DD273969A5 - USE OF HALOGENALKYL, ALKENYL AND ALKINYLAZOLE AS SYNERGISTS FOR SCHAEDLINGSBEKAEMPFUNG - Google Patents

Abstract

The present invention relates to the use of novel haloalkyl, alkenyl and alkynyl-azoles of the general formula (I) in which X is a nitrogen atom or a CH group, R is optionally substituted tert.-alkyl or optionally substituted cycloalkyl and A is one of the moieties wherein R1 is halo, alkoxy or trialkylsilyloxy, R2 is hydrogen or halo and R3 is halo, and their salts are synergists in pesticides. Formula (I)

Description

Use of haloalkyl, alkenyl ur.d alkynyl azoles as synergists for pest control

Field of application of the invention

The present invention relates to the use of novel haloalkyl, alkenyl and alkynyl-azoles as synergists in agents for combating Sohädlingen.

Characteristic of the known state of the art

It has already been disclosed that certain herbicides, such as, for example, Be ^ -amino-O-tert-butyl-O-ethylthio-benzo-ethylthio-1,2,4-triazin-5-one, 1-amino-3-one (2,2-dimethy-propyl) -6- (ethylthio) -1,3,5-triazine-2,4-dione 6-chloro-2-ethylamino-4-isopropylamino-1,3,5 triazine 1-methoxy-1-.9-ethyl-3- (3,4-dichlorophenyl) urea; 1,3-dimethyl-1- (ben '<50-1.3-thiazol-2-yl) -urea or 3 ⁱ -Cyolohexyl-5,6-trimethylenuraoii, photoeynthese-inhibiting properties (cf. · z. B. Carl Fedtke, Biochemistry and Physiology of Herbioide Action, Springer Verlag, 1982). A disadvantage of these herbicidal compounds, however, is that not always all occurring weeds and grass weeds are fully detected or that at some high on v / endmeng some crop species are partially damaged.

Synergistisehe mixtures of insecticidal agents, eg. B. of pyrethroids, with certain methylenedioxyphenyl derivatives, eg. B. Piperonyl butoxide, as synergists are also already known (see, for example, BK Naumann, Chemistry of pesticides, Springer-Verlag Berlin, Volume 7 (1981) pages 3-6) In practice, conditions never fully satisfying.

Object of the invention

The aim of the invention is to provide novel compounds which are suitable as synergists for pest control.

Presentation of the essence of the invention

There have now been new haloalkyl, alkenyl and alkynylazoles of the general formula (I)

(I)

in which

X represents a nitrogen atom or a CH group,

R ¹ is optionally substituted fiü tert "alkyl or represents optionally substituted cycloalkyl and

A is one of the groupings -C-G, -C =C- or

r ¹ r ²

-C CH-,

I ₁ I ₂

R ¹ R ^

wherein 5

R ^{1 stands} for Haloger, Alkoxy or TrialkylsiJyloxy «

R ^{2 is} hydrogen or halogen and 10

R ³ stands for halogen «

and their salts are found ·

In the following, salts of the compounds of the formula (I) are to be understood as meaning the acid addition salts and metal salt complexes. «

Furthermore, it has been found that the haloalkyl-alkenyl- and alkynyl-azoles of the formula (I)

f ~ l dl

in which

X "R and A have the meanings given above, and their salts are given" if one

(*) For fur "that X and R have the meanings given above, and

A for the grouping -C = C- is j in which

I i

R ¹ R ²

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R ^{1 is} halogen and R ^{2 is} hydrogen, Azolyl ketones of the general formula (II)

t f ^ l on

in which

15

X and R have the meanings given above,

in a conventional manner with suitable halogenating agents, or

20

(b) in the event that X and R have the meanings given above, and

A "represents the grouping -C = C-, in which

R ¹ R ²

R ¹ is alkoxy or trialkylsilyloxy and

R ^{2 is} hydrogen,

30

Azolyl ketones of the general formula (II)

ii

Ii ^ l (in

RC-CH ₇ -KTs ^ N ^Λ

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in which

X and Ώ have the meanings given above,

in a manner known per se in the presence of a strong base and in the presence of a diluent β 10

with an alkylating agent or a SiJ.ylie-

implements or

(c) in the event that X and R have the meanings given above, and

A represents the grouping -C = C-,

Chlorovinyl-azole derivatives of the general formula (Ia)

(Ia)

Cl

in which

X and R have the meanings given above,

dehydrochlorinated by reaction with a strong base in the presence of a diluent, or

(d) in the case where X and R have the meanings given above, and

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A is the moiety -C-CH- , wherein

R ¹ R ²

R ¹ , R ² and K ^{3 have} the abovementioned meaning 10,

Alkenyl benzenes of the general formula (Ib)

R-C = CH-N 1 N (Ib)

R ¹

in which 20

X »R and R ^{1 have} the meanings given above,

with halogen compounds of the formula (IZI) 25

R ² -R ³ (III)

in which *

_R 2 _and p 3 have the meaning just given,

in the presence of a diluent, or

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It) for the case »that X and R have the above given meanings and

A for the grouping -C = S = C-stent * in which

F ¹ R ²

¹⁰ ι

R * has the meaning given above and

R ^{2 is} halogen, Hslogenalkyl-azoles of the formula (Ic)

F ³

ϊ γ ·

R ¹ R ² 20 in which

X / R and R have the meanings given above

have and 25

R ² and R ^{3 are} halogen,

dehydrohalogenated by reaction with a strong base in the presence of a diluent and 30

optionally added to the compounds of formula (I) thus obtained an acid or a metal salt by conventional methods.

The present invention further relates to the confused

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The use of compounds of the general formula (I) and their salts as synergists for combating pests, preferably of plant and particularly preferably animal pests, and also Lynergietic mixtures of compounds of the formula (I) and their salts and known photosynthetic inhibiting herbicides (for weed control ) and particularly preferably synergistic mixtures of compounds of the formula (I) and their salts and known arthropodicides, in particular insecticides and acaricides (for the control of arthropods) and the use of these mixtures for combating pests, preferably for the control of arthropods.

The present invention also relates to. new herbicidal compositions containing known photosynthesis inhibiting herbicides on the one hand and erfindungs.gemäße compounds of formula (I) and their salts as synergists teadererseits and the use of this center. ', as herbicides,

Furthermore, the present invention particularly relates

preferably new pesticides which contain the compounds of the formula (I) and their salts as synergists in addition to arthropodiziden, in particular insects!

and acaricidal agents and use 30

this pest control product «

As arthropodicides (substances active against arthropods) virtually all customary active substances are suitable (cf., B, K, -H, buffel, crop protection and pest control).

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fungsmittel, Thierne Verlag Stuttgart, 1977, and Farm Ohemicala Handbook 1979, Master Publishing Co., Willoughby, 1979).

The compounds of the general formula (I) and their salts are preferred together with arthropodiziden

1 · Carbaiaidsäureestern and / or

2. carboxylic acid esters including natural and synthetic pyrethroids and / or

3. Phosphorus compounds such as phosphoric acid and phosphonic acid esters including the thiol and thiono compounds

used.

Although the new compounds of the general formula (I) and their salts do not have their own herbicidal activity at the customary application rates, they also-as was also found-cause a substantial increase in the herbicidal activity of photosynthee inhibitor active substances. The synergistic effect found here is totally unexpected and surprising.

Since the exact synergistisohe effect found also affects those weeds that are insufficiently damaged or even nicht-detected by the photosynteheeh inhibitors used in the sole application at usual rates, inventea a

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synergistic drug formulations are a valuable addition to the technique of.

Surprisingly, the effect of the active compound combinations according to the invention of compounds of the formula (I) and their salts and known arthropodicides against arthropods is substantially higher than the effect of these individual components or the sum of the effects of the individual components. It is also much higher than the effect of drug combinations with the known commercially available synergist piperonyl butoxide. The compounds of the formula (I) which can be used according to the invention and their salts show excellent synergistic activity not only in the case of an active substance class, but also in the case of active substances from a wide variety of chemical substance groups.

The synergistic effect of the compounds of the general formula (I) and their salts is particularly preferred

1) carbamic acid esters of the formula (IV)

R ⁶

in which

for an optionally substituted carbocyclic or heterocyclic aromatic radical or for an optionally substituted

-lixed oxime radical (the radicals R * explained below are preferred),

R ^{5 is} C ₁ -C ₄ -AUyI and

R ^{6 is} hydrogen, C ₁ -C ₄ -AUyI or a. ¹ ^

Rest Y stands, where

Y is the radical -CO-Ji ⁷ ; wherein

R ⁷ is halogen, C ₁ -C ₄ -AUyI, C ₁ -C ₄ alkoxy, Cg-Cg-Alkeribxy, C3-Cg-alkynoxy, C ₁ -C ₄ -AUyRhIo, C ₁ -C ₄ -AUyI-amino "Di-C ₁ -C ₄ -AUyl.asnino" C ₁ -C ₄ alkyl-hydroxylamino, represents optionally halogen "nitro" cyano "trifluoromethyl, C ₁ -C ₄ -AUyI _{1 is} C ₁ -C ₄ alkoxy "C ₁ -C ₄ -Ulynoxy, C ₁ -C ₄ -alkylthio" C ₁ -C ₄ -autoxy-carbonyl-substituted phenoxy "phenylthio or phenylamino" for 2,3-dihydro-2,2-dimethyl-7 benzofuranyl or for

the rest -0-N = C stands "in which \ ⁹

R ^{8 is} hydrogen, C ₁ -C ₄ alkyl

or di-C 1 -C 3 -alkyl-pentamino-carbonyl and

R ^{9 is} Cj-C ₄ -alkyl, C ₁ -C ₄ 35

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Cyano-C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -alkyl-C ₁ -C ₄ -alkyl,

or the two radicals R ⁸ and R ⁹ together are optionally interrupted by oxygen ι sulfur, SO or SO 2 interrupted C ₂ -Cg alkanediyl, or

in which

Y is the radical -S _o (0) _p -R ¹⁰ , in which

ο for 1 or 2 and

20

ρ stands for 0, 1 or 2

(if ο stands for 2, ρ means 0) and

R ^{10 is} optionally halogen

substituted C ₁ -C ₄ -alkyl, C ₃ -C ₅ -

Alkenyl, C ₃ -C 9 -alkynyl or C ₃ -C 12 -cycloalkyl, optionally substituted by halogen, cyano, nitro, trifluoromethyl, trifluoromethoxy, trifluoromethane

