SE441451B - O-ARYL-N-PHOSPHONOMETHYLGYCINONITRIL FOR USE AS HERBICID, HERBICIDIC COMPOSITION AND HERBICIDIC PROCEDURE - Google Patents
O-ARYL-N-PHOSPHONOMETHYLGYCINONITRIL FOR USE AS HERBICID, HERBICIDIC COMPOSITION AND HERBICIDIC PROCEDUREInfo
- Publication number
- SE441451B SE441451B SE7713047A SE7713047A SE441451B SE 441451 B SE441451 B SE 441451B SE 7713047 A SE7713047 A SE 7713047A SE 7713047 A SE7713047 A SE 7713047A SE 441451 B SE441451 B SE 441451B
- Authority
- SE
- Sweden
- Prior art keywords
- phosphonomethylglycinonitrile
- mol
- solution
- acid
- solid
- Prior art date
Links
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- 125000003118 aryl group Chemical group 0.000 claims description 9
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- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
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- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 4
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- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
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- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
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- 150000007860 aryl ester derivatives Chemical group 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- FXCLIEYDXXVEAI-UHFFFAOYSA-N benzene;dichloromethane Chemical compound ClCCl.C1=CC=CC=C1 FXCLIEYDXXVEAI-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QEASXYHBCOBLEU-UHFFFAOYSA-N bis(2,4,6-trimethylphenyl) hydrogen phosphite Chemical compound CC1=CC(C)=CC(C)=C1OP(O)OC1=C(C)C=C(C)C=C1C QEASXYHBCOBLEU-UHFFFAOYSA-N 0.000 description 1
- XAEQVLOIPHAOOW-UHFFFAOYSA-N bis(2-chlorophenyl) hydrogen phosphite Chemical compound C=1C=CC=C(Cl)C=1OP(O)OC1=CC=CC=C1Cl XAEQVLOIPHAOOW-UHFFFAOYSA-N 0.000 description 1
- ZUAGNRHSAPEJRW-UHFFFAOYSA-N bis(2-methoxyphenyl) hydrogen phosphite Chemical compound COC1=CC=CC=C1OP(O)OC1=CC=CC=C1OC ZUAGNRHSAPEJRW-UHFFFAOYSA-N 0.000 description 1
- PDPQEMNLXUGHNS-UHFFFAOYSA-N bis(3,4-dichlorophenyl) hydrogen phosphite Chemical compound C=1C=C(Cl)C(Cl)=CC=1OP(O)OC1=CC=C(Cl)C(Cl)=C1 PDPQEMNLXUGHNS-UHFFFAOYSA-N 0.000 description 1
- VZOSMKZCDPKGHW-UHFFFAOYSA-N bis(3-methylphenyl) hydrogen phosphite Chemical compound CC1=CC=CC(OP(O)OC=2C=C(C)C=CC=2)=C1 VZOSMKZCDPKGHW-UHFFFAOYSA-N 0.000 description 1
- ZJRNBGVJGIFZRO-UHFFFAOYSA-N bis(3-nitrophenyl) hydrogen phosphite Chemical compound C=1C=CC([N+]([O-])=O)=CC=1OP(O)OC1=CC=CC([N+]([O-])=O)=C1 ZJRNBGVJGIFZRO-UHFFFAOYSA-N 0.000 description 1
- ZOLLZXLIZDRUPF-UHFFFAOYSA-N bis(4-chlorophenyl) hydrogen phosphite Chemical compound C=1C=C(Cl)C=CC=1OP(O)OC1=CC=C(Cl)C=C1 ZOLLZXLIZDRUPF-UHFFFAOYSA-N 0.000 description 1
- MWZWOLDTGUGECQ-UHFFFAOYSA-N bis(4-methoxyphenyl) hydrogen phosphite Chemical compound C1=CC(OC)=CC=C1OP(O)OC1=CC=C(OC)C=C1 MWZWOLDTGUGECQ-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003940 butylamines Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca+2].OP(O)(O)=O.OP(O)(O)=O YYRMJZQKEFZXMX-UHFFFAOYSA-N 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- WORJEOGGNQDSOE-UHFFFAOYSA-N chloroform;methanol Chemical compound OC.ClC(Cl)Cl WORJEOGGNQDSOE-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- LNZMEOLVTKHUAS-UHFFFAOYSA-N cyclohexane;dichloromethane Chemical compound ClCCl.C1CCCCC1 LNZMEOLVTKHUAS-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- JNXDHIIQYKMEDV-UHFFFAOYSA-N dinaphthalen-2-yl hydrogen phosphite Chemical compound C1=CC=CC2=CC(OP(OC=3C=C4C=CC=CC4=CC=3)O)=CC=C21 JNXDHIIQYKMEDV-UHFFFAOYSA-N 0.000 description 1
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- PSLIMVZEAPALCD-UHFFFAOYSA-N ethanol;ethoxyethane Chemical compound CCO.CCOCC PSLIMVZEAPALCD-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000019713 millet Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- XYQQPUALUKWVRH-UHFFFAOYSA-N phenoxy(phenylsulfanyl)phosphinous acid Chemical compound P(SC1=CC=CC=C1)(OC1=CC=CC=C1)O XYQQPUALUKWVRH-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000002426 superphosphate Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical class C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- ZFXYFBGIUFBOJW-UHFFFAOYSA-N theophylline Chemical compound O=C1N(C)C(=O)N(C)C2=C1NC=N2 ZFXYFBGIUFBOJW-UHFFFAOYSA-N 0.000 description 1
- 229960000278 theophylline Drugs 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- NWEPJDPAVFDLBY-UHFFFAOYSA-N trichloromethylphosphonic acid Chemical compound OP(O)(=O)C(Cl)(Cl)Cl NWEPJDPAVFDLBY-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 230000009105 vegetative growth Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—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
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4084—Esters with hydroxyaryl compounds
-
- 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
-
- 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
-
- 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
- A01N57/24—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing heterocyclic 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)]
- C07F9/3804—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
-
- 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
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Molecular Biology (AREA)
- Agronomy & Crop Science (AREA)
- Biochemistry (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Cosmetics (AREA)
Description
7713047-4 2 endast med en diester. När en stark syra sätts till en monoester (se formeln IV nedan), kan den enda arylestergruppen hydrolyseras från molekylen. 7713047-4 2 only with a diester. When a strong acid is added to a monoester (see formula IV below), the single aryl ester group can be hydrolyzed from the molecule.
De N-fosfonometylglycinonitriler med formeln I, där x och b är 0, framställs genom att man bildar en blandning, som väsentligen består av en fosforsyraester med formeln Z (aryl X a-O)2 ë-H (ll) där X, Z och a har den ovan angivna definitionen, och l,3,5-tricyanometylhexa- hydro-l,3,5-triazin (även kallad N-metylenglycinonitriltrimer) med formeln (EHZCN f N\ CHZ U çHZ , I un) 2 \ /N-CHZCN Clíz och upphettar blandningen till en tillräckligt förhöjd temperatur för att initiera reaktionen och upprätthåller en tillräcklig temperatur för att underhålla _ reaktionen mellan fosforsyraestern och triazinen för framställning av N-fos- fonometylglycinonitrilen I. Även om ett lösningsmedel inte är nödvändigt vid förfarandet enligt uppfinningen, är det ibland önskvärt att använda ett lösningsmedel av enkelhets- skäl och för att underlätta reaktionen. Ett lösningsmedel är även användbart för att reglera reaktionstemperaturen. Det använda lösningsmedlet är ett sådant i vilket triazinen är löslig och som inte reagerar med någon av reaktanterna.The N-phosphonomethylglycinonitriles of formula I, where x and b are 0, are prepared by forming a mixture consisting essentially of a phosphoric acid ester of formula Z (aryl X aO) 2 ë-H (II) where X, Z and a has the above definition, and 1,3,5-tricyanomethylhexahydro-1,3,5-triazine (also called N-methylene glycinonitrile trimer) of the formula (EHZCN f N \ CHZ U çHZ, I un) 2 CH 2 Cl 2 and heats the mixture to a sufficiently elevated temperature to initiate the reaction and maintains a sufficient temperature to maintain the reaction between the phosphoric acid ester and the triazine to produce the N-phosphonomethylglycinonitrile I. Although a solvent is not necessary in the process of the invention, it is sometimes desirable to use a solvent for simplicity and to facilitate the reaction. A solvent is also useful for controlling the reaction temperature. The solvent used is one in which the triazine is soluble and which does not react with any of the reactants.
Sådana inerta lösningsmedel omfattar acetonitril, etylacetat, tetrahydrofuran och liknande.Such inert solvents include acetonitrile, ethyl acetate, tetrahydrofuran and the like.
Man har funnit, att reaktionstemperaturen kan vara så låg som ca 25°C till ca ll0°C. Högre temperaturer kan användas, men inga motsvarande fördelar erhålls därigenom, eftersom reaktionen är väsentligen fullständig när tempera- turen nätt 85°C.It has been found that the reaction temperature can be as low as about 25 ° C to about 110 ° C. Higher temperatures can be used, but no corresponding advantages are obtained thereby, since the reaction is substantially complete when the temperature reaches 85 ° C.
Som framgår av de ovanstående formlerna II och Ill bör förhållandet mellan fosforsyraestern och triazinen vara 3 till l för bästa resultat. Högre eller lägre förhållanden kan användas, men inga motsvarande fördelar erhålls därigenom, eftersom man vid högre förhållanden skulle behöva separera överskott av fosforsyraester och biproduktbildning är möjlig vid lägre förhållan- den mellan ester och triazin.As shown in the above formulas II and III, the ratio of the phosphoric acid ester to the triazine should be 3 to 1 for best results. Higher or lower ratios can be used, but no corresponding advantages are obtained thereby, since at higher ratios it would be necessary to separate excess phosphoric acid ester and by-product formation is possible at lower ratios between ester and triazine.
Reaktionen utförs vanligtvis vid atmosfärstryck av ekonomiska skäl. 7713047-4 3 Emellertid kan högre eller lägre tryck användas, men inga åtföljande fördelar erhålls därigenom.The reaction is usually carried out at atmospheric pressure for economic reasons. 7713047-4 3 However, higher or lower pressures can be used, but no associated benefits are obtained thereby.
För att framställa föreningar med formeln I, där b är l och x är 0, dvs. föreningar med formeln Z (aryl Xa-O)-E' -CH I OH H -N-cH -cN (iv) 2 2 där X, Z och a har den ovan angivna definitionen, bildar man endast en lösning av en förening med formeln Z I' H (aryl Xa-Oiz-P -CH 2~N -Cl-lz-CN (V) där X, Z och a har den ovan angivna definitionen, i ett lösningsmedel som innehåller minst en molekvivalent vatten och håller lösningen vid omgivnings- temperatur, varvid en av (aryl Xa-O)grupperna hydrolyseras. Det föredragna lösningsmedlet för hydrolysen är aceton. Det önskade materialet isoleras med hjälp av standardförfaranden, såsom fraktionerad kristallisation eller vakuumav- dunstning av lösningsmedlet och andra flyktiga hydrolysprodukter, varvid det önskade materialet kan kristalliseras ur något lämpligt lösningsmedel.To prepare compounds of formula I, where b is 1 and x is 0, i.e. compounds of the formula Z (aryl Xa-O) -E '-CH 1 OH H -N-cH -cN (iv) 2 wherein X, Z and a have the above definition, only a solution of a compound with formula ZI 'H (aryl Xa-Oiz-P -CH 2 -N -Cl-1z-CN (V) wherein X, Z and a have the above definition, in a solvent containing at least one molar equivalent of water and keeping the solution at ambient temperature, whereby one of the (aryl Xa-O) groups is hydrolyzed.The preferred solvent for the hydrolysis is acetone.The desired material is isolated by standard methods such as fractional crystallization or vacuum evaporation of the solvent and other volatile hydrolysis products, wherein the desired the material can be crystallized from any suitable solvent.
För att framställa de föreningar med formeln I, där b är 0 och x är l, dvs. föreningar med formeln Z H ll (aryl Xa-0)2-P -CH -N-cH -CN.R (Vi) 2 2 där X, Z och a har de ovan angivna betydelserna, löser man en förening med formeln V i ett vattenfritt lösningsmedel, såsom kloroform, och sätter en stark syra till denna lösning, antingen i ett lösningsmedel eller i vissa fall som sådan, under omrörning vid omgivningstemperatur under en tillräcklig tid för att tillåta föreningen med formeln V och syran att reagera, så att föreningen med formeln VI bildas. I många fall faller den önskade produkten ut i kristallin form ur reaktionslösningen. I andra fall tillsätter man en 50-50 volymblandning av kloroform och dietyleter för att åstadkomma produktkristallisation eller för att separera den från reaktionslösningen som en olja.To prepare the compounds of formula I, where b is 0 and x is 1, i.e. compounds of the formula ZH II (aryl Xa-O) 2-P -CH -N-cH -CN.R (Vi) 2 2 where X, Z and a have the meanings given above, a compound of the formula V is dissolved in a anhydrous solvent, such as chloroform, and add a strong acid to this solution, either in a solvent or in some cases as such, with stirring at ambient temperature for a sufficient time to allow the compound of formula V and the acid to react, so that the compound with formula VI is formed. In many cases the desired product precipitates in crystalline form from the reaction solution. In other cases, a 50-50 by volume mixture of chloroform and diethyl ether is added to effect product crystallization or to separate it from the reaction solution as an oil.
Föreningarna med formeln Vi är salter av diestern med formeln V och kan även representeras av forrneln lO 7713047-4 z H* , z (aryi xa-mz-ë-CH -N -cH -cN.R'¿ (v11) 2 2 där X, Z och a har den ovan angivna definitionen och R I är anjonen av den starka syran.The compounds of formula Vi are salts of the diester of formula V and may also be represented by the formula 10 7713047-4 z H *, z (aryi xa-mz-ë-CH -N -cH -cN.R'¿ (v11) 2 2 where X, Z and a have the above definition and RI is the anion of the strong acid.
Belysande för de grupper som är substituerade på fenyl, naftyl eller bifenylyl och representeras av X är t.ex. halogen, såsom klor, fluor och brom; alkyl, såsom metyl, etyl, propyl och butyl; alkoxi, såsom metoxi, etoxi och propoxi; alkyltio, såsom metyltio, etyltio och propyltio; liksom metylendioxi, cyano, trifluormetyl och nitro. Det framgår av formeln att de grupper som representeras av X kan vara lika eller olika på samma arylring.Illustrative of the groups which are substituted on phenyl, naphthyl or biphenylyl and represented by X are e.g. halogen, such as chlorine, fluorine and bromine; alkyl such as methyl, ethyl, propyl and butyl; alkoxy such as methoxy, ethoxy and propoxy; alkylthio such as methylthio, ethylthio and propylthio; as well as methylenedioxy, cyano, trifluoromethyl and nitro. It can be seen from the formula that the groups represented by X may be the same or different on the same aryl ring.
Starka syror, som är användbara vid framställningen av salterna med stark syra med formeln I, Vi och VII omfattar t.ex. p-toluensuifonsyra, p- klorbensensulfonsyra, triklorättiksyra, oxalsyra, fluorborsyra, klorvätesyra, bromvätesyra, jodvätesyra, trifluorättiksyra, pentafluorpropionsyra, heptafluor- smörsyra, trifluormetansulfonsyra, salpetersyra, svavelsyra, fosforsyra, triklor- metanfosfonsyra, perklorsyra, metansulfonsyra och liknande. _ Vid framställning av salterna med stark syra med formlerna I, VI och VII är det föredraget att använda diestern av fosfonsyran och den starka syran i lika molförhâllanden för att underlätta isoleringen av saltet med stark syra. Högre eller lägre förhållanden mellan ester och syra kan användas, även om isoleringen av produkten görs svårare på grund av närvaron av ett överskott av den ena av reaktanterna.Strong acids, which are useful in the preparation of the salts with strong acid of formula I, Vi and VII include e.g. p-toluenesulfonic acid, p-chlorobenzenesulfonic acid, trichloroacetic acid, oxalic acid, fluoroboric acid, hydrochloric acid, hydrobromic acid, iodohydric acid, trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, trifluoromethanesulfonic acid sulfuric acid sulfuric acid, nitric acid. In the preparation of the strong acid salts of formulas I, VI and VII, it is preferred to use the diester of the phosphonic acid and the strong acid in equal molar ratios to facilitate the isolation of the salt with strong acid. Higher or lower ratios of ester to acid can be used, although the isolation of the product is made more difficult due to the presence of an excess of one of the reactants.
' Hydrolys av de N-fosfonometylglycinonitriler som representeras av formeln l för att få N-fosfonometylglycin kan enkelt och snabbt utföras genom upphettning av glycinonitrilen till måttliga temperaturer (60°-l00°C) i blandning l,0l molekvivalent) av en vattenlösning av klorvätesyra eller bromvätesyra, som med åtminstone ett litet överskott utöver en molekvivalent (t.ex. lämpligen är 1,0 normala och företrädesvis minst 2,0 normala. Med användning av konc. vattenlösning av klorväte- eller bromvätesyra sker en tillfredsställande hydrolys till N-fosfonometylglycin inom 21+ timmar vid rumstemperatur.Hydrolysis of the N-phosphonomethylglycinonitriles represented by the formula I to obtain N-phosphonomethylglycine can be carried out easily and rapidly by heating the glycinonitrile to moderate temperatures (60 ° -100 ° C) in a mixture of 1,01 molar equivalents) of an aqueous solution of hydrochloric acid. or hydrobromic acid, which with at least a slight excess in addition to one molar equivalent (eg suitably 1.0 normal and preferably at least 2.0 normal. Using a concentrated aqueous solution of hydrochloric or hydrobromic acid, a satisfactory hydrolysis to N-phosphonomethylglycine takes place within 21+ hours at room temperature.
Föreningarna representerade av formeln I är användbara som herbicider för applikation både före 'och efter uppkomst.- Följande allmänna förfaranden visar de föredragna metoderna för framställning av de olika föreningarna enligt uppfinningen.The compounds represented by formula I are useful as herbicides for application both before and after emergence. The following general procedures show the preferred methods for preparing the various compounds of the invention.
Diarylestrarna med formeln V framställs företrädesvis med någon av följande två metoder.The diaryl esters of formula V are preferably prepared by one of the following two methods.
