PL170158B1 - Method of obtaining novel aryl halogenoalkyl pyrazoles - Google Patents

Abstract

1 The method of producing new a ry l - chlo row coa lk i lop i ra z l i o the formula I in which R1 denotes C1 - 8-a lk and l; C3 -8 - cycle Loa lk and I; cycles loa lkeny l, cycles loa lk and loa lk i l or cycles loa lkeny loa lk and l; C2-8 -a lkeny l or alk in y l; ben zy l; The above-mentioned group R1 can be tied to the volume of the class, the amin group, the nitro group, the jan group, the syllable, and the syllable, the group lk i lo t io, XX? ? -CYR8, -CR9, YR10 or NR11R12; R 2 o know as C1 -5 - chlo row coa lk and l; R 3 signify a tom of the boy; R 4 stands for rupe R1, t ioa lk il, a lkok sya lk il, or po l ia lkok sya lk il, ka rbamy l, a chlo rupe, g rupe am in, g rupe nit rupe c janowa, hyd rok syl, C1 - 10th rocyclly containing as he te roatoms O, S (O) mi / or NR 18. C6 - 1 2 -a ry l, a ra lk i l or a lka ry l, X X? ? -CYR 13, -CR1 4, YR 15 or NR 16R 1 7, the current proof of the two groups of R 4 can be connected to the saturated and / or not saturated current and / or not saturated with the carbon volume , - (C = X) - and / or he te diamond O, S (O) mi / or NR 18, form r for cp ie rsheet cycle has up to 9 terms, possibly under s set to any other group of R 4 groups; p r z c zym when this mo tek w i e ra O? -C-NR1 8.Then this cycle is good p ie r s c ien in jmn and e j 6 c of lons X with meaning O, S (O) m. NR19 or CR20R2 1; Y denote O or S (O) m or NR 2 2, R8 - R 2 2 denote I and the volume of hydrogen or one group R 4, m denote 0 - 2.an denote 1-5 o ra z oo are admitted to plant saline water from Janów, characterized by the fact that the relationship between B. . . . . . . . . . . . . . . . . . . . . . I PL

Description

The subject of the invention is a process for the preparation of new herbicidal aryl-haloalkylpyrazoles, which are used as an active ingredient of herbicides.

Various compounds of the substituted 3-aryl- and 5-arylpyrazole type are known from the literature. Such compounds have various uses, e.g. as synthesis intermediates, pharmaceuticals and herbicides.

Among the substituted 3-aryl-5-haloarylpyrazoles and 5-aryl-3-haloalkylpyrazoles known in the art are compounds having different radicals as substituents for the aryl and / or pyrazole moiety, e.g., alkyl, carboxyl, alkoxycarbonyl, formyl, phenyl and phenyl substituted with various groups, such as alkyl, halogen or nitro, etc. For example, compounds of this type are known in which the aryl moiety is a substituted or unsubstituted phenyl, in which the substituents are alkyl, cycloalkyl, alkaryl, halogen, trifluoromethyl, etc. and the pyrazoyl radical is substituted at various positions on nitrogen or carbon atoms with alkyl, halogen, alkoxy, heterocyclic groups, S (O) _n R groups, where n is 0-2, and R may be various radicals, such as being substituents on an aryl or pyrazole moiety.

With known compounds of the above type useful as herbicides, it is usually necessary to apply rates as high as 5 or 10 or more kilograms per hectare to achieve proper weed control. It is therefore an object of the present invention to provide a new group of arylpyrazole compounds having a uniquely high unit phytotoxic activity against a spectrum of weeds, including narrow-leaved and broad-leaved weeds, and a high degree of protection for many crops, especially cereals and / or row crops such as wheat, barley, corn, soybeans, peanuts, etc.

170 158

The compounds according to the invention, optionally in the form of agriculturally acceptable salts or hydrates, have the general formula I.

wherein R 1 is C 1-8 alkyl; C3-8 cycloalkyl; cycloalkenyl, cycloalkylalkyl or cycloalkenylalkyl; C2-8-alkenyl or alkynyl; benzyl; the above R 1 groups may be substituted by halogen, amino, nitro, cyano, hydroxy, alkoxy, alkylthio,

X X

II II

-CYR8, -CR ₉ , YR10, or NR11R12; R2 is C1-5 haloalkyl; R3 is halogen; R4 is Ri group, thioalkyl, alkoxyalkyl, or polyalkoxyalkyl, carbamyl, halogen, amino, nitro, cyano, hydroxyl, C1-10 heterocyclyl containing 0, S (O) _m and / or NRis C6-12 aryl as heteroatoms , aralkyl or alkaryl,

X X

II II

-CYR13, -CR14 YR15 or NR16R17, wherein any two R4 groups may be linked via a saturated and / or unsaturated carbon atom, - (C = X) - and / or a heterostoke, O, S (O) _m and / or NRis, forming a cyclic ring of up to 9 members, optionally substituted with any of R4; where, when this bridge includes

ABOUT

II

-C-NR18, then this cyclic ring has at least 6 members, X is O, S (O) _m , NR19 or CR20R21,

Y is O or S (O) m or NR22;

Rs - R22 are hydrogen or one of the R4 groups; m is 0-2 and n is 1-5.

A preferred subgroup of substituted arylpyrazole compounds of the present invention is formed by the compounds of formula II

and their agriculturally acceptable salts and hydrates, in which

Ri is C1-5 alkyl, alkylthio, alkoxyalkyl, C2-4 alkenyl, benzyl, which groups may be optionally substituted with halogen, amino, nitro, cyano, hydroxy or

X ll

-C-YR ₈ ;

170 158

R2, R3, X, Y, and Rs are as defined for Formula I;

Rs is hydrogen or halogen;

R6 and R7 are as defined for the R4 group in Formula I.

Particularly preferred active ingredient compounds are those of formula ΠΙ.

and the agriculturally acceptable salts and solvates thereof, wherein Ri is C1-5 alkyl;

R2, R3 and R5 are as defined above,

R7 is hydrogen or an R4 group, and R6 and R7 are joined via a saturated and / or unsaturated carbon atom, - (C = X) - and / or an O, S (O) _m and / or NRis heterostube to form a cyclic ring having to 9 members, optionally substituted with any of R4 groups, when the bridge contains O

II

-C-NRis-, then said cyclic ring has at least 6 members, a

X, Y, Ri8 and m are as defined above.

Even more preferred are compounds of Formula II and the agriculturally acceptable salts and hydrates thereof, wherein Ri is methyl;

R2 is CF3, CF2Cl or CF2H;

R3 is chlorine or bromine;

R5 is fluoro;

R 6 is chlorine;

R7 is propargyloxy, allyloxy, polyalkoxy, OCH (R23) COR24 where R23 is hydrogen, methyl or ethyl and R24 is YR10 or NR11R12;

Rc and R7 are connected via a -OCH2 (C = O) N (Ris) bridge - forming a fused six-membered ring, and

Y, R10-R12 and R18 are as defined above.

Preferred compounds according to the invention include: 4-Chloro-3- (4-chloro-2-fluoro-5-propargyloxyphenyl) -1-methyl-5-trifluoromethyl-1H-pyrazole,

Ethyl 2- [2-Chloro-5- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolyl-3) -4-fluorophenoxy] propionate, [2-Chloro-5- (4-chloro-1) -methyl-5-trifluoromethyl-1H-pyrazolyl-3) -4-fluorophenoxy] 1-methylethyl acetate,

4-Chloro-3- [4-chloro-2-fluoro-5- (methoxymethoxy) phenyl] -1-methyl-5-trifluoromethyl-olH-pyrazole,

4-Chloro-3- [4-chloro-2-fluoro-5- (methoxyethoxy) phenyl] -1-methyl-5-trifluoromethylolH-pyrazole, [2-Chloro-5- (4-chloro-1-methyl- 5-trifluoromethyl-1H-pyrazolyl-3) -4-fluorophenoxy] aclan-1,1-dimethylethyl,

[2-chloro-5- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolyl-3) -4-fluorophenoxy] acetic acid,

2-Chloro-5- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolyl-3) -4-fluorobenzoate 2-ethoxy-1-methyl-2-ketoethyl,

170 158

2-Chloro-5- (4-chloro-1-methyl-5-fluoromethyl-1H-pyrazol-3) -4-aluorobenzoate 2-methoxy-1-methyl-2-ketoethyl,

Ethyl 2-Chloro-5- (4-chloro-1-methyl-5 - fluoroimethyl-1H-pyrazolyl-3) -4-fluorobenzoate, 2-Chloro-5- (4-chloro-1-methyl] oa-tri? ] uoromethyl-1H-pyrazolla 3) -4-amethylethyl aluorobenzoate,

6- (4-Chloro-1-Imethyl-a - difluoromethyl-1H-pyrazole) o-3) -7-fluoro-4- (propynyi) o-2) -2a H-1,4-benzoxazinone-3 ( 4H).

While all of the above compounds show particular utility in a variety of crops, trials so far have shown Compounds Nos. 135,137,261,282 and 446 to be of greatest interest. These compounds provide exceptional control of resistant broadleaf weeds such as amaranth, turnip, velvet and shoot in a variety of crops such as like corn, soybeans and nuts, as well as trees and vines in forest management. The other compounds of the present invention show excellent herbicidal activity against weeds in other crops such as wheat and barley.

Some of the compounds of the present invention may have more than one possible stereoisomer, and these stereoisomers may differ in herbicidal effectiveness. The structures shown in the drawings include all possible stereoisomers.

The above compounds can be applied in various ways, e.g. pre-emergence and / or post-emergence, superficially, to soil prior to plant emergence, etc.

As used herein, the terms alkyl, alkenyl, and alkynyl, used alone or in combination terms, e.g., haloalkyl, haloalkenyl, alkoxy, alkoxyalkyl, and the like, include straight-chained and branched radicals. The preferred alkyl radicals are lower alkyls having 1-4 carbon atoms and the preferred alkenyl and alkynyl radicals are those having 2-4 carbon atoms.

The term haloalkyl denotes alkyl radicals substituted with one or more halogen atoms (chlorine, bromine, iodine or fluorine); preferred radicals of this group are those having 1 to 4 carbon atoms, especially halogenomethyl radicals, for example trifluoromethyl. In polyhaloalkyl radicals, the halogen atoms can be the same or different.

Representative, non-limiting examples of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, and cycloalkenylalkyl radicals are:

Methyl, ethyl, isomeric propyls, butyls, pentiles, hexyls, heptyls, octyls, nonyls, deciles etc .; vinyl, allyl, 2-butenyl, methylallyl, isopmeric butenyls, pentenyls, hexenyls, heptenyls, octenyls; ethynyl, isomeric propynyls, butynyls, pentyls, hexynyls etc .; alkoxy, polyacoxy, alkoxyalkyl and polyalkoxyalkyl analogs of the above alkyl groups, e.g. methoxy, ethoxy, propoxy, butoxyl, pentoxy and hexyloxy and the corresponding polyalkoxyl and alkoxyalkyls, e.g. methoxymethoxy, methoxyethoxy, ethoxymethoxy, ethoxyethoxy, methoxymethyl, methoxymethyl, , isopropoxymethyl, butoxymethyl, isobutoxymethyl, t-butoxymethyl, pentoxymethyl, hexyloxymethyl, etc., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopeptyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl etc .; isomeric cyclopentenyls, cyclohexenyls, and cyclopentenyls having one or two unsaturations; representative aralkyl and alkaryl aryl groups are phenyl, isomeric tolyls and xylls, benzyl, naphthyl etc.

Representative mono-, di-, and trihaloalkyl radicals include: chloromethyl, chloroethyl, bromomethyl, bromoethyl, iodomethyl, iodoethyl, chloropropyl, bromopropyl, iodopropyl, 1,1a, chloro-methyl, 1,1-avubromomethyl, 10 ^ -lucum; 2-chloro-2-aromopropyl, 2-chloro-3-aromopropyl, trifluoromethyl, trichloromethyl etc., is 1,2-dibromopropyl, 2,3-dibromopropyl, 2,3-dibromopropyl, etc.

Representative heterocyclic radicals include alkylthiodiazoles, piperidyl; piperidylalkyl; dioxolanylalkyl; thiazolyl; alkylthiazolyl; benzothiazolyl; halobenzothiazolyl; furyl; alkyl-substituted furyl; furylalkyl; pyridyl; alkylpyridyl; alkyloxazolyl; tetrahydrofuridotoxyl; 3-cyanothienyl; thienylalkyl; alkyl-substituted thienyl: 4,5-polyaatkylenethienyl; piperidyl; alkylpiperidyl; pyridyl; di- or tetrahydropyridyl; alkyltetrahydromorpholinyl; alkylmorpholinyl; azabicyclononyl; diazacycloalanyl; benzoalkylpyrrolidyl; oxazolidyl; perhydroxazolidyl; alkyloxazolidyl; furyloxyoxyoxyhdyl; thienyloxazolidyl; pyridyloxazolidyl; pyrimides? 170 158 oxazolidyl; benzooxazolidyl; C3-7 ^ -SF ^ irocy ^ 1 <1 (o ^ Il <yl ^^^^^^ "Lid.yl; alkylaminoalkenyl; alkyldenimino; pyrrolidyl; piperidonyl; perhydroazepinyl; perhydroazocinyl; pyrazolyl; dihydropyrazolyl; piperazinyl; perhydro-1,4- diazepinyl; quinolyl; isoquinolyl; di-, tetra-, and perihoquinolyl or -isoquinolyl; indolyl and di- and perhydroindolyl; and said heterocyclic groups substituted with such radicals as those given in the definitions of Formulas I - III.

The term agriculturally acceptable salt of the compounds represented by the above formulas as used herein means a salt or salts which readily ionize in an aqueous medium to form the cation or anion of these compounds and the corresponding anion or cation salt, which salts do not adversely affect the herbicidal properties of the given herbicide and which allow for the preparation of various mixtures, e.g. herbicide-antidote formulations, without the problems of mixing, suspending, stability, application equipment, packaging, etc.

The term herbicidally effective amount means the amount of the herbicide needed to cause significant damage or destruction to a significant proportion of the undesirable plants or weeds treated. Although there is no strict rule, it is economically desirable that 80-85% or more of the weeds be destroyed, although economically significant suppression of weed growth may occur at much lower levels, especially with some very harmful herbicide tolerant plants. .

A process for the preparation of compounds of Formula I wherein R 1 is C 1 -6 alkyl; C3-8cycloalkyl; cycloalkenyl, cycloalkylalkyl or cycloalkenylalkyl; or alkynyl;

benzyl; the above R 1 groups may be substituted by halogen, amino, nitro, cyano, hydroxy, alkoxy, alkyl,

X X

II II

-CYR8, -CR9 YR10 or NRnRn; R2 is C1-5 haloalkyl; R3 is halogen; R4 is Ri, thioalkyl, alkoxyalkyl; or polyalkoxyalkyl, carbamyl, halogen, amino, nitro, cyano, hydroxy, C 1-10 heterocyclyl containing 0, S (O) _m and / or NR18, C6-12 aryl, aralkyl or alkaryl as heteroatoms,

X X

II II

-CYRI13, -CR 14, YRi- or NR16R1-, wherein any two R4 groups may, be linked via a saturated and / or unsaturated carbon atom, - (C = X) - and / or heterostoke 0, S (O) _m and / or NRis to form a cyclic ring of up to 9 members, optionally substituted with any of R4 groups; where, when this bridge includes

ABOUT

II

-C-NRi8, then said cyclic ring has at least 6 members, X is 0, S (O) _m , NR, 9 or CR20R21, Y is 0 or S (O) _m or NR22; Rs - R22 are hydrogen or one of the R4 groups; m is 0-2, and n is 1-5, and their agriculturally acceptable salts and hydrates include the compound of formula B,

wherein R1, R2, R4 and n are as defined above, is reacted with a halogenating compound.

170 158

Any solvent which does not clearly interfere with the course of the reaction may be used in the reaction, or the reaction may be carried out in the absence of a solvent. Such solvents include, but are not limited to, organic acids, inorganic acids, hydrocarbons, halogenated hydrocarbons, aromatic hydrocarbons, ethers, and sulfides, sulfoxides, and sulfones. Halogenating agents suitable for the above reaction include bromine, chlorine, N-bromosuccinimide, N-chlorosuccinimide, sulfuryl chloride, etc. For some halogenating agents it is preferable to use an organic peroxide or light as a catalyst. The amount of the halogenating agent may be from less than 1 molar equivalent to the excess. The reaction temperature is from -100 ° C to 200 ° C, preferably 10 - 100 ° C. The reaction can be carried out in a period ranging from a few minutes to several weeks depending on the amount of reagents, reaction temperature, etc. After completion of the reaction, the product is isolated by diluting the reaction mixture with water, and the product is isolated by a method such as crystallization or solvent extraction. If necessary, the product is purified by known methods.

The compound of formula IUa is preferably used

Hive

wherein Ri is C1-5 -alkyl, R2 is C1-5 haloalkyl, Rs is hydrogen or halogen, R6 is hydrogen or R4, R represents a hydrogen reverse or a R4 group, and R6 and R7 may be joined via a saturated and / or unsaturated carbon atom, - (C = X) - and / or an O, S (O) _m and / or NRi8 heterostube to form a cyclic ring having to 9 members, optionally substituted with any of R4 groups, which when the bridge includes

ABOUT ' '

II

-C-NR18-, then said cyclic ring has at least 6 members and X, Y, R4, R8-R22 and m are as defined in formula I.

Most preferably, a compound of formula Ilia is used in which Ri is methyl: R2 is CF3, CF2Cl or CF2H; R5 is fluoro and R6 and R7 are as defined above, and a halogenating agent in which a chlorine or bromine atom is present.

Examples 1-4 describe the preparation of compounds of formula B and examples 5-7 of compounds of formula I. The melting point is abbreviated mp. The boiling point was abbreviated as bp.

Example 1

This example describes the preparation of 3- (2,5-difluorophenyl) -1-methyl-5-trifluoromethyl-1H-pyrazole (Compound No. 40) and 5- (2,5-difluorophenyl) -1-methyl-3-trifluoromethyl-pyrazole (Link No.20)

A. 28.5 g of 2,5-difluoroacetophenone and 26 g of ethyl trifluoroacetate were mixed in 400 ml of anhydrous ether and cooled in an ice bath. Then 42 ml of 25% (w / w) sodium methoxide in methanol were added over 5 minutes. After stirring for 1 hour at room temperature, the reaction mixture was extracted with water, the water was acidified and extracted with methylene chloride to give 42 g of 1- (2,5-difluorophenyl) -3-trifluoromethylpropanedione-1,3.

B. 34.5 g of 1- (2,5-difluorophenyl) -3-trifluoromethylpropanedione-1,3 were dissolved in 250 ml of acetic acid and 9.5 ml of methylhydrazine was slowly added. The mixture was heated at 100 ° C for 5 minutes, then cooled and diluted with ether. The ether solution was washed with water and potassium carbonate solution and then dried over sulfate

170 158 magnesium, filtered and concentrated. The residue was chromatographed to give 9.5 g of 3- (2,5-difluorophenyl) -1-methyl-5-trifluoromethyl-1H-pyrazole.

Calculated for C 1 H 7 N 2 F-: C 50.39%% H 2.69%; N 10.68%

Found: 0 50 ,, ^!: ^ *%; H 2.72%; N 10.64%, and 21.22g 0 - (^ ,: 0 ^ d \ uufil ^ (^^ <^ phenyl) t1 - ^ ethyl-; 9-d-6f ^ f ^ iromethyld1H ^ pyra: zolf ( mp 98 - 99 ° C)

Calculated for C 11 H 7 N 2 F-: C 50.39%; H 2.69%; N 10.68%

Found: C 50.63%; H 2.65%; N 10.40%.

Example 2

This example describes the preparation of 0-2,4-difuoro-phenyl) -3-difluoromeryl-1H-pyrazole (Compound No. 6)

A. To a solution of 9 "g (" 206 mol) 2 ', 4' -difluoroacetophenone (commercially available) in 4 "ml of diethyl ether was added at. [Deg.] C 4, ml of (2 ^ mol) ethyl trifluoroacetate. At 0 ° C, 8 ml of 20% (w / w) sodium methoxide in methanol were added over 10 minutes. The reaction mixture was stirred overnight at 20 ° C. The mixture was poured into 9 mL of ice water and 21.9 mL (1.97 mol) of acetic acid was added. The organic layer was washed twice with water, dried over anhydrous MgSO4, and concentrated in vacuo to give 62.80 g (97%) of 4- (2,4-difluorophenyl) -1,1,1-fluoro-6o-4-hydroxybutene-9-one -2 in the form of a yellow olef; H NMR (CDCl ₃ ) ppm: 6.61 (s, 1H), 6.87 (m, 1H), 6.97 (m, 1H), 7.97 (m, 1H).

Calculated for C10H5F5O2: C 47.64; H ^ ,,,.

Found: (7, -5.70; 16 1.96.

B. At 24 ° C, 10 µg φ, mol) of the product from step A was dissolved in 0.1 ml of glacial acetic acid and 2 ml (1.64 mol) of anhydrous hydrazine was added over 0 minutes. The reaction mixture was heated to 90 ° C for 0 minutes. The reaction mixture was cooled and poured into 9 mL of ice water. The slurry was filtered and the cake washed with water and air dried to afford 13.86 g (94%) of 0-2,4-difuoro-phenyl) -3- [beta] -fluoromethyl-1H-pyrazole as a white solid, m.p. 107-158 ° C.

Calculated for C10H5N2; C 48.4; H 2.9; N 11.29.

Found: C 48.98; H 2.9; N 11.92.

Example 9

This example describes the preparation of 3-2,4-difluorophenyl) -1-methyl-O-trifluoromethyl-1H-pyrazole (Compound No. 42) and 0-2,4-difluoromethyl) -1 -I-methyl-3- -r6jffuoromethylolH-pyrazole (Compound No. 21)

A suspension of 19.6 g (1.00 mol) of the product from step B, 7.7 g (0.006 mol) of K2CO3 and 9.7 ml (1.66 mol) of methyl iodide in 15 ml of acetone was stirred overnight at 20 ° C. The solution was diluted with ml of cold water and extracted three times with ethyl acetate. The acetate extracts were washed with brine, dried over anhydrous MgSO4, and concentrated in vacuo. The residue was purified by chromatography using 0% ethyl acetate in hexane as eluent to give 8.9 g (08%) of 9-2,4-difluoro-phenyl) -1-methyl-5-fluoromethyl-1H-pyrazole as a white solid at mt 01 ° C.

Calculated for C11H7F5N2: C 50.39; H 2.69; NI 0, 8.

Found: C 50), 3 (); H 2.70; NS 0.70.

The chromatography described in the above recipe gave a second fraction which was separated and concentrated, and the residue was crystallized to give 4 g (28% yield) of 0-2,4-difuorofemyl) -1-I-methyl-3-- β-fluoromethyl-1H-pyrazole in the form of a white solid at 1.1. 97-98 ° C.

Calculated for C11H7F5N2: C 50.39; H 2.69; NS 1.66.

Found: C 50.4; H2.77; N 11, 7.

