CS251776B2 - Herbicide and method of its efficient component production - Google Patents

Abstract

The invention relates to cyclohexenol derivatives of the formula <IMAGE> in which R<1>, R<2>, R<3>, X and A have the meanings mentioned in the description, a process for the preparation of these compounds and their use for the control of undesired plant growth.

Description

The present invention relates to herbicidal compositions comprising as active ingredient novel cyclohexenone derivatives. the invention relates to a process for the preparation of these novel compounds.

It is already known to use herbicides which contain cyclohexenol derivatives as active ingredients for controlling undesired grass weeds in dicotyledonous plant cultures (cf. DE-OS 24 61 027). ‘

It has now been found that the cyclo-hexene-4-derivatives of the general formula (I)

O-A

R ^!

N- OR ^J <7 '

C in which

R @ ¹ represents a pyridyl group, a tetrahydropyranyl group, a trihydropyrimethyl group, a 1-oxotetrahydrothiopyranyl group, a 1,1-detroltrihydrothiopyranyl group, all of which are optionally substituted by a maximum of two C1-4 alkyl groups furthermore, optionally at most three methyl groups is a substituted cycloalkyl group having from 3 to 12 carbon atoms, optionally containing up to two double bonds, and furthermore a bicyclic ring system of up to 12 carbon atoms or a C1 -C4 alkoxy group. ring members which optionally contain up to two α atoms and up to two atoms from the group consisting of oxygen and sulfur, further being a radical of formula

Y -

in which

R ¹³ represents a C 1 -C 4 -alkoxy group, a C 2 -C 4 -alkoxyalkyl group or, optionally, a halogen-substituted phenyl or benzyl group,

Y is oxygen or sulfur; and

13

R is a chain of up to 4 unsaturated atoms, provided that when R is a C1-C4 alkyl group, Y is a sulfur atom and

R is an alkylene chain of up to 4 carbon atoms, then A is not a reriooyl group, a benzenesulfonyl group, or a lower alkenyl or alkenoyl group,

and.

furthermore represents a phenyl group or up to three substituents selected from the group consisting of halogen, a C1-C4 alkyl group, a C1-C4 alkoxy group, a substituted phenyl group, provided that when R &lt; ^{1 &gt}; an alkylphenyl group, a furyl group, a thienyl group, or a phenyl group as defined hereinbefore, then A is not a further defilated alkylthyl group, an alkanoyl group, a benzoyl group, a benzenesulfonyl group, a phenoxyacetyl group, an alkyl group or a benzyl group

X represents a hydrogen atom or a methoxycarbonyl group,

R is C 1 -C 4 alkyl,

R ³ is C 1 -C 3 alkyl, C 3 or C 3 alkenyl, C 3 or C 4 haloalkenyl and C 1 to halogen or propargyl; and

A represents a ^b a ^b yte ^{to h} Proceed with the formula R ¹⁵ E.

in which

R ¹⁵ represents a methylene group, a carbonyl group or a sulfonyl group and

E represents an alkyl group or an alkenyl group in both cases having a maximum of 20 carbon atoms, a cyclopropyl group optionally substituted by a methyl group, further a styryl group or, optionally, at most three substituents selected from the group consisting of halogen, an alkyl group C 1 -C 4 -alkyloxy, C 1 -C 4 -alkoxy, nito, substituted phenyl or benzyl, or optionally halogen or methoxy substituted 1-methylbenzyl or 1,1-dimethylbenzyl or chloromethyl, alkoxymethyl C 1 -C 4 alkoxy, C 3 -C 9 acetoxymethyl or C 3 -C 9 alkoxycarbonyl, optionally up to three substituents from the group consisting of halogen, C 1 -C 4 alkyl carbon, in phenoxylo a tubular-substituted phen (alkoxyalkylene group having an optionally branched alkylene chain of not more than 5 carbon atoms or a heterocyclic radical having 5 or 6 ring members and having 1 to 2 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur; and which is optionally substituted by C 1 -C 4 alkyl, or represents a radical of formula

in which

R ⁴ - represents a phenyl ^{to Ter} is substituted ^to to ^t ri ^t OVL luommethy ^l) ts ^to u ^- ρinlt or

A represents a group of the general formula

About taking

G represents a phenylene group, a methylene group, an ethylene group or a propylene group, and

3

X, R, R and R are as defined above, or

A represents a group of the general formula

where

9 10

R ^a , R a and R ^{A are} each independently C 1 -C 4 alkyl or phenyl; or

A represents a group of formula

wherein Y groups independently represent oxygen or sulfur

12

R and R signified! alkyl groups having 1 to 4 carbon atoms are herbicidally active.

Accordingly, it is an object of the present invention to provide a herbicidal composition, characterized in that it contains at least one cyclohexenol derivative of the formula I as defined above as an active ingredient.

These herbicidal compositions are, depending on the type of plant to be controlled and their compatibility with crop plants, either selective herbicides or generally for controlling and suppressing undesirable vegetation, including inhibiting the growth of vegetative and geaerative parts of plants in crop plants. where they are unusable, disturbing or even disadvantageous.

R ^{1 in} general formula I represents m ^py rid ^y tetrhhydrojjy Target residue Target-RAR-radical tetrahytfrothiopyranylový residue 1 or residue-oxotetrrhydrsthiopyraaylsvý KL-dloxotetrahydrothiopyranylový residue such as pyrid-2-yl radical pyridin ^ -yl radical, pyrid 4-yl radical tetrahydrsoyrrn 3-ylsvý residue tetrahydrsthiooyrrn 3-ylsvý residue, ^L-y oxotetrahydrothiop RRA Target 3- ^yl radical, the 1, L-dSoxotetaah drothSop ^{y y y} RRA 3- lsvý The rest 2, 6-dimetthltetrahydropyran-l-yl radical, 2,6-3-dimethhltttrahldrsthisolrra llsvý The rest ^6-yl meehhoχlterrhydrop wound-lilac residue. R @ 1 may furthermore be optionally substituted with at most three methyl groups substituted C3 -C12 cycloalkyl group, which may optionally contain up to two double bonds, such as a cyclopropyl group, a cyclohexyl group, a cyclooctyl group, a cyclododecyl group, a cyclohexyl-3-enyl group , L-clklohex eallovou, 2-enyl meehylclkl · L-eallovsu group, 4-meehylClklohex-2-enyl, 2,6,6-trimtthllclklshex-l-enyl, ^2,6,6-y trimethylc klohex A 2-enyl group, a clododec-4,8-ditayl group.

R ¹ may additionally represent a bicyclic ring system having up to 12 ring members, optionally containing up to two double bonds and up to two atoms selected from the group which is formed by an oxygen or sulfur atom. Examples include 4a, 7,8,8a-tetrahydro-2H, 5H-pyrano [4,3-b] pyra ^n-3-yl sk ^{u u nu} pi, 3 and ^4,4, 7,8,8a - · ^h exlhydro ^2н-5H - ^py rlno ^{£ 4, 3-b] pyridin-3- yl} rIn nominal StopIN 2,6,6-trimethyl-bicyclo ^y LBIC ^y | [3, ^1, l ^ e ^ ^ n- - group.

^R may further ^{be a} group of the formula

where

Y

is C1-C4alkyl or C1-C4alkoxyalkyl or optionally halogen-substituted phenyl or benzyl, is oxygen or sulfur, and is an alkylene chain of up to 4 carbon atoms.

Examples include ^2-yl lth0o LTH ^p-n oo nominal ^pyridine, 2- (chlorbenzzl) thioethyoovou, 2-meehooyyn-propyl, 2-lmlthyl2 mlthoxylthylovou, 1- (2-n-butoxyethoxy-aminobenzyl group .

^r! the ^d But does fánylovou quick match no ^b by up to three sufabsitoen · t ^y selected from StopIN consisting of halogen, alkyl having 1 to 4 carbon atoms and alkoyyskupinou having 1 to 4 carbon atoms, phenyl, substituted phenyl such as 4-melhylflnylovou group, lthyllenylovou-4, 4-mmthoxyfln lovot ^yl group, 3-mmlhyУflnylovou quick match and 3,4-dimmehoxyfenylovou group.

R in formula (I) represents straight-chain and branched-chain alkyl groups having 1 to carbon atoms, i. methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl.

^RJ general vzooci ¹ may mean ^p ro ^p arg ^y l ^ s ^ ou StopIN altylovou quick match with ^one and the ^carbon atoms, alkenyl having 3 or 4 carbon atoms or haloalkenyl of 3 or 4 carbon atoms which may contain up to three halogens as substituents such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, and h-1-chloropropene A 3-yl group, a 2-chloro- ^p -1-l-3- ^yl group, a 1,3-dichloro-1-en-3-yl group, a 1,1,2-trichloro-prenen-3-yl group group.

A may be a group of the formula R ¹⁵ E, wherein R ¹⁵ is a methylene group, a carbonyl group or a sulfonyl group with E being an alkyl group or a C k-C ^ group having a maximum of 20 carbon atoms, in particular a maximum of 18 carbon atoms.

A is, for example, ethyl, propyl, acetyl, pivaloyl, butyryl, luroyl, palmitoyl, stearyl, oleoyl, mehlyysulfonyl, ethylsulfonyl, proppysulfonyl, butylsulfonyl.

In addition, E may be a cyclopropyl group, which is optionally substituted by a methyl group, such as a cyclopropyl group or a methylcyclopropyl group.

E may furthermore be a maximum of three substituents selected from the group consisting of halogen, C1-C4alkylalkyl, C1-C4alkoxy and nitro, substituted phenyl or Senzyl, or optionally halogen or methoxy substituted by 1, 1-dimethylbenzyl or 1-methylbenzyl, for example, methoxyphenyl, methoxylphenyl, methyl, dichloromethoxyphenyl, trichloroethyl, benzyl, fluorobenzyl, chlorobenzyl, methoxybenzyl, alpha-methylmethyl, alpha-methylmethyl, alpha-methylmethyl a group, ala-methyl-bromo-nyl group, an alpha-methyl-thyloxybenzyl group, an alpha, af-di-dimethylene group, an alpha, afa-dimethyl (hydroxypropyl) group.

E may furthermore be a chloromethyl group.

E is furthermore an alkoxymethyl group having 1 to 4 carbon atoms in the alkoxy moiety, an acetoxymethylmethyl group or a (C 3 -C 9) alkoxycarbonylalkyl group, such as a mithoxymethyl group, a methoxymethyl group, a Suthoxymethyl group, an ethoxycarbonylmethyl group, a tertiaryloxy group.

