CA1075030A - Herbicidal compositions and pyrazole derivatives - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
The present invention provides a herbicidal composition including a compound having the formula (I)

Description

1075(~30 This invention relates to the use of pyrazole deriva-tives as herbicides.
This application is a divisional application copending application No. 222,945 filed March 24, 1975.
According to copending application No. 222,945 there is provided a compound having the formula R ~ Xn ~I) N~N

R

wherein; Rl represents hydrogen atom or an alkyl group;
R2 represents an alkyl group or an alkenyl group;
X represents a halogen atom, a nitro group, an alkyl group, a halogenated alkyl group, an alkoxy group, an alkane-sulfonyl group, a cyano group, an alkylthio group, an aliphatic acyl group or a benzoyl group;
n is 1, 2, 3 or 4 and when n is 2, 3 or 4, the sub-stituents X may be the same or different; and Y represents an oxygenatom or sulfuratom and providedthat -X is other than a 2-chloro or 4-nitro substituent when and R are methyl n is 1 and Y is an oxygen atom andprovided that when n is 1, 2 or 3, and Y is oxygen at least one of the radicals X, Rl and R2 is other than alkyl or a salt thereof or an organic acid ester thereof.
In copending application No. 299,625 filed March 23, 1978 which is also a divisional application of copendino application No. 222,945, there are provided herbicidal compositions containing pyrazolederivativeshaving the formula (I) and salts and esters thereof as defined above, where X repre-sents a 2-chloro or-4-nitro substituent Rl and R represent 1075~)30 methyl groups, n is 1 and Y represents an oxygen atom.
(The syntheses of 1~3-dimethyl-4-(2-chlorobenzoyl)-5-hydroxypyrazole and 1,3-dimethyl-4-(4-nitrobenzoyl)-5-hydroxy-pyrazole are briefly disclosed without any indication of their properties in "The Chemistry of Heterocyclic Compounds" (Russian origin, 1972, No. 6, 799-804)).
According to the present invention there is provided a herbicidal composition including a compound having the formula ¦¦ ,r~ Xn , Rl ~ ~ I C

N ~
¦ OH

wherein Rl is an alkyl group; R2 is an alkyl group, X is an alkyl group and n is 1, 2, or 3 and when n is 2 or 3 the substituents -X may be the same or different, or a salt thereof or an organic acid ester thereof together with an agriculturally acceptable carrier or diluent.
The present invention also provides a method for the control of unwanted plants which comprises applying to said plants or the soil a herbicidal composition containinga compound having the formula (I) or a salt or ester thereof as defined ~ above wherein Rl is an alkyl group; R is an alkyl group, X is - an alkyl group and n is 1, 2, or 3 and when n is 2 or 3 the sub-stituents X may be the same or different, or a salt thereof or an organic acid ester thereof together with an agriculturally acceptable carrier or diluent.
The compounds of the above-mentioned formula (I) may be - present in the form of the tautomerism as shown below.

.

~075~30 R ~ C

(IV) E C ~ ~ 0~/ ~Oi~
~ ¢ ~ ~ N~ N

R R

(II) (I) (III) (wherein R, R r and .X~ and. n ha~e the same meaning as above In the above-mentioned formula (I), R is preferably a straight or branched alkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, e. g. a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, ~-pentyl, isopentyl, s-amyl, 2-methylbutyl, t-amyl, n-hexyl,

2-hexyl, 2-methylpentyl, 3-mcthylpentyl, 4-methylpentyl, 3-hexyl, 2-ethylbutyl, 2-methyl-2-pentyl or 2, 2-dimeth~lbutyl group.

R preferably is a straight or branched alkyl group haYing 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, as exemplif ied with regard to R

--` 1075()30 X is pre~er~ ly a strai~ht or branched alkyl group having 1 to 4 carbon atoms such as a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl group, particularly a methyl group;
A most preferable group in view of their herbicidal activities of the compounds having the above formula ( I ) includes those wherein Rl is methyl group, R2 is r.lethyl group, X is a :
methyl group and n is 1, 2 or 3, when n is 2 or 3, the substituents X being the same or dif ferent .
The salts of the compounds of the above-mentioned formula --(I) include the salts with monovalent to trivalent metallic ions such as sodium, potassium, calcium, magnesium, aluminium, iron, manganese, zinc, nickel, cobalt or copper; the salts with complex ions such as [Cu(H2O)2] , [Mn(H2(~2] , [Ni(H2O)4]
lAl(OH)], lZn(OH)], [Cu(OH)], [Cu(NH3)2] or [Co(NH2CH2CH2NH2)] ; the salts with ammonium ion such as ~ -4 3 3 2( 2H5)2~ N H3CH(CH3)2, N H3CH2CH OH
or N H3CH2CH2OC2H5; the salts with mineral acids such as hydrochloric acid, sulfuric acid, nitric acid or hydrobromic acid.

The organic acid esters of the compounds of the above- ~ -mentioned formula (I) in particular include esters which are capable of releasing the original compounds (I) by decomposition upon application. Acids which provide such esters include:

. .

~075030 ~1) an aliphatic, alicyclic or aromatic carboxylic acid of the formula R COOH
wherein R is a straight or branched alkyl group having 1 to 17 carbon atoms such as a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, heptyl, undecyl, tetradecyl or heptadecyl group;
an alkyl group having 1 to 4 carbon atoms, particularly 1 to 2carbon atoms, and substituted with 1 to 4 halogen atoms, such as a chloromethyl, bromomethyl, iodomethyl, 2, 2, 2 -trichloro-ethyl, 2, 2-dibromoethyl, 2, 2, 2-tribromoethyl, 2-iodoethyl, 2, 2-di-iodoethyl, or 1, 2, 2-tetrafluoroethyl group;
a ætraight or branched alkenyl group having 2 - 17 carbon atoms, particularly 3 - 5 carbon atoms, such as. a vinyl, isopropenyl, propenylJ l-methyl-2-propenyl, 2-methyl-2-propenyl, 2-butenyl, 15 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-butenyl, 1-methyl-3-butenyl, 2 -methyl- 3 -butenyl, 2 -heptenyl, 2 -unde cenyl, 2 -tetra -decenyl, 2-heptadecenyl, 3-heptadecenyl or 8, ll-heptadecadienyl group;
a 5- to 7-membered cycloalkyl group such as a cyclopentyl, cyclohexyl or cycloheptyl group;
a phenyl group which may have 1 to 3 substituents selected Irom a nitro group, a halogen atom and an alkyl group of 1 to 4 carbon atoms, particularly 1 carbon atom, such as a phenyl, 2-nitrophenyl, 4-nitrophenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2-chloro-phenyl, 4-chlorophenyl, 2-bromophenyl, 4-bromophenyl, 2, 4-dichlorophenyl, 2, 4, 6 -trichlorophenyl or 2 -chloro -4 -nitrophenyl group;
a phenylalkyl group which may have 1 - 3 substituents selected from nitro groups and halogen atoms in the phenyl moiety and which has 1 - 5 carbon atoms, particularly 1 or 2 carbon atoms, in the alkyl moiety, such as a benzyl, phenethyl, phenylpropyl, phenylbutyl, phen~pentyl, 4-nitrobenzyl, 4-nitro-phenethyl, 2-chlorobenzyl, 4-chlorophenethyl, 2-bromobenzyl, - -4-bromophenethyl, 3-(2, 4-dichlorophenyl)propyl or 4-(2, 4, 6-trichlorophenyl)butyl group;
a styryl group;
or a phenoxyalkyl group which may have 1 or 2 substituents selected from halogen atoms and methyl groups in the phenyl moiety and has 1 to 3 carbon atoms in the all~l moiety;

(2) a carbamic acid of the formula 5 ~ NCO . OH -wherein R and R individually represent a straight or branched aL~yl group having 1 - 4carbon atoms such as a methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl group or R4 and R5 jointly represent pentamethylene group;

(3) a sulfonic acid of the formula R6 _ S02 - 0 ~075030 wherein R represents a straight or branched alkyl group having 1 - 4 carbon atoms such as a methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl group;
an alkyl group substituted with 1 - 3 halogen atoms and having 1 - 3 carbon atoms, partia~larly 1 or 2 carbon atoms such as a chloromethyl, bromomethyl, iodomethyl, trifluoro-methyl, l-chloroethyl, l-bromoethyl or 1,1-dichloroethyl group;
or a phenyl group which may be substituted by a straight or branched alkyl of 1 - 12 carbon atoms, particularly 1 or 2, carbon atoms, e. g., a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or dodecyl group or by a halogen atom, e. g., chlorine;
.
t4) a diester of thiophosphoric acid of the formula R70~~~
7 ~P - OH
wherein the substituents R7 may be the same or different and represent a straight or branched lower alkyl group having 1 - 4 carbon atoms such as a methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl group;

(5) a monoester of carbonic or thiocarbonic acid of the formula p R8 _ y - b OH
wherein R represents a straight or branched lower all;yl group having 1 - 4 carbon atoms such ~s a methyl, ethyl, n-propyl, .. . . . . .
. ~ ~
.

l:`

1~)7S030 isopropyl, n-butyl, isobutyl or s-butyl group;
a phenyl group;
or a phenylalkyl group which may have 1 - 3 substituents selected from nitro groups and halogen atoms in the phenyl moiety S and which has 1 or 2 carbon atoms in the alkyl moiety, such as a benzyl, phenethyl, 4-nitrobenzyl, 2-chlorobenzyl, 4-chloro-phenethyl, 2-bromobenzyl, 2,4-dichlorobenzyl or 2, 4, 6-trichloro-benzyl group;
and Y represents an oxygen atom or sulfur atom;

(6) a dibasic acid of the formula O ~ O ~ -:
HO C R C ¦-OH
Jm wherein m is O or 1;
R is an alkylene group having 1 to 10 carbon atoms such as a methylene, ethylene, trimethylene, tetramethylene, octa-methylene or decamethylene group; a vinylene group; an o-, m, or ~-phenylene group; or a carbon-carbon bond; and (7) a 3-oxo-4-isoxazolin-2-yl carboxylic acid of the formula R10 o - ~C ~ O~ N CO OH

.