Example 4

This example describes the preparation of 3-2,5-difluorophenyl) -1-methyl-5-difluoromethyl-1H-pyrazole (Compound No. 4,)

The size of 8.0 g (94 mmol) of anhydrous 0-2,5-difluorophenyl) -1-netyl-3-trifluoromeryl-1H-pyrazole in 100 ml of anhydrous toluene was refluxed in a device equipped with Dean-Stark drop catcher and 9.20 ml of dimethyl sulfate was added. The mixture was heated to reflux at

Reflux for 5 hours, allowed to cool and washed with 10% (w / v) aqueous NaOH solution. The organic layer was dried over anhydrous MgSO4 and concentration yielded 7.74 g (86.2%) of a clear, almost colorless oil with an nD of 1.4925 (25 ° C).

Calculated for C11H7N2F5: C 50.39%; H2.69%; N 10.68%.

Found: C 50.48%; H 2.72%; N 10.64%.

Example 5

This example describes the preparation of 4-chloro-3- (2,5-difluorophenyl) -1-methyl-5-tetrafluoromethyl-1H-pyrazole (Compound No. 361)

At 25 ° C, 5.24 g of 2-2,5-difuoro-phenyl) -1-methyl-3-tetrafluoromethyl-1H-pyrazole was dissolved in 40 ml of glacial acetic acid and 2.1 g (0.1 g 03 mole) of chlorine gas. The reaction mixture was stirred for 2 hours. The reaction solution was poured into 200 ml of ice-water, and extracted with ethyl acetate. The organic layer was washed with water, saturated NaHCO3, and brine, dried over anhydrous MgSO4, and stripped in vacuo. The residue was purified by chromatography using 3% ethyl acetate in hexane as eluant to give 5.87 g (99%) of 4-chloro-3-2,5-dwujluorofenylo) -1-methyl-5-trójfluoIΌmerylo-lH-pyrazole as a light yellow oil on ²⁵ D 1.4977.

Calcd for CnH ₆ C1iF5N _2: C, 44.54; H 2.04; N 9.44; Cl 11.95.

Found: C 44.53; H 2.00; N 9.44; Cl 11.94.

Example 6

This example describes the preparation of 4-chloro-3- (2,5-dujluorophenyl) -1-methyl-5-trifluoromethyl-1H-pyrazole (Compound No. 389)

To 5.00 g of 3- (2,5-difluorophenyl) -1-methyl-d-trifluoromethyl-1H-pyrazole dissolved in 50 ml of acetic acid was added 15 ml of sulfuryl chloride. The mixture was gently refluxed with a 2 ml portion of sulfuryl chloride added every 15 minutes. After 6 hours, the mixture was cooled, then diluted with water and extracted with ether. The ether was washed three times with water, dried over benzene, MgSO4, filtered and concentrated. The residue was chromatographed to give 4-chloro-d-2,5-dujluorophenyl) -1-methyl-5-trifluoromethyl-1H-pyrazole in quantitative yield.

Calculated for Cn H5N3O2Cl1F5: C 38.67%; H 1.48%; N 12.30%.

Found: C 38.73%; H 1.48%; N 12.34%.

Example 7

This example describes the preparation of N-chloro-3- (4-chloro-2-fluoro-5-methoxyphenyl-1-1-methylethyl) -5-trifluoromethyl-1H-pyrazole (Compound No. 489).

2.0 g of N- was added to a solution of 1.6 g of 3- (4-chloro-2-ί-uoro-d-methosyphenyl) -1- (1-methylethyl) -5-trifluoromethyl-1H-pyrazole in 20 ml of dimethylformamide. chlorosuccinimide. The solution was heated to 80 ° C for 2 hours, allowed to cool, and poured into ice water. The aqueous mixture was extracted three times with methylene chloride and the combined organic extracts were washed with water, dried with magnesium sulfate to give a crude oil after concentration. The oil was chromatographed and flask distilled to yield 1.54 g of 4-chloro-3-4-dCloro-2-fluoro-d-methoxyphenyl) -1- (1-methylethyl) -5-trifluoromethyl-1H- pyrazole as a yellow oil with nD 1.5192 (24 ° C).

Calculated for C14H12N2O1F4Cl1; C 45.31%; H 3.26%; N 7.55%.

Found: C 45.19%; H 3.27%; N 7.49%.

170 158

TABLE 1

PHYSICAL DATA OF 1-METHYL-5-ARYLOPYRAZOLA

Relationship no R2 R3 Rs Ró R? Physical data (m.t., Sep., Sun) 62 cf ₂ h Cl F. H. F. n _D , 1.5162 (25 ° C) 63 cf ₃ Cl F. Cl ch ₃ 71.0-72.0 ° C 64 cf ₂ h Cl F. Cl ch ₃ 91.0 ° C 65 cf ₃ Cl H. NO ₂ H. 122.5- 123.5 ° C 66 cf ₃ Cl H. Cl H. 68.9 - 69.6 ° C 67 cf ₂ ci Cl H. Cl H. 65.1-66.0 ° C 68 cf ₃ Br F. H. F. 53.0 ° C 69 cf ₃ Cl F. H. F. 69.0 ° C 70 cf ₃ Cl F. NO ₂ F. 88.0 ° C 71 cf ₃ CI F. oh ₃ F. nD 1.5062 (25 ° C) 72 cf ₃ CI F. no ₂ OCH3 123.0 - 124.0 ° C 73 cf ₃ Cl F. nh ₂ oh ₃ 120.0-120.5 ° C 74 cf ₃ Cl F. Cl oh ₃ 100.0 ° C 75 cf ₃ Cl F. F. H. 43.0 - 44.0 ° C 76 cf ₃ Cl F. Cl OCH ₂ C = CH 116.5-117.0 ° C 77 cf ₃ Cl F. F. no ₂ 57.0 - 58.5 ° C 78 cf ₃ Cl F. oh ₃ no ₂ 108.0 ° C 79 cf ₃ Cl F. Cl H. 73.0 - 74.0 ° C 80 cf ₃ Cl CI Cl F. 71.5-72.5 ° C

Table 2

PHYSICAL DATA OF 1-METHYL-3-ARYLOPYRAZOLA

Relationship no r ₂ r ₃ r ₅ Ró R? Physical data (m.t., Sep., Sun) 1 2 3 4 5 6 7 81 cf ₃ Cl H. ΝΟ2 H. 93.0 - 95.0 ° C 82 cf ₃ Cl H. Cl H. 68.2 - 69.2 ° C 83 CF2C1 Cl H. Cl H. 37.0 - 38.4 ° C

170 158

Table 2 (continued)

1 2 3 4 5 6 7 84 CF3 Cl Cl Cl F. 64.0 ° C 85 CF3 Cl Cl Cl H. 78.5-79.5 ° C 86 CF3 Cl Cl Cl NO2 118.0-120.0 ° C 87 CF3 Cl Cl Cl N (SO ₂ CH3) 2 137.00 88 CF3 Cl Cl Cl NHCOCF3 125.0 ° C 89 CF3 Cl Cl Cl SO2Cl 127.0 - 128.0 ° C 90 CF3 Cl Cl Cl N (SO2CH2CH3) 2 185.0 ° C 91 CF3 Cl Cl Cl NHSO2 CH3 160.0 ° C 92 CF3 Cl Cl Cl NHSO2 CH2CH3 125.0 ° C 93 CF3 Cl Cl Cl SH 100.0 ° C 94 CF3 Cl F. Br OCH3 76.0 - 77.0 ° C 95 CF3 Cl F. Br OH 83.0 - 84.0 ° C 96 CF3 Cl F. Br OH 112.0-113.5 ° C 97 CF3 Cl F. Br OCH (CH3) CO2 Et nD, 1.5217 (25 ° C) 98 CF3 Cl F. Cl 2- (4,5-dihydroxazole and l) 110.0 ° C 99 CF3 Cl F. Cl 4-morpholinyl 98.0 - 99.0 ° C 100 CF3 Cl F. Cl 2 - 1,3-dioxolanyl) nD 15348 (25 ° C) 101 CF3 Cl F. Cl 2- (1,3-dithiolanyl) clear, colorless oil 102 CF3 Cl F. Cl 2--1,3-oxathiolanyl) nD 15614 (25 ° C) 103 CF3 Cl F. Cl C (CH3) 2C = N nD 1.5274 (25 ° C) 104 CF3 Cl F. Cl C (CH3) = NOCH2CO2Et nD 1.5203 (25 ° C) 105 CF3 Cl F. Cl C (CH3> NOCH ₂ CONH2 96.0 ° C 106 CF3 Cl F. Cl CH (CH3) CsN nD, 15280 (25 ° C) 107 CF3 Cl F. Cl CH (CH3) OH 85.0 - 87.0 ° C 108 CF3 Cl F. Cl CH2Br 112.0-114.0 ° C 109 CF3 Cl F. Cl CH2Cl 100.0-102.0 ° C 110 CF3 Cl F. Cl CH2CO2CH3 64.0 - 65.0 ° C 111 CF3 Cl F. Cl CH2CO2H 139.0- 141.0 ° C 112 CF3 Cl F. Cl CH2CONH2 185.0- 189.0 ° C 113 CF3 Cl F. Cl CH2CONHCH2CH2Cl 187.0 ° C 114 CF3 Cl F. Cl CH2CONHCH3 212.0 ° C 115 CF3 Cl F. Cl CH2C = N 89.0-91.0 ° C 116 CF3 Cl F. Cl CH2O CH2CH2F 57.0 ° C 117 CF3 Cl F. Cl CH2O CH2CH2OCH3 nD, 15155 (25 ° C) 118 CF3 Cl F. Cl CH2O CH2CH3 34.0 - 37.0 ° C 119 CF3 Cl F. Cl CH2OCH2CO2CH (CH3) 2 55.0 ° C 120 CF3 Cl F. Cl CH2O CHoCsCH 44.0 ° C 121 CF3 Cl F. Cl CH2OC0CH3 90.0 ° C 122 CF3 Cl F. Cl CH2OH 103.0-104.0 ° C 123 CF3 Cl F. Cl CH2SCH2CO2 Et 63.0 ° C 124 CF3 Cl F. Cl CH3 72.0 - 74.0 ° C 125 CF3 Br F. Cl CH3 93.0 - 95.0 ° C 126 cf ₂ h Cl F. Cl CH3 115.0 ° C 127 CF3 Cl F. Cl CH = C (CH3) CO2 Et 54.0 ° C 128 CF3 Cl F. Cl CH = CHCO2CH3 117.0 ° C 129 CF3 Cl F. Cl CH = NOCH2CO2Et nD 15,330 (25 ° C) 130 CF3 Cl F. Cl CH = NOCH2CO2H 170.0 ° C 131 CF3 Cl F. Cl CH = NOCH2CONH2 169.0 ° C 132 CF3 Cl F. Cl CHBr2 89.0 - 92.0 ° C 133 CF3 Cl F. Cl CHO 70.0 - 72.0 ° C 134 CF3 Cl F. Cl CO2-ccklohexyl nD, 1.5287 (25 ° C)

170 158

Table 2 (continued)

1 2 3 4 5 6 7 135 cf ₃ Cl F. Cl CO ₂ CH (CH ₃ ) ₂ 69.0 ° C 136 cf ₃ Cl F. Cl CO ₂ CH (CH ₃ ) CH ₂ CH ₃ nD, 1.5150 (25 ° C) 137 cf ₃ Cl F. CI CO ₂ CH (CH ₃ ) CO ₂ CH ₃ nD, 1.5190 (25 ° C) 138 cf ₃ Cl F. Cl CO ₂ CH (CH ₃ ) CO2 Et nD, 1.5119 (25 ° C) 139 cf ₃ Cl F. Cl CO ₂ CH ₂ CH (CH ₃ ) 2 nD, 1.5158 (25 ° C) 140 cf ₃ Cl F. Cl CO ₂ CH ₂ CH (CH ₃ ) CH ₂ CH ₃ nD, 1.5145 (25 ° C) 141 cf ₃ Cl F. Cl CO ₂ CH ₂ CH ₂ CH (CH ₃ ) ₂ nD, 1.5132 (25 ° C) 142 cf ₃ Cl F. Cl CO ₂ CH ₂ CH ₂ OCH ₃ 64.0 ° C 143 cf ₃ Cl F. CI CO ₂ CH ₂ CO ₂ Et 83.0 ° C 144 cf ₃ Cl F. Cl every ₂ ch ₂ oh 92.0 ° C 145 cf ₃ Cl F. CI every ₂ ch ₂ oh ₃ 77.0 ° C 146 cf ₃ Cl F. Cl every ₂ ch ₃ 78.0 ° C 147 cf ₃ Cl F. Cl CChCHFCCbEt nD, 1.5112 (25 ° C) 148 cf ₃ Cl F. Cl CO ₂ Et 88.0 ° C 149 cf ₃ Cl F. Cl CO2H 179.0-180.0 ° C 150 cf ₃ Cl F. Cl CO2 n-butyl clear oil 151 cf ₃ Cl F. Cl CO ₂ t-butyl nD, 1.5130 (25 ° C) 152 cf ₃ Cl F. Cl coch ₃ 134.0- 135.0 ° C 153 cf ₃ Cl F. Cl CON (CH ₃ ) ₂ clear oil 154 cf ₃ Cl F. Cl CONHC (CH ₃ ) ₂ CH ₂ OH 115.0 ° C 155 cf ₃ Cl F. Cl conhch ₂ ch ₂ ci 129.0 ° C 156 cf ₃ Cl F. Cl conhch ₂ ch ₂ oh 143.0 ° C 157 cf ₃ Cl F. Cl CONHCH3 172.0 ° C 158 cf ₃ Cl F. Cl CONHN (CH ₃ ) ₂ 172.0 ° C 159 cf ₃ Cl F. Cl conhoch ₂ every ₂ ch ₃ 95.0 ° C 160 cf ₃ Cl F. Cl COSCH (CH ₃ ) ₂ nD, 1.5475 (25 ° C) 161 cf ₃ Cl F. Cl COSCH (CH ₃ ) CO ₂ Et nD, 1.4723 (25 ° C) 162 cf ₃ CI F. Cl F. 45.5 - 46.5 ° C 163 cf ₃ Cl F. Cl H. 34.0 - 35.0 ° C 164 CC1 ₃ Cl F. Cl H. 62.0 - 64.0 ° C 165 cf ₂ h Cl F. Cl H. 61.0 ° C 166 cf ₃ Cl F. Cl N (CH ₃ ) CH ₂ CH ₂ CH ₃ nD, 1.5030 (25 ° C) 167 cf ₃ Cl F. Cl N (COCF ₃ ) CH ₂ CH = CH ₂ 75.0 ° C 168 cf ₃ Cl F. Cl N (COCF ₃ ) CH ₂ CO ₂ Et 76.0 - 79.0 ° C 169 cf ₃ Cl F. Cl N (COCF ₃ ) CH ₂ CsCH nD, 1.5061 (25 ° C) 170 cf ₃ Cl F. Cl N (COCF ₃ ) CH ₃ nD, 1.5004 (25 ° C) 171 cf ₃ Cl F. Cl N (COCH ₃ ) CH (CH ₃ ) ₂ COCH ₃ 140.0 ° C 172 cf ₃ Cl F. Cl N (SO ₂ CH ₂ CH ₂ CH ₃ ) 2 138.0 ° C 173 cf ₃ Cl F. Cl N (SO2CH ₂ CH ₃ ) ₂ 135.0 ° C 174 cf ₃ Cl F. Cl N (SO ₂ CH ₃ ) 2 205.0 ° C 175 cf ₃ Cl F. Cl N (SO2N (CH ₃ ) 2) 2 149.0- 153.0 ° C 176 cf ₃ Cl F. Cl NEt ₂ nD, 1.5262 (25 ° C) 177 cf ₃ Cl F. Cl nh ₂ 96.0 - 98.0 ° C 178 cf ₂ h Cl F. Cl nh ₂ 110.0- 111.5 ° C 179 cf ₃ Cl F. Cl NHCH (CH ₃ ) 2 nD, 1.5361 (25 ° C) 180 cf ₃ CI F. Cl NHCH (CH ₃ ) CO ₂ Et 55.0 - 57.0 ° C 181 cf ₃ CI F. Cl NHCH (CH ₃ ) CO ₂ H. 167.0- 169.0 ° C 182 cf ₃ Cl F. Cl NHCH (CH ₃ ) CONHCH ₃ 134.0- 135.0 ° C 183 cf ₃ Cl F. Cl nhch ₂ ch = ch ₂ nD, 1.5483 (25 ° C) 184 cf ₃ Cl F. Cl NHCH ₂ CO ₂ Et 114.0-116 ° C 185 cf ₃ Cl F. Cl NHCH2CO2H 176.0-182.0 ° C

170 158

Table 2 (continued)

1 2 3 4 5 6 7 186 CF3 Cl F. Cl NHCH2CSCH 73.0 ° C 187 CF3 Cl F. Cl NHCH3 nD, 1.5509 (25 ° C) 188 CF3 Cl F. Cl NHCO2 Et 74.0 - 76.0 ° C 189 CF3 Cl F. Cl NHCOCF3 137.0-138.0 ° C 190 CF3 Cl F. Cl NHCOCH2CO2CH3 155.0 ° C 191 CF3 Cl F. Cl NHCOCH2OCH3 163.0- 165.0 ° C 192 CF3 Cl F. Cl NHPO (OEt) 2 84.0 - 87.0 ° C 193 CF3 Cl F. Cl NHSO2CF3 300.0 ° C 194 CF3 Cl F. Cl NHSO2CH2CH2CH3 81.0 ° C 195 CF3 Cl F. Cl NHSO2CH2CH3 112.0 ° C 196 CF3 Cl F. Cl NHSO2CH3 108.0 ° C 197 CF3 Cl F. Cl NO2 102.0-104.0 ° C 198 CF2H Cl F. Cl NO2 91-92.5 ° C 199 CF3 Cl F. Cl O (CH2) 5CO2 Et nD, 1.5077 (25 ° C) 200 CF3 Cl F. Cl O (CH2) 5CO2H nD, 1.5174 (25 ° C) 201 CF3 Cl F. Cl O (CH2) 5CONHCH2CH2OH 62.0 - 64.0 ° C 202 CF3 Cl F. Cl O (CH2) 5CONHCH3 118.0-120.0 ° C 203 CF3 Cl F. Cl O- (2-chloro-4-trifluoro- methyl) phenyl nD, 1.5356 (25 ° C) 204 CF3 Cl F. Cl O- (2-nitfo-4-trifluoromethylphenyl) 119.0 ° C 205 CF3 Cl F. Cl O- (4-trifluoroethylene) phenyl nD, 1.5275 (25 ° C) 206 CF3 Cl F. Cl O- (p-niirophenyl) nD, 1.5796 (25 ° C) 207 CF3 Cl F. Cl O-n-dodecyl nD, 1.4985 (25 ° C) 208 CF3 Cl F. Cl O-n-hexyl nD, 1.5104 (25 ° C) 209 CF2H Cl F. Cl OC (CH3) 2CH2Cl nD, 1.5210 (25 ° C) 210 CF3 Cl F. Cl OC (CH3) 3 nD, 1.5128 (25 ° C) 211 CF3 Cl F. Cl OCF2H 45.0 ° C 212 CF3 Cl F. Cl OCH (CH2CH3) CO2 Et nD, 1.4309 (25 ° C) 213 CF3 Cl F. Cl OCH (CH2CH3) CO2H 139.0-140.0 ° C 214 CF3 Cl F. Cl OCH (CH2CH3) CONHCH3 152.0 ° C 215 CF3 Cl F. Cl OCH (CH3) (2- (4,5-dihydro- xazolil)) nD, 1.5336 (25 ° C) 216 CF3 Cl F. Cl OCH (CH3) 2 nD, 1.5169 (25 ° C) 217 CF3 Cl F. Cl OCH (CH3) OCH 59.5-61.5 ° C 218 CF3 Cl F. Cl OCH (CH3) CH2OCH3 clear oil 219 CF3 Cl F. Cl OCH (CH3) CO2 (CH2) 2Cl nD, 1.5168 (25 ° C) 220 CF3 Cl F. Cl OCH (CH3) CO2 (CH2) 3CH3 nD, 1.5005 (25 ° C) 221 CF3 Cl F. Cl OCH (CH3) CO2 (CH2) 4Cl nD, 1.5155 (25 ° C) 222 CF3 Cl F. Cl OCH (CH3) CO2-Na ⁺ 51.0- 60.0 ° C 223 CF3 Cl F. Cl OCH (CH3) CO2CH (CH3) 2 clear colorless oil 224 CF3 Cl F. Cl OCH (CH3) CO2CH (CH3) CH2CH3 nD, 1.5031 (25 ° C) 225 CF3 Cl F. Cl OCH (CH3) CO2CH2CH (CH3) 2 nD, 1.5037 (25 ° C) 226 CF3 Cl F. Cl OCH (CH3) CO2CH2CO2 Et nD, 1.5061 (25 ° C) 227 CF3 Cl F. Cl OCH (CH3) CO2CH2OCH3 nD, 1.5120 (25 ° C) 228 CF3 Cl F. Cl OCH (CH3) CO2CH3 nD, 1.5175 (25 ° C) 229 CF3 Cl F. Cl OCH (CH3) CO2Ei nD, 1.5106 (25 ° C) 230 CF3 Cl F. Cl OCH (CH3) CO2H 150.0- 151.0 ^o C 231 CF3 Cl F. Cl OCH ^^^ t-butyl nD, 1.4999 (25 ° C) 232 CF3 Cl F. Cl OCH (CH3) CON (CH3) 2 light yellow oil 233 CF3 Cl F. Cl OCH (CH3) CONH2 152.0 ° C

170 158

Table 2 (continued)

