Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
lOo<.~
~his invention provides a compound of the general formula
~ ~ O-CH-C-Y-Z (I)
R(n) Rl(nl)
in which
n represents an integer from 1 to 3,
nl represents an integer from 0 to 3, and n and nl rnay be the same or
different,
R represents a halogen atam, CF3, (Cl-C4)-aIkyl, or nitro,
Rl represents hydrogen, a halogen atom, or (Cl-C4)-aIkyl, and any two or
more of the R and Rl moieties may be the same or different,
X represents -0- or -CH2-,
Y represents -O-, -S- or -NH- and
Z represents a cyanoethyl group or a radical of the general formula
-A-CI-OR3~
b
in which
A represents a methylene group which.r,~ay be unsubstituted or substituted by
-CH3, -C2H5, -COCH3 or by another radical of the general formula -COOR'3, or
a phenylene or styryl radical which radicals rnay be unsubstituted or
substituted in the ring by one
lOg~ 1573
or two of the same or different substituents
selcctcd from halogen atoms and (Cl-C4)-alkyl
and nitro groups, and
R3 and R'3, which may be the same or different, each rep-
resents a (Cl-C4)-alkyl group.
Preferred compounds of the general formula I are those
in which a halogen is chlorine and/or bromine, alkyl groups
or moieties are those having 1 or 2 carbon atoms, n = 1 or 2,
nl = O and Y represents an oxygen atom.
Especially preferred are compounds in which (R)n rep-
resents 4-Cl, 2,4-Cl, 4-Br, 2-Cl, 4-Br or 4-CF3, nl = O and
X and Y represent oxygen atoms. Z preferably represents a
cyanoethyl group, e.g. the 2-cyanoethyl group, or a radical
of the general formula -A-COOR3, in which A = -CH2-, -CH(CH3)-
or -CH(C2H5)-.
The invention also provides a process for the preparation
of a compound of the general formula I, which comprises
reacting
a) a compound of the general formula
R)~_ X -~-O-CH-C-YII ~Il)
in which n, nl, R, Rl, X and Y have the meanings given
above, or an alkali metal or ammonium salt thereof with
10~3
a compound of the general formula
Hal-Z (III)
in which Z has the meaning given above and Hal represents
a halogen atom, or
b) a compound of the general formula
~ -X- ~ - 0-CH-C-Hal ~IV)
R (n) (nl )
in which n, nl, R, Rl, X and Hal have the meanings given
above,
with a compound of the general formula
HYZ (V)
in which Y and Z have the meanings given above,
or an alkali metal or ammonium salt thereof,
optionally in the presence of an acid-binding agent.
In the formulas II and III, Hal preferably represents a
chlorine or bromine atom.
Compounds of the general formula I have herbicidal pro-
perties, exhibiting a good action against a broad spectrum of
weeds in both pre-emergence and post-emergence treatment.
Thus, compounds of this invention may be used to combat, for
example, grass-type weeds such as oat grass (Avena), foxtail
S73
grass lAlopecurus), rye-grass ~Lolium) and bristle-grass,
hen-grass and crab-grass (Setaria, Echinocloa and Digitaria),
in dicotyledonous crop plants.
With some of the compou~s it is possible to control
selectively even grass-type weeds in cereals.
Even when high doses are applied, soya beans, peanuts,
dwarf beans, field beans, peas, lucerne, flax, cabbage, rape,
cucumber, sunflower, tobacco, carrots, celery and sugar beet
are generally not damaged.
As a result of their specific action against weeds,
especially wild oats, foxtail-grass, rye-grass and millet-
grass, a compound of the present invention may be used in
fields strongly affected by weeds in preference to a number
of the successful known herbicidal agents such as, for example,
Alachlor, Monolimuron, Linuron, Pyrazon, Phenmedipham, sodium
trichloroacetate, Fluorodifen and Mecoprop.
Further, the quantity necessary for the complete des-
truction of the weeds is generally far lower than in the
case of the above-mentioned known herbicides.
An additional advantage of compounds of the present
invention is their low toxicity to warm-blooded animals.
Accordingly, the present invention provides a method
of combating weed grasses, which comprises applying the com-
pound of the invention to the weed grass or to the area or
soil infested with, or liable to infestation by, a weed grass.
