Note: Descriptions are shown in the official language in which they were submitted.
5~244
rr}le plesent invention relates to herbici~ally active
pyridyloxyphenoxy unsaturated derivatives as well as herbicidal
composition comprising said derivatives as an ac-tive ingredient.
Recently, many herbicides have been proposed and used
to eliminate agricultural labour. l~owever, various problems with
respect to herbicidal effects and safety have been found in prac-
tical application of the herbicides.
Herbicides which have no significant adverse effect on
the desired plants but are effective against noxious weeds in
small doses and are significantly safe without any environmental ~-
pollution have always been desired.
It has now been found that certain pyridyloxyphenoxy
unsaturated derivatives are sa-ti.sfactory herbicides and have
improved herbicidal effects.
According to the present invention -there are provided
pyridyloxyphenoxy unsaturated derivatives having the formula
Cl
Cl~_ 0 ~3--OCHCH=CElZ (I )
CH3 ~
wherein ~ re?resents -CH2oHr C~ or -C09R' an~ R represen-~s
a group selected from hydrogen, organic saltSlinorganic salts,
alkyl containing 1 to 6 carbon atoms, haloalkyl containing 1 to
6 carbon atoms and one halosen atom, alkenyl containing 2 to 6
carbon atoms, alkynyl containing 2 to 6 carbon atoms, phenyl
which may be substituted with: halogen, alkyl containing 1 to 6
carbon atoms, benzyl, alkoxyalkyleneoxyalkyl wherein each alkyl
group contains 1 to 6 carbon atoms, pyridylmethyl; and alkoxy
alkyl wherein each alkyl group contains 1 to 6 carbon atoms and
R' represents an alkyl group having 1 to 6 carbon atoms.
~,~"" -1- ;'
"` 115~4
The pyridyloxyphenoxy unsaturated derivatives having
the formula (I) of the present invention have superior herbicidal
activity to gramineous weeds such as barnyard grass, crab grass
and Johnson grass in comparison with the compounds described in
Japanese Unexamined Patent Publication No. 131540/1977 such as
~-[4-(3,5-dichloropyrid~2-yloxy)phenoxy] valerianic acid deriva-
:20
~ la-
.. . ..
.. ... .. .
1 15~2J~4
tives such as methyl and isopropyl esters or the sodium salt and
in Japanese Unexamined Patent Publication Nos. 48432/1976 and
87173/1977 such as ~-[4-(3,S-dichloropyrid-2-yloxy)phenoxy] pro
pionic acid derivatives such as methyl and ethyl es$ers or ammon-
ium and sodium salts. The compounds of formula I also have
s~perior herbicidal activities in comparison with butoxyethyl
~[4-(3,5,~-trichloropyrid-2-yloxy)phenoxy] propionate disclosed
in Japanese Unexamined Patent Publication No. 15382/lg78.
The compounds of formula I have superior residual
activity in soil in soil treatment and also have excellent herbi-
cidal effects such as long suppression of weeds in post emergence;
long suppression of the recovery of the weeds from an incomplete
suppresslon thereof in foliage treatment; growth control of grown
weeds and excellent sta~ility to the factors normally varying the
activity of the herbicides such as caused by rain-fall, atmos-
pheric moisture and high temperature thus having stable activity.
The compounds of formula I have a methyl group at r-position of
the pyridyloxyphenoxy isobutenyl compounds, whereby special herbi-
cidal effects especially, a significant herbicidal effect against
2Q gramineous weeds such as Johnson ~rass, dent foxtail, barnyard
grass and large crab grass is present~
The compounds of formula I have significant selectivity
without phytoto~icity to broad leaf crop plants such as radish,
soybeam, adzuki bean, peanut, cotton, flax, beat, sugar beet,
potato, colza, sweet potato, cucumber, olive, Chinese cabbage,
lettuce, tomato, eggplant, radish, onion, watermelon, strawberry,
pimento, sunflower, tea, coffee, rubber, peppermint, and hop and
tobacco plants and completely control gramineous weeds. The com-
pounds of formula I can be applied as herbicides by desirable
methods in every season such as by soil treatment and foliage
treatment in post-emergence and pre-emergence. Typi~al gramineous
weeds which are effectively controlled by the herbicides of the
1 15~24~1
present invention are as follows: Johnson grass, quack grass,
para-grass, southern sandbar, finger grass, bermuda grass, crow-
foot grass, large crab grass, crab grass, barnyard grass, jungle
rice, cattail grass, goose grass, cogon grass, wrinkle grass,
southern cut grass, bearded splangle top, red splangle top,
mexican splangle top, brown top panicum, sour paspalum, water
paspalum, natal grass r raoul grass, green foxtail, bristly fox-
tail and yellow foxtail.
The compounds of :Eormula I have a low vapor pressure
and have no phytotoxic effect on growing gramineous plants such
as wheat, barley, oat, rye.
The pyridyloxyphenoxy unsaturated derivatives having
the formula (I) can be produced by the following processes.
1) The pyridyloxyphenoxy unsaturated derivatives having
the formula (I)
Cl
Cl--~ O ~OCHCH=CHZ (I)
CH3
(Z is defined abov ) can be produced by reacting an unsaturated
halide having the formula
Hal - CHCH=CHZ' (II)
C~I3
(Z' is Z defined above or a group convertible to Z and Hal is a
halogen atom) with a pyridyloxyphenol having the formula
Cl ~ O- ~ OH (III~ ~
2~
in the presence of a base at a temperature from 0 to~l50C for
1 to 20 hours and if necessary, converting Z' into Z. In the
formula, the groups convertible to Z include cyano, halogen, and
other functional groups. Suitable bases include alkali metal
hydroxides such as sodium hydroxide or potassium hydroxide;
alkali metal carbonates such as sodium carbonate, potassium car-
bonate or sodium bicarbonate; alcoholates such as sodium ethylate
and tertiary amines such as triethyl amine, dimethyl aniline or
pyridine. Suitable reaction media include water, acetone, methyl-
ethyl ketone, methanol, isopropanol, butanol, dimethylformamide,dimethylsulfoxide, tetrahydrofuran, benzene, toluene, xylene,
chlorobenzene, chloroform, carbon tetrachloride and dichloro-
ethane. The resultinq compound can be converted into the desired
pyridyloxyphenoxy unsaturated derivative by the following pro-
cesses.
The pyridyloxyphenoxy unsaturated derivatives of
formula (I) can be produced directly by reacting a pyridyloxy-
phenol having the formula
Cl
Cl~ O ~3 OH
N
with a halopentenoic compound or a halopentenol compound having
the formula
Hal-CHCH=CHZ
in the presence of a base in a suitable solvent at a temperature
from 0 to 150C for 1 to 20 hours.
The pyridyloxyphenoxy unsaturated acid esters having
the formula
2~a~
Cl
Cl ~ r ~ ~ OCHCI;=C;.COOR
. CH3
can be produced by reacting the pyridyloxyphenol having the
formula
Cl
Cl ~ ~ o ~ OE~ (III)
with a halopentenoic acid to proc~uce a pyridyloxyphenoxy unsat-
urated acid having the formula
Cl
{ ~ ~ OCHCH=CI;COO;; ~IV)
N
~}l3
and then, reacting the corresponding compound having the ~ormula
ROE~ with the pyridyloxyphenoxy unsaturated acid (IV) or its acid
halide having the formula
Cl
C1 ~ ~ O - ~ - OCHCH=CHCOHal (IV'~
in a suitable solvent or in the absence of a solvent at a temp- ~
erature from 0 to 150C for 1 to 20 hours.
1 ~58~4
The pyridyloxyphenoxy unsaturated acid halide (IV') can
be easily obtained by reacting a halogenating agent, such as
thionyl chloride and phosphorus trihalides with the pyridyloxy-
. phenoxy unsaturated acid of formula (IV).
The pyridyloxyphenoxy unsaturated acid thiol esters
having the formula Cl
Cl ~ O ~ _OCHCH=CHCOSR'
N
CH3
can be also produced by reacting a pyridyloxyphenoxy unsaturated
acid of formula (IV) or its acid halide of formula (IV') with
the corresponding mercaptan in the presence of a base as a dehydro-
halogenation agent in a suitable inert solvent in the absence of
a solvent at a temperature from -10 to 150C ~or 1 to 20 hours.
