PROCEDURE FOR THE PRODUCTION OF NEW N-SULFOHYDROXY-ALKANE-AMINOALKAN-PHOSPHONIC ACIDS AND OF THEIR ALKALI SALTS

The invention concerns a procedure for the production of new N-Sulfohydroxy-alkane-aminoalkanphosphonsäuren and from their Alkalisa] zen. Described as well as in the DE-OS 2713827 N-Sulfoa] kan aminoa] kanphosphoneäuren a procedure for their Herste] lung, after which Chlorbzw. Hydroxya] kan CSU] fonate at higher temperature with Aminoalkanphosphonsäuren, which carry at least a replaceable hydrogen atom at the group of nitrogens, to be converted. Available the according to invention, new N-Sul fohydroxy A] kan to aminoalkanphosphonsäuren leaves itself by the general formula: POsl H2/R B,--C--N R2 I0 in R, for - H, - OH 3 ' - C2 H5 “- CöHs” - GH2 NH2 “- C2 H PO, H 2” 1 2 for - H or - PO3 H2, R3 for - CnH2 n_I (OH) SO, H or - CI 2 PO, H2, n for a number from 3 to 12, R for IN SUCH A WAY - H (if, differently of - CH2 PO, H2) or for - CnH2 n, _I (OH) H and n' for a number from 3 to 12 stand and the acid hydrogen by A] ka] for i, how Sodium or potassium, to be replaced can characterize. The new N-CSU] fohydroxyalkan aminoa] differ from that so far admitted Aminoa kanphosphonsäuren] kanphosphonsäuren thereby that one or both hydrogen atoms at the nitrogen by Sulfohydroxya] kanreste are replaced. To its production one sets A] ka] iea] for CPU von Aminophosphonsäuren of the general formula: R! PO H2 C N I \ ù 1t2 where have z5 H, and B2 the meaning indicated above and R-S for hydrogen or - CH2 PO3 H2 stands around, in A] ka] ischer solution with A] kal zen from hydraulic XY .ha] ogenalkansulfonsäuren or Epoxy A] kansulfonsäuren, 3 to 12 C-atoms in A] kankette surcharges, with boiling temperature of the solution or under pressure at temperatures between II0 and 1500 C. A become appropriate] ka] isalze of phosphonic acids and A] ka] isa] CPU von Hydroxy- - halogenalkansu] or Epoxy A fonsäuren] kansu] fonsäuren in the Mo] relationship of I: i to I: 2, preferably 1: 1 to I: 1,5. brought to the reaction. A s of alkali salts of Aminophosphonsäuren are completely generally suitable those such Aminoa] kan - phosphonic acids, which carry at least a replaceable hydrogen at the group of nitrogens and which correspond to the managing formula. In detail is there: The Natriumoder of potassium salts of the Aminomethan phosphonic acid, the l-Aminoäth an-2-phosphonsäure, Imino to - methane phosphonic acid as well as l-Aminoalkan-i, l-diphosphonsäure, for example Aminomethan diphosphonsäure, l-Aminoäthan-1, l-diphosphonsäure, l-Aminopropan-i, l-diphosphonsäure, Benzy] - aminodiphosphonsäure, 1,2-Diaminoäth on-i, l-diphosphonsäure, 3-Hydroxy-l-aminopropan-l, I-d1phosphonsäure, 2-Carboxy-l-aminoäLhan-l, l-diphosphonsäure, 3-Hydroxy-l-aminopropan-l, l-diphosphonsäure and l-Aminopropan-l, l, 3-triphosphonsäure. Alkali salts of the 2,3-Epoxypropan-l-sulfonsäure are preferred begun, which one from Epiohlorhydrin and Alkalisu] fit ME IN SUCH A WAY, easily to manufacture can. Other Epoxysulfonate, which is accessible to the conversion, like e.g. 2,3-Epoxyhexan-l-sulfonat, 2,3-Epoxyhexan-4-sulfonat, 1,2-Epoxyoctan-3-sulfon RK, 2,3-Epoxyundekan-l-sul fen RK, 2,3-Epoxydodekan-l-sul fen RK and 9,10Epoxyoctadekan-l-sulfonat, receives one by Epoxydieren of