DK143565B - METHOD FOR PREPARING 1-AMINOALKAN-1,1-DIPHOSPHONIC ACIDS - Google Patents
METHOD FOR PREPARING 1-AMINOALKAN-1,1-DIPHOSPHONIC ACIDS Download PDFInfo
- Publication number
- DK143565B DK143565B DK251577AA DK251577A DK143565B DK 143565 B DK143565 B DK 143565B DK 251577A A DK251577A A DK 251577AA DK 251577 A DK251577 A DK 251577A DK 143565 B DK143565 B DK 143565B
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- DK
- Denmark
- Prior art keywords
- phosphoric acid
- acetonitrile
- diphosphonic acids
- diphosphonic
- aminoalkan
- Prior art date
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- 239000002253 acid Substances 0.000 title description 11
- 150000007513 acids Chemical class 0.000 title description 9
- 238000000034 method Methods 0.000 title description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 33
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 28
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 14
- 150000002825 nitriles Chemical class 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- -1 alkyl nitrile Chemical class 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- GPCTYPSWRBUGFH-UHFFFAOYSA-N (1-amino-1-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(N)(C)P(O)(O)=O GPCTYPSWRBUGFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- PCTMREJZUSEOQD-UHFFFAOYSA-N (1-amino-1-phosphonopropyl)phosphonic acid Chemical compound CCC(N)(P(O)(O)=O)P(O)(O)=O PCTMREJZUSEOQD-UHFFFAOYSA-N 0.000 description 1
- ZDULHUHNYHJYKA-UHFFFAOYSA-N 2-propan-2-ylsulfonylpropane Chemical compound CC(C)S(=O)(=O)C(C)C ZDULHUHNYHJYKA-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 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
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 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
- 239000000010 aprotic solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- WKJHMKQSIBMURP-UHFFFAOYSA-N tridecanenitrile Chemical compound CCCCCCCCCCCCC#N WKJHMKQSIBMURP-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000010626 work up procedure 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)
Description
fSi) (19) DANMARK Vr|/fSi) (19) DENMARK Fr | /
|j| da) FREMUEGGELSESSKRIFT <n) 1U3565 B| J | da) PROCEDURE WRITING <n) 1U3565 B
DIREKTORATET FOR PATENT- OG VAREMÆRKEVÆSENETDIRECTORATE OF THE PATENT AND TRADEMARKET SYSTEM
(21) Ansøgning nr. 2515/77 (51) IntCI.3 C 07 F 9/38 (22) Indleveringsdag 7· jun. 1977 (24) Løbedag 7· jun. 1977 (41) Aim. tilgængelig 10. dec. 1977 (44) Fremlagt 7· sep. 1981 (86) International ansøgning nr.(21) Application No. 2515/77 (51) IntCI.3 C 07 F 9/38 (22) Filing date 7 · Jun. 1977 (24) Race day 7 · Jun. 1977 (41) Aim. available Dec. 10; 1977 (44) Posted 7 Sep. 1981 (86) International application no.
(86) International indleveringsdag (85) Videreførelsesdag - (62) Stamansøgning nr. -(86) International filing day (85) Continuation day - (62) Master application no. -
(30) Prioritet 9. jun. 1976, 2625767, DE(30) Priority 9 Jun. 1976, 2625767, DE
(71) Ansøger BENCKISER-KNAPSACK GMBH, D-6802 Ladenburg/Neckar, DE.(71) Applicant BENCKISER-KNAPSACK GMBH, D-6802 Ladenburg / Neckar, DE.
(72) Opfinder Klaus Sommer, DE: Guenter Raab, DE.(72) Inventor Klaus Sommer, DE: Guenter Raab, DE.
(74) Fuldmægtig piougmann & Vingtoft Patent bur eau.(74) Plenipotentiary & Vingtoft Patent bur eau.
(54) Fremgangsmåde til fremstilling af 1 -aminoalkan-1,1 -diphosphonsyrer.(54) Process for Preparation of 1-Aminoalkane-1,1-diphosphonic Acids.
Den foreliggende opfindelse angår en særlig fremgangsmåde til frem-stilling af 1-aminoalkan-l,1-diphosphonsyrer.The present invention relates to a particular process for the preparation of 1-aminoalkane-1,1-diphosphonic acids.
