CA1077518A - Process for producing 1-aminoalkane-1,1-diphosphonic acids - Google Patents
Process for producing 1-aminoalkane-1,1-diphosphonic acidsInfo
- Publication number
- CA1077518A CA1077518A CA278,707A CA278707A CA1077518A CA 1077518 A CA1077518 A CA 1077518A CA 278707 A CA278707 A CA 278707A CA 1077518 A CA1077518 A CA 1077518A
- Authority
- CA
- Canada
- Prior art keywords
- nitrile
- acid
- phosphorous acid
- reaction
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000002253 acid Substances 0.000 title description 12
- 150000007513 acids Chemical class 0.000 title description 7
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000002825 nitriles Chemical class 0.000 claims abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 36
- -1 Lewis acid compound Chemical class 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 4
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 claims description 3
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- ZDULHUHNYHJYKA-UHFFFAOYSA-N 2-propan-2-ylsulfonylpropane Chemical compound CC(C)S(=O)(=O)C(C)C ZDULHUHNYHJYKA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 239000000010 aprotic solvent Substances 0.000 claims description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- WKJHMKQSIBMURP-UHFFFAOYSA-N tridecanenitrile Chemical compound CCCCCCCCCCCCC#N WKJHMKQSIBMURP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 125000002947 alkylene group Chemical group 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical compound OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 241001584898 Cerma Species 0.000 description 1
- VXCUURYYWGCLIH-UHFFFAOYSA-N Dodecanenitrile Chemical compound CCCCCCCCCCCC#N VXCUURYYWGCLIH-UHFFFAOYSA-N 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009089 cytolysis Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- 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 Table
- 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 ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or 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)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
The present invention provides a process for producing a l-aminoalkane-l,l-diphosphonic acid having the general formula
The present invention provides a process for producing a l-aminoalkane-l,l-diphosphonic acid having the general formula
Description
75~3 The present invention rel~tes to a process for producing l~minoalkane~ diphosphonic acids : r The production of l;aminoalkane-l,l-diphosphonic acids by reaction of alkyl nitrile with phosphorus halides is disclosed in Cerma~n Ratent No. 1,002,355, However, satisfactory yields could be attained only with phosphorus tribromide.
j Further, the reaction of nitriles with phosphorous .l acid in the presence of hydrogen halide is disclosed in laid-open German Patent Application No. 2,048,913. The two processes have the disadvantage that because of the intensely corrosive : properties of the phosphorus halides and hydrogen halides certain / difficulties are encountered with the apparatus in production on an industrial scale. .
It has now been found that these disadvantages can be avoided and that it is possible to obtain, in a simple manner, l-aminoalkane-l,l-diphosphonic acids having the general formula HO 11 I 11 ~ OH
~P - C -- P
: HO / ¦ OH
wherein R represents a hydrocarbon radical containing 1 to 12 carbon atoms, when nitriles having the general formula R-CN, :~:
wherein R has the meaning defined hereinbefore, are reacted with .`.
phosphorous acid at temperatures from 140 to 210C.
According to the present invention therefore there .
; is provided a process for producing a l-aminoalkane-l,l-diphos-~ phonic acid having the general formula , ~ O NH
HO 11 I 2 I~OH
HO ~ 0~ , !
wherein R represents a hydrocarbon radical containing 1 to 12 carbon atoms which comprises reacting a nitrile having the general formuIa R-CN, wherein R is as above with phosphorous acid at a temperature from 140 to 210C. :
~, .
~77~L8 Suitable nitriles, the hydxocarhon radic~l of which contains l to 12 C atoms include aliphatic, branched or straight-chain hydrocarbon nitriles, Particularly preferred are acetonitrile, propionitrile, butyronitrile, lauryl cyanide and diethox~phosphono propionitrile The nitriles and the phosphorous acid are suitably reacted in a molar ratio o approximately 1:2. Alternatively a mixture containing 1 mole of nitrile, 1.6 moles of phosphorous acid and 0.2 mole of pyrophosphorous acid are reacted while heating to the aforesaid temperature range.
Since phosphorous acid normally disproportinates into PH3 and H3PO4 at ternperatures from 160 to 200C, it was surprising that stable mixtures which react to form aminoalkane diphosphonic acids are formed at the above temperatures without forminy appreciahle amounts of PH3 or H3PO4. It is believed that adduct formation of nitrile occurs with the phosphorous acid since only a small amount of nitrile is distilled off despite the fact that the boiling point thereof is substantially exceeded (for example, acetonitrile has a boiling point of 82~C).
