CA2129121A1 - Mixtures of optically active cyclohexenone oxime ethers, their preparation and intermediates therefor, and use thereof as herbicides - Google Patents

Abstract

Mixtures of optically active cyclohexenone oxime ethers, with an R and S configuration in the oxime ether section of formula (I) where R1 = C1-C6 alkyl; X = NO2, CN, halogen, C1-C4 alkyl, C1-C4 halogen alkyl; n = 0-3 or 1-5 if all X
substituents are halogen; R2 = C1-C4-alkoxy-C1-C6-alkyl, C1-C4-alkythio-C1-C6-alkyl, optionally substituted C3-C7 cycloalkyl, optionally substituted C5-C7 cycloalkenyl, optionally substituted 5-membered saturated heterocyclic ring containing 1 or 2 oxygen and/or sulphur atoms, optionally substituted 6 or 7-membered heterocyclic ring with 1 or 2 non-adjacent oxygen and/or sulphur atoms which may be saturated or singly or doubly unsaturated, optionally substituted aromatic 5-membered heterocyclic ring containing one to two N atoms and one O or S atom, phenyl or pyridyl both of which may bear 1-3 substituents: halogen, NO2, CN, alkyl, alkoxy, alkylthio, halogen alkyl, alkenyloxy, alkinyloxy and/or -NRaRb; Ra = H, alkyl, alkenyl or alkinyl and Rb =
H, alkyl, alkenyl, alkinyl, acyl or optionally substituted benzoyl; and their agriculturally usable salts, and esters of C1-C10 carboxylic acids and inorganic acids of compounds (I), with the proviso that the mixtures contain at least 75 mol % isomers with R configuration in the oxime ether part.

Description

o.z. 0050/43017 Mixtures of optically active cyclohexenone oxime ethers, their preparation and intermediates therefor, and use thereof as herbicides De~cription The present invention relate~ to novel mixture~
of optically active cyclohexenone oxime ethers, of R- or S-configuration in the oxime ether moiety, of the general formula I

~ N - O - CH~ ~ r where the ~ub~tituent~ have the following meaning~:
Rl i~ a Cl-C~-alkyl group;
X i~ nitro, cyano, halogen, Cl-C,-alkyl or Cl-C,-halo-alkyl;
n is 0 to 3 or 1 to 5 if all the Xs are halogen;
R' i~
a Cl-C,-alkoxy-Cl-C~-alkyl or Cl-C,-alkylthio-Cl-Cc-alkyl group;
a C3-C7-cycloalkyl group or a C5-C7-cycloalkenyl group, It being pos~ible if de~ired for these groups to carry one to three ~ubstituent~ selected from a group 20. con~isting of Cl-C,~alkyl, Cl-C,-alkoxy, Cl-C,-alkylthio, Cl-C~-haloalkyl, hydroxyl and halogen;
_ a 5-membered saturated heterocycle which contains one or two oxygen and/or ~ulfur atom~ a~ heteroatoms and which can, if de~ired, additionally carry one to thre~
substituent~ selected from a group consisting of Cl-C~-alkyl, Cl-C~-alkoxy, Cl-C~-alkylthio and Cl-C~-halo-alkyl;
a 6- or 7-membered ~aturated or mono- or diun-~aturated heterocycle which contain~ one or two oxygen or , - 2 - O.Z. 0050/43017 sulfur atoms or an oxygen atom and a sulfur atom as heteroatom~, :
it being po~ible if desired for the heterocycle additionally to carry on~ to three ~ubstitu~nt~ ~elected from a group consisting of hydroxyl, halogen, Cl-C~-alkyl, C1-C,-alkoxy, C,-C,-alkylthio and Cl-C~-haloalkyl;
a 5-membered heteroaromatic, containing one to ~:
thre~ heteroatom~ select~d from a group co~si~ting of one or two nitrog~n at~m~ and an oxygen or sulfur atom, it b~ing possible fox the heteroaromatic if desired additionally to carry one to three substituent~ `
selected from a group consisting of halogen, cyano, Cl-C,-alkyl, Cl-C,-alkoxy, Cl-C,-alkylthio, Cl-C,-haloalkyl, C2-C~-alkenyl, C~-C~-alkenyloxy and Cl-C~-alkoxy-Cl-C,-alkyl;
a phenyl or pyridyl group, it being pos~ible for these aromatic~ if de~ired additionally to carry one to three ~ubstituen~ 3elected from a group con~isting of halogen, nitro, cyano, Cl-C,-alkyl, Cl-C~-alkoxy, Cl-C,-alkylthio~ C1-C,-haloalkyl, C3-C~-alkenyloxy, C3-Cc-alkynyloxy a,~d an amino group -NR'Rb, where R' is hydrogen, Cl-C,-alkyl, C3-Cc-alkenyl or C3-Cc-alkynyl and Rb i~ hydrog~n~ C1-C~-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, Cl-Cc-acyl or benzoyl which if de~ired ~:
can in turn carry one to three radicals selected from a group con~i~ting of nitro, cyano, halogen, Cl-C4-alkyl, Cl-C4-alkoxy, C,-C4-alkylthio and Cl-C,-haloalkyl; :
_ and the agriculturally utili~able ~alts and e~t¢rs of C~-C10-carboxylic acid~ and inorganic acid~ of the compound~ I, with the proviso that the mixture~ contain at lea~t 75 mol% of i~omer~ of R-configuration in the oxLme ether moiety.
The invention additionslly relates to a process for preparing these compounds, their use as herbicid0~

- 3 - O.Z. 0050/43017 and herbicidal a~ent~ which co~tain these compound~ as active substance~.
The invention furthermore relates to novel mixtures of optically active hydroxylamine~, of R- or S S-configuration, of the formula III

~N O- CH2 - C - O ~ r~I

where i~ nitro, cyano, halogen, Cl-C~-alkyl or Cl-C,-halo-alkyl and n i~ O to 3 or 1 to 5 if all the X~ are halogen, with the provi~o that the mixture~ contain at lea~t 75 mol~ of i~omsr~ of R-configuration, and a proceff~ for ~;
preparing the intermediate~
Herbicidally active cyclohexanedione~ of the formul~
.
OH
~N - o - R~

RC
o .' ~

are already known fro~ the literature, where Rot Rd and R
have, inter alia~ th~ following meanings:
- US 4,440,566 ~R = ethyl or propyl; ~d Z benzyl; R-_= 2-ethylthiopropyl);
- EP-A 238,021 and EP-A 125,094 (Rc = ethyl or propyl;
Rd = benzyl or but-2 enyl; R = a su~tituted 5-membered heteroaryl radical);
- EP-A 80,301 (Rc = ethyl or propyl; Rd 3 benzyl or but-2-enyl; R - substituted phenyl);
- DE-A 3,838,309 (R ~ ethyl or propyl; Rd ~ a ~ub- :
~tituted 4-phenylbutylene Gr 4-phenylbutenylene - 4 - O.Z. OOSO/43017 radical; R - a ~ubstituted S- to 7-membered hetero-cycle);
- EP-A 456,112 (Rc ethyl or propyl; FP - a substitu-ted 3-phenoxypropylene or 2-phenoxyethylene radical;
R - a ~ubstituted 5- to 7-membered hoterocycle).
The herbicidal propertie~ of the~e compound~, in particular with re~pect to their selectivity for weeds in graminaceous crop plants, however, may only give limited ~atisfaction.
Thus it was an ob~oct of the presont invontion to provido novol mixturos of cyclohexonono oxim~ ethers having improved solectivity for w~od~ in graminaceous crops such a8 rice and m~izo.
Accordingly we have found t~at this object is achievod by mixtur~ of optically active cycloh~xenone -oxime othors I. Wo have additionally found herbicidal compositions which contain those mixture~
Tho mixtures of optically active cycloh~xenone oxime othors I are obtain~blo in variou~ ways, namely prefor~bly in a manner known p~r se from already known cyclohexenono~ of the formula II (DE-A 3,838,309, EP-A 243,313, ~P-A 456,112) and the corresponding mixture~ of optically active hydroxylamines of the formula III (cf. EP-A 169,521): ~;

O H ~;
C ~ H~N O CH2 1--O ~ ~~~~
~ Rl CH3 _ rs II~

OH N - o CN2 C - O

C\ C~3 \~ Rl ~ 2129121 :..

