Cyclohexenone derivatives, preparation and use thereof as herbicides

The present invention relates to novel cyclohexanone derivatives having a herbicidal action, to agents based on such cyclohexanone derivatives, and to processes for their preparation and use as herbicides.
The herbicidal action of oxime ethers having a cyclohexenone structure and nonaromatic substituents in the 5-position is known from EP 71,707.
It is further known that certain 2-acyl-3-hydroxycyclohex-2-en-1-ones regulate plant growth (EP 123,001 and EP 126,713).
We have found that cyclohexenone derivatives of the formula ##STR2## where A is oxygen or NOR.sup.8, where R.sup.8 is alkyl of 1 to 4 carbon atoms, alkenyl of 3 or 4 carbon atoms, alkynyl of 3 or 4 carbon atoms, haloalkyl or haloalkenyl of 2 to 4 carbon atoms and 1 to 3 halogen atoms, chlorothienyl or alkoxyalkyl of 2 to 4 carbon atoms,
B is O, S, SO or SO.sub.2,
X is hydrogen or methoxycarbonyl,
R.sup.1 is hydrogen, carbonylalkyl of 2 to 18 carbon atoms or benzoyl or an inorganic or organic cation,
R.sup.2 is alkyl of up to 4 carbon atoms,
R.sup.3 and R.sup.4, independently of each other, are each hydroxyl, chlorine, bromine, thioalkylcarboxyl, thiocarbonylalkyl, alkylcarbonyloxy each of up to 4 carbon atoms or R.sup.3 and R.sup.4 are together alkoxy of up to 3 carbon atoms and hydroxyl or together alkylthio of up to 3 carbon atoms and hydroxyl or together epoxy,
R.sup.5 and R.sup.6, independently of each other, are each hydrogen or methyl or R.sup.5 and R.sup.6 are together methyleneoxyethylene,
R.sup.7 is hydrogen or methyl,
have a powerful herbicidal action, preferably on species of the family of the grasses (Gramineae). They are compatible and thus selective in broad-leaf crops and also in monocotyledons which do not belong to the Gramineae. In addition, numerous compounds are also selective in Gramineae crops such as wheat and rice and at the same time control undesirable grasses. They are biologically superior to comparable compounds.
Examples of R.sup.1 in the formula I are: hydrogen, acetyl, propionyl, butyryl, pivaloyl, palmitoyl, stearoyl, benzoyl, sodium, potassium, ammonium, calcium, magnesium, trialkylammonium, tetraalkylammonium, trialkylbenzylammonium, trialkylsulfonium and trialkylsulfoxonium.
Examples of R.sup.2 in the formula I are: methyl, ethyl, n-propyl, i-propyl, n-butyl and i-butyl.
Examples of R.sup.3 and R.sup.4 are: alkoxy such as methoxy, ethoxy, n-propoxy or i-propoxy, alkylthio such as methylthio, ethylthio or n-propylthio, hydroxyl, bromine, chlorine, thioalkylcarboxyl such as thiomethylcarboxyl or thioethylcarboxyl, thiocarbonylalkyl such as thiocarbonylmethyl or thiocarbonylethyl, dimethylamino, acetoxy, propionyloxy, butyryloxy and epoxy.
Examples of R.sup.8 are: methyl, ethyl, n-propyl, i-propyl, allyl, (E)-2-butenyl, 2-fluoroeth-1-yl, 2-chloroeth-1-yl, (E)-3-chloro-2-propenyl, 1,1,2-trichloroprop-1-en-3-yl, chlorothienyl, propargyl, methoxymethyl and methoxyethyl.
The cyclohexenone derivatives of the formula I where A is NOR.sup.8 and R.sup.1 is hydrogen can be obtained by reacting compounds of the formula ##STR3## where R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and X have the abovementioned meanings, with alkoxyammonium compounds of the formula R.sup.8 ONH.sub.3 Y, where Y is an anion. To this end the two reactants are reacted with each other, for example in a solvent in the presence of a base at from 0.degree. C. to the boiling point of the solvent. Suitable bases are for example carbonates, hydrogencarbonates, acetates, alcoholates, oxides or hydroxides of alkali and alkaline earth metals, in particular sodium, potassium, magnesium or calcium, or organic bases, such as pyridine or tertiary amines.
Suitable solvents are for example dimethyl sulfoxide, alcohols such as methanol, ethanol or isopropanol, benzene, toluene, hydrocarbons and chlorohydrocarbons, such as chloroform, dichloroethane, hexane or cyclohexane, esters, such as ethyl acetate, or ethers, such as dioxane or tetrahydrofuran.
The reaction is complete within a few hours, and the reaction product can be isolated by concentrating the mixture, partitioning the residue between methylene chloride and water and distilling off the solvent under reduced pressure.
The compounds of the formula I where A is NOR.sup.8 and R.sup.1 is hydrogen can also be obtained by reacting the compounds of the formula I where A is oxygen and R.sup.1 is hydrogen with appropriate alkoxyamines of the formula R.sup.8 -ONH.sub.2 in a suitable diluent; suitable reaction temperatures range in general from 15.degree. to 70.degree. C. The alkoxyamine can be used in the form of an aqueous solution; depending on the solvent used for the other reactant, a one- or two-phase reaction mixture is obtained.
Suitable solvents for the reaction are for example alcohols, such as methanol, ethanol, isopropanol or cyclohexanol, hydrocarbons and chlorohydrocarbons, such as hexane, cyclohexane, methylene chloride, toluene or dichloroethane, esters, such as ethyl acetate, nitriles, such as acetonitrile, and cyclic ethers, such as tetrahydrofuran.
Alkali metal salts of compounds I can be obtained by treating the compounds with alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium alcoholate or potassium alcoholate in aqueous solution or in an organic solvent, such as methanol, ethanol, acetone or toluene.
Other metal salts, for example the managanese, copper, zinc, iron, calcium, magnesium and barium salts, can be prepared from the sodium salts in a conventional manner (by reaction with salts of the metals with inorganic acids), as in the same way the ammonium and phosphonium salts can be prepared by means of ammonia or phosphonium, sulfonium or sulfoxonium hydroxides.
The compounds of the formula I where A is oxygen can be prepared, for example from the corresponding cyclohexane-1,3-diones II ##STR4## by literature methods (Tetrahedron Lett. 29, (1975), 2491).
It is also possible to prepare compounds of the formula I where A is oxygen via the enol ester intermediate obtained on reacting compounds of the formula II with acid chlorides in the presence of bases and subsequently rearranged with certain imidazole or pyridine derivatives (Japanese Preliminary Published Application 79/063,052).
The compounds of the formula II can be obtained by literature method as given for example in German Laid-Open Application DOS 3,219,490.
It is also possible to introduce the substituents R.sup.3 and R.sup.4 at a later stage, preferably directly into compounds of the formula I where A is oxygen.
Suitable precursors are compounds of the formula ##STR5## where literature reactions can be carried out on the double bond, for example addition of halogens, hydrogen halides, mercaptans, thiolcarboxylic acids, mercaptocarboxylic acids or epoxidation.
The epoxy derivatives thus obtained can serve as starting materials for further syntheses based on opening the oxirane ring, for example reaction with mercaptans, water or alcohols with or without acid or base catalysis.
