GUANIDATED AMINOPHOSPHONIC ACID COMPOUNDS

Abstract: Novel guanidated aminophosphonic acid compounds their use as biocides and their intermediates. The compounds are guanidated N-(aminoalkyl) aminoalkanephosphonic acid derivatives and are characterized in that they comprise both a phosphonic acid type group and at least one guanidino group and also in that they are based on alkylene amines. The compounds have the general formula: (I) wherein Z and Z' are hydrogen, a lower alkyl group or an alkali metal, Y is hydrogen or an amidine group, m is 1-3, n is 4-16 and p is 1-3. The compounds can be prepared by reacting a halogenoalkanephosphonic acid compound with an alkylene di- or polyamine followed by guanidation of the so obtained product. The compounds are particularly useful as fungicides and especially as fungicides for industrial purposes.

Description: GUANIDATED AMINOPHOSPHONIC ACID COMPOUNDS The present invention relates ' to novel guanidated aminophosphonic acid compounds and to the use of these compounds as biocides. The invention further relates to 5. a process for the preparation of the guanidated amino¬ phosphonic acid compounds and to novel aminophosphonic acid compounds useful as intermediates in this process. The novel compounds of the invention have the gene- * ral formula 10. wherein Z and Z', which may or may not be equal, are * hydro¬ gen, a lower alkyl group having 1 to 4 carbon atoms or an alkali metal, Y is hydrogen or an amidine group, m is 1 to 3, n is 4 to lβ and p is 1 to 3« The invention -also covers acid addition salts. 15• The compounds of the above given formula can be class¬ ed as guanidated N-(aminoalkyl)aminoalkanephosphonic acid derivatives and in the formula the lower alkyl esters, half esters and also the alkali metal mono- or di- salts are in¬ cluded. 20. The compounds are characteristic in that they contain both a phosphonic acid type group, ~ *** and at least one g , and in that they are based on alkylene amines. The pure compounds of the free phosphonic acids are 25. fine white crystalline solids, and they are all soluble in water. The solubility in water decreases somewhat with in¬ creasing chain lengths.."The esters are less soluble in water but soluble in alcohols and other solvents. As a rule the acid addition salts of the guanidated aminophosphonic acid compounds are much more soluble in water than the free acids and also more soluble in alcohols. Preferred compounds are those containing alkylene 5. groups having from 4 to 1 carbon a oms, and especially from 6 to 14 carbon atoms. Further, compounds of the gene¬ ral formula I given above wherein p equals 1 are preferred, i.e. the compounds based on alkylene diamines . Compounds wherein m is 1 are preferred to those wherein m equals 2 10. or 3- It should be understood that when p is 2 or 3, n does not necessarily have to be the same for the different alkyl¬ ene groups. These might of course vary as a result of the use of technical amines having varying chain lengths as 15. starting material. It should further be understood that when p is 2 or 3 . either one, two or three of the Y-groups may be amidine groups, ^NH 2 the rest being hydrogen. This depends on the guanidation reagent used in the preparation process and will be describ- 20. ed more in detail below. However, compounds wherein all groups Y are hydrogen are preferred. The invention also relates to a method for the pre¬ paration of guanidated N-(aminoalkyl)aminoalkanephosphonic acid derivatives of the above given formula (I), said method 25- comprising reacting a halogenoalkanephosphonic acid compound with- an alkylene di- or polyamine and guanidation of the so obtained product. The first step of the preparation method comprises reacting a halogenoalkanephosphonic acid compound having 