Note: Descriptions are shown in the official language in which they were submitted.
~L~5~ii7
The present invention relates to heterocyclic ether
type phenoxy fatty acid derivatives and herbicidal compositions
containing them.
Various compounds have been used as herbicides for
many years. These herbicides have been used to eliminate
labour and to improve the productivity of agricultural and
horticultural crops.
Herbicides having superior herbicidal characteristics
are always required. Herbicides for agricultural and horti-
cultural use are preferably compounds which selectively controlthe weeds in a small dose without toxicity to the crops. The
known herbicides do not always have optimum herbicidal
characteristics.
-2- *
Z67
Substituted pyridyloxyp~enoxy fatty acid herbicides
which are heterocyclic ether type phenoxy fatty acid derivatives
have been disclosed in Japanese Unexamined Patent Publication
Wo. 106735/1976. Benzimidazole, bPnzthiazole, and benzoxazole
derivatives~and herbicidal effect of these compounds have been
disclosed in Japanese Unexamined Patent Publication No.
40767/1978.
The present invention provides heterocyclic ether
type phenoxy fatty acid derivatives which are useful in
herbicidal compositions having excellent herbicidal activity
against various weeds, especially gramineous weeds and substan-
tially non-phytotoxicity to broad leaf crop plants.
The present invention also provides a process for
producing such herbicidal compounds.
According to the present invention there are provided
compounds having the formula
(X)n ~ f H ~ O-CH-COR (I)
wherein X represents a halogen atom;
n is 0, 1 or 2; Rl represents a hydro~en atom or a lower alkyl
group; R represents -OH; an -O- alkyl group; an -OM group
wherein M is an inorganic or organic salt moiety; an N ~ R3
\ R4
group, an O-lower alkenyl group; an O- benzyl group; an O-lower
alkylalkoxy group; the O-phenyl group; the -O- c~_lohexyl group;
an -O- haloalkyl group, an -O- lower alkynyl group or an -O-
cyanoalkyl group; and R3 and R respectively represent a hydrogen
atom or a lower alkyl group.
Z~7
In the formula (I), R2 can be an -OM group which
includes-CNa, -OK, --2 Ca, -0-12 Mg, an -OH lower alkylamino
group, an -OH ethanol-amino group, an -OH lower alkyl ethanolamino
group or the -ONH4 group. Such compounds are water soluble
and can be used in an aqueous solution.
The heterocyclic ether type phenoxy fatty acid
derivatives having the quinoline ring and having the
formula (I) of the present invention are the novel compounds.
The heterocyclic ether type phenoxy fatty acid
derivatives (I) of the present invention are unique compounds
which are effective for controlling gramineous weeds without
any phytotoxicity to broad leaf crop plants as well as broad
leaf weeds especially in a post-emergence treatment.
Typical compounds of the present invention having the
formula (I) are shown in Table (1) together with their physical
properties.
3Z~7
Table 1
C ' Rl
( )n ~ N ~ O - CH - COR
Comp. X R ¦ R2 I Physical property
_
1 H CH3 OH mp 188-189 C W.C.
o
2 H CH OCH3 mp 98-99 C W.C.
3 H CH3 C2H5 oily at room temp.
19 7
4 6-Cl CH3 C2H5 nD ~ = 1.5814
_ o
H CH3 ONa mp >280 C W.C.
_
6 H CH3 N(CH3)2 mp 108-109 C W.C.
_
7 H H OCH3 oily at room temp.
_ _
8 6-F CH OH mp 158-159 C W.C.
3 _
9 6-F CH3 OCH3 mp 97C W.C.
6-F CH3 C2H5 mp 60-61 C W.C.
o
11 6-Br CH3 OH _ mp 171-172 C W.C.
_ _ O
12 6-Br CH3 OCH3 mp 117 C W.C
o -
13 6-Br CH3 C2H5 mp 96-97 C W.C.
20 14 6-I CH3 OCH3 mp 126-127 C W.C.
_ 20 colorless
6-I CH3 C2H5 nD = 1.6237 liqîd
16 6-Cl CH3 OH mp 176-177 C W.
17 6-Cl CH3 OCH3 - mp 94-95 C W.C.
18 6-Cl CH3 N(CH3)2 mp 122-123 C W.C.
. 19 pale yello~
19 6-F CH3 oC3H7n nD = 1.5700 liquid
20 colorless
6-F CH3 oC3H7-i nD = 1.5632 liquid
21 6-F CH3 Oc4H-gn mp 45.5-47 C W.C.
22 6-F CH3 oC4H-gi nD 1.5593liquid
pale yello~
23 6-F CH3 OC4H-gt nD = 1~5580 liquid
. 20.5 colorless
24 6-F CH3 5 11 nD --1 5572liquid
.
-- 5 --
~ 5~3Z6~7
Comp. ¦ X l Rl l R2 Physical property
No ~ ~ ¦ OCH2 ~ nD = 1.5972 yellow
26 6-F CH3 O(CH2)2OCH3 mp 62-63 C W.C.
