3-(4-cyanophenyl)uracils

The present invention relates to 3- (4-cyanophenyl) uracils of the general formula I.<chemistry id="chem0001" num="0001"><img file="EP0808310B1_D0001.tif" /></chemistry> in which the variables have the following meaning:<dl id="dl0001"><dt>A</dt><dd>Methyl or amino;</dd><dt>R¹</dt><dd>Hydrogen or fluorine;</dd><dt>R²</dt><dd>C.₁-C₄Haloalkyl;</dd><dt>R³</dt><dd>Hydrogen or halogen;</dd><dt>R⁴</dt><dd>Hydrogen, C₁-C₄Haloalkyl, C.₁-C₄-Alkyl, C₃-C₆Cycloalkyl, C₃-C₄Alkenyl, C₃-C₄-Alkynyl, (C₁-C₄-Alkyl) carbonyl, C₁-C₄Cyanoalkyl, C₁-C₄-Alkoxy-C₁-C₄-alkyl, CH₂-CO-XR⁵ or CH (CH₃) -CO-XR⁵;</dd><dt>X</dt><dd>a chemical bond, oxygen or -N (R⁶)-;</dd><dt>R⁵</dt><dd>Hydrogen, C₁-C₆-Alkyl, C₃-C₈Cycloalkyl, C₃-C₆Alkenyl, C₃-C₆Alkynyl, C₁-C₆-Alkoxy-C₁-C₆-alkyl or (C₁-C₆-Alkoxy) carbonyl-C₁-C₆-alkyl;</dd><dt>R⁶</dt><dd>Hydrogen, C₁-C₆-Alkyl or C₁-C₆-Alkoxy.</dd></dl>

The invention also relates to<ul id="ul0001" list-style="dash"><li>the use of the compounds I as herbicides and / or for the desiccation and / or defoliation of plants,</li><li>herbicidal agents and agents for the desiccation and / or defoliation of plants which contain the compounds I as active substances,</li><li>Process for combating undesired plant growth and for desiccating and / or defoliation of plants with the compounds I,</li><li>Process for the preparation of the compounds I and of herbicidal agents and agents for the desiccation and / or defoliation of plants using the compounds I, and</li><li>Intermediates of the formulas III and IV from which the compounds I can be obtained.</li></ul>

EP-A 255 047 is of particular importance with regard to the compounds I with A = methyl, since 3-aryluracils of the formula II are already quite generally used in this publication<chemistry id="chem0002" num="0002"><img file="EP0808310B1_D0002.tif" /></chemistry> in which<ul id="ul0002" list-style="none" compact="compact"><li>R^a for hydrogen, C_1-4-Alkyl, C_1-4Haloalkyl, formyl or C_2-6-Alkanoyl,</li><li>R^b for C_1-4-Alkyl or C_1-4Haloalkyl,</li><li>R³'for hydrogen, halogen or C₁-C₄-Alkyl,</li><li>R^c for an ether group or a radical R-CO-O-, R-CS-O- or R-SO₂-O- and</li><li>R^d represent halogen or cyano, and the salts of the compounds II with R^a = Hydrogen, described as a herbicide.</li></ul>

Examples of 3-phenyluracils in which the phenyl ring is a cyano group para to the uracil residue (R^d) carries, as well as their herbicidal effect are not to be found in this document.

Certain 1-amino-3-phenyluracils, which, however, do not carry a cyano group on the phenyl ring, are already taught as herbicides in EP-A 517 181 and JP-A 05/025 143.

EP-A-260 621 and EP-A-542 685 describe specially substituted 3- (4-cyanophenyl) uracils and their use for weed control.

However, the herbicidal or desiccant / defoliant properties of the known compounds are not always completely satisfactory. This invention was therefore based on new, in particular herbicidally active compounds, as a task with which undesired plants can be controlled more effectively than before.

The task also extends to the provision of new desiccant / defoliant connections.

Accordingly, the 3- (4-cyanophenyl) uracils of the formula I and their herbicidal activity have been found.

Furthermore, herbicidal compositions have been found which contain the compounds I and have a very good herbicidal action. In addition, processes for the preparation of these compositions and processes for controlling undesired vegetation using the compounds I have been found.

Furthermore, it was found that the compounds I are also suitable for defoliation and desiccation of parts of plants, for which crop plants such as cotton, potatoes, rapeseed, sunflower, soybeans or field beans, in particular cotton, are suitable. In this regard, agents for the desiccation and / or defoliation of plants, methods for producing these agents and methods for the desiccation and / or defoliation of plants with the compounds I have been found.

Depending on the substitution pattern, the compounds of the formula I can contain one or more centers of chirality and are then present as mixtures of enantiomers or diastereomers. The invention relates both to the pure enantiomers or diastereomers and to their mixtures.

The for the substituents R¹ to R⁶ or as residues on phenyl rings or heterocycles, organic molecular parts - like the meaning halogen - are collective terms for individual lists of the individual group members. All carbon chains, that is to say all alkyl, haloalkyl, alkoxy, alkylcarbonyl, alkenyl and alkynyl parts can be straight or branched. Unless stated otherwise, halogenated substituents preferably carry one to five identical or different halogen atoms.

In detail, for example:<ul id="ul0003" list-style="dash"><li>Halogen for: fluorine, chlorine, bromine or iodine;</li><li>C.₁-C₄-Alkyl and the alkyl parts of C₁-C₆-Alkoxy-C₁-C₆-alkyl and (C₁-C₆-Alkoxy) carbonyl-C₁-C₆-alkyl for: Methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2- Dimethylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1- dimethylbutyl, 1,2-dimethylbutyl , 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-2-methylpropyl;</li><li>C.₁-C₄-Halogenalkyl for: a C₁-C₄-Alkylrest as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example Chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2- Chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, petafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1- (fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl, 1- (bromomethyl) -2-bromethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl;</li><li>C.₃-C₆-Alkenyl for: Prop-1-en-1-yl, prop-2-en-1-yl, 1-methylethenyl, n-buten-1-yl, n-buten-2-yl, n-buten-3-yl, 1- Methyl-prop-1-en-1-yl, 2-methyl-prop-1-en-1-yl, 1-methyl-prop-2-en-1-yl or 2-methyl-prop-2-en- 1-yl, n-penten-1-yl, n-penten-2-yl, n-penten-3-yl, n-penten-4-yl, 1-methyl-but-1-en-1-yl, 2-methyl-but-1-en-1-yl, 3-methyl-but-1-en-1-yl, 1-methyl-but-2-en-1-yl, 2-methyl-but-2- en-1-yl, 3-methyl-but-2-en-1-yl, 1-methyl-but-3-en-1-yl, 2-methyl-but-3-en-1-yl, 3- Methyl-but-3-en-1-yl, 1,1-dimethyl-prop-2-en-1-yl, 1,2-dimethyl-prop-1-en-1-yl, 1,2-dimethyl-prop-2-en-1-yl, 1-ethyl-prop-1-en-2-yl, 1-ethyl prop-2-en-1-yl, n-hex-1-en-1-yl, n-hex-2-en-1-yl, n-hex-3-en-1-yl, n-hex 4-en-1-yl, n-hex-5-en-1-yl, 1-methyl-pent-1-en-1-yl, 2-methyl-pent-1-en-1-yl, 3- Methyl-pent-1-en-l-yl, 4-methyl-pent-1-en-1-yl, l-methyl-pent-2-en-1-yl, 2-methyl-pent-2-en- 1-yl, 3-methyl-pent-2-en-1-yl, 4-methyl-pent-2-en-1-yl, 1-methyl-pent-3-en-1-yl, 2-methyl pent-3-en-1-yl, 3-methyl-pent-3-en-1-yl, 4-methyl-pent-3-en-1-yl, 1-methyl-pent-4-en-1-yl, 2-methyl-pent-4-en-1-yl, 3-methyl-pent-4-en-1-yl, 4-methyl-pent-4- en-1-yl, 1,1-dimethyl-but-2-en-1-yl, 1,1-dimethyl-put-3-en-1-yl, 1,2-dimethyl-but-1-en- 1-yl, 1,2-dimethyl-put-2-en-1-yl, 1,2-dimethyl-but-3-en-1-yl, 1,3-dimethyl-put-1-en-1- yl, 1,3-dimethyl-but-2-en-1-yl, 1,3-dimethyl-put-3-en-1-yl, 2,2-dimethyl-but-3-en-1-yl, 2,3-dimethyl-put-1-en-1-yl, 2,3-dimethyl-but-2-en-1-yl, 2,3-dimethyl-put-3-en-1-yl, 3, 3-dimethyl-but-1-en-1-yl, 3,3-dimethyl-put-2-en-1-yl, 1-ethyl-but-1-en-1-yl, 1-ethyl-but-2-en-1-yl, 1-ethyl-but-3-en-1-yl, 2-ethyl-but-1- en-1-yl, 2-ethyl-but-2-en-1-yl, 2-ethyl-but-3-en-1-yl, 1,1,2-trimethyl-prop-2-en-1- yl, 1-ethyl-1-methyl-prop-2-en-1-yl, 1-ethyl-2-methyl-prop-1-en-1-yl or 1-ethyl-2-methyl-prop-2- en-1-yl;</li><li>C.₃-C₆-Alkynyl and the alkynyl parts of C₃-C₆-Alkynyloxy and (C₃-C₆-Alkynyl) carbonyl for: Prop-1-in-1-yl, prop-2-in-1-yl, but-1-in-1-yl, but-1-in-3-yl, but-1-in-4-yl, But-2-in-1-yl, pent-1-in-1-yl, n-pent-1-in-3-yl, n-pent-1-in-4-yl, n-pent-1- in-5-yl, n-pent-2-in-1-yl, n-pent-2-in-4-yl, n-pent-2-in-5-yl, 3-methyl-but-1- in-3-yl, 3-methyl-but-1-in-4-yl, n-hex-1-in-1-yl, n-hex-1-in-3-yl, n-hex-1- in-4-yl, n-hex-1-in-5-yl, n-hex-1-in-6-yl, n-hex-2-in-1-yl, n-hex-2-in- 4-yl, n-hex-2-in-5-yl, n-hex-2-in-6-yl, n-hex-3-in-1-yl, n-hex-3-in-2- yl, 3-methyl-pent-1-in-1-yl, 3-methyl-pent-1-in-3-yl, 3-methyl-pent-1-in-4-yl, 3-methyl-pent-1-in-5-yl, 4-methyl-pent-1-in-1-yl, 4-methyl-pent-2- in-4-yl or 4-methyl-pent-2-in-5-yl;</li><li>C.₁-C₆-Alkoxy and the alkoxy parts of C₁-C₆-Alkoxy-C₁-C₆-alkyl and (C₁-C₆-Alkoxy) carbonyl-C₁-C₆-alkyl for: Methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy, n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1- Dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, n-hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy;</li><li>(C.₁-C₄-Alkyl) carbonyl for: methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, 1-methylethylcarbonyl, n-butylcarbonyl, 1-methylpropylcarbonyl, 2-methylpropylcarbonyl, 1,1-dimethylethylcarbonyl;</li><li>C.₃-C₈Cycloalkyl for: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl;</li></ul>

