Novel substituted thieno[3,2-b]pyran-5,7-diones of the general formula (I) ##STR1## Processes for their preparation and their use as herbicides and as plant growth regulators and novel intermediates of the formula (VI) ##STR2## (in which R.sup.1, R.sup.2, X, Y and Z have the meaning given in the description).

The present invention relates to novel, substituted thieno 
[3,2-b]pyran-5,7-diones to processes and novel intermediates for their 
preparation, and to their use as endoparasiticides, herbicides and as 
plant growth regulators. 
It has been disclosed that certain tetrahydropyran-2,4-diones have 
herbicidal properties (cf. EP-A-0,345,635). 
Novel substituted thieno[3,2-b]pyran-5,7-diones of the general formula (I) 
and of their tautomeric forms 
##STR3## 
have now been found, in which R.sup.1 represents hydrogen, straight-chain 
or branched radicals from the series comprising alkyl, alkenyl, alkynyl 
alkylsulphonyl, alkylcarbonyl, alkenylcarbonyl, in each case substituted 
or unsubstituted phenyl, benzoyl or benzenesulphonyl, 
R.sup.2 represents straight-chain or branched radicals from the series 
comprising alkyl, alkenyl, alkynyl, halogenoalkyl, cycloalkyl, in each 
case substituted or unsubstituted phenyl or benzyl, 
X and Y independently of one another represent hydrogen, halogen, cyano, 
nitro, straight-chain or branched alkyl, alkenyl, alkynyl, halogenoalkyl, 
cycloalkyl, alkylcarbonyl, alkoxycarbonyl, alkyloxy, alkylthio, 
halogenoalkoxy, halogenoalkylthio, alkylamino, dialkylamino, in each case 
substituted or unsubstituted aryl, aralkyl, aryloxy or arylthio, or 
X and Y together with the adjoining C atoms form a carbocyclic ring which 
is optionally interrupted by hetero atoms and 
Z represents oxygen or .dbd.NOR.sup.3, 
where 
R.sup.3 represents hydrogen and straight-chain or branched radicals from 
the series comprising alkyl, alkenyl, alkynyl, halogenoalkyl, 
halogenoalkenyl, halogenoalkynyl, cycloalkyl, substituted or unsubstituted 
phenyl, phenylalkyl, 
and their tolerated salts are possible. 
Furthermore, it has been found that the novel thieno[3,2-b]pyran-5,7-diones 
of the general formula (I) and their tautomeric forms 
##STR4## 
in which R.sup.1 represents hydrogen, straight-chain or branched radicals 
from the series comprising alkyl, alkenyl, alkynyl alkylsulphonyl, 
alkylcarbonyl, alkenylcarbonyl, in each case substituted or unsubstituted 
phenyl, benzoyl or benzenesulphonyl, 
R.sup.2 represents straight-chain or branched radicals from the series 
comprising alkyl, alkenyl, alkynyl, halogenoalkyl, cycloalkyl, in each 
case substituted or unsubstituted phenyl or benzyl, 
X and Y independently of one another represent hydrogen, halogen, cyano, 
nitro, straight-chain or branched alkyl, alkenyl, alkynyl, halogenoalkyl, 
cycloalkyl, alkylcarbonyl, alkoxycarbonyl, alkyloxy, alkylthio, 
halogenoalkoxy, halogenoalkylthio, alkylamino, dialkylamino, in each case 
substituted or unsubstituted aryl, aralkyl, aryloxy or arylthio, or 
X and Y together with the adjoining C atoms form a carbocyclic ring which 
is optionally interrupted by hetero atoms and 
Z represents oxygen or NOR.sup.3, where 
R.sup.3 represents hydrogen and straight-chain or branched radicals from 
the series comprising alkyl, alkenyl, alkynyl, halogenoalkyl, 
halogenoalkenyl, halogenoalkynyl, cycloalkyl, substituted or unsubstituted 
phenyl or phenylalkyl, 
and their tolerated salts are obtained when 
a) Thieno[3,2-b]pyran-5,7-diones of the formula (II) 
##STR5## 
in which X and Y have the abovementioned meaning, 
are reacted with an acid chloride of the formula (III) 
##STR6## 
in which R.sup.2 has the abovementioned meaning, if appropriate in the 
presence of a base and if appropriate in the presence of a diluent to give 
the enol ester and the product is subsequently reacted in the same or in 
another diluent at a temperature between 0.degree. C. and 100.degree. C., 
to give the C-acylated product if appropriate in the presence of a 
reaction auxiliary, or 
b) when the thienopyran-2,4-diones of the general formula (II) are reacted 
with a carboxylic acid of the general formula (IV) 
EQU R.sup.2 --COOH (IV) 
in which 
R.sup.2 has the abovementioned meaning, if appropriate in the presence of a 
diluent and if appropriate in the presence of a dehydrating reagent and if 
appropriate in the presence of a reaction auxiliary, at a temperature 
between 0.degree. C. and 100.degree. C., 
or 
c) when thieno[3,2-b]pyran-5,7-diones of the formula (II) are reacted with 
an acid chloride of the formula (III), if appropriate in the presence of a 
Lewis acid, to give derivatives of the general formula (I) in which t 
represents oxygen and R.sup.1 represents hydrogen in a single step, 
d) or when, in the case where Z represents .dbd.NOR.sup.3 in formula (I) 
thieno-[3,2-b]pyran-5,7-diones of the formula (I) 
##STR7## 
in which Z represents oxygen and the remaining radicals have the 
abovementioned meaning, 
are reacted with a corresponding hydroxylamine or its ammonium compounds 
R.sup.3 ONH.sub.2 and R.sup.3 ONH.sub.3.sup..sym. W.sup..crclbar. 
respectively, wherein W.sup..crclbar. represents an anion equivalent of an 
inorganic acid and R.sup.3 has the abovementioned meaning, at a 
temperature between 0.degree. C. and 80.degree. C., those thieno 
[3,2-b]pyran-5,7-dione derivatives of the formula (I) in which Z denotes 
an oxime ether group (.dbd.NOR.sup.3) being obtained. 
The compounds of the formula (I) in which 
R.sup.1 represents straight-chain or branched radicals from the series 
comprising alkyl, alkenyl, alkynyl, alkylsulphonyl, alkylcarbonyl, 
alkenylcarbonyl, in each case substituted or unsubstituted phenyl, 
benzenesulphonyl or benzoyl, 
and R.sup.2, X, Y, and Z have the above mentioned meaning, 
are obtained in a following reaction step if the compounds of the formula 
(I) in which 
R.sup.1 represents hydrogen are reacted with compounds of the formula (IX) 
EQU R.sup.1 --V (IX) 
in which 
R.sup.1 represents straight-chain or branched radicals from the series 
alkyl, alkenyl, alkynyl, alkylsulphonyl, alkylcarbonyl, alkenylcarbonyl, 
in each case substituted or unsubstituted phenyl, benzenesulphonyl or 
benzoyl, and V represents halogen, especially chlorine, bromine or iodine 
(process e). 
The compounds of the formula (I) are highly suitable for use as 
endoparasiticides, in particular in the field of veterinary medicine. 
Finally, it has been found that the novel thieno [3,2-b]pyran-5,7-diones of 
the general formula (I) in which Z denotes an oxime ether group 
(.dbd.NOR.sup.3), have an unexpected herbicidal action, and derivatives in 
which Z denotes oxygen have plant-growth-regulating properties. 
The invention preferably relates to compounds of the formula (I) and their 
tautomeric forms in which 
R.sup.1 represents hydrogen, straight-chain or branched radicals from the 
series comprising C.sub.1 -C.sub.7 -alkyl, C.sub.3 -C.sub.6 -alkenyl, 
C.sub.3 -C.sub.6 -alkynyl, C.sub.1 -C.sub.6 -alkylsulphonyl, C.sub.1 
-C.sub.6 -alkylcarbonyl, C.sub.1 -C.sub.6 -alkenylcarbonyl, in each case 
substituted or unsubstituted phenyl, benzenesulphonyl or benzoyl, 
R.sup.2 represents straight-chain or branched radicals from the series 
comprising C.sub.1 -C.sub.7 -alkyl, C.sub.2 -C.sub.6 -alkenyl, C.sub.2 
-C.sub.6 -alkynyl, C.sub.1 -C.sub.7 -halogenoalkyl having 1 to 15 
identical or different halogen atoms, C.sub.3 -C.sub.7 -cycloalkyl or in 
each case substituted or unsubstituted phenyl or benzyl, 
X and Y independently of one another represent hydrogen, halogen, cyano, 
nitro, straight-chain or branched C.sub.1 -C.sub.7 -alkyl, C.sub.2 
-C.sub.6 -alkenyl, C.sub.2 -C.sub.6 -alkynyl, C.sub.1 -C.sub.7 
-halogenoalkyl having 1 to 15 identical or different halogen atoms, 
C.sub.3 -C.sub.6 -cycloalkyl, C.sub.1 -C.sub.6 -alkylcarbonyl, C.sub.1 
-C.sub.6 -alkyloxycarbonyl, C.sub.1 -C.sub.7 -alkyloxy, C.sub.1 -C.sub.7 
-alkythio, 1-5 halogeno-C.sub.1-4 -alkoxy, 1-5 halogeno-C.sub.1-4 
-alkythio, C.sub.1 -C.sub.7 -alkylamino, C.sub.1 -C.sub.7 -dialkylamino, 
in each case substituted or unsubstituted aryl, aralkyl, aryloxy or 
arylthio, or 
X and Y together form a carbocyclic ring which consists of 4 to 8 carbon 
atoms and which is optionally interrupted by hetero atoms such as 
nitrogen, oxygen or sulphur, and 
Z represents oxygen or NOR.sup.3, where 
R.sup.3 represents hydrogen and straight-chain or branched radicals from 
the series comprising C.sub.1 -C.sub.7 -alkyl, C.sub.2 -C.sub.6 -alkenyl, 
C.sub.2 -C.sub.6 -alkynyl, C.sub.1 -C.sub.7 -halogenoalkyl having 1 to 15 
identical or different halogen atoms, C.sub.2 -C.sub.6 -halogenoalkenyl 
having 1 to 11 identical or different halogen atoms, C.sub.2 -C.sub.6 
-halogenoalkynyl having 1 to 9 identical or different halogen atoms, 
C.sub.3 -C.sub.6 -cycloalkyl, or substituted or unsubstituted phenyl or 
benzyl, 
suitable substituents on the aromatic radicals being halogen, cyano, nitro, 
straight-chain or branched alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, 
alkylthio, halogenoalkylthio, alkylsulphinyl, halogenoalkylsulphinyl, 
alkylsulphonyl, halogenoalkylsulphonyl, alkylenedioxy, 
halogenoalkylenedioxy, 
and their tolerated salts. 