3Π

methylthio, Cj-C ₄ alkyl or C ₁ -C ₄ -

Alkoxy-substituted phenyl, benzyl

or phenylethyl or for the Feet

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R ^{11 is} C ₁ -C ₄ -Al) CyI, C ₃ -C ₅ -alkenyl, C ₃ -C ₅ -alkynyl, C ₃ -C ₆ -cycloalkyl or benzyl ^ and

R ^{12 is} C ₁ -C ₄ -alkyl, C ₃ -C ₅ -alkenyl, C ₃ -C ₅ -alkynyl, C ₃ -C ₆ -cyclo-C ₁ -

alkyl, benzyl, phenylethyl, HaIogencarbonyl, Forinyl, C ₁ -C ₄ -alkyl-carbonyl, C ₁ -C ₄ -alkoxy-CBrbonyl, C ^ C ^ alkoxyphenoxy-carbonyl, _{C3-C5-alkynoxy-carbonyl,} C ₃ - C5 "alkenoxy-cerbonyl, C" _{1 "} -C" _{4 "} -alkylthiocarbonyl, C" _{1 "} -C" _{4 "} -alkyl-arnino-carbonyl, C" _{1 "} -C" _{4 "} -alkyl-hydroxylamino-carbonyl , _m C" _{1 "} -C" _{1 "} -alkyl- phenoxycarbonyl, di-C ₁ -C ₄ -alkylamino-cirbonyl _{; i-} phenylthio-carbonyl, phenoxycarbonyl, 2,3-dihydro-2,2-dimethyl-7-benzofuranyloxy-carbonyl, optionally substituted by halogen, Cyano, nitro, trifluoromethyl, C ₁ -C ₁₀ -A ^ yI or C ₁ -C ₄ -alkoxy substituted phenyleulfenyl, phenyleulfinyl, phenylbulfonyl or phenyl, or the radical

-CO-O-N ^ C, in which

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the meaning given above for R ⁸ and

the exercises specified for R.

Meaning has ¹⁰

r. furthermore, int rest -N the

Radicals R ** and R * together for an optionally direct oxygen or

¹ ^ sulfur interrupted hydrocarbons

stoffkeftte stand with 3 to 8 carbon atoms and in which further R * ^ can also stand for the same radical to which the radical -S _o (0) _p -R ^10th

30 is bound.

AIb active ingredient components most preferably Bind carbamic acid esters of the formula (IV), in

which 25

R ⁴ is optionally substituted by Cj-C ₄ -alkyl, C ₃ -C ₄ alkenyl, Cj-C ₄ -alkoxy, Cj-C ₄ alkoxy-methyl, C ₁ -C ₄ -AIkYUhIO, C ₁ -C ₄ - Alkylthi-p-methyl, C ₁ -C ₄ -alkylamino, di (C ₁ -C ₄ -alkyl) -BmInO, di- (C ₃ -C ₄ -alkenyl) -amino, halogen, dioxolanyl, methyl-

lendioxy and / or radicals substituted by the Reut -N = CH-N (CH ₃ ) _2, bus of the series phenyl, naphthyl, 2,3-dihydro-7-benzofAlBryl, pyrazole

IyI or pyrimidinyl, or in which

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for an alkylidene aminoreet of the formula

-N = C,

\ 16

in which 10

R ¹⁵ and R ^{16 have} the meaning given above for R ⁶ or R ⁹ , and

R ^{5 is} C _1-4 -alkyl and

Ή * is hydrogen or Cj-C ^ alkyl (preferably hydrogen).

As examples of the carbamic acid esters of the formula (IV), mention may be made of the following N-methylcarbamic acid esters:

2-methylphenyl -, 2-ethylphenyl-, 2-hexypropylphenyl-, 2-sec-butylphenyl-, 2-methoxy-phenyl- ,

2-ethoxy-phenyl , 2-iso-propoxy-phenylene, 4-methyl-25

phenyl, 4-ethyl-phenyl , 4-n-prebphenyl-phenyl, 4-methoxy-phenyl, 4-ethoxy-phenyl, 4-n-propoxy-phenyl, 3,4,5-trimethyl phenyl, 3,5-dimethyl-4-methylthio-phenyl, 3-methyl-4-dimethylaminophenyl, 2-ethylthiomethyl-phenyl, 1-naphthyl, 2 | 3-dihydro-2,2-dimethyl-7 benzofuranyl, 2,3- (dimethylmethylenedioxy) -phenyl, 2- (4,5-dimethyl-1,3-dixolan-2-yl) -phenyl, 1-methylthio-ethylidene-amino, 2 -Methyl thio-2-mypyopropyl idenamino-, 1- (2-cyanoethylthio) -ethylideneamino- and Ϊ-methylthiomethyl-

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2,2-dimethyl-propylideneamino-N-tnethyl-carbamidiBureeeler.

The synergietic action of the compounds of general formula (I) is further preferred

2) Carboxylic acid esters of the formula (V)

RR ¹ ^ CO-O-CH-R ¹⁹ (V)

In which

R ^{17 is} an unsubstituted or cyclic alkyl, which is optionally substituted by halogen, alkyl, cycloalkyl, alkenyl optionally substituted by halogen, alkyl and / or alkoxy, by phenyl or styryl, optionally substituted by halogen, optionally halogen-substituted ,, Reets from the series alkyl, alkoxy, alkyldendioxy and / or alkylthio are substituted, by spiro-cyclic, optionally halogen-substituted cycloalk (en) yl, which is optionally benzannelated, in

which one further

R ^{18 is} hydrogen, alkyl, haloalkyl, alkenyl, alkynyl or cyano, and

R is an optionally substituted alkyl

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or aryl radical or for a heterocyclic

ift

stands "or together with R and the carbon atom to which bride residues are bound forms a cyclopentenone ring.

Especially preferred as active ingredient components are carboxylic acid esters of the formula (V) in which

R ¹⁷ (a) for the rest

-CH = C

/ R ²⁰

H ₃ C is CH ₃ , in which

R ²⁰ for Wäeerstoff, methyl, fluorine, Chlorine or bromine is and

R ² * is methyl, fluorine, chlorine, bromine, C ₁ -C ₂ fluoroalkyl or C ₁ -C ₂ -ChIoTfIuOralkyl or optionally substituted by

Halogen and / or optionally halogen-substituted radicals of the series C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio and / or C ₁ -C ₂ -alkylenedioxy-substituted phenyl, or

wherein both radicals R ²⁰ and R ^{21 are} C ₂ -C ₅ -AlkBHdIy ₁ I (Alkyl.en) btehen;

or in which 35

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R ¹⁷ (b) stands for Rent -CH-R ²² , in which

I ₂₃

R ^{22 is} optionally halogen

and / or · gen-Bubetituierte by optionally halo radical · the series C ₁ -C ₄ -alkyl, C ₁ -G ₄ -alkoxy, C ₁ -C ₄ -alkylthio or C ^ -Co-Alkylenedioxy represents substituted phenyl and

R "is laopropyl or cyclopropyl;

or in which

__ R ¹⁷ (c) for methyl or one of the radicals CH ₃

-CH ₃ ,

H ₃ C CH 3 H ₃ C CH »25

H ₃ C CH ₃

"_ Where the dotted lines are in front

Indicate double bonds,

and in which

R ^{18 represents} hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -HaIOgCnBl-

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kyl is cyano or ethynyl and

R * 'for the radicals from the series phenyl, "furyl or tetrahydrophthalimido * where this · ⁿ may be substituted by radicals from the series halogen Cj-C ^ j alkyl, C ₂ -C ₄ alkenyl and / or C ₁ -C _4- alkoxy C ₂ -C ₄ -alkenoxy, C ₁ -C ₄ -alkylthio, C ₁ -C ₂ -alkylenedipxy, phenoxy and / or benzyl, which in turn may be substituted by -halogen and where R ^{19 is} preferably 5,6-tetrafluorophenyl or 4-methylthio-2,3,5,6-tetrafluorophenyl, 3,4-dichlorophenyl, tetrahydrophthalimido or phenoxyphenyl, 1 which may be substituted in one or both phenyl rings by halogen4

Furthermore, the naturally occurring pyrethroids (such as pyrethreum) are particularly preferred as carboxylic acid esters of the formula (V),

As examples of the carboxylic acid esters of the formula

(V) may be mentioned:

Acetic acid (2,2,2-trichloro-1- (3,4-dichloro-phenyl) -ethyl) -ester, 2,2-dimethyl-3- (2-methyl-propen-1-yl) -cyclopropane-carboxylic acid (3,4,5,6-tetrahydrophthalimido-methyl) -, 2,2-dimethyl-3- (2,2-dichloro-vinyl) -cyclopropane-carbonic acid (3-phenoxybenzyl) ester, 2,2 -Dimethyl-3- (2,2-dichlorovinyl> cyclopropane-carboxylic acid (α-cyano-3-phenoxy-benzyl) ester, 2,2-dimethyl-3- (2,2-dichloro-1-yl-1-yl) -cyclopro-

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pancarboneaure-ia-cyano-ii-fluoro-3-phenoxybenzyl) ester, 2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylic acid (2,3,5,6-tetrafluorobenzyl) - ester, 2,2-dimethyl-3- (2,2-dibromovinyl) cyclopropanecarboxylic acid (a-cyano-3-phenoxybenzyl) ester and 3-methyl-2- (4-chlorophenyl) butane -eäure- (α-cyano-3-phenoxy-benzyl) -ester;

Next, the synergistic effect of the connec tions of the general formula (I) is preferably at

3) Phosphoric acid and phosphonic acid esters of the general formula (VI)

_ _ft R ²⁴ -WP (VI)

20 \ q-r26

in which

Q is 0, S, -NH- or a direct bond between and

25? A

between the central P atom and R '°,

F ²⁴ and R ^{25 are the} same or different and represent optionally substituted alkyl or aryl, and

R ^{co represents} hydrogen, optionally substituted alkyl, aryl, heteroaryl, aralkyl, alkenyl, di-

oxanyl or an oximreet or for the same

the remainder is bound to the e, and

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W identifies the same or different and for O or S.

