CS203163B2 - Method of preparing derivatives of imidazole or 1,2,3-triazole - Google Patents

Description

(54) A process for the preparation of imidazole or 1,2,4-triazole derivatives

The invention relates to a process for the preparation of certain heterocyclic compounds which are derivatives of imidazole or 1,2,4-triazole. Said compounds are useful in controlling fungal infections in plants.

The present invention provides a process for the preparation of imidazole or 1,2,4-triazole derivatives of formula I

R * R ⁶ R ¹ R ^Z

is hydrogen, halogen, C 1-6 alkyl or C 1-6 alkoxy, wherein at least 6 of R ¹ to R ¹⁰ are hydrogen and X is imidazol-1-yl- or 1,2,4-triazol-1-yl or addition salts thereof acid salts or metal complexes, characterized in that a compound of the general formula II is reacted in a polar solvent at a temperature of 10 to 120 ° C.

R * R ^z ,

where

R is C 1-4 alkyl, cyano, phenyl optionally substituted with one, two or three halogens, C 1-4 -alkyl-, nitro-, trifluoromethyl-, cyano-, phenyl-, C 1-4 -alkoxy or (C 1-4-) -alkylene) dioxo groups,

Z represents a C = O group or a derivative thereof which is a ketal, hydrazone, semicarbazone, oxime or imine group, each of the symbols

Ri to Rio that are the same or different where

R ¹ to R ⁵ , Z and X are as defined above, or a salt thereof with a compound of general formula

where

R ⁶ and R ⁶ to R ¹⁰ are as defined above and

Q is halogen.

The compounds of the invention contain chiral centers. Usually, the compounds of the invention are obtained in the form of racemic mixtures. However, these or other mixtures can be separated into the individual isomers by methods known per se.

The term 'halogen' in the substrates refers to fluorine, chlorine, bromine or iodine.

Preferably, all R ¹ to R ⁵ and / or all R ⁶ to R ¹⁰ are hydrogen or one or two of R ¹ to R ⁵ and / or one or two of R ⁶ to R ¹⁰ are halogen, wherein the others are hydrogen atoms. Particular preference is given to those compounds in which R ³ , R ⁶ and / or R ⁸ represent halogen atoms (especially fluorine, chlorine or bromine), the other symbols being hydrogen atoms.

Suitable salts are those with inorganic or organic acids, for example hydrochloric, nitric, sulfuric, acetic or oxalic acids.

Suitable metal complexes are suitably complexes containing copper, zinc; manganese or iron. The complexes preferably have the general formula

ASz. yH2O where

R, Z, R ¹ to R ¹⁰ and X are as defined above,

M represents metal,

A is an anion (e.g., chloride, bromide, iodide, nitrate, sulfate or phosphate anion), n is 2 or 4 and y is 0 or an integer from 1 to 12.

Specific examples of the compounds of the invention are given in Table I. All R ¹ , R ² , R ⁴ , R ⁵ , R ⁹ and R ¹⁰ are hydrogen and Z is C = O.

Compound No. RR ³ R ⁶ R ⁷ R ⁸ Imidazol-1-yl (I) Melting point (° C) 1,2,4-Triazol-1-yl (T)

oo in 00 WHAT CD WHAT O WHAT m rH 05 / in 0- rH lf) 00 QO rH CD CO CD lf) CM O lf) 05 / in CM 00 rH CM CM rH rH CM rH lf5 Η HH rH rH rH rH rH rH Ή rH rH OO rH rH WHAT rH rH rH rH Om rH rH rH ‘8T8 > N > N ’$? > N > N > N > N > N > N ‘ST > N > N φ > N > N > N > N > N > N > N > N > N > N > N Honors Honor p «M □ Honor Honor Honor Honor Honor Honor 'O Honor honor O Honor Honor Honor Honor Honor Honor Honor Honor Honor Honor Rf CO 00 CO rH in CM Φ 00 CM CM 00 O 05 / 00 O OO lf) 00 CM Ή CD lf) O CD CO CO in CM O lf) WHAT CD lf) CM OO O CM WHAT CM rH 00 rH 0m OM rH in rH rH H rH rH rH rH rH rH rH rH rH rH rH rH rH rH rH rH rH rH

KKQhXSEKuKoffifrihSKQhKoofflOUOfflfioooQ

T ⁴ 'Τ ⁴ ** Γ * | _L | μ ^ ι ± || ^ 4κΐ ^ ΐ1 (Η-ΐμ ^ Ι-ΗΗ-ΐμ ^ ΜΗ ^ μ4Ι ^ μΜμΜμΜ1-ΜΛμ4 * Η ^ Ι-ΗΛΐ-Η *> * ΗΗΗΗ- (ΗΜ

