CA1159843A - Carbonylaminourethanes, and herbicides and fungicides containing these compounds - Google Patents

Abstract

Abstract of the Disclosure: Urethanes of the general formula

Description

- l - O.Z~ 0050/034525 Carbonylaminourethanes, and he.rbicides and fungicides containing these compounds The present in~ention relates to novel valuable urethanes which contain a carbonylamino group, to pro- -cesses for the preparation of these urethanes, to herbi-cides and fungicides containing these compounds, and to processes for controlling undesired plant growth and fungi by means of these compounds.
The use of ethyl N-[3-(N'-phenylcarbamyloxy)-phenyl]-carbamate and methyl N-[3-(N'-3~-methylphenyl-carbamyloxy)-phenyl]-carbamate as herbicides is known (German Published Application DAS 1,567,151).
It is also known that meta-(3,3-dimethylureido)-benzyl N-(tert,-butyl)-carbamate has herbicidal proper-ties (U.S. Patent 3,756,250), Further, it is known that 1-[2-(2,4-dichloro-phenyl)-2-(2-propenyloxy)-ethyl~-imidazole may be used as a fungicide (British Patent 1,318,590), We ha~e found that urethanes of the general form-ula NXCORl Y A-O-CO-¢

where Rl is unsubstituted or halogen-, alkoxy-, alkoxy-carbonyl- or cyano-substituted alkyl, cycloalkyl, alkenyl or alkynyl (eg. methyl, ethyl, isopropyl, n-propyl, 9~r~

- 2 O.Z. 0050/034525 n-butyl, sec.-butyl, tert.-butyl, iso-butyl, sec.-pentyl, chloromethyl, ,~-dichloroethyl, dichloromethyl, methoxy-methyl, acetoxymethyl, cyanomethyl, cyclopropyl, cyclo-hexyl, -methyl-cyclopropyl, sec.-propenyl or ethynyl) or alkoxy (eg. methoxy, ethoxy, n-propoxy, iso-propoxy, tert.-butoxy or sec -butoxy), cycloalkoxy (eg. cyclo-hexoxy or cyclopentylmethoxy), alkenyloxy (eg. prcpenyl-oxy), alkynyloxy (eg, sec -butynyloxy), cyanoalkoxy (eg, 2-cyanoethoxy), haloalkoxy (eg 2-chloroethoxy or 1,3-difluoro-iso-propoxy), alkylthio (eg. methylthio, ethyl-thlo, n-propylthio or tert.-butylthio), alkenylthio or al~ynylthio, Y is hydrogen, alkyl (eg. methyl or tert -butyl), halogen (eg. fluorine, chlorine or bromine), alkoxy (eg.
methoxy) or haloalkyl (eg. trifluoromethyl), A is unsubstituted or alkyl-substituted alkylene, for example of 1 to 8 c~rbon atoms (eg. methylene, methyl-methylene, dimethylmethylene, ethylmethylene, propylene, hexylene, ethylene, methylethylene, methylpropylene, ethylpropylene, methylpentylene or dimeth~lpropylene), R2 is hydrogen, alkyl (eg, methyl, ethyl or isa-propyl), al~oxyalkyl (eg, methoxymethyl or 2-methoxy-ethyl), haloal~yl (eg. chloromethyl) or unsubstituted or alkyl- or halogen-substituted benzyl, R is alkyl which is unsubstituted or substituted by halogen or by alkoxy or by unsubstituted or substituted aryl (eg. methyl, ethyl, 2~chloroethyl, 2-methoxyethyl, benzyl, isopropyl, n-propyl, 4-chlorobenzyl, n-butyl, sec.-butyl, tert.-butyl, iso-butyl, 2,4-dichlorobenzyl, _ 3 _ o.Z. 0050/034525 a-methyl-2-chlorobenzyl, 2-ethylhexyl or n-decyl) or is unsubstituted or halogen-substituted alkenyl (eg allyl, 2-chloroprop-l-en-3-yl or but-1-en-3-yl), unsubstituted or halogen- or alkoxy-substituted alkynyl (eg. propargyl, but-l-yn-3-yl or 3 methylbut-l-yn-3-yl) or unsubstituted or alkyl-substituted cycloalkyl (eg. cyclopentyl, cyclo-hexyl, 3-methylcyclohexyl, 2,6-dimethylcyclohexyl, cyclo-heptyl, 4-tert.-butylcyclohexyl, cyclooctyl, cyclododecyl or 3,5-dimethylcyclohexyl), phenyl or monosubstituted or polysubstituted phenyl, the substituents being alkyl, haloalkyl~ alkoxyalkyl, cycloalkyl, halogen, alkoxy, halo-alkoxy, nitro, aryl, aryloxy, thiocyanato, cyano, ~5 ~5 NH-C-R4, NHCooR4, NHCON , CooR4, CON , S-R4, So2R4, d \R4 \~4 oSo2R4, -Co-R4 or S02N , where R4 and R5 each indep-endently of one another are hydrogen or unsubstituted, monosubstituted or polysubstituted aryl, or one of R4 and R5 has one ofthe other meanings given for ~2 (~3 thus being, eg., phenyl, 4-fluorophenyl, 2-methoxyphenyl,

3-methylphenyl, 2-fluorophenyl, 3-methyl-5-iso-propyl-phenyl, 3-ethylphenyl, 3-chlorophenyl, 2,4,~-trimethyl-phenyl, 3-fluorophenyl, 3-chloro-4-fluorophenyl, 3,4-dimethylphenyl, 3-trifluoromethylphenyl, 4-methylphenyl, - 3,4-difluorophenyl, 3-chloro-4-methylphenyl, 4-bromo-phenyl, 4-iodophenyl, 4-chlorophenyl, 2-chlorophenyl, 2-chloro-4-fluorophenyl, 3-isopropylphenyl, 4-ethylphenyl, 5~
_ O.Z. 0050/034525 3-methoxycarbonylaminophenyl, 4-ethoxyphenyl1 2-methyl-phenyl, 3-methoxyphenyl, 4-cyanophenyl, 2,~-dimethyl-phenyl, 2,4-dichlorophenyl, 3-methyl-4-chlorophenyl, - 3,4-dichlorophenyl, 3-chloro-4-bromophenyl, 3-trifluoro-methyl-4-chlorophenyl, 3-chloro-4-difluoromethoxyphenyl 9 3-(1,1,2,2-tetrafluoroethoxy)-phenyl or 3,4-dichloro-5-methylphenyl), exhibit a good herbicidal action on undesired plants and are at the same time well tolerated by crops The novel compounds furthermore have a fungicidal action. They can therefore be used as crop protection agents.
The novel compounds can be prepared by, for ex-ample, the following processes:
Process I:
A hydroxy compound of the general formula ~HCORl / A - OH

is reacted with an isocyanate of the general formula R3-NCO, where Rl, R3, Y and A have the above meanings; in the novel compound produced, R2 is H. The reaction is carried out in the presence or absence of a conven-tional catalyst for isocyanate reactions, for example a tertiary amine teg triethylamine or 1,4-diazabicyclo-(2,2,2)-octane), a nitrogen-containing heterocycle (eg.
pyridine or 1,2-dimethylimidazole) or an organic tin compound (eg. dibutyl-tin diacetate or dimethyl-tin _ 5 _ O.Z. 0050/034525 dichloride), in the presence or absence of a solvent which is inert under the reaction conditions, for ex-ample a hydrocarbon (eg. naphtha, gasoline, toluene, pentane or cyclohexane), a halohydrocarbon (eg. methylene chloride, chloroform, dichloroethane, chlorobenzene or o-, m- or p-dichlorobenzene), a nitrohydrocarbon (eg.
nitrobenzene or nitromethane), a nitrile (eg. aceto-nitrile, butyronitrile or benzonitrile), an ether (eg.
diethyl ether, tetrahydrofuran or dioxane), an ester (eg. ethyl acetate or methyl propionate), a ketone (eg.
acetone or methyl ethyl ~etone) or an amide (eg. di-methylformamide or formamide), at from O to 150C, pre-ferably from 40 to 100C. (S. Petersen in Methoden der Org Chemie, volume VIII, page 131, Georg-Thieme-Verlag, Stuttgart, 4th edition (1952)).
Process II:
An aniline of the general formula / ~2 A-O-CON
y " R3 where Y, A, R2 and R3 have the above meanings,is reacted with a compound of the general formula X - C -O
where X is a leaving group (eg. chlorine, bromine or Rl-C-O-) and R1 has the above meanings, in a suitable ~r~
- 6 - o.Z. 0050/034525 solvent, for example water, an alcohol (eg methanol, ethanol or isopropanol) or one of those mentioned ~or process I, in the presence of a conventional acid acceptor, for example an alkali metal hydroxide, carbon-ate or bicarbonate, an alkaline earth metal oxide, hydroxide, carbonate or bicarbonate or a tertiary organic base (eg, triethylamine, pyri*ine, N,N-dimethyl-aniline, N,N-dimethylcyclohexylamine, quinoline or tri-butylamine), at from -20 to 150C, preferably ~rom 20 to 80C (German Laid-Open Application DOS 1,643,763).
Process III:
A chlorocarbonic acid ester of the general form-ula NHCORl A-OCOCl ~R2 is reacted with an amine of the general formula H-~

