Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
59~'~
- 1 Type Ia
.The invention relates to certain new phenoxycarboxylic
acid carbonylalkyl esters, to a process for their pre-
paration and to their use as herbicides.
It is already known that certain phenoxycarboxylic
acid esters have herbicidal properties. Thus, for
example, 5-(2-chloro-4-trifluoro-methyl-phenoxy)-2-nitro-
a-phenoxy-propionic acid methyl ester and 5-(2.-chloro-4-
trifluoromethyl-phenoxy~-2-nitro--phenoxy-propionic acid
ethyl ester can be used for comb.ating we.eds (see U.S.
10 Patent Sp.ecific.ation 4,093,446 and DE-OS (German Published
Specification) 2,.311,638). The activity of these sub-
stances is good, both when they are used in accordanc~
wi.th the pre-emergence meth.cd and wh:en they are used in
accordance wi.th the post-emergence method. However, a dis-
15 advantage is that the attack on some broad-leaved weeds and
graminaceous weeds which are di~ficult to combat is not
always. complete~ Furkhermore, the tolerance in some
crops, for example cereals, is not always completely
adequate.
The present inve.ntion now pr.ovides, as new compounds,
the phenoxycarboxylic acid carbonylalkyl esters o~ the
general formula
R1 R3
3 ~ ~ N2 (I),
in which
25. Rl' R2' R3, and R , independe.ntly of one another~
each represent hydrogen or alkyl,
R5 represents hydroxyl, alkoxy (which is optionall-J
substituted by alkoxy, alky.lthio, dialkylamlno,
cyano or halogen), alkenoxy, al~ynoxy, arall~oxy,
~ ~,t~.r
Le A 19 470 ~
aryloxy or the radical N
\ R7
wherein
R6 is hydrogen, alkyl of from 1 to 4 carbon atoms, sub-
stituted alkyl of from 1 to 4 carbon atoms in the alkyl part wherein
the substituents are selected from the group consisting of alkoxy
of from 1 to 4 carbon atoms, alkylthio of from 1 to 4 carbon atoms,
dialkylamino of from 1 to 4 carbon atoms in each alkyl group, and
Cyanoi alkenyl of from 3 to 8 carbon atoms, benzyl, phenylethyl,
phenyl or substituted phenyl wherein the substituents are selected
from the group consisting of alkyl of from 1 to 4 carbon atoms,
alkoxy of from 1 to 4 carbon atoms, alkylthio of from 1 to 4 carbon
: atoms, alkoxy-carbonyl of from 1 to 4 carbon atoms ln the alkoxy
moiety, fluorine, chlorine, bromine, trifluoromethyl and nitro; and
R7 is ~vr~Le~r alkyl of from 1 to 4 carbon a-toms,
suhstituted alkyl of from 1 to 4 carbon atoms in th~ alkyl part
wherein the substituents are selected from the group consisting
of alkoxy of from 1 to 4 carbon atoms, alkylthio of from 1 to 4
carbon atoms, dialkylamino of from 1 to 4 carbon atoms in each
alkyl grGup, and cyano; alkenyl of from 3 to 8 carbon atoms, benzyl,
phenylalkyl, phenyl or substituted phenyl wherein the subs-tituents
are selected from the group consisting of alkyl of from 1 to 4
carbon atoms, alkoxy of from 1 to 4 carbon atoms, alkylthio of
from 1 to 4 carbon atoms, alkoxy-carbonyl of from 1 to 4 carbon
atoms in the alkoxy moiety, fluorine, chlorine, bromine, trifluoro-
methyl and nitro~ or
R6 and R7, together with the nitron atom to which they are
bonded, represent piperidyl or perhydroazepinyl, in each case
--2--
optionally substituted by 1 to 3 methyl or ethyl ~roups, and
X represents hydrogen or chlorine.
It has been found that the phenoxy-carboxylic acid
carbonylalkyl esters of the formula (I) have powerful herbicidal
proper-ties.
Preferably, in formula (I), R , R , R and R , independently
of one another, each represent hydrogen or methyl, and
R5 represents hydroxyl, Cl-C4-alkoxy (which is optionally
substituted by Cl-C4-alkoxy, Cl-C4-alkylthio, di-Cl-C4-alkylamino,
cyano or chlorine), C3-C~-alkenoxy, C3-C6-alkynoxy, benzyloxy,
phenoxy or the radieal -NR R .
The invention also provides a process :Eor the preparation
of a phenoxyearboxylie aeid earbonylalkyl ester of the formula (I)
in which a phenoxyearboxylie aeid ehloride of the general formula
Cl ~ o-C-CO-Cl
CF3 ~ ~ O ~ > ~2 ~II),
X
in whieh
Rl~ R2 and X have the meanings ind.ieated above, is reaeted
with an ~-hydroxy-earboxylie aeid derivative of the formula
: ~ .
~, ~ 4~ 5L~ 7
-- 4 --
H0 C-Co-R5 (III),
R4
in which
R3 3 R4 and R5 have the meanings indicated above,
if appropriate in the presence of an acid acceptor and if
appropriate in the presence of a diluent.
Surprisingly, the phenoxycarboxylic'acid carbonyl-
alkyl esters according to th:e invention have a considerably
better herbicidal action than the compounds 5-(2-chloro-4-
. trifluo.romethyl-phenoxy)-2-nitro-a-phenoxy-propionic acid
lO methyl ester and 5-(2.-chloro-4-trifluoromethyl-phenoxy)-2-
nitro-~-phenoxy-propionic acid ethyl ester, wh.ich are known
from the state of the art and are subs'tances of the same
type of action which are very closely reIated chemically.
A particular ad~antage is that the substances according to
15 the invention are more suitable for destroying broad-
: leaved weeds and gramlnace.ous weeds which are di~icult to
combat, such as Ga~iu~ and Cyperus, especially when used in
accordance with the pre-emergence method, than the previously
known substances mentioned. In addition, the active com-
20 pounds according to the invention are distinguished by a
better tolerance in cereals, when applied in accordance with
the post-emergence method~ than the previously known sub-
stances mentioned.