27 ~ ~ jOCH2CH=CH2 n21= 1.5728 cllrldSs
Optical rotation Physical
temp. property
Compound [a ] D
(solvent concen-
tration)
_
28 COOCH3 F [~]32= +31.2so 91
H -C- O ~ ~ (CHC13; C=1.18%) W.C.
___ CH3 l
29 COOCH3 ~ [a] 32= +36.4 m.p.
H- C-~O ~ O~~ ~ (CHC13; C=0.99%) 91-92 C
_ W. C .
NMR SPECTRUM OF COMPOUNDS
Compound _
No.
1 (~ ppm, DMSO-d6); 1.55(3H,d), 4.7(1H,q), 6.7-8.2
(10H,m), 11.0(lH)
2 (~ ppm, CDCQ3); 1.6(3H,d)~ 3.7(3H,s), 4.7(1H,q),
6.7-8.0(lOH,m)
3 (~ ppm, CDCQ3); 1.2(3H,t), 1.6(3H,d), 4.15(2H,q),
4.65(lH,q), 6.75-8.05(lOH,m)
_ _ .
4 (~ ppm, CDCQ3); 1.2(3H,t), 1.6(3H,d), 4.15(2H,q),
4.65(lH,q), 6.8-8.0(9H,m)
_ _
6 (~ ppm, CDCQ3); 1.6(3H,d), 3.0(6H,d), 4.9(1H,q),
6.8-8.1(lOH,m)
7 (~ ppm, CDCQ3); 3.75(3H,s), 4.55(2H,s), 6.7-8.1
(lOH,m)
-- 6 --
11~26~
Compound
No.
8 (~ ppm, DMS0-d6); 1.55(3H,d), 4.8(1H,q), 6.8-8.4
(9H,m), 12.9(1H,b s)
g (~ ppm, CDCQ3); 1.6(3H,d), 3.7(3H,s), 4.7(lH,q),
6.75-8.0(9H,m)
(~ PEm~CDcQ3); 1.25(3H,t), 1.6(3H,d), 4.2(2H,q),
4.7(lH,q), 6.7-8.0(9H,m)
11 ~ ppm, DMSO-d6); 1.55(3H,d), 4.8(1H,q), 6.8-8.4
(9H,m), 13.0(1H,b s)
l _
12 (~ ppm, CDCQ3); 1.6(3H,d), 3.7(3H,s), 4.7(lH,q),
6.7-8.0(9H,m)
13 (~ ppm, CDCQ3); 1.2(3H,t), 1.6(3H,d), 4.15(2H,q),
4.7(1H,q), 6.7-8.0(9H,m)
14 (~ ppm, CDCQ3); 1.6(3H,d), 3.7(3H,s), 4.7(1H,q),
6.7-8.0(9H,m)
(~ ppm, CDCQ31; 1.2(3H,t), 1.6(3H,d), 4.2(2H,q),
4.7(lH,q), 6.7-8.0(9H,m)
16 (~ ppm, DMSO-d6); 1.56(3H,d), 4.84(lH,q); 16.80-
8.40, 9H-6.91(2H,d), 7.17(2H,d), 7.57(2H, s), 7.96
(lH, s), 8.27(lH, d)]
17 (~ ppm, CDCQ3); 1.57(3H,d), 3.68(3H,s), 4.68(1H,q);
[6.75-8.10, 9H-6.83(2H,d), 7.13(2H,d), 7.96(1H,d)]
18 (~ ppm, CDCQ3); 1.59(3H,d), 2.92(3H,s), 3.08~3H,s),
4.91(1H,q); ~6.75-8.05, 9H-6.84(2H,d), 7.13 (2H,d),
7.91tlH,d)]
19 (~ ppm, CDCQ3); 0.85(3H,t), 1.60(3H,d), 1.71(2H,m),
4.11(2H,t), 4.72(1H,q); [6.75-8.15, 9H-6.88(2h,d),
7.14(2H,d), 7.94(lH,d)]
(~ ppm, CDCQ3); 1.19(3H,d), 1.26(3H,d), 1.59(3H,d),
4.65(1H,q), 5.04(1H,m); [6.75-8.10, 9H-6.84(2H,d),
7.13(2H,d), 7.92(lH,d)]
_ _
21 (~ ppm, CDCQ3); 0.88(3H,t), 1.00-2.10(4H,m), 1.60
(3H,d), 4.15(2H,t), 4.73(1H,q); [6.70-8.15 ,9H-6.90
(2H,d), 7.15(2H,d), 7.95(1H,d)]
_................. _ .
22 (~ ppm, CDCQ3); 0.88(6H,d), 1.62(3H,d), Ca. 1.85
(lH,m), 3.92(2H,d), 4.73(1H,q); ~6.75-8.10, 9H-6.86
(2H,d), 7.11(2H,d), 7.95(1H,d)]
67
Compound
No.