(A) En acetonitril-lösning (50 ml) av l,3J-tricyanometyl-hexahydrd-l,3,5- m. i AD' 7.1 7713047-4 triazin (3,4 g, 0,167 mol) och diarylfosfit (0,050 mol) blandas i ett reaktionskärl och upphettas från 45°C till 85°C under från l till 90 timmar, tills all tosfit eller triazin är förbrukad enligt bestämning genom NMR-analys. Om NMR-spektral- analysen indikerar att det inte finns nâgra föroreningar, isoleras produkten genom vakuumkoncentration. Om föroreningar är närvarande, isoleras produkten och renas genom kristallisation eller kromatografiskt. I några fall kan diester- produkten vara svår att isolera i högren form, eftersom hydrolys sker när man försöker utföra isolationen.(A) An acetonitrile solution (50 ml) of 1,3J-tricyanomethyl-hexahydride-1,3,5-m. In AD '7.1 7713047-4 triazine (3.4 g, 0.167 mol) and diaryl phosphite (0.050 mol ) is mixed in a reaction vessel and heated from 45 ° C to 85 ° C for from 1 to 90 hours, until all the phosphite or triazine is consumed as determined by NMR analysis. If the NMR spectral analysis indicates that there are no impurities, the product is isolated by vacuum concentration. If impurities are present, the product is isolated and purified by crystallization or chromatography. In some cases, the diester product can be difficult to insulate in high-purity form, as hydrolysis occurs when trying to perform the insulation.
(B) En blandning av en diarylfosfit (0,05 mol) och l,3,5-tricyanometyl- hexahydro-l,3,5-triazin (3,4 g, 0,0l67 mol) satsas i ett reaktionskärl och upp- herras mi från eo° :in 1oo°c under från zo minuter :in 1 timme, nns au fosfat eller triazin har förbrukats enligt bestämning genom NMR-spektralanalys.(B) A mixture of a diaryl phosphite (0.05 mol) and 1,3,5-tricyanomethylhexahydro-1,3,5-triazine (3.4 g, 0.067 mol) is charged to a reaction vessel and mr from eo °: in 100 ° C for from zo minutes: in 1 hour, nns au phosphate or triazine have been consumed as determined by NMR spectral analysis.
Produkterna renas genom kristallisation eller kromatografi.The products are purified by crystallization or chromatography.
Monoarylestrarna av N-fosfonometylglycinonitril framställs genom att man löser diarylestern i aceton, som innehåller en liten mängd vatten (vanligen ca 2 vikt-96 vatten) och rör om reaktionsblandningen under från 18 till 72 timmar. Monoestrarna är vanligen kristallina och uppsamlas genom filtrering, tvättas med aceton och lufttorkas.The monoaryl esters of N-phosphonomethylglycinonitrile are prepared by dissolving the diaryl ester in acetone, which contains a small amount of water (usually about 2 wt-96 water) and stirring the reaction mixture for from 18 to 72 hours. The monoesters are usually crystalline and are collected by filtration, washed with acetone and air dried.
Salterna av diarylestrarna med starka syror framställs lämpligen medelst följande allmänna förfarande. En lösning av den starka syran (eller syran som sådan) (0,0l mol) sätts droppvis till en kloroformlösning av diestern vid omgivningstemperatur och det hela får stå. Om kristaller bildas, uppsamlas de genom filtrering, tvättas med 50 volymprocentig kloroform-eterblandning och lufttorkas. Annars tillsätter man en 50 volymprocentig kloroform-eterblandning för att bringa saltet att kristallisera eller att skiljas ut ur lösningen som en olja.The salts of the diaryl esters with strong acids are conveniently prepared by the following general procedure. A solution of the strong acid (or acid as such) (0.01 mol) is added dropwise to a chloroform solution of the diester at ambient temperature and the whole is allowed to stand. If crystals form, they are collected by filtration, washed with 50% by volume of chloroform-ether mixture and air-dried. Otherwise, a 50% by volume chloroform-ether mixture is added to cause the salt to crystallize or to separate from the solution as an oil.
Hydrolys av de N-fosfonometylglycinonitriler som representeras av formeln I för att få N-fosfonometylglycin utförs enkelt genom följande allmänna förfarande. De råa eller renade reaktionsprodukterna av en díarylfosfit med I,3,i-tricyanometyl-hexahydro-l,3,5-triazin hydrolyseras genom att man därtill sätter åtminstone ett litet överskott utöver en molekvivalent (t.ex. minst 1,01 mol) av en vattenlösning av klorvätesyra eller bromvätesyra och upphettar blandningen till ca IOOOC under flera timmar under återflödesbetingelser, tills det har fastställts genom NMR-spektralanalys att väsentligen all glycinonitril har hydrolyserats till N-fosfonometylglycim Man extraherar sedan reaktionsbland- ningen två gånger med kloroform för att avlägsna den fenol som bildats under hydrolysen, och de vattenhaltiga skikten filtreras och indunstas till torrhet. Den fasta återstoden löses i vatten, och man kyler lösningen till 0°C för att åstadkomma kristallisation av N-fosfonometylglycinen.Hydrolysis of the N-phosphonomethylglycinonitriles represented by formula I to obtain N-phosphonomethylglycine is easily performed by the following general procedure. The crude or purified reaction products of a diaryl phosphite with 1,3,3-tricyanomethyl-hexahydro-1,3,5-triazine are hydrolyzed by adding to it at least a small excess in addition to one molar equivalent (eg at least 1.01 mol) of an aqueous solution of hydrochloric acid or hydrobromic acid and heats the mixture to about 100 DEG C. for several hours under reflux conditions, until it has been determined by NMR spectral analysis that substantially all of the glycinonitrile has been hydrolysed to N-phosphonomethylglycim. the phenol formed during the hydrolysis, and the aqueous layers are filtered and evaporated to dryness. The solid residue is dissolved in water, and the solution is cooled to 0 ° C to effect crystallization of the N-phosphonomethylglycine.
De råa eller renade reaktionsprodukterna av en diarylfosfit med l,3,5- 'lO 7713047-4 6 tricyanometyl-hexahydro-l,3,5-triazin kan hydrolyseras genom att man därtill sätter en bas vald bland alkalimetallhydroxider eller en tetraalkylammonium- hydroxid, där alkylgrupperna innehåller från l till 4 kolatomer, bildar en blandning av föreningen och basen i vatten, upphettar blandningen för att utföra fullständig hydrolys till ett salt av N-fosfonometylglycin och sedan omvandlar saltet till N-fosfonometylglycin genom att föra en vattenlösning av saltet i kontakt med katjonbytarharts.The crude or purified reaction products of a diaryl phosphite with 1,3,5-tricyanomethyl-hexahydro-1,3,5-triazine can be hydrolyzed by adding thereto a base selected from alkali metal hydroxides or a tetraalkylammonium hydroxide. where the alkyl groups contain from 1 to 4 carbon atoms, form a mixture of the compound and the base in water, heat the mixture to perform complete hydrolysis to a salt of N-phosphonomethylglycine and then convert the salt to N-phosphonomethylglycine by contacting an aqueous solution of the salt with cation exchange resin.
De följande försöken tjänar till att belysa uppfinningen ytterligare, varvid alla delar är i vikt såvida inget annat speciellt anges.The following experiments serve to further illustrate the invention, all parts being by weight unless otherwise specifically indicated.
Exempel l Di(p-klorfenyl)fosfit (23,32 g, 7896 ren, 0,06 mol) och- l,3,5-tricyano- metyl-hexahydro-l,3,5-triazin (ll-,08 g, 0,02 mol) blandades i ett reaktionskärl vid omgivningstemperatur, och blandningen upphettades till l00°C under 20 minuter, vilket gav 0,0-di(p-klorfenyl)-N-fosfonometylglycinonitril i l0096-igt utbyte, 27 g, nål = 1,57a7.Example 1 Di (p-chlorophenyl) phosphite (23.32 g, 7896 pure, 0.06 mol) and 1,3,5-tricyanomethyl-hexahydro-1,3,5-triazine (11-, 08 g (0.02 mol) was mixed in a reaction vessel at ambient temperature, and the mixture was heated to 100 ° C for 20 minutes to give 0,0-di (p-chlorophenyl) -N-phosphonomethylglycinonitrile in 10096 yield, 27 g, needle = 1.57a7.
Exempel 2 _ En acetonitril-lösning (l0 ml) av di(BJL-dimetylfenyßfosíit (8,7 g, 0,03 mol) sattes till en acetonitril-lösning (50 ml) av l,3,S-tricyanometyl-hexahydro- l,3,5-triazin (2,0l+ g, 0,01 mol), och blandningen upphettades vid 55°C under 90 timmar. Filtrering av den fasta substansen och avdunstning av lösningsmedlet gav en burgundfärgad olja, som enligt NMR-analys innehöll den önskade produkten och aminalen av denna produkt. Kromatografi av oljan (8,0 g) över silikagel (#50 g) med 5096 cyklohexan/5096 etylacetat (fraktioner om 60 ml) gav 0,0-di(3,4- dimetylfenyD-N-fosfonometylglycinonitril i íraktionerna 30-41, som smälte vid 6l-6lI-°C efter avlägsning av lösningsmedlet. Den fasta substansen omkristallise- rades ur koltetraklorid-isooktan, smältpunkt 63-66°C, 3,1 g erhållet (4096 utbyte).Example 2 An acetonitrile solution (10 ml) of di (BJL-dimethylphenylphosphite (8.7 g, 0.03 mol) was added to an acetonitrile solution (50 ml) of 1,3,5-tricyanomethyl-hexahydrol-1 , 3,5-triazine (2.0l + g, 0.01 mol), and the mixture was heated at 55 ° C for 90 hours Filtration of the solid and evaporation of the solvent gave a burgundy oil which according to NMR analysis contained the Chromatography of the oil (8.0 g) over silica gel (# 50 g) with 5096 cyclohexane / 5096 ethyl acetate (60 ml fractions) gave 0,0-di (3,4-dimethylphenylD-N -phosphonomethylglycinonitrile in fractions 30-41, melting at 61 DEG-61 DEG C. after removal of the solvent, the solid was recrystallized from carbon tetrachloride isooctane, m.p.
Exempel 3 En omrörd lösning av 0,02 mol di(p'-metyltiofenyDfosfít och 0,0067 mol l,3,5-tricyanometyl-hexahydro-l,3,5-triazin upphettades till 80°C under 1,0 timmar, vilket gav en mörkröd olja. Hälften av provet placerades sedan i kylskåp under 8 dagar och gav en halvfast massa. Provet omkristalliserades sedan ur 70 ml koltetraklorid, vilket gav en röd fast substans. Den fasta substansen löstes i - 100 ml het koltetraklorid och tiltrerades genom celite täckt med 5,0 g silikagel.Example 3 A stirred solution of 0.02 moles of di (p'-methylthiophenyl) phosphite and 0.0067 moles of 1,3,5-tricyanomethyl-hexahydro-1,3,5-triazine was heated to 80 ° C for 1.0 hour, which Half of the sample was then placed in a refrigerator for 8 days to give a semi-solid mass. The sample was then recrystallized from 70 ml of carbon tetrachloride to give a red solid. The solid was dissolved in 100 ml of hot carbon tetrachloride and filtered through celite. covered with 5.0 g of silica gel.
Filtratet koncentrerades till 50 ml och sattes i kylskåp över natten. Suspensionen filtrerades, vilket gav 1,8 g (4596) av en vit fast substans, som identifierades som 0,0-di(p-metyltioienyD-N-fosíonometylglycinonitril med en smältpunkt av 61+- 65°C och med följande analys.The filtrate was concentrated to 50 ml and refrigerated overnight. The suspension was filtered to give 1.8 g (4596) of a white solid, which was identified as 0,0-di (p-methylthioienylD-N-fosionomethylglycinonitrile, m.p. 61 DEG-65 DEG C. and with the following analysis.
NII _17' A) 7713047-4 7 Beräknat: C 51,8, H 4,9, N 7,1, Funnet: C 51,7, H 4,9, N 7,1.Calculated: C 51.8, H 4.9, N 7.1, Found: C 51.7, H 4.9, N 7.1.
Exemgel 4 En lösning av di(o-metoxifenyl)fosfit (8,05 g, 91% ren, 0,025 mol) och l,3,5-tricyanometyl-hexahydro-1,3,5-triazin (1,7 g, 0,0083 mol) upphettades vid 55°C under 73 timmar och filtrerades sedan. Filtratet koncentrerades till en mörkbrun olja (9,6 g). Oljan (5,8 g) fästes på 8 g silikagel och extraherades med 80 ml etylacetat. Etylacetatlösningen koncentrerades, och den resulterande oljan fästes på 4,0 g silikagel. Denna silikagel extraherades med 70 ml etylacetat, och lösningen koncentrerades under vakuum till att ge en blekgul olja, nšz = l,5542.Example Gel 4 A solution of di (o-methoxyphenyl) phosphite (8.05 g, 91% pure, 0.025 mol) and 1,3,5-tricyanomethyl-hexahydro-1,3,5-triazine (1.7 g, 0 .0083 mol) was heated at 55 ° C for 73 hours and then filtered. The filtrate was concentrated to a dark brown oil (9.6 g). The oil (5.8 g) was attached to 8 g of silica gel and extracted with 80 ml of ethyl acetate. The ethyl acetate solution was concentrated, and the resulting oil was attached to 4.0 g of silica gel. This silica gel was extracted with 70 ml of ethyl acetate, and the solution was concentrated in vacuo to give a pale yellow oil, nšz = 1.5542.
Den gula oljan befanns vara 0,0-di(o-metoxifenyD-N-fosfonometylglycinonitril som innehöll en liten mängd o-metoxifenol.The yellow oil was found to be 0,0-di (o-methoxyphenyl) -N-phosphonomethylglycinonitrile which contained a small amount of o-methoxyphenol.
Exemgel 5 En lösning av 1,3,5-tricyanometyl-hexahydro-1,3,5-triazin (13,6 g, 0,066 mol) och difenylfosfit (46,8 g, 0,2 mol) i acetonitril (100 ml) upphettades vid 55°C under 48 timmar. NMR för den råa reaktionsblandningen indikerade fullständig omsättning till 0,0-diienyl-N-fosfonometylglycinonitril. Acetonitri- len avlägsnades i vakuum, vilket gav 57 g (94,4%) av en viskös svart olja. Oljan löstes i kloroform, l14g silikagel tillsattes och blandningen indunstades till torrhet 1 vakuum. Den produktimpregnerade silikagelen placerades sedan i en kolonn innehållande en uppslamning av kloroform och silikagel (200 g) och eluerades tills produkten inte längre pâvisades i eluatet genom NMR. Kloroform- eluaten koncentrerades, löstes i metylenklorid och tvättades tvâ gånger med kall %-ig KOH (100 ml) och sedan med vatten. Metylenkloridskiktet torkades över MgSOa, íiltrerades och indunstades till att kvarlämna 37,9 g av en ljusgul olja, som stelnade efter att ha fått stå. Den fasta substansen hade en smältpunkt av 64-67,5°C och identifierades som QO-difenyl-N-fosfonometylglycinonittil, erhâllen i 75%-igt utbyte.Example 5 A solution of 1,3,5-tricyanomethyl-hexahydro-1,3,5-triazine (13.6 g, 0.066 mol) and diphenyl phosphite (46.8 g, 0.2 mol) in acetonitrile (100 ml) was heated at 55 ° C for 48 hours. NMR of the crude reaction mixture indicated complete conversion to 0,0-diienyl-N-phosphonomethylglycinonitrile. The acetonitrile was removed in vacuo to give 57 g (94.4%) of a viscous black oil. The oil was dissolved in chloroform, 14 g of silica gel was added and the mixture was evaporated to dryness in vacuo. The product impregnated silica gel was then placed in a column containing a slurry of chloroform and silica gel (200 g) and eluted until the product was no longer detected in the eluate by NMR. The chloroform eluate was concentrated, dissolved in methylene chloride and washed twice with cold% KOH (100 mL) and then with water. The methylene chloride layer was dried over MgSO 4, filtered and evaporated to leave 37.9 g of a light yellow oil, which solidified on standing. The solid had a melting point of 64-67.5 ° C and was identified as QO-diphenyl-N-phosphonomethylglycinonitrile, obtained in 75% yield.
Exemgel 6 En acetonitrillösning (100 ml) av di(m-to1yl)fos;fit (l0,7 g, 0,04 mol) och I1,3,5-tricyanometyl-hexahydro-1,3,5-triazin (2,72 g, 0,0133 mol) upphettades till 50°C under 3 dagar. Lösningen blev vinröd till färgen, och lösningsmedlet avdunstades till att kvarlämna 12,4 g av en röd olja 02,496 utbyte). Oljan (9,0 g) kromatograferades över silikagel och eluerades med 6096 cyklohexan/4096 etylacetat, varvid fraktioner om 60 ml togs. Fraktionerna 45-63 var ren 0,0- di(m-tolyl)-N-fosíonometylglycinonitril, nås = 1,5467 (l,25 g, 14% utbyte), som hade följande analys.Example 6 An acetonitrile solution (100 ml) of di (m-tolyl) phosphite (10.7 g, 0.04 mol) and 1,3,3-tricyanomethyl-hexahydro-1,3,5-triazine (2, 72 g, 0.0133 mol) was heated to 50 ° C for 3 days. The solution turned burgundy to the color, and the solvent was evaporated to leave 12.4 g of a red oil (02.449 yield). The oil (9.0 g) was chromatographed on silica gel eluting with 6096 cyclohexane / 4096 ethyl acetate to take 60 ml fractions. Fractions 45-63 were pure 0,0- di (m-tolyl) -N-phosonomethylglycinonitrile, reach = 1.5467 (1.25 g, 14% yield), which had the following analysis.
Beräknat: C 61,81, H 5,80, N 8,48, Funnet: C 61,75, H 5,81, N 8,41. 7713047-4 8 ExemEel 7 En lösning av di(m-nitrofenyl)fosfit (l5,2 g, 8396 ren, 0,0392 mol) och 1,3,S-tricyanometyl-hexahydro-1,3,S-triazin (2,66 g, 0,013 mol) i acetonitril upphettades till SOOC under 20 timmar. NMR-analys indikerade fullständig reaktion. Lösningen filtrerades, och lösningsmedlet avlägsnades i vakuum, vilket kvarlämnade 13 g _av en bärnstensfärgad olja identifierad som 0,0-di(m- nitrofenyD-N-fosfonometylglycinonitril, som gav följande analys.Calculated: C 61.81, H 5.80, N 8.48, Found: C 61.75, H 5.81, N 8.41. Example 7 A solution of di (m-nitrophenyl) phosphite (1.5.2 g, 8396 pure, 0.0392 mol) and 1,3,5-tricyanomethyl-hexahydro-1,3,5-triazine (2 .66 g, 0.013 mol) in acetonitrile was heated to SOOC for 20 hours. NMR analysis indicated complete reaction. The solution was filtered, and the solvent was removed in vacuo to leave 13 g of an amber oil identified as 0,0-di (m-nitrophenylD-N-phosphonomethylglycinonitrile, which gave the following analysis.
