Note: Descriptions are shown in the official language in which they were submitted.
121478~
The present invention relates to N-aclyanthranilic
acid derivatives, a process for their manufacture, herbici-
des with contain these derivatives as active ingredients,
and a method of controlling undesirable plant growth using
these compounds.
It has been disclosed that substituted N-acyl-
anthranilic acid derivatives are intermediates for the
synthesis of pharmacological and herbicidal compounds
(French Patent 2,121,341 and German Laid-Open Applications
DOS 2,914,915, DOS 3,000,309 and DOS 3,037,970), herbicidal
active ingredients (Belgian Patent 648,259) or fungicidal
active ingredients (DOS 2,759,121).
It has now been found that N-acylanthranilic acid
derivatives of the formula I
Rl y
~ C-Y'-R (I)
NH-~-R2
where R1 is halogen, nitro, C1-C4-alkyl, C1-C4-alkoxy,
C~-C4-haloalkyl, C1-C4-haloalkoxy or C1-C4-haloalkylmercapto,
R is unsubstituted or C1-C4-alkyl-substituted thienyl or
is phenyl which is m-substituted, p-substituted or m- and
p-substituted by C1-C4-haloalkyl, C1-C4-haloalkoxy, C1-C4-
haloalkylmercapto, C1-C4-haloalkylsulfinyl, C1-C4-halo-
alkylsulfonyl or C1-C4-alkylsulfonyl, R is a straight-
chain or branched alkyl, alkenyl, or alkynyl radical of not
more than 12 carbon atoms which is unsubstituted or substi-
tuted by halogen, cyano, thiocyano, nitro, C2-C4-alkyl-
carbonyl C -C -alkoxy, C2-C4- -
~*
,~ . ..
~2~7~
- 2 - ~.Z. 0050/36410
a~kenY~OXY~ C2-C4-a~kYnY~OXY, Cl-c4-a~kylmercapto~
Cz-C4-alkenylnercapto, C2-C4-alkynylmercapto, C2-C5-
alkoxycarbonyl, C2-C5-a~kylmercaptocarbonyl or C3-C4-
a~kenylcarbonyl, or is C3-C7-cyc~oa~ky~ wh;ch is unsub-
stituted or substituted by C1-C4-alkyl, C1-C4-alkoxy,
C1-C4-a~ky~mercapto, C1-C4-alkylsulfonyl, halogen,
tr~fluoromethy~, n~tro or cyano, a 2-~2-alkoxyethoxy)-
ethyl, 2-~2-a~kenoxyethoxy)-ethyl or 2-~2-alkynoxyethoxy)-
ethyl radical of not more than 8 carbon atoms, a 3-(2-
alkoxyethoxy)-n-propy~ radical of not more than 9 carbon
atoms, phenyl ~hich is unsubstituted or substituted by
halogen, C1-C4-a~kYl~ C1~C4-haloalkyl, C1-C4-alkoxy,
C1-C4-haloalkoxy, C1-C4-alkylmercapto, C1-C4-halo-
alkylmercapto, nitro or cyano, or ;s phenoxyalkyl of 7 to 12
carbon atoms, phenoxyalkenyl of 8 to 12 carbon atoms,
phenoxyalkynyl of 8 to 12 carbon atoms or phenylalkyl of
7 to 12 carbon atoms, each of which is unsubstituted or
substituted by halogen, C1-C4-alkyl, C1-C4-h~loalkyl,
C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylmercapto, C1-C4-
haloalkylmercapto, nitro or cyano, and Y and Y' are
each oxygen or sulfur, ~ith the prov;so that R2 may fur-
thermore be unsubstituted or halogen-substitutet phenyl if
R1 is fluorine, are very ~ell tolerated by crops
and have a more powerful herb;c1dal action than conven-
tional herbicidal N-acylanthrani~;c ac;d der;vat;ves.
In formula ~, R1 is, for example, halo-
g n, n;tro, C1 C4 alkyl, C1-C4-alkoxy, C1-C4-halo-
alkyl, Ct-C4-haloalkoxy or C1-C4-haloalkyLmercapto,
eg. 'luorine, chlor;ne, brom;ne, iod;ne, nitro, methyl,
ethyl, isopropyl, n-propyl, ;sobutyl, tert.-butyl, tr;-
chloromethyl, difluorochloromethyl, trif~uoromethyl, di-
fluoromethyl, Z,2,1,1-tetrafluoroethyl, methoxy, ethoxy,
isopropoxy, n-butoxy, trifluoromethoxy, hexafluoroisoprop-
oxy, difluoromethy~mercapto or trifluoromethylmercapto,
or a radical of the formula Y"-Cf2CtZ~3, where Y" is oxy-
gen or su~fur and the radicals Z independentl~ of one ano-
ther are each hydrogen, fluorine, chlorine, bromine or
~, .
7~(i
iodine, eg. 2,2,1,1-tetrafluoroethoxy, l,1-difluoroethoxy,
2,2,1,1-tetrafluoroethylmercapto or 1,1-difluoroethyl-
mercapto.
In formula I, R is, for example, thien-3-yl or
thien-2-yl which is unsubstituted or substituted by C1-C4-
alkyl, preferably by methyl, or is aryl, eg. phenyl or
naphthyl, in particular phenyl, which may carry the following
substituents in the m-, p- or m- and p-position:
4 Y ~ 1 C4-haloalkoxy, Cl-C4-haloalkyl
Cl-C4-haloalkylsulfinyl, C1-C4-haloalkylsulfonyl, halogen
or C1-C4-alkylsulfonyl, such as methylmercapto, ethyl-
mercapto, isopropylmercapto, chloromethoxy, fluoromethoxy,
difluoromethoxy, difluorochloromethoxy, trifluoromethoxy,
trichloromethoxy, 1,1,2,2-tetrafluoroethoxy, 1,1,2,2-
trifluoro-2-chloroethoxy, 1,1,1,-trifluoro-2-bromoethoxy,
1,1,2,3,3,3-hexafluoro-n-propyloxy, pentafluoroethoxy,
hexafluoroisopropoxy, difluoromethylmercapto, trifluoro-
methylmercapto, pentafluoroethylmercapto, 1,1,2,2-tetra-
fluoroethylmercapto, trichloromethylmercapto, dichloro-
fluoromethylmercapto, trifluoromethylmercapto, methyl-
sulfonyl, ethylsulfonyl, isopropylsulfonyl, trifluoro-
methylsulfonyl, pentafluoroethylsulfonyl, trifluoromethyl-
sulfinyl, fluorine, chlorine, bromine, iodine, trifluoro-
methyl, difluorochloromethyl, difluoromethyl, 1,1,2,2-
tetrafluoroethyl or pentafluoroethyl.