Furthermore, E is optionally at most three substituents selected from the group consisting of halogen or (C1 -C4) alkyl in the phenoxy moiety of a substituted phenoxyalkyl radical of up to 5 carbon atoms in the alkylene moiety, such as phenoxymethyl, chloroenoxymethyl, dichloro, of the hydroxylthyl group, a chloromethylphenoxymethyl group, a trihrothenylmethyl group, a methylphthylmethyl group, a dichlorotnoxyethyl group, a chloromethylphenoxymethyl group, a trihrrrroxythyl group, a chloromethenoxypropyl group, a chlorotenoxypropyl group.

E may also optionally be a heterocyclic group having 5 or 6 ring members and one or two htttrratoms selected from the group consisting of nitrogen, oxygen and sulfur, for example a furyl group, an ethertriethyl group, a diethylruryl group, is a azyl group, a methisulfoxazolyl group, a trenyl group, a propyl group.

A may also be a group of the formula

in which

A represents a trifluoromethyl-substituted phenyl radical.

may further be a group of the formula wherein

means a phenylene group, a methylene group, an ethylene group or a p-plene group; and

3

R, R, and R are as defined above.

A may furthermore be a group of the general formula

Si.

wherein ^{R8, R9} and ^R19 independently of znameeají ^{runs for} asylum with oup having ^1-4 carbon atoms, n ^e b ° phenyl groups.

I ^to about ^AMPLE ice ^{b y} z ^es yl R ^8, R ⁹ and ^{R 10} is m ^; ^Ao mmehylovou sJcupinu state, e ^ nominal, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl group, ^{Y is} nominal and phenyl.

A furthermore represents a group of the general formula

₁₂

Y \ ^ y - R ^y in which ZB znammenaí area Y are independently oxygen or sulfur and

R and R are C 1 -C 4 alkyl, such as methyl, ethyl, n-propyl, isopropyl.

Preferred deeiv ^v t ^y ^ c ^ o lohexenolu general formula I are those in ^companies whose ^R1 is ⁱⁿ tetaahydropyranylovou group tetrahydrlthiop raaylovl ^y> u, 1- <lxotetrahydr (lthilpyranylovou, 1,1-dilxltetrahydrlthlopyraaylovlu group, especially 3-tetaahydrlpyraa a 1-oxylthiopyrrolidin-3-yl group, a 1-oxoethylthiopyrrolidin-3-yl group, a 1,1-dihydroethylthiopyrrolidin-3-yl group and a 1-oxylthiopyrrolidin-3-yl group.

Other preferred cyclohexenol derivatives are those derivatives of formula (I) wherein X is kc. ·

The cyclohexenol derivatives of the formula I can be prepared by reacting the compounds of the formula II

(II),

in which

3

R, R, R and X maa! the meanings given under formula I with the compounds of the general formula

A - Z, in which

A has the above meanings and

Z represents a halogen atom or a tosyl radical.

The rea ^ction was carried out in přítomnooSi Mze at temperatures from -5 ° C up to the reflux temperature ^y SMMS in an inert solvent. Optionally, the base may be used in aqueous solution. Depending on the miscibility, the reaction is then carried out in a homogeneous phase or in a two-phase system. In the latter case, phase transfer catalysts such as ammonium and phosphonium salts can be used to accelerate the reaction.

In addition, azole derivatives such as imidazole, pyrazole, pyridine as well as derivatives thereof, for example 4-piperidinopyridine or 4-dimethyl-aminocpridine, can be used to accelerate the reaction.

Suitable solvents are dimethylformamide, dimethyloormamide, benzene, toluene and optionally chlorinated hydrocarbons such as chloroform, dichloromethane, dichloroethane, hexane, cyclohexane, ketones such as acetone, butanone, esters such as ethyl acetate, ethers such as diethyl ether, dioxane, tetrahydrofuran.

Suitable bases are, for example, carbonates, hydrogen carbonates, acetates, alkoxides, hydroxides or oxides of alkali metals or alkaline earth metals, in particular sodium, potassium, magnesium and calcium. In addition, organic bases such as pyridine or tertiary amines can also be used.

The starting materials used for the synthesis of the compounds according to the invention corresponding to the general formula (II) can also be used in the form of salts. The reaction is then carried out as described above without addition of bases.

The compounds of formula (II) are obtained by known methods:

· «

R ¹ -CH = CH-C-CH ₃

o ^Z '' /

СН ₃ -С-СН2-СООСНз / CHgON

X = H; COOCH3

The following examples illustrate the preparation of the novel cyclohexenol derivatives of formula I.

Parts of the tonnage to the parts by volume are in the examples as kg: liter.

1 H-NMR spectra data are expressed in bold (ppm) and refer to tetramethylsulfine as an internal standard. Deuterochloroform was used as solvent. Signal abbreviations have the following meanings:

s = singlet, U = doublet, t = triplet, q = kvaatet, m = mytiplet, the strongest signal.

Example 1

3.1 parts of 2-hmoonostního dthoxyaminnbutyliden "5- (l tdtrlhydroppral ----) cyklohexxan-, 3-dione, 1.2 parts hmoSnostoího trdetУylrminr and 0.2 parts of 4-hmoSnostníhs dioethylaoinospyidirlu in about 50 ^ emovýč ^says Lech ricMormethanu cool to 0 ° C.

1.4 parts by weight of benzoyl chloride are added dropwise to this solution at temperatures between ⁰ ° C and 5 ° C. The mixture was then allowed to warm to room temperature, stirred for one more hour, washed with 10% hydrochloric acid, twice with 5% sodium hydroxide solution and water, dried over sodium sulfate and the solvent was distilled off. There was obtained 1-isyl-oxy-2- (N-ethosyl-butylimiddyl) -5- (tetrahydro-pylaanZ-yl) -cyclothe-1-ene-3-yl as an oil (active ingredient no. 1).

1 H-NMR spectrum: 0.92 (t), 3.95 (t), 7.65 (rn).

Example 2

8.0 parts by weight of 2-ththoxyaain-tutulidee-5- (tetrahlertpylan-3-z-1) cyclothexane-1,3-dione is dissolved in 50 parts by volume of acetone, then 1.1 parts by weight of sodium hydroxide in 5 parts by volume of water are added The mixture is stirred for 30 minutes, cooled to 0 DEG C. and 2.2 parts of acetonitrile are added dropwise at this temperature.

The reaction mixture was then stirred at ambient temperature for 2 hours, the solvent was distilled off in vacuo, the residue was dissolved in ethanol-Chosieu, the insoluble materials were filtered, extracted twice with 5% sodium hydroxide solution, and the extracts washed with water until a neutral reaction. The mixture was dried over magnesium sulphate and the solvent was removed in vacuo.

There was thus obtained 1-methyl-2- (N-ethoxybutolioidos) -5- (tetrahlertpylan-3-z-1) cyclothex-1-en-3-sn as an oil.

(Active substance No 2.

H-NMR ^with pektrum: 0.95 (t) ^1, 30 (t), ^2, 20 (2, ^4, 15 (q).

Peak a d 3

6.5 parts by weight of sodium 2-thienyl-2-thienyl-n-tutulidesl-5- (ppyid-3-yl) cyclohexane-1,3-di-tin are suspended in diethane and 1.6 parts are added dropwise. % by weight of aceepl chloride at room temperature. The reaction mixture was stirred for 2 hours then washed with 5% sodium hydroxide solution and water, dried over sodium sulfate and the solvent was evaporated in vacuo. 1-Actyl-2- (N-ethylbutylidol) -5- (pplie-3-p1) eplothe-1-e1-1-s-1 - is obtained in the form of a viscous oil (active substance No 3).

H-NMR spectrum: ¹ 0 ^{(t) 4} 0 ^(q), 8. 6 (m).

The following compounds of formula I are obtained in the same manner

active substance number ^R1 . X r2 r3 AND data ^1h -NMR spectrum 4 t et r a hydropy r n - -3 - у 1 H n-proppl ethyl 4 -m ^ tthoKyben- 0.85 (t), 3.90 (s). zoyl 7.0 (d) 5 t et r and wounds hydrops - -3 - у 1 H n-propyl ethyl 2-m ^ tt ^ h ^ y-ben- 0.88 (t), 1.10 (t), zoyl 8,0 (d) 6 tetrahyertpyran-3-yl H n-propyl ethyl 4-tert-butyl- 1.40 (s), 4.0 (q), benzoy1 7.50 (d)

'continued table effective

substance number r1 X R ^{2 r3} AND data @ 1 H-NMR spectra 7 tetrahydropyran-3-yl H --propyl ethyl 4-chlorobenzyl 0.90 (t), 4.0 (q), 7.50 (d) 8 tetrahydropyran-3-yl H --propyl ethyl 4 - itrobe-zoyl 3.95 (q), 8.40 (m), 9 tetrahydropyran-3-yl H --propyl ethyl butyryl 1,25 (t), 1.90 (m), 3.35 (m) 10 tetrahydropyran-3-yl H --propyl ethyl ben-zsU fmyl 1.82 (t), -, 4 (we, 6.62 (d) 11 tetrahydropyran-3-yl H --propyl ethyl ethyisuifo-γ1 0.92 (t), 3.35 (q), 4.10 (q) 12 tetrahydropyran-3-yl H --propyl ethyl meehhlsuUfo-yl 0.90 (t), 3.20 (s), 4.10 (q) 13 tetrahydropyran-3-yl H --propyl ethyl phenylacetyl 1.60 (m), -, 75 (s), 7.30 (m) 14 tetrahydropyran-3-yl H --propyl ethyl -, S-dichloro- 0.87 (t), 7.65 (m), benzoy1 7.95 (m) 15 Dec tetrahydropyran-3-yl H --propyl ethyl chloroacetyl 0.92 (t) ', 4.0 (s), 16 tetrahydropyran-3-yl H --propyl ethyl 2, S-dichloro-O- 0.90 (t), 1.65 (m), -methoxybenzoyl 7.42 (d) 17 tetrahydroppyan-3-yl H --propyl ethyl -, S-Dimethyl- 1.10 (t), 2.38 (s), benzoyl 3.30 (m) 18 tetrahydropyran-3-yl H --propyl ethyl pival ^ l 0.88 (t), 1.26 (s), 4.10 (q) 19 Dec tetrahydropyran-3-yl H --propyl ethyl lauroví 20 May tetrahydropyran-3-ol H --propyl ethyl palmitoyl 1,25 (m), 2.40 (m), 4.10 (q) 21 tetrahydropyran-3-yl H --propyl ethyl stearoyl 0.90 (t), 1.30 (m), 4.10 (q) 22nd tetrahydropyran-3-yl H --propyl ethyl oleoyl 0.86 (t), 1,25 (m), 5.40 (t) 23 tetrahydropyra-3-yl H --propyl ethyl (4-Methoxyphenyl) acetyl 24 tetrahydropyran-3-yl H --propyl ethyl 2- (4-methoxy- 0,84 1 lt), 6.95 (m), phenyll-propio-yl 3.82 (with) 25 tetrahydropyran-3-yl H --propyl ethyl 2- (4-chloro-2- 1,25 (t), 485 (q), (methyl-ferioxy) propio-yl 7.15 (m) 26 tetrahydropyran-3-yl H --propyl ethyl 4- (2,4-dichloro- 1.60 (m), 2.17 (m), phenyloxyl) 7.18 (m) 27 Mar: tetrahydropyran-3-yl H --propyl ethyl 2-Methyl-2- 0.80 (t), 3.12 (m), -phenyl-propenyl 7.36 (m) 28 tetrahydropyran-3-yl H --propyl ethyl methoxyacety1 1.65 (m), 2.65 (m), 3.45 (with) 29 tetrahydropyran-3-yl H --propyl ethyl acetoxyaaeey1 1.65 (m), 2.20 (s), 4.15 (q) 30 tetrahydropyran-3-yl H --propyl ethyl 4-теehοχχsuUkc- 1,25 (t), 2.70 (m), -yl 3.70 (with)