Particularly preferably, the invention relates to compounds of the formula 
(I) and their tautomeric forms in which 
R.sup.1 represents hydrogen, straight-chain or branched and radicals from 
the series comprising C.sub.1 -C.sub.6 -alkyl, C.sub.3 -C.sub.4 -alkenyl, 
C.sub.2 -C.sub.4 -alkynyl, C.sub.1 -C.sub.4 -alkylsulphonyl, C.sub.1 
-C.sub.4 -alkylcarbonyl, C.sub.2 -C.sub.5 -alkenylcarbonyl, or in each 
case substituted or unsubstituted phenyl, benzenesulphonyl or benzoyl, 
R.sup.2 represents straight-chain or branched radicals from the series 
comprising C.sub.1 -C.sub.6 -alkyl, C.sub.1 -C.sub.4 -alkenyl, C.sub.2 
-C.sub.4 -alkynyl, C.sub.1 -C.sub.6 -halogenoalkyl having 1 to 13 
identical or different halogen atoms or C.sub.3 -C.sub.6 -cycloalkyl, in 
each case substituted or unsubstituted phenyl or benzyl 
X and Y independently of one another represent hydrogen, halogen, cyano, 
nitro, straight-chain or branched C.sub.1 -C.sub.6 -alkyl, C.sub.2 
-C.sub.5 -alkenyl, C.sub.2 -C.sub.5 -alkynyl, C.sub.1 -C.sub.6 
-halogenoalkyl having 1 to 13 identical or different halogen atoms, 
C.sub.3 -C.sub.6 -cycloalkyl, C.sub.3 -C.sub.6 -alkylcarbonyl, C.sub.1 
-C.sub.6 -alkyloxycarbonyl, C.sub.1 -C.sub.6 -alkyloxy, C.sub.1 -C.sub.6 
-alkylthio, C.sub.1 -C.sub.6 -alkylamino, C.sub.1 -C.sub.6 -dialkylamino, 
in each case substituted or unsubstituted aryl, aralkyl, aryloxy or 
arylthio, or 
X and Y together with the adjoining C atoms form a carbocyclic ring which 
consists of 4 to 8 carbon atoms and which is optionally interrupted by 
hetero atoms such as nitrogen, oxygen or sulphur, and 
Z represents oxygen or NOR.sup.3, where 
R.sup.3 represents hydrogen and straight-chain or branched radicals from 
the series comprising C.sub.1 -C.sub.6 -alkyl, C.sub.2 -C.sub.4 -alkenyl, 
C.sub.2 -C.sub.4 -alkynyl, C.sub.1 -C.sub.6 -halogenoalkyl having 1 to 13 
identical or different halogen atoms, C.sub.2 -C.sub.4 -halogenoalkenyl 
having 1 to 7 identical or different halogen atoms, C.sub.2 -C.sub.4 
-halogenoalkynyl having 1 to 5 identical or different halogen atoms, 
C.sub.3 -C.sub.6 -cycloalkyl, or substituted or unsubstituted phenyl or 
benzyl, 
suitable substituents on the aromatic radicals being halogen, cyano, nitro, 
straight-chain or branched C.sub.1 -C.sub.4 -alkyl, 1-5-halogeno-C.sub.1-4 
-alkyl-C.sub.1-4 alkoxy, 1-5-halogeno-C.sub.1-4 -alkoxy, C.sub.1-4 
-alkylthio, 1-5-halogeno-C.sub.1-4 -alkylthio, C.sub.1-4 -alkylsulphinyl, 
1-5-halogeno-C.sub.1-4 -alkylsulphinyl, C.sub.1-4 -alkylsulphonyl, 
1-5-halogeno-C.sub.1-4 -alkylsulphonyl, C.sub.1-2 -alkylenedioxy, 
1-4-halogeno-C.sub.1-2 -alkylenedioxy, 
and their tolerated salts with monovalent and divalent metal cations, in 
each case substituted or unsubstituted ammonium ions, phosphonium ions, 
sulphonium ions and sulphoxonium ions. 
The invention particularly preferably relates to compounds of the formula 
(I) and their tautomeric forms in which 
R.sup.1 represents hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, 
i-butyl, t-butyl, n-pentyl, i-pentyl, allyl, n-butenyl, i-butenyl, 
propinyl, acetyl, propionyl, acroyl, isobutyryl, pivaloyl, valeroyl, 
phenyl, benzoyl, 4-methylbenzoyl, 4-ethylbenzoyl, 4-n-propylbenzo-yl, 
4-isopropylbenzoyl, 4-n-butylbenzoyl, 4-i-butylbenzoyl, 4-t-butylbenzoyl, 
2,4,6-trimethylbenzoyl, p-methylphenylsulphonyl, benzenesulphonyl, 
R.sup.2 represents methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, 
i-butyl, t-butyl, n-pentyl, i-pentyl, s-pentyl, t-pentyl, neo-pentyl, 
n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, in each case 
substituted or unsubstituted phenyl or benzyl, 
X and Y independently of one another represent hydrogen, fluorine, 
chlorine, bromine, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, 
i-butyl, s-butyl, t-butyl, n-pentyl, cyclopropyl, cyclobutyl, cyclopentyl, 
cyclohexyl, methoxy, ethoxy, n-propyloxy, i-propyloxy, n-butyloxy-, 
i-butyloxy, t-butyloxy, n-pentyloxy or neo-pentyloxy, methylthio-, 
ethylthio-, n-propylthio, i-propylthio, n-butylthio-, i-butylthio, 
t-butylthio, n-pentylthio, dimethylamino, diethylamino, dipropylamino, 
dibutylamino, methoxymethyl, ethoxymethyl, methylthiomethyl, 
ethylthiomethyl, 1-methoxyethyl, 2-methoxythioethyl, 1,3-dimethoxypropyl, 
2-ethoxy-ethyl, 1-methyl-2-methylthio-ethyl, 
2-methyl-1-methylthiomethylpropyl, 1-methyl-butyl, 2-methyl-1-propenyl, 
phenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 2,4-dichlorophenyl, 
4-methoxyphenyl, 2,4,6-trimethylphenyl, 3,5-dibromophenyl, 
4-methylthiophenyl, 4-fluorophenyl, or 
X and Y together with the adjoining C atoms form a carbocyclic ring which 
consists of 5 to 6 carbon atoms and which is optionally interrupted by 
hetero atoms such as nitrogen, oxygen or sulphur, and 
Z represents oxygen or NOR.sup.3, where 
R.sup.3 represents hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, 
i-butyl, t-butyl, allyl, prop-2-ynyl, 3-fluoropropyl, 
trans-3-chloro-prop-2-enyl, transbut-2-enyl, cis-3-chloro-prop-2-enyl, 
but-2-ynyl, 2-methoxyethyl, E-4(4-fluorophenyl)but-2-enyl, 
E-4(4-chlorophenyl)but-2-enyl, E-4(4-tert.-butylphenyl)but-2-enyl, 
E-4(4-trifluorophenyl)but-2-enyl; E-4-phenyl-but-2-enyl, 2-thienyl, 
3-thienyl; 5-chloro-thienyl or optionally substituted benzyl, 
suitable substituents on the aromatic radicals being halogen, cyano, nitro, 
methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, 
chloromethyl, fluoromethyl, dichloromethyl, trichloromethyl, 
difluoromethyl, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, 
methylsulphinyl, methylsulphonyl, trifluoromethylsulphinyl, 
trifluoromethylsulphonyl, 
and their tolerated salts for example with monovalent metal cations, in 
particular sodium, potassium, or an equivalent of a polyvalent cation, for 
example an alkaline earth metal cation, in particular magnesium, calcium 
and also agriculturally utilised cations such as manganese, copper, zinc 
and iron cations, and also ammonium, phosphonium, sulphonium and 
sulphoxonium cations such as ammonium, tetraalkylammonium, 
benzyltrialkylammonium, trialkylsulphonium or trialkylsulphoxonium. 
The abovementioned definitions of radicals, or illustrations, which are 
general or mentioned in ranges of preference, apply correspondingly to end 
products and to the starting materials and intermediates. These 
definitions of radicals can be combined with each other as desired, but 
that is to say also between the particular ranges of preference. 
If, for example, thieno-[3,2 -b]pyran-5,7-dione and butyry chloride are 
used as educts, the course of the reaction of process (a) according to the 
invention can be outlined by the following equation: 
##STR8## 
In this process, the thieno-[3,2-b]pyran-5,7-dione first reacts to give the 
enol ester and the product subsequently reacts, with an acid or basic 
catalyst, in the same or in a different solvent, to give the 
thieno[3,2-b]-6-butyryl-pyran-5,7-dione according to the invention. 
In the presence of a Lewis acid catalyst 
thieno[3,2-b]-6-butyryl-pyran-5,7-dione is obtained in a single reaction 
step according to the invention (process c). 
If, for example, thieno-[3,2-b]pyran-5,7-dione and butyric acid are used as 
educts, the course of the reaction of process (b) according to the 
invention can be outlined by the following equation: 
##STR9## 
In this case, the thieno[3,2-b]pyran-5,7-dione reacts with the carboxylic 
acid in question in the presence of a dehydrating reagent such as, for 
example, inorganic acid chlorides, and in the presence of a catalyst, to 
give the thieno [3,2-b]pyran-5,7-dione according to the invention. 
