Note: Descriptions are shown in the official language in which they were submitted.
-
lO9~Z40
-- 1 --
Case 5-11548/=
NOVEL PHENOXY-PHENOXY-ALKANECARBOXYLIC ACID DERIVATIVES
HAVING A HERBICIDAL ACTION, THEIR PRODUCTION~
COMPOSITIONS CONTAINI~C IH~M~ AND THEIR USE_
The present invention relates to novel phenoxy-phenoxy-
alkanecarboxylic acid derivatives which have a herbicidal
action and an action regulating plant growth, to processes
for producing them, to compositions containing these
derivatives as active substances, and also to the use of
these phenoxy-phenoxy-alkanecarboxylic acid derivatives,
or of compositions containing them~ for regulating plant
growth.
The phenoxy-phenoxy-alkanecarboxylic acid derivatives
are novel compounds and correspond to the formula I
; '
C~ o-~ -B .(I)
P
in which
Rl is hydrogen, Cl-C4 alkyl or C2-C3 alkoxyalkyl,
A is the cyano group or a radical -COR, wherein
R is a radical -OR3, SR4-NR5R6 or -N-R2, wherein
~3 is hydrogen or
~k
.: . . ,. .. : : ~ . :
~ .
..
.
.
,.. ~ .
~C~91 2 40
- 2 -
the cation of a base 1 M m ~3 wherein
M is an alkali metal cation or alkaline-earth metal
cation, or an Fe, Cu, Zn, Mn or Ni cation, or an
ammonium group
~- N -Rd ~ and
/\
Rb Rc
m as integer 1, 2 or 3 takes into account the valency
of the cation, whilst Ra~ Rb, Rc and Rd independently
of one another are hydrogen, benzyl or a Cl-C4 alkyl
group unsubstituted or substituted by -OH, -NH2 or
Cl-C4 alkoxy, and in addition
R3 is a Cl-C12 alkyl group which is unsubstituted or :
substituted by halogen, nitro, cyano, Cl-C8 alkoxy, .
Cl-C8 alkylthio, C2-C8 alkanoyl, bis (Cl-C4 alkyl) ~.
amino, tris (Cl-C4 alkyl) ammonium, C3-C8 cycloalkyl,
C3-C8 cycloalkenyl, or by a phenyl, phenoxy or 5- or
6-membered heterocyclic radical having 1 to 3 hetero :~
atoms, each of which is unsubstituted or for its
part mono- or polysubstituted by halogen, Cl-C4 alkyl
or Cl-C4 alkoxy, or R3 is an unsubstituted or
substituted C3-C18 alkenyl group, :
a C3-C8 alkynyl group, a C3-C12 cycloalkyl group
unsubstituted or substituted by halogen or Cl-C4 alkyl,
or R3 is a phenyl group which is unsubstituted or
mono- or polysubstituted by halogen, Cl-C4 alkyl,
Cl-C4 alkoxy, Cl-C4 alkylthio, N02 or CF3, or R3
is a S- or 6-membered heterocyclic ring having 1 to 3
hetero at s, and
R4 is the same as R3,
R5 and R6 independently of one another are each hydrogen,
or an alkyl group which can be unsubstituted or
.. . . ., . - : .
.-: ~ -- , . - ~ .. .
. - ,, . -
~: ' . ; '' -
.
i
109~240
substituted by hydroxyl or alkoxy, or they are each alkoxy,
alkenyl, alkynyl, phenyl or benzyl, and the phenyl rings can
be mono- or polysubstituted by halogen, alkyl, alkoxy, alkylthio,
cyano or nitro, or
R5 and R6 together with the nitrogen atom to which they are bound can
form a 5- or 6-membered heterocycle, which can also contain a
second hetero atom, nitrogen oxygen or sulfur,
R2 is a preferably branched-chain alkylene group bound by a double
bond to the nitrogen atom,
B is a hydrogen or halogen atom, or a cyano or nitro group,
C is halogen, cyano, nitro or trifluoromethyl,
D is hydrogen, halogen, or a cyano, nitro or trifluoromethyl
group,
E is a halogen atom or a Cl-C4 alkyl group, and
P is the number 1 or 2.
In this formula, the alkyl groups are both branched-chain and
straight-chain and contain the given number of carbon atoms. The radicals
R5 and R6 are preferably hydrogen and Cl-C4 alkyl groups. Some among them
can however also be substituted alkyl groups, or one of them can be an
unsubstituted or substituted phenyl group or benzyl, or together with the
nitrogen atom to which they are bound they can also form a heterocycle pre-
ferably containing 5 or 6 ring members.
This invention discloses a novel group of phenoxy-phenoxy-
and phenoxy-phenylthio-alkanecarboxylic acid derivatives, respectively,
which in small applied amounts already exhibit a strong herbicidal action
~ 3 ~
.
.
. . ' , . -:
lO91Z~O
and/or are able to regulate plant growth in some other manner useful in
agriculture.
The novel active substances cf the formula I can be used as
herbicides in the pre-emergence process but mainly
- 3a -
,,,~ , ~
, ' " ' '` '
.~ ' ' ' ~ .
-- 4 --
in the post-emergence process. They have a good action
against broad-leaved plants (dicotyledons).
The derivatives according to the invention also have
a favourable growth-regulating action (growth inhibition).