If 5-(296-dichloro-4-trifluoromethyl-phenoxy)-2-
25. nitro-a-p~enoxy-propionyl chloride and hydroxyacetic acid
methyl ester are used as starting materials, the course of
the process according to the invention can be represented
by the following equation:
CH3
Cl 0-CH-C0-C1
CF~ o-~3-No2 + HO-CH2-CO-OCH3
CH~
Cl 0-CH-C0-0-CH2-C0-OCH3
CF3- ~ -0- ~ -No2
Cl
Le A 19 470
.. .. .. . . .. . . . . . . .. ... .
5~7
The ~ormula (IT) provides a gen.eral definition of
the phenoxycarboxylic acid chIorides required as starting
materials in carrying out the process according to the
invention. In this formula, Rl, R2 and X preferably
have those meanings which have already been mentioned
as preferred in conne.ction with the description of the
substances of the formula (I).
Examples of phenoxycarboxylic acid chlorides of the
formula (II) which may be mentioned are: 5-(2-chloro-4-
trifluoromethyl-phenoxy)~2-nit.ro-a-phenoxy- and 5-(2,6-
dichloro-4-trifluoromethyl-phenoxy)-2-nitro-a-phenoxy-
propionyl chloride.
The phenoxycarboxylic acid chIorides of the formula
(II) are known., or they. can be.prepared by cus.tomary
methods (see U.S. Pate.nt Specification 4,093,446). A
phenoxycarboxylic acid chloride which has not yet been
disclosed in the literature. can be synthesised by reacting
a phenoxycarboxyl.ic acid of the general ~ormula
,_~Cl ~ O-C\-CO-OH tIV),
CF~- ~ -O- ~ -N02R
X
.20 in which
Rl 3 R2 and X h.ave the meanings indicated above,
wi.th. a chlorinating agent, for example thionyl chloride,
if appropriate using a diluent, for example benzene or
ethylene chloride~ at a temperature between 10 and 100C,
and, when the reaction has ended, removing highly volatile
components by distillation.
T~e phenoxycarboxylic acids of the formula (IY) are
likewise known, or they can be prepared by customary pro-
cesses (see. U.S. Patent Specification 4,C93,446). Thus,
a compound of the formula (IV) is obtained b~J reacting a
phen.oxycarboxylic acid e.s.te.r of the general formula
Le A l9 470
.
1 ~L L~ 54 7
-- 6 --
CF~ 0~ NOz ( V ),
in which
Rl, R2 and X have. the meanings indicated above and
R repres:ents alkyl (especially methyl or ethyl),
wi.th an aqueous alkali metal hydroxide solution, preferably
with sodium hydroxide solution or potassium hydroxide
solut.ion, which is optionally diluted with an organic
so.lvent, for example methanol, ethanol or dioxan, at a
temperature bet`w.e.en 20 and 100C.
Examples of the phenoxycarboxylic acids of the
formula (I~) which may be mentioned are: 5-(2-chloro-~4-
trifluo.romethyl-phenoxy)-2-nitro-~ phenoxy- and 5-(2,6-
dichloro-4-trifluoromethyl-phenoxy)-2-nitro-a-phenoxy-
propionic acid.
The phenoxycarboxylic acid esters of the formula (~)
are also known, or they can be prepared by customary pro-
cesses (see U.S. Patent Specification 4,o~3,446). Thus,
a compound of the formula (V) is obtained by reacting a
phenol derivative of the general formula
.20
Cl OH
CF~ ~ O- ~ -No2 (~I),
in which
X has. the meaning indicated abo.ve,
or a s.odium salt or potassium salt thereof, with an
halogenocarboxylic acid e.s.ter of the general Iormula
25. H~l-C-CO-OR (~II),
Le A l9 470
s~
in which
Rl and R2 havethe meaningsindicated abo:ve,
`R represents alkyl (especially methyl or ethyl)
and
Hal represents chlorine or bromine,
if appropriate in the presence of an acid-binding agent,
for example sodium methylate or potassium carbonate, and
if appropriate using a polar diluent, for example methanol,
acetonitrile or sulpholane~ at a temperature between 20
10 and 100C.
Examples of the phenoxycarboxylic acid esters of the
formula (V) which may be mentioned are: 5-(2.-.chIoro-4-
trifluoromethyl-phenoxy)-2-nitro-a-phenoxy- and 5-(2,6--
dichloro-4-trifluoromethyl-phenoxy)-2-nitro-a-phenoxy-
15 propionic acid methyl ester and ethyl ester,
The phenol derivatives of the formula (~I) are known(see. U.S. Patent Specification Ll ,093~446). Examples of
the phenol derivatives of the formula (~I) which may be
mentioned are: 5-(2-chloro-4-trifluoromethyl-pheno~y)-2-
20 nitro-phenol and 5-(2~.6-dichloro-4-trifluoromethyl-phenoxy)-
2-nitro-phenol.
~ he a-halogeno-carboxylic acid esters of the formula
(VII) are also known. Examples of these which may be
ment.ioned are: a-chloro-propionic acid methyl ester and
25 ethyl ester and.a-bromo-propionic acid methyl ester and
ethyl ester.
The formula (III) provides a general. definition of
the a-hydroxycarboxylic acid deri~atives also required as
starting materials in carrying out the process according
3 to the invention. In this formula, R3, R4 and R5 pre-
ferably have those meanings which have already been
mentioned as preferred for these radicals in connection
with the description of the compounds of the formula (I).
The a-hydroxy-carboxylic acid derivati.ves of the
35 formula (III) are known, or they can be prepared by custom-
Le A 19 470
5~7
-- 8 --
ary processes (see``DE-OS (German Publish.ed Specification)
2,201,432).
The a-hydroxy-carboxylic acid amides of the general
formula
R3 /R6
HO-C-co_N 7 (IIIa)
.
in which
R3, R4, R6 and R7 have the meaning indicated above,
some of which have not hitherto been disclosed in the
literature~ are obtained, for example, by reacting an ~-
halo.geno-carboxylic acid amide of the general formula
Hal-C-CO-N / 7 (VIII )
in which
R3, R4, R6 and R7 have. the meanings indicated above
and
i5 Hal represents chlorine or bromine,
wi:th excess sodium acetate or potassium ac.et.ate in a first
stage, if app.ropriate in the presence of a cataly~t, for
example tetrabutylammonium bromide, and if appropriate
using a dil.uent, for example acetic acid or toluene, at a
20temperature between 20 and 200C, and deacylating the
ac.e.toxycarboxylic acid amide. thereby formed, of the
general ~ormula
CH3-CO-O-C-CO-N/R (IX),
R4 R7
in which
25. R3, R4, R and R7 have .the meanings indicated ab.ove,
in a second stage by react.ion wi.th di.lute. aqueous-alc~ic
Le A 19 470
.
