CA2173607A1

CA2173607A1 - Herbicidal aza bisphosphonic acid compositions

Info

Publication number: CA2173607A1
Application number: CA002173607A
Authority: CA
Inventors: Karl Joseph Fisher; Frank Xavier Woolard; John Montgomery Gerdes
Original assignee: Individual
Current assignee: Syngenta Ltd
Priority date: 1993-10-07
Filing date: 1994-10-07
Publication date: 1995-04-20
Also published as: NZ274000A; WO1995010188A2; IL111180A; CN1134657A; EP0722268A1; HUT74893A; IL114381A0; IL111180A0; ZA947814B; AU7790194A; FI961520A; CZ101596A3; WO1995010188A3; AU690581B2; NO961389D0; NO961389L; FI961520A0; BR9407762A; TW401276B; PL313820A1

Abstract

Herbicidal compositions comprising: (A) a compound of formula (I), wherein R1 is hydrogen, hydroxy, C1-C4 alkoxy, halogen, C1-C4 alkyl, C1-C4 haloalkyl, hydroxy-C1-C4-alkyl, hydroxy-C1-C4-alkoxy or N(R6)(R7) wherein R6 and R7 are each independently hydrogen or C1-C3 alkyl; R2 and R3 are each independently hydrogen; hydrocarbyl; substituted hydrocarbyl; hydrocarbyloxy; substituted hydrocarbyloxy; hydrocarbyl-S(O)m-; or substituted hydrocarbyl-S(O)m-; or R2 and R3 together form a 3-6 membered carbocyclic ring, optionally substituted with halogen, hydroxy, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio or N(R8)(R9) wherein R8 and R9 are each independently hydrogen or C1-C12 alkyl; and R4 and R5 are each independently hydrogen; hydrocarbyl; substituted hydrocarbyl;
hydrocarbyloxy; substituted hydrocarbyloxy; hydrocarbylthio; substituted hydrocarbylthio; pyridyl; substituted pyridyl; or are of the formula N(R10)(R11) wherein R10 and R11 are independently hydrogen, hydrocarbyl or substituted hydrocarbyl; or R4 and R5 together with the nitrogen to which they are bound form an aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimine, piperidine, tetrahydropyridine, pyrazole, imidazole, pyrrole, triazole, tetrahydropyrimidine, dihydroimidazole, pyrroline, azetidine, perhydroindole, perhydroquinoline, perhydroisoquinoline or pyrrolidine ring, any of which may be optionally substituted with C1-C12 alkyl, halo, C6-C10 aryl, C6-C10 aryl substituted with halo or C1-C6 alkyl, C7-C16 aralkyl, C7-C16 aralkyl substituted with halo or C1-C6 alkyl, nitro, halo-C1-C10-alkyl, C1-C10 alkoxy, C1-C10 alkylthio, C1-C10 alkylsulfonyl, phenoxy, phenoxy substituted with halo or C1-C6 alkyl, C1-C10 alkenyl or cyano; or R2 and R4 together with the nitrogen and carbon atoms to which they are bound form an aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimine, piperidine, tetrahydropyridine, pyrazole, imidazole, pyrrole, triazole, tetrahydropyrimidine, dihydroimidazole, pyrroline, azetidine, perhydroindole, perhydroquinoline, perhydroisoquinoline or pyrrolidine ring, any of which may be optionally substituted with C1-C12 alkyl, halo, C6-C10 aryl, C6-C10 aryl substituted with halo or C1-C6 alkyl, C7-C16 aralkyl, C7-C16 aralkyl substituted with halo or C1-C6 alkyl, nitro, halo-C1-C10-alkyl, C1-C10 alkoxy, C1-C10 alkylthio, C1-C10 alkylsulfonyl, phenoxy, phenoxy substituted with halo or C1-C6 alkyl, C1-C10 alkenyl or cyano; and m is 0, 1 or 2; and agrochemically acceptable salts thereof; and (B) an agrochemically acceptable carrier therefor. In other aspects, this invention is directed to a method of controlling the growth of plants comprising applying to the area where control is desired an herbicidally effective amount of a compound of formula (I) above; as well as to certain novel compounds having a structure within the scope of formula (I) above.

Description

~ WO 95/10188 2 ~ 7 3 ~ ~ 7 PCT/GB94/02183 }~ERBICTDAL AZA BISPHOSPHONIC ACID CO~POSITIONS

FIELD OF THE INVENTION
.

~ In one aspect, this invention relates to herbicidal aza-bisphosphonic acid compositions comprising (A) an aza-bisphosphonic acid wherein the nitrogen atom and the carbon atom to which the two phosphonic acid groups are bound are linked with a single carbon atom and (B) a suitable carrier therefor. In another aspect, this invention is directed to a method of controlling the growth of plants comprising applying to the area where control is desired an herbicidally effective amount of such an aza-bisphosphonic acid compound. In yet another aspect, this invention is directed to certain novel aza-bisphosphonic acid compounds.

BACKGROUND OF THE INVENTION

The need for effective herbicides requires no special emphasis. The control of weeds and undesirable vegetation is of great economic importance since weed competition inhibits the production of foliage, fruit or seed of agricultural crops. The presence of weeds can reduce harvesting efficiency and the quality of the harvested crop.
Weeds on noncropped areas may cause a fire hazard, undesirable drifting of sand or snow, and/or irritation to persons with allergies. Thus, suppression of undesirable weed growth is very advantageous.

Moreover, it is highly desirable to possess her~i-cides which exhibit desirable efficacy against plants when applied postemergently, but which further exhibit little significant activity when applied preemergently. Such herbi-cides will, for example, permit the control of weeds already present in a field but will not harm crops which have not yet emerged.

WO 95/10188 PCT/GB9~/02183 ~
~173~7 Accordingly, it is an object of this invention to provide effective novel herbicidal compositions and a novel method of controlling weeds, as well as certain novel herbi-cidal compounds. It is a further object of this invention to provide novel compositions, methods and herbicidal compounds which exhibit admirable postemergent control coupled with no significant preemergent control.

While certain bisphosphonic and aza-bisphosphonic acid herbicidal compounds have been disclosed in the art, such herbicidal compounds do not possess a structure wherein the carbon atom to which the two phosphonic acid groups are bound is linked to the nitrogen of the amino group via a single carbon atom.

Thus, Japanese Patent Publication 54-147925 (Nissan Chemical) discloses herbicidal bisphosphonic acid compounds wherein the phosphonic acid groups are bound to a single carbon atom. Such compounds are of the Formula:

O X O
(HO) p C P - (OH) Y

wherein X and Y are each hydrogen, halogen, alkyl or cycloalkyl; or salts thereof.

Herbicidal aza-bisphosphonic acid compounds wherein the carbon to which the two phosphonic acid groups are bound is directly linked to the nitrogen atom of the amino group are disclosed in U.S. Patent 4,447,256 (Suzuki et al.); British Patent 1,508,772 (Devlin); Japanese Patent Publication 54-37829 (Nissan Chemical); Japanese Patent Publication 54-144383 (Nissan Chemical); Japanese Patent Publication 55-98105 (Nissan Chemical); and in "Herbicide Properties of Aminophosphonic Acid Derivatives", Dr. Y. Okamoto, 1st Inter-national Congress on Phosphorus Compounds, Rabat, October 17-21, 1977, pp. 649-652.

WO 95/10188 ~ 1 7 3 6 ~ 7 PCT/GB9'1/02183 Japanese Patent Publication 55-98193 discloses certain herbicidal compounds of the formula .~
~"\
~Y

wherein R is H, lower alkyl or halogen; X is -CH2-, S or 0; Y
is H, lower alkyl or halogen; and alkali salts thereof.

Although certain aza-bisphosphonic acid compounds wherein the carbon to which the two phosphonic acid groups are bound is linked to a nitrogen atom via a single carbon atom have been disclosed in the art, these particular compounds are not indicated to have herbicidal activity. Thus, U.S. Patent 3,962,318 discloses compounds useful as flame retardants;
German Patent DE 2754821 discloses compounds useful as chelators in water treatment; and U.S. Patent 5,133,972, U.S.
Patent 4,990,503, European Patent Publication 96,931, European Patent Publication 96,933, European Patent Publication 186,405, European Patent Publication 274,138, European Patent Publication 522,576 and German Patent Publication DE 3,804,686 all disclose pharmaceutical uses for the specific compounds disclosed therein.