In formula I, R is, for example, a straight-
chain or branched alkyl, alkenyl or alkynyl radical of
not more than 12, preferably not more than 4, carbon atoms,
which is unsubstituted or substituted by halogen, cyano,
thiocyano, nitro, C2-C4-alkylcarbonyl, Cl-C4-alkoxy,
=
" r
~1
lzl~7sa
- 4 - O.z. 0050/36410
C2-C4-alkenyloxy, C2-C4-alkynyLoxy, C1-C4-alkyl-
mercapto, C2-C4-alkenylmercapto, C2-C4-alkynylmer-
capto, C2-C5-alkoxycarbonyl, C2-Cs-alkylmercapto-
carbonyl or C3- or C4-alkenylcarbonyl, e~ methyl, ethyl,
n-propyl, ;sopropy~, n-butyl, ;sobutyl, sec.-butyl, tert.-
butyl, n-pentyl, tert.-amyl, n-hexyl, pent-3-yl, 1,2-d;-
methyl-n-propyl, 1,3-d;methyl-n-buty~, 1-ethyl-2-methyl-
n-propyl, 1,2,2-trimethyl-n-propy~, 1,2-d;methyl-n-hex-4-yl,
heptyl, octyl, nonyl, decyl, undecyl, dodecyl, allyl,
methallyl, crotyl, 2-ethyl-hex-2-enyl, hex-5-enyl, Z-
methyl-but-2-enyl, 2-methyl-but-3-enyl, but-1-en-3-yl,
2-methyl-but-1-en-4-yl, 2-methyl-but-Z-en-4-yl, 3-methyl-
but-1-en-3-yl, propargyl, but-1-yn-3-yl, but-2-ynyl, 2-
chloroethyl, 2-chloro-n-propyl, 3-chloro-n-propyl, 2-chloro-
sec.-butyl, Z-chloro;sobutyl, 2-fluoro-sec.-butyl, 2-fluoro-
;sobutyl, 2-fluoro;sopropyl, chloro-tert.-butyl, 2,2,2-
trifluoroethyl, Z-cyanoethyl, 2-cyano-n-propyl, 3-cyano-
n-propyl~ 4-cyano-n-butyl, 3-cyano-prop-2-enyl, 4-cyano-
but-Z-ynyl, 2-nitroethyl, 2-n;tro-n-propyl, 3-nitro-n-
propyl, 3-n;tro-prop-2-enyl, propan-2-onyl, butan-2-onyl,
but-3-en-2-onyl, methoxyethyl, ethoxyethyl, 3-methoxy-
propyl, methoxy;sopropyl, 3-methoxybutyl, 1-methoxybut-2-
yl, ethoxy-tert.-butyl, methoxy-tert.-butyl, 2-methoxy-n-
butyl, 4-methoxy-n-butyl, 2-allyloxyethyl, 2-propargyloxy-
Z5 ethyl~ 2-a~lyloxy-n-propyl, 2-propargyloxy-n-propyl, 3-
allyloxy-n-propyl, 4-allyloxy-but-2-ynyl, 2-methylmercapto-
ethyl, 2-ethylmercaptoethyl, 3-methylmercapto-n-propyl,
2-allylmercaptoethyl, 2-propargylmercaptoethyl, 2-allyl-
mercapto-n-propyl, vinylcarbonylethyl, 2-thiocyanoethyl,
2-th;ocyano-n-propyl, 3-th;ocyano-n-propyl, 4-th;ocyano-
n-butyl, 3-methoxycarbonyl-prop-2-yl, 3-ethoxycarbonyl-
prop-2-yl, 3-methylmercaptocarbonyl-prop-2-yl, 3-ethyl-
mercaptocarbonyl-prop-2-yl, 3-methoxycarbonyl-prop-Z-enyl,
3-ethoxycarbonyl-prop-2-enyl, 3-ethoxycarbonyl-prop-2-ynyl
or 3-n~butoxycarbonyl-prop-2-ynyl, or is C3-C7-cyclo-
alkyl which is unsubstituted or substituted by C1-C4-
alkyl, C1-C4-alkoxy, C1-C4-alkylmercapto, C2-C4-
121478~
- 5 - ~.z. 0050/36410
alkylsulfonyl, halogen, trifluoromethyl, nitro or cyano,
eg. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
cycloheptyl, 2- or 3-methylcyclopentyl, 2-, 3- or 4-methylo
cyclohexyl, 2~, 3- or 4-methoxycyclohexyl, 2-~ 3- or 4-
methylmercaptocyclohexyl, 2-, 3- or 4-methylsulfonylhexyl,
2-, 3- or 4-chlorocyclohexyl, 2-, 3- or 4-trifluoromethyl-
cyclohexyl, 2-, 3- or 4-nitrocyclohexyl or 2-, 3- or 4-
cyanocyclohexyl, or is a 2-~2-alkoxyethoxy)-ethyl, 2-t2-
alkenoxyethoxy)-ethyl or 2-~2-alkynoxyethoxy)-ethyl radi-
cal of not more than 8 carbon atoms, eg. 2-(2-methoxy-
ethoxy)-ethyl, 2-~2-al~yloxyethoxy)-ethyl or 2-~2-propar-
gyloxyetho%y~-ethyl, or a 3-~2-alkoxyethoxy)-n-propyl
rad;cal of not more than 9 carbon atoms, eg. 3-(2-methoxy-
ethoxy)-n-propyl or is phenyl ~hich is unsubstituted or
subst;tuted by halogen, C1-C4-alkyl, C1-C4-haloalkyl,
C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylmer-
cap~o, C1-C4-haloalkylmercapto, n;tro or cyano, or is
phenoxyalkyl of 7 to 12 carbon atoms, phenoxyalkenyl of
8 to 12 carbon atoms, phenoxyalkynyl of 8 to 12 carbon
atoms or phenylalkyl of 7 to 12 carbon atoms, each of which
is unsubstituted or subst;tuted by halogen, C1-C4-alkyl,
