Unite States Patent (191: Fol-Y Et Al.
Unite States Patent (191: Fol-Y Et Al.
Unite States Patent (191: Fol-Y Et Al.
Fol-y et al..
[54] PHENOXYALKYLOXAZOLINES, AS
SlELlEClllVE HERBICIDES IN CEREALS
[11]
[45]
4,225,336
Sep. 30, 1980
[75] Inventors: Werner Fdry, Basel; Hermann Remp?er, Ettingen, both of Switzerland; Georg Pissiotas, Lorrach, Fed. Rep. of Germany; Otto Rohr, Therwil; Beat Biihner,
Binningen, both of Switzerland
[57]
ABSTRACT
O-GH;
ZO
OCH-C
N-Cl-lz
[63]
[30]
[51] [52]
or
R2 N
(RIM
Int. lCl.2 ...................................... .. AOIN 9/28 US. Cl. ......................................... 1. 71/88; 71/94;
R3
R1 is halogen, tri?uoromethyl, cyano or nitro R2 is hydrogen, halogen or cyano R3 is halogen trifluoromethyl or cyano and
n is l or 2.
4/1975
9/ 1977
cereal.
4,133,675
1/1979
4 Claims, No Drawings
1
HERBICIDES IN CEREALS
4,225,336
I
2
R CH2 (II)
PHENUXYALKYLOXAZOLINES, AS SELECTIVE
2-0
CROSS-REFERENCE TO RELATED 5
0 OCH-C0-'N
APPLICATION
\cn
This is a continuation-in-part of our application Ser. No. 974,195, ?led Dec. 28, 1978, now abandoned.
DETAILED DISCLOSURE
Instead of the ethyleneimide, it is also possible to subject a phenoxyalkylethylamide of the formula III
R (111)
substituted phenozryalkyloxazolines, herbicidal compo sitions which contain these compounds as active ingre dients, and to methods of selectively controlling weeds
in crops of cereals.
0""CH2
wherein R and Z are as de?ned for formula I, whilst X can be the OH group, a halogen atom or a sulfonic acid
N-CI-IZ
25
Suitable solvents are in particular aprotic water~solu ble solvents, such as low molecular alcohols, ketones,
wherein
R represents hydrogen or methyl and -
or R2
(R0,,
0
N 35
tions, for example in the presence of sulfuric acid, if X represents the hydroxyl group. Suitable catalysts for the cyclisation are the alkali metal salts or tertiary ammonium salts of halides and sulfonic acids.
The cyclisation occurs at room temperature, but the reaction mixture can be heated to the boil in order to
R3
cides and growth regulators is known from US. Pat. No. 3,877,821. Herbicidal compositions which contain
the formula V
legungsschrift 2,613,697. Three of these oxazolines are disclosed in the published Japanese Patent Publication
No. 52 139 034. The present phenoxyalkyloxazolidines exhibit an ef fective herbicidal action when employed in low rates of
l
Hal-CH
application and surprisingly do not harm cerals in spite of their good action against monocotyledonous weeds. The phenoxyalkyloxazolines of the present invention
have a low toxicity to warm-blooded animals and their
wherein Hal represents a halogen atom and R is as defined for formula I, in the presence of an acid accep
tor.
This reaction is also carried out in a water-miscible solvent or else in a halogenated hydrocarbon, under
normal pressure and at a temperature which can be
The compounds of the formula I are obtained by known reaction methods of chemical synthesis. In a ?rst process, phenoxyalkylethyleneimides of the formula Ill
between room temperature and the boiling point of the reaction mixture. Preferably, the reaction mixture is re?uxed.
The acid acceptor can be an aqueous alkali metal hydroxide, such as KQH and NaOH, and also another .
4,225,336
' .
4
-continued
I o
base, such as ammonia, a carbonate (K2003, NaHCOg), an alcoholate (NaOCH3, potassium tert-butylate), and
also an organic base, such as triethylamine etc. If an
z-o
Compound _ Z
/ O-('ZH--'C\
R
I R
\N
Physical data
desirably obtained by amidation from the correspond ing phenoxyphenoxypropionic acids and pyridyloxy phenoxypropionic acids, for example those described in German Offenlegungsschrift 2,223,894, 2,531,643, 2,546,251 and 2,652,384.