The compounds of the formula I where B is SO or SO.sub.2 can also be obtained by oxidizing appropriate precursors where the sulfur is in a lower state of oxidation. Oxidizing agents are for example oxygen, ozone, peroxy compounds, such as hydrogen peroxides, per-acids, hydroperoxides, halogens, inorganic halogen compounds, such as hypochlorite, chlorate, nitrogen compounds, such as nitric acid and dinitrogen pentoxide, or salts of metals of higher valence, such as lead, bismuth, vanadium, manganese, chromium or cobalt salts. Anodic oxidation is also possible. The oxidation can be carried out not only at the final stage but, in principle, at any stage of the synthesis route described above.

The examples which follow illustrate the preparation of the novel compounds. Parts by weight relate to parts by volume as the kilogram relates to the liter.
EXAMPLE 1
14.8 parts by weight of 2-propionyl-5-(5,6-dihydro-2H-pyran-3-yl)-3-hydroxy-2-cyclohexen-1-one are dissolved in 100 parts by volume of dichloromethane, and m-chloroperbenzoic acid is added at room temperature, and the reaction is monitored by means of thin layer chromatography. After the reaction has ended, the precipitated m-chlorobenzoic acid is filtered off, the filtrate is washed twice with semiconcentrated sodium bicarbonate solution and water and dried over sodium sulfate, and the solvent is distilled off under reduced pressure to leave 2-propionyl-5-(3,4-epoxy-tetrahydropyran-3-yl)-3-hydroxy-2-cyclohexen-1-one (compound No. 30).
EXAMPLE 2
3.0 parts by weight of 2-propionyl-5-(3,4-epoxytetrahydropyran-3-yl)-3-hydroxy-2-cyclohex-1-one, 1.8 parts by weight of (E)-3-chloro-2-propenyloxyammonium chloride, 1.1 parts by weight of sodium bicarbonate and 100 parts by volume of methanol are stirred at room temperature for 16 hours. The solvent is distilled off under reduced pressure, 50 parts by volume of water and 50 parts by volume of dichloromethane are added to the residue, after vigorous stirring the phases are separated, and the organic phase is dried over sodium sulfate. Distilling off the solvent under reduced pressure leaves 2-[1-((E)-3-chloro-2-propenyloxyimino)propyl]-5-(3,4-epoxytetrahydropyran-3-yl)-3-hydroxy-2-cyclohexen-1-one (compound No. 401).
The following compounds can be obtained in a similar manner:
(The .sup.1 H-NMR data are given in .delta. (ppm) and relate to tetramethylsilane as internal standard. Abbreviations: s=singlet, d=dublet, m=multiplet, q=quartet).
TABLE 1______________________________________ ##STR6##No. R.sup.1 R.sup.2 R.sup.3 and R.sup.4 B .sup.1 H-NMR data______________________________________ 1 H Methyl Cl S 2 H Methyl Cl O 3 H Methyl Cl SO 4 H Methyl Cl SO.sub.2 5 H Methyl Br S 6 H Methyl Br O 7 H Methyl Br SO 8 H Methyl Br SO.sub.2 9 H Methyl OH S 10 H Methyl OH O 11 H Methyl OH SO 12 H Methyl OH SO.sub.2 13 H Methyl Epoxy S 14 H Methyl Epoxy O 15 H Methyl Epoxy SO 16 H Methyl Epoxy SO.sub.2 17 H Ethyl Cl S 18 H Ethyl Cl O 19 H Ethyl Cl SO 20 H Ethyl Cl SO.sub.2 21 H Ethyl Br S 22 H Ethyl Br O 23 H Ethyl Br SO 24 H Ethyl Br SO.sub.2 25 H Ethyl OH S 26 H Ethyl OH O 27 H Ethyl OH SO 28 H Ethyl OH SO.sub.2 29 H Ethyl Epoxy S 30 H Ethyl Epoxy O 31 H Ethyl Epoxy SO 32 H Ethyl Epoxy SO.sub.2 33 H n-Propyl Cl S 34 H n-Propyl Cl O 1.0(t), 3.9(m), 4.4(m) 35 H n-Propyl Cl SO 36 H n-Propyl Cl SO.sub.2 37 H n-Propyl Br S 38 H n-Propyl Br O 2.0(d), 3.0(m), 4.6(s) 39 H n-Propyl Br SO 40 H n-Propyl Br SO.sub.2 41 H n-Propyl OH S 42 H n-Propyl OH O 1.0(t), 1.6(q), 3.8(m) 43 H n-Propyl OH SO 44 H n-Propyl OH SO.sub.2 45 H n-Propyl Epoxy S 46 H n-Propyl Epoxy O 47 H n-Propyl Epoxy SO 48 H n-Propyl Epoxy SO.sub.2 49 H n-Butyl Cl S 50 H n-Butyl Cl O 51 H n-Butyl Cl SO 52 H n-Butyl Cl SO.sub.2 53 H n-Butyl Br S 54 H n-Butyl Br O 55 H n-Butyl Br SO 56 H n-Butyl Br SO.sub.2 57 H n-Butyl OH S 58 H n-Butyl OH O 59 H n-Butyl OH SO 60 H n-Butyl OH SO.sub.2 61 H n-Butyl Epoxy S 62 H n-Butyl Epoxy O 63 H n-Butyl Epoxy SO 64 H n-Butyl Epoxy SO.sub.2 65 Na.sup.+ Methyl Cl S 66 Na.sup.+ Methyl Cl O 67 Na.sup.+ Methyl Cl SO 68 Na.sup.+ Methyl Cl SO.sub.2 69 Na.sup.+ Methyl Br S 70 Na.sup.+ Methyl Br O 71 Na.sup.+ Methyl Br SO 72 Na.sup.+ Methyl Br SO.sub.2 73 Na.sup.+ Methyl OH S 74 Na.sup.+ Methyl OH O 75 Na.sup.+ Methyl OH SO 76 Na.sup.+ Methyl OH SO.sub.2 77 Na.sup.+ Methyl Epoxy S 78 Na.sup.+ Methyl Epoxy O 79 Na.sup. + Methyl Epoxy SO 80 Na.sup.+ Methyl Epoxy SO.sub.2 81 Na.sup.+ Ethyl Cl S 82 Na.sup.+ Ethyl Cl O 83 Na.sup.+ Ethyl Cl SO 84 Na.sup.+ Ethyl Cl SO.sub.2 85 Na.sup.+ Ethyl Br S 86 Na.sup.+ Ethyl Br O 87 Na.sup.+ Ethyl Br SO 88 Na.sup.+ Ethyl Br SO.sub.2 89 Na.sup.+ Ethyl OH S 90 Na.sup.+ Ethyl OH O 91 Na.sup.+ Ethyl OH SO 92 Na.sup.+ Ethyl OH SO.sub.2 93 Na.sup.