SK45296A3 - Herbicidal composition on aza bisphosphonic acid base - Google Patents

Abstract

Herbicidal compositions comprising: (A) a compound of formula (I), wherein R<1> is hydrogen, hydroxy, C1-C4 alkoxy, halogen, C1-C4 alkyl, C1-C4 haloalkyl, hydroxy-C1-C4-alkyl, hydroxy-C1-C4-alkoxy or N(R<6>)(R<7>) wherein R<6> and R<7> are each independently hydrogen or C1-C3 alkyl; R<2> and R<3> are each independently hydrogen; hydrocarbyl; substituted hydrocarbyl; hydrocarbyloxy; substituted hydrocarbyloxy; hydrocarbyl-S(O)m-; or substituted hydrocarbyl-S(O)m-; or R<2> and R<3> 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<8>)(R<9>) wherein R<8> and R<9> are each independently hydrogen or C1-C12 alkyl; and R<4> and R<5> are each independently hydrogen; hydrocarbyl; substituted hydrocarbyl; hydrocarbyloxy; substituted hydrocarbyloxy; hydrocarbylthio; substituted hydrocarbylthio; pyridyl; substituted pyridyl; or are of the formula N(R<10>)(R<11>) wherein R<10> and R<11> are independently hydrogen, hydrocarbyl or substituted hydrocarbyl; or R<4> and R<5> 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 R<2> and R<4> 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

There is no need to emphasize the importance of the need for new effective herbicides. The suppression of weeds and undesirable vegetation is of immense economic importance, as weed competition reduces the production of agricultural crops grown for feed, fruits or seeds. The presence of weeds may reduce the harvesting efficiency and the quality of the harvested crops. Weeds on crops-free areas can cause fire hazards, unwanted transmission of sand or snow and / or irritation to allergy sufferers. Thus, suppressing unwanted weed growth is very advantageous.

In addition, it is highly desirable to have herbicides having the desired activity against plants in post-emergence application, but which further exhibit little significant activity in pre-emergence application. Such herbicides will, for example, allow the suppression of weeds already present in the field, but will not damage crops that have not yet been introduced.

It is therefore an object of the present invention to provide novel effective herbicidal compositions and a novel method for weed control, as well as certain novel herbicidal compounds. It is a further object of the present invention to provide novel herbicidal compositions, methods of weed control and herbicidal compounds that achieve admirable postemergence control that is not associated with significant pre-emergence control.

Although certain herbicidal compounds based on bisphosphonic and azabisphosphonic acids have been published in the prior art, these compounds do not have a structure in which the carbon atom to which the two phosphonic acid groups are attached is attached to the amino nitrogen atom via a single carbon atom.

Japanese Patent Publication 54-147925 (Nissan Chemical) discloses herbicidally active bisphosphonic acid compounds wherein phosphonic acid groups are bonded to a single carbon atom. Such compounds are those of the formula

0X0 n | n (HO) ₂ -P-C-P- (OH) ₂ Y wherein X and Y are each hydrogen, halogen, alkyl or cycloalkyl or salts thereof.

Herbicidally active azabisphosphonic acids wherein the carbon atom to which the two phosphonic acid groups are attached is directly bonded to the nitrogen atom of the amino group are described in U.S. Pat. 4,447,256 (Suzuki et al.); British patent no. 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 International Congress on Phosphorus Compounds, Rabat, October 17-21, 1977, p. 649 - 652

some

Japanese Patent Publication 55-98193 relates to herbicidally active compounds of the general formula h ₂ ° ₃ p

R

I

C ₃ • o ₃ h ₂

Wherein R is hydrogen, lower alkyl or halogen; X is -CH ₂ - or a sulfur or oxygen atom; and Y is hydrogen, lower alkyl or halogen; and their alkali salts.

Although certain azabisphosphonic acid compounds wherein the carbon atom to which the two phosphonic acid groups are attached are bonded to the nitrogen atom through a single carbon atom are known in the art, herbicidal activity has not been described. U.S. Pat.

No. 962,318 discloses compounds useful as flame retardants; German patent DE 2 754 821 discloses compounds useful as chelating agents for water treatment and U.S. Pat. No. 5,133,972, U.S. Pat. No. 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 disclose the pharmaceutical use of certain compounds.

SUMMARY OF THE INVENTION

In one aspect, the present invention provides a herbicidal composition which comprises (I) wherein:

R ² and R ³ (A) a compound of formula I,

R ⁴ R ² PO ₃ H ₂ \ II

R ^J PO ₃ H ₂

R ² and R ³

R ² and R ³

R ² and R ³

R ⁴ and R ⁵

R ⁴ and R ⁵ are hydrogen, hydroxy, C 1 -C 4 alkoxy, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 hydroxyalkyl, C 1 -C 4 hydroxyalkoxy Or a group of formula N (R ⁶ ) (R ⁷ ), wherein R ⁶ and R ⁷ are each independently hydrogen or C 1 -C 3 alkyl;

each independently represents a hydrogen atom; hydrocarbyl; substituted hydrocarbyl? hydrocarbyloxy; substituted hydrocarbyloxy group? hydrocarbyl-S (O) _m -; or a substituted hydrocarbyl-S (O) _m - group; or taken together form a three to six membered carbocyclic ring optionally substituted with halogen, hydroxy, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 alkylthio or N (R ⁸ ) ( R ⁹ ) wherein R ⁸ and R ⁹ are each independently hydrogen or C 1 -C 12 alkyl and are each independently hydrogen; hydrocarbyl; substituted hydrocarbyl; hydrocarbyloxy; substituted hydrocarbyl5 oxy; hydrocarbyl; substituted hydrocarbylthio; pyridyl; substituted pyridyl; or a group of formula N (R ¹⁰ ) (R ¹¹ ) wherein R ¹⁰ and R ¹¹ are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl; or

R ⁴ and R ⁵ together with the nitrogen atom to which they are attached form aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulphinyl, thiomorpholine sulphonyl, hexamethylenimine, piperidine, tetrahydropyridine, pyrazole, pyrimidine, pyrrolidine, pyrrolidine, pyrrolidine, pyrrole, pyrrole, pyrrole, pyrrole, pyrrole, pyrrole, pyrrole, , a perhydroquinoline, perhydroisoquinoline or pyrrolidine ring, each of which rings is optionally substituted with a substituent selected from the group consisting of C 1 -C 12 alkyl, halogen, C 6 -C 10 aryl, C 6 -C 10 aryl substituted halogen or (C1-C6) -alkyl, (C1-C6) -alkyl, (C1-C6) -alkyl, substituted by halogen or (C1-C6) -alkyl, nitro, halogen (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy, (C 1 -C 10) alkylthio, (C 1 -C 10) alkylsulfonyl, phenoxy, halogen-substituted phenoxy, or (C 1 -C 6) -alkyl, (C 1 -C 10) alkenyl and cyano; or r 2 and together with the nitrogen atom and the carbon atom to which they are attached form aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimine, piperidine, tetrahydropyridine, pyrimidine, triazole, imidazole, imidazole, imidazole, imidazole, imidazole, , a perhydroindole, perhydroquinoline, perhydroisoquinoline or pyrrolidine ring, each of which is optionally substituted with a substituent selected from the group consisting of C 1 -C 12 alkyl, halogen, C 6 -C 10 aryl, C 6 -C 10 aryl; is substituted with halogen or alkyl of 1 to 6 carbon atoms, aralkyl of 7 to 16 carbon atoms, aralkyl of 7 to 16 carbon atoms substituted with halogen or alkyl of 1 to 6 carbon atoms, nitr C 1 -C 10 haloalkyl, C 1 -C 10 alkoxy, C 1 -C 10 alkylthio, C 1 -C 10 alkylsulfonyl, phenoxy, phenoxy substituted with halogen or C 1 -C 6 alkyl C 1 -C 10 alkenyl and cyano; and m is 0, 1 or 2;

or an agrochemically acceptable salt thereof; and (B) an agrochemically acceptable carrier for the compound.

A further aspect of the present invention is a method of controlling the growth of plants, which comprises applying a herbicidally effective amount of a compound of the formula I as defined above to the area in which this is to be achieved.

Yet another aspect of the present invention are certain novel compounds whose structure is within the scope of Formula I above.

