EP0000023A1 - Omega-substituted pentyl ureas, their preparation and their use as fungicides - Google Patents

Abstract

ω-substituted pentylurea derivatives, several processes for their preparation and their use as fungicides. The compounds of the general formula <IMAGE> in which R represents R¹, CO-R², CO-NH-R³ or CO-OR <4> where R¹ represents unsubstituted or substituted alkyl or benzyl, R² represents a hydrocarbon radical R³ represents an alkyl radical or phenyl radical Q for CN, CO-NH2, COOH or COOalkyl are obtained if, for example a 2-cyan - 2-alkoxyimino-acetamide in the presence of a strong base with an ω-substituted pentyl isocyanate. Other manufacturing processes are also described. The active compounds according to the invention have a strong fungitoxic action and are suitable for use as crop protection agents for combating fungi. In particular, they show a high protective and curative activity against phycomycetes.

Description

The present invention relates to new ω-substituted pentylurea derivatives, several processes for their preparation and their use as fungicides.

As has been known for a long time, zinc-ethylene-1,2-bis-dithiocarbamidate and N-trichloromethylthio-tetrahydrophthalimide are used in particular as agricultural and horticultural fungicides; the compounds mentioned are of great importance among the commercial products (cf. R. Wegler, "Chemistry of Plant Protection Products and Pest Control", Volume 2, pages 65 and 108, Berlin / Heidelberg / New York (1970)). The effect at low concentration levels is not always satisfactory. These fungicides are also not curative.

The fungicidal activity of some isonitrosocyanacetamide derivatives is also known (cf. DT-OSS 1 693 052, 2 118 317, 2 312 956, 2 350 910, 2 436 654, 2 436 655, 2 603 643 and 2 635 697 and US-PSS 3,625,987, 3,769,423, 3,919,284, 3,954,992 u: id 3,957,847. Here too, the effectiveness is not reliable at low application rates. and plant damage is seen at normal concentrations.

in welcher

• R für R¹, C_O-_R ², CO-NH-R3 oder für CO-OR⁴ steht, wobei
• R für unsubstituiertes Alkyl mit 1 bis 10 Kohlenstoffatomen steht; ferner für substituiertes Alkyl mit 1 bis 4 Kohlenstoffatomen steht, welches als Substituenten eine Vinylgruppe, eine Alkinylgruppe mit bis zu 4 Kohlenstoffatomen, eine Alkylcarbonylgruppe mit 2 bis 5 Kohlenstoffatomen, eine Alkoxycarbonylgruppe mit 2 bis 5 Kohlenstoffatomen, eine Alkenoxycarbonyl- oder Alkinoxycarbonyl-Gruppe mit 4 bis 5 Kohlenstoffatomen, eine Aminocarbonyl-, N-Alkylaminocarbonyl-oder N-Cycloalkylaminocarbonyl-Gruppe mit jeweils bis zu 7 Kohlenstoffatomen, oder eine N-Phenylaminocarbonylgruppe, die am Phenylrest gegebenenfalls niedere Alkylgruppen und/oder Chloratome als weitere Substituenten besitzen kann, enthält; ferner für Benzyl steht, welches im aromatischen Teil durch Methyl-, Methoxy-, Methylendioxy-, Nitro-, Trifluormethyl-, Benzoyl-, Mono- oder Dichlorbenzoyl-, Phenyl- oder Phenoxy-Gruppen oder durch 1 bis 4 Chloratome substituiert sein kann; und
• R² für einen geraden oder verzweigten, gesättigten oder ungesättigten Kohlenwasserstoffrest mit bis zu 8 Kohlenstoffatomen steht, welcher durch Chlor-oder Bromatome bzw. durch eine Cyangruppe substituiert sein kann, und
• _R ³ für einen geraden oder verzweigten Alkylrest mit bis zu 11 Kohlenstoffatomen steht, welcher durch eine Cyangruppe oder durch einen Carbonyloxyalkylrest mit bis zu 5 Kohlenstoffatomen substituiert sein kann, oder für einen Phenylrest steht, der durch Methyl-, Nitro- oder TrifluormethylGruppen bzw. durch Chloratome substituiert sein kann, und
• _R ⁴ für eine gesättigte oder ungesättigte aliphatische Gruppe mit bis zu 4 Kohlenstoffatomen steht, und
• Q für CN, CO-NH₂, COOH oder CO-OR⁵ steht, wobei
• R eine Alkyl-Gruppe mit 1 bis 4 Kohlenstoffatomen bedeutet,

gefunden. Sie besitzen starke fungizide Eigenschaften.Now the W-substituted pentylurea derivatives of the general formula have been added as new substances

in which

• R is R ^1, _OR ² C, CO-NH-R 3 or CO-OR ^4, wherein
• R represents unsubstituted alkyl of 1 to 10 carbon atoms; furthermore stands for substituted alkyl with 1 to 4 carbon atoms, which as a substituent is a vinyl group, an alkynyl group with up to 4 carbon atoms, an alkylcarbonyl group with 2 to 5 carbon atoms, an alkoxycarbonyl group with 2 to 5 carbon atoms, an alkenoxycarbonyl or alkynoxycarbonyl group with 4 contains up to 5 carbon atoms, an aminocarbonyl, N-alkylaminocarbonyl or N-cycloalkylaminocarbonyl group each with up to 7 carbon atoms, or an N-phenylaminocarbonyl group which may have lower alkyl groups and / or chlorine atoms as further substituents on the phenyl radical; furthermore stands for benzyl, which in the aromatic part can be substituted by methyl, methoxy, methylenedioxy, nitro, trifluoromethyl, benzoyl, mono- or dichlorobenzoyl, phenyl or phenoxy groups or by 1 to 4 chlorine atoms; and
• R ^{2 represents} a straight or branched, saturated or unsaturated hydrocarbon radical having up to 8 carbon atoms, which can be substituted by chlorine or bromine atoms or by a cyano group, and
• _R ^{3 represents} a straight or branched alkyl radical having up to 11 carbon atoms, which can be substituted by a cyano group or by a carbonyloxyalkyl radical having up to 5 carbon atoms, or represents a phenyl radical, by methyl, nitro or trifluoromethyl groups or by Chlorine atoms can be substituted, and
• _R ^{4 represents} a saturated or unsaturated aliphatic group with up to 4 carbon atoms, and
• Q represents CN, CO-NH ₂ , COOH or CO-OR ⁵ , where
• R represents an alkyl group with 1 to 4 carbon atoms,

found. They have strong fungicidal properties.

The substances according to the invention can exist as oxime derivatives in two different geometric structures:

In the following, the spatial structure is omitted; For the purposes of the present application, the given formulas (Ia) should in any case also include the corresponding formula according to the spatial structure (Ib).