4m4h44M> -hM- <m-ihhUh4 - <> * hh * i> mp- <ημ ημημμηημημημημημηηημμ mm hm hm Ο ffioouoouooKKfcfafafc.fafafafatahCfatMffifaKuEfaÍt:

»* X * m o x + x x +

HNn ^ infoSooaoriNrt ^ incNeaoHNn ^ intDScoOH

HrtrtHHHrtrlHHNNNNNMNNNNCOn + Me Cl Cl H Cl T 129-131 + Me F Cl H Cl T 135-138

Compound No. RR ³ R ⁶ R ⁷ R ⁸ Imidazol-1-yl (I) Melting point (° C)

1,2,4-Triazol-1-yl (T)

00 WHAT CM WHAT lf) CD ID -Φ WHAT lf) WHAT 00 in WHAT lf) O • Φ 05 / O O O 05 / 05 / in v — 1 WHAT CM Φ WHAT O Φ O lf) WHAT WHAT Φ what WHAT 00 WHAT O) t> lf) ΙΌ rH Φ rH O O CM rH CD rH rH r * H rH rH rH t-H rH rH r-H rH rH rH rH rH rH rH rH rH rH τ — 1 t-H rH rH > N > N > N > N > N > tM > N and? > N > N > N > N) > N > N > N > N > N > N > N > n > N > N > N > N > N > N > N ca ca ca ca ca ca WHAT P4 O ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca ca WHAT O in 00 WHAT φ 00 CM ΙΌ CM CM O O what φ WHAT 05 / O 00 05 / in l> lf) Φ rH CD CM WHAT WHAT [> » Φ O in WHAT WHAT φ CM what 00 what CD WHAT in in O WHAT O O O CM rH rH rH rH rH rH rH rH rH rH τ — 1 rH rH rH rH rH rj. rH rH rH rH rH rH rH rH

«» - <> -) £ -Η £ —Ι ^ Η £ -Η £ - <& Η

EKKKKKKEEKKKKEEKKKKEKiSEKfafafeKKKEK oo ^

KkuEukfflEofcSoKEKoO 0 0 UO & btaKufcBtaSQK ^^ υ ££ έα) α) ΡΗΡΡα) οορΦα; + ιυυΦα; α) φ (ΐ) θ) α) ^ ΦΦΦ www D 2 § td s * g N 2 2 L 2 2 ^www W 2 2 W 2 2 w 2 2 2

XX +++ +++++++ XX χ χ + +

M <iriccii> -ocqT-icqcO'4iincoi> coo) Or-icMco'd <iocD> .oocr) Or-icMco ^ thiir) cncQcocOcQcO ^^^^^^^^ iST ^ inininininininiOinincDcococococo + Me * Cl HF F 104 to 106

67+ Me Cl H F Η T 95 to 97 x Me Η Η H F T 119 to 120 + Et F Η H F T 110 to 112

Compound No. R R 3 R 6 R 7 Imidazol-1-yl (I) Melting point (° C)

1,2,4-Triazol-1-yl (T)

rH CM CD rH CD tí tí O LO CM WHAT O CM WHAT t> s tí tí tí • 1— » rH tí tí rH tí > N > N > N CD > N > N > N > N > N what tí tí O tí tí tí tí tí 00 O 00 CD 00 LO O O CD LO CM CM O CM WHAT t> rH rH t * H rH rH rH rH

gmuZoou p 'H 1 - I - µ-rf (D + j + j + j + JQJOJCUCDCD w W w 2 § 2.2 S + + + X! + X! XI □ ΗΝσΐ ^ ιηιθ (- Μ * Compounds 14 and 18 are mutual diastereoisomers, compound 13 is a mixture of these diastereoisomers.

These compounds are a mixture of diastereoisomers.

These compounds are diastereoisomers with each other.

These compounds are individual diastereoisomers.

The process of the invention can be carried out, for example, by first reacting a compound of formula II with an alkali metal hydride (e.g. sodium hydride) in a suitable solvent such as dimethylformamide or tetrahydrofuran) to form an alkali metal salt which is reacted with e.g. or phenyl is an aralkyl halide, for example bromide (preferred) or chloride.