The pyridyloxyphenoxy pentenols having the formula
~20
Cl ~ ~ O ~ ~ OCXCH=CHCH20E~
CE13
can be produced by hydrogenating the pyridyloxyphenoxy unsaturated
acid of formula (IV) or its acid halide of formula (IV') or its :
ester, with a reducing agent, such as sodium borohydride and
lithium aluminum hydride, in a suitable inert solvent at a temp-
erature from -20 to 100C for 1 to 20 hours.
These compounds of formula I are produced by the main
reaction of the pyridyloxyphenol (III) with the unsaturated
halide (II) and if necessary, converting the product into the
object compound.
The following are processes for converting the product
obtained by the main reaction.
a) The pyridyloxyphenoxy unsaturated derivatives having
the formula (I) can be produced by reacting a pyridyloxyphenoxy
unsaturated acid having the formula
Cl
Cl -~ O _~3OC~ICH=C~ICOO~I tIV)
C~13
with a compound having the formula
ROH
(R ls defined above~ in the presence of a catalyst, such as an
aromatic sulfonic acid such as benzenesulfonic acid, toluenesul-
fonic acid or ~-naphthalenesulfonic acid; an anhydrous sulfate
such as anhydrous copper sulfate or anhydrous iron sulfate; phos-
phorus oxy-chloride, phosphoric acid anhydride, boron trifluoride
or acidic ion-exchanger at a temperature from 20 to 150C or
under reflux for 1 to 20 hours.
b) The pyridyloxyphenoxy unsaturated derivative having
the formula (I~ can be produced by reacting a pyridyloxyphenoxy
unsaturated acid having the formula
Cl
' .
Cl ~ O ~ OCI:CH=C~ICOO~I (IV)
with a base, such as alkali metal hydroxides, alkaline earth
metal hydroxides and organic bases e.g. amines and amino compounds,
in a reaction medium at a temperature from 0 to 100C for 0.5 to
10 hours.
c) The pyridyloxyphenoxy unsaturated derivatives having
" ~ 15824d,!
the formula tI) can be produced by reacting pyridylphenoxy pen-
tenoyl halide having the formula
Cl
Cl ~ ~ O ~ OCHCH=CHCOHal (V)
CH3
with a compound having the formula
ROH, R'SH
(R and R' are defined above) in the presence of a base as a
dehydrohalogenation agent in a reaction medium or excess of the
compound having the formula
ROH
or in the absence of a reaction medium, at a temperature from
10 to 150C for 1 to 20 hours. Suitable dehydrohalogenation
agents which are inorganic or organic bases include alkali metal
hydroxides such as sodium hydroxide or potassium hydroxide;
alkali metal carbonates such as sodium carbonate, potassium car-
~ bonate or sodium bicarbonates; alcoholates such as sodium ethylate;
;~ 20 and tertiary amines such as triethyl amine, dimethyl aniline orpyridine. Suitable reaction media include acetone, methyl ethyl
ketone, dimethylformamide, dime-thylsulfoxide, tetrahydrofuran/
benzene, toluene, xylene, chlorobenzene, chloroform, carbon tetra-
chloride and dichloroethane. The pyridyloxyphenoxy pentenoic
halide of formula (V) can be produced by reacting the pyridyloxy-
phenoxy unsaturated acid of formula (IV~ with thionyl chloride or
phosphorus trihalide in a solvent.
d) The pyridyloxyphenoxy pentenoate having the formula
Cl ~ O ~ OCHCH=CHCOOM (VI)
1~82~
wherein M is an alkali metal, an alXaline earth metal, a heavy
metal or an amino group including an alkylamino and an arylamino
group; can be easily produced by neutralizing the corresponding
acid or acid halide with the corresponding base. The reaction
is preferably carried out in a solvent at a temperature higher
than room temperature.
e) The pyridyloxyphenoxy pentenol derivatives having
the formula Cl
Cl~ ~ o ~ OCHCH=C~ICH2OB (VII)
CH3
wherein B represents hydrogen atom, an alkyl carbonyl, a halo-
alkyl carbonyl, an aryl carbonyl, an alkylamino carbonyl or an
arylaminocarbonyl group can be easily produced by reacting 4-
halo-2-pentenol or its ester with a pyridyloxyphenol having the
formula
Cl
{ ~ ~ OH (III)
The reaction is preferably carried out in a solvent in the
presence of a base. When the pyridyloxyphenoxy pentenol (B=H)
is produced can be esterified to obtain the corresponding ester.
f) ~he pyridyloxyphenoxy pentenols having the formula
Cl ~ O ~ OCHCH=CHCH2OIi (VIII)
CH3
~I 158~414
.
can be produced by reducing a pyridyloxyphenoxy unsaturated
derivative having the formula
Cl- { ~ O ~ OCHCH=CHCOA'
CH3
(A' is OR, or a halogen atom) obtained in the processes of a),
b), c), d~ or e) in the presence of a reducing agent, such as
li hium aluminum hydride and sodium borohydride, in a reaction
medium at a temperature from -20 to 100C for 1 to 20 hours.
If necessary, the resulting pyridyloxyphenoxy pentenol is ester-
ifying with the corresponding acid to obtain its esters.
The present invention will be further illustrated by
way of the following Examples.
Preparation 1:
Methyl 4-[4~~3,5-dichloropyrild-2-yloxy)phenoxy~-(2)-
pentenoate
~ ~ To a solution of 12.8 g (0.05 mole) of 4-~3,5-dichloro-
pyrldF2-y1Oxy~phenol and 11.6 g t0.06 mole of methyl 4-bromo-(2)-
pentenoate in 70 ml of methanol, 7.6 g (0.055 mole) of potassium
carbonate was added and the mixture was refluxed for 3 hours.
The reaction mixture was extracted with ether and the ether phase
was washed with water, then with dilute hydrochloriç acid and
then with water and dehydrated over anhydrous sodium sulfate.
The ether was distilled off and low ~oiling compounds were dis-
tilled off at 140C in vacuum under 0.01 mmHg to obtain 16.4 g
~yield of 89.2%) of orange viscous liquid having n20 1.5548.
Pre~aration 2:
. . :
4-~4-(3,5~dichloropyrld-2-yloxy)phenoxy]-(2~-pentenoic
_.
acid
A solution of sodium ethylate was prepared by adding
, -- 1 0 --
~ 1582~fl~
.
O.9 g (0.04 mole) of sodium metal in 70 ml of ethanol and 9.0 g
(0.035 mole) of 4-(3,5-dichloropyrid-2-yloxy)phenol was added
thereto , 9.4 g (0.045 mole) of ethyl 4-bromo-(2)-pentenoate was
then added. The mixture was refluxed for 3 hours, 24 ml of 10%
aqueous solution of sodium hydroxide was then added to the mix-
ture and the mixture was further refluxed for 30 minutes. The
reaction mixture was poured into 150 ml of water to obtain a 501-
ution of sodium 4-r4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-
pentenoa~e. Concentrated hydrochloric acid was added to the sol-
ution to provide acidic conditions whereby an oily product was
formed and solidified. The solid product was filtered and dried
and recrystallized from ethanol to obtain 9.7 g (yield of 78.3~)
of white powdery crystals having a melting point of 157 to 159C.
Preparation 3:
50dium 4-~4-(3,5 dichloropyrid-2-ylox~)phenoxy]-(2)-
~entenoate-
17.7 gram (0.05 mole) of 4-[4-~3,5-dichloropyrid-2-
yloxy)phenoxy]-(2)-pentenoic acid was dissolved in 24.1 g (0.05
mole) of a 5% aqueous solution of sodium hydroxide. Water was
then distilled off to obtain 180 g (yield of 95.5%) of white
powdery crystals having a melting point of 240 to 245C. By the
same method, the potassium salt can be obtained using potassium
hydroxide. A calcium, iron, zinc, magnesium, manganese or
aluminum salt can be obtained by r~acting-the corresponding metal
salt with an aqueous solution of the sodium or potassium salt.
Pre~aration 4:
4-[4-~3,5-dichloropy~rid-2-~loxy)phenoxy]-(2) pentenoic
acid dimethylamine salt
In 30 ml of 5~ dimethylamine aqueous solution, 14.2 g
(0.04 mole) of 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pen-
tenoic acid was dissolved and the excess of dimethylamine and
~ater were then distilled off on a rotary evaporator to obtain
:~15~2~4
15.6 g (yield Qf97,4%~ of orange viscous liquid. By the same
method, the ammonium salt, methylamine salt, ethylamine salt,
n-propylamine salt, isopropylamine salt, diethylamine salt,
di-n-propylamine salt, di-isopropylamine salt, dibutylamine
salt, triethylamine pyridine salts and picoline salts of 4-[4-3,5-
dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoic acid were obtained.