+ Ethyl Epoxy S 94 Na.sup.+ Ethyl Epoxy O 95 Na.sup.+ Ethyl Epoxy SO 96 Na.sup.+ Ethyl Epoxy SO.sub.2 97 Na.sup.+ n-Propyl Cl S 98 Na.sup.+ n-Propyl Cl O 99 Na.sup.+ n-Propyl Cl SO100 Na.sup.+ n-Propyl Cl SO.sub.2101 Na.sup.+ n-Propyl Br S102 Na.sup.+ n-Propyl Br O103 Na.sup.+ n-Propyl Br SO104 Na.sup.+ n-Propyl Br SO.sub.2105 Na.sup.+ n-Propyl OH S106 Na.sup.+ n-Propyl OH O107 Na.sup.+ n-Propyl OH SO108 Na.sup.+ n-Propyl OH SO.sub.2109 Na.sup.+ n-Propyl Epoxy S110 Na.sup.+ n-Propyl Epoxy O111 Na.sup.+ n-Propyl Epoxy SO112 Na.sup.+ n-Propyl Epoxy SO.sub.2113 Na.sup.+ n-Butyl Cl S114 Na.sup.+ n-Butyl Cl O115 Na.sup.+ n-Butyl Cl SO116 Na.sup.+ n-Butyl Cl SO.sub.2117 Na.sup.+ n-Butyl Br S118 Na.sup.+ n-Butyl Br O119 Na.sup.+ n-Butyl Br SO120 Na.sup.+ n-Butyl Br SO.sub.2121 Na.sup.+ n-Butyl OH S122 Na.sup.+ n-Butyl OH O123 Na.sup.+ n-Butyl OH SO124 Na.sup.+ n-Butyl OH SO.sub.2125 Na.sup.+ n-Butyl Epoxy S126 Na.sup.+ n-Butyl Epoxy O127 Na.sup.+ n-Butyl Epoxy SO128 Na.sup.+ n-Butyl Epoxy SO.sub.2129 K.sup.+ Methyl Cl S130 K.sup.+ Methyl Cl O131 K.sup.+ Methyl Cl SO132 K.sup.+ Methyl Cl SO.sub.2133 K.sup.+ Methyl Br S134 K.sup.+ Methyl Br O135 K.sup.+ Methyl Br SO136 K.sup.+ Methyl Br SO.sub.2137 K.sup.+ Methyl OH S138 K.sup.+ Methyl OH O139 K.sup.+ Methyl OH SO140 K.sup.+ Methyl OH SO.sub.2141 K.sup.+ Methyl Epoxy S142 K.sup.+ Methyl Epoxy O143 K.sup.+ Methyl Epoxy SO144 K.sup.+ Ethyl Epoxy SO.sub.2145 K.sup.+ Ethyl Cl S146 K.sup.+ Ethyl Cl O147 K.sup.+ Ethyl Cl SO148 K.sup.+ Ethyl Cl SO.sub.2149 K.sup.+ Ethyl Br S150 K.sup.+ Ethyl Br O151 K.sup.+ Ethyl Br SO152 K.sup.+ Ethyl Br SO.sub.2153 K.sup.+ Ethyl OH S154 K.sup.+ Ethyl OH O155 K.sup.+ Ethyl OH SO156 K.sup.+ Ethyl OH SO.sub.2157 K.sup.+ Ethyl Epoxy S158 K.sup.+ Ethyl Epoxy O159 K.sup. + Ethyl Epoxy SO160 K.sup.+ Ethyl Epoxy SO.sub.2161 K.sup.+ n-Propyl Cl S162 K.sup.+ n-Propyl Cl O163 K.sup.+ n-Propyl Cl SO164 K.sup.+ n-Propyl Cl SO.sub.2165 K.sup.+ n-Propyl Br S166 K.sup.+ n-Propyl Br O167 K.sup.+ n-Propyl Br SO168 K.sup.+ n-Propyl Br SO.sub.2169 K.sup.+ n-Propyl OH S170 K.sup.+ n-Propyl OH O171 K.sup.+ n-Propyl OH SO172 K.sup.+ n-Propyl OH SO.sub.2173 K.sup.+ n-Propyl Epoxy S174 K.sup.+ n-Propyl Epoxy O175 K.sup.+ n-Propyl Epoxy SO176 K.sup.+ n-Propyl Epoxy SO.sub.2177 K.sup.+ n-Butyl Cl S178 K.sup.+ n-Butyl Cl O179 K.sup.+ n-Butyl Cl SO180 K.sup.+ n-Butyl Cl SO.sub.2181 K.sup.+ n-Butyl Br S182 K.sup.+ n-Butyl Br O183 K.sup.+ n-Butyl Br SO184 K.sup.+ n-Butyl Br SO.sub.2185 K.sup.+ n-Butyl OH S186 K.sup.+ n-Butyl OH O187 K.sup.+ n-Butyl OH SO188 K.sup.+ n-Butyl OH SO.sub.2189 K.sup.+ n-Butyl Epoxy S190 K.sup.+ n-Butyl Epoxy O191 K.sup.+ n-Butyl Epoxy SO192 K.sup.+ n-Butyl Epoxy SO.sub.2______________________________________
TABLE 2__________________________________________________________________________ ##STR7##No. R.sup.1 R.sup.2 R.sup.3 and R.sup.4 R.sup.6 R.sup.7 B X .sup.1 H-NMR__________________________________________________________________________ data193 H Ethyl Epoxy H H O COOCH.sub.3194 H Ethyl Cl H H O COOCH.sub.3195 Trimethylbenzylammonium n-Propyl Epoxy H H O H196 H n-Propyl Epoxy Methyl Methyl O H197 H n-Propyl Cl H H O COOCH.sub.3198 H n-Propyl Br H H O COOCH.sub.3__________________________________________________________________________
TABLE 3__________________________________________________________________________ ##STR8##No. R.sup.1 R.sup.2 R.sup.3 and R.sup.4 X .sup.1 H-NMR data__________________________________________________________________________199 H Methyl Cl H200 H Methyl Br H201 H Methyl OH H202 H Methyl Epoxy H203 H Ethyl Cl H204 H Ethyl Br H205 H Ethyl OH H206 H Ethyl Epoxy H207 H n-Propyl Cl H208 H n-Propyl Br H 1.0(t), 1.7(q), 4.0(s)209 H n-Propyl OH H210 H n-Propyl Epoxy H 1.0(t), 2.5(m), 4.1(m)211 H n-Butyl Cl H212 H n-Butyl Br H213 H n-Butyl OH H214 H n-Butyl Epoxy H215 Na.sup.+ Methyl Cl H216 Na.sup.+ Methyl Br H217 Na.sup.+ Methyl OH H218 Na.sup.+ Methyl Epoxy H219 Na.sup. + Ethyl Cl H220 Na.sup.+ Ethyl Br H221 Na.sup.+ Ethyl OH H222 Na.sup.+ Ethyl Epoxy H223 Na.sup.+ n-Propyl Cl H224 Na.sup.+ n-Propyl Br H225 Na.sup.+ n-Propyl OH H226 Na.sup.+ n-Propyl Epoxy H227 Na.sup.+ n-Butyl Cl H228 Na.sup.+ n-Butyl Br H229 Na.sup.+ n-Butyl OH H230 Na.sup.+ n-Butyl Epoxy H231 K.sup.+ Methyl Cl H232 K.sup.+ Methyl Br H233 K.sup.+ Methyl OH H234 K.sup.+ Methyl Epoxy H235 K.sup.+ Ethyl Cl H236 K.sup.+ Ethyl Br H237 K.sup.+ Ethyl OH H238 K.sup.+ Ethyl Epoxy H239 K.sup.+ n-Propyl Cl H240 K.sup.+ n-Propyl Br H241 K.sup.+ n-Propyl OH H242 K.sup.+ n-Propyl Epoxy H243 K.sup.+ n-Butyl Cl H244 K.sup.+ n-Butyl Br H245 K.sup.+ n-Butyl OH H246 K.sup.+ n-Butyl Epoxy H247 H n-Propyl Cl COOCH.sub.3248 H Ethyl Cl COOCH.sub.3249 Trimethylbenzylammonium Ethyl Cl H250 Trimethylbenzylammonium n-Propyl Cl H251 Tetramethylammonium Ethyl Epoxy H252 Tetramethylammonium Ethyl Cl COOCH.sub.3__________________________________________________________________________
