IL99203A - Process for the preparation of aminomethylphosphonic acid and aminomethylphosphinic acid - Google Patents
Process for the preparation of aminomethylphosphonic acid and aminomethylphosphinic acidInfo
- Publication number
- IL99203A IL99203A IL9920391A IL9920391A IL99203A IL 99203 A IL99203 A IL 99203A IL 9920391 A IL9920391 A IL 9920391A IL 9920391 A IL9920391 A IL 9920391A IL 99203 A IL99203 A IL 99203A
- Authority
- IL
- Israel
- Prior art keywords
- acid
- phenyl
- water
- formula
- alkyl
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 18
- 238000002360 preparation method Methods 0.000 title claims description 7
- MGRVRXRGTBOSHW-UHFFFAOYSA-N (aminomethyl)phosphonic acid Chemical compound NCP(O)(O)=O MGRVRXRGTBOSHW-UHFFFAOYSA-N 0.000 title abstract description 14
- OHWRASKXEUIFFB-UHFFFAOYSA-N NCP(O)=O Chemical compound NCP(O)=O OHWRASKXEUIFFB-UHFFFAOYSA-N 0.000 title abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 150000007513 acids Chemical class 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 239000000543 intermediate Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- LFSFPNIUQADDIM-UHFFFAOYSA-N benzamidomethylphosphonic acid Chemical compound OP(O)(=O)CNC(=O)C1=CC=CC=C1 LFSFPNIUQADDIM-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000005711 Benzoic acid Substances 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- HKYGSMOFSFOEIP-UHFFFAOYSA-N dichloro(dichloromethoxy)methane Chemical compound ClC(Cl)OC(Cl)Cl HKYGSMOFSFOEIP-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UUALUIHRPLSOCI-UHFFFAOYSA-N (1-amino-2-oxopropyl)phosphonic acid Chemical compound C(C)(=O)C(P(O)(=O)O)N UUALUIHRPLSOCI-UHFFFAOYSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- FDNUAHPLMXZWLS-UHFFFAOYSA-N (acetamidomethyl)phosphonic acid Chemical compound CC(=O)NCP(O)(O)=O FDNUAHPLMXZWLS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QLAUIXHXGPSZQW-UHFFFAOYSA-N aminomethyl(methyl)phosphinic acid Chemical compound CP(O)(=O)CN QLAUIXHXGPSZQW-UHFFFAOYSA-N 0.000 description 1
- JYVWZHOGCZHONC-UHFFFAOYSA-N aminomethyl(phenyl)phosphinic acid Chemical compound NCP(O)(=O)C1=CC=CC=C1 JYVWZHOGCZHONC-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- NTYBHEKOVMEONU-UHFFFAOYSA-N benzamidomethyl(methyl)phosphinic acid Chemical compound CP(O)(=O)CNC(=O)C1=CC=CC=C1 NTYBHEKOVMEONU-UHFFFAOYSA-N 0.000 description 1
- BBPSHEVQDYJYJA-UHFFFAOYSA-N benzamidomethyl(phenyl)phosphinic acid Chemical compound C=1C=CC=CC=1P(=O)(O)CNC(=O)C1=CC=CC=C1 BBPSHEVQDYJYJA-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical class NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- MLCHBQKMVKNBOV-UHFFFAOYSA-N phenylphosphinic acid Chemical compound OP(=O)C1=CC=CC=C1 MLCHBQKMVKNBOV-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur 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
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
-
- 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
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Aminomethanephosphonic acid and aminomethylphosphinic acids are interesting biologically active compounds or intermediates for the production of biologically active compounds. Such compounds having the formula (I), in which R?1 is OH, C1?-C4?-alkyl or phenyl, can be produced in a technically easy manner, by reacting with water at 80 to 300 C compounds having the formula (II), in which R?2 is H, C1?-C6?-alkyl, benzyl, phenyl, if necessary substituted by C1?-C4?-alkoxy and/or halogen, and R?1 has the same meaning as above.
Description
PROCESS FOR THE PREPARATION OF AMINOMETHYLPHOSPHONIC ACID __■ : AND AMINOMETHYLPHOSPHINIC ACIDS HOECHST AKTIENGESELLSCHAFT HOE 90/F 249 Dr. E/PP Description Process for the preparation of aminomethylphosphonic acid and aminomethylphosphinic acids Herbicidal and plant-growth-regulating actions are known of aminomethylphosphonic acid; aminomethylphosphinic acids are also industrially valuable compounds having a biological activity or can be used as intermediates for the preparation of biologically active compounds (see the article by L. Maier "Advances in the Chemistry of Amino-phosphinic Acids" in the periodical "Phosphorus and Sulfur" 1983, Vol. 14, p. 295-322, in particular 317-323 and literature cited therein) . Aminomethylphosphonic acid is furthermore valuable as an intermediate for the preparation of N-phosphonomethylglycine (see EP-A-214,578) .
