DE4020384A1 - Fungicidal O-benzyl oxime ether derivs. - useful as insecticides and nematocides for protecting plants, materials and in veterinary and hygiene areas - Google Patents

Abstract

O-Benzyl-oxime-ether derivs of formula (I) are new. X = CH2, CH(1-4C)alkyl, CH(1-4C)alkoxy, CH(1-4C) alkylthio, N(1-4C)alkoxy; Y = O, S or NR5; R15R2,R5 = H or 1-4Calkyl; Z1, Z2 = H, halo, Me, MeO or CN; R3, R4 = H, CN, opt. branched 1-10C alkyl, 1-4C haloalkyl, 3-6C (halo)cycloalkyl, 3-6C cylcoalkyl 1-4C alkyl, 1-4Calkoxy 1-4Calkylthio 1-4C alkyl, arylthiol1-4Calkyl, 2-6C alkenyl, 2-5C haloalkenyl 3-6C (halo)cycloalkenyl, 2-6C alkynyl, 1-6C(halo)alkoxy, 1-4C alkylthio, benzylthio (1-4C)alkyl carbonyl, opt. substd. phenyl- or benzylcarbonyl 1-4C alkoxycarbonyl, opt substd. phenoxy- or benzyloxy carbonyl, or opt. substd. aryl, aryloxy, aryl thio, aryl(1-4C)alkyl, aryl (2-4C)alkenyl heteroaryl, heteroaryloxy, heteroarylthio, hetroaryloxy (1-4C) alkyl, hetero aryloxy1-4C alkenyl, heteroaryloxy 1-4C alkyl (sic), heterocyclyl or heterocyclyloxy; N(R6)2 or CON(R7)2; R6 = H, 1-6C alkyl or opt. substd. phenyl; R7 = H or 1-4C alkyl; or R3 + R4 = carbo or heterocyclic ring opt. substd; or R3 or R4 = halo; opt. substits. are H, CN, NO2, 1-4C alkyl, 1-4C alkoxy, heteroaryl, heteroaryloxy, 3-6C cycloalkyl, heterocyclyl or heterocyclyloxy. USE - (I) are fungicides useful for treating e.g. materials, plants and leather. They are also pesticides active against insects, nematodes etc. They are also useful in hygiene and veterinary areas. Dosage is 0.01-10 pref. 0.1-1 kg/ha.

Description

The present invention relates to new O-benzyl oxime ethers and Methods for controlling pests, in particular fungi, Insects, nematodes and spider mites with these compounds.

It is known to use substituted phenylacetic acid oxime derivatives as fungicides (EP 2 53 213) to use. However, their effect is unsatisfactory.

It has surprisingly been found that O-benzyl oxime ethers of the general Formula I.

in the
X CH₂, CH-C₁-C₄-alkyl, CH-C₁-C₄-alkoxy, CH-C₁-C₄-alkylthio, N-C₁-C₄-alkoxy
YO, S, NR⁵,
R¹, R², R⁵ H, C₁-C₄ alkyl,
Z¹, Z² are the same or different and are H, halogen, methyl, methoxy, cyano,
R³, R⁴ are the same or different and are hydrogen, cyano, optionally branched C₁-C₁₀-alkyl, C₁-C₄-haloalkyl, C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl , C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkylthio-C₁-C₄-alkyl, arylthio-C₁-C₄-alkyl, C₂-C₆-alkenyl, C₂-C₅-haloalkenyl, C₃-C₆-cycloalkenyl , C₃-C₆-halocycloalkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₄-alkylthio, benzylthio, C₁-C₄-alkylcarbonyl, optionally subst. Phenylcarbonyl, optionally subst. Benzylcarbonyl, C₁-C₄-alkoxycarbonyl, optionally subst. Phenoxycarbonyl, optionally subst. Benzyloxycarbonyl, optionally subst. Aryl, if necessary subst. Aryloxy, optionally subst. Arylthio, possibly subst. Aryl-C₁-C₄-alkyl, optionally subst. Aryl-C₁-C₄-alkenyl, optionally subst. Aryloxy- C₁-C₄-alkyl, optionally subst. Arylthio-C₁-C₄-alkyl, optionally subst. Hetaryl, possibly subst. Hetaryloxy, optionally subst. Hetarylthio, possibly subst. Heteroary-C₁-C₄- alkyl, optionally subst. Hetaryl-C₁-C₄-alkenyl, optionally subst. Hetaryloxy-C₁-C₄- alkyl, optionally subst. Heterocyclyl, optionally subst. Heterocyclyloxy mean
N (R⁶) ₂, the meanings of R⁶ being the same or different and H, C₁-C₆-alkyl, optionally subst. Phenyl mean
-CO-N (R⁷) ₂, where the meanings of R⁷ are the same or different and are H, C₁-C₄-alkyl;
where "possibly subst." in addition to hydrogen, the radicals halogen, cyano, nitro, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₁₀-alkoximino-C₁-C₂-alkyl, aryl, aryloxy, Mean benzyloxy, hetaryloxy, C₃-C₆-cycloalkyl, heterocyclyl, heterocyclylooxy,
R³ and R⁴ together can form a carbocyclic or heterocyclic ring, which can be replaced by the "optionally subst." mentioned radicals can be substituted and
R³ and R⁴ can be halogen,
have an excellent fungicidal, insecticidal, nematicidal and acaricidal activity which is better than that of the known phenylacetic acid derivatives.

The fungicidal activity is preferred.