I tysk patentskrift nr. 10 02 355 er fremstillingen af 1-amino-alkan-1,1-diphosphonsyrer ved omsætning af alkylnitril med phosphor--halogenider beskrevet, idet der dog kun kunne opnås tilfredsstillende udbytter med phosphortribromid.German Patent Specification No. 10 02 355 discloses the preparation of 1-amino-alkane-1,1-diphosphonic acids by reaction of alkyl nitrile with phosphorus halides, however satisfactory yields of phosphorus tribromide could only be obtained.
0 Det er endvidere kendt fra tysk offentliggørelsesskrift nr.0 It is also known from German publication no.
^ 20 48 913 at omsætte nitriler med phosphorsyrling i nærværelse af :) hydrogenhalogenid.To react nitriles with phosphoric acid in the presence of:) hydrogen halide.
0 t - Begge fremgangsmåder har den ulempe, at der ved den tekniske fremstil- ^ ling optræder visse apparatmæssige vanskeligheder på grund af phos- 3 2 143565 phorhalogenidernes eller hydrogenhalogenidernes stærkt korrosive egenskaber.0 t - Both processes have the disadvantage that in the technical manufacture certain apparatus difficulties occur due to the highly corrosive properties of the phosphorus halides or hydrogen halides.
Fra tysk fremlæggelsesskrift nr. 2203340 er det kendt at fremstille l-aminoalkan-l,l-diphosphonsyrer ud fra amider og phosphorsyrling ved omsætning ved temperaturer mellem 120 og 200°C, men ved denne reaktion skal der anvendes phosphorpentoxid, hvilket nødvendiggør særlige forsigtighedsregler, da phosphorpentoxid og phosphorsyrling kan reagere kraftigt under udvikling af phosphin.From German Patent Specification No. 2203340 it is known to prepare 1-aminoalkan-1,1-diphosphonic acids from amides and phosphoric acid when reacting at temperatures between 120 and 200 ° C, but in this reaction phosphorus pentoxide must be used, which requires special precautions, as phosphorus pentoxide and phosphoric acid can react strongly during phosphine development.
Det har nu vist sig, at disse ulemper kan undgås, og at 1-amino-alkan-1,1-diphosphonsyrer med den almene formelIt has now been found that these disadvantages can be avoided and that 1-amino-alkane-1,1-diphosphonic acids of the general formula
HO 0 NH~ O OHHO 0 NH ~ O OH
\ll 12 «/\ ll 12 «/
p - c - Pp - c - P
Ho'^ i ^OHHo '^ i ^ OH
hvor R betegner en carbonhydridgruppe med 1-12 carbonatomer, på enkel måde kan fremstilles ved omsætning af nitriler med den almene formel R-CN, hvor R har den ovenfor anførte betydning, med phosphor-syrling, hvilken omsætning ifølge opfindelsen udføres i fravær af hydrogenhalogenid og ved temperaturer mellem 140 og 200°C.wherein R represents a hydrocarbon group having from 1 to 12 carbon atoms, which can be readily prepared by reacting nitriles of the general formula R-CN, wherein R is as defined above, with phosphorus acidation, which reaction according to the invention is carried out in the absence of hydrogen halide and at temperatures between 140 and 200 ° C.
Som nitriler kan anvendes aliphatiske, forgrenede eller ligekædede nitriler. Særlig foretrukne nitriler er acetonitril, propionitril, butyronitril og laurylcyanid.As nitriles can be used aliphatic, branched or straight chain nitriles. Particularly preferred nitriles are acetonitrile, propionitrile, butyronitrile and lauryl cyanide.
Nitrilerne og phosphorsyrlingen anvendes hensigtsmæssigt i et molforhold på ca. 1:2.The nitriles and phosphoric acid are suitably used in a molar ratio of approx. 1: 2.
En anden mulighed består i at bringe en blanding indeholdende 1 mol nitril, 1,6 mol phosphorsyrling og 0,2 mol pyrophosphorsyrling til omsætning under opvarmning til det nævnte temperaturområde.Another option is to bring a mixture containing 1 mole of nitrile, 1.6 mole of phosphoric acid and 0.2 mole of pyrophosphoric acid to react under heating to said temperature range.
