CA1100995A - N-sulphoalkane-aminoalkane phosphonic acids and their alkali salts and process for their production - Google Patents
N-sulphoalkane-aminoalkane phosphonic acids and their alkali salts and process for their productionInfo
- Publication number
- CA1100995A CA1100995A CA299,893A CA299893A CA1100995A CA 1100995 A CA1100995 A CA 1100995A CA 299893 A CA299893 A CA 299893A CA 1100995 A CA1100995 A CA 1100995A
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- Canada
- Prior art keywords
- acid
- compound
- ch2po3h2
- po3h2
- cnh2nso3h
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
- C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing 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 System
- 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, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
- C07F9/3839—Polyphosphonic 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 System
- 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, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
- C07F9/3839—Polyphosphonic acids
- C07F9/3873—Polyphosphonic acids containing nitrogen substituent, e.g. N.....H or N-hydrocarbon group which can be substituted by halogen or nitro(so), N.....O, N.....S, N.....C(=X)- (X =O, S), N.....N, N...C(=X)...N (X =O, S)
Abstract
ABSTRACT OF THE DISCLOSURE
The present invention provides a N-sulphoalkane-amino-alkane phosphonic acid having the general formula wherein R1 is H, CH3, C2H5, C6H5, CH2NH2 or C2H4PO3H2, R2 is H or PO3H2, R3 = CnH2nSO3H or CH2PO3H2, where n is from 1 - 11 and R4 = H (when R3 is other than CH2PO3H2) or CnH2nSO3H
where n is 1 - 11 and provided that R2 is PO3H2 when R, is hydrogen, R3 is CH2PO3H2 and R4 is CnH2nSO3H
or a salt thereof.
The acids can be readily produced in good yields and their solubility in water is very good for most purposes. They are good complexing agents with respect to divalent and poly-valent metal ions and can be applied with advantage wherever good complexing efficiency is required. Their hydrolysis re-sistance at high temperatures is particularly good so that they are applicable in all the cases in which temperatures above 100°
are applied. They can be used in any medium in which the water softeners have an adverse effect or in which the influence of polyvalent metal ions is to be eliminated. This applied in particular to the treatment of hard water, baths for treating textiles, papermaking and tanning.
The present invention provides a N-sulphoalkane-amino-alkane phosphonic acid having the general formula wherein R1 is H, CH3, C2H5, C6H5, CH2NH2 or C2H4PO3H2, R2 is H or PO3H2, R3 = CnH2nSO3H or CH2PO3H2, where n is from 1 - 11 and R4 = H (when R3 is other than CH2PO3H2) or CnH2nSO3H
where n is 1 - 11 and provided that R2 is PO3H2 when R, is hydrogen, R3 is CH2PO3H2 and R4 is CnH2nSO3H
or a salt thereof.
The acids can be readily produced in good yields and their solubility in water is very good for most purposes. They are good complexing agents with respect to divalent and poly-valent metal ions and can be applied with advantage wherever good complexing efficiency is required. Their hydrolysis re-sistance at high temperatures is particularly good so that they are applicable in all the cases in which temperatures above 100°
are applied. They can be used in any medium in which the water softeners have an adverse effect or in which the influence of polyvalent metal ions is to be eliminated. This applied in particular to the treatment of hard water, baths for treating textiles, papermaking and tanning.
Description
. --\ ~1009~
The pr~scnt ,inven-tion rela-tes to ~-sulphoal~anc-~mino-alkane phosp]lonic ac..ds, their alkali me~al sal-ts and a process for their production.
In West Gc.rman Patent No. 2,313,416 N-carboxy-alkyl-aminoalkane diphosphonic acids and ~'carboxy-methyl-aminoaryl- ~ ~;
alkane diphosphonic acids are described. British Pa~ent No. .
1,142,294 relates to carboxy-aminoalkane phcsphonic acids which contain the grouping >NC~-12PO3H2 which are obtained, for example, by reaction of aminoacetic acid with formaldehyde and phosphorus trichloride in the presence of wa-ter.
The N-carboxy-alkyl-aminoalkane, diphosphonic acids, ;, which are described in German Patent No. 2,318,416, are ob-tained by react,ing aminoalkane di- or tri- phosphonic acids in an alkaline medium with formaldehyde and alkali metal cyanide in '~
specific molar ratios while heating.
According'to the present invention there are provided N-sulphalkane arninoalkane.phosphonic acids,which may be repre-sented by .the.general formula PO3H2 :
Rl - C - N~
wherein R 1s H, CH3, C2H5, C6~l5~ CH2NH2 or C2 4 3 2 2 ~:
R3 is CnH2nSO3H or CH2PO3H2, wherein n is 1 - 11 and R4 is H
(when R3 i.s not CH2 3 2) n 2n 3 where n is 1 - 11 provided that R2 i5 PO3H2 when Rl is hydrogen, R3 is CH2PO3H
and R4 is CnH2 SO3H and the acid hy~rogen can be replaced by alkali metal such as sodium and potassium.
The N-sulphoalkane-aminoalkane phosphonic acids in the present invention differ from the knowyl phosphonic acids in that the hydrogen atoms at the nitrogen are replaced by alkane-sulphonic acid groups.
-, ., s For their production the alkali metal salts here of th~
aminophosphonic acids having the aeneral formula ¦ / R3 Rl - C - N
wherein 1 g ~ CH3~ C2H5~ C6H5'C2H4PO3H2~ CH2NH2, R2 is H or P3H2' and R3 is H or CH2PO3H2 are reacted in an alkaline medium with the alkali metal salts or chloro- or hydroxy- alkane sulphonic acids having the general formula ClCnH2nS3H or HOCnH~nSO3H, wherein n is from 1 to 11, in a molar ratio of approximately 1:1 to 1:2 with heating. The reaction is desixably carried out at a pII of at least 9 and at elevated temperature.
