DE2737259A1 - N-CARBOXYALKANE AMINOALKANE DIPHOSPHONIC ACIDS, N-CARBOXYALKANE-AZACYCLOALKANE DIPHOSPHONIC ACIDS AND N-CARBOXYALKANE AMINOARYLALKANE DIPHOSPHONIC ACIDS AND THE PROCESS FOR THEIR PRODUCTION - Google Patents

Description

BENCKISERKNAFSACK GMBH 6802 LAOENRURG / NECKAR

Ai- port 2 · Poet compartment

Telephone * * (06203) 771 Telegraph 0463061 Wire address BEKA Ladenburg

June 11, 1977

Pj / br.li / Bi - BK 159 -

N-carboxyalkane-aainoalkane-diphoaphonic acids, N-carboxyalkane-asacycloalkane-diphosphonic acids and N-carboxyalkane-aainoarylalkanediphoaphonic acids as well as processes for their production

The present invention relates to N-carboxyalkane-aainoalkane-diphoaphonic acids, N-carboxyalkane-azacycloalkane-diphosphonic acids and N-carboxyalkane-aainoarylalkane-diphosphonic acids, so vie a process su their manufacture.

From DT-PS 23 18 46 are N-carboxyaethyl-aainoalkan-diphosphonic acids and N-carboxyaethyl-aminoarylalkane-diphosphonic acids known, the «an by the implementation of Aainoalkan- or Aainoarylalkan-diphosphonsäuren ia alkaline medium alt foraaldehyde and alkali metal cyanide is obtained by heating to 70-150 ° C.

This method has the disadvantage that it is very large when working with alkali metal cyanides, especially technical ones Mafistab, is required and therefore extensive safety precautions are essential.

Surprisingly, it has now been found that aan both the the German patent 23 18 416 known compounds as

909809/0227

Registered office of the company: Ladenburg / Neckar · District Court of Mannhelm, Reg. No. B1305 ■ Managing Director: Dr. Karlheinz Ernst, Dr. Theodor Riehm & 26 / & 73 / 10,000 NL

BENCKISER-KNAPSACK GMBH Ö302 LADENBÜRG / NECKAR

Air Port 2 PO Box 2/3 / £ D S

Telephone * * (06203) 771 Telegraph 046306t Wire address BEKA Ladenburg

also new N-carboxyalkane-aainoalkane-diphosphonic acids, N-carboxyalkane-acacycloalkane-diphosphonic acids and N-carboxyalkanaoarylalkane diphosphonic acids can be produced under more favorable working conditions, if aainoalkane, azacycloalkane or aainoarylalkanephosphonic acids of the general Foreel

B-C N

in the BH, (CHg) _x -CH ₃ , C ₃ H ₄ OH, CH ₂ COOH, C ₆ H ₅ , (CH ₂ J _n -N (CH ₂ COOH) ₂ , (CH ₂ J _n -PO ₃ H ₂ ,

where η - 1 or 2 and χ - 0 - 10 or with ring formation with B ₂ - (CH-), _

B ₁ - PO ₃ H ₂

B ₂ m H, CH. or susaaaen with B to form a ring

- < ^CH 2> 3-5

are old straight-chain or reverse-chain haloalkanaonocarboxylic acids old 2 to 12 carbon atoms or old haloalkane carbonic cures bsw. their alkaline salts or esters at tea temperatures tob 50 - 160 ° C la Molrerhiltnia τοη 1 ι 1 to 1 1 3 in vftfirigea Medina uasetst.

909809/0227

Registered office of the company: Ladenburg / Neckar ■ District court Mannhelm, Reg. Nr. B1305 · Managing director: Dr. Karlheinz Ernst, Dr. Theodor Rlehm 3-26 / 8.73 / 10,000 NL