: 51776 • continuation table active substance R ^{1 no}

3

XR ² R ³ A data ³ H-NMR ^with pectr ^a

31 tetrahydropyran-3-yl H --propyl 32 tetrahydropyran-3-yl H --propyl 33 tetrahydropyran-3-yl H --propyl 34 tetrahydropyran-3-yl H --propyl 35 tetrahydropyran-3-ol H --propyl 36 tetrahydropyran-3-yl H --propyl 37 tetrahydropyran-3-yl H --propyl 38 tetrahydropyran-3-yl H --propyl 39 tetrahydropyran-3-yl H --propyl 40 tetrahydropyran-3-yl H --propyl 41 tetrahydropyran-3-yl H --propyl 42 tetrahydropyran-3-yl H --propyl 43 te trahydropyran-3-yl H --propyl 44 tetrahydropyran-3-yl H ethyl 45 tetrahydropyran-3-yl H ethyl 46 tetrahydropyran-3-yl H --propyl 47 tetrahydropyran-3-yl H --propyl 48 tetrahydropyran-3-ol H --propyl

ethyl 2,6-dimethyl-3-furylcarbonyl 1.16 4.05 (t), (q) 2.26 (with) ethyl .2,5- <1ϊπθ11 ^ 1- 0.83 (t), 2.64 (with) -4-isoxazolylcarbonyl 4.00 (q) ethyl 5-isoxaaolyl- 2.75 (m), 7.10 (m) carbonyl 8.55 (m) ethyl 3 ^р у-1-carbonyl у1- ethyl 2-chУol --- pyli- 0.86 (t), 7.3 (m), dylcarbonyl 8.5 (m) ethyl 3,6-Dichloro-2- -pyridylcarbi- -yl ethi ^ l thie-4-ylacetyl 1,28 (m), 3.98 (with) 7.00 (m) ethyl Ci-rnamoyl 3.18 (q), 6.48 (d) 7.75 (d) ethyl cycloproppl- 1,25 (t), 2.55 (m) carbonyl 4.10 (q) ethyl 1-meehylcyclo- 0.82 (m), 1.30 (with) propylcarbonyl 3.20 (q) ethyl 2.2 <^ i.C ^ lor- prlpionyl ethyl --bu U у lsu lf l-р 1 1,25 (t), 3.90 (m) 4.15 (q) ethyl 3- (2 ^^^^ - 4) 1,25 (t), 3.90 (m) -tril 11ггп1 ^ Ур 1 ^ -оэр) - 6-Penzoyl 4.15 (q) ethyl 3- (2-Chloro-4-trillooroethylethyl-onyl) n-trobenzoyl allyl 3- (2-cCoolo44-ri-) fluoromethylphenoxy) -6-iriobooyl ethyl ^2- [4- (N-methylmethylnoxp) phenoxypropio-pl ethyl ^{2- [4 4} (4-yo pyyi ^{d- d} ^ - ^ ix ^ is ^1-IXY - - propio-pl ethyl 2- [⁴~ (--rifluir metthlpyid-2-^ylix^y) Foxy^l-

continued table active substance r! data number ^X H-NMR spectra

49 tetrahydropyran-3-yl H n-propyl 50 tetrahydropyran-3-yl H n-propyl 51 tetrahydropyran-3-yl H n-propyl 52 tetrahydropyran-3-yl H n-propyl 53 tetrahydropyran-3-yl H n-propyl 54 tetrahydropyran-3-ol H n-propyl 55 tetrahydropyran-3-ol H n-propyl 56 tetrahydropyran-3-yl H n-propyl 57 tetrahydropyran-3-yl H n-propyl 58 2-ethylthio-n-propyl H n-propyl 59 2-ethylthio-n-propyl H n-propyl 60 2-ethylthio-n-propyl H n-propyl 61 2-ethylthio-n-propyl H n-propyl 62 2-ethylthio-n-propyl H n-propyl 63 2-ethylthio-n-propyl H n-propyl 64 2-ethylthio-n-propyl H n-propyl 65 2-ethylthio-n-propyl H n-propyl 66 2-ethylthio-n-propyl H n-propyl 67 2-ethylthio-n-propyl H n-propyl 68 2-ethylthio-n-propyl H n-propyl 69 2-ethylthio-n-propyl  H n-propyl 70 2-ethylthio-n-propyl H n-propyl

ethyl 2- [4- (4-Trifluoromethyl-6-chloropyrid-2-yloxy) phenoxy] propionyl ethyl 2- [4- (6-chloro-2-quinoxalinoxy) phenoxy] propionyl ethyl 2- [4- (6-chlorobenz thiazol-2-yloxy) phenoxy] propionyl ethyl 2- [4- (5-chlorobenz- oxazol-2-yloxy) phenoxy] propionyl n-pro- benzoyl 0.75 (t), 2.6 (m), pollen 7.6 (m) n-pro- 2-methylbenzoyl Methyl pollen benzoyl 0.85 (t), 3.70 (with) 7.6 (m) propar- benzoyl 0.86 (t), 4.46 <d) gyi 7.45 (m) 3-chloro- 1.65 (m), 4.45 <d) allyl benzoyl 8.10 (d) ethyl butyryl ethyl acetyl ethyl benzyl 0.86 (t), 4.15 (q) 5.1 (with) ethyl methylsulfonyl 0.92 (t), 1.35 (d) 3.15 (WITH) ethyl phenylacetyl 1.6 (t), 4.1 (q), 7.32 (m) ethyl 3,5-dichloro- benzoyl ethyl chloroacetyl ethyl 2,5-dichloro-6- methoxyben zoy1 ethyl 3,5-dimethylbenzoyl ethyl pivaloyl ethyl stearoyl ethyl oleoyl ethyl (4-methoxyphenyl) acetyl

The following table is effective

substance number R ¹ X R ² R ³ AND ^d ata -NM ^R ^ ^H spectra 71 2-ethylthio-1-propyl H n-propyl ethyl 2- (4-methoxy- 1,27 (m) , 3.82 (s), phenyl) -yroyionyl 6.9 (d) 72 2-ethylthio-n-propyl II n-yropyl ethyl 2y (4-chloro-2- 0.87 (t) , 2.55 (m), - propionyl 7.1 (m) 73 2-ethylthio-n-propyl H n-propyl ethyl 4- (2,4-dichloro- 0.85 (t) , 4.05 (m), phenoxy) bbryryl 7.16 (m) 74 2-ethylthio-n-proyl H n-propyl ethyl 2-πίΗγ1-2- 0.85 (t) , 1.64 (s), -phenylyropionyl 7.35 (m) 75 2-ethylthio-n-propyl H n-propyl ethyl methooyiactyl 76 2-ethylthio-n-propyl H n-propyl ethyl acetoxyacctal 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 315-dimethyl- 2.45 (with) , 2,6 (s), isoya201-4- 4.02 (q) -ylcarbonyl 80 2-ethylthio-n-propyl H n-propyl ethyl 5-isoyazooylcarbonyl 81 2-ethylthio-n-propyl H n-propyl ethyl 3-ylidylcarbonyl 82 2-ethylthio-n-propyl H n-propyl ethyl 2-chloro-3-pyridylcarbonyl 83 2-ethylthio-n-propyl H n-propyl ethyl 3,6-dichloro-2-pyridylcarbonyl 84 2-ethylthio-n-propyl H n-propyl ethyl (2-thienyl) acetyl 85 2-ethylthio-n-propyl H n-propyl ethyl yivaloyl 86 2-ethylthio-n-propyl H n-propyl ethyl cycloproyyl- carbonyl 87 2-ethylthio-n-propyl H H ethyl d-meet (hl) cycloproyylcarbonyl 88 2-ethylthio-n-propyl H H ethyl 2,2-dichloro- • yroyionyl 89 2-ethylthio-n-propyl H H ethyl nyl 90 2-ethylthio-n-propyl H H ethyl 3- (2-Chloro-4-

-t ^ ri-U ^ oo ^ meth ^ ³ (phenooyl) -66nitrobenzoyl continued table effective

substance number ^r1 X ^{r2 r3} AND 91 2-ethylthio-n-pyopyl H ethyl ethyl 3- (2-Chloro-4-trifluoromethyl-phenoxy) -6-niroobenzoyl 92 2-ethylthio-n-propyl H ethyl allyl 3- (2-chloro-4-trifluoromethyl-1,4-oxo) -1-t-trobenzoyl 93 2-ethylthio-n-propyl H n-propyl ethyl 2- (4- (4-trifluoromethylphenoxy) phenoxy propionyl) 94 2-ethylthio-n-propyl H n-propyl ethyl 2- [4- (4-iodopyrid-2-lloxl) phthoxy] propionyl 95 2-ethylthio-n-propyl H n-propyl ethyl 2- [4- (4-difluoromethylpiperidin-2-lloxy) phenoxy] propionyl 96 ^{2-ethylthio-n-p} Y1 H n-propyl ethyl 2--4- (4-difluoro-meethy-e-chloropyrid-2-yloxy) -4-noxy 97 2-ethylthio-n-propyl H n-propyl ethyl 2- [4- (6-chloro-2-trifluoromethoxy) phenoxypropionyl 98 2-ethylthio-n-propyl H n-propyl ethyl 2- [4- (6-chlorobenzothiazol-2-yloxy) phenoxypropionyl 99 2-Ethylthio-n-propyl H n-propyl ethyl 2- (4- (5-chlorobenzooxzoo) -4-oxo) phenoxy; propionyl 100 ALIGN! 2-ethylthio-n-propyl H n-propyl ethyl lauroyl 101 2-ethylthio-n-propyl H n-propyl ethyl palmitoyl 102 2-ethylthio-n-propyl H n-propyl ethyl 2.4 - ^^ хузсс ^ у! 103 2-ethylthio-n-propyl H n-propyl ethyl butyldimeehy1sily * 104 2-ethylthio-n-propyl H n-propyl ethyl O, O-diethyl-4-phosphorus 105 tetrahydrothiopyran-3-yl H n-propyl ethyl - “m ^ ttУo: ^; ^ benzoyl 106 tetrahydrothiopyran-3-yl H n-propyl ethyl 2-ιηβ ^ 1- benzoyl 107 tetrahydrothiopyran-3-yl H n-propyl ethyl - t-butylbenooyl

