DE2929953A1 - METHOD FOR PRODUCING SALTS OF (-) CIS-1,2-EPOXYPROPYLPHOSPHONIC ACID WITH AMINO ACIDS - Google Patents
METHOD FOR PRODUCING SALTS OF (-) CIS-1,2-EPOXYPROPYLPHOSPHONIC ACID WITH AMINO ACIDSInfo
- Publication number
- DE2929953A1 DE2929953A1 DE19792929953 DE2929953A DE2929953A1 DE 2929953 A1 DE2929953 A1 DE 2929953A1 DE 19792929953 DE19792929953 DE 19792929953 DE 2929953 A DE2929953 A DE 2929953A DE 2929953 A1 DE2929953 A1 DE 2929953A1
- Authority
- DE
- Germany
- Prior art keywords
- cis
- acid
- amino acids
- salts
- amino acid
- 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.)
- Withdrawn
Links
- 150000001413 amino acids Chemical class 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title 1
- 235000001014 amino acid Nutrition 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- XWCIXXXLOAAWPU-IHWYPQMZSA-N [(z)-prop-1-enyl]phosphonic acid Chemical compound C\C=C/P(O)(O)=O XWCIXXXLOAAWPU-IHWYPQMZSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000006735 epoxidation reaction Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 4
- ODKSFYDXXFIFQN-BYPYZUCNSA-N L-arginine Chemical compound OC(=O)[C@@H](N)CCCN=C(N)N ODKSFYDXXFIFQN-BYPYZUCNSA-N 0.000 claims description 3
- 229930064664 L-arginine Natural products 0.000 claims description 3
- 235000014852 L-arginine Nutrition 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 2
- 150000001447 alkali salts Chemical class 0.000 claims description 2
- 238000001640 fractional crystallisation Methods 0.000 claims description 2
- KAZDQJDOHTVZDQ-VDQHJUMDSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2,5-diaminopentanoic acid Chemical compound NCCC[C@H](N)C(O)=O.NCCCC[C@H](N)C(O)=O KAZDQJDOHTVZDQ-VDQHJUMDSA-N 0.000 claims 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical class [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- AHLPHDHHMVZTML-BYPYZUCNSA-N L-Ornithine Chemical compound NCCC[C@H](N)C(O)=O AHLPHDHHMVZTML-BYPYZUCNSA-N 0.000 description 3
- 239000004472 Lysine Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 235000019766 L-Lysine Nutrition 0.000 description 2
- AHLPHDHHMVZTML-UHFFFAOYSA-N Orn-delta-NH2 Natural products NCCCC(N)C(O)=O AHLPHDHHMVZTML-UHFFFAOYSA-N 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229960003104 ornithine Drugs 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- GGTYBZJRPHEQDG-WCCKRBBISA-N (2s)-2,5-diaminopentanoic acid hydrochloride Chemical compound Cl.NCCC[C@H](N)C(O)=O GGTYBZJRPHEQDG-WCCKRBBISA-N 0.000 description 1
- GLVYLTSKTCWWJR-UHFFFAOYSA-N 2-carbonoperoxoylbenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1C(O)=O GLVYLTSKTCWWJR-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 1
- 239000004475 Arginine Substances 0.000 description 1
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- UTJLXEIPEHZYQJ-UHFFFAOYSA-N Ornithine Natural products OC(=O)C(C)CCCN UTJLXEIPEHZYQJ-UHFFFAOYSA-N 0.000 description 1
- 235000009697 arginine Nutrition 0.000 description 1
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000018977 lysine Nutrition 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 238000003756 stirring Methods 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65502—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a three-membered ring
- C07F9/65505—Phosphonic acids containing oxirane groups; esters thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Communicable Diseases (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pharmacology & Pharmacy (AREA)
- Oncology (AREA)
- Animal Behavior & Ethology (AREA)