C 45,93, H 3,34, N 14,28, C 45,80, H 3,39, N 14,27.C 45.93, H 3.34, N 14.28, C 45.80, H 3.39, N 14.27.
ExemEe18 Di(p-metoxifenyl)fosfit (0,05 mol, 15,63 g, 94% ren) och l,3,5-tricyano- Beräknat: ' Funnet: metyl-hexahydro-1,3,5-triazin (3,4 g, 0,0167 mol) löstes' i acetonitril, och lösningen upphettades till återflöde under l timme. Lösningsmedlet avdunstades i vakuum, vilket gav en mörkbrun olja (19,0 g). Denna olja '(5 g) utsattes för högtrycksvätskekromatografi med användning av en blandning av cyklohexan och etylacetat (40/60 vol.96) för återvinning av 4,1 g 0,0-di(p-metoxifenyl)-N- fosfonometylglycinonitril som en olja, n? = l,5541, 82% utbyte.Example 18 Di (p-methoxyphenyl) phosphite (0.05 mol, 15.63 g, 94% pure) and 1,3,5-tricyano Calculated: Found: Methyl hexahydro-1,3,5-triazine (3 4 g, 0.0167 mol) was dissolved in acetonitrile, and the solution was heated to reflux for 1 hour. The solvent was evaporated in vacuo to give a dark brown oil (19.0 g). This oil (5 g) was subjected to high pressure liquid chromatography using a mixture of cyclohexane and ethyl acetate (40/60 vol.96) to recover 4.1 g of 0,0-di (p-methoxyphenyl) -N-phosphonomethylglycinonitrile as a oil, n? = 1, 5541, 82% yield.
ExemEel 9 En blandning av 1,3,i-tricyanometyl-hexahydro-l,3,5-triazin (2,04 g, 0,01 mol) och di(p-fluorfenyl)fosfit (8,8 g, 91,696 ren, 0,03 mol) i acetonitril (50 ml) upphettades till 55°C under 70 timmar. Reaktionsblandningen filtrerades, och lösningsmedlet avlägsnades i vakuum, vilket gav en brun olja, nâj = 1,5270, som var 9296 ren 0,0-di(p-fluorfenyD-N-fosfonometylglycinonitril.Example 9 A mixture of 1,3,1-tricyanomethyl-hexahydro-1,3,5-triazine (2.04 g, 0.01 mol) and di (p-fluorophenyl) phosphite (8.8 g, 91.696 pure, 0.03 mol) in acetonitrile (50 ml) was heated to 55 ° C for 70 hours. The reaction mixture was filtered, and the solvent was removed in vacuo to give a brown oil, nâj = 1.5270, which was 9296 pure 0,0-di (p-fluorophenyl-N-phosphonomethylglycinonitrile).
ExemEel 10 Di(m-klorfeny1)fosíit (9,93 g, 91,596 ren, 0,03 mol) löstes i acetonitril (20 ml) och sattes till 1,3,fi-tricyanometyl-hexahydro-1,3,5-triazin (204 g, 0,01 mol) löst i acetonitril (50 ml), och blandningen upphettades till 55°C under 70 timmar.Example 10 Di (m-chlorophenyl) fosite (9.93 g, 91.596 pure, 0.03 mol) was dissolved in acetonitrile (20 ml) and added to 1,3, tr-tricyanomethyl-hexahydro-1,3,5-triazine (204 g, 0.01 mol) dissolved in acetonitrile (50 ml), and the mixture was heated to 55 ° C for 70 hours.
Acetonitrilen avlägsnades i vakuum, vilket kvarlämnade en ljusröd olja, nâj = 1,56%, som var 92% ren 0,0-di(m-kIorfenyD-N-fosfonometylglycinonitril.The acetonitrile was removed in vacuo to give a light red oil, njaj = 1.56%, which was 92% pure 0,0-di (m-chlorophenylD-N-phosphonomethylglycinonitrile.
Följande föreningar kan också framställas med de ovan angivna förfaran- dena: 0,0-di(p-cyanoíenyD-N-fosfonometylglycinonitril 0,0-di(p-bifenylyD-N-fosfonometylglycinonitril Exemgel 11 Den i Exempel 10 framställda diestern (4,0 g, 0,099 mol) löstes i 100 ml Z96-ig vattenlösning av aceton, och lösningen omrördes vid omgivningstemperatur under 6» dagar, under vilken tid en fast substans bildades. Den fasta substansen uppsamlades, tvättades med aceton och torkades, víket gav 1,55 g (60%) O-m- as! 7713047-4 9 klorfenyl-N-fosfonometylglycinonitril som en fast substans med en smältpunkt av 1s1-1s2°c och med följande analys.The following compounds can also be prepared by the above procedures: 0,0-di (p-cyanoyleneD-N-phosphonomethylglycinonitrile 0,0-di (p-biphenylyd-N-phosphonomethylglycinonitrile Example 11 The diester prepared in Example 10 (4, 0 g, 0.099 mol) was dissolved in 100 ml of Z96-aqueous solution of acetone, and the solution was stirred at ambient temperature for 6 days, during which time a solid formed. The solid was collected, washed with acetone and dried, yielding 1 g. 55 g (60%) of chlorophenyl-N-phosphonomethylglycinonitrile as a solid with a melting point of 1s1-1s2 ° C and with the following analysis.
Beräknat: C 41,5, H 3,9, N 10,8, Funnet: C 41,5, H 3,9, N 10,8.Calculated: C 41.5, H 3.9, N 10.8, Found: C 41.5, H 3.9, N 10.8.
Exemgel 12 _ Den i Exempel 9 framställda diestern (2,38 g, 0,069 mol) löstes i 296-ig vattenlösning av aceton (100 ml) och omrördes vid omgivningstemperatur under 3 dagar. Den resulterande uppslamningen filtrerades och den fasta substansen tvättades med aceton, vilket gav 0,87 g av en brun fast substans med en smältpunkt av 258-262°C. Moderluten fick stå under 6 veckor, och den resulterande fasta substansen uppsamlades och tvättades med aceton, vilket gav ytterligare 0,8 g material med samma smältpunkt, som ldentifierades som O-p- fluorfenyl-N-fosfonometylglycinonitril i 98%-igt utbyte och med följande analys.Example Gel 12 The diester prepared in Example 9 (2.38 g, 0.069 mol) was dissolved in 296 g of aqueous acetone (100 ml) and stirred at ambient temperature for 3 days. The resulting slurry was filtered and the solid was washed with acetone to give 0.87 g of a brown solid, m.p. 258-262 ° C. The mother liquor was allowed to stand for 6 weeks, and the resulting solid was collected and washed with acetone to give an additional 0.8 g of material with the same melting point, which was identified as Opfluorophenyl-N-phosphonomethylglycinonitrile in 98% yield and with the following analysis .
Beräknat: C 44,3, H 4,1, N 11,5, ' runner: c 44,3, H 4,2, N 11,5.Calculated: C 44.3, H 4.1, N 11.5, Runner: C 44.3, H 4.2, N 11.5.
ExemEel 13 Op-difenyl-N-fosfonometylglycinonitril (l,51 g, 0,005 mol) omrördes i 50 ml 2N saltsyra under upphettning, tills allt material var löst (2 timmar). En bärnstensíärgad olja observerades i bottnen av kolven och befanns vara fenol.Example 13 Op-diphenyl-N-phosphonomethylglycinonitrile (1.51 g, 0.005 mol) was stirred in 50 ml of 2N hydrochloric acid under heating until all the material was dissolved (2 hours). An amber oil was observed in the bottom of the flask and was found to be phenol.
Kolven kyldes till rumstemperatur, och man tvättade saltsyralösningen tvâ gånger med metylenklorid (25 ml) för att avlägsna allt utgångsmaterial och fenol som bildats under reaktionen. Saltsyralösningen kyldes sedan i ett isbad, varvid kristaller började bildas. Kristallerna uppsamlades, tvättades med kallt vatten och lufttorkades. Kristallerna identifierades som O-fenyl-N-iosfonometylglycino- nitril och hade ingen distinkt smältpunkt. Kristallerna gav följande analys.The flask was cooled to room temperature, and the hydrochloric acid solution was washed twice with methylene chloride (25 ml) to remove any starting material and phenol formed during the reaction. The hydrochloric acid solution was then cooled in an ice bath, whereby crystals began to form. The crystals were collected, washed with cold water and air dried. The crystals were identified as O-phenyl-N-iosphonomethylglycinonitrile and had no distinct melting point. The crystals gave the following analysis.
Beräknat: C 47,79, H 4,90, N 12,39, Funnet: C 47,52, H 4,93, N 12,12.Calculated: C 47.79, H 4.90, N 12.39, Found: C 47.52, H 4.93, N 12.12.
Exemgel 14 0,0-di(m-tolyD-N-fosfonometylglycinonitrii (4,0 g, 0,012 mol) löstes i aceton (50 ml) innehållande vatten (1 ml) och omrördes under 60 dagar vid omgivningstemperatur. Man fick tre omgångar kristaller. De första två om- gângarna av kristaller hade en smältpunkt av l6l-l66°C och bestämdes vara orena. Den tredje omgången hade en smältpunkt av 179-l79,5°C och befanns vara analytiskt ren O-m-tolyl-N-fosfonometylglycinonitril, som erhölls i 53%-igt utbyte och hade följande analys.Example 14 14-O-di (m-tolyD-N-phosphonomethylglycinonitrile (4.0 g, 0.012 mol) was dissolved in acetone (50 ml) containing water (1 ml) and stirred for 60 days at ambient temperature to give three batches of crystals The first two batches of crystals had a melting point of 161-166 ° C and were determined to be impure.The third batch had a melting point of 179-179.5 ° C and was found to be analytically pure Om-tolyl-N-phosphonomethylglycinonitrile, which was obtained in 53% yield and had the following analysis.
Beräknat: C 50,0, H 5,5, N ll,7, Funnet: C 50,0, H 5,5, N 11,7.Calculated: C 50.0, H 5.5, N 11.7. Found: C 50.0, H 5.5, N 11.7.
Exemgel 15 0,0-di(m-nitroíenyl)-N-fosfonometylglycinonitril (3,l5 g, 0,008 mol) lös- l0 7713047-4 tes i aceton (50 ml) och vatten (1 m1) och omrördes vid rumstemperatur under 16 timmar. Bildad fast substans uppsamlades och tvättades med aceton, vilket gav 1,1 g (5196) utbyte, av ett material identifierat som O-m-nitrofenyl-N~fosfono- metylglycinonitril med en smältpunkt av l74-176°C med sönderdelning och med följande analys.Example 15 0.0-Di (m-nitroenyl) -N-phosphonomethylglycinonitrile (3.5 g, 0.008 mol) was dissolved in acetone (50 ml) and water (1 ml) and stirred at room temperature for 16 hours. hours. The solid formed was collected and washed with acetone to give 1.1 g (5196) yield, of a material identified as O-m-nitrophenyl-N-phosphonomethylglycinonitrile having a melting point of 174-176 ° C with decomposition and with the following analysis.
C 40,0, H 3,4, N 15,6, C 40,0, H 3,4, N 15,5.C 40.0, H 3.4, N 15.6, C 40.0, H 3.4, N 15.5.
ExemEel 16 En acetonitril-lösning (100 ml) av di(m-trifluortolyßfosfit (ll,64 g, 0,03l4 moi) och 1,3,5-tricyanometyl-hexahydro-l,3,5-triazin (2,15 g, 0,0l05 mol-96) upphettades vid 50°C under natten. Acetonitrilen avdunstades under Beräknat: Funnet: vakuum, och fast substans började bildas. Det återstående materialet löstes i aceton (50 ml) och vatten (1 ml) och omrördes under natten vid omgivnings- temperatur, under vilken tid fast ' substans bildades. Den fasta substansen uppsamlades och tvättades med aceton, vilket gav 3,5 g 09,596) av en vit fast substans med en smältpunkt av l95-l96°C och identiflerades som O-m- trifluortolyl-N-fosfonometylglycinonitril med följande analys. ' C 40,8, H 3,4, N 9,5, C 41,0, l-l 3,5, N 9,7.Example 16 An acetonitrile solution (100 ml) of di (m-trifluorotolysphosphite (11, 64 g, 0,03,14 (0.055 mol-96) was heated at 50 DEG C. The acetonitrile was evaporated under Calculated: Found: vacuum, and solid began to form, the remaining material was dissolved in acetone (50 ml) and water (1 ml) and stirred under The solid was collected and washed with acetone to give 3.5 g (09.596) of a white solid, m.p. 195-196 ° C, and was identified as trifluorotolyl-N-phosphonomethylglycinonitrile by the following assay. C 40.8, H 3.4, N 9.5, C 41.0, 1-1.5, N 9.7.
ExemEel 17 0,0-di(p-klorfenyl)-N-fosfonometylglycinonitril (9,0 g, 0,024 mol) löstes i aceton (50 ml) och vatten (l ml) och omrördes vid rumstemperatur under 2 dagar.Example 17 0.0-Di (p-chlorophenyl) -N-phosphonomethylglycinonitrile (9.0 g, 0.024 mol) was dissolved in acetone (50 ml) and water (1 ml) and stirred at room temperature for 2 days.
Beräknat: Funnet: En fast substans bildades, som uppsamlades och vägde 2,35 g. Den fasta substansen hade en smältpunkt av 170°C med sönderdelning och identiíierades som O-p-klorfenyl-N-fosfonometylglycinonitri1. Moderluten fick stå under flera veckor, och ytterligare 0,85 g uppsamlades. Det totala utbytet av produkten var 3,2 g (5196 utbyte).Calculated: Found: A solid was formed, which was collected and weighed 2.35 g. The solid had a melting point of 170 ° C with decomposition and was identified as O-p-chlorophenyl-N-phosphonomethylglycinonitrile. The mother liquor was allowed to stand for several weeks, and an additional 0.85 g was collected. The total yield of the product was 3.2 g (5196 yield).
ExemEel 18 21 g av en lösning innehållande 83,8 vikt-% di(3-metyl-lß-nitrofenyfifosfit (0,05 mol) och l,3,S-tricyanometyl-hexahydro-l,3,5-triazin« (3,4 g, 0,0l67 mol) löstes i 100 ml acetonitril och upphettades till 70°C under l timme. Acetonitril- lösningsmedlet avlägsnades under vakuum, och återstoden löstes i 50 ml aceton innehållande l ml vatten och omrördes vid omgivningstemperatur. Kristallerna (4,3 g, 30% utbyte) identifíerades som O-(3-metyl-4-nitrofenyl)-N-fosfonometyl- glycinonitril med en smältpunkt av l8l-l82°C. Materialet hade följande analys.Example 18 21 g of a solution containing 83.8% by weight of di (3-methyl-1β-nitrophenyl) phosphite (0.05 mol) and 1,3,5-tricyanomethyl-hexahydro-1,3,5-triazine (3 (4 g, 0.0l67 mol) was dissolved in 100 ml of acetonitrile and heated to 70 DEG C. for 1 hour, the acetonitrile solvent was removed in vacuo and the residue was dissolved in 50 ml of acetone containing 1 ml of water and stirred at ambient temperature. (3 g, 30% yield) was identified as O- (3-methyl-4-nitrophenyl) -N-phosphonomethylglycinonitrile having a melting point of 181-182 ° C. The material had the following analysis.
C 42,1, H 4,2, N 14,7, C 42,2, H 4,3, N 14,7.C 42.1, H 4.2, N 14.7, C 42.2, H 4.3, N 14.7.
Exemgel 19 0,0~di(p-metoxifenyD-N-íosfonometylglycinonitril (3,0 g, 0,0082 mol) Beräknat: Funnet: :fm t: .ml 7713047-4 ll löstes i aceton (50 ml) och vatten (1 ml) och omrördes vid omgivningstemperatur under 3 månader. Under denna period bildades fast substans. Den fasta substansen avlägsnades genom filtrering, tvättades med aceton och torkades. Den fasta substansen identifierades som O-p-metoxifenyl-N-fosfonometylglycinonitril och hade en smältpunkt av l85-l95°C med sönderdelning. Materialet gav _ följande analys.Example Gel 19 0.0-di (p-methoxyphenyl-D-N-isphonomethylglycinonitrile (3.0 g, 0.0082 mol) Calculated: Found: fm t: ml 7713047-4 μl was dissolved in acetone (50 ml) and water ( 1 ml) and stirred at ambient temperature for 3 months, during which time the solid formed, the filter was removed by filtration, washed with acetone and dried, the solid was identified as Op-methoxyphenyl-N-phosphonomethylglycinonitrile and had a melting point of 185 DEG. 195 DEG C. with decomposition The material gave the following analysis.
Beräknat: C 46,9, H 5,1, N 11,0, Funnet: C 47,1, l-l 5,2, N 10,8.Calculated: C 46.9, H 5.1, N 11.0, Found: C 47.1, 1-1 5.2, N 10.8.
Exemgel 20 Di(o-klorfenyl)fosfit (19,5 g, 80 vikt-%, 0,05 mol) sattes till en aceto- nitril-lösning (50 ml) av 1,3,5-tricyanometyl-hexahydro-lß,fi-triazin (3,4 g, 0,0l640 mol) och upphettades till 70°C under 2 timmar. En 15 ml portion av reaktionslösningen koncentrerades och löstes i aceton (50 ml) och vatten (l ml) och omrördes under natten, varvid fast substans bildades. Den fasta substansen uppsamlades, tvättades med aceton och torkades, vilket gav 3,2 g (8496 utbyte) av ett material identifierat som O-o-klorfenyl-N-fosfonometylglycinonitril med en smältpunkt av l70-i7l°C och med följande analys.Example gel Di (o-chlorophenyl) phosphite (19.5 g, 80% by weight, 0.05 mol) was added to an acetonitrile solution (50 ml) of 1,3,5-tricyanomethyl-hexahydrol-1β, fi-triazine (3.4 g, 0.01640 mol) and heated to 70 ° C for 2 hours. A 15 ml portion of the reaction solution was concentrated and dissolved in acetone (50 ml) and water (1 ml) and stirred overnight to give a solid. The solid was collected, washed with acetone and dried to give 3.2 g (8496 yield) of a material identified as O-o-chlorophenyl-N-phosphonomethylglycinonitrile, m.p. 170 DEG-170 DEG C. and with the following analysis.
