Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~ 2 - HOE 83/F 236
The present ;nvention relates to novel conpounds
of the general formula I
R l _x~ O-CH-A~C-N-C-N
- ~Ra
in which
S X denotes O or -CH~-,
Y denotes 0~ S or NR ;
A1 denotes a direct bond, -CH2-CH2- or -CH=CH-;
R denotes the radical
~ or R ~ N
~here ~ = CH or N,
a - u or S and
n = O or 1;
R2 denotes ~C1-C~)-alkyl, ~here~ if y a NRS~ R~ and
R5~ togeth~r Yith the nitrogen a~om, can ~orm a
5-me~b~red or 6-membered ring, in ~h;ch one -CH-
group oay be repl~ced by O or NH;
R3 and R4 independently of one another denote hydrogen
or ~C1-C4)-alkyl, or together denote the group
/t~3
=CH-N ~ and, if R3 - hydrogen, R4 also
\CH3
denotes the group -CO-R8, -COOR8 or -CO-NHR ;
R5 denotes hydrogen or ~C1-C4)-alkyL;
R6 and R7 independently of one another denote ~, F, Cl,
~r, CH~ CF3, N02 or CN; and
R denotes (C1-C83-alkyl, (C3 C6) alk y ,
optionally ~ono- or di-subs~ituted by halogen,
~z~
or CF3 or (c1-c~)-alkyln
Preferred compounds of the general for~ula I here
are çompounds in which X and Y denote oxygen, A denotes
a direct bond, R2 denotes methyl or ethyl and R3 3nd R4
each denote hydrogen or together denote the dimethyl-
aminomethylene radical; R6 denotes CF3, F, Cl or Br; R7
denotes H, Cl or er; Z denotes CH or N; n denotes zero
and Q denotes a or S.
The invention also relates to a process for th~
preparation of the compounds of the general formula I,
which comprises reacting compounds of the general Formula
II
Rl-X~O CH-A~C~' I I
;n which "Hal" denotes chlorine or bromine, with com-
pounds of the general ~ormula IlI
R ;
N-CcNH II
R~ y
~2
The compounds of the general formula II are known,
or they can be prepared by kno~n processes, such ~s those
described, for example, in 6er~an Offenlegungsschrift
2,623,55R, G~rman Offenlegungsschrift 2,914,300, European
Otfenlegungsschrift 50,019 and Belgian Pat~nt ~89,7~3.
Th~ co~pounds of the general formula III are like~ise
kno~n; their preparation i-~ described~ for example, in
German O~fenlegungsschrift 2,353,~04.
The compounds of the formula llI are preferably
employed in the process according ~o the in~ention in
the form of their hydrochloric acid or sulfur;c acid
saLts.
The reactions are carried out in the presence
of inorgan;c or organic bases~ the alkali ~etal hydroxides
being preferred here.
~r Suitable solvents are hydrocarbons or halogeno-
,~.
~Z4!2~
~,
hydrocarbons which are ;nert under the reaction condi-
tions, such as, for example, toluene, xylene or methylene
chloride.
If the reaction is carr;ed out in methylene
chlor;de, it i5 advisable to add ~ater. A procedure is
then preferably follQwed in ~hich, for examp!e, the sul-
fur;c dcid salts of the compounds III are initially intro-
dused into a mixture of ~ater and methylene chlorlde at
temperatures of -10C to +40C and the compounds II and
and t~ice the molar a~ount of aqueous sodium hydroxide
solution are added dropwise from separate vessels. De-
pending on their solubility, the compounds accord;ng to
the ;nvention are worked up and isolated by filtrat;on
with suc~ion or by evaporation of the methylene chloride
phase.
The compounds of the general formula I according
to the inYention have a center of asymmetry and are
usually present in racemic form. Ho~ever, it is also
possible to use optically active starting substances of
the g~neral formula II in the preparation process des-
cribed, the preparation of these subst~nces being des-
cribed, ~or example, in Europ~an Pat~nt 2,800. The des-
ired isom~rs are thereby obtained in high optical purity.
On the basis of biological activity, the D-isomers are
preferred. The general formuLa I thus comprises both
the race~ates and the D-iso~ers o~ the compounds accord-
ing to th~ invention.