1 2 3 4 5 6 7 234 cf ₃ Cl F. Cl OCH (CH ₃ ) CONHCH ₂ CH ₂ C1 104.0 ° C 235 cf ₃ Cl F. Cl OCH (CH ₃ ) CONHCH ₂ CH ₂ OH 131.0 ° C 236 cf ₃ Cl F. Cl OCH (CH ₃ ) CONHCH ₂ CO ₂ CH ₃ 111.0- 112.0 ° C 237 cf ₃ Cl F. Cl OCH (CH ₃ ) CONHCH ₃ 134.5-135.5 ° C 238 cf ₃ Cl F. Cl OCH (CH ₃ ) CONHSO ₂ CH ₃ 159.0 ° C 239 cf ₃ Cl F. Cl OCH (CH ₃ ) COOCH ₂ CH ₂ - -OCH ₂ CH ₂ OMe nD, 1.5047 (25 ° C) 240 cf ₃ Cl F. Cl OCH (CH ₃ ) ON nD, 1.5223 (25 ° C) 241 cf ₃ Cl F. Cl OCHiEOCChCHiCfth nD, 1.5026 (25 ° C) 242 cf ₃ CI F. Cl OCH (Et) CO ₂ CH ₃ 1.5127 (25 ° C) 243 cf ₃ Cl F. Cl OCH (Et) CO ₂ n-butyl nD, 1.4983 (25 ° C) 244 cf ₃ Cl F. Cl OCH (Et) CO ₂ t-butyl 63.0 - 65.0 ° C 245 cf ₃ Cl F. Cl OCH (Et) CONH ₂ 153.0 ° C 246 cf ₃ CI F. Cl OCH (Et) CsN nD, 1.5167 (25 ° C) 247 cf ₃ Cl F. Cl OCH (OCH ₃ ) CO ₂ CH ₃ nD, 1.5174 (25 ° C) 248 cf ₃ Cl F. Cl OCH (OCH ₃ ) CO ₂ H. light yellow oil 249 cf ₃ Cl F. Cl OCH (OCH ₃ ) CONHCH ₃ 96.0 ° C 250 cf ₃ CI F. Cl OCH ₂ (1,3-dioxolanyl-2) 102.5-104.5 ° C 251 cf ₃ Cl F. Cl OCH ₂ (2-pyridyl) 122 - 123 ° C (decomposition) 252 cf ₃ Cl F. Cl OCH ₂ (5- (2-chloro) thiophene) 78-80 ° C 253 cf ₃ Cl F. Cl OCH ₂ (oxiranyl) 85.5 - 86.5 ° C 254 cf ₃ Cl F. Cl OCH ₂ (tetrahydro-2H-pyranyl-2) 88.5 - 90.0 ° C 255 cf ₃ Cl F. Cl OCH ₂ C (CH ₃ ) ₂ CO ₂ CH ₃ nD, 1.5087 (25 ° C) 256 cf ₃ Cl F. Cl OCH ₂ C (CH ₃ ) ₂ CONHCH ₃ sticky oil 257 cf ₃ Cl F. Cl OCH ₂ C (Et) = NOCH ₂ CO ₂ Et nD, 1.5147 (25 ° C) 258 cf ₃ Cl F. Cl OCH ₂ C (Et) = NOCH ₂ CO ₂ H. 128.0 ° C 259 cf ₃ Cl F. Cl OCH ₂ C (Et) = NOCH ₂ CONH ₂ 173.0 ° C 260 cf ₃ Cl F. Cl OCH ₂ C (Et) = NOCH ₃ nD, 1.5216 (25 ° C) 261 cf ₃ Cl F. Cl oh ₂ c = ch 89.5-91.0 ° C 262 cf ₃ Br F. Cl oh ₂ oh 107.0 ° C 263 cf ₃ Cl F. Cl oh ₂ cf ₃ 68.0 ° C 264 cf ₃ Cl F. Cl OCH ₂ CH (OCH ₃ ) ₂ 62.0 ° C 265 cf ₃ CI F. Cl OCH ₂ CH ₂ (1,3-dioxanyl-2) 74.0 - 75.0 ° C 266 cf ₃ Cl F. Cl OCH ₂ CH ₂ Br nD, 1.5470 (25 ° C) 267 cf ₃ CI F. Cl OCH ₂ CH ₂ CH ₂ CH ₃ nD, 1.5153 (25 ° C) 268 cf ₃ Cl F. Cl oh ₂ ch ₂ ch ₂ oh ₃ nD, 1.5175 (25 ° C) 269 cf ₃ Cl F. Cl oh ₂ ch ₂ f 103.0 ° C 270 cf ₃ Cl F. Cl oh ₂ ch ₂ oh ₃ 93.0 - 94.0 ° C 271 cf ₃ Cl F. Cl OCH ₂ CH ₂ SCH (CH ₃ ) CO ₂ Et nD, 1.5275 (25 ° C) 272 cf ₃ Cl F. Cl OCH ₂ CH ₂ SCH ₂ CO ₂ Et nD, 1.5321 (25 ° C) 273 cf ₃ Cl F. Cl OCH ₂ CH ₂ SCH ₃ nD, 1.5464 (25 ° C) 274 cf ₃ Cl F. Cl oh ₂ ch ₂ so ₂ ch ₃ clear oil 275 cf ₃ Cl F. Cl oh ₂ ch ₂ soch ₃ 87.0 ° C 276 cf ₃ Cl F. Cl oh ₂ ch ₃ 80.0 ° C 277 cf ₃ Br F. Cl oh ₂ ch = ch ₂ 52.5 ° C 278 cf ₃ Cl F. Cl oh ₂ ch = ch ₂ 76.0 ° C 279 cf ₃ Cl F. Cl OCH ₂ CO ₂ '(CH _{3) 2} CHNH ₃ ⁺ 123.0-125.0 ° C 280 cf ₃ Cl F. Cl OCH ₂ CO ₂ Na ⁺ 250.0 ° C 281 cf ₃ Cl F. Cl OCH ₂ C0 _2- cyclohexyl 150.0 ° C 282 cf ₃ Cl F. Cl OCH ₂ CO ₂ CH (CH ₃ ) ₂ 134.0- 135.0 ° C 283 cf ₂ h Cl F. Cl OCH ₂ CO ₂ CH (CH ₃ ) ₂ 129.0-130.0 ° C

170 158

Table 2 (continued)

1 2 3 4 5 6 7 284 C2F5 H. F. Cl OCH ₂ CO ₂ CH (CH ₃ ) 2 91-92 ° C 285 CF2CI Cl F. Cl OCH ₂ CO ₂ CH (CH ₃ ) 2 98 ° C 286 cf ₃ Cl F. Cl OCH ₂ CO ₂ CH (CH ₃ ) CH ₂ CH ₃ 101.0-103.0 ° C 287 CF3 Cl F. Cl OCH ₂ CO ₂ CH ₂ CH (CH ₃ ) CH ₂ CH ₃ 96.0 ° C 288 CFa Cl F. Cl OCH ₂ CO ₂ CH ₂ CH ₂ CH (CH ₃ ) ₂ 128 ° C 289 cf ₃ Cl F. Cl oh ₂ every ₂ ch ₃ 108.0-110.0 ° C 290 cf ₃ Cl F. Cl OCH ₂ CO ₂ Et 130.0-131.0 ° C 291 cf ₃ Cl F. Cl OCH ₂ CO2H 174.0 ° C 292 cf ₃ Cl F. Cl OCH ₂ CO ₂ n-butyl 96.0 - 98.0 ° C 293 cf ₃ Cl F. Cl OCH ₂ CO ₂ n-pentyl 91.0-93.0 ° C 294 cf ₃ Cl F. Cl OCH ₂ CO ₂ t-butyl 127.0 ° C 295 cf ₃ Cl F. Cl OCH ₂ COCH ₂ CH ₃ 93.0 ° C 296 cf ₃ CI F. Cl OCH ₂ CONH ₂ 191.0 ° C 297 cf ₃ Cl F. Cl OCH ₂ CONHCH (CH ₃ ) ₂ 130.0 ° C 298 cf ₃ Cl F. Cl oh ₂ conhch ₃ 144.0-145.0 ° C 299 cf ₃ Cl F. Cl OCH ₂ CONHN (CH ₃ ) ₂ 146.0- 148.0 ° C 300 cf ₃ Cl F. Cl OCH ₂ COSCH (CH ₃ ) ₂ 96.0 - 97.0 ° C 301 cf ₃ H. F. Cl oh ₂ oh 113.0 ° C 302 cf ₂ h Cl F. Cl oh ₂ c = ch 68.0 - 69.0 ° C 303 CF2C1 Cl F. Cl oh ₂ oh nD, 1.5544 (24 ° C) 304 cf ₃ Cl F. Cl oh ₂ on 98.0 ° C 305 cf ₃ Cl F. Cl oh ₂ oh ₂ ch ₂ f nD, 1.5150 (25 ° C) 306 cf ₃ Cl F. Cl oh ₂ oh ₂ ch ₂ oh ₃ nD, 1.5134 (25 ° C) 307 cf ₃ Cl F. Cl oh ₂ oh ₂ c = ch nD, 1.5275 (25 ° C) 308 cf ₃ Cl F. Cl oh ₂ oh ₃ 54.5 - 55.0 ° C 309 cf ₃ Cl F. Cl oh ₂ sch ₃ 78.0 - 79.0 ° C 310 cf ₃ Cl F. Cl oh ₂ so ₂ ch ₃ 137.0 ° C 311 cf ₃ Cl F. Cl oh ₂ soch ₃ 109.0-111.0 ° C 312 cf ₃ Cl F. Cl oh ₃ 70.0-71.0 ° C 313 cf ₃ Br F. Cl oh ₃ 85.0 - 86.0 ° C 314 cf ₂ h Cl F. Cl oh ₃ 128.0-130.0 ° C 315 CF2C1 Cl F. CI oh ₃ nD, 1.6399 (26 ° C) 316 cf ₃ Cl F. CI oh = ch ₂ 57.0 ° C 317 cf ₃ Cl F. Cl OCHFCO ₂ CH (CH ₃ ) ₂ 96.0 ° C 318 cf ₃ Cl F. CI OCHFCChEt 60.0 ° C 3) 9 cf ₃ Cl F. Cl OCHFCO2H 116.0 ° C 320 cf ₃ Cl F. Cl OCHFCOSCH (CH ₃ ) ₂ 65.0 ° C 321 cf ₃ Cl F. Cl OCOCH2CI nD, 1.5299 (25 ° C) 322 cf ₃ Cl F. Cl OCOCH ₂ OCH ₃ 76.0 - 78.0 ° C 323 cf ₃ Cl F. Cl ococh ₃ 53.0 - 55.0 ° C 324 cf ₃ Cl F. Cl OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OMe nD, 1.5111 (25 ° C) 325 cf ₃ Cl F. CI OH 123.0- 126.0 ° C 326 cf ₃ Br F. Cl OH 83.0 ° C 327 cf ₃ H. F. Cl OH 131.0 ° C 328 cf ₂ h Cl F. Cl OH 113.0-114.0 ° C 329 CF2C1 Cl F. Cl OH 107-109 ° C 330 cf ₃ Cl F. Cl SPA ₂ CH ₃ 64.0 - 65.5 ° C 331 cf ₃ Cl F. CI OSO ₂ n-propyl nD, 1.5213 (25 ° C) 332 cf ₂ h Cl F. Cl O-t-butyl nD, 1.5276 (25 ° C) 333 cf ₃ Cl F. Cl SCF2H nD, 1.5321 (25 ° C) 334 cf ₃ Cl F. Cl SCH (CH ₃ ) ₂ clear oil

170 158

Table 2 (continued)

1 2 3 4 5 6 7 335 CF3 Cl F. Cl SCH (CH3) CO2 Et nD, 1.5345 (25 ° C) 336 CF3 Cl F. Cl SCH2CH2OCH3 57.0 ° C 337 CF3 Cl F. Cl SCH2CO2CH (CH3) 2 nD, 1.5358 (25 ° C) 338 CF3 Cl F. Cl SCH2CO2Et 63.0 - 64.0 ° C 339 CF3 Cl F. Cl SCH2CO2H 128.0 ° C 340 CF3 Cl F. Cl SCH2CONH2 167.0 ° C 341 CF3 Cl F. Cl SCH2 <ohCH 98.0 ° C 342 CF3 Cl F. Cl SCH3 89.0 - 90.0 ° C 343 CF3 Cl F. Cl SH 56.0 - 58.0 ° C 344 CF3 Cl F. Cl SO2 (pyrazolild1) 155.0 ° C 345 CF3 Cl F. Cl SO2CH (CH3) 2 132.0 ° C 346 CF3 Cl F. Cl SO2Cl 116.0-117.0 ° C 347 CF3 Cl F. Cl SO2N (CH3) 2 118.0 ° C 348 CF3 Cl F. Cl SO2NHCH3 113.0 ° C 349 CF3 Cl F. Cl SOCH (CH3) 2 119.0 ^o C 350 CF3 Cl F. Cl trans - H = C (CH3) CO2H 213 ° C 351 CF3 Cl F. Cl trans - H = CHCO 2 H 209 ° C 352 CF3 Cl F. F. H. nD, 1.6284 (25 ° C) 353 CF3 Cl F. F. NH2 82.0 ° C 354 CF3 Cl F. F. Cl 50.0-51.0 ° C 355 CF3 Cl F. F. N02 90.5-91.5 ° C 356 CF3 Cl F. F. NHCOCH3 115.0- 116.0 ° C 357 CF3 Cl F. F. N (SO2CH3) 2 176.5 ° C 358 CF3 Cl F. F. NHSO2 CH3 163.0-164.0 ° C 359 CF3 Cl F. F. NHCO CH2O CH3 152.0- 154.0 ° C 360 CF3 Cl H. OCH3 N02 114.0-115.0 ° C 361 CF3 Cl F. H. F. nD, 1.4977 (25 ° C) 362 CF2 Br F. H. F. nD, 1.6267 (25 ° C) 363 CF3 Cl F. H. OC (CH3) 2CH2Cl nD, 15145 (25 ° C) 364 CF2H Cl F. H. F. nD, 15218 (25 ° C) 365 CF2H Br F. H. F. 61.5 ° C 366 CF3 Cl F. NH2 OCH3 62.5 - 63.5 ° C 367 CF3 Cl F. NH2 OCH2CH2F 135.0 ° C 368 CF3 Cl F. NH2 OEt 136.0 ° C 369 CF3 Cl F. NH2 OCH2OCH 72.0 ° C 370 CF3 Cl F. NH2 OCH (CH3) CCH nD, 1.5450 (25 ° C) 371 CF3 H. F. NH2 OCH3 121.5- 123.0 ° C 372 CF3 Br F. NH2 OCH3 85.0 - 86.0 ° C 373 CF3 Cl F. NH2 OCH2CH2OCH2CH2OCH2CH2OMe nD, 15254 (25 ° C) 374 CF3 Cl F. NH2 F. 84.0 - 86.0 ° C 375 CF3 Cl F. NH2 OC (CH3) 3 light yellow oil 376 CF3 Cl F. NH2 N (CH3) CH2CH2CH3 nD, 1.5352 (25 ° C) 377 CF3 Cl F. NH2 NEt2 nD, 1.5321 (25 ° C) 378 CF3 Cl F. NH2 4-morpholinyl 165.0- 166.0 ° C 379 CF3 Cl F. NH2 N (COCH3) CH (CH3) 2 178.0 ° C 380 CF3 Cl F. NH2 OCH2CH2SCH3 nD, 15591 (25 ° C) 381 CF2H Cl F. NH2 O-t-butyl nD, 1.5443 (25 ° C) 382 CF3 Cl F. NH2 OCH2CF3 66.0 ° C 383 CF3 Cl F. NH2 NHCH2CH = CH2 112.0 ° C 384 CF3 Cl F. OCH2OCH NO2 142.0 ° C 385 CF3 Cl F. oh ₂ c = ch NH2 94.0 - 96.0 ° C

170 158

Table 2 (continued)

1 2 3 4 5 6 7 386 CF3 Cl F. OCH2CO2Et NO2 95.0 - 96.0 ° C 387 CF3 Cl F. OCH3 NO2 116.0 ° C 388 CF3 H. F. NO2 F. 80.0-81.0 ° C 389 CF3 Cl F. NO2 F. nD, 1.5276 (25 ° C) 390 CF3 Cl F. NO2 OCH3 115.0- 116.0 ° C 391 CF3 Cl F. NO2 OCH2CH2F 134 ° C 392 CF3 Cl F. NO2 OCH2CH3 99.0 ° C 393 CF3 Cl F. NO2 SCH2CO2Et 79.0 ° C 394 CF3 Cl F. NO2 OCH2C = CH 105.0 ° C 395 CF3 Cl F. NO2 OCH (CH3) C = CH 107.5 - 108.0 ° C 396 CF3 Br F. NO2 F. 45.5 ° C 397 CF3 Br F. NO2 OCH3 144.5 - 145.5 ° C 398 CF3 H. F. NO2 OCH3 140.0- 141.5 ° C 399 CF3 Cl F. NO2 OCH2CH2OCH2CH2OCH2OMe nD, 1.5188 (25 ° C) 400 CF3 Cl F. NO2 OCH2CO2Et 104.0 ° C 401 CF3 Cl F. NO2 OC (CH3) 3 80.0 ° C 402 CF3 Cl F. N02 N (CH3) CH2CH2CH3 nD, 1.5534 (25 ° C) 403 CF3 Cl F. NO2 NHCH (CH3) 2 100.0 ° C 404 CF3 Cl F. NO2 NEt2 nD, 1.5387 (25 ° C) 405 CF3 Cl F. 4- im ^ and ^ ^ oHnyl 136.0- 137.0 ° C 406 CF3 Cl F. N02 N (COCH3) CH (CH3) 2 123.00 407 CF3 Cl F. NO2 SCH (CH3) CO2 Et nD, 1.5543 (25 ° C) 408 CF3 Cl F. NO2 OH 86.0 ° C 409 CF3 Cl F. NO2 OCH2COCH2CH3 109.0 ° C 410 CF3 Cl F. NO2 OCH2COCH2CH3 103.0 ° C 411 CF3 Cl F. NO2 OCH (CH3) CH2OCH3 nD, 1.5263 (25 ° C) 412 CF3 Cl F. NO2 OCH2CH2CH2OCH3 67.0 ° C 413 CF3 Cl F. NO2 N (COCF3) CH2CH2CH2OCH3 105.0 ° C 414 CF2H Cl F. NO2 F. 80.0 ° C 415 CF2H Cl F. NO2 OCH3 416 CF3 Cl F. NO2 OCH2CH2SCH3 nD, 1.5587 (25 ° C) 417 CF2H Br F. NO2 F. 83.0 - 85.0 ° C 418 CF2H Br F. NO2 OCH3 154.0-156.0 ° C 419 CF2H Cl F. NO2 O-t-butyl 71.0-73.0 ° C 420 CF3 Cl F. NO2 OCH2CF3 108.0-109.0 ° C 421 CF3 Cl F. NO2 NHCH2CH = CH2 54.0 - 56.0 ° C 422 CF3 Cl F. NO2 N (COCF3) CH2CH = CH2 91.0 ° C 423 CF3 Cl F. OCH3 NH2 light yellow oil 424 CF3 Cl F. OCH3 Cl 88.0 ° C 425 CF3 Cl F. OCH3 NHCOCH2CO2CH3 1110 ° C 426 CF3 Cl F. OCH3 NHCOCH (CH3) 2 134.0 ° C 427 CF3 Cl F. OCH3 H. 97.0 ° C 428 CF3 Cl F. OCHFCO2Et NO2 84.5 - 85.5 ° C 429 CF3 Cl F. OH NO2 mp 89.0 - 90.0 ° C 430 CF3 Cl F. SCH2CO2Et NO2 90.0 ° C 431 CF3 Cl H. OCH2CO2Et NO2 88.0 ° C 432 CF3 Cl H. H. OCH3 bp 0.8 120.0 ° C 433 CF3 Cl H. H. CF3 bp 3.0 80.0-120.0 ° C 434 CF3 Cl H. F. H. 35.5 - 36.5 ° C

Table 3 lists various other compounds in Formula 1 that do not conform to Tables 1 and 2.

17, 108

Table 9

Relationship no

Name

Building

Analysis (%) calculate, find.

490

4-chloro-3- (6-fluoro-2,3-dihydro-1,4-benzoxathiinyl-7) -1-ethyl-5-trifluoromethyl-1H-plrazole M.p. 93.0

Cl

= T ^CF 3

N ^ ⁿ - ^ch 3

C. 44.27 44.34 H. 2.57 2.57 Cl 10.05 F. 21.55 N 7.94 7.98 S. 9.09

496

4-chloro-3- (6-fluoro2,3-iihydro-1,4-benzokaathiinyl-7) -1-methyl-5-trifluoromethyl-1H-plrazole S, S-dioxide

T. mp 200.0

497

4-chloro-3- (6-fluoro-2,3-dihydro-1,4-benzoyl-7) -s-oxide - 1-m-yl-5-trifluoromethyl-1H-pyrazole

M.p. 159.0

C 40.58 40.70 H 2.36 2.35 Cl 9.21 F 19.75 N 7.28 7.26 S 8.33 C 42.34 42.54 H 2.46 2.43 Cl 9.61 F 20.61 N 7.60 7.58 S 8.70

498

6- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolyl-3) -7-fluoro-4- (propyn-2-yl) 2H, 4H-1,4-benzothiazinone-3 M.p. 174.0

CH, -C = CH • CF, • ch /

499

6- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolly-3 -) - 7-fluoro-2H, 4H-1,4-benzothlazinone-3

M.p. 220.0

H -N

Cl

CF, ch ₃

44,

4-chloro-3- (3-chloromethylene-6-fluoro-2,3-dihydrobenzofuranyl-5) -1-methyl-5-trifluoromethyl-1H-pyrazole M.p. 121.0

CH-C1

C. 47.59 47.69 H. 2.50 2.51 Cl 8.78 F. 18.82 N 10.41 10.36 S. 7.94 C. 42.69 42.73 H. 2.20 2.49 Cl 9.69 F. 20.78 N 11.49 11.40 S. 8.77 C. 45.80 45.80 H. 2.20 2.36 Cl 19.31 F; 20.70 N 7.63 7.62

8- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazol-3) -7fluoro-2,4-dihydro-1H-Imldazo / ^_ 2,1-benzoxazine-c_7-1,4 Tt 118.0 - 120.0

C 48.08 H 2.96 Cl 9.46 F 20.28 N 14.95

48.54

3.10

441

170 158

Table 3 (continued)

442

4-chloro-3- (7-fluoro-2,3-dihydro-1,4-benzoxathiinyl-6) -1-methyl-5-trifluoromethyl-1H-pyrazole

M.p. 125.0

Cl CF,

C. 44.27 44.30 H. 2.57 2.52 Cl 10.05 F. 21.55 H. 7.94 7.93 S. 9.09

443 £ - [[6- (4-chloro-3-methyl-5-trifluoromethyl-1H-pyrazolyl-3) -7-fluoro-3-keto-4H-1,4-benzoxazinyl-4jr- (E-methylacetate ethyl

Tt sticky oil? ^H 3 and £ CH-CO-CH ₂ -CH ₃

[—CH,

C. 48.07 48.04 H. 3.59 3.32 Cl 7.88 F. 16.90 N 9.34 9.62

444

2- [5- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolyl _o- 3) -2,4-difluorophenyl] _ -4,5,6,7-tetrahydro-1H, 2H-isoindoledione- 1.3

M.p. 76.0 - 78.0

h ₃ cn. _n .

445

6- (4-chloro-1-methyl-5-trifluoromethyl-1H-plrazolyl-3) -4-ethyl-7-fluoro-2H, 4H-1,4-benzoxazinone-3

M.p. 95.0 - 97.0

446

6- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolyl-3) -4-ethyl-7-fluoro-4- (propyn-2-yl) -2H, 4H-1,4-benzoxazinone-3 M.p. 142.0 - 143.0

O / ^CH 2 / _ // \\

Cl

= NO- ^CF 3 V- ^ch 3

-CH

C. 51.19 52.29 H. 2.94 3.30 Cl 7.95 F. 21.31 N 9.43 9.14 C. 47.70 47.51 H. 3.20 3.22 Cl 9.39 F. 20.12 N 11.12 C. 49.56 49.58 H. 2.60 2.62 Cl 9.14 F. 19.60 N 10.84 10.85

447

6- (4-chloro-1-methyl-5-trifluoromethyl-2H-para-irazolyl-3) -4-ethyl-7-fluoro-2,3-dihydro-3-keto-4-cyanomethyl-4H-1 , 4-benzoxazine Tt 102.0 - 103.0

C 46.35 46.03 H 2.33 2.34

Cl 9.12 F 19.55 N 14.41

448

6- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolyl-3) -4-ethyl-7-fluoro-2,3-dihydro-3-keto-4- (2-methylamino-2-ketoethyl ) -4H-1,4-benzoxazine

M.p. 223.0 - 225.0

C.