• a) ein 2-Cyan-2-alkoxyimino-acetamid der Formel
  
  in welcher
  • R¹ die oben angegebene Bedeutung besitzt, in Gegenwart einer starken Base mit einem W -substituierter Pentyl- isocyanat der Formel
    
    in welcher
  • Q die oben angegebene Bedeutung besitzt, umsetzt, oder
• b) den 1-(5-substituierten Pentyl)-3-(2-cyan-2-oximino-acetyl)-harnstoff der Formel
  
  in welcher
  • Q die oben angegebene Bedeutung besitzt, in Gegenwart eines Säurebindemittels, bzw. ein Alkali-, Erdalkali- oder Ammoniumsalz des Harnstoffs der Formel IV mit einem Alkylierungsmittel der Formel
    
    in welcher
  • R¹ die oben angegebene Bedeutung besitzt, und
  • X für eine "Abgangsgruppe" wie Chlor, Brom, Jod, Alkoxy-, Alkyl- bzw. Arylsulfonyl steht, und ferner für die Gruppe (CH₃O-)₂PO-O steht, wenn R für Methyl steht,
  
  umsetzt, bzw.
• c) den Harnstoff der Formel IV mit einem Säurederivat der Formel
  
  in welcher
  • _R ² die oben angegebene Bedeutung besitzt und
  • T für Chlor, Brom, Jod oder die Gruppe R²-CO-O steht, umsetzt, bzw.
• d) den Harnstoff der Formel IV mit einem Isocyanat der Formel
  
  oder mit einem Carbamidsäurehalogenid der Formel
  
  in welchen Formeln
  • R³ die oben genannte Bedeutung besitzt und
  • Y für Chlor, Brom oder Jod steht,
  
  umsetzt, bzw.
• e) den Harnstoff der Formel IV mit einem Kohlensäureester der Formel
  
  in welcher
  • R⁴ die oben angegebene Bedeutung besitzt und
  • Z für Chlor oder den Rest R⁴-O-CO-O steht, umsetzt;
  
  weiterhin kann man noch diejenigen Verbindungen der Formel I, in denen R für R¹ und Q für die Gruppe CO-OR⁵ steht, dadurch erhalten, daß man gemäß einer weiteren Verfahrensvariante
• f) eine nach Verfahren b) synthetisierte Carbonsäure der Formel
  
  in welcher
  • R¹ die weiter oben angegebene Bedeutung besitzt,
  
  in Gegenwart eines Säurebindemittels, bzw. eines Alkali-, Erdalkali- oder Ammonium-Ions, mit einem Alkylierungsmittel der Formel
  
  in welcher
  • _X und R die oben genannte Bedeutung besitzen,

umsetzt.It has also been found that W-substituted pentylurea derivatives of the formula Ia or Ib are obtained when

• a) a 2-cyan-2-alkoxyimino-acetamide of the formula
  
  in which
  • R ^{1 has} the meaning given above, in the presence of a strong base with a W-substituted pentyl isocyanate of the formula
    
    in which
  • Q has the meaning given above, implements, or
• b) the 1- (5-substituted pentyl) -3- (2-cyano-2-oximino-acetyl) urea of the formula
  
  in which
  • Q has the meaning given above, in the presence of an acid binder, or an alkali, alkaline earth or ammonium salt of the urea of the formula IV with an alkylating agent of the formula
    
    in which
  • R ^{1 has} the meaning given above, and
  • X represents a "leaving group" such as chlorine, bromine, iodine, alkoxy-, alkyl- or arylsulfonyl, and furthermore represents the group (CH ₃ O-) ₂ PO-O when R represents methyl,
  
  implements or
• c) the urea of the formula IV with an acid derivative of the formula
  
  in which
  • _R ^{2 has} the meaning given above and
  • T represents chlorine, bromine, iodine or the group R ² -CO-O, or
• d) the urea of the formula IV with an isocyanate of the formula
  
  or with a carbamic acid halide of the formula
  
  in what formulas
  • R ^{3 has} the meaning given above and
  • Y represents chlorine, bromine or iodine,
  
  implements or
• e) the urea of the formula IV with a carbonic acid ester of the formula
  
  in which
  • R ^{4 has} the meaning given above and
  • Z represents chlorine or the radical R ⁴ -O-CO-O, is reacted;
  
  furthermore, those compounds of the formula I in which R represents R ¹ and Q represents the group CO-OR ^{5 can} be obtained in that, according to a further process variant
• f) a carboxylic acid of the formula synthesized by process b)
  
  in which
  • R ^{1 has} the meaning given above,
  
  in the presence of an acid binder, or an alkali, alkaline earth or ammonium ion, with an alkylating agent of the formula
  
  in which
  • _X and R have the meaning given above,

implements.

The compounds according to the invention show a good fungicidal action. They are protective, curative and even eradicative, they also have systemic and / or locosystemic properties. Surprisingly, they show better plant tolerance than the isonitrosocyanacetamide derivatives known from the prior art. Compared to the dithiocarbamidates and the N-trichloromethylthio-tetrahydrophthalimide, they have the advantage of curative and eradicative effects.

The compounds according to the invention represent a valuable enrichment of the technology because of the many possibilities of their superior biological application. Another essential aspect of this invention is that new active ingredients with properties that are useful in practice are made available at a time because of signs of resistance of older active ingredients there is a pronounced need for new fungicides.

If 1- (5-cyanopentyl) -3- (2-cyan-2-oximino-acetyl) urea and benzyl chloride are used as starting materials, and ethyldiisopropylamine is used as a proton acceptor, the course of the reaction can be represented by the following formula:

The compounds according to the invention are defined by the formula I. In it, R preferably represents R ¹ , and R preferably represents alkyl having 1 to 6 carbon atoms; furthermore for such alkyl having 1 to 2 carbon atoms, which is represented by a vinyl group, by an alkylcarbonyl group having 2 to 5 carbon atoms, by alkoxycarbonyl having 2 to 5 carbon atoms, by aminocarbonyl, by N-alkylaminocarbonyl or N-cycloalkylaminocarbonyl up to 7 carbon atoms, is substituted by N-phenylaminocarbonyl, which may contain lower alkyl substituents and / or chlorine atoms in the phenyl radical, or for benzyl, which contains methyl, methoxy, methylenedioxy, nitro or trifluoromethyl groups or Can carry 1 to 2 chlorine atoms as substituents.

R is particularly preferred for the following structural elements of _R ¹ _: methyl, ethyl, methoxycarbonylmethyl, 1- (methoxycarbonyl) ethyl-1, tert-butylcarbonylmethyl and aminocarbonylmethyl.

An interesting active ingredient is the compound of the general formula I in which R represents methyl.

• Die nach Verfahren a) benötigten 2-Cyan-2-alkoxyimino-aceta- mide der Formel II sind größtenteils bekannte Verbindungen (vgl. hierzu Ber. 54, 1342 (1911), ferner DT-OS 2 312 956 und die Deutsche Patentanmeldung P 2 623 847 vom 28.5.1976 Le A 17 1361; dasselbe gilt für die umzusetzenden Isocyanate (III) (Liebigs Ann.Chem. 562, 104 (1949) und DT-OS 1 913 273).

For the manufacture of the starting products, please note:

• The 2-cyano-2-alkoxyimino-acetamides of the formula II required by process a) are mostly known compounds (cf. Ber. 54, 1342 (1911), also DT-OS 2 312 956 and the German patent application P 2 623 847 of May 28, 1976 Le A 17 1361; the same applies to the isocyanates (III) to be reacted (Liebigs Ann. Chem. 562, 104 (1949) and DT-OS 1 913 273).

• 2-Cyan-2-methoxyimino-acetamid, 2-Cyan-2-äthoxyimino-acetamid, 2-Cyan-2-octyloxyimino-acetamid;
• ω -Cyanpentylisocyanat, ω-Methoxycarbonyl-pentylisocyanat, ω-Isopropoxycarbonyl-pentvlisocyanat und o-Butoxycarbonylpentylisocyanat.

The following raw materials are to be mentioned here:

• 2-cyan-2-methoxyimino-acetamide, 2-cyan-2-ethoxyimino-acetamide, 2-cyan-2-octyloxyimino-acetamide;
• ω-cyanpentyl isocyanate, ω-methoxycarbonyl pentyl isocyanate, ω-isopropoxycarbonyl pentyl isocyanate and o-butoxycarbonyl pentyl isocyanate.