The radicals listed in the general formula I can have the following meanings, for example:
X can be C₁-C₄-alkylidene (e.g. methylidene, ethylidene, n- or iso-propylidene, n-, iso-, sec- or tert-butylidene), C₁-C₄-alkoxymethylidene (e.g. methoxy -, Ethoxy-, n- or iso-propoxy, n-, iso-, sec.- or tert.-butoxymethylidene), C₁-Cth-alkylthiomethylidene (e.g. methyl, ethyl, n- or iso-propyl , n-, iso-, sec.- or tert.-butylthiomethylidene), C₁-C₄-alkoxyimino (e.g. methoxy-, ethoxy-, n- or iso-propoxy-, n-, iso-, sec.- or tert-butoxyimino),
Y can O, S, NR⁵,
R¹, R², R⁵ can be H or C₁-C₄-alkyl (e.g. methyl, ethyl, n- or iso-propyl, n-, iso-, sec.- or tert.-butyl),
Z¹, Z² can be H, halogen (e.g. fluorine, chlorine, bromine, iodine), methyl, methoxy, cyano,
R³, R⁴ can be the same or different and can be hydrogen, cyano, optionally branched C₁-C₁₀ alkyl (e.g. methyl, ethyl, n- or iso-propyl, n-, iso-, sec.- or tert.- Butyl, n-, iso-, sec.-, tert.- or neo-pentyl, n-hexyl, n-decyl),
C₁-C₄ haloalkyl (e.g. trifluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, fluorodichloromethyl, difluorochloromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2-chloroethyl, 2,2,2-trichloroethyl, pentachloroethyl) ,
C₃-C₆-cycloalkyl (e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl),
C₃-C₆-halocycloalkyl (e.g. 2,2-difluorocyclopropyl, 2,2-dichlorocyclopropyl, 2,2-dibromocyclopropyl, 2,2-dichloro-3-methylcyclopropyl, tetrafluorocyclobutyl),
C₃-C₆-cycloalkyl-C₁-C₄-alkyl (e.g. 1-methylcyclopropyl, 2,2-dimethylcyclopropyl, 1-methylcyclohexyl),
C₁-C₄-alkoxy-C₁-C₄-alkyl (e.g. methoxymethyl, ethoxymethyl, n- or iso-propoxymethyl, n-, iso-, sec.- or tert-butoxymethyl, 2-methoxy-prop-2- yl, 2-ethoxyprop-2-yl, 2-n- or iso-propoxyprop-2-yl, 2-n-, iso-, sec- or tert-butoxy-prop-2-yl),
C₁-C₄-alkylthio-C₁-C₄-alkyl (e.g. methylthiomethyl, ethylthiomethyl, n- or iso-propylthiomethyl, n-, iso-, sec.- or tert.-butylthiomethyl, 2-methylthioprop-2-yl, 2-ethylthioprop-2-yl, 2-n- or iso-propylthio-prop-2-yl, 2-n-, iso-, sec- or tert-butylthio-prop-2-yl),
Aryl (phenyl) thio-C₁-C₄-alkyl (e.g. phenylthiomethyl, 2-chlorophenylthiomethyl)
C₂-C₆ alkenyl (e.g. vinyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 3-methyl-2-butenyl, 2-methyl-2- penten-5-yl),
C₂-C₅-haloalkenyl (e.g. 2,2-difluorovinyl, 2,2-dichlorovinyl, 3,3,3-trifluoropropenyl, 3,3,3-trichloropropenyl, 3-chloro-2-propenyl),
C₃-C₆-cycloalkenyl (e.g. cyclopent-1-enyl, cyclopentadienyl, cyclohex-1-enyl),
C₃-C₆-halocycloalkenyl (e.g. pentafluorocyclopentadienyl, pentachlorocyclopentadienyl),
C₂-C₄ alkynyl (e.g. ethynyl, 1-propynyl, 1-propargyl),
C₁-C₄ alkoxy (e.g. methoxy, ethoxy, n- or iso-propoxy, n-, iso-, sec- or tert-butoxy),
C₁-C₄-alkylthio (e.g. methylthio, ethylthio, n- or iso-propylthio, n-, iso-, sec.- or tert.-butylthio), benzylthio,
C₁-C₄ haloalkoxy (e.g. trifluoromethoxy, pentafluoroethoxy, 1,1,2,2-tetrafluoroethoxy),
NR⁶₂ (e.g. amino, methylamino, dimethylamino, ethylamino, diethylamino, di-n-propylamino, di-iso-propylamino, di-n-butylamino, di-iso-butylamino),
C₁-C₄ alkylcarbonyl (e.g. acetyl, propionyl, butyryl, isobutyryl, pivaloyl),
if necessary subst. Phenylcarbonyl (e.g. benzoyl, 4-chlorobenzoyl),
if necessary subst. Benzylcarbonyl (e.g. benzylcarbonyl),
C₁-C₄ alkoxycarbonyl (e.g. methoxycarbonyl, ethoxycarbonyl, n- or iso-propoxycarbonyl, n-, iso-, sec- or tert-butoxycarbonyl),
if necessary subst. Phenoxycarbonyl (e.g. phenoxycarbonyl, 4-chlorophenoxycarbonyl),
if necessary subst. Benzyloxycarbonyl (e.g. benzyloxycarbonyl),
-CO-N (R⁷) ₂ (e.g. aminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl, di-iso-propylaminocarbonyl, phenylaminocarbonyl, N-methyl-N-phenylaminocarbonyl),
if necessary subst. Aryl (e.g. phenyl, naphthyl, anthryl),
if necessary subst. Aryloxy (e.g. phenoxy, naphthoxy, anthroxy),
if necessary subst. Arylthio (e.g. phenylthio),
if necessary subst. Aryl-C₁-C₄-alkyl (e.g. benzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 2-methyl-3-phenylpropyl, 2-methyl-2-phenylpropyl, 4-phenylbutyl),
if necessary subst. Aryl-C₁-C₄-alkenyl (e.g. phenyl-1-ethenyl, 2-phenyl-1-propenyl, 2,2-diphenylethenyl, 1-phenyl-1-propen-2-yl, 1-phenyl-1- ethenyl),
if necessary subst. Aryloxy-C₁-C₄-alkyl (e.g. phenoxymethyl),
if necessary subst. Arylthio-C₁-C₄-alkyl (e.g. phentylthiomethyl),
if necessary subst. Heteroaryl (e.g. pyridyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, pyrimidinyl, 2,6-pyrimidinyl, 1,5-pyrimidinyl, thienyl, 2-thienyl, 3-thienyl, furyl, 2-furyl, 3-furyl, 1-pyrrolyl, 1-imidazolyl, 1,2,4-triazolyl, 1,3,4-triazolyl, 4-thiazolyl, 2-benzothiazolyl),
if necessary subst. Heteroaryloxy (e.g. 2-pyridyloxy, 2-pyrimidinyloxy),
if necessary subst. Heteroarylthio (e.g. 2-pyridylthio, 2-pyrimidinylthio, 2-benzothiazolylthio),
if necessary subst. Heteroaryl-C₁-C₄-alkyl (e.g. 2-pyridylmethyl, 3-pyridylmethyl),
if necessary subst. Heteroaryloxy-C₁-C₄-alkyl (e.g. furfurylmethoxy, thienylmethoxy, 3-isoxazolylmethoxy, 2-oxazolylmethoxy, 2-pyridylmethoxy),
if necessary subst. Heteroaryl-C₂-C₄-alkenyl (e.g. 2′-furyl-2-ethenyl, 2′-thienyl-2-ethenyl, 3′-pyridyl-2-ethenyl),
if necessary subst. Heterocyclyl (e.g. oxiranyl, 1-aziridinyl, 1-azetidinyl, 1-pyrrolidinyl, 2-tetrahydrofuryl, 2-tetrahydropyranyl, 3-tetrahydropyranyl, 1-piperidinyl, 1-morpholinyl, 1-piperazinyl, 1,3-dioxanyl, 3-tetrahydrothiopyranyl),
if necessary subst. Heterocycloxy (e.g. 2-dihydropyranyloxy, 2-tetrahydropyranyloxy).

The radicals referred to in the above as “optionally substituted” are beside Hydrogen z. B. fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, iso-propyl, tert-butyl, methoxy, ethoxy, iso-propoxy, tert-butoxy, Trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, trifluoromethoxy, 1,1,2,2-tetrafluoroethoxy, methoxyiminomethyl, ethoxyiminoethyl, n-propoxyiminomethyl, n-butoxyiminomethyl, n-pentoxyiminomethyl, n-hexoxyiminomethyl, Allyloxyiminomethyl, benzyloxyiminomethyl, iso-propoxyiminomethyl, iso-butoxyiminomethyl, tert-butoxyiminomethyl, methylimino 1-ethyl, ethoxyimino-1-ethyl, n-propoxyimino-1-ethyl, n-butoxyimino 1-ethyl, n-pentoxyimino-1-ethyl, n-hexoxyimino-1-ethyl, allyloxyimino 1-ethyl, benzyloxyimino-1-ethyl, phenyl, phenoxy, benzyloxy, Imidazol-1-yl, piperazin-1-yl, 4-morpholinyl, piperidin-1-yl, pyridyl-2- oxy, cyclopropyl, cyclohexyl, oxiranyl, 1,3-dioxan-2-yl, 1,3-dioxolan-2- yl, tetrahydropyran-2-yloxy.

The group

can also be the remainder of a carbo- or heterocyclic oxime (e.g. Cyclopentanone oxime, cyclohexanone oxime, cycloheptanone oxime, 2-adamantanone oxime, D-campheroxime, 1-tetralonoxime, 1-indanone oxime, 9-fluorenone oxime, 1-methyl-4- Piperidone oxime, violuric acid, N, N-dimethylvioluric acid).

The radicals R³ and R⁴ together then form z. B. a cyclopentyl, cyclohexyl, Cycloheptyl, Adamantyl, Camphenyl, Tetralin, Indan- or Fluorene ring.

Likewise one of the radicals R³ or R⁴ halogen (e.g. fluorine, chlorine, bromine, Iodine).

Of the compounds with R³, R⁴ hydrogen, the compounds are preferred, in which either only R³ or only R⁴ is hydrogen, in particular the compounds in which R³ is hydrogen.

The new compounds of general formula I can in the preparation due to the C = C or C = N double bonds as E / Z isomer mixtures attack. These can be done in the usual way, e.g. B. by crystallization or chromatography into the individual components.  

Both the individual isomeric compounds and their mixtures are encompassed by the invention and are useful as pesticides.

The preparation of the compound of general formula I according to claim 1 is carried out, for example, as described in scheme 1 (Z¹, Z² is H).

The compounds of general formula I in which X = CH₂, CH-alkyl, Is CH-alkoxy, for example, from the keto esters 4 Prepare the Wittig or Wittig-Horner reaction (cf. EP 3 48 766, DE 37 05 389, EP 1 78 826). Analog connections 5 are also obtained from the keto esters 2.

