DD284002A5 - PROCESS FOR PREPARING CYCLOHEXAN-1,3-DIONES - Google Patents

Abstract

The invention relates to a process for the preparation of * of the formula I or I ', wherein the substituents R 1 to R 7 have the meaning given in the description. The preparation is carried out, for example, by reacting cyclohexanediones with a pyridine. The compounds according to the invention are used as herbicidal agents. Formula I, I '{* agent herbicide}

Description

Process for the preparation of cyclohexane-1,3-diones

Field of application of the invention

The present invention relates to a process for the preparation of novel cyclohexanediones having a herbicidal action, to agrochemical compositions containing these cyclohexanediones and to their use for controlling unwanted plant growth.

Characteristic of the known state of the art

Numerous substituted cyclohexane-1-diones having herbicidal activity have already become known. These compounds are not always satisfactory in terms of potency Affects selectivity and applicability

O

Object of the invention

The present invention provides a process for the preparation of a novel herbicide which selectively controls weeds in crops of cereals millet and rice at low application rates and with good biodegradability.

Presentation of the essence , the invention

The object of the invention is to select from a number of chemical compounds those which possess the desired selective herbicidal action and to formulate them in such a way that the farmer only has to mix them with water to the desired dilution and then inject them can provide as well as processes for the preparation of the herbicidally active compounds

-JLe-

Surprisingly, it has been found that the new cyclohexanes 1 ^ 3-diones of the general formula I or I, ^{1 have} good herbicidal activity

According to the invention new Gyclohexan-l ^L i3-diones of the formula I or I * can be prepared.

R ⁷ O a.Ji ¹ OO λ I Μ {* ί ^y '<

S O or

R ⁵ R ⁶ R * R

wherein

R and R ^ are independently hydrogen! Halogen ι nitro; cyano; C ₁ -C ₄ -alkyl C ₁ -C ₄ -alkoxy; C ₁ -C ₄ -alkyl-S (O) _n -; COR ⁸ ; C.-C.-haloalkoxy; or C.-C.-haloalkyl;

3 4 5

R ^ R and R are independently hydrogen; or optionally up to three times, identically or differently, by halogeno-nitro Cyanof C ₁ -C ₄ -alkyl-C ₁ -C ₄ -alkoxy; C ₁ -C ₄ -alkyl-S (O) _n -., C ₁ -C ₄ -alkyl ^ Haloalkyl ^, Q ^ - ^ - haloalkyl-S (O) - or C ₁ -C ₄ -haloalkoxy-substituted phenyl or benzyl;

• 2 -

R ^{6 is} hydrogen; Ci-Ci, -Alkyl, Ci-Ci, -Alkoxycarbonyl; or Cyano ",

R ⁷ OH; or 0 ^Θ Μ®;

R ⁸ OH; Ci-C, alkoxy; NH ₂ ; Ci-Ci, -Alkylamino; or di-Ci-Cu-alkylamino;

η is 0.1 or 2;

M is a cation equivalent of a metal ion or an optionally up to three times by Ci-Ci, -Alkyl, Ci-Ci, -Hydroxyalkyl.-, or Ci-Ci ₁ -Akk-

oxy-Ci-Ci, alkyl groups substituted ammonium ion.

means.

In the definitions used in this description, the specified generic terms, as well as the substituents obtainable by combining individual sub-concepts, include, for example, the following specific individual substituents, this list being not a limitation of the invention:

Alkyl : methyl, ethyl, n -propyl, i -propyl, n -butyl, sec -butyl, i -butyl and tert -butyl; preferably methyl, ethyl and i-propyl.

Halogen: fluorine, chlorine, bromine and iodine; preferably fluorine, chlorine and bromine; particularly preferably (for R ¹ and R ² ) fluorine and chlorine and bromine.

Haloalkyl: fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl and 2,2,2-trichloro-chyl; preferably trichloromethyl, difluorochloromethyl and dichlorofluoromethyl.

Alkoxy: methoxy, ethoxy, propyloxy, i-propyloxy, n-butyloxy, i-butyloxy, s-butyloxy and t-butyloxy; preferably methoxy.

Haloalkoxy: fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy and 2,2,2-trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.

Alkoxycarbonyl: methoxycarbonyl, ethoxycarbonyl, 4-propyloxycarbonyl, i-propyloxycarbonyl and n-butyloxycarbonyl; preferably kethoxycarbonyl and ethoxycarbonyl.

284 0 0

Alkylthio! Methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, i-butylthio, s-butylthio or t-butylthio; preferably methylthio and ethylthio.

Alkylsulfinyl : methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, i-propylsulfinyl, n-butylsulfinyl, sec-butylsulfinyl, i-butylsulfinyl; preferably methylsulfinyl] and ethylsulfinyl.

Alkylsulfonyl: methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, i-propylsulfonyl, n-butylsulfonyl, sec-butylsulfonyl, i-butylsulfonyl; preferably methyl and ethylsulfonyl.

In view of their chemical structure, the compounds of the formula I can be regarded as 1,3-cyclohexanediones acylated in position 2. Numerous tautomeric forms can be derived from this basic structure. The invention includes all tautomers.

Each separated by a semicolon individual meaning of the substituents R ¹ to R ⁷ are to be regarded as subgroups of these substituents. The invention also includes the definitions of the compounds of formula I obtainable by deleting one or more of these subgroups.

The compounds of the formula I and I 'are present in an equilibrium of the two forms according to the following equation:

R ¹ R ¹

R ⁷ V

g * 4-R «Ϊ J

i I ^v i = i R3-! 5 N) / \ ( V

I ¹

In the case of the hydroxy compounds (R ⁷ = OH) kaini, in addition to the three enol forms In, Ia '''and Ia ¹ , the triketoform Ia''also occur according to the following equilibrium equilibrium:

-A-

I ö_4 Vr ' ). X-ft Vr »

Yes, I "

(Ia (R ⁷ = OH)

IT X. IT

_R 3_! ! V, _r3 _! ι- V

R ^ X ^ O ^ - R ^ X ^N OH

Ia ¹

The invention encompasses all tautomeric structures derivable from the basic structure I or I ¹ and their salts (A ⁷ = OM).

In addition, the compounds of the formula I or i '(in particular by the radicals R ³ to R ⁶ on the cyclohexane system) may be unsymmetrically substituted. The invention encompasses both the racemate and the enriched and optically pure forms of the respective stereoisomers.

The unsymmetrically substituted compounds of the formula I are generally used as racemates in the processes described in this application, although non-chiral starting materials are used. The stereoisomers can then be separated by methods known per se, such as fractional crystallization after salification with optically pure bases, acids or metal complexes, or by chromatographic methods due to physicochemical properties.

Both the racemate and stereoisomeric forms are encompassed by the invention.

- 5 - 234002

Emphasizing are the compounds of the formula I or

Ri_! ! ^or Ri-i;. '

D S η 6 D 5 T> 6

KK KK

¹

wherein the pyridinecarbonyl radical is attached via position 2 of the pyridine system. .

Also to be emphasized are the compounds of the formula I or I ¹

R ² R ²

\ R ¹ \ R ¹

ψ fi ^{x. /} ^. ^/ ff fl

ί ΰ-If I '·' .C-If I

R3-i _N I _x ^N ° of ^the R3 ₇ ! _s S ^N

R ^{s /} \ ⁶ R ⁵ R ⁶

I I '

wherein the radicals R ¹ and R ² are bonded in positions 3 and 5 of the pyridine system.

Preference is given to the compounds of the formula I or

_R 3_! · "the ,_! Il

-R ^ V \) R ^ V

I ¹

wherein the radicals R ¹ and R ² in the positions 3 and 5 of the pyridine ring and the Pyridincarbonylsystem are linked via the position 2 of the pyridine ring.

Particular preference is given to the compounds of the formula I or I ¹

^Rl \ ^Rl \

^R i _ / '~ \ _ _R i? IL / ~ \ _ _R 2

! ! "the 3_J Il

I ¹

in which

R ^{1 is} hydrogen; Halogen; nitro; cyano; Ci-C, alkyl; C ₁ -C ₁ -alkoxy; C ₁ -C ₁ , alkyl-S (O) -; COR ⁸ ; C ₁ -C _1, haloalkoxy; or C ₁ -C ₁ , haloalkyl; R ^{2 is} hydrogen; Halogen; nitro; cyano; C ₁ -C ₁ alkyl; C ₁ -C ₁ -alkoxy; C ₁ -Ci ₁ -HaIOgOHaIkOXy; C ₁ -C ₁ alkyl-S (O) - ", or C ₁ -C ₁ -haloalkyl; R ^3, R ¹ * and R ^5, independently of each other hydrogen; C ₁ -C ₁ alkyl; or optionally up in trisubstituted by halogen, nitro, cyano, C ₁ -C ₁ -alkyl, C ₁ -C ₁ -alkoxy, C ₁ -C ₁ -alkyl-S (O) -, C ₁ -C ₁ -haloalkyl, C ₁ -C 4 haloalkyl-SiO) - or C ₁ -C ₁ -haloalkoxy-substituted phenyl or benzyl;

R ^{8 is} hydrogen; C ₁ -C ₁ alkoxycarbonyl; or cyano; R ⁷ OH; or 0®M® R ⁸ OH; Ci-Ci ₁ -alkoxy; NH ₂ ; C ₁ -Cu alkylamino; or di-C 1 -C 18 -alkylamino;

η 0, 1 or 2;

© M is a cation equivalent of an alkali, alkaline earth or ammonium ion; Mono-Ci-Cit-alkylammonium; Di-Ci-Cu-alkyl ammonium; TrX-C ₁ -Ci ₁ -alkylammonium; or triethanolammonium ions; means.

Particularly noteworthy are in the abovementioned compounds of the formula I or I ¹ in the scope of the broadest generic meaning as well as, in the highlighted, preferred and particularly preferred generic definitions each subgroup mentioned below:

a) compounds of the formula I or I ¹ in which at least one of the radicals R ³ to R ^{6 is} hydrogen,

b) compounds of the formula I or I 'in which at least two of the radicals R ³ to R ^{6 are} hydrogen,

c) compounds of the formula I or I 'in which R ^{6 is} cyano and R ^{5 is} hydrogen,

d) compounds of Fornelnel I or I ¹ in which R ^& Cyan, P ^{5 is} hydrogen and R ³ and R ¹ * independently of one another are hydrogen or C ₁ -C 12 -alkyl,

e) compounds of the formula I or T ¹ in which R ^{6 is} Ci-Ci, alkoxycarbonyl,

f) compounds of Fornel I or I 'in which R ^{7 is} OH,

g) compounds of the formula I or I ¹ in which R ^{7 is} OM,

h) compounds of the formula I or I ¹ in which R ^{1 is} hydrogen, chlorine, fluorine, nitro, trifluoromethyl, methoxy, bromine, methylthio, methylsulfonyl, carboxy, trichloromethyl or methyl,

i) compounds of the formula I or I 'in which R ^{2 is} hydrogen, chlorine, nitro, methylthio, methylsulfinyl, mothylsulfonyl, methyl, fluorine, trifluoromethyl or trichloromethyl.

Particular mention should be made of combinations of subgroups a) to e) with h) and i) both as free acid (group f)) and as salts (group g)).

Particular preference is given to the compounds of the formula I or I '

R ^{1 is} hydrogen; Fluorine; Chlorine; Bromine; nitro; cyano; Methyl; trifluoromethyl; trichloromethyl; methoxy; methylthio; methylsulfinyl; Methylsulfonyl carboxy; carbamoyl; methoxycarbonyl; or ethoxycarbonyl; R ^{2 is} hydrogen; Fluorine; Chlorine; nitro; trifluoromethyl; trichloromethyl; methylthio; methylsulfinyl; or methylsulfonyl; R ^{3 is} hydrogen; Ci-C3-alkyl, phenyl; benzyl; or chlorphenyl.l; R ¹ * hydrogen; or methyl; R ^{5 is} hydrogen; or methyl; R ^{6 is} hydrogen; cyano; Methyl; or Ci-Cj-alkoxycarbonyl;

R ⁷ OH; or 0®M® M is a cation equivalent of the sodium, lithium, calcium, trimethylammonium or triethanolammonium ion.

To be mentioned as individual compounds are 2- (3-chloro-5-trifluoromethylpyridin-2-yl-carbonyl) -cyclohex-1-en-1-ol-3-one

2- (3-chloro-5-methylsulfonyl-pyridin-2-yl-carbonyl) cyclohex-l-en-lol-3-one.

The compounds of the formula Ia or Ia ¹ , in which the radicals R ¹ to R ^{6 are} as previously defined and R ^{7 is} OH can be prepared by

a) Reaction of cyclohexanediones of the formula II in which the radicals R ³ to R ^{6 are} as defined above, with a pyridine of the formula III, in which R ¹ and R ^{2 are} as previously defined v, X is halogen, preferably chloro is _L or bromine , the rest

0-C-OR ⁸ , or -OC-H-4-R ² and R ^{8 is} Ci-Ci, -alkyl, phenyl or benzyl, in the presence of a base

II III Ia (R ⁷ = OH)

or 3_ | ü V

R »'V V

R5 ^/ V

Ia ¹ (R ⁷ = OH) or

b) thermal rearrangement of an ester of the formula IV or IV ¹ , wherein the radicals R ¹ to R ^{6 are} as defined above

R ³ -!

I i

UK « V

R ^{5 /} V IV

R ³ -

/ V

I i

-H- -fR ²

R ^{s /} N

Ia (R ⁷ = OH)

or

or

i Γι

• / ^R1 o-tt-4 4-R ²

_R 3_!

R ⁵

-If -fR ²

IV

Ia ¹ (R ⁷ = OH)

preferably in the presence of cyanide.

The salts of the formula Ib or Ib ¹ , wherein the radicals R ¹ to R ⁶ as before

-Θ..Θ

are defined, and R ^{7 is} 0 M, can be prepared by

c) reacting a cyclohexanedione Ia or Ia ¹ , wherein R ¹ to R ^{6 are} as defined above, and R ⁷ OH means with a base V, wherein B OH is M and M is as defined above

- 10 -

distress p5 ' ? ⁷ δ • y ^Rl / _R 3_! V Γι • λ " / X, R ' Ia A / • R ^sX \ • V / X, -4 -JR ² -> Ib \ SI - «· 4-R ² R ⁵ ' (R ⁷ = 'V' (R ⁷ (R ⁷ oV) • · Ia G p p OH) oV) • C- R3! _N κ \ y ii • V R ^{s /} 'ν Ib ¹ _ ¹ (R ⁷ = • / MI ρ 2 ir τ Iv • · S OH) + B V

The esters of the formula IV or IV ¹ are valuable intermediates for the preparation of the herbicidal end products Ia or Ia ¹ according to process variant b). The invention thus also relates to the new esters IV or IV. ¹ However, the esters IV or IV ¹ can also be formed as by-products in the acylation according to process variant a).

d) Furthermore, the compounds of the formula Ic or Ic ¹ in which one or more of the radicals R ¹ to R ^{s is} Ci-Ci, -alkyl-S (O) - with η = 1 or 2, and the remaining radicals as before are defined by oxidation of a thioether of the formula Id or Id ¹ , wherein the radical to be oxidized from the group R ¹ to R ⁶ Ci-Ci, -Alkyl-S (O) - with

η = 0. and the remaining radicals are as previously defined

- 11 -

4-R ²

R3!

+ -R ²

R 'i

a t

Id (thioether with η = 0) oxidation

Ic (sulfinyl or sulfonyl compound with η = 1 or 2)

?. U

-tR ²

j I Il W

^R 7 \ / \ ^R s X ^ ^R

R ⁵ R ⁵

Id ¹ (thioether with η = 0)

.R ¹

_3 I Il W R - · ·

Ic ¹ (sulfinyl or sulfonyl compound with η = 1 or 2)

Such oxidations are familiar to the person skilled in the art (eg Methodicum Chimicum, Ed. F. Körte, 9th Thieme Verlag Stuttgart 1976, Vol. 7 pages 696-698 and the references cited therein for the oxidation to sulfenes and Vol. 7, pages 751-755 and the literature mentioned there for the oxidation to sulfonates).

Preference is given to oxidation with H2O2 and with peracids, in particular with 3-chloroperbenzoic acid.

By suitable choice of bases, solvents and other reaction parameters, such as temperature, concentration etc., the O-acylation according to the following scheme can become the main reaction:

- ¹² -

ft Ri? M

/ \ ff / V / S V

^r3-A a⁺ ~ Λs ~ * ~ '^R3r.y ·,

i \ Iv 1 \ I \

II III IV

and or

Λ S *

R ⁵ 'V \ _N ^

In the C-acylation according to process variant a), it has proved to be advantageous to work the reaction in the presence of small amounts of cyanide. A low cyanide concentration can be ensured, for example, by the addition of acetone cyanohydrin.

The rearrangement of the ester IV or IV ¹ can also be carried out advantageously under the action of cyanide ions and in the presence of a base.

Although the synthesis of the compounds of the formula Ia or Ia ¹ outlined as reaction a) describes a process by which in principle all compounds encompassed by formula Ia or Ia ¹ can be prepared, it may be expedient for economic or procedural reasons to use certain compounds of the invention Formula Ia or Ia ¹ in other, encompassed by formula I or I 'derivatives. Examples of such conversions are, in addition to the reaction c) and d), for example, Vptfahren in which R ^{6 is} ester, halogen or Cyanoradikal. These radicals can analogously to the reactions shown below in Scheme 1 (Ha> Hb, Hc or Hd) even at the stage of the compounds

of the formula I are carried out. Such derivatization reactions are familiar to the person skilled in the art.