The 1- (5-substituted pentyl) -3- (2-cyano-2-oximinoacetyl) ureas of the formula IV required as starting materials according to process variants b) to c) have hitherto not been known. They are prepared by using, for example, W-cyanopentyl isocyanate (cf. Liebigs Ann. Chem. 562, 104 (1949), cyanopentyl carbamic acid chloride (DT-OS 2 626 828 rLe A 17 135]), ω-isocyanato-caproic acid alkyl ester (cf. DT- OS 1 913 273), ω-dhenoxycarbonylamino-caproic acid (cf. DT-OS 1 720 606, also Chem. Abstr. 71, 50689 (1969)) or ω-isocyanatocaproic acid chloride (DT-AS 1 222 919) dissolved or suspended in one If ω-phenoxycarbonylamino-caproic acid is used as the starting material, 5-carboxypentylurea is obtained as the ammonium salt. Acidification with a mineral acid gives the free ureidopentylcarboxylic acid. The ω-substituted 1-pentylurea is now with excess cyanoacetic acid in the presence of dicarboxylic anhydride to give 1- (5-substituted pentyl) -3- (2-cyanoacetyl) urea; toluene can serve as solvent. In a third stage, said urea is dissolved in water or in mixtures of water with methanol, ethanol, propanol, glycol monomethyl ether, glycol monoethyl ether, acetonitrile, dioxane or tetrahydrofuran with a salt of nitrous acid at a temperature of 20 to 70 ^° C., preferably at 40 to 50 ° C, by adding an organic carboxylic acid, such as acetic acid or a mineral acid, such as sulfuric acid or by mixing organic carboxylic acids with mineral acids to a pH of 4 to 6, preferably to a pH of 5 to 5.6 brought. The oximation is complete after about 2 hours. The reaction mixture is brought to a pH of 1.8 to 3.5, preferably of, by adding further mineral acid at a temperature which is between the freezing point of the solution and about 30 ° C., preferably between +2 and 10 ° C. about 2. The 1- (5-substituted pentyl) -3- (2-cyan-2-oximino-acetyl) urea of the formula IV is either separated by diluting the reaction mixture with water and, after the product has been separated off, washed with water and dried, or the compound is taken up in a solvent such as ethyl acetate, methyl acetate, ethyl formate or methyl propionate, the solution of the reaction product obtained is washed with water, dried with sodium sulfate, for example, and product IV is precipitated by adding petroleum ether, or the solution is evaporated.

Finally, the urea of the formula IV can also be reacted with an ester of nitrous acid, e.g. Isoamyl nitrite, on a 1- (5-substituted pentyl) -3- (2-cyanoacetyl) urea can be obtained.

• Dimethylsulfat, Diäthylsulfat, 2-Brombutan, 1-Jodpentan, 1-Bromhexan, 1-Bromdecan, Allylchlorid, Methallylchlorid, 1-Chlorbuten-2, Propargylchlorid, 1-Chloraceton, 1-Brom-3,3-dimethyl-butanon-2, 2-Brom-4,4-dimethyl-pentanon-3, Bromessigsäuremethylester, Chloressigsäure-sek.-butylester, 2-Bromvaleriansäurebutylester, 4-Chlor-buttersäure-äthylester, Chloracetamid, N-Methyl-chloracetamid, N-Äthylchloracetamid, N-sek.-Butyl-chloracetamid, N-Hexylchloracetamid, N-Cyclopropyl-chloracetamid, N-Cyclopentylchloracetamid, N-Cyclohexylchloracetamid, Bromacetanilid, N-2-Äthylphenyl-, N-2-Methylphenyl-, N-2-Isopropylphenyl-, N-2-tert.-Butylphenyl-, N-3-Methylphenyl-, N-4-Methylphenyl-, N-2,6-Dimethylphenyl-, N-2-Chlorphenyl-, N-3-Chlorphenyl-, N-4-Chlorphenyl-, N-3,4-Dichlorphenyl-, N-3,5-Dichlorphenyl-und N-2-Methyl-4-chlorphenyl-chloracetamid, -2-chlorpro- pionamid und -2-chlorbutyramid, Benzylchlorid, 2-, 3- oder 4-Xylylchlorid, 2-, 3- oder 4-Methoxybenzylbromid, 3,4-Methylendioxybenzylchlorid, 3-Nitrobenzylchlorid, 4-Nitrobenzylchlorid, 4-Trifluormethylbenzylchlorid, 2-, 3- oder 4-Chlorbenzylchlorid, 3,4-Dichlorbenzylchlorid, 2-Phenyl-benzylchlorid, 4-Phenyl-benzylchlorid, 4-Benzoylbenzylchlorid, 4-(2-, 3- oder 4-Chlorbenzoyl)-benzylchlorid, 4-(2,3-, 2,4-, 2,5-, 2,6-, 3,4- oder 3,5-Dichlorbenzoyl)-benzylchlorid, 2-, 3- oder 4-Phenoxybenzylchlorid, ar.-Tetrachlor-o-, Tetrachlor-m- und Tetrachlor-p-xylylchlorid.

The alkylating agents of formula v required for process b) are mostly known, laboratory-typical compounds. If they have not yet been described, they can be obtained by processes which are known in principle. The following are examples of starting materials of the formula V:

• Dimethyl sulfate, diethyl sulfate, 2-bromobutane, 1-iodopentane, 1-bromohexane, 1-bromodecane, allyl chloride, methallyl chloride, 1-chlorobutene-2, propargyl chloride, 1-chloroacetone, 1-bromo-3,3-dimethyl-butanone-2, 2-bromo-4,4-dimethyl-pentanone-3, methyl bromoacetate, sec-butyl chloroacetic acid, butyl 2-bromovalerate, ethyl 4-chloro-butyrate, chloroacetamide, N-methyl-chloroacetamide, N-ethylchloroacetamide, N-sec .-Butyl-chloroacetamide, N-hexylchloroacetamide, N-cyclopropyl-chloroacetamide, N-cyclopentylchloroacetamide, N-cyclohexylchloroacetamide, bromoacetanilide, N-2-ethylphenyl, N-2-methylphenyl, N-2-isopropylphenyl, N-2 -tert.-butylphenyl, N-3-methylphenyl, N-4-methylphenyl, N-2,6-dimethylphenyl, N-2-chlorophenyl, N-3-chlorophenyl, N-4-chlorophenyl , N-3,4-dichlorophenyl, N-3,5-dichlorophenyl and N-2-methyl-4-chlorophenyl chloroacetamide, -2-chloropropionamide and -2-chlorobutyramide, benzyl chloride, 2-, 3- or 4-xylyl chloride, 2-, 3- or 4-methoxybenzyl bromide, 3,4-methylenedioxybenzyl chloride, 3-nitrobenzyl chloride, 4-nitrobenzyl chloride, 4-trifluoromethylbenzyl chloride, 2-, 3- or 4-chlorobenzyl chloride, 3,4-dichlorobenzyl chloride, 2-phenyl-benzyl chloride, 4-phenyl-benzyl chloride, 4-benzoylbenzyl chloride, 4- (2-, 3- or 4-chlorobenzoyl) benzyl chloride, 4- (2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dichlorobenzoyl) - benzyl chloride, 2-, 3- or 4-phenoxybenzyl chloride, ar.-tetrachloro-o-, tetrachlor-m- and tetrachloro-p-xylyl chloride.

• Acetanhydrid, Propionsäureanhydrid, Chloracetylchlorid, Dichloracetylchlorid, Trichloracetylchlorid 2,3-Dibrompropionsäurechlorid, Isobuttersäurechlorid, 2-Chlorisobuttersäureclorid, Valeriansäurechlorid, Isovaleriansäurechlorid, 2-Äthylhexansäurechlorid, Cyanessigsäurechlorid, Acrylsäurechlorid, Acrylsäurechlorid, Methacrylsäurechlorid, Crotonsäurechlorid.