C1-C4-haloalky~, C1-C4-alkoxy, C1-C4-haloalkoxy,
C1-C4-alkylmercapto, C1-C4-haloalkylmercapto, n;tro
or cyano, eg. phenyl, 2-, 3- or 4-chlorophenyl, 2,3-, 2,4-,
2,5-, 2,6-, 3,5- or 3,6-d;chlorophenyl, 2,4,5- or 2,4,6-
tr;chlorophenyl, 2-, 3^ or 4-cresyl, 2,3-, 2,4-, 2,5-, 2,6-,
3,5- or 3,6-dimethylphenyl, 2-chloro-4-trifluoromethyl-
phenyl, 2-, 3- or 4-trifluoromethylphenyl, 2-, 3- or 4-
n;trophenyl, 2,4-d;n;trophenyl, Z-chloro-4-nitrophenyl,
2-nitro-4-chlorophenyl, 2-, 3- or 4-cyanophenyl, 2-chloro-
4-cyanophenyl, 2-cyano-4-n;trophenyl, 2-, 3- or 4-methoxy-
phenyl, 2-, 3- or 4-chlorodifluoromethoxyphenyl, 2-, 3-
or 4-methylmercaptophenyl, 2-, 3- or 4-trifluoromethyl-
mercaptophenyl, 2-~2'-, 3'- or 4C-chlorophenyl)-ethyl~
2-(2',4'-dichlorophenyl)-ethyl, 2-(2',4',6'-trichloro-
phenyl)-ethyl, 2-(3',5'-dichlorophenyl)-ethyl, 2-(o-, m-
or p-tolyl)-ethyl, 2-(3',4'-xylyl)-ethyl, 2-(2'-, 3'- or
~Z1478~
4'-trifluoromethylphenyl)-ethyl, 2-(o-, m- or p-anisyl)-
ethyl, 2-(o-, m- or p-difluoromethoxyphenyl)-ethyl, 2-(o-,
m- or p-chlorodifluoromethoxyphenyl)-ethyl, 2-(o-, m- or
p-methylmercaptophenyl)-ethyl, 2-(o-, m- or p-trifluoro-
methylmercaptophenyl)-ethyl, 2-(o-, m- or p-cyanophenyl)-
ethyl, 2-(0-, m- or p-thiocyanatophenyl)-ethyl, 3-(o-, m-
or p-chlorophenylO-n-propyl, 3-(o-, m- or p-trifluoro-
methylphenyl)-n-propyl, 2-phenylethyl, 3-phenyl-n-propyl,
4-phenyl-n-butyl, 5-phenyl-n-pentyl, 2-(o-, m- or p-nitro-
phenyl)-ethyl, 2-(3'-chloro-4'-methoxyphenyl)-ethyl, 2-
(4'-chloro-3'-methocyphenyl)-ethyl, 2-(2'-chloro-4'-tri-
fluoromethylphenyl)-ethyl, 2-phenoxy-ethyl, 3-phenoxy-n-
propyl, 4-phenoxy-n-butyl, 2-(o-, m- or p-chlorophenoxy)-
ethyl, 2-(2',4'-dichlorophenoxy)-ethyl, 2-(o-, m- or p-
cresyloxy)-ethyl, 2-(o-, m- or p-trifluoromethylphenoxy)-
ethyl, 2-(2'-chloro-4'-trifluoromethylphenoxy)-ethyl, 3-
(o-, m- or p-chlorophenoxy)-n-propyl, 4-phenoxy-but-2-ynyl,
4-(p-chlorophenoxy)-butyn-2-yl, 4-phenoxy-but-2-enyl, 3-
(2',4'-dichlorophenoxy)-n-propyl, 3-(3'-trifluoromethyl-
phenoxy)-n-propyl or 4-(p-chlorophenoxy)-but-2-enyl.
R2 may furthermore be unsubstituted or halogen-
substituted phenyl, if R1 is fluorine. Examples of
appropriate radicals are phenyl, 3-fluorophenyl, 4-fluoro-
phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-bromophenyl and
4-iodophenyl.
Preferred compounds of the formula I are those in
which Rl is halogen, R2 is a phenyl radical which is
substituted by Cl-C4-haloalkyl, C1-C4-haloalkoxy or C1-C4-
haloalkylmercapto, or is unsubstituted or halogen-substituted
phenyl if R1 is fluorine, and R3 is a straight-chain or
branched alkyl, alkenyl or alkynyl radical of not more than
6 carbon atoms which is unsubstituted or substituted by
halogen, cyano, C2-C4-alkylcarbonyl, C1-C4-alkoxy, C2-C4-
alkenyloxy, C2-C4-alkynyloxy or C1-C4-alkylmercapto, or is
C3-C7-CyClo~
~.
lZ~47~
- 7 - O.Z. 0050/36410
alkyl, alkyl of not morc than 3 carbon atoms wh;ch ;s sub-
stituted by C2-C5-alkoxycarbonyl or C2-C5-alkylmer-
captocarbonyl, a 2-t2-alkoxyethoxy)-ethyl, 2-~Z-alkenoxy-
ethoxy)-ethyl or 2-(2-alkynoxyethoxy)-ethyl radical of not
more than 8 carbon atoms, phenyl ~hich is unsubstituted
or subst;tuted by a-kyl, haloalkyl, alkoxy or haloalkoxy,
each of not morc than 2 carbon atoms, halogen, n;tro or
cyano, or is phcnoxyalkyl of 7 to tO carbon atoms, phenoxy-
alkenyl of 8 to 10 carbon atoms, phenoxyalkynyl of 8 to 10
1û carbon atoms or phenylalkyl of 7 to 1û carbon atoms, each
of ~h;ch ;s unsubstituted or subst;tuted by alkyl, halo-
alkyl, a~koxy or haloalkoxy, each of not more than 2 car-
bon atoms, halogen, n;tro or cyano, and Y and Y' are each
oxygen.