If, for example, thieno[3,2-b]-6-butyryl-pyran-5,7-dione having a carbonyl 
group in the side chain and hydroxylamine or its ammonium compound such as 
ethoxyamine hydrochloride are used as educts, the course of the reaction 
of process (d) according to the invention can be outline by the following 
equation: 
##STR10## 
If 8-methyl-thione[3,2-b]-6-(1-ethoxyiminopropyl)-pyran-5,7-dione and 
iodomethane are used as educts the course of the reaction of process (e) 
according to the invention can be outlined by the following equation: 
##STR11## 
Formula (II) provides a general definition of the 
thieno-[3,2-b]pyran-5,7-diones required as educts for carrying out 
processes (a), (b) and (c) according to the invention. In this formula 
(II), R.sup.1, X and Y preferably represent those radicals which have 
already been mentioned in connection with the description of the 
substances of the formula (I) according to the invention as being 
preferred for these substituents. The thieno[3,2-b]pyran-5,7-diones of the 
formula (II) are known or can be prepared from 
2-acetyl-3-hydroxythiophenes (V) by processes known per se. [T. Kraft, 
Recueil 86, 971 (1967)]. 
The 2-acetyl-3-hydroxythiophenes (V) can be successfully synthesised by 
reacting 2,5-dihydroxy-2,5-dimethyl1,4-dithiane with propiol esters (cf. 
T. Kraft, Recueil 86, 971 (1967)) or by reacting 
2,5-dihydroxy-2,5-dimethyl-1,4-dithiane with .alpha.-halogenoacrylic 
esters. 
##STR12## 
Alternatively, it is also possible to synthesise 
2-acetyl-3-hydroxy-thiophenes by reacting .beta.-halogen-substituted 
.alpha.,.beta.-unsaturated esters with 
2,5-dihydroxy-2,5-dimethyl-1,4-dithione or by reacting .beta.-thioxo 
esters with .alpha.-halogenoacetone (DE 3,925,719, 1989) or by 
dehydrogenation of 2-acetyl-3-keto-4,5-dihydrothiophene of the formula 
(VI) (DE 2,615,885, 1976). 
##STR13## 
The .beta.-thioxo esters are known [F. Duus, Tetrahedron 28, 5923 (1972)]. 
The 2-acetyl-3-keto-4,5-dihydrothiophenes of the formula (VI) 
##STR14## 
are new and also a subject of the invention. They can be obtained by 
reacting 2,5-dihydroxy-2,5-dimethyl-1,4-dithiane with acrylic esters of 
the formula (VII): 
##STR15## 
Formula (III) provides a general definition of the acid chlorides 
furthermore required as educts for carrying out processes (a) and (c) 
according to the invention, and formula (IV) provides a general definition 
of the carboxylic acids furthermore required as educts for carrying out 
process (b) according to the invention. In these formulae (III) and (IV), 
R.sup.2 preferably represents those radicals which have already been 
mentioned in connection with the description of the substances of the 
formula (I) according to the invention as being preferred for this 
substituent. The acid halides of the formula (III) and the carboxylic 
acids of the formula (IV) are generally known compounds of organic 
chemistry. 
Formula (IX) provides a general definition of the organo-halogen compounds 
furthermore required as educts for carrying out process (e). 
In this formula R.sup.1 represents those residues except hydrogen, which 
have been mentioned in connection with the description of the substances 
of the formula (I) according to the invention as being preferred for 
R.sup.2. 
The compounds of the formula (IX) are generally known compounds in organic 
chemistry. 
Formula (I) provides a general definition of the 
thieno-[3,2-b]pyran-5,7-diones required as educts for carrying out process 
(c) according to the invention. In this formula (I), R.sup.1, R.sup.2, X 
and Y preferably represent those radicals which have already been 
mentioned in connection with the description of the substances of the 
formula (I) according to the invention as being preferred for these 
substituents. However, in the case of process (d) according to the 
invention Z represents an oxime ether group (.dbd.NOR.sup.3) in which 
R.sup.3 preferably represents those radicals which have also already been 
mentioned in connection with the description of the substances of the 
formula (I) according to the invention as being preferred for these 
substituents: 
The compounds of the formula (I) in which R.sup.1 is hydrogen can occur in 
several tautomeric forms which differ from the formula (I) and which are 
also part of the invention. 
In the event that olefinically unsaturated substituents are present, E and 
Z isomers can occur in a known fashion and are equally part of the 
invention. 
Suitable diluents for carrying out the processes (a), (b), (c) and (e) 
according to the invention are inert organic solvents. These include, in 
particular, aliphatic, alicyclic or aromatic hydrocarbons such as, for 
example, benzene, toluene, xylene, petroleum ether, hexane, cyclohexane, 
ethers such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol 
dimethyl ether or ethylene glycol diethyl ether, ketones such as acetone 
or butanone, nitriles such as acetonitrile or propionitrile, amides such 
as dimethylformamide, dimethylacetamide, N-methylformanilide, 
N-methylpyrrolidone or hexamethylphosphoric triamide, esters such as ethyl 
acetate, or sulphoxides such as dimethyl sulphoxide, or sulphones such as 
sulpholane, alcohols such as methanol, ethanol or isopropanol, or 
chlorinated hydrocarbons such as chloroform or dichloromethane. 
Processes (a), (b) and (e) according to the invention are preferably 
carried out in the presence of a suitable reaction auxiliary. Suitable 
reaction auxiliaries are all inorganic and organic bases which can 
customarily be used. The following are preferably used: hydrides, 
hydroxides, amides, alcoholates, carbonates or hydrogen carbonates of 
alkali metals such as, for example, sodium hydride, sodium amide, sodium 
hydroxide, sodium methylate, sodium ethylate, potassium t-butylate, sodium 
carbonate or sodium hydrogencarbonate, and also tertiary amines such as, 
for example, triethylamine, N,N-dimethylaniline, pyridine, 
N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene 
(DBN) or diazabicycloundecene (DBU), oxides of alkaline earth metals such 
as magnesium oxide or calcium oxide. 
The base is added in a stoichiometric amount or in an excess. 
Examples which may be mentioned of acidic or basic catalysts for process 
(a), (c) and (e) according to the invention are aluminum chloride, zinc 
chloride, zinc acetate, trifluoromethylsulphonic acid, tin tetrachloride, 
4-dimethyl-aminopyridine and 4-pyrrolidinopyridine. 
When carrying out processes (a), (b) and (c) according to the invention, 
the reaction temperatures can be varied within a substantial range. In 
general, the processes are carried out at temperatures between -20.degree. 
C. and 150.degree. C., preferably at temperatures between 0.degree. C. and 
100.degree. C., very particularly preferably at temperatures between 
20.degree. C. and 80.degree. C. 
For carrying out process (a), (b) and (c) according to the invention, 0.8 
to 2.5 mol, preferably 1.0 to 1.5 mol, of acid chloride of the formula 
(III) or 1.0 to 1.5 mol of carboxylic acid of the formula (IV) (process 
(b)) and, if appropriate, 0.8 to 2.5 mol, preferably 1.0 to 1.5 mol, of 
reaction auxiliary are generally employed per mole of 
thieno[3,2-b]pyran-5,7-dione of the formula (II). 
The reaction is carried out and the reaction products are worked up and 
isolated by generally customary methods (cf. also the Preparation 
Examples). 
Suitable diluents for carrying out process (d) according to the invention 
are inert organic solvents. These include, in particular, aliphatic, 
alicyclic or aromatic hydrocarbons such as, for example, benzene, toluene, 
xylene, petroleum ether, hexane, cyclohexane, ethers such as diethyl 
ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl ether or 
ethylene glycol diethyl ether, ketones such as acetone or butanone, 
nitriles such as acetonitrile or propionitrile, amides such as 
dimethylformamide, dimethylacetamide, n-methylformanilide, 
N-methylpyrrolidone or hexamethylphosphoric triamide, esters such as ethyl 
acetate, or sulphoxides such as dimethyl sulphoxide, or sulphones such as 
sulpholane, alcohols such as methanol, ethanol or isopropanol, chlorinated 
hydrocarbons such as chloroform or dichloromethane. 
Process (d) according to the invention is preferably carried out in the 
presence of a suitable reaction auxiliary. Suitable reaction auxiliaries 
are all inorganic and organic bases which can customarily be used. The 
following are preferably used: hydrides, hydroxides, amides, alcoholates, 
carbonates or hydrogencarbonates of alkali metals such as, for example, 
sodium hydride, sodium amide, sodium hydroxide, sodium methylate, sodium 
ethylate, potassium t-butylate, sodium carbonate or sodium 
hydrogencarbonate, and also tertiary amines such as, for example, 
triethylamine, N,N-dimethylaniline, pyridine, N,N-dimethylaminopyridine, 
diazabicyclooctane (DABCO), diazabicyclononene (DBN) or 
diazabicycloundecene (DBU), oxides of alkali earth metals such as 
magnesium oxide or calcium oxide. 
The base is added in a stoichiometric amount or in an excess. 
When carrying out processes (c), (d) and (e) according to the invention the 
reaction temperatures can be varied within a substantial range. In 
general, the process is carried out at temperatures between -20.degree. C. 
and 150.degree. C., preferably at temperatures between 0.degree. C. and 
80.degree. C., 
For carrying out process (d) according to the invention, 0.8 to 2.5 mol, 
preferably 1.0 to 1.5 mol, of hydroxylamine or its ammonium compound 
R.sup.3 ONH.sub.2 or R.sup.3 ONH.sub.3.sup..sym. W.sup..crclbar. and, if 
appropriate, 0.8 to 2.5 mol, preferably 1.0 to 1.5 mol, of reaction 
auxiliary are generally employed per mole of thieno[3,2-b]pyran-5,7-dione 
of the formula (I). W.sup..crclbar. in this context represents an anion of 
an inorganic acid such as chloride, bromide, iodide, hydrogen sulphate or 
phosphate. 
For carrying out process (e) according to the invention, 0.8 to 2.5 mol, 
preferably 1.0 to 1,5 mol, of organohalogen compound of the formula (IX) 
and, if appropriate, 0.8 to 2.5 mol, preferably 1.0 to 1,5 mol, of 
reaction auxiliary are generally employed per mole of 
thieno[3,2-b]pyran-5,7-dione of the formula (I) in which R.sup.1 
represents hydrogen. 
The reaction is carried out and the reaction products are worked up and 
isolated by generally customary methods (cf. also the Preparation 
Examples). 