Alkensulfonaten according to conventional methods. For dfe production of Sulfo hydroxyalkan to aminoalkanphosphonsäuren CPU also chlorine hydroxy A] kansulfonate in alkaline medium with Aminophosphonsäuren at temperatures between 90 and 150°C can be converted as Sulfonsäurea] kalisa]. One works favourably at i00 to 130°C in pressure vessels. A] kalichlor hydroxysulfonate, which can be used, are 2-Hydroxy-3-ch] orpropanI0 - la-sul fonat, 3-Hydroxy-4-ch] orbutan l CSU] fen RK, 2-Hydroxy-3-chlorbutan-l-sul fen RK and 2-Methyl -2-hydrexy-3-chlerpropan-l-s u] fona the new phosphonic acids are characterised thereby that them good Komp] opposite 2und multi-valued Meta]] ions are more exbildner, and they can be begun with advantage anywhere, where a good Komp] exbindevermögen opposite multi-valued Meta] lionen are necessary. BesonIS ders to emphasize is still their resistance to hydrolysis at high temperatures, so that they are applicable in all the cases, in which also temperatures over 100°C is used. Thus they can find in all media use, in which the Härtebildner of the water disturbs or in those Einf] üsse of multi-valued Meta] lionen to be switched off are. In detail here the processing of hard water, Textilbehand] more ungsbäder to call the paper trade and the Gerbung are. Also these phosphonic acids are suitable for the Stabi] isierung the water hardness in unterstöchiemetrischen quantities, i.e. for the execution of the so-called “threshold procedure”. The new phosphonic acids combine the characteristics of such connections, the Hydroxyoder Aminoßruppentragen in itself both. Particularly to emphasize the extraordinarily good solubility of the free acids is in aqueous media, which is missing to most well-known Aminophosphonsäuren. Thus 100 g/100 separate rel from the “connections described in the examples in the Mindestfal]. Example I " 48 g amine COMET hand phnsphonsäure and 57 g KOH in 200 ml water are solved and together with 42 g Natriumepoxypropan sulfonat 6 to 8 h under return flow cooked. One neutralizes m t a cation exchanger with Essfgsäure and treats the solution for the distance of the Alka/iionen. After evaporation of the received solution the arrears, which exist mainly out N-Sulfo-hydroxypropan-aminomethan-diphosphonsäure, are washed and dried with Methano]. Yield: 72 G. 3S Anal yse: gef.: C: 15,0, N: 4.3%, P: 18.6%, S: 9.9% more ber.: C: 14.60%, N: 4.26%, P: 18.82%, S: 9.74%. Di in subordinated quantities formed to (N-sulfohydroxypropan) - amlnomethan D [phosphonic acid could be isolated both by Dfinnschichtals also by Säulenchromatographie and identified analytically. In appropriate way one receives phosphonic acid in 68%iger yield the N-Sulfohydroxypropan-l-aminoäthan-l, l-diphosphonsäure from 50 g 1-Aminoäthan-1,1-d}. When further product forms, in particular with increase of the Epoxypropansulfonat quantity, Bisen sulfohydroxypropan) - l-aminoäth an-1, l-diphosphonat. Analysis: more ger.: N: 4.3%, P: 18, I %, S: 9, I % more ber.: N: 4.08%, P: 18.05%, S: 9.34%. With use of 60 g 2-Carboxy-l-aminoäthan-l, l-diphosphonsäure one receives the N-sulfohydroxypropan-2-sarboxy-l-aminoäthan-1, l-diphosphonsäure in 66%iger yield. Using 51 g Imino to m thylenphosphonsäure one receives in 74%iger yield N-Until (phosphonomethyl) - to 