With regard to the use of the compounds of the formula I according to the invention as herbicides and / or as defoliant / desiccant compounds, the variables preferably have the following meanings, individually or in combination:<dl id="dl0002"><dt>A</dt><dd>Amino or methyl;</dd><dt>R¹</dt><dd>Hydrogen or fluorine;</dd><dt>R²</dt><dd>C.₁-C₄-Haiogenalkyl, particularly preferably trifluoromethyl, chlorodifluoromethyl or pentafluoroethyl;</dd><dt>R³</dt><dd>Hydrogen or halogen, especially hydrogen, chlorine or bromine;</dd><dt>R⁴</dt><dd>Hydrogen, C₁-C₄Haloalkyl, C₁-C₄-Alkyl, C₃-C₆Cycloalkyl, C₃-C₄Alkenyl, C₃-C₄-Alkynyl, (C₁-C₄-Alkyl) carbonyl, C₁-C₄-Alkoxy-C₁-C₄-alkyl, -CH₂-CO-XR⁵, -CH (CH₃) -CO-XR⁵ or C₁-C₄Cyanoalkyl such as cyanomethyl, 1-cyanoeth-1-yl, 2-cyanoeth-1-yl, 1-cyanoprop-1-yl, 2-cyanoprop-1-yl, 3-cyanoprop-1-yl, 1-cyanoprop-2 -yl, 2-cyanoprop-2-yl, 1-cyanobut-1-yl, 2-cyanobut-1-yl, 3-cyanobut-1-yl, 4-cyanobut-1-yl, 1-cyanobut-2-yl , 2-cyano-but-2-yl, 1-cyanobut-3-yl, 2-cyanobut-3-yl, 1-cyano-2-methyl-prop-3-yl, 2-cyano-2-methyl-prop -3-yl, 3-cyano-2-methyl-prop-3-yl and 2-cyano-methyl-prop-2-yl;</dd><dt>X</dt><dd>a chemical bond, oxygen or -N (R⁶)-;</dd><dt>R⁵</dt><dd>Hydrogen, C₁-C₆-Alkyl, C₃-C₈Cycloalkyl, C₃-C₆Alkenyl, C₃-C₆Alkynyl, C₁-C₆-Alkoxy-C₁-C₆-alkyl or (C₁-C₆-Alkoxy) carbonyl-C₁-C₆-alkyl, especially hydrogen, C₁-C₆-Alkyl, C₃-C₈Cycloalkyl, C₁-C₆-Alkoxy-C₁-C₆-alkyl or (C₁-C₆-Alkoxy) carbonyl-C₁-C₆-alkyl,</dd><dt>R⁶</dt><dd>Hydrogen, C₁-C₆-Alkyl or C₁-C₆-Alkoxy.</dd></dl>

The compounds Ia (= ̂ I with A = amino, R¹ = Fluorine, R² = Trifluoromethyl, R³ = Hydrogen):<chemistry id="chem0003" num="0003"><img file="EP0808310B1_D0003.tif" /></chemistry><tables id="tabl0001" num="0001"><table frame="all"><title> Table 1</title><tgroup cols="2" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="left">No.</entry><entry namest="col2" nameend="col2" align="left">R⁴</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Ia.01</entry><entry namest="col2" nameend="col2" align="left">H</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.02</entry><entry namest="col2" nameend="col2" align="left">CH₃</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.03</entry><entry namest="col2" nameend="col2" align="left">C.₂H₅</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.04</entry><entry namest="col2" nameend="col2" align="left">nC₃H₇</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.05</entry><entry namest="col2" nameend="col2" align="left">CH (CH₃)₂</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.06</entry><entry namest="col2" nameend="col2" align="left">nC₄H₉</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.07</entry><entry namest="col2" nameend="col2" align="left">iC₄H₉</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.08</entry><entry namest="col2" nameend="col2" align="left">sc₄H₉</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.09</entry><entry namest="col2" nameend="col2" align="left">C (CH₃)₃</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.10</entry><entry namest="col2" nameend="col2" align="left">Cyclopropyl</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.11</entry><entry namest="col2" nameend="col2" align="left">Cyclobutyl</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.12</entry><entry namest="col2" nameend="col2" align="left">Cyclopentyl</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.13</entry><entry namest="col2" nameend="col2" align="left">Cyclohexyl</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.14</entry><entry namest="col2" nameend="col2" align="left">CH₂CN</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.15</entry><entry namest="col2" nameend="col2" align="left">CH₂CH₂CN</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.16</entry><entry namest="col2" nameend="col2" align="left">CH (CH₃) CN</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.17</entry><entry namest="col2" nameend="col2" align="left">C (CH₃)₂CN</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.18</entry><entry namest="col2" nameend="col2" align="left">C (CH₃)₂CH₂CN</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.19</entry><entry namest="col2" nameend="col2" align="left">CH₂Cl</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.20</entry><entry namest="col2" nameend="col2" align="left">CH₂CH₂Cl</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.21</entry><entry namest="col2" nameend="col2" align="left">CH (CH₃) CH₂Cl</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.22</entry><entry namest="col2" nameend="col2" align="left">CH₂CF₃</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.23</entry><entry namest="col2" nameend="col2" align="left">CHCl₂</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.24</entry><entry namest="col2" nameend="col2" align="left">CF₂Cl</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.25</entry><entry namest="col2" nameend="col2" align="left">CF₃</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.26</entry><entry namest="col2" nameend="col2" align="left">C.₂F₅</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.27</entry><entry namest="col2" nameend="col2" align="left">CF₂H</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.28</entry><entry namest="col2" nameend="col2" align="left">CH₂-CH = CH₂</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.29</entry><entry namest="col2" nameend="col2" align="left">CH (CH₃) -CH = CH₂</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.30</entry><entry namest="col2" nameend="col2" align="left">CH₂-CH = CH-CH₃</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.31</entry><entry namest="col2" nameend="col2" align="left">CH₂-C≡CH</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.32</entry><entry namest="col2" nameend="col2" align="left">CH (CH₃) -C≡CH</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.33</entry><entry namest="col2" nameend="col2" align="left">CH₂-COOH</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.34</entry><entry namest="col2" nameend="col2" align="left">CH₂-CO-OCH₃</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.35</entry><entry namest="col2" nameend="col2" align="left">CH₂-CO-OC₂H₅</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.36</entry><entry namest="col2" nameend="col2" align="left">CH₂-CO-OnC₃H₇</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.37</entry><entry namest="col2" nameend="col2" align="left">CH₂-CO-OCH (CH₃)₂</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.38</entry><entry namest="col2" nameend="col2" align="left">CH (CH₃) -CO-OCH₃</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.39</entry><entry namest="col2" nameend="col2" align="left">CH (CH₃) -CO-OC₂H₅</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.40</entry><entry namest="col2" nameend="col2" align="left">CH (CH₃) -CO-OnC₃H₇</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.41</entry><entry namest="col2" nameend="col2" align="left">CH (CH₃) -CO-OC (CH₃)₂</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.42</entry><entry namest="col2" nameend="col2" align="left">CH₂-COO- (CH₂)₂-Oh₃</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.43</entry><entry namest="col2" nameend="col2" align="left">CH₂-COO- (CH₂)₂-Oh₃</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.44</entry><entry namest="col2" nameend="col2" align="left">CH (CH₃) -COO- (CH₂)₂-Oh₃</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.45</entry><entry namest="col2" nameend="col2" align="left">CH (CH₃) -COO- (CH₂)₂-OC₂H₅</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.46</entry><entry namest="col2" nameend="col2" align="left">CH₂-CONH₂</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.47</entry><entry namest="col2" nameend="col2" align="left">CH₂-CONHCH₃</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.48</entry><entry namest="col2" nameend="col2" align="left">CH₂-CONHC₂H₅</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.49</entry><entry namest="col2" nameend="col2" align="left">CH₂-CON (CH₃)₂</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.50</entry><entry namest="col2" nameend="col2" align="left">CH (CH₃) -CONH₂</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.51</entry><entry namest="col2" nameend="col2" align="left">CH (CH₃) -CONHCH₃</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.52</entry><entry namest="col2" nameend="col2" align="left">CH (CH₃) -CONHC₂H₅</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.53</entry><entry namest="col2" nameend="col2" align="left">CH (CH₃) -CON (CH₃)₂</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.54</entry><entry namest="col2" nameend="col2" align="left">CO-CH₃</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.55</entry><entry namest="col2" nameend="col2" align="left">CO-C₂H₅</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.56</entry><entry namest="col2" nameend="col2" align="left">CO-CH (CH₃)₂</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.57</entry><entry namest="col2" nameend="col2" align="left">CO-nC₄H₉</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.58</entry><entry namest="col2" nameend="col2" align="left">CH₂-Oh₃</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.59</entry><entry namest="col2" nameend="col2" align="left">CH (CH₃) -Oh₃</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.60</entry><entry namest="col2" nameend="col2" align="left">CH (CH₃) -OC₂H₅</entry></row><row><entry namest="col1" nameend="col1" align="left">Ia.61</entry><entry namest="col2" nameend="col2" align="left">CH (CH₃) CH₂-Oh₃</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Ia.62</entry><entry namest="col2" nameend="col2" align="left">CH₂-OC₂H₅</entry></row></tbody></tgroup></table></tables>