where Rl, R2, R3, Y a~d A have the meanings gi~en above, under the same conditions as in process II.
To prepare the hydroxy compound required in process I, an aniline of the general formula A - OH

_ 7 _ o.Z. 0050/034525 where Y and A have the meanings given above, is reacted with a compound of the general formula X - C - Rl J
O ..

where X is a leaving group (eg. chlorine, bromine or Rl C O) and Rl has the above meanings, under the condi-O

tions described for process II.
An anil~ne of the general formula ~ A - OH
y where Y and A ha~e the above meanings, is obtained by reducing a nitro compound of the general formula 5~
Y
where Y has the above meanings and Z is an unsubstituted or alkyl-substituted hydroxyalkyl, carbonylalkyl, hydroxy-alkenyl or carbonylalkenyl radical (British Patent 758,993, and U.S. Patents 2,680,136 and 4,021,487).
The aniline required for process II is obtained by reacting a 3-(hydroxyalkyl)-nitrobenzene with an iso-cyanate and then reducing the nitrourethane obtained.
The chlorocarbonic acid ester employed in pro-cess III is obtained by phosgenating one o~ the hydroxy compounds employed in process I.

- 8 - O.Z. 0050/034525 The methods and Examples which follow illustrate the preparation of the novel urethanes and of their intermediates.
Method A
m-(l-Hydroxypropyl)-aniline 150 parts by weight of m-nitropropiophenone are dissolved in 1,500 parts by volume of tetrahydrofuran (THF), mixed with 60 parts by weight of Raney nickel and hydrogenated in a 2.5 liter autoclave at 70C and 50 bar hydrogen pressure, until the pressure remains constant.
The mixture is filtered, the filtrate is freed from sol-vent and the residue is recrystallized from petroleum ether. This gives 109 parts by weight of a compound, of melting point 69C, which has the following structural formula N~2 ,~
C~-OH

Method B
3-(1-Hydroxyethyl)-phenylpropionamide 103 parts by weight of 3-amino--methylbenzyl alcohol are dissolved in 600 parts by weight of THF and 84 parts by weight of NaHC03 are added. 69 4 parts by weight of propionyl chloride are slowly added drop-wise, the mixture is stirred overnight and is then filtered, the solution is concentrated and the residue is recrystallized from toluene/cyclohexane. This _ g .. O.Z. 0050/034525 gives llO parts by weight of a ~Ihite compound, of melt-ing point 77-79C, which has the following structural formula: N~COC2H5 ..
CH-OH

The following compounds, ~or example, can be synthesized ~y following this procedure:
.. .

NHCOR

. A - OH

R Y Am.p.(C) OC~3 H CH(CH3)78- 80 SCH3 H CH(CH3)121-122 C2H5 H C~2 69- 71 C2H5 H CH(C2H5)93~ 94 C2H5 H CH2CH(CH3)CH2 oil t-C4Hg H CH2 90- 92 C~H5 4Cl CH2 Method C
0-(3-Nitrobenzyl)-N-(3,4-dichlorophenyl)-urethane lOO parts by weight of 3-nitrobenzyl alcohol are dissolved in 500 parts by weight of THF,. 3 drops - 10 - O.Z. 0050/034525 of dibutyl-tin diacetate.and 123 parts by weight of 3,4- dichlorophenyl isocyanate are added, the mixture is stirred overnight and concentrated and the residue is stirred with toluene. The product is filtered o~f and dried, giving 155 parts by weight of a white compound~
- of melting point 182 - 184C, which has the following structural formula~

Cl CH20CONX~C l A similar method may be used, for example, to prepare 0-(3-nitrobenzyl)-N-t3-trifluoromethylphenyl)-urethane, melting point 97-99C, and 0-(3-nitrobenzyl)-N-(3-chlorophenyl)-urethane, melting point 123-125C
Method D
0-(3-Aminobenzyl)-N-(3,4-dichlorophenyl)-urethane 440 parts by weight of tin-II chloride are added to a suspension of 15~ parts by wei~ht of 0-(3-nltro-benzyl)-N-(3,4-dichlorophenyl)-urethane in 1,100 parts by volume of alcohol and 100 parts by volume of concen-trated hydrochloric acid, and the mixture is stirred for

4 days at 20C It is then rendered strongly alkaline with concentrated sodium hydroxide solution, whilst being cooled efficiently; thereafter the mixture is filtered and the residue is repeatedly extracted by stirring with THF. The combined THF solutions are dried and con-centrated, and the crude product thus left is recrystal-lized from toluene/ethyl acetate. This gives 130 ~ O.Z. 005~/034525 parts by weight of white.crystals, of melting point 138-140C, having the following structural formula:

~ CH20CONH~C1 A similar method may be used to prepare, for example, 0-(3-aminobenzyl)-N-(3-trifluoromethylphenyl)-urethane, which is an oil, and 0-(3-aminobenzyl)-N-~3-chlorophenyl)-urethane, of melting point 111-113C.
Method E
N-[3-(Chlorocarbonyloxymethyl)-phenyl]-O-methylurethane A solution of 54 parts by weight of N-(3-hydroxymethylphenyl)-O-methylurethane and 23 7 parts by weight of pyridine in 300 parts by volume of methylene 10. chloride is slowly added dropwise, in the course of 3 hours, to a mixture of 45 parts by weight of phosgene and 50 parts by volume of methylene chloride at -20C.
The batch is then stirred for 2 hours at -10C, 400 ml o~ ice water are added, and the organic phase is separ-ated off, dried over sodium sul~ate, filtered and con-centrated under reduced pressure at 20C. This gives 48 parts of a viscous oil which according to infrared spectroscopy and NMR spectroscopy has the following structure:

C~2-0-CO-C 1 - 12 - O.Z. 0050/034525 - EXAMP~E 1 6.6 parts by weight of phenyl isocyanate and a few drops of triethylamine are added to 10 parts by weight of N-(3-hydroxymethylphenyl)-0-methylurethane in 100 parts by weight of THF After the mixture has stood for two days, it is concentrated and the residue is recrystallized from toluene. This gives 13.8 parts by weight of white crystals, of melting point 139-141C, having the following structural formula (active ingredient No 1) [~
CH20CONX~

24.9 parts by weight o~ 0-(3-~minobenzyl)-N-(3,4-dichlorophenyl)-urethane aredissolved in 200 parts by weight of THF, and 9 6 parts by weight of NaHC03, followed ~y 8 4 parts by weight of cyclopropanecarboxylic acid chloride, are added. The mixture is stirred for 8 hours and filtered, the filtrate is concentrated and the residue is triturated with cyclohexane and filtered off.
This gi~es 27 9 parts by weight of a compound, of melting point 163-165C, which has the following structure (active ingre~ient No. 2) NHC0 ~ Cl ~ C~20CO~ Cl - 13 - O.Z. 0050/034525 28 parts by weight o~ N-[3-(chlorocarbonyloxy-methyl)-phenyl]-O-methylurethane are dissolved in 50 parts by weight of toluene. 31 g of 3-chloro-N-methylaniline in 150 parts by weight of toluene are added dropwise at,20C and the reaction solution is stirred for 8 hours. It is then extracted by shaking 3 times with dilute hydrochloric acid. The solution is then dried and concentrated, the oily residue is caused to crystallize by means of petroleum ether, and the product is filtered off, It consists of white crystals of melting point 64-67C, having the following structural formula (active ingredient No, 3) CH20cON~r~cI