Beräknat: C 41,5, H 3,9, N 10,8, Funnet: C 41,4, H 3,9, N 10,7.Calculated: C 41.5, H 3.9, N 10.8, Found: C 41.4, H 3.9, N 10.7.
Exemgel 21 0,0-di(p-fluorfenyi)-N-fosfonometylglycinonitril (2,_38 g, 0,069 mol) om- rördes i en 50 volym96-ig blandning av koltetraklorid och metylenklorid, filtrerades och metansulfonsyra (0,67 g, 0,069 mol) tillsattes. Lösningen fick stå under natten, och de bildade kristallerna uppsamlades genom filtrering och tvättades med koltetraklorid, vilket gav 2,68 g av ett vitt kristallint material identifierat som metansulfonsyrasaltet av 0,0-di(p-fluorfenyl)-N-fosfonometylglycinonitril.Example 21 21-O-di (p-fluorophenyl) -N-phosphonomethylglycinonitrile (2.38 g, 0.069 mol) was stirred in a 50 volume 96 μg mixture of carbon tetrachloride and methylene chloride, filtered and methanesulfonic acid (0.67 g, 0.069 mol) was added. The solution was allowed to stand overnight, and the crystals formed were collected by filtration and washed with carbon tetrachloride to give 2.68 g of a white crystalline material identified as the methanesulfonic acid salt of 0,0-di (p-fluorophenyl) -N-phosphonomethylglycinonitrile.
Detta salt hade en smältpunkt av l32-l32,5°C och gav följande analys.This salt had a melting point of 132-132.5 ° C and gave the following analysis.
Beräknat: C 44,2, H 4,0, N 6,5, S 7,4, Funnet: C 44,0, H 4,0, N 6,6, S 7,5.Calculated: C 44.2, H 4.0, N 6.5, S 7.4, Found: C 44.0, H 4.0, N 6.6, S 7.5.
ExemEel 22 p-Toluensulfonsyra (1,9 g, 0,0l mol) återloppskokades i bensen (100 ml), och närvarande vatten avlägsnades genom azeotropisk behandling med bensen.Example 22 p-Toluenesulfonic acid (1.9 g, 0.01 mol) was refluxed in benzene (100 ml), and water present was removed by azeotropic treatment with benzene.
Denna bensenlösning sattes till en bensen-metylenkloridlösning (50/50 volym-96, 100 ml) av 0,0-difenyl-N-fosíonometylglycinonitril (3,02 g, 0,1 mol). Blandningen omrördes under 1 minut vid rumstemperatur, varvid kristallisation skedde. Den resulterande uppslamningen omrördes vid rumstemperatur under natten och filtrerades sedan, vilket gav en vit fast substans identifierad som p-toluensulfon- syrasaltet av 0,0-difenyl-N-fosfonometylglycinonitril (1538 g, 92,496 utbyte) med en smältpunkt av l52-153°C. Föreningen gav följande analys. _20 7713047-4 12 Beräknat: _ C 55,7, H 4,9, N 5,9, Funnet: C 55,4, H 4,9, N 5,7; Exemgel 23 En kloroformlösning av p-klorbensensulfonsyra (l,92 g, 0,01 mol) sattes till en kloroformlösning av 0p-difenyl-N-fosfonometylglycinonitril (3,0 g, 0,01 mo1). Blandningen omrördes, och efter 10 minuter började kristallisation.This benzene solution was added to a benzene-methylene chloride solution (50/50 volume-96, 100 ml) of 0,0-diphenyl-N-phosphonomethylglycinonitrile (3.02 g, 0.1 mol). The mixture was stirred for 1 minute at room temperature, whereupon crystallization took place. The resulting slurry was stirred at room temperature overnight and then filtered to give a white solid identified as the p-toluenesulfonic acid salt of 0,0-diphenyl-N-phosphonomethylglycinonitrile (1538 g, 92.496 yield) with a melting point of 152-153 ° C. The compound gave the following analysis. Calculated: C 55.7, H 4.9, N 5.9, Found: C 55.4, H 4.9, N 5.7; Example 23 A chloroform solution of p-chlorobenzenesulfonic acid (1.92 g, 0.01 mol) was added to a chloroform solution of Oβ-diphenyl-N-phosphonomethylglycinonitrile (3.0 g, 0.01 mol). The mixture was stirred, and after 10 minutes crystallization began.
Uppslamningen omrördes under natten, filtrerades och den fasta substansen tvättades med kloroform, vilket kvarlämnade 4,0 g av en vit fastsubstans (81%), smältpunkt 149-15 loC, identifierad som p-klorbensensulfonsyrasaltet av 0,70- difenyl-N-fosfonometylglycinonitril med följande analys.The slurry was stirred overnight, filtered and the solid washed with chloroform to leave 4.0 g of a white solid (81%), mp 149-15 ° C, identified as the p-chlorobenzenesulfonic acid salt of 0.70-diphenyl-N-phosphonomethylglycinonitrile with the following analysis.
Beräknat: C 51,0, H 4,1, N 5,7, Funnet: C 50,7, H 4,1, N 5,7.Calculated: C 51.0, H 4.1, N 5.7, Found: C 50.7, H 4.1, N 5.7.
' ExemEel 24 En kloroformlösning (20 ml) av triklorättiksyra (l,63 g, 0,01 mol) sattes till en kloroformlösning (100 ml) av 0,0-difenyl-N-fosíonometylglycinonitril (3,0 g, 0,01 mol) och omrördes under natten vid rumstemperatur. Kristallisatlon kunde inte framkallas, och lösningsmedlen avlägsnades i vakuum, vilket kvarläm- nade en iiusgui ena, 3,75 g (30%) n? = 1,su1o identifierad som :fader- ättiksyrasaltet av Op-difenyl-N-fosfonometylglycinonitril med följande analys.Example 24 A chloroform solution (20 ml) of trichloroacetic acid (1.63 g, 0.01 mol) was added to a chloroform solution (100 ml) of 0,0-diphenyl-N-phosonomethylglycinonitrile (3.0 g, 0.01 mol ) and stirred overnight at room temperature. Crystallisation could not be developed, and the solvents were removed in vacuo to leave a solution of 3.75 g (30%). = 1, sulo identified as: the father-acetic acid salt of Op-diphenyl-N-phosphonomethylglycinonitrile by the following analysis.
Beräknat: C 43,9, H 3,5, N 6,0, Funnet: C 43,9, H 3,5, N 5,9. g Exemgel 25 En acetonlösning (25 ml) av oxalsyradihydrat (1,26 g, 10 mol) sattes till en acetonlösning av 0,0-difenyl-N-fosfonometylglycinonitril (3,20 g, 10 mol).Calculated: C 43.9, H 3.5, N 6.0, Found: C 43.9, H 3.5, N 5.9. g Example Example An acetone solution (25 ml) of oxalic acid dihydrate (1.26 g, 10 mol) was added to an acetone solution of 0,0-diphenyl-N-phosphonomethylglycinonitrile (3.20 g, 10 mol).
Efter 10 minuter började saltet kristallisera ur lösningen. Lösningen omrördes under natten, kyldes och den fasta substansen (1,9 g) uppsarnlades och tvättades med aceton. En andra omgång erhölls genom koncentrering av moderluten, 0,8 g.After 10 minutes, the salt began to crystallize from the solution. The solution was stirred overnight, cooled and the solid (1.9 g) was collected and washed with acetone. A second batch was obtained by concentrating the mother liquor, 0.8 g.
Utbytet var 2,7 g, 69%, smältpunkten 165°C med sönderclelning. Kristallerna identifierades som oxalsyrasaltet av 0,0-difenyl-N-fosfonometylglycinonitril och hade följande analys.The yield was 2.7 g, 69%, melting point 165 ° C with decomposition. The crystals were identified as the oxalic acid salt of 0,0-diphenyl-N-phosphonomethylglycinonitrile and had the following assay.
Beräknat; c 52,1, H 4,4, N 7,1, Funnet: C 52,1, H 4,4, N 7,1.Calculated; c 52.1, H 4.4, N 7.1, Found: C 52.1, H 4.4, N 7.1.
ExemEel 26 En eterlösning av perklorsyra sattes till en kloroform-eterlösning av 0,0- difenyl-N-fosfonometylglycinonitril (3,0 g, 10 mol). Perkloratsaltet kristallise- rade sakta som vita prismor. Den fasta substansen,identifierad som perklorsyra- saltet av 0,0-difenyl-N-fosfonometylglycinonitril, uppsamlades och tvättades med eter-kloroform, vilket gav 0,73 g, 1896 utbyte, smältpunkt 166-l68°C. Saltet hade följande analys. 7713047-« 13 Beräknat: c 44,7, H 4,0, N 7,0, C 44,8, H 4,0, N 7,0.Example 26 An ether solution of perchloric acid was added to a chloroform-ether solution of 0,0-diphenyl-N-phosphonomethylglycinonitrile (3.0 g, 10 mol). The perchlorate salt crystallized slowly as white prisms. The solid, identified as the perchloric acid salt of 0,0-diphenyl-N-phosphonomethylglycinonitrile, was collected and washed with ether-chloroform to give 0.73 g, 1896 yield, mp 166-168 ° C. The salt had the following analysis. Calculated: c 44.7, H 4.0, N 7.0, C 44.8, H 4.0, N 7.0.
ExemEel 27 En kloroform-metanol-lösning av triklormetanfosfonsyra (l,99 g, 0,01 Funnet: mol) sattes till en kloroformlösning av 0,0-difenyl-N-fosfonometylglycinonitril (3,0 g, 10 mol). Efter l0 minuter tillsattes eter, och inga kristaller bildades.Example 27 A chloroform-methanol solution of trichloromethanephosphonic acid (1.99 g, 0.01 Found: mol) was added to a chloroform solution of 0,0-diphenyl-N-phosphonomethylglycinonitrile (3.0 g, 10 mol). After 10 minutes, ether was added, and no crystals formed.
Petroleumeter tillsattes till precis före grumlingspunkten. Efter 10 minuter började kristaller bildas, och det hela fick stå under ytterligare 10 minuter.Petroleum ether was added just before the cloud point. After 10 minutes, crystals began to form, and the whole was allowed to stand for another 10 minutes.
Kristallerna uppsamlades i två omgångar, 2,9 g, 5896 utbyte, smältpunkt 145- 146°C. Kristallerna identifierades som triklormetanfosfonsyrasaltet av 0,0- difenyl-N-fosfonometylglycinonitril och hade följande analys.The crystals were collected in two batches, 2.9 g, 5896 yield, mp 145-146 ° C. The crystals were identified as the trichloromethane phosphonic acid salt of 0,0-diphenyl-N-phosphonomethylglycinonitrile and had the following analysis.
C 38,3, H 3,4, N 5,6, C 38,3, H 3,5, N 5,6.C 38.3, H 3.4, N 5.6, C 38.3, H 3.5, N 5.6.
ExemEel 28 En eterlösning av fluorborsyra sattes till en kloroform-eterlösning av Beräknat: Funnet: 0,0-difenyl-N-fosionometylglycinonitril (3,0 g, 10 mol). Lösningen omrördes under natten, och den fasta substansen filtrerades, tvättades med eter-kloroform (50/50), vilket kvarlämnade vita kristaller, l,l g, 28% utbyte, smältpunkt 156- l58°C, identifierade som fluorborsyrasaltet av 0,0-difenyl-N-fosfonometyl- glycinonitril med följande analys.Example 28 An ether solution of fluoroboric acid was added to a chloroform-ether solution of Calculated: Found: 0,0-diphenyl-N-fosionomethylglycinonitrile (3.0 g, 10 mol). The solution was stirred overnight, and the solid was filtered, washed with ether-chloroform (50/50) to leave white crystals, 1.1 g, 28% yield, mp 156-185 ° C, identified as the hydrochloric acid salt of 0.0 diphenyl-N-phosphonomethylglycinonitrile by the following assay.
C 46,2, H 4,1, N 7,2, C 46,0, H 4,2, N 7,2.C 46.2, H 4.1, N 7.2, C 46.0, H 4.2, N 7.2.
ExemEel 29 Gasformig vätebromid bubblades in i en kloroformlösning av 0,0-difenyl- Beräknat: Funnet: N-fosfonometylglycinonitril (3,0 g, 10 mol). Lösningen fick stå under natten, då hydrobromiden kristalliserade. Kristallerna uppsamlades och tvättades med eter, vilket kvarlämnade 3,0 g, 78% utbyte, identifierat som vätebromidsaltet av 0,0- difenyl-N-fosfonometylglycinonitril med följande analys.Example 29 Gaseous hydrogen bromide was bubbled into a chloroform solution of 0,0-diphenyl-Calculated: Found: N-phosphonomethylglycinonitrile (3.0 g, 10 mol). The solution was allowed to stand overnight as the hydrobromide crystallized. The crystals were collected and washed with ether to give 3.0 g, 78% yield, identified as the hydrogen bromide salt of 0,0-diphenyl-N-phosphonomethylglycinonitrile by the following analysis.
C 47,0, H 4,2, N 7,3, C 47,1, H 4,3, N 7,4.C 47.0, H 4.2, N 7.3, C 47.1, H 4.3, N 7.4.
ExemEel 30 En 57%-ig lösning av jodvätesyra (2 ml) sattes till en kloroformlösning av Beräknat: Funnet: 0,0-difenyl-N-fosfonometylglycinonitril (3,0 g, 10 mol). Lösningen blev grumlig och fick en gyllene färg. Efter 2 timmar hade ingen fast substans bildats, varför eter tillsattes till grumlingspunkten och kristallisation började. Lösningen ornrördes ytterligare l timme, och den fasta substansen identifierad som hydrojodidsaltet av 0,0-difenyl-N-fosfonometylglycinonitril, uppsamlades som ljusgula plattor, smältpunkt l63-l64°C, 2,4 g, 5696 utbyte. Saltet hade följande analys. 7713047-4 l4 Beräknat: C 41,9, H 3,8, I 29,5, C 41,8, H 3,8, I 29,3.Example 30 A 57% solution of hydroiodic acid (2 ml) was added to a chloroform solution of Calculated: Found: 0,0-diphenyl-N-phosphonomethylglycinonitrile (3.0 g, 10 mol). The solution became cloudy and took on a golden color. After 2 hours no solid had formed, so ether was added to the cloud point and crystallization began. The solution was stirred for an additional 1 hour, and the solid identified as the hydroiodide salt of 0,0-diphenyl-N-phosphonomethylglycinonitrile was collected as pale yellow plates, mp 163-164 ° C, 2.4 g, 5696 yield. The salt had the following analysis. 7713047-4 14 Calculated: C 41.9, H 3.8, I 29.5, C 41.8, H 3.8, I 29.3.
ExemEel 31 Trifluorättiksyra (l,l4 g, 10 mol) sattes till en kloroformlösning av 0,0- Funnet: difenyl-N-fosfonometylglycinonitril (3,0 g, 10 mol). Lösningen ornrördes under natten och lösningsmedlet avdunstades i vakuum, vilket kvarlämnade en ljusgul olja, 4,0 g, 9696 utbyte, nzj = 1,5l72, identifierad som trifluorättiksyrasaltet av D QO-difenyl-N-fosfonometylglycinonitril.Example 31 Trifluoroacetic acid (1.4 g, 10 mol) was added to a chloroform solution of 0.0- Found: diphenyl-N-phosphonomethylglycinonitrile (3.0 g, 10 mol). The solution was stirred overnight and the solvent was evaporated in vacuo to give a pale yellow oil, 4.0 g, 9696 yield, nz = 1.5172, identified as the trifluoroacetic acid salt of D QO-diphenyl-N-phosphonomethylglycinonitrile.
ExemEel 320 Trlfluormetansulfonsyra (l,50 g, 10 mol, finfördelad) sattes till en kloroformlösníng av Oß-difenyl-N-fosfonometylglycinonitril (3,0 g, 10 mol).Example 320 Trifluoromethanesulfonic acid (1.50 g, 10 mol, triturated) was added to a chloroform solution of Oβ-diphenyl-N-phosphonomethylglycinonitrile (3.0 g, 10 mol).
Reaktionsblandningen omrördes vid rumstemperatur under 2 timmar, och eter tillsattes till grumlingspunkten. Produkten kristalliserade. Efter att ha fått stå under I timme, uppsamlades den fasta substansen och tvättades med kloroform- eter (5096), vilket gav 3,8 g, 8496 utbyte, smältpunkt ll9-l20°C, identifierat som trifluormetansiilfonsyrasaltet av 0,0-difenyl-N-fosfonomet-ylglycinonitril med följande analys.The reaction mixture was stirred at room temperature for 2 hours, and ether was added to the cloud point. The product crystallized. After standing for 1 hour, the solid was collected and washed with chloroform ether (5096) to give 3.8 g, 8496 yield, mp 119-120 ° C, identified as the trifluoromethanesulfonic acid salt of 0,0-diphenyl- N-phosphonomethyl-ylglycinonitrile by the following assay.
C 42,5, H 3,6, N 6,2, C 42,7, H 3,5, N 6,2. _ Exemgel 33 Till en kloroformlösning av 0,0-dlfenyl-N-fosfonometylglycinonitril Beräknat: Funnet: (l5,1 g, 0,05 mol) sattes metansulfonsyra (5,0 g, 0,051 mol), och lösningen omrördes under 2 timmar vid omgivningstemperatur. En fast substans föll ut och uppsamlades, tvättades med eter samt tørkades. Den fasta substansen vägde ,90 g och identifierades som metansulfonsyrasaltet av QO-difenyl-N-fosfono- metylglycinonitril med en smältpunkt av l47-l50°C. Utbytet av saltet var 82,196.C 42.5, H 3.6, N 6.2, C 42.7, H 3.5, N 6.2. Example 33 To a chloroform solution of 0,0-diphenyl-N-phosphonomethylglycinonitrile Calculated: Found: (1.5.1 g, 0.05 mol) was added methanesulfonic acid (5.0 g, 0.051 mol), and the solution was stirred for 2 hours at ambient temperature. A solid precipitated and was collected, washed with ether and dried. The solid weighed 90 g and was identified as the methanesulfonic acid salt of QO-diphenyl-N-phosphonomethylglycinonitrile, m.p. 147-150 ° C. The yield of the salt was 82,196.
Saltet hade följande analys. ' Beräknat: C 44,2, H 4,0, N 6,5, S 7,4, Funnet: C 44,0, H 4,0, N 6,6, S 7,5.The salt had the following analysis. Calculated: C 44.2, H 4.0, N 6.5, S 7.4, Found: C 44.0, H 4.0, N 6.6, S 7.5.
