DE2144125A1 - Dithiocarboamic acid salts or urea derivs - from urea derivs and dithio-carbamic acid salts, fungicides, microbicides - Google Patents

Abstract

Cpds. of gen. formula (I):- where R and R'= H, methyl or ethyl; R' may also be:- A = alkylene (max 4C); R + R' + N may form a 5-6-membered heterocyclic ring opt. contng. -O and/or -N; B = NH-R", or O-R"; R" = H, alkyl (is not >20C), cycloalkyl (is not >6C) or aryl opt. substd. with lower alkyl, nitro and/or halogen; n = 1 when R' = H, methyl or ethyl; n = 2 when R' = are prepd. by reacting a cpd. (II): or its mineral salts, with a cpd. (III):- or its mineral salts; where R and R"' = H, methyl or ethyl; R"' may also be M = ammonium or alkalimetal; R + R"' + N = as signified for R + R' + N; in the presence of polar solvents pref. at 10-80 degrees C. (I) are esp. active against Phytophtora intestans and Fusicladium dendriticum, and also have microbicidal activity against a wide range of partly pathogenic micro-organisms. They are also active against blue- and green algae.

Description

Dithiocarbamic acid salts of urea derivatives, process for their Production and its fungicidal and microbicidal use The present invention relates to new dithiocarbamic acid salts of urea derivatives, which are fungicidal and have microbicidal properties and a method for their preparation.

As has long been known, it is used as a pungicide in agriculture and in horticulture in particular zinc-ethylene-1,2-bis-dithiocarbamidate is used; the compound mentioned is of great importance among commercial products (cf. R. Wegler, Chemistry of Plant Protection and Pest Control Agents ", Volume 2, page 65, Berlin / Heidelberg / New York (1970)). The effect at low application concentrations however, it is not always satisfactory. The curative fungicidal effect is also beneficial for the Practice completely inadequate.

Furthermore, the compound does not have a sufficient microbicidal effect.

It has been found that the new dithiocarbamic acid salts of urea derivatives of the formula in which R and R 'stand for hydrogen methyl and ethyl, where R' also stands for the group can stand, where A stands for alkylene with up to 4 carbon atoms, furthermore R and R 'together with the connecting nitrogen atom can stand for a 5- to 6-membered heterocycle, which can optionally also contain oxygen and / or nitrogen as further heteroatoms and B for the groups NH-R ", SR "and OR" stands, where R "stands for hydrogen, alkyl with up to 20 carbon atoms, cycloalkyl with up to 6 carbon atoms and for aryl, the latter optionally being substituted by lower alkyl, nitro and / or halogen and n for the number 1 stands when R 'stands for hydrogen, methyl and ethyl, and stands for the number 2 when R' stands for the group have strong fungicidal and microbicidal properties.

It has also been found that the dithiocarbamic acid salts of urea derivatives of the formula (I) are obtained when urea derivatives of the formula in which B has the meaning given above, or its mineral acid salts with dithiocarbamic acid ammonium or alkali metal salts of the formula in which R and R "'stand for hydrogen, methyl and ethyl and R"' also stands for the group can stand, where A has the meaning given above and M stands for ammonium and for an alkali metal, furthermore R and R "'together with the connecting nitrogen atom stand for a 5- to 6-membered heterocycle, which optionally also contains oxygen as further heteroatoms and / or nitrogen may be reacted in the presence of polar solvents.

Surprisingly, the dithiocarbamic acids according to the invention show Salts of urea derivatives have a better fungicidal and microbicidal effect than known connections.

In addition to the protective effect, there is another one that is more important in practice clear curative effect added. The compounds according to the invention therefore provide a real asset to technology.

If the sodium salt of dimethyl dithiocarbamic acid and n-butylguanidinium sulfate are used as starting materials, the course of the reaction can be represented by the following equation: If the ammonium salt of ethylene-1,2-bis-dithio = carbamic acid and the hydrochloride of phenyl-biguanidine are used as starting materials, the reaction equation is as follows: The urea derivatives required as starting materials are generally defined by the formula (II). In this formula, B preferably stands for the groups NH-R " and SR "and R" preferably represent alkyl having up to 20 carbon atoms, cyclohexyl and phenyl, the latter preferably being substituted by methyl, chlorine, bromine and / or nitro. Most of the compounds are known; for the rest, reference is made to the section "Preparation of the precursors" in the preparation examples.