The following compounds may be prepared analogously:

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~ 21 ~ O~Z~ 0050/034525 The active ingredients may be applied as such, in the form of formulations, or application forms prepared therefrom, e.g., as directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizlng, dusting, broadcast~ng or water-ing. The forms of application depend entirely on the purpose for which the agents are being used; in any case they should ensure as fine a distribution of the active ingredlent as possible. The agents generally contain from 0.1 to 95~ especially 10 to 80%
(wt%) of active ingredient.
For the preparatlon of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high bolling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatlc hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloro-form, carbon tetrachloride, cyclohexanol, cyclohexanone, chloro-benzene, isophorone, etc., and strongly polar solvents such as 20 dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, water, etc. are suitable.
Aqueous formulations may be prepared from emulsion con-centrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingre-dients as such or dissolved in an oil or solvent may be homogen-ized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, ad-herent, emulsifying or dispersing agent and possibly solvent or oil.

- 22 - O.Z. 0050/034525 Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalene-sulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether ~ulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty aclds, salts of sulfated hexadecanols, hepta-decanols, and octadecanols, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and 10 naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and form-aldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctyl-phenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkyl-phenol polyglycol ethers, trlbutylphenyl polyglycol ethers, al~yl-aryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxy-ethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixlng or grinding the active ingredients with a solid carrier.
EXAMPLE I
90 parts by weight of compound 1 is mixed with 10 parts by weight of N-methyl-~-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

- 23 ~ ~ ~ ~~~~ C.Z. 0~50~034525 EXAMP~E II
10 parts by weight of compound 2 is dissolved in a mixture consistlng of 90 parts by weight o~ xylene, 6 parts by weight of the adduct of 8 to 10 moles o~ ethylene oxide with 1 mole of oleic acid-N-mono~thanolamide, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 2 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil~
EXAMPLE III
20 parts by weight of compound 2 is dissolved in a ~ixture 10 consisting of 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight of the adduct of 7 moles of ethylene oxide wlth 1 mole of isooctylphenol, and 5 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil.
E~AMPLE I~
20 parts by weight of compound 3 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles 20 of ethylene oxide with 1 mole of castor oil.
EXAMP~E V
80 parts by weight of compound 1 is well ~ixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-~-sulfonic acid, 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel, and triturated in a hammer mill.

- 24 - O.Z. 0050/034525 EXAMPLE VI
5 parts by weight of compound 1 is intimately mixed with 95 parts by weight of particulate kaolin. A dust is obtained containing 5~ by weight of the active ingredient.
EXAMPLE VII
30 parts by weight of compound 1 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingre-dient is obtained having good adherence.EXAMPLE VIII
40 parts by weight of compound 1 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-form-aldehyde condensate, 2 parts of silica gel and 48 parts of water.
A stable aqueous dlspersion is obtained.
EXAMPLE IX
20 parts of compound 1 is intimately mixed with 12 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a 20 phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.
The influence of various representatives of the novel herbicidal urethanes on the growth of unwanted and crop plants is demonstrated in greenhouse experiments.
The vessels employed were plastic flowerpots having a volume of 300 cm , and which were filled with a sandy loam containing about 1.5% humus. The seeds of the test plants were sown shallow, and separately, accordlng to species.

25 ~ O.Z. 0050/034525 In the preemergence treatment, the active ingredients were lmmediately applied to the surface of the soil as a suspension or emulsion in water by spraying through finely distributing nozzles.
The amount of active ingredient applied in this treatment was equivalent to 3.0 kg/ha.
After the agents had been applied, the vessels were lightly sprinkler-irrigated to induce germination and growth. Transparent plastlc covers were then placed on the vessels until the plants had taken root. The cover ensured uniform germination of the plants, insofar as this was not impaired by the chemicals. The comparative agent employed in this method (at the same application rate) was m-(3,3-dimethylureido)-benzyl-N-(tert-butyl)-carbamate (A).
For the postemergence treatment, the plansts were ~irst grown in the vessels to a height of from 3 to 10 cm, depending on growth form, before being treated. For this treatment, either plants whlch had been sown directly in the pots and grown there were selected, or plants which had been grown separately as seedlings and transplanted to the experlment vessels a few days before treatment. ~he amount of active ingredient applied in this treat-ment varied, depending on the active ingredient, and was either0.25, 0.5, 1.0 or 2.0 kg/ha. The comparative agents employed were the prior art compounds methyl-N-t3-(N'-3'-methylphenylcarbamoyl-oxy)-phenyl]-carbamate (B) at 0.25, 0.5 and 1.0 kg/ha, and ethyl-N-[3-(N'-phenylcarbamoyloxy)-phenyl]-carbamate (C) at 2.0 kg/ha.
No cover was placed on the vessels. The pots were set up in the greenhouse - species from warmer areas at from 20 to 35 C, - 26 - O.Z. 0050/034525 and species from moderate climates at 10 to 25C. The experiments were run for from 2 to 4 weeks. During this period, the plants were tended and their reactions to the various treatments asses-sed. The scale used for assessment was 0 to 100, 0 denoting no damage or normal emergence, and lO0 denoting nonemergence or complete destruction of at least the visible plant parts.
The results show that the novel compounds have, on postemer-gence application, a better herbicidal action than the comparative agents on a number of unwanted plants. In addition, a number of 10 compounds according to the invention are better tolerated by certaln crop plants than the comparative agentsO When the novel compounds are applied preemergence, a herbicidal action is also observed.
If the crop plants tolerate the active ingredients less well~
appllcatlon technlques may be used in which the agents are sprayed frrom sultable equipment ln such a manner that the leaves of sensitive crop plants are if possible not touched, and the agents reach the soil or the unwanted plants growing beneath the crop plants (post-directed, lay-by treatment).
In view of the good tolerance of the active ~ngredients and the many application methods posslble, the agents accord~ng to the invention, or mixtures containing them, may be used not only on the crop plants listed in Table 1, but also in a much larger range of crops for removing unwanted plants.
The followlng crop plants may be mentloned by way o~ example:

