DK149473B - PROCEDURE FOR PREPARING AMINOMETHAN PHOSPHONIC ACIDS - Google Patents
PROCEDURE FOR PREPARING AMINOMETHAN PHOSPHONIC ACIDS Download PDFInfo
- Publication number
- DK149473B DK149473B DK148679AA DK148679A DK149473B DK 149473 B DK149473 B DK 149473B DK 148679A A DK148679A A DK 148679AA DK 148679 A DK148679 A DK 148679A DK 149473 B DK149473 B DK 149473B
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- DK
- Denmark
- Prior art keywords
- added
- water
- phosphorus trichloride
- phosphonic acids
- reaction
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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 System
- 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, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
Description
i 149473in 149473
Opfindelsen angår en særlig fremgangsmåde til fremstilling af aminomethan-phosphonsyrer af den i indledningen til kravet angivne art.The invention relates to a particular process for the preparation of aminomethane phosphonic acids of the kind set forth in the preamble to the claim.
Sådanne forbindelser har i vidt omfang været anvendt 5 til plantebeskyttelse på grund af en herbicid aktivitet med et bredt spektrum. Den herbicide aktivitet ledsages af en lav residual aktivitet, dvs. den aktive bestanddel nedbrydes relativt let i jorden.Such compounds have been widely used for plant protection due to a broad spectrum herbicidal activity. The herbicidal activity is accompanied by a low residual activity, ie. the active ingredient is decomposed relatively easily in the soil.
Man har i litteraturen beskrevet adskillige synteseme-10 toder til fremstilling af aminomethan-phosphonsyrer af den pågældende art.Several synthetic methods for the preparation of aminomethane phosphonic acids of the kind in question have been described in the literature.
De kendte fremgangsmåder til fremstilling af aminomethan-phosphonsyrer ud fra phosphortrihalogenid, ammoniak eller amin og aldehyd udmærker sig ved, at det udbytte 15 og den renhed, man opnår, ikke er tilfredsstillende.The known processes for preparing aminomethane phosphonic acids from phosphorus trihalide, ammonia or amine and aldehyde are distinguished by the fact that the yield and the purity obtained are not satisfactory.
Det er opfindelsens formål at tilvejebringe en Fremgangsmåde af den i indledningen til kravet angivne art, ved hvis hjælp man sættes i stand til at fremstille aminome-than-phosphonsyrerne i højt udbytte og i høj renhed.SUMMARY OF THE INVENTION It is an object of the invention to provide a process of the kind set forth in the preamble to the claim, by which it is possible to prepare the high yield and high purity of the amino-phosphonic acids.
20 Fremgangsmåden ifølge opfindelsen er ejendommelig ved det i den kendetegnende del af kravet angivne. Det har overraskende vist sig, at man ved at gennemføre omsætningen mellem phosphortrihalogenid og ammoniak, ammoniumsalt eller amin i nærværelse af vand, således at man 25 overholder det angivne molære forhold mellem vand og phosphortrihalogenid, opnår et større udbytte og en større renhed af aminomethan-phosphonsyrerne. Ved ingen af de kendte fremgangsmåder arbejder man inden for det særlige interval for forholdet mellem vand og phosphor-30 trihalogenid, der er angivet i det foreliggende krav, 2 U9473 og ej heller kan man under anvendelse af de kendte fremgangsmåder opnå slutprodukter i så højt udbytte og så høj renhed som ved fremgangsmåden ifølge opfindelsen.The method according to the invention is characterized by the characterizing part of the claim. Surprisingly, it has been found that by conducting the reaction between phosphorus trihalide and ammonia, ammonium salt or amine in the presence of water, so as to comply with the stated molar ratio of water to phosphorus trihalide, a greater yield and a higher purity of aminomethane are obtained. phosphonoacids. In none of the known processes does one operate within the particular range of the ratio of water to phosphorus trihalide disclosed in the present claim 2 U9473 nor can end products in such high yields be obtained using the known methods. and as high in purity as in the process of the invention.
Det ønskede slutprodukt udvindes fra reaktionsblandingen 5 ved at reducere reaktionsvoluminet eller ved indføring i et med vand blandbart opløsningsmiddel, fortrinsvis et organisk opløsningsmiddel.The desired final product is recovered from the reaction mixture 5 by reducing the reaction volume or by introducing it into a water-miscible solvent, preferably an organic solvent.