In this procedure, usually the compound of formula II is dissolved in a solvent and an equivalent amount of alkali metal hydride is added and the aralkyl halide is added dropwise when the reaction occurs.

After the reaction, the product may be isolated by pouring it into water and the resulting solid recrystallized from a suitable solvent or by purifying the resulting oil by column chromatography or other suitable technology.

Addition salts and metal complexes of compounds of formula I may be prepared by known methods. For example, the complexes may be prepared by reacting the non-complexed compound with a metal salt in a suitable solvent.

The compounds are effective fungicides, in particular against the following diseases:

Piricularia oryzae on rice,

Puccinia recondita, Puccinia striiformis and other rust on wheat,

Puccinia hordei, Puccinia striiformis and other rust on barley and rust on other host plants such as coffee, apple, vegetables and ornamental plants,

Plasmopara viticola on vines,

Erysiphe graminis (powdery mildew) on barley and wheat and other powdery mildew on various host plants, such as Sphaeroitheca fuliginea on cucumbers, Podosphaera leucotricha on apple trees and Uncinula necator on vines,

Cercospora arachidicola in groundnuts and other Cercospora species such as sugar beet, banana and soybeans,

Botrytis cinerea (gray mold) on tomatoes, strawberry, grapevine and other host plants,

Phytophthora infestans (tomato) on tomatoes,

Venturia inaequalis (scab) on apple trees.

Some of the compounds of the invention also have a broad range of activity against fungi in vitro. They have activity against various fruit diseases occurring on fruit after harvest (for example Penicillium digatatum and Penicillium italicum on oranges, Gleosporium musarum on bananas. Some of the compounds are effective as seed dressings against Fusarium spp., Septoria spp., Tilletla spp. (seed-borne wheat disease), Ustilago spp ,, and Pyrenophora spp. on cereals.

Some of the compounds are also active against Rhizoctonia solani, an important disease of cotton and rice.

The compounds of the invention also have a certain plant growth regulating effect (particularly an effect of stunting vegetative growth of monocotyledonous and dicotyledonous plants) and an antibacterial effect (e.g. against Erwinia amylovora) and an antiviral effect (e.g. against mosaic) and herbicidal and algicidal effect.

For fungicidal purposes, the compounds of formula (I) may be used as such, but are conveniently used in the form of compositions into which they are incorporated. The present invention provides a fungicidal composition comprising a compound of formula I as defined above, or a salt or metal complex thereof, and a carrier or diluent.

The compounds according to the invention can be applied in various ways in the control of plant fungi and in the treatment of plants and hay, for example, as such or in the form of compositions directly on the leaves of plants which are infected or expected to be infected. shrubs and trees or the seeds or the environment in which the plants, shrubs or trees grow or are to be grown. The compounds or compositions can be applied as sprays, dusts or creams or pastes. They can be applied to any part of the plant, shrub or tree, for example, to leaves, stems, branches or roots or to the soil surrounding the roots or to the seeds before sowing.

The term plant refers to both seedlings and shrubs and trees. The fungicidal effect of the invention is preventive, protective, prophylactic or uprooting.

The compounds according to the invention are preferably used in the form of compositions for agricultural and horticultural purposes. The type of composition used will always depend on the particular intended purpose.

The compositions may take the form of dusts or granules containing the active ingredient and a solid diluent or carrier such as kaolin, bentonite, diatomaceous earth, dolomite, calcium carbonate, talc, magnesium oxide powder, fuller's earth, gypsum, Hewwitt clay, diatomaceous earth and kaolin. The seed dressing compositions may comprise, for example, a seed adhesion promoter (e.g., mineral oil).

The compositions may also take the form of dispersible powders, granules or grains containing a surfactant to facilitate dispersion of the powder or grains in liquids. These compositions may also contain fillers and suspending agents.

Aqueous dispersions or emulsions may be prepared also so that the active ingredient or active ingredient dissolved in an organic solvent optionally containing one or ^one more wetting agents, dispersants or emulsifiers, and then adding the mixture to water optionally containing wetting, dispersing or emulsifying agents. Suitable organic solvents are ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, xylenes and trichlorethylene.

The compositions to be used as sprays may also be in the form of aerosols in which the composition is maintained in a container under pressure in the presence of a propellant, for example fluorotrichloromethane or dlfluordichloromethane.

By varying the application, the various compositions can be better adapted by adding suitable additives, for example additives to improve the distribution, adhesion or rain resistance of the compounds on the treated surfaces.