The yield of l-aminoalkane~ diphosphonic acids can be increased by approximately 5 to 10% by adding catalytic amounts of Lewis acids to the reaction mixture. Aluminium chloride, zinc chloride, aluminium bromide and antimony penta-- chloride are for example suitablè as catalysts.
The alkali or alkaline earth metal salts can be produced by neutraliza~ion of an aqueous suspension of the aminoalkane diphosphonic acids by means of alkali or alkaline earth metal hydroxides. Sometimes alkali metal salts are distinguished by - the fact that they have a better solubility than the free acid.
However, the solubility usually is adequate for using the compounds either alone or in combination with chelating agents or stabilizers in the most diverse fields of application, or example, in the
j Further, the reaction of nitriles with phosphorous .l acid in the presence of hydrogen halide is disclosed in laid-open German Patent Application No. 2,048,913. The two processes have the disadvantage that because of the intensely corrosive : properties of the phosphorus halides and hydrogen halides certain / difficulties are encountered with the apparatus in production on an industrial scale. .
It has now been found that these disadvantages can be avoided and that it is possible to obtain, in a simple manner, l-aminoalkane-l,l-diphosphonic acids having the general formula HO 11 I 11 ~ OH
~P - C -- P
: HO / ¦ OH
wherein R represents a hydrocarbon radical containing 1 to 12 carbon atoms, when nitriles having the general formula R-CN, :~:
wherein R has the meaning defined hereinbefore, are reacted with .`.
phosphorous acid at temperatures from 140 to 210C.
According to the present invention therefore there .
; is provided a process for producing a l-aminoalkane-l,l-diphos-~ phonic acid having the general formula , ~ O NH
HO 11 I 2 I~OH
HO ~ 0~ , !
wherein R represents a hydrocarbon radical containing 1 to 12 carbon atoms which comprises reacting a nitrile having the general formuIa R-CN, wherein R is as above with phosphorous acid at a temperature from 140 to 210C. :
~, .
~77~L8 Suitable nitriles, the hydxocarhon radic~l of which contains l to 12 C atoms include aliphatic, branched or straight-chain hydrocarbon nitriles, Particularly preferred are acetonitrile, propionitrile, butyronitrile, lauryl cyanide and diethox~phosphono propionitrile The nitriles and the phosphorous acid are suitably reacted in a molar ratio o approximately 1:2. Alternatively a mixture containing 1 mole of nitrile, 1.6 moles of phosphorous acid and 0.2 mole of pyrophosphorous acid are reacted while heating to the aforesaid temperature range.
Since phosphorous acid normally disproportinates into PH3 and H3PO4 at ternperatures from 160 to 200C, it was surprising that stable mixtures which react to form aminoalkane diphosphonic acids are formed at the above temperatures without forminy appreciahle amounts of PH3 or H3PO4. It is believed that adduct formation of nitrile occurs with the phosphorous acid since only a small amount of nitrile is distilled off despite the fact that the boiling point thereof is substantially exceeded (for example, acetonitrile has a boiling point of 82~C).
The yield of l-aminoalkane~ diphosphonic acids can be increased by approximately 5 to 10% by adding catalytic amounts of Lewis acids to the reaction mixture. Aluminium chloride, zinc chloride, aluminium bromide and antimony penta-- chloride are for example suitablè as catalysts.
The alkali or alkaline earth metal salts can be produced by neutraliza~ion of an aqueous suspension of the aminoalkane diphosphonic acids by means of alkali or alkaline earth metal hydroxides. Sometimes alkali metal salts are distinguished by - the fact that they have a better solubility than the free acid.
However, the solubility usually is adequate for using the compounds either alone or in combination with chelating agents or stabilizers in the most diverse fields of application, or example, in the
- 2 ~7~518 ~
treatment of water, in the textile industry ~nd in paper making, The reaction can also be carried out in solvents and the aprotic solvents having boiling points above 150C, for example, tetramethylene sulphone, diisopropyl sulphone, diglycol dimethyl ether and diglycol diethyl ether are partlcularly suitable.
The present invention will be further illustrated by way of the following Examples.