Hvis der anvendes ammoniak som reaktant, kan dette være vandig ammoniak. Hvis der anvendes et vandopløseligt 10 ammoniumsalt, kan dette være ammoniumchlorid, ammonium acetat, ammoniumbromid, ammoniumcarbonat eller ammonium-phosphat.If ammonia is used as a reactant, this may be aqueous ammonia. If a water-soluble 10 ammonium salt is used, this may be ammonium chloride, ammonium acetate, ammonium bromide, ammonium carbonate or ammonium phosphate.
Det produkt, der fremkommer i henhold til opfindelsen, krystalliserer let og kemisk homogent, og hverken NMR-15 eller IR-spektret viser nogen kontaminering. Udbyttet andrager mere end 90 % og andelen af aminomethan-phosphon-syreforbindelser i det dannede produkt er over 98 %.The product obtained according to the invention crystallizes readily and chemically homogeneously, and neither the NMR-15 nor the IR spectrum shows any contamination. The yield is more than 90% and the proportion of aminomethane-phosphonic acid compounds in the product formed is above 98%.
Yderligere detaljer ved opfindelsen illustreres ved de følgende eksempler.Further details of the invention are illustrated by the following examples.
20 EKSEMPEL 1EXAMPLE 1
Til en beholder, der er forsynet med en omrører, tilfører man 300 ml vand, og under omrøring tilsætter man 137 g phosphortrichlorid, og til opløsningen, hv.is temperatur er hævet, tilsætter man 75 g 50 % vandig glycinopløs-25 ning. Reaktionsblandingen opvarmes til kogepunktet under konstant omrøring, og efter 30 minutters forløb tilsætter man langsomt 200 g 37 % vandig formaldehyd-opløsning. Efter reaktionen destillerer man vandet fra. Den fremkomne sirup opløses i varm ethanol. Ethanolopløsnin-30 gen afkøles, hvorpå der bundfældes et krystallinsk pro- 149473 3 dukt indeholdende N,N-diphosphonomethylglycin med en renhed på 97 %. Dekompositionspunkt: 210 °C, udbytte: 93 S. I dette eksempel udføres omsætningen mellem phos-phortrichlorid og glycin i nærværelse af ca. 18,8 mol 5 vand per mol phosphortrichlorid.To a vessel equipped with a stirrer is added 300 ml of water and, with stirring, 137 g of phosphorus trichloride are added and to the solution where temperature is raised 75 g of 50% aqueous glycine solution is added. The reaction mixture is heated to the boiling point with constant stirring and after 30 minutes 200 g of 37% aqueous formaldehyde solution are slowly added. After the reaction, the water is distilled off. The resulting syrup is dissolved in hot ethanol. The ethanol solution is cooled and a crystalline product is precipitated containing N, N-diphosphonomethylglycine with a purity of 97%. Decomposition point: 210 ° C, yield: 93 S. In this example, the reaction between phosphorus trichloride and glycine is carried out in the presence of ca. 18.8 moles of water per mole of phosphorus trichloride.
EKSEMPEL 2EXAMPLE 2
Til en beholder, der er forsynet med et termometer, en omrører og en tilbagesvaler, tilsættes der 125 ml vand. Under omrøring og afkøling tilsætter man 51,7 10 g phosphortrichlorid, og temperaturen holdes under 40 °C. Når tilsætningen af phosphortrichlorid er afsluttet, tilsætter man 50 g iminodieddikesyre til blandingen, og der opvarmes til kogning. Blandingen opvarmes under tilbagesvaling, og der tilsættes 119 g 38 % vandig form-15 aldehyd indenfor 45 minutter. Når formaldehydet er tilsat, koges blandingen i 3 timer. To tredjedele af vandet destilleres fra, opløsningen fortyndes med ethanol, og man lader blandingen henstå under afkøling, de bundfældede krystaller filtreres fra, vaskes med ethanol 20 og vand og tørres. Der fremkommer en meget ren N-phospho-nomethyliminodieddikesyre med dekompositionspunkt 208 °C, udbytte 95 %. 1 dette eksempel udføres omsætningen mellem phosphortrichlorid og iminodieddikesyre i nærværelse af ca. 18,4 mol vand per mol phosphortrichlorid.To a container equipped with a thermometer, a stirrer and a reflux condenser is added 125 ml of water. With stirring and cooling, 51.7 g of phosphorus trichloride are added and the temperature is kept below 40 ° C. When the addition of phosphorus trichloride is complete, 50 g of iminodiacetic acid are added to the mixture and heated to boiling. The mixture is heated at reflux and 119 g of 38% aqueous formaldehyde is added within 45 minutes. When the formaldehyde is added, the mixture is boiled for 3 hours. Two-thirds of the water is distilled off, the solution is diluted with ethanol and the mixture is allowed to cool, the precipitated crystals are filtered off, washed with ethanol 20 and water and dried. A very pure N-phosphomomethyliminodiacetic acid is obtained with decomposition point 208 ° C, yield 95%. In this example, the reaction between phosphorus trichloride and iminodiacetic acid is carried out in the presence of ca. 18.4 moles of water per mole of phosphorus trichloride.
