AU653954B2 - Process for producing aminomethanephosphonic acid and aminomethylphosphinic acids - Google Patents
Process for producing aminomethanephosphonic acid and aminomethylphosphinic acids Download PDFInfo
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- AU653954B2 AU653954B2 AU83095/91A AU8309591A AU653954B2 AU 653954 B2 AU653954 B2 AU 653954B2 AU 83095/91 A AU83095/91 A AU 83095/91A AU 8309591 A AU8309591 A AU 8309591A AU 653954 B2 AU653954 B2 AU 653954B2
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- MGRVRXRGTBOSHW-UHFFFAOYSA-N (aminomethyl)phosphonic acid Chemical compound NCP(O)(O)=O MGRVRXRGTBOSHW-UHFFFAOYSA-N 0.000 title claims abstract description 16
- OHWRASKXEUIFFB-UHFFFAOYSA-N NCP(O)=O Chemical class NCP(O)=O OHWRASKXEUIFFB-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 238000000034 method Methods 0.000 title claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 15
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 239000000543 intermediate Substances 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 241001136792 Alle Species 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims 1
- 210000004072 lung Anatomy 0.000 claims 1
- 239000002689 soil Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 150000007513 acids Chemical class 0.000 description 10
- 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
- 239000005711 Benzoic acid Substances 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000706 filtrate 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
- 239000000203 mixture Substances 0.000 description 3
- FDNUAHPLMXZWLS-UHFFFAOYSA-N (acetamidomethyl)phosphonic acid Chemical compound CC(=O)NCP(O)(O)=O FDNUAHPLMXZWLS-UHFFFAOYSA-N 0.000 description 2
- 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
- NYPYHUZRZVSYKL-UHFFFAOYSA-N 2-azaniumyl-3-(4-hydroxy-3,5-diiodophenyl)propanoate Chemical compound OC(=O)C(N)CC1=CC(I)=C(O)C(I)=C1 NYPYHUZRZVSYKL-UHFFFAOYSA-N 0.000 description 1
- -1 Bewzyl Chemical group 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
- ZVQSISKECFIRMH-UHFFFAOYSA-N acetamidomethyl(methyl)phosphinic acid Chemical compound CC(=O)NCP(C)(O)=O ZVQSISKECFIRMH-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
- 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
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- 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
OPI DATE 17/03/92 NTlAOJP DATE 30/04/92 INTEI.. APPLN. ID 83095 91 PCT NUMBER PCT/EP91/01494 !ER DIE 'S (PCT) (51) Internationale Patentklassifikation 5 Internationale Veriiffentlichungsnummer: WO 92/03449 C07F 9/30, 9/38 Al (43) Intemnationales Verb!'fentlichungsdatuni: 5. Mflrz 1992 (05.03.92) (21) Intemnationales Aktenzeichen: PCT/EP9I/01494 (81) Bestimmungsstaaten: AT (europflisches Patent), AU, BB, BE (europflisches Patent), BF (OAPI Patent), BG, BJ (22) Internationales Anineldedatumn: 7. August 1991 (07.08.91) (QAPI Patent), BR, CA, CF (OAPI Patent), CG (OAPI Patent), CH (europffisches Patent), CI (OAPI Patent), CM (OAPI Patent), DE (europ~isches Patent), DK (eu- Prioritatsdateii: rop~irches Patent), ES (europflisches Patent), FI, FR P 40 26 027.5 17. August 1990 (17.08.90) DE (europitisches Patent), GA (QAPI Patent), GB (europdisches Patent), GN (OAPI Patent), GR (europflisches Patent), HU, IT (europflisches Patent), JP, KP, KR, L&, (71) Anmielder (Itir alle Bestimmungsstaalen ausser US): HO- LU (europiiisches Patent), MC, MG, ML (OAPI Patent), ECHST AKTIENGESELLSCHAFT [DE/DE]; Post- MR (QAPI Patent), MW, NL I 'uropflisches Patent), fach 80 03 20, D-6230 Frankfurt am Main 80 NO, PL, RO, SD, SE (europiiisches Patent), SN (OAPI Patent), SU+,TD (OAPI Patent), TG (OAPI Patent), US.
