Dithiinetetra(thio)carboximides
View Patent ↗The present invention relates to novel dithiinetetra(thio)carboximides, to processes for preparing these compounds, to compositions comprising these compounds, and to the use thereof as biologically active compounds, especially for control of harmful microorganisms in crop protection and in the protection of materials and as plant growth regulators.
1. A compound of formula (I)
in which
X 1 is O or S,
X 2 is O or S,
X 3 is O or S,
R 1 and R 2 are the same or different and are each hydrogen, C 1 -C 8 -alkyl which is optionally substituted with one or more halogen, OR 3 , or COR 4 , C 3 -C 7 -cycloalkyl which is optionally substituted with one ore more halogen, C 1 -C 4 -alkyl, or C 1 -C 4 -haloalkyl, or are aryl or aryl-(C 1 -C 4 -alkyl) which in each case is optionally substituted with one or more halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, COR 4 , or sulphonylamino,
R 3 is hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkylcarbonyl or aryl which is optionally substituted with one or more halogen, C 1 -C 4 -alkyl, or C 1 -C 4 -haloalkyl,
R 4 is hydroxyl, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy,
and salts thereof.
2. The compound of claim 1 , in which
R 1 and R 2 are the same or different and are each hydrogen, C 1 -C 6 -alkyl which is optionally substituted with one or more fluorine, chlorine, bromine, OR 3 , or COR 4 , C 3 -C 7 -cycloalkyl which is optionally substituted with one or more chlorine, methyl, or trifluoromethyl, or are phenyl or phenyl-(C 1 -C 4 -alkyl) which in each case is optionally substituted with one or more fluorine, chlorine, bromine, methyl, trifluoromethyl, COR 4 , or sulphonylamino,
R 3 is hydrogen, methyl, ethyl, methylcarbonyl, ethylcarbonyl, or phenyl which is optionally substituted with one or more fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl, or trifluoromethyl,
R 4 is hydroxyl, methyl, ethyl, methoxy or ethoxy.
3. The compound of claim 1 , in which R 1 and R 2 are each methyl.
4. A compound of formula (I-a)
in which
R 1 and R 2 are the same or different and are each hydrogen, C 1 -C 8 -alkyl which is optionally substituted with one or more halogen, OR 3 , or COR 4 , C 3 -C 7 -cycloalkyl which is optionally substituted with one or more halogen, C 1 -C 4 -alkyl, or C 1 -C 4 -haloalkyl, or are aryl or aryl-(C 1 -C 4 -alkyl) which in each case is optionally substituted with one or more halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, COR 4 , or sulphonylamino,
R 3 is hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkylcarbonyl or aryl which is optionally substituted with one or more halogen, C 1 -C 4 -alkyl, or C 1 -C 4 -haloalkyl,
R 4 is hydroxyl, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy,
and salts thereof.
5. A compound of formula (I-b)
in which
R 1 and R 2 are the same or different and are each hydrogen, C 1 -C 8 alkyl which is optionally substituted with one or more halogen, OR 3 , or COR 4 , C 3 -C 7 -cycloalkyl which is optionally substituted with one or more halogen, C 1 -C 4 -alkyl, or C 1 -C 4 -haloalkyl, or are aryl or aryl-(C 1 -C 4 -alkyl) which in each case is optionally substituted with one or more halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, COR 4 , or sulphonylamino,
R 3 is hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkylcarbonyl or aryl which is optionally substituted with one or more halogen, C 1 -C 4 -alkyl, or C 1 -C 4 -haloalkyl,
R 4 is hydroxyl, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy,
and salts thereof.