- 5 - o.Z. 0050/43017 A suitable salt of the hydroxylamine III is preferably used, in particular it~ hydrochloride, and the reaction i~ carried out in the heterogeneous phase in an inert sol~ent, for example in dimethyl sulfoxide, in an alcohol ~uch as methanol, ethanol and isopropanol, in an aromatic hydrocarbon such as benzene and toluene, in a chlorinated hydrocarbon ~uch as chloroform and 1,2-di-chloro~thane, in an aliphatic hydrocarbon ~uch as hexano and cyclohexane, in an e~ter such as ethyl acetate or in a~ ether ~uch as diethyl ether, dioxane and tetrahydro-furan.
The reaction is conducted in the pre~ence of a ba~e, an amount of b~se of about 0.5 to 2 molar equiva~
lents, bas~d on the amm~nium compound, normally being ~ufficient.
Suitable ba~es are, for example, carbonates, hydrogencarbonate~, acetates, alkoxides or oxide~ of alkali metals or alkaline earth metals, in particular sodium hydroxide, potassium hydroxide, magnesium oxide or calcium oxide. Organic bases such as pyridine and tert-amines such as triethylamine are additionally suitable.
The reaction is preferably carried out in methanol using sodium hydrogen carbonate as a base.
A variant of the process consi~ts in carrying out the reaction without base with the free hydroxylamine ba~es III, for example in the form of an aqueous 801u-tion; depending on the solvent used for the compound II, a ~ingle-phase or two-phase reaction mixture i~ obtained.
Suitable solvents for this variant are, for example, alcohols such a~ methanol, ethanol, isopropanol and cyclohexanol, aliphatic and aromatic, unchlorinated or chlorinated hydrocarbon~ such as hexane, cyclohexane, methylene chloride, toluene and 1,2-dichloroethane, e~ters ~uch as ethyl acetate, nitrile~ ~uch a~ aceto-nitrile and cyclic ethers ~uch as dioxane and tetrahydro-furan.
The cyclohexenone II and the mixture of optically - - 6 - o.Z. 0050/43017 active hydroxylamines III or their salts are expediently employed in an approximstely ~toichiometric ratio, but in some ca~es an exce~ of one or the other componente, up to about 10 mol%, can be advantageous.
The reaction temperature i~ in general from 0C
to the boiling point of the reaction mixture, preferably from 20 to 80C.
The reaction i8 complete after a few hour~. The product can be i~olated in a customary manner, for ex~mple by concentrating the mixture, partitioning the residue in methylene chlorid~/water and distilling off the solvent under reduced pre~sure.
Particular requirement~ with respect to the pre~Qure do not have to be taken into account; in general, the reaction is ther~fore carried out at at~
mospheric pressure or under the autogenous pressure of the respective diluent.
On account of their acidic character, the opti~
cally active cyclohexenone oxime ethers I can form salts of alkali metal or alkaline earth metal compounds, as well a~ enol esters.
Alkali metal salts of the compound~ I can be obtained by treating the 3-hydroxycyclohexenone compounds with sodium hydroxide or alkoxide or potas~ium hydroxide or alkoxide in agueous solution or in an organic solvent _uch as methanol, ethanol, acetone and toluene.
Other metal salts such as manganeYe, copper, zinc, iron, calcium, magnesium and barium salts can also be prepared from the sodium salts in a cu_tomary manner, a3 well as ammonium and pho~phonium Qalts by meanQ of ammonia, or phosphonium, Qulfonium or sulfoxonium hydroxidea.
The esters of the cQmpounds I are al~o obtainable in a cu_tomary manner ( cf., for example, Organikum, VEB
DeutQcher Verlag der Wissen~chaften, Berlin, 17th edi-tion, (1988) pp. 405-408).
The novel mLxture~ of optically active - 7 - O.Z. 0050/43017 hydroxylamine~ III can be prepared via a number of known proce~s ~tep~ starting from known precur~or~:

N x /C~ t HO C~ - C O
D N - O~ C~3 C or.
O H Xn ~-VI I ~ - o~2 - C O ~ .
CN

e D 1~2~-CH2CH~-o~
~N--O--C~- C- 0 O .
Y~I
L - a leaving group, for example halogen such a~
chlorine, bromine or iodi~e, or CH3502-O-.
The optically active alkylati~g agent~ V (Tetra-hedron Lett. 29, (1988) 5493; J. Org. Chem. 52 (198~
3587; EP-A 172 719; EP-A 230 379; US 4~841,079), but if de~ired ai~o the optically active carbinol IV (Chem.
Pharm. Bull. 33, (1985) 1955) i~ preferably coupled by the_Mit~unobu variant (Synthe~i~ 1, 1981; J. Med. Chem.
33, (1990) 187) with a cyclic hydroxyimide VI and the prot~cted hydroxylamine derivative VII ob~ained in thi~
proce~ cleaved to give the fr~e optically actiYe hydroxylamine III, for example u~ing 2-aminoethanol.
In the cyclic hydroxyLmide3 VI D i~, for example, C2-C3-alkylene, C2-alkenylene or a 5- or 6-membered rlng with or without a nitrogen atom, which can be ~aturated, ~ 21~9121 - 8 - O.Z. 005~/43017 partially unsaturated or aromatic, for ~xample phenylene, pyridinylene, cyclopentylene, cyclohexylene or cyclo-hexenylene.
For sxample, the following ~ub~tance~ are ~uit-able:

N-ON ~ NLCH ~ N-O~

O O
.

~0 ¢ ' ~0 ~

~0 .The reaction of the optically active alkylating agent~ V with the hydroxyLmide3 VI i~ expediently carried out in the pre~ence of a base. Suitable ba~e~ are prin-cipally all tho~e which ar~ able to deprotonate the hydroxyimide~ VI without atta~king the Lmide ~y~tem.
The~ ar~ particularly the ~o-called non-nucleophilic ba~e~.
_ Examples which may be mentioned are inorganic bases such a~ alkali metal and alkaline earth metal carbonates, alkali metal and alkaline earth metal hydro-gencarbonate~, organic ba~e~ ~uch a~ aliphatic, cyclo-aliphatic and aromatic tertiary ~mine~ However, mixtures of the~e base~ can al50 be u~ed.
Individual compounds which may be li~ted by way of axample are the following base~: ~odium carbonate, `~ 212~121 - - 9 - O.Z. 0050/43017 potassium carbonate, magnesium carbonate, calcium carbonate, barium carbonate, the hydrogencarbonate~ of these metals, trimethylamine, triethylamine, tributyl-amine, ethyldiisopropylamin~, N,N-dimethylaniline, 4-lN,N-dimethylamino)pyridine, diazabicyclooctane, diazabicycloundecane, N-methylpiperidine, 1,4-dimethyl-piperazine, pyridine, quinoline, bipyridine and phenan-throline. The inexp~nsive bases sodium carbonate and potassium carbonate are preferred.
The base is generally added in equivalent amounts up to an excess of 5 equivalents, based on the hydroxy-imide. A greater excess is possible, but as a rule conv~ys no additional advantages. The uso of a small amount of ba~e i~ also pos~ibl~. ~owever, an amount of base from 1 to 3 equivalents, in particular from 1 to 2 equivalents, based on the hydroxyimide VI, is preferably employed.
The use of nucleophilic bas~s, for example alkali metal and alkaline earth metal hydroxides, in particular ~odium hydroxide and potassium hydroxid~, is also pos-~ibl~. In thi~ case, it is advantageous to employ the base in equivalent amounts with re~pect to the hydroxy-imide VI to prevent a nucleophilic attack of the hydroxyl ions on the carboxyl function of the imide group.
The optically active alkylating agents V are expediently reacted with the hydroxyimides VI in a ~olvent which is inert under the reaction conditions.
Advantageous ~olvents are, for exampls, polar aprotic solvents such as dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane and cyclic urea~. The amount of solvent i~ generally not critical.
The reaction of the optically active alkylating agents V with the hydroxyimides VI can al~o be carried out u~ing phase tran~fer catalysis. In thi~ case, ~ol-vents forming two phases with water, preferably chloro-hydrocarbons, are employed.
Useful phase transfer catalysts are the ` 2129121 -- - 10 - O.Z. OOS0/43017 quaternary ammonium and phosphonium salts, polyethylene qlycols, polyethylene glycol ethers and crown ethers customarily used for ~uch purpose~, as are described, for example, in Dehmlow et al., Phase Transfer Catalysi~
(1980), pp. 37-45 and pp. 86-93, Verlag Chemie, Weinheim.
The phase transfer catalysts are expediently employed in amounts from 1 to 10% by volume, preferably in amounts from 3 to 5% by volume, based on the volume of the reaction mixture.
10The optically active alkylating agent~ V are generally reacted with the hydroxyimide~ VI in a temper-ature range from 0 to 140C, pr~ferably from 20 to 100C, in pRrticular from 40 to 80C. A procedure i~ advantageo-u~ly u~ed here in which the hydroxyimide VI is introduced into the solvent together with the base and the alkyla-ting agent V is metered into this solution. In thi~
procedure, it may prove convenient to add the hydroxy-m~de at a lower temperature, for ex~mple at from 0 to 50C, and to heat the reaction mixture to the actual reaction temperature only after this addition.
After reaction is complete, the cooled reaction mixture is expediently treated with water, the hydroxyl-amine derivatives VII formed precipitating a~ crystalline ~olid~ or as oil~. The hydroxylam;ne derivatives obtained in this way can be further purified, if desired, by recrystalliz~tion or by extraction.
The hydroxylamine derivative~ VII can be tem-porarily stored or immediately converted into the opti-cally active hydroxylam;nes III having a free amino group.
This conversion can be carried out by proces~es known per se, as ar~ described, for example, in D~-A 3,615,973 and the papers cited therein. Preferably, the proces~ as described in DE-A 3,615,973 is used, according to which the optically active hydroxylamines III were liberated by means of ethanolamine. The liberation of the optically active hydroxylamines III

. .