- 27 - O.Z. 0050/034525 Botanical name Common name Allium cepa onions Ananas comosus pineapples Arachis hypogaea peanuts (groundnuts) Asparagus officinalis asparagus Avena sativa oats Beta vulgaris spp. altissima sugarbeets Beta vulgarls spp. rapa fodder beets Beta vulgaris spp. esculenta table beets, red beets 10 Brassica napus var. napus rape Brassica napus var. napobrassica Brasslca napus var. rapa turnips Brassica rapa var. silvestris Camellia sinensis tea plants Carthamus tinctorius safflower Carya illinoinensis pecan trees Citrus limon lemons Citrus maxlma grapefruits Citrus reticulata mandarins 20 Citrus sinensis orange trees Coffea arabica (Coffea canephoral Coffea liberica) coffee plants Cucumis melo melons Cucumis sativus cucumbers Cynodon dactylon Bermudagrass in turf and lawns Daucus carota carrots Elais guineensis oil palms Fragaria vesca strawberries `- 28 - ~ O.Z. 0050~034525 ~otanical name Common name _ _ _ . _ _ Glycine max soybeans Gossypium hirsutum (Gossypium arboreum cotton Gossypium herbaceum Gossypium vitifolium) Helianthus annuus sunflowers Helianthus tuberosus Hevea brasiliensis rubber plants Hordeum vulgare barley Humulus lupulus hops Ipomoea batatas sweet potatoes Juglans regia walnut trees Lactuca sativa lettuce Lens culinaris lentils Linum usitatlssimum flax Lycopersicon lycopersicum tomatoes Malus spp. apple trees Manihot esculenta cassava Medicago sativa alfalfa (lucerne) Mentha piperita peppermint Musa spp. banana plants Nicothiana tabacum tobacco (N. rustica) Olea europaea olive trees Oryza sativa rice Panicum miliaceum Phaseolus lunatus limabeans Phaseolus mungo mungbeans Phaseolus vulgaris snapbeans, green beans, dry beans Pennisetum glaucu~
Petroselinum crispum parsley spp. tuberosum 3B~
- 2 - O.Z. 0050/034525 30tanical name Common name ... . . _ _ Picea abies Norway spruce Abies alba fir trees Pinus spp. pine trees Pisum sativum English peas Prunus avium cherry trees Prunus domestica plum tree,s Prunus dulcis almond trees Prunus persica peach trees 10 Pyrus communis pear trees Ribes sylvestre redcurrants Ribes uva-crispa gooseberries Ricinus communis castor-oil plants Saccharum officinarum sugar cane Secale cereale rye Sesamum indicum sesame Solanum tuberosum Irish potatoes Sorghum bicolor (s. vulgare) sorghum Sorghum dochna 20 Spinacia oleracea spinach Theobroma cacao cacao plants Tri~olium pratense red clover Triticum aestivum wheat Vaccinium corymbosum blueberries Vaccinium vitis-idaea cranberries Vicia faba tick beans Vigna sinensis (V. unguiculata) cow peas Vitis vinifera grapes Zea mays Indian corn, sweet corn, maize - 30 - O.Z. 0050/034525 To increase the spectrum o~ action and to achieve synergistic effects~ the novel urethanes may be mixed and applied together with numerous representatives of other herbicidal or growth--regulating active ingredient groups. Examples of suitable mixture components are diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenyl~ carbamates, thiolcarbamates, halocarboxyllc acids, trlazines, amides, ureas, dlphenyl ethers, triazinones, uracils, benzofuran derivatives, cyclohexane-1,3-dione derivatives, etc. A number of active ingre-10 dients which, when combined with the new compounds, give mixturesuseful for widely varying applications are given below by way of example:

