Herbicidal cyclohexanol derivatives, compositions, and method of use therefor

The present invention relates to cyclohexenol derivatives and to herbicides which contain these compounds as active ingredients.
It has been disclosed that cyclohexenol derivatives can be used for controlling undesirable grasses in broadleaved crops (German Laid-Open Application DOS No. 2,461,027).
We have found that cyclohexenol derivatives of the formula ##STR2## where R.sup.1 is a 5-membered, 6-membered or 7-membered heterocyclic structure which contains 1 or 2 heteroatoms or ring members from the group consisting of N, O, S, SO and SO.sub.2 and can be unsubstituted or substituted by not more than 2 alkyl or alkoxy groups,
or cycloalkyl of 3 to 12 carbon atoms which is unsubstituted or substituted by not more than 3 methyl groups and may contain not more than 3 double bonds,
or a bicyclic ring system which contains not more than 12 ring members and may contain not more than 2 double bonds and not more than 2 atoms from the group consisting of S and O,
or a radical of the general structural formula B--Y--C--, where B is alkyl, alkoxyalkyl or an unsubstituted or halogen-substituted phenyl or benzyl radical, Y is oxygen or sulfur and C is an alkylene chain of not more than 4 carbon atoms, with the proviso than when B is alkyl, Y is sulfur and C is an alkylene chain, then A is not benzoyl, benzenesulfonyl, alkanoyl or alkenoyl,
or alkyl, or phenyl which is unsubstituted or substituted by not more than 3 substituents from the group consisting of halogen, alkyl, alkoxy, alkylsulfonyl and nitro, with the proviso that when R.sup.1 is alkylphenyl, furyl, thienyl or substituted phenyl, then A is not alkylsulfonyl, alkanoyl, aroyl, arylsulfonyl, phenoxyacetyl, alkyl or benzyl,
X is hydrogen or methoxycarbonyl,
R.sup.2 is alkyl of 1 to 4 carbon atoms,
R.sup.3 is alkyl of 1 to 3 carbon atoms, alkenyl of 3 or 4 carbon atoms, haloalkenyl of 3 or 4 carbon atoms and 1 to 3 halogen substituents, or propargyl, and
A is a radical of the general structure DE, where
D is methylene, CO or SO.sub.2 and
E is an alkyl or alkenyl radical of not more than 20 carbon atoms, unsubstituted or methyl-substituted cycloalkyl of not more than 6 carbon atoms, or styryl, or is a phenyl or benzyl radical which is unsubstituted or substituted by not more than 3 substituents from the group consisting of halogen, alkyl, alkoxy and nitro, or is a 1-methylbenzyl or 1,1-dimethylbenzyl radical which is unsubstituted or substituted by halogen or methoxy, or is haloalkyl of not more than 3 carbon atoms and 3 halogen atoms, alkoxymethyl, acetoxymethyl or alkoxycarbonylalkyl, or is phenoxyalkylene which is unsubstituted or substituted in the phenoxy moiety by not more than 3 substituents from the group consisting of halogen, alkyl, alkoxy and methylsulfonyl, and which possesses a straight-chain or branched alkylene chain of not more than 5 carbon atoms, or E is a heterocyclic structure which contains 5 or 6 ring members and 1 or 2 heteroatoms from the group consisting of N, O and S and can be unsubstituted or substituted by halogen, alkyl, alkoxy, amino or dialkylamino, or is heteroarylalkyl, or
A is a radical of the formula ##STR3## where R.sup.4 is a phenyl, pyridyl, benzothiazolyl, benzoxazolyl, quinoxalinyl or quinolyl radical which is substituted by trifluoromethyl, halogen or alkyl, or
A is a radical of the formula ##STR4## where R.sup.5 and R.sup.6 are each halogen or CF.sub.3, or A is a radical of the formula ##STR5## where R.sup.7 is halogen or lower alkyl or A is a radical of the formula ##STR6## where G is phenylene or an alkylene chain of not more than 6 carbon atoms, or
A is a radical of the formula ##STR7## where R.sup.8, R.sup.9 and R.sup.10 independently of one another are each alkyl or phenyl, or
A is a radical of the formula ##STR8## where the radicals Y independently of one another are each oxygen or sulfur, and R.sup.11 and R.sup.12 are each lower alkyl, possess herbicidal activity. Depending on the spectrum of plants to be controlled and on the toleration by crop plants, they either are selective herbicides or are used generally for controlling and inhibiting undesirable vegetation, including inhibition of the growth of vegetative and generative parts of crop plants, where these are useless, a hindrance or even disadvantageous.
In formula I, R.sup.1 is a 5-membered, 6-membered or 7-membered heterocyclic structure which contains 1 or 2 heteroatoms or ring members from the group consisting of N, O, S, SO and SO.sub.2 and can be unsubstituted or substituted by not more than 2 alkyl or alkoxy groups, such as pyridyl, pyrimidyl, 5,6-dihydro-2H-pyranyl, tetrahydropyranyl, 5,6-dihydro-2H-thiopyranyl, tetrahydrothiopyranyl, 1-oxotetrahydrothiopyranyl, 1,1-dioxotetrahydrothiopyranyl, tetrahydrofuryl, tetrahydrothienyl or 1,3-dioxepanyl radicals, eg. pyrid-2-yl, pyrid-3-yl, pyrid-4-yl, pyrimid-5-yl, 4,6-dimethoxypyrimid-5-yl, 5,6-dihydro-2H-pyran-3-yl, tetrahydropyran-3-yl, 5,6-dihydro-2H-thiopyran-3-yl, tetrahydrothiopyran-3-yl, 1-oxotetrahydrothiopyran-3-yl, 1,1-dioxotetrahydrothiopyran-3-yl, tetrahydrofur-3-yl, tetrahydrothien-3-yl, 2,6-dimethyltetrahydropyran-3-yl, 2,6-dimethyltetrahydrothiopyran-3-yl, 6-methoxytetrahydropyran-3-yl, 1,3-dioxepan-5-yl, 2-i-propyl-1,3-dioxepan-5-yl or benzo-1,3-dioxol-5-yl.
R.sup.1 can furthermore be cycloalkyl of 3 to 12 carbon atoms which is unsubstituted or substituted by not more than 3 methyl groups and may contain not more than 3 double bonds, eg. cyclopropyl, cyclohexyl, cyclooctyl, cyclododecyl, cyclohex-b 3-enyl, cyclohex-1-enyl, 2-methylcyclohex-1-enyl, 4-methylcyclohex-3-enyl, 2,6,6-trimethylcyclohex-1-enyl, 2,6,6-trimethylcyclohex-2-enyl or cyclododeca-4,8-dienyl; a bicyclic ring system which contains not more than 12 ring members and may contain not more than 2 double bonds and not more than 2 atoms from the group consisting of S and O, eg. 4a,7,8,8a-tetrahydro-2H,5H-pyrano[4,3-b]pyran-3-yl, 3,4,4a,7,8,8a-hexahydro-2H,5H-pyrano[4,3-b]pyran-3-yl or 2,6,6-trimethylbicyclo[3,1,1]hept-3-yl; a radical of the general structural formula B--Y--C--, where B is C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxyalkyl or an unsubstituted or halogen-substituted phenyl or benzyl radical, Y is oxygen or sulfur and C is an alkylene chain of not more than 4 carbon atoms, eg. 2-ethylthio-n-propyl, 2-(chlorobenzyl)-thioethyl, 2-methoxy-n-propyl, 1-methyl-2-methoxyethyl or 1-(2-n-butoxyethoxy)-ethyl; C.sub.1 -C.sub.4 -alkyl; or phenyl which is unsubstituted or substituted by not more than 3 substituents from the group consisting of halogen, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkylsulfonyl and nitro, eg. 4-methylphenyl, 4-ethylphenyl, 4-methoxyphenyl, 3-methylphenyl, 4-methylsulfonylphenyl or 3,4-dimethoxyphenyl.