BENCKISER-KNAPSACK GMBH 0302 LADENBÜRG / NECKAR Air Port 2 - P.O. Box

Telephone * * (06203) 771 Telegraph 0463061 Wire address BEKA Ladenburg

In this way, compounds of the general formula are obtained

R B-C N

in which R and R. have the meaning mentioned above, while

B- - (CH ₂ ) COOH, ■ - 2 - 12, straight or Terxveigt-

chained,

-CH - COOH
I.
CH ₂ - COOH

B £ - H, CH, B or, forming a bing, «it B (CH ₂ ) ^ y

New compounds of this type are N-carboxyethane-asacycloheptan-2- _y 2-diphosphonic acid ₍ N-Carbozjrpentan-1-aainoethane-1fl-diphosphonic acid, N-carboxyethane-1-aminoethane-ltl-diphosphonic acid, N-carboz7-2 _y 2-diaeth7l -aainoaethane-diphosphonic acid _t N-10-carboxydekan-aainoaethane-diphosphonic acid, Ν, Ν-Bie-10-carboxydekan-aeino- ■ ethane-diphosphonic acid and N- (l, l-diphosphonoprop-l-yl) -DL-aainosuccinic acid.

Suitable compounds for the carboxylation of aainoalkane, aminoaryl alkanoic or asacyeloalkane-phosphonic acids are, among others, the mono-chloro- or broaacetic acid, 6-broahexanoic acid, 3-chloropropionic acid, 3-chloro-2,2-di «ethyl propionic acid (B-chloro

909809/0227

Seat of the company Ladenburg / Neckar ■ District court Mannhelm, Reg. Nr. B1305 · Managing director: Dr. Karlheinz Ernst, Dr. Theodor Rlehm 3.26 / 8.73 / 10,000 NL

BENCKISER-KNAPSAOK GMBH tttO2 LADENb-JRG / NECKAR

Air. Hafe.i 2 · P.O. Box

Telephone * * (06203) 771 Telegraph 0463061 Wire address BEKA Ladenburg

pimelic acid), 11-bromundecanoic acid, and as a dicarboxylic acid the bromosuccinic acid.

To prepare the substances according to the invention, it is possible to dissolve the aminophosphonic acid in an excess of alkali lye and then to introduce the halocarboxylic acid in such a way that the pH does not fall below k. The process can be carried out much more elegantly if only as much alkali lye as is required for the desired pH value between 4 and 12, preferably 7 and 9, is required. The further metering of alkali and halocarboxylic acid is then controlled as a function of the pH.

In uneven cases, the phosphonic acid is advantageously suspended and halocarboxylic acid in water and completely or partially neutralized with alkali hydroxide. The response time and Temperature using the heat of neutralization 0.5 to 3 hours and at 50-160 ° C, advantageously at 80 to 120 ° C.

In this way, completely or partially neutralized salts are obtained as reaction products, which by means of cation exchange ^ in the free acids can be converted.

It is also easily possible, instead of alkali hydroxide, e.g. alkali carbonate or for special applications alkali and alkaline earth hydroxides together, e.g. sodium and calcium

909809/0227

Registered office of the company: Ladenburg / Neckar · District Court of Mannhelm, Reg. No. B1305 ■ Managing Director: Dr. Karlheinz Ernst, Dr. Theodor Riehm 126/173 / 10,000 NL

BENCKISERKNAPSACK GMBH tSdO2 LADEiMbüRG / NECKAR _ _ _o

Αιτ. Port; i 2 P.O. Box £. I $ f £, 0 *

Telephone * * (06203) 771 Telegraph 0463061 Wire address BEKA Ladenburg

hydroxide or alkali heavy metal hydroxide, sB sodium n inate _t sodium zincate or sodium stannate should be used.

Products made in this way are particularly suitable for anti-corrosion oils ttel and for products in the treatment τοη use watering suitable.

Depending on the properties or the desired application, the solutions are used directly and the salts crystallize or after ion exchange the acid according to known methods, like evaporation concentration or precipitation bsw. extraction with organic solvents.

In the case of the carboxylation, the one used is obtained, depending on τοη Molar ratios and the amino-phosphonic acid used, single or multiple carboxyalkylated products. at with a molar ratio of the reactants of 1 to 1, N-carboxyalkane-aainoalkane-diphosphonic acids are preferably obtained. A molar ratio of the reactants of alinophosphonic acid to halocarboxylic acid of 1 to 2 to 1 3 preferably gives N, N-bis-carboxyalkane-aainoalkane-diphosphonic acids.