25 EKSEMPEL 3EXAMPLE 3
Til en beholder, der er forsynet med en omrører og en tilbagesvaler, tilsættes 175 ml vand, og under omrøring tilsættes 69 g phosphortrichlorid.To a vessel equipped with a stirrer and a reflux condenser is added 175 ml of water and with stirring 69 g of phosphorus trichloride are added.
44,5 g N-methy1-glycin tilsættes yderligere. Under om-30 røring tilsættes 188,4 g 38 % vandig formaldehyd-opløs- 149473 4 ning, idet man holder reaktionsblandingen kogende. Når tilsætningen er færdig, koges blandingen i 2 timer, og der inddampes til halvt volumen. Efter tilsætning af ethanol og afkøling vaskes det bundfældede, krystal-5 linske produkt med vand og tørres. Det fremkomne N- phosphonomethyl-N-methyl-glycin har en renhed på 97 %. Udbytte 90 S. I dette eksempel udføres omsætningen mellem phosphortrichlorid og N-methylglycin i nærværelse af ca. 19,4 mol vand per mol phosphortrichlorid.44.5 g of N-methyl-glycine are further added. With stirring, 188.4 g of 38% aqueous formaldehyde solution is added keeping the reaction mixture boiling. When the addition is complete, the mixture is boiled for 2 hours and evaporated to half volume. After adding ethanol and cooling, the precipitated, crystalline product is washed with water and dried. The resulting N-phosphonomethyl-N-methyl-glycine has a purity of 97%. Yield 90 S. In this example, the reaction between phosphorus trichloride and N-methylglycine is carried out in the presence of ca. 19.4 moles of water per mole of phosphorus trichloride.
10 EKSEMPEL 4EXAMPLE 4
Til en beholder, der er forsynet med en omrører og en tilbagesvaler, og hvori der er indfyldt 525 ml vand, tilsættes 206 g phosphortrichlorid under omrøring, således at temperaturen ikke overskrider 40 °C. 27 g 15 ammoniumchlorid indføres derpå, og der opvarmes til kogning, og 565 g 38 % vandig formaldehyd-opløsning tilsættes, og der koges i 1 time. Når reaktionen er afsluttet, afkøles blandingen til stuetemperatur, og det bundfældede, krystallinske materiale filtreres fra 20 opløsningen. Den fremkomne nitrilotrimethanphosphonsyre har en renhed på 97 %. I dette eksempel udføres omsætningen mellem phosphortrichlorid og ammoniumchlorid i nærværelse af ca. 19,5 mol vand per mol phosphortrichlorid.To a container equipped with a stirrer and a reflux condenser, containing 525 ml of water, is added 206 g of phosphorus trichloride with stirring so that the temperature does not exceed 40 ° C. 27 g of ammonium chloride are then introduced and heated to boiling, and 565 g of 38% aqueous formaldehyde solution are added and boiled for 1 hour. When the reaction is complete, the mixture is cooled to room temperature and the precipitated crystalline material is filtered from the solution. The resulting nitrilotrimethane phosphonic acid has a purity of 97%. In this example, the reaction between phosphorus trichloride and ammonium chloride is carried out in the presence of ca. 19.5 moles of water per mole of phosphorus trichloride.
