DE2401388A1 - 3-THIOALLOPHANIC ACID DERIVATIVES - Google Patents

Description

Dr. Michael Hann 2401388 December 31 :. 1 ^r 73 Patent Attorney H / W

63 casting
Ludwigstrasse 67

lil

Rohm and Haas Company, Philadelphia, Pa., USA 3-THIOALLOPHANIC ACID DERIVATIVES

Priority: January 22, 1973 / USA /

Ser.Nos. 325 277 and 325 783

This invention relates to new derivatives of 3-thioallcphanoic acid. These compounds are biologically active and act as fungicides, including in particular the systemic fungicide.

These new derivatives of 3-thioallophanoic acid possess the formula

NHCIiHC-X

(I)

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in which XR ^{1 is} O- or R ¹ S-, where R ^{1 is} one of the following radicals:

a) a straight or branched alkyl radical with 1 to carbon atoms, μ

b) an alkyl radical with 1 to 12 carbon atoms substituted with halogen, preferably chlorine, or methoxy groups,

c) an alkenyl radical with 2 to 12 carbon atoms,

d) an alkynyl radical with 3 to 12 carbon atoms,

e) a phenyl radical,

f) a phenyl radical substituted by halogen, preferably chlorine, methyl methoxy or nitro,

g) a benzyl radical or

h) a benzyl radical substituted by halogen, preferably chlorine, methyl, methoxy or nitro;

Y is a heterocyclic radical with 5 or 6 cyclic atoms, the heteroatom 0, S or N or a any combination of two of these heteroatoms with up to three and by acetoxymethyl, chlorine, Methyl or nitro can be substituted; R is hydrogen or methyl;

Z is halogen, preferably chlorine, methyl, methoxy or nitro and
η is 0 to 3. .

Typical heterocyclic radicals are furyl, imidazolyl, Isothiazolyl, isoxazolyl, N-methylpyrryl,

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Oxadiazolyl, oxazolyl, pyridyl, pyrimidyl, pyrryl, thiadiazolyl, thiazolyl, thienyl, triazinyl and the triazolyl radical. Preferred heterocyclic radicals include 2-furyl, 5-isothiazolyl, 1-methylpyrryl, 2-pyridyl, 2-pyrryl, 4-thiazolyl and 2-thienyl radical a.

Among the preferred derivatives, the most preferred are those in which Y is 2-furyl or Is 2-thienyl and R is hydrogen and among these compounds are those of the formula

N = CH-I η,

^{Λ0 /} .. (II)

NHCNHC-X

HJ

to be emphasized once again.

Among the hydrocarbon radicals given in the definition of R ^ the alkyl radicals are the preferred and, among these, the lower alkyl radicals with 1 up to 6 carbon atoms, in particular methyl or ethyl.

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Not very much is known in the literature about similar compounds. There is a more recent interest in 1,2-bis (3-methoxy (or ethoxy) carbonyl-2-thioureido) benzene, which is mentioned in Belgian patent specification 722 080 and is used as a fungicide. Biologically active compounds of formula

S ΟΙ Il

NHCNHCO-alkyl

in the Z inter alia a benzylidene amino radical or its chlorine-, methoxy- or nitro-substituted Deri can be vat are known from GB-PS 1 214 415.

New derivatives according to the invention of the formula I can can be prepared by either (A) a compound of the formula

Y-C = O with a compound of the formula

NHCNHC-X. (V)

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or 0

Il

(B) with a compound of the formula XC-NCS, optionally in the presence of a basic tertiary amine, with a compound of the formula _; ,,

R.
-JY.

(VI)

implements.

In general, the compounds of formula I can be prepared by processes necessary for their preparation from analog connections are known.

Details of the two basic preparative methods, both of which start from ο-phenylenediamine, are given below:

An ο-phenylenediamine is combined with a hydrocarbyloxycarbonyl isothiocyanate to produce a 4- (2-aminophenyl) -3-thioallophanate reacted, which then with a Aldehyde or ketone with formation of the corresponding Schiff base, i.e. a 4- (2-methylenaminophenyl) -3-thioallophanate reacted. The following sequence of reactions explains these reactions. The symbols have the definition already given.

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(III)

Formula V + Y-C = O

X-C-NCS-

(IV)

Formula I.

(V)

NHCNHC-X

The isothiocyanates of Formula IV are readily obtained by known methods. One of these procedures is that a chloroformate ester with ammonium or potassium thiocyanate in the presence of an inert solvent, such as acetone, 2-methoxyethanol, ethyl acetate, butyl acetate or toluene, by heating, for example to a temperature in the range 25-100 ⁰ C, is implemented. The equation below shows a reaction with potassium thiocyanate

X-C-Cl + KSCN

Solvent "> X-CNCS

+ KCl (IV)

The isothiocyanate can be purified by distillation, but this procedure often occurs significant thermal degradation or polymerization. Therefore, crude isothiocyanate is often used from

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as identified by infrared analysis for a subsequent reaction with an amine used.

Ill

The reaction of an 'o-phenylenediamine of the formula III with an isothiocyanate of the formula IV is usually carried out with approximately equivalent amounts of the starting materials in the presence of an inert solvent such as ether, 2-methoxyethanol, ethyl acetate, butyl acetate or toluene. The implementation is progressing generally light in a temperature range from -2O ⁰ C. The 4- (2-aminophenyl) -3-thioallophanates of the formula V generally crystallize out of the reaction mixture and are purified by customary purification processes, such as recrystallization. Prolonged heating of these compounds should be avoided as it leads to formation. of a benzimidazole in the following manner

could lead.

The 4- (2-aminophenyl) -3-thioallophanates are then mixed with the heterocyclic aldehyde or ketone in the presence an inert solvent, such as an aromatic '

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table hydrocarbon, and a catalytic amount of an acid such as p-toluenesulfonic acid, reacted. The implementation is in most cases in the
Carried out at the reflux temperature of the solvent, but very often in the temperature range from 50 to
150 ^° C. Difficulties can arise with acid-sensitive aldehydes such as furfuraldehyde, and for this reason modified procedures are used which are discussed later. A typical reaction with thiophene-2-carboxaldehyde or 2-thienyl methyl ketone is given below:

(V)

NHCNHC-X

Il I S 0

N = O

NHCNHC-X

1 B-

B. Solvent

Acid, warmth

The o-phenylenediamines and the heterocyclic aldehydes and ketones are for the most part commercial products.

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Other heterocyclic aldehydes or methyl ketones can be prepared by known methods. For example, a heterocyclic ring can be converted into an aldehyde by formylation with carbon monoxide or convert hydrogen cyanide or N-methylformanilide, by reacting a halomethyl derivative with hexamethylenetetramine or using the Grignard reagent with ethoxymethylaniline, by hydrolysis of a dihalomethyl derivative or by reducing an acid halide derivative.

The following table I gives an overview of typical Compounds of formula V useful in making the compounds of the invention.

Table I.

See.
Example Zn =

X =

Formulas

Decomposition point (d) in ⁰ C literature data

1, etc.

2, etc.

9, etc.
10
11
22nd

H
H

4-CH _q
5-N (T

OCH.

ocJ

4- (or 5-) cl
4- (or 5-) CH,
4- (or 5-) OCH.
4- (or 5-) N0 _o ^:

L OcJ

OC

oh; oh;

GB-PS 1 GB-PS 1 GB-PS 1 GB-PS 1 183-185 168-170 184-185 211-212

214 415 214 415 214 415 214 415 (d) (d) (d) (d)

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- ίο -

Working method 2

An o-phenylenediamine is used with an equivalent amount • a heterocyclic aldehyde or ketone for production of an o- (methylenamino) aniline (Schiffsche Base), reacted, which afterwards with the Hydrocarbyloxy-'carbonylisothiocyanat is reacted to form a compound of formula I. The reaction sequence is given below:

(III)

Ή,

+ Y-C = O

Il

Formula VI + X-C-NCS

(IV)

Formula I.