WO 95/10188 PCT/GB9~/02183 SUMM~RY OF THE lNV~iN~llON

In one aspect, this invention is directed to a herbicidal composition comprising:

(A) A compound of the Formula (I):

R \ iR2 P3H2 N - C C R (I) 5 ~ '3 wherein R1 is hydrogen, hydroxy, Cl-C4 alkoxy, halogen, C1-C4 alkyl, Cl-C4 haloalkyl, hydroxy-Cl-C4-alkyl, hydroxy--Cl-C4-alkoxy or N(R6)(R7) wherein R6 and R7 are each indepen-dentlY hydrogen or3Cl C3 a y ;
R and R are each independently hydrogen; hydro-carbyl; substituted hydrocarbyl; hydrocarbyloxy; substituted hydrocarbyloxy; hydrocarbyl-S(O)m~; or substituted hydrocar-byl-S(O)m~i or R and R together form a 3-6 membered carbocyclic ring, optionally substituted with halogen, hydroxy, C1-C6 alkyl, C1-C6 alkoxy, Cl-C6 alkylthio or N(R8)(R9) wherein R
and R are each independently hydrogen or C1-C12 alkyl; and R and R are each independently hydrogen; hydro-carbyl; substituted hydrocarbyl; hydrocarbyloxy; substituted hydrocarbyloxy; hydrocarbylthio; substituted hydrocarbylthio;
pyridyl; substituted pyridyl; or are of the formula N(R10)(Rll) wherein R10 and R11 are independently hydrogen, hydrocarbyl or substituted hydrocarbyl; or R4 and R5 together with the nitrogen to which they are bound form an aziridine, piperazine, morpholine, thiomor-pholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimine, piperidine, tetrahydropyridine, pyrazole, imidazole, pyrrole, triazole, tetrahydropyrimidine, dihydro-imidazole, pyrroline, azetidine, perhydroindole, perhydro-quinoline, perhydroisoquinoline or pyrrolidine ring, any of which may be optionally substituted with C1-C12 alkyl, halo, C6-C10 aryl, C6-C10 aryl substituted with halo or Cl-C6 alkyl, ~ WO95/10188 2 ~ ~ 3 ~ ~ 7 pcTlGBs~/o2l83 C7-Cl6 aralkyl, C7-Cl6 aralkyl substituted with halo or Cl-C6 Cl ClO-alkYl' Cl-ClO alkoxy, C -C alkyl thio, Cl-ClO alkylsulfonyl, phenoxy, phenoxy substituted with Cl 2C6 alkyl, Cl-ClO alkenyl or cyano; or R and R together with the nitrogen and carbon atoms to which they are bound form an aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomor-pholine sulfonyl, hexamethyleneimine, piperidine, tetrahydro-pyridine, pyrazole, imidazole, pyrrole, triazole, tetrahydro-pyrimidine, dihydroimidazole, pyrroline, azetidine, perhydro-indole, perhydroquinoline, perhydroisoquinoline or pyrrolidine ring, any of which may be optionally substituted with Cl-Cl2 alkyl, halo, C6-ClO aryl, C6-ClO aryl substituted with halo or Cl-C6 alkyl, C7-Cl6 aralkyl, C7-Cl6 aralkyl substituted with halo or Cl-C6 alkyl, nitro, halo-Cl-Cl0-alkyl, Cl-ClO alkoxy, Cl-ClO alkylthio, Cl-ClO alkylsulfonyl, phenoxy, phenoxy substituted with halo or Cl-C6 alkyl, Cl-ClO alkenyl or cyano;
and m is 0, l or 2;
and agrochemically acceptable salts thereof; and (B) An agrochemically acceptable carrier therefor.

In another aspect, this invention is directed to a method of controlling the growth of plants comprising applying to the area where control is desired an herbicidally effective amount of a compound of Formula (I) above.

In yet another aspect, this invention is directed to certain novel compounds having a structure within the scope of Formula (I) above.

2~6~ -6-DETAILED DESCRIPTION OF ~HE PREFERRED EMBODIMENTS

The herbicidal compositions of this invention com-prise a bisphosphonic acid compound of the Formula (I):

N C - C R (I) R5 ~ R3 P3H2 wherein R1 is hydrogen, hydroxy, C1-C4 alkoxy, halogen, C1-C4 alkyl, C1-C4 haloalkyl, hydroxy-Cl-C4-alkyl, hydroxy--C1-C4-alkoxy or N(R6)(R7) wherein R6 and R are each indepen-dently hydrogen or3C1 C3 y ;
R and R are each independently hydrogen; hydro-carbyl; substituted hydrocarbyl; hydrocarbyloxy; substituted hydrocarbyloxy; hydrocarbyl-S(O)m-; substituted hydrocar-byl-S(O)mi or R2 and R3 together form a 3-6 membered carbocyclic ring, optionally substituted with halogen, hydroxy, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio or N(R )(R ) wherein R
and R9 are each independently hydrogen or C1-C12 alkyl; and R4 and R5 are each independently hydrogen; hydro-carbyl; substituted hydrocarbyl; hydrocarbyloxy; substituted hydrocarbyloxy; hydrocarbylthio; substituted hydrocarbylthio;
pyridyl; substituted pyridyl; or are of the formula N(R10)(Rll) wherein R10 and R11 are independently hydrogen, hydrocarbyl or substituted hydrocarbyl; or R4 and R5 together with the nitrogen to which they are bound form an aziridine, piperazine, morpholine, thiomor-pholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimine, piperidine, tetrahydropyridine, pyrazole, imidazole, pyrrole, triazole, tetrahydropyrimidine, dihydro-imidazole, pyrroline, azetidine, perhydroindole, perhydro-quinoline, perhydroisoquinoline or pyrrolidine ring, any of whish may be optionally substituted with C1-C12 alkyl, halo, C6-C10 aryl, C6-C10 aryl substituted with halo or C1-C6 alkyl, C7-C16 aralkyl, C7-C16 aral~yl substituted with halo or C1-C6 WO9S/10188 _7_ PCT/GB94/02183 Cl C1o~alkYl~ C1-C10 alkoxy, C -C alkyl thio, C1-C10 alkylsulfonyl, phenoxy, phenoxy substituted with 1 2C6 alkyl, C1-C10 alkenyl or cyano; or R and R together with the nitrogen and carbon atoms to which they are bound form an aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomor-pholine sulfonyl, hexamethyleneimine, piperidine, tetrahydro-pyridine, pyrazole, imidazole, pyrrole, triazole, tetrahydro-pyrimidine, dihydroimidazole, pyrroline, azetidine, perhydro-indole, perhydroquinoline, perhydroisoquinoline or pyrrolidine ring, any of which may be optionally substituted with Cl-C12 alkyl, halo, C6-C10 aryl, C6-C10 aryl substituted with halo or C1-C6 alkyl, C7-C16 aralkyl, C7-C16 aralkyl substituted with halo or C1-C6 alkyl, nitro, halo-C1-C10-alkyl, C1-C10 alkoxy, C1-C10 alkylthio, C1-C10 alkylsulfonyl, phenoxy, phenoxy substituted with halo or C1-C6 alkyl, C1-C10 alkenyl or cyano;
and M is 0, 1 or 2;
and agrochemically acceptable salts thereof.

Preferably:
R1 is hydrogen, hydroxy, halogen or C1-C4 alkyl;
R2 and R3 are independently hydrogen; C1-C12 alkyl;
lkenyl; C -C12 alkynyl; halo-C1 C12 y 2 2 12 alkynyl; C6-C14 aralkyl; C -C alkoxy;

R and R are independently C1-C6 alkyl; C2-C6 alkenyl; C2-C6 alkynyl; halo-C1-C6 alkyl; halo-C2-C6 alkenyl;
halo-C1-C6-alkynyl; pyridyl; substituted pyridyl; phenyl;
substituted phenyl; C7-C14 aralkyl; or substituted C7-C14 aralkyl; or R4 and R5 together with the nitrogen to which they are bound form a tetrahydropyrimidine, tetrahydropyridine, imidazole ring or a -(CH2)n-N- ring wherein n is 2-6, option-ally substituted with halogen, hydroxy, C1-C6 alkoxy, nitro, C1-C6 alkyl, C7-C16 aralkyl or C1-C6 alkylthio groups-WO9S/10188 PCT/GB9~/02183 ~3607 -8-More preferably, Rl is hydrogen or hydroxy;
R2 and R3 are each independently hydrogen or Cl-C6 alkyl; and R4 and R5 are each independently hydrogen, Cl-C6 alkyl, Cl-C6 alkenyl, benzyl, benzyl substituted with Cl-C6 alkyl or halo or R4 and R5 together with the nitrogen to which they are bound form a pyrrolidine or piperidine ring, either of which may be optionally substituted with fluorine, hydroxy, Cl-C6 alkoxy or Cl-C6 alkyl.

