# US 9,775,355 B2 · Guanidine derivative compounds

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- Number: US 9,775,355 B2
- Document ID: US9775355B2
- Status: Granted
- Kind: B2
- Application number: 14/966,256
- Filed: 2015-12-11
- Published: 2016-04-07
- Granted: 2017-10-03
- Earliest claimed: 2009-06-30
- Assignees: Monsanto Technology LLC
- Applicants: Monsanto Technology LLC; Flamel Technologies
- Inventors: Ronald J. Brinker; Olivier Soula; Alain Lemercier
- Web page: https://patentgrep.com/patent/US9775355B2

## CPC

- A01N 47/44: Guanidine; Derivatives thereof
- A01N 37/40: having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
- A01N 39/04: Aryloxy-acetic acids; Derivatives thereof
- A01N 57/20: containing acyclic or cycloaliphatic radicals
- C07C 279/02: Guanidine; Salts, complexes or addition compounds thereof
- C07C 279/04: having nitrogen atoms of guanidine groups bound to acyclic carbon atoms of a carbon skeleton
- C07C 279/12: being further substituted by nitrogen atoms not being part of nitro or nitroso groups
- C07C 279/20: containing any of the groups [IMAGE cpc-sch-C07C-0971.gif], X being a hetero atom, Y being any atom, e.g. acylguanidines
- C07F 9/3813: {N-Phosphonomethylglycine; Salts or complexes thereof}
- C07F 9/3817: {Acids containing the structure (RX)2P(=X)-alk-N...P (X = O, S, Se)}
- C08G 73/0206: {Polyalkylene(poly)amines}
- A01N: PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF (preservation of food or foodstuff A23); BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES (preparations for medical, dental or toiletry purposes which kill or prevent the growth or proliferation of unwanted organisms A61K); PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

## Abstract

The present invention provides guanidine compounds and salts thereof that may be useful, for example, in the preparation of herbicidal compositions. The compounds may be used, for example, to prepare N-phosphonomethylglycine guanidine salts having improved herbicidal efficacy over glyphosate alone.

## Claims

### Claim 1

A guanidine compound or a salt thereof having the formula:
wherein R4 is —(CH2)m—(NR9(CH2)n)x—NR10R11, —(CH2)m—CH(NH2)CH(NH2)R11 or polyethyleneimino; R5, R6, R7 and R8 are independently hydrogen or C1-C5 hydrocarbyl;
R9 and R10 are independently hydrogen or C1-C5 hydrocarbyl; R11 is C1-C30 hydrocarbyl; and
m, n and x are independently an integer from 1 to 10.

### Claim 2 (depends on 1)

The compound of claim 1 wherein R5, R6, R7 and R8 are independently hydrogen or C1-C5 alkyl.

### Claim 3 (depends on 1)

The compound of claim 1 wherein R4 is 3,6,9,12,15,18-hexaazatriacontyl or (2,3-diamino)tallow and R5, R6, R7 and R8 are hydrogen.

### Claim 4 (depends on 1)

The compound of claim 1 wherein R4 is 3,6,9,12,15,18-hexaazatriacontyl or (2,3-diamino)tallow and R5, R6, R7 and R8 are methyl.

### Claim 5 (depends on 1)

The compound of claim 1 wherein R4 is polyethyleneimino and R5, R6, R7 and R8 are hydrogen.

### Claim 6 (depends on 1)

The compound of claim 1 wherein R4 is polyethyleneimino and R5, R6, R7, and R8 are methyl.

### Claim 7 (depends on 1)

An aqueous herbicidal composition comprising the compound of claim 1 and an herbicide component comprising one or more herbicides.

### Claim 8 (depends on 7)

The composition of claim 7 wherein the herbicide component comprises glyphosate.

### Claim 9 (depends on 7)

The composition of claim 7 wherein the herbicide component comprises one or more water-soluble herbicides selected from the group consisting of acifluorfen, acrolein, amitrole, asulam, benazolin, bentazon, bialaphos, bromacil, bromoxynil, chloramben, chloroacetic acid, clopyralid, 2,4-D, 2,4-DB, dalapon, dicamba, dichlorprop, difenzoquat, diquat, endothall, fenac, fenoxaprop, flamprop, flumiclorac, fluoroglycofen, flupropanate, fomesafen, fosamine, glufosinate, imazameth, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, ioxynil, MCPA, MCPB, mecoprop, methylarsonic acid, naptalam, nonanoic acid, paraquat, picloram, quinclorac, sulfamic acid, 2,3,6-TBA, TCA, triclopyr and water-soluble salts thereof.

### Claim 10 (depends on 9)

The composition of claim 9 wherein the herbicide component comprises dicamba.

### Claim 11 (depends on 9)

The composition of claim 9 wherein the herbicide component comprises 2,4-D.