- 13 -

Advantageously, the above reactions are carried out in a reaction-inert solvent. In this case come as inert solvents, hydrocarbons such as benzene, toluene or xylene; Ethers, such as diethyl ether, methyl isopropyl ether, glyme, diglyme, cyclic ethers, such as tetrahydrofuran and dioxane, ketones, such as acetone, methyl ethyl ketone, amides, such as dimethylformamide, N-methylpyrrolidone, sulfoxides, such as dimethyl sulfoxide, or chlorinated hydrocarbons, such as dichloromethane, trichloromethane, Tetrachloromethane or tetrachloroethane, alcohols such as methanol, ethanol, isopropanol, propanol, butanol, etc. into consideration.

Also, solvent mixtures may be used advantageously as organic solvents in admixture with water in some cases.

The reaction temperature can be varied within wide limits. Suitable reaction temperatures are, for example, '.wischen -20 ⁰ C and the reflux temperature of the reaction mixture. Preferably, the reaction is carried out at a temperature between 0 ⁰ C and 100 ⁰ C.

In the case of the reactions a) and b), it is advantageous to work with base addition. Suitable bases include i.a. Sodium, potassium and calcium hydroxides, alkali and alkaline earth carbonates, amines such as triethylamine or heterocycles such as pyridine, 4-dimethylaminopyridine, DABCO and alkali metal hydrides.

The reactions a) and b) can also be advantageously carried out under phase transfer conditions in two-phase systems. Such reactions are well known to those skilled in the art (e.g., described in Dehmlow and Dehmlow, Phase Transfer Catalysis, Verlag Chemie, Weinheim 1983; W.E. Keller, Phase Transfer Reactions Vol. 1 and Vol. 2, G. Thieme Verlag, Stuttgart 1986, 1987).

The cyclohexanediones of the formula II are either known or they can be prepared analogously to processes known from the literature.

- 14 -

General access to the cyclohexanediones II is made possible by the following malonic ester synthesis, in which the specifically substituted cyclohexanediones Ha, Hb or Hc can be prepared in accordance with the following scheme from an aldehyde or ketone VI and acetone:

Scheme 1

R ³ 'V

VI

VIII +

+ CH ₃ -C -CH ₃

VII

COOR ¹ CHR ⁵ CO

Michael

COOR ¹ addition

• ^{y X}

CH ₃

ff

VIII

R ^{s /} V

Ha (R ⁶ = COOR ¹ , R ¹

C ₁ -C ₁ alkyl)

Saponify

Ha

+ decarboxylic acid

Hb (R ⁶ = H)

The compounds of the formula Hc in which the radicals R ³ to R 'are defined above and R ^{6 is} cyano, can be modified in a modification of Reaction Scheme 1 by Michael addition of cyanoacetic acid ester XIII in which R ^{5 is} as previously defined and R C ¹ -C 12 alkyl refers to the ketone VIII wherein R ³ and R ¹ * are as previously defined.

Scheme 2

VIII

COOR ¹ CHR ⁵ CN

XIII

Hc (R ⁶ = CN)

In the case of the pyridinecarboxylic acid derivatives III, in particular the acid chlorides are preferred.

- 15 -

The pyridine-2-carboxylic acid chloride IHa can be advantageously prepared by a Pd-catalyzed carbonylation reaction according to the following Reaction Scheme 3:

Scheme 3

V Ntal

Saponify

XI -

R ¹ OlI Et ₃ N

CO Pd cat

C00R '

XI

halogenate

Ri "R ²

^Ζ · ^Β · ^SOzClz or (COCl; 2

CO-X XIV IIIa (X = halogen)

In the above scheme, Hal is halogen (primarily chlorine); R ¹ Cj-Ci, -Alkyl and Pd-Kat is preferably PdCl2 (TPP) 2 a tri-henyl hoshpinkomplex of palladium.

The Picolinsaurederivate XI, IHa and XIV mentioned in Scheme 3 are valuable intermediates for the synthesis of cyclohexanedioi invention I. For the most part, these compounds are new.

Thus, the invention also applies to the novel picololauric derivatives of the formula XV

Il

XV,

CO-Y

wherein

Y OH; Ci-Ci ₁ -alkoxy; or halogen; and

R ¹ and R ^{2 are} independently halogen, nitro; cyano; Ci-C haloalkyl; Ci-C, alkyl; Ci-Cι, alkoxy; or Ci-Ci, -alkyl-S (O) -; and

η 0; 1; or 2;

means

- 16 -

with the proviso that when Y is chlorine and R ^{1 is} in position 3 and R ^{2 is} in position 5, R ¹ and R ^{2 are} not both together chlorine or both together methyl or when R ^{1 is} nitro R ² not methyl.

Preference is given to the picolinic acid derivatives of the formula XV ¹ ,

R ² · R ¹

l] j XV ',

W CO-Y

Y OH; Ci-Ci ₁ -alkoxy; or halogen; and

R ¹ and R ^{2 are} independently halogen, nitro; cyano; Ci-Ci _1- haloalkyl; Ci-C, alkyl; Ci-C, alkoxy; or Ci-Ci, -alkyl-S (O) -; and η 0; 1; or 2; with the proviso that when Y is chlorine, R ¹ and R ^{2 are} not both together chlorine or both together are methyl or R ^{1 is} nitro and R ^{2 is} methyl.

Particularly preferred are the compounds of formula XV ¹ , wherein

Y OH; Ci-C, alkoxy; or halogen; R ^{1 is} hydrogen; and R ^{2 is} C ₁ -C ₁ -alkoxy, C ₁ -C 4 -haloalkyl; or cyano means.

Also particularly preferred are the compounds of formula XV ¹ , wherein

Y OH; Ci-Ci ₁ -alkoxy; or halogen;

R ^{1 is} Ci-C u -alkoxy; Ci-C haloalkyl; or cyano; and R ^{2 is} Waser off.

Particular mention should be made in the compounds of the formula XV as well as the compounds which are particularly preferred, and the compounds XV 'which are acid chlorides, ie those compounds in which Y is chlorine.

- 17 -

264 O O 2

The compounds of the formula I are highly active plant active ingredients which, at suitable application rates, are outstandingly suitable as selective herbicides for weed control in crops of useful plants. That is, at these application rates, the active compounds of the formula I are characterized by good selective herbicidal properties against weeds. In particular, cereals such as rye, barley, oats, wheat and corn but also other crops such as millet, rice, cotton, sugarcane or soybean or permanent crops (such as vines or plantations) remain virtually undamaged at low application rates. With increased application rates, the culture mushrooms are only slightly affected in their growth. If very high application rates are applied, the substances of formula I exhibit total herbicidal properties. The application rates are generally 0.001 to 4 kg, preferably 0.005 to 2 kg of active substance per hectare.

At high expenditure, the compounds of formula I can also be used as Totalherbicide. They are particularly suitable for weed control on paths, squares, tracks or other areas where a complete kill of the plants growing there is desired.

The Selective-herbicidal Action Her compounds of the invention is found both in the pre-eminent and the post-operative application. These agents can be used equally well in preemergence and postemergence procedures for selective weed control.

Advantageously, the active compounds or agents according to the invention can also be applied to the propagation material of the crop. Particularly noteworthy here is the seed dressing. Propagation material is seeds, cuttings or other parts of the plant from which the crop can be grown. The reproductive material treated with an effective amount of a compound of formula I is also a counterpart of the invention.

The invention also relates to herbicidal compositions containing a novel active ingredient of the formula I, as well as methods for pre- and post-environmental weed control.

- 18 -

The compounds of the formula I are used in unchanged form or preferably as agents together with the auxiliaries customary in formulation technology and are therefore used, for example, in to emulsion concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, also encapsulations in e.g. processed polymeric substances in a known manner. The application methods such as spraying, misting, dusting, scattering or pouring are selected in the same way as the type of means according to the objectives and the prevailing conditions.

The formulations, i. the agents, preparations or compositions containing the active substance of the formula I and, where appropriate, one or more excipients or excipients which are solid or liquid, are prepared in a known manner, e.g. by intimately mixing and / or grinding the active ingredients with diluents, e.g. with solvents, liquid solid carriers, and optionally surface-active compounds (surfactants).

Possible solvents and extenders are: Aromatic hydrocarbons, preferably the fractions Ce to Ci21, such as, for example, Xylene mixtures or substituted naphthalenes, phthalic esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl or ethyl ketones such as cyclohexanone, strongly polar solvents such as N-methyl 2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oils, such as epoxidized coconut oil or soybean oil or water.

As solid carriers, e.g. For dusts and dispersible powders, ground natural minerals are generally used, such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. As granular, adsorptive granule carriers are porous types such. Pumice, broken brick, sepiolite or bentonite, as non-sorptive carrier materials

e.g. Calcite or sand in question. In addition, a variety of vorgrar.ulierten materials of inorganic or organic nature, in particular dolomite or crushed Pflanzenrückständo be used.

Depending on the nature of the active compound of the formula I to be formulated, surface-active compounds may be nonionic, cationic and / or anionic surfactants having good emulsifying, dispersing and wetting properties. Surfactants are also surfactant mixtures.

Suitable anionic surfactants may be both so-called water-soluble soap-fiber and water-soluble synthetic surface-active compounds.

As soaps, the alkali, alkaline earth or optionally substituted ammonium salts of higher fatty acids (C10-C22), e.g. the Na or K salts of OeI or stearic acid, or of natural fatty acid mixtures, e.g. from coconut or tallow oil can be obtained, called. Furthermore, the fatty acid methyl taurine salts should be mentioned.

More often, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are generally present as alkali, alkaline earth or optionally substituted ammonium salts and have an alkyl radical of 8 to 22 carbon atoms, alkyl also including the alkyl moiety of acyl radicals, e.g. the Na or Ca salt of lignosulfonic acid, of dodecylsulfuric acid ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids.

This subheading also covers the salts of sulfuric acid esters and sulphonic acids of fatty alcohol-ethylene oxide adducts. The sulfonated Benziir ^ dazolderivate preferably contain 2-sulfonic acid groups and a fatty acid radical having 8 to 22 carbon atoms. Alkylarylsulfonates are e.g. the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalene

- 20 -

sulfonic acid or a Naphthalinsul.'onsäure-formaldehyde condensation product.

Furthermore, corresponding phosphates, e.g. Salts of the phosphoric acid ester of a p-nonylphenol (4-14) -Ethylenoxid adduct or phospholipids in question.

Suitable nonionic surfactants are primarily polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated acids and alkylphenols, the 3 to 10 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols can contain.

Other suitable ionic surfactants are the water-soluble. ⁰ O to 250 Euhylenglykolethergruppen and 10 to IOC Propylenglykolethe .. groups containing Polypropylene glycol, Ethylendiaminopolypropylenglykol and alkylpolypropylene glycol having 1 to 10 carbon atoms in the alkyl chain, said compounds usually contain per propylene glycol unit 1 to 5 ethylene glycol units.

Non-ionic polyethoxyethanols, castor oil polyglycol ethers, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol may be mentioned as examples of nonionic surfactants.

Also suitable are fatty acid esters of polyoxyethylene sorbitan, such as the polyoxyethylene sorbitan trioleate.

The cationic surfactants are, above all, quaternary ammonium salts which contain as N-substituents at least one alkyl radical having 8 to 22 carbon atoms and have as further substituents lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates _: for example, stearyltrimethylammonium chloride or benzyldi (2-chloroethyl) -ethylammonium bromide.

- 2i -

The surfactants commonly used in the formulation technique are i.a. described in the following publications:

"1986 International McCutcheon's Emulsifiers & Detergents" Glen Rock, N.J., USA, 1986; H. Stäche, "Tensid-Taschenbuch", 2nd edition.,

C. Hanser Verlag, Munich, Vienna, 1981;

M. and J. Ash. "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-1981.

The active ingredient preparations generally contain 0.1 to 95%, in particular 0.1 to 80% active ingredient of the formula I, 1 to 99.9% of one or more solid or liquid additives and 0 to 25 % of a surfactant.

In particular, preferred formulations are composed as follows: (% = weight percent).

Emulsifiable Concentrates: Active Ingredient: Surfactants: Liquid Carrier:

1 to 20%, preferably 5 to 10% 5 to 30%, preferably 10 to 20%

50 to 94%, preferably 70 to 5%

dusts:

Active ingredient:

solid carrier:

0.1 to 10%, preferably 0.1 to 1% 99.9 to 90%, preferably 99.9 to 99%

Suspension Concentrates: Active Ingredient: Water: Surfactant:

5 '.Ls 75%, preferably 10 to 50% to 25%, preferably 88 to 30% 1 to 40%, preferably 2 to 30%

Wettable powder: Active ingredient: surfactant! solid carrier:

0.5 to 90%, preferably 1 to 80% 0.5 to 20%, preferably 1 to 15% 5 to 95%, preferably 15 to 90 %

granules "

Active ingredient "0.5 to 30%, preferably 3 to 15 % solid carrier" 99.5 to 70 %; preferably 97 to 85 %

While concentrated products are preferred as merchandise », the end user generally uses diluted medications. The forms of application can be diluted down to 0.001 % of active ingredient

The compositions may also contain other additives such as stabilizers, defoamers, viscosity regulators, binders, adhesives and fertilizers or other active ingredients for the purpose of obtaining special liqueurs.

embodiments The following examples illustrate the invention « hq ₁ You are playing games HqIo compounds , the formula I H!,!, "Reactions with cyclohexanediones , the , formula II

Η, Ι ^ Ι ^ Ι, _i 2- (3 'ChI ₁ Or-5-1rifluormethyl-pyridin-ff-yl-carbonyl) ~ cyclohex-l-en-l-ol-S-on

To a solution of 2.2 g (20 mmol) of 1,3-cyclohexanedione and 7 ml (50 mmol) of triethylamine in 25 ml of dichloromethane are added dropwise 4.9 g (20 mmol) of s-chloro-S-trifluoromethylpyridine ^ -carboxylic acid chloride maintaining the temperature at 35 ⁰ C rises "the mixture is then stirred for 15 hours at room temperature," the black

Suspeneion is charged with 250 ml Oichlormethan diluted ', at 0 to 5 ° with IN HCl to pH 1 and washed 2x with HgO ₀ The product is gonutscht then 5% NaHCO, -Löeung extracted ^ ¹ cold with 37% HCl precipitated " and dried Man isolated 4ψΟ g (63 %) of the title compound of the formula

Cl

as crystals, mp _e 102-105 ⁰ C (comp, No. l> 005th).

- 23 -

H.1.1.2. 2- (5-trifluoromethylpyrid -2-yl-carbonyl) -cyclohex-1-en-1-ol-3-o- n To a solution of 9.5 g (85 mmol) of 1,3-cyclohexanedione and 24 ml (170 mmol) triethylamine in 85. il dichloromethane werien dropwise at 2O-25 ° C, 20.4 g (85 mmol) of 5-trifluoromethylpyridine-2-carbonyl chloride added dropwise. After stirring for 4 hours at room temperature, 0.8 ml of acetone cyanohydrin are added and the mixture is stirred for a further 15 hours. The reaction solution is diluted with 200 ml of dichloromethane, adjusted at 0-5 ⁰ C with HCl IN to pH 1, washed 2x with water and extracted with NaHCO 3) solution 5%. This is washed with dichloromethane, adjusted to pH 1 with HCl 37 % , the precipitated product is filtered by suction and dried.

17.2 g (71%) of the title compound of the formula are isolated

ΑΛ-Ο-

• * N = "I IJ

as crystals of mp. 95-97 ° C (Comp. No. 1,010).

Analogously to the above preparation process, the compounds of Table 1 can be synthesized:

H .1.1.3. 2- (3-chloro-5-methylthio-pyridin-2-yl-carbonyl) cyclohex-l-en-l-

ol-3-one

4.4 g (0.048 mol) of 1,3-cyclohexanedione and 10.6 g (0.048 mol) of 3-chloro-5-methylthiopyridine-2-carboxylic acid chloride are prepared analogously to H.1.1.1. implemented and cleaned.

7.2 g (50.4%) of the title compound of the formula are isolated

, / ~ \ -C-CH ₃

i ί

^ * ^{7 N} 0H as crystals of mp. 113 ° C (dec.) (Comp. No. 1,018).

- 24 · -

H.1.1 4. (3-Chloro-5-methylsulfonyl-pyridin-2-yl-carbonyl) -eyelohex-1

en-l-ol-3-one

To a suspension of 10.2 g (40 mmol) of S-chloro-S-methylsulfonyl-pyridine-2-carboxylic acid chloride in 80 ml of dichloromethane at 0-5 ⁰ C, a solution of 5.6 g (50 mmol) 1.3 -Cyclohexandione and 14 ml (100 mmol) of triethylamine in 50 ml of dichloromethane. After stirring for 3 hours at room temperature, 0.5 ml of acetone cyanohydrin are added to the suspension thus obtained. The mixture is then stirred for 3 hours at room temperature. The dark brown suspension is diluted with 20 ml of dichloromethane, adjusted to pH 1 at ⁰ ° -5 ° C. with 1N HCl and washed twice with H ₂ O. The product is then extracted with NaHCO ₃ solution 5%, precipitated cold with HCl 37%, sucked and dried.

10.4 g (78.9%) of the title compound of the formula are isolated

^C1 \ _

• H- (^ -SO ₃ CH ₃

i π ^{N = /} \ ^{/ n} oh

as white crystals of the mp> 200 ° C (Zers.) (Ed. No. 1.020).