The compounds of the formula I exhibit a good
herbicidal action and good s~lectivity in important large-
scale crops. They are suitable for ~electively combat-
ing broad-leav~d and graminaceous annual and perennial
~eeds in agriculturally i~portant crops~ such as, for
example, ~heat, rice, mai~e, sugar be~t, ~oybean and
cotton) by the pre-e~ergence and post-emergence ~ethod.
Moreover, the s~bst~nces according to the invention e~-
hibit good gro~th-regul3ting properties on crop plants.
They have a reguLating effect on the endogenous ~etabol-
ism of plants and can thus be used for controlled infLu-
encing of the contenes of plants and for facilitating
z%
harvesting, such as~ for example, for des;ccation, abs-
ciss;on or growth compression. Furthermore, they are
also suitable for general control and inhibition of un-
desirable vegeta~ive growth, without thereby destroying
the plants. Inhibi~ion of vegetative gro~th is of great
i~portance in many monocotyledonous and dicotyledonous
crops, since lodging can thereby be reduced or completely
prevented.
The compounds according to the invention also
exhibit a surprising activity as herbicide antidotes
(safeners). They can thus antagonize, that is to say
completely eliminate, phytotoxic effects arising from
the use of various herbicides on crop plants. It is
thereby possible to use known herbicides selectively in
crops where use ~as not hitherto possible.
The agents according to the invention can be
appLied as ~ettable powders, emulsifiable concentrates,
solutions ~hich can be sprayed, dusting agents, dressing
agents, dispersions, granules or microgranules in the
usual formulations.
~ ettable po~ders are products wh;ch are uniformly
dispersible in ~ater and ~h;cho in addition to the active
substance and ~part from a diluent or inert substance,
if appropriate, also contain wetting agents, for example
polyoxyethylated alkylphenols, polyoxyethylated fatty
alcohols and ~lkyl- or alkylphenyl-sulfonates, and dis-
persing ~gents, for example sodium lignin-sulfonate~
sodiu~ 2,2'-dinaphthylmethane-6,6'-disulfona~e, sodium
dibutylnaphthaleneswlfonate or sodium oleyl-methyl-taur-
ide. ~hey are prepared in the customary manner, ~forexample by grinding and mixing the comPonents.
E~ulsifiable concentrates can be pr~pared~ for
example, by diss~lving the ac~ive substance ;n an inert
organic solvent, for example butanol, cyclohexanone,
dimethylfor0amide, xylene or higher-boiling aro~atics
or hydrocarbons, w;th the addition of one or mor~ emulsi-
fiers. In the cas@ of l;qu;d active subs~ances, all or
some of this solven~ content can also be dispensed with.
Examples of em~lsifiers which can be used: calcium alkyl-
-- 6 --arylsulfonat2s, such as Ca dodecylbenzenesulfonate, or
non-ionic e~ulsifiers, such as fatty acid polyglycol
esters, aLkylaryl polyglycol ethers, fatty alcohol poly-
glycol ethers, propyl2ne o~ide/ethylene oxide condens-
ation products, fatty alcohol/propylene oxide/ethyleneoxide condensation products, alkyl polyglycol ethers,
sorbitan fa~ty acid esters, polyoxyethyLene sorbitan
fatty acid esters or polyoxyethylene sorbi~ol esters~
Dusting agents can be obtained by grinding the
active substance with finely divided, solid substances,
for exa~ple ealc or natural clays, such as kaolin,
bentonite, pyrophiLite or diatomaceous earth.
Granules can be prepared either by spraying the
active substance onto adsorbent, granular inert material
or by applyiny active substance concentrates to the sur-
face of carriers, such as sand or kaolinites, or granular
inert material by means of binders, for example Polyvinyl
alcohol, sodium polyacrylate or mineral oils. Suitable
act;ve substances can al50 be granulated in the usual
~anner for the prepara~ion of fertilizer granules, if
desired mixed with fertilizers~
~ he active substance concentration in wettable
pouders is, tor ~xample, about 10 to 90X by ~eight~ the
remainder to ~ake up to 100X by ~eight consisein~ of the
usual formuLaeion constituents. The active substance
concen~ra~ion in emulsifiable concentrates can be about
10 to ~OX by ~ight. Dust-like formulations usually con-
tain 5 to 20~ by ~eight of active substance~ and solut;ons
~hich can be sprayed contain about 2 to 20X by ~eight.
