3-aryluracil derivatives and their use for weed control

3-Aryluracil derivatives of the formula I ##STR1## in which --W-- is the group ##STR2## where the ring nitrogen atom is bonded via the C atom; R.sub.1 is hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.3 alkenyl or C.sub.4 alkenyl or C.sub.3 alkynyl or C.sub.4 alkynyl; PA0 R.sub.2 is halogen or cyano; PA0 R.sub.3 is hydrogen or halogen; PA0 R.sub.4 is hydrogen, halogen or C.sub.1 -C.sub.4 alkyl; PA0 R.sub.5 is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 haloalkyl; or R.sub.4 and R.sub.5 together are --(CH.sub.2).sub.n --; PA0 n is the number 3 or 4; PA0 R.sub.13 is C.sub.1 -C.sub.4 alkyl, C.sub.3 alkenyl or C.sub.4 alkynyl or C.sub.3 alkynyl or C.sub.4 alkynyl; and PA0 Q is one of the groups a) to e): ##STR3## where R.sub.6 to R.sub.12 are substituents, m is 3, 4 or 5, X is oxygen or sulfur and t is 2, 3 or 4, and if R.sub.1 is hydrogen, the agrochemically acceptable salts of compounds of the formula I. the compounds of formula I have herbicidal properties and are suitable as the active ingredient in a herbicide.

The present invention relates to novel 3-aryluracils of the formula I: 
##STR4## 
in which --W-- is the group 
##STR5## 
where the ring nitrogen atom is bonded via the C atom; R.sub.1 is 
hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.3 
alkenyl or C.sub.4 alkenyl or C.sub.3 alkynyl or C.sub.4 alkynyl; 
R.sub.2 is halogen or cyano; 
R.sub.3 is hydrogen or halogen; 
R.sub.4 is hydrogen, halogen or C.sub.1 -C.sub.4 alkyl; 
R.sub.5 is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 haloalkyl; or R.sub.4 
and R.sub.5 together are --(CH.sub.2).sub.n --; 
n is the number 3 or 4; 
R.sub.13 is C.sub.1 -C.sub.4 alkyl, C.sub.3 alkenyl or C.sub.4 alkenyl or 
C.sub.3 alkynyl or C.sub.4 alkynyl; and 
Q is one of the groups a) to e): 
a) 
##STR6## 
where R.sub.6 is hydrogen, C.sub.1 -C.sub.8 alkyl, C.sub.3 -C.sub.7 
cycloalkyl or C.sub.3 -C.sub.7 cycloalkyl-C.sub.1 -C.sub.4 alkyl; 
b) 
##STR7## 
where R.sub.6 is as defined under a); R.sub.7 is hydrogen, C.sub.1 
-C.sub.8 alkyl, C.sub.2 -C.sub.8 alkenyl, C.sub.2 -C.sub.8 alkynyl, 
C.sub.3 -C.sub.7 cycloalkyl, phenyl, or phenyl which is substituted by 
halogen, C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy, or benzyl, or 
benzyl which is substituted by halogen, C.sub.1 -C.sub.4 alkyl or C.sub.1 
-C.sub.4 alkoxy; 
c) 
##STR8## 
where R.sub.6 is as defined under a); R.sub.8 and R.sub.9 independently 
of one another are hydrogen, C.sub.1 -C.sub.8 alkyl, C.sub.2 -C.sub.8 
alkenyl, C.sub.2 -C.sub.8 alkynyl, phenyl, or phenyl which is substituted 
by halogen, C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy, or benzyl, 
or benzyl which is substituted by halogen, C.sub.1 -C.sub.4 alkyl or 
C.sub.1 -C.sub.4 alkoxy; or R.sub.8 and R.sub.9 together are 
--(CH.sub.2).sub.m --; and 
m is the number 3,4 or 5; 
d) 
##STR9## 
where R.sub.6 is defined under a); R.sub.10 is C.sub.1 -C.sub.8 alkyl, 
C.sub.2 -C.sub.8 alkenyl, C.sub.2 -C.sub.8 alkynyl, C.sub.1 -C.sub.4 
alkoxy-C.sub.1 -C.sub.6 alkyl, hydroxy-C.sub.1 -C.sub.6 alkyl or C.sub.1 
-C.sub.8 haloalkyl; and 
X is oxygen or sulfur; 
e) 
##STR10## 
where R.sub.6 is as defined under a); R.sub.11 and R.sub.12 independently 
of one another are hydrogen or C.sub.1 -C.sub.4 alkyl; 
t is the number 2, 3 or 4; and 
X is oxygen or sulfur; and 
if R.sub.1 is hydrogen, also the agrochemically acceptable salts of 
compounds of the formula I. 
The 3-aryluracils of the formula I according to the invention in which the 
group-W-is in the amide form Ia 
##STR11## 
or in the imino ether form Ib 
##STR12## 
in which R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.13 and Q are 
as defined under formula I, and the salts of these compounds which are 
possible, are herbicidally active and are suitable as active ingredients 
of herbicides. The present invention therefore also embraces herbicides 
which comprise the compounds according to the invention as active 
ingredients, processes for the preparation of these compounds, and the use 
of such compounds, or compositions, for controlling weeds. 
Other herbicidally active 3-aryluracil derivatives are disclosed, for 
example, in EP-A-0 195 346, in which uracils with Q as carboxylic acid 
groups and ester groups are disclosed; EP-A-0 255 047, in which uracils 
with Q as ether, (thio)carbonyloxy and sulfonyloxy groups are disclosed; 
and EP-A-0 260 621, in which uracils with Q as ether, alkylcarbonyloxy, 
alkoxycarbonyloxy and alkoxycarbonyl groups are disclosed. 
In the formula I, Ia and Ib of the 3-aryluracils according to the 
invention, halogen in the definitions of the radicals R.sub.2, R.sub.3 and 
R.sub.4 is fluorine, chlorine, bromine and iodine. The alkyl, alkenyl and 
alkynyl radicals R.sub.1, R.sub.4 and R.sub.5 and the corresponding 
radicals R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11 and 
R.sub.12, which are suitable as substituents in Q, can be straight-chain 
or branched, and this also applies to the alkyl moiety of the haloalkyl 
and alkoxy groups. Examples of such alkyls which may be mentioned are 
methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl or t-butyl, 
examples of alkenyls which may be mentioned are allyl, methallyl or 
but-2-en-1-yl, and examples of alkynyls which may be mentioned are 
propargyl, but-2-in-1-yl, but-3-in-1-yl and pent-4-in-1-yl. Alkoxyalkyl in 
the definitions of the radical R.sub.10 is, for example, methoxymethyl, 
methoxyethyl or ethoxyethyl. The radicals R.sub.10 are identical. A 
haloalkyl group can have one or more (identical or different) halogen 
atoms, examples of a polyhalogenated alkyl group which may be mentioned 
being trifluoromethyl and pentafluoroethyl. The cycloalkyl radicals 
R.sub.6 and R.sub.7 which are suitable as substituents are, for example, 
cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl. 