Furthermore, the following 3- (4-cyanophenyl) uracils of the formula I are particularly preferred:<ul id="ul0004" list-style="dash" compact="compact"><li>the compounds Ib.01 - Ib.62, which differ from the corresponding compounds Ia.01 - Ia.62 only in that R¹ Hydrogen means:<chemistry id="chem0004" num="0004"><img file="EP0808310B1_D0004.tif" /></chemistry></li><li>the compounds Ic.01 - Ic.62, which differ from the corresponding compounds Ia.01 - Ia.62 only in that A is methyl:<chemistry id="chem0005" num="0005"><img file="EP0808310B1_D0005.tif" /></chemistry></li><li>the compounds Id.01 - Id.62, which differ from the corresponding compounds Ia.01 - Ia.62 only in that R¹ Hydrogen and A methyl mean:<chemistry id="chem0006" num="0006"><img file="EP0808310B1_D0006.tif" /></chemistry></li><li>the compounds Ie.01 - Ie.62, which differ from the corresponding compounds Ia.01 - Ia.62 only in that R³ Chlorine means:<chemistry id="chem0007" num="0007"><img file="EP0808310B1_D0007.tif" /></chemistry></li><li>the compounds If.01 - If.62, which differ from the corresponding compounds Ia.01 - Ia.62 only in that R³ Chlorine and A methyl mean:<chemistry id="chem0008" num="0008"><img file="EP0808310B1_D0008.tif" /></chemistry></li><li>the compounds Ig.01 - Ig.62, which differ from the corresponding compounds Ia.01 - Ia.62 only in that A methyl, R¹ Hydrogen and R³ Chlorine mean:<chemistry id="chem0009" num="0009"><img file="EP0808310B1_D0009.tif" /></chemistry></li></ul>

The 3- (4-cyanophenyl) uracils of the formula I can be obtained in various ways, for example by one of the following processes:

Procedure A):

Cyclization of an enamine ester of the formula III or an enamine carboxylate of the formula IV in the presence of a base:<chemistry id="chem0010" num="0010"><img file="EP0808310B1_D0010.tif" /></chemistry>

L¹ means low molecular weight alkyl, preferably C₁-C₄-Alkyl, or phenyl.

As a rule, cyclization is carried out in an inert organic solvent or diluent which is aprotic, for example in an aliphatic or cyclic ether such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, in an aromatic compound such as benzene and toluene or in a polar solvent such as dimethylformamide and dimethyl sulfoxide. Mixtures of polar solvent and a hydrocarbon such as n-hexane are also suitable. Depending on the starting compound, water can also be suitable as a diluent.

Suitable bases are preferably alkali metal alcoholates, in particular the sodium alcoholates, alkali metal hydroxides, in particular sodium hydroxide and potassium hydroxide, alkali metal carbonates, in particular sodium carbonate and potassium carbonate, and metal hydrides, in particular sodium hydride. When using sodium hydride as the base, it has proven advantageous to work in an aliphatic or cyclic ether, in dimethylformamide or in dimethyl sulfoxide.

Normally, 0.5 to 2 times the molar amount of base, based on the amount of III or IV, is sufficient for the reaction to succeed.

In general, the reaction temperature is from (-78) ° C to the boiling point of the respective reaction mixture, in particular from (-60) to 60 ° C.

If A in formula III or IV is hydrogen, the product of the process is obtained as a metal salt, the metal corresponding to the cation of the base used. The salt can be isolated and purified in a manner known per se or, if desired, converted into the free compound I with A = hydrogen by means of acid.

Procedure B):

Methylation of a compound I, in which A is hydrogen, in the presence of a base:<chemistry id="chem0011" num="0011"><img file="EP0808310B1_D0011.tif" /></chemistry>

Examples of suitable methylating agents are methyl halides, preferably methyl chloride, iodide or bromide, and also dimethyl sulfate, methanesulfonate (methyl mesylate), methyl benzenesulfonate, methoxy (p-toluenesulfone) (methyl tosylate), p-bromobenzenesulfonyl methane (methyl brosylate) and trifluoromethanes (trifluoromethane) Diazomethane into consideration.

As a rule, one works in an inert organic solvent or in an aprotic solvent, for example in an aliphatic or cyclic ether, preferably in 1,2-dimethoxyethane, tetrahydrofuran or dioxane, in an aliphatic ketone, preferably in acetone, in an amide, preferably in dimethylformamide, in a sulfoxide, preferably in dimethyl sulfoxide, in a urea such as tetramethylurea and 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone, in a carboxylic acid ester such as ethyl acetate, or in a halogenated aliphatic or aromatic hydrocarbon such as dichloromethane and chlorobenzene.

Suitable bases are inorganic bases, for example carbonates such as sodium carbonate and potassium carbonate, hydrogen carbonates such as sodium and potassium hydrogen carbonate, or alkali metal hydrides such as sodium hydride and potassium hydride, and organic bases, for example amines such as triethylamine, pyridine and N, N-diethylaniline, or alkali metal alcoholates such as sodium methoxide, Sodium ethanolate and potassium tert-butoxide.

The amount of base and methylating agent is preferably in each case 0.5 to 2 times the molar amount, based on the amount of starting compound.

In general, the reaction temperature is from 0 ° C to the boiling point of the reaction mixture, in particular from 0 to 60 ° C.

A preferred process variant is that the salt of I obtained from the cyclization of III (A = H) or IV (A = H) according to process A) without isolation from the reaction mixture, the excess base, for example sodium hydride, sodium alcoholate or sodium carbonate, may contain to methylate.

Unless it can be prepared directly under basic conditions by the cyclization described as method a), the salts of those compounds I in which A is hydrogen can also be obtained from the process products of method a) in a manner known per se. For this purpose, for example, the aqueous solution of an inorganic or organic base is mixed with the substituted 3- (4-cyanophenyl) uracil I, in which A stands for hydrogen. Salt formation normally takes place at 20-25 ° C with sufficient speed.