They inhibit the growth in particular of dicotyledonous
plants, and can be used in a profitable manner for example
as follows:
- reduction of vegetative growth in the case of soya-bean
plants and similar leguminosae, an effect which leads to
an increase in the yield of these crops;
- reduction of the undesirable growth of side shoots on
tobacco plants, the leading shoots of which have been
cut, an effect which promotes the formation of larger
and better leaves; and
- reduction of the growth of grass and of dicotyledonous
plants, such as fruit trees, ornamental trees, shrubs
and hedges, for the purpose of economising in the
amount of cutting work.
The compounds of the present invention are negligibly
toxic to warm-blooded animals, and application of the
compounds presents no problems. The suggested amounts to
apply are between 0.1 and 5 kg per hectare.
Phenoxy-phenoxy-alkanecarboxylic acid derivatives
having a herbicidal action and similar chemical structure
have already become known from a series of recent
publications. Reference is made in this respect to the
German Offenlegungsschriften Nos. 2,311,638, 2,609,461,
2,623,558, 2,639,796, 2,643,438, 2,652,384 and 2,730,591,
and also to C.A. 86 (1977) 134 874x. The present compounds
are different from those mentioned in these publications,
and exhibit, in spite of their pronounced action on
dicotyledonous weeds, excellent selectivity with respect to
.
.
1091240
-- 5 --
broad-leaved cultivated plants, such as sugar beet and
soya-bean plants.
The novel compounds of the formula I are produced
by methods known per se for the synthesis of phenoxy-
phenoxy-alkanecarboxylic acids and derivatives thereof.
One of these processes comprises reacting according
to the invention an appropriately substituted halogeno-
phenol of the formula II
- D
C ~ Hal (II)
,
in which "Hal" is a halogen atom, preferably chlorine or .
bromine, and C and ~ have the meanings defined
under the formula I, with an appropriately substituted
hydroxy-phenoxy-alkanecarboxylic acid derivative of the
.. . - ~
formula III 1
,, 0 -.C - A
HO ~ B 2 (III),
r ~
Ep
in which B, E, p, Rl, R2 and A are as defined ~1nder the
formula I, in the presence of a base.
A second process comprises using according to the
invention an appropriately substituted m-hydroxy-
diphenyl ether of the formula IV
D OH
B (IV),
Ep
in which B, C, D, E and p are as defined under the formula
I, as the starting material, and reacting this with an
- . ~ . . . ~.
1o~g1 2 4~
a-halogenoalkanoic acid derivative of the formula V
Hal - C - A (V)
R2
in which "Hal" is a halogen atom, preferably chlorine or
bromine, and Rl, R2 and A are as defined under the formula
I, in the presence of a base.
If in these processes there is used as starting material
(A=COOH) Gf the formulae III and V, respec~ively, a
carboxylic acid, this group can subsequently be converted,
for example by esterification, and so forth, into another
derivative of the formula I as defined. Conversely, it is
possible with use of an ester of the formulae III and V,
respectively, to finally convert the ester group by saponi-
fication into the free carboxylic acid or into a salt
thereof.
The reactions mentioned can be performed in the presence
or absence of solvents or diluents inert to the reactants.
Polar organic solvents such as methyl ethyl ketone, dimethyl-
formamide, dimethylsulfoxide, and so forth, are preferred.
The reaction temperatures are between O and 200C, and
the duration of the reaction, depending on starting material,
the chosen reaction temperature and the solvent, is between
1 hour and several days. The reaction is performed as a
rule at normal pressure. The customary bases (condensation
agents), for example KOH, NaOCH3, NaHC03, H2C03, potassium-
tert-butylate, and so forth, are suitable for the reaction,
but also organic bases are suitable, such as triethylamine,
and the like.
The starting materials of the formulae II to V are in
some cases known. Starting materials of these formulae
which have still not been described can be readily produced
...
'~
~09lZ40
-- 7 --
by customary processes and techniques. Phenoxyphenols
of the formula IV can be produced for example by the
methods described in J.A.C.S. 61, 2702 (1939), or in
Chem. Abstracts 54, 922h (1960).
The following Examples illustrate the processes
according to the invention. Further active substances
produced in a corresponding manner are listed in the
Table which follows. Temperature values are given in
degrees Centigrade, and percentages in per cent by weight.
, - - . ~ .,
:
,
. ~ - . ' ' ~, , ,
1~)91Z40
-- 8 --
Example 1
a- [3-(2'-Cnloro-4'-trifluoromethylphenoxy)-4-chloro-
phenoxy]-propionic acid methyl ester
, O-C~I-COOCH3 '' ''
OE 3
Cl Cl
a) 11.5 g o~ 2-chloro-4-trifluoromethyl-2'-chloro-S'-
hydroxydiphenyl ether is dissolved in 50 ml of 2-butanone,
and, after the addition of 30 ml of 2-bromopropionic acid
methyl ester, 12 g of potassium carbonate and a spatula-tip
of potassium iodide, the whole is stirred overnight at
80C. The reaction product is diluted with 100 ml of
acetone and filtered off. The solvent is distilled off,
and the residue is distilled under high vacuum to yield
12.8 g of the above-mentioned product, which has a
boiling point of 147C at 0.04 Torr.