Surprisingly, compounds of the formula I also exhibit
good action against harmful fungi on commercially valuable
-- 5 --
~0'~ ~;73
materials as well as against phytopathogenic fungi, such as,
for example, Piricularia oryzae, rust fungus, Botrytis cinerea,
Plasmopara viticola, Phytophthora infestans, true types of
mildew, Rhizoctonia solani, Septoria nodorum, Ustilago nuda,
Phoma betae, Pythium ultimum and Helminthosporium gramineum.
Accordingly, the present invention also provides a me~hod
of combating fungal infections, which comprises applying a
compound of the invention to the fungus or to an object,
material or area infected with, or liable to infection with,
a fungus.
For application as fungicide to a commercial substrate,
the compound may be used, for example, as an additive to
lacquers, varnishes and paints.
For use as protective agent for plants the compound may
be formulated as a dust, spray powder, dispersion or emulsion
concentrate. The total content of active substance is gener-
ally, depending on the formulation, from 2-80% by weight.
In addition they may contain the usual adhesives, wetting
agents, dispersing agents, fillers and carriers. They may
also be mixed with other fungicides.
The invention therefore also provides a herbicidal
and/or fungicidal preparation, which comprises a compound
of the general formula I and a suitable carrier therefor.
The herbicidal or fungicidal preparation may contain one
or more customary formulation auxiliaries and inert substances
and generally contains from 2 to 95% by weight of the active
substance of formula I. The preparation may, for example, be
~I.O~ ~S73
in the form of a wettable powder, emulsifiable concentrate,
sprayable solution, dusting agent or granulate.
A wettable powder is a preparation uniformly dispersible
in water, and in addition to the active substance contains,
apart from a diluent or inert substance, a wetting agent, for
example a polyoxethylated alkyl phenol, a polyoxethylated oleyl
or stearyl amine, or an alkyl or alkylphenyl sulphonate and a
dispersing agent, for example the sodium salt of ligninsul-
phonic acid, 2,2'dinaphthylmethane-6,6'-disulphonic acid or
f oleoylmethyltaurine acid.
An emulsifiable concentrate may be ob~ained by dissolving
the active substance in an organic solvent, for example,
butanol, cyclohexanone, dimethylformamide, xylene or an aromatic
substance having relatively high boiling point.
A dusting agent or sprayable powder may be obtained by
grinding the active substance with a finely divided solid
substance, for example talcum or a natural clay, such as kaolin,
bentonite, pyropyhllite or diatomaceous earth.
A sprayable solution, us~ed widely in spray cans, contains
the active substance dissolved in an organic solvent, and in
addition, for example, as propellant, a mixture of fluorochloro-
hydrocarbons and/or carbon dioxide.
A granulate may be prepared either by spraying the active
substance on to adsorptive, granulated inert material, or by
applying the active substance concentrate by means of an
adhesive, for example polyvinyl alcohol, or the sodium salt of
polyacrylic acid, or a mineral oil, to the surface of a carrier
10~4573
substance, e.g. sand, kaolinite or granulated inert material.
Alternatively, suitable active substances may be formulated in
the manner usual for the production of manure granules, if
desired in admixture with manure.
The concentration of the active substance in the herbi-
cidal preparation may vary according to the formulation. In
a wettable powder, the concentration of active substance may
vary, for example, from 10 to 80%, the remainder consisting
of the above-mentioned formulation additives. In an emulsifiable
concentrate, the concentration of active substance may be from
10 to 80%. A dusting agent usually contains from 5 to 20%
of active substance, and a sprayable solution from 2 to 20%.
The content of active substance in a granulate depends to some
extent on whether the active compound is liquid or solid and
on the choice of granulating auxiliary, filler and other material.
For application, the commercially customary concentrate
may, if necessary, be diluted in the usual manner, for example
by means of water in the case of a wettable powder or emulsi-
fiable concentrate. Dusting agents, granulated preparations
and sprayable solutions are generally not diluted with further
inert substances before use. The quantity required for appli-
cation varies depending on the external conditions such as
temperature and humidity, and may vary, for example, from 0.1
kg/ha to 10 kg/ha of active substance, but is preferably from
0.1 to 3 kg/ha. The active substance according to the inven-
tion may be combined with one or more other herbicides and/or
soil insecticides.
73
The following Examples illustrate the invention.
PREPARATION EXAMPLES
Example 1
2-~4'(4"-Chlorophenoxy)-phenoxy~-propionyllactic acid methyl
ester
A solution of 81 grams of 2- ~4'(4"-chlorophenoxy)-
phenoxy]-propionic acid and 48 grams of 2-bromopropionic acid
methyl ester in 160 ml of acetone was heated at the boil for
8 hours, while stirring, with 40 grams of potassium carbonate.