The active substance content in granules parely depends
on whether the aceive compound is presen~ in li~uid or
solid for~ and ~hich granulaeion auxiliaries, fill2rs
and the like are used.
The active substance for~ulations mentioned also
contain, if appropriate, the particular customary ~acki-
fiers, ~etting agents, dispersing ayents~ e~ulsif;ers,
penetration agents, solvents~ fillers or carriers.
For use, the concentrates in the commercially
avaiLable form are diluted~ if appropria~e, in the cus-
~ >~ ~ g ~
-- 7 --tomary manner, ~or example by means of hater in the case
of wettable powders, emulsifiable concentrates, disper-
sions and somet;mes also microgranules. Dust-like and
granular formulations and solutions which can sprayed
are usually not further diluted with additional inert
substances before use.
Mixtures or mixed formulations with other act;ve
substances, such as, for example, insecticides, acari-
cides~ herbicides, fertili~ers, growth regulators or
fungicides, are also possible, where relevant.
Some formulation examples are described below:
Example A
_ _
A dust;ng agent is obtained by ~ixing 10 parts
by ~eight of active substance and 90parts by weight of
talc, as the ;nert substance, and comminut;ng the ~ix-
ture in an impact mill.
Example 3
A powder wh;ch is read;ly dispersible and ~et-
table in water is obtained by mixing ZS parts by weight
o~ active substance, ~4 parts by ~eight of kaolin-contain-
ing quartx, as ~he inert substance, 10 parts by weight
of potassium lignin-sulfonat~ and 1 part by ~eight of
sodium ol~yl-methyl t~uride, as the ~etting agent and
dispersing agent, and grinding the mixtur~ in a pinned
disc mill.
A dispersion concentration which is readily dis-
persi~le in water is obtained by mixing 20 parts by
~eight of active ~ubstance with 6 parts by ~eight of
alkylphenol polyglycol ether tTriton X 207), 3 parts by
~eight o~ isotridecanol polyglycol ether t8 moles of
ethylene oxide) and 71 parts by ~eight of paraffinic
mineral oil tboil;ng range, for example, about 255 to
above 377C), and grinding the ~ixture to a fineness of
less than S microns i~ a balL mill.
Example D
An emulsifiable concentrate ;s ob~ained trom 15
parts by ~eight of active substance, 75 parts by weight
of cyclohexanone9 as the solvent, and 10 parts by ~eight
~Z~7~
-- 8
of oxyethylated nonylphenol, as the emulsif;er.
A~ Preparation Exa~ples
xample 1
N-(2-[4-(2,4-Dichlorophenoxy)-phenoxy]-propionyl)-0-
methyl-isourea
6.2 9 (0.05 mole) of methylisourea sulfate are
dissolved in 50 ml of water and 100 ml of methylene chlor-
ide and the solution is cooled to 0C. At 0C, 8 9 of 50%
~trength aqueous sodium hydroxide solution (0.1 mole)
10 and 17.3 9 (O.OS ~ole) of 2-[4-(2,4-dichlorophenoxy)-
phenoxyJ-propionyl chloride, dissolved in sa ml of tolu-
ene, are simultaneously added dropwise. The mixture is
stirred at 0C for 1 hour and at 30C for 3 hours. The
organic phase is separ~ted off, washed with 100 ml of
water and dried over sodium sulfate. The solvent is dis-
tilled off under reduced pressure. 17.5 9 (95~ of theory)
of N-(2-t4-(2,4-dichlorophenoxy)-phenoxy]-propionyl)-0-
methyl-isourea are obtained as the residue in the form
of colorless crystals of melting point 9~-97C.