Particularly preferred cbmpounds for use in the herbicidal compositions and method of this invention include:
2-(R-alpha-methylbenzylamino)ethyl-l,l-bisphosphonic acid;
2-(2-methylpropylamino)ethyl-l,l-bisphosphonic acid;
2-[l-(4-methyl-l,3-imidazolyl)]ethyl-l,l-bisphos-phonic acid;
2-(l-pyrrolidinyl)ethyl-l,l-bisphosphonic acid;
2-(l-piperdinyl)ethyl-l,l-bisphosphonic acid;
2-(propylamino)ethyl-l,l-bisphosphonic acid;
2-(N,N-methylethylamino)ethyl-l,l-bisphosphonic acid;
2-(n-butylamino)ethyl-l,l-bisphosphonic acid;
2-(2-propenylamino)ethyl-l,l-bisphosphonic acid;
2-[l-(l,2,3,6-tetrahydropyridinyl)]ethyl-l,l-bis-phosphonic acid; and 2-(N,N-dipropylamino)ethyl-l,l-bisphosphonic acid.

In another aspect, this invention is directed to certain classes of novel aza-bisphosphonic acid compounds.

One of such classes of novel aza-bisphosphonic acid compounds within the scope of this invention include those of the structural Formula II:

~ WO95/10188 9 ~ 1 7 3 ~ ~ ~ pCT/GBg4l02l83 R13 _ N CH2 CH3 2 (II) '~03H2 wherein Rl2 and Rl3 are each independently hydrogen, Cl-C6 straight chain or branched alkyl, hydroxy, C2-C6 alkenyl, Cl-C6 alkoxy or Cl-C6 alkoxy-Cl-C6 alkyl; and agriculturally acceptable salts thereof. Specific compounds within the scope of this genus include:

2-(N,N-di-n-butylamino)ethyl-l,l-bisphosphonic acid;
2-(N,N-diethylamino)ethyl-l,l-bisphosphonic acid;
2-(N,N-di-~-propylamino)ethyl-l,l-bisphosphonic acid;
2-(propylamino)ethyl-l,l-bisphosphonic acid;
2-(isopropylamino)ethyl-l,l-bisphosphonic acid;
2-(propylamino)ethyl-l,l-bisphosphonic acid, tetra-butylammonium salt;
2-(propylamino)ethyl-l,l-bisphosphonic acid, tri-butylamine salt;
2-(t-butylamino)ethyl-l,l-bisphosphonic acid;
2-(n-butylamino)ethyl-l,l-bisphosphonic acid, 2-(n-hexylamino)ethyl-l,l-bisphosphonic acid, tetra-butylammonium salt;
2-(but-3-enylamino)ethyl-l,l-bisphosphonic acid;
2-(n-hexylamino)ethyl-l,l-bisphosphonic acid;
2-(n-isobutylamino)ethyl-l,l-bisphosphonic acid;
2-(n-ethylamino)ethyl-l,l-bisphosphonic acid;
2-(prop-2-enylamino)ethyl-l,l-bisphosphonic acid;
2-(methoxyamino)ethyl-l,l-bisphosphonic acid;
2-(N-methoxy,N-methylamino)ethyl-l,l-bisphosphonic acid;
2-~N-hydroxy,N-methylamino)ethyl-l,l-bisphosphonic acid; and 2-(2-ethoxyethylamino)ethyl-l,l-bisphosphonic acid.
-WO9~/10188 2 ~ 7 3 ~ o - PCTIGB94/02183 ~

Novel aza-bisphosphonic acids within the scope of this invention also include those of Formula III:

Ar (-C-) N C CH (III) (R16~ ~ Rl5q R19 R17 P03H2 wherein q is 0-lO; j is 0-3; Rl4 and Rl5 are each indepen-dently hydrogen or Cl-C6 alkyl; Ar is benzene, pyridine, pyrimidine, pyridazine, naphthalene, pyrazole, imidazole, triazole, thiazole, furan, thiophene, pyrrole, oxazole or thiadiazole; Rl6 is halo, Cl-ClO alkyl, aryl, substituted aryl, benzyl, substituted benzyl, nitro, halo-Cl-Cl0-alkyl, lkoXy C -C1 0 alkylthio, Cl C10 phenoxy, substituted phenoxy, Cl-ClO alkenyl or cyano; and Rl , Rl8 and Rl9 are each independently hydrogen, Cl-ClO
alkyl, Cl-ClO substituted alkyl, C7-ClO aralkyl or C2-ClO
alkenyl;
and agriculturally acceptable salts thereof.
When q is 2 or more, each Rl4 and Rl5 may themselves independently be hydrogen or Cl-C3 alkyl. Similarly, when j is 2 or more, each Rl6 may be the same or different.

Specific compounds within the scope of this genus include:
2-(alpha-methylbenzylamino)ethyl-l,l-bisphosphonic acid;
2-(2-methylbenzylamino)ethyl-l,l-bisphosphonic acid;
2-(3-methylbenzylamino)ethyl-l,l-bisphosphonic acid;
2-(2-phenylethylamino)ethyl-l,l-bisphosphonic acid;
2-(benzylamino)ethyl-l,l-bisphosphonic acid;
2-(S-alpha-methylbenzylamino)ethyl-l,l-bisphosphonic acid; and 2-(R-alpha-methylbenzylamino)ethyl-l,l-bisphosphonic acid.
2-(R-alpha-methylbenzylamino)ethyl-l,l-bisphosphonic acid, tetrabutyl ammonium salt.

WO 95/10188 ~ 3 ~ PCT/GB91/02183 Yet another novel genus of compounds within the scope of this invention are compounds of Formula (IV):

~ P03H2 A N - CH2 - CH (IV) wherein A is an alkylenidene radical of 3-6 carbon atoms optionally substituted with C1-C6 alkyl, and agriculturally acceptable salts thereof. Specific compounds within the scope of this genus include:
2-(1-pyrrolidi~yl)ethyl-1,1-bisphosphonic acid;
2-(2,5-dimethyl-1-pyrrolidinyl)ethyl-1,1-bisphos-phonic acid;
2-(1-pyrrolidinyl)ethyl-1,1-bisphosphonic acid, tetramethylammonium salt;
2-(1-pyrrolidinyl)ethyl-1,1-bisphosphonic acid, tributylamino slat;
2-(1-pyrrolidinyl)ethyl-1,1-bisphosphonic acid, trimethylsulfonium salt;
2-(1-hexamethyleneiminyl)ethyl-1,1-bisphosphonic acid;
2-(4-methyl-1-piperidinyl)ethyl-1,1-bisphosphonic acid;
2-(2-methyl-1-piperidinyl)ethyl-1,1-bisphosphonic acid; and 2-(3-methyl-1-piperidinyl)ethyl-1,1-bisphosphonic acid.

Another novel genus of compounds within the scope of this invention are those of Formula (V):

' N P0 H
,. I , 3 2 20 B C - C R
H P3H2 (V) wherein R20 is hydrogen or hydroxyl; and B is a C2-C4 alkylidene linking group, optionally substituted with C1-C6 alkyl;

~ ~- 7 3 ~ ~ 7 -12- PCT/GB94/02183 ~

and agriculturally acceptable salts thereof.

Specific compounds within the scope of this genus include:

l-(2-piperidinyl)-l-hydroxymethane-l,l-bisphosphonic acid;
l-(2-pyrrolidinyl)-l-hydroxymethane-l,l-bisphos-phonic acid; and l-(2-pyrrolidinyl)-l-hydroxymethane-l,l-bisphos-phonic acid, tributylamine salt.

Another class of compounds within the scope of this invention are those of Formula VI:

jR21 ~03H2 H2N C C- OH (VI) wherein R2l and R22 are each independently Cl-C6 alkyl or together constitute a C3-C5 alkylidene group optionally sub-stituted with Cl-C6 alkyl; and agrochemically acceptable salts thereof.

Illustrative compounds within the scope of this invention include:

2-amino-l-hydroxy-2-methylpropyl-l,l-bisphosphonic acid, hydrochloride salt; and l-(l-aminocyclopentyl)-l-hydroxymethyl-l,l-bisphos-phonic acid.

Yet another novel genus of compounds within the scope of this invention are compounds of Formula (VII):

R~25 , 3H2 , , 2 CH (VII) (CR R )t ~ WO95/10188 21 7 3 6 ~ 7 PCT/GB94/02183 wherein t is 2, 3 or 4; R23 and R24 are each independently hydrogen, Cl-ClO alkyl, halo, nitro, Cl-Cg alkoxy, Cl-ClO
aralkyl, cyano, trifluoromethyl or represent a unit of unsat-uration; and R25 is hydrogen, Cl-C6 alkyl, C7-C~0 aralkyl~
halo, nitro, trifluoromethyl or cyano. Each R and R may themselves be different members of the group listed above.