Example 1 A mixture of 82 g of dry phosphorous acid and 21 g of acetonitrile was heated to 180C over 1 hour and left at this temperature for 1 hour. The crop of crystals thus obtained was heated with 100 ml of water for a short period, filtered and dried, whereupon 78 g of l-aminoethane~ diphosphonic acid were obtained. This corresponds to a yield of 74.3%.
Analysis:
obtained: C 11.9~ ~ 6.7~ P 30.1~
calculated: C 11.72~ N 6.83~ P 30.21%
Example 2 At 80C, 82 g of anhydrous phosphorous acid and 0.1 g of AlC13 were dissolved in 20.5 g of anhydrous acetonitrile.
This mixture was heated to 170C over 2 hours while a small amount of acetonitrile was condensing in the reflux condenser.
; This was followed by stirring for 1 hour at the same temperature.
A solid white mass was thus obtained. This mass was boiled with 100 ml of H2O, whereupon the white crystals were filtered with suction and washed with H2O.
After drying for 3 hours in a drying cabinet 92.5 g of l-aminoethane-l,l~iphosphonic acid were obtained, This corres-ponds to a yield of 90.2~ The product shows the following analysis;
.
10775~L~
obtained: C 11,7~ N 6~9~ P 30,4~
calculated: C 11.72% N 6.83~ P 30,21%
Example 3 At 80C, 482 ~ of phosphorous acid and 0,5 g o AlC13 were dissolved in 133 g of acetonitrile. This solution was fed dropwise by means of a heated dropping funnel to a reactor with reflux condenser. The reactor was heated to a temperature of 180 to 190C. After 1/2 hour the crystallization started.
The ratè of drop addition was so adjusted that the temperature 1~ at the bottom of the réactor was between 170 and 185C. After 2 1/2 hours the reaction was completed. The further treatment was like that described in the preceding Examples.
Yield: 523 g, i.e., 85.0~ of the theoretical yield.
Example 4 A mixture containing 1/2 mole of acetonitrile, 0.8 mole of phosphvrous acid and 0.1 mole of pyrophosphorous acid was ~ reacted in the manner described in Example 1.
; ` Yield: 76.5 g, i.e.~ 74.2% of the theoretical yield.
Example 5 51 g of acetonitrile and 205 g of phosphorous acid were dissolved at 80C and this solution was fed into a heated dropping funnel. 250 ml of tetramethylene sulphone ~as the solvent- were put into a reactor fitted with reflux condenser ;
and stirrer and heated to 130C. The solution of phosphorous acid and acetonitrile was then added dropwise such that the temperature of the solvent was not below 180C. ~ white crystallizate separated and on completing the reaction and cooling to room :
temperature this crystallizate was filtered off. It was ~- washed with a small amount of water and with methanol. A~ter drying for 3 hours in a drying cabinet at 120C, 205 g of l-aminoethan~l,l-diphosphonic acid were obtained, corresponding to ~; a yield o 80.4%.
75~ :
~. :
Exam~le 6 In an oil~heated enamelled 2~1itre kneader ~ro~ided with re1ux condenser 820 g of phosphorous acid and 210 g of acetonitrile were slowly heated to 190C, while a small amount of acetonitrile was boiling in the relux condenser. The initially thinly liquid reaction mixture slowly turned viscous and finally crystalline. After 2 hours a white brittle product was discharged.
After washing with methanol and H2O and drying at 120C in a drying cabinet 809 g of l-aminoethane ~ diphosphonic acid were obtained corresponding to a yield of 78.9~.
Example 7 55 g of propionitrile and 164 g of phosphorous acid were dissolved at 80C in a reactor fitted with stirrer and reflux condenser, whereupon 0.5 g of AlC13 was added and the reaction mixture was heated to 190C. Ater 2 hours the white mass thus formed was stirred up wlth hot H2O (60C). After cooling to room temperature the mass was mixed with ethanol, filtered with suction, washed with ethanol and dried at 110C in a drying cabinet until the weight was constant. 158 g of l-aminopropane-l,l-diphosphonic acid were obtained. The product showed the following analysis: !
obtained: C 17.0% N 6.5% P 28.3%
computed: C 16.45% N 6.39% P 28.28%
~- Example 8 At 80~C 36.3 g of lauric nitrile were diluted with 33 g of phosphorous acid and 0.1 g of AlC13 and heated to 180C, whereupon the solution was left for 1 hour at this temperature.