The reaction of the o-phenylenediamine with the carbonyl compound is usually carried out in the presence of an inert solvent such as benzene or toluene. The reaction is usually carried out at the reflux temperature of the solvent, but frequently in the range from 50-150 ^° C. The reaction can be promoted by removing the water formed. As a solvent

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- li -

alcohol can be used, but in this case the reaction is carried out ^{below 0 ° C.} In most cases these Schiff bases are known compounds.

The reaction of the compounds of the formula VI with an isothxocyanate is usually carried out in the presence of an inert solvent such as ether, 2-methoxyethanol, ethyl acetate, butyl acetate or toluene. The reaction proceeds well at room temperature and a range from -20 to 100 ^° C. is considered as the temperature range for carrying out the reaction.

Other conventional methods can be used for the preparation of some of the specified intermediates will. For example, 2-aminonitrobenzene can be reacted with an isothiocyanate of the formula IV, where one compound of the formula

JSHCNHC-X

obtained, which is then reduced to a compound of formula V, for example by a metal acid Combination.

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The invention is explained in more detail in the following examples.

Example 1 ^{; i}

Preparation of methyl 4 [] 2- (furfurylideneamino) phenyl ·] -3-thioallophanate Procedure 1

To 11 g (0.049 mol) of methyl 4- (2-aminophenyl) -3-thioallophanate in 200 ml of benzene were added 5.75 g (0.06 mol) of furfural and a catalytic amount of ρ-toluenesulphonic acid. The reaction mixture is heated to reflux for 4 hours and 0.9 ml of water from the azeotropic mixture is collected in a trap. The reaction mixture is then cooled and a yellow solid is obtained which, after isolation and drying, weighs 8.1 g and has a decomposition point of 150-152 ° C. (d). This corresponds to a yield of 55% of methyl 4- [2- furfurylideneamino) pheny IJ -3-thioallophanate.

Procedure 2

A slurry of 52.4 g potassium thiocyanate (0.54 mol) in 162 g butyl acetate was heated to 50-55 ° C. 52.4 g of methyl chloroformate (0.565 mol) were added rapidly and a slight exothermic reaction was observed. The reaction mixture was ^{heated to 60 °} C. for 4 hours and 2.6 liters of carbon dioxide developed, measured by a wet test meter.

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The methoxy carbonyl ^{isothiocyanate mixture obtained was cooled to 10 °} C. and kept ready for a subsequent reaction.

To 39.2 g of o-phenylenediamine (0.362 mol) (which if necessary 2.2 g Ν, Ν-dimethylaniline were added) 37.0 g of furfural (0.385 mol) in 119 g of toluene were added. The reaction mixture was at 35 ° C for 0.5 hour heated to form a solution, which was then evacuated to a pressure of 55 mm, as 93 g of one Toluene water distillate were collected. The one left behind o- (2-Fufurylideneamino) aniline residue was cooled to ambient temperature and 3.0 g Triethylamine added.

To the above Methoxycarbonylisothiocyanatmischung of 1O ⁰ C and then 7 g of triethylamine were added the above o- (2-Furfurylidenamino) aniline slowly so that the temperature remained below 35 ° C. The reaction mixture was then stirred for one hour and then ^{cooled to 10 °} C. and the solid was filtered off. The solid was then washed with 100 ml of cold toluene and 300 ml of water and then dried ^{to 100 g of a yellow solid with a melting point of 155 156 ° C.} This corresponds to a 90% yield of methyl 4 - [_ 2- (furfurylideneamino) phenylj-3-thioallophanate.

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In GB-PS 1 214 415, example 11 describes a process for the preparation of l-benzylideneamino-2- (3-methoxycarbonyl-2-thioureidb) -benzene. It is provided that Methoxycarbonylisothiocyanat with 2-Benzylidenaminoanilin in acetone at -5 ⁰ C reacts to room temperature. · According to this method could with o- (2-Furfurylidenamino) aniline no Γ2- 4- (Fur fury Iidenamino) phenylj-3 thioallophanate can be isolated. Likewise, this product was not formed when triethylamine was omitted. The use of a base is necessary when reactions of acid-sensitive aldehydes or their Schiff bases are carried out.

Example 3

Production of ethyl 4- [2- (furfurylideneamino) phenyl-3-thiothiolallophanate

S-ethylchlorothiol format (0.2 mol) was added at room temperature to a slurry of 20 g of potassium thiocyanate (0.206 mol) in 125 ml of 2-methoxyethanol. After stirring for 3 hours, the solvent was driven off from the reaction mixture. Then 3 g of triethylamine were added and this mixture was reacted according to the procedure of Example 1 with o- (2-furfurylideneamino) aniline (0.185 mol) which contained 3 g of triethylamine. The product as the compound of Example ¹ 1 isolated and

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24.5 g of a yellow solid were obtained. In the recrystallization from benzene to give 14.3 g of yellow needles, with decomposition at 157 - 158 melted ⁰ C (d). This corresponded to a yield of 23% of ethyl 4- [j2- (furfurylideneamino) phenyl] -3-thiothiolallophanate.

• Information about the in Examples 4 to 16 and in Other compounds obtained in the examples not dealt with in the text are shown in Table II.

Example 17

Production of methyl-4 - ^ - (thenylidenamino) phenyl! -3-thioallophanate

A reaction mixture of 4.5 g of methyl 4- (2-aminophenyl) -3-thioallophanate (0.02 mol), 2.24 g of thiophene-2-carboxaldehyde (0.02 mol) and 100 ml of benzene was at reflux temperature for Stirred for 48 hours and the water was separated from the azeotropic distillate. The cooled reaction mixture was filtered, 3.5 g of a solid residue being obtained which had a decomposition temperature of 175 ^° C. (d). This corresponded to a yield of 55% of methyl 4- j_2- (thenylideneamino) phenyIj-3-thioallophanate.

Example 20

Preparation of methyl 4-r2- (thenylideneamino) -4 (or 5) -chlorophenyl-3-thioallophanate

To 10 g of 4-chloro-o-phenylenediamine (0.07 mol) in 175 ml of ether 8 g of methoxycarbonyl isothiocyanate (0.068 mol) were added

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given a temperature below 25 ⁰ C. A slurry formed which was filtered off and the solid residue became 12.3 g of a yellow solid having a melting temperature of 184-185 ° C _; , dried with decomposition. A second sample of 6.1 g was recrystallized from 2-methoxyethanol, 4.3 g of a product having a melting point of 183 to 185 ° C. being obtained. The combined products corresponded to a 92% yield of methyl 4- (2-amino-4 (or 5) -chlorophenyl) -3-thioallophanate.

To 6 g of methyl 4- (2-amino-4 (or 5) -chlorophenyl) -3-thioallophanate (0.023 mol) in 250 ml of benzene was added 2.8 g of 2-thiophenecarboxaldehyde (0.025 mol), which was 0.2 g contained p-toluenesulfonic acid, given. The reaction mixture was refluxed for 6 hours and water was separated from the azeotropic mixture. The solvent was removed leaving an orange-brown residue which was digested with ether to give 4 g of an orange-yellow solid which melted with decomposition at 173-175 ° C (d). Analysis indicated that the product was a mixture so it was further reacted with 3 g of 2-thiophenecarboxylic aldehyde as outlined above. The product was isolated as above and 3.3 g of an orange-yellow solid were obtained which ^{melted at 183 to 184 °} C. (d) with decomposition. This corresponded to a 41% yield of methyl 4- [2- (thenylideneamino) -4- (or 5) -chlorophenylj-3-thioallophanate.