- Medicinal Chemistry (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
T 51 909 - el - T 51 909 - el -
Anmelder; ITALCHEMI S.p.A. Applicant ; ITALCHEMI SpA
Corso Porta Vittoria, 31, Mailand, ItalienCorso Porta Vittoria, 31, Milan, Italy
Verfahren zur Herstellung von Salzen der (-)CIS-1,2-Epoxypropylphosphonsäure mit AminosäurenProcess for the preparation of salts of the (-) CIS-1,2-epoxypropylphosphonic acid with amino acids
Gegenstand der Erfindung ist ein neues Verfahren zur Herstellung von Salzen der (-J-cis-i^-Epoxypropylphosphonsäure mit Aminosäuren mit der allgemeinen Formel (I)The invention relates to a new process for the preparation of salts of (-J-cis-i ^ -epoxypropylphosphonic acid with amino acids with the general formula (I)
CH,- CH - CH . PO " . ÄH (i)CH, - CH - CH. PO ". ER (i)
wobei A eine Aminosäure, vorzugsweise eine natürliche Aminosäure wie Lysin, Arginin, Ornithin, Zystein und andere darstellt.where A is an amino acid, preferably a natural amino acid such as lysine, arginine, ornithine, cysteine and other represents.
In der deutschen Auslegeschrift 28 20 794 der Anmelderin wird ein Verfahren zur Herstellung der Verbindungen (I) beschrieben, das darin besteht, daß man im wesentlichen äquimolare Mengen von (-)-cis-1,2-Epoxypropylphosphonsäure und von Aminosäure im wässrigen oder in wässrig-alkoholischem Milieu reagieren läßt.In the applicant's German Auslegeschrift 28 20 794, a process for the preparation of the compounds (I) described, which consists in the fact that one essentially equimolar amounts of (-) - cis-1,2-epoxypropylphosphonic acid and reacts with amino acids in an aqueous or in an aqueous-alcoholic medium.
Es wurde nun festgestellt, daß die der Formel (I) entsprechenden Salze mit in Bezug auf die als Ausgangsprodukt eingesetzte Propenylphospho.nsäure allgemein höheren Ausbeuten und in einem reineren Zustand erhalten werden können, wenn die entsprechenden Salze der cis-Propenylphosphonsäure (II) mit denselben Aminosäuren einer Epoxydierung nach folgendem Schema unterzogen werden:It has now been found that the salts corresponding to the formula (I) are also used in relation to the starting product Propenylphospho.nsäure used generally higher yields and can be obtained in a purer state if the corresponding salts of cis-propenylphosphonic acid (II) with the same amino acids after an epoxidation be subjected to the following scheme:
030008/0667030008/0667
H HH H
^ N PO,". tE Epoxydierung^ N PO, ". TE epoxidation
3 3 ^ (D 3 3 ^ (D
wobei A die schon erwähnte Bedeutung hat.where A has the meaning already mentioned.
Es ist noch im einzelnen zu erwähnen, daß, wenn A eine optisch aktive Aminosäure darstellt, als Ergebnis der Epoxydierung eine Mischung von diastereoisomeren Salzen erhalten wird, die durch fraktionierte Kristallisation getrennt werden können.It should also be mentioned in detail that when A represents an optically active amino acid, as a result of the Epoxidation a mixture of diastereoisomeric salts is obtained, which are separated by fractional crystallization can be.
Die Epoxydierung kann durch an und für sich schon bekannte Methoden erreicht werden, z. B. mit Peroxysäuren (insbesondere mit Perbenzoesäure, m-Chlorperbenzoesäure, Monoperphthalsäure) oder mit HpO2, am besten in Anwesenheit von Alkalisalzen von Phosphorwolframsäuren.The epoxidation can be achieved by methods already known per se, e.g. B. with peroxy acids (especially with perbenzoic acid, m-chloroperbenzoic acid, monoperphthalic acid) or with HpO 2 , best in the presence of alkali salts of phosphotungstic acids.