. . . . .. , .. .. ....... . , . ., .. ~
- 9 -
sodium hydroxide sol~ltion at a temperature between 20
and 150C.
Examples o~ the a-hydroxy-carboxylic acid deri~atives
of the form~la (III) which may be mentioned are: the
methyl ester, ethyl ester, n-propyl ester, iso-propyl
e3ter, n-butyl ester, iso-butyl ester, sec.-butyl ester,
tert.-butyl ester, ben~yl ester, phenyl ester, methylamide,
ethylamide, n-propylamide, iso-propylamide, n-butylamide,
iso-butylamide, dimethylamide, diethylamide, di-n-propyl-
amide, di-iso-propylamide, N-methyl-N-iso-propylamide, N-
methyl-N-iso-butylamide, N-methyl-N~sec.-butylamide, di-
(2-ethylhexyl)-amide, N-methyl-N-(2-cyano-ethyl)-amide, di-
(2-methoxy-ethyl)-amlde,. diallylamide, N-methyl-N-propar~yl-
ami.de, N-methyl-N-(1-methyl-propargyl)-amide,. dipropargyl-
amide, cyclopentylamide, N-methyl-N-cyclopentylamide, cyclo-
hexylamide, N-methyl-N.-cyclohexylamide, anilide, 2-nitro-,
3-nitro and 4-nitro-phenylamide, 2-chloro-, 3-chloro- and
4-chlorophenylamide, 2,4-dichloro-, 2,5-dichloro-, 3,4-
dichloro- and 3,5-dichloro-phenylamide, 2-methyl-, 3-methyl-
and 4-methyl phenylamide, N-methyl-anilide, N-methyl-N-(2-
methyl-phenyl)-amide, N-methyl-M-(2-nitrophenyl)-amide,
N-methyl-N-(3-nitrophenyl)-amide, N-methyl-M-(4-nitrophenyl)-
amide, N-methyl-N-(2-chlorophenyl)-amide, N-methyl-N-(3-
chlorophenyl)-amide, N-methyl-N-(4-chlorophenyl)-amide,
25. N-methyl-N-(3-nitro-6-methyl-phenyl)-amide, N-ethyl-anilide,
N-ethyl N-(2-nitro-phenyl)-amide, N-ethyl-N-(3-nitro-
phenyl)-amide, N-ethyl-N-(4-nitro-phenyl)-amide, N-ethyl-N-
(2-chloro-phenyl)-amide, N-eth~Jl-N-(3-chloro-phenyl)-
amide, N-ethyl-N-(4-chloro-phenyl)-amide, N-ethyl-N-(3-
nitro-6-methyl-phenyl)-amide, N-propyl-anilide, N-propyl-
N-(2-nitro-phenyl)-amide, N-propyl-N-(3-nitro-phenyl)-
amide, N-propyl-N-(4-nitro-phenyl)-amide, N-propyl-N-(2-
chlo.ro-phenyl)-amide, N-propyl-N-(3-chloro-phenyl)-amlde ,
N-propyl-N-(4-chloro-phenyl)-amide, N-propyl-N-(2-methyl-
phenyl)-amide, N-propyl-M-(~-methyl-phenyl)-amide, N-
Le A 19 470
-- 10 -
propyl-N-(4-methyl-phenyl)-amide, N-propyl-M-(3 nitro-
6-methyl-phenyl)~amide, N-butyl-anilide, N-butyl-N-(2-
nitro-phenyl)-amide, N-~utyl-N-(3-nitro-phenyl)-amide,
N-butyl-N-(4-nitro-phenyl)-amide, N-butyl-N-(2-chloro-
phenyl)-amide, N-butyl-N-(3-chloro-phenyl)-amide, N-butyl-
N-(4-chloro-phenyl)-amide, N-butyl-N-(2-methyl-phenyl)-
amide, N-butyl-N-(3-methyl-phenyl)-amide, N-butyl-N-(4-
methyl-phenyl)-amide, N-butyl-N-(3-nitro-6-methyl-phenyl)-
amide, N-isobutyl-anilide, N-iso butyl-N-(2-nitro-phenyl)-
amide, N-iso-butyl-N-(3-nitro-phenyl)-amide, N-iso-butyl-
N-(4-nitro-phenyl)-amide, N-iso-butyl-N-(2-chloro-phenyl)-
amide, N-iso-butyl-N-(3-chloro-phenyl)-amide, N-iso butyl-
N-(4-chloro-phenyl)-amide, N-iso-butyl-N-12-methyl-phenyl)-
amide~ N-iso-butyl-N-(3-methyl-phenyl)-amide, N-iso--
butyl-N-(4-methyl-phenyl)-amide~ N-iso-butyl-N-(3-nitro~6-
methylphenyl)-amide, naphth-l-ylamide, naphth-2-ylamide,
N-methyl-N-naphth-l-ylamide, N-methyl-N-naphth-2-ylamide,
N-ethyl-N-naphth-l-ylamide, N-ethyl-N-naphth-2-ylam:ide, N-
n-propyl-N-naphth-2-ylamide) N-iso~propyl-N-naphth-2-yl-
amide, N-n-butyl-N-~aphth-2-ylamide, N-iso-butyl-N naphth-
2-ylamide, benzylamide, dibenzylamide, N-methyl-N-butyl-
amide, ~-ethyl-N-benzylamide, N-propyl-N-ben~ylamide, N-
butyl-N-~enzylamide, pyrrolidide, 2-methyl-pyrrolidide,
morpholide, piperidide, 2-methyl-piperidide, 4-methyl-
piperidide, 2,4-dimethyl-piperidide, 2,4,6-trimethyl-
piperidide, 2-ethyl-piperidide, 4-ethyl-piperidide, 2,4-
diethyl-piperidide, 2,4,6-triethyl-piperidide, 2-~ethyl-4-
ethyl-piperidide, 2-ethyl-4-methyl-piperidide, 2-methyl-5-
ethyl-piperidide, 2-ethyl-5-methyl-piperidide, 2-methyl-6-
ethyl-piperidide, 1,233,4-tetrahydroindolide, 2-methyl-
1,2,3,4-tetrahydroindolide, perhydroindolide, 2-methyl-
perhydroindolide, 2,2-dimethyl-perhydroindolide, 1,2,3,4-
tetrahydroquinolide, 2-methyl-1,2,3,4-tetrahydroquinolide,
perhydroquinolide, 2-methyl-perhydroquinolide, 4-methyl-
perhyd.roqulnolide, 1,2,3,4-tetrahydroiso-qulnolide and
perhydroisoquinolide o~ hydroxyacetic acid, ~-hydroxy-
Le A 19 470
1 ~{~ 7
propionic acid and ~-hydroxy-iso-butyric a.cid.