~0
Cl~ ~O-CH-C-N= -NH~
Example 2
N-~2-C4-t4-Chloroben2yl)-Phenoxy]-Propionyl)-0-methyl-
__
isourea
_._
6.2 g (0.05 ~ol~) of methylisourea sulfate are
25 dissoLved in 100 ml of methylene chLoride and 50 ml of
water at 0C. 15.4 g (O.OS mole) of 2-t4-(4-rhloro-
benzyl~-phenoxy] propionyl chloride, dissolved in 50 ml
of toluene, and 8 9 of SOZ strength aqueous sodium hy-
droxide solution (D.1 mole) are simultaneously ~dded
drop~ise. The mixture is stirred at 0C for 1 hour and
at 40C for 2 hours and the organic phase ;s separated
off. After drying over sod;um sulfate, the solvent is
distilled off under redured pressure. 13 g (75~ of
th~ory) of N-(~-t4-~4-chlorobenYyl)-phenoxy]-propionyl-
0-~ethyl-isourea are obtained in the form of a light
bro~n oil.
~2~
_ 9 _
t: 1~ CH 2 ~ O- CH-C-N=C -NH 2
O OC~ 3
E x a
N-(Z-t4 (~-Trifluoromethylphenoxy)-phenoxy]-propionyl)-
0-methyl-isourea
1Z.3 9 tO~1 mole) of methylisourea sul~ate are
dissolved ;n 80 ml of water and 150 mL of methylene chlor-
ide at 0C. 34.4 9 (0.1 mole) of 2-C4-(4-trifluoromethyl-
phenoxy)-phenoxy~-propionyl chloride, dissolved in 70 ml
of toLuene, and 16 9 of 50g strength aqueous sodium hyd-
1D roxide solution (0.2 mole) are simultaneously added drop-
~ise, ~hile cooling with ice~ The mixture is stirred
at 0C for 1 hour and at 40C for 3 hours and the organic
phase is separated off~ ~ashed with 200 ml of water and
dried over soclium sulfate. After the solvent has be~n
distilled off under reduced pressure, 35 9 (92% of theory)
of N-(2-~4-~4-trifluoromethylphenoxy)-phenoxy3-propionyl)-
0-methyl-isourea are obtained in the form of a yello~
o i ~ .
F 3 ~ ~ O-CH C-N=C-NH 2
O OC~ 3
t :~a~p~e 1
N-~2-C4-(6-Chlorobenzothiazol-2-yloxy) ~henoxy~-propionyl)-
O~methyl- _ourea_
12.3 9 (0.1 ~ole) of methylisourea sulfate are
dissolved in 80 ml of ~a~er and 150 ml of methylene
chloride at O~C. 36.7 g (0.1 mole) of ~t4-~6 chloro-
benzothiazol-2-ylo~y)-phenoxy3-propionyl chloride, dis-
soLved in 70 ml of toluene, and 16 g of ~0~ strength
aqueous sodium hydroxide solution ~0.2 moLe) are simul-
taneously added drop~ise at 0C, with vigorous stirring.
The mixture is stirred at 0C for 1 hour and at 40C
~or 2 hours. The precipitate ~hich has separated out is
Z~2~
- 10 -
filtered off ~ith suction and washed with 50 ml of ether.
27 9 of N-(2-[4-~6-chlorobenzothiazol-Z-yloxy)-phenoxy]-
propionyl)-O~methyl-isourea are obtained in the form of
colorless crystals of melting point 142C. The organic
phase is separated off from the mother liquor, washed
with 200 m! of ~ater and dried over sodium sulfate. After
the solvent has been distilled off under reduced pressure,
a light brown solid is obtained, which is bsiled up with
100 ml of e~her. After cooling, ~he solid is filtered
off ~ith suction to give a further 8.5 9 of N-(2-~4-(6-
chlorobenzothiazol-2-yloxy)-phenoxy]-propionyl)-0-methyl-
isourea in the form of colorless crystals of melting
point 141-142C. Total yield: 35.5 9 ~88X of theory).
O'`~)-O~CH~-N=~-~H 2
The follo~ing compounds listed in Table 1 can
be obtained in ~n analogous manner.
