Note: Descriptions are shown in the official language in which they were submitted.
3~
N-Phenylamino Acid Esters and Their Production
The present invention has been divided out of
Canadian Patent Application Serial No. 492,126 filed October 3,
1935.
This invention rela-tes to novel N-phenylamino acid
esters and their production and their use as intermediates in
the preparatlon of quinoxalines.
The inven-tion provides compounds of the formula:
O R2 R3 X ¦ ¦
R O-C-lH-l ~ N ~ (I)
2 O
wherein X is a hydrogen atom, a fluorine atom or a chlorine
atom, R2 is a hydrogen atom or a methyl group, R is a
hydrogen atom or a methyl group and R4 is a Cl 4 alkyl group.
These compounds are useful in the preparation of
quinoxalines of the formula.
~~
wherein A is a group of the formula: -CH-N- or -C=N- in which
R2 l3 R
R is a hydrogen atom or a methyl group, R3 is a hydrogen atom
or a methyl group and the nitrogen atom is bonded to the
benzene ring.
3 ~ L~ ~
-- 2
The quinoxalines are useful as intermediates in the
preparation of tetrahydrophthalimides of the general formula:
~A~X~o
Ri
1 C5 alkyl group, a C3-C alkenyl
C3-C5 alkynyl group or a Cl-C3 alkoxymethyl group, X and A are
as defined above.
The compounds of the formula
R ~ X )l (I)
2 O
wherein X, R , R3 and R are as defined above can be prepared
by reacting an N-nitrophenylphthalimide of formula (IV)
o
~ X ~ (IV)
with an amin acid ester of the formula:
R3
HN-CH-COOR (VIII)
wherein R , R and R are each as deEined above in an amount
of 2.5 to ~ equivalents to one equivalent of the N-nitro-
phenylph-thalimide (IV) in a solvent (e.g. dioxane, dimethyl-
formamide, dimethylsulfoxide) at a -terr.perature of 50 to 200C.
To obtain the quinoxalinesof the formula (II) the
N-phenylarnino acid ester(I)is subjected to reductive cyclization
with an appropriate reducing agent, for instance, iron in an
acid (e.g. acetic acid) to give the dihydroquinoxalinone (VI)
~3
o,~N~b3 J
More specifically, the N-phenylamino acid ester (I) is treated
with 3 to 10 equivalent amounts of powc1ery iron such as
electrolytic iron or reduced iron in a solvent (e.g. water,
alcohol, acetic acid, ethyl acetate) in the existence of an
excessive amount of an acid (e.g. acetic acid, hydrochloric
acid) at a temperature of 50 to 200C.
The N-nitrophenylphthalimide (IV) is per se known
and obtainable by the method as described in EP-A-0077938A.
Typical examples for production of the compounds (I)
and (VI) are illustra-tively shown in the Eollowing Examples.
Example 1
2-(4-Fluoro-3-nitrophenyl)-4,5,6,7-te-trahydro-2H-
isoindole-1,3-dione (5.8 g) was added to a mixture of glycine
methyl ester hydrochloride (7.5 g), triethylamine (6 g) and
r~ J~
1,4-dioxane (50 ml?, and the resultant mixture was
heated under xeflux for 4 hours, followed by addition of
water and extraction with ethyl acetate. The extract was
washed with water, dried and concentrated. The residue was
crystallized from methanol to give 2-(4-methoxycarbonyl-
methylamino-3-nitrophenyl)-4,5,6,7-tetrahydro-2H-iso-
indole-1~3-dione t2.6 g). m.p., 220C.
In the same manner as above, the N-phenylamino
acid esters (I) as shown in Table l were obtained:
Table 1
O R2 R3 X
R O-C-CH-N ~ N ~ (I)
CompoundX R R3 R4 Physical constant
No.