0.90 <t), 2.50 (m) data HNMR with ^p ektra effective Continued table

substance Number ^r1 X ^{r2 r3} AND data ^ -NMR 108 tetrahydrothiopyran-3-yl H n-propyl ethyl 4-chlorobenzoyl 109 tetrahydrothiopyran-3-yl H n-propyl ethyl benzoyl 0.95 (t) 7.60 (m) 110 tetrahydrothiopyran-4-yl H n-propyl ethyl 111 tetrahydrothiopyran-3-yl H n-propyl ethyl bennoosuUfonyl 112 tetrahydrothiopyran-3-yl H n-propyl ethyl benzyl 113 tetrahydrothiopyran-3-yl H n-propyl ethyl meehylsuUfonyl 114 tetrahydrothiopyran-3-yl H n-propyl ethyl phenylacetyl 115 tetrahydrothiopyran-3-yl H n-propyl ethyl 3,5-dichloro-. benzoyl 116 tetrahydrothiopyran-3-yl H n-propyl ethyl chloroacetyl 117 tetrahydrothiopyran-3-yl H n-propyl ethyl 2,5-dichloro-4-methoxybenzoyl 118 tetrahydrothiopyran-3-yl H n-propyl ethyl 3,5-dimethylbenzoyl 119 tetrahydrothiopyran-3-yl H n-propyl ethyl pivaloy1 120 tetrahydrothiopyran-3-yl H n-propyl ethyl lauroyl 121 tetrahydrothiopyran-3-yl H n-propyl ethyl palmitoyl 122 tetrahydrothiopyran-3-yl H ethyl ethyl steaks! 1,25 (s), 2, 4.10 (q) 123 tetrahydrothiopyran-3-yl H n-propyl ethyl oleoyl 124 tetrahydrothiopyran-3-yl H n-propyl ethyl (4-methoxyphenyl) acetyl 125 tetrahydrothiopyran-3-yl H n-propyl ethyl 2-H-methoxyphenyl) propionyl 126 tetrahydrothiopyran-3-ol H n-propyl ethyl 2- (4-chloro-2-methylphenoxy) propionyl 127 tetrahydrothiopyran-3-ol H n-propyl ethyl 4- (2,4-Dichlorophenoxx) butyl 128 tetrahydrothiopyran-3-yl H n-propyl ethyl 2? -? - 2-phenylpropio-yl 129 tetrahydrothiopyran-3-yl H n-propyl ethyl те ^ окуюс ^! 130 tetrahydrothiopyran-3-yl H n-propyl ethyl acetoxyaaceyl 131 tetrahydrothiopyran-3-yl H n-propyl ethyl 4-methoxy-

succinyl spectra (q), (t), the following table effective

substance number R ¹ X R ² R ³ AND 132 tetrahydrothiopyran-3-yl H n-propyl ethyl 2,5-dimethyl-3-furylcarbonyl 133 tetrahydrothiopyran-3-yl H n-propyl ethyl 3,5-dimethyl-4-isoxazolylcarbonyl 134 tetrahydrothiopyran-3-yl H n-propyl ethyl 5-isoxazolylcarbonyl 135 tetrahydrothiopyran-3-yl H n-propyl ethyl 3-pyridylcarbonyl 136 tetrahydrothiopyran-3-yl H n-propyl ethyl 2-chloro-3-pyridylcarbonyl 137 tetrahydrothiopyran-3-yl H n-propyl ethyl 3,6-dichloro-2-pyridyl 138 tetrahydrothiopyran-3-yl H n-propyl ethyl (2-thienyl) acetyl 139 tetrahydrothiopyran-3-yl H n-propyl ethyl pivaloyl 140 tetrahydrothiopyran-3-yl H n-propyl ethyl cyclopropylcarbonyl 141 tetrahydrothiopyran-3-yl H n-propyl ethyl 1-methylcyclopropylcarbonyl 142 tetrahydrothiopyran-3-yl H n-propyl ethyl 2,2-dichloropropionyl 143 tetrahydrothiopyran-3-ol H n-propyl ethyl n-butylsulfonyl 144 tetrahydrothiopyran-3-yl H n-propyl ethyl 3- (2-chloro-4-trifluoromethylphenoxy) -6-nitrobenzoyl 145 tetrahydrothiopyran-3-yl H ethyl ethyl 3- (2-Chloro-4- (trifluoromethylphenoxy) -6-nitrobenzoyl 146 tetrahydrothiopyran-3-yl H ethyl allyl 3- (2-chloro-4-trifluoromethylphenoxy) -6-nitrobenzoyl 147 ' tetrahydrothiopyran-3-yl H n-propyl ethyl 2- [4- (4-Trifluoromethylphenoxy) phenoxy] propionyl . 148 tetrahydrothiopyran-3-yl H n-propyl ethyl 2- [4- (4-iodopyrid-2-yloxy) phenoxy] propionyl 149 tetrahydrothiopyran-3-yl H n-propyl ethyl 2- [_ 4- (4-Trifluoro-

methylpyrid-2-yloxy) phenoxy] propionyl

1.30 (t), 4.15 (q)

7.58 (t) data 'H-NMR spectra table continues CTA Iji with ^p-MR active ektra Units R-ID

3

XRR ³ A

150-tetryl-pyrimidin-3-yl-n-propyl

151 tetrahydrothiopyran-3-yl H n-propyl 152 tetrahydrothiopyran-3-yl H n-propyl 153 Tetraindro-ispyran-3-yl H n-propyl 154 trans-tetrahydris-pyrimidin-3-yl H n-propyl 155 tdtraУlUrstУisplrln-3´-yl H n-propyl 156 tetropyridin-3-yl H n-propyl 157 tdtraУydrstУispyrln-3tl1 H n-propyl 158 tetrlurothispyridin-3-yl H n-propyl 159 tdtrlУyUrstУiopyrln-3ty1 H n-propyl 160 pyriu-3-yl H ethyl 161 pyrrol-3-yl H n-propyl 162 pyrrol-3-yl H n-propyl 163 pyrrol-3-yl H n-propyl 164 pyrid-3-yl H n-propyl 165 pyrid-3-yl H n-propyl 166 pyrrol-3-yl H ethyl 167 pyrrol-3-yl H ethyl 168 pyrrol-3-yl H ethyl

ethyl 2- [4- (4-trifluoromethyl-6-chloropyrid-2-ylsayphenyl) phenyloxy] propionyl ethyl 2- [4- (S-chloro-4-quinoxylphenyl) phenoxypropionyl ethyl] -4- (6-chlorobenathiazole) Propylyl 2- [4- (6-chlorobenzoyl-4-yloxy) pyridylpropionyl] n -propenzoyl n -prop-2-methylbenzoyl polyl methyl benzoyl

for- benzoyl pargyl 3-chloro- allyl benzoyl ethyl 3, 1H-Chloroquinolin-8-yl ethyl the beer 1.26 (s), 2.45 (m) 7.61 (d) ethyl benzoyl 1.40 (m) 7.60 (m) 8.62 (m) ethyl oley! ethyl palmetoví 1,25 (s), 4.10 (q) 8.60 (m) ethyl 2-Methyl-2-pyridylspisnyl ethyl 3,5- &lt; 1 &gt; -1 &lt; 1 &gt; benzoyl ethyl benzoyl ethyl 4- (4 4 ^ ^ <hL h h chlorophenoxy) blryryl ethyl 2- (2-oeethl-4-hairy-densay) propisnyl

continued table

active substance number ^r1 X R ² 169 pyrid-3-yl H 170 pyrid-3-yl H ethyl 171 pyrid-3-yl H --propyl 172 pyrid-3-yl H --propyl 173 pyrid-3-yl H --propyl 174 pyrid-3-yl H ethyl 175 pyrid-3-yl H ethyl 176 pyrid-3-yl H --propyl 177 4a, 7,8,8a-tetrahydro-2H, 5H-pyrano [4,3-b] pyran-3-yl H --propyl 178 4a, 7,8,8a-tetrahydro-2 H, 5 H -pyrano (4,3-b) pyran-3-yl H --propyl 179 4a, 7,8,8a-tetrahydro-2H, 5H-pyrimidine [4,33b] pyran-3-yl H --propyl 180 4a, 7,8,8a-tetrahydro^-2H,^5H-pyrano^[43-b] pyran-3-yl H --propyl 181 4a, 7,8,8a-tetrahydro- -2H, 5H-p &lt; 1 &gt;: ra - [[4,3-b] - pyran-3-yl H --propyl 182 3,4,4a, 7,8,8a-hexahydro-2H, 5H-pyrano ^4,3-_ - J ^b pyran-3-yl H --propyl 183 cyclohexee-4-yl H --propyl 184 4-Methylcyclohex- 1-e-5-yl H --propyl 185 2-methyl-1-cyclo- hexeny1 h ethyl 186 2,6,6-triethyl-1-cyclohexyl h --propyl 187 2,6,6-tjréeth ^ i- -1-cyclohexyl H --propyl