ExemEel 34 En eterlösning (10 ml) av salpetersyra (70 vikt-96, 0,9 g, 0,01 mol) sattes till en kloroformlösning (100 ml) innehållande 0,0-difenyl-N-fosfonometyl- glycinonitril (3,0 g, 0,01 mol). Ingen grumling skedde. Ytterligare dietyleter tillsattes, och sedan isooktan (20 ml), varvid fast substans började kristallisera ur lösningen. Blandningen omrördes under I timme vid omgivningstemperatur, och kristallerna uppsamlades, tvättades med kloroform och lufttorkades. Kristallerna vägde 2,66 g och identifierades som salpetersyrasaltet av 0,0-dífenyl-N- fosfonometylglycinonitril med en smältpunkt av ll6-ll6,5°C. Utbytet var 72% av det teoretiska. Saltet hade följande analys. f» r (Ilir- 7713047-4 Beräknat: C 49,32, H 4,42, N 11,5, C 49,2, H 14,42, N 11,5.Example 34 An ether solution (10 ml) of nitric acid (70 wt-96, 0.9 g, 0.01 mol) was added to a chloroform solution (100 ml) containing 0,0-diphenyl-N-phosphonomethylglycinonitrile (3.0 g, 0.01 mol). No turbidity occurred. Additional diethyl ether was added, and then isooctane (20 ml), whereupon solid began to crystallize from solution. The mixture was stirred for 1 hour at ambient temperature, and the crystals were collected, washed with chloroform and air dried. The crystals weighed 2.66 g and were identified as the nitric acid salt of 0,0-diphenyl-N-phosphonomethylglycinonitrile having a melting point of 166-166 ° C. The yield was 72% of theory. The salt had the following analysis. Calcd: C 49.32, H 4.42, N 11.5, C 49.2, H 14.42, N 11.5.
Exemgel 35 Till en lösning av (LO-difenyl-N-fosfonometylglycinonitríl (3,0 g, 0,01 Funnet: mol) i kloroform (100 ml) sattes en eterlösning av 9896 svavelsyra (1,0l g, 0,01 mol). Ytterligare kloroform tillsattes, och blandningen omrördes under 2 timmar.To a solution of (LO-diphenyl-N-phosphonomethylglycinonitrile (3.0 g, 0.01 Found: mol) in chloroform (100 ml) was added an ethereal solution of 9896 sulfuric acid (1.0 g, 0.01 mol) Additional chloroform was added, and the mixture was stirred for 2 hours.
Den fasta substansen avlägsnades genom filtrering och tvättades med kloroform, sedan eter samt torkades, vilket gav 3,9 g av ett material identifierat som svavelsyrasaltet av 0,0-difenyl-N-fosfonometylglycinonitril med en smältpunkt av l5l-l5l,5°C. Saltet erhölls i l0096-igt utbyte och hade följande analys.The solid was removed by filtration and washed with chloroform, then ether and dried to give 3.9 g of a material identified as the sulfuric acid salt of 0,0-diphenyl-N-phosphonomethylglycinonitrile, m.p. 115-115.5 ° C. The salt was obtained in l0096 exchange and had the following analysis.
C 45,0, H 4,28, S 8,01, c 44,90, H 4,27, s 2,05.C 45.0, H 4.28, S 8.01, C 44.90, H 4.27, s 2.05.
ExemEel 36 En eterlösning av fosforsyra (0,01 mol) sattes till en kloroformlösning av Beräknat: Funnet: 0,0-difenyl-N-fosfonometylglycinonitril (3,0 g, 0,01 mol) vid omgivningstempe- ratur under omrörning. Lösningen blev genast grumlig. En olja fanns i bottnen av kolven. Efter kylning avdekanterades lösningsmedlet, indunstades till torrhet och torkades över vatteníritt magnesiumsulfat. Det fasta materialet identifierades som tosforsyrasaltet av 0,0-difenyl-N-fosfonometylglycinonitril med en smält- punkt av 7l+,5-78,5°C. Saltet erhölls i 2596-igt utbyte och hade följande analys.Example 36 An ether solution of phosphoric acid (0.01 mol) was added to a chloroform solution of Calculated: Found: 0.0-diphenyl-N-phosphonomethylglycinonitrile (3.0 g, 0.01 mol) at ambient temperature with stirring. The solution immediately became cloudy. An oil was in the bottom of the flask. After cooling, the solvent was decanted off, evaporated to dryness and dried over anhydrous magnesium sulfate. The solid was identified as the phosphoric acid salt of 0,0-diphenyl-N-phosphonomethylglycinonitrile having a melting point of 71 +, 5-78.5 ° C. The salt was obtained in 2596 yield and had the following analysis.
C 115,0, H 14,5, N 7,0 C 44,8, H 4,6, N 7,1.C 115.0, H 14.5, N 7.0 C 44.8, H 4.6, N 7.1.
ExemEel 37 En heterogen lösning av 0,0-difenyl-N-fosfonometylglycinonitril (60,l+ g, 0,2 mol) i etanol (500 ml) kyldes i ett isbad, och torr HCl bubblades igenom.Example 37 A heterogeneous solution of 0,0-diphenyl-N-phosphonomethylglycinonitrile (60.1 + g, 0.2 mol) in ethanol (500 ml) was cooled in an ice bath, and dry HCl was bubbled through.
Lösningen fick stå, etyleter tillsattes, och en vit fast substans uppsamlades Beräknat: Funnet: genom sugfiltrering. Mer vit fast substans bildades genom bubbling av torr HCl genom etanol-eter-moderluten vid ca OOC, och den uppsamlades och tvättades med eter. Utbytet var 62,7 g, (93%) av hydrokloridsaltet av 0,0-difenyl-N- - fosfonometylglycinonitril, smältpunkt ll2-l23°C. Saltet hade följande analys.The solution was allowed to stand, ethyl ether was added, and a white solid was collected Calculated: Found: by suction filtration. More white solid formed by bubbling dry HCl through ethanol-ether mother liquor at about 0 ° C, and it was collected and washed with ether. The yield was 62.7 g, (93%) of the hydrochloride salt of 0,0-diphenyl-N- - phosphonomethylglycinonitrile, m.p. The salt had the following analysis.
C 53,19, H 4,79, N 8,27 C 53,51, H 4,78, N 8,30.C 53.19, H 4.79, N 8.27, C 53.51, H 4.78, N 8.30.
Exemgel 38 Di(2,4,6-trlmetylfenyDfosfit (17,8 g, 0,05 mol) sattes till en acetonitril- lösning (50 ml) av 1,3,S-tricyanometyl-hexahydro-1,3,5-triazin (3,4 g, 0,0l6l+ Beräknat: F unnet: mol), och blandningen upphettades till 80°C under 18 timmar. Den svarta lösning som bildades filtrerades och koncentrerades till en olja. En portion (7 g) kromatograíerades över silikagel (450 g) med 70% cyklohexan/3096 etylacetat (fraktioner om 60 ml), vilket gav l,0g (14%) 0,0-di(2,4,6-trimetylfenyU-N- _-__....._...__..._._...._._.._...._.. . 7713047-4 16 fosfonometylglycinonitril, smäitpunkt l18-120°C, i fraktionerna 28-40, som kristalliserade efter att ha fått stå. Produkten hade följande analys.Example 38 Di (2,4,6-trimethylphenyl) phosphite (17.8 g, 0.05 mol) was added to an acetonitrile solution (50 ml) of 1,3,5-tricyanomethyl-hexahydro-1,3,5-triazine (3.4 g, 0,016l + Calculated: Found: mol), and the mixture was heated to 80 ° C for 18 hours, the black solution formed was filtered and concentrated to an oil, a portion (7 g) was chromatographed on silica gel ( 450 g) with 70% cyclohexane / 3096 ethyl acetate (60 ml fractions) to give 1.0 g (14%) of 0,0-di (2,4,6-trimethylphenyl-N- _...__..._._...._._.._...._ ... 7713047-4 16 phosphonomethylglycinonitrile, melting point l18-120 ° C, in fractions 28-40, which crystallized after standing.The product had the following analysis.
C 65,27, H 7,04, N 7,25 C 65,38, H 7,07, N 7,18.C 65.27, H 7.04, N 7.25, C 65.38, H 7.07, N 7.18.
Exempel 39 En lösning av diesterprodukten från Exempel 3 (0,025 mol) i våt aceton (50 ml) upphettades vid âterflödestemperatur under 2 timmar och fick sedan stå vid omgivningstemperatur under 5 dagar. Suspensionen filttrerades, vilket gav en oren rosaaktig fast substans (0,9 g). Fíltratet placerades i en kolv med propp och Beräknat: Funnet: fick stå vid omgivningstemperatur under ytterligare 30 dagar. Den resulterande susperisionen filtrerades, och den fasta substansen tvättades med aceton (50 ml).Example 39 A solution of the diester product of Example 3 (0.025 mol) in wet acetone (50 ml) was heated at reflux temperature for 2 hours and then allowed to stand at ambient temperature for 5 days. The suspension was filtered to give a crude pinkish solid (0.9 g). The filtrate was placed in a stoppered flask and Calculated: Found: allowed to stand at ambient temperature for a further 30 days. The resulting suspension was filtered, and the solid was washed with acetone (50 ml).
Man fick 4,5 g (66%) 0-p-metyltio-N-fosfonometylglycinonitril som en vit fast substans, smältpunkt 250-253°C (sönderdelning). Produkten hade följande analys.4.5 g (66%) of O-p-methylthio-N-phosphonomethylglycinonitrile were obtained as a white solid, m.p. 250-253 ° C (dec.). The product had the following analysis.
C 44,12, H 4,81, N 10,29 C 44,26, H 4,86, N 10,22 Exempel 40 Difenyltiofosfit (8,2 g, 0,0246 mol) och l,3,5-tricyanometylhexahydro- Beräknat: Funnet: 1 1,3,5-triazin (l,68 g, 0,00823 mol) löstes i acetonitril (50 ml) och upphettades till 6OI-65OC under 2 timmar. Den resulterande oljan kromatograferades över silikagel (450 g) elueradmed 60% cyklohexan/ 40% etylacetat (fraktioner om 60 ml), vilket gav 1,6 g (20%)av 0,0-difeny1-N-tiofosfonometylglycinonitril, nâj = 1,5847,. i fraktion 30. Produkten hade följande analys. c 56,60, H 4,75, N 8,80, s 10,07 C 56,40, H 4,80, N 8,73, S 10,25.C 44.12, H 4.81, N 10.29 C 44.26, H 4.86, N 10.22 Example 40 Diphenylthiophosphite (8.2 g, 0.0246 mol) and 1,3,5-tricyanomethylhexahydro Calculated: Found: 1 1,3,5-triazine (1.88 g, 0.00823 mol) was dissolved in acetonitrile (50 ml) and heated to 60 DEG-65 DEG C. for 2 hours. The resulting oil was chromatographed on silica gel (450 g) eluting with 60% cyclohexane / 40% ethyl acetate (60 ml fractions) to give 1.6 g (20%) of 0,0-diphenyl-N-thiophosphonomethylglycinonitrile, n 5847 ,. in fraction 30. The product had the following analysis. c 56.60, H 4.75, N 8.80, s 10.07 C 56.40, H 4.80, N 8.73, S 10.25.
Exempel 41 En acetonitril-lösning (100 ml) av di(ß-nafty1)fosfit (33,5 g, 0,1 mol) och l,3,5-trícyanometyl-hexahydro-1,3,5-triazin (20,4 g, 0,1 mol) upphettades till âterflöde underyl timme och koncentrerades sedan till en rödbrun olja. Ett 10 Beräknat: Funnet: grams prov renades genom högtrycksvätskekromatografi över silikagel, varvid man eluerade med 6096 cyk1ohexan/4096 etylacetat (fraktioner om 20 ml). Frak- tionerna 45-64 slogs samman och koncentrerades, och den resulterande oljan kristailiserades ur koltetraklorid, vilket gav 1,1 g 0,0~di(ß-naftyD-N-fosfono- metylglycinonitril som en mattgul färgad fast substans, srnältpunkt 104-105°C.Example 41 An acetonitrile solution (100 ml) of di (β-naphthyl) phosphite (33.5 g, 0.1 mol) and 1,3,5-tricyanomethyl-hexahydro-1,3,5-triazine (20, 4 g, 0.1 mol) was heated to reflux for underyl hour and then concentrated to a red-brown oil. A Calculated: Found: gram sample was purified by high pressure liquid chromatography over silica gel, eluting with 6096 cyclohexane / 4096 ethyl acetate (20 ml fractions). Fractions 45-64 were combined and concentrated, and the resulting oil was crystallized from carbon tetrachloride to give 1.1 g of 0,0-di (β-naphthyD-N-phosphonomethylglycinonitrile as a pale yellow solid, m.p. 105 ° C.
Produkten gav följande analys.The product gave the following analysis.
C 68,65, H 4,76, N 6,96 C 68,58, H 4,79, N 6,92 Exempel 42 En omrörd lösning av di(3,4-metylendioxifenyDfosfit (0,05 mol) och i,3,5- trícyanometyl-hexahydro-l,3,5-triazin (0,0l67 mol) i acetonitril (75 ml) upp- Beräknat: Funnet: Mj) '15 7713047-4- 17 hettades till 75°C under 3 timmar och fick sedan stå vid omgivningsternperatur under natten. Den resulterande lösningen koncentrerades till en bärnstensfärgad olja. Till en kloroformlösning (100 ml) av oljan (7,6 g, 0,02 mol), sattes metansulfonsyra (l,92 g, 0,02 mol) droppvis. Efter omrörning under 15 minuter tillsattes eter (200 ml), och en vit fast substans föll ut. Den fasta substansen omkristalliserades tvâ gånger ur aceton, vilket gav 4,6 g (47%) av metansulíon- syrasaltet av 0,0-di(3,4-metylendioxiíenyU-N-fosfonometylglycinonitril, smält- punkt l35-l36,5°C. Produkten hade följande analys.C 68.65, H 4.76, N 6.96 C 68.58, H 4.79, N 6.92 Example 42 A stirred solution of di (3,4-methylenedioxyphenylphosphite (0.05 mol) and i, 3,5-Tricycanomethyl-hexahydro-1,3,5-triazine (0.0l67 mol) in acetonitrile (75 ml) was calculated to be heated to 75 ° C for 3 hours. and then allowed to stand at ambient temperature overnight. The resulting solution was concentrated to an amber oil. To a chloroform solution (100 mL) of the oil (7.6 g, 0.02 mol) was added methanesulfonic acid (1.92 g, 0.02 mol) dropwise. After stirring for 15 minutes, ether (200 ml) was added and a white solid precipitated. The solid was recrystallized twice from acetone to give 4.6 g (47%) of the methanesulic acid salt of 0,0-di (3,4-methylenedioxyenyl) -N-phosphonomethylglycinonitrile, m.p. The product had the following analysis.
Beräknat: c 44,45, H 3,94, N 5,76 runner; c 44,26, H 3,94, N 5,71.Calculated: c 44.45, H 3.94, N 5.76 runner; c 44.26, H 3.94, N 5.71.
ExemEel 43 En lösning av 0,01 mol av den bärnstensfärgade oljan i Exempel 42 i våt aceton (70 ml) återloppskokades under 4 dagar. Den bärnstensfärgade lösningen fick sedan stå under en dag vid omgivningstemperatur. Den resulterande suspenslonen flltrerades, vilket gav 1,7 g O-(3,4-metylendioxifenyI)-N-íosfono- metylglycinonitril som en vit fast substans, smältpxlnkt l60-l6l°C.Example 43 A solution of 0.01 mol of the amber oil of Example 42 in wet acetone (70 ml) was refluxed for 4 days. The amber solution was then allowed to stand for one day at ambient temperature. The resulting suspension was filtered to give 1.7 g of O- (3,4-methylenedioxyphenyl) -N-isphonomethylglycinonitrile as a white solid, m.p. 160-161 ° C.
ExemEel 44 En omrörd lösning av di(3,4-diklorfenyl)fosfit (0,04 mol) och l,3,5- tricyanometyl-hexahydro-l,3,5-triazin (0,0l3 mol) i acetonitril (40 ml) upphetta- des till 30°C och hölls så under 18 timmar. Den resulterande lösningen koncent- rerades till en olja, våt aceton (80 ml) tillsattes, och blandningen återloppskoka- des under 80 timmar. Den resulterande suspensionen filtrerades, vilket gav en vit fast substans, som tvättades med aceton (50 ml) för att ge 6,3 g (53%) O-(3,4- diklorfenyU-N-fosfonometylglycinonitril, smältpunkt l69-l70°C.Example 44 A stirred solution of di (3,4-dichlorophenyl) phosphite (0.04 mol) and 1,3,5-tricyanomethyl-hexahydro-1,3,5-triazine (0.013 mol) in acetonitrile (40 ml ) was heated to 30 ° C and kept for 18 hours. The resulting solution was concentrated to an oil, wet acetone (80 ml) was added, and the mixture was refluxed for 80 hours. The resulting suspension was filtered to give a white solid, which was washed with acetone (50 ml) to give 6.3 g (53%) of O- (3,4-dichlorophenyl-N-phosphonomethylglycinonitrile, m.p. 169-170 ° C .
ExemEel 45 ' Difenylíosíit (234 g, 1,0 mol) sattes till en acetonitril-lösning (300 ml) av l,3,5-tricyanometyl-hexahydro-l,3,5-triazin (68 g, 0,333 mol) och upphettades vid 75-82°C under 3 timmar. Lösningen kyldes och koncentrerades i vakuum, vilket gav en svart olja, som huvudsakligen var produkten i Exempel 5. Ett prov av denna olja (101 g) fästes på silikagel (som var löst i kloroform, mer silikagel tillsattes och lösningsmedlet indunstades), och detta material kromatograíerades över silikagel (1,1 kg) eluerad med kloroform (l-liters-fraktioner). Fraktionerna 13-14 slogs samman, koncentrerades och omkristalliserades ur diklormetan~ cyklohexan, vilket gav 51 g 0,0-diienyl-N-fosfonometylglycinonítril.Example 45 'Diphenyliosite (234 g, 1.0 mol) was added to an acetonitrile solution (300 ml) of 1,3,5-tricyanomethyl-hexahydro-1,3,5-triazine (68 g, 0.333 mol) and heated at 75-82 ° C for 3 hours. The solution was cooled and concentrated in vacuo to give a black oil which was essentially the product of Example 5. A sample of this oil (101 g) was attached to silica gel (which was dissolved in chloroform, more silica gel was added and the solvent was evaporated), and this material was chromatographed on silica gel (1.1 kg) eluting with chloroform (1 liter fractions). Fractions 13-14 were combined, concentrated and recrystallized from dichloromethane-cyclohexane to give 51 g of 0,0-diienyl-N-phosphonomethylglycinonitrile.
