Note: Descriptions are shown in the official language in which they were submitted.
aye --
I 0050/3~813
Herbic1dal diphenyl ethers and their use for
controlling undesirable plant growth
The present invention relates to diphPnyl ethers,
- herbicides which contain these compounds as active in-
gradients and -their use for controlling undesirable plant
growth
Various herbicidal active ingredients which belong
to the class consisting of diphenyl ethers and carry a
substituted aminosulfonyl radical ortho to the vitro
group have been disclosed in the literature German Laid-
Open Applications DOS 2,261,918 and DOS 2,833,021).
We have found that diphenyl ethers of the formula
I
Z3 N02
z2 SNEEZER
n it
Ox em
where z1 and z2 independently of one another are each
hydrogen, halogen, vitro, cyan, carboxyl, C1-C4-alkyl~
C1-C4-haloalkyl or C1-C4-alkoxy, Z3 is halogen, vitro,
Sweeney C1-C4-alkY~ C1-c4-haloalkyl~ C1-C4-alkoxy~
C1-C~,-haloalkoxy, C1-C4-alkylmercapto, C1-C4-halo-
alkylmercaPto~ C1-C4-alkylsulfinyl, C1-C4-haloalkylsul-
final, C1-C4-alkylsulfonyl or c1-C4-haloalkylsulfonyl,
X is hydrogen C1-C4-alkyl, unsu~stituted or halogen-
substituted azalea of not more than 7 carbon atoms, an alkali metal ion or an unsubstituted or alkyl-substituted
ammanium ion, R is C1-C20-alkyl, C1-C12-haloalkyl,
an unsubstituted or halogen-substituted araliphatic radix
eel of 7 to 20 carbon atoms, cycloalkyl of 3 to 12 carbon
atoms, unsubstituted or substituted phenol, amino, C1-C4-
alkylamino or di-C1-C~-alkYlamino~ and n and m indepen-
deftly of one another are each 00 1 or 2, have a total or
selective herbicidal action, depending on the formulation
and dosage.
In formula I, z1 and z2 independently of one
another are each hydrogen, halogen, vitro, cyan, carboxyl,
I
- 2 - OOZE. 0050/36813
C1-C4-alkyl, C1-C4-haloalkyl or C~-C4-alkoxY, ego
foreign, chlorine, bromide, iodine, methyl, ethyl, n-pro-
pow isopropyl, n-butyl, tert.-butyl~ trifluoromethyl, dip
fluoromethyl, fluoromethyl, trichloromethyl, dichloro-
methyl, chloromethyl, difluorochloromethyl, 1-chloroethyl,
2-chloroethyl, 1-fluoroethyl, 2-fluoroethyl, Roy-
chloroethyl, 2,2,2-trifluoroethyl, 1,1,2,Z-tetrafluoro-
ethyl, 1,1,2-trifluoro-2~chloroethyl~ spinet
fluoroethyl, methoxy, eighth, n-propoxy, isopropoxy or
ter~.obutoxy, Z3 is halogen, vitro, cyan, C1-C4-alkyl,
C1-C4-haloalkyl, C1-C4-alkoxy, c1-C4-haloalkoxY~
C1-C4-alkylmercapto, Cl-C4-haloalkylmercapto, Cluck-
alkylsulfinyl, C1-C4-haloalkylsuLfinyl" C1-G4-alkYlsul-
phenol or C1~C4-haloalkylsulfonyl~ ego fluorine, chlorine,
bromide, iodine, methyl, ethyl, n-propyl, isopropyl, n-
bottle, tert.-butyl, trifluoromethyl, difluoromethyl,
fluoromethylO trichloromethyl~ dichlorome~hyl, sheller
methyl, difluoromethyl, 1-chloroethyl, 2Ochloroethyl, 1-
fluoroethyl, floral, 2,2,2-trichloroethyl, 2,2,2-
trifluoroethyl, 1,1,2,2-tetrafluoroethyl, trifler-
2 chloroethyl, 1,1,Z,2,2-pentafluoroethyl, methoxy, ethics,
n-propoxy~ isopropoxy, tert~-butoxy, trichloromethoxy, in-
fluoromethoxy, 1-chloroethoxy, 2-chloroethoxy, flyer-
ethics, 2-fluoroethoxy, 2,2,2-trichloroethoxy, try-
Z5 fluoroethoxy, 1,1,2,2-tetrafluoroethoxy, punt-
fluoroethoxy, methylmercapto, ethylmercapto, trichloro-
methylmercapko, trifluoromethylmercapto, methylsulfinyl,
ethylsulfinyl, methylsulfonyl, ethylsulfonyl or trifler-
methylsulfonyl, X is hydrogen, C1-C4-alkyl, ego methyl,
ethyl, n-proPyl, propel, n bottle or tert.-butyl, us-
substituted or halogen-substituted azalea of not more than
7 carbon atoms, ego acutely, pronely, chloroacetyl, dip
chloroacetyl or bouncily, an alkali metal ion, ego sodium
or potassium, or an unsubstituted or alkyl~substituted
ammonium ion, ego ammonium, methylammonium, dim thylammon-
sum, trimethylammonium, ~etramethylammonium, ethylammonium,
diethylammonium, triethylammonium or n-butylammonium~ and
- 3 - OOZE. 0050/36813
R is C1~C20-alkyl, preferably C1-C7-alkYl, in portico-
far C~-C4-alkyL, ego methyl, ethyl, n propel, isopropyl,
n-butyl, tertl-butyl or the isometric ponytail, Huxley or hop-
twill radicals C1-C12-haloalkyl, preferably C1-C~-
5 haloalkyl, ego chloromethyl, trichloromethyl, sheller
ethyl, 2-fluoroethyl, sheller n-propyl or chlorine-
bottle, an unsubstituted or halogen-substituted araliphatic
radical of 7 to 20, in particular 7 to 9, carbon atoms,
ego bouncily 4-chlorobenzyl, 2~4-dichlorobenzyl, phenethyl
1û or phenylpropyl, or cycloalkyl of 3 to 1Z, preferably 3
to 6, and in particular 5 or 6, carbon atoms, ego cycle-
propel, cyclobutyl, cyclopentyl or cyclohexyl, or is pie-
nil which is unsubstitu~ed or substituted by halogen, such
as fluorine, chlorine or bromide, by C1-C4-alkyl, such
as methyl or ethyl, by C1-C4-alkoxy, such as methoxy
or ethics, by C1-C4-haloalkyl, such as trifluoromethyl,
by vitro or by cyan, or is amino, C1-C4-alkylamino
or di-C1-C4-alkylamino, ego methyl amino, ethyl amino,
n-propylamino, iso~ropy~amino, n-butylamino, dimethylamino,
diethylamino, di-n-propylamino, diisopropylamino or din-
butylamino.