23 (~ ppm, CDCQ3); 1.43(9H,s), 1.58(3H,d), 4.63(lH,q);
[6.80-8.10, 9H-6.91(2H,d), 7.18(2H,d), 7.94(1H,d)]
24 (~ ppm, CDCQ3); 0.87(3H,t), 1.05-1.55(6H,m), 1.62
(3H,d), 4.17(2H,t), 4.74(1H,q); ~6.80-8.15, 9H-6.91
(2H,d), 7.19(2H,d), 7.99(1H,d)]
(~ ppm, CDCQ3); 1.62(3H,d~, 4.78(1H,q), 5.20(2H,s);
[6.75-8.15, 14H-6.88(2H,d), 7.15(2H,d), 7.97(1H,d)]
26 (~ ppm, CDCQ3); 1.63(3H,d), 3.33(3H,s), 3.60(2H,t),
4.32(2H,t), 4.77(1H,q); [6.75 8.20, 9H-6.90(2H,d),
7.15(2H,d), 8.00(lH,d)]
27 (~ ppm, CDCQ3); 1.63(3H,d), 4.67(2H,d), 4.78(lH,q);
(5.00-6.20, 3H,m); ~6.80-8.10, 9H-6.91(2H,d),
7.08(2H,d), 7.90(lH,d)]
28 (~ ppm, CDCQ3); 1.63(3H~d), 3.76(3H,s), 4.75(1H,q);
[6.80-8.20, 9H-6.91(2H,d), 7.17(2H,d), 8.02(1H,d)]
29 (~ ppm, CDCQ3); 1.61(3H,d), 3.75(3H,s), 4.76(lH,q);
~6.80-8.20, lOH-6.92(2H,d), 7.18(2H,d), 8.07(lH,d)]
_
~1~15~2~7
The compound (I) of the present invention can be
produced by the following processes:-
A) By the condensation of a compound having theformula
( )n ~ ~ (II)
N Hal
wherein X and n are defined above, and Hal designates a halo-
~en atom; with 4-hydroxyphenoxy fatty acid derivative havins
the formula
Rl
HO ~ OCH -- COR ( I I I )
wherein Rl and R2 are defined above, in the presence of an
inorganic or organic base, such as sodium hydroxide, potassium
hydroxide or potassium carbonate, at a suitable temperature.
The reaction can be carried out in an inert solvent such as
dimethylformamide, dimethylsulfoxide~ or acetonitrile;
B) By the condensation of a compound having the
formula (II) with a hydroquinone monobenzyl ether naving the
formula
HO~ O CH~ ( IV)
in the presence of an inorganic or organic base to produce
a compound having the formula
(X)n ~ o ~3 oCH2~3
_ 9 _
267
wherein X and n are defined above; then hydrogenation of the
product in the presence of a catalyst, such as palladium-
carbon catalyst, to cause debenzylation and to yield a com-
pound having the formula
~ N ~ ~30~ (VI)
wherein X and n are defined above; and then condensation of
the product with an ~-halofatty acid derivative having the
formula R
2 (VII)
Hal - CH - COR
wherein R1, R2 and Hal are defined above; in the presence of
an inorganic or organic base, such potassium carbonate in a
polar organic solvent, such as methyl ethyl ketone, acetoni-
trile or dimethylformamide;
C~ The product obtained by the process A) or B) may
be converted into the other compounds of formula I by hydrol-
ysis, esterification, ester interchange, salt formation or
amidation.
In the process A), the reaction is preferably car-
ried out at 50 to 200C, especially at 80 to 100C, at a
molar ratio of the compound (II): 4-hydroxyphenoxy fatty acid
derivative (III) of 1:0.2 to 5.0, preferably 1:0.5 to 2.0
and especially 1:0.8 to 1.5. The inorganic or organic bases
include in any base which is useful for the condensation of
the compound (II) and the compound (III). The concentration
of the starting materials in the inert solvent may be in a
range of 5 to 50 wt. %, preferably 10 to 30 wt. %.
In the process B), the reaction is preferably car-
ried out at 50 to 200C, especially at 100 to 150C, at a
molar ratio of a compound (II): a hydroquinone monobenzyl
ether (IV) of 1:0.2 to 5.0
~L~ 67
preferably 1:0.5 to 2.0, especially 1:0.8 to 1.5. The inorganic
or organic base includes any base which is useful for the
condensation of the compound (II) and the compound (IV). The
reaction is preferably carried out in an inert solvent at a
concentration of the starting material of 5 to 50 wt.%,
preferably 10 to 30 wt.%. The hydrogenation of the resulting
intermediate (V) is carried out under conditions for the
debenzylation to yield the compound (VI). The hydrogen
pressure is preferably in the range of 1 to 5 atm., more
preferably 1 to 2 atm. The reaction of the compound (VI) with
the ~halofatty acid derivative (VII) is preferably carried out
at 80 to 100C at a molar ratio of the compound (VI): the
compound (VII) of 1:0.2 to 5.0, preferably 1:0.5 to 2.0, and
especially 1:0.8 to 1.5. The inorganic or organic base may
be the same. The concentration of the starting materials in
the inert solvent may be in a range of 5 to 50 wt.~, preferably
10 to 30%.
In the process C), the conditions of the hydrolysis,
the esterification, the ester interchange, the neutralization
and the amiaation can be selected as desired. These conditions
are known by a person skilled in the art.