The starting product, 2-chloro-4-trifluoromethyl-2'-
chloro-5'-hydroxydiphenyl ether, is produced as follows:
b) 20 g (0.33 mol) of pulverised potassium hydroxide is
placed into 200 ml of dimethyl sulfoxide, and 48 g (0.3 mol)
of 2-chloro-3-methoxyphenol is added in portions. After
everything has gone into solution, 70 g (0.33 mol) of
3,4-dichlorobenzotrifluoride is added dropwise fairly
quickly, and stirring is maintained for about 12 hours
at 150C (bath temperature). The reaction product is
poured into ice/water, and extracted with toluene/ethyl
acetate (1:1). The solvent is distilled off to leave 91 g
of 2-chloro-4-trifluoromethyl-2'-chloro-5'-methoxydiphenyl
ether in the form of oil, which is distilled under high
vacuum; boiling point 119-123C at 0.25 Torr; yield 59.5 g
.. , .,, , ... .. . , , , ~, . _, _ . _ .. . _ . , ... . .... , . .. ., . .. , .. . , . .. .. , .. , . , . ,, _ .. _ .
.. .. . .. .. .
.. , :
.
, ~,, "~
.. - - .
~' ' . .
IQ91~40
(59% of theory).
c) 32 g of 2-chloro-4-trifluoromethyl-2'-chloro-5'-
methoxydipheny~ ether is diss~lved in 700 ml of glacial
acetic acid, and 170 ml of 48% hydrobromic acid is added.
The mixture is refluxed for 60 hours with stirring at a
bath temperature of 120C, and the glacial acetic acid is
subsequently distilled off. The oil remaining behind is
taken up in toluene, and washed with a solution of
sodium bicarbonate/sodium thiosulfate. The solvent is
distilled off to leave 28 g of 2-chloro-4-trifluoromethyl-
2'-chloro-5~-hydroxydiphenyl ether in the form of viscous
oil, which is distilled under high vacuum; yield 19.5 g;
boiling point 132C at 0.25 Torr.
Example 2
a-l3-(4'-Trifluoromethylphenoxy)-4,6-dichlorophenoxy]-
propionic acid methyl ester
CH3
0-CH-COOC~3
CF3 ~ 0 ~ 1
Cl
34 g (0.1 mol) of 3-(4'-trifluoromethylphenoxy)-a-
(phenoxy)-propionic acid methyl ester (produced analogously
to Example 1) is dissolved in 100 ml of glacial acetic
acid, and at 40C chlorine is fed in in excess. The reac-
tion is followed by means of gas-chromatography. After
the reaction has ended, the reaction mixture is stirred
for a further half hour, and excess chlorine is removed
by the introduction of nitrogen. The solvent is distilled
off, and the oil thus obtained is distilled under high
vacuum to yield 34.5 g of the above product in the form
.
. ~ .
....
91Z40
- 10 -
of oil, which is distilled under high vacuum; boiling
point 163-165C at 0.07 Torr.
Example 3
a- [ 3-(4'-Trifluoromethylphenoxy)-S-methylphenoxy]-
propionic acid methyl ester
- 0-CH-C00CH3
CF3 ~ o ~ CH3
CH
a) 13.0 g (0.0485 mol) of 5-(4-trifluoromethylphenoxy)-
m-cresol, 7.6 g (0.055 mol) of potassium carbonate and
50 ml of methyl ethyl ketone are refluxed for 2 hours
with stirring. There is then added at 50C 8.4 g
(0.05 mol) of 2-bromopropionic acid methyl ester, and
the mixture is stirred at 50C for 15 hours. After cooling,
it is filtered, and the filtrate is concentrated in vacuo.
The residue is filtered with methylene chloride through
a small column to obtain 16.1 g (93.6% of theory) of the
above product in the form of a clear light-yellow oil
having a refractive index of nD = 1.5104. The starting
material, 5-(4-trifluoromethylphenoxy-m-cresol, is
produced as follows:
b) 35.5 g ~0.25 mol) of orcinol.H20 (3,5-dihydroxytoluene)
is dissolved in 200 ml of dimethyl sulfoxide, and 31.3 g
(0.5 mol) of potassium hydroxide (90%), which is finely
pulverised, is added. As soon as everything has gone into
solution, 45.1 g (0.25 mol) of 4- chlorobenzenetriflu-
oride is added, and the reaction mixture is stirred at
150C for 20 hours. It is then cooled, 200 ml of 10% HCl
is added, and extraction is performed with methylene
chloride. The organic phase is dried, and concentrated
~7
, . . .,, . .. .. , . . ~ . ~ , .
- . , - . . -
- - , , - - .. . ..
........ .. . .
- , , .
,., . . , , . , :
,
1091240
- 11 -
by evaporation. The residue is separated through a
small silica gel column with methylene chloride. There
is obtained as the main fraction 29.8 g (44.4/O of theory)
of 5-(4-trifluoromethylphenoxy)-m-cresol in the form of
clear light-yellow oil having a refractive index of
nD - 1.5322.
Example 4
a-[3-(4'-Trifluoromethylphenoxy)-5-methyl-6-chlorophenoxyl-
propionic acid methyl ester
CH3
O -CH -COOCH
CF3 ~ ~ Cl 3
CH3
a) 1.7 g (0.0056 mol) of 5-(4'-trifluoromethylphenoxy)-
2-chloro-m-cresol is stirred with 0.23 g (0.0062 mol) of
potassium carbonate in 20 ml of ethyl methyl ketone for 2
hours under reflux. There is then added at 50C 1.0 g
~0.0062 mol) of 2-bromopropionic acid methyl ester, and
the mixture is stirred at 60C for 15 hours. It is sub-
sequently filtered and the filtrate is concentrated by
evaporation. The residue is filtered with methylene
chloride through a small column, and the main fraction is
concentrated by evaporation to yield 1.6 g (76.2% of
theory) of thP above product in the form of yellow oil
having the refractive index nD - 1.5119.
