Note: Descriptions are shown in the official language in which they were submitted.
WO 2017/140612 CA 03014687 2018-08-15
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Quinazolinedione-6-carbonyl derivatives and their use as herbicides
The invention relates to the technical field of the herbicides, especially
that of the herbicides for
selective control of weeds and weed grasses in crops of useful plants.
WO 2015/058519 Al describes quinazolinedione-6-carbonylcyclohexanediones as
herbicides. However,
the compounds known from these documents do not always have adequate
herbicidal efficacy and/or
compatibility with crop plants.
It has now been found that quinazolinedione-6-carbonyl derivatives which
differ from the compounds
known from the prior art in that they bear other cyclohexanedione radicals
than those described in WO
2015/058519 Al are of particularly good suitability as herbicides.
The present invention thus provides quinazolinedione-6-carbonyl derivatives of
the formula (1) and salts
thereof
0 x (:)
,R'
(I),
N'Z
in which
X is nitro, halogen, cyano, formyl, thiocyanato, (C1-C6)-alkyl, (C1-C6)-
haloalkyl, (C2-C6)-alkenyl,
(C2-C6)-haloalkenyl, (C2-C6)-alkynyl, (C3-C6)-haloalkynyl, (C3-C6)-cycloalkyl,
(C3-C6)-halocycloalkyl,
(C3-C6)-cycloalkyl-(CI-C6)-alkyl, (C3-C6)-halocycloalkyl-(CI-C6)-alkyl, COW,
OR', CORI, 0S02R2,
S(0)R2, SO2OR', SO2N(102, NRISO2R2, NRICORI, (C ,-C6)-alkyl-S(0)R2, (CI-C6)-
alkyl-OR', (Cr
C6)-alkyl-OCOR1, (CI-C6)-alkyl-OSO2R2, (CI-C6)-alkyl-COORI, (Ci-C6)-alkyl-
S020R1, (CI-C6)-alkyl-
CON(R')2, (CI-C6)-alkyl-SO2N(R1)2, (CI-C6)-alkyl-NRICOR', (CI-C6)-alkyl-
NWSO2R2 or NR' R2,
Z is Oor S,
W is hydrogen, nitro, halogen, cyano, (CI-CO-alkyl, (CI-CO-haloalkyl or
(C1-C4)-alkoxY,
RI is (CI-CIO-alkyl, (C2-Cl0)-alkenyl, (C2-C10)-alkynyl, halo-(C1-C10)-
alkyl, halo-(C2-C10)-alkenyl,
halo-(C2-Cl0)-alkynyl, (C3-Cio)-cycloalkyl, halo-(C3-Cio)-cycloalkyl, (CI-C4)-
alkyl-(C3-C7)-cycloalkyl,
(C3-C7)-cycloalkyl-(CI-C6)-alkyl, (C3-C7)-cycloalkyl-(C3-C7)-cycloalkyl, halo-
(C3-C7)-cycloalkyl-(CI-
C6)-alkyl, (C3-C12)-cycloalkenyl, halo-(C3-
Ci2)-
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cycloalkenyl, (CI-C6)-alkoxy-(C1-C6)-alkyl, (C1-C6)-alkoxy-(C2-C6)-alkenyl,
(C1-C6)-alkyl-(C3-C7)-
cycloalkyl, (C1-C6)-alkoxy-(C3-C7)-cycloalkyl, di-(C1-C6)-alkoxy-(C3-C7)-
cycloalkyl, (C3-C7)-
cycloalkoxy-(CI-C6)-alkyl, (C3-C7)-cycloalkoxy-(C1-C6)-alkoxy-(C1-C6)-alkyl,
(C1-C6)-alkoxy-(C1-C6)-
alkoxy-(C1-C6)-alkyl, (C1-C6)-alkylthio-(C1-C6)-alkyl, (C1-C6)-alkylsulfinyl-
(C1-C6)-alkyl, (C1-Co)-
alkylsulfonyl-(C1-C6)-alkyl, (C1-C6)-allcylamino.-(CI-C6)-alkyl, di-(C1-C6)-
alkylamino-(C1-C6)-alkyl,
halo-(C1-C6)-alkylamino-(Ci-C6)-alkyl, (C3-C7)-cycloalkylamino-(C1-C6)-alkyl,
(C1-C6)-alkylcarbonyl,
halo-(C1-C6)-alkylcarbonyl, (C3-C7)-cycloalkylcarbonyl, (C1-C6)-
alkoxycarbonyl, (C3-C7)-
cycloalkoxycarbonyl, (C3-C7)-cycloalkyl-(C1-C6)-alkoxycarbonyl, (C1-C6)-
alkylaminocarbonyl, di-(CI-
C6)-alkylaminocarbonyl, (C3-C7)-cycloalkylaminocarbonyl, cyano-(C1-C6)-alkyl,
hydroxy-(C1-C6)-alkyl,
(C3-C7)-cycloalkenyl-(C1-C6)-alkyl, halo-(C1-C6)-alkoxy-(Ci-C6)-alkyl, (C1-C6)-
alkoxyhalo-(C1-C6)-
alkyl, halo-(CI-C6)-alkoxyhalo-(C1-C6)-alkyl, halo-(C3-C7)-cycloalkoxy-(C1-C6)-
alkyl, (C3-C7)-
cycloalkenyloxy-(C1-C6)-alkyl, halo-(C3-C7)-cycloalkenyloxy-(C1-C6)-alkyl, di-
(C1-C6)-alkoxy-(C1-C6)-
alkyl, (Ci-C6)-alkoxy-(C1-C6)-alkylcarbonyl, (CI-C6)-alkoxycarbonyl-(C1-C6)-
alkyl, halo-(C1-C6)-
alkoxycarbonyl, (C1-C10)-alkoxy, halo-(C1-C10)-alkoxy, (C3-C12)-cycloalkoxy,
halo-(C3-C7)-cycloalkoxy,
(C3-C7)-cycloalkyl-(C1-C6)-alkoxy, (C2-C12)-alkenyloxy, halo-(C2-C10)-
alkenyloxy, (C2-C10)-alkynyloxy,
halo-(C3-C10)-alkynyloxy, (CI-C6)-alkoxy-(C1-C6)-alkoxy, (Ci-C6)-
alkylcarbonyloxy, halo-(C2-C12)-
alkylcarbonyloxy, (C3-C7)-cycloalkylcarbonyloxy, (C1-C6)-alkylcarbonyl-(C1-C6)-
alkoxy, (C1-C6)-
alkylamino, di-(C1-C6)-alkylamino, halo-(C1-C6)-allcylamino, halodi-(Ci-C6)-
alkylamino, (C3-C12)-
cycloalkylamino, (Ci-C6)-allcylcarbonylamino, halo-(Ci-C6)-alkylcarbonylamino,
(C1-Cso)-
alkylsulfonylamino, halo-(C1-C10)-alkylsulfonylamino, (C3-C7)-cycloalkyl-(C1-
C6)-alkylamino,
hydroxyl, amino, NHCHO, or
R' is phenyl, phenylsulfonyl, W'-(phenyl), V-(0-phenyl), W'-(S-phenyl),
W1-(S02-phenyl), W2-
(SO2CH2-phenyl) or W2-(SCH2-phenyl), where the phenyl rings of the eight
aforementioned radicals
each bear s R3 substituents,
R2 is hydrogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C2-C6)-alkenyl, (C2-
C6)-haloalkenyl, (C2-C6)-
allcynyl, (C2-C6)-haloalkynyl, (C3-C6)-cycloalkyl, (C3-C6)-halocycloalkyl, (CI-
C6)-alky1-0-(C1-C6)-alkyl,
(C3-C6)-cycloalkyl-(C1-C6)-alkyl, phenyl, phenyl-(C1-C6)-alkyl, pyridyl or (C1-
C6)-alkylpyridyl, where
the phenyl or pyridyl rings of the four aforementioned radicals each bear s R3
substituents,
Q is a Q1, Q2, Q3, Q4 or Q5 radical,
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0 0 RP3
Re2
3 RC 2 Rnk 0
Rc
= ="
Rn1
RC4RC1 R R ORP
RP2
C5 Rn2 ON
P4
Qi Q2 Q3 Q4 Q6
Rd l is hydroxyl or SR4,
Re2, le, Ft'', Rc5, Rc6 and le are each independently hydrogen or (C1-C4)-
alkyl,
RP' is hydrogen, (C1-C6)-alkylsulfonyl, (C1-C4)-alkoxy-(C1-C6)-
alkylsulfonyl, or phenylsulfonyl,
thiopheny1-2-sulfonyl, benzoyl, benzoy1-(CI-C6)-alkyl or benzyl, each of which
is substituted by n
identical or different radicals from the group consisting of halogen, (C1-C4)-
alkyl and (C1-C4)-alkoxy,
RP2 is (C1-C4)-alkyl,
RP3 is hydrogen, (C1-C4)-alkyl, (C3-C8)-cycloalkyl, (C1-C4)-alkyl-
(C3-C8)-cycloalkyl or (C3-C6)-
halocycloalkyl,
RP' is (C1-C4)-alkyl, (C3-C8)-cycloalkyl, (C1-C4)-alkyl-(C3-C8)-
cycloalkyl or (C3-C6)-halocycloalkyl,
RP' is hydrogen, CO2(C1-C6)-alkyl or S(0).(CI-C6)-alkyl,
Y is 0 or CO,
Y1 is an ethylene or vinylene group,
Y2 is 0, CO or CH2,
W' is (CI-C10)-alkylene, (C2-C6)-alkenylene or (C2-C6)-alkynylene,
W2 is (C1-C10)-alkylene,
R3 is halogen, cyano, hydroxyl, amino, nitro, -C(=0)R3a, -
C(=0)0R38
,
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-C(=0)(NR3a)2, -C(=S)NH2, -C(=0)NHCN, -C(=0)NHOH, -SH, -S02(NR38)2, -SO2NHCN, -
SO2NHOH,
-OCN, -SCN, -SF5, (C1-C6)-alkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, halo-(CI-
C6)-alkyl, halo-(C2-C6)-