TABLE 4__________________________________________________________________________ ##STR9##No. R.sup.2 R.sup.3 and R.sup.4 B R.sup.8 .sup.1 H-NMR data__________________________________________________________________________253 Methyl Cl S Ethyl254 Methyl Cl S Allyl255 Methyl Cl S ( .sub.-- E)-2-Butenyl256 Methyl Cl S ( .sub.-- E)-3-Chloro-2-propenyl257 Methyl Cl S Propargyl258 Methyl Cl O Ethyl259 Methyl Cl O Allyl260 Methyl Cl O ( .sub.-- E)-2-Butenyl261 Methyl Cl O ( .sub.-- E)-3-Chloro-2-propenyl262 Methyl Cl O Propargyl263 Methyl Cl SO Ethyl264 Methyl Cl SO Allyl265 Methyl Cl SO ( .sub.-- E)-2-Butenyl266 Methyl Cl SO ( .sub.-- E)-3-Chloro-2-propenyl267 Methyl Cl SO Propargyl268 Methyl Cl SO.sub.2 Ethyl269 Methyl Cl SO.sub.2 Allyl270 Methyl Cl SO.sub.2 ( .sub.-- E)-2-Butenyl271 Methyl Cl SO.sub.2 ( .sub.-- E)-3-Chloro-2-propenyl272 Methyl Cl SO.sub.2 Propargyl273 Methyl Br S Ethyl274 Methyl Br S Allyl275 Methyl Br S ( .sub.-- E)-2-Butenyl276 Methyl Br S ( .sub.-- E)-3-Chloro-2-propenyl277 Methyl Br S Propargyl278 Methyl Br O Ethyl279 Methyl Br O Allyl280 Methyl Br O ( .sub.-- E)-2-Butenyl281 Methyl Br O ( .sub.-- E)-3-Chloro-2-propenyl282 Methyl Br O Propargyl283 Methyl Br SO Ethyl284 Methyl Br SO Allyl285 Methyl Br SO ( .sub.-- E)-2-Butenyl286 Methyl Br SO ( .sub.-- E)-3-Chloro-2-propenyl287 Methyl Br SO Propargyl288 Methyl Br SO.sub.2 Ethyl289 Methyl Br SO.sub.2 Allyl290 Methyl Br SO.sub.2 ( .sub.-- E)-2-Butenyl291 Methyl Br SO.sub.2 ( .sub.-- E)-3-Chloro-2-propenyl292 Methyl Br SO.sub.2 Propargyl293 Methyl OH S Ethyl294 Methyl OH S Allyl295 Methyl OH S ( .sub.-- E)-2-Butenyl296 Methyl OH S ( .sub.-- E)-3-Chloro-2-propenyl297 Methyl OH S Propargyl298 Methyl OH O Ethyl299 Methyl OH O Allyl300 Methyl OH O ( .sub.-- E)-2-Butenyl301 Methyl OH O ( .sub.-- E)-3-Chloro-2-propenyl302 Methyl OH O Propargyl303 Methyl OH SO Ethyl304 Methyl OH SO Allyl305 Methyl OH SO ( .sub.-- E)-2-Butenyl306 Methyl OH SO ( .sub.-- E)-3-Chloro-2-propenyl307 Methyl OH SO Propargyl308 Methyl OH SO.sub.2 Ethyl309 Methyl OH SO.sub.2 Allyl310 Methyl OH SO.sub.2 ( .sub.-- E)-2-Butenyl311 Methyl OH SO.sub.2 ( .sub.-- E)-3-Chloro-2-propenyl312 Methyl OH SO.sub.2 Propargyl313 Methyl Epoxy S Ethyl314 Methyl Epoxy S Allyl315 Methyl Epoxy S ( .sub.-- E)-2-Butenyl316 Methyl Epoxy S ( .sub.-- E)-3-Chloro-2-propenyl317 Methyl Epoxy S Propargyl318 Methyl Epoxy O Ethyl319 Methyl Epoxy O Allyl320 Methyl Epoxy O ( .sub.-- E)-2-Butenyl321 Methyl Epoxy O ( .sub.-- E)-3-Chloro-2-propenyl322 Methyl Epoxy O Propargyl323 Methyl Epoxy SO Ethyl324 Methyl Epoxy SO Allyl325 Methyl Epoxy SO ( .sub.-- E)-2-Butenyl326 Methyl Epoxy SO ( .sub.-- E)-3-Chloro-2-propenyl327 Methyl Epoxy SO Propargyl328 Methyl Epoxy SO.sub.2 Ethyl329 Methyl Epoxy SO.sub.2 Allyl330 Methyl Epoxy SO.sub.2 ( .sub.-- E)-2-Butenyl331 Methyl Epoxy SO.sub.2 ( .sub.-- E)-3-Chloro-2-propenyl332 Methyl Epoxy SO.sub.2 Propargyl333 Ethyl Cl S Ethyl334 Ethyl Cl S Allyl335 Ethyl Cl S ( .sub.-- E)-2-Butenyl336 Ethyl Cl S ( .sub.-- E)-3-Chloro-2-propenyl337 Ethyl Cl S Propargyl338 Ethyl Cl O Ethyl339 Ethyl Cl O Allyl340 Ethyl Cl O ( .sub.-- E)-2-Butenyl341 Ethyl Cl O ( .sub.-- E)-3-Chloro-2-propenyl342 Ethyl Cl O Propargyl343 Ethyl Cl SO Ethyl344 Ethyl Cl SO Allyl345 Ethyl Cl SO ( .sub.-- E)-2-Butenyl346 Ethyl Cl SO ( .sub.-- E)-3-Chloro-2-propenyl347 Ethyl Cl SO Propargyl348 Ethyl Cl SO.sub.2 Ethyl349 Ethyl Cl SO.sub.2 Allyl350 Ethyl Cl SO.sub.2 ( .sub.-- E)-2-Butenyl351 Ethyl Cl SO.sub.2 ( .sub.-- E)-3-Chloro-2-propenyl352 Ethyl Cl SO.sub.2 Propargyl353 Ethyl Br S Ethyl354 Ethyl Br S Allyl355 Ethyl Br S ( .sub.-- E)-2-Butenyl356 Ethyl Br S ( .sub.-- E)-3-Chloro-2-propenyl357 Ethyl Br S Propargyl358 Ethyl Br O Ethyl359 Ethyl Br O Allyl360 Ethyl Br O ( .sub.-- E)-2-Butenyl361 Ethyl Br O ( .sub.-- E)-3-Chloro-2-propenyl362 Ethyl Br O Propargyl363 Ethyl Br SO Ethyl364 Ethyl Br SO Allyl365 Ethyl Br SO ( .sub.-- E)-2-Butenyl366 Ethyl Br SO ( .sub.-- E)-3-Chloro-2-propenyl367 Ethyl Br SO Propargyl368 Ethyl Br SO.sub.2 Ethyl369 Ethyl Br SO.sub.2 Allyl370 Ethyl Br SO.sub.2 ( .sub.-- E)-2-Butenyl371 Ethyl Br SO.sub.2 ( .sub.-- E)-3-Chloro-2-propenyl372 Ethyl Br SO.sub.2 Propargyl373 Ethyl OH S Ethyl374 Ethyl OH S Allyl375 Ethyl OH S ( .sub.-- E)-2-Butenyl376 Ethyl OH S ( .sub.-- E)-3-Chloro-2-propenyl377 Ethyl OH S Propargyl378 Ethyl OH O Ethyl379 Ethyl OH O Allyl380 Ethyl OH O ( .sub.-- E)-2-Butenyl381 Ethyl OH O ( .sub.-- E)-3-Chloro-2-propenyl382 Ethyl OH O Propargyl383 Ethyl OH SO Ethyl384 Ethyl OH SO Allyl385 Ethyl OH SO ( .sub.