The 5-(4'-trifluoromethylphenoxy)-2-chloro-m-cresol
used as starting material is produced as follows:
b) 13.4 g (0.05 mol) of 5-(4-trifluoromethylphenoxy)-m-
cresol (for production of this see Example 3b) is dissolved
in 50 ml of glacial acetic acid. To this solution is added
droFwise at 15C 3.8 g of chlorine (0.055 mol) in 25 ml of
J
..... ~ .. . ... .. .... ... . . .. . .. . .. .. ... ...
- : '
- ~ . -, :-
. . ~ .,
109~Z40
- 12 -
glacial acetic acid, in the course of which the tempera-
ture is held at 15C. The internal temperature is
subsequently allowed to rise to room temperature. After
15 minutes, the reaction mixture is poured into water; it
is extracted with methylene chloride, the organic phase is
dried with sodium sulfate and is concentrated in vacuo.
The residue is chromatographed with hexane through a small
silica gel column. The main fraction yields a clear
light-coloured oil, which crystallises on being triturated
with petroleum ether. There is thus obtained 1.7 g
(11.3 % of theory) of 5-(4-trifluoromethylphenoxy)-2-chloro-
m-cresol as a white product having a melting point of
106-110C.
Example 5 l~
a-[3-(4'-Trifluoromethylphenoxy)-5-methyl]-propionitrile ;~
CF3 ~ ~ CH3
CH3
13.0 g (0.0485 mol) of 5-(4'-trifluoromethylphenoxy)-
m-cresol (for production of this see Example 3b), 7.6 g
(0.055 mol) of potassium carbonate and 50 ml of methyl
ethyl ketone are refluxed for 2 hours. There is then
added at 40C 6.7 g (0.05 mol) of 2-bromopropionitrile,
and the mixture is stirred at 60C for 15 hours. It is
subsequently cooled and filtered, and the filtrate is
concentrated in vacuo. The residue is filtered with
methylene chloride through a small silica gel column to
thus yield 14.4 g (90.0% of theory) of the above product
in the form of a clPar brown oil having the refractive
index nD s 1.5174.
~"
- . .
~ ;' ' ' . ' ' ~ "
~: , .' .
~09lZ40
- 13 -
Example 6
~-[3-(4'-Trifluoromethylphenyl)-5-methylphenoxy]-propionic
acid
O - CH-COOH
CF3 ~ ~ CH3
CH3
39.0 g (O.ll mol) of a- 13-(4'-trifluoromethylphenoxy)-
3-methylphenoxy]-propionic acid methyl ester (for its
production see Example 3a) is dissolved in lOO ml o~
methanol, and a solution of lO.l g of sodium hydroxide
(100%) in lO ml of water is added, in the course of which
the temperature rises. The mixture is stirred at 50C - -
for one further hour; lOO ml of ice/water is added to the
reaction mixture, and the whole is acidified with concen- ,
trated hydrochloric acid. The produc~ which has precipitated
is taken up in 200 ml of methylene chloride and dried. It
is concentrated by evaporation to yield 23.8 g (63.4% of
theory) of the above product in the form of a light-yellow
crystalline powder having a melting point of 88-90C.
ExamPle 7
-[3-(4'-Trifluoromethylphenoxy)-5-methylphenoxy]-propionic
acid allylamide
OCH-CONEICH2-CH~CH2
CH3
a) 7.0 g (O.Ol9 mol) of a-13-(4'-trifluoromethylphenoxy)-5-
methylphenoxy-propionic acid chloride is dissolved in 20 ml
_ _ _ ,, .____. _ _ . ,. . . , , . . . ~ . ., .. _ _.. , .. . ~.. . ... .... .
. . . :
. .
. ,
1091240
- 14 -
of methylene chloride, and at 10C is added 2.8 g (0.042
mol) of allylamine. After 1 hour, 100 ml of water is
added; the organic phase is then separated, and dried
with sodium sulfate. ~t is concentrated by evaporation
to obtain a clear light-yellow oil, which crystallises
on being triturated with petroleum ether. In this manner
is obtained the above product in the form of white
crystals in a yield of 5.0 g (69.4% of theory3; melting
point 94-96C. The acid chloride used as starting product
is produced as follows:
b) 20 ml of thionyl chloride is added at room temperature
to 13.8 g (0.04 mol) of a-(3-(4'-trifluoromethylphenoxy)-
5-methylphenoxy)-propionic acid (for production of this
see Example 6), and the temperature is then raised to 50C.
The reaction mixture is left to stand at this temperature
for 2 hours, and is subsequently concentrated by evapor-
ation; to the residue is added 50 ml of toluene, and the
whole is evaporated to dryness in a good vacuum to thus
yield, in the form of clear dark-brown oil, 14.3 g (100%
of theory) of a-(3-(4'-trifluoromethylphenoxy)-5-methyl-
phenoxy)-propionic acid chloride.
ExamPle 8
a-l3-(2'-Chloro-4'-trifluoromethylphenoxy)-6-chlorophenoxy]-
propionic acid methyl ester
Cl O~H-COOCH3
CF3-~ O--~ ~--Cl
35.9 g of 3-(2'-chloro-4'-trifluoromethylphenoxy)~a-
phenoxy-propionic acid methyl ester is dissolved in 100 ml
of glacial acetic acid. Into this solution is then passed,
. .