The salts of the compounds of the formula I are, in particular, alkali 
metal salts, for example sodium salts and potassium salts; alkaline earth 
metal salts, for example calcium salts and magnesium salts; ammonium 
salts, i.e. unsubstituted ammonium salts and mono- or polysubstituted 
ammonium salts, for example triethylammonium salts and methylammonium 
salts, and salts with other organic bases, for example with pyridine. 
The possible existence of at least one asymmetric carbon atom in the 
compounds of the formula I results in the fact that the compounds can 
exist in optically active individual isomers as well as in the form of 
racemic mixtures. Active substances of the formula I in the present 
invention are to be understood as meaning the pure optical antipodes as 
well as their racemates. Unless specific mention is made of the individual 
optical antipodes, the formula indicated is to be understood as meaning 
those racemic mixtures which are formed in the particular preparation 
process. Where appropriate, the existence of an aliphatic C.dbd.C double 
bond can also result in geometric isomers. In the case of those compounds 
of the formula I in which R.sub.1 is hydrogen, it is also not excluded 
that keto/enol tautomerism 
##STR13## 
exists. The formula I is intended to embrace all these isomeric forms 
which are possible as well as mixtures thereof. 
Amongst the compounds of the formula I, the following meanings of the 
radicals below must be emphasised: 
a) R.sub.1 is hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, 
C.sub.3 alkenyl or C.sub.4 alkenyl, or C.sub.3 alkynyl or C.sub.4 alkynyl, 
in particular methyl, allyl or propargyl; and/or 
b) R.sub.2 is cyano, in particular fluorine, chlorine, or bromine; and/or 
c) R.sub.3 is hydrogen or fluorine; and/or 
d) is R.sub.4 methyl, in particular hydrogen or fluorine; and/or 
e) R.sub.5 is methyl, trifluoromethyl, pentafluoroethyl; or R.sub.4 and 
R.sub.5 together form an alkylene bridge, n being the number 3 or 4in 
particular the number 3; and/or 
f) R.sub.7 is hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.3 -C.sub.5 alkenyl, 
C.sub.3 -C.sub.5 alkynyl or benzyl; and/or 
g) R.sub.10 is C.sub.1 -C.sub.5 alkyl, C.sub.3 -C.sub.5 alkenyl, C.sub.3 
-C.sub.5 alkynyl or hydroxyethyl; X is preferably oxygen; and/or 
h) R.sub.11 and R.sub.12 independently of another are methyl, in particular 
hydrogen, and t is the number 2 or 3; and/or 
i) R.sub.13 is C.sub.1 alkyl or C.sub.2 alkyl, allyl or propargyl. 
Preferred 3-aryluracil derivatives of the formula I are those in which 
R.sub.1 is C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.3 
alkenyl or C.sub.4 alkenyl or C.sub.3 alkynyl or C.sub.4 alkynyl; in 
particular those in which R.sub.1 is methyl, allyl or propargyl; R.sub.1 
is preferably methyl. 
Other preferred 3-aryluracil derivatives of the formula I are those in 
which Q is a radical of the formula 1 in which R.sub.6 is as defined under 
formula I; in particular those in which R.sub.6 is hydrogen, C.sub.1 
-C.sub.5 alkyl or C.sub.3 -C.sub.6 cycloalkyl. 
Other preferred 3-aryluracil derivatives of the formula I are those in 
which Q is a radical of the formula 2, in which R.sub.6 and R.sub.7 are as 
defined under formula I; in particular those in which R.sub.6 is hydrogen 
or C.sub.1 -C.sub.5 alkyl; and R.sub.7 is hydrogen, C.sub.1 -C.sub.5 
alkyl, C.sub.3 -C.sub.5 alkenyl, C.sub.3 -C.sub.5 alkynyl or benzyl. 
Other preferred 3-aryluracil derivatives of the formula I are those in 
which Q is a radical of the formula 3, in which R.sub.6, R.sub.8 and 
R.sub.9 are as defined under formula I; in particular in which R.sub.6 is 
hydrogen or C.sub.1 -C.sub.5 alkyl; and R.sub.8 and R.sub.9 are in each 
case methyl. 
Other preferred 3-aryluracil derivatives of the formula I are those in 
which Q is a radical of the formula 4, in which R.sub.6, R.sub.10 and X 
are as defined under formula I; in particular those in which R.sub.6 is 
hydrogen, C.sub.1 -C.sub.5 alkyl or C.sub.3 -C.sub.6 cycloalkyl; and 
R.sub.10 is C.sub.1 -C.sub.5 alkyl, C.sub.3 -C.sub.5 alkenyl, C.sub.3 
-C.sub.5 alkynyl or hydroxy-C.sub.2 -C.sub.4 alkyl. 
Other preferred 3-aryluracil derivatives of the formula I are those in 
which Q is a radical of the formula 5, in which R.sub.6, R.sub.11, 
R.sub.12, t and X are as defined under formula I; in particular those in 
which R.sub.6 is hydrogen, C.sub.1 -C.sub.5 alkyl or C.sub.3 -C.sub.6 
cycloalkyl; R.sub.11 and R.sub.12 independently of one another are 
hydrogen or methyl; and t is the number 2 or 3; R.sub.11 and R.sub.12 are 
preferably hydrogen. 
Particularly preferred 3-aryluracil derivatives of the formula Ia are those 
in which R.sub.1 is hydrogen, methyl, allyl or propargyl; R.sub.2 is 
fluorine, chlorine, bromine or cyano; R.sub.3 is hydrogen or fluorine; 
R.sub.4 is hydrogen, fluorine or methyl; R.sub.5 is methyl, 
trifluoromethyl or pentafluoroethyl; or R.sub.4 and R.sub.5 together are 
--(CH.sub.2).sub.n --; and n is the number 3 or 4; and in which, in 
particular, R.sub.1 is hydrogen or methyl; R.sub.2 is fluorine, chlorine, 
bromine or cyano; R.sub.4 is fluorine or hydrogen; or R.sub.4 and R.sub.5 
together are --(CH.sub.2).sub.n --in which n is the number 3. 
Other particularly preferred 3-aryluracil derivatives of the formula Ib are 
those in which R.sub.2 is fluorine, chlorine, bromine or cyano; R.sub.3 is 
hydrogen or fluorine; R.sub.4 is hydrogen, fluorine or methyl; R.sub.5 is 
methyl, trifluoromethyl or pentafluoroethyl; or R.sub.4 and R.sub.5 
together are --(CH.sub.2).sub.n --; n is the number 3 or 4; and R.sub.13 
is methyl, ethyl, allyl or propargyl; and in which, in particular, R.sub.2 
is fluorine, chlorine, bromine or cyano; R.sub.4 is hydrogen or fluorine 
and n is the number 3. 