Hovel N-acylanthranil;c ac;d der;vat;ves are those
of the formula
C-Y -R~
b~ N~_C_F~2
o
~here R1 ;s halogen, n;tro, C1-C4-alkyl, C1-C4-
alkoxy, C1-C4-ha~oalkyl~ C1-C4-haloalkoxy or C1-C4-
haLoalkylmerCapto, R2 is phenyl which is substitutedmeta or para, or meta and para, by
C1-C4-haloalkyl, C1-C4-haloalkoxy, C1-C4-halo-
alkylmercapto, C1-C4-haloalkylsulf;nyl, C1-C4-halo-
alkylsulfonyl or C1-C4-alkylsulfonyl, R3 is ammonium
~h;ch ;s unsubstituted or subst;tuted by C1-C4-alkyl
C~-C4-hydroxyalkyl, C1-C4-haloalkyl or C2-C5-
alkoxyalkyl, or is a straight-chain or branched alkyl,
alkenyl or alkynyl radical of not more than 1Z carbon
atoms ~h;ch is unsubstituted or subst;tuted by halogen,
cyano, thiocyano, n;tro, C2-C4-alkylcarbonyl, C1-C4-
a~koxy~ C2-C4-a~keny~oxy~ C2-C4-alkynyloxy~ C1-C4-
alkylmercapto, C2-C4-alkenylmercapto, C2-C4-alkynyl-
1:Z14780
- 8 - ~.Z. 0050/36410
mercapto, C2-C5-alkoxycarbony~, C2-C5-alky~mercapto-
carbony~ or C3- or C4-a~keny~carbony~ or ;s a 2-~2-
a~kox~ethoxy)-ethyl, 2-(2-a~kenoxyethoxy~-ethyl or 2-~2-
alk~noxyethoxy)-ethyl radica~ of not ~ore than 8 carbon
S atoms, a 3-~2-alkoxyethoxy)-n-propyl rad~cal of not more
than 9 carbon atoms, or phenyl which 15 unsubst;tuted or
substituted by halogen, C~-C4-a~ky~, C1-C4-haloalkyl,
Cl-C4-a~koxy~ C1-C4-ha~Oa~koxy~ c1_c4_alkylmer-
capto, C1-C4-haloalky~mercapto, nitro or cyano, or is
phenoxyalkyl of 7 to 12 carbon atoms, phenoxyalkenyl of
8 to 12 carbon atoms, phenoxyalkynyl of 8 to 12 carbon
atons or phenyLalkyl of 7 to 12 carbon atoms, each of wh;ch
i5 unsubst;tuted or subst;tuted by ha~ogen, C1-C4-a~kyl,
C1-C4-haloalk~l, C1-C4-alkoxy~ C1-C4-haloalkoxy,
C1-C4-alkylmercapto, C1-C4-haloalkylmercapto, nitro
or cyano, and Y and Y' are each oxygen or sulfur, w;th the
proviso that R2 may furthermore be unsubstituted or
halogen-subst;tuted aryl ~f R1 is fluorine.
The N-acylanthranilic acid der;vatives of the
formula I are obta;ned by reacting a a~pound of the formula
R~ Y
~ C-Y'-R3
: ~NH2 ~I2),
where R1, Y~ Y' and R3 have the above mean;nss,
with a compound of the formula
. ~ O
" ~ I I I ),
~here R2 has the above mean;ngs and Hal ;s halogen, in
the presence or absence of an ;nert organ;c solvent or ;n
water and ;n the presence or absence of an ac;d acceptor,
at from 0 to 80C (process A). The reaction can be
~4
~2147~3V
- 9 - O.Z. 0050/36410
carried out under atmospheric or superatmospheric pressure,
cont~nuously or batch~ise.
If methyl 6-chloroanthranilate and 3-trifluoro-
methy~mercaptobenzoyl fluor;de are used as start~ng ~ate-
r;aLs, the course of the react;on can be represented bythe follo~;ng equat;on: C1
2C~3 ~ F-C- ~ NH-C ~
The N-acylanthran;l;c ac;d derivat;ves of the for-
mula I are also obta;ned by react~g a o~und of the formula
~1 Y tIV)~
2
~here R1, Y and R2 have the above mean;ngs,
~ith à compound of the formula
R3-Y'-H ~V),
~here R3 and Y' have the above mean;ngs " n the presence
or absence of an ;nert organ;c solvent or d;rectly in an
excess of the compound of the formula V, ;n the presence
or absence of an ;norgan;c or tert;ary organ;c base as a
catalyst, at from 0 to 190C (process B). The react;on
can be carr;ed out under atmospher;c or superatmospher;c
pressure, cont;nuously or batch~ise.