After cooling to 20C the inorganic salts were filtered off.
The acetone was distilled off from the filtrate and the residue
was distilled in vacuo.
91 grams (87% of the theoretical yield) of the following
compound having a Bpo 1 : 190 - 191C were obtained.
Cl - ~ - O - ~ -O-CH-C-O-CH-C-OCH3
Example 2
2- L4'(2",4"-Dichlorophenoxy)-phenox~ -propionylglycolic acid
methyl ester
61 grams of 2-~4'-(2",4"-dichlorophenoxy)-phenoxy] -
propionic acid and 24 grams of chloracetic acid methyl ester
were dissolved in 200 ml of butanone. After adding 26 grams
of potassium carbonate, the mixture was heated at the boil for
8 hours while stirring. The reaction mix~ure was cooled to
_ g _
~0~573
20C and the inorganic salts were filtered off. The butanone
in the filtrate was distilled off and the ester formed was
purified by vacuum distillation.
67 grams ~90.0% of the theoretical yield) of the following
compound having a Bpo 05 : 207 - 208C were obtained.
Cl~O-~-O-CH-C-O-CH2-C-OCH3
~ O O
Cl
Example 3
2-~4'-(2",4"-Dichlorophenoxy)-phenoxy~ -propionylthioglycolic
acid methyl ester
48 grams of thioglycolic acid methyl ester were dissolved
in 200 ml of toluene. At a temperature of 20 to 40C, 156
grams of 2-~4'-(2",4"-dichlorophenoxy)phenoxy~-propionic acid
chloride, dissolved in 150 ml of toluene, and 48 grams of dry
triethylamine, dissolved in 50 ml of toluene, were added drop-
wise simultaneously. The mixture was then stirred for 2 hours
at 40C. The triethylamine chlorohydrate formed was suction
filtered. The toluene in the filtrate was distilled off and
the residue was purified by distillation at 0.2 torr.
180 grams (96% of the theoretical yield) of the follow-
ing compound having a Bpo 2 : 230 - 232C were obtained.
Cl- ~ 0- ~ O-CH C~-S-CH2-1CI-OC~3
- 10 -
109~573
Example 4
2-~4'-(4"-Bromophenoxy)-phenoxy~-propionic acid 2-cyanoethyl
ester
30 grams of 3-hydroxypropionic acid nitrile were dissolved
in 150 ml of toluene. At a temperature of 20 to 40C, 143
grams of 2-[4'-(4"-bromophenoxy)-phenoxy]-propionic acid chloride,
dissolved in 100 ml of toluene, and 40 grams of dry triethyl-
amine, dissolved in 50 ml of toluene, were simultaneously added
dropwise. The mixture was then stirred for 2 hours at 40C,
cooled to 20C, suction filtered and the toluene was distilled
off from the filtrate. 151 grams of residue were obtained.
Distillation of the residue yielded 138 grams (88% of the
theoretical yield) of the following compound having a Bpo 1 :
208 - 210C.
Br-~-O- ~-O-CH-C-O-CH2-CH2 -C_N
Example 5
2-t4'-~4"-Trifluoromethylphenoxy)-phenoxy~-propionic acid
4-methoxycarbonyl henyl ester
P .
23 grams of 4-hydroxybenzioc acid methyl ester and 17
grams of dry triethylamine were dissolved in 120 ml of toluene.
At 20 to 40C a solution of 52 grams of 2- E'-(4"-trifluoro-
methylphenoxy)-phenox~ -propionic acid chloride in 80 ml of
toluene was added dropwise. After the mixture had been stirred
at 40C for 2 hours~ it was cooled to 20C, triethylamine
10~4573
clllorohydrate was filtered off with suction and the toluene
was distilled off from the filtrate. The oil obtained was
recrystallised from n-hexane.
64 grams (92% of the theoretical yield) of the following
compound having a melting point of 78 - 79C were obtained.
~ ~ -0-CH-C-O- ~ -IC-O-CH3
Example 6
2-14'-(2",4"-Dichlorophenoxy)-phenoxy~-propionyloxy (2-aceto-
acetic acid methyl ester)
70 grams of the sodium salt of 2- L4'-(2",4"-dichlorophenoxy)-
phenoxy3 -propionic acid were suspended in 300 ml of benzene
and 32 grams of 2-chloracetoacetic acid methyl ester were
added. Stirring was carried out at 80C for 8 hours then the
mixture was cooled and sodium chloride was filtered off. The
toluene was removed by distillation.