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Example 21

Preparation of methyl 4- £ 2- (thenylideneamino) -4 (or 5) -chlorophenyl -3-thioallophanate _; To a mixture of 9.5 g of 4-chloro-o-phenylenediamine (0.067 mol) in 250 ml of benzene was added 7.5 g of 2-thiophenecarboxaldehyde (0.067 mol). The mixture was refluxed for 3 hours. Half of its volume was then stripped off, 25 ml of hexane was added and the mixture was cooled to give an oil. The oil was separated and concentrated; but it was found that it was a mixture. It was heated to reflux temperature for two hours with a further 2.5 g of 2-thiophenecarboxaldehyde and then cooled, a solid being formed which, after isolation and drying, weighed 4.1 g. 3.2 g of an oily solid were isolated from the filtrate. The solids were combined and recrystallized from hexane / ether (50:50) to give 5.2 g of a solid having a melting point of 69-70 ⁰ C were obtained. This corresponds to a 33% yield of 2-thenylideneamino-4 (or 5) -chloroaniline.

To 4 g of 2-thenylideneamino-4 (or 5) chloroaniline (0.017 mol) in 120 ml of ether were added 2 g of methoxycarbonyl isothiocyanate (0.017 mol) was added and the mixture was stirred at room temperature for one hour. The received yellow solid was filtered off, washed with ether

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and dried to give 1.8 g of a solid ν obtained which with decomposition at 143-144 ⁰ C melted (d). This corresponded to a yield of 30% of methyl 4 - [_ 2- (thenylideneamino) -4 (or 5) chlorophenyl-3-thioallophanate.

Example 23

Preparation of methyl 4- r2 - (^ - methyl-2-thenylideneamino) -phenyl-3-thioallophanate

A reaction mixture of 15 g of o-phenylenediamine (0.139 mol), 19 g of 2-acetylthiophene (0.151 mol) and 200 ml of benzene was heated to reflux temperature for 56 hours, the water formed being separated off. The solvent was removed and a yellow solid was obtained as a residue. This residue was treated with _v hexane and then from benzene / hexane (1: 1) to give 15.4 g of 2- (methyl-2-thenylidenamino) aniline was obtained.

To a solution of 5 g of 2- (ed-methyl-2-thenylideneamino) aniline (0.0232 mol) in 175 ml of ether was added dropwise 3 g of methoxycarbonyl isothiocyanate (0.0256 mol) at a Temperature in the range of 24 - 28 ° C added. The yellow solution obtained was freed from the solvent, whereby an oily solid was obtained. This solid was treated with cold ether and then filtered off

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trated to give 2 g of a with decomposition at 126 - 127 ⁰ C remained melting solid. This corresponds to a yield of 26% of methyl 4 - [_ 2 - (* 1-methyl-2-theny1idenamino) phenylj-3-thioal1ophanate.

Example 24

Preparation of methyl 4-r2- (2-pyrrolylmethyleneamino) -phenylj -3-thioallophanate

A solution of 15 g ο-phenylenediamine (0.139 mol) in 45 ml of methanol was cooled to -10 ⁰ C. A solution of 13.2 g of pyrrole-2-carboxaldehyde (0.139 mol) in 45 ml of methanol was added to this solution at a temperature below -5 ° C. The reaction mixture was cooled to less than -5 ° C for 0.5 hour during which time a yellow precipitate formed. The solid was filtered off to give 10.5 g of this solid were obtained, which at 106 - 108 ⁰ C melted. After further standing still 12.4 g solids separated from the filtrate with a melting point from 106 to 108 ⁰ C from. The combined solids corresponded to an 89% yield of 2- (2-pyrrolylmethyleneamino) aniline.

To a solution of 5 g of 2- (2-pyrrolylmethyleneamino) aniline (0.027 mol) in 175 ml of ether was added 3.7 g Methoxycarbonyl isothiocyanate (0.315 mol) was added and the mixture was stirred for one hour. The received Solid was filtered off and yielded 5.1 g of a yellow

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Solid dried, decomposed at 178 -. 179 ° C melted. This corresponded to a yield of 63% of methyl 4- [2- (2-pyrrolylmethyleneamino) phenylj-3-thioallophanate. ^il1

Example 25

Preparation of methyl 4- {l-. (1-methyl-2-pyrrolylmethyleneamino) phenyl] -3-thioallophanate A mixture of 10 g of ο-phenylenediamine (0.0926 mol), 10.1 g of N-methylpyrrole-2-carboxaldehyde (0.0926 mol) and 175 ml of benzene were heated to boiling under reflux cooling for one hour, the water formed being separated off. The mixture was then separated from the solvent and a dark oil remained as a residue. This oil was treated twice with 100 ml of hot hexane and the extracts of the hot hexane gave 10.2 g of a yellow oil on cooling. This oil was dissolved in 100 ml of ether, which would correspond to 0.05 moles of 2- (1-methyl-2-pyrrolylmethylamino) aniline if it were pure. 70 ml of this solution (0.035 mol) was reacted with 5 g of methoxycarbonyl isothiocyanate (0.043 mol) to give a solid. 4.1 g of this solid, which melted at 155-157 ° C., were obtained and it was found that it was a mixture of the desired product with methyl 4- (2-aminophenyl) -3-thioallophanate. 3.8 g of this solid were in 175 ml of benzene, the 0.1 g of p-toluene

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containing sulfonic acid, suspended and further reacted with 3 g of N-methylpyrrole-2-carboxaldehyde (0.095 mol) while heating to reflux for 3 hours. The reaction mixture was _; ,, Then treated in the warm with charcoal for 0.5 hour, filtered off and the solvent was driven off from the filtrate, an oily solid remaining. This was treated with ether, 2.4 g of a solid having a melting point of 171 to 172 ^° C. (with decomposition) being obtained. This corresponded to a yield of 22% of methyl 4- [2- (1-methyl-2-pyrrolylmethyleneamino) phenyl -3-thioallophanate.

Example 26

Preparation of methyl 4- [2- (5-isothiazolylmethyleneamino) phenyl-3-thioallophanate

A reaction mixture of 9.4 g of o-phenylenediamine (0.0867 mol), 9.8 g of 5-isothiazole carboxaldehyde (0.0867 mol) and 80 ml of benzene was heated to reflux temperature for two hours, the water of reaction being separated off. The solvent was removed and a red-orange oily residue was obtained. This residue was treated with 100 ml of cooled ether / hexane (1: 1) to give 9.1 g of a red-orange solid became. It was confirmed to be 2- (5-isothiazolylmethyleneamino) aniline by infrared analysis, which was obtained in 52% yield.

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3.5 g of methoxycarbonyl isothiocyanate were added to a solution of 5 g of 2- (5-isothiazolylmethyleneamino) aniline (0.0246 mol) in 100 ml of ether (0.03 mol) was added and the mixture was stirred for one hour. A red-orange fell Solid, which was filtered off and, after drying, 3.5 g of one which melts at 176-177 ° C. with decomposition Solid. It was 4-L2- (5-isothiazolylmethyleneamino) phenylJ-3-thioallophanate, which was obtained in 46% yield.

Example 27

Preparation of methyl 4- [2- (2-pyridy! Methylenamino) phenyl -3-thioallophanate

A reaction mixture of 7.1 g of methyl 4- (2-aminophenyl) -3-thioallophanate (0.0316 mol), 3.7 g of 2-pyridinecarboxaldehyde (0.0346 mol), 0.2 g of p-toluenesulfonic acid and 250 ml of benzene was refluxed for 3 hours. On cooling it turned a dark yellow solid by-product was obtained which was filtered off and weighed 3.2 g. The filtrate was treated with 150 ml of hexane, 4.3 g of a purple-colored solid were obtained which melted at 144-145 ° C. with decomposition. It was methyl 4 - [_ 2-pyridy lme thy lenamino) -phenyIJ-3-thioallophanate, which was obtained in 43% yield.

Tables II, III, IV and V give the identity of the typical compounds made and their physical and analytical values.

