IL47972A - N-phosphonomethylglycines and herbicidal compositions containing them - Google Patents

Abstract

1366379 N-phosphonomethyl glycine and derivatives thereof MONSANTO CO 22 Oct 1971 [10 March 1971 9 Aug 1971] 49263/71 Heading C2P [Also in Division A5] Compounds of Formula I where R, R<SP>1</SP> and R<SP>2</SP> are each -OH; -NR<SP>4</SP>R<SP>5</SP> where R<SP>4</SP> and R<SP>5</SP> are each H, C 1-4 alkyl or hydroxyalkyl or C 2-4 alkenyl or R<SP>4</SP> and R<SP>5</SP> together with N form a heterocyclic ring; -OR<SP>3</SP> where R<SP>3</SP> is C 1-18 hydrocarbyl or hydrocarbyloxyhydrocarbyl optionally substituted by 1 to 3 halogen atoms, the hydrocarbyloxyhydrocarbyl groups also being optionally substituted by one or more hydrocarbyloxy groups, or a -C n H 2n -NR<SP>4</SP>R<SP>5</SP> group where n is 1 to 4; or -OR<SP>6</SP> where R<SP>6</SP> is alkali metal, alkaline earth metal, Cu, Zn, Mn, Ni, ammonium or organic ammonium, provided (i) that no more than 2 of R, R<SP>1</SP> and R<SP>2</SP> are selected from -NR<SP>4</SP>R<SP>5</SP> and -OR<SP>3</SP>, (ii) that when R<SP>6</SP> is arylammonium it is the cation of a primary amine, (iii) that no more than 2 of R, R<SP>1</SP> and R<SP>2</SP> are -OR<SP>6</SP> when R<SP>6</SP> is ammonium or organic ammonium, and (iv) that no more than 2 of R, R<SP>1</SP> and R<SP>2</SP> are -OH; and salts of the compound of Formula I in which R, R<SP>1</SP> and R<SP>2</SP> are each -OH with an acid having a pK of 2 5 or less are claimed per se. Compounds of Formula I, including the compound in which each of R, R<SP>1</SP> and R<SP>2</SP> is -OH (N-phosphonomethyl glycine), which compounds may be used as the active ingredients in conventional pesticidal compositions, may be prepared by phosphonomethylation of a glycine, by phosphite addition to azomethines or by oxidation of the corresponding phosphinic compounds. The amides and esters may also be prepared by reacting the corresponding acid halide or the methyl ester with the corresponding amine or alcohol. The salts may be prepared by partial or complete neutralization with the appropriate base. [GB1366379A]

Description

Hovel CO This invention relates to novel are useful as herbicides or This invention further relates to phytotoxicant compositions and to icidal term as used herein means materials which effectively control all plants in a given locus or selectively control the growth of one or more plants species in the presence of other In like and are used to identify the overall and selective control activity of the compounds and compositions of this The term as used herein is inclusive of the actions of inhibiting or and destroying or otherwise diminishing the occurrence and activity of plants and is applicable to any of the stated or any combination The term as used herein means terrestrial plants and aquatic The term is inclusive of gerininating emerging seedlings and herbaceous vegetation including the roots and as well as established woody The term means algae end higher aquatic The term aquatic means aquatic plants which are botanically higher than algae and is inclusive of vegetative organisms growing in water in which a major part of such organisms are normally largely roots as in as in Yallisneria or entire plants such as the term aquatic is inclusive of all water plants whether normally in their environing water such as solid such as as well as species which appear to grow normally in all respects either or rooted such as Anacharis or The of the invention are methylglycine derivative of the 6 wherein and designates or OR R can also designate where designates lower alkyl substituted or phenoxyalkyl and R 4 and R 5 are independently selected hydroxyalkyl 4 up to 4 carbon alkenyl of up to 4 carbon or R and R 5 form together with the nitrogen to which they are attached a 5 or 6 heterocyclic and R is a cation selected from the group consisting of cations of alkali alkaline earth ammonium or organic ammonium provided that at least one of and or is and at least one of R and R2 is or The term halogen as employed herein means iodine and The term encompasses cesium and and the term earth includes strontium and The organic ammonium salts of the above defined compounds are those were 6 represents a substituted ammonium moiety derived from a low molecular weight organic having a molecular weight about amines include the alkylene amines containing not more than 2 amine such as isobutylamine heptylemine dodecylamine tridecylamine pentadecylamine methylethylamine methylhexylamine methyloctadecylamine ethylbutylamine ethyloctylamine dimethylamine diethylamine diisoamylamine dihexylamine dioctylamine triisobutylamine and ine primary aryl amines such as methoxyaniline ethoxy niline phenylenediamine o and the hetrooyclic amines such as azepine and the Among the preferred compounds of this invention are those 1 of the above formula wherein least one of and is and the members of One compound encompassed by the above is This is the compound The remainder of the compounds accordance