The compounds may be used in the form of mixtures with a fertilizer (for example nitrogen or phosphorus containing fertilizer). Preference is given to those compositions which contain only fertilizer granules into which the compound of the invention is introduced, for example by coating.

The compositions may also be in the form of liquid preparations, which are used as a dipping bath or spray. Such compositions are generally aqueous dispersions or emulsions containing the active ingredient in the presence of one or more wetting, dispersing, emulsifying or suspending agents. These agents may be cationic, anionic or non-ionic agents. Suitable cationic agents are quaternary ammonium compounds, for example cetyltrimethylammonium bromide.

Suitable anionic agents are soaps, salts of aliphatic monoesters of sulfuric acid (e.g. sodium lauryl sulfate) and salts of sulfonated aromatic compounds (e.g. sodium dodecylbenzenesulfonate, sodium, calcium or ammonium lignosulfonate, corresponding butylnaphthalenesulfonate and a mixture of diisopropyl and triisopropylnaphthalenesulfonate).

Suitable nonionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl or cetyl alcohol or with alkyl phenols such as octyl or nonylphenol and octyl cresol. Other nonionic agents include partial esters derived from long chain fatty acids and hexite anhydrides, condensation products of these partial esters with ethylene oxide and lecithins. Suitable suspending agents are hydrophilic colloids (e.g., polyvinylpyrrolidone and sodium carboxymethylcellulose) and resins of vegetable origin (e.g., gum arabic and tragacanth).

Compositions intended for use in the form of aqueous dispersions or emulsions are conveniently supplied in the form of a concentrate containing a high proportion of the active compound or compounds, and the concentrate is then diluted with water before use. These concentrates often withstand long-term storage and, after such storage, can be diluted with water to form aqueous compositions which are homogeneous for a period of time sufficient to be applied by conventional spray equipment. The concentrates suitably contain up to 95%, preferably 10 to 85%, for example 26 to 60% by weight of the active ingredient (s). After dilution with water to form aqueous compositions, the resulting compositions may contain varying amounts of the active ingredient (s) depending on the intended use. However, aqueous compositions containing 0.0005 or 0.01 to 10% by weight of the active ingredient (s) are usually used.

The compositions of the invention may also contain other compounds having a biological effect (for example, growth stimulants such as gibberellins and other compounds having a complementary fungicidal or insecticidal effect) and stabilizers, for example epoxy compounds (for example epichlorohydrin). As other fungicidal compounds, a compound capable of controlling ear diseases in cereals such as wheat such as Septoria, Gibberella, Helminthsporum and black mold can be used.

The following examples serve to illustrate the invention in more detail. The temperature is given in ° C. Example 1

2- (1,2,4-Triazol-1-yl) -3-phenyl-4'-chlorobutyrophenone (compound 2)

Stage 1.

2,4'-Dichloroacetophenone (0.03 mol) and 1,2,4-triazole (0.03 mol) were suspended in acetonitrile i (50 ml) and cooled to -20 ° C. Triethylamine (0) was added dropwise with stirring. After stirring for 2 hours at -20 ° C, the mixture was poured into water, the product was filtered off, washed with water, dried and crystallized from toluene to give pale yellow needles of 2- (1,2,4-triazole-1-). yl] -4'-chloroacetophenene, m.p. 151-153 ° C.

Analysis for C10H8ON3Cl calculated:

% C, 54.2%;% H; 3.6%;

% C, 54.2%;% H; 3.7%;% N 19.1%;

Stage 2.

2- (1,2,4-Triazol-1-yl) -4'-chloroacetophenone (0.01 mol) was dissolved in dimethylformamide (5.0 ml) at room temperature and treated with sodium hydride (0.01 mol) ). When the reaction is complete (after 3 hours), the mixture is cooled to 0 ° C and α-methylbenzyl chloride (0.01 mol) is added dropwise with stirring. After stirring at room temperature for 20 hours, the mixture was poured into water and the product was filtered off. Recrystallization from chloroform / petroleum ether (60-80 ° C) gave the title compound as a colorless crystalline solid, mp 163-165 ° C.

Analysis for C18H1BON3Cl calculated:

% C, 66.4%;% H, 4.9%;

DfllO7Ot1A ‘

66.5% C, 4.9%: H, 13.0% N.

Example 2

This example illustrates two of the fungicidal agents:

1. Emulsifiable concentrate

Compound 13 200 g / kg Arylan SBC acid 100 ALIGN! g / kg Arylan PWS 200 g / kg dimethylformamide to· 1 kg 2. Powder suitable as mordant seed merger 14 250 g / kg dodecylbenzene 30 g / kg miastek 52 to 1 kg

Example 3

The compounds are tested against various foliar fungal diseases of plants. This testing technique is used.