H. 1.2.1. Preparation of 2- (S-chloro-S-methylsulfonylpyridine) -yl-car-

carbonyl) cyclohex-l-en-l-ol-3-one

To a solution of 3 g (0.01 mol) of 2- (3-chloro-5-methylthiopyridin-2-ylcarbonyl) -cyclohex-1-en-l-ol-3-one in 5 ml of dichloromethane is added under cooling 20-30 ⁰ C., a solution of 4.1 g (0.02 mol) 3-chloroperbenzoic acid 85% in 50 ml of dichloromethane. The mixture is then stirred for 4 hours at room temperature. The yellow suspension is filtered off from the chlorobenzoic acid and evaporated on a rotary evaporator. The resulting mass is triturated with 50 ml of ether, sucked and dried.

1.8 g (51.6%) of the title compound of the formula are isolated

as crystals of the mp 15O ⁰ C (2 * rs.) (Comp. No. 1,020).

Table 1

- 25 -

284 υ υ 2

Compounds of the formula

⁰ S f I R ² R ³ H R- H R ⁵ H R ⁶ phys. data Cl H H H H Mp 144-146 ° C ^R \ i I 'i • · ^/ vv H H H H H Verb no. Cl H H H H Mp 106-107 ⁰ C 1001 R ¹ H H H H H resin 1002 Cl CF ₃ H H H H Mp 102-105 ⁰ C 1003 Cl H H H H H 1004 H NO ₂ H H H H 1005 H Cl H H H H 1006 Cl H H H H H 1007 NO ₂ CF ₃ H H H H Mp 95-97 ° C 1008 H H H H H H 1009 NO ₂ H H H H H 1010 CF ₃ Cl H H H H 1011 H Cl H H H H 1012 OCH ₃ Cl H H H H 1013 CN Cl H H H H 1014 OCH ₃ Cl H H H H 1015 CN SCH ₃ H H H H Mp> 113 ° C (Zers) 1016 br SOCH ₃ H H H H Mp 134-136 ° C 1017 SCH ₃ SO ₂ CH ₃ H H H H Mp> 150 ° C (Zers) 1018 SO ₂ CH ₃ Cl H H H H 1019 Cl H H H H H 1020 Cl SO ₂ CH ₃ H H H H 1021 Cl CH ₃ H H H H 1022 SOCH ₃ F H H H H Mp 113-115 ° C 1023 SO ₂ CH ₃ CF ₃ H H H H 1024 H F H H H H 1025 H CF ₃ H H H H 1026 Cl F H H H H 1027 H CCl ₃ H H H H 1028 F H H H H H 1029 F CCl ₃ H H H H 1030 CF ₃ Cl H H H H 1031 H H CH ₃ H H H 1032 CCl ₃ Cl CH ₃ H H H Mp 117-124 ° C 1033 Cl H CH ₃ H H H 1034 CCl ₃ Cl CH ₃ H H H 1035 CH ₃ H CH ₃ H H H 1036 Cl CF ₃ CH ₃ H H H Mp 93-103 ⁰ C 1037 Cl H CH ₃ H H H 1038 H NO ₂ H 1039 H 1040 Cl 1041 NO ₂ H

- 26 -

Verb no. R ¹ R ² R ³ R " H R ⁵ H R ⁶ H phys. data 1042 NO ₂ Cl CH ₃ H H H 1043 CF ₃ H CH ₃ H H H 1044 H CF ₃ CH ₃ H H H Mp 99-101 ⁰ C 1045 OCH ₃ H CH ₃ H H H 1046 CN H CH ₃ H H H 1047 OCH ₃ Cl CH ₃ H H H 1048 CN Cl CH ₃ H H H 1049 br Cl CH ₃ H H H 1050 SCH ₃ Cl CH ₃ H H H 1051 SO ₂ CH ₃ Cl CH ₃ H. Il H 1052 Cl SCH ₃ CH ₃ H H H 1053 Cl SOCH ₃ CH ₃ H H H 1054 Cl SO ₂ CH ₃ CH ₃ H H H 1055 SOCH ₃ Cl CH ₃ H H H 1056 SO ₂ CH ₃ H CH ₃ H H H 1057 H SO ₂ CH ₃ CH ₃ H H H 1058 H CH ₃ CH ₃ H H H 1059 Cl F CH ₃ H H H 1060 H CF ₃ CH ₃ H H H 1061 F F CH ₃ H H H 1062 F CF ₃ CH ₃ H H H 1063 CF ₃ F CH ₃ H H H 1064 H CCl ₃ CH ₃ H H H 1065 CCl ₃ H CH ₃ H H H 1066 Cl CCl ₃ CH ₃ H H H 1067 CCl ₃ Cl CH ₃ H H H 1068 CH ₃ H CH ₃ H H H 1069 Cl Cl C ₂ H ₅ H H H 1070 Cl H C ₂ H ₅ H H H 1071 H Cl C ₂ H ₅ H H H 1072 H H C ₂ H ₅ H H H 1073 Cl CF ₃ C ₂ H ₅ H H H 1074 NO ₂ H C ₂ H ₅ H H H 1075 H NO ₂ C ₂ H ₅ H H H 1076 NO ₂ Cl C ₂ H ₅ H H H 1077 CF ₃ H C ₂ H ₅ H H H 1078 H CF ₃ C ₂ H ₅ H H H 1079 OCH ₃ H η - u _ H H H 1080 CN H C ₂ H ₅ H H H 1081 OCH ₃ Cl C ₂ H ₅ H H H 1082 CN Cl C ₂ H ₅ H H H 1083 br Cl C ₂ H ₅ H H H 1084 SCH ₃ Cl C ₂ H ₅ H H H 1085 SO ₂ CH ₃ Cl C ₂ H ₅ H H H 1086 Cl SCH ₃ C ₂ H ₅ H H H 1087 Cl SOCH ₃ C ₂ H ₅ H H H 1088 Cl SO ₂ CH ₃ C ₂ H ₅ H H H 1089 SOCH ₃ Cl C ₂ H ₅ H H H 1090 SO ₂ CH ₃ H C ₂ H ₅ H H H 1091 H SO ₂ CH ₃ C ₂ H ₅ H H H 1092 H CH ₃ C ₂ H ₅ H H H 1093 Cl F C ₂ H ₅

- 27 -

284

Verb no. R ¹ R ² R ³ R * H R ⁵ H R ⁶ H phys. data 1.C94 H CF ₃ C ₂ H ₅ H H H 1095 F F C ₂ H ₅ H H H 1096 F CF ₃ C ₂ H ₅ H H H 1097 CF ₃ F C ₂ H ₅ H H H 1098 H CCl ₃ C ₂ H ₅ H H H 1099 CCl ₃ H C ₂ H ₅ H H H 1100 Cl CCl ₃ C ₂ H ₅ H H H 1101 CCl ₃ Cl C ₂ H ₅ H H H 1102 CH ₃ H C ₂ H ₅ H H H 1103 Cl Cl nC ₃ H ₇ H . H H 1104 Cl H Ti-C ₃ H ₇ H H H 1105 H Cl UC ₃ H ₇ H H H 1106 H H Ti-C ₃ H ₇ H H H 1107 Cl CF ₃ Ti-C ₃ H ₇ H H H 1108 NO ₂ H nC ₃ H ₇ H H H 1109 H NO ₂ Ti-C ₃ H ₇ H H H 1110 NO ₂ Cl Ti-C ₃ H ₇ H H H 1111 CF ₃ H Ti-C ₃ H ₇ H H H 1112 H CF ₃ Ti-C ₃ H ₇ H H H 1113 OCH ₃ H Ti-C ₃ H ₇ H H H 1114 CN H Ti-C ₃ H ₇ H H H 1115 OCH ₃ Cl Ti-C ₃ H ₇ H H H 1116 CN Cl Ti-C ₃ H ₇ H H H 1117 br Cl Ti-C ₃ H ₇ H H H 1118 SCH ₃ Cl Ti-C ₃ H ₇ H H H 1119 SO ₂ CH ₃ Cl Ti-C ₃ H ₇ H H H 1120 Cl SCH ₃ Ti-C ₃ H ₇ H H H 1121 Cl SOCH ₃ Ti-C ₃ H ₇ H ii H 1122 Cl SO ₂ CH ₃ Ti-C ₃ H ₇ H H H 1123 SOCH ₃ Cl Ti-C ₃ H ₇ H H H 1124 SO ₂ CH ₃ H Ti-C ₃ H ₇ H H H 1125 H SO ₂ CH ₃ Ti-C ₃ H ₇ H H H 1126 H CH ₃ Ti-C ₃ H ₇ H H H 1127 Cl F Ti-C ₃ H ₇ H H H 1128 H CF ₃ Ti-C ₃ H ₇ H H H 1129 F F Ti-C ₃ H ₇ H H H 1130 F CF ₃ Ti-C ₃ H ₇ H H H 1131 CF ₃ F Ti-C ₃ H ₇ H H H 1132 H CCl ₃ Ti-C ₃ H ₇ H H H 1133 CCl ₃ H Ti-C ₃ H ₇ H H H 1134 Cl CCl ₃ Ti-C ₃ H ₇ H H H 1135 CCl ₃ Cl Ti-C ₃ H ₇ H H H 1136 CH ₃ H Ti-C ₃ H ₇ H H H 1137 Cl Cl XC ₃ H ₇ H H H 1138 Cl H iC ₃ H ₇ H H H 1139 H Cl 1-C ₃ H ₇ H H H 1140 H H 1-C ₃ H ₇ H H H 1141 Cl CF ₃ iC ₃ H ₇ H H H Mp 72-75 ° C 1142 NO ₂ H iC ₃ H ₇ H H H 1143 H NO ₂ 1-C ₃ H ₇ - H H H 1144 NO ₂ Cl 1-C ₃ H ₇ H H H 1145 CF ₃ H 1-C ₃ H ₇

- 28 -

No.

1,146 1,147 1,148 1,149 1,150 1,151 1,152 1,153 1,154 1,155 1,156 1,157 1,158 1,159 1,160 1,161 1,162 1,163 1,164 1,165 1,166 1,167 1,168 1,169 1,170 1,171 1,172 1,173 1,174 1,175 1,176 1,177 1,178 1,179 1,180 1,181.

1,182 1,183 1,184 1,185 1,186 1,187 1,188 1,189 1,190 1,191 1,192 1,193 1,194 1,195 1,196 1,197

R ¹

OCH ₃

CN

OCH ₃

CN

br

SCH ₃ SO ₂ CH ₃

Cl

Cl

Cl

SOCH ₃ SO ₂ CH ₃

Cl

CF ₃

CCl ₃

Cl

CCl ₃

Ch ₃

Cl

Cl

Cl

NO ₂

NO ₂

CF ₃

OCH ₃

CN

OCH ₃

CN

br

SCH ₃ SO ₂ CH ₃

Cl

Cl

Cl

SOCH ₃ SO ₂ CH ₃

Cl

R ² R ³ R " H R ⁵ H R ⁶ H phys. data CF ₃ 1-C ₃ H ₇ H H H Mp 1O3-1O6 ° C H 1-C ₃ H ₇ H H H H iC ₃ H ₇ H H H Cl iC ₃ H ₇ H H H Cl 1-C ₃ H ₇ H H H Cl 1-C ₃ H ₇ H H H Cl 1-C ₃ H ₇ H H H Cl 1-C ₃ H ₇ H H H SCH ₃ iC ₃ H ₇ H H H SOCH ₃ iC ₃ H ₇ H ' H H SO ₂ CH ₃ 1-C ₃ H ₇ H H H Cl iC ₃ H ₇ H H H H iC ₃ H ₇ H H H SO ₂ CH ₃ iC ₃ H ₇ H H H CH ₃ 1-C ₃ H ₇ H H H F iC ₃ H ₇ H H H CF ₃ 1-C ₃ H ₇ H H H F XC ₃ H ₇ H H H CF ₃ 1-C ₃ H ₇ H H H F iC ₃ H ₇ H H H CCl ₃ iC ₃ H ₇ Λ H H H 1-C ₃ H ₇ H H H CCl ₃ 1-C ₃ H ₇ H H H Cl iC ₃ H ₇ H H H H iC ₃ H ₇ H H COOC ₂ H ₅ Cl nC ₃ H ₇ H H COOC ₂ H ₅ H nC ₃ H ₇ H H COOC ₂ H ₅ Cl nC ₃ H ₇ H H COOC ₂ H ₅ H nC ₃ H ₇ H H COOC ₂ H ₅ CF ₃ nC ₃ H ₇ H H COOC ₂ H ₅ H nC ₃ H ₇ H H COOC ₂ H ₅ NO ₂ nC ₃ H ₇ H H COOC ₂ H ₅ Cl nC ₃ H ₇ H H COOC ₂ H ₅ H nC ₃ H ₇ H H COOC ₂ H ₅ CF ₃ Ti-C ₃ H ₇ H H COOC ₂ H ₅ H n - C ₃ H ₇ H H COOC ₂ H ₅ H nC ₃ H ₇ H H COOC ₂ H ₅ Cl nC ₃ H ₇ H H COOC ₂ H ₅ Cl nC ₃ H / H H COOC ₂ Hs Cl nC ₃ H ₇ H H COOC ₂ H ₅ Cl Ti-C ₃ H ₇ H H COOC ₂ H ₅ Cl Ti-C ₃ H ₇ H H COOC ₂ H ₅ SCH ₃ Ti-C ₃ H ₇ H H COOC ₂ H ₅ SOCH ₃ Ti-C ₃ H ₇ H H COOC ₂ H ₅ SO ₂ CH ₃ Ti-C ₃ H ₇ H H COOC ₂ H ₅ Cl nC ₃ H ₇ H H COOC ₂ H ₅ H Ti-C ₃ H ₇ H H COOC ₂ H ₅ SO ₂ CH ₃ Ti-C ₃ H ₇ H H COOC ₂ H ₅ CH ₃ Ti-C ₃ H ₇ H H COOC ₂ H ₅ F Ti-C ₃ H ₇ H H COOC ₂ H ₅ CF ₃ Ti-C ₃ H ₇ H H COOC ₂ H ₅ F Ti-C ₃ H ₇

- 29 -

Verb no.

1,198 1,199 1,200 1,201 1,202 1,203 1,204 1,205 1,210 1,211 1,212 1,213 1,221 1,211 1,216 1,213 1,221 1,220 1,216 1,217 1,218 1,219 1,220 1,222 1,222 1,222 1,222 1,225 1,230 1,231 1,232 1,233 1,230 1,235 1,236 1,237 1,238 1,239 1,240 1,241 1,242 1,243 1,244 1,245 1,246 1,247 1,248 1,249

R ¹ R ² R ³ R " H R ⁵ H R ⁶ phys. data F CF ₃ IV-C ₃ H ₇ H H COOC ₂ H ₅ CF ₃ F nC ₃ H ₇ H H COOC ₂ H ₅ H CCl ₃ Ti-C ₃ H ₇ H H C00C? H ₅ CCl ₃ H nC ₃ H ₇ H H COOC ₂ H ₅ Cl CCl ₃ nC ₃ H ₇ H H COOC ₂ H ₅ CCl ₃ Cl nC ₃ H ₇ H H COOC ₂ H ₅ CH ₃ H nC ₃ H ₇ H H COOC ₂ H ₅ Cl Cl 1-C ₃ H ₇ H H COOCH ₃ Cl H 1-C ₃ H ₇ H H COOCH ₃ H Cl 1-C ₃ H ₇ H · H COOCH ₃ H H 1-C ₃ H ₇ H H COOCH ₃ Cl CF ₃ iC ₃ H ₇ H H COOCH ₃ Mp 91-92 ° C NO ₂ H iC ₃ H ₇ H H COOCH ₃ H NO ₂ 1-C ₃ H ₇ H H COOoH ₃ NO ₂ Cl 1-C ₃ H ₇ H H COOCH ₃ CF ₃ H 1-C ₃ H ₇ H H COOCH ₃ H CF ₃ 1-C ₃ H ₇ H H COOCH ₃ OCH ₃ H 1-C ₃ H ₇ H H COOCH ₃ CN H XC ₃ H ₇ H H COOCH ₃ OCH ₃ Cl iC ₃ H ₇ H H COOCH ₃ CN Cl 1-C ₃ H ₇ H H COOCH ₃ br Cl 1-C ₃ H ₇ H H COOCH ₃ SCH ₃ Cl 1-C ₃ H ₇ H H COOCH ₃ SO ₂ CH ₃ Cl 1-C ₃ H ₇ H H COOCH ₃ Cl SCH ₃ 1-C ₃ H ₇ H H COOCH ₃ Cl SOCH ₃ 1-C ₃ H ₇ H H COOCH ₃ Cl SO ₂ CH ₃ 1-C ₃ H ₇ H H COOCH ₃ SOCH ₃ Cl 1-C ₃ H ₇ H H COOCH ₃ SO ₂ CH ₃ H iC ₃ H ₇ H H COOCH ₃ H SO ₂ CH ₃ iC ₃ H ₇ H H COOCH ₃ H CH ₃ iC ₃ H ₇ H H COOCH ₃ Cl F iC ₃ H ₇ H H COOCH ₃ H CF ₃ iC ₃ H ₇ H H COOCH ₃ F F iC ₃ H ₇ U H COOCH ₃ F CF ₃ 1-C ₃ H ₇ H H COOCH ₃ CF ₃ F iC ₃ H · / H H COOCH ₃ H CCl ₃ 1-C ₃ H ₇ H H COOCH ₃ CCl ₃ H 1-C ₃ H ₇ H H COOCH ₃ Cl CCl ₃ 1-C ₃ H ₇ H H COOCH ₃ CCl ₃ Cl iC ₃ H ₇ H H COOCH ₃ CH ₃ H 1-C ₃ H ₇ H H COOCH ₃ Cl Cl CH ₃ H H COOCH ₃ Cl H CH ₃ H H COOCH ₃ H Cl CH ₃ H H COOCH ₃ H H CH ₃ H H COOCH ₃ Cl CF ₃ CH ₃ H H COOCH ₃ NO ₂ H CH ₃ H H COOCH ₃ H NO ₂ CH ₃ H H COOCH ₃ NO ₂ Cl CH ₃ H H COOCH ₃ CF ₃ H CH ₃ H H COOCH ₃ H CF ₃ CH ₃ H H COOCH ₃ OCH ₃ H CH ₃ COOCH ₃