While having a favourable toxicity to warm-blooded species, the active 
compounds are suitable for combating pathogenic endoparasites which occur 
in humans and in productive livestock, breeding animals, zoo animals, 
laboratory animals, experimental animals and pets in animal keeping and 
livestock breeding. They are active against all or individual stages of 
development of the pests and against resistant and normally sensitive 
strains. By combating the pathogenic endoparasites, it is intended to 
reduce disease, deaths and reduced performance (for example in the 
production of meat, milk, wool, hides, eggs, honey etc.), so that more 
economical and simpler animal keeping is made possible by employing the 
active compounds. The pathogenic endoparasites include cestodes, 
trematodes, nematodes and acantocephala, in particular: 
From the order of the Pseudophyllidea, for example Diphyllobothrium spp., 
Spirometra spp., Schistocephalus spp., Ligula spp., Bothridium spp., 
Diplogonoporus spp.. 
From the order of the Cyclophyllidea, for example Mesocestoides spp., 
Anoplocephala spp., Paranoplocephala spp., Moniezia spp., Thysanosomsa 
spp., Thysaniezia spp., Avitellina spp., Stilesia spp., Cittotaenia spp., 
Andyra spp., Bertiella spp., Taenia spp., Echinococcus spp., Hydatigera 
spp., Davainea spp., Raillietina spp., Hymenolepis spp., Echinolepis spp., 
Echinocotyle spp., Diorchis spp., Dipylidium spp., Joyeuxiella spp., 
Diplopylidium spp.. 
From the subclass of the Monogenea, for example Gyrodactylus spp., 
Dactylogyrus spp., Polystoma spp.. 
From the subclass of the Digenea, for example Diplostomum spp., 
Posthodiplostomum spp., Schistosoma spp., Trichobilharzia spp., 
Ornithobilharzia spp., Austrobilharzia spp., Gigantobilharzia spp., 
Leucochloridium spp., Brachylaima spp., Echinostoma spp., Echinoparyphium 
spp., Echinochasmus spp., Hypoderaeum spp., Fasciola spp., Fasciolides 
spp., Fasciolopsis spp., Cyclocoelum spp., Typhlocoelum spp., 
Paramphistomum spp., Calicophoron spp-, Cotylophoron spp., Gigantocotyle 
spp., Fischoederius spp. Gastrothylacus spp., Notocotylus spp., Catatropis 
spp., Plagiorchis spp., Prosthogonimus spp., Dicrocoelium spp., Eurytrema 
spp., Troglotrema spp., Paragonimus spp., Collyriclum spp., Nanophyetus 
spp., Opisthorchis spp., Clonorchis spp., Metorchis spp., Heterophyes 
spp., Metagonimus spp.. 
From the order of the Enoplida, for example Trichuris spp., Capillaria 
spp., Trichomosoides spp., Trichinella spp.. 
From the order of the Rhabditida, for example Micronema spp., Strongyloides 
spp.. 
From the order of the Strongylida, for example Stronylus spp., 
Triodontophorus spp., Oesophagodontus spp., Trichonema spp., Gyalocephalus 
spp., Cylindropharynx spp.,. Poteriostomum spp., Cyclococercus spp., 
Cylicostephanus spp., Oesophagostomum spp., Chabertia spp., Stephanurus 
spp., Ancylostoma spp., Uncinaria spp., Bunostomum spp., Globocephalus 
spp., Syngamus spp., Cyathostoma spp., Metastrongylus spp., Dictyocaulus 
spp., Muellerius spp., protostrongylus spp., Neostrongylus spp., 
Cystocaulus spp., Pneumostrongylus spp., Spicocaulus spp., 
Elaphostrongylus spp., Parelaphostrongylus spp., Crenosoma spp., 
Paracrenosoma spp., Angiostrongylus spp., Aelurostrongylus spp., 
Filaroides spp., Parafilaroides spp., Trichostrongylus spp., Haemonchus 
spp., Ostertagia spp., Marshallagia spp., Cooperia spp., Nematodirus spp., 
Hyostrongylus spp., Obeliscoides spp., Amidostomum spp., Ollulanus spp.. 
From the order of the Oxyurida, for example Oxyuris spp., Enterobius spp., 
Passalurus spp., Syphacia spp., Aspiculuris spp., Heterakis spp.. 
From the order of the Ascaridia, for example Ascaris spp., Toxascaris spp., 
Toxocara spp., Parascaris spp., Anisakis spp., Ascaridia spp.. 
From the order of the Spirurida, for example Gnathostoma spp., Physaloptera 
spp., Thelazia spp., Gongylonema spp., Habronema spp., Parabronema spp., 
Draschia spp., Dracunculus spp.. 
From the order of the Filariida, for example Stephanofilaria spp., 
Parafilaria spp., Setaria spp., Loa spp.,.Dirofilaria spp., Litomosoides 
spp., Brugia spp., Wuchereria spp., Onchocerca spp.. 
From the order of the Gigantorhynchida, for example Filicollis spp., 
Moniliformis spp., Macracanthorhynchus spp., Prosthenorchis spp.. 
The productive livestock and breeding animals include mammals such as, for 
example, cattle, horses, sheep, pigs, goats, camels, water buffaloes, 
donkeys, rabbits, fallow deer, reindeer, fur-bearing animals such as, for 
example, minks, chinchilla, raccoon, birds such as, for example, chickens, 
geese, turkeys, ducks, fresh water and salt water fish such as, for 
example, trout, carp, eels, reptiles, insects such as, for example, 
honeybee and silk worm. 
Laboratory and experimental animals include mice, rats, guinea pigs, golden 
hamsters, dogs and cats. 
Pets include dogs and cats. 
The administration can be prophylactic or therapeutic. 
The active compounds are administered, directly or in the form of suitable 
preparations, enterally, parenterally, dermally, nasally, by treating the 
environment, or with the aid of active-compound-containing shaped 
articles, such as, for example, strips, plates, bands, collars, ear tags, 
limb bands or marking devices. 
The active compounds are administered enterally, for example orally, in the 
form of powders, tablets, capsules, pastes, drinks, granules, orally 
administrable solutions, suspensions and emulsions, boli, medicated feed 
or drinking water. Dermal administration is effected, for example, in the 
form of dipping, spraying or pouring-on and spotting-on. Parenteral 
administration is effected, for example, in the form of injection 
(intramuscular, subcutaneous, intravenous, intraperitoneal) or by 
implants. 
The following are suitable preparations: 
solutions, such as solutions for injection, or else solutions, concentrated 
for oral administration after dilution, solutions for use on the skin or 
in body cavitities, pour-on or spot-on formulations, gels; 
emulsions and suspension for oral or dermal administration and for 
injection; semi-solid preparations; 
formulations in which the active compound is incorporated in a cream base 
or in an oil-in-water or water-in-oil emulsion base; 
solid preparations such as powders, premixes or concentrates, granules, 
pellets, tablets, boli, capsules; aerosols and inhalants, shaped articles 
containing active compounds. 
Solutions for injection are administered intraveneously, intramuscularly 
and subcutaneously. 
Solutions for injections are prepared by dissolving the active compound in 
a suitable solvent and, if desired, adding additives such as solubilisers, 
acids, bases, buffer salts, antioxidants or preservatives. The solutions 
are sterile-filtered and decanted. 
The following may be mentioned as solvents: physiologically acceptable 
solvents such as water, alcohols such as ethanol, butanol, benzyl acohol, 
glycerol, propylene glycol, polyethylene glycols, N-methyl-pyrrolidone, 
and mixtures of these. 
If appropriate, the active compounds can also be dissolved in 
physiologically acceptable vegetable or synthetic oils which are suitable 
for injection. 
The following may be mentioned as solubilisers: solvents which aid the 
dissolution of the active compound in the main solvent, or which prevent 
its precipitation. Examples are polyvinylpyrrolidone, polyoxyethylated 
castor oil or polyoxyethylated sorbitan esters. 
Preservatives are: benzyl alcohol, trichlorobutanol, p-hydroxybenzoic 
esters, n-butanol. 
Oral solutions are administered directly. Concentrates are administered 
orally after previous dilution to the use concentrations. Oral solutions 
and concentrates are prepared as described above in the case of the 
solutions for injection and working under sterile conditions can be 
dispensed with. 
Solutions for use on the skin are administered dropwise, painted on, rubbed 
in, sprinkled on or sprayed on. These solutions are prepared as described 
above in the case of the solutions for injection. 
It may be advantageous to add thickeners during preparation. Thickeners 
are: inorganic thickeners such as bentonites, colloidal silica, aluminum 
monostearate, or organic thickeners such as cellulose derivatives, 
polyvinyl alcohols and their copolymers, acrylates and methacrylates. 
Gels are applied to the skin or painted on the skin or incorporated into 
body cavities. Gels are prepared by adding such an amount of thickener to 
solutions which have been prepared as described in the case of the 
solutions for injection, that the result is a clear composition of 
cream-like consistency. The thickeners used are the thickeners mentioned 
further above. 
Pour-on or spot-on formulations are poured or sprinkled onto limited area 
of the skin, the active compound penetrating the skin and acting 
systemically. 
Pour-on or spot-on formulations are prepared by dissolving, suspending or 
emulsifying the active compound in suitable dermatologically acceptable 
solvents or solvent mixtures. If desired, further adjuvants such as 
colorants, resorption accelerators, antioxidants, agents which impart 
protection against light, or tackifiers, are added. 
The following may be mentioned as solvents: water, alkanols, glycols, 
polyethylene glycols, polypropylene glycols, glycerol, aromatic alcohols 
such as benzyl alcohol, phenylethanol, phenoxyethanol, esters such as 
ethyl acetate, butyl acetate, benzyl benzoate, ethers such as alkylene 
glycol alkyl ethers such as dipropylene glycol monomethyl ether, 
diethylene glycol mono-butyl ether, ketones such as acetone, methyl ethyl 
ketone, aromatic and/or aliphatic hydrocarbons, vegetable or synthetic 
oils, DMF, dimethylacetamide, N-methylpyrrolidone, 
2,2-dimethyl-4-oxy-methylene-1,3-dioxolane. 
Colorants are all colorants which are released for use on animals and which 
can be suspended or dissolved. 