5-amino-4-chloro-2-phenyl-3(2H)-pyridazinone 5-amino-4-bromo-2-phenyl-3(2H)-pyridazinone 5-amino-4-chloro-2-cyclohexyl-3(2H)-pyridazinone 5-amino-4-bromo-2-cyclohexyl-3(2H)-pyridazinone 5-methylamlno-4-chloro-2-(3-trifluoromethylphenyl)-3(2H)-20 -pyridazinone 5-methylamino-4-chloro-2-(3-d,~ -tetrafluoroethoxyphenyl)--3(2H)-pyridazinone 5-dimethylamino-4-chloro-2-phenyl-3(2H)-pyridazinone 4,5-dimethoxy-2-phenyl-3(2H)-pyridazinone 4,5-dimethoxy-2-cyclohexyl-3(2H)-pyridazinone 4,5-dimethoxy-2-(3-trifluoromethylphenyl)-3(2H)-pyridazinone 5-methoxy-4-chloro-2-(3-trifluoromethylphenyl)-3(2H)-pyridazinone 5-amino-4-bromo-2(3-methylphenyl)-3(2H)-pyridazinone - 31 - O.Z. 0050/034525 3~ methylethyl)-lH-2,1,3-benzothiadlazin-4(3H)-one-2,2-dioxide and salts 3-(1-methylethyl)-8-chloro-lH-2,1,3-benzothiadiazin-4(3H)-one--2,2-dioxide and salts 3-(1-methylethyl)-8-fluoro-lH-2,1,3-benzothiadiazin-4(3H)-one--2,2-dioxide and salts 3-(1-methylethyl)-8-methyl-lH-2,1,3-benzothiadiazin-4(3H)-one--2,2-dioxide and salts l-methoxymethyl-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)--one-2,2-dioxide l-methoxymethyl-8-chloro-3-(1-methylethyl)-2,1,3-benzothia-diazin-4(3H)-one-2,2-dioxide l-methoxymethyl-8-fluoro-3-(1-methylethyl)-2,1,3-benzothiadiazin--4(3H)-one-2,2-dioxide l-cyano-8 chloro-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)--one-2,2-dioxide l-cyano-8-fluoro-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)--one-2,2-dioxide l-cyano-8-methyl-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)--one-2~2-dioxide l-cyano-3-(1-methylethyl)-2,1,3-benzothladiazln-4(3H)-one-2,2--dioxide l-azidomethyl-3-(1-methylethyl)-2,1,3-benzothiadiazin-4(3H)--one-2,2-dioxide 3-(1-methylethyl)-lH-pyridino-~3,2-e]-2,1,3-thiadiazin-(4)-one--2,2-dioxide A~ ~ 3 - 32 - O.Z. 0050/034525 N-(1-ethylpropyl)-2,6-dinitro-3,LI-dimethylaniline N-(1-methylethyl)-N-ethyl-2,6-dinitro-4-trifluoromethylaniline N-n-propyl-N-R-chloroethyl-2,6-dinitro-4-trifluoromethyl-aniline N-n-propyl-N-cyclopropylmethyl-2,6-dinitro-4-trifluoromethyl-aniline N-bis-(n-propyl)-2,6-dinitro-3-amino-4-trifluoromethylaniline N-bis-(n-propyl)-2,6-dinitro-4-methylaniline N-bis-(n-propyl)-2,6-dinitro-4-methylsulfonylaniline 10 N-bi 9- ( n-propyl)-2,6-dinitro-4-aminosulfonylaniline bis-(~-chloroethyl)-2,6-dinitro-4-methylaniline N-ethyl-N-(2-methylallyl)-2,6-dinitro-4-trifluoromethylaniline 3,4-dichlorobenzyl N-methylcarbamate 2,6-di-tert.butyl-4-methylphenyl N-methylcarbamate isopropyl N-phenylcarbamate 3-methoxyprop-2-yl N-3-fluorophenylcarbamate isopropyl N-3-chlorophenylcarbamate but-1-yn-3-yl N-3-chlorophenylcarbamate 20 4-chlorobut-2-yn-1-yl N-3-chlorophenylcarbamate methyl N-3,4-dichlorophenylcarbamate methyl N-(4-aminobenzenesulfonyl)-carbamate 0-(N-phenylcarbamoyl)-propanone oxime N-ethyl-2-(phenylcarbamoyl)-oxypropionic acid amide 3'-N-isopropylcarbamoyloxypropionanilide ethyl-N-(3-(N'-phenylcarbamoyloxy)-phenyl)-carbamate methyl-N-(3-(N'-methyl-N'-phenylcarbamoyloxy)-phenyl)-carbamate - 33 - O.Z. 0050/034525 isopropyl-N-(3-(N'-ethyl-N'-phenylcarbamoyloxy)-phenyl)--carbamate methyl-N-(3-(N'-3-methylphenylcarbamoyloxy)-phenyl)-carbamate methyl-N-(3-(N'-4-fluorophenylcarbamoyloxy)-phenyl)-carbamate methyl-N-(3-(N'-3-chloro-4-fluorophenylcarbamoyloxy)-phenyl)--carbamate ethyl-N-t3-N'-(3-chloro-4-fluorophenylcarbamoxyloxy)-phenyl~--carbamate ethyl-N-[3-Nr-(3~4-di~luorophenylcarbamoyloxy)-phenyl]-carbamate methyl-N-~3-(N'-3,4-difluorophenylcarbamoyloxy)-phenyl]-carbamate methyl N-3-(4'-fluorophenoxycarbonylamino)-phenylcarbamate ethyl N-3-(2'-methylphenoxycarbonylamlno)-phenylcarbamate methyl N-3-(4'-fluorophenoxycarbonylamino)-phenylthiolcarbamate methyl N-3-(2',4',5'-trimethylphenoxycarbonylamino)-phenylthiol-carbamate methyl N-3-(phenoxycarbonylamino)-phenylthiolcarbamate p-chlorobenzyl N,N-dlethylthiolcarbamate ethyl N,N-di-n-propylthiolcarbamate n-propyl N,N-di-n-propylthiolcarbamate 2,3-dichloroallyl N,N-diisopropylthiolcarbamate 2,3,3-trichloroallyl N,N-diisopropylthiolcarbamate 3-methyl-5-isoxazolylmethyl N,N-diisopropylthiolcarbamate 3-ethyl-5-isoxazolylmethyl N,N-diisopropylthiolcarbamate ethyl N,N-di-sec.-butylthiolcarbamate 34 O.Z. 0050/034525 benzyl N,N-di-sec.-butylthiolcarbamate ethyl N-ethyl-N-cyclohexylthiolcarbamate ethyl N-ethyl-N-bicyclo-~2.1.1]-heptylthiolcarbamate S-(2,3-dichloroallyl)-(2,2,4-trimethylazetidine)-1-carbothiolate S-(2,3,3-trichloroallyl) (2,2,4-trimethylazetidlne)-1-carbothiolate S-ethylhexahydro-1-H-azepine-l-carbothiolate S-benzyl-(3-methylhexahydro-1-H-azepine-l)-carbothiolate S-benzyl-(2,3-dimethylhexahydro-1-H-azepine-l)-carbothiolate S-ethyl-(3-methylhexahydro-1-H-azepine-l)-carbothlolate n-propyl N-ethyl-N-n-butylthiolcarbamate 2-chloroallyl N,N-dimethyldithiocarbamate N-methyldithlocarbamic acld, sodium salt trichloroacetlc acid, sodium salt ~,~-dichloropropionic acid, sodium salt ~,~-dichlorobutyric acid, sodium salt -tetrafluoropropionic acid, sodium salt ~-methyl-~,~-dichloropropionic acid, sodium salt methyl~ -chloro-~-(4-chlorophenyl)-propionate 20 methyl ~,R-dichloro-~-phenylpropionate benzamido oxyacet~c acid 2,3,5-triiodobenzoic acid (salts, esters, amides) 2,3,6-trichlorobenzolc acid ~salts, esters, amides) 2,3,5,6-tetrachlorobenzoic acid (salts, esters, amides) 2-methoxy-3,6-dichlorobenzoic acid (salts, esters, amides) 2-methoxy-3,5,6-trichlorobenzoic acid tsalts, esters, amides) 3-amino-2,5,6-trichlorobenzoic acid (salts, esters, amides) 0,S-dimethyltetrachlorothioterephthalate 35 - O.Z. 0050/034525 dimethyl-2,3,5,6-tetrachloroterephthalate dlsodium 3,6-endoxohexahydrophthalate 4-amlno-3,5,6-trichloropicolinic acid (salts) ethyl 2-cyano-3-(N-methyl-N-phenyl)-aminoacrylate isobutyl 2-~4-(4'-chlorophenoxy)-phenoxy]-propionate methyl 2-~4-(2',4'-dichlorophenoxy)-phenoxy]-propionate methyl 2-~4-(4'-tri~luoromethylphenoxy)-phenoxy]-propionate 2-~4-(2'-chloro-4'-trifluorophenoxy)-phenoxy]-propionic acid, sodium salt 2-~4-(3',5'-dichloropyridyl-2-oxy)-phenoxy]-propionic acid, sodium salt ethyl 2-(M-benzoyl-3,4-dichlorophenylamino)-propionate methyl 2-(N-benzoyl-3-chloro-4-fluorophenylamino)-propionate isopropyl 2-(N-benzoyl-3-chloro-4-fluorophenylamino)-propionate 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine 2-chloro-4-ethylamino-6-(amino-2'-propionitrile)-1,3,5-triazine 2-chloro-4-ethylamino-6-(2-methoxypropyl)-2-amino-1,3,5--triazine 2-chloro-4-ethylamino-6-butyn-1-yl-2-amino-1,3,5-triazine 2-chloro-4,6-bisethylamino-1,3,5-triazine 2-chloro-4,6-bisisopropylamino-1,3,5-triazine 2-chloro-4-isopropylamino-6-cyclopropylamino-1,3,5-triazine 2-azido-4-methylamino-6-isopropylamino-1,3,5-triazine 2-methylthio-4-ethylamino-6-isopropylamino-1,3,5-triazine 2-methylthio-4-ethylamino-6-tert.butylamino-1,3,5-triazine 4~
.
- 36 - O.Z. 0050/034525 2-methylthio-4,6-bisethylamino-1,3,5-triazlne 2-methylthio-4,6-bisisopropylamino-1,3,5-triazine 2-methoxy-4-ethylamino-6-isopropylamino-1,3,5-triazine 2-methoxy-4,6-bisethylamino-1,3,5-triazine 2-methoxy-4,6-bisisopropylamino-1,3,5-triazine 4-amino-6-tert.butyl-3-methylthio-4,5-dihydro-1,2,4-triazin-5-one 4-amlno-6-phenyl-3-methyl-4,5-dihydro-1,2,4-triazin-5-one lO 4-isobutylidenamino-6-tert.butyl-3-methylthio-4,5-dihydro_1,2,4_ -triazin-5-one l-methyl-3-cyclohexyl-6-dimethylamino-1,3,5-triazin-2,4-dione 3-tert.butyl-5-chloro-6-methyluracil 3-tert.butyl-5-bromo-6-methyluracil 3-lsopropyl-5-bromo-6-methyluracil 3-sec.butyl-5-bromo-6-methyluracil 3-(2-tetrahydropyranyl)-5-chloro-6-methyluracll 3-(2-tetrahydropyranyl)-5,6-trimethyleneuracil 20 3-cyclohexyl-5,6-trimethyleneuracil 2-methyl-4-(3'-trifluoromethylphenyl)-tetrahydro-1,2,4-oxa-diazine-3,5-dione 2-methyl-4-(4'-fluorophenyl)-tetrahydro-1,2,4-oxadiazine-3,5--dione 3-amino-1,2,4-triazole l-allyloxy-1-(4-bromophenyl)-2-tl',2',4'-triazolyl-(l')]--ethane (salts) 1-(4-chlorophenoxy)-3,3-dimethyl-1-(lH-1,2,3-triazol-1-yl)-30 -butan-2-one - 37 - O.Z. 0050/034525 N,N-diallylchloroacetamide N-isopropyl-2-chloroacetanilide N-(l-methylpropy~n-2-yl)-2-chloroacetanilide 2-methyl-6-ethyl-N-propargyl-2-chloroacetanilide 2-methyl-6-ethyl-N-ethoxymethyl-2-chloroacetanilide 2-methyl-6-ethyl-N-(2-methoxy-1-methylethyl)-2-chloroacetanilide 2~methyl-6-ethyl-N-(isopropoxycarbonylethyl)-2-chloroacetanilide 2-methyl-6-ethyl-N-(4-methoxypyrazol~l-yl-methyl)-2-chloro-10 -acetanilide 2-methyl-6-ethyl-N-(pyrazol-l-yl-methyl)-2-chloroacetanilide 2,6-dimethyl-N-(pyrazon-l-yl-methyl)-2-chloroacetanilide 2,6-dimethyl-N-(4-methylpyrazol-1-yl-methyl)-2-chloro-acetanilide 2,6-dimethyl-N-(1,2,4-triazol-1-yl-methyl)-2-chloroacetanilide 2,6-dimethyl-N-(3,5-dimethylpyra~ol-1-yl-methyl)-2-chloro-acetanilide 2,6-dimethyl-N-(1,3-dioxolan-2-yl-methyl)-2-chloroacetanllide 2,6-dimethyl-N-(2-methoxyethyl)-2-chloroacetanilide 2,6-dimethyl-N-isobutoxymethyl-2-chloroacetanilide 2,6-diethyl-N-methoxymethyl-2-chloroacetanil~de 2,6-diethyl-N-n-butoxymethyl-2-chloroacetanilide 2,6-diethyl-N-ethoxycarbonylmethyl-2-chloroacetanilide 2,3,6-trimethyl-N-(pyrazol-l-yl-methyl)-2-chloroacetanilide 2,3-dimethyl-N-isopropyl-2-chloroacetanilide 2,6-diethyl-N-(propoxyethyl)-2-chloroacetanilide 38 - O.Z. 0050/034525 2-(2-methyl-4-chlorophenoxy-N-methoxyacetamide 2-( -naphthoxy)-N,N-diethylpropionamide 2,2-diphenyl-N,N-dimethylacetamide ~-(3,4,5-tribromopyrazol-1-yl)-N,N-dimethylpropionamide N-(l,l-dimethylpropynyl)-3,5-dichlorobenzamide N-l-naphthylphthalamic acid propionic acid 3~4-dichloroanilide -cyclopropanecarboxylic acid 3,4-dichloroanilide methacrylic acid 3,4-dichloroanilide 2-methylpentanecarboxylic acid 3,4-dichloroanilide 5-acetamido-2,4-dimethyltrifluoromethanesulfone anilide 5-acetamido-4-methyltrifluoromethanesulfone anilide 2-propionylamino-4-methyl-5-chlorothiazole 0-(methylsulfonyl)-glycolic acid