The preferred diphenyl ethers are compounds of the
formula I where z1, zZ and Z3 independently ox one
another are each hydrogen, halogen, Cook haloalkyl
or C1-C4-haloalkylmercapto, X is hydrogen, C1-C4-
alkyd or an alkali metal ion, R is C1-C20-alkyl or C1-
C1~-haloalkyl or is phenol which is unsubstituted or
substituted by halogen, C1-C4-alkyl, C1-C4-alkoxy,
c1-C4-haloalkyl, vitro or cyan, n is 0, 1 or 2 and
3û m is I Diphenyl ethers of the formula I where to Jo
hydrogen, ZZ is chlorine and Z3 is trifluoromethyl are
particularly preferred especially those of the formula
I which contain a 2-chloro-4-trifluoromethylphenoxy radical.
Diphenyl ethers of the formula I are obtained by
reacting a sulfonyl halide of the formula
issue
Al 4 OOZE Owe
3~0~J~)2 ( I I )
Z Shoal
where z1, I Z3 and n have the above meanings and
Hal is halogen, with not Less than an equimolar amount of
a compound of the formula
~12NS-~,
( I I I
em
where R and m have the above meanings, in an inert organic
solvent and in the presence or absence of an acid acceptor
at from -20 to ~150C, in particular from 0 to 120C.
The reaction can be carried out bushes or continuously,
under atmospheric or supera~mospheric pressure.
The process for the preparation of the diphenyl
ethers of the formula I can be represented, by way of
example, by the following equation:
F3C 2 H2NS2C~3 _ F3 0 No
Of Sol Of S-NHso2cH3
US The starting materials are employed in about
stoichiometric amounts to. from 0.9 to 1.1 moles of
starting material III are employed per mole of II. If
necessary an acid acceptor can be added to complete the
reaction. Furthermore, the hydrogen halide formed during
the reaction can be expelled by passing in an inert gas,
ego nitrogen Advantageously, the process is carried out
as follows: a solution of the sulfonyl halide II in an
inert organic solvent is run, if appropriate simultaneously
with an equimolar amount of an acid acceptor, into a soul-
ton of the starting material III in an inert organic sol-
vent at from ~20 to ~150C, preferably from 0 to +120C.
To complete the reaction, stirring is continued
~2~93~S
- 5 - OOZE. 0~50/36R13
for from 0.5 to 48, preferably from Z to 1Z, hours at
from 0 to 60C. The reaction mixture is filtered and
evaporated down, and the desired end products can be is
fated by reprecipitation or recrysealli2ation or by stir-
ring with water. If necessary, they can be purified by chromatography.
The diphenyl ethers of the formula I are also ox-
twined by reacting a sulfonamide of the formula
Al
Z3 ~12
(IV)
Z S NH
n
O X
n
where z1~ z2, z3~ X and n have the above meanings
and Hal is halogen with not less than an equimolar amount
of a compound of the formula
Claus-
I where R and m have the above meaning sin an inert organic
solvent and in the presence or absence of an acid acceptor
at from -20 to ~150C, in particular from 0 to 120C.
The reaction can be carried out bushes or continuously,
under atmospheric or super atmospheric pressure.
The diPhenyl ethers of the formula I in which m
and n are each 1 or Z can also be obtained by oxidation
of a compound of the formula I in which m and n are each
0, by means of a suitable oxidizing agent.
Compounds of the formula I where X is hydrogen can
subsequently be converted into compounds of the formula
Z5 I where X is alkyd, unsubstituted or halogen substituted
assailed an alkali metal ion or an ammonium ion by using the
conventional alkylation, acylation or neutralization
reactions.