.
- 11 - O.Z. 0050/43017 using other ba~es such as aqueous inorganic bases, with amines, hydrazine~ or hydroxylamines or by means of aqueous acids is also poQsible.
The optically active hydroxylamine~ III can be i~olated from the reaction mixture~ obtained by the~e proce~se~ by means of customary working-up method~, for example by extraction or by crystallization. To increa~e the tendency of these hydroxylamines III to crystallize, it may often be beneficial to convert the~e into their salts with inorganic acid or organic acids. To this end, dilute solutions of these acid~ are generally reacted with the hydroxylamine derivativeo, namely expediently in equivalent amounts. Like the optically active hydroxyl-amines III (baving a free amino gropp), the hydroxyl-a _o~ium salts obtained can be directly processed to the optically active cyclohexenone oxime athers of the formula I or alternatively stored, if desired.
The optical purity of the intermediates III and of the cyclohexenone oxime ether~ I depend~ on the optical purity of the carbinols IV or alkylating agent~
V employed. According to the invention, carbinols IV
having the R-configuration or alkylating agent~ V having the R-configuration are employed, namely with as high an optical purity as possible, 80 that in the preparation of the optically active hydroxylamines III and of the opticalIy active cyclohexenone oxLme ether~ I, isomer mixture~ are obtained in each ca~e who~e content of i~omer~ having the R-configuration on the methyl-~ub-~tituted C atom (in the oxime ether moiety) i~ at lea~t 75 mol%, in particular 90 to 100 mol%.
The optically active cyclohexenone oxim~ ether~
I can be obtained during the preparation a~ i~omer mixture~, both E/Z isomer mixture~ (position of the oxime ether moiety relative to R1) and diastereoi~omer mixture~
being po~ible. If desired, the isomer mixture~ can be ~eparated by the method~ cu~tomary for thi~ purpo~e, for example by chromatography or by cry~tallization.

.-``` 212~121 :
- 12 - O.~ 0050/43017 The optically active cyclohexenone oxLm~ ethers I can be written in ~everal tautomeric form~, which are all included by the invention.
The collective terms used in th~ definition of the ~ubstitu~nt~
- halogen, -Cl-C~-alkyl, Cl-C,-alkoxy, Cl-C,-alkylthio, Cl-C,-halo- ~ :
alkyl, - C2-C6-alkenyl, C2-C6-alkenyloxy, - C3-C,-alkenyl, C3-C6-alkenyloxy, C3-C6-alkynyl, C3-C,-alkynyloxy, - Cl-C~-acyl ~, are a ~hort way of writing an individual ligt of the ~ -individual group memb~rs. All the al~yl, alkoxy, alkyl-thio, haloalkyl, alkenyl, alkenylo~y, alkynyl and alkynyloxy moieties can be straight-chain or branched.
The haloalkyl moieties can carry identical or different halogen atoms.
The following term~ ~pecifically mean, for example - halogen: fluorine, chlorine, bromine and iodine;
- Cl-C~-alkyl: methyl, ethyl, n-propyl, l-methylethyl, n-butyl, l-methylpropyl, 2-methylpropyl and l,1-di-methylethyl;
- Cl-C~-alkoxy; methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpxopoxy, 2-methyl-propoxy and l,l-dLmethylethoxy;
- C,-C~-alkylthio: methylthio, ethylthio 9 n-propylthio, l-methylethylthio, n-butylthio, l-met~ylpropylthio, _ 2-methylpropylthio and 1,1 dLmethylethylthio;
- Cl-C4-haloalkyl: fluoromethyl, difluoromethyl, trifluoromethyl, chlorodifluoromethyl, dichloro-fluoromethyl, trichloromethyl, l-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-tri~luoro-ethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoro-ethyl; ` ~;

212~121 - 13 - O.Z. 0050/43017 - C2-C~-alkenyl: ethenyl and C3-C6-alkenyl such a~
l-propenyl, 2-propenyl, l-methylethenyl, l-butenyl, 2-butenyl, 3-butenyl, l-methyl-l-propenyl, l-methyl-2-propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, l-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, l-methyl-l-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dLmethyl-2-propenyl, 1,2-dimetbyl-1-propenyl, 1,2-dimethyl-2-propenyl, l-ethyl-l-propenyl, l-ethyl-2-propenyl, l-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, l-methyl-l-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pent~nyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentQnyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dLmethyl-2-butenyl, 1,l-dLmethyl-3-butenyl, 1,2-dLmethyl-l-butenyl, 1,2-dLmethyl-2-butenyl, 1,2-dLmethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dLmethyl-3-butenyl, 2,2-dLmethyl-3-butenyl, 2,3-dimethyl-l-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dLmethyl-l-butenyl, l-ethyl-l-butenyl, l-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-_ 3-butenyl, 1,1,2-trimethyl-2-propenyl, l-ethyl-1-methyl-2-propenyl,l-ethyl-2-methyl-1-propenyland 1-ethylo2-methyl-2-propenyl;
- C2-Cc-alkenyloxy: ethenyloxy and C3-C6-alkenyloxy ~uch a~ 2-propenyloxy, 2-butenyloxy, 3-butenyloxy, 1-methyl-2-propenyloxy, 2-methyl-2-propenyloxy, 2-pentenyloxy, 3-pentenyloxy, 4-pentenyloxy, l-methyl-2-butenyloxy, 2-methyl-2-butenyloxy, ~.

- 14 - O.Z. 0050/43017 3-methyl-2-butenyloxy, 1-methyl-3-butenyloxy, 2-methyl-3-butenyloxy, 3-methyl-3-butenyloxy, ~ :
1,1-dimethyl-2-propenyloxy, 1,2-dimethyl-2-propenyloxy, 1-ethyl-2-propenyloxy, 2-hexenyloxy, 3-hexenyloxy, 4-hexenyloxy, 5-hexenyloxy, l-methyl-2-pentenyloxy, 2-methyl-2-pentenyloxy, 3-methyl-2-pentenyloxy, 4-methyl-2-pentenyloxy, 1-methyl-3-pentenyloxy, 2-methyl-3-pentenyloxy, 3-methyl-3-pentenyloxy, 4-methyl-3-pentenyloxy, l-methyl-4-pentenyloxy, 2-methyl-4-pentenyloxy, 3-methyl-4-pentenyloxy,4-methyl-4-pentenyloxy,1,l-dimethyl-2-butenyloxy, 1,2-dimethyl-2-butenyloxy, 1,2-dLmethyl-3-butenyloxy, 1,3-dLm~thyl-2-butenyl-oxy, 1,3-dimethyl-3-butenyloxy, 2,2-dimethyl-3-butenyloxy, 2,3-dim~thyl-2-butenyloxy, 2,3-dimethyl-3-butenyloxy; 1-ethyl-2-butenyloxy, l-ethyl-3-butenyloxy,2-~thyl-2-butenyloxy,2-ethyl-3-butenyloxy, 1,1,2-trimethyl-2-propenyloxy, l-ethyl-l-methyl-2-propenyloxyandl-ethyl-2-methyl-2-propenyloxy;
With re~pect to their herbicidal activity, cyclohexenone~ of the formula I are preferred in whi~h the variable~ have the following meaning~:
R~ Cl-C6-alkyl such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, preferably ethyl and propyl;
X - nitro, cyano, - halogen, preferab~y fluorine, chlori~ and bromine; ~ -- Cl-C4-alkyl, preferably methyl;
_ - C~-C~-haloalkyl, preferably difluoromethyl, tri- ~:
fluoromethyl, 2,2,2-trifluoroethyl and penta-fluoroethyl; ~ :
halogen i~ particularly preferred; ~-n 0 to 3 or 1 to 5 if all the Xa ar~ halogen; 0 to 3 ~::
i~ particularly preferred;

