DD232050A5 - PROCESS FOR PREPARING PHOSPHONIC ACID DIESES - Google Patents
PROCESS FOR PREPARING PHOSPHONIC ACID DIESES Download PDFInfo
- Publication number
- DD232050A5 DD232050A5 DD85273479A DD27347985A DD232050A5 DD 232050 A5 DD232050 A5 DD 232050A5 DD 85273479 A DD85273479 A DD 85273479A DD 27347985 A DD27347985 A DD 27347985A DD 232050 A5 DD232050 A5 DD 232050A5
- Authority
- DD
- German Democratic Republic
- Prior art keywords
- group
- formula
- phosphonic acid
- carbon atoms
- reaction
- Prior art date
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- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 title description 3
- 238000004519 manufacturing process Methods 0.000 title 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- -1 Phosphonic acid diesters Chemical class 0.000 claims abstract description 6
- 150000003008 phosphonic acid esters Chemical class 0.000 claims abstract description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 125000000547 substituted alkyl group Chemical group 0.000 claims 1
- 238000007327 hydrogenolysis reaction Methods 0.000 abstract description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 7
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- 239000008098 formaldehyde solution Substances 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- KGSVNOLLROCJQM-UHFFFAOYSA-N 2-(benzylamino)acetic acid Chemical compound OC(=O)CNCC1=CC=CC=C1 KGSVNOLLROCJQM-UHFFFAOYSA-N 0.000 description 3
- 108010049175 N-substituted Glycines Proteins 0.000 description 3
- 238000003776 cleavage reaction Methods 0.000 description 3
- 238000006264 debenzylation reaction Methods 0.000 description 3
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000007017 scission Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- ULOLIZHBYWAICY-UHFFFAOYSA-N ethyl 2-(benzylamino)acetate Chemical compound CCOC(=O)CNCC1=CC=CC=C1 ULOLIZHBYWAICY-UHFFFAOYSA-N 0.000 description 2
- 150000002332 glycine derivatives Chemical class 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- JZUFKLXOESDKRF-UHFFFAOYSA-N Chlorothiazide Chemical class C1=C(Cl)C(S(=O)(=O)N)=CC2=C1NCNS2(=O)=O JZUFKLXOESDKRF-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- NTNZTEQNFHNYBC-UHFFFAOYSA-N ethyl 2-aminoacetate Chemical compound CCOC(=O)CN NTNZTEQNFHNYBC-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- NXJCBFBQEVOTOW-UHFFFAOYSA-L palladium(2+);dihydroxide Chemical compound O[Pd]O NXJCBFBQEVOTOW-UHFFFAOYSA-L 0.000 description 1
- IMACFCSSMIZSPP-UHFFFAOYSA-N phenacyl chloride Chemical compound ClCC(=O)C1=CC=CC=C1 IMACFCSSMIZSPP-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003491 tear gas Substances 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/44—Amides thereof
-
- 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
- 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
- A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
-
- 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
- A01N57/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing aromatic radicals
-
- 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)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Environmental Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Dentistry (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Titel der Erfindung:Title of the invention:
Verfahren zur Herstellung von Phosphonsäure-diestern Anwendungsgebiet der Erfindung:Process for the preparation of phosphonic acid diesters Field of application of the invention:
Die Erfindung betrifft ein Verfahren zur Herstellung von N-substiuierten Phosphonsäureestern der Familie des N-Phosphonomethylglycins, die für die Synthese von Herbiziden brauchbar sind.The invention relates to a process for the preparation of N-substituted phosphonic acid esters of the family of N-phosphonomethylglycine, which are useful for the synthesis of herbicides.