The substances obtained according to the present invention can be used wherever a good Koaplexbindeverögen against 2- and polyvalent metal ions is required. They are particularly characterized by their resistance to hydrolysis at high temperatures. They can be used in • all media in which the hardness components 4 ··

909809/0227

Registered office of the company: Ladenburg / Neckar · District Court of Mannhelm, Reg. No. B1305 · Managing Director: Dr. Karlheinz Ernst. Dr. Theodor Riehm 3 ^ 6 / 8.73 / 10,000 NL

BENCKISERKNAPSACK GMbH <6802 LADENBURG / NECKAR - - ~ "- _{c Q}

Ar.) Port 2 ■ PO Box £ ISI JL Xi +

Telephone * * (06203) 771 Telegraph 0463061 Wire address BEKA Ladenburg

Disturbing water or in which any influences of polyvalent Metal ions should be switched off. In detail here are the treatment of hard water, textile treatment baths, to mention papermaking and tanning. These phosphonic acids are also suitable for stabilization the water hardness in sub-stoichiometric amounts. Even They can be used as stabilizers for dispersions and suspensions to serve.

Since the products according to the invention have the properties of phosphonic acids and aminocarboxylic acids, they offer application advantages over the phosphonic acids or the Aminocarboxylic acids alone, which have the sum of the properties of the individual components.

Example It

Be in a stirred tank with a thermometer and reflux condenser 6.72 kg 50% potassium hydroxide solution and 2.05 kg 1-aminoethane-1,1-diphosphonic acid added in such a way that the sump temperature does not exceed 60 ° C. * A solution is then added dropwise within 1 hour of 1.89 kg of monochloroacetic acid in 2.2 kg of water and then heated to 100 ° C for 3 hours.

After desalting an aliquot of the reaction product by means of a strongly acidic cation exchange "" and concentration of the solution, the N.N-bis-carboxymethane-l-aminoethane-l,! -

909809/0227

Company headquarters: Ladenburg / Neckar · Mannheim District Court, Reg. No. B1305 ■ Managing Director: Dr. Karlheinz Ernst, Dr. Theodor Rlehm 3.26 / 8.73 / 10,000 NL

BENCKISER-KNAPSAOK GMBH 6802 LADENBURG / NECKAR η T O T O t: Q At. Hafe / i 2 ■ P.O. Box £. I α / ί D ϊ »

Telephone * * (06203) 77t telegraph 0463081 Wire address BEKA Ladenburg

diphosphonic acid can be obtained by crystallization with methanol / ethanol in a yield of $ 91.3 of theory.

The product shows the following analysis

calculated t Ct 22.40 %, Nt 4.36 %, Pt 19.29 $ gef.t Ct 22.6 i, Nt k, k%, Pt 19.3 %

Molar ratio of CtPtN - 5.99 »1.98 t 1. Example 2t

28 g of potassium hydroxide are dissolved in 100 al of water and 20.5 g l-anrinoethane-ljl-diphoephone acid entered. Then there ■ 13.9 g of broaacetic acid and refluxed for 3 hours.

The reaction product is treated with an acid exchanger (Lewatit S 100) and the solution is concentrated. A light yellow, viscous oil results, which is crystallized with methanol / ethanol. After drying in a water jet vacuum at 80 ° C., 25.4 g of N-carboxymethane-1-aminoathane-II-diphosphonic acid are obtained, which corresponds to a yield of 96.6 % of theory.

Analysis: calculated t Ct 18.26 % _t Nt 5.32 %, Pt 23.55 %, measured t Ct 17.6 %, Nt 5.2 Jl, Pt 23.3 %

Molar ratio of CtPtN - 3.95 <2.02 t 1.

909809/0227

Company headquarters: Ladenburg / Neckar ■ Mannhelm District Court, Reg. No. B1305 ■ Managing Director: Dr. Karlheinz Ernst, Dr. Theodor Rlehm 126 / 8.73 / 10,000 NL

BENCKISER-KNAPSAOK GMbH · ββΟ2 LAUENBURG / NECKAR - "~" ~ _{c Q}

Ar., Hafe.i 2 · P.O. Box A / SI />) «J

Telephone * * (06203) 771 Telegraph 04 63061 Wire address BEKA Ladenburg

Example 3 *

47.8 g of aminonethane-diphosphonic acid are dissolved in 148 g of 50% potassium hydroxide solution Dissolved at 60 C and a solution of 99t4 g of potassium salt added to the monochloroacetic acid in 250 ml of water. Afterward is heated to 80 - 90 ° C for 3 hours.