On cooling the solid white mass thus formed to room temperature it was stirred up with a mixture of water and methanol, whereupon it was filtered with suction, properly washed with methanol and dried at 80C over P2O5 in a Yacuum dryer until the weight was constant 55.4 g of l-aminododecane~ diphosphonic acid ~ 77S~8 were obtained. 'rhe yield was sa ~ 2%
An~lysis:
obtained: C 41,8% N 4.2% P18.0%
calculated: C 41.74% N4.06% P 17.94 ~i ~
', .
' '`~
~ ~' .3 ;' , .
' .
: i ~
treatment of water, in the textile industry ~nd in paper making, The reaction can also be carried out in solvents and the aprotic solvents having boiling points above 150C, for example, tetramethylene sulphone, diisopropyl sulphone, diglycol dimethyl ether and diglycol diethyl ether are partlcularly suitable.
The present invention will be further illustrated by way of the following Examples.
Example 1 A mixture of 82 g of dry phosphorous acid and 21 g of acetonitrile was heated to 180C over 1 hour and left at this temperature for 1 hour. The crop of crystals thus obtained was heated with 100 ml of water for a short period, filtered and dried, whereupon 78 g of l-aminoethane~ diphosphonic acid were obtained. This corresponds to a yield of 74.3%.
Analysis:
obtained: C 11.9~ ~ 6.7~ P 30.1~
calculated: C 11.72~ N 6.83~ P 30.21%
Example 2 At 80C, 82 g of anhydrous phosphorous acid and 0.1 g of AlC13 were dissolved in 20.5 g of anhydrous acetonitrile.
This mixture was heated to 170C over 2 hours while a small amount of acetonitrile was condensing in the reflux condenser.
; This was followed by stirring for 1 hour at the same temperature.
A solid white mass was thus obtained. This mass was boiled with 100 ml of H2O, whereupon the white crystals were filtered with suction and washed with H2O.
After drying for 3 hours in a drying cabinet 92.5 g of l-aminoethane-l,l~iphosphonic acid were obtained, This corres-ponds to a yield of 90.2~ The product shows the following analysis;
.
10775~L~
obtained: C 11,7~ N 6~9~ P 30,4~
calculated: C 11.72% N 6.83~ P 30,21%
Example 3 At 80C, 482 ~ of phosphorous acid and 0,5 g o AlC13 were dissolved in 133 g of acetonitrile. This solution was fed dropwise by means of a heated dropping funnel to a reactor with reflux condenser. The reactor was heated to a temperature of 180 to 190C. After 1/2 hour the crystallization started.
The ratè of drop addition was so adjusted that the temperature 1~ at the bottom of the réactor was between 170 and 185C. After 2 1/2 hours the reaction was completed. The further treatment was like that described in the preceding Examples.
Yield: 523 g, i.e., 85.0~ of the theoretical yield.
Example 4 A mixture containing 1/2 mole of acetonitrile, 0.8 mole of phosphvrous acid and 0.1 mole of pyrophosphorous acid was ~ reacted in the manner described in Example 1.
; ` Yield: 76.5 g, i.e.~ 74.2% of the theoretical yield.
Example 5 51 g of acetonitrile and 205 g of phosphorous acid were dissolved at 80C and this solution was fed into a heated dropping funnel. 250 ml of tetramethylene sulphone ~as the solvent- were put into a reactor fitted with reflux condenser ;
and stirrer and heated to 130C. The solution of phosphorous acid and acetonitrile was then added dropwise such that the temperature of the solvent was not below 180C. ~ white crystallizate separated and on completing the reaction and cooling to room :
temperature this crystallizate was filtered off. It was ~- washed with a small amount of water and with methanol. A~ter drying for 3 hours in a drying cabinet at 120C, 205 g of l-aminoethan~l,l-diphosphonic acid were obtained, corresponding to ~; a yield o 80.4%.
75~ :
~. :
Exam~le 6 In an oil~heated enamelled 2~1itre kneader ~ro~ided with re1ux condenser 820 g of phosphorous acid and 210 g of acetonitrile were slowly heated to 190C, while a small amount of acetonitrile was boiling in the relux condenser. The initially thinly liquid reaction mixture slowly turned viscous and finally crystalline. After 2 hours a white brittle product was discharged.