The present invention will be further illustrated by
way of the following Examples.
Zf~7
Example l:
Methyl i-t4_ ( 2- quinolyloxy)phenoxy)propionate
(Compound No. 2)
In 50 ml of dimethylsulfoxide, 12 g of hydroquinone mono-
benzyl ether, 8. 2 g of 2-chloroquinoline and 8. 3 g of potassium
carbonate were dissolved and the mixture was heated at 150 to 160C
for 4 hours to ~ause reaction. AftercooliD~ the reactionmlx~ure.was
poured into water and the product was extracted with ether for several
times. The ether layer was washed with an aqueous solution of
sodium hydroxide and then with water and the ether layer was the
dehydrated over sodium sulfate. The solvent was distilled off.
The resu~ting crude crystal was washed with diisopropyl ether to
yield 12 g (yield 75''70) of 2-(4-benzyloxyphenoxy)quinoline. All of
the intermediate was dissolved in 200 ml of a mixed solvent consisting of
tetrahydrofuran and ethanol (5:1) and 1. 5 g of palladium-carbon type
catalyst was added. 880 ml of hydrogen gas was fed into the mixture
to effect hydrogenation at the atmospheric pressure. After
hydrogenation, the catalyst was separated by suction filtration and
the solvent was distilled off. The residue was washed with chloro-
form-n-hexane type solvent to yield 6. 3 g ~yield 74~0) of white
crystal of 2-(4-hydroxyphenoxy)quinoline (m.p. 177C).
In 50 rnl of methyl ethyl ketone, 2. 37 g of the product,
2.1 g of methyl c~-bromopropionate and 2. O g of potassium carbonate
were added and the mixture was refluxed for 5 hours to effect reaction.
After cooling to the room temperature, the precipitated product
was separated by filtration and the solvent was distilled off to
yield 2.2 g (yield 68%) of the object compound.
- 12 -
67
Example 2
2-[4-t2-q~inolvloxy)phenoxy]propionic acid
N,N-dimethylamide (Compound No. 6)
In 100 ml of methyl ethyl ketone, 2.3 g of the inter-
mediate of Example 1 of 2-(4-hydroxyphenoxy)quinoline, 1.8 g
of N,N-dimethyl-~-bromopropionic acid amide and 1.4 g of
potassium carbonate were added and the mixture was refluxed
for 5 hours. After the reaction, the precipitated crystal was
separated by filtration and the so]vent was distilled off.
The product was dried under reduced pressure. The resulting
crude crystals were recrystallized from a solvent of methanol-
water to yield 3.6 g (yield 88%) of white crystal of the object
compound.
The compound of formula I can be used in the form
of a herbicidal composition.
In the preparation of the herbicidal compositions, the
compound of formula I can be uniformly mixed with or dissolved
in suitable adjuvants including solid carriers such as clay,
talc, bentonite and diatomaceous earth; liquid carriers such
as water, alcohols (e.g. methanol and ethanol), aromatic
hydrocarbons (e.g. benzene, toluene, or xylene), chlorinated
hydrocarbons, ethers, ketones, esters (e.g. ethyl acetate),
acid amides (e.g. dimethylformamide).
- 13 -
~Z6~7
if desired also with an emulsifier, a dispersing agent, a
suspending agent, a wetting agent, a spreader, or a stabilizer
to form a solution, an emulsifiable concentrate, a wettable
powder, a flowable suspension, a dust or a granule, which is
applied if desired, by diluting it with suitable diluent.
It is possible to combine the compound of the present
invention with another herbicide, or an insecticide, a fungicide,
a plant growth regulator or a synergistic agent.
Examples of the herbicidal compositions of the present
invention are given in which parts are parts by weight.
Solution:
Active ingredient: 5 to 75 wt.%, preferably 10 to
50 wt.%, especially 15 to 40 wt.%.
Solvent: 95 to 25 wt.%, preferably 88 to
30 wt.%, especially 82 to 40 wt.%.
Surfactant: 1 to 30 wt.%, preferably 2 to 20
wt.%.
Emulsifiable concentrate:
.
Active ingredient: 2.5 to 50 wt.%, preferably 5 to
45 wt.%, especially 10 to 40 wt.%.
Surfactant: 1 to 30 wt.%, preferably 2 to
25 wt.%, especially 3 to 20 wt.%.
Liquid carrier: 20 to 95 wt.%, preferably 30 to
93 wt.%, especially 57 to 85 wt.%.
Dust:
Active ingredient: 0.5 to 10 wt.%.
Solid carrier: 99.5 to 90 wt.~.
Flowable suspension:
. .
Active ingredient: 5 - 75 wt.%, preferably 10-50 wt.%
~ater: 94 - 25 wt.%, preferably 90-30 wt.%
Surfactant: 1 - 30 wt.%, preferably 2-20 wt.
-14-
5~Z67
Wettable powder:
Active ingredient: 2.5 to 90 wt.%, preferably 10 to
80 wt.%, especially 20 to 75 wt.%.