The following is a detailed description of the invention.

The herbicidal compositions of the present invention comprise a bisphosphonic acid compound of formula I

R ⁴ R ² PO ₃ H ₂ (I) after ₃ h ₂ where

R ^ is hydrogen, hydroxy, C 1 -C 4 alkoxy, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 hydroxyalkyl, C 1 -C 4 hydroxyalkyl carbon or a group of formula N (R ⁶ ) (R ⁷ ) wherein R ⁶ and R ⁷ are each independently hydrogen or C 1 -C 3 alkyl;

R ² and R ³ are each independently hydrogen; hydrocarbyl; substituted hydrocarbyl; hydrocarbyloxy; substituted hydrocarbyloxy; hydrocarbyl-S (O) _m -; or a substituted hydrocarbyl-S (O) _m - group; or

R ² and R ^{3 taken} together form a three to six membered carbocyclic ring optionally substituted by halogen, hydroxy, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio or N ( R ⁸ ) (R ⁹ ) wherein R ⁸ and R ⁹ are each independently hydrogen or C 1 -C 12 alkyl; and

R ⁴ and R ⁵ are each independently hydrogen; hydrocarbyl; substituted hydrocarbyl; hydrocarbyloxy; substituted hydrocarbyloxy; hydrocarbyl; substituted hydrocarbylthio; pyridyl; substituted pyridyl; or a group of formula N (R ¹⁰ ) (R ¹¹ ) wherein R ¹⁰ and R ¹¹ are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl; or

R ⁴ and R ⁵ together with the nitrogen atom to which they are attached form aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethylenimine, piperidine, tetrahydropyridine, pyrazole, tetrahydropyridine, pyrrolidine, pyrrolidine, pyrrolidine, pyrrolidine, pyrrolidine, pyrrolidine, pyrrolidine, pyrrolidine, pyrrole, , a perhydroquinoline, perhydroisoquinoline or pyrrolidine ring, each of which rings is optionally substituted with a substituent selected from the group consisting of C 1 -C 12 alkyl, halogen, C 6 -C 10 aryl, C 6 -C 10 aryl substituted halogen or alkyl of 1 to 6 carbon atoms, aralkyl of 7 to 16 carbon atoms, aralkyl of up to 16 carbon atoms substituted with halogen or alkyl of 1 to 6 carbon atoms, nitro, halogen (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy, (C 1 -C 10) alkylthio, (C 1 -C 10) alkylsulfonyl, phenoxy, halo-substituted phenoxy, (C 1 -C 6) -alkyl, alkenyl C1-C10-cyano; or

R ² and R ⁴ together with the nitrogen atom and the carbon atom to which they are attached form aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimine, piperidine, tetrahydropyridine, pyrazole, triazole, imidazole, triazole, imidazole, triazole, imidazole, triazole, imrazole, imidazole, triazole, imidazole, , azetidine, perhydro indole, perhydroquinoline, perhydroisoquinoline or pyrrolidone rings, each of which is optionally substituted with a substituent selected from the group consisting of C 1 -C 12 alkyl, halogen, C 6 -C 10 aryl, aryl, aryl carbon atoms substituted with halo or C 1 -C 6 alkyl, C 7 -C 16 aralkyl, C 7 -C 16 aralkyl substituted with halogen or C 1 -C 6 alkyl, nitro, C 1 -C 10 haloalkyl, C 1 -C 10 alkoxy, C 1 -C 10 alkylthio, C 1 -C 10 alkylsulfonyl, phenoxy, halo-substituted or C 1 -C 6 -alkyl phenoxy C 1 -C 10 alkenyl and cyano; and m is 0, 1 or 2;

or an agrochemically acceptable salt thereof.

In the compounds of formula I, preferably r ¹ is hydrogen, hydroxy, halogen or C 1 -C 4 alkyl;

R ² and R ³ are each independently H; C 1 -C 12 alkyl; (C 2 -C 12) alkenyl; (C 2 -C 12) alkynyl; haloalkyl of 1 to 12 carbon atoms; haloalkenyl of 2 to 12 carbon atoms; haloalkynyl of 2 to 12 carbon atoms; (C 6 -C 14) aralkyl; C 1 -C 12 alkoxy or C 1 -C 12 alkylthio;

R ⁴ and R ⁵ are each independently C 1 -C 6 alkyl; (C 2 -C 6) alkenyl; (C 2 -C 6) alkynyl; (C 1 -C 6) haloalkyl; haloalkenyl of 2 to 6 carbon atoms; haloalkynyl having 2 to 6 carbon atoms; pyridyl; substituted pyridyl; phenyl; substituted phenyl; (C 7 -C 14) aralkyl; or substituted (C7 -C14) aralkyl; or

R ⁴ and R ⁵ together with the nitrogen atom to which they are attached form a tetrahydropyrimidine, tetrahydropyridine or imidazole ring or a ring having the structure - (CH ₂ ) _n -N-, wherein n represents a number from 2 to 6, each of which rings is optionally substituted with halogen, hydroxy, (C1-C6) alkoxy, nitro, (C1-C6) alkyl, (C1-C6) aralkyl or (C1-C6) alkylthio.

In the compounds of formula I, particularly preferred

R ¹ is H or OH;

R ² and R ³ are each independently hydrogen or C 1 -C 6 alkyl; and

R ⁴ and R ⁵ are each independently hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkenyl, benzyl or benzyl substituted with C 1 -C 6 alkyl or halogen; or

R ⁴ and R ⁵ together with the nitrogen atom to which they are attached form a pyrrolidine or piperidine ring, each of which is optionally substituted by fluorine, hydroxy, C 1 -C 6 alkoxy or C 1 -C 6 alkyl

In the herbicidal compositions and method of the invention, particular preference is given to compounds selected from the group consisting of:

2- (R-α-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,

2- (1-pyrrolidinyl) ethyl-1,1-bisphosphonic acid,

2- (1-piperidyl) 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-bisphosphonic acid,

2- (2-propenylamino, ethyl-1,1-bisphosphonic acid),

2- [1- (1,2,3,6-tetrahydropyridyl)] ethyl-1,1-bisphosphonic acid; and

2- (N, N-dipropylamino) ethyl-1,1-bisphosphonic acid.

In another aspect, the invention provides certain classes of novel azabisphosphonic acid compounds.

One such class of novel azabisphosphonic acid compounds within the scope of this invention includes compounds of Formula II

13th

12

N: h.

Pooh

I ^{3 2}

-CH (II) after ₃ h ₂ where

R ¹² and R ¹³ are each independently hydrogen, straight or branched chain alkyl of 1 to 6 carbon atoms, hydroxy, alkenyl of 2 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms or alkoxyalkyl of 1 to 6 carbon atoms in alkyl and 1 to 6 carbon atoms in the alkoxy radical;

and agriculturally acceptable salts thereof. Specific compounds of this kind include

2- (N, N-di-n-butylamino) ethyl-1,1-bisphosphonic acid;

2- (N, N-diethylamino) ethyl-1,1-bisphosphonic acid;

2- (N, N-di-n-propylamino) ethyl-1,1-bisphosphonic acid;

2- (propylamino) ethyl-1,1-bisphosphonic acid?

2- (isopropylamino) ethyl-1,1-bisphosphonic acid;

2- (propylamino) ethyl-1,1-bisphosphonic acid tetrabutylammonium salt;

2- (propylamino) ethyl-1,1-bisphosphonic acid tributylamine salt;

2- (tert-butylamino) ethyl-1,1-bisphosphonic acid;

2- (n-butylamino) ethyl-1,1-bisphosphonic acid;

2- (n-hexylamino) ethyl-1,1-bisphosphonic acid tetrabutylammonium salt;

2- (but-3-enylamino) ethyl-1,1-bisphosphonic acid;

2- (n-hexylamino) ethyl-1,1-bisphosphonic acid;

2- (n-isobutylamino) ethyl-1,1-bisphosphonic acid;

2- (n-ethylamino) ethyl-1,1-bisphosphonic acid;

2- (prop-2-enylamino) ethyl-1,1-bisphosphonic acid;

2- (methoxyamino) ethyl-1,1-bisphosphonic acid;

2- (N-methoxy-N-methylamino) ethyl-1,1-bisphosphonic acid;

2- (N-hydroxy-N-methylamino) ethyl-1,1-bisphosphonic acid;

and

2- (2-ethoxyethylamino) ethyl-1,1-bisphosphonic acid.