Especially preferred are 3-aryluracil derivatives of the formula I in which 
-W- is the group 
##STR14## 
R.sub.1 is hydrogen or methyl; R.sub.2 is fluorine, chlorine, bromine or 
cyano; R.sub.3 is hydrogen or fluorine; R.sub.4 is hydrogen; R.sub.5 is 
methyl, trifluoromethyl, pentafluoroethyl; or R.sub.4 and R.sub.5 together 
are --(CH.sub.2).sub.n --; n is the number 3; and Q is one of the groups 
a) to e): 
##STR15## 
in which R.sub.6 is hydrogen, C.sub.1 -C.sub.5 alkyl or C.sub.3 -C.sub.6 
cycloalkyl; 
##STR16## 
in which R.sub.6 is as defined under a); and R.sub.7 is hydrogen, C.sub.1 
-C.sub.4 alkyl, allyl or benzyl; 
c) 
##STR17## 
in which R.sub.6 is as defined under a); 
d) 
##STR18## 
in which R.sub.6 is as defined under a); and R.sub.10 is C.sub.1 -C.sub.5 
alkyl or 
e) 
##STR19## 
in which R.sub.6 is as defined under a); R.sub.11 and R.sub.12 are in each 
case hydrogen; t is the number 2 or 3; or R.sub.11 is hydrogen and 
R.sub.12 is methyl; n is the number 2; and X is oxygen or sulfur. 
Mention must be made of the following as preferred individual compounds of 
the formula I: 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]-benzaldehyde, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]acetophenone oxime methylether, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]acetophenone ethylene ketal, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]benzophenone ethylene ketal, 
3-[4-chloro-3-(3-methylbutyryl)phenyl]-1-methyl-6-trifluoromethyl-2,4(1H, 
3H)pyrimidinedione, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]acetophenone, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]phenyl-1-(i)propyl ketone, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]phenyl-1-(n)butyl ketone, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]phenyl-1-(3-methylbutyl) keton, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]phenyl-1-cyclopropyl ketone, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]phenyl-1-ciclopentyl ketone, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]phenyl-1-cyclohexyl ketone, 
2-chloro-4-fluoro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H) 
-pyrimidinyl]acetophenone, 
2-chloro-4-fluoro-5-[3,6-dihydro-2,6-dioxo-3,4-dimethyl 
1(2H)-pyrimidinyl]acetophenone, 
2,4-Difluoro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyri 
midinyl]acetophenone, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-pentafluoroethyl-1(2H)-pyrimid 
inyl]phenyl-1-(i)propyl ketone, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]propiophenone, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-pentafluoroethyl-1(2H)-pyrimid 
inyl]propiophenone, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]phenyl-1-(n)propyl ketone, 
2-bromo-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidin 
yl]acetophenone, 
2-fluoro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]acetophenone, 
2-chloro-4-fluoro-5-[3,6-dihydro-2,6-dioxo-3,4-dimethyl-1(2H)-pyrimidinyl]p 
ropiophenone, 
2-chloro-4-fluoro-5-[1,2,4,5,6,7-hexahydro-1-methyl-2,4-dioxo 
3H-cyclopenta[d]pyrimidin-3-yl]acetophenone, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]-4-fluorobenzaldehyde, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]acetophenone oxime, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]acetophenonoxime ethyl ether, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]acetophenonoxime isopropylether, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]acetophenonoxime allyl ether, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]acetophenone oxime benzyl ether, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]benzal oxime 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2)-pyrimidin 
yl]acetophenone oxime (i)butyl ether, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]acetophenone N,N-dimethylhydrazone, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]benzaldehyde N,N-dimethylhydrazone, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]acetophenone methyl ethylene acetal, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]acetophenone propylene acetal, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]benzaldehyde dimethoxy acetal, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]benzaldehyde ethylene acetal, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]acetophenone propylene dithio acetal, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]acetophenone ethylene dithio acetal, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]acetophenone methyl ethylene dithio acetal, 
2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl-1(2H)-pyrimidi 
nyl]benzaldehyde isopropyl oxime. 
The process according to the invention for the preparation of the compounds 
of the formula I and the salts thereof is analogous to known processes and 
comprises, 
a) for the preparation of those 3-aryluracil derivatives of the formula I 
in which R.sub.1 is hydrogen, and, if appropriate, metal salts of these 
compounds, subjecting a compound of the formula IIa or IIb 
##STR20## 
in which R.sub.2, R.sub.3, R.sub.4, R.sub.5 and Q are as defined under 
formula I and R.sub.14 is C.sub.1 -C.sub.6 alkyl, preferably C.sub.1 
-C.sub.4 alkyl, to a cyclisation by treatment with a base, and, if 
desired, converting a resulting salt of the uracil derivative of the 
formula IIc 
##STR21## 
in which R.sub.2, R.sub.3, R.sub.4, R.sub.5 and Q are as defined and 
M.sub.1 .sym. is a cation, for example an alkali metal ion, into the 
compounds of the formula I in which R.sub.1 is hydrogen (protonated form) 
by treatment with an acid; 
b) for the preparation of those 3-aryluracil derivatives of the formula I 
in which R.sub.1 is C.sub.1 -C.sub.4 alkyl, C.sub.3 alkenyl or C.sub.4 
alkenyl, C.sub.3 alkynyl or C.sub.4 alkynyl or C.sub.1 -C.sub.4 haloalkyl, 
alkylating a uracil derivative of the formula Ic 
##STR22## 
in which R.sub.2, R.sub.3, R.sub.4, R.sub.5 and Q are as defined under 
formula I, in the presence of an alkylating agent containing a suitable 
C.sub.1 -C.sub.4 alkyl, C.sub.3 alkenyl or C.sub.4 alkenyl, C.sub.3 
alkynyl or C.sub.4 alkynyl or C.sub.1 -C.sub.4 haloalkyl group; the 
O-alkylation product of the formula Id 
##STR23## 
can also be obtained as a further product, in which R.sub.13' is as 
defined for R.sub.1, with the exception of hydrogen; 
c) for the preparation of those 3-uracil derivatives of the formula I in 
which R.sub.1 is C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, 
C.sub.3 alkenyl or C.sub.3 alkenyl or C.sub.3 alkynyl or C.sub.4 alkynyl 
and Q is a group 
##STR24## 
in which R.sub.6 is C.sub.1 -C.sub.8 alkyl, C.sub.3 -C.sub.7 cycloalkyl or 
C.sub.3 -C.sub.7 cycloalkyl-C.sub.1 -C.sub.4 alkyl, reacting a carboxylic 
acid derivative of the formula III 
##STR25## 
in which R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are as defined 
under formula I and Z is halogen, preferably chlorine, or a leaving group, 
preferably N,O-dimethylhydroxylamino, with an organometal compound of the 
formula 
EQU R.sub.6' --M.sub.2 (VIIa) 
EQU or 
EQU R.sub.6' --M.sub.3 --G (VIIb), 
in which 
R.sub.6' is C.sub.1 -C.sub.8 alkyl, C.sub.3 -C.sub.7 cycloalkyl or C.sub.3 