Surfactant: 0.5 to 20 wt.%, preferably 1 to
15 wt.%, especially 2 to 10 wt.%
Solid carrier: 5 to 90 wt.~, preferably 7.5 to 88
wt.%! especially 16 to 56 wt.%
Granule:
Active ingredient: 0.5 to 30 wt.%
` 10 Solid carrier: 99.5 to 70 wt.%
The emulsifiable concentrate is prepared by dissolving
the active ingredient in the liquid carrier together with the
surfactant. The wettable powder is prepared by admixing the active
ingredient with the solid carrier and the surfactant and the
mixture is~pulverized. The flowable suspension is prepared by
suspending and dispersing a finely divided active ingredient in
an agueous solution of a surfactant. The dust, the solution,
the granule etc. are prepared by mixing the active ingredient
with the adjuvant.
In the following compositions, the following ad~uvants
are used.
So~pol-2680*
POE-hormylnonylphenolether 50 wt. parts
POE-nonylphenolether 20 "
POE-sorbitan alkyl ester 10 "
Ca-alkylbenzenesulfonate 20 "
Sorpol-5039*
POE-alkylarylether sulfate 50 "
Silica hydrate 50 "
Carplex*
Silica hydrate 100 "
Zeeklite*
Clay 100 "
-15-
~15~267
Sorpol W-150*
POE-nonylphenolether 100 wt. parts
* Trademark~
Composition 1: Wettable powder:
Compound No. 1 50 wt.parts
Zeeklite A* 46 "
Sorpol 5039*~Toho Chem.) 2 "
Carplex 2 "
* Trademark
These components were uniformly mixed and pulverized
to prepare a wettable powder. The wettable powder was diluted
with water at 50 to 1, 000 times and the diluted solution was sprayed
at a dose of 5 to 1000 g of the active ingredient per 10 ares.
Corriposition 2: Emulsifiable concentrate:
Compound No. 4 20 wt.parts
Xylene 7 5
Sorpol 2680~Toho Chem.) 5 "
* Trademark
The components were uniformly mixed to prepare an emul-
sifiable concentrate. The emulsifiable concentrate was diluted with
water at 50 to 1, 000 times and the diluted solution was sprayed at a
dose of 5 to 1000 g of the active ingredient per 10 ares.
Composition 3: Aqueous solution-
Compound No. 5 30 wt. parts
Sorpol W-150*~Toho Chem.) 10 "
Water 6 0 "
* Trademark
~5~267
The component~ were mixed to dissolve them and to prepare
an aqueous s'olution. The aqueous solution wa~ diluted with water
at 50 to 1, 000 times and the diluted solution was sprayed at a dose
OI 5 to 1000 g. of the active ingredient per 10 ares.
As the other herbicides, the following he~bicid'es
were respectively used 2-(2, 4-dichloropheno:~y)propionic acid,
2, 4 - dichlorophenoxyacetic acid, 3 - ( 3 - trifluoromethylphenyl~ - l, 1-
dimethylurea,3-(4-methylphenethyloxyphenyl)- l-methyl- 1 -methoxy urea,
3-(methoxycarbonylamino~phenyl-N-(3-methylphenyl) carbamate,
3-(ethoxycarbonylamino)-phenyl-N-phenylcarbamate, 3-isopropyl-lH-
2,1, 3-benzo thiadiazine-(4)-3H- one-2, 2-dioxide, 5-amino-4-chlor
2-phenylpyridazine- 3-one, 3- cycl'ohexyl- 5, 6-trimethyleneuracil,
2-chloro-4-ethylamino-6-isopropylamino-1, 3, 5-triazine, 2-chloro-
4, 6-di(ethylamino~-1, 3, 5-triazine, 2-methylthio-4, 6-bistisopropyl-
amino)-1, 3, 5-triazine, 4-amino-4, 5-dihydro-3-methyl-6 phenyl-
l, 2, 4-triazine- 5- one, 4-amino-6-t-butyl-4, 5-dihydro- 3 -methylthio-
l, 2, 4-triazine- 5-one, 2-chloro-4-trifluoromethylphenyl-3' -ethoxy-4-nit_
rophenyl ether or sodium-5-¦2-chloro-4-(trifluoromethyl) phenoxy~-2-
nitro benzoate.
It is also possible to combine the compound of the present
invention with the other herbicidal compounds such as are described in
"Weed Control Handbook'l (Vol. I 6th edition 1977; Vol. II 8th edition
1978) issued by the British Crop Protection Council edited by J.D.
Fryer l~A & R.J. Makepeace BSc . Blackwell Scientific Publication~
-- 17 --
267
The heterocyclic ether type phenoxy fatty acid
derivatives of the present invention have an excellent herbi-
cidal effect on various weeds especially gramineous weeds
in soil treatment or in foliage treatment, without any
phytotoxicity to broad leaf crop plants such as cotton, soy-
bean, radish, cabbage, eggplant, tomato, sugar beet, ground
nut, peas, beans, linseed, sunflower, safflower, potato,
tobacco, alfalfa and onion etc. Therefore, the heterocyclic
ether type phenoxy fatty acid derivatives of the present
invention are suitable for selective control of gramineous
weeds in a culture of a broad leaf crop plant as herbicide
for agricultural and horticultural fields especially up-land
fields.