76 grams of yellow oil having a refractive index of
nD25 = 1.5593 were obtained.
Cl- ~ -0- ~ -0-CH-C-0-CH-C-0-CH3
Cl CH3
The compounds listed in the following Tables were prepared
in accordance with the processes in Examples 1 to 6.
Table 1: 10~ ~3
-o- ~ -O-CH-C-O-A-C-OR3
O O
R(n) Rl
(nl)
I: A = -CH(CH3)-
Example R(n) 1(nl) 3 BP~
.. _ ... .
7 4-Cl H CH3 Bp, 190 - 191
8 2,4-Cl H CH3 0.1'
9 3,4-Cl H CH Po.ol: 188 - 190
11 2-Cl,4-Br H CH3 pO l196 - 198
12 4-CF3 H CH PQ.05198 - 200
3 ~ 3-CE~ j H ¦ CH3 pO ~~82 185
16 3-CF3,4-C1 ~ CH B ~1
7 ! 2-Cl l ¦ CH3 ¦ Bp 5-86 - 87
19 3-Cl,4-CH~ H CH3 ~0.11~32 - 184
4-Cl 3-CH3 CH3 Bp :190 191
2l2 2,4-Cl 3-CH3 CH3 Po,05: 194 196
23 2,4-C1 H 2 5 Po 1194 - 196
24 2-Cl,4-Br H 2 5 Po 1198 - 200
2 5 p~ ~:199 - 200
2-Cl,4-CF3 H C2H5 B
27 4-CF3 - H C H Po 05185 _ 87
2 5 Po.2204 - 206
- 13 -
~O~i~573
Table 1 (continued)
Example r I ~ nl ~ ~3 P(C)
28 3,4-Cl H -C H B
2 5 Po.l: 201 - 202
29 2-Cl H 2 5 Po 05194 - 195
4-Cl H ~CH3 Po 2183 - 184
31 2,4-Cl H ~CH3 Po.l'185 - 186
32 3,4-Cl H ~CH3 Po 1191 - 194
332-Cl,4-Br H C~-CH3
34 4-Br H ~CH3 Po 1198 199
4-C~3 H ~CH Po 1187 - 188
36 2,4-Cl 3-CH3CH~CH3 Po.l:188 - 189
37 4-Cl H ~ ~CH3 Po.l195 - 197
38 2,4-C1 H ~ ~C~ Po.l202 - 204
39 4-Br H 2 ~CH Po os199 - 201
402-Ci,4-Br H-CH-CH~CH3 Bp :- 207 - 208
- 14 -
10~4~73
Table 1: (continued)
Ex R(n) Rl ~ b-p- (C~
41 - 4-CF3 H -CH2-CH~SH3b Po't 186 - 188
42 2,4_CI 3-~U~ -~ 2~ ~''05~ 204 - 206
II s A ~ -CH2-
Example ~) 1(n1)R3 b.p./m.p,( ~)
,_, __ _
43 4 Cl H -CH3 5 9 9
44 4_Br H ~ -CH3 0'01S 193 _ 194
4-C~3 ~ -CH3 b~P~o5s 175 - 177
46 2-Cl,4-~r H -CH3 b.p ; 205 - 20~
,D~
- 47 4-Cl H CH ~ CH b.~,1s 201 - 203
48 4-Br ~ CH~ CH3 b 4
49 4-CF3 ~2 CH3 b~Po~o~s 178 - 17~
S0 2,4~Cl H-OH2-CH\ 3 b,po,o5, 212 - 214
CH3 m.p- ~9 101
51 2-Cl,4-~r HCH~ 3 ~Po.1t 207 - 209
3 ~p. 94 - ~5
- 15 -
1094~73
, H2 c~ 3
III: A = -CH-
}:xan~ple R(n) 1 (nl ~1 R3 b.p./m.p. (C)
. . .. _. _ I ., ~__
52 4-Cl ~ H -CH3 P ~ 05 ~ 186 - 187
;3 4-Br ~1 -CH3 b ~;5 188 - 190
54 4-C~3 H CH3 0; 1 ~ 178
2, 4-Cl H -CH3 b ; 5 t 195 - 196
56 2-Cl, 4-Br H -CH3 P; 1 s 205 - 208
57 ¦ 4-Cl ~ CH2-CH\ 3 ¦ 0, I
58 4-Er H 2 3 0 ' 1 194 - 197
59 ~ 4-C 3 ¦ H ;-Cl~ 3 ~ 0; 5: 176 - 177
2, 4-Cl H -CH2-~ H3 P; 1: 197 ~ 198
61 Z-Cl, 4-B:r H CH2 CH3 oP; o5 204 - 205
. ~ . . .