The novel azabisphosphonic acids of the invention also include compounds of formula III

R ¹⁴ R ¹⁸ PO ^ H

I II

Ar - (-C-) n --NC - CH (III) / I ^q III (R ¹⁶ ) R ¹⁵ R ¹⁹ R ¹⁷ PO ₃ H ₂ wherein q represents 0 to 10;

j is 0 to 3;

R ¹⁴ and R ¹⁵ are each independently hydrogen or C 1 -C 6 alkyl;

Ar represents a benzene, pyridine, pyrimidine, pyridazine, naphthalene, pyrazole, imidazole, triazole, thiazole, furan, thiophene, pyrrole, oxazole or thiadiazole residue;

R ¹⁶ is halogen, C 1 -C 10 alkyl, aryl, substituted aryl, benzyl, substituted benzyl, nitro, haloalkyl of 1 to 10 carbon atoms, alkoxy of 1 to 10 carbon atoms, alkylthio of 1 to 10 carbon atoms, (C 1 -C 10) alkylsulfenyl, phenoxy, substituted phenoxy, (C 2 -C 10) alkenyl, or cyano; ar ¹⁷ , r ¹⁸ and R ¹⁹ are each independently hydrogen, C 1 -C 10 alkyl, substituted C 1 -C 10 alkyl, C 7 -C 10 aralkyl or C 2 -C 10 alkenyl;

and agriculturally acceptable salts thereof.

When q is 2 or higher, each of R ¹⁴ and R ¹⁵ is a non-dependent hydrogen atom or a C 1 -C 3 alkyl group. Similarly, if j is a number of 2 or greater, then the radical R ¹⁶ at each occurrence may be the same or different.

Specific compounds of this kind include:

2- (α-methylbenzylamino) ethyl-1,1-bisphosphonic acid;

2- (2-methylbenzylamino) ethyl-1,1-bisphosphonic acid;

2- (3-methylbenzylamino) ethyl-1,1-bisphosphonic acid;

2- (2-phenylethylamino) ethyl-1,1-bisphosphonic acid;

2- (benylamino) ethyl-1,1-bisphosphonic acid;

2- (S-α-methylbenzylamino) ethyl-1,1-bisphosphonic acid;

2- (R-α-methylbenzylamino) ethyl-1,1-bisphosphonic acid;

2- (R-α-methylbenzylamino) ethyl-1,1-bisphosphonic acid tetrabutylammonium salt.

Yet another novel type of compounds of the invention are compounds of formula IV (IV)

CH.

? ° A

-CH after ₃ h ₂ where

A is C 3 -C 6 alkyleneidene, optionally substituted with C 1 -C 6 alkyl;

and agriculturally acceptable salts thereof.

Specific compounds of this kind include

2- (1-pyrrolidinyl) ethyl-1,1-bisphosphonic acid;

2- (2,5-dimethyl-1-pyrrolidinyl) ethyl-1,1-bisphosphonic acid;

2- (1-pyrrolidinyl) ethyl-1,1-bisphosphonic acid tetraammonium salt;

2- (1-pyrrolidinyl) ethyl-1,1-bisphosphonic acid tributylamine salt;

the trimethylsulfonium salt of 2- (1-pyrrolidinyl) ethyl-1,1-bisphosphonic acid;

2- (1-hexamethyleniminyl) ethyl-1,1-bisphosphonic acid;

2- (4-methyl-1-piperidyl) ethyl-1,1-bisphosphonic acid;

2- (2-methyl-1-piperidyl) ethyl-1,1-bisphosphonic acid; and 2- (3-methyl-1-piperidyl) ethyl-1,1-bisphosphonic acid.

Another new type of compounds of the invention includes compounds of formula V (V)

^P0 A t —R ²⁰ J> ° _A where

R ²⁰ represents a hydrogen atom or a hydroxyl group; and

B is C 2 -C 4 alkylidene linking, optionally substituted with C 1 -C 6 alkyl;

and agriculturally acceptable salts thereof.

Specific compounds of this kind include:

1- (2-piperidyl) -1-hydroxymethane-1,1-bisphosphonic acid; 1- (2-pyrrolidinyl) -1-hydroxymethane-1,1-bisphosphonic acid and 1- (2-pyrrolidinyl) -1-hydroxymethane-1,1-bisphosphonic acid tributylamine salt.

Another class of compounds of the invention are compounds of formula VI

R ²¹ PO-JH ₉

I I

H, N — C-C-OH (VI)

I I

R ²² PO ₃ H ₂ where

R ²¹ and R ²² are each independently C 1 -C 6 alkyl or together form C 3 -C 5 alkylidene optionally substituted with C 1 -C 6 alkyl;

and agronomically acceptable salts thereof.

Illustrative of such compounds of the invention include 2-amino-1-hydroxy-2-methylpropyl-1,1-bisphosphonic acid hydrochloride salt; and

1- (1-Aminocyclopentyl) -1-hydroxymethyl-1,1-bisphosphonic acid.

Yet another novel type of compounds of the invention are compounds of formula VII

N-CH.

PO, H

I ²²

CH 3 ^O 3 2 (VII) wherein t represents 2, 3 or 4;

R ²³ and R ²⁴ are each independently hydrogen, C 1 -C 10 alkyl, halogen, nitro, C 1 -C 9 alkoxy, C 1 -C 10 aralkyl, cyano, trifluoromethyl or an unsaturation unit; and

R ²⁵ is hydrogen, C 1 -C 6 alkyl, C 7 -C 10 aralkyl, halogen, nitro, trifluoromethyl or cyano. .

Each of R ²³ and R ²⁴ may itself be a different member of the abovementioned set of residues.

Illustrative examples of such compounds of the invention include

2- [1- (2-methyl-1,4,5,6-tetrahydro-1,3-pyrimidinyl)] ethyl-1,1-bisphosphonic acid; and

2- [1- (4-methyl-1,3-imidazolyl)] ethyl-1,1-bisphosphonic acid.

The above formulas are to be construed to include tautomeric forms of the structures depicted, as well as physically distinguishable modifications of these compounds, which may, for example, result from different arrangement of molecules in the crystalline lattice, inability of parts of the molecule to or by intermolecular hydrogen bonds or other mechanisms.

The compounds of these formulas may exist in enantiomeric forms. The invention encompasses both individual enantiomers and mixtures thereof with any ratio of the two components.

The term hydrocarbyl, whether as a single substituent or as part of the definition of a larger group (for example, hydrocarbyloxy or hydrocarbylS (O) _m - and the like), means hydrocarbon groups having 1 to 16 carbon atoms. Thus, hydrocarbyl includes, for example, straight or branched chain alkyl groups of 1 to 16 carbon atoms (such as methyl, ethyl, propyl, isopropyl, sec-hexyl and hexyl); cycloalkyl groups of 3 to 16 carbon atoms (such as cyclo20 propyl, cyclobutyl and cyclohexyl); alkenyl groups of 2 to 16 carbon atoms (such as allyl and crotyl); (C 2 -C 16) alkynyl groups (such as propynyl); phenyl; phenylalkyl; alkyl-phenyl; alkenylfenylskupina; alkinylfenylskupina; alkyl benzyl; alkenylbenzylskupina; alkinylbenzylskupina; naphthyl, etc.

Substituted as used in connection with the term hydrocarbyl (or similar terms unless otherwise indicated) means hydrocarbyl groups as defined above containing one or more substituents selected from the group consisting of halogen (i.e., fluoro, chloro, bromo) and iodine); C 1 -C 10 alkoxy; an alkyl-S (O) _m - group in which the alkyl moiety contains 1 to 10 carbon atoms; cyano; nitro; carboxy and functional groups of salts, amides and esters of carboxylic acids; C 2 -C 10 alkanoyl; and phenyl optionally substituted with one or more C 1 -C 10 alkyl, C 1 -C 10 alkoxy, alkyl-S (O) _m -, wherein the alkyl moiety contains 1 to 10 carbon atoms, nitro, atoms fluorine, chlorine or bromine, cyano or trifluoromethyl. In the above definitions, m is 0, 1, or 2.