The amidation is carried out by methods which are in
10
5 6 7
8 9
10
4-chlorophenyl 4-cyanophenyl
4-chloro-2-tri?uoromethyl
themselves known by reacting the halides or the anhy dride of these acids with ethyleneimine, the correspond ing haloethylamines, or with a 2-amino-ethyl sulfonate. The following Examples illustrate a process of the present invention for obtaining such compounds. Parts and percentages are by weight. Further compounds
is
11
12
phenyl 4-chloro-2-nitrophenyl
4-bromo-2-nitrophenyl
The novel
(pyridyloxy)-phenoxy]-alkyloxazolines exhibit a strong herbicidal action in relatively low rates of concentra 20 obtained in analogous manner are listed in the subse tion. quent table.
The compounds of the formula I can be used as herbi
cides in pre-ernergent and especially in post-emergent application. Their action is directed in particular against 25 monocotyledonous weeds and they can be used for selective weed control in crops of dicotyledonous 50 g of 50% NaOH and 1 g of tetrabutylammonium plants, for example in soya. However, they are also bromide are added to 39 g (0.1 mole) of a-[4~(3',5 suitable for selective weed control in crops of certain
EXAMPLE 1
are added and the methylene chloride phase is sepa rated, dried over magnesium sulfate and concentrated. A small amount of ether is added to the oily residue,
The present invention also provides herbicidal com positions which contain a compound of the formula I as active component. Such compositions can be in the
form of conventional solid formulations (dusts, tracking whereupon the product crystallises. The crystals are 35 powders, granules), water-dispersible concentrates
(wettable powders, emulsions, emulsi?able concen
trates and pastes), or solutions, and are formulated by
collected by ?ltration and dried, affording 25.3 g of ?nal product with a melting point of lll1l3 C. (known)
EXAMPLE 2
A suspension of 25.4 g of 4-(4'-tritluoromethyl carriers, with or without the addition of dispersants or phenoxy)-phenol, 23.6 g of a-bromopropionic acid-2 solvents which are inert to the active substances. The chloroethylamide and 20 g of anhydrous potassium carbonate in 250 ml of ethylene methyl ketone is stirred 45 active substances can be processed to the following formulations: for 18 hours at re?ux temperature. The reaction mixture
is ?ltered and the ?ltrate is concentrated in vacuo. The ' oily residue (19.5 g) is dissolved in 75 m1 of methylene chloride and, after addition of 2.5 g of tetrabutylam
The compositions of the present invention are ob tained in known manner by homogeneously mixing and grinding active substances of the formula I with suitable
solid formulations: dusts, tracking powders, granules (coated granules, impregnated granules and homoge
perature in a nitrogen atmosphere. The methylene chlo ride phase is separated, washed with water, dried and
concentrated in vacuo, affording 13.6 g of the title com
cation are ordinarily from 0.1 to 10 kg, preferably from 0.25 to 5 kg, of active substance per hectare. The active
60 ample as follows (parts are by weight):
Z-Q
Compound Z
oc|:H-c \ R \N
R Physical data
2-chloro-4-trifluoromethylphenyl 2,4-dichlorophenyl
(a)
5 parts of one of the active substances of the formula
I .
5
951 parts of talc;
4,225,336
ethylene oxide,
(b)
2 parts of active substance
5 parts of sodium aluminium silicate, 14 parts of cetyl polyglycol ether with 8 moles of the
1 part of oleyl polyglycol ether with 5 moles of the
ethylene oxide,
2 parts of spindle oil,
ground.
Granulate
The following substances are used to prepare a 5%
granulate:
5 parts of one of the active substances of the formula
I;
0.25 part of epichlorohydrin; 0.25 part of cetyl polyglycol ether; 3.25 parts of polyethylene glycol; 91 parts of kaolin (particle size 0.3-0.8 mm).