- ~ :
.. ,
. . . ~ ,: .
.
1(~91240
- 15 -
with thorough stirring, the theoretically required
amount of chlorine, with the temperature being held at
40C. The reaction mixture is stirred for half an hour
and the solvent is distilled off. Ligroin is added to
the oily residue, and the crystals which have precipitated
are filtered off. The title product thus obtained has
a melting point of 79-80C~
Example 9
a-[3-(2'-Chloro-4'-trifluoromethyl)-6-chloro-4-iodophenoxy)-
propionic acid methyl ester CH3
Cl O~H-COOCH
cF3~ o~
Cl
41 g of 3-(2'-chloro-4'-trifluoromethylphenoxy)-a-6-
chlorophenoxy-propionic acid methyl ester is dissolved in
150 ml of glacial acetic acid. To this solution is added
dropwise a solution of 20.5 g of iodine chloride in 30 ml
of glacial acetic acid, and the reaction mixture is allowed
to fully react for 15 minutes (slightly exothermic reaction)
and, after the addition of 200 ml of water, the mixture is
heated at 90C for 3 hours. There is then added a 5%
sodium bisulfite solution until the mixture is decolorised,
a~d the oil which has precipitated is extracted with
toluene/ethyl acetate (1:1). The solvent is distilled
off to leave 47 g of oil which crystallises after the
addition of ligroin. The crystals are filtered off to
yield 32 g of the title product in the form of a white
crystalline mass having a melting point of 102-105C.
'' ' , ' . ~
. , . ~ , . .
.
,
,
~O~lZ~O
- 16 -
Example 10
a-l3-(2'-Chloro-4'-trifluoromethylphenoxy~-6-chloro-4-
cyanophenoxyl-propionic acid methyl ester
CH3
Cl 0-~H-COOCH3
CF3~ ._0~ - CN
Cl
27 g of 3-(2'-chloro-4'-trifluoromethylphenoxy)-a-6-
chloro-4-iodophenoxy-propionic acid methyl ester is
dissolved in 50 ml of N-methyl-2-pyrrolidone. There is
then added, with slow stirring, 6 g of copper-I-cyanide.
Under a weak flow of nitrogen, the reaction mixture
is heated to 140C bath temperature, and is stirred for 3
hours at this temperature. After cooling, the copper-I-
iodide which has precipitated is filtered off, and the
filtrate is slowly introduced into a mixture of 25 ml of
25% ammonia and 75 g of ice. The crystals which have
precipitated are filtered off and dried. The yield is
21 g of the crystalline title product having a melting
point of 121-124C.
.
- :: :- .
' . ~ . ,
l~)9~Z~(~
- 17 -
C-~ -0--\ ~ B
4 Ep5
No. C D B Ep Rl ... __ Physical
. . _ - . . _ constants
1 CF3 _ 5 CH3 CH3 ~ CH=CH2 m.p. 94-96
2 CF3 _ Cl 4 Cl CH3 COOCH3 b.p.163-5/0.07
3 CF3 ~ ~ 5 CH3 CH3 COOCH3 nD1.5104
4 CF3 ~ Cl 5 CH3 c~3 COOCH3 n21.5119
CF3 ~ ~ 5 CH3 C~I3 CN n21.5174
6 CF3 _ _ 5 CH3 CH3 COOH m.p. 88-90
7 CF3 Cl _ 4 Cl CH3 COOCH3 b.p.147/0.04 Torr
8 CF3 Cl _ 4 Cl CH3 COOH m.p. 129-132
9 CF3 Cl _ 5 Cl C~3 COOCH3 b.p. 153-5/0.02
Torr
CF3 Cl Cl 4 Cl CH3 COOCH3 m.p. 79-80
11 CF3 Cl CN 4 Cl CH3 COOCH3 m.p. 121-124
12 CF3 Cl No2 4 Cl CH3 COOH
13 CF3 Cl No2 4 Cl CH3 COOCH3 m.p. 106-10
14 CF3 Cl No2 4 Cl c~3 COS--~ ~._, 1
CF3 Cl No2 4 Br CH3 COOCH3 -
16 CF3 Cl N2 4 Br CH3 o~H2-CH=CH2
17 ~F3 Cl NQ2 4 Br CH3 CONHC2H5
18 CF3 Cl CN 4 Cl CH3 CN oil
19 CF3 Cl CN 4 Cl CH3 COOH
CF3 Cl CN 4 Cl CH3 COSC2H5
.