~075030 wherein R is hydrogen atom or a halogen atom.

Preferred acids for esterification include the carboxylic acid having the above formula -~herein R is a halogen~lkyl group having 1-2 carbon atoms and 1-4 halogen atoms, an aL~cenyl group having 3-5 carbon atoms, a 5- or 6-membered cycloallcyl group, a phenyl group, optionally having 1-3 substituents selected from nitro groups, methyl groups and halogen atoms; a phenylalkyl group having 1 or 2 carbon atoms in the alkyl moiety and optionally having 1-3 substituents selected from nitro groups and halogen atoms in the phenyl moiety; or a phenoxyalkyl group having 1 or 2 carbon atoms in the alkyl moiety and optionally having 1 or 2 substituents selected from halogen atoms and nitro groups; the sulfonic acids having the above formula wherein R is an alkyl group of 1 - 3 carbon atoms, a halogenoalkyl group of 1 or 2 carbon atoms and 1-3 halogen atoms or a phenyl group optionally having Cl or C2 alkyl or halogen substituents; and the dibasic acids having the above formula wherein R is an alkylene group of 1 - 3 carbon atoms and m is zero or 1.

Compounds having the above-mentioned formula (I) which may be employed in the present herbicidal composition are illustratively exemplified as hereundcr (Compound No.
will be frequently referred to hereinbelow).

. ~ --- . . .

~07s030 Compound ~ Compound 1. 1,3-dimethyl-4-(4-methylbenzoyl)-5-hydroxypyrazole 2. 1,3-dimethyl-4-(3-methylbenzoyl)-5-hydroxypyrazole 3. 1,3-dimethyl-4-(4-tert-butylbenzoyl)-5-hydroxypyrazole

4. 1,3-dimethyl-4-(3,4-dimethylbenzoyl)-5-hydr~xypyrazole

5. 1,3-gimethyl-4-(3,5-dimethylbenzoyl)-5-hydroxypyrazole

6. 1,3-dimethyl-4-(2-methylbenzoyl)-5-hydroxypyrazole

7. 1,3-dimethyl-4-(2,4-dimethylbenzoyl)-5-hydroxypyrazole Of the above-illustrated pyrazole compounds compound No. 6, may be mentioned as preferable The compounds having ~e above formula(l), saltsthereoi and organic acid estersthereofcan be readily prepared, for example, bythe following processes.

PROCESS A
The 5-hydroxypyrazole derivatives(VI)can be easily ~ prepared by reactingthe 5-pyrazolone derivatives(V~) with the acylhalides(VIII),inthe presence of an acid-binding agent;
asinthefollowingequation:

R ~ ~ Xn ~ CO ~

(VII) (VI~) (VI) `
(wherein R , R , ~ and n havethe same meanings as above an~
lIalrneans a halogen atom).

-, ~075~30 The above reaction may be preferably effected in the presence of a solvent. As the solvent employable, any solvent may be used without particular limitation if it wot~ld not participate in the reaction and there may be mentioned, for instance, ethers or mixtures thereof such as diethyl ether, tetrahydrofuran, diethyl ether!dioxan, tetrahydrofuran/dioxan;
halogenated hydrocarbons such as dichloromethane, carbon tetrachloride; secondary or tertiary alcohols such as isopropanol, isobutanol, t-butanol; and the like. In particular, ethers and secondary alcohols are preferably employed. The reaction is also preferably effected in the presence of a catalyst.

The catalyst may be an alkaline earth metal hydroxide such as calcium hydroxide. In particular, calcium hydroxi~e is preferably used. The amount of a catalys. to be employed is preferably l - 2 moles per mole of the start.ng material (VII). The reaction temperature is not particularly critical and the reaction may be effected at room temperature or - a reflux temperature of the solvent employed. Particularly, the reaction may be preferably conducted at a reflux temperature of the solvent employed. The reactioll period may vary mainly upon the reaction temperature and the sort of the reagent employed, but it is usually within a range of about 1 to 1~ hours.
The acyl halides which may be employed in the above-mentioned reaction may be, for example, acid chlorides or acid bromides.

~075l)30 After completion of tlle reaction, the desircd compounds may be recovered from the reaction mixture by a conventional method. ;~he starting materials of the formula (VII) may be prepared according to the method disclosed in Chemische Berichte, 43, 2106 (1910).

.
PROCESS B

The compounds having the formula (I) are obtainable by heating the corresponding 5-halogenopyrazole aerivatives (IX) with 10 alkali metal hydroxides such as sodium hydroxide or potassium - hydroxide.

~ / ~ " n~ /Xn 2 aLkali metal hydroxide ,. ~ R2 (IX) (I) wherein R, R, X and n have the same meanings as above.

In the above- mentioned reaction, water may be employed as a solvent or a mixture of water with an org:lnic solvent may be used and, as such organic solvents, may be mentioned, '.~

for example, ethers such as tetrahydrofuran or dioxan and alcohols such as metllanol or ethanol.The reaction temperature is not particularly critical and the reaction may be effected at room temperature or a reflux temperature of the solvent and, particularly, it can be preferably effected at a temperature around the reflux temperature of the solvent, The reaction ~` period depends mainly upon the reaction temperature and the reagent employed, but is usually about 1 to 10 hours.
Thestarting materials of the formula (IX) are prepared according to the method disclosed in Chemische Berichte, 50, 737 (1917) and United Kingdom Patent Specification No. 1 2G8 608.

PROCESS C
The organic acid esters of the compounds having the formula (I) are easily prepared by reacting the compounds of the formula (I) with an acylating agent as shown in the following scheme. X

I CO~ n C~SXn ~;~OR N;~
acylating agent 1 2 (I) (X) wherein R., R, X, and n have the same meanings as above and R represents a residue of an organic acid.

-13~

.'. ' ' ' ' ' ` ' ' 10751)30 The al~ove-mentioned reaction m ay be preferably cffected in the presence of a solvent. As the solvent which may be employed, there is no particular limitation on a solvent if it does not participate in the present reaction and, for example, ethers or mixtures thereof such as diethyl ether, tetrahydrofuran, diethyl ether/dioxane, tetrahydrofuran dioxan; aromatic hydrocarbons such as benzene, toluene, xylene; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride and, in particular, the aromatic hydrocarbons and ethers are preferably employed. Theacylating agents which may be employed are acyl halides such as acid chlorides and acid bromides; carboxylic acids in the presence of carbodiimides such as 1, 3-dichlorohexyl- -carl~odiimi~e; or acid anhydrides. Acid chlorides are preferable and the reaction is effected in the presence of an acid binding agent. The reaction temperature is not particularly critical and the reaction is usually conducted at room temperature to the reflux temperature of the solvent. The reaction period may vary mainly upon the reaction temperat~lre and the reagent used but is usually about 1 - 24 hours.

PROCESS D
The salts of the compound having the formula (I) with a metallic, a complex ion and ammonium ion are formed by adjusting a pH of a solution of the compound of 1he formula (I) to not less than about 3 in the presence of a cation. As the sol~Tent which may be used for the formation of the abo~Te-mentioned 1~5030 salts, there is no particular limitation and, for instance, are preferably employed water; alcohols such as methanol or ethanol; ethers such as tetrahydrofuran or dioxan; aromatic hydrocarbons such as benzene; halogenated hydrocarbons such as dichloromethane or chloroform or mixtures of these organic solvents with water. Depending upon changes in cation valency and solvent, various salts having different coordinate proportions of the compound having the formula (I) and the cation of l:l, 1:2, 1:3 and the like are formed.

ID PROCESS E -The salts of the compound having the formula (I) and a mineral ac;d are easily prepared by mixing the compound hav,ng the formula ~I) with the mineral acid in a suitable solvent. As the solvent which may be used, there is no particular limi.ation lS and there may be preferab~y mentioned, for instance, water; - -alcohols such as methanol or ethanol; ethers such as tetrahydroluran or dioxane, aromatic hydrocarbons such as benzene; halogenated hydrocarbons such as dichloromethane or chloroform; or mixtures of these organic solvent and water. In general, the salts with the mineral acid are formed at a pH not more than about 3.