with the generic formula are of the compounds of the present are new and novel herbicides or phytotoxl glycine In Itself Is a very effective phytotoxl or Because 1t Is relatively insoluble 1n water and conventional organic not as readily amenable to commercial formulation as are many of Its It 1s therefore generally preferred to utilize the readily soluble compounds of this Invention which at the hydrogens In the hydroxy groups of has been replaced an alkal i metal or the equivalent of an earth metal or an equivalent of or nickel or has been combined ammonia or an organic The amino alkyl esters of are also efficacious phytotoxl these other by the above general formul a are water soluble but yet exhibit the same high magnitude of city as the The amine salts are easily They are solids which have no clear melting point and which decompose upon The glycines can be prepared by the methyl on of a with choromethylphosphonlc They also can be prepared by the phosphite addition to For the reaction of ethyl glyclnate with maldehyde and diethyl phosphi results in the formation of the trlethyl ester of the compounds under consideration can be readily obtained by the oxidation of the corresponding amlnophosphinic compounds utilizing chloride and other oxidizing The are granular or crystalline solid materials generally soluble in The acid halides of are prepared by for example chloro derivatives can be prepared by the reaction of with or anhydrous solvent such as an ether or other organic The esters of can be prepared by the acid halide in a with the appropriate or alcohol in the of hydrogen halide acceptor such as pyridine and the or by an ester interchange reaction with the methyl ester of thy lgly In accordance with this invention it has been found that the of germinating emerging maturing and established woody and herbaceous vegetation and aquatic plants can be controlled by exposing the emerging seedlings or above ground portions of maturing and established or the aquatic plants to the action of an ef ective amount of the glycines of the present The compounds can be used as admixtures of two or more or in admixture an These compounds are effective as phytotoxicants or the selective control of the growth of one or more monocotyledonous ecies one or more dicotyledonous species in the presence of other monocotyledons these compounds are characterized by broad spectrum they control the growth of a wide variety of plants including but not limited to conifer fir and the monocotyledons and dicotyledons In the following which illustrate the and throughout the parts and pe cent are by weight unless otherwise 1 Gaseous hydrogen chloride was led through a suspension of 6 of in excess methyl alcohol until a clear solution was The solution was concentrated at reduced pressure and the residue mixed with a of methanol containing at least one equivalent of The solvent was removed at reduced pressure and the residue extracted with ether until The granular solid was finally extracted with methanol to remove triethylamine The insoluble methyl was obtained in excellent After from dilute the product melted with decomposition at for The following esters were prepared according to the above procedure melt with decomposition at temperature chloroethyl ethyl cyclohexyl propyl A mixture of 10 of methyl methylglycinate and excess concentrated aqueous ammonium hydroxide was heated at the reflux temperature for two The solution was then concentrated at reduced the residue washed with ether and and the granular product stirred with a mixture of excess glacial acetic acid in precipitated solid was washed with methanol and crystallized from dilute The of with was 8 or of the theoretical founds 3 A mixture of 20 of methyl methylglycinate and about 23 of pyrrolidine was heated on a steam hath for two Excess amine was then removed at reduced pressure and the residue washed with ether and The gummy product was stirred with a mixture of excess glacial acetic acid in methanol and the with methanol and the 2 with was obtained in a yield of 12 or of the theoretical The product from dilute ethanol for Other compounds of the present invention that can made in general accordance with the foregoing procedures Konolithium salt of Monosodium salt of salt of salt of Monosodium salt of salt of salt of salt of salt of Honopotassium salt of ci l cina e e lycinate Preparation Of 0 1 to 10 of phospho stirred magnetically under nitrogen was added S lithium To this mixture was slowly added 1 of and stirring nuod overnight under very slow nitrogen flow while as phosphonomethyl glycinate was then added and the mixture After 2 the mixture was filtered and the clear filtrate diluted to with Upon standing a white solid precipitated which contained lithium The lithium mercaptide was removed by dissolving the solid in ml of chloroform and precipitating with of The white solid remaining was identified as 0 0 OLi Preparation of H 0 t to 20 of one molar freshly papered potassium hydroxide w added glyoinate the mixture allowed to stand 6 