Durch die nachfolgenden Beispiele wird das der Erfindung zugrundeliegende Verfahren veranschaulicht, ohne daß diesen Beispielen eine einschränkende Bedeutung beizumessen ist.The process on which the invention is based is illustrated by the following examples, without this Examples should be given a restrictive meaning.
(-)cis-epoxvpropvlphosphonsaures Salz des L-Arginins(-) cis-epoxvpropvlphosphonic acid salt of L-arginine
13,3 g (0,1 M) von cis-Propenylphosphonsäure (bromometrische Bestimmung: 91 %) werden in 80 ml Isopropanol gelöst; es werden 11 g (0,06 M) L-Arginin hinzugefügt, und es wird 60 Minuten lang gerührt. Das pH wird auf 5,6-5,7 mit Triäthylamin gebracht, danach werden 0,5 g Na2WO^.2H2O und 0,1 g EDTA-Na2, gelöst in 1,5 ml Wasser, hinzugefügt.13.3 g (0.1 M) of cis-propenylphosphonic acid (bromometric determination: 91 %) are dissolved in 80 ml of isopropanol; add 11 g (0.06 M) L-arginine and stir for 60 minutes. The pH is brought to 5.6-5.7 with triethylamine, then 0.5 g of Na 2 WO ^ .2H 2 O and 0.1 g of EDTA-Na 2 , dissolved in 1.5 ml of water, are added.
Es wird auf 48-500C erwärmt und 16,3 ml 3096-igem H2O2 V/V zugetropft, wobei die Temperatur bei 50-550C gehaltenIt is heated to 48-50 0 C and 16.3 ml 3096-strength H 2 O 2 v / v was added dropwise, keeping the temperature at 50-55 0 C held
wird. " *will. "*
030008/0667030008/0667
— Jr —- Jr -
Es wird 60 Minuten lang gerührt, und es wird dann abgekühlt, der Niederschlag (15 g) abfiltriert und dreimal aus Äthanol-Wasser umkristallisiert.The mixture is stirred for 60 minutes and then cooled, the precipitate (15 g) filtered off and recrystallized three times from ethanol-water.
Schmelzpunkt « 212-2170C mit Zersetzung.Melting point "212-217 0 C with decomposition.
Analyse: für C9H21OgN^P Molekulargewicht =312Analysis: for C 9 H 21 OgN ^ P molecular weight = 312
#C %K JON %P #C % K JON % P
ber. 34,61 6,73 17,95 9,93calc. 34.61 6.73 17.95 9.93
gef. 34,33 7,00 17,71 9,73found 34.33 7.00 17.71 9.73
- + 13,3 (C « 596 in H2O).- + 13.3 (C «596 in H 2 O).
PMR-Spektrum (in D2O) ζ, : 1,47 (CH,); 1,6-2 2,85 (CH-P); 3-3,3 (CH,CH2NH); 3,7 (CH-NH2).PMR spectrum (in D 2 O) ζ,: 1.47 (CH,); 1.6-2 2.85 (CH-P); 3-3.3 (CH, CH 2 NH); 3.7 (CH-NH 2).
(-)cis-epoxvpropYlphosphonsaures Salz des L-Lysins(-) cis-epoxvpropYlphosphonic acid salt of L-lysine
13,3 g (0,1 M) cis-Propenylphosphonsäure (bromometrische Bestimmung : 9190 werden in 80 ml Isopropanol gelöst; es werden 0,1 M (29 g zu 50% in H2O) L-Lysin hinzugefügt, und die Mischung wird 60 Minuten lang gerührt. Es werden 0,5 g Na2WO^.2H2O und 0,1 g EDTA.Na2, gelöst in 1,5 ml Wasser, hinzugefügt.13.3 g (0.1 M) cis-propenylphosphonic acid (bromometric determination: 9190 are dissolved in 80 ml isopropanol; 0.1 M (29 g at 50% in H 2 O) L-lysine are added, and the mixture The mixture is stirred for 60 minutes, 0.5 g of Na 2 WO ^ .2H 2 O and 0.1 g of EDTA.Na 2 , dissolved in 1.5 ml of water, are added.