The ammonium resp.

Alkali salts of. Dithiocarbamic acids are defined by the above formula (III). In this formula, R preferably represents hydrogen and methyl and R ″ 'preferably represents methyl and the group in which A preferably represents the ethylene, 1-methyl-ethylene and 1,2-dimethyl-ethylene group and M preferably represents ammonium and sodium. The compounds are well known.

Suitable diluents when carrying out the invention Process all polar solvents in question.

These preferably include water and water-miscible organic ones Solvents, such as from the series of alcohols methanol, ethanol, isopropanol, from the series of ketones acetone, from the series of carboxylic acids or carboxylic acid derivatives Glacial acetic acid, acetonitrile, dimethylformamide, and tetrahydrofuran are also used as solvents and dioxane can be used. The organic solvents can also be diluted with water will.

The reaction temperatures can be varied within a relatively wide range will. In general, one works between 0 and 1000C, preferably between 10 and 800C.

The processes mentioned are preferably carried out in stoichiometric proportions. However, deviations of up to 50% are without significant reduction in yield possible. In detail one can proceed in such a way that one 1 mol of the urea derivative of the formula (I) or of the corresponding mineral acid Salt obtained by adding a mineral acid to the urea derivative is presented in aqueous or alcoholic solution and 1 mole of a water-soluble Ammonium or alkali salt of a monodithiocarbamic acid also in solution adding with stirring; in the case of bis-dithiocarbamic acids, 2 moles are a urea derivative to use per mole of bis-dithiocarbamidate. It is also possible the other way round to proceed and to submit the dithiocarbamidate in solution and the urea derivative or add its mineral acid salt in solid form or in solution. In the end it is also possible for both reactants to be dissolved at the same time in an initially charged solvent or added to water or an aqueous solvent mixture with stirring will.

The active ingredients according to the invention are highly fungitoxic Effect on and are characterized by a wide range of effects. Your good Tolerance for higher plants allows their use as a pesticide against fungal diseases. They damage crops in the control the necessary concentrations of mushrooms. The compounds are non-toxic to each other Warm-blooded animals.

Fungitoxic agents in crop protection are used for control of fungi from various classes of fungi, such as Archimycetes, Phycomycetes, Ascomycetes, Basidiomycetes and Fungi imperfecti.

The active ingredients according to the invention can be used against parasitic ones Fungi on above-ground parts of plants, against fungi causing tracheomycosis, the attack the plant from the ground, against seed-borne fungi as well as against soil-dwelling fungi Mushrooms.

The following are important fungi to be controlled with the active ingredients: Phytophthora infestans and Fusicladium dendriticum, which are the causative agents of the herbaceous and Tuber rot, potato and tomato wilt or as a causative agent of apple scab are of great economic importance.

The active compounds according to the invention can be used in the customary formulations such as solutions, emulsions, suspensions, powders, pastes and granulates. These are made in a known manner, e.g. B. by mixing the active ingredients liquefied pressurized liquids with extenders, i.e. liquid solvents Gases and / or solid carriers, optionally using surface-active substances Agents, that is to say emulsifiers and / or dispersants. In the case of use of water as an extender can be, for. B. also organic solvents as auxiliary solvents be used. The main liquid solvents that can be used are: aromatics, such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated ones aliphatic hydrocarbons such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane, or paraffins, e.g. B. petroleum fractions, Alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, Methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water; with liquefied gaseous Extenders or carriers are liquids that are meant to be used in normal Temperature and under normal pressure are gaseous, z. B. aerosol propellants, such as halogenated hydrocarbons, e.g. B. Freon; as solid carrier materials: natural rock flour, such as kaolins, are, talc, chalk, quartz, attapulgite, montmorillonite, or diatomaceous earth, and synthetic minerals such as fumed silica, alumina and Silicates; as emulsifiers: non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. B.