30. the formula wherein Z and Z τ , as above, independent of each other are OMPI hydrogen, a lower alkyl group having 1 to 4 carbon atoms or an alkali metal, and m is 1 to 3 . preferably 1, and wherein X is a halogen, suitably chlorine or bromine and most preferably chlorine, with an alkylene di- or poly- 5. amine of the formula H 2 (CH 2 ) n NH p (CH 2 ) n NH 2 wherein n is 4 to lβ and p is 0, 1 or 2. Diamines of this type are suitably used as starting material. The reaction between the halogenoalkanephosphonic acid compound and the amine is carried out in aqueous so- 10. lution and at an elevated temperature. The temperature is suitably within the range of from 50 to 100°C and prefer¬ ably from 70 to 100°C. The reaction rate will of course vary with the temperature and also with the starting mate¬ rials; usually a reaction time of up to about 20 hours will 15. be sufficient. The reaction can be carried out under re¬ flux. After the reaction is completed water and optionally excess of unreacted amine are removed, e.g. by distillat¬ ion, and the product is isolated. The aminoalkylaminophosphonic acid derivatives of the 20. general formula are then guanidated using conventional guanidation reagents such as * cyanamide, O-alkylisoureas, S-alkylisothioureas or salts of these etc. The temperature at the guanidation is not critical but may vary within wide limits, from room 25. temperature up to about 100°C. The guanidation step is car¬ ried out under neutral or alkaline conditions and when the reaction is completed the reaction product solution is neut¬ ralized. The compounds can then be crystallised for isolat¬ ion. 30. The above general preparation method applies to all the compounds. As concerns the acid addition salts these will vary with the guanidation reagent used and so will thenumber of guanidated amino groups. The acid addition salt will further vary with the neutralizing agents used in the process. In the first reaction ' step the molar ra¬ tio of di- or polyalkylene amine to halogenophosphonic 5. acid compound is suitably within the range of from 2:1 to 8:1 and preferably within the range of from 4:1 to 6:1. In the guanidation step it is usually sufficient to have a ratio of 1:1 between the guanidation reagent and the amino groups to be guanidated, although an excess of the 10. guanidation reagent may be used. As shown in the general formula I the novel compounds of the present invention may contain both guanidated pri¬ mary and secondary amino groups. Compounds containing one or several guanidated secondary amino groups, i.e. those 15. in which Y is an amidine group, may be prepared using cyan- amide as guanidation reagent. In contrast to the urea de¬ rivatives cyanamide is an unspecific guanidation reagent and will randomly guanidate both primary and secondary amino groups, while the ureas will predominantly guanidate 20. the primary amino groups. The aminoalkylaminophosphonic acid compounds of the general 'formula (II) wherein Z and Z', which may or may not be equal, are hydro¬ gen-, a lower alkyl group having 1 to 4 carbon atoms or an 25. alkali metal, m is 1 to 3, n is 4 to 16 and p is 1 to 3, which are intermediates in the preparation of the guanidat¬ ed aminophosphonic acid compounds , are novel and claimed per se. n is suitably 6 to 14. The novel guanidated compounds of the present invent- 30. ion can be in the form of the free phosphonic acids or phos- phonates or in the form of acid addition salts. Both salts of mineral acids and organic acids can be prepared. When cyanamide is used as the guanidation reagent the acid addi¬ tion salt is suitably prepared by adding the desired acid OMPI in or after the guanidation step and when ureas are used as guanidation reagents an isouronium compound or isothio- uronium compound