When the hydrocarbyl group is an substituted aryl radical (e.g., phenyl, benzyl or naphthyl), the substituents of the aryl radical may be selected from the group of substituents mentioned in the preceding paragraph, with nitro being also a suitable substituent. One or more such substituents may be present. The term substituted pyridyl refers to a pyridyl radical containing the substituents listed above for substituted aryl radicals.

Further, unless otherwise stated, the term alkyl includes straight, branched and cyclic alkyl groups. In the above definitions, halogen means fluorine, chlorine, bromine and iodine. In polyhalogenated groups, the halogens may be the same or different.

The compounds of the invention are potent herbicides which can be used postemergence and are useful against a wide range of plant species, including broadleaf and grass plants.

The present invention also provides a method of controlling undesirable vegetation, which comprises applying a herbicidally effective amount of a compound of the invention together with an inert diluent or carrier to the site at which it is desired to control such vegetation. suitable for herbicidal application.

By herbicide is meant a substance having an inhibitory inhibitory or modifying effect on undesirable plant growth. The inhibitory suppressing or modifying effect includes all deviations from natural development, such as complete killing, growth retardation, defoliation, desiccation, regulation, offshoot curvature, leaf burning stimulation, dwarf mold development, and the like. The herbicidal adjuvant is used in the same sense. By herbicidally effective amount is meant any amount by which such suppression or modification can be achieved when applied to unwanted plants alone or to an area where such plants grow. Plants also include germinated seeds, emerging seedlings and stabilized vegetation, including roots and aerial parts of plants.

The term agriculturally acceptable salt is well understood by those skilled in the art. The term includes alkali metal salts, ammonium, phosphonium and sulfonium salts, their organic derivatives and the like.

In general, the compounds of the invention wherein R ¹ represents a hydrogen atom can be produced by reacting tetraethyl vinylidene bis (phosphonate) with a suitable amine. This reaction is conveniently carried out at a temperature of about 0 to about 100 ° C in the presence of a suitable non-reactive solvent such as acetonitrile, diethyl ether, toluene, tetrahydrofuran and the like. The ester group can be removed using bromotrimethylsilane or aqueous hydrochloric acid.

Tetraethylvinylidenebis (phosphonate) can be prepared as described by C. Degenhardt et al., J. Org. Chem. Vol. 51, p. 3488-3490 (1986). The amine used is commercially available or can be prepared by procedures well known in the art, for example, from the corresponding bromides by Gabriel synthesis (see Vogel, A Textbook of Practical Organic Chemistry, 3rd edition, p. 569).

In the preparation of compounds where the amine contains sensitive groups, the ester groups need to be esterified first using a compound such as bromotrimethylsilane. Such groups can subsequently be hydrolytically removed by treatment with water.

Alternatively, in the preparation of compounds wherein R ¹ is other than hydrogen, a suitable carboxylic acid, amide or nitrile thereof is treated with phosphorous trichloride and phosphorous acid or phosphorous trioxide, as is well known to those skilled in the art.

The compositions of the invention comprise a compound of formula I as defined above and a suitable carrier. Such carriers are well known to those skilled in the art.

The compounds of the invention are useful as herbicides and can be applied at various concentrations and by various methods known to those skilled in the art. These compounds are useful in suppressing the growth of unwanted vegetation by post-emergence application to the site at which such suppression is to be achieved. In practice, the compounds of the present invention are administered in the form of compositions comprising various adjuvants and carriers known to facilitate dispersion or are commonly used directly for this purpose. The choice of composition and route of administration for any given compound may affect its efficacy, and with this in mind, this choice must be made. Thus, the compounds of the invention may be formulated as wettable powders, emulsifiable concentrates, powdered powders or dusts, concentrated flowable suspensions, solutions, suspensions or emulsions, or controlled release forms such as microcapsules. Such compositions may contain the active ingredient from a very small amount, such as about 0.5%, to high amounts, such as up to 95% or more by weight. The optimum amount for each given compound will depend on the type of plants to be suppressed. The application level will usually be in the range of about 0.01 to about 11 kg / ha, preferably about 0.02 to about 4.5 kg / ha.

The wettable powders consist of finely divided particles which disperse readily in water or other liquid carriers. These particles contain the active ingredient entrapped in a solid matrix. Conventional solid matrices include fuller mixture, kaolin clays, silica and other readily wetted organic or inorganic solids. Wettable powders generally contain about 5 to about 95% of the active ingredient and a small amount of wetting, dispersing or emulsifying agent.

Emulsifiable concentrates are homogeneous liquid compositions which are dispersible in water or other liquid and may consist solely of the active ingredient and a liquid or solid emulsifier, but may also contain a liquid carrier such as xylene, heavy aromatic gasoline, isophorone and other non-volatile organic solvents . Prior to use, these concentrates are dispersed in water or other liquid and are usually applied to the treatment area as a spray. The content of active ingredient in the concentrate may range from about 0.5 to about 95% by weight.

Dusts are granular mixtures of the active ingredient with finely divided solids, such as talc, clay, various flours and other organic or inorganic solids, which act as dispersants and carriers.

Microcapsules are usually formed by droplets of the active substance or its solution enclosed in an inert porous sheath which allows the sealed substance to escape into the environment at a controlled rate. The encapsulated droplets typically have a diameter in the range of about 1 to about 50 μιη. The sealed liquid usually constitutes about 50 to 95% by weight of the capsule and may contain, in addition to the active compound, a solvent. Various materials for forming microcapsule or membrane shells include natural and synthetic rubbers, cellulose-based materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.

Other useful compositions suitable for herbicidal applications include simple solutions, active ingredients in a solvent in which the ingredient is completely soluble to form a solution of the desired concentration, such as water, acetone, alkylated naphthalenes, xylene, and other organic solvents. Pressure spray packs may also be used. When applied from such a spray package, the active ingredient is dispersed into the finely divided form due to the evaporation of the low boiling dispersant solvent used as the carrier. Examples of suitable solvents are freons.

Many of the above compositions contain wetting, dispersing or emulsifying agents. Examples thereof include alkyl and alkylarylsulfonates and sulfates and salts thereof; polyhydric alcohols, polyethoxylated alcohols; esters and aliphatic amines. When used, such materials generally comprise from about 0.1% to about 15% by weight of the composition.

All of the above compositions can be manufactured as packages containing the herbicide together with other ingredients such as diluents, emulsifiers, surfactants and the like. It is also possible to produce the compositions only in a tank, whereby the individual components are supplied separately to the treatment site and are subsequently mixed.

The compounds of the invention are also useful in combination with other herbicides and / or defoliants, desiccants, growth inhibitors and the like. These other substances may comprise about 5 to about 95% by weight of the active ingredients of the composition. Such combinations often exhibit a higher level of weed control efficiency, and the results thus obtained cannot be achieved using separate herbicide-based compositions.

Examples of other herbicides, defoliants, desiccants and plant growth inhibitors with which the compounds of the present invention can be combined include the following characterized substances.