Preparation 5:
Ethyl 4-[4-(3,5-dichloro~yrid-2-~loxy)phenoxy]-(2)-
pentenoate ~i
A mixture of 17.7 g (O.OS mole) of 4-[4-(3,5-dichloro-
pyrid-2-yloxy)phenoxy]-(2)-pentenoic acid, 50 ml of ethanol, 50
ml of benzene and 3 g of concentrated sulfuric acid was refluxed
for 4 hours with the removal of water in a distillation trap.
The reaction mixture was diluted with 100 ml of benzene and washed
with water and the benzene phase was dehydrated over anhydrous
sodium sulfate. BenzPne was distilled off and low boiling com-
pounds were distilled off a 140C in vacuum under 0.01 mmHg to
obtain 15.2 y (yield of 82.8%) of orange viscous liquid having
~D 1 . 5697.
Preparation 6:
sec-Butyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2
pentenoate
A mixture of 10.6 g (0.03 mole) of 4-[4-(3,5-dichloro-
pyrid-2-yloxy)phenoxy]-2-pentenoic acid and 30 ml of thionyl
chloride was refluxed for 6 hours. Excess thionyl chloride was
distilled off from the reaction mixture and the residue of the
acid chloride was admixed with 30 ml of sec-butanol. After the
addition, the reaction mixture was gradually heated at 60C for
5 hours. Excess o~ sec-butanol was distilled off to obtain 10.7
g (yield of 90.3%) or orange viscous liquid having nD 1.5565
- 12 -
~ ~5~2~L
. ~
Preparation 7:
Allyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-
pentenoate
11.2 grams (0~03 mole) of 4~4-(3,5-dichloropyrid-2-
yloxy)phenoxy] (2)-pentenoyl chloride obtained by the process
of Preparation 6 was added to a mixture of 2.3 g (0.04 mole) of
allyl alcohol, 2.6 g (0.033 mole) of pyridine and 100 ml of
anhydrous toluene with stirring and cooling and the mixture
was stirred at room temperature for 3 hours. The prodl~ct was
washed with water and dehydrated over anhydrous sodium sulfate.
Toluene was distilled off and low boiling compounds were dis-
tilled off at 140C in vacuum under 0.01 mmHg to obtain 9.8 g
(yield of 86.5~ of orange viscous liquid having n20 1.5706.
In accordance with the same process except using 2-butenyl
alcohol or l-butynyl alcohol instead of allyl a]cohol, each
esterification was carried out to obtain butenyl 4-[4-(3,5-
dichloropyrid-2-yloxy)phenoxy] - (2)-pentenoate and butynyl
4-[4-(3,5-dichloropyrid-2-yloxy)pllenox~] - (2)-pentenoate.
~ Preparation 8:
:~ '
Methoxvethoxyethyl 4-[4-~3,5~dichloropvrid-2-yloxy)
.
phenoxv]-(2)-~entenoate
~ mixture of 35.5 g (0.1 mole) of 4-[4-(3,5-dichloro-
pyrid-2-yloxy)phenoxy]-(2)-pentenoic acid, 24 g (0.~ mole) of
2-(2-methoxyethoxy)ethanol; 100 ml of benzene and 5 g of con~
centrated sulfuric acid was refluxed for 7.5 hours until the
distillation of water was finished. After the reaction, the
benzene phase was sequentially washed with water, with 5%
aqueous solution of sodium bicarbonate and with water and
dehydrated over anhydrous sodium sulfate. Benzene was distilled
off and low boiling compounds were distilled off at 120C in a
vacuum under 0.06 mm~lg to obtain 38.6 g ~yield of 84.5%) of
orangish yellow viscous liquid having nD 1.5685. In accordance
- 13 -
,i
1 :~582~'~
with the same process except using 2-(2-ethoxyethoxy)ethanol or
2-(2-n-propoxyethoxy)ethanol instead of 2-~2 methoxyethoxy)
ethanol, each esterification was carried out to obtain ethoxy-
ethoxy ethyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-penten-
oate or n-propoxyethoxyethyl 4-[4-~3,5-dichloropyrid-2-yloxy)
phenoxy]-(2)-pentenoate.
Preparation 9:
Pyrid~lmethyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-
(2)-pentenoate
A mixture of 11.2 g (0.03 mole) of 4-[4-(3,5-dichloro-
pyrid-2-yloxy)phenoxy]-(2)-pentenoyl chloride and 7.1 g (0.065
mole) of 3-hydroxymethylpyridine in 50 ml of benzene was heated
for 4 hours with stirring. After the reaction, the reaction
mixture was cooled and sequentially washed with water, with 5
aqueous solution of sodium bicarbonate, with water, with 5~
hydxochloric acid and with water and dehydrated over anhydrous
magnesium sulfate. Benzene was distilled off to obtain 12 g
(yield of 92.3%) of reddish brown viscous liquid having n20
1.5670~ In accordance with the same process except using benzyl
alcohol instead of 3-hydroxymethylpyridine, the esterification
was carried out to obtain benzyl 4-[4-(3,5-dichloropyrid-2-
yloxy)phenoxy] (2~-pen~enoate.
Preparation 10:
3-Methoxy-3-methylbutyl 4-[4-(3,5-dichloropyrid-2-
yloxy)phenoxy]-~2)~pentenoate
In 50 ml of methylethyl ketone, 5.1 g (0.02 mole) of
4~(3,5-dichloropyrid-2-yloxy~phenol and 6.1 g (0.022 mole) of
3-methoxy-3-methylbutyl 4-bromo-2-pentenoate were dissolved and
3.0 g (0.022 mole) of potassium carbonate was added to the solu-
tion at room temperature with stirring. The mixture was refluxed~or 5 hours. After cooling, the mixture was filtered. 200 ml
of benzene was added to the filtrate and washed twice with 50 ml
- 14 -
`! 1 158244
of saturated aqueous solution of sodium bicarbonate and then
thrice with 50 ml of water and dehydrated over anhydrous sodium
sulfate. Benzene was distilled off and low boiling compounds
were distilled off at 105~C in a vacuum under 0.12 mmHg to obtain
8.1 g (yield of 89.1%) of pale brown viscous liquid having n20
1.5547. In accordance with the same process except using 3- -
ethoxy-3-methylbutyl-4-bromo-2-pentenoate instead of 3-methoxy-
3-methyl-butyl-4-bromo-(2)-pentenoate, the synthesis was carried
out to obtain 3-ethoxy-3-methylbutyl 4-[4-(3,5-dichloropyrid-2-
yloxy)phenoxy]-(2)-pentenoate.
Pr~paration 11:
S-Methyl 4-[4-(3~5-dichloropyrid-2-yloxy)phenoxy]-(2)
pentenothiolate
In 100 ml of toluene, 2.9 g (0.06 mole) of methyl mer-
captan and 7.6 g (O.055 mole) of potassium carbonate were dis-
solved and 20.5 g (0.05 mole) of 4-[4-(3,5-dichloropyrid-2-yloxy)
phenoxy]-(2)-pentenoyl bromide was added to the solution at 5 to
lO~C with stirring to cause reaction at room temperature for 4
hours. Water was added to the reaction mixture and toluene phase
was washed with wa~er and dehydrated over anhydrous sodium sulfate.
Toluene was distilled off to obtain 16.7 g (yield of 86.9%) of
orange viscous liquid having n20 1.6072. In accordance with the ;
same process except using ethyl mercaptan, propyl mercaptan or
butyl mercaptan instead of methyl mercaptan, each synthesis was
carried out to obtain S-ethyl, S-propyl or S-~utyl 4-[4-(3,5-
dichloropyrid-2-yloxy)phenoxy]-(2~-pentenothiolate.