30 -

Verb no. R ¹ R ² R ³ R " H R ⁵ H P ⁶ phys. data 1250 CN H CH ₃ H H COOCH ₃ 1251 OCH ₃ Cl CH ₃ H H COOCH ₃ 1252 CN Cl CH ₃ H H COOCH ₃ 1253 br Cl CH ₃ H H COOCH ₃ 1254 SCH ₃ Cl CH ₃ H H COOCH ₃ 1255 SO ₂ CH ₃ Cl CH ₃ H H COOCH ₃ 1256 Cl SCH ₃ CH ₃ H H COOCH ₃ 1257 CJ. SOCH ₃ CH ₃ H H COOCH ₃ 1258 Cl SO ₂ CH ₃ CH ₃ H H COOCH ₃ 1259 SOCH ₃ Cl CH ₃ H' H COOCH ₃ 1260 SO ₂ CH ₃ H CH? H H COOCH ₃ 1261 H SO ₂ CH ₃ CH ₃ H H COOCH ₃ 1262 H CH ₃ CH ₃ H H COOCH ₃ 1263 Cl F CH ₃ H H COOCH ₃ 1264 H CF ₃ CH ₃ H H COOCH ₃ 1265 F F CH ₃ H H COOCH ₃ 1266 F CF ₃ CH ₃ H H COOCH ₃ 1267 CF ₃ F CH ₃ H H COOCH ₃ 1268 H CCl ₃ CH ₃ H H COOCH ₃ 1269 CCl ₃ H CH ₃ H H COCCH ₃ 1270 Cl CCl ₃ CH ₃ H H COOCH ₃ 1271 CCl ₃ Cl CH ₃ H H COOCH ₃ 1272 CH ₃ H CH ₃ CH ₃ H COOCH ₃ 1273 Cl Cl CH ₃ CH ₃ H H Mp 131-133 ° C 1274 Cl H CH ₃ CH ₃ H H 1275 H Cl CH ₃ CH ₃ H H 1276 H H CH ₃ CH ₃ H H 1277 Cl CF ₃ CH ₃ CH ₃ H H Mp 95-98 ^c C 1278 NO ₂ H CH ₃ CH ₃ H H 1279 H NO ₂ CH ₃ CH ₃ H H 1280 NO ₂ Cl CH ₃ CH ₃ H H 1231 CF ₃ H CH ₃ CH ₃ H H 1282 H CF ₃ CH ₃ CH ₃ H H 1283 OCH ₃ H CH ₃ CH ₃ H H 1284 CN H CH ₃ CH ₃ H H 1285 OCH ₃ Cl CH ₃ CH ₃ H H 1286 CN Cl CH ₃ CH ₃ H H 1287 br Cl CH ₃ CH ₃ H H 1288 SCH ₃ Cl CH ₃ CH ₃ H H 1289 SO ₂ CH ₃ Cl CH ₃ CH ₃ H H 1290 Cl SCH ₃ CH ₃ CH ₃ H H 1291 Cl SOCH ₃ CH ₃ CH ₃ H H 1292 Cl SO ₂ CH ₃ CH ₃ CH ₃ H H 1293 SOCH ₃ Cl CH ₃ CH ₃ H H 1294 SO ₂ CH ₃ H CH ₃ CH ₃ H H 1295 H SO ₂ CH ₃ CH ₃ CH ₃ H H 1296 H CH ₃ CH ₃ CH ₃ H H 1297 Cl F CH ₂ CH ₃ H H 1298 H CF ₃ CH ₃ CH ₃ H H 1299 F F CH ₃ CH ₃ H H 1300 F CF ₃ CH ₃ CH ₃ H H 1301 CF ₃ F CH ₃ H

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Verb no. R ¹ R ² R ³ R ¹ * R ⁵ H R ⁶ phys. data 1302 H CCl ₃ CH ₃ CH ₃ H K 1303 CCl ₃ H CH ₃ CH ₃ H H 1304 Cl CCl ₃ CH ₃ CH ₃ H H 1305 CCl ₃ Cl CH ₃ CH ₃ H H 1306 CH ₃ H CH ₃ CH ₃ H H 1307 Cl Cl CH ₃ CH ₃ H COOC ₂ H ₅ 1308 Cl H CH ₃ CH ₃ H COOC ₂ H ₅ 1309 H Cl CH ₃ CH ₃ H COOC ₂ H ₅ 1310 H H CH ₃ CH ₃ H COOCj-H ₅ 1311 Cl CF ₃ CH ₃ CH ₃ H COOC ₂ H ₅ 1312 NO ₂ H CH ₃ CH ₃ H COOC ₂ H ₅ 1313 H NO ₂ CH ₃ CH ₃ H COOC ₂ H ₅ 1314 NO ₂ Cl CH ₃ CH ₃ H COOC ₂ H ₅ 1315 CF ₃ H CH ₃ CH ₃ H COOC ₂ H ₅ 1316 H CF ₃ CH ₃ CH ₃ H COOC ₂ H ₅ 1317 OCH ₃ H CH ₃ CH ₃ H COOC ₂ H ₅ 1318 CN H CH ₃ CH ₃ H COOC ₂ H ₅ 1319 OCH ₃ Cl CH ₃ CH ₃ H COOC ₂ H ₅ 1320 CN Cl CH ₃ CH ₃ H COOC ₂ H ₅ 1321 br Cl CH ₃ CH ₃ H COOC ₂ H ₅ 1322 SCH ₃ Cl CH ₃ CH ₃ H COOC ₂ H ₅ 1323 SO ₂ CH ₃ Cl CH ₃ CH ₃ H COOC ₂ H ₅ 1324 Cl SCH ₃ CH ₃ CH ₃ H COCC ₂ H ₅ 1325 Cl SOCH ₃ CH ₃ CH ₃ H COOC ₂ H ₅ 1326 Cl SO ₂ CH ₃ CH ₃ CH ₃ H COOC ₂ H ₅ 1327 SOCH ₃ Cl CH ₃ CH ₃ H COOC ₂ H ₅ 1323 SO ₂ CH ₃ H CH ₃ CH ₃ H COCC ₂ H ₅ 1329 H SO ₂ CVI ₃ CH ₃ CH ₃ H COC-J ₂ H ₅ 1330 H CH ₃ CH ₃ CiI ₃ H OXV ₂ H ₅ 1331 Cl F CH ₃ CH ₃ H COOC ₂ H ₅ 1332 H CFj CH ₃ CH ₃ K COOC ₂ H ₅ 1333 F F CH ₃ CH ₃ K COOC ₂ H ₅ 1334 F CF ₃ CH ₃ CH ₃ H COOC ₂ H ₅ 1335 CF ₃ F CH ₃ CH ₃ H COOC ₂ H ₅ 1336 H CCl, CH ₃ CH ₃ H COOC ₂ H ₅ 1337 CCl ₃ H CH ₃ CH ₃ H COOC ₂ Hs 1338 Cl CCl ₃ CH ₃ CH ₃ H COOC ₂ H ₅ 1339 CCl ₃ Cl CH ₃ CH ₃ H COOC ₂ H ₅ 1340 CH ₃ H CH ₃ CH ₃ H COOC ₂ H ₅ 1341 Cl Cl C ₆ H ₅ H H H 1342 Cl H C ₆ H ₅ H H H 1343 H Cl C ₆ H ₅ \\ H H 1344 H H C ₆ H ₅ H H H 1. 345 Cl CF ₃ C ₆ H ₅ H H H Mp.> 150 ° C (Zer 1346 NO ₂ H C ₆ H ₅ H H H 1347 H NO ₂ C ₆ H ₅ H H H 1348 NO ₂ Cl C ₆ H ₅ H H H 1349 "F ₃ H C ₆ H ₅ H H H 1350 H CF ₃ C ₆ H ₅ H H H 1351 OCH ₃ H C ₆ H ₅ H H H 1352 CN H C ₆ H ₅ H H H 1353 OCH ₃ Cl C ₆ H ₅ H H

R ¹ R ² - R ³ 32 - H 2 R ⁵ H 8 4 0 H 02 Verb no. CN Cl C ₆ H ₅ R " H H R ⁶ H phys. data 1354 br Cl C ₆ H ₅ H H H 1355 SCH ₃ Cl C ₆ H ₅ H H H 1356 SO ₂ CH ₃ Cl C ₆ H ₅ H H H 1357 Cl SCH ₃ C ₆ H ₅ H H H 1358 Cl SOCH ₃ C ₆ H ₅ H H H 1359 Cl SO ₂ CH ₃ C ₆ H ₅ H H H 1360 SOCH ₃ Cl C ₆ H ₅ H H H 1. 361 SO ₂ CH ₃ H C ₆ H ₅ H H H 1362 H SO ₂ CH ₃ C ₆ H ₅ H ¹ H H 1363 H CH ₃ C ₆ H ₅ H H H 1364 Cl F C ₆ H ₅ H H H 1365 H CF ₃ C ₆ H ₅ H H H 1366 F F C ₆ H ₅ H H H 1367 F CF ₃ C ₆ H ₅ H H H 1368 CF ₃ F C ₆ H ₅ H H H 1369 H CCl ₃ C ₆ H ₅ H H H 1370 CCl ₃ H C ₆ H ₅ H H H 1371 CI CCl ₃ C ₆ H ₅ H H H 1372 CCl ₃ Cl C ₆ H ₅ H H H 1373 CH ₃ H C ₆ H ₅ H CH ₃ CH ₃ 1374 Cl Cl H H CH ₃ CH ₃ 1375 Cl H H H CH ₃ CH ₃ 1376 H Cl H H CH ₃ CH ₃ 1377 H H H H CH ₃ CH ₃ 1378 Cl CF ₃ H H CH ₃ CH ₃ 1379 NO ₂ H H H CH ₃ CH ₃ 1380 H NO ₂ H H CH ₃ CH ₃ 1301 NO ₂ Cl H H CH ₃ CH ₃ 1382 CF ₃ H H H CH ₃ CH ₃ 1383 H CF ₃ H H CH ₃ CH ₃ 1384 OCH ₃ H H H CH ₃ CH ₃ 1385 CN H H H CH ₃ CH ₃ 1386 OCH ₃ Cl H H CH ₃ CH ₃ 1387 CN Cl H H CH ₃ CH ₃ 1388 br Cl H H CH ₃ CH ₃ 1389. SCH ₃ Cl H H CH ₃ CH ₃ 1390 SO ₂ CH ₃ Cl H H CH ₃ CH ₃ 1391 Cl SCH ₃ H H CH ₃ CH ₃ 1392 Cl SOCH ₃ H H CH ₃ CH ₃ 1393 Cl SO ₂ CH ₃ H H CH ₃ CH ₃ 1394 SOCH ₃ Cl H H CH ₃ CH ₃ 1395 SO ₂ CH ₃ H H H CH ₃ CH ₃ 1396 H SO ₂ CH ₃ H H CH ₃ CH ₃ 1397 H CH ₃ H H CH ₃ CH ₃ 1398 Cl F H H CH ₃ CH ₃ 1399 H CF ₃ H H CH ₃ CH ₃ 1400 F F H H CH ₃ CH ₃ 1401 F CF ₃ H H CH ₃ CH ₃ 1402 CF ₃ F H H CH ₃ CH ₃ 1403 H CCl ₃ H H CH ₃ CH ₃ 1404 CCl ₃ H H 1405

J -

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Verb no. R ¹ 1406 Cl 1407 CCl ₃ 1408 CH ₃ 1409 Cl 1410 Cl 1411 H 1412 H 1413 Cl 1414 NO ₂ 1415 H 1416 NO ₂ 1417 CF ₃ 1418 H 1419 OCH ₃ 1420 CN 1421 OCH ₃ 1422 CN 1423 br 1424 SCH ₃ 1425 SO ₂ CH ₃ 1426 Cl 1427 Cl 1428 Cl 1429 SOCH ₃ 1430 SO ₂ CH ₃ 1431 H 1432 H 1433 Cl 1434 H 1435 F 1436 F 1437 CF ₃ 1438 H 1439 CCl ₃ 1440 Cl 1441 CCl ₃ 1442 CH ₃ 1:44 ?, Cl 1444 Cl 1445 H 1446 H 1447 Cl 1448 NO ₂ 1449 H 1450 NO ₂ 1451 CF ₃ 1452 H 1453 OCH ₃ 1454 CN 1455 OCH ₃ 1456 CN 1457 br

R ²

CCl ₃ Cl H Cl H

Cl H

CF ₃ H

NO ₂ Cl H

CF ₃ HH

Cl Cl Cl Cl Cl SCH ₃ SOCH ₃ SO ₂ CH ₃ Ci w

SO ₂ CH ₃ CH ₃ F

CF ₃ F

CF ₃ F

CCl ₃ H

CCl ₃ Cl H

Cl H

Cl H

CF ₃ H

NO ₂ Cl H

CF ₃ HH

Cl Cl Cl

R ³

C ₆ Hs-C ₆ H ₅ -C ₆ H ₅ -C ₆ H ₅ -C ₆ Hs-C ₆ H ₅ -C ₆ H ₅ -C ₆ Hs-C ₆ H ₅ -C ₆ H ₅ -C ₆ H ₅ -C ₆ H ₅ -C ₆ H ₅ -C ₆ H ₅ -C ₆ H ₅ -C ₆ Hs-C ₆ H ₅ -C ₆ H ₅ -C ₆ H ₅ -C ₆ H ₅ -C ₆ H ₅ -C ₆ Hs-C ₆ H ₅ -C ₆ H ₅ -C ₆ H ₅ -C ₆ H ₅ -C ₆ H ₅ -C ₆ H ₅ -Ci'Is-C ₆ H ₅ -C ₆ Hs-C ₆ H ₅ -C ₆ H ₅ -C ₆ H ₅ -4-C 1-4 C1-4 C1-4 C1-4 C1-4-Cl-4-C1-4-Cl-4-C1-4 -Cl-4-C1-4 C1-4 C1-4 C1-4-C1

CH ₂ -CH ₂ -CH ₂ - -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -LH ₂ -fH ₂ -CH ₂ -CH ₂ - CH ₂ -C ₆ H., C ₆ H ₁ , C ₆ H ₁ , C ₆ H, C ₆ H, C ₆ Hu C ₆ H,

C ₆ Hi,

C ₆ H, C ₆ H t, C ₆ H, C ₆ Hi, C ₆ Hi, C ₆ H ₁ , C ₆ Hi,

V H R ⁵ R ⁶ H CH ₃ CH ₃ H CH ₃ CH ₃ H CH ₃ CH ₃ H H H H H H H H H H H H H H H H H H Ή H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H ι ' H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H

Phys. DaL ^ n

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Verb no. R ¹ R ² R ³ R " H R ⁵ H R ⁶ H phys. data 1458 SCH ₃ Cl 4-Cl-C ₆ H, H H H 1459 SO ₂ CH ₃ Cl 4-Cl-C ₆ Hu H H H 1460 Cl SCH ₃ 4-Cl-C ₆ Hi, H H H 1461 Cl SOCH ₃ 4-Cl-C ₆ Hi, H H H 1462 Cl SO ₂ CH ₃ 4-Cl-C ₆ Hi, H H H 1463 SOCH ₃ Cl 4-Cl-C ₆ Hi, H H H 1464 SO ₂ CH ₃ H 4-Cl-C ₆ Hi, H H H 1,465 H SO ₂ CH ₃ 4-Cl-C ₆ Hi, H H H • 1466 H CH ₃ 4-Cl-C ₆ Hu H H H 1467 Cl F 4-Cl-C ₆ Hi, ¹ H H H 1468 H CF ₃ 4-Cl-C ₆ Hu H H H 1469 F F 4-Cl-C ₆ Hi, H H H 1470 F CF ₃ 4-Cl-C ₆ Hu H H H 1471 CF ₃ F 4-Cl-C ₆ Hu H H H 1472 H CCl ₃ 4-Cl-C ₆ Hu H H H 1473 CCl ₃ H 4-Cl-C ₆ Hu H H H 1474 Cl CCl ₃ 4-Cl-C ₆ Hu H H H 1475 CClj Cl 4-Cl-C ₆ Hu H H H 1476 CH ₃ H 4-Cl-C ₆ Hu H CH ₃ H 1477 Cl Cl CH ₃ H CH ₃ H 1478 C ¹ H CH ₃ H CH ₃ H 1479 H Cl CH ₃ H CH ₃ H 1480 H H CH ₃ H CH ₃ H 1481 Cl CF ₃ CH ₃ H CH ₃ H 1482 NO ₂ H CK ₃ H CH ₃ H 1483 H NO ₂ CH ₃ H CH ₃ H 1484 NO ₂ Cl CH ₃ H CH ₃ H 1485 CF ₃ H CH ₃ H CH ₃ H 1486 H CF ₃ CH ₃ H CH ₃ H 1487 OCH ₃ H CH ₃ H CH ₃ H 1488 CN H CH ₃ H CH ₃ H 1489 OCH ₃ Cl CH ₃ H CH ₃ H 1490 CN Cl CH ₃ H CH ₃ H 1491 br Cl CH ₃ H CH ₃ H 1492 SCH ₃ Cl CH ₃ H CH ₃ H 1493 SO ₂ CH ₃ Cl CHj H CH ₃ H 1494 Cl SCH ₃ CH ₃ H CH ₃ H 1495 Cl SOCH ₃ CH ₃ H CH ₃ H 1496 Cl SO ₂ CH ₃ CH ₃ H CH ₃ H 1497 SOCH ₃ Cl CH ₃ H CH ₃ H 1498 SO ₂ CH ₃ H CH ₃ H CH ₃ H 1499 H SO ₂ CH ₃ CH ₃ H CH ₃ H 1500 H CH ₃ CH ₃ H CH ₃ H 1501 Cl F CH ₃ H CH ₃ H 1502 H CF ₃ CH ₃ H CH ₃ H 1503 F F CH ₃ H CH ₃ H 1504 F CF ₃ CH ₃ H CH ₃ H 1505 CF ₃ F CH ₃ H CH ₃ H 1506 H CCl ₃ CH ₃ H CH ₃ H 1507 CCl ₃ H CH ₃ H CH ₃ H 1508 Cl CCl ₃ CH ₃ H CH ₃ H 1509 CCl ₃ Cl CH ₃