Charakterisitk der bekannten technischen Lösungen:Characteristic of the known technical solutions:
Bekannt sind zahlreiche herbizid wirksame Verbindungen aus der Familie des N-Phosphonomethylglycins (US-PSenNumerous herbicidally active compounds from the family of N-phosphonomethylglycine (US Pat
3 455 675, 4 388 103 und 4 397 676; FR-PS 2 129 327; EP-A 53 871, 54 382 und 73 574; PCT WO 83/03608, GB-PS 2 090 596, BE-PSen 894 244, 894 245, 894 590, 894 591, 894 592, 894 593, 894 594 und 894 595). 203,455,675, 4,388,103 and 4,397,676; FR-PS 2 129 327; EP-A 53 871, 54 382 and 73 574; PCT WO 83/03608, GB 2,090,596, BEs 894,244, 894,245, 894,590, 894,591, 894,592, 894,593, 894,594 and 894,595). 20
Beschrieben wurde auch bereits die Bildung von Triestern des N-Phosphonomethylglycins durch Umsetzung von Ethylglycinat mit Formaldehyd und Diethylphosphit (FR-PS 2 129 327) Dieses Verfahren befriedigt aber nicht, weil die Bildung von Ν,Ν-Bis(phosphonomethyl)glycin begünstigt wird. Deshalb wird gemäß einem anderen Verfahren N-Phosphonome-The formation of triesters of N-phosphonomethylglycine by reacting ethylglycinate with formaldehyde and diethylphosphite has also been described (FR-PS 2 129 327). However, this process is unsatisfactory because the formation of .alpha.,. Bis-bis (phosphonomethyl) glycine is favored. Therefore, according to another method, N-phosphonome
/2/ 2
thylglycin durch Umsetzung eines N-Arylalkylglycins mit Formaldehyd und Phosphoriger Säure und anschließender Umsetzung der N-Arylalkylgruppe durch Einwirkung von Bromwasserstoff- oder Iodwasserstoffsäure hergestellt (FR-PS 2 193 830). Aber auch dieses Verfahren befriedigt nicht wegen der erzielten niedrigen Ausbeuten und wegen der Entstehung von Benzylbromid, das als Tränengas wirkt. Es wurde deshalb weiterhin versucht, N-Phosphonomethylglycin durch Umsetzung von N-substituiertem Glycin mit Formaldehyd und Phosphoriger Säure und anschließender hydrierender Spaltung des erhaltenen N,N-disubstituierten N-Phosphonomethylglycins herzustellen. Nachteilig an diesem Verfahren ist, daß in stark verdünntem Medium gearbeitet werdem muß und daß es sehr lange dauert. In jüngster Zeit schließlich hat man sich anderen Reaktionspartnern zugewandt und Aminomethylphosphonsäure mit Glyoxal in Gegenwart von SO2 umgesetzt (EP-A 81 459).thylglycine by reaction of an N-arylalkylglycine with formaldehyde and phosphorous acid and subsequent reaction of the N-arylalkyl group by the action of hydrobromic or hydroiodic acid produced (FR-PS 2,193,830). But even this method is not satisfactory because of the low yields achieved and because of the formation of benzyl bromide, which acts as tear gas. It was therefore further attempted to prepare N-phosphonomethylglycine by reacting N-substituted glycine with formaldehyde and phosphorous acid and then hydrogenating cleavage of the resulting N, N-disubstituted N-phosphonomethylglycine. A disadvantage of this method is that you have to work in very dilute medium and that it takes a very long time. Recently, finally, it has turned to other reactants and aminomethylphosphonic reacted with glyoxal in the presence of SO 2 (EP-A 81 459).
Ziel der Erfindung:Object of the invention:
Ziel der Erfindung ist die Bereitstellung eines sehr einfachen und verbesserten Verfahrens zur Herstellung von herbizid wirksamen Verbindungen unter Einsatz von einfachen Reaktionspartnern, vor allem von Glycin und seinen einfachen Derivaten. *The aim of the invention is to provide a very simple and improved process for the preparation of herbicidally active compounds using simple reactants, especially glycine and its simple derivatives. *
Darlegung des Wesens der Erfindung:Explanation of the essence of the invention:
Es wurde nun gefunden, und dies ist Gegenstand der Erfindung, daß man neue N-Phosphonomethylglycinverbindungen, ausgehend von Derivaten des N-substituierten Glycins und Formaldehyd herstellen kann, die ihrerseits den Zugang zu herbizid wirksamen Verbindungen eröffnen.It has now been found, and this is the subject of the invention, that it is possible to prepare novel N-phosphonomethylglycine compounds starting from derivatives of N-substituted glycine and formaldehyde, which in turn open up access to herbicidally active compounds.