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Table II

.general formula

example

1 OCH ₃ H H (or 5) -Cl 2 OC ₂ H ₅ H H (or 5) -CH 3 SC ₂ H ₅ H H (or 5) -OC 4th OC ₄ H ₉ -U H H 5-Cl ₂ 5 OC ₈ H _l7 -n H H 6th 00, H-
D D H H 7th OCH ₃ CH ₃ H 8th OCH ₃ CH ₃ C (O) OCH ₂ H 9 OCH ₃ H 4th 10 OCH ₃ H 4th 11 OCH ₃ H 4th 12th OCH ₃ H 4, 13th OCH ₃ NO ₂ H 14th OCH ₂ CCl ₃ H H 15th OCH ₂ CH = CH ₂ H H 16 OCHC ₆ H ₅ H H

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Table III

general formula

example R. X W. Z * 5) -Cl 17th H OCH ₃ H H 5) -Cl 18th H OC ₂ H ₅ H H 5) -N0 ₂ 19th H OCH ₃ Cl H 20th H OCH ₃ H 4th (or 21 H OCH ₃ H 4th (or 22nd H OCH ₃ H 4th (or 23 CH "■ OCH " H H

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Table IV

N = CHY NHCNHCOOCH ..

Ill

general formula

example

0-

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Tabel V 155-6 (d) ^C 14 ^H 13 ^N 3 ° 3 ^S C. Analysis **
H · N 13.9 (13.8) 0 S. • 10.5) 113-115 (d) C ₁₅ H ₁₅ N ₃ O ₃ S 55.5 (55.3) 4.3 (4.4) 13.3 (13.1) 15.9 (16.0) 10.6 ( 9.8) Example melting point empirical
oc (d) * formula 157-158 (d) ^C 15 ^H 15 ^N 3 ° 2 ^S 2 56.9 (57.2) 4.8 (4.8) 12.6 (12.7) 15.1 (15.2) 10.1 ( 19.3) 1 122-124 (d) C ₁₇ H ₁₉ N ₃ O ₃ S 54.0 (54.0) 4.5 (4.7) 12.2 (12.1) 9.6 (10.1) 19.2 ( 9.4) 2 84-85 (d) Λ * ti M Γ \ Ο
\ j [J. Λ "-J IN Λ V / Λ O 59.2 (58.9) 5.6 (5.9) 10.4 (10.5) 13.9 (14.1) 9.3 ( 8.0) 3 172-173 (d) ^C 19 ^H 15 ^N 3 ° 3 ^S 62.4 (62.8) 6.6 (6.3) 11.5 (11.8) 12.2 (12.0) 8, K 8.2) 4th 127-128 (d) ^C 15 ^H 15 ^N 3 ° 3 ^S 62.5 (62.7) 4.1 (4.2) 13.2 (13.3) 13.1 (13.3) 8.2 ( 10.0) 5 149-150 56.8 (57.4) 4.8 (4.8) 11.2 (11.2) 15.2 (15.6) 10.1 ( 8.5) O 6th 188-189 ^C 14 ^H 12 ^C1N 3 ° 2 ^S 54.4 (54.3) 4.5 (4.6) 12.5 (12.2) 21.3 (21.6) 8.6 ( 9.5) +0 co
00 "7 168-169 (d) C ₁₅ H ₁₅ N ₃ O ₃ S 49.6 (49.6) 3.6 (3.5) 13.3 (13.1) 14.3 (14.6) 9.5 ( 9.8) * " O . -8th 163-164 (d) ^C 15 ^H 15 ^N 3 ° 4 ^S 56.8 (57.0) 4.8 (4.9) 12.6 (12.5) 15.2 (15.1) 10, K 9.6) _l ^ 9 202-203 ^C 14 ^H 8 ^C1 2 ^N 3 ° 3 ^S 54.0 (54.4) 4.6 (4.7) 11.4 (11.2), 19.2 (19.3) 9.6 ( 8.8) 10 206-208 (d) ^C 14 ^H 12 ^N 4 ° 5 ^S 45.5 (45.6) 2.1 (2.7) 16.1 (16.0) 13.2 (13.2) 8.6 ( 8.9) uv 11 166-167 (d) C _n -H ₁ , Cl ₀ N ₀ O ₀ S 48.2 (48.6) 3.5 (3.4) 10.0 (9.8) 23.0 (22.9) 9.2 ( 7.9) 12th 42.8 (43.0) 2.9 (3.0) 11.4 (11.4) 7.6 ( 13th 14th

Table V (continued)

CJ
CD
OO
Approx
CD

Melting point Empirical C. Analysis ** H N 0 S. 8.9 (8.7) At- . ⁰ C (d) * formula (8.5) game i08-110 (d) ^C 16 ^H 15 ^N 3 ° 3 ^S 58.3 (58.3) 5.2 (4.6) 12.9 (12.8) 15.0 (14.6) 15th 161-162 (d) ^C 20 ^H 17 ^N 3 ° 3 ^S 62.0 (63.1) 4.5 (4.5) 10.7 (11.1) 13.0 (12.7) 19.2 (19.3) 16 163-165 (d) ^C 14 ^H 13 ^N 3 ° 2 ^S 2 52.7 (52.4) 4.1 (4.2) 13.2 (13.2) 18.1 (18.0) 17th 136-137 (d) ^C 15 ^H 15 ^N 3 ° 2 ^S 2 54.1 (53.1) 4.5 (4.4) 12.6 (12.8) 9.6 (10.0) 18.1 (18.0) 18th 149-151 (d) C ₁₄ H ₁₂ ClN ₃ O ₂ S ₂ 47.7 (47.5) 3.4 (3.5) 11.9 (11.8) 9, K 9.3) 18.1 (17.7) 19th 183-184 (d) C ₁₄ H ₁₂ ClN ₃ O ₂ S ₂ 47.6 (47.6) 3.4 (3.5) 11.9 (11.4) 9.0 (9.9) ti 20th 143-144 (d) ^C 14 ^H 12 ^C1N 3 ° 2 ^S 2 47.7 (47.6) 3.4 (3.1) 11.9 (11.7) 9.0 (9.7) 19.3 (19.4) 21 203-204 (d) ^C 14 ^H 12 ^N 4 ° 4 ^S 2 · 46.2 (45.7) 3.3 (3.6) 15.4 (15.5) 17.6 (17.7) 10.6 (10.5) 22nd 126-127 (d) ^C 15 ^H 15 ^N 3 ° 2 ^S 2 54.0 (54.0) 4.5 (4.5) 12.6 (12.5) 9.6 (9.9) 10.0 (10.0) 23 178-179 (d) C ₁₄ H ₁₄ N ₄ O ₂ S 55.7 (56.2) 4.7 (4.4) ' 18.5 (19.0) 10.6 (10.6) 20.0 (19.8) 24 171-172 (d) ^C 15 ^H 16 ^N 4 ° 2 ^S 57.0 (57.2) 5.1 (5.0) 17.8 (17.4) 10.0 (10.6) 10.2 (10.5) 25th 176-177 (d), 48.7 (48.9) 3.8 (3.9) 17.5 (17.4) 10.0 (9.8) 26th 144-145 (d) ^C 15 ^H 14 ^N 4 ° 2 ^S 57.3 (57.0) 4.5 (4.5) 17.9 (17.8) - 10.2 (10.1) 27

* Melts with decomposition

** The number in brackets is based on the empirical formula
calculated theoretical value

GO CX) CX)

The invention also provides a particularly preferred process for the preparation of compounds

N = CH

NHCNHOX

tt Il

S O

(VII)

available, where in this formula X, Z and η have the meaning already given and W is hydrogen, acetoxymethyl, Is chlorine, methyl or nitro. In this particularly preferred mode of operation, a compound is the formula

i = CH
^l 2

(VIII)

It

reacted with an isothiocyanate of the formula SCN-C-X, where W, X, Z and η are as defined above and the reaction takes place in the presence of an organic base in the manner of a tertiary amine.

409830 / 1H5.