The ~-halogenocarboxylic acid amides o~ the formula
(~III) are known, or they can be prepared analogously to
known processes. They are obtained, for example by
reactin.g an a-halogenocarboxylic acid halide, ~or example
chloroacetyl chloride, with ammonia or a primary or
secondary amine, if appropriate in the presence of an acid
acceptor, ~or example potassium hydroxide (see J. Agric.
Food Chem. 4 (1956), 518-522).
~xamples o~ the halogenocarboxylic acid amides of
the formula (VIII) which may be mentioned are: the methyl-
amide, ethylamide, n-propyl-amide, iso-propylamide, n-
butylamide, iso-butylamide, dimethylamide,. diethylamide,
di-n-propylamide~ di-iso-propylamide, N-methyl-N-iso-propyl-
amide, N-methyl-N-iso-butylamide, N-methyl-N-sec.-butylamide,
di-~2-ethyl-hexyl)-amide, N-methyl-N-(2-cyano-ethyl)-amide,
di-(2-methoxy-ethyl)-amide, diallylamide, N-methyl-N-propar-
gyl-ami.de, N-methyl-N-(l-methyl-propargyl)-amide, dipropar-
~yl-amide, cyclopentyl-amide, N-methyl-N-cyclopentyl-amide,
cyclohexyl-amide, N-methyl-N-cyclohexyl-amide, anilide, 2-
nit.ro-, 3-nitro- and 4-nit.ro-phenylamide, 2-chloro-, 3-
chloro- and 4-chlorophenylamide, 2,4-dichloro-, 2,5-di-
chlo.ro-, 3,4-dichloro- and 3,5-dichloro-phenylamide, 2-
methyl-, 3-methyl- and 4-methyl-phenylamide, N-methyl-
anilide, N-methyl-N-(2-methyl-phenyl)-amide, N-methyl-N-
(2-nitro-phenyl)-amide, N-methyl-N-(3-nitro-phenyl)-amide,
N-methyl-N-(4-nit.ro-phenyl)-amide, N-methyl-N-(2-chloro-
phenyl)-amide, N-methyl-N-(3-chloro-phenyl)-amide, N-
methyl-N-(4-chloro-phenyl)-amide, N-methyl-N-(3-nitro-6-
methyl-phenyl)-amide, N-ethyl-anilide, N-ethyl-N-(2-
nitro-phenyl)-amide, N-ethyl-N-(3-nitro-phenyl)-amide,
N-ethyl-N-(4-nitro-phenyl)-amide, N-ethyl-M-(2-chloro-
phenyl)-amide, N-ethyl-M-(3-chloro-phenyl)-amide, N-ethyl-
M-(4-chloro-phenyl)-ami~e, N-ethyl-M-(3-nitro-6-methyl-
35 phenyl)-amide, N-propyl-anilide, N-propyl-M-.(2-nitro-phenyl)-
Le A 1~ 470
g5~
- 12 -
amide~ N-propyl-N-(3-nitro-phenyl)-amide,` M-propyl-N-(4-
nitro-phenyl)-amide,` N-propyl-N-(2-chloro-phenyl)-amide,
N-propyl-N-(3-chloro-phenyl)-amide, N-propyl-N-(4-chloro-
phenyl)-amide, N-propyl-N-(2-methyl-phenyl)-amide, N-propyl-
N-(3-methyl-phenyl)-amide, N-propyl-N-(4-methyl-phenyl)-
amide, N-propyl-N-(3-nitro-6-methyl-phenyl)-amide, N-butyl-
anilide, N-butyl-N-(2-nitro-phenyl)-amide, N-butyl-N-(3-
nitro-phenyl)-amide, N-butyl-N-(4-nitro-phenyl)-amide, N-
butyl-N-(2-chlor~-phenyl)-amide, N-butyl-N-(3-chloro-
phenyl)-amide, N-butyl-N-(4-chloro-phenyl)-amide~ N-butyl-N-
(2-methyl-phenyl)-ami.de, N-butyl-N-(3-methyl-phenyl)-amide,
N-butyl-N-(4-methylphenyl)-amide, N-butyl-N-(3-nitro-6-
methyl-phenyl)-amide, N-isobutyl-anilide, N-iso-butyl-N-(2-
. nitro-phenyl)-amide, N-iso-butyl-N-(3~nitro-phenyl)-amide,
N-iso-butyl-N-(4-nitro-phenyl)-amide, N-iso-butyl-N-(2
chlo.ro-phenyl)-amide, N-iso-butyl-N-(3-chloro-phenyl)-amide,
N-iso-b.utyl-N-(4-chloro-phenyl)-amide, N-iso-butyl~N-(2-
methyl-phenyl)-amide, N-iso-b.utyl-N-(3-methyl-phenyl)-amide,
N-iso-b.utyl-N-(4-methyl-phenyl)-amide, N-iso-b~ltyl-N-~3-
nitro-6-methyl-phenyl~-amide, naphth-l-ylamide, naphth-2-
ylamide, N-methyl-N-naphth-l-ylamide, N-methyl-N-naphth-
2-ylamide, N-ethyl-N-naphth-l-ylamide, N-ethyl~N-naphth-2-
ylamide, N-n-propyl-N-naphth-2-ylamide, N-iso-propyl-N-
. naphth-2-ylamide, N-n-butyl-N-naphth-2-ylamide, N-iso-butyl-
N-naphth-2-ylamide, benzylamide, dibenzylamide, N-methyl-N-
benzylamide, N-ethyl-N-benzylamide, N-propyl-N-benzylamide,
N-b.utyl-N-benzylamide, pyrrolidide, 2-methyl-pyrrolidide,
morpholide, piperidide, 2-methyl-piperidide, 4-methyl-
piperidide, 2,4-dimethyl-piperidide, 2,4,6-trimethyl-piper-
idide, 2-ethyl-piperidide, 4-ethyl-piperidide, 2,4-diethyl-
piperidide, 2,4,6-triethyl-piperidide, 2-methyl-4-ethyl-
piperidide, 2-ethyl-4-methyl-piperidide, 2-methyl-5-ethyl-
piperidide, 2-ethyl-5-methyl-piperidide, 2-methyl-6-ethyl-
piperidide, 1,2,3,4-tetrahydroindolide, 2-methyl-1,2,3,4-
t.etrahydroindolide, perhydroindolide, 2-methyl-perhydroindolide,
Le A 19 470
..