### Claim 12 (depends on 7)

The composition of claim 7 wherein the herbicide component comprises one or more herbicides of limited water solubility selected from the group consisting of acetochlor, aclonifen, alachlor, ametryn, amidosulfuron, anilofos, atrazine, azafenidin, azimsulfuron, benfluralin, benfuresate, bensulfuron-methyl, bensulide, benzofenap, bifenox, bromobutide, bromofenoxim, butachlor, butamifos, butralin, butroxydim, butylate, cafenstrole, carbetamide, carfentrazone-ethyl, chlomethoxyfen, chlorbromuron, chloridazon, chlorimuron-ethyl, chlornitrofen, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal-dimethyl, chlorthiamid, cinmethylin, cinosulfuron, clethodim, clodinafop-propargyl, clomazone, clomeprop, cloransulam-methyl, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop-butyl, daimuron, desmedipham, desmetryn, dichlobenil, diclofop-methyl, diflufenican, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dinitramine, dinoterb, diphenamid, dithiopyr, diuron, EPTC, esprocarb, ethalfluralin, ethametsulfuron-methyl, ethofumesate, ethoxysulfuron, etobenzanid, fenoxaprop-ethyl, fenuron, flamprop-methyl, flazasulfuron, fluazifop-butyl, fluchloralin, flumetsulam, flumiclorac-pentyl, flumioxazin, fluometuron, fluorochloridone, fluoroglycofen-ethyl, flupoxam, flurenol, fluridone, fluroxypyr-1-methylheptyl, flurtamone, fluthiacet-methyl, fomesafen, halosulfuron, haloxyfop-methyl, hexazinone, imazamox, imazosulfuron, indanofan, isoproturon, isouron, isoxaben, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, mefenacet, mesotrione, metamitron, metazachlor, methabenzthiazuron, methyldymron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, molinate, monolinuron, naproanilide, napropamide, naptalam, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxyfluorfen, pebulate, pendimethalin, pentanochlor, pentoxazone, phenmedipham, piperophos, pretilachlor, primisulfuron, prodiamine, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propyzamide, prosulfocarb, prosulfuron, pyraflufen-ethyl, pyrazolynate, pyrazosulfuron-ethyl, pyrazoxyfen, pyributicarb, pyridate, pyriminobac-methyl, quinclorac , quinmerac, quizalofop-ethyl, rimsulfuron, sethoxydim, siduron, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron, sulfosulfuron, tebutam, tebuthiuron, terbacil, terbumeton, terbuthylazine, terbutryn, thenylchlor, thiazopyr, thifensulfuron, thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron, trietazine, trifluralin, triflusulfuron and vernolate.

### Claim 13 (depends on 8)

The composition of claim 8 comprising from about 1% to about 50% by weight of glyphosate on an acid equivalent basis.

### Claim 14 (depends on 8)

The composition of claim 8 wherein the composition is an aqueous herbicidal concentrate comprising from about 300 to about 600 grams per liter glyphosate on an acid equivalent basis.

### Claim 15 (depends on 8)

The composition of claim 8 wherein the composition is an aqueous herbicidal concentrate comprising from about 420 to about 600 grams per liter glyphosate on an acid equivalent basis.

### Claim 16 (depends on 8)

The composition of claim 8 wherein the composition is an aqueous herbicidal concentrate comprising from about 480 to about 540 grams per liter glyphosate on an acid equivalent basis.

### Claim 17 (depends on 8)

The composition of claim 8 wherein the composition is a ready-to-use aqueous composition comprising from about 1 to about 50 grams per liter glyphosate on an acid equivalent basis.

### Claim 18 (depends on 8)

The composition of claim 8 wherein the composition is a solid herbicidal composition comprising from about 10% to about 80% by weight of glyphosate on an acid equivalent basis.

### Claim 19 (depends on 7)

The composition of claim 7 further comprising at least one surfactant.

### Claim 20

A guanidine compound or a salt thereof having the formula:
wherein R5, R6, R7 and R8 are independently hydrogen or C1-C5 hydrocarbyl, R12 is hydrogen, C8-C30 alkyl, or C8-C30 alkenyl, and x and y are independently an integer from 2 to 20.

### Claim 21 (depends on 20)

The compound of claim 20 wherein R5, R6, R7 and R8 are independently hydrogen or C1-C5 alkyl.

### Claim 22 (depends on 20)

The compound of claim 20 wherein R12 is C12-C18 alkyl or C12-C18 alkenyl.

### Claim 23 (depends on 20)

The compound of claim 20 wherein the compound has a weight average molecular weight of from about 500 to about 7,000.

### Claim 24 (depends on 20)

An aqueous herbicidal composition comprising the compound of claim 20 and an herbicide component comprising one or more herbicides.

### Claim 25 (depends on 24)

The composition of claim 24 wherein the herbicide component comprises glyphosate.