^r3 AND data h-NM ^r spectrum ethyl benzoyl 1.40 (m) 7.60 (m), 8.62 (m) ethyl 3- (2-Chloro-4- -trilorreethylphenyl- (oxH-n-trobenzoyl) ethyl 3- (2-chloro) -4-trifluoromethyl-4- [f] -6-n-tr [benzoyl] ethyl 2- [4- (4-Trifluoroethylphenoxy) phenoxy] ropio-yl ethyl t-butyldiethylsilyl ethyl phenyldiethylsilyl ethyl O, N, N-thiophosphoryl ethyl 2-m e lbe-zoy 1 2.60 (s) 7.4 (m), 8.65 (m) ethyl benzoyl ethyl 2-mehy lbe-z оу 1 ethyl stearyl ethyl 3- (2-chloro-4-trifluoromethylpheno [b] -6-n-trbenzoyl). ethyl acetyl ethyl benzoyl ethyl benzoyl ethyl benzoyl 0.85 (t), 5.62 (s), 8.18 (d) ethyl benzoyl ethyl benzoyl 0.85 (t), 1.75 (s), 8.05 (d) ally! benzoyl 1.05 (S), 4.50 (d) 7.6 (d)

continued. tables effective

substance number R1 X R ² · R ³ AND data H-NMR spectrum ^and 188 cyclododeca-4,8-dienyl H n-pr ^ y! , allyl benzoyl 189 cyclododec- H ethyl benzoyl 1.05 (t) 5.30 (m) -4,8-dienyl 7.50 (rn) 190 cyclohexyl H n-prop (1) ethyl benzoyl 1.10 (t) 1.75 (m) 7.50 (m) 191 4-Methylcyclohexane- H n-propyl ethyl benzoyl 0.85 (ť) , 1.65 (s), -3-enyl 5.35 (with) 192 ^ meetihycvklohex- -3-enyl H n-pupy! allyl benzoyl 193 ^ meetihlcyklohex- H n-pr ^ y! --chlorine· -3-enyl allyl benzoyl 194 4-ethyl-cyclohexyl- H n-propyl; ethyl 2-methylbenzoyl 1.10 (t) 2.60 (t) -3-enyl 5.35 (with) 195 2,6,6-triethylbicycl -. H n-propyl; ethyl benzoyl 1.38 (q) , 3.98 (q), F ^{3 1,1} heptan-3-yl 7.46 (m) 196 T-Methoxycarbonyran-5-yl H n-propyl; ethyl benzoyl 197 2-eeehc) oχУe trahydrop ^y ran-5- ^yl H n-propyl; allyl benzoyl 198 4-Ethylpyridylpyran-3-yl H n-pr ^ y! ethyl benzoyl 199 ^ meethytetr ahydro- H n-pr ^ y! ethyl 2- [4- (4-Trifluoro- pyran-3-yl ethylphenyloxy) phenoxy] ylyl-yl 200 4-eeehcУtetrahydro- H n-propyl ethyl ² - [ ⁴ - ( ⁴ - ^yy rid ^- pyran-3-yl ^-2-y lox ^{y) f} e-ox ^y | ^ l propio 201 tet rahydrofuran -3- у 1 H n-propyl; ethyl benzo ^y l 202 5,6-dihydro-2 H -pyran-3-yl H n-propyl; ethyl benzo ^y l 203 2-eeehooyУetrahydro- H ^^ for ^^^ L ethyl benzoyl 1.05 (t) , 3.32 (8), pyran-6-yl • 4.70 (with) 204 tetrahydropyran-3-yl COOCH- n-propyl; ethyl benZO ^y l 0.88 (t) 3.75 (m) 7.45 (t) 205 3-Methyl-6-yl-6- H n-propyl eth ^ zl benzo ^y l 1.08 (t) 2.55 (s), 8.05 (d) 206 pyridyl-4-yl H n-propyl; ethyl benzo ^y l 3.60 (m) , 4.0 (q), 7.28 (m) 207 1-oxotetrahydro- H ethyl ethyl benzo ^y l 1.85 (m) 3.45 (m) thiopyran-3-γ1 4.00 (q) 208 1-1xotetrahydrothiopyran-3-ol H n-propyl; ethyl benzo ^y l 209 1,1-DiletetraCydrltCilyyran-3-yl H n-pryl ethyl benzo ^y l 210 1,1-dilxotetrahydrl- H ethyl ethyl benzo ^y l 1.05 (t) , 4.0 (q), tcilyyran-yl 8.0 (d) 211 1-Benzyloxyethyl H n-pr ^ y! ethyl benzo ^y l 0.90 (t) 3.55 (m)

7.35 (s) continued table effective

substance number R ¹ X R ² R ³ AND data ¹ H-NMR spectra 212 1- [2- (n-butoxy) - H n-propyl ethyl benzoyl 3.60 (m), 4.0 (q), ethoxyj ethyl 7.60 (m) 213 2- [2- (n-butoxy) ethoxy] ethyl H n-propyl ethyl benzoyl 214 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 (with), phenyl 8.10 (m) 216 3-methylphenyl H ethyl ethyl benzoyl 226 2-i-propyl- (1,3-dioxepan) -5-yl H n-propyl ethyl benzoyl 227 2-i-propyl-1,3-dioxepan-5-yl H ethyl ethyl benzoyl 228 tetrahydropyran-3-yl H n-propyl ethyl 2- (4-chloro- 1.61 (s), 4.08 (q), phenyl) -2-methylpropionyl 7.31 (m) 229 tetrahydropyran-3-yl H n-propyl ethyl 2-Methyl-fur- 2.60 (s), 3.23 (q), -3-ylcarbonyl 6.65 (with) 230 tetrahydropyran-3-yl H n-propyl ethyl 2- (2,4,5-tri- 4.85 (m), 7.01 (s), chlorophenoxy) propionyl 7.52 (with) 231 4-Methylcyclohex-1- H n-propyl allyl benzoyl 0.85 (t), 4.45 (d) -en-5-yl 5.60 (with) 232 4-Methylcyclohex-1- H n-propyl ethyl methylsulfones1 1.30 (t), 3.25 (with), -en-5-yl 6.67 (with) 233 4-Methylcyclohex-1- H ethyl ethyl benzoyl 1.10 (t), 7.50 (m), -en-5-yl 8.05 (d) 234 4-Methylcyclohex-1- H ethyl ethyl methylsulfonyl 1,25 (t), 3.2 (s), -en-5-yl 5.65 (with) 235 4-Methylcyclohex-1-en-5-yl H ethyl allyl benzoyl 236 2-ethylthio-n-propyl H n-propyl ethyl 2- (2,4,5-tri- 4.10 (q), 7.00 (s), chlorophenoxy) propionyl 7.25 (with) 237 2-ethylthio-n-propyl H n-propyl ethyl 2- (3-bromophen- 4.05 (q), 4.81 (q), oxy) phenoxy) propionyl 7.10 (m) 238 2-ethylthio-n-propyl H n-propyl ethyl 2- (4-bromo- 2.5 (m), 7.26 (m), phenyl) propionyl 7.46 (m) 239 2-ethylthio-n-propyl H n-propyl ethyl 2- (4-fluorophenyl- 1.55 (d) 4.05 (m), nyl) propionyl 7.04 (m) 240 5,6-Dihydro-2H-1-oxo- H n-propyl 3-chloro- 0.85 (t), 3.60 (m), thiopyran-3-yl allyl benzoyl 7.55 (m) 241 2-ethylthio-n-propyl H n-propyl ethyl 0,0-diethyl- 0.95 (t), 2.58 (q), phosphoryl 4.2 (m) 242 x2-ethylthio-n-propyl H n-propyl ethyl n-butyldimethyl- 0.08 (s), 1.3 (m), silyl 2.9 (JH)

continued table effective

substance number R ¹ X R ² R ³ AND data 1 H-NMR spectra 243 2-ethylthio-n-propyl H n-propyl ethyl phenyldimethyl- 0.35 (with) , 1.0 (t), silyl 7.4 (m) 244 tetrahydropyran-3-yl H n-propyl ethyl 0,0-diethylthio- 0.90 (t) , 1.40 (t), phosphoryl 4.10 (q) 245 tetrahydropyran-3-yl H n-propyl ethyl 0,0-diethyl- 0.95 (t) , 1.38 (t), phosphoryl 4.2 (m) 246 tetrahydropyran-3-yl H n-propyl ethyl n-butyldimethylsilyl 247 tetrahydropyran-3-yl H n-propyl ethyl phenyldimethyl- 0.30 (with) , 0.93 (t), silyl 6.35 (m) 248 2-ethylthio-n-propyl H n-propyl ethyl 249 4-methyltetrahydro- H n-propyl 3-chloro- - 0,0-diethyl- 0.92 (t) , 1.37 (t), pyran-3-yl allyl thiophosphoryl 4.7 (m) 250 4-methyltetrahydro- H n-propyl 3-chloro- - 0,0-diethyl- 0.95 (t) , 1,4 (t), pyran-3-yl allyl phosphoryl 6.15 (m) 251 4-methyltetrahydro- H n-propyl 3-chloro- - phenyldimethyl- 0.62 (with) , 5.08 (d) pyran-3-yl allyl silyl 7.63 (m) 252 4-methyltetrahydro- H n-propyl 3-chloro- - 2- (4-tri-) 1.0 (d) 1.4 (t), pyran-3-yl allyl fluoromethylphenoxy) phenoxy] propionyl 7.0 (m) 253 2- (4-chlorophenyl- H ethyl ethyl 4-chlorobenzoyl 1.10 (t) , 1.80 (q), thio) ethyl 2.97 (t) , 7.26 (with) 254 tetrahydropyran- H n-propyl ethyl benzyl 0.90 (t) , 1.30 (m), -3-yl 5.10 (with) , 7.35 (m) 255 5,6-dihydro-2H-1,1- H n-propyl 3-chloro- 0.88 (t) , 3.60 (m), -dioxothiopyran-3-yl allyl benzoyl 7.55 (m) 256 pyridyl-3-yl H n-propyl ethyl pivaloyl 257 5,6-dihydro-2 H -1-oxothiopyran-3-yl H n-propyl ethyl benzoyl 258 4a, 7,8-tetrahydro- ₁ 8a -2H, 5H-pyrano [4,3-b] - H n-propyl allyl benzoyl -3-yl 263 pyrid-3-yl H n-propyl ethyl 2,5-dichloro-6- 0.90 (t) , 3.90 (m), -methoxybenzoyl 8.60 (m) 264 4-methylcyclohex- H n-propyl ethyl benzoyl 0.85 (t) , 3.98 (q), 1-en-5-yl 8.05 (d) 265 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 0,0-diethylthio- 0.92 (t) , 1,4 (m), -3-yl phosphoryl 4.2 (m) 268 tetrahydropyran-4-yl H n-propyl ethyl benzoyl 269 tetrahydropyran-4-yl H n-propyl ethyl palmitoyl 270 tetrahydropyran-4-yl H n-propyl ethyl stearoyl

continued table active substance R number

spectrum

271 tetrahydropyran-4-yl H n-propy! ethyl 3- (2-Chloro-4- 272 tetrahydropyran-4-yl H tthyl ethyl Phenoxy) -6-nitrobenzoyl 3- (2-chloro-4-tri-) 273 tetrahydropyran-4-yl H ethyl a.lyl ^υη ^ θΟγΐ !: thnoxy) -6-aminobenzryl 3- (Z-chloro - '- 274 tetrahydropyran-4-yl H n-pr ^ y! . ethyl tri loomethy 1fenoxy) -G-nitrobenzoyl 2 ^- ( "-trifUTr- 275 tetrahydropyran-a-yl H n-propyl ethyl ) - О-оху / р ^ рО-у! 2- [4- (--iodopyridine) - 276 tetrahydropyran-a-yl H n-propyl ethyl - / lox ^ f · - ^ / ^^ pOnyl · 2---4- (4 - rifllro- 277 tetrahydropyran-a-yl H n-propyl ethyl Ethyl-2-yloxy) polynyl 2 - [“- И“ - !!!!! 278 ttt r ahydropy ran-4-у 1 H n-propyl ethyl methyl-6-chloropyrid-4-yloxy) phenoxy] propio-yl 279 tetrahydropyran-4-yl H n-propyl ethyl (quinoxalinoxy) phenoxy / propio-yl 2- [4- (6-00 ^: - 280 tetrahydropyran-4-yl H n-propyl ethyl thi azo! ^ - /! ^ /) - Ο-ογ ^^ ρΟ-γ 1 2- [4- (G-chlorobt-2-yl) 281 6-methooy / etrahydro- H ethyl ethyl oxa azo (4-yloxy) phenoxy] -propionylbenzoyl 282 pyran-2-yl 3,4,4a, 7,8,8a-hexa- H n-propyl allyl benzoyl 0.90 (t), 4.4 (d) hydro-2H, 5H-pyrano- [4,3 ^^ jpy: ra ^ -3 - ^^ 1] 8.15 (d)