Illustrative compounds within the scope of this invention include:

2-[l-(2 methyl l,4,5,6 tetrahydro l,3 pyrimidinyl)]-ethyl-l,l,bisphosphonic acid; and 2-[l-(4-methyl-l,3-imidazolyl)]ethyl-l,l-bisphos-phonic acid.

The formulae given above are intended to include tautomeric forms of the structures drawn therein, as well as physically distinguishable modifications of the compounds which may arise, for example, from different ways in which the molecules are arranged in a crystal lattice, or from the inability of parts of the molecule to rotate freely in rela-tion to other parts, or from geometrical isomerism, or from intra-molecular or inter-molecular hydrogen bonding, or other-wlse .

The compounds of such formulae can exist in enan-tiomeric forms. The invention includes both individual enan-tiomers and mixtures of the two in all proportions.

As is employed herein, the term "hydrocarbyl", whether representing a substituent on its own or whether it is part of the definition of a larger group (e.g., as in hydro-carbyloxy, hydrocarbyl-S(O)m-, etc.) is intended to include hydrocarbyl groups having from l to 16 carbon atoms. The term hydrocarbyl therefore includes, for example, Cl to Cl6 alkyl including both straight and branched chain isomers (e.g., methyl, ethyl, propyl, isopropyl, sec-hexyl and hexyl); cyclo-alkyl of 3 to 16 carbon atoms (e.g., cyclopropyl, cyclobutyl and cyclohexyl); C2 to Cl6 alkenyl including for example allyl WO 95/10188 ~ :L 7 ~ ~ ~ 7 PCT/GB9~/02183 ~

and crotyl; C2 to C16 alkynyl (e.g., propynyl); phenyl;
phenylalkyl; alkylphenyl, alkenylphenyl, alkynylphenyl, alkyl-benzyl, alkenylbenzyl, alkynyl benzyl, naphthyl and the like.

The term "substituted" when applied to the term "hydrocarbyl" (or to a similar term unless specifically defined otherwise) is intended to include hydrocarbyl groups, as defined above, having one or more substituents selected from the group consisting of halogen (i.e., fluorine, chlo-rine, bromine, and iodine); C1_l0 alkoxy; C1_l0 alkyl-S(O)m-;
cyano; nitro; carboxy, and salts, amides and esters thereof;
alkanoyl of 2 to 10 carbon atoms; and phenyl optionally substituted by one or more C1_l0 alkyl, Cl_10 alkoxy, C1_l0 alkyl-S(O)m~, nitro, fluorine, chlorine, bromine, cyano, or CF3 groups. In the above definitions, m is 0, 1 or 2.

Further, when the hydrocarbyl radical is a substi-tuted aryl radical (e.g., phenyl, benzyl or naphthyl), the substituents may include one or more of the substituents listed in the last foregoing paragraph, and may also include nitro. The term "substituted pyridyl" is intended to include those substituents detailed above for substituted aryl radicals.

In addition, unless specified otherwise, the term "alkyl" is intended to include straight chain, branched and cycloalkyl compounds. The above definitions the term "halo-gen" includes fluoro, chloro, bromo and iodo groups. In polyhalogenated groups the halogens may be the same or different.

The compounds of the present invention have been found to be active herbicides, possessing utility as post-emergence herbicides and useful against a wide range of plant species including broadleaf and grassy species.

This invention therefore also relates to a method for controlling undesirable vegetation comprising applying to a locus where control of such vegetation is desired subsequent ~ WOg5/10188 15 21~ 3 6 0~

to the emergence of such vegetation a herbicidally effective amount of a compound as described herein, together with an inert diluent or carrier suitable for use with herbicides.

The terms "herbicide" and ~'herbicidal" are used herein to denote the inhibitive control or modification of undesired plant growth. Inhibitive control and modification include all deviations from natural development such as, for example, total killing, growth retardation, defoliation, desiccation, regulation, stunting, tillering, stimulation, leaf burn and dwarfing. The term "herbicidally effective amount" is used to denote any amount which achieves such control or modification when applied to the undesired plants themselves or to the area in which these plants are growing.
The term "plants" is intended to include germinated seeds, emerging seedlings and established vegetation, including both roots and above-ground portions.

The term "agriculturally acceptable salt" is easily determined by one of ordinary skill in the art and includes alkali metal, ammonium, phosphonium, sulfonium salts, organic derivatives thereof, and the like.

The compounds of this invention wherein Rl is hydro-gen may generally be prepared by reacting tetraethyl vinyl-idene bis(phosphonate) with an appropriate amine. Such reaction is typically carried out at between about o and about 100C in the presence of a suitable nonreactive solvent, such as acetonitrile, diethyl ether, tolene, tetrahydrofuran, and the like. The ester groups may then be removed using bromotrimethylsilane or àqueous hydrochloric acid.

Tetraethyl vinylidene bis(phosphonate) may be prepared in accordance with the method disclosed by C.
Degenhardt et al., J. Org. Chem., Vol 51, pp 3488-3490 (1986).
The amines employed are either commercially available or may be prepared by means well known to one of s~ill in the art, e.g., preparation from the corresponding bromides by a Gabriel Synthesis (see Vogel, "A Textbook of Practical Organic Chemistry", 3d Ed., pp 569).

WO95/10188 2 ~ 7 3 6 ~ ~ - 16- PCTIGB94/02183 ~

For the production of compounds wherein the amine contains sensitive groups, the ester groups may first be transesterified by the use of a compound such as bromotri-methylsilane. Such groups can be subsequently unblocked by hydrolysis with water.

Alternatively, for producing compounds wherein Rl is other than H, the appropriate carboxylic acid, amide or nitrile can be converted employing PCl3 and phosphorous acid or P2O3 utilizing means well known to those of skill in the art.

The compositions of this invention comprise a com-pound of Formula (I) above and a suitable carrier, which carriers are well known to one of ordinary skill in the art.

The compounds of the present invention are useful as herbicides and can be applied in a variety of ways known to those skilled in the art, at various concentrations. The compounds are useful in controlling the growth of undesirable vegetation by post-emergent application to the locus where control is desired. In practice, the compounds are applied as formulations containing the various adjuvants and carriers known to or used in the industry for facilitating dispersion.
The choice of formulation and mode of application for any given compound may affect its activity, and selection will be made accordingly. The compounds of the invention may thus be formulated as wettable powders, as emulsifiable concentrates, as powders or dusts, as flowables, as solutions, suspensions or emulsions, or in controlled-release forms such as micro-capsules. These formulations may contain as little as about 0.5~ to as much as amount 95% or more by weight of active ingredient. The optimum amount for any given compound will depend upon the nature of plants to be controlled. The rate of application will generally vary from about O.Ol to about lO
pounds per acre, preferably from about 0.02 to about 4 pounds per acre.

~ wos5llol88 ~ 7 3 G ~`7 PCT/GB94/02183 Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid car-riers. The particles contain the active ingredient retained in a solid matrix. Typical solid matrices include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic solids. Wettable powders normally contain about 5%
to about 95% of the active ingredient plus a small amount of wetting, dispersing, or emulsifying agent.

Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid, and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingre-dient may range from about 0.5% to about 95% of the concen-trate.

Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers.

Microcapsules are typically droplets or solutions of the active material enclosed in an inert porous shell which allows escape of the enclosed material to the surroundings at controlled rates. Encapsulated droplet are typically about l to 50 microns in diameter. The enclosed material typically constitutes about 50 to 95% of the weight of the capsule, and may include solvent in addition to the active compound. Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, poly-acrylonitriles, polyacrylates, polyesters, polyamides, poly-ureas, polyurethanes and starch xanthates.

WO9S/10188 - ~ 7 ~ ~ ~ 7 -18- PCT/GB94/02183 Other useful formulations for herbicidal appli-cations include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired con-centration, such as water acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurized sprayers, wherein the active ingredient is dispersed in finely-divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as the Freons, may also be used.

Many of these formulations include wetting, dispers-ing or emulsifying agents. Examples are alkyl and alkylaryl sulfonates and sulfates and their salts; polyhydric alcohols;
polyethoxylated alcohols; esters and fatty amines. These agents when used normally comprise from 0.1% to 15% by weight of the formulation.

Each of the above formulations can be prepared as a package containing the herbicide together with other ingre-dients of the formulation (diluents, emulsifiers, surfactants etc.). The formulations can also be prepared by a tank mix method, in which the ingredients are obtained separately and combined at the grower site.