Preparat on 12:
- 4-[4-(3,5-Dichloropyrid-2-yloxy)phenoxy]-(2)-penten-1-ol
In 50 ml of ether, 0.9 g (0.0226 mole) of lithium
aluminum hydride was suspencled. A solution of 8.4 g (0.0226
mole) of 4-~4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoyl
chloride in 50 ml of ether was then added dropwise to the suspen-
~ - 15 -
2 ~ 4
sion at 10 to 15C over 30 minutes. After the addition, the
mixture was stirred at room temperature for 1 hour and the
reaction mixture was poured into 100 ml of ice water. The
ether phase was washed with water and dehydrated over anhydrous
sodium sulfate and ether was distilled off to obtain 6.0 g
(yield of 77.9%) of orangish yellow viscous liquid having n20
1.578~.
Preparation 13:
2-Chloroethyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-
(2)-pentenoate
In 50 ml of benzene, 5.6 g (0~015 mole) of 4-~4-(3,5-
dichloropyrid-2-yloxy)phenoxy]-(2)-pentenoyl chloride and 1.3 g
(0~017 mole) of ethylene chlorohydrin were mixed~ The mixture
was refluxed over 3 hours until the generation of hydrogen
chloride ceased. After cooling, the reaction mixture was washed
with 5% aqueous solution of sodium hydroxide and then with water.
The benzene layer was dehydrated over anhydrous sodium sulfate
and ~enzene was distilled off and low boiling compounds were
distilled off in vacuum under 110C/0.07 mmHg to obtain 5.2 g
~ield of 83~2%) of orange viscous li~uid having n20 1.5700. In
accordance with the same process except using ethylene-bromohydrin
2,2,2-trichloroethyl alcohol or 3-chloropropyl alcohol instead of
ethylenechlorohydrin, each synthesis was carried out to obtain
2-bromoethyl, 2,2,2-trichloroethyl or 3-chloropropyl 4-[4-(3,5-
dichloropyrid-2-yloxy)phenoxy~-(2)-pentenoate.
Preparation 14:
p-Tolyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy]-(2)-
pentenoate
In 20 ml of acetone, 5.6 g (0.015 mole) of 4-[4-(3,5-
dichloropyrid-2~yloxy)phenoxy]-(2)-pentenoyl chloride was dis-
solved. The solution was added dropwise to a solution of l.S g
(0.015 mole) of 4-methylphenol and 1.3 g (0.15 mole) of sodium
- 16 -
~82~
bicarbonate in 20 ml of acetone at lO to 15C with cooling over
lO minutes. After the addition, the reaction mixture was stirred
at room temperature for l hour, and was then poured into water.
The resulting oily product was extracted with benzene.
The benzene layer was washed with 5% aqueous solution of sodium
hydroxide and then, with water and dehydrated over anhydrous sodium
sulfate-. Benzene was distilled off and low boiling compounds were
distilled off in vacuum under 1 00C/0. 08 mmHg to obtain 5. 8 g (yield
of 86. 5%) of brown viscous liquid having n D 1. 5699. In accor-
dance with the same process except using phenol,
3-methylphenol or 4-chlorophenol instead of 4-methylphenol, each
synthesis was carried out to obtain phenyl, 3-methylphenyl or 4-chloro-
phenyl 4- ~4- (3, 5- dichloropyrid- 2-yloxy)phenoxy~- (2 )- pentenoate .
The typical compounds obtained by said processes will be
exemplified. The compound numerals are referred in the following
des cription .
Compound No. 1
4-~4-(3. 5-dichloropyrid-2-yloxy)phenoxy~-(2)-
pentenoic acid: white powdery crystal
m.pO 157 to 159C
Compound No. 2
Sodium ~-~ 4- ( 3, 5- dichloropyrid- 2 - yloxy)phe noxy~-
(2)-pentenoate: white powdery crystal
m.p. 241 to 245C
C ome~ No . 3
4~ 4- (3 . 5- dichloropyrid- 2- yloxy)phenoxy~- (2 )-
pentenoic acid diethyl amine salt: orange viscous liguid
Compound No. 4
Methyl 4-( 4- (3, 5- dichloropyrid- 2-yloxy)phenoxy~-
(2)-pentenoate: orange viscous liquid n D 1. 5548
b.p.>130C/0.01 mmHg
~ ~15~24~
Compound No. S
Ethyl 4-( 4- ~ 3, 5- dichloropyrid- 2- yloxy)phe noxy) -
(2)-pentenoate: orange viscous liquid n D 1. 5697
b.p. > 135C/O.a7 mmHg
n- Propyl 4-[ 4- (3, 5- dichloropyrid- 2-yloxy)phenoxy~-
(2)-pentenoate: orange viscous liquid nD 1 . 5614
b.p. > 120C/0. 1 mmHg
Compound NoO 7
iso- Propyl 4-(4-(3, 5-dichloropyrid-2-yloxy~phenoxy) -
(2~-pentenoate: orange viscous liquid n D 1. 5593
b.p. > 130C/0.01 mmHg
Cornpound No._
sec-Butyl 4-~4-(3,5-dichloropyrid-2-yloxy)phenoxy)-
(2)-pentenoate: orange viscous liquid nD 1. 5565
b.p. > 120C/0.2 mmHg
ompound No. 9
2-Chloroethyl 4-~4-(3,5-clichloropyricl-2-yloxy)phenoxy~-
(2)-pentenoate: orang~e viscous liquid n2D0 1. 5770
b.p. > llO~C/0.07 mmHg
Compound No. 10
2-Bromoethyl 4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy3-
(2)-pentenoate: orange viscous liquid nD 1. 5810
b.p. > 125C/0. 1 mmHg
Com~und No . I 1
Allyl 4-[ 4-(3, 5-dichloropyrid-2-yloxy)phenoxy)-(2)-
pentenoate: orange viscous liquid nD 1. 5706
b.p. > 120C/0. 1 mmHg
~:15~244
Compound No. 12
Propargyl 4-[ 4- (3, 5- dichloropyr id- 2-yloxy)phenoxy3-
(2)-pentenoate: orange viscous liquid n 1. 5905
b . p . > 1 3 0C / 0. 06 mmEIg
Compound No. 13
Phenyl 4-~4-(3,5-dichloropyrid-2-yloxy)phenoxy)-
(2)-pentenoate: orange viscous liquid nD 1 5601
b . p . > 1 1 0C / 0 . 07 mmHg
Compound No. 14
Methoxyethoxyethyl 4-~4-(3,5-dichloropyrid-2-yloxy)-
phenoxy~ (2)-pentenoate: brown viscous liquid n2D 1. 5685
b . p . > 12 5C / 0 . 07 rnmHg
Compound No 15
Pyridylmethyl 4-~4- ( 3, 5 - dichloropyrid- 2- yloxy)-
phenoxy~-(2)-pentenoate: brown viscous liquid nD 1. 5670
b . p . > 1 1 0C / 0. 07 mmHg
Cornpound No. 16
-
p-Tolyl4-~4-(3J 5-dichloropyrid-2-yloxy)phenoxy~-
~2)-penteno~te: brown viscous liquid n D 1. 5699
b.p. >100C/0.08 m}nHg
Compound No. 17
3-Methoxy-3-methylbutyl 4-~4-(3,5-dichloropyrid-2-yloxy)-
phenoxy) - ( 2) - pentenoate: light brow n vis cous liq uid
n D 1 . 5547
b . p . ~ 1 1 0C / 0 . 1 mmHg
Cor pound No. 18
S- Methyl 4-~4- (3, 5-dichloropyrid- 2-ylo~y)phenoxy)-
(2)-pentenothiolate: brown viscous liquid nD 1. 6072
-- 19 --
~ ~8244
Comeound No. 19
S-Ethyl4-~4-(3,5-dichloropyrid-2-yloxy)phenoxy~-
(2)-pentenothiolate: brown viscousliquid nD 1.5973
Compound No. 20
S-n-Propyl-4-~4-(3,5-dichloropyrid-2-yloxy)phenoxy)-
(2)-pentenothiolate: brown viscousliquid nD 1.6002
b.p.> 125C/0.04 m mHg
Compound No. 21
S-n-Butyl-4-~4-(3,5-dichloropyrid-2-yloxy)phenoxy)-
~2)-pentenothiolate: brown viscous liquid nD 1.6120
b.p. ~120C/0.03 m mHg
Compound No. 22
4-[4-(3,5-dichloropyrid-2-yloxy)phenoxy~-(2)-
penten-1-ol: orange yellow viscousliquid
nD 1.5784
The compounds of formula I produced by said syntheses
have significant herbicidal effect and non-phytotoxicity to many
crop plants and can be applied to up-land, paddy fields,
orchards, forests and non-cultured grounds by soil treatment or
foliage treatment by selecting a suitable method of application
and a suitable dose of the active ingredient.