-- E)-2-Butenyl386 Ethyl OH SO ( .sub.-- E)-3-Chloro-2-propenyl387 Ethyl OH SO Propargyl388 Ethyl OH SO.sub.2 Ethyl389 Ethyl OH SO.sub.2 Allyl390 Ethyl OH SO.sub.2 ( .sub.-- E)-2-Butenyl391 Ethyl OH SO.sub.2 ( .sub.-- E)-3-Chloro-2-propenyl392 Ethyl OH SO.sub.2 Propargyl393 Ethyl Epoxy S Ethyl394 Ethyl Epoxy S Allyl395 Ethyl Epoxy S ( .sub.-- E)-2-Butenyl396 Ethyl Epoxy S ( .sub.-- E)-3-Chloro-2-propenyl397 Ethyl Epoxy S Propargyl398 Ethyl Epoxy O Ethyl 1.3(t), 2.5(m), 3.3(s)399 Ethyl Epoxy O Allyl 1.1(t), 3.5(m), 4.6(d)400 Ethyl Epoxy O ( .sub.-- E)-2-Butenyl401 Ethyl Epoxy O ( .sub.-- E)-3-Chloro-2-propenyl 2.0(m), 3.5(m), 6.35(d)402 Ethyl Epoxy O Propargyl403 Ethyl Epoxy SO Ethyl404 Ethyl Epoxy SO Allyl405 Ethyl Epoxy SO ( .sub.-- E)-2-Butenyl406 Ethyl Epoxy SO ( .sub.-- E)-3-Chloro-2-propenyl407 Ethyl Epoxy SO Propargyl408 Ethyl Epoxy SO.sub.2 Ethyl409 Ethyl Epoxy SO.sub.2 Allyl410 Ethyl Epoxy SO.sub.2 ( .sub.-- E)-2-Butenyl411 Ethyl Epoxy SO.sub.2 ( .sub.-- E)-3-Chloro-2-propenyl412 Ethyl Epoxy SO.sub.2 Propargyl413 n-Propyl Cl S Ethyl414 n-Propyl Cl S Allyl415 n-Propyl Cl S ( .sub.-- E)-2-Butenyl416 n-Propyl Cl S ( .sub.-- E)-3-Chloro-2-propenyl417 n-Propyl Cl S Propargyl418 n-Propyl Cl O Ethyl 1.3(t), 1.6(q), 4.4(s)419 n-Propyl Cl O Allyl420 n-Propyl Cl O ( .sub.-- E)-2-Butenyl421 n-Propyl Cl O ( .sub.-- E)-3-Chloro-2-propenyl 1.0(t), 3.9(m), 4.5(d)422 n-Propyl Cl O Propargyl423 n-Propyl Cl SO Ethyl424 n-Propyl Cl SO Allyl425 n-Propyl Cl SO ( .sub.-- E)-2-Butenyl426 n-Propyl Cl SO ( .sub.-- E)-3-Chloro-2-propenyl427 n-Propyl Cl SO Propargyl428 n-Propyl Cl SO.sub.2 Ethyl429 n-Propyl Cl SO.sub.2 Allyl430 n-Propyl Cl SO.sub.2 ( .sub.-- E)-2-Butenyl431 n-Propyl Cl SO.sub.2 ( .sub.-- E)-3-Chloro-2-propenyl432 n-Propyl Cl SO.sub.2 Propargyl433 n-Propyl Br S Ethyl434 n-Propyl Br S Allyl435 n-Propyl Br S ( .sub.-- E)-2-Butenyl436 n-Propyl Br S ( .sub.-- E)-3-Chloro-2-propenyl437 n-Propyl Br S Propargyl438 n-Propyl Br O Ethyl 1.3(t), 3.9(m), 4.65(s)439 n-Propyl Br O Allyl 1.9(d), 4.5(d), 4.6(s)440 n-Propyl Br O ( .sub.-- E)-2-Butenyl 0.95(t), 1.8(d), 4.6(s)441 n-Propyl Br O ( .sub.-- E)-3-Chloro-2-propenyl 0.95(t), 1.5(q), 6.3(d)442 n-Propyl Br O Propargyl443 n-Propyl Br SO Ethyl444 n-Propyl Br SO Allyl445 n-Propyl Br SO ( .sub.-- E)-2-Butenyl446 n-Propyl Br SO ( .sub.-- E)-3-Chloro-2-propenyl447 n-Propyl Br SO Propargyl448 n-Propyl Br SO.sub.2 Ethyl449 n-Propyl Br SO.sub.2 Allyl450 n-Propyl Br SO.sub.2 ( .sub.-- E)-2-Butenyl451 n-Propyl Br SO.sub.2 ( .sub.-- E)-3-Chloro-2-propenyl452 n-Propyl Br SO.sub.2 Propargyl453 n-Propyl OH S Ethyl454 n-Propyl OH S Allyl455 n-Propyl OH S ( .sub.-- E)-2-Butenyl456 n-Propyl OH S ( .sub.-- E)-3-Chloro-2-propenyl457 n-Propyl OH S Propargyl458 n-Propyl OH O Ethyl 1.0(t), 2.6(m), 4.1(q)459 n-Propyl OH O Allyl460 n-Propyl OH O ( .sub.-- E)-2-Butenyl461 n-Propyl OH O ( .sub.-- E)-3-Chloro-2-propenyl462 n-Propyl OH O Propargyl463 n-Propyl OH SO Ethyl464 n-Propyl OH SO Allyl465 n-Propyl OH SO ( .sub.-- E)-2-Butenyl466 n-Propyl OH SO ( .sub.-- E)-3-Chloro-2-propenyl467 n-Propyl OH SO Propargyl468 n-Propyl OH SO.sub.2 Ethyl469 n-Propyl OH SO.sub.2 Allyl470 n-Propyl OH SO.sub.2 ( .sub.-- E)-2-Butenyl471 n-Propyl OH SO.sub.2 ( .sub.-- E)-3-Chloro-2-propenyl472 n-Propyl OH SO.sub.2 Propargyl473 n-Propyl Epoxy S Ethyl474 n-Propyl Epoxy S Allyl475 n-Propyl Epoxy S ( .sub.-- E)-2-Butenyl476 n-Propyl Epoxy S ( .sub.-- E)-3-Chloro-2-propenyl477 n-Propyl Epoxy S Propargyl478 n-Propyl Epoxy O Ethyl 1.35(t), 2.0(m), 3.3(s)479 n-Propyl Epoxy O Allyl480 n-Propyl Epoxy O ( .sub.-- E)-2-Butenyl 0.95(t), 1.5(m), 3.3(s)481 n-Propyl Epoxy O ( .sub.-- E)-3-Chloro-2-propenyl482 n-Propyl Epoxy O Propargyl483 n-Propyl Epoxy SO Ethyl484 n-Propyl Epoxy SO Allyl485 n-Propyl Epoxy SO ( .sub.-- E)-2-Butenyl486 n-Propyl Epoxy SO ( .sub.-- E)-3-Chloro-2-propenyl487 n-Propyl Epoxy SO Propargyl488 n-Propyl Epoxy SO.sub.2 Ethyl489 n-Propyl Epoxy SO.sub.2 Allyl490 n-Propyl Epoxy SO.sub.2 ( .sub.-- E)-2-Butenyl491 n-Propyl Epoxy SO.sub.2 ( .sub.-- E)-3-Chloro-2-propenyl492 n-Propyl Epoxy SO.sub.2 Propargyl493 n-Butyl Cl S Ethyl494 n-Butyl Cl S Allyl495 n-Butyl Cl S ( .sub.-- E)-2-Butenyl496 n-Butyl Cl S ( .sub.-- E)-3-Chloro-2-propenyl497 n-Butyl Cl S Propargyl498 n-Butyl Cl O Ethyl499 n-Butyl Cl O Allyl500 n-Butyl Cl O ( .sub.-- E)-2-Butenyl501 n-Butyl Cl O ( .sub.-- E)-3-Chloro-2-propenyl502 n-Butyl Cl O Propargyl503 n-Butyl Cl SO Ethyl504 n-Butyl Cl SO Allyl505 n-Butyl Cl SO ( .sub.-- E)-2-Butenyl506 n-Butyl Cl SO ( .sub.-- E)-3-Chloro-2-propenyl507 n-Butyl Cl SO Propargyl508 n-Butyl Cl SO.sub.2 Ethyl509 n-Butyl Cl SO.sub.2 Allyl510 n-Butyl Cl SO.sub.2 ( .sub.-- E)-2-Butenyl511 n-Butyl Cl SO.sub.2 ( .sub.