H.

Cl

F.

N

45.67

3.11

8.43

18.06

13.32

45.75

3.10

449

O, - [ ^- 6- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolyl-3) -7-fluoro-2,3-dihydro-3-keto-4H-1,4-benzoxazinyl 1,1-dimethylethyl acetate

M.p. 161.0 - 162.0

C 49.20 H 3.91 Cl 7.04 F 16.39 N 9.06

49.45

4.06

17, 108

Table 9 (continued)

40, α - / "1-methylethyl 6- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolyl-3) -7-fluoro-3-keto-4H-1,4-benzoxazinyl-4_7acetate

M.p. 176.0 - 177.0

CH, nui ^{3 [beta]} CH ₂ -C-O-CH-CH ₃

Cl CF,

_N / NCH,

4 C. 48.07 48.25 H. 3.59 3.70 Cl 7.88 F. 16.90 N 9.34 9.30

401 d / - / 6- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolyl-3) -7-fluoro-2,3-dihydro-3-keto-3-keto-4H-1 , 4-benzoxazinyl-4- ethyl acetate Mp 131.0 - 133.0

C 46.86 47.00

H 3.24 3.24

Cl 8.14 F 17.44 N 9.64

402

0, - ["6- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolyl-3) -7-fluoro-2,3-dihydro-3-keto-4H-1,4-benzosazinyl-4 ^ acetamide

M.p. 215.0 - 217.0

C. 44.30 44.34 CF, H. 2.73 2.73 Cl 8.72 N-CH, F. 18.69 N 13.78

Acid and 409 ^_ ^ 6- (4-chloro-1-methyl-5-trifluoromethyl-1 H-3-pirazolllo) -7-fluoro-2,3-dihydro-3-oxo-2H-1,4-benzoxazinyl-acetic acid 4 R Mp 194.0 - 196.0

C.

H.

Cl

F.

N

44.19 44.13 2.47 2.33 8.70

18.64

10.31

404

6- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolyl-3) 7- fluoroΓO-4 - ['tetΓahydro-2H-pyranyl-2) methyl ^ -2H, 4H-1,4-benzoxazinone- 3

M.p. 133.0 - 135.0

CH.

6- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolium-3) -7-fluorQ-4- [ ^- (1 (-dlokaolanyl-2) methyl ^ -2H, 4H-1,4-bensoxazinone -3

M.p. 150.5 - 151.5

C 50.96 51.23 H 4.05 4.16 Cl 7.92 F 16.97 N 9.38

Cl Cl - CH,

C. 46.86 46.81 H. 3.24 3.24 Cl 8.14 F. 17.44 N 9.64 9.56

400

170 158

Table 3 (continued)

456

6- (4-chloro-1-methyl-5-tri? Uoromethyl-1H-pyrazolyl-3) -7-fluoro-4- (prop-2-enyl) -2H, -4H-1,4-benzoxazinone-3 M.p. 84.0 - 86.0

N — CH,

C 49.31 H 3.10 Cl 9.10 F 19.50 N 10.78

49.27

3.08

457

6- (4-chloro-1-methyl-5-trifluoro-1H-pyrazolyl-3) —4- [ ^_ 2- (1,3-dioxanyl-2) ethyl] N - 7-fluoro-2H, 4H- 1,4-benzocazinone-3

M.p. 125.5 - 127.5

Cl CF,

-CH,

C 49.20 H 3.91 Cl 7.64 F 16.39 N 9.06

49.44

3.97

8.80

458

6- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolyl-3) -7-i'luoro-4- (2-methoxyethyl) -2H, 4H-1,4-benzoxazinone-3

Tt 91.5 - 92.5 (ch ₂ ) ₂ —o-ch ₃

C 47.13 H 3.46 Cl 8.69 F 18.64 N 10.31

47.27

3.51

459

6- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolyl-3) -7-fluoro-4 - ["(p-iridinyl-2) methyl ^ -2Η, 4H-1,4-benzocazinone-3

M.p. 137.0 - 139.0

C 51.77 H 2.97 Cl 8.04 F 17.24 N 12.71

51.50

2.99

12.57

460

6- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolyl-3) -7-fluoro-4-methoxymethyl-2H, 4H-1,4-benzoxazinone-3

Tt 156.5 - 157.5 ch ₂ -o-ch ₃

Cl CF, (kb

C 45.76 45.93 H 3.07 3.21

Cl 9.00 F 19.30 N 10.67

461

6- (4-chloro-1-methyl-5-trifluoromethyl-1H-plrazolyl-3) -7-fluoro-4-netyl-; 2β1,4H-1,4-benzoxazinone-3

M.p. 140.5 - 141.5

CH, r N Cl CF

C. 46.23 46.24 H. 2.77 2.71 Cl 9.75 F. 20.90 N 11.55 11.68

6- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolly-3) -2H, 4H-1,4-benzoxazinone-3 Tt 216.0 = q — C ^F 3 _V n-ch ₃

C. 47.08 47.04 H. 2.74 2.75 Cl 10.69 F. 17.18 N 12.67 12.66

462

170 158

Table 3 (continued)

463

6- (4-chloro-1-methyl-5-trifluoromethyl-1H-plrazolyl-3) -7-fluoro-2H, 4H-1,4-benzoxazinone-3

M.p. 207.0

464

6- (4-chloro-1-methyl-5-trifluoromethyl-1H-plrazolyl-3) -7-fluoro-2-methoxy-4 (prop-2-ynyl) -2H, 4H-1,4-benzokaaaynone- 3

M.p. 101.0 - 103.0

_n / n_ οη ₅

C. 44.65 44.66 H. 2.31 2.31 Cl 1D, 14 F. 21.73 N 12.02 11.97 C. 48.88 48.95 H. 2.90 3.00 Cl 0.49 F. 10.19

N 10.06

465

6- (4-chloro-1-methyl-5-trifluoromethyl-1H-plrazol-3) -2,7-difluoro-4- (prop-2-ynyl) -2H, 4H-1,4-benzoxazinone-3 M.p. 114.0 - 116.0

CH ₂ —C »CH kT

CH,

Cl

CF,

C 47.37 47.55 H 2.24 2.45

Cl 8.74 F 23.42 N 10.36

466

0 / - / “6- (4-chloro-1-methyl-5-trie;) fluoromethyl-1H-pyrazolyl-3) -2,7-difluoro-3keto-4H-1,4-benzoxazinyl-4_7-acetate ethyl

M.p. 114.5 - 116.0

CH "- <SO-CH, -CH, ι 2 z and μ _ _Z C1

Λ & ιί ^{F 0} F | CF, CH,

C 45.00 45.00

H 2.89 2.81

Cl 7.81 F 20.94 N 9.26

467

6- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolyl-3) -2,7-difluoro-2H, 4H-1,4-benzoxazinone-3

M.p. 186.5 - 187.5

C 42.47 42.61 H 1.92 2.13

Cl 9.64 F 25.84 N 11.43

468

6- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolyl-3) -7-fluoro-2-methyl-4 (prop-2-yiyl) -2H, 4H-1,4-benzoxazinone-3

Y * t. 150.0 - 151.0

C 50.82 50.76

H 3.01 3.02

Cl 8.82 F 18.92 N 10.46

6- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolyl-3) -7-fluoro-2-methyl-2H, 4H-1,4-benzoxazinone-3

M.p. 187.0 - 189.0

C 46.23 46.43 H 2.77 2.80

Cl 9.75 F 20.90 N 11.55

469

170 158

Table 3 (continued)

1 2 3 4 470 2- / ~ 4- (4-chloro-1-methyl- Cl with ^CF 3 C. 43.70 43.81 -5-trifluoromethyl-1H-pi- J— ~ i H. 3.21 3.22 razolyl-3) -5-fluoro-4- ° 2 ^N V ^ ^X CH, Cl 8.06 -nitrophenoxy 7-propionate ° Az AND 3 F. 17.28 ethyl CH ₃ -CH ₂ -0-C-fH-O F. N 9.56 M.p. 136.0 - 138.0 ^CH 3 471 6- (4-chloro-1-methyl-5-tn5j- CH ₂ -C = CH C. 52.00 52.00 fluoroaethyl-1H-pyrazolyl- AND Cl H. 3.39 3.38 -3) -2-ethyl-7-fluoro-4-. 0 N. Cl 8.53 - (prop-2-ynyl) -2H, 4H-1.4- AAA li! l F. 18.28 benzocazinone-3 M.p. 126.5 - 127.5 CH ₃ -CH ₂ ~ \ ^CH 3 cf ₃ N 10.11 472 6- (4-chloro-1-methyl-5-tri- H. Cl C. 47.70 47.75 fluoromethyl-1H-plrazolyl- ⁰ / H. 3.20 3.18 and Ii ^S I ¹¹ 1 Μ, -3) -2-ethyl-7-fluoro-2H, 4H- 2F ₃ Cl 9.39 -1,4-benzoxazinone-3 CH ₃ -CH ₂ ^u f N F. 20.12 M.p. 191.0 - 192.0 CHj N 11.12 473 6- (4-chloro-1-methyl-5-trio J- Π C. 56.97 56.77 fluoromethyl-IH-plrazolyl- J ch ₂ -c = ch H. 3.04 3.07 -3) -7-fluoro-2-phenyl-4- L r Cl CF Cl 7.64 - (prop-2-ynyl) -2H, 4H-1.4- / 3 F. 16.39 9.06 -benzoxazinone-3 ULA 3 ^ - ^CH 3 N M.p. 146.0 - 147.0 474 ^ ”6- (4-chloro-1-methyl-5- CH, C. 45.03 44.99 trifluoromethyl-1H-pyrazo- II ęH you CH- CF_ H. 2.36 2.27 IIIo-3) -5-fluoro-1- (prop-2- WITH Cl 8.31 enyl) -2-tri J fluoromethyl-7- and —F F. 31.17 -1H-benzimidazole OF -C ^ CH, N 13.13 13.18 M.p. 96.0 ³ 475 7- (4-chloro-1-methyl-5-tri- £ ° ^ H Cl Λ C. 45.04 45.10 fluoromethyl-1H-plrazol-3) - H. 2.04 2.04 -6-fluoro-1H-clnoxalinone-2 lc l1 1 and Cl 10.23 M.p. 250.0 ^ν - <η ₃ F. 21.92 N 16.16 16.16 476 7- (4-chloro-1-methyl-5-tri- Cl = t-cf ₃ C. 44.65 44.61 fluoromethyl-1H-pyrazolyl- H. 2.31 2.27 -3) -6-fluoro-2H, 4H-1,4-benzo ί T Tl with «- CH ₃ Cl 10.14 xaszynon-3 ° ^F F. 21.73 M.p. 242.0 N 12.02 11.99 477 7- (4-chloro-1-methyl-5-tri- C. 42.69 42.73 fluoromethyl-1H-pyrazolyl-3) -6-fluoro-2H, 4H-1,4-ben- - | 3 H. Cl 2.20 9.69 2.23 zothiazinon-3 ηΛ ^ ν ' / N- CH ^ F. 20.78 11.40 F. N 11.49 M.p. 225.0 S. 8.77 8.79

170 158

Table 3 (continued)

478

7- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolyl-3) -6-fluoro-3,4-dlhydro-1H-quinoxalinone-2

M.p. 240.0

C. 44.78 44.76 H. 2.60 2.59 Cl 10.17 F. 21.80 N 16.07 16.06

479

7- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolyl-3) -6-fluoro-4- (prop-2-ynyl) -2H, · -4H-1,4-benzoxazinone-3 M.p. 181.0

Cl

CF,

CH,

CH ₂ -C = CH

C. 49.56 49.48 H. 2.60 2.56 Cl 9.14 F. 19.60 N 10.84 10.95

480

5H (4-chloro-1H-methylH5H-trifluoromethyl-1H-pyrazolyl-3) - “- fluoro-1- (propenyl-2) -2-trifluoromethyl-1H-benzimidazole

Mp n _D 1.5186 (25 ° C)

Cl CF,

/ N — CH,

CH, I ² CH CH,

C 45.03 45.08 H 2.36 2.25

Cl 8.31 F 31.17 N 13.13 13.20

481

4-chloroH3H / "3-chloro-methylene) -5-fluoro-2,3-dlhydrobenzofuranyl-6-7-1-methyl-5-tri-fluoromethylH (Z) -1HHplH razole

M.p. 140.5 - 142.5

C. 45.80 45.64 H. 2.20 2.22 Cl 19.31 F. 20.70 N 7.63 7.60

482

4-chloro-2 - / "3-chloro methylethyl) -5-fluoro-2,3-dPhydrobenzofuranyl-6-7-1-methyl-5-tri-fluoromethyl- (E) -1H-pyrazole M.p. 132.0 - 135.0

483 phenol 2,4,6-trichloro-3- (4-chlorOH1Hmethyl-5-trifluoromethylH1H-pPrazollloH3) hemihydrate

Mp 122.5 0.5 H ₂ 0

484 Methyl <f- / ^- 4-chloro-5- (4-chloro-2-fluoro-5-methoxyphenyl) -3-trifluoromethyl-1H-pyrazolyl-7acetate

Mp transparent glass (mp ^^ 130-150 ° C) ^m

CH ₂ -CO-CH ₃

C. 45.60 45.71 H. 2.20 2.23 Cl 19.31 F. 20.70 N 7.63 7.63 C. 34.77 33.87 H. 1.33 1.46 Cl 37.32 F. 15.00 N 7.37 7.14 C. 41.92 42.01 H. 2.51 2.50 Cl 17.68 F. 18.95 N 6.98 6.98

* Flask-to-flask distillation

170 158

Table 3 (continued)

485

3,3 '- / "divithiobisC1-chloro-fluoro-1,3-enylene) -7-bis (4-chloro-1-methyl-5-trifluoromethyl) -1H-plrazole 169.0

CF.

CH

Cl _Z SF

CF,

Cl ¹ Cl—

AND

CH,

486

3- / ^- 2-chloro-5- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazol-3) -4-fluorophenoxy-7-dihydro-5H-furanone-2

M.p. nD 1.5352 (25 ° C)

487

2-chloro-5- (4-chloro-1-methyl-5-TR5; Jfluorometylo · plrazolllo-1 H-3) -4-fluorofenylo_7 -e- ^[_ 5- (4-chloro-1-methyl-IH- 5trójfluorometylo pyrazolyl-3) -4-fluorophenyl-7-propionitrile

Mp 130.0 - 134.0

c 38.39 38.61 H. 1.46 1.55 Cl 20.60 F. 22.08 N 8.14 8.06 S. 9.32 9.24 C. 43.61 43.58 H. 2.44 2.48 Cl 17.16 F. 18.39 N 6.78 6.68 C. 44.34 44.41 H. 1.93 2.01 Cl 20.94 F. 22.44 N 10.34 10.36

488

2- ^[_ 2-chloro-5- (4-chloro-1-methyl-5-trifluoromethyl-1H-3-pyrazolyl) -4-fluorofenylo_7-4,4-dwumetylooksazolidyna

M.p. 106.0

_n / N— ch ₃

489

4-chloro-3- (4-chloro-2-fluoro-5-methoxyphenyl) -1- (1-methylethyl) -5-trifluororethyl-1H-pyrazole M.p. nD 1.5192 (24 ° C)

N ^xN ^ CH — CH,

490

4-chloro-3- ^ .4-chloro-2-fluoro-5 - / - 4- (methoxymethyl) - 1,3-dioxolanyl-2-7phenyl} -1-methyl-5-trifluoromethyl-1H-pyrazole

M.p. nD 1.5218 (25 ° C)

H, COH, C-HC, ^ 3 2 _Z >)

Cl CF,

491

N-4- / X4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolyl-3) -5-fluoro-2-nitrophenyl-7-2,2,2-trifluoro-N- (prop-2-enyl) acetamide

M.p. nD 1.5143 (25 ° C)

H ₂ C:

and '0-CH

Cl

_n / NC ^H 3

Cl CF, ^CF 3 ^C -? ^ J

CH

CH,

CH,

C. 46.85 46.71 H. 3.19 3.24 Cl 17.29 F. 18.53 N 10.24 10.23 C. 45.30 45.19 H. 3.26 3.27 Cl 19.10 F. 20.48 N 7.55 7.49 C. 44.77 44.75 H. 3.29 3.32 Cl 16.52 F. 17.71 N 6.53 6.56

C 40.48 H 2.12 Cl 7.47 F 28.02 N 11.80

40-71

2.13, 70

^ 2

170 158

Table 3 (continued)

492

4 _- / ^- (4-chloro-1-methyl-5 _- trifluoromethyl-1H-pyrazolyl-3) -5-fluoro-2-nitro-N- (prop-2-enyl) aniline

M.p. 99.0

Cl CF,

H ₂ C = CH-H ₂ C-HN y N -CH ₃

C 44.40 44.53

H 2.93 2.97

Cl 9.36 F 20.07 N 14.79 14.76

493

Methyl N- / 4- (4-chloro-1-matyl-5 _- trifluoromatyio-1H-pyrazolyl-3) -5-fluoro-2-nitrophenyl-7-glycinate Tt 176.0

Cl ° ² Χί ch; -oc-ch, -n ^x

CF,

CH,

C 40.94 40.96 H 2.70 2.75

Cl 8.63 F 18.50 N 13.64 13.74

494 acetate / Ethyl 4- (4-chloro-1-methyl-5-trifluoromatyl-1H-pyrazolyl-3) -5-fluoro-2-nitrophenoxy-7butyrate M.p. 117.0-118.0

CH ₃ -CH ₂ -Gt ^ -CH-Of <O

HE

CH _3-? H ₂

C 45.00 44.96 H 3.55 3.48

Cl 7.81 F 16.75 N 9.26

495 / 4- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazolyl-3) -5-fluoro-2-nitrophanoxy-7matoksymatyiu Tt 113.5-114.5 o ₂ n

CH, -O-C-CH-O ^{3 10} and

CH,

Cl

F.

CH,

C 40.79 40.93 H 2.74 2.73

Cl 8.03 F 17.21 N 9.51

496 acetate / -4- (4-0) 110 [beta] -1-1 [beta] -thyl-5-triuoromatyio-1H-pyrazolyl-3) -5-fluoro-2-nitrophanoxy-7-phanyiomatyi, M.p. 160.0-161.0

C 49.25 49.16 H 2.89 2.88

Cl 7.27 F 15.58 N 8.61

497

4-chloro-3- ( ^- 2-fluoro-4'-methylthioethoxy) - nitrophenyl-7-1-methyl-5-tΓfluoomatyl-1H-pyrazole

Tt 69.0 ch ₃ -s-ch ₂ -ch _2- i

C.

H.

Cl

F.

N

S.

4064

2.92

8.57

18.37

10.16

7.75

40.45

2.87

10.16

- / ^- 4- (4-chloro-1-matylo-5-tróJfluoromatylo-3-1Hpirazolilo) -5-fluoro-2-nitrophenoxy] ^r-butyl acetate

M.p. 65.0

C. 45.00 44.97 / ^CF 3 H. 3.55 3.56 Cl 7.81 ^N x F. 16.75 CHj N 9.26 9.29

498 and?

170 158

Table 3 (continued)

1 2 3 4 499 4-chloro-3- (2,4-dimethoxy-5- OoN Cl C. 42.70 42.77 nitrophanyl) -1-Inatyl-5-tri- 2 \ H. 3.03 3.04 CH 2 -O-e _ | CF ₃ fluorornethyl-1H-pyrazole , x ^N - ^CH 3 Cl 9.69 M.p. 158.0 0-CH F. 15.59 3 N 11.49 11.50 500 1-bromo-N - / “2-chloro-5- (4- F. Cl C. 37.92 38.41 chloro-1-methyl-5-trifluo- H. 2.12 2.26 romethyl-1H-pyrazolyl-3) - Cl_ A- ^CF 3 Br 16.82 -4-fluorophenylcyclopropane- / Ν— N Cl 14.93 carbonamide M.p. 80.0-94.0 [> 7- ^ Br 0 1 ch ₃ F. N 16.00 8.85 8.80 501 4-chloro-1-chloromethyl-3- Cl C 39.91 40.03 - (2,4-difluorophenyl) -5- cf ₃ H. 1.52 1.50 trifluoromethyl-1H-pyrazole UJ- - CH ₂ - Cl Cl 21.42 M.p. nD 1.5096 (25 ° C) N F. 28.69 F. N 8.46 8.49

TESTS OF THE PRE-EASTIC CICACIDAL ACTION

As already mentioned, the compounds according to the present invention have been found to be surprisingly effective as herbicides.

The pre-emergence herbicidal activity trials were conducted as follows:

The topsoil was placed in the aluminum bowl and compacted so that the soil surface was 0.95 - 1.27 cm below the top of the bowl. A certain number of seeds of individual species of annual monocotyledons and dicotyledons and / or vegetative shoots of perennials were placed on the soil surface. A known amount of the active ingredient is dissolved or dispersed in an organic solvent, e.g. acetone, or water as a carrier and then applied directly to the seed substrate, which is covered with untreated topsoil until the pan is full. After treatment, the bowls were placed on a bench in the greenhouse, where the soil was irrigated from below as needed to ensure adequate moisture for germination and growth.

Within about 10-14 days (usually 11 days) after seeding and treatment, the bowls were observed and the results (percent inhibition) recorded.

Tables 4 and 4A below summarize the results of trials on the pre-emergence herbicidal activity of compounds of this invention against weeds. The herbicidal activity indices given in these tables relate to the percent inhibition of a particular plant species.

Plant species commonly considered as weeds used in one test series, the results of which are given in the tables, were identified by letter markings above the columns according to the following legend:

Yens - edible tobacco Could - wolf Anbg - annual panicle Cobu - turnip Sejg - Aleppo sorghum Vele - fibrous velvet Good - roof slope Inmu - sieve cabbage Bygr - one-sided weed Wibw - wild buckwheat

In the tables below, when present, the symbol C indicates 100% control and the symbol N indicates that plants have been planted but for one reason or another no data were obtained.