Aminomethylphosphonic acid can be prepared from acyl-aminomethylphosphonic acids by hydrolysis with hydrochloric acid (US-A-2,304,156? US-A-2,328,358; M. Soroka, Synthesis 1989, 547). It is a disadvantage of this process that the aminomethylphosphonic acid can only be obtained in high yields during working-up when special measures are applied. For example, H. Soroka describes working-up with the aid of pyridine or propylene oxide, which cause the separation of hydrogen chloride from the aminomethylphosphonic acid. Another disadvantage is that, without complicated ultrapurification, the acylamino-methylphosphonic acids contain traces of formaldehyde, due to the production process. The treatment with hydrochloric acid in the hydrolysis then results in the formation of bischloromethyl ether as undesirable by-product, which has been identified clearly as a carcinogenic working substance. There is therefore a demand for hydrolysis processes which can be carried out on an industrial scale and which exclude the formation of 99203/2 the by-product bischloromethyl ether.
The invention relates to a process for the preparation of compounds of the formula I in which R1 is hydroxyl, preferably Ci-Cj,-alkyl, in particular methyl, or is phenyl, which comprises reacting acylaminomethylphosphonic or acylamino-methylphosphinic acids of the formula II in which R2 is hydrogen, alkyl having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, or is benzyl or phenyl, unsubstituted or substituted by one or more radicals from the group comprising C1-C4-alkyl, C^-C^-alkoxy and halogen, and R1 is as defined above, with water essentially as sole reagent at 80 to 300°C, preferably 150 to 250°C.
Some of the starting substances of the formula II are known, or some are accessible analogously to known methods. For example, the acylaminomethylphosphonic acids of the formula II can be prepared from N-(hydroxymethyl) -amides and PC13 (see US-A-2 , 328, 358; US-A-2 f 304 , 156 or H. Soroka, Synthesis 1989, 547 and literature cited therein) .
The acylaminomethylphosphonic acids as well as the acylaminomethylphosphinic acids of the ^rmula II can also be prepared by the process ir erman Patent - Application P 4,026,026.7.
Examples of preferred starting substances of the formula II are formylaminomethylphosphonic acid, acetyl-aminomethylphosphonic acid, benzoylaminomethylphosphonic acid, (acetylaminomethy1) (methylJphosphinic acid and (benzoylaminomethy1) (phenyl)phosphinic acid.
The starting substances of the formula II are treated with water, if appropriate with an excess of water, and the mixture is brought to reaction temperature, and it may be necessary to carry out this process under pressure, as a function of the temperature.
The extent of the excess of water is not particularly critical for the reaction; for example, for reasons of better handling, it may be advantageous to use a 2 to 30 molar, preferably 10 to 25 molar, excess of water. The reaction temperatures are 80 to 300°C, preferably 150 to 250°C. The reaction times depend on the substrate, reaction temperature and pressure and are generally in the range from 5 to 40 hours, preferably 10 to 35 hours.
When the reaction is complete, working-up can be carried out in a simple manner, for example by removing the carboxylic acid as a solid (for example benzoic acid) or by distillation (for example acetic acid). The resulting aminomethylphosphonic acid, or aminomethylphosphinic acids, generally already have high purity. If appropriate, they can be obtained in ultrapure form by customary methods, preferably by crystallization.
Example 1 20 g (0.093 mol) of benzoylaminomethylphosphonic acid and 20 g of water were placed in a sealed tube and maintained at 200°C for 20 hours. After cooling, the reaction material was digested with 100 ml of water. The benzoic acid was subsequently filtered off with suction. The filtrate was concentrated in vacuo by distillation until it had reached an internal temperature of 75°C. There remained 10.3 9 (100 % of theory) of aminomethylphos-phonic acid which, according to 31P-NMR spectrum analysis, had a purity of 95 %.
Example 2 20 g (0.093 mol) of benzoylaminomethylphosphonic acid and 20 g of water were placed in a sealed tube and maintained at 150°C for 20 hours. After cooling, the reaction material was then digested with methanol and filtered off with suction. 8.2 g (80 % of theory) of aminomethylphosphonic acid of a decomposition point of 310°C were obtained.
Example 3 20 g (0.093 mol) of benzoylaminomethylphosphonic acid and 20 g of water were refluxed for 30 hours. After cooling, the reaction material was digested with 100 ml of methanol and filtered off with suction. 5.3 g (52 % of theory) of aminomethylphosphonic acid of a decomposition point of 275°C were obtained. Unreacted benzoylaminomethylphosphonic acid could be isolated from the filtrate.