.

The compounds of the above-mentioned formula (I) and salts and organic acid esters thereof have been found to possess a selective toxicity to weeds.

. - :' iO7S030 In a paddy field, particularly potent herbicidal effects can be obtained against perennial weeds such as those of the family Cyperaceae, for example, "Hotarui" (Scirpus hotarui Ohwi), (Cvperus serotinus Rottb, ) flatstage/and the like and those of the family Alismataceae, (Sagittaria trifolia L. ) (Sagittaria pygmea for example,. arrowhead (Omodaka)/and arrowhead (Urikawa), / Miq. ) which are difficult to control by conventional herbicides, by pre- -and post- emergenee treatrnent.ip.~oil without any harmful effect on newly-transplanted rice plants and growing rice;plants.
Furthermore, broad-leaved weeds such as monocotyledonous weeds such as those of the family Gramineae, for example, barnyardgrass, panic grass and the like, weeds of the family Scrophulariaceae, for example, false pimpernel, "Murasakisagigoke" (Mazus miquelii Makino), "Abunome" (Dopatrium junceum Hamilt) and the like, weeds of the family Cruciferae, for example, wavy bittercress, marsh yellow cress; " Mizutagarashi" (Cardamine lyrate Bunge) and the like, weeds of the family Lythraceae, for example, toothcup, "Mizumatsuba" (Rotala mexicana Chzm. ) and the like, and weeds of the family Compositae, for example, ragwort, American false daisy and the like.

In upland field, pre- and post- emergcnce treatment in soil has shown particularly potent effect against weeds of the family Caryophyllaceae, for example, common chic~iweed, bog stichwort, mouse-ear chick~veed, pearlwort and the li~e and, furthermore, weeds of the family Portulacacea, for example, , common purslane and the like, weeds of the family Amaranthaceae, `for example, -: . rough pi~weed and the like, weeds of the family Chenopodiaceae, for example, "Akaza" (Chenopodium album L. ), white goose-foot, "Koakaza" (C. ficifolium Smith) and the likè, weeds of the family Commelinaceae, for example, Asatic dayflower and the like, weeds of the family Labiatae, for example, henbit, "Kiranso" (Ajuga decumbens Thunb. ) and the ~ike, weeds of the family Oxalidaceae, for example, creeping wood sorrel, violet ~ood sorrel and the like, weeds of the family Leguminosae for example, "Nekohagi" (Lespedeza pilos Sieb et Zucc. ), hairy vetch, common vetch and the like, and weeds of the family Euphorbiaceae, for example, Virginia cooperleaf, milk purslane and the like can be effectively controlled. Narrow leaved weeds, in particular, those of the family Cyperaceae, such as chufa and the like are effectively controlled and those of the family Gramineae_ such as wheatgrass, crab-grass, Digitaria timorens Balansa, "Akinoenokorogusa" (Setaria Faberi Herrmann), foxtail and the like are also effectively controlled; On the other hand, crops such as rice plants, cereals, sugar beets, pulses, cotton plants, radishes, tomàtoes, carrots, Chinese cabbages, lettuces and the like do not suffer from phytotoxicity.

Additionally, the compounds having the above-mentioned formula (I) are effective as herbicides in other applications, e. g.
in a fruit-garden, an unplanted field or a forest.

~07s030 The compounds in this invention may be formulated for use to the preparations commonly employed as a herbicide, for example, powdery dusts, coarse dusts, fine granules, granules, wettable powders, emulsifiable concentrates, aqueous liquids, aqueous solutions, oil suspensions and so on, with admixture of a carrier or diluent and, if required, other auxiliary agents.
` The carrier as used herein means a synthetic or natural, inorganic or organic substance that can assist an active compound to reach the portion to be treated, and make it easy to store, transport or handle the active compound for admixing in the herbicidal composition.

As suitable solid carriers may be mentioned inorganic substances such as clays (which may be represented by I~aolinite, Montmorillonite or Attapulgite), talc, mica, pyrophyllite, pumice, vermiculite, gypsum, calcium carbonate, dolomite, diatomaceous earth, magnesium carbonate, apatite, zeolite, SiiiCiC anhydride, -and synthetic calcium silicate; vegetable organic substances such as soy-bean meal, tobacco powder, walnut powder, wheat flour;
wood meal, starch, and crystalline cellulose; synthetic or natural high polymer compounds such as cumarone resin, petroleum resin, alkyd resin, polyvinyl chloride, polyalkylene glycol, ketone resin, ester gum, copal gum, and dammar gum; waxes such as carnauba wax or beeswax; or urea.

As suitable liquid carriers may be n~cntioned paraffin or ~075030 naphthene hydrocarbons such as kerosene, mineral oil, spindle oil or white oil; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, or methylnaphthalene; chlorinated hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene, monochlorobenzene or o-chlorotoluene; ethers such as dioxan or tetrahydrofuran; ketones such as acetone, methylethylketone, diisobutylketone, cyclohexanone, acetophenone, or isophorone; esters such as ether acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate -or diethyl succinate; alcohols such as methanol, n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol or benzyl alcohol; ether alcohols such as ethylene glycol ethyl ether, or diethylene glycol butyl ether; polar aprotic solvents such as dimethylformamide or dimethyl sulfoxide; or ~ater. ~ -As surface active agents, for example for emulsification, dispersion, wetting, spreading, binding, controlled disintegration, stabilizing the active ingredient, improving fluidity or rust proofing one may use any non-ionic, anionic, cationic or amphoteric surfactant, but non-ionic and/or anionic agents are preferr--d.
As suitable non-ionic surface active agents may be mentioned, for example, polymerization adducts of ethylene oxide to hig,her alcohols such as lauryl alcohol, stearyl alcohol, oleyl alcohol and the like, polymerization adducts of etl-ylene oxide to all~l phenols such as isooctyl phenol, nonyl phenol and the like, pol~merizatioll adduct~

of cthylene oxide to all;yl naphtl~ols such as butyl naphthol, octyl naphthol and the like, polymerization adducts of ethylene oxide to higher fatty acids such as palmitic acid, stearic acid, oleic acid and the like, polymerization adducts of ethylene oxide to mono- -or di-alkyl phosphoric acids such as stearyl phosphoric acid, dilauryl phosphoric acid and the like, polymerization, adducts of ethylene oxide to amines such as dodecyl amine, stearic acid amide and the like, polymerization adducts of ethylene oxide to higher fatty acid esters of polyhydric alcohols such as sorbitan and said fatty acid esters, polymerization adducts of ethylene oxide to propylene oxide and so on. As suitable anionic suriace active agents may be mentioned, for example, alkyl sulfate salts such as sodium lauryl sulfate, oleyl sulfate amine salt and the like, alkyl sulfonate salts such as sodium dioctyl sulfosuccinate, sodium 2-ethylhexene sulfonate and the like, aryl su]fonate salts such as sodium isopropylnaphthalene sulfonate, sodium methylene-- bisnaphtl~alene sulfonate, sodium ligninsulfonate, sodium dodecylbenzene sulfonate and the like.

Moreover, the herbicidal compositions of this invention may be used in combination with high molecular compounds or other auxiliary agents such as casein, gelatin, albumin, glue, sodium alginate, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohQl and the like for improved properties and increased biological cffects thereof.

~075U30 The above-mentioned carriers and various auxiliary agents may be used alone or in any desired combination depending on the type of preparation, thc application and other factors.

In general, the herbicidal composition of this invention may contain the active compound (I) in an amount of 0.1 - 99%
by weight, based upon the composition.

Dusts may conveniently contain, for example, 1 to 25%
by weight of the active compound, the remainder being a solid carrier.

Wettable powders may conveniently contain, for example, - --25 - 90% by weight of the active compound, the remain<3er being a solid carrier and a dispersing and wetting agent, if required, together with a protective colloidal agent, a thixotropic agent, an anti-foaming agent and the like.

Granules may conveniently contain 1 - 35% by weight of the active compound, a major portion of the remainder being .
a solid carrier. The active compound is homogeneously admixed with the solid carrier or adhered or adsorbed onto the carrier suriace and the size of a granule is about 0. 2 - 1. 5 mm.

Emulsifiable concentrates may conveniently contain, for example, 5 - 50% by weight of the active compound and al~ont 5 -20~o by weight of an emulsifying agent, the remainder being a liquid carrier, together with a corrosive inhibitor if required.

; ' ' ' ' ' ' : ' :-: -~0'7S030 The herbicidal compositions of this invention, which are formulated into various types of preparations as above, may be applied in a paddy or dry field at 10 - 2000 g, preferably 100 - 500 g, of the active ingredient per 10 ares for pre- or post-S emergence soil treatment to control weeds effectively. Also, in order to control weeds unselectively in unplanted areas such as roads, grounds, house sites, railways and the like, an - -application rate of the active ingredient of 200 - 4000 g per 10 ares can be effective.