The heterocyclic ether type phenoxy fatty acid
derivatives of the present invention are also effective as
herbicides for controlling various weeds in the agricultural
and horticultural fields such as up-land, paddy fields and
orchards as well as non-cultivated lands such as playground,
vacant land, and railway sides.
The herbicidal composition usually contains 0.5 to
95 wt. % of the compound of the present invention as the ac-
tive ingredient and the remainder of the adjuvants in con-
centrated form. The dose of the compound of the present in-
vention depends on the weather conditions, soii conditions,
form of the composition, season of an application, type of
crop plant and types of weeds. It is usually in a range of
1 to 5000 g, preferably 5 to 1000 g, of the compound of the
invention per 10 acres~
The herbicidal activities of the hcterocyclic cther
type phenoxy fatty acid derivatives of the prcsent invention
are illustrated in the following Tests.
- 18 -
~S~2~7
In the following tests, the herbicidal effects of the
compounds of the present invention on gramineous weeds including
rice are shown together with non-phytotoxicity of the same
compounds to broad leaf crop plants as well as broad leaf weeds
especially, non-phytotoxicity of the same compounds to broad
leaf weeds in ?ost-emergence. These remarkable selectivities
have not been found by other compounds.
Test 1: Tests for herbicidal effect in soil treatment:
Each of a plurality of plastic boxes having a length
of 15 cm, a width of 22 cm and a depth of 6 cm was filled with a
sterilized diluvium soil and seeds selected from rice (Oryza
sativa), barnyard grass (Echinochloa crus-galli), large crab-
grass tDigitaria adscendens), lambsquarters (Chenopodium
ficifolium), common purslane (Postuloca oleracea), hairy gal-
insoga (Galinsoga ciliata), yellow cress (Rorippa atrovirens)
seeds were sown to a depth of about 1.5 cm. Each solution of
each herbicidal composition was uniform~y sprayed on the surface
of the soil to give the specific dose of the active ingredient.
_19 _
~ 3~5~267
The solution was prepared by diluting, with water, a
wettable powder, an emulsifiable concentrate or a solution described
in Examples of the composition except varying the active ingredient~
The solution was sprayed by a small spray. Three weeks after the
treatment, the herbicidal effects to rice and various weeds were
observed and rated by the following Standar~s. ~h6 results are shown
in Table 2.
Standard rating:
5: Growth control of more than 90%
(subsantial suppression)
4: Growth control of 70 to 90%
3: Growth control of 40 to 70%
2: Growth control of 20 to 40%
1: Growth control of 5 to 20%
0: Growth control of less than 5%
(non-herbicidal effect)
Note: Ri: Rice
Ba.: Barnyard grass
L. C.: Large crab grass
La.: Lambsquarters
2 0 C . P .: Common pur slane
H. G .: Hairy galin soga
Y. C.: Yellow cress
_ 20 --
Table 2-1
~ ¦ L, C, ¦ L~. ¦ C. P, ¦ H. G. ¦ Y. C
11 5ooo 5 55 5 2 22 2 32
1 00 5 5 5 3 3 3 4
2 50 5 5 5 1 2 3 3
100 1 5 . 5 5 v 5
3 50 5 5 4 2 3 3 3
4 100 5 5 5 4 4 4 4
a 2 3 3
5 lO0 5 S 4 2 2 2 2
100 5 5 . 5 2 0 2 2
6 50 5 5 4 1 0 1 1
7100 4 5 4 0 0 2 2
50. 4 1 5 4 0 __ 1
-- 21 --
2ti7
Table 2-2
Dose of
CNmo.P Comp. Ri B~ L C, La C. P. H, G. Y,
100 5 5 5 3 3 3 3
8 50 5 5 5 2 2 2
- 1200 5 5 5 3o 2 3o 3
9 50 5 5 5 2 1 2 2
~ 5 5 0 0 0 0
. lO0 5 5 5 - 3 3 4 4
2 2 3 3
0 0 0 0
Table 2-3
comP.¦ Comp. Ri Ba L.C. C.A. C.P. H.G. Y.C
No .(~ /a) _
100 5 5 5 2 2 2 2
11 50 5 5 5 1 1 1 0
55_ 5_ - o 0 0 ~0
100 5 5 5 2 2 3 2
1250 5 5 5 1 1 I
5- 5 5 0 0 0 0
I 100 5 5 --5 2 2 2 2
131 50 5 5 -5 I 1 1 1
1 25 5 5 5 0 0 0 0
I 100 5 5 5 2 2 2 2
1450 5 5 5 I 1 1 1
. 1 25 5 5 5 0 0 0 0
100 5 5 5 2 2 2 2
5 5 5 1 1 1 1
~ 25 5 5 5 0 . .. 0
.