After washing with methanol and H2O and drying at 120C in a drying cabinet 809 g of l-aminoethane ~ diphosphonic acid were obtained corresponding to a yield of 78.9~.
Example 7 55 g of propionitrile and 164 g of phosphorous acid were dissolved at 80C in a reactor fitted with stirrer and reflux condenser, whereupon 0.5 g of AlC13 was added and the reaction mixture was heated to 190C. Ater 2 hours the white mass thus formed was stirred up wlth hot H2O (60C). After cooling to room temperature the mass was mixed with ethanol, filtered with suction, washed with ethanol and dried at 110C in a drying cabinet until the weight was constant. 158 g of l-aminopropane-l,l-diphosphonic acid were obtained. The product showed the following analysis: !
obtained: C 17.0% N 6.5% P 28.3%
computed: C 16.45% N 6.39% P 28.28%
~- Example 8 At 80~C 36.3 g of lauric nitrile were diluted with 33 g of phosphorous acid and 0.1 g of AlC13 and heated to 180C, whereupon the solution was left for 1 hour at this temperature.
On cooling the solid white mass thus formed to room temperature it was stirred up with a mixture of water and methanol, whereupon it was filtered with suction, properly washed with methanol and dried at 80C over P2O5 in a Yacuum dryer until the weight was constant 55.4 g of l-aminododecane~ diphosphonic acid ~ 77S~8 were obtained. 'rhe yield was sa ~ 2%
An~lysis:
obtained: C 41,8% N 4.2% P18.0%
calculated: C 41.74% N4.06% P 17.94 ~i ~
', .
' '`~
~ ~' .3 ;' , .
' .
: i ~
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS;
1. A process for producing a l-aminoalkane-l,l-diphosphonic acid having the general formula , wherein R represents a hydrocarbon radical containing 1 to 12 carbon atoms which comprises reacting a nitrile having the general formula R-CN, wherein R is as above with phosphorous acid at a temperature from 140 to 210°C.
2. A process as claimed in claim 1, in which R is a saturated aliphatic hydrocarbon radical.
3. A process according to claim 1, in which the nitrile is selected from acetonitrile, propionitrile, butyronitrile and lauryl cyanide.
4. A process as claimed in claim 1,2 or 3, in which the molar ratio of nitrile to phosphorous acid is about 1:2.
5. A process according to claim 1, in which the reaction is carried out in the presence of a catalyst.
6. A process according to claim 5, in which the catalyst is a Lewis acid compound.
7. A process as claimed in claim 5, inwhich the catalyst is selected from A1C13, ZnC12, AlBr3 and SbC15.
8. A process as claimed in claim 1, 2 or 3, in which the reaction is effected in the presence of an aprotic solvent having a boiling point above 150°C.
9. A process as claimed in clalm 1, 2 or 3, in which the reaction is effected in the presence of a solvent selected from tetramethylene sulphone, diisopropyl sulphone, diglycol dimethyl ether and diglycol diethyl ether.
10. In a process of producing 1-amino alkane-1,1-diphosphonic acid of the formula in which R indicates a hydrocarbon radical with 1 to 12 carbon atoms, or a group of the formula wherein R1 is hydrogen or lower alkyl and R1 is an alkylene group containing 1 to 4 carbon atoms, the step which comprises reacting a nitrile of the formula R - CN
in which R is as defined above, with phosphorous acid at a temperature between about 140°C and about 200°C.