- a Cl-C6-alkyl group such as methyl, ethyl, n-propyl, 2i2~
`
. - 15 - O.Z. 0~50/43017 1-methylethyl, n-butyl, l-methylpropyl, 2-methyl-propyl and 1,1-dimethylethyl, n-pentyl, l-methylbutyl, 2-methylbutyl, 3-methylbutyl, l,1-di-methylpropyl, 1,2-dimethylpropyl, 2,2-dL~ethyl-propyl, l-ethylpropyl, n-hexyl, l-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dLmethylbutyl, 1,2-dimethylbutyl, 1,3-di-methylbutyl, 2,2-dLmethylbutyl, 2,3-dLmethylbutyl, 3,3-~;methylbutyl, l-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-~thyl-2-methylpropyl, where the alkyl group is ~ubstituted by Ca-C,-alkoxy, pr~f~rably methoxy, ethoxy, 1-methylethoxy or 1,1-dimethylethoxy, or by Cl-C~-alky~thio, preferably methylthio or ethylthio, namely preferably in the 1-, 2- or 3-position;
2-ethylthiopropyl is very particularly preferred;
- a C3-C7-cycloalkyl group or a C5-C~-cycloalkenyl group such a~ cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclohexenyl and cycloheptenyl, wherQ the~e group~ can be unsub-~tituted or can carry one to three of the following ~ub~tituents~
Cl-C,-alkyl, Cl-C,-alkoxy, C~-C,-alkylthio and Cl-C~-haloalkyl; 1-methylthio-1-cyclopropyl i5 very particularly preferred;
- a 5-memb~red ~aturated h~terocycle ~uch as tetra-hydrofuranyl, tetrahydrothienyl, dioxolanyl, di-thiolanyl snd oxathiolanyl, in particular tetrahy-_ drofuranyl, tetrahydrothienyl and dioxolanyl, where the~e ring~ can be un~ub~tituted or ca~ carry one to three ~ub~tituents selected from a group consisting of Cl-C,-alkyl, Cl-C,-alkoxy, Cl-C4-alkylthio and Ci-C,-haloalkyl;
35 - a 5-mem~ered heteroaromatic such a~ pyrrolyl, pyrazolyl, Lmidazolyl, isoxazolyl, oxazolyl, iso-thiazolyl, thiazolyl, furanyl and thienyl, in . - 16 - o.Z. 0050/43017 particular isoxazolyl and furanyl, where th~ 5-membered heteroaromatic can be unsubstituted or can carry one to three substituents selected from a group consisting of Cl-C~-alkyl, C,-C,-alkoxy, Cl-C~-alkylthio, Cl-C,-haloalkyl and Cl-C,-alkoxy-Cl-C,-alkyl sùch a~ methoxymethyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 2-methoxy-l-methylethyl, ethoxymethyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 2-ethoxy-1-methyl-ethyl and l-ethoxy-l-methylethyl, preferably methoxy~thyl and ethoxyethyl, C2-C,-alkenyl such aB ethenyl and C3-C~-alkenyl, preferably l-methyleth~n-l-yl, C2-C~-alkenyloxy such as ~thenyloxy and C3-C~-al-kenyloxy, in particular l-methylethen-l-yloxy, - a 6- or 7-membered heterocycle which a) can be ssturated, for example tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-3-yl, tetr~hydrothiopyran-4-yl and dioxepan-5-yl, b) can be mono- or diunsaturated, for example di-hydropyran-3-yl, dihydropyran-4-yl, dihydrothio-pyran-3-yl and dihydrothiopyran-4-yl, where the heterocycles can be unsubstituted or can carry one to three substituents ~elected from a group con~i~ting sf hydroxyl, halogen, C,-C~-alkyl, C~ alkoxy, Cl-C~-alkylthio and Cl-C4-haloalkyl;
tetrahydropyran-3-yl, tetrahydropyran-4-yl and tetrahydrothiopyran-3-yl are very particularly preferred;
- _ a phenyl or pyridyl group, both of which can be unsubstituted or can carry one to three ~ubstituent~
~elected from a group con~i~ting of C1-C,-alkyl, Cl-C~,-alkoxy, Cl-C~-alkylthio, Cl-C,-haloalkyl, C3-C6-alkenyloxy, preferably 2-propenyloxy and 2-butenyloxy, C3-C~-alkynyloxy such as 2-propynyloxy, 2-butynyloxy, 3-butynyloxy, 1-methyl-2-propynyloxy, 2-pentynyloxy, 3-pentynyloxy, 4-pentynyloxy, 212912~
- 17 - o.Z. ~050/43017 l-methyl-3-butynyloxy, 2-methyl-3-butynyloxy, l-methyl-2-butynyloxy, 1,1-dLmethyl-2-propynylox~, l-ethyl-2-propynyloxy, 2-hexynyloxy, 3-hexynyloxy, ~ :~
4-hexynyloxy, 5-hexynylo~y, l-methyl-2-pentynyloxy, -:
1-methyl-3-pentynyloxy, 1-methyl-4-pentynyloxy, 2-methyl-3-pentynyloxy, 2-methyl-4-p~tynyloxy, 3-methyl-4-pentynyloxy, 4-methyl-2-pe~tynyloxy, 1,1-dLmethyl-2-butynyloxy, 1,1-dimethyl-3-butynyl-oxy,l,2-dLmethyl-3-butynyloxy,2,2-dLmethyl-3-buty-nyloxy, 1-~thyl-2-butynyloxy, 1-ethyl-3-butynyloxy, 2-ethyl-3-butynyloxy and l-ethyl-l-m~thyl-2-pro-py~yloxy, prefer~bly 2-propynyloxy a~d 2-butynyloxy;
one of th~ three substituents on th~ phenyl or pyridyl ring can al80 b~ an amino group -NR~Rb, wh~r~
R' i~ :
hydrogen, Cl-C~-alkyl, preferably mQthyl or ~thyl, -~
C3-Cc-alkenyl, preferably 2-propenyl or 2-but~nyl, C3-C~-alkynyl, preferably 2-propynyl or 2 butynyl, and ~ :~
Rb i~
hydrogen, Cl-C,-al~yl, preferably methyl or ethyl, C3-C6-alkenyl, preferably 2-propenyl or 2-butenyl, C3-C~-alkynyl, preferably 2-propynyl or 2 butynyl, or i8 Cl-C6-acyl such a~ acetyl, propionylO butyryl, 2-methylpropionyl, n-pentanoyl, 2-methy~butyryl, 3 methylbutyryl, 2,2-dLmethylpropionyl, n-hexanoyl, _ 2-methylpentanoyl, 3-methylpentanoyl~ 4-methyl-pentanoyl,2,2-dLmethylbutyryl,2,3-dimethylbutyryl, 3,3-dLmethylbutyryl and 2-ethylbutyryl, pr~ferably acety~ or propionyl, or benzoyl which can be un~ub~tituted or can in turn carry one to three radical~ selected from a group con~i~ting of nitro, cyano, halogen, preferably fluorine, chlorine and bromine, Cl-C~-alkyl, - 18 - O.Z. 0050/43017 preferably methyl, Cl-C,-alkoxy, preferably methoxy and ethoxy, Cl-C,-alkylthio, preferably methylthio, and Cl-C~-haloalkyl, preferably tri~luoromethyl.
Suitable ~alt~ of the compound~ of the formula I
are agriculturally utilizable ~alts, for example alkali metal ~alt~, in particular the ~odium or potas~ium ~alt, alkaline earth metal ~alts, in particular the calcium, magnesium or barium ~alt, the manganese, copper, zinc or iron salt or the ammonium, phosphonium, sulfonium or sulfoxonium salt~, for example ammonium salts, tetra-alkyla _ onium salt~, benzyltrialkylammonium salts, trialkylsulfonium salts or trialkylsulfoxonium salts.
Ester- of Cl-C1O-carboxylic acids are in par-ticular undsrstood a- meaning C~-C,-al~ylcarboxylic acids such as metbanecarboxylic acid (acetic acid), ethanecar-boxylic acid (propionic acid), propanecarboxylic acid (butyric acid), l-methylethanecarboxylic acid (isobutyric acid), butanscar~oxylic acid, l-methylpropaneoarboxylic acid, 2-methylpropanecarboxylic acid, l,l-d~methyl-ethanecarboxylic acid, pentanecarboxylic acid, 1-meth-ylbutanecarboxylic acid, 2-methylbutanecarboxylic acid, 3-methylbutanecarboxylic acid, 1,1-dimethylpropane-carboxylic acid, 1,2-dimethylpropanecarboxylic acid, 2,2-dimethylpropanecarboxylic acid, l-ethylpropane-carboxylic acid, benzoic acid and benzoic acids~ubstituted by halogen, hexanecarboxylic acid, l-methyl-pentanecarboxylic acid, 2-methylpentanecarboxylic acid, 3-methylpentanecarboxylicacid,4-methylpentanecarboxylic acid, l,l-dimethylbutanecarboxylic acid, 1,2-dimethyl-butanecarboxylic acid, 1,3-dimethylbutanecarboxylic acid, 2,2-dimethylbutanecarboxylic acid, 2,3-dimethyl-butanecarboxylic acid, 3,3-dimethylbutanecarboxylic acid, l-ethylbutanecarboxylic acid, 2-ethylbutanecarboxylic acid, 1,1,2-trimethylpropanecarboxylic acid, 1,2,2-tri-methylpropanecarboxylic acid, l-ethyl-l-methylpropane-carboxylic acid and l-ethyl-2-m~thylpropanecarboxylic acid.
.. ..