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Verb no. R ¹ R ² R ³ CH ₃ R " H R ^s R ⁶ H phys. data 1510 CH ₃ H H H CH ₃ CN 1511 Cl Cl H H H CN 1512 Cl H H H H CN 1513 H Cl H H H CN 1514 H H H H H CN 1515 Cl CF ₃ H H H CN 1516 NO ₂ H H H H CN 1517 H NO ₂ H H H CN 1518 NO ₂ Cl H H H CN 1519 CF ₃ H H H H CN 1520 H CF ₃ H H H CN 1521 OCH ₃ H H H H CN 1522 CN H H H H CN 1523 OCH ₃ Cl H H H CN 1524 CN Cl H H H CN 1525 br Cl H H H CN 1526 SCH ₃ Cl H H H CN 1527 SO ₂ CH ₃ Cl H H H CN 1528 Cl SCH ₃ H H H CN 1529 Cl SOCH ₃ H H H CN 1530 Cl SO ₂ CH ₃ H H H CN 1531 SOCH ₃ Cl H H H CN 1532 SO ₂ CH ₃ H H H H CN 1533 H SO ₂ CH ₃ H H H CN 1534 H CH ₃ H H H CN 1535 ul F H H H CN 1536 H CF ₃ H H H CN 1537 F F H H H CN 1538 F CF ₃ H H H CN 1539 CF ₃ F H H H CN 1540 H CCl ₃ H H H CN 1541 CCl ₃ H H H H CN 1542 Cl CCl ₃ H H H CN 1543 CCl ₃ Cl H H H CN 1544 CH ₃ H CH ₃ H H CN 1545 · Cl Cl CH ₃ H H CN 1546 Cl H CH ₃ H H CN 1547 H Cl CH ₃ H H CN 1548 H H CH ₃ H H CN 1549 Cl CF ₃ CH ₃ H H CN 1550 NO ₂ H CH ₃ H H CN 1551 H NO ₂ CH ₃ H H CN 1552 NO ₂ Cl CH ₃ H H CN 1553 CF ₃ H CH ₃ H H CN 1554 H CF ₃ CH ₃ H H CN 1555 OCH ₃ H CH ₃ H H CN 1556 CN H CH ₃ H H CN 1557 OCH ₃ Cl CH ₃ H H CN 1558 CN Cl CH ₃ H H CN 1559 br Cl CH ₃ H H CN 1560 SCH ₃ Cl CH ₃ H H ci; 1561 SO ₂ CH ₃ Cl H

- 36 -

Verb no. R ¹ R ² R ³ CH ₃ R " H R ⁵ H R ⁶ phys. data 1562 Cl SCH ₃ CH ₃ H H CN 1563 Cl SOCH ₃ CH ₃ H H CN 1564 Cl SO ₂ CH ₃ CH ₃ H H CN 1565 SOCH ₃ Cl CH ₃ H H CN 1566 SO ₂ CH ₃ H CH ₃ H H CN 1567 H SO ₂ CH ₃ CH ₃ H H CN 1568 H CH ₃ CH ₃ H H CN 1569 Cl F CH ₃ H H CN 1570 H CF ₃ CH ₃ H H CN 1571 F F CH ₃ , H H CN 1572 F CF ₃ CH ₃ H H CN 1573 CF ₃ F CH ₃ H H CN 1574 H CCl ₃ CH ₃ H H CN 1575 CCl ₃ H CH ₃ H H CN 1576 Cl CCl ₃ CH ₃ H H CN 1577 CCl ₃ Cl CH ₃ H H CN 1578 CH ₃ H C ₆ H ₅ H H CN 1579 Cl Cl C ₆ H ₅ H H COOCH ₃ 1580 Cl H C ₆ H ₅ H H COOCH ₃ 1581 H Cl C ₆ H ₅ H H COOCH ₃ 1582 H H C ₆ H ₅ H H COOCH ₃ 1583 Cl CF ₃ COOCH ₃ Fp.> 180 ° C ₆ H ₅ H H Dec. 1584 NO ₂ H C ₆ H ₅ H H COOCH ₃ 1585 H NO ₂ C ₆ H ₅ H H COOCH ₃ 1586 NO ₂ Cl C ₆ H ₅ H H COOCH ₃ 1587 CF ₃ H C ₆ H ₅ H H COOCH ₃ 1588 H CF ₃ C ₆ H ₅ H H COOCH ₃ 1589 OCH ₃ H C ₆ H ₅ H H COOCH ₃ 1590 CN H C ₆ H ₅ H H COOCH ₃ 1591 OCH ₃ Cl C ₆ H ₅ H H COOCH ₃ 1592 CN Cl C ₆ H ₅ H H COOCH ₃ 1593 br Cl C ₆ H ₅ H H COOCH ₃ 1594 SCH ₃ Cl C ₆ H ₅ H H COOCH ₃ 1595 SO ₂ CH ₃ Cl C ₆ H ₅ H H COOCH ₃ 1596 Cl SCH ₃ C ₆ H ₅ H H COOCH ₃ 1597 Cl SOCH ₃ C ₆ H ₅ H H COOCH ₃ 1598 Cl SO ₂ CH ₃ C ₆ H ₅ H H COOCH ₃ 1599 SOCH ₃ Cl C ₆ H ₅ H H COOCH ₃ 1600 SO ₂ CH ₃ H C ₆ H ₅ H H COOCH ₃ 1601 H SO ₂ CH ₃ C ₆ H ₅ H H COOCH ₃ 1602 H CH ₃ C ₆ H ₅ H H COOCH ₃ 1603 Cl F C ₆ H ₅ H H COOCH ₃ 1604 H CF ₃ C ₆ H ₅ H H COOCH ₃ 1605 F F C ₆ H ₅ H H COOCH ₃ 1606 F CF ₃ C ₆ H ₅ H H COOCH ₃ 1607 CF ₃ F C ₆ H ₅ H H COOCH ₃ 1608 H CCl ₃ C ₆ H ₅ H H COOCH ₃ 1609 CCl ₃ H C ₆ H ₅ H H COOCH ₃ 1610 Cl CCl ₃ C ₆ H ₅ H H COOCH ₃ 1611 CCl ₃ Cl C ₆ H ₅ H H COOCH ₃ 1612 CH ₃ H COOCH ₃

- 37 -

Verb no. R ¹ H R ² R ³ H R- H R ⁵ R ⁶ phys. data 1613 H SCH ₃ H H H H Fp.> 140 ° Z 1614 H SOCH ₃ H H H H 1615 CO ₂ H SO ₂ CH ₃ H H H H 1616 CO ₂ H H CH ₃ H H H Fp.> 150 ° Z 1617 CO-.H H H C ₃ H ₇ (D H H 1618 CO ₂ H H H:. phenyl H H 1619 CO ₂ CH ₃ H H H H H 1620 CO ₂ C ₂ H ₅ H H H H H 1621 CO ₂ M ₂ H H H H H 1622 CN H H H H H 1623 CO ₂ H H H H H H 1624 CO ₂ CH ₃ CH ₃ H H H H 1625 CO ₂ H CHi H H H H 1626 CO ₂ CII ₃ C ₂ H ₅ H H H H 1627 CO ₂ CH ₃ C ₂ H ₅ H H H H 1628 CO ₂ H br H H H H 1629 Cl br CH ₃ CH ₃ H H 1630 H CF ₃ CH ₃ CH ₃ CH ₃ H Mp 65-70 ⁰ C 1631 Cl CF ₃ H H CH ₃ H 1632 Cl OCH ₃ H H H H 1633 Cl SC ₂ H ₅ H H H H 1634 Cl SOC ₂ H ₅ H H H H 1635 SC ₂ H ₅ SO ₂ C ₂ H ₅ H H H H 1636 SOC ₂ H ₅ Cl H H H H 1637 SO ₂ C ₂ H ₅ Cl H H H H 1638 H Cl H H H H 1639 Cl SO ₂ C ₂ H ₅ H H H H 1640 Cl SO ₂ C ₃ H ₇ (D. H H H H 1.64; Cl SOC ₃ H ₇ (D H H H H 1642 Cl SC ₃ H ₇ (D H H H H 1643 Cl OCH ₃ H : -i H H 1644 Cl OC ₃ H ₇ (D H H H H 1645 H br H H H H 1646 OCH ₃ H H Mp. 79-85 ° C

234 ο 02

H. 1.2. Preparation of salts of the formula I

H. 1.2.1. Sodium salt of 2- (3-chloro-5-trifluoromethylpyridin-2-yl)

carbonyD-cyclohex-l-en-l-ol-S-on

3.2 g of 2- (3-chloro-5-trifluoromethylpyridin-2-yl-carbonyl) -cyclohex-l-en-lol-3-one are dissolved in 20 ml of methanol, treated with 0.54 g of sodium methylate and 15 min stirred at room temperature. Thereafter, the rotary evaporator is evaporated to dryness. The residue is triturated with diethyl ether, filtered off and dried.

Isolated in quantitative yield, the title compound of the formula

I Il

0 na

as a colorless solid (verb.

Analogously to the above preparation process, the salts of the table can be synthesized.

Table 2

Compounds of the formula

? ^C f R ³ .

N I

Verb no. R ¹ R ² R ³ H R ¹ * H R ⁵ K R ⁶ Na® phys. data 2001 Cl Cl H H H H Li® 2002 Cl Cl H H H H 1/2 Ca ² ® 2003 Cl Cl H H H H NH (CH ₃ ) ₃ ® 2004 Cl Cl H H H H NH (C ₂ H ₅ OH) ₃ ^O - 2005 Cl Cl H H H H ν ® Na 2006 Cl CF ₃ H H H H Li® colorless fez 2007 Cl CF ₃ H H H H 1/2 Ca ² ® 2008 Cl CF ₃ H H H H NH (CH ₃ ) ₃ ® 2009 Cl CF ₃ H H H H NH (C ₂ H ₅ OH) ₃ ® 2010 Cl CF ₃ H H H H Na® 2011 NO ₂ H H H H H Li® 2-012 IoO ₂ H H H H H 1/2 Ca ² ® 2013 NO ₂ H H H H K NH (CH ₃ ) ₃ ® 2014 NO ₂ H H H H H NH (C ₂ H ₅ OH) ₃ ^O 2015 NO ₂ H H

Verb no. R ¹ H NO ₂ R ³ H R- H R ⁵ H R ^b Μ® phys. data 2016 H NO ₂ H H H H Na ⁰ 2017 H NO ₂ H H H H Li ⁰ 2018 H NO ₂ H H H H 1/2 Ca ^{2 @} 2019 H NO ₂ H H H H NH (CH ₃ ) ₃ ® 2020 H H H H H H NH (C ₂ HSOH) ₃ ⁰ 2021 H H H H H H Na ⁰ 2022 H H H H H H Li ⁰ 2023 H H H H H H 1/2 to ²⁰ 2024 H H H H H H NH (CH ₃ ) ₃ ^Θ 2025 Cl CCl ₃ H H H H NH (C ₂ H ₅ OH) ₃ ^O 2026 Cl CCl ₃ H H H H Na ⁰ - 2027 Cl CCl ₃ H H H H Li ⁰ 2028 Cl CCl ₃ H H H H 1/2 to ²⁰ 2029 Cl CCl ₃ H H H H NH (CH ₃ ) ₃ ^O 2030 F CF ₃ H H H H NH (C ₂ H ₅ OH) ₃ ^O 2031 F CF ₃ H H H H Na ⁰ 2032 F CF ₃ H H H H Li ⁰ 2033 F CF ₃ H H H H 1/2 to ²⁰ 2034 F CF ₃ H H H H NH (CH ₃ ) ₃ ^Θ 2035 Cl Cl CH ₃ H H H NH (C ₂ H ₅ OH) ₃ ^O 2036 Cl Cl CH ₃ H H H Θ Na 2037 H τ · © Lx

C © © ci © m © ro © © © ro © ro © CO © egg © i © ro © ΓΟ © η) © © η) © ro © ro © (O © © (Tj © ro W N O / "* \ •H O • rl κ 55 • Η CM CJ 55 •H N U m η O 55 O ο O K ro O " ro N K ir. " N K ιΛ κ K ιθ K K N in K " CM U)  ^ *. O K K υ K K ^ " O K K - • ^. υ α 1- < CM κ K · "* CSI K r-H K υ K K " κ ' U ro K * ΓΟ K * T * O ro K " K K 55 ro K κ ro K K ro K K ro K 55 co K K K K κ rc υ K © O κ K O K " K K υ O K κ ^Ä υ N K CSI ο K t -I CJ K K ro ro fO m K κ ΓΟ κ O CM ro c K ro K K K Ph Ph K K r · « κ υ K κ 55 O K K K K K O ro O O O ίΟ CM O 55 O ro O r <1 K K ro U W O CM N K S3 CSI K K K K H r-4 O m 1-1 r-H Ph υ ro 55 O K ro K O O ro K K CJ 55 O K O O O CO K 55 ι I K 55 CM K .H O Ph υ \ Q CM O r * H O υ VD K • i-l O r- I N iH O ro K O CM K 55 CM if) K I. O rh St st O Ph O K ο if) O O in W (v r-l O O O -H O N O K N ο K 55 N O K > 00 O CM N CO O CM ro CM CM CO N OO CO rh st rh K O K O σ " O O st O CJ O 55 O st O cn N co N st CM CM rg O O O K ^^ O O N st N ^ J N If) CM O O ο O CM N C N N 55 OO ^ - O CM

-HX "

C © ro © CO © © co © ro © ro © CD © © (O © ro j © ro © CD © © CD © ro © ro © CD © © (O © ro © ro © CD β> 55 • rl ec α , '- \ 55 • rl ec υ / -χ 33 55 •H ec O / -ν 33 55 •H ec CJ 55 Π) ο 33 ►J ro O - ro O , -I ro O rJ ro O 33 Q in 33 33 ec 33 m 33 33 ec in 33 ec 33 in 33 33 ec 33 in X U) 33 33  - ^ υ 33 ^ " O 33 33 CJ 33 33 - ^. υ 33 T3 1-4 W -H M 33 rvi 33 r-H N 33 α CJ 33 33 U 33 * ir * CJ 33 33 33 U 33 3 = SC CJ 33 55 33 _K 55 33 55 rs X 33 " 33 33 1- 33 33 33 55 ro 33 33 55 ro 33 55 ro 33 33 55 ro 33 33 55 I *] 33 ro 33 ro 33 O ro O ro 33 υ U 33 33 CJ 33 _K I O ^, 33 α ΓΝ 33 33 I CJ υ C 33 C I 33 U 33 cn ro ro I "; V C ro 33 ro C ro r * * 33 r-i ro 33 (M ro 33 r-i O pi (M rt O 33 33 CJ rh O ro CJ (M O ro CJ r-i I ro ^. CJ (M I ro CJ CJ 33 CJ 33 O C O 33 O C CJ 33 33 ro rh CJ ro U ro (M O ft r-i ro r-i ro ro fs O U 33 U rh r-l 33 (M (M SC CJ rh rh C C O r-i (M C O 5h CJ CJ CJ ro O CJ ΓΟ O O υ CJ υ ro I Ph r-I O r-i VO (M 1-I rh C VO (M C r-l VO ec r-i CJ ro VO (M O ro Γ- ec r-i CJ Γ- r-l Ü ro OO Sh 33 O VO CJ υ rh O VO (M O Γ U r-l O r- CJ (M O ec O r-i CJ ec O (M υ ec Ο r-i O ec O r-i O ec ec CO CJ υ ec OO ec iO υ ec OO CJ 33 VO r-i VO (M Γ- r-i Γ r-i O ^ cj O O\ O  J- O Ο σ> O m ec VO ec VO CSI Γ ec Γ Ph O O U-I O O Ο ΙΛ Ο O VO ec VO cv) r- ec Γ- rg OO O O O O O Μ ec ec ec ec ec Ph ι- * U (U

-Hi'