Die Erfindung betrifft somit ein Verfahren zur Herstellung von Phosphonsäurediestern der FormelThe invention thus relates to a process for the preparation of phosphonic diesters of the formula
/3/ 3
OR1 R .OR 1 R.
I II i
O = P- CH2 - N - CH2 - CO - OH (I)O = P-CH 2 - N - CH 2 - CO - OH (I)
in derin the
R eine durch Wasserstoff abspaltbare Gruppe, vorzugsweise eine Arylalkylgruppe und R eine hydrolysierbare Gruppe bedeutet. 10R is a hydrogen-releasable group, preferably an arylalkyl group and R is a hydrolyzable group. 10
Die Gruppe R kann im einzelnen eine Gruppe der FormelThe group R can in detail be a group of the formula
R4 R 4
Ar-C- (II)Ar-C- (II)
A'A '
sein, in derbe in the
Ar eine aromatische Gruppe, vorzugsweise eine Arylgruppe und insbesondere eine Phenylgruppe ist. Diese Gruppe Ar· kann gegebenenfalls einen oder mehrere Substituenten aufweisen, die die während des Verfahrens ablaufenden Reaktionen nicht beeinträchtigen (Alkyl-, Alkoxy-, Nitrogruppen und andere, wobei die Anzahl Kohlenstoffatome vorzugsweise höchstens 6 beträgt), jedoch ergibt sich kein besonderer Vorteil aus der Verwendung derartiger Substituenten.Ar is an aromatic group, preferably an aryl group and especially a phenyl group. This group Ar may optionally have one or more substituents which do not interfere with the reactions occurring during the process (alkyl, alkoxy, nitro groups and others, the number of carbon atoms being preferably at most 6), but no particular advantage arises from US Pat Use of such substituents.
3 4 R und R bedeuten jeweils ein Wasserstoffatom oder eine Ar-Gruppe oder eine Alkylgruppe mit vorzugsweise höchstens 6 Kohlenstoffatomen.R 4 and R 4 each represent a hydrogen atom or an Ar group or an alkyl group having preferably at most 6 carbon atoms.
Beispiele für die Gruppen R sind die Benzyl-, !-Phenylethyl-, 1-Pheny]propyl-, Naphthylmethyl-, 1-Naphthylethyl-, 1-Naphthylpropyl-, Diphenylmethyl- und Trityl- (= Triphenylmethyl-) Gruppen und die Benzylgruppe wird bevorzugt.Examples of the groups R are the benzyl,! -Phenylethyl, 1-phenyl] propyl, naphthylmethyl, 1-naphthylethyl, 1-naphthylpropyl, diphenylmethyl and trityl (= triphenylmethyl) groups and the benzyl group prefers.