Alkyl aryl polyglycol ethers, alkyl sulfonates, alkyl sulfates and aryl sulfonates; -As a dispersant: e.g. B. lignin, sulphite and methyl cellulose.

The active compounds according to the invention can be used in the formulations in Mixture with other known active ingredients, such as fungicides, insecticides and acaricides.

The formulations generally contain between 0.3 and 95 percent by weight Active ingredient, preferably between 0.5 and -90.

The active ingredients can be used as such, in the form of their formulations or the application forms prepared therefrom, such as ready-to-use solutions, emulsions, Suspensions, powders, pastes and granules. The application happens in the usual way, e.g. B. by spraying, spraying, dusting, scattering and pouring.

The active ingredients according to the invention are generally at active ingredient concentrations sufficiently effective between 0.0001 and 0.5 percent by weight. When using Aqueous active ingredient preparations can increase the active ingredient concentrations in larger Ranges fluctuate and are then approximately between 0.0005 and 2.0 r-. Will the Active ingredients applied according to special application methods, e.g. B. after the ULV process (ultra-low-volume), the active ingredient concentrations are higher, e.g. B. between 20 and 80%.

The substances according to the invention are also of interest as microbicides. ] Due to their superior antimicrobial effects, which can be applied on a wide scale from microorganisms, the compounds are used for many purposes of disinfection, Suitable for preservation and antimicrobial treatment; also lies a good effect against blue and green aliens.

As microorganisms, their control is of economic importance are to be mentioned: Aspergillus niger, Penicil = lium camerunense and Paecilomyces varioti as a representative of resistant molds, as well as Trichophyton mentagrophytes as a common athlete's foot. Candida albicans and Saccharomyces spec. belong to the Yeasts, which often appear as pathogenic forms. Escherichia coli, Bacterium proteus, Pseudomonas pyocyanea and Staphylococcos aureus are gram-negative or gram-positive germs, some of them are pathogenic.

Some of the compounds of the invention also have an insecticidal effect Effect.

The following examples give an overview the possible applications.

Example A: Phytophthara-T-est solvent: 4.7 parts by weight acetone Dispersant: 0.) parts by weight of alkylaryl polyglycol ether, water, 95 parts by weight The concentration of active substance required for the desired concentration is mixed in the spray liquid necessary amount of active ingredient with the specified amount of solvent and diluted of the concentrate with the specified amount of water, which contains the additives mentioned.

Young tomato plants (Bonny best) with 2 - 6 leaves until dripping wet. The plants remain for 24 hours at 2000 and a relative humidity of 70% in the greenhouse. Afterward the tomato plants with an aqueous spore suspension of Phytophthora infestane inoculated. The plants are in a humid chamber with a 100% Humidity and a temperature of 18-2000.

After 5 days, the attack on the tomato plants as a percentage of the untreated, however, inoculated control plants were also determined. 0% means no infestation, 100% means that the infestation is just as high as in the control plants.

Active ingredients, active ingredient concentrations and results are shown in the following table: Table Phytophthora test Infestation in% of the infestation of the untreated control an active ingredient concentration Active ingredient (in §) of 0.025 0.0062 / GH7 S as \ Mn 64 86 NC / 2 (known) H7; 73 91 (> -CS) Zn 73 91 73 J 2 (known) CH3 5 NH II 0 C * SH H2N-C-NH-C12H25 -18- 40 CH3.- CH3 S NH lt 1! -NC-SH. H2N-C H2N-C-NH-014-H29 18 40 CH3 CH3 5 NH NC-SH H2N-C-NH-C16H33 18 74 CH3 CH3 S NH tt lt NC-SH H2N-C-NH-C18H37 26 90 CH3 Example B: Fusicladium test (apple scab) / curative solvent: 4.7 parts by weight: acetone emulsifier: 0.3 parts by weight alkylaryl polyglycol ether water: 95 parts by weight The amount of active ingredient required for the desired concentration of active ingredient in the spray liquid is mixed with the specified amount of solvent and diluted the concentrate with the specified amount of water, which contains the additives mentioned.

Young apple seedlings that are in the 4-6 leaf stage will with an aqueous conidia suspension of the apple scab pathogen (Fusicladium dendriticum Fuck.) And inoculated for 18 hours in a humid chamber at 18 - 20 ° C and 100 ffi relative humidity. The plants are then placed in the greenhouse. They dry off.