The herbicidal compositions of this invention may preferably be blende d with other herbicides for broader herbicidal spectra ' and, in some cases, a synergistic effect may be observed. As examples of such other herbicides may be mentioned, for instance, triazine type herbicides such as 2-methylthio-4, 6-bisethylamino-1, 3, 5-triazine; 2-chloro-4, 6-bisethylamino-1, 3, 5-triazine; 2-' ~ methoxy-4-ethylamino-6-isopropylamino-1, 3, 5-triazine; 2-chloro -4 -ethylamino - 6 -is opropylamino - s -triazine; 2 -methylthio -4, 6-bis -(isopropylamino)-s-triazine; and 2-methylthio-4-ethylamino-6-isopropylamino-s-triazine, 2, 4-dichlorophenoxyacetic acid and its methyl, ethyl or butyl ester; 2-chloro-4-methylphenoxy-acetic acid phenoxy type herbicides such as 4-chloro-2-methyl-phenoxyacetic acid or ethyl 2-methyl-4-chlorophenoxybutyrate, diphenyl ether type herbicides such as 2, 4, 6-trichlorophenyl-4' -nitrophenyl ether; 2, 4-dichlorophenyl-4Lnitrophenyl ether; or 3, 5-dimethylphenyl-4'-nitrophenyl ether, urea type herbicides such as 3 -( 3, 4 -diclllorophenyl)- 1-methoxy- 1 -methylurea; 3 -(3, 4-dichlorophenyl)-1, 1 -dimethylurea; or 3-(4-chlorophenyl)-1, l-dimethylurea, carbamate type herbicides such as 3-methoxycarbonylaminophenyl-N-(3-methylphenyl) carbamate;
isopropylN-(3-chlorophenyl) carbamate; ormethylN-(3,4-dichlorophenyl) carbamate, uracil type herbicides such as 5-bromo - 3 - s -butyl - 6 -methyluracil; or 1 - cyclohexyl - 3, 5 -propylene -uracil; thiolcarbamate type herbicides such as S-(4-chlorobenzyl) - 10 N,N-diethylthiolcarbamate; S-ethyl N-cyclohexyl-N-ethylthiol-carbamate; S-ethyl-hexahydro-lH-azepine-l-carbothioate;
or S -ethyl-N, N-di-n-propylthiocarbamate; pyridinium salt type herbicides such as 1,1' -dimethyl-4, 4' -bispyridinium dichloride;
phosphorus type herbicides such as N-(phosphonomethyl)-glycine, n ~ -trifluoro-2, 6 -dinitro-N, N-dipropyl-p-toluidine; 4-(methylsulfonyl)2, 6-dinitro-N, N-dipropylaniline; acid anillde type herbicides such as 2-chloro-2', 6' -diethyl-N-(butoxymethyl) . -acetanilide; 2 -chloro-2', 6' -diethyl-N-(methoxymethyl)acetanilide;
or 3,4 -dichloropropionanilide; 5-t-butyl-3-(2,4-dichloro-5-. 20 isopropoxyphenyl)-1, 3, 4-oxadiazolin-2-one; 2-[N-isopropyl, N -(4-chlorophenyl) -carbamoyll -4-chloro-5 -methyl-4-isoxazolin-: 3 -one; 3 -isopropylbenzo-2-thia-1, 3-diazinone(4) 2, 2-dioxide;
or 3-(2-methylphenoxy)-pyridazine, but they are not critical.

The herbi cidal con~positions of this invention ma~ also be .

,~
:

"` 1075~30 applied ~Yith admixture of plant growth regulators stlch as sodiuln naphthyl acetate; 1, 2 -dihydropyridazine -3, 6 -dione; or gibberellins, fungicides such as methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate; 1, 2-bis(3-methoxycarbonyl-2-thioureido) benzene; 3-hydroxy-5-methylisoxazole; N-2, 3-dichlorophenyl-tetrachlorophthalamic acid; 5 -methyl s -triazole -( 3, 4 -b)benz -thiazole; 0, 0-diisopropyl-S -benzylphosphorothioate; pentachloro-nitrobenzene; Kasugamycin; brasticidin S; or 4, 5, 6, 7 -tetrachlorophthalide; insecticides such as 0, 0-diethyl 0-(2-isopropyl-4-methyl-6-pyrimidinyl)phosph orothioate; 0, 0-diethyl S-2-[(ethylthio)ethyl]phosphorodithioate; 1-naphthyl N-methylcarbamate; 0, 0-dimethyl 0 -( 3 -methyl- 4 -nitrophenyl) -thiophosphate; 0, 0-dimethyl S-(N-methylcarbamoylmethyl)-phosphorodithioate; S-methyl-N-[(methylcarbamoyl)oxyl-thio-acetimidate; 0, 0-dimethyl S -(N-methyl-N-formylcarbamoyl-methyl)phosphorodithioate; 0, 0-dimethyl S-2-(ethyltllio)ethyl-phosphorodithioate; 0, 0-diethyl S -2[(ethylthio)ethyl] -phosphorodithioate; or 0, 0-dimethyl- 1 -hydroxy-2, 2, 2 -trichloro-ethylphosphonate or fertilizers.

The preparation of compounds having the above formula (I) and herbicidal compositions containing com-pounds having the above formula (I) will be more fully illustrated by way of the following Examples:which are compounds of copendingappIicatiOnsNos~ 222,945 and 299,625 except where indicated by an asterisk which are compounds accord-ing to the present invention.

~0 EX~MPLE 1 , 1, 3-Dimethyl-4 -(4 -nitrobenzoyl) -5 -h~droxypyrazole In 22 ml of dry dioxan was dissolved 2. 24 g of 1,3-dimethyl- - -5-pyrazolone and then 2. 96 g of potassium hydroxide added thereto.
3.71 g of p-nitrobenzoyl chloride was added dropwise thereto while stirring at room temperature. After completion of the dropwise addition, the mixture was heated under reflux for 1 hour. After completion of the reaction, the reaction mixture was allowed to cool and then 40 ml of a 2N hydrochloric acid solution was added thereto. Crystalline material thus separated was recovered by filtration and washed with water to give 4.38 g --of crude crystals. This product was recrystallized from methanol to give 3.62 g of the desired product as pale yellow prisms having a melting point of 234 - 235 C. Yield 69.3%
Analysis: -~alculated for C12HIlN304 C, 55. 17; H, 4.24; N, 16 09%
Found C, 55. 17; H, 4.14; N, 16. 06%

æXAMPLE 2 1,3-Dimethyl-4-(2,4-dichloro~enzoyl)-5-hydroxypyraz_ In 65 ml of isopropanol were suspended 4.48 g of 1,3-dimethyl-5-pyrazolone and 3 g of calcium hydroxide and the resulting suspension was heated under reflux for 30 minutes with stirring. After cooling, 8.4 g of 2,4-dichlorol)enzoyl chloride was added dropwise thereto. After co~npletion of the dropwise ~07S030 addition, the mixture was hcated under reflux for 2 hours, The solvent was distilled off from the reaction mixture and 15 ml.
of water was added to the residue. The mixture was made acidic with 23 ml of a 2N hydrochloric acid solution and extracted with 69 ml of chloroform. The chloroform layer was washed with water and the organic phase separated and dried. The chloroform was distilled off. The residue was recrystallized from ethanol to give 7. 6 g of the desired product as colourless prisms of mp 165 - 166 C. Yield 66. 7%
Analysis:
Calculated for C12HllN34 C, 50. 55; H, 3- 53; N, 9. ~2;
Cl, 24. 88%
Found C, 50, 85; H, 3. 54; N, 9. 81;
Cl, 24. 55%

l-Methyl-3-n-propyl-4-(2-chlorobenzoyl)-5-hydroxypyrazole 1, 4 g of 1 -methyl-3 -n-propyl-5 -pyrazolone was dissolved in 10 ml of dioxan with heating and then l. 5 g of calcium chloride was added to the resulting solution. 1.75 g of 2-chlorobenzoyl chloride was added dropwise with stirring at 50 C. After completion of the dropwise addition, the mixture was heated under reflux for 1 hour. After completion of thc reaction, the reaction mixture was allowed tG cool and 100 ml of a 2N hydrochloric acid solution was added thereto. The mixturc was extracted with 70 ml of chloroform and an organic laycr scparated. The la~er was washed with water, dried over anhydrous sodium sulfate and the solvent distilled off to give 2 g of brown oily residlle.
The residue thus obtained was dissolved in asmall amount of benzene and adsorbed on a silica gel column, which was then eluted with benzene/ethanol (50:1) to give 0. 6 g of crystals.
The crystals were recrystallized from methanol/water (7:3) to give 0, 25 g of the desired product as colourless prisms having a melting point of 125 - 126C.
Yield 9. 2%
Analysis:

Calculated for C14H15ClN22 C, 60- 33; H~ 5, 42; N~ 10, 05;
Cl, 12, 72%
Found C, 60,44; H, 5, 43; N, 10, 25;
Cl, 12, 72%