C © © © CO © ro © ro © co © © CO © ro © rl © CO ι © © CO © ro © tn © © © CO © ro © ro © CO © © CO O) χ •H CM CJ f _% 33 • rl CM CJ 33 33 55 • rl CM O 33 • Η CM U / - * » 33 • rl CM CJ U "k - ¹ ro O 33 υ O X - ¹ O S? tn O X i-l CO 33 CM 33 m 33 33 CM in X X CM X in X X CM X in X X CM O ti 33 - ^. CJ 33 33 33 33 X ^. CJ X X - ^, O X X - ^ V) U F-H CM 33 F-H Jz; CM X F-H N "./ N F-H CM X F-H α 33 33 O 33 33 33 33 CJ X X X X CJ X X X X CJ X X X X 33 ro 33 33 33 \ ^ / ro X X nw / P-X X X Γ0 X X ro * 33 CJ ro X U ro X X ro ro X X CJ Γ0 m CJ - 33 I U 33 33 I υ X X CJ CJ X X I O X Ph I p- 33 33 C I 33 33 33 C I X X I I P-X X C I X C ro 33 33 CM C ro ro X C ro X X C C ro X X C ΓΊ O r- O CM O υ X O X ro ro CJ X P-. ro CJ CJ 33 I ro 33 Jz; O I I X X I rl X iH f_l I ro X O pH I pi C υ 33 C C X (3 cj X υ CJ C O X O C I ro CM CM ro I ro ο O ro I ro η CM 33 C CJ 33 O O O X X C O i-l C CJ Ph Ph • -4 Pi O I 33 sz: I X .H rh CJ ro I Ph O U 33 C C X C υ CJ O i-l C CM VO CM F-H CJ ro r < CM O 33 OO , ^. 33 33 O ON CM X X VD r-i Ü i-i O CM Ph OO O OO O CTi ΟΛ σ> O O F-H O Q) O O CM O CM O X ο ο i-l CJ CM F-H CM CO Jz; CM CM OO σι CM CO CM CM 00 O CM co OO O OO OO X σ \ X cn i-l O O ^Ä O O O <t O σι O r-i CM OO CM CM CM σ \ CM cn CM O in O O in O O CM OO O-i CM CTi CM O O O O F-H CM CM CM CM

264002

C © © ro © ro (?) CO (!) W CO © η © ro © (D © W (D © ro © ro W (O W W (D (D ro © ro W co W ω CD 0 ro O) • -s • rl ec C) S5 • rl ec C) cc • rl ec O • ~> \ cc Sh • rl ec C) 4-) "Ss ro O ro O CC - ¹ C) O CC - ¹ ro O CC - * ro co cc in ec cc m X ec in cc * ec cc m CC cc ec U-J Q pi - ^. C) 55 ^^ K - ^ C) CC cc ^^ C) l / l M i-H N i-h: (Vl cc r-H α ίπ cc C) CC CC 5C O " O CC K C) cc CC cc CC P? CC cc CC ^Ä cc cc P5 cc U-J ro π " th fO CC ro K cc cc rl cc CC ^Ä U ro cc ^Ä O ro cc Sh O ro CC cc Sh O ro cc K m I υ I CJ * I CJ CC I O ftf Ä cc  rl I cc CC • rl I CC • rl I cc cc CC • rl I cc K •H ro • rl ro ro • rl ro (V) •H ro K " iH υ cc Ph ro CJ υ K O cc CC O (Vl υ cc CM ro U i ~ H) I ro CJ Ph I I CC I ro Sh O I t * CJ cc υ • rl υ cc O • rl • rl CC (Vl •H O CC Sh •H CJ I ro iH I ro ι I ro ro O (Vl I ro CC (-J I pm " C cj rh r-l •H U υ r-H Ph Ph O Ph O CC • rl CJ CC O •H 1-1 ro I U cj I O O υ I Ph I Ph (VI Ph C O •H l-H •H VO (Vl CC • rl r-H eg O Ve rl O ro ec O iH υ ec C-J rh  Η ro ec O ec Cv) eg CC Sh Ph CVI U  -Η ec CJ υ Ph ec Sh (Vl CC ec pH υ r-l υ CJ O CC OO O CJ ro Ct OO Sh (-J ro Cv) Ph ec r-H cv) ec rh ec O ec O O CJ CJ cr> Ph -cl eg ec CVI ec ec ιΛ O O ιΛ O Cv! ec ec ec ec

Verb no. R ¹ H R ² R ³ R " H R ⁵ H R ⁶ M® phys. data 2125 H NO ₂ 1-C ₃ H ₇ H H H NH (C ₂ H ₅ OH) ₃ ^O 2126 H H iC ₃ H ₇ H H H N / A 2127 H H 1-C ₃ H ₇ H H H Li® 2128 H H iC ₃ H ₇ H H H 1/2 to ²⁰ 2129 H H iC ₃ H ₇ H H H NH (CH ₃ ) ₃ ^O 2130 Cl H 1-C ₃ H ₇ H H H NH (C ₂ H ₅ OH) ₃ ^O 2131 Cl CCl ₃ iC ₃ H ₇ H H H N / A 2132 Cl CCl ₃ 1-C ₃ H ₇ H H H Li ⁰ 2133 Cl CCl ₃ iC ₃ H ₇ H H H 1/2 to ²⁰ 2134 Cl CCl ₃ iC ₃ H ₇ H H H NH (CH ₃ ) ₃ ® 2135 F CCl ₃ 1-C ₃ H ₇ H H H NH (C ₂ H ₅ OH) ₃ ^O - 2136 F CF ₃ iC ₃ H ₇ H H H XT © Na 2137 F CF ₃ iC ₃ H ₇ H H H Li® 2138 F CF ₃ iC ₃ H ₇ H H H 1/2 Ca ² ® 2139 F CF ₃ 1-C ₃ H ₇ H H H NH (CH ₃ ) ₃ ⁰ 2140 Cl CF ₃ iC ₃ H ₇ H H H NH (C ₂ H ₅ OH); ⁰ 2141 Cl Cl C ₆ Kd H H H XT © Na 2142 Cl Cl C ₆ H ₅ H H H Li ⁰ 2143 Cl Cl C ₆ H ₅ H H H 1/2 Ca ² ® 2144 Cl Cl C ₆ H ₅ H H H NH (CH ₃ ) ₃ ® 2145 Cl Cl C ₆ H ₅ H H H NH (C ₂ H ₅ OH) ₃ ⁹ 2146 CF ₃ C ₆ H ₅ H Na ⁰

Verb no. R ¹ R ² R ³ R- H R ⁵ H R ⁶ Li® phys. data 2147 Cl CF ₃ C ₆ H ₅ H H H 1/2 Ca ² ® 2148 Cl CF ₃ C ₆ H ₅ H H H NH (CH ₃ ) ₃ ® 2149 Cl CF ₃ C ₆ H ₅ H H H NH (C ₂ H ₅ OH) ₃ ^O 2150 Cl CF ₃ C ₆ H ₅ H H H Na® 2151 NO ₂ H C ₆ H ₅ H H H Li® 2152 NO ₂ H C ₆ H ₅ H H H 1/2 Ca ² ® 2153 NO ₂ H C ₆ H ₅ H H H NH (CH ₃ ) 3® 2154 NO ₂ H C ₆ H ₅ H H H NH (C ₂ H ₅ OH) ₃ ^O 2155 NO ₂ H C ₆ H ₅ H H H Na® 2156 H NO ₂ C ₆ H ₅ H H H Li® 2157 H NO ₂ C ₆ H ₅ H H H 1/2 Ca ² ® 2158 H NO ₂ C ₆ H ₅ H H H NH (CH ₃ ) 3® 2159 H NO ₂ C ₆ H ₅ H H H NH (C ₂ H ₅ OH) ₃ ® 2160 H NO ₂ C ₆ H ₅ H H H Na® 2161 H H C ₆ H ₅ H H H Li® 2162 H H C ₆ H ₅ H H H 1/2 Ca ² ® 2163 H H C ₆ H ₅ H H H NH (CH ₃ ) 3® 2164 H H C ₆ H ₅ H H H NH (C ₂ H ₅ OH) ₃ ^O 2165 H H C ₆ H ₅ H H H © Na 2166 Cl CCl ₃ C ₆ H ₅ H H H Li ⁰ 2167 Cl CCl ₃ C ₆ H ₅ H H H 1/2 to ²⁰ 2168 Cl CCl ₃ C ₆ H ₅ H

Verb no.

2169

2170

2171

2172

2173

2.17a

2175

2176

2177

2178

2179

2180

2181

2182

2183

2184

2.1CS

2186

2187

2188

2189

2190

R ¹

Cl Cl F F F F F

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

NO ₂

NO ₂

NO ₂

NO ₂

NO ₂

R ² R ³ CCl ₃ C ₆ H ₅ CCl ₃ C ₆ H ₅ CF ₃ C ₆ H ₅ CF ₃ C ₆ H ₅ CF ₃ C ₆ H ₅ CF ₃ C ₆ H ₅ CF, C ₆ H ₅ Cl CH ₃ Cl CH ₃ Cl CH ₃ Cl CH ₃ Cl CH ₃ CF ₃ CH ₃ CF ₃ CH ₃ CF ₃ CH ₃ CF ₃ CH ₃ CF ₃ CH ₃ H CH ₃ H CH ₃ H CH ₃ H CH ₃ H CH ₃

H H H H H H

CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃

R ⁵ H R ⁶ H H H H H H H H H H υ H H H H H H H H H H H H H H H H

H H H H H H H

H H H H H H H

.θ

NH (CH ₃ ) ₃ ®

NH (C ₂ H ₅ OH) ₃ ®

ff>

.Θ

Li

1/2 Ca ² ®

NH (CH ₃ ) ₃ ®

NH (C ₂ H ₅ OH) ₃ ®

Na ¹

Li ⁰

1/2 to ²⁰

NH (CH ₃ ), ⁰

NH (C ₂ H ₅ OH) ₃ ^O

N / A

Li®

1/2 to ²⁰

NH (CH ₃ ), ⁰

NH (C ₂ H ₅ OH) ₃ ^O

Na®

Li ⁰

1/2 to ²⁰

NH (CH ₃ ) ₃ ®

NH (C ₂ H ₅ OH) ₃ ^O

phys. data

O O IO

Verb no.

2,191 2,192 2,193 2,194 2,195 2,196 2,197 2,198 2,199 2,200 2,201 2,202 2,203 2,204 2,205 2,206 2,207 2,208 2,209 2,210 2,211 2,212

R ¹ H R ² R ³ R " R ⁵ H R ⁶ H NO ₂ CH ₃ CH ₃ H H H NO ₂ CH ₃ CH ₃ H H H NO ₂ CH ₃ CH ₃ H H H NO ₂ CH ₃ CH ₃ H H H NO ₂ CH ₃ CH ₃ H H H H CH ₃ CH ₃ H H H H CH ₃ CH ₃ H H H H CH ₃ CH ₃ H H H H CH ₃ CH ₃ H H Cl H CH ₃ CH ₃ H H Cl CCl ₃ CH ₃ CH ₃ H H Cl CCl ₃ CH ₃ CH ₃ H H Cl CCl ₃ CH ₃ CH ₃ H H Cl CCl ₃ CH ₃ CH ₃ H H F CCl ₃ CH ₃ CH ₃ H H F CF ₃ CH ₃ CH ₃ H H F CF ₃ CH ₃ CH ₃ H H F CF ₃ CH ₃ CH ₃ H H F CF ₃ CH ₃ CH ₃ H H Cl CF ₃ CH ₃ CH ₃ CH ₃ H Cl Cl CH ₃ H CH ₃ H Cl CH ₃ H H

, Θ

χτ ^Θ Na

τ · ©

Lx 1/2 approx

2 ©

NH (CH ₃ )

NH (C ₂ H ₅ OH)

Na®

Li®

1/2 approx

2 ©

NH (CH ₃ )

NH (C ₂ H ₅ OH) ₃

XT ©

N / A

τ · ©

Lx

1/2 Ca NH (CH ₃ )

2 ©

NH (C ₂ H ₅ OH)

χτ © Na

τ · ©

Lx 1/2 approx

2 ©

NH (CH ₃ )

NH (C ₂ HsOH)

Na® Li®

phys. data

0 02

© (Ο © ΓΟ © ro © CO © (0 © ro © ro © (0 © co © ro © (U © © CO © ro © © (0 © r * CM υ / • - ^ 33 Sh CM O , - ^ 33 CM O y-v Sh CM 33 • ri CM U ^ -> ro O ro O CO O co O t * CM 33 in © CM 33 in © CM 33 Λ 33 m CNl 33 - ^. U 33  ri -. O 33 • H ~ - O O 33 υ ι- * I-) i-H hi I-I (M © CM (M r-H V ^ ρ ~ * U 33 O 33 υ • ri - 33 υ 33 \ / V ^ © sq V ^ © Sh 33 33 r 33 33 (0 ©

33 33

333353333333333333333333333333333333

O

33

33 33 33 33

υ υ ο ο ο

3333333333333333333333

υουοουοοουυ

333333333333333333333333333333333333333333

CJ

333333333333333333333333 UOOOOOCJOCJCJCJO

33 33 33 33 33 33 33 33 υ υ O υ υ O υ O

ο ο ο υ

Ph

Pho

Pho

33

33

Sh

Π3 33

υυυυυουο

Sh

S5

33 33

33 33 33 33

IT) VO

CM CM

CM CM ο)

O r-l CM CO <f ιΛ VO P-. OO CTi O r < CM CO <f CV) CV) CM CM CM CM CN) CM CM CM CO CO CO CO CO CV) CM CVJ CNJ CM CM CM CM CM CM CM CM CM CM CM

CMCMCMCMCMCVJCMCMCMCMCMCMCMCMCMCMCM

Verb no. R ¹ H R ² H R ³ R " H R ⁵ R ⁶ M® phys. data 2235 Cl CCl ₃ CH ₃ H CH ₃ H NH (C ₂ H ₅ OH) 3® 2236 Cl CCl ₃ CH ₃ H CH ₃ H Na® 2237 Cl CCl ₃ CH ₃ H CH ₃ H Li® 2233 Cl CCl ₃ CH ₃ H CH ₃ H 1/2 Ca ² ® 2239 Cl CCl ₃ CH ₃ H CH ₃ H NH (CH ₃ ) ₃ ® 2240 F CF ₃ CH ₃ H CH ₃ H NH (C ₂ H ₅ OH) ₃ ^O 2241 F CF ₃ CH ₃ H CH ₃ H XT © Na 2242 F CF ₃ CH ₃ H CH ₃ H Li® 2243 F CF ₃ CH ₃ H CH ₃ H 1/2 Ca ² ® 2-244 F CF ₃ CH ₃ H CH ₃ H NH (CH ₃ ) ₃ ® 2245 Cl Cl CH ₃ H CH ₃ H NH (C ₂ H ₅ OH) ₃ ^O - 2246 Cl Cl H H H CN © Na 2247 Cl Cl H H H CN τ · © Li 2248 Cl Cl H H H CN ? © 1/2 approx 2249 Cl Cl H H H CN NH (CH ₃ ) ₃ ® 2250 Cl CF ₃ H H H CN NH (C ₂ H ₅ OH) ₃ ^O 2251 Cl CF ₃ H H H CN Na® 2252 Cl CF ₃ K H H CN Li® 2253 Cl CF ₃ H H H CN 1/2 to ²⁰ 2254 Cl CF ₃ H H H CN NH (CH ₃ ) 3® 2255 NO ₂ H H H H CN NH (C ₂ H ₅ OH) a® 2256 H H CN XT © Na

-51-

C © © CO © ro ®ro © <0 © © (O © m ®ro © ro © i © ro © ro © © (O © © σ) © to © ro © ro © © ro O) CM CJ / - ^ • rl CM CJ X 55 • rl CM O 55 • rl CM CJ / ~ \ 33 55 •H CM O (TJ a ro 'S  J CJ X 55 - ¹ ro • -N X 55 ►J ro O 55 · "" O 55 CM p ^ O υ 55 CM O CJ CM X O O 55 CM JT * in CJ £ 5 CM U) O ^^ (J in X CJ 33 m X CJ - ^. CJ m X O ^ *. O X O ^ * -. H 33 r-I 33 X i-H 55 X X r-ι X X i-l CM X r-l 55 JT * CM X 55 55 CM X 55 33 CM X 55 fr * υ X 55 O CJ X O cj O X O Ϊ5 O X υ S X O 33 X X X X X 55 X X 55 33 X X 33 CJ 33 CM X 33 X CJ 33 ro X O 55 ro X 33 55 O CM X X X X X 55 r-i ro X X 55 Ph ro X 33 55 55 O 55 X 55 O rh O O Ph 33 CJ 55 X X O X X O υ O X X X υ X X CM CSI X X U ro η CM " X O O X X X r-l r- I X X Ph Ph © O 33 X 55 X X X CJ  Η CJ ro Ph O X 55 33 1-" νο X r < O υ i-H X VO r- cm 33 VO CM X VO X CM O Ό · Γ- χα in O CM VO X X CM CM VO K CM Γ ** O r-l CM f- Ph CM 33 CM CM O CM CM X CM CM CJ O CM CM ^{1 s} CM OO O CM CO CM OO X CM co i-H U CV ₁ OO 55 VO VO VO O <N σ> CM CM CM CM CM r-l CM ec in O CM CM X CM νο X CM r- CJ CM CM 55 CM CM in CM O in CM O CM CM VD VO Γ-. CM Ph CM CM CM CM CM CM CM I .. •

Verb no.