/4/ 4
R ist eine hydrolysierbare Gruppe. Beispiele für derartige hydrolysierbare Gruppen sind die gegebenenfalls substituierten Kohlenwasserstoffgruppen, vor allem die Alkyl- oder Phenylgruppen, gegebenenfalls substituiert mit Halogenatomen oder mit Phenyl-, Cyano-, Alkoxy- und/oder Alkoxycarbonylgruppen. R enthält allgemein höchstens 12 Kohlenstoffatome und ist vorteilhafterweise eine Alkylgruppe mit 1 bis 6 Kohlenstoffatomen oder die PhenylgruppeR is a hydrolyzable group. Examples of such hydrolyzable groups are the optionally substituted hydrocarbon groups, especially the alkyl or phenyl groups, optionally substituted by halogen atoms or by phenyl, cyano, alkoxy and / or alkoxycarbonyl groups. R generally contains at most 12 carbon atoms and is advantageously an alkyl group of 1 to 6 carbon atoms or the phenyl group
10 10
Beim Verfahren zur Herstellung der Verbindungen der Formel (I) wird ein Phosphit oder Phosphonsaureester der FormelIn the process for the preparation of the compounds of formula (I) is a phosphite or phosphonic acid ester of the formula
0-R1 0-R 1
II
O=P-H (III)O = P-H (III)
in der R wie oben definiert ist, mit Formaldehyd und einem N-substituierten Derivat von Glycin umgesetzt, wo-0 bei der an das Stickstoffatom gebundene Substituent ein mit Wasserstoff abspaltbarer Substituent ist. Das N-substituierte Glycinderivat ist in der Praxis eine Verbindung der Formel R-NH- CH- - CO - OH.in which R is as defined above, reacted with formaldehyde and an N-substituted derivative of glycine, where -O in the substituent attached to the nitrogen atom is a hydrogen-releasable substituent. The N-substituted glycine derivative is in practice a compound of the formula R-NH-CH- - CO - OH.
Die Umsetzung erfolgt allgemein bei einer Temperatur von 0 bis 1000C, vorzugsweise von 10 bis 900C durch einfaches Vermischen der Reaktionspartner. Zwar können die Reaktionspartner im Verhältnis zueinander in großem Überschuß (Molverhältnisse 3 : 1 bis 1 : 3) eingesetzt werden; vorteilhafter ist es jedoch, in der Praxis dem stöchiometrischen Verhältnis so nahe wie möglich zu kommen und um nicht mehr als 20 mol-% von diesem stöchiometrischen Verhältnis abzuweichen. Darin liegt sogar einer der wichtigen Vorteile des erfindungsgemäßen Verfahrens, daß die Reaktionspartner nicht im Überschuß über die jeweiligThe reaction is generally carried out at a temperature of 0 to 100 0 C, preferably from 10 to 90 0 C by simply mixing the reactants. Although the reactants in relation to each other in large excess (molar ratios 3: 1 to 1: 3) can be used; however, in practice it is more advantageous to come as close as possible to the stoichiometric ratio and not deviate from this stoichiometric ratio by more than 20 mol%. This is even one of the important advantages of the process according to the invention that the reactants are not in excess of the respective
/5/ 5
anderen Reaktionspartner eingesetzt werden müssen. Ein weiterer Vorteil des erfindungsgemäßen Verfahrens sind die guten Ausbeuten, die bei der Herstellung der neuen Verbindungen erzielt werdenmust be used other reactants. Another advantage of the process according to the invention is the good yields which are achieved in the preparation of the new compounds
5 5
Der Formaldehyd wird in einer der bequem zugänglichen Formen eingesetzt. Die gebräuchlichste Form ist die Verwen dung einer wäßrigen Formaldehydlösung mit einer Konzentration von 1 % bis zur Sättigung, vorzugsweise von 30 bis 40 %.The formaldehyde is used in one of the conveniently accessible forms. The most common form is the use of an aqueous formaldehyde solution at a concentration of 1% to saturation, preferably from 30 to 40%.
Die Umsetzung kann in Gegenwart eines inerten Lösungsmittels vorgenommen werden. Manchmal ist ein derartiges Lösungsmittel unnütz, aber das Reaktionsmedium enthält üblicherweise Wasser, vor allem wegen des Einsatzes von Formaldehyd in Form der wäßrigen Lösung.The reaction can be carried out in the presence of an inert solvent. Sometimes such a solvent is useless, but the reaction medium usually contains water, mainly because of the use of formaldehyde in the form of the aqueous solution.