-C.sub.7 cycloalkyl-C.sub.1 -C.sub.4 alkyl; 
M.sub.2 is an alkali metal ion, preferably lithium; 
M.sub.3 is an alkaline earth metal ion or a metal of sub-group one or two 
of the Periodic System, preferably magnesium; and 
G is halogen, preferably chlorine or bromine; 
d) for the preparation of those 3-aryluracil derivatives of the formula I 
in which R.sub.1 is C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, 
C.sub.3 alkenyl or C.sub.4 alkenyl or C.sub.3 alkynyl or C.sub.4 alkinyl, 
and Q is a group 
##STR26## 
in which R.sub.6 is hydrogen, C.sub.1 -C.sub.8 alkyl, C.sub.3 -C.sub.7 
cycloalkyl or C.sub.3 -C.sub.7 cycloalkyl-C.sub.1 -C.sub.4 alkyl, 
oxidising a carbinol of the formula IV 
##STR27## 
in which R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are as defined 
under formula I; 
e) for the preparation of those 3-aryluracil derivatives of the formula I 
in which Q is a group 
##STR28## 
in which R.sub.6 and R.sub.7 are as defined under formula I, by reacting 
an aldehyde or ketone of the formula I in which Q is a group 
##STR29## 
with a hydroxylamine of the formula H.sub.2 N--O--R.sub.7 (VIII); 
f) for the preparation of those 3-aryluracil derivatives of the formula I 
in which Q is a group 
##STR30## 
in which R.sub.6, R.sub.8 and R.sub.9 are as defined under formula I, by 
reacting an aldehyde or ketone of the formula I in which Q is a group 
##STR31## 
with a hydrazine of the formula 
##STR32## 
g) for the preparation of those 3-aryluracil derivatives of the formula I 
in which Q is a group 
##STR33## 
in which R.sub.6, R.sub.10, R.sub.11, R.sub.12 and X are as defined under 
formula I, by reacting an aldehyde or ketone of the formula I in which Q 
is a group 
##STR34## 
with an alcohol or thiol of the formula R.sub.10 --X--H (Xa) or 
##STR35## 
h) for the preparation of those 3-aryluracil derivatives of the formula Ib 
(imino ether form) 
##STR36## 
first subjecting a uracil of the formula Ic 
##STR37## 
in which R.sub.2, R.sub.3, R.sub.4, R.sub.5 and Q are as defined under 
formula I to a halogenation, obtaining the uracil of the formula V, 
##STR38## 
in which Y is halogen, preferably chlorine, and reacting the compound of 
the formula V subsequently with an alcohol of the formula R.sub.13 -OH 
(XIa) or with the corresponding alcoholate of the formula R.sub.13 
--O.sup..crclbar. M.sub.4.sup..sym. (XIb), in which R.sub.13 is as defined 
under formula I and M.sub.4.sup..sym. is an alkali metal ion or alkaline 
earth metal ion, catalysed by a base; 
i) for the preparation of those 3-aryluracil derivatives of the formula I 
in which R.sub.2 is cyano, reacting a compound of the formula I in which 
R.sub.2 is halogen with a metal cyanide of the formula XII 
EQU M.sub.5 (CN).sub.s (XII), 
in which M.sub.5 is an alkali metal ion or a metal of sub-group one or two 
of the Periodic System and s is the number 1 or 2; 
j) for the preparation of those 3-aryluracil derivatives of the formula I 
in which R.sub.1 is C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, 
C.sub.3 alkenyl or C.sub.4 alkenyl or C.sub.3 alkynyl or C.sub.4 alkynyl 
and Q is a group 
##STR39## 
in which R.sub.6 is C.sub.1 -C.sub.8 alkyl or C.sub.3 -C.sub.7 
cycloalkyl-C.sub.1 -C.sub.4 alkyl, reacting a reactive acid derivative of 
the formula III 
##STR40## 
in which Z is a halogen, preferably chlorine, with an organometal compound 
of the formula XIII 
##STR41## 
in which R.sub.14 is C.sub.1 -C.sub.6 alkyl, preferably C.sub.1 -C.sub.4 
alkyl, 
R.sub.15 is hydrogen, C.sub.1 -C.sub.7 alkyl, C.sub.3 -C.sub.7 cycloalkyl, 
C.sub.3 -C.sub.7 cycloalkyl-C.sub.1 -C.sub.3 alkyl, and 
M.sub.2.sup..sym. is an alkali metal cation, preferably lithium or sodium, 
and hydrolysing and decarboxylating the resulting intermediates of the 
formula VI 
##STR42## 
in which R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are as defined under 
formula I in an acid-catalysed subsequent reaction to give the 
3-aryluracils of the formula I; 
k) for the preparation of those 3-aryluracil derivatives of the formula I 
in which Q is a group 
##STR43## 
in which R.sub.6 is as defined under formula I and R.sub.7 is C.sub.1 
-C.sub.8 alkyl, C.sub.2 -C.sub.8 alkenyl, C.sub.2 -C.sub.8 alkynyl, 
C.sub.3 -C.sub.7 cycloalkyl, benzyl oder benzyl which is substituted by 
halogen, C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy converting an 
oxime of the formula I in which Q is a group 
##STR44## 
into a reactive alkali metal salt and subsequently converting the latter 
with a compound of the formula XIV 
EQU R.sub.7 --Z' (XIV), 
in which Z' is a leaving group, preferably halogen; and, if desired, and 
with the proviso that R.sub.1 is hydrogen, converting a compound of the 
formula I obtained in accordance with these process variants which have 
been listed into a salt. 
The cyclisation by process variant a) can be carried out expediently by 
treating the compound of the formula IIa or IIb with a base at 
temperatures between -78.degree. C. and the reflux temperature of the 
reaction mixture, in an inert protic organic solvent such as an alcohol, 
for example methanol, ethanol or isopropanol; an inert aprotic organic 
solvent such as an aliphatic or cyclic ether, for example 
1,2-dimethoxyethane, tetrahydrofuran or dioxane, or an aromatic, for 
example benzene or toluene; an inert aprotic, polar organic solvent, for 
example dimethylformamide or dimethyl sulfoxide, it being possible for 
such solvents to be used, if appropriate, in a two-phase mixture with a 
hydrocarbon, for example n-hexane or toluene; or water. Suitable bases 
are, preferably, sodium alcoholates, alkali metal hydroxides, in 
particular sodium hydroxide or potassium hydroxide, alkali metal 
carbonates, in particular sodium carbonate or potassium carbonate, or 
sodium hydride. If sodium hydride is used as the base, the solvent is 
preferably an aliphatic or cyclic ether, dimethylformamide or dimethyl 
sulfoxide, it being possible for each of these solvents to be used in the 
form of a mixture with toluene. 
When the cyclisation has ended, the product exists in the form of the 
corresponding alkali metal salt if one of the abovementioned or related 
bases are used. This alkali metal salt can be isolated and purified in a 
manner known per se, or it is possible to acidify the mixture so as to 
isolate the particular compound of the formula I. To this end, a mineral 
acid is preferably used, such as hydrochloric acid, or a strong organic 
acid, such as acetic acid or p-toluenesulfonic acid. 
In process variant b), the term "alkylated" means the introduction of a 
C.sub.1 -C.sub.4 alkyl, C.sub.3 alkenyl or C.sub.4 alkenyl, C.sub.3 
alkynyl or C.sub.4 alkynyl, or C.sub.1 -C.sub.4 haloalkyl group at the 
unsubstituted nitrogen atom of the uracil ring. The alkylating agent used 
is expediently a C.sub.1 -C.sub.4 alkyl halide, C.sub.3 alkenyl or C.sub.4 
alkenyl halide or C.sub.3 alkynyl or C.sub.4 alkynyl halide, in particular 
the chloride or bromide in question, or sulfonate, or a polyhalogenated 
C.sub.1 -C.sub.4 alkane, for example chlorodifluoromethane, or a mono- or 
polyhalogenated alkene, for example tetrafluoroethene. 