2,279 2,280 2,281 2,282 2,283 2,284 2,285 2,286 2,287 2,288 2,289 2,290 2,291 2,292 2,293 2,294 2,295 2,296 2,297 2,298 2,299 2,300

R ¹ F R ² R ³ H R " H F CF ₃ H H Cl CF ₃ H H Cl Cl H H Cl Cl H H Cl Cl H H Cl Cl H H Cl Cl H H Cl CF ₃ H H Cl CF ₃ H H Cl CF ₃ H H Cl CF ₃ H H NO ₂ CF ₃ CH ₃ H NO ₂ H CH ₃ H NO ₂ H CH ₃ H NO ₂ H CH ₃ H NO ₂ H CH ₃ H H H CH ₃ H H NO ₂ CH ₃ H H NO ₂ CH ₃ H H NO ₂ CH ₃ H H NO ₂ CH ₃ H NO ₂

H H H H H H H H H H H H H H H H H H

CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN

NH (CH ₃ ) ₃ ® NH (C ₂ H ₅ OH) ₃ ^O

Li *

1/2 Ca ² ®

NH (CH ₃ ) ₃ ^O

NH (C ₂ H ₅ OH) ₃ ^O

N / A"

Li "

1/2 to ²⁰

NH (CH ₃ ) ₃ ^Θ

NH (C ₂ H ₅ OH) ₃ ⁰ .. ©

N / A

Li ⁰

1/2 to ²⁰

NH (CH ₃ ) ₃ ^O

NH (C ₂ H ₅ OH) ₃ ⁰ "©

N / A'

Li ¹ =

1/2 to ²⁰

NH (CH ₃ ) ₃ ^O

NH (C ₂ H ₅ OH) ₃ ^O

phys. data

Verb no. R ¹ H R ² H R ³ R " H R ⁵ H R ⁶ Μ® phys. data 2301 H H CH ₃ H H CN Na ⁰ 2302 H H CH ₃ H H CN Li ⁰ 2303 H H CH ₃ H H CN 1/2 to ²⁰ 2304 H H CH ₃ H H CN NH (CH ₃ ) ₃ ^Θ 2305 Cl CCl ₃ CH ₃ H H CN NH (C ₂ H ₅ OH) ₃ ^O 2306 Cl CCl ₃ CH ₃ H H CN XT ^Θ Na 2307 Cl CCl ₃ CH ₃ H H CN Li ⁰ 2308 Cl CCl ₃ CH ₃ H H CN 1/2 to ²⁰ 2309 Cl CCl ₃ CH ₃ H H CN NH (CK ₃ ) ₃ ^Θ 2310 F CF ₃ CH ₃ H H CN NH (C ₂ H ₅ OH) ₃ ^O 2311 F CF ₃ CH ₃ H H CN N / A - 2312 F cr ₃ CH ₃ H H CN Li ⁰ 2313 F CF ₃ CH ₃ H H CN 1/2 to ²⁰ 2314 F CF ₃ CH ₃ H H CN NH (CH ₃ ) a ⁰ 2315 Cl Cl CH ₃ H H CN NH (C ₂ H ₅ OH) ₃ ^O 2316 Cl Cl C ₆ H ₅ -CH ₂ - H H H Na ⁰ 2317 Cl Cl C ₆ H ₅ -CH ₂ - H H H Li ⁰ 2318 Cl Cl C ₆ H ₅ -CH ₂ - H H H 1/2 to ²⁰ 2319 Cl Cl C ₆ H ₅ -CH ₂ - H H H NH (CH ₃ ) ₃ ^O 2320 Cl CF ₃ C ₆ H ₅ -CH ₂ - H H H NH (C ₂ H ₅ OH) ₃ ^O 2321 Cl CF ₃ C ₆ H ₅ -CH ₂ - H H H Na ⁰ 2322 C ₆ H ₅ -CH ₂ - H Li ⁰

284

C © © (0 © ro © ro © (0 © © (0 © ro © ro © © f © ro © tn © ro © (0 © © (O © ro © ro © © © nt © ro O) CVJ υ / - ^ 55 •H cn O 'S •H IV a CJ / • ^ 33 •H CV) O ^ \ 33 •H CM CJ <^ - "\ 4J  fc ro O ro O -I ro O 33 ►J ro O 55 ►J ro (0 CV) 33 in 33 CVJ in 33 " CV) in 33 33 CVJ 33 m SG CV) IC O Ul Pi ^ " α 33 »- CJ 33 33 33 O 33 33 • ^ CJ 33 33 33 υ M r-H CM 33 F-H r-l CM 33 CM r-H a ίί * υ T3 33 K CJ 33 K 33 33 CJ 33 33 33 CJ 33 33 33 rc 33 I 33 ^Ä 33 55 I 33 33 CM I 33 I I 33 33 CM I 33 33 I I 33 33 33 55 33 CM 33 CM CM ac 33 33 CM 33 33 55 CM N 33 33 CJ I 33 33 33 33 33 CJ 33 33 33 33 I 33 33 I in O I I 33 O CJ I 03 I in υ I 33 03 CJ I O I I 33 ro CM 33 I vn CM In the I U) CM 33 I in CM I in I CM pc; 33 I »Γ * VD 33 33 I 33 I 33 VD 33 33 I 33 33 33 I CJ I CM O VD O vD to CJ CM O VD CJ I CM VD u> CJ I CM I in 33 I O I in 33 I O CJ I tn 33 I O I in 33 I CJ O I in 33 33 I OJ 33 33 υ CM N υ CM 33 33 CJ CM ro 33 CJ I OJ VD I in 33 In the 33 O O ω I ul 33 33 VD I in 33 r-l r-l VO I " CJ 33 U I O 33 U J ^ J25 O CJ O 33 I O O U tn ro VD In the CM VD I tn N u> I in VD I in O O ro U < CJ O 33 O 33 O O 33 33 CJ 33 i-H O CJ ro VU 55 O VD 5C 33 J25 η to 33 VD f { f { O ro P! CJ 55 33 O O υ 33 CJ CJ υ CJ wi O tn £ ζ CM O i-h; pH vo O 33 33 O VO 33 33 r-l U • O U CSJ r. 55 _ _ CM Ι5ζ co r ^ F-H CM O Il  H CO CVJ O co CO 33 CO co 33 {r- W 0) O CVJ CO CM CO co CVJ CO co CO ü co r-l CVJ 00 O OJ CVJ CO 33 CM 00 33 CM CM CO CV) O CVJ CO co $ < co ^ J. CO σ \ co co σ> CO ^) - (J CVJ CVJ CVJ CVI co CVJ co CM <r CO ιΛ co O co ιΛ co O CO CVJ CVJ CVJ co CV) CO CM CM CO CO CO CO cv) CVJ CV) CM

-53 "-

C © • © ΓΟ to © © Π) ®ro © ro © Π) © © © ro © ro I © ro © © cO © ro © ro © π) © © CO © ro © ro 'S • rl O 's • Η CM 33 S =; • rl CM O ^^ rc • rl CM O 33 Dat • O ^ - ^ O ro ro O ro ^ ro O ro ro O V) 'S in CM ro in e ro O K in e ro CNJ p "] U) e ro CM e in > -. φ p "] e e υ e O O e υ e O e O e > e O CJ ο O CM N _- / (M O O (-I N _- / O O r-l CM α O O ο O O O O ro e O O O ro e O 33 ο O i-H ^Ä N _- / O O e O O e » 33 - O ro ro - O O ro 33 - O O ro 33 S e e - e e ^Ä e - O e e - O e e e O O ro e O O ro S O O ro I O O e O O e O O e N I e O O C) - O O - O O cc e CM e O O O e O O e O O O e ιη B - O in m O in - O I O I - e  η e O e in e O e in e O - in CM - U) e = U) e - U) e - e e m e e υ Ui e O U) e O U) e Pd U) e O J O in O in I O U) I ΓΜ I e e CM ro O in CM in in ro U) in U) in e (H ro e O e rh e e (H ro O e e O e CM O O (H U) O υ r ~ { U) in O (H U) in e U) in I υ O l / l O O O e O O e N O e m (H ro e in U) t \ ro U) O U) e (H (H U) e υ t \ O O t { (H O Su O e O u> O O O O O ro υ VO ro CJ t-i , -I , -J VO (H 1-I CM e ro (H (H ro m CM O O in r \ O ro VO CM O r-H CO O (η co in , -4 CO in O (H CO VO CM e O O CM CO O CM co rh r-H O CVJ CO rh O CM CO O CM OO (H CM O O CM OO O CM CO CM t-t <f (η r-H in t \ VO O O CO co O co σ> O CO CM σ \ in in CM in CM VO in O CO co in CO O co in si CO CM CM in CM VO CM VO CO CM CO co CO co CVJ CM CM CVJ CM

4 O O 2

π © © <ο © © (O © η ro © Π) © © CO © ro © ro t (O © © n) © ro © ro © <0 © © ro Φ ro © ro O) 55 • Η CVJ CJ / - \ • -Ν 55 • rl CVJ υ 33 55 •H CVJ O 33 ^Ä •H CVJ O (O (O - ¹ η O ro _l ro O m ►J CO O ro -3 ro b P 33 ro CVJ 33 in 33 η CVJ 33 in 33 ro CVJ 33 m 33 ro CVJ 33 in V) O 33 υ ρ ** U 33 CJ 33 O 33 O 33 CJ 33 U 33 , C O υ r-I N O O r-i CM O U r-i CM O O ι I CM α O ο ro 33 υ O δ ro p ~ J O O O ro th O O O ro 33 O O ο 33 55 CJ ο 33 U O 33 55 CJ O 33 55 & 33 ο CJ ro - 33 υ ro * υ υ ro rc O CJ ro 33 33 33 O 33 55 O W W O 33 Xi - O 33 33 O CJ ro O CJ ro 33 O CJ ro 33 O CJ ro ιη U O 33 in in CJ O 33 in CJ O 33 in CJ O 33 33 ιη 33 O CJ SG 33 33 O O EC in 33 O CJ 33 in - O O U) 33 O O in O O © U> 33 33 CJ O U) 33 33 CJ O • η O U) - O O CJ O CJ U) 33 O O Φ 33 O O in 33 O in O ro CJ in O ro O in 33 O O CM 33 33 p * 33 33 B r-i ro 33 33 fm 33 W CM 55 O U) in 33 u> in CJ # - { U) m 33 U fm U) in 33 55 CJ 33 O th CJ O CJ 33 O O 33 33 CM ω in 33 U) in rh CJ ro U) in ro U) in 33 O O 33 33 CJ 33 O rh {r- CJ 33 (M fm CJ 33 No. VO 55 U) • -I CVJ U) VO O CJ ro U) i-H O ro U) • νο r- O U r ^ 33 Ü r ^ CJ r-i U OO CVJ (M O CO VO 55 CO co CO r-i CJ ro CO OO fm CJ ro Q) CVJ cn Ö CVJ CVI 33 CVJ CO U O r-i CVJ co fm OJ 00 55 co 33 CVJ OO rh υ CVJ co fm O VO r- CJ O OO CO σ " 33 CO CO r-i co -fr fm CVJ VO CVJ OJ O CS OO co O co ITI CO O CO UI CVJ CVJ P ^ CVJ OO cvi OO CO CO CO co CVJ CVJ CVJ CVJ

- 57 -

H.2.1. Preparation of Pyridincarbonsa'urehalogenide of formula II H.2.1.1. Preparation of 5-trifluoromethylpyridine-2-carboxylic acid chloride

To a suspension of 22.9 g (0.1 mol) of 5-trifluoromethylpyridine-2-carboxylic acid potassium salt and 10 drops of DMF in 250 ml of toluene 9.8 ml (0.11 mol) of oxalyl chloride are added dropwise, the temperature rises to 40 ⁰ C and a lively gas development begins. The mixture is then stirred at 40 ⁰ C for 2 hours. The light brown suspension is then evaporated on a rotary evaporator, with 250 ml of ether abs. stirred, filtered and evaporated again.

17.8 g (85%) of the title compound of the formula are isolated

J! V \ o-ci

as a brown OeI (verb No. 3.078).

H. 2.1.2. Preparation of S-chloro-st-.rifluoromethyl-pyridine - ^ - carboxylic acid -

ethyl ester

216 g (1 mol) of 2,3-dichloro-5-trifluoromethylpyridine, 16.7 g of [PdCl ₂ (PPh ₃ ) ₂ ] and 420 ml (3 mol) of triethylamine are dissolved in 3.3 l of ethanol under CO ₂ atmosphere at 50 stirred bar and 100 ⁰ C for 14 hours. The mixture is then evaporated at 40 ⁰ C on Rotavapor. The resulting mass is stirred with 2 1 ether, filtered off from triethylamine hydrochloride and evaporated on a rotary evaporator. This gives 245 g of a brown oil which is purified on silica gel with ethyl acetate / hexane (1: 9).

206.8 g (81.6 %) of the title compound of the formula are isolated

I ^X COOC ₂ Hs

as yellow OeI (verb no. 3.005).

- 58 -

28 4 ο υ 2

H.2.1.3. Preparation of S-chloro-S-trifluoromethylpyridine -carboxylic acid e 76 g (0.3 mol) of ethyl 3-chloro-5-trifluoromethylpyridine-2-carboxylate are stirred with 165 ml (0.33 mol) of 2N NaOH for 6 hours. The resulting solution is washed twice with methylene chloride. The aqueous solution is then adjusted to pH 1 with hydrochloric acid 37% and the product is filtered off with suction and dried in vacuo at room temperature.

65 g (96 X) of the title compound of the formula are isolated

as white crystals of mp. 135 ° C (Zers.) (Ed. No. 3,039).

H.2.I.A. Preparation of S-chloro-S-trifluoromethylpyridine-carboxylic acid

chloride

16.9 g (75 mmol) of 3-chloro-5-trifluorometbylpyridine-2-carboxylic acid are suspended in 75 ml of hexane. After addition of 2 drops of DMF, 7 ml (80 mmol) of oxalyl chloride in 25 ml of hexane are added dropwise. Subsequently, it is stirred at 50 ^° C. for A hours until the evolution of gas has ended. The reaction solution is filtered and evaporated on a rotary evaporator.

18 g (98%) of the title compound of the formula are isolated

\ oci

as a yellow OeI (Verb. No. 3.073).

Analogously to the above preparation methods, the compounds of Table 3 can be synthesized.

H. 2.1.5. Preparation of 3,5-dichloro-pyridine-2-carboxylic acid ethyl ester 250 g (1.3 mol) of 2,3,5-trichloropyridine 95% are prepared according to the procedure H.2.1.2. implemented and cleaned.

- 59 -

1A7g (51.5%) of the title compound is isolated as a yellow oil of the formula

^C V \ / ^C1

π ι

^N N ⁷ ^ CO-OC ₂ H ₅ as a yellow OeI (Comp. No. 3.139).

H.2.1.6. Preparation of ethyl 3-chloro-5-methylthio-2-carboxylate In a suspension of 1/9 g (0.16 mol) of potassium tert-butoxide and A, 8 g of polyethylene glycol. ¹ . 1500 in 480 ml of toluene are introduced at 25-30 ⁰ C 8.6 g (0.18 mol) of methyl mercaptan. The mixture is then stirred at 35 ^° C. for 15 minutes. The resulting white suspension is cooled to -30 ⁰ C and mixed with 35.2 g (0.16 mol) of ethyl 3,5-dichloro-pyridine-2-carboxylate, allowed to warm to 20-25 ⁰ C and at this temperature Stirred for 15 hours. The reaction mixture is filtered off from the potassium chloride and evaporated on a rotary evaporator. This gives 41 g of a yellow oil, which is purified on silica gel with petroleum ether / ether (3: 1).

16 g (43.3%) of the title compound of the formula are isolated

^CH3 ~ V \ / ^C1

\ A / ° - ^C2Hs

0 as yellow OeI (verb no. 3,018).

H.2.1; 7th Preparation of 3-chloro-5-m <3-thylthiopyridine-2-carboxylic acid 22 g (0.095 mol) of ethyl 3-chloro-5-methylthiopyridine-2-carboxylate are prepared analogously to H.2.1.3. implemented and cleaned.

18.3 g (94.7%) of the title compound of the formula are isolated

^CH3 ~ V \ - ' ^C1

Ii i

• ·

C00H as white crystals (verb No. 3.052).

- 60 -

H.2.1.8. Preparation of 3-chloro-5-methylthiopyridine-2-carboxylic acid chloride 9.8 g (0.048 mol) of 3-chloro-5-methylthiopyridine-2-carboxylic acid are suspended in 65 ml of hexane and 25 ml of dichloroethane. After adding 2 drops of DHF and warming to 55 ⁰ C A, 9 ml (0.055 mol) of oxalyl chloride are added dropwise. The mixture is then stirred for 4 hours at 55 ° C until the gas evolution is complete. The reaction solution is filtered and evaporated on a rotary evaporator.

10.6 g (99.5%) of the title compound of the formula are isolated

vv

η i V \ o-ci

as yellow waxy crystals (Ed # 3,086).

H. 2 2 .1. Ethyl 3-chloro-5-methylsulfonyl-pyridine-2-carboxylate To a solution of 16.2 g (70 mmol) of S-chloro-S-methylthiopyridine -carboxylic acid ethyl ester in 50 ml of dichloromethane is added 44 g (140 mmol) of 3-chloroperbenzoic acid 55% in 150 ml of dichloromethane is added dropwise so that the temperature does not exceed 30 ° C. After stirring for 15 hours at room temperature, another 19 g (70 mmol) of 3-chloroperbenzoic acid 55% in 75 ml of dichloromethane are added dropwise to the suspension in order to complete the reaction. Subsequently, the mixture is stirred for 3 hours at room temperature. The white suspension is diluted with about 200 ml of dichloromethane and filtered off from the precipitated 3-chlorobenzoic acid. The resulting solution is washed with NaHCO 3 solution 5% and with water. The solution is evaporated on a rotary evaporator.