Resorption accelerators are, for example, DMSO, spreading oils such as 
isopropyl myristate, dipropylene glycol pelargonate, silicone oils, fatty 
acid esters, triglycerides, fatty alcohols. 
Antioxidants are sulphites or metabisulphites such as potassium 
metabisulphite, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole, 
tocopherol. 
Agents which impart protection against light are, for example, novantisolic 
acid. 
Tackifiers are, for example, cellulose derivatives, starch derivatives, 
polyacrylates, natural polymers such as alginates, gelatin. 
Emulsions can be administered orally, dermally or as injections. 
Emulsions are either of the water-in-oil type or of the oil-in-water type. 
They are prepared by dissolving the active compound either in the 
hydrophobic or in the hydrophilic phase and homogenising this phase with 
the solvent of the other phase, with the aid of suitable emulsifiers and, 
if appropriate, further adjuvants such as colorants, resorption 
accelerators, preservatives, antioxidants, agents which impart protection 
against light, viscosity-increasing substances. 
The following may be mentioned as hydrophobic phase (oil): paraffin oils, 
silicone oils, natural vegetable oils such as sesame seed oil, almond oil, 
castor oil, synthetic triglycerides such as caprilic/caproic acid 
bigylceride, triglyceride mixture with vegetable fatty acids of chain 
length C.sub.8-12 or other specifically selected natural fatty acids, 
partial glyceride mixtures of saturated or unsaturated, optionally also 
hydroxylcontaining, fatty acids, mono- and diglycerides of the C.sub.8 
/C.sub.10 -fatty acids. 
Fatty acid esters such as ethyl stearate, di-n-butyryl adipate, hexyl 
laurate, dipropylene glycol pelargonate, esters of a branched fatty acid 
of medium chain length with saturated fatty alcohols of chain length 
C.sub.16 -C.sub.18, isopropyl myristate, isopropyl palmitate, 
caprylic/caproic acid esters of saturated fatty alcohols of chain length 
C.sub.12 -C.sub.18, isopropyl stearate, oleyl oleate, decyl oleate, ethyl 
oleate, ethyl lactate, waxy fatty acid esters such as artificial duck's 
uropygial fat, dibutyl phthalate, diisopropyl adipate, ester mixtures 
related to the latter, etc. 
Fatty alcohols such as isotridecyl alcohol, 2-octyldodecanol, cetylstearyl 
alcohol, oleyl alcohol. 
Fatty acids such as, for example, oleic acid and its mixtures. 
The following may be mentioned as hydrophilic phase: water, alcohols such 
as, for example, propylene glycol, glycerol, sorbitol and their mixtures. 
The following may be mentioned as emulsifiers: nonionic surfactants, for 
example polyoxyethylated castor oil, polyoxyethylated sorbitan monooleate, 
sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate, 
alkylphenol polyglycol ethers; ampholytic surfactants such as disodium 
N-lauryl-.beta.-iminodipropionate or lecithin; anionic surfactants such as 
Na lauryl sulphate, fatty alcohol ether sulphates, the monoethanolamine 
salt of mono/dialkyl polyglycol ether orthophosphoric esters; cationic 
surfactants such as cetyltrimethylammonium chloride. 
The following may be mentioned as further adjuvants: caprylic/caproic acid 
esters of saturated fatty alcohols of chain length C.sub.12 -C.sub.18, 
isopropyl stearate, oleyl oleate, decyl oleate, ethyl oleate, ethyl 
lactate, waxy fatty acid esters such as artificial duck's uropygial fat, 
dibutyl phthalate, diisopropyl adipate, ester mixtures related to the 
latter, etc. 
Fatty alcohols such as isotridec-yl alcohol, 2-octyldodecanol, cetylstearyl 
alcohol, oleyl alcohol. 
Fatty acids such as, for example, oleic acid and its mixtures. 
The following may be mentioned as hydrophilic phase: water, alcohols such 
as, for example, propylene glycol, glycerol, sorbitol and their mixtures. 
The following may be mentioned as emulsifiers: nonionic surfactants, for 
example polyoxyethylated castor oil, polyoxyethylated sorbitan monooleate, 
sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate, 
alkylphenol polyglycol ethers; ampholytic surfactants such as disodium 
N-lauryl-.beta.-iminodipropionate or lecithin; anionic surfactants such as 
Na lauryl sulphate, fatty alcohol ether sulphates, the monoethanolamine 
salt of mono/dialkyl polyglycol ether orthophosphoric esters; cationic 
surfactants such as cetyltrimethylammonium chloride. 
The following may be mentioned as further adjuvants: viscosity-increasing 
and emulsion-stabilising substances such as carboxymethylcellulose, 
methylcellulose and other cellulose derivatives and starch derivatives, 
polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrolidone, 
polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, 
polyethylene glycols, waxes, colloidal silica, or mixtures of the 
substances listed. 
Suspensions can be administered orally, dermally or as injections. They are 
prepared by suspending the active compound in an excipient liquid, if 
appropriate with the addition of further adjuvants such as wetting agents, 
colorants, resorption accelerators, preservatives, antioxidants agents 
which impart protection against light. 
Excipient liquids which may be mentioned are all homogenous solvents and 
solvent mixtures. 
Wetting agents (dispersants) which may be mentioned are the surfactants 
given further above. 
Other adjuvants which may be mentioned are those given further above. 
Semi-solid preparations can be administered orally or dermally. They differ 
from the above-described suspensions and emulsions only on the basis of 
their higher viscosity. 
To prepare solid preparations, the active compound is mixed with suitable 
excipients, if appropriate with the addition of adjuvants, and the mixture 
is formulated as desired. 
Excipients which may be mentioned are all physiologically acceptable solid 
inert substances. Suitable as such are inorganic and organic substances. 
Inorganic substances are, for example, sodium chloride, carbonates such as 
calcium carbonate, hydrogen carbonates, aluminum oxides, silicas, clays, 
precipitated or colloidal silicon dioxide, phosphates. 
Organic substances are, for example, sugars, cellulose, foodstuffs and 
animal feeds such as powdered milk, animal meals, cereal meals and coarse 
cereal meals, and starches. 
Adjuvants are preservatives, antioxidants, colorants, which have already 
been mentioned further above. 
Other suitable adjuvants are lubricants and gliding agents such as, for 
example, magnesium stearate, stearic acid, talc, bentonites, substances 
which promote disintegration such as starch or crosslinked 
polyvinylpyrrolidone, binders such as, for example, starch, gelatin or 
linear polyvinylpyrrolidone, and also dry binders such as microcrystalline 
cellulose. 
The active compounds can exist in the preparations also as a mixture with 
synergists or with other active compounds which act against pathogenic 
endoparasites. Such active compounds are, for example, 
L-2,3,5,6-tetrahydro-6-phenylimidazothiazole, benzimidazole carbamates, 
praziquantel, pyrantel, febantel. 
Ready-for-use preparations contain the active compound in concentrations 
from 10 ppm-20 per cent by weight, preferably from 0.1-10 per cent by 
weight. 
Preparations which are diluted prior to use contain the active compound in 
concentrations from 0.5-90 per cent by weight, preferably from 5 to 50 per 
cent by weight. 
In general, it has proved advantageous to administer amounts of 
approximately 1 to approximately 100 mg of active compound per kg of body 
weight per day to achieve effective results. 
The active compounds according to the invention can be used as defoliants, 
desiccants, agents for destroying broad-leaved plants and, especially, as 
weed-killers and growth regulators. By weeds, in the broadest sense, there 
are to be understood all plants which grow in locations where they are 
undesired. Whether the substances according to the invention act as total 
or selective herbicides depends essentially on the amount used. 
The active compounds according to the invention can be used, for example, 
in connection with the following plants: Dicotyledon weeds of the genera: 
Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, 
Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, 
Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, 
Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, 
Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus 
and Taraxacum. 
Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, 
Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, 
Arachis, Brassica, Lactuca, Cucumis and Cucurbita. 
Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, 
Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, 
Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, 
Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, 
Dactyloctenium, Agrostis, Alopecurus and Apera. 
Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, 
Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium. 
However, the use of the active compounds according to the invention is in 
no way restricted to these genera, but also extends in the same manner to 
other plants. 
The compounds are suitable, depending on the concentration, for the total 
combating of weeds, for example on industrial terrain and rail tracks, and 
on paths and squares with or without tree plantings. Equally, the 
compounds can be employed for combating weeds in perennial cultures, for 
example afforestations, decorative tree plantings, orchards, vineyards, 
citrus groves, nut orchards, banana plantations, coffee plantations, tea 
plantations, rubber plantations, oil palm plantations, cocoa plantations, 
soft fruit plantings and hopfields, on lawns, turf and pasture-land, and 
for the selective combating of weeds in annual cultures. 
The compounds of the formula (I) according to the invention are suitable 
for selectively combating monocotyledon weeds in monocotyledon and 
dicotyledon cultures, both by the pre-emergence and the post-emergence 
method. 
The active compounds can be converted into the customary formulations, such 
as solutions, emulsions, wettable powders, suspensions, powders, dusting 
agents, pastes, soluble powders, granules, suspension-emulsion 
concentrates, natural and synthetic materials impregnated with active 
compound, and very fine capsules in polymeric substances. 
These formulations are prepared in a known manner, for example by mixing 
the active compounds with extenders, that is liquid solvents and/or solid 
carriers, optionally with the use of surface-active agents, that is 
emulsifying agents and/or dispersing agents and/or foam-forming agents. 
In the case of the use of water as an extender, organic solvents can, for 
example, also be used as auxiliary solvents. As liquid solvents, there are 
suitable in the main: aromatics, such as xylene, toluene, or 
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, mineral and vegetable oils, alcohols, such as 
butanol or glycol as well as their ethers and esters, ketones, such as 
acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, 
strongly polar solvents, such as dimethylformamide and dimethyl 
sulphoxide, as well as water. 