The active substance is mixed with epichlorohydrin and the mixture is dissolved in 6.parts of acetone. Then
Emulsi?able Concentrate
The following ingredients are mixed to manufacture a 25% emulsi?able concentrate: 25 parts of one of the active substances of the formula
I,
5 parts of a mixture of nonylphenolpolyoxyethoxy
Wettable Powders 25 The active substances of the invention are also of The following constituents are used for prepare (a) a interest for combined application with a number of 50%, (b) a 25% and (c) a 10% wettable powder: herbicides of the phenylurea and triazine series in cereal crops, maize, sugar cane and in fruit growing and viti
(a)
herbicides (pre- and postemergent control). Preemergent herbicidal action (germination inhibition)
In a greenhouse, immediately after sowing the test
plants in seed dishes the surface of the soil is treated with an aqueous suspension of the active substances obtained from a 25% wettable powder. Four different concentration series were used, corresponding to 4, 2, l
40 and 0.5 kg of active substance per hectare respectively.
(b)
25 parts of the above active substance, 5 parts of sodium oleylmethyltauride,
The seed dishes are kept in the greenhouse at 2225 C. and 50 to 70% relative humidity. The test is evaluated 3
45
weeks later according to the following rating: 0=plants undamaged (as untreated control); 1~9=intermediate stages of damage;
(C)
10 parts of the above active substance,
3 parts of a mixture of the sodium salts of saturated
substance emulsion in rates to 0.5, l, 2 and 4 kg of active substance per hectare and kept at 2426 C. and 45-60% relative humidity. The test was evaluated, as in sponding carriers (kaolin and chalk) and then these are 55 the preemergent test, 5 and 15 days after treatment in mixed and ground, to yield wettable powders of excel accordance with the same rating.
82 parts of kaolin. The indicated active substance is applied to the corre
Post-emergent action in the ?eld A field in which winter wheat of the variety >TAM
stance. Such suspensions are used for preemergent con 60 101 had been sown in October was treated the follow
plants.
45% paste:
(wild oats), the most prominent weed, was encountered Paste in the l-5 leaf stage, in parcels with dilute aqueous The following substances are used to manufacture a 65 active substance emulsions, so that the parcels were
I)
7
the following table:
Compound rate of application in kg/ha
No. 1 A
Hoe 23 408
4,225,336
1. A method for controlling weeds in crops of cereals
wheat and of the wild oats was rated in accordance with the scale referred to above. The results are reported in
2
5 8
3
2
10 l0
8
N-CHZ
2 7
2
0 7
0 5
2
9 l0
7
9 l0
9 l0
3
wherein R represents hydrogen or methyl and Z represents a substituted phenyl radical or pyrid-2-yl radical
3,953,442
This concentration was not tested.
A ?eld in which summer barley of the type CM-67 had been sown in the middle of February was treated
R:
(RD):
o
N
Ra
R1 dilute aqueous active substance emulsions, so that the tro, parcels were sprayed with 2, 1.5, l, 0.75 and 5 kg 25
respectively of active substance per hectare. The test was
wherein
represents halogen, trifluoromethyl, cyano or ni
R2 represents hydrogen, halogen or cyano, R3 represents halogen, tri?uoromethyl or cyano, and
n is l or 2; I _
evaluated after 22 days in April and the state of the plants was rated invaccordance with the above scale. The results are reported in the following table.
Plant rate of
to an area where cereal crop is growing or expected to grow. 30 2. A method according to claim 1, wherein the phe
noxyalkyloxazoline used is '
application in
kg/ha ' 2
Summer barley
1.5 l 0.75 0.5
avena fatua
2 1.5 l 0.75 0.5
ethyl}-oxazoline.
Compound
No. l A
Hoe 23 408
O 9
O
0 9
O
0 9
0
0 7
0 6
0
l0 l0
l0
l0 l0
9
l0 l0
6
l0 l0
10 l0
5
We claim:
45
5O
55
60