The alkylation is expediently carried out in the presence of an inert 
protic organic solvent such as a lower alkanol, for example ethanol, if 
desired as a mixture with water; of an inert, aprotic organic solvent, 
such as an aliphatic or cyclic ether, for example 1,2-dimethoxyethane, 
tetrahydrofuran or dioxane; of a ketone, for example acetone or 
butan-2-one; or of an inert, aprotic, polar organic solvent, for example 
dimethylformamide, dimethyl sulfoxide or acetonitrile, and in the presence 
of a base, such as sodium hydride, of an alkali metal hydroxide, in 
particular sodium hydroxide or potassium hydroxide, of an alkali metal 
alcoholate, in particular sodium alcoholate, or of an alkali metal 
carbonate or alkali metal hydrogen carbonate, in particular sodium 
carbonate, potassium carbonate, sodium hydrogen carbonate or potassium 
hydrogen carbonate, at temperatures between 0.degree. C. and the reflux 
temperature of the reaction mixture, preferably at temperatures between 
50.degree. C. and 100.degree. C. In a preferred embodiment, the uracil 
derivative of the formula Ic is first treated with the base, such as 
sodium hydride, sodium ethanolate or sodium carbonate, in the solvent and, 
after a brief reaction time, the halide in the same solvent is added. In a 
further embodiment, the uracil derivative Ic is reacted together with a 
dialkyl sulfate in the presence of an alkali metal hydrogen carbonate, in 
particular sodium hydrogen carbonate or potassium hydrogen carbonate, in 
the solvent, for example acetone, at reflux temperature. As a rule, the 
reaction is complete within a relatively short time or after a few hours, 
depending on the solvent used. 
The reaction by process variant c) is expediently carried out using a 
carboxylic halide of the formula III in which Z is preferably chlorine, 
and an organometal compound of the formula VIIa or VIIb, in an aprotic 
organic solvent, preferably aliphatic or cyclic ethers for example diethyl 
ether, dimethoxyethane or tetrahydrofuran. The reaction temperatures are 
generally between -80.degree. C. and 0.degree. C., preferably at 
temperatures around -70.degree. C. To react the reactive carboxylic acid 
derivatives of the formula III in which Z is an N,O-dimethylhydroxylamino 
group, an organometal compound of the formula VIIa or VIIb is employed, 
but preferably the Grignard compound VIIb in tetrahydrofuran at 0.degree. 
C. 
In the oxidation according to process variant d), it is expedient to 
oxidise a benzyl alcohol of the formula IV with a suitable oxidant, for 
example pyridinium dichromate, pyridinium chlorochromate, potassium 
permanganate, ruthenium tetroxide or manganese dioxide, in an inert 
organic solvent, for example in chlorinated hydrocarbons such as carbon 
tetrachloride or dichloromethane, or in an aliphatic nitrile such as 
acetonitrile. Other solvents which can be employed are acetic acid or 
mineral acids, for example sulfuric acid. The reaction temperatures used 
are between -20.degree. C. and +50.degree. C., preferably between 
0.degree. C. and +30.degree. C. In a preferred embodiment, the uracil 
derivative of the formula IV is oxidised with pyridinium chlorochromate in 
dichloromethane. 
The oximation of a 3-aryluracil derivative of the formula I, in which Q is 
an aldehyde or ketone group, with unsubstituted or O-substituted 
hydroxylamine of the formula VIII according to process variant e) is 
expediently carried out in an organic solvent, for example in a lower 
alcohol, preferably methanol, ethanol or isopropanol, if desired in a 
mixture with water, at temperatures between 0.degree. C. and the boiling 
point of the reaction mixture. The reagent hydroxylamine of the formula 
VIII can be employed in the form of the free base or in the form of an 
acid addition salt, for example as the hydrochloride salt or the hydrogen 
sulfate salt. The oximation proceeds spontaneously or with basic catalysis 
by addition of an organic base, for example pyridine, triethylamine or 
4-dimethylaminopyridine, or by addition of an alkali metal carbonate, 
alkali metal hydrogen carbonate, alkaline earth metal carbonate or 
alkaline earth metal hydrogen carbonate, for example sodium carbonate or 
potassium carbonate. 
The hydrazone formation of a 3-aryluracil derivative of the formula I, in 
which Q is an aldehyde group or ketone group, with unsubstituted or 
substituted hydrazine of the formula IX according to process variant f) is 
expediently carried out in an organic solvent as indicated in the case of 
the oximation in process variant e). The hydrazine of the formula IX can 
be employed in the form of the free base or as the acid addition salt, for 
example as the hydrochloride or the hydrogen sulfate. The hydrazone 
formation proceeds spontaneously or is base-catalysed by addition of an 
organic base, for example pyridine, triethylamine or 
4-dimethylaminopyridine, or of an alkali metal carbonate, alkali metal 
hydrogen carbonate, alkaline earth metal carbonate or alkaline earth metal 
hydrogen carbonate, for example sodium carbonate, potassium carbonate or 
potassium hydrogen carbonate. 
The (thio)acetalisation of a 3-aryluracil derivative of the formula I, in 
which Q is an aldehyde group or a ketone group, with an alcohol or thiol 
of the formula Xa or Xb according to process variant g) is expediently 
effected in an inert organic solvent, for example in an aromatic 
hydrocarbon, preferably benzene, toluene or xylene, or in a halogenated 
hydrocarbon, preferably chloroform, at temperatures between -30.degree. C. 
and the boiling point of the reaction mixture, with an addition of either 
a catalytic amount, stoichiometric amount or excess of a carboxylic acid 
or organic sulfonic acid, for example p-toluenesulfonic acid, or a mineral 
acid, for example hydrochloric acid or sulfuric acid. The water of 
reaction formed during this process can be subjected to azeotropic 
distillation, for example, or removed from the reaction mixture by 
absorption in an alkali/alkaline earth aluminium silicate (molecular 
sieve). 
The halogenation by process variant h) is expediently effected by using a 
halogenating agent, for example thionyl chloride, phosphorus pentachloride 
or phosphorus oxychloride, or phosphorus pentabromide or phosphoryl 
bromide, without or in an inert organic solvent, for example n-hexane, 
benzene, toluene, xylene, dichloromethane, chloroform, 1,2-dichloroethane 
or chlorobenzene, at reaction temperatures between 0.degree. C. and the 
reflux temperature of the reaction mixture, preferably between 80.degree. 
C. and 120.degree. C. 
If necessary, an organic base, for example triethylamine, pyridine or 
4-dimethylaminopyridine, can be added to the reaction. If thionyl chloride 
is used, it is also expedient to add a catalytic amount of 
N,N-dimethylformamide. 
The 2-halopyrimidinone of the formula V is reacted in an excess of the 
particular alcohol of the formula XIa as the solvent at temperatures 
between 0.degree. C. and +50.degree. C., preferably at room temperature, 
in the presence of a suitable organic base, for example pyridine. If the 
reaction of the 2-halopyrimidinone of the formula V is reacted with the 
corresponding alcoholate of the formula XIb, then M.sub.4 .sym. is 
preferably an alkali metal ion, for example the sodium or potassium ion, 
or an alkaline earth metal ion, for example a calcium or magnesium ion. 