The process for the preparation of the diphenyl
ethers of the formula I by reacting a compound of the
formula IV with a compound of the formula V can be
3t3~5
- 6 - OOZE. 0050/36813
represented by Jay of example, by the hollowing equation:
F~C 0 No I CLASSIC -MCi~ Fur 0 2
C l N~12 C l S-NH-50
The starting materials are employed in about
stoichiometric amounts, to. from 0.9 to 1.1 moles of
S starving material V are employed per mole of IVY If
necessary, an acid acceptor can be added to complete the
reaction. Furthermore, the hydrogen halide formed during
the reaction can be expelled by passing in an inert gas,
ego nitrogen Advantageously, the process is curried out
as follows: a solution of the sulfonyl halide V in an
inert organic solvent is run, if appropriate simultaneously
with an e~ui~olar amount of an acid acceptor, into a soul-
lion of the starting material IV in an inert organic sol-
vent, at from -20 to ~150C, preferably from 0 to +120C.
To complete the reaction, stirring is continued
for prom 0.5 to 48, preferably from 2 to 1Z, hours, the
temperature being kept at from 0 to 60C. The reaction
mixture is then evaporated down, and the end products of
the formula I can be isolated by reprecipitation or no-
crystallization or by stirring with water. If necessary,
they can be purified by chromatography.
For both processes, organic solvents which are in-
oft under the particular reaction conditions are used.
Examples of suitable solvents are halo hydrocarbons, in
Particular chlorohydrocarbons, ego tetrachloroethylene,
1,1,2,2- or 1~1,1,2-tetrachloroethane, dichloropropane,
ethylene chloride, dichlorobutane, chloroform, sheller-
naphthalene, dichLoronaphthalene, carbon tetrachloride,
1,1~1- or 1,1,2-trichloroe~hane, trichloroethylene, punt
chloroethane, o-, m- or p-difluorobenzene, 1,2-dichloro-
ethanes 1,1~dichloroethane, 1,2-cis-dichloroethylene,
chLorobenzene, ~luorobenzene, bromobenzene, iodobenzene,
o-, p- or m-dichloroben2ene, o-, p- or m-dibromobenzene,
owe m- or p-chlorotoluene or 1,2,4-trichlorobenzene,
~2293D~5
` - 7 - OOZE. 0050/36813
ethers ego ethyl propel ether, methyl tert.-butyl ether,
n-butyl ethyl ether, d;-n-butyl ether, diisobutyl ether,
dismal ether, diisopropyL ether, anisole, finitely,
cyclohexyl methyl ether, deathly ether, ethylene glycol dip
methyl ether, tetrahydrofuran~ Dixon, thioanisole or
I '-dichlorodiethyl ether, nitrohydrocarbons, such as
nitromethane, nitroethane, nitrobenzene, o-, my or p-
chloronitrobenzene or o-nitrotoluene~ nitrites, ego asset-
nitrite, butyronitrile, isobutyronitrile, benzonitrile or
m~chlorobenzonitrile, aliphatic and cycloaliphatic hydra-
carbons, ego Hutton, inane, nonage, o-, m- or p-cymene,
gasoline fractions boiling within a range from 7û Jo
190C, cyclohexane, methylcyclohexane, decline, petrol
Lomb ether, hexane, naphtha, 2,2,4-trimethylpentane,
2,2,3-tr;methylpentane, 2,3,3-trimethylpentane or octane,
ester, ego ethyl acetate, ethyl acetoacetate or isobutyl
acetate, asides, ego formamide, methylformam;de or dip
methylformam;de, kittens, ego acetone or methyl ethyl key
tone, and mixtures of these. Advantageously, the solvent
is used in an amount of from 100 to 2,000, preferably prom
200 to 7U0~ % by weight, based on the starting materials.
Suitable acid acceptors are all conventional acid
acceptors. These preferably include tertiary amine,
alkaline earth metal compounds, ammon;um compounds alkali
metal compounds and mixtures of these, but zinc compounds
can also be used. Examples of suitable basic compounds
are potassium hydroxide, sodium hydroxide, potassium car-
borate, sodium carbonate, lithium hydroxide, lithium car-
borate, sodium bicarbonate, potassium bicarbonate, calcium
hydroxide, calcium oxide, barium oxide, magnesium hydroxide
magnesium oxide, barium hydroxide, calcium carbonate, Meg
noisome carbonate, magnesium bicarbonate, magnesium ace-
late, zinc hydroxide zinc oxide, zinc carbonate, zinc
bicarbonate, zinc acetate, sodium format, sodium
acetate, trimethylamine, triethylamine, tripropylamine,
triisopropyl~mine, tributylamine, triisobutylamine~ in-
sec.-butylamine, tri-tert.-butylamine, tribenzylamine,
~;~293~;
.
- 8 - 0.Z. 0~50/36813
tricyclohexylam;ne, triamylamine~ d;;sopropylethylamine,
~rihexylam;ne, N,N-dimethylanil;ne, N,~J-diethylaniline,
N,N-diprouylaniline, NUN dimethyltoluidine, N,N-diethyl-
Teledyne, NUN dipropyltoluidine, N,N-dimethyl-p-am;no-
pardon, N,N-diet-hyl-p~aminopyridine, NON-dipropyl-p-
aminopyridine, N-methylpyrrolidone, N-ethylpyrrolidone,
N-methylD;peridine, N-ethylpiperidine, N-methylpyrroli-
dine, N-ethylpyrrolidine, N-methylimidazole, N-ethylimi-
dazzle, N-methylpyrrole, N-ethylpyrrole, N-methylmorpho-
10 line, N ethylmorpholine, N-methylhexamethyleneimine, N-
ethylhexamethyleneimine, pardon, quinoline, ~X-picoline,
î~p;coline, ~-picoline, isoquinoline~ pyrimidine, acrid
dine, N,N,N',NI-tetramethylethyLenediamine, N,N,N',N'-
tetraethylethylenediamine, quinoxaline, quinazoline, N-
propyldiisoPropylamine, N~N'-dimethylcyclohexylamine,
letdown, letdown, trifurylamine and triethylene-
Damon
The starting compounds are prepared by methods
known from the literature. For example, the ethers of the
20 formulae II and IV are obtained by the procedures desk
cried in German Laid-Open Applications DOS 2,833,021
and DOS 3,21Z,1~5. The compounds of the formulae III
and V are available generally, or can likewise be prepared
by methods known from the literature.