Example 4 21.3 g (0.1 mol) of benzoylaminomethylmethylphosphinic acid and 42 g of water were placed in a sealed tube and maintained at 200°C for 20 hours. After cooling, the mixture was digested with water, and benzoic acid was removed by filtration with suction. The filtrate was evaporated to dryness in vacuo. The crystalline residue was digested with methanol and filtered off with suction. 8 g (73 % of theory) of aminomethylmethylphosphinic acid - - of a melting point of 255-261°C were obtained.
Example 5 20 g (0.073 mol) of benzoylaminomethylphenylphosphinic acid and 40 ml of water were placed in a sealed tube and maintained at 225°C for 23 hours. The benzoic acid was then removed by filtration with suction, followed by rinsing with water. The filtrate was concentrated to dryness in vacuo. There remained 12.5 g (100 % of theory) of crude aminomethylphenylphosphinic acid. After diges-tion with methanol, the substance obtained had a melting point of 276-278eC.
Example 6 14.4 g (0.094 mol) of acetylaminomethylphosphonic acid and 28 g of water were fed into a sealed tube and maintained at 200°C for 20 hours. The mixture was then cooled, and the resulting reaction solution was freed in vacuo from water and acetic acid. The residue was digested with a mixture of 30 ml of methanol and 1 ml of water. 9.6 g (92 % of theory) of aminomethylphosphonic acid of a decomposition point of 270-278°C were obtained.
Claims (8)
1. A process for the preparation of compounds of the formula I OH in which R1 is hydroxy!, C1-CA-alkyl or phenyl, which comprises reacting acylamlnomethylphosphonlc or acylamino-methylphosphinic acids of the formula II in which R2 is hydrogen, alkyl having 1 to 6 carbon atoms, benzyl or phenyl, unsubstituted or substituted by one or more radicals from the group comprising alkoxy and halogen, and R1 is as defined above, with water essentially as sole reagent, at 80 to 300 °C.
2. The process as claimed in claim 1, in which R1 is hydroxy1.
3. The process as claimed in claim 1, in which R1 is methyl, ethyl or phenyl.
4. The process as claimed in claim 1, 2 or 3, in which R2 is H, Ci-Ca-alkyl, benzyl or phenyl.
5. The process as claimed in claim 1, 2 or 3, in which R2 is phenyl.
6. The process as claimed in one or more of claims 1 to 5, in which the reaction temperature is 150 to 250°C.
7. The process as claimed in one or more of claims 1 to 6, in which a 2 to 30 molar excess of water, based on 1 mol of compound of the formula II, is employed.
8. The process as claimed in one or more of claims 1 to 7, in which the reaction time is in the range from 5 to 40 hours.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4026027A DE4026027A1 (en) | 1990-08-17 | 1990-08-17 | METHOD FOR PRODUCING AMINOMETHANEPHOSPHONIC ACID AND AMINOMETHYL PHOSPHINIC ACIDS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IL99203A0 IL99203A0 (en) | 1992-07-15 |
| IL99203A true IL99203A (en) | 1995-08-31 |
Family
ID=6412399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL9920391A IL99203A (en) | 1990-08-17 | 1991-08-15 | Process for the preparation of aminomethylphosphonic acid and aminomethylphosphinic acid |
Country Status (18)
| Country | Link |
|---|---|
| EP (1) | EP0543845B1 (en) |
| JP (1) | JP3111076B2 (en) |
| KR (1) | KR100214903B1 (en) |
| CN (1) | CN1028996C (en) |
| AT (1) | ATE118008T1 (en) |
| AU (1) | AU653954B2 (en) |
| BR (1) | BR9106767A (en) |
| CA (1) | CA2089650C (en) |
| DE (2) | DE4026027A1 (en) |
| DK (1) | DK0543845T3 (en) |
| ES (1) | ES2069901T3 (en) |
| GR (1) | GR3015357T3 (en) |
| HU (1) | HU213457B (en) |
| IE (1) | IE912920A1 (en) |
| IL (1) | IL99203A (en) |
| PT (1) | PT98700B (en) |
| WO (1) | WO1992003449A1 (en) |