Es wird auf 48-50°C erwärmt und 16,3 ml 30%-iges H2O2 V/V zugetropft, wobei die Temperatur bei 5O-55°C mit Wasserbad gehalten wird. Es wird 60 Minuten lang gerührt, dannIt is heated to 48-50 ° C. and 16.3 ml of 30% H 2 O 2 V / V are added dropwise, the temperature being kept at 50-55 ° C. with a water bath. It is stirred for 60 minutes, then
- 4 030008/0667 - 4 030008/0667
abgekühlt und sodann 150 ml absolutes Äthanol hinzugefügt. Ein gummiartiges Produkt fällt aus, die Flüssigkeit wird abdekantiert und das ausgefüllte Produkt mit absolutem Äthanol wieder aufgenommen.cooled and then 150 ml of absolute ethanol added. A gummy product precipitates out, which becomes liquid decanted off and the filled-in product was taken up again with absolute ethanol.
Es werden 17 g Produkt erhalten, das bei 170-1720C mit Zersetzung (n.c.) schmilzt.There are obtained 17 g of product which melts at 170-172 0 C with decomposition (nc).
Das Produkt wird dreimal aus Methanol umkristallisiert.The product is recrystallized three times from methanol.
Schmelzpunkt = 165°C mit Zersetzung.Melting point = 165 ° C with decomposition.
Analyse für cqH21N2°6P Molekulargewicht = 284Analysis for c q H 21 N 2 ° 6 P molecular weight = 284
ber. 38,03 7,39 9,86 10,91calc. 38.03 7.39 9.86 10.91
gef. 38,18 7,43 9,81 10,96found 38.18 7.43 9.81 10.96
« + 9,32 (C - W in H2O)«+ 9.32 (C - W in H 2 O)
PMR-Spektrum (in D2O) ζ> : 1,4-2,1 (CH3, (CH2)^); 2,8(CH-P); 3,3 (CH); 3,7 (CHNH2); 2,9-3,2 ()PMR spectrum (in D 2 O) ζ>: 1.4-2.1 (CH 3 , (CH 2 ) ^); 2.8 (CH-P); 3.3 (CH); 3.7 (CHNH 2 ); 2.9-3.2 ()
Beispiel example ττ
(-)cis-epoxypropvlphosphonsaures Salz des L-Ornithins(-) cis-epoxypropylphosphonic acid salt of L-ornithine
6,7 g (0,05 M) cis-Propenylsphosphonsäure (bromometrische6.7 g (0.05 M) cis-propenylphosphonic acid (bromometric
Bestimmung : 91%) werden zu einer Mischung von 8,5 g (0,05 M) L-Ornithin HCl, 40 ml 80%-igem Äthanol und 2 g (0,05 M) NaOH hinzugefügt. Es werden 0,25 g Na2WO2O und 0,05 g EDTA.Na2, gelöst in 1 ml H2O, hinzugefügt. -Determination: 91%) are added to a mixture of 8.5 g (0.05 M) L-ornithine HCl, 40 ml 80% ethanol and 2 g (0.05 M) NaOH. 0.25 g of Na 2 WO 2 O and 0.05 g of EDTA.Na 2 , dissolved in 1 ml of H 2 O, are added. -
030008/0667030008/0667
- Jet -- Jet -
Es wird auf480C erwärmt, und 8,2 ml 30#-iges H2O2 V/V hinzugefügt, wobei die Temperatur bei 50-550C mit Wasserbad gehalten wird.It is heated auf48 0 C, and 8.2 ml 30 # hydride H 2 O 2 v / v added, the temperature being maintained at 50-55 0 C with water bath.