Chloro-alkane sulphonates are reacted at temperatures of approximately 100C. Hydroxy-methane sulphonates noticeably react with the aminophosphonates at temperatures as low as 60C.
The reaction with higher l-hydroxy-alkane-l-sulphonates, as for example, l-hydroxy-ethane-l-sulphonate, is somewhat slower.
However, in the case of 2-hydroxy-ethane-1-sulphonates it has been found that it is required to operate at temperatures be-tween 180 and 240C under pressure.
The sodium or potassium salts of l-chloro-ethane-2-sulphonic acid, l-chloro-propane-2-sulphonic acid,l-chloro-pro-pane-3-sulphonic acid, 2-chloro-butane-4-sulphonic acid, 1-chloro-butane-4-sulphonic acid, 1-chloro-octane-2-sulphonic acicl and 3-chloro- undecane-l-sulphonlc acid are suitable as chloro sulphonates.
Hydroxy-methane sulphonate, l-hydroxy-ethane-l-sul-phonate, 2-hydroxy-ethane-1-sulphonate, 1,2-dihydroxy-ethane-1,2-disulphonate and hydroxy-carboxy-methane sulphonate have been used as hydroxy-all;ane sulphonates.
Any aminoalkane phosphonic acid which carries at least one substitutable hydrogen at the nitrogen group and has the above fcrmula is suitable as the phosphonic-acid component.
Depending on the molar ratios chosen, mono- or di-substituted sulphoalkane -aminoalkane-di- or tri-phosphonic acids are obtained in the reaction with the alkali metal salts of the chloro-alkane sulphonic acids.
When 2-hydroxy-ethane-1-sulphonate is used for the reaction with aminoalkane phosphonic acids, then only produc-ts which carry a suIphoalkane aroup at the nitrogen are obtained.
Instead of the l-hydroxy-ethane-l-sulphonates, the aldehydes or acetals can be reacted together with alkali metal bisulphite.
Instead of using the 2~hydroxy-ethane-1-sulphonates, the starting products serving for the production of the hydroxy-ethane sulphonic acid can be used and reacted with the corres-ponding phosphonates. Thus, it is possible to react carbyl 0 sulphate, which is neutralized with alkali metal hydroxides or~hos~ ~ r);c ' carbonates prior to the reaction, with aminoalkane~ ~si~-acids in an alkaline medium to the corresponding N-sulphalkane-amino-alkane phosphonic acids according to the following reactio pattern: O r î3Na2 H21 o NaOH~ RC-NflC~i C~12SO3Na + Na2So4 + H2O
Rf-N1~2 + I'12C ~ S2 P03Na2 P03Na2 0 The actual sulphalkylation occurs at temperatures fro approximately 130 to 240C under pressure.
Another possibility is the reaction of mixtures of ethylene oxide and NaliSO3 (from which the hydroxy-ethane 995i sulphonic acid can also be produced) directly with aminophos-phonic acids. For this purpose the aminophosphon~te is suitably mixed with the sodium-busulphite solution, whereupon the ethylene oxide is eitller injected or added dropwise. Tn this case the sequence in which the products are added is of decisive importance since oxiranes can react with bo-th the sod-ium bisulphite and the NH2 group to aminoalkane phosphonates.
, Thus, when changing the sequence of the addition primarily N-5p~ o~ a k5 hydroxy-alkane-aminoalkane ~ *~xnrb~ are formed. If the defined sequence is maintained, then these hydroxy-alkane derivatives are formed only in minor amounts. If ethylene oxide and NallSO~ is used, then the reaction, which is represented by the equation hereafter, is also carried out at temperatures from 180 to 240C.
I 03Me21 03Me2 R~C-~i2 + Mel-~O3 + H2C~ /CH2 ~ R C-NHCH2~12S3Me P03Me20 P3Me2 The phosphonic acids of the present invention can be readily produced in good yields and their solubility in water is very good for most purposes. They are yood complexing agents with respect to divalent and polyvalent metal ions and can be applied with advantaye wherever good complexing efficiency is required. Their hydrolysis resistance at high temperatures is particularly good so that they are applicable in all the ca~es in which temperatures above 100C are applied. They can be used in any medium in which the water softeners have an adverse effect or in which the influence of polyvalent metal ion~ is to be eliminated. This applies in particular to the treatment of hard waterl baths for treating textiles, papermaking and tanning.
The phosphonic acids of the present invention are also 9~
suitable for stabillzing the hardness of water in amounts below the stoichiometric value, i~e., for carrying out the so called "threshold process".
The extremely good solubility of the free acids which is lacking in most of the known aminophosphonic acids must be mentioned in particular. Thus, in the lowest case 100 g of the compounds described in the examples dissolve per 10Q ml.
The present invention will be further illustrated by way of the following examples.
Ex~mple 1 47.8 g of aminomethane diphosphonic acid and 50 g of NaOH are dissolved in 3U0 ml of water, whereupon a solution of 42 g of sodium-chloro-ethane sulphonate in 150 ml of water is added dropwise to the first solution at temperatures between 30 and 50C whlle stirring. The mixture is then boiled for one hour while stirring vigorously. After cooling the mixture it is weakly acidified with dilute hydrochloric acid. It is then filtered from possibly precipitating aminomethane diphosphonic acid. The solution is then treated with a cation exchanger in order to recover the free sulphophosphonic acid. After concen-trating the solution it is crystallized by adding methanol or rethanol. The N-sulphoethanc-aminomethane diphosphonic acid shows a calcium chelating power of 22.8 g of Ca per 100 g at pH 10. Yield: 92~ of the theoretical yield.
Analysis:
obtained: C 12.4%~ N 4.6%, P 19~8o S 11.1%
computed: C 12~04%~ N 4.68%, P 20.71% S 10.72%
Example 2 A solution of the sodium salt of aminomethane diphosphonic acid procduced from 47~ 8 g of aminomethane diphosphonic acid and 60 C3 of NaOH in 300 ml of water is added to a solution of 90 g of sodium chloro-ethane sulphonate in 250 ml of water while stir-ring. On completing the addition, the solution is boiled for 5 _ .