-- E)-3-Chloro-2-propenyl512 n-Butyl Cl SO.sub.2 Propargyl513 n-Butyl Br S Ethyl514 n-Butyl Br S Allyl515 n-Butyl Br S ( .sub.-- E)-2-Butenyl516 n-Butyl Br S ( .sub.-- E)-3-Chloro-2-propenyl517 n-Butyl Br S Propargyl518 n-Butyl Br O Ethyl519 n-Butyl Br O Allyl520 n-Butyl Br O ( .sub.-- E)-2-Butenyl521 n-Butyl Br O ( .sub.-- E)-3-Chloro-2-propenyl522 n-Butyl Br O Propargyl523 n-Butyl Br SO Ethyl524 n-Butyl Br SO Allyl525 n-Butyl Br SO ( .sub.-- E)-2-Butenyl526 n-Butyl Br SO ( .sub.-- E)-3-Chloro-2-propenyl527 n-Butyl Br SO Propargyl528 n-Butyl Br SO.sub.2 Ethyl529 n-Butyl Br SO.sub.2 Allyl530 n-Butyl Br SO.sub.2 ( .sub.-- E)-2-Butenyl531 n-Butyl Br SO.sub.2 ( .sub.-- E)-3-Chloro-2-propenyl532 n-Butyl Br SO.sub.2 Propargyl533 n-Butyl OH S Ethyl534 n-Butyl OH S Allyl535 n-Butyl OH S ( .sub.-- E)-2-Butenyl536 n-Butyl OH S ( .sub.-- E)-3-Chloro-2-propenyl537 n-Butyl OH S Propargyl538 n-Butyl OH O Ethyl539 n-Butyl OH O Allyl540 n-Butyl OH O ( .sub.-- E)-2-Butenyl541 n-Butyl OH O ( .sub.-- E)-3-Chloro-2-propenyl542 n-Butyl OH O Propargyl543 n-Butyl OH SO Ethyl544 n-Butyl OH SO Allyl545 n-Butyl OH SO ( .sub.-- E)-2-Butenyl546 n-Butyl OH SO ( .sub.-- E)-3-Chloro-2-propenyl547 n-Butyl OH SO Propargyl548 n-Butyl OH SO.sub.2 Ethyl549 n-Butyl OH SO.sub.2 Allyl550 n-Butyl OH SO.sub.2 ( .sub.-- E)-2-Butenyl551 n-Butyl OH SO.sub.2 ( .sub.-- E)-3-Chloro-2-propenyl552 n-Butyl OH SO.sub.2 Propargyl553 n-Butyl Epoxy S Ethyl554 n-Butyl Epoxy S Allyl555 n-Butyl Epoxy S ( .sub.-- E)-2-Butenyl556 n-Butyl Epoxy S ( .sub.-- E)-3-Chloro-2-propenyl557 n-Butyl Epoxy S Propargyl558 n-Butyl Epoxy O Ethyl559 n-Butyl Epoxy O Allyl560 n-Butyl Epoxy O ( .sub.-- E)-2-Butenyl561 n-Butyl Epoxy O ( .sub.-- E)-3-Chloro-2-propenyl562 n-Butyl Epoxy O Propargyl563 n-Butyl Epoxy SO Ethyl564 n-Butyl Epoxy SO Allyl565 n-Butyl Epoxy SO ( .sub.-- E)-2-Butenyl566 n-Butyl Epoxy SO ( .sub.-- E)-3-Chloro-2-propenyl567 n-Butyl Epoxy SO Propargyl568 n-Butyl Epoxy SO.sub.2 Ethyl569 n-Butyl Epoxy SO.sub.2 Allyl570 n-Butyl Epoxy SO.sub.2 ( .sub.-- E)-2-Butenyl571 n-Butyl Epoxy SO.sub.2 ( .sub.-- E)-3-Chloro-2-propenyl572 n-Butyl Epoxy SO.sub.2 Propargyl__________________________________________________________________________
TABLE 5__________________________________________________________________________ ##STR10##No. R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.6 and R.sup.7 R.sup.8 .sup.1 H-NMR data__________________________________________________________________________573 H n-Propyl OH Dimethylamino H Ethyl574 H n-Propyl OH Methylthio H Ethyl575 H n-Propyl OH Ethylthio H Ethyl576 H n-Propyl OH Methylcarbonylthio H Ethyl577 H n-Propal OH Carboxylmethylthio H Ethyl578 H n-Propyl H Methylthio H Ethyl579 H n-Propyl H Ethylthio H Ethyl580 H n-Propyl H Methylcarbonylthio H Ethyl581 H n-Propyl H Carboxylmethylthio H Ethyl582 Benzoyl n-Propyl OH Methylthio H Ethyl583 H Ethyl H Methylcarbonylthio H Ethyl584 H Ethyl H Methylcarbonylthio H Allyl585 H Ethyl H Methylcarbonylthio H Propargyl586 H Methyl H Methylcarbonylthio H Ethyl587 H Methyl H Methylcarbonylthio H Allyl588 Benzoyl n-Propyl R.sup.3 and R.sup.4 = Epoxy H Ethyl589 Stearoyl n-Propyl R.sup.3 and R.sup.4 = Epoxy H Ethyl590 H n-Propyl Methylthio OH Methyl Ethyl591 H n-Propyl Ethylthio OH Methyl Ethyl672 H n-Propyl R.sup.3 and R.sup.4 = Epoxy Methyl Ethyl 0.96(t), 3.91(q), 4.09(q)__________________________________________________________________________
TABLE 6__________________________________________________________________________ ##STR11##No. R.sup.2 R.sup.3 and R.sup.4 R.sup.8 .sup.1 H-NMR data__________________________________________________________________________592 Methyl Cl Ethyl593 Methyl Cl Allyl594 Methyl Cl ( .sub.-- E)-2-Butenyl595 Methyl Cl ( .sub.-- E)-3-Chloro-2-propenyl596 Methyl Cl Propargyl597 Methyl Br Ethyl598 Methyl Br Allyl599 Methyl Br ( .sub.-- E)-2-Butenyl600 Methyl Br ( .sub.-- E)-3-Chloro-2-propenyl601 Methyl Br Propargyl602 Methyl OH Ethyl603 Methyl OH Allyl604 Methyl OH ( .sub.-- E)-2-Butenyl605 Methyl OH ( .sub.-- E)-3-Chloro-2-propenyl606 Methyl OH Propargyl607 Methyl Epoxy Ethyl608 Methyl Epoxy Allyl609 Methyl Epoxy ( .sub.-- E)-2-Butenyl610 Methyl Epoxy ( .sub.-- E)-3-Chloro-2-propenyl611 Methyl Epoxy Propargyl612 Ethyl Cl Ethyl613 Ethyl Cl Allyl614 Ethyl Cl ( .sub.-- E)-2-Butenyl615 Ethyl Cl ( .sub.-- E)-3-Chloro-2-propenyl616 Ethyl Cl Propargyl617 Ethyl Br Ethyl618 Ethyl Br Allyl619 Ethyl Br ( .sub.-- E)-2-Butenyl620 Ethyl Br ( .sub.-- E)-3-Chloro-2-propenyl621 Ethyl Br Propargyl622 Ethyl OH Ethyl623 Ethyl OH Allyl624 Ethyl OH ( .sub.-- E)-2-Butenyl625 Ethyl OH ( .sub.-- E)-3-Chloro-2-propenyl626 Ethyl OH Propargyl627 Ethyl Epoxy Ethyl628 Ethyl Epoxy Allyl629 Ethyl Epoxy ( .sub.-- E)-2-Butenyl630 Ethyl Epoxy ( .sub.