The compounds of the present invention are also use-ful when combined with other herbicides and/or defoliants, desiccants, growth inhibitors, and the like. These other materials can comprise from about 5% to about 95% of the active ingredients in the formulations. These combinations frequently provide a higher level of effectiveness in con-trolling weeds and often provide results unattainable with separate formulations of the individual herbicides.

Examples of other herbicides, defoliants, desiccants and plant growth inhibitors with which the compounds of this invention can be combined are:

A. Benzo-2,1,3-thiadiazin-4-one-2,2-dioxides such as bentazone;

~ wossllol88 2 ~ 7 3 ~ ~ ~ PCT/GB94/02183 B. hormone herbicides, particularly the phenoxy alkanoic acids such as MCPA, MCPA-thioethyl, dichlorprop, 2,4,5-T, MCPB, 2,4-D, 2,4-DB, mecoprop, trichlopyr, fluroxy-pyr, clopyralid, and their derivatives (e.g. salts, esters and amides);
C. l,3-dimethylpyrazole derivatives such as pyrazoxyfen, pyrazolate and benzofenap;
~ D. Dinitrophenols and their derivatives (e.g.
acetates such as DNOC, dinoterb, dinoseb and its ester, dinoseb acetate;
E. dinitroaniline herbicides such as dinitramine, trifluralin, ethalfluralin, pendimethalin; and oryzalin;
F. arylurea herbicides such as diuron, flumeturon, metoxuron, neburon, isoproturon, chlorotoluron, chloroxuron, linuron, monolinuron, chlorobromuron, daimuron, and meth-abenzthiazuron;
G. phenylcarbamoyloxyphenylcarbamates such as phen-medipham and desmedipham;
H. 2-phenylpyridazin-3-ones such as chloridazon, and norflurazon;
I. uracil herbicides such as lenacil, bromacil and terbacil;
J. triazine herbicides such as atrazine, simazine, aziprotryne, cyanazine, prometryn, dimethametryn, simetryne, and terbutryn;
K. phosphorothioate herbicides such as piperophos, bensulide, and butamifos;
L. thiolcarbamate herbicides such as cycloate, vernolate, molinate, thiobencarb, butylate*, EPTC*, triallate, diallate, ethyl esprocarb, tiocarbazil, pyridate, and dimepi-perate;
M. l,2,4-triazin-5-one herbicides such as metamitron and metribuzin;
N. benzoic acid herbicides such as 2,3,6-TBA, dicamba and chloramben;
O. anilide herbicides such as pretilachlor, butachlor, the corresponding alachlor, the corresponding com-pound propachlor, propanil, metazachlor, metolachlor, aceto-chlor, and dimethachlor;

WO 9S/10188 ~! 1 7 3 S ~ 7 --2 0-- PCT/GB94102183 P. dihalobenzonitrile herbicides such as dichlo-benil, bromoxynil and loxynil;
Q. haloalkanoic herbicides such as dalapon, TCA and salts thereof;
R. diphenylether herbicides such as lactofen, fluroglycofen or salts or esters thereof, nitrofen, bifenox, acifluorfen and salts and esters thereof, oxyfluorfen and fome~safen; chlornitrofen and chlomethoxyfen;
S. phenoxyphenoxypropionate herbicides such as diclofop and esters thereof such as the methyl ester, fluazi-fop and esters thereof, haloxyfop and esters thereof, quizalofop and esters thereof and fenoxaprop and esters thereof such as the ethyl ester;
T. cyclohexanedione herbicides such as alloxydim and salts thereof, sethoxydim, cycloxydim, sulcotrione, tralkoxydim, and clethodim;
U. sulfonyl urea herbicides such as chlorosulfuron, sulfometuron, metsulfuron and esters thereof; benzsulfuron and es~ers thereof such as the ester thereof methyl, DPX-M6313, chlorimuron and esters such as the ethyl ester thereof, pirimisulfuron and esters such as the methyl ester thereof, DPX-LS300 and pyrazosulfuron;
V. imidazolidinone herbicides such as imazaquin, imazamethabenz, imazapyr and isopropylammonium salts thereof, imazethapyr;
W. arylanilide herbicides such as flamprop and esters thereof, benzoylprop-ethyl, diflufenican;
X. amino acid herbicides such as glyphosate and gluyfosinate and their salts and esters, sulphosate, and bilanafos;
Y. organoarsenical herbicides such as MSMA;
z. herbicidal amide derivative such as napropamide, propyzamide, carbetamide, tebutam, bromobutide, isoxaben, naproanilide, diphenamid, and naptalam;
AA. miscellaneous herbicides including ethofumesate, cinmethylin, difenzoquat and salts thereof such as the methyl sulfate salt, clomazone, oxadiazon, bromofenoxim, barban, tridiphane, (in the ratio 3:1) flurochloridone, quinchlorac and mefanacet;

WO95/10188 2 1 7 3 6 0 ~ PCT/GB94/02183 BB. examples of useful contact herbicides include bipyridylium herbicides such as those in which the active entity is paraquat and those in which the active entity is diquat.

* These compounds are preferably employed in combination with a safener such as 2,2-dichloro-N,N-di-2-propenylacetamide (dichlormid).

These formulations can be applied to the areas where control is desired by conventional methods. Dust and liquid compositions, for example, can be applied by the use of power-dusters, boom and hand sprayers and spray dusters. The formu-lations can also be applied from airplanes as a dust or a spray or by rope wick applications.

The following are examples of typical formulations.

5% dust:5 parts active compound 95 parts talc 2% dust:2 parts active compound 1 part highly dispersed silicic acid 97 parts talc These dusts are formed by mixing the components then grinding the mixture to the desired particle size.

Wettable powders:

70%:70 parts active compound 5 parts sodium dibutylnaphthylsulfonate

3 parts naphthalenesulfonic acid/phenolsulfonic acid/formaldehyde condensate (3:2:1) 10 parts kaolin 12 parts Champagne chalk 2~73~ 22-40%:40 parts active compound 5 parts sodium lignin sulfonate 1 part sodium dibutylnaphthalene sulfonic acid 54 parts silicic acid 25%:25 parts active compound

4.5 parts calcium lignin sulfate 1.9 parts Champagne chalk/hydroxyethyl cellulose (1:1) 1.5 parts sodium dibutylnaphthalene sulfonate 19.5 silicic acid 19.5 parts Champagne chalk 28.1 parts kaolin 25%:25 parts active compound 2.5 parts isooctylphenoxy-polyethylene-ethanol 1.7 parts Champagne chalk/hydroxyethyl cellulose (1:1) 8.3 parts sodium aluminum silicate 16.5 parts kieselguhr 46 parts kaolin 10%:10 parts active compound 3 parts of a mixture of sodium salts of saturated fatty alcohol sulfates

5 parts naphthalenesulfonic acid/
formaldehyde condensate 82 parts kaolin These wettable powders are prepared by intimately mixing the active compounds with the additives in suitable mixers, and grinding the resulting mixture in mills or rollers.

: Z ~ 0 '7 Emulsifiable concentrate:

25%: 25 parts active substance 2.5 parts epoxidized vegetable oil l0 parts of an alkylarylsulfonate/fatty alcohol polyglycol ether mixture 5 parts dimethylformamide 57.5 parts xylene The amount of the present compositions which consti-tute a herbicidally effective amount depends upon the nature of the seeds or plants to be controlled. The rate of appli-cation of active ingredients varies from about 0.0l to about 25 pounds per acre, preferably about 0.l0 to about l0 pounds per acre with the actual amount depending on the overall costs and the desired results. It will be readily apparent to one skilled in the art that compositions exhibiting lower herbi-cidal activity will require a higher dosage than more active compounds for the same degree of control.

EXAMPLES

The following examples are intended to further illustrate the present invention and are not intended to limit the scope of this invention in any manner whatsoever.