is selected for the preparation of acid addition salts. As examples of salts of organic acids can 5. be mentioned those of lower organic acids such as formates and acetates, those of higher organic acids such as oleat- es and stearates. Benzoates may also be used. The type of acid salt will of course also have to be selected with respect to the intended use of the compound in order not 10. to have any negative effects in this use. Particularly claimed compounds according to the in¬ vention are the novel compounds of formula I wherein Z and Z' both are hydrogen, m is 1 or 2, n is 6 to 14 and p is 1 and the corresponding intermediates of formula II wherein 15.. Z and Z - both are hydrogen, m is 1 or 2, n is 6 to 14 and p is 1. The invention also covers the use of the guanidated aminophosphonic acid compounds as biocides, and particular¬ ly as plant protecting agents, antimicrobial agents and in- 20. secticides. For this purpose it is in most cases sufficient to use the crude reaction product resulting from the react¬ ion between the halogenoalkanephosphonic acid or phospho- nate and the amine in the guanidation step without an in¬ termediate recrystallisation. The guanidated product will 25. then contain the novel compounds of the invention as the main component and the rest will consist of guanidated di- or higher alkyleneamines and of intermediate unguanidated aminoalkylaminophosphonic acid compounds. Guanidated di- or higher alkyleneamines are previously known to have bio- 30. cidal effect and it has been found that the intermediate aminophosphonic acid compounds of the present invention in some cases possess biocidal effect and this makes it possib¬ le to utilize a crude reaction product. The products, or compounds, can be formulated in conventional manner and 35. used with inert carriers or diluents. They may be useful in several areas; for example as bactericides, fungicides, insecticides, herbicides etc. The compounds are particular¬ ly useful as fungicides both for industrial purposes, in wood treatment and especially as fungicides for agricul¬ tural and horticultural purposes. The use of the compounds as fungicides in agriculture and horticulture, and especial ly as foliar fungicides is a preferred embodiment of the 5. invention. It should also be mentioned that the compounds have other utilities; they might for example be used as chelating agents. The invention is further illustrated in the follow- • ing -examples which, however, are not intended to limit 10. the same. Example 1 A. Preparation of N-(12-a-minododecyl)-aminomethanephos- phonic monohydrate. Compound 1 A. Chloromethanephosphonic acid (15.1 g 3 115.7 mmoles) 15. and 1,12-diaminododecane (100 g, 0.5 moles) were heated under reflux in water (160 cm ) for 20 hours. The water was then distilled off and ethanol (250 cur) was added. The phosphonic acid was filtered off and dried. The crude yield was 30.7 g (85 % ) • A sample was purified by recrys- 20. tallization from water/ethanol to give N-(12-aminododecyl)- -aminomethanephosphonic acid monohydrate as a fine white crystalline solid having a melting point of 234 C. B. Preparation of N-(12-guanidinododecyl)-aminomethane- phosphonic acid monohydrate. Compound ' 1 B. 25. N-(12-aminododecyl)-aminomethanephosphonic acid ' mono¬ hydrate (2.5 g, 8 mmoles), sodium hydroxide (1.3 g, 38 mmoles) and S-methylisothiouronium chloride (2.0 g, 16.4 mmoles were dissolved in water (120 cm ) and heated at 90 C for 4 hours. The solution was acidified to pH 1 with 30. hydrochloric acid, and evaporated. Methanol (100 cm ) was added and sodium ' chloride was filtered off. " The filtrate was neutralized to pH 6 with propylene oxide. The solid so formed was filtered off and washed with methanol (50 cm ) . 