It is particularly advantageous to prepare the sodium salt by dissolving the 3- (4-cyanophenyl) uracil I (A = hydrogen) in aqueous sodium hydroxide solution at 20-25 ° C., with approximately equivalent amounts of 3- (4-cyanophenyl) uracil and Sodium hydroxide can be used. The salt of 3- (4-cyanophenyl) uracil can then be isolated, for example, by precipitation with a suitable inert solvent or by evaporation of the solvent.

Salts of 3- (4-cyanophenyl) uracils, the metal ion of which is not an alkali metal ion, can usually be prepared by salting the corresponding alkali metal salt in aqueous solution. In this way, for example, 3- (4-cyanophenyl) uracil metal salts which are insoluble in water can be produced.

Procedure C):

Reaction of a 3- (4-cyanophenyl) uracil of the formula I, where A is hydrogen, with an electrophilic amination reagent in the presence of a base:<chemistry id="chem0012" num="0012"><img file="EP0808310B1_D0012.tif" /></chemistry>

So far, 2,4-dinitrophenoxyamine has proven particularly useful as an amination reagent, but hydroxylamine-O-sulfonic acid (HOSA), for example, which is already known from the literature as an amination reagent, can also be used (cf. e.g. E. Hofer et al., Synthesis 1983 , 466; W. Friedrichsen et al., Heterocycles <u>20</u> (1983) 1271; H. Hart et al., Tetrahedron Lett.<u>25</u> (1984) 2073; B. Vercek et al., Months. Chem.<u>114</u> (1983) 789; G. Sosnousky et al., Z. Naturforsch.<u>38</u> (1983) 884; RS Atkinson et al., J. Chem. Soc. Perkin Trans. 1987, 2787).

The amination can be carried out in a manner known per se (see, for example, T. Sheradsky, Tetrahedron Lett. 1948, 1909; MP Wentland et al., J. Med. Chem. <u>27</u> (1984) 1103 and in particular EP-A 240 194, EP-A 476 697 and EP-A 517 181, where the amination of uracil is taught).

The reaction is usually carried out in a polar solvent, for example in dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide or in ethyl acetate, which has hitherto proven to be particularly suitable.

Suitable bases are, for example, alkali metal carbonates such as potassium carbonate, alkali metal alcoholates such as sodium methylate and potassium tert-butoxide or alkali metal hydrides such as sodium hydride.

The amount of base and aminating agent is preferably in each case 0.5 to 2 times the molar amount, based on the amount of starting compound.

Depending on the meaning of R⁴ it may be necessary to protect these substituents before the amination in a manner known per se. This is particularly recommended if R⁴ stands for hydrogen.

Procedure D):

Ether cleavage of a 3- (4-cyanophenyl) uracil of the formula I, in which R⁴ Alkyl, cycloalkyl, alkenyl or alkynyl means:<chemistry id="chem0013" num="0013"><img file="EP0808310B1_D0013.tif" /></chemistry>

The ether cleavage is usually carried out using an acid, for example using hydrogen bromide, hydrogen iodide or pyridinium hydrochloride, using a Lewis acid such as aluminum trichloride, tribromide, triiodide, boron trichloride, tribromide, trifluoride and iron trichloride, or using trimethylsilyl iodide. In addition, lithium salts such as lithium chloride or mixtures of an inorganic iodide and trimethylsilyl chloride can also be used in order to cleave the ether bond. In individual cases, the bond can also be split under hydrogenation conditions using hydrogen in the presence of a hydrogenation catalyst such as platinum and palladium on activated carbon.

Allyl ether (R⁴ = Allyl) can also be converted into the corresponding phenols in a manner known per se, for example by isomerization in the presence of a transition metal catalyst to give the enol ether and cleavage of the latter, preferably under slightly acidic conditions (see, for example, T. Greene and PGM Wutz in " Protective Groups in Organic Synthesis ", John Wiley &amp; Sons, 2nd edition New York 1991, pp. 42ff.).

Usually one works in an inert solvent or diluent, e.g. B. in an aliphatic, cyclic or aromatic hydrocarbon such as n-pentane, petroleum ether, cyclohexane, benzene, toluene or xylene, an aliphatic or cyclic ether such as diethyl ether, tert-butyl methyl ether, dimethoxyethane and tetrahydrofuran, an aliphatic or aromatic halogenated hydrocarbon such as dichloromethane, Chorbenzol, 1,2-dichloroethane and the dichlorobenzenes, an alcohol such as methanol, ethanol and tert-butanol, an amide such as dimethylformamide and N-methylpyrrolidone, an amine such as ammonia, or in a mixture of such solvents.

A reaction without a solvent can also be advantageous.

With regard to particularly preferred embodiments, reference is made to the statements in Houben-Weyl, "Methods of Organic Chemistry", Georg Thieme Verlag, 4th Edition, Stuttgart 1979, Vol. 6 / 1a / 1, p. 309ff and in RC Larock, "Comprehensive Organic Transformations ", VCH-Publishers, Weinheim 1989, pp. 501ff and to the literature cited therein.

Procedure E):

Alkylation of a 3- (4-cyanophenyl) uracil of the formula I in which R⁴ Hydrogen means in the presence of a base:<chemistry id="chem0014" num="0014"><img file="EP0808310B1_D0014.tif" /></chemistry>

The alkylation can, for example, with the halide, preferably the chloride or bromide, the sulfate, sulfonate, preferably the methanesulfonate (mesylate), benzenesulfonate, p-toluenesulfonate (tosylate), p-bromobenzenesulfonate (brosylate), the trifluoromethanesulfonate (trifoverbate) or the diazonate an unsubstituted or substituted alkane, cycloalkane, haloalkane, alkene or alkyne.

Usually one works in an inert organic solvent, especially aprotic solvents, eg aliphatic and cyclic ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, aliphatic ketones such as acetone, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, ureas such as tetramethylurea and 1,3-dimethyltetrahydro-2 (1H) pyrimidinone, carboxylic acid esters such as acetic acid or ethyl acetate Halogenated aliphatic or aromatic hydrocarbons, such as dichloromethane and chlorobenzene, can be considered.

Suitable bases are both inorganic bases, for example alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal hydrogen carbonates such as sodium and potassium hydrogen carbonate, or alkali metal hydrides such as sodium hydride and potassium hydride, and also organic bases, for example amines such as triethylamine, pyridine and N, N-diethylaniline alcohol, or alkali metal alkali Sodium methoxide, ethanolate and potassium tert-butoxide.

The amount of base and alkylating agent is preferably 0.5 to 2 times the molar amount, based on the amount of I with R.⁴ = Hydrogen.

In general, a reaction temperature of 0 ° C to the boiling point of the reaction mixture is recommended, in particular from 0 to 60 ° C.

Any regioselectivity problems with starting compounds with A = hydrogen can be avoided in a manner known per se (use of 2 equivalents of base, introduction of a protective group, etc.).

Procedure F):

Acylation of a 3- (4-cyanophenyl) uracil of the formula I, where R⁴ Means hydrogen with a suitable acylating agent.<chemistry id="chem0015" num="0015"><img file="EP0808310B1_D0015.tif" /></chemistry>

Suitable acylating agents are, for example, the acid halides, in particular the acid chlorides, the anhydrides, isocyanates or sulfonyl chlorides of alkane carboxylic acids. However, the free acids or their anhydrides are also suitable, provided that a condensing agent such as carbonyldiimidazole and dicyclohexylcarbondiimide is used.

As a rule, one works in an inert organic solvent or diluent, which is preferably aprotic, for example in an aliphatic or cyclic ether such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, an aliphatic ketone such as acetone, an amide such as dimethylformamide, a urea such as tetramethylurea and 1,3-dimethyltetrahydro2 (1H) -pyrimidinone, a carboxylic acid ester such as ethyl acetate, or an aliphatic or aromatic halogenated hydrocarbon such as dichloromethane and chlorobenzene.

With regard to suitable bases, the proportions and the reaction temperature, reference is made to the statements under process E).

Procedure G):

Substitution of halide by cyanide:<chemistry id="chem0016" num="0016"><img file="EP0808310B1_D0016.tif" /></chemistry>

Hal represents halogen, preferably fluorine, bromine or iodine.

Suitable cyanides are in particular metal cyanides, for example the alkali metal cyanides such as lithium, sodium and potassium cyanide, the alkaline earth metal cyanides such as magnesium cyanide, or also transition metal cyanides such as copper cyanide.