Plants are grown in Jonh Innes pot compost (No. 1 or “Seed” as required) in 4 cm mini pots. A layer of fine sand is placed at the bottom of the pots to facilitate the uptake of the test compound by the roots.

The test compounds are formulated either by grinding in a ball mill with aqueous Dispersol T or by dissolving in acetone / ethanol and diluting the solution to the desired concentration just prior to use. In foliar diseases, a 100 ppm active ingredient suspension is sprayed onto the leaves and the suspension is introduced through the soil to the roots of the same plant. (Spraying is applied to the maximum containment and root dressing to a final concentration of about 40 ppm of active ingredient on dry soil. Tween 20 is added to the formulation to a final concentration of 0.1% prior to applying the spray to cereals.)

In most tests, the test compound is applied to soil (roots) and leaves (by spraying) one or two days before inoculation of the plants with diseases. An exception to this is the Erysiphe gramlnis test, in which plants are inoculated 24 hours before treatment. After inoculation, the plants are placed in a suitable environment which allows the infection to break out and then incubated until the disease can be evaluated. The period between inoculation and evaluation varies from 4 to 14 days depending on the disease and the environment.

Disease control is characterized by the following steps:

= no disease - 0 to 5% = 6 to 25% = 26 to 60% / o = more than 60%.

The results are shown in Table II.

Table II Compound number Puccinia recondita on wheat Erysiphe graminis on barley Piricularia oryzae on rice Plasmopara Phytophtho- Botrytis cinerea on tomatoes viticola on the vine ra iníestans on tomatoes 1 4 4 0 2 0 2 2 4 4 1 0 1 3 4 4 0 0 0 4 4 3 0 3 3 5 3 4 1 0 0 4 6 3 4 2 0 0 2 7 3 4 3 0 0 2 8 4 4 2 0 0 0 9 3 3 0 0 0 3 10 4 4 0 0 0 0 11 2 4 1 0 0 2 12 4 4 2 0 0 2 13 4 4 2 0 2 0 14 4 4 3 0 2 3 15 Dec 4 4 2 0 0 3 16 4 4 0 4 0 2 17 4 4 3 0 2 1 18 4 4 0 0 0 4 19 Dec 4 4 0 3 0 3 20 May 4 4 1 3 0 3 21 4 4 0 0 1 0 22nd 3 4 0 0 0 0 23 1 2 0 3 24 4 4 0 1 3 25 4 4 0 0 1 3 27 Mar: 4 3 0 2 1 2 31 1 0 0 2 32 0 1 1 0 0 0 33 3 0 0 3 34 4 4 1 2 3 35 4 4 4 1 1 4 36 4 4 3 0 0 4 37 4 4 4 2 0 3 38 4 4 3 0 0 1 40 2 4 0 0 0 0 41 4 4 0 0 0 3 42 3 4 0 0 2 43 4 4 0 0 0 2 44 4 4 0 0 0 3 45 3 4 0 0 1 2 46 3 4 2 0 1 4 47 3 4 0 0 1 4 48 3 4 2 0 1 4 49 3 4 0 0 3 50 3 4 2 0 0 51 4 4 0 0 0 '4 53 3 4 0 0 0 3 54 4 4 0 0 3 56 4 4 3 1 1 4 57 4 4 3 0 2 4 58 4 4 3 3 0 3 61 3 4 0 4 0 3 62 4 4 0 4 63 ii 4 2 0 1 3 64 2 4 0 0 0 3 65 4 4 3 0 0 4 66 3 4 3 0 2 3 67 3 4 3 0 1 3 68 4 4 0 0 0 3 69 4 4 3 1 1 4

Compound number 11 Puccinia recondita on wheat Erysiphe graminis on barley Piricularia oryzae on rice Plasmopara viticola on wine vine 12 Phytophthora infestans on tomatoes Botrytis cinerea on tomatoes' 70 2 4 1 3 1 3 71 3 4 0 0 0 2 72 4 4 0 0 0 3 73 3 4 2 0 0 3 74 3 4 3 0 0 1 75 4 4 0 0 0 3 76 4 4 0 0 0 4 77 2 4 0 0 3 78 4 3 2 0 0 3 Example 4 Disputes Venturia inaequalis, as a kid ·

This example illustrates the protective effect of compounds (at a concentration of 50 ppm) against various fungal diseases of fruit.