The acid anhydrides and acid halides of the formula VI required for the reaction according to process c) are compounds customary in the laboratory. To be mentioned here:

• Acetic anhydride, propionic anhydride, chloroacetyl chloride, dichloroacetyl chloride, trichloroacetyl chloride, 2,3-Dibrompropionsäurechlorid, isobutyryl, 2-Chlorisobuttersäureclorid, valeryl chloride, isovaleryl chloride, 2-Äthylhexansäurechlorid, cyanoacetyl chloride, acrylic acid chloride, acrylic acid chloride, methacrylic acid chloride, crotonic.

The isocyanates of the formula VII or the carbamic acid halides of the formula VIII required for the reaction according to process d) are likewise known compounds; the carbamic acid halides are prepared by addition of hydrogen halide to the isocyanates of the formula VI.

• Methyl-, Äthyl-, Propyl-, Butyl-, Isobutyl-, Hexyl-, Decyl-isocyanat oder -carbamidsäurechlorid,
• ω-Cyanäthyl-isocyanat,
• 1-Cyan-1-methyl-äthyl-isocyanat,
• ω-Cyanpropyl-isocyanat,
• ω-Cyanpentyl-isocyanat,
• ω-Cyanhexyl-isocyanat,
• ω-Cyanoctyl-isocyanat,
• ω-Cyannonyl-isocyanat,
• ω-Cyandecyl-isocyanat,
• ω-Cyanundecyl-isocyanat,
• Methoxycarbonylmethyl-isocyanat,
• Äthoxycarbonylmethyl-isocyanat,
• Butoxycarbonyläthyl-isocyanat,
• Isobutoxycarbonyläthyl-isocyanat,
• 1-Methoxycarbonyl-1-methyl-äthyl-isocyanat,
• 1-Propoxycarbonyl-1-methyl-äthyl-isocyanat,
• 1-Äthoxycarbcnyl-1-äthyl-äthyl-isocyanat,
• 1-Isobutoxycarbonyl-l-äthyl-äthyl-isocyanat,
• Methoxycarbonyl-propyl-isocyanat,
• Methoxycarbonyl-pentyl-isocyanat,
• Isopropoxycarbonyl-pentyl-isocyanat,
• sek.-Butyloxyloxycarbonyl-pentyl-isocyanat,
• 2-Äthoxycarbonyl-2-äthyl-butyl-isocyanat,
• γ-Äthoxycarbonyl-octyl-isocyanat,
• Methoxycarbonyl-decyl-isocyanat,
• Äthoxycarbonyl-decyl-isocyanat,
• Propoxycarbonyl-decyl-isocyanat,
• Butoxycarbonyl-decyl-isocyanat,
• Methoxycarbonyl-undecyl-isocyanat,
• Phenylisocyanat, 2- und 4-Tolylisocyanat, 3- und 4-Nitrophenylisocyanat, 2-, 3- und 4-Chlorphenylisocyanat, 3,4-Dichlorphenylisocyanat, 3,5-Dichlorphenylisocyanat und 2-Trifluormethylisocyanat.

The following connections are worth mentioning:

• Methyl, ethyl, propyl, butyl, isobutyl, hexyl, decyl isocyanate or carbamic acid chloride,
• ω-cyanoethyl isocyanate,
• 1-cyan-1-methyl-ethyl-isocyanate,
• ω-cyanopropyl isocyanate,
• ω-cyanopentyl isocyanate,
• ω-cyanhexyl isocyanate,
• ω-cyanoctyl isocyanate,
• ω-cyannonyl isocyanate,
• ω-cyanodecyl isocyanate,
• ω-cyanundecyl isocyanate,
• Methoxycarbonylmethyl isocyanate,
• Ethoxycarbonylmethyl isocyanate,
• Butoxycarbonylethyl isocyanate,
• Isobutoxycarbonylethyl isocyanate,
• 1-methoxycarbonyl-1-methyl-ethyl-isocyanate,
• 1-propoxycarbonyl-1-methyl-ethyl-isocyanate,
• 1-ethoxycarbonyl-1-ethyl-ethyl-isocyanate,
• 1-isobutoxycarbonyl-1-ethyl-ethyl-isocyanate,
• Methoxycarbonyl-propyl-isocyanate,
• Methoxycarbonyl pentyl isocyanate,
• Isopropoxycarbonyl pentyl isocyanate,
• sec-butyloxyloxycarbonyl-pentyl-isocyanate,
• 2-ethoxycarbonyl-2-ethyl-butyl isocyanate,
• γ-ethoxycarbonyl octyl isocyanate,
• Methoxycarbonyl-decyl-isocyanate,
• Ethoxycarbonyl-decyl-isocyanate,
• Propoxycarbonyl decyl isocyanate,
• Butoxycarbonyl-decyl-isocyanate,
• Methoxycarbonyl-undecyl-isocyanate,
• Phenyl isocyanate, 2- and 4-tolyl isocyanate, 3- and 4-nitrophenyl isocyanate, 2-, 3- and 4-chlorophenyl isocyanate, 3,4-dichlorophenyl isocyanate, 3,5-dichlorophenyl isocyanate and 2-trifluoromethyl isocyanate.

The carbonic acid esters required by process e) are also known compounds. Worth mentioning are: dimethyl pyrocarbonate, diethyl pyrocarbonate, ethyl chloroformate, methyl chloroformate, isopropyl chloroformate, sec-butyl chloroformate, isobutyl chloroformate, allyl chloroformate and methyl chloroformate.

To prepare the compounds according to the invention according to process a), the 2-cyano-2-alkoximinoacetamide is dissolved in an inert water-free solvent such as dioxane, tetrahydrofuran or diisopropyl ether with e.g. Sodium hydride or potassium tert-butoxide was converted into the anion of the amide and then reacted with ω-substituted pentyl isocyanate at a moderately elevated temperature. When the reaction has ended, the mixture is acidified slightly in the cold with an organic carboxylic acid, then the reaction product according to the invention is precipitated by adding water or the solution of the reaction product in the organic solvent is washed out and carefully evaporated.

To prepare those compounds of the formula I according to the invention in which R is R ¹ , according to process b), the reaction is preferably carried out in the presence of polar solvents such as dimethyl sulfoxide, dimethylformamide, dimethylacetamide, acetone, methyl ethyl ketone, methylene chloride, chloroform, chlorobenzene, toluene, dioxane, Tetrahydrofuran, acetonitrile, benzonitrile or ethyl acetate.

All customary hydrogen halide acceptors can be used as acid binders in process b). These include alkali hydroxides, alkali carbonates and other suitable alkali salts. Examples include Sodium carbonate, sodium bicarbonate, borax (disodium tetraborate) and trilithium phosphate. If you work in the presence of water, it can be neutralized by adding sodium hydroxide solution. Organic acid binders can also be used, e.g. tertiary amines. These include triethylamine, dimethylbenzylamine, dimethylaniline, pyridine, picoline, quinoline, ethyldiisopropylamine and ethyldicyclohexylamine.

The reaction temperatures can be varied within a wide range in process b). Generally one works between about -50 and about + 120 ° C, preferably between -5 and + 80 ° C.

The reactions can also be carried out in mixtures of water and a water-miscible organic solvent or in heterogeneous systems consisting of water and a water-immiscible or only partially miscible solvent; the temperature range of the reaction here lies between the freezing point of the water or the solidification point of the aqueous solution and approximately 100 ° C., preferably -5 ° to + 80 ° C.