Usually one works in an ether such as tetrahydrofuran, dioxane and 1,2-dimethoxyethane, or in an aprotic, polar solvent, for example an alkyl nitrile such as aceto-, propio- and butyronitrile, an alkyl urea such as N, N, N ', N'-tetramethyl urea, an open-chain or cyclic dialkylamide such as dimethylformamide, N-methyl-2-pyrrolidone, 1,2-dimethyl-imidazolidine 2-one and 1,2-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, a dialkyl sulfoxide such as dimethyl sulfoxide, or in hexamethylphosphoric triamide.

According to the previous knowledge, the presence of a catalyst can have an advantageous effect on the course of the reaction. Usable catalysts are, for example, transition metals and their complexes or salts, for example compounds of copper such as copper (I) chloride, iodide, cyanide, or of nickel such as nickel bis-triphenylphosphine dibromide.

For starting compounds V with A = hydrogen, it is advisable to work in the presence of a base, in particular weakly nucleophilic bases, both inorganic bases, for example alkali metal carbonates such as sodium and potassium carbonate, alkali metal hydrogen carbonates such as sodium and potassium hydrogen carbonate, or alkali metal hydrides such as sodium hydride and potassium hydride, and also organic bases, for example amines such as triethylamine, pyridine and N, N-diethylaniline.

The proportions are usually not critical. In general, about one to ten times the amount of cyanide and base, based on the amount of V, is sufficient.

The reaction temperature is usually 50 to 250 ° C; To increase the selectivity of the reaction, it may also be advisable to work at lower temperatures, in particular at about 20 ° C.

With regard to various embodiments of this implementation, see Houben-Weyl, "Methods of Organic Chemistry", Georg Thieme Verlag, 4th Edition, Stuttgart 1985, Vol. E5, pp. 1444ff. as well as reference to the literature given there.

Procedure H):

Halogenation of a 3- (4-cyanophenyl) uracil of the formula I, in which R³ Means hydrogen<chemistry id="chem0017" num="0017"><img file="EP0808310B1_D0017.tif" /></chemistry>

The halogenation is usually carried out in an inert organic solvent or diluent. For chlorination and bromination, for example, aliphatic carboxylic acids such as acetic acid or chlorinated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride can be used. Low-boiling aliphatic carboxylic acids such as acetic acid are particularly preferred for iodination.

Elemental chlorine or bromine, or sulfuryl chloride or sulfuryl bromide are particularly suitable for chlorination and bromination, at a reaction temperature of preferably 0 to 60 ° C., in particular 10 to 30 ° C.

If desired, the chlorination and bromination can be carried out in the presence of an acid-binding agent, sodium acetate and tertiary amines such as triethylamine, dimethylaniline and pyridine being particularly preferred.

Elemental iodine is particularly preferred as the iodinating agent, in which case the reaction temperature is approximately 0 to 110 ° C., preferably 10 to 30 ° C.

Iodination in the presence of a mineral acid such as fuming nitric acid is particularly advantageous.

The amount of halogenating agent is not critical; normally equimolar amounts of halogenating agent or an excess of up to about 200 mol%, based on the starting material to be halogenated, are used.

Excess iodine can be removed, for example, after the reaction by means of saturated aqueous sodium bisulfite solution.

Procedure I):

Substitution of the nitro group of 3- (4-cyano-3-nitrophenyl) uracilen VI by a group -OR⁴: <chemistry id="chem0018" num="0018"><img file="EP0808310B1_D0018.tif" /></chemistry>

The nitro group is usually substituted by reacting VI with an alcoholate MOR⁴, where M stands for a metal atom, preferably lithium, sodium or potassium (see, for example, Org. Synth. Coll. Vol. III, 293).

As a rule, one works either in the alcohol HOR⁴, the alcoholate of which is used, or in an inert organic solvent or diluent, for example in an aromatic hydrocarbon such as toluene and the xylenes, in an ether such as diethyl ether, tetrahydrofuran and 1,2-dimethoxyethane, or in a halogenated hydrocarbon such as dichloromethane and chlorobenzene .

The reaction temperature is generally from 0 to 150 ° C, preferably at room temperature (about 20 ° C) to the boiling point of the respective reaction mixture.

The amount of alcoholate is usually not critical; about 1 to 3 equivalents of alcoholate per mole of VI are preferred.

The 3- (4-cyano-3-nitrophenyl) uracils V are in turn, for example, from 3- (4-halo-3-nitrophenyl) uracils VII<chemistry id="chem0019" num="0019"><img file="EP0808310B1_D0019.tif" /></chemistry> obtainable by substituting cyano for the halogen. The information given in procedure G) applies accordingly.

The 3- (4-halo-3-nitrophenyl) uracils VII in turn can be, for example, by nitration of 3- (4-halophenyl) uracils VIII<chemistry id="chem0020" num="0020"><img file="EP0808310B1_D0020.tif" /></chemistry> with nitric acid, nitrating acid, with an inorganic nitrate such as sodium, potassium and ammonium nitrate or with an organic nitrate such as amyl nitrate.

Suitable solvents for the nitration are preferably inorganic acids such as nitric acid and sulfuric acid, organic acids such as acetic acid, or anhydrides such as acetic anhydride.

The reaction temperature is usually (-20) to 50 ° C, preferably (-10) to 30 ° C.

The amount of nitrating agent is not critical; it is usually from one to ten times the molar amount, based on the amount of VI.

Procedure K):

Conversion of 3- (4-aminophenyl) uracil IX into compounds I using the Sandmeyer method:<chemistry id="chem0021" num="0021"><img file="EP0808310B1_D0021.tif" /></chemistry>

In this type of reaction, the procedure is usually such that the amino group is converted into the diazonium salt in a manner known per se, and this is then carried out in the presence of a transition metal catalyst, in particular a copper (I) salt, advantageously copper (I) cyanide Metal cyanide, preferably with lithium, sodium or potassium cyanide.

With regard to the process conditions, reference is made, for example, to the explanations in C. Ferri, "Reactions in Organic Chemistry", Georg Thieme Verlag, Stuttgart 1978, p. 319 and in Organic Synthesis Coll. Vol 1, S 514 (1941).

The starting compounds IX can preferably be prepared by reducing the corresponding nitro compounds with hydrogen in the presence of a metal catalyst consisting of Raney nickel, palladium or platinum, or with a reducing agent, for example a stannous salt or iron. Further details of this known reaction can be found, for example, in DE-A 37 24 399.

The nitrated precursors corresponding to the compounds IX are in turn expedient by nitrating phenyl compounds X.<chemistry id="chem0022" num="0022"><img file="EP0808310B1_D0022.tif" /></chemistry> available. The statements made regarding the nitration of 3- (4-halophenyl) uracils VII in process I) apply accordingly to the nitration of phenyluracils X.

Procedure L):

Direct cyanation of a phenyl compound X:<chemistry id="chem0023" num="0023"><img file="EP0808310B1_D0023.tif" /></chemistry>

The cyanation can be carried out without a solvent or in an inert solvent or diluent, for example in an aliphatic, cyclic or aromatic hydrocarbon such as n-pentane, petroleum ether and cyclohexane, an aliphatic or cyclic ether such as diethyl ether, tert-butyl methyl ether, dimethoxyethane and tetrahydrofuran , an aliphatic or aromatic halogenated hydrocarbon such as dichloromethane, chloroform, 1,2-dichloroethane and the dichlorobenzenes, an alcohol such as ethanol, methanol and tert-butanol, an amide such as dimethylformamide and N-methylpyrrolidone, or an amine such as ammonia. Mixtures of such solvents are also suitable.

Suitable cyanide sources are alkylthiocyanates such as methylthiocyanate {cf. e.g. synth. Commun.<u>20</u>, 71 (1990)}, chlorosulfonyl isocyanate (see, for example, Org. Synth. Coll. Vol VI, p. 465), dicyane, cyanogen chloride and cyanogen bromide, and also trichloroacetonitrile {see. on this Gazz. Chim. Italian<u>122</u>, 283 (1992)}.

The temperatures are normally from (-20) to 150 ° C., preferably from (-10) ° C. to the boiling point of the respective reaction mixture.

The ratio of cyanating agent to IX is not critical; it is usually 1: 1 to 10: 1.

Modifications to this implementation are described, inter alia, in Houben-Weyl, "Methods of Organic Chemistry", Georg Thieme Verlag, Vol. E5, 4th Edition, Stuttgart 1985, pp. 1447 ff and in the literature cited therein.

The starting compounds of the formulas VI, VII, VIII and IX are known or can be prepared in a manner known per se (cf., for example, EP-A 255 047, EP-A 517 181 and JP-A 05/025 143).

The enamine esters of formula III are new. They can also be used as herbicides.

They can be produced by methods known per se, e.g. B. one of the following methods: M):<chemistry id="chem0024" num="0024"><img file="EP0808310B1_D0024.tif" /></chemistry>

It is preferred to work essentially anhydrous in an inert solvent or diluent, particularly preferably in the presence of an acidic or basic catalyst.