(72) Erfinder; und Erfinder/Anmelder (nur flir US) KLEINER, Hans-Jerg [DE/DE]; Altk6nigstra~e I1I a, D-6242 Kronberg Veroffentllcht Mit internationalem Rec/zerehenbericht.
(74) Gemteinsamer Vertreter: HOECHST AKTIENGESELL- SCHAFT; Zentrale Patentabteilung, Postfach 80 03 D-6230 Frankfurt am Main 80 (DE).
653954 (54)Titte: PROCESS FOR PRODUCING AMINOMETHANEPHOSPHONIC ACID AND AMINOMETH-YLPHOSPHl- NIC ACIDS (54) Ilezeichnung: VERFAHREN ZUR HERSTELLUNG VON AMINOMETHANPHOSPHONSAURE UND AMINOMET-
HYL-PHOSPHINSAUREN
H
2NCH 2p
O
00) 0 R'
RICNHCH
2 P
O
(57) Abstract Aminornethanephosphonic acid and aminomethyiphosphinic acids are interesting biologically active compounds or intermediates for the production of biologically active compounds. Such compounds having the formula in which RI is OH,
C
1
-C
4 -alkyl or phenyl, can be produced in a technically easy manner, by reacting with water at 80 to 300 OC compounds having the formula in which R 2 is H, C 1
-C
6 alkcyl, benzyl, phenyl, if necessary substituted by CX- 4 -alkoxy and/or halogen, and R1 has the same meaning as above.
(57) Zusammenfassung Aminomethanphosphonstiure und Aminomethyl-phosphinstiuren sind ais biologisch aktive Verbindungen oder als Zwischenprodukte zur Herstellung bieulogisch aktiver Verbindungen interessant. ErfindungsgemaRl k8nnen derartige Verbindungen der Formel worin R1 OH, CX- 4 'A*tyI oder Phenyl bedeutet, in einer t'inisch einfachen Weise hergestelit werden, indem man Verbindungen der Formel worm -R 2 H, C 1
-C
6 .Alkyl, Bewzyl, Phenyl, das gegebenenfalls durch C,-C 4 -Akl -Alkoxy und/oder Halogen substituiert ist, bedeutet und RI wie oben definiert ist, mit Wasser bei 80 bis 300 00 -xmsetzt, Siehe Rflckseite WO 92/03449 1 PCT/EP91/01494 Description Process for the preparation of aminomethanephosphonic acid and aminomethylphosphinic acids Herbicidal and plant-growth-regulating actions are known of aminomethanephosphonic 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 Aminophosphinic Acids" in the periodical "Phosphorus and Sulfur" 1983, Vol. 14, p. 295-322, in particular 317-323 and literature cited therein). Aminomethanephosphonic acid is furthermore valuable as an intermediate for the preparation of N-phosphonomethylglycine (see EP-A-214,578).
Aminomethanephosphonic acid can be prepared from acylaminomethanephosphonic 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 aminomethanephosphonic acid can only be obtained in high yields during working-up when special measures are applied. For example, M. Soroka describes working-up with the aid of pyridine or propylene oxide, which cause the separation of hydrogen chloride from the aminomethanephosphonic acid. Another disadvantage is that, without complicated ultrapurification, the acylaminomethanephosphonic 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 the by-product bischloromethyl ether.
1 ^s/s 2 The invention relates to a process for the preparation of compounds of the formula I O R-
H
2 NCH
I
OH
in which R 1 is hydroxyl, Cl-C 4 -alkyl, preferably Ci-C 2 alkyl, in particular methyl, or is phenyl, which comprises reacting acylaminomethanephosphonic or acylaminomethylphosphinic acids of the formula II 2 R1 R2CONHCH 2 P H
OH
in which R 2 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 Ci-C 4 -alkyl, C 1
-C
4 -alkoxy and halogen, and R 1 is as defined above, with water, 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 acylaminomethanephosphonic acids of the fcrmula II can be prepared from N-(hydroxymethyl)amides and PC13 (see US-A-2,328,358; US-A-2,304,156 or M. Soroka, Synthesis 1989, 547 and literature cited therein).
The acylaminomethanephosphonic acids as well as the acylaminomethylphosphinic acids of the formula II can also be prepared by the process in German Patent Application P 4,026,026.7.
ra:I, Examples of preferred starting substances of the 1 ;3.