alkenyl, halo-(C2-C6)-alkynyl, (C3-C8)-cycloalkyl, halo-(C3-C8)-cycloallcyl,
(CI-C6)-alkyl-(C3-C7)-
cycloalkyl, (C3-C7)-cycloalkyl-(CI-C6)-alkyl, (C3-C8)-cycloalkenyl, halo-(C3-
C8)-cycloalkenyl,
alkoxy-(C1-C6)-alkyl, (C3-C7)-cycloalkoxy-(CI-C6)-alkyl, (Ci-C6)-alkoxy-(C1-
C6)-alkoxy-(CI-C6)-alkyl,
(CI-C6)-alkylthio-(C1-C6)-alkyl, (CI-C8)-alkylsulfinyl-(CI-C6)-alkyl, (CI-C8)-
alkoxyhalo-(C1-C6)-alkyl,
cyano-(CI-C6)-alkyl, hydroxy-(CI-C6)-alkyl, (CI-C6)-alkoxy, halo-(CI-C6)-
alkoxy, (C3-C8)-cycloalkoxy,
halo-(C3-C8)-cycloalkoxy, (C3-C8)-cycloalkyl-(Ci-C6)-alkoxy, (C2-C6)-
alkenyloxy, halo-(C2-C6)-
alkenyloxy, (CI-C6)-alkoxy-(Ci-C6)-alkoxy, (C2-C6)-alkylcarbonyloxy, (Ci-C6)-
alkylthio, halo-(CI-C6)-
alkylthio, (C3-C8)-cycloalkylthio, (CI-C6)-alkylsulfinyl, halo-(C1-C6)-
alkylsulfinyl, (C1-C6)-
alkylsulfonyl, halo-(Ci-C6)-alkylsulfonyl, (C3-C8)-cycloalkylsulfonyl, (CI-C6)-
alkylamino,
halo-(CI-C6)-alkylamino, halodi-(Ci-C8)-alkylamino or (C3-C8)-cycloalkylamino,
or
two vicinal R3 radicals together with the two carbon atoms to which they are
bonded form a 5- to 7-
membered ring which contains v carbon atoms and p identical or different atoms
from the group of
oxygen, sulfur and nitrogen, and bears t oxo groups,
R3a is hydrogen, (CI-C6)-alkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, (C3-C6)-
cycloalkyl, (C3-C6)-
cycloalkyl-(CI-C6)-alkyl or phenyl,
R4 is (CI-C4)-alkyl, or phenyl substituted by p radicals from the group of
halogen, nitro, cyano, (CI-
C4)-alkyl, (CI-C4)-haloalkyl, (CI-C4)-alkoxy and (CI-C4)-haloalkoxy,
n is 0, 1 or 2,
p is 0, 1, 2, 3 or 4,
s is 0, 1, 2,3,4 or 5,
t is 0, 1, 2, 3 or 4,
v is 2,3, 4, 5, 6 or 7.
In the formula (I) and all the formulae which follow, alkyl radicals having
more than two carbon atoms
may be straight-chain or branched. Alkyl radicals are, for example, methyl,
ethyl, n-propyl or isopropyl,
n-, iso-, t- or 2-butyl, pentyls, hexyls such as n-hexyl, isohexyl and 1,3-
dimethylbutyl. Analogously,
alkenyl is, for example, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-
yl, but-2-en-l-yl, but-3-en-
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1-yl, 1-methylbut-3-en-1-y1 and 1-methylbut-2-en-l-yl. Alkynyl is, for
example, propargyl, but-2-yn-l-
yl, but-3-yn-l-yl, 1-methylbut-3-yn-l-yl. The multiple bond may be in any
position in each unsaturated
radical. Cycloalkyl is a carbocyclic saturated ring system having three to six
carbon atoms, for example
cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Analogously, cycloalkenyl
is a monocyclic alkenyl
5 group having three to six carbon ring members, for example cyclopropenyl,
cyclobutenyl, cyclopentenyl
and cyclohexenyl, where the double bond may be in any position. (C1-C10)-
Alkylene is correspondingly
a methylene group, an ethylene group, or a propylene, butylene, pentylene,
hexylene, heptylene,
octylene, nonylene or decylene group, in each case unbranched.
Halogen is fluorine, chlorine, bromine or iodine.
If a group is polysubstituted by radicals, this should be understood to mean
that this group is substituted
by one or more identical or different radicals selected from the radicals
mentioned. The same applies to
the formation of ring systems by different atoms and elements. At the same
time, the scope of the claims
shall exclude those compounds known by the person skilled in the art to be
chemically unstable under
standard conditions.
Depending on the nature of the substituents and the manner in which they are
attached, the compounds
of the general formula (I) may be present as stereoisomers. If, for example,
one or more asymmetric
carbon atoms are present, enantiomers and diastereomers may occur.
Stereoisomers likewise occur when
n is 1 (sulfoxides). Stereoisomers can be obtained from the mixtures obtained
in the preparation by
customary separation methods, for example by chromatographic separation
processes. It is likewise
possible to selectively prepare stereoisomers by using stereoselective
reactions with use of optically
active starting materials and/or auxiliaries. The invention also relates to
all the stereoisomers and
mixtures thereof that are encompassed by the general formula (I) but are not
defined specifically. Owing
to the oxime ether structure, the compounds of the invention may also occur as
geometric isomers (E/Z
isomers). The invention also relates to all the E/Z isomers and mixtures
thereof that are encompassed by
the general formula (I) but are not defined specifically.
The compounds of the formula (I) are capable of forming salts. Suitable bases
are, for example, organic
amines, such as trialkylamines, morpholine, piperidine or pyridine, and also
ammonium, alkali metal or
alkaline earth metal hydroxides, carbonates and hydrogencarbonates, especially
sodium hydroxide and
potassium hydroxide, sodium carbonate and potassium carbonate and sodium
hydrogencarbonate and
potassium hydrogencarbonate. These salts are compounds in which the acidic
hydrogen is replaced by
an agriculturally suitable cation, for example metal salts, especially alkali
metal salts or alkaline earth
metal salts, in particular sodium and potassium salts, or else ammonium salts,
salts with organic amines
or quaternary ammonium salts, for example with cations of the formula [NRR'R¨R-
1 in which R to
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R" each independently of one another represent an organic radical, in
particular alkyl, aryl, aralkyl or
allcylaryl. Also suitable are alkylsulfonium and alkylsulfoxonium salts, such
as (CI-C4)-
triallcylsulfonium and (CI-C4)-trialkylsulfoxonium salts.
The compounds of the formula (I) can form salts through adduct formation of a
suitable inorganic or
organic acid, for example mineral acids such as HC1, HBr, H2SO4, H3PO4 or
HNO3, or organic acids, for
example carboxylic acids such as formic acid, acetic acid, propionic acid,
oxalic acid, lactic acid or
salicylic acid or sulfonic acids such as p-toluenesulfonic acid, with a basic
group such as amino,
allcylamino, dialkylamino, piperidino, morpholino or pyridino. In such a case,
these salts will comprise
the conjugate base of the acid as the anion.