212912 ~
.
- 19 - O.Z. 0050/43017 PREPARATIO~ ~XAMPLES
(R)-2-~1-(2-(4-ehlorophenoxy)propyloxyimino]propyl]-3-hydroxy-5-(1-methylthioeyelopropyl)-2-eyelohexen-1-one A mixture of 1.0 g (3.9 mmol) of 3-hydroxy-5-(1-methylthioeyelopropyl)-2-propionyl-2-eyclohexen-l-one, 0.95 g (4.7 mmol) of (R)-0-~2-(4-ehlorophenoxy)-propyllhydroxylamine and 80 ml of methanol was ~tirred for 24 hours and then eoneentrated under r~dueed pres-sure. The re~idue was taken up in tert-butyl methyl ether, after whieh the ether pha~e was extraeted with 10~ ;
strength by weight ~odium hydroxide ~olution. The aqueous phase was in turn ~xtraeted with tert-butyl methyl ether and then aeidified with 10~ ~trength by weight hydroehlo-rie aeid. It wa~ finally extraeted onee more with tert-butyl methyl ether, after whieh the organie phase was dried over sodium sulfate and eoneentrated under redueed pressure. Yield: 59%; ta]~5 - - 13.1 (e 3 l.Q; in methanol); --~H-NMR (200 MHz, in CDCl3): ~ - 0.77 ppm (m,2~); 0.97 ppm (m,2~); 1.10 ppm (t,3H); 1.35 ppm (d,3H); 1.60 ppm (m,lH); 2.13 ppm (8,3~); 2.40 - 2.80 ppm (m,4H); 2.90 ppm (q,2~); 4.20 ppm (m,2H); 4.6~ ppm (m,lH); 6.90 ppm ;~
(d,2H); 7.20 ppm (d,2H); 14.20 ppm (b~,lH).
PRECURSOR
(R)-O-t2-(4-~hlorophenoxy)propyllhydroxylamine -~
24.9 g (0.143 mol) of diethyl azodiearboxylat~
were ~lowly added dropwi~e to a solution of 23.3 g (0.143 mol) of N-hydroxyphthalLmide, 33.3 g (0.127 mol) of triphenylpho~phine and 23.7 g (0.127 mol) of (R)- -2-(4-ehlorophenoxy)-1-propanol tCAS Reg. No. 92471-63-1, Chem. Pharm. Bull. 33, (1985) 1955] in 300 ml of tetra-hydrofuran. After a weakly exothermic reaetion, the mixture wa~ ~tirred for about a furth~r 15 hours and then concentrated. By ehromatography of the re~idue on ~iliea gel (eyelohexane/ethyl acetate 1:1), 42 g of (R)-N-t2-(4-ehlorophenoxy)propoxy]phthalimide were obtained.
This erude phthal;~;de produet was ~ubseguently 212gl~ 1 - 20 - O.z. 0050/43017 treated ~lowly with 100 ml of ethanolamine. After 5 hours at 60C, the reaction mixture was poured into ice-water, extracted with methylene chloride, and the combined organic phase~ were washed with water, dried over ~odium ~ulfate and concentrated under reduced pre~sure. Yield:
81%; ta]25 ~ -20.8 (c ~ 1.0; in methanol).
H-NMR (360 M8z, in CDCl~ 1.25 ppm (d,3H); 3.75 ppm (dd,lH); 3.85 ppm (dd,lH); 4.65 ppm (m,lH); 5.50 ppm (b~,28); 6.90 ppm (d,2H); ?.20 ppm (d,2H). ~ -In the following Tab}e I, further opt~cally -active hydroxylamine~ III are shown which w~re prepared or can be prepared in the ~ame way. The Table~ 2 to 8 ~ ~ -contain optically active cyclohexenone oxime ether~ I
according to the invention. -. ~

21 2 1 2 9 1 2 1 . Z . 0050/430l7 Table 1 H X
H2N 0--CH2 C 0~ III
` :.

' ' :
No. Xn Phys. data ~Rotational value ~a] D25;
c= 1.0, in CH30H / lH-NMR lppm] ) ~:;
1 . 01 2-Cl -34 . 1 1 . 02 3-Cl -23 . 2 1 . 03 4-Cl -2U . 8 20 1 . 04 2, 4-C12 -27 . 5 1. 05 2-CH3, 4-Cl -26 . 2 1. 06 2, 4-F2 -21. 5 1. 07 4-F -27 . 5 22 O.~. 0050/43017 212~121 Table 2 .
Cl "~ ,, N CH2 C 0 ~
~ ~ I (Xn = 2-Cl) R2 ~ C CH3 ~ R
'. ~

No. R1 R2 Phys. data ~Rotational value [a] D25;
c = 1.0, in CH30H/
lH-NMR ~ppm]/
m.p. [C]) `~
2.01 Ethyl (RS)-2H Tetrahydropyran-3-yl -42.0 2.02 Ethyl (R)-2H-Tetrahydropyran-3-yl 2.03 Ethyl (S)-2H-Tetrahydropyran-3-yl 2.Q4 Ethyl 2H-Tetrahydropyran-4-yl -37.2 2.05 Ethyl (RS)-2H-Tetrahydrothiopyran-3-yl -34.6 2.06 Ethyl ~R)-2H-Tetrahydrothiopyran-3-yl 2.07 Ethyl (S)-2H-Tetrahydrothiopyran-3-yl -2.08 n-Propyl (RS~-2H-Tetrahydropyran-3-yl -33.6 2.09 n-Propyl (R)-2H-Tetrahydropyran-3-yl 2.10 n-Propyl (S)-2H-Tetrahydropyran-3-yl 2.11 n-Propyl 2H-Tetrahydropyran-4-yl -38.9 2.12 n-Propyl (RS)-2H-Tetrahydrothiopyran-3-yl -27.6 2.13 n~Propyl (R)-2H-Tetrahydrothiopyran-3-yl 2.14 n-Propyl (S~-2H-Tetrahydrothiopyran-3-yl 35 2.15 Ethyl Phenyl 2.16 Ethyl 2,4,6-Trimethylphenyl 2.17 Ethyl 4-(Prop-2-ynyloxy)phenyl 2.18 n-Propyl 4-Fluoro-3~nitrophenyl 2.19 n-Propyl (RS)-2-(Ethylthio)prop-1-yl 2.20 Ethyl 1-Methylthiocycloprop-1-yl 2.21 Ethyl 1,3-Dimethylpyrazol-5-yl 2.22 n-Propyl 3-Isopropyli~oxazol-5-yl 2.23 n-Propyl (RS)-Cyclohex-3-en-1-yl 23 O.Z. 005~/43017 212~121 .

Table 3 Cl H
~ N CH2 C 0 ~ I (Xn = 3-Cl~ ;~
R2 ~ C CH3 \\ R~
' ~ ~' No. Rl R2 Phys. data (Rotational value [a] D25; ;,,, c in CH30~
1H-NMR [ppm]/
m.p. lC]) 3.01 Ethyl (RS)-2H-Tetrahydropyran-3-yl -13.2 3.02 Ethyl (R)-2H-Tetrahydropyran-3-yl 3.03 Ethyl (S)-2H-Tetrahydropyran-3-yl 3.04 Ethyl 2H-Tetrahydropyran-4-yl -17.1 3.05 Ethyl (RS)-2H-Tetrahydrothiopyran-3-yl -11.8 3.06 Ethyl (R)-2H-Tetrahydrothiopyran-3-yl 3.07 Ethyl (S)-2H-Tetrahydrothiopyran-3-yl 3.08 n-Propyl (RS)-2H-Tetrahydropyran-3-yl -11.7 3~09 n-Propyl (R)-2H-Tetrahydropyran-3-yl 3.10 n-Propyl (S)-2H-Tetrahydropyran-3-yl 3~ 3.11 n-Propyl 2H-Tetrahydropyran-4-yl -12.5 3.12 n-Propyl (RS)-2H-Tetrahydrothiopyran-3 yl - 8~3 3.13 n-Propyl (R3-2H-Tetrahydrothiopyran-3-yl 3.14 n-Propyl (S)-2H-Tetrahydrothiopyran-3-yl 3.I5 Ethyl Phenyl -17.4 3.16 Ethyl 2,4,6-Trimethylphenyl -15.6 3.17 Ethyl 4-(Prop-2-inyloxy)phenyl -14.9 3.18 n-Propyl 4-Fluor-3-nitrophenyl -ll.g 3.19 n-Propyl (RS)-2-(Ethylthio)prop-1-yl -12.7 3.20 Ethyl 1-Methylthiocycloprop-l-yl -14.9 3.21 Ethyl 1,3-Dimethylpyrazol-5-yl 3.22 n-Propyl 3-Isopropylisoxazol-5-yl 3.23 n-Propyl (RS)-Cyclohex-3-en-1-yl -15.0 3.24 n-Propyl l-Methylthiocycloprop-1-yl -lS.1 24 O.Z. 0050/43017 212~121 ~. .