3 formula II are formylaminomethanephosphonic acid, acetylaminomethanephosphonic acid, benzoylaminomethanephosphonic acid, (acetylaminomethyl)(methyl)phosphinic acid and (benzoylaminomethyl)(phenyl)phosphinic acid.
The starting substances of the formula II are treated with water, if appropriate with an excess of water, and the mir'-,re 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 molar, preferably 10 to 25 molar, excess of water. The reaction temperatures are 80 to 300 0 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 aminomethanephosphonic 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 g (0.093 mol) of benzoylaminomethanephosphonic 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 Suntil it had reached an internal temperature of ji There remained 10.3 g (100 of theory) of aminomethane- -4phosphonic acid which, according to 31 P-NMR spectrum analysis, had a purity of 95 Example 2 g (0.093 mol) of benzoylaminomethanephosphonic acid and 20 g of water were placed in a sealed tube and maintained at 150 0 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 aminomethanephosphonic acid of a decomposition point of 310°C were obtained.
Example 3 g (0.093 mol) of benzoylaminomethanephosphonic 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 benzoylaminomethanephosphonic 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 0 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 g (0.073 mol) of benzoylaminomethylphenylphosphinic
O
O I i P ii- 1Llli-l acid and 40 ml of water were placed in a sealed tube and maintained at 225 0 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 digestion with methanol, the substance obtained had a melting point of 276-278°C.
Example 6 14.4 g (0.094 mol) of acetylaminomethanephosphonic acid and 28 g of water were fed into a sealed tube and maintained at 200 0 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 aminomethanephosphonic acid of a decomposition point of 270-278 C were obtained.
I -f'
L
Claims (10)
1. A rocess for the preparation of compounds of the formula I R1 H 2 NCH2P I in which R 1 is hydroxyl, C 1 -C 4 -alkyl or phenyl, which com- prises reacting acylaminomethanephosphonic or acylamino- methylphosphinic acids of the formula II 2 /R 1 R 2 CONHCH 2 P OH in which R 2 is hydrogen, alkyl having 1 to 6 carbon atoms, benzyl or phenyl, unsubstituted or substituted by one or more radicals from the group comprising C 1 -C 4 -alkyl, Ci-C 4 alkoxy and ha.'-gen, and R 1 is as defined above, with water, at 80 to 300°C.
2. The process as claimed in claim 1, in which R 1 is hydroxyl.
3. The process as claimed in claim 1, in which R 1 is Smethyl, ethyl or phenyl.
4. The process as claimed in claim 1, 2 or 3, in which R 2 is H, C 1 -C 3 -alkyl, benzyl or phenyl.
5. The process as claimed in claim 1, 2 or 3, in which R 2 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
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 to 40 hours. 8 HOE 90/F 249 Abstract of the disclosure: Process for the preparation of aminomethanephosphonic acid and aminomethylphosphinic acids Aminomethanephosphonic acid and aminomethylphosphinic acids are interesting as biologically active compounds or as intermediates for the preparation of biologically active compounds. According to the invention, such compounds of the formula I 0 /R 1 H 2 NCH2P I OH in which R 1 is OH, C 1 -C 4 -alkyl or phenyl, can be prepared in a technically simple manner by reacting compounds of the formula II 0 R 1 II R 2 CONHCH 2 OH in which R 2 is H, Cl-C 6 -alkyl, benzyl, phenyl, optionally substituted by C 1 -C 4 -alkyl, -alkoxy and/or halogen, and R 1 is as defined above, with