- 29 -

The o-furfurylideneaminoanilines (formula VIII) are in described in the literature, see for example Chemical Abstracts _61, 8280b and 1486Of (1964) and j> 7_, 11629m (1967). It is obtained through implementation of an o-phenylenediamine with an equivalent amount of a furfuraldehyde, optionally in the presence of a tertiary amine, according to the following equation

OCH " ¹

X ₀ / -W ^ formula (VIII)

in which W, Z and η have the above meaning. The reaction is usually carried out in the presence of an inert solvent such as benzene or toluene. The reaction is carried out in most cases at the reflux temperature of the solvent, but can often be in the temperature range from 50 to 150 ⁰ C to work. Alcohol can be used as · solvent, but the reaction is carried in such a case at einer'Temperatur of 0 ⁰ C or lower before. The reaction is promoted by removing the water of reaction to the extent that it is formed. The presence of a tertiary base, such as triethyl

409830/1 U5

amine or Dime thy lamin sometimes acts as a Stabilizing agent, but it is not necessary to work in the presence of a tertiary base.

The tertiary amine compounds which may be used have, as a rule, an ionization constant in the range of 5 ICT χ χ ³ to 5 10 ^-5 at 25 ° C. Typical tertiary amines are trimethylamine, triethylamine, tripropylamine, triisobutylamine, methyldiethylamine, tetramethylethylenediamine, N, N-dimethylethanolamine and dimethylaniline. Preferred tertiary amine compounds are triethylamine and tripropylamine. The amount of amine used is usually in the range from 0.5 to 20 mol%. In the case of triethylamine with a molecular weight of 101, this means about 0.5 to about 20 g per mole of the starting materials. Preferably about 5 to 15 mol% are used. The amine can be added to or divided between the o-furfurylideneaminoaniline starting materials or the hydrocarbyloxycarbonyl isothiocyanate starting material.

The reaction of o-furfurylideneaminoaniline of the formula VIII with an isothiocyanate in the presence of a tertiary amine (RN) is usually carried out in an inert solvent such as ether, 2-methoxyethanol, ethyl acetate, butyl acetate or toluene. The starting materials can be used in equimolar amounts, but an excess of isothiocyanate of up to 100%, preferably in the range of 20-40%, is often used.

4098 30/1145

The reaction proceeds readily and proceeds in a temperature range from -20 ⁰ C up progressing well. The 4-f_2- (Furfurylidenamino) phenylj-3-thioallophanates of the "formula III crystallize out of the reaction mixture as a rule and are purified by simple procedures such as recrystallization. Excessive heating of these compounds should be avoided because they can lead to the formation of a benzimidazole. The following equation shows the reaction sequence:

SCN-C-X

R ₃ N

(VIII)

N = CH

NH-C-NHC-X

It Il

S 0

(VII)

The need for a tertiary amine, such as triethylamine, to be present during the reaction of compounds of the formula VIII was made by the following experiments

demonstrated.

409830/1145

A.

Known procedure for the preparation of 4-J_2- (Benzylidenamino) phenylJ-3-thioallophanate In GB-PS 1 214 415 it is stated on page 2 that the following reaction is used to prepare alkyl 4 - [_ 2- (benzylideneamino) phenyIJ-3-thioallophanate to manufacture:

.N = R ₄

SCN-COR

Il

NHCNHCOR

Il Il

S 0

In these formulas, X is hydrogen, chlorine, or nitro

Methyl,

R is an alkyl radical with 1 to 4 carbon atoms and

R, a benzal radical or one substituted by chlorine, nitro or methoxy Benzal residue.

In the patent it is stated that the reaction in an inert organic solvent, such as acetone, Ethyl acetate, methyl ethyl ketone, methanol, ethanol, dioxane,

409830/1145

Benzene or toluene at a temperature of -20 to 50 ⁰ C, preferably -10 to 30 ⁰ C, normally in a period of 10 minutes to one hour, occasionally but can also be carried out in a few hours. No further details are given.

A typical reaction of this type was carried out as follows: to 15 g ο-phenylenediamine (0.139 moles) of benzaldehyde in toluene (0.142 mol) were added at 80 ⁰ C 15 g. The reaction mixture was slowly ^{distilled at about 80 °} C. in order to remove the solvent and the water and to concentrate the mixture, 40 g of o-benzylideneaminoaniline being obtained as residue (solution A).

19.8 g of methyl chloroformate (0.21 mol) were added at 45 ° C. to 20.2 g of potassium thiocyanate (0.21 mol) in 75 ml of ethyl acetate. The resulting slurry was stirred for 2 hours at 45 ° C and then cooled to 10 ⁰ C. There was obtained a slurry of Methoxycarbonylisothiocyanat, slowly added to the solution A prepared in advance was added at 35 ⁰ C. The reaction mixture was then stirred for one hour. The solid precipitate obtained was filtered off, washed with water and dried. 24.5 g of methyl 4-jj2- (benzylideneamino) .phenyl-3-thioallophanate with a melting point of 142 to 144 ° C. were obtained in a yield of 55%. It follows that the general method of operation of GB-PS 1 214 415 for the production of this type of ship

409830/1145

shear base of a benzaldehyde is useful.

Unsuccessful attempts to produce 4-j_2- (furfurylideneamino) phenyl-3-thioallophanate according to the teaching
GB-PS 1 214 415
Procedure 1

There were 30.0 g of o-phenylenediamine (0.278 mol) in 365 ml of toluene was heated to 60 ⁰ C under vacuum until the toluene
began to boil. 28.0 grams of furfural (0.292 moles) was then added over 15 minutes and the toluene and water were distilled off until 81.5 grams of one
concentrated toluene solution of the product remained (solution B).

To 40.5 g of potassium thiocyanate (0.419 mol) in 150 ml of ethyl acetate were added at 45 ⁰ C 40.5 g of methyl chloroformate (0.428
Mole) given quickly. The reaction mixture was for
Stirred for 2 hours at 45 ° C and then cooled to 10 ⁰ C. This is the methoxycarbonyl isothiocyanate starting material.

To this cold methoxycarbonyl isothiocyanate solution
solution B was slowly added at less than 35 ° C. The contents of the reaction vessel became very
dark. The reaction mixture was at for one hour
Stirred at ambient temperature and then cooled ^{to 10 ° C.} A solid separated out and was filtered off, washed with ether, suspended in 300 ml of water and

409830/1 145

was then dried to 50.2 g. A 5 g sample of this product was washed with hot gasoline and then dried to give an impure solid was obtained, "the with decomposition at 135-136 ⁰ C, melted The product was identified by its infrared spectrum as l, 2-bis- (3rd methoxycarbonyl-2-thioureido) benzene

NHC (S) NHCOOCH ₃ MC (S) NHCOOCH ₃

identified, see Belgian patent specification 722 080.

Procedure 2

To 30 g of o-phenylenediamine (0.278 mol) were dissolved in 325 ml methanol was added dropwise at 0 ⁰ C 28 g added furfural (0.292 mol). The reaction mixture was ^{stirred at 0} ° C. for one hour and then it was concentrated at ambient temperature to give 82.7 g of an oily concentrate (solution C).

To 40.5 g of potassium thiocyanate (0.417 mol) in 110 ml of acetone was added 39.8 g of methyl chloroformate (0.417 mol). The reaction mixture was stirred under heating and reflux for 0.5 hours and then cooled to 0 ⁰ C. This is the methoxycarbonyl isothiocyanate starting material.

40 98 30/1145

Solution C was slowly added at 0 ^{° C. to this methoxycarbonyl isothiocyanate suspension.} After the addition was complete, the reaction mixture was allowed to warm to room temperature over 0.5 hour. Then 732 ml of water were added and a tarry residue separated out. All attempts to isolate a characterizable product from this organic residue failed.