.
a F H H C~2CH3 m.p~ 166.8C
b F H CH3 CH2CH3 m.p., 159.2C
c Cl H H CH2CH3 m.p., 153 - 154 C
Fxample 2
2-(4-Methoxycarbonylmethylamino-3-nitrophenyl)-
4,5,6,7-tetrahydro-2H-isoindole~1,3-dione (2.06 g) was
dissolved in a mixture of acetic acid (20 ml) and ethyl
acetate t20 ml), and the resultant solution was dropwise
added to a mixtu~e of 5 % aqueous acetic acid (10 ml) and
iron powder (4 g) at 70 to 80C, followed by stirring at the
same temperature for 3 hours.- The reaction mixture was
~,¢~r~
allowed to cool, diluted with water and extracted with ethyl
acetate. The extract was washed with sodium bicarbonate
solution, dried and concentrated to give 2-(3,4-dihydro-
2(1H)-quinoxalinon 7-yl)-4,5,6,7-tetrahydro 2H-isoindole-
1,3-dione (1.3 g). m.p., 208 - 209C.
In the same manner as above, the dihydroquino-
xalinones (VI) as shown in Table 2 were obtained.
Table 2
R3
(VI)
-
Compound X R2 R3 Physical constant
No.
_ _ _
d ~ H CH3 m.p., 263.4C
e F H H m.p., 236.6C
f F CH3 H m.p., > 220C
g ~1 H H m.p., 174C
Example 3
2-(3,4-Dihydro 6-fluoro-2(lH)-quinoxalinon-7-yl)-
4,5,6,7-tetrahydro-2H-isoindole-1,3-dione (0~43 g) was
added to a mixture of sodium hydroxide (0.16 g), water (2.1
ml) and 30 ~ aqueous hydrogen peroxide (0.21 ml), and the
resultant mixture was stirred at room temperature for 16
hours. Ether was added thereto to separate an aqueous
layer, which was adjusted to pH 4 with acetic acid. The
precipitated crystals were collected by filtration and
washed with water to give 2-(6-fluoro-2(lH)-quinoxalinon-7-yl)-
-- 6
4,5,6,7-tetrahydro-2~-isoindole-1,3-dione (0.32 g) m.p., ~300C.
The tetrahydrophthAlimides can be obtained by
reacting a quinoxaline of the formula:
o
A~l \ ~
wherein X and A are each as defined above,with a halide of
the formula:
R1_y (III)
wherein R is as defined above and Y is a chlorine atom, a
bromine atom or an iodine atom in a solvent in the presence
of a dehydrohalogenating agent at a temperature of 0 to 50C
for a period of 0.5 to 24 hours.
In the above reaction, the halide ~III) and the
dehydro-halogenating agent are used respectively in amounts
of 1 to 3 equivalents per equivalent of the quinoxaline
(II). Examples of the solvent are ethers (e.g. diethyl
ether, diisopropyl ether, dioxane, tetrahydrofuran,
ethylene glycol, dimethyl ether), acid amides (e.g.
formamide, N,N-dimethylformamide, N,N-dimethylacetamide),
sulfur compounds (e.g. dimethylsulfoxide), and their
mixtures. Inorganic bases (e.g. sodium hydride), organic
lithium compounds (e~g. n-butyl lithiumf methyl lithium,
lithium diisopropylamide), etc. may be used as the
dehydro-halogenating agent.
3 ~
After completion of the reaction, the reaction
mixture is subjected to an ordinary post-treatment such as
extraction with an organic solvent and concentration. If
desired, any conventional purification procedure, such as
recrystallization or chromatography, may be employed.
Practical and presently preferred embodiments
for the production of the tetrahydrophthalimides (I) are
illustratively shown in the following Examples.
Example 4
10Sodium hydride (33 mg) was suspended in N,N-
dimethylformamide (1.5 ml), and the resultant suspension was
cooled to -30C. 2-(3,4-Dihydro-6-fluoro-2(1H)-quinoxalin-
7-yl~-4,5,6,7-tetrahydro-2H-isoindole-1,3-dione (400 mg~ was
added thereto at -30C, followed by stirring for 30 minutes.