The dose of the active ingredient of the compound of
formula I depends upon the weather conditions, soil conditions,
form of the composition, season of the application and method of
the application and types of crop plants and weeds and the stage
of growth of the weeds. It is usually in a range of O.Ol to lO
kg preferably O.l to 5 kg especially 0.5 to 3 kg per hectare in
the soil treatment or the foliage treatment.
it is usually applied in a concentration of lO to lO,000
ppm preferably lO0 to 5,000 ppm especially 250 to 3,000 ppm of
the active ingredient. When the application of the herbicidal
composition is by spraying from an airplane, the concentration
- 20 -
~ ~5~2~
of the active ingredient is usually in the range of lO,000 to
75,000 ppm. For example, 0.5 to 1.5 kg of the active ingredient
is sprayed at a rate of 20 to 50 liter/ha.
When the compound of formula I is used as a herbicide,
the compound can be used in the original form and also in the
form of compositions such as granules, wettable powers, dusts,
emulsifiable concentrates, fine powers, flowables, suspensions,
etc. to impart the superior effect.
In the preparation of the herbidical compositions, the
compound of the present invention can be uniformly mixed with or
dissolved in suitable adjuvants such as solid carrier such as
talc, bentonite, clay, kaolin, diatomaceous earth, silica gel,
vexmiculite, lime, siliceous sand, ammonium sulfate or urea;
liquid carriers such as alcohols, dioxane, acetone, cyclohexanone,
methyl naphthalene or dimethylformamide; surfactants as emul-
sifiers dispersing agents or wetting agents such as alkyl sulfate,
alkylsulfonate, polyoxyethyleneglycol ethers, polyoxyethylene-
alkylaryl ethers such as polyoxyethylenenonylphenol ether or
polyoxyethylenesorbitane monoalkylate; and carboxymethyl cellulose,
gum arabic and other adjuvants.
~ :
The amounts of the active i~gredients, adjuvants and
additives in the herbicidal aompositions of the present inven-
tion will be further illustrated.
Wettable powder:
Active ingredient: 5 to 95 wt. ~ preferably 20 to 50 wt.
Surfactant : l to 20 wt. % preferably 5 to lO wt. ~
Solid carrier : 5 to 85 wt. % preferably 40 to 70 wt. %
The active ingredient is admixed with the solid carrier
and the surfactant and the mixture is pulverized.
Emulsifiable concentrate:
Active ingedient: 5 to 95 wt. % preferably 20 to 70 wt. ~
Surfactant : l to 40 wt. % preferably 5 to 20 wt.
~ ~ S~2~
Liquid earrier : 5 to 90 wt. % preferably 30 to 60 wt.
The aetive ingredient is dissolved in the liquid
earrier and the surfaetant is admixed.
Dust:
Aetive ingredient: 0~ 5 to 10 wt. ~6 preferably 1 to 5 wt. g6
Solid earrier : 99 . 5 to 30 wt. % preferably 99 to 95 wt. %
The aetive ingredient is mixed with f ine solid earri~r
and the mixture is pulverize~.
Granule:
Active ingredient: 0. 5 to 40 wt. '71O preferably 2 to 10 wt. %
Solid carrier : 99. 5 to 60 wt. % preferably 98 to 90 wt. %
The active ingredient is sprayed on the solid carrier or
further coated with the solid carrier to form the granule.
Other herbicides may be incorporated in
the herbicidal composition of the present invention
Suitable additional herbieides inelude: earboxylie aeid type.
eompounds such as 2,3,6-trichlorobenzoic acid and salts thereof,
2,3,5,6-tetrachlorobenzoic acid and salts thereof, 2-methoxy-3,S,6-
triehlorobenzoic acid and salts thereof, 2-methoxy-3,6-dichlorobenzoic
acid and salts thereof, 2-methyl-3,6-dichlorobenzoic acid and salts
thereof, 293-dichloro-6-methylbenzoic acid and salts thereof, 2,4-
dichlorophenoxyacetic acid and salts and esters thereof, 2,4,5-
triehlorophenoxyacetie aeid and salts and esters thereof, 2-methyl 4-
ehlorophenoxyacetie acid and salts and esters thereof, 2-(2,4, 5-tri-
chlorophenoxy) propionic acid and salts and esters thereof, 4-~2,4-
dichlorophenoxy~ butyric acid and salts and esters thereof, 4-~2-methyl-
4-chlorophenoxy) butyrie acid and salts and esters thereof, 2,3,6-tri-
chlorophenylacetic acid and salts thereof, 3,6-endoxohexahydrophthalate
and salts thereof, dimethyl 2, 3, 5, 6-tetrachloroterephthalate, trichloro-
acetic acid and salts thereof, 2, 2-dichloropropionic acid and salts thereof
and 2, 3-dichloroisobutyric acid and salts thereof; and carbamic acid type
cornpounds such as S-ethyl N,N-di(n-propyl) thiolcarbamate, S-n-propyl
- 22 -
1 1 5 ~ 4
N, N-di(n-propyl) thiolcarbamate, S-ethyl N-ethyl-N-(n-butyl) thiolcarba-
mate, S-n-propyl N-ethyl-N-(n-butyl) thiolcarbamate, S-2-chloroallyl
~,N-diethyl dithiocarbamate. N-methyl dithiocarbamate, S-ethyl
hexahydro lE~-azepine-l-carbothioate. S-(4-chlorobenzyl) N,N-diethyl
thiolcarbamate, S-benzyl N,N-di-sec-butyl thiolcarbamate, isopropyl
N-phenyl carbamate, isopropyl N-(3-chlorophenyl) carbamate, 4-chloro-
o-butyn-2-yl N-(3-chlorophenyl) carbamate, methyl N-(3, 4-dichloro-
phenyl carbamate and me-thyl-N-(4-aminobenzene sulfonyl) carbamate;
phenol type compounds such as 2-sec-butyl-41 6 dinitro phenol and salts
thereof and pentachlorophenol and salts thereof; urea type compounds
such as 3- (3, 4-dichlorophenyl~ 1, 1-dimethyl urea, 3-phenyl- 1, 1- dimethyl
urea, 3 - ( 3, 4 - dichlorophenyl) - 3 -methoxy- 1, 1- dimethylurea, 3 - (4- chlor o-
phenyl) - 3-methoxy- 1, 1- dimethyl urea, 3- ( 3, 4- dichlorophenyl)- 1 -n-butyl-
1- methylure a, 3 - ( 3, 4 - dichlorophenyl) - 1- methoxy- 1- methylurea, 3 - ( 4 -
chlorophenyl)- 1 - methoxy- 1 -methylurea , 3- (3, 4- dichlorophenyl)- 1 ,1, 3 -trimethylurea, 3-(3, 4-dichlorophenyl) 1, l-diethylurea, 1-(2-methyl-
cyclohexyl)-3-phenylurea, 1-(5-t-butyl-1,3,4-triadia7ol-2-yl)-1,3-
dimethylurea, 3- (3- chloro- 4-methylphenyl)- 1 ,1 -dimethylurea, 3- (3-
chloro-4-methoxyphenyl)-1,1-dimethylurea and dichloralurea; triazine
type compounds such as 2-chloro-4,6-bis(ethylamino)-s-triazine, 2-
chloro-4-ethylamino-6-isopropyl-amino-s-triazine, 2-chloro-4,6-bis
(methoxypropylamino)-s-triazine, 2-methoxy-4, 6-bis~isopropylamino)-
s-triazine, 2-methylmercapto- 4, 6-bis(isopropylamino~- s-triazine,
2-methylmercapto-4,6-bis(ethylamino)-s-triazine, 2-methylmercapto-
4-ethylamino-6-isopropylamino-s-triazine, 2-choloro-4,6-bis(iso-
propylamino)- s -triazine, 2-methoxy- 4, 6-bis (ethylamino)- s- triazine,