Table 4 H ~.
~ OH N O CH2 - I ~ Cl I (Xn = 4-Cl) R2 ~ C CH3 Rl O ~, No. R1 R2 Phys. data ~Rot. value ~a]D25;
c = 1.0, .
in CH30H/
lH-NMR [ppm]/ ;~
. ~ m.p. [C]) 4.01 Ethyl (RS)-2H-Tetrahydropyran-3-yl -11.9 4.02 Ethyl (R)-2H-Tetrahydropyran-3-yl 4.03 Ethyl (S)-2H-Tetrahydropyran-3-yl 4.04 Ethyl 2H-Tetrahydropyran-4-yl -12.4 4.05 Ethyl (RS)-2H-Tetrahydrothiopyran-3-yl -10.3 4.06 Ethyl (R)-2H-Tetrahydrothiopyran-3-yl 4.07 Ethyl ts)-2H-Tetrahydrothiopyran-3-yl 4.08 n-Propyl (RS)-2H-Tetrahydropyran-3-yl -10.8 4.09 n-Propyl (R)-2H-Tetrahydropyran-3-yl 4.10 n-Propyl (S)-2H-Tetrahydropyran-3-yl 4.11 n-Propyl 2a-Tetrahydropyran-4-yl - 8.9 4.12 n-Propyl (RS)-2H-Tetrahydrothiopyran-3-yl -12.1 4.13 n-Propyl (R)-2H-Tetrahydrothiopyran-3-yl 4.14 n-Propyl (S)-2H-Tetrahydrothiopyran-3-yl 4.15 Et~yl Phenyl -12.6 4.16 Ethyl 2,4,6-Trimethylphe~yl -13.0 4.17 Ethyl 4-(Prop-2-inyloxy)phenyl -13.0 4.18 n-Propyl 4-Fluor-3-nitrophenyl - 8.1 4.19 n-Propyl (RS)-2-(Ethylthio)prop-l-yl -11.5 4.20 Ethyl 1-Methylthiocycloprop-1-yl -13.1 4.21 Ethyl 1,3-Dimethylpyrazol-5-yl 4.22 n-Propyl 3-Isopropylisoxazol-5-yl 4.23 n-Propyl ~RS)-Cyclohex-3-en-1-yl 4.24 n-Propyl l-Ethylthiocycloprop-l-yl - 9.7 4.25 Ethyl l-Ethylthiocycloprop-l~yl -12.3 4.26 n-Propyl l-Propylthiocycloprop-l-yl - 9.1 4.27 Ethyl 1-Propylthiocycloprop-l-yl -12.6 :

O.Z. 0050/43017 `-`,` 212~121 Table 5 Cl OH N O CH2 C O ~ Cl R2 ~ C C~3 I (Xn - 2,4-Clz) Rl ~
' "'~
No. Rl R2 Phys. data (Rotational value la] D25;
lS ' c = 1.0, .
in CH30H/
1H-NMR [ppm]/
m.p. [C~

5.01 Ethyl (RS)-2H-Tetrahydropyran-3-yl -36.5 5.02 Ethyl (R)-2H-Tetrahydropyran-3-yl 5.03 Ethyl (S)-2H-Tetrahydropyran-3-yl 5.04 Ethyl 2H-Tetrahydropyran-4-yl -35.5 5.05 Ethyl (RS)-2H-Tetrahydrothiopyran-3-yl -25.3 5.06 Ethyl (R)-2H-Tetrahydrothiopyran-3-yl 5 . 0? . Ethyl (S)-2H-Tetrahydrothiopyran-3-yl 5.08 n-Propyl (RS)-2H-Tetrahydropyran-3-yl -32.5 5.09 n-Propyl (R)-2H-Tetrahydropyran-3-yl 5.10 n-Propyl (S)-2H-Tetrahydropyran-3-yl 5.11 n-Propyl 2H-Tetrahydropyran-4-yl -34.2 5.12 n-~ropyl (RS)-2H-Tetrahydrothiopyrar.-3-yl -22.2 5.13 n-Propyl (R)-2H-Tetrahydrothiopyran-3-yl 5.14 n-Propyl (S)-2~-Tetrahydrothiopyran-3-yl 5.*~ Ethyl Phenyl 5.16 Ethyl 2,4,6-Trimethylphenyl 5.17 Ethyl 4-(Prop-2-ynyloxy)phenyl 5.18 n-Propyl 4-Fluoro-3-nitrophenyl 5.19 n-Propyl (RS)-2-(Ethylthio)prop-l-yl 5.20 Ethyl l-Methylthiocycloprop-l-yl 5.21 Ethyl 1,3-Dimethylpyrazol-5-yl 5 . 22 n-Propyl 3-Isopropylisoxazol-5-yl 5.23 n-Propyl tRs)-cyclohex-3-en-l-yl .

26 O . Z . 0050/43017 : , Table 6 N - 0 - C~2 - C - 0 ~ Cl R1 I (Xn = 2-CH3, 4-Cl) No. Rl R2 Phys. data (Rotational value [a]D25;
c = 1.0, in CH30H/
lH-NMR [ppm]~
m.p. ~C]) ~~

6.01 Ethyl (RS)-2H-Tetrahydropyran-3-yl -26.5 6.02 Ethyl (R)-2H-Tetrahydropyran-3-yl 6.03 Ethyl (S)-2H-Tetrahydropyran-3-yl 6.04 Ethyl .H-Tetrahydropyran-4-yl -16.3 6.05 Ethyl (RS)-2H-Tetrahydrothiopyran-3-yl -17.1 6.06 Ethyl (R)-2H-Tetrahydrothiopyran-3-yl 6.07 Ethyl (S)-2H-Tetrahydrothiopyran-3-yl 6.08 n-Propyl (RS)-2H-Tetrahydropyran-3-yl -24.7 6.09 n-Propyl (R)-2H-Tetrahydropyran-3-yl 6.10 n-Propyl (S~-2H-Tetrahydropyran-3-yl 6.11 n-~ropyl 2H-Tetrahydropyran-4-yl -24.9 6.12 n-Propyl (RS)-2H-Tetrahydrothiopyran-3-yl -19.0 6.13 n-Propyl (R~-2H-Tetrahydrothiopyran-3-yl 6.1~ n-Propyl (S)-2H-Tetrahydrothiopyran~3-yl 35 6.15 Ethyl Phenyl 6.16 Ethyl 2,4,6-Trimethylphenyl 6.17 Ethyl 4-(Prop-2-ynyloxy)phenyl 6.18 n-Propyl 4-Fluoro-3-nitrophenyl 6.19 n-Propyl (RS)-2-(Ethylthio)prop-1-yl 6.20 Ethyl 1-Methylthiocycloprop-1-yl 6.21 Ethyl 1,3-Dimethylpyrazol-5-yl 6.22 n-Propyl 3-Isopropylisoxazol-5-yl 6.23 n-Propyl (RS)-Cyclohex-3-en-1-yl ~":" ' . ' 27 O.Z. 0050/43017 ` 212~121 .

Table 7 ~ ~
. ~
H \ ~:
N O C~2 C 0~ F :
R2 ~ C CH3 R1 I (Xn = 2~ 4-F2) O
: ~ ' No. R1 R2 Phys. data ~ -(Rotational value [~]D25~
c ~ 1.0, in CH30H/
lH-NMR [ppm]/
m.p. [C]) -7.01 Ethyl (RS)-2H-Tetrahydropyran-3-yl - 9.2 7.02 Ethyl (R)-2H-Tetrahydropyran-3-yl 7.03 Ethyl (S)-2H-Tetrahydropyran-3-yl 7.04 Ethyl 2H-Tetrahydropyran-4-yl -13.2 7.05 Ethyl (RS)-2H-Tetrahydrothiopyran-3-yl -10.5 7.06 Ethyl (R)-2H-Tetrahydrothiopyran-3-yl 7.07 Ethyl (S)-2H-Tetrahydrothiopyran-3-yl 7.08 n-Propyl (RS)-2H-Tetrahydropyran-3-yl - 6.6 7.09 n-Propyl (R)-2H-Tetrahydropyran-3-yl 7.10 n-Propyl (S)-2H--Tetrahydropyran-3-yl 7.11 n-Propyl 2~-Tetrahydropyran-4-yl -15.3 7.12 n-Propyl (RS)-2H-Tetrahydrothiopyran-3-yl -13.8 7.13 n-Propyl (R)-2H-Tetrahydrothiopyran-3-yl 7.14 n-Propyl (S)-2H-Tetrahydrothiopyran-3-yl 7.~ Ethyl Phenyl -15.3 7.16 Ethyl 2,4,6-Trimethylphenyl -17.3 7.17 Ethyl 4-~Prop-2-ynyloxy)phenyl -14.7 7.18 n--Propyl 4-Fluoro-3-nitrophenyl -11.3 7.19 n-Propyl (RS)-2-(Ethylthio)prop-l-yl -10.5 7.20 Ethyl 1-Methylthiocycloprop-l-yl -14.6 7.21 Ethyl 1,3-Dimethylpyrazol-5-yl 7.22 n-Propyl 3-Isopropylisoxazol-5-yl 7.23 n-Propyl (RS)-Cyclohex-3-en-1-yl -13,4 7.24 n-Propyl l-Methylthiocycloprop-1-yl - 8.9 .