Following the procedure as in the above Examples 1 to 3, the following compounds were prepared, 1, 3-dimethyl 4-(3 -chlorobenzoyl)-5-hydroxypyrazole m,p, 176, 5 - 177, 5C
1, 3-dimethyl-4-(4-chlorobenzoyl)-5-hydroxypyra~Aole m,p. 202 - 204C
1, 3 -dimethyl-4 -( 3, 4-dichloroben~oyl) -5 -hydroxypyrazole m,p, 255 - 257C

* 1, 3-dimethyl-4-(4-methylbenzoyl)-5-hydroxypyrazole m,p, 114 - 116C
* 1,3-dimethyl-4-(3-methylbenzoyl)-5-hydroxypyrazole m. p. 145 - 146C
1,3-dimethyl-4-(2-methoxybenzoyl)-5-hydroxypyrazole m. p. 162. 5 - 163.5C
1,3 -dimethyl-4 -(3 -nitrobenzoyl) - 5 -hydroxypyrazole m. p. 246 - 247 C
1,3-dimethyl-4-(3, 5-dinitrobenzoyl)-5-hydroxypyrazole m.p. 261 - 262C
1,3 -dimethyl-4 -(4 -bromobenzoyl) - 5 -hydroxypyrazole m.p. 207 - 208C
1,3-dimethyl-4-(3, 5-dichlorobenzoyl)-5-hydroxypyrazole m. p. 248 - 249C
1, 3-dimethyl-4-(2-nitrobenzoyl)-5-hydroxypyrazole m.p. 233 - 234C
1, 3-dimethyl-4-(4-benzoylbenzoyl)-5-hydroxypyrazole m.p. 194- 195C
1, 3 -dimethyl-4 -(2 -lluorobenzoyl) - 5 -hydroxypyrazole m.p. 158 - 159C
1,3-dimethyl-4-(2-bromobenzoyl)-5-hydroxypyrazole m.p. 154 - 156C
1,3-dimethyl-4-(2, 5-dichlorobenzoyl)-5-hydroxypyrazole m.p. 183 - 184C
1,3-dimethyl-4-(4-methoxybenzoyl)-5-hydroxypyrazole m.p. 214 - 21~C

~a7so30 1,3-dimethyl-4-(3,4-dimethoxybenzoyl)-5-llydroxypyra7,ole m,p. 154 - 155C
* 1,3 -dimethyl-4-(4-t-butylbenzoyl) -5-hydroxypyrazole m.p. 172 - 173C
* 1,3-dimethyl-4-(3,4-dimethylbenzoyl)-5-hydroxypyrazole m.p. 197^ 198C
1,3-dimethyl-4-(3, 5-dimethylbellYoyl)-5-hydroxypyrazole m.p. 165 - 167C
1,3-dimethyl-4-(2-chloro-4-nitrobenzoyl)-5-hydroxypyrazole m.p. 197 - 197, 5C

1 -methyl -4-(2 -chlorobenzoyl) -5 -hydroxypyrazole m.p. 107 - 11ûC
1,3-dimethyl-4-(3,5-dimethoxybenzoyl)-5-hydroxypyrazole m.p. 181 - 182C
1, 3-dimethyl-4-(2-nitro -5-methylbenzoyl)-5-hydroxypyrazole m.p. 257 - 258C

1,3-dimethyl-4-(4-methanesulfonylbenzoyl)-5-hydroxypyrazole m. p. 257 - 259C
1 -isopropyl-3-methyl-4-(2-chlorobenzoyl) -5-hydroxypyrazole nD 1. 5705 ;- 1,3-dimethyl-4 -(2 -iodobenzoyl) -5 -hydroxypyrazole m.p. 171 - 172C

1,3 -dimethyl-4 -(4 -fluorob~nzoyl) - 5 -hydroxypyrazole m.p. 1~1 C
1,3-dimethyl-4-(4-cyanobenzoyl)-5-hydroxypyrazole m. p. 208C

., :, .

.

1,3 -dimethyl -4 -(2 -acetylbenzoyl) - 5 -hydroxypyrazole m.p. 142 - 143C
1,3-dimethyl-4-(2,4, S-trichlorol~enzoyl)-S-hydroxypyrazole m.p. 156 - 157C
- 5 1,3-dimethyl-4-(2,3,4,5-tetrachlorobenzoyl)-5-hydroxypyrazole m.p. 225 - 226C
1,3-dimethyl-4-(3 ~ ethyl-4-nitrobenzoyl)-5-hydroxypyrazole m.p. 252 - 254C
1,3-dimethyl-4-(2-nitro-4-chloroben~oyl)-5-hydroxypyrazole m.p. 223 - 224C
1,3-dimethyl-4-(3,4, 5-trimethoxybenzoyl)-5-hydroxypyrazole m,p. 189 - 191C
1 -ethyl - 3 -methyl -4 -(2,4 -dichlorobenzoyl) - 5 -hydroxypyrazole m.p. 176 - 177C
1-ethyl-3-methyl-4-(2-nitro-4-chlorobenzoyl)-5-hydroxypyrazole m.p. 196 - 197C
:

1,3-Dimethyl-4-(2,4-dichlorobenzoyl)-5-mercaptopyrazole ( a) 1. 0 g of 5 - chloro - 1,3 -dimethylpyrazole, 1. 05 g of anhydrous aluminium chloride and 1,66 g of 2,4-dichlorobenzoyl chloride were dissolved in 6 ml of tetrachloroethane and the resulting solution heated under reflux for 8 hours. After completion of the reaction, the reaction mixture was pvured into water and an organic layer was separated. 7 ml of a 5% aqueous solution of sodium hydroxide was added thereto and the mixture was stirred -:- . .. . : . - . . - . . .
. ~ . .
.~ - ~ . . . : . .
- - - : : ' ~ - -~075U30 for 1 l~our, Then, the organic layer was dried over anhydrous sodium sulfate and the solvent distilled off, The resulting oily substance was crystallized from ethanol to give 1. 82 g of S-chloro 4-(2, 4-dichlorobenzoyl)1, 3-dimethylpyrazole as prisms melting at 101. 5 - 102. 5C. Yield 78, 3%
Analysis:
- Calculated for C12HgCl3N20 C, 47. 48; H, 2. 99; N, 9. 23;
` Cl, 35; 04%
Found C, 47. 49; H, 2. 96; N, 9. 31;
Cl, 34. 91%

(b) A mixture of 0. 3 g of 5-chloro-4-(2, 4-dichlorobenzoyl)-1, 3- -- dimethylpyrazole, 2.1 g of sodium hydrogen sulfide dihydrate and 6 ml of ethanol was heated under reflux on a water bath for 3 hours.
After completion of the reaction, the ethanol was distilled off IS under reduced pressure from the reaction mixture and 15 ml of water was added followed by extraction with benzene. To the aqueous layer was added concentrated hydrochloric acid to adjust the pH to 1 and the mixture was extracted with chloroform. The extract was washed with water and then dried over anhydrous sodium sulfate. The solvent was distilled off to give the crude crystalline substance, which was then recrystallizcd fron n-hex~ne to give 0.10 g of the desired product as a yellow powder ha~ring a melting point of 85 - 8~ C. Yield 33. 3%.

' - - '` ` ' .

-~075030 Analysis:
Calculated for C12HloN2OSC12: C, 47- 85; H, 3- 35; N~ 9- 30;
S, 10, 65; Cl, 23. 54%
Found C, 47. 76; H, 3. 43; N, 9, 38;
- S, 1 1. 02; Cl, 23. 24%

1, 3-Dimethyl-4-(2, 6-dichlorobenzoyl)-5-hydroxypyrazole In 5 ml of water was dissolved 0. 56 g of potassium hydroxide and a solution of 1. 56 g of 5-chloro-4-(2, 6-dichlorobenzoyl)1, 3-dimethylpyrazole in 10 ml of ethanol was added thereto. The mixture was heated under reflux for 12 hours. After completion cf the reaction, tihe reaction mixture was allowed to cool and extracted with benzene. The aqueous layer was separated and 2N HCl solution was added to adjust the pH to 3 - 4, when a crystalline substance separated out. The resulting crystalline substance was recovered by filtration and recrystallized from ethanol to give 0. 68 g of the desired product as colourless needles melting at 249. 5 - 250. 5C. Yield 48. oyO
Analysis:
Calculated for C12HlOC12N2 2 Cl, 24. 88%
- Found C, 50. 38; H, 3. 53; N, 9.90;
Cl,- 24.57%

. -.

~07S030 Following the procedures of the above-n cntioned :E:xample 5 the following compounds were prepared.