Alternatively, one can proceed in such a way that connections of the Formula 7 or 9 condensed with suitable reagents, e.g. B. for X = CH₂ with Formaldehyde (see DE 33 17 356), for X = CH-alkyl a) with aldehydes (cf. D.M. Brown J. Chem. Soc. 1948, 2147) or b) first with N, N-dimethylformamide dimethyl acetate, followed by reaction with a Grignard reagent (analogous to C. Jutz Chem. Ber. 91, 1867 (1958)), for X = CH-O-alkyl with  Formic acid ester followed by alkylation (see EP 1 78 826). Further Manufacturing instructions for the compounds of formula 5 and I with X = CH-O-alkyl are described in EP 1 78 826.

Another way to prepare the compounds of formula I with X = CH-alkyl and YR₂ = COOAlk is the reaction of ketene acetals with phenylchlorocarbenes (see N. Slougui, G. Rousseau, Synth. Commun. 12 (5) 401-7 (1982)).

For compounds of the general formula I in which X = CH-S-alkyl, can they are produced by the methods from EP 2 44 077 or 3 10 954.

The intermediates of formulas 3, 6 and 8 can be derived from the compounds Manufacture 2, 5 and 7 by making them according to known methods halogenated, e.g. B. with chlorine, bromine, N-bromosuccinimide in an inert Solvent (e.g. CCl₄, cyclohexane) under exposure to z. B. one Mercury vapor lamp or radical starters, such as. B. dibenzoyl peroxide, or by the residues L as via suitable intermediates (L = halogen, OH) e.g. B. mesylate, tosylate, acetate or triflate.

The oxime ethers of the formula I with X = N-O-alkyl can be obtained from 4a) Reaction with O-alkylhydroxylamine hydrochloride or b) with hydroxylamine hydrochloride and subsequent alkylation with an alkylating agent (such as alkyl iodide, dialkyl sulfate, etc.) (see. DE 36 23 921).

Likewise, analogous to the method in EP 2 54 426, a phenylacetic ester of Formula 9 with a base (such as NaOMe, NaH, NaH, K-tert-butoxide, etc.) in a solvent (such as diethyl ether, toluene, tert-butanol etc.) in transferred its anion and with a suitable nitrosating agent (such as e.g. As methyl nitrite, amyl nitrite, tert-butyl nitrite, etc.) are oximized. The resulting oximate is treated with an alkylating agent (such as Alkyl iodide, dialkyl sulfate) alkylated.

The same procedures are also applicable to the compounds of the formula 2 and 7 transferable, the resulting oxime ether 5 as known EP 2 54 426) via the intermediate 6 (L = z. Halogen) in the target compounds I can be transferred.

Usually, the rest of the manufacturing processes described above Y-R1 = alkoxy.

The compounds with YR¹ = OH (11) can be prepared from the compounds of the general formula I in which YR¹ = COOalkyl (10) by methods known from the literature (Organikum 16th edition, p. 415, 622) (see scheme 2 ).

Alternatively, the nitriles 12 can be used in a known manner (see Organikum 16th edition, p. 424f (1985)) can be converted into the carboxylic acids 11.

The carboxylic acids 11 obtained in this way can be prepared in a manner known per se produce the acid chlorides 14 (see Organikum 16th edition, p. 423f B. (1985)). The conversion of 14 into the amides 15 takes place analogously to the organic agent 16th edition p. 412 (1985).

The thiolesters 13 are obtained from the acid chlorides 14 (analogously to Houben-Weyl Vol. 8 pp. 464ff (1952)).

Alternatively, the thiolesters 13 can also be prepared from the acids 11 (analogous to Houben-Weyl vol. E5 p. 855f (1985)).

The preparation of the amides 15 with R¹, R⁵ = H can also according to the literature Processes are carried out from the nitriles 12 (see also Synthesis 1980, 243).

The preparation of the compounds of general formulas 2 and 7 with ortho-methyl substitution on the aromatic (R² = H) is known.
(YR 1 = O alkyl; see EP 1 78 826, EP 2 60 832).

Those required for the preparation of the compounds of general formula I. Oximes are either known or can be according to one of the methods in Scheme 3 shown methods are produced.  

Scheme 3

Methods for the implementation of 16 or 18 to 17 can be found in Houben-Weyl, Vol. 10/4 (1968).

Furthermore, Aldoxime 19 can be chlorinated by known methods and with e.g. B. cyanide to the derivatives 17 (R⁴ = CN) are implemented (cf. M. R. Zimmermann J. f. Practical Chemistry 66, 359 (1902)).

The special derivatives with R³ = CN, R⁴ = alkoxyalkyl are described in EP 74 047, with R³ = CN, R⁴ = alkylthioalkyl according to EP 1 50 822 and with R³ = CN, R⁴ = alkyl according to DE 23 04 848 manufactured.

For sterically hindered ketones, the method comes with Me₃SiO-NH-SiMe₃ (R.U. Hoffmann, G.A. Buntain, Synthesis 1987, 831).

Scheme 4

The representation of the new compounds of general formula I according to Claim 1 is carried out, for example, by using an oxime of the formula 17 a substituted benzyl compound 6 in L is a leaving group (e.g. Chloride, bromide, p-toluenesulfonate, methanesulfonate, triflate, acetate) means implements. R¹-R⁴, X and Y have the meanings given above.  

The implementations described can e.g. B. in an inert solvent (e.g. acetone, acetonitrile, dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone or pyridine) using a base (e.g. sodium carbonate, Potassium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, Sodium methylate).

The reactions can also be carried out in a two-phase system (e.g. dichloromethane, Water) with the aid of a suitable phase transfer catalyst (e.g. cetyltrimethylammonium chloride, benzyltrimethylammonium chloride) be performed.

Another way to prepare the compounds I (YR¹ = Oalkyl, X = CH-Oalkyl or N-Oalkyl, L = Cl, Br, tosylate, mesylate) Scheme 5.

Scheme 5

This synthesis sequence takes place up to compound 22 analogously to that in FIGS Methods described in EP 2 44 786.

So you can N-hydroxyphthalimide with halides or sulfonic acid esters 6 in the presence of an acid binding agent (e.g. triethylamine, potassium carbonate etc.) in a suitable solvent (e.g. N-methylpyrrolidone, Transfer DMF etc.) into the imide ether 21.

The cleavage to the O-substituted hydroxylamine 22 can be done with mineral acid (e.g. HCl; see Houben-Weyl Vol. 10/1 p. 1181ff.) or in the basic (e.g. with Hydrazine, ethanolamine).  

The amine 22 is converted into I in a manner known per se (cf. D. Otzanak, J.C.S. Chem. Commun. 1986, 903).

The following examples and regulations are intended to help manufacture the new Explain active ingredients and the new intermediates.

Regulation 1 3,4-dichloroacetophenone oxime

12.0 g (0.17 mol) hydroxylammonium hydrochloride and 18.9 g (0.1 mol) 3,4-dichloroacetophenone are in a mixture of 20 ml of H₂O, 100 ml Added methanol and 8 g (0.1 mol) of pyridine. After refluxing for 1 h acidified with 2N HCl and extracted with 3 × 100 ml of tert-butyl methyl ether. The org. Phase is washed with water, with Na₂SO₄ dried and concentrated. 19.6 g (96% of theory) of crystals fall with it a melting point of 92 ° C, which according to 1 H-NMR to 90% from trans-oxime consist.

Regulation 2 2-oximino-2-tetrahydropyran-2'-yl-acetonitrile

265.4 g (2.05 mol) of tetrahydrofuran-2-carbaldehyde oxime are dissolved in 2 l Diethyl ether submitted at -55 to -60 ° C. Then 153.5 g (2.15 mol) chlorine introduced and the temperature increased to -20 ° C; 1 h stir, then concentrate on a rotary evaporator at 10 ° C, the residue take up in 1.5 l of diethyl ether and overnight with exclusion of light Stir ice cooling. It is then filtered off and 147.3 g with ice cooling (2.27 mol) potassium cyanide in 1 l of methanol at 10-15 ° C (exothermic). After stirring for 5 h at room temperature (20 ° C), the precipitate is filtered off with suction and washed twice with diethyl ether. The org. Phases are between Distributed tert-butyl methyl ether and water and the residue of the ether phases crystallized from dichloromethane / n-hexane at 0 ° C.