After a reasonable dwell time, the plants are treated with the spray liquid, which was prepared in the manner indicated above, sprayed to runoff. The plants are then returned to the greenhouse.

15 days after the inoculation, the apple seedlings are infected in Percentage of the untreated, but also inoculated control plants determined.

0 ffi means no infestation, 100% means that the infestation is exactly is as high as in the control plants.

Active ingredients, active ingredient concentrations, the residence time between inoculation and spraying and the results are shown in the table below: Table Fusicladium test / curative Infestation in% of the infestation of the Residence time untreated control Active ingredient in hours of an active ingredient concentration 42 (in) from 0.1 / CH, Zn 8'3 (ON-CS) Zn 83 MCH3 J 2 (known) CH3 S NH , NC-SH. H2N-CH-C1 2H25 0 CH3 CH3 \ S NH NC-SH "H2N-C-NH-C1, H ,, 50 CH3 CH3 S NH ON-C-SH. H2N-C-NH-C16H33 27 CH3 CH S NH 3 \ -b'-5H I1 53 H2N-C-NH-C18H37 CH3 Example C: Fusicladium test (apple scab) / Protective solvent: 4.7 parts by weight acetone Emulsifier: 0.3 parts by weight alkylaryl polyglycol ether, water: 95 parts by weight The amount of active ingredient required for the desired concentration of active ingredient in the spray liquid is mixed together with the stated amount of solvent and diluted Concentrate with the specified amount of water, which contains the additives mentioned.

Young apple seedlings are sprayed with the spray liquid are in the 4 - 6 leaf stage, up to dripping wet.

The plants remain at 200 ° C. and a relative atmospheric humidity for 24 hours of 70% in the greenhouse. They are then washed with an aqueous suspension of conidia of the apple scab pathogen (Fusicladium dendriticum Fuck.) inoculated and 18 hours long incubated in a humidification chamber at 18-200C and 100 fG relative humidity.

The plants are then returned to the greenhouse for 14 days.

15 days after the inoculation, the percentage infestation of the seedlings is determined of the untreated, but also inoculated control plants.

0% means no infestation 100% means that the infestation is exactly the same is high as in the control plants.

Active ingredients, active ingredient concentrations and results are shown in the following table: Table Fusicladium test / Protective Infestation in% of the infestation of the untreated control an active ingredient concentration Active ingredient (in%) of 0.0062 0.00156 / CH S 3 Mn 75 CH3 J 2 (known) tCH S \ / CH,. ) Z 31 36 J.Innt) (known) CH3 S NH NC-SH H2N-C-NH-C12H25 2 4 CH3 CH3 S NH \ -C-SH. H2N-C'1-NH-C1 4H29 4 9 CH3 CH3 S NH lt 1? wN-C-SH. H2N-C-NH-C16H33 4 17 CH3 CH3 S NH lt lt -C-SH H2N-C-NH-C18H37 9 17 CH3 Example D: Microbicidal Effect / Reciprocal Sprout Inhibition Values The table shows the reciprocal sprout inhibition values for some selected species from the three groups bacteria, fungi and yeasts. This expresses the dilutions of the compounds mentioned at which the growth of the selected microorganisms is completely inhibited when these compounds are added to a nutrient medium that is optimal for the organisms. The microorganisms used for this inhibition test are widespread and are known to be resistant to conventional chemical preservatives and disinfectants.

The germ inhibition values listed are obtained using the usual dilution method determined as follows: The preparations to be tested are in the specified diluent prepared in different concentrations.

In the prepared, filled with standardized nutrient substrates Test tubes are given certain amounts of the organ-dissolved preparations.

All work is carried out under sterile conditions.

The incubation of the various microorganisms given in the table takes place at 300C.

The sprout inhibition values given in the table show the concentrations at which no growth occurs yet.