35- The crude yield after drying of guanidinophosphonic acid was 2.6 g (91 % ) . A sample was recrystallized from hot water to give N-(12-guanidinododecyl)-aminomethane- phosphonic acid monohydrate as a fine white crystalline solid having a melting point of 129-130°C. Example 2 A. Preparation of N-(6-aminohexyl)-aminomethanephosphonic acid monohydrate. Compound 2 A. • Chloromethanephosphonic acid (6.5 g, 49.8 mmoles) 5. and 1.6-diaminohexane (34.8 g, 300 mmoles) were dissolved in water (130 cm ) and heated under reflux for 20 hours. The water was removed and ethanol (250 era ) was added to the solid residue. The phosphonic acid was filtered off and dried. The crude yield was 10.4 g (92 % ) . A sample 10. was purified by recrystallization from water/ethanol to give N-(6-aminohexyl)-aminomethanephosphonic acid monohyd¬ rate as a fine white crystalline solid having a melting point of 235°C B. Preparation of N-(6-guanidinohexyl)-aminomethanephos- 15. phonic acid monohydrate. Compound 2 B. N-(6-aminohexyl)-aminomethanephosphonic acid mono¬ hydrate (6.1 g, 26.7 mmol) , sodium hydroxide (4.15 g, 104 mmoles) and S-methylisothiouronium chloride (6.3 g, 49.8 mmoles) were dissolved in water (50 cm ) and heated 20. at 6θ°C for 4 hours. The solution was acidified to pH 1 with hydrochloric acid and evaporated. Methanol (50 cm ) was added and sodium chloride was filtered off. The filt¬ rate was neutralized to pH 6 with propylene oxide. The sticky precipitate was dissolved in cold water 25- (50 era ) and acetone added dropwise until the solution just became opaque. A few drops of water were added to clear the solution which was then stored in a fridge for sev.eral days. The crystals formed were filtered off, wash- • ed with acetone and dried in a vacuum oven at 60 C to 30. yield N-(6-guanidinohexyl)-aminomethanephosphonic acid monohydrate (4.3 g > 60 % ) as a fine white crystalline solid having a melting point of 182 C. Example 5 A. Preparation of N-(10-aminodecyl)-aminomethanephosphonic 35- acid monohydrate. Compound 5 . . Chloromethanephosphonic acid (5-5 g } 42 mmoles) and 1.10-diaminodecane (44 g, 255 mmoles) were heated under reflux in water (200 cm ) for 20 hours. The water was re- moved and ethanol (400 cm ) added to the solid residue. The phosphonic acid was filtered off -and dried. The crude yield was 11.4 g (87 % ) . A sample was purified by recrys¬ tallization from water/ethanol to give N-(lO-aminodecyl)- 5. -aminomethanephosphonic acid monohydrate as a fine white crystalline solid having a melting point of 238°C. B. Preparation of N-(10-guanidinodecyl)-aminomethanephos- phonic acid monohydrate. Compound 5 B. N-(lθ-aminodecyl)-aminomethanephosphonic acid mono- 10. hydrate (4.1 g, 14.4 mmoles), S-methylisothiouronium chlo¬ ride (3.65 g, 28.9 mmoles) and sodium hydroxide (2.8 g, 70 mmoles) wer.e dissolved in water (100 cm ) and heated in an oil bath at 70°C for 4 hours. The clear solution was then acidified to pH 1 with concentrated hydrochlorid acid 15« and the volatile components were removed on a rotary eva¬ porator. The oily residue was dissolved in methanol (100 cm *5 ) and sodium chloride filtered off (3-4 g, 83 % ) • Pro¬ pylene oxide was then added to the filtrate until pH 6. The crude guanidinophosphonic acid was washed with 20. methanoi (50 cm 3 ) and dried. The yield was 4.2 g (89 % ) . Recrystallization from water/acetone and drying at 60 C gave N-(lO-guanidinodecyl)-aminomethanephosphonic acid monohydrate (3.8 g, 81 % ) as a fine white crystalline so¬ lid having a melting point of 133-134°C. 25. Example 4 A. Preparation of N-(8-aminooetyl)-2-aminoethanephosphonic acid monohydrate. Compound 4 A. Diethylbromoethanephosphonate (15-3 g, 0.062 moles) and 1.8-diaminooctane (54.0 g, 0.375 moles) were heated 30. under reflux in water (250 cm 5 ) for 5 hours. The