days at room solution was concentrated in vacuo leaving a chloroform soluble syrup which was triturated twice with ether to yield g of a brittle glassy This solid was powdered and redried at in vacuo and was as H 0 The following compounds were also prepared monosodium salt dibromohex hos honometh l l cinate dichlorophenyl of with Sodium salt of glycine methyl amide with Dipotassium salt of octylamide solid decomposing at with salt of ethyl glycinate with salt of phenoxyethyl Softening point Disodium salt of greater than dichlorop 6 The herbicidal activity of various compounds of this invention is demonstrated as The active ingredients are applied in spray form to 14 or 21 day old specimens of various plant The a water or organic solution containing active ingredient and a surfactant parts salt of acid and 65 parts tall oil condensed with ethylene oxide in the ratio of 11 moles ethylene oxide to 1 mole is applied to the plants in different sets of pans at several rates per active The treated plants are placed in a house and the effects are observed and recorded after approximat 2 weeks or approximately as is indicated in ihe last column of Table The herbicidal activity index used in Table I is as follows RESPONSE INDEX PLANT RESPONSE INDEX injury 0 Severe injury 3 injury 1 Killed Moderate injury 2 The plant species utilized in these tests are identified by letter in accordance the following A Soybean Smartweed B Sugar Beet L C Wheat Downy Brome D Pace Spp E Sorghum 0 Oocklebur P Crabgrass Gr Wild Buckwheat I COMPOUND RATE Λ 0 D I J I I 1 1 4 4 20 II 2 2 2 2 4 4 3 4 4 4444 2 IV 5 1 4 5 3 3 2 3 2 V 3 2 3 3 3 2 2 34 2 VI 4 4 3 4 4 3 4 3444 2 VII 4 4 3 4 3 3 3 4 3 1 4 43 2 2 IX 4 4 3 4 3 3 4444 2 X 4 4 2 4 34 4 544 2 XI 4 4 2 4 44 4 4444 2 XII 4 4 4 4 44 2 to old All other tests conducted on old These readings made after 11 The following are the compounds to the Eoman numerals in the EOMAN I II Me III l IV V VI VII VIII IX X XI lycinete XII ide hydrate The compositions of this invention are extremely in minimum tillage methods of crop for in those instances where it is desirable to plant a sodded or otherwise vegetated acreage with corn or the like without plowing or Compound Number solid MP XIII yrrolldlnenido glycine decomposition XIV salt of ethyl glyclnate XV Butyroamlde of glycine Allyl of glycine XVII of glycine XVIII Plperidlnyl amide of glycine XIX of glycine XX of glycine XXI Allyl XXII Isopropyl of glycine XXIII Octyloxy glyclnate XXIV Potassium salt of diethyl glycine solid MP TABLE Compound Compound Number Name xxv tal low ethyl ester XXVI Glycin tallow methyl ester XXVII glydnate XXVIII solid MP XXIX solid MP 136 XXX glydnate solid MP XXXI ethy solid MP of Ethylglycinate hydrochloride is neutralized with triethyl amine and then formaldehyde mole and diethyl phosphite are added and the mixture heated to about for 5 A five component mixture is is isolated by chromatography and is recovered as a yellow oil which has a boiling point of at Kg and has the C H N P Found C H N P 16 The compounds defined on page lines 3 to were tested as herbicides as set forth They uoed at 20 per acre and showed substantial activity against the following species of Canada Thistle Morning Lambs Smartweed Johnson Grass Downy Brome Barnyard Grass Velvet Leaf The following compounds al prepared and Chi oropropyl nate sol Calcul ated C H N CI Found C H N glyclnate sol C H N Found C H N glyclnate ated C H N CI Found C N CI phenyl glyclnate Calculated C H Found C H N D chlorophenyl glyclnate Calculated C H N Found C H N x l of the above materials when applied to the weeds employed In the tests of the application at 10 per acre killed essentially of the weeds The compositions of this invention are extremely useful n minimum til lage methods of crop for In those Instances where 1t Is desi rable to plant a sodded or otherwise vegetated acreage with corn or the without plowing or otherwise mechanically preparing a seed the crop seed can be dri ll planted 1n combination wi th a prior or subsequent application of a composition of this Invention to undeslred growing vegetation provided that the composition 1s appl ied before the emergence of the crop The compositions of nvention are also useful sod alfal renovation or conversion for In situations where a sod or parts thereof has become overgrown with undesirable plant species the plants In said area can be sprayed w th a phytotox c composition of Invention to control all growing plants and from about 2 to 24 hours later depending upon weather conditions the desired species can be seeded Into the dying Where a bed s to be prepared about 2 to 3 weeks should elapse between treatment and seed bed In order to provide sufficient time for the In an alternate method of sod the area can be seeded and immediately sprayed with a composition of this In either the seeds fall among the vegetation and as the sprayed plants wither and they act as a mulch and moisture retaining layer in which the seeds can This method is particularly useful in the spot renovation