Desiccant

Diaryl ethers and processes for their preparation and herbicidal and desiccant compositions containing them

Desiccant Abstract
A compound represented by the formula (I) or its salt and herbicidal and desiccant use thereof: ##STR1## wherein X, Y are independently hydrogen, halogen, cyano, nito, or (C.sub.1-6)haloalkyl; Z is oxygen or sulfur; and ##STR2##

Desiccant Claims
What is claimed is:

Ar is pyridyl, pyrimidyl, pyridazinyl, triazolyl, thiazolyl, isothiazolyl, or phenyl, or pyridyl, pyrimidyl, triazolyl, thiazolyl, isothiazolyl, or phenyl substituted with up to five substituents independently selected from halogen, (C.sub.1-6)alkyl, halo(C.sub.1-6)alkyl, (C.sub.1-6)alkoxy, (C.sub.1-6)alkylthio, halo(C.sub.1-6)alkoxy, (C.sub.1-6)alkylsulfonyl, (C.sub.1-6)alkylsulfinyl, di(C.sub.1-6)alkylaminocarbonyl, cyano, nitro, amino, hydroxy, (C.sub.1-6)alkylsulfonylamino, (C.sub.1-6)alkoxycarbonyl(C.sub.1-6)alkoxy, (C.sub.1-6)alkxylcarbonylamino, bisbenzoylamino, aminoacetyl, aminotrifluoroacetyl, or amino(C.sub.1-6)alkylsulfonate.

3. The compound or its salt according to claim 1, wherein

X is fluorine, and

Y is chlorine, and

Z is oxygen or sulfur, and

Ar is 2-pyridyl, 3-pyridyl, 4-pyridyl, 3-bromo-2-pyridyl, 5-bromo-2-pyridyl,6-bromo-2-pyridyl,3-chloro-2-yridyl,5-chloro-2-pyridyl,6 -chloro-2-pyridyl,3-fluoro-2-pyridyl,6-fluoro-2-pyridyl,3-cyano-2-pyridyl,5 -cyano-2-pyridyl,6-cyano-2-pyridyl,3-nitro-2-pyridyl,5-nitro-2-pyridyl,6-ni tro-2-pyridyl,3-trifluoromethyl-2-pyridyl,4-trifluoromethyl-2-pyridyl,5-tri fluoromethyl-2-pyridyl,6-trifluoromethyl-2-pyridyl,5-amino-2-pyridyl,3-dime thylaminocarbonyl-2-pyridyl,3-metlylsulfonyl-2-pyridyl,3-isopropylsulfonyl- 2-pyridyl,6-chloro-3-trifluoromethyl-2-pyridyl,3,5,6-trifluoropyridyl,2-pyr imidyl,4-pyrimidyl,5-bromo-2-pyrimidyl,4-chloro-2-pyrimidyl,4-trifluoromiet hyl-2-pyrimidyl,4,6,-dimethoxy-2-pyrimidyl,2,6-dimethoxy-4-pyrimidyl,4,6-di methoxy-2-triazinyl,phenyl,2-iodophenyl,2-trifluoromethoxyphenyl,2-nitrophe nyl,4-nitrophenyl,4-aminophenyl,4-hydroxyphenyl,4-methylsulfonylaminophenyl ,4-(1-ethoxycarbonylethoxy)phenyl,2-cyanophenyl,2-cyano-3-fluorophenyl,2-cy ano-4-fluorophenyl,2-amino-4-(1-ethoxycarbonylethoxy)-phenyl,2-cyano-4-nitr ophenyl,4-amino-2-cyanophenyl,4-nitro-2-trifluoromethylphenyl,4-amino-2-tri fluoromethylphenyl,4-acetylamino-2-trifluoromethylphenyl,4-(1-ethoxycarbony lethoxy)2-nitrophenyl,5-chloro-4-(1-ethoxycarbonylthoxy)-2-nitrophenyl,3-me thyl-4-nitro-5-isothiazolyl, or 5-nitro-2-thiazolyl.

4. A herbicidal composition which comprises an effective amount of a compound of claim 1 and an agricultural adjuvant.

5. A method for controlling weeds, which comprises applying to the locus to be protected a herbicidally effective amount of a compound of claim 1.

6. A method for controlling weeds in a corn field which comprises applying a herbicidally effective amount of a compound of claim 1 to the corn field.

7. A method for controlling weeds in a soybean field which comprises applying a herbicidally effective amount of a compound of claim 1 to the soybean field.

8. A method for controlling weeds, which comprises applying to the locus to be protected a herbicidally effective amount of a compound of claim 1 in combination with another herbicide for providing an additive or synergistic herbicidal effect.