water and excess diamine were then distilled off. Concentrated hydro¬ chloric acid (280 cm 5 ) was added and the solution heated under reflux for 8 hours. The solution was then evaporated to dryness on a rotary evaporator and the residue was dis- 35» solved in methanol (75 cm ) and propylene oxide wad added to pH 6. The phosphonic acid was filtered off and dried. The crude yield was 10.2 g (60.5 % ) • A sample was purified by recrystallization from water/ethanol to give N-(8-amino- octyl)-2-aminoethanephosphonic acid monohydrate as a fine white crystalline solid having a melting point of 210 C. B. Preparation of N-(8-guanidinooctyl)-2-aminoethanephos- phonic acid monohydrate. Compound 4 B. 5. N-(8-aminooctyl)-2-aminoethanephosphonic acid mono¬ hydrate (4.0 g, 0.0148 moles), S-methylisothiouronium chlo¬ ride (3-75 g } 0.0296 moles) and potassium hydroxide (3.32 g_ 0.0592 moles) were dissolved in water (60 cπr) and heat¬ ed in an oil bath at 80 C for 4.5 hours. The clear solution 10. was then acidified to pH 2 with concentrated hydrochloric acid and the volatile components were removed on a rotary evaporator. The oily residue was dissolved in methanol (75 - cm ) and potassium chloride filtered off (3-5 g_ 79-3 % ) • Propylene oxide was then added to the filtrate until pH 6. 15. The sticky precipitate was dissolved in cold water (50 cm ) and acetone added dropwise until the solution just became opaque. A few drops of water were added to clear the solu¬ tion which was then stored in a fridge for several days. The crystals formed were filtered off, washed with acetone 20. and dried in a vacuum oven at 6θ°C to yield N-(8-guanidino- octyl)-2-aminoethanephosphonic acid monohydrate (2.7 g_ 58.4 ' % ) as a fine white crystalline solid having a melting point of 108°C. Example 5 25- A. Preparation of N-(8-aminooctyl)-aminomethanephosphonic acid monohydrate. Compound 5 A. Chloromethanephosphonic acid (7-5 g, 58 mmoles) and 1.8-diaminooctane (50.0 g, 347 mmoles) were dissolved in water (130 cm ) and heated under reflux for 20 hours. The - 30. water was then removed and ethanol (250 era ) added to the solid residue. The phosphonic acid was filtered off and dried. The crude yield was 13-3 g (90 % ) . A sample was purified by recrystallization from water/ethanol to give N-(8-aminooctyl)-aminomethanephosphonic acid monohydrate 35. as fine white solid having a melting point- of 242°C. B. Preparation of N-(8-guanidinooctyl)-aminomethanephos- phonic acid monohydrate. Compound 5 B. N-(8-aminooctyl)-aminomethanephosphonic acid mono- hydrate (5.6 g, 21.9 mmoles), ^-methylisothiouronium chlo¬ ride (5.53 g, 43.7 mmoles) and potassium hydroxide (4.9 g_ 87.3 mmoles) were dissolved in water (50 cm ) and heated in an oil bath at 60°C for 4 hours. The solution was cool- 5. ed and acidified to pH 1 with concentrated hydrochloric acid. The volatile components were removed on a rotary eva¬ porator and methanol (50 cm ) added to the residue. Potass¬ ium chloride (5.9 g, 80 % after drying) was filtered off and propylene oxide added to the filtrate until pH 6. 10. The supernatant liquors were decanted off from the oil formed on addition of the propylene oxide and the oil washed with methanol (50 cm ) . Acetone (75 cm ) was added and the solvents removed on a rotary evaporator. The solid so formed was dried in a vacuum oven at 6θ°C (5 hours), to 15. give crude guanidinophosphonic acid (5.8 g, 89 % ) • Recrys¬ tallization from water/acetone gave N-(8-guanidinooctyl)- -aminomethanephosphonic acid monohydrate (3-9 g, 60 % ) as a fine white crystalline solid having a melting point of 170°C. 20. Example 6 A. Preparation of N-(4-aminobutyl)-aminomethanephosphonic acid monohydrate. Compound 6 A. Chloromethanephosphonic acid (7.0 g, 53.6 mmoles) and 1,4-diaminobutane (30-0 g, 