* 1, 3 -dimethyl-4 -( 2, 4 -dimethylbenzoyl) - 5 -hydroxypyrazole m. p. 95 - 96C
` * 1,3-dimethyl-4-(2-methylbellzoyl)-5-hydroxypyrazole m.p. 82-83C

1, 3 -Dimethyl-4 -( 2 -chlorobenzoyl) - 5 -acetoxypyrazole In a mixture of 20 ml of benzene and 0. 51 g of triethylamine was dissolved 1. 25 g of 1, 3-din~ethyl-4-(2-chlorobenzoyl)-5-hydroxypyrazole and 0. 4 g of acetyl ch]oride was added dropwise at room temperature with stiFring. After completion of the dropwise addition, the mixture was stirred at room temperature for 3 hours. After completion of the reaction, water was added lS to the reaction mixture to dissolve the salts and an organic layer separated. The organic layer was dried ovcr anhydrous sodium sulfate and the solvent distilled off. The resulting oily substance was recrystallised from n-hexane to give crude crystalline substance which was recrystallized from methanol to give 1. 20 g of the desired product as colourless prisms melting at 78 - 79 C. Yield 82. 2%.
Analysis:

14 13 2 3 ~ 5 . 45; H, 4. 48; 1~, 9. 57;
Cl, 12. 11%

Found C, 57, 50; H, 4. 45; N, 9. 61;
Cl, 12, 23%
IR spectrum (liquid paraffin) ~ 1793 cm S 1, 3-Dimethyl-4-(2, 4-dichlorobenzoyl)-5-lauroyloxypyrazole In 10 ml of benzene was dissolved 0. 285 g of 1, 3-dimethyl-4-(2, 4- dichlorobenzoyl)-5-hydroxypyrazole and then 0. 2 ml of triethylamine was added thereto. Under ice-cooling, a solution of 0. 27 g of lauroyl chloride in 5 ml of benzene was added dropwise thereto, After completion of the dropwise addition, the resulting mixture was stirred at room temperature for 19 - hours, After completion of the reaction, ether was added to ~ .
3 - the reaction mixture, which was then washed successively with ;~ water, lN HCl, a saturated aqueous solution of sodium hydrogen lS carbonate and a saturated aqueos solution of sodium chloride.
Then, the reaction mixture was dried over anhydrous sodium sulfate and the solvent distilled off. The resulting residue was recrystallized from n-hexane under cooling with dry-ice to give 0. 46 g of the desired product as white crystals melting at 56C.
Yield 98. 0%.
~- Analysis:

Calculated for C24H32C12N2O3: C, 61. 66; H, 6. 90; N, 5.99;
Cl, 15.17% l, 3-dimethvl-4-~". 4-dichlorobenzoyl-5-(4-methylbenzoyloxy)-pyrazole m, p. 94 C"
Found C, G1. 27; H, 6. 94; N, 5. ~4;
Cl, 15. 11%

.

- `~

10~5~)30 IR spectrum (liquid paraffin) ~f 1790 cm 1, 3-Dimethyl-4-(2, 4-dichlorobenzoyl)-5-chloroacetoxypyrazole In a mixture of 10 ml of bcnzene and 0. 2 ml of triethyl-amine was dissolved 0. 285 g of 1, 3-dimethyl-4-(2, 4-dichloro-` benzoyl~-5-hydroxypyrazole and then a solution of 0.18 g of chloroacetylchloride in 5 ml of benzene was added dropwise under ice-cooling and stirring. After completion of the dropwise addition, the resulting mixture was stirred at room temperature for 2 hours. After completion of the reaction, ether was added to the reaction mixture and the mixture then washed successively with 3 portions of 50 ml of water and dried over anhydrous f ' sodium sulfate. Then, the solvent was distilled off and the resulting residue recrystallized fron n-hexane to give 0. 297 g of the desired product as white crystals melting at 120 - 122C.
Yield 82. 0%.
Analysis:

14 11 3 2 3 ' . 50; H, 3. 07; N, 7. ~5;
Cl, 29. 415!o Found C, 46. 25; ~I, 3. 08; N, 7. 81;
Cl, 29, 32%
IR spectrum (liquid paraffin) ~c 0 17gO cm Following the procedures of the above mentioned ~:xamples ~075030 6 to 8 the following compounds were prepared, 1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-stearoyloxypyrazole m. p. 57 - 61C
1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-crotonyloxypyrazole m. p. 87 - 89C
1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-benzoyloxypyrazole m.p. 138 - 139C
1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-acetoxypyrazole m.p. 81 - 82C
1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-acetylthiopyrazole nl7' 5 1.5890 1,3 -dimethyl -4 -(2,4 -dichlorobenzoyl) - 5 -propionyloxypyrazole m. p, 48C

1,3-dimethyl -4-(2,4-dichlorobenzoyl)-5-isobutyryloxypyrazole m.p. 101 - 102C
1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-linoleyloxypyrazole nl3 8 1. 5196 1,3-dimethyl-4-(2-chloro-4-nitrobenzoyl)-5-benzoylox,vpyrazole m.p. 163C
- 1,3-dimethyl-4-(2-chloro-4 -nitrobenzoyl)-5-(4-chlorobenzoylQxy) --pyrazole m. p. 194C
1,3-dimethyl-4-(2-chloro-4-nitrobenzoyl)-5-(2-chloro-4-nitrobenzoyloxy)pyrazole m.p. 182 - 184C
.

,.~ - ~ . ~ -- ~: ' . ' .: . .
. , .

-` ~07S030 1, 3-dimethyl-4-(2-chloro-4-nitrol)enzoyl)-5-cinllamoyloxypyr~zole m. p. 164C
bis-[l, 3-dimetllyl-4-(2-chloro-4-nitrobenzoyl)-5-pyrazolyl]
6uccinate m. p. 203C
1,3-dimethyl-4-(2-chloro-4-nitrobenzoyl)-5-acetoxypyrazole m. p. 133C
1,3-dimethyl-4-(2-chloro-4-nitrobenzoyl)-5-pivaloyloxypyrazole m. p. 157 - 158C
1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-phenylacetoxypyrazole m. p. 74 - 76~C
1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-(4-chloropi.enylacetoxy)-pyrazole m.p. 130 - 131C
1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-cyclohexylcarbonyloxy pyrazole m. p. 98 - 99C
1,3-dimethyl-4-(2,4-di chlorobenzoyl)-5-(2,4-dichlorophenoxy-acetoxy)pyrazole m.p. 107 - 108C
1,3-dimethyl-4-(2,4-di chlorobenzoyl)-5-(2,4-dichlorobenzoyloxy)-pyrazole m.p. 168 - 169 C
bis-[1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-pyrazolyl] sebacate m.p. 143 - 144C
1,3-dimctbyl-4-(2,4-dichlorol)enzoyl)-5-(4-methylbenzoyloxy)pyrazole m.p. 197 - 198C

, ?~0 ~075(~30 1,3-Dimethyl-4-(2,4-dichlorobenzoyl)-5-pyrazolflmethanesulîonate In a mixture of 0.1 g of triethylamine and 5 ml of dry benzene was dissolved 0.29 g of 1,3-dimethyl-4-(2,4-di chloro-benzoyl)-5-hydroxypyrazole and then 0.1 g of methanesulfonyl chloride was added dropwise at room temperature with stirring.
After completion of the dropwise addition, the resulting mixture was stirred at room temperature for 12 hours~ After completion of the reaction, 10 ml of water was added to the reaction mixture and organic layer separated~ The organic layer was dried over anhydrous sodium sulfate and the solvent distilled off. The resulting residue was recrystallized from n-hexane to give 0.3 g of the desired product as white needles melting at 73 - 74 ~:.
Yield 83. 3%~ -Analysis:
Calculated for C13H12C12N24SC~ 42- 99 H~ 3- 33; N~ 7 71;
S,8,83; Cl, 19.25%
P'ound C,42. 64; H, 3. 37; N, 7.76;
S,9.15; Cl, 19.23%
IR spectrum (liquid paraffin) ~SO 1355 cm 1180cm 1 Following the procedures of the above-mentioned Example 9 the following compounds were prepared.

- , :
- ~ ' ' ' ' ' ' : '' 1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-pyrazolyl 4-toluenesulfonate m. p. 122 - 124C
1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-pyrazolyl bcnzcnesulfonate m p. 88 - 89C
1,3-dimethyl-4-(2-nitro-4-chlorobenzoyl)-5-pyrazolyl 4-toluenesulfonate m.p, 129 - 130C
1,3-dimethyl-4-(2-nitro-4-chlorobenzoyl)-5-pyrazoiyl benzenesulfonate m,p. 127 - 138C
1-ethyl-3-methyl-4-(2,4-dichlorobenzoyl)-5-pyrazolyl 4-toluenesulfonate m, p. 115 - 116C
1-ethyl-3-methyl-4-(2-nitro-4-chlorobenzoyl)-5-pyrazolyl 4-toluenesulfanate m. p. 100 - 101C
i~ 1,3-dimethyl -4-(2-chlorobenzoyl)-5-pyrazolyl methanesulfonate m.p. 97 - P~8C ~-, 15 EXAMPLE 10 1,3-Dimethyl-4 ~(2,4-dichlorobenzoyl)-5-(5-meth,yl-3-oxo-4-isoxazolin - 2 -ylcarbonyloxy) -pyrazole In 4 ml. of dry benzene was-dissolved o.1 g of 3-hydroxy-5-methylisoxazole and then 0. 5 g of liquid phosgcne was added 2~ thereto. After stirring at room temperature for 1 hour, the mixture was heated under reflux for 1 hour. After completion - of the reaction, the reaction mixture was allowed to cool and the ~` excess phosgene and benzene distilled off nnder reduced pressure.