As solid carriers there are suitable: for example ammonium salts and ground 
natural minerals, such as kaolins, clays, talc, chalk, quartz, 
attapulgite, montmorillonite or diatomaceous earth, and ground syn 
minerals, such as highly disperse silica, alumina and silicates, as solid 
carriers for granules there are suitable: for example crushed and 
fractionated natural minerals such as calcite, marble, pumice, sepiolite 
and dolomite, as well as synthetic granules of inorganic and organic 
meals, and granules of organic material such as sawdust, coconut shells, 
maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents 
there are suitable: for example non-ionic and anionic emulsifiers, such as 
polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, 
for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl 
sulphates, arylsulphonates as well as albumen hydrolysis products; as 
dispersing agents there are suitable: for example lignin-sulphite waste 
liquors and methylcellulose. 
Adhesives such as carboxymethylcellulose and natural and synthetic polymers 
in the form of powders, granules or latexes, such as gum arabic, polyvinyl 
alcohol and polyvinyl acetate, as well as natural phospholipids, such as 
cephalins and lecithins, and synthetic phospholipids, can be used in the 
formulations. Further additives can be mineral and vegetable oils. 
It is possible to use colorants such as inorganic pigments, for example 
iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such 
as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, 
and trace nutrients such as salts of iron, manganese, boron, copper, 
cobalt, molybdenum and zinc. The formulations in general contain between 
0.1 and 95 per cent by weight of active compound, preferably between 0.5 
and 90%. 
For combating weeds, the active compounds according to the invention, as 
such or in the form of their formulations, can also be used as mixtures 
with known herbicides, finished formulations or tank mixes being possible. 
Suitable herbicides for the mixtures are known herbicides such as, for 
example, N-(2-benzothiazolyl)-N,N'-dimethylurea (METABENZTHIAZURON) for 
combating weeds in cereals; 
4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one (METAMITRON) for 
combating weeds in sugar beet, and 
4-amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one 
(METRIBUZIN) for combating weeds in soya beans; furthermore also 
2,4-dichlorophenoxyacetic acid (2,4-D); 4-(2,4-dichlorophenoxy)-butyric 
acid (2,4-DB); 2,4-dichlorophenoxypropionic acid (2,4-DP); 
methy12-[[[[[(4,6-dimethoxypyrimidin-2-yl)-amino]-carbonyl]-amino]-sulphon 
yl]-methyl]-benzoate (BENSULFURON); 3-isopropyl-2,1,3-benzothiadiazin-4-one 
2,2-dioxide (BENTAZONE); 3,5-dibromo-4-hydroxy-benzonitrile (BROMOXYNIL); 
5-amino-4-chloro-2-phenyl-2,3-dihydro -3-oxy-pyridazrne (CHLORIDAZON); 
2-chloro-N-{[(4-methoxy 
-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl}-benzene-sulphonamide 
(CHLORSULFURON); N,N-dimethyl-N'-(3-chloro-4-methylphenyl)-urea 
(CHLOR/TOLURON); 5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoic 
acid (ACIFLUORFEN); methyl 5-(2,4-dichloro-phenoxy}-2-nitrobenzoate 
(BIFENOX); 5-(2-chloro-4-(trifluoromethyl) 
-phenoxy)-N-methylsulphonyl-2-nitrobenzamide (FOMESAFEN); 
2-ethoxy-1-methyl-2-oxo-ethyl 5-(2-chloro-4-trifluoro 
-methyl)-phenoxy)-2-nitrobenzoate (LACTOFEN); 2-[4,5-dihydro-4-methyl-4 
-(1-methylethyl-5-oxo -1H-imidazol-2-yl]-5-ethyl-3-pyridine carboxylic 
acid (IMAZETHAPYR); 2-(4,5-dihydro-4-methyl-4-(1-methylethyl) 
-5-oxo-1H-imidazol-2-yl)-3-quinoline-carboxylic acid 
(IMAZAQUIN);ethy12-((4-chloro-6-methoxy-2-pyrimidinyl) 
-aminocarbonyl)-aminosulphonyl)-benzoate (CHLORIMURON); 
4-amino-6-t-butyl-3-ethylthio-1,2,4-triazin-5(4H)-one (ETHIOZIN); 
N-(3-trifluoromethylphenyl)-N,N-dimethylurea (FLUOMETURON); 
[(4-amino-3,5-dichloro-6-fluoro -2-pyridinyl)-oxy]-acetic acid or its 
1-methylheptyl ester 
(FLUROXYPYR);methy12-[4,5-dihydro-4-methyl-4-(1-methylethyl) 
-5-oxo-1H-imidazol-2-yl]-4(5)-methylbenzoate (IMAZAMETHABENZ); 
3,5-diiodo-4-hydroxybenzonitrile (IOXYNIL); 
N,N-dimethyl-N'-(4-isopropylphenyl)-urea (ISOPROTURON); 
(2-methyl--4-chlorophenoxy)-acetic acid (MCPA); 
(4-chloro-2-methylphenoxy)-propionic acid (MCPP); 
N-methyl-2-(1,3-benzothiazol-2-yloxy)-acetanilide (MEFENACET); 
2-{[[((4-methoxy-6-methyl-1,3,5-triazin 
-2-yl)-amino)-carbonyl]-amino]-sulphonyl}-benzoic acid or its methyl ester 
(METSULFURON); N-(1-ethylpropyl) -3,4-dimethyl-2,6-dinitroaniline 
(PENDIMETHALIN); 3-(ethoxycarbonylaminophenyl) 
N-(3,-methylphenyl)-carbamate (PHENMEDIPHAM); 
4-ethylamino-2-t-butylamino-6-methylthio-s-triazine (TERBUTRYNE); methyl 
3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl]-amino]-sulp 
honyl]-thiophene-2-carboxylate (THIAMETURON); 
2,6-dinitro-4-trifluoromethyl-N,N'-dipropylaniline (TRIFLURALIN). 
Surprisingly, some mixtures also show a synergistic action. 
A mixture with other known active compounds, such as fungicides, 
insecticides, acaricides, nematicides, bird repellants, plant nutrients 
and agents which improve soil structure, is also possible. 
The active compounds can be used as such, in the form of their formulations 
or in the use forms prepared therefrom by further dilution, such as 
ready-to-use solutions, suspensions, emulsions, powders, pastes and 
granules. They are used in the customary manner, for example by watering, 
spraying, atomizing or scattering. 
The active compounds according to the invention can be applied either 
before or after emergence of the plants. They can also be incorporated 
into the soil before sowing. 
The amount of active compound used can vary within a substantial range. It 
depends essentially on the nature of the desired effect In general, the 
amounts used are between 10 g and 10 kg of active compound per hectare of 
soil surface, preferably between 5 g and 5 kg per ha. 
The preparation and use of the active compounds according to the invention 
can be seen from the following examples.

SYNTHESIS EXAMPLES 
Example 1 
##STR16## 
Thieno[3,2-b]-6-butyryl-pyran-5,7-dione by process (b) 
18.64 g (0.111 mol) of thieno[3,2-b]pyran-5,7-dione are initially 
introduced together with 80 ml of butyric acid. 30 ml of phosphoryl 
chloride are then added dropwise, and the mixture is stirred for 2 hours 
at 80.degree. C. It is allowed to cool and 60 ml of ethanol are carefully 
added dropwise with cooling. The precipitate which has separated out is 
filtered off with suction and washed with a little ethanol. 
For purification, the product is recrystallised from ethanol. 
Yield: 10.80 g (40.85% of theory) 
Melting point: 108.degree.-109.degree. C. 
EXAMPLE 2 
##STR17## 
by process (d) Thieno[3,2-b]-6-(1-ethoxyiminobutyl)-pyran-5,7-dione 
4.76 g (0.02 mol) of Thieno[3,2-b]-6-butyryl-pyran-5,7-dione are initially 
introduced together with 60 ml of methanol. 2.00 g (0.024 mol) of sodium 
hydrogencarbonate and 2.34 g (0.24 mol) of ethoxyamine hydrochloride are 
then added. The mixture is stirred at room temperature and subsequently 
concentrated to dryness. The residue is taken up in 50 ml of methylene 
chloride, the mixture is washed once with water, twice with saturated 
sodium hydrogen-carbonate solution and again with water, dried with sodium 
sulphate, and the solvent is removed in vacuo. 2.8 g (49.8% of theory) of 
oxime ether of melting point m.p. 61.degree.-62.degree. C. are obtained. 
EXAMPLE 2a 
##STR18## 
Thieno[3.2-b]-6-butyryl-pyran-5,7-dione by process (a) 
Step 1 
33.64 g (0.02 mol) of thieno-[3,2-b]pyran-5,7-dione are initially 
introduced together with 50 ml of methylene chloride and 26.24 g (0.26 
mol) of triethylamine, a solution of 23.60 g (0.22 mol) of butyryl 
chloride in 40 ml of methylene chloride is added dropwise, and the mixture 
is refluxed for 4 hours and stirred for 12 hours at 20.degree. C. The 
solution is poured into 200 ml of water, and the organic phase is dried 
with magnesium sulphate and the solvent removed in vacuo. The crude 
product is purified by chromatography (silica gel, methylene chloride), 
and the solvent is removed in vacuo. 26.5 g (56% of theory) of thieno 
[3,2-b]-7-butyryloxy-pyran-5-one of melting point m.p.: 
55.degree.-56.degree. C. are obtained. 
Step 2 
8.90 g (0.037 mol) of thieno[3,2-b]7-butyryloxy-pyran-5-one are initially 
introduced together with 50 ml of 1,2-dichloroethane. 9.87 g (0.074 mol) 
of aluminium chloride are then added. The mixture is stirred for 2 hours 
at 20.degree. C. and then evaporated in vacuo on a rotary evaporator. The 
residue is then poured onto 60 g of ice and 60 ml of concentrated 
hydrochloric acid and the mixture is subjected to filtration with suction. 
The precipitate is subsequently stirred into 300 ml of 7N NaOH and again 
subjected to filtration with suction. The mother liquor is then acidified 
and the precipitate is filtered off with suction. 1.20 g (13.5% of theory) 
of thieno[3,2-b]-6-butyryl-pyran-5,7-dione of melting point m.p.: 
108.degree.14 109.degree. C. are obtained. 