Das Reaktionsprodukt kann mit Hilfe aller an sich bekannten Methoden isoliert werdenThe reaction product can be isolated by all methods known per se
20 20
Die Verbindungen der Formel (I) können in bekannte herbi zide Verbindungen der FormelThe compounds of the formula (I) can be converted into known herbi zide compounds of the formula
OR1 OR 1
O=P- CH2 - NH - CH2 - CO - OH (IV)O = P-CH 2 -NH-CH 2 -CO-OH (IV)
überführt werden, durch einfache Abspaltung der Gruppe R mit Wasserstoff. Dies ist meistens eine Debenzylierung.be converted by simple cleavage of the group R with hydrogen. This is usually a debenzylation.
Diese Debenzylierung wird vorteilhafterweise in wäßrigem oder alkoholischem Medium bei Raumtemperatur oder erhöhter Temperatur sowie erhöhtem Druck oder bei Atmosphärendruck vorgenommen. Die üblichen Katalysatoren für die hydrierende Abspaltung der in Frage kommenden Reste R können hierbei eingesetzt werden. Geeignete Katalysatoren sind Palladium, Platin und Raney-Nickel. Diese Katalysatoren können mit oder ohne inerten Träger VerwendungThis Debenzylierung is advantageously carried out in aqueous or alcoholic medium at room temperature or elevated temperature and elevated pressure or at atmospheric pressure. The usual catalysts for the hydrogenative cleavage of the radicals R in question can be used here. Suitable catalysts are palladium, platinum and Raney nickel. These catalysts can be used with or without inert carrier
finden. Man-kann auch die genannten Metalle, vor allem Palladium und Platin in Form von Salzen, Hydroxiden oder Oxiden verwenden, die unter der Einwirkung des Wasserstoffs in das entsprechende Metall überführt werden. Die Katalysatoren auf Basis von Palladium wie Palladium auf Aktivkohle oder Palladium auf Bariumsulfat oder Palladiumhydroxid auf Aktivkohle werden als Katalysatoren für die Debenzylierung bevorzugt. Nach beendeter Reaktion kann der Katalysator abfiltriert und das Filtrat eingedampft werden. Hierdurch erhält man die Verbindung der Formel (IV) in praktisch reinem Zustand. Ein wichtiger Vorteil liegt darin, daß die Reaktionszeit für diese Debenzylierung relativ kurz ist, weshalb geringe Mengen an Katalysator verwendet werden können.Find. It is also possible to use the said metals, above all palladium and platinum, in the form of salts, hydroxides or oxides, which are converted into the corresponding metal under the action of hydrogen. The catalysts based on palladium such as palladium on activated carbon or palladium on barium sulfate or palladium hydroxide on activated carbon are preferred as catalysts for the debenzylation. After completion of the reaction, the catalyst can be filtered off and the filtrate are evaporated. This gives the compound of formula (IV) in a substantially pure state. An important advantage is that the reaction time for this debenzylation is relatively short, which is why small amounts of catalyst can be used.