After working up the reaction solution, as in the previous example described, one receives 75.2 g of Ν, Ν-bis-carboxyaethanaminomethan-diphosphonic acid.

Analysis made.t Ct 19.56 %, Nt 4.56 %, Pt 20.17 % gef.t Ct 20.3 Jt, Nt 4.7 Jt, P: 20.3 %

Molar ratio of CtPtN - 5.04 t 1.95 <1. Example 4t

95.5 g of aminomethane diphosphonic acid are dissolved in 224 g of 50% potassium hydroxide solution dissolved at 60 ° C., 300 ml of water and 54.3 g of methyl chloroacetate were added. After 3 hours of boiling under reflux one cools down.

After working up the solution with an acid exchanger, concentrating, crystallizing and drying, 115 g of N-carbozymethane-aminomethane-diphoephonic acid are obtained, which corresponds to a yield of 92.3 %

909809/0227

Company headquarters: Ladenburg / Neckar ■ Mannheim District Court, Reg. No. B1305 ■ Managing Director: Dr. Karlheinz Ernst, Dr. Theodor Riehm 3.26 / 173 / 10,000 NL

BENCKISER-KNAPSAOK GMBH ββΟ2 LAUENBURG / NECKAR

Telephone * * (06203) 771 Telegraph 0463061 Wire address BEKA Ladenburg

corresponds to the theory.

Analysis: calculated Ct Ik, kl%, Nt 5.62 Jt, Pt 24.87 % gef.t Ct 15.1 %, Nt 5.7 _% Pt 25.0 Jt.

Molar ratio t CtPtN - 3.09 t 1.98 t 1. Example 5t

13.4 g of phenylamino-ethane-diphosphonic acid are dissolved in a solution of 8 g of NaOH in 100 ml of water so that the temperature does not exceed 60 ° C. and then 4.8 g of nonochloroacetic acid are added. The reaction solution is then kept at 110 ° C. for 3 hours:
Exchanger.

at 110 C, lets it cool and does not treat a strongly acidic one

15 g of crystalline N-carboxy-ethane-phenyla-bino-ethane-diphosphonic acid are obtained from the concentrated solution with methanol.

Analysis «her.t Ct 33.23 %, Nt 4.31 %, Pt 19.05 %, found Ct 32.8 J», Nt 4.3 Jf ₁ Pt 18.6 %.

Molverh.ι CtPtN - 8.9 t 1.95 t 1. Example 6t

54.8 g of l-aninopropane-l-diphosphonic acid are dissolved in 200 μl of water stirred in and slowly 14.6 g of basic zinc carbonate were added. After the evolution of gas has ceased, 140 g of 50%

909809/0227

Registered office of the company: Ladenburg / Neckar ■ AmtsgerlchtMannheim, Reg. Nr.B1305 ■ Managing director: Dr. Karlheinz Ernst, Dr. Theodor Riehm 126 / 8.73 / 10,000 NL

BENCKISER-KNAPSAOK GMbHödO2 LADENb-JRG / NECKAR

Telephone * * (06203) 771 Telegraph 0463061 Wire address BEKA Ladenburg

Lye is added and, after cooling to 50 ° C., 47.3 g of monochloroacetic acid entered in portions.

After boiling under reflux for 2 hours, a clear, pale yellow colored solution of the Kaliuazinkalses of N ₁ N-biscarboxymethane-1-aminopropane-1,1-diphosphonic acid is obtained. Thin-layer chromatographic studies show a minimum conversion of 90 % of theory. Part of the solution is worked up as described in the previous examples.