15.3 g (83%) of the title compound of the formula are isolated:

Il I t ·

V NjOC ₂ H ₅

as crystals of the mp 90-93 ⁰ C (Ref No. 3.017)

- ⁶ I-28400

H. 2.2. 2 3-Chloro-5-niethylsulfonyl-pyridine- 2- carboxylic acid To a mixture of 55 ml (55 mmol) NaOH IN and 5.5 ml ethanol is added 13.2 g (50 mmol) of S-chloro-S-methylsulfonyl-pyridine - ^ - Carboxylic acid ethyl ester given, the temperature avif 32 ⁰ C increases. The mixture is then stirred for 3 hours at room temperature. The solution is diluted with 150 ml H2O, washed 2x with Dichlormathan and then made strongly acidic at 0-5 ⁰ C and HCl 37%. The precipitated product is filtered off, washed with a little ice water and dried.

10.4 g (88.3%) of the title compound of the formula s Cl are isolated

• ·

as crystals of mp> 150 ° C (Zers.) (Comp. No. 3.051).

H 2.2.3. 3-Chloro-5-methylsulfonyl-pyridine-2-carbon acid aureide 9.9 g (42 mmol) of 3-chloro-5-methylsulfonyl-pyridine-2-carboxylic acid are dissolved in 100 ml of toluene with 4.4 ml (60 mmol) of thionyl chloride Boiled for 2 hours at reflux. The brown suspension is evaporated on a Rotavapor.

10.4 g (97.5%) of the title compound of the formula H ₃ CO ₂ S _{x are} isolated. Cl

t · *

Il

'; Ci

as brown wax (verb No. 3,086).

table

- 62 -

284 O O 2

Compounds of the formula

"\ A / ^R1

Il

V \ o-y

Verb no.

3 3 3 3 3 3 3 3 3, 3, 3

 3

 3

 3

 3

 Third

.001 .002 .003 .004, 005, 006, 007 008 009 010 011 012 013 014 015 016

3017

018 .019 .020 .021 .022 .023 .024 .025 .026 .027 .028 .029 .030 .031 .032, 033, 034 035 036 037 038 039 040 041 042 043

3044

R ¹ R ² Cl Cl Cl H H Cl H H Cl CF ₃ NO ₂ H H NO ₂ NO ₂ Cl CF ₃ H H CF ₃ OCH ₃ H CN H OCH ₃ Cl CN Cl br Cl SCH ₃ Cl SO ₂ CH ₃ Cl Cl SCH ₃ Cl SOCH ₃ Cl SO ₂ CH ₃ SOCH ₃ Cl SO ₂ CH ₃ H H SO ₂ CH ₃ H CH ₃ Cl F H CF ₃ F F F CF ₃ CF ₃ F H CCl ₃ CCl ₃ H Cl CCl ₃ CCl ₃ Cl CH ₃ H Cl Cl Cl H H Cl H H Cl CF ₃ NO ₂ H H NO ₂ NO ₂ Cl CF ₃ H H CF ₃

OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OC ₂ Hf OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OC ₂ Hj OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OC ₂ H ₅ OH OH OH OH OH OH OH OH OH

phys , dates OeI OeI 'Mp. 56-58 ⁰ C Oei Mp. 89-91 ° C

Mp 43-45 ⁰ C

Mp. 77-8O ° C mp. 90-93 ⁰ C oil

OeI OeI

Mp 157 ° C (decomp.)

Mp> 125 ° C (decomp.)

Mp 135 ° C (decomp.)

Mp 135 ° C (decomp.)

Mp 129-131 ° C

- 63 -

28 4 ο ο 2

Verb no. R ¹ 3045 OCH ₃ 3046 CN 3047 OCH ₃ 3048 CN 3049 br 3050 SCH ₃ 3051 SO ₂ CH ₃ 3052 Cl 3053 Cl 3054 Cl 3055 SOCH ₃ 3.05C SO ₂ CH ₃ 3057 H 3058 H 3059 Cl 3060 H 3061 V 3062 T 3063 CF ₃ 3064 H 3065 CCl ₃ 3066 Cl 3067 CCl ₃ 3068 CH ₃ 3069 Cl 3070 Cl 3071 H 3072 H 3073 Cl 3074 NO ₂ 3075 H 3076 NO ₂ 3077 CF ₃ 3078 H 3079 OCH ₃ 3080 · CN 3081 OCH ₃ 3082 CN 3083 br 3084 SCH ₃ 3085 SO ₂ CH ₃ 3086 Cl 3087 Cl 3088 Cl 3089 SOCH ₃ 3090 SO ₂ CH ₃ 3091 H 3092 H 3093 Cl 3094 H

R ² Y phys. data H OH K OH Cl OH Cl OH Cl OH Cl OH Cl OH Mp> 150 ° C ( SCH ₃ OH firmly SOCH ₃ OH SO ₂ CH ₃ OH Cl OH H OH SO ₂ CH ₃ OH CH ₃ OH Mp> 135 ° C ( F OH Mp> 143 ° C ( CF ₃ OH F OH CF ₃ OH F OH CCl ₃ OH H OH CCl ₃ OH Cl OH H OH Cl Cl Mp 54-56 ° C H Cl firmly Cl Cl firmly H Cl CF ₃ Cl Oei H Cl NO ₂ Cl Cl Cl H Cl Oei CF ₃ Cl Oei H Cl Λ Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl SCH ₃ Cl firmly SOCH ₃ Cl SO ₂ CH ₃ Cl Cl Cl H Cl SO ₂ CH ₃ Cl CH ₃ C.i. Oei F Cl Oei CF ₃ Cl

(Zers.) (Zers.)

Verb no. R ¹ R ^{2 γ} ι phys. data 3095 F F Cl 3096 F CF ₃ Cl 3097 CF ₃ F Cl 3098 H CCl ₃ Cl 3099 CCl ₃ H Cl 3100 Cl CCl ₃ Cl 3101 CCl ₁ Cl Cl 3,102 CH ₃ H Cl 3103 Cl OCH ₃ OC ₂ H ₅ 3104 Cl OCH ₃ OH firmly 3105 Cl OCH ₃ Cl firmly 3106 H OCH ₃ OC ₂ H ₅ 3107 H OCiI ₃ OH 3108 H OCH ₃ Cl 3109 H OC ₁ H ₇ (J) OC ₂ H ₅ 3110 H OC ₃ H ₇ (I) OH 3111 H OC ₃ H ₇ O.) Cl 3112 H OCH ₃ OCH ₃ Mp 27-74 ⁰ C 3113 H SCH ₃ OC ₂ H ₅ Mp 46-48 ⁰ C 3114 H SCH ₃ OH Mp 159-16C ° C 3115 H SCH ₃ Cl firmly 3116 Cl SC ₂ Hs OH 3117 Cl SC ₂ H ₅ OC ₂ H ₅ 3118 Cl SC ₂ H ₅ Cl 3119 Cl SOC ₂ H ₅ OH 3120 Cl SOC ₂ H ₅ OC ₂ H ₅ 3121 Cl SuC ₂ H ₅ Cl 3122 Cl SO ₂ C ₃ H; (i) OH 3123 Cl SOC ₃ H ₇ (i / OH 3124 Cl SC ₃ H ₇ (I) OH 3125 Cl SO ₂ C ₃ H ₇ (I) OC ₂ H ₅ 3,126 Cl SOC ₃ H ₇ (J.) OC ₂ H ₅ 3127 Cl SC ₃ H ₇ (D OC ₂ H ₅ 3128 Cl SO ₂ C ₃ H ₇ (D. Cl 3129 Cl SOC ₃ H ₇ (I) Cl 3130 Cl SC ₃ H ₇ (O Cl 3131 Cl OC ₃ H ₇ (X) OH 3132 Cl OC ₃ H ₇ (D OC ₂ H ₅ 3133 Cl OC ₃ H ₇ (D Cl 3134 SCH ₃ SCH ₃ OC ₂ H ₅ Mp 60-7O ⁰ C 3135 Cl br OH 3136 Cl br OC ₂ H ₅ 3137 Cl br Cl 3138 Cl OCH ₃ OCH ₃ Mp. 7? -74 ° C 3139 Cl Cl COOC ₂ H ₅ Oei

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284 0 0

F. formulation Examples

Example Fl .: Formulation Examples of Active Ingredients of the Formula I.

(% = Weight percent)

a) emulsion concentrates a) b) c)

Active substance according to Table 1 or 2 20% 40% 50%

Ca-dodecylbenzenesulfonate 5% 8% 5.8%

Castor oil polyethylene glycol ether>

(36 moles EO) 5% - Tributylphenoyl polyethylene glycol ether

(30 mol EO) - 12% 4.2%

Cyclohexanone - 15% 20%

Xylene mixture 70% 25% 20%

From such concentrates, emulsions of any desired concentration can be prepared by dilution with water.

b) solutions

Active ingredient according to Table 1 or 2 ethylene glycol monomethyl ether polyethylene glycol MG 400 N-methyl-2-pyrrolyl ion

Epoxidized coconut oil

The solutions are suitable for use in the form of very small drops.

c) Granules a) b)

Active ingredient according to Table 1 or 2 5% 10%

Kaolin 94%

Highly dispersed silica 1%

Attapulgite - 90%

The active ingredient is dissolved, sprayed onto the carrier and the solvent is then evaporated in vacuo.

a) b) c) 80% 10% 5 20% - - - 70% - - 20% 5 90

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d) dusts a) b) c) Active ingredient according to Table 1 or 2 2% 5% 8 % Highly dispersed silicic acid 1 % 5% 5% talc 97% - 10% kaolin 90% 77%

Intimately mixing the excipients with the active ingredient gives ready-to-use dust.

e) spray powder a) b) Active ingredient according to Table 1 or 2 20% 60 Na ligninsulfonate 5% 5 Na lauryl sulfate 3% 6 Ocuylphenolpolyethylenglykolether (7-8 mol EO) - 2 Highly dispersed silicic acid 5% 27 kaolin 67%

The active ingredient is well mixed with the additives and ground well in a suitable mill. This gives wettable powders, which can be diluted with water to the suspension of any desired concentration.

f) extruder granules

Active ingredient according to Table 1 or 2 10%

Na lignosulfonate 2%

Carboxymethylcellulose 1%

Kaolin 87%

The active ingredient is mixed with the additives, ground and moistened with water. This mixture is extruded and then dried in a stream of air.

g) serving granules

Active ingredient according to Table 1 or 2 3%

Polyethylene glycol (MW 200) 3%

Kaolin 94%

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The finely ground active substance is applied uniformly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coating granules are obtained.

h) suspension concentrate

Active ingredient according to Table 1 or 2 40%

Ethylene glycol 10%

Nonylphenol polyethylene glycol ether (15 moles EO) 6%

Na lignosulphonate 10%

Carboxymethylcellulose 1%

37% aqueous formaldehyde solution 0.2%

Silicone oil in the form of a 75% aqueous emulsion 0.8%

Water 32%

The finely ground active substance is intimately mixed with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.

B. Biological Examples

Example B 1 : Pre-emergent herbicidal action Immediately after sowing the test patches in seed trays in the greenhouse, the soil surface is treated with an aqueous dispersion of the active ingredients obtained from a 25% strength emulsion concentrate. Different rates of active substance / hectare are tested. The seed trays are kept in the Gowachshaus at 22-25 ° C and 50-70% relative humidity, and the trial evaluated after 3 weeks.

The herbicidal effect is evaluated in a nine-stage (1 = complete damage to the test plant, 9 = no herbicidal effect on the test plant) Boniturschema compared to untreated control group.

Boniturnoten 1 to 4 (especially 1 to 3) indicate a good to very good herbicidal action. Boniturnoten from 6 to 9 (especially from 7 to 9) indicate a good tolerance (especially in crops). The test results for Compound No. 1.005 are summarized in Table 4.

Table 4 2000 Application rate [g / ha] 5000 250 125 Herbicidal action 60 7 1000 9 9 9 9 test plant 8th 7 9 9 9 9 barley 8th 9 9 9 9 9 wheat 7 9 9 9 9 9 Corn 1 8th 2 2 2 5 sorghum 1 1 1 1 1 1 Abutilon 1 1 1 1 2 3 Chenopodium Sp. 1 1 1 1 4 6 Solanum nigrum 1 Veronica Sp. rust-emergence Example B 2: 1

A number of weeds, both monocotyledonous and dicotyledonous, are sprayed onto the plants after emergence (at the 4- to 6-leaf stage) with an aqueous dispersion of active ingredient at a dosage of 250 g to 2 kg of active substance per hectare and at 24 ° -26 ° C and maintained at 45-60% relative humidity. 15 days after treatment, the experiment is evaluated according to the Boniturschema described in Example Bl.

The test results for compound 1.005 are summarized in Table 5.

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Table 5 2000 application rate tg / h 9 a] 9 1000 5000 9 2 50 test plant 8th 9 9 9 barley 8th 9 9 9 wheat 7 9 9 9 Corn 7 8th 2 9 sorghum 1 8th 1 9 Rice (dry) 1 1 1 3 Abutilon 1 1 3 2 Chenopodium Sp 2 1 2 Solanum nigrum 2 3 sinapis Herbicidal efficacy for water rice (paddy) Example B 3:

The water weeds Echinochloa crus galli and Monocharia vag. are sown in plastic cups (60 cm ² surface, 500 ml volume). After sowing, make up to the surface with water. 3 days after sowing, the water level is raised slightly above the surface (3-5 mm). The application is carried out 3 days after sowing with an aqueous emulsion of the test substances by spraying on the vessels at an application rate of 60 to 250 g AS per hectare. The plant cups are then placed in the greenhouse under optimal growth conditions for the rice weeds, ie at 25 ° -30 ° C and high humidity. The evaluation of the experiments takes place 3 weeks after application. The compounds according to Table 1 damage the weeds, but not the rice.

Claims (2)

claims 1. A method for Horstellung of cyclohexane-1,3-dionan of the formula I or I 'and their salts> χ Ο Ο/ Χ / χ Ο V A u4 4-r ' ρ? _3 IIV or _d3 I II V ^ / \ / V "/ \ / V ^ ₇ wherein R ¹ and R ^{2 are} independently hydrogen; Halogen; nitro; cyano; Ci-C, alkyl; Cι-Cι, alkoxy; Ci-Cu-alkyl-SiO) -; COR ⁸ ; Ci-Ci ₁ -Halogenalkoxy; or Ci-Ci, -Halogenalkyl; R ³ , R ¹ * and R ^{5 are} independently hydrogen; C-Ci. A.lkyl; or optionally up to three times, identically or differently, by halogen, nitro, cyano, C ₁ -C 4 -alkyl, C ₁ -C ₁ -alkoxy, C ₁ -C 4 -alkyl-S (O) -, C ₁ -C 4 -haloalkyl, C ₁ -C 4 -alkyl -Ci, -haloalkyl-S (O) - or Ci-Ci, -haloalkoxy sub- substituted phenyl or benzyl; R ^{6 is} hydrogen; Ci-Ci, -Alkyl, Ci-Ci, -Alkoxycarbonyl; or cyano; R ⁷ OH; or 0®M®; R ⁸ OH; Ci-Cw-alkoxy; NH2; Ci-Ci, alkylamino; or di-Ci-Ci, -Alkylamino; η 0, 1 or 2; M is a cation equivalent of a metal ion or an optionally up to three times by Ci-Ci, -Alkyl, Ci-Ci, -Hydroxyalkyl, or Ci-Ci ₁ -Akk- oxy-Ci-Ct, alkyl groups substituted ammonium ion characterized by the reaction of cyclohexanediones of the formula II, with a pyridine of the formula III, wherein X is halogen or den rest OC-OR ⁸ , or -OC-4 4-R ² and R ^{8 is} Ci-Ci, -alkyl, phenyl or benzyl means in the presence of a base II III b) the thermal rearrangement of an ester of the formula IV or IV ¹ , ψ 0 • ν .C- (j) -C-H-4-R ² * _N C-H-FR ² / \. V _R3 _i ^N i V IV y »Ia (r7 = OH) and / or ft ft Jv ft // ^ ³ AA VlU 4-R ² R ^ (V A ^v IV ¹ Ia "(R ⁷ = OH) -72- 28400 and optionally reacting the resulting cyclohexanedione of formula I or 1 * 7 wherein R represents OH with a base of formula V HOM to the salt and optionally oxidation of a cyclohexanol ion 8 of the formula I or I *> · wherein one or more of the radicals R ¹ to R ^{6 is} C ₁ -C ₄ -alkyl-S- with H ₃ O ₂ or peracids O 2ο herbicidal composition, characterized - that it contains a compound of formula I according to claim 1 in addition to other excipients and / or excipients « Use of compounds of the formula I, characterized in that they are used for controlling undesired plant growth, A method of controlling unwanted plant growth characterized by the fact that a compound of the formula I according to claim 1 or an agent according to claim 2 is allowed to act on the plant or its habitat to be controlled. 5 «A method according to claim 4V characterized in that it is used for controlling weeds or grasses in crops« Process according to claim 4, characterized in that it is used for the pre- or postemergent control of weeds or grasses in cereals, cotton, soya, corn, rice, sugar cane or millet. "