Examples of useful complementary herbicides are:

A) benzo-2,1,3-thiadiazin-4-one 2,2-dioxides such as bentazone;

B) hormonal herbicides, in particular phenoxyalkanoic acids such as MCPA, MCPA-thioethyl, dichlorprop, 2,4,5-T, MCPB, 2,4-D, 2,4-DB, mecoprop, trichlopyr, fluroxypyr, clopyralide and derivatives thereof (e.g., salts, esters and amides);

C) 1,3-dimethylpyrazole derivatives such as pyrazoxyphene, pyrazolate and benzofenap;

D) dinitrophenols and derivatives thereof (e.g. acetates) such as DNOC, dinoterb, dinoseb and its ester, dinoseb acetate;

E) dinitroaniline herbicides such as dinitramine, trifluralin, etalfluralin, pendimethalin; and oryzalin;

F) aryl urea herbicides such as diuron, flumeturon, metoxuron, neburon, isoproturon, chlorotoluron, chloroxuron, linuron, monolinuron, chlorobromuron, daimuron and metabenzthiazuron;

G) phenylcarbamoyloxyphenylcarbamates such as phenmedipham and desmedipham;

H) 2-phenylpyridazin-3-ones such as choridazone and norflurazone;

27) uracil herbicides such as lenacil, bromacil and terbacil;

J) triazine herbicides such as atrazine, simazine, aziprotryne, cyanazine, prometryn, dimetametryn, simetryne and terbutryn;

K) phosphorothioate herbicides such as piperophos, bensulide and butamiphos;

L) thiolcarbamate herbicides such as cycloate, vernolate, molinate, thiobencarb, butylate, EPTC, triallate, diallate, ethyl esprocarb, thiocarbazil, pyridate and dimepiperate;

M) 1,2,4-triazin-5-one based 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 compound propachlor, propanil, metazachlor, metolachlor, acetochlor and dimetachlor;

P) dihalobenzonitrile herbicides such as dichlobenil, bromoxynil and ioxynil;

Q) haloalkanoic acid herbicides such as dalapone, TCA and salts thereof;

R) diphenylether herbicides such as lactofen, fluroglycofen or salts or esters thereof, nitrofen, bifenox, acifluorophen and salts and esters thereof, oxyfluorophen and fomesafen, chlornitrophen and chloromethoxyphene;

S) phenoxyphenoxypropionate herbicides such as diclofop and its esters such as methyl ester, fluazifop and its esters, haloxyfop and its esters, quizalofop and its esters and fenoxaprop and its esters such as ethyl ester;

T) cyclohexanedione herbicides such as alloxydim and its salts, setoxydim, cycloxydim, sulcotrione, tralkoxydim and cletodim;

U) sulfonylurea herbicides such as chlorosulfuron, sulfometuron, metsulfuron and their esters, benzsulfuron and its esters such as its methyl ester, DPX-M6313, chlorimuron and its esters such as its ethyl ester, pirimisulfuron and its esters such as its methyl ester DPX-LS300 and pyrazosulfuron;

V) imidazolidinone herbicides such as imazaquin, imazametabenz, imazapyr and its isopropylammonium salt and imazetapyr;

W) arylanilide herbicides such as flamprop and its esters, benzoylprop-ethyl and diflufenican;

X) amino acid herbicides such as glyphosate and gluyfosinate and salts and esters thereof, sulphosate and bilanafos;

Y) organic arsenic compound herbicides such as MSMA;

Z) herbicidally active amide derivatives such as napropamide, propyzamide, carbetamide, tebutam, bromobutide, isoxaben, naproanilide, diphenamide and naptalam;

AA) various other herbicides such as etofumesate, cinmetylin, difenzoquat and its salts such as methyl sulfate salt, clomazone, oxadiazone, bromophenoxim, barban, tridiphane, (in a 3: 1 ratio) flurochloridone, quinchlorac and mefanacet;

BB) contact herbicides in which bipyridylium herbicides, such as herbicides in which the active ingredient is paraquat, and herbicides in which the active ingredient is diquat, are useful examples.

* These compounds are preferably used in combination with safety enhancers such as 2,2-dichloro N, N-di-2-propenylacetamide (dichloramide).

These compositions are generally applied to the area where vegetation control is to be achieved by conventional methods. For example, powder and liquid formulations may be applied using powered sprayers, hand and arm sprayers, and spray sprayers. Compositions such as dusts or sprays can also be applied from aircraft. A wick application can also be used.

The following are examples of typical means

5% dust on 5 parts of the active compound parts of talc

2% dust 2 parts of the active compound parts of highly disperse silica 97 parts of talc

The abovementioned dusts are prepared by mixing the desired ingredients and grinding the resulting mixture into particles of the desired size.

Wettable powders

70% 70 5 3 10 12 parts of the active compound parts of sodium dibutylnaphthalene sulfonate parts of naphthalene sulfone condensate parts parts acid, phenolsulfonic acid and formaldehyde (3: 2: 1) kaolin chalk Champagne 40% 40 parts of the active compound 5 parts sodium lignosulfonate 1 part dibutylnaphthalenesulfonic acid sodium salt 54 parts of silicic acid 25% 25 parts of the active compound 4.5 part kalciumlignínsulfátu 1.9 part. mixtures of chalk Champagne and hydroxyethylcellulose (1: 1) 1.5 part dibutylnaphthalenesulfonic acid sodium salt 19.5 part of silicic acid 19.5 part chalk Champagne 28.1 part kaolin 25% 25 parts of the active compound 2.5 part and zooktylphenoxypolyethylenethanol 1.7 part mixtures of chalk Champagne and hydroxyethylcellulose (1: 1) 8.3 part sodium aluminosilicate 16.5 part diatomaceous earth 46 parts kaolin

10 parts by weight of the active compound parts by weight of a mixture of sodium salts of sulfonated saturated aliphatic alcohols 5 parts of naphthalenesulfonic acid-formaldehyde condensate 82 parts of kaolin

The wettable powders mentioned above are prepared by homogenously mixing the active compound with the ingredients in a suitable mixer and grinding the resulting mixture in a mill or roller.

Emulsifiable concentrate

25% by weight of the active compound

2.5 parts of epoxidized vegetable oil parts of a mixture of alkylarylsulfonate and polyglycol ether of aliphatic alcohol parts of dimethylformamide

57.5 parts.xylene

The amount of the composition according to the invention representing a herbicidally effective amount depends on the type of seeds or plants to be suppressed. The degree of application of the active ingredients is in the range of about 0.01 to about 28 kg / ha, preferably about 0.11 to about 11 kg / ha, the amount actually used will depend on the total cost and the desired results. It will be appreciated by those skilled in the art that in order to achieve the same degree of inhibition, compositions with lower herbicidal efficacy will have to be used at higher dosages than those based on more active compounds.

The invention is illustrated by the following examples. These examples are illustrative only and do not limit the scope of the invention in any way.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

Preparation of 2- [1- (1,2,4-triazole)] ethyl-1,1-bisphosphonic acid (Compound No. 3)

One gram of 1,2,4-triazole is dissolved in 40 ml of tetrahydrofuran. The solution was cooled to -78 ° C under nitrogen, then n-butyllithium (974 mg) was added dropwise. The white suspension is stirred at -78'C for 5 minutes.

After warming to room temperature, the mixture was stirred for 45 minutes, then re-cooled to -78 ° C and tetraethylvinylidene phosphonate (4.78 g) was added dropwise over 20 minutes. After the addition was complete, the mixture was stirred for 15 minutes at -78 ° C, then warmed to O'C and stirring was continued for 1 hour. The reaction was quenched with 10 mL of water and the tetrahydrofuran was removed under the same pressure. The crude product obtained is mixed with 35 ml of aqueous potassium carbonate solution. The mixture was extracted with dichloromethane (3.times.100 ml). The extracts were combined, dried (MgSO4) and the solvent removed under the same pressure. The resulting low-viscosity oil was subjected to column chromatography on silica gel using 10% methanol in dichloromethane as eluent. 1.3 g of tetraethyl 2- [1- (1,2,4-triazole) ethyl 1,1-bisphosphonate are obtained. Compound 3 is obtained from this by hydrolysis by heating a dichloromethane solution of tetraethyl ester and 500 mol% bromotrimethylsilane at 45 ° C for 4 hours, then removing the volatiles under the same pressure. The oily residue was refluxed with water for 30 minutes and cooled to room temperature. Water was removed under high vacuum to isolate compound 3 in quantitative yield.

Example 2

Preparation of 1-hydroxy- (2-amino-2-methyl) propyl-1,1-bisphosphonic acid (Compound No. 8)

To a 250 ml three-necked round-bottomed flask fitted with a condenser, mechanical stirrer, oil bath and thermometer was added 2.37 g of 2-aminoisobutyric acid, 85 ml of chlorobenzene and 3.2 g of phosphorous acid. The mixture was heated to reflux for 1 hour and then cooled to 50 ° C, followed by the addition of phosphorus trichloride (9.62 g). The mixture was heated to reflux for 5 hours with stirring.

After this time, the mixture was allowed to cool to room temperature and carefully decanted with chlorobenzene. Fresh chlorobenzene (85 mL) and 80 mL of 6N hydrochloric acid were added to the residue. The resulting mixture was heated to reflux with stirring. After 6 hours, the resulting yellowish suspension was cooled to room temperature, subjected to vacuum filtration through dicalite, and the volatiles were removed under high vacuum. The colorless syrup obtained is triturated with ethanol with heating in a steam bath. After isolation by vacuum filtration, 3.09 g of product 8 is obtained as a white solid.