' ~
1091240
- 18 -
No. C D B ~p 1 Physical
constants
_ - . _. _ . __ . ,
21 CF3 Cl _ 5 CH3 CH3 COOCH3
22 CF3 Cl _ 5 CH3 CH3 COOH
23 CF3 Cl _ 5 CH3 CH3 O~H2-CH=CH2
24 CF3 Cl Br 4 Br CH3 COOCH3
CF3 Cl Br 4 Br CH3 oxxH2c-=cH
26 CF3 Cl Br 4 Br CH3 COOCH2~ , ~XH3
27 CF3 Cl Cl 4 Cl CH3 COOC2H5 m.p. 49-51
28 CF3 Cl Cl 4 Cl CH3 ~ CH-CH2 m.p. 47-So
29 CF3 Cl Cl 4 Cl CH3 ~ CH=CH2 oil
CF3 Cl Cl 4 Cl CH3 iso C3H7
31 CF3 Cl Cl 4 Cl CH3 CCN(CH3)0CH3 oil
32 CF3 Cl Cl 4 Cl CH3 COO--\ H \- m.p. 53-55
33 CF3 Cl Cl 4 Cl CH3 COS--~ ~. m.p. 86-890
34 CF3 Cl Cl 4 Cl CH3 COO-~ ~. m.p. 118.119
CF3 Cl Cl 4 Cl CH3 COOH m.p. 147-149
36 CF3 Cl Cl 4 Cl CH3 4 9 m.p. 49-52
37 CF3 Cl Cl 4 Cl CH3 COOisoC4Hg m.p. 58-Sgo
38 CF3 Cl Cl 4 Cl CH3 ~ 2CHC2H5 oil :
39 CF3 Cl Cl 4 Cl CH3 ox~H C=CH m.p. 47-49
CF3 Cl Cl 4 Cl CH3 COOC2H4Cl oil
~;
._. . _,. _ __ _ __ ., . _ . ~ . _ . _ ~.
., , ~ ; , ~ i . .
,'.'' "~ ' . ' ' .
. ' . . ` , , ':
~' '' ' ~ ~ ' ' ' ',
3.091~40
- 19 -
No. C ¦ D B Ep Rl A -- Physical
. _ . con~tants
41 CF3 Cl Cl 4 Cl CH COON=(CH3)2 oil
42 CF3 Cl Cl 4 Cl CH ~X~2H4CN m.p. 75-79
43 CF3 Cll Cl 4 Cl CH3 ~ CH20CH3 oil
44 CF3 Cl ¦ Cl 4 Cl CH3 OOOC2H40CH3 oil .
CF3 Cl Cl 4 Cl CH3 COOC H N/ \o oil
46 CF3 Cl Cl 4 Cl CH3 CONH2 m.p. 94-96
47 CF3 Cl Cl 4 Cl CH3 CON\ /- m.p.115-117
48 CF3 Cl Cl 4 Cl CH3 2 4 3 m.p.89-91
49 CF3 Cl Cl 4 Cl CH3 COOCH2CF3 m.p. 48-51
,.~-\.
. 50 CP3 Cl Cl 4 Cl CE3 CONH ~ m.p. 124-125'
51 CF3 Cl Cl 4 Cl CH3 T`. .~- oil
C,CH
52 CF3 Cl No2 4 Cl CH3 COSCH3 oil
53 ¦ CF3 Cl _ 4 N02 CH3 COOCH3 b.p.190~0.04 Tor~
54 I CF3 Cl Br 4 Cl CH3 COOCH3 m.p. 88-91
55 CF3 Cl I 4 Cl CH3 COOCH3 m.p. 102-105
, . ... .. ~
105~Z40
- 20 -
_ _ . . .
No. C D BEp Rl A Phys ical
l . cons tants . ¦
56 CF3 Cl - 2 Cl 4 _ . CH3 -COOCH3 b.p.162/0.05 Torr
57 CF3 CN _ 4 Cl CH3 COOCH3 m.p. 104-108
58 CF3 CN Cl 4 Cl c~3 COOCH3 m.p. 105-107
59 CF3 N02 ~4 Cl C~3 COOCH3 b p 183-5/0 05
60 CF3 No2 Cl 4 Cl CH3 CN oil
61 CF3 No2 Cl 4 Cl CH3 COOH
62 CF3 No2 Cl 4 Cl CH3 COS--\ H \-
63 CF3 No2 No2 4 Cl CH3 COOCH3 b.p.> 200/0 01
64 CF3 N2 N02 4 Cl CH3 COOC2H40CH3
65 CF3 N2 N02 4 Cl CH3 o~C2H40CH3
66 Cl CN Cl 4 Cl CH3 COOCH3 m.p. 113-4
67 Cl CN Cl 4 Cl CH3 COOC2H5
68 Cl CN Cl 4 Cl CH3 COOH m.p. 115
69 Cl CN Cl 4 Cl CH3 CCOisoC4Hg oil .
70 Cl CN Cl 4 Cl CH3 COOnC4Hg oil :~
71 Cl CN Cl 4 Cl H COOCH3 m.p. 114-116
CH3
72 Cl CN Cl 4 Cl CH3~ ~ H2 OE 2H3 oil
73 Cl CN Cl 4 Br CH3¦COOnC3H7 oil
_ _ .. ,, .. ___ . ............ ~................. _ ,,
.
,
, . . -
109124(~
- 21 -
_ . _ .... . _ . ....... __
No. C D ~¦Ep Rl A , Physical
cons tants
75 Cl CN Br4 BrC~3 COOCH3 m.p. 107-9
76 Cl CN _5 Cl CH3 COOCH3 l n251.5736
77 Cl No2 _ 4 Cl CH3 COOCH3
78 Cl No2 _ S Cl CH3 COOCH3
79 Cl No2 Cl 4 Cl CH3 COOCH3 resin
80 Cl Cl CN 4 Cl CH3 COOCH3
81 Cl Cl I 4 Cl CH3 COOCH3
82 Cl Cl Cl 4 Cl CH3 COOCH3 b.p. 190/o.ool
Torr
83 Cl Cl Cl 4 Cl CH3 COO~ .
84 Cl Cl Cl 4 Cl CH3 ~X~H2CH=CH2 oil
Cl Cl NO 4 Cl CH3 CCOC2H4Cl
~--~ . '
86 Cl Cl NO 4 Cl CH3 ~X~H2 \ /
87 Cl Cl No2 Cl CH3 ~OOisoC3H7
88 Cl Cl _ 4 Cl CH3 COOCH3 oil
B9 Cl Cl No2 4 Cl CH3 COOCH3 m.p. 95-6
90 Cl Cl Cl 4 Br CH3 COOCH3 b.p. 200o/0 001
31 Cl Br N02 2 Cl 4 Cl H CONH2
32 Cl Br N02 2 Cl 4 Cl CH3 XX~H2 (CH3)2
33 Cl Br No2 2 Cl 4 Cl H COOH
",;
_ _ _ ___. . _. . . ... ~ .