The sodium ion is preferred. 
When preparing the 3-aryluracil derivatives of the formula I in which 
R.sub.2 is a cyano group according to process variant i) an aromatic 
halogen substituent (R2=halogen) is exchanged for a cyano group by means 
of a metal cyanide of the formula XII. The latter is, in particular, a 
transition metal cyanide, preferably copper (I) cyanide. The exchange 
reaction is expediently effected in the presence of an aprotic, polar 
solvent such as alkylnitrile, for example acetonitrile, propionitrile or 
butyronitrile, or in the presence of an alkylurea, for example 
tetramethylurea, or of a dialkylamide, for example dimethylformamide, or 
of an dialkyl sulfoxide, for example dimethyl sulfoxide, or in 
N-methyl-2-pyrrolidone, 1,3-dimethyl-imidazolidin-2-one, 
1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone, hexamethylphosphoric 
triamide, at temperatures between +80.degree. C. and +200.degree. C., 
preferably between +150.degree. C. to +200.degree. C. 
In the preparation of the 3-aryluracils of the formula I according to 
process variant j), a compound of the formula III can expediently be 
reacted with an organometal compound of the formula XIII in an inert, 
aprotic organic solvent, for example in aliphatic or alicyclic ether, 
preferably 1,2-dimethoxyethane, tetrahydrofuran or dioxane, or in an 
inert, aprotic polar solvent, for example dimethylformamide, 
N-methylpyrrolidone, 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone or 
dimethyl sulfoxide, it being possible for such solvents to be used, if 
desired, in a two-phase mixture with hydrocarbons, for example n-hexane, 
cyclohexane or toluene. The bases employed are alkali metal hydrides, 
preferably sodium hydride or lithium hydride. The reaction temperature is 
between -20.degree. C. and +50.degree. C., preferably at room temperature. 
Acid hydrolysis and the subsequent decarboxylation of the 
.beta.-ketodiester intermediates of the formula VI is expediently effected 
in the presence of a mineral acid, for example sulfuric acid or 
hydrobromic acid, with or without solvent. Suitable solvents which are 
possible are lower carboxylic acids, preferably acetic acid. The reaction 
temperatures are between +80.degree. C. and +140.degree. C., preferably 
between +100.degree. C. and +120.degree. C. 
The oxime derivatives of the formula I in which Q is a group 
##STR45## 
and R.sub.7 is C.sub.1 -C.sub.8 alkyl, C.sub.2 -C.sub.8 alkenyl, C.sub.2 
-C.sub.8 alkynyl, C.sub.3 -C.sub.7 cycloalkyl or unsubstituted or 
substituted phenyl or benzyl, are expediently prepared in accordance with 
process variant k) by alkylating the corresponding oxime of the formula I, 
in which R.sub.7 is hydrogen, with a suitable alkylating agent, for 
example with alkyl halide, preferably with alkyl chloride, alkyl bromide 
or alkyl iodide, or a dialkyl sulfate in a lower alcohol, for example 
methanol or ethanol, or in an aliphatic or cyclic ether, for example 
dimethoxyethane, tetrahydrofuran or dioxane, preferably in an aprotic 
inert polar solvent, for example dimethylformamide, N-methylpyrrolidone or 
1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone or dimethyl sulfoxide, 
at temperatures between -10.degree. C. and +70.degree. C., preferably 
between 0.degree. C. and +80.degree. C. The bases used are alkali metal 
alcoholates or, preferably, alkali metal hydrides, such as sodium hydride. 
The salts of the resulting compounds of the formula I in which R.sub.1 is 
hydrogen can be prepared in a manner known per se, for example by 
dissolving the compounds of the formula I in a solution of a respective 
inorganic or organic base. As a rule, salt formation takes place within a 
short time at room temperature. In an embodiment, the sodium salt is 
prepared by dissolving the uracil derivative I in aqueous sodium hydroxide 
solution at room temperature, equivalent amounts of the uracil derivative 
and of sodium hydroxide being used. The solid salt can be isolated by 
precipitation with a suitable inert solvent or by evaporation of the 
solvent. In a further embodiment, an aqueous solution of an alkali metal 
salt of the uracil derivative I is introduced into an aqueous solution of 
a salt having a metal cation other than an alkali metal cation, the second 
metal salt of the uracil derivative being prepared. As a rule, this 
embodiment is used for the preparation of uracil metal salts which are 
insoluble in water. 
The resulting compounds of the formula I and the salts thereof can be 
isolated and purified by methods known per se. A person skilled in the art 
is furthermore familiar with the sequence in which it is expedient to 
carry out certain reactions under process variants a) to k) so as to avoid 
undesirable competitive reactions which are possible. 
If no targeted synthesis is effected for isolating pure isomers, the 
product can be obtained in the form of a mixture of two or more isomers. 
The isomers can be separated by methods known per se. If desired, pure 
optically active isomers can be prepared, for example, by synthesis from 
corresponding optically active starting materials. 
The starting compounds of the formulae IIa and IIb are novel and can be 
prepared analogously to known processes, for example EP-A-0 260 621, for 
example in accordance with reaction schemes 1 and 2 below (methods aa), 
bb), cc), dd), ee) and ff)). 
##STR46## 
The reaction by method aa) in reaction scheme 1 is expediently carried out 
in the presence of an anhydrous, aprotic, organic solvent, for example an 
aliphatic or cyclic ether, preferably diethyl ether, 1,2-dimethoxyethane, 
tetrahydrofuran or dioxane; an aliphatic or aromatic hydrocarbon, for 
example n-hexane, benzene, toluene or xylene; or of an inert aprotic, 
polar, organic solvent, for example dimethylformamide or dimethyl 
sulfoxide; or a halogenated aliphatic hydrocarbon, for example methylene 
chloride, chloroform, carbon tetrachloride or 1,2-dichloroethane, and in 
the presence or absence of a base, for example triethylamine or pyridine, 
where the latter can act both as a solvent and as a base, or a metal 
hydride, for example sodium hydride or potassium hydride. The reaction 
temperatures are preferably in the range from approximately -80.degree. C. 
to +50.degree. C., preferably at -30.degree. C. and room temperature. 
The reaction by method bb) is carried out analogously to method aa), except 
that the reaction temperature is in the range from -80.degree. C. to 
+150.degree. C., preferably between 0.degree. C. and +130.degree. C. 
The reaction by method cc) is expediently carried out by reacting the 
compounds of the formulae XVIII and XIX with each other in an anhydrous 
solvent and at increased temperature, with acid catalysis. Suitable 
solvents are, in particular, organic solvents which form azeotropes with 
water, for example benzene, toluene or xylenes; or halogenated 
hydrocarbons, for example methylene chloride, chloroform, carbon 
tetrachloride and chlorobenzene; or aliphatic or cyclic ethers, for 
example 1,2-dimethoxyethane, tetrahydrofuran or dioxane. Acid catalysts 
which are suitable are, in particular, strong mineral acids, for example 
sulfuric acid or hydrochloric acid, organic acids, for example 
p-toluenesulfonic acid and polyphosphoric acid, or acidic cation 
exchangers, for example "Amberlyst 15" (Fluka). The temperature range for 
this reaction is between +70.degree. C. and +120.degree. C., preferably at 
the boiling point of the reaction mixture. These reaction conditions 
simultaneously allow rapid removal of the water of reaction which has 
formed. 