.,
Wenn bekannte, nicht veresterte herbizid wirksame Verbindungen angestrebt werden,wie das N-Phosphonomethylglycin selbst, kann die Verbindung der Formel (IV) in an sich bekannter Weise vollständig oder teilweise hydrolysiert werden, beispielsweise durch Erhitzen mit einer- Lösung eines sauren oder alkalischen Mittels, insbesondere eines Hydroxids oder Carbonats eines Alkali- oder Erdalkalimetalls oder einer Säure wie Chlorwasserstoff säure (Salzsäure), Schwefelsäure, Phosphonsäure, Perchlorsäure oder einer Arylsulfonsäure. Diese Hydrolyse kann auch von einer Salzbildung oder einerUmwandlung in andere herbizid wirksame Verbindungen begleitet sein. Auf die Hydrogenolyse nach der Erfindung kann somit eine Hydrolyse und/oder die Überführung in ein Salz folgenIf known non-esterified herbicidally active compounds are desired, such as the N-phosphonomethylglycine itself, the compound of the formula (IV) can be completely or partially hydrolyzed in a manner known per se, for example by heating with a solution of an acidic or alkaline agent, in particular a hydroxide or carbonate of an alkali or alkaline earth metal or an acid such as hydrochloric acid (hydrochloric acid), sulfuric acid, phosphonic acid, perchloric acid or an arylsulfonic acid. This hydrolysis may also be accompanied by salt formation or conversion to other herbicidally active compounds. The hydrogenolysis according to the invention can thus be followed by hydrolysis and / or conversion into a salt
30 30
Ausführungsbeispiele:EXAMPLES
Es wurden 39 g N-Benzylglycin, 80 ml Wasser und 20,3 ml wäßrige Formaldehydlösung entsprechend 0,248 mol Formaldehyd miteinander vermischt. Dann wurden bei Raumtempera-39 g of N-benzylglycine, 80 ml of water and 20.3 ml of aqueous formaldehyde solution corresponding to 0.248 mol of formaldehyde were mixed together. Then at room temperature
/7/ 7
tür 58 g (0,248 mol) Dxphenylphosphit (C6H5O)2PH(O) zugetropft. Nach 30 min ließ man die Temperatur auf 300C ansteigen und rührte noch eine Stunde. Dann wurde filtriert, mit Wasser gewaschen und getrocknet. Nach Umkristallisation aus einem Gemisch aus Isopropylether und Isopropanol in einem Vol.-Verhältnis von 10:1 erhielt man 57,4 g eines weißen Pulvers, das bei 910C schmolz (Ausbeute 59,1 %) und aus der Verbindung der Formel58 g (0.248 mol) of Dxphenylphosphit (C 6 H 5 O) 2 PH (O) was added dropwise. After 30 minutes, the temperature was allowed to rise to 30 0 C and stirred for an hour. It was then filtered, washed with water and dried. Recrystallization from a mixture of isopropyl ether and isopropanol in a vol. Ratio of 10: 1 gave 57.4 g of a white powder, which melted at 91 0 C (yield 59.1%) and from the compound of formula
C .,H1-O CH0-C^HC, H 1 -O CH 0 -CH
65| j 2 6 5 65 | j 2 6 5
0 = P - CH„ -N - CH0 - COOH0 = P - CH "-N - CH 0 - COOH
I 2 2 (V)I 2 2 (V)
C6H5OC 6 H 5 O
bestand.duration.