9. A method for controlling weeds of claim 5 wherein the compound of claim 1 is applied to soil as a preemergent herbicide.

10. A method for controlling weeds of claim 5 wherein the compound of claim 1 is applied to plant foliage.

11. A method for controlling weeds of claim 8 wherein the another herbicide is an acetanilide, or a sulfonylurea.

12. A method to desiccate a plant which comprises applying to the plant a desiccatively effective amount of a compound of claim 1.

13. A method to desiccate a plant of claim 12 wherein the plant to which the compound is applied is a potato plant or a cotton plant.

Description
A class of diaryl ethers and compositions thereof which are useful in the control of weeds is of the general formula ##STR3##

wherein

X, Y are hydrogen, halogen, cyano, nitro, or (C.sub.1-6)haloalkyl;

Z is oxygen or sulfur;

Q is selected from ##STR4## ##STR5##

Ar is a substituted or unsubstituted aryl or heteroaryl ring; When Q is Q.sub.3 or Q.sub.6, substituted phenyl is excluded.

BACKGROUND OF THE INVENTION

Various substituted phenyl ethers (I.sup.1) are known in the literature. ##STR6##

Q may be pyrazole, imidazole, imidazolidine-2,4-dione, triazolinone, tetrazolinone, aminouracil, etc. R may be hydrogen, alkyl, cycloalkyl, alkenyl or alkynyl. U.S. Pat. No. 5,496,956 discloses arylpyrazoles with the R group selected from propargyl, allyl, or substituted alkyl. JP 6,256,312 discloses phenylimidazoles with the R group selected from hydrogen, (C.sub.1-10)alkyl. (C.sub.1-5)haloalkyl, (C.sub.3-5)alkenyl, (C.sub.3-5)alkynyl, or (C.sub.3-6)cycloalkyl. U.S. Pat. No. 5,125,958 discloses triazolinones with the R group selected from substituted phenyl group. JP 57,197,268 discloses hydantoins with the R group selected lower alkyl. U.S. Pat. No. 4,902,337 discloses hydantoins with the R group selected from hydrogen, alkyl, cycloalkyl, alkenyl or alkynyl. JP 525173 discloses pyrimidinediones with the R group selected from hydrogen, (C.sub.1-10)alkyl, (C.sub.1-5)haloalkyl, (C.sub.3-5)alkenyl, (C.sub.3-5)alkynyl, or (C.sub.3-6)cycloalkyl. U.S. Pat. No. 4,985,065 discloses phenyltetrazolinones with the R group selected from substituted phenyl group. No heteroaryl derivatives were claimed as R. WO 9,602,523 discloses substituted aryliminothiadiazoles with the R group selected from hydrogen, alkyl, cycloalkyl, alkenyl or alkynyl. U.S. Pat. No. 4,452,981 discloses phenylurazoles with the R group selected from (C.sub.1-3)alkyl, allyl, or propargyl. EP-A-517181(which corresponds to U.S. Pat. No. 5,280,010) discloses aminouracil compounds wherein Q is amino uracil and R is a lower alkyl group. WO96/07323 and WO96/08151 disclose some known uracil compounds. In WO96/08151 the generic representation is significantly broader than the disclosures set forth in it, and in the prior art patents. The specific aminouracil compounds of the formula (I) mentioned below are not known and are novel.

The present invention reveals that some diaryl ethers represented by the general formula (I) or their salts have a potent herbicidal activity with good crop safety.

DESCRIPTION

The need continues for novel and improved herbicidal compounds and compositions. This invention relates to novel diaryl ethers, compositions comprising diaryl ethers, and the use of diaryl ethers and compositions thereof as broad spectrum herbicides which are effective against both monocot and dicot weed species in preemergence and postemergence application and are sometimes safe to crops. The compounds and compositions of the present invention can also be sometimes used as desiccants. This invention also includes methods of preparing these compounds and intermediates thereof as well as methods of using the compound as herbicides.