EKSEMPEL 5 25 Til en beholder, der er forsynet med omrører og til bagesvaler, tilsættes 350 ml vand, og under omrøring tilsættes yderligere 138 g phosphortrichlorid, mens temperaturen holdes på ca. 40 °C. 62 g cyclohexylamin-hy-drochlorid tilsættes, blandingen opvarmes til kogning, ·· 149473 5 og efter kogning deraf i 30 minutter tilsættes 108 g benzaldehyd. Blandingen koges i 2 timer og afkøles slutteligt til stuetemperatur. Der fremkommer pyclohexylimino-bisphenylmethanphosphonsyre med en renhed på 97 ?ό. Udbyt-5 te: 92 %. I dette eksempel udføres omsætningen mellem phosphortrichlorid og cyclohexylamin i nærværelse af ca. 19,5 mol vand per mol phosphortrichlorid.EXAMPLE 5 To a container equipped with a stirrer and a baking cooler is added 350 ml of water and with stirring an additional 138 g of phosphorus trichloride is added while maintaining the temperature of approx. 40 ° C. 62 g of cyclohexylamine hydrochloride are added, the mixture is heated to boiling, and after boiling for 30 minutes, 108 g of benzaldehyde are added. The mixture is boiled for 2 hours and finally cooled to room temperature. Pyclohexylimino-bisphenylmethane phosphonic acid with a purity of 97 ° frem is obtained. Yield 5: 92%. In this example, the reaction between phosphorus trichloride and cyclohexylamine is carried out in the presence of ca. 19.5 moles of water per mole of phosphorus trichloride.
EKSEMPEL 6EXAMPLE 6
Til 350 ml vand i en beholder, der er forsynet med en 10 omrører og tilbagesvaler, tilsættes 138 g phosphortri chlorid, således at temperaturen ikke overskrider 40 °C. Der tilsættes derpå 15 g ethylendiamin og reaktions-blandingen opvarmes til kogning. Efter kogning i 30 minutter tilsættes der 170 g af en 38 % vandig formalde-15 hyd-opløsning, hvorefter blandingen afkøles til stuetemperatur. Det fremkomne hvide, krystallinske produkt er Ν,Ν,Ν',Ν'-tetraphosphonomethylethylendiamin. Udbytte 93 7ά, renhed 98 %, dekomposition ved 214 °C. I dette eksempel udføres omsætningen mellem phosphortrichlorid 20 og ethylendiamin i nærværelse af ca. 19,5 mol vand per mol phosphortrichlorid.To 350 ml of water in a vessel equipped with a stirrer and reflux, add 138 g of phosphorus tri chloride so that the temperature does not exceed 40 ° C. 15 g of ethylenediamine are then added and the reaction mixture is heated to boiling. After boiling for 30 minutes, 170 g of a 38% aqueous formaldehyde solution is added and the mixture is cooled to room temperature. The resulting white crystalline product is Ν, Ν, Ν ', Ν'-tetraphosphonomethylethylenediamine. Yield 93 7ά, purity 98%, decomposition at 214 ° C. In this example, the reaction between phosphorus trichloride 20 and ethylenediamine is carried out in the presence of ca. 19.5 moles of water per mole of phosphorus trichloride.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HU78NI213A HU177486B (en) | 1978-04-11 | 1978-04-11 | Process for preparing phosphonic acid derivatives |
| HUNI000213 | 1978-04-11 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK148679A DK148679A (en) | 1979-10-12 |
| DK149473B true DK149473B (en) | 1986-06-23 |
| DK149473C DK149473C (en) | 1986-12-01 |
Family
ID=11000006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK148679A DK149473C (en) | 1978-04-11 | 1979-04-10 | PROCEDURE FOR PREPARING AMINOMETHAN PHOSPHONIC ACIDS |
Country Status (30)
| Country | Link |
|---|---|
| JP (1) | JPS554362A (en) |
| AR (1) | AR227625A1 (en) |
| AT (1) | AT373602B (en) |
| BE (1) | BE875501A (en) |
| BG (1) | BG34334A3 (en) |
| BR (1) | BR7900568A (en) |
| CA (1) | CA1135279A (en) |
| CH (1) | CH642666A5 (en) |
| CS (1) | CS239903B2 (en) |
| DD (1) | DD142888A5 (en) |
| DE (1) | DE2914294C2 (en) |
| DK (1) | DK149473C (en) |
| EG (1) | EG13622A (en) |