6. A compound of formula (I-c)
in which
R 1 and R 2 are the same or different and are each hydrogen, C 1 -C 8 -alkyl which is optionally substituted with one or more halogen, OR 3 , or COR 4 , C 3 -C 7 -cycloalkyl which is optionally substituted with one or more halogen, C 1 -C 4 -alkyl, or C 1 -C 4 -haloalkyl, or are aryl or aryl-(C 1 -C 4 -alkyl) which in each case is optionally substituted with one or more halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, COR 4 , or sulphonylamino,
R 3 is hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkylcarbonyl or aryl which is optionally substituted with one or more halogen, C 1 -C 4 -alkyl, or C 1 -C 4 -haloalkyl,
R 4 is hydroxyl, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy,
and salts thereof.
7. A method for controlling phytopathogenic harmful fungi, comprising applying a compound of claim 1 , 4 , 5 , or 6 to the phytopathogenic harmful fungi, their habitat, or combinations thereof.
8. A composition for controlling phytopathogenic harmful fungi, comprising the compound of claim 1 , 4 , 5 , or 6 and an extender, a surfactant, and combinations thereof.
9. A process for producing a composition of claim 1 , 4 , 5 , or 6 , comprising mixing a compound of claim 1 with an extender, a surfactant, or combinations thereof.
10. A process for preparing a compound of claim 1 , 4 , 5 , or 6 comprising
A)
(1) reacting a succinic monoamide of formula (VI)
in which R is hydrogen, C 1 -C 8 -alkyl which is optionally substituted with one or more halogen, OR 3 , or COR 4 , C 3 -C 7 -cycloalkyl which is optionally substituted with one or more halogen, C 1 -C 4 -alkyl, or C 1 -C 4 -haloalkyl, or aryl or aryl-(C 1 -C 4 -alkyl) which in each case is optionally substituted with one or more halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, COR 4 , or sulphonylamino, with an excess of thionyl chloride, optionally in the presence of a diluent,
(2) removing excess thionyl chloride to form a product mixture,
(3) adding an organic solvent, water, and optionally a phase transfer catalyst to the product mixture, and
(4) isolating a compound of claim 1 by a chromatography process, or
B) reacting a dichloromaleimide of formula (VII)
in which
R 2 is hydrogen, C 1 -C 8 -alkyl which is optionally substituted with one or more halogen, OR 3 , or COR 4 , C 3 -C 7 -cycloalkyl which is optionally substituted with one or more halogen, C 1 -C 4 -alkyl, or C 1 -C 4 -haloalkyl, or aryl or aryl-(C 1 -C 4 -alkyl) which in each case is optionally substituted with one or more halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, COR 4 , or sulphonylamino, and
X 3 is O or S,
with a dichloromaleimide of formula (VIII)
in which
R 1 is hydrogen, C 1 -C 8 -alkyl which is optionally substituted with one or more halogen, OR 3 , or COR 4 , C 3 -C 7 -cycloalkyl which is optionally substituted with one or more halogen, C 1 -C 4 -alkyl, or C 1 -C 4 -haloalkyl, or aryl or aryl-(C 1 -C 4 -alkyl) which in each case is optionally substituted with one or more halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, COR 4 , or sulphonylamino,
X 1 is O or S, and
X 2 is O or S,
and an inorganic thiosulphate in a solvent or solvent mixture.
11. The compound of claim 4 , 5 , or 6 , in which
R 1 and R 2 are the same or different and are each hydrogen, C 1 -C 6 -alkyl which is optionally substituted with one or more fluorine, chlorine, bromine, OR 3 , or COR 4 , C 3 -C 7 -cycloalkyl which is optionally substituted with one or more chlorine, methyl, or trifluoromethyl, or are phenyl or phenyl-(C 1 -C 4 -alkyl) which in each case is optionally substituted with one or more fluorine, chlorine, bromine, methyl, trifluoromethyl, COR 4 , or sulphonylamino,
R 3 is hydrogen, methyl, ethyl, methylcarbonyl, ethylcarbonyl, or phenyl which is optionally substituted with one or more fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl, or trifluoromethyl,
R 4 is hydroxyl, methyl, ethyl, methoxy or ethoxy.
12. The compound of claim 4 , 5 , or 6 in which R 1 and R 2 are each methyl.