In formula I, R.sup.2 is straight-chain or branched alkyl of 1 to 4 carbon atoms, ie. methyl, ethyl, n-propyl, i-propyl, n-butyl, sec.-butyl, i-butyl or tert.-butyl.
In formula I, R.sup.3 is propargyl, alkyl of 1 to 3 carbon atoms, alkenyl of 3 or 4 carbon atoms or haloalkenyl of 3 or 4 carbon atoms which can contain not more than three halogen substituents, eg. methyl, ethyl, n-propyl, i-propyl, n-butyl, sec.-butyl, i-butyl, tert.-butyl, allyl, 1-chloroprop-1-en-3-yl, 2-chloroprop-1-en-3-yl, 1,3-dichloroprop-1-en-3-yl or 1,1,2-trichloroprop-1-en-3-yl.
A can be a radical of the general structure DE, where D is methylene, CO or SO.sub.2 and E is alkyl or alkenyl of not more than 20 carbon atoms, in particular not more than 18 carbon atoms.
A is therefore, for example, ethyl, propyl, acetyl, pivaloyl, butyryl, lauroyl, palmitoyl, stearyl, oleoyl, methylsulfonyl, ethylsulfonyl, propylsulfonyl or butylsulfonyl.
E can furthermore be unsubstituted or methylsubstituted cycloalkyl of 3 to 6 carbon atoms, eg. cyclopropyl, methylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or methylcyclohexyl; a phenyl, benzyl, 1-methylbenzyl or 1,1-dimethylbenzyl radical which is substituted by not more than 3 substituents from the group consisting of halogen, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, amino and nitro, eg. methylphenyl, methoxyphenyl, nitrophenyl, dichloromethoxyphenyl, trichlorophenyl, benzyl, fluorobenzyl, chlorobenzyl, methoxybenzyl, .alpha.-methylbenzyl, .alpha.-methylchlorobenzyl, .alpha.-methylbromobenzyl, .alpha.-methylmethoxybenzyl, .alpha.,.alpha.-dimethylbenzyl or .alpha.,.alpha.-dimethylchlorobenzyl; haloalkyl of not more than 3 halogen atoms and 3 carbon atoms, eg. chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, trifluoromethyl or 1,1-dichloroethyl; C.sub.1 -C.sub.4 -alkoxymethyl, acetoxymethyl or alkoxycarbonylalkyl of, in total, 3 to 9 carbon atoms, eg. methoxymethyl, ethoxymethyl, butoxymethyl, ethoxycarbonylmethyl or ethoxycarbonylethyl; phenoxyalkylene which is unsubstituted or substituted in the phenoxy moiety by not more than 3 substituents from the group consisting of halogen, C.sub.1 -C.sub.4 -alkyl and C.sub.1 -C.sub.4 -alkoxy, eg. phenoxymethyl, chlorophenoxymethyl, dichlorophenoxymethyl, chloromethylphenoxymethyl, trichlorophenoxymethyl, methylphenoxyethyl, dichlorophenoxyethyl, chloromethylphenoxyethyl, trichlorophenoxyethyl, chlorophenoxypropyl or dichlorophenoxypropyl; or an unsubstituted or substituted heterocyclic radical which has 5 or 6 ring members and 1 or 2 heteroatoms from the group consisting or N, O and S, eg. furyl, methylfuryl, dimethylfuryl, isoxazolyl, methylisoxazolyl, thienyl, pyridyl, chloropyridyl or dichloropyridyl.
A can furthermore be a radical of the formula ##STR9## where R.sup.4 is a phenyl, pyridyl, benzothiazolyl, benzoxazolyl, quinoxalinyl or quinolyl radical which is substituted by trifluoromethyl, halogen or alkyl, examples of R.sup.4 being dichlorophenyl, trifluoromethylphenyl, trifluoromethylpyridyl, chlorotrifluoromethylpyridyl, dichloropyridyl, iodopyridyl, chloroquinoxalinyl, chlorobenzothiazolyl or chlorobenzoxazolyl;
a radical of the formula ##STR10## where R.sup.5 is, for example, trifluoromethyl, chlorine or bromine and R.sup.6 is, for example, fluorine, chlorine or bromine;
a radical of the formula ##STR11## where R.sup.7 can be chlorine, bromine, methyl or ethyl;
a radical of the formula ##STR12## where G is phenylene, methylene, ethylene, propylene, tetramethylene, pentamethylene, hexamethylene or heptamethylene, and R.sup.1, R.sup.2 and R.sup.3 have the above meanings;
a radical of the formula ##STR13## where R.sup.8, R.sup.9 and R.sup.10 independently of one another are each alkyl or phenyl, examples of R.sup.8, R.sup.9 and R.sup.10 being methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec.-butyl, tert.-butyl and phenyl; or
a radical of the formula ##STR14## where the radicals Y independently of one another are each oxygen or sulfur, and R.sup.11 and R.sup.12 are each C.sub.1 -C.sub.4 -alkyl, such as methyl, ethyl, n-propyl or i-propyl.
Preferred cyclohexenol derivatives of the formula I are those in which R.sup.1 is a 6-membered heterocyclic structure, in particular one which contains one heteroatom or ring member from the group consisting of O, S, SO or SO.sub.2. Examples of appropriate radicals are tetrahydropyranyl, tetrahydrothiopyranyl, 1-oxotetrahydrothiopyranyl and 1,1-dioxotetrahydrothiopyranyl, in particular tetrahydropyran-3-yl, tetrahydrothiopyran-3-yl, 1-oxotetrahydrothiopyran-3-yl and 1,1-dioxotetrahydrothiopyran-3-yl. Other preferred cyclohexenol derivatives of the formula I are those in which X is hydrogen.
Cyclohexenol derivatives of the formula I can be obtained by a method in which a compound of the formula ##STR15## where R.sup.1, R.sup.2, R.sup.3 and X have the meanings stated for formula I, is reacted with a compound of the formula A--Z, where A has the above meanings and Z is halogen or tosyl. The reaction is carried out in an inert solvent, in the presence of a base at from -5.degree. C. to the boiling point of the mixture. If necessary, the base can be employed in aqueous solution. Depending on the miscibility, the reaction is then carried out in the homogeneous phase or in a two-phase system. In the latter case, the reaction can be accelerated by using a phase-transfer catalyst, such as an ammonium or phosphonium salt.
The reaction can also be accelerated by using an azole, such as imidazole or pyrazole, or pyridine or its derivatives, eg. 4-piperidinopyridine or 4-dimethylaminopyridine.
Suitable solvents are dimethyl sulfoxide, dimethylformamide, benzene, toluene, hydrocarbons and chlorohydrocarbons, eg. chloroform, dichloromethane, dichloroethane, hexane or cyclohexane, ketones, eg. acetone or butanone, esters, eg. ethyl acetate, and ethers, eg. diethyl ether, dioxane or tetrahydrofuran.
Examples of suitable bases are carbonates, bicarbonates, acetates, alcoholates, hydroxides and oxides of alkali metals and alkaline earth metals, in particular of sodium, potassium, magnesium and calcium. Organic bases, such as pyridine or tertiary amines, can also be used.
Salts of compounds of the formula II can also be used as starting materials for the synthesis of the novel compounds. In this case, the reaction is carried out in the manner described above, but without the addition of a base.
Compounds of the formula II are obtained by conventional processes: ##STR16##

The Examples which follow illustrate the preparation of the novel cyclohexenol derivatives of the formula I.