Diluent: Ethylglycol Table Microbicidal effect / reciprocal germ inhibition values id ooo ooo ddri o 'oo oo 0) 0 U3 C \ i \ D Wko M pc \ I 0 O r3 ol O 0 0 amh ooo docd cuoa, Ln c cu aio r- r- Pt 8 Plcd c, Paecilo- Candida Saccha- o Pseudo-- O oo Iu H romyces o monas o O o cd ok + 1 com varioti o spec. coccus pyocycoli Active ingredient ense N a, c I o, cd ooo oooo oho o oo cdoP, 2NC5lt) S o 72,000 15,000 15,000 30,000 24,000 A ooo mkm M CO CO e cz oo rl I 0 0 0 adm ooo PF: 5 zucd Ln O Nile OUO v £ H2N-b'-NH-C12H25> 80,000 80,000 80,000 80,000 72,000 72.0b0 location ri ooo tRO O 0 0 5 NH cuok cdhd Ln n tl PiB co a r1 r rl r OOO c) h OOO t1 OOOOO d> S m. . @ N o AH c) O> a: + O CU CM m: t (M sF rr from left to right x S W. P: I m I d N OJ st: m CM <m: t IMM 91 I> M = C :) MV w æ | Z o cm + ~ s S; NN ta ndno X mx " h \ OOP: ri w »VC) D v Example E: Microbicidal Action / Tanning Agent Solution Natural tanning agents are protected against fungal growth by adding the active ingredients, as can be seen from the following table.

The concentration data relate to the active ingredient.

This is distributed in a suitable solvent, the tanning solution added and brought to the concentrations shown in the table (g active ingredient per liter of solvent).

In the table: - no mold growth + mold growth table microbicidal effect / tanning agent solution solvent: ethylglycol Active ingredient concentration g / l fungal growth Control O + 1 + o-oxydiphenyl 5+ (known) 10 CH3 S NH 0.1 according to NC-SH. H2N-O-NH-C14H29 9 CH3 Example F: Microbicidal Effect / Disinfecting Carpet Washing For disinfecting carpet washing with simultaneous antimicrobial treatment of the carpet fibers, a detergent with the composition indicated overleaf is used. The carpets are brushed on the carpet washing machine for 1 minute with a solution of the specified detergent, washed, rinsed for 1 minute and dried at 60 ° C. in a stream of warm air. With this treatment, the carpets are cleaned, disinfected and given an antimicrobial finish.

Samples of the treated carpets are placed on inoculated agar plates and form growth-free zones, the size of which is determined and thus the antimicrobial Show effectiveness.

The table provides information on the concentration and size of the emm zones emerged.

Table of microbicidal effects / disinfecting carpet washing Composition of the detergent: 7 parts by weight of nonylphenyl polyglycol ether 2 parts by weight of active ingredient Size of the carpet samples: 2 x 2 cm Inhibition zones in mm Active ingredient detergent- staphylo- tricho- concentration coccus phyton in% aureus mentagr. Control 0.3 0 0 (untreated) CH S NH lt lt 2 -C-SH H2N-C-NH-C14H29 0.3 3 1 CH3 Table of microbicides and algicidal effects / disinfection of circulating water Active ingredient concentration Time in minutes KeiYr- ml / m) according to the number of active ingredients / addition ~ ml G 1,520,000 CH S NH 15 15,000 dd dd NC-SH. H2N-O-NH-C14H29 20 30 100,000 CH3 60 175,000 120 800.00G 15 22,000 CH S NH 30 80,000 dd n PC-SH H2N-C-NH-C12H25 20 60 120,000 CH3 120 1,000,000 Production examples Example 1: A solution of 0.2 mol of sodium N, N-dimethyldithiocarbamidsaures in 200 ml of methanol is heated to boiling with stirring and a solution of 0.1 mol of n-butylguanidinium sulfate, dissolved in 200 ml of methanol, in the dithiocarbamidate solution added dropwise. The mixture is stirred for about 1 hour, then cooled to 2000 and the precipitated sodium sulfate is filtered off. The mother liquor is distilled off in vacuo, the oily residue is dissolved in a mixture of 100 ml of n-propanol and 70 ml of ether and the solution is cooled to OOC. The product which crystallizes out after trituration is filtered off with suction, washed with ether and dried at a temperature of 50 ° C. and a pressure of 200 torr.