Table 1
R1-X ~ o-8H-C-N=C-N
~R2
__ ___ ~__ ___ _
_- Boiling point
~NxOample IFI.l X Y R~ R~ Rd ~lting point
__ ~ __ . ~- __ _~
S ! 1~ O O OH3 ~H 11
i!i n O O C2Hs H
7 n O S CH3 H H
8 C~ O S C~13 ~1 ~1
Table 1 ( cont inued)
___ __ _ _ _~
ExarnpleR' X ~! R2 R~ R~ (C)
' _ __ __ _ ___ _ _
9 F 9 C n C1 O S) ~ 2H3 ~H H
F3C ~ O O CH3 H H
11 Cl Cl O O CH3 H H
1 2 ~ O O CH 3 H ~1
13 ~ O O CH 3 ~I H
Cl
4 ~ O O C2H5 lI ~I
E~r
1 5 Cl~l O O C ~H 5 }I H
'l 6 C:l~ O S CH3 H
17 F 3 C ~ -CH 2 ~ -NH CH, }I
18 F ~ O O CH3 H H
19 F ~7 O O CH, H H
- 12 -
Example 20
N-(2-t4-(2,~-Dichlorophenoxy)-phenoxy]-propionyl)-N'-
dimethylaminomethylene-0-methyL-isourea
__ _
19.2 9 (0.05 mole) of N-(2-[4-(2,4-dichlorophen-
oxy)-phenoxy]-propionyl)-0-methyl-isourea ~Example 1)
and 9 9 (0.06 mole~ of dimethylfrJrmamide diethyl acetal
are mixed ~ith one another. After addition of 1/~ ml
of concentrated sulfuric acid, the mixture is heated
rapidly to 100CO It is stirred at 100C for 3 m;nutes
and allowed to cool to room temperature. The resulting
light brown oil is freed from all the volatile consti~u-
ents under an oil pump at 60-70C/0.01 bar. 19.5 9 (88%
of theory) of N-(2-t4-(2~4-dichlorophenoxy)-phenoxy]-
propionyl)-N'-dimethylaminomethylene-0-methyl-isourea
are obtained in the form of a light bro~n viscous oil.
Cl
Cl ~ O ~ H-C-N=C N=CH-N ~
O C~3 ~ CH 3
The following compvunds listed in Table 2 can
be prepared in an analogous manner.
Table 2
__
Rl~-X~ ~R~
, . ~ __ . . . _ ,, ,
EX- 2 Boiling point
I~O.le Rl X Y R meOting point
~ ~ - - - ~ -
21 F3C~ O O C~3
2 2 ~ CH a O CH J
;2 3 Cl~ O ~; CH3 . . .
~z~
13 -
T a b l e 2 t c o n t i n u e d )
_ _ Boiling point
E~)le R ~ X Y R 2 ( t' ) ' nD
r Br ___~_
24 1:1~ O O ~
Cl~ O O ~ 2H 5
N
26 C~S~ O O CH3
2 7 C~ O O CH 3
28 ~ O O CH3
- 14 -
B. ~iolog;cal ExamPles
1. Herbicidal action
The present compounds according to the invention
exhibit a good herbicidal activity against a broad spec-
trum of economically ;mpor~ant monocotyledonous and di-
coeyledonous harmful plants. The active substances also
have a good action against perennial species which are
difficult to combat. It is irrelevant here whether the
su~stances are applied by pre-sow;ng, pre-emergence or
1D post-emergence spraying. If the compounds according to
the invention are applied to the soil surface by the pre-
so~ing or pre-emergence method befors germination of the
~eeds, the emergence of seedlings is not completely pre-
vented. The weeds grow to the cotyledon stage, but their
growth then stops and they finally die completely after
3-S weeks.
~ hen the active substances are applied to the
green parts of plants by the post-emergence ~ethod, a
drastic stop to gro~th likewise occurs very rap;dly after
the treatment and the ~eeds remain at the gro~h stage
of the time of application or die rompletely after a
certain period, so that ~eed competition, wh;ch is harm-
ful to the crop plants, can in this ~ay be eliminated
very early and permanently by using the nov~l agents
according to the invention. Although the compounds
acçording to the invention also exhibit an excellen~
herbicidal ~ctivity, ~specially a~ainst monocotyledon-
ous ~eeds, plants in ~conomically important crops9 such
as, for example, ~heat, barley~ rye, rice~ maize, sugar
~eet, cotton and soybean, are damaged only partly or in
significantly, or not at all. Compared with the prior
art, the present substances according to the invention
therefore have a substantialLy improved selectiYity to-
~ards crop plants. For these reasons, the present com-
pounds are particularly suitable for co~bating undesir-
able plant gro~th in agricultural~y useful pl~nts. The
damage to the ~eeds and the tol~rance by the crsP plants
has been rated ;n a key ~rom 0 to 5.