After suction and drying, 208 g (66% of theory) remain spectroscopically pure substance with the melting point m.p .: 105-106 ° C.

Regulation 3 3-methoxy-3-methyl-2-oximino-butyronitrile

53.6 g (0.46 mol) of 2-methoxy-2-methyl-propionaldehydroxime are dissolved in ether (approx. 1 M) at -5 ° C to -10 ° C. After gassing 35.8 g (0.5 mol) Chlorine is stirred at this temperature for 1 h, then concentrated at 10 ° C. and the residue taken up in diethyl ether. 24.7 g (0.5 mol) sodium cyanide 375 ml of methanol / H₂O 20: 1 are presented at 10 ° C and the above ethereal solution quickly added dropwise. After 4 h at room temperature suction filtered and washed 2 × 100 ml MeOH. The combined solutions are tight  one and subject it to a distribution between methyl tert-butyl ether and water. Drying or organic phase (Na₂SO₄), concentrate and crystallize (dichloromethane / n-hexane) leads to 41.1 g (63% of theory) a white powder with a melting point of 102-104 ° C.

Regulation 4 3-methoxy-2- [2 ′ - (phthalimidooxy) methyl] phenyl-acrylic acid methyl ester

10 g (35 mmol) of 3-methoxy-2- (2'-bromomethyl) phenyl-acrylic acid methyl ester, 5.7 g (35 mmol) of hydroxyphthalimide, 3.9 g (38.6 mmol) of triethylamine and 50 ml of N-methylpyrrolidone are combined and stirred at 60 ° C. for 2 h. Then you pour on ice water, suck off the residue, wash it with Water and iso-propanol and dries i. Vac. 9.0 g (70% d. Th.) Crystalline product with the melting point 156-158 ° C.

1 H-NMR (CDCl₃): δ = 3.60 (s, 3H); 3.75 (s, H); 5.12 (s, 2H); 7.13 (dbr, 1H); 7.35 (m. 2H); 7.62 (s, 1H); 7.7-7.9 (m, 5H).

Regulation 5 3-methoxy-2- (2'-aminooxymethyl) phenyl-acrylic acid methyl ester

10.0 g (27 mmol) of the product from instruction 4 is in 150 ml of methanol dissolved and with 1.4 g of hydrazine hydrate (27 mmol) for 2 h at room temperature touched. The precipitate is filtered off with suction, the mother liquor is evaporated down with Diethyl ether stirred, the precipitate suctioned off again and the mother liquor constricted. 6.0 g (92% of theory) of a yellow oil result (Purity according to 1 H-NMR approx. 90%).

1 H-NMR (CDCl₃): δ = 3.71 (s, 3H); 3.80 (s, 3H); 4.60 (s, 2H); 5.35 (sbr, 2H); 7.0-7.50 (m, 4H); 7.58 (s, 1H).

Regulation 6 2-methoxyimino-2- (2'-phthalimidooxymethyl) phenylacetic acid methyl ester

2.0 g (7 mmol), 2-methoxyimino-2- (2'-bromomethyl) phenylacetic acid methyl ester, 1.1 g (7 mmol) hydroxyphthalamide, 0.8 g (7.7 mmol) triethylamine are dissolved in 10 ml of N-methylpyrrolidone and stirred at 70 ° C. for 2 h. To Working up is mixed with ice water, the crystals are suctioned off with Washed water and methyl tert-butyl ether and dried.  

1.5 g (58% of theory) of crystals with the melting point remain 152-155 ° C.

1 H-NMR (CDCl₃): δ = 3.83 (s, 3H); 3.98 (s, 3H); 5.07 (s. 2H); 7.15 (dbr, 1H); 7.45 (mc, 2H); 7.60-7.85 (m, 5H).

Regulation 7 2-methoximino-2- (2'-aminooxymethyl) phenylacetic acid methyl ester

15.0 g (41 mmol) of product from regulation 6 are mixed with 2.1 g (42 mmol) Hydrazine hydrate in 150 ml of methanol was stirred for 2 hours at room temperature. The The residue is filtered off with suction, the mother liquor is evaporated down with diethyl ether triturated, the residue is suctioned off again, the mother liquor concentrated. It 7.8 g (80% of theory) of an acid-sensitive oil remain.

1 H-NMR (CDCl₃): δ = 3.90 (s, 3H); 4.03 (s, 3H); 4.59 (s. 2H); 5.35 (sbr, 2H); 7.15 (dbr, 1H); 7.40 (sbr, 3H).

Example 1 3-methoxy-2- [2 ′ [1 ′ ′ - (3 ′ ′ ′, 5 ′ ′ ′ - dichlorophenyl) -1 ′ ′ - methyl] -iminooxyme-thyl] - phenyl-acrylic acid methyl ester (No. 582, Tab. 1)

0.6 g (25 mmol) sodium hydride powder are placed in 100 ml acetonitrile, 5.1 g (25 mmol) of 3,5-dichloroacetone phenoxime were added and 1 h on Reflux cooked. Then 9.3 g (33 mmol) of 2- (2'-bromomethyl) phenyl-3- added methoxy-acrylic acid methyl ester in 50 ml of acetonitrile and others Boiled at reflux for 4 h. After narrowing i. Vac. is between methyl tert. Butyl ether and sat. Distributed ammonium chloride solution, the org. Phase with Washed water and the residue obtained by concentration from methyl butyl ether / n-hexane crystallized. 4.6 g (45% of theory) of one are obtained Substance with melting point m.p .: 87-88 ° C.

1 H-NMR (CDCl₃): δ = 2.19 (s, 3H); 3.70 (s, 3H); 3.81 (s, 3H); 5.15 (s. 2H); 7.08 (m, 1H); 7.17 (m. 3H); 7.50 (m. 3H); 7.58 (s, 1H).

Example 2 3-methoxy-2- [2 ′ - (1 ′ ′ - cyano- (1 ′ ′ - methoxy-1 ′ ′ - methylethyl) iminooxymethyl-hyl] - phenyl-acrylic acid methyl ester (No. 36, Tab. 1)

3.3 g (23 mmol) of 3-methoxy-3-methyl-2-oximino-butyronitrile, 6.6 g (23 mmol) of 2- (2'-bromomethylphenyl) -3-methoxy-acrylic acid methyl ester and 3.2 g ( 23 mmol) of potassium carbonate in 60 ml of N, N-dimethylformamide for 15 h at room temperature. touched. Then it is concentrated, taken up in ethyl acetate, washed with 3 × 50 ml of water, the org. Phase over sodium sulfate, concentrated and chromatographed on silica gel (toluene / ethyl acetate 40: 1).
Yield: 7.0 g (88% of theory) of an oil.
IR (film): 1285, 1258, 1189, 1180, 1131, 1111, 1069, 1008 cm -1.

Example 3 2-methoximino-2- [2 ′ - (1 ′ ′ - (3 ′ ′ ′, 5 ′ ′ ′ - dichlorophenyl) -1 ′ ′ - methyl) iminoo-xymethyl] - phenylacetic acid methyl ester (No. 582, Tab. II)

0.6 g (25 mmol) NaH are placed in 50 ml acetonitrile and at room temperature. 5.1 g (25 mmol) of 3,5-dichloroacetophenone oxime were added. After 1 h at 9.4 g (33 mmol) of 2-methoximino-2- (2'-bromomethyl) phenyl- methyl acetate was added dropwise in 50 ml of acetonitrile and a further 4 h on Heated to reflux. After concentration, distribute between water / methyl tert. Butyl ether, wash the org. Phase with water, drying the org. phase With sodium sulfate and concentration, the residue is subjected to column chromatography subjected to silica gel (methyl tert-butyl ether / hexane). It 5.4 g (53% of theory) of crystals with a melting point of 95-97 ° C. result.

1 H-NMR (CDCl₃): δ = 2.17 (s, 3H); 3.82 (s, 3H); 4.02 (s, 3H); 5.15 (s. 2H); 7.20 (dbr, 1H); 7.25-7.55 (m, 6H).

Example 4 3-methoxy-2- [2 ′ - (1 ′ ′ - (4 ′ ′ ′ - bromophenyl) 1 ′ ′ - methyl) iminooxymethyl] phen-ylacrylic acid methyl ester (No. 593, Tab. I)

2.37 g (10 mmol) of methyl 3-methoxy-2- (2'-aminooxymethyl) phenylacrylate, 1.99 g (10 mmol) 4-bromoacetophenone, 2 ml water, 0.8 g pyridine and 10 ml of methanol are combined and 24 h at room temperature. stirred. After concentration, partition between water / methyl tert-butyl ether, wash the org. Phase with 2 N HCl and wash neutral with NaHCO₃ is concentrated and chromatographed on SiO₂ (MtBE / hexane). The result is 2.1 g (51% of theory Th.) Crystals, mp: 105-107 ° C.

1 H-NMR (CDCl₃): δ = 2.22 (s, 3H); 3.70 (s, 3H); 3.80 (s, 3H); 5.15 (s. 2H); 7.16 (dbr, 1H); 7.33 (m. 2H); 7.45 (m, 5H); 7.58 (s, 1H).  

Example 5 2-methoximino-2 [2 ′ - (1 ′ ′ - (4 ′ ′ ′ - nitrophenyl) 1 ′ ′ - methyl) iminooxymethyl] phenyl methyl acetate (No. 614, Tab. II)

2.38 g (10 mmol) of methyl 2-methoximino-2- (2'-aminooxymethyl) phenylacetate, 1.65 g (10 mmol) 4-nitroacetophenone, 2 ml water, 0.8 g Pyridine and 10 ml of methanol are reacted as in Example 4. 2.1 g (55% of theory) of crystals with a fixed point of 87-89 ° C. are obtained.

1 H-NMR (CDCl₃): δ = 2.22s, 3H); 3.81 (s, 3H); 4.02 (s, 3H); 5.18 (s. 2H); 7.20 (dd, 1H); 7.4 (m. 3H); 7.75 (dd. 2H); 8.18 (dd, 2H).

Example 6 3-methoxy-2- [2 ′ - (1 ′ ′ - (4 ′ ′ ′ - chlorophenyl) iminooxymethyl] phenylacrylic acid methyl ester (No. 95 Tab. 5)

a) 5.5 g (15 mmol) of 3-methoxy-2- [2 ′ - (phthalimidooxy) methylphenylacrylsäuremethylester (from regulation 4) are placed in 100 ml of methanol and 0.75 g (15 mmol) of hydrazine hydrate were added at room temperature. After 15 minutes at this temperature, the mixture is concentrated and the product is triturated Residue with methyl tert-butyl ether and sucks off the cleavage product. The mother liquor is concentrated, taken up in 50 ml of methanol and dropwise with 2.1 g (15 mmol) of 4-chlorobenzaldehyde in 50 ml of methanol plus 1 drop of pyridine added.

After stirring overnight at 23 ° C, the product could be suctioned off with Wash and dry methanol.

2.9 g (54% of theory) of crystals with the mp: 87-89 ° C. were obtained.

1 H-NMR (CDCl₃): δ = 3.66 (s, 3H); 3.80 (s, 3H), 5.13 (s, 2H); 7.17 (m, 1H), 7.35 (m, 4H), 7.50 (me, 3H); 7.60 (s, 1H); 8.06 (s, 1H).

b) 1.3 g (55 mmol) of NaH powder become slow under a nitrogen atmosphere mixed with 50 ml of methanol (hydrogen evolution). Then you give at room temperature 7.8 g (50 mmol) of 4-chlorobenzaldehyde oxime in 50 ml Methanol too. After stirring for half an hour, 14.3 g (50 mmol) 3-methoxy-2- (2'-bromomethyl) phenyl-acrylic acid methyl ester in 50 ml Methanol was added dropwise and 48 h further at room temperature. touched. The White The residue is filtered off, washed with methanol and dried. Man receives 1.9 g (11% of theory) of product with the melting point: 82-84 ° C.

The compounds listed in Tables I-IV can be prepared in a corresponding manner.

Table III

Table V

Table VI

Generally speaking, the new compounds are characterized by a excellent effectiveness against a wide range of phytopathogenic agents Mushrooms, in particular from the classes of the Ascomycetes and Basidiomycetes, out. They are partially systemic and can be used as leaf and Soil fungicides are used.

The fungicidal compounds are particularly interesting for combating a variety of fungi on different crops or their Seeds, especially wheat, rye, barley, oats, rice, corn, lawn, Cotton, soy, coffee, sugar cane, fruit and ornamental plants in horticulture, Viticulture and vegetables - such as cucumbers, beans and squashes -.

The new compounds are particularly suitable for controlling the following plant diseases:
Erysiphe graminis (powdery mildew) in cereals,
Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants,
Podosphaera leucotricha on apples,
Uncinula necator on vines,
Puccinia species on cereals,
Rhizoctonia species on cotton and lawn,
Ustilago species on cereals and sugar cane,
Venturia inaequalis (scab) on apples,
Helminthosporium species on cereals,
Septoria nodorum on wheat,
Botrytis cinerea (gray mold) on strawberries, vines,
Cercospora arachidicola on peanuts,
Pseudocercosporella herpotrichoides on wheat, barley,
Pyricularia oryzae on rice,
Phytophthora infestans on potatoes and tomatoes,
Fusarium and Verticillium species on different plants,
Plasmopara viticola on vines,
Alternaria species in vegetables and fruits.

The compounds are applied by treating the plants with the active ingredients sprayed or dusted or the seeds of the plants with the active ingredients treated. It is used before or after infection Plants or seeds through the mushrooms. It will be the mushrooms or the ones before Fungus infestation to protect plants, seeds, materials or the soil treated with a fungicidal effective amount of the active ingredient.  

The new substances can be converted into the usual formulations such as solutions, emulsions, suspensions, dusts, powders, pastes and Granules. The application forms depend entirely on the purposes; in any case, they should have a fine and even distribution ensure the effective substance. The wording is in manufactured in a known manner, e.g. B. by stretching the active ingredient with Solvents and / or carriers, optionally using Emulsifiers and dispersants, where in the use of Water as a diluent other than organic solvents Auxiliary solvents can be used. As auxiliaries come for it essentially in question: solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), Alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanone), amines (e.g. Ethanolamine, dimethylformamide) and water; Carriers like natural Rock flours (e.g. kaolins, clays, talc, chalk) and synthetic Rock flour (e.g. highly disperse silica, silicates); Emulsifier, such as nonionic to anionic emulsifiers (e.g. polyoxyethylene fatty alcohol Ethers, alkyl sulfonates and aryl sulfonates) and dispersants, such as Lignin sulfite liquor and methyl cellulose.

The fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90 wt .-% active ingredient.

Depending on the type of effect desired, the application rates are between 0.02 and 3 kg of active ingredient or more per hectare. The new compounds can can also be used in material protection (wood protection), e.g. B. against Paecilomyces variotii. When treating seeds, in general Amounts of active ingredient from 0.001 to 50 g, preferably 0.01 to 10 g, per kilogram Seed needed.

The agents or the ready-to-use preparations made therefrom, such as solutions, emulsions, suspensions, powders, dusts, pastes or Granules are used in a known manner, for example by Spraying, atomizing, dusting, scattering, pickling or pouring.