The finely crystalline, white product obtained melts at 1030C. the Yield is 42.6 g (90% of theory) with a content of 98.9% of N, N-dimethyldithiocarbamic acid n-butylguanidinium salt.

Furthermore, the following compounds of the formula manufactured: Example RR 'B n Fp (Or) No. 2 CH3 CH3 NH- (CH2) 4-O, H-OH3 1 83-84 O2H5 3 CH3 CH3 NH-O12H25- (n) 1 94-96 4 CH3 CH3 NH-O14H29- (n) 1 89-93 5 CH3 CH3 NH-O16H33- (n) 1 91-94 6 CH3 CH3 NH-O18H37- (n) 1 99-100 N Cl 129 o "Hwiffi 7 CH3 CH, 1 (and decomp.) NH 148 tI 8 CH3 CH3 NH-C-NH 1 (and decomp.) NH NO2 128 9 CH3 OH3 NH-C-NH 1 (and decomp.) NH 161 II 10 CH3 CH3 NH-C-NH / \ OH3 1 (and decomp.) NH 154 11 CH3 CH3 NH-C-NH 9 1 (and decomp.) CH3 NH 170 12 CH2-CH2- ° -CH2-CH2 NH-C-NH 1 (and decomp.) NH 170 according to 13 CH2-CH2-0-CH2-CH2 NH-C-NH <1 (and decomp.) Cl Example RR 'B n Fp (° C) No. NH 158 14 CH2-CH2-0-CH2-CH2 NH-C-NH to 1 (and decomp.) Cl NH 168 15 OH2-CH2-0-OH2-OH2 NH-O-NH zuCl 1 (u decomp.) NH NO2 150 16 CH2-CH2-0-CH2-CH2 NH-C-NH 4 1 (1st dec.) NH 155 17 CH2-CH2-0-CH2-CH2 NH-O-NHN02 1 (and decomp.) NH 170 NHOttNHO 18 CH2-CH2-0-CH2-CH2 NH C H3 CH7 5 (and decomp.) NH 171 NHO'tNHy 19 CH2-CH2-0-CH2-CH2 NH-C-NH to 1 (and decomp.) CH3 CH2 S NH 150 20 H Nil 0 "NH / \ 2 (and decomp.) 20 H CH2-NH-C-SH NH-C-NHc =)) CH2 S NH 155 21 H 1 II NH »6-NH / \ OH 2 (and decomp.) CH2-NH-C-5H Example RR 'B n Pp ( No. 5 NH CH2 S NH 128 1, 1 gs 2 (and decomp.) 22 H CH2-NH-C-SH NH-C-IE 2 (and decomp.) CH3 CH2 S NH 145 1? 23 H CH2-NH-C-SH NH-O-NII to Cl 2 (and decomp.) CH2 S NH 117 1 dd dd 24 H CH2-NH-C-SH NH-C-NH 9 2 (and decomp.) Cl CH2 S NH 143- 1? H 25 H OH2-NH-O-SH NH-C-NH <2 (and decomp.) Cl CH2 S NH 150 I, 26 H CH2-NH-C-SH NH-O-NH1 \ N02 2 (and decomp.) CH2 S NH 133 27 H tt lt 2 (and decomp.) 27 H CH2-NH-C-SH NH-C-NH 9 2 (and decomp.) N02 CH2 S NH 146 28 H lt NHCNH / \ OH 2 NH-C-NH v CH3 2 (and decomp.) CH2-NH-C-SH CH3 CH2 S NH CHD 148 29 H CH2-NH-C-SH NH-C-NH <2 (and decomp.) CH3 Example RR 'B n Fp (° C) No. CH2 S Nile Cl 89 t L lt II lt 30 H CH2-NH-C-SH NH-O-NH / \ 2 (and decomp.) CH3 CH2 S NH 92 according to II 31 H OH2-NH-O-SH NH-C-NH <Cl 2 (and decomp.) CH3 CH2 S Nile 142 II according to 32 H OH2-NH-O-5H NH-O-NH CH? CH3 2 (and decomp.) Cl CH2 S NH 138 33 H lt NHCNil0 / \ 2 NH-C-NH) 2 (and decomp.) OH2NHO5H CHD CH2 S 126 according to 34 H CH2-NH-C-SH -S-CH3 2 (and decomp.) Representation of the preliminary products The preliminary products are obtained in a manner known in principle.