-- E)-3-Chloro-2-propenyl631 Ethyl Epoxy Propargyl632 n-Propyl Cl Ethyl633 n-Propyl Cl Allyl634 n-Propyl Cl ( .sub.-- E)-2-Butenyl635 n-Propyl Cl ( .sub.-- E)-3-Chloro-2-propenyl636 n-Propyl Cl Propargyl637 n-Propyl Br Ethyl 1.6(q), 2.6(m), 4.1(q)638 n-Propyl Br Allyl 1.0(t), 3.9(m), 5.4(m)639 n-Propyl Br ( .sub.-- E)-2-Butenyl 1.0(t), 1.7(m), 2.9(m)640 n-Propyl Br ( .sub.-- E)-3-Chloro-2-propenyl 1.5(q), 2.9(t), 4.0(s)641 n-Propyl Br Propargyl642 n-Propyl OH Ethyl643 n-Propyl OH Allyl644 n-Propyl OH ( .sub.-- E)-2-Butenyl645 n-Propyl OH ( .sub.-- E)-3-Chloro-2-propenyl646 n-Propyl OH Propargyl647 n-Propyl Epoxy Ethyl 1.3(t), 2.3(m), 3.1(s)648 n-Propyl Epoxy Allyl 0.95(t), 3.1(s), 4.5(d)649 n-Propyl Epoxy ( .sub.-- E)-2-Butenyl650 n-Propyl Epoxy ( .sub.-- E)-3-Chloro-2-propenyl 1.35(t), 2.0(m), 3.3(s)651 n-Propyl Epoxy Propargyl652 n-Butyl Cl Ethyl653 n-Butyl Cl Allyl654 n-Butyl Cl ( .sub.-- E)-2-Butenyl655 n-Butyl Cl ( .sub.-- E)-3-Chloro-2-propenyl656 n-Butyl Cl Propargyl657 n-Butyl Br Ethyl658 n-Butyl Br Allyl659 n-Butyl Br ( .sub.-- E)-2-Butenyl660 n-Butyl Br ( .sub.-- E)-3-Chloro-2-propenyl661 n-Butyl Br Propargyl662 n-Butyl OH Ethyl663 n-Butyl OH Allyl664 n-Butyl OH ( .sub.-- E)-2-Butenyl665 n-Butyl OH ( .sub.-- E)-3-Chloro-2-propenyl666 n-Butyl OH Propargyl667 n-Butyl Epoxy Ethyl668 n-Butyl Epoxy Allyl669 n-Butyl Epoxy ( .sub.-- E)-2-Butenyl670 n-Butyl Epoxy ( .sub.-- E)-3-Chloro-2-propenyl671 n-Butyl Epoxy Propargyl__________________________________________________________________________
TABLE 7__________________________________________________________________________No. A B X R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7 R.sup.8__________________________________________________________________________673 NOR.sup.8 O H C.sub.3 H.sub.7 CO Propyl --O-- --CH.sub.2 OC.sub.2 H.sub.4 -- H Ethyl 0.90(t), 1.0(t), 1.24(t)674 NOR.sup.8 O H Benzoyl Propyl O CH.sub.2 OC.sub.2 H.sub.4 H Ethyl 0.86(t), 1.09(t), 7.3-8.2(m)675 NOR.sup.8 O H Acetyl Propyl O CH.sub.2 OC.sub.2 H.sub.4 H Ethyl 0.88(t), 1.25(t),__________________________________________________________________________ 2.19(s)
The cyclohexenone derivatives of the formula I, and their salts, may be applied for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used, but they must ensure as fine a distribution of the active ingredients according to the invention as possible.
For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, and paraffin, tetrahydrocarbons such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are suitable.
Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols and octadecanols, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol or formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.
Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate and ureas, and vegetable products such as grain flours, bark meal, wood meal and nutshell meal, cellulosic powders, etc.
The formulations contain from 0.1 to 95, and preferably from 0.5 to 90, % by weight of active ingredient.
Examples of formulations are given below.
I. 90 parts by weight of compound no. 647 is mixed with 10 parts by weight of N-methyl-.alpha.-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.
II. 20 parts by weight of compound no. 648 is dissolved in a mixture consisting of 80 parts by weight of xylene, 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 the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of active ingredient.
III. 20 parts by weight of compound no. 650 is 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 moles of ethylene oxide and 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of active ingredient.
IV. 20 parts by weight of compound no. 637 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280.degree. C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of active ingredient.
V. 20 parts by weight of compound no. 638 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-.alpha.-sulfonic acid, 17 parts by weight of the sodium salt of a ligninsulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained containing 0.1% by weight of active ingredient.
VI. 3 parts by weight of compound no. 640 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of active ingredient.
VII. 30 parts by weight of compound no. 478 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.
VIII. 20 parts of compound no. 480 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.
IX. 10 parts by weight of compound no. 440 is mixed with 90 parts by weight of a mixture consisting of 93 parts by weight of xylene and 7 parts by weight of the adduct of 8 moles of ethylene oxide and 1 mole of nonylphenol. A solution is obtained containing 10 wt % of the active ingredient.