In the Examples, parts by weight bear the same relation to parts by volume as that of the kilogram to the liter.
The .sup.1 H-NMR data are given as .delta. values (ppm) and are based on tetramethylsilane as an internal standard. The solvent used as CDCl.sub.3. Abbreviations for the signal structures are as follows: s=singlet, d=doublet, t=triplet, q=quartet, m=multiplet, strongest signal.
EXAMPLE 1
3.1 parts by weight of 2-ethoxyaminobutylidene-5-(tetrahydropyran-3-yl)-cyclohexane-1,3-dione, 1,2 parts by weight of triethylamine and 0.2 part by weight of 4-dimethylaminopyridine in 50 parts by volume of dichloromethane are cooled to 0.degree. C., and 1.4 parts by weight of benzoyl chloride are added dropwise to this solution at from 0.degree. to 5.degree. C. The mixture is then allowed to reach room temperature, after which it is stirred for a further hour, washed with 10 percent strength hydrochloric acid and twice with 5 percent strength sodium hydroxide solution and water, and dried over sodium sulfate, and the solvent is distilled off. 1-Benzoyloxy-2-(N-ethoxybutyrimidoyl)-5-(tetrahydro-pyran-3-yl)-cyclohex-1-en-3-one are obtained as an oil (active ingredient no. 1)
.sup.1 H-NMR spectrum: 0.92 (t), 3.95 (t), 7.65 (m).
EXAMPLE 2
8.0 parts by weight of 2-ethoxyaminobutyldiene-5-(tetrahydropyran-3-yl)-cyclohexane-1,3-dione are dissolved in 50 parts by volume of acetone, after which 1.1 parts by weight of sodium hydroxide in 5 parts by volume of water are added, the mixture is stirred for 30 minutes and then cooled to 0.degree. C., and 2.2 parts by weight of acetyl chloride are added dropwise at this temperature. Thereafter, the mixture is stirred for 2 hours at room temperature, the solvent is distilled off under reduced pressure, the residue is dissolved in methylene chloride, the insoluble constituents are filtered off, the solution is extracted twice with 5 percent strength sodium hydroxide solution, washed neutral with water and dried over magnesium sulfate and the solvent is distilled off under reduced pressure. 1-Acetoxy-2-(N-ethoxybutyrimidoyl)-5-(tetrahydropyran-3-yl)-cyclohex-1-en-3-one is obtained as an oil (active ingredient no. 2).
.sup.1 H-NMR spectrum: 0.95 (t), 1.30 (t), 2.20 (s), 4.15 (q).
EXAMPLE 3
6.5 parts by weight of the sodium salt of 2-ethoxyaminobutylidene-5-(pyrid-3-yl)-cyclohexane-1,3-dione are suspended in dichloromethane, and 1.6 parts by weight of acetyl chloride are added dropwise to the suspension at room temperature. Stirring is continued for 2 hours, after which the mixture is washed with 5 percent strength sodium hydroxide solution and water and dried over sodium sulfate, and the solvent is distilled off under reduced pressure. 1-Acetoxy-2-(N-ethoxybutyrimidoyl)-5-(pyrid-3-yl)-cyclohex-1-en-1-one is obtained as a viscous oil (active ingredient no. 3).
.sup.1 H-NMR data: 1.0 (t), 4.0 (q), 8.6 (m).
The following compounds of the formula I are obtained in a similar manner: ##STR17##
__________________________________________________________________________Com-poundno. R.sup.1 X R.sup.2 R.sup.3 A .sup.1 H--NMR__________________________________________________________________________ data 4 tetrahydropyran-3-yl H n-propyl ethyl 4-methoxybenzoyl 0.85 (t), 3.90 (s), 7.0 (d) 5 tetrahydropyran-3-yl H n-propyl ethyl 2-methylbenzoyl 0.88 (t), 1.10 (t), 8.0 (d) 6 tetrahydropyran-3-yl H n-propyl ethyl 4-tert.-butylbenzoyl 1.40 (s), 4.0 (q), 7.50 (d) 7 tetrahydropyran-3-yl H n-propyl ethyl 4-chlorobenzoyl 0.90 (t), 4.0 (q), 7.50 (d) 8 tetrahydropyran-3-yl H n-propyl ethyl 4-nitrobenzoyl 3.95 (q), 8.40 (m) 9 tetrahydropyran-3-yl H n-propyl ethyl butyryl 1.25 (t), 1.90 (m), 3.35 (m) 10 tetrahydropyran-3-yl H n-propyl ethyl benzene sulfonyl 1.82 (t), 3.4 (m), 6.62 (d) 11 tetrahydropyran-3-yl H n-propyl ethyl ethylsulfonyl 0.92 (t), 3.35 (q), 4.10 (q) 12 tetrahydropyran-3-yl H n-propyl ethyl methylsulfonyl 0.90 (t), 3.20 (s), 4.10 (q) 13 tetrahydropyran-3-yl H n-propyl ethyl phenylacetyl 1.60 (m), 3.75 (s), 7.30 (m) 14 tetrahydropyran-3-yl H n-propyl ethyl 3,5-dichlorobenzoyl 0.87 (t), 7.65 (m), 7.95 (m) 15 tetrahydropyran-3-yl H n-propyl ethyl chloroacetyl 0.92 (t), 4.0 (s) 16 tetrahydropyran-3-yl H n-propyl ethyl 2,5-dichloro-6- 0.90 (t), 1.65 (m), 7.42 (d) methoxybenzoyl 17 tetrahydropyran-3-yl H n-propyl ethyl 3,5-dimethylbenzoyl 1.10 (t), 2.38 (s), 3.30 (m) 18 tetrahydropyran-3-yl H n-propyl ethyl pivaloyl 0.88 (t), 1.26 (s), 4.10 (q) 19 tetrahydropyran-3-yl H n-propyl ethyl lauroyl 20 tetrahydropyran-3-yl H n-propyl ethyl palmitoyl 1.25 (m), 2.40 (m), 4.10 (q) 21 tetrahydropyran-3-yl H n-propyl ethyl stearoyl 0.90 (t), 1.30 (m), 4.10 (q) 22 tetrahydropyran-3-yl H n-propyl ethyl oleoyl 0.86 (t), 1.25 (m), 5.40 (t) 23 tetrahydropyran-3-yl H n-propyl ethyl (4-methoxyphenyl)- acetyl 24 tetrahydropyran-3-yl H n-propyl ethyl 2-(4-methoxyphenyl)- 0.84 (t), 6.95 (m), 3.82 (s) propionyl 25 tetrahydropyran-3-yl H n-propyl ethyl 2-(4-chloro-2-methyl- 1.25 (t), 4.85 (q), 7.15 (m) phenoxy)-propionyl 26 tetrahydropyran-3-yl H n-propyl ethyl 4-(2,4-dichloro- 1.60 (m), 2.17 (m), 7.18 (m) phenoxy)-butyryl 