### Claim 26 (depends on 24)

The composition of claim 24 wherein the herbicide component comprises one or more water-soluble herbicides selected from the group consisting of acifluorfen, acrolein, amitrole, asulam, benazolin, bentazon, bialaphos, bromacil, bromoxynil, chloramben, chloroacetic acid, clopyralid, 2,4-D, 2,4-DB, dalapon, dicamba, dichlorprop, difenzoquat, diquat, endothall, fenac, fenoxaprop, flamprop, flumiclorac, fluoroglycofen, flupropanate, fomesafen, fosamine, glufosinate, imazameth, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, ioxynil, MCPA, MCPB, mecoprop, methylarsonic acid, naptalam, nonanoic acid, paraquat, picloram, quinclorac, sulfamic acid, 2,3,6-TBA, TCA, triclopyr and water-soluble salts thereof.

### Claim 27 (depends on 26)

The composition of claim 26 wherein the herbicide component comprises dicamba.

### Claim 28 (depends on 26)

The composition of claim 26 wherein the herbicide component comprises 2,4-D.

### Claim 29 (depends on 24)

The composition of claim 24 wherein the herbicide component comprises one or more herbicides of limited water solubility selected from the group consisting of acetochlor, aclonifen, alachlor, ametryn, amidosulfuron, anilofos, atrazine, azafenidin, azimsulfuron, benfluralin, benfuresate, bensulfuron-methyl, bensulide, benzofenap, bifenox, bromobutide, bromofenoxim, butachlor, butamifos, butralin, butroxydim, butylate, cafenstrole, carbetamide, carfentrazone-ethyl, chlomethoxyfen, chlorbromuron, chloridazon, chlorimuron-ethyl, chlornitrofen, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal-dimethyl, chlorthiamid, cinmethylin, cinosulfuron, clethodim, clodinafop-propargyl, clomazone, clomeprop, cloransulam-methyl, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop-butyl, daimuron, desmedipham, desmetryn, dichlobenil, diclofop-methyl, diflufenican, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dinitramine, dinoterb, diphenamid, dithiopyr, diuron, EPTC, esprocarb, ethalfluralin, ethametsulfuron-methyl, ethofumesate, ethoxysulfuron, etobenzanid, fenoxaprop-ethyl, fenuron, flamprop-methyl, flazasulfuron, fluazifop-butyl, fluchloralin, flumetsulam, flumiclorac-pentyl, flumioxazin, fluometuron, fluorochloridone, fluoroglycofen-ethyl, flupoxam, flurenol, fluridone, fluroxypyr-1-methylheptyl, flurtamone, fluthiacet-methyl, fomesafen, halosulfuron, haloxyfop-methyl, hexazinone, imazamox, imazosulfuron, indanofan, isoproturon, isouron, isoxaben, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, mefenacet, mesotrione, metamitron, metazachlor, methabenzthiazuron, methyldymron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, molinate, monolinuron, naproanilide, napropamide, naptalam, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxyfluorfen, pebulate, pendimethalin, pentanochlor, pentoxazone, phenmedipham, piperophos, pretilachlor, primisulfuron, prodiamine, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propyzamide, prosulfocarb, prosulfuron, pyraflufen-ethyl, pyrazolynate, pyrazosulfuron-ethyl, pyrazoxyfen, pyributicarb, pyridate, pyriminobac-methyl, quinclorac , quinmerac, quizalofop-ethyl, rimsulfuron, sethoxydim, siduron, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron, sulfosulfuron, tebutam, tebuthiuron, terbacil, terbumeton, terbuthylazine, terbutryn, thenylchlor, thiazopyr, thifensulfuron, thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron, trietazine, trifluralin, triflusulfuron and vernolate.

### Claim 30 (depends on 25)

The composition of claim 25 comprising from about 1% to about 50% by weight of glyphosate on an acid equivalent basis.

### Claim 31 (depends on 25)

The composition of claim 25 wherein the composition is an aqueous herbicidal concentrate comprising from about 300 to about 600 grams per liter glyphosate on an acid equivalent basis.

### Claim 32 (depends on 25)

The composition of claim 25 wherein the composition is an aqueous herbicidal concentrate comprising from about 420 to about 600 grams per liter glyphosate on an acid equivalent basis.

### Claim 33 (depends on 25)

The composition of claim 25 wherein the composition is an aqueous herbicidal concentrate comprising from about 480 to about 540 grams per liter glyphosate on an acid equivalent basis.

### Claim 34 (depends on 25)

The composition of claim 25 wherein the composition is a ready-to-use aqueous composition comprising from about 1 to about 50 grams per liter glyphosate on an acid equivalent basis.

### Claim 35 (depends on 25)

The composition of claim 25 wherein the composition is a solid herbicidal composition comprising from about 10% to about 80% by weight of glyphosate on an acid equivalent basis.

### Claim 36 (depends on 24)

The composition of claim 24 further comprising at least one surfactant.