N-ethoxymethyl-2,6-dimethyl-anilide 0-(methylaminosulfonyl)-glycolic acid N-isopropylanilide 0-(isopropylaminosulfonyl)-glycolic acid N-but-l-yn-3-yl-anilide 0-(methylaminosulfonyl)-glycolic acid hexamethyleneamide 2,6-dichlorothiobenzamlde 2,6-dichlorobenzonitrile 3,5-dibromo-4-hydroxybenzonitrile (salts) 3,5-diiodo-4-hydroxybenzonitrlle (salts) 3,5-dibromo-4-hydroxy-0-2,4-dinitrophenylbenzaldoxime (salts) 3,5-dibromo-4-hydroxy-0-2-cyano-4-nitrophenylbenzaldoxime (salts) pentachlorophenol, sodium salt - 39 - O.Z. 0050/034525 2,4-dichlorophenyl-4'-nitrophenyl ether 2,4,6-trichlorophenyl-4'-nitrophenyl ether 2-fluoro-4,6-dichlorophenyl-4'-nitrophenyl ether 2-chloro-4-trifluoromethylphenyl-4'-nitrophenyl ether 2,4'-dlnitro-4-trifluoromethyl-diphenyl ether 2,4-dichlorophenyl-3'-methoxy-4'-nitro-phenyl ether 2-chloro-4-trifluoromethylphenyl-3'-ethoxy-4'-nitro-phenyl ether 2-chloro-4-trifluoromethylphenyl-3'-carboxy-4'-nitro-phenyl ether (~alts) 10 2,4-dichlorophenyl-3'-methoxycarbonyl 4'-nitro-phenyl ether 2-(3,4-dichlorophenyl)-4-methyl-1,2,4-oxadiazolidine-3,5-dione 2-(3-tert.butylcarbamoyloxyphenyl)-4-methyl-1,2,4-oxadiazolidine--3,5-dione 2-(3-lsopropylcarbamoyloxyphenyl)-4-methyl-1,2,4-oxadiazolidine--3,5-dlone 2-phenyl-3,1-benzoxazinone-(4) (4-bromophenyl)-3,4,5,9,10-pentaazatetracyclo-t5,4,1,02'6'0,8'11]--dodeca-3,9-diene 2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranylmethane sulfonate 20 2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzo~uranyldimethylamino-sulfate 2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyl-(N-methyl-N--acetyl)-amlnosulfonate 3,4-dichloro-1,2-benzisothiazole N-4-chlorophenyl-allylsuccinimide 2-methyl-4,6-dinitrophenol (salts, esters) 2-sec.butyl-4,6-dinitrophenol (salts, esters) 2-sec.butyl-4,6-dinitrophenol acetate .r~ 3 - 40 - O.Z. 0050/034525 2-tert.butyl-4,6-dinitrophenol acetate 2-tert.butyl-4,6-dinitrophenol (salts) 2-tert.butyl-5-methyl-4,6-dinitrophenol (salts) 2-tert.butyl-5-methyl-4,6-dinitrophenol acetate 2-sec.amyl-4,6-dinltrophenol (salts, esters) 1-(~,~-dimethylbenzyl)-3-(4-methylphenyl)-urea l-phenyl-3-(2-methylcyclohexyl)-urea 10 1-phenyl-1-benzoyl-3,3-dimethylurea 1-(4-chlorophenyl)-1-benzoyl-3,3-dimethylurea 1-(4-chlorophenyl)-3,3-dimethylurea 1-(4-chlorophenyl)-3-methyl-3-but-1-yn-3-yl-urea 1-(3,4-dichlorophenyl)-3,3-dtmethylurea 1-(3,4-dichlorophenyl)-1-benzoyl-3,3-dimethylurea 1-(3,4-dichlorophenyl)-3-methyl-3-n.butylurea 1-(4-lsopropylphenyl)-3,3-dimethylurea 1-(3-trifluoromethylphenyl)-3,3-dimethylurea l-(~,~,~,~-tetrafluoroethoxyphenyl)-3,3-dimethylurea 1-(3-tert.butylcarbamoyloxyphenyl)-3,3-dimethylurea 1-(3-chloro-4-methylphenyl)-3,3-dimethylurea 1-(3-chloro-4-metho~yphenyl)-3,3-dimethylurea 1-(3,5-dichloro-4-methoxyphenyl)-3,3-dimethylurea 1-~4-(4'-chlorophenoxy)-phenyl]-3,3-dimethylurea 1-~4-(4'-methoxyphenoxy)-phenyl]-3,3-dimethylurea l-cyclooctyl-3,3-dimethylurea l-(hexahydro-4,7-methanoindan-5-yl)-3,3-dimethylurea 1-~1- or 2-(3a,4,5,7,7a-hexahydro)-4,7-methanoindanyl]-3,3-di-30 methylurea - 41 - O.Z. 0050/034525 1-(4-fluorophenyl)-3-carboxymethoxy-3-methylurea l-phenyl-3-methyl-3-methoxyurea l-(4-chlorophenyl)-3-methyl-3-methoxyurea 1-(4-bromophenyl)-3-methyl-3-methoxyurea 1-(3,4-dichlorophenyl)-3-methyl-3-methoxyurea 1-(3-chloro-4-bromophenyl)-3-methyl-3-methoxyurea 1-(3-chloro-4-isopropylphenyl)-3-methyl-3-methoxyurea 1-(3-chloro-4-methoxyphenyl)-3-methyl-3-methoxyurea 1-(3-tert.butylphenyl)-3-methyl-3-methoxyurea 10 1-(2-benzthiazolyl)-1,3-dimethylurea 1-(2-benzthiazolyl)-3-methylurea 1-(5-trifluoromethyl-1,3,4-thiadiazolyl)-1,3-dimethylurea imldazolidin-2-one-1-carboxylic acid isobutylamlde 1,2-dimethyl-3,5-diphenylpyrazolium-methylsulfate 1,2,4-trimethyl-3,5-diphenylpyrazolium-methylsulfate 1,2-dimethyl-4-bromo-3,5-diphenylpyrazolium-methylsulfate 1,3-dimethyl-4-(3,4-dichlorobenzoyl)-5-(4-methylphenylsulfonyloxy)--pyrazole 2,3,5-trichloropyrldlnol-(4) l-methyl-3-phenyl-5-(3'-trifluoromethylphenyl)-pyridone-(4) l-methyl-4-phenylpyridinium chloride l,l-dimethylpyridinium chloride 3-phenyl-4-hydroxy-6-chloropyridazine 1,1'-dimethyl-4,4'-dipyridylium-di(methylsulfate) 1,1'-di-(3,5-dimethylmorpholine-carbonylmethyl)-4,4'-dipyridylium dichloride 1,1'-ethylene-2,2'-dipyridylium dibromide - 42 - O.Z. 0050/034525 3-[1-(N-ethoxyamino)-propylidene]-6-ethyl-3,4-dihydro-2H-pyran--2,4-dione 3-~1-(N-allyloxyamino)-propylidene~-6-ethyl-3,4-dihydro-2H-pyran--2,4-dione 2-tl-(N-allyloxyamino)-propylidene]-5,5-dimethylcyclohexane-1,3--dione (salts) 2-~1-(N-allyloxyamino-butylidene]-5,5-dimethylcyclohexane-1,3--dione (salts) 2-~1-(N-allyloxyamino-butylidene]-5,5-dimethyl-4-methoxycarbonyl-10 -cyclohexane-1,3-dione (salts) 2-chlorophenoxyacetic acld (salts, esters, amides) 4-chlorophenoxyacetlc acld (salts, esters, amides) 2,4-dichlorophenoxyacetic acid (salts, esters, amides) 2,4,5-trichlorophenoxyacetic acid (salts, esters, amides) 2-methyl-4-chlorophenoxyacetic acid (salts, esters, amides) 3,5,6-trichloro-2-pyridinyl-oxyacetic acid (salts, esters, amides) methyl ~-naphthoxyacetate 2-(2-methylphenoxy)-propionic acid (salts, esters, amides) 20 2-(4-chlorophenoxy)-propionic acid (salts, esters, amldes) 2-(2,4-dichlorophenoxy)-propionic acid (salts, esters, amides) 2-(2,4,5-trichlorophenoxy)-propionic acid (salts, esters, amides) 2-(2-methyl-4-chlorophenoxy)-propionic acid (salts, esters, amides) 4-(2,4-dichlorophenoxy)-butyric acid (salts, esters, amides) 4-(2-methyl-4-chlorophenoxy)-butyric acid (salts, esters, amides) cyclohexyl-3-(2,4-dichlorophenoxy)-acrylate 9-'nydroxyfluorenecarboxylic acid-(9) (salts, esters) 2,3,6-trichlorophenylacetic acid (salts, esters) 4-chloro-2-oxobenzothiazolin-3-yl-acetic acid (salts, esters) ~als~3 - 43 - O.Z. 0050/034525 gibelleric acid (salts) disodium methylarsonate monosodium salt of methylarsonic acid M-phosphonomethyl-glycine (salts) N,N-bis-(phosphonomethyl)-glycine (salts) 2-chloroethyl 2-chloroethanephosphonate ammonium-ethyl-carbamoyl-phosphonate dl-n-butyl-l-n-butylamino-cyclohexyl-phosphonate trlthiobutylphosphlte 10 0,0-diisopropyl-5-(2-benzosul~onylaminoethyl)-phosphorodithionate 2,3-dihydro-5/6-dimethyl-1,4-dithiin-1,1,4,4-tetraoxide 5-tert.butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4-oxa-diazolone-(2) 4,5-dichloro-2-trifluoromethylbenzimldazole (salts) 1,2,3,6-tetrahydropyrldazlne-3,6-dione (salts) succinic acid mono-N-dimethylhydrazide (salts) (2-chloroethyl)-trlmethylammonium chloride (2-methyl-4-phenylsulfonyl)-trifluoromethanesul~one anilide 1,1-dimethyl-4,6-diisopropyl-5-indanyl ethyl ketone 20 sodium chlorate ammonium thiocyanate calcium cyanamide 2-chloro-4-trifluoromethyl-3'-ethoxycarbonyl-4'-nitrophenyl ether 1-(4-benzyloxyphenyl)-3-methyl-3-methoxyurea 2-tl-(2,5-dimethylphenyl)-ethylsul~onyl]-pyridine-N-oxide l-acetyl-3-anilino-4-methoxycarbonyl-5-methylpyrazole ~&;9~t~3 - 44 - O.Z. 005~/034525 3-anilino-4-methoxycarbonyl-5-methylpyrazole 3-tert.butylamino-4-methoxycarbonyl-5-methylpyrazole N-benzyl-N-isopropyl-trimethylacetamide methyl 2-[4-(4'-chlorophenoxymethyl)-phenoxy]-propionate methyl 2-t4-(5'-bromopyridyl-2-oxy)-phenoxy]-propionate methyl 2-t4-(5'-iodopyridyl-2-oxy)-phenoxy]-propionate n-butyl 2-t4-(5'-iodopyridyl-2-oxy)-phenoxy~-propionate 2-chloro-4-trlfluoromethylphenyl-3'-(2-fluoroethoxy)-4'-nitro-phenyl ether lO 2-chloro-4-trifluoromethylphenyl-3 (ethoxycarbonyl)-methyl-thlo-4-nitrophenyl ether 2,4,6-trlchlorophenyl-3(ethoxycarbonyl)-methylthio-4-nitro-phenyl ether 2-tl-(N-ethoxamino)-butylidene]-5-(2-ethylthiopropyl)-3--hydroxy-cyclohex-2-en-1-one (salts) 2-tl-(N-ethoxamino)-butylidene]-5-(2-phenylthiopropyl)-3--hydroxy-cyclohex-2-en-1-one (salt 3 ) ethyl 4-t4-(4'-trifluoromethyl)-phenoxy]-pentene-2-carboxylate 20 2-chloro-4-trifluoromethyl-3'-methoxycarbonyl-4'-nitrophenyl ether 2,4-dichlorophenyl-3'-carboxy-4'-nitrophenyl ether (salts) 4,5-dimethoxy-2-(3-~ trifluoro-~-oromoethoxyphenyl)-3--(2H)~pyridazinone 2,4-dichlorophenyl-3'-ethoxy-ethoxy-ethoxy-4'-nitrophenyl ether 2,3-dihydro-3~3-dimethyl-5-benzofuranyl-ethane sulfonate N-t4-methoxy-6-methyl-1,3,5-triazin-2-yl-aminocarbonyl]--2-chlorobenzene sulfonamide 1(3-chloro-4-ethoxyphenyl)-3,3-dimethylurea 45 ~ 3 o . Z ~ 0050/034525 ethyl 2-methyl-4-chlorophenoxy-thioacetate 2-chloro-3,5-diiodo-4-acetoxy-pyridine 1(-4-~2-(4-methylphenyl)-ethoxy]-phenyl-3-methyl-3-methoxyurea.
In investigations into the herbicidal action on preemergence application in the greenhouse at a rate of 3.0 kg of active ingre-dient per hectare, new compounds nos. 76, 94, 36 and 98 were better tolerated by crop plants than prior art active ingredient A.
In investigations lnto selective herbicidal action on ~ost-10 emergence application in the greenhouse, active ingredient no. 109has a better herbicidal action at 0.5 kg/ha, no. 123 at 0.5 g/ha, no. 90 at 1.0 kg/ha and no. 63 at 0.5 kg/ha, and, in particular, are better tolerated by crop plants than prior art active ingre-dient B at 0.5 o r 1.0 kg/ha.
In selective weed control on postemergence treatment in the greenhouse, active ingredients nos. 13 and 14 have, at 0.25 kg/ha, a better herbicidal and selective action than prior art active ingredient B at 0.25 kg/ha.
New compounds nos. 108 and 121 also have, at l.0 kg/ha and on 20 postemergence application in the greenhouse, a much better her-bicidal action than prior art active ingredient B.
In investigations into the selective herbicidal action on postemergence application in the greenhouse, active ingredient no. 88 is, at 2.0 kg/ha, better tolerated than prior art active ingredient C.
In investigations into the herbicidal action on postemergence application in the greenhouse at 2 kg o~ active ingredient per hectare, compound no. 36 exhibited a good herbicidal action.