Particular preference is given to phosphoric acid and phosphoric acid esters of the formula (VI) in which

10 ₇ . ₇ c

R ^ and F ^{D are the} same or different and for C 1 -C 4 -alkyl or phenyl,

R ^{26 is} hydrogen or alkyl of 1 to 4 carbon atoms optionally substituted by halogen, hydroxyl, cyano, optionally halogen-substituted phenyl, carbamoyl, alkylsulfonyl, alkylsulfinyl, alkylcarbonyl, alkoxy, alkylthio, alkoxycarbonyl, alkylaminocarbonyl, the latter each up to 6 carbon atoms, is substituted alkenyl with * up to 4 carbon atoms, which is optionally substituted by halogen, optionally halogen-substituted phenyl or Cj-C ^ alkoxycarbonyl, or the radical of the general formula

-N = C, where \ 28

R ²⁷ and R ^{28 have} the meaning given above for R ⁸ or R ⁹ , or are cyano or phenyl,

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and in which

R ^{26 is} also dioxanyl which is substituted by the same radical "to which R ^{25 is} bonded, or R ^{26 is} the same radical to which it is bonded, or R ^{26 is} phenyl which is optionally substituted by methyl, nitro, cyano, _{and the like} Haloge ^. and / or methylthio. stands, where

R ² ° also particularly preferably represents optionally substituted by C ₁ -C ₄ -alkoxy, Cj-C ₄ alkylthiomethyl, Cj-C ^ alkyl and / or halogen-substituted hateroaromatische radicals, such as pyridinyl, quinolinyl, quinoxalinyl, pyrimidinyl or Bonzo- 1,2,4-triazinyl is ·

Specifically, may be mentioned:

0,0-Dimethyl- or O, O-Diethyl-O- (2,2-, i-chloro-t-or 2,2-dibromovinyl) -phosphoric acid ester, 0,0-diethyl-O- (4-nitro-phenyl) -thionophosphoric acid ester, 0.0-dimethyl-O-methyl-4-methylthio-phenyl) -thionophosphoric acid ester, 0.0-dimethyl-1- (3-methyl-4-nitrophenyl-1-thionophosphoric acid ester, O-ethyl-Sn-propyl -O- (2,4-dichlorophenyl) thionophosphorusaurate, 3r, O-ethyl-Sn-propyl-O- (4-methylthio-phenyl) -thionophosphoric acid ester, 0,0-dimethyl-S- (4-oxo-1H) , 2,3-benzotriazine (3) yl-methyl) -thionothio phosphate, 0-methyl-0- (2-iso-propyl-6-methoxy-pyrimidin (4) yl) -thionomethanephosphonic acid ester, 0,0-di-

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Ethyl O- (2-iso-propyl-6-methylpyrimidin (4) yl) -t.hionophosphoric acid ester, O _# O -dithyl-1- (3-chloro-4-diethyl-coumarin (7) yl) - thionophosphorus sucyl ester, 0.0-dimethyl-2,2,2-trichloro-1-hydroxy-β-than-phosphonic acid ester, 0,0-dimethyl-S (methylaminocarbonylmethyl) -thionophosphoric acid ester.

In the general formulas optionally substituted tert.-alkyl R is an alkyl group having preferably 4 to 12, in particular 4 to S carbon atoms, wherein at least one carbon atom must have bonds of 4 directly adjacent carbon atoms and wherein this alkyl group by one or more, preferably 1 to 3, in particular 1 or 2 identical or different substituents may be substituted. "Preferred substituents are halogen atoms (fluorine, chlorine, bromine and / or iodine, preferably fluorine and / or chlorine).

As preferred tertiary Alkylgrjppen are listed: (CH ₃ J ₃ C, Cl-CH ₂ -C (CHg) ₂ -, F-CH ₂ -C (CHg) ₂ -, CH ₃ -C (C ₂ H ₅ J ₂ - and (CH ₃ ) ₃ C-CH ₂ -C (CH ₃ ) ₂ -,

Optionally substituted cycloalkyl R is cycloalkyl having preferably 3 to 7, in particular 3 to 6 and very particularly preferably 5 or 6 ring members (such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl) , wherein the cycloalkyl radical by one or more, preferably 1 to 3, in particular a Substitjesiten can be substituted. AIk substituents are alkyl having preferably 1 to 4, in particular 1 or 2 carbon atoms and halogen (fluorine, chlorine,

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Bromine and iodine, preferably fluorine or chlorine). Particular preference is given to 1-methylcyclopentyl and 1-methylcyclohexyl.

In the definition of λ, halogen R ¹ , R ² and R ³ denote fluorine, chlorine, bromine and iodine, by preference fluorine, chlorine and bromine, in particular chlorine and bromine and more preferably chlorine ·

Alkoxy R * is alkoxy with preferably 1 to 6, in particular 1 to 4 and particularly preferably 1 or 2 carbon atoms.

The alkyl groups in the trialkylsilyloxy radical R ¹ contain

preferably 1 to 4, in particular i or 2 carbon

atoms per alkyl group. Particularly preferred is the trimethylsilyloxy radical.

A is particularly preferred for the groups

-C = CH; -C = CH-, -C = CH-, -C = CH- and -CCl ₂ -CHCl-. IIIl Cl OCH ₃ OC ₂ H ₅ 0

Si (CH ₃ ) ₃

X is preferably a nitrogen atom (which is the besting moiety of a 1,2,4-triazol-1-yl ring).

Preferred salts of the (basic) compounds of the formula (I) are their salts with hydrohalic acids, such as. As the hydrochloric acid and hydrobromic acid, also phosphoric acid, nitric acid,

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mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, much as ζ, Β. Acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid and sulfonic acids, such as. P-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid,

Furthermore, the addition products of salts of metals of II. To IV. Main and the I and II and IV to VIII. Subgroup of the Periodic Table of the Elements with the compounds of formula (I) are listed.

The compounds of the formula (I) are preferably in free form (ie not in the form of a salt).

In the preferred inventive haloalkyl, alkenyl and alkynyl-azoles of the formula CI)

X for a nitrogen atom or a CH group, R is optionally substituted by halogen

tert-alkyl having 4 to 8 carbon atoms or optionally substituted by alkyl having 1 to 4 carbon atoms and / or halogen-substituted cycloalkyl having 3 to 6 carbon atoms and

30 _R 3

A represents the groupings -CBC-, -C = ⁵ C- or-C-CH-

F ¹ Ft <F ¹ F ²

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in which

R ^{1 is} halogen (preferably bromine or chlorine) »

Alkoxy of i to 4 carbon atoms or is Trimethyleilyloxy "

10 ~

R ^{A is} hydrogen or halogen (preferably

Bromine or chlorine) and

r3 is halogen (preferably bromine or chlorine).

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

X represents a nitrogen atom or a CH group (preferably a nitrogen atom) »

R is optionally substituted by chlorine and / or fluoro-substituted tert-alkyl of 4 to β carbon atoms (preferably tart, butyl) or ofgebogen-25

optionally substituted by chlorine »methyl» ethyl * and / or isopropyl substituted cyclopropyl »cyclopentyl or cyclohexyl and

A represents the group -C = C- or

A for. the grouping -C = C-,

R ¹ R ²

in which 35

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2739 (59

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(a) R ^{1 is} chlorine, methoxy, ELhoxy or tri-

thylsilyloxy stands and

ι R ^{2 is} hydrogen, or

(b) R ¹ and R ^{2 are} chlorine, or

A stands for the grouping -C-CH-,

Rl R ² 15

wherein

R ¹ , R ² and R ^{3 are} chlorine.

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

X for a nitrogen atom,

R represents the radicals JCHg) ₃ C-, Cl-CH ₂ C (CHg) ₂ - * F-CH ₂ C (CHg) ₂ -, CH ₃ -C (C ₂ Hg) ₂ or (CH ^) ₃ C- CH ₂ -C (CH _3. ) ₂ - and

A for the groupings -C "C-, -CC1 = H,

30 -C (OGJ-I ₃ ) ^ CH-, -C (OC ₂ H ₅ ) = CH -, - C (OSi (CH ₃ ^ g) = CH- or CClg-CHCl-.

If, for example, 3,3-dimethyl-1- (1,2,4-tri-1-yl) -butan-2-one is used as the starting material, and phosphorus oxytrichloride and phosphorus pentachloride are used as starting materials.

Le A 24 959

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means, the course of the process variant (a) according to the invention can be represented by the following formula:

POCi ₃

(CH ₃ ) ₃ CC-CH ₂ -NV ^ N

PCl

If, for example, 3,3-dimethyl-> 1,2- (1,2,4-triazol-1-yl) -butan-2-one is used as the starting material , diethyl sulfate as the alkylating agent and sodium hydride as the strong base, the course of the process variant according to the invention can be used (b) are represented by the formula scheme below:

j (CH ₃ ) ₃ CC «CH-

If, for example, 3,3-dimethyl-1- (1,2,4-triazole-1-yl) -2-chlorobut-1-ene is used as the starting material and sodium ethylate as the strong base, the course of the process variant according to the invention can be used (c) are represented by the formula scheme below:

Ci N. N

IIIC ₂ H ₅ ONa II

30 (CH ₃ ) J ₃ CC = CH-NVv ^ N> ^

If, for example, 3,3-dimethyl-1- (1,2,4-triazol-1-yl) -2-chloro-butene and bromine are used as starting materials, the course of process variant (d) according to the invention can be represented by the following formula scheme been:

Le A 24 959

- 29 -

Br, f

CCHN ^ N> (CH _{3) 3} CC-CH

Cl Cl Br

If, for example, 3,3-dimethyl-1- (1,2,4-triazole-1-yl) -1,2-dibromo-2-chloro-butane is used as the starting material and sodium ethylate as the strong base, the sequence can be used the process variant (s) according to the invention are represented by the following formula:

2 (CHg) ₃ CC-CH-NV ^ N

CCHNV ^ N> (CHg) ₃ CCC

Cl Br Cl Br

The methods for carrying out the method according to the invention are

variant (a) and (b) as starting materials to be used azolyl ketones are known (see, z, B "DE-OS

2 431 407, EP 0 031 911, EP 0 054 865, DE-OS 2 610 022, DE-OS 2 638 470, DE-OS 2 820 361, DE-OS 3 145 857, DE-OS

3,145,858) j or, according to methods known in

as prepared by reacting the corresponding halomethyl ketone with the corresponding azole in the presence of an inert organic solvent such as acetone or acetonitrile, and in the presence of an acid binder _t such as Kaliumca carbonate or triethylamine, at temperatures between 20 ⁰ C and 150 ⁰ C. ,

The to be used as starting materials for carrying out the process variant (c) according to the invention

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Chlorovinyl-azole derivatives of the formula (Ia) are novel compounds and can be prepared according to the inventive process variants (a) and (b). Si · are part of the present invention «

The alkenyl-uzols of the formula (Ib) to be used as starting materials for carrying out the process variant (d) according to the invention are likewise novel compounds and can be prepared according to the process variants (a) and (b) according to the invention. »They are likewise part of the present invention.

The Halcgenalkyl-azoles of the formula (Ic) to be used as starting materials for carrying out the process variant (e) according to the invention are likewise novel compounds and can be prepared according to process (d) according to the invention "These compounds are likewise part of the present invention"

Suitable halogenating agents for process variant (a) according to the invention are all halogenating agents which are customarily used for the conversion of aliphatic ketones into the corresponding vinyl halides, in particular phosphorus pentahalides, for example phosphorus pentachloride and phoephorpentabromide, and also phosphoroxytrihalides, for example phosphoroxytrichloride and phosphorus oxytribromide.

in question.

The process variant (a) according to the invention is preferably carried out without a diluent

Le A 24 959

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The reaction temperatures may be 5 when carrying out

the process variant (a) according to the invention can be varied within a substantial range. In general, one works at temperatures between 20 ⁰ C and 200 ⁰ C, preferably at temperatures between 40 ⁰ C and 180 ⁰ Ci

In carrying out the process of the invention,

variant (a) is used for 1 mole of the azolyl ketone of the formula (II) is preferably 1 to 2 moles of the halogenating agent.

The halovinyl-azole derivatives of the formula (Ib)

R-C = CH-NV ^ J (aO>

20 R ¹

in which

R and X have the meanings given above, and R * is halogen, such as chlorine or bromine, »

can be also obtained by the azolyl-ketones of the formula (II) with triphenylphosphine and a Hexahalogenethan as hexachloroethane or hexabromoethane, in the temperature range from 60 ⁰ C to 200 ⁰ C, preferably in the temperature range from 80 ⁰ C to 180 ⁰ C. without Diluent umeetzt (see also the manufacturing instructions). _

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As alkylating agent or silylating agent for process variant (b) according to the invention, use is made in particular of dialkyl sulfates, such as ζ. Β. Dimethyl sulfate and diethyl sulfate, or Trialkyleilylhalogenide, such as. B. trimethylsilyl chloride.

Strong bases are found in the implementation of the

Method variant (b) according to the invention all conventional strong anorganißchen and organic bases in question. These preferably include alkali metal hydrides or alkali metal amides, such as sodium hydride or amide and potassium hydride or amide; tertiary alkylamines such as triethylamine, alkali metal alcoholates such as sodium methylate, sodium ethylate and potassium tert -butylate; and alkali hydroxides »such as sodium hydroxide and potassium hydroxide.

As diluents come in the implementation of the

Process variant (b) according to the invention all customary inert organic solvents into consideration. Particularly suitable are ethers, such as dioxane and tetrahydrofuran; Formamides, such as dimethylformamide; and sulfoxides, as dimethylsulfoxide ·

When carrying out process variant (b) according to the invention, the reaction temperatures can be converted into a larger range. In general, one works at temperatures between 20 ⁰ C and 100 ⁰ C, preferably between 40 ⁰ C and 80 ⁰ C *

In deij carrying out the process variant (b) according to the invention is used for 1 mole of the azolyl ketone of

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2739 *

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Formula (II) preferably 1 mole of the alkylating agent.

For the process variant (<:) according to the invention, suitable strong bases are all customary strong inorganic and organic bases. These preferably include alkali metal hydrides or alkali metal amides, such as sodium hydride or amide and potassium hydride or amide; tortiare alkylamines such as triethylamine) alkali metal alcoholates such as sodium methylate, sodium ethylate and potassium tert-butylate; and alkali hydroxides such as sodium hydroxide and potassium hydroxide.

Suitable diluents for carrying out the process variant (c) according to the invention are all customary inert organic solvents. Again, there are particular suitable ethers, such as dioxane and tetrahydrofuran; Formamides, such as dimethylformamide; Sulfoxides, such as dimethyl sulfoxide, and alcohols, such as ethanol *

The reaction temperatures can be varied within a substantial range when carrying out the process variant (c) according to the invention. In general, one works at temperatures between ^{0 0} C and 120 ⁰ C * preferably between 20 ⁰ C and 100 ⁰ C.

When carrying out the method according to the invention

Riante (c) is used for 1 mol of the chlorovinyl-azole derivative of the formula (Ie) preferably 1 to 2 moles of base.

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The process variant (d) according to the invention is carried out using halogen compounds of the formula (III). In formula (III), R * and R 1 are preferably chlorine and / or bromine "in particular chlorine". Examples of the halogen compounds of the formula (III) are chlorine (Cl ₂ ), bromine (Br ₉ ) and "bromine chloride" ( BrCW) - the latter optionally generated in situ from bromine and chlorine jj - called --f

Suitable diluents for carrying out process variant (d) according to the invention are all customary inert organic solvents. Particular preference is given to halogenated hydrocarbons, such as, for example, "methylene chloride 1" 2-dichloroethane "chloroform" tetrachloromethane. , Chlorobenzene and dichlorobenzene «

The Reaktionstemperatur.en can lose within a substantial range in the inventive Vetfahrensvariante (d) "in general carried out at temperatures between ⁰ C and 200 ⁰ C, preferably at temperatures between 20 ⁰ C and 150 ⁰ C.

In. When carrying out the process variant (d) according to the invention, 1 to 3 mol of a halogen compound of the formula (III) are preferably employed per mole of alkenylrazole of the formula (Ib).

For the process variant (e) according to the invention, suitable strong bases are all customary strong inorganic and organic bases. These preferably include _ ₅ alkali metal hydrides or alkali metal amides, such as Nstriumhydrid or

Le A 24 959

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amide and potassium hydride or amide; tertiary alkylamines such as triethylamine; Alkali metal alcoholates such as sodium methoxide, sodium ethylate and potassium tert -butylate; and alkali hydroxides, such as sodium hydroxide and potassium hydroxide,

AIb diluents come in the implementation of the

Process variant (s) according to the invention all conventional inert organic solvents into consideration, Again, particularly suitable are ethers, such as dioxane and tetrahydrofuran; Formamides, such as dimethylformamide; Sulfoxides, such as dimethyl sulfoxide, and alcohols, such as ethanol.

The reaction temperatures can be varied in carrying out the process variant (e) according to the invention in a larger range. "In general, one operates at temperatures between ^{0 0} C and 120 ⁰ C, preferably between 20 ⁰ C and 100 ⁰ C,

In the. Implementation of process variant (e) according to the invention is preferably carried out using 1 to 2 moles of base per mole of the haloalkylazole of the formula (Ic).

For the preparation of Slureadditions salts of the compounds of general formula (I) ν rzugsweise already> context are "_ those acids, with the description represents erfindungegeme ι acid addition salts as preferred acids genar i were

The acid addition salts of the compounds of the formula (I) 35

Le A 24 959

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can in a simple manner by customary salt formation methods, eg. By dissolving a compound of general formula (I) in a suitable inert solvent and adding the acid. For example, hydrochloric acid, and in known Weiae z, B. by filtration, isolated and optionally by washing 10

cleaned with an inert organic solvent

become·

For the preparation of Metalloalz-Xomplexen of the compounds of general formula (I) are preferably those salts of metals in question, which have already been described above.

The metal complexes of compounds of general formula (I) can be easily obtained by conventional methods. B. by dissolving the metal salt in alcohol, z, Bi ethanol, and adding to a solution of compounds of general formula (I). It is possible to isolate metal salt complexes by filtration in known Weiss, Zt B., and optionally to purify them by recrystallization.

As photosynhether-herbicidal active substances for the above-mentioned active compound combinations mentioned, the following compounds of the general formulas (VII-A) to (VII-J) are preferably mentioned:

Le A 24 959

73 9 69

- 37 -

(λ) Triezinone derivatives of the formula

in which

X * is amino, optionally substituted alkyl idenamino or alkyl of 1 to 2 carbon atoms;

X ^{2 is} alkylthio of 1 to 2 carbon atoms, alkyl and dialkylamino each of 1 bit 2 carbon atoms in each alkyl part or alkyl of 1 to 4 carbon atoms; and

X is optionally substituted by halogen-substituted tert-butyl or optionally substituted phenyl,

(B) Triazinedione derivatives of the formula

"NN ..

TT (VII-B)

in

X ^. for amino, optionally substituted Al

Le A 24 959

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kylidenamino or alkyl having 1 bio 2 carbon atoms;

X ^{5 is} alkylthio of 1 to 2 carbon atoms, alkyl and dialkylamino each of 1 to 2 carbon atoms in each alkyl part or alkyl of 1 to 4 carbon atoms; and

X ^{6 is} alkyl having 1 to 6 carbon atoms or ι is optionally substituted phenyl «

(C) Triazine derivatives of the formula

X ⁷

N ₅ T ^ N

(VII-C)

in which

Υ. ^{7 represents} chlorine, alkoxy or alkylthio with each 1 to 2 carbon atoms;

X ⁸ represents Alkylemino having 1 to 4 carbon atoms in the alkyl moiety; and

X ^{9 represents} optionally cyano-substituted alkyl having 1 to 4 carbon atoms.

(D) Harvestoff derivatives of the formula

N-CO-N (VII-D)

χΐΐ / \ _χ 13

Le A 24 959

27394-9

- 39 -

in which

X ^{10 is} optionally substituted phenyl »

Benzthiazolyl or optionally substituted thiadiazolyl is)

1O ₁₁

X ^{11 is} hydrogen or methyl; X ^{12 is} methyl; and

X ^{13 is} hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 2 carbon atoms or alkynyl of 2 to 4 carbon atoms «

(E) Carboxililide derivatives of the formula 20

X 1 -CCMNH-X ¹⁵ (VII-E)

in which

X ^lH for alkyl with up to 6 carbon atoms «

Alkoxy of 1 to 4 carbon atoms, alkenyl of 2 to 4 carbon atoms or cycloalkyl of 3 to 6 carbon atoms; and

_1t .

X ^{19 is} optionally substituted phenyl

stands.

Le A 24

10 35

273

40 -

(F) Uraci1 derivatives of the formula 5

I ¹ I ₉ ^(VII " ^F) N ¹⁹

in which

X ^{16 is} alkyl of 1 to 6 carbon atoms or cycloalkyl of 5 to 7 carbon atoms

stands;

X ^{17 is} halogen;

Χ ^{18 is} alkyl having 1 to 2 carbon atoms, or

X * 'and X * together represent a optionally substituted alkylene chain or an optionally substituted fused benzene ring; and

X ¹⁹ represents the CO or SO 2 group , (G) biscarbamate derivatives of the formula

(VII-G) NH-CO- ^X21

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273949

- 41 -

in which

X ^{20 is} alkyl of 1 to 4 carbon atoms or optionally substituted phenyl; and

X ^{21 is} alkoxy of 1 to 4 carbon atoms or dialkylamino of 1 to 2 carbon atoms in each alkyl portion.

(H) Pyridazinone derivatives of the formula

in which

X ^{22 is} optionally substituted phenyl;

χ23 is aminoalkylamino or dialkylamino each having 1 or 2 carbon atoms in each alkyl moiety; and

30 X ²⁴ stands for halogen.

(J) Hydrpxybenzonitri! Derivatives of the formula

Le A 24 959

- 42 ~

(VLI-J)

in which

X ²⁵ for halogen eteht; and X ²⁶ stands for halogen.

Particular preference is given to the following photosynether inhibitors of the general formulas (VII-A) to (VII-J):

(A) Triazinone derivatives of the formulas

^ n

1 ι

(VII-A-I) (metribuzin)

(VII-A-2)

(VII-A-3)

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(VII-A-4) (Metimony tron)

(CH

Jl (VII-A-5) (isomethiozine)

15 (B) Triazinedione derivative of the formula

(CH ₃ )

(VII-S-I)

(Ametridione

(C) Triazine derivatives of the formulas

^C 2 ^H 5 "

Cl H - CH (CH ₃ )

(VII-C-I) (atrazine)

SCHj H-CH (CH ₃ )

(VII-C-2) 'Ametryn)

Le A 24

27396

- 44 -

COHC-KH ' OCH ₃ H-CH (CHg) ₂ (VII-C-3) (atraton) Cl CSK CH ₃ \ | CH ₃ ^ (VII-C-4) (cyanazine)

yun _;

QCH, 15

(VI1-C-5) (prometon) (CH _{3) 2} CH-KH '' * ^s ^ w mv ¹ H CH (CH _{3) 2}

SCH ₃

20 M ^ v ^ Ki (VII-C-6)

νΛν - - -

J M (Prometry)

'^^ N' ^ ^V ^ NH-CH (CH ₃ ) ₂

J CH ₃ ) ₂ CH-KH '^^ N' ^ ^V ^ NH-CH (CH ₃

Cl

25 NsT ^ N (VII-C-7)

I | l (Propazine)

), CH-NH ^^ N ^^ NH-CH (CH ₃₎ o

Cl

_ _N ^ N NiT (VII-C-8)

³⁰ I H (simazine)

OCH ₃ * sTMi

(VII-C-9) 35 L II (Simeton)

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SCH '

(VII-C-IO) (Simetryn)

'2 ^Μ 5 ·

SCH, (VII-C-II)

j] (Terbutryn)

NH-C (CH ₃ J ₃ "

^C 2 ^H 5 ·

Cl (C ₂ Hg) ₂

(VII-C-12) (trietaxin)

(D) Urea derivatives of the formulas

Cl

Cl

-NH-CO-N (VII-D-I) (Linuron)

1-CO-NH-CH, (VII-D-2) (methabenzothiazuron)

CH-

(CH ₂ ) ₂ CH

(VII-D-3) NH-CO-N (CH ₃ ) 2 (Ieoproturon)

NH-CO-NH-CH ₃ (VÜ-D-4) (benzthiazuron)

Le A 24

2739 * 9

N - N

J! i (CH _{3) 3} C-SO ₂ - ^ v5 ^ NC

CH ₃ (VII-D-5) (buthiuron)

Cl

H-CO-N-CH ₃ CH ₃ -CH-C = CH

(VII-D-6) (buturon)

br

NH-CO-N / CH ₃

Cl (VII-D-7) (chlorobromuron)

(VII-D-8) NH-CO-N (CH ₃ ) ₂ (chloroxuron)

Cl

CH

₃ - '

NH-CO-N (CHg) ₂ (VII-D-9) (chloro-olurone)

Cl

C1-C T-NH-CO-N (CH ₃ )

(VII-D-IO) (Diuron)

N N

-2 "5 -CO-NH-CH ₃

CH:

(VII-D-H) (ethidimuron)

(VII-D-12)

NH-CQ-N (CH ₃ ) 2 (Fenuroni

Le A 24

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H-CO-N (CH ₃ ) ₂

CF, (VII-D-13) (fluometuronic acid)

Cl

CHO

H-CO-N (CH ₃ ) ₂

(VII-D-14) (Metoxuron)

Cl

H-CO-N (VII-D-15) (Moaolinurone)

Cl-C7-NH-CO-N (CHg) ₂

(VII-D-16) (Monuron)

Cl

Cl

H-CO-N (Vn-D-17) (Neburone)

N N

JI JL CO-NH-CH ^

(VII-D-18) (Tebut, hiuron)

CH-

ClF ₂ CS

NH-CO-N (CH ₃ ) ₂ (VII-D-19)

(Thiochlortnethyl)

Cl

(E) Carboxanilide derivatives of the formulas

Cl

H _? C = C-CO-HH CHO

(VII-E-D (chloroanocryl)

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(VII-E-2) (Cypromide)

nC _a H ₇ \

Cl

CH.

CII-CO-NH

(VII-E-3) (Kareil)

nC ₃ H ₇ \

Cl

CH.

CH-CO-NH

(VII-E-4) (pentanochlor)

Cl

CH ₃ -CH ₂ -CO-NH

(VII-E-5) (Propani1)

Cl

CH ₃ -O-CO-NH-

(VII-E-fe) (Swep)

(F) Uracil DerivaLe of formulas

, , X ^ H

(VII-F-I) (Lenacil)

, (VII'F-2) (bromacil)

Le A 24

CH,

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2739

(VII-F-3) (Isocil)

(VII-F-4) (Terbacil)

(ViT-F-5) (Benlazon)

(G) Biecarbamate derivatives of the formulas

NH-CO-OC ₂ H ₅

-CO-NH

(VII-G-D (Desmed ipham)

NH-CO-N (CH ₃ ) ₂

-CO-NH-C (CH ₃ ) ₃

(VII-ff-2) (keratinilates)

Le A 24 959

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NH-CO-O-CH ₃

-CO-NH

CH, (VII-G-3) (Phenmedipham)

(H) pyridazinone derivatives of the formulas

Η-

(VII-H-I) (pyrazole)

(VII-H-2) (Meflurazon)

(VII-H-3) (norflurazon)

(J) HydroxybenzoniLri1-DerivaL of the formulas

Br ·

Br (VII-J-I) (Bromoxynil)

OH

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(VII-J-2) (chloroxynil)

(VII-J-3) (ioxynil)

Lo A 24

27394

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The photosynthesis enzymes of the formulas (VII-A) to (VII-J) are known (see, for example, Carl Fedlke, Biochemistry and Physiology of Herbicidal Action * Springer-Verlag, 1982).

The weight ratios of the active ingredients in the new drug combinations may vary in relatively large areas. "In general, one part by weight of photosynthetic active ingredient (herbicidal active ingredient) accounts for 0 * 25 to 100, preferably 5 to 50, especially 10 to 20, parts by weight of compound Formula (I) (synergist) «

The Photoeynthesehemmer agents have strong herbicidal activity. Nevertheless, they have weeds against some _2Q , such as B, Galum aparine, Iopmoea hederacoa, Datura stramonium, Cirsium arvense, Convolvulus arvensis, or Solanum nigrum, and some grass weeds, such as B, Agropyron repens, Avena fatua, Cynodon dactylon, Cyperus ex., And Lolium rigidum have not always sufficient effect. The erfindungfagemäßen drug combinations extend the spectrum of activity of the compounds of the formulas (VTI-A) to (VII-J), thereby enabling a fight against this by the herbicidal active ingredients alone difficult or impossible to control weeds.

Di? Inventive drug combinations of photographic

Synthesis inhibitors and compounds of the formula (I) can be used, for example, in the following plants: i

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Dikotvle weeds of the genera? Sintpis, Lepidiumi Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium # Urtica, Senecio, Amaranthus, Portuleca, Xanthium, Convolvulus, Ipomoea, Polygonum, Seebania, Ambrosia, Cireium, Carduus, Sonchus, Solanum, Rorippa, Rota

Ia, Lindernia, Lamiura, Veronica, Abutilon, Emex _} Datura, 10

Viola, Ga'eopsis, Papaver, Centaurea.

Dicotyledonous cultures of the genera} Gossypium, Glycine, Beta, Daucus, Phaseolus, Pieum, Solanum, Linum, Vicia, Nicotiana, Lycopereicon, Arachia, Braesica, Lactuca, Cucumis, Cuburbita.

Monocotyledonous weeds of the genera. ' Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Feituca, Eleusine, Brachiaria, LoIum, Bromus, Avona, Cyperue, Sorghum, Agropyrone, Cynodon, Monochoria, Fimbrietylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Iechaemum, Sphenoclea, Dac tyloctenium, agro- ty, / leccurus, apera «

Monocotyledonous Cultures of the Genera · Oryzs, Zee, Tritieum, Hordeum, Avena, Seeale, Sorghum, Panicum, Saccharum, Pineapple., Asparagus, Allium.

However, the use of the erfindungsgenäßen drug combinations is not limited to these genera, but extends in the same way to other plants.

The active compound combinations according to the invention show, in particular, in addition to a good action against grass-like

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(monocots) Weeds also have a good herbicidal action on dicotyledonous weeds.

The new active substance combinations for weed control can be used either as newts or in their formulations as a mixture with other known herbicides for controlling weeds, in which case ready-to-use formulations or tank mixes are possible. Also a mixture with other known active ingredients, such as fungicides. Insecticides, acaricides, nematicides, bird repellents, plant growth regulators and soil conditioners are possible.

The new drug combinations can never be used in the form of their formulations or the use prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. The application takes place in the usual way, for example by pouring, spraying, spraying, spreading.

The active substance combinations according to the invention for controlling weeds can be applied both before and after sowing, as well as after emergence of the plants, together or in separate applications. The order of the application does not matter.

When using the synergists according to the invention, the usual application rate of the herbicide of the formulas (VII-A) to (VII-J) can be reduced.

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bizidem PhotoBynthesehemmer active ingredient is in flat treatment between 0.01 and 3.0 kg / ha, preferably between 0.05 and 2.0 kg / ha. The expenditure on synergistic compounds of the formula (I) for surface treatment is between 0.1 and 10 kg / h, preferably between 0.5 and 3 kg / ha.

The good herbicidal action of the active compound combinations according to the invention is evident from use example (A). While the individual active ingredients have weaknesses in the herbicidal action, the combinations show a weed effect which goes beyond a simple activity summation.

A synergistic effect is always present in herbicides if the herbicidal action of the active substance combination is greater than the sum of the effects of the individual active substances applied.

The active compound combinations according to the invention of arthropodicides and compounds of the formula (I) and salts thereof and the arthropodicidal pesticides which contain these active compound combinations not only have a rapid knock-down effect, but also cause the killing of animal pests, preferably of arthropods, in particular Insects and arachnids (including mites) found in agriculture (including animal husbandry), in forestry, in stockpile and material protection, and in the household and sanitary sector. 3ie _: are against Norway. sensitive and resistant »/ / as well as against all

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or a single development would be effective.

The animal pests which can be controlled using the compounds of formula (I) and their salts * include, for example!

From the order of Iaopoda e.g. Oniscus asellus, Arma

dillidium vulgaris, Porcellio scsber.

From the order of diplopoda e.g. Blaniulue guttula

tus.

From the order of Chilopoda e.g. Geophilus carpopha

gus »Scutigera spec«

From the order of Symphyla e.g. Scutigerella immacu-

lata.

From the order of Thysanura e.g. Lepiema saccharine. Auρ of the order of Collembola e.g. Onychiurus armatus. From the order of Orthoptera e.g. Blatta Oriental, Periplaneta americana, Leucophaea maderae, Blattella

germanica »Acheta domestic. Gryllotalpa epp., Locusta migratoria migratorioidee, Melanoplue differential ie,

Schistocerca gregaria. From the order of the Dermaptera e.g. Forficula auricula

ria,

From the order of isoptera e.g. Reticulitermes «pp .. From the order of the Anoplura e.g. Phylloxera vnstatrix « Pemphigus βρρ. # Pediculum humanue corporia, Haematopinus

epp., Linognathus spp.

From the order of Mallophaga e.g. Trichodocte * epp. » Damalinea spp. From the order of Thysanoptera e.g. Hercinothrips

femoralis, thrips tabaci.

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From the order of the heteropter "e.g. Eurygaslsr epp., ♦

DysdercuB intermediu «» Piesma square ·, üimex lectula-

rius, Rhodnius prolixus »Trietoma epp.

Aue of the Order of the Homoptera · eg Aleurodes brassicae »Bemiiia tubaci, Trialeurodes vaporariorum» Aphia gossypii, Brevicoryne braeeicae, Cryptomyzus ribie, Aphis fabae, Doralie pomi , Eriosoma lanigerum, Hyalopterue arundinie, Macroeiphum «venae« Hyzus epp. »Phorodon humuli, RhopaloBiphum pedi , Empoaeca epp, »Euecelie hilobatub» Nephotetlix cincticepe »Lecan ium corni» Saieuetia oleae »Laodelphax elriatellue, Nilaparvata lugens» Aonidiella aurantii »Aspidiotus hederae» Pseudococcus spp, Psylla epp.

From the order of Lepidoptera e.g. Pectinophora gossypiella Bupalus piniarius Cheimatobia brumaia Lithocolletis blancardella Hyponomeuia padella Plutella maculipennis Malacosoma neustria Euproctis chryeorrhoea Lymanlria spp, Bucculatrix thurberiella Phyllocnistis citrella Agrotis ipp. Euxor spp. Feltia spp. Earias insulana Keliolhis epp »» SpocOplera exigua »Mamestra brassicae» Panolis flammea »Prodenia litura» SpodopLera «pp.» Trichoplusia ni »Carpocapsa pomonellaj Pieris spp.» Chilo spp. »Pyrausta nubilalis» Ephestia kuehniella, Galleria mellonella »Tineola bissel1iella» Tinea pellionella »Hofmannophila pseudospretella» Cacoecia podana »Capua reliculana» Chorietoneura fumiferana »Clysia ambiguella» Hoir.ona Aiagnanitna »Tortrix viridana.

From the order of Coleoptera e.g. Änobium puncLaLum »35

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Fhizoperlha dominica, Acanthoecelides obtectus, Acan-5

ihoscr / iif'.eB obtectus, Hylotrupes bajulue, Ageleetic · alni, Leptinotarsa decemlineala, Phaedon cochleariae, Diabrotica «pp., PsylHodes chrysocephala, Epilachna varivo etie, Atomaria epp., Oryznephilwa surinamenu: e, Antho ^ nomue spp ·, Sitophilue spp · Otiorrhynchue eulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermetes «pp.» Trogoderma spp., Anthrenus spp., AttagenuB spp. »Lyctue epp., MeligeLaene-U ¹ S, Ptinue epp.» NipLus hololeucuu, Gibbium psylloides, Tribolium epp., Tenebrio moiitor, Agriotee opp., Cono derb Bpp ,, Melolontha melolontha, Amphimallon solsti tialis, Costelytra zealandica.

From the order of Hymenoptera ζ «Β · Diprion epp., Hoplocampa epp ,, Lasius spp ·, Monomorium pharaonie, Veepr.

Aue of the Order of the Dipter «e.g. Aedes epp ·, Anopheles

spp., Culex spp., Droeophila melanogaster, Mueca epp., Fannia spp., Calliphra erythrocephala, Lucilia spp., Chrysontyia spp, Cuterebra epp., Gastrophilus spp., Hy pobosca Bpp., Stomoxys spp, Oestrus βρρ , Hypoderma spp, Tabanus jpp. Tannia epp, Bibio hortulanus, Oscinella frit, Phorbia epp, Pegomyia h. Oecyami, Ceratitie capitata, Dacus oleae, Tipula paludosa.

From the Ordn'jrig the siphonaptera e.g. Xenopsylla cheo-

pis, CeraLophyllue opp ,.

From the order of the arachnids, e.g. Scorpio maurus, LatrodecLus mactans · From the order of Acarina e.g. Acarus siro, Argas

Le A 24 959

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spp., Ornithodoros spp., Dormanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus · ρρ · »Fhipicephalus spp ·, Amblyomma epp ,, Hyalomma · · · · Ixodes spp., Peoroptee epp ,, Chorioptes« pp., Sarcopte »spp . »TarsonemuB spp ,, Bryobia praetiosa, Panonychus epp., Tetranychu epp ··

The active compound combinations of the compounds of the formula (I) and their salts and the other active compounds can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, depending on their respective physical and / or chemical properties. Aerosols, active substance-impregnated natural and synthetic substances, Feinstverkapaelungen in polymeric materials and in encapsulants for seeds, in addition in formulations with Brenneätzen, such as smoke cartridges, -doses, spirals, etc., as well as ULV KaIt and warm mist formulations.

These formulations are prepared in a known manner, e.g. by mixing the active compounds with diluents, eleo liquid solvents, liquefied gases under pressure and / or solid carriers, optionally with the use of surface-active agents, ie emulsifiers and / or dispersants and / or foam-forming agents. In the case of using water as extender, »e.g. also organic solvents can be used as auxiliary solvents. As liquid solvents come essentially

Le A 24 959

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aromatics such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. Petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl butobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water; by liquefied gaseous extenders or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; come as solid carriers

2Q in question: e.g. ground natural minerals, such as kaolins,

Clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and ground synthetic minerals such as finely divided silica, alumina and silicates; as solid carriers for granules come in

__ question: e.g. 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 sago meal, coconut shells, corncob and tobacco

__ stem; suitable emulsifiers and / or foam-formers are: e.g. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example .A ^ ylarylpgjyglyh & l ethers, alkyl sulfonates, alkyl sulfates, Arylsulf onr.te and

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Protein hydrolysates of all dispersants are suitable: e.g. Lignin-ffulf i tablaugen * md Methylcolulose «

E »may be used in the formulations adhesives such as carboxymethylcellulose, natural and synthetic powdery« granular or latex-like polymer «such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids, we cephalins and lecithins, and synthetic phoepholipido« Other additives may be mineral and vegetable be oils «

As further additives, dyes such as inorganic

Pigments, Jt.B, 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.

The formulations generally contain between 0.1 and 95% by weight of active ingredient, preferably between C, 5 and 9U of X.

The application of the active compound combinations according to the invention takes place in the form of their commercially available formulations and / or the use forms prepared from these formulations.

The total active ingredient content (including synergist) of the formulations prepared from the commercial formulations may vary widely

Le A 24 959

2739 * 9

- 62 -

Active ingredient concentration of the use form ^ can be from 0.001 to 95% by weight of active compound combination, preferably between 0.01 and 10% by weight.

The application is done in a custom forms adapted to the application forms.

When used against hygiene and Vorratsschadlinge the drug combinations for the control of arthropods characterized by an excellent residual effect on wood and clay and by a good alkali stability on cold substrates.

The weight ratios of the synergists of the general formula (I) or their salts and active substances (arthropodicides or herbicides) can be varied within a relatively wide range. In general, the compounds of the formula (I) or their salts used as synergists with the other active ingredients in mixing ratios between 1 × 100 and 100! 1, preferably

between 1: 20 and 20 J 1, in particular between 1. ' 25

and 10 5 1 (parts by weight) used.

The good arthropodizide effect of the active compound combinations according to the invention from compounds of the formula (I) or their salts and arthropodicides is evident from the use examples (B) and (C).

In addition to the properties indicated, the compounds of the formula (I) according to the invention also have a growth-regulating action.

The production process according to the invention will be explained with reference to the following preparation examples:

Le A 24 959

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example 1

¹

(Process variant a)

A solution of 50 g (0.29 mol) of 3,3-dimethyl-1- (1,2,4-triazol-1-yl) -butan-2-one in 100 ml of phosphorus oxychloride is added with stirring 93 g (0.45 mol) Phocphorpentachlorid added "The reaction mixture is heated for 2 hours at 100 ⁰ C, then poured onto ice" adjusted with concentrated sodium hydroxide to pH 8 and extracted with dichlorine. After removal of the dichloromethane on a rotary evaporator, the residue is distilled.

This gives 42 g (76 X of theory) of 2-chloro-3,3-dimethyl · -1- (1,2,4-triazol-1-yl) -but-1-ene of boiling point 77 ° C / 0, 08 mbar.

(Additional method variant):

396 g (1.7 mol) of hexachloroethane and 437 g (1.7 mol) of trichloroethane

phenylphosphine are slowly heated together with 284 g (1.7 mol) of 3,3-dimethyl-1- (1,2,4-triazol-1-yl) -butan-2-one. At 70 ⁰ C internal temperature occurs an exothermic

Reaction, wherein the temperature St.igt to 115 ⁰ C.

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- 64

The Reaktionegemisch is heated in an oil bath at 170 ⁰ C 5

17U stirred at ⁰ C and 6 hours »By." m Er.ilten is dissolved in the dark product 1.5 1 of dichloromethane and treated with 2 1 of water. While stirring, the mixture is adjusted to pH 6-7 with potassium carbonate, the organic phase is separated off and concentrated on a rotary evaporator. The backsand is extracted with hot petroleum ether (3 times for 1 l) and the extract is evaporated. The remaining oil is distilled.

One obtains 221 g (70 X of theory) of 2-chloro-3,3-dime-1S

thyl-1- (1,2,4-triazol-1-yl) -but-1-ene of boiling point 85 ° C / 0.12 tnbar.

Example 2

(CH ₃ J ₃ CC = CH- (variant b)

To a solution of 50 g (0.29 mol) of 3,3-dimethyl-1- (1,2,4-triazol-1-yl) -butan-2-one in 200 ml of dimethylformamide is carefully added 9 g (0, 3 moles) of 80 percent sodium hydride. After stirring for 10 minutes 46.2 g (0.3 mol) of diethyl sulfate are added dropwise at 30 - 40 ⁰ C and the reaction mixture is stirred for 2 hours at 60 ⁰ C then the mixture is poured into water. The product is extracted with dichloromethane, the solvent removed on a rotary evaporator and the

35 «·

Le A 24 959

273

- 65 -

Residue distilled over a Vigreux column.

This gives 16 g (26 X of theory) of 2-ethoxy-3,3-dimethyl-1 - (1,2,4-triezol-1-yl) -but-1-one of bp 85-90 ° C / 0.665 mbar.

Example 3

(Method variant c)

To a solution of 3 g (0.13 mol) of sodium in 100 ml of ethanol are added at 20 ⁰ C 18.6 g (0 «l mole) of 3,3-dimethyl-l- (l, 2,4-triazol- 1-yl) -2-chloro-but-1-ene and heated at reflux for 1 hour. Then remove the excess ethanol on a rotary evaporator, pour the residue into water and extract the product with you! > Rmethan. After removal of the solvent, the residual oil is distilled.

This gives 11 g (74% of theory) of 3,3-dimethyl-l- (l, 2 _# 4-triazol-l-yl) -but-l-in the boiling point of 150 ⁰ C / 0.266 mbar.

I i

at game 4 Cl Cl I (CHO) oC-C-CH- ³ ** TI Le A 24 959 I Cl

2739

- 66 -

g (process variant d)

In a boiling solution of 55.7 g (0.3 mol) of 2-chloro-3,3-dimethyl-l- (l, 2,4-triazol-l-yl) -butene and 200 ml of chlorobenzene are added within approx "45 minutes 42 g of .ρ (0.6 mol) of chlorine introduced." Upon cooling, the precipitated solid is filtered off and the filtrate is concentrated on a rotary evaporator. "The remaining oily residue is distilled under reduced pressure.

One receives 49.6 g (64 X of Theoria) 3,3-Dimelhyl-l

(1,2,4-triazol-1-yl) -1,2,2-trichloro-butane of boiling point 88 ⁰ C to 94 ° C / 0, l mbar.

Example S

(CH ₃ ) qC -CC-

³³ II

25 Cl Cl

(Provide variant e)

1.3 g (0.055 mol) of sodium are added to 80 ml of ethanol, then 12, β g (0.05 mol) of 3,3-dimethyl-1- (1,2,4-triazol-1-yl) - Added l, 2,2-trichloro-butane thereto and the reaction mixture is stirred at 50 ⁰ C for about 15 hours. After concentration on a rotary evaporator, the residue is partitioned between methylene chloride and water and the organic phase is separated off. After drying with sodium sulphate, the mixture is filtered, the filtrate is concentrated

Le A 24 959

2739 * 9

- 67 -

and the residue is distilled under reduced pressure.

This gives 7.1 g (65 % of theory) of 1 ^ -Di methyl-li 1,2,4-triazo * -l-yl) -butene of boiling point 87 ⁰ C and 93 ⁰ CZO, Λ mbar.

The following compounds of general formula (I) are obtained in the manner and according to the process of the invention.

receive:

Ex -

No. R

Boiling point X (° C / mbar)

(CH ₃ J ₃ C-

(CH ₃ J ₃ C-

Cl -C = CH-

OCH

-C "CH-

-CH- 88 / 0.2 N, .74 / 0.133

8th

CH

Cl-CH ₂ -C-

Cl

-C "CH-

N 130 / 0.266

Cl -C-CH-

I i

Cl Cl

N CFp * 95 ⁰ C]

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Beiap.-Nr, F Boiling point X (° C / mbar)

10

F-CH ₂ -C-

CH ₃ Cl

-C-CH-75/0, B

12

^S CH,

CM ₃ O-Si (CH ₃ ) ₃

, (CH ₃ ) ₃ C- -C-CH N 80 / 0.266 ΓΊ OCH, I -C-CH N 125 / 0.532 CH ₃ ι-ι ^0C 2 ^H 5 -C "CH- N 126 / 0.266

N 128 / 0.2

15

CH-

Cl -C = CH-N 103 / 0.133

V'2 ^H 5

CH ₃ -C-

^C 2 ^H 5 Cl -C "CH- N 84 / 0.133

17

CHo Cl

I ³ I

(CH ₃ J ₃ C-CH ₂ -C- -C "CH-N 100 / 0.133

Le A 24

27

- 69 -

Example of Use A (Herbic Synergism) Pre-emergence Test

Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkyloryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of herbicidal active ingredient or synergist or a mixture of herbicidal active substance .g and synergists with the stated amount of solvent »are added to the specified amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Seeds of the test plants are seeded in normal soil 2Q and watered after 24 hours with a herbicidal preparation or with the synergistic preparation or with the preparation of synergists and herbicidal active ingredient. It is advisable to keep the Wasserr.onge per unit area expediently constant. The active ingredient concentration in the accessory _ ₅ reitung does not matter, "the decisive factor is only the amount of active ingredients per unit area. After three weeks, the degree of damage of the plants is rated as X damage in comparison to the development of the unhindered control. It means:

0 X «no effect (like untreated control)

100 X ^c total annihilation

Active ingredients »Effort Tons and results are shown in Table A below.

Le A 24 959

273 9

-. 70 -

Pre-emergence Te9L

Table A

Synergistic effect of compounds of the formula (I) («Synergist S) and 4-amino-6-tert-butyl-3-methylthiol, 2,4-triazin-5-one (VII-AI) (« herbicide H) Ipomoea hederacea, The application rate in kg / ha refers to the content of active ingredient.

X damage at

15 Structure of the synergist (III) C 1 Ν - 55-1 (CHq) ₃ CC = CH-NX ^ (S) kg / ha (H) kg / ha Ipomoea H hederacea S H ♦ S 90 70 (1) 0.3 1.0 0.07 0.07 10 10 O 20 ι πι (CH ₃ J ₃ CC = CH-NVy ^ N 30 100 (6) (CH ₃ ) ₃ C-CSC-NV ^ N 0.3 2.0 0.1 0.1 10 10 O 80 100 2ο (3) CH ₃ Cl N _-- Cl-CHo-C C = C-NV ^ N 0.3 2.0 0.1 0.1 10 10 10 90 90 (8th) 0.3 2.0 0.1 0.1 10 10 O

30 ^CH 3

Le A 24 959

Table A (continued) Ji damage at Structure dee (S) (H) Ipomoea hederacea Synergists kg / ha kg / ha H S H + S

I I J 0.3 0.1 10 - 50

(7) (CH ₃ J ₃ CC = CH-NVv ^ N 2.0 0.1 10 0 60

OC ₂ H ₅ N ₅ -

I I j 0.3 0.1 10 - 30

(2) (CHo) oC-C «CH NVv ^ N 2,0 0,1 10 0 60

w w "-

CH ₃ Cl N_- *

Il I I 0.3 0.1 10 - 90

(10) F-CH ₂ -CC = CH-NV ^ N 2.0 0.1 10 0 100

CH ₃

Le A 24 959

In the following use examples (B) and (C), the synergistic Wirkeamkeit the inventive compounds of formula (I) in combination with arthropodicides to be explained «

Examples of the arthropodicides which can be used according to the invention are listed below!

<A) Γ I

0-CO-NHCH ₃ OCH (CH ₃₎

(Propoxur)

(B)

(Carbofuran)

0-CO-NHCH ₃

(C) Cl ₂ C = CH-OP (OCH ₃ ) ₂ (DDVP)

(D)

(E) (CH ₃ ) ₂ C = C

H ₃ C

0OCH ₂ -

(Tetramethrin)

(Resmethrin)

Le A 24 959

- 73 -

(F) Br

.-OtS ^ S> 0OC

(DeUamethrin)

(G)

C "CH> v.

(H)

(I) Cl

H ₃ CZNCH

(CypermeLhrin)

AGMs.

H ₃ C

^ COOCH ₂

(IR Lrans)

(Bioreemethrin)

(Cyfluthrin)

Le A 24

Examples of the insecticidal synergists which can be used according to the invention are listed below:

synergist

No , formula

(1)

Cl

Compound from Preparation Example No.

(2)

, C-C = CH-Cl

(3)

CH.

ClCH ₉ -CC =

Il

CH ₃ Cl

(4)

CH

CC

II

CH ₃ Cl

(5)

? 2 »5

CHo-C

CC

I i

C ₂ H ₅ Cl

(CH ₃ UC-C = CH-3 3,

OCH ₃

(7)

CH

₃ ) ₃ 3 3

C OC ₂ H ₅

Le A 24 959

- 75 r

synergist

(9)

formula

<β> (CH ₃ ) ₃ CC = CH-

_CH3 (CHg) ₃ C-CH ₂ -C

(10) (CH _{3) 3} CC

³³ I

Cl

- "CH-N '" ^, Cl Cl ¹ ^ = N compound from Herodellungigesispiel no.

17

(U)

C-CH-Cl

15

(12)

(13)

OCH

H-

OC ₂ H ₅ 12

13

Le A 24

273 9 * 9

- 76 -

Connection bub

5 synergist hereditary

No formula example no.

o £ "

(14) </ -C = CH-N " ¹ ^

OC ₂ H ₅

Le A 24

27396

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Usage of BiB B (insecticidal synergism) KTgQ-Aeroeoltesl Teettiere: Mueca domeetica οσ] strain Weymanns

(resistant to CarbamaLe and phosphoric acid ester)

Solvent: acetone For the preparation of a suitable preparation of active ingredient

one dissolves the active ingredients "synergists and active ingredient / synergist mixtures, in the solvent"

In the center of a gas-tight glass chamber of 1 m ^ large, there are three wire-cage cages in which there are 20 experimental animals each. · After the chamber has been closed again, 2 ml of dec. Drug preparation dusted «The condition of the animals is constantly controlled by the glass walls from the outside and

determines the time required for the animals to have a 50 Xige knock-down effect (KT ₅₀ ). If, after 60 minutes, a KT§q is reached, the X-rate of the knocked-down animals is determined.

Active substances, amounts of active substance and times at which one

50 Xige knock down effect is present and the XrSatz of the animals after 60 minutes knock down (K, Do) gone & oen hen from the following table:

Le A 24 959

Table B

KTgQ-AeroBolteet with male Muaca dornestica (strain and carbamate Weymanns) resident against phosphoric acid ester

Active ingredients / synergists

A B C

1 2 3 4 5 b 7 8 9

Concentration in mg / m ^ active substances ♦ synergists

20

10

10

20 20 20 20 20 20 20 20 20 KTgg within v. 60 minutes (X K. D. after 60 minutes)

None (60 * * 2 X) None (60 · «25 X) 23 " 36 * Knee (60 * «0 X) ^ None (60 * * 0 00 X) None (60 * = 0 X) None (60 ' * 0 X) None J60 · * 0 X) None (60 *   0 X) None (60 * «0 X) None (60 ' * 0 X) None (60 ' = 0 X)

Table 3 - continued

KTqf aerosol test with male phosphoric acid ester resistant Musca doinestica (strain

'and carbamate- Weymanna)

drugs . synergists Concentration in mg / m active ingredients + synergists 20 KTgη within (X K. 0. after v. 60 minutes 60 minutes) = 0x) 10 20 None (60 * = 0x) 11 20 None (60 · »0 X) 12 20 None (60 * = 0x) 13 20 None (60 * * 0 X) 14 10 None (60 * λ 4 1 10 10 45 ' A ♦ 2 10 + 10 33 * A 4 3 10 10 36 * λ 4 4 10 + 10 31 · A 4 5 10 * 10 33 * A 4 6 10 + 10 38 ' A 7 10 + 10 47 ' A 8th 10 49 '

, I

Table B - continued

KTgg Aeroeoltent with phosphoric acid ester resistant male Musca dornestica (Staima

and carbamate

Weymanns)

drugs ♦ synergists Concentration in fngfm agents ♦ · synergists + 10 KT ^ q within v, 60 minutes (X K. D. after 60 minutes) λ + 9 10 + 10 43 ' A 10 10 20 35 * A 11 10 • ♦ 10 36 * λ + 11 10 ♦ 8th 36 * A  f 11 10 • j- 5 37 ' λ + 11 10  » 2 37 ' A + 11 10 + 1 38 " A + 11 10 10 46 ' A 12 10 10 32 * A + 13 10 10 33 * A + 14 10 10 38 * B + 11 10 + 5 22 * B 11 10 22 *

Table B - continued

KTgQ-AeroBolteet with male Husca dornestica (Weymanns strain) resistant to phosphoric acid ester and carbamates

drugs / synergists Concentration in mg / m active ingredients + synergists + 2 * ^T 50 (X K. within v. D. after 60 60 minutes to go) B ♦ 11 10 + 1 26 * B + 11 IG + 20 26 * C 11 10 + IC 13 " C 11 10 5 15 ' C 11 10 15 *

- 82 =

Example C (insecticide synergism) KTgQ aerosol test

Teetties-egg MuBca domestic «do ¹ , strain Hans (resistant to pyrethroids

Solvent Acetone For the preparation of a suitable preparation of active ingredient

you lose the active ingredients »synergists and active ingredient / synergist mixtures» in the solvent «

In the middle of a gastight glass chamber of 1 m ³ size are hung three wire cages containing 20 experimental animals each. "After the chamber has been closed again, 2 ml of the active ingredient preparation are atomized in it. The condition of the test animals is determined by the glass walls of continuously controlled externally and determines the time necessary for a 50 Xige knock-down effect (KTg _n ) of the animals. "If no KTgg is reached after 60 minutes, the X-set of Kncck down gone animals is bestintmt,

Active ingredients, drug amounts and times at which a

50 Xige knock down effect and the X-rate of the animals knocked down after 60 minutes (K.D.) are shown in the following table:

Le A 24 959

Table C

KTgQ-AeroBolteet with male Husca domestic resistant to pyrethroids «(Stamm Harn)

Wirkatorf · / Synergists Concentration in rog / m ³ active ingredients + synergists 20 KT ₅ Q inside (X KD after V, cn ι W W 60 minutes minutes) D 10 20 None (60 '»0 X) e 20 20 None (60 * = 30 X) F 4 20 None (60 '= 22 X) G 4 20 None (60 • = ο χ) H 10 20 None (60 '= 0X) I 2 20 52 ° 1 None (60 '* 0 X) 2 None (60 • * ο χ) 3 None (60 * * 2X) 4 43 ' 5 None (60 • «ο χ) 6 42 ' 7 34 '

Table C - continued

KTgg-Aeroeolteet with male Musca dornestica (strain Hans) resistant to Pyrethroi.de

drugs / synergists Concentration in mg / mr active ingredients + synergists ♦ 20 KTgQ within (X K. D. nach v. 60 minutes 60 minutes) * 20 X) 8th 4 20 None (60 ' a 0 X) 9 4 20 None (60 * B 0 X) 10 4 20 None (60 * «15 X) 11 4 20 None (60 * = 0x) 12 20 None (60 * * 0 X) 13 20 None (60 * «0 X) 14 10 None (60 * D 4 11 10 10 41 * e ♦ 11 10 5 44 * e 11 10 20 42 * F ♦ 11 4. 10 14 * F 4 11 4 5 10 * F + 11 4 19 '

Table C - continued

gQitest with pyrethroid-resistant male Musca dornestica (Stemm Hane)

drugs / synergists Concentrate active ingredients ion in mg / m ^J ♦ synergists 2 KT ^ g within v. 60 minutes (X K. D. after 60 minutes) F 11 A 1 21 * F + 11 4 10 30 ' G * 11 4 + 20 40 ' H ii 10 10 40 * H * 11 10 2 53 ' I * 1 2 2 25 * I 2 2 + 2 43 * I + 3 2 + 2 45 · 1 4 2 2 47 * t ♦ 8th 2 ♦ 2 17 " Ϊ 9 2 * 2 38 * r + 10 2 10 40 ' I 11 2 * 32 '

CO vO Os.

Table C - continued

KTijQ-Aeroeoiteel «lit against pyrethroids resistant male Mupca dornestica (Tribe Hans)

Active ingredients / synergists

I I I I I

11 11 11 11 12 13

Concentration in active ingredients ♦ synergists

2 2 2 2 2 2

8 4 2 1 2 2

^ q within v, 60 minutes (X K. D. after 60 minutes) 32 * 34 · 48 * 36 * 36 * 33 *

vO Os.

Claims (3)

- 87 - Fatentansprüha 1 · Use of haloalkyl, alkenyl and alkynylazoles of the general formula (I) in which X represents a nitrogen atom or a CH group, R is optionally substituted tert-alkyl or optionally substituted cyanoalkyl and A is one of the groupings -C ^ C-, -C = C- or R -C - CH I ₁ I ₂ R ¹ R stands, wherein R is halogen, alkoxy or trialkylsilyloxy, ρ
R is hydrogen or halogen and R is halogen, and their salts, which are known to be used as synergists for pest control » 2. Use according to Anspruoh 1, characterized in that in the general formula (I) X represents a nitrogen atom or a CJH group, R is optionally substituted by halogen tert-alkyl having 4 to 8 carbon atoms or f'Jr optionally duroh alkyl having 1 to 4 carbon atoms and / or halogen-substituted cycloalkyl having 3 to 6 carbon atoms, and R ³ A for the groupings -C = O-, -0 GH- or -C = C-R stands, in which R 'is halogen, alkoxy of 1 to 4 carbon atoms or is trimethylsloxy, R stands for hydrogen peroxide or halogen and for halogen. - 89 - 3 «Use according to claim 1, characterized daduroh that in the general formula (I) X stands for a nitrogen atom or a GH group, R is optionally substituted by chlorine and / or Fl .r substituted tert-alkyl having 4 to 8 carbon atoms or optionally chloro, methyl, ethyl and / or isopropyl substituted cyclopropyl, cyolopentyl or cyclohexyl and A is the moiety -C-C- or A is the moiety -G = C- I i R ¹ n ² ti Sx in which (a) R ^{1 is} chloro, methoxy, ethoxy or Trimethylsilyloxy is and R ^{2 is} hydrogen, or (b) R ¹ and R ^{2 are} chlorine, or A is the moiety -C CH- I ₁ I ₂ R ¹ R ^ stands, wherein R ¹ , R ² and R ^{3 are} chlorine ·