30 minutes with reflux. After treating the solution with a cation exchanger and evaporating the solution thus obtained to dryness, the N,N-bis-sulphoethane aminomethane diphosphonic acid is obtained as a colorless oil. The analysis showed the following results:
obtained: N 3.6~, P 14.9%, S 15.8%
computed: N 3.44%, P 15.21%, S 15.75%
Example 3 50 g of l-aminoethane-l, l-diphosphonic acid and 40 g of chloro-ethane sulphonic acid are suspended in 200 ml of water. 240 g of a 30% caustic potash liquor are added dropwise while stlrrin(l vigorously, followed by boiling for one hour with reflux. In order to recover the free N-sulphoethane-l-aminoethane-l, 1-diphosphonic acid, the solution is treated with a cation ex-changer as in the preceding examples. The solution thus ob-tained is concentrated by evaporation and the oily residue is washed out by suspending it in methanol or ethanol.
The analysis of the dried residue showe~ the followinc results:
obtained: C 15.2%, N 4.6%, P 19.4%, S 10.9%
computed: C 15.34%, N 4.47%, P 19.78%, S 10.22%
Example 4 ef ~Qn ~
50 g of 1- _ -1, l-diphosphonic acid and 70 9 of KOil are dissolved in 200 ml of water, whereupon 54 g of potassium-chloro-butane sulphonate in 80 ml of water are added dropwise at a temperature between 40 and 50C while stirring. After the addition is completed the solution is kept boiling for 1.5 hours, whereupon the solution is weakly acidificd and treated with an acid exchanger in order to recover the N-sulphobutane 1-aminoethane-l, l-diphosphonic acid. The analysis of the dried substance showed the following results:
obtained: N 4.2%, P 17.8%, S 9.8%
computed: N 4.11%, P 18.16%, S 9.39%
"~ ~310~9~5 Example_5 - G~E l~P~
From 50 g of aminoethane~ diphosphonic acid ~ and 50 g of NaOH or the corresponding amount of KOH the tetrasodium or f ~P ~
tetrapotassium salt of -the~ 'is obtained in the manner des-cribed in the precedir,y Examples. It is reacted with the sodium or potassium salt of the l-chloro-octane-2-su'phonic acid - as in the preceding examples and on removing the alkali ions by means of a cation exchanger and evaporating the solution thus obtained in a water-jet vacuum the N-sulphooctane-l-aminoethane- ;
10 1, l-diphosphonic acid is obtained.
Analysis:
. obtained: N 3.6%~ P 15.7%r S 8.3%
computed: N 3.52%, P 15.61~, S 8.05%
Example 6 :
66 g of phenyl-aminomethane diphosphonic acid and 48 g of potas-sium-chloro-ethane sulphonate are sus~ended in 200 ml of water.
70 g of KOH in 100 ml of water are then added while stirring.
After boiling for one hour with reflux the solution thus obtaine~
is passed over a cation exchanger in the manner described here-inbefore in order to remove the alkali metal ions and the potas-sium chloride formed, whereupon the solution is concentrated.
Analysis:
obtained: N 3.8~, P 16.2%, S 8.9~ .
computed: N 3.74%, P 16.55%, S 8.57%
From 75 g of 1-aminopropane-1,1,3-triphosphonic acid, 48 g of sodium-chloro-ethane sulphonate and 70 g of NaO~, a solution in 350 ml of water is produced. This solution is kept boiling for 2 hours. On cooling and treating it with a cation exchanger a solution of N-sulphoethane-l-aminopropane-1~1,3-triphosphonic acid is obtained. After concentrating the solution by evapora-tion the analysis produced the following results:
, obtained; N 3.6~, P 22.4~, S 7.~
computed: N ~.44%, P 22.8 ~, S 7.88%
_xample_ 55 g of l-aminopropane-l,l-dlphosphonic acid and 48 g of sodium chloro-propane sulphonate are dissolved in 400 ml of water and mi,;ed wi~h 100 g of a 50% solution of caustic soda. The mixture is then boiled with reflux for one hour, whereupon it is treatecl with a cation exchanger in order to recover the N-sulphopropane-l-aminopropane~ diphosphonic acid. The dry residue of the ~10 solution is analy7.ed with the following result:
obtained: N 4.4%, P 18.0%, S 9.6%
computed: N 4.11%, P 18.16~, S 9.39 Example 9 50 g of imino-bis-me~hane phosphonic acid and 38 g of chloro-ethane sulphonic acid are dissolved in 400 ml of water. This solution is mixed with 62 g of NaOEI and kept boiling for 45 minutes. After treating this solution with a cation exchanger and evaporating it the analysis showed the following results:
obtained: C :l5.0% N 4.5%, P 19.9%, S 10.0%
computed: C 15.34%, N 4.47%, P 19.78~, S 10.22%
~xample 10 _ A so].ution of 48 g of aminomethane diphosphonic acid, 56 g of KOH and 39 g of HOCH2SO3K is stirred for 3 hours at 70 to 75C.
In order to recover a crystalline salt, the solution is care-full.y mixed with methanol and allowed to stand for some time.
The crystallizate is dried in vacuo at 80C.
Example 11 27 g of 1,2-diaminoethane-1,1-diphosphonic acid and 38 g of potassium-1,2-dihydroxy-e-thane-1,2-disulphonate are dissolved in 125 ml of 2N KOH. The solution is then kept for 2 hours at 70 to 80C, whereupon it is concentrated by evaporation in -~
vacuo to one half its volume arld mixed with methanol. On allowin~ the concen~rated solut.ion to stand a crystallizate is obtained and after dryin~ it in vacuo at 50C the analysis showed the following results:
obtained: X 26.8%, C 8.8%, N 5.2%, P 10.5%, S 11.9%
Example 12 50 g of l-aminoethane-1, 1-diphosphonic acid and 43 g of KOH
are dissolved in 300 ml of water. 28 g of potassium bisulphite and 8 g trioxane are added in portions. After keeping this mixture for 2 hours at 50C, 1-aminoethane-1, 1-diphosphonic 10 acid could no longer be detected ln the thin-layer chromatogram.