,, .
., The residue was dissolved in 5 ml of dry benzene and a solution of 0. 3 g of 4-(2, 4-dichlorobenzoyl)-1, 3-dimethyl-S-hydroxypyr~zole and 0. 1 g of triethylamine in 5 ml of dry benzene was added dropwise at room temperature with stirring. After completion of the dropwise addition, the mixture was stirred at room temperature for a further 1 hour. After completion of the reaction, 10 ml of water was added to the reaction mixture and an organic layer separated. The organic layer was washed successively with lN HCl, a saturated aqueous solution of sodium hydrogen carbonate and water.and dried over anhydrous sodium sulfate. Then, the solvent was distilled off and the resulting residue was recrystallized from benzene/hexane to give 0. 25 g of the desired product as white needles melting at 180 - 182 C. Yield 61. 0%.
Analysis:
1517Hl~C12N3O5 C, 49.78; H, 3 19; N 10 24 Cl, 17. 28%
Found C, 49.75; II, 3. 31; N, 10. 31;
Cl, 17. 05%
lR spectrum (liquid paraffin) ~)c 1785 cm Following the procedures of the above-mentioned Example 10 the following compound was pr~pared.
1, 3-dimethyl-4~2, 4-dichlorobenzoyl)-5-(3-o~o-4-chloro-5-methyl-4 -isoxazolin -2 -ylcarbonyloxy) -pyrazole m. p. 204 - 206C

~ ' .

~075030 1, 3-Dimethyl-4-(2, 4-dichlorobenzoyl)-5-methoxycarbonyloxypyrazole In a mixture of 20 ml of dry benzene and 0. 28 g of triethylamine was dissolved 0, 72 g of 1, 3-dimethyl-4-(2, 4-dichlorobenzoyl)-5-hydroxypyrazole and then 0. 26 of methyl chlorocarbonate was added dropwise at room temperature with stirring. After completion of the dropwise addition, the mix'.ure was stirred at room temperature for 1 hour. After completion of the reaction, the reaction mixture was allowed to stand for 12 hours and then 30 ml of water was added thereto. A benzene layer separated and the aqueous layer was extracted with benzene.
The benzene layer and the benzene extract were combined, and the mixture washed with water and dried over anhydrous sodium sulfate. Then, the solvent was distilled off and the resulting residue was recrystallized from a small amount of n-hexane to give 0. 77 g of the desired product as white crystals melting at 86 - 88 C. Yield 92%.
Analysis:

Calculated for C14H12Cl2N24 C, 49. 00; E, 3- 5~; N, 8-16;
Cl, 20.66%
Found C, 49. 05; H, 3. 56; N, 8. 33;
Cl, 20. 44%
IR spectrum (liquid paraffin) ~c=o 1771 cm ~ollowing the procedures of the abo~e-mentioned Example 11 the following compounds were prepared.

1075~)30 1, 3-dimetllyl-4-(2, 4-dichlorobenzoyl)-5-rl-propoxycarbonyloxypyrazole m. p. 59 - 62C
1, 3-dimethyl-4-(2, 4-dichlorobenzoyl)-5-benzyloxycarbonyloxypyrazole m.p. 87 - 90C
bis-[1, 3-dimethyl-4-(2, 4-dichlorobenzoyl)-5-pyrazolyl carbonate m.p. 166 - 168C
` 1, 3-dimethy -4-(2, 4-di chlorobenzoyl)-5-phenoxycarbonyloxypyrazole m.p. 159 - 160C
1, 3-dimethyl-4-(2, 4-dichlorobenzoyl)-5-phenylthiocarbonyloxypyrazole --m.p. 83 - 84C ~-~
1, 3-dimethyl-4-(2, 4-dichlorobenzoyl)-5-n-butylthiocarbonyloxypyrazole nD6 1. 5618 1, 3-dimethyl-4-(2, 4-dichlorobenzoyl)-5-ethylthiocarbonyloxypyrazole nD ~. 5751 1, 3-dimethyl-4-(2, 4-dichlorobenzoyl)-5-benzylthiocarbonyloxypyrazole nD3 1. 5904 1,3-Dimethyl-4-(2,4-dichlorobenzoyl)-5-hydroxypyrazole calcium salt `3 In 50 ml of water was suspended 2. 85 g of 1, 3-dimethyl- -4-(2, 4-dichlorobenzoyl)-5-hydroxypyrazole and the suspension ,j~ was dissolved in about 5 ml of a 2N aqueous solution of sodium hydroxide. A solution of 1.11 g of calcium chloride in 10 ml of water was added and the resulting mixture was stirred. The precipitate so obtained was recovered by filtration and dried to give 2. 4 g of the desired product as white powder melting at about 260C. Yield 79. 0%.

.

-Analysis:
Calculated for C12HgN2O2Cl2Ca. 2H2O: C, 44. 73; H, 3. 44; N, 8. ~9%
Found C, 47. 88; H, 3. 23; N, B. 83%

Following the procedure of the above-mentioned Example 12 the following compounds were prepared 1, 3-dimethyl-4-(2, 4-dichlorobenzoyl)-5-hydroxypyrazole n~agnesium ` ` salt m. p. ca. 270C
l, 3-dimethyl-4-(2, 4-dichlorobenzoyl)-5-hydroxypyrazole aluminium salt m. p. ca. 155C
1, 3-dimethyl-4 -(2, 4-dichiorobenzoyl) -5 -hydroxypyrazole iron salt m. p. ca. 170C
1, 3-dimethyl-4-(2, 4-dichlorobenzoyl)-5-hydroxypyrazole copper salt - --m.p. zbove 300C
1, 3 -dimethyl-4 -( 2, 4 -dichlorobenzoyl) - 5 -hydroxypyrazole sodium salt 15- m.p. above 300C

1, 3 -Dimethyl -4 -( 2, 4 -dichlorobenzoyl) - 5 -hydroxypyrazole _ i ; isopropylamine salt In 50 ml of benzene was suspended 2. 85 g of 1, 3-dimethyl-4-(2, 4-dichlorobenzoyl)-5-hydroxypyrazole and 0. 7 g of isopropyl-amine was added to the suspension with stirring. Then, the mixture was stirred at room temperature for about 1 hour. The solvent was distilled off and the rcsidue cooled. The solid material was recovered by filtration, wasl-cd witll petroleum etl er and dried ~075030 to give 3. 2 g of the desired product as white powdery substance melting at 130 - 140C . Yield` 9 3, 2%.
Analysis:
Calculated for C15H1gClaN3O2: C, 52, 34; H, 5. 56; N, 12. 21%
Found C, 52, 09; H, 5. 72; N, 12. 59%

1, 3 -Dimethyl-4 -( 2, 4 -dichlorobenzoyl) -5 -hydroxypyrazole hydrochloride To 0. 3 g of 1, 3-dimethyl-4-(2, 4-di chlorobenzoyl)-5-hydroxypyra~7O1e waæ added 2 ml of concentrated HCl and the resulting mixture was stirred at room temperature for 6 hours. After completion of the reaction, the reaction mixture uras allowed to cool ~nd the desired product was recovered by filtration. The product was washed with a small amount of methanol and then with n-hexane -and dried to give 0. 20 g of the desired product as a white powder having a melting point of 115 - 125C (with decomposition) Yield 57. 1%, Analysis - -12 11 2 3 2 ~ 44. 82; H, 3. 45; N, 8. 71;
Cl, 33. 07% - - - -Found C, 45. lli; H, 3. 57; N, 8. 85;
Cl, 32. 93%

Following the procedures of the above-mentiolled Examplc 14 the following compound was prepared.

- - - :

~075~130 , ; 1, 3-dimethyl-4-(3, 4-dimethoxybenzoyl)-5-hydroxypyrazole hydrochloride m.p. 164 - 165 C

.. . .