If S-chloro-2-m-tr;fluoromethylmercaptophenyl-4~-
3,1-benzoxazin-4-one and n-propyl alcohol are used as
start;ng materials, the course of the react;on can be
represented by the follo~ing equation:
~6
~i
~21478~
_ 10 _ o.z. 0050/3641
~C3H7~ c~e~
SCF3 SCF3
Advantageously, solvents or diluents wh;ch are
;nert under the part;cular reaction condit;ons are used
for bo~h react;on A and reaction ~. Examples of su;table
compounds are halohrdrocarbons, ;n part;cular chloro-
hydrocarbons, eg. tetrach~oroethylene, 1,1,2,2- and 1,1,1,2-
tetrachloroethane, d;chloropropane, methylene chlor;de,
d;chlorobutane, chloroform, chloronaphthalene, dichloro-
naphthaleneO carbon tetrachlor;de, 1,1,1- and 1,1,2-tr;-
chloroethane, tr;chloroethylene, pentachloroethane, o-, m-
and p-d;fluorobenzene, 1,1- and 1,2-d;chloroethane,
1 ,2-c Is-dichloroethylene, chlorobenzene, fluoro-
benzene, bromobenzene, iodobenzene, o-, m- and p-dichloro-
benzene, o-, p- and m-d~bromobenzene, o-, m- and p-chloro-
toluene and 1,2,4-tr;chlorobenzene; ethers, eg. ethyl pro-
pyl ether, methyl tert.-butyl ether, n-butyl ethyl ether,
di-n-butyl ether, d;isobutyl ether, diisoamyl ether, diiso-
propyl ether, anisole, phenetole, cyclohexyl methyl ether,
diethyl ether, ethylene glycol dimethyl ether, tetrahydro-
furan, dioxane, thloan;sole and ~ dichlorodiethylether; n;trohydrocarbons, eg. n;tromethane, n;troethane,
n;trobenzene, o-, m- and p-chloron;trobenzene and o-nitro-
toluene; n;tr;les, eg. acetonitr;le, butyron;tr;le, ;so~
butyronitr;le, benzon;tr;le and m-chlorobenzon;tr;le;
al;phat;c and cycloal;phat;c hydrocarbons, eg. heptane,
pinane, nonane, o-, m- and p-cymene, gasol;ne ~ract;ons
bo;l;ng with;n a range ~rom 70 to 19QC, cyclohexane,
methylcyclohexane, decalin, petroleum ether, hexane,
naphtha, 2,2,4-tr;methylpentane, 2,2,3-trimethylpentane,
2,3,3-tr;methylpentane and octane; esters, eg. ethyl ace-
tate, ethyl acetoacetate and ;sobutyl acetate; am;des, eg.
78~
~ O.Z. 0050/36410
formam;de, methyl formamide and d;methylformamide, ketones,
eg. acetone and methyl ethyl ketone, and, ;f appropr;ate,
water and mixtures of these so~vents. Advantageously, the
solvent is used in an amount of from 100 to 2000, prefe-
rably from 200 to 700, X by weight, based on star~ing
material II.
Any convent;onal acid acceptor can be used for
react;on A. Preferred ac;d acceptors ;nclude tertiary
am;nes, alkal;ne earth meta~ compounds, ammon;um compounts
and alkali metal compounds, as we~l as mixtures of these.
Zinc compounds may also be used. Examp~es of bas;c com-
pounds are potass;um hydroxide, sod;um hydroxide, potas-
s;um carbonate, sodium carbonate, lith;um hydroxide, lith-
;um carbonate, sod;um bicarbonate, potassium b;carbonate,
ca~c;um hydrox;de, ca~c;um ox;de, bar;um oxide, magnes;um
hydrox;de, magnes;um ox;de, barium hydrox;de, calc;um car-
bonate, magnesium carbonate, magnesium bicarbonate, mag-
nes;um acetate, z;nc hydroxide, z;nc oxide, zinc carbon-
ate, z;nc blcarbonate, z;nc acetate, sodium formate, so-
d;um acetate, trimethylamine, tr;ethylam;ne, tripropyl-
am;ne, tri;sopropylam;ne, tr;butylam;ne, tr;;sobutylamine,
tr;-sec.-butylam;ne, tr;-tert.-butylam;ne, tribenzylamine,
tr;cyclohexylamine, triamylam;ne, trihexylamine, N,N-di-
methylaniline, N,N-diethylaniline, N,N-dipropylaniline,
N,N-dimethyltolu;d;ne, N,N-diethy~toluidine, N~N-dipropyl-
tolu;d;ne, N,N-d;methyl-p-am;nopyridine, N,N-diethyl-p-
aminopyr;dine, N,N-d;propyl-p-am;nopyridine, N-
methylpyrrolidone, N-ethylpyrrol;done, N-methylp;peridine,
N-ethylpiper;dine, N-methylpyrrolidine, N-ethylpyrrol;d;ne,
N-methylimidazole, N-ethylimidazole, N-methylpyrrole, N-
ethylpyrrole, N-methylmorpholine, N-ethylmorphol;ne, N-
methylhexamethylene;mine, N-ethylhexamethylene;mine~
pyridine, quino~ine, a -picoline, ~ -picoline , ~ -
picoline, isoquinoline, pyrimidine, acridine, N,N,N',N'-
tetramethylethylenediamine, N,N,N',N'-tetraethyl-
ethylenediamine, quinoxaline, quinazoline, N-propyl-
diisopropylamine, N,N-dimethylcyclohexylamine, 2,6-luti-
iZ1~8~
- 12 - O~Z. 005~/3~410
d;ne, 2,4-lut;dine, trifurfurylam;ne and triethylenedi-
amine.
Advantageously, the acid acceptor ;s used ;n an
amount of from 80 to 120X based on the start;ng mater;al
5 II. Suitable catalysts for react;on B are the above ;n-
organic or tert;ary organic bases, but it is also possible
to use an alka~; metal or alkaline earth metal hydride,
such a lithium hydr;de, sod;um hydride or calcium hydride.
Advantageously, the catalyst ;s used ;n an amount of from
70 to 99.5Z, based on the start;ng materia~ IY.
The starting materials of the formula ~I and III
are used in about stoichiometric amounts, ie. the starting
material of the formula III is advantageously used in an
amount of from 90 to 110%, based on the starting mater;al
of the formula II.
The starting materials of the formulae IV and V
can be used in stoichiometric amounts, but ;~ ;s advan-
tageous to employ an excess of not more than 30%, based
on starting material of the formula IV, of the starting
mater;al of the formula V. However, it ;s also possible
to use the start;ng mater;al of the formula V directly as
the solvent.
Process A ;s advantageously carried out as fol-
lows: the acyl hal;de of the formula III and an equ;va-
lent amount of the ac;d acceptor are fed, via two feeds,;nto about an equivalent amount of the anthranilic acid
compound of the formula II ;n an inert organic solvent or
;n water, at from 0 to 80C. Stirr;ng ;s then con-
tinued for from 5 to 60 m;nutes at room temperature. To
isolate the N acylanthran;l;c acid der;vative, the m;~ture
is treated w;th water, w;th d;lute acid or, where the radi-
cal R3 is covalently bonded, w;th d;lute alkali to sepa-
rate off by-products, such as the unreacted anthranilic
acid compound, the acyl chlor;de or the hydrochlor;de of
the base, and can be dr;ed and then evaporated down. If
necessary, the end product may be further purified by
recrystallization or chromatography.