3-amino-2-hydroxy-propan-l-su] fonsäure. Analysis: gef.: N: 4.1%, P: 17.8%, S: 9.4% more ber.: N: 4.08%, P: 18.05%, S: 9.34%. Example 2: The Tetrakaliumsalz from 50 g Aminoäthanl, [- diphosphonsäure becomes together with 5 g Ka] ium-2,3-epoxyhexan-l-su] fonat in autoclaves a 3 h long on 130 to 135°G heats up. In accordance with cooling of the pressure vessel, as under example described 1, yield will continue to proceed: 68 g analysis: more ger.: N: 3.8%, more ber.: N: 3.63%, P: 15.9%, S: 8.5% P: 16,0 “%, S: 8.30%. Example 3: In a agitatable pressure vessel 48 g become Aminomethan diphosphonsäure, 72 g KOH and 58 g potassium methy] - hydroxy CH] or-propansu] fonat solved in 500 ml water. Under Bühren the mixture 4 h to 130 to 1350C is heated up. After the cooling with hydrochloric acid weakly one acidifies, if require! I, by ausgefa] lener amine COMET action phosphonic acid filtered off and for the production of the free N-CSU] fo-methy] - hydroxy propane aminomethan phosphonsä ure, as in example i, proceed. Yield: Analysis: more ger.: N: 4.2%, P: 18.0%, S: 9.6% more ber.: N: 4.08%, P: 18.05%, S: 9.34%. In appropriate way one receives from Ka] ium-2-hydroxy-3-chlor-butan-l-su] fen to RK the N-CSU] fo-bydroxy-chlorine-butane-aminomethan-D phosphonic acid. Example 4:51 g 1-Aminoäthan-l, l-diphosphonsäure are solved with 87 g KOH in 400 m] water. Under strong agitating one drips 49 g 3,4-Epoxy-butan-l-sul fonsäure, solved in B0 m] water, to and cooks afterwards 7 h under Rückf] uß. The further processing of the reaction mixture takes place, how described 1 in example. Analysis: more ger.: N: 4.0%, P: 17.3%, S: 9.2% more ber.: N: 3.92%, P: 17.34%, S: 8.98%. Become in place of Epoxy butansulfonsäure 52 g 1,2-Epoxyoctan-3-sulfonsäure receive in such a way one the n (Sulfohydroxy penty]) - propane) - to l-aminoäthan-l, l-diphosphonsäure. Analysis: begun, more ger.: N: 3.5%, P'. 15.2%, S: 7.5% more ber.: N: 3.39%, P: 14.99%, S: 7.76%. When using 65 g 2,3-Epoxy-undecan-sulfonsäure one receives fo-hydroxy - and CAN] - l-aminoäthan-l, l-diphosphonsäure to 92 g n (CSU]. Analysis: gef.: N: 3.2%, P: 13.4%, S: 7.4% more ber.: N: 3.08%, P: 13.06%, S: 7.04%. Example 5: One sch] ämmt 53.5 g Pheny] - amine COMET action phosphonic acid and 36 g 2-Hydroxy -3-chlor-propan-l-sulfonsäure in 200 ml water up and drips under strong agitating and cooling 175 g 50%ige KOH too, whereby one holds the temperature with 10°O. The mixture is heated up afterwards under agitating into a pressure vessel 3 to 4 h on a temperature of 130°C. S after cooling one touches the solution with hydrochloric acid easily and filters off, if necessary, - 5 - NR “3B7065 of small quantities more been ruled out Phenylaminomethan diphosphonsäure and treats the solution with a cation exchanger. In such a way received solution of the n (Sulfo hydroxypropan) - - phenylaminomethan diphosphonsäure is evaporated, the arrears 2mal are washed and dried with methanol. Yield: 73.9 G. Analysis: more ger.: N: 3.6%, P: 15.1%, S: 7.7% more ber.: N: 3.46%, P: 15.29%, S: 7.91%. In appropriate procedure one receives 71 g n (Sulfohydroxy butane) with 40 g 3-Hydroxy-4-chlor-butan-l-sulfonI0 acid - phenylaminomethan diphosphonsäure. To alyse: gef.: N: 3.5%, P: 14.5%, S: 7.8% more ber.: N: 3.34%, P: 14.78%, S: 7.65%.