27 tetrahydropyran-3-yl H n-propyl ethyl 2-methyl-2-phenyl- 0.80 (t), 3.12 (m), 7.36 (m) propionyl 28 tetrahydropyran-3-yl H n-propyl ethyl methoxyacetyl 1.65 (m), 2.65 (m), 3.45 (s) 29 tetrahydropyran-3-yl H n-propyl ethyl acetoxyacetyl 1.65 (m), 2.20 (s), 4.15 (q) 30 tetrahydropyran-3-yl H n-propyl ethyl 4-methoxysuccinyl 1.25 (t), 2.70 (m), 3.70 (s) 31 tetrahydropyran-3-yl H n-propyl ethyl 2,5-dimethyl- 1.16 (t), 2.26 (s), 4.05 (q) 3-furylcarbonyl 32 tetrahydropyran-3-yl H n-propyl ethyl 3,5-dimethyl-4- 0.83 (t), 2.64 (s), 4.00 (q) isoxazolylcarbonyl 33 tetrahydropyran-3-yl H n-propyl ethyl 5-isoxazolylcarbonyl 2.75 (m), 7.10 (m), 8.55 (m) 34 tetrahydropyran-3-yl H n-propyl ethyl 3-pyridylcarbonyl 35 tetrahydropyran-3-yl H n-propyl ethyl 2-chloro-3-pyridyl- 0.86 (t), 7.3 (m), 8.5 (m) carbonyl 36 tetrahydropyran-3-yl H n-propyl ethyl 3,6-dichloro-2- pyridylcarbonyl 37 tetrahydropyran-3-yl H n-propyl ethyl thien-2-yl-acetyl 1.28 (m), 3.98 (s), 7.00 (m) 38 tetrahydropyran-3-yl H n-propyl ethyl cinnamoyl 3.18 (q), 6.48 (d), 7.75 (d) 39 tetrahydropyran-3-yl H n-propyl ethyl cyclopropylcarbonyl 1.25 (t), 2.55 (m), 4.10 (q) 40 tetrahydropyran-3-yl H n-propyl ethyl 1-Methyl-cyclo- 0.82 (m), 1.30 (s), 3.20 (q) propyl-carbonyl 41 tetrahydropyran-3-yl H n-propyl ethyl 2,2-dichloropropionyl 42 tetrahydropyran-3-yl H n-propyl ethyl n-butylsulfonyl 1.25 (t), 3.90 (m), 4.15 (q) 43 tetrahydropyran-3-yl H n-propyl ethyl 3-(2-chloro-4-tri- fluoromethylphenoxy)- 6-nitrobenzoyl 44 tetrahydropyran-3-yl H ethyl ethyl 3-(2-chloro-4-tri- fluoromethylphenoxy)- 6-nitrobenzoyl 45 tetrahydropyran-3-yl H ethyl allyl 3-(2-chloro-4-tri- fluoromethylphenoxy)- 6-nitrobenzoyl 46 tetrahydropyran-3-yl H n-propyl ethyl 2-[4-(4-trifluoromethyl- phenoxy)-phenoxy]-pro- pionyl 47 tetrahydropyran-3-yl H n-propyl ethyl 2-[4-(4-iodopyrid-2-yl- oxy)-phenoxy]- propionyl 48 tetrahydropyran-3-yl H n-propyl ethyl 2-[4-(4-trifluoromethyl- pyrid-2-yloxy)-phenoxyl]- propionyl 49 tetrahydropyran-3-yl H n-propyl ethyl 2-[4-(4-trifluoromethyl- 6-chloropyrid-2-yloxy)- phenoxy]-propionyl 50 tetrahydropyran-3-yl H n-propyl ethyl 2-[4-(6-chloro-2-quin- oxalinoxy)-phenoxy]- propionyl 51 tetrahydropyran-3-yl H n-propyl ethyl 2[4-(6-chlorobenzthiazol- 2-yloxy)-phenoxy]- propionyl 52 tetrahydropyran-3-yl H n-propyl ethyl 2-[4-(5-chlorobenzoxazol- 2-yloxy)-phenoxy]- propionyl 53 tetrahydropyran-3-yl H n-propyl n-propyl benzoyl 0.75 (t), 2.6 (m), 7.6 (m) 54 tetrahydropyran-3-yl H n-propyl n-propyl 2-methylbenzoyl 55 tetrahydropyran-3-yl H n-propyl methyl benzoyl 0.85 (t), 3.70 (s), 7.6 (m) 56 tetrahydropyran-3-yl H n-propyl propargyl benzoyl 0.86 (t), 4.46 (d), 7.45 (m) 57 tetrahydropyran-3-yl H n-propyl 3-chloro- benzoyl 1.65 (m), 4.45 (d), 8.10 (d) allyl 58 2-ethylthio-n-propyl H n-propyl ethyl butyryl 59 2-ethylthio-n-propyl H n-propyl ethyl acetyl 60 2-ethylthio-n-propyl H n-propyl ethyl benzyl 0.86 (t), 4.15 (q), 5.1 (s) 61 2-ethylthio-n-propyl H n-propyl ethyl methylsulfonyl 0.92 (t), 1.35 (d), 3.15 (s) 62 2-ethylthio-n-propyl H n-propyl ethyl phenylacetyl 1.6 (t), 4.1 (q), 7.32 (m) 63 2-ethylthio-n-propyl H n-propyl ethyl 3,5-dichlorobenzoyl 64 2-ethylthio-n-propyl H n-propyl ethyl chloroacetyl 65 2-ethylthio-n-propyl H n-propyl ethyl 2,5-dichloro-6- methoxybenzoyl 66 2-ethylthio-n-propyl H n-propyl ethyl 3,5-dimethylbenzoyl 67 2-ethylthio-n-propyl H n-propyl ethyl pivaloyl 68 2-ethylthio-n-propyl H n-propyl ethyl stearoyl 69 2-ethylthio-n-propyl H n-propyl ethyl oleoyl 70 2-ethylthio-n-propyl H n-propyl ethyl (4-methoxyphenyl)- acetyl 71 2-ethylthio-n-propyl H n-propyl ethyl 2-(4-methoxyphenyl)- 1.27 (m), 3.82 (s), 6.9 (d) propionyl 72 2-ethylthio-n-propyl H n-propyl ethyl 2-(4-chloro-2-methyl- 0.87 (t), 2.55 (m), 7.1 (m) phenoxy)-propionyl 73 2-ethylthio-n-propyl H n-propyl ethyl 4-(2,4-dichloro- 0.85 (t), 4.05 (m), 7.16 (m) phenoxy)-butyryl 74 2-ethylthio-n-propyl H n-propyl ethyl 2-methyl-2-phenyl- 0.85 (t), 1.64 (s), 7.35 (m) propionyl 75 2-ethylthio-n-propyl H n-propyl ethyl methoxyacetyl 76 2-ethylthio-n-propyl H n-propyl ethyl acetoxyacetyl 77 2-ethylthio-n-propyl H n-propyl ethyl 4-methoxysuccinyl 78 2-ethylthio-n-propyl H n-propyl ethyl 2,5-dimethyl-3- furylcarbonyl 79 2-ethylthio-n-propyl H n-propyl ethyl 3,5-dimethyl- 2.45 (s), 2.6 (s), 4.02 (q) isoxazol-4-yl-carbonyl 80 2-ethylthio-n-propyl H n-propyl ethyl 5-isoxazolylcarbonyl 81 2-ethylthio-n-propyl H n-propyl ethyl 3-pyridylcarbonyl 82 2-ethylthio-n-propyl H n-propyl ethyl 2-chloro-3-pyridyl- carbonyl 83 2-ethylthio-n-propyl H n-propyl ethyl 3,6-dichloro-2-pyridyl- carbonyl 84 2-ethylthio-n-propyl H n-propyl ethyl (2-thienyl)-acetyl 85 2-ethylthio-n-propyl H n-propyl ethyl pivaloyl 86 2-ethylthio-n-propyl H n-propyl ethyl cyclopropylcarbonyl 87 2-ethylthio-n-propyl H H ethyl (1-methyl)-cyclopropyl- carbonyl 88 2-ethylthio-n-propyl H H ethyl 2,2-dichloropropionyl 89 2-ethylthio-n-propyl H H ethyl n-butylsulfonyl 90 2-ethylthio-n-propyl H H ethyl 3-(2-chloro-4-trifluoro- methylphenoxy)-6-nitro- benzoyl 91 2-ethylthio-n-propyl H ethyl ethyl 3-(2-chloro-4-trifluoro- methylphenoxy)-6-nitro- benzoyl 