| ZA (1) | ZA916502B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2683222B1 (en) * | 1991-10-31 | 1995-05-19 | Rhone Poulenc Agrochimie | PROCESS FOR PRODUCING AMINOALKANEPHOSPHONIC ACIDS, SALTS AND / OR ESTERS. |
| CN104762689B (en) * | 2015-04-09 | 2017-01-04 | 泰索新材料科技（杭州）有限公司 | A kind of fire-retardant Nylon 6 fiber and preparation method thereof |
| CN104746168B (en) * | 2015-04-09 | 2016-10-12 | 泰索新材料科技（杭州）有限公司 | A kind of fire-retardant Nylon 66 fiber and preparation method thereof |
| CN104762688B (en) * | 2015-04-09 | 2017-01-04 | 泰索新材料科技（杭州）有限公司 | A kind of fire-retardant Nylon 66 and preparation method thereof |
| CN104744507B (en) * | 2015-04-09 | 2016-11-09 | 泰索新材料科技（杭州）有限公司 | A kind of aminomethyl phenyl phosphinic acid and preparation method thereof |
| RU2613837C1 (en) * | 2015-12-03 | 2017-03-21 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет" "МИСиС" | METHOD OF PRODUCING ION-PLASMA VACUUM-ARC CERAMETALLIC Ti-Ni COATING FOR CARBIDE CUTTING TOOL OF EXPANDED USE |
| CN108927292B (en) * | 2017-05-24 | 2021-10-22 | 中蓝连海设计研究院有限公司 | Aminophosphonic acid compound and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3824961A1 (en) * | 1988-07-22 | 1990-01-25 | Basf Ag | Process for the preparation of bis(aminomethyl)phosphinic acid, and acidic or basic salts thereof |
| HU203360B (en) * | 1988-11-25 | 1991-07-29 | Monsanto Co | Process for producing n-acylamino methylphosphonates |
-
1990
- 1990-08-17 DE DE4026027A patent/DE4026027A1/en not_active Withdrawn
-
1991
- 1991-08-07 ES ES91914121T patent/ES2069901T3/en not_active Expired - Lifetime
- 1991-08-07 BR BR919106767A patent/BR9106767A/en not_active Application Discontinuation
- 1991-08-07 AT AT91914121T patent/ATE118008T1/en not_active IP Right Cessation
- 1991-08-07 DK DK91914121.8T patent/DK0543845T3/en active
- 1991-08-07 DE DE59104516T patent/DE59104516D1/en not_active Expired - Fee Related
- 1991-08-07 EP EP91914121A patent/EP0543845B1/en not_active Expired - Lifetime
- 1991-08-07 WO PCT/EP1991/001494 patent/WO1992003449A1/en active IP Right Grant
- 1991-08-07 AU AU83095/91A patent/AU653954B2/en not_active Ceased
- 1991-08-07 CA CA002089650A patent/CA2089650C/en not_active Expired - Fee Related
- 1991-08-07 HU HU9300423A patent/HU213457B/en unknown
- 1991-08-07 JP JP03513167A patent/JP3111076B2/en not_active Expired - Fee Related
- 1991-08-15 IL IL9920391A patent/IL99203A/en not_active IP Right Cessation
- 1991-08-16 PT PT98700A patent/PT98700B/en not_active IP Right Cessation
- 1991-08-16 CN CN91105718A patent/CN1028996C/en not_active Expired - Fee Related
- 1991-08-16 ZA ZA916502A patent/ZA916502B/en unknown
- 1991-08-16 IE IE292091A patent/IE912920A1/en unknown
-
1993
- 1993-02-16 KR KR1019930700446A patent/KR100214903B1/en not_active IP Right Cessation
-
1995
- 1995-03-10 GR GR950400515T patent/GR3015357T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0543845B1 (en) | 1995-02-01 |
| ATE118008T1 (en) | 1995-02-15 |
| DE59104516D1 (en) | 1995-03-16 |
| JP3111076B2 (en) | 2000-11-20 |
| KR100214903B1 (en) | 1999-08-02 |
| AU8309591A (en) | 1992-03-17 |
| PT98700B (en) | 1999-01-29 |
| EP0543845A1 (en) | 1993-06-02 |
| WO1992003449A1 (en) | 1992-03-05 |
| JPH06500310A (en) | 1994-01-13 |
| BR9106767A (en) | 1993-08-24 |
| PT98700A (en) | 1992-07-31 |
| IE912920A1 (en) | 1992-02-26 |
| CA2089650C (en) | 2001-10-23 |
| ZA916502B (en) | 1992-04-29 |
| DE4026027A1 (en) | 1992-02-20 |
| HU213457B (en) | 1997-06-30 |
| GR3015357T3 (en) | 1995-06-30 |
| AU653954B2 (en) | 1994-10-20 |
| CN1059148A (en) | 1992-03-04 |
| ES2069901T3 (en) | 1995-05-16 |
| CA2089650A1 (en) | 1992-02-18 |
| HU9300423D0 (en) | 1993-05-28 |
| DK0543845T3 (en) | 1995-06-19 |
| CN1028996C (en) | 1995-06-21 |
| IL99203A0 (en) | 1992-07-15 |
| HUT64355A (en) | 1993-12-28 |
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