The Examples which follow illustrate the prepare-
lion of the compounds of the formula I by the above pro-
cusses. Parts by weight bear the same relation to parts
by volume as that of the kilogram to the liter.
EXAMPLE 1
4.95 parts by weight of metnanesulfonamide and
3.95 parts by weight of pardon are added simultaneously
to a solution of 19.Z parts by weight of sheller'-
trifluoromethylphenoxy~-6-nitrophenylsulfenyl chloride in
200 parts by volume of absolute tetrahydrofuran, after
US which the reaction mixture is stirred for 2 hours at 40C,
cooled stirred into 500 parts by volume of water and then
acidified with 2 N hydrochloric acid. The precipitate
~LZ~:93~Si
9 Oat I 0050/36813
is filtered off under suction and recrystallized from 1,Z-
dichLoroethane to give 18.1 parts by weight ~82% yield)
of3-C2'-chloro-4'-trifluoromethylphenoxyl-6-n;tropheenyl-
N-methanesuLfonylsuLfenamide of melting point 215-~18C
(compound No. 1).
EXAMPLE 2
8 parts by weight of sheller trifler-
methylphenoxy~-6-nitrophenyl~N~methanesulfonylsulffenamide
and 3.25 parts by weight of 30X strength sodium methyl ate
are suspended in 100 parts by volume of absolute Matthew
not, and the suspension is heated to the reflex tempera-
lure. It is then evaporated down under reduced pressure
to give 8~37 parts by weight (100X yield) of the sodium
salt of 3-C2'-chloro-4'-trifluoromethylphenoxy~-6-nitro-
PhenyL-N-methanesulfonylsulfenamide of melting point 188-
191C (compound No. I
EXAMPLE 3
A solution of 3.8 parts by weight of sheller-
4'-trifluoromethylphenoxy~-6-nitrophenyl-N-me~haneesulfonyl-
Z0 sulfonamide and 3~85 parts by weight of 85X strength m-
chloroperbenzoic acid in 150 parts by volume of chloroform
is stirred at room temperature for 12 hours, after which
the reaction mixture is extracted with dilute sodium ho-
dioxide solution and water, dried with magnesium sulfate,
filtered and evaporated to dryness. 8 parts by weight
(87% yield) of 3-C2'-chloro-4'-trifluoromethylphenoxy~-6
nitrophenyl-N-methanesulfonylsulfinamide of melting point
178-18?C are obtained compound No. I
EXAMPLE 4
A solution of 8.8 parts by weight of 3-C2 '-sheller-
4'-trifluoromethylphenoxy~-6-nitrophenyl-N-methaneesulfonyl-
sulfonamide and 9.36 parts by weight of 85% strength m-
chloroperbenzoic acid in 150 parts by volume of chloroform
is stirred at 40C for 4 hours, after which the reaction
35 solution is extracted with dilute sodium hydroxide solution
and water, dried with magnesium sulfate filtered and
evaporated to dryness. 9 parts by weight (95% yield) of
~22~L5
- 10 - OOZE. OOZE
3-C2'-chloro-4'-erifluoromethylphenoxy]-6-nitropheenyl-N-
methanesulfonylsuLfonamide of refractive index n2D5 1.5469
are obtained compound No. 4).
EXAMPLE 5
A mixture of 10 parts by weight of sheller
4'~trifluoromethylphenoxy]-6-nitrophenyl-N-methaneesulfo
nylsulfenamide, I parts by weight of dim ethyl sulfate
and 3~2 parts by weight of potassium carbonate in 100
parts by volume of acetone is stirred for 2 hours at 64C,
after which the mixture is filtered and the reaction soul-
lion is evaporated to dryness. Recrystallization fromdiisopropyl ether gives 7 parts by weight t69X yield) of
3-C2'-chloro-4'-trifluoromethylphenoxy]-6-nitropheenyl-N-
methyl-N methanesulfonylsulfenamide of melting Point 128-
130C compound No. 5).
EXAMPLE 6
3.9 parts by weight of benzenesulfonamide are
added, a little at a time Jo a solution of 9.1 parts by
weigh of 3-C2'-chloro-4'-trifluoromethylphenoxyJ-6-nitro-
phenylsulfenyl chloride in So parts by volume of pardon.
The reaction mixture is stirred for 3 hours at 40C, after
which it is stirred into water and acidified with 3 N ho-
drochloric acid, and the precipitate which separates out
is filtered off under suction and recrystallized from 1,Z-
dichloroethane to give 7 parts by weight t77X yield) of
25 3-~2'-chloro~4'-trifluoromethylphenoxy]-6-nitropheenyl-N-
benzenesulfonylsulfenamide of molting point 170-178C
compound No. 6).
For instance the following compounds of the formula
F3C O N2
Of S - N - S
n n
on X em
may be obtained analogously.