92 2-ethylthio-n-propyl H ethyl allyl 3-(2-chloro-4-trifluoro- methylphenoxy)-6-nitro- benzoyl 93 2-ethylthio-n-propyl H n-propyl ethyl 2-[4-(4-trifluoromethyl- phenoxy)-phenoxy]-propionyl 94 2-ethylthio-n-propyl H n-propyl ethyl 2-[4-(4-iodopyrid-2-yl- oxy)-phenoxy]-propionyl 95 2-ethylthio-n-propyl H n-propyl ethyl 2-[4-(4-trifluoromethyl- pyrid-2-yl-oxy)-phenoxy]- propionyl 96 2-ethylthio-n-propyl H n-propyl ethyl 2-[4-(4-trifluoromethyl- 6-chloropyrid-2-yloxy)- phenoxy]-propionyl 97 2-ethylthio-n-propyl H n-propyl ethyl 2-[4-(6-chloro-2-quin- oxalinoxy)-phenoxy]- propionyl 98 2-ethylthio-n-propyl H n-propyl ethyl 2-[4-(6-chlorobenzthiazol- 2-yloxy)-phenoxy]- propionyl 99 2-ethylthio-n-propyl H n-propyl ethyl 2-[4-(5-chlorobenzoxazol- 2-yloxy)-phenoxy]- propionyl100 2-ethylthio-n-propyl H n-propyl ethyl lauroyl101 2-ethylthio-n-propyl H n-propyl ethyl palmitoyl102 2-ethylthio-n-propyl H n-propyl ethyl 2,4-phenoxyacetyl103 2-ethylthio-n-propyl H n-propyl ethyl butyl-dimethyl-silyl104 2-ethylthio-n-propyl H n-propyl ethyl O,O--diethylthio- 0.90 (t), 2.50 (m) phosphoryl105 tetrahydrothiopyran-3-yl H n-propyl ethyl 4-methoxybenzoyl106 tetrahydrothiopyran-3-yl H n-propyl ethyl 2-methylbenzoyl107 tetrahydrothiopyran-3-yl H n-propyl ethyl 4-t-butylbenzoyl108 tetrahydrothiopyran-3-yl H n-propyl ethyl 4-chlorobenzoyl109 tetrahydrothiopyran-3-yl H n-propyl ethyl benzoyl 0.95 (t), 3.95 (q), 7.60 (m)110 tetrahydrothiopyran-3-yl H n-propyl ethyl butyryl111 tetrahydrothiopyran-3-yl H n-propyl ethyl benzenesulfonyl112 tetrahydrothiopyran-3-yl H n-propyl ethyl benzyl113 tetrahydrothiopyran-3-yl H n-propyl ethyl methylsulfonyl114 tetrahydrothiopyran-3-yl H n-propyl ethyl phenylacetyl115 tetrahydrothiopyran-3-yl H n-propyl ethyl 3,5-dichlorobenzoyl116 tetrahydrothiopyran-3-yl H n-propyl ethyl chloroacetyl117 tetrahydrothiopyran-3-yl H n-propyl ethyl 2,5-dichloro-6- methoxybenzoyl118 tetrahydrothiopyran-3-yl H n-propyl ethyl 3,5-dimethylbenzoyl119 tetrahydrothiopyran-3-yl H n-propyl ethyl pivaloyl120 tetrahydrothiopyran-3-yl H n-propyl ethyl lauroyl121 tetrahydrothiopyran-3-yl H n-propyl ethyl palmitoyl122 tetrahydrothiopyran-3-yl H ethyl ethyl stearoyl 1.25 (s), 2.40 (t), 4.10 (q)123 tetrahydrothiopyran-3-yl H n-propyl ethyl oleoyl124 tetrahydrothiopyran-3-yl H n-propyl ethyl (4-methoxyphenyl)- acetyl125 tetrahydrothiopyran-3-yl H n-propyl ethyl 2-(4-methoxyphenyl)- propionyl126 tetrahydrothiopyran-3-yl H n-propyl ethyl 2-(4-chloro-2-methyl- phenoxy)-propionyl127 tetrahydrothiopyran-3-yl H n-propyl ethyl 4-(2,4-dichlorophenoxy)- butyryl128 tetrahydrothiopyran-3-yl H n-propyl ethyl 2-methyl-2-phenyl- propionyl129 tetrahydrothiopyran-3-yl H n-propyl ethyl methoxyacetyl130 tetrahydrothiopyran-3-yl H n-propyl ethyl acetoxyacetyl131 tetrahydrothiopyran-3-yl H n-propyl ethyl 4-methoxysuccinyl132 tetrahydrothiopyran-3-yl H n-propyl ethyl 2,5-dimethyl-3- furylcarbonyl133 tetrahydrothiopyran-3-yl H n-propyl ethyl 3,5-dimethyl-4- isoxazolylcarbonyl134 tetrahydrothiopyran-3-yl H n-propyl ethyl 5-isoxazolylcarbonyl135 tetrahydrothiopyran-3-yl H n-propyl ethyl 3-pyridylcarbonyl136 tetrahydrothiopyran-3-yl H n-propyl ethyl 2-chloro-3-pyridyl- carbonyl137 tetrahydrothiopyran-3-yl H n-propyl ethyl 3,6-dichloro-2-pyridyl138 tetrahydrothiopyran-3-yl H n-prpoyl ethyl (2-thienyl)-acetyl139 tetrahydrothiopyran-3-yl H n-propyl ethyl pivaloyl140 tetrahydrothiopyran-3-yl H n-propyl ethyl cyclopropylcarbonyl141 tetrahydrothiopyran-3-yl H n-propyl ethyl 1-methyl-cyclo- propyl-carbonyl142 tetrahydrothiopyran-3-yl H n-propyl ethyl 2,2-dichloropropionyl143 tetrahydrothiopyran-3-yl H n-propyl ethyl n-butylsulfonyl144 tetrahydrothiopyran-3-yl H n-propyl ethyl 3-(2-chloro-4-trifluoro- methylphenoxy)-6-nitrobenzoyl145 tetrahydrothiopyran-3-yl H ethyl ethyl 3-(2-chloro-4-trifluoro- methylphenoxy)-6-nitro- benzoyl146 tetrahydrothiopyran-3-yl H ethyl allyl 3-(2-chloro-4-trifluoro- methylphenoxy)-6-nitro- benzoyl147 tetrahydrothiopyran-3-yl H n-propyl ethyl 2-[4-(4-trifluoromethyl- 1.30 (t), 4.15 (q), 7.58 (t) phenoxy)-phenoxy]-propionyl148 tetrahydrothiopyran-3-yl H n-propyl ethyl 2-[4-(4-iodopyrid-2-yl- oxy)-phenoxy]-propionyl149 tetrahydrothiopyran-3-yl H n-propyl ethyl 2-[4-(4-trifluoromethyl- pyrid-2-yloxy)-phenoxy]- propionyl150 tetrahydrothiopyran-3-yl H n-propyl ethyl 2-[4-(4-trifluoromethyl-6- chloropyrid-2-yloxy)-phen- oxy]-propionyl151 tetrahydrothiopyran-3-yl H n-propyl ethyl 2-[4-(6-chloro-2-quin- oxalinoxy)-phenoxy]- propionyl152 tetrahydrothiopyran-3-yl H n-propyl ethyl 2-[4-(6-chlorobenzthiazol- 2-yloxy)-phenoxy]-propionyl153 tetrahydrothiopyran-3-yl H n-propyl ethyl 2-[4-(6-chlorobenzoxazol- 2-yloxy)-phenoxy]-propionyl154 tetrahydrothiopyran-3-yl H n-propyl n-propyl benzoyl155 tetrahydrothiopyran-3-yl H n-propyl n-propyl 2-methylbenzoyl156 tetrahydrothiopyran-3-yl H n-propyl methyl benzoyl157 tetrahydrothiopyran-3-yl H n-propyl propargyl benzoyl158 tetrahydrothiopyran-3-yl H n-propyl 3-chloro- benzoyl allyl159 tetrahydrothiopyran-3-yl H n-propyl ethyl 3,7-dichloroquino- lino-8-yl160 pyrid-3-yl H ethyl ethyl pivaloyl 1.26 (s), 2.45 (m), 