However, if the salts of the urea of the formula IV are used as starting materials in process b), the reaction must be carried out at low temperatures, preferably at -30 ° C. to -10 ° C., and weakly acidified after the reaction has ended.

Reaction temperatures and reaction time in process b) are determined by the activity of the starting products of the formula V. Advantageously, a small amount of an iodide is added to the mixtures before the reaction, unless a compound of the formula V with iodine is used as the leaving group. As a result, the reaction rate is increased and the risk of the formation of compounds with a nitron structure is reduced (cf. Houben-Weyl, "Methods of Organic Chemistry", Volume 10/4, Stuttgart (1968)).

The explanations given in process b) also apply correspondingly to process variants f) when a carboxylic acid of the formula X is to be converted into a product of the formula I according to the invention in which R represents R and Q represents the group CO-OR ⁵ .

The preparation of the compounds of the formula I according to the invention, in which R represents CO-R, by process c) is carried out in an anhydrous organic solvent in a temperature range between -50 ° C. and + 120 ° C., preferably at 0 to 50 ° C. made, with a tert. Amine is used to bind the acid.

Process d) according to the invention is expediently carried out in a diluent. All inert organic solvents are suitable as such. Dimethyl sulfoxide, dimethylformamide, dimethylacetamide and ethyl acetate are preferably used, and also ketones, such as e.g. Acetone, methyl ethyl ketone and diethyl ketone, also ether, such as e.g. Tetrahydrofuran, chlorinated hydrocarbons, e.g. Methylene chloride and chloroform, nitriles such as e.g. Acetonitrile and benzonitrile and aromatics such as e.g. Toluene and chlorobenzene.

Basic catalysts can be used as auxiliaries in process d); for example tertiary amines, such as triethylamine or pyridine, and tin-2-ethylhexanoate. Instead of the isocyanates of the formula VII, the corresponding carbamic acid halides of the formula VIII can be used in each case Find. In this case, additional tertiary amine is required to bind the hydrohalic acid released in the reaction.

The reaction temperatures can be varied within a wide range in process d). Generally one works in the range between -20 and + 120 ° C, preferably between +10 and 70 ° C.

The preparation of the compounds of formula I according to the invention, in which R represents CO-O-R, after process step e) is carried out analogously to the procedure according to process b).

Depending on the working conditions, the active compounds according to the invention precipitate in crystalline form or remain dissolved in the organic solvent and can then be separated out after washing out the solution with water by carefully concentrating the solution or by adding a few clear organic solvents, such as carbon tetrachloride, cyclohexane or dibutyl ether.

If the compounds according to the invention are dissolved in a water-miscible solvent, they can also be filled in by adding water. As far as the special conditions of the work-up processes allow, the solutions of the active substances according to the invention or the still solvent-moist suspensions of the active substances should be made weakly acidic.

The compounds according to the invention partly decompose at a higher temperature; in these cases the melting points can only be determined with little accuracy or not at all. The presence of certain structural elements can be seen from the NMR spectra. The IR spectra also show characteristic absorption bands.

The active substances according to the invention have a strong fungitoxic effect. They do not damage crops in the concentrations necessary to control fungi. For these reasons, they are suitable for use as crop protection agents for combating fungi. Fungitoxic agents in crop protection are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomyccces, Basidiomycetes, Deuteromycetes.

The active compounds according to the invention can be used against parasitic fungi which attack above-ground parts of plants or attack the plants from the ground, and against seed-borne pathogens. They can therefore also be used for soil and seed treatment.

The active ingredients in particular show a high protective and curative activity against phycomycetes. There are also good effects against Mycosphaerella and Rhizoctonia species and against rust fungi.

The active compounds according to the invention not only have the good properties of excellent commercial preparations, but also have considerable advantages. These lie primarily in the ability of the substances according to the invention to penetrate the plant. They can be absorbed by the seed surface, by the roots and also by aerial plant organs after external applications. They also have the advantageous ability to have a locosystemic effect, ie to exert a deep effect in the plant tissue and thereby to eliminate fungal pathogens which have already penetrated into the tissue of the host plant.

In a certain concentration range, some substances according to the invention are also effective as growth regulators for plants.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, P _L lver, pastes and granules. These are made in a known manner, e.g. B. by mixing the active ingredients with extenders, that is liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents. In the case of the use of water as an extender, e.g. B. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated 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, methyliaobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; Liquefied gaseous extenders or carriers mean those liquids which are gaseous at normal temperature and pressure, e.g. B. aerosol propellants such as dichlorodifluoromethane or trichlorofluoromethane; as solid carrier materials: natural rock meals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock meals, such as highly disperse silica, aluminum oxide and silicates; as an emulsifier; non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as a dispersant: e.g. B. lignin, sulfite and methyl cellulose.

In addition to the above formulation options, it should be noted that the substances according to the invention together with sucrose, dextrose, dextrins, with anhydrous calcium sulfate or calcium sulfate hemihydrate, and with carboxylic acids, e.g. Fumaric acid or 4-hydroxylbenzoic acid, or can also be formulated together with weakly acidic ion exchangers.

The active compounds according to the invention can be present in the formulations in mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, herbicides, bird repellants, growth agents, plant nutrients and agents which improve soil structure.

The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They are used in the usual way, e.g. by pouring, spraying, spraying, dusting, scattering, dry pickling. Wet pickling, wet pickling, slurry pickling or incrustation.

When used as leaf fungicides, the active compound concentrations in the use forms can be varied within a substantial range. They are generally between 0.5 and 0.0005 percent by weight, preferably between 0.2 and 0.001.

In the case of seed treatment, amounts of active ingredient of 0.01 to 50 g per kilogram of seed, preferably 0.5 to 5 g, are generally required.

For soil treatment, amounts of active ingredient from 1 to 1000 g per cbm of soil, preferably from 10 to 200 g, are required.

The possible uses explain the following usage examples:

Example A

Phytophthora test (tomato) / protective

The amount of active ingredient required for the desired active ingredient concentration in the spray liquid is mixed with the stated amount of solvent and the concentrate is diluted with the stated amount of water which contains the additives mentioned.

The spray liquid is used to spray young tomato plants with 2 to 4 leaves until they drip wet. The plants remain in the greenhouse for 24 hours at 20 ° C. and a relative humidity of 70%. The tomato plants are then inoculated with an aqueous spore suspension of Phytophthora infestans. The plants are placed in a humid chamber with 100% humidity and a temperature of 18 to 20 ° C.

The infestation of the tomato plants is determined after 5 days. The rating values received are converted to percent infestation. 0 means no infection, 100% means that the plants are completely infected.

Active substance, active substance concentration and results are shown in the table below:

Example B

Phytophthora test (tomatoes) / curative

The amount of active ingredient required for the desired active ingredient concentration in the spray liquid is mixed with the stated amount of solvent and the concentrate is diluted with the stated amount of water which contains the additives mentioned.

Young tomato plants with 2 to 4 leaves are inoculated with an aqueous spore suspension of Phytophthora infestans. The plants stand for 7 hours at 20 ° C and a relative humidity of 100%.

After a short drying time, the plants are sprayed to runoff point with the spray liquid which has been prepared in the above-mentioned manner and then placed in a humid chamber with 100% atmospheric humidity and a temperature of 18 to 20 ° C.

The infestation of the tomato plants is determined after 5 days. The rating values received are converted to percent infestation. 0 t means no infection, 100% means that the plants are completely infected.

Active substances, active substance concentration and results are shown in the following table:

Example C Seed dressing test / wheat stone fire (seed-borne mycosis)

To produce a suitable dry mordant, the active ingredient is stretched with a mixture of equal parts by weight of talc and kieselguhr to a fine powdery mixture with the desired active ingredient concentration.