Suitable solvents or diluents are, in particular, water solvents which are azeotropically miscible with water, for example aromatics such as benzene, toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene, aliphatic and cyclic ethers such as 1,2 -Dimethoxyethane, tetrahydrofuran and dioxane, or cyclohexane, but also alcohols such as methanol and ethanol, into consideration.

Suitable acidic catalysts are preferably strong mineral acids such as sulfuric acid and hydrochloric acid, phosphorus-containing acids such as orthophosphoric acid and polyphosphoric acid, organic acids such as p-toluenesulfonic acid and acidic cation exchangers such as "Amberlyst 15" (Fluka).

Suitable basic catalysts are, for example, metal hydrides such as sodium hydride and particularly preferably metal alcoholates such as sodium methoxide and ethanolate.

Appropriately, XI and the β-ketoester XII are used in an approximately stoichiometric ratio or one works with a slight excess of one or the other component, up to about 10 mol%.

A quantity of catalyst of 0.5 to 2 mol%, based on the quantity of a starting material, is normally sufficient.

In general, the reaction is carried out at a temperature of 60 to 120 ° C., for the rapid removal of water formed, preferably at the boiling point of the reaction mixture. N):<chemistry id="chem0025" num="0025"><img file="EP0808310B1_D0025.tif" /></chemistry>

L² means C₁-C₄-Alkyl or phenyl.

This reaction can be carried out, for example, in an inert, water-miscible, organic solvent, for example an aliphatic or cyclic ether such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, or a lower alcohol, in particular ethanol, the reaction temperature being normally from 50 to 100 ° C, preferably at the boiling point of the reaction mixture.

However, the reaction can also be carried out in an aromatic diluent such as benzene, toluene and o-, m-, p-xylene, in which case either the addition of an acidic catalyst such as hydrochloric acid and p-toluenesulfonic acid or a base, for example an alkali metal alcoholate such as Sodium methoxide and sodium ethanolate, is recommended. In this process variant too, the reaction temperature is normally 50 to 100 ° C., but preferably 60 to 80 ° C.

With regard to the quantitative ratios, the information for method M) applies. O):<chemistry id="chem0026" num="0026"><img file="EP0808310B1_D0026.tif" /></chemistry>

The reaction is conveniently carried out in the presence of an essentially anhydrous aprotic organic solvent or diluent, for example an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, an aliphatic or aromatic hydrocarbon such as n-hexane, benzene, toluene and o-, m-, p-xylene, a halogenated, aliphatic hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene, an aprotic, polar solvent such as dimethylformamide, hexamethylphosphoric triamide and dimethyl sulfoxide, or a mixture of the solvents mentioned.

If desired, it is also possible to work in the presence of a metal hydride base such as sodium and potassium hydride or an organic tertiary base such as triethylamine and pyridine, where the organic base can simultaneously serve as a solvent.

The starting materials are expediently used in a stoichiometric ratio or one works with a slight excess of one or the other component up to about 10 mol%. If one works without solvent in the presence of an organic base, this is present in a large excess.

The reaction temperature is preferably (-80) to 50 ° C, in particular (-60) to 30 ° C.

In a particularly preferred embodiment, the enamine ester III obtained is converted directly (ie “in situ”) into excess product I according to process A) into the corresponding product of value I. P):<chemistry id="chem0027" num="0027"><img file="EP0808310B1_D0027.tif" /></chemistry>

L³ means C₁-C₄-Alkyl or phenyl.

This reaction is advantageously carried out in an aprotic, polar solvent or diluent such as dimethylformamide, 2-butanone, dimethyl sulfoxide and acetonitrile, advantageously in the presence of a base, for example an alkali metal or alkaline earth metal alcoholate, in particular a sodium alkanolate such as sodium methoxide, an alkali metal or alkaline earth metal carbonate , in particular sodium carbonate, or an alkali metal hydride such as lithium and sodium hydride.

Usually 1 to 2 times the molar amount of base, based on the amount of XIV or XVI, is sufficient.

The reaction temperature is generally 80 to 180 ° C, preferably at the boiling point of the reaction mixture.

With regard to the quantitative ratios of the starting compounds, the information for method M) applies.

In a particularly preferred embodiment, a sodium alcoholate is used as the base and the alcohol formed in the course of the reaction is distilled off continuously. The enamine esters III prepared in this way can be cyclized to a salt of the substituted 3- (4-cyanophenyl) uracils I without isolation from the reaction mixture according to process A). Q):<chemistry id="chem0028" num="0028"><img file="EP0808310B1_D0028.tif" /></chemistry>

This reaction is advantageously carried out in an essentially anhydrous, aprotic, organic solvent or diluent, for example in the presence of an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, an aliphatic or aromatic hydrocarbon such as n-hexane, benzene , Toluene and o-, m-, p-xylene, a halogenated, aliphatic hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene, an aprotic, polar solvent such as dimethylformamide, hexamethylphosphoric triamide and dimethyl sulfoxide, or a mixture of the solvents mentioned.

If desired, it is possible to work in the presence of a metal hydride base such as sodium and potassium hydride, an alkali metal or alkaline earth metal alcoholate such as sodium methoxide, ethanolate and potassium tert-butoxide, or an organic nitrogen base such as triethylamine and pyridine, where the organic base can simultaneously serve as a solvent .

The starting materials are expediently used in stoichiometric amounts or one of the components is used in excess, up to about 20 mol%. If one works without solvent in the presence of an organic base, this is advantageously present in an even larger excess.

The reaction temperature is generally from (-80) to 150 ° C, preferably from (-30) ° C to the boiling point of the reaction mixture.

The enamine carboxylates of formula IV are also new; They can also be prepared in a manner known per se, for example from an aniline derivative of the formula VIII according to the following reaction scheme: (G11)<chemistry id="chem0029" num="0029"><img file="EP0808310B1_D0029.tif" /></chemistry> (G12)<chemistry id="chem0030" num="0030"><img file="EP0808310B1_D0030.tif" /></chemistry>

The reaction according to reaction equation 1 is preferably carried out in an anhydrous inert aprotic solvent, for example in a halogenated hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene, an aromatic hydrocarbon such as benzene, toluene and o-, m-, p-xylene, or an aliphatic or cyclic ethers such as diethyl ether, dibutyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane.

When XIX is reacted with XVIII in accordance with equation (G11), the reaction temperature is generally about 70 to 140 ° C., in particular 100 to 120 ° C.

The reaction according to reaction equation (G12) is an aminolysis, which is usually either without a solvent [cf. e.g. J. Soc. Dyes Col.<u>42</u>, 81 (1926), Ber. <u>64</u>, 970 (1931); Org. Synth., Coll. Vol. IV, 80 (1943) and JACS<u>70</u>, 2402 (1948)] or in an inert anhydrous solvent / diluent, in particular in an aprotic solvent, for example in an aromatic such as toluene and o-, m-, p-xylene or a halogenated aromatic such as chlorobenzene.

It is recommended to work in the presence of a basic catalyst, for example a higher boiling amine [see e.g. B. Helv. Chim. Acta<u>11</u>, 779 (1928) and US 2,416,738] or pyridine.

The reaction temperature is preferably about 130 to 160 ° C.

In both reactions {(G11) and (G12)}, the starting compounds are expediently used in approximately stoichiometric amounts or one works with a slight excess of one or the other component up to approximately 10 mol%. If one works in the presence of a basic catalyst, a catalyst amount of 0.5 to 2 mol%, based on the amount of one of the starting materials, is normally sufficient.

The subsequent reaction of the compounds of the formula XX thus prepared with the amine XXI is advantageously carried out in a largely anhydrous solvent / diluent at atmospheric pressure, particularly preferably in the presence of an acidic catalyst.

To prepare enamine carboxylates IV with A = amino, it is advisable to use compounds XXI with a protected amino group (for example as a hydrazone).

Suitable solvents / diluents are, in particular, water which is azeotropically miscible with water, for example aromatics such as benzene, toluene and o-, m-, p-xylene or halogenated hydrocarbons such as carbon tetrachloride and chlorobenzene.

Suitable catalysts are in particular strong mineral acids such as sulfuric acid, organic acids such as p-toluenesulfonic acid, phosphorus-containing acids such as orthophosphoric acid and polyphosphoric acid or acidic cation exchangers such as "Amberlyst 15" (Fluka).

In general, the reaction temperature is about 70 to 150 ° C; however, to rapidly remove the water of reaction formed, the reaction mixture is advantageously carried out at the boiling point of the reaction mixture in question.

Unless otherwise stated, all of the processes described above are expediently carried out at atmospheric pressure or under the autogenous pressure of the respective reaction mixture.