water, at 80 to 300"C. t I' i IN i TERNATIONAL SEARCH REPORT International Application No PCT/EP 91/01494 [1 I. CLASSIFICATION OF SUBJECT MATTER (if several classification symbols apply, Indicate all) According to International Patent Classification (IPC) or to both National Classification and IPC Int.Cl. 5 C 07 F 9/30; C 07 F 9/38 II. FIELDS SEARCHED Minimum Documentation Searched 7 Classification System I Classification Symbols Int.Cl. 5 C 07 F Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included in the Fields Searched III, DOCUMENTS CONSIDERED TO BE RELEVANT' Category Citation of Document, with indication, where appropriate, of the relevant passages 12 Relevant to Claim No, 1 Y DE, A, 3824961 (BASF AG) 25 January 1990 1-8 see the whole document Y EP, A, 0370992 (MONSANTO COMPANY) 30 May 1990 1-8 see the whole document Y CHEMICAL ABSTRACTS, vol. 107, No. 5, 3 August 1987 1-8 Columbus, Ohio, US; abstract No. 39933, PULWER M.J. "a convenient synthesis of aminomethylphosphonic acid" see abstract Y SYNTHESIS. No. 7 1989, STUTTGART DE pages 547- 1-8 548; SOROKA M. "comments on the synthesis of' aminomethylphosphonic see the whole document Special categories of cited documents: 10 later document publish:d :iter the International filing date document defining the general state of the art which is not or priority date and not in onflict with the application but considered to be of particular relevance cited to understand the prlcilple oe theory underlying the invention earlier document but published on or after the international document o particular relevance: the claimed Invention filing dat cannot be considered novel or cannot be considered to documen which may throw doubts on priority claim(s) or Involve an inventive step which i1 cited to establish the publication date of another document of particular relevance' the claimed invention cition r thr spcial reason i document o particular relevance the claimed Invenon caion or oer special reason a speciied) cannot be considered to involve an Inventive step when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu. other means ments, such combination being obvious to a person skilled document published prior to the international filing date but in the art, later than the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing of this International Search Report 28 October 1991 (28.10.91) 25 November 1991 (25.11.91) International Searching Authority Signature of Authorized Offcer EUROPEAN PATENT OFFICE Form PCTIISAI210 (second sheet) (January 1915) i A'. L n I- ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. EP 9101494 SA 50041 This annex lists the patent family members relating to the patent documents cited in the above-mentioned international search report. The members are as contained in the European Patent Office EDP file on The European Patent Office is in no way liable for these particulars which are merely given for the purpose of information. 28/10/91 SFor more details aout his nnex see Oicil Journal of the European Patent O N. W For more details about this annex see Official Journal of the European Patent Office, No. 12I12 INTERNATIONALER RECI-ERCHENBERICHT PCT/EP 91/01494 IInterilstonales Aktenzeichen 1. KLASSIFIKATION DES ANMELDUNGSGEGENSTANDS (bel mehreren Kiasslfilkatloiusymboki sind alle sknZUgeben) 6 Nach der Internationaien ratcntlklassfikatlon (11PC oder nail, der nationalen Kiassifikalion und der IPC Int.K1. 