Wheat seed is contaminated with 5 g of Tilletia caries chlamydospores per kg of seed. For dressing, shake the seeds with: the dressing in a sealed glass bottle. The seeds are exposed to moist clay under a covering layer of a layer of gauze and 2 cm of moderately moist compost soil in the refrigerator at 10 ° C for 10 days at optimal germination conditions for the spores.

Subsequently, the germination of the spores on the wheat grains is determined microscopically, each of which contains around 100,000 spores. The fewer spores have sprouted, the more effective the active ingredient will be.

Active ingredients, active ingredient concentrations in the pickling agent, amounts of pickling agent applied and the percentage of germs in the spores are shown in the table below:

Example D Phytotoxicity test

_Man vermischt die für die gewünschte Wirkstoffkonzentration in der Spritzflüssigkeit nötige Wirkstoffmenge mit der angegebenen Menge des Lösungsmittels und verdünnt das Konzentrat mit der angegebenen Menge Wasser, welches die genannten Zusätze enthält. Mit der Spritzflüssigkeit bespritzt man junge Tomaten bis zur Tropfnässe. Nach dem Abtrocknen werden die Pflanzen im Gewächshaus bei einer Temperatur von +20°C und ca. 70 relativer Luftfeuchtigkeit aufgestellt.

_M an mixes the amount of active ingredient required for the desired active ingredient concentration in the spray liquid with the stated amount of solvent and dilutes the concentrate with the stated amount of water which contains the additives mentioned. The spray liquid is used to spray young tomatoes to the point of dripping wet. After drying, the plants are placed in the greenhouse at a temperature of + 20 ° C and approx. 70 relative air humidity.

• 1 bedeutet keine Schäden
• 9 bedeutet, daß die Pflanzen total geschädigt bzw. abgestorben sind.

The plants are repeatedly evaluated for damage. The evaluation is based on a rating scheme from 1 to 9.

• 1 means no damage
• 9 means that the plants are totally damaged or dead.

The observation period is usually 4 days.

Active substances, active substance concentration and results are shown in the table below:

Manufacturing examples example 1

(Herstellung erfolgt gemäß Verfahren b))

(Manufactured according to method b))

500 g of 1- (5-cyanopentyl) -3- (2-cyan-2-oximino-acetyl) urea (1.99 mol), 2 ltr. Acetonitrile, 260 g of dimethyl sulfate (2.06 mol) are placed at 40 ° C. With good stirring, a solution of 84 g of sodium hydroxide, dissolved in 440 ml of water, is added in about 22 minutes until a pH of about 8 is reached. Then the reaction mixture is immediately adjusted to a pH of 5. The reaction product is precipitated by adding ice. It is separated off, washed salt-free with water and dried at 60 ° C. and a pressure of 1 m Hg. Yield: 503 g of 1- (5-cyanopentyl) -3- (2-cyan-2-methoxyimino-acetyl) urea, mp. 92 ° C., that is 95% of theory. The compound can be recrystallized from water or from isopropyl alcohol.

550 g (2,47 Mol) 1-(5-Cyanpentyl)-3-(2-cyanacetyl)-harnstoff, 625 g Wasser, 625 g Dioxan, 188 g techn. Natriumnitrit werden bei 50⁰C durch langsamen Zusatz von etwa 15 tiger Schwefelsäure auf einen pH-Wert von 5 eingestellt. Man rührt zwei Stunden, gibt dann 5 ltr. Wasser und 5 ltr. Äthylacetat hinzu. Es wird auf 2°C abgekühlt und durc:h weitere Zugabe von 15 %iger Schwefelsäure ein pH-Wert von 2 eingestellt. Die organische Phase wird abgetrennt und die wäßrige Phase ein zweites Mal mit 2 ltr. Äthylacetat gerührt. Die Äthylacetatlösung wird zweimal mit je 2 ltr. Wasser, welches zur besseren Trennung eine geringe Menge Natriumsulfat gelöst enthält, gewaschen und zweimal über Natriumsulfat getrocknet. Durch Zugabe von Petroläther wird das Reaktionsprodukt ausgefällt. Es wird mit einer Mischung aus Petroläther und Äthylacetat im Verhältnis 4:1 gewaschen und bei 60°C und einem Druck von C,1 mm Hg getrocknet. Ausbeute: 504 g 1-(5-Cyanpentyl)-3-(2-cyan-2-oximino-acetyl)-harnstoff von Fp. 147°C.Preliminary product:

550 g (2.47 mol) 1- (5-cyanopentyl) -3- (2-cyanoacetyl) urea, 625 g water, 625 g dioxane, 188 g techn. Sodium nitrite is adjusted to a pH value of 5 at 50 ^° C. by slowly adding about 15% sulfuric acid. Stir for two hours, then give 5 liters. Water and 5 ltr. Ethyl acetate added. It is cooled to 2 ° C. and a pH of 2 is adjusted by further addition of 15% sulfuric acid. The organic phase is separated and the aqueous phase with a second time 2 ltr. Ethyl acetate stirred. The ethyl acetate solution is twice with 2 ltr. Water, which contains a small amount of sodium sulfate in solution for better separation, washed and dried twice over sodium sulfate. The reaction product is precipitated by adding petroleum ether. It is washed with a mixture of petroleum ether and ethyl acetate in a ratio of 4: 1 and dried at 60 ° C and a pressure of C, 1 mm Hg. Yield: 504 g of 1- (5-cyanopentyl) -3- (2-cyan-2-oximino-acetyl) urea of mp 147 ° C.

A second crystal fraction (approx. 70 g) can be obtained from the mother liquor by concentration.

For further purification, the product can be recrystallized from water, diethyl ketone or ethyl acetate.

90,4 g (1,06 Mol) Cyanessigsäure, 163 g (1,05 Mol) 1-(5-Cyan- pentyl)-harnstoff, 200 ml trockenes Toluol werden in 35 Minuten mit 135,6 g (1,32 Mol) Essigsäureanhydrid versetzt. Man erwärmt die Reaktionsmischung 3 Stunden auf 60 bis 67°C. Die Reaktionslösung wird bei ca. 70°C filtriert. Das Reaktionsprodukt scheidet sich beim Abkühlen aus. Es wird abgesaugt, mit Toluol gewaschen und bei 60°C und einem Druck von 0,1 mm Hg getrocknet. Ausbeute: 137,8 g 1-(5-Cyanpentyl)-3-(2-cyanacetyl)-harnstoff. Fp. 112°C. Die Verbindung kann aus Toluol, Athylacetat oder aus Wasser umkristallisiert werden. Fp. 113,5°C.Intermediate:

90.4 g (1.06 mol) of cyanoacetic acid, 163 g (1.05 mol) of 1- (5-cyano-pentyl) urea, 200 ml of dry toluene are mixed with 135.6 g (1.32 mol ) Acetic anhydride added. The reaction mixture is heated at 60 to 67 ° C. for 3 hours. The reaction solution is filtered at approx. 70 ° C. The reaction product is eliminated on cooling. It is filtered off, washed with toluene and dried at 60 ° C and a pressure of 0.1 mm Hg. Yield: 137.8 g of 1- (5-cyanopentyl) -3- (2-cyanoacetyl) urea. Mp 112 ° C. The compound can be recrystallized from toluene, ethyl acetate or water. Mp 113.5 ° C.