ExemEel 46 Difenylfosfit (33,43 g, 0,1 mol, 7096 ren) och l,3,5-tricyanometyl- hexahydro-l,3,5-triazin (6,73 g, 0,033 mol) omrördes i en kolv och upphettades till 100°C (med ett oljebad). Efter 40 minuter var reaktionen fullständig (NMR- 7713047-4 18 analys). Den råa reaktionsblandningen hydrolyserades genom att man tillsatte 150 ml 2N HC! och âterloppskokade under 16 timmar. Det erhållna materialet extraherades med kloroform (för avlägsning av fenolen) två gånger, och de vattenhaltiga skikten filtrerades och indunstades till torrhetför att ge en brun orange fast substans, som löstes i 60 ml vatten och kyldes till OOC. De resulterande kristallerna uppsamlades och lufttorkades, vilket gav 10,7g N- fosfonometylglycin. Analys-95+% rent. Ytterligare omgångar isolerades genom indunstning och tillsats av etanol. Alla dessa material innehöll varierande mängder ammoniumklorid och aminometylfosfonsyra. Moderlutarna från de ovanstående kristallisationerna innehöll huvudsakligen fosíorsyra (4,4 g). i Exempel 47 i ' Di(p-metoxifenyl)fosfit 00,82 g, 0,1 mol, 95,596 ren)'och 1,3,5-tricayno- metyl-hexahydro-l,3,5-triazin (6,81 g, 0,0333 mol) blandades, omrördes och upphettades till l00°C. Efter 15 minuter hade all hexahydrotriazin lösts i fosfiten; en alikvot indikerade att reaktionen var ungefär 50% fullständig.Example 46 Diphenyl phosphite (33.43 g, 0.1 mol, 7096 pure) and 1,3,5-tricyanomethylhexahydro-1,3,5-triazine (6.73 g, 0.033 mol) were stirred in a flask and heated to 100 ° C (with an oil bath). After 40 minutes the reaction was complete (NMR analysis). The crude reaction mixture was hydrolyzed by adding 150 ml of 2N HCl! and refluxed for 16 hours. The resulting material was extracted with chloroform (to remove the phenol) twice, and the aqueous layers were filtered and evaporated to dryness to give a brown orange solid, which was dissolved in 60 ml of water and cooled to 0 ° C. The resulting crystals were collected and air dried to give 10.7 g of N-phosphonomethylglycine. Analysis-95 +% pure. Additional batches were isolated by evaporation and addition of ethanol. All of these materials contained varying amounts of ammonium chloride and aminomethylphosphonic acid. The mother liquors from the above crystallizations contained mainly fossil acid (4.4 g). in Example 47 in 'Di (p-methoxyphenyl) phosphite 00.82 g, 0.1 mol, 95.596 pure)' and 1,3,5-tricaynomethyl-hexahydro-1,3,5-triazine (6.81 g, 0.0333 mol) were mixed, stirred and heated to 100 ° C. After 15 minutes, all of the hexahydrotriazine had dissolved in the phosphite; an aliquot indicated that the reaction was approximately 50% complete.
Blandningen upphettades under ytterligare. l5_wminuter och hydrolyserades sedan och upparbetades som beskrivits i Exempel 46. NMR för den första omgången ,1 g (torr) indikerar ren N-fosfonometylglycin. Inga andra omgångar kunde erhållas i ren form. NMR för moderluten indikerar en komplex blandning.The mixture was further heated. 15 minutes and then hydrolyzed and worked up as described in Example 46. NMR for the first batch, 1 g (dry) indicates pure N-phosphonomethylglycine. No other rounds could be obtained in pure form. NMR for the mother liquor indicates a complex mixture.
Exempel 48 Di-p-klorfenylfosfit (19,6 g, 0,05 mol, 78% ren) och l,3,5-tricyanometyl- hexahydro«1,3,5-triazin (3,41 g, 0,0167 mol) blandades vid rumstemperatur (ingen exoterm). Uppslamningen upphettades till 100°C under 20 minuter (NMR utförd på en alikvot indikerade att reaktionen var fullständig). Efter upparbetnings- och hydrolysförfaranden beskrivna i Exempel 46 isolerades 4,8 g N-fosfonometyl- glycín (första omgång 56%). Den andra omgången om 0,44 g var NHALCI. NMR- analyser av moderlutarna var mycket komplexa, vilket indikerade att hydrolys- betingelserna var för stränga för optimala utbyten.Example 48 Di-p-chlorophenyl phosphite (19.6 g, 0.05 mol, 78% pure) and 1,3,5-tricyanomethylhexahydro-1,3,5-triazine (3.41 g, 0.0167 mol ) was mixed at room temperature (no exotherm). The slurry was heated to 100 ° C for 20 minutes (NMR performed on an aliquot indicated that the reaction was complete). Following the work-up and hydrolysis procedures described in Example 46, 4.8 g of N-phosphonomethylglycine (first batch 56%) were isolated. The second batch of 0.44 g was NHALCI. NMR analyzes of the mother liquors were very complex, which indicated that the hydrolysis conditions were too strict for optimal yields.
Exempel 49 - Tetrametylammoniumhydroxidsaltet av N-fosíonometylglycin framställ- des genom att man löste 6 g (0,02 mol) QO-difenyl-N-fosfonometylglycinonitril i ml vatten innehållande 14,5 g (0,08 mol) tetrametylammoniumhydroxid och sedan 'upphettade blandningen under 16 timmar vid l00°C tills NMR-spektral- analys indikerade att all glycinonitrilen hade omsatts till tetrametylammonium- hydroxidsaltet av N-fosfonometylglycin. Lösningen kyldes och extraherades med metylenklorid för avlägsning av fenolen och vakuumkoncentrerades sedan, vilket gav en blandning av tetrametylammoniumsalterna. Den utvunna saltprodukten löstes i 20 rnl vatten och placerades i en jonbyturlcolorin packad mod ett kommersiellt katjonbytarharts ("Dowex 50") och eluerades sedan med vatten vid »w Lita , 7713047-4 19 rumstemperatur. Eluatet koncentrerades, vilket gav 2,4 g av en beigefärgad kristallin fast substans (7196 utbyte). Den kristallina fasta substansen befanns genom NMR-spektrumanalys vara väsentligen ren N-fosfonometylglycin.Example 49 - The tetramethylammonium hydroxide salt of N-phosonomethylglycine was prepared by dissolving 6 g (0.02 mol) of QO-diphenyl-N-phosphonomethylglycinonitrile in ml of water containing 14.5 g (0.08 mol) of tetramethylammonium hydroxide and then heating the mixture. for 16 hours at 100 ° C until NMR spectral analysis indicated that all the glycinonitrile had been converted to the tetramethylammonium hydroxide salt of N-phosphonomethylglycine. The solution was cooled and extracted with methylene chloride to remove the phenol and then vacuum concentrated to give a mixture of the tetramethylammonium salts. The recovered salt product was dissolved in 20 ml of water and placed in an ion exchange culture packed against a commercial cation exchange resin ("Dowex 50") and then eluted with water at room temperature, 7713047-4 19 room temperature. The eluate was concentrated to give 2.4 g of a beige crystalline solid (7196 yield). The crystalline solid was found by NMR spectrum analysis to be substantially pure N-phosphonomethylglycine.
Exempel 50 Dinatriumsaltet av N-fosfonometylglycin framställdes genom blandning av 6,04 g (0,02 mol) 0,0-difenyl-N-fosfonometylglycinonitril med 50 ml vatten innehållande 3,2 g (0,08 mol) natriumhydroxid och sedan upphettning av bland- ningen under kontinuerlig omrörning under l timme vid 70°C, vid vilken tidpunkt NMR-spektrumanalys av reaktionsblandningen indikerade att ca 1/3 av reaktions- blandningen hade omsatts till dinatriumsaltet. Fortsättning av reaktionen under ytterligare 4 timmar vid 70°C indikerade genom NMR-spektrumanalys en 4096-ig omsättning till dinatriumsaltet. Ytterligare upphettning under D15 timmar till 70°C resulterade i en 80 till 9096-ig omsättning till dinatriumsaltet. Reaktions- produkten koncentrerades sedan för att ge en mörkt bärnstensfärgad glasliknande fast substans. N-fosfonometylglycin framställdes genom upplösning av den fasta substansen i vatten och satsning av lösningen i en jonbytarkolonn packad med ett kommersiellt katjonbytarharts ("Dowex 50"). Kolonnen eluerades med vatten vid rumstemperatur. Eluatet koncentrerades för att ge 2,7 g (8096 utbyte) av en ljust färgad fast substans, som enligt NMR-spektrumanalys var väsentligen ren N- fosfonometylglycin.Example 50 The disodium salt of N-phosphonomethylglycine was prepared by mixing 6.04 g (0.02 mol) of 0,0-diphenyl-N-phosphonomethylglycinonitrile with 50 ml of water containing 3.2 g (0.08 mol) of sodium hydroxide and then heating the mixture with continuous stirring for 1 hour at 70 ° C, at which time NMR spectrum analysis of the reaction mixture indicated that about 1/3 of the reaction mixture had been converted to the disodium salt. Continuation of the reaction for an additional 4 hours at 70 ° C indicated by NMR spectrum analysis a 4096-g reaction to the disodium salt. Further heating for D15 hours to 70 ° C resulted in an 80 to 9096% conversion to the disodium salt. The reaction product was then concentrated to give a dark amber glass-like solid. N-phosphonomethylglycine was prepared by dissolving the solid in water and loading the solution into an ion exchange column packed with a commercial cation exchange resin ("Dowex 50"). The column was eluted with water at room temperature. The eluate was concentrated to give 2.7 g (8096 yield) of a light colored solid, which according to NMR spectrum analysis was essentially pure N-phosphonomethylglycine.
Exempel 51 Den herbicida aktiviteten efter uppkomst hos olika föreningar enligt uppfinningen demonstreras som följer. De aktiva ingredienserna appliceras i sprayform på' lll-Zl dagar gamla exemplar av olika växtarter. Sprayen, en vattenlösning eller organiskt lösningsmedel/vatten-lösning innehållande aktiv ingrediens och ett ytaktivt ämne (35 delar butylaminsalt av dodecylbensen- sulfonsyra och 65 delar tallolja kondenserad med etylenoxid i förhållandet ll moler etylenoxid per l moi tallolja) appliceras på plantorna i olika satser av trâg i olika doser (kg per hektar) aktiv ingrediens. De behandlade plantorna placeras i ett växthus och verkningarna observeras och registreras efter ca 2 veckor eller ca ll veckor. Värdena anges i Tabellerna I och II. _ Det index för herbicid aktivitet efter uppkomst som används i Tabellerna I och Il är som följer: 7713047-4 Plantsvar _I_n_d5>¿ 0-2496 skada 0 -4996 skada I 50-7496 skada 2 75-9996 skada 3 i' Alla dödade l: Arter som inte var x närvarande vid behandlingstidpunkten I dessa tabeller anger WAT veckor efter behandling (weeks after treatment) óch plantarterna som behandlats representeras var och en av en kodbokstav enligt följande: A - Kanadatistel (Cirsium arvense) K - Hönshirs (Echinochloa crusgalli) B - Tistelskräppa (Xanthium) L - Sojaböna (Glycine max) C -Indisk malva (Cissampelos pareira) M - Sockerbeta D - Blomman för dagen (Ipomoea) N - Vete E - Vägmâlla (Chenopodium album) O - Ris_ 'F - Bitterpilört (Polygonum) P - Durra G - "Nutsedge" (Cyperus) Q - Vilt bovete (Erigonum) H - Kvickrot (Agropyron repens) R - Sesbaniahampa I - Ogräsdurra (Sorghum halepense) S - Panicum Spp II - Luddlosta (Bromus tectorum) T - Blodhirs (Digítaria) .W , -.,.- _..._.._.__.._._..._...._._,..,._-.Example 51 The herbicidal activity after emergence of various compounds of the invention is demonstrated as follows. The active ingredients are applied in spray form to'll-Zl days old specimens of various plant species. The spray, an aqueous solution or organic solvent / water solution containing active ingredient and a surfactant (35 parts of butylamine salt of dodecylbenzenesulfonic acid and 65 parts of tall oil condensed with ethylene oxide in the ratio of 11 moles of ethylene oxide per 10 moi tall oil) are applied to the plants in different batches of trough in different doses (kg per hectare) active ingredient. The treated plants are placed in a greenhouse and the effects are observed and registered after about 2 weeks or about 11 weeks. The values are given in Tables I and II. The index for herbicidal activity after emergence used in Tables I and II is as follows: 7713047-4 Plant response _I_n_d5> ¿0-2496 damage 0 -4996 damage I 50-7496 damage 2 75-9996 damage 3 in 'All killed l : Species that were not x present at the time of treatment In these tables, WAT indicates weeks after treatment and the plant species treated are each represented by a code letter as follows: A - Canadian thistle (Cirsium arvense) K - Chicken millet (Echinochloa crusgalli) B - Thistle scab (Xanthium) L - Soybean (Glycine max) C -Indian mallow (Cissampelos pareira) M - Sugar beet D - The flower of the day (Ipomoea) N - Wheat E - Vägmâlla (Chenopodium album) O - Ris_ 'F - Bitterpilört ( Polygonum) P - Durra G - "Nutsedge" (Cyperus) Q - Vilt bovete (Erigonum) H - Kvickrot (Agropyron repens) R - Sesbaniahampa I - Ogräsdurra (Sorghum halepense) S - Panicum Spp II - Luddlosta (Bromus tectorum) T - Blodhirs (Digítaria) .W, -., .- _..._.._.__.._._..._...._._, .., ._-.
TABELL I växtarter WAT Förenin 11,2 11,2 21 11,2 4,48 11,2 7715047-4 MNF! f-lNo-l MVQ' v-lv-iv-l r-lNv-l 7713047-4 22 Wfifi 9101M01 r-i WICWWFIMM 51 n-iNr-ífl' mfl-a m Nr-lmm MMNF! flfifl' v *f ¶'§'¶'¶'<'<2'fi'<'<"<' MMNNI-l CÛ¶C fl' fñ '=f¶'m<' MCÛFIQ' fil-ir! 211 ONNH-iN-lmmmmm .m .öf_m~xm> [fl¶'¶'¶' Q-awmøxmme-Nmoxv- N ff! mvmv 73.63 ~ ...Amm/É. @.m ~.~H ~.H~ @«.« Nßfifl wfm ~_HH w,m ~.HH w.m ~.HH w.m ~.HH w.m ~.~H å E43 <3... a ma va ma NH .S ofi m mcmcwhmm TABELL I (forts) växtarter _ IVAT kg/ha Förening 11,2 16 17 11,2 18 7713047-4 23 1. s 11,2 ,6 11,2 , 1, s l? 19 21 22 23 7713047-4 MQ' hv HM :N fà-Ov P -x... :u *å :mf-vw > HQ' A Gm -å -P L.TABLE I plant species WAT Förenin 11.2 11.2 21 11.2 4.48 11.2 7715047-4 MNF! f-lNo-l MVQ 'v-lv-iv-l r-lNv-l 7713047-4 22 W fifi 9101M01 r-i WICWWFIMM 51 n-iNr-í fl' m fl- a m Nr-lmm MMNF! flfifl 'v * f ¶'§'¶'¶' <'<2'fi' <'<"<' MMNNI-l CÛ¶C fl 'fñ' = f¶'m <'MCÛFIQ' fil-ir! 211 ONNH-iN-lmmmmm .m .öf_m ~ xm> [fl¶'¶'¶ 'Q-awmøxmme-Nmoxv- N ff! Mvmv 73.63 ~ ... Amm / É. @ .M ~. ~ H ~ .H ~ @ «.« Nß fifl wfm ~ _HH w, m ~ .HH wm ~ .HH wm ~ .HH wm ~. ~ H å E43 <3 ... a ma va ma NH .S o fi m mcmcwhmm TABLE I (cont.) Plant species IVAT kg / ha Association 11.2 16 17 11.2 18 7713047-4 23 1. s 11.2, 6 11.2, 1, sl? 19 21 22 23 7713047-4 MQ 'hv HM: N fà- Ov P -x ...: u * å: mf-vw> HQ 'A Gm -å -P L.
O få _U~=:~ b-l .J :à m mv < I~ av E”.O få _U ~ =: ~ b-l .J: à m mv <I ~ av E ”.
R Ln .X 53 Sv .E C ü) L.R Ln .X 53 Sv .E C ü) L.
:O LY- 11,2 24 24 11,2, s 11, s 26 27 28 29 F) f"l N v-'l N N N 1-4 F? r-I d' 01 Q' <1' F) N F) F) Vi m F) <7 Öl Ü r- v» I-l Lñ r-l Q' Q' O (Û IJ» r'- TABELL I (forts) växtarter :al *ul HI 311 OI ml ml Ql ul :nl <1 WAT k /ha Förenin 31 32 33 \Û (Wi \Û c- c- v f- a-l l-fl r-í IH F! 1-4 34 11,2 36 7713047-4 LÖ 1. -, 1. 37 38 7713047-4 26 Mlmmwvw NNO hl HI mlmm-a wlmmfimm fulvN-im-:r huiflxwß rfllw-Nwvv I-'lr-IPÅWM ffiNl-lflN VMNfiM cl ul ml Aætoë _ jun/ä. »dimma Him ~.AH NJA min.: O LY- 11,2 24 24 11,2, s 11, s 26 27 28 29 F) f "l N v-'l NNN 1-4 F? RI d '01 Q' <1 'F) NF) F) Vi m F) <7 Öl Ü r- v »Il Lñ rl Q 'Q' O (Û IJ» r'- TABLE I (cont.) Plant species: al * ul HI 311 OI ml ml Ql ul: nl <1 WAT k / ha Förenin 31 32 33 \ Û (Wi \ Û c- c- v f- al l- fl r-í IH F! 1-4 34 11,2 36 7713047-4 LÖ 1. -, 1. 37 38 7713047-4 26 Mlmmwvw NNO hl HI mlmm-a wlmm fi mm fulvN-im-: r hui fl xwß r fl lw-Nwvv I-'lr-IPÅWM f fi Nl-l fl N VMN fi M cl ul ml Aætoë _ jun / ä. »DimA min ~. .