2-methoxy-4-ethylamino-6-isopropylamino-s-triazine, 2-methyl-
mercapto-4-(2-methoxyeth~ylamino)-6-isopropylamino-s-triazine,
2-~2-chloro-4-ethylamino-s-triazine-6-yl) amino-2-methyl propionitrile,
4-amino-6-t-butyl-3-methylthio-1,2,4-triazine-5-~4H)-one, and 3-
cyclohexyl-6-dimethylamino- 1-methyl-s-triazine-2,4-(lH, 3H) dione;
ether type compounds such as 2,4-dichloro-4'-nitrodiphenyl ether,
2, 4, 6~ trichloro- 4' - nitrodiphenyl ether, 2, 4- dichloro- 6-fluoro- 4' -
nitrodiphe nyl ether, 3- methyl- 4' - nitrodiphe nyl ethe r, 3, 5- dimethyl-
4'-nitrodiphenyl ether. 2,4'-dinitro-4-trifluoromethyl diphenyl ether,
-- 23 --
~ :~5~2~
2, 4- dichloro- 3' -methoxy- 4' - nitrodiphe nyl ether, 2- chloro- 4- trifluoro-methyl- 4' - nitrodiphe nyl ether, 2 - chloro- 4- triEl uoromethyl 3 ' - ethoxy-4'-nitrodiphenyl ether, 2-chloro-4-trifluoromethyl-3'-ethoxy cabonyl-
4'-nitrodiphenyl ether and 2-chloro-4-trifluoromethyl~3'-ethoxy
carbonyl ethoxy - 4 ' - nitrodiphenyl ether; anilide type
compounds such as N (3,4-dichlorophenyl)propionamide, '
N-(3,4-dichlorophenyl~2-methylacrylamide, N-(3-chloro-4-methy]-
phenyl) - 2- methylpentamide, N- ( 3, 4- dichlorophenyl) -trimethyl acetamide,
N-(3J4-dichlorophenyl)- 2, 2 -dimethyl valeramide, N-isoprophyl-N-
phenylchloroacetamide, N-n-butoxymethyl-N-(2,6-diethylphenyl)
chloroacetamide and N-n-methoxymethyl-N-~2,6-diethylphenyl) chloro-
acetamide; u~acil type compounds such as 5-bror~o-3-sec-butyl-6-methyluracil,
5-bromo-3-cyclohexyl-1,6-dimethyluracil, 3-cyclohexyl-5,6-trimethy-
leneuracil, 5-bromo-3-isopropyl-6-methyluracil, and 3-tert.-butyl-5-
chloro- 6 - methyluracil;
nitrile type compounds such as 2.6-dichlorobenzonitrile, diphenyl-
acetonitrile, 3,5-dibromo-4-hydroxybenzonitrile, and 3,5-diiodo- 4-hydroxy-
bel~zoni~rile, others such as 2-chloro-N,N-diallylacetamide, N-(l,l-dimethyl)-
propynyl)-3, 5-dichlorobenzamide, maleic hydrazide, 3-amino-lJ
2,4-triazole, mono-sodium methane arsonate, di-sodium methane
arsonate, N,N-dimethyl-2,2-diphenyl acetamide, N,N-di(n-propyl)-
2,6-dinitro-4-trifluoromethyl aniline, N,N-di(n-propyl)-2,6-dinitro-4-
methyl aniline, N,N-di(n-propyl)-2,6-dinitro-4-methylsulfonyl aniline,
0-(2,4-dichlorophenyl)-0-methyl-N-isopropyl phosphoramide thioate,
4-amino- 3, 5, 6-trichloropicolinic acid, 2, 3-dichloro- 1, 4-naphthoquinone,
dimethoxythiocarbonyldisulfide, 3-isopropyl-lH-2,1,3-benzothiadiazinc-
4 ( 3 H) - one - 2, 2 - dioxide, 6, 7 - dihydrodipyrido ~1, 2 - a : 2 ' : 1 ' - c) pyr azi -
nium salt, 1, 1 ' - dimethyl-4, 4 ' - bipy:ridinium salt, 3, 4, 5, 6- tetrahydro-
.
-- 24 --
~ ~5~2a~4
3, 5-dimethyl- 2H- 1, 3, 5-thiadia~ine- ~- thione, 1, 2-dimethyl_3, 5-di
phenylpyra~olium methyl sulfate, N-sec-butyl-2, 6-dinitro-3~ 4-xylidine,
N- s e c . - b utyl- 4- t- b utyl- 2, 6 - dinitroaniline, N3, N3 - diethyl- 2, 4- di nitro-
6-trifluoromethyl- 1, 3-phenylenediamine, 1,1~1 -trifluoro(4' -phenyl-
sulfonyl)-methane sulfono-O-toluidine, 2-(1-naphthoxy)-N,N-diethyl
propionamide, 2-t-butyl-4-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4
oxadiazole-2(3H)one,4-chloro-5-methylamino-2-(o~Jo~,o( -triluforo-m-
tolyl)-3(2H)-pyridazinone) N-cyclopropylmethyl-~,o(,o~-trifluoro-2,6-
dinitro-N-propyl-p~toluidine and N-phosphonomethyl glycine, ets~.
When the other herbicide described is mixed with the com-
pound of formula I the ratio of the compounds and the
dose of the cornpounds are selected depending upon the selectivities and
herbicidal effects of the compound~ to the crop plants and the control
of noxious weeds treated therewith.
The following are examples of the preparation of the
herbicidal compositions. However, the types and the ratio
of the adjuvants are not limited and can be varied from con-
ventional considerations of herbicidal compositions.
Composition No. 1: Wettable powder:
Active ingredient 30wt.%
Sodium higher alcohol sulfate 5 wt. %
Clay 65wt.% ~`
These components were uniformly mixed and pulverized to -
prepare a wettable powder.
-- 25 --
~5~
Com osition No. 2. Emulsifiable concentrate:
P
Active ingredient 25wt.%
Polyoxyethylenealkylaryl ether l O wt. ~0
C alcium dinaphthylmethanes ulfonate 5 wt . %
~ylene 6 0 wt . %
These components were uniformly mixed to prepare an
emulsifiable concentrate.
3: Granules:
Active ingredient 3 wt. %
Bentonite 40 wt. %
Clay 50 wt. %
Sodium lignin sulfonate 7 wt. %
These components were uniformly mixed and pulverized
and then, kneaded with water and granulated and dried to prepare
granulates .
Composition No. 4: Dust:
Active ingredient 2 wt. %
Clay 9 8 wt . %
The components were rnixed and pulverized to prepare a
dust.
- 26 --
2 4 ~
C omposition No . 5: Wettable powder:
Active ingredient3 0 wt . %
Kaolin 43 wt . %
White carb on 2 0 wt . %
Polyvinyl alcohol 5 wt. %
Polyoxyethylenenonylphenol 2 wt. %
These components were uniformly mixed and pulverized to
prepare a wettable powder.
Composition No. 6: Emulsif_ble concentrate:
Active ingredient 50wt.%
Polyoxyethyle ne nonylphenol 5 wt . %
Alkylarylsulfonate5 wt. %
Xylene 40 wt. %
These components were uniforrrlly mixed to prepare an
emulsifiable concentrate.
Com~osition No. 7: Granules:
Active ingredient 5 wt.%
Siliceous sand 92 wt.(~o
White carbon 3 wt. %
These components were uniformly mixed and pulverized and
then, kneaded with water and granulated and dried to prepare a granulate,
-- 27 --
~ 15~2~4
.
Composition No. 8: Dust:
Active ingredient 3 wt. %
White carbon 2 wt. %
Kaolin 9 5 wt . %
These components were mixed and pulverized to prepare
a dust.
The herbicidal activity of the compounds of the present
invention will be further illustrated by certain experimental tests.
In the experiments, the following reference compounds
were used as comparative tests.
Reference Compound (A)
C1
Cl ~ O ~~ O-CH CH2CH2 COONa
c~3
Reference Compound (B)
Cl
Cl ~O ~ O-CH CH2cH2coocH3
CH3 ;~;~
Reference Compound (C)
C1
C1 ~ O ~)--O-GH CH2CH2COOc3H7 -i
CH3
-- 28 --
2 ~ ~1
Referencc Compound (D)
Cl
Cl ~ 0 ~ 0 - CH C00NE~ 4
I
CH3
Reference Compound (E)
Cl
Cl ~ O --1~3 0 - CHCOOC 2H 5
Reference Compound (F)
Cl ~ 0~ OCHCOS~ ~H 5
-- 29 --
1 :~582~4
EXPERIMENT 1:
-
Test for crop plants and up-land weeds in pre-emergence
(pre-germination) soil treatment.