Example 13 53 g of l-aminopropane-l,l-diphosphonic acid with 30 g of a 30% .
formaldehyde solution and 180 ml of water are heated for 30 minutes to 80C. AEter cooling the mixture a solution of 28 g of K2S2O5 in 375 ml of 2N KO~I is added dropwise and the tempera-ture is kept at 65C for one hour.
Example 14 -25.6 g of imino-bis-methane phosphonic acid with 190 ml of 2M NaOH and 20 g of HOCH2SO3Na H2O in 100 ml of H2O are kept 20 for 2 hours at 60 to 70C. After cooling, the sodium salt of the nitrilo-sulphomethane-bis-methane phosphonic acid is preci-pitated by adding methanol.
~xample 15 In a pressure vessel a solution of the tetrapotassium salt of 48 g of aminomethane diphosphonic acid and 45 g of potassium-2-hydroxy-ethane-l-sulphonate (potassium-isethionate) in 200 ml of water is kept for 5 to 6 hours at temperatures of 190 to 230C. After cooling the solution thus formed, it is slightly acidified with dilute hydrochloric acid, whereupon it is 30 treated with a cation exchanger and concentrated in a water-jet vacuum. After washing the residue with ethanol the N-sulpho-ethane-aminomethane diphosphonic acid is obtained as colourless ~L009~S
oil having the following composition:
obtained: C 12.2%, N 4.5~, P 20~0~, S 11.0%
computed: C 12.04%, N 4.68%, P 20.71%, S 10.72%
Example 16 From 51 g of l-aminoethane-l,l-diphosphonic acid and 40 g of NaOEI or 56 g of KOH as well as 40 g of sodium-isethionate 64 g of N-~ulphoethane-l-aminoethane-1,1-diphosphonic acid are ob-tained.
Analysis:
obtained: C 15.7%, N 4.6%, R 20.0%, S 10.1%
computed: C 15.34%, N 4.47%, P 19.78%, S 10.22%
Example 17 From 55 g of l-aminopropane~ diphosphonic acid, 40 y of NaO~I
and 40 g of sodium-2-hydroxy-ethane-1-sulphonate ~sodium isethio-nate) 62 g of N-sulphoethane-l-amino-propane-l,l-diphosphonic acid were obtained after reaction at 200 to 220C and treatment with a cation exchanger. The analysis produced the following results:
obtaincd: N 4.1%, P 19.5%, S 9.4~
computed: N 4.28%, P 18.96%, S 9.79%
Example 18 From 67 g of phenyl-aminomethane diphosphonic acid and 40 g of sodium-isethionate in 250 ml of water N-sulphoethane-phenyl-amino-methane diphosphonic acid is obtained in the same manner as in Example 15.
Analysis:
obtained: N 3.9%, P lÇ.9%, S 8.3%
computed: N 3.74%, P 16.55%, S 8.56%
Example 19 From 51 g of imino-bis-methane phosphonic acid, 40 g of NaOH an~
40 g of sodium isethionate in 250 ml of water 56 g of N,N-bis-phosphonomethane-amino-ethane sulphonic acid are obtained.
99~
~nalysis:
obtained: C 15.1%, N 4.4%, P 19.9~, S 10.5 computed: C 15L34%I N 4.47%, P 19.78~l S 10.22 Analysis and RF values of the thin layer chromato-grams are in agreement with the product obtained in the phosphonomethylate of Taurin by means of phosphorous aeid and formaldehyde.
Example 20 75 g of 1-aminopropane-1,1,3-triphosphonic acid and 84 g of KOH
along with 46 g of potasslum~2-hydroxy-ethane-1-sulphonate are dissolved in 250 ml of water and heated ln a steel autoclave for 6 to 8 hours to temperatures of approximately 21~C. In order t produce the free N-sulphoethane-l-aminopropane-1,1,3-triphosphon ie acid, the solution formed is eooled and then slightl~ acidi-fied with dilute hydrochlorie aeid, whereupon it is treated with a eation exchanger and eoncentrated in a water-jet vacuum.
.fter washing the residue with methanol or ethanol the free acid is obtained as a eolorless oil, which crystallizes on standing for a lengthy peliod. The analysis of the product shows the following result:
obtained: C 14.1~, N 3.5%, P 23.0~, S 7.7%
eomputed: C 14.75%, N 3.44%, P 22.82~, S 7.87n.
. ~
The pr~scnt ,inven-tion rela-tes to ~-sulphoal~anc-~mino-alkane phosp]lonic ac..ds, their alkali me~al sal-ts and a process for their production.
In West Gc.rman Patent No. 2,313,416 N-carboxy-alkyl-aminoalkane diphosphonic acids and ~'carboxy-methyl-aminoaryl- ~ ~;
alkane diphosphonic acids are described. British Pa~ent No. .
1,142,294 relates to carboxy-aminoalkane phcsphonic acids which contain the grouping >NC~-12PO3H2 which are obtained, for example, by reaction of aminoacetic acid with formaldehyde and phosphorus trichloride in the presence of wa-ter.
The N-carboxy-alkyl-aminoalkane, diphosphonic acids, ;, which are described in German Patent No. 2,318,416, are ob-tained by react,ing aminoalkane di- or tri- phosphonic acids in an alkaline medium with formaldehyde and alkali metal cyanide in '~
specific molar ratios while heating.