-I ~22~5
I 0050/36813
No. n m X R Mop. C~; n25;
wavelength of a band in
the infrared spectrum
..
7 0 2 acutely . methyl
8 o 2 ammonium methyl
9 0 2 dimethylammonium methyl
10 0 2 ethyl methyl
11 1 2 methyl methyl
12 2 2 methyl methyl
13 2 2 sodium methyl 250 (decomposition)
14 1 2 sodium methyl 240
15 o 2 H ethyl
16 0 2 sodium ethyl
17 0 2 methyl ethyl
18 1 2 H ethyl
19 2 2 H ethyl
20 1 2 sodium ethyl
21 2 2 sodium ethyl
22 0 2 H n propel
23 0 2 sodium n-propyl
24 1 Z H n-propyl
25 2 2 H n-propyl
26 1 2 sodium n-propyl
27 2 2 sodium n-propyl
I 0 2 H i-propyl
29 1 2 H i-propyl
30 2 2 H i-propyl
31 0 2 sodium i-propyl
32 1 2 sodium i-propyl
33 2 2 sodium i-propyl
34 0 2 methyl i-propyl
35 0 2 H n-butyl
36 1 2 H n-butyl
37 2 2 H n-butyl
38 0 2 sodium n-butyl
39 1 2 sodium n-butyl
40 2 2 sodium n-butyl
41 0 2 H chloromethyl
42 1 2 H chl~romethyl
43 2 2 H chloromethyl
44 0 2 sodium chloromethyl
45 1 2 sodium chloromethyl
o
O
~2293~S
- 12 - OOZE. Allah
No. n m .X R Mop. C]; nD5;
wavelength ox a band in
the infrared spectrum
. . . . . _ .
46 2 2 sodium chloromethyl
47 0 2 H bouncily
48 0 2 sodium bouncily
49 0 2 H chlorobenzyl
50 0 2 sodium chlorobenzyl
51 0 2 sodium phenol 150 (decomposition)
52 1 2 H phenol 70-75
53 2 2 H phenol 90-92
54 0 2 methyl phenol 145-148
55 1 2 sodium phenol
56 2 2 sodium phenol
57 n 2 H 4~chlarophenyl 168 - 170
58 0 2 sodium 4-chloropheny} 145 (decomposition)
59 0 2 methyl 4-chlorophenyl 128-132
60 0 2 ethyl 4-chlorophenyl
61 1 2 H 4-chlorophenyl 75-B2
62 2 2 H 4-chlorophenyl 75-80C
63 0 2 H 2-chlorophenyl 110-113
64 0 2 sodium 2-chlorophenyl 100 (decomposition)
0 2 methyl 2-chlorophenyl 130-140
66 1 2 H 2-chlorophenyl
67 2 2 H 2-chlorophenyl 170-174
68 0 2 H 4-~luorophenyl 115-120
69 û 2 sodium 4 Pluorophenyl 70 (decomposition)
70 0 2 methyl 4-tluorophenyl 1.6141
71 1 2 H 4-~luorophenyl oil
72 2 2 H 4-~luorophenyl oil
73 0 2 H 4-bromophenyl 145-150
74 0 2 sodium 4-bromophenyl }60 (decomposition)
75 0 2 methyl 4-bromophenyl 64-66
76 1 2 H ,4-bromophenyl 240
77 2 2 H 4-bromophenyl ' oil
78 0 2 H 2,6-dlchlorophenyl 168 - 172
79 0 2 sodium 2,6-dlchlorophenyl
8û 0 2 methyl 2,6-dichlorophenyl
81 0 2 H 2,4-dichlorophenyl
82 0 2 sodium 2,4 dichlorophenyl
83 0 2 H sheller nitrophenyl
84 0 2 sodium 4-chloro-3-nitrophenyl
'
O
~2~93~S
- 13 w OOZE. 0050/36B13
No. n m X R Mop. okay; nD5;
wavelength ox a band in
the infrared spectrum
85 0 2 methyl 4-ohloro-3-nitrophenyl
86 0 2 H 2-nitrophenyl
87 0 2 sodium 2-nitrophenyl
88 0 2 H 4-nitrophenyl
89 o 2 sodium 4-nitrophenyl
90 o 2 methyl 4-nitrophenyl
91 a 0 H ~-nitrophenyl
92 1 0 H 4-nitrophenyl
93 2 0 H 4-nitrophenyl
94 1 1 H 4-nltrophenyl
95 2 1 H 4-nitrophenyl
96 2 2 H 4-nitrophenyl
97 0 2 H 4-cyanophenyl
98 0 2 sodium 4-cyanophenyl
99 0 2 H 4-methylphenyl 198 - 202
100 0 2 sodium 4-methylphenyl 85 (decomposition)
101 0 2 methyl 4-methylphenyl 106-110
102 0 2 H 3-nitrophenyl 148-152
103 0 2 sodium 3-nitrophenyl 105 (decomposition)
104 0 2 methyl 3-nitrophenyl 128-134
105 0 2 H 4-methoxyphenyl 165-172
106 0 2 sodium 4-methoxyphenyl 90
107 û 2 methyl 4-methoxyphenyl 98-106
108 1 2 H 4-methoxyphenyl 192-196 (decomposition)
109 2 2 H 4-m0khoxyphenyl
110 0 2 H 4-trlfluoromethoxyphenyl
111 0 2 H 4-trl~luoroethylphenyl
112 0 2 sodium 4-trifluoromethylphenyl
113 0 2 H 3-trifluoromethylphenyl
114 0 2 sodium 3-trifluoromethylphenyl
115 o 2 H 2,2,2-tri~luoroethyl
116 0 2 sodium 2,2,2-tri~luoroethyl
117 2 2 H 2,2,2-trifluoroethyl
118 0 2 H methyl amino
119 0 2 H ethyl amino
120 0 2 H propylamino
121 0 2 H isopropyl amino
122 2 2 H 4-methylphenyl 56-60
123 1 2 H 4-Methylphenyl 165-170 decomposition
124 2 2 H 3-Nitrophenyl oil
125 1 2 H 3-Nitrophenyl 65-70
126 2 2 sodium 2-chlorophenyl 93-98
O
S
"` ~Z29~4S
14 - OOZE. 0050/3681
For example the ~ollowlng diphenyl ethers ox the formula may also
be obtained: z1
En. no. Z3~ n m X R Mop. I no
- . . . . .