~8 ~.Z. 0050/43017 -- ` 2 1 2 3 1 ? 1 Table 8 H

~ N O - CH2 - C - O ~ F
- R2 ~ C CH3 ~ R1 I (Xn = 4-F) O ' !:

No. Rl R2 Phys. data (Rotational value ~a]D25;
c - 1.0, in CH30~/
lH-NMR [ppm]/
m.p. [Cl) 8.01 Ethyl tRS)-2H-Tetrahydropyran-3-yl -19.2 8.02 Ethyl (R)-2H-Tetrahydropyran-3-yl 8.03 Ethyl (S)-2H-Tetrahydropyran-3-yl 8.04 Ethyl 2H-Tetrahydropyran-4-yl ~19.1 8.05 Ethyl (RS)-2H-Tetrahydrothiopyran-3-yl -17.9 8.06 Ethyl (R)-2H-Tetrahydrothiopyran-3-yl 8.07 Ethyl (S)-2H-Tetrahydrothiopyran-3-yl 8.08 n-Propyl (RS)-2H-Tetrahydropyran-3-yl -18.3 8.09 n-Propyl (R)-2H-Tetrahydropyran-3-yl 8.10 n-Propyl (S)-2H-Tetrahydropyran-3-yl 8.11 n-Propyl 2H-Tetxahydropyran-4-yl -21.9 8.12 n-Pr.opyl (RS)-2H-Tetrahydrothiopyran-3-yl -17.9 ~:
8.13 n-Propyl (R)-2H-Tetrahydrothiopyran-3-yl 8.14 n-Propyl (S)-2H-Tetrahydrothiopyran-3-yl 8.~5 Ethyl Phenyl -18.3 :
8.16 Ethyl 2,4,6-Trimethylphenyl -19.3 :~
8.17 Ethyl 4-(Prop-2-ynyloxy)phenyl -20.3 8.18 n-Propyl 4-Fluoro-3-nitrophenyl -16.5 .
8.19 n-Propyl (RS)-2-(Ethylthio)prop-1 yl -14.5 8.20 Ethyl l-Methylthiocycloprop-l-yl ~19.1 8.21 Ethyl 1,3-Dimethylpyrazol-5-yl ~-.
8.22 n-Propyl 3-Isopropylisoxazol-5-yl `~
8.23 n-Propyl (RS)-Cyclohex-3-en-1-yl -20.5 8.24 n-Propyl 1-Methylthiocycloprop-l-yl -18.4 : .

29 O.Z. 0050/43017 212~121 The optically active cyclohexenone oxime ethers I are suita-ble, both as isomer mixtures and in the form of the pure isomers, as herbicides especially for combating pli~nts from the Gramineae species. They are generally tolerated and are thus selective in broadleaved crops and in monocotyledons not belonging to the Gramineae. Some of the cyclohexenone oxime ethers I according to the invention are also suitable for selectively combating unwanted grasses in Gramineae.

The optically active cyclohexenone oxime ethers I, or herbicidal agents containing them, may be applied for instance in the form of directly sprayable solutions, powders, su3pensions (including high-percentage aqueous, oily or other suspensions), dispersions, em~lsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering.
The forms of application depend on the purpose for which the agents are being used, but they should ensure as fine a -~
distribution of the active ingredients according to the invention as possible.

The compounds I are generally suitable for the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct. Suitable inert additives are 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 hydrocar-bons, e.g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, chlorobenzene, isophorone or strongly polar solvents such as N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrroli-done or water.

Aqueous formulations ~ay be prepared from emulsion concen-trates, dispersions, pastes, wettable powders or water-dis-persible granules by adding water. To prepare emulsions, pastes or oil dispersions the ingredients as such or dis-solved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsi-fie~s. ~owever, concentrates which are suitable for dilution with water may also be prepared from active ingredient, O.Z. 0050/43017 ` ` 212~ 121 wetting agent, adherent, dispersing or emulsifying agent and possibly solvent or oil.
., ~
Surfactants are: alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, e.g., ligninsul-fonic acid, phenolsulfonic acid, naphthalenesulfonic acid and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylaryl sulfonates, and alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of fatty alcohol glycol ethers, condensation product~ of sulfonated naphtha-lene and naphthalene derivative-~ with formaldehyde, con-densation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octyl-phenol ethers, ethoxylated isooctylphenol, ethoxylatedoctylphenol and ethoxylated nonylphenol, alkylphenol poly-glycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyox-yethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin- -sulfite waste liquors and methyl cellulose.

Powders, dusts and broadcasting agents may be prepared by :~
mixing or jointly grinding the active ingredients with a solid carrier. -~
- - ~ .
Granules, e.g., coated, impregnated and homogeneous gran-ules, may be prepared by bonding the active ingredients to solid carriers. Solid carriers are mineral earths such as silicic acids, silica gels, silicates, talc, kaolin, atta-pulguQ clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium ~ ~
surfate, magnesium oxide, ground plastics, fertilizers such -~-as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain meals, bark -meal, wood meal and nutshell meal, cellulosic powders or other solid carriers. -~0 The formulations contain generally between 0.01 and 95, and preferably between 0.5 and 90, % by weight of active ingre-dient. The active ingredients are used in a purity of 90 to : '' 3~ 1 2 9 1 2 1 z . 0050/430l7 100, and preferably 95 to lO0, % (according to the NMR
spectrum).

Examples of formulations are as follows:

I. A solution of 90 parts by weight of compound no. 2.05 and 10 parts by weight of N-methyl-a-pyrrolidone, which is suitable for application in the form of very fine drops.

II. A mixture of 20 parts by weight of compound no. 2.12, 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 dodecylbenzene~ulfonic acid, and 5 parts by lS weight of the adduct of 40 moles of eth~lene oxide and 1 mole of castor oil. By finely dispersing the mixture in 100,000 parts by weight of water~ an aqueous dispersion containing 0.02wt% of the active ingredient is obtained.

III. An aqueous dispersion of 20 parts by weight of com-pound no. 4.20, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide and l mole of castor oil. A mixture of this dispersion with 100,000 parts by 2S weight of water contains 0.02wt% of the active ingredient.

IV. An aqueous dispersion of 20 parts by weight of compound no. 4.12, 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction having a boilin~ point of ;~
from 210 to 280C, and 10 parts by weight of the adduct of -~
40 moles of ethylene oxide and 1 mole of sastor oil~ The mixture of this dispersion with 100,000 parts by weight of water contains 0.02wt% of the active ingredient.

V. A hammer-milled mixture of 80 parts by weight of com-pound no. 4.19, 3 parts by weight of the sodium salt of diisobutylnaphthalene-a-sulfonic acid, 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel. By finely dispersing the mixture in 20,000 parts by weight of water, a spray liquor containing O.lwt~ of the active ingredient is obtained.

-~2 ~.Z. 0050/43017 `: 212~121 VI. An intimate mixture of 3 parts by weight of compound no. 6.01 and 97 parts by weight of particulate kaolin. The dust contains 3wt% of the active ingredient.
VII. An intimate mixture of 30 parts by weight of compound no. 6.05, 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil sprayed onto the surface of this silica gel. This formulation of the active ingredient exhibits good adherence.
VIII. A stable aqueous dispersion of 40 parts by weight of compound no. 6.11, 10 parts of the sodium salt of a phenol- -sulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water, which dispersion can be further diluted.
~ .:
IX. A stable oily dispersion of 20 parts by weight of compound no. 6.12, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil.

X. A hammer-milled mixture of 1~ parts by weight of com-25- pound no. 2.01, 4 parts by weight of the sodium salt of diisobutylnaphthalene-a-sulfonic acid, 20 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a ;
sulfite waste liquor, and 38 parts by weight of silica gel and 38 parts by weight of kaolin. By finely disper~ing the mixture in 10,000 parts by weight of water, a spray liquor containing O.lwt~ of the active ingredient is obtained.

The active ingredients or the herbicidal agents containing th~m may be applied pre- or postemergence. If certain crop 3S plants tolerate the active ingredients less well, applica-tion 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 uncovered soil or the leaves of unwanted plants growing beneath the crop plants (post-directed, lay-by treatment).