The reaction by method dd) is expediently carried out in an inert organic 
solvent which is miscible with water, for example in an aliphatic or 
cyclic ether, preferably 1,2-dimethoxyethane, tetrahydrofuran or dioxane; 
or in a lower alcohol, preferably ethanol, at temperatures between 
+50.degree. C. and +100.degree. C., preferably at the boiling point of the 
reaction mixture; or in an aromatic solvent, for example benzene, toluene 
or xylene, in the presence of an acidic catalyst, for example hydrochloric 
acid or p-toluenesulfonic acid, and at temperatures between +50.degree. C. 
and +100.degree. C., preferably between +60.degree. C. and +80.degree. C. 
The reaction of the compounds of the formulae XXI and XXII by method ee) is 
expediently carried out in an anhydrous inert aprotic solvent, a 
hydrocarbon, for example benzene, toluene or xylene, a halohydrocarbon, 
for example dichloromethane or chloroform or an ether, for example diethyl 
ether, 1,2-dimethoxyethane, tetrahydrofuran or dioxane, in the presence of 
a base, for example pyridine, triethylamine or 4-dimethylaminopyridine, at 
temperatures between -50.degree. C. and the reflux temperature of the 
reaction mixture, preferably between -5.degree. C. and 35.degree. C. 
The reaction of the compounds of the formulae XXIII and XXIV is expediently 
carried out in an anhydrous inert aprotic solvent at temperatures between 
+70.degree. C. and +140.degree. C., preferably between +100.degree. C. and 
+120.degree. C. 
Suitable solvents are aromatic hydrocarbons, for example benzene, toluene 
and xylenes; halogenated hydrocarbons, for example carbon tetrachloride, 
trichloroethane, tetrachloroethane and chlorobenzene; or aliphatic and 
cyclic ethers, for example dibutyl ether, 1,2-dimethoxyethane, 
tetrahydrofuran and dioxane. The subsequent reaction of the compound which 
has been prepared in this manner, of the formula XXV, with carbamates of 
the formula XXVI is expediently carried out in an anhydrous solvent and in 
the presence of an acidic catalyst at increased temperature. 
Solvents which are suitable are preferably organic solvents which form 
azeotropes with water, for example aromatic hydrocarbons, preferably 
benzene, toluene and xylenes; halogenated hydrocarbons, for example carbon 
tetrachloride and chlorobenzene, and acidic catalysts which are suitable 
are preferably strong mineral acids, for example sulfuric acid; organic 
acids, for example p-toluenesulfonic acid; acids which contain phosphorus, 
for example orthophosphoric acid and polyphosphoric acid; or acidic cation 
exchangers, for example "Amberlyst 15" (Fluka). The temperatures employed 
are in the range from +70.degree. C. to 150.degree. C., preferably at the 
boiling point of the reaction mixture. This makes it possible for the 
water of reaction to be removed. 
The reaction of the amine of the formula XXIV with the diketene of the 
formula XXVII in accordance with method ff) is expediently carried out in 
an anhydrous, inert aprotic solvent, for example a halogenated 
hydrocarbon, preferably methylene chloride, chloroform, carbon 
tetrachloride or chlorobenzene; or an aromatic hydrocarbon, for example 
benzene, toluene or a xylene; or an aliphatic or cyclic ether, for example 
diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran or dioxane. The 
reaction proceeds with basic catalysis, for example in the presence of 
4-pyrrolidinopyridine, 4-dimethylaminopyridine, 
1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene, 
1,8-diazabicyclo[5.4.0]undec-7-ene or diethylamine, and exothermally, 
which is why it is carried out in a temperature range from -10.degree. C. 
to +50.degree. C., preferably at room temperature. The subsequent reaction 
of the compound obtained in this manner, of the formula XXV, with the 
carbamate of the formula XXVI is carried out analogously to the procedure 
described under method ee). 
The starting compounds XV, XVIII, XX, XXI, XXII and XXVI required in 
process variants aa) to ff) are known. 
The starting compound of the formula XVI (variant aa) can be prepared from 
the compound of the formula XXIV by reaction with phosgene or diphosgene, 
by known, analogous methods. 
The starting compound of the formula XVII (variant bb)) can be prepared 
from the compound of the formula XXIV by reaction with chloroformates, by 
known, analogous methods. 
The starting compound of the formula XIX (variant cc)) can be prepared from 
the compound of the formula XXIV by reaction with metal cyanates, by 
known, analogous methods. 
The starting compound of the formula XXIV (variant ee) and ff)) can be 
prepared from the compound of the formula XXIX 
##STR47## 
by reducing the nitro group, by known, analogous methods. 
The starting compound of the formula XXIX can be prepared from the compound 
of the formula XXX 
##STR48## 
by nitration, by known, analogous methods. 
The intermediates of the formulae IIa, IIb, IV, V and VI are novel; they 
were synthesised specifically for the synthesis of the active ingredients 
of the formula I according to the invention and are part of the present 
invention. 
It has now been found that the compounds of the formula I according to the 
invention (also termed "active ingredients" hereinafter) as well as the 
enol ethers or salts thereof are valuable active ingredients which have 
herbicidal properties and are suitable for controlling weeds, including 
grass weeds, inter alia Agropyron repens, Alopecurus myosuroides, Avena 
fatua, Bromus inermis, Echinochloa crus-galli, Poa annua, Sorghum 
halepense, Abutilon theophrasti, Amaranthus retroflexus, Cassia 
obtusifolia, Chenopodium album, Galium aparine, Matricaria chamomilla, 
Sinapis arvensis and Stellaria media, in various crops of useful plants, 
inter alia rice crops, in particular paddy rice, wheat, maize, soya beans, 
oilseed rape and cotton. In addition, the compounds are pre- and 
post-emergence herbicides. Some representatives of the compounds of the 
formula I have shown good selectivity, for example in the control of weeds 
in crops of soya beans and cotton. 
For practical purposes, a concentration from 1 g to 3 kg of the compound of 
the formula I per ha, preferably from 10 g to 1 kg/ha, is usually 
sufficient to achieve the desired herbicidal effect. To achieve the 
desired herbicidal effect in combination with optimum toleration by crop 
plants, the range from 10 to 100 g/ha is particularly favourable for 
pre-emergence treatment, and 100 to 1,000 g/ha for post-emergence 
treatment. 
The herbicides according to the invention comprise an effective amount of 
at least one compound of the formula I, or of an enol ether or salt 
thereof, and, as a rule, additionally formulation auxiliaries. They 
contain expediently at least in each case one formulation auxiliary from 
each of the following groups: 
solid carriers; 
solvents or dispersants; 
surfactants (wetting agents and emulsifiers); 
dispersants (without surfactant action); and 
stabilisers. 
As a rule, the pesticidal preparations comprise, besides the active 
ingredients of the formula I, 1 to 99% of a formulation auxiliary from the 
group of the 
solid carriers; 
solvents or dispersants; 
dispersants (without surfactant action); and 
stabilisers; and 0 to 25%, in particular 0.1 to 25%, of a surfactant 
(wetting agents and emulsifiers). 