| ES (1) | ES471960A1 (en) |
| FR (1) | FR2422675B1 (en) |
| GB (1) | GB2021589B (en) |
| GR (1) | GR67713B (en) |
| HU (1) | HU177486B (en) |
| IL (1) | IL57008A0 (en) |
| IN (1) | IN149779B (en) |
| IT (1) | IT1118553B (en) |
| LU (1) | LU81126A1 (en) |
| NL (1) | NL7902854A (en) |
| NO (1) | NO160373C (en) |
| PL (1) | PL123998B1 (en) |
| PT (1) | PT69461A (en) |
| RO (1) | RO78631A (en) |
| SU (1) | SU776561A3 (en) |
| TR (1) | TR20811A (en) |
| YU (1) | YU41154B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL72142A0 (en) * | 1983-08-17 | 1984-10-31 | Stauffer Chemical Co | Preparation of phosphonomethylated amino acids |
| GB2154588B (en) * | 1984-02-20 | 1987-10-07 | Sunlead Chemical Industry Co L | A process for preparation of n-phosphonomethyl glycine |
| JPS6134834U (en) * | 1985-07-24 | 1986-03-03 | 三菱農機株式会社 | Mounting device for fertilizer tank, etc. on riding paddy field work machine with fertilization device |
| HU205944B (en) * | 1988-02-08 | 1992-07-28 | Nitrokemia Ipartelepek | Process for producing n-phosphono-methyl-imino-diacetic acid |
| GB8825589D0 (en) * | 1988-11-02 | 1988-12-07 | Albright & Wilson | Purification |
| HU203360B (en) * | 1988-11-25 | 1991-07-29 | Monsanto Co | Process for producing n-acylamino methylphosphonates |
| JP2525977B2 (en) * | 1991-10-17 | 1996-08-21 | 昭和電工株式会社 | Process for producing N-acylaminomethylphosphonic acid |
| US5495042A (en) * | 1993-11-04 | 1996-02-27 | Cytogen Corporation | Non-alkaline purification of aminophosphonic acids |
| TR200402620T4 (en) * | 2001-01-12 | 2004-11-22 | Basf Aktiengesellschaft | Method for the production of N-phosphonomethyliminodiacetic acid |
| CN100400543C (en) * | 2006-09-08 | 2008-07-09 | 四川贝尔实业有限责任公司 | Method for preparing Phosphonomethyl iminodiacetic acid (PMIDA) through hydrolysis of imino diacetonitrile |
-
1978
- 1978-04-11 HU HU78NI213A patent/HU177486B/en not_active IP Right Cessation
- 1978-07-21 ES ES471960A patent/ES471960A1/en not_active Expired
- 1978-08-03 SU SU782643651A patent/SU776561A3/en active
-
1979
- 1979-01-30 BR BR7900568A patent/BR7900568A/en unknown
- 1979-03-30 CH CH296679A patent/CH642666A5/en not_active IP Right Cessation
- 1979-04-03 GR GR58770A patent/GR67713B/el unknown
- 1979-04-03 GB GB7911510A patent/GB2021589B/en not_active Expired
- 1979-04-03 IN IN332/CAL/79A patent/IN149779B/en unknown
- 1979-04-03 FR FR7908315A patent/FR2422675B1/en not_active Expired
- 1979-04-05 IL IL57008A patent/IL57008A0/en unknown
- 1979-04-06 LU LU81126A patent/LU81126A1/en unknown
- 1979-04-06 CS CS792378A patent/CS239903B2/en unknown
- 1979-04-07 EG EG208/79A patent/EG13622A/en active
- 1979-04-09 AT AT0263179A patent/AT373602B/en not_active IP Right Cessation
- 1979-04-09 DE DE2914294A patent/DE2914294C2/en not_active Expired
- 1979-04-09 RO RO7997178A patent/RO78631A/en unknown
- 1979-04-10 TR TR20811A patent/TR20811A/en unknown
- 1979-04-10 BG BG7943195A patent/BG34334A3/en unknown
- 1979-04-10 YU YU850/79A patent/YU41154B/en unknown
- 1979-04-10 DK DK148679A patent/DK149473C/en not_active IP Right Cessation
- 1979-04-10 PT PT69461A patent/PT69461A/en unknown
- 1979-04-10 NO NO791217A patent/NO160373C/en unknown
- 1979-04-10 PL PL1979214793A patent/PL123998B1/en unknown
- 1979-04-11 JP JP4409879A patent/JPS554362A/en active Pending
- 1979-04-11 CA CA000325294A patent/CA1135279A/en not_active Expired
- 1979-04-11 DD DD79212157A patent/DD142888A5/en not_active IP Right Cessation
- 1979-04-11 BE BE0/194546A patent/BE875501A/en not_active IP Right Cessation
- 1979-04-11 AR AR276155A patent/AR227625A1/en active
- 1979-04-11 IT IT67767/79A patent/IT1118553B/en active
- 1979-04-11 NL NL7902854A patent/NL7902854A/en not_active Application Discontinuation
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