According'to the present invention there are provided N-sulphalkane arninoalkane.phosphonic acids,which may be repre-sented by .the.general formula PO3H2 :
Rl - C - N~
wherein R 1s H, CH3, C2H5, C6~l5~ CH2NH2 or C2 4 3 2 2 ~:
R3 is CnH2nSO3H or CH2PO3H2, wherein n is 1 - 11 and R4 is H
(when R3 i.s not CH2 3 2) n 2n 3 where n is 1 - 11 provided that R2 i5 PO3H2 when Rl is hydrogen, R3 is CH2PO3H
and R4 is CnH2 SO3H and the acid hy~rogen can be replaced by alkali metal such as sodium and potassium.
The N-sulphoalkane-aminoalkane phosphonic acids in the present invention differ from the knowyl phosphonic acids in that the hydrogen atoms at the nitrogen are replaced by alkane-sulphonic acid groups.
-, ., s For their production the alkali metal salts here of th~
aminophosphonic acids having the aeneral formula ¦ / R3 Rl - C - N
wherein 1 g ~ CH3~ C2H5~ C6H5'C2H4PO3H2~ CH2NH2, R2 is H or P3H2' and R3 is H or CH2PO3H2 are reacted in an alkaline medium with the alkali metal salts or chloro- or hydroxy- alkane sulphonic acids having the general formula ClCnH2nS3H or HOCnH~nSO3H, wherein n is from 1 to 11, in a molar ratio of approximately 1:1 to 1:2 with heating. The reaction is desixably carried out at a pII of at least 9 and at elevated temperature.
Chloro-alkane sulphonates are reacted at temperatures of approximately 100C. Hydroxy-methane sulphonates noticeably react with the aminophosphonates at temperatures as low as 60C.
The reaction with higher l-hydroxy-alkane-l-sulphonates, as for example, l-hydroxy-ethane-l-sulphonate, is somewhat slower.
However, in the case of 2-hydroxy-ethane-1-sulphonates it has been found that it is required to operate at temperatures be-tween 180 and 240C under pressure.
The sodium or potassium salts of l-chloro-ethane-2-sulphonic acid, l-chloro-propane-2-sulphonic acid,l-chloro-pro-pane-3-sulphonic acid, 2-chloro-butane-4-sulphonic acid, 1-chloro-butane-4-sulphonic acid, 1-chloro-octane-2-sulphonic acicl and 3-chloro- undecane-l-sulphonlc acid are suitable as chloro sulphonates.
Hydroxy-methane sulphonate, l-hydroxy-ethane-l-sul-phonate, 2-hydroxy-ethane-1-sulphonate, 1,2-dihydroxy-ethane-1,2-disulphonate and hydroxy-carboxy-methane sulphonate have been used as hydroxy-all;ane sulphonates.
Any aminoalkane phosphonic acid which carries at least one substitutable hydrogen at the nitrogen group and has the above fcrmula is suitable as the phosphonic-acid component.
Depending on the molar ratios chosen, mono- or di-substituted sulphoalkane -aminoalkane-di- or tri-phosphonic acids are obtained in the reaction with the alkali metal salts of the chloro-alkane sulphonic acids.
When 2-hydroxy-ethane-1-sulphonate is used for the reaction with aminoalkane phosphonic acids, then only produc-ts which carry a suIphoalkane aroup at the nitrogen are obtained.
Instead of the l-hydroxy-ethane-l-sulphonates, the aldehydes or acetals can be reacted together with alkali metal bisulphite.
Instead of using the 2~hydroxy-ethane-1-sulphonates, the starting products serving for the production of the hydroxy-ethane sulphonic acid can be used and reacted with the corres-ponding phosphonates. Thus, it is possible to react carbyl 0 sulphate, which is neutralized with alkali metal hydroxides or~hos~ ~ r);c ' carbonates prior to the reaction, with aminoalkane~ ~si~-acids in an alkaline medium to the corresponding N-sulphalkane-amino-alkane phosphonic acids according to the following reactio pattern: O r î3Na2 H21 o NaOH~ RC-NflC~i C~12SO3Na + Na2So4 + H2O
Rf-N1~2 + I'12C ~ S2 P03Na2 P03Na2 0 The actual sulphalkylation occurs at temperatures fro approximately 130 to 240C under pressure.
Another possibility is the reaction of mixtures of ethylene oxide and NaliSO3 (from which the hydroxy-ethane 995i sulphonic acid can also be produced) directly with aminophos-phonic acids. For this purpose the aminophosphon~te is suitably mixed with the sodium-busulphite solution, whereupon the ethylene oxide is eitller injected or added dropwise. Tn this case the sequence in which the products are added is of decisive importance since oxiranes can react with bo-th the sod-ium bisulphite and the NH2 group to aminoalkane phosphonates.
, Thus, when changing the sequence of the addition primarily N-5p~ o~ a k5 hydroxy-alkane-aminoalkane ~ *~xnrb~ are formed. If the defined sequence is maintained, then these hydroxy-alkane derivatives are formed only in minor amounts. If ethylene oxide and NallSO~ is used, then the reaction, which is represented by the equation hereafter, is also carried out at temperatures from 180 to 240C.
I 03Me21 03Me2 R~C-~i2 + Mel-~O3 + H2C~ /CH2 ~ R C-NHCH2~12S3Me P03Me20 P3Me2 The phosphonic acids of the present invention can be readily produced in good yields and their solubility in water is very good for most purposes. They are yood complexing agents with respect to divalent and polyvalent metal ions and can be applied with advantaye wherever good complexing efficiency is required. Their hydrolysis resistance at high temperatures is particularly good so that they are applicable in all the ca~es in which temperatures above 100C are applied. They can be used in any medium in which the water softeners have an adverse effect or in which the influence of polyvalent metal ion~ is to be eliminated. This applies in particular to the treatment of hard waterl baths for treating textiles, papermaking and tanning.