This invention relates to diaryl ether compounds having the general formula I and their salts ##STR7##

wherein

X, Y are independently hydrogen, halogen, cyano, nitro, or (C.sub.1-6)haloalkyl and

Z is oxygen or sulfur and

Q is selected from ##STR8## ##STR9##

R.sub.1 is halogen;

R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are independently hydrogen, (C.sub.1-6)alkyl, or (C.sub.1-6)haloalkyl;

When R.sub.3 and R.sub.5 are taken together with the atoms to which they are attached, they represent a four to seven membered substituted or unsubstituted ring optionally interrupted by O, S(O).sub.n or N--R.sub.4, and optionally substituted with one to three (C.sub.1-6)alkyl group or one or more halogen atoms;

R.sub.6 is hydrogen, (C.sub.1-6)alkyl, (C.sub.2-6)alkenyl, (C.sub.2-6)alkynyl, (C.sub.1-6)haloalkyl, (C.sub.2-6)haloalkenyl, (C.sub.2-6)haloalkynyl, (C.sub.1-6)cyanoalkyl, (C.sub.1-6)alkoxy-(C.sub.1-6)alkyl, or (C.sub.1-6)alkylthio-(C.sub.1-6)alkyl;

A.sub.1 and A.sub.2 are independently oxygen or sulfur;

B is CH or N;

R.sub.7 and R.sub.8 are each independently hydrogen, (C.sub.1-6)alkyl optionally substituted with one or more halogen atoms, or (C.sub.3 -C.sub.6)cycloalkyl optionally substituted with one or more halogen atoms, and when R.sub.7 and R.sub.8 are taken together with the atoms to which they are attached, they represent a four to seven membered substituted or unsubstituted ring optionally interrupted by O, S(O).sub.n or N--R.sub.4, and optionally substituted with one to three (C.sub.1-6)alkyl groups or one or more halogen atoms;

n is an integer of 0, 1, or 2.

R.sub.9 and R.sub.10 is hydrogen, (C.sub.1-6)alkyl, acyl, or (C.sub.1-6)alkylsulfonyl or R.sub.9 and R.sup.10 may form a ring consisting of polymethylene, (CH.sub.2).sub.m, groups, where m is an integer of 2, 3, 4 or 5, together with the nitrogen atom of NR.sub.9 R.sub.10, which may or may not have a (C.sub.1-6)alkyl substituent.

D is carbon, oxygen, sulfur or a nitrogen atom, sulfoxide or sulfone;

n.sub.1 is 0, 1, 2, or 3;

R.sub.11 is hydrogen, hydroxyl, C.sub.1-3 alkoxy, C.sub.1-3 haloalkoxy, C.sub.2-5 alkylcarbonyloxy, or C.sub.2-5 haloalkylcarbonyloxy, nitro, or amino;

R.sub.12 is hydrogen, hydroxyl, or halogen;

When R.sub.11 and R.sub.12 are bonded to the same carbon atom, they may form a carbonyl bond.

When R.sub.11 and R.sub.12 are bonded to adjacent carbon atoms, they may form a epoxide ring;

The ring to which R.sub.11 and R.sub.12 are attached may be saturated or unsaturated and may contain single or double bonds.

E--G is N.dbd.N, CH.dbd.N, N.dbd.CH, or CH.dbd.CH.

Some compounds of formula (1) and their intermediates may occasionally exist as geometrical or optical isomers and the present invention includes all of these isomeric forms.

Some compounds of the formula (I) and their intermediates may form a salt with an acidic substance or a basic substance. The salt with an acidic substance may be an inorganic acid salt such as a hydrochloride, a hydrobromide, a phosphate, a sulfate or a nitrate. The salt with a basic substance may be a salt of an inorganic or organic base such as a sodium salt, a potassium salt, a calcium salt, a quarternary ammonium salt such as ammonium salt or a dimethylamine salt.

Ar is a substituted or unsubstituted aryl or heteroaryl ring; When Q is Q.sub.3 or Q.sub.6, substituted or unsubstituted phenyl is excluded.

This invention also relates to compositions containing those compounds and methods for using those compounds and compositions. The compounds and compositions of the present invention are especially useful for the selective control of undesirable plant species occasionally in the presence of crops. The compounds and compositions of the present invention can also be used as desiccants.

The compositions of the present invention may be used in admixture with or in combination with other agricultural chemicals, fertilizers or phytotoxicity-reducing agents. In such a case, they may exhibit even better effects or activities. As other agricultural chemicals, herbicides, fungicides, antibiotics, plant hormones, insecticides, or acaricides may, for example, be mentioned. Especially with herbicidal compositions having the compounds of the present invention used in admixture with or in combination with one or more active ingredients of other herbicides, it is possible to improve the herbicidal activities, the range of application time(s) and the range of applicable weed types. Further, the compounds of the present invention and an active ingredient of another herbicide may be separately formulated so they may be mixed for use at the time of application, or both may be formulated together. The present invention covers such herbicidal compositions.

The blend ratio of the compounds of the present invention with the active ingredient of other herbicides can not generally be defined, since it varies depending on the time and method of application, weather conditions, soil type and type of formulation.