Preference is given to compounds of the general formula (I) in which
X is halogen, (CI-C6)-alkyl, (CI-C6)-haloalkyl, (C2-C6)-alkenyl, (C3-
C6)-cycloalkyl, (C3-C6)-
halocycloalkyl, OR', S(0)R2, SO2N(R1)2, NR'SO2R2, NRICORI, (C1-C6)-alkyl-
S(0)õR2 or (CI-C6)-
alkyl-OR',
Z is 0,
W is hydrogen, Cl, Me0, methyl or ethyl,
RI is (CI-CIO-alkyl, (C2-C10)-alkenyl, (C2-Clo)-alkynyl, halo-(CI-C10)-
alkyl, halo-(C2-Cio)-alkenyl,
halo-(C2-C10)-alkynyl, (C3-CO-cycloalkyl, halo-(C3-C10)-cycloalkyl, (CI-C4)-
alkyl-(C3-C7)-cycloalkyl,
(C3-C7)-cycloalkyl-(CI-C6)-alkyl, (Ci-C6)-alkoxy-(CI-C6)-alkyl, (CI-C6)-alkyl-
(C3-C7)-cycloalkyl, (C1-
C6)-alkylthio-(CI-C6)-alkyl, (Ci-C6)-alkylsulfinyl-(C1-C6)-alkyl, (CI-C6)-
alkylsulfonyl-(C1-C6)-alkyl,
cyano-(C1-C6)-alkyl, (CI-C10)-alkoxy, halo-(CI-Clo)-alkoxy, (CI-C6)-alkoxy-(C1-
C6)-alkoxy, (Ci-C6)-
alkylamino or di-(CI-C6)-alkylamino,
RI is phenyl bearing s R3 substituents,
R2 is (CI-C4)-alkyl,
is a Q', Q2, Q2, Q4 or Q5 radical,
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7
0 0 RP3
Rc2
Re3 IRC2 1 Y / =
1\1\' I Rni
0
ni 0 R1' =
R
R (\Z c4 Rn5 Rp2
Rn2 CN
Qi Q2 Q3 Q4 Q5
Rd 1 is hydroxyl,
Rc2, Ro, Rc45 -c5,
K Re6 and Rd2 are each independently hydrogen or methyl,
RP' is hydrogen,
RP2 is (C1-C4)-alkyl,
RP3 is hydrogen, (C1-C4)-alkyl or cyclopropyl,
is cyclopropyl,
Rn2 is hydrogen,
Y is 0 or CO,
Y1 is an ethylene or vinylene group,
Y2 is CH2,
R3 is halogen, cyano, hydroxyl, amino, nitro, -C(=0)R38, C(---
0)0R3a,
-C(=0)(NR3a)2, -C(=S)NH2, -C(=0)NHCN, -C(=0)NHOH, -SH, -SO2NH2, -SO2NHCN,
-SO2NHOH, -OCN, -SCN, -SF5, (C1-C6)-alkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl,
halo-(C1-C6)-alkyl, halo-(C2-C6)-alkenyl, halo-(C2-C6)-alkynyl, (C3-C8)-
cycloalkyl, halo-(C3-C8)-
cycloalkyl, (C1-C6)-alkyl-(C3-C7)-cycloalkyl, (C3-C7)-cycloalkyl-(C1-C6)-
alkyl, (C3-C8)-cycloalkenyl,
halo-(C3-C8)-cycloalkenyl, (CI-C6)-alkoxy-(C1-C6)-alkyl, (C3-C7)-cycloalkoxy-
(C1-C6)-alkyl, (C1-C6)-
alkoxy-(C1-C6)-alkoxy-(Ci-C6)-alkyl, (CI-C6)-alkylthio-(C1-C6)-alkyl, (C1-C8)-
alkylsulfinyl-(C1-C6)-
alkyl, (C1-C8)-alkoxyhalo-(C1-C6)-alkyl, cyano-(C1-C6)-alkyl, hydroxy-(C1-C6)-
alkyl, (C1-C6)-alkoxy,
halo-(C1-C6)-alkoxy, (C3-C8)-cycloalkoxy, halo-(C3-C8)-cycloalkoxy, (C3-C8)-
cycloalkyl-(C1-C6)-
alkoxy, (C2-C6)-alkenyloxy, halo-(C2-C6)-alkenyloxy, (C1-C6)-alkoxy-(Ci-C6)-
alkoxy, (C2-C6)-
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alkylcarbonyloxy, (C1-C6)-alkylthio, halo-(C1-C6)-alkylthio, (C3-C8)-
cycloalkylthio, (C1-C6)-
alkylsulfinyl, halo-(C1-C6)-allcylsulfinyl, (C1-C6)-alkylsulfonyl, halo-(C1-
C6)-alkylsulfonyl, (C3-C8)-
cycloalkylsulfonyl, (CI-C6)-alkylamino, di-(C1-C6)-alkylamino, halo-(C1-C6)-
alkylamino, halodi-(Ci-
C8)-alkylamino, (C3-C8)-cycloalkylamino or methylenedioxo,
R3a is hydrogen or (C1-C6)-alkyl,
n is 0, 1 or 2,
s 1s0, 1,2,3,4or5.
Particular preference is given to compounds of the general formula (I) in
which
X is F, Cl, Br, methyl, ethyl, cyclopropyl, trifluoromethyl, methoxy,
methoxymethyl,
IS methoxyethoxymethyl, SMe or SO2Me,
Z is 0,
W is hydrogen,
RI is (C1-C10)-alkyl, (C2-C10)-alkenyl, (C2-C10)-alkynyl, halo-(C1-C10)-
alkyl, halo-(C2-C10)-alkenyl,
halo-(C2-C10)-alkynyl, (C3-C10)-cycloalkyl, halo-(C3-C10)-cycloalkyl, (CI-C4)-
alkyl-(C3-C7)-cycloalkyl,
(C3-C7)-cycloalkyl-(C1-C6)-alkyl, (C1-C6)-alkoxy-(Ci-C6)-alkyl, (C1-C6)-alkyl-
(C3-C7)-cycloalkyl, (CI-
C6)-alkylthio-(C1-C6)-alkyl, (C1-C6)-allcylsulfinyl-(C1-C6)-alkyl, (C1-C6)-
alkylsulfonyl-(C1-C6)-alkyl, or
RI is phenyl bearing s R3 substituents,
R2 is methyl or ethyl,
Q is a Q1, Q2, Q3, Q4 or Q5 radical,
0 0 RP3
170
Fe\
Rni) 0
Rc3 NY2
N\ I
n
, 0
R
Y)(FRci Rci ORP'N
RP2 R
e5 CN
Rc4 Rn2
Q1 Q2 03 Q4 05
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Rd is hydroxyl,
Rc2, Rc3, Rc4, RCS, --co
K and Re' are each independently hydrogen or methyl,
RP' is hydrogen,
RP2 is (C1-C4)-alkyl,
RP3 is hydrogen, (C1-C4)-alkyl or cyclopropyl,
R' is cyclopropyl,
Rn2 is hydrogen,
Y is 0 or CO,
Y' is an ethylene or vinylene group,
Y2 is CH2,
R3 is halogen, cyano, nitro, (C1-C6)-alkyl, (C2-C6)-alkenyl, (C2-C6)-
alkynyl,
halo-(C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C1-C6)-alkoxy, halo-(Ci-C6)-alkoxy,
(C1-C6)-alkoxy-(Ct-C6)-
alkyl, (C1-C6)-alkylthio, (C1-C6)-alkylsulfinyl, (CI-C6)-alkylsulfonyl, phenyl
or methylenedioxo,
s is 0, 1, 2, 3, 4 or 5.
In all the formulae specified hereinafter, the substituents and symbols have
the same meaning as
described in formula (1), unless defined differently.
Inventive compounds with Q = Q1, Q2, Q3, Q4 or Q5 can be prepared, for
example, inter alia, according
to Scheme 1 analogously to the methods cited in WO 2009/018925 Al.
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Scheme 1
0 X 0 0 X 0
Ri Ri
N.-
HO CI
(III)
(II)
R2 R2
./Q-H
0 X 0
R1
I Ii (1)
/112
The quinazolinedione-6-carbonyl chlorides (II) and their parent
quinazolinedione-6-carboxylic acids
(III) can be prepared, for example, by the methods described in W02015058519.
5
It may be appropriate to alter the sequence of the reaction steps. For
instance, benzoic acids bearing a
sulfoxide cannot be converted directly to their acid chlorides. One option
here is first to prepare the
= amide at the thioether stage, and then to oxidize the thioether to the
sulfoxide.