Da phosphorsyrling ved temperaturer på 160 - 200°C normalt spaltes i PH^ og H^PO^, kunne det ikke ventes, at der ved disse temperaturer dannes stabile blandinger, der kan omsættes til aminoalkan--diphosphonsyrer, uden at der derved optræder nævneværdige mængder 3 U3565 PH^ eller Η3Ρ04· Det må antages, at der foregår adduktdannelse af nitril til phosphorsyrlingen, da der kun afdestillerer en ringe mængde nitril trods betragtelig overskridelse af kogepunktet. F.eks. har acetonitril et kogepunkt på 82°C.Since phosphoric acid at temperatures of 160 - 200 ° C is normally decomposed into PH 2 and H 2 PO quantities 3 U3565 PH ^ or Ρ3Ρ04 · It is believed that nitrile adduct formation to the phosphoric acid occurs, since only a small amount of nitrile is distilled off despite considerable boiling point. Eg. For example, acetonitrile has a boiling point of 82 ° C.
Udbyttet af l-aminoalkan-l,l-diphosphonsyrer kan yderligere hæves 5 - 10%, når der tilsættes katalytiske mængder Lewis-syrer.The yield of l -aminoalkane-1,1-diphosphonic acids can be further raised 5-10% when catalytic amounts of Lewis acids are added.
Som katalysatorer kan f.eks. anvendes aluminiumchlorid, zinkchlorid, aluminiumbromid og antimonpentachlorid.As catalysts, e.g. aluminum chloride, zinc chloride, aluminum bromide and antimony pentachloride are used.
Alkali- eller jordalkalimetalsaltene kan fremstilles ved neutralisation af en vandig opslæmning af arainoalkan-1,1-diphosphonsyrerne ved hjælp af alkalimetal- eller jordalkalimetalhydroxider. Alkalimetalsaltene udmærker sig bl.a. ved bedre opløselighed end den frie syre. Opløseligheden er dog i almindelighed tilstrækkelig til, at syrerne kan anvendes enten alene eller i kombination med chelat-dannere eller stabilisatorer på de mest forskellige anvendelsesområder, f.eks. ved vandbehandling, i tekstilsektoren og ved papirfremstilling.The alkali or alkaline earth metal salts can be prepared by neutralizing an aqueous slurry of the arainoalkane-1,1-diphosphonic acids by means of alkali metal or alkaline earth metal hydroxides. The alkali metal salts are distinguished, among other things. at better solubility than the free acid. However, the solubility is generally sufficient for the acids to be used either alone or in combination with chelating agents or stabilizers in the most diverse applications, e.g. in water treatment, in the textile sector and in papermaking.
Omsætningen kan også foretages i opløsningsmidler. Til dette formål er de aprotiske opløsningsmidler, hvis kogepunkt ligger over 150°C, seerlig velegnede, f.eks. tetramethylensulfon, diisopropylsulfon, diglycoldimethylether og diglycoldiethylether.The reaction can also be carried out in solvents. For this purpose, the aprotic solvents whose boiling point is above 150 ° C are particularly suitable, e.g. tetramethylene sulfone, diisopropyl sulfone, diglycold dimethyl ether and diglycold diethyl ether.
Fremgangsmåden ifølge opfindelsen belyses nærmere ved nedenstående eksempler:The process according to the invention is further illustrated by the following examples:
Eksempel 1.Example 1.
En blanding af 82 g tør phosphorsyrling og 21 g acetonitril opvarmes i løbet af 1 time til 180°C og holdes i 1 time ved denne temperatur. Den resulterende krystalmasse opvarmes i kort tid med 100 ml vand og frafiltreres. Efter tørring fås 78 g 1-aminoethan--1,1-diphosphonsyre, hvilket svarer til et udbytte på 74,3% af det teoretiske.A mixture of 82 g dry phosphorus acid and 21 g acetonitrile is heated over 1 hour to 180 ° C and kept for 1 hour at this temperature. The resulting crystal mass is heated briefly with 100 ml of water and filtered off. After drying, 78 g of 1-aminoethane-1,1-diphosphonic acid is obtained, which corresponds to a yield of 74.3% of theory.
Analyse:Analysis:
Fundet: C 11,9 N 6,7 P 30,1Found: C 11.9 N 6.7 P 30.1
Beregnet: C 11,72 N 6,83 P 30,21.Calculated: C 11.72 N 6.83 P 30.21.
143565 4143565 4
Eksempel 2.Example 2.