The phosphonic acids of the present invention are also 9~
suitable for stabillzing the hardness of water in amounts below the stoichiometric value, i~e., for carrying out the so called "threshold process".
The extremely good solubility of the free acids which is lacking in most of the known aminophosphonic acids must be mentioned in particular. Thus, in the lowest case 100 g of the compounds described in the examples dissolve per 10Q ml.
The present invention will be further illustrated by way of the following examples.
Ex~mple 1 47.8 g of aminomethane diphosphonic acid and 50 g of NaOH are dissolved in 3U0 ml of water, whereupon a solution of 42 g of sodium-chloro-ethane sulphonate in 150 ml of water is added dropwise to the first solution at temperatures between 30 and 50C whlle stirring. The mixture is then boiled for one hour while stirring vigorously. After cooling the mixture it is weakly acidified with dilute hydrochloric acid. It is then filtered from possibly precipitating aminomethane diphosphonic acid. The solution is then treated with a cation exchanger in order to recover the free sulphophosphonic acid. After concen-trating the solution it is crystallized by adding methanol or rethanol. The N-sulphoethanc-aminomethane diphosphonic acid shows a calcium chelating power of 22.8 g of Ca per 100 g at pH 10. Yield: 92~ of the theoretical yield.
Analysis:
obtained: C 12.4%~ N 4.6%, P 19~8o S 11.1%
computed: C 12~04%~ N 4.68%, P 20.71% S 10.72%
Example 2 A solution of the sodium salt of aminomethane diphosphonic acid procduced from 47~ 8 g of aminomethane diphosphonic acid and 60 C3 of NaOH in 300 ml of water is added to a solution of 90 g of sodium chloro-ethane sulphonate in 250 ml of water while stir-ring. On completing the addition, the solution is boiled for 5 _ .
30 minutes with reflux. After treating the solution with a cation exchanger and evaporating the solution thus obtained to dryness, the N,N-bis-sulphoethane aminomethane diphosphonic acid is obtained as a colorless oil. The analysis showed the following results:
obtained: N 3.6~, P 14.9%, S 15.8%
computed: N 3.44%, P 15.21%, S 15.75%
Example 3 50 g of l-aminoethane-l, l-diphosphonic acid and 40 g of chloro-ethane sulphonic acid are suspended in 200 ml of water. 240 g of a 30% caustic potash liquor are added dropwise while stlrrin(l vigorously, followed by boiling for one hour with reflux. In order to recover the free N-sulphoethane-l-aminoethane-l, 1-diphosphonic acid, the solution is treated with a cation ex-changer as in the preceding examples. The solution thus ob-tained is concentrated by evaporation and the oily residue is washed out by suspending it in methanol or ethanol.
The analysis of the dried residue showe~ the followinc results:
obtained: C 15.2%, N 4.6%, P 19.4%, S 10.9%
computed: C 15.34%, N 4.47%, P 19.78%, S 10.22%
Example 4 ef ~Qn ~
50 g of 1- _ -1, l-diphosphonic acid and 70 9 of KOil are dissolved in 200 ml of water, whereupon 54 g of potassium-chloro-butane sulphonate in 80 ml of water are added dropwise at a temperature between 40 and 50C while stirring. After the addition is completed the solution is kept boiling for 1.5 hours, whereupon the solution is weakly acidificd and treated with an acid exchanger in order to recover the N-sulphobutane 1-aminoethane-l, l-diphosphonic acid. The analysis of the dried substance showed the following results:
obtained: N 4.2%, P 17.8%, S 9.8%
computed: N 4.11%, P 18.16%, S 9.39%
"~ ~310~9~5 Example_5 - G~E l~P~
From 50 g of aminoethane~ diphosphonic acid ~ and 50 g of NaOH or the corresponding amount of KOH the tetrasodium or f ~P ~
tetrapotassium salt of -the~ 'is obtained in the manner des-cribed in the precedir,y Examples. It is reacted with the sodium or potassium salt of the l-chloro-octane-2-su'phonic acid - as in the preceding examples and on removing the alkali ions by means of a cation exchanger and evaporating the solution thus obtained in a water-jet vacuum the N-sulphooctane-l-aminoethane- ;
10 1, l-diphosphonic acid is obtained.
Analysis:
. obtained: N 3.6%~ P 15.7%r S 8.3%
computed: N 3.52%, P 15.61~, S 8.05%
Example 6 :
66 g of phenyl-aminomethane diphosphonic acid and 48 g of potas-sium-chloro-ethane sulphonate are sus~ended in 200 ml of water.
70 g of KOH in 100 ml of water are then added while stirring.
After boiling for one hour with reflux the solution thus obtaine~
is passed over a cation exchanger in the manner described here-inbefore in order to remove the alkali metal ions and the potas-sium chloride formed, whereupon the solution is concentrated.
Analysis:
obtained: N 3.8~, P 16.2%, S 8.9~ .
computed: N 3.74%, P 16.55%, S 8.57%
From 75 g of 1-aminopropane-1,1,3-triphosphonic acid, 48 g of sodium-chloro-ethane sulphonate and 70 g of NaO~, a solution in 350 ml of water is produced. This solution is kept boiling for 2 hours. On cooling and treating it with a cation exchanger a solution of N-sulphoethane-l-aminopropane-1~1,3-triphosphonic acid is obtained. After concentrating the solution by evapora-tion the analysis produced the following results:
, obtained; N 3.6~, P 22.4~, S 7.~
computed: N ~.44%, P 22.8 ~, S 7.88%
_xample_ 55 g of l-aminopropane-l,l-dlphosphonic acid and 48 g of sodium chloro-propane sulphonate are dissolved in 400 ml of water and mi,;ed wi~h 100 g of a 50% solution of caustic soda. The mixture is then boiled with reflux for one hour, whereupon it is treatecl with a cation exchanger in order to recover the N-sulphopropane-l-aminopropane~ diphosphonic acid. The dry residue of the ~10 solution is analy7.ed with the following result:
obtained: N 4.4%, P 18.0%, S 9.6%
computed: N 4.11%, P 18.16~, S 9.39 Example 9 50 g of imino-bis-me~hane phosphonic acid and 38 g of chloro-ethane sulphonic acid are dissolved in 400 ml of water. This solution is mixed with 62 g of NaOEI and kept boiling for 45 minutes. After treating this solution with a cation exchanger and evaporating it the analysis showed the following results:
obtained: C :l5.0% N 4.5%, P 19.9%, S 10.0%
computed: C 15.34%, N 4.47%, P 19.78~, S 10.22%
~xample 10 _ A so].ution of 48 g of aminomethane diphosphonic acid, 56 g of KOH and 39 g of HOCH2SO3K is stirred for 3 hours at 70 to 75C.