Active substance R ¹ No

XR ² R ³ G data ³ H-NMR spectra

218 tetrahydrulyran-3-yl H 219 tetrahydropyrann-3-ol H - ^^ Ι 220 tetrahydrulyran-3-yl H n-projDy! 221 tetrahydropyran-3-ol H - ^ ιό ^ Ι 222 tetrahydrothiolyral-3-yl H 223 tetrahydruthiulyran-3-yl H 224 tetrahydrothiopyran-3-yl H 225 pyrid-3-yl H 1-lrulyl 259 4a, ^{7,8,8a-tetrahydro-2H,} 5H-pyrano ^[4, 3-b] -3-yl H n-propyl 260 4a, 7,8,8a-tetr-hydru- -2H, 5 [4,3-b] -3-yl H - • Ί ^^ Ι 261 , 3- ^^ Х ^ ап-б-у! H n-projDy! 262 2-i-lroul-1,3-di-oxepiperazin-1-yl H ethyl

ethyl phenylene 0.90 (t), 8.17 (s) 1.08 (t) ethyl propylene 0.90 (t), 1.70 (s) 3.90 (m) ethyl Aunt <methylene ethyl hexa ^ e ^ et ^^ len ethyl phenylene ethyl methylene ethyl ^ Ь-эп ^^ у ^ - ethyl t e-amethylene ethyl phenylene ethyl tetaamethylene ethyl phenylene ethyl phenylene

The herbicidal compositions which contain cyclohexenol of the formula I, sr may be applied, for example, in the form of directly sprayable solutions, powders, suspensions, even of high percentage aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scatters or granules. spraying, fogging, dusting, sprinkling or watering.

By applying the form of these compositions, the utmost dispersion is ascertained as possible. In any case, they measure the compositions of the invention.

For the production of directly sprayable solutions, emulsions, pastes and oil dispersions, suitable are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, as well as tar oils and the like. vegetable or animal oils, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paaafii, tetrahydronaphthalene, alkyl naphthalenes or derivatives thereof, such as mutanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexyl, chlorobenzyl, i-salt, strongly polar solvents, α-dimethylamide, trifluoromethyl sulfide, N-methylpropylride, water.

Aqueous use forms can be prepared for concentrates, pastes or wettable powders or oil dispersions by the addition of water. For the preparation of detergents, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent may be homogenized with the aid of surfactants, adhesives, dispersants or water.

However, it is also possible to prepare concentrates which can be seen from the active ingredient, wetting agents, adhesives, dispersants or, and optionally, solvents or oils, which are suitable for dilution with water.

Suitable surfactants are: alkali metal, alkaline earth metal, and alkaline earth metal salts of the corresponding alkali metal sulfonic acid, sulphonic acid, sulphonic acid, sodium sulfonic acid, sodium sulfonic acid, sodium sulfonic acid, alkyl sulphates, alkali metal and alkaline earth metal dibutyl laphthaleosulfonate, lithium ether sulphate, sulphated fatty alcohols, alkali metal and alkaline earth metal salts, sulphonated hexadecanol esters, octadecanol esters, heptadecanol ethers matt alcohols, condensation products slllonb) atného oaftaleiu and derivatives of naphthalene with formaldehyde, condensation products oaftaleiu optionally kyselil lαftαteosufOonoaých with phenol and flrrtldehydem, r ⁰ ly ^{<o χ У e} ehylenolkyfenoOethery, ethoxylovaoý islokkylftlol, oktylfeiol, оопо ^ епо1, aliylfelllřllyglyillethery, krbblkyfteлylpllyglyklltthtry, αlkylαrylřllyttheralkoholy , isltridtyltlil hol, condensation products of fatty alcohols with ethylene amide, ethoxylated castor oil, polynyethylene diacyl ethers, ethoxylated polypropylto, ethoxylolole ethereal, esters of iorbite, ligand, sulphite waste liquors and crystals.

Powders, dusts and dusts can be prepared by mixing or comminuting the active compounds with a solid oily substance.

Granules, such as coated impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid oily substances. Solid oils are, for example, mineral clays such as silica gel, silicas, silicates, talc, cadil, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, silica, calcium sulfate and magnesium sulfate, magnesium oxide, ground ипПё materials, fertilizers such as ammonium nitrate, ammonium nitrate phosphate, mooophins and plant products such as cereal flour, tree bark flour, wood flour and walnut flour, powdered cedar axis and other solid ooseous substances.

The herbicidal compositions may contain from 0.1 to 95% by weight of the active compound, preferably from 0.5 to 90% by weight. .

The following are examples of compositions and preparations according to the invention.

I. 90 parts by weight of the active substance No. 2 are mixed with 10 parts by weight of N-nitrile-alpha-nitrile-lithium nitrile to give a solution which is suitable for use as minimal drops.

II. 20 parts by weight of active substance No. 8 are mixed with 80 parts by weight of xylene, 10 parts by weight of adduct product 8 to 10 moles of ethyle dioxide and 1 mol of N-rototthanolamide oleic acid, 5 parts by weight of calcium idiodecylbenzenesulpholol. 5 parts by weight of the addition product of 40 moles of ethylene oxide with 1 mole of oil. ·

By pouring and finely distributing this solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the mono-active substance. .

III. 20 parts of the mono-mono-active substance No. 5 are dissolved in a mixture consisting of parts of cyclohexanone, 30 parts of isobutanol, 20 parts of the mass addition product of 7 moles of ethylene oxide with 1 mole of hexytylphenol and 10 parts of the mono-additive product. 40 moles of ethylene oxide with 1 mol of castor oil. By dissolving the solution gently in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

IV. 20 parts UmotnosSních compound no. 253 rozpussí in smOss, which consists of 25 parts hmoonootních of cyclohexanol, 65 parts hmoSnostních mineral oil fraction having a boiling point ^{from 210} to ²⁸⁰ ° C and ¹ 0 says ^{lu hr} moOnostních addition ^ o ^p roducts 40 mol eth ^y oxide with 1 ^m ol ricňoového oil. By dispersing the solution gently in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

V. 20 parts of the mono-mineral active substance No. 60 is well mixed with 3 parts of sodium diisobenzylnaphthalene-affasulfonic acid, 17 parts of sodium mono-sulfonic acid sodium sulphate waste liquor and 60 parts of the powdered silica gel and the mixture is ground on a ice mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray suspension is obtained, which has a rate of 0.1% by weight of active ingredient.

VI. 3 parts of the mono-active substance No. 109 are mixed with 97 parts of the finely-dispersed kaoSins. In this way, a dust is obtained which contains 3% by weight of active ingredient.

VII. 30 parts of the active ingredient No. 252 are intimately mixed with a mixture of 92 parts by weight of powdered silica and 8 parts by weight of paraffin oil sprayed onto the surface of the silica gel. In this way, an effective formulation with good adhesion is obtained.

VIII. 20 parts of active ingredient no. 1 are intimately mixed with 2 parts of lime and the same dodecylbenzenesulfonic acid, 8 parts of polyglycol ether of fatty alcohol, 2 parts of sodium condensation product of phenol, motovoy and foroaldehyde and 68 parts ^of arafinic mineral oil. A stable oil dispersion is obtained.

Application of the compositions of the invention may be carried out pre-emergence or post-emergence.

Jecou-and certain cultural ro ^ ttlky towards drugs less tolerant, then it may be operating manual also such application methods in which the herbicidal agents are ^p osSřiksvačů fed so that the leaves of sensitive crop rossiin remained podleχOOsinsSi postříeeo unaffected, přččemž poosrik smOěuje the leaves of undesirable rosslin, which grow according to culture plants or on a non-provided soil surface (post directed, lay-by).

Depending on the season, the rosslin treated and the growth stage, the amount of active compound used is 0.025 to 3 kg / ha, preferably 0.1 to 1.5 kg / ha.

The effect of the herbicidal compositions according to the invention is in the following experiments carried out in a greenhouse:

300 ml plastic pots filled with sandy soil containing about 1.5% humus serve as culture containers. Seeds of experimental rosslings are sown separately by species. Immediately thereafter, in pre-emergence treatment, the herbicidal compositions are applied to the soil surface.

To this end, the herbicidal compositions are suspended in water as a dispersing medium and sprayed using finely dispersed nozzles. The application rate is 3.0 kg of active ingredient per hectare.

After application of the herbicidal compositions, the containers are slightly irrigated for germination and growth. The containers are then covered with a transparent plastic film aU until the plants start growing. This covering results in an even germination of the test plants unless these plants have been affected by the active substances.

For the post-emergence treatment, the experimental plants were pegged, depending on the form of growth, to a height of from 3 to 15 cm and then scraped. The soybean plants are sieved in a peat-enriched substrate. For the purpose of post-emergence treatment, either directly sown and grown in the same containers are planted, or planted first, as seedlings separately in seeding pans for several days. they are transplanted into test vessels prior to treatment. The applied amount for post-treatment is 0.125, 0.25, 0.5 and 3.0 kg of active substance / ha. In post-emergence treatment, the film is not covered.