7.61 (d)161 pyrid-3-yl H n-propyl ethyl benzoyl 1.40 (m), 7.60 (m), 8.62 (m)162 pyrid-3-yl H n-propyl ethyl oleyl163 pyrid-3-yl H n-propyl ethyl palmitoyl 1.25 (s), 4.10 (q), 8.60 (m)164 pyrid-3-yl H n-propyl ethyl 2-methyl-2-phenyl- propionyl165 pyrid-3-yl H n-propyl ethyl 3,5-dimethylbenzoyl166 pyrid-3-yl H ethyl ethyl 3,5-dimethylbenzoyl167 pyrid-3-yl H ethyl ethyl 4-(2,4-dichloro- phenoxy)-butyryl168 pyrid-3-yl H ethyl ethyl 2-(2-methyl-4-chloro- phenoxy)-propionyl169 pyrid-3-yl H methyl ethyl benzoyl 1.40 (m), 7.60 (m), 8.62 (m)170 pyrid-3-yl H ethyl ethyl 3-(2-chloro-4-trifluoro- methylphenoxy)-6- nitrobenzoyl171 pyrid-3-yl H n-propyl ethyl 3-(2-chloro-4-trifluoro- methylphenoxy)-6- nitrobenzoyl172 pyrid-3-yl H n-propyl ethyl 2-[4-(4-trifluoromethyl- phenoxy)-phenoxy]-propionyl173 pyrid-3-yl H n-propyl ethyl t-butyl-dimethyl-silyl174 pyrid-3-yl H ethyl ethyl phenyl-dimethyl-silyl175 pyrid-3-yl H ethyl ethyl O,O--diethylthio- phosphoryl176 pyrid-3-yl H n-propyl ethyl 2-methylbenzoyl 2.60 (s), 7.4 (m), 8.65 (m)177 4a,7,8,8a-tetra- H n-propyl ethyl benzoyl hydro-2H,5H--pyrano- [4,3-b]pyran-3-yl178 4a,7,8,8a-tetra- H n-propyl ethyl 2-methylbenzoyl hydro-2H,5H--pyrano- [4,3-b]pyran-3-yl179 4a,7,8,8a-tetra- H n-propyl ethyl stearyl hydro-2H,5H--pyrano- [4,3-b]pyran-3-yl180 4a,7,8,8a-tetra- H n-propyl ethyl 3-(2-chloro-4-trifluoro- hydro-2H,5H--pyrano- methylphenoxy)-6- [4,3-b]pyran-3-yl nitrobenzoyl181 4a,7,8,8a-tetra- H n-propyl ethyl acetyl hydro-2H,5H--pyrano- [4,3-b]pyran-3-yl182 3,4,4a,7,8,8a-hexa- H n-propyl ethyl benzoyl hydro-2H,5H--pyrano- [4,3-b]pyran-3-yl183 cyclohexen-4-yl H n-propyl ethyl benzoyl184 4-methylcyclohex- H n-propyl ethyl benzoyl 0.85 (t), 5.62 (s), 8.18 (d) 1-en-5-yl185 2-methyl-1-cyclo- H ethyl ethyl benzoyl hexenyl186 2,6,6-trimethyl-1- H n-propyl ethyl benzoyl 0.5 (t), 1.75 (s), 8.05 (d) cyclohexenyl187 2,6,6-trimethyl-1- H n-propyl allyl benzoyl 1.05 (s), 4.50 (d), 7.6 (d) cyclohexenyl188 cyclododeca-4,8-dienyl H n-propyl allyl benzoyl189 cyclododeca-4,8-dienyl H ethyl ethyl benzoyl 1.05 (t), 5.30 (m), 7.50 (m)190 cyclohexyl H n-propyl ethyl benzoyl 1.10 (t), 1.75 (m), 7.50 (m)191 4-methyl-cyclohex-3-enyl H n-propyl ethyl benzoyl 0.85 (t), 1.65 (s), 5.35 (s)192 4-methyl-cyclohex-3-enyl H n-propyl allyl benzoyl193 4-methyl-cyclohex-3-enyl H n-propyl 3-chloro- benzoyl allyl194 4-methyl-cyclohex-3-enyl H n-propyl ethyl 2-methylbenzoyl 1.10 (t), 2.60 (t), 5.35 (s)195 2,6,6-trimethylbicyclo- H n-propyl ethyl benzoyl 1.38 (q), 3.98 (q), 7.46 (m) [3.1.1]heptan-3-yl196 2-methoxytetrahydro- H n-propyl ethyl benzoyl pyran-5-yl197 2-methoxytetrahydro- H n-propyl allyl benzoyl pyran-5-yl198 4-methyltetrahydro- H n-propyl ethyl benzoyl pyran-3-yl199 4-methyltetrahydro- H n-propyl ethyl 2-[4-(4-trifluoromethyl- pyran-3-yl phenoxy)-phenoxy]-propionyl200 4-methyltetrahydro- H n-propyl ethyl 2-[4-(4-iodopyrid-2-yloxy)- pyran-3-yl phenoxy]-propienyl201 tetrahydrofuran-3-yl H n-propyl ethyl benzoyl202 5,6-dihydro-2H-- H n-propyl ethyl benzoyl pyran-3-yl203 2-methoxytetrahydro- H n-propyl ethyl benzoyl 1.05 (t), 3.32 (s), 4.70 (s) pyran-6-yl204 tetrahydropyran-3-yl COOCH.sub.3 n-propyl ethyl benzoyl 0.88 (t), 3.75 (m), 7.45 (t)205 2-methylpyrid-6-yl H n-propyl ethyl benzoyl 1.08 (t), 2.55 (s), 8.05 (d)206 pyrid-4-yl H n-propyl ethyl benzoyl 3.60 (m), 4.0 (q), 7.28 (m)207 1-oxotetrahydro- H ethyl ethyl benzoyl 1.85 (m), 3.45 (m), 4.00 (q) thiopyran-3-yl208 1-oxotetrahydro- H n-propyl ethyl benzoyl thiopyran-3-yl209 1,1-dioxotetrahydro- H n-propyl ethyl benzoyl thiopyran-3-yl210 1,1-dioxotetrahydro- H ethyl ethyl benzoyl 1.05 (t), 4.0 (q), 8.0 (d) thiopyran-3-yl211 1-benzyloxyethyl H n-propyl ethyl benzoyl 0.90 (t), 3.55 (m), 7.35 (s)212 1-[2-n-butoxy)- H n-propyl ethyl benzoyl 3.60 (m), 4.0 (q), 7.60 (m) ethoxy]ethyl213 2-[2-(n-butoxy)- H n-propyl ethyl benzoyl ethoxy]ethyl214 4-fluorophenyl H n-butyl ethyl benzoyl 1.35 (m), 4.0 (q), 7.05 (t)215 3-methyl-4-methoxy- H n-propyl ethyl benzoyl 2.14 (s), 3.88 (s), 8.10 (m) phenyl216 3-methyl-phenyl H ethyl ethyl benzoyl226 2-i-propyl(-1,3-di- H n-propyl ethyl benzoyl oxepan)-5-yl227 2-i-propyl(-1,3-di- H ethyl ethyl benzoyl oxepan)-5-yl228 tetrahydropyran-3-yl H n-propyl ethyl 2-(4-chlorophenyl)-2- 1.61 (s), 4.08 (q), 7.31 (m) methyl-propionyl229 tetrahydropyran-3-yl H n-propyl ethyl 2-methyl-fur-3-yl- 2.60 (s), 3.23 (q), 6.65 (s) carbonyl230 tetrahydropyran-3-yl H n-propyl ethyl 2-(2,4,5-trichloro- 4.85 (m), 7.01 (s), 7.52 (s) phenoxy)-propionyl231 4-methylcyclohex-1- H n-propyl allyl benzoyl 0.85 (t), 4.45 (d), 5.60 (s) en-5-yl232 4-methylcyclohex-1- H n-propyl ethyl methylsulfonyl 1.30 (t), 3.25 (s), 6.67 (s) en-5-yl233 4-methylcyclohex-1- H ethyl ethyl benzoyl 1.10 (t), 7.50 (m), 8.05 (d) en-5-yl234 4-methylcyclohex-1- H ethyl ethyl methylsulfonyl 1.25 (t), 3.2 (s), 5.65 (s) en-5-yl235 4-methylcyclohex-1- H ethyl allyl benzoyl en-5-yl236 2-ethylthio-n-propyl H n-propyl ethyl 2-(2,4,5-trichloro- 4.10 (9), 7.00 (s), 7.52 (s) phenoxy)-propionyl237 2-ethylthio-n-propyl H n-propyl ethyl 2-(3-bromophenoxy)- 4.05 (q), 4.81 (q), 7.10 (m) phenoxy)-propionyl238 