16,5 g N-Benzylglycin, 28 ml Wasser und 13,8 g Diethylphosphit (C7H1-O)5PH(O) wurden miteinander vermischt. Dann wurden bei 200C 9 ml einer wäßrigen, 37 %igen Formaldehydlösung (0,11 mol) zugegeben. Man beobachtete keinerlei exotherme Reaktion. Dann wurde 5 h auf 500C erwärmt, anschließend abgekühlt und mit 40 ml CH„C1_ versetzt. Die organische Phase wurde abgetrennt; dann wurden 40 ml Wasser und anschließend 100 ml wäßrige In Natronlauge 5 zugegeben. Die wäßrige Phase wurde abdekantiert, mit CH-Cl7 extrahiert und angesäuert. Die organische Phase wurde getrocknet und eingedampft. Man erhielt 23,5 g (Ausbeute 7 4 %) Verbindung der Formel16.5 g of N-benzylglycine, 28 ml of water and 13.8 g of diethyl phosphite (C 7 H 1 -O) 5 PH (O) were mixed together. Then, at 20 ° C., 9 ml of an aqueous 37% formaldehyde solution (0.11 mol) was added. No exothermic reaction was observed. Then for 5 hours, at 50 0 C is heated, then cooled and treated with 40 ml CH "C1_. The organic phase was separated; then 40 ml of water and then 100 ml of aqueous sodium hydroxide 5 were added. The aqueous phase was decanted off, extracted with CH-Cl 7 and acidified. The organic phase was dried and evaporated. This gave 23.5 g (yield 7 4%) of the compound of the formula
C2H5O CH2-C6H5 C 2 H 5 O CH 2 -C 6 H 5
O=P- CH2 N - CH9 - COOHO = P - CH 2 N - CH 9 --COOH
(VI)(VI)
C2H5OC 2 H 5 O
/8/8th
Es wurde eine in situ Verseifung von Ethyl-N-benzylglycinat durchgeführt. Hierzu wurden 0,5 1 wäßrige, 30-%ige NaOH-Lösung (5 mol) und 1 1 Wasser miteinander vermischt und zu dieser Lösung im Verlauf einer Stunde 965 g Ethyl-N-benzylglycinat gegeben. Die Temperatur stieg auf 450C an. Ethanol wurde abdestilliert; dann wurde abgekühlt und 0,82 1 6n Salzsäure zugegeben. N-Benzylglycin fiel aus. Dann wurden 690 g Diethylphosphit sowie 0,45 1 wäßrige, 37 %ige Formaldehydlösung (5 mol) zugegeben und 5 1/2 Stunden auf 500C erwärmt. Dann wurde wie im Beispiel 2 verfahren. Man erhielt 1116g (Ausbeute 71 %) Verbindung der Formel (VI).In situ saponification of ethyl N-benzylglycinate was carried out. For this purpose, 0.5 1 aqueous, 30% NaOH solution (5 mol) and 1 1 of water were mixed together and added to this solution over the course of an hour 965 g of ethyl N-benzylglycinat. The temperature rose to 45 0 C. Ethanol was distilled off; then it was cooled and 0.82 liters of hydrochloric acid were added. N-benzylglycine precipitated. Then 690 g of diethyl phosphite and 0.45 1 aqueous, 37% formaldehyde solution (5 mol) were added and heated to 50 0 C for 5 1/2 hours. Then the procedure was as in Example 2. 1116 g (yield 71%) of compound of the formula (VI) were obtained.
72347234
Claims (7)
R und R die bereits angegebenen Bedeutungen haben.1
R and R have the meanings already given.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8402988A FR2560198B1 (en) | 1984-02-23 | 1984-02-23 | ESTERS OF THE N-PHOSPHONOMETHYLGLYCIN FAMILY AND THEIR USE FOR THE PREPARATION OF KNOWN HERBICIDES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DD232050A5 true DD232050A5 (en) | 1986-01-15 |
Family
ID=9301450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DD85273479A DD232050A5 (en) | 1984-02-23 | 1985-02-22 | PROCESS FOR PREPARING PHOSPHONIC ACID DIESES |
Country Status (22)
| Country | Link |
|---|---|
| EP (1) | EP0153261B1 (en) |
| JP (1) | JPS60193995A (en) |
| KR (1) | KR850007065A (en) |
| AT (1) | ATE40376T1 (en) |
| AU (1) | AU584600B2 (en) |
| BR (1) | BR8500765A (en) |
| CA (1) | CA1256447A (en) |
| DD (1) | DD232050A5 (en) |
| DE (1) | DE3567874D1 (en) |
| DK (1) | DK84185A (en) |
| ES (1) | ES8607975A1 (en) |
| FI (1) | FI75831C (en) |
| FR (1) | FR2560198B1 (en) |
| GB (1) | GB2155476B (en) |
| HU (1) | HU197022B (en) |