16 -- _
10~4 573
Table -: (R) ~ ~ -0-CH-C-0-Z
EXample(R)n Z b-P-,(C~
No.
_ .
62 4-Cl -CH2CH2C=N b.p.0~1 20Q - 203
63 2,4-Cl n b.p~~1 214 - 216
64 4-Br " b-p-o,o5: 207 - 210
652-C1,4-CF3 0,05: 190 192
66 4-Cl -CH(CH3)C_N 0'1 196 - 198
67 2,4-Cl n b.p. ~ ~ 1 200 ~ 202
fi8 4-Br ~ 0~05.~
69 4-CF3 n b.p. 0~l 184 - 186
702-Cl, 4-Br ~ b.p. 206 - 209
- 17 -
10~573
Exal[ ple( R) n ;~ m.p. ( C )
.. . _ _, .. , ._ . __
71 4-Cl ~ OCH3 64-66
72 2, 4-Cl ~ C-OCH;~, 85-87
73 4-Cl -~-CO-CH2 -CH5 44-47
. 74 4-CF3 ~-Cl 91-92
2, 4-Cl ~-C-OCH2 -CH3 67-70
76 2, 4-Cl ~-C=C-C-OCH3 102-104
. 77 4-CF3 ~)-C-OCH3 67 69
78 2 ,4-~:1 _~ 101-103
,Co~~CHS .
79 4- Cl --~C-OCH3 81-82
80 2, 4- Cl ~0 3 104-106
-- 18 --
109~;73
~Q ~CH--C--S--CH2~ R3
O
R(n) R~
~ample R(n)R1 (n1 ) R3 ~ C)
_
81 4-Cl ~ --C~I3 Bpo 2:220 -- 222
82 4--Cl ~ C~3 Bpo 05: 214 -- 216
83 4--Cl --C~2 C~ Bpo 05: 223 -- 224
84 2,4-Cl E[ ~CE13 13po.1: 234 -- 236
2, 4~Cl ~ C}13 ~P0 . 1 237 -- 239
86 ~CI?3 El c ~~3 Bpo. 2: 19~ -- 197
87 CF3 1~ _ ~P0 ~ Z~7 ~ 210
109~S73
Example 88
2-~4'-(2",4"-Dichlorobenzyl)-phenoxy~-propionyllactic acid
methyl ester
44 grams of 2-L4'-(2",4"-dichlorobenzyl)-phenoxy~-
propionic acid~ 27 grams of 2-bromopropionic acid methyl ester,
21 grams of anhydrous potassium carbonate and 100 ml of acetone
were stirred at 60C for 8 hours. After cooling to 20C the
inorganic salts were filtered off. The acetone was distilled
off from the filtrate and the residue was distilled in vacuo.
51 grams (91.6% of the theoretical yield) of the follow-
ing compound having a Bpo 05 : 165 - 166C were obtained.
Cl- ~ C 2 ~ -0-CH cl-o-$ -IC~-OCH3
Cl
Example 89
2-14'(4"-Chlorophenoxy)-phenoxy] -propionyltar~ronic acid
diethyl ester
32 grams of the sodium salt of 2-~4'-(4"-chlorophenoxy)-
phenox~ -propionic acid, 27 g of bromomalonic acid diethyl
ester, 1 ml of dimethylformamide and 150 ml of toluene were
stirred at 80C for 18 hours. After filtering off the sodium
bromide with suction, the toluene and the excess of bromo-
malonic acid diethyl ester were distilled off from the filtrate.
43 grams of light yellow oil (96.0% of the theoretical
- 20 -
10~ ~573
yield) ~ere obtained. nD25 : 1.5300.