Examples of such preparations are:

• I. 90 parts by weight of compound no. 429 (Tab. I) are mixed with 10 parts by weight of N-methyl-α-pyrrolidone and receives a solution that is suitable for use in the form of tiny drops.  
• II. 20 parts by weight of compound no. 14 (Tab. II) are in a Dissolved mixture, which consists of 80 parts by weight of xylene, 10 parts by weight of Addition product of 8 to 10 moles of ethylene oxide with 1 mole of oleic acid N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct and There is 40 moles of ethylene oxide with 1 mole of castor oil. By pouring out and finely distributing the solution in water gives an aqueous Dispersion.
• III. 20 parts by weight of compound no. 49 (Tab. I) are in one Dissolved mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight Parts of isobutanol, 20 parts by weight of the adduct of There is 40 moles of ethylene oxide with 1 mole of castor oil. By pouring and finely distributing the solution in water gives an aqueous Dispersion.
• IV. 20 parts by weight of compound no. 56 (Tab. I) are in a Dissolved mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight Dividing a mineral oil fraction from boiling point 210 to 280 ° C and 10 parts by weight of the adduct of 40 moles of ethylene oxide There is 1 mole of castor oil. By pouring and finely distributing the Solution in water gives an aqueous dispersion.
• V. 80 parts by weight of compound no. 14 (Tab. I) are mixed with 3 parts by weight. Parts of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 10 parts by weight of the sodium salt of a lignosulfonic acid a sulfite waste liquor and 7 parts by weight of powdered silica gel well mixed and ground in a hammer mill. By A spray mixture is obtained by finely distributing the mixture in water.
• VI. 3 parts by weight of compound no. 17 (Tab. II) are mixed with 97 parts by weight. Partially finely divided kaolin mixed intimately. You get on this Wise a dust containing 3 wt .-% of the active ingredient.
• VII. 30 parts by weight of compound no. 16 (Tab. I) are mixed with a Mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil, which is on the surface of this silica gel was sprayed, mixed intimately. You get on this Refinement of the active ingredient with good adhesiveness.  
• VIII. 40 parts by weight of compound no. 571 (Tab. I) are mixed with 10 parts by weight. Parts of sodium salt of a phenolsulfonic acid-urea-formaldehyde Condensates, 2 parts by weight of silica gel and 48 parts by weight of water intimately mixed. A stable aqueous dispersion is obtained. An aqueous dispersion is obtained by dilution with water.
• IX. 20 parts by weight of compound no. 616 (Tab. I) are mixed with 2 parts by weight. Parts of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight Fatty alcohol polyglycol ether, 2 parts by weight of sodium salt one Phenolsulfonic acid-urea-formaldehyde condensate and 68% by weight Parts of a paraffinic mineral oil are intimately mixed. Man maintains a stable oily dispersion.

The agents according to the invention can also be used together in these forms of use with other active ingredients, such as. B. herbicides, insecticides, Growth regulators and fungicides, or also with fertilizers are mixed and applied. When mixed with fungicides in many cases the fungicidal activity spectrum is enlarged.

The following list of fungicides with which the compounds of the invention can be combined, the possible combinations explain, but not limit.

Fungicides which are combined with the compounds according to the invention can include:

Sulfur, dithiocarbamates and their derivatives, such as
Ferridimethyldithiocarbamate,
Zinc dimethyldithiocarbamate,
Zinc ethylene bisdithiocarbamate,
Manganese ethylene bisdithiocarbamate,
Manganese zinc, ethylenediamine bis-dithiocarbamate,
Tetramethylthiuram disulfide,
Ammonia complex of zinc (N, N-ethylene-bis-dithiocarbamate),
Ammonia complex of zinc (N, N-propylene-bis-dithiocarbamate),
Zinc (N, N'-propylene-bis-dithiocarbamate),
N, N'-polypropylene bis (thiocarbamoyl) disulfide;

Nitroderivatives, such as
Dinitro- (1-methylheptyl) phenylcrotonate,
2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate,
2-sec-butyl-4,6-dinitrophenyl-isopropyl carbonate,
5-nitro-isophthalic acid di-isopropyl ester;

heterocyclic substances, such as
2-heptadecyl-2-imidazoline acetate,
2,4-dichloro-6- (o-chloroanilino) -s-triazine,
O, O-diethyl phthalimidophosphonothioate,
5-amino-1- [bis- (dimethylamino) phosphinyl] -3-phenyl-1,2,4-triazole,
2,3-dicyano-1,4-dithioanthraquinone,
2-thio-1,3-dithiolo [4,5-b] quinoxaline,
1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester,
2-methoxycarbonylamino-benzimidazole,
2- (furyl- (2)) - benzimidazole,
2- (thiazolyl- (4)) - benzimidazole,
N- (1,1,2,2-tetrachloroethylthio) tetrahydrophthalimide,
N-trichloromethylthio-tetrahydrophthalimide,
N-trichloromethylthio-phthalimide,
N-dichlorofluoromethylthio-N ′, N′-dimethyl-N-phenyl-sulfuric acid diamide,
5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,
2-rhodanmethylthiobenzthiazole,
1,4-dichloro-2,5-dimethoxybenzene,
4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone,
Pyridine-2-thio-1-oxide,
8-hydroxyquinoline or its copper salt,
2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine,
2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxide,
2-methyl-5,6-dihydro-4H-pyran-3-carboxylic acid anilide,
2-methyl-furan-3-carboxylic acid anilide,
2,5-dimethyl-furan-3-carboxylic acid anilide,
2,4,5-trimethyl-furan-3-carboxylic acid anilide,
2,5-dimethyl-furan-3-carboxylic acid cyclohexylamide,
N-cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carboxamide,
2-methylbenzoic acid anilide,
2-iodo-benzoic acid anilide,
N-formyl-N-morpholine-2,2,2-trichloroethyl acetate,
Piperazin-1,4-diylbis- (1- (2,2,2-trichloro-ethyl) -formamide,
1- (3,4-dichloroanilino) -1-formylamino-2,2,2-trichloroethane,
2,6-dimethyl-N-tridecyl-morpholine or its salts,
2,6-dimethyl-N-cyclododecyl-morpholine or its salts,
N- [3- (p-tert-butylphenyl) -2-methylpropyl] cis-2,6-dimethylmorpholine,
N- [3- (p-tert-butylphenyl) -2-methylpropyl] piperidine,
1- [2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-t-riazole,
1- [2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole,
N- (n-propyl) -N- (2,4,6-trichlorophenoxyethyl) -N'-imidazol-yl-urea,
1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone, -
1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanol, -
α- (2-chlorophenyl) -α- (4-chlorophenyl) -5-pyrimidine-methanol,
5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine,
Bis- (p-chlorophenyl) -3-pyridinemethanol,
1,2-bis (3-ethoxycarbonyl-2-thioureido) benzene,
1,2-bis (3-methoxycarbonyl-2-thioureido) benzene;

as well as various fungicides, such as
Dodecylguanidine acetate,
3- [3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide,
Hexachlorobenzene,
DL-methyl-N- (2,6-dimethyl-phenyl) -N-furoyl (2) -alaninate,
DL-N- (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) alanine methyl ester,
N- (2,6-dimethylphenyl) -N-chloroacetyl-D, L-2-aminobutyrolactone,
DL-N- (2,6-dimethylphenyl) -N- (phenylacetyl) alanine methyl ester,
5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo-1,3-oxazolidine,
3- [3,5-dichlorophenyl- (5-methyl-methoxymethyl] -1,3-oxazolidine-2,4-dio-n,
3- (3,5-dichlorophenyl) -1-isopropylcarbamoylhydantoin,
N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide, -
2-cyano- [N- (ethylaminocarbonyl) -2-methoximino] acetamide,
1- [2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4-triazole,
2,4-difluoro-α- (1H-1,2,4-triazolyl-1-methyl) -benzhydryl alcohol,
N- (3-chloro-2,6-dinitro-4-trifluoromethyl-phenyl) -5-trifluoromethyl-3-chloro-2-aminopyridine,
1 - ((bis- (4-Fluorophenyl) methylsilyl) methyl) -1H-1,2,4-triazole.

Examples of use

Methyl 2- (phenoxymethyl) -phenylglyoxylate O-methyloxime (A) - known from EP 2 53 213 - used.  

Application example 1 Efficacy against wheat brown rust

Leaves of potted wheat seedlings of the "Kanzler" variety were pollinated with spores of the brown rust (Puccinia recondita). After that the pots were placed in a high chamber at 20 to 22 ° C for 24 hours Humidity (90 to 95%). During this time, they germinated Spores out and the germ tubes penetrated the leaf tissue. The infected plants were then washed with aqueous spray liquors which Contained 80% active ingredient and 20% emulsifier in the dry matter, sprayed soaking wet. After the spray coating had dried on, the Test plants in the greenhouse at temperatures between 20 and 22 ° C and 65 to 70% relative humidity set up. After 8 days it was Extent of rust fungus development on the leaves determined.

The result shows that the active ingredients from Table I No. 49, 429, 56, 14, 15, 16, 17, 582, 578, 573, 592, 571, 704, 705, 616, from Table II No. 17, 644 when used as a 0.025% (% by weight) spray mixture is a better one Show fungicidal activity (95%) as the known comparative active ingredient A (50%).