Analyzes calculated at Ci 25.09 Jt, Nt 4.18 %, Pt 18.48 % found : Ci 24 ,? %, Nt 4.2 i, Ps 18.2 %

Nolverh.t CtPtN - 6.81> 1.96: 1. Example 7t

90 g of potassium hydroxide are dissolved in 250 μl of distilled water and 103.6 g of aza-eycloheptane-2,2-diphosphonic acid are added to this solution in such a way that the temperature does not exceed 60.degree. After adding 38 g of nonochloroacetic acid, the mixture is heated to 110 ° C. for 2 1/2 hours. It is allowed to cool and then, according to the method described in Example 1, 102.5 g of N-carbozymethane-aza-cycloheptane-2 _f 2-diphosphonic acid are obtained from the solution.

Analysis t ber.t Ct 30.49%, 4.44% Nt, Pt 19.66 $ gef.ι Ct 30.0%, 4.5% Nt, Pt 20.0%.

Molar ratio of CtNtP - 7.8 t 1 t 2.

909809/0227

Registered office of the company Ladenbury / Nrckur ■ Aiit & gpn Jii M.inn! ..m, Req Nr B13O5 (.Jeschiif'.sfüli'i'r IJr K λ W-.tarz F.rnst, Dt Ihfodor R-ehrn 3.26 / B.73 / 10 000 Nl-

BENCKISER-KNAPSAOK GMbH 6602 LADENÖURG / NECKAR

Telephone * * (06203) 771 Telegraph 0463061 Wire address BEKA Ladenburg

* ( / 73

Example 8t

41 g of 1-Aainoäthan-l, 1-diphosphonic acid are drilling in 187 S 30% potassium hydroxide solution and 39 g of 6-bromohexane acid at 60 ° C admitted. To complete the reaction will Slowly heated to 100 C and 3 hours at this temperature left. After work-up, certainly Example 1 is given ■ of N-carboxypentane-1-aninoethane-1,1-diphosphonic acid.

By measuring the free amino groups using the Van Slyke method, a conversion of 73.4 % of theory was determined.

Example 9i

In a mixture of 51 g of 1-ethane-l, 1-diphosphonic acid, 27.2 g of 3-chloropropionic acid and 150 μl of water are added with stirring 140 g of 50% potassium hydroxide solution were added dropwise at 70 ° C. over the course of one hour and then the clear solution was refluxed for 2 hours cooked.

After the solution has been worked up, 57 * 5 g of N-carboxyethanol-aainoethane-1,1-diphosphonic acid are obtained.

Analyzes her.ι Ct 21.67 % * Nt 5.05 % _f P * 22.35 t gef.t Ct 20.5 t, Nt 4.8 $, Pt 21.3 %

Molar ratio CtNtP «4.98 t 1 t 2.

909809/0227

Company headquarters: Ladenburg / Neckar ■ Mannhelm District Court, Reg. No. B1305 ■ Managing Director: Dr. Karlheinz Ernst, Dr. Theodor Rlehm 3.26 / 8.73 / 10,000 NL

BENCKISER-KNAPSACK GMbHödO2 LAOEnB-JRG / NECKAR

Telephone * * (06203) 771 Telegraph 0463061 Wire address BEKA Ladenburg

Example IQt

34.6 g of 3-chloro-2,2-dimethylpropionic acid (β-chloropivalic acid) are added under Behren to a solution of 47.8 g of aminonethane-diphospfaonic acid in 288 g of 30% potassium hydroxide solution. The solution is heated to the boil within one hour and kept at this temperature for 2 hours. After working up N-2-Carbozy _t-2 was 2-dimethylethane-aminomethane dipho8phonsäure obtained.

By determining the primary amino groups in the solution, a conversion of 73-5 % of theory could be determined.

Example 11t

54.7 g of l-aminopropane-ljl-diphoephonic acid are dissolved in 150 g of 40 (iger Dissolved sodium hydroxide solution and added 49 »5 DL-bromosuccinic acid at 60 ° C. It takes 2 hours to complete the reaction cooked at the inflow.

Quantitative thin-layer chromatography in the solution 21 g of 1-aminopropane-l, 1-diphosphonic acid and 51 »4 g of N- (l, l-diphosphonoprop-l-yl) -DL-aminosuccinic acid be detected.