Successful attempts to produce 4 - {_ 2- (furfury-1idenamino) phenyIJ -3-thioalophanate process 1

5 g of N, N-dimethylaniline (0.04 mol) and 56 g of furfural (0.58 mol) ^{were added at 35 °} C. to 60 g of o-phenylenediamine (0.56 mol) in 500 ml of toluene. The toluene and water were distilled off at 35 ° C. under a vacuum of 50 mm until 150.3 g of a concentrated toluene solution remained. To this solution, 4 g of triethylamine (0.04 mol) was added and then the solution was allowed to cool to ambient temperature (solution D).

To 81 g of potassium thiocyanate (0.835 mol), which were slurried in 300 ml of butyl acetate at 6O ⁰ C, was added 81 g of methyl chloroformate (0.86 mol) rapidly. The reaction mixture formed a yellow slurry and it was ^{stirred at 60 °} C. for 2 hours. The product was ^{cooled to 10 °} C. and 2 g of triethylamine (0.02 mol) were added. This is the methoxycarbonyl isocyanate source. 409830 / 1US

Solution D was added to this cooled methoxycarbonyl isothiocyanate solution at less than 35 ° C. The reaction mixture was stirred for one hour and then ^{cooled to 10 °} C., a solid precipitating out. The solid was separated by filtration, slurried in 600 ml of water and dried to obtain 151.5 g of a product having a melting point 154-155 ⁰ C were obtained. This product was found by analysis to contain 54.6% C, 4.2% H and 14.0% N; the calculated values for C ₁₇ H ₁₀ N ₀ O ₀ S are 55.3% C, 4.4% H

14 13 3 3 · ' ⁷

and 13.8% N. The product obtained in 90% yield is 4- [_2- (furfurylideneamino) phenyl] -3-thioallophanate. Its structure was confirmed by its infrared spectrum. It contained some potassium chloride as an impurity.

Procedure 2

To 30 g ο-phenylenediamine (0.278 mol) in 325 ml toluene at 60 ⁰ C, was added 28 g of furfural (0.292 mol).

The Toluolwassermischung mm was distilled off at 60 ⁰ C and at a vacuum of 130 until a residue of 55 g remained. To this residue were 2 g of triethyl

amine (0.02 mol) given (solution E).

To 40.5 g of potassium thiocyanate (0.417 mol) suspended in 150 ml of ethyl acetate, 40.5 g of methyl chloroformate (0.429 mol) were quickly added at 45 ° C. This reaction mixture was stirred for 2 hours at 45 ° C and then cooled to 10 ⁰ C. This is the starting methoxycarbonyl isothiocyanate

^fabric * 409830/1145

To this methoxycarbonyl isothiocyanate slurry, 4 g of triethylamine (0.04 mol) was added and then solution E was added at less than 35 ° C. over 15 minutes. After stirring for one hour, the solid was filtered off, washed with 300 ml of water and dried. 57.3 g of a product with a melting point of 154-155 ° C. were obtained. Analysis of this product found 55.3% C, 4.3% H and 13.7% N; the calculated values for C ₁₇ H ₁₀ N ₀ O ₀ S are 55.4% C, 4.3% H

14 13 3 3 ⁷ '

and 13.85% N. The product obtained is

is 4 - [^ 2- (Furfurylidenamino) phenyl] -3-thioallophanate,

which was obtained in a yield of 68%.

In the following Table V A the structure of similar 4- [_2- (furfurylideneamino) phenyl] -3-thioallophanates which were produced according to the successful method according to C and identified as in Example 28.

Table II above gives the decomposition or Melting points and analytical values of compounds obtained after the successful method according to C were manufactured.

409830/1145

The 4- (2-methylenaminophenyl) -3-thioallophanate according to of the invention are excellent fungicides. They are particularly useful for combating phytopathogenic fungi, belonging to the groups of Ascomycetes and Fungi Imperfecti, effective. The following types of phytopathogenic Fungi are examples of types of fungi that can be controlled with the products according to the invention: Acanthorhynchus; Acanthostigma; Acremonium; Acrostalagmusj Ascospora; Aspergillus, e.g., A. oryzae, A. repens, and A. terreus; Botryosphaeria; Botryosporium; Botrytis, e.g. B. cinerea; Calonectria; Calosphaeria; Cenengium; Cephalosporium; Cephalothecium; Ceratostomella; Cerospora, e.g., C. apii; Cercosporella; Claviceps; Cleistothecopsis; Coccomyces; Cryptosporella; Dasyschypha; Diaporthe; Didymaria; Didymellina; Didymospoeria; Dothidella; Endothia; Epichloe; Erysiphe, e.g., E. gram-inis and E. polygoni; Fabraea; Fusidium; Gibberella; Gloeosporium, e.g., G. aridum, G. fagi, G. musarum, and G. quercinum; Glomerella, e.g. G. cingulata and G. gossypii; Gnomonia; Guignardia; Herpotrichia; Hyalodema; Hypoderma; Hypodermella; Hypoxylon; Keithia ;. Leptosphaeria; Lophodermium; Meliola; Microsphaera; Monilia; Monilinia, e.g., M. fructicola; Mycogons; Mycosphaerella; Nectria, e.g., N. episphaeria; Neofabraea; Neopeckia; Nummullaria; Oidiopsis; Oidium; Oospora ;. Ophiobolus; Penicillium, e.g. P. diversum, P. funiculosum, P. italicum, "P. ' oxalicum and P. vernaculosum; Phabdocline; Phacidiella; Phyllactinia; Phyllachora; Physalospora; Piricularia, e.g., P. oryzae; Plectodiscella; Pleosphaerulina; Pleospora; Plowrightia; Podospaera; ·

409830 / 114B

Pseudopeziza; Pyrenopeziza; Pyrenophora; Quularia; Ramularia; Rhytisma; Rosellinia; Rhizina; Sclerotinia, e.g., S. sclerotiorium; Septocylindriumj Sphaerotheca, e.g., S. fuliginea; Spherulina; Sterigmatqcystis; Taphrina; Thielavia; Titea; Trochila; Tricholadia; Trichosphoeria; Uncinula; Ustilaginoidea; Valsa; Venturia; Verticillium, e.g. V. albo-atrum.

These 4- (2-methylenaminophenyl) -3-thioallophanates exhibit a high degree of systemic fungicidal activity, which means that these fungicides are able to protect a plant against attack by fungi both internally and externally. A discussion of the possible mode of action of systemic fungicides can be found in "World Review of Pest Control" 2 (3), · 1963, where examples of this effect with phenylthio semicarbazides are given. Explanations of systemic fungicides in the decade following this article can be found in "PANS" 18_ (1), 1972. This article deals with the properties of systemic fungicides, including benzimidazoles and related compounds such as certain 3-thioallophanates.

The fungicides according to the invention can be added to the seeds, the plants or the soil. As systemic Fungicides, they are especially effective when applied as floor sprays.

409830 / 114S '

To test these compounds as fungicides, a preliminary test was first carried out in which the compounds at 300 ppm were used and the plants were sprayed so that a carrier nerve of etx ^ a 1400 Liters / ha (150 gallons / A) drained. The spray solution or suspension was prepared by weighing a Amount of the fungicide under consideration was dissolved in a 50:50 mixture of acetone and methanol and then added the same volume of water.