Example of use 2 Efficacy against Pyricularia oryzae (protective)

Leaves of rice seedlings of the "Bahia" variety grown in pots were with aqueous emulsions containing 80% active ingredient and 20% emulsifier in the Contained dry matter, sprayed to runoff and with 24 hours later an aqueous spore suspension of Pyricularia oryzae. The test plants were then grown in climatic chambers at 22 to 24 ° C and 95 to 99% relative humidity. After 6 days the extent of the disease was determined.

The result shows that the active ingredients from Table I No. 429, 583, 593, 592, 571, 706, 616, from Table II No. 14, 15, 16, 17, 582, 592, 571, 769, 782, 672, 644, 583 when used as a 0.05% (wt .-%) spray mixture show a very good fungicidal effect (100%).

The new compounds are also suitable for class pests effectively combat insects, arachnids and nematodes. You can in crop protection as well as in the hygiene, storage protection and veterinary sectors can be used as pesticides.  

Harmful insects belong to the order of the butterflies (Lepidoptera) for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua, reticulans, Cheimatobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diataea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupocilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholita funebrana, Grapholita molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keifferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flamea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scarba, Plutella xylostella, Pseudoplusia includens, Phyacionia frustrana, Scrobipalpula absoluta, Sitotroga cerelalla, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Tirichoplusia ni, Zeiraphera canadensis.

From the order of the beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthomonus grandis, Anthomonus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, Diabrotica 12-punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Onlema oryzae, Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus, Sitophilus granaria.  

From the order of the two-winged species (Diptera), for example Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Contarina sorghicola, Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia canicularis, Gasterophilus intestinalis, Glossia morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Litriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula oleracea, Tipula paludosa.

From the order of the thrips (Thysanoptera), for example Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi, Thrips tabaci.

From the order of the hymenoptera (Hymenoptera), for example, Athalia pink, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium, pharaonis, Solenopsis geminata, Solenopsis invicta.

From the order of the bugs (Heteroptera), for example, Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedium, Eurygaster integriceps, Euchistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis, Thyanta perditor.

The class of nematodes includes, for example, root gall nematodes, e.g. B. Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, cysts forming nematodes, e.g. B. Globodera rostochiensis, Heterodera avenae, Hetrodera glycinae, Heterodera schatii, Heterodera triflolii, stick and Leaf flakes, e.g. B. Belonolaimus longicaudatus, Ditylenchus destructor, Ditylenchus dipsaci, Heliocotylenchus multicinctus, Longidorus elongatus, Radopholus similis, Rotylenchus robustus, Trichodorus primitivus, Tylenchorhynchus claytoni, Tylenchorhynchus dubius, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi.

The active ingredient concentrations can be used for pest control in the ready-to-use preparations in larger Ranges can be varied.  

Generally they are between 0.0001 and 10%, preferably between 0.001 and 0.1%.

The active ingredients can also be used with great success in the ultra-low-volume process (ULV) can be used, whereby it is possible to use formulations with more than 95% by weight of active ingredient or even the active ingredient without additives.

The amount of active ingredient for pest control is less than Field conditions 0.01 to 10, preferably 0.1 to 1.0 kg / ha.

Example of use 3 Tetranychus telarius, red spider, contact effect, spray test

Potted bush beans that show the second pair of foliage are in the Spray booth sprayed to runoff point with the aqueous active ingredient preparation. The plants come on the turntable and are from all sides sprayed with a total of 50 ml of spray mixture. The plants have to show strong mite infestation and abundant egg laying. The effect will be rated after 5 days using a binocular. Attention is paid to whether all stages are recorded evenly. The plants stand during this Time under normal greenhouse conditions.

Example of use 4 Musca domestica, housefly, permanent contact

Both parts of a Petri dish with a diameter of 10 cm are included 1 ml of the acetone solution of the active ingredients is lined. After evaporation of the solvent, bring 10 flies and cotton wool into each Shell them, close them and count the animals on their back after 24 hours.

If an effect of 80-100% mortality occurs at 0.01 mg / petri dish, then the test continues with falling concentrations.

Application example 5 Plutella maculipennis, cabbage cockroach, prevents food

Young kohlrabi leaves are immersed for 3 seconds in the aqueous preparation of the test substance and on a round filter moistened with 0.5 ml of water (Φ 9 cm) placed in a petri dish (Φ 10 cm). That’s what Leaf with 10 caterpillars in the 4th larval stage and the petri dish closed. After 48 hours, the rate of seizure prevention is assessed in%.  

Claims (10)