170 158

Table 4

PRE-EAST TESTS% PLANT INHIBITATION

Relationship no Dose kg / ha Y e n s AND n b g S. e j g D 0 b r B y g Γ M. about g 1 c 0 b at V e e AND n m at IN and b in 62 11.21 0 0 thirty 0 twenty thirty 0 60 twenty twenty 63 11.21 0 C. C. c C. C. 60 C. C. C. 64 11.21 10 90 80 90 80 80 10 C. c C. 65 ) 11.21 0 70 70 0 thirty twenty 0 90 N 80 66 11.21 0 50 90 60 10 C. twenty 90 50 90 67 11.21 0 40 40 40 0 90 0 80 50 90 68 * 11.21 thirty 0 10 0 10 thirty 0 40 0 N 69 11.21 0 0 0 0 0 thirty 0 50 0 0 70 11.21 0 40 80 twenty 40 80 twenty 90 80 80 71 11.21 0 90 40 10 0 thirty 0 60 thirty 70 72 11.21 0 twenty 60 twenty 60 40 twenty 90 90 90 73 11.21 0 0 0 0 0 0 0 50 twenty 0 74 1.12 0 10 60 twenty twenty 50 0 90 90 C. 75 11.21 twenty 0 50 twenty twenty 90 10 80 thirty 50 76 1.12 0 10 0 10 0 40 twenty 50 60 C. 77 11.21 0 80 40 10 thirty 0 0 thirty thirty twenty 78 11.21 0 0 0 0 0 0 0 0 0 0 79 11.21 twenty 90 80 80 80 C. thirty C. C. C. 80 11.21 0 90 80 70 70 60 60 C. 80 90 81 ) 11.21 0 60 90 80 60 thirty twenty 90 twenty C. 82 11.21 thirty 60 C. C. C. C. 40 C. 80 C. 83 11.21 twenty 40 C. 90 60 thirty 40 90 60 90 84 11.21 thirty C. C. C. C. 90 80 C. C. C. 85 11.21 0 c C. C. C. C. 40 C. C. C. 86 11.21 0 0 0 0 0 twenty 10 90 thirty C. 87 11.21 10 10 thirty twenty 40 70 10 90 70 90 88 11.21 10 twenty thirty 10 10 10 twenty 80 twenty C. 90 11.21 0 10 50 10 10 10 0 twenty 10 thirty 91 1.12 0 0 0 0 0 90 twenty C. 90 70 92 1.12 0 0 0 0 0 80 twenty 90 twenty 80 94 1.12 twenty c c c c 90 60 C. C. C. 95 1.12 twenty thirty 50 twenty 50 40 twenty 90 80 c 96 1.12 twenty C. 90 c 80 C. 60 C. C. c 97 1.12 twenty 80 50 80 50 40 90 C. 90 c 99 11.21 thirty 80 90 c 90 90 80 C. C. c 100 1.12 0 90 90 c 70 80 twenty C. c c 101 1.12 0 70 80 80 40 80 thirty C. c 90 102 1.12 twenty 60 90 80 80 C. thirty C. c C. 103 1.12 0 twenty 40 70 twenty 60 0 50 40 c 104 1.12 0 twenty 80 80 10 80 twenty 90 80 70 105 1.12 twenty 0 60 40 70 80 10 90 80 80 106 1.12 0 thirty 80 80 80 60 twenty 80 90 C. 107 1.12 0 twenty 40 thirty 80 C. twenty 90 80 80 108 11.21 twenty 50 90 C. C. 90 80 C. C. C. 109 1.12 0 twenty 80 twenty 90 70 thirty 90 90 c 110 1.12 0 0 0 0 twenty 70 50 C. 80 70 111 11.21 60 80 80 70 40 C. 90 C. C. c

170 158

Table 4 (continued)

Relationship no Dose kg / ha Y e n s AND n b g S. e j g D 0 b r B y g r M. 0 g 1 c 0 b at V e e AND n m at IN and b in 112 11.21 80 C. 90 twenty C. C. 40 c c 90 113 11.21 0 10 thirty 0 80 thirty 0 80 80 40 114 11.21 90 c 90 60 C. C. 70 C. C. C. 115 1.12 0 40 70 70 80 80 twenty c C. 90 116 1.12 0 90 90 80 90 90 50 c 90 C. 117 1.12 0 C. 70 90 C. 90 70 c C. C. 118 1.12 0 C. 90 C. 90 C. 80 90 C. C. 119 11.21 70 10 80 80 C. C. C. C. C. C. 120 1.12 10 70 80 70 80 80 thirty C. 90 C. 121 11.21 70 c 80 70 C. C. 60 C. C. c 122 1.12 0 twenty 40 twenty 80 80 40 C. C. 70 123 1.12 thirty 0 40 70 thirty C. 50 C. 80 90 124 11.21 twenty c C. C. C. C. C. c C. C. 125 1.12 0 c C. 90 C. 90 thirty c C. C. 126 1.12 0 c C. C. C. C. 50 c C. C. 127 1.12 0 0 twenty 0 thirty 70 twenty c 90 C. 128 1.12 0 0 thirty 0 0 80 70 c 70 c 129 1.12 0 0 60 40 twenty C. 90 c 90 c 130 1.12 twenty 0 70 thirty thirty C. 90 c C. 90 131 1.12 twenty 0 70 thirty 40 C. 80 c 90 C. 132 11.21 thirty 60 70 80 90 C. 70 c 90 c 133 1.12 twenty twenty 80 0 80 70 40 c C. 70 134 1.12 0 50 40 70 10 twenty thirty 70 60 90 135 1.12 0 c C. C. C. 90 90 c C. C. 137 1.12 twenty 70 50 80 80 C. C. c C. 90 138 1.12 twenty 40 thirty 90 50 c C. c C. C. 142 1.12 0 10 twenty 70 40 c 60 c 90 50 143 1.12 10 10 40 twenty twenty 90 80 c C. C. 144 1.12 10 10 twenty 10 thirty 80 C. c 80 70 145 1.12 60 0 thirty twenty thirty c 70 c C. 70 146 1.12 twenty C. C. C. C. c 90 c c C. 147 1.12 thirty 0 40 10 40 80 twenty c 80 70 148 1.12 0 70 50 80 90 c 90 c c C. 149 1.12 twenty 0 twenty 0 twenty 90 thirty c 70 60 150 1.12 0 70 90 80 60 40 60 90 80 C. 151 1.12 0 c C. C. 90 70 90 90 90 c 152 1.12 0 70 twenty 70 60 90 twenty C. 90 90 153 1.12 thirty c C. 50 C. 90 10 c C. 90 154 1.12 thirty 10 c 10 90 C. C. c C. C. 155 1.12 0 90 90 thirty 80 90 70 c C. c 156 1.12 twenty twenty C. twenty 90 C. 80 c C. 90 157 1.12 50 C. 90 80 C. C. 80 c C. C. 158 1.12 10 thirty 80 70 80 C. 50 c C. 90 159 (11.21 C. 90 C. 90 C. C. C. c C. C. 160 1.12 0 twenty 80 50 thirty thirty 40 40 twenty 90 161 11.21 60 40 90 80 C. C. C. c C. C. 162 1.12 twenty 80 C. 90 70 80 70 90 80 C. 163 11.21 50 C. C. C. C. C. C. C. C. C.

170 158

Table 4 (continued)

Relationship no Dose kg / ha Y e n s AND n b g S. e J. g D 0 b r B y g r M. 0 g 1 c 0 b at V e 1 e AND n no at in and b in 164 + 11.21 10 70 80 c twenty c 40 c c c 165 11.21 40 C. C. c C. c C. c c c 166 1.12 thirty 70 80 80 40 50 50 90 90 c 167 0 11.21 0 50 80 c 70 50 40 90 C. c 168 11.21 0 0 0 0 0 thirty thirty 80 thirty c 169 1.12 0 twenty 80 c 50 40 thirty 70 80 90 170 β 11.21 0 thirty 90 c 80 C. 40 C. C. C. 171 11.21 twenty 40 80 50 90 60 40 c 70 80 172 1.12 twenty thirty 0 0 twenty 0 0 thirty 80 80 173 1.12 twenty C. 60 90 70 60 thirty 80 80 80 174 1.12 0 thirty 80 60 50 70 thirty 90 90 90 175 11.21 0 80 twenty 40 70 80 10 80 10 90 176 11.21 twenty C. C. C. 90 C. 80 C. C. C. 177 11.21 twenty C. 90 90 C. C. 90 C. C. C. 179 1.12 0 70 90 90 70 80 80 90 C. C. 180 1.12 0 0 0 40 thirty 90 80 C. 90 c 181 11.21 thirty c 80 C. 90 C. C. c C. c 182 11.21 90 c C. c C. c c c C. c 183 + 1.12 0 50 80 90 twenty 70 70 90 90 c 184 11.21 0 twenty 0 twenty thirty C. 60 C. C. c 185 11.21 twenty C. 80 c C. C. c C. c c 186 1.12 0 40 60 c twenty 80 70 C. 80 c 187 + 1.12 0 thirty 70 50 twenty 40 40 80 c c 188 11.21 twenty 60 80 70 80 C. 80 C. 80 c 189 1.12 0 0 0 10 0 50 thirty 80 80 80 190 1.12 0 twenty twenty 10 10 C. thirty C. 90 c 191 11.21 0 0 twenty thirty 70 70 40 C. 80 c 192 11.21 0 C. 90 c 90 90 90 c C. c 193 11.21 50 C. 50 60 40 C. C. c c c 194 1.12 twenty 0 thirty twenty 0 80 thirty 90 60 80 195 1.12 0 0 twenty twenty 50 C. 90 c 80 thirty 1.12 0 N 0 N 0 0 0 N N N 196 1.12 50 0 0 twenty 60 80 50 C. C. 70 197 11.21 0 0 thirty thirty 80 60 80 c c C. 199 1.12 0 0 twenty twenty twenty 70 40 c 80 60 200 1.12 0 0 0 0 thirty C. 80 ' c 90 60 201 1.12 0 0 twenty 0 thirty 70 70 c 80 thirty 202 1.12 0 0 twenty twenty twenty 60 50 60 70 80 204 1.12 0 0 0 0 0 0 0 0 0 0 206 11.21 0 0 twenty 0 10 twenty twenty 0 twenty 40 207 0 1.12 0 0 0 0 0 0 0 0 0 0 208 1.12 thirty 50 80 C. 60 60 80 80 70 c 209 1.12 0 0 0 0 twenty twenty 0 twenty 0 0 210 1.12 twenty twenty 80 70 40 80 thirty 80 80 c 211 1.12 10 80 C. c C. C. 80 C. C. c 212 1.12 twenty thirty 50 80 70 80 70 C. c 90 213 1.12 twenty 90 50 90 C. 60 50 C. c 80 214 1.12 thirty 80 70 70 90 80 50 c c C.

170 158

Table 4 (continued)

Relationship no Dose kg / ha Y e n s AND n b g S. e j g D 0 b r B y g r M. 0 g 1 c 0 b at V e e AND n m at IN and b in 215 1.12 0 60 40 twenty 80 80 thirty C. C. 90 216 1.12 thirty C. C. C. 90 C. 80 C. C. C. 217 1.12 twenty c C. c C. c 80 c C. c 218 1.12 0 50 40 70 80 c 70 c C. c 219 1.12 thirty 60 50 60 70 90 90 c C. 70 220 1.12 50 70 60 70 70 80 90 90 90 60 221 1.12 thirty thirty 50 50 twenty 80 80 80 C. thirty 222 1.12 40 80 thirty 60 80 70 80 c C. C. 223 1.12 40 60 50 60 60 80 90 c 90 40 224 1.12 0 40 70 80 70 60 C. c 50 C. 1.12 0 N N N 0 0 0 N N N 225 1.12 thirty 90 60 80 60 50 80 c C. 60 226 1.12 thirty twenty 40 50 50 80 90 90 C. 50 227 1.12 thirty 50 50 40 70 80 90 C. c 60 228 1.12 twenty 60 50 80 50 80 C. 90 c 60 229 1.12 60 C. C. C. 90 C. 90 C. c C. 230 1.12 twenty 60 80 60 90 90 60 C. c C. 231 1.12 0 twenty 40 50 thirty 0 40 40 twenty twenty 232 1.12 40 C. 80 70 90 C. thirty C. C. C. 233 1.12 thirty 80 70 50 90 90 thirty c c c 234 1.12 twenty 40 50 thirty 40 70 thirty c c 90 235 1.12 thirty 90 70 thirty C. C. thirty c c C. 236 1.12 thirty 90 90 C. 50 C. C. c c C. 237 1.12 60 90 90 80 C. C. 40 c c C. 238 1.12 50 10 twenty twenty twenty 70 C. c c 80 1.12 40 10 10 0 0 80 c c c 70 239 1.12 thirty thirty 50 50 thirty 80 90 c c thirty 240 1.12 0 80 90 C. 80 C. 90 c c C. 241 1.12 twenty C. 60 90 60 50 50 c 70 80 242 1.12 thirty 90 thirty 90 40 80 60 c c 80 243 1.12 twenty 80 thirty 60 thirty 60 70 c 90 60 244 1.12 thirty 0 10 50 0 0 0 twenty 0 10 245 1.12 0 60 60 thirty 80 80 thirty 90 C. C. 246 1.12 0 90 80 C. 70 80 90 90 c C. 247 1.12 thirty twenty 50 twenty 50 C. 70 C. 90 80 248 1.12 thirty thirty twenty 0 40 90 50 C. 90 90 249 1.12 60 C. 90 80 C. C. 50 C. c C. 250 1.12 0 thirty 60 90 80 90 10 C. 70 c 253 1.12 twenty thirty 60 40 80 90 twenty 90 90 90 254 1.12 0 80 70 80 70 twenty thirty C. 70 C. 255 1.12 0 0 thirty 40 0 90 60 90 90 80 256 1.12 0 60 60 40 80 80 40 C. C. C. 257 1.12 0 10 twenty twenty 0 70 thirty 90 80 80 258 1.12 0 twenty 40 10 twenty 80 C. 80 C. 70 259 1.12 0 0 0 0 0 60 N thirty twenty 0 260 1.12 0 twenty thirty C. twenty thirty thirty 40 50 80 261 11.21 thirty C. C. C. C. C. C. C. C. C. 262 112 40 C. c C. C. c 80 c C. c

170 158

Table 4 (continued)

Relationship no Dose kg / ha Y e n s AND n b g s e j g D 0 b r B y g r M. 0 g 1 c 0 b at V e e AND n m at in and b in 263 1.12 0 C. C. C. C. C. C. c c c 264 1.12 thirty 60 70 C. 80 c 70 c 90 0 265 1.12 0 90 80 90 twenty twenty twenty 70 60 c 266 1.12 thirty 70 50 C. 90 70 40 40 80 c 267 1.12 thirty 60 90 90 70 70 70 90 80 c 268 1.12 0 40 60 C. 60 70 60 90 80 c 269 1.12 twenty C. C. C. 90 90 60 C. C. c 270 1.12 thirty 70 70 C. 90 C. 60 C. c c 271 1.12 thirty 50 80 80 80 80 70 80 80 c 272 1.12 40 twenty 80 70 90 C. 70 C. c c 273 1.12 twenty 80 70 60 C. c 40 c c c 274 1.12 0 twenty 40 twenty 80 80 0 c c 60 275 1.12 twenty twenty 40 twenty 80 c 70 c c c 276 1.12 twenty C. C. C. C. c 80 c c c 277 1.12 twenty C. c C. c 90 50 c c c 278 1.12 twenty c 90 C. 90 C. 70 c c c 279 11.21 C. 90 C. C. 90 C. C. c c c 280 11.21 90 50 80 40 80 C. c c 90 c 281 1.12 0 0 0 0 0 40 80 70 twenty 50 282 1.12 40 twenty thirty twenty twenty 90 thirty c thirty 90 283 1.12 40 twenty twenty 0 0 C. C. c 70 70 286 1.12 0 0 twenty twenty 50 C. C. c 0 80 289 1.12 70 thirty 70 twenty twenty 90 50 c 40 90 290 1.12 80 thirty thirty twenty twenty C. C. c 40 90 291 1.12 thirty thirty 40 twenty twenty C. C. c 40 C. 292 1.12 40 twenty 40 twenty twenty C. 40 80 thirty 80 293 1.12 twenty 0 twenty 0 twenty C. 80 C. 0 70 294 + 1.12 0 0 twenty twenty twenty 70 80 70 0 90 295 1.12 0 40 60 50 50 60 thirty 70 60 C. 296 1.12 thirty 0 0 0 thirty 90 90 C. C. C. 297 1.12 0 twenty 40 60 80 twenty 10 90 70 90 298 1.12 50 thirty thirty twenty 80 C. 40 C. C. C. 299 1.12 0 0 twenty twenty 70 C. 80 C. c 70 300 1.12 twenty 0 0 0 0 C. 80 C. 40 50 301 11.21 0 0 0 90 twenty thirty 0 40 40 90 302 1.12 0 C. 90 C. C. C. 90 C. c C. 304 1.12 10 80 80 C. 80 c 90 c c C. 305 1.12 0 90 90 C. 90 70 thirty c 90 C. 306 1.12 0 60 40 C. 80 80 70 c c C. 307 0 1.12 thirty 80 80 C. 70 C. 90 90 90 C. 308 1.12 40 C. C. C. C. C. 80 C. C. C. 309 1.12 40 C. 90 C. c c 80 C. C. C. 310 1.12 twenty 90 70 twenty 80 c thirty C. C. C. 311 1.12 60 C. 90 90 C. c 60 c c C. 312 11.21 60 c C. C. c c C. c c C. 313 1.12 thirty c C. C. c c 90 c c C. 314 1.12 twenty 80 90 C. 90 c 80 c c C. 316 1.12 0 c 90 C. 90 90 50 c c C.

170 158

Table 4 (continued)

Relationship no Dose kg / ha Y e n s AND n b g s e j g D 0 b r B y g r M. about g 1 c 0 b at V e 1 e AND n m at IN and b in 317 1.12 10 90 70 60 60 90 c C. 80 c 318 11.21 70 C. 90 C. C. C. c C. C. c 319 1.12 twenty 80 40 70 thirty 90 50 c 80 c 320 1.12 0 60 40 40 thirty C. 90 c 80 c 321 1.12 twenty twenty thirty 80 60 60 twenty c 50 c 322 1.12 0 twenty thirty 80 thirty C. thirty c 60 c 323 1.12 0 60 70 90 70 80 twenty c 50 c 324 1.12 twenty 70 50 70 80 C. thirty 90 90 c 325 11.21 0 90 C. C. C. 90 90 C. C. c 326 11.21 twenty C. 90 c 90 C. 80 C. C. c 327 11.21 0 0 0 0 0 0 0 twenty 0 0 328 1.12 0 10 40 90 0 70 twenty C. 0 c 330 1.12 twenty 60 80 80 70 80 twenty c c c 331 1.12 0 thirty 40 70 twenty 70 50 80 70 80 332 1.12 0 60 80 70 60 80 0 80 70 90 333 1.12 0 70 90 C. 70 90 40 c c 90 334 1.12 0 60 70 80 80 40 40 70 80 c 335 1.12 0 0 0 0 0 C. C. c 90 80 336 1.12 0 thirty 60 80 40 90 60 80 80 90 337 1.12 10 0 thirty twenty 70 C. 70 c 80 80 338 1.12 twenty twenty twenty twenty 70 c 50 80 80 70 339 1.12 thirty 10 0 0 10 80 90 C. 90 90 340 1.12 twenty 80 70 40 80 c C. C. C. 90 341 0 1.12 twenty c 90 90 70 90 90 C. c C. 342 1.12 thirty c C. C. 90 c 80 C. c c 343 11.21 0 0 0 twenty 0 twenty 0 50 thirty 80 344 1.12 0 0 0 0 0 0 0 60 0 0 345 1.12 0 0 twenty twenty thirty twenty 0 70 50 70 346 11.21 thirty 0 0 0 0 80 thirty C. C. 60 347 11.21 0 80 70 70 80 80 thirty c 90 80 348 1.12 40 60 40 twenty 80 C. C. c C. 70 349 1.12 0 twenty 60 thirty 70 thirty twenty 80 70 80 352 11.21 twenty thirty 50 40 thirty 80 60 90 60 80 353 11.21 0 80 70 twenty 50 80 80 C. C. C. 354 1.12 0 twenty 70 thirty 60 twenty twenty 90 thirty c 355 11.21 0 0 thirty 0 twenty 0 thirty 80 thirty 90 356 11.21 thirty c C. 80 90 C. 40 C. C. C. 357 11.21 twenty thirty 80 40 70 80 twenty 60 90 70 358 11.21 70 60 50 thirty 80 C. 80 C. C. 70 359 1.12 twenty 0 twenty 0 40 40 thirty 90 90 C. 360 11.21 0 0 0 0 0 0 0 0 0 0 361 11.21 0 0 40 60 80 50 0 90 50 80 362 11.21 0 50 80 60 50 80 twenty 90 60 c 363 11.21 0 0 40 twenty 0 0 0 50 0 60 364 11.21 0 thirty 80 80 80 70 twenty C. 60 90 365 11.21 thirty 70 C. C. C. 90 thirty c 70 90 366 11.21 twenty C. c C. c 50 50 c 70 C. 367 11.21 0 0 0 0 0 0 0 0 0 0

170 158

Table 4 (continued)

Relationship no Dose kg / ha Y e n s AND n b g s e j S. D about b r B y g Γ M. about g 1 c 0 b at V e 1 e AND n m at IN b in 368 11.21 0 0 0 0 0 0 0 thirty 0 0 369 11.21 0 0 0 0 0 thirty 0 80 thirty 80 370 11.21 0 0 twenty 0 0 twenty 0 thirty thirty 80 371 11.21 0 0 0 0 0 0 0 0 0 0 372 11.21 0 0 0 0 0 0 0 40 10 0 373 11.21 0 0 0 0 0 0 0 0 0 twenty 374 11.21 0 0 thirty 0 0 0 0 80 thirty 90 375 11.21 0 0 0 0 0 0 0 0 0 0 376 11.21 0 0 twenty 0 0 twenty 0 70 80 thirty 377 11.21 0 0 60 twenty 40 twenty 0 90 80 twenty 378 11.21 0 twenty 50 0 80 70 0 50 80 thirty 379 11.21 0 0 0 0 0 0 0 thirty 0 50 380 11.21 0 0 0 0 0 twenty 0 thirty 0 0 381 1.12 0 0 twenty 0 0 0 0 0 0 0 382 11.21 0 0 0 0 0 40 0 70 0 80 383 11.21 10 10 0 twenty 10 50 10 70 70 40 11.21 0 0 0 0 0 40 0 60 60 twenty 384 11.21 0 0 0 0 twenty 0 0 0 thirty 0 385 11.21 0 0 0 0 thirty 0 0 twenty 0 0 386 11.21 0 0 0 0 40 twenty 0 80 80 40 387 11.21 0 0 0 0 0 0 0 0 0 0 388 11.21 0 thirty 0 0 0 thirty 10 80 50 80 389 11.21 thirty c c c c C. 70 C. C. C. 390 11.21 twenty c c c c C. 80 c c c 391 1.12 twenty c c 80 c 70 50 c c c 392 1.12 thirty c c c c C. 60 c c c 393 1.12 0 0 twenty 0 twenty 80 0 80 twenty 40 394 1.12 10 thirty 80 90 60 50 40 90 c c 395 1.12 10 thirty 80 C. 50 thirty 40 70 80 c 396 11.21 thirty C. c 90 90 C. 70 c C. c 397 1.12 twenty twenty 80 90 90 50 twenty 80 80 90 398 1.12 0 0 0 0 0 0 0 0 0 0 399 1.12 0 0 thirty 0 80 40 twenty 70 c 90 400 11.21 80 thirty thirty twenty 60 0 0 90 80 90 401 1.12 thirty 60 80 40 thirty 40 twenty 80 80 c 402 1.12 0 thirty 60 80 thirty 0 0 40 50 80 403 11.21 twenty 40 90 90 80 70 80 80 70 C. 404 11.21 thirty 60 90 C. 70 80 thirty 90 90 C. 405 11.21 thirty 50 90 50 80 70 60 C. 80 c 406 11.21 twenty thirty 90 40 C. 80 60 c C. 90 407 11.21 40 twenty twenty twenty 40 C. C. c 80 80 408 <3 11.21 twenty 80 70 twenty thirty 70 40 c 80 C. 409 + 11.21 0 0 40 twenty twenty 40 twenty 50 N N 410 + 11.21 0 thirty 60 40 60 40 thirty 60 70 thirty 411 1.12 0 90 C. C. 80 80 40 90 C. C. 412 1.12 0 twenty 40 thirty 50 70 40 60 50 80 413 11.21 0 twenty 60 50 40 40 twenty 70 40 90 414 11.21 twenty C. 90 60 60 C. twenty C. C. C.