~1478~
- 13 - O.Z. OOS0l36410
Process ~ ;s advantageously carr~ed out as fol-
~ows: the 4H-3,1-benzoxaz;n-4-one of the formula IV ;s
;ntroduced into a so~ution of not less than an equ;valent
amount of the start;ng material of the formula V in an ;n-
ert organic solvent, or directly into an excess of thestarting material cf the formula V, in the presence or ab-
sence of an ;norgan;c or tert;ary organ;c base as a cata-
~yst, at from 0 to 150C. Stirring ;s then cont;nued
for from 10 to 240 m;nutes at from Z5 to 190C. How-
ever, ;t ;s also poss;ble to ;ntroduce the starting mate-
r;al of the formula V ;nto a solut;on of the 4H-3,1-benz-
oxaz;n-4-one of the formula IY, 3nd to carry out the re-
act;on ;n She manner descr;bed above. To lsolate the
N-acy~anthran;l;c acid der;vat;ve, any excess starting
mater;al of the formula V can be removed under reduced
pressure, and the procedure described under process A
then followed.
The Examples which follow ;llustrate the prepara-
tion of same N-acylanthranilic acid derivatives of the
formula I.
EXAMPLE 1
358 parts of benzoyl chlor;de and 258 parts of
tr;ethylam;ne wereintroduced, v;a t~o feeds, into a stir-
red ~;xture of 350 parts of 6-fluoroanthranilic acid and
400C parts of methylene chloride at from 25 to 30C in
the course of 20 minutes. The reaction m;xture was st;rred
for 30 m;nutes at 25C, after wh;ch it was st;rred ;nto
4000 parts of d;lute hydrochlor;c ac;d. The prec;pitate
wh;ch separated out was f;ltered off under suct;on, washed
w;th water and taken up ;n d;lute sod;um hydrox;de solu-
t;on, and the resulting solution was extracted three times
~ith ethyl acetate. The aqueous phasewas then stirred
into dilute hydrochloric acid, the precipitate wh;ch
separated out was filtered off under suction, ~ashed with
water and dried, and 560 parts (96X of theory) of N-ben-
zoyl-6-fluoroanthranil;c ac;d of melting point 169-171C
were obta;ned.
.~
~21478~
- 14 O.z. 0050/3~410
EXAMPLE 2
15 parts of N-benzoyl-6-fluoroanthranilic ac;d
;n a m;xture of 210 parts of methanol and 10.53 parts of
30X strength sod;um me~hylate were st;rred to g;ve a clear
solut;on, wh;ch was then evaporated down under reduced
pressure. 16.4 parts (100X of theory) of sod;um N-benzoyl-
6-fluoroanthranilate of melting po;nt 207C (decompo-
s;t;on) were obtained.
EXAMPLE 3
9 9 of S~fluoro-2-phenyl-3,1-benzoxaz;n-4-one were
mixed w;th 35.7 ~ of phenol at 45C ;n the presence of
a pellet of sod;um hydrox;de as a catalyst, and stirr;ng
was then continued for 3 hours at 185C. The excess
phenol ~asd;stilled off under reduced pressure, and the
res;due wh;ch rema;ned was first stirred w;th water and f;l-
tered off unter suct;on, and then st;rred with a 2:1 mix-
ture of petroleum ether and d;ethyl ether and once aga;n
f;ltered off under suction. The product was dried to give
10 9 t78X of theory) of phenyl N-benzoy~-6-fluoroanthrani-
late of melt;ng po;nt 130-132C.
EXAMPLE 4
0.2 part of tr;ethylaminewas added, as a catalyst,
to a m;xture of 5 parts of 5-chloro-3-(3'-d;fluoromethoxy-
phenyl)-3,1-benzoxazin-4-one and 14 parts of methanol, and
the mixture wasstirred for 2 hours at 65C. Itwas then
evaporated down under reduced pressure, the res;due was
tr;turated w;th water, washed and dr;ed, and 5.3 parts
t96X of theory) of methyl N-t3-tr;fluoromethoxybenzoyl)-
6-chloroanthran;late of melting point 73-75nC were ob-
ta;ned.
12147~
- 15 - 0~Zo OQ50/ 36410
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- 16 - O.Z. 0050/36410
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- 17 - O.Z. 0050/36410
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- 20 - O.Z. 0050/36410
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- 22 - O.Z. 0050/36410
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- 24 - O.Z. 0050/36410
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1214780
- 25 - O.Z. 0050/36410
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- 26 - O.Z. 0050/36410
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- 28 - O~Z. 0050/36410
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The N-acylanthranilic acid derlvatives of the for-
mula I may be applied for instance in the form of directly
sprayable solutions, powders, suspensions (including high-
-percentage aqueous, oily or other suspensions), disper-
05 sions, emulsions, oil dispersions, pastes, dusts, broad-
casting agents, or granules by spraying, atomizing,
dusting, broadcasting or watering. m e forms of applica-
tion depend entirely on the purpose for which the agents
are being used, but they must ensure as fine a distribu-
tion of the actlve ingredients according to the inventionas possible.
For the preparation of solutions, emulsions, pastes
and oil dlspersions to be sprayed dlrect, mineral oil frac-
tions of medlum to high boiling point, such as kerosene or
diesel oil, ~urther coal-tar olls, and oils of vegetable
or animal origin, aliphatic, cyclic and aromatic hydro-
carbons such as benzene, toluene, xylene, paraffin, tetra-
hydronaphthalene, alkylated naphthalenes and their
derivatives such as methanol, ethanol, propanol, butanol,
chloroform, carbon tetrachloride, cyclohexanol, cyclo-
hexanone, chlorobenzene, isophorone, etc., and strongly
polar solvents such as dimethylformamide, dimethyl sulf-
oxide5 N-methylpyrrolidone, water, etc. are suitable.