122 2,4-dichlorophenoxy 0 2 H methyl
123 2,4-dlchlorophenoxy 0 2 sodium methyl
124 2,4-dibromophenoxy 0 2 H methyl
125 2,4-dibromophenoxy 0 2 sodium methyl
126 3-chloro-4-tri~luoro- 0 2 H methyl
methylphenoxy
127 3-chloro-4-trifluoro- 0 2 sodium methyl
methylphenoxy
128 2,6-dichloro-4-tri- 0 2 H methyl
~luoromethylphenoxy
129 2,6-dichloro-4-tri- 0 2 sodium methyl
l'luoromethylphenoxy
130 2,6-dichloro-4-tri- 0 2 methyl methyl
~luoromethylphenoxy
1}1 2,6-dichloro-4~tri- 0 2 H isopropyl
~luoromethylphenoxy
132 2,6-dichloro-4-tri- 0 2 H phenol
~luoromethylphenoxy
133 2,6-dichloro-4-tri- 0 2 H 4-chlorophenyl
~luoromethylphenoxy
134 2,6-dichloro-4-tri- 0 2 H 4-tluorophenyl
~luoromethylphenoxy
an
:
~l22~34S
- 15 - OOZE. 0050/36813
The diphenyl ethers of the formula I, and salts
thereof, may be applied for instance in the form of direct-
lye spray able solutions, powders, suspensions (including
high-percentage aqueous, oily or other suspensions),
05 dispersions emulsions, oil dispersions, pastes, dusts,
broadcasting agents, or granules by spraying, atomizing,
dusting, broadcasting or watering. The forms of applique-
anion depend entirely on the purpose for which the agents
are being used, but they must ensure as fine a duster-
lo button of the active ingredients according to the invent
lion as possible.
For the preparation of solutions, emulsions, pastes
and oil dispersions to be sprayed direct, mineral oil free-
lions of medium to high boiling point, such as kerosene or
diesel oil, further coal-tar oils, and oils of vegetable
or animal origin, aliphatic, cyclic and aromatic hydra-
carbons such as Bunsen, Tulane, xylener paraffin, twitter-
hydronaphthalene, alkylated naphthalenes and their
derivatives such as methanol, ethanol, propanol, buttonhole,
chloroform, carbon tetrachloride, cyclohexanol, cycle-
hexanone, chlorobenzene, isophorone, etc., and strongly
polar solvents such as dimethylformamide, dim ethyl sulfa
oxide, and N-methylpyrrolidone, and water are suitable.
Aqueous formulations may be prepared from emulsion
concentrates, pastes, oil dispersions or wettable powders
by adding water. To prepare emulsions, pastes and oil disk
pensions the ingredients as such or dissolved in an oil or
solvent may be homogenized in water by moans of wetting or
dispersing agents, adherents or emulsifiers. Concentrates
which are suitable for dilution with water may be prepared
from active ingredienkr wetting agent, adherent, emulsify-
in or dispersing agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline
earth metal and ammonium salts of ligninsulfonic acid,
naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl
sulfonates, alkyd sulfates, and alkyd sulfonates, alkali
metal and alkaline earth metal salts of dibutylnaphthalene-
N
No
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sulfonic acid laurel ether sulfate, fatty alcohol sulk
fates, alkali metal and alkaline earth metal salts of
fatty acids, salts of sulfated hexadecanols, Hyatt
decanols, and octadecanols, salts of sulfated fatty Alcoa
05 hot glycol ethers, condensation products of sul~onatednaphthalene and naphthalene derivatives with formaldehyde,
condensation products of naphthalene or naphthalenesul-
ionic acids with phenol and formaldehyde, polyoxyethylene
octylphenol ethers, ethoxylated isooctylphenol, elk-
lo oxylated octylphenol and ethoxylated nonylphenol f alkyd-
phenol polyglycol ethers, tributylphenyl polyglycol
ethers, alkylaryl polyether alcohols, isotridecyl alcohol,
fatty alcohol ethylene oxide condensates, ethoxylated
castor oil, polyoxyethylene alkyd ethers, ethoxylated
polyoxypropylene, laurel alcohol polyglycol ether acutely,
sorbitol esters, lignin, sulfite waste liquors and methyl
cellulose.
Powders, dusts and broadcasting agents may be
prepared by mixing or grinding the active ingredients with
a solid carrier.