10 Collections of compounds of the formula (I) and/or salts thereof which
can be synthesized by the
abovementioned reactions can also be prepared in a parallelized manner, in
which case this may be
accomplished in a manual, partly automated or fully automated manner. It is
possible, for example, to
automate the conduct of the reaction, the workup or the purification of the
products and/or
intermediates. Overall, this is understood to mean a procedure as described,
for example, by D. Tiebes in
= 15 Combinatorial Chemistry ¨ Synthesis, Analysis, Screening (editor:
Gunther Jung), Wiley, 1999, on
pages 1 to 34.
For the parallelized conduct of the reaction and workup, it is possible to use
a number of commercially
available instruments, for example Calypso reaction blocks from Barnstead
International, Dubuque,
Iowa 52004-0797, USA or reaction stations from Radleys, Shirehill, Saffron
Walden, Essex, CBI 1 3AZ,
England, or MultiPROBE Automated Workstations from Perkin Elmer, Waltham,
Massachusetts 02451,
USA. For the parallelized purification of compounds of the general formula (I)
and salts thereof or of
intermediates which occur in the course of preparation, available apparatuses
include chromatography
apparatuses, for example from ISCO, Inc., 4700 Superior Street, Lincoln, NE
68504, USA.
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The apparatuses detailed lead to a modular procedure in which the individual
working steps are
automated, but manual operations have to be carried out between the working
steps. This can be
circumvented by using partly or fully integrated automation systems in which
the respective automation
modules are operated, for example, by robots. Automation systems of this type
can be obtained, for
example, from Caliper, Hopkinton, MA 01748, USA.
The implementation of single or multiple synthesis steps can be supported by
the use of polymer-
supported reagents/scavenger resins. The specialist literature describes a
series of experimental
protocols, for example in ChemFiles, Vol. 4, No. 1, Polymer-Supported
Scavengers and Reagents for
Solution-Phase Synthesis (Sigma-Aldrich).
Aside from the methods described here, compounds of the general formula (I)
and salts thereof can be
prepared completely or partially by solid-phase-supported methods. For this
purpose, individual
intermediates or all intermediates in the synthesis or a synthesis adapted for
the corresponding procedure
are bound to a synthesis resin. Solid-phase-supported synthesis methods are
described adequately in the
technical literature, for example Barry A. Bunin in "The Combinatorial Index",
Academic Press, 1998
and Combinatorial Chemistry ¨ Synthesis, Analysis, Screening (editor: Gunther
Jung), Wiley, 1999. The
use of solid-phase-supported synthesis methods permits a number of protocols,
which are known from
the literature and which for their part may be performed manually or in an
automated manner. The
reactions can be performed, for example, by means of IRORI technology in
microreactors from Nexus
Biosystems, 12140 Community Road, Poway, CA92064, USA.
Both in the solid and in the liquid phase, the implementation of individual or
several synthesis steps may
be supported by the use of microwave technology. The specialist literature
describes a series of
experimental protocols, for example in Microwaves in Organic and Medicinal
Chemistry (editor: C. 0.
Kappe and A. Stadler), Wiley, 2005.
The preparation by the processes described here gives compounds of the formula
(I) and salts thereof in
the form of substance collections, which are called libraries. The present
invention also provides
libraries comprising at least two compounds of the formula (I) and salts
thereof.
The compounds of the invention have excellent herbicidal efficacy against a
broad spectrum of
economically important mono- and dicotyledonous annual harmful plants. The
active ingredients also
act efficiently on perennial weeds which produce shoots from rhizomes, root
stocks and other perennial
organs and which are difficult to control.
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The present invention therefore also provides a method for controlling
unwanted plants or for regulating
the growth of plants, preferably in plant crops, in which one or more
compound(s) of the invention is/are
applied to the plants (for example harmful plants such as monocotyledonous or
dicotyledonous weeds or
unwanted crop plants), the seed (for example grains, seeds or vegetative
propagules such as tubers or
shoot parts with buds) or the area on which the plants grow (for example the
area under cultivation). The
compounds of the invention can be deployed, for example, prior to sowing (if
appropriate also by
incorporation into the soil), prior to emergence or after emergence. Specific
examples of some
representatives of the monocotyledonous and dicotyledonous weed flora which
can be controlled by the
compounds of the invention are as follows, though there is no intention to
restrict the enumeration to
particular species.
Monocotyledonous harmful plants of the genera: Aegilops, Agropyron, Agrostis,
Alopecurus, Apera,
Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus,
Dactyloctenium, Digitaria,
Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca,
Fimbristylis, Heteranthera, Imperata,
Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris,
Phleum, Poa, Rottboellia,
Sagittaria, Scirpus, Setaria and Sorghum.
Dicotyledonous weeds of the genera: Abutilon, Amaranthus, Ambrosia, Anoda,
Anthemis, Aphanes,
Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea,
Chenopodium, Cirsium,
Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia, Galeopsis,
Galinsoga, Galium,
Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha,
Mercurialis, Mullugo,
Myosotis, Papaver, Pharbitis, Plantago, Polygohum, Portulaca, Ranunculus,
Raphanus, Rorippa, Rotala,
Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus,
Sphenoclea, Stellaria, Taraxacum,
Thlaspi, Trifolium, Urtica, Veronica, Viola and Xanthium.
If the compounds of the invention are applied to the soil surface before
germination, either the
emergence of the weed seedlings is prevented completely or the weeds grow
until they have reached the
cotyledon stage, but then they stop growing and ultimately die completely
after three to four weeks have
passed.
If the active ingredients are applied post-emergence to the green parts of the
plants, growth stops after
the treatment, and the harmful plants remain at the growth stage at the time
of application, or they die
completely after a certain time, so that in this manner competition by the
weeds, which is harmful to the
crop plants, is eliminated very early and in a sustained manner.
Although the compounds of the invention have outstanding herbicidal activity
against
monocotyledonous and dicotyledonous weeds, crop plants of economically
important crops, for example
dicotyledonous crops of the genera Arachis, Beta, Brassica, Cucumis,
Cucurbita, Helianthus, Daucus,
Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Miscanthus,
Nicotiana, Phaseolus,
Pisum, Solanum, Vicia, or monocotyledonous crops of the genera Allium, Ananas,
Asparagus, Avena,
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Hordeum, Oryza, Panicum, Saccharum, Secale, Sorghum, Triticale, Triticum, Zea,
in particular Zea and
Triticum, will be damaged to a negligible extent only, if at all, depending on
the structure of the
particular compound of the invention and its application rate. For these
reasons, the present compounds
are very suitable for selective control of unwanted plant growth in plant
crops such as agriculturally
useful plants or ornamental plants.
In addition, the compounds of the invention, depending on their particular
chemical structure and the
application rate deployed, have outstanding growth-regulating properties in
crop plants. They intervene
in the plants' own metabolism with regulatory effect, and can thus be used for
the controlled influencing
of plant constituents and to facilitate harvesting, for example by triggering
desiccation and stunted
growth. In addition, they are also suitable for general control and inhibition
of unwanted vegetative
growth without killing the plants. Inhibition of vegetative growth plays a
major role for many mono- and
dicotyledonous crops since, for example, this can reduce or completely prevent
lodging.
By virtue of their herbicidal and plant growth regulatory properties, the
active ingredients can also be
used to control harmful plants in crops of genetically modified plants or
plants modified by conventional
mutagenesis. In general, the transgenic plants are characterized by particular
advantageous properties,
for example by resistances to certain pesticides, in particular certain
herbicides, resistances to plant
diseases or pathogens of plant diseases, such as certain insects or
microorganisms such as fungi, bacteria
or viruses. Other specific characteristics relate, for example, to the
harvested material with regard to
quantity, quality, storability, composition and specific constituents. For
instance, there are known
transgenic plants with an elevated starch content or altered starch quality,
or those with a different fatty
acid composition in the harvested material.
It is preferable with a view to transgenic crops to use the compounds of the
invention in economically
important transgenic crops of useful plants and ornamentals, for example of
cereals such as wheat,
barley, rye, oats, millet/sorghum, rice and corn or else crops of sugar beet,
cotton, soybean, oilseed rape,
potato, manioc, tomato, peas and other vegetables.
Preferably, the compounds of the invention can be used as herbicides in crops
of useful plants which are
resistant, or have been made resistant by genetic engineering, to the
phytotoxic effects of the herbicides.
Conventional ways of producing novel plants which have modified properties in
comparison to existing
plants consist, for example, in traditional cultivation methods and the
generation of mutants.