I 20,5 g vandfrit acetonitril opløses ved 80°C 82 g vandfri phos-phorsyrling og 0,1 g AlCl3. Denne blanding opvarmes i løbet af 2 timer til 170°C, hvorved der i tilbagesvalingskøleren kondenseres noget acetonitril. Derpå omrøres blandingen i 1 time ved denne temperatur. Der fås en fast, hvid masse. Denne koges med 100 ml vand, og de hvide krystaller frasuges og eftervaskes med vand.In 20.5 g of anhydrous acetonitrile, at 80 ° C, 82 g of anhydrous phosphoric acid and 0.1 g of AlCl3 are dissolved. This mixture is heated to 170 ° C over 2 hours, whereby some acetonitrile is condensed in the reflux condenser. Then the mixture is stirred for 1 hour at this temperature. A solid white mass is available. This is boiled with 100 ml of water and the white crystals are extracted and washed with water.
Efter 3 timers tørring i tørreskab fås 92,5 g 1-aminoethan-l,1--diphosphonsyre, hvilket svarer til et udbytte på 90,2% af det teoretiske.After 3 hours of drying in a drying cabinet, 92.5 g of 1-aminoethane-1,1-diphosphonic acid is obtained, which corresponds to a yield of 90.2% of theory.
Analyse:Analysis:
Fundet: C 11,7 N 6,9 P 30,4Found: C 11.7 N 6.9 P 30.4
Beregnet: C 11,72 N 6,83 P 30,21.Calculated: C 11.72 N 6.83 P 30.21.
Eksempel 3.Example 3
I 133 g acetonitril opløses ved 80°C 482 g phosphorsyrling og 0,5 g AlCl^. Denne opløsning dryppes gennem en opvarmelig tildrypnings-tragt under kraftig omrøring til en til 180 - 190°C opvarmet reaktionsbeholder med tilbagesvalingskøler. Efter 1/2 times forløb indtræder krystallisation. Tildrypningshastigheden reguleres på en sådan måde, at temperaturen ligger mellem 170 og 185°C. Efter 21/2 times forløb er reaktionen endt. Der oparbejdes som beskrevet i de ovennævnte eksempler.In 133 g of acetonitrile dissolve at 80 ° C 482 g of phosphoric acid and 0.5 g of AlCl 2. This solution is dripped through a heated drip funnel with vigorous stirring to a reflux condenser heated to 180-190 ° C. After 1/2 hour, crystallization occurs. The rate of drip is regulated in such a way that the temperature is between 170 and 185 ° C. After 21/2 hours, the reaction is over. Work up as described in the above examples.
Udbytte: 523 g, hvilket svarer til 85,0% af det teoretiske.Yield: 523 g, which corresponds to 85.0% of theory.
Eksempel 4.Example 4
En blanding indeholdende 1/2 mol acetonitril, 0,8 mol phosphorsyrling og 0,1 mol pyrophosphorsyrling omsættes som beskrevet i eksempel 1.A mixture containing 1/2 mole of acetonitrile, 0.8 mole of phosphoric acid and 0.1 mole of pyrophosphoric acid is reacted as described in Example 1.
Udbytte: 76,5 g, hvilket svarer til 74,2% af det teoretiske.Yield: 76.5 g, which corresponds to 74.2% of theory.
c 1A3S65 5c 1A3S65 5
Eksempel 5.Example 5
51 g acetonitril og 205 g phosphorsyrling opløses ved 80°C, og denne opløsning hældes i en opvarmet tildrypningstragt. I en reaktionsbeholder med tilbagesvalingskøler og omrører hældes 250 ml tetra-methylensulfon som opløsningsmiddel, og der opvarmes til 180°C.Dissolve 51 g of acetonitrile and 205 g of phosphoric acid at 80 ° C and pour this solution into a heated dropping funnel. In a reflux condenser and stirrer reaction vessel, pour 250 ml of tetramethylene sulfone as solvent and heat to 180 ° C.
Nu tildryppes phosphorsyrling/acetonitril-opløsningen på en sådan måde, at opløsningsmiddeltemperaturen ikke falder under 180°C. Der udskilles et hvidt krystallisat, som efter endt reaktion og afkøling til stuetemperatur frafiltreres. Det eftervaskes med en ringe mængde vand og med methanol. Efter 3 timers tørring i tørreskab ved 120 C fås 205 g l-aminoethan-l,l-diphosphonsyre, hvilket svarer til et udbytte på 80,4% af det teoretiske.Now the phosphoric acid / acetonitrile solution is dripped in such a way that the solvent temperature does not fall below 180 ° C. A white crystalline precipitate is separated, which is filtered off after reaction and cooling to room temperature. It is washed with a small amount of water and with methanol. After 3 hours of drying in a drying cabinet at 120 C, 205 g of 1-aminoethane-1,1-diphosphonic acid is obtained, which corresponds to a yield of 80.4% of theory.