Es wird 3 Stunden lang gerührt. Sodann werden 150 ml absolutes Äthanol hinzugefügt, das gummi artige Produkt wird abdekantiert und dreimal aus Äthanol-Wasser 2:1 urakristallisiert. It is stirred for 3 hours. Then 150 ml absolute ethanol is added, the rubber-like product is decanted off and uracrystallized three times from ethanol-water 2: 1.
Es wird ein Produkt erhalten, das bei 191-1930C mit Zersetzung (n.c.) schmilzt.There is obtained a product which melts at 191-193 0 C with decomposition (nc).
Analyse für CßH N0>P Molekulargewicht » 270Analysis for C ß H N0> P molecular weight »270
#C %K ' JiN %P #C % K ' JiN % P
- + 10,2 (C - 5% in H2O)- + 10.2 (C - 5% in H 2 O)
PMR-Spektrum (in D2O) % : 1,48 (CH31- 1,7-2 2,8-3,3 (CH-P, CH2NH2); 3,45 (CH); 3,85 (CHNH2).PMR spectrum (in D 2 O) % : 1.48 (CH 31 - 1.7-2 2.8-3.3 (CH-P, CH 2 NH 2 ); 3.45 (CH); 3, 85 (CHNH 2 ).
030008/0667030008/0667
Claims (6)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT26304/78A IT1097578B (en) | 1978-07-31 | 1978-07-31 | METHOD FOR PREPARING ACID SALTS (-) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE2929953A1 true DE2929953A1 (en) | 1980-02-21 |
Family
ID=11219184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19792929953 Withdrawn DE2929953A1 (en) | 1978-07-31 | 1979-07-24 | METHOD FOR PRODUCING SALTS OF (-) CIS-1,2-EPOXYPROPYLPHOSPHONIC ACID WITH AMINO ACIDS |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5562097A (en) |
| BE (1) | BE877644A (en) |
| DE (1) | DE2929953A1 (en) |
| DK (1) | DK291479A (en) |
| ES (1) | ES483027A1 (en) |
| FR (1) | FR2432523A1 (en) |
| GB (1) | GB2026492A (en) |
| IT (1) | IT1097578B (en) |
| LU (1) | LU81553A1 (en) |
| NL (1) | NL7905458A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH660306A5 (en) * | 1984-10-05 | 1987-04-15 | Schering Spa | WATER-SOLUBLE PHARMACEUTICAL COMPOSITIONS BASED ON SALTS OF (-)CIS-1,2-EPOXYPROPYLPHOSPHONIC ACID WITH AMINO ACIDS. |
| CH660305A5 (en) * | 1984-10-05 | 1987-04-15 | Schering Spa | WATER-SOLUBLE PHARMACEUTICAL COMPOSITIONS BASED ON SALTS OF (-)CIS-1,2-EPOXYPROPYLPHOSPHONIC ACID WITH AMINO ACIDS. |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3625982A (en) * | 1968-05-15 | 1971-12-07 | Merck & Co Inc | (1,2-epoxypropyl)phosphonous acid derivatives |
| JPS5414924A (en) * | 1977-07-01 | 1979-02-03 | Kanebo Ltd | Preparation of (-)-cis-1,2-epoxypropylphosphonic acid derivative |
-
1978
- 1978-07-31 IT IT26304/78A patent/IT1097578B/en active
-
1979
- 1979-07-11 DK DK291479A patent/DK291479A/en unknown
- 1979-07-12 BE BE2/57947A patent/BE877644A/en not_active IP Right Cessation
- 1979-07-12 NL NL7905458A patent/NL7905458A/en not_active Application Discontinuation
- 1979-07-16 GB GB7924643A patent/GB2026492A/en not_active Withdrawn
- 1979-07-18 FR FR7918632A patent/FR2432523A1/en active Pending
- 1979-07-24 DE DE19792929953 patent/DE2929953A1/en not_active Withdrawn
- 1979-07-25 JP JP9553779A patent/JPS5562097A/en active Pending
- 1979-07-27 LU LU81553A patent/LU81553A1/en unknown