1-Bromo-2-propyne (165 mg) was added thereto at -30~C, and
the temperature was gradually raised to room temperature
(e.g. 20 - 25~C), followed by stirring for 6 hours. The
reaction mixture was admixed with water and extracted with
ethyl acetate. The extract was washed with water, dried and
concentrated. The residue was purified by silica gel thin
layer chromatography using a mixture of ethyl acetate and
hexane (1 : 2) as an eluant to give 2-[3,4-dihydro-6-
fluoro-1-(2-propionyl)-2(1H)-quinoxalinon-7-yl]-4,5,6,7-
tetrahydro-2H-isoindole-1,3-dione (80 mg). m.p., 205.6C.
25The tetrahydrophthalimides as shown in Table
3 were ob~ained in the same manner as above.
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It has been found tha-t the tetrahydrophthalimides
show a high herbicidal activity against a wide variety of weeds
including broad-leaved weeds, Graminacaeous weeds, Commelina-
ceous weeds and Cyperaceous weeds in the agricultural plowed
field by foliar or soil treatment without producing any
material phytotoxicity in various agricultural crops such as
corn, wheat, rice, soybean or cotton. Examples o broad-
lea~ed weeds are wild buckwheat (Polygonum con~olvulus), pale
smartweed (Polygonum lapathifolium), common purslane
(PortuIaca oleracea), common chickweed
tStellaria media), common lambsquarters (Chenopodium album3,
redroot pigweed (Amaranthus retroflexus), radish (Raphanus
sativus), wild mustard (Sin~is arvensis), hemp sesbania
(Sesbania exaltata)~ sicklepod (Cassia obtusifolia),
velvetleaf lAbutilon theophrasti), prickly sida (Sida
spinosa), field pansy (Viola arvensis), catchweed bedstraw
(Galium aparine) r ivyleaf morningglory (Ipomoea hederacea~,
tall morningglory ~Ipomoea purpurea), henbit (Lamium
amplexicaure), jimsonweed (Datura stramonium), black
nightshade (Solanum niyxum), persian speedwell (Veron_ a
persica), common cocklebur (Xanthium pensylvanicum~, common
sunflower (Helianthus annuus), etc. Examples of Grami-
naceous weeds are Japanese millet (Echinochloa frumentacea),
barnyardgrass (Echinochloa crus-galli), green foxtail
(Setaria viridis), large crabgrass (Diqitaria sanguinalis)
annual bluegrass (Poa annua), blackgrass (Alopecurus
myosuroides~, oats IAvena sativa), wild oats ~Avena fatua~,
johnsongrass (Sorqhum halepense)~ etc. Examples of
Commelinaceous weeds are asiatic dayflower (Commelina
communis), etc. Examples of Cyperaceous weeds are yellow
nutsedge (Cyperus esculentus), etc.
Further, the tetrahydrophthalimides
are effecti~e in exterminating paddy field
weeds including Graminaceous weeds such as barnyardgrass
(Echinochloa oryzicola), broad-leaved weed such as common
falsepimpernel (Lindernia procumbens), indian toothcup
(Rotala indica) and waterwort (Elatine triandra), Cype-
raceous weeds such as hardstem bulrush (Scirpus juncoides)
and needle spikerush ~Eleocharis acicularis) and others such
as monochoria (Monochoria vaqinalis) and arrowhead
(Saqittaria pyqmaea), without any phytotoxicity to rice
plants on flooding treatment.