Granules, e.g., coated, impregnated or homogeneous
granules, may be prepared by bonding the active inure-
dints to solid carriers. Examples of solid carriers are
mineral earths such as silicic acid, silica gels,
US silicates, talc, kaolin, attapulgus clay, limestone, lime,
chalk, bole, loss, clay, dolomite, diatomaceous earth,
calcium sulfate, magnesium sulfate, magnesium oxide
ground plastics/ fertilizers such as ammonium sulfate,
ammonium phosphate, ammonium nitrate, and ureas, and
vegetable products such as grain flours, bark meal, wood
meal, and nutshell meal, cellulosic powders, etc.
The formulations contain from 0.1 to 95, and prefer-
ably 0.5 to 90, I; by weight of active ingredient.
Examples of formulations are given below.
o
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I. Jo parts by weight of compound no. 3 is mixed
with lo parts by weight of N-methyl-alpha-pyrrolidone. A
mixture is obtained which is suitable fox application in
the form of very fine drops.
05 II. lo parts by weight of compound no. 4 is dozily-
vied in a mixture consisting of 90 parts by weight of
zillion 6 parts by weight of the adduce of 8 to 10 moles
of ethylene oxide and l mole of oleic acid-N-monoethanol-
aside, 2 parts by weight of the calcium salt of dodecyl-
lo benzenesulfonic acid, and 2 parts by weight of the adduce
of 40 moles of ethylene oxide and l mole of castor oil.
III. 20 parts by weight of compound no. 5 is dozily-
vied in a mixture consisting of 60 parts by weight of
cyclohexanone, 30 parts by weight of isobutanol, 5 parts
by weight of the adduce of 7 moles of ethylene oxide and
1 mole of isooctylphenol, and 5 parts by weight of the
adduce of 40 moles of ethylene oxide and l mole of castor
oil.
IV. 20 parts by weight of compound no. 106 is disk
I solved in a mixture consisting of 25 parts by weight ofcyclohexanol, 65 parts by weight of a mineral oil fraction
having a boiling point between 210 and 280C, and
10 parts by weight of the adduce of I moles of ethylene
oxide and 1 mole of castor oil. By pouring the solution
into 100,000 parts by weight of water and uniformly disk
tributing it therein, an aqueous dispersion is obtained
containing 0.02% by weight of the active ingredient.
V. 80 parts by weight of compound no. 1 is well
mixed with 3 parts by weight of the sodium salt of dyes-
butylnaphthalene-alpha-sulfonic acid, lo parts by weight
of the sodium salt of a iignin-sulfonic acid obtained from
a sulfite waste liquor, and 7 parts by weight of powdered
silica gel, and triturated in a hammer mill.
VI. S parts by weight of compound no. 2 is
intimately mixed with 95 parts by weight of particulate
kaolin. A dust is obtained containing I by weight of the
active ingredient.
I,
o
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- I - OOZE. ooze
VII. 30 parts by weight of compound no. 122 is
intimately mixed with a mixture consisting of 92 parts by
weight of powdered silica gel and 8 parts by weight of
paraffin oil which has been sprayed onto the surface of
05 this silica gel. A formulation of the active ingredient is
obtained having good adherence.
VOW 20 parts of compound no. 13 is intimately
mixed with 2 parts of the calcium salt of dodecylbenzene-
sulfonic acid, 8 parts of a fatty alcohol polyglycol
lo ether, 2 parts of the sodium salt of a phenolsulfonic
acid-urea-formaldehyde condensate and 68 parts of a purify
phonic mineral oil. A stable oily dispersion is obtained.
The active ingredients, or agents containing them,
may be applied pro- or post emergence. If certain crop
plants tolerate the active ingredients less well when they
are applied post emergence, application techniques may be
used in which the herbicidal agents are sprayed from
suitable equipment in such a manner that the leaves of
sensitive crop plants are if possible not touched, and the
agents reach the soil or the unwanted plants growing
beneath the crop plants (post-directed, lay-by treatment).
The amount of active ingredient applied depends on
the time of the year, the plants to be combated and their
growth stage, and varies from 0.025 to 3 kg/ha, but is
preferably from 0.05 to l kg/ha.
The herbicidal action of the diphenyl ethers of the
formula I is demonstrated in greenhouse experiments.
The vessels employed were plastic flowerpots having a
volume of 300 cm3, and which were filled with a sandy loam
containing about 1.5% humus. The seeds of the test plants
were sown shallow, and separately, according to species.
or the reemergence treatment the active ingredients
were applied to the surface of the soil immediately after
the seeds had been sown. The compounds were emulsified or
suspended in water as vehicle, and sprayed through finely
distributing nozzles. The application rate was 3.0 kg of
active ingredient per Hector. After the agents had been
o
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applied, the vessels were lightly sprinkler-irrigated to
induce germination and growth. Transparent plastic covers
were then placed on the vessels until the plants had taken
root. The cover ensured uniform germination of the plants,
05 insofar as this was not impaired by the active inure
dints.
For the post emergence treatment, the plants were
first grown in the vessels to a height of from 3 to 15 cm,
depending on growth form, before being treated. The rice
lo plants were grown in a peat-enriched substrate. For this
treatment, either plants which had been sown directly in
the pots and grown there were selected, or plants which
had been grown from seedlings and were transplanted to the
pots a few days before treatment. the application rates
for post emergence treatment were 0.06, 0.25 and 3.0 kg of
active ingredient per Hector.