in which R is as defined above, with phosphorous acid at a temperature between about 140°C and about 200°C.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2625767A DE2625767C3 (en) | 1976-06-09 | 1976-06-09 | Process for the preparation of 1-aminoalkane-1,1-diphosphonic acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1077518A true CA1077518A (en) | 1980-05-13 |
Family
ID=5980129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA278,707A Expired CA1077518A (en) | 1976-06-09 | 1977-05-18 | Process for producing 1-aminoalkane-1,1-diphosphonic acids |
Country Status (11)
| Country | Link |
|---|---|
| AT (1) | AT348545B (en) |
| BE (1) | BE855548A (en) |
| CA (1) | CA1077518A (en) |
| DE (1) | DE2625767C3 (en) |
| DK (1) | DK143565C (en) |
| FR (1) | FR2354339A1 (en) |
| GB (1) | GB1530856A (en) |
| IT (1) | IT1076181B (en) |
| LU (1) | LU77509A1 (en) |
| NL (1) | NL7706256A (en) |
| SE (1) | SE7706659L (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3047107A1 (en) * | 1980-12-13 | 1982-07-29 | Hoechst Ag, 6000 Frankfurt | METHOD FOR PRODUCING 1-AMINO-ALKANE-1,1-DIPHOSPHONIC ACIDS |
| DE3149454A1 (en) * | 1981-12-14 | 1983-06-23 | Chemische Werke Hüls AG, 4370 Marl | METHOD FOR THE PRODUCTION OF POLYACRYLNITRILE POLYPHOSPHONIC ACID AND THEIR USE AS A FLAME RETARDANT |
| DE3232753A1 (en) * | 1982-04-19 | 1984-03-08 | Chemische Fabrik Budenheim Rudolf A. Oetker, 6501 Budenheim | Process for the preparation of 1-aminoalkane-1,1-diphosphonic acids |
| DE3214307A1 (en) * | 1982-04-19 | 1983-11-17 | Chemische Fabrik Budenheim Rudolf A. Oetker, 6501 Budenheim | Process for the preparation of 1-aminoalkane-1,1-diphosphonic acids |
| DE3611522A1 (en) * | 1986-04-05 | 1987-10-08 | Henkel Kgaa | DIPHOSPHONYLATED OXONITRILE, METHOD FOR THE PRODUCTION AND THEIR USE IN MICROBISTATIC COMPOSITIONS AND MICROBISTATICALLY EFFECTIVE DIPHOSPHONYLATED OXONITRILE CONTAINERS |
| DE3724653A1 (en) * | 1987-07-25 | 1989-02-02 | Henkel Kgaa | OLEFINIC DIPHOSPHONE ACIDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS THRESHOLDER, AND COMPLEXING COMPOSITIONS CONTAINING OLEFINIC DIPHOSPHONE ACIDS |
| DE3724654A1 (en) * | 1987-07-25 | 1989-02-02 | Henkel Kgaa | HYDROXYACETONITRILDIPHOSPHONIC ACID, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
| US5043099A (en) * | 1990-07-13 | 1991-08-27 | Kreh Robert P | Mono- and di-substituted (diphosphonoalkylamino methyl)-4-hydroxybenzenesulfonic acid |
| US5221487A (en) * | 1991-10-24 | 1993-06-22 | W. R. Grace & Co.-Conn. | Inhibition of scale formation and corrosion by sulfonated organophosphonates |
-
1976
- 1976-06-09 DE DE2625767A patent/DE2625767C3/en not_active Expired
-
1977
- 1977-02-16 IT IT20348/77A patent/IT1076181B/en active
- 1977-05-18 CA CA278,707A patent/CA1077518A/en not_active Expired
- 1977-05-23 GB GB21603/77A patent/GB1530856A/en not_active Expired
- 1977-06-07 DK DK251577A patent/DK143565C/en active
- 1977-06-07 AT AT402677A patent/AT348545B/en not_active IP Right Cessation
- 1977-06-07 NL NL7706256A patent/NL7706256A/en not_active Application Discontinuation
- 1977-06-08 SE SE7706659A patent/SE7706659L/en unknown
- 1977-06-08 FR FR7717529A patent/FR2354339A1/en not_active Withdrawn
- 1977-06-09 LU LU77509A patent/LU77509A1/xx unknown
- 1977-06-09 BE BE178334A patent/BE855548A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DK251577A (en) | 1977-12-10 |
| FR2354339A1 (en) | 1978-01-06 |
| DE2625767C3 (en) | 1980-06-04 |
| BE855548A (en) | 1977-10-03 |
| LU77509A1 (en) | 1977-09-19 |
| SE7706659L (en) | 1977-12-10 |
| DE2625767B2 (en) | 1979-08-23 |
| DK143565B (en) | 1981-09-07 |
| AT348545B (en) | 1979-02-26 |
| DK143565C (en) | 1982-02-01 |
| GB1530856A (en) | 1978-11-01 |
| ATA402677A (en) | 1978-07-15 |
| DE2625767A1 (en) | 1977-12-15 |
| IT1076181B (en) | 1985-04-27 |
| NL7706256A (en) | 1977-12-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |