DD297963A5 - N-ARYL NITROGEN HETEROCYCLES, METHOD AND NEW INTERMEDIATE PRODUCTS FOR THEIR PREPARATION AND THEIR USE AS HERBICIDES AND PLANT GROWTH REGULATORS - Google Patents

Abstract

The invention relates to new N-aryl-nitrogen heterocycles of the general formula in which Het is a heterocycle of the formula R 1 is hydrogen or halogen and R 2 is halogen or a radical XR 9, and the remaining radicals are as defined in the description have, processes and novel intermediates for their preparation and their use as herbicides and plant growth regulators. Formula (I) and formula

Description

BAYER AKTIENGESELLSCHAFT 5090 Leverkusen, Bayerwerk Group Management RP

Patents Group KM / jö-c

(Ib)

N-aryl-nitrogen heterocycles, processes and novel intermediates for their preparation and their use as herbicides and plant growth regulators

The invention relates to novel N-aryl-nitrogen heterocycles, to a plurality of processes and to novel intermediates for their preparation and to their use as herbicides

^ώυ and plant growth ^regulators .

It is known that certain N-aryl nitrogen heterocycles, such as, for example, the compound 1- (2-chloro-4-trifluoromethylphenyl) -5-methyl-4-nitropyrazole, have herbicidal properties (cf., for example, EP 200 872),

The herbicidal activity of these prior art compounds against problem weeds, however, as well as their compatibility with important crops is not completely satisfactory in all fields of application. "~

So far, nothing is known about a plant growth-regulating effect of the previously known compounds. 35

Le A 26 501-foreign countries

- 2 - J37963

There were new N-aryl-nitrogen heterocycles of the general formula (I)

(I)

in which

Het for a heterocycle of the formula

R ⁴ R ⁵ 0 R ⁸ ^ O

0-< N-{

IN-; I N- or I N- stands,

R ³ R ^c

R ^{1 is} hydrogen or halogen and R ^{2 is} halogen or a radical -XR ⁹ ,

in which

R ^{3 is} hydrogen, alkyl or haloalkyl

,

and

R ^{4 is} hydrogen, halogen, alkyl or haloalkyl or

R ³ and R ⁴ together represent doubly linked alkanediyl,

R ^{5 is} hydrogen, halogen, alkyl or haloalkyl, 35

Le A 2 6 501

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R ^{6 is} hydrogen, alkyl «alkoxyalkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, halo

genalkinyl or represents optionally substituted cycloalkyl,

R ^{7 is} hydrogen, alkyl, alkoxyalkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl,

Haloalkynyl or optionally substituted »cycloalkyl and

R ^{8 is} hydrogen, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl or haloalkynyl

stands or

R 'and R ⁸ together for doubly linked

Alkanediyl, 20

Each R ⁹ is optionally substituted Alkyl, alkenyl, alkynyl or cycloalkyl

and

X is oxygen or sulfur, found.

Furthermore, it has been found that the novel N-aryl-nitrogen heterocycles of the general formula (I)

(I)

Le A 26 501

in which 5

Het for a heterocyclic of the formula

R ⁴ R ⁵ O R ⁸

N-; N- or N- stands,

¹⁰ R

R * is hydrogen or carbon and

R ^ stands for halogen or a radical -X-R ^ "15

in which

R ^{3 is} hydrogen, alkyl or haloalkyl

and 20

R ^{4 is} hydrogen, halogen, alkyl or haloalkyl or

R ³ and R ⁴ together for doubly linked Alkandiyl stand,

R ^{5 is} hydrogen, halogen, alkyl or haloalkyl Bteht,

R ^{6 is} hydrogen, alkyl, alkylalkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl or optionally substituted cycloalkyl,

35

Le A 2 6 501

231363

R ^{7 is} hydrogen "alkyl" alkoxyalkyl "haloalkyl" alkenyl "haloalkenyl" alkynyl "

Haloalkynyl or optionally substituted cycloalkyl and

R ^{8 is} hydrogen "alkyl" haloalkyl "alkenyl" haloalkenyl "alkynyl or haloalkynyl

stands or

R ⁷ and R ⁸ together for doubly linked

Alkanediyl stand «15

R ⁹ for each optionally substituted Alkyl "alkenyl" is alkynyl or cycloalkyl

and

χ stands for oxygen or sulfur «

according to one of the methods described below:

(a) N-aryl-nitrogen heterocycles of the formula (Ia) are obtained.

(Ia)

I -χ > / j

in which

Le A 26

R ⁴ ' ^{1 is} hydrogen, alkyl or haloalkyl or together with R ^{3 represents} a double ver

established alkandiyl residue Bteht,

R ⁵ ' ^{1 represents} hydrogen, alkyl or haloalkyl

and 10

R ¹ , R ^ and R ³ are as defined above

to have,

when 4-cyanophenylhydrazines of the formula (II)

R ¹ 's _r £ r * v _N ^' CN

(II) HgN-NH ^^ V ^^ R ²

in which 20

R * and R ^ have the meaning given above,

with 1,3-diketones of the formula (III),

r J

R ³ ^ -C-CH-CR ⁵ " ¹ (III)

Il Il 0

in which 30

R ³ , R ^4-1 and R ⁵ ' ^{1 have} the abovementioned meaning,

Le A 26

Z3} 3%

or with derivatives of these diketones, such as, for example, enol ethers, enol esters; If appropriate, ketals, enol ether ketals, enamines or O-halovinyl ketones are reacted in the presence of a diluent and if appropriate in the presence of a reaction auxiliary; 10

(b) men ^sf ei \ N-aryl lt Stickstof fheterocyclen of formula (Ib),

_R 4-2 r5-1 _R l 'NCX) -CN (Ib)

R ²

in which

R ⁴ " ^{2 is} halogen,

R ⁵ " ^{1 represents} hydrogen, alkyl or haloalkyl and

\ 9 τ

R ¹ , R 'and R * ^{3 have} the abovementioned meaning

to have,

when N-aryl-nitrogen heterocycles of the formula ^(IJ) '

if

R ³ 35

Le A 2 6 501

(Ij)

R ° R ²

in which 5

R ¹ , R ² , R ³ and R ⁵ " ^{1 have} the abovementioned meaning,

with a halogenating agent, if appropriate in the presence of a »diluent converts;

(c) N-aryl-nitrogen heterocycles of the formula (Ic) are obtained.

in which 20

R ⁵ " ² stands for Helogen and R ¹ IK ² , R ³ and R ⁴ are as defined above

have, 25

when N-aryl-pyrazolinones of the formula (IV),

R <

(Iv) 30

in which

Le A 26

- 9 - Ζ9Ϊ963

R * , R ² »R ³ and R ^{4 have} the meaning given above«

with a Halogenierungemittel «optionally in the presence of a diluent and optionally in the presence of a reaction auxiliary;

(d) one obtains N-aryl-Stschlackoffheterocyclen of formula (Id),

(Id)

in which 20

R, R ² and R have the meaning given above »

when 4-cyanophenylhydrazines of the formula (II) »25

R ¹ 's _r ^ v _v ^ c _N

(II)

in which 30

R ¹ and R ^{2 have} the meaning given above »

Le A 26

- 10 -

297363

with iminocarbon esters of the formula (V),

R ⁷ Cf

RIO-OC = NCOR ¹¹ (V)

in soft 10

H ¹ ^ and R ¹¹ are each independently alkyl and

R ^{7 has} the abovementioned meaning, if appropriate in the presence of a diluent;

(e) N-aryl-nitrogen heterocycles of the formula (Ie) are obtained «

in which

R ⁸ " ^{1 represents} alkyl" haloalkyl, alkenyl "haloalkenyl, alkynyl or haloalkynyl

and

R ¹ R and R have the meaning given above ι

Le A 26

-U-

2W963

when N-aryl-nitrogen heterocycles of the formula (Id),

in which

R ¹ , R ² and R 'are as defined above

have , 15

with alkylating agents of the formula (VI), _R 8-1_ _E 1 _(VI) ·, w

in which

R® " ^{1 has} the meaning given above and

E ^{1 stands} for an electron attracting leaving group,

t 1is reacted in the presence of a reaction auxiliary, if appropriate in (rain waiting a diluent and gegebenenf;

(f) N-aryl-nitrogen heterocycles of the formula (If) are obtained;

Le A 26

- 12 -

R ⁸ " ² ^ OR ¹

N (If)

in which

R ⁷ ~ * and R ⁸ "" ² together represent a doubly linked alkanediyl radical "

when amidrium of the formula (VII) «

R ⁷ " ¹

R ⁸ ~ ² -NH-C = N-NH ~ <V-CN (VII)

_ _N in which

R ⁷ "^ and R ⁸ " ^ have the meaning given above "

optionally reacted with phosgene in the presence of a diluent and optionally in the presence of a reaction!

(g) one obtains N-aryl-nitrogen heterocycles of the formula ^(Ig) '

Le A 26 501

- 13 - 29? S63

in which 5

R ¹ , r ² and R ^{6 have} the meaning given above

when phenylhydrazides of the formula (VIII)

R ²

NC-, NH-NH-CR ⁶ (VIII)

in which

4 Ο A ·

Rj R and R have the abovementioned meaning,

optionally reacted with phosgene in the presence of a diluent and optionally in the presence of a reaction auxiliary;

(h) N-aryl-nitrogen heterocycles of the formula (Ih) are obtained,

" ^X " ^F

in which

Le A 26

- 14 - ZSlS (, 3

R *, R ³ , R ⁴ , R 1, R ⁹ and X have the abovementioned meaning,

alternatively, when (") N-aryl-nitrogen heterocycles of the formula

R ⁴ R ⁵

in which

R ² " ^{1 is} halogen and

R ¹ , R ³ , R ⁴ and R ^{5 have} the meaning given above »

with alcohols or thiols of the formula (IX), R ⁹ -XH (IX)

in which F ⁹ and X have the abovementioned meaning,

if appropriate in the presence of a diluent and if appropriate in the presence of a reaction aid or if one reacts

Lo A 26

(&) (Thio) Phenol derivatives of the formula (X), R ⁴ R ⁵ R ¹

ν C y-cn (χ)

XK

in which

R ¹ , R ³ , R ⁴ , R ^ and X have the abovementioned meaning,

with Alkyliarunga- or "acylating agents of the formula (XI), R ⁹ -E ² (XI) in which

R ^{9 has} the abovementioned meaning and E ² for an electron attracting departure

group stands,

if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary;

(i) N-aryl-nitrogen heterocycles of the formula (Ii) are obtained,

Le A 26

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Z31363

in which 10

R ¹ , R ² , R ³ and R ^{5 have} the abovementioned meaning,

alternatively also when l-arylpyrazolyl-4-carboxylic acid ester of the formula (XII)

R ¹² O-CO

(XII)

in which

R ^{12 is} alkyl and

R ¹ »R ² * R ³ and R ^{5 have} the abovementioned meaning,

saponified in the presence of an acidic or basic catalyst and optionally in the presence of a diluent and then thermally decarboxylated «

Le A 26

- 17 -

Finally, it has been found "that the new N-aryl-nitrogen heterocycles of the general formula (I) have herbicidal and plant-growth-regulating properties"

Surprisingly, the N-aryl-nitrogen heterocycles of the general formula (I) according to the invention show a significantly higher herbicidal activity against important problem weeds with a comparably good or better crop selectivity compared to the known from the prior art N-aryl-nitrogen heterocycles, such as the compound l- (2-chloro-4-trifluoromethylphenyl) -S-methyl-A-nitropyrazole, which are chemically and functionally obvious compounds «

In addition, the compounds of the formula (I) according to the invention unexpectedly additionally show a plant-growth-regulating action.

The N-aryl-nitrogen heterocycles according to the invention are generally defined by the formula (I). Preferred compounds of the formula (I) are those in which

Het is a heterocycle of the formula

, _n R ⁴ R ⁵ 0 R ⁸ ^ 0

R ⁶

or N- stands,

Le A 26 501

- 18 -

K 'is hydrogen, "fluorine" is chlorine or bromine, and 5

R ** is fluorine "chlorine or bromine or a radical -XR ⁹ "

in which

 10

R ^{3 is} hydrogen »for straight-chain or branched alkyl having t to 6 carbon atoms or for straight-chain or branched haloalkyl mi; 1 to 4 carbon atoms and 1 bib 9 same or different halogen

atoms stands and

R ⁴ is hydrogen, "fluorine" chlorine "bromo" iodo "for

straight-chain or branched alkyl having 1 bio 6 carbon atoms or for geraidkettigee

or branched heloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms or

R3 and ^R4 represent a doubly linked gerneineam Alkandiylreet having 2 to 6 carbon atoms "

R ^{5 is} hydrogen, fluorine "chlorine" is bromine "iodine" is straight-chain or branched alkyl with 1 bie

6 carbon atoms or represents straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms "

Le A 26 501

R ^{6 is} hydrogen for each straight-chain or branched alkyl having 1 to 6 carbon atoms

Substituons "alkenyl having 3 to 6 carbon atoms" alkynyl having 3 to 6 carbon atoms "haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms" haloalkenyl with

3 to 6 carbon atoms and 1 bi »5 same or different halogen atoms, halogenoalkynyl having 3 to 6 carbon atoms and up to 5 identical or different halogen atoms or alkoxyalkyl each having 1 to

Carbon atoms in the individual straight-chain or branched alkyl parts or represents optionally mono- or polysubstituted or differently substituted cycloalkyl having 3 to 7 carbon atoms

suitable substituents being: halogen, and in each case straight-chain or branched alkyl or alkoxy having in each case up to 4 carbon atoms.

R ⁷ for hydrogen "for each straight-chain? or branched alkyl having 1 to 6 carbon atoms "alkenyl having 3 to 6 carbon atoms" alkynyl having 3 to 6 carbon atoms "

Hülogenalkyl having 1 to 4 carbon atoms and

1 to 9 identical or different halogen atoms "haloalkenyl having 3 to 6 carbon atoms and 1 to 5 identical or different halogen atoms" haloalkynyl having 3 to 6 carbon atoms and 1 to 5

equal

Le A 26 501

- 20 -

or different halogen atoms or alkoxyalkyl having in each case 1 to 4 carbon atoms in the individual straight-chain or branched alkyl parts or represents optionally mono- or polysubstituted by identical or different substituents cycloalkyl having 3 to 7 carbon atoms, where as substituents

come into question: halogen, and in each case straight-chain or branched alkyl or alkoxy having in each case 1 to 4 carbon atoms and

R ^{8 is} hydrogen or in each case straight-chain or branched alkyl having 1 to 6 carbon atoms, alkenyl having 3 to 6 carbon atoms, alkynyl having 3 to 6 carbon tetalsms, haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogeno

men, haloalkenyl having 3 to 6 carbon atoms and 1 to 5 identical or different halogen atoms or haloalkynyl with. 3 to 6 carbon atoms and 1 to 5 identical or different halogen atoms or

R ⁷ and R ⁸ together represent a doubly linked alkanediyl radical having 2 to 6 carbon atoms and 30

R ^ for each straight-chain or branched

Alkyl of 1 to 8 carbon atoms, alkenyl of 2 to 0 carbon atoms, alkynyl of 3 to 8 carbon atoms, haloalkyl of 1 to 35

Le A 26 501

- 21 - 237363

to 8 carbon atoms and 1 to 17 identical or different halogen atoms.

Alkenyl having 2 to 8 carbon atoms and 1 to 15 identical or different Ha'ogenatomen "haloalkynyl having 3 to 8 carbon atoms and 1 to 13 identical or different halogen atoms, for cyanoalkyl" AIk-

oxyalkyl "alkylthioalkyl" haloalkoxyalkyl, alkoxyalkoxyalkyl "(bis-alkoxy) alkyl" (bis-alkylthio) alkyl "alkylcarbonylalkyl, alkoxycarbonylalkyl or alkoxyalkoxycarbonylalkyl each having 1 to 8 carbon atoms in the

individual alkyl moieties and optionally 1 to 9 identical or different halogen atoms "for optionally mono- or polysubstituted or differently substituted cycloalkyl, cycloalkyloxycarbonylalkyl or cycloalkyl

alkylalkyl having in each case 3 to 7 carbon atoms in the cycloalkyl part and optionally 1 to 4 carbon atoms in the straight-chain or branched alkyl tail "being as

Substituents in each case come into question: halogen

and in each case straight-chain or branched alkyl or alkoxy having in each case 1 to 4 carbon atoms "R ⁹ additionally represents in each case optionally substituted by alkyl having 1 to 4 carbon atoms substituted oxetanylalkyl" tetra "

hyc'rofuranylalkyl "Tetrahydrofuranylalky.loxycerbonylalkyl or tetrahydropyranylalkyl having in each case 1 to 3 carbon atoms in the respective

Le A 36 501

- 22 -

291963

or R ^{9 is} optionally einfsich or more than or equal to or

differently substituted aralkyl having 6 to 10 carbon atoms in the aryl moiety and 1 to 4 carbon atoms in the straight-chain or branched alkyl moiety is "where as aryl substituents in question komntin:

Halogen »cyano» nitro »in each case straight-chain or branched alkyl» alkoxy »alkylthio or alkoxycarbonyl having in each case 1 to 4 carbon atoms or in each case straight-chain or

branched haloalkyl »haloalkoxy or

Halogenoalkylthio each having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms and

X is oxygen or sulfur.

Particularly preferred are Verbindvingen of formula (I) »in which

Het i> - 'r a heterocyclic of the formula

0 R^8th _V 0 C< N <

N-; N ~ or N- stands, R ^{1 is} hydrogen »fluorine or chlorine and

Le A 26 501

- 23 - 237963

R ^{2 is} fluorine "chlorine or a radical -XR ⁹ , 5

in which

R ^{3 is} hydrogen, methyl, ethyl, η- or i-

Propyl, n-, i-, b- or t-butyl, for fluoromethyl, difluoroethyl, trifluoromethyl,

Chloromethyl, dichloromethyl, trichloromethyl, Difluorchlorrr.athyl or dichlorofluoromethyl Bteht and

R ^ is hydrogen, fluorine, chlorine, bromine, for

Methyl, ethyl, η- or i-propyl, n-, i-, s- or t-butyl, for fluoromethyl, difluoromethyl, irifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, dif luorchlorinethyl or

Dichlorofluoromethyl or

R ³ and R 1 together represent a. 1,3-propanediyl radical, a 1,4-butanediyl radical or a 1,5-pentanediyl radical,

R ⁵ for nitrogen, fluorine, chlorine, bromine, for

Methyl, ethyl, η- or i-propyl, n-, i-, s- or t-butyl, for fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl,

Trichloromethyl, difluorochloromethyl or di

chloe luormethyl sweht «

Le A 2 6 501

- 24 - 231963

R ^{6 is} hydrogen for methyl, ethyl, η- or i-propyl, n-, i-, s- or t-butyl, in each case

methyl, ethyl or tert-butyl, for allyl, for n- or i-butenyl, for chloroallyl, for dichloroallyl, for mono-, di- or trisubstituted by fluorine and / or chlorine

Propargyl, for chloropropargyl, for methoxy

methyl or each optionally optionally one to five times, identically or differently by fluorine, chlorine, methyl and / or methoxy substituted cyclopropyl, cyclopentyl or

Cyclohexyl stands, R ^{7 is} hydrogen, methyl, ethyl, η- or

i-propyl, n-, i-, s- or t-butyl, for each mono-, di- or trisubstituted by fluorine and / or chlorine-substituted methyl, ethyl

or t-butyl, allyl, n- or i-butenyl, chloroallyl, dichloroallyl, propargyl, chloropropargyl, methoxymethyl, or each optionally one to five times, the same or different

Fluoro, chloro, methyl and / or methoxy substituted cyclopropyl, cyclopentyl or cyclohexyl and

R ^{8 is} hydrogen, methyl, ethyl or η-

i-propyl, n-, i-, β- or t-butyl, for each mono-, di- or trisubstituted by fluorine and / or chlorine-substituted methyl, ethyl

Le A 26 501

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237963

or t-butyl | for allyl, for η- or i-

Butenyl, for Chiorallyl, for DichloralIyI, for Propargyl or chloropropargyl or R 'and R ° together represent a 1,3-propynediamine,

a 1,4-butanediyl radical or a 1,5-pentanediyl radical,

R 'is methyl, ethyl, η- or i-propyl, n-, i-, e- or t-butyl, allyl, propargyl, in each case straight-chain or branched pentyl,

Hexyl, butenyl, pentenyl, hexenyl, butynyl,

Pentinyl or hexynyl, in addition, in each case straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms, haloalkynyl or haloalkenyl having in each case 3 to 5 carbon atoms and in each case 1 to 8 glei

or in particular halogen fluorine, chlorine or bromine, in each case straight-chain or branched cyanoalkyl, alkoxyalkyl, alkylthioalkyl, haloalkoxyalkyl, alkoxyalkoxyalkyl, alkylcarbonylal

kyl, alkoxycarbonylalkyl o <le; · alkoxyalkoxycarbonylalkyl having in each case 1 to 5 carbon atoms in the individual alkyl portions, moreover in each case optionally one to three times, identically or differently, by methyl,

Methoxy, fluorine or chlorine substituted cyclopropylmethyl, cyrlopentylmethyl, cyclohexylmethyl, cyclopropylo. ^ ^ rbonylmethyl,

Le A 26 501

- 26 - 297S63

Cyclopentyloxycarbonylmethyl "cyclohexyloxycarbonylmethyl" cyclopropyl "cyclopentyl or

Cyclohexyl stands for "optionally substituted by methyl or ethyl oxetanylmethyl" oxetanylethyl , tetrahydrofuranylmethyl "tetrahydrofuranylethyl" tetrahydrofuranyliaethyloxycarbonylmethyl, tetrahydrofuranyl

pyranylmethyl or tetrahydropyranylethyl or is in each case optionally mono- to trisubstituted by identical or different substituted benzyl or phenylethyl

Substituents in each case come into question:

Fluorine "chlorine" bromine "cyano, nitro" methyl "ethyl" η- or i-propyl, η- "i-" or t-butyl "methoxy" ethoxy "n- or i-propoxy, methylthio" ethylthio «Methoxycarbonyl,

Ethoxycarbonyl "trifluoromethyl, trifluoro-

methoxy or trifluoromethylthio and

X stands for oxygen or sulfur "

Very particular preference is given to compounds of the formula (I) embedded image in which

Het for a heterocycle of the formula

OR ⁸ ^ 0

³⁰

O R ^ 0

N- or j N- stands,

R ¹ = R ^{1 is} hydrogen or fluorine and

Le A 26 501

- 27 - 297363

R ^{2 is} fluorine or a radical -XR ⁹ , wherein 5

R ^{3 is} hydrogen, methyl, ethyl, η- or i-propyl, n-, i-, β- or t-butyl, fluoromethyl, difluoromethyl or trifluoromethyl and 10

R ^{4 is} hydrogen, chlorine, bromine, methyl or trifluoromethyl or

R ³ and R ⁴ together represent a 1,3-propanediyl radical or an A, 4-butanediyl radical,

R ^{5 is} hydrogen, chlorine, bromine, methyl, ethyl, t-butyl or trifluoromethyl,

R ^ is methyl, ethyl, η- or i-propyl, n-, i-, o- or t-butyl, trifluoromethyl, fluoro-1,1-dimethylethyl or optionally mono- to fivefold, the same or different Fluorine, chlorine or methyl substituted cyclopropyl,

R ^{7 is} methyl and

R ^{8 is} hydrogen, methyl, ethyl, allyl, proppergyl, fluoromethyl, difluoromethyl or trifluoro

methyl stands or

Le A 2 6 501

- 28 -

Ζ3Ψ963

R ⁷ and R ⁸ together represent a 1,3-propanediyl radical or a 1,4-butanediyl radical «

R ^{9 represents} methyl, ethyl, η- or i-propyl, n-, i-, B- or t-butyl, allyl, propargyl, in each case straight-chain or branched pentyl,

Hexyl, butenyl, pentenyl, hexenyl, butynyl,

Pentinyl or hexynyl, furthermore represents jewitile straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms or haloalkenyl having 3 to 5 carbon atoms and each having 1 to 5 identical or different

which are halogen atoms, in particular fluorine, chlorine or bromine, in each case straight-chain or branched cyanoalkyl, alkoxyalkyl, alkoxyalkoxyalkyl or alkoxycarbonylalkyl having in each case 1 to 5 carbon atoms in the

individual alkyl moieties, furthermore in each case optionally mono- to trisubstituted by identical or different methyl, methoxy, fluorine or chlorine-substituted cyclopropylmethyl, cyclopentylmethyl, cyclohexylmethyl,

Cyclopropyloxycarbonylethyl, cyclopentyloxycarbonylmethyl, cyclonexyloxycarbonylmethyl, cyclopropyl, cyclopentyl, cyclohexyl, for each oxetanylroethyl, optionally substituted by methyl or ethyl,

tanylethyl, Tetrwhydrofuranylmethyl, Tetrahydrofuranylmethyloxycarbonylmethyl or tetrahydropyranylmethyl is odor for jeweile

Le A 26 501

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231363

benzyl or phenylethyl which is optionally monosubstituted to trisubstituted by identical or different substituents are in each case suitable as substituents: fluorine "chlorine" bromine "cyano" nitro "methyl" ethyl "η- or i-propyl" η- "i-" β - or t-butyl «Mr ^; thcxy "ethoxy" n- or i-propoxy "methylthio" ethylthio, methoxy

carbonyl «ethoxycarbonyl» trifluoromethyl «trifluoromethoxy or trifluoromethylthio and

X is oxygen or sulfur. 15

Specifically, in addition to the compounds mentioned in the preparation examples, the following N-aryl-nitrogen heterocycles of the general formula (I) may be mentioned:

(I) Het '"~

Le A 26 501

- 30 -

2379 * 3

Het

CHp = CH-CHp O

W "

F is -O-CH ₂ -C <

CH

CH ₂ = CH-CH ₂ OCH

CH ₂ -OCH ₃ <CH ₂ -OCH ₃

Ho Hl · - <

CH

CH ₂ = CH-CH ₉ O

CH

CH ₂ = CH-CH ₂ O

Ho

I  <

CH

CH ₂ = CH-CH ₂ O -O-CH ₂ -CN

CH

CH ₂ = CH-CH ₂ O -O-CH ₂ -COOC ₂ H ₅

30

CH

CH ₂ = CH-CH, O

-O-CH ₂ -CO- (H

CH

Le A 26 501

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237963

Het

CH ₂ = CH-CH ₂ O

Πρ U

N- F

CH

-O-CH-COOC ₂ H ₅ CH ₃

CH ₂ = CH-CH ₂ O F O Il I y ~ -O-CH-CO- ( H CH ₃ CH ₂ = CH-CH ₂ O F CH ₃ I y ~ -O-CHp-C-O-CHp- <II CH ₃ F Il ^u 0 CHp = CH-CHp OI y ~ CH ₃ F -O-CH ₂ -CO- (CH ₂ J ₃ -CH ₃ O CHp = CH-CHp OI ^N " -O-CH-CN CH ₃ CH ₃

CH ₂ = CH-CH ₂ O

N-F-O-CH ₂ -CH ₂ -O-CH ₃

CH

CHp = CH-CH, O

F is -O-CH ₂ -CH <

CH.

OCH

OCH

2 6 5 0 1

- 32 -

Het

CHo ⁼ CH ** CHo rJ 0 / 0 N CH ₃ 0 _ ^ 0 IN \ N- N- 0 J> CHp-CHp = CH \ N- CH ₃ N \ N-IN N L Tn CH ₂ = CH-CH ₂ CH ₃ N 0 CHo ⁼ CH "CHo Ct V ^ CH ₃ \ N- CH ₂ = CH-CH ₂ N IN 0 _y / CH ₃ CH ₂ = CH-CH ₂ I CH ₃ CHo ⁼ CH ^- CHo Ct N.O

N- F

CH ₂ CH ₂ -OCH ₃

S-CH ₂ -C <

I is CH ₂ -OCHr ₅ CH ₃

F -S- <H

F -S- <H

F -S-CH ₂

F -S-CH ₂ -CN

F -S-CH ₂ -COOC ₂ H ₅

S-CH ₂ -CO- (H

3 >

2 6 5 0 1

- 33 -

Z 9? 963

Het

CH ₂ = CH-CH ₂ O

Ho 0

Si {

CH

N-F -S-CH-COOC ₂ H ₅

CHO

CH ₂ = CH-CH ₂ O

CH ₃ CHp = CH-CHp 0

N-CH

CH ₂ = CH-CHo 0

N- F

CH ₃ CH ₂ = CH-CH ₂ O

N-CH

CH ₂ = CH-CHo 0

CH

CHp = CH-CH ₂ O

"Ν- <

CH-

-S Il -CH-C- I ο- / η 2- < ο- ' CH ₃ -S -CHp-C ² Il -0-CH

-S-CH ₂ -CO- (CH ₃ ) ₃ -CH ₃ O

F -S-CH-CN

CH

N-F -S-CH ₂ -CH ₂ -O-CH ₃

N-F -S-CH ₂ -CH <

OCH,

6 5 0 1

- 34 - 237363

Het R ¹ R ²

CHo = CH-CH _? 0

i

N-F -OCH ₃

CH ₃

CH ₂ = CH-CH ₂ O

N- J = N "CH ₃ F -OC ₂ H ₅ CHp = CH-CHp 0 ^ *. JJ IN- F -O-CH (CHO) ₂ CH ₃ CH ₂ = C-CH ₂ 0 I N- J = N "CH ₃ F -O-CH ₂ -CH = CH ₂

CH ₂ = CH-CH ₂ O

I N-J-N '

F is -O-CH ₂ -CH = CH-CH ₃

CH ₃

CH ₂ = CH-CH ₂ O

In

J = N "

F is -O-CH ₂ -CH = CH-Cl

CH ₃ 0 4 F -O-CH-CH = CHp I CH ₂ = CH-CH ₂ Λ Pi CH ₃ J- CH ₃

- 35 - 299963

Het

CH ₂ = CH-CHp ₁ O

N-CH ₃ CH ₂ = CH-CH ₂ O

N-CHf

F is -O-CH ₂ -C = CH

F -0-CH-CSCH

CH

CH ₂ = CH-CH, Ο

N-F-O-CH ₂ -C = CH ₂

CH

CH ₂ = CH-CH-, 0

CH

CH ₂ = CH-CH, 0

CH

CHp = CH-CH ₂ O 2 v ^

CH

CHp = CH-CHp O ² x2 <

N- F

CH

N-F-O-CH ₂ -CH ₂ -OC ₂ H ₅

F is -O-CH-CH ₂ -OC ₂ H ₅

CH

N-F-O-CH ₂ -CH-OCH ₃

CHO

-0-CH ₂ - /

2 6 5 0 1

- 36 -

Het

CHp = CH-CHp O

N- N "CH ₃

CHp = CH-CHp O

N-CH ₃

: Ho ο

IN

CH

CHp = CH-CHp 0 N-

CH ₃

CHp = CH-CHp O N-CH,

CH ₂ = CH-CHp O

CH

CHp = CH-CHp O

Ηϊf CHo

I -O-CH ₂ -C-OC ₂ H ₅

F -0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

F is -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

-O-CHp-C-CH ²

F is -O-CH-C-CHo

I ³

CHO

F -SCH _:

F -SC ₂ H ₅

CH

6 5 0 1

CH ₂ = CH-CH ₂ Ο CH ₃

CH ₃ CH ₂ = CH-CHO

CH ₃ CH ₂ = CH-CH ₂

6 5Ot

199963

Het R ¹ R ²

'Ν (

N-F -S-CH (CH-,);)

CH ₂ = CH-CH ₂

N-F -S-CH ₂ -CH = CH ₂

N-F -S-CH ₂ -CH = CH-Cl N-F -S-CHO-CH = CH-CHo

' ²

CH ₃ 0 0 0 N F -S-CH-CH = CHp I CH ₂ = CH-CH ₂ \ N- \ N- N- CH ₃ I N N CH ₃ F -S-CH ₂ -CHCH CHo ⁼ CK * "CHo I CH ₃ F -S-CH-C = "CH I CH ₂ = CH-CH ₂ CH ₃ N CH ₃

- 38 -

Het

CHp = CH-CHp O

N- = Ν "CH ₃

CHp = CH-CHp O

I is N-CH ₃ CHp = CH-CHp O

N-CH ₃

CHp = CH-CHp O NF -S-CH ₂ -C = CH ₂ CH ₃

F -S-CH ₂ -CH ₂ -OC ₂ H ₅

F is -S-CH-CH ₂ -OC ₂ H ₅

CH-

F -S-CH ₂ -CH-OCH ₃

CHp = CH-CHp 0

² ^ g

N-F-S-CH ₂ r (

CH-

CH ₂ = CH-CH ₂ O

CH-

N-F-S-CH ₂ -C-OC ₂ H ₅

CHo = CH-CHp 0 2> ^.

CHr

F -S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

2 6 5 0 1

- 39 -

Het

CH ₂ = CH-CH, O

-Mo U

i- <

N- F -S-CH ₂ -CH ₂ -O ^- CH ₂ ^- CH ₂ ^- OC ₂ H ₅

CH,

CH ₂ = CH ^- CH ₂ A 0 Ti \ M N- / CH JN 3 Cl ν / CH J = N 3 N • Cl CH

F -S ^- CH ^- C ^- CH ₃

r <

CH-

Cl CHo N-

CH ₃

Cl CH ₃ N-

^ = N CH ₃

N-

CH

3,

F -0-CHo-C <

CH ₂ -OCH ₃

I CH ₂ -OCH ₃

CH-

N-F -0- (H

-Oh

F -O ^- CH

F -O-Cu ₂ ^- CN

6 5 0 1

- 40 -

197263

Cl CH-

N-F-U-CH ₂ -COOC ₂ H ₅

Cl CH-

N-

CH-

Cl CH ₃ N-

CH ₃

Cl CH _: N-

CH-

Cl

CH-

Cl CH-

N-

CH,

Cl CH, II / -Q-CH ₂ -CO- ^ H

-O-CH-COOC ₂ H ₅

CH-

II / I F -O-CH-C-O- <H

CK

N-F -O-CH ₂ -CO-CH ₂ - <

-O-CH ₂ -CO- (CH ₂ ) ₃ -CH ₃ O

CH,

F -O-CH-CU

CH-

2 6 5Of

- 41 -

Z91S63

Cl CH-

N-F-O-CH ₂ -CH ₂ -O-CH ₃

CH,

Cl

N-F-O-CH ₂ -CH <

CH,

Cl CH ₃

N- F

CH-

Cl CH-

N-

CH.

Cl CH-

N-

CH-

Cl CH ₃

N-CH ₃

Cl CH-

N- F

CH-

OCH

OCH

CH ₂ -OCH ₃ S-CH ₂ -C <

I CH ₂ -OCH ₃

CH-

-S - (H -S- <H -S-CH.

-S-CH ₂ -CN

- 42 -

23Ϊ363

Het

Cl CH-

N-F -S-CH ₂ -COOC ₂ H ₅

Cl

N-

CH-

Cl CHr

N- F

CH

Cl CH-

N- F

N =

CH-

Cl CH-

N- F

CH-

Cl CH-

N-

CH-

Cl CH-

Il /

-S-CH ₂ -CO- ^ H -S-CH-COOC ₂ H ₅

CH-

-S-CH-CO / H CH ₃

-S-CH ₂ -C-O-CH ₂ - < ^/ I

Il 0 '

N- F -S-CH-CN = N ' I 3 CH ₃

 '2 6 5 0 f

- 43 -

Het

Cl CH ₃

N-CH

F -S-CH ₂ -CH ₂ -O-CH ₃

Cl CH

N-F -S-CH ₂ -CH <

CH

CH-

CH-

Cl

CH-

Cl

CH-

OCH

OCH

-OCH

-OC ₂ H ₅

j N- N F -0-CH ( CH ₃ ) ₂ CH ₃ CHo - ( Cl -N- F -0-CH ₂ -CH = C CH ₃ CHO Cl

F is -O-CH ₂ -CH = CH-CH ₃

- 44 -

137963

Cl CH-

N-

CH-

-O-CH ₂ -CH = CH-Cl

Cl CH-

CH-

N-F-O-CH-CH = CH-

CH-

Cl CH-

N-F-O-CH ₂ -C = CH

CH

Cl

N-F-O-CH-C = TH

N =

CH

CH-

Cl CH-

N- F

CH-

Cl CH-

CH-

-O-CH ₂ -C = CH ₂

N-F-O-CH ₂ -CH ₂ -OC ₂ H ₅

Cl CH _: N-

F is -O-CH-CH ₂ -OC ₂ H ₅

CH.

2 6 5 0

- 45 -

191963

Cl CH ₃

F is -O-CH ₂ -CH-OCH ₃

CHO

Cl CH-

N-H = N "

^{ 3

Cl CH ₃

N-

-0-CH ₂ - <

CHCl CH *

N- F

CH ₃

I ³

-O-CH ₂ -C-OC ₂ H ₅ CH ₃

-0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

CH Cl

N- F -0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

CH-Cl

C-I ₃

Cl CH _:

V = A

CH

N-F-O-CH ₂ -C-CH ₃

Il -0 "CH-C-CHo

³ CH ₃

N- F

5Ot

Cl

N- F

CH, Cl

^ = N ^J 3

N-

CH-Cl CH ₃

N-CH ₃ Cl CHr

N-

CH-Cl CHr

N-

CH-! I CHr

N- F

N =

CHr Cl CH-

N-

CHr

F "SC ₂ H ₅

F -S-CH (CH ₃ ) ₂

F -S-CH ₂ -CH = CH ₂

F -S-CH ₂ -CH = CH-Cl

-S-CH ₂ -CM = CH-CH ₃

F -S-CH-CH = CH ₂

CH-

6 5Ot

- 47 -

299963

Cl CH-;

S-CH ₂ -C =CH

CH

Cl

N-F -S-CH-CHCH

H = N ^l 3 CH-

Cl

N- F

CH

Cl CH-

N- F

S-CH ₂ -CH ₂ -OC ₂ H ₅

CH-

Cl CH,

N-

CH-

F is -S-CH-CH ₂ -OC ₂ H ₅

CHO.

Cl CH.

N-F -S-CH ₂ -CH-OCH ₃

CH-CH,

C! CH.

S-CHO <

CH

2 6 5 0

- 48 19? 963

Cl CH.

N- s

CH-

F is -S-CH ₂ -C-OC ₂ H ₅

CH ₃

Cl CH-

N-

F -S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

CH-

Cl CH,

N-F -S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

CH-

Cl CH-

F is -S-CH ₂ -C-CH ₃

CH-

Cl CH-

N- F -S-CH-C-CH ₃

CH-

CH-

Cl CH-

N-

F is -O-CH ₂ -C <

CF,

CH * CH ₂ -OCH ₃ CH ₂ -OCH ₃

Cl CH-

N- F

- • Ν

CF

6 5Oi

- 49 -

239963

Cl CH-

N- F

CF,

Cl CH-

CF,

Cl CH-

 N =

CF,

Cl

N-

CF.

Cl CH

== N

N-

/ CF

Cl CH ₃

CF,

-Oh

F -O-CH-

L N- N CH ₃ F -0-CH ₂ CN / CF ₃ N- Cl F -0-CH ₂ -COOC ₂ H ₅

Ii / -ι

-O-CH ₂ -CO- (H

-O-CH-COOC ₂ H ₅

Il / - i

-O-CH-C-O- ^ H CH,

IeA 2 6 5 0

- 5η -

Cl

F is -O-CH ₂ -CO-CH ₂

CF.

Cl

N-

H = N'Cl CH-

N •

CF,

Cl CH-

N- F

CF ₃

Cl CH,

t \

N M = N "

₃

Cl CH,

N-CF ₃ Cl CH.

N-

^ = N

'3, r (

-O-CH ₂ -CO- (CH ₂ J ₃ -CH ₃ O

F -O-CH-CN

-O-CH ₂ -CH ₂ -O-CH ₃

F is -O-CH ₂ -CH <

OCH

OCH,

CH ₂ -OCH ₃

-S-CH ₂ -C <

I CH ₂ -OCH ₃

CH,

F -S- (H

6 5 0

- 51 -

Cl CH.

N-

-s / η

CFr

Cl CH ₃ N-

F -S-CH.

CF ₃

Cl CH ₃ N-

= N -S-CH ₂ -CN

CFr

Cl

N- F

S-CH ₂ -COOC ₂ H ₅

CF,

Cl

N-

= N II / IF -S-CH ₂ -CO- ^ H

CF,

Cl CH.

N- F

S-CH-COOC ₂ H ₅

CF ₃

Cl CH ₃ N-

F -S-CH

¹¹ /

CF, CH.

6 5Ot

- 52 -

J97363

Het

Cl CH.

N- F

CF

-C-O-CHO A

Cl

CF.

N-F -S-CH ₂ -CO- (CH ₂ J ₃ -CH ₃

Cl CH-

CF

N-F-S-CH-CN

CH-

Cl CH-

N-F -S-CH ₂ -CH ₂ -O-CH ₃

CF ₃

Cl CH, N-

.j- = n '

3 Cl CH-

F -S-CH ₂ -CH <

CF

Cl CH ₃

N-

CF,

OCH,

OCH,

N-F -OCH-

F -OC ₂ H ₅

^IeA 2 6 5 Of

- 53 -

^RJ

Cl CH;

3 Cl CH,

F is -O-CH (CH ₃ ) ₂

N-F-O-CH ₂ -CH = CH ₂

CF ₃

Cl CH ₃

N-

CF,

Cl CH-

N-

CF

Cl CH-

0-CH ₂ -CH = CH-CH ₃

F is -O-CH ₂ -CH = CH-Cl

N- N CH ₃ N WlIO F -O-CH-CH = C I N- \ N- I / CF ₃ Cl F -O-CH ₂ -C = C CF ₃ F -O-CH-C = CH I Cl CH ₃ CF ₃

6 5 0 1

- 54 -

Cl CH-

N-F-O-CH ₂ -C = CH ₂

Γ1 CH.

N-

CF.

Cl CH.

N-

CF,

Cl CH.

N-

CF

Cl

= K

N =

N-

CF,

Cl CH.

N-

CF _:

Cl CH.

► = n "~ CF-,

CH-

F is -O-CH ₂ -CH ₂ -OC ₂ H ₅

F is -O-CH-CH ₂ -OC ₂ H ₅

CH ₃

F is -O-CH ₂ -CH-OCH ₃

CHO

-0-CH ₂ - <

o-CH.

F is -O-CH ₂ -C-OC ₂ H ₅

F -0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

IeA 2 6 5 it ι

- 55 -

299963

Cl CH ₃ F -O-CH ₂ -CH ₂ -O - / N- ti 0 II / · ^Ν CF ₃ CH ₃ F -O-CH ₂ -C-CH ₃ Cl N / N- 0 Il C 3 CH ₃ F II-O-CH-C-CH ₃ CH ₃ Cl \ ( N- C 3 CH ₃ F -SCH ₃ Cl N- CF ₃ CH ₃ F -SC ₂ H ₅ Cl N-

₂ -CH ₂ -OC ₂ H ₅

CJ. CH-s.

N-

F -S-CH (CH ₃ ) ₂

CF

Cl CH-

N- F

CF

-S-CH ₂ -CH = CH ₂

2 6 5

- 56 -

Het

Cl CHo N-

N =

F -S-CH ₂ -CH = CH-Cl

CF,

Cl CH-

N-F -S-CH ₂ -CH = CH-CH ₃

CFr

Cl CH-

N-

F -S-CH-CH = CH ₂

CF,

Cl CH-

CF,

Cl CH-

Cl CH-

N-

CF,

CH-

N-F -S-CH ₂ -CSCH

N- F -S-CH C = CH y -N ' I CF CH ₃ Cl γ _ < ^CH 3 J N = n " F -S-CH ₂ -C = CH _? I / CF IN I LJiO = 3 _ 3

-S-CH ₂ -CH ₂ -OC ₂ H ₅

^leA 2 6 5Ot

- 57 -

Z97S63

Het

Cl CH ₃ NF -S-CH-CH ₂ -OC ₂ H ₅

CFr Cl CH-

N- F

CFr Cl CH

-S-CH ₂ -CH-OCH ₃ CHO

N- F

- '

CF, Cl

N-CH

F is -S-CH ₂ -C-OC ₂ H ₅

CF-CH-

Cl CHr.

N-CF ₃ Cl C

F -S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

N-F -S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

CF ₃

Cl

CF F -S-CH ₂ -C-CH ₃

3,

0

- 58 - Z97S63

Cl CHo N / ³ F 0 Il rv II -S-CH-C-CH I CF ₃ CH ₃ ? H ₃

CO

F -OCH ₂ 3-C <

CH-

CH-

CH-

CH-

CH ₂ -OCH ₃ CH ₂ -OCH ₃

N-F -0- <H

-o- (w

N-F -0-CH

F -0-CH₂CN

N-F-O-CH ₂ -COOC ₂ H ₅

6 5Of

- 59 -

R ¹ R ²

N-

¹¹ /

F is -O-CH ₂ -CO- <H

CH,

N-F-O-CH-COOC ₂ H ₅ CH ₃

CH-

N-F-O-CH -C-O- (H

CH-

CH-

N- F

CH ₃

c6- 0 -CH ₂ -CO- (CH ₂ ) ₃ -CH ₃ O

N-F-O-CH-CN

CH-

'· 2 6 5 0

- 60 -

237963

R ¹ R ²

CH-

-O-CH ₂ -CH ₂ -O-CH ₃

CH *

F is -O-CH ₂ -CH <

OCH

OCH

CH-

CH ₂ -OCH ₃ -S-CH ₂ -C <

CH ₂ -OCH ₃

CH-

N- F -S- (H

CH ₃

-S- < H

CH-

N-F -S-CH-

CH-

N-F -S-CH ₂ -CN

6 5 0 1

- 61 -

237963

Het

R ¹ R ²

F -S-CH ₂ -COOC ₂ H ₅

CH-

N-

F -S-CH ₂ -CO-Zh

CH-

N-F -S-CH-COOC ₂ H ₅

CH-

CH-

F -S-CH

Il /

-C-O- ^ H

CH-

CH-

N- F

-S-CH ₂ -CO-CH ₂ - (

Il 0 '

N-F -S-CH ₂ -C-O- (CH ₂ ) ₃ -C'H ₃

6 5 0

- 62 - Z3J363

Het

R ¹ R ²

CHr

N-F-S-CH-CN

CH-

CH-

-S-CH ₂ -CH ₂ -O-CH ₃

CH,

N-F -S-CH ₂ -CH <

OCH

OCH

CH-

N-F -OCH-

CH-

¹ ^ A _n / "

F -OC ₂ H ₅

CH-

N-F-O-CH (CH ₃ ) ₂

CH-

-O-CH ₂ -CH ₂ CH ₂

501

- 6 3 - 29? 963

Het R ¹ R ²

CH-

F is -O-CH ₂ -CH = CH-CH ₃

CH-

W- F

-O-CH ₂ -CH = CH-Cl

CH,

N- F

-O-CH-CH = CH ₂

LHo

CH-

N-F-O-CH ₂ -C 1 CH

CH-

CH-

CH-

N-F-O-CH-C = CH

CH-

N-F-O-CH ₂ -CHCH ₂

CHr

F is -O-CH ₂ -CH ₂ -OC ₂ H ₅

IeA 2 6 5 0 1

R ¹ R ²

CH-

F is -O-CH-CH ₂ -OC ₂ H ₅

CHO

N-F-O-CH ₂ -CH-OCH ₃

N-F -0-CH *

CH-

N- F

-O-CH ₂ -C-OC ₂ H ₅

CH-

N- F -0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

CH-

N- F

-OCH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

F is -O-CH ₂ -C-CH ₃

6 5 0 f ^!

- 65 - 191963

Het R ¹ R ²

CH.

CH-

I!

N - F - O - CH - C - CH '

CH.

F-SCH,

CH.

Cr ** -

-SC ₂ H ₅

CH-

N- F

-S-CH (CH ₃ ) ₂

CH.

N- F

o ^- CH = CHo

CH.

N-F -S-CHO-CH = CH-Cl

CH.

N- F

-S-CH ₂ -CH = CH-CH ₃

6 5

- 66 - 137963

Het R ¹ R ²

CH.

CHr

N-F -S-CH-CH = CH-

CH.

N-F -S-CH ₂ -CHCH

CH.

N-F -S-CH-C = CH

CH-

N-F -S-CH ₂ -C =CH ₂

CH.

F -S-CH ₂ -CH ₂ -OC ₂ H ₅

CH.

N-F -S-CH-CH ₂ -OC ₂ H ₅

CH.

LeA 2 6 5 0 1

Het

CH-

N- F

-S-CHO-CH-OCHo 2 j 3

CH-

-S-CH ₂ - <

O-

CH-

N- F

-S-CH ₂ -C-OC ₂ H ₅ CHo

CH-

N-F -S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

CH-

N-F -S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

F is -S-CH ₂ -C-CH ₃

CH

N- F

-S-CH-C-CH ₃

CH-

UA 26 50

- 68 - 297363

Het R ¹ R ²

Cl

N-

F is -O-CH ₂ -C <

CH ₂ -OCH ₃

CH ₂ -OCH ₃ ^! 3

Cl

I F

-Q- ^ H

Cl

"N

F -O-CH ₂

Cl

F is -O-CH ₂ -CN

Cl

N-

F -O-CH ₂ -COOCH ₃

Cl

F is -O-CH ₂ -COOC ₂ H ₅

LeA 2 6 5 0 1

- 69 -

237 * 63

Het

Cl

N-

Cl

N-

Cl

Cl

Cl

Cl

"N

F is -O-CH ₂ -CO- (h

IF -O-CH-COOC ₂ H ₅

CH-

2- ^ n-1/1

IF -O-CH-CO- (H = NI ^N '

O-CHO-C-O-CHO <

² Il ² OJ

F is -O-CH ₂ -CO- (CH ₂ ).

F -O-CH-CN

CH-

5 0 1

- 70 - 297363

Hei

Cl

-O-CH ₂ -CH ₂ -O-CH ₃

Cl

"N

F is -O-CH ₂ -CH <

OCH

OCH

Cl

"N CH ₂ -OCH ₃ S-CH ₂ -C <

I CH ₂ -OCH ₃

Cl

RVR

F -S- (H

"N

Cl

M- -S- / H

Cl

F -S-CH.

"N

N-

F -S-CH ₂ -CN

6 5

- 71 -

Het

^RJ

Cl

"N

F -S-CH ₂ -COOC ₂ H ₅

Cl

¹¹ / F -S-CH ₂ -CO- ^

Cl

S-CH-COOC ₂ H ₅ CH ₀

Cl

N-

F -S-CH

¹¹ / -CO-Hf H

CH-

Cl

in- r

I F -S-CHo-C-O-CH- <

N ~

Cl

"N

S 5 0 1

Het

- 72 -

R ¹ R ²

Cl

N-

Cl F -S-CH-CN

I CH ₃

F -S-CH ₂ -CH ₂ -O-CH ₃

Cl

-N-

I F -S-CHp-CH <

OCH

OCH

Cl

-N-F -OCH-

Cl F -OC ₂ H ₅

Cl

"NF-OCH (CHg) ₂

Cl

NF-O-CH ₂ -CH = CH ₂

UA 2 6 5 0 1

- 73 -

297563

Het

R ¹ R ²

Cl

F is -O-CH ₂ -CH = CH-CH ₃

Cl

N-

F is -O-CH ₂ -CH = CH-Cl

Cl

"N

-O-CH-CH = CHp CH ₃

IF -O-CH ₂ -C = CH

Cl

Cl

Cl

Cl

"N

F is -O-CH-C = CH

I CH ₃

F is -O-CH ₂ -C = CH ₂

CH ₃

F is -OCH ₂ -CH ₂ -OC ₂ H ₅

IeA 2 6 5 0 1

- 74 -

239963

R ¹ R ²

313

Cl

IF -O-CH-CH ₂ -OC ₂ H ₅

Cl

Cl

CH,

-O-CH ₂ -CH-OCH ₃ CH ₃

-0-CHO <

Cl

"N

Cl

"N

-O-CH ₂ -C-OC ₂ H ₅ CH ₃

F -0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

Cl

IF -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

35

Cl

F is -O-CH ₂ -C-CH ₃

Le A 26 5i ; l

- 75 -

19? 963

Het

R ¹ R ²

Cl

-O-CH-C-CH-CH ₃

Cl F -SCH ₃

Cl

F -SC ₂ H ₅

Cl

IF -S-CH (CH ₃ J ₂

Cl F -S-CH ₂ -CH = CH ₂

Cl S-CH ₂ -CH = CH-Cl

CO ' F -S-CH ₂ -CH = CH-CH ₃

IeA 2 6 5 0 1

- 76 -

Hel

Cl

N-N

F -S-CH-CH = CH-

Cl

"N

F -S-CH ₂ -C =CH

Cl

"N

F -S-CH-CHCH

CH.

Cl

N-K

I F

-S-CH ₂ -C = CH ₂ CH ₃

Cl

F -S-CH ₂ -CH ₂ -OC ₂ H ₅

Cl

N-

F is -S-CH-CH ₂ -OC ₂ Ht;

6 5 0 1

- 77 -

Het R ¹ R ²

Cl

"N

-S-CH ₂ -CH-OCH ₃ CH ₃

Cl

IF -S-CH ₂ -

ci

Cl

-S-CH ₂ -C-OC ₂ H ₅

Cl

IF -S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

"N

F is -S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

F is -S-CH ₂ -C-CH ₃

F is -S-CH-C-CHo

I ³

6 5 Oi

- 78 -

R ¹ R ²

Cl

STILL-

"N -O-CH ₂ -C"

I is CH ₂ -OCM ₃ CH ₃

Cl

Cl

N-N

-ο- / η

Cl

H -O-CH ₂

Cl

H -O-Ch ₂ -CN

Cl

H -O-CH ₂ -COOC ₂ H ₅

Cl

LeA 2 6 5 0 1

- 79 -

Het

R ¹ R ²

Cl

N-

-O-CH-COOC ₂ H ₅ CH ₃

Cl

RQR

-0-CH CH ₃

¹¹ /

-C-O- (H

Cl

-O-CH ₂ -CO-CH ₂ - / I

π

Il ^β ο-

Cl

-O-CH ₂ -CO- (CH ₂ ) ₃ -CH ₃ O

Cl

H-0-CH-CN

CH-

Cl

-O-CH ₂ -CH ₂ -O-CH ₃

IeA 2 6 5 0 1

- 80 -

Hel

R ¹ R ²

Cl

N-

IH -O-CH ₂ -CH <

OCH ^

"STILL-:

Cl

.NH -S-CH ₂ -C <

CH-

CH ₂ -OCH ₃ CH ₂ -OCH ₃

Cl

N-H -S- <H

Cl

N-

-s-Yh

Cl

NH-S-CH ₂

Cl

• Ν-

IH-S-CH ₂ -CN

Cl

IH-S-CH ₂ -COOC ₂ H ₅

6 5 0 1

- 81 -

231963

Het

Cl

Cl

"N

Cl

N-

Cl

rrr

"N *" o ~ L "rio ~ L» ~

IH-S-CH-COOC ₂ H ₅

CH ₃ O

Il

-S-CH-C- (CHo

-S-CH ₂ -C-O- (

Cl

"N

H is -S-CH ₂ -C-O- (CH ₂ ) ₃ -CH ₃

Cl

H-S-CH-CN

CH.

6 5 0 1

82 - 299963

Het

R ¹ R ²

Cl

H is -S-CH ₂ -CH ₂ -O-CH ₃

Cl

N-

H is -S-CH ₂ -CH <

OCH

OCH *

CH-

N- H -OCK ·

N-H -C ¹ C ₀ H

2 ⁿ 5

CH-

N-H-O-CH (CH ₃ ) ₂

N- H

-O-CH ₂ -CH = CH ₂

N-H-O-CH ₂ -CH = CH-CH ₃

LeA 2 6 50

- 83 -

2373S3

Het

CH,

N-H-O-CH ₂ -CH = CH-Cl

CH-

N- H

-0-CH-CH = CHo

I

CHn

CH-

-O-CH ₂ -C = CH

CH,

N-H-O-CH-C = TH

CH-

CH-

N-H-O-CH ₂ -C = CH ₂

CHO

CH,

N-H-O-CH ₂ -CH ₂ -OC ₂ H ₅

CH.

CH,

N-H-O-CH-CH ₂ -OC ₂ H ₅

IeA 2 8 5 0 1

- 84 23 ^ 363

N-H-O-CHv-CH-OCH-

CH-

CH-

N-H-O-CH ₂ -

N- H

CH-

-O-CH ₂ -C-OC ₂ H ₅

CH-

N- H

-0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

S ^ N ^ ^N "

H is -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

CH-

0-CH ₂ -C-CH ₃

N- H -0-CH-C-CH ₃

CH-

6 5 0 1

- 85 -

237 963

Het R ¹ R ²

CH-

N-H-SCH.

N- H "SC ₂ H ₅

CH-

N-H-S-CH (CH ₃ ) ₂

H is -S-CH ₂ -CH = CH ₂

N- H

-S-CH ₂ -CH = CH-Cl

CHr

N- H

-S-CH ₂ -CH = CH-CH ₃

CH-

N - H - -S-CH-CH = CHo

I ²

CHO

UA 2 6 5 0 1

- 86 -

237363

Hel

-S-CH ₂ -CHCH

CH-

N- H

CH,

N- H

-S-CH-CSCH CH ₃

-S-CH ₂ -C -CH ₂ CH-3

CH,

N- H

-S-CH ₂ -CH ₂ -OC ₂ H ₅

CH.

N- H

-S-CH-CH ₂ -OC ₂ H ₅

CH.

CHO

λ!

N-H-S-CH ₂ -CH-OCH ₃

CH,

6 5 0 1

- 87 -

237963

Het

CH,

N- H

-S-CH ₂ - <

CHr

N-H-S-CH ₂ -C-OC ₂ H ₅

CH

CH-

N-H-S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

CHr

N-H-S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

N-H-S-CH ₂ -C-CH ₃

N-H-S-CH-C-CH-

CH,

(CH ₃ J ₃ C

Z = N

F is -O-CH ₂ -C <

CH,

CH ₂ -OCH ₃ CH ₂ -OCH ₃

UA 2 6 50 1

- 88 -

Z31963

Het

R ¹ R ²

P-f

(CH _{3) 3} C

N- F

N- F

-Oh

(CH ₃ J ₃ C

P-HT

(CH ₃ J ₃ C

N- F

N- F

0-CH ₂ -CN

(CH ₃ J ₃ C

(CH ₃ J ₃ C

i (CH ₃ J ₃ C

O γ

N-

N-

N-

F is -O-CH ₂ -COOC ₂ H ₅

F -O-CH ₂

Il /

-C-O- ^ H

0-CH-COOC ₂ H ₅

(CH ₃ J ₃ C

LeA 2 6 5 0

- 89 -

237363

Het

(CH _{3) 3} C

N-

N-

(CHg) ₃ C

(CH _{3) 3} C

N-

(CH _{3) 3} C

(CH _{3) 3} C

(CH _{3) 3} C

N •

O ν

N-

N-

N-

(CH _{3) 3} C

-O-CH-C-O- (H

CHO

F -O-CH ₂ -CO-CH ₂ - /

F is -O-CH ₂ -CO- (CH ₂ ) ₃ -CH ₃

F -O-CH-CN

CH ₃

F is -O-CH ₂ -CH ₂ -O-CH ₃

F is -O-CH ₂ -CH <

OCH,

OCH

F -S-CH ₂ -C <

CH,

CH ₂ -OCH ₃ CH ₂ -OCH ₃

UA 26 50 1

- 90 -

Z ^ 963

Het

R ¹ R ²

(CH _{3) 3} C

N-

N-

-s / h

(CH ₃ ) ₃ C (CH ₃ J ₃ C

S-CH ₂

(CH _{3) 3} C

pn

F -S-CH ₂ -CN

(CH ₃ ).

F -S-CH ₂ -COOC ₂ H ₅

(CH _{3) 3} C

F -S-CHp-C-O- (H

(CH _{3) 3} C

F -S-CH-COOC ₂ H ₅

CH-

UA 2 6 5 0!

Het.

(CH ₃ J ₃ C

J-w

F ^-

-C-O- ^ H

O N -S-CH CH ₃

-S-CHO-C-O-CHo 2 υ 2

(CHg) ₃ C 0-

o-t

(CH ₃ J ₃ C

-S-CH ₂ -CO- (CH ₂ J ₃ -CH ₃ O

(CH ₃ J ₃ C

N-

0 '/

N-

F -S-CH-CN

CH-

F -S-CH ₂ -CH ₂ -O-CH ₃

(CH ₃ J ₃ C

ο- <

N-F -S-CH ₂ -CH <

OCH,

(CH ₃ J ₃ C

N-

(CHg) ₃ C

IeA 2 6 5 0V

- 92 -

HeL R ¹ R ²

N - F - OC ₂ H ₅ (CH ₃ J ₃ C

I N-F-O-CH (CH ₃ ) ₂ (CH ₃ ) ₃ C

N - F - O - CH ₂ --CH = CH ₂ (CHg) ₃ C

0 0-Hf

N-F-O-CH ₂ -CH = CH-CHt

(CH ₃ J ₃ C

I N-F-O-CH ₂ -CH = CH-Cl (CH ₃ ) ₃ C

N-F-O-CH-CH = CH ₂

(CH ₃ ) ₃ C CH ₃

(CH _{3) 3} C

F -O-CH ₂ -CHCH

LeA 2 6 5 0

Het

O N-

(CH ₃ J ₃ C

F is -O-CH-C = CH

CH

N-

(CH ₃ J ₃ C

F -0-CHo-C = CH-

CH

(CH ₃ J ₃ C

O N-

-O-CH ₂ -CH ₂ -OC ₂ H ₅

(CH _{3) 3} C

F -O-CH-CH ₂ -OC ₂ H ₅ CHo

O is N-O-CH ₂ -CH-OCH ₃ CH ₃

Ο- /

N-F-O-CH ₂

CH ₃ ; ₃ c

(CH ₃ J ₃ C

CH

F is -O-CH ₂ -C-OC ₂ H ₅

CH,

6 5

- 94 -

Het R ¹ R ²

N- F -0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

= N "(CHg) ₃ C

N- F -0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

Z = Vi ' (CH ₃ ) ₃ C

O PH _n (CHg) gC O ο- < N- (CH _{3) 3} C 0 (CH ₃ J ₃ C 0 N (CHg) gC 0 (CHg) ₃ C F 0 Il-O-CH ₂ -C-CH ₃ IN- IN- F 0 Il-O-CH-C-CHq I I F -SCH ₃ F -SC ₂ H ₅ F -S-CH (CH ₃ J ₂

Uk 2 6 50 1

- 95 -

Het

(CH ₃ ) ₃ C (CH ₃ ) ₃ C

J (CH ₃ J ₃ C

_(CH3 J ₃ C (CHg) ₃ C (CHg) ₃ C

N •

N-y

N-

N •

O N-

NS-CH ₂ -CH = CH ₂

F -S-CH ₂ -CH = CH-Cl

S-CH ₂ "CH = CH" CH ₃

F -S-CH-CH = CHo I

CH

F -S-CH ₂ -C =CH

(CH _{3) 3} C

F -S-CH-C = CH

I CH ₃

F -S-CH ₂ -C =C CH ₃

6 5

Hel

O N- -S-CH 2 ^^ 2 ~ ^^ 2

(CH ₃ );

(CH _{3) 3} C

N-F -S-CH-CH ₂ -OC ₂ H ₅

CHO

(CH ₃ ).

-S-CHO-CH-OCHo 2 j

CH ₃

Ü N-

F -S-CH ₂

(CH _{3) 3} C

CH

(CH _{3) 3} C

N-F-S-CH ₂ -C-OC ₂ H ₅

CHO

0 f

N- F

-S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

(CH _{3) 3} C

0 · /

N-

F is -S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

(CHg) ₃ C

UA 2 6 5 0

- 97 -

Het

(CH ₃ J ₃ C

(CHg) ₃ C

N-

N-

O '/

N-

F is -S-CH ₂ -C-CH ₃

F is -S-CH-C-CH ₃

o-C-CHo, 3

CH ₂ F

O /

N-

q-C-CHO! 3

CH ₂ F

• t

N-

CH ₃ -C-CH ₃ CH ₂ F

(0-

CH ₃ -C-CHg

CH ₂ F CH.

-o-Yh

F -O-CH ₂

F is -O-CH ₂ -CN

ItA 2 6 50 1

- 9fa -

HeL R ¹ R ²

C is N-F-O-CH ₂ -COOC ₂ H ₅

CH ₃ -C-CH ₂ CH ₂ F

\ Il /

N-F-O-CHo-C-O- <H

CH ₂ F

N-F-O-CH-COOC ₂ H ₅

UA 26 50

CH ₃ -C-CH ₃ 0 0 CH ₃ 0 Μ I CH ₂ F | nf Z = N "-C-CH ₃ I N- F Il / c-o-Zh CH ₂ F -C-CHq I CH ₂ F -O-CH- I CH ₃ I CH ₃ -C-O-CHp- <It O -0-CH ₂ Il ^ 0 CH ₃

- 99 -

Hel

CH ₃ -C-CH ₃

CH ₂ F 0 -CH ₂ -CO- (CH ₂ ) ₃ -CH ₃ O

CH ₃ -C-CHO I 0 0 CH ₂ F IN IN 0 ff -C-CH ^ I -C-CH-, I L? CH ₂ F CH ₂ F CH ₃ -C-CHq I CH ₂ F CH ₃ CH ₃

F -O-CH-CN

CH

F is -O-CH ₂ -CH ₂ -O-CH ₃

F is -O-CH ₂ -CH <

OCH

OCH

F -S-CH ₂ -C <

CH ₂ -OCH ₃

CH

CH ₂ -OCH ₃

UA 2 6 5 0-1

- 100 -

Het R ¹ R ²

N-

F -S- <H

CH ₃ -C-CH ₃ CH ₂ F

O /

N-

-S - (^ H

CH ₃ "C-CH ₃ CH ₂ F

O γ

N-

F -S-CH ₂

CH ₃ -C-CH ₃ CH ₂ F

N-

-S-CH ₂ -CN

CH ₂ F

F -S-CH ₂ -COOC ₂ H ₅

CHo-C-CH ₃ , 3

CH ₂ F

UA 2 6 5

Het

ο- /

N- F

H /

-S-CH ₂ -CO- / H

CH ₃ -C-CH ₃ CH ₂ F

O is N- -S-CH-COOC ₂ H ₅

CH ₃ -C-CH-,

³

CH ₂ F CH-

N-F -S-CH

Il / ι

CH ₂ F

O N-

F -S-CH ₂ -CO-CH ₂ - /

CH ₃ -C-CHO CH ₂ F

NS-CH ₂ -CO- (CH ₂ ) ₃ -CH ₃

CH ₃ -C-CH ₃ CH ₂ F

UA 2 6 5 0 1

- 102 -

Het R ¹ R ²

29J963

O O N- CHq-C - CHq I O F -S-CH-CNT IN- CH ₂ F I is N-CH ₃ -C-CH ₃ CH ₃ CH ₃ -C-CH ₃ CH ₂ F CH ₂ F F -S-CH ₂ -CH ₂ -OCH ₃ F OCH ₃ -S-CH ₂ -CH <OCH ₃

N- H -0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

CHo-C-CHq 3, 3

CH ₂ F

ο- <

N- H -0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

CH ₃ -C-CH ₃ CH ₂ F

UA 2 6 5 0 1

- 103 -

Hei

N-H-O-CH ₂ -C-CH ₃

CHo-C-CHq! 3

CH ₂ F

N-

J = N'CH ₃ -C-CH ₃ H -O-CH-C-CH3

CH

CH ₂ F

O N-H-SCH ^

CH ₃ -C-CH ₃ CH ₂ F

O NH -SC ₂ H ₅

CH ₃ -C-CH ₃ CH ₂ F

O NH-S-CH (CH ₃ ) ₂

I ₃ -U-Un ₃ CH ₂ F

IeA 2 6 5Ot

- 104 -

Het

R ¹ R ²

CH ₃ -C-CH ₃

S-CH ₂ -CH = CH ₂

CH ₂ F

Ρ- <

N - H S - CH ₂ --CH = CH - Cl

CHo-C-CH-, 3 j 3

CH ₂ F

0 N-CH ₃ -C-CH ₃ H -S-CH ₂ -CH = CH-CH ₃ '

CH ₂ F

O N-

CH ₃ -C-CH ₃ CH ₂ FH -S-CH-CH = CH

CH

0 N

CHo-C-CHo 3 j 3

CH ₂ F

UA 26 50 1

- 105 -

Het

R ¹ R ²

CH ₃ -C-CH ₃ CH ₂ FH -S-CH-C = CH

CH

O-(

CH ₃ -C-CH ₃ CH ₂ F oC ^ CHo 2,

CH ₃

H is -S-CH ₂ -CH ₂ -CC ₂ H ₅

H is -S-CH-CHo-OCoHc

CH ₃ -C ^- CH ₃

CH ₂ F

CH ₃ -C-CH ₃ CH ₂ FH -S-CH ₂ -CH-OCH ₃

I. CH ₃

UA 2 6 5Of

- 106 -

299963

H -S-CH ₂

CH ₃ -C-CH ₃

CH ₂ F

N-

S-CH ₂ -C-OC ₂ H ₅

CH ₃ -C-CH ₃ CH ₂ F

N-

H is -S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

! CH ₂ F

O N-

H is -S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

CH ₂ F

N-H-S-CH ₂ -C-CH ₃

CH ₂ F

8 50

- 107 -

Het

CH ₃ -C-CH ₃

CH ₂ F CHO 0

H-R-CH-C-CH-

CH

N- F

CH ₃

CHo 0

CH

CHO 0 ^ N

N- F

CH

CHO 0 ^ N- <

j-N ^

CH

CH,

CH ₂ -OCH ₃ O-CH ₂ -C <

I CH ₂ -OCH ₃

CH-

-Oh

CH ₃ TJ 0 F -O-CH ₂ -CN IN \ N- CH ₃ N CHo ^ 0 Jf F -O-CH ₂ -COOC ₂ H ₅ \

2 6 5 0 1

- 108 -

N-

CUr

CH ₃

CH

CH

CHO

i <

CH

CH. F -O-CH ₂

Il / - -CO- ^ H

F -O-CH-COOC ₂ H ₅

CH-

¹¹ /

-C-O- ^ H

-0-CH CH ₃

-O-CH ₂ -CO-CH ₂

CHQ 0 Jf 0 F -O-CH ₂ -CO- (CH ₂ ) ₃ -CH ₃ II N \ N- N ^ 0 CH ₃ CH ₃ 0 Jf F -0-CH-CN rl L A CH ₃ CH ₃ N CHO

-O-CH ₂ -CH ₂ -O-CH ₃

υ 5 0

- 109 -

Z97963

Het

CHo 0 Ν

N - F - O - CH ₂ --CH <

CH ₃ CHo 0

in the

N-

CH ₃ CH ₃ 0

HM

N-

CH

OCH

-S-CH ₂ -C <I

OCH

CH ₂ -OCH ₃

I is CH ₂ -OCH ₃ CH ₃

" ^s v ^H

CH

N-

CH, CH ₃ 0

-- -1

N-CH

-S- / H

CH

CH

CHo 0 I N-

CH-

-S-CH ₂ -CN

S-CH ₂ -COOC ₂ H ₅

ItA 2 6 5 0 1

- HO

Zn 963

Het

CHq O

N-CH ₃

CH

hq

Si- < i

n-

CH

CH

N-

CH

Hq O

^V N- {

n-

CH

CH ₃ O

N-

CH ₃ CH ₃ O

CH ₃ CH ₃ O

In-

-S-CH

, -C-O- ^ H

-S-CH-COOCpHc

I ²

CH

-S-CH

-CO- ( H

CH

F -S-CH ₂ -CO-CH ₂ - (

-S-CH ₂ -CO- (CH ₂ J ₃ -CH ₃ O

-S-CH-CN CH ₃

-S-CH ₂ -CH ₂ -O-CH ₃

7 * 5 O f

- in - 29? S63

Het R ¹ R ²

CHo 0

Ho

N-F -S-CH ₂ -CH <

CH ₃ CH, O

CH ₃

UA 2 6 50 1

OCH <

CH ₃ 0 _ / 11 0 Γι 0 F -OCH ₃ CH ₃ -N- N- N- I N F -OC ₂ H ₅ CH ₃ CHo 0 "N- CH ₃ lJ F -O-CH (CH ₃ ) ₂ CH ₃ ^CH 3 TJ F -O-CH ₂ -CH = C Γι CH ₃

OCH ₃

CHo 0

N-F-O-CK ₂ -CH = CH-CH ₃

F is -O-CH ₂ -CH = CH-Cl

- 112 - 299963

Het R ¹ R ²

CH ₃ 0

CH ₃ O } = rf ti 0 0 y F - F -O-CH-CH = CH ₂ I CH ₃ rf -N- rf CH ₃ t N IN F -0-Chg-CSCH CH ₃ CH ₃ O F CH ₃ CH ₃ N j = CHo SJ F -0-CH-CSCH CH ₃ N j = I CH ₃ CH ₃ -O-CH ₂ -C = CH ₂ CH ₃ -O-CHg-CH ₂ -OC ₂ H ₅

F is -O-CH-CH ₂ -OC ₂ H ₅

CH ₃ CH ₃

F is -O-CH ₂ -CH-OCH ₃

CH ₃

UA 2 6 5 0 1

- 113 -

29? 363

Het

CHO 0 ^ N

N- F

-0-CHO /

CH ₃

CHo 0 N

CH

N-

CH ₃

I ³

F is -O-CH ₂ -C-OC ₂ H ₅ CH ₃

F -0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

CH ₃

CHo 0 N

CH

CHo 0

N-

-O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

CH ₃ CHo 0

N = n 'CH.

N-

CHr

-Ο-CH ₂ ^- C-CH ₃

F is -O-CH-C-CHo

I ³

CHO

F -SCH-

6 5 0 1

- 114 - 19? 963

Het R ¹ R ²

CHo 0

F "SC ₂ H ₅

CH ₃ CH ₃ 0

N-F -S-CH (CH ₃ ) ₂ CH ₃

CHq O

Hl · - <

N-F -S-CH ₂ -CH = CH ₂

CH ₃ CHo 0

N-F -S-CH ₂ -CH = CH-Cl

CH ₃

CHO 0 ^ N

KF -S-CH ₂ -CH = CH-CH ₃

CH ₃ CHO. 0

N-F -S-CH-CH = CHO CH ₃ CH ₃

CHo 0

N-F -S-CH ₂ -C =CH

^CH

UA 2 6 5 0 1

- 115 -

Ζ9Ϊ963

Het

CH ₃ O F -S-CH-CSCH I CH ₃ CH ₃ CH ₃ O F -S-CH ₂ -C = CH ₂ CH ₃ I N-CH ₃ F -S-CH ₂ -CH ₂ -OC ₂ H ₅ CHq O -N-- < CH ₃ CHq O

CH

F -S-CH-CH ₂ -OC ₂ H ₅ CHq

CHq O

-N <

I N J-N "

CH

-S-CH ₂ -CH-OCH ₃ CH ₃

CHq O

CH

F -S-CH ₂

0-

CHq O

-N

CH

-S-CHo-C-OC-,

CHQ

6 5 0 1

- 116 -

Hel

CH ₃

N-F -S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

CHO

CHo Ν

N- F

CH ₂ -S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

CHo * S3 0 0 IN \ N- CH ₃ N ^C "3

CH

Il

N-F -S-CH-C-CHr

CH

FoCH V

F is -O-CH ₂ -C <

CH-CH ₂ -OCH ₃ CH ₂ -OCH ₃

FoCH ²

N- F

CH.

F ₂ CH

N- F

CH.

-Oh

6 5 0 1

- 117 -

ZS? 963

Het

FpCH O

v <

v- <

N- F

CH

FpCH OV i

CH

N-F-O-CH ₂ -CN

FpCH O γ

O γ-Hf

CH

FpCH O

N-F-O-CH ₂ -COOC ₂ H ₅

0-CH ₂ -CO- / H

CH

FpCH O ²

CH

N-F-O-CH-COOCpHc CH,

FpCH O

V

N- F

CH

• O-CH-C-O- (H CHo

FpCH O

v

v <

N - F O - CHp - C - O - CHp 2 "2

CH-

IeA 2 6 50 1

- 118 2Θ7Θ63

Het

FoCH 0

² Ν {

I N J = n '

CH

0-CH ₂ -CO- (CH ₂ O

FoCH 0

² V <

V- <

CH

N-F-O-CH-CN

CH

FoCH 0

² > i

N-F-O-CH ₂ -CH ₂ -O-CH ₃

CH

F ₂ CH 0

V-C

N-F-O-CH ₂ -CH <

CH

OCH

FoCH 0

² γ i

N- H

CH

CH ₂ -OCH ₃ S-CH ₂ -C <

I CH ₂ -OCH ₃ CHO

FoCH 0

N- H -S- <H

FoCH 0

N- H

S- ^ H

5 0 1

- 119 -

IS? 963

Hel

FoCH 0

² V <

N-H-S-CH-

CH '

F ₂ CH O

N- H

-S-CH ₂ -CN

CH.

FoCH 0

² ^ f

N-H-S-CH ₂ -COOC ₂ H ₅

CH

FoCH 0

II / N-H-S-CH ₂ -C -O- <H

CH

FoCH 0

² V

H is -S-CH-COOC ₂ H ₅

CH CHr

F ₂ CH 0

N-H-S-CH-C-O- H

CH-

CH

FoCH 0

² > f

N- H

-S-CHo-C-O-CH-

L · * Il έ

2 6 5 0 1

- 120 -

137263

Het N F ₂ CH N O N F ₂ CH N F ₂ CH 11 rl R ² • F ₂ CH CH ₃ CH ₃ \ N- n ' O < N- CH ₃ O- ff FpCH ² V \ N- H -S-CH ₂ -CO (CH ₂ J ₃ -CH ₃ CH ₃ O O < N- "N Il 0 F ₂ CH ₃ CH ₃ N- FpCH O ² ν- < O U CH ₃ H -S-CH-CN CH ₃ H -S-CH ₂ -CH ₂ -O-CH ₃ H OCHo -S-CH-CH <OCH ₃ F -OCH ₃ F -OC ₂ H ₅

I N-F-O-CH (CH ₃ ) g

CHO

^leA 2 6 5 0 1

121 -

Has R ¹ R ²

F ₂ CH O

IN

F -O-CH ₂ -CHSCH ₂

CH ₃

F ₂ CH O

I is N-F-O-CH ₂ -CH = CH-CH ₃

CH ₃ F ₂ CH O

'"- F -O-CH ₂ -CH = CH-Cl

CH ₃ F ₂ CH 0

^ I-F -O-CH-CH = CH ₂ ^

CH ₃ CH ₃

F ₂ CH 0

Vl- F-O-CH ₂ -CSCH 25

F ₇ CH 0

γ <

N-F-O-CH-C = CH I

CH ₃ - CH ₃ CH ₂ F ^ Ο

F -O-CH ₂ -C = CH ₂ CH ₃ ^ "3

Le A 26 501

- 122 -

Het

R ¹ R ²

F ₂ CH O

² ν *

N-F-O-CH ₂ -CH ₂ -OC ₂ H ₅

CH

F _? CH O

N-F-O-CH-CH ₂ -OC ₂ H ₅

CH

CH

F _? CH O

j-l /

CH

-O-CH ₂ -CH-OCH ₃ CH ₃

FoCH 0

² y

N-F-O-CH ₂ - (

O-

CH

F _? CH 0 ² ^

^CH

CH

F is -O-CH ₂ -C-OC ₂ H ₅

CHQ

F ₇ CH 0 ²

N- F -0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

CH

FoCH 0

F is -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

CH.

IeA 2 6 5 0t

- 123 -

Het R ¹ R ²

FoCH O ²

j = /

F is -O-CH ₂ -C-CH ₃

CH ₃

F ₂ CH 0

N- F -0-CH-C-CH ₃

CH ₃ ^^ 3

F ₇ CH O ² N

N- H -SCH ₃

CH ₃ FoCH 0

N- H "SC ₂ H ₅

CH ₃ F ₂ CH 0

N-H-S-CH (CH ₃ ) ₂

CH ₃ F ₂ CH 0

N - H - -S - CHp - CH = CHo CH ₃

FpCH 0 ^ N- <

CH _{3 (}

H is -S-CH ₂ -CH "CH-C1

2 6 5Oi

- 124 -

Het R ¹ R ²

19? $ 63

FpCH O

² v. Chr

N-H -S-CH ₂ -CH = CH-CH ₃

CH ₃ FpCH O

N-H-S-CH-CH = CH ₂

CH ₃ CH ₃

FoCH O ² ><

N-H-S-CH ₂ -CSCH

CH ₃ F ₂ CH O

N-H-S-CH-CSCH

CH ₃ CH ₃

FpCH O ²

N-H-S-CH ₂ -C = CH ₂ CH ₃ CH ₃

FpCH O ^{2 N} <

N-H-S-CH ₂ -CH ₂ -OC ₂ H ₅

CH ₃

F ^ CH 0

( N-H-S-CH-CH ₂ -OC ₂ H ₅

CH ₃ ,

2 6 5 0 1

- 125 -

237963

FpCH O

² γ

CH

N-H-S-CH ₂ -CH-OCH ₃

CHO

FoCH O

² γ <

N-H-S-CH ₂ -

CH

FpCH 0

CH-

N-H-S-CH ₂ -C-OC ₂ H ₅

CH-

FpCH 0

² >

> - i

N-H-S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

CH

FpCH 0

N-H-S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

CH-;

FpCH 0

N-H-S-CH ₂ -C-CH ₃

CH-

FpCH 0

² ^

CH-

H is -S-CH-C-CH-

CH-

2 6 50 1

- 126 -

1 θ? 263

CH ₂ -OCH ₃

-O-CH ₂ -C <

I CH ₂ -OCH ₃

N- F

-o- (u

N-F-O-CH-

N-F-O-CH ₂ -CN

N-F-O-CH ₂ -COOC ₂ H ₅

N-F-Q-CH ₂ -CO- ^ H

IeA 2 6 5.0 1

- 127 -

Het

R ¹ R ²

N- F

N- F

-O-CH-COOC ₂ H ₅ CH ₃

0 -0-CH-C-

CH-

F -O-CH ₂ -CO-CH ₂ - /

N-F-O-CH ₂ -CO- (CH ₂ J ₃ -CH ₃

N- F -0-CH-CN CH ₃

N-F-O-CH ₂ -CH ₂ -O-CH ₃

2 fi 5 0 1

- 123 297363

vi

N-F-O-CH ₂ -CH <

OCH

OCH,

N-F -S-CH ₂ -C <

CH ₂ -OCH ₃

N- F -S- <H

N- F

N-F-S-CH ₂

N-F -S-CH ₂ -CN

F -S-CH ₂ -COOC ₂ H ₅

6 5Ot

- 129 -

R ¹ R ²

N- F

Il / -

-S-CHo-C-O- <H

N- F

-S-CH-COOC ₂ H ₅ CH,

N-F -S-CH

Il / -C-O- (H

CH,

F -S-CH ₂ -CO-CH ₂ -

N-F -S-CH ₂ -C-O- (CH ₂ ) ₃ -CH ₃

N-F-S-CH-CN

CH ₃

6 5 0 T

- 130 - JS9963

HeI R ¹ R ²

N- F

OCH ₃ N-F -S-CH ₂ CH <

OCH ₃

N-F -OCH ₃

N- F

N / \

N-F-O-CH (CHo) p

  ι

N-F-O-CH ₂ -CH = CH ₂

jk

N-F-O-CH ₂ -CH = CH-CH ₃

UA 2 6 5 0 1

- 131 -

Het R ¹ F ² N-F -O-CH ₂ -CH = CH-Cl O I I N- F -O-CH-CH = CH _? CH ₃

N-F-O-CH ₂ -CSCH

N-F-O-CH-C = CH

CH ₃

N-F-O-CHo-C = CH?

CH ₃

N-F-O-CH ₂ -CH ₂ -OC ₂ H ₅

N-F-O-CH-CHo-OCpHc

j 225 CH ₃

2? 50 1

197963

Het R ¹ R ²

N-F-O-CH ₂ -CH-OCH ₃

CH ₃

F -O-CH ₂ - (

N-F-O-CH ₂ -C-OC ₂ H ₅

CH.

N- F -0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

, N F -0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

N-F-O-CH ₂ -C-CH ₃

Kj ^ ~ ' - ° -f-^C"^CH3

CH ₃

^1βΑ 2 6 5 0 1

Het

N-F -S-CHO-CH = CH-CHo

N-F -S-CH-CH = CHo

I ²

CH ₃

IeA 2 6 5 0

- 134 -

Het R ¹ R ²

297363

N-F -S-CHo-CSCH

N-F -S-CH-CSCH

CH ₃

N-F -S-CHo-C = CHo

CH ₃

N-F -S-CH ₂ -CH ₂ -OC ₂ H ₅ N-F -S-CH-CH ₂ -OC ₂ H ₅

CHO

F -S-CH ₂ -CH-OCH ₃

CH ₃

UA 2 6 5Of

- 135 -

Het

R ¹ R ²

N-F-S-CH ₂

CH ₃

³

N-F-S-CH ₂ -C-OC ₂ H ₅

F -S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

jk

F is -S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

F is -S-CH ₂ -C-CH ₃

N-F • S-CH-C-CHo

³

CH ₃

Br CH

H -O-CH ₂ -C <

CH,

CHO-Ocho

CH ₂ - ^! 3

UA 2 6 5 0!

- 136 -

267363

Het

Br CHo

N- H

Br CH,

N- H

CH-

Br CH-

CH-

Br CH-

CH-

Br CH-

N-

CH-

br

C = <-o- / h

N-H-0-CH *

H -O-CH ₂ -CN

-O-CH ₂ -COOC ₂ H ₅

N-H-O-CH-

Br CH.

N-

H -O-CH-COOC ₂ H ₅

CH:

CH-

IeA 2 6 5 0 1

- 137 -

Z31963

Het

br

N- H

CH

Br CH.

N- H

N =

CH,

Br CH-

N- H

CHr

Br CH-

N- H

CH.

br

N- H

CH,

Br CH

N - N "

CH,

Br CHo

CH,

N- H

-0-CH CH ₃

¹¹ / -CO- (H

-O-CH ₂ -CO-CH ₂ - (

-O-CH-CNI CH ₃

-O-CH ₂ -CH ₂ -O-CH ₃

-O-CH ₂ -CH <

OCH.

OCH,

CH ₂ -OCH ₃ ^- C \

I CH ₂ -OCH ₃ Ch

UA 2 6 5Oi

- 138 - ZS7963

Br CH-

N- H -S-K H

CH '

N- H

Br CH.

CH. Br CH.

CH, Br CH,

N- H

CH. Br CH-

N-

CH.

Br CH,

CHO

-S - (^ H

N-H-S-CH ₂

N-H-S-CH ₂ -CN

-S-CH ₂ -COOC ₂ H ₅

-S-CH ₂ -C-

H is -S-CH-COOC ₂ H ₅

UA

- 139 -

Het

Br CHr

N-

> = N '\ -Hrj

br

H is -S-CH-C-

CH-

 -Λ

-S-CHO-C-O-CHO <

O-

br

N- H

CH-

Br CH

CHr

Br CH-

N-

CHr

Br CH-

N-

CH-

Br CH _:

-S-CH ₂ -CO- (CH ₂ ) ₃ -CH ₃ O

N-H-S-CH-CN

CH

-S-CH ₂ -CH ₂ -O-CH ₃

H is -S-CH ₂ -CH <

OCH

OCH

F -OCH-

IeA 2 6 50 1

- 140 -

Br CH ₃

F -OC ₂ H ₅

CH.

Br CH-

I = N "

F is -O-CH (CH ₃ ) ₂

CH,

br

N-

F is -O-CH ₂ -CH = CH ₂

Br CH-

N-F-O-CH ₂ -CH = CH-CH ₃

CH

Br CH-

N-

-O-CH ₂ -CH = CH-Cl

CH.

Br CH.

F is -O-CH-CK = CH ₂

CH-

Br CH-

N-F-O-CH ₂ -CHCH

CH,

UA 2 6 5 0!

- 141 -

Het

Br CH-

CH-

N-F-O-CH-C = ¹ CK

CH-

Br CH-

F is -O-CH ₂ -C = CH ₂

CH-

CH-

Br CH-

N-

H = N "uri ₃

Br CH-

F is -O-CH ₂ -CH ₂ -OC ₂ H ₅

CH-

F is -O-CH-CH ₂ -OC ₂ H ₅ CH,

Br CHo

N-F-O-CH ₂ -CH-OCH ₃ CHo

Br CH-

N-

CH-

-0-CH ₂ - <

Br CH-CHO

CH-

F is -O-CH ₂ -C-OC ₂ H ₅

CH-

UA 2 5 5 0 1

- 142 -

Het R ¹ R ²

Br CH ₃

N- F -0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

CH ₃

Br CH ₃

N- F -0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

CH ₃ / H ₃ CH ₃ F 0 j) Br N \ N- ν ' " -O-CH ₂ -C-CH π F 0 / H ₃ / H ₃ -O-CH-C-CH, 1 N-CH ₃ Λ I br Γι F t / H ₃ -SCH ₃ CH ₃ A br F L = -SC ₂ H ₅ CH ₃ Br N F t -S-CH (CH ₃ ) ₂ CH ₃ br CH ₃

IeA 2 6 5 0

- 143 -

Het R ¹ R ²

br

J * - F -S-CH ₂ -CH = CHg CH ₃ Br CH ^

N-F -S-CH ₂ -CH = CH-Cl

CH ₃

Br CH ₃

N-F -S-CH ₂ -CH = CH-CH ₃

CH ₃

Br CH ₃

N-F -S-CH-CH = CH ₂

CH ₃ CH ₃

Br CH ₃

F -S-CH ₂ -CHCH

CH ₃

Br CH ₃

D-

F -S-CH-CSCH

I CH ₃ CH ₃

Br CH,

N-F -S-CHg-C = CH ₂ CH ₃ -CH ₃

UA 2 6 5 0 1

- 144 -

R ¹ R ²

Br CHr

F -S-CH ₂ -CH ₂ -OC ₂ H ₅

CH

br

N-F -S-CH-CH ₂ -OC ₂ H ₅

CH-

Br CH-

N- F

CH-

- S-CHp ^- CH "OCHo CH-,

Br CH.

N-

F -S-CH ₂

 - (

CH.

Br CH.

N- F

CH.

-S-CH ₂ -C-OC ₂ H ₅

CH.

Br CH.

F -S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

Br CH.

N-

F -S-CH ₂ -CH ₂ -O-CH ₂ -CK ₂ -OC ₂ H ₅

CH.

6 5 0t

2 * 1963

Het

R ¹ R ²

Bry CH ₃ F O Il O Il N- Il -S-CH-C-CHo I I / 'CH ₃ CH ₃ F br \ N- £ CH ₃ ( i

H -O-CH ₂ -C <

CH-

CH ₂ -OCH ₃ CH ₂ -OCH ₃

Cl

N- H

N- H

-0- \ H

N- H -0-CH «

Cl

C6

H -O-CH ₂ -CN

IeA 2 6 5 0 1

- 146 - 237963

Het

Cl

H -O-CH ₂ -COOC ₂ H ₅

Cl

N-

H -O-CH ₂ -C-

N-H-O-CH-COOC ₂ H ₅

Cl

H -0-CH

Il /

-C-O- ^ H

CH-

Cl

Cl

σ>

H -O-CHp-CO-CH ₉ - <

² Il ² O-

H is -O-CH ₂ -C-O- (CH ₂ ) ₃ -CH ₃

6 5 3 t

- 147 -

231363

Het

Cl H -O-CH-CN CH ₃ Cl H -O-CH ₂ -CH ₂ -O-CH ₃ Cl H OCH ₃ -O-CH ₂ -CH <OCH ₃ 06- Cl H CH ₂ -OCH ₃ -S-CH ₂ -C <I CH ₂ -OCH ₃ CH ₃ 06-

Cl

CC

H -S-C H

Cl

Cl

06 '· «

-S-CH

2 6 5 0 1

- 148 -

237363

Het

Cl

-S-CH ₂ -CN

Cl

N-H-S-CH ₂ -COOC ₂ H ₅

¹¹ / -S-CH ₂ -CO- <H

^ N ^

H is -S-CH-COOC ₂ H ₅

Cl

N-H-S-CH-C-

CH,

Cl

Cl

H is -S-CH ₂ -CO-CH;

² Il "o-

H is -S-CH ₂ -CO- (CH ₂ ) Jj-CH ₃

UA 2 6 5 0

- K19 - 29Ϊ963

Het

Cx "-

M-S-CK-CN

Cl

N-H -S-CHj-CH ₂ -O-CH ₃

H -S-CH ^ -CH <

OCH

Ci »

HIGH,

Cl

N-

H is -OC ₂ H ₅

Cl

H -O-CH (CH ₃ ) ₂

Cl

-O-CH ₂ -CH = CH ₂

6 5Ot

- 150 -

Ζβ? 963

Hei

Cl

H is -O-CH ₂ -CH = CH-CH ₃

Cl

H -O-CH ₂ -CH-CH-Cl

Cl

Cl

H is -O-CH-CH = CH ₂

CHO

H -O-CH ₂ -CHCH

Cl

N-

Cl

H -O-CH-CSCH

CH ₃

H is -O-CH ₂ -C = CH ₂

CHO

Cl

-O-CH ₂ -CH ₂ -OC ₂ H ₅

UA 2 6 5 0

- 151 - Ζ9Ϊ963

N- H

-O-CH-CH ₂ -OC ₂ H ₅

CH,

CC

-O-CH ₂ -CH-OCH ₃

CH,

Cl

-0-CH ₂ - <

CH.

N- H

-O-CH ₂ -C-OC ₂ H ₅

CHr

Cl

H -0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O,

Cl Γ "ζ" * - ^Η -0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

Cl

CC--

II-O-CH ₂ -C-CH ₃

6 5 0 1

- 152 -

Has

Cl

H is -C-CH-C-CH,

CH,

H-SCH,

N- H

-SC ₂ H ₅

N-H-S-CH (CH ₃ ) ₂

N-H -S-CH ₂ -CH = CH ₂

N - H - -S - CH ₂ --CH = CH - Cl H is -S-CH ₂ -CH = CH-CH ₃

IeA 2 6 5 0 1

- 153 -

Het

Cl X J H -S-CH-CH = CHo I H CH ₃ -S-CH ₂ -CSCH Cl H -S-CH-CSCH I CH ₃ Cl Cl H -S-CH ₂ -C = CH ₂ CH ₃ N- Cl vs. I H -S-CH ₂ -CH ₂ -OC ₂ H ₅ 06- Cl

H "S-CH-CH ₂ -OC ₂ H ₅

CH

2 6 5 01

- 154 267S63

R ¹ R ²

Cl

H is -S-CH ₂ -CH-OCH ₃

CH.

Cl

N-H-S-CH ₂

rC

CH,

-S-CH ₂ -C-OC ₂ H ₅

Cl l ·

H is -S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

Cl

N-H-S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

Cl

co-

-S-CH ₂ -C-CH ₃

Cl

N-H-S-CH-C-CH,

CH,

δ 5 0 1

- 155 -

Z97S63

Het

R ¹ R ²

N-

CH ₂ -OCH ₃

0-CH ₂ -C <

I CH ₂ -OCH ₃

N-F-O-CH ₂

N- F

-O-CH ₂ -CN

JL J * ~ ^F -O-CH ₂ -COOCoHc

Yoke ^ N ^ ^{Δ 2 5}

JN-F .0-CH ₂ -CO-Zh "

2 6 5Ot

- 156 -

291963

Hel

(CH ₃ ).

N-F-O-CH-COOC ₂ H ₅ CH ₃

(CH.

1 ^N

F -O-CH

Il /

c-o-Zh

CH-

J N-

(CH ₉ ), CH ^ N- ^

F -O-CH ₂ -CO-CH ₂ - ^

ο-

N- F

(CH.

IN-

,) oCH ^^ N / '- O - CH ₂ --CO - (CH ₂ ) ₃ --CH ₃ O

0-CH-CN CH ₃

(CH.

) Cha ^ ^N ~ ^F - ⁰ - ^C H2-CH ₂ -0-CH ₃

UA 2 6 5 0 1

- 157 -

Hei

R ¹ R ²

(CH

N-F-O-CH ₂ -CH <

OCH

OCH

NF-S-CH ₂ -C <

CH-

CH ₂ -OCH ₃ CH ₂ -OCH ₃

I N F -S- <H

N -s / h

(CH

A.

F -S-CH ₂

(CH

I N-F -S-CH ₇ -CN

(CH-F -S-CH ₂ -COOC ₂ H ₅

2 6 5 0

- 158 - Ζ97Θ63

Het

(CHr

N-F -S-CH.

¹¹ /

, -CO- <H

(CH ₃ ).

N-F -S-CH-COOC ₂ H ₅

(CH.

jk

J N-

,) oCH - ^^ N- ^

F -S-CH

¹¹ /

-C-O- (H

(CH.

N-F -S-CHp-CO-CH ₇ - /

IN

-S-CH ₂ -CO- (CH ₂ J ₃ -CH ₃ O

JN

-S-CH-CN CH ₃

2 6 5 0 1

- 159 -

Het

(CH ₃ );

f -S-CH ₂ -CH ₂ -O-Ch ₃

n-

F -S-CH ₂ -CH <

OCH

OCH

(CH

N-F -0CH

(CH- _N _ _F

Jn-f -o-ch (ch ₃ ) ₂

(CH ₃ ).

KJ

jk

f -O-CH ₂ -CH = CH ₂

jk

(CH.

N- F

-CH = CH-CH

^leA 2 6 5

- 160 -

Het R ¹ R ²

291963

(CH _q ) _? ( F -O-CH ₂ -CH = CH-Cl (CH ₃ ) ₂ ( F -O-CH-CH = CH ₇ I ² CH ₃ F -O-CH ₂ -C ^ CH O Jk I N-: h ^^ n / O T N - O L N-

4-Λ ^ / ^Ν

F -O-CH-CSCH

CH ₃

! N-F -0-CH _? -C = CH _?

CH ₃

In-f -O-CH ₂ -CH ₂ -OC ₂ H ₅

jJ ^ n ^ ^N

F is -O-CH-CH ₂ -OC ₂ H ₅

CH ₃

UA 2 6 5 0 1

- 161 -

Hel

R ¹ Π ²

(CH.

IN-

0-CH ₂ -CH-OCH ₃ CHO

(CH ₃ );

jn

-O-CHO <

(CH.

I N ^^ N- ^

O-

CHO

I ³

0-CH ₂ -C-OC ₂ H ₅ CH ₃

(CHr

In-f -O-Ch ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

(O) pC

N- F -0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

(CH

^ N-F-O-CH ₂ -C-CH ₃

(CH ₃ ) ₂ CH> ^ N>'

I! F is -O-CH-C-CH.

CH-

IeA 2 6 B 0

- 162 -

Het R ¹ R ²

N- H -SCH ₃

N-H (CH ₃ :

(CH ₃ :

N-H-S-CH (CHo)

N-H -S-CH ₂ -CH = CH ₂ N - H - S - CHO - CH = CH - Cl

(CH ₃ ;

N-H -S-CHO-CH = CH-CH.

(CH ₃ :

N-H-S-CH-CH = CH.

<ch ₃ : "

CH ₃

UA 2 6 SOI

- 163 -

Hel 3 2 R ¹ R ² O Jk I N- (CH ₃ ) gCH - ^^^ O "_w; 6- H -S-CH ₂ -CHCH O Jk JL ^N " H -S-CH-CSCH j O CH ₃ / pit \ λ ti _ ^ ^ ovt - ^^ H -S-CH ₂ -C = CH ₂ Oh, Jk. (CHO) ₂ CH- ^ N '^' CH ₃ H -S-CH ₂ -CH ₂ -OCgH ₅ H -S-CH-CH ₂ -OC ₂ H ₅ CH ₃

jk

N-H-S-CH ₂ -CH-OCH-,

2, 3

CH ₃

2 6 5 0 1

- 164 -

Hei

S-CH ₂ - (

^CH

H is -S-CH ₂ -C-OC ₂ H ₅

CHO

In-h -S-CH ₂ -CH ₂ -O-Ch ₂ -CH ₂ -OCH ₃ N-H-S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

(CH ₃ )

-S ^- CH ₂ -C -CHg

H is -S-CH-C-CH ₃

CH ₃

CH

N-F-O-CH ₂ -C <

CH ₂ -OCH ₃

j CH ₂ -OCH ₃

~ 3

2 β 5Of

- 165 -

Het R ¹ R ²

N- F

-ο- / η

N-F-O-CH,

N- F

-O-CH ₂ -CN

N-F-O-CH ₂ -COOC ₂ H ₅

N-F-O-CHo-C-O- (H

6 5 0 1

- 166 -

237963

Het

N-F-O-CH-COOC ₂ H ₅

CH ₃

N-F-O-CH

Il / -C-O- <H

CH.

N-F-O-CH ₂ -CO-CH ₂ - ^

N-F-O-CH ₂ -CO- (CH ₂ J ₃ -CH ₃ O

N-F 0-CH-CN CH ₃

F is -O-CH ₂ -CH ₂ -O-CH ₃

6 5 0

- 167 -

23? 963

-.2

N-F-O-CH ₂ -CH <

OCH. OCH

CH ₂ -OCH ₃ N-H -S-CH ₂ -C <

I is CH ₂ -OCH ₃ CH ₃

N-H -S- (H

N- H

N- H

-S-CH ₂

N-H-S-CH ₂ -CN

6 5Of

- 168 -

J197S63

N-H-S-CH ₂ -COOC ₂ H ₅

N-H-S-CH ₂ -C-

N-H-S-CH-COOCpHc

I ^{2 5}

CHn

N-H-S-CH

-C-O- < H

N-H -S-CHo-C-O-CH- (

N-H-S-CH ₂ -C-O- (CH ₂ ) ₃ -CH ₃

6

- 169 -

Het R ¹ R ²

N-H-S-CH-CN

CH ₃

N-H-S-CH ₂ -CH ₂ -O-CH ₃

N-H -S-CH ₂ -CH <OCH ₃ OCH ₃

N- F

N-F -OCoHn

^{2 5}

N-F-O-CH (CH ₃ ) ₂

6 5 0 J

- 170 -

Hei R ¹ R ²

jk

N-F-O-CHo-CH = CHp

jk

N-F-O-CH ₂ -CH = CH-CH; N-F-O-CHo-CH = CH-Cl

nF-O-CH-CH = CH ₂

CH

jk

N- F

0-CH ₂ -CHCH

N-F-O-CH-CSCH

CH

UA 2 6 50 1

- 171 -

Het R ¹ R ²

N-F -U-CH ₂ -C =CH ₂

CH * 3

N-F-O-CH ₂ -CH ₂ -OC ₂ H ₅

F is -O-CH-CH ₂ -OC ₂ H ₅

N- F

CHr

-O-CH ₂ -CH-OCH ₃

CH-

F -O-CH ₂ -

N- F

CHO

I ³

-O-CH ₂ -C-OC ₂ H ₅ CH ₃

UA 2 6 5 0

- 172 -

Het R ¹ R ²

, N F -0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

N- F -0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

N- F

N-F-O-CH-C-CH3

CH

N- F -SCH.

N- F

UA 2 6 SOI

- 173 -

Het R ¹ R ²

F -S-CH (CHg) ₂

N- F

N- F

-S-CH ₂ -CH = CH-Cl

N-F -S-CH ₂ -CH = CH-CH ₃ N-F -S-CH-CH = CHo

I ²

F -S-CH ₂ -CHCH

UA 2 6 5 O I

- 174 -

Z91963

Het R ¹ R ²

jk

N-F -S-CH-CSCH

CH-

jk

1 ^h

N- F

-S-CH ₂ -C = CH ₂ CH ₃

IN

F -S-CH ₂ -CH ₂ -OC ₂ H ₅

N-F -S-CH-CH ₂ -OC ₂ H ₅

CHO

jk

F -S-CH ₂ -CH-OCH ₃

CHO

jk

N-F-S-CH ₂

2 6 5 0 1

- 175 -

Hei

R ¹

^CH

N-F-S-CH ₂ -C-OC ₂ H ₅

CH

N-F -S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

N-F -S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

N-F-S-CH ₂ -C-CH ₃

^C X

N-F-S-CH-C-CH,

CH

Cl

N-F-O-CH ₂ -C <

CHr CH ₂ -OCH ₃ CH ₂ -OCH ₃

6 S O 1

- 176 -

Het

Cl

N- F

Cl

Cl

Cl

N- F

N- F

Cl

N- F

Cl

N-

Cl

N- F

Cl

N- F

-Oh

-O-CH ₂ -CN

-O-CH ₂ -COOC ₂ H ₅ 0

¹¹ / F -O-CH ₂ -COC H

-O-CH-COOCoHc

I ^{2 5}

CHO

¹¹ / -O-CH-CO- <H

CH-

UA 2 6 5 0 1

- 177 297363

N-F-O-CH ₂ -CO-CH ₂

* II ²

-C

ty

N- F

N- F

N-F-O-CH ₂ -CO- (CH ₂ J ₃ -CH ₃ O

N-F-O-CH-CN

CHr

-O-CH ₂ -CH ₂ -O-CH ₃

N-F-O-CH ₂ -CH <

OCH

-S-CH ₂ -C

OCH

CH ₂ -OCH ₃

I CH ₂ -OCH ₃

CH

N- F -S- (H

2 6 5 0 1

- 178 -

291S63

Het

== N

N- F

N- F

N- F

η Ί

N- F

N-L = N ^

-S-CH ₂ -CN

-S-CH ₂ -COOC ₂ H ₅ O

Il / -η

-S-CH ₂ -CO- <H -S-CH-COOCpH ₅

I ²

CH ₃

N-F -S-CH

CH-

Il / 1

-C-O- <H

-S-CH ₂ -CO-CH ₂ -C

ι N- -S-CH ₂ -CO- (CH ₂ ) ₃ -CH ₃ O.

le / * Z 6 S o 1

- 179 -

137 9 £ 3

Het

R ¹

Cl

F -S-CH-CN

CH-

Cl

N-F -S-CH ₂ -CH ₂ -O-CH ₃

Cl

F -S-CH ₂ -CH <

OCH,

OCH ^

br

N-F -OCH-

br

N- F "OC ₂ H ₅

Br \

-n '

F is -O-CH (CH ₃ ) ₂

br

N-

-O-CH ₂ -CH = CH ₂

br

N-F-O-CH ₂ -CH = CH-CH ₃

UA 2 6 5 0 1

I I br N- R ¹ R ² br 1 t N- F -O-CH ₂ -CH = CH-Cl B _% F -O-CH-CH = CH ₂ \ N- CH ₃ F -O-CH -C = CH

br

F is -O-CH-C = CH

U = V

Sv

Q-

V Λ-

uv

CH ₃

F is -O-CH ₂ -C = CH ₂

CH ₃

F is -O-CH ₂ -CH ₂ -OC ₂ H ₅

\ V

br

Y-N

N-F-O-CH-CHo-OCoHc

CH ₃ Br

N-F-O-CH ₂ -CH-OCH ₃

CH ₃

2 5 5 0 1

- 181 -

237963

br

N- F

br

br

N-W

br

= *

N-

br

br

br

br

N- F

-0-CHO /

CH-

N-F 0 -CH ₂ -C-OC ₂ H ₅

F -0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃ F is -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

F is -O-CH ₂ -C-CH ₃

F -O-CH-C-CH '

CH.

F -SCH.

6 5 0 1

- 182 -

Het

br

N-

br

D-Br

N-

br

Br \

== N

F -S-CH (CH ₃ J ₂

F -S-CH ₂ -CH = CH ₂

F -S-CH ₂ -CH = CH-Cl F -S-CH ₂ -CH = CH-CH ₃

F -S-CH-CH = CH.

br

N-F -S-CH ₂ -CHCH

br

br

N-F -S-CH-C = CH

-S-CH ₂ -CSCH ₂ CHo

IeA 2 6 5 0

6 5 0

- 183 -

299963

br

N-F -S-CH ₂ -CH ₂ -OC ₂ H ₅

br

N-F -S-CH-CH ₂ -OC ₂ H ₅

CH,

br

N-F -S-CH ₂ -CH-OCH ₃

br

N-F -S-CH ₂ - <

br

N-F-S-CH ₂ -C-OC ₂ H ₅ CH-3

br

N-F -S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

br

N-F -S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

Br ν

Il N-F -S-CH ₂ -C-CH ₃

- 184 -

Het

Br \

N- F

-S-CH-C-CH ₃

CH-

Ν "F -O-CH ₂ -C <

CF, CH ₂ -OCH ₃

CH ₂ -OCH ₃

^ = N '3

CF.

N- F •

CF,

N- F

CF,

N- F

CF,

CF,

CF

CF ₃ ,

-Oh

-0-CH.

-0-CH ₂ -0-CH ₂ -CN -COOC ₂ H ₅

^ieA 2 6 5 0 1

- 185 -

297363

CF,

CF,

N- F

CF,

CF

CF,

CF,

CF,

CF,

CF,

CF,

N- F

CFo N- F

CF,

N- F

CF ₃ N-F

¹¹ / -O-CH ₂ -CO- <1H

N-F-O-CH-COOC ₂ H ₅

CH-

N-F -0-CH

Il J -CO- ^ H

CH-

-O-CH ₂ -CO-CH ₂ -

-O-CH ₂ -CO- (CHg) ₃ -CH ₃ O

-O-CH-CN CH ₃

-O-CH ₂ -CH ₂ -O-CH ₃

CF,

IsA 2 6 S 0 1

- 186 -

F is -O-CH ₂ -CH <

OCH

CF,

CF,

N-F -S-CH ₂ -C <

CF,

CH-

CH ₂ -OCH ₃ CH ₂ -OCH ₃

CF,

CF,

CF,

CF,

CF,

N- F

CF,

N- F

CF *

H- F

CF,

N- F

Cfo

³ N F

-S- <H -S- (H -S-CH ₂ -S-CH ₂ -CN -S-CH ₂ -COOC ₂ H ₅

CF,

LeA 2 6 5 0 1

- 187 -

CF.

N- F

CF.

CF,

CF,

CF.

N- F

CF,

CF,

N- F

CF,

CFr,

N- F

CF, ¹¹ / -S-CH ₂ -CO- ^ H

F -S-CH-COOC ₂ H ₅

CH,

N-F -S-CH

Il / -CO- ^ H

CH-

-S-CHO-CO-CH ₇ - <

-S-CH ₂ -CO- (CH ₂ ) ₃ -CH ₃ O

N-F-S-CH-CN

CH

-S-CH ₂ -CH ₂ -O-CH ₃

IeA 2 6 5 0

- 188 -

Het R ¹ R ²

237263

CF ₃

N- F. -S-CH ₂ -CH <

CCH ₃

CF ₃ 10 CF

OCH ₃

N-H-OCH ₃

CF ₃

^{15 1} NH-OC ₂ H ₅

CF ₃

CF ₃

N- H

20 W

CF ₃

CF ₃

N-H-O-CH ₂ -CH = CH ₂

25 ^CF 3

CF ₃

N-H-O-CH ₂ -CH = CH-CH ₃ CF ₃ 30 CF ₃

N - H - O - CH ₂ - CH £ C1

Le A 26 501

- 189 -

Het

CFr

N-H-O-CH-CH = CH-

CF

CF,

CF

CF

CF

N- H

CF

CF

CF ₃

CF,

CF

CF

N- H

CF

N- H

CF

CH

N - H - 0 CH ₂ - C = CH

O-CH-C 1 CH ₃ CH ₃

N-H-O-CH ₇ -C = CH

CH

N-H-O-CH ₂ -CH ₂ -OC ₂ H ₅

-O-CH-CHp-OCoHc CH ₃

-O-CHp-CH-OCHo CH ₃

UA 2 6 5 0 1

- 190 -

N- H

-0-CH ₂ - <

O-

CF,

CF,

CFo N- H

CFo N- H

V H

CF ₃ N-H

CF ₃ N-H

CF,

CH,

-O-CH ₂ -C-OC ₂ H ₅ CHo

-0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

-O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

CF,

-O-CH ₂ -C-CH ₃

CF,

CF,

-O-CH-C-CH3 CH,

N- H -SCH-

CF,

LeA 2 6 5 0 1

- 191 -

CF,

N- H "SC ₂ H ₅

CF,

r < ^CF3

N-H-S-CH (CH ₃ ) ₂

CF

CF,

N- H

CF, o-CH = CHo

N =

N - H S - CH ₂ --CH = CH - Cl

CF,

CF,

N-H -S-CH ₂ -CH = CH-CH ₃

CF *

CF ₃

CF,

N - H - -S-CH-CH = CHo

I ²

CHQ

CF,

H is -S-CH ₂ -C = CH

CF,

6 5 0

- 192 -

CF,

CF

CF

N- H

3 N- H

Cfo

CF

CF,

CF.

CF,

CF,

N- H

CF ₃ N-H

CFo N- H

CF ₃ N-H S-CH-C = CH CH ₃

S-CHo ^- C = CHo CHo

N-H-S-CH ₂ -CH ₂ -OC ₂ H ₅

-S-CH-CH ₂ -OC ₂ H ₅

CH-

-S-CH ₂ -CH-OCH ₃

CH.

-S-CH ₂

CF, CH,

S-CH ₂ -C-OC ₂ H ₅ CHo

UA 2 6 5 0 1

- 193 -

N-H-S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

CF

CF

N-H-S-CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

CF,

Ν "Η -S-CH ₂ -C-Cn ₃

CF,

VH -S-CH-C-CH ₃

CF,

CH.

C ₂ H ₅

N- F

^C 2 ^H 5

0-CH ₂ -C <

CH ₂ -OCH ₃

CH,

^C 2 ^H 5

N- F -o- / h

^C 2 ^H 5

6 5 0 J

- 194 -

Het

^C 2 ^H 5

^C 2 ^H 5

N- FC ₂ H ₅

-0-CH ₂

N-F-O-CH ₂ -CN

^C 2 ^H 5

N-F-O-CH ₂ -COOC ₂ H ₅

'2' 5

^C 2 ^H 5

, ^C 2 ^H 5 N- F

y ^C 2 ^H 5

Il /

-Q-CH ₂ -CO- ^ H -O-CH-COOC ₂ H ₅

^C 2 , ^C 2 ^H 5 F CH ₃ 0 Il N- II / -O-CH-C-O - (^ H ^{Η Η} 5 F (N- / · ^C 2 ^H 5 CH ₃ -O-CHo-C-O-CHO 2 n 2 O ^2H 5

LeA 2 6 5 0 1

- 195 -

Het

^C 2 ^H 5

^C 2 ^H 5 N- F

^C 2 ^H 5

N- F

^C 2 ^H 5

-O-CH ₂ -CO- (CH ₂ ) ₃ -CH ₃ O

-O-CH-CN CH ₃

N-F-O-CH ₂ -CH ₂ -O-CH ₃

^C 2 ^H 5

^C 2 ^H 5

^C 2 ^H 5

N-

^C 2 ^H 5

N- H

^C 2 ^H 5

^C 2 ^H 5

-O-CH ₂ -CH <

OCH

ochr

-S-CH ₂ -C <

CH ₂ -OCH ₃ CH ₂ -OCH ₃

C2 ^H 5

N- H -S ~ <H

C ₂ H ₅

₂ H ₅ M-H -S- <H

LeA 2 6 5 O 1

- 196 -

Het

^C 2 ^H 5 Iv-H

C ₅ H

2 "5

     · f

N- H -S-

CH ₂ -CN

^C 2 * ^w A * * b ^C 2 ^H 5 / ^{N C} 2 ^H 5 H -S-CH ₂ -COOC ₂ H ₅ 0 < , ^C 2 ^H 5 ^C 2 ^H 5 CoHc Γ- < ²⁵ N- -S-CH-C-O-Zh 0 C H 0 ^2H 5 -S-CH ₂ -CO-Zh N- k, ' H I CH ₃ / ^{N C} 2 ^H 5 -S-CH ₂ -CO-CH-II H Il 0 / 25 H N- -S-CH-COOC ₂ H ₅ I CH ₃

UA 26 50 1

- 197 -

Het R ¹ R '

237963

CoH

/ C *

N- H

-S-CH ₂ -CO- (CH ₂ Jg-CH ₃

^C 2 ^H 5 , ^C 2 ^H 5 H -S O \ N- * J CH-CN I / ^ ^C 2 ^H 5 Chg

C ₂ H ₅

N-H-S-CIl ₂ -CH ₂ -O-CH ₃

, ^C 2 ^H S

I = K OCH ₃

N-H-S-CH ₂ -CH <

^C 2 ^H 5

OCH ₃

C ₂ H ₅ N-F -OCH ₃

^C 2 ^H 5

F -OC ₂ H ₅

^C 2 ^H 5

^C 2 ^H 5 N-F-O-CH (CHg) ₂

^C 2 ^H 5

UA 2 6 5 0 1

- 198 -

Het R ¹ R ²

Z 37963

^C 2 ^H 5

^C 2 ^H 5

^C 2 ^H 5

N-F-O-CHo-CH = CH--

^C 2 ^H 5

N-F-O-CHo-CH = CH-CH-

^C 2 ^H 5

N-F-O-CH ₂ -CH = CH-Cl 5

^C 2 ^H 5

N-F-O-CH-CH = CH _: C ₂ H ₅ CH ₃

^C 2 ^H 5

N-F-O-CHo-C = CH

^C 2 ^H 5

^C 2 ^H 5

N-F-O-CH-C = CH

C ₂ H ₅ CH

^C 2 ^H 5

N-F-O-CH ₂ -C = CH ₂

^C 2 ^H 5, ^CH 3

UA 2 6 5 0 1

- J. 99 -

R ¹ R ²

nV

F is -O-CH ₂ -CH ₂ -OC ₂ H ₅

^C 2 ^H 5

^C 2 ^H 5

^C 2 ^H 5

^C 2 ^H

2 "5

^C 2 ^H 5 N- F

^C 2 ^H 5

N- F

^C 2 ^H 5

N- F

^C 2 ^H 5 -O-CH-CH ₂ -OC ₂ H ₅

-O-CH ₂ -CH-OCH ₃ CHO

-0-CH ₇ - <

0 " ^F

^C 2 ^H 5

^C 2 ^H 5 N-F-O-CH ₂ -C-OC ₂ H ₅ CH ₃

-O-CH ₂ -CH ₂ -OCH ₂ -CH ₂ -OCh ₃

^C 2 ^H 5

F is -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

6 5 0 1

Het F ¹ R ²

^C 2 ^H 5

COHC

2 5 u

N-F-O-CHo-C-CH-

COHC

2 5 n

N-F-O-CH-C-CH-

C ₂ H ₅ CHf

C ₂ N ₅

N- H -SCH ₃

^C 2 ^H 5

N- H "SC ₂ H ₅

^C 2 ^H 5

C ₂ H ₅ H -S-CH (CH ₃ ) ₂ RZV ^C 2 ^H ₅ H -S-CH ₂ -CH = CH ₂ , C ₂ H ₅ rV Z = N " ^C 2 ^H ₅ H -S-CH ₂ -CH = CH-Cl pn

CoH

2 ⁿ 5

^lflA 2 6 5 0

- 201 -

157363

Het

R ¹ R ²

N - H - ^ - S - CH ₂ --CH = CH - CH ₃

^C 2 ^H 5

/ ^C 2 ^H 5

C ₉ H

2 ⁿ 5

N- H

^C 2 ^H 5 S-CH-CH = CH ₉ CH ₃

^C 2 ^H 5

N-H-S-CH ₂ -C 1 CH

, ^C 2 ^H b

^C 2 ^H 5

^C 2 ^H 5

N- H

^C 2 ^H 5 N- H

^C 2 ^H 5 CH ₃

S-CH ₉ -C = CH, 2 j 2

CH ₃

N-H-S-CH ₂ -CH ₂ -OC ₂ H ₅

^C 2 ^H 5

^C 2 ^H 5 N- H

^C 2 ^H 5, -S-CH-CH ₂ -OC ₂ H ₅

CHO

UA 2 6 5 0 1

-

337963

R ¹ R ²

^C 2 ^H 5

^C 2 ^H 5

^C 2 ^H 5 N- H

^C 2 ^H 5 N- H

^C 2 ^H 5

-S-CH ₂ -CH-OCH ₃

-S-CH ₂ - (

CH-

N-H-S-CH ₂ -C-OC ₂ H ₅

^C 2 ^H 5 ^C 2 ^H 5

^C 2 ^H 5

^C 2 ^H 5

^C 2 ^H 5

^C 2 ^H 5

N-H-S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

^C 2 ^H 5

N-H-S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

C _? H ₅

2 5 "

N-H-S-CH ₂ -C-CH ₃

CpHc

2 5 "

N-H-S-CH-C-CH ₃

CH-

LeA 2 6 5 L

- 203 -

297363

Hel

(CHg) ₃ C

CH ₂ -OCH ₃ -O-CH ₂ -C <

I CH ₂ -OCH ₃

CH-

(CH _{3) 3} C

N- F "°" 7

(CH ₃ J ₃ C

N- F

(CH ₃ J ₃ C

N-F-O-CH.

(CH _{3) 3} C

N-F-O-CH ₂ -CN

(CHg) ₃ C

N-F-O-CH ₂ -COOC ₂ H ₅

(CHg) ₃ C

¹¹ /

F -O-CH ₂ -CO- ^ H

2 6 5 0

- 204 -

Het

R ¹ R ²

(CH ₃ J ₃ C

N-F-O-CH-COOCoHc

S , CO

CH.

(CH ₃ J ₃ C

N-F -O-CH-CO- { H

CH-

(CH _{3) 3} C

N- F

-0-CHp-C-O-CHO /

² Il ² O-

N- F

(CH _{3) 3} C

-O-CH ₂ -CO- (CH ₂ J ₃ -CH ₃ O

(CH ₃ J ₃ C

N-F-O-CH-CN

CH-

(CHg) ₃ C

N-F-O-CH ₂ -CH ₂ -O-CH ₃

(CHg) ₃ C

N - F - O - CH ₂ --CH <

OCH

OCH

IeA 2 6 5

- 205 -

Cl CH,

K-F-OCH,

N - F - OC ₂ H ₅

Cl CH *

N- i? -O-CH (CHg) ₂

Cl CH

N- F

Cl CH,

N-F-O-CH ₂ -CH = CH-CH ₃

Cl CH,

N-F-O-CHo-CH = CH-Cl

Cl CH ₃

Li-

F is -O-CH-CH = CHp

I ²

CHO

Cl / JH ₃

F -O-CH ₂ -CSCH

SOI

- 206 -

29/963

Hei

Cl CH ₃

V = K ³

N- F

Cl CH-O-CH-CSCH CHr

-O-CH ₂ -C = CH ₂

Cl CH-

N- F f

Cl CH ₃

N- F

Cl

N- F

Cl CH,

N- F

Cl

N-F-O-CH ₂ -CH ₂ -OC ₂ H ₅

-O-CH-CH ₂ -OC ₂ H ₅ CH ₃

-O-CHO-CH-OCH ₃ 2,

0-

CH,

-O-CH ₂ -C-OC ₂ H ₅

Cl. CH,

V = K

N- F -0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

\ A 2 6 5 0

- 207 -

Cl

N- F -0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

Cl

N-F-O-CH ₂ -C-CH ₃

Cl CH,

N-F-O-CH-C-CH-

CH-

Cl V

N-F-SCH,

N =

Cl CH-

N- F -SC ₂ H ₅

Cl CH-

N-F -S-CH (CH ₃ J ₂

Cl CH,

N-F -S-CH ₂ -CH = CH ₂

Cl CH,

N-F -S-CH ₂ -CH = CH-Cl

2 6 5Of

- 208 -

ZJ? 9 63

Het

Cl CH-

N-F -S-CH - CH = CH-CH,

Cl CH-:

N-F -S-CH-CH = CH-

CHr

Cl

N- F

Cl CH-

V <

N- F •

 N =

Cl CH ₃

N- F

-S-CH ₂ -CSCH

-S-CH-CSCH

CH-;

CH ₃ Cl CH ₃

f Cl CH ₃

N-F -S-CH-CH ₂ -OC ₂ H ₅

CH ₃ Cl CH ₃

, N-F -S-CH ₂ -CH-OCH ₃

CHO

Le A 26

- 209 -

297965

Cl CH-

N-F-S-CH ₂ -

Cl CHr

N-F-S-CH ₂ -C-OC ₂ H ₅

CHO

Cl

N-F -S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

Cl CHr

N- F

-S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

Cl CHo

N- F

S-CH ₂ -C-CH ₃

Cl CH

N-F -S-CH-C-CHr

CH-

N-F-O-CH ₂ -C <

CHr

CH ₂ -OCH ₃ CH ₂ -OCH ₃

N- F

6 S01

- 210 -

Het

N- F

-Oh

N-F -O-CH-

N-F-O-CH ₂ -CN

N-F-O-CH ₂ -COOC ₂ H ₅

N- F

¹¹ / -O-CH ₂ -CO- ^ H

F -O-CH-COOC ₂ H ₅

CH-

F -0-CH

¹¹ / -C-O ~ \ H

CHr

N-F-O-CH

-CO-CHo- (

6 5 0 1

- 211 Z97963

N-F-O-CH ₂ -CO- (CH ₂ ) ₃ -CH ₃

N - F - O - CH - CN CH ₃

IT NF-O-CHO-CH ₇ -O-CHO

N-F-O-CH ₂ -CH <

OCH.

OCH ^

N-F -S-CH ₂ -C <

CH ₂ -OCH ₃ CH ₂ -OCH ₃

N- F -S- <H

N- F

-s / h

ι N-F -S-CH.

UA 2 6 5 0 1

- 212 -

231363

N-F -S-CH ₂ -CN

V '

N-F -S-CH ₂ -COOC ₂ H ₅

N-F -S-CH

₂ -C-O- <H

N- F

-S-CH-COOC ₂ H ₅ CH,

N- F

II /

-S-CH-CO- ( H

CH-

N- F

N- F. -S-CH ₂ -CO- (CH ₂ J ₃ -CH ₃

N-F-S-CH-CN

CH-

26 50 1

- 213 -

237963

Het

R ¹

N-F -S-CH ₂ -CH ₂ -O-CH ₃

N-F -S-CH ₂ -CH <

OCH

OCH

N-F -OCHn

F-CH.

N - F - OC ₂ H ₅

F-CH.

N-F-O-CH (CH ₃ ) ₂

F-CH ₂

N- F

F-CH ₂

F-CH ₂

-O-CH ₂ -CH = CH ₂

N-F-O-CH ₂ -CH = CH-CH ₃

2 5 5 0 7

- 214 -

297363

N-F-O-CH ₂ -CH = CH-Cl

F-CH ₂

N-F-O-CH-CH = CHo

F-CH ₂ CH ₃

Γ-

F -0-CHo-C = CH

F-CH ₂

N-F-O-CH-CSCH

F-CH ₂ CH ₃

N - F - O - CHo - C = CH '

F-CH ₂ CH ₃

F is -O-CH ₂ -CH ₂ -OC, H ₅

"Ν F-CH ₂

N-F-O-CH-CH ₂ -OC ₂ H ₅

F-CH ₂ CH ₃

UA 2 6 5 0 1

- 215 -

Hei

R ¹ R ²

N-

-O-CH ₂ -CH-OCH ₃

F-CH

N-

-O-CH ₂ - (

F-CH ₂

CH-

N-

F is -O-CH ₂ -C-OC ₂ H ₅

F-CH ₂

CH-

N- F -0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

F-CH ₂

N- F

-O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

F-CH.

N-F-O-CH ₂ -C-CH ₃

F-CH ₂

F is -O-CH-C-CH ₃

F-CH

CH-

- 216 -

1S7363

Het R ¹ R ²

N- F -SCH-

F-CH ₂

N- F -SC ₂ H ₅

F-CH.

N-F -S-CH (CH ₃ J ₂

F-CH ₂

N- F

-S-CH ₂ -CH = CH ₂

F-CH

N-F -S-CH ₂ -CH = CH-Cl

F-CH '

N-F -S-CH ₂ -CH = CH-CH ₃

F-CH,

i N-F -S-CH-CH = CH ₂

F-CH,

CH-

2 6 5 O

- 217 -

Het

R ¹ R ²

N- F

F-CH ₂

N-

F-CH- -S-CH-CH ₃ CSCH

W-F -S-CH ₂ -C = CH ₂

F-CH 1 CH-

N-F -S-CH ₂ -CH ₂ -OC ₂ H ₅

F-CH ₂

F is -S-CH-CH ₂ -OC ₂ H ₅

F-CH ₂ CH,

N- F

F-CH- -S-CHO-CH-OCHo 2 j

CH,

rv

F-CH

2 6 5 0

- 218 2S7363

F-CH

N- F

F-CH.

F-CH ^

F-CH ₂

N-

F-CH ₂ Cl

CH-Cl

N- F

CH-

CH ^ I ³

-S-CH ₂ -C-OC ₂ H ₅ CH ₃

-S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

N-F-S-CH ₂ -C-CH ₃

F is -S-CH-C-CH ₃

CH-

N-F-O-CH ₂ -C <CH,

CH ₂ -OCH ₃ CH ₂ -OCH ₃

2 6 5 0

- 219 -

Cl

N- F -o- / h

CH-

Cl

N-

F -O-CH-

CH.

Cl

F is -O-CH ₂ -CN

CH

Cl

N-F-O-CH ₂ -COOC ₂ H ₅

CH-

Cl

N-

CH-

Cl

N-F-O-CH-COOC ₂ H ₅

CH,

Cl

CH

M /

F is -O-CH-C-O- (Η

3 ¹ CH:

6 5

- 220 -

237S63

Cl

CH-

Cl

Cl

N-

CH ₃ Cl

N-

CH.

Cl

N-

CH.

Cl

N-

CH,

Cl

N-

CH-

N-F-O-CHo-C-O-i

N-F-O-CH ₂ -CO- (CH ₂ ) ₃ -CH ₃

F -O-CH-CN

CH

-O-CH ₂ -CH ₂ -O-CH ₃

F is -O-CH ₂ -CH <

OCH.

OCH.

F -S-CH ₂ -C <

CH.

CH ₂ -OCH ₃ CH ₂ -OCH ₃

IeA 2 6 5Of

- 221 -

237363

Rl R ²

Cl

CH

Cl

F -S-CH ₂

Cl

N-F -S-CH ₂ -CN

CH-Cl

N-F-O-CH ₂ -COOC ₂ H ₅

CH _:

Cl

N-F -S-CH.

Il / j-C-0- <H

Cl

F -S-CH-COOC ₂ H ₅

Cl

N- F

CH-

II -S-CH-C-

CHO

^ΛβΛ 2 6 5 0

- 222 -

139963

Cl

F -S-CH ₂ -CO-CH ₂

Cl

N- F

Cl ν

N =

CH ₃ Cl

CH,

Cl

CH,

Cl

CH-

Cl

CH-

-S-CH ₂ -CO- (CH ₂ J ₃ -CH ₃ O

-S-CH-CN CH ₃

N-F -S-CH ₂ -CH ₂ -O-CH ₃

F -S-CH ₂ -CH <

OCH

OCH

N-F -OCH-

N- F "OC ₂ H ₅

26 50 1

- 223 -

R ¹

C ?.

N-F-0-CH (CHO)

" ³

CH ₃ Cl

N-F-O-CHo-CH = CH

CH-

Cl

CHr

Cl

CH-

Cl

CH-

Cl

CH ₃ Cl

F is -O-CH ₂ -CH = CH-CH ₃

CH ₃ ,

F is -O-CH ₂ -CH = CH-Cl

N-F-O-CH-CH = CH

CH

0-CH ₂ -CSCH

-0-CH = CH-C

CH

6

- 224 -

Cl

-O-CH ₂ -C = CH ₂ CHo

Cl

N-F-O-CHo-CHo-OC ₇ Hc

CH,

Cl

H = N '

N-F-O-CH-CH ₂ -OC ₂ H ₅ CHo

Cl

N- F

zwr

-O-CH ₂ -CH-OCH ₃ CHO

Cl

CH-

0-CHO /

Cl

CH-

CH.

F is -O-CH ₂ -C-OC ₂ H ₅ CH,

Cl

CH

F -0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

3 ·

& 2 6 5

- 225 -

Cl

N- F -0-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

CH-

Cl

^ = N

N-

-O-CH ₂ -C-CH ₃

Cl

F is -O-CH-C-CH ₃

CH *

CH.

·>

N- F -SCH-

N- F -SC ₂ H ₅

N-F -S-CH (CH ₃ ) ₂

N-F -S-CH ₂ -CH = CH ₂

N-F -S-CH ₂ -CH = CH-Cl

26 50 1

- 226 -

Het

N-F -S-CH ₂ -CH = CH-CH ₃

N-F -S-CH-CH = CH ₂

CHQ

N-F -S-CH ₂ -CHCH

N-F -S-CH-C = CH

I CH ₃

N-F -S-CHo-C = CHo

Ct I C *

CHQ

F -S-CH ₂ -CH ₂ -OC ₂ H ₅

N-F -S-CH-CH ₂ -OC ₂ H ₅

CH,

'N-F -S-CH ₂ -CH-OCH ₃

CH,

2 6 50 1

- 227 -

N- F

N- F

CH,

-S-C-CHO OCpH

N-. F -S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OCH ₃

N- F

-S-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -OC ₂ H ₅

_N _ _F -S-CH ₂ -C-CH ₃

N-F-S-CH-C-CH-

CH.

2 6 5Ot

- 228 -

397963

When using, for example, 4-cyeno-2 # 5-difluorophenylhydrazine and acetylacetone as starting materials, the reaction procedure of process (a) according to the invention can be represented by the following formula:

H ₂ NN -2H ₂ O

N + CHo-C-CHo-C-CH *

Il * Il

O O

If, for example, 4- (3,5-dimethyl) .pyrazol-1-yl) -2,5-difluorobenzonitrile is used as the starting compound and sulfuryl chloride is used as the halogenating agent, then the reaction mixture of the process (b) according to the invention can be represented by the following formula scheme:

Le A 26

- 229 -

If, for example, 1- (2,5-fluoro-4-cyanophenyl) -4H-pyrazolin-5-one is used as starting compound and phosphorus oxychloride in the presence of triphenylphosphine as halogenating agent, the course of the reaction of process (c) according to the invention can be determined by the following formula Shown schematically

POC1 ₃ / P <C ₆ H ₅ > 3

Cl F

If, for example, 4-cyano-2-fluoro-5-isopropoxy]) oxyphenylhydrazine and N-ethoxycarbonyl-2,2-dimethylprcpanimic acid esters ale are used as starting materials, the reaction path of the process (d) according to the invention can be represented by the following formula:

H ₂ NN

-2C ₂ H ₅ OH

C (CHg) ₃

C ₂ H ₅ -OC = N-COOC ₂ H ₅

v OF

(CHg) gC

0-CH (CHg) ₂

Le A 26

- 230 -

19P263

For example, using 1- (4-cyano-2-fluoro-5-allyloxyphenyl) -3-t-butyl-4H-1, 2 _# 4-triazolin-5-one and propargyl bromide as starting materials, the reaction blept according to the invention to process (e) by the following formula:

HN {

(CHg) ₃ C

0-CH ₂ -CH = CH ₂

+ HCSC-CH ₂ -Br

20

-HBr

(CHg) ₃ C

0-CH ₂ -CH = CH ₂

If, for example, piperidin-2-one (2,5-difluoro-4-cyanophenylhydrazone is used as external compound , the course of the reaction of process (f) according to the invention can be represented by the following formula:

25 30

35

Le A 26 501

- 231 -

139963

If, for example N-pivaloyl-N ¹ - (4-cyano-2-fluoro-5-methoxyphenyl) -hydrazine al * output Ever bond, then the Reaktioneablauf of the inventive method (g) through the following reaction scheme can be represented:

-2HC1

0 F

ff

(CHg) ₃ C

OCH.

If, for example, 4- (3,4,5-trimethylpyrazol-1-yl) -2-fluorobenzonitrile and tert-butyltroracan are used as starting materials, the reaction sequence of the process (h-a) according to the invention can be represented by the following formula ## STR5 ##

CH

N ♦ (CHg) ₃ C-SH

RF

CH ₃ CH ₃ F

SC (CHg) ₃

Le A 26 501

- 232 -

1Θ7 & 63

If, for example, 4- (1-pyrazolyl) -2-hydroxybenzonitrile and allyl bromide are used as starting materials, the course of the reaction of the process (h-β) according to the invention can be represented by the following formula scheme:

N + CHo = CH-CH ₉ -Br

-HBr ρ = λ r =

0-CH ₂ -CH = CH ₂

If, for example, 4-Ois carbonyl-pyrazol-1-yl) -2,5-difluorobenzonitrile is used as the starting compound, then the reaction sequence of process (i) according to the invention can be represented by the following formula: laenema!

C ₂ H ₅ O-CO CH ₃ F

H ₂ O

CH ₃ F

-C ₂ H ₅ OH -CO ₂

CH:

The 4-cyanophenyl hydrazines required for carrying out the processes (a) and (d) according to the invention as outer transition set off are generally represented by the formula (II)

Le A ? <:. 501

- 233 -

defined "In this formula (II), R ¹ and R ² preferably represent those radicals" the ready in connection with the description of erfindungi - substances of the formula (I) as being preferred for these Subeti called tuenten "

The 4-Cyanophon "hyira ;; ne of the formula (II) are not yet known ^nn: iibonfalls subject of the invention,

They are obtained "when 4-fluorobenzonitriles of the formula (XIII)" 15

(XIII)

in which

R ² " ^{1 is} halogen and R ^{1 has} the meaning given above

with hydrazine hydrate, optionally in the presence of a diluent such as ethanol at temperatures zvrinchen 20 ⁰ C and 130 ⁰ C and reacting the thus obtainable 4-cyano-phenylhydrazine of formula (Ila)

-NHo (Ila)

Le A 26

- 234 - 199363

in which 5 R * and r3 ~ 1 dig have the meaning given above »

optionally in a subsequent step with alcohols or Y-thiols of the formula (IX) 10

R ⁹ -XH (IX) in which

ι. each optionally substituted alkyl, alkenyl, alkynyl or cycloalkyl and

X is oxygen or sulfur,

zwiechf optionally in the presence of a diluent, for example acetonitrile, and optionally in the presence of a reaction! 1f "means such as Matrium'hydrid or potassium hydroxide at temperatures / n O ⁰ C and 80 ⁰ C is reacted.

4-cyanophenylhydrazines of the formula (lib),

R ¹

NC ^ ^ --NH-NH ₂ (lib) tfz

in which

Le A 26 SOl

- 235 - 237963

R * has the meaning given above and 5

R ^{9 is} each optionally substituted alkyl ι alkenyl »alkynyl or cycloalkyl,

Alternatively, "when roan 4-aminobenzonitriles of the formula (XIV) _{1 is obtained}

^R NC- ζ / ~ N

H ₂ (XIV)

.H ⁹ O

in which

R * and R ⁹ (as defined above have »

initially diazotized in the usual manner with sodium nitrite in the equivalent of an acid such as hydrochloric acid and then also reduced in a generally conventional manner with a reducing agent such as tin dichloride.

4-fluorobenzonitriles of the formula (XIII) are known or obtainable in analogy to known processes (cf. for example EP · 191 185; US 3 97d 127j DE 2104312; J. Heterocycl, Chem JLS, 1373-1378 [1978] DE i. 2,711,332; PCT Int. Appl.

W087 / 7602; JP 56/79660; Zh. org. Khim. 2 »1257-1259 [1967]; J. Chem. Res., Synop. 1984 . 382-383; Collect. Czech. Chem «Commun. £ 9, 992-1000 [1984]; Collect. Csech. Chem. Comnmn. 4J2, 2001-2017 [1977]).

Le A 2 6

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4-Ainobenzonitriles of the formula (XIV) are likewise known or obtainable in analogy to known processes (cf., for example, JP 46/3368, EP 100 172 or EP 224 001).

Dia for carrying out the process (b) furthermore required as starting materials 1,3-diketones sia in general formula (III) In this formula (III), R 1 preferably represents those radicals which have already been used in connection with the description of the invention Substances of the formula (I) have been mentioned as being preferred for these substituents.

R ⁴ " ¹ is preferably hydrogen" is straight-chain or branched alkyl having 1 to 6 carbon atoms or represents straight-chain or branched "haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms" in particular hydrogen "methyl" ethyl " or i-propyl- "i-, s- or t-butyl" for fluoromethyl "difluoromethyl" trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, difluorochloromethyl or dichlorofluoromethyl.

R ⁵ " ¹ is preferably hydrogen, straight-chain 3-membered or branched alkyl having 1 to 6 carbon atoms or straight-chain © * or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms.

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especially for hydrogen, "methyl, ethyl" η- or i-propyl-, i- _# β- or t-butyl "for fluoromethyl difluoromethyl * trifluoromethyl, chloromethyl, chloromethyl, trichloromethyl, difluorochloroethyl or dichlorofluoromethyl

1,3-diketoae of the formula (III) and derivatives dionor diketone vi "b" ipielaweiee enol ethers "enoleatres" ketals "eno." Ttit -k "tple _P enamines or beta-halo-vinyl ketones are" well known compounds of organic chemistry "

The N-aryl-nitrogen heterocycles required as starting materials for carrying out the process (b) according to the invention are generally defined by the formula (Ij). In this formula (Ij), R ¹ , R ² and R ^{3 are} preferably those radicals which are already In connection with the description of the substances of the formula (I) according to the invention have been mentioned as preferred for these substituents

R ^{5 '1} is preferably hydrogen, "straight-chain or branched" alkyl group having 1 to 6 carbon atoms or straight-chain or branched halogenoalkyl mil I to 4 carbon atoms and 1 to 9 identical or different

Halogen atoms "especially for hydrogen"

Methyl "ethyl" η- or i-propyl-n-, i- "s- or t-butyl" for fluoromethyl "difluoromethyl" tri

Le A 2 6 501

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fluoroethyl * chloromethyl "dichloromethyl, trichloromethyl-difluorochloromethyl or dichlorofluoromethyl"

The N-aryl-nitrogen heterocycles of the formula (Ij) are compounds according to the invention and can be obtained by means of the processes (a), (h-a), (h-β) and (i) according to the invention.

The N-aryl-pyrazolinones required as starting materials for carrying out the process (c) according to the invention are generally defined by the formula (IV). In this formula (IV), β-thene R ¹ IR ² , R ³ and R ^{4 are} preferably those radicals which have been mentioned in connection with the description of the compounds of the formula (I) according to the invention as being preferred for these substituents.

The N-arylpyrazolinones of the formula (IV) are not yet known and likewise the subject of the invention "they are obtained" when β-ketoesters of the formula (XV)

R ³ -C-CH-COOR ¹³ (XV)

0 R ⁴

in which 30

R ^{13 is} alkyl, in particular methyl or ethyl, and

Le A 26 50 1

- 239 -

19Ϊ963

r4 have the abovementioned meanings "5 with 4-cyanophenylhydrazines of the formula (II)"

R ¹

Jο Jf ^

in which

R * and R ^{2 have} the abovementioned meaning,

given case in the presence of a diluent such as ethanol and optionally in the presence einee reaction auxiliary agent e such as sulfuric acid at temperatures between 20 ⁰ C and 120 ⁰ C.

, implements.

β-ketoesters of the formula (XV) are generally known compounds of organic chemistry «

The for carrying out the inventive method

(d) Iminocarbon esters required as starting materials are generally defined by the formula (V). In this formula (V), R preferably represents those radicals which have already been mentioned in connection with the description of the invention.

dungsgemaßen substances of formula (I) have been mentioned as preferred for this substituent «

Le A 26

- 240 -

and R * * preferably stand independently of one another for straight-chain or branched alkyl having 1 to 4 carbon atoms, in particular for methyl or ethyl.

The iminocarbon esters of the formula (V) are known or obtainable in analogy to known processes (cf., for example, Chem. Ber., 119, 2444-2457, (1986) J. Bull., 1981, Soc., Jpn., 51, 3943-3944; Lett., 1982, 1015-1016, Chem. Lett., 1978, 1403-1404, J. Amer., Chem., Soc., 95, 3957-3963

[19733; Y, org. Chem. 36., 3251-3252 [19713]. 15

For carrying out the process (e) required as starting materials N-aryl-nitrogen heterocycles are generally defined by the formula (Id). In this formula (Id), R ¹ , R ² and R ^{7 2} ^ preferably represent those radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for these sub-substituents.

The N-aryl-nitrogen heterocycles of the formula (Id) are compounds according to the invention and can be obtained by means of the process (d) according to the invention,

The alkylating agents which are furthermore required as starting materials for carrying out the process (e) according to the invention are generally defined by the formula (VI). In this formula (VI), R ⁸ " ^{1 is} preferably

Le A 26 SOl

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in each case straight-chain or branched alkyl having 1 to 6 carbon atoms "alkenyl having 3 to 6 carbon atoms, alkynyl having 3 to 6 carbon atoms" haloalkyl having 1 to 4 carbon atoms and 1 to the same or different halogen atoms, haloalkenyl having 3 to 6 carbon atoms and 1 to 5 identical or different halogen atoms or halogenoalkynyl having 3 to 6 carbon atoms and 1 to 5 identical or different halogen atoms «

R ⁸ " ¹ in particular represents methyl, ethyl, η- or i-propyl, n-, i-, s- or t-butyl, in each case mono-, di- or trisubstituted by fluorine and / or chlorine, methyl, ethyl ocitr t Butyl, for allyl, for n- or i-butenyl, for chloraliyi, for dichloroalkyl, for propargyl or for chloropropargyl. "

E * is preferably halogen, in particular chlorine, bromine or iodine, or in each case optionally substituted alkylsulfonyloxy, alkoxysulfonyloxy or arylsulfonyloxy, for example methanesulfonyloxy, trifluoromethanesulfonyloxy, methoxysulfonyloxy, ethoxysulfonyloxy or p-toluenesulfonyloxy.

The alkylating agents of the formula (VI) are generally known compounds of organic chemistry «

The stubborn implementation of the method (f) required as starting materials Amidrazone are by 35

Le A 26 501

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3.99963

Funnel (VII) is defined in general terms. In this formula (VII), R ¹ and ² preferably represent those radicals which have already been mentioned as preferred for these substituents in connection with the description of the compounds of the formula (I) according to the invention.

R and R are preferably together a double-linked Alkandiylreat having 2 to 6 carbon atoms «in particular for a 1 * 3-Propandiylrest, a 1« 4-ButandiylreBt or a 1 «5-Pentandiylrest, 15

The amidrazones of the formula (VII) are not yet known. They are obtained in analogy to known methods (cf.

e.g. US 4 080 192 or DE-OS 1 957 783) "if one

Lactams of the formula (XVI),

R ⁸ " ² -NH-CR ⁷ " ¹ (XVI)

in which 25

R ^ "* and R® ~ 2 have the meaning given above"

first in a 1st stage with a halogenating agent such as phosphorus oxychloride * thionyl chloride or phosgene optionally in the presence of a diluent such as ethanol or dioxane and optionally in the presence of a Roaktionshilfsmittels such as triethylamine or triethylamine

Le A 26 SOl

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Reacting pyridine at temperatures between ^{0 0} C and 50 ⁰ C and then the thus obtained imide chlorides of the formula (XVII) ₄

R ⁸ " ² -N» CR ⁷ " ¹ (XVII)

Cl 10 in which

R ⁷ " ¹ and R ⁸ " ^{2 have} the meanings given above, with 4-cyanophenylhydrazines of the formula (ID ₄

(II) ^ ν

R ¹ 20

in which

R ¹ and R ² raise the meaning given above,

optionally in the presence of a diluent such as ethanol and optionally in the presence of a reaction auxiliary such as triethylamine or pyridine at temperatures between ^{0 0} C and 80 ⁰ C implemented.

Lactones of formula (XVI) are well known compounds of organic chemistry. "

Le A 26

- 244 -

237963

The phenylhydrazides which are never required for carrying out the process (g) according to the invention are generally defined by the formula (VIII). In this formula (VIII), F ¹ , R ² and R ^{6 are} preferably those radicals which have already been described in connection with the description of the substances of the formula (I) according to the invention were preferably named for these sub-substituents. «

The phenylhydrazides of formula (VIII) are not yet known «

They are obtained "when 4-Cyanophenylhydrazines of the formula (II),

R ² ^ l

in which

R ¹ and R ^{2 have} the meaning given above «25

with acylating agents of the formula (XVIII)

R ⁶ -CE ³ (XVIII)

0 30

η which

R "has the meaning given above and 35

Le A 26

- 245 -

E ^{3 is} an electron attracting leaving group, preferably halogen or a Reut

R ^ -C-O- stands «where R ^ is the abovementioned

and especially for chlorine "10

optionally in the presence of a diluent such as dichloroethane and optionally in the presence eiiies reaction auxiliary such as triethylamine at temperatures between - 20 ⁰ C and + 60 ⁰ C implemented.

Acylating agents of the formula (XVIII) are generally known compounds c.or organic chemistry «

The N-aryl-nitrogen heterocycles required as starting materials for carrying out the process according to the invention »(ha) are generally defined by the formula (Ik). In this formula (Ik), R ¹ , R * ³ , R ⁴ and R ^{5 are} preferably those Radicals "which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention"

R ^ -I preferably represents fluorine "is chlorine or Broic" in particular fluorine door "

The N-aryl-nitrogen hsterocycles of the formula Ck) bind compounds according to the invention and can be obtained by means of the processes (a), (b), (c) or (i) 35 according to the invention

Le A 26 501

- 246 -

Alk \ Β for carrying out the process according to the invention Ch-oc) furthermore required as external ingredients alcohols or thiols are generally defined by the formula (IX)). In this formula (IX), R ⁹ and X preferably represent those radicals "which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention"

The alcohols and thiols of formula (IX) are well-known compounds of organic chemistry «

The (thio) phenol derivatives required for carrying out the process (h-β) according to the invention are generally defined by the formula (X). In this formula (X), R ¹ , R ³ , R ⁴ , R ⁵ and X are preferably those radicals which have already been mentioned as preferred for these substituents in connection with the description of the compounds of the formula (I).

The (thio) phenol derivatives of the formula (X) are not yet known and are likewise the subject of the invention. "

They are obtained either when N-aryl-nitrogen heterocycles of the formula (Ik),

30 ^RR

N (Ik)

Le A 26 501

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297263

in which 5

R ² ~ * is halogen, in particular fluorine and R *, R ?, r4 and F! ^{5 have} the meaning given above «

with Natriumhydrcgensulfid optionally in the presence of a diluent such as methanol "ethanol or mixtures thereof with water and optionally in the presence of a reaction aid such as NatriuiTürydroxid or potassium carbonate" given in the presence of a nitrogen or Argonschutzgasatomosphare at temperatures between O ⁰ C and 50 ⁰ C or if N-Aryl-Nitrogen Heterocycles of Formtile (II) «

: n (id

in which 25

R ¹ , R ³ "R ^ and R ^ have the meaning given above and

R ⁹ " ^{1 is} allyl or benzyl, 30

with conventional reducing agents "such as molecular hydrogen in the presence of a conventional

Le A 26 501

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Hydrogenation catalyst »such as TrimethyleiIyIiodid or Trie-Triphenylphoephin-rhodium chloride optionally in the presence of a diluent such as ethanol or dichloromethane and optionally in the presence of a reaction aid such as diazabicyclooctane (DABCO) at temperatures between 20 ⁰ C and 120 ⁰ C implemented.

N-aryl-nitrogen heterocycles of the formula (Ik) are compounds according to the invention and can be obtained by means of the processes (a), (b)> (c) or (i) according to the invention.

N-aryl-nitrogen heterocycles of the formula (II) are likewise compounds according to the invention and can be obtained by means of the processes (a), (b), (c) and (i) according to the invention.

The alkylating agents which are furthermore required as external agents for carrying out the process (h-β) according to the invention are generally defined by the formula (XI). In these forms! (XI) R ⁹ preferably represents those radicals which have already been mentioned as preferred for this substituent in connection with the description of the substances of the formula (I) according to the invention.

E 1 is preferably halogen, in particular chlorine, bromine or iodine, or each optionally substituted alkylsulfonyloxy, alkoxy

Le A 26 501

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sulfonyloxy or arylsulfonyloxy »such as methanesulfonyloxy, trifluoromethanesulfonyloxy, methoxysulfonyloxy. Ethoxyaulfonyloxy or p-To1uo1 sulfonyloxy «

The alkylation with formula (XI) are well known compounds of organic chemistry «

The N-arylpyrazolyl-4-carboxylic acid esters required as starting materials for carrying out the process (i) according to the invention are generally defined by the formula (XII). In this formula (XII), R ^1, R ^2, R ³ and R ⁵ preferably represent those resistant · already mentioned in connection with the description CISR invention substances of the formula (I) as being preferred fvir these substituents "

R ¹ 2 preferably represents tertiary or branched alkyl tait 1 to 4 carbon atoms, in particular methyl or ethyl ·

The N-arylpyre.zolyl-4-carboxylic acid esters of the formula (XII) are not yet known.

They are obtained »when acrylic ester derivatives of the formula (XIX),

3

I COOR ¹²

R ¹⁴ -C "C <(Xi">

, CR ⁵

Il ο

Le A 26 501

in which 5

R ³ , R ⁵ and R ^{12 have} the abovementioned meaning and

R ** for an alkoxy-chain or for a dialkylaminoreet with. in each case 1 to 4 carbon atoms in the *** individual geradkett.igen or branched alkyl parts, in particular with in each case 1 to 2 carbon atoms in the individual alkyl parts stands «

with 4-cyanophenylhydrazines of the formula (II)> 15

(Ii)

in which

R ¹ and R ^{2 have} the meaning given above

optionally in the presence of a diluent 25

such as ethanol or ethylene glycol monoethyl ether and optionally in the presence of a reaction aid agent wio example, hydrochloric acid or sulfuric acid at temperatures between 20 ⁰ C and 150 ⁰ C is reacted ·

Acrylic ester derivatives of the formula (XIX) are known or obtainable in analogy to known processes (cf., e.g.

Le A 26

- 251 - 23? 36 3

EP 257 882; JP 62/148482; PCT Int. Appl. WO 86/1202; EP 188,094; US 4,555,517; EP 104 432; J. org, Chera. 49, 140-152 [1984]; Austral. J. Chem. 34. * 2401-2421 [1981]; BE 888 389; US 4,277,418; Farmaco. Ed, Sei. 34 »898-906 • [1979]; J, chem. Soc. Perkin Trans, 1, 1979 ; 464-471; J, chem, Soc. Perkin Trans, 1, 1978 . 1041-1046).

Suitable diluents for carrying out the process (a) according to the invention are inert organic solvents. These include, in particular, aliphatic or aromatic, optionally halogenated Kohlan hydrogens, such as, for example, benzene, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, ethers, such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether , Nitriles such as acetonitrile or propionitrile, amides such as dimethylformamide, Diniethylacetamid, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide, esters such as ethyl acetate, sulfoxides such as dimethyl sulfoxide, alcohols such as methanol, ethanol or propanol or

2 pounds of acids, like acetic acid,

If appropriate, the process (a) according to the invention is carried out in the presence of a suitable reaction auxiliary. As such, inorganic mineral acids, for example hydrochloric acid or sulfuric acid, are particularly suitable. It is also possible to use the 4-Cyanophenylhydrazine in question as starting materials

Le A 26 501

of the formula (II) in the form of corresponding acid addition salts "such as hydrochlorides"

The Reaktionstemperatvren can be varied in carrying out the process (a) according to the invention in a wider range. "In general, one operates at temperatures between -20 ⁰ C and 180 ⁰ C, preferably at temperatures between 20 ⁰ C and 120 ⁰ C,

For carrying out the process (a) according to the invention, 4-cyanophenylhydrazine of the formula is employed per mole of 4-cyano-phenylhydrazine

(II) or "to a corresponding acid addition salt in general 0.5 to 10.0 moles of 1,3-D.lketon of the formula

(III) or to a corresponding derivative and optionally from 0.01 to 1.0 mol of reaction auxiliary.

The reaction, workup and isolation of the N-aryl-nitrogen heterocycles of the formula (Ia) is carried out according to generally conventional methods (see also the Herstellungsbeiepiele).

When using 1,3-diketones of the formula (III) in which the substituent R * ~ * is different from the substituent Fc ", isomer mixtures of compounds of the formula (IaI) are generally obtained,

_R4 -l _R5 -l _F l 30

(IAI)

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and compounds of the formula (Ia2)

(Ia2)

in which

R ¹ , R ² , R ³ "R ⁴ " ¹ and R ⁵ " ¹ each have the meaning given above"

With the aid of these isomer mixtures, the desired reaction products of the formula (Ia) can be isolated by customary separation processes (distillation "crystallization" chromatography).

As halogenating agent for carrying out the invention

Conventional halogenating agents are suitable according to process (b). Sulfuryl chloride is particularly preferably used as elemental chlorine or elemental

Bromine as halogenating agent, 25

Suitable diluents for carrying out the process (b) according to the invention are inert organic solvents. These include in particular aliphatic «« vlicyclische or aromatic «optionally

halogenated hydrocarbons such as benzene benzene toluene xylene chlorobenzene o-dichlorobenzene petroleum ether hexane cyclohexane dichloromethah chloroform or carbon tetrachloride

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The reaction temperatures can be varied within a substantial range when carrying out the process (b) according to the invention. In general, one works at temperatures between O ⁰ O and 150 ⁰ C, preferably at temperatures between 35 ⁰ C and 70 ⁰ C.

For carrying out the process according to the invention (b), in general from 1.0 to 5.0 mol of preferably 1.0 to 2.0 mol of halogenating agent are employed per mole of N-aryl-nitrogen-containing heterocycle of the formula (Ij). The reaction is carried out by working up and isolation of the reaction products by generally customary methods (see also the Preparation Examples).

Suitable halogenating agents for carrying out process (c) according to the invention also include conventional halogenating agents. With particular preference to use inorganic acid halides such as phosphorus oxychloride »thionyl chloride, phosgene, phosphorus tribromide or diphosphanes (Cl ₃ CO-CO-Cl).

Suitable diluents for carrying out the process (c) according to the invention are inert organic solvents. These include in particular aliphatic alicyclic or aromatic "optionally halogenated hydrocarbons" such as gasoline "benzene" toluene »xylene» chlorobenzene »0-dichlorobenzene« petroleum ether »hexane« cyclohexane »dichloromethane» chloroform or carbon tetrachloride or basic diluents such as pyridine. It is

Le A 26 501

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also "possible to use a corresponding excess of halogenating agent at the same time as a diluent"

The process (c) according to the invention is preferably carried out in the presence of a suitable reaction auxiliary. "Suitable such compounds are in particular customary auxiliary nucleophiles, for example triphenylphosphine" dimethylaniline or dimethylformamide "

The reaction temperatures can be varied within a substantial range when carrying out process (c) according to the invention. In general, one works at temperatures between ^{0 0} C and 200 ⁰ C, preferably at temperatures between 30 ⁰ C and 150 ⁰ C,

For carrying out process (c) according to the invention, 1.0 to 10.0 mol of preferably 1.0 to 5.0 mol of halogenating agent and optionally 0.01 to 1.0 are generally employed per mole of N-arylpyrazolinone of the formula (IV) Mol, preferably 0.05 to 0.1 mol

Reaction aids.

The reaction procedure "work-up and isolation of the reaction products by generally customary methods (see also the preparation examples).

Suitable diluents for carrying out process (d) according to the invention are inert organic solvents. These include in particular aliphatic alicyclic or aromatic "optionally

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halogenated hydrocarbons "such as benzene" benzene "toluene" xylene "chlorobenzene" petroleum ether "hexane" cychexane "dichloromethane" chloroform "carbon tetrachloride" ether "such as diethyl ether" dioxane "tetrahydrofuran or ethylene glycol dimethyl or diethyl ether" ketones such as acetone or butanone "nitriles" such as acetonitrile or propionitrile "amides" such as dimethylformamide, dimethylacetamide "N-methylformanilide" N-mothylpyrrolidone or hexamethylphosphoric acid triamide "esters such as ethyl acetate" sulfoxides "such as dimethyine sulfoxide or alcohols" such as methanol "ethanol or propanol"

The reaction temperatures can be varied within a substantial range "in carrying out the process (d) In general," carried out at temperatures between ⁰ ° C and 180 ° C preferably at temperatures between 50 ⁰ C and 150 ⁰ C *

For carrying out the process (d) according to the invention, in general from 10 to 3 mols, preferably 1.0 to 2.0 mols, of iminocarbon ester of the formula (V) are employed per mole of 4-cyanophenylhydrazine of the formula (II) The reaction is carried out "Working up and isolation of the reaction products is carried out in accordance with generally customary methods (see also the preparation examples)."

For carrying out the process (s) according to the invention, suitable inert diluents are "organic solvents". Aliphatic is preferably used

Le A 26 501

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cyclic or aromatic "optionally halogenated hydrocarbons" such as gasoline "benzene" toluene "xylene" pentane "hexane" heptane "cyclohexane" petroleum ether "ligroin" methylene chloride "chloroform" carbon tetrachloride "chlorobenzene or dichlorobenzene" ethar "such as diethyl ether" diisopropyl ether "dioxane" tetrahydrofurin or ethylene glycol diethyl ether or dimethyl ether "ketones" such as acetone "butanone" methyl isopropyl ketone or methyl isobutyl ketone "esters" such as ethyl acetate "nitriles" such as acetonitrile or propionitrile or amides "such as dimethylformamide" dimethylacetamide "N-methylpyrrolidone or hexamethylphosphoric acid triamide" If alkylating agents of the formula ( VI) in liquid form "so it is also possible" to use these in a corresponding excess simultaneously as a diluent «

Suitable reaction auxiliaries for carrying out the process (e) according to the invention are all customarily usable inorganic and organic bases. "Preference is given to using alkali metal hydrides" hydroxides "-amides" carbonates or bicarbonates "such as, for example, sodium hydride" sodium amide "sodium hydroxide" sodium carbonate "or potassium carbonate Sodium hydrogencarbonate "or tertiary amines" such as triethylamine "N" N-dimethylaniline "pyridine" 4- (N, N-dimethylamino) -pyridine "diazabicyclooctane (DABCO)" diazabicyclononene (DBN) or diazabicycloundecene (DBU) "

L e A 26 501

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The reaction temperatures can be varied in a wider range when carrying out the production process (e). In general, one works zwiochen -20 ⁰ C and +150 ⁰ C * preferably between ^{0 0} C and ♦ 100 ⁰ C.

In order to carry out process (e) according to the invention, in general from 10 to 15 mol per mole of N-aryl-nitrogen-heterocycle of the formula (Id) are used, preferably from 0 to 5.0 mol of alkylating agent of the formula (VI) 1.0 to 3.0 MoI _1, preferably 1.0 to 2.0 moles of reaction auxiliary.

The reaction procedure "work-up and isolation of the reaction products by generally customary methods (see also the preparation examples).

Ale diluents for carrying out the processes (f) and (g) according to the invention are suitable inert organic solvents. These include in particular aliphatic alicyclic or aromatic "optionally halogenated hydrocarbons" such as gasoline "benzene" toluene "xylene" chlorobenzene "0-dichlorobenzene" petroleum ether "hexane" cyclohexane "dichloromethane" chloroform or carbon tetrachloride.

The processes (f) and (g) according to the invention are preferably carried out in the presence of a suitable reaction auxiliary. Ale such are all common bases in question. Tertiary amines, such as triethylamine, N, N-dimethylaniline, are particularly preferred.

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Pyridine, Ν, Ν-diraethylaminopyridine, diazabicyclooctane (DABCO) ₁ diazabicyclononene (DBN) or diazabicycloundecene (DBU),

The reaction temperatures can be varied within a substantial range "in general carried out at temperatures between -20 ⁰ C and 160 ⁰ C in carrying out the process (f) and (g) according to the invention, preferably at temperatures between ⁰ C and 150 ⁰ C. .

To carry out the process (f) according to the invention, in general 1.0 to 5.0 mol, preferably 1.0 to 1.5 mol, of phosgene and optionally 1.0 to 5.0 mol are employed per mole of amidrazone of the formula (VII). preferably 1.0 to 3.0 moles of reaction auxiliary.

The Reaktionscomplication «workup and isolation of the reaction products by generally accepted methods.

In order to carry out process (g) according to the invention, in general 1.0 to 5.0 mol of preferably 1.0 to 1.5 mol of phosgene and optionally 1.0 to 5.0 mol are employed per mole of phenylhydrazide of the formula (VIII) Preferably, 1.0 to 3.0 moles of reaction auxiliaries.