340 mmoles) were heated under re- 25. flux in water (200 cm ) for 20 hours. The water was then distilled off and acetone (110 cm 5 ) was added. The phospho¬ nic acid was filtered off and dried. The crude yield was 9.8 g (91 % ) . A sample was purified by recrystallization from water/ethanol to give N-(4-aminobutyl)-aminomethane- 30. phosphonic acid monohydrate as a fine white crystalline so¬ lid having a melting point of 258°C. B. Preparation of N-(4-guanidinobutyl)-a- * ϊiinomethanephospo- nic acid monohydrate. Compound 6 B. N-(4-aminobutyl)-aminomethanephosphonic acid monohyd- 35. rate (3.8 g, 19 mmoles), sodium hydroxide (3-0 g, 76 mmoles) and S-methylisothiouronium chloride (4.8 g, 38 mmoles) were dissolved in water (50 cm 5 ) and heated at 70°C for 4 hours. The solution was acidified to pH 1 with hydrochloric acid URΪ OMPI and evaporated. Methanol (100 cm 5 ) was added and sodium chloride was filtered off. The filtrate was neutralized to pH 6 with propylene oxide. The sticky precipitate was dissolved in a minimum of cold water and acetone added drop- 5. wise until the solution just became opaque. A few drops of water were added to clear the solution which was then stored in a fridge for several days. The crystals formed were filtered off, washed with acetone and dried in a va¬ cuum oven at 6θ°C to yield N-(4-guanidinobutyl)-aminome- 10. thanephosphonic acid monohydrate (2.9 g, 63 % ) as a fine white crystalline solid having a melting point of 160- -161°C. Example 7 Preparation of N-(9~aminononyl)aminomethanephosphonic acid 15. monohydrate. Compound 7A. Chloromethanephosphonic acid (4.0 g, 30.6 mmoles) and 1.9-diaminononane ' (20.1 g, 127.2 mmoles) were dissolved in water (100 cm ) and the resultant solution heated under re¬ flux for 20 hours. The water was then distilled off and 20. methanol (80 cm ) added to the residue. The solid was fil- tered off, washed with methanol (2 x 50 crrr) and dried in a vacuum oven at 60°C for three hours to yield the crude N- -(9~aminononyl)aminomethanephosphonic acid monohydrate (6.5 g, 78.5 % ) , havin -a melting point of 240-24l°C. 25. Example 8 Preparation of the di-potassium salt of N-(8-guanidino-oc- typaminomethanephosphonic acid. Compound 8. N-(8-guanidino-octyl)aminomethanephosphonic acid mono¬ hydrate (3.0 g, ' 10.07 mmoles) and potassium hydroxide (1.13 30. g, 20.14 mmoles) were dissolved in water (100 cm J ). The water was then distilled off and methanol (80 cm- * ) added to the re¬ sidue. Filtration and then evaporation of the methanol, follo¬ wed by drying in a vacuum oven at 6θ°C for three hours gave the crude di-potassium salt as a white solid (2.7 g, 71.7 % ) . 35. Identification of compounds The structures of the compounds were ascertained by nuclear magnetic resonance ( H-, 5 C-, 1* ^N- and 51 P-) spectra and mass spectra. All compounds give very strong (M+l) -peaks (in most cases the base peak) using FAB- (Fast Atom Bombardment) mass spectrometry, see below Compound Molecular weight (M+l) 1A 294 295 5- 2A 210 211 3A 266 267 4A 252 253 5A 238 239 6A 182 183- 10.. IB 336 337 2B 252 253 3B 308 309 4B 294 295 5B 280 281 15- Example 7 Fungicidal activity test Compounds prepared as above were screened for their fungicidal activity. The fungicidal activity of the substances was examin- 20. ed using a mycelial growth inhibition test on agar accord¬ ing to the following method. The substances were dissolved in sterilized potatoe dextrose agar (PDA) to give concentrations of 500 and 1000 ppm respectively. The mixtures were then poured onto stan- 25. dard petri dishes with 9 cm diameter. A 5 mm diameter agar plug with lively growing mfycelia (cultivated on PDA) was placed in the center of each petri dish. After incubation at +28 C for 7 to 21 days (depending on the growth rate of the