_ _ _ . . _ _ . _ _ . , ... . . .. , . .. . ..... .. . _ __
- - . .
r , ~ , '
'
`` lC~91Z40
- 22 -
_ _ __ _ .. _ . _ ,
~o. C D 3 Ep Rl A Phys iGal
constants
__ . l
94 Cl 3r N02 C1 4 !E cos ~
95 Cl 8r N02~ Cl 4 Cl H COSC2H4SCH3
96 Cl Br N22 Cl 4 Cl H COOC2EI4SCH3
97 Cl Br N022 Cl 4 Cl H CN
98 Br Br No2 4 Cl CH3 COOCH3
99 Br Br N2 4 Cl CH3 CONHCH3
3r 3 ~2 Cl ~3 ON\ /0
101 Cl Cl Cl 4 Cl CH3 OoXH2 2 oilb.po,OOl 200
102 Cl Cl Cl 4 Cl CH3 CON(CH3)0CH3 oil
103 Cl Cl Cl 4 Cl CH3 COC2H4Cl oil
104 Cl Cl Cl 4 Cl CH3 COOfHC2H5 oil b.p.O,OOl 210
105 Cl Cl Cl 4 Cl c~3 COOC2H40CX3 oil b.p.O,OOl 230
10~ Cl Cl Cl 4 Cl CH3 2 4 oil
107 Cl Cl Cl 4 Cl c~3 2 4 3 oil
108 Cl Cl Cl 4 Cl CH3 COOC2H4N(CH3)2 oil
109 No2 _ _ 4 Cl CH3 COOCH3 oil :
110 ~2 ~ N02 4 Cl ca3 COOCH3
111 No2 _ _ 5 Cl CH3 COOCH3
112 No2 Cl Cl 4 Cl CH3 COOCH3 m.p. 98-99
11' No2 Cl _ 5 Cl CH3 COOCH3 resin
114CN _ N02 4 Cl CH3 COOCH3 .
-
- -: : - ' --, "' '` ' :
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.: , . .
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.. ~ .
1091i~40
The compositions according to the invention are
produced in a manner known per se by the intimate mixing
and grinding of the active substances of the formula I
with suitable carriers and/or distributing agents,
optionally with the addition of antifoaming agents,
wet-ting agents, dispersing agents and/or solvents, all
inert to the active substances. The active substances
can be obtained and used in the following forms:
solid preparations: dusts, scattering agents, granules
(coated granules, impregnated granules
and homogeneous granules);
water-dispersible concentrates of active substance:
wettable powders, pastes, emulsions a~d
emulsion concentrates; and
liquid preparations: solutions.
The concentration of active substance in the compo-
sitions according to the invention is 1 to 80 per cent by
weight, and when being applied the compositions can if
necessary contain the active substances also at a lower
concentration, such as about 0.05 to l per cent by weight.
Other biocidal active substances or compositions can
be added to the compositions according to the invention.
Thus, the novel compositions can contain, in addition to the
stated compounds of the formula I, for example insecticides,
fungicides, bactericides, fungistatics, bacteriostatics,
nematocides or further herbicides, in order to widen the
sphere of action.
The production of the compositions according to the
invention is further illustrated by the following formu-
lation examples.
___ . _ ... . . .. , .. . . . , , _., .. , . ... , . ;.. , .. , . . . . -- . _ .. . .
. : ''
:, ..
,
,
1091Z40
- 24 -
Wettable powder
The following constituents are used to produce a) a
70% wettable powder and b) a 10% wettable powder:
a) 70 parts of active substance,
parts of sodium dibutyl-naphthalene sulfonate,
3 parts of naphthalenesulfonic acid/phenolsulfonic
acid/formaldehyde condensate (3:2:1),
parts of kaolin, and
12 parts of Champagne chalk; and
b) 10 parts of one of the active substances of the
formula I,
3 parts of a mixture of the sodium salts of ,
saturated fatty alcohol sulfates,
parts of naphthalenesulfonic acid/formaldehyde
condensate, and
82 parts of kaolin.
The given active substance is absorbed onto the appro- -
priate carriers (kaolin and chalk), and the material is
subsequently mixed and ground with the remaining constituents.
Wettable powders having excellent wetting and suspension
properties are obtained. It is possible to obtain from
wettable powders of this kind suspensions containing 0.1
to 8% of active substance, and these suspensions are suitable
for combating weeds in crops of cultivated plants.
Paste
The following materials are used to produce a 45% paste:
parts of an active substance of the formula I,
parts of sodium aluminium silicate,
14 parts of cetyl polyglycol ether having 8 mols
of ethylene oxide,
1 part of oleyl polyglycol ether having 5 mols
~ j .
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: , - . .
, ~ .. , , . - . ,
- . , . .
: ~ - - .. .-
- . . - :. , . -: -
..
.