The active ingredients, or agents containing them, may be applied pre- or postmergence. If certain crop plants tolerate the active ingredients less well, application techniques may be used in which the herbicidal agents are sprayed from suitable equipment in such a manner that the leaves of sensitive crop plants are if possible not touched, and the agents reach the soil or the unwanted plants growing beneath the crop plants (post-directed, lay-by treatment).
The amounts of active ingredient applied depends on the time of the year, the plants to be combated and their growth stage, and varies from 0.01 to 3 kg/ha, but is preferably from 0.05 to 0.5 kg/ha.
The action of the cyclohexenone derivatives of the formula I on plant growth is demonstrated in greenhouse experiments.
The vessels employed were plastic flowerpots having a volume of 300 cm.sup.3, and which were filled with a sandy loam containing about 3.0% humus. The seeds of the test plants were sown shallow, and separately, according to species. For the preemergence treatment, the active ingredients were applied to the surface of the soil immediately after the seeds had been sown. The compounds were emulsified or suspended in water as vehicle, and sprayed through finely distributing nozzles. The application rate was 3.0 kg of active ingredient per hectare. After the agents had been applied, the vessels were lightly sprinkler-irrigated to induce germination and growth. Transparent plastic covers were then placed on the vessels until the plants had taken root. The cover ensured uniform germination of the plants, insofar as this was not impaired by the active ingredients.
For the postemergence treatment, the plants were first grown in the vessels to a height of from 3 to 15 cm, depending on growth form, before being treated. For this treatment, either plants which had been sown directly in the pots and grown there were selected, or plants which had been grown from seedlings and were transplanted to the pots a few days before treatment. The application rate for postemergence treatment was 0.125 kg of active ingredient per hectare. No covers were placed on the vessels in this method.
The pots were set up in the greenhouse - species from warmer areas at from 20.degree. C. to 35.degree. C., and species from moderate climates at 10.degree. to 25.degree. C. The experiments were run for 2 to 4 weeks. During this period, the plants were tended and their reactions to the various treatments assessed. The scale used for assessment was 0 to 100, 0 denoting no damage or normal emergence, and 100 denoting nonemergence or complete destruction of at least the visible plant parts.
The plants used in the experiments were Alopecurus myosuroides, Avena fatua, Avena sativa, Digitaria sanguinalis, Echinochloa crus-galli, Lolium multiflorum, Medicago sativa, Setaria italica, Sinapis alba, Sorghum halepense, Triticum aestivum, and Zea mays.
Grasses from the Gramineae family were well combated with a preemergence application of 3.0 kg/ha of, for example, compounds 647, 648, 650, 637, 638, 640, 478 and 440. Sinapis alba (broadleaved crop plant) suffered no damage whatsoever.
Compounds 647, 648, 650 and 401 are suitable, at a rate of 0.125 kg/ha, for controlling, postemergence, a broad spectrum of unwanted grassy plants. Volunteer crop plants from the Gramineae family are also combated. Alfalfa--a broadleaved crop plant--remain completely uninfluenced.
Unwanted grassy species are well combated by postemergence applications of active ingredients 438, 439 and 674; wheat remains unaffected.
In view of the spectrum of weeds which can be combated, the tolerance of the active ingredients according to the invention by crop plants, the desired influence on the growth of crop plants, and in view of the numerous application methods possible, the compounds according to the invention may be used in a large number of crop plants.
The following crops may be mentioned by way of example:
______________________________________Botanical name Common name______________________________________Allium cepa onionsAnanas comosus pineapplesArachis hypogaea peanuts (groundnuts)Asparagus officinalis asparagusBeta vulgaris spp. altissima sugarbeetsBeta vulgaris spp. rapa fodder beetsBeta vulgaris spp. essculenta table beets, red beetsBrassica napus var. napus rapeseedBrassica napus var. napobrassica swedesBrassica napus var. rapa turnipsBrassica rapa var. silvestris tea plantsCamellia sinensisCarthamus tinctorius safflowerCarya illinoinensis pecan treesCitrus limon lemonsCitrus maxima grapefruitsCitrus reticulata mandarinsCitrus sinensis orange treesCoffea arabica (Coffea canephora, coffee plantsCoffea liberical)Cucumis melo melonsCucumis sativus cucumbersCynodon dactylon bermudagrassDaucus carota carrotsElaeis guineensis oil palmsFragaria vesca strawberriesGlycine max soybeansGossypium hirsutum (Gossypium arboreum, cottonGossypium herbaceum, Gossypium vitifolium)Helianthus annuus sunflowersHelianthus tuberosus Jerusalem artichokeHevea brasiliensis rubber plantsHordeum vulgare barleyHumulus lupulus hopsIpomoea batatas sweet potatoesJuglans regia walnut treesLactua sativa lettuceLens culinaris lentilsLinum usitatissimum flaxLycopersicon lycopersicum tomatoesMalus spp. apple treesManihot esculenta cassavaMedicago sativa alfalfa (lucerne)Mentha piperita peppermintMusa spp. banana plantsNicotiana tabacum (N. rustica) tobaccoOlea europaea olive treesOryza sativa ricePhaseolus lunatus limabeansPhaseolus mungo mungbeansPhaseolus vulgaris snapbeans, green beans, dry beansPennisetum glaucum pearl milletPetroselinum crispum spp. tuberosum parsleyPicea abies Norway spruceAbies alba fir treesPinus spp. pine treesPisum sativum English peasPrunus avium cherry treesPrunus domestica plum treesPrunus dulcis almond treesPrunus persica peach treesPyrus communis pear treesRibes sylvestre redcurrantsRibes uva-crispa gooseberriesRicinus communis castor-oil plantsSaccharum officinarum sugar caneSecale cereale ryeSesamum indicum sesameSolanum tuberosum Irish potatoesSpinacia oleracea spinachTheobroma cacao cacao plantsTrifolium pratense red cloverTriticum aestivum wheatVaccinium corymbosum blueberriesVaccinium vitis-idaea cranberriesVicia faba tick beansVigna sinensis (V. unguiculata) cow peasVitis vinifera grapesZea mays Indian corn, sweet corn, maize______________________________________
To increase the spectrum of action and to achieve synergistic effects, the cyclohexenone derivatives of the formula I may be mixed and applied together with numerous representatives of other herbicidal or growth-regulating active ingredient groups. Examples or suitable mixture components are diazines, 4H-3, 1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran derivatives, quinolinecarboxylic acid derivatives, etc.
It may also be useful to apply the compounds of the formula I, or herbicidal agents containing them, either alone or in combination with other herbicides, in admixture with other crop protection agents, e.g., agents for combating pests or phytopathogenic fungi or bacteria. The compounds may also be mixed with solutions of mineral salts used to remedy nutritional or trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added.

Number	Name	Date
4316737	Guigues et al.	Feb 1982
4422864	Becker et al.	Dec 1983
4596877	Becker et al.	Jun 1986
4602935	Becker et al.	Jul 1986
4612036	Jahn et al.	Sep 1986
4624696	Keil et al.	Nov 1986
4654073	Jahn et al.	Mar 1987
4668275	Keil et al.	May 1987
4761172	Jahn et al.	Aug 1988
4761486	Zeeh et al.	Aug 1988

Number	Date	Country
136647	Apr 1985	EPX
136702	Apr 1985	EPX
177913	Apr 1986	EPX
218233	Apr 1987	EPX
3601066	Jul 1987	DEX

Cyclohexenone derivatives, preparation and use thereof as herbicides

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