| IE (1) | IE850203L (en) |
| IL (1) | IL74169A (en) |
| PL (1) | PL147957B1 (en) |
| PT (1) | PT79998B (en) |
| RO (1) | RO90931B (en) |
| YU (1) | YU45234B (en) |
| ZA (1) | ZA85726B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2560198B1 (en) * | 1984-02-23 | 1987-05-07 | Rhone Poulenc Agrochimie | ESTERS OF THE N-PHOSPHONOMETHYLGLYCIN FAMILY AND THEIR USE FOR THE PREPARATION OF KNOWN HERBICIDES |
| FR2579210B1 (en) * | 1985-03-21 | 1987-09-11 | Rhone Poulenc Agrochimie | PREPARATION OF PHOSPHONATE GROUP HERBICIDES AND INTERMEDIATES FROM BENZOXAZINES |
| DE4326887A1 (en) * | 1993-08-11 | 1995-02-16 | Hoechst Ag | Process for the preparation of N-substituted aminoalkylenephosphonic esters |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1436843A (en) * | 1972-07-21 | 1976-05-26 | Ici Ltd | Preparation of n-phosphonomethyl-glycine |
| RO67869A (en) * | 1972-12-11 | 1981-06-22 | Mensanto Co,Us | PROCESS FOR THE PREPARATION OF N-PHOSPHONOMETHYL GLUCIUM N-OXIDES DERIVATIVES |
| US3835000A (en) * | 1972-12-21 | 1974-09-10 | Monsanto Co | Electrolytic process for producing n-phosphonomethyl glycine |
| HU173170B (en) * | 1974-06-27 | 1979-03-28 | Chinoin Gyogyszer Es Vegyeszet | Process for producing n-phosphonomethyl-glycine |
| DE2860342D1 (en) * | 1977-08-11 | 1981-02-12 | Ciba Geigy Ag | Glycylmethyl-phosphinic acid derivatives, their preparation and their use |
| EP0055695A1 (en) * | 1980-12-30 | 1982-07-07 | Ciba-Geigy Ag | Process for preparing N-phosphonomethyl glycine |
| US4422982A (en) * | 1982-06-30 | 1983-12-27 | Stauffer Chemical Company | Method for preparation of N-phosphonomethylglycine |
| FR2560198B1 (en) * | 1984-02-23 | 1987-05-07 | Rhone Poulenc Agrochimie | ESTERS OF THE N-PHOSPHONOMETHYLGLYCIN FAMILY AND THEIR USE FOR THE PREPARATION OF KNOWN HERBICIDES |
-
1984
- 1984-02-23 FR FR8402988A patent/FR2560198B1/en not_active Expired
-
1985
- 1985-01-25 IL IL74169A patent/IL74169A/en unknown
- 1985-01-29 CA CA000473047A patent/CA1256447A/en not_active Expired
- 1985-01-29 GB GB08502164A patent/GB2155476B/en not_active Expired
- 1985-01-29 IE IE850203A patent/IE850203L/en unknown
- 1985-01-30 ZA ZA85726A patent/ZA85726B/en unknown
- 1985-01-30 AU AU38163/85A patent/AU584600B2/en not_active Ceased
- 1985-02-21 AT AT85420029T patent/ATE40376T1/en active
- 1985-02-21 DE DE8585420029T patent/DE3567874D1/en not_active Expired
- 1985-02-21 KR KR1019850001078A patent/KR850007065A/en not_active Application Discontinuation
- 1985-02-21 JP JP60033630A patent/JPS60193995A/en active Pending
- 1985-02-21 PT PT79998A patent/PT79998B/en not_active IP Right Cessation
- 1985-02-21 EP EP85420029A patent/EP0153261B1/en not_active Expired
- 1985-02-21 PL PL1985252061A patent/PL147957B1/en unknown
- 1985-02-21 BR BR8500765A patent/BR8500765A/en unknown
- 1985-02-22 DK DK84185A patent/DK84185A/en not_active Application Discontinuation
- 1985-02-22 ES ES540626A patent/ES8607975A1/en not_active Expired
- 1985-02-22 DD DD85273479A patent/DD232050A5/en unknown
- 1985-02-22 YU YU273/85A patent/YU45234B/en unknown
- 1985-02-22 FI FI850733A patent/FI75831C/en not_active IP Right Cessation
- 1985-02-22 HU HU85673A patent/HU197022B/en not_active IP Right Cessation
- 1985-02-23 RO RO117743A patent/RO90931B/en unknown
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