- 46 - O.Z. 0050/034525 In investigations into the herbicidal action on postemergence application in the greenhouse at 1 kg of active ingredient per hectare, compounds nos. 109 and 114 exhibited a good herbicidal action.
In investigations into the herbicidal action on postemergence application in the greenhouse at 2 kg of active ingredient per hectare, compounds nos. 47 and 62 exhibit~ed a good herblcidal action.
In investigations into the herbicidal action on postemergence 10 application in the greenhouse at 0.5 kg of active ingredient per hectare, compounds nos. 101, 63 and 107 exhibited a good herbicidal action.

Table 1 List of plant names Botanical name Abbreviation in tables Common name Abutilon theophrasti Abutilon theoph. velvet leaf - Amaranthus spp. - pigweed Arachys hypogaea Arachys hypog. peanuts Avena sativa - oats 20 Euphorbia genlculata - South American member of the spurge family Gossypium hirsutum - cotton Hordeum vulgare - barley Mercurialis annua - annual mercury Sinapis alba - white mustard Solanum nigrum - black nightshade Triticum aestivum - wheat _ _ _ ~ 8 ~ 3 - 47 - O.Z. 0050/034525 The novel active ingredients have a strong fungitoxlc action on phytopathogenic fungi, especially from the Ascomycetes class.
The following fungi may be mentioned by way of example: Erysiphe graminis in wheat, Erysiphe cichoriacearum in cucumbers, Uncinula necator in grapes, and Podosphaera leucotrichia in apples.
When the novel compounds are employed to protect crop plants, the fungicidal agents contain from 0.1 to 95J and preferably from 0.5 to 90, % (wt%) of active lngredient. The application rates depend on the type of effect desired, and range from 0.01 to 3 kg 10 and more of active ingredient per hectare, but are preferably from 0.01 to 1 kg/ha.
The active ingredients according to the invention may also be mixed with other, prior art; fungicides. In many cases, the spectrum of fungicidal action is increased; with a number of these fungicidal compositlons, synergistic effects also occur, i.e., the fungicidal action of the comblnation product is greater than the effect of the individual components added together.
Examples of fungicides which may be combined with the active ingredients according to the invention are as follows:
20 sulfur dithiocarbamates and derivatives thereof, such as ferric dimethyldithiocarbamate zinc dimethyldithiocarbamate zinc ethylenebisthiocarbamate tetramethylthiuram disulfide manganese-zinc ethylenediamine-bisdithiocarbamate zinc-(N,N'-propylene-bisdithiocarbamate) ammonia complex of zinc-(N,N'-ethylene)-bisdithiocarbamate and ~L~L59~3 - 48 - O.Z. 0050/034525 N,N' polyethylene-bis-(thiocarbamoyl)-disulfide ammonia complex o~ zinc-(N,M'-propylene-bisdithiocarbamate) and N,N'-polypropylene-bis-(thiocarbamoyl)-disulfide nitro derivatives, such as dinitro-(l-methylheptyl)-phenylcrotonate 2-sec-butyl-4,6-dinitrophenyl-3,5-d~methylacrylate 2-sec-butyl-4,6-dinitrophenylisopropylcarbonate heterocycllc compounds, such as N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalim~de N-trichloromethylthio-tetrahydrophthalimide 2-heptadecyl-2-imidazoline acetate 2,4-dichloro-6-(o-chloroanilino)-s-triazine 0,0-diethylphthalimidophosphorothioate 5-amino-1-tbls-(dimethylamino)-phosphynyl]-3-phenyl-1,2,4--triazole 2,3-dicyano-1,4-dlthiaanthraquinone 2-thio-1,3-dithio-(4,5-b)-quinoxaline methyl l-(butylcarbamoyl)-2-benzimidazole carbamate 4-(2-chlorophenylhydrazono)-3-methyl-5-isooxazolone pyridine-2-thiol-1-oxide 8-hydroxyquinoline and its copper salt 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxide 2-t~uryl-(2)3-benzimidazole piperazine-1,4-diyl-bistl-(2,2,2-trichloroethyl)-formamide]
2-tthiazolyl-(4)]-benzimidazole 5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine bis-(p-chlorophenyl)-3-pyridinemethanol 1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene 1,2-bis-(3-methoxycarbonyl)-2-thioureido)-benzene - 49 - O.Z. 0050/034525 and varlous fungicides, such as dodecylguanidine acetate 3-[2-(3,5-dimethyl 2-oxycyclohexyl)-2-hydroxyethyl]-glutarimide hexachlorobenzene N-dichlorofluoromethylthio-N,N'-dimethyl-N-phenylsulfuric acid diamide 2,5-dimethylfuran-3-carboxanilide 2-methylbenzoic acid anilide 2-iodobenzoic acid anilide 10 1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane 2,6-dimethyl-N-tridecylmorpholine and its salts 2,6-dimethyl-N-cyclododecylmorpholine and its salts 1-(4-chlorophenoxy)-3,3-dimethyl-1-(lH-1,2,4-triazol-1-yl)-2-butanone 1-(4-chlorophenoxy)-3,3-dimethyl-1-(lH-1,2,4-triazol-1-yl)-2-butanol -(2-chlorophenyl)- -(4-chlorophenyl)-5-pyrimidine-methanol.
For the following experiment, the prior art active ingredient l-t2-(2,4-dichlorophenyl)-2-(2-propenyloxy)-ethyl]-imidazole was used as comparative agent D.
Action on wheat mildew Leaves of pot-grown wheat seedlings of the "Jubilar" variety are sprayed with aqueous emulsions consisting of 80% (by weight) of active ingredient and 20% of emulsifier, and dusted, after the sprayed-on layer has dried, with spores of wheat mildew (Erysiphe graminis var. tritici). The plants are then placed in a greenhouse at 20 to 22C and 75 to 80% relatlve humidity. The extent of mildew spread is determined after 10 days. The results o~ this experiment show that active ingredient nos. 35, 36, 62, 87, lOl, 108, 109 and 121 have a better fungicidal action than prior art compound D.