Specific examples of the tetrahydrophthalimides are
2-[1-(2-propenyl)-2(1~)-quinoxalinon-7-yl]-4,5,6,7-tetrahydro-
2H-isoindole-1,3 dione, 2 [3,4-dihydro-1-(2-propynyl)-2(lH)-
quinoxalinon-7-yl]-4,5,6,7-tetrahydro-2H-isoindole-1,3-dione,
2-[6-fluoro-1-(2-propenyl)-2(lH)-quinoxalinon-7-yl]-4,5,6 t 7-
tetrahydro-2H-isoindole-1,3-dione, 2-[3,4-dihydro-6-fluoro-1-
(2-propynyl)-2(lH)-quinoxalinon-7-yl]-4,5,6,7-tetrahydro-2H-
isoindole-1,3~dione, etc.
- 13 -
On the practical usage of the tetrahydrophthal-
imides they may be applied in any preparation form such
as emulsifiable concentrates, wettable powders, suspensions,
~ranules, etc. in combination with conventional solid or
liquid carriers or diluents as well as surface active agents
or auxiliary agents. The content of the tetrahydrophthal-
imides as the active ingredient in such formulation form
is usually within a range of 0.05 to 90 % by weight, pre-
ferably of 0.1 to 80 % by weight. Examples of the solid
carrier or diluent are fine powders or granules of kaolin
clay, attapulgite clay, bentonite, terra alba, pyrophyllite,
talc, diatomaceous earth, calcite, walnut powders, urea,
ammonium sulfate and synthetic hydrous silicate, etc. As
the liquid carrier or diluent, there may be exemplified
aromatic hydrocarbons (e.g. xylene, methylnaphthalene),
alcohols (e g. isopropanol, ethylene glycol, cellosolve~,
ketones (e.g. acetone, cyclohexanone, isophorone), soybean
oil, cotton seed oil, dimethylsulfoxide, N,N-dimethylform-
amide, acetonitrile, water, etc.
The surface active agent used for emulsification,
dispersion or spreading may be any of the anionic and
non-ionic type of agents. Examples of the surface active
agent include alkylsulfates, alkylarylsulfonates, dialkyl-
sulfosuccinates, phosphates of polyoxyethylenealkylaryl
~5 ethers, polyoxyethylene alkyl e~hers, polyoxyethylene
C~
alkylaryl ethers, polyoxyethylene ~olyoxypropylene block
copolymer, sorbitan fatty acid esters, polyoxyethylene
sorbitan fatty acid esters, etc. Examples of the auxiliary
agents include ligninsulfonates, sodium alginate, polyvinyl
alcohol, gum arabic, CMC (carboxymethyl cellulose3, PAP
(isopropyl acid phosphate), etc.
Practical embodiments of the herbicidal composi-
tion according to the invention are illustratively shown in
the following examples wherein parts are by weight. The
compound number of the active ingredient corresponds to the
one in Table 3.
Formulation Exam~le 1
Fifty parts of Compound No. 14, 3 parts of calcium
ligninsulfonate, 2 parts of sodium laurylsulfate and 45
parts of synthetic hydrous silicate were thoroughly mixed
while being powdered to form a wettable powder.
Formulation Example 2
Five parts of Compound No. 8, 14 parts of poly-
oxyethylenestyrylphenyl ether, 6 parts of calcium dodecyl-
benzenesu]fonate, 30 parts of xylene and 45 parts of N,N-
dimethylformamide were thorou~hly mixed to form an emulsi-
fiable concentrate.
Formulation Example 3
Two parts of Compound No. 5, 1 part of synthetic
hydrous silicate, 2 parts of calcium ligninsulfonate, 30
parts of bentonite and 65 parts of kaolin clay were thor-
oughly mixed ~hile being powdered. The mixture ~as then
kneaded with water, granulated and dried to form aranules.
Formulation Example 4
Twenty-five parts of Compound No. 8 were mixed with
3 parts of polyoxyethylene sorbitan monooleate, 3 parts of
carboxymethyl cellulose and 69 parts of water and pulveriæed
until the particle size of the mixture became less than 5
microns to form a suspension.