EXAMPLE l Preparation of 2-[l-(l,2,4-triazole)lethyl-l,l-bisPhosphonic acid (ComPound No. 3) One gram of l,2,4-triazole was dissolved in 40 ml of THF and cooled to -78C in a nitrogen atmosphere. n-Butyl-lithium (974 mg) was then added dropwise and the resultant white suspension stirred at -78C for five minutes. After warming to room temperature, the mixture was stirred for 45 minutes and then cooled again to -78C. Tetraethyl vinyl-WO9S/10188 PCT/GB94/02183 ~
~ 7 -24- _ idinebiphosphonate (4.78 gm) was then added dropwise over a 20 minute period. When the addition was complete, the mixture was stirred for 15 minutes at -78C, then warmed to 0C and stirring continued for one hour. The reaction was quenched with 10 ml of water and the THF removed under reduced pressure to give the crude product which was then combined with 35 ml of aqueous K2C03 solution. The resulting mixture was extracted with 3 X 100 ml portions of dichloromethane. The extracts were combined, dried (MgS04), and the solvent removed under reduced pressure to afford a mobile oil. Column chroma-tography on silica gel with 10% methanol/dichloromethane provided 1.3 gm of tetraethyl 2-~1-(1,2,4-triazole)ethyl-1,1-bisphosphonate. Hydrolysis of this material to form Compound 3 was achieved by heating a dichloromethane solution of the tetraethyl ester and 500 mol% of bromotrimethylsilane at 45C
for four hours and then removing the volatiles in vacuo.
Refluxing the residual oil with water for 30 minutes followed by cooling to room temperature and removal of the water under high vacuum resulted in the isolation of 3 in quantitative yield.

PreParation of l-hYdroxv-r2-amino-2-methYl~r bisPhosphonic acid (Com~ound No. 8) To a three-necked 250 ml round-bottomed flask equipped with a condenser, mechanical stirrer, oil bath and thermometer were added 2.37 gm of 2-aminoisobutyric acid, 85 ml of chlorobenzene and 3.2 gm of phosphorous acid. The mixture was heated at reflux for one hour and then cooled to 50C. Phosphorus trichloride (9.62 gm) was then added and the mixture again heated to refluxing with stirring for five hours. At the end of this time, the mixture was allowed to cool to room temperature and the chlorobenzene carefully decanted. Fresh chlorobenzene (85 ml) and 80 ml of 6N HCl were then added and the mixture heated to refluxing with stir-ring. After six hours, the yellowish suspension was cooled to ~ WO95/10188 2 ~ 7 3 6 0 7 PCT/GBg4/02183 room temperature, vacuum filtered through dicalite, and the volatiles removed under high vacuum to afford a colorless syrup. Trituration with ethanol under steam heating provided 3.09 gm of product 8 as a white solid after isolation by vacuum filtration.

Preparation of l-hydrcxy-l-f2-pyrrolidino) bisphos~honic acid (Compound No. 9~

To a 200 ml three-necked flask equipped with a mechanical stirrer and reflux condenser carrying a nitrogen bubbler were added 4 gm of proline; 5.7 gm of phosphorous acid and 25 ml of dioxane. Phosphorus trichloride (9.6 gm) was then added dropwise at 80C and the mixture stirred at 80C
for two hours. After cooling the reaction mixture to room temperature, water (150 ml) was added to the resulting mixture was filtered through activated carbon. The filtrate was evaporated under reduced pressure and the residual clear oil placed in a vacuum oven (60C) overnight. At the end of this time the residue was triturated with EtOH and the resulting white solid isolated by vacuum filtration. Drying the solid in a vacuum oven at 60OC afforded 5.9 gm of Compound 9.

PreParation of 2-(but-3-envlamino)ethyl-1,1-~isphosphonic acid (Compound No. 29) A solution of 1.08 gm of 1-aminobut-3-ene in five ml of methanol was added to 3.8 gm of tetraethyl vinylidinebis-phosphonate at room temperature. After the resulting mixture had stirred overnight, an additional 0.12 gm of 1-aminobUt-3-ene was added and the stirring continued for an additional four hours. The reaction mixture was then concentrated under WO9S/10188 PCT/GB94/02183 ~
217~7 -26-reduced pressure to yield 4.56 gm of tetraethyl 2-(but-3-enyl-amino)ethyl-l,1-bisphosphonate. A 4.4 gm sample of this material was combined with five ml of acetonitrile and 7.2 ml of bromotrimethylsilane. After stirring at room temperature for 48 hours, the solution was heated to refluxing for four hours and then concentrated under reduced pressure. The resulting tetra(trimethylsilyl) ester was hydrolyzed by refluxing with 25 ml of water for 30 minutes. Removal of the volatile materials by lyophylization afforded 3.2 gm of Com-pound 20 as a stiff, colorless, hygroscopic foam.

Preparation of 2-(3-methYl-l-PiperidinYl)ethY
bisPhosPhonic acid (Com~ound No. 37) A solution of one ml of 3-methylpiperidine in five ml of methanol was added dropwise to 2.43 gm of tetraethyl vinylidinebisphosphonate at room temperature. The reaction was stirred overnight and the mixture then concentrated under reduced pressure to yield 3.4 grams of tetraethyl 2-(3-methyl-1-piperidinyl)ethyl-1,1-bisphosphonate. A portion of this material (3.37 gm) was dissolved in five ml of acetonitrile followed by the additlon of five ml of bromotrimethylsilane.
The resulting mixture was refluxed overnight, then allowed to cool to room temperature, and then concentrated under reduced pressure. Water (25 ml) was added to the residual oil and the mixture stirred for three hours. Removal of the water and other volatile components under high vacuum afforded 2.84 gm of 37 as a stiff, hygroscopic, colorless foam.

WO 95/10188 --27-- 2 1~ 3 6 ~ 7 PCT/GB9~/02183 Preparation of 2-(4 methylbenzylamino)ethvl-1,1-bisphosphonic acid (Compound No. 67) To a 100 ml boiling flask were added 3.5 gm of tetraethyl vinylidine-1,1-bisphosphonate, 20 ml of acetoni-trile, and 1.5 gm of 4-methylbenzylamine. The resulting mixture was magnetically stirred overnight at room tempera-ture. At the end of this time, the solvent was removed under reduced pressure to give 4.66 gm of tetraethyl 2-(4-methyl-benzylamino)ethyl-1,1-bisphosphonate. A portion of this material (3.87 gm) was placed in a 100 ml boiling flask equipped with a magnetic stirrer and refluxed for four hours with 25 ml of concentrated HCl. Removal of the volatile materials under high vacuum afforded 3.21 gm of 67 as a color-less, hygroscopic glass.

Employing a process similar to those described above, the following compounds, listed in Table I, were prepared:

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C) ~ _I ,1 _I ,1 WO 95/10188 ~ ~ 7 ~ PCT/GB94/02183 HERBICIDAL SCREENING TESTS

The compounds listed in the foregoing table were tested for herbicidal activity by various methods and at various rates of application. The results of some of these tests are given below. Results obtained in herbicidal screening are affected by a number of factors including: the amount of sunlight, soil type, soil pH, temperature, humidity, depth of planting, plant growth stage, application rate as ~
well as many other factors. All testing procedures are admin-istered with the least amount of variability possible. State of the art e~uipment and techniques are employed to enable the screening process to remain consistent and reliable.

PRE-EMERGENCE HERBICIDAL SCREENING TEST

on the day preceding treatment, seeds of several different weed species were planted in sandy loam soil con-taining only trace organic matter. Propagules were sown in individual rows using one species per row across the width of an aluminum flat (19.5 x 9.5 x 6 cm). The grass weeds planted were green foxtail (Setaria viridis) ("SETVI"), wild oat (Avena fatua) ("AVEFA"), barnyardgrass (Echinochloa crus-galll) ( "ECHCG"). Broadleaf weeds utilized were wild mustard (Brassica kaber) also known as (sinapis arvensis) ("SINAR"), velvetleaf (Abutilon theophrasti) ("ABUTH") and morningglory (Ipomoea spp.) ("IPOSS")-. Additionally, yellow nutsedge (Cyperus esculentus) ("CYPES"), nutlets were sown. Seeding depths ranged from 1.0 to 1.5 cm and plant densities ranged from 3 to 25 plants per row depending on individual plant species.

Solutions of the test compounds were prepared by weighing out 18.8 and 74.7 mg for 1 and 4 kg/ha applications respectively, of the test compound into a 60 ml wide-mouth bottle, then dissolving the compound in 14.0 ml of deionized water containing 0.5% v/v Tween 20~ (polyoxyethylene sorbitan monolaurate emulsifier) as a surfactant. Additional solvents, wo 95~l0l88 ~ ~ 7 3 ~ ~ 7 5 PCTIGBs~/02183 ~

not exceeding 2 ml (15~ of spray volume), were used if needed to dissolve the compound.

The soil surface was sprayed inside an enclosed linear spray table with the nozzle set at 30.5 cm (12 inches) above the soil line. The spray table was calibrated to deliver 748 L/ha (80 gal/A) with the application rate being 4.0 kg/ha or 1.0 kg/ha (as indicated in Table II below).
After treatment the flats were placed into a greenhouse and watered overhead by sprinkling. The greenhouse environmental systems provided the plants with natural and artificial (via metal halide lamps) lighting to attain 14 hours of light per day. Day and night temperatures were maintained at 29 and 21C respectively.