Example 3

Preparation of 1-hydroxy-1- (2-pyrrolidino) -1,1-bisphosphonic acid (Compound No. 9)

To a 200 ml three-necked flask equipped with a mechanical stirrer and reflux condenser with a nitrogen bubbler was added 4 g proline, 5.7 g phosphorous acid and 25 ml dioxane. Phosphorus trichloride (9.6 g) was added dropwise at 80 ° C. The mixture was stirred at 80 ° C for 2 hours, cooled to room temperature, and water (150 mL) was added. The resulting mixture was filtered through charcoal. The filtrate was evaporated under the same pressure and the clear oil obtained was placed in a vacuum oven (60 ° C) overnight. At the end of drying, the residue was triturated with ethanol and the white solid was collected by suction filtration and dried in a vacuum oven at 60 ° C. 5.9 g of compound 9 is obtained.

Example 4

Preparation of 2- (but-3-enylamino) ethyl-1,1-bisphosphonic acid (Compound No. 29)

A solution of 1.08 g of 1-aminobut-3-ene in 5 ml of methanol is added at room temperature to 3.8 g of tetraethylvinylidene bisphosphonate. The resulting mixture was stirred overnight, then an additional 0.12 g of 1-aminobut-3-ene was added and stirring was continued for a further 4 hours. The reaction mixture was then concentrated under the same pressure to give 4.56 g of tetraethyl 2- (but-3-phenylamino) ethyl 1,1-bisphosphonate. A sample (4.4 g) of this material was mixed with 5 ml of acetonitrile and 7.2 ml of bromotrimethylsilane. The resulting mixture was stirred at room temperature for 48 hours. The solution was heated to reflux for 4 hours and concentrated under the same pressure. The tetra (trimethylsilyl) ester obtained is hydrolyzed by refluxing with 25 ml of water for 30 minutes. Volatiles were removed from the mixture by lyophilization to give 3.2 g of 20 as a thick colorless hygroscopic foam.

Example 5

Preparation of 2- (3-methyl-1-piperidyl) ethyl-1,1-bisphosphonic acid (Compound No. 37)

A solution of 1 ml of 3-methylpiperidine in 5 ml of methanol is added dropwise to 2.43 g of tetraethylvinylidene bisphosphonate at room temperature. The reaction mixture was stirred overnight and then concentrated under the same pressure. 3.4 g of tetraethyl 2- (3-methyl-1-piperidyl) ethyl 1,1-bisphosphonate are obtained. A portion of this material (3.37 g) was dissolved in 5 mL of acetonitrile. To the solution was added 5 mL of bromotrimethylsilane. The resulting mixture was heated to reflux overnight, allowed to cool to room temperature and concentrated under the same pressure. Water (25 ml) was added to the oily residue and the resulting mixture was stirred for 3 hours. Removal of water and other volatile components under high vacuum afforded 2.84 g of compound 37 as a thick hygroscopic colorless foam.

Example 6

Preparation of 2- (4-methylbenzylamino) ethyl-1,1-bisphosphonic acid (Compound No. 67)

3.5 g of tetraethylvinylidene-1,1-bisphosphonate, 20 ml of acetonitrile and 1.5 g of 4-methylbenzylamine are added to a 100-ml flask. The resulting mixture was stirred magnetically at room temperature overnight, then the solvent was removed under the same pressure. 4.66 g of tetraethyl 2- (4-methylbenzylamino) ethyl 1,1-bisphosphonate are obtained. a portion of this material (3.87 g) was placed in a 100 ml beaker equipped with a magnetic stirrer and refluxed with 25 ml of concentrated hydrochloric acid for 4 hours. The volatiles were removed under high vacuum to give 3.21 g of compound 67 as a colorless hygroscopic glass.

Example 7

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Tests for herbicidal activity

The compounds characterized in the above table were tested for herbicidal activity by various methods and at different application rates. The results of some of these tests are shown below. As will be appreciated by those skilled in the art, the results obtained in the herbicidal activity assays are influenced by a number of factors. Examples of such factors include sunshine, soil type, soil pH, temperature, humidity, sowing depth, plant growth stage, herbicide application rate, as well as other numerous factors. All test procedures shall be performed to include the lowest range of variability. Known equipment and techniques are used to make the test methods consistent and reliable.

Preemergence herbicidal activity test

The day before treatment, seeds of several different weed species are sown in loam-sand soil containing only trace amounts of organic matter. Propagules are sown in individual rows across a width of 19.5 x 9.5 x 6.0 cm aluminum dish so that each row contains seeds of only one species. Green weed plants (Setaria viridis, SETVI), deaf oats (Avena fatua, AVEFA) and chicken marsh (Echinochloa crusgalli, ECHCG) are used as weed weed plants. Mustard (Brassica kaber, also known as Sinapsis arvensis, SINAR), abutilone (Abutilon theophrasti, ABUTH) and worm (Ipomoea spp., IPOSS) are used as broadleaf weed plants. Also planted are the nuts of Cyperus esculentus (CYPES). The sowing depth ranges from 1.0 to 1.5 cm and the density ranges from 3 to 25 plants per line, depending on the plant type.

The test compound solution is prepared by weighing 18.8 or 74.7 mg (for applications at 1 and 4 kg / ha) of the test compound into a 60 ml wide-necked flask and then dissolving the compound in 14.0 ml deionized water containing 0.5% by volume of Tween 20 emulsifier (polyoxyethylene sorbitan monolaurate). Additional solvents are used, if necessary, to dissolve the compounds with a volume not exceeding 2 ml (15% of the spray volume).

The soil surface is sprayed inside a closed linear spray bench so that the nozzle is positioned 30.5 cm above the soil surface. The spray volume applied to the test areas is set at 748 liters / ha The treatment intensity is 4.0 or 1.0 kg / ha (as shown in Table II). After treatment, the test areas are placed in a greenhouse. Water is supplied by sprinkling. Greenhouse management systems provide plants with natural and artificial (halogen lamps) lighting of 14 hours a day. The daytime temperature is maintained at 29 ° C and the night temperature is maintained at 21 ° C.

The degree of weed control is measured and recorded 17 to 21 days after treatment, expressed as a percent control compared to the growth of the same plant species with the same vegetation length on the untreated control area. Percent suppression includes total plant damage that occurs by all factors and includes inhibition of emergence, stunting, malformations, chlorosis, and other types of damage. The degree of suppression varies from 0 to 100%, where 0 means that the test compound has no effect because growth on the treated area is the same as on the untreated control area and 100 means complete killing of the plant. If a dash is given in the tables, this means that this test was not performed at this level of application.

Postemergence herbicidal activity test

The soil is prepared and sown with the same plant species using the same procedure as described in the pre-emergence test. The test site for the post-emergence test shall be placed in a greenhouse where the same environmental conditions as those specified in the pre-emergence test shall be maintained with water being sprayed onto the plants. Plants are allowed to grow for 10 to 12 days (or until the desired growth stage) prior to application of the test compounds. Spraying is carried out on grass weeds when they are in the three to four leaf stage and on broadleaf weeds in the one to two leaf stage. The chess plants have a height of 5 to 7 cm when applied.

The plants are sprayed from a distance of 30.5 cm above the leaves with the same spray solution prepared for the pre-emergence tests. The treatment rate is 4.0 or 1.0 kg / ha (as shown in Table III). Thereafter, the treated plants are returned to the greenhouse and the daily irrigation is carried out without wetting the leaves, the weed suppression rate is detected and recorded 17 to 21 days after treatment, expressed as a percentage suppression compared to the growth of the same plant species with the same the length of vegetation on the untreated control area. The same percent suppression scale (up to 100%) was used to evaluate the pre-emergence efficacy.