In order to recover a crystalline salt, the solution is care-full.y mixed with methanol and allowed to stand for some time.
The crystallizate is dried in vacuo at 80C.
Example 11 27 g of 1,2-diaminoethane-1,1-diphosphonic acid and 38 g of potassium-1,2-dihydroxy-e-thane-1,2-disulphonate are dissolved in 125 ml of 2N KOH. The solution is then kept for 2 hours at 70 to 80C, whereupon it is concentrated by evaporation in -~
vacuo to one half its volume arld mixed with methanol. On allowin~ the concen~rated solut.ion to stand a crystallizate is obtained and after dryin~ it in vacuo at 50C the analysis showed the following results:
obtained: X 26.8%, C 8.8%, N 5.2%, P 10.5%, S 11.9%
Example 12 50 g of l-aminoethane-1, 1-diphosphonic acid and 43 g of KOH
are dissolved in 300 ml of water. 28 g of potassium bisulphite and 8 g trioxane are added in portions. After keeping this mixture for 2 hours at 50C, 1-aminoethane-1, 1-diphosphonic 10 acid could no longer be detected ln the thin-layer chromatogram.
Example 13 53 g of l-aminopropane-l,l-diphosphonic acid with 30 g of a 30% .
formaldehyde solution and 180 ml of water are heated for 30 minutes to 80C. AEter cooling the mixture a solution of 28 g of K2S2O5 in 375 ml of 2N KO~I is added dropwise and the tempera-ture is kept at 65C for one hour.
Example 14 -25.6 g of imino-bis-methane phosphonic acid with 190 ml of 2M NaOH and 20 g of HOCH2SO3Na H2O in 100 ml of H2O are kept 20 for 2 hours at 60 to 70C. After cooling, the sodium salt of the nitrilo-sulphomethane-bis-methane phosphonic acid is preci-pitated by adding methanol.
~xample 15 In a pressure vessel a solution of the tetrapotassium salt of 48 g of aminomethane diphosphonic acid and 45 g of potassium-2-hydroxy-ethane-l-sulphonate (potassium-isethionate) in 200 ml of water is kept for 5 to 6 hours at temperatures of 190 to 230C. After cooling the solution thus formed, it is slightly acidified with dilute hydrochloric acid, whereupon it is 30 treated with a cation exchanger and concentrated in a water-jet vacuum. After washing the residue with ethanol the N-sulpho-ethane-aminomethane diphosphonic acid is obtained as colourless ~L009~S
oil having the following composition:
obtained: C 12.2%, N 4.5~, P 20~0~, S 11.0%
computed: C 12.04%, N 4.68%, P 20.71%, S 10.72%
Example 16 From 51 g of l-aminoethane-l,l-diphosphonic acid and 40 g of NaOEI or 56 g of KOH as well as 40 g of sodium-isethionate 64 g of N-~ulphoethane-l-aminoethane-1,1-diphosphonic acid are ob-tained.
Analysis:
obtained: C 15.7%, N 4.6%, R 20.0%, S 10.1%
computed: C 15.34%, N 4.47%, P 19.78%, S 10.22%
Example 17 From 55 g of l-aminopropane~ diphosphonic acid, 40 y of NaO~I
and 40 g of sodium-2-hydroxy-ethane-1-sulphonate ~sodium isethio-nate) 62 g of N-sulphoethane-l-amino-propane-l,l-diphosphonic acid were obtained after reaction at 200 to 220C and treatment with a cation exchanger. The analysis produced the following results:
obtaincd: N 4.1%, P 19.5%, S 9.4~
computed: N 4.28%, P 18.96%, S 9.79%
Example 18 From 67 g of phenyl-aminomethane diphosphonic acid and 40 g of sodium-isethionate in 250 ml of water N-sulphoethane-phenyl-amino-methane diphosphonic acid is obtained in the same manner as in Example 15.
Analysis:
obtained: N 3.9%, P lÇ.9%, S 8.3%
computed: N 3.74%, P 16.55%, S 8.56%
Example 19 From 51 g of imino-bis-methane phosphonic acid, 40 g of NaOH an~
40 g of sodium isethionate in 250 ml of water 56 g of N,N-bis-phosphonomethane-amino-ethane sulphonic acid are obtained.
99~
~nalysis:
obtained: C 15.1%, N 4.4%, P 19.9~, S 10.5 computed: C 15L34%I N 4.47%, P 19.78~l S 10.22 Analysis and RF values of the thin layer chromato-grams are in agreement with the product obtained in the phosphonomethylate of Taurin by means of phosphorous aeid and formaldehyde.
Example 20 75 g of 1-aminopropane-1,1,3-triphosphonic acid and 84 g of KOH
along with 46 g of potasslum~2-hydroxy-ethane-1-sulphonate are dissolved in 250 ml of water and heated ln a steel autoclave for 6 to 8 hours to temperatures of approximately 21~C. In order t produce the free N-sulphoethane-l-aminopropane-1,1,3-triphosphon ie acid, the solution formed is eooled and then slightl~ acidi-fied with dilute hydrochlorie aeid, whereupon it is treated with a eation exchanger and eoncentrated in a water-jet vacuum.