Cl- ~ -0- ~ -0-CH-IC-0-CH
Example 90
2-[4'-(2",4"-Dichlorophenoxy)-phenoxy~-propionyltartronic acid
diethyl ester
35 g of the sodium salt of 2-[4'-(2",4"-dichlorophenoxy)-
phenoxy~-propionic acid, 27 grams of bromomalonic acid diethyl
ester, 1 ml of dimethylformamide and 150 ml of toluene were
stirred at 80C for 18 hours. After cooling to 20C and fil-
tering off the sodium bromide with suction, the toluene and
the excess bromomalonic acid diethyl ester were distilled off
from the filtrate.
47 grams of light yellow oil (97% of the theoreticalyield) were obtained. nD25 : I.5337.
Cl-~ ~ -0- ~ -0-CH-CI-0-CH
~ O COOC2H5
Cl
Example 91
2-~4'-(2",4"-Dichlorophenoxy)-phenoxy~-propionylglycine
methyl ester
-
At a temperature of 10C - 15C a solution of 24 grams
10~i~573
(O~076 mole) of 2-[4'-(2~,4~-dichlorophenoxy)-phenoxy]-
propiunic acid chloride in 40 ml of tolu~ne were added drop-
wise over a period of 30 minuteB to 14 grams (0.152 mole) of
gl~cine ester, ~reshly relea~ed from glycine methyl ester
chlorohydrate, dissolved in 80 ml of toluene. The mixture
wa~ then ~tirred for 2 houra at 15 to 22C. The resulting
glycine metbyl e~ter chlorohydrate Wa8 filtered off with 8UC-
tion. The toluene wa8 distilled off in vacuo from the filtrate.
30 grams o~ light yellow oil, ~ 25 : 1.5652 w~re o~tained.
Cl ~ o ~ ~-~E~ CH2-C-OCH3
Cl 0 H 0
There ~hould also be mentioned 2-~'-t4N-chlorophenoxy~-
phenoxy]-propionylthioglycolic ~cid methyl eYter.
BIOLOGICAL EX~MPLES
~BRBICIDES
In these Example~, result~ were determined by evaluation
according to Bolle'~ ~cheme (NachrichteDblatt des Deutschen
Pflanze~schutzdi2nstes 16, 1964, 92 - 94).
- 22 -
10'3~;73
Evaluation scheme
Numerical Percentage damage to
value Weeds Crops
100 0
2 97.5 to < 100 > 0 to 2.5
3 95to < 97.5 > 2.5 to 5
4 9Oto < 95 > 5 to 10
85to < 9O > 10 to 15
6 75to < 85 > 15 to 25
7 65to < 75 > 25 to 35
8 32.5 to < 65 > 35 to 67.5
9 0 to < 32.5 > 67.5 to 100
Example I: Pre-emergence treatment
Seeds of various grasses were sown in pots and spray
powders or emulsion concentra~es of a number of compounds of
the invention were sprayed in different doses on to the soil
surface. Fluorodifen and Mecoprop were used as comparison
agents. The pots were then placed in a greenhouse for 4 weeks
and the results determined by evaluation according to Bolle's
scheme. The results are shown in Table A. As can be seen,
the compounds according to the invention listed in Table A
exhibit a very good action against weed grasses. For most
types of grass this is true even at very low dosages, for
example 0.15 kg of active substance/ha. Fluorodifen and
; Mecoprop are substantially weaker in their action against grasses.
. , ~ .
lO~S73
Table A:
Weed evalu~tion number in the caee of pre-emergence tre~tment
Compound Dosage Types of plant
according t ~Cg/ha A S ~
to E:xample ALSA LO EC
2.5 2 2 3
0.6 3 3 5 2
2 2.5 3 1 1 t
0.6 4 2 1 2
8 2.5 3 1 1 2
0.6 3 2 2 3
2.5
0.6 1 3 - 1 2
11 2.5 2
0.6 2 2
12 2.5
0.6 2 2 2
13 2.5 2
0.6 4 2
26 2.5 2
0.6 2 2
37 2.5
0.6 3 2 3 3
38 2.5 - 1 1 1
0.6 - 3 3 4
41 2.5
0.6 . 3
43 2.5 2
~1.6 3 2 1 2
44 2.5
0.6 1 2
47 2.5 2
0.6 4 2 2 3
53 2.5
0.6 . 1 2
54 2.5
0.6 2
-- 24 --
.