1. O-benzyl oxime ether of the general formula I in the
X CH₂, CH-C₁-C₄-alkyl, CH-C₁-C₄-alkoxy, CH-C₁-C₄-alkylthio, N-C₁-C₄-alkoxy,
YO, S, NR⁵,
R¹, R², R⁵ H, C₁-C₄ alkyl,
Z¹, Z² are the same or different and are H, halogen, methyl, methoxy, cyano,
R³, R⁴ are the same or different and are hydrogen, cyano, optionally branched C₁-C₁₀-alkyl, C₁-C₄-haloalkyl, C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl , C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkylthio-C₁-C₄-alkyl, arylthio-C₁-C₄-alkyl, C₂-C₆-alkenyl, C₂-C₅-haloalkenyl, C₃-C₆-cycloalkenyl , C₃-C₆-halocycloalkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₄-alkylthio, benzylthio, C₁-C₄-alkylcarbonyl, optionally subst. Phenylcarbonyl, optionally subst. Benzylcarbonyl, C₁-C₄-alkoxycarbonyl, optionally subst. Phenoxycarbonyl, optionally subst. Benzyloxycarbonyl, optionally subst. Aryl, if necessary subst. Aryloxy, optionally subst. Arylthio, possibly subst. Aryl-C₁-C₄-alkyl, optionally subst. Aryl-C₂-C₄-alkenyl, optionally subst. Aryloxy-C₁-C₄-alkyl, optionally subst. Arylthio-C₁-C₄-alkyl, optionally subst. Hetaryl, possibly subst. Hetaryloxy, optionally subst. Hetarylthio, possibly subst. Hetaryloxy-C₁-C₄-alkyl, optionally subst. Hetaryloxy-C₁-C₄-alkenyl, optionally subst. Hetaryloxy-C₁-C₄-alkyl, optionally subst. Heterocyclyl, optionally subst. Heterocyclyloxy mean
N (R⁶) ₂, the meanings of R⁶ being the same or different and H, C₁-C₆-alkyl, optionally subst. Phenyl mean
-CO-N (R⁷) ₂, where the conditions of R⁷ are the same or different and are H, C₁-C₄-alkyl,
where "possibly subst." in addition to hydrogen, the radicals halogen, cyano, nitro, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₁₀-alkoximino-C₁-C₂-alkyl, aryl, aryloxy, Benzyloxy, hetaryl, hetaryloxy, C₃-C₆-cycloalkyl, heterocyclyl, heterocyclyloxy,
R³ and R⁴ together can form a carbocyclic or heterocyclic ring, which can be replaced by the "optionally subst." above radicals can be substituted and
R³ or R⁴ can be halogen. 2. O-benzyl oxime ether of the formula II with the definitions given in claim 1 of the radicals X, Y, R¹ to R⁷, Z¹, Z². 3. O-benzyl oxime ether of the formula III with the definitions of radicals X, Y, R¹ to R⁷ given in claim 1. 4. Compounds of formula II according to claim 2 in the X CH₂, CH-C₁-C₄- Means alkyl, CH-C₁-C₄-alkoxy, CH-C₁-C₄-alkylthio and the others Radicals Y, R¹ to R⁷, Z¹, Z² the definitions given in claim 1 to have. 5. Compounds of formula II according to claim 2, in which
X CH₂, CHCH₃, CHC₂H₅, CHOCH₃, CHOC₂H₅, CHSCH₃, CHSC₂H₅,
YO,
R¹ C₁-C₄ alkyl,
R² H, methyl,
R³, R⁴ are the same or different and are hydrogen, cyano, optionally branched C₁-C₁₀-alkyl, C₁-C₄-haloalkyl, C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl , C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkylthio-C₁-C₄-alkyl, arylthio-C₁-C₄-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₂-C₄-haloalkenyl , C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₁-C₄-alkylcarbonyl, C₁-C₄-alkoxycarbonyl, optionally subst. Aryl, if necessary subst. Aryloxy, optionally subst. Arylthio, possibly subst. Aryl-C₁-C₄-alkyl, optionally subst. Aryl-C₂-C₄-alkenyl, optionally subst. Aryloxy-C₁-C₄-alkyl, optionally subst. Hetaryl, possibly subst. Hetaryloxy, optionally subst. Hetarylthio, possibly subst. Heterocyclyl mean
N (R⁶) ₂, where R⁶ are the same or different and H, C₁-C₆-alkyl, C₃-C₆-cycloalkyl, optionally subst. Phenyl,
-CO-N (R⁷) ₂, where R⁷ are the same or different and are H, C₁-C₄-alkyl;
where "possibly subst." is the radicals specified in claim 1,
R³ and R⁴ together can form a carbocyclic or heterocyclic ring, which can be replaced by the "optionally subst." radicals mentioned may be substituted,
R³ or R⁴ can be halogen and
Z¹, Z² are hydrogen, fluorine, chlorine, bromine, iodine, methyl, cyano or methoxy. 6. O-benzyl oxime ether of the formula II according to claim 2, in which X is NOCH₃, NOC₂H₅ means and the other radicals Y, R¹ to R⁷, Z¹, Z² in Claim 1 have given definitions. 7. Compounds of formula II according to claim 2 in the
X NOCH₃, NOC₂H₅,
YO,
R¹ C₁-C₄ alkyl,
R² H, C₁-C₂ alkyl,
R³, R⁴ are the same or different and are hydrogen, cyano, optionally branched C₁-C₁₀-alkyl, C₁-C₄-haloalkyl, C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl , C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkylthio-C₁-C₄-alkyl, arylthio-C₁-C₄-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₂-C₄-haloalkenyl , C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₁-C₄-alkylcarbonyl, C₁-C₄-alkoxycarbonyl, optionally subst. Aryl, if necessary subst. Aryloxy, optionally subst. Arylthio, possibly subst. Aryl-C₁-C₄-alkyl, optionally subst. Aryl-C₂-C₄-alkenyl, optionally subst. Hetaryl, possibly subst. Hetaryloxy, optionally subst. Hetarylthio, possibly subst. Heterocyclyl mean
N (R⁶) ₂, where R⁶ are the same or different and H, C₁-C₆-alkyl, C₃-C₆-cycloalkyl, optionally subst. Phenyl,
CO-N (R⁷) ₂, where R⁷ are the same or different and are H, C₁-C₄-alkyl;
where "possibly subst." is the radicals specified in claim 1,
R³ and R⁴ together can form a carbocyclic or heterocyclic ring, which can be replaced by the "optionally subst." radicals mentioned may be substituted,
R³ or R⁴ can be halogen and Z¹, Z² are hydrogen. 8. fungicide, comprising an inert carrier and a fungicidally effective amount of an O-benzyl oxime ether of the formula I. in the
X CH₂, CH-C₁-C₄-alkyl, CH-C₁-C₄-alkoxy, CH-C₁-C₄-alkylthio, N-C₁-C₄-alkoxy,
YO, S, NR⁵,
R¹, R², R⁵ H, C₁-C₄ alkyl,
Z¹, Z² are the same or different and are H, halogen, methyl, methoxy, cyano,
R³, R⁴ are the same or different and are hydrogen, cyano, optionally branched C₁-C₁₀-alkyl, C₁-C₄-haloalkyl, C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl , C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkylthio-C₁-C₄-alkyl, arylthio-C₁-C₄-alkyl, C₂-C₆-alkenyl, C₂-C₅-haloalkenyl, C₃-C₆-cycloalkenyl , C₃-C₆-halocycloalkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₄-alkylthio, benzylthio,
C₁-C₄ alkylcarbonyl, optionally subst. Phenylcarbonyl, optionally subst. Benzylcarbonyl,
C₁-C₄ alkoxycarbonyl, optionally subst. Phenoxycarbonyl, optionally subst. Benzyloxycarbonyl, optionally subst. Aryl, if necessary subst. Aryloxy, optionally subst. Arylthio, possibly subst. Aryl-C₁-C₄-alkyl, optionally subst. Aryl-C₂-C₄-alkenyl, optionally subst. Aryloxy-C₁-C₄-alkyl, optionally subst. Arylthio-C₁-C₄-alkyl, optionally subst. Hetaryl, possibly subst. Hetaryloxy, optionally subst. Hetarylthio, possibly subst. Hetaryloxy-C₁-C₄-alkyl, optionally subst. Hetaryloxy-C₁-C₄-alkenyl, optionally subst. Hetaryloxy-C₁-C₄-alkyl, optionally subst. Heterocyclyl, optionally subst. Heterocyclyloxy mean
N (R⁶) ₂, the meanings of R⁶ being the same or different and H, C₁-C₆-alkyl, optionally subst. Phenyl mean
-CO-N (R⁷) ₂, where the conditions of R⁷ are the same or different and are H, C₁-C₄-alkyl;
where "possibly subst." in addition to hydrogen, the radicals halogen, cyano, nitro, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₁₀-alkoximino-C₁-C₂-alkyl, aryl, aryloxy, Benzyloxy, hetaryl, hetaryloxy, C₃-C₆-cycloalkyl, heterocyclyl, heterocyclyloxy,
R³ and R⁴ together can form a carbocyclic or heterocyclic ring, which can be replaced by the "optionally subst." above radicals can be substituted and
R³ or R⁴ can be halogen. 9. A method of combating fungi, characterized in that the fungi or the materials, plants, seeds or the soil threatened by fungal attack are treated with a fungicidally effective amount of a compound of the formula I. in the
X CH₂, CH-C₁-C₄-alkyl, CH-C₁-C₄-alkoxy, CH-C₁-C₄-alkylthio, N-C₁-C₄-alkoxy,
YO, S, NR⁵,
R¹, R², R⁵ H, C₁-C₄ alkyl,
Z¹, Z² are the same or different and are H, halogen, methyl, methoxy, cyano,
R³, R⁴ are the same or different and are hydrogen, cyano, optionally branched C₁-C₁₀-alkyl, C₁-C₄-haloalkyl, C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl , C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkylthio-C₁-C₄-alkyl, arylthio-C₁-C₄-alkyl, C₂-C₆-alkenyl, C₂-C₅-haloalkenyl, C₃-C₆-cycloalkenyl , C₃-C₆-halocycloalkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₄-alkylthio, benzylthio, C₁-C₄-alkylcarbonyl, optionally subst. Phenylcarbonyl, optionally subst. Benzylcarbonyl, C₁-C₄-alkoxycarbonyl, optionally subst. Phenoxycarbonyl, optionally subst. Benzyloxycarbonyl, optionally subst. Aryl, if necessary subst. Aryloxy, optionally subst. Arylthio, possibly subst. Aryl-C₁-C₄-alkyl, optionally subst. Aryl-C₁-C₄-alkenyl, optionally subst. Aryloxy-C₁-C₄-alkyl, optionally subst. Arylthio-C₁-C₄-alkyl, optionally subst. Hetaryl, possibly subst. Hetaryloxy, optionally subst. Hetarylthio, possibly subst. Heteroaryl-C₁-C₄-alkyl, optionally subst. Hetaryloxy-C₁-C₄-alkenyl, optionally subst. Hetaryloxy-C₁-C₄-alkyl, optionally subst. Heterocyclyl, optionally subst. Heterocyclyloxy mean
N (R⁶) ₂, the meanings of R⁶ being the same or different and H, C₁-C₆-alkyl, optionally subst. Phenyl mean
-CO-N (R⁷) ₂, where the conditions of R⁷ are the same or different and are H, C₁-C₄-alkyl,
where "possibly subst." in addition to hydrogen, the radicals halogen, cyano, nitro, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₁₀-alkoximino-C₁-C₂-alkyl, aryl, aryloxy, Benzyloxy, hetaryl, hetaryloxy, C₃-C₆-cycloalkyl, heterocyclyl, heterocyclyloxy,
R³ and R⁴ together can form a carbocyclic or heterocyclic ring, which can be replaced by the "optionally subst." above radicals can be substituted and
R³ or R⁴ can be halogen. 10. Connections of the formulas