The tetrahydrophthalimides thus formulated in
any suitable formulation are useful for the pre-
emergence or post-emergence control of undesired weeds by
soil or foliar treatment as well as flood fallowing
treatment. These treatments include the application to the
soil surface prior to or after transplanting or
incorporation into the soil. The foliar treatment may be
effected by spraying the herbicidal composition containing
the tetrahydrophthalimides over the top of the plants.
It may also be applied directly to the weeds if care is
taken to keep the chemical off the crop foliage.
The tetrahydrophthalimides
may be used together with other herbicides to improve their
activity as herbicides, and in some cases, a s~nergistic
effect can be expected. Further, they may be applied in
combination with insecticides, acaricides, nematocides,
fungicides, plant growth regulators, fertiliæers, soil
improvers, etc.
Furthermore, the tetrahydrophthalimides can be
used as herbicides applicable to agricultural plowed field
as well as paddy field. They are also useful as herbicides
to be employed for orchards, pasture land, lawns, forests, non-
3. ~¢~51~3~
- 16 -
agricultural fields, etc.
The dosage rate of the tetrahydrophthalimides
may vary depending on the prevailing weather conditions, the
formulation used, the prevailing season, the mode of appli-
cation, the soil involved, the crop and weed species, etc.
Generally, however r the dosage rate is from 0.02 to 100
grams, preferably from 0~05 to 50 grams, of the active in-
gredient per are. The herbicidal composition
formulated in the form of an emulsifiable concentrate,
a wettable powder or a suspension may ordinarily be employed
by diluting it with water at a volume of 1 to 10 liters per
are, iE necessary, with the addition of an auxiliary agent
such as a spreading agent. Examples of the spreading agent
include, in addition to the surface active agents as noted
above, polyoxyethylene resin acid (ester), ligninsulfon-
ate, abietylenic acid salt, dinaphthylmethane~disulfonate,
paraffin, etc. The composition formulated in the form of
granules may normally be applied as such without dilution.
The biological data of the tetrahydrophthalimides
as herbicides is illustratively shown in the following
Examples wherein the phytotoxicity to crop plants and the
herbicidal activity on weeds were observed visually as to
the degree of germination as well as the growth inhibition
and rated with an index 0, 1, 2, 3, ~ or 5, in which the nu-
meral "0" indicates that no material difference is seen in
comparison with the untreated plant and tlle numeral "5" which
indicates complete inhibition or death of the test plants.
~ f~
- 17 -
The compounds shown in Table 4 below were used for
comparison.
Table 4
.
No. Chemical structure ¦ Remarks
A Cl Commercially
~ ~-~ available herbi-
Cl~/ \ ~ ~/ \~NO2 cide; "chloro-
~ Cl nitrofen"
Test Example 1
Cylindrical plastic pots (diameter, 10 cm; heignt,
10 cm) were filled with upland field soil, and the seeds of
Japanese millet, tall morningglory and velvetleaf were sowed
therein and covered with soil. A designated amount of the
test compound formulated into an emulsifiable concentrate
according to Formulation Example 2 was diluted with water,
and the dilution was sprayed onto the soil surface by means
of a small hand sprayer at a spray volume of 10 liters per
are. The test plants were further grown in a greenhouse for
20 days, and the herbicidal activity was examined.
The results are shown in Table 5.
18 -
Table 5
Compound Dosage Herbicidal activity
No. (g/are)
Japanese Tall morning- Velvet-
millet glory leaf
~ ~ ~ 5
18 20 5 5 S
14 20 5 5 5
17 1200 55 5 55
/ l O
Test Example 2
Cylindrical plastic pots (diameter, 10 cm; height,
10 cm) were filled with upland field soil, and the seeds of
Japanese millet, radish and velvetleaf were sowed therein
and cultivated in a greenhouse for 10 days. A designated
amount of the test compound formulatedinto an emulsifiable
concentrate according to Formulation Example 2 was diluted
with water containing a spreading agent, and the dilution
was sprayed over the foliage of the test plants by means of
a small hand sprayer at a spray volume of 10 liters per are.