However one active ingredient of other herbicide may be incorporated usually in an amount of 0.01 to 100 parts by weight, per one part by weight of the compounds of the present invention. Further, the total dose of all of the active ingredients is usually from 1 to 10000 g/ha, preferably from 5 to 500 g/ha. The present invention covers such herbicidal compositions.

As the active ingredients of other herbicides, the following (common name) may be mentioned. Herbicidal compositions having the compounds of the present invention used in combination with other herbicides, may occasionally exhibit a synergistic effect.

1. Those that are believed to exhibit herbicidal effects by disturbing auxin activities of plants, including a phenoxy acetic acid type such as 2,4-D, 2,4-DB, 2,4-DP, MCPA, MCPP, MCPB or naproanilide (including the free acids, esters or salts thereof), an aromatic carboxylic type such as 2,3,6 TBA, dicamba, dichlobenil, a pyridine type such as picloram (including free acids and salts thereof), triclopyr or clopyralid and others such as naptalam, benazolin or quinclorac.

2. Those that are believed to exhibit herbicidal effects by inhibiting photosynthesis of plants including a urea type such as diuron, linuron, isoproturon, chlorotoluron, metobenzuron, tebuthiuron or fluometuron, a triazine type such as simazine, atrazine, cyanazine, terbuthylazine, atraton, hexazinone, metribuzin, simetryn, ametryn, prometryn or dimethametryn, a uracil type such as bromacil, terbacil or lenacil, an anilide type such as propanil or cypromid, a carbamate type such as swep desmedipham or phenmedipham, a hydroxybenzonitrile type such as bromoxynil or ioxynil, and others such as pyridate, bentazon and methazole.

3. A quaternary ammonium salt type such as paraquat, diquat or difenzoquat, which is believed to be converted to free radicals by itself to form active oxygen in the plant and thus to exhibit quick herbicidal effects.

4. Those which are believed to exhibit herbicidal effects by inhibiting chlorophyll biosynthesis in plants and abnormally accumulating a photsensitizing peroxide substance in the plant body, including a diphenyl ether type such as nitrofen, lactofen, acifluorfen-sodium, oxyfluorfen, fomesafen, bifenox, or chlomethoxyfen, a cyclic amide type such as chlorphthalim, flumioxadine or flumiclorac-pentyl, and others such as oxadiazon, sulfentrazone or thidiazimin.

5. Those which are believed to exhibit herbicidal effects characterized by whitening activities by inhibiting chromogenesis of plants such as carotenoids including a pyridazinone type such as norflurazon, chloridazon or metflurazon, a pyrazol type such as pyrazolate, pyrazoxyfen or benzofenap, and others such as fluridone, fluramone, diflufencam, methoxyphenone, clomazone, amitrole, sulcotrione or isoxaflutole.

6. Those which exhibit herbicidal effects specifically to gramineous plants including an aryloxyphenoxypropionic acid type such as diclofop-methyl, pyrofenop-sodium, fluazifop-butyl, haloxyfop-methyl, quizalofop-ethyl, fenoxaprop ethyl, or cyhalofopbutyl and a cyclohexanedione type such as alloxydim-sodium, sethoxydim, clethodim or tralkoxydim.

7. Those which are believed to exhibit herbicidal effects by inhibiting amino acid biosynthesis of plants, including a sulfonylurea type such as chlorimuron-ethyl, nicosulfuron, metsulfuron-methyl, triasulfuron, primisulfuron, tribenuron-methyl, chlorosulfuron, bensulfuron-methyl, sulfometuron-methyl, prosulfuron, halosulfuronmethyl, thifensulfuron-methyl, rimsulfuron, azimsulfuron, flazasulfuron, imazosulfuron, cyclosulfamuron, flupyrsulfuron, a triazolopyrimidinesulfonamide type such as flumetsulam or metosulam, an imidazolinone type such as imazapyr, imazethapyr, imazaquin, imazamox, imazameth, imazamethabenz methyl, a pyrimidinesalicylic acid type such as pyrthiobac-sodium, bispyribac-sodium or pyriminobac-methyl, and others such as glyphosate, glyphosate-ammonium, iglyphosate-isopropylamine or sulfosate.

8. Those which are believed to exhibit herbicidal effects by interfering with the normal metabolism of inorganic nitrogen assimilation such as glufosinate, glufosinate-ammonium, phosphinothricin or bialophos.

9. Those which are believed to exhibit herbicidal effects by inhibiting cell division of plant cells, including a dinitroaniline type such as trifluralin, oryzalin, nitralin, pendamethalin, ethafluralin, benefin and prodiamine, an amide type such as bensulide, napronamide, and pronamide, a carbamate type such as propham, chlorpropham, barban, and asulam, an organophosphorous type such as amiprofosmethyl or butamifos and others such as DCPA and dithiopyr.