~0~73
Con~ound Dosage Type~ of plant
according ~ Kg/ha A S )
to Example AL SA LO E~
2.5
0.6 2
56 2.5 3
0.6 4 2
57 2.5 2 1 ~ 1
0.6 3 2 2 2
63 2.5
0.6 2 3 2
64 5 . 0
1.2 - -- 2
6~ 5.0 ~
1.2 -- -- 2
68 5.0
1 .2
72 2. 5 2 3
0.6 3 6 3 3
73 2.5 4 2 1 2
0.6 ~i 4 2 3
2.5 3 1 1 3
0.6 4 ~ 3 4
Fluorodifen 2. 5 7 t 1 4
0.6 8 5 8 8
0.15 8 7 8 9
2.5 4 3 5 3
M~oprop 0. 6 7 6 8 7
0.15 8 ~ 9 8
SA ~ Setari~ :
LO ~ Lolium
EC - Echinc~clllo~
AS -- Ac!~ive ~ub~tarce
-- 25 - - -
~n~73
Example II: Post-emergence treatment
Seeds of various grasses were sown in pots and cultivated
in the greenhouse. 3 weeks after sowing, a number of compounds
of the invention were applied in different doses on to the plants
in the form of spray powders or emulsion concentrates, and after
standing for 4 weeks in the greenhouse the action of the compounds
was evaluated according to Bolle's scheme. Fluorodifen and
Mecoprop were used as a comparison.
As can be seen from the results listed in Table B, com-
lo pounds of the invention exhibit a good to very good action
against the weed grasses, and are superior to the known agents
Fluorodifen and Mecoprop.
Example III: Post-emergence treatment
Using the same method as in E~ample II (Post-emergence
treatment), various crop plants were sprayed with suspensions
or emulsions of compounds of the invention mentioned in Examples
I and II. Even at a high dosage of 2.5kg/ha, soya beans, peanuts,
dwarf beans, field beans,~peas, lucerne, flax, cabbage, rape,
cucumber, sunflower, tobacco, carrots, celery and sugar beet showed
no damage. Barley and wheat showed no reaction to the preparaticns
according to E~amples 1, 2, 8, 11, 37, 38, 43, 47~ 53, 56 and 57.
Similar results were obtained when the compounds were
sprayed on to the soil surface in the pre-emergence method.
-26-
109.~573
Table B:
Weed evaluation nunibera in the case of post-emergence treatment
Compound Dosage ~pe~ of plant
according ( Kg/ha A S )
to Exa~ple AL S.A LO
t 2.5
0.6 1 1 4
2 2.5 -- 1 t
0.6 -- 4 3
8 2.5 - 1 2
0.6 - 2 5 3
2.5
0.6 2
11 2,5
0.6 2
12 2.5
0.6 t
13 2.5 1 1 1 t
0.6 1
26 2.5
0.6
37 2,,5 3 2 - ~
0.6 4 4 -- 1
38 2.5 - 1 3
4 5
41 2. 5
0.6 1 1 2
43 2.5 1 1 4
1~.6 2 2 5
4~ 2.5 I ~ 1 1
0.6
47 2.5 - 1 2 2
0.6 - ~i 6
53 2.5
0.6 1 - 1 .
54 2.5
0.6
-- 27 --
:
.
'
109'~ 73
Co~und Doaage Types of plant
according ( ~g/ha A S )
to E:xan~ple AL SA LO I~C AV
. . .
2.5
0.6
56 2.5 -- t
0.6 -- 1 1 1
57 2.5
0,.6 4
63 2.5 1 1 4
006 4 1 7
64 2.5 - -- 3
0.6 -- - 6
67 2.5 1 1 - 1
0.6 1 3 - 1
68 2.5 - 4
0.6 5 6
2.5 t
0.6 2 1 2
2.. 5 8 2 6 4 8
Flllorodife~ 0.6 8 3 8 6 8
0.15 9 5 9 8 9
2.5 8 7 8 8 8
oprop 0. 6 9 8 9 9 9
0.15 9 9 9 9 9
AV -- ~el~a
AL - ~ ,
8A - Set~ria
~Ch~nochloe~
-- 28 --
10~ 1~73
BIOLOGICAL EXAMPLES
~GICIDES
In these Examples, the following were used as comparison
agents:
A = Combination of 5,6-diyhdro-2methyl-1,4~oxathiin-
3-carboxanilide and methoxyethyl Hg silicate
B = Manganese ethylene-1,2-bis-dithiOcarbamate
D = Tetramethylthiuram-disulphide (TMTD)
E = S-ethyl-N-(3-dimethylam nopropyl)-thiolcarbamate
hydrochloride (Prothiocarb).