Alternatively, novel plants with modified properties can be generated with the
aid of recombinant
methods (see, for example, EP-A-0221044, EP-A-0131624). For example, there
have been descriptions
in several cases of:
genetic modifications of crop plants for the purpose of modifying the starch
synthesized in the
plants (for example WO 92/11376, WO 92/14827, WO 91/19806),
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transgenic crop plants which are resistant to particular herbicides of the
glufosinate type (cf., for
example, EP-A-0242236, EP-A-242246) or glyphosate type (WO 92/00377) or of the
sulfonylurea type (EP-A-0257993, US-A-5013659),
transgenic crop plants, for example cotton, which is capable of producing
Bacillus thuringiensis
toxins (Bt toxins), which make the plants resistant to certain pests (EP-A-
0142924, EP-A-
0193259),
transgenic crop plants having a modified fatty acid composition (WO 91/13972),
genetically modified crop plants with novel constituents or secondary
metabolites, for example
novel phytoalexins, which bring about an increased disease resistance (EPA
309862,
EPA0464461),
genetically modified plants having reduced photorespiration, which have higher
yields and higher
stress tolerance (EPA 0305398),
transgenic crop plants which produce pharmaceutically or diagnostically
important proteins
("molecular pharming"),
- transgenic crop plants which feature higher yields or better quality,
transgenic crop plants which feature a combination, for example, of the
abovementioned novel
properties ("gene stacking").
Numerous molecular biology techniques which can be used to produce novel
transgenic plants with
modified properties are known in principle; see, for example, I. Potrykus and
G. Spangenberg (eds.)
Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin,
Heidelberg, or Christou,
"Trends in Plant Science" 1 (1996) 423-431.
For such recombinant manipulations, nucleic acid molecules which allow
mutagenesis or sequence
alteration by recombination of DNA sequences can be introduced into plasmids.
With the aid of standard
methods, it is possible, for example, to undertake base exchanges, remove
parts of sequences or add
natural or synthetic sequences. To join the DNA fragments with one another,
adapters or linkers can be
placed onto the fragments, see, for example, Sambrook et al., 1989, Molecular
Cloning, A Laboratory
Manual, 2nd edition, Cold Spring Harbor Laboratory Press, Cold Spring Harbor,
NY, or Winnacker
"Gene und Klone" [Genes and clones], VCH Weinheim 2nd edition 1996.
For example, the generation of plant cells with a reduced activity of a gene
product can be achieved by
expressing at least one corresponding antisense RNA, a sense RNA for achieving
a cosuppression effect,
or by expressing at least one suitably constructed ribozyme which specifically
cleaves transcripts of the
abovementioned gene product. To this end, it is firstly possible to use DNA
molecules which encompass
the entire coding sequence of a gene product inclusive of any flanking
sequences which may be present,
and also DNA molecules which only encompass portions of the coding sequence,
in which case it is
necessary for these portions to be long enough to have an antisense effect in
the cells. It is also possible
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to use DNA sequences which have a high degree of homology to the coding
sequences of a gene
product, but are not completely identical to them.
When expressing nucleic acid molecules in plants, the protein synthesized may
be localized in any
5 desired compartment of the plant cell. However, to achieve localization
in a particular compartment, it is
possible, for example, to join the coding region to DNA sequences which ensure
localization in a
particular compartment. Such sequences are known to those skilled in the art
(see, for example, Braun et
al., EMBO J. 11 (1992), 3219-3227, Wolter et al., Proc. Natl. Acad. Sci. USA
85 (1988), 846-850;
Sonnewald et al., Plant J. 1(1991), 95-106). The nucleic acid molecules can
also be expressed in the
10 organelles of the plant cells.
The transgenic plant cells can be regenerated by known techniques to give rise
to entire plants. In
principle, the transgenic plants may be plants of any desired plant species,
i.e. not only
monocotyledonous but also dicotyledonous plants.
Thus, transgenic plants can be obtained whose properties are altered by
overexpression, suppression or
inhibition of homologous (= natural) genes or gene sequences or expression of
heterologous (= foreign)
genes or gene sequences.
The compounds of the invention can be used with preference in transgenic crops
which are resistant to
growth regulators, for example dicamba, or to herbicides which inhibit
essential plant enzymes, for
example acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS)
or
hydroxyphenylpyruvate dioxygenases (HPPD), or to herbicides from the group of
the sulfonylureas, the
glyphosates, glufosinates or benzoylisoxazoles and analogous active
ingredients.
When the active ingredients of the invention are employed in transgenic crops,
not only do the effects
toward harmful plants observed in other crops occur, but frequently also
effects which are specific to
application in the particular transgenic crop, for example an altered or
specifically widened spectrum of
weeds which can be controlled, altered application rates which can be used for
the application,
preferably good combinability with the herbicides to which the transgenic crop
is resistant, and
influencing of growth and yield of the transgenic crop plants.
The invention therefore also provides for the use of the compounds of the
invention as herbicides for
control of harmful plants in transgenic crop plants.
The compounds of the invention can be applied in the form of wettable powders,
emulsifiable
concentrates, sprayable solutions, dusting products or granules in the
customary formulations. The
invention therefore also provides herbicidal and plant-growth-regulating
compositions which comprise
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the compounds of the invention.
The compounds of the invention can be formulated in various ways, according to
the biological and/or
physicochemical parameters required. Possible formulations include, for
example: wettable powders
(WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable
concentrates (EC),
emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable
solutions, suspension
concentrates (SC), dispersions based on oil or water, oil-miscible solutions,
capsule suspensions (CS),
dusting products (DP), dressings, granules for scattering and soil
application, granules (GR) in the form
of microgranules, spray granules, absorption and adsorption granules, water-
dispersible granules (WG),
water-soluble granules (SG), ULV formulations, microcapsules and waxes.
These individual formulation types are known in principle and are described,
for example, in:
Winnacker-Ktichler, "Chemische Technologie" [Chemical Technology],
volume 7, C. Hanser Verlag Munich, 4th Ed. 1986, Wade van Valkenburg,
"Pesticide Formulations",
Marcel Dekker, N.Y., 1973, K. Martens, "Spray Drying" Handbook, 3rd Ed. 1979,
G. Goodwin Ltd.
.. London.
The formulation auxiliaries required, such as inert materials, surfactants,
solvents and further additives,
are likewise known and are described, for example, in: Watkins, "Handbook of
Insecticide Dust Diluents
and Carriers", 2nd Ed., Darland Books, Caldwell N.J.; H.v. Olphen,
"Introduction to Clay Colloid
Chemistry", 2nd Ed., J. Wiley & Sons, N.Y.; C. Marsden, "Solvents Guide", 2nd
Ed., Interscience, N.Y.
1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp.,
Ridgewood N.J., Sisley and
Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y.
1964; Schonfeldt,
"Grenzflachenaktive Athylenoxidaddukte" [Interface-active Ethylene Oxide
Adducts], Wiss.
Verlagsgesellschaft, Stuttgart 1976; Winnacker-Ktichler, "Chemische
Technologie" [Chemical
Engineering], volume 7, C. Hanser Verlag Munich, 4th Ed. 1986.
On the basis of these formulations, it is also possible to produce
combinations with other pesticidally
active substances, for example insecticides, acaricides, herbicides,
fungicides, and also with safeners,
fertilizers and/or growth regulators, for example in the form of a finished
formulation or as a tankmix.
Suitable safeners are, for example, mefenpyr-diethyl, cyprosulfamide,
isoxadifen-ethyl, cloquintocet-
mexyl and dichlormid.
Wettable powders are preparations uniformly dispersible in water which,
alongside the active ingredient
apart from a diluent or inert substance, also comprise surfactants of an ionic
and/or non-ionic type
(wetting agent, dispersant), e.g. polyethoxylated allcylphenols,
polyethoxylated fatty alcohols,
polyethoxylated fatty amines, fatty alcohol polyglycolethersulfates,
alkanesulfonates,
alkylbenzenesulfonates, sodium lignosulfonate, sodium 2,2'-dinaphthylmethane-
6,6'-disulfonate, sodium
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dibutylnaphthalenesulfonate or else sodium oleoylmethyltaurate. To produce the
wettable powders, the
active herbicidal ingredients are finely ground, for example in customary
apparatuses such as hammer
mills, blower mills and air-jet mills, and simultaneously or subsequently
mixed with the formulation
auxiliaries.