170 158

Table 4 (continued)

Relationship no Dose kg / ha Y e n s AND n b g s e j g D 0 b r B y g r M. 0 g 1 c 0 b at V e e AND n m at in 1 b in 415 1.12 0 thirty 80 thirty 80 40 twenty 90 90 70 416 1.12 10 70 80 twenty 80 thirty 60 80 C. thirty 417 1.12 twenty 0 thirty 0 0 twenty 0 60 40 thirty 418 112 twenty twenty 70 40 70 thirty 70 80 60 50 419 1.12 0 twenty thirty thirty 10 70 twenty 80 60 80 420 1.12 0 twenty 80 80 70 twenty twenty 60 50 C. 421 11.21 0 80 90 C. 40 C. 80 C. 90 C. 422 11.21 0 70 90 C. 70 70 40 C. 70 C. 423 11.21 0 0 0 0 0 0 0 50 twenty twenty 424 11.21 0 0 40 twenty 0 0 0 40 0 thirty 425 11.21 0 0 70 twenty twenty C. 40 C. C. thirty 426 11.21 0 0 50 10 50 40 0 70 60 70 427 (11.21 0 0 0 0 0 0 0 0 10 0 428 11.21 0 0 0 0 twenty thirty 0 90 70 70 429 11.21 0 thirty thirty 10 twenty 0 0 thirty 50 10 430 11.21 twenty 0 thirty 0 0 70 40 60 thirty twenty 431 11.21 0 0 0 0 0 0 0 60 twenty 0 432 11.21 0 twenty 50 70 10 twenty 10 C. 10 90 433 11.21 0 0 0 0 0 0 0 0 0 0 435 11.21 0 40 60 thirty 70 C. twenty c 90 90 + 11.21 N N N 0 0 0 0 0 0 0 436 + 11.21 N N N 0 0 0 0 0 0 0 11.21 twenty 0 0 0 0 thirty 0 40 twenty 10 437 + 11.21 0 0 0 0 40 80 thirty 80 80 60 438 1.12 0 thirty 60 40 thirty 70 50 80 80 40 439 1.12 0 0 0 0 0 80 50 50 60 40 440 11.21 0 thirty 50 70 40 50 twenty 60 40 C. 441 1.12 0 40 40 twenty 80 90 twenty C. C. 70 442 11.21 10 60 80 70 C. 80 twenty C. c C. 443 1.12 0 80 10 50 40 90 80 C. 90 c 444 1.12 0 thirty 80 twenty thirty 0 0 0 N N 445 1.12 10 C. 80 C. 80 C. C. c C. C. 446 1.12 60 c 80 90 80 c c 90 C. c 447 1.12 thirty c 40 80 90 c c c c c 448 1.12 80 c 90 80 C. c c c c c 449 (M2 0 60 80 50 60 thirty thirty 70 10 thirty 450 1.12 0 0 10 0 twenty 80 twenty 90 10 40 451 1.12 twenty 0 twenty twenty thirty c 70 80 50 70 452 1.12 80 c 90 70 C. c c C. c c 453 1.12 0 0 0 0 0 90 twenty c thirty 80 454 (1.12 0 c 80 80 80 90 80 c c c 455 1.12 40 c 90 C. 90 c C. c c c 456 1.12 40 c 80 C. 80 c C. c c c 457 1.12 0 c 70 40 60 c 40 90 90 c 458 (1.12 50 c 90 C. 90 c C. c C. c 459 1.12 10 c 60 70 90 c 70 c C. c 460 (1.12 twenty c 90 C. 90 c 70 c C. c 461 1.12 60 c 90 C. 90 c thirty c c c

170 158

Table 4 (continued)

Relationship no Dose kg / ha Y e n s AND n b S. S. e j g D about b r B y g r M. 0 g 1 c 0 b at V e 1 e Ϊ n m at IN 1 b in 462 11.21 0 0 0 0 60 80 50 90 c c 463 1.12 50 thirty 70 50 80 c 80 C. c c 464 1.12 0 c 70 80 70 90 thirty C. c c 465 11.21 twenty c C. c c C. C. c c c 466 11.21 70 0 0 10 0 90 50 c 80 c 467 11.21 10 twenty 10 10 80 0 10 c c 80 468 1.12 0 90 50 90 60 80 70 90 c C. 469 1.12 twenty twenty twenty 10 80 70 twenty c c C. 1.12 twenty 40 0 0 40 80 10 c c c 470 1.12 0 0 0 0 0 twenty 40 twenty 0 0 471 11.21 twenty 90 80 80 twenty thirty thirty 90 80 c 472 11.21 0 0 0 0 twenty twenty 10 90 70 50 473 11.21 0 0 0 0 0 0 0 10 N thirty 474 11.21 0 80 c c 90 C. 70 C. 90 C. 475 11.21 twenty 70 60 thirty 80 C. 40 c c c 476 11.21 0 0 0 0 0 0 0 0 0 0 477 11.21 0 thirty 0 0 0 0 0 0 0 0 478 11.21 thirty 80 70 40 c C. C. c c c 479 11.21 0 0 0 0 0 0 0 0 0 0 480 11.21 0 0 0 0 0 0 0 0 0 0 481 11.21 0 40 thirty 60 twenty thirty 0 70 60 90 482 11.21 thirty 80 60 c 80 c 80 c c c 484 β 5.61 0 0 twenty 0 0 twenty 0 60 twenty twenty 485 11.21 0 twenty thirty thirty 0 0 0 thirty thirty 70 486 1.12 0 70 60 80 80 90 twenty 80 C. 80 487 11.21 0 0 0 0 0 50 0 40 twenty 0 489 11.21 0 90 80 c thirty 10 0 10 0 10 1.12 0 0 0 0 0 0 0 0 0 0 490 1.12 0 60 50 60 60 70 40 c 80 90 491 11.21 0 0 0 0 0 0 0 0 0 0 492 11.21 0 0 0 0 0 0 0 0 0 0 493 11.21 twenty 0 0 0 0 0 0 10 twenty 0 494 11.21 0 0 0 0 0 0 0 10 twenty 10 495 1.12 0 0 0 0 0 10 0 10 0 0 496 1.12 0 0 0 0 0 0 0 0 0 0 497 11.21 0 0 0 0 0 twenty 0 0 0 0 498 11.21 0 0 0 0 80 50 10 c 70 90 499 11.21 0 0 0 0 0 0 0 0 0 0 501 11.21 twenty 90 60 90 90 80 twenty c 90 40 1.12 0 0 0 0 0 ABOUT 0 thirty twenty twenty

* Poor germination (9 Uneven germination of turnips + Excessive black leg (Poor sprouting Sejg) FREQUENT BLACK LEG-Inmu, Wibw

170 158

Table 4A

PRE-EAST TESTS% PLANT INHIBITATION

Relationship no Dose kg / ha Y e n s AND n b g S. e j g D 0 b r B y g r M. 0 g 1 C. 0 b at V e 1 e AND n m at IN and b in 89 11.21 10 0 0 0 0 twenty 0 90 70 thirty 93 1.12 0 0 0 0 0 thirty twenty twenty 10 twenty 98 1.12 0 0 70 60 thirty 80 twenty 90 70 60 136 1.12 0 90 90 C. 70 80 80 90 90 C. 139 1.12 twenty twenty 40 80 thirty 70 70 C. 90 90 140 1.12 0 thirty 70 60 0 70 80 90 70 70 141 1.12 0 twenty 50 70 twenty 80 70 70 80 90 178 1.12 0 twenty 10 thirty 10 50 twenty C. 90 C. 198 1.12 0 0 0 0 0 0 0 90 twenty 70 203 11.21 0 0 twenty 10 0 10 twenty 0 0 0 205 11.21 0 0 twenty 0 0 0 0 10 thirty 10 251 1.12 0 50 70 80 0 40 thirty 60 twenty 90 252 1.12 0 thirty 60 60 twenty 40 thirty twenty 10 10 285 1.12 0 0 0 0 50 C. 80 C. 10 80 287 1.12 thirty 0 0 0 0 70 90 c 60 80 288 1.12 0 0 0 0 0 C. thirty c twenty 90 303 11.21 0 C. C. C. C. c C. c C. C. 315 11.21 twenty C. c C. C. c c c c C. 329 1.12 0 0 0 0 0 70 0 c 90 C. 350 1.12 0 0 0 0 0 80 10 c C. 50 351 1.12 0 0 0 0 0 80 80 c C. C. 488 1.12 0 thirty 40 80 70 70 0 c 60 C. 500 11.21 0 10 70 80 thirty 60 40 70 thirty 90

POST-EMERGENCY ACTION TESTS The post-emergence herbicidal activity of some of the various compounds of the present invention was demonstrated in greenhouse trials as follows. The soil from the top layer was placed in aluminum bowls with holes in the bottom and compacted so that the soil surface was 0.95 -1.27 cm below the upper edge of the bowl. A certain number of seeds of individual species of different annual dicotyledonous and monocotyledonous plants and / or vegetative suckers of perennials were placed and pressed into the soil surface. The seeds and / or vegetative shoots were covered with soil and its level was leveled. The bowls were placed on a bench in the greenhouse and the soil was irrigated from below as needed. When the plants reached the desired age (two to three weeks), each pan individually transferred to a spraying chamber and sprayed by means of spray, resulting in spraying at a pressure of 170.3 kPa (pressure 10 lb / ⁱⁿ²⁾ and noting the application rate. The spray liquid contains enough of a mixture of emulsifiers to obtain a spray liquid (solution or suspension) containing about 0.4% by volume of emulsifier. The spray liquid contains sufficient test compound to achieve application rates of active ingredient corresponding to those in Tables 5 and 5A, with a total spray volume corresponding to an actual volume of 1,870 l / ha (200 gallons / acre). The bowls were placed back in the greenhouse and watered as before. In about 10-14 days (usually 11 days), and in some cases still 24-28 days (usually 25 days) after spraying, damage to the plants was observed as compared to the control plants. The rates of herbicidal post-emergence reported in these Tables represent the percent inhibition of a particular plant species.

170 158

Table 5

POST EMERGENCY TESTS% PLANT INHIBITATION

Relationship no Dose kg / ha Y e n s AND n b g S. e J. g D 0 b r B y g r M. 0 g 1 c 0 b at V e e AND n m at IN and b in 62 11.21 0 0 0 0 0 0 0 10 0 0 63 11.21 0 twenty 70 twenty twenty c 0 C. 40 C. 64 11.21 0 twenty twenty 0 thirty 60 twenty 60 twenty 80 65 11.21 0 0 50 10 70 50 40 70 thirty 70 66 11.21 0 0 80 thirty twenty 70 0 50 thirty C. 67 11.21 twenty twenty 80 40 40 70 twenty 80 40 c 68 λ 11.21 0 0 0 0 0 0 0 0 0 0 69 11.21 0 0 0 0 0 10 0 10 0 0 70 11.21 0 10 10 10 40 40 thirty 50 twenty N 71 11.21 0 0 0 0 0 twenty thirty twenty twenty 40 72 11.21 10 10 10 twenty 50 thirty 60 90 thirty 90 73 11.21 0 0 0 0 0 0 10 twenty twenty twenty 74 1.12 10 0 10 10 10 twenty twenty 40 40 90 75 11.21 0 0 0 0 0 10 0 0 0 60 76 1.12 10 40 40 thirty 50 50 40 90 70 C. 77 11.21 0 twenty twenty 0 twenty 10 twenty thirty 60 60 78 11.21 0 0 10 10 0 10 10 40 40 thirty 79 11.21 10 60 thirty twenty twenty 60 twenty C. 90 C. 80 11.21 0 0 0 0 0 10 10 60 0 N 81 11.21 50 0 70 10 70 60 40 80 10 90 82 11.21 10 0 40 twenty thirty 90 0 twenty thirty 60 83 11.21 twenty 0 60 40 40 80 70 C. 90 C. 84 11.21 10 10 40 0 10 50 twenty c 0 N 85 11.21 twenty 60 90 50 70 C. 40 c twenty C. 86 11.21 10 thirty 80 0 80 C. 70 c 60 C. 87 11.21 10 10 40 0 twenty 70 50 c thirty 40 88 11.21 0 10 70 10 50 C. C. c 60 C. 90 11.21 0 10 0 10 0 60 thirty c 50 50 91 1.12 10 50 40 40 thirty 60 C. 40 50 80 92 1.12 twenty thirty 40 50 thirty C. 80 c 80 80 94 112 10 90 90 c C. 90 80 c 80 C. 95 1.12 10 60 50 40 80 80 C. c 70 c 96 1.12 40 C. C. c C. C. 90 c C. c 97 112 50 70 60 90 c 90 C. c c c 99 11.21 10 C. C. 90 c C. 90 c c c 100 112 twenty c c C. c c 80 c 80 c 101 112 thirty 90 70 C. c c C. c C. c 102 1.12 twenty 90 c C. 90 c 60 c c c 103 1.12 10 40 70 thirty 80 80 60 c 70 c 104 1.12 twenty thirty 80 40 50 C. 70 c 40 c 105 1.12 twenty thirty twenty 0 twenty 40 twenty 80 thirty c 106 112 10 thirty 40 twenty 60 C. 60 c 60 90 107 1.12 10 0 twenty 0 thirty 50 50 90 40 90 108 11.21 0 90 90 C. C. C. C. C. C. C. 109 1.12 10 40 twenty 0 thirty 60 40 c 40 90 110 1.12 twenty thirty 40 twenty 70 80 60 c thirty C. 111 = 11.21 thirty 0 twenty twenty 60 C. C. c 80 c

170 158

Table 5 (continued)

Relationship no Dose kg / ha Y e n s AND n b g S. e J. g D 0 b r B y g r M. 0 g 1 c 0 b at V e e AND n m at IN 1 b in 112 11.21 40 thirty thirty 0 60 80 60 C. 40 70 113 11.21 0 0 0 0 0 thirty twenty 50 0 twenty 114 11.21 10 10 0 0 0 50 twenty 50 10 60 115 1.12 twenty 40 40 twenty 80 60 60 C. 60 C. 116 1.12 twenty 80 70 70 80 C. C. C. 80 80 117 1.12 twenty 90 C. c C. C. 90 C. 90 C. 118 1.12 thirty thirty thirty twenty thirty 60 80 90 thirty c 119 11.21 twenty C. C. C. C. C. C. C. C. c 120 1.12 10 40 80 50 80 C. 90 C. 70 c 121 11.21 twenty 40 90 90 C. C. 90 C. 90 c 122 1.12 twenty twenty 70 twenty 70 80 60 C. 50 90 123 1.12 twenty 0 50 60 50 C. 70 C. thirty 90 124 11.21 twenty 70 C. 50 90 C. 70 C. 90 C. 125 1.12 0 twenty 0 0 0 thirty 40 C. thirty C. 126 1.12 10 40 thirty 0 50 60 thirty 90 40 80 127 1.12 twenty twenty C. 80 60 C. C. C. C. C. 128 1.12 twenty thirty C. C. 50 C. C. C. 90 C. 129 1.12 thirty 40 90 80 80 90 C. C. 90 C. 130 1.12 twenty twenty 70 thirty 40 C. C. C. 40 C. 131 1.12 thirty twenty 50 twenty 0 c c c 40 c 132 11.21 thirty 60 C. 80 C. c c c C. c 133 1.12 40 0 50 twenty 50 c c c 40 80 134 1.12 twenty C. C. C. C. c c c C. c 135 1.12 twenty C. c C. c c c c c c 137 1.12 twenty C. c C. c c c c c c 138 1.12 twenty C. c C. c c c c c c 142 1.12 thirty C. c C. c c c c c c 143 112 twenty C. 0 C. c c c c c c 144 112 twenty 60 90 C. 70 c c c c c 145 1.12 twenty 80 80 c 70 80 c c c c 146 112 thirty 80 80 40 90 c c c 90 c 147 1.12 thirty 0 70 0 80 c c c 40 c 148 112 twenty C. c c c c c c c c 149 112 twenty 0 40 0 thirty c 70 c 50 c 150 112 twenty c c c C. c c c 90 c 151 112 twenty c c c C. c c c 80 c 152 112 twenty thirty twenty 40 0 50 40 60 50 90 153 112 10 40 90 40 thirty c 40 c 50 90 154 1.12 twenty twenty 70 40 80 c 80 c 40 80 155 112 twenty thirty 80 90 80 c 40 c 50 80 156 112 10 thirty 70 60 thirty c 80 c thirty 80 157 112 twenty 50 80 40 60 80 50 c 70 c 158 112 twenty 50 80 60 50 c 80 c twenty 90 159 11.21 50 50 C. C. C. c C. c 80 C. 160 112 thirty 70 80 60 80 c c c 80 C. 161 11.21 twenty C. C. C. C. c c c C. c 162 112 10 10 40 thirty twenty 50 twenty thirty 10 90 163 11.21 thirty 60 50 thirty 60 c thirty c thirty C.

170 158

Table 5 (continued)

Relationship no Dose kg / ha Y e n s AND n b g S. e J. g D 0 b r B y g r M. 0 g 1 C. 0 b at V e e AND n m at IN and b in 164 11.21 0 0 0 0 0 twenty 40 twenty 40 thirty 11.21 0 thirty thirty 0 twenty twenty 40 thirty 60 twenty 165 11.21 10 80 80 80 80 C. 40 C. twenty C. 166 1.12 0 twenty thirty 0 0 twenty twenty 60 thirty 90 167 11.21 0 60 C. 60 90 90 90 C. C. C. 11.21 twenty 60 80 50 80 80 70 C. 90 C. 168 11.21 40 twenty 80 twenty 70 80 C. C. 60 C. 169 1.12 thirty thirty 80 thirty 50 90 70 90 50 c 170 11.21 twenty 50 80 40 70 90 70 90 70 c 11.21 0 40 80 twenty 80 90 80 C. 90 c 171 11.21 0 10 50 thirty 50 twenty 40 c thirty c 172 1.12 twenty 0 40 twenty thirty 50 60 80 thirty thirty 173 1.12 twenty 0 40 twenty twenty 70 80 70 thirty 60 174 1.12 twenty 0 40 twenty thirty 60 70 80 thirty 80 175 11.21 twenty 40 90 90 90 C. 60 C. 60 c 176 11.21 twenty 90 90 80 90 C. 90 c 90 c 177 11.21 10 60 C. C. C. C. C. c C. c 179 1.12 thirty 80 90 60 80 C. 70 c 80 c 180 1.12 thirty 40 90 70 C. 90 80 c C. c 181 11.21 40 50 C. 80 C. 90 C. c c c 182 11.21 twenty C. C. C. c C. C. c c c 183 1.12 0 40 80 50 60 80 80 90 50 c 184 11.21 thirty twenty 60 twenty 70 C. C. c 60 c 185 11.21 twenty thirty 80 thirty 70 90 90 c 80 c 186 1.12 thirty 80 80 90 80 C. 80 c 80 c 187 1.12 0 40 70 thirty 40 40 70 80 thirty 90 188 11.21 thirty 80 C. C. 90 90 C. c 80 c 189 1.12 thirty twenty 60 twenty 40 50 40 80 40 80 190 1.12 twenty 0 50 twenty thirty C. 90 c 50 50 191 11.21 10 thirty C. twenty 60 c 40 90 90 C. 192 11.21 thirty C. C. C. C. c C. C. C. c 193 11.21 0 twenty 70 60 80 c c C. 80 90 194 1.12 twenty 50 70 thirty 80 90 90 c 60 90 195 1.12 thirty thirty thirty 40 80 90 C. c 50 80 196 1.12 thirty thirty 60 40 70 90 90 c 60 80 197 11.21 10 50 80 thirty C. 80 90 c 90 C. 199 1.12 thirty thirty 80 thirty 60 C. 50 c 50 thirty 200 1.12 twenty twenty twenty thirty thirty c 80 c 60 50 201 1.12 0 0 twenty twenty 0 c 70 c 40 50 202 1.12 twenty 0 thirty twenty twenty c 60 80 thirty 50 204 1.12 0 0 twenty 0 0 0 10 twenty 0 thirty 206 11.21 0 thirty 90 50 80 70 40 c 60 C. 207 1.12 0 0 twenty 0 0 thirty thirty 40 thirty twenty 208 1.12 10 60 90 60 90 c 90 c C. C. 209 1.12 10 0 0 0 0 twenty twenty 40 0 40 210 1.12 10 10 10 10 10 90 50 40 twenty 90 211 1.12 0 twenty 70 50 70 80 60 C. thirty C. 212 1.12 40 90 90 80 C. 90 90 c 90 90

170 158

Table 5 (continued)

Relationship no Dose kg / ha Y e n s AND n b g s e j g D 0 b r B y g r M. 0 g 1 c 0 b at V e e AND n m at IN and b in 213 1.12 thirty twenty 10 thirty 40 60 c 90 90 90 214 1.12 thirty 60 60 80 40 60 90 60 90 90 215 1.12 10 thirty 50 40 80 C. C. C. C. 90 216 1.12 10 60 C. 80 80 90 60 C. 60 C. 217 1.12 twenty 90 90 C. 90 90 90 C. 90 C. 218 1.12 thirty C. C. C. C. C. 90 C. 90 C. 219 1.12 60 50 c C. C. C. C. C. 90 90 220 1.12 40 C. 90 90 C. C. C. C. C. C. 221 1.12 50 90 90 C. C. C. 90 C. C. C. 222 1.12 80 0 twenty 90 90 90 80 c C. 90 223 1.12 thirty 90 90 C. C. 90 C. c C. C. 224 1.12 40 50 80 60 90 90 C. c 80 C. 225 1.12 thirty 90 90 60 C. C. C. c 90 C. 226 1.12 thirty 60 70 C. C. 90 C. c C. 90 227 1.12 60 90 90 C. C. 90 C. c 90 90 228 1.12 80 90 C. C. C. C. c c C. C. 229 1.12 40 70 C. 90 C. C. c c C. C. 230 1.12 40 thirty 50 thirty 90 C. c c 60 90 231 1.12 twenty 0 twenty twenty 70 50 50 90 40 80 232 1.12 10 C. C. C. 90 90 C. c 90 C. 233 1.12 10 60 40 50 90 90 C. 90 90 90 234 1.12 10 0 10 0 0 50 90 C. twenty C. 235 1.12 0 0 0 0 0 50 90 C. 10 90 236 1.12 10 50 90 C. 50 C. 90 C. C. 90 237 1.12 twenty 40 60 60 90 90 90 C. 70 90 238 1.12 thirty twenty 60 twenty 40 80 80 90 40 C. 239 1.12 80 90 90 C. C. C. C. C. C. 90 240 1.12 thirty C. C. c c c c C. c C. 241 1.12 twenty C. 50 90 c 60 80 C. 70 90 242 1.12 thirty 60 50 90 c 90 90 C. c C. 243 1.12 thirty 60 50 C. c 90 90 c 90 C. 244 1.12 twenty twenty twenty 0 thirty 50 40 50 50 50 245 1.12 twenty thirty thirty 90 50 90 90 C. 90 90 246 1.12 thirty C. C. C. c C. C. C. C. C. 247 1.12 60 40 80 C. c 90 90 c C. C. 248 1.12 60 40 60 50 c 90 90 90 90 C. 249 1.12 thirty 90 90 C. c 80 90 C. C. C. 250 1.12 10 C. C. c c C. 90 C. C. 90 253 1.12 10 90 90 90 80 80 80 C. 90 C. 254 1.12 10 C. C. C. c C. C. c C. C. 255 1.12 40 C. C. c c C. C. c C. C. 256 1.12 40 80 c 90 90 80 90 c 90 C. 257 1.12 twenty 50 80 60 70 C. 70 c 60 90 258 1.12 thirty 40 60 thirty 50 c 80 c 80 90 259 1.12 twenty 0 0 0 0 thirty 70 thirty 40 40 260 1.12 twenty thirty 50 60 80 60 40 c 60 90 261 - 11.21 twenty C. C. C. C. C. C. c C. C. 262 1.12 twenty C. C. C. c C. c c C. C.