.. , . .. . .. ..... . . ....... _ .. .. ...... . . .. ... . .
` .lL1~S~'7
- 13 -
2,2-dimethyl-perhydroindolide, 1,2,.3,4.-te.trahydroquinolide,
2-methyl-1,2,3,4.-tetrahydroquinol.ide, perhydroquinolide,
2-methyl-perhydroquinolide, 4-methyl-perhydroquinolide,
1,2,3,4-tetrahydroisoquinolide and perhydroisoquinolide
of chloroacetic acid, ~-chloropropionic acid and a-
chloroisobutyric acid.
The process according to t.he invention is preferably
carried out using a suitable solvent or diluent. Suitable
solvents or diluents are. vi.rtually any of the inert
organic solvents. These include, as prefe.rences,
aliphatic and aromatic, optionally chlorinated hydro-
carbons, such as benzine, benzene, toluene, xylene,
methylene. chloride,. ethylene chloride,. chloroform,
carbon tetrachlorideS: chIorobenzene and o-dichIorobenzene;
ethers, such as. di.ethyl ether and di.butyl ether, tetra-
hydrofuran and dioxan, ketones, such as acetone, methyl
ethyl ketone, methyl isopropyl ketone and methyl isobutyl
ke.tone; nitriles, such as acetonitrile and propionitrile;
and aprot.ic polar solven~s, ~or example dimethylformamide,
.2Q dimethylsupho~ide, sulpholane and hexamethylphosphoric
acid triamide.
Any of the customary acid-binding agents can be used
as an acid accept-or. ~lkali metal carbonates and
alc.ohol.atesj such as sodium carbonate and potassium
25. carbonate and sodium methylate or ethylate and potassium
methylate or ethylate, and furthermore aliphat.ic, aromatic
or heterocyclic amines, for example triethylamine~ tri-
me.thylamine, dimethylaniline, dimethylben~ylamine and
pyridine,.have p.roved particularly suitable.
The reaction temperature can be. vari.ed ~ithin a sub-
stantial range. In ge.neral~ the reaction is carri.ed out
at ~rom -20 to +100C, preferably from 0 to 50C.
In ge.neral, the process according to ~he invention
is carried out. under normal pressure.
For carrying QUt th.e process accoraing to.the invention,
in ge.r.eral 1 to 1.5 mo.les 3 pre.ferabIy 1 to l.2 males, of
Le .~ 19 470
)5A~7
- 14
a-hydroxy-carbo:xylic acid der.ivative of the formula (III)
and l to 5 moles of acid-binding agent are employed per
mole of phenoxycarboxylic acid chloride of the formula
(II). In general, the reaction is carried out in a
suitable diluent and the reaction mixture is stirred at
the required temperature for several hours. An organic
solvent~ for example toluene, is then added and the organic
phase is worked up in the customary manner by washing and
drying it and disti.lling off the solvent.
Some of the new compounds are obtained in the form
of oils, some of which cannot be distilled wi.thout decom-
position, but can be freed from the last. volatile con-
sti.tue.nts by so.-called "incipient distillation~', that is
to say by prolonged heating to moderately elevated tempera-
tures under reduced pressure, and can be purified in this
manner. The refractive index is used for their character-
is.ation.
If the products are. obtained in solid form,. they can
be purified by recrystallis.ation. The melting point is
then us.ed for their characterisation.
The active compounds according to the invention
influence plant growth and can therefore be used as
defoliants, desiccants, agents for destroying broad-
le.aved plants, germination inhibitors and, especially,
as weed-~illers. By l'weeds" in the broadest sense
there are meant plants growing in places where they
are not desired.
Whether the compounds according to. the invention
act as. total herbicides or selective herbicides depends
3 essentially on the amount used.
The active compounds according to the present
invention may be used, for e~ample, to combat the
following plants:
dicotyl.edon we.eds of the gen'era Sina~ls, Lep;'diu ,
' G~alium, Ste~llaria,~ Matric~aria, ~:nth'e~is, Ga}irsoga,
Le A 19 470
''Chen'o'p'o'dium,''Ur't'i'ca,' Ser~ecio,'~ar~nt~hus, PortuIaca,
.. . ~ .. . .. .. . .. . .. . .
Xanthium, Convoli~ulus~ Ipo~oea,''~ol'y'gonum, Ses_arlla,
Ambrosia, Cirsium,' Carduus, Sonchus, Ror~ppa, Rotala,
Linde~rnia, Lamium, Veronica, Abutilon,''Emex,''Dat`ura,
iola, GaIeopsis, ~ , Centaurea and''Solanum; and
monocotyledon weeds of the genera Echinochloa,
Setaria, Panicum, Digitaria, Phleum, Poa, Festuca,
Eleusine~ Brachiaria~L-ol~ium~ Bromus~ ~vena, Cyperus~
Sorghum, Agropyron, Cynodon3 Monochoria, Fimbristylis,
Sagittaria,'Eleo'ch'aris,' Sci'r'p`us,'' às'p'al'um,''I cha'emum,
''Sphencclea., ~ ,''AOro tis, ' l pecurus and
Apera.
