Note: Descriptions are shown in the official language in which they were submitted.
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
12
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
-1-
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
1 2
(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
--3--
--` 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-
107S030
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
R4
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).
-
--10--
,
~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,
'.~
--12--
1075030
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
--14--
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.
--15--
. - :'
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,
--16--
,
107S030
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
--18--
~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~
--19--
107S030
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.
--20--
~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
--22--
S 07S030
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
.
-23-
,~
:
"` 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
-24-
-- 1075030
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
- --25--
~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%
EXAMPLE 3
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
--26--
107S030
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
--27--
1075030
* 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
--28--
~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
.,
--29--
:, .
1075030
.
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
:
EXAMPLE 4
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
--30--
-:- . .. . : . - . . - . . .
. ~ . .
.~ - ~ . . . : . .
- - - : : ' ~ - -
~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%
EXAMPLE 5
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%
--32--
. -
.
~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
EXAMPLE 6
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%
--33--
1075030
Found C, 57, 50; H, 4. 45; N, 9. 61;
Cl, 12, 23%
IR spectrum (liquid paraffin) ~ 1793 cm
EXAMPLE 7
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%
.
--34--
- `~
10~5~)30
IR spectrum (liquid paraffin) ~f 1790 cm
EXAMPLE 8
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
--35--
~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
.
--36--
,.~ - ~ . ~ -
- ~: ' . ' .: . .
. , .
-` ~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
--37--
~075(~30
EXAMPLE 9
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.
38-
- , :
- ~ ' ' ' ' ' ' : ''
1075030
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.
,, .
.,
--39--
1075030
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
--40-- -
~ ' .
~075030
EXAMPLE 11
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.
--41--
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
EXAMPLE 12 -
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%.
.
--42--
-
1075030
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
EXAMPLE 13
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
--43--
~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%
EXAMPLE 14
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.
--44--
- - - :
~075~130
,
; 1, 3-dimethyl-4-(3, 4-dimethoxybenzoyl)-5-hydroxypyrazole
hydrochloride m.p. 164 - 165 C
.. . .
EXAMPLE 15
:'
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--
1075030
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.
--46--
107S030
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.
EXAMPLE 17
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.
EXAMPLE 18
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
--47--
.,
~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.
EXAMPLE 19 -
- ,
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.
EXAMPLE 2 0
-,
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.
--48--
- 1075()30
EXAMPLE 21
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.
EXPERIMENT 1
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
--49--
~.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~.
- ' "
--50--
:-
1075030
~ 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
EXPERIMENT 2
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
--52--
' ' .