Emulsifiable concentrates are produced by dissolving the active ingredient in
an organic solvent, for
example butanol, cyclohexanone, dimethylformamide, xylene, or else relatively
high-boiling aromatics
or hydrocarbons or mixtures of the organic solvents, with addition of one or
more ionic and/or nonionic
surfactants (emulsifiers). Examples of emulsifiers which may be used are:
calcium alkylarylsulfonates
such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty
acid polyglycol esters,
alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-
ethylene oxide
condensation products, alkyl polyethers, sorbitan esters, for example sorbitan
fatty acid esters, or
polyoxyethylene sorbitan esters, for example polyoxyethylene sorbitan fatty
acid esters.
Dusting products are obtained by grinding the active ingredient with finely
distributed solids, for
example talc, natural clays, such as kaolin, bentonite and pyrophyllite, or
diatomaceous earth.
Suspension concentrates may be water- or oil-based. They may be prepared, for
example, by wet-
grinding by means of commercial bead mills and optional addition of
surfactants as have, for example,
already been listed above for the other formulation types.
Emulsions, for example oil-in-water emulsions (EW), can be produced, for
example, by means of
stirrers, colloid mills and/or static mixers using aqueous organic solvents
and optionally surfactants as
already listed above, for example, for the other formulation types.
Granules can be produced either by spraying the active ingredient onto
adsorptive granular inert material
or by applying active ingredient concentrates to the surface of carriers, such
as sand, kaolinites or
granular inert material, by means of adhesives, for example polyvinyl alcohol,
sodium polyacrylate or
else mineral oils. Suitable active ingredients can also be granulated in the
manner customary for the
production of fertilizer granules - if desired as a mixture with fertilizers.
Water-dispersible granules are produced generally by the customary processes
such as spray-drying,
fluidized-bed granulation, pan granulation, mixing with high-speed mixers and
extrusion without solid
inert material.
For the production of pan, fluidized-bed, extruder and spray granules, see
e.g. processes in "Spray-
Drying Handbook" 3rd Ed. 1979, G. Goodwin Ltd., London, J.E. Browning,
"Agglomeration", Chemical
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and Engineering 1967, pages 147 ff.; "Perry's Chemical Engineer's Handbook",
5th Ed., McGraw-Hill,
New York 1973, pp. 8-57.
For further details regarding the formulation of crop protection compositions,
see, for example, G.C.
Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York,
1961, pages 81-96 and
J.D. Freyer, S.A. Evans, "Weed Control Handbook", 5th Ed., Blackwell
Scientific Publications, Oxford,
1968, pages 101-103.
The agrochemical preparations contain generally 0.1 to 99% by weight,
especially 0.1 to 95% by weight,
of compounds of the invention.
In wettable powders, the active ingredient concentration is, for example,
about 10 to 90% by weight, the
remainder to 100% by weight consisting of customary formulation constituents.
In emulsifiable
concentrates, the active ingredient concentration may be about 1% to 90% and
preferably 5% to 80% by
weight. Dust-type formulations contain 1% to 30% by weight of active
ingredient, preferably usually 5%
to 20% by weight of active ingredient; sprayable solutions contain about 0.05%
to 80% by weight,
preferably 2% to 50% by weight of active ingredient. In the case of water-
dispersible granules, the
active ingredient content depends partially on whether the active compound is
in liquid or solid form and
on which granulation auxiliaries, fillers, etc., are used. In the water-
dispersible granules, the content of
active ingredient is, for example, between 1% and 95% by weight, preferably
between 10% and 80% by
weight.
In addition, the active ingredient formulations mentioned optionally comprise
the respective customary
stickers, wetters, dispersants, emulsifiers, penetrants, preservatives,
antifreeze agents and solvents,
fillers, carriers and dyes, defoamers, evaporation inhibitors and agents which
influence the pH and the
viscosity.
On the basis of these formulations, it is also possible to produce
combinations with other pesticidally
active substances, for example insecticides, acaricides, herbicides,
fungicides, and also with safeners,
fertilizers and/or growth regulators, for example in the form of a finished
formulation or as a tankmix.
For application, the formulations in commercial form are, if appropriate,
diluted in a customary manner,
for example in the case of wettable powders, emulsifiable concentrates,
dispersions and water-
dispersible granules with water. Dust-type preparations, granules for soil
application or granules for
scattering and sprayable solutions are not normally diluted further with other
inert substances prior to
application.
The required application rate of the compounds of the formula (I) varies with
the external conditions,
including, inter alia, temperature, humidity and the type of herbicide used.
It can vary within wide
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limits, for example between 0.001 and 1.0 kg/ha or more of active substance,
but it is preferably
between 0.005 and 750 gjha.
The examples listed in the tables below were prepared analogously to the
methods mentioned above or
can be obtained analogously to the methods mentioned above. These compounds
are very particularly
preferred.
The abbreviations used mean:
Ph = phenyl Me = methyl Et = ethyl
Table 1: Inventive compounds of the general formula (I) in which Q is Q3,
R2 is methyl, and W
and RP' are hydrogen, and Z is oxygen.
HO 0 X 0
R1
IA -IN
N0
p3
C H3
No. RP2 RP3 X R' Physical data
('H-NMR, DMSO-d6 or CDC13 ,400 MHz)
1-1 Me H Me Ph
1-2 Me H Me 2-Me-Ph (DMSO-d6): 7.69 (d,1H), 7.46
(d,1H),
7.37-7.27 (m,4H), 7.22 (d,1H), 3.57
(s,3H), 3.55 (s,3H), 2.61 (s,3H), 2.06
(s,3H)
-3 Me Me Me 2-Me-Ph (DMSO-d6): 7.58 (d,1H), 7.42
(d,1H),
7.37-7.30 (m,3H), 7.22 (d,1H), 3.57
(s,3H), 3.41 (s,3H), 2.57 (s,3H), 2.54
(s,3H), 2.05 (s,3H)
-4 Me H Me 2-Me,4-F-Ph (DMSO-d6): 7.70 (d,1H), 7.46
(d,1H),
7.30-7.22 (m,2H), 7.27 (s,1H), 7.13
(m,1H), 3.57 (s,3H), 3.55 (s,3H), 2.61
(s,3H), 2.06 (s,3H)
-5 Me H Me 2-Et-Ph (DMSO-d6): 7.69 (d,1H), 7.46
(d,1H),
7.37-7.26 (m,4H), 7.21 (d,1H), 3.57
(s,3H), 3.55 (s,3H), 2.60 (s,3H), 2.38
(q,2H), 1.07 (t,3H)
-6 Me H Me 2-CF3-Ph
-7 Me H Me 2-CN-Ph
1-8 Me H Me 2-Me0-Ph (DMSO-d6): 7.68 (d,1H),
7.44 (d,1H),
7.41 (d,1H), 7.28 (s,1H), 7.24 (dd,1H),
7.17 (d,1H), 7.04 (dd,1H), 3.73 (s,3H),
3.56 (s,3H), 3.55 (s,3H), 2.59 (s,3H)
1-9 Me H Me 3-Me0-Ph
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No. RP2 RP3 X R1 Physical data
(111-NMR, DMSO-d6 or CDCI3 ,400 MHz)
1-10 Me H Me 4-Me0-Ph
1-11 Me H Me 2-F-Ph
1-12 Me H Me 3-F-Ph
1-13 Me H Me 4-F-Ph
1-14 Me H Me 2-Cl-Ph
1-15 Me H Me 3-CI-Ph
1-16 Me H Me 4-Cl-Ph
1-17 Me H Me 2,6-Me2-Ph
1-18 Et H Me Ph
1-19 Et H Me 2-Me-Ph (DMSO-d6): 77.1 (d,1H), 7.45
(d,1H),
7.37-7.29 (m,4H), 7.22 (d,1H), 3.93
(q,2H), 3.58 (s,3H), 2.55 (s,3H), 2.06
(s,3H)
1-20 Et H Me 2-CF3-Ph
1-21 Et H Me 2-CN:Ph
1-22 Et H Me 2-Me0-Ph
1-23 Et H Me 3-Me0-Ph
1-24 Et H Me 4-Me0-Ph
1-25 Et H Me 2-F-Ph
1-26 Et H Me 3-F-Ph
1-27 Et H Me 4-F-Ph
1-28 Et H Me 2-Cl-Ph
1-29 Et H Me 3-CI-Ph
1-30 Et H Me 4-CI-Ph
1-31 Et H Me 2,6-Me2-Ph
1-32 Me H Cl Ph
1-33 Me H Cl 2-Me-Ph (DMSO-d6): 7.75 (d,1H), 7.58
(d,1H),
7.38-7.28 (m,4H), 7.23 (d,1H), 3.58
(s,3H), 3.54 (s,3H), 2.07 (s,3H)
1-34 Me H Cl 2-CF3-Ph
1-35 Me H Cl 2-CN-Ph
1-36 Me H Cl 2-Me0-Ph
1-37 Me H Cl 3-Me0-Ph
1-38 Me H Cl 4-Me0-Ph
1-39 Me H Cl 2-F-Ph
1-40 Me H Cl 3-F-Ph
1-41 Me H Cl 4-F-Ph
1-42 Me H Cl 2-Cl-Ph
1-43 Me H Cl 3-CI-Ph
1-44 Me H Cl 4-C1-Ph
1-45 Me H Cl 2,6-Me2-Ph
1-46 Et H Cl Ph
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No. RP2 RP3 X R.' Physical data
(1H-NMR, DMSO-d6 or CDC13 ,400 MHz)
1-47 Et H Cl 2-Me-Ph
1-48 Et H Cl 2-CF3-Ph
1-49 Et H CI 2-CN-Ph
1-50 Et H Cl 2-Me0-Ph
1-51 Et H Cl 3-Me0-Ph
1-52 Et H CI 4-Me0-Ph
1-53 Et H Cl 2-F-Ph
1-54 Et H Cl 3-F-Ph
1-55 Et H Cl 4-F-Ph
1-56 Et H Cl 2-Cl-Ph
1-57 Et H Cl 3-Cl-Ph
1-58 Et H Cl 4-CI-Ph
1-59 Et H CI 2,6-Me2-Ph
Table 2: Inventive compounds of the general formula (I) in which Q is Q2,
Y1 is an ethylene bridge,
Y2 is CH2, R2 is methyl, le is hydroxyl, W, Rc2 and lel are hydrogen, and Z is
oxygen.