Each pot of 600 cm2 was filled with up-land soil and seeds
of wheat, barley, soybean, radish, barnyard grass and large crab
grass were sown in a depth of 0. 5 cm. Each emulsifiable concentrate
prepared in accordance with the method of Composition No. 2 was
diluted with water to give the specific concentration of the compound
for the application of 1 Klit. /ha. and the diluted solution was uniformly
sprayed on the soil surface. Twenty days after
the treatment, the herbicidal effect and
the phytotoxicity of the crop plants were observed and rated as follows:
The experiments were separately carried out as stated in
Tables .
Herbicidal effect or phytotoxicity:
10: Complete growth suppression is found;
9: Growth suppression of from 90 to 100%9
8: Growth suppression of from 80 to 90%;
~: Growth suppression of from 70 to 80%;
6: (;rowth suppression oi from 60 to 70%;
5: Growth suppression of from 50 to 60%;
4: Grol,vth suppression of from 40 to 50%;
3: Growth suppression of from 30 to 40%;
2: Growth suppression of from 20 to 30%;
1: Growth suppression of from 0 to 20%,
0: No herbicidal effect.
-- 30 --
~ 15824~
Wh.: Wheat Ba.: Barley
So.: Soybean Ra~: Radish
B.G.: Barnyard Grass Cr.G.: Large Crab Grass
(panicuxn crus-galli linnaeus) ~digitaria sanguinalis scopoli)
Results of Tests in pre-emergence soil treatments
Table 1 (Test 1-1 )
Compound ingre-
No. dier~t Wh. Ba. So. Ra.B. G. Cr. G.
_ (kg/ ha) ~ ~
Compound 0. 5 5 3 0 0 10 10
No. 1 _ 0.25 1 0 0 0 10 10
Compound 0. 5 5 3 0 0 10 10
No. 2 _. 0.25 1 0 0 0 10 10
Compound 0. 5 6 4 0 0 10 10
No. 3 _ 0.25 1 0 0 0 10 10
Compound 0. S 6 4 0 0 10 10
No 4 0.25 1 0 0 0 10 10
. _........... ,_ _
Compound 0. 5 6 4 0 0 10 10
No. 5 _ 0.25 2 0 _ 0 0 10 10
Compound 0. 5 5 4 0 0 10 10
No. 6 0. 25 1 0 0 0 10 10
Cornpound 0. 5 5 3 O O 10 10
No. 7 0. 2 5 0 _0 _ 0 0 _ _0_ 10 _
Compound 0. 5 5 3 0 0 10 10
No. 8 0.25 _ 0 0 _ 0 0 10 10
Compound 0. 5 5 3 0 0 10 10
No. 9 0.25 0 0 _ 0 110 10
Compour~d 0. 5 ~ 5 -- 4 O -o 10 10
No. 10 0.25 0 0 0 0 10 10
Compound 0. 5 5 3 _ 0 0 10 -10
No. 11 0.25 0 0 0 0 10 10
Compou~d O. 5 6 4 O O 10 10
No. 12 0.25 2 1 0 0 8
rReference 0. S 3 4 0 0~ ~ 6
Comp. (A) 0. 25 1 2 0 0 6 2
Reference 0. 5 6 7 0 0 4 5
Comp. (B) 0.25 3 4 0 0 1 _ _ 3
Reference 0. 5 4 3 0 0 4 5
Comp. (C) 0. 25 2 1 0 0 2 2
ReIerence 0. 5 ~ 5- 4 O O 6 7
Comp. (D) 0. 2 5 3 . 2 0 0 3 4
Reference 0. 5 - 7 7 0 _~ ~_
Comp (E ) 0 . 2 5 _ 3 4 0 0 2 3
- 31 -
2 41 4
.,
Table 2 tTest 1-2)
C ompound DnCgivee _ _
No. (dkg7ha)Wh. Ba. So. Ra B. G. Cr. G
Compound 0~ 5 5 3 0 0 10 10
No . 13 0. 2 5 2 _ I _ 0 0 _ 1 0 I 0
Compound 0. 5 2 2 0 0 10 10
No. 14 _ 0.25 1 1 0 0 10 10
Compound 0. 5 2 2 0 0 1 0 1 0
No. 15 0.25 1 1 0 o I 10 10
Cornpound 0. 5 2 _ O l 10
No. 16 0.25 1 1 0 o I 10 10
_ _ _ , _
Table 3 tTest 1-3)
_ ~ Dose _ __ . _ _
C ompoundianCgrvee-
No.(dkg7ha) . Wù. Ba. So. Ra. B. G. Cr. G
Compound 0. 5 0 0 0 0 l O 10
No 17 0 2 5 0 0 0 _ 1 0 1 0
_ . . ~
Table-4 (Test 1-4)
_ ._ _ . __ .
' Dtse .
C ompound anglrVee-
No. dient Wh. Ba. So. Ra. B. G.Cr. G.
. . (kg/ha) _ ~ .
Compound 0. S 0 0 0 0 10 10
No. 18 0.25 0 0 0 0 10 10 :
Compound 0. 5 O O O 0~ 10 10
No. 19 0.25 0 0 0 0 10 10
Reference 0 . S 2 3 0 0 3 4
Comp . (F ) _ 0. 2 S 1 1 0 0 1 2
-- 32 --
1 158~
able 5 (Test 1-5)
_ _ ¦ Dose __ _ _ .
Compound active
No. ingredient Wh. Ba. So. Ra. B. &. Cr. G .
¦ Compound(kgO/h5a) o û O O 1 0 10
I No. 22 0. 25 0 0 _ - 0 _ o ¦ 10 10
1 ~l5~2~
EXPERIMENT 2:
.
Test for crop plants and up-land weeds in pre-emergence
soil treatment. Each polyethylene pot of 2,000 cm2 was filled with up-land
soil and seeds of rice, maize~ wheat, soybean, cotton, radish, barn-
yard grass, large crab grass, dent foxtail, johnson grass and goose
foot (25 seeds for each plant) were sown in a depth of 0.5
cm. Each emulsifiable concentrate prepared in accordance with
the method of Composition No. 2 was diluted with water to give 0. 25,
û. 125 and 0. 0625 Kg/ha. of the active ingredient, and the diluted
solution was uniformly sprayed on the surface of the soil at a rate of 200 ml
per pot. Twen~y day~ after the treatment, the herbicidal effect and
the phytotoxicity of the crop plants were observed and rated as describ-
ed above.
Ric.: Rice
Mai.: Maize
Wh.: Wheat
So.: Soybean
Cot.: Cotton
Ra.: Radish
B.G.: Barnyard Grass (panicum crus-galli linnaeus)
Cr.G.: Large Crab Grass (digitaria sanguinalis scopoli)
D.F.: Dent Foxtail (alopecurus aequalis sobolewski var
amurensis ohwi)
J . G .: Johnson Grass (sorghum halepense~
G.F.: Goose Foot ~chenopodium album linnaeus var
centrorubrum makino) ~ -
.~
-- 34 --
~ ~5~2~L~
oo oc oo oo oo oo oo
r---- _ _ O
. 0 0~ O CO O ~ O O O O O O O O~
Q
~d ~ o o o o o o o o o o o o o o
E~ ~ _l _. ~ _l ~ _. _l _ ~ ,. ~ ~ ~ _
.,, __ I _ ~ _
~, C7
. oo oo 00 oo oo oo oo
O _ _- ~ ~ _l _. ~ _~ ~ _l ~
Ul _ _ _ .
~ _ . O O O O o o O O C~ O O o o O
O I P4 r~ l _I ~ I~ r~l ~1 1 ~1 _I _I ~ 1
~aa,C~" ---I---- ----
æ 0O 0O 0O 0O c~o 0O 0O
~d ~ 'I --- -
~ CD O C~ O O O O O O O C) O O O O O
a) a~ ~
_ __ __
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a~ .__ __
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- 35 -
1 ~5824
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-- 36 --
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-- 38 --
EXPERIMENT 3:
Test for crop plants and up-land weeds in (post-emer-
gence or post germination) foliage treatment. Each pot of 600
cm was filled with up-land soil and seeds of corn, barley,
soybean, radish, barnyard grass and large crab grass were sown.