The degree of weed control was evaluated and recorded 17-21 days after treatment as a percentage of weed control as compared to the growth of the same species of the same age in an untreated control flat. Percent control is the total injury to the plants due to all factors including:
inhibited emergence, stunting, malformation, chlorosis and other types of plant injury. The control ratings range from 0 to 100 percent, where 0~ represents no effect with growth equal to the untreated control and where 100% represents complete kill. A dash indicates that no test was performed at that level of application.

POST-EMERGENCE HERBICIDAL EVALUATION

The soil was prepared and seeded with the same species and methodology described for the pre-emergence test.
Post-emergence flats were placed in the greenhouse under the same environmental conditions as described for the pre-emergence flats and watered overhead by sprinkling. Plants were grown for 10 to 12 days (or to the appropriate growth stage) prior to compound application. Grasses were sprayed at a 3 to 4 leaf stage and broadleaves at a 1 to 2 leaf stage.
Yellow nutsedge was 5 to 7 cm tall at application.

-WO95/10188 -55- ~ 6~ 7 PCT/GB94/02183 Plants were sprayed 30.5 cm (12 inches) above the foliage with the same spray solution as prepared for the pre-emergence test. The application rate was 4.0 kg/ha or l.0 kg/ha (as indicated in Table III below). Treated plants were then returned to a greenhouse and watered daily without wet-ting the foliage. The degree of weed control was evaluated 17-21 days after application and recorded as percentage of control as compared to the growth of the same species in an untreated control flat of the same age. The percent control scale (0-100%) used to evaluate the pre-emergence treatment was also applied to the post-emergence treatment.

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2~6~7 The above date indicates the efficacy of the present claimed compounds when applied post-emergently, coupled with their safety to plants when applied pre-emergently.

Claims

WHAT IS CLAIMED IS:

1. A herbicidal composition comprising:

(A) A compound of the Formula (I):

(I) wherein R1 is hydrogen, hydroxy, C1-C4 alkoxy, halogen, C1-C4 alkyl, C1-C4 haloalkyl, hydroxy-C1-C4-alkyl, hydroxy--C1-C4-alkoxy or N(R6)(R7) wherein R6 and R7 are each indepen-dently hydrogen or C1-C3 alkyl ;
R2 and R3 are each independently hydrogen; hydro-carbyl; substituted hydrocarbyl; hydrocarbyloxy; substituted hydrocarbyloxy; hydrocarbyl-S(O)m-; or substituted hydro-carbyl-S(O)m-; or R2 and R3 together form a 3-6 membered carbocyclic ring, optionally substituted with halogen, hydroxy, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio or N(R8)(R9) wherein R8 and R9 are each independently hydrogen or C1-C12 alkyl; and R4 and R5 are each independently hydrogen; hydro-carbyl; substituted hydrocarbyl; hydrocarbyloxy; substituted hydrocarbyloxy; hydrocarbyl-S(O)m-; substituted hydrocar-byl-S(O)m ; pyridyl; substituted pyridyl; or are of the formula N(R10)(R11) wherein R10 and R11 are independently hydrogen, hydrocarbyl or substituted hydrocarbyl; or R4 and R5 together with the nitrogen to which they are bound form an aziridine, piperazine, morpholine, thiomor-pholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimine, piperidine, tetrahydropyridine, pyrazole, imidazole, pyrrole, triazole, tetrahydropyrimidine, dihydro-imidazole, pyrroline, azetidine, perhydroindole, perhydro-quinoline, perhydroisoquinoline or pyrrolidine ring, any of which may be optionally substituted with C1-C12 alkyl, halo, C6-C10 aryl, C6-C10 aryl substituted with halo or C1-C6 alkyl, C7-C16 aralkyl, C7-C16 aralkyl substituted with halo or C1-C6 alkyl, nitro, halo-C1-C10-alkyl, C1-C10 alkoxy, C1-C10 alkyl-thio, C1-C10 alkylsulfonyl, phenoxy, phenoxy substituted with halo or C1-26 alkyl, C1-C10 alkenyl or cyano.
R2 and R4 together with the nitrogen and carbon atoms to which they are bound form an aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomor-pholine sulfonyl, hexamethyleneimine, piperidine, tetrahydro-pyridine, pyrazole, imidazole, pyrrole, triazole, tetrahydro-pyrimidine, dihydroimidazole, pyrroline, azetidine, perhydro-indole, perhydroquinoline, perhydroisoquinoline or pyrrolidine ring, any of which may be optionally substituted with C1-C12 alkyl, halo, C6-C10 aryl, C6-C10 aryl substituted with halo or C1-C6 alkyl, C7-C16 aralkyl, C7-C16 aralkyl substituted with halo or C1-C6 alkyl, nitro, halo-C1-C10-alkyl, C1-C10 alkoxy, C1-C10 alkylthio, C1-C10 alkylsulfonyl, phenoxy, phenoxy substituted with halo or C1-C6 alkyl, C1-C10 alkenyl or cyano;
and m is 0, 1 or 2;
and agrochemically acceptable salts thereof; and (B) An agrochemically acceptable carrier therefor.

2. A composition in accordance with claim 1 wherein R1 is hydrogen or hydroxy.

3. A composition in accordance with claim 2 wherein R2 and R3 are each independently hydrogen or C1-C6 alkyl.

4. A composition in accordance with claim 3 wherein R4 and R5 are each independently hydrogen, C1-C6 alkyl, C1-C6 alkenyl, benzyl or benzyl substituted with C1-C6 alkyl or halo.

5. A composition in accordance with claim 3 wherein R4 and R5 together with the nitrogen to which they are bound form a pyrrolidine or piperidine ring, optionally substituted with fluorine, hydroxy, C1-C6 alkoxy or C1-C6 alkyl.

6. A composition in accordance with claim 1 wherein:
R1 is hydrogen, hydroxy, halogen or C1-C4 alkyl;
R2 and R3 are independently C1-C12 alkyl; C2-C12 alkenyl; C2-C12 alkynyl; halo-C1-C12 alkyl, halo-C2-C12 2 C12 alkynyl; C6-C14 aralkyl; C1-C12 alkoxy;
or C1-C12 alkylthio;
R4 and R5 are independently hydrogen; C1-C6 alkyl;
C2-C6 alkenyl; C2-C6 alkynyl; halo-C1-C6 alkyl; halo-C2-C6 alkenyl; halo-C1-C6-alkynyl; pyridyl; substituted pyridyl;
phenyl; substituted phenyl; C7-C14 aralkyl; or substituted C7-C14 aralkyl; or R4 and R5 together with the nitrogen to which they are bound form a tetrahydropyrimidine, tetrahydropyridine or imidazole ring or a (CH2)n-N- ring wherein n is 3-6, option-ally substituted with halogen, hydroxy, C1-C6 alkoxy, nitro, C1-C6 alkyl C7-C16 aralkyl or C1-C6 alkylthio groups.

7. A composition in accordance with claim 6 wherein R1 is hydrogen or hydroxy;
R2 and R3 are each independently hydrogen or C1-C6 alkyl; and R4 and R5 are each independently hydrogen, C1-C6 alkyl, C1-C6 alkenyl, benzyl, benzyl substituted with C1-C6 alkyl or halo or R4 and R5 together with the nitrogen to which they are bound form a pyrrolidine or piperidine ring, optionally substituted with fluorine, hydroxy, C1-C6 alkoxy or C1-C6 alkyl.

8. A composition in accordance with claim 1 wherein component (A) comprises 2-(1-pyrrolidinyl)ethyl-1,1-bisphos-phonic acid; 2-(1-piperdinyl)ethyl-1,1-bisphosphonic acid;
2-(propylamino)ethyl-1,1-bisphosphonic acid; 2-(N-methyl-N-ethylamino)ethyl-1,1-bisphosphonic acid; 2-(n-butylamino)-ethyl-1,1-bisphosphonic acid; 2-(2-propenylamino)ethyl-1,1-bisphosphonic acid; 2-(R-alpha-methylbenzylamino)ethyl-1,1-bisphosphonic acid; 2-(2-methylpropylamino)ethyl-1,1-bis-phosphonic acid; 2-[1-(4-methyl-1,3-imidazolyl)]ethyl-1,1-bisphosphonic acid; or 2-[1-(1,2,3,6-tetrahydropyridinyl)]-ethyl-1,1-bisphosphonic acid.