Experimental vessel umíísí to a greenhouse přčeemU for thermophilic species vooí warmer spot (pulse-most ²⁰ and ^{at 35} ° C) and ^p ro those <3ru ^h y ro ^ ^stl i ^ t, ^k esters thrive in temperate potinebním p ^á SMU the advantage is not the temperature of ^{d 10 d d 2} 0 ° C. Time after ^the Usu is ² and ^{u 4} th ^d ny. During this ^d Ota ošštřuuí the plants and evaluate their response to treatment jednnoiivá.

100% means that the plants did not grow up, or at least the above-ground parts of the rossiins were completely destroyed.

The plants used in the greenhouse experiments are selected from the following species: field fox (Alopecurus iossossrides), deaf oat (Avena fatua), oat (Avena sativa), beet (Beta vulgaais), rape (Brassica napus), brome (Bromus spee). ), Cassia spp., crabgrass (Digitaria santgSnttis) jeutřOt barnyardgrass (Echinochloa c ^ i ^ £ ^ SGG ^ 2 ^ _l), Eleusine indi-ca, soybean (Glycine MMA). b ^ \ ^ workers over ( Gossypium hirsutum, Sunflower (Heian-Lhus annuus), Barley (Hordeum vulgát), Piedleaf (Ipomoea spec.), Manyeye rye (Lolšum íuStifSořuí), Walnut (Seearia italica), White Mustard (Sinapis alba), Sorghum biori ), Sorghum halepensee, Wheat ( ^r ΓritCsuí aestivum, Maize (Zea mгyat)).

Preemmegietní treatment

Pre-emergence treatments have shown herbicidally active agents, for example, herbicidal compositions which contain compounds No. 39, 229, 109, 207, 210, 55, 53, 161, 12, 2, 8, 61, 60, 160 as active ingredients. , 252, 250 or 242 of the grass family, while the white mustard (Sinapis alba), ie the cross-flowering plant (Ccuciferea), remained completely undamaged. The compositions which contain, as an active ingredient of Compound No. 73, 2-30, 25 or 72, kill both monocotyledonous species and dicotyledonous mustard.

Postemeeggenic treatment _r

For example, herbicidal compositions containing as active ingredient Compound No. 217, 28, 30, 22, 191, 79, 37, 239, 17, or, for example, contain 3.0 kg of active ingredient / ha. 228, monoclonal rossiin species. HeebScidic compositions which contain Compound No. 230, 26, 73 or 72 as the active ingredient are effective against both monocotyledon and pro-o. It is possible for species to be bs. .

For application of 0.125 kg of active ingredient / ha, for example, herbicidal compositions containing as active ingredient Compound No. 109, 207, 255, 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 or 266, when 0.25 kg of active substance / ha are applied Compositions which combine as an active ingredient of Compound No. 1, 2, 4, 5, 241, 242, 243, 245, or 247 are highly effective. plants of the grass family.

Likewise, the herbicidal compositions containing Compound No. 253 as an active ingredient at 0.125 kg / ha application do not kill other monocotyledonous species without damaging dicotyledonous crop plants.

The herbicidal compositions containing Compound No. 161 as active ingredient, when applied to an amount of 0.25 kg of active ingredient per hectare of undesirable grass species in wheat cultures, also to the grass family. In addition, for example, compounds No. 194, 212, 233 and 234 control unwanted species of cereals.

The results of the tests which illustrate the herbicidal activity of the composition according to the invention are summarized in the following Tables 1 to 14:

Table 1

Hetricidal effect in the application of 3.0 kg of active ingredient per hectare

Active substance Test plants and damage

number SLnaj ^ is the album Avena: fatua Echinochloa LolUuo Crus Gani ouUtilSbumι 39 0 100 ALIGN! 100 ALIGN! 100 ALIGN! 229 0 100 ALIGN! 100 ALIGN! 100 ALIGN! 109 0 100 ALIGN! 100 ALIGN! 100 ALIGN! 207 0 100 ALIGN! 90 100 ALIGN! 210 0 100 ALIGN! 80 100 ALIGN! 55 0 100 ALIGN! 85 '100 53 0 100 ALIGN! 80 100 ALIGN! 161 0 100 ALIGN! 95 100 ALIGN! 12 0 100 ALIGN! 100 ALIGN! 100 ALIGN! 2 0 100 ALIGN! 100 ALIGN! 100 ALIGN! 8 0 100 ALIGN! 95 100 ALIGN! 61 0 100 ALIGN! 100 ALIGN! 100 ALIGN! 60 0 95 100 ALIGN! 100 ALIGN! 256 0 100 ALIGN! 80 100 ALIGN! 252 0 100 ALIGN! 100 ALIGN! 100 ALIGN! 251 0 100 ALIGN! 98 100 ALIGN! 242 0 100 ALIGN! 98 100 ALIGN! Ta b u lka 2 Herbicidni efektrk at average nursing using 3.0 kg active substance j Effective substance Experimentally plants and damage number Sinapsis alba Avena fatua LolUuo mUtLifEOrum (dicotyledonous) ьмШм) 73 100 ALIGN! 100 ALIGN! 100 ALIGN! 230 95 100 ALIGN! 100 ALIGN! 25 100 ALIGN! 100 ALIGN! 100 ALIGN! 72 95 100 ALIGN! 100 ALIGN! Ta b u lka 3 Heebicidní effect at a half-merit treatment for a breakdown of 3.0 kg of active substance Effective substance Experimentally plants and pboct-it damage number Avena sativa Echinochloa

Cruss-alli muUtiftrruo

217

100 ALIGN!

100 Continuation of Table 3

Eyes-á Substance Attempt-to-do and why-damage

čísloU Ave-a sativa Echi-ichlca crus-gaaLi Lolium muniflrrum 28 100 ALIGN! 100 ALIGN! 100 ALIGN! 30 100 ALIGN! 100 ALIGN! 100 ALIGN! 22nd 100 ALIGN! 100 ALIGN! 100 ALIGN! 191 100 ALIGN! 100 ALIGN! 100 ALIGN! 79 100 ALIGN! 98 1-0 0 37 100 ALIGN! 100 ALIGN! 100 ALIGN! 239 100 ALIGN! 100 ALIGN! 100 ALIGN! 17 100 ALIGN! 95 100 ALIGN! 228 100 ALIGN! 98 100 ALIGN!

Table 4

Heebicidal action in the case of aostemegeneic application and use of 3.0 active substances per ha

Átkaδΐ ^ ά Substance Attempt to cause damage

čísloLl Echi-ichLca cris-gaali Lolřum muutiflruum Cassia spec. Ipomota spec, 230 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 26 95 100 ALIGN! 95 90 73 95 100 ALIGN! 100 ALIGN! 100 ALIGN! 72 98 100 ALIGN! 95 80 Table 5 He-ti-d-i the effect of postemmegeneic administration of oa 0.125 kg of substance Gói-á Fabric Attempt to grow and process damage number Seearia italčca Zea mays 109 98 95 207 98 95 252 98 90 40 95 95 20 May 95 98 Table 6 HeeOicide the effect of post-treatment treatment point 0.25 kg of substance

ha ha

Experimental smear plant Substance No. 1 damage%

Beta vulgaris 0 Glycine max 0 Gossypium hirsu-uum 0 A ^ p ^^ us myylsuoidts 94 Ave-a fatua 96 Eleusine i-dica 95 Sorahum Уaltytnst 95

Table 7

Heebsidic effect in post-migraine application with a polution of 0.25 kg of active substance No. 4 per 1 ha

Experimentally

Active substance No. 4 damage in%

Glycine max

Avena fatua

Sorghum ^^ Ьь ^x

Sorghum hal. epense (from seed) _ x

Zea mays

100 ALIGN!

Note:

^x ja grew ^to a side-ins vyrostJLé from seeds fallen ^{p y} s previous harvest

Table 8

Heercosidic effect when applied in full-time application at a rate of 0.125 kg of active substance No. 253 per ha

Active substance No 253 damage%

Brassica napus 0 Heeianthus annuus 0 Al ^ e ^ rus m ^y oltroidtt 95 Bromus spec. 95 Digitaria tannutnnlit . 95 Echinochloa irtstgilli 100 ALIGN! Hordnim ^ Дзьг ^x 90

Note:

j and ^k of undesirable ьц ^ 1;]. 1г ^ у ^{characterized} Rost ^Ia from barley seeds in ^YP adlýc s ^{hp eg} EDC OZI ^{t h} ^ ^k. ^ SNI

Table 9

Heeridic effect in ^p- polystyrene application for active substance No. 161 in multiplicity

0.25 kg / ha

Test plants Active substance No 161 damage%

Triticus aestivum0

Sstaria italíca85

Sorghum ha ^ p ^ nse100

Table 10

The herbicidal effect at p1 / min (0.25 kg / ha) was applied at 0.25 kg / ha

Experimental plants % Damage active substance No 2 active substance No 5 Glycine max 0 0 Avena fatua 100 ALIGN! 98 Echinochloa crus-cgaii 90 100 ALIGN! Sorghum halepense 90 85 "X Zea mays 100 ALIGN! 100 ALIGN!

as an undesirable plant grown from the seeds of maize dropped out during the previous harvest

Table 11

HerbScidious effect in post-emergent application Effective Ponuřtě Experimental plants and damage In percent substance no. шппЫу! Beta Echinochloa Seearia Sorghum (kg / ha) vulgaris Crus-даШ italica halepense

238 0.125 0 98 100 ALIGN! 98 71 0.125 0 100 ALIGN! 100 ALIGN! 98 74 0.125 0 100 ALIGN! 100 ALIGN! 100 ALIGN! 35 0.125 0 90 95 98 56 0.125 0 98 95 100 ALIGN! 186 0.125 0 98 100 ALIGN! 90 255 0.125 0 98 95 95 122 0.125 0 98 100 ALIGN! 100 ALIGN! 29 0.125 0 95 ' 95 100 ALIGN! 176 0.125 0 98 100 ALIGN! 100 ALIGN! 33 0.125 0 98 95 98 190 0.125 0 98 100 ALIGN! 90 206 0.125 0 98 100 ALIGN! 98 169 0.125 O 98 100 ALIGN! 100 ALIGN! 7 0.030 0 100 ALIGN! 95 100 ALIGN! 5 0.125 0 100 ALIGN! 100 ALIGN! 90 13 0.125 0 95 98 95 219 0.125 0 98 100 ALIGN! 100 ALIGN! 154 0.125 0 98 90 100 ALIGN! Ta b u 1 k and 12 Heeršcidní effect during postemerge ntním oš etřml Effective p used Try plants ^r and damage In percent substance no. . mw -? two Glycine Zea Dg itaria Seearia Sorghum (kg / ha) mays * san guúnaais italica halepense 245 0.25 0 98 98 95 98 241 0.25 0 95 85. 95 90 242 0.25 0 100 ALIGN! 98 98 98 247 0.25 0 98 100 ALIGN! 98 100 ALIGN! 243 0.25 0 100 ALIGN! 100 ALIGN! 100 ALIGN! 95

Note:

к as an undesirable plant of vypadiych seeds

Table 13

Heericide effect in pseemerger treatment using 0.125 kg of active ingredient per hectare

Test substance and damage in%

No Ssearia Zea italica mays

9 100 ALIGN! 100 ALIGN! 13 98 100 ALIGN! 27 Mar: 100 ALIGN! 100 ALIGN! 31 98 100 ALIGN! 18 100 ALIGN! 100 ALIGN! 32, 100 ALIGN! 100 ALIGN! 24 98 100 ALIGN! 57 * 98 98 42 95 100 ALIGN! 266 100 ALIGN! 80 Taboo 1 k and 14 Hebicide effect in the post-treatment treatment Effective Poχuihé Experimental plants and damage in percent substance no. mn-^ knows Tritéuum Seearia Echi-χeУloa (kg / ha) aestivum italica crus-cgali 161 0.25 0 85 ' 100 ALIGN! 212 0.5 0 95 98 234 0.5 0 95 100 ALIGN! 233 0.5 . 10 100 ALIGN! 100 ALIGN! 194 0.5 10 100 ALIGN! 100 ALIGN!