1019 g ω-Cyanpentylisocyanat werden in 4,8 ltr. trockenem Toluol gelöst. Unter Rühren wird Ammoniak über die Lösung geleitet bis nichts mehr aufgenommen wird. Das Reaktionsprodukt scheidet sich ab. Es wird abgetrennt, mit Toluol, Isopropanol und mit Wasser gewaschen und bei 60°C und einem Druck von 0,1 mm Hg getrocknet. Ausbeute: 1092 g 1-(5-Cyan- pentyl)-harnstoff. Fp. 143-144°C.Starting product:

1019 g ω-cyanopentyl isocyanate in 4.8 ltr. dissolved dry toluene. With stirring, ammonia is added to the solution guided until nothing is recorded. The reaction product separates out. It is separated off, washed with toluene, isopropanol and with water and dried at 60 ° C. and a pressure of 0.1 mm Hg. Yield: 1092 g of 1- (5-cyano-pentyl) urea. Mp 143-144 ° C.

(The compound can also be prepared from 5-aminocapronitrile and potassium cyanate).

Example 2

(Herstellung erfolgt gemäß Verfahren b))

(Manufactured according to method b))

25.1 g (0.1 mol) of 1- (5-cyanopentyl) -3- (2-cyan-2-oximino-acetyl) urea, 100 ml of acetonitrile and 17 g of 1-bromohexane are placed at 40 ° C. and 13 g of ethyldiisoproyplamine were added dropwise in 30 minutes. The mixture is kept at 40 ° C. for a further 30 minutes, 1 ml of acetic acid, 400 ml of methylene chloride and water are added. The methylene chloride solution is washed three times with water and evaporated in vacuo. The residue crystallizes after treatment with petroleum ether. Yield 25 g of 1- (5-cyanopentyl) -3- (2-cyan-2-hexyloximino-acetyl) urea. Mp 47 ° C.

Example 3

(Herstellung erfolgt gemäß Verfahren c))

(Manufactured according to method c))

25.1 g (0.1 mol) of 1- (5-cyanopentyl) -3- (2-cyan-2-oximino-acetyl) urea, 100 ml of acetonitrile and 9.3 g (0.1 mol) of propionic acid chloride submitted and 7.9 g of pyridine added dropwise. After 18 hours, the reaction mixture is filtered and the compound according to the invention is precipitated by adding ice, separated off, washed with water and dried at 60 ° C. and under a pressure of 0.1 mm Hg. Yield: 26.6 g of 1- (5-cyanopentyl) -3- (2-cyan-2-propionyloximino-acetyl) urea. Mp 116.5 ° C.

Example 4

(Herstellung erfolgt gemäß Verfahren d))

(Manufactured according to method d))

25.1 g (0.1 mol) of 1- (5-cyanopentyl) -3- (2-cyan-2-oximino-acetyl) urea, 100 ml of dry acetonitrile and 6 g of methyl isocyanate are introduced. 100 mg of triethylenediamine are added. In an exothermic reaction, 1- (5-cyanopentyl) -3- (2-cyan-2-methylaminocarbonyloximinoacetyl) urea is formed. It is suctioned off, washed with acetonitrile and dried at 60 ° C. and a pressure of 0.1 mm Hg. Mp 141.5-146.5 ° C (dec.) _IR (CHCl ₃ ): CO 18 ₀ 5 cm ^-1 .

herstellen:

As described in the above examples, the following compounds of the general formula

produce:

Example 22

Die Herstellung der Verbindung erfolgt gemäß Herstellungsverfahren b) durch Methylierung der entsprechenden HydroxyVerbindung, die nachstehend beschrieben wird. Fp. 155°C.

The compound is prepared according to production process b) by methylation of the corresponding hydroxy compound, which is described below. Mp 155 ° C.

72 g 1-(5-Aminocarbonyl-pentyl)-3-(2-cyanacetyl)-harnstoff, 125 ml Wasser, 125 ml Dioxan, 23,2 g Natriumnitrit und 1 ml Essigsäure werden bei 50°C durch langsames Zutropfen von 15 %icer Schwefelsäure auf pH 4,5 bis 5 eingestellt. Man rührt während 2 Stunden bei 50°C, verdünnt mit 600 ml Wasser und 600 ml Äthylazetat, kühlt dann auf 20°C ab und stellt die Reaktionsmischung auf einen pH-Wert von 2 ein. Die Kristalle werden abgetrennt, mit Wasser gewaschen und in Vakuum getrocknet. Man erhält 61,3 g 1-(5-Aminocarbonyl-pentyl)-3-(2-cyan-2-oximino-acetyl)-harnstoff von Fp. 187-189°C.Preliminary product:

72 g of 1- (5-aminocarbonylpentyl) -3- (2-cyanoacetyl) urea, 125 ml of water, 125 ml of dioxane, 23.2 g of sodium nitrite and 1 ml of acetic acid are added at 50 ° C. by slowly adding 15% icer sulfuric acid adjusted to pH 4.5 to 5. The mixture is stirred at 50 ° C. for 2 hours, diluted with 600 ml of water and 600 ml of ethyl acetate, then cooled to 20 ° C. and the reaction mixture is adjusted to a pH of 2. The crystals are separated, washed with water and dried in vacuo. 61.3 g of 1- (5-aminocarbonylpentyl) -3- (2-cyan-2-oximino-acetyl) urea of mp 187-189 ° C. are obtained.

Intermediate:

This intermediate is prepared analogously to the intermediate specified in Example 1, starting from 1- (5-aminocarbonylpentyl) urea. Mp 164 ^v C.

Starting product:

502 g (2 mol) of phenoxycarbonylamino-caproic acid, 1.2 l of chlorobenzene, 0.6 l of ethylene chloride, 0.4 g of antimony trichloride and 1 g of dimethylformamide are initially introduced, while cooling with ice. At 9 ° C, 256 g (2.15 mol) of thionyl chloride are added dropwise in 90 minutes. The reaction mixture is stirred for a further 4 hours. Then a part of the solvent is distilled off at a bottom temperature of 31 ° C at 11 Torr. Ammonia is then passed onto the reaction mixture at −20 ° C. until nothing is absorbed. After the addition of 1.6 1 31% aqueous ammonia solution, the mixture is slowly heated to boiling and kept at the boiling temperature for about 6 hours. The crystals are separated off, washed with water and dried at 70 ° C. in vacuo: t. Yield 171 g of 1- (5-aminocarbonylpentyl) urea of mp. 208 ° C.

Example 23

Die Herstellung der Verbindung erfolgt nach Verfahren b). Fp. 172°C.

The connection is produced by method b). Mp 172 ° C.

Example 24

Die Herstellung erfolgt nach Verfahren b). Fp. 167°C.

The production takes place according to method b). Mp 167 ° C.

48,2 g (0,2 Mol) 1-(5-Carboxypentyl)-3-(2-cyanacetyl)-harnstoff, 50 ml Wasser, 50 ml Dioxan und 15,2 g Natriumnitrit werden auf 50°C erwärmt. Es wird sodann sov:.el einer Mischung aus 13 g Schwefelsäure und 90 g Wasser zugetropft, daß ein pH-Wert von 4,6 resultiert. Man hält noch 2 Stunden bei 50°C, kühlt dann auf ca. 1°C ab, gibt 400 ml Wasser hinzu und vermindert den pH-Wert durch weiteres Zutropfen von verdünnter Schwefelsäure auf 2,5. Die Kristalle werden abgetrennt, mit Wasser gewaschen und bei 60°C im Vakuum getrocknet. Die Ausbeute beträgt 51,7 g an 1-(5-Carboxy- pentyl)-3-(2-cyan-2-oximino-acetyl)-harnstoff von Fp. 201°C.Preliminary product:

48.2 g (0.2 mol) of 1- (5-carboxypentyl) -3- (2-cyanoacetyl) urea, 50 ml of water, 50 ml of dioxane and 15.2 g of sodium nitrite are heated to 50 ° C. It is then added dropwise to a mixture of 13 g of sulfuric acid and 90 g of water to give a pH of 4.6. The mixture is kept at 50 ° C. for a further 2 hours, then cooled to approx. 1 ° C., 400 ml of water are added and the pH is reduced to 2.5 by further dropwise addition of dilute sulfuric acid. The crystals are separated off, washed with water and dried at 60 ° C. in vacuo. The yield is 51.7 g of 1- (5-carboxypentyl) -3- (2-cyan-2-oximino-acetyl) urea of mp. 201 ° C.