0 0 x 0
0 N 0
CI
1-1,
No. X Physical data
(11-1-NMR, DMSO-d6 or CDCI3 ,400 MHz)
2-1 Me Ph
2-2 Me 2-Me-Ph (DMSO-d6): 7.55 (d,1H), 7.40 (d,1H),
7.37-
7.27 (m,3H), 7.23 (d,1H), 3.56 (s,3H), 3.1
(m,1H), 2.75 (m,1H), 2.56 (s,3H), 2.20 (d,1H),
2.15 (m,2H), 2.06 (s,3H), 1.95 (m,1H), 1.70
(dt,1H), 1.62 (m,1H)
2-3 Me 2-Me,4-F-Ph (DMSO-d6): 7.55 (d,1H), 7.40 (d,1H),
7.30
(dd,1H), 7.23 (dd,1H), 7.13 (m,1H), 3.56
(s,3H), 3.1 (m,1H), 2.75 (m,1H), 2.52 (s,3H),
2.20 (d,1H), 2.15 (m,2H), 2.06 (s,3H), 1.95
(m,1H), 1.70 (dt,1H), 1.62 (m,1H)
2-4 Me 2-Et-Ph (DMSO-d6): 7.55 (d,1H), 7.41-7.32
(m,4H),
7.22 (d,1H), 3.56 (s,3H), 3.1 (m,1H), 2.75
(m,1H), 2.52 (s,3H), 2.20 (d,1H), 2.15 (m,2H),
2.38 (q,2H), 1.95 (m,1H), 1.70 (dt,1H), 1.62
(m,1H), 1.07 (t,3H)
2-5 Me 2-CF3-Ph
2-6 Me 2-CN-Ph
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No. X R Physical data
(11-1-NMR, DMSO-d6 or CDCI3 ,400 MHz)
2-7 Me 2-Me0-Ph (DMSO-d6): 7.56 (d,1H), 7.42 (dd,1H),
7.39
(d,1H), 7.25 (d,1H), 7.16 (d,1H), 7.04 (dd,1H),
3.73 (s,3H), 3.55 (s,3H), 3.1 (m,1H), 2.75
(m,1H), 2.52 (s,3H), 2.20 (d,1H), 2.15 (m,2H),
2.06 (s,3H), 1.95 (m,1H), 1.70 (dt,1H), 1.62
(m,1H)
2-8 Me 3-Me0-Ph
2-9 Me 4-Me0-Ph
2-10 Me 2-F-Ph
2-11 Me 3-F-Ph
2-12 Me 4-F-Ph
2-13 Me 2-CI-Ph
2-14 Me 3-CI-Ph
2-15 Me 4-Cl-Ph
2-16 Me 2,6-Me2-Ph
2-17 Cl Me
2-18 Cl C2H40Me
2-19 Cl CH2-Ph
2-20 Cl Ph
2-21 Cl 2-Me-Ph
2-22 Cl 2-CF3-Ph
2-23 Cl 2-CN-Ph
2-24 Cl 2-Me0-Ph
2-25 Cl 3-Me0-Ph
2-26 Cl 4-Me0-Ph
2-27 Cl 2-F-Ph
2-28 Cl 3-F-Ph
2-29 Cl 4-F-Ph
2-30 Cl 2-Cl-Ph
2-31 Cl 3-CI-Ph
2-32 Cl 4-CI-Ph
2-33 Cl 2,6-Me2-Ph
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Table 3:
Inventive compounds of the general formula (I) in which Q is Q', Y is a CO
group, le is
hydroxyl, R2, Rc2, le, le and le are methyl, W is hydrogen, and Z is oxygen.
0 0 X 0
H,C
õR
H 1C
0 0 N
H,C CH, CH,
No. X R' Physical data
(11-1-NMR, DMSO-d6 or CDC13 ,400 MHz)
3-1 Me Ph
3-2 Me 2-Me-Ph (DMSO-d6): 7.60 (d,1H), 7.42 (d,1H),
7.37-
7.28 (m,3H), 7.24 (d,1H), 3.56 (s,3H), 2.60
(s,3H), 2.07 (s,3H), 1.35 (s,12H)
3-3 Me 2-Me,4-F-Ph (DMSO-d6): 7.60 (d,1H), 7.43 (d,1H),
7.34-
7.24 (m,2H), 7.14 (m,1H), 3.56 (s,3H), 2.60
(s,3H), 2.07 (s,3H), 1.35 (s,12H)
3-4 Me 2-Et-Ph (DMSO-d6): 7.60 (d,1H), 7.43 (d,1H),
7.40-
7.28 (m,3H), 7.23 (d,1H), 3.56 (s,3H), 2.59
(s,3H), 2.39 (q,2H), 1.35 (s,12H), 1.08 (t,3H)
3-5 Me 2-CF3-Ph
3-6 Me 2-CN-Ph
3-7 Me 2-Me0-Ph
3-8 Me 3-Me0-Ph
3-9 Me 4-Me0-Ph
3-10 Me 2-F-Ph
3-11 Me 3-F-Ph
3-12 Me 4-F-Ph
3-13 Me 2-Cl-Ph
3-14 Me 3-C1-Ph
3-15 Me 4-C1-Ph
3-16 Me 2,6-Me2-Ph
3-17 Cl Me
3-18 Cl C2H40Me
3-19 Cl CH2-Ph
3-20 Cl Ph
3-21 Cl 2-Me-Ph
3-22 Cl 2-CF3-Ph
3-23 Cl 2-CN-Ph
3-24 Cl 2-Me0-Ph
3-25 Cl 3-Me0-Ph
3-26 Cl 4-Me0-Ph
3-27 Cl 2-F-Ph
3-28 Cl 3-F-Ph
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No. X R1 Physical data
(1H-NMR, DMSO-d6 or CDC13 ,400 MHz)
3-29 Cl 4-F-Ph
3-30 Cl 2-Cl-Ph
3-31 Cl 3-Cl-Ph
3-32 Cl 4-Cl-Ph
3-33 Cl 2,6-Me2-Ph
Table 4: Inventive compounds of the general formula (I) in which Q is Q4,
R2 is methyl, WI' is
cyclopropyl, W and Rft2 are hydrogen, and Z is oxygen.