Using such auxiliaries as well as others, the compounds of the formula I, 
i.e. the herbicidal active ingredients, can be converted into the 
customary formulations such as dusts, powders, granules, solutions, 
emulsions, suspensions, emulsifiable concentrates, pastes and the like. 
In general, the compounds of the formula I and the enol ethers thereof are 
insoluble in water, while the salts, in particular the alkali metal salts 
and ammonium salts, are generally water-soluble and can be manufactured by 
the methods customary for compounds which are insoluble, or soluble, in 
water, using the known formulation auxiliaries. The compositions can be 
prepared in the manner known per se, for example by mixing the active 
ingredient in question with solid carriers, by dissolving or suspending it 
in suitable solvents or dispersants, with or without surfactants as 
wetting agents or emulsifiers and/or dispersants, or by diluting 
previously produced emulsifiable concentrates with solvents or 
dispersants. 
The following are essentially suitable as solid carriers: 
natural minerals such as chalk, dolomite, limestone, clays and silica or 
salts thereof, for example Keiselguhr, kaolin, bentonite, talc, 
attapulgite or montmorillonite; 
synthetic minerals such as highly-disperse silica, alumina or silicates; 
organic substances such as cellulose, starch, ureas or synthetic resins; or 
fertilisers such as phosphates or nitrates. Such carriers can exist, for 
example, in the form of powders or granules. 
Solvents or dispersants which are suitable are essentially: aromatics, such 
as benzene, toluene, xylene and alkylnaphthalenes; -chlorinated aromatics 
and chlorinated aliphatic hydrocarbons such as chlorobenzenes, 
chloroethylenes or methylene chloride; -aliphatic hydrocarbons such as 
cyclohexane or paraffins, for example petroleum fractions; alcohols such 
as butanol or glycol and their ethers and esters; -ketones such as 
acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; or 
strongly polar solvents or dispersants such as dimethylformamide, 
N-methylpyrrolidone or dimethyl sulfoxide (such solvents preferably having 
flashpoints of at least 30.degree. C. and boiling points of at least 
50.degree. C.), or water. Other suitable solvents or dispersants are 
so-called liquefied gaseous extenders or carriers, which are products 
which are gaseous at room temperature and under atmospheric pressure. 
Examples of such products are, in particular, aerosol propellents such as 
halohydrocarbons, for example dichlorodifluoromethane. If the herbicide 
according to the invention is a gas packed in a pressure bottle, then it 
is expedient to use a solvent in addition to the propellent. 
The surfactants (wetting agents and emulsifiers) can be non-ionic compounds 
such as: condensation products of fatty acids, fatty alcohols or 
fatty-radical-substituted phenols with ethylene oxide; fatty acid esters 
and fatty acid ethers of sugars or polyhydric alcohols; products obtained 
from sugars or polyhydric alcohols by condensation with ethylene oxide; 
block copolymers of ethylene oxide and propylene oxide; or 
alkyldimethylamine oxides. 
The surfactants can also be anionic compounds such as: soaps; fatty sulfate 
esters, for example sodium dodecyl sulfate, sodium octadecyl sulfate and 
sodium cetyl sulfate; alkylsulfonates, arylsulfonates or fatty aromatic 
sulfonates, such as alkylbenzenesulfonates, for example calcium 
dodecylbenzenesulfonate or butylnaphthalenesulfonate; or more complex 
fatty sulfonates, for example the amide condensation product of oleic acid 
with N-methyltaurine, or dioctyl sodium sulfosuccinate. 
Finally, the surfactants can be cationic compounds such as 
alkyldimethylbenzylammonium chlorides, dialkyldimethylammonium chlorides, 
alkyltrimethylammonium chlorides or ethoxylated ammonium chlorides. 
The following are essentially suitable as dispersants (without surfactant 
action): lignin, sodium salts and ammonium salts of ligninsulfonic acids, 
sodium salts of maleic acid anhydride/diisobutylene copolymers, sodium 
salts and ammonium salts of sulfonated polycondensation products of 
naphthalene and formaldehyde, or sulfite liquors. 
Dispersants which are particularly suitable as thickeners or anti-settling 
agents are, for example, methylcellulose, carboxymethylcellulose, 
hydroxyethylcellulose, polyvinyl alcohols, alginates, caseinates and blood 
albumin. 
Examples of suitable stabilisers are: acid-binding agents, for example 
epichlorohydrin, phenyl glycidol ethers, or soya epoxides; antioxidants, 
for example gallic esters or butylhydroxytoluene; UV absorbers, for 
example substituted benzophenones, diphenylacrylonitrile esters or 
cinnamates; or deactivators, for example salts of 
ethylenediaminotetracetic acid, and polyglycols. 
The herbicides according to the invention comprise, as a rule, between 
0.001 and 95 per cent by weight, preferably between 0.5 and 75 per cent by 
weight, of one or more compounds of the formula I according to the 
invention as active ingredient(s). For example, they can exist in a form 
which is suitable for storage and for transport. As a rule, the active 
ingredient concentration in such formulations, for example emulsifiable 
concentrates, is in a relatively high range, preferably between 1 and 50 
per cent by weight, in particular between 5 and 30 per cent by weight. 
These formulations can then, for example with the same or different inert 
substances, be diluted to the active ingredient concentration which is 
suitable for use in practice, i.e. preferably approx. 0.001 to 10 per cent 
by weight, in particular approximately 0.005 to 5 per cent by weight. 
However, the active ingredient concentrations can also be lower or higher. 
As already mentioned, the herbicides according to the invention can be 
prepared in a manner known per se. 
To prepare pulverulent preparations, the active ingredient, i.e. at least 
one compound of the formula I according to the invention, can be mixed 
with a solid carrier, for example by grinding the substances together. 
Alternatively, the solid carrier can be impregnated with a solution or 
suspension of the active ingredient, and the solvent or dispersant can 
then be removed by evaporation, heating or filtration by suction under 
reduced pressure. Such pulverulent compositions can be rendered readily 
wettable with water by an addition of surfactants or dispersants, so that 
they can be converted into aqueous suspensions which are suitable, for 
example, as crop sprays. 
The active ingredient of the formula I can also be mixed with a surfactant 
and a solid carrier to form a wettable powder which is dispersible in 
water, or it can be mixed with a solid, pregranulated carrier to form a 
product in the form of granules. 
If desired, the active ingredient of the formula I can be dissolved in a 
solvent which is not miscible with water, for example a high-boiling 
hydrocarbon. The latter expediently comprises dissolved emulsifier, so 
that the solution is self-emulsifying when added to water. On the other 
hand, the active ingredient can be mixed with an emulsifier, and the 
mixture can then be diluted to the desired concentration with water. 
Moreover, the active ingredient can be dissolved in a solvent, and the 
solution can then be mixed with an emulsifier. Such a mixture can also be 
diluted to the desired concentration with water. In this manner, 
emulsifiable concentrates or ready-to-use emulsions are obtained. 
The herbicides described can be used according to the invention by 
customary application methods such as spraying, atomising, dusting, 
pouring or scattering.