170 158

Table 5 (continued)

Relationship no Dose kg / ha Y e n s AND n b g s e J. g D 0 b r B y g Γ M. 0 g 1 c 0 b at V e e AND n m at IN 1 b in 263 1.12 thirty thirty 70 70 70 80 60 c 60 90 264 1.12 40 C. C. C. C. C. C. c C. C. 265 1.12 twenty C. c c c c 90 c 90 C. 266 1.12 twenty c c 90 c c C. c 90 C. 267 1.12 10 c c C. 90 90 90 c 90 c 268 1.12 twenty 80 90 C. C. 90 C. c 50 90 269 1.12 thirty 90 C. 70 90 C. 90 c 90 N 270 1.12 60 90 90 C. C. C. 90 c 90 C. 271 1.12 twenty 70 40 60 50 C. C. c 50 C. 272 1.12 thirty 60 40 50 60 C. C. c 60 c 273 1.12 twenty 70 40 80 50 C. 60 90 60 c 274 1.12 0 40 50 50 thirty C. 60 70 40 80 275 1.12 twenty 40 80 70 50 C. 80 90 40 c 276 1.12 twenty 50 50 thirty 80 90 thirty 90 50 N 277 1.12 twenty 90 C. 90 C. C. 80 C. 60 C. 278 1.12 40 C. c C. C. C. C. C. 90 c 279 11.21 50 10 c 80 C. C. C. C. C. c 280 11.21 60 0 c 40 80 C. C. C. C. c 281 1.12 0 0 0 0 0 thirty thirty thirty thirty thirty 1.12 0 0 0 0 0 50 40 twenty 0 60 282 1.12 10 0 twenty 0 thirty 70 C. C. 10 C. 283 1.12 0 10 50 . thirty 40 90 c c 50 90 286 1.12 twenty 0 thirty 0 50 C. c c thirty 90 289 1.12 twenty 10 50 twenty 60 90 c c 40 C. 290 1.12 twenty 0 40 10 50 C. c c 60 c 291 1.12 thirty 0 thirty twenty twenty C. c c 40 90 292 1.12 10 0 0 0 40 60 80 c twenty C. 293 1.12 twenty 0 twenty 0 60 C. c c 10 C. 294 1.12 0 twenty thirty twenty twenty 80 50 50 twenty thirty 1.12 0 0 0 0 0 90 80 80 0 0 295 1.12 thirty 60 80 thirty 50 90 70 90 80 c 296 1.12 twenty 0 10 10 10 90 90 C. thirty 90 297 1.12 10 twenty twenty twenty 0 60 60 80 twenty C. 298 1.12 twenty thirty thirty thirty twenty 90 C. C. 60 C. 299 1.12 twenty twenty thirty thirty thirty C. C. c thirty 90 300 1.12 40 0 60 twenty 80 C. C. c thirty 90 301 11.21 0 10 60 40 60 60 twenty thirty twenty 90 302 1.12 10 C. C. C. C. C. C. c C. C. 304 1.12 thirty 90 C. 80 C. 90 90 c c C. 305 1.12 10 80 70 90 C. C. C. c c C. 306 1.12 40 C. C. C. C. C. C. c c C. 307 1.12 twenty 90 c c C. C. 90 c 90 C. 308 1.12 twenty C. c c c 90 90 c 90 c 309 1.12 60 C. c c c C. C. c 90 c 310 1.12 thirty 40 40 thirty 60 C. 80 90 60 c 311 1.12 40 C. 80 c 90 C. C. c 80 c 312 - 11.21 10 c c c C. C. C. c 90 c 313 1.12 twenty c 90 c c c 70 c 60 c

170 158

Table 5 (continued)

Relationship no Dose kg / ha Y e n s AND n b g S. e j g D 0 b r B y g r M. 0 g 1 C. 0 b at V e e AND n m at IN b in 314 1.12 thirty 90 90 C. C. C. 90 C. 90 C. 316 1.12 twenty thirty 50 40 40 50 50 60 thirty C. 317 = 1.12 twenty twenty 70 0 70 C. C. C. 80 c 318 = 11.21 40 40 C. 80 90 c C. C. 90 c 319 = 1.12 twenty 0 0 0 0 c C. C. 60 c 320 = 1.12 twenty twenty 80 thirty 70 c C. C. 80 c 321 1.12 0 0 twenty twenty twenty thirty 60 C. thirty c 322 1.12 thirty 70 80 50 60 60 80 90 50 c 323 1.12 twenty 50 thirty twenty thirty 80 70 90 thirty c 324 1.12 twenty C. C. C. C. 90 C. C. 90 90 325 - 11.21 10 C. c c 90 C. c C. 90 c 326 11.21 twenty C. c c 90 C. c C. 50 c 327 11.21 0 twenty 0 twenty 50 50 thirty 50 10 90 328 1.12 0 40 50 twenty 60 50 80 C. thirty c 330 1.12 10 twenty 60 thirty 90 90 90 c 60 c 331 1.12 thirty 80 C. C. 90 C. C. c 90 c 332 1.12 0 twenty 50 thirty 60 80 60 c 60 c 333 1.12 0 thirty 40 thirty 80 60 50 80 40 c 334 1.12 twenty 40 40 twenty thirty 70 50 80 50 90 335 1.12 twenty thirty 90 80 80 C. C. C. 90 c 336 1.12 twenty 60 60 90 90 c 80 c 80 c 337 1.12 twenty twenty 60 80 50 c C. c 60 c 338 1.12 twenty thirty 90 90 80 c c c 80 c 339 1.12 0 0 0 thirty 40 c c c 50 90 340 1.12 0 thirty thirty 0 50 c c c 60 ' c 341 1.12 twenty C. C. C. C. c c c 90 c 342 1.12 40 90 90 C. C. c c c 80 c 343 11.21 twenty thirty 60 40 40 80 80 80 60 80 344 1.12 10 0 0 0 0 twenty twenty 40 0 0 345 1.12 0 0 0 0 twenty 40 twenty thirty twenty twenty 346 11.21 thirty 0 twenty 10 10 50 50 c 60 70 347 11.21 0 50 70 thirty 80 c 80 90 60 60 348 1.12 0 twenty thirty twenty 50 c 50 80 40 40 349 1.12 twenty twenty 0 twenty twenty thirty 40 60 thirty 60 352 11.21 0 0 10 0 0 10 10 0 0 90 353 11.21 10 90 c c 90 90 80 C. 90 C. 354 1.12 10 thirty 40 twenty 0 twenty 10 10 thirty thirty 355 11.21 10 10 40 10 60 90 40 50 40 C. 356 11.21 twenty twenty 90 thirty 80 80 40 90 thirty c 357 1.12 0 0 10 10 10 twenty 10 thirty 10 twenty 358 11.21 10 0 10 10 twenty 90 thirty 90 90 90 359 1.12 0 0 0 0 0 0 10 10 0 70 360 11.21 0 0 0 0 0 0 0 40 twenty 50 361 11.21 10 0 0 0 10 0 10 10 0 thirty 362 11.21 10 0 0 0 0 0 10 10 0 twenty 363 11.21 0 0 thirty thirty twenty 90 thirty C. thirty 90 364 11.21 0 0 0 10 0 twenty 10 10 10 40 365 11.21 0 thirty 80 thirty thirty 70 thirty 90 twenty C.

170 158

Table 5 (continued)

Relationship no Dose kg / ha Y e n s AND n b g S. e J. g D 0 b r B y g r M. 0 g 1 C. 0 b at V e e AND n m at IN and b in 366 - 11.21 10 thirty 60 60 80 C. 40 C. 60 C. 367 11.21 0 0 0 10 10 thirty twenty twenty 10 N 368 11.21 0 0 0 0 0 0 10 10 10 N 369 11.21 0 twenty 0 0 thirty twenty twenty twenty 40 90 370 11.21 0 10 10 10 40 twenty twenty thirty thirty C. 371 11.21 0 0 0 0 0 0 0 0 0 0 372 11.21 0 0 0 0 twenty thirty twenty twenty twenty 60 373 11.21 0 10 10 10 80 twenty 50 50 50 90 374 11.21 0 10 40 10 40 90 twenty 60 80 C. 375 11.21 0 0 10 0 10 twenty 10 10 twenty thirty 376 11.21 0 C. 60 50 50 60 80 90 90 90 377 11.21 twenty 90 thirty 90 60 90 90 90 - 90 90 378 11.21 0 0 0 0 10 40 twenty twenty 90 90 379 11.21 0 0 10 10 thirty 40 40 C. twenty C. 380 11.21 0 0 thirty twenty twenty 40 thirty 50 thirty 70 381 1.12 0 0 0 0 0 twenty twenty 0 twenty 0 382 11.21 0 0 twenty 0 thirty thirty thirty 60 50 90 383 11.21 0 0 twenty 0 0 thirty twenty 40 twenty 10 384 11.21 0 0 0 0 0 0 twenty thirty twenty 50 385 11.21 0 thirty 0 0 twenty 40 thirty 40 50 40 386 11.21 0 0 0 0 0 80 60 50 50 50 387 11.21 0 0 0 0 thirty 10 10 thirty thirty 50 388 \ 11.21 0 0 0 0 thirty 10 10 N 10 twenty 389 - 11.21 10 90 90 80 90 C. 50 C. C. C. 390 - 11.21 10 C. C. c 90 C. 60 C. 90 c 391 1.12 twenty thirty thirty 10 60 90 twenty thirty twenty c 392 1.12 10 40 60 40 90 C. 40 80 40 c 393 1.12 twenty 0 twenty 10 twenty C. 90 C. 0 N 394 1.12 10 80 90 40 90 80 thirty C. 60 c 395 1.12 10 twenty 60 thirty 40 50 twenty 60 thirty c 396 11.21 10 thirty thirty twenty twenty C. twenty 90 40 c 397 1.12 0 twenty 60 10 70 40 twenty 40 thirty 80 398 1.12 0 0 0 0 0 0 0 0 0 0 399 1.12 thirty 50 40 60 70 50 70 90 60 90 400 11.21 thirty 0 twenty 0 thirty 90 thirty C. 90 C. 401 1.12 10 40 40 thirty 50 60 thirty 90 thirty C. 402 1.12 0 twenty twenty twenty twenty 80 50 90 thirty C. 403 11.21 thirty 50 C. 90 C. C. 90 C. C. C. 403 11.21 10 60 90 90 c c 90 C. 90 C. 405 11.21 twenty twenty 50 thirty c c 90 90 C. C. 406 11.21 10 0 thirty 10 twenty thirty thirty C. 40 90 407 11.21 40 twenty C. C. 90 C. C. c C. C. 408 11.21 twenty 40 70 thirty 60 50 50 c 80 C. 11.21 0 40 40 0 40 40 80 c 80 C. 409 11.21 0 0 thirty 0 40 60 90 70 thirty 70 11.21 0 40 70 twenty 40 70 80 70 60 80 410 11.21 0 0 80 60 0 50 60 90 60 C.

170 158

Table 5 (continued)

Relationship no Dose kg / ha Y e n s AND n b g s e j g D 0 b r B y g r M. 0 g 1 c 0 b at V e e AND n m at IN and b in 411 1.12 0 0 50 0 50 60 twenty 90 thirty c 1.12 thirty 40 80 50 80 80 40 C. 60 c 412 1.12 0 0 twenty twenty twenty 40 thirty 50 twenty 50 413 11.21 0 twenty 50 thirty 70 80 60 C. 40 C. 414 11.21 10 C. C. C. 90 C. 40 c C. c 415 1.12 thirty 50 thirty thirty 80 50 40 90 thirty c 416 1.12 twenty 40 60 thirty thirty 50 50 80 40 60 417 1.12 twenty twenty 50 thirty 40 60 60 90 50 80 418 1.12 0 0 0 twenty thirty thirty 0 60 0 70 1.12 0 0 twenty twenty twenty 40 thirty thirty thirty 60 419 1.12 0 twenty 70 0 50 50 50 C. 40 C. 420 1.12 0 10 0 0 40 50 40 60 60 90 421 11.21 thirty 80 C. C. C. C. C. C. C. C. 422 11.21 0 50 90 60 80 70 70 C. 80 C. 423 11.21 0 0 0 0 0 thirty 40 thirty twenty 90 424 11.21 0 0 twenty 0 10 10 40 90 twenty 90 425 11.21 0 0 0 0 0 40 40 80 60 60 11.21 0 0 0 0 0 50 50 60 50 50 426 = 11.21 0 0 0 0 0 40 thirty thirty twenty 40 427 11.21 0 0 0 0 0 0 10 0 0 0 428 11.21 0 0 0 twenty twenty 90 40 80 60 60 429 11.21 40 twenty 50 0 40 twenty twenty 90 C. 60 430 11.21 0 thirty 60 twenty thirty 50 50 90 thirty 80 431 11.21 0 0 0 0 0 10 twenty 10 twenty 10 432 11.21 0 twenty C. 10 twenty 40 twenty 60 C. C. 433 11.21 0 0 0 0 0 0 0 0 0 0 435 11.21 0 40 80 twenty 60 80 60 C. 0 c 436 11.21 0 0 50 0 0 twenty thirty twenty 40 0 437 11.21 0 0 thirty 0 0 60 thirty 40 thirty 50 11.21 0 0 twenty 0 0 40 twenty thirty 0 50 438 1.12 thirty 50 40 twenty thirty 70 60 80 thirty 90 439 1.12 twenty 0 50 twenty thirty 40 60 80 thirty 80 440 11.21 twenty 60 60 thirty 50 90 70 C. 70 C. 441 1.12 10 thirty 40 twenty thirty 80 80 80 40 80 442 11.21 0 thirty 50 twenty 50 90 50 C. 70 C. 443 1.12 twenty C. C. C. C. C. C. c 90 c 444 1.12 40 0 60 0 twenty 80 80 c thirty thirty 445 1.12 40 c C. c C. C. C. c 90 c 446 1.12 40 c 90 c C. C. c c C. c 447 1.12 twenty 40 thirty 60 80 C. c c 90 70 448 1.12 twenty thirty 40 twenty 50 90 70 80 twenty 40 449 1.12 10 thirty 50 40 60 C. 80 c 10 40 450 1.12 10 40 40 thirty 40 C. 80 c twenty 50 451 1.12 twenty 0 0 0 twenty 40 40 50 twenty 50 452 1.12 10 twenty 40 0 40 C. 80 70 60 90 453 1.12 twenty 40 40 twenty 50 c C. 80 thirty 50 454 1.12 thirty C. C. c C. c c C. 90 80 455 1.12 twenty c c c c c 80 c C. 90

170 158

Table 5 (continued)

Relationship no Dose kg / ha Y e n s AND n b g S. e j g D 0 b r B y g r M. 0 g 1 C. 0 b at V e e AND n m at IN 1 b in 456 1.12 50 C. 90 C. 80 C. C. C. 70 90 457 112 10 70 90 C. C. C. 90 C. C. 60 458 1.12 twenty C. C. C. c c 80 C. C. C. 459 1.12 twenty c C. c c c C. C. c C. 460 1.12 twenty c C. c c c 80 C. c C. 461 1.12 twenty c C. c c c C. C. c C. 462 11.21 0 thirty 50 twenty 10 40 thirty C. 40 90 463 1.12 40 thirty 60 90 c 90 C. C. c 90 464 1.12 twenty c C. C. c C. C. C. c C. 465 11.21 50 c C. C. c C. C. c c C. 466 11.21 40 40 80 50 70 C. c c c C. 467 11.21 40 80 80 40 90 C. 80 c c C. 468 1.12 thirty C. C. C. C. 90 c c c C. 469 1.12 twenty 10 thirty twenty 80 80 80 c 60 90 470 1.12 0 0 0 0 0 twenty twenty 0 0 0 471 11.21 40 90 c 70 C. C. C. c C. C. 472 11.21 10 twenty 50 twenty thirty 60 50 c c 70 473 11.21 0 0 0 10 0 60 thirty 50 thirty 50 474 11.21 twenty 80 C. 90 C. C. C. c C. C. 475 11.21 10 twenty 70 0 60 C. thirty c C. 90 476 11.21 0 0 0 0 0 0 0 0 0 0 477 11.21 0 0 0 0 0 0 0 0 0 0 478 11.21 0 twenty twenty twenty twenty 70 70 90 40 80 479 11.21 0 0 0 0 0 10 10 0 0 0 480 11.21 0 0 0 0 0 thirty 0 twenty 50 0 481 11.21 10 50 90 40 50 90 40 c 40 90 482 11.21 twenty C. C. c C. 90 c c c C. 484 5.61 0 0 0 0 thirty 50 twenty 60 50 80 485 11.21 0 0 twenty 0 twenty 60 60 80 thirty 90 486 112 thirty thirty 10 twenty 40 80 70 40 40 80 487 11.21 0 0 0 0 0 twenty thirty 70 twenty 80 489 11.21 10 10 10 0 0 twenty twenty 90 0 thirty = 112 0 0 0 0 0 twenty 0 0 twenty 0 490 112 twenty 60 c 90 C. C. 70 C. 80 C. 491 11.21 0 0 thirty 0 40 50 50 60 thirty 70 492 11.21 0 0 0 twenty 0 10 0 0 0 0 493 11.21 0 0 twenty 0 50 40 40 50 twenty 60 11.21 0 0 0 0 thirty 0 0 twenty twenty 40 494 11.21 0 0 0 0 0 twenty twenty twenty 0 10 495 112 0 0 0 0 twenty twenty twenty 40 50 50 496 112 0 0 0 0 0 0 10 10 thirty 0 497 11.21 0 0 0 0 0 0 0 0 twenty 40 498 11.21 0 0 0 0 0 80 50 90 thirty 90 499 11.21 10 0 10 0 thirty twenty twenty twenty twenty 40 501 11.21 0 50 60 thirty thirty 80 thirty 80 thirty 50 112 0 0 0 0 0 0 0 0 0 0

a Generally sparse Wibw growth - VOLATILE = Cobu germination uneven \ SAMPLE ERROR DUE TO VOLATILE

170 158

Table 5A

POST EMERGENCY TESTS% PLANT INHIBITATION

Relationship no Dose kg / ha Y e n s AND n b g S. e j g D 0 b r B y g r M. 0 g 1 c 0 b at V e e AND n m at IN 1 b in 89 11.21 0 10 70 10 twenty C. C. C. 80 80 93 1.12 0 10 40 50 70 60 70 90 60 90 98 1.12 0 70 90 90 80 C. C. C. 80 80 136 1.12 10 c C. C. C. C. c c C. C. 139 112 10 90 C. C. c c 90 c C. C. 140 1.12 10 C. C. C. c c C. c 90 90 141 112 0 90 90 C. 70 c 90 c ' 80 C. 178 112 0 90 70 90 70 c 90 c 70 C. 198 1.12 0 50 70 70 50 90 70 c C. C. 203 11.21 0 twenty 60 thirty 50 60 60 c 60 90 205 11.21 0 40 70 50 10 80 60 c 60 90 251 112 10 80 C. C. 90 C. 90 c 70 90 252 112 twenty 90 c C. 90 C. C. c C. C. 285 1.12 40 thirty 50 40 70 C. C. c c C. 287 1.12 10 0 80 10 70 C. C. c twenty 90 288 1.12 10 0 twenty 0 50 C. C. c 90 C. 303 11.21 70 C. C. C. C. C. C. c C. C. 315 11.21 twenty C. c C. c C. C. c C. C. 329 112 0 90 90 90 90 C. 90 c C. C. 350 1.12 thirty twenty 70 0 60 90 C. c C. C. 351 112 thirty thirty 60 40 70 C. C. c C. C. 488 1.12 0 90 C. 90 90 C. C. c C. c 500 11.21 - - - 0 0 0 0 0 0 0 11.21 0 50 90 70 90 c c c 90 c

Herbicides, including concentrate compositions that require dilution before use, can contain at least one active ingredient and a liquid or solid excipient. These compositions are prepared by mixing the active ingredient with an excipient such as a diluent, carrier, or conditioning agent. The result is formulations in the form of fine powders, granules, pellets, solutions, dispersions or emulsions. Thus, the active ingredient can be combined with adjuvants such as fine-grained solids, liquids of organic origin, water, wetting agents, dispersants, emulsifiers and any suitable mixtures thereof.

Suitable wetting agents include alkylbenzene and alkyl naphthalene sulfonates, sulfuric acid esters of fatty alcohols, amines, amino acids, sodium isothionate long-chain acid esters, sodium sulfosuccinate esters, sulfate and sulfonic fatty acid esters, sulfonation products resulting from the refining of petroleum, sulfonic oils two-third row acetylene glycols, polyoxyethylene alkyl phenols (especially isooctylphenol and nonylphenol), and polyoxyethylene mono fatty acid esters and hexite anhydride (e.g. sorbitan). Preferred dispersants are methyl cellulose, polyvinyl alcohol, sodium ligninsulfonates, polymeric alkyl naphthalene sulfonates, sodium naphthalene sulfonate and polymethylene bisnaphthalene sulfonate.