909809/0227

Company headquarters: Ladenburg / Neckar ■ Mannheim District Court, Reg. No. B1305 - Managing director: Dr. Karlheinz Ernst, Dr. Theodor Riehm 3.26 / 8.73 / 10,000 NL

BENCKISER-KNAPSACK GMBH ■ & M2 LAOENB'JRG / NECKAR

Telephone * * (06203) 771 Telegraph 0463061 Wire address BEKA Ladenburg

Example 12t

47.8 g of aminoethane-diphosphonic acid are dissolved in 150 g of 50% potassium hydroxide solution and 88.8 g of 11-bromundecanoic acid are added to this solution at 80.degree. After boiling aa reflux for 2 hours and cooling the solution, thin-layer chromatographic examinations showed that about 30% aaineoethane-diphosphonic acid, about 60 % N-10-carboxydekan-aainomethane-diphosphonic acid and about 10 % N / N-bis-10-carboxyde-aminomethane -diphosphonic acid can be detected.

Example 13t

In a 1 a 'agitator tank old reflux condenser, healing, built-in pH-Einstabaeßkette and 2 dropping funnels are in 292.2 kg of water and 69.8 kg of 50% potassium hydroxide solution, 127.7 kg of 1-alinoethane-1,1-diphosphonic acid solved. The solution is heated to 80 ° C using the neutralization «heat and from the both templates 147.7 kg of 80% monochloroacetic acid solution and approx. 362 kg 5O5tiger potassium hydroxide solution added. The addition is controlled in such a way that that the pH value la reaction aediua is between 8.0 and 8.9. Due to the heat of reaction that occurs, the reaction mixture can be kept at 80 to 90 ° C. After the end of the feed, old potassium hydroxide solution is adjusted to a pH of 8.5 and the solution was stirred at 90-100 ° C. for a further hour.

The resulting solution has a content of approx. 20 % N, N-biscarboxyethylene-l-aainoethane-lfl-diphosphonic acid.

909809/0227

"it? of the company: Ladenburg / Neckar · Mannheim District Court, Reg. No. B1305 · Managing Directors: Dr Karlheinz Ernst, Dr Theodor Riehm 3.26 / 8th "3 / 10,0OO NL

BENCKISERKNAPf ACK GMBH ββΟ2 LADEnB-JRG / NECKAR

Telephone * (06203) 771 Telegraph 0463061 Wire address BEKA Ladenburg

Example Ui

58.7 g of 3-hydroxy-l-aainopropane-l, l-diphosphonic acid are introduced into a solution of 84 g of KOH in 300 μl of water. The solution is heated to 60.degree. C. and 56 g of 3-chloropropionic acid are added while vigorously stretching so that the temperature slowly rises to 80.degree. After 3 hours of refluxing, a pale yellow solution results. After working up the solution by means of a strongly acidic ion exchanger, concentration, crystallization and drying, 81 g of slightly yellowish hygroscopic crystals are obtained. The thin-layer chromatographic analysis shows a content τοη approx. 20 % N-carboxyethane-3-hydroxy-l-aainopropane-l, l-diphosphonic acid and approx. 80 % N, N-bis-carbocyethane-3-hydroxy-l-aainopropane-' l, l-dipho8phonic acid.

example

24.9 g of 2-carboxy-l-aainoethane-l, l-diphoephone acid are used in 50 ° C dissolved in 119 al 30J potassium hydroxide solution with Buhren and added this temperature entered 19 g of 5-broarianic acid. You cook 3 l / 2 hours as backflow, cools down, treats the solution as a cation exchanger, constricts the acid solution almost to acid Dry up and crystallize old oil from methanol, ethanol and acetone fractionated. The yield of 2-carboxy-l, l-diphospkono-ethane-1-aminopentanoic acid is 24.5 g *

Analysis bor. 1 Ct 27.52 ft, Nt 4.01 t, Pt 17.74 % f.t Ct 27.5 % t Ni 3.9 if Pt 17.8 %

MolTerh.t CiPtN - 8.23 1 2.06 1 1.