0 x o
N,R1
N N
CH,
No. X R' Physical data
(1H-NMR, DMSO-d6 or CDCI3 ,400 MHz)
4-1 Me Ph
4-2 Me 2-Me-Ph (DMSO-d6): 8.65 (s,1H), 7.82
(d,1H), 7.51
(d,1H), 7.38-7.28 (m,3H), 7.22 (d,1H), 3.59
(s,3H), 2.63 (s,3H), 2.52 (m,1H), 2.06
. (s,3H), 1.24 (m,4H)
4-3 Me 2-CF3-Ph
4-4 Me 2-CN-Ph
4-5 Me 2-Me0-Ph
4-6 Me 3-Me0-Ph
4-7 Me 4-Me0-Ph
4-8 Me 2-F-Ph
4-9 Me 3-F-Ph
4-10 Me 4-F-Ph
4-11 Me 2-Cl-Ph
4-12 Me 3-C1-Ph
4-13 Me 4-C1-Ph
4-14 Me 2,6-Me2-Ph
4-15 Cl Me
4-16 Cl C2H40Me
4-17 Cl CH2-Ph
4-18 Cl Ph
4-19 Cl 2-Me-Ph
4-20 Cl 2-CF3-Ph
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No. X R1 Physical data
('H-NMR, DMSO-d6 or CDC13 ,400 MHz)
4-21 Cl 2-CN-Ph
4-22 Cl 2-Me0-Ph
4-23 Cl 3-Me0-Ph
4-24 Cl 4-Me0-Ph
4-25 Cl 2-F-Ph
4-26 Cl 3-F-Ph
4-27 Cl 4-F-Ph
4-28 Cl 2-CI-Ph
4-29 Cl 3-Cl-Ph
4-30 Cl 4-Cl-Ph
4-31 Cl 2,6-Me2-Ph
Table 5:
Inventive compounds of the general formula (I) in which Q is Q5, R2 is methyl,
WI is
cyclopropyl, W is hydrogen, and Z is oxygen.
0 0 x o
,R
CN
N0
CH3
5
No. X R' Physical data
('H-NMR, DMSO-d6 or CDCI3 ,400 MHz)
5-1 Me Ph
5-2 Me 2-Me-Ph (DMSO-
d6): 8.31 (s,1H), 7.75 (d,1H), 7.47
(d,1H), 7.35-7.28 (m,3H), 7.23 (d,1H), 3.57
(s,3H), 3.10 (m,1H), 2.65 (s,3H), 2.06
(s,3H), 1.05 (m,4H)
5-3 Me 2-CF3-Ph
5-4 Me 2-CN-Ph
5-5 Me 2-Me0-Ph
5-6 Me 3-Me0-Ph
5-7 Me 4-Me0-Ph
5-8 Me 2-F-Ph
5-9 Me 3-F-Ph
5-10 Me 4-F-Ph
5-11 Me 2-C1-Ph
5-12 Me 3-Cl-Ph
5-13 Me 4-C1-Ph
5-14 Me 2,6-Me2-Ph
5-15 Cl Me
=
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No. X Physical data
(11-1-NMR, DMSO-d6 or CDC13 ,400 MHz)
5-16 Cl C2H40Me
5-17 Cl CH2-Ph
5-18 Cl Ph
5-19 Cl 2-Me-Ph
5-20 Cl 2-CF3-Ph
5-21 Cl 2-CN-Ph
5-22 Cl 2-Me0-Ph
5-23 Cl 3-Me0-Ph
5-24 Cl 4-Me0-Ph
5-25 Cl 2-F-Ph
5-26 Cl 3-F-Ph
5-27 Cl 4-F-Ph
5-28 Cl 2-CI-Ph
5-29 Cl 3-CI-Ph
5-30 Cl 4-C1-Ph
5-31 Cl 2,6-Me2-Ph
B. Formulation examples
a) A dusting product is obtained by mixing 10 parts by weight of a compound
of the formula (I)
and/or salts thereof and 90 parts by weight of talc as an inert substance and
comminuting the
mixture in a hammer mill.
b) A readily water-dispersible, wettable powder is obtained by mixing 25
parts by weight of a
compound of the formula (1) and/or salts thereof, 64 parts by weight of kaolin-
containing quartz
as an inert substance, 10 parts by weight of potassium lignosulfonate and 1
part by weight of
sodium oleoylmethyltaurate as a wetting agent and dispersant, and grinding the
mixture in a
pinned-disk mill.
c) A readily water-dispersible dispersion concentrate is obtained by mixing
20 parts by weight of a
compound of the formula (1) and/or salts thereof with 6 parts by weight of
alkylphenol
polyglycol ether ( Triton X 207), 3 parts by weight of isotridecanol
polyglycol ether (8 BO)
and 71 parts by weight of paraffinic mineral oil (boiling range for example
about 255 to above
277 C), and grinding the mixture in a friction ball mill to a fineness of
below 5 microns.
= 20 d) An emulsifiable concentrate is obtained from 15 parts by
weight of a compound of the formula
(I) and/or salts thereof, 75 parts by weight of cyclohexanone as a solvent and
10 parts by weight
of ethoxylated nonylphenol as an emulsifier.
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e) Water-dispersible granules are obtained by mixing
75 parts by weight of a compound of the formula (1) and/or salts thereof,
parts by weight of calcium lignosulfonate,
5 5 parts by weight of sodium lauryl sulfate,
3 parts by weight of polyvinyl alcohol and
7 parts by weight of kaolin,
grinding the mixture in a pinned-disk mill, and granulating the powder in a
fluidized bed by
spray application of water as a granulating liquid.
0 Water-dispersible granules are also obtained by homogenizing and
precomminuting, in a colloid
mill,
25 parts by weight of a compound of the formula (I) and/or salts thereof,
5 parts by weight of sodium 2,2'-dinaphthylmethane-6,6'-disulfonate
2 parts by weight of sodium oleoylmethyltaurate,
1 part by weight of polyvinyl alcohol
17 parts by weight of calcium carbonate and
50 parts by weight of water,
then grinding the mixture in a bead mill and atomizing and drying the
resulting suspension in a
spray tower by means of a one-phase nozzle.
C. Biological examples
1. Pre-emergence herbicidal action against harmful plants
Seeds of monocotyledonous and dicotyledonous weed plants and crop plants are
laid out in sandy loam
in wood-fiber pots and covered with soil. The compounds of the invention,
formulated in the form of
wettable powders (WP) or as emulsion concentrates (EC), are then applied to
the surface of the covering
soil in the form of an aqueous suspension or emulsion at a water application
rate equating to 600 to 800
1/ha, with addition of 0.2% wetting agent. After the treatment, the pots are
placed in a greenhouse and
kept under good growth conditions for the trial plants. The damage to the test
plants is scored visually
after a test period of 3 weeks by comparison with untreated controls
(herbicidal activity in percent (%):
100% activity = the plants have died, 0% activity = like control plants). For
example, inventive
compound nos. 1-2, 1-3, 1-4, 1-5, 1-8, 1-19, 2-2, 2-3, 2-4, 2-7, 3-2, 3-3, 3-
4, 4-2 and 5-2, at an
application rate of 0.32 kg or less per hectare, showed at least 80% efficacy
against Setaria viridis und
Matricaria inodora.
At the same time, inventive compounds leave Gramineae crops such as barley,
wheat, rye,
millet/sorghum, corn or rice virtually undamaged when applied pre-emergence,
even at high active
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ingredient dosages. In addition, some substances are also harmless to
dicotyledonous crops such as soya,
cotton, oilseed rape, sugar beet or potatoes. Some of the inventive compounds
exhibit high selectivity
and are therefore suitable for controlling unwanted vegetation in agricultural
crops by the pre-emergence
method.
2. Post-emergence herbicidal action against harmful plants
Seeds of monocotyledonous and dicotyledonous weed and crop plants are laid out
in sandy loam soil in
wood-fiber pots, covered with soil and cultivated in a greenhouse under good
growth conditions. 2 to 3
weeks after sowing, the test plants are treated at the one-leaf stage. The
compounds of the invention,
formulated in the form of wettable powders (WP) or as emulsion concentrates
(EC), are then sprayed
onto the green parts of the plants in the form of an aqueous suspension or
emulsion at a water
application rate equating to 600 to 800 1/ha, with addition of 0.2% wetting
agent. After the test plants
have been left to stand in the greenhouse under optimal growth conditions for
about 3 weeks, the action
of the preparations is assessed visually in comparison to untreated controls
(herbicidal action in percent
(%): 100% activity = the plants have died, 0% activity = like control plants).
For example, inventive
compound nos. 1-2, 1-3, 1-4, 1-5, 1-8, 1-19, 2-2, 2-3, 2-4, 2-7, 3-2, 3-3, 3-
4, 4-2 and 5-2, at an
application rate of 0.08 kg or less per hectare, showed at least 80% efficacy
against Abuthilon
theophrasti and Amaranthus retroflexus. At the same time, inventive compounds
leave Gramineae crops
such as barley, wheat, rye, millet/sorghum, corn or rice virtually undamaged
when applied post-
emergence, even at high active ingredient dosages. In addition, some
substances are also harmless to
dicotyledonous crops such as soya, cotton, oilseed rape, sugar beet or
potatoes. Some of the compounds
of the invention have high selectivity and are therefore suitable for
controlling unwanted vegetation in
agricultural crops by the post-emergence method.