Eksempel 6.Example 6
I et olieopvarmet, emaljeret 2 liters æltekar med tilbagesvalipgs-køler opvarmes 820 g phosphorsyrling og 210 g acetonitril langsomt til 190°C, hvorved noget acetonitril koger under tilbagesvaling.In an oil-heated, 2-liter kneading pot with reflux condenser, 820 g of phosphoric acid and 210 g of acetonitrile are slowly heated to 190 ° C, whereby some acetonitrile boils under reflux.
Den i begyndelsen tyndtflydende reaktionsblanding bliver langsomt viskos og endelig krystallinsk. Efter 2 timers forløb kan et hvidt, smuldrende produkt udtages. Efter vask med methanol/E^O og tørring ved 120°C i tørreskab fås 809 g l-aminoethan-l,l-diphosphonsyre, hvilket svarer til et udbytte på 78,9% af det teoretiske.The initially thin liquid reaction mixture slowly becomes viscous and finally crystalline. After 2 hours, a white, crumbly product can be removed. After washing with methanol / E 2 O and drying at 120 ° C in a drying cabinet, 809 g of 1-aminoethane-1,1-diphosphonic acid is obtained, which corresponds to a yield of 78.9% of theory.
Eksempel 7.Example 7
55 g propionitril og 164 g phosphorsyrling opløses i en reaktionsbeholder med omrører og tilbagesvalingskøler ved 80°C. 0,5 g AlClg tilsættes, og denne reaktionsblanding opvarmes til 190°C. Efter 2 timers forløb udrøres den dannede hvide masse med 60°C varmt vand, tilsættes ethanol efter afkøling til stuetemperatur, frasuges, eftervaskes med ethanol og tørres i tørreskab ved 110°C til konstant vægt. Der fås 158 g l-aminopropan-l,l-diphosphonsyre.Dissolve 55 g of propionitrile and 164 g of phosphoric acid in a reaction vessel with stirrer and reflux condenser at 80 ° C. 0.5 g of AlClg is added and this reaction mixture is heated to 190 ° C. After 2 hours, the resulting white mass is stirred with 60 ° C hot water, ethanol after cooling to room temperature, suctioned off, washed with ethanol and dried in a drying cabinet at 110 ° C to constant weight. 158 g of 1-aminopropane-1,1-diphosphonic acid are obtained.
Analyse:Analysis:
Fundet: C 17,0 N6,5 P 28,3Found: C 17.0 N6.5 P 28.3
Beregnet: C 16,45 N 6,39 P 28,28.Calculated: C 16.45 N 6.39 P 28.28.
Applications Claiming Priority (2)
| 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 |
| DE2625767 | 1976-06-09 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK251577A DK251577A (en) | 1977-12-10 |
| DK143565B true DK143565B (en) | 1981-09-07 |
| DK143565C DK143565C (en) | 1982-02-01 |
Family
ID=5980129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK251577A DK143565C (en) | 1976-06-09 | 1977-06-07 | METHOD FOR PREPARING 1-AMINOALKAN-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 |
| DE3724654A1 (en) * | 1987-07-25 | 1989-02-02 | Henkel Kgaa | HYDROXYACETONITRILDIPHOSPHONIC ACID, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
| 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 |
| 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 AT AT402677A patent/AT348545B/en not_active IP Right Cessation
- 1977-06-07 DK DK251577A patent/DK143565C/en active
- 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 |
| NL7706256A (en) | 1977-12-13 |
| AT348545B (en) | 1979-02-26 |
| DE2625767A1 (en) | 1977-12-15 |
| FR2354339A1 (en) | 1978-01-06 |
| GB1530856A (en) | 1978-11-01 |
| CA1077518A (en) | 1980-05-13 |
| BE855548A (en) | 1977-10-03 |
| DK143565C (en) | 1982-02-01 |
| IT1076181B (en) | 1985-04-27 |
| ATA402677A (en) | 1978-07-15 |
| LU77509A1 (en) | 1977-09-19 |
| DE2625767B2 (en) | 1979-08-23 |
| DE2625767C3 (en) | 1980-06-04 |
| SE7706659L (en) | 1977-12-10 |
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