Example 2b 
##STR19## 
by process (c) Thieno[3,2-b]-6-(4-methyl)-benzoyl-pyran-5,7-dione 
15.46 (0.10 mol) of 3-methylbenzoyl chloride and 2.73 g (0.02 mol) of zinc 
chloride are initially introduced together with 100 ml of toluene, and 
then 16.82 g (0.10 mol) of thieno[3,2-b]pyran-5,7-dione is added slowly at 
20.degree. C. After stirring at 20.degree. C. for 12 hours the solvent is 
removed in vacuo and the residue is stirred with ether. Following 
filtration with suction the crude product is recrystallised from 
acetonitrile. Yield: 13.63 g (48% of theory) Melting point: 
167.degree.-168.degree. C. 
Example 2c 
##STR20## 
Thieno[3,2-b]-6-(1-ethoxyiminopropyl)-7-methoxy-pyran-5-one by process (e) 
0.50 g(1.78 mmol) of thieno[3,2-b]-6-(1-ethoxyiminopropyl)-pyran-5,7-dione 
are initially introduced together with 30 ml of acetone. 0.33 g (2.31 
mmol) of iodomethane and 0.25 g (1.78 mmol) of potassium, carbonate are 
then added. The mixture is heated under reflux for 14 hours, allowed to 
cool and then evaporated to dryness. The residue is taken up into 100 ml 
of dichloromethane, washed twice with water, dried over magnesium sulphate 
and the solvent removed in vacuo to give an oily product. 
Yield: 0.43 g (82% of theory) 
.sup.7 NMR(DMSO).delta.=1.05-1.35 (6H, t, 2.times.CH.sub.3), 2.50 (3H, s, 
CH.sub.3), 2.70 (2H, q, CH.sub.2), 4.10 (3H, s, OCH.sub.3), 4.20 (2H, q, 
OCH.sub.2), 6.75 (7H, d, thiophene-H) ppm. 
TABLE 1 
__________________________________________________________________________ 
Preparation Examples of the compound of the formula (I) 
##STR21## (I) 
No. 
X Y Z R.sup.1 R.sup.2 m.p. [.degree.C.] 
__________________________________________________________________________ 
3 H H NOCH.sub.3 H Propyl 87-88 
4 H H 
##STR22## H Propyl 
5 H H 
##STR23## H Propyl 
6 CH.sub.3 
H NOC.sub.2 H.sub.5 
H Propyl 104-105 
7 CH.sub.3 
H 
##STR24## H Propyl 
8 CH.sub.3 
H 
##STR25## H Propyl 
9 H CH.sub.3 
O H Propyl 138 
10 H CH.sub.3 
NOC.sub.2 H.sub.5 
H Propyl 86-87 
11 H CH.sub.3 
NOCH.sub.3 H Propyl 87-88 
12 H CH.sub.3 
##STR26## H Propyl 
13 H CH.sub.3 
##STR27## H Propyl 
14 CH.sub.3 
CH.sub.3 
NOC.sub.2 H.sub.5 
H Propyl 
15 CH.sub.3 
CH.sub.3 
##STR28## H Propyl 
16 CH.sub.3 
CH.sub.3 
##STR29## H Propyl 
17 C.sub.2 H.sub.5 
H NOC.sub.2 H.sub.5 
H Propyl 
18 H C.sub.2 H.sub.5 
NOC.sub.2 H.sub.5 
H Propyl 
19 H Cl NOC.sub.2 H.sub.5 
H Propyl 
20 Cl H NOC.sub.2 H.sub.5 
H Propyl 
21 Cl Cl NOC.sub.2 H.sub.5 
H Propyl 
22 H H O H Ethyl 
23 H H 
##STR30## H Ethyl 
24 H H 
##STR31## H Ethyl 
25 H CH.sub.3 
O H Ethyl 163-164 
26 H CH.sub.3 
NOC.sub.2 H.sub.5 
H Ethyl 131-132 
27 H CH.sub.3 
##STR32## H Ethyl 81-82 
28 H CH.sub.3 
##STR33## H Ethyl 
29 CH.sub.3 
H 
##STR34## H Ethyl 
30 CH.sub.3 
H 
##STR35## H Ethyl 
31 Cl Cl 
##STR36## H Ethyl 
32 Cl H 
##STR37## H Ethyl 
33 H Cl 
##STR38## H Ethyl 
34 Br H 
##STR39## H Ethyl 
35 H SCH.sub.3 
##STR40## H Ethyl 
36 H OCH.sub.3 
##STR41## H Ethyl 
37 CH.sub.3 
H O H Propyl 75-76 
38 CH.sub.3 
H O H Ethyl 89-90 
39 H H O H Methyl 
40 H H O H Propyl 
41 H H O H 
##STR42## 
42 H H O H 
##STR43## 
43 H H O H 
##STR44## 
44 H H O H 
##STR45## 
45 H H O H 
##STR46## 
46 H H O H 
##STR47## 
47 H H 
##STR48## H Methyl 
48 H H 
##STR49## H Methyl 
49 H H 
##STR50## H Methyl 
50 H H 
##STR51## H Methyl 
51 H H 
##STR52## H Methyl 
52 H H 
##STR53## H Methyl 
53 H H 
##STR54## H Ethyl 
54 H H 
##STR55## H Ethyl 
55 H H 
##STR56## H Ethyl 
56 H H 
##STR57## H Ethyl 
57 H H 
##STR58## H Ethyl 
58 H H 
##STR59## H Ethyl 
59 H H 
##STR60## H Propyl 
60 H H 
##STR61## H Propyl 
61 H H 
##STR62## H Propyl 
62 H H 
##STR63## H Propyl 
63 H H 
##STR64## H Propyl 
64 H H 
##STR65## H Propyl 
65 H H NOCH.sub.3 H 
##STR66## 
66 H H NOC.sub.2 H.sub.5 
H 
##STR67## 
67 H H NOCH.sub.3 H 
##STR68## 
68 H H NOC.sub.2 H.sub.5 
H 
##STR69## 
69 H H NOCH.sub.3 H 
##STR70## 
70 H H NOC.sub.2 H.sub.5 
H 
##STR71## 
71 H H NOCH.sub.3 H 
##STR72## 
72 H H NOC.sub.2 H.sub.5 
H 
##STR73## 
73 H H NOCH.sub.3 H 
##STR74## 
74 H H NOC.sub.2 H.sub.5 
H 
##STR75## 
75 H H NOCH.sub.3 H 
##STR76## 
76 H H NOC.sub.2 H.sub.5 
H 
##STR77## 
77 H H O 
##STR78## 
Propyl 
__________________________________________________________________________ 
EXAMPLES OF THE PREATION OF THE EDUCTS 
Synthesis of thieno-[3,2-b]pyran-5,7-dione 
Example II-1 
##STR79## 
2.07 g (0.00966 mol) of 2-ethoxycarbonylacetyl-3-hydroxythiophene are 
refluxed for 1 hour together with 50 ml of absolute xylene. Meanwhile, the 
xylene is slowly distilled off, during which process the product separates 
out as a solid and is subsequently filtered off with suction. 
Yield: 0.4 g (22% of theory) 
Melting point: 223.degree.14 225.degree. C. 
The following are synthesised analogously: 
Examples II-2 
##STR80## 
C.sub.13 H.sub.8 O.sub.3 S Melting point: 214.degree.-215.degree. C. NMR 
(CDCl.sub.3): .delta.=5.6 (s, 1H), 7.2 (s, 1H), 7.4-7.6 (m, 5H) ppm 
IR (KBr): 1640; 1560; 1480; 1400 cm.sup.-1 
Example II-3 
##STR81## 
C.sub.8 H.sub.6 O.sub.3 S Melting point: 210.degree.-212.degree. C. IR 
(KBr): 1680; 1560; 1510; 1330 cm.sup.-1 
MS: 182 (65%); 140 (100%) 112 (30%) 
Example II-4 
##STR82## 
C.sub.8 H.sub.6 O.sub.3 S Melting point: 220.degree.-221.degree. C. NMR 
(DMSO): .delta.=2.25 (s, 3H); 5.4 (s, 2H); 7.6 (s, 1H) ppm 
Synthesis of 2-ethoxycarbonylacetyl-3-hydroxy-thiophene 
##STR83## 
4.8 g (0.0337 mol) of 2-acetyl-3-hydroxythiophene in 150 ml of diethyl 
carbonate are heated to 90.degree.-100.degree. C. 5 g of small sodium 
pieces are then added. Stirring is continued for 15 hours at 
90.degree.-100.degree. C. To decompose remainders of sodium, a little 
ethanol is added. For working up, the mixture is extracted twice using 75 
ml of water, the aqueous phase is then acidified with 10 ml of 
concentrated HCl, extracted 3 times with 50 ml portions of ether, dried, 
distilled in vacuo, and the fraction between 70.degree. and 100.degree. C. 
(0.6 mbar, educt) and between 113.degree. and 118.degree. C. (0.4 mbar 
product) is collected. 
The purification is carried out by means of column chromatography, using 
ethyl acetate/cyclohexane (1:1) as the eluant. 
Yield: 0.5 g (6.9% of theory). 
Synthesis of 2-acetyl-3-hydroxythiophene 
Example V-1 
##STR84## 
4.65 g (0.086 mol) of sodium methylate are suspended in 100 ml of toluene. 
A suspension of 7.6 g (0.0843 mol) of acetonylmercaptan in 150 ml of 
toluene is then added. After this, 7.1 g (0.0843 mol) of methyl propiolate 
are added dropwise. The mixture is refluxed for 1 hour. After cooling, a 
solution of 4.5 ml of concentrated H.sub.2 SO.sub.4 in 120 ml of water is 
added dropwise. The toluene phase is separated off and washed 3 times 
using 50 ml portions of water, dried and concentrated. The batch is 
distilled and the crude fraction is collected between 85.degree. C. and 
90.degree. C. at 15.9 mbar. Weight of the crude product: 6 g. The crude 
product is introduced into 48 ml of 1N NaOH, and the mixture is extracted 
using ether. The aqueous phase is acidified using 2N HCl and extracted 
with ether. After the mixture has been dried and concentrated in vacuo, it 
is triturated with ether. 
Yield: 1.2 g (10% of theory) 
Melting point: 48.degree.-50.degree. C. 
The following were synthesised analogously: 
Example V-2 
##STR85## 
C.sub.12 H.sub.10 O.sub.2 S Melting point: 93.degree.-94.degree. C. 