The reaction procedure "processing and isolation of the reaction products is carried out according to generally customary methods (see also the Heratellungsbeispiele),

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Suitable diluents for carrying out the process according to the invention (h-10 are inert organic solvents · These include, in particular, aliphatic alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, benzene «toluene» xylene «chlorobenzene, petroleum ether« HeXBn ₁ cyclohexane ₄ dichloromethane, Chloroform "carbon tetrachloride" ether "such as diethyl ether" dioxane "tetrahydrofuran or ethylene glycol dimethyl or diethyl ether" ketones such as acetone or sr butanone "nitriles such as acetonitrile or propynitrile, amides" such as dimethylformamide "dimethylacetamide"N-methyl'if ormanil id "N -Methylpyrrolidone or Hexamethylphoephorsauretriamid, esters "such as ethyl acetate or sulfoxides" such as dimethyl sulfoxide "It is also possible as the reactants in question alcohols of the thiols of the formula (IX) in a corresponding, excess at the same time to use as a diluent

The process (ha) according to the invention is preferably carried out in the presence of a suitable reaction solvent. "Suitable are all customary inorganic and organic bases." Preference is given to using alkali metal hydrides, hydroxides, amides, alkoxides or carbonates, for example sodium hydride. Sodium niide, sodium hydroxide "potassium hydroxide" sodium methylate "sodium ethylate" potassium t-butylate or potassium carbonate or tertiary amines "such as triethylamine" N "N"

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Dimethylitnilin "pyridine, N, N-dimethylaninopyridine, diazabicyclooctane (DABCO)" diazabicyclononene (OBN) or oiazabicycloundecene (DBU),

The reaction temperatures can be varied within a substantial range when the process according to the invention is carried out (h- <x). In general, one works at temperatures between ^{0 0} C and 150 ⁰ C, preferably at temperatures between 20 ⁰ C and 120 ⁰ C,

For carrying out the process (ha) according to the invention, in general 1.0 to 3.0 mols, preferably 1.0 to 1.5 mols, of alcohol or thiol of the formula (IX) and 1.0 to 3.0 mols are added per mole of N-aryl-nitrogen-heterocycle of the formula (Ik). preferably 1.0 to

2.0 moles of reaction auxiliaries. The Reakti.onsdurchftihrung «workup and isolation of the reaction products by generally customary methods (see also the preparation examples).

Suitable diluents for carrying out the process (h-β) according to the invention are inert organic solvents. Preferably, aliphatic alicyclic or aromatic "optionally halogenated hydrocarbons" such as gasoline "benzene" toluene "xylene" pentane "hexane" heptane "cyclohexane" petroleum ether «ligroin« methylene chloride «chloroform« carbon tetrachloride «chlorobenzene or« ether «such as diethyl ether« diisopropyl ether "

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Dioxane, tetrahydrofuran or ethylene glycol diethyl ether or dimethyl ether, ketones such as acetone butanone, methyl isopropyl ketone or methyl isobutyl ketone, esters such as ethyl acetate, acids such as acetic acid, nitriles such as acetonitrile or propionitrile amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone or Hexamethylphosphoric Acid Triamide "If one uses all reactants alkylating agent of the formulas (VI), (VII) or (XI) in liquid form, it is also possible to use these in a corresponding excess simultaneously as a diluent.

Suitable reaction auxiliaries for carrying out the process (h-β) according to the invention are all customary inorganic and organic bases. It is preferred to use alkali metal hydrides, hydroxides, amides, carbonates or bicarbonates, for example sodium hydride, sodium amide, sodium hydroxide, sodium carbonate or Sodium hydrogencarbonate "or else tertiary amines" such as triethylamine "Ν, Ν-dimethylaniline, pyridine, 4- (N, N-dimethylamino) -pyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU),

The reaction temperatures in the process of the invention (h-ß) can be varied within a substantial range "in general carried out between -20 ⁰ C and + 150 ⁰ C, preferably between ⁰ ° C and + 100 ⁰ C.

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To carry out the process (h-ß) is used per mole of (thio) phenol derivative of the formula (X) is generally 1.0 to 20.0 mol, preferably in each case 1.0 to 15.0 mol, of alkylation or "Acylating agent of the formula (XI) and optionally 1.0 to 3.0 mol, preferably 1.0 to 2.0 mol of reactions! Ifsmittel, a" The Reaktionsdurchflihrung, workup and isolation of the reaction products of formula (Ih) is carried out according to customary methods "

Suitable diluents for carrying out the process (i) according to the invention are inorganic or organic solvents. It is preferred to use polar solvents, in particular alcohols, such as, for example, methanol, ethanol or propanol, or mixtures thereof with water

Suitable reaction auxiliaries for carrying out process (i) according to the invention are all catalysts customarily used for such ester saponifications and decarboxylations. Preferably bases are used, for example sodium hydroxide, sodium alcoholate or sodium carbonate or acids, for example hydrochloric acid, hydrobromic acid or sulfuric acid.

When carrying out the process (i) according to the invention, the reaction temperatures can be varied within a substantial range. In general, one works at temperatures between 2Q ⁰ C and 250 ⁰ C, preferably at temperatures between 50 ⁰ C and 150 ⁰ C,

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To carry out process (i) S according to the invention, in general 1.0 to 15.0 mol of arylpyrazolyl-4-carboxylic acid ether of the formula (XII) are used, preferably 1.0 to 2.5 molar equivalents per mole. acidic or basic reaction auxiliary and heated for several hours to the required reaction temperature. The work-up and isolation of the reaction products by generally customary methods.

Depending on the reaction temperature and the reaction time, it is also possible to isolate the intermediately occurring 1-arylpyrezolyl-4-carboxylic acids and to decarboxylate them in a separate reaction step.

The active compounds according to the invention can be used as defoliants "desiccants" herbicides and especially as weedkillers. Weeds in the broadest sense are understood to mean all plants that "grow up in places" where they are undesirable. Whether the substances according to the invention act as total or selective herbicides «depends essentially on the amount used.

The active ingredients according to the invention can e.g. to be used in the following plants: 30

Dikotvle weeds of the genera? Sinapis "Lepidium" Galium "Stellaria" Matriceria, Anthemis "Galinsoga" Cheno-

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podium »Urtica« Senecio, Amaranthus, Portulacai Xanthium «Convolvulus, Ipomoea» Polygonum «Sesbania, Ambrosia, Cirsium, Carduus« Sonchus »Solarium, Rorippa« Rotala «Lindf? rnia« Lamium, Veronica «Abutilon, Emex, Datura« Viola ,, Galeopeie, Papaver «CenLaurea,

Dikotvle cultures of the genera: Gosaypium "Glycine, Beta" DaucuB, Phaseolus, Piaum, Solanum, Linum, Ipomoea, Vicia "Nicotiana, Lycopersicon, Arachis" Brassica, Lacvuca, Cucumis, Cucurbita "

Monocotyledonous weeds of the genera} Echinochloa, Setaria, Panicum, Digitaria, Phleum «Poa, Festuca» Eleusine, Brachiaria, Loium, Broraue, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis «Sagittaria, Eleocharis, Scirpue, Paspalum, Iachaemum , Sphenoclea «Dactyloctenium« Agrostis, Alopecurue, Apera «

Monocot cultures of the genera; Oryza, Zea, Triticum, Hordeum, Avene, Secnle "Sorghum, Panicum, Saccharum" Pineapple "Asparagus, i \ llium"

However, the use of the active compounds according to the invention is by no means restricted to these genera "but extends equally to other plants."

The compounds are useful depending on the concentration for Totalunkrünfbtzäznpfung, for example. on industrial and railway tracks and on paths and squares

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and without tree cover. "Likewise, the weed control compounds may be used in permanent crops" e.g. Forest "ornamental, fruit" wine "citrus" nut, banana, coffee "tea" "rubber" oil palm, cocoa, berry fruit and hop plants and used for selective weed control in annual crops «

In this case, the active compounds of the formula (I) according to the invention can be used to combat dicotyledonous weeds in monocotyledonous and dicotyledonous crops, such as, for example, soybeans or wheat, with particular success. "The intermediates of the formula (X) also have good herbicidal activity."

In addition, the active compounds according to the invention intervene in the metabolism of the plants and can therefore be used as growth regulators. «

For the mode of action of plant growth regulators, according to previous experience, an active substance can also exert several different effects on plants. The effects of the substances depend essentially on the time of application in relation to the stage of development of the plant and of the plants or their plants The amount of active substance applied and the type of application "In any case, growth regulators are supposed to influence crops in a specific way"

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Under the influence of growth regulators, plant leaf foliage can be controlled "to achieve defoliation of the plants at a desired time." Such defoliation plays a major role in the mechanical harvesting of cotton, but is also important in other crops, e.g. in viticulture to facilitate the harvest of interest · Kine defoliation of plants can also be undertaken to minimize the transpiration of plants before transplanting «

The active ingredients can be converted into the usual formulations

«how solutions« emulsions «spray powders« suspensions «powders« dusts »pastes« soluble powders «granulates« suspension emulsion concentrates «active ingredient-impregnated natural and synthetic substances as well as microencapsulations in polymeric substances«

These formulations are prepared in a known manner by mixing the active compounds with extenders, ie liquid solvents and / or solid carriers, if appropriate with the use of surface-active agents, ie emulsifiers and / or dispersants and / or foam-forming agents.

In the case of using water as an extender, e.g. organic solvents can also be used as auxiliary solvents "As liquid solvents, aromatic hydrocarbons such as xylene

Le A 26 501

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2S? 9t> 3>

Toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride aliphatic hydrocarbons such as cyclohexane or paraffins; Petroleum fractions "mineral and vegetable oils" alcohols "such as butanol or glycol and their ethers and esters" ketones such as acetone "methyl ethyl ketone" methyl isobutyl ketone or cyclohexanone "strongly polar solvents" such as dimethylformamide and dimethyl sulfoxide "and water,

Suitable solid carriers are:

z, B, ammonium salts and natural flours "like kaolin" Clay "talc" Chalk "quartz" Attapulgite "montmorillonite or diatomaceous earth and synthetic minerals" such as finely divided silica "alumina and silicates" as solid carriers for granules: z "B" crushed and fractionated natural rocks such as calcite "marble" pumice "sepiolite" dolomite and synthetic granules of inorganic and organic flours, and granules of organic material such as sawdust "coconut shells" corn cobs and tobacco stalks; suitable emulsifiers and / or foam formers are: e.g. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid ethers, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers "alkylsulfonates" alkylsulfates "aryl sulfonates and protein hydrolysates; suitable dispersants are: e.g. Lignin-sulphite liquors and methylcellulose.

It can in the formulations adhesives such as carboxymethylcellulose «natural and synthetic powdery« 35

Le A 26 501

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2973 * 3

granular or latex-form polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese,

Boron, copper, cobalt, molybdenum and zinc are used. 15

The formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%,

The active compounds according to the invention can be used for herbicides as such or in their formulations also in admixture with known herbicides for controlling weeds, ready-to-use formulations or tank mixes being possible »25

For the mixtures, known herbicides such as e.g. 1-amino-6-ethylthio-3- (2,2-dimethylpropyl) -1,3,5-triazine-2,4 (1H, 3H) -dione (amothydione) or N- (2-benzthiazolyl) -N, N'-dimethylurea (metabenzthiazuron) for weed control in cereals; 4-Amino-3-methyl-6-phenyl-l, 2,4-triazine-5 (4H) -one (metamitron) for weed control in sugar beet and 4-amino-6- (1,1-dimethylethyl) -3- methylthio-l, 2,4-triazine-5 (4H) -one (metribuzin) to weed

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Combination in soybeans "in question" Also mixtures with 2 * 4-dichlorophenoxyacetic acid (2,4-D); 2,4-dichlorophenoxypropionic acid (2,4-DP); 4- (2,4-dichlorophenoxy) -butanoic acid (2,4-DB); (2-methyl-4-chlorophenoxy) acetic acid (MCPA); (4-chloro-2-methylphenoxy) -propionic acid (MCPP); [(4-amino-3 _# 5-dichloro-6-fluoro-2-pyridinyl) -oxy] -acetic acid or its 1-methylheptyleeter (FLUROXYPYR); 2- [4- (2,4-dichlorophenoxy) -phenoxy] -propionic acid

Methyl or its ethyl ester (DICLOFOPCMETHYL]);

2- {4 - [(6-chloro-2-benzoxazolyl) oxy] -phanoxy} -propanoic acid, its methyl or ethyl ester (FENOXAPROP);

Methyl 5- (2,4-dichlorophenoxy) -2-nitrobenzoate (BIFENOX); Chloroacetic acid-N-dinethoxymethyl) -2,6-diethylanil id

(Alachlor);

2-chloro-N- (2,6-dimethyl-phenyl) -N-C (IH) -pyrazol-1-yl-methyl] -acetamide (METAZACHLOR);

2-Ethyl-6-ethyl-N- (1-methyl-2-methoxyethyl) chloroacetanilide (METOL &CHLOR);

N- (l-ethylpropyl) -3,4-dimethyl-2,6-dinitroaniline

(PENDIMETHALIN); 2,6-dinitro-4-trifluoro-ethyl-N, N-dipropylaniline (TRIFLURALINE);

N _> N-dimethyl-N '- (3-chloro-4-methylphenyl) -harneteate

(CHLORTOLÜRON);

Ν, Ν-dimethyl-N '- (4-i-propylphenyl) urea (ISOPROTURONE); 2-C4 _# 5-dihydro-4-methyl-4-isopupryl-5-oxo (1H) -imidazol-2-yl] -5-ethyl-pyridine-3-carboxylic acid (IMAZETHAPYR);

Methyl 2- [4,5-dihydro-4-methyl-4- (1-methylethyl) -5-IH-oxü

imidazol-2-yl _(] -4 (5) -methylbenzoate (imazamethabenz);

Le A 2 6 501

2- [5-Methyl-5- (1-methylethyl) -4-oxo-2-ira-diazolin-2-yl] -3-quinolinecarboxylic acid (IMAZAQUIN) j

3,5-dibromo-4-hydroxybenzonitrile (BROMOXYNIL); 3,5-diiodo-4-hydroxybenzonitrile (IOXYNIL); N-methyl-2- (1,3-benzthiazol-2-yloxy) -acetanilide (MEFENACET);

Ethyl 2- {C (4-chloro-6-methoxy-2-pyrimidinyl) -aminocarbonyl] araino-sulfonyl} -benzoate (CHLORIMURONE); 2-chloro-N- {C (4-methoxy-6-methyl-1,3-> 5-tria2in-2-yl) τamino] -carbonyO-benzenesulfonaraid (CH3 LORSULFURONE); 2 - {[[((4-methoxy-6-methyl-l _i 3 _{<5-triazin-2-yl)} amino) carbonyl] amino] -8ulfonyl} -benzoic acid or its Methylester (metsulfuron);

3 - [[[C (4-methoxy-6-methyl-l _# 3 _{<5-triazin-2-yl)} amino] carbonyl 3 amino] sulfonyl 3-t '\ iophen-2-carboxylic acid methyleeter ( THIAMETHURON);

N, N-Diieopropyl-S- (2 _<i 3 3-trichloroallyl) -thiolcarbamat (triallate);

4-ethylamino-2-t-butylamino-6-methylthio-8-triazine (TERBUTRYNE); 3-isopropyl-2'-1 '3-benzothiadiazin-4-one-2'-dioxide (BENTAZON);

4-amino-6-t-butyl-3-ethylthio-1, 2,4-triazine-5 (4H) -one (EtHIOZIN);

2-C (2-chlorophenyl) methyl] -4 <4-dimethylieoxazolidin-3-one [DIMETHAZONE];

exo-1-methyl-4- (1-methylethyl) -2- (2-methylphenylmethoxy) -7-oxabicyclo- (2,2, l) -heptene (CINMETHYLIN) and 0- (6-chloro-3-) Phenyl-pyridazin-4-yD-S-octyl-thiocarbpate (PYRIDATE) are possible. Some mixtures surprisingly also show a synergistic effect.

Le A 26 501

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It is also possible to combine it with other known active substances such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and soil conditioners.

The active substances can be applied as such "in the form of their formulations or the forms of use prepared therefrom by further dilution" such as ready-to-use solutions "suspensions" emulsions "powders" pastes and granules. "The application is carried out in the usual way" by casting "spraying »Spraying» Sprinkling «

The active compounds according to the invention can be applied both before and after emergence of the plants. «

Si * may also be incorporated into the soil before sowing: the «

The amount of active substance applied may vary over a wider range when used as herbicides. "It depends essentially on the type of effect desired. In general, the application rates are between 0 _Λ 01 and 10 kg of active ingredient per hectare of soil surface, preferably between 0 and 5 kg per hectare.

When used as growth regulators in the formulations, the active compounds according to the invention can also be mixed with other known active compounds

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"fungicides * insecticides" acaricides and herbicides as well as in mixtures with fertilizers and other growth regulators,

The active ingredients can be used as such * in the form of their formulations or the resulting application forms such as ready-to-use solutions, emulsifiable concentrates, emulsions, foams, suspensions, wettable powders, pastes, soluble powders, and granules. The application is done in the usual way "z, B. by pouring "spraying" spraying "scattering" dusting "foaming * brushing U8W" · It is also possible * to apply the active ingredients according to the ultra-low-volume method or to inject the active ingredient preparation or the active ingredient itself into the soil the seed of

Treated plants,

The application rates can also be varied within a relatively wide range when used as growth regulators. In Ugernein, 0 * 01 to 50 kg of active ingredient per hectare of soil surface are used, preferably 0 * 05 to 10 kg.

For the period of application, * the application of the growth regulators shall be carried out in a preferred period of time "the exact delimitation of which depends on the climatic and vegetative conditions,

Le A 26 501

, ₂₇₄

Manufacturing Example BDXele Example 1 / ^CH 3 ^F _N

CH ₃ F

(Method a) 15

21 * 1 g (0 ^ 125 mol) of 4-cyano-2,5-ce if luorphenylhydrazin and 12.5 g (O, 125 μl) of 2,4-pentanedione are stirred for 2 hours at room temperature in 250 ml of ethanol. The mixture is then heated at 70 ^° C. for 15 hours and then concentrated in vacuo. The residue is stirred with petroleum ether and filtered with suction.

This gives 28 g (96 % of theory) of 4- (3, S-dimethyl-J.- ₂ c pyrazolyl) -2 | 5-difluorobenzonitrile of melting point 122 ⁰ C.

Le A 26

275 -

19? 9

Example 2

(Method a)

To 6.76 g (0.04 mol) of 4-cyano-2,5-difluorophenylhydrazine in 40 ml of glacial acetic acid are added 5.2 ml (0.04 mol) of 2-acetylcyclohexanone (see, for example, J 'org, Chem, 3jl , 14 / 15-1429 [1969]), stirred for 2 hours at room temperature, then stirred the Beaktionsmischung in 250 ml of ice water, extracted with dichloromethane, dried over sodium sulfate, concentrated in vacuo and the residue crystallized from dichloromethane / n-hexane to «

3.21 g (23.5 % of theory) of 4- (5-methyl-3,4-tetramethylene-1-pyrazolyl) -2,5-difluorobenzonitrile are obtained

of melting point 120 ^° C. 25

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Example 3 5

Cl CH ₃ F

CH ₃ F

(Method b)

To 2.3 g (0.01 mol) of 4- (3,5-diirylthyl-1-pyrazolyl) -2,5-difluorobenzonitrile in 50 ml of dichloromethane are added 1.68 g (»1 ml, 0.012 mol). Sulphuryl chloride, stirred for hours at 35 ^° C., allowed to come to room temperature, dried over sodium sulphate, concentrated in vacuo, and the residue is purified by stirring with petroleum ether.

2.0 g (75 X of theory) of 4- (3,5-dimethyl

4-chloro-l-pyrazolyl) -2,5-difluorobenzonitrile of melting point 153 ⁰ C ₁

Le A 26

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29996b

Example 5

(Method c)

To 15 g (0.068 mol) of 1- (4-cyano-3-fluorophenyl) -3,4-tetramethylene (1H, 4H) -pyrazolin-5-one in 28.8 ml (0.2 mol) of phosphorus oxychloride are added 1.78 g (0.0068 mol) of triphenylphosphine and heated to reflux for 15 hours. For workup, the cooled R ^ action mixture is added to 300 ml of ice water, stirred for 1 hour, precipitated product is filtered off with suction, washed with water

and dried «20

This gives 15.2 g (81 X of theory) of 1- (4-cyano-3-fluorophenyl) -5-chloro-3,4-tetramethylenepyrazole of melting point 84-86 ⁰ C.

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Example 5 5

(Method d)

8.45 g (0.05 mol) of 4-cyano-2,5-difluorophenyl hydrazine and

12 g (0.078 mol) of N-ethoxycarbonylethanimidric acid, ethyl-15

esters (cf., for example, Chem. Ber., Ü 9, 2444-2457 [1986]) are heated to reflux temperature in 50 ml of xylene for 8 hours, then cooled to room temperature, filtered off with suction and quenched with dichloromethane / petroleum ether,

This gives 5.91 g (50 % of theory) of 1- (4-cyano-2,5-)

difluorophenyl) -3-methyl-4 _# 5-dihydro-l _# 2,4-triazolin-5-one of melting point 174 ^° C.

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Example 6 5

(Method e)

2.36 g (0.01 mol) of 1- (4-cyano-2,5-difluorophenyl) -2- <c methyl-4,5-dihydroxy-1,2,4-triazolin-5-one and 1, 52 g

(0.011 mol) of potassium carbonate in 20 ml of acetonitrile are heated for 2 hours at reflux temperature, then cooled to 25 ⁰ C, treated with an 80 percent solution of 1.31 g (0.011 mol) of propargyl bromide in toluene 2Q and heated for further 4 hours at reflux temperature.

For workup, the mixture is concentrated in vacuo, the residue taken up in dichloromethane, washed with saturated aqueous sodium bicarbonate and water, dried over sodium sulfate, concentrated in vacuo and recrystallized from dichloromethane / petroleum ether.

2.16 g (79 % of theory) of 1- (4-cyano-2,5-difluorophenyl-3-methyl-4-propargyl-4,5-dihydro-1,2,4-triazoline-5- on of the melting point 127 ⁰ C,

Le A 26

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199363

Example '/ 5

C (CHg) ₃

^{3 3}

(Method g)

Into a solution of 20.24 g (0.08 mol) of 1-M-cyano-2,5-difluorophenyl) -2-pivaloylhydrazine in 200 ml of toluene are introduced 11 * 9 g (0 * 12 mol) of phosgene * then dropwise with stirring 24.24 g (0 * 24 mol) of triethylamine in 20 ml of toluene and heated to 100 ⁰ C for one hour. "For workup, remove excess phosgene, precipitated Triethylaminhydrochlorid filtered off * concentrated in vacuo and the residue crystallized from dichloromethane / Petroleum ether around «

This gives 14 * 33 q (64 X of theory) of 3- (4-cyano-2 * 5-difluorophenyl) -5-t-butyl-l * 3 * 4-oxadiazolin-2-one of melting point 137 ⁰ C.

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137963

Example 8 5

Cl CHo F

0-CH ₂ -CH ₂ -OC ₂ H ₅ (method h-oO

To 2.7 (0.01 mol) of 4- (3,5-dimethyl-4-chloro-l-pyrazolyl) -jc 2,5-difluorobenzonitrile in 50 ml of ethylene glycol monomethyl ether are added at 0 ⁰ C 0.8 g (0.025 mol 80% sodium hydride (in paraffin oil), stirred for 4 hours at ^{0 0} C and then for 15 hours at room temperature for workup is slowly added while cooling 200 ml of water 2Q, stirred for one hour at room temperature, filtered off precipitated solid, washed with water and dry «

This gives 3.2 g (95 X of theory) of 4- (3,5-dimethyl-4-chloro-1-pyrazolyl) -2- (2-ethoxyethoxy) -5-fluorobenzonitrile melting point of 86 ⁰ C.

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Example 9 5

(Method h-cx)

To 3 g (0.011 mol) of 4- (5-methyl-3; 4-tetramethylene-lpyrazolyl) -2,5-difluorobenzonitrile in 30 ml of absolute acetonitrile are added successively 1.02 ml (0.011 mol) of isopropyl mercaptan and 0.84 g (0.015 mol) powdered potassium hydroxide · Subsequently, the mixture is stirred at 40 ⁰ C until no in the thin-layer chromatogram

Output product is more detectable, then with

Dichloromethane and filtered "The filtrate is concentrated in vacuo, the residue on silica gel (eluent: cyclohexane / ethyl acetate 3: 1) and chromatographed from η-hexane recrystallized"

This gives 1.7 g (47 X of theory) of 4- (5-methyl-3,4-tetramethylene-l-pyrazolyl) -5-fluoro-2-isopropylthiobenzonitrile of melting point 105 ⁰ C,

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Example 10

CH ₃

0-CH ₂ -CH ₂ -OC ₂ H ₅

(Method h-a)

To 0.51 g (0.017 mol) of sodium hydride in 30 ml of N-methylpyrrolidone are added dropwise at room temperature with stirring 1.7 ml (0.017 mol) of 2-ethoxyethanol, stirred for a further 15 minutes at room temperature, then 4.1 g (0.015 Mol) 4- (5-methyl-3,4-tetramethylene-l-pyrazolyl) -2,5-difluorbenzonitri1 and then stirred at 80 ⁰ C until no in the thin-layer chromatogram

Starting product is more detectable. For work-up

The cooled reaction mixture is stirred into 200 ml of ice water, extracted with toluene, dried over sodium sulfate, concentrated in vacuo, chromatographed on silica gel (eluent: cyclohexane / ethyl acetate

2: 1) and recrystallized from diethyl ether / n-hexane. «

3.51 g (66% of theory) of 4- (5-methyl-3,4-tetramethylene-1-pyrazolyl-2- (2-ethoxyethoxy) -5-fluoro

Benzonitrile of melting point 84 ⁰ C, 30

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J97963

In a corresponding manner and in accordance with the general manufacturing specifications, the following N-

Aryl-nitrogen heterocycles of the general formula (I):

CN

Hel

table

Ex. R ^J no.

He t melting point / ⁰ C

CH ₃ ^ ₁

11 F -O-CH ₂ -CH ₂ -OC ₂ H ₅ || J

103

Cl

12 H -S-CH ₂ -COOC ₂ H ₅

N-112-114

Cl

13 H -O-CH ₂ -CH ₂ -OCH ₃

14 H

0-CH ₂ -CH ₂ -OC ₂ H ₅

06-

Cl

co

69-72

N-62-64

15 H -0-CH <

CH ₂ F

chof

o6

Le A 26

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Table 1 - FortBetzuna

Ex., R ¹ R ²

No.

Hei melting point / ⁰ C

Cl

16 F F

N-112-113

Cl

17 F -S-CH ₂ -COOC ₂ H ₅

rrS

Cl

N-106-108

18 F -O-CH ₂ J-CH ₂ -OC ₂ H ₅

19 F F

N-107-109

CH-

ι / CH

TT

NW H ^

146-149

20 F OCH *

CH ₃ ^ ₁ / CH,

³ TT *

NS ^^ CHj

179-181

21 F -S-CH ₂ -COOC ₂ H ₅

136-137

22 F -O-CH ₂ -CH ₂ -OCH ₃

^CH 3 ^N 7T-7T ^ ^CH 3

₁

127-128

CH ₂ F

23 F -O-CH <

CH ₂ F ^ CH,

94-96

Le A 26

-

Table 1 - continued

Ex. R ¹ no.

Het melting point / ⁰ C

Cl

24 H -O-CH, - <25 H F 26 H F

HN ^ ⁰

Hoc ^ N ^ N

H ₃ CN ^ ⁰

123-125

246-250

181-186

27 F -O-CH ₂ -CH ₂ -O-CH ₃

2 2

28 F-O-CH ₂ -CSCH

136

29 F -O-CH ₂ -CH = CH ₂

₁ ^

H Il ¹¹⁸ N ^ N ^; ^

30 F -O-CH (CH ₃ ) ₂

Le A 26

- 287 -

Table 1 - continued

Ex. R ^J no.