The reaction mixtures are generally worked up by methods known per se, for example by removing the solvent, distributing the residue in a mixture of water and a suitable organic solvent and working up the organic phase onto the product.

The 3- (4-cyanophenyl) uracils of the formula I can contain one or more centers of chirality and are then usually obtained as mixtures of enantiomers or diastereomers. If desired, the mixtures can be separated into the largely pure isomers by the methods customary for this, for example by means of crystallization or chromatography on an optically active adsorbate. Pure optically active isomers can also be produced, for example, from corresponding optically active starting materials.

3- (4-Cyanophenyl) uracile I, in which A is hydrogen, can be converted into their salts, preferably into their alkali metal salts, in a manner known per se (cf. also production method b)).

Salts of I, the metal ion of which is not an alkali metal ion, can be prepared in a conventional manner by salting the corresponding alkali metal salt, as can ammonium, phosphonium, sulfonium and sulfoxonium salts using ammonia, phosphonium, sulfonium or sulfoxonium hydroxides.

The compounds I and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of the pure isomers - as herbicides. The herbicidal compositions containing I control vegetation very well on non-cultivated areas, particularly when high amounts are applied. In crops such as wheat, rice, maize, soybeans and cotton, they act against weeds and grass weeds without significantly damaging the crop plants. This effect occurs especially at low application rates.

Depending on the particular application method, the compounds I or herbicidal compositions comprising them can also be used in a further number of crop plants for eliminating undesired plants. For example, the following crops can be considered: Allium cepa, pineapple comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spp. altissima, Beta vulgaris spp. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesutumum, Glycine arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spp., Manihot esculenta, Medicago sativa, Musa spp., Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spp., Pisum sativum, Prunus av Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (see vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.

In addition, the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.

The 3- (4-cyanophenyl) uracils I are also suitable for the desiccation and / or defoliation of plants.

As desiccants, they are particularly suitable for drying out the above-ground parts of crops such as potatoes, rapeseed, sunflower and soybeans. This enables fully mechanical harvesting of these important crops.

Also of economic interest is the ease of harvesting, which is made possible by the temporally concentrated decrease or decrease in the adhesive strength on the tree in the case of citrus fruits, olives or other types and varieties of pome, stone and nuts. The same mechanism, that is to say the promotion of the formation of separating tissue between the fruit or leaf and shoot part of the plants, is also essential for easily controllable defoliation of useful plants, in particular cotton.

In addition, the shortening of the time interval in which the individual cotton plants ripen leads to an increased fiber quality after the harvest.

The compounds I or the compositions comprising them can be sprayed, atomized, for example in the form of directly sprayable aqueous solutions, powders, suspensions, including high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, sprays or granules. Dusting, scattering or pouring can be used. The application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.

The following are essentially considered as inert auxiliaries for the production of directly sprayable solutions, emulsions, pastes or oil dispersions: mineral oil fractions from medium to high boiling point such as kerosene and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffins, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, for example amines such as N-methylpyrrolidone and water.

Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the substrates as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. However, concentrates consisting of active substance, wetting agent, adhesive, dispersant or emulsifier and possibly solvent or oil can also be prepared which are suitable for dilution with water.

The surfactants (adjuvants) are the alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, for example Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols as well as of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives Formaldehyde, condensation products of naphthalene or the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl, tributylphenyl, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol condensates, ethoxylated castor oil, polyoxyethylene or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors or methylcellulose .

Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.

Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral soils such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Urea and vegetable products such as flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.

The concentrations of the active ingredients I in the ready-to-use preparations can be varied over a wide range. In general, the formulations contain from 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).

The following formulation examples illustrate the preparation of such preparations:<ul id="ul0005" list-style="none"><li>I. 20 parts by weight of the active ingredient are dissolved in a mixture consisting of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 Moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.</li><li>II. 20 parts by weight of compound no. I.01 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide on 1 Mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which contains 0.02% by weight of the active ingredient.</li><li>III. 20 parts by weight of the active ingredient are dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction with a boiling point of 210 to 280 ° C. and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which contains 0.02% by weight of the active ingredient.</li><li>IV. 20 parts by weight of active ingredient No. I.02 are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel and ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained which contains 0.1% by weight of the active ingredient.</li><li>V. 3 parts by weight of active ingredient No. I.03 are mixed with 97 parts by weight of finely divided kaolin. In this way, a dusting agent is obtained which contains 3% by weight of the active ingredient.</li><li>VI. 20 parts by weight of the active ingredient are intimately mixed with 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a phenol-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.</li><li>VII. 1 part by weight of compound no. I.04 is dissolved in a mixture consisting of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. A stable emulsion concentrate is obtained.</li><li>VIII. 1 part by weight of compound no. I.05 is dissolved in a mixture consisting of 80 parts by weight of cyclohexanone and 20 parts by weight of Emulphor EL¹) consists. A stable emulsion concentrate is obtained.</li></ul>

The active ingredients I or the herbicidal compositions can be applied pre- or post-emergence. If the active ingredients are less compatible for certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not struck wherever possible, while the active ingredients are applied to the leaves of undesirable plants growing below them or the uncovered floor area (post-directed, lay-by).

The application rates of active ingredient I are 0.001 to 3.0, preferably 0.01 to 1 kg / ha of active substance (as), depending on the control target, the season, the target plants and the growth stage.

To broaden the spectrum of activity and to achieve synergistic effects, the 3- (4-cyanophenyl) uracils I can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together. For example, 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and their derivatives, aminotriazoles, anilides, aryloxy- / heteroaryloxyalkanoic acids and their derivatives, benzoic acid and their derivatives, benzothiadiazinones, 2- (hetaroyl / Aroyl) -1,3-cyclohexanediones, heteroaryl aryl ketones, benzylisoxazolidinones, meta-CF₃-Phenyl derivatives, carbamates, quinoline carboxylic acid and their derivatives, chloroacetanilides, cyclohexane-1,3-dione derivatives, diazines, dichloropropionic acid and their derivatives, dihydrobenzofurans, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridonic acids and their derivatives, halogen carbons 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3,4,5,6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols, aryloxy- and heteroaryloxyphenoxypropionic acid esters, Phenylacetic acid and its derivatives, 2-phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acids and their derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides and uracils.

1) ethoxylated castor oil (caster oil)

It may also be useful to apply the compounds I alone or in combination with other herbicides, mixed with other crop protection agents, for example with agents for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are used to remedy nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates can also be added.

Manufacturing examples

example 1

step 1

3- [4-Cyano-3-methoxy-phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione

Sodium methoxide solution was added to a solution of 3- [4-cyano-3-nitro-phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (2.4 g) in 50 ml of anhydrous methanol (2.8 g of a 30 percent solution in methanol). The reaction mixture was then heated to reflux for 5 hours. After cooling, first water (50 ml) and then up to a pH of 3 -4 10% aqueous hydrochloric acid were added. The precipitate formed was then separated off, washed with water and petroleum ether and dried. Yield: 1.1 g; M.p .:&gt; 230 ° C.

Level 2

1-amino-3- [4-cyano-3-methoxy-phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (Verb.1.01)

To a solution of 3- [4-cyano-3-methoxy-phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (1.1 g) in 15 ml of ethyl acetate was added potassium carbonate (1 , 0 g) and 2,4-dinitrophenoxyamine (0.8 g). The mixture was then stirred at 55-60 ° C. for 15 hours, after which the solid fraction formed was separated off and washed with in each case 30 ml of ethyl acetate and diisopropyl ether. The combined filtrates were washed twice with 25 ml of water, dried over sodium sulfate and then concentrated. After crystallization with 10 ml of diisopropyl ether, 0.6 g of product of value was obtained. M.p .:&gt; 230 ° C.

Example 3

1-Amino-3- [4-cyano-3-hydroxy-phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (Verb.1.04)

1-Amino-3- [4-cyano-3-methoxyphenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (2.0 g) and pyridinium hydrochloride (2.1 g ) were stirred at 200-210 ° C for 2 hours. After cooling, the reaction mixture was dissolved in 100 ml of n-butanol, after which the solution was washed three times with 30 ml of water each time. The organic phase was dried over sodium sulfate and then freed from the solvent. After crystallization with 10 ml of diisopropyl ether and chromatographic purification of the crude product (mobile phase: dichloromethane / ethyl acetate = 9: 1 to 1: 1), 0.4 g of product of value was obtained. M.p .:&gt; 230 ° C.

Example 4

3- [3-allyloxy-4-cyano-phenyl] -1-methyl-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (Verb. 1.05)

To a solution of 3- [3-allyloxy-4-cyano-phenyl] -1-methyl-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (10.1 g) in 130 ml Potassium carbonate (4.6 g) and methyl iodide (2.1 ml, dissolved in 20 ml of dimethylformamide) were added to dimethylformamide. After stirring for 20 hours at room temperature, 150 ml of water were added to the reaction mixture, after which the precipitate formed was separated off, washed with water and petroleum ether and dried. Yield: 2.5 g; M.p .: 158-160 ° C.