.fter washing the residue with methanol or ethanol the free acid is obtained as a eolorless oil, which crystallizes on standing for a lengthy peliod. The analysis of the product shows the following result:
obtained: C 14.1~, N 3.5%, P 23.0~, S 7.7%
eomputed: C 14.75%, N 3.44%, P 22.82~, S 7.87n.
. ~
Claims (16)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A N-sulphoalkane-aminoalkane phosphonic acid having the general formula wherein R1 is H, CH3, C2H5, C6H5, CH2NH2 or C2H4PO3H2, R2 is H or PO3H2, R3 = CnH2nSO3H or CH2PO3H2, R4 is H (when R3 is other than CH2PO3H2) or CnH2nSO3H, and n is 1 - 11 or a salt thereof, provided that R2 is PO3H2 when R1 is hydrogen, R3 is CH2PO3H2 and R4 is CnH2nSO3H.
2. A compound as claimed in claim 1, in which R2 is the-PO3H2 group.
3. A compound as claimed in claim 2, in which R3 is the group -CHnH2nSO3H, where n is as in claim 1.
4. A compound as claimed in claim 1, which is an alkali metal salt.
5. A compound as claimed in claim 1, which is N-sulphoethane-amino methane 1,1-diphosphonic acid.
6. A compound as claimed in claim 1, which is N,N-bis-sulphoethane-amino methane-1,1-diphosphonic acid.
7. A compound as claimed in claim 1, which is N-sulphoethane-1-aminoethane-1,1-diphosphonic acid.
8. A compound as claimed in claim 1, which is N-sulphobutane-1-amino-ethane 1,1-diphosphonic acid.
9. A compound as claimed in claim 1, which is N-sulphooctane-1-amino ethane-1,1-diphosphonic acid.
10. A compound as claimed in claim 1, which is N-sulphoethane-1-aminopropane-1,1,3-triphosphonic acid.
11. A compound as claimed in claim 1, which is N-sulphopropane-1-aminopropane-1,1-diphosphonic acid.
12. A compound as claimed in claim 1, which is N-sulphoethane-phenyl-aminomethane-1,1-diphosphonic acid.
13. A process for producing an N-sulphoalkane-amino-alkane phosphonic acid, a N-sulphoalkane-aminoalkane phosphonic acid, having the general formula Wherein R1 iS H, CH3, C2H5, C6H5, CH2NH2, or C2H4PO3H2, R2 is H or PO3H2, R3 is CnH2 SO3H or CH2PO3H2, R4 is H (when R3 is other than CH2PO3H2) or CnH2nSO3H, and n is 1 - 11, provided that R2 is PO3H2 when R1 is hydrogen, R3 is CH2PO3H2 and R4 is CnH2nSO3H
or a salt thereof which comprises treating an alkali metal salt of an aminophosphonic acid having the general formula wherein R1 is H, CH3, C2H5, C6H5, C2H4PO3H2, or CH2NH2, R2 is H
or PO3H2, and R3 is H, or CH2PO3H2 in an alkaline medium with a chloro- or hydroxy-alkane sulphonic acid or an alkali metal salt thereof having the general formula C1CnH2nSO3H or HOCnH2nSO3 H, wherein n is 1 to 11, or compounds which form the hydroxy-alkane sulphonate in situ in a molar ratio of 1:1 to 1:2 with heating.
or a salt thereof which comprises treating an alkali metal salt of an aminophosphonic acid having the general formula wherein R1 is H, CH3, C2H5, C6H5, C2H4PO3H2, or CH2NH2, R2 is H
or PO3H2, and R3 is H, or CH2PO3H2 in an alkaline medium with a chloro- or hydroxy-alkane sulphonic acid or an alkali metal salt thereof having the general formula C1CnH2nSO3H or HOCnH2nSO3 H, wherein n is 1 to 11, or compounds which form the hydroxy-alkane sulphonate in situ in a molar ratio of 1:1 to 1:2 with heating.
14. A process according to claim 13, in which the reaction with hydroxy-alkane sulphonic acids is carried out at temperatures from 180 to 240°C under pressure.
15. A process according to claim 13 or 14 in which the reaction is carried out at a pH value of at least 9.
16. A process as claimed in claim 13 or 14, in which the hydroxy alkane sulphonate is formed in situ by the reaction carbyl sulphate, aldehydes or ethylene oxide with an alkali metal sulphite.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19772713827 DE2713827C3 (en) | 1977-03-29 | 1977-03-29 | N-SuIfoalkan-aminoalkanephosphonic acids, their alkali metal salts and process for their preparation |
| DEP2713827.8 | 1977-03-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1100995A true CA1100995A (en) | 1981-05-12 |
Family
ID=6004988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA299,893A Expired CA1100995A (en) | 1977-03-29 | 1978-03-29 | N-sulphoalkane-aminoalkane phosphonic acids and their alkali salts and process for their production |
Country Status (3)
| Country | Link |
|---|---|
| BE (1) | BE865443A (en) |
| CA (1) | CA1100995A (en) |
| DE (1) | DE2713827C3 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2758306C3 (en) * | 1977-12-27 | 1981-05-27 | Benckiser-Knapsack Gmbh, 6802 Ladenburg | Process for the preparation of N-sulfoalkanaminoalkanephosphonic acids or their alkali salts |
-
1977
- 1977-03-29 DE DE19772713827 patent/DE2713827C3/en not_active Expired
-
1978
- 1978-03-29 CA CA299,893A patent/CA1100995A/en not_active Expired
- 1978-03-29 BE BE186375A patent/BE865443A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE2713827A1 (en) | 1978-10-05 |
| DE2713827C3 (en) | 1980-02-07 |
| BE865443A (en) | 1978-07-17 |
| DE2713827B2 (en) | 1979-06-13 |
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