Het melting point / ⁰ C

31 F -S-CH ₂ -COOC ₂ H ₅

110

32 F

33 F

-O-CH (CH ₂ F) ₂

-O-CH-COOC ₂ H ₅ CH ₃

34 F -O-CH (CH ₂ F) ₂

Ti U

H ₃ C ^ ₁ , / Cl

TT

H ₃ C ^ ρ / ΈΓ

35 F -O-CH ₂ CM ₂ -OC ₂ H ₅ || ||

110

86

116

97

36 F -S-CH ₂ -COOC ₂ H ₅

94

H ₃ C

37 F -O-CH ₂ CH ₂ -O-CH ₃

₁ • Br

TT

104

Le A 26 SOl

- 288 -

197363

Table 1 - continued

Ex. R ¹ No,

Het melting point / ⁰ C

38 F -O-CH ₂ -CH ₂ CH ₂

^ ₁

n ^ n

126

39 F -O-CH (CH ₂ F) ₂

122

40 F -S-CH ₂ -COOC ₂ H ₅ ] j |

107

4i ρ -O-CH ₂ -CSCH

HI

104

42 F -O-CH (CH ₃ ) ₂

43 F -S-CH ₂ -COOCH ₃

H ₃ CV

Il 1 108

MVN ^ VCHO

I ³

H ₃ CV,,

TTI

Il Il 103

* 3

44 F -S-CH ₂ -COOCH ₃

106

Le A 26

- 289 -

Z37963

Table 1 - continued

, R ¹ R ²

No.

Het melting point / ⁰ C

45 F -ε-CH ₂ -COOCH (CH ₃ ) ₂ yy] 135

46 F -S-CH ₂ H

120

47 F-O-CH ₂ CH ₂ OCH ₃

48 F -0-CH ₂ -C «CH

H ₃ C

Ml 112

141

49 F

0-CR ₂ CH = CH ₂

tl

120

50 F -0-C ₃ H ₇ -no

N 1

tl

99

Le A 26

- 290 - ·

Production of Ausaangsverbindunaen 5

BeiiDJel II-l To 30 g (0.19 mol) of 2,4,5-trifluorobenzonitrile (cf., e.g.

EP-A 191 181) in 120 ml of ethanol gives nan 11 g (0.22 mol) of hydrazine hydrate, heated for 2 hours at reflux temperature, cooled to room temperature, concentrated in vacuo, the residue is stirred with 50 ml of water, sucks precipitated product off and dry.

This gives 24 g (75 X of theory) of 4-cyano-2,5-difluorophenylhydrazine of melting point 158 ⁰ C.

Le A 26

- 291 -

Example II-2

H ₂ N-

To 90 g (0.65 mol) 2 _f 4-difluorobenzonitrile (cf.

EP-A 122 693) in 300 ml of methanol are added dropwise with stirring 45 g (0.9 mol) of hydrazine hydrate , heated for

3 hours at reflux temperature then concentrated in vacuo

a «stirred the Rückatand with 300 ml Waaeer, sucks and dries»

This gives 73 g (74 X of theory) of 4-cyano-3-flaorphenylhydrazin of melting point 136 ⁰ C. 20

Le A 26

- 292 -

Example II-9

H ₂ N-

To 13 g (0 * 076 mol) of 4-cyano-2'-5-difluorophenylhydrazine

in 100 nl Heihanoi van 5 g (0 * 125 mole) of powdered sodium hydroxide * then heated door 6 hours jerk-flow temperature "then concentrated in vacuo gives the residue in 50 ml watter" neutralized by dropwise addition of acetic acid, "a" aaugt precipitated Solid and crystallized from toluene to.

This gives 9 g (65 X of theory) of 4-cyano-2-fluoro-5-methoxyphenylhydrazin of melting point 155-156 ⁰ C, 20th

L «A 2 6 SOl

- 293 -

Example IV-I

To 11 g (0 (08 h)) of 4-cyano-3-fluorophenylhydrazine in ethanol, there are added nano 11 »3» 1 (0.096 mol) 2-lthoxy-

IS carbonylcyclohexanone (cf., "BJ chain" 8oc. D 1970 .

326-327) (heated for 6 hours at RUcKfluBtemperatur, then cools to 60 ⁰ C, is added to 0.5 ml of sulfuric acid, stirred for 15 hours at 60 ⁰ C ₄ then 500 al of water, the precipitated product is sucked off, "wipes ait water after and dries.

One obtains 17.7 g (99% of theory) of 1- (4-Cyano-3-fluorophenyl) -3,4-tetramethylene IH, 4H) -pyrezolin-5-one of melting point 218-220 ⁰ C. 25

Le A 26 BO l

294 -

Example VIII-1

(CH ₃ J ₃ CC-NH-NH

To 16.9 g (0.1 mol) of 4-cyano-2,5-difluorophenylhydrazine and 12.4 g (0.105 mol) of triethylamine in 50 ml of dichloromethane is added dropwise at ^{0 0} C with stirring and ice cooling 12.05 g ( 0.1 mol) pivaloyl chloride, stirred for 10 hours at 20 ⁰ C after completion of the addition, then concentrated in vacuo, the residue is partitioned between dichloromethane and water, the organic phase is dried iLer sodium sulfate and the solvent is removed in vacuo

24.85 g is obtained (98 Ά of theory) of 1- (4-cyano-2,5-difluorophenyl) -2-pivaloylhydrazin a melting point of 167 ⁰ C.

Example XI ; Melting point: 116 ^° C.

Example X-2 ! 30 CH

Melting point! > 260 ° C

Le A 26 501

- 295 -

Application Examples 5

In the following application examples, the compound shown below was used as the comparative substance:

πΓ ²

(A) Cl

CF ₃

l- (2-chloro-4-trifluoromethylphenyl) -5-methyl-4-nitropyrazole

(known from EP-A 200 872 / Example 19) 25

Le A 26 501

- 296 -

197363

Example A Prβ-emergence Teat Solvent! 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with Wasoer to the desired concentration.

Seeds of the test plants are sown in normal soil and watered after 24 hours with the preparation of active ingredient. "It is advisable to keep the amount of water per unit area reasonably constant, the drug concentration in the preparation does not matter, only the application rate of the active ingredient per unit area is crucial. After three weeks, the degree of damage to the plants is rated in X damage in comparison to _{development, he} d untreated control "where:

OX- no effect (like untreated control) 100 X = total destruction

A clear superiority in the effectiveness as well as in the crop selectivity over the prior art zoigen in this test, for example, the compounds according to the Heretellungsbeispielen 10 «14. 16, 17. 18 and

23. '35

Le A 26 501

° Example B

Poat-emergence Teet Solvent: 5 parts by weight acetone Emulsifier! 1 Gowichtsteil alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent. The stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

With the preparation of active compound is injected test plants, which have a height of 5 - 15 cm so that the particular desired amounts of active ingredient per unit area are applied. The concentration of the spray mixture is chosen so that the respective desired amounts of active substance are applied in 2000 1 of water / ha. After three weeks, the degree of damage of the plants is rated in % S damage in comparison to the development of the untreated control.

OX = no effect (like untreated control)

100 X = total annihilation 30

Significant superiority in efficacy as well as in the nut selectivity of the prior art is demonstrated in this test e.g. the compounds according to the following production examples: 9, 10 "12" 14 "16" 17, 18, 23 and 44.

Le A 26 501

- 298 - 291963

Example C 5

Defoliation and drying of leaves in cotton

Solvent: 30 parts by weight of dimethylformamide emulsifier: 1 part by weight of polyoxyethylene sorbitan

monolaurate

To prepare a suitable preparation of active compound, 1 part by weight of active compound with the stated amounts of solvent and emulsifier and filled with water to the desired concentration.

Cotton plants are grown in the greenhouse until fully unfolding the 5th leaf. At this stage, the plants are sprayed dripping wet with the active ingredient preparations. After 1 week, the leaf fall and the drying out of the leaves are scored in comparison with the control plants. It means:

0 no drying out of the leaves, no leaf fall ** + slight drying of the leaves »low leaf fall

+ + severe dehydration of the leaves, strong leaf fall very strong dehydration of the leaves, very strong leaf fall

A clear superiority compared to the unbehan-

In this test, for example, the compounds according to the following manufacturing examples: 13 and 16.

Le A 26 501

Claims (4)

- 299 - Fatentana prawn 5 N-aryl-nitrogen heterocycles of the general formula (I) » in which 15 Het for a heterocycle of the formula R ⁴ R ⁵ 0 R ⁸ _V 0( N( N- j I N- odor I N- stands, R ^{1 is} hydrogen or halogen and R ^{2 is} halogen or a radical -XR ⁹ , in which R ^{3 is} hydrogen, alkyl or haloalkyl and R ^{4 is} hydrogen, halogen, alkyl or Haloalkyl is or R ³ and R ⁴ together represent doubly linked alkanediyl, Le A 26 R ^{5 is} hydrogen, halogen, alkyl or Haloalkyl is R ^{6 is} hydrogen, alkyl, alkoxyalkyl, Haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl or optionally substituted cycloalkyl, R ^{7 is} hydrogen, alkyl, alkoxyalkyl, Haloalkyl, alkenyl, haloalkenyl, Alkynyl, haloalkynyl or optionally substituted cycloalkyl and R ^{8 is} hydrogen, alkyl, haloalkyl, Alkenyl, haloalkenyl, alkynyl or haloalkynyl or b7 and R ⁸ together represent divalent alkanediyl, R ^ is in each case optionally substituted alkyl, alkenyl, alkynyl or cycloalkyl stands and
30 X stands for oxygen or sulfur » Le A 26 501 - 301 - 2, N-aryl-nitrogen heterocycles of the formula (I) according to claim 1, in which Het for a heterocycle of the formula ι kj_, ι _M _ "j_" ι vi_ stands R ^{1 is} hydrogen, fluorine, chlorine or bromine ^And R * is fluorine, chlorine or bromine or a radical -XR ⁹ , in which
20 R ^{3 is} hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms or straight-chain or branched haloalkyl having 1 to 4 25 Carbon atoms and 1 to 9 identical or different halogen atoms and R ^{4 is} hydrogen, fluorine, chlorine, bromine, iodine, 30 for straight-chain or branched alkyl with 1 to 6 carbon atoms or for straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 same or different HaIo-35 genatomen stands or Le A 26 501 - 302 - 231363 R ³ and R ^ together for a zwaifachverknüpften Alkandiylrest with 2 to 6 Carbon atoms, R 1 represents hydrogen, fluorine, chlorine, bromine, iodine, branched or branched alkyl having 1 to 6 carbon atoms or straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms,
15 R ° is hydrogen, in each case straight-chain or branched alkyl having 1 to 6 carbon atoms, alkenyl having 3 to 6 carbon atoms, alkynyl having 3 to 6 Carbon atoms, haloalkyl with 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, haloalkenyl having 3 to 6 carbon atoms and 1 to 5 identical or different ² 'halogen atoms, haloalkynyl with 3 to 6 carbon atoms and 1 to 5 identical or different halogen atoms or alkoxyalkyl having in each case 1 to 4 carbon atoms in the individual straight-chain or branched alkyl parts or represents optionally mono- or polysubstituted, identically or differently substituted cycloalkyl having 3 to 7 carbon atoms, suitable substituents being suitable! Halogen, as well as ever because straight-chain or branched alkyl or alkoxy each having 1 to 4 carbon atoms, Le A 2 6 501 - 303 - R ^{7 is} hydrogen, in each case straight-chain or branched alkyl having 1 to 6 carbon atoms, alkenyl having 3 to 6 carbon atoms, alkynyl having 3 to 6 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, halo ·· genalkenyl with 3 bit 6 carbon atoms and 1 to 5 identical or different halogen atoms, haloalkynyl having 3 to 6 carbon atoms and 1 to 5 identical or different halogen atoms or alkoxyalkyl having in each case 1 to 4 carbon atoms in the individual straight-chain or branched alkyl parts or for optionally simple or polysubstituted, identically or differently substituted cycloalkyl having 3 to 7 carbon atoms, suitable substituents being: halogen, and in each case straight-chain or branched Alkyl or alkoxy each having 1 to 4 Carbon atoms and R® for hydrogen or for each straight chain or branched alkyl of 1 to 6 carbon atoms, alkenyl of 3 to 6 Carbon atoms, alkynyl of 3 to 6 carbon atoms, haloalkyl of 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, haloalkenyl of 3 to 6 carbon atoms and Le A 26 501 - 304 - 291363 1 to 5 identical or different halogen atoms or halogenoalkynyl having 3 to 6 carbon atoms and 1 to 5 identical or different halogen atoms or 7 ft R and R together represent a di-linked alkanediyl radical having from 2 to 6 carbon atoms R ^{9 is in} each case straight-chain or branched alkyl having 1 to 8 carbon atoms, Alke nyl of 2 to 8 carbon atoms, alkynyl of 3 to 8 carbon atoms, haloalkyl of 1 to 8 carbon atoms and 1 to 17 same or different halo. genatomen, haloalkenyl with 2 to 8 Carbon atoms and 1 to 15 identical or different halogen atoms, halogenoalkynyl having 3 to 8 carbon atoms and 1 to 13 identical or different halogen atoms, for cyanoalkyl, alkoxyalkyl, alkenyl kylthioalkyl, helogenalkoxyalkyl, alkoxyalkoxyalkyl, (bis-alkoxy) alkyl, (bis-alkylthio) alkyl, alkylcarbonylalkyl, alkoxycarbonylalkyl or alkoxyalkoxycarbonylalkyl each having 1 to 8 carbon tetoff in the individual alkyl moieties and optionally 1 to 9 identical or different halogen atoms, for optionally mono- or polysubstituted, identically or differently substituted cycloalkyl, cycloalkyl, alkyloxycarbonylalkyl or cycloalkylalkyl Le A 26 501 - 305 - with in each case 3 to 7 carbon atoms in the cycloalkyl moiety and optionally 1 to 4 carbon atoms in the straight-chain, branched or branched alkyl moiety, suitable substituents being in each case: halogen and in each case straight-chain or * Q branched alkyl or alkoxy with, respectively 1 to 4 carbon atoms »R furthermore represents in each case optionally substituted by alkyl of 1 to 4 carbon atoms substituted oxetanylalkyl, tetrahydrofuranylalkyl, * ° Tetrahydrofuranylalkyloxycarbonylalkyl or tetrahydropyranylalkyl having in each case 1 to 3 carbon atoms in the respective alkyl moieties, or R ^{9 represents} optionally mono- or polysubstituted or differently substituted aralkyl mi * -. 6 to 10 carbon atoms in the aryl moiety and 1 to 4 carbon atoms in the straight-chain or branched alkyl moiety, being suitable as aryl substituents! Halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy, alkylthio or alkoxycarbonyl having in each case 1 to 4 carbon atoms or in each case ^ O straight or branched halogen alkyl, haloalkoxy or haloalkylthio having in each case 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms and X stands for oxygen or sulfur » Le A 26 501 - 306 - 3. Process for the preparation of N-aryl-nitrogen heterocycles of the formula (I) ¹⁰ in which HeL for a heterocyclic of the formula R ^{1 is} hydrogen or halogen and R ^ is halogen or a radical -XR ^y , in which R ^{3 is} hydrogen, alkyl or haloalkyl 25 stands and R ^{4 is} hydrogen * halogen, alkyl or haloalkyl is ader R ^J and R * together for doubly linked Alkandiyl are available » Le A 26 - 307 - 231363 R ^{5 is} hydrogen, halogen, alkyl or potassium alkyl, R ^{6 is} hydrogen, alkyl, alkoxyalkyl, Haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl or optionally substituted cycloalkyl stands, R ^{7 is} hydrogen, alkyl, alkoxyalkyl, Haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl or optionally substituted cycloalkyl and R ⁸ is hydrogen or, alkyl, haloalkyl, alkenyl, haloalkenyl, haloalkynyl i Alkenyl, haloalkenyl, alkynyl or R ⁷ and R ⁸ together for doubly linked Alkandiyl stand,
25 Each R ⁹ is optionally substituted alkyl, alkenyl, alkynyl or cycloalkyl and X is oxygen or sulfur, characterized in that Le A 26 501 - 308 - (a) N-aryl-nitrogen of heterocycles of Fr.r mX ^ (Ia), in which _R 4-l _f y _r Waseeretoff, alkyl or haloalkyl or together with F ^{3 is} a doubly linked alkanediyl radical, R ⁵ " ^{1 represents} hydrogen, alkyl or haloalkyl and R, R ² and R ^{3 have} the abovementioned meaning, when 4-Cyanophenylhydrazine of formula 25 (ΪΙ) 'CN (II) in which R ¹ and R ^{2 have} the abovementioned meaning, Le A 26 - 309 - with 1,3-diketones of the formula (III), "4-1 F 1 -C-CH-CR ⁵ " ¹ (III) Il O O in which F ³ i R ⁴ " ¹ and R ⁵ " ^{1 have} the meaning given as "n", or with derivatives of these diketone, such as enoletharn, enol esters, ketals, enol ether ketals, enamines or Θ-halovinyl ketones optionally in the presence of a diluent and optionally in the presence of a reaction auxiliary; or that one (b) N-aryl-nitrogen heterocycles of the formula (Ib), _R 4-2 _R 5-l (Ib) in which R ⁴ " ^{2 is} halogen, R ⁵ " ^{1 represents} hydrogen, alkyl or haloalkyl stands and Le A 26 501 - 310 - 29 ^ 963 R, R ² and R ^{3 have} the abovementioned meaning, obtained when N-aryl-nitrogen heterocycles of the formula (Ij) : n (Ij) R ² in which 15 R ¹ , R ² , R ³ and R ⁵ " ^{1 have} the abovementioned meaning, optionally with a halogenating agent 20 in the presence of a diluent reacted; or that one (c) N-aryl-nitrogen heterocycles of the formula (Ic), (Ic) in which R ⁵ " ^{2 is} halogen and R ¹ , R ² , R ³ and R ^{4 have} the abovementioned meaning, Le A 26 - 311 - obtained when N-aryl-pyrazolinones of the formula (IV) ₁ in which R ¹ , R ² , R ³ and R ^{4 have} the meaning given above » with a halogenating agent, optionally in the presence of a diluent and optionally in the presence of a reaction auxiliary; or that one (d) N-aryl-nitrogen heterocycles of the formula (Id), (Id) in which R ¹ , R ² and R ^{7 have} the abovementioned meaning to have, obtained when 4-cyanophenylhydrazines of the formula (II) Le A 26 - 312 - 237313 2 ^<in in Veer R ¹ and R ² are as defined above to have, with iminocarbon esters of the formula (V), R ⁷ 0
R ¹⁰ -OC = NCOR ⁿ (V) in which R ^^ and R ** are each independently alkyl and R ^{7 has} the meaning given above, optionally in the presence of a Verdünungs- ^ÄO means by means; or that one (e) N-aryl-nitrogen heterocycles of the formula (Ie), Le A 26 501 - 313 - in which 5 R ⁸ " ^{1 represents} alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl or haloalkynyl and R *, R * and R 'are as defined above, obtained when N-aryl-nitrogen heterocycles of the formula (Id) R ¹ N (id) R ² in which R ¹ , R ^ and R ^{7 have} the abovementioned meaning, with alkylating agents of the formula (VI), _R 8-1_ _E 1 in which 30 r8 ~ 1 has the meaning given above and E ^{1 is} an electron attracting leaving group, Le A 26 - 314 - if appropriate in the presence of a diluent and if appropriate in the presence of a reaction! 1fsmittels; or that one (f) N-aliyl-nitrogen heterocycles of the formula (If), (If) in which 7-1 ft -? · R and R together represent a doubly linked alkanediyl radical, obtained when amidrazones of the formula (VII), R ⁷ " ¹ ft ₉ l
R ⁸ " ² -NH-C = N-NH- <y> -CN (VII) in which R ⁷ ~ * and R ° -2 have the abovementioned meaning, optionally reacted with phosgene in the presence of a diluent and optionally in the presence of a reaction auxiliary B; or that one Le A 26 501 - 315 - Z97963 (g) N-aryl-nitrogen heterocycles of the formula (Ig) » (Ig) R ⁶ R ² in which R, R * and P ^{6 have} the abovementioned meaning, receives »if you phenylhydrazides of the formula (VIII), R ² 0 yx II , NC- <> -NH-NH-CR ⁶ (VIII) in which R ¹ , R ² and R 1 have the abovementioned meaning, with phosgene optionally in the presence of a diluent and optionally in Gegen reacting a reaction aid converts; or that one (h) N-aryl-nitrogen heterocycles of formula 35 Le A 26 - 316 - R ⁴ R ⁵ X-R ^ in which 10 R ¹ , R ³ | R ⁴ | R ⁵ , R ^?> And X have the abovementioned meaning> gets when you get 15 (α) N-aryl-nitrogen tetrahydrofenes of the formula (Ik), R ⁴ R ⁵ R ¹ 20 L / R ² " ¹ in which
R ² ~ * is halogen and R ¹ , R ³ , R ⁴ and R ^ have the abovementioned meaning, with alcohols or thiols of the formula (IX), R ⁹ -XH (IX) in which 35 Le A 2 6 501 - 317 - R ⁹ and X have the abovementioned meaning, 5 if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, or in that (P) (thio) Phenol derivatives of the formula (X), R ⁴ R ⁵ _ -. XH in which R ¹ , R ³ , R ⁴ , R ⁵ and X have the abovementioned meaning, with alkylating or acylating agents of the formula (XI), R ⁹ -E ² (XI) 25 in which R ^{9 has} the abovementioned meaning and . Έτ for an electron attracting waste group stands, Le A 26 - 318 - ZS7963 if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary; or that one (i) N-aryl-nitrogen heterocycles of the formula (Ii), (Ii) in which R ¹ , R ² , R ³ and R ^{5 have} the abovementioned meaning, when l-arylpyrazolyl-4-carboxylic acid ester of the formula (XII) K ¹² O-CO (XII) in which R ^{12 is} alkyl and R ¹ , R ² , R ³ and R ⁴ have the abovementioned meaning, saponified in the presence of an acidic or basic catalyst and optionally in the presence of a diluent and then thermally decarboxylated ♦ Le A 26 - 319 - 231363 4 "Herbicides and plant growth-regulating agents" characterized by a content of at least one N-aryl-nitrogen heterocycle of the formula (I) according to
to claims 1 to 3. 5 "Method for controlling weeds" thereby characterized in that N-aryl-Sticketoffheterocyclen of formula (I) according to claims 1 to 3 act on the weeds and / or their habitat
leaves. 6, Use of N-aryl-nitrogen heterocycles of Formula (I) according to claims 1 to 3 for controlling weeds and / or as plant growth regulators. ² ^ 7, process for the preparation of herbicides and / or lance-growth-regulating agents »characterized in that m &sub1; N-aryl-nitrogen-containing heterocycles of the formula (I) according to Claims 1 to 3 are mixed with extenders and / or surface-active substances, 8. 4-Cyanophenylhydrazines of the formula (II) in which R ^{1 is} hydrogen or halogen and Le A 26 501 - 320 - 231963 F ^{2 is} halogen or a radical -XR ⁹ , 5 in which X is oxygen or sulfur and Each R ⁹ is optionally substituted alkyl, alkenyl, alkynyl or cycloalkyl stands· 9 »N-aryl-pyrazolinones of the formula (IV), in which
20 R * is hydrogen or halogen, R ^{2 is} halogen or a radical -XR ⁹ , in which
25 X is oxygen or sulfur and Each R ⁹ is optionally substituted Alkyl, alkenyl, alkynyl or cycloalkyl 30 stands, F ^{3 is} hydrogen, alkyl or haloalkyl and Le A 2 6 501 - 321 - 29? 363 R ^{4 is} hydrogen, halogen, alkyl or haloalkyl or R ³ and R ⁴ together represent double-linked alkanediyl. 10, (thio) phenol derivatives of the formula (X), in which R ^{1 is} hydrogen or halogen and R ^{J is} hydrogen, alkyl or haloalkyl and R ^{4 is} WnF-oxygen, halogen, alkyl or haloalkyl or R ³ and R ⁴ together represent doubly linked alkanediyl, R ^{5 is} hydrogen, halogen, alkyl or haloalkyl. Le A 26 501 - 322 - 11. Process for the preparation of 4-cyanophenylhydrazines of the formula (II) (II)
i - ** V ^ R ² in which Rl is hydrogen or halogen and R ^ is halogen or a radical -XR ⁹ , 15 in which X is oxygen or sulfur and Each R ⁹ is optionally substituted alkyl, alkenyl, alkynyl or cycloalkyl, characterized in that 4-fluorobenzonitriles of the formula (XIII) (XIII) ^f r2-1 in which R ² " ^{1 is} halogen and R ^{1 has} the meaning given above, Le A 26 501 - 323 - with hydrazine hydrate, if appropriate in the presence of a diluent, and the 4-cyano-phenylhydrazines of the formula (HA) thus obtained, in which 15 R ¹ and R ^{1 have} the meanings given above, optionally in a subsequent 2 step with Alcohols or thiols of the formula (IX), R ⁹ -XH (IX) in which 25 R ° is in each case optionally substituted Alkyl, alkenyl, alkynyl or cycloalkyl and stands for oxygen or sulfur, optionally in the presence of a diluent and optionally in the presence of a Reactive agent reacted or that one 35 Le A 26 - 324 - 297263 4-Cyanophenylhydrazines of the formula (Ib) ι NH-NH ₂ (lib) in which R ^{1 has} the meaning given above and F represents in each case optionally substituted alkyl, alkenyl, alkynyl or cycloalkyl, with 4-aminobenzonitrile of the formula (XIV), (XIV) in which R ¹ and R have the abovementioned meaning, first diazotized with sodium nitrite in the presence of an acid and then reduced with a reducing agent. Le A 26 - 325 - 297363 12. Process for the preparation of N-aryl-pyrazolinones of the formula (IV) in which R ^{1 is} hydrogen or halogen, R ^{z is} halogen or a radical -XR ⁹ , in which X is oxygen or sulfur and Each R ⁹ is optionally substituted Alkyl, alkenyl, alkynyl or cycloalkyl, R ^{3 is} hydrogen, alkyl or haloalkyl is 25 and R ^{4 is} hydrogen, halogen, alkyl or haloalkyl or R ³ and R ⁴ together for double-linked alkane stand diyl, characterized in that fJ-ketoesters of the formula (XV) Le A 26 - 326 - R ³ -C-CH-C 00 R ¹³ (XV) OR ⁴ in which R ^{13 is} alkyl and 10 R ³ and R ^{4 have} the abovementioned meaning, with 4-cyanophenylhydrazines of the formula (II), NH-NH ₂ (II) in which R ¹ and R have the abovementioned meaning, optionally in the presence, of a diluent and optionally in the presence of a Reak-Z5 implementation of the aid 13 »Process for the preparation of (thio) phenol derivatives of the formula (X) 30 _R 4 _R 5 Le A 26 501 - 327 - J97363 in which 5 R * is hydrogen or halogen and R ^{3 is} hydrogen, alkyl or haloalkyl and 10 R ^{4 is} hydrogen, halogen, alkyl or haloalkyl or R ³ and R ⁴ together represent doubly linked alkanediyl, R ^ is hydrogen, halogen, alkyl or haloalkyl, characterized in that mar. N-aryl-nitrogen heterocycles of the formula (Ik) in which R ² " ¹ for halogen eteht and R ¹ , R ³ , R ⁴ and R ^{5 have} the abovementioned meaning, Le A 26 - 328 - with sodium hydrogen sulfide> optionally in the presence of a diluent and optionally in the presence of a reactive nsufsmittels, optionally in the presence of a nitrogen or argon-6chutzgaeatomosphäre or that N-aryl-nitrogen heterocycles of the formula (H), 10 (II) in which F *, K ³ , R ⁴ and R ^{5 have} the abovementioned meaning and _, R ⁹ " ^{1 is} allyl or benzyl, with reducing agents in the presence of a hydrogenation catalyst, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction agent. Le A 26