:' l-Allyl-3-n~ethyl-4-(2, 4-dichlorobenzoyl)-5-hydroxypyrazole A suspension of 1. 4 g of 1-allyl-3-methyl-2-pyrazolin-5-one and 0. 74 g of calcium hydroxide in 20 ml of isopropanol was heated under reflux with stirring for 1. 5 hours, After cooling, to the resulting mixture ~ras added dropwise 2. 3 g of 2, 4-dichlorobenzoyl chloride. ~fter completion of the dropwise addition, the resulting mixture was heated under reflux for 5. 5 :' hours. After. completion of the reaction, the solvent was distilled off and to the residue was added 3 ml of 2N hydrochloric acid to adjust pH to 3. 0. The mixture was then extracted with chloroform and the extract solvent distilled off from the extract. The residue was dissolved in a small amount of benzene and the solution was ,` washed with water, dried over anhydrous sodium sulfate and the j ~ ~ solvent distilled off. The resulting residue was recrystallized from isopropyl ether containing a small amount of methylene ; ~ ~ chloride to give 1. 18 g of the desired product as white crystals melting at 161 - 163C. Yield 40. 7%.
Analysis:
Calculated for Cl2Hl6N2cl2o3 C~ 47- 86; H~ 3- 35; N~ 9- 30;
Cl, 23. 54%
Found C, 47. 33; H, 3, 41; N, 9. 06;
Cl, 23.31%

---~5--EXAMPL:E lG
1 -A11~1-3 -m ethyl-4 -(2, 4 -dichlorobenzoyl) -5 -pyrazolyl 4-toluenesulfonate A solution of 180 mg of 1-allyl-3-methyl-4-(2,4-dichloro-benzoyl)-5-hydroxypyrazole in 6 ml of benzene and 58. 4 mg of triethylamine was stlrred at room temperature for 1 hour and 110 mg of 4-toluenesulfonyl chloride was added. Then, the resulting mixture was heated under reflux for 1 hour. A~ter -completion of the reaction, water was added to the reaction mixture and an organic layer was separated. The organic layer was dried over anhydrous sodium sulfate, the solvent distilled off and the resulting oily substance was recrystallized from benzene/
n-hexane to give 173 mg of the desired product as colourless prisms melting at 113 - 114 C. Further, the solvent was distilled off from the mother liquor and recrystallization from n-hexane gave 26 ml of the desired product. Total yield 73. 9%.
Analysis:
Calculated for C21H184N2SCl2 C~ 54- 20; H~ 3- 90; N~ 6- 09;
S, 6. 89; Cl, 15. 245'o Found C, 54. 45; H, 3. 98; N, 6. 09;
S, G. 80; Cl, 15. l9~o Following the above procedures the following con~pounds were prepared.

l-allyl-3-mcthyl-~ -(2-chloro-4 -nitrn~)cn7,0yl)-5-y~r~zolyl 4 -toluenesulfollate m. p. 96 - 99C
, 1-allyl-3-methyl-4-(2, 4-dichlorobenzoyl)-5-(4-chlorobell~oyloxy) pyrazole m. p. 155 - 157C
1 -allyl -3 -methyl-4 -( 2, 4 -dichlorobenzoyl) - 5 -isobutyryloxypyrazole rr..p. 62 - 63C

Examples of the preparations of herbicidal compositions are given below. All parts are given by weight hereinafter unless otherwise stated.

GRANULES
70 Parts of l, 3-di~thyl-4- (2,4 dichlorbbenzoyl) -5-hydroxy-E~yrazole were finel~r ~l~rized and 30 parts of clay were added thereto.
The mixture was bl~ded in a mixer to form a premix, 10 Parts of the premix were homogeneously blended with 60 parts of clay and 30 parts of bentonite in a mixer. To the resulting blend was added an appropriate amount of water. The mixture was hleaded in akneader, extruded through a screen having a diameter of 0. 8 mm and dried in a draft drier at 50 C. The so-obtained product was adjusted by a shifter to give granules.

GRANULES
70 Parts of l-allyl-3-nE~t-hyl-4-(2,4 dichlorbbenzoyl)-5-benzyl-thiocar'Donyl~r,lzole was finely pulverized and 30 parts of bentonlte ~-a ~. To the r~sult:ing bler~ was a~ded an a~p~iate -anDunt of water. The ., ~075030 mixture was kneaded in a kneader, extruded through ascreen having a diameter of 0. 8 mm and dried in a draft drier at 50 C.
The so-obtained product was adjusted by ashiiter to give granules.

- , GR~NULES
35 Parts of 1-~3 di~[ethyl-4-(2,4 dichlorobenzoyl)-5~
E~yrazole and 35 p~rts of S-(4-~hlorobenz~l)N,_-diefflylff~iolca~amate were finely p~Lverized ~ 30 parts of precipit~ted calcium carbonate were added thereto. Th~ mixture was blended in a mixer to form a premix. 20 Parts of the premix were homogeneouslyblended with 50 part~ of clay and 30 parts of bentonite ina mixer. To the resulting blend is added an appropriate amount of water. The mixture was kneaded in a kneader, extruded through a screen having a diameter of 0. 8 mm and dried in a draft drier at 50 C. The so-obtained product was adjusted by a shifter to give gran.ules.

-, WETTABLE POWDER
,,, 50 Parts of 1,3~ et~l-4-(2-chloro-4-nitrbbe~zoyl)-5-hydr~y- -E~yrazole 29 parts of clay, 10 parts of diatanaceous earth, 5 parts of precipitated calcium carbonate, 3 parts of sodium ligninsulfonate, - 2 parts of "Newcoal" 1106 (Trade name, Nihon Nyukazai K. K. ) and 1 part of polyvinyl alcohol were homogeneously blended in a mixer and pulverized three timcs by means of a hammer mill.

- 1075()30 SOLUTIONS
30 Parts of 1,3-dinet~1-4-(2,4-dichlorobenzoyl)-~h~dro~y-l?~rajzole iso~lanine s~lt l l?art of "~ewcoal" 565 ~trade name, Nihon ~cazai K.K.) and 69 parts of water were blended and ha~gen-eously dissolved to form solutions.
~ ., Experimental results obtained using herbicidal compositions thus prepared are given below. The test compounds are formulated according to the procedure in the above-mentioned Example 20 as wettable powders, each containing 50~0 by weight of the active compound of this invention.

Paddy field weed treatment tests on soil filled with water 3 Polyethylene pots (hereinafter abbreviated as A, B and C), each having a surface area of 45 cm, were packed with paddy field soil. Into Pot A were transplanted rice plant seedlings (two plants, variety: ~inmaze ) at the 2. 5 leaves stage and two tubers of arrowhead as a representative of perennial ~.07s030 weed. In Pot B, seeds of monochoria, false pimpernel and "Abunome" (Dopatrium junceum Hamilt) as representatives `; of broad-leave weed were well admixed with the soil, one grown slender spikerush was transplanted thereinto and two tubers of flatstage as perenial weed were placed into the soil. In Pot C, seeds of barnyardgrasse and "I~otarui" (Scirpus hotarui Ohwi) were well admixed with the soil and two tubers of arrowhead as perenial weed were placed into the soil. The Pots A, B
- and C were kept in a greenhouse for 3 days under paddy field conditions. After rooting of plants, suspensions of the test formulations were applied to the soil at 10 ml per pot under waterlogged conditions. After 20 days, the herbicidal effect on each weed and phytotoxicity of the rice plant were observed and evaluated. The results are shown in Table 1 wherein effective dose (g/a) means the minimum dose for a growth inhibition rate (chlorotic area on the surface of plant) of not less than 70~.

- ' "

:-~ o o oo o o ~ o o o o o o '~ oo ~ ~r ~ er ~r . _ _ _ , o o U~ o U~ ..
~ O 1~ Ir~ ~ 1~) N N
1~ 1~
~ ~ 5 I ~ r~ r` O N N N ' ~1 a) 1~: . .. _ _ _1 , .
~ ~ ~ ~ O U~ U~ In In U~
_I ~ r~ . O N r~ r~ N N .

E~ R .Y o I~ N Il~ U) Il') ~ ~ N N N N
_ S~ . In' ~ ISl O O O N N

a y ~ O O O u~ ~ _ l _ ~bq U~ U~ O O U~ Il~
m ~ t~ t` N Ir) N N
~. ' _ ~ Z ~ N ~r IJ~ ~ I~
. ~O _ _ ~07s030 Pre-emergence soil treatment test on field weeds A field soil was placed in polyethylene pots having a surface area of 150 cm and seeds of barnyard-grass, ( Cyperus microiria steud. ) crabgrass, green foxtail, goose grass and chufa/as representatives of narrow-leaved weeds and of shepherd's purse as a representative of broad-leaved weeds were sown and covered with the soil.

Similar polyethylene pots having a surface area of 150 cm were filled with a field soil and sown with seeds of asatic dayflower as a narrow-leaved weed and of common chickweed eye, corn spurrey, pigweed , common purslane, and white goose-foot, as broad-leaved weeds.
Immediately after soil-covering, a suspenslon of the test compound was applied to the soil surface in each pot. After 20 days from the application, herbicidal ef fects against every weed were observed . The results are shown in Table 2 wherein the ratings for evaluation are the same as in Experiment l and shown by means of ef f ective 2 0 dose ( g/a ) .
Table 2 . . , ,, __ .
Herbicidal activity in f ield (Effective dose g/a) 1~ r rr~r~
~ ~ ~ O ~ ~ ~ ~ ~ ~ 0~ ~

; 30 ' ' .

Claims (4)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A herbicidal composition including a compound having the formula (I) wherein R1 is an alkyl group; R2 is an alkyl group, X is an alkyl group and n is 1, 2 or 3 and when n is 2 or 3 the substituents X
may be the same or different, or a salt thereof or an organic acid ester thereof together with an agriculturally acceptable carrier or diluent.

2. A composition as claimed in claim 1, in which in the compound of formula I, R1, R2 and X are methyl and n is 1 or 2.

3. A composition as claimed in claim 1, in which the compound of formula I is 1,3-dimethyl-4-(2-methyl benzoyl)-5-hydroxy pyrazole.

4. A method for the control of unwanted plants in an area of land which comprises applying to the plants a herbicidal composition as claimed in claim 1, 2 or 3 in an amount from 10 to 4,000 g per 10 area of said land.