~5~267
Table 2-4
Comp, Dose oi- Ri Ba L, C, La. C. P. H. G. Y. C
100 5 . 5 5 2 2 2 2
16 50 5 5 5 1 1 1 1
0 _ 0 0 0
I 00 5 5 5 2 2 -- ~-- 2 2
17 ` 50 5 5 5 1 1 1 1
5 _ 5 0 0 0 0
. 100 5 5-- 5----2 2 2 2
18 50 5 5 5 0 1 0
0 0 0 0
100 5 5 --5 2 2
19 50 5 5 5 1 1 1 0
5 5 _ 0 0 0 0
1 00 5 5 5 2 2 2 2
1 1 1 1
0 0 0 0
100 5 5 5 2 . 2 2 2
21 50 5 5 5 1 1 1 1
0 0 0 0
. 100 5 . 5 5 2 2 2 2
. 2250 5 5 5 .1 1 1
5_ 5 S 0 0 0_ 0
1 00 5 5---5 ~ 2 2 2 2
23 50 5 5 5 1 1 1
0 0 0 0
100 5 5 5 2 2 2 2
24 50 - 5 5 5 1 I l. I
5_ 0_0 0
.. 1 00 5 5 5 - 2 2 2 2
1 1 I 1
0 0 0 __
1 00 5 - -5 5 1 1 I
26 50 5 5 5 0 0 0
0 0 0
100 5 5 5 2 2 2
27 50 5 5 5 1 1 1 1
0_ 0 0
-- 23 --
z~
Table 2-5
Comp. Dose of Ri ¦ Ba L.C. ha. ¦ C.P. H.G. Y.C.
No Comp;
100 5 5 5 0 0 0 0
0 0 0 0
28 25 5 5 5 0 0 0 C
12.5 S 5 5 0 0 0 0
100 5 5 5 0 0 0 0
0 0 0 0
29 25 5 5 4 0 0 0 0
12.5 4 ~ 4 0 0 0 0
- 24 -
3267
Test 2: Tests for herbicidal effect in foliage treatment:
Each of a plurality of plastic boxes having a length
of 15 cm, a width of 22 cm, a depth of 6 cm was filled with a
sterilized diluvium soil and seeds selected from
rice, large crab-grass, lambsquarters L. var. common purslane,
hairy galinsoga, yellow cress and tomato seeds were sown in the
form of spots to a depth of about 1.5 cm. When the weeds had
grown to 2 to 3 leaf stage, each solution of each herbicidal
composition was uniformly sprayed to foliages at each dose of
each active ingredient shown in Table 3. The solution was
prepared by diluting, with water, a wettable powder, an emulsi-
fiable concentrate or a solution described in the Examples of
the composition except varying the active ingredient and the
solution was uniformly sprayed by a small spray on all of foliages
of the plants.
Two weeks after the spray treatment, the herbicidal
effects on the weeds and tomato were observed and rated by the
standard shown in Test 1. The results are shown in Table 3.
-25-
67
Table 3-1
Dose of
Comp. Comp. Ri L.C. La. C.P. H.G. Y.C. Tomato
No. I (g/a)
1 100 5 5 21 2 3
1~ ~ 3 1
2 100 5 5 5 3 2 4 0
52 _ ~ 3 0 .
3 100 5 5 5 3 2 5
4 3 ~ 2 ~ 0 .
4 100 5 5 3 2 3 4
1 1 1 2 0
_ _ .
100 5 5 2 1 2 3
4 2 0 2 2 0
_ .
6 100 3 3 3 0 2 3 0
l 150 ~ 2 2I 0 I 1 1 2 0 .
~15~Z67
Table 3-2
Comp. ¦ Comp ¦ Rl ¦ L. C . ¦ La- C . P . H . G . Y . C .
-- ¦ (g/a) ¦ l
100 5 5 4 5 3 4
8 S0 5 5 2 3 2 2
0 0 0 0
_ 1 00 5 5 2 1 2 3
9 50 5 5 1 1 1 2
5_ 5 I l 1 2
100 5 5 3 3 2 4
10 50 5 5 2 2 2 3
1 1 -2 _ 2
Table 3-3
Comp. C mp. ¦ Ri L . C . La. C . P. H . G . Y. C
100 5 5 1 1 2 2
11 50 5 5 0 0 ' 1 1
0 0 0_ 0
100 5 5 2 2 2 2
12 50 5 5 I 1 1
0 0 0 0
100 5 5 2 2 2 2
13 50 5 5 1 1 1 1
- 0 0 0 0
1 00 5 5 - 2 1 - 2- 2
14 50 5 5 0 0 I 1
1200 4 5 0 1 -~ 2 2
0 0 1 1
4 5 0 0 0 0
-- 27 --
-
Z67
Table 3-4
. Comp. ¦ Dose of Ri ~ L.C. La. ~ C.P. H.G. ~ Y.C.