9. A method of controlling the growth of plants comprising applying to the locus of such plants a herbicidally effective amount of a compound of the Formula (I):

(I) wherein R1 is hydrogen, hydroxy, C1-C4 alkoxy, halogen, C1-C4 alkyl, C1-C4 haloalkyl, hydroxy-C1-C4-alkyl, hydroxy--C1-C4-alkoxy or N(R6)(R7) wherein R6 and R7 are each indepen-dentlY hydrogen or C1-C3 alkyl;
R2 and R3 are each independently hydrogen; hydro-carbyl; substituted hydrocarbyl; hydrocarbyloxy; substituted hydrocarbyloxy; hydrocarbyl-S(O)m-; or substituted hydrocar-byl-S(O)m-;
R2 and R3 together form a 3-6 membered carbocyclic ring, optionally substituted with halogen, hydroxy, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio or N(R8)(R9) wherein R8 and R9 are each independently hydrogen or C1-C12 alkyl; and R4 and R5 are each independently hydrogen; hydro-carbyl; substituted hydrocarbyl; hydrocarbyloxy; substituted hydrocarbyloxy; hydrocarbylthio; substituted hydrocarbylthio;
pyridyl; or are of the formula N(R10)(R11) wherein R10 and R11 are independently hydrogen, hydrocarbyl or substituted hydro-carbyl; or R4 and R5 together with the nitrogen to which they are bound form an aziridine, piperazine, morpholine, thiomor-pholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimine, piperidine, tetrahydropyridine, pyrazole, imidazole, pyrrole, triazole, tetrahydropyrimidine, dihydro-imidazole, pyrroline, azetidine, perhydroindole, perhydro-quinoline, perhydroisoquinoline or pyrrolidine ring, any of which may be optionally substituted with C1-C12 alkyl, halo, C6-C10 aryl, C6-C10 aryl substituted with halo or C1-C6 alkyl, C7-C16 aralkyl, C7-C16 aralkyl substituted with halo or C1-C6 alkyl, nitro, halo-C1-C10-alkyl, C1-C10 alkoxy, C1-C10 alkyl-thio, C1-C10 alkylsulfonyl, phenoxy, phenoxy substituted with halo or C1-C6 alkyl, C1-C10 alkenyl or cyano.
R2 and R4 together with the nitrogen and carbon atoms to which they are bound form an aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomor-pholine sulfonyl, hexamethyleneimine, piperidine, tetrahydro-pyridine, pyrazole, imidazole, pyrrole, triazole, tetrahydro-pyrimidine, dihydroimidazole, pyrroline, azetidine, perhydro-indole, perhydroquinoline, perhydroisoquinoline or pyrrolidine ring, any of which may be optionally substituted with C1-C12 alkyl, halo, C6-C10 aryl, C6-C10 aryl substituted with halo or C1-C6 alkyl, C7-C16 aralkyl, C7-C16 aralkyl substituted with halo or C1-C6 alkyl, nitro, halo-C1-C10-alkyl, C1-C10 alkoxy, C1-C10 alkylthio, C1-C10 alkylsulfonyl, phenoxy, phenoxy substituted with halo or C1-C6 alkyl, C1-C10 alkenyl or cyano;
or m is 0, 1 or 2; or an agrochemically acceptable salt thereof.

10. A method in accordance with claim 9 wherein is hydrogen or hydroxy.

11. A method in accordance with claim 10 wherein R2 and R are each independently hydrogen or C1-C6 alkyl.

12. A method in accordance with claim 11 wherein R4 and R5 are each independently hydrogen, C1-C6 alkyl, C1-C6 alkenyl, benzyl or benzyl substituted with C1-C6 alkyl or halo.

13. A method in accordance with claim 11 wherein R4 and R5 together with the nitrogen to which they are bound form a pyrrolidine or piperidine ring.

14. A method in accordance with claim 9 wherein R1 is hydrogen, hydroxy, halogen or C1-C4 alkyl;

R2 and R3 are independently C1-C12 alkyl; C2-C12 alkenyl; C2-C12 alkynyl; halo-C1-C12 alkyl, halo-C2-C12 alkenyl; halo-C2-12 alkynyl; C6-C14 aralkyl; C1-C12 alkoxy;
or C1-C12 alkylthio;
R4 and R5 are independently hydrogen; C1-C6 alkyl;
C2-C6 alkenyl; C2-C6 alkynyl; halo-C1-C6 alkyl; halo-C2-C6 alkenyl; halo-C1-C6-alkynyl; pyridyl; substituted pyridyl;
phenyl; or substituted phenyl; C7-C14 aralkyl; C7-C14 substi-tuted aralkyl; or R4 and R5 together with the nitrogen to which they are bound form a tetrahydropyrimidine, tetrahydropyridine or imidazole ring or a -(CH2)n-N- ring wherein n is 3-6, option-ally substituted with halogen, hydroxy, C1-C6 alkoxy, nitro, C1-C6 alkyl C7-C16 aralkyl or C1-C6 alkylthio groups.

15. A method in accordance with claim 14 wherein R1 is hydrogen or hydroxy;
R2 and R3 are each independently hydrogen or C1-C6 alkyl; and R4 and R5 are each independently hydrogen, C1-C6 alkyl, C1-C6 alkenyl, benzyl, benzyl substituted with C1-C6 alkyl or halo or R4 and R5 together with the nitrogen to which they are bound form a pyrrolidine or a piperidine ring optionally substituted with fluorine, hydroxy, C1-C6 alkoxy or C1-C6 alkyl.

16. A method in accordance with claim 9 wherein said compound is 2-(1-pyrrolidinyl)ethyl-1,1-bisphosphonic acid;
2-(1-piperdinyl)ethyl-1,1-bisphosphonic acid; 2-(propylamino)-ethyl-1,1-bisphosphonic acid; 2-(N,N-methylethylamino)ethyl-1,1-bisphosphonic acid; 2-(n-butylamino)ethyl-1,1-bisphos-phonic acid; 2-(2-propenylamino)ethyl-1,1-bisphosphonic acid;
2-(R-alpha-methylbenzylamino)ethyl-1,1-bisphosphonic acid;
2-(2-methylpropylamino)ethyl-1,1-bisphosphonic acid;
2-[1-(4-methyl-1,3-imidazolyl)]ethyl-1,1-bisphosphonic acid;
or 2-[1-(1,2,3,6-tetrahydropyridinyl)]ethyl-1,1-bisphosphonic acid.

17. A compound having the structural Formula II:

( II) wherein R12 and R13 are each independently hydrogen, C1-C6 straight chain or branched alkyl, hydroxy, C2-C6 alkenyl, C1-C6 alkoxy or C1-C6 alkoxy-C1-C6 alkyl; and agriculturally acceptable salts thereof.

18. A compound of Formula III:

(III) wherein q is 0-10, j is 0-3; R14 and R15 are each indepen-dently hydrogen or C1-C6 alkyl; Ar is benzene, pyridine, pyrimidine, pyridazine, naphthalene, pyrazole, imidazole, triazole, thiazole, furan, thiophene, pyrrole, oxazole or thiadiazole; R16 is halo, C1-C10 alkyl, aryl, substituted aryl, benzyl, substituted benzyl, nitro, halo-C1-C10-alkyl, C1-C10 alkoxy C1-C10 alkylthio, C1-C10 alkylsulfenyl, phenoxy, substituted phenoxy, C1-C10 alkenyl or cyano; and R17, R18 and R19 are each independently hydrogen, C1-C10 alkyl, C1-C10 substituted alkyl, C7-C10 aralkyl or C2-C10 alkenyl;
and agriculturally acceptable salts thereof.

19. A compound of Formula (IV):

(IV) wherein A is an alkylenidene radical of 3-6 carbon atoms optionally substituted with C1-C6 alkyl, and agriculturally acceptable salts thereof.

20. A compound of Formula (V):

(V) wherein R20 is hydrogen or hydroxyl; and B is a C2-C4 alkylidene linking group, optionally substituted with C1-C6 alkyl;
and agriculturally acceptable salts thereof.

21. A compound of Formula (VI):

(VI) wherein R21 and R22 are each independently C1-C6 alkyl or together constitute a C3-C5 alkylidene group optionally sub-stituted with C1-C6 alkyl; and agriculturally acceptable salts thereof.

22. A compound of the Formula (VII) (VII) wherein t is 2, 3 or 4; R23 and R24 are each independently hydrogen, C1-C10 alkyl, halo, nitro, C1-C9 alkoxy, C1-C10 aralkyl, cyano, trifluoromethyl or represent a unit of unsaturation; and R25 is hydrogen, C1-C6 alkyl, C7-C10 aralkyl, halo, nitro, trifluoromethyl or cyano.