33 O.Z. 0050/43017 ` 212~121 The application rates depend on the objective to be achieved, the time of the year, the plants to be combated and their growth stage, and are from 0.001 to 3, preferably 0.01 to 1, kg of active ingredient per hectare.
In view of the numerous application methods possible, the optically active cyclohexenone oxime ethers I or the agents containing them may also be used in a further number of crops for eliminating unwanted plants. Those which follow are given by way of example:
_ . . . ~ .
Allium cepa onions _ _ .
Ananas comosus pineapples .
15 Arachis hypogaea peanuts (groundnuts) Asparagus officinalis asparagus _ _ .
Beta vulgaris spp. altissima sugarbeets _ Beta vulgaris spp. rapa fodUer be~ts Brassica napus var. napus rapeseed Brassica napus var.napobrassica swedes _ ' Brassica rapa var. silvestris _ _ _ _ : : ~
Camellia sinensis tea plants _ _ _ ~ .
Carthamus tinctorius safflower _ _ _ ~
Carya illinoinensis pecan trees , _ _ _ Citrus limon lemons _ _ _ _ _ _ _ Citrus sinensis orange trees _ _ _ . ~
Coffea arabica (Coffea canephora, coffee plants 30 Coffea liberica) . _ ~T . ,, _ _ Cucumis sativus cucumbers _ _ _ Cynodon dactylon Bermudagrass ~ .
Daucus carota carrots .~ . . . _ Elais guineensis oil palms _ _ _ _ _ Fragaria vesca strawberries _ _ , , ~
Glycine max soybeans _ , _ _ _ _ _ _ Gossypium hirsutum (Gossypium cotton arboreum, Gossypium herbaceum, 40 Gossypium vitifolium~
Helianthus annuus sunflowers _ .
Hevea brasiliensis rubber plants _ 34 o.Z. 0050/43017 :-`` 212~l21 . , Hordeum vulgare barley ~ . 1 s ~ _ lus hops Ipomoea batatas sweet potatoes 5 Juglans regia walnut trees _ Lens culinaris lentils Linum usitatissimum flax Lycopersicon lycopersicum tomatoes Malus spp. apple trees ` .: .
Manihot esculenta cassava Medicago sativa alfalfa (lucerne) ~:~
.
Musa spp. banana piants ..................................... ............................ ... .................................... . ~:
Nicotiana tabacum (N. rustica) . tobacco :
.
lS Olea europaea . . olive trees Oryza sativa rice .
Phaseolus lunatus limabeans :: :
: : ~
Phaseolus vulgaris snapbeans, green be-ans, dry beans Picea abies Norway spruce , .-~
Pinus spp. pine trees -~ ., .
Pisum sativum English peas : ~
~.
Prunus avium cherry trees ~ .
. : ~ .
~J Prunus persica peach trees .-~
. i.
Pyrus communis pear trees :-.
Ribes sylvestre redcurrants Ricinus communis castor-oil plants _ 30 Saccharum officinarum sugar cane _ Secale cereale rye Solanum tuberosum Irish potatoes ~ ~:
Sorghum bicolor (s. vulgare) sorghum .
35 Theobroma cacao cacao plants .
Trifolium pratense red clover Triticum aestivum wheat Triticum durum wheat Vicia faba tick beans Vitis vinifera grapes .
Zea mays Indian corn, sweet corn, maize -O.Z. 0050/43017 ` 2129121 To increase the spectrum of action and to achieve synergis-tic effects, the optically active cyclohexenone oxime ether~
I may be mixed and applied together with numerous represen-tatives of other herbicidal or growth-regulating active 5 ingredient groups. Examples of suitable components are ;
diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazi- ;~
nones, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarba-mates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran deriva-tives, cyclohexane-1,3-dione derivatives bearing in the 2-position for example a carboxy or carbimino group, quino-linecarboxylic acids, imidazolinones, sulfonamides, sulfony- -~
lureas, thetero)-aryloxyphenoxypropionic acids and salts, e~ters, amides thereof, etc. --~
lS
It may also be useful to apply the compounds I, 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. Further interest 20 attaches to the miscibility with solutions of mineral salts `
used to remedy nutritional or trace element deficiencies.
Non-phytotoxic oils and oil concentrates may also be added. -~

Use examples -The herbicidal action of the unsaturated cyclohexenone oxime ethers of the formula I is demonstrated in greenhouse experiments:

The vessels employed were plastic flowerpots filled with a sandy loam containing about 3.0% humus. The seeds of the test plants were sown separately, according to species.

For- the preemergence treatment, the active ingredients emulsified or suspended in water were applied immediately after the seeds had been sown, and sprayed through finely distributing nozzles. The vessels were lightly sprinkler-ir-rigated 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.

36 O.Z. 0050/43017 `` 212~121 For the postemergence treatment, plants were used which had been sown in the pots and grown there, or they were grown separately as seedlings and transplanted to the pots a few days before treatment. The plants were grown, depending on -~
5 growth form, to a height of 3 to 15 cm before being treated ~-with the compounds, suspended or emulsified in water. The application rates for postemergence treatment were 0.06 and 0.03 kg/ha. -:: -The pots were set up at temperatures, specific to this species, of ~0 to 35C, or 10 to 25C. The experiments were run for from 2 to 4 weeks. During this period the plants -- ;
were tended and their reactions to the various treatments ;
assessed.
The assessment scale was O to 100, 100 denoting nonemergence "~
or complete destruction of at least the visible plant parts, and O denoting no damage or normal growth.

The plants used in the greenhouse experiments were Echinoch-loa crus-galli, Oryza sativa, Setaria italica and Setaria viridis.

Compounds 4.12 and 4.20, applied postemergence at a rate of 25 0.06 or 0.03 kg/ha, controlled unwanted grasses very well -~
and were simultaneously tolerated by rice as an example for ~`
a crop plant.

Claims (9)

We claim:

1. Mixtures of optically active cyclohexenone oxime ethers, of R- or S- configuration in the oxime ether moiety, of the general formula I

I

where the substituents have the following meanings:

R1 is a C1-C6-alkyl group;
X is nitro, cyano, halogen, C1-C4-alkyl or C1-C4-haloal-kyl;
n is 0 to 3 or 1 to 5 if all the X's are halogen;
R2 is a C1-C4-alkoxy-C1-C6-alkyl or C1-C4-alkylthio-C1-C6-alkyl group;

a C3-C7-cycloalkyl group or a C5-C7-cycloalkenyl group, these groups being unsubstituted or bearing from one to three substituents selected from a group consisting of C1-C4-alkyl, C1-4-alkoxy, C1-C4-alkylthio, C1-C4-haloal-kyl, hydroxyl and halogen;

a 5-membered saturated heterocycle which contains one or two oxygen and/or sulfur atoms as heteroatoms and which is unsubstituted or bears from one to three substituents - selected from a group consisting of C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio and C1-C4-haloalkyl;

a 6- or 7-membered heterocycle having one or two oxygen or sulfur atoms or one oxygen and one sulfur atom as he-teroatoms and which is saturated or mono- or diunsatura-ted, the heterocycle being unsubstituted or bearing from one to three substituents selected from a group consi-sting of hydroxyl, halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio and C1-C4-haloalkyl;

a 5-membered heteroaromatic, containing one to three he-teroatoms selected from the group consisting of one or two nitrogen atoms and one oxygen or sulfur atom, this heteroaromatic being unsubstituted or bearing from one to three substituents selected from a group consisting of halogen, cyano, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-al-kylthio, C1-C4-haloalkyl, C2-C6-alkenyl, C2-C6-alkenyloxy and C1-C4-alkoxy-C1-C4-alkyl;

a phenyl or pyridyl group, these aromatics being unsub-stituted or bearing from one to three substituents se-lected from a group consisting of halogen, nitro, cyano, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-halo-alkyl, C3-C6-alkenyloxy, C3-C6-alkynyloxy and an amino group -NRaRb, where Ra is hydrogen, C1-C4-alkyl, C3-C6-alkenyl or C3-C6-al-kinyl and Rb is hydrogen, C1-C4-alkyl, C3-C6-alkenyl, C3-C6-alky-nyl, C1-C6-acyl or benzoyl which if desired may in turn bear from one to three radicals selected from a group consisting of nitro, cyano, halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio and C1-C4-haloalkyl;

and the agriculturally utilizable salts and esters of C1-C10-carboxylic acids and inorganic acids of compounds I, with the proviso that the mixtures contain at least 75 mol% of isomers of R-configuration in the oxime ether moiety.

2._ Optically active cyclohexenone oxime ethers I as set forth in claim 1 having R-configuration in the oxime ether moiety.

3. A method of manufacturing mixtures of optically active cyclohexenone oxime ethers I as set forth in claim 1, wherein a cyclohexenone of the formula II

II

is reacted in conventional manner in an inert organic solvent with a mixture of optically active hydroxylami-nes of the formula III

III

or with a salt of such optically active hydroxylamines.

4. A herbicidal agent containing inert additives and a her-bici?ally effective amount of a mixture of optically ac-tive cyclohexenone oxime ethers I as set forth in claim 1.

5. A method of combating the growth of unwanted plants, wherein a herbicidally effective amount of a mixture of optically active cyclohexenone oxime ethers I as set forth in claim 1 is allowed to act on the plants, their habitat or their seed.

6._ Mixtures of optically active hydroxylamines having R-and S-configuration of the formula III

III

where X is nitro, cyano, halogen, C1-C4-alkyl or C1-C4-halo-alkyl;
and n is 0 to 3 or 1 to 5 when all X's are halogen, with the proviso that the mixtures contain at least 75 mol% of isomers of R-configuration.

7. Optically active hydroxylamines III as set forth in claim 6 having R-configuration.

8. A method of manufacturing mixtures of optically active hydroxylamines of the formula III as set forth in claim 5, wherein a mixture of optically active 2-phenoxypropyl compounds of the formula IV

IV

where L is a nucleophilically substitutable leaving group, _ is reacted in the presence of a base with a cyclic hy-droxyimide of the formula V

V

where D is C2 or C3-alkylene, C2-alkenylene or a 5- or 6-membered ring which is saturated or mono-, di- or tri-unsaturated and may if desired contain a nitrogen atom as ring member, and the product VI

VI

is cleaved acidically or basically.

9. A method as claimed in claim 8, wherein the optically active hydroxylamine III is liberated from the product VI by means of ethanolamine.