NMR (CDCl.sub.3): .delta.=2.4 (s,3H), 7.0 (s, 1H), 7.4 (m,3H), 7.6 (m, 2H), 
11.6 (s, 1H) ppm 
IR (KBr): 1600; 1480; 1420; 1370; 1340 cm.sup.-1 
Example V-3 
##STR86## 
C.sub.7 H.sub.8 O.sub.2 S 
(Process .alpha.) 
42.1 g (0.78 mol) of sodium methylate are suspended in 1000 ml of toluene. 
70.3 g (0.78 mol) of 2,5-dihydroxy-2,5-dimethyl-1,4-dithiane and 190 g 
(1.28 mol) of ethyl .beta.-chloro-crotonate are added. 
The mixture is subsequently refluxed for 2 hours. It is allowed to cool, 
and a solution of 41.7 ml of concentrated H.sub.2 SO.sub.4 in 1100 ml of 
water is added to the reaction mixture. 
The organic phase is separated off, and the aqueous phase is re-extracted 
with toluene. The combined organic phases are washed with water and 
subsequently dried over sodium sulphate. 
After the desiccant has been filtered off, the solvent is removed in vacuo. 
The residue is introduced into 450 ml of 1N NaOH solution and extracted 
once with ether. The aqueous phase is acidified with 2N HCl and extracted 
with ether. The organic phases are dried over sodium sulphate. After the 
desiccant has been separated off and the solvent has been removed in 
vacuo, the residue is crystallised by trituration with ether. 
Yield: 20 g (16% of theory) 
Melting point: 74.degree.-75.degree. C. 
IR (KBr): 1490; 1440; 1220; 1040 cm.sup.-1 
NMR (CDCl.sub.3) .delta.=2.3 (s, 3H); 2.45 (d, 3H); 6.5 (d, 1H); 11.7 (s, 
1H) ppm 
MS: 156 (100%); 141 (100%) 
Process .beta.) 
A solution of 2.92 g (0.02 mol) of ethyl .beta.-thioacetoacetate in 10 ml 
of absolute benzene is added dropwise to a solution of 0.6 g (0.025 mol) 
of sodium hydride in 50 ml of absolute benzene, under a nitrogen 
atmosphere. 
The mixture is subsequently refluxed for 30 minutes. 
2.78 g (0.03 mol) of chloroacetone, dissolved in 20 ml of absolute benzene, 
are then added dropwise, and the mixture is refluxed for another 3 hours. 
After this, the batch is poured into ice-water and acidified. The organic 
phase is separated off, and the solvent is removed in vacuo. 
The residue is taken up in 100 ml of absolute DMSO. Under a nitrogen 
atmosphere, 0.72 g (0.03 mol) of sodium hydride are added and the batch is 
subsequently stirred for 2 hours. The batch is subsequently introduced 
into water and acidified. The aqueous phase is extracted with ether and 
the organic phase is dried over sodium sulphate. 
After removing the solvent in vacuo, the product is purified by 
chromatography (eluent : ethyl acetate/cyclohexane 1:1). 
Yield: 470 mg (15% of theory) 
The following were synthesised analogously: 
Example V-4 
##STR87## 
C.sub.9 H.sub.10 O.sub.2 S (pale yellow oil) 
NMR (CDCl.sub.3): .delta.=2.3 (s, 3H); 2.4-2.5 (m, 2H); 2.6-2.7 (m, 2H); 
2.85-2.95 (m, 2H); 11.8 (s, 1H) ppm 
MS: 182 (56%); 167 (100%) 
Example V-5 
##STR88## 
C.sub.6 H.sub.4 Cl.sub.2 O.sub.2 S Melting point : 84.degree.-85.degree. C. 
NMR (CDCl.sub.3): .delta.=2.15 (s, 3H); 11.9 (s, 1H) ppm 
Example V-6 
Synthesis of 2-acetyl-3-hydroxy-4-methylthiophene 
##STR89## 
36.0 g (0.227 mol) of 2-acetyl-3-keto-4-methyl-4,5-dihydrothiophene are 
initially introduced into 260 ml of methylene chloride 21.9 ml of 
sulphuryl chloride in 260 ml of methylene chloride are then added dropwise 
at 0.degree. C. While the sulphuryl chloride/methylene chloride mixture is 
added dropwise, a stream of nitrogen is passed into the solution to expel 
the HCl gas which is formed. When the addition is complete, stirring is 
continued for 30 minutes at 10.degree.-15.degree. C. The mixture is then 
introduced into 600 ml of water, and the organic phase is extracted with a 
5% strength NaHCO.sub.3 solution, dried and concentrated in vacuo. 
For purification, the product is distilled. 
Yield: 23.1 g (65% of theory) 
Boiling point: 112.degree.-115.degree. C. (1.0 mbar) 
Melting point: 42.degree.-43.degree. C. 
Synthesis of 2-acetyl-3-keto-4-methyl-4,5-dihydrothiophene 
[(VI), R'=CH.sub.3 ; R=H] 
Example VI-1 
##STR90## 
26.13.g (.about.0.5 mol) of sodium methylate are suspended in 1.0 l of 
toluene. 88.15 g (0.5 mol) of methyl 3-acetonylmercaptopropionate are then 
added dropwise at 70.degree. C., and stirring is continued for 3 hours at 
70.degree. C. The mixture is allowed to cool and introduced into a mixture 
of 750 ml of ice-water and 60 ml of glacial acetic acid. The organic phase 
is separated off and stirred into 1.5 l of 10% strength sodium hydroxide 
solution. The aqueous phase is acidified using glacial acetic acid and 
extracted with methylene chloride, dried, and concentrated in vacuo. 
For purification, the product is distilled. 
Yield: 38.6 g (53.4% of theory) 
Boiling point: 63.degree.-65.degree. C. (0.5 mbar) 
Synthesis of methyl 3-acetonylmercaptopropionate 
##STR91## 
90.1 g (0.5 mol) of 2,5-dihydroxy-2,5-dimethyl-1,4-dithiane are initially 
introduced into 100 ml of absolute tetrahydrofuran. 1.0 g of piperidine is 
then added, and 94.7 g (0.945 mol) of methyl acrylate are added dropwise 
at 10.degree.-15.degree. C, during which process another two portions of 
0.5 g of piperidine are added at the same time. The mixture is 
subsequently stirred for 60 minutes at 60.degree. C. It is allowed to cool 
and introduced into 500 ml of water. 
The mixture is extracted with methylene chloride, dried, and concentrated 
in vacuo. For purification, the product is distilled. 
Yield: 147.30 g (81.9% of theory) 
Boiling point: 98.degree.-100.degree. C. (2.1 mbar) 
Example A 
In-vivo nematode test 
Trichostrongylus colubriformis/sheep 
Sheep which had been infected experimentally with Trichostrongylus 
colubriformis were treated after the prepatency time of the parasite had 
elapsed. The active compounds were administered orally in the form of pure 
active compound in gelatin capsules. 
The degree of effectiveness is determined by counting the worm eggs 
excreted with the faeces before and after the treatment. 
Complete standstill of egg excretion after the treatment means that the 
worms were expelled or damaged in such a way that they no longer produce 
eggs (dosis effectiva). 
Tested active compounds and effective dosage rates (dosis effectiva) can be 
seen from the table which follows. 
______________________________________ 
Active compound dosis effectiva in 
Example No. mg/kg 
______________________________________ 
26 100 
______________________________________ 
Example B 
In-vivo nematode test 
Haemonchus contortus/sheep 
Sheep which had been infected experimentally with Haemonchus contortus were 
treated after the prepatency time of the parasite had elapsed. The active 
compounds were administered orally in the form of pure active compound in 
gelatin capsules. 
The degree of effectiveness is determined by counting the worm eggs 
excreted with the faeces before and after the treatment. 
Complete standstill of egg excretion after the treatment means that the 
worms were expelled or damaged in such a way that they no longer produce 
eggs (dosis effectiva). 
Tested active compounds and effective dosage rates (dosis effectiva) can be 
seen from the table which follows. 
______________________________________ 
Active compound dosis effectiva in 
Example No. mg/kg 
______________________________________ 
26 50 
______________________________________ 
Example C 
Pre-emergence test 
Solvent: 5 parts by weight of acetone 
Emulsifier: 1 part by weight of alkylaryl polyglycol ether 
To produce a suitable preparation of active compound, 1 part by weight of 
active compound is mixed with the stated amount of solvent, the stated 
amount of emulsifier is added and the concentrate is diluted with water to 
the desired concentration. 
Seeds of the test plants are sown in normal soil and, after 24 hours, 
watered with the preparation of the active compound. It is expedient to 
keep constant the amount of water per unit area. The concentration of the 
active compound in the preparation is of no importance, only the amount of 
active compound applied per unit area being decisive. After three weeks, 
the degree of damage to the plants is rated in % damage in comparison to 
the development of the untreated control. The figures denote: 
0%=no action (like untreated control) 
100%=total destruction 
In this test, a powerful action against weeds is shown by the compounds of 
Preparation Examples 10, 26 and 27, while displaying a good compatibility 
with crop plants such as, for example, oilseed rape and soya bean. 
Example D 
Post-emergence test 
Solvent: 5 parts by weight of acetone 
Emulsifier: 1 part by weight of alkylaryl polyglycol ether 
To produce a suitable preparation of active compound, 1 part by weight of 
active compound is mixed with the stated amount of solvent, the stated 
amount of emulsifier is added and the concentrate is diluted with water to 
the desired concentration. 
Test plants which have a height of 5-15 cm are sprayed with the preparation 
of the active compound in such a way as to apply the particular amounts of 
active compound desired per unit area. The concentration of the spray 
liquor is so chosen that the particular amounts of active compound desired 
are applied in 1,000 l of water/ha. After three weeks, the degree of 
damage to the plants is rated in % damage in comparison to the development 
of the untreated control. 
The figures denote: 
0%=no action (like untreated control) 
100%=total destruction 
A clearly superior activity against weeds compared with the prior art is 
shown in this test, for example, by the compounds according to Preparation 
Examples 10, 26 and 27, while displaying good compatibility with crop 
plants such as, for example, wheat, sugar beet and oilseed rape.