10. Those which are believed to exhibit herbicidal effects by inhibiting protein sysnthesis of plant cells, including a acetanilide type such as alachlor, metolachor, propachlor, acetochlor (including combinations with herbicide safeners) and dimethenamid.

11. Those in which the mode of action causing the herbicidal effects are not well understood including the dithiocarbamates such as thiobencarb, EPTC, diallate, triallate, molinate, pebulate, cycloate, butylate, vernolate or prosulfocarb and miscellaneous herbicides such as MSMA, DSMA, endothall, ethofumesate, sodium chlorate, pelargonic acid and fosamine.

Examples of Combinations with Other Herbicides

(Note: Weed species abbreviations are from the Composite List of Weeds published by the Weed Science Society of America, 1989.)

The following examples illustrate the utility of combinations of compounds of this invention and existing herbicides. The methods used are identical to those for the application of single compounds except the commercial formulations of existing herbicides were added to the spray mixture in the appropriate amounts before spraying.

Combination Example 1

Pre-emergent Application of Compound 9-1 with Metolachlor

Percent Control of Broadleaf Weeds

Treatment Rate (g ai/ha) AMARE ABUTH CASOB IPOHE CHEAL
AMBEL
Comp. 9-1 62.5 100 95 10 50 100 40
Metolachlor 1121 100 20 10 20 90 30
Comp. 9-1 + 62.5 + 100 100 100 70 100 80
Metolachlor 1121

Percent Control of Grass Weeds

Treatment Rate (g ai/ha) SETVI ECHCG SORHA DIGSA
Comp. 9-1 62.5 90 0 0 20
Metolachlor 1121 100 100 100 100
Comp. 9-1 + 62.5 + 100 100 100 100
Metolachlor 1121

Combination Example 2

Pre-emergent Application of Compound 9-1 with Dimethenamid

Percent Control of Broadleaf Weeds

Treatment Rate (g ai/ha) AMARE ABUTH CASOB IPOHE CHEAL
AMBEL
Comp. 9-1 62.5 100 95 10 50 100
40
Dimethenamid 520 100 40 40 0 30
40
Comp. 9-1 + 62.5 + 100 100 70 100 100
100
Dimethenamid 520

Percent Control of Grass Weeds

Treatment Rate (g ai/ha) SETVI ECHCG SORHA DIGSA
Comp. 9-1 62.5 90 0 0 20
Dimethenamid 1121 100 100 100 100
Comp. 9-1 + 62.5 + 100 100 100 100
Dimethenamid 1121

Combination Example 3

Post-emergent Application of Compound 9-1 with Nicosulfuron

Percent Control of Broadleaf Weeds

Treatment Rate (g ai/ha) AMARE ABUTH CASOB IPOHE CHEAL
AMBEL
Comp. 9-1 31.25 60 60 0 80 90 40
Nicosulfuron 23 70 55 30 70 70
0
Comp. 9-1 + 62.5 + 95 80 10 85 95 40
Nicosulfuron 23

Percent Control of Grass Weeds

Treatment Rate (g ai/ha) SETVI ECHCG SORHA DIGSA
Comp. 9-1 31.25 10 0 10 10
Nicosulfuron 23 85 95 85 80
Comp. 9-1 + 31.25 + 90 90 95 60
Nicosulfuron 23

Combination Example 4

Postemergent Application of Compound 9-1 with Pyridate

Percent Control of Broadleaf Weeds

Treatment Rate (g ai/ha) AMARE ABUTH CASOB IPOHE CHEAL
AMBEL
Comp. 9-1 31.25 60 60 0 80 90 40
Pyridate 527 90 60 10 80 85 40
Comp. 9-1 + 31.25 + 95 100 40 90 85 85
Pyridate 527

Percent Control of Grass Weeds

Treatment Rate (g ai/ha) SETVI ECHCG SORHA DIGSA
Comp. 9-1 31.25 10 0 10 10
Pyridate 527 95 50 10 10
Comp. 9-1 + 31.25 + 85 60 30 60
Pyridate 527

Those compounds also may show utility as chemical desiccants to be used as harvest aids for crops such as cotton and potatoes. Preliminary studies are conducted in a greenhouse in which potato plant foliage was sprayed with solutions containing different compounds described in this invention. Greater than 90% necrosis of leaf tissue was observed within 1 week after application, when 100 g to 1000 g ai/ha were included in the treatment. Likewise, when cotton plants were treated, 100% necrosis of leaf tissue was observed within 48 hours after treatment.