Aqueous formulations may be prepared from emulsion
concentrates, pastes, oil dispersions or wettable powders
by adding water. To prepare emulsions, pastes and oil dis-
persions the ingredients as such or dissolved in an oil or
solvent may be homogenized in water by means of wetting or
dispersing agents, adherents or emulsifiers. Concentrates
3~ which are sultable for dilution with water may be prepared
from active ingredient, wetting agent, adherent, emulsify-
ing or dispersing agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline
earth metal and ammonium salts of ligninsulfonic acid,
naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl
sulfonates, alkyl sulfates, and alkyl sulfonates, alkali
~214~7g~
- 31 - O.Z. 0050/36~10
metal and alkallne earth metal salts of dibutylnaphthalene-
sulfonic acid, lauryl ether sulfate, fatty alcohol sul-
fates, alkali metal and alkaline earth metal salts of
fatty acids, salts of sulfated hexadecanols, hepta-
05 decanols, and octadecanols, salts of sulfated fatty alco-
hol glycol ethers, condensation products of sulfonated
naphthalene and naphthalene derlvatives with formaldehyde,
condensation products of naphthalene or naphthalenesul-
fonlc acids with phenol and formaldehyde, polyoxyethylene
octylphenol ethers, ethoxylated isooctylphenol, eth-
oxylated octylphenol and ethoxylated nonylphenol, alkyl-
phenol polyglycol ethers, tributylphenyl polyglycol
ethers, alkylaryl polyether alcohols, isotrldecyl alcohol,
~atty alcohol ethylene oxlde condensates, ethoxylated
castor oil, polyoxyethylene alkyl ethers, ethoxylated poly-
oxypropylene, lauryl alcohol polyglycol ether acetal,
sorbitol esters, llgnln, sulflte waste liquors and methyl
cellulose.
Powders, dusts and broadcasting agents may be
prepared by mixing or grinding the active ingredients with
a solid carrier.
Granules, e.g., coated, impregnated or homogeneous
granules, may be prepared by bonding the active ingre-
dients to solid carriers. Examples of solid carriers are
mlneral earths such as slllcic acld, slllca gels,
silicates, talc, kaolin, attapulgus clay, limestone, lime,
chalk, bole, loess, clay, dolomite, diatomaceous earth,
calcium sulfate, magnesium sulfate, magnesium oxide,
ground plastics, fertilizers such as ammonium sulfate,
ammonium phosphate, ammonium nitrate, and ureas, and vege-
table products such as grain flours, bark meal, wood meal,
and nutshell meal, cellulosic powders, etc.
The formulations contain from 0.1 to 95, and prefer-
ably 0.5 to 90, % by weight of active ingredient.
Examples of formulations are given below.
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I. 90 parts by weight of compound no. 1 is mixed
with lO parts by weight of N-methyl-alpha-pyrrolidone. A
mlxture is obtained which is suitable for application in
the form of very fine drops.
05 II. 20 parts by weight of compound no. 2 is
dissolved in a mixture consisting of 90 parts by weight of
xylene, 6 parts by weight of the adduct of 8 to 10 moles
of ethylene oxide and 1 mole of olelc acid-N-monoethanol-
amide, 2 parts by weight of the calcium salt of dodecyl-
benzenesulfonic acid, and 2 parts by weight of the adduct
of 40 moles of ethylene oxide and 1 mole of castor oil.
III. 20 parts by weight of compound no. 5 is
dlssolved in a mixture consisting o~ 60 parts by weight of
cyclohexanone, 30 parts by weight of isobutanol, 5 parts
by welght of the adduct of 7 moles of ethylene oxide and
1 mole of isooctylphenol, and 5 parts by weight of the
adduct of 40 moles of ethylene oxlde and 1 r.~ole of castor
oil.
IV. 20 parts by weight of compound no. 21 is
dissolved in a mixture consisting of 25 parts by weight of
cyclohexanol, 65 parts by weight of a mineral oil fraction
having a boiling point between 210 and 280C, and
10 parts by weight of the adduct of 40 moles of ethylene
oxide and 1 mole of castor oil. By pouring the solution
into 100,000 parts by weight of water and uniformly
distributing it therein, an aqueous dispersion is obtained
containing 0.02% by weight of the active ingredient.
V. 80 parts by weight of compound no. 5 is well
mixed with 3 parts by weight of the sodium salt of diiso-
butylnaphthalene-alpha-sulfonic acid, 10 parts by weight
of the sodium salt of a lignin-sulfonic acid obtained from
a sulfite waste liquor, and 7 parts by weight of powdered
silica gel, and triturated in a hammer mill.
VI. 5 parts by weight of compound no. 1 is
intimately mixed with 95 parts by weight of particulate
kaolin. A dust is obtained containing 5% by weight of the
active ingredient.
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_ 33 - O.Z. 0050/36410
VII. 30 parts by weight of compound no. 21 is
intimately mixed with a mixture consisting of 92 parts by
weiæht of powdered sllica gel and 8 parts by weight of
paraffin oil which has been sprayed onto the surface of
05 this silica gel. A formulation of the active ingredient is
obtained having good adherence.
VIII. 20 parts of compound no. 1 is intimately mixed
with 2 parts of the calcium salt of dodecylbenzenesulfonic
acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts
of the sodlum salt of a phenolsulfonic acid-urea-form-
aldehyde condensate and 68 parts of a paraffinic mineral
oil. A stable oily dispersion is obtalned.
The actlve lngredlents, or agents contalning them,
may be applled pre- or postemergence. If certain crop
plants tolerate the active ingredients less well when they
are applied postemergence, application technlques may be
used in which the herblcidal agents are sprayed from
sultable equlpment ln such a manner that the leaves of
sensitive crop plants are lf possible not touched, and the
agents reach the soil or the unwanted plants growlng
beneath the crop plants (post-directed, lay-by treatment).
m e amount of active ingredient applled depends on
the time of the year, the plants to be combated and their
growth stage, the type of soil and the application method
-25 employed, and varies from 0.1 to 5 kg/ha and more, but is
preferably from 0.25 to 2.0 kg/ha.
The herbicidal action of the N-acylanthranilic acid
derivatives of the formula I is demonstrated in greenhouse
experiments.
The vessels employed were plastic flowerpots having a
volume of 300 cm3, and which were filled with a sandy loam
containing about 1.5% humus.