Claims (22)

A herbicidal composition comprising (A) a compound of formula I R ⁴ R ² PO ₃ H ₉ \ II. N - C - C - R ¹ (I) a ₃ ¹ R ^s R ^J PO ₃ H ₂ where R ¹ is hydrogen, hydroxy, C 1 -C 4 alkoxy, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 hydroxyalkyl, C 1 -C 4 hydroxyalkoxy or a group of formula N (R ⁶ ) (R ⁷ ), wherein R ⁸ and R ⁷ are each independently hydrogen or C 1 -C 3 alkyl; R ² and R ³ are each independently hydrogen; hydrocarbyl; substituted hydrocarbyl; hydrocarbyloxy; substituted hydrocarbyloxy; a hydrocarbyl-S (O) _m - group; or a substituted hydrocarbyl-S (O) _m - group; or R ² and R ^{3 taken} together form a three to six membered carbocyclic ring optionally substituted by halogen, hydroxy, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio or N ( R ⁸ ) (R ⁹ ) wherein R ⁸ and R ⁹ are each independently hydrogen or C 1 -C 12 alkyl; and R ⁴ and R ⁵ are each independently hydrogen; hydrocarbyl; substituted hydrocarbyl; hydrocarbyloxy; substituted hydrocarbyloxy; a hydrocarbyl-S (O) _m - group; or a substituted hydrocarbyl-S (O) _m - group; pyridyl; substituted pyridyl; or a group of formula N (R ¹⁰ ) (R ¹¹ ) wherein R ¹⁰ and R ¹¹ are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl; or R ⁴ and R ⁵ together with the nitrogen atom to which they are attached form aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulphinyl, thiomorpholine sulphonyl, hexamethylenimine, piperidine, tetrahydropyridine, pyrazole, pyrimidine, pyrrolidine, pyrrolidine, pyrrolidine, pyrrole, pyrrole, pyrrole, pyrrole, pyrrole, pyrrole, pyrrole, , a perhydroquinoline, perhydroisoquinoline or pyrrolidine ring, each of which rings is optionally substituted with a substituent selected from the group consisting of C 1 -C 12 alkyl, halogen, C 6 -C 10 aryl, C 6 -C 10 aryl substituted halogen or alkyl of 1 to 6 carbon atoms, aralkyl of 7 to 16 carbon atoms, aralkyl of 7 to 16 carbon atoms substituted with halogen or alkyl of 1 to 6 carbon atoms, nitro, halogen (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy, (C 1 -C 10) alkylthio, (C 1 -C 10) alkylsulfonyl, phenoxy (78), halogen-substituted phenoxy or C 1 -C 6 -alkyl, (C 1 -C 10) alkenyl and cyano; or R ² and R ⁴ together with the nitrogen and carbon atom to which they are attached form aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimine, piperidine, tetrahydropyridine, pyrimidine, pyrazole, imidazole, triazole, imidazole, triazole, imidazole, triazole, imidazole, triazole, imidazole, triazole, imidazole, , an azetidine, perhydroindole, perhydroquinoline, perhydroisoquinoline or pyrrolidine ring, each of which rings is optionally substituted with a substituent selected from the group consisting of C 1 -C 12 alkyl, halogen, C 6 -C 10 aryl, C 6 -C 10 aryl substituted with halogen or alkyl of 1 to 6 carbon atoms, aralkyl of 7 to 16 carbon atoms, aralkyl of 7 to 16 carbon atoms substituted with halogen or alkyl of 1 to 6 carbon atoms, nitros C 1 -C 10 haloalkyl, C 1 -C 10 alkoxy, C 1 -C 10 alkylthio, C 1 -C 10 alkylsulfonyl, phenoxy, halo or C 1 -C 6 alkyl substituted phenoxy C 1 -C 10 alkenyl and cyano; and m is 0, 1 or 2; or an agrochemically acceptable salt thereof; and (B) an agrochemically acceptable carrier for the compound. The herbicidal composition according to claim 1, characterized in that R ¹ represents a hydrogen atom or a hydroxy group. The herbicidal composition according to claim 2, characterized in that R and R are each independently hydrogen or C 1 -C 6 alkyl. A herbicidal composition according to claim 3, characterized in that R ⁴ and R ⁵ each independently represent a hydrogen atom of a C 1-6 alkyl group, a C 2-6 alkenyl group, a benzyl group or a benzyl group substituted with a C 1-6 alkyl group or halo. A herbicidal composition according to claim 3, characterized in that R ⁴ and R ⁵ together with the nitrogen atom to which they are attached form a pyrrolidine or piperidine ring which is optionally substituted by fluorine, hydroxy, C 1 -C 6 alkoxy or C 1 -C 6 alkyl. The herbicidal composition of claim 1, wherein: R ¹ is hydrogen, hydroxy, halogen or C 1 -C 4 alkyl; R ² and R ³ are each independently C 1 -C 4 alkyl 12 carbon atoms; (C 2 -C 12) alkenyl; (C 2 -C 12) alkynyl; haloalkyl having 1 to 12 carbon atoms; haloalkenyl of 2 to 12 carbon atoms; haloalkynyl having 2 to 12 carbon atoms; (C 6 -C 14) aralkyl; C 1 -C 12 alkoxy or C 1 -C 12 alkylthio; R ⁴ and R ⁵ are each independently hydrogen, C 1 -C 6 alkyl; (C 2 -C 6) alkenyl; (C 2 -C 6) alkynyl; (C 1 -C 6) haloalkyl; haloalkenyl of 2 to 6 carbon atoms; haloalkynyl having 2 to 6 carbon atoms; pyridyl; substituted pyridyl; phenyl; substituted phenyl; (C 7 -C 14) aralkyl; or substituted (C7 -C14) aralkyl; or R ⁴ and R ⁵ together with the nitrogen atom to which they are attached form a tetrahydropyrimidine, tetrahydropyridine or imidazole ring or a ring having the structure - (CH ₂ ) _n -N-, wherein n represents a number from 3 to 6, each of which rings is optionally substituted with halogen, hydroxy, (C1-C6) alkoxy, nitro, (C1-C6) alkyl, (C1-C6) aralkyl or (C1-C6) alkylthio. A herbicidal composition according to claim 6, wherein it is a hydrogen atom or a hydroxy group; R ² and R ³ are each independently hydrogen or C 1 -C 6 alkyl; and R ⁴ and R ⁵ are each independently hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, benzyl or benzyl substituted with C 1 -C 6 alkyl or halogen; or R ⁴ and R ⁵ together with the nitrogen atom to which they are attached form a pyrrolidine or piperidine ring, each of which is optionally substituted with fluorine, hydroxy, C 1 -C 6 alkoxy or C 1 -C 6 alkyl. The herbicidal composition according to claim 1, characterized in that it comprises as component A 2- (1-pyrrolidinyl) ethyl-1,1-bisphosphonic acid, 2- (1-piperidyl) 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-α-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-tetrahydropyridyl)] ethyl-1,1-bisphosphonic acid. 9. A method of inhibiting the growth of plants, comprising applying to the locus of said plants a herbicidally effective amount of a compound of formula (I). R \ I I N-C-C J PO ₃ ^H 2 (I) PC> 3 ^H 2 where R ¹ is hydrogen, hydroxy, C 1 -C 4 alkoxy, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 hydroxyalkyl, C 1 -C 4 hydroxyalkoxy or a group of formula N (R ⁶ ) (R ⁷ ) wherein R ⁶ and R ⁷ are each independently hydrogen or C 1 -C 3 alkyl; R ² and R ³ are each independently hydrogen; hydrocarbyl; substituted hydrocarbyl; hydrocarbyloxy; substituted hydrocarbyloxy; a hydrocarbyl-sCo1- group; or a substituted hydrocarbyl-S (O) _m - group; or R ² and R ^{3 taken} together form a three to six membered carbocyclic ring optionally substituted by halogen, hydroxy, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio or N (R 2) ⁸ ) (r 9), wherein R ⁸ and R 6 are each independently hydrogen or C 1 -C 12 alkyl; and R ⁴ and R ⁵ are each independently hydrogen; hydrocarbyl; substituted hydrocarbyl; hydrocarbyloxy; substituted