NJA å .fifiš Nw av m m mcwcæhmm E-fl m m -| :dl m m f-n ml N w -| hlmf-ao O! m N fi' Iul m N N fzll m N N ctl -| -4 o cI-aflf-c Växtarter mlmma mlmN-u Olm-u-c Zlmfao TABELL II :IINH-a Alu-NA Wxoaæ fif... ana x E+ n! Ewy-vw Förenin l 1.12 0,28 27 1,12 4' 0,28 4 ,6 4 1,12 4 7713047-4 0,28 4,48 Q' M M F? ä' P1 F) r-l M F! M O M N N O N N N v-l N N V1 F) N O r-l v-l v-l O n-i v-i Q' N I-l N ' o" fl' T 7713047-4 TABELL II (fortsJ växtarter BI* :<1 ml bl UI fal NI nå! OI OI ml ml OI Zl El Q! WAT kg/ha FöreÅnln l._l2 0,28 0,056 1,12 1,12 .6 28 w:- N m N <- N N H <- N w:- N q Å» <- N N N -4 --| m N m N m f-a N f-a N '-4 N a m f-l N ' 6 Ü' T 1,12 0,28 4.48 13 01 01 m N <1' ä' N r-l Pl r-i Pl I-{ M F) N r-š N r-l N Pl P3 FI N N N N r-i O N O u-I v-i <1' H 2 ' 6 'W Q' n, , 16%' .NJA å .fifi š Nw av m m mcwcæhmm E-fl m m - | : dl m m f-n ml N w - | hlmf-ao O! m N fi 'Iul m N N fzll m N N ctl - | -4 o cI-a fl f-c Plant species mlmma mlmN-u Olm-u-c Zlmfao TABLE II: IINH-a Alu-NA Wxoaæ fi f ... ana x E + n! Ewy-vw Förenin l 1.12 0.28 27 1.12 4 '0.28 4, 6 4 1.12 4 7713047-4 0.28 4.48 Q' M M F? ä 'P1 F) r-l M F! MOMNNONNN vl NN V1 F) NO rl vl vl O ni vi Q 'N Il N' o "fl 'T 7713047-4 TABLE II (cont. Plant species BI *: <1 ml bl UI fal NI nå! OI OI ml ml OI Zl El Q! WAT kg / ha FöreÅnln l._l2 0,28 0,056 1,12 1,12 .6 28 w: - N m N <- NNH <- N w: - N q Å »<- NNN -4 - | m N m N m fa N fa N '-4 N am fl N' 6 Ü 'T 1.12 0.28 4.48 13 01 01 m N <1' ä 'N rl Pl ri Pl I- {MF) N r-š N rl N Pl P3 FI NNNN ri ONO uI vi <1 'H 2' 6 'WQ' n,, 16% '.
TABELL n (mms) växtarter Efll MI ml bl ul :nl m! m! nl OI ml ml o! zl 2! AI Förenin 14 1,12 1,12 .6 16 1,12 4 0,28 4 29 17 1,12 0,28 18 1,12 7713047-4 19 1.12 0,28 1,12 771so47§4 TABELL II (forts) växtarter BI MI ml *fil uy fal m! mf D] OI ml ml Zl' Zl .JI wm' k /ha in Foren 21 1,12 22 1,12 0,28 23 1,12 MIVQ' OMP! den; Nfffl' GVU' PICÛCÛ r-IWN DNs-l I-IGN 24 N H <- N '-4 v- m o <1- »<1 f-n <1- m N <- m '-1 m N f-i <1- N o 'f-I .-| f-l m N o N .-4 o 'm f-f f-a m H N w --| I I* I m 0.28 26 *f m *f m *f <1' N -4 <1' N <1' N *f N N .-4 N N P4 H N N f" N f" '-4 H -4 F* -4 N f-a N '-4 N .~ _ f-u <1' <.~ växtarter TABELL II (forts) Bl MI ml hl ul ful I-:JI NI DI OI ml ml OI Zl E! 1-1! wzvr k /ha örenin F 1,12 0,28 1,12 0,28 1,12 0,28 1.12 0.29 1.12 0,29 27 28 29 31 TABELL II (forts) Växtarter 7713047-4 E-ßl MI ml bl UI tal m! å! D! m! ml OI Zl El n-Il WAT k /ha Förenin 32 33 0,28 34 32 OI 1Q12 0,29 1,12 0,28 36 1,12 4 0,2a 4 TABELL II (forts) Växtarter BI MI ml n! UI ml tål nål D! Oll ml ml OI Zl Zl Al Förenin 37 1,12 0,28 39 1,12 0,28 42 33 l._l2 0,28 7113047-4 7713047-4 34 Exempel 52 Den herbicida aktiviteten före uppkomst hos olika föreningar enligt uppfinningen demonstreras som följer. Matjord av god kvalitet placeras i aluminiumtråg och packas till ett djup av 9,5 mm till 13 mm från överdelen av varje trâg. Ett förutbestämt antal frön eller vegetativa groddar av var och en av flera växtarter placeras ovanpå jorden i varje trâg och pressas sedan ned. l-lerbicida kompositioner (såsom beskrivits i Exempel 51), som använder de aktiva ingredienserna enligt uppfinningen, appliceras genom blandning med eller införlivande i det översta jordskiktet.TABLE n (mms) plant species E fl l MI ml bl ul: nl m! m! nl OI ml ml o! zl 2! AI Förenin 14 1.12 1.12 .6 16 1.12 4 0.28 4 29 17 1.12 0.28 18 1.12 7713047-4 19 1.12 0.28 1.12 771so47§4 TABLE II (cont. ) plant species BI MI ml * fi l uy fal m! mf D] OI ml ml Zl 'Zl .JI wm' k / ha in Foren 21 1.12 22 1.12 0.28 23 1.12 MIVQ 'OMP! the; Nff fl 'GVU' PICÛCÛ r-IWN DNs-l I-IGN 24 NH <- N '-4 v- mo <1- »<1 fn <1- m N <- m' -1 m N fi <1- N o 'fI .- | f-l m N o N.-4 o'm f-f f-a m H N w - | II * I m 0.28 26 * fm * fm * f <1 'N -4 <1' N <1 'N * f NN.-4 NN P4 HNN f "N f"' -4 H -4 F * -4 N fa N '-4 N. ~ _ Fu <1' <. ~ Plant species TABLE II (cont.) Bl MI ml hl ul ful I-: JI NI DI OI ml ml OI Zl E! 1-1! wzvr k / ha örenin F 1.12 0.28 1.12 0.28 1.12 0.28 1.12 0.29 1.12 0.29 27 28 29 31 TABLE II (cont.) Plant species 7713047-4 E-ßl MI ml bl UI tal m! oh! D! m! ml OI Zl El n-Il WAT k / ha Förenin 32 33 0.28 34 32 OI 1Q12 0.29 1.12 0.28 36 1.12 4 0.2a 4 TABLE II (continued) Plant species BI MI ml n! UI ml can withstand needle D! Oll ml ml OI Zl Zl Al Förenin 37 1.12 0.28 39 1.12 0.28 42 33 l._l2 0.28 7113047-4 7713047-4 34 Example 52 The herbicidal activity before emergence of various compounds according to the invention is demonstrated that follows. Good quality topsoil is placed in aluminum troughs and packed to a depth of 9.5 mm to 13 mm from the top of each trough. A predetermined number of seeds or vegetative sprouts of each of several plant species are placed on top of the soil in each trough and then pressed down. 1-Lerbicidal compositions (as described in Example 51) using the active ingredients of the invention are applied by mixing with or incorporating into the topsoil.
' Vid denna metod skall den jord .som krävs för att täcka fröna och groddarna vägas och blandas med en herbicid komposition, som innehåller en känd mängd aktiv ingrediens. Trâgen fylls sedan med blandningen och jämnas till.In this method, the soil required to cover the seeds and seeds shall be weighed and mixed with a herbicidal composition containing a known amount of active ingredient. The trays are then filled with the mixture and leveled.
Bevattning utförs genom att man låter jorden i trâgen absorbera fuktighet genom öppningar i trågbottnarna. Trâgen som innehåller frön och vegetativa groddar l5 placeras på en våt sandbänk och hålls under ca två veckor under vanliga solljus- och bevattningsbetingelser. Vid slutet av denna period noteras antalet uppkomna plantor av varje art och jämförs med en obehandlad kontroll. Värdena anges i Tabell III. e Det index för herbicid aktivitet före uppkomst som används nedan är baserat på den genomsnittliga kontrollen av varje art enligt följande: Procent kontroll Index 0-2596 0 26-5096 1 51-7596 2 76- 100% 3 Växtarterna är identifierade i Tabell Ill med samma kodbokstäver som användes i Exempel 51.Irrigation is performed by allowing the soil in the troughs to absorb moisture through openings in the trough bottoms. The troughs containing seeds and vegetative sprouts l5 are placed on a wet sand bench and kept for about two weeks under normal sunlight and irrigation conditions. At the end of this period, the number of plants emerging from each species is noted and compared with an untreated control. The values are given in Table III. The pre-emergence herbicidal activity index used below is based on the average control of each species as follows: Percent control Index 0-2596 0 26-5096 1 51-7596 2 76- 100% 3 The plant species are identified in Table III with the same code letters used in Example 51.
TABELL III Växtarter MI UI HI :ål OI m! n: *al m! flïl kg/ha Fören in 11.2 11,2 11.2 11,2 11,2 11,2 11,2 11.2 11.2 11.2 11,2 11 77,130 47- 4 11.2 12 11.2 13 11,2 14 11,2 11,2 16 7713047-4 xl o o c o o hl o_ o o o o HI o o o o o :I o o o c o UI Q o o o o k 3 hl o o o o o ä 'IJ a: ml o o o o o 'T Vi š-l DI o c o o o 3 .TABLE III Plant species MI UI HI: eel OI m! n: * al m! ï ïl kg / ha Fören in 11.2 11.2 11.2 11.2 11.2 11.2 11.2 11.2 11.2 11.2 11.2 11 77,130 47- 4 11.2 12 11.2 13 11.2 14 11.2 11.2 16 7713047 -4 xl oocoo hl o_ oooo HI ooooo: I oooco UI Q ooook 3 hl ooooo ä 'IJ a: ml ooooo' T Vi š-l DI ocooo 3.
E A UI c o o o o A LLl m É ml o o o Q o ml A o A o N m N N N N .C 1- r u~ r a~ \ A A A A A x A A A A A E c a) ß m m O 1-4 ,5 A A- A N N IL _11._2 22 36 o o o o o o o ,o O N N N f |~ n n-l n-l v-I r-l v-I ø-l P7 <1' III N N N 11,2 26 11.2 27 11,2 11,2 28 29 11,2 O O O O O O O O O O O O O O O O O O O O N (Û N N v n r-l 1-4 1-4 r-l Pl N P1 01 J TABELL III (forts) Växtarter :dl UI HI IEI UI Enl BJI DI UI :nl fiïl kg/ha ll Förenin 33 11,2 34 11,2 1112 36 11,2 37 11,2 38 37 11,2 39 11,2 40 11,2 42 7713047-4 7713047-4 38 g Av de i Tabellerna I och Il redovisade testresultaten kan man se att den herbicida aktiviteten efter uppkomst för föreningarna enligt uppfinningen för det mesta är allmän till sin natur. I vissa speciella fall visas emellertid viss selektivitet. Å andra sidan visar testresultaten avseende den herbicida aktivite- ten före uppkomst tydligt selektiviteten för verkan på. kanadatistel och nâgra andra arter. Med hänsyn härtill bör det inses att varje enskild art som valts för de ovanstående testen är en representativ medlem av en erkänd växtart- familj.EA UI coooo A LLl m É ml ooo Q o ml A o A o N m NNNN .C 1- ru ~ ra ~ \ AAAAA x AAAAAE ca) ß mm O 1-4, 5 A A- ANN IL _11._2 22 36 ooooooo, o ONNN f | ~ n nl nl vI rl vI ø-l P7 <1 'III NNN 11,2 26 11.2 27 11,2 11,2 28 29 11,2 OOOOOOOOOOOOOOOOOOOON (Û NN vn rl 1-4 1 -4 rl Pl N P1 01 J TABLE III (cont.) Plant species: dl UI HI IEI UI According to BJI DI UI: nl fi ïl kg / ha ll Förenin 33 11,2 34 11,2 1112 36 11,2 37 11,2 38 37 11.2 39 11.2 40 11.2 42 7713047-4 7713047-4 38 g From the test results reported in Tables I and II it can be seen that the herbicidal activity after emergence of the compounds according to the invention is mostly general to its In some special cases, however, some selectivity is shown.On the other hand, the test results for the herbicidal activity before emergence clearly show the selectivity for the effect on Canadian thistle and some other species.In view of this, it should be understood that each individual species selected for the O The default test is a representative member of a recognized plant species family.
De herbicida kompositionerna enligt uppfinningen, inklusive koncentrat som kräver utspädning före .applicering på plantorna, innehåller från 5 till 95 viktdelar av minst en aktiv ingrediens och från 5 till 95 viktdelar av ett adjuvans i flytande eller fast form, t.ex. från ca 0,25 till 25 viktdelar vätmedel, från ca 0,25 till 25 viktdelar av ett dispergermedel och från 4,5 till ca 914,5 viktdelar av ett inert flytande utdrygningsmedel, t.ex. vatten, varvid alla delar är i vikt av den totala kompositionen. Där så krävs kan från ca 0,1 till 2,0 viktdelar av det' inerta flytande utdrygningsmedlet ersättas av en korrosionsinhibitor eller ett antiskummedel, eller bådadera. Kompositionernaframställs genom att 'man blandar den aktiva ingrediensen med ett adjuvans innefattande spädningsmedel, utdrygningsmedel, bärare och konditioneringsmedel för att bilda kompositioner i form av finfördelade partikelformiga fasta substanser, pellets, lösningar, dispersioner eller emulsioner. Sålunda kan den aktiva ingrediensen användas med ett adjuvans såsom en finfördelad fast substans, en vätska av organiskt ursprung, vatten, ett vätmedel, ett dispergermedel, ett emulgermedel eller någon lämplig kombination av dessa. Ur ekonomisk och bekvämlighetssynpunkt är vatten det föredragna spädningsmedlet. _ _ _ De herbicida kompositionerna enligt uppfinningen, 'speciellt vätskor och lösliga pulver, innehåller företrädesvis som konditioneringsinedel ett eller flera ytaktiva ämnen i tillräckliga mängder för att göra en given komposition lätt dispergerbar i vatten eller i olja. Införlivandet av ett ytaktivt medel i kompositionerna förbättrar kraftigt deras effektivtet. Med termen "ytaktivt ämne" avses att vätmedel, dispergermedel, suspensionsmedel och emulgermedel .ingår däri. Anjoniska, katjoniska och icke-joniska medelkan användas med samma enkelhet.The herbicidal compositions of the invention, including concentrates which require dilution before application to the plants, contain from 5 to 95 parts by weight of at least one active ingredient and from 5 to 95 parts by weight of an adjuvant in liquid or solid form, e.g. from about 0.25 to 25 parts by weight of wetting agent, from about 0.25 to 25 parts by weight of a dispersant and from 4.5 to about 914.5 parts by weight of an inert liquid excipient, e.g. water, all parts being by weight of the total composition. Where required, from about 0.1 to 2.0 parts by weight of the inert liquid excipient may be replaced by a corrosion inhibitor or an antifoam, or both. The compositions are prepared by mixing the active ingredient with an adjuvant comprising diluents, excipients, carriers and conditioners to form compositions in the form of finely divided particulate solids, pellets, solutions, dispersions or emulsions. Thus, the active ingredient may be used with an adjuvant such as a finely divided solid, a liquid of organic origin, water, a wetting agent, a dispersing agent, an emulsifying agent or any suitable combination thereof. From an economic and convenience point of view, water is the preferred diluent. The herbicidal compositions according to the invention, in particular liquids and soluble powders, preferably contain as conditioning component one or more surfactants in sufficient amounts to make a given composition readily dispersible in water or in oil. The incorporation of a surfactant into the compositions greatly improves their effectiveness. By the term "surfactant" is meant that wetting agents, dispersants, suspending agents and emulsifying agents are included therein. Anionic, cationic and non-ionic agents can be used with the same simplicity.
Föredragna vätmedel äralkylbensen- och alkylnaftalensulfonater, sulfate- rade fettalkoholer, aminer eller syraamider, lângkedjiga estrar av natriumisotio- nat, estrar av natriumsulfosuccinat, sulfaterade eller sulfonerade fettsyraestrar, petroleumsulfonater, sulfonerade vegetabiliska oljor, polyoxietylenderivat av fenoler och alkylfenoler (speciellt isooktylfenol och nonylfenol) och polyoxiety- lenderivat av mono-högre-fettsyraestrarna av hexitolanhydrider (t.ex. sor- l5 7713047-4 39 bitan). Föredragna dispergermedel är metylcellulosa, polyvinylalkohol, natrium- lignin, sulfonater, polymera alkylnaftalensulfonater, natriumnaftalensulfonat, polymetylenbisnaftalensulfonat och natrium-N-metyl-N-(långkedjig syra)-taura- ter. _ ~ Vattendispergerbara pulverkompositioner kan göras så att de innehåller en eller flera aktiva ingredienser, ett inert fast utdrygningsmedel och ett eller flera vät- och dispergermedel. De inerta fasta utdrygningsmedlen är vanligen av mineralursprung, såsom de naturliga lerorna, kiselgur och syntetiska mineraler härledda från kiseldioxid och liknande. Exempel på sådana utdrygningsmedel innefattar kaoliniter, attapulgitlera och syntetiskt magnesiumsilikat. Det vatten- dispergerbara pulvret enligt uppfinningen innehåller vanligen från ca 5 till ca 95 viktdelar aktiv ingrediens, från ca 0,25 till 25 viktdelar vätmedel, från ca 0,25 tili 25 viktdelar dispergermedel och från 4,5 till 94,5 viktdelar inert fast utdrygningsmedel, varvid alla delar är i vikt av den totala kompositionen. Där så krävs kan ca 0,1-2,0 viktdelar av det fasta inerta utdrygningsmedlet ersättas av en korrosionsinhibitor eller antiskummedel eller båda.Preferred wetting agents are alkylbenzene and alkylnaphthalene sulfonates, sulphated fatty alcohols, amines or acid amides, long chain esters of sodium isotonate, esters of sodium sulphosuccinate, sulphated or sulphonated fatty acid esters, petroleum sulphonyl phenylsolphenylene phenyl sulphonylphenylene phenyl sulphonylene polyphenylene phenolic sulphonyls polyoxyethylene derivatives of the mono-higher fatty acid esters of hexitol anhydrides (eg sorbitan). Preferred dispersants are methylcellulose, polyvinyl alcohol, sodium lignin, sulfonates, polymeric alkylnaphthalene sulfonates, sodium naphthalene sulfonate, polymethylene bisnaphthalene sulfonate and sodium N-methyl-N- (long chain acid) taurates. Water-dispersible powder compositions may be formulated containing one or more active ingredients, an inert solid excipient and one or more wetting and dispersing agents. The inert solid excipients are usually of mineral origin, such as the natural clays, diatomaceous earth and synthetic minerals derived from silica and the like. Examples of such excipients include kaolinites, attapulgite clay and synthetic magnesium silicate. The water-dispersible powder of the invention usually contains from about 5 to about 95 parts by weight of active ingredient, from about 0.25 to 25 parts by weight of wetting agent, from about 0.25 to 25 parts by weight of dispersant and from 4.5 to 94.5 parts by weight of inert solid. excipients, all parts being by weight of the total composition. Where required, about 0.1-2.0 parts by weight of the solid inert excipient may be replaced by a corrosion inhibitor or antifoam or both.