100 5 5 2 2 1 2
16 50 5 5 1 1 0
5_ _0 0 0 0
100 5 5 2 2 I 2
17 50 5 5 1 1 0
5 0 0 0 0
100 5 5 1 1 1 1
18 50 5 5 0 0 0 0
4 5 0 0 0 0
100 5. 5 ~ 2 2 2 2
19 50 5 5 1 1 1 1
_ 0 0 0 0
100 5 5 2 2 2 2
1 1 1 1
. 25 5 5 0 0_0 0
100 5 5 2 2 2 2
21 50 5 5 1 1 1 1
5_ 0 0 0 0
100 5 5 2 2 2 2
22 50 5 5 1 1 1 1
. .... 25 5 5 0 0 0 0
100 5 5 2 22` 2
23 50 5 5 1 1 1 1
0 0 0 0
100 5 5 2 2 2 2
24 50 5 5 1 1 I 1
0 0 0 0
100 5 5 1 1 1 2
0 0 0 1
_ 0 _ 0 0
_1 00 5 5 1 2
26 50 5 5 1 0 0 1
0 0 0 0
100 5 5 2 1 1 2
27 50 5 5 1 0 0
. 25 5 5 0 0 0 0
-- 28 --
~5~267
Table 3-S
Dose of _
Comp . Comp . RiL . C .La . C . P . H . G . Y . C .
No .( g/a )
100 5 5 1 1 1
0 0 0 0
28 25 5 5 0 0 0 0
12.5 5 5 0 0 0 0
100 5 5 0 0 0 0
0 0 0 0
29 25 5 5 0 0 0 0
12.5 5 5 0 0 0 0
Z~7
Test 3: Tests for phytotoxicity to crop plants (foliage
treatment:
Each of a plurality of plastic boxes having a length
of lS cm, a width of 22 cm, and a depth of 6 cm was 'illed
with a sterilized diluvi~m soil and seeds selected .rom cotton,
soybean, radish, cabbage and egsplant seeds were sown in the
form of spots to a depth of about 1.5 cm. When the plants
had grown to lea.-emergence stage, each solution of each her-
bicidal composition was uniformly sprayea on the foliage at
each dose of each active ingredient shown in Table 4. The
solution was prepared by diluting, with water, a wettable
pow~er, an emulsifiable concentrate or a solution described
in the Examples of the composition except varying the active
ingredient and the solution was unifor~iy sprayed by a smal'
spray on all foliage of the plants.
Two weeks after the spray treatment, the phytotox-
icities to the plants were observed and rated by the following
standard. The results are shown in Table 4.
Stanaard rating-
5: Co~plete death of plant
4: Serious phytotoxicity to plant
3: Fair phytotoxici'y to plant
2: Slight phytotoxicity to plant
1: Only slight phytotoxicity to plant
0: Non phytotoxicity
Note: Cot.: Cotton Cab.: Cabbage
Soy.: Soybean Egg.: Eggplant
Rad.: Radish
_ 30 -
~ ~ 5~267
Table 4- 1
Dose of
N o ( g / a ) C ot . S oy . Et a d . C ab . E g g .
0 0 0 0 0
4 S0 1 1 I ~ 1
_able 4-2
¦ Dose of l
Compound Compound Cot. Soy. Rad. Cab . Egg.
No. (g¦a~ _
8 50 1 0 1 1 0 0
0 0 0 1 0 0
~ 1 1 0 1 0 0
0 1 0 0 1 0 0 . .
1 1 1 0 1 0 0
0 i 0 0 1 0 0
_
Table 4-~
. Dose of
Compound C ompound Cot . Soy. Rad. Cab . Egg .
No. (~/a) _
0 ~ 1 0--- ___--0-
__ 2 5 0 - 0 0 0 0
12 50 0 1 0 0 0
0 0 0 0 0
13- 50 - 0 1 0 0 0
1 0 1 0 0 _ 0
14 50 1 0 1 0 1 0 0 0
S0-~-- 1 0 1 0 j 0 0 0
1 0 1 0 1 0 0 0 _
~s~z~i7
Table 4- 4
-
Dose of
Compound Compound Cot. Soy. Rad. Cab . Egg.
No . (~ /a )
1650 0 1 ~ 0
25 0 0 1 0 1 0 1 0
-1750 0 1 1 1 1 1 1 1
25 0 0 1 0 1 0 1 0
18 50 -I I I
0 0 1 0 1 0 1 0
19 255 1 1 1 1 l
20 - 50 0 1 1 1 - 1 1
0 ~ I 0 0 0
21 - 50 0 1 1 1 1 1
0 1 0 1 I !
22 50 0 1 1 1 I
0 0 0 0 0
23 50 0 1 1 i
0 I ! I
24 50 0 1 1 1 1
0 0 1 0 0 0
0 0 1 1 -I
1 0 0 0 0 1 0
26 50 1 0 1 ` 0 0 0
1 0 0 0 0 0
27 50 1 0 1 ` 1 0 0
2S I o 0 0 0 0
- 32 -
67
Table 4-5
Dose of _
Compound Compound Cot. Soy. Rad. Ca~. Egg.
No.(g/a)
10~ O O O O O
28 50 0 0 0 0 0
0 0 0 0 0
' 100 O O O O O
29 50 0 0 0 0 0
0 0 0 0 0
- 33 -