The pots were set up in the greenhouse - species from
warmer areas at from 20 to 35C, and species from
moderate climates at lo to 25~C. The experiments were run
for 2 to 4 weeks. During this period, the plants were
tended and their reactions to the various treatments
assessed. The scale used for assessment was O to 100, 0
denoting no damage or normal emergence, and loo denoting
non emergence or complete destruction of at least the
visible plant parts.
The plants used in the experiments were ~maranthus
retroflexus, Arachis hypogaea, Arena saliva, Sinatra
Cygnus, Chenopodium album, Echinochloa crus-galli, Gallium
apron, Ipomoea sup., Ours saliva, Synapse alga, Selenium
nigrum, and Triticum aestivum.
On reemergence application, for example compounds
nos. 4, 106 and 122 proved to be herbicidally effective,
and selective in oats selected as an exemplary cereal.
On post emergence application of for instance 3.0 kg
of active ingredient per Hector r compounds nos. 1, 2 r 3 r
4 and 5 had a strong herbicidal action on broad leaved
I,
I
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unwanted plants; compounds nos. 3, 4 and Al and compound
no. 13 were also effective on grasses such as barnyard-
grass Compounds nos. 1 and 3 are suitable for the select
live control of unwanted plants at low application rates
OX such as 0~06 or 0.25 kg/ha.
In view of the numerous application methods possible,
the compounds according to the invention may be used in a
further large number of crops for removing unwanted wild
grasses or grassy crop plants growing where they are not
lo desired
The following crops may be mentioned by way of
example:
Botanical name Common name
_
15 Gallium cope onions
Bananas comosus pineapples
Arachis hypogaea peanuts (groundnuts)
Asparagus of~icinalis asparagus
Arena saliva oats
I Beta vulgarism sup. altissima sugar beets
Beta vulgarism sup. nape odder beets
Camellia sinensis tea plants
Carthamus tinctures safflower
Carve illinoinensis pecan trees
25 Citrus lion lemons
Citrus maxima grapefruits
Citrus reticulate mandarins
Citrus sinensis orange trees
Coffee Arabic (Coffee conifer,
30 Coffee Liberia coffee plants
Cucumis memo melons
Cucumis sativus cucumbers
Sundown dactyl on Bermuda grass in turf
and lawns
35 Caucus karat carrots
flats guineensis oil palms
E'xagaria vesca strawberries
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Botanical name Common name
Gleason Max soybeans
Gossypium hirsutum
05 (Gossypium arboretum cotton
Gossyplum herbaceum
Gossypium vitifolium)
Helianthus annuls sunflowers
Helianthus tuberosus Jerusalem artichoke
10 Hove brasiliensis rubber plants
Hordeum vulgar barley
Cumulus lapels hops
Ipomoea batatas sweet potatoes
Juglans Regina walnut trees
15 Lens culinaris lentils
Linus usitatissimum flax
Lycopersicon lycopersicum tomatoes
Mauls sup. apple trees
Monet esculenta cohesive
20 Medic ago saliva alfalfa (Lucerne)
Month paperweight peppermint
Muse sup. banana plants
Nicothiana tabacum tobacco
(N. rustic)
25 Olga europaea olive trees
Ours saliva rice
Panicum miliaceum millet
Fossils lunatus lima beans
Fossils mango mungbeans
30 Fossils vulgarism snap beans, green beans,
dry beans
Pennisetum glaucoma pearl millet
Petroselinum crispum parsley
Pica abides Norway spruce
35 Boyce alga fir trees
Pious sup. pine trees
Possum sativum English peas
o
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Botanical name Common name
.
Prunes avium cherry trees
Prunes domestic plum trees
05 Prunes dualizes - almond trees
Prunes Persia peach trees
Pyres communist pear trees
Robes Sylvester redcurrants
Robes uva-crispa gooseberries
10 Rosins communist castor-oil plants
Saccharum officinarum sugar cane
Scale cereal rye
Sesamum indicum sesame
Selenium tubexosum Irish potatoes
15 Sorghum buckler (s. vulgar) sorghum
Sorghum dochna forgo
Spanish oilers spinach
Theobroma cacao cacao plants
Trifolium pretense red clover
I Triticum aestivum wheat
Vaccinium corymbosum blueberries
Vaccinium vitis-idaea cranberries
Viola Ahab tick beans
Vegan sinensis TV unguiculata) cow peas
25 Votes vinier grapes
Zeta may Indian corn, sweet
corn, maize
To increase the spectrum of action and to achieve
synergistic effects, the diphenyl ethers of the formula I
may be mixed and applied together with numerous represent-
natives of other herbicidal or growth regulating active
ingredient groups. Examples of suitable mixture components
are doziness OH 3,1-benzoxazine derivatives, benzothiadia-
intones 2,6-dinitroanilines, N-phenylcarbamates, they'll-
carbamates, halocarboxylic acids, treasons, amides,ureas, other diphenyl ethers, triazinones, uracils, buoyancy-
Furman derivatives, cyclohexane~l,3-dione derivatives, etc.
I
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- 23 I o. z . Q050/36813
It may also be useful to apply the diphenyl ethers of
the formula I, either alone or in combination with other
herbicides, in admixture with other crop protection
agents, e.g., agents for combating pests or footpath-
05 genie fungi or bacteria. The compounds may also be mixed with solutions of mineral salts used to remedy nutritional
or trace element deficiencies. Non-phytotoxic oils and oil
concentrates may also be added.
I.
I;