Wettable powders are water-dispersible formulations containing at least an active ingredient, an inert solid filler and one or more wetting agents and dispersants. The inert solid fillers are mostly organic substances such as natural clays, diatomaceous earth, synthetic silica-derived materials, etc. Examples of such fillers are kaolinite, attapulgite clay and synthetic magnesium silicate. Wettable powder compositions usually contain from more than 0.5 to 60 parts by weight (preferably 5-20 parts by weight) of active ingredient, about 0.25 to 25 parts by weight (preferably 1-15 parts by weight) of a wetting agent, about 0.25 - 25 parts by weight (preferably 1-15 parts by weight) of a dispersant and from 5 to about 95 parts by weight (preferably 5-50 parts by weight) of an inert solid filler, based on the total weight of the formulation. If desired, about 0.1-2.0 parts by weight of the filler may be replaced with a corrosion inhibitor, an antifoam, or a mixture thereof.

Other formulations of the composition include dust concentrates containing 0.1-60% by weight of the active ingredient on a suitable filler. These formulations may be diluted before use to a concentration of about 0.1-10% by weight.

Aqueous suspensions or emulsions can be prepared by mixing a non-aqueous solution of the water-insoluble active ingredient and emulsifier with water until homogeneous, followed by homogenization to obtain a stable very fine particle emulsion. The small particle size of the resulting concentrated suspension is its characteristic feature, thanks to which, after dilution and spraying, a very even coverage of the preparation is obtained. The active ingredient content of such formulations is about 0.1-60% by weight, preferably 5-50% by weight, with the upper limit of the concentration being determined by the solubility of the active ingredient in the solvent.

Concentrates are usually solutions of the active ingredient in water-immiscible or only partially water-miscible solvents containing a surfactant. Suitable solvents for the active ingredient are dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, hydrocarbons, and water-immiscible ethers, esters and ketones. Other highly concentrated concentrates can be prepared by dissolving the active ingredient in a solvent and then diluting the solution, e.g. with kerosene, to a spray concentration.

Concentrated agent formulations generally contain about 0.1-95 parts (preferably 5-60 parts by weight) of active ingredient, about 0.24-50 (preferably 1-25 parts by weight) of surfactant and, optionally, about 4-94 parts by weight of solvent. based on the total weight of the emulsifiable oil.

Granules are physically solid particulate preparations containing the active ingredient adhering to or dispersed within a solid matrix, that is, an inert fine filler. A surfactant, for example as mentioned above, may be present in the formulation to facilitate the release of the active ingredient from the granulate particles. Natural clays, pyrophilics, illite, vermiculite, etc. can be used as solid fillers. Preferred fillers are porous, readily absorbable pre-fabricated particles such as pre-fabricated and sieved attapulgite, thermally expanded particulate vermiculite and fine clays, e.g. kaolin clays, hydrated. attapulgite and bentonite clays. These fillers are sprayed on or mixed with the active ingredient to form granules.

The granular compositions may contain from about 0.1 to 30 parts by weight of active ingredient per 100 parts by weight of clay and up to about 5 parts by weight of surfactant per 100 parts by weight of clay.

The compositions may also contain other additives, e.g. fertilizers, other herbicides, other pesticides, antidotes, etc., as adjuvants or in admixture with any of the adjuvants mentioned above. The chemical compounds that can be included in the agents include, for example, triazines, ureas, sulfonylureas, carbamates, acetamides, acetanilides, uracils, acetic acid or phenol derivatives, thiolcarbamates, triazoles, benzoic acid derivatives, nitriles, heterophenyl ethers, nitrophenyl ethers, phenyl, pyridines and the like, such as:

Heterocyclic Azomine Compounds / Sulfur 2-Chloro-4-ethylammo-6-isopropylamino-s-tri; azine 2-Chloth-46-diisopropylamino-s-triazine

2-Chloro-4,6-dimylamino-s-triazine

3- isopropyl-2,2-dioxydo-1H, 3H-2,3 ₎ 3-ben3otiadi; orynoa-4

3-Amino-1,2,4-triazole

6,7-dihydropyridio 1,2-: 2 ', 1' - salt:)) ^ iira_vd; ^ ynow

170 158

5-Bromo-3-isopropyl-6-methyluracil

11'-Dimethyl-4,4'-bispyridine

2- (4-Isopropyl-4-methyl-5-ketoimidaaollnyl-2) -quinolecarboxylic acid-3

Salt of isopropylamine and 2-4-isopropyl-4-methyl-5-ketoimidazolinyl-2) nicotinic acid

Methyl 6- -4-isopropyl-4-methyl-5-oxoimidaaolinyl ^^ m-tooueeecarboxylate and methyl 2-4-isopropyl-4-methyl-5-oxoimidazolinyl-2) -p-oluenecarboxylate

Ureas / Sulfonylureas N- (4-ch] orc) phenoxyyphenyl-N, N-dimetholurea N, N-dimethyl-N'I (3-chloIΌ-4-methylphenylurea 3--3 ₎ 4-Dichloro-phenyl) -1,1- dimethylurea 1,3-Dimethyl-3-Ibeezoliazollio-2) urea 3-Ip-Chlorophenyl) -1,1-two-methyl Ioi-towel

1-Butyl-3-I3,4-dichlorophenyl) -1-methylurea

2- Chloro-N- [4-methoxy-6-methyl-1,3,5-oiiaynyl-2) aminocarbonyl] benzenesulfonamide Nd (2-methoxycarbbnylphenylsulfinyl) -IN '--4,6-bis-difluoromethoxypyrimidin Io-2) unicorn

Methyl 2--4,6-dimetholopyrimidinyl-2) aminocarbonylaminosulfonylbenzoate 2--4,6-dimethylpyrimidinyl-2) aminocarbonylaminosulfonylmethylbenzoate 2-I4,6-Dimethoxypyrimidinyl-d) aminocarbonylaminosulfonylmethyl 1,3,5-Ioiaayyylo-d) aminocarbonylaminosul (Όny (methyl benzoate

Carbamates / Thiolcarbamates Diethyldithiocarbamate 2 -: h ^ l (^ i ^ c ^ ^ lyl N, N-Diethylthiolcarbamate S - 4-3-chlorobenzyl)

Isopropyl Nd'olcarbamate N, N-Diisopropylthiolcarbamate S-2,3-dichloroallyl N, N-dipropylthiolcarbamate SN, N-Dipropylthiolthiolcarbamate S-propyl N, N-Diisopropylthiolcarbamate S-2,3,3-chloroallylchloroallyl.

Ac ^ idy 2-Chloro-N, N-diallylacetamide N, N-Dimethyl-2,2-diphenylacetamide

N- (2,4-Dimethylthienyl-3) -N-I1-methoxypropyl-2) -2-chloroacetamide

N- (1H-pyrazolyl-1-methyl-N-I2,4-dimethylthienyl-3) -2-chloroacetamide

N- (1-PyriazolylIl-methyl) -N-I4,6-dimethoxypyrimidinyl-5) -2-chloIΌacetamide

N- (2,4-Dimethyl-5-trifluuromethylsulConylaminophen (o) -acetamide

N-Isopropyl-2-chloroacetanilide

N-Isopropyl-1- (3.5.5 djm ethyl-clohexen-1-l-lo-2-chloro-cetamcl

2 ', 6' -Diethyl-N-butoxymethyl-2-chloroacetanilide

2 ', 6' -Dieethyl-N- (2-n-propoxyethyl) -2-chloIΌacetanilide

2 ', 6' -Dimethyl-N- (1-pyrazoyl o- - -moyylI-2-chloroacotanllide

2 ', 6' -Disetyl-IN-methoxymetyio-2-chloroacetanilide

2'-Methyl-6 '-etholo-N-I2-methoxs'propyl-2) -2-chloIΌacetanilide

2'-Methyl-6'-ethyl-N-ethoxymethyl-2-chloroIacetanilide α, α, a-Trifluoro-2,6-dinitro-N, N-dipropyl-pdoIuidine

N- (1,1-Dimethiopropynyl) -3,5-dichlorobenzamide

Acids / Esters / Alcohols 2,2-Dichloro-propionic acid 2-Methyl-4-chloro-phenoxyacetic acid 2,4-dichlorophenoxyacetic acid 2-4-2,4-Dichlororeeoxyypheoxy] propionate 3-amino-2,5-diacetic acid Chlorobenzoic acid 2 -ιηε- ^ γ-3 ^ -diclHorobenzoic acid 2,3,6-IoocchloIΌphenylacetic acid N-1 -n aphthous acid 'ofta! amy

170 108

Sodium 0-2-ChloIΌ-4dr6jfluoromethylphenoxyd2-mtrobenzoate

4.6- Dwunitio - o-II-row. butylphenol

Butyl N-Phosphonomethylglycine and its salts (R) -2 - Tr6fuoΓomeryl6ydinyl-2-oxy) phenoxy] pyropionate.

Ethers

2,4-Dichlorophenol 4-nitrophenyl ether

2-chloro-8, δ, δ trifluoro-p-dolll-3-deo-oxydiirophenyl phenyl ether

0--2-ChloIΌ-d-trifluoIΌmeeylphenoxy) -N - neeylsulfonyl

2-nitrobenzamide

0--2-Chloro-4dr6jfluoromethylphenoxide2d ^ itrobenzoate

-carboethoxyethyl

Various

2.6- Dichlorobenzonitrile

Sodium hydrogen methanesonate

Disodium methanarsonate

2--2-Chlorophenyl) methyl-4,4-dimethyl-3-isoxazolidinone-3-exo-1-methyl-4- (- -neejyloriiyld2- (2-methylphenylmethoxydo-oxabicyc) [2.2.1 jheptnn Glyphosate and its salts .

As fertilizers useful in combination with the active ingredients, mention may be made of ammonium nitrate, urea, potash, and superphosphate. Other useful additives are materials in which plants take root and grow, such as compost, manure, humus, sand, etc.

The herbicidal formulations of the types described above are shown in the following examples which illustrate some of their variants.

I. Emulsifiable concentrates wt.%

A. Compound No. 9.8 11.00

A complex of an organic phosphate and a hydrophobic aromatic or aliphatic base in the form of free acid (e.g. GAFAC RE-6W produced by

GAF Corp.). 5.59

Block copolymer of polyoxyethylene and eolioxyproeylene with butanol (e.g.

Tergitol XH produced by Union Crrbide Copp.n 1J1

Phenol 5.34

Monochlorobenzene 76.96

100.00

B. Compound No. 261 25.00

A complex of organic phosphate and a hydrophobic aromatic or aliphatic base in the form of a free acid (e.g. GAFAC RE-61, 5.00

Block copolymer of polyoxyhrylate and polyoxypropylene with butanols (e.g.

Tergitol XH) 1.60

Cyclohexanone 4.70

Monochlorobenzene 63.65

100.00

C. Compound No. 291 12.00

A complex of an organic phosphate and a hydrophobic aromatic or aliphatic base in free acid form (e.g. GAFAC RE-61, produced by

GAF Corp.) 6.00

Block copolymer of polyoxyethylene and polyoxypropylene with butanol (e.g.

Tergitol XH produced by Union □ ηΓόΜε (^ opp. · E50

Cyclohexanone 5.50

Aromatic 2, 75.00

100.00% by weight

D. Compound No. 229 20.00

Complex of organic phosphate and a hydrophobic aromatic or aliphatic base in free acid form (e.g. GAFAC RE-610) 5.00

Block copolymer of polyoxyethylene and polyoxypropylene with butanol (e.g.

Tergitol XH) 2.00

Cyclohexanone 5.00

Monochlorobenzene 68.00

100.00

E. Compound No. 312 11

A complex of an organic phosphate and a hydrophobic aromatic or aliphatic base in free acid form (e.g. GAFAC RE-610 from

GAF Corp.) 5.59

Block copolymer of polyoxyethylene and polyoxypropylene with butanol (e.g.

Tergitol XH produced by Union Carbide Corp.) Ι, Π

Cyclohexanone 5.34

Monchlorobenzene 76.99

100.00

F. Compound No. 282 25.00

Complex of organic phosphate and a hydrophobic aromatic or aliphatic base in free acid form (e.g. GAFAC RE-610) 5.00

Block copolymer of polyoxyethylene and polyoxypropylene with butanol (e.g.

Tergitol XH) 1.60

Cyclohexanone 4.77

Monchlorobenzene 66.65

100.00

II. Liquid preparations

A. Compound No. 261 25.00

Methylcellulose 0.30

Colloidal silica 111 ^ 50

Sodium lignosulfonate 3.5 0

N-methyl-N-oleiiotaurinic acid sodium salt 1.00

Water 66.70

100.00

B. Compound No. 270 45.00

Methylcellulose 0, 0

Colloidal silica 1.55

Sodium lignosulfonate 3, ^ 50

N-methyl-N-oleylauric acid sodium salt 1.00

Water 44.70

100.00

C. Compound No. 294 333.00

Methylcellulose 0, 3

Colloidal silica 1.55

Sodium lignosulfonate 3.55

N-methyl-N-oleylauric acid sodium salt 3.0

Water 66.00

100.00

170 158% by weight

D. Compound No. 135 23.00

Methylcellulose 0.50

Colloidal silica 2.00

Sodium lignosulfonate 3.50

N-methyl-N-oleylauric acid sodium salt 2.00

Water 69.00

100.00

E. Compound No. 148 45.00

Methylcellulose 0.30

Colloidal silica 1.50

Sodium lignosulfonate 3.50

N-methyl-N-oleylauric acid sodium salt 1.00

Water 47.70

100.00

III. Powders for suspensions

A. Compound No. 261 25.00

Sodium lignosulfonate 3.00

N-methyl-N-oleylauric acid sodium salt 1.00

Amorphous (synthetic) silica 71, qq

100.00

B. Compound No. 312 45.00

Dioctyl sodium sulfosuccinate 1.25

Calcium lignosulfonate 1.75

Amorphous (synthetic) silica 52.00

100.00

C. Compound No. 237 10.00

Sodium lignosulfonate 3.00

Sodium N-methyl-N-oleyl taurate 1.00

Kaolinite clay 86.00

100.00

D. Compound No. 463 30.00

Sodium lignosulfonate 3.00

Sodium N-Methyl N-oleyl taurate 1.00

Kaolin 56.00

Amorphous silica (synthetic)] Q, Q

100.00

E. Compound No. 446 75.00

Dioctyl sodium sulfosuccinate 1.25

Calcium Lignosulfonate 175

Kaolin 12.00

Synthetic amorphous silica 10.00

100.00

F. Compound No. 482 15.00

Sodium lignosulfonate 3.00

Sodium N-methyl-N-oleyloutinate 1.00

Synthetic amorphous silica 10.00

Kaolinite clay 71.00

100.00

170 158

IV. Granules - *% by weight

A. Compound No. 47 15.00

Dipropylene glycol 5.00

Granulated attapulgite (20/40 mesh) 80.00

100.00

B. Compound No. 390 H.OO

Dipropylene glycol 5.00

Diatomaceous earth (20/40) 80.00

100.00

C. Compound No. 399 1.00

Ethylene glycol 5, (00

Methylene blue 0.10

Pyrophyllite 93.90

100.00

D. Compound No. 393 5.00

Ethylene glycol 5.00

Pyrophyllite (20/40) 90.00

100.00

E. Compound No. 312 H.OO

Propylene glycol 5.00

Granulated attapulgite (20/40 mesh) 80.00

100.00

F. Compound No. 324 25.00

Diatomaceous earth (20/40) 77, QQ

100.00

G. Compound No. 261 5.00

Ethylene glycol 5, () 0

Methylene blue 0, 0

Pyrophyllite (20/40) 88.00

100.00

V. Suspension concentrates

A. Compound No. 262 11.00

Nonylphenol ethxylate (9.5 mol. Ethyl) Sterox NJ 11.80

Sodium lignosulfonate (Reax 88B) 11.22

Water 55.00

100.00

B. Compound No. 446 32.55

Potassium salt of the condensation product of naphthalenesulfonate and formaldehyde (DAXAD 11 KLS) 9.00

Nonylphenol ethoxylate (10 mole ethyl t.) (Igepal CO-660) 9.00

Water 49 / .5

100.00

C. Compound No. 76 11.00

Dioctyl sodium sulfosuccinate Aerosol OTB 11.00

Castor oil + 36 ethylene oxide (FloMo 3G) 11.00

Water 77.00

100.00

170 158% by weight

D. Compound No. 261 15.0

Nonylphenol ethoxylate (9.5 mol. Ethyl) Sterox NJ 1.0

Sodium lignosulfonate (Reax 88B) 5.0

Water 79.0

100.0

E. Compound No. 290 30.0

Potassium salt of the condensation product of naphthalenesulfonate and formaldehyde (DAXAD 11 KLS) 4,0

Nonylphenol ethoxylate (10 moles ethyl t.) (Igepal CO-660) 2.0

Water 64.0

100.00

F. Compound No. 135 18.0

Nonylphenol ethoxylate (9.5 mol. Ethyl) Sterox NJ 14.0

Sodium lignosulfonate (Reax 88B) 12.2

Water 56.0

100.0

G. Compound No. 148 34.0

Potassium salt of the condensation product of naphthalenesulfonate and formaldehyde (DAXAD 11 KLS) 8,0

Nonylphenol ethoxylate (10 mole ethyl t.) (Igepal CO-660) 10.0

Water 48.0

100.0

H. Compound No. 482 14.0

Dioctyl sodium sulfosuccinate Aerosol OTB 3.0

Castor oil + 36 ethylene oxide (FloMo 3G) 3.0

Water 80.0

100.0

VI. Liquid concentrates

A. Compound No. 76 20.0

Xylene 80.0

100.0

B. Compound No. 229 10.0

Xylene 90.0

100.0

C. Compound No. 217 25.0

Xylene 75.0

100.0

D. Compound No. 482 15.0

Xylene 85.0

100.0

VII. Microcapsules

A. Compound No. 135 encapsulated in a polyurea 4.5 shell

Reax® C-21 1.5

NaCl 5.0

Water 89.0

100.0

170 158% by weight

B. Compound No. 137 encapsulated in a 20.0 polyurea shell

Reax® 88B 2.0

NaN O, 10.0

Xylene 30.0

Water 38.0

100.0

C. Compound No. 138 Encapsulated in a Polyurea 4.8

Reax® 88B 1, ^

NaNOs 5.0

Kerosene 20.0

Water 6 * 9.0

100.0

D. Compound No. 148 encapsulated in a poly (urea-formaldehyde) 50.0 shell

Reax® C-21 1, 5

NaCl 8.5

Petroleum oil (Aromatic 200) 20.0

Water 20.0

100.0

E. Compound No. 229 encapsulated in a poly (thiourea formaldehyde) shell 30.0

Reax® C-21 2.0

NaCl 8.0

Xylene 30.0

Water 30.0

100.0

F. Compound No. 261 encapsulated in polyurea 7,: 5

Reax® 88B 1, 5

NaCl 8.0

Aromatic 200 30.0

Water 53.0

100.0

G. Compound No. 308 Encapsulated In Poly (Melamine Formaldehyde) 9.0 Sheath

Reax® 88B 2.0

NaNO, 10.0

Kerosene 40.0

Water 3390

100.0

H. Compound No. 446 Encapsulated in Poly (Urea Formaldehyde) Shell 115.0

Reax® 88B 10.0

NaNO, 8.0

Xylene 42.0

Water 25.0

100.0

I. Compound No. 312 encapsulated in polyurea 22.0 sheath

Reax® 88B 2.0

NaCl 8.0

Xylene 35.0

Water 33.0

100.0

17, 108

Effective amounts of the compounds according to the invention are applied to soil containing seeds or vegetative shoots, or they are incorporated into the soil by any known method. The application of liquid or solid formulations of the agent to the soil can be carried out, for example, with the use of motor sprayers, hand-held and boom sprayers, and duster-sprayers. The formulations can also be applied from airplanes as dusts and spray liquids thanks to their effectiveness at low doses. The exact amount of active ingredient to be applied depends on many factors, including the plant species and stage of development, soil type and condition, amount of rainfall and the particular application of the compound. In the selective pre-emergence treatment, that is to say on the soil, a rate of from about "0 g / ha) to about 11.2 kg / ha is applied. A preferred rate is from about 0.001 kg / ha (1.0 g / ha) to about 0.1 kg / ha (0.0 g / ha). Higher or lower dosages may be required in some cases. One skilled in the art will readily determine the optimal dose upon reading this description and the examples therein.

The term soil is used herein in its broadest sense and includes all known soils as defined in Webster's New International Dictionary, Second Edition, Unabridged (1961). Thus, this term covers all substances or environments in which plants can take root or grow, not only soil, but also compost, manure, muck, clay, silt, sludge, clay, humus, sand, etc., adapted as carriers supporting plant growth.

170

Publishing Department of the UP RP. Circulation of 90 copies. Price PLN 6.00

Claims (3)

Patent claims 1. A process for the preparation of new aryl-haloalkylpyrazoles of formula I wherein Ri means Ci - aHcil; C3-8 cycloalkyl; cycloalkenyl, cycloalkylalkyl or cycloalkenylalkyl; C2-8-ancenyl or alkynyl; benzyl; the above R 1 groups may be substituted by halogen, amino, nitro, cyano, hydroxy, alkoxy, alkylthio, X X -CYR8, -CR9, YR10 or NR, R, ₂ ; R2 is CO5 -: lilor ^ o ^{^} halogenalkyl; R3 is halogen; R 4 is R 1, thioalkyl, alkoxyalkyl, or polyalkoxyalkyl, carbamyl, halogen, amino, nitro, cyano, hydroxy, Cla () - heterocyclyl containing O, S (O) m and / or NR 1 heteroatoms C 6-10 aryl, aralkyl or alkaryl, X X II II --CYR3, -CR 14, YRo or NR10R10, any two R4 groups may be linked via a saturated and / or unsaturated carbon atom, --C = X) - and / or O, S (O) m and / or NR, forming a cyclic ring of up to 9 members, optionally substituted with any of R4; where, when this bridge includes ABOUT II -C-NR18, then said cyclic ring has at least 6 members X is O, S (O) m, NR19 or CR20R21; Y is O or S (O) m or NR22; R8 - R22 are hydrogen or one of the R4 groups; m is 0-2 and n is 1-5, and the agriculturally acceptable salts and hydrates thereof, characterized in that the compound of formula B Wherein R 1, R 2, R-4 and n are as defined above, is reacted with a halogenating compound. 2. The method according to p. A compound according to claim 1, characterized in that the compound of formula Ilia is used in which R1 is C1-5 alkyl, R2 is C1-5 haloalkyl, R5 is hydrogen or halogen, R6 is hydrogen or R4, R7 is hydrogen or R4 and R6 and R7 can be joined via a saturated and / or unsaturated carbon atom, - (C = X) - and / or a hetero-bridge, O, S (O) _m, and / or NR18, to form a cyclic ring of up to 9 members, optionally substituted with any of the R4 groups, which when the bridge includes ABOUT II -C-NRis-, then said cyclic ring has at least 6 members and X, Y, R4, R8-R22 and m are as defined in formula I. 3. The method according to p. The process of claim 2, wherein R 1 is methyl; R2 is CF3, CF2Cl or CF2H; R5 is fluoro and Re and R7 are as defined above, and a halogenating agent in which a chlorine or bromine atom is present.