2-ethylthio-n-propyl H n-propyl ethyl 2-(4-bromophenyl)- 2.5 (m), 7.26 (m), 7.46 (m) propionyl239 2-ethylthio-n-propyl H n-propyl ethyl 2-(4-fluorophenyl)- 1.55 (d), 4.05 (m), 7.04 (m) propionyl240 5,6-dihydro-2H--1-oxo- H n-propyl 3-chloro- benzoyl 0.85 (t), 3.60 (m), 7.55 (m) thiopyran-3-yl allyl241 2-ethylthio-n-propyl H n-propyl ethyl O,O--diethylphosphoryl 0.95 (t), 2.58 (q), 4.2 (m)242 2-ethylthio-n-propyl H n-propyl ethyl n-butyl-dimethyl-silyl 0.08 (s), 1.3 (m), 2.9 (m)243 2-ethylthio-n-propyl H n-propyl ethyl phenyl-dimethyl-silyl 0.35 (s), 1.0 (t), 7.4 (m)244 tetrahydropyran-3-yl H n-propyl ethyl O,O--diethylthio- 0.90 (t), 1.40 (t), 4.10 (q) phosphoryl245 tetrahydropyran-3-yl H n-propyl ethyl O,O--diethylphosphoryl 0.95 (t), 1.38 (t), 4.2 (m)246 tetrahydropyran-3-yl H n-propyl ethyl n-butyl-dimethyl-silyl247 tetrahydropyran-3-yl H n-propyl ethyl phenyl-dimethyl-silyl 0.30 (s), 0.93 (t), 6.35 (m)248 2-ethylthio-n-propyl H n-propyl ethyl249 4-methyltetrahydro- H n-propyl 3-chloro- O,O--diethylthio- 0.92 (t), 1.37 (t), 4.7 (m) pyran-3-yl allyl phosphoryl250 4-methyltetrahydro- H n-propyl 3-chloro- O,O--diethylphosphoryl 0.95 (t), 1.4 (t), 6.15 (m) pyran-3-yl allyl251 4-methyltetrahydro- H n-propyl 3-chloro- phenyl-dimethyl-silyl 0.62 (s), 5.08 (d), 7.63 (m) pyran-3-yl allyl252 4-methyltetrahydro- H n-propyl 3-chloro- 2-[4-(4-trifluoromethyl- 1.0 (d), 3.4 (t), 7.0 (m) pyran-3-yl allyl phenoxy)-phenoxy]- propionyl253 2-(4-chlorophenyl- H ethyl ethyl 4-chlorobenzoyl 1.10 (t), 1.80 (q), 2.97 (t), thio)-ethyl 7.26 (s)254 tetrahydropyran- H n-propyl ethyl benzyl 0.90 (t), 1.30 (m), 5.10 (s), 3-yl 7.35 (m)255 5,6-dihydro-2H--1,1- H n-propyl 3-chloro- benzoyl 0.88 (t), 3.60 (m), 7.55 (m) dioxothiopyran-3-yl allyl256 pyridyl-3-yl H n-propyl ethyl pivaloyl257 5,6-dihydro-2H--1- H n-propyl ethyl benzoyl oxothiopyran-3-yl258 4a,7,8,8a-tetra- H n-propyl allyl benzoyl hydro-2H,5H--pyrano- [4,3-b]-3-yl263 pyrid-3-yl H n-propyl ethyl 2,5-dichloro-6- 0.90 (t), 3.90 (m), 8.60 (m) methoxy-benzoyl264 4-methylcyclohex- H n-propyl ethyl benzoyl 0.85 (t), 3.98 (q), 8.05 (d) 1-en-5-yl265 cyclododecyl H n-propyl ethyl benzoyl 0.90 (t), 3.97 (q), 8.04 (d)266 tetrahydrofur-3-yl H n-propyl ethyl benzoyl 0.85 (t), 3.85 (q), 7.50 (m)267 tetrahydrothiopyran- H n-propyl ethyl O,O--diethylthio- 0.92 (t), 1.4 (m), 4.2 (m) 3-yl phosphoryl268 tetrahydropyran-4-yl H n-propyl ethyl benzoyl269 tetrahydropyran-4-yl H n-propyl ethyl palmitoyl270 tetrahydropyran-4-yl H n-propyl ethyl stearoyl271 tetrahydropyran-4-yl H n-propyl ethyl 3-(2-chloro-4-tri- fluoromethyl-phenoxy)- 6-nitrobenzoyl272 tetrahydropyran-4-yl H ethyl ethyl 3-(2-chloro-4-tri- fluoromethyl-phenoxy)- 6-nitrobenzoyl273 tetrahydropyran-4-yl H ethyl allyl 3-(2-chloro-4-tri- fluoromethyl-phenoxy)- 6-nitrobenzoyl274 tetrahydropyran-4-yl H n-propyl ethyl 2-[4-(4-trifluoromethyl- phenoxy)-phenoxy]-propionyl275 tetrahydropyran-4-yl H n-propyl ethyl 2-[4-(4-iodopyrid-2-yloxy)- phenoxy]-propionyl276 tetrahydropyran-4-yl H n-propyl ethyl 2-[4-(4-trifluoromethylpyryl- 2-yloxy)-phenoxy]O,O---277 tetrahydropyran-4-yl H n- propyl ethyl 2-[4-(4-trif luoromethyl-6- chloro-pyrdi-2-yloxy)- phenoxy]-propionyl278 tetrahydropyran-4-yl H n-propyl ethyl 2-[4-(6-chloro-2-quinoxalinoxy)- phenoxy]-propionyl279 tetrahydropyran-4-yl H n-propyl ethyl 2-[4-(6-chlorobenzthiazol-2- yloxy)-phenoxy]-propionyl280 tetrahydropyran-4-yl H n-propyl ethyl 2-[4-(6-chlorobenzoxazol-2- yloxy)-phenoxy]-propionyl281 6-methoxy-tetrahydro- H ethyl ethyl benzoyl pyran-2-yl282 3,4,4a,7,8,8a-hexa- H n-propyl allyl benzoyl 0.90 (t), 4.4 (d), 8.15 (d) hydro-2H,5H--pyrano- [4,3-b]pyran-3-yl__________________________________________________________________________
__________________________________________________________________________ ##STR18##Compoundno. R.sup.1 X R.sup.2 R.sup.3 G .sup.1 HNMR data__________________________________________________________________________218 tetrahydropyran-3-yl H n-propyl ethyl phenylene 0.90(t), 1.08(t), 8.17(s)219 tetrahydropyran-3-yl H n-propyl ethyl propylene 0.90(t), 1.70(s), 3.90(m)220 tetrahydropyran-3-yl H n-propyl ethyl tetramethylene221 tetrahydropyran-3-yl H n-propyl ethyl hexamethylene222 tetrahydrothio- H n-propyl ethyl phenylene pyran-3-yl223 tetrahydrothio- H n-propyl ethyl methylene pyran-3-yl224 tetrahydrothio- H n-propyl ethyl tetramethylene pyran-3-yl225 pyrid-3-yl H n-propyl ethyl tetramethylene259 4a,7,8,8a-tetra- H n-propyl ethyl phenylene hydro-2H,5Hpyrano- [4,3-b]-3-yl260 4a,7,8,8a-tetra- H n-propyl ethyl tetramethylene hydro-2H,5Hpyrano- [4,3-b]-3-yl261 2-i-propyl-1,3- H n-propyl ethyl phenylene dioxepan-5-yl262 2-i-propyl-1,3- H ethyl ethyl phenylene dioxepan-5-yl__________________________________________________________________________
The cyclohexenol derivatives of the formula I 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, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone, and water 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 and 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 0.5 to 90, % by weight of active ingredient.