hydrocarbyloxy; hydrocarbyl; substituted hydrocarbylthio; pyridyl; or a group of formula N (R ¹⁰ ) (R ¹¹ ) wherein R ¹⁰ and R ¹¹ are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl; or R ⁴ and R ⁵ together with the nitrogen atom to which they are attached form aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulphinyl, thiomorpholine sulphonyl, hexamethylenimine, piperidine, tetrahydropyridine, pyrazole, pyrimidine, pyrrolidine, pyrrolidine, pyrrolidine, pyrrole, pyrrole, pyrrole, pyrrole, pyrrole, pyrrole, pyrrole, , a perhydroquinoline, perhydroisoquinoline or pyrrolidine ring, each of which rings is optionally substituted with a substituent selected from the group consisting of C 1 -C 12 alkyl, halogen, C 6 -C 10 aryl, C 6 -C 10 aryl substituted halogen or alkyl of 1 to 6 carbon atoms, aralkyl of 7 to 16 carbon atoms, aralkyl of 7 to 16 carbon atoms substituted with halogen or alkyl of 1 to 6 carbon atoms, nitro, halogen (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy, (C 1 -C 10) alkylthio, (C 1 -C 10) alkylsulfonyl, phenoxy, halogen-substituted phenoxy, (C 1 -C 6) alkyl, alkenyl C1-C10-cyano; or R ² and R ⁴ together with the nitrogen atom and the carbon atom to which they are attached form aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimine, piperidine, tetrahydropyridine, pyrimidine, triazole, imidazole, triazole, imidazole, triazole, imidazole, triazole, imidazole, triazole, imidazole, , an azetidine, perhydroindole, perhydroquinoline, perhydroisoquinoline or pyrrolidine ring, each of which rings is optionally substituted with a substituent selected from the group consisting of C 1 -C 12 alkyl, halogen, C 6 -C 10 aryl, C 6 -C 10 aryl which is substituted by halogen or alkyl of 1 to 6 carbon atoms, aralkyl of 7 to 16 carbon atoms, aralkyl of 7 to 16 carbon atoms which is substituted by halogen or alkyl of 1 to 6 carbon atoms, nitro C 1 -C 10 haloalkyl, C 1 -C 10 alkoxy, C 1 -C 10 alkylthio, C 1 -C 10 alkylsulfonyl, phenoxy, halo-substituted or C 1 -C 6 -alkyl phenoxy C 1 -C 10 alkenyl and cyano; and m is 0, 1 or 2; * or agrochemically acceptable salts thereof. 10. The method according to claim 9, characterized in characterized in that R ¹ is H or OH. A process according to claim 10, wherein R ² and R ³ are each independently hydrogen or C 1 -C 6 alkyl. A process according to claim 11, wherein R ⁴ and R ⁵ are each independently C 1 -C 6 alkyl C 2 -C 6 alkenyl, benzyl or benzyl substituted with C 1-6 alkyl or halogen. A process according to claim 11, wherein R ⁴ and R ⁵ together with the nitrogen atom to which they are attached form a pyrrolidine or piperidine ring. 14. The method of claim 9 wherein R ¹ is hydrogen, hydroxy, halogen or C 1 -C 4 alkyl; R ² and R ³ are each independently C 1 -C 12 alkyl; (C 2 -C 12) alkenyl; (C 2 -C 12) alkynyl; haloalkyl of 1 to 12 carbon atoms; haloalkenyl of 2 to 12 carbon atoms; haloalkynyl of 2 to 12 carbon atoms; (C 6 -C 14) aralkyl; C 1 -C 12 alkoxy or C 1 -C 12 alkylthio; R ⁴ and R ⁵ are each independently hydrogen, C 1 -C 6 alkyl; (C 2 -C 6) alkenyl; (C 2 -C 6) alkynyl; (C 1 -C 6) haloalkyl; haloalkenyl of 2 to 6 carbon atoms; haloalkynyl having 2 to 6 carbon atoms; pyridyl; substituted pyridyl; phenyl; substituted phenyl; (C 7 -C 14) aralkyl; or substituted (C7 -C14) aralkyl; or * R ⁴ and R ⁵ together with the nitrogen atom to which they are attached form a tetrahydropyrimidine, tetrahydropyridine or imidazole ring or a ring having the structure - (CH ₂ ) _n -N-, ^{wherein n} represents a number of 3 to 6, each of these rings is optionally substituted with halogen, hydroxy, C 1 -C 6 alkoxy, nitro, C 1 -C 6 alkyl, C 7 -C 16 aralkyl or C 1 -C 6 alkylthio. 15. The method of claim 14, which is hydrogen or hydroxy; each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a benzyl group or a benzyl group substituted with an alkyl group having 1 to 6 carbon atoms or a halogen; or together with the nitrogen atom to which they are attached form a pyrrolidine or piperidine ring from which: R ^J R ² and R ³ R ⁴ and R ⁵ R ⁴ and R ^{5 are} each optionally substituted with fluoro, hydroxy, C 1 -C 6 alkoxy or C 1 -C 6 alkyl 16. The method of claim 9, wherein the active compound is a compound selected from the group consisting of 2- (1-pyrrolidinyl) ethyl-1,1-bisphosphonic acid, 2- (1-piperidyl) 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-bisphosphonic acid, 2- (2-propenylamino) ethyl-1,1-bisphosphonic acid, 2- (R-α-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-tetrahydropyridyl)] ethyl-1,1-bisphosphonic acid. ¹⁷ 17. Compounds of formula (II): ^3H2 R ^{13 -} N - CH _{2 -} CH (II) where after ₃ h ₂ R ¹² and R ¹³ are each independently hydrogen, straight or branched chain alkyl of 1 to 6 carbon atoms, hydroxy, alkenyl of 2 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms or alkoxyalkyl of 1 to 6 carbon atoms in alkyl and 1 to 6 carbon atoms in the alkoxy radical; and agriculturally acceptable salts thereof. 18. Compounds of formula III R ¹⁴ R ¹⁸ PO _q H _? I II Ar - (- C -) - NC - CH (III) / I ^q III (R ¹⁶ R ¹⁵ R ¹⁹ R ¹⁷ PO ₃ H ₂ wherein q represents 0 to 10; j is 0 to 3; R ¹⁴ and R ¹⁵ are each independently hydrogen or C 1 -C 6 alkyl; Ar represents a benzene, pyridine, pyrimidine, pyridazine, naphthalene, pyrazole, imidazole, triazole, thiazole, furan, thiophene, pyrrole, oxazole or thiadiazole residue; R ¹⁶ is halogen, C 1 -C 10 alkyl, aryl, substituted aryl, benzyl, substituted benzyl, nitro, haloalkyl of 1 to 10 carbon atoms, alkoxy of 1 to 10 carbon atoms, alkylthio of 1 to 10 carbon atoms, (C 1 -C 10) alkylsulfenyl, phenoxy, substituted phenoxy, (C 2 -C 10) alkenyl, or cyano; and R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently hydrogen, C 1 -C 10 alkyl, substituted C 1 -C 10 alkyl, C 7 -C 10 aralkyl or C 2 -C 10 alkenyl; and agriculturally acceptable salts thereof. Compounds of formula IV / Ά A N · CH. f ° 3 ^H 2 CH PO.H., j 2 (IV) where A is C 3 -C 6 alkyleneidene, optionally substituted with C 1 -C 6 alkyl; and agriculturally acceptable salts thereof. Compounds of Formula V L ₃ ° ^h I _ ^{3 2} ₃ Η cέ ° ₂ (A) wherein R ²⁰ represents a hydrogen atom or a hydroxyl group; and B represents an alkylidene linking group of 2 to 5 carbon atoms C 4 optionally substituted by C 1 -C 6 alkyl; and agriculturally acceptable salts thereof. Compounds of formula VI R ²¹ ΡΟ, I I H, N — C-C-OH (VI) I I R ²² PO ₃ H ₂ where R ² - and - R ²² are each independently C 1 -C 6 alkyl or taken together form C 3 -C 5 alkylidene optionally substituted with C 1 -C 6 alkyl; and agriculturally acceptable salts thereof. where Compounds of formula (VII), (25) - CH. R PO, H. (VII) t is 2, 3 or 4; R ²³ and R ²⁴ are each independently hydrogen, C 1 -C 10 alkyl, halogen, nitro, C 1 -C 9 alkoxy, C 1 -C 10 aralkyl, cyano, trifluoromethyl or an unsaturation unit; and R ²⁵ is hydrogen, C 1 -C 6 alkyl, C 7 -C 10 aralkyl, halogen, nitro, trifluoromethyl or cyano.