- 1979-07-31 ES ES483027A patent/ES483027A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB2026492A (en) | 1980-02-06 |
| IT7826304A0 (en) | 1978-07-31 |
| ES483027A1 (en) | 1980-04-16 |
| FR2432523A1 (en) | 1980-02-29 |
| LU81553A1 (en) | 1979-10-31 |
| NL7905458A (en) | 1980-02-04 |
| JPS5562097A (en) | 1980-05-10 |
| IT1097578B (en) | 1985-08-31 |
| BE877644A (en) | 1979-11-05 |
| DK291479A (en) | 1980-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE1795808C2 (en) | Process for the preparation of 2,2,6,6-tetramethyl-4-oxopiperidine | |
| DD220026A5 (en) | METHOD FOR PRODUCING 3-POSITION AMINO-SUBSTITUTED PYRIDAZINE DERIVATIVES | |
| DE2826452A1 (en) | METHOD FOR PRODUCING SUBSTITUTED GUANIDINES | |
| EP0608693B1 (en) | Process for the preparation of folic acid | |
| DE2929953A1 (en) | METHOD FOR PRODUCING SALTS OF (-) CIS-1,2-EPOXYPROPYLPHOSPHONIC ACID WITH AMINO ACIDS | |
| DE1212984B (en) | Process for the production of basic substituted coumarones | |
| DE1745780B2 (en) | 1-SULFONYLAETHYL-2-METHYL-5-NITROIMIDAZOLE AND THE METHOD OF MANUFACTURING IT | |
| DE930988C (en) | Process for the preparation of basic alkylated tetrahydrocarbazoles or indoles | |
| DE3535451A1 (en) | METHOD FOR PRODUCING N-ALKYL-SUBSTITUTED HYDROXYLAMMONIUM CHLORIDES AND NEW N-ALKYL-SUBSTITUTED HYDROXYLAMMONIUM CHLORIDES | |
| DE1670143C3 (en) | ||
| DE1192647B (en) | Process for the production of thiol or thionothiolphosphonic acid esters | |
| DE2350395C3 (en) | N- (m-Trifluoromethylthiophenyl) piperazine, its salts, process for their preparation and their use as an intermediate compound for the preparation of piperazine derivatives | |
| EP0088359A2 (en) | Amidinophosphonic acids | |
| DE1046063B (en) | Process for the production of new, amoebicidal acetanilides | |
| DE917669C (en) | Process for the preparation of diimino ethers of Lachtimen | |
| DE697661C (en) | Process for the preparation of N-alkylated ª ‰ - (p-oxyphenyl) -isopropylamines | |
| EP0240918A1 (en) | Diphosphonylated oxonitriles, process for their preparation, their use in microbistatic compositions, and microbistatic compositions containing diphosphonylated oxonitriles | |
| DE2625848A1 (en) | SUBSTITUTED 1,2,4-OXADIAZOLIDIN-3-ONE COMPOUNDS, PROCESS FOR THEIR PRODUCTION AND THEIR USE AS PLANT PROTECTION PRODUCTS | |
| AT203496B (en) | Process for the preparation of new tertiary amines | |
| DE1745780C3 (en) | l-Sulfonyläthyl ^ -methyl-S-nitroimidazole and process for their preparation | |
| DE942027C (en) | Process for the preparation of substituted 2-iminothiazolidines | |
| DE2218248C3 (en) | Picolinic acid dithiocarbamates | |
| AT350579B (en) | PROCESS FOR THE PREPARATION OF NEW ARYLTRIFLUOROETHYLAMINES, THEIR SALT AND OPTICAL ISOMERS | |
| AT229884B (en) | Process for the production of new organic phosphorus compounds | |
| AT211823B (en) | Process for the preparation of new aryloxyacetic acid amides |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8139 | Disposal/non-payment of the annual fee |