respective fungus) the growth diameter was" measured and 30. compared with that of untreated dishes. Several plant pathogenic fungi belonging to different subdivisions and representative of important crop diseases were used in the tests. -In the tables below the results are shown by classi- 35. fying the compounds according to the following scale: 0 = 0-25 % inhibition of growth, 1 = 26-50 % inhibition of growth, 2 * = 51-75 % inhibition of growth, 3 = 76-99 % in¬ hibition of growth, 4 = 100 % inhibition of Table 1 Efficacy of Compound Fungus Dosage 1 B 3 B 5 B (ppm) Pyricularia oryzae 5-00 1 4 2 Botrytis cinerea 500 3 4 0 Rhizoctonia solani 500 1 1 0 _ " _ 1000 4 2 n.t . Septoria nodorum 500 1 • 4 1 _ " _ 1000 2 4 2 Drechslera . sativa 500 3 4 n.t. 1000 3 4 3 Fusarium avenaceum 1000 n.t. Note: n.t. = not tested Table 2 Efficacy of Compound Fungus Dosage 1A 2A 3A 4A 5A 6A 2B 4B (ppm) Drechslera sativa 500 n.t . n.t 3 3 n.t. n.t. n.t. 2 _ " _ 1000 4 2 3 3 2 2 2 n.t Septoria nodorum 500 n.t. 0 Note: -n.t. = not ' tested

Claims: Claims 1. Guanidated N-(aminoalkyl)aminoalkanephosphoniJ acid derivatives having the general formula wherein Z and Z', which may or may not be equal, are hyd¬ rogen, a lower alkyl group having 1 to 4 carbon atoms or 5. an alkali metal, Y is hydrogen or an amidine group, m is 1 to 3, n is 4 to 16 and p is 1 to 3, or their acid addi¬ tion salts. 2. Compounds according to claim 1, wherein p is 1. 3. Compounds according to claim 1, wherein m is 1. 10. 4. Compounds according to claim 1, wherein Z and Z' are hydrogen. 5- A process for the preparation of guanidated N- -(aminoalkyl)aminoalkanephosphonic acid derivatives having the general formula 15. wherein Z and Z', which may or may not be equal, are hyd¬ rogen, a lower alkyl group having 1 to 4 carbon atoms or -an alkali metal, Y is hydrogen or an amidine group, m is 1 to " 3", n is 4 to l6 ~ and p is 1 to 3, or acid addition salts thereof by reacting a . halogenoalkanephosphonic acid 20 or phosphonate having the general formula wherein Z and Z' have the above given meaning, m is 1 to 3 and X is halogen, with a di- or polyamine having the general formula WIPO H 2 N (CH 2 ) n NH ,(CH 2 ) n NH 2 wherein n has the above given meaning and p is 0, 1 or 2, in aqueous solution at an elevated temperature for forma¬ tion of an aminoalkylaminophosphonic acid derivative which is subsequently guanidated by reacting it with a guanida¬ tion reagent. 6. A process according to claim 5 wherein the molar ratio of the amine to the halogenoalkanephosphonic acid or phosphonate is within the range of from 2:1 to 8:1. 7. A process according to claim 5 wherein the guanida¬ 10. tion reagent is S-methylisourea, O-methylisourea, or salts thereof, or cyanamide. 8. Aminoalkylaminophosphonic acid derivatives having the general formula wherein Z and Z', which may or may not be equal, are hydro- 15- gen, a lower alkyl group having 1 to 4 carbon atoms or an alkali metal, m is 1 "to 3, n is 4 to 16 and p is 1 to 3. 9. Aminoalkylaminophosphonic acid derivatives accord¬ ing to claim 8, wherein Z and Z' are hydrogen, m is 1, p is 1 and n is 6 to 14. 20. 10. Use of guanidated N-(aminoalkyl)aminoalkanephos¬ phonic acid derivatives having the general formula wherein Z and Z r , which ' may or may not be equal, are hydro¬ gen, a lower alkyl group having 1 to 4 carbon atoms or an alkali metal, Y is hydrogen or an amidine group, m is 1 to 25. 3, n is 4 to 16 and p is 1 to 3, or their acid addition salts, as biocides. OMPI

Inventors: CAMERON DAVID G, HUDSON HARRY ROBINSON, LAGERLUND INGER, PIANKA MAX, STROEMBERG ANITA, CAMERON, DAVID, G., HUDSON, HARRY, ROBINSON, LAGERLUND, INGER, PIANKA, MAX, STROEMBERG, ANITA
Applicants: KENOGARD AB
Application year: 1984
Main classification: C07F9
IPC codes: A01N57, C07F9