;
The actlve compounds according to the present
invention may be used, for example, as selective herbicides
in the following cultures:
dicotyledon cultures of the genera ~ ,
''~lycine, Beta,''Dauc'us,''Phas'eolus,''Pi's'um,''So'l'an'um,''Li'num,
' lpoffloea~ Vicia, Nicoti~ana, ~ , ~ràchis,
___ _. _ __
''Brassica, Lactuca,' Cucumis and Cucurbita; and
20monocotyledon cultures of the genera ~ , ~ea,
Triticum, Hordeum, vena?''Secale, Sorghum~ Pa~ um,
Saccharum~ ~nanas, ~spara~s and ~l'llum.
.
However, the use of the active compounds according
to the invention is in no way restrlcted to these genera
but also embraces other plants, in the same way.
Depending on the concentrations, the compounds
can be used for the total combating of weeds, for example
on industrial terrain and railway tracks and on paths
and squares with or without trees. Equally, the compounds
3 can be employed for combating weeds in perennial. cultures,
for example afforestations, decorative tree plantings,
orchards, vineyards, citrus groves, nut orchards, banana
plantations, coffee plantations, tea plantatlons, rubber
plantatlons, oil palm plantations, cacao plantat~'ons~
soft frult plantings and hopfields, and for the selective
combating of we:eds in annual. cultures`.
Le A 19 470
- 16 -
. The act.ive.:compounds according to the invention
display a very good action against broad-leaved weeds and
graminaceous weeds. They can be used, in particular, for
removing broad-leaved weeds and graminaceous weeds which axe
difficult to combat, such as Galium and ~ . For
further improvement of their action spectrum, combinations
with other herbicides, above all wit11 N benzthiazol-2-yl-
N,N'-dimethyl-urea, are possible.
The active. compounds. can be. converted into the customary
formulations, such as solutions, emulsions, suspensions,
powders, foams, pastes, granules, natural and synthetic
materials impregnated wi.th active compound, and very fine
capsules in polymeric substances.
These formulations may be produced in known manner, for
example by mi~ing the active. compounds with extenders, that
is to say liquid or solid diluents or carriers, optionally
with the use of surface-active agents,. that is to say
emulsifying agents and/or dispersing agents and/or foam-
forming agents. In the case of bhe use of water as
an extender, organic solvents can, for example, also
be used as auxiliary solvent-s.
. As liquid di.luents or carriers, especially solvents,
there are suitabIe in the main, aromatic hydrocarbons,
such as xy.lene,: toluene or alkyl naphthalenes, chlorinated
aromatic or. chIorinated aliphatic hydrocarbons, such
as. chIorobenzenes,. chloroethylenes or methylene chloride,
aliphatic or alicyclic hydrocarbons, such as cyclohexane
or paraffins, for example mineral oil fractions, alcohols,
such as butanol or glycol as well as their ethers and
30 . e.sters, ketones, such as acetone, methyl ethyl ketone,
methyl isobutyl keto.ne or cyclohexanone, or strongly
polar solvents., such as dimethylformamide and dimethyl-
sulphoxi.de, as we.ll as water.
As solid carriers. there may be used ground ~.atural
35 ~ mi.nerals, such as kaolins~ clays,. talc,. chalk, quartz,
Le A 19 470
'7
attapulgite.~:.montmorillonite or diatomace.ous earth, and
ground synthet:i:c. minerals, such as highly-dispersed
silicic acid, alumina and silicates. As solid carriers
for granules. there may be used crushed and fractionated
natural rocks such as calcite, marble, pumice, sepiolite
and dolomite, as well as synthetic granules of inorganic
and organic meals, and granules of organic material
such as sawdust,. coconut shells, maize cobs and tobacco
stal~s.
As. emulsifying and/or foa~-forming agents there
may be. us.ed non-ionic and anionic emulsifiers, such
as polyoxyethylene-fatty: acid esters, polyoxyethylene-
fatty alcohol ethers, for example alkylaryl polyglycol
ethers, alkyl sulphonates, al~cyl sulphates, aryl sul-
phonates as well as albumin hydrolysis products. Di.s-
persing agents include~ for example, lignin sulphite
waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural
and synthetic polymers in the form of powders, granules
or latices, such as gum arabic, polyvinyl alcohol and
polyvinyl acet.ate,. can be used in the formulatlons.
It is possible to. use colorants such as inorganic
pigm~nts, for example iron oxide, titanium oxide and
Prussian. Blue, and organic dyestuffs, such as allzarin
dyes.tuffs, azo dyestuffs. or metal phthalocyanine dyestuffs,
and trace nutrients, such as salts of iron, manganese,
boron, copper,. cobalt, molybdenum and zinc.
The formulations in generaI contain from 0.1 to
95 per cent by we:ight of active compound, preferabl~J
from 0.5 to 90 per. cent by weight.
The active compounds according to the invention, as
such or in the form of their formulations, can also be used,
for. combating weeds, as mixtures with other herbicides,
finished formulations or tan~c ~icing being possible. Ml~-
tures:wi.th o~her ~no~n active. compo~mds, such as ~urgicides,
: Le A 19 470
.~ 54'7
- 18 -
insecticides, acaricides, nematicides, bird repellants,
growth factors, plant nutrients and agents which improve
soil structure, are also possible.
The active compounds can be used as such, in the
form of their formulations or in the use forms prepared
therefrom by further dilution, such as ready-to-use solu-
tions, SU3pe~iOnS, emulsions, powders, pastes and granules.
They are used in the customary manner~ for example by
watering, spraying, atomising or scattering.
The active compounds according to the invention can
be applied either before or after emergence of the plants.
They are preferably applied before emergence of the plants,
that is to say by the pre-emergence method. They can
also be incorporated into the soil be~ore sowing.
The amount of active compound used ca~ vary within
a substantial range. It depen~ essentially on the
nature of the desired effect. In general1 the amounts
used are from 0.05 to l0 kg of active compound per hectare,
preferably from 0.l to 5 kg /ha.