Example IV
Barley seeds infected with Ustilago nuda td1egree of
infection 15%) were dressed with compounds according to the
invention in the concentrations given in Table C. sown in pots,
and cultivated first at a low temperature and later at higher
temperatures (20C) in a greenhouse. The combination A was
used as co~parison agent. 10-12 weeks later, the sound stems and
the stems infected with Ustila~o nuda were counted, the degree
of infection was determined in each case, and finally the degree
of action calculated. The results are shown ir~ Table C.
-29-
~0'3 ~S73
Table C~
Compound ~ffect in % of 1 g o~ dressing agent
according per 100 kg of ~eed
to Example
250 200 100 50 25
.
1 (50 % ~trength) 100 95 60
37 (50 % strength) - - - 100 80
89 (50 % strength) - - - 100 90
13 (50 % ~trengt~ 100 70
43 (50 % ~trength) - - - 100 70
~ , . . . . .. .
73 (50 % strength) - 100 95 50
A ~50 % strength) 100 sa go
untreated infected
p'~ ' '
Table C ~hows the excellent action, ~uperior to that of
the cGmpari~o~ agent ~, of compound~ o~ the i~vention ~gainst
U~til~a~o nuda.
Example V:
Summer barley ~eed~ naturally infected with Helmintho-
~vorium arami eum, with a degree o~ infeation of 24 X, were
dre~sed in various concentration~ with 50 % dre~sing agent~
containing the agent~ ~hGwn in Table D. The seeds were sown
in trays which were ~ubseguently placed in a greenhouse. Later,
- - 30 -
~09~73
both the plant~ infected with He ~intho-cDorium r ~ neum and
those that were 20und were counted, the degree of infection
in each case Wa8 determined, and finally the degree of action
w~ calculated. The result are given in Table D.
Table D:
Dre~sinq agent . Effect in ~ of 1 g of dreQsing age~t
according to per 100 kg of seed
Example
. 300 250 200 100
__ _ . . . ___
67 (50 % ~trength) _ _ 100 80
.. .. . _ . .
a (50 % ~trength) _ 100 95
~ _ . ~_ ..
B (80 % ~trength) 75 _ 60
--_ ~ _
u~treated infected .
plant~ 0
,~ , .
. . . _ ~he ~ 8 in T~ble ~ shGw t~e excellent actio~ of the
compound o~ th~ $nvention agai~t H2lmintho~0rium Dnd the
~periority oE thi~ mercury-free ~ompo~nd over the me~cury-
free compari~on agent B and ~he ~ercury-containi~g c ~ riJo~
agent A.
ExamDle VI-
.
Sugar beet ~ed~ naturally infected with Phoma betae
uith a degree of infection of approximat~ly 60 %~ ~ere dreA~ed
with the compound o~ the in~ention shGwn in Table E and ~i~h
co~p~rison agent D, pla~ in tray~ ~nd cultivated ~t 20C i~
greenhou~. 3 wOEek~ ~ter sowing, the ~ug~r beet plant~
31 -
10~t~S73
were examined for infection with Phoma betae and the degree
of action of the compound of the invention was determined.
The results are shown in Table E.
Table E:
Dressing agent Effect in % of 1 g of active
according to substance per 100 kg of seed
Example
300 200 100 50
-
56 (50% strength) - - 100 80
D (80% strength) 100 95 85 75
untreated infected 0
plants
Example VII:
The compound shown in Table F was uniformly dis~ributed
and mixed into a soil uniformly but heavily infected with
Pythium ultimum. The soil treated in this manner was intro-
duced into plastic po~s and 10 pea seeds were then sown in
each pot. The procedure was repeated with agent E for com-
parison. 8 to 10 days after sowing, the evaluation of the
experiments was carried out by determining the number of sound
plants that had emerged and calculating the degree of action
of the compound of the invention. The controls used were pots
containing infected, untreated earth.
- 32 -
10!? ~;73
Ta~le F-
Compound Effect irl % of 1 mg of active
according ~ubstance per kg of soil
to Example
200 100 50 25
, . . ~
26 100 100 100 80
E 80 70 60
~treated
infect:ed
plantQ o
Table~ nd F show the excelle~t ~lmgicidal action of
t}le co~pound~s, whic~h i~ sup~rior to t~at of the ca~pari~on
age~ts D ~nd E. - -
-- 33 --