In addition to the abovementioned ones, the following Table 2 lists further 3- (4-cyanophenyl) uracils I which were prepared or can be prepared in an analogous manner:<chemistry id="chem0031" num="0031"><img file="EP0808310B1_D0031.tif" /></chemistry><tables id="tabl0002" num="0002"><table frame="all"><tgroup cols="7" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="22.50mm" /><colspec colnum="2" colname="col2" colwidth="22.50mm" /><colspec colnum="3" colname="col3" colwidth="22.50mm" /><colspec colnum="4" colname="col4" colwidth="22.50mm" /><colspec colnum="5" colname="col5" colwidth="22.50mm" /><colspec colnum="6" colname="col6" colwidth="22.50mm" /><colspec colnum="7" colname="col7" colwidth="22.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="left">No.</entry><entry namest="col2" nameend="col2" align="left">A</entry><entry namest="col3" nameend="col3" align="left">R¹</entry><entry namest="col4" nameend="col4" align="left">R²</entry><entry namest="col5" nameend="col5" align="left">R³</entry><entry namest="col6" nameend="col6" align="left">R⁴</entry><entry namest="col7" nameend="col7" align="left">Mp [° C]</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">1.01</entry><entry namest="col2" nameend="col2" align="left">NH₂</entry><entry namest="col3" nameend="col3" align="left">H</entry><entry namest="col4" nameend="col4" align="left">CF₃</entry><entry namest="col5" nameend="col5" align="left">H</entry><entry namest="col6" nameend="col6" align="left">CH₃</entry><entry namest="col7" nameend="col7" align="left">&gt;230</entry></row><row><entry namest="col1" nameend="col1" align="left">1.02</entry><entry namest="col2" nameend="col2" align="left">NH₂</entry><entry namest="col3" nameend="col3" align="left">H</entry><entry namest="col4" nameend="col4" align="left">CF₃</entry><entry namest="col5" nameend="col5" align="left">H</entry><entry namest="col6" nameend="col6" align="left">CH₂CH = CH₂</entry><entry namest="col7" nameend="col7" align="left">177-179</entry></row><row><entry namest="col1" nameend="col1" align="left">1.03</entry><entry namest="col2" nameend="col2" align="left">CH₃</entry><entry namest="col3" nameend="col3" align="left">H</entry><entry namest="col4" nameend="col4" align="left">CF₃</entry><entry namest="col5" nameend="col5" align="left">H</entry><entry namest="col6" nameend="col6" align="left">CH₃</entry><entry namest="col7" nameend="col7" align="left">&gt;230</entry></row><row><entry namest="col1" nameend="col1" align="left">1.04</entry><entry namest="col2" nameend="col2" align="left">NH₂</entry><entry namest="col3" nameend="col3" align="left">H</entry><entry namest="col4" nameend="col4" align="left">CF₃</entry><entry namest="col5" nameend="col5" align="left">H</entry><entry namest="col6" nameend="col6" align="left">H</entry><entry namest="col7" nameend="col7" align="left">&gt;230</entry></row><row><entry namest="col1" nameend="col1" align="left">1.05</entry><entry namest="col2" nameend="col2" align="left">CH₃</entry><entry namest="col3" nameend="col3" align="left">H</entry><entry namest="col4" nameend="col4" align="left">CF₃</entry><entry namest="col5" nameend="col5" align="left">H</entry><entry namest="col6" nameend="col6" align="left">CH₂CH = CH₂</entry><entry namest="col7" nameend="col7" align="left">158-160</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">1.06</entry><entry namest="col2" nameend="col2" align="left">NH₂</entry><entry namest="col3" nameend="col3" align="left">H</entry><entry namest="col4" nameend="col4" align="left">CF₃</entry><entry namest="col5" nameend="col5" align="left">H</entry><entry namest="col6" nameend="col6" align="left">CH (CH₃)₂</entry><entry namest="col7" nameend="col7" align="left">185-187</entry></row></tbody></tgroup></table></tables>

Preparation of the starting compounds:

Example 5

3- [4-Cyano-3-nitro-phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione

To a solution of 3- [4-fluoro-3-nitro-phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (31.9 g) in 250 ml of anhydrous N, N -Dimethylformamide was added to potassium carbonate (16.6 g) and potassium cyanide (7.8 g). The reaction mixture was then stirred for a total of 45 hours at 75-80 ° C., since potassium cyanide (together 4.6 g) was added twice since the reaction was not complete. For working up, water (250 ml) was added to the reaction mixture after cooling. A pH of 2-3 was then set by adding 60 ml of 1N hydrochloric acid. After nitrogen had been blown through the suspension for 4 hours to drive off the hydrocyanic acid, the precipitate formed was separated off, washed with water and petroleum ether and dried. Yield: 17.0 g; M.p .: 135 ° C.

Example 6

3- [4-Cyano-2-fluoro-5-nitro-phenyl] -1-methyl-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione

To a solution of 3- [2,4-difluoro-5-nitro-phenyl] -1-methyl-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (2.5 g) in Potassium cyanide (0.5 g) was added to 50 ml of anhydrous dimethyl sulfoxide. The reaction mixture was then stirred for 10 hours at room temperature, potassium cyanide (0.16 g) being added again after 5 hours. For working up, the solvent was largely removed at 80 ° C. in a high vacuum. The residue was taken up in 150 ml of water, washed three times with 30 ml of water each time, dried over sodium sulfate and concentrated. After chromatography on silica gel (dichloromethane as eluent) and crystallization with petroleum ether, 1.2 g of product of value were obtained; M.p .: 155-157 ° C.

Examples of use (herbicidal activity)

The herbicidal activity of 3- (4-cyanophenyl) uracile I was demonstrated by the following greenhouse tests:

Plastic flower pots with loamy sand with about 3.0% humus as a substrate served as culture vessels. The seeds of the test plants were sown separately according to species.

In pre-emergence treatment, the active ingredients suspended or emulsified in water were applied directly after sowing by means of finely distributing nozzles. The vessels were lightly sprinkled to promote germination and growth, and then covered with clear plastic covers until the plants had grown. This cover causes the test plants to germinate evenly, unless this was affected by the active ingredients.

For the purpose of post-emergence treatment, the test plants, depending on the growth habit, were first grown to a height of 3 to 15 cm and only then treated with the active ingredients suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days before the treatment. The application rate for post-emergence treatment was 0.0156 or 0.0078 kg / ha aS (active substance).

The plants were kept at temperatures of 10 to 25 ° C or 20 to 35 ° C, depending on the species. The trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to each treatment evaluated.

Evaluation was carried out on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal growth.

The plants used in the greenhouse experiments are composed of the following types: <tables id="tabl0003" num="0003"><table frame="all"><tgroup cols="3" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="center">Latin name</entry><entry namest="col2" nameend="col2" align="center">German name</entry><entry namest="col3" nameend="col3" align="center">English name</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Abutilon theophrasti</entry><entry namest="col2" nameend="col2" align="left">Chinese hemp</entry><entry namest="col3" nameend="col3" align="left">velvet leaf</entry></row><row><entry namest="col1" nameend="col1" align="left">Galium aparine</entry><entry namest="col2" nameend="col2" align="left">Burdock herb</entry><entry namest="col3" nameend="col3" align="left">catchweed bedstraw</entry></row><row><entry namest="col1" nameend="col1" align="left">Ipomoea subspecies</entry><entry namest="col2" nameend="col2" align="left">Magnificent wind species</entry><entry namest="col3" nameend="col3" align="left">morningglory</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Solanum nigrum</entry><entry namest="col2" nameend="col2" align="left">Black nightshade</entry><entry namest="col3" nameend="col3" align="left">black nightshade</entry></row></tbody></tgroup></table></tables>

At an application rate of 0.0156 or 0.0078 kg / ha aS, compound no. I.01 showed a very good activity against the abovementioned plants in the post-emergence process.

Examples of use (desiccative / defolian effectiveness)

Young, 4-leafed (without cotyledons) cotton plants served as test plants and grown under greenhouse conditions (relative humidity 50 to 70%; day / night temperature = 27/20 ° C.).

The young cotton plants were treated to runoff with aqueous preparations of the active compounds (with the addition of 0.15% by weight of the fatty alcohol alkoxylate Plurafac LF 700, based on the spray mixture). The amount of water applied was the equivalent of 1000 l / ha. After 13 days, the number of leaves dropped and the degree of defoliation in% were determined.

No leaf fall occurred in the untreated control plants.