The present invention also provides a herbicidal com-
position containing as active ingredient a compound of the
present invention in admixture with a solid diluent or
carrier or in admixture with a liquid diluent or carrier
containing a surface-active agent.
The present invention also provides a method of
combating weeds which comprises applying to the weeds,
or to a habitat thereof, a compound of the present invention
alone or in the form of a composition containing as active
ingredient a compound of the present invention in admixture
with a diluent or carrier.
~ he present invention further provides crops protected
from damage by weeds by being grown in areas in which
immediately prior to and/or during the time of the growing
a compound of the present invention was applied alone
or in admixture ~ith a diluent or carrier.
1e A l9 470
35~
-- 19 -
It wi.ll be.:s.een that the usual me.thods of p.r.oviding
a harvested crop may be impr.o.ved by: the present invention.
The herbicidal activity of the compounds of this
invention is illustrated by the following biotest Examples.
In these Examples, the compounds according to
the present invention are each identifi.ed by the number
(given in brackets) of the corresponding preparative
Example, which will be found later in this specification.
The known comparison comp.ounds are identified
as follows:
(A) = ~ 51 o~ox~2H
lc~3
(B ) = Cl ~p-C~-COOC}~3
F3C~ ~;2
EXampIe A
-
Pre emerge.nce. tes.t
Solvent: 5 parts. by weight of acetone
Emulsifier: l part by weight of alkylaryl polygl.ycol
ether
To produce a suitable preparation of active compound,
l part by weight of act.i.ve compound was mixed wi.th
the stated amount of sol.vent,. the stated amount of emul-
sifier was added and the. concentrate was diluted with
water to. the desired concentration.
Se.eds of the test plants were sown in normal soil
and, after 24 hours, watered with the preparation of
the active compound. It was expedient to keep constant
the amount. of water per unit area. The concentration
~e A 19 470
.
'7
- 2C -
. of the active compound in the preparation was of no
importance, only the amount of acti:ve compound appli.ed
per unit area being decisive. Afte.r three weeks, the
degree of damage to the plants was determined in %
damage in comparison to the development of the untreated
control. qthe figures denoted:
0% ~ no action (like untreated control)
100~ = total destruction
In this test,. the compound (lLI) exhibi.ted a con-
siderably better activity against' Cyper'us than the known
comparison substance (A).
Example B
Pre-emergence test
Solvent: 5 parts by weight. of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
To produce a suitable preparation of acti~e compound,
1 part by weight of active compound was mi~ed with the
stated amount of sol.vent, the stated amount of emulsifier
was added and the concentrate was diluted with water
: to the desired concentration.
Seeds of the test plants were sown in normal soil
and, after 24 hours, watered with the preparation of
the active compound. It was expedient to keep constant
25. the amount of water per unit area. The concentration
of the active compound in the preparation was of no
: importance, only the amount of active compound applied
per unit area being decisive. ~fter three weeks, the
degree of damage to the plants was determined in %
damage in comparison to the development of the untreated
control. The figures denoted:
0% - no action (like untreated control)
100% = total destruction
In this. test,. the compounds (2) ard (13) exhiblted a
35 . considerabIy b.e.tter action against Galiu~ than t.he known
comparison subs.tance (3).
Le A 19 470
4~S~7
- 21 -
Example C
Post-emergence Test
Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
To produce a suitable preparation of active compound
1 part by weight of active compound was mixed with the
stated amount of solvent, the stated amount of emulsifier
was added and the concentrate was then diluted with
water to the desired concentration.
Test plants. which had a height o~ 5-15 cm were
sprayed with the preparation of the active compound
in such a way as. to apply the amounts, of' active compound
per unit area which we.re prescribed. The concentration
of the spray liquor was so chosen that the amounts of
active. compound prescrib.ed we:re applied in 2,000 1 of
water/ha. After three weeks, the degree of damage
- to the plants was rated in % damage in comparison to
the de.velopment of the untreated control. The flgures
denoted:
0% = no action (like untreated control)
100% = total. destruction.
In this test,. the. compound ~14) showed a considerably
b.etter tolerance in wheat. than the known comparison substance
25. (A), whilst h.aving an equally good action aga.inst' Stellaria
and Matricaria.
Le A 19 470
iV~'7
- ~2
Example D
Defoliation and desiccation of the leaves of cotton
Solvent: 30 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of polyo~yethylene sorbitan
monolaurate
To produce a suitable preparation of active compound,
1 part by weight of active compound was mixed with the sta-ted
amounts of solvent and emulsifier and the mixture was made
up to the desired concentration with water
Cotton plants were grown in a greenhouse until the
5th secondary leaf had unfolded completely. In this
stage, the plants were sprayed with the preparation of
active compound until dripping wet. After 1 week, the
shedding of leaves and the desiccation of the leaves were
rated, in comparison with the control plants.
The figures of merit have the following meanings:
0 denotes no desiccation of the leaves,
no shedding of leaves
+ denotes slight desiccation of the leaves,
slight shedding of leaves
++ denotes severe desiccation of the leaves,
severe shedding of leaves
+++ denotes very severe desiccation of the leaves,
very severe shedding of leaves.
In this test, the active compounds (5), (12) and (14)
caused a very severe dessication of the leaves, a very
severe shedding of leaves.
Le A 19 ~70
S~L7
Example E
Inhibition of growth of cotton
Solvent: 30 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of polyoxyethylene sorbitan
monolaurate
To produce a suitable preparation of active compound,
1 part by weight of active compound was mixed with the
stated amounts of solvent and emulsifi.er and the ~ixture
was made up to the desired concentration with water.
Cotton plants were grown in a greenhouse until the
5th secondary lea~ had unfolded completely. In this
stage, the plants were sprayed with the preparations of
active compound until dripping wet~ After 3 weeks, the
additional growth oE the plants was measured and the
inhibition of ~rowth in per cent of the additional growth
of the control plants was calculated. 100~ inhibition of
growth meant that growth had stopped and 0% denoted a
growth correspondiny to that of the control plants.
In this test, compared with the control, active
compound (12) exhibited a powerful inhibition of growth.
Pre_ rative Examples
Exa~ple l:
-- -- .
