, metalated, the metal atom is replaced by an aliphatic radical and then saponified under acidic conditions, and the use of the compounds of formula I as sequestering agents. Examples of R are the methyl, ethyl, propyl, isopropyl, butyl and sec-butyl radical, and also the AIIyI- and called the methallyl residue. R ₁ preferably denotes the methyl and ethyl radical. The alkylation or substitution of the phosphonosuccinic acid tetraalkyl esters is carried out in such a way that the phosphonosuccinic acid-te- traalkyl ester first metalated by z. B. with stoichiometric amounts of alkali metals, such as lithium or potassium and especially sodium, or with stoichiometric amounts of alkali metal compounds, which salts with CH-acidic compounds form able, z. B. alkali amides such as sodium amide, alkali hydrides such as sodium hydride, or alkali metal alcoholates such as sodium methylate, sodium ethylate or Potassium tert-butoxide, converts and then the obtained alkali phosphonosuccinic acid tetraalkyl ester compounds with the usual alkylating agents means, such as alkyl halides, e.g. B. Methyl bromide, methyl iodide, ethyl chloride, Allyl bromide, methallyl chloride, butyl iodide, Cyclohexyl bromide, bejicyl chloride, dialkyl sulfates, like methyl sulfate and ethyl sulfate, Alkyl sulfonic acid esters, such as p-toluenesulfonic acid ester, trialkyl phosphates, such as Trimethyl phosphate or triethyl phosphate, can react. Also come as alkylating agents also the phosphonosuccinic acid tetraalkyl esters in Consideration The metalation and alkylation of the phosphonosuccinic acid tetraalkyl esters is preferably carried out in inert organic solvents such as aromatic Hydrocarbons, 1st, benzene, toluene, xylene, or ethers, such. B. ether, tetrahydrofuran, made, the metalation usually proceeds with positive heat tint. It may therefore have to be cooled. The alkylation takes place at temperatures between 10 and 18O ⁰ C, preferably 20 and 140 ° C carried out, The resulting "-substituted phosphonosuccinic acid tetraalkyl ester-can then be purified by vacuum Destillationn. When alkylating or substituting the phosphono succinic acid tetraalkyl ester with phosphonobuccin stinic acid tetraalkyl esters are mixtures of phosphono succinic acid trialkyl esters, tetraalkyl esters, «-Alkyl phosphonosuccinic acid trialkyl esters and obtained tetraalkyl esters or their sodium salts. the Alkylation is carried out in such a manner that phosphonosuccinic acid tetraalkyl ester-be reacted with alkali metal alkoxides or alkali metals at 80-170 ° C, preferably 100-150 ⁰ C. The amount of alkali alcoholate or alkali metal is decisive for the proportion of the -alkyl-phosphonosuccinic acid-alkyl esters in the mixtures. When using 0.5 mol Alkali metal (alcoholate) per mole of phosphonosuccinic acid tetraalkyl ester, a mixture is obtained which leads to about 50% from -alkylated and about 50% from not alkylated phosphonosuccinic acid alkyl esters consists of using one mole of alkali metal (II) (alcoholate) per mole of phosphonobernsieic acid tetra- alkyl ester, the mixture consists essentially of -alkylated phosphonosuccinic acid trialkyl esters. The resulting «-alkyl-phosphonosuccinic acid-alkyl esters are then by heating with saponified concentrated hydrochloric acid. The saponification can also be carried out in two stages by