Das Zwischenprodukt wird entsprechend den Angaben für das Zwischenprodukt nach Beispiel 1 ausgehend von 1-(5-Carboxy- pentyl)-harnstoff hergestellt. Fp. 158°C.Intermediate:

The intermediate product is prepared starting from 1- (5-carboxypentyl) urea in accordance with the information for the intermediate product according to Example 1. Mp 158 ° C.

260,5 g (1,04 Mol) Phenoxycarbonylamino-capronsäure werden in 500 ml Dioxan suspendiert. Unter äußerer Kühlung werden 800 ml 33 %ige wäßrige Ammoniak-Lösung zugetropft. Die Mischung wird innerhalb von 3 Stunden auf 90°C gebracht und während 6 Stunden auf dieser Temperatur gehalten. Man destilliert einen Teil des Lösungsmittels ab und säuert mit Schwefelsäure auf einen pH-Wert von 3 an. Nach Abkühlen der Mischung auf 3°C werden die Kristalle abgesaugt und mit Wasser gewaschen. Die Ausbeute beträgt 116 g 1-(5-Carboxypentyl)-harnstoff von Fp. 167-181°C.Starting product:

260.5 g (1.04 mol) of phenoxycarbonylamino-caproic acid are suspended in 500 ml of dioxane. 800 ml of 33% strength aqueous ammonia solution are added dropwise with external cooling. The mixture is brought to 90 ° C. in the course of 3 hours and kept at this temperature for 6 hours. Part of the solvent is distilled off and acidified to pH 3 with sulfuric acid. After Ab cooling the mixture to 3 ° C., the crystals are suctioned off and washed with water. The yield is 116 g of 1- (5-carboxypentyl) urea of mp. 167-181 ° C.

Example 25

9,8 g der Verbindung gemäß Beispiel 24, 100 ml Acetonitril, 1,8 g Natriumcarbonat und 4,8 g Dimethylsulfat werden während 5 Stunden bei 70°C gehalten. Hiernach kühlt man auf 2°C ab, fügt 100 g Wasser und Eis hinzu und trennt die abgeschiedenen Kristalle ab. Man wäscht dieselben mit Wasser und erhält 9 g 1-(5-Methoxycarbonyl-pentyl)-3-(2-cyan-2-methoxyimino-acetyl)-harnstoff von Fp. 91°C.

9.8 g of the compound according to Example 24, 100 ml of acetonitrile, 1.8 g of sodium carbonate and 4.8 g of dimethyl sulfate are kept at 70 ° C. for 5 hours. Thereafter, the mixture is cooled to 2 ° C., 100 g of water and ice are added, and the crystals separated off. They are washed with water and 9 g of 1- (5-methoxycarbonyl-pentyl) -3- (2-cyan-2-methoxyimino-acetyl) urea of mp 91 ° C. are obtained.

Claims (6)

1. α-substituted pentylurea derivatives of the general formula

in which R represents R ¹ , _CO -R ² , CO-NH-R ³ or CO-OR ⁴ , where R represents unsubstituted alkyl of 1 to 10 carbon atoms; furthermore stands for substituted alkyl with 1 to 4 carbon atoms, which as a substituent is a vinyl group, an alkynyl group with up to 4 carbon atoms, an alkylcarbonyl group with 2 to 5 carbon atoms, an alkoxycarbonyl group with 2 to 5 carbon atoms, an alkenoxycarbonyl or alkynoxycarbonyl group with 4 up to 5 carbon atoms, an aminocarbonyl, N-alkylaminocarbonyl or N-cycloalkylaminocarbonyl group each with up to 7 carbon atoms, or an N-phenyl.-aminocarbonyl group which may have lower alkyl groups and / or chlorine atoms as further substituents on the phenyl radical, contains; furthermore stands for benzyl, which in the aromatic part can be substituted by methyl, methoxy, methylenedioxy, nitro, trifluoromethyl, benzoyl, mono- or dichlorobenzoyl, phenyl or phenoxy groups or by 1 to 4 chlorine atoms; and R ^{2 represents} a straight or branched, saturated or unsaturated hydrocarbon radical with up to 8 carbon atoms, which can be substituted by chlorine or bromine atoms or by a cyano group, and _R ^{3 represents} a straight or branched alkyl radical with up to 11 carbon atoms, which can be substituted by a cyano group or by a carbonylalkyl alkyl radical with up to 5 carbon atoms, or represents a phenyl radical which is substituted by methyl, nitro or trifluoromethyl groups or can be substituted by chlorine atoms, and R ^{4 represents} a saturated or unsaturated aliphatic group with up to 4 carbon atoms, and O represents CN, CO-NH ₂ , COOH or CO-OR ⁵ , where R ^{5 represents} an alkyl group with 1 to 4 carbon atoms, 2. Process for the preparation of cyanopentylurea derivatives, characterized in that a) a 2-cyan-2-alkoxyimino-acetamide of the formula

in which R has the meaning given above, in the presence of a strong base with an ω-substituted pentyl isocyanate of the formula

in which Q has the meaning given above, implements, or b) the 1- (5-substituted pentyl) -3- (2-cyano-2-oximino-acetylurea of the formula

in which Q has the meaning given above,
in the presence of an acid binder, or an alkali, alkaline earth or ammonium salt of the urea of formula IV with an alkylating agent of the formula

in which R has the meaning given above, and X represents a "leaving group" such as chlorine, bromine, iodine, alkoxy-, alkyl- or arylsulfonyl, and furthermore represents the group (CH ₃ O-) ₂ PO-O when R ^{1 represents} methyl,
implements or c) the urea of the formula IV with an acid derivative of the formula

in which R ^{2 has} the meaning given above and T represents chlorine, bromine, iodine or the group R ² -CO-O, or d) the urea of the formula IV with an isocyanate of the formula

or with a carbamic acid halide of the formula

in what formulas R ^{3 has} the meaning given above and Y represents chlorine, bromine or iodine,
implements or e) the urea of the formula IV with a carbonic acid ester of the formula

in which R ^{4 has} the meaning given above and Z represents chlorine or the radical R ⁴ -O-CO-O,
implements;
and furthermore optionally those compounds of the formula I in which R represents R ¹ and Q represents the group CO-OR ⁵ , in that according to a further process variant f) a carboxylic acid of the formula synthesized by process b)

in which R has the meaning given above,
in the presence of an acid binder, or an alkali-earth alkali or ammonium ion, with an alkylating agent of the formula

in which X and R ^{5 have} the meaning given above,
implements. 3. Fungicidal compositions, characterized by a content of at least one ω-substituted pentylurea derivative according to claim 1. 4. A method for combating fungi, characterized in that ω-substituted pentylurea derivatives according to claim 1 are allowed to act on fungi or their habitat. 5. Use of ω-substituted pentylurea derivatives according to claim 1 for combating fungi. 6. A process for the preparation of fungicidal agents, characterized in that ω-substituted pentylurea derivatives according to claim 1 are mixed with extenders and / or surface-active agents.