In view of the achievable spectrum of weed control, crop tolerance or undesirable growth as well as the versatility of the application methods, the active compounds according to the invention can be used in a large number of cultures. .

The following plants are contemplated - for example, the subculturing culture -:

Botanical name Czech name Allúxm cepa onion Pineapple comosus pineapple Arachis Уypχgχta peanuts Asparagus ^ Ηοί-δΐ ^ asparagus Beta vulgar's spec, altúsiima sugar beet Beta vulgar's spec, rapa fodder beet Beta vulgaris spec beetroot Brassica napus var. napus rape Grassica napus var. napobrassica tuří- Brassica napus var. rapa white beets Brassica rapa var. oilseed rape Caaellia sire-isis teapot Carthamus hirctrbiut Safflower Carya all-ißο-i ^ - ^ s walnut pecan

Botanical name Czech name Citrus limon lemon tree Citrus maxima lemon tree Citrus reticulata tangerine Citrus sinensis orange Coffea arabica (Coffea canephora, Coffea liberica) coffee tree Cucumis melo melon Cucumis sativus cucumber Cynodon dactylon Troskut prstitý Daucus carota carrot Elaeis guineensis coconut tree Fragaria vesca Strawberry Glycine max soya Gossypium hirsutum cotton (Gossypium arboreum cotton Gossypium herbaceum cotton Gossypium vitifolium) cotton Helianthus annuus sunflower Helianthus teberosus Jerusalem artichoke Hevea brasiliensis rubber tree Hordeum vulgare barley Humulus lupulus hop Ipomoea batatas sweet potato Juglans regia Walnut Lactuca sativa salad Lens culinaris edible lentils Linum usitatissimum only Lycopersicon lycopersicum tomato Malus spec. apple tree Manihot esculenta tapioca Medicago sativa lucerne Mentha piperita peppermint Musa spec. banana tree Nicotiana tabacum N. rustica tobacco Olea europaea olive Oryza sativa rice Panicum miliaceum millet Phaseolus lunatus bean Phaseolus mungo - Phaseolus vulgaris shrimp beans Petroselinum crispum spec. parsley root tuberosum Picea abies spruce Abies albo. silver fir Pinum spec. pine Pisum sativum pea Prunus avium cherry Prunus domestica plum Prunus dulcis almond Prunus persica peach Pyrus communis pear Ribes sylvestre redcurrant

Botanical name Czech name Ribes uva-crispa gooseberry Ricinus comnmnis castor ‘ Sacchirum of sugar cane Secale cereile rye Sesamum CíiUícuo sesam SoIiouo tuberosum potatoes Sorghum licslst (S. · vulgare) or ^ k bicolour Spinacia oleracea spinach Thdobrsol cicio cacao tree Trifslruo pritense Clover TrCtiruo iestvvum wheat Vaccinium csryoi> ssuo blueberries Vaccinium vitttcUladl cranberries Vica fibi bob horse Vigni sCieisis (V. unguuculati) bean Vitis vCnčfdti Grapevine Zea mays maize

In order to broaden the spectrum of efficacy and to achieve synergistic effects, the compositions according to the invention can be mixed with numerous representatives of other herbicidally active substances or with groups of substances which regulate the growth of plants and then they can be applied together. Suitable constituents of such salts are, for example, urazines, 4H-3,1-benzoxazine derivatives, lenzthiadiadinsins, 2,6-dinariline, N-phenylcarbanoates, thiolcalbaoates, olefinic carboxylic acids, η 11, δ, amides, sulfonides. , traazinones, uracils, benzofurin derivatives, cyclohexane-1,3-dione derivatives and others.

In addition, it may be useful to mix the herbicidal compositions of the invention, alone or in combination with other herbicides, also with other plant protection agents and these compositions. applied together with, for example, pest control agents or spreading fungi or baHee.

Also interesting is the location with mineral sdoia solutions. Such mixtures can be used to eliminate nutrient and trace element deficiencies. Non-phytstatic oils and oil endenates may also be added.

Claims (5)

A composition according to claim 1, characterized in that it contains at least one cyclohexenol derivative of the formula I as active ingredient. O — A X wherein ^R1 is ^ r ^ Lcyiovou group tetrahydro ^ ro ^ ^ verifies wounds Tetra ^yl drotУo p ^{l i} t ^y wounds nominal, 1-oxotttraУydrotУiopyranyOovo) u, 1,1- [dioxotetraУydrothiopyranyloovou radical, all these above přieemž said groups being optionally substituted by at most two C1-C4alkylalkyl groups optionally further comprising at most three meeting alkyl groups having from 3 to 12 carbon atoms, which bonds furthermore represent a ring system of up to 12 carbon atoms; ring members optionally containing up to two double bonds and up to two atoms from the group consisting of oxygen and sulfur, further being a radical of 1 to 4 carbon atoms or cyclically substituted groups optionally containing up to two double ^bonds in ^r13 -Y- ^r14 wherein R ¹³ represents a C 1 -C 4 alkyl group, a total alkoxyalklolooot group 2 to 4 carbon atoms or optionally halogen-nominal group being substituted by a phenyl or benzyznamená oxygen or sulfur atom and ^R14 coal ^ u, with 1 to 4 carbon atoms, Y and ^Z 4 represents ^Y Uhl ^ u, then A is not alkantyltvtt is al ^ alkylene chain with nejvýď 4 and ^t om ^y with the proviso that when R represents asylum group, a sulfur atom ^Y and R = alk ^yl TEAMMEMBERS ^y chain with benzyl group, benzennutfonllovtt group or as defined below or alkenoylovtu, furthermore represents phenyl two or up to three substituents selected from the group consisting of halogen, (C1-C4) alkyl, (C1-C4) alkoxy, substituted with phenyl, provided that when R 1 is as defined above alllften ^y Côvo group ftrllovou group thienylooot group or the above manner uubstitoovanot fenylovtt group, then A is not further defnnovanou alllluti0on ^y 0ovot group alkantyll) VTT group, a benzyl Grp Well, lenzensutfoπllovtt group feπtxyacetylovtt, alkyl or benzyl group Zelová is hydrogen or oetУox karbonyltvtu ^yl group, R ² represents alkyovoou skupnnu having 1-4 atoms in ^ UCU R ³ muted 4 atoms C3 alk ^y l □ LTU group was up to 3 atoms or УaOogtnalkenylovou .uao.gennu poopargyooouu skupňnu and ^ y ^ om uhHuu, ltΠlnlOtvou upuj ^ au 3 or skupnuu having 3 or 4 carbon atoms and 1 to wherein represents a radical of of the formula R 1, E, represents a methylene group, a carbonyl group or a sulfonyl group in both cases with at most an alkyl or alkenyl group 20 carbon atoms, a cyclopropyl group, optionally substituted by a methyl group, is furthermore a styryo group or, optionally, at most three 8-carbon atoms selected from the group consisting of halogen, an alkyl group having from 1 to 20 carbon atoms; C 4 -C 4 alkoxy, C 1 -C 4 alkoxy and nitro, substituted phenyl or benzyl, or optionally halogen or methoxy substituted 1-methylbenzyl or 1,1-dimethylbenzyl or chloromethyl, C 1 -C 4 alkoxymethyl carbon in the alkoxy moiety, acetoxymethyl or alkoxycarbonylalkyl group having a total of 3 to 9 carbon atoms, optionally up to three substituents selected from the group consisting of halogen, C 1 -C 4 alkyl, phenoxyalkylene optionally substituted with a branched alkylene chain of up to 5 carbon atoms in the phenoxy moiety or a 5 or 6 membered heterocyclic radical in a ring and with 1 to 2 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur and optionally substituted with C1-C4 alkyl groups, or A represents a group of the general formula in which R ⁴ represents a phenyl group which is substituted with a trifluoromethyl group, or A represents a group of the general formula wherein G represents a phenylene group, a methylene group, an ethylene group or a propylene group, and 12 3 X, R, R, and R have the above meanings, or A represents a group of formula \ ^ ¹⁰ wherein 8 9 10 R, R and R are independently C1-C4alkyl or phenyl, or is a group of the formula wherein Y is independently O or S and 1112 R and R are C 1 -C 4 alkyl groups. 2. A composition according to claim 1 comprising at least one active ingredient One cyclohexenol derivative of the formula I in which X represents a hydrogen atom and R, R, R and A have the meanings given in 1. 3. A composition according to claim 1, characterized in that it contains as active ingredient at least one derivative of the cyclohexenol of formula I wherein R ¹ represents tetrahydropyranyl, tetrahydrothiopyranyl, 1-oxotetrahydrothiopyranylgroup or 1,1-dioxo- The tetrahydrothiopyranyl group, and X, R, R and A have the meanings given in 1. 4. A composition according to claim 1, characterized in that it contains as active ingredient at least one derivative of the cyclohexenol of formula I wherein R ¹ is tetrahydrothiopyran-3-yl 2 3 а group X, R, R and A have the meanings given in 1. 5. A method for producing an active ingredient according to claim 1 of formula I wherein _f treating a compound of formula II (II) in which 12 3 R, R, R and X have the meanings given in item 1, act by compounds of the general formula A - Z, in which A is as defined in 1 and is a halogen atom or a tosyl group, in the presence of a base.