5 C07F9/30 C07F9/38 11, RECIIER.CIIIERTE SAClIGEIIIETE Recherchierter Mlndestpriftltoff Recherchlerle nicht zum Mindcstprtlfsloff gehorende Vcrbfcntlichungcn, sowelithdese unter die fecherchlerten Sachgebicte fallen a JI. EINSCIILAGIGE VEROFFENTLICIUNGEN 9~ Art., Kennzeichnung der V'orliffentlichung I sowelt erforderlich tinter Angabo der nia~geblichen Tclle 1 2 Octr. Anspruch Nr.1 3 Y OEA3 824 961 (BASF AG) 25. Januar 1990 1-8 siehe das ganze Dokument Y EP,A,0 370 992 (MONSANTO COMPANY) 30. Mai 1990 8 siehe das ganze Dokument Y CHEMICAL ABSTRACTS, vol. 107, no. 5, 1-8 3. August 1987, Columbus, Ohio, US; abstract no. 39933, PULWER 'a convenient synthesis of aminomethyiphosphonic acid' siehe Zusammenfassung 0 lesondere Kategorlen von angegebeaen Veriiffcntlichungcn to Verliffentlichung, die den ailgemeinen Stand der Technik IT' Spitcre VerOiffntiichung, die nach den, lntcrnationalon An- definhert, aber n icht a is bes-ondirs bedcutnani an.uschcfl 1st meldedatumn oder denm 11frirlisdaluni vertlffentlicht "orden 'E Anntm oiededaun ledcersnlt modert 1st er Interna- ist und mit der Annieldung nicht kollidiert, sondern nur zumn tionen Aokmint, dasun leortch 1a woden hac dc Verstlndnis des dcr Ernung zugrundeiicgcnden Ptinzips tionalenoder dcr ihr sugrundcllegenden Theorie angegeben Ist L Vertiffentlichung, die geelitnet 1st, einen Prlnriltisanspruch ''Vrietihn o eodrrPd ug i enpuh zweifelhaft erscheinen zu Ilassen, oder durch die dat Verb(f- Vclfeichgvnbsodr edungdehanpc- fentlichungsdatum einci andeven im Recherchenbeticht ge. te Erfindung kann ,ilcht alt tneu oder auf erflndcrischer TAIlg- hannten V'crdIffntlichung Weclcl werden soil oder die aut eineni keit beitih nd betrachtet wctdeh anderen Y WendrnCrh n.Obn1t(i uscur)V etffeniichun van besonderer Dedeutung; die beannsruch- sdrnbiodrnGub auf cinen nIt dle Ofsfubrung t r Ind n nnnctatafefneice ttgctt '0 Vellffntllcungdie ulend bctrachtct werdcn, wenn die Verliffentlichunt mit cine HeM11Mun, tine Ausstclling oder andere MaIlnahmen cie oder nenrerco anderen Vertlffentlichungcn diestr Kate- bezicht gorle In Verbindlung gebrachl wIrd uhd dierte VcrhindunR illr Vertiffentlichung,. die vor leni In;rnationalcn Ahhmeidcda- einch i'ahmann nhtiliegend it ton,, aber nach dim lirnonprucittin rioritidalum vernffeht- 'A Verliffeniichung, die Nlitglcd derselhen I'atcntfaniille it lictit worden Ist IV. flEsCiiEi.SN(;U iDaturn des Absclolssrs der lnternatinsin Rcchtrche Absondedaturn dmr Ittnatinhalen Recherchenberichts
28.OKTOBER 1991 25. 11. 91 Interniationale Rechorchonhichdrde tlnterschtift des hevnlim~chtlitlen nedlinsteten EF)ROrAISCIIFES PATIENTAMIT BESLIER L.M. 'rmbiall N.IlSA/21 tO al tti1t omw, 19AS) Inerla~oaI Atezechn PCT/EP 91/01494
111. EINSCIILAGIGE VEROFnN1IUaIUNGEN (rortseizang von Blatt 2) Anr0 Kennzelchnung der Veriffu;q-,.Lung, soweft erforderlich unter Angibe der ma0geblichan-Tele Detr. .Anspnach N7. Y SYNTHESIS. 1-8 Nr. 7, 1.989, STUTTGART DE Seiten 547 548; SOROKA 'comments on the synthesli of ami nomethyl phosphonic' siehe das ganze Dokument Foqubtil PCTIISA/2 10 (Zesezbetoi) 4Jauuu 1905P K, ANHANG ZUM INTERNATIONALEN RECHERCHENBERICHT OBER DIE INTERNATIONALE PATENTANMELDUNG NR. EP 9101494 SA 50041 In diesein Anhang sind die Milglieder der ratentfamilien dcr im ohengenannten internationalen Recherchcnbericht angerdhrten Patentdokumente angegeben. Die Angaben Obher die Faniilienniitglieder entsprechen dem Stand der Datei des Europilischen Patentamts am Diese Angaben dienen flu! zur Unterrichtung und erfolgen ohne Gewihr. 28/10/91 Im Recherchenbericbt Datum der' MitgIied(er) der Datum der' angeffihrtes Patientdokument T Vcruiflcntlichung FPatentfamilie T Verfiffentlichung OE-A-3824961 25-01-90 Keine EP-A-0370992 30-05-90 AU-A- 4552389 31-05-90 CA-A- 2003852 25-05-90 US-A- 5041627 20-08-91 A F~r nihere F~nzelheiten zu diesem Anhung :siehe Amtsblatt des Europisehen Patentamnts, Nr.12/82 k r