The general procedure for the fungicide tests was to keep potted plants in the correct State of growth for susceptibility to to test plant disease were selected on one moving tape and then allowed to dry. The right plants were then matched with the appropriate Inoculated fungal spores and then allowed to incubate until symptoms of disease developed. It was then measured or estimated the effectiveness of the control. The percentage of effectiveness of the fight was expressed by the following system of letters:

A = 97 - 100% control B = 90 - 96% control C = 70 - 89% control D = 50 - 70% control E = ineffective, <C 50% control

A09830 / 1U5

Table VI gives an overview of the plants and plant diseases used in this study. Table VII shows the effectiveness of the control in the preliminary test. _; ,,

409830/1145

Table VI (continued)

PRE-CHECK OF PLANT DISEASE NGEN- to Fungal disease
(Inoculation, spores ml) Plant (age) Incubation
(Time and temperature) O
CO
OO
OO 1. Botrytis burn
Botrytis cinerea . , .S ₁
Faba bean (10 days)
Vicia faba 3 days
(26.7 to 27.8 ⁰ C) (150,000)
2. Bean powder meltau
Erysiphe polygoni Dwarf bean (2 weeks)
• Phöseolus vulgaris 10 days
(Surroundings) 1983Oi (10-25,000)
3. Rice burn
Piricularia oryzae Rice (2 weeks)
Oryza sativa 1 day * + 5-8 days
(26.7 - 27.8 ° C) cn (10-25 000)
4. Tomato late brandy
Phytophthora infestans Tomato (3 weeks)
Lycopersicum esculentum 1.5-2 days (12.8 ° C)
2 - 3 days (21.1 ° C) (50-60,000)
5. Soft grape melt dew
Plasmopora viticola Grape seedling (3-4 leaves
Vitis vinifera stage) 2 days (21.1 ⁰ C) *
4 days (surroundings) (150,000)
6. Barley Helminthosporium
Helminthosphorium teres Barley (6 days)
Hordeum vulgar 1 day (21.1 ⁰ C) *
1 day (26.7 ⁰ C)
3-4 days (23.9 ° C) (10-15,000)

Table VI

PREVIEW OF PLANT DISEASES "·

Fungal disease (budding, spores ml)

Plant (age)

Incubation

(Time and temperature)

. . 7th Cercospora fire
Cercospora apii 4 » (25,000) 098 8th. Wheat leaf rust
Puccinia recondita 30 / (60,000) 1145

Celery (6-8 weeks

Transplanted)
Apium graveοlen s

Wheat (6 days)
Triticum vulgar

1 day (26.7 ⁰ C) * 14 - 18 days (surrounding area)

1 day (21,

6-8 days (surrounding area)

* high humidity

CO OO OO

Table VII

CD OO CJ

WEATHER KSAMK EIT D ER B E K Ä M P FUNG AT 3 0 0 . PPM Ver
search B.
cinerea E.
polygoni P.
oryzae P.
infestans P.
viticola H.
teres C.
apii P.
recondita

1 A. A. A. E. 2 A. A. E. E. 3 A. A. A. E. 4th A. A. B. E. 5 E. B. E. - 6th A. A. B. E. 7th A. A. Ά E. 8th A. A. B. E. 9 D. • A E. E. 10 A. A. B. E. 11 B. A. B. E. 12th E. C. E. E. 13th B. A. A. E. 14th • A A. A. E. 17th A. A. B. E.

E. A. D. E. - B. E. - C. E. - D. E - E. E. - E. E. - B. E. - C. E. - D. E. - D. E. - D. E. - E. E. - E. E. - C. E. D.

• Ρ-Ln

CD

CO 00 OO

Table VII (continued)

Ver B. E. P. P. P. H. C. P. search cinerea polygoni oryzae infestans viticola teres apii recondita 18th B. A. B. E. E. D. 19th A. A. B. E. - E. C. 20th B. A. E. E. - E. B. 21 D. A. E. E. E. D. O 22nd C. E. E. E. E. E. co 00 23 B. A. C. E. E. E. A. co O 24 B. A. B. E. E. E. D. "" ν 25th A. A. C. E. - E. A. 26th B. A. A. E. E. E. D. 27 B. A. C. E. _ E. C.

CO OO OO

Using some of these tests typical of the invention, secondary and special tests were performed, which are described below. '"'

A. Dosage-Response Studies

1. Bean powder meltau (Erysiphe polygoni)

A known amount of the fungicide to be tested was dissolved in acetone and washed with deionized water, containing 0.05 ml of an emulsifier per 100 ml of water, diluted. The emulsifier was a modified phthalic glyceral alkyd resin. The concentration was adjusted to 25 ppm and this basic solution was subsequently Double the volumes diluted so that after a few dilutions a concentration of 1.5 ppm is reached became. There were horticultural kidney bean seedlings with the differently concentrated solutions until they drained off (drip-off) sprayed using two replicates per treatment. The bean plants were allowed to dry for 20 hours and then polygoni with a spore suspension of Erysiphe inoculated with 2 × 10 ^ · spores per ml. The inoculated Plants and control plants were then kept in a greenhouse at 23.9-26.7 ° C for 10 days. It was the number of meltau damage was then counted and the effectiveness of the control was determined according to the following formula calculated:

409830 / 1US

Effectiveness of the fight

- 48 -

Damage control plants -

Damage treated plants χ 100

Damage control plants

The results are shown in Table VIII.

A09830 / 1U6

Table VII I. Dosing Reactic
Bean powder melti , 5 98 , 4 the fight
6.2 3.1 , 6 96 ,1 msStudy effectiveness
25th ■ 12.5 , 9 95 , 3 94 , 6 36 , 6 IU Ver
search 100 , 7 98 , 4 86 ,1 85 , 5 in % at
1.5 ppm t-l 99 63 , 9 83 »7 34, , 0 95.7 2 97 0 29 0 0 3 91 100 0 "95, »5 - 4th 0 "8th 100 100 , 4 92, ,1 - 6th 100 , 3 86 ,8th 98 ,8th 0 7th 100 75 , 9 68, , 3 39 ,8th 8th 9S ₁ , 6 94, , 9 30, ,8th 49, , 3 ' _ 9 87 85 > o 96, ,1 0 0 10 100 98 ,8th 82, 7th 92, 7th _ 11 91 98 , 0 95 3 78 Λ 12th 100 2 100 79 96, 2 17th 100 8th 96, , 2 100 7th 80, 5 91.5 18th 100 6th 87 , 5 86 6th 0 Λ 0 19th 95 0 62, 0 _ 20th 94, 100 0 96, 8th _m 21 91 100 · 100 • 94, 3 22nd 100 100 100 1 96, 2 M. 23 100 0 100 98 8th 97 7th 24 100 98 5 98 0 79 8th 25th 100 95 26th 99 89.7 27 53.7

4 09-830 / 1141

2. Cucumber powder dew

Cucumber seedlings which had two well-developed primary leaves and a third small primary leaf were sprayed with various concentrations of methyl 4- \ 2- (furfurylideneamino) phenyl 3-thioallophanate (Example 1) until they drained off. The leaves of the plants were then allowed to dry for a few hours and then inoculated with a spore suspension of Sphaerotheca fuliginea containing about 2 × 10 ^ "ascospores per ml , 7 ° C. Eleven days after application of the fungicide, the disease had developed enough to be determined and the effectiveness of the fungicide to be determined.

% Control Efficacy for Compound 50 25 12.5 6.3 3.1 1.6 ppm

Example 1 100 100 99.6 97.9 94.3 72.5

B. Remaining effectiveness after weathering

In order to determine the effectiveness of the fungicides of the invention after weathering, some test plants after the application of the chemicals subjected to a simulated rain from a height of 2.54 cm before they have been inoculated with the phytopathogenic fungal spores.

The results compiled in Table IX were found for various plant diseases.