Examples include: a) N-dodecyl guanidinium sulfate Mixture of 139 g of S-methylisothiourea sulfate (0.5 mol) and 200 ml of ethanol is a solution of 185 g of dodecylamine through a dropping funnel at about 50 ° C. while stirring (1 mol) was added dropwise in 500 ml of ethanol. After the addition will heated to boiling with further stirring, the resulting methyl mercaptan through driven out a gentle stream of nitrogen and absorbed in a sodium hydroxide template. The reaction is complete when in the nitrogen discharge with moistened lead acetate paper the detection of methyl mercaptan is only weak or completely negative. Methyl mercaptan gives an intense yellow color on lead acetate paper. The hot reaction solution is then filtered off from undissolved parts (funnel and filter beforehand warm up to at least 800C). The dodecylguanidine sulfate crystallizes in the filtrate immediately off. After standing overnight, it is cooled to 1000 and suctioned off.

It is washed with ice-cold methanol / ether (= 1: 1) and 241 is obtained g of crude product (after drying at 50 ° C. and 100 Torr), that is 87.2% of theory. A pure product is obtained by recrystallization from 80% by volume of ethanol, for 240 g of crude product about 1000 ml are required.

b) N- (2-methyl-3-chlorophenyl) -biguanidinium chloride. 141.5 are dissolved g (1 mol) of -2-methyl-3-chloroaniline in a solution of 85 ml of concentrated hydrochloric acid and 400 ml of water in the heat. Rinse with a further 100 ml of water in a stirred flask, add 84 g of dicyandiamide and reflux for 6 hours. After cooling down One sucks off, washed with a little water and dried. 213 g of crude product are obtained, that's 70% of theory. Recrystallization can be done from hot water in the presence made of activated carbon.

c) S-methyl-isothiourea The compound is commonly known received preparative instructions (see Organic Syntheses, Coll. Vol. III (1955), P. 440).

Claims (6)

Patent claims: 1) Dithiocarbamic acid salts of urea derivatives of the formula in which R and R 'stand for hydrogen, methyl and ethyl, where R' can also stand for the group S lt A-NH-C-SH, where A stands for alkylene with up to 4 carbon atoms, furthermore R and R 'together with the connecting nitrogen atom stand for a 5- to 6-membered heterocycle, which can optionally also contain oxygen and / or nitrogen as further heteroatoms and B stands for the groups NH-R ", SR "and OR" stands, where R "stands for hydrogen, alkyl with up to 20 carbon atoms, cycloalkyl with up to 6 carbon atoms and for aryl, the latter optionally being substituted by lower alkyl, nitro and / or halogen and n for the number 1 stands when R 'stands for hydrogen, methyl and ethyl, and stands for the number 2 when R' stands for the group stands. 2) Process for the preparation of dithiocarbamic acid salts of urea Der1't'en, characterized in that urea derivatives of the formula in which B has the meaning given in claim 1 or its mineral acid salts with dithiocarbamic acid ammonium or alkali metal salts of the formula in which R and R't 'stand for hydrogen, methyl and ethyl and R "' also stands for the group can stand, where A has the meaning given in claim 1 and M stands for ammonium and for an alkali metal, furthermore R and R "'together with the connecting nitrogen atom stand for a 5- to 6-membered heterocycle, optionally also as further May contain heteroatoms oxygen and / or nitrogen, reacts in the presence of polar solvents. 3) Fungicidal and microbicidal agent, characterized by a Content of dithiocarbamic acid salts of urea derivatives according to Claim 1. 4) method for combating fungi and microbes, characterized in that that dithiocarbamic acid salts of urea derivatives according to claim 1 on fungi, Allows microbes or their habitat to act. 5) Use of dithiocarbamic acid salts of urea derivatives according to claim 1 for combating fungi and microbes. 6) processes for the production of fungicidal and microbicidal agents, characterized in that dithiocarbamide = acidic salts of urea derivatives according to claim 1 mixed with extenders and / or surface-active agents.