of lawns or golf greens or fairways since the herbicidal effect of the compositions of this invention is greatly decreased or totally inactivated by contact with seeds which are in the soil can germinate and grow without any apparent effects from the spraying of the unwanted plants prior to the time that the seed actually The compositions of this invention provide a wide spectrum of weed control and are also extremely useful as general herbicides as well as in controlling unwanted plants in tree and various For it has been found that by directing a spray of the compositions of this invention at the unwanted plants while essentially preventing such spray from contacting the leaves of that such unwanted plants are controlled while there is no apparent injury to the In such directed the spray can fall on the woody portion of the fruit tree or other tree without any apparent the directed spray method of control is useful with crops such as plantation and in orchards such as citrus in vineyards and in bramble crops and in nursery crops to control the undesired and in crops such as sugarcane and the The compositions of this invention are also useful for control of weeds between cropping seasons for the renovation of stale seed beds and the In applying the compositions of this invention to the plants which it is desired to control it has been found to be desirable Plantago lanceolata pratense glomerata Daucus carota Solanum carolinense Solanum Franseria Festuca arundinaceae Festuca rubra spj Cynodon dactylon diffusa or communis Fennisetum clandestinum spp cordata Ottochloa nodosa Axonopus Scleria bancara na nudiflora The phytotoxicant including concentrates which require dilution prior to application to the of this invention contain at least one active ingredient and an adjuvant in liquid or solid The compositions are prepared by admixing the active ingredient with an adjuvant including diluents extenders carriers and conditioning agents to provide compositions in the form of particulate dispersions or Thus the active ingredient can be used with an adjuvant such as a divided a liquid of organic a wetting a dispersing an emulsifying agent or any suitable combination of From the viewpoint of economy and water is the preferred particularly with the highly glycine salts such as the alkali metal salts and amine and ammonium With these solutions containing as high as five pounds or more of active materials per gallon can be readily The phytotoxicant compositions of this particularly liquids and soluble powders preferably contain as a conditioning agent one or more agents in amounts sufficient to render a given composition readily dispersible in water or in The incorporation of a agent into the compositions greatly enhances their By the term s in naphthalene sulfonates sulfated fatty amines or acid long chain acid esters of sodium esters of sodium sulfosuccinate sulfated or sulfonated fatty acid esters petroleum sulfonated vegetable di ertiary acetylenic polyoxyethylene derivatives of isooctylphenol and and polyoxyethylene derivatives of the fatty acid esters of hexitol hydrides Preferred dispersants are methyl polyvinyl sodium lignin polymeric naphthalene sodium naphthalene poly ethylene bisnaphthalenesulfonate and sodium chain laurates powder compositions can be made containing one or more active ingredients an inert solid er and one or more wetting and dispersing The inert solid extenders are usually of mineral origin such as the natural diatomaceous earth and synthetic minerals derived from silica and the Examples of such extenders include attapulgite clay and synthetic magnesium The powder of this invention usually contain from about 5 to about 95 parts by weight of active from about to 25 parts by weight of wetting from about to 25 parts by weight of dispersant and from to about parts by weight of inert solid all parts being by weight of the total Where from about to parts by weight of the solid inert extender can be placed by a corrosion inhibitor or agent or Aqueous suspensions can be prepared by mixing together and grinding an aqueous slurry of active ient in the presence of dispersing agents to obtain a concentrated very Emulsifiable oils are usually solutions of active gredient in or partially solvents together with a surface active Suitable solvents for the active ingredient of this invention include hydrocarbons and le esters or The emulsifiable oil compositions generally contain from about 5 to 95 parts active about 1 to 50 parts surface active agent and about 4 to 94 parts all parts being by weight based on the total weight of emulsifiable Although compositions of this invention can also contain other for example phytotoxicants and plant growth pesticides and the like used as adjuvants or in combination with any of the it is preferred to employ the compositions of this invention alone with sequential treatments with the other fertilizers and the like for maximum For the field could be sprayed with a composition of this invention either before or after being treated