:-: ~ -
~091240
- 25 -
of ethylene oxide
2 parts of spindle oil,
parts of polyethylene glycol, and
23 parts of water.
The active substance is intimately mixed and ground
with the additives in apparatus suitable for the purpo~e.
There is o~tained a paste from which can be produced, by
dilution with water, suspensions of any desired
concentration.
Emulsion concentrate
The following constituents are mixed together to
produce a 25% emulsion concentrate:
parts of an active substance of the formula I,
parts of a mixture of nonylphenolpolyoxyethylene
and calcium dodecylbenzene sulfonate,
parts of cyclohexanone, and
parts of xylene.
This concentrate can be diluted with water to give emulsions
of suitable concentration, e.g. 0.1%, and such emulsions are
suitable for combating weeds in crops of cultivated plants.
The novel phenoxy-a-phenoxyalkanecarboxylic acids and
their derivatives of the formula I, and also the compo-
sitions containing them, have an excellent selectively
herbicidal action against weeds in the widest variety of
cultivated crops. They also have an action regulating
the growth of plants.
Although the novel active substances of the formula I
are effective both for pre-emergence and post-emergence
application, the post-emergence application of these
active substances as contact herbicides appears to deserve
preferenc~; however, the pre-emergence application thereof
is also of interest. The novel active substances of the
'~ ' :' ' :.
lO91Z40
- 26 -
fonmula I are preferably applied to the crops of cultivated
plants after emergence of the plants, with the active
substances being formulated for example as 25% wettable
powders, or for e~ample as 20% emulsifiable concentrates,
and diluted with water.
The following test methods serve ~o verify the
suitability of the novel active substances of the formula
I as herbicides (pre- and post^emergence), and to prove
the superiority of them over known active substances of
similar structure.
Pre-emer~ence herbicidal action (inhibition of germination)
Immediately after sowing the test plants in seed trays
in a greenhouse, the surface of the soil is treated with
aqueous dispersions of the active substance, which have
been prepared from a 25% emulsion concentrate, and from
a 25% wettable powder containing active substances which
cannot be produced as emulsion concentrates owing to
inadequate solubility. Four different concentration series
are used, corresponding to 4, 2, 1 and 0.5 kg of active ~ -
substance per hectare. The seed trays are left in the
greenhouse at 22-25C with 50-70% relative humidity, and
the test is evaluated after 3 weeks, with the results being
assessed according to the following scale of ratings:
1 = plants have not germinated or have fully died off,
2-3 ~ very intense action,
4-6 = moderate action,
7-8 - slight action,
9 = no action (as in the case of untreated control
plants).
The following are used as test plants:
Hordeum (barley) Setaria italica
Triticum (wheat) Echinochloa crus galli
Zea (maize) Beta vulgaris
;;J
_ _ . ., . . . .. . . _. ~ _ .. , .. _ .... . ,. ... .. . . .. _.. ,_ .. .. __ ..... .
~- : -
l~)9~Z40
- 27 -
Sorghum hybr. (millet) Sida spinosa
Oryza (rice) Sesbania exaltata
Glycine (soya bean) Amaranthus retroflexus
Gossypium (cotton) Sinapis alba
Avena fatua Ipomoea purpurea
Lolium perenne Galium aparine
Alopecurus myosuroides Pastinaca sativa
Bromus tectorum Rumex sp.
Cyperus esculentus Chrysanthemum leucum
Rottboellia exaltata Abutilon sp.
Digitaria sanguinalis Solanium nigrum
Post-emer~ence herbicidal action (contact herbicide)
A largish number (at least 7) of weeds and of culti-
vated plants, both monocotyledonous and dicotyledonous,
are sprayed after emergence (in the 4- to 6-leaf stage)
with an aqueous active-substance dispersion in dosage
amounts of 0.06, 0.125, 0.25 and 0.5 kg of active
substance per hectare, and they are then kept at 24-26C
with 45-60% relative humidity. The test is evaluated at
least 15 days after treatment, and the results are assessed
according to the same scale of ratings as used in the
pre-emergence test.
The tested compounds according to the present invention
exhibited on some plants a pronounced contact-herbicidal
action, and effected on many plants a cessation of growth,
a sign of the growth-inhibiting properties of these
compounds.
Reduction of ~rowth of grasse~
Seeds of the grasses Lolium perenne, Poa pratensis,
Festuca ovina and Dactylis glomerata are sown in a soil/
peat/sand mixture (6:3:1) in plas~ic trays and watered in
the usual manner. The emerged grasses are cut back each
~:,
~' '~" .
. ' :.
.
,
.
11)91;~40
- 28 -
week to a height of 4 cm, and are sprayed 40 days after
sowing and 1 day after the last cutting with aqueous
spray liquors of an active substance of the formula I.
The amount of active substance is equivalent to 5 kg of
active substance per hectare. The growth of the grasses
is evaluated lO and 21 days after application.
Reduction of ~rowth of cereals
Spring wheat (Triticum aestivum), spring barley
(Hordeum vulgare) and rye (Secale) are sown in sterilised
soil in plastic trays and are grown in a greenhouse.~ The
shoots of the cereals are treated, 5 days after sowing,
with a spray liquor of the active substance. This leaf
application is equivalent to 6 ~g of active substance
per hectare. An evaluation is made after 21 days.
The tested active substances according to the
invention produce an appreciable reduction in growth
both of the grasses and of the cereals.
~,J
.. . , . , , ~
' ' : ' :'
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