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4026027 | 1990-08-17 | ||
| DE4026027A DE4026027A1 (en) | 1990-08-17 | 1990-08-17 | METHOD FOR PRODUCING AMINOMETHANEPHOSPHONIC ACID AND AMINOMETHYL PHOSPHINIC ACIDS |
| PCT/EP1991/001494 WO1992003449A1 (en) | 1990-08-17 | 1991-08-07 | Process for producing aminomethanephosphonic acid and aminomethylphosphinic acids |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU8309591A AU8309591A (en) | 1992-03-17 |
| AU653954B2 true AU653954B2 (en) | 1994-10-20 |
Family
ID=6412399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU83095/91A Ceased AU653954B2 (en) | 1990-08-17 | 1991-08-07 | Process for producing aminomethanephosphonic acid and aminomethylphosphinic acids |
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. |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU616818B2 (en) * | 1988-11-25 | 1991-11-07 | Monsanto Company | Preparation of n-acyl-aminomethylphosphonates |
Family Cites Families (1)
| 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 |
-
1990
- 1990-08-17 DE DE4026027A patent/DE4026027A1/en not_active Withdrawn
-
1991
- 1991-08-07 DK DK91914121.8T patent/DK0543845T3/en active
- 1991-08-07 WO PCT/EP1991/001494 patent/WO1992003449A1/en active IP Right Grant
- 1991-08-07 EP EP91914121A patent/EP0543845B1/en not_active Expired - Lifetime
- 1991-08-07 BR BR919106767A patent/BR9106767A/en not_active Application Discontinuation
- 1991-08-07 HU HU9300423A patent/HU213457B/en unknown
- 1991-08-07 CA CA002089650A patent/CA2089650C/en not_active Expired - Fee Related
- 1991-08-07 AT AT91914121T patent/ATE118008T1/en not_active IP Right Cessation
- 1991-08-07 DE DE59104516T patent/DE59104516D1/en not_active Expired - Fee Related
- 1991-08-07 AU AU83095/91A patent/AU653954B2/en not_active Ceased
- 1991-08-07 ES ES91914121T patent/ES2069901T3/en not_active Expired - Lifetime
- 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 IE IE292091A patent/IE912920A1/en unknown
- 1991-08-16 ZA ZA916502A patent/ZA916502B/en unknown
- 1991-08-16 CN CN91105718A patent/CN1028996C/en not_active Expired - Fee Related
- 1991-08-16 PT PT98700A patent/PT98700B/en not_active IP Right Cessation
-
1993
- 1993-02-16 KR KR1019930700446A patent/KR100214903B1/en not_active IP Right Cessation
-
1995
- 1995-03-10 GR GR950400515T patent/GR3015357T3/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU616818B2 (en) * | 1988-11-25 | 1991-11-07 | Monsanto Company | Preparation of n-acyl-aminomethylphosphonates |
Also Published As
| Publication number | Publication date |
|---|---|
| GR3015357T3 (en) | 1995-06-30 |
| EP0543845A1 (en) | 1993-06-02 |
| EP0543845B1 (en) | 1995-02-01 |
| ZA916502B (en) | 1992-04-29 |
| JP3111076B2 (en) | 2000-11-20 |
| HU9300423D0 (en) | 1993-05-28 |
| DE59104516D1 (en) | 1995-03-16 |
| DE4026027A1 (en) | 1992-02-20 |
| ES2069901T3 (en) | 1995-05-16 |
| PT98700B (en) | 1999-01-29 |
| AU8309591A (en) | 1992-03-17 |
| BR9106767A (en) | 1993-08-24 |
| CA2089650A1 (en) | 1992-02-18 |
| HU213457B (en) | 1997-06-30 |
| WO1992003449A1 (en) | 1992-03-05 |
| CA2089650C (en) | 2001-10-23 |
| DK0543845T3 (en) | 1995-06-19 |
| IL99203A (en) | 1995-08-31 |
| PT98700A (en) | 1992-07-31 |
| JPH06500310A (en) | 1994-01-13 |
| IL99203A0 (en) | 1992-07-15 |
| HUT64355A (en) | 1993-12-28 |
| ATE118008T1 (en) | 1995-02-15 |
| CN1059148A (en) | 1992-03-04 |
| CN1028996C (en) | 1995-06-21 |
| IE912920A1 (en) | 1992-02-26 |
| KR100214903B1 (en) | 1999-08-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MK14 | Patent ceased section 143(a) (annual fees not paid) or expired |