CH3
Cl 0-CH-C0-0-CH2-C0-N ~
CF3 ~ 0- ~ -No2 CH3 (l)
Cl
. A solution of 12...5 g ~27 mmol) of 5-(2,.6.-dichloro-
4-trifluoromethyl~phe:noxy)-2-nit.ro-~-.phe:noxy-p.rop.ionyl
~e A 19 470
5~'7
_ ~4 -
chloride in 30 ml o~ toluene was added dropwise to a
solution3 cooled to 0 to:5C, ,ef 5 g (30 mmol) of hydroxy-
acetic acid N-methyl-anilide and 10 ml of pyridine in 70
ml of toluene. The reaction mixture was stirred at room
temperature overnight, diluted with 300 ml of toluene,
washed until neutral, dried and filtered and the filtrate
was concentrated. 13 g (81% of theory) of 5-(2~6-dichloro~
4-trifluoromethyl-phenoxy)-2-nitro-~-phenoxy-propionic
acid N--methyl-N-phenyl-carbamoyl-methyl ester were obtained
in the form of a yellowish tinged oil of refractive
index n24: 1.5607.
The compounds of the formula (I) listed in the follow-
ing Table 1 were prepared analogously to ~xample 1:
T a b ~l e
R1 R3
C1 o-c~co-o-c-co-R5 (I)
CF3- ~ ~~ ~ -N0 R4
MOlting point
Example 4 ( C); re~ract-
No. X Rl R2 R3 R R5 ive index:
2 H H CH3 H ~ -oc4H9-n nD4:1~5227
3 H H CH3 H H -N ~ n24:l95606
CH3
4 H H H H H -C2H5 88
H H CH3 H H -NtCH3)2 n24:1,5235
6 H H CH~ H H -NtCH2-CH=CH2)2 n24:1,5124
7 H H CH3 H H - ~ n24:1,5132
8 H H CH3 H H - ~ nD5:1~5215
CH3
Le A 19 470
. . . . ,. ~.... .. . .. .. .
Si4~7
- 25 -
M<ing point
No. X Rl R2 R3 R4 R5 ( C)~ refract-
g H H C~3 H H ~ ~ CH3 nD4:1 d 5312
lo H H CH3 H CH3 -N ~ nD4:1.5760
CH3
11 H H CH3 H CH3 -0C2~5 nDl 1J5221
12 Cl H CH3 H H -oc4H9-n n~4:1~5606
13 H H C~3 H H -C2H5 n24:1,5297
14 Cl H CH3 H H -C2H5 n24:1~5330
Cl H CH3 H C~l3 -C2HS
16 Cl H CH3 H H -N(CH2 ~ )2 44
17 C1 H CH3 H H -NH ~ 60
CF
18 Cl H CH3 H H ~ Cl 46
19 Cl H CH3 H CH3 -N ~ ) 132
Cl H CH3 CH3 CH3 -C2H5 nD2~ }19
21 Cl H 3 -OCH3 n2D'5:1,542
The phenoxycarboxylic acid chlorides to be. used as
starting materials could be prepared, for example, as follows:
EXample II-l
_ - CH~
Cl O-CH-CO-Cl
CF3-(~c-o-(~(-No2
Le A 19 470
- . .
1~4~5~7
- 26 -
9.7 g (82 mmol) of thionyl chlorlde were added drop-
wise to a solution of 30 g (68 mmol) of 5-(2,.6.-dichloro-4-
trifluoromethyl-phenoxy)-2-nitro-~-phenoxy-propionic acid
and 0.5 ml of dimethylformamide in 100 ml of 1,2-dichloro-
ethane at room temperature. The mixture was heated underreflux for 4 hours. Active charcoal was added, the mix-
ture was filtered and the filtrate was concentrated. ~fter
digesting the oily resi.due with 100 ml of ligroin, Z6.2 g
(84% of theory) of 5-(2,6.-dichloro-4-trifluoro-methyl-
phenoxy)-2-nitro-~-phenoxy-propionyl chloride were obtained
in the form of yellow crystals of melting point 92C.
The phenoxycarboxylic acids required as precursors
could be prepared, for example,as follows:
Example IV 1
CH~
C1 O-C~-CO-OH
CF3- ~ ~~ ~ _N02
Cl
1.35 ~ (0.3 mol) of 5-(2,.6-dichloro-4-trifluoromethyl-
phenoxy)-2-nitro-a-phenoxy-propionic acid methyl ester and
30 ml of concentrated sodium hydroxide solution were
stirred in 400 ml of acetonitrile and 150 ml of water at
20C for 24 hours. The solution was concentrated, the
residue was taken up in 500 ml of water and the aqueous
mixture was acidified with 50 ml of concentrated hydro-
chloric acid. 93 g (71% of theory) of 5-(2,6-dichloro-4-
trifluoromethyl-phenoxy)-2-nitro-~-phenoxy-propionic acid
were. obtained in the form of pale yellow crystals with a
melting point of 146C (after recrystallisation from toluene/
cyclohexane).
The phenoxycarboxylic acid esters required as pre-
cursors could be prepared as follows, for ecample:
Le ~ 19 470
~V~t7
- 27 -
' Ex'amp'l'e''~-1
CH
Cl 0-C'H-C0-OCH3
CF3~ No2
Cl
40 g (0.24 mol) of ~-bromo-propionic acid methyl
ester we.re added dropwise to a mixture, warmed to 50C, of
73.6 g (0.2 mol) of 5-(2,.6-dichlo.ro-4-trifluoromethyl-
phenoxy~-2-nitro-phenol, 32 g of potassium carbonate and
200 ml of acetonitrile. The reaction mixture was heated
under reflux for 5 hours and then poured into 1 litre of
water and the aqueous mixture was extracted with 1 litre of
toluene. The to.luene phase was washed with 300 ml of lN
aqueous sodium hydroxide solution and then with 500 ml of
water. After distilling off the solvent in: vac:uo, 74 g
(81% of theory) of 5-(2,6-dichloro-4-trifluoromethyl-
phenoxy)-2-nitro-~-phenoxy-propionic acid methyl ester were
obtained as an oil which crystallised on adding methanol
giving crystals with a melting point of 78C.
Le A 19 470