For the postemergence treatment, the plants were
first grown in the vessels to a height of from 3 to 15 cm,
depending on growth form, before being treated. The rice
plants were gro~n ln a peat-enriched substrate. For this
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- 34 - ~.Z. 0050/36410
treatment, elther plants which had been sown directly ln
the pots and grown there were selected, or plants which
had been grown from seedllngs and were transplanted to the
pots a ~ew days before treatment. The application rates
05 were ~rom 0.5 to 3.0 kg of active ingredient per hectare.
The pots were set up in the greenhouse - species from
warmer areas at from 20 to 35C, and species from
moderate cllmates at 10 to 20C. The experiments were run
for 2 to 4 weeks. During this period, the plants were
tended and their reactions to the varlous treatments
assessed. The scale used for assessment was O to 100, 0
denoting no damage or normal emergence, and 100 denoting
nonemergence or complete destruction of at least the
vlsible plant parts.
Ihe plants used in the experiments were Arachis
hypogaea, Centaurea cyanus, Chenopodium album, Chrysan-
themum segetum, Cyperus iria, Desmodium tortuosum, Hordeum
vulgare, Mercurialis annua, Nicandra physaloldes, Oryza
sativa, Sesbania exaltata, Urtica urens, Zea mays, Cyperus
esculentus, Avena fatua, and Galium aparlne.
The experiments show that for instance compounds
nos. 1, 5 and 21, applied postemergence at a rate of
0.5 kg/ha, have a selective herbicidal action, parti-
cularly on certain unwanted plants from warmer climates.
Compounds nos. 2 and 243, applied postemergence at a rate
of 1.0 kg/ha, are also selectively active. For example
compounds nos. 3, 46 and 234, applied postemergence at a
rate of 3.0 kg/ha, are well tolerated by crop plants and
combat unwanted plants in grass crops.
In view of the good tolerance by numerous broadleaved
and other crops and the numerous application methods
possible, the herbicides according to the invention, or
agents containing them, may be used in a ~urther large
number of crops for removing unwanted plant growth.
m e following crops may be ment~oned by way of
example:
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- 35 - O.Z. 0050/36410
Botanical name Common name
Allium cepa onions
Ananas comosus pineapples
05 Arachis hypogaea peanuts (groundnuts)
Asparagus officinal.is asparagus
Avena satlva oats
8eta vulgaris spp. altissima sugarbeets
Beta vulgaris spp. rapa fodder beets
lO Beta vulgaris spp. esculenta table beets, red beets
Camellia slnensls tea plants
Carthamus tinctorius safflower
Carya lllinolnensis pecan trees
Cltrus limon lemons
15 Cltrus maxima grapefruits
Cltrus retlculata mandarlns
Cltrus slnensls orange trees
Coffea arablca (Coffea canephora,
Coffea liberlca) coffee plants
20 Cucumis melo melons
Cucumls satlvus cucumbers
Cynodon dactylon Bermudagrass in turf
and lawns
Elais gulneensls oll palms
25 Fragarla vesca strawberries
Glycine max soybeans
Gossypium hirsutum
(Gossypium arboreum cotton
Gossyplum herbaceum
30 GoSSypium vitifolium)
Hellanthus annuus sunflowers
Hellanthus tuberosus
Hevea braslliensls rubber plants
Hordeum vulgare barley
35 Humulus lupulus hops
Ipomoea batatas sweet potatoes
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- 36 - O.Z. 0050~36410
Juglans regia walnut trees
Lens culinaris lentlls
Linum usitatissimum flax
Lycopersicon lycopersicum tomatoes
05 Malus spp. apple trees
Manlhot esculenta cassava
Medicago sativa alfal~a (lucerne)
Mentha piperita peppermint
Musa spp. banana plants
10 Nicothiana tabacum tobacco
(N. rustica)
Olea europaea olive trees
Oryza sativa rice
Panlcum mlliaceum
15 Pha~eolus lunatus limabeans
Phaseolus mungo mungbeans
Phaseolus vulgaris snapbeans, green beansJ
dry beans
Pennisetum glaucum
20 Petroselinum crispum parsley
spp. tuberosum
Picea abies Norway spruce
Abies alba ~lr trees
Pinus spp. pine trees
25 Pisum sativum English peas
Prunus avium cherry trees
Prunus domestica plum trees
Prunus dulcis almond trees
Prunus persica peach trees
30 Pyrus communis pear trees
Ribes sylvestre redcurrants
Ribes uva-crispa gooseberries
Ricinus communis castor-oil plants
Saccharum officinarum sugar cane
35 Secale cereale rye
Sesamum lndicum sesame
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_ 37 _ O.Z. 0050/36410
Botanical name Common name
_
Solanum tuberosum Irlsh potatoes
Sorghum bicolor (s. vulgare) sorghum
05 Sorghum dochna
Spinacia oleracea spinach
Theobroma cacao cacao plants
Trifolium pratense red clover
Tritlcum aestivum wheat
10 Vaccinium corymbosum blueberries
Vacclnium vitis-idaea cranberries
Vicla faba tlck beans
Vigna sinensis (V. unguiculata) cow peas
Vitis vinifera grapes
15 Zea mays Indian corn, sweet
corn, maize
To lncrease the spectrum of action and to achieve
synerglstic effect~ the N-acylanthranilic acid derivatives
of the formula I, or agents containing them, may be mixed
; and applied together with numerous representatives of
other herbicidal or growth-regulating active ingredient
groups. Examples of suitable mixture components are di-
azlnes, 4H-3,1-benzoxazine derivatives, benzothiadi-
azinones, 2,6-dinitroanilines, N-phenylcarbamates, thiol-
carbamates, halocarboxylic acids, trlazines, amldes, other
ureas, trlazinones, uraclls, benzofuran derivatives, cyclo-
hexane-1,3-dione derivatives, etc.
It may also be useful to apply the novel compounds,
or herbicidal agents containing them, either alone or in
combination with other herbicides, in admixture with other
crop protection agents, e.g., agents for combating pests
or phytopathogenic fungi or bacteria. The compounds may
also be mixed with solutions of mineral salts used to
remedy nutritional or trace element deficiencies. Non-
-phytotoxic olls and oil concentrates may also be added.