The test plants were further grown in the greenhouse for 20
days, and the herbicidal activity was examined.
The results are shown in Table 6.
? r~
-- 19 --
Table 6
Compound Dosage ¦ Herbicidal activity
No. (g/are)
Japanese ¦ Radish ¦ Velvetleaf ¦
10 ~ ~ ~ ~
I~ ~.5
17 5 4 5 5
l l 2.5 1 0 ¦ 0 _
Test Example 3
Cylindrical plastic pots (diameter, 8 cm; height,
12 cm) were filled with paddy field soil r and the seeds of
barnyardgrass (Echinochloa oryzicola3 and broad-leaved weeds
(e.g. common falsepimpernel, indian toothcup, waterwort)
were sowed in 1 to 2 cm depth. Water was poured therein to
make a flooded condition, and rice seedlings at the 2-leaf
skage were transplanted therein and grown in a greenhouse.
Six days ~at that time the weeds began to germinate) there-
after, a designated amount of the test compound formulated in
an emulsifiable concentrate according to Formulation Example
2 and diluted with water (5 ml) was applied to the pots by
q~ 3~
- 20 -
perfusion. The test plants were grown for further 20
days in the greenhouse, and the herbicidal activity was
examined.
The results are shown in Table 7.
Table 7
Compound Dosage Herbicidal activity
No. (g/are)
Rice plant Barnyard- Broad-leaved
grass weed
0- 5 5
14 10 1 4 5
_
¦ 20
Test Example 4
Vats (33 cm x 23 cm x 11 cm) were filled with
upland field soil, and the seeds of soybean, cotton, corn,
common cocklebur, tall morningglory, velvetleaf, redroot
pigweed, black nightshade, barnyardgrass and green foxtail
were sowed therein to 1 to 2 cm depth. A designated amount of
the test compound formulated in an emulsifiable concentrate
according to Formulation Example 2 was diluted with water,
and the dilution was sprayed onto the soil surface by means
of a small hand sprayer at a spray volume of 10 liters per
are. The test plants were further grown in a greenhouse
for 20 days, and the herbicidal activity was examined.
The results are shown in Table 80
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~ 21 -
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- 22 -
Test Example 5
Vats (33 cm x 23 cm x 11 cm~ were filled with
upland field soil, and the seeds of wheat, catchweed
bedstraw, persian speedwell, common chickweed, cornmon
lambsquarters, pale smartweed, wild buckwheat and annual
bluegrass were sowed therein to 1 to 2 cm depth. A designated
amount of the test compound forrnulated into an emulsifiable
concentrate according to Formulation Example 2 was diluted
with water, and the dilution was sprayed onto the soil
surface by means of a small hand sprayer at a spray volume
of 10 liters per are. The test plants were further grown in
2 greenhouse for 27 days, and the herbicidal activity was
examined.
The results are shown in Table 9.
-- 23 --
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:~
,G -
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- 2~ -
Test Example 6
Vats (33 cm x 23 cm x 11 cm) were filled with
upland field soil, and the seeds of corn, wheat, sugar beet,
common cocklebur, velvetleaf, black nightshade, tall morning-
glory, common lambsquarters and green foxtail were sowedtherein and cultivated for 18 days in a greenhouse. A
designated amount of the test compound formulated in an
emulsifiable concentrate according to Formulation Example 2
was diluted with water containing a spreading agent, and the
dilution was sprayed over the foliage of the test plants by
means of a small hand sprayer at a spxay volume of 5 liters
per are. The test plants were further grown in the green-
house for ZO days, and the herbicidal activity was examined.
At the time of application, the test plants were generally
at the 1 to 4 leaf staqe and 2 to 12 cm in height, although
the growth stage of the test plants varied depending
on their species.
Th~ results are shown in Table 10.
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