909809/0227

Registered office of the company: Ladwiburg / Neckar ■ AmtsgerlchtMannhelm, Reg. Nr.B1305 - Managing director: Dr. Karlheinz Emst. Dr. Theodor Rlehm 3.26 / 8.73 / 10,000 NL

BENCKISER-KNAP ^ ACK GMBH tW02 LADEiMbJRG / NECKAR

Telephone * * (06203) 771 Telegraph 0463061 Wire address BEKA Ladenburg

Example I6i

6.9 g of l-aainododecane-lil-diphosphonic acid are dissolved in 56 g of 10% potassium hydroxide solution, 2.8 g of 3-chloro-2,2-di-ethylpropionic acid are added at 60 ° C. and refluxed for 3 hours. After working up the reaction solution by means of an acidic cation exchanger, filtering and concentrating the acid solution, 6 g of N-2-carboxy7 ~ 2 _f 2-di-methylthane-1-aainododecan-1 , 1-diphosphonic acid are obtained by crystallization from methanol / water.

Analyzes bor.ι Ct 45.84 % _t Nt 3.14 %, Pt 13.91 % gef.i Ct 47.8 %, Nt 3.2 %, Pt 14.4 yrs.

Melrerh.t CtPtN - 17.43 »2.03» 1 ·

909809/0227

8ttz der GeeeHachaft: Lemnburg / Neckar ■ Mannheim District Court, Reg. No. B1305 · Managing Director: Dr. Karlheinz Ernst. Dr. Theodor Rlehm NL

Claims (2)

BENCKISER-KNAPtACK GMBH · Ö802 LAÜEnBJRG / NECKAR o _ o "- _ An. Hafe.i 2 · Postfach A I V / (Of Fernruf * * (06203) 771 Telegraph 0463061 Wire address BEKA Ladenbure 16 patent claims 1. Process for the preparation of N-carboxyalkane-aainoalkane, N-carboxyalkane-azacycloalkane and N-carboxyalkane-aminoarylalkane-phoaphonic acids, characterized in that «of aminoalkane, azacycloalkane or aminoarylalkane-phosphonic acids the general formula R - C N in RH, (CH ₀ ) CH-, C ₀ H ₁ OH, CH ₀ COOH, C mm Z J Jm * k tm (CH ₂ ) _n -N- (CH ₂ C00H) ₂ , (CH ₂ J _n -I where η - 1 or 2 and χ - 0 - 10, or with ring formation with R "B ₁ - PO ₃ H ₂ Rg - H, CH- or with ring formation with R - (CH ₂ ), _ are, with straight or branched-chain haloalkane monocarboxylic acids or haloalkane dicarboxylic acids or their alkali salts or esters at temperatures of 50 - 160 C in a molar ratio of 1: 1 to 1 t 3 in an aqueous medium at a pH between k and 12, preferably 7 and 9 »implements. 909809/0227 Registered office of the company: Ladenburg / Neckar · District Court of Mannhelm, Reg. No. B1305 ■ Managing Director: Dr. Karlheinz Ernst, Dr. Theodor Rlehm 3.26 / a73 / 10,000 NL BENCKISERKNAPtACK GMBH · ddO2 LAÜEivbJRG / NECKAR - _ _o "- Atr. Port 2 · P.O. Box AI > J / £ b Telephone * * (06203) 771
Telegraph 0463061
Wire address BEKA Ladenburg 17th 2. / N-carboxyalkane-aminoalkane-diphosphonic acids, N-carboxyalkanasacyeloalkane-diphoaphonic acids and N-carboiyalkane-aaiinoarylalkane-diphoephone acids the general formula B-C N In the RH, CH ₃ , - (CH ₂ J ₁₀ CH ₃ , CgH ₅ , C ₃ H ₄ OH, CHgCOOH or with ring formation with R- ■ (CH ")., B ₂ - H, R- or with ring formation with B - - (CH ₂ ) -, B ₃ - (CH ₂ ) ^ COOH, m - 2 - 12, CH ₃ -C (CHJ ₂ -COOH and -CH - COOH CH ₂ - COOH. 909809/0227 Company headquarters: Ladenburg / Neckar ■ Mannheim District Court, Reg. No. B1305 ■ Managing Director: Dr. Karlheinz Ernst, Dr. Theodor Rlehm 3.26 / 8.73 / 10,000 NL