In this key:
~z~
-- 15 -
0 = no action ~damage)
1 = 0 - 20% act;on
2 = 20 - 40% ac~ion
3 = 40 - 60% action
4 = 60 - 80X action
5 = 80 - 100% action.
a) Action against weeds
Seeds of monocotyLedonous and dicotyledonous
~eeds ~ere placed in loam soil in plastic pots ( 9 cm)
and covered with soil. The compounds according to the
invention, formulated as we~tabLe powders or as e~ulsion
concentrates, ~ere sprayed onto the soiL surface ~pre-
emergence method) or onto the pLants which had developed
to the 4-leaf stage (post-emergence method) in the form
of aqueous suspensions or emulsions. The amount of water
appLied per pot corresponded, ~hen converted, to 60n liters/
ha~ After the treatment, the test pots ~ere placed in
a greenhouse and the test pLants were gro~n under good
growing conditions (temperature: 23 ~ 1C; relative
atmospheric humidity 60-B0%). After aboue 3 ~eeks, the
damage to the ~Lants was rated visually. Untreated con-
~rols were used for comparison.
As can be seen from thQ values in Tables 3 and
4, the compounds according to the invention exhibi~ a
Z5 very ~ood herbicidal activity against economically impor-
tan~ monocotyLedonous and dicotyl~donous harmful plants
when applied by the pr~-~mergence or ~ost-emergence method.
Table 3
Herbicidal ~ctivity in the pr~emer~ence method
___ __ _~_ __
Example No! EC6 L~M ALM STM
_________ __ ___
1 2 .b 5 S _ 4
~ 0.~ 5 5 3
2 ~.4 ~ 5 5
2 0"6 S 5 ~ 4
3 2.~ 5 5 5 5
3 0.6 5 ~!i 5
~ __ __ __ _ _
~r
,~;29L;Z~t~ %
- 16 -
ECG = Echinochloa crus gall;
LOM = Lolium multiflorum
ALM = Alopecurus myosuroides
STM = St~llaria media
Selectivity
Compounds 1, 2~ 3 and ~ according to the inven-
tion are comple~ely ~olerated by soybean, cotton and
sugar beet crop plan~s and other dicotyledonous crop
plants, ~ithout a harmful effece being observed, ~hen
1û applied in amounts of 2.4 kg of active substance. Com-
pounds 1, ~ and 2 are also completely selective in cereal
varieties (wheat and rice).
Table 4
_ .
Herbicidal activity by the post-emergence method
_, _ _ _ __
Exsmple Nol EC6 LOM AL~
_ ___ __
1 24 5 5
L~
2. ~
~ ane sugar plants ~re grown under greenhouse
condi~ions at 25-35~C and about 65% atmospheric humidity.
Various amounts of the formuLated agents were suspended
in water, ~hich addi~iQnally ~oneained about 0.25X by
~eighe o~ a surface-active agent (nonylphenol).
In each case û.~ ml of ~he suspensions ~ere
7'~2
~ f.o
- 17 -
applied ~ith the aid of a syringe in the sp;ndle region
at ~he height of last visible leaf blade ("dewlap") (10
plants per test group). The plants ~ere 6 months old
at the time of application.
After 5 ~eeks, the Plants were harvested~ the
foliage was re~oved and the 14 upper internodes ~ere
analyzed ;n each case together in groups for sucrose con-
Sent and juice purity by means of the so-called "press
method" (T. Tanimoto, Hawaiin Planters Record, 57, 133
~1964]).
The sugar content here is determined polarimet-
rically and expressed in "pol~ percentage of cane"; this
figure corresponds to the percentage of sucrose in the
solution, under the assumption that sucrose is the only
substance in the sugar soLution ~hich rotates the plane
of polarized light. The determination of the "pol. per-
centage of cane" ;s a recognized method for determin;ng
the sugar content of sugar cane~
The results are shown ;n Table S.
Table S
___, __
~ount oppli~d Ju;ce putity Sucro~e content
~/pl~nt) (X) ~pol. X r~ne)
~__ _ __ __
Control ~.8 ~.9
~ample 3 10 75 11.5
'?4 1 1 n2
Ex~ple 4 10 72 lû.2
71 10.1