The efficacy of the compounds against powdery mildew (Podosphaera leucotricha) and powdery mildew (Uncinula necator) is determined. The tests are as follows:

Small plants of apple tree (Jonathan) and vines about 3 weeks old, grown in small pots of 3 cm diameter, are first sprayed with a solution or suspension of the test compound, allowed to dry overnight in a greenhouse, and infested with spores of disease the following day. that the plants are placed in an enclosure and the disease spores inflated into the enclosure are allowed to settle on the plants for 4 to 6 hours without flow.

Percent infection of plant leaves with disease is carried out in apple trees after 8 days and in vine plants after 9 to 10 days.

Further, tests are carried out on the activity of the compounds against apple scab (Venturia inaequalisj). These tests are carried out as follows:

The parasite is transferred from plant to plant using an agar culture that provides a highly pathogenic fungus.

Infected leaves are removed from the "stock" infested plants 13 days prior to inoculation. Spores are removed from the leaves by mixing in a small volume of deionized water, counted and then adjusted to 100,000 spores / ml. The suspension is sprayed onto the lower leaves of the apple seedlings of one of three susceptible species, i.e. Jonathan, Granny Smith and Red Delicious. The inoculated seedlings were immediately placed in a high humidity and 19 ° C room and left there for 48 hours. After this incubation period, the plants are placed in a growth space where disease is allowed to develop. The disease is easily evaluated 12 or 13 days after incubation.

The test compound is administered 24 hours after inoculation.

The same assessment system as in Table II is used. The results are shown in Table III.

Table III

Disease control Podosphaera leuchotricha on apple trees Uncinula necator on the vine Venturia inaequalis on apple trees 0 1—2 0 1 2 0 1 4 1 2 4 2 3 4 0—2 4 4 2 2 4 1 1 4 1 0 1 0 4 0 1 0 2 4 4 4 4 4 4 4 4 1 4 0 4 4 2 4 4 3 2 1 2 4 4 2 4 4 4 4 4 4 0 4 1 4 4 3 1 4 2 2 4 1 0 2 0

Claims (3)

OBJECT OF THE INVENTION A process for the preparation of imidazole or 1,2,4-triazole derivatives of the general formula I R is C 1-4 alkyl, cyano, phenyl optionally substituted with one, two or three halogens, C 1-4 -alkyl-, nitro-, trifluoromethyl-, cyano-, phenyl-, C 1-4 -alkoxy or (C 1-4 -alkylene) ) Dioxo groups Z represents a C = O group or a derivative thereof which is a ketal, hydrazohal, semicarbazone, oxime or imine group, each of the symbols R 1 to R ¹⁰ , which are the same or different, represent hydrogen, halogen, C 1-4 -alkyl- or C 1-4 -alkoxy, wherein at least 6 of the substituents R ¹ -R ¹⁰ are hydrogen and X is imldazol-1-yl or 1,2,4-triazol-1-yl or their acid addition salts or metal complexes, characterized in that a compound of formula II is reacted in a polar solvent at a temperature of 10 to 120 ° C in a polar solvent CH. · I * x # ni) where R ¹ to R ⁵ , Z and X are as defined above, or a salt thereof, with a compound of formula III -HR CH- & R ³ R ® (III) where R ⁶ and R ⁶ to R ¹⁰ are as defined above and Q is halogen. 2. Method of claim 1 for the preparation of compounds of formula I wherein R represents Ci-4 alkyl and Z, R ¹ to R ¹⁰ and X are as defined in paragraph 1, or their acid addition salts with acids, characterized in that as Compounds of formula (III) employ compounds wherein R is C 1-4 alkyl and R ⁶ to R ¹⁰ and Q are as defined in point 1. 3. The process of item 1 for preparing compounds of formula I wherein R is C1-4 alkyl or phenyl optionally substituted with two or three halogens, C1-4 alkyl-, nitro-, trifluoromethyl-, cyano-, phenyl-, C1-4 alkoxy or (C 1 alkylene) dioxo groups and Z, R ¹ to R ¹⁰ and X are as defined in point 1 or their acid addition salts or metal complexes, characterized in that compounds of formula III are those wherein R is C 1-4 alkyl or phenyl optionally substituted with two or three halogens, C 1-4 alkyl, nitro, trifluoromethyl, cyano, phenyl, C 1-4 alkoxy or (C 1-4 alkylene) dioxo and R ⁶ to R 7 ¹⁰ and Q are as defined in 1.