Each emulsifiable concentrate prepared in accordance with the
method of Composition No. 2 was diluted with water to give the
specific concentration of the compound and the diluted solution
was uniformly sprayed at a rate of 1 kl/ha, when the gramineous
weeds were grown to 3 leaf stage and the broad-leaf weeds were
grown to the first divergence state. Fifteen days after the
treatment, the herbicidal effect and the phytotoxicity of the
crop plants were observed and rated as described above:
Wh.~ ~heat
Ba.: Barley
So.: Soybean
Ra.: Radish
B.G.: Barnyard Grass (panicum crus-galli
linnaeus)
Cr.G.: Larye Crab Grass (digitaria sanguinalis
scopoli)
_ ~9 _
1 :1582~
The experiments were separately carried out as stated in Tables.
Table 10 (Test 3- 1)
_ _ __ _ __
Compound Concen-
No. t(rppm)n Wh. Ba. So. Ra. B. G. Cr. G.
_ _ _ . _~_ _~_ _Compound 500 0 0 0 0 10 10
No 1 250 0 0 0 0 10 10
~ _ _~
Compound 500 0 0 0 0 10 10
No. 2 25û O O O O 10 10
Compound 500 0 ~ 0~ 0 10 10
No. 3 250 0 0 0 0 10 10
CompouDd 500 0 0 ~0 - 010 10
No 4 250 0 0 0 0 10 10
. _.
Compound 500 O O O O 10 10
No. 5 250 0 0 0 0 10 10
Compound 500 0~ 0-- 0 0 10 10
No. 6 250 0 0 0 0 10 10
Compound 500 0 0 0 0 10 10
No. 7 250 _ 0 0 _0 0 10 10
Compound 500 0 0 0 0 10 i 0
No. 8 250 0 0 0 0 10 10
Compound 500 O O O O 10 l o
No. 9 250 0 0 0 0 10 10
Compound 500 0 0 0 0 10 ~ 0
No . 11 250 0 0 _ 0 _10_ _ _ 10
Reference 500 2 3 0 0 6 ,~
Comp. (A) 250 1 1 _ O _ 2 4
Reference 500 3 4 0 0 6 6
Comp. ~B) 250 _ 2 _ 1_ _0 0 3 _ 2
Reference 500 2 3 0 0 4 4
Com~. (C) 250 _ 0_ _ 1_ r O 1 ~
Reference 500 3 4 0 0 5 6
Comp. (D) 250 2 2 O O 6
Reference 500 _ ~ 0 6
Comp. (E) 250 3 3 0 _ 3 - 4
_. _ _ __ ~ -~
-- 40 --
1 1582~4
Table 11 (Test 3-2)
_ __ _,_ . . _ I ~ .
C oncen-
Compound
No. tration Wh. Ba. So. Ra. B. G. Cr. G.
(ppm)
Compound 500 i O 10 b o 1 o 1 o
No . 14 2 5 0 1 0 _ 10 0 _ 0 10 10
C ompound5 00 10 10 0 0 10 10
No. 15 2 50 10 10 0 . 0 10 10
Compound 500 10 10 0 0 10 10
No . 1 6 _ 2 5 0 1 0 .. 1 0 0 _ . 0_ 1 0 _ 1 0
Table 12 ~Tes$ 3-3)
- _ _ j _ _ ~ I _ . i
Concen-
Compoundtration
No. (ppm) Wh. Ba. So. Ra. B. G. CrO G.
~ __ ~ _ . _ _ _ ~
Compound S00 3 2 O O 10 . :l O
_No. 17 250 O O _ _ _ O _10 _ 10
Table 13 (Test 3-4)
___ ._ . ~__ __ _._ _.
Concen-
Compound tration
: ~ No. ~ (ppm) Wh. Ba.. So. Ra.B. Go Cr. G.
. ~ , . . . _ . ~ _ . ,. _ . _ ~ .. _~. _ . __.
Compound 500 2 2 O O 10 :l O
No . 18 2 5 0~ . 0 1 _. ~ . ~.~_ 1 0 _1~0
Compound 500 10 9 0 0 10 10
No 19 250 6 _ 8 ~ 0 ~~_ 10 ~ 10
Reference 500 4 4 6 ~l 10 - I n
.~o~.~F) _ ZS0 2 _2 . 3 ~ 3_ 10 _ 1_
-- 41 --
2 4 4
Table 14 (Test 3-5)
. _ I Concen- ~ ~ _
Compound tration
No. . (ppm) Wh. Ba. So. Ra.B. G. Cr. G.
Compound 500 0 0 0 0 10 10
No. 22 250 0 0 _. 0 10 10
.
.
:~ '
-- 4~ --
~L 1582~
EX PERIMENT 4:
-
Test for crop plants and up-land weeds in post-emergence foliage
tre~tment. Each polyethylene pot of 2,000 cm2 w~s filled with up-land
soil and seeds of rice, maize~ wheat, soybean, cotton, radish, barn-
yard grass, crab grass, dent foxtail, johnson grass and goose foot
(25 seeds for each plant) were sown. Each emulsifiable
concen trate prepared in accordance with
the method of Composition No. 2 was diluted with water to give the
concentration of 125, 62.5 and 31.25 ppm and the diluted solutionwas
uniformly sprayed at a rate of 20. 0 ml per pot. when the plants were
grown to 2 to 4 leaf stages. Twenty days from the
treatment, the herbicidal effect and the
phytotoxicity of the crop plants were observed and rated as described
above .
Ric. Rice
Mai.: Maize
Wh.: Wheat
So.: Soybean
Cot.: Cotton
2 0 Ra .: Radish
B.G.: Barnyard Grass (panicum crus-galli linnaeus)
Cr.G.: Large Crab Grass (digitaria sanguinalis scopoli)
DoF~ Dent Foxtail (alopecurus aequalis sobolewski var ~-
amurensis ohwi)
JoGo: Johnson Grass (sorghum halepense)
G~F~ S~;oose Foot (chenopodium album linnaeus ~rar
centrorubrum makino)
-- 43 --
1 ~5~2~4
The experiments were separately carried out as stated in Tables.
Table 15 (Test 4-1 )
-
Compound Concen- Wh. So. Cot . Ra. B . G. Cr. G. D.F . J . G. G .
No tration
_ ~ _ _ ._ __ _ _
Compound 125 0 0 0 0 10 10 10 10 0
No. 1 62.5 0 0 0 0 10 10 10 9 0
Compound 125 0 - 0 0 0 10 10 i 0 10 0
o. 2 ~2.5 0 0 0 1 0 10 10 10 9 _0
Compound 1 2 5 0 0 0 0 10 10 10 9 0
No 3 62. 5 0 0 0 0 10 10 lO ~ 0
Cornpound 12 5 0 O O O 1 0 1 0 1 01 0 O
No. 4 6205 û _O ¦ O O 10 10 10 10 O
Compound 125 0 0 - 0 0 10 10 10 10 0
No. 5 _ 62. 5 0 0 0 0 10 10 10 10_ 0
Compound 12 5 0 0 0 0 i o 1 o 1 o1 o o
No . 6_ _ 6 2 . 5 O û O O 1 0 _ 1 O 1 01 0 O
Compound 125 0 0 0 0 10 10 10 10 0
No. 7 62. 5 0 0 0 0 10 10 10 9 _ 0
Compound 12 5 0 0 0 0 1 0 1 0 1 0 10 0
No. ~ 62. 5 _ O O O O 10 _ 10 10 10 O
Compound 12 5 0 0 0 0 10 10 10 10 0
No. 9 62.5 L -o -o 1o 1o 1o_ 8 ~ ~. ~ :
Compound 125 O O O O lû lO 10 10 O
No 11 62.5 0 0 0_ _ 0 10 10 10 .~ 0
:Reference 125 2 O O O 3 _ 4 4 4 O
_62 . 5 1 O O _g ~ _ 2 2 _1 ~ 0
Reference 12 5 3 0 0 0 5 6 6 5 0
C omp . (B ) 6 2 . 5 2 0 0 0 3_ 4 .3 2_ n
Re:Eerence 12 5 2 O O O 4 5 6 4 (!
Comp~ (C) _62. 5 0 0 0 0 2 2 3 2 0
Reference 125 2 0 ` 0 0 5 5 5 4 - n
Com~. (D) 62. 5 1 0 0 0 3 2 3 1 0
Reference 12 5 3 0 b o - 6 7 7 6 n
Comp . (E ) 6 2 5 2 0 0 0 4 4 3 3~4 O
2 ~
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-- 45 --
~ ~582~
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-- 46 --