Claims (2)

O.Z. 0050/034525 The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A urethane of the general formula , where R1 is unsubstituted or halogen-, alkoxy-, alkoxy-carbonyl- or cyano-substituted alkyl, cycloalkyl, alkenyl or alkynyl, or alkoxy, cycloalkoxy, alkenyloxy, alkynyloxy, cyanoalkoxy, halo-alkoxy, alkylthio, alkenylthio or alkynylthio, Y is hydrogen, alkyl, halogen, alkoxy, or haloalkyl, A is unsubstituted or alkyl-substituted alkylene, R2 is hydrogen, alkyl,alkoxyalkyl, haloalkyl, or unsubstituted or alkyl- or halogen-substituted benzyl, R3 is alkyl which is unsubstituted or substituted by halogen or by alkoxy or by unsubstituted or substituted aryl, or is unsub-stituted or substituted or halogen-substituted alkenyl, unsub-stituted or halogen- or alkoxy-substituted alkynyl, or unsub-stituted or or alkyl-substituted cycloalkyl, phenyl or monosub-stituted or polysubstituted phenyl, the substituents being alkyl, haloalkyl, alkoxyalkyl, cycloalkyl, halogen, alkoxy, haloalkoxy, nitro, aryl, aryloxy, thiocyanato, cyano, NH-?-R4, NHCOOR4, , COOR4, , S-R4, SO2R4, OSO2R4, -CO-R4 or , where R4 and R5 each independently of one another are hydrogen or unsubstituted, mono-substituted or polysubstituted aryl, or one of R4 and R5 has one of the other meanings given for R2.

O.Z. 0050/034525

2. A process for combating fungi, wherein the fungi or the objects to be protected against fungus attack are treated with a urethane of the general formula where R1 is unsubstituted or halogen-, alkoxy-, alkoxy-carbonyl- or cyano-substituted alkyl, cycloalkyl, alkenyl or alkynyl, or alkoxy, cycloalkoxy, alkenylthio, alkynyloxy, cyanoalkoxy, halo-alkoxy, alkylthio, alkenylthio or alkynylthio, Y is hydrogen, alkyl, halogen, alkoxy, or haloalkyl, A is unsubstituted or alkyl-substituted alkylene, R2 is hydrogen, alkyl,alkoxyalkyl, haloalkyl, or unsubstituted or alkyl- or halogen-substituted benzyl, R3 is alkyl which is unsubstituted or substituted by halogen or by alkoxy or by unsubstituted or substituted aryl, or is unsub-stituted or substituted or halogen-substituted alkenyl, unsub-stituted or halogen- or alkoxy-substituted alkynyl, or unsub-stituted or or alkyl-substituted cycloalkyl, phenyl or monosub-stituted or polysubstituted phenyl, the substituents being alkyl, haloalkyl, alkoxyalkyl, cycloalkyl, halogen, alkoxy, haloalkoxy, nitro, aryl, aryloxy, thiocyanato, cyano, NH-?-R4, NHCOOR4, , COOR4 , , S-R4, SO2R4, OSO2R4, -CO-R4 or , where R4 and R5 each independently of one another are hydrogen or unsubstituted, mono-substituted or polysubstituted aryl, or one of R4 and R5 has one of the other meanings given for R2.