Vattenhaltiga suspensioner kan framställas genom att man blandar samman och maler en vattenhaltig uppslamning av vatten-olöslig aktiv ingrediens i närvaro av dispergermedel för att få en koncentrerad uppslamning av mycket finfördelade partiklar. Den resulterande koncentrerade vattenhaltiga suspen- sionen kännetecknas av sin extremt lilla partikelstorlek, så att täckningen blir mycket homogen när den är spädd och sprayas och innehåller vanligen från 5 till ca 95 viktdelaraktiv ingrediens, från ca 0,25 till 25 viktdelar dispergernnedel och från ca 4,5 till 94,5 viktdelar vatten.Aqueous suspensions can be prepared by mixing and grinding an aqueous slurry of water-insoluble active ingredient in the presence of dispersants to obtain a concentrated slurry of very finely divided particles. The resulting concentrated aqueous suspension is characterized by its extremely small particle size, so that the coating becomes very homogeneous when diluted and sprayed and usually contains from 5 to about 95 parts by weight of active ingredient, from about 0.25 to 25 parts by weight of dispersant and from about 4 .5 to 94.5 parts by weight of water.
Emulgerbara oljor är vanligen lösningar av aktiv ingrediens i med vatten oblandbara eller delvis oblandbara lösningsmedel med ett ytaktivt ämne.Emulsifiable oils are usually solutions of active ingredient in water-immiscible or partially immiscible solvents with a surfactant.
Lämpliga lösningsmedel för den aktiva ingrediensen enligt uppfinningen inne- fattar kolväten och med vatten oblandbara etrar, estrar eller ketoner. De emulgerbara oljekompositionerna innehåller i allmänhet från ca 5 till 95 delar aktiv ingrediens, ca l till 50 delar ytaktivt medel och: ca ll till 94 delar lösningsmedel, varvid alla delar är i vikt baserat på totaivikten av emulgerbar olja. Även om kompositioner enligt uppfinningen även kan innehålla andra tillsatser, t.ex. konstgödningsämnen, fytotoxiska ämnen och växttillväxtregulato- rer, pesticider och liknande använda som adjuvans eller i kombination med något av de ovan beskrivna adjuvansen, är det föredraget att använda kompositionerna enligt uppfinningen separat med följdbehandlingar med de andra fytotoxiska ämnena, konstgödningsämnena etc. för maximal verkan. Exempelvis skulle fältet kunna besprutas med en komposition enligt uppfinningen antingen före eller efter 7713047-4 40 behandlingen med konstgödningsämnena, andra fytotoxiska ämnen och liknande.Suitable solvents for the active ingredient of the invention include hydrocarbons and water-immiscible ethers, esters or ketones. The emulsifiable oil compositions generally contain from about 5 to 95 parts of active ingredient, about 1 to 50 parts of surfactant and: about 11 to 94 parts of solvent, all parts being by weight based on the total weight of emulsifiable oil. Although compositions according to the invention may also contain other additives, e.g. fertilizers, phytotoxic substances and plant growth regulators, pesticides and the like used as adjuvants or in combination with any of the adjuvants described above, it is preferred to use the compositions of the invention separately with sequential treatments with the other phytotoxic substances, fertilizers etc. for maximum effect. For example, the field could be sprayed with a composition according to the invention either before or after the treatment with the fertilizers, other phytotoxic substances and the like.
Kompositionerna enligt uppfinningen kan även blandas med de andra materialen, t.ex. konstgödningsämnen, andra fytotoxiska ämnen, etc. och appliceras i en enda applikation. Kemikalier som kan användas i kombination med de aktiva ingredienserna enligt uppfinningen antingen samtidigt eller i följd innefattar t.ex. triaziner, karbamider, karbamater, acetamider, acetanilider, uraciler, ättik- syror, fenoler, tiolkarbamater, triazoler, bensoesyror, nitriler och liknande.The compositions according to the invention can also be mixed with the other materials, e.g. fertilizers, other phytotoxic substances, etc. and applied in a single application. Chemicals that can be used in combination with the active ingredients of the invention either simultaneously or sequentially include e.g. triazines, ureas, carbamates, acetamides, acetanilides, uracils, acetic acids, phenols, thiol carbamates, triazoles, benzoic acids, nitriles and the like.
Konstgödningsämnen som kan användas i kombination med de aktiva ingredienserna innefattar 't.ex. ammoniumnitrat, karbamid, kaliumkarbonat och superfosfat.Fertilizers that can be used in combination with the active ingredients include 'e.g. ammonium nitrate, urea, potassium carbonate and superphosphate.
När man arbetar enligt uppfinningen appliceras verksamma mängder av glycinonitrilerna på plantorna, eller på jorden som innehåller plantorna, eller införlivas i vattenmedier på något lämpligt sätt. Appliceringen av flytande och . partikelformiga kompositioner på plantor eller jord kan utföras med lämpliga metoder, t.ex. kraftpudrare, bom- och handsprutor och spraypudrare. Komposi- tionerna kan även appliceras från flygplan som ett puder eller en spray pâ grund av sin effektivitet i låga doser. Appliceringen av herbicida kompositioner på _ vattenväxter utförs vanligen genom att man sätter kompositionerna till vatten- mediet i det område där kontroll av vattenväxterna önskas.When working according to the invention, effective amounts of the glycinonitriles are applied to the plants, or to the soil containing the plants, or incorporated into aqueous media in any suitable manner. The application of liquid and. particulate compositions on plants or soil can be performed by suitable methods, e.g. power powders, boom and hand sprayers and spray powders. The compositions can also be applied from aircraft as a powder or a spray due to their effectiveness in low doses. The application of herbicidal compositions to aquatic plants is usually carried out by adding the compositions to the aqueous medium in the area where control of the aquatic plants is desired.
Applicering av en verksam mängd av föreningarna enligt uppfinningen på plantan ärlviktig och kritisk för utövandet av uppfinningen. Den exakta mängd aktiv ingrediens som skall användas beror på det önskade svaret i' plantan liksom på andra faktorer som växtarten och dess utvecklingsstadium och nederbörds- mängden liksom den speciella glycin som används. Vid bladbehandling för reglering av vegetativ växt, appliceras de aktiva ingredienserna i mängder från ca 0,112 till ca 22,4 eller mer kg/hektar. Vid behandlingar före uppkomst kan applikationsdosen vara från ca 0,56 till ca 22,1; eller mer kg/hektar. Vid applikationer för kontroll av vattenväxter appliceras de aktiva ingredienserna i mängder från ca 0,01 delar per miljon till ca 1000 delar per miljon, baserat på vattenmediet. En verksam mängd för fytotoxisk eller herbicid kontroll är den mängd som är nödvändig för total eller selektiv kontroll, dvs. en fytotoxisk eller herbicid mängd. Det förmodas att fackmannen på området,pâ basis av vad som utlärs i denna beskrivning inklusive exemplen, lätt kan bestämma den ungefärliga applikationsdosen. Även om uppfinningen beskrivits med avseende på speciella modifika- tioner, skall dessa detaljer inte uppfattas som begränsningar annat än i den mån som anges i de följande kraven. al. _.fx\_ J.. _.Application of an effective amount of the compounds of the invention to the plant is important and critical to the practice of the invention. The exact amount of active ingredient to be used depends on the desired response in the plant as well as on other factors such as the plant species and its stage of development and the amount of precipitation as well as the particular glycine used. In foliar treatment for regulating vegetative growth, the active ingredients are applied in amounts from about 0.112 to about 22.4 or more kg / hectare. In pre-emergence treatments, the application dose may be from about 0.56 to about 22.1; or more kg / hectare. In applications for control of aquatic plants, the active ingredients are applied in amounts from about 0.01 parts per million to about 1000 parts per million, based on the aqueous medium. An effective amount for phytotoxic or herbicidal control is the amount necessary for total or selective control, ie. a phytotoxic or herbicidal amount. It is believed that those skilled in the art, based on what is taught in this specification including the examples, can readily determine the approximate application dose. Although the invention has been described with respect to particular modifications, these details are not to be construed as limitations other than to the extent set forth in the following claims. al. _.fx \ _ J .. _.
Claims (9)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/750,327 US4067719A (en) | 1976-12-13 | 1976-12-13 | O-Aryl N-phosphonomethylglycinonitriles and the herbicidal use thereof |
| US05/756,521 US4083898A (en) | 1976-12-13 | 1977-01-03 | Process for preparing O-aryl, N-phosphonomethylglycinonitriles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| SE7713047L SE7713047L (en) | 1978-06-14 |
| SE441451B true SE441451B (en) | 1985-10-07 |
Family
ID=27115259
Family Applications (7)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SE7713047A SE441451B (en) | 1976-12-13 | 1977-11-18 | O-ARYL-N-PHOSPHONOMETHYLGYCINONITRIL FOR USE AS HERBICID, HERBICIDIC COMPOSITION AND HERBICIDIC PROCEDURE |
| SE8301810A SE8301810D0 (en) | 1976-12-13 | 1983-03-30 | PROCEDURE FOR PREPARING N-PHOSPHONOMETHYLGYLIN AND ITS TIOANALOGUE |
| SE8301808A SE8301808L (en) | 1976-12-13 | 1983-03-30 | PROCEDURE FOR PREPARING A SALT OF N-PHOSPHONOMETHYLGYLINE AND ITS TIOANALOGUE |
| SE8301809A SE8301809L (en) | 1976-12-13 | 1983-03-30 | PROCEDURE FOR PREPARING N-PHOSPHONOMETHYLGYLIN AND ITS TIOANALOGUE |
| SE8301805A SE8301805D0 (en) | 1976-12-13 | 1983-03-30 | PROCEDURE FOR PREPARING O-ARYL-N-PHOSPHONOMETHYLGYCINON NITRILS |
| SE8301807A SE8301807D0 (en) | 1976-12-13 | 1983-03-30 | PROCEDURE FOR PREPARING O-ARYL-N-PHOSPHONOMETHYLGYCINON NITRILS |
| SE8301806A SE8301806D0 (en) | 1976-12-13 | 1983-03-30 | PROCEDURE FOR THE PREPARATION OF O-ARYL-N-PHOSPHONOMETHYLGYCINONITRIL SALTS |
Family Applications After (6)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SE8301810A SE8301810D0 (en) | 1976-12-13 | 1983-03-30 | PROCEDURE FOR PREPARING N-PHOSPHONOMETHYLGYLIN AND ITS TIOANALOGUE |
| SE8301808A SE8301808L (en) | 1976-12-13 | 1983-03-30 | PROCEDURE FOR PREPARING A SALT OF N-PHOSPHONOMETHYLGYLINE AND ITS TIOANALOGUE |
| SE8301809A SE8301809L (en) | 1976-12-13 | 1983-03-30 | PROCEDURE FOR PREPARING N-PHOSPHONOMETHYLGYLIN AND ITS TIOANALOGUE |
| SE8301805A SE8301805D0 (en) | 1976-12-13 | 1983-03-30 | PROCEDURE FOR PREPARING O-ARYL-N-PHOSPHONOMETHYLGYCINON NITRILS |
| SE8301807A SE8301807D0 (en) | 1976-12-13 | 1983-03-30 | PROCEDURE FOR PREPARING O-ARYL-N-PHOSPHONOMETHYLGYCINON NITRILS |
| SE8301806A SE8301806D0 (en) | 1976-12-13 | 1983-03-30 | PROCEDURE FOR THE PREPARATION OF O-ARYL-N-PHOSPHONOMETHYLGYCINONITRIL SALTS |
Country Status (36)
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| JP (1) | JPS5373543A (en) |
| AR (1) | AR223311A1 (en) |
| AT (1) | AT359772B (en) |
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| BG (2) | BG36634A3 (en) |
| BR (1) | BR7707676A (en) |
| CA (1) | CA1098529A (en) |
| CH (2) | CH636752A5 (en) |
| CY (1) | CY1061A (en) |
| DD (1) | DD145273A5 (en) |
| DE (1) | DE2751631A1 (en) |
| DK (1) | DK511677A (en) |
| EG (1) | EG12818A (en) |
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| IT (1) | IT1088890B (en) |
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| MX (1) | MX4714E (en) |
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| OA (1) | OA05804A (en) |
| PH (2) | PH16387A (en) |
| PL (1) | PL113273B1 (en) |
| PT (1) | PT67295B (en) |
| SE (7) | SE441451B (en) |
| TR (1) | TR20178A (en) |
| YU (1) | YU275677A (en) |
| ZM (1) | ZM8377A1 (en) |
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|---|---|---|---|---|
| AR027024A1 (en) | 1999-12-23 | 2003-03-12 | Basf Ag | PROCEDURE FOR THE PREPARATION OF N-PHOSPHONOMETILGLYCIN |
| CN110156838A (en) * | 2013-05-14 | 2019-08-23 | 北京美倍他药物研究有限公司 | Phosphoric acid/phosphonate derivative and its medical usage |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1445087A (en) * | 1972-11-08 | 1976-08-04 | Ici Ltd | Preparing n-phosphonomethylglycine and nitrile intermediates therefor |
| JPS5295640A (en) * | 1976-02-05 | 1977-08-11 | Nissan Chem Ind Ltd | N-(diphenylphosphonomethyl)aminoacetonitrile |
| JPS604840B2 (en) * | 1976-11-04 | 1985-02-06 | 日産化学工業株式会社 | Cyanomethylaminomethylphosphonate derivatives and herbicides containing the derivatives as active ingredients |
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1977
- 1977-11-16 EG EG643/77A patent/EG12818A/en active
- 1977-11-17 NL NL7712653A patent/NL7712653A/en not_active Application Discontinuation
- 1977-11-17 ES ES464216A patent/ES464216A1/en not_active Expired
- 1977-11-18 DE DE19772751631 patent/DE2751631A1/en not_active Withdrawn
- 1977-11-18 DK DK511677A patent/DK511677A/en not_active Application Discontinuation
- 1977-11-18 CA CA291,165A patent/CA1098529A/en not_active Expired
- 1977-11-18 ZM ZM7783A patent/ZM8377A1/en unknown
- 1977-11-18 AU AU30754/77A patent/AU510196B2/en not_active Expired
- 1977-11-18 GR GR54843A patent/GR66150B/el unknown
- 1977-11-18 DD DD77214294A patent/DD145273A5/en unknown
- 1977-11-18 NO NO773959A patent/NO151547C/en unknown
- 1977-11-18 BG BG7839915A patent/BG36634A3/en unknown
- 1977-11-18 NZ NZ185720A patent/NZ185720A/en unknown
- 1977-11-18 BG BG7737829A patent/BG28423A3/en unknown
- 1977-11-18 JP JP13800977A patent/JPS5373543A/en active Granted
- 1977-11-18 PT PT67295A patent/PT67295B/en unknown
- 1977-11-18 FI FI773495A patent/FI67558C/en not_active IP Right Cessation
- 1977-11-18 MX MX776570U patent/MX4714E/en unknown
- 1977-11-18 PL PL1977202250A patent/PL113273B1/en unknown
- 1977-11-18 FR FR7734834A patent/FR2373553A1/en active Granted
- 1977-11-18 IL IL53425A patent/IL53425A/en unknown
- 1977-11-18 GB GB48084/77A patent/GB1556322A/en not_active Expired
- 1977-11-18 AT AT825177A patent/AT359772B/en not_active IP Right Cessation
- 1977-11-18 SE SE7713047A patent/SE441451B/en not_active IP Right Cessation
- 1977-11-18 IN IN1627/CAL/77A patent/IN146347B/en unknown
- 1977-11-18 CY CY1061A patent/CY1061A/en unknown
- 1977-11-18 CH CH1411377A patent/CH636752A5/en not_active IP Right Cessation
- 1977-11-18 BR BR7707676A patent/BR7707676A/en unknown
- 1977-11-18 OA OA56318A patent/OA05804A/en unknown
- 1977-11-18 YU YU02756/77A patent/YU275677A/en unknown
- 1977-11-18 PH PH20450A patent/PH16387A/en unknown
- 1977-11-18 HU HU77MO994A patent/HU184655B/en unknown
- 1977-11-18 IT IT29814/77A patent/IT1088890B/en active
- 1977-11-18 IE IE2354/77A patent/IE45917B1/en unknown
- 1977-11-28 TR TR20178A patent/TR20178A/en unknown
- 1977-12-12 AR AR270319A patent/AR223311A1/en active
-
1980
- 1980-04-28 KE KE3045A patent/KE3045A/en unknown
-
1982
- 1982-03-30 CH CH196382A patent/CH636885A5/en not_active IP Right Cessation
-
1983
- 1983-03-30 SE SE8301810A patent/SE8301810D0/en not_active Application Discontinuation
- 1983-03-30 SE SE8301808A patent/SE8301808L/en not_active Application Discontinuation
- 1983-03-30 SE SE8301809A patent/SE8301809L/en not_active Application Discontinuation
- 1983-03-30 SE SE8301805A patent/SE8301805D0/en not_active Application Discontinuation
- 1983-03-30 SE SE8301807A patent/SE8301807D0/en not_active Application Discontinuation
- 1983-03-30 SE SE8301806A patent/SE8301806D0/en not_active Application Discontinuation
- 1983-07-14 PH PH29231A patent/PH18774A/en unknown
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