with other phytotoxicants and the The compositions of this invention can also be admixed with the other other and applied in a single Chemicals useful in tion with the active ingredients of this invention either taneously or sequentially include for example tr acetanilides acetic phenol thiolcarbamates triazoles benzoic nitriles and the like such as acid 2 henox acid salt 3 ethyl acid acid acid 4 salt azine ether acid acid methanecarsonate Fertilizers useful in combination with the active gredients include for example ammonium and When operating in accordance with the present effective amounts of the glycines are applied to above ground portions of plants The application of liquid and particu late solid herbicidal compositions to above ground portions of plants can be carried out by conventional power boom and hand sprayers and spray The compositions can also be applied from airplanes as a dust or a spray because of their effectiveness at low The cation of herbicidal compositions to aquatic plants is usually carried out by spraying the compositions on the aquatic plants in the area where control of the aquatic plants is The application of an effective amount of the compounds of this invention to the plant is essential and critical for the the piscat as well as such other factors as the plant species and stage of development and the amount of rainfall as well as the specific flycine In foliar treatment for the control of vegetative the active ingredients are applied in amounts from about to about 20 or more pounds per In applications for the control of aquatic the active ingredients are applied in amounts of from about parts per million to about 1000 parts per based on aquatic effective amount for or herbicidal control is that amount necessary for overall or selective a or herbicidal It is believed that one skilled in art can readily determine from the teachings of this including the approximate application The compositions of this invention are also useful as harvesting aids in many for the crop could be sprayed with the compositions of this invention to reduce the bulk of unwanted material and make the harvesting of the crops Such crops for and root crops such as sugar red and the insufficientOCRQuality

Claims (1)

1. A derivative of the formula 3 6 wherein and designates or OR R can also designate designates lower alkyl substituted alkoxy or phenoxy alkyl and R and R5 are independently selected from xyalkyl up to 4 carbon alkenyl of up to 4 carbon or R 4 and R 5 form together wit the nitrogen to which they are attached a 5 or 6 membered heterocyclic and R is a cation selected from the group consisting of cations of alkali ne earth ammonium or organic ammonium provided that at least one of and or is and at least one of R and is or 3 A compound in accordance with Claim 1 wherein R and R is an alkyl group containing from to 18 carbon alkenyl having from 2 through S carbon haloalkyl or haloalkenyl 1 through carbon atoms and from 1 1 through 3 halogens and and R are or A compound of Claim 2 wherein R 3 is alkyl or haloalkyl and R and R are or A compound of Claim 3 wherein and are A compound of Claim 2 wherein is A compound of Claim 2 wherein is compound of Claim 2 wherein is A compound of Claim 2 wherein is A compound Claim 2 wherein is compound of Claim 1 wherein one of and is and the remaining members are A compound of Claim 10 wherein R is organic A compound of Claim 11 wherein said organic ammonium is selected from the group consisting of heterocyclic or said organic ammonium group containing from 1 to 18 carbon A compound in accordance with Claim which is A compound in accordance with Claim 6 which is A compound in accordance with Claim 1 which is Substituted derivatives and their defined in claim substantially as an e fective amount of a compound claimed in any of claims 1 to A phytotoxic composition according to claim wherein the active ingredient is an A pnytotoxic composition according to claim w erei active ingredient is a A phytotoxic composition according to claim wherein the active ingredient a A phytotoxic composition according to any of claims 17 to wherein the active ingredient is in the of an alkali metal Phytotoxic compositions containing as active ingredient a compound as defined in any of claims 1 to substantially as hereinbefore described and with reference to the A method of controlling which comprises applying a phytotoxic amount of a compound defined in any of claims 16 to such A method of controlling vegetation by the application of a compound claimed in any of claims to substantially as hereinbefore described and with reference to the In a method of crop cultivation with minimum tillage wherein said crop is planted ingrowing the a of a composition of of claime 16 to before the crop plants emerge from the soil A according to claim wherein crop seed is planted before the growing vegetation is contacted with the A method according to claim wherein the crop plant is planted after contacting the growing vegetation with the insufficientOCRQuality