Examples of formulations are given below.
I. 90 parts by weight of compound no. 2 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. 8 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 the active ingredient.
III. 20 parts by weight of compound no. 5 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 the active ingredient.
IV. 20 parts by weight of compound no. 253 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.degree. 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 the active ingredient.
V. 20 parts by weight of compound no. 60 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 lignin-sulfonic 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 the active ingredient.
VI. 3 parts by weight of compound no. 109 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.
VII. 30 parts by weight of compound no. 252 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. 1 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.
The active ingredients, or agents containing them, may be applied pre- or postemergence. 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 amount of active ingredient applied depends on the time of the year, the plants to be combated and their growth stage, and varies from 0.025 to 3 kg/ha, but is preferably from 0.1 to 1.5 kg/ha.
The action of the cyclohexenol 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 1.5% 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. The soybean plants were grown in a peat-enriched substrate. 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 rates for postemergence treatment were 0.125, 0.25, 0.5 and 3.0 kg of active ingredient per hectare. No covers were placed on the pots in this treatment.
The pots were set up in the greenhouse--species from warmer areas at from 20.degree. 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 of complete destruction of at least the visible plant parts.
The plants used in the experiments were Alopecurus myosuroides, Avena fatua, Avena sativa, Beta vulgaris, Brassica napus, Bromus spp., Cassia spp., Digitaria sanguinalis, Echinochloa crus-galli, Eleusine indica, Glycine max., Gossypium hirsutum, Helianthus annuus, Hordeum vulgare, Ipomoea spp., Lolium multiflorum, Setaria italica, Sinapis alba, Sorghum bicolor, Sorghum halepense, Triticum aestivum, and Zea mays.
PREEMERGENCE APPLICATION
For examples compounds nos. 39, 229, 109, 207, 210, 55, 53, 161, 12, 2, 8, 61, 60, 160, 252, 250 and 242 proved to be herbicidally effective on plants from the Gramineae family, whereas mustard (Sinapis alba), a dicotyledonous member of the Cruciferae family, remained completely undamaged. On the other hand, compounds nos. 73, 230, 25 and 72, on preemergence application, controlled both the grassy plants tested and the broadleaved plant mustard.
POSTEMERGENCE APPLICATION
For example compounds nos. 217, 28, 30, 22, 191, 79, 37, 239, 17 and 228, applied postemergence at a rate of 3.0 kg/ha, controlled grassy plants. Compounds nos. 230, 26, 73 and 72 had an action both on grassy and broadleaved plants.
On application of 0.125 kg/ha, for instance compounds nos. 109, 207, 252, 40, 20, 238, 71, 74, 35, 56, 186, 255, 122, 29, 176, 33, 190, 206, 169, 7, 5, 13, 219, 254, 9, 27, 31, 18, 32, 24, 57, 42 and 266, and for example compounds nos. 1, 2, 4, 5, 241, 242, 243, 245 und 247 applied at a rate of 0.25 kg/ha were extremely effective on plants from the Gramineae family, Compound no. 253, at 0.125 kg/ha, also controlled unwanted grassy plants without damaging broadleaved crops. Unwanted grassy species were selectiely combatted in a cereal crop wheat, which is also a member of the Gramineae family, by 0.25 kg/ha of compound no. 61. Further, for instance compounds nos. 194, 212, 233 and 234 controlled unwanted grasses in cereals.
In view of the broad spectrum of weeds combatted, the tolerance by crop plants and 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. esculenta table beets, red beetsBrassica napus var. napus rapeseedBrassica napus var. napobrassica swedesBrassica napus var. rapa turnipsBrassica rapa var. silvestrisCamellia sinensis tea plantsCarthamus tinctorius safflowerCarya illinoinensis pecan treesCitrus limon lemonsCitrus maxima grapefruitsCitrus reticulata mandarinsCitrus sinensis orange treesCoffea arabica (Coffea canephora, coffee plantsCoffea liberica)Cucumis melo melonsCucumis sativus cucumbersCynodon dactylon Bermudagrass in turf and lawnsDaucus carota carrotsElais guineensis oil palmsFragaria vesca strawberriesGlycine max soybeansGossypium hirsutum cotton(Gossypium arboreumGossypium herbaceumGossypium vitifolium)Helianthus annuus sunflowersHelianthus tuberosus Jerusalem artichokeHevea brasiliensis rubber plantsHordeum vulgare barleyHumulus lupulus hopsIpomoea batatas sweet potatoesJuglans regia walnut treesLactuca sativa lettuceLens culinaris lentilsLinum usitatissimum flaxLycopersicon lycopersicum tomatoesMalus spp. apple treesManihot esculenta cassavaMedicago sativa alfalfa (lucerne)Mentha piperita peppermintMusa spp. banana plantsNicothiana tabacum tobacco(N. rustica)Olea europaea olive treesOryza sativa ricePanicum miliaceum milletPhaseolus lunatus limabeansPhaseolus mungo mungbeansPhaseolus vulgaris snapbeans, green beans, dry beansPetroselinum crispum parsleyspp. tuberosumPicea 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 potatoesSorghum bicolor (s. vulgare) sorghumSpinacia 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 (post-directed)______________________________________
To increase the spectrum of action and to achieve synergistic effects, the novel cyclohexenol derivatives may be mixed and applied together with numerous representatives of other herbicidal or growth-regulating active ingredient groups. Examples of 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 acids, etc.
It may also be useful to apply the cyclohexenol derivatives 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	Date	Country	Kind
3336140	Oct 1983	DEX
3342630	Nov 1983	DEX

Number	Name	Date	Kind
3989737	Sawaki et al.	Nov 1976
4422864	Becker et al.	Dec 1983

Number	Date	Country
0082694	Jun 1983	EPX
0104876	Apr 1984	EPX
2110673	Jun 1983	GBX

Herbicidal cyclohexanol derivatives, compositions, and method of use therefor

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Sawaki et al., C.A. vol. 82 (1975), 82: 170218n, p. 477.
Chemical Abstracts, vol. 86, p. 397, No. 16357h (1977).