409830 / 1UB

Table IX

CD CX) CaJ O

fin

Weathering Studies on example (17) with various diseases g / 100 liters) 60
^ Rain
without with Level of Fungicides ( 30th
rain
without with A A illness 7.5
rain
without with 15th
rain
without with AWAY A 'A Botrytis at
Faba - bean B E B C A A B C Meltau bean powder AWAY AWAY B E B A Rice brandy C E C E B A -. - Cucumber powder rme1tau B A • B A _ ■ _ -. Celery Cerospora A A A A Meltau wheat powder C B B A

Cn

ΓΟ CD

OO OO GO

C. Systemic examinations upon ingestion by the root

1.Rice brandy (Piricularia oryzae)

Rice seedlings 2.5 to 7.5 cm high were grown in 7.5 cm plastic pots. The compound of Example 17 was dissolved in acetone: methanol: water in a ratio of 1: 1: 2 and then the concentration was adjusted so that 15 ml of the spray solution contained a predetermined dose in ppm. This solution was used to provide the plants with water by watering the soil. The treated rice seedlings were maintained under standard greenhouse conditions at about 27 ⁰ C. They were then inoculated with P. Oryzae spores and the effectiveness was determined after 6 days. The following results were obtained:

Example ppm in soil pouring water% effectiveness of

Combat

17 150 91.7

300 98.0

2. Cucumber powder meltau (Sphaerotheca fuliginea)

There were cucumber seedlings with well-developed leaves grown in 7.5 cm plastic pots with 15 ecm of a solution which contained different amounts (in ppm) of the compound of Example 17 were watered. the

409830/1 U5

- "53 -

Seedlings were then spread over the leaf portion with a spore suspension of S. fuliginea (the 2 χ 10 ^ · ascospores per ml) inoculated. The inoculated plants were immediately placed in a temperature greenhouse from 29 to 32 ° C and were periodically examined for the occurrence of the disease. It became the following Get results:

Example ppm in Bodengxesswasser Effectiveness of the control - 6 weeks after Pouring the soil

125 250 500

E.
E.
A.

As another assessment of the duration of systemic activity the plants used in the weathering test according to Part B, Table IX, were kept and periodically on the Examination of the formation of powdered cucumber dew. The following observations were made:

example

Weeks after application of the fungicide

Minimum effective concentration in ppm to control> 50% melt dew to surrender without rain / with rain

3
4th
5

150 150 300

<75 600 600

409830 / 1U5

The compounds according to the invention give at low levels Dosages a good control of the plant diseases under consideration over 5 weeks after application on the leaf apparatus or dur., ch soaking the soil.

3. Wheat powder meltau (Erysiphe graminis)

I "

a. by soil soaking

The soil of 5 to 7 day old wheat plants which had grown in plastic pots to a height of 3.5 to 5 cm was soaked with 15 ml of an aqueous solution containing the compound of Example 17 as a typical compound according to the invention. The plants were then placed in a greenhouse at about 24 ^° C. for two days and then inoculated by sprinkling the spores of wheat plants infected with powder meltau over them. Disease incidence was checked 6 days after inoculation. The following results were obtained:

Example effectiveness of the fight at. 10 ppm 20 ppm

17 -C- C control (E)

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b. by treating the semen

Wheat seeds were treated with different dosages of the compound of Example 17 by treating 40 g of wheat in a pot with one ml of acetone and 0.5 ml of water and the amount of the fungicide that 31.7, 62.5, 125 or 250 g / 100 kg of the fungicide were present. The treated seeds were planted in the soil in 6.25 cm pots using 4 replicates per treatment. The pots were placed in a greenhouse at 21 - 24 ⁰ C, where, until the seedlings had a height of about 5 cm reached. The plants were then inoculated using a spore suspension of E. graminis containing about 30,000 spores / ml. The plants were dried and placed in a greenhouse at 21-24 ° C so that the disease could develop. 17 days after planting, the proportion of diseased plants was determined and the effectiveness of the control of the disease was determined with the following results:

Effectiveness of the fight treatment 31.7 g 62.5 g. 125 g 250 g / 100 kg

Example 17 C D D C Control (E)

D. Extinction Attempts

Cucumber seedlings were at the two-leaf stage of development with a spore suspension from Sphaerotheca

409 8 ^; 30 / 1U5

fuliginea, which is about 2 χ 10. Contained ascospores per ml, inoculated. 48 hours later, the plants were given a series of doses of various test compounds. sprayed. 10 days later, the proportion of diseased plants was determined by the existing damage and the eradicated plants compared to the number of damage in untreated plants were determined. The following results were obtained:

Treatment ppm over leaf applied-% eradication applied fungicide

100 100 100 100 100 100 0

E. Control of fruit rot in storage, such as nectar brown rot (monilinia fructicola), by dipping after harvest

For an evaluation for the immersion application, partially ripe nectarines were injured by striking and immediately immersed in a 300 or 600 ppm solution of the test compound, dissolved in acetone: methanol: water in a ratio of 1: 1: 2. The fruit was dried at room temperature and then with a suspension of 30 10 ^J spores of

^ 09830/1145

example 1 25th 12.5. 6.3 example 17th 25th 12.5 6.3 untreated

Monilinia fructicola inoculated. Then the fruit became stored at 24.4 or 14.4 ° C until a brown-red appeared on the treated fruits. It became the following Effect of control observed: u

% Disease

At- Chemical 24.4 ° C a 14.4 ⁰ C 14.4 ⁰ C game dive ppm week after a two

Inoculation week weeks

1 300 1.4 ' 0 0 - 600 1.6 0 0 Con
trolls 4.0 4.0 23.0

F. Comparison with known fungicides

Some comparisons have been made between the connection of Example 1 of this invention and compounds known from GB-PS 1,214. The following will be some representative results are given:

1. Comparison of rice brandy (Piricularia oryzae)

Rice seedlings were made by application over the leaf with the compounds under consideration at different concentrations, which are given in ppm, treated and then inoculated with the rice burn disease in the manner already indicated.

Direct comparisons were made with the following compounds of GB-PS 1 214 415:

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Connection name

A 1-Benzylideneamino ~ 2- (3-methoxycarbonyl-2-thioureido) -benzene

¹ B 1- (4-chlorobenzylideneamino) -2- (3-methoxycarbonyl-2-thioureido) benzene

C 1- (4-methoxybenzylideneamino) -2- (3-methoxy carbonyl-2-thioureido) benzene

D 1- (3-Nitrobenzylideneamino-2- (3-ethoxycarbonyl-2-thio ^ reido) benzene

The following results were obtained:

Control effectiveness upon treatment 1200 600 300 150 75 37.5 ppm

example 1 A. A. A. A. B. B. Connection A. C. D. E. Έ E E. Connection B. C. D. D. E. E. E. Connection C. A. B. B. D. E. E. Connection D. B. C. D. E. E. E. untreated (E)

2. Experiments across the inhibition zone with different Fungal organisms

There were 20 ecm of potato dextrose agar (KDA) in a 9 .cm plastic plate given. Of those in question Fungicides, solutions of various concentrations were made. One 6.35 mm antibiotic disc was dipped in each solution and then placed in the center of the agar plate. At opposite Sides on the edges of the petri plate were mycelia

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mats of some mushrooms are placed on the surface of the agar. The plates were then kept under such conditions that the growth of the respective organism was promoted. After 3 to 6 days, the growth was determined and the zone of inhibition was measured. The following index was used to identify the inhibition:
+++ strong

ι "

++ massive + weak - none

There were comparisons with the compounds of GB-PS 1 214 415, that is, the compounds. A - D, such as previously specified, carried out. In Table XI the results are given:

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Table XI

Inhibition of fungal growth

Treatment ppm in Aspergillus Fusarium Sclerotinia Zythia

Trial disc terreus roseum sclerotiorum pinastria

"Culmorum"

example 1 1000 500 250 125 OO Comparison A 1000 οα
O 500 250 125 Comparison B 1000 500 250

CO OO OO

Table XI (continued)

Inhibition of fungal growth

Treatment ppm in Aspergillus Fusarium Sclerotinia Zythia

Trial disc terreus roseum sclerotiorum pinastria

"Culmorum"

comparison C. 1000 500 * ·> 250 CD CO
OO comparison D. 1000 CO
O 500 ** - 250

CO CO OO

G. Influence of fungicide application on fermentation of grape juice

• It is desirable that one used on grapes Fungicid does not affect the fermentation rate of the grape juice in winemaking.

A related study was therefore carried out on the influence of the compound of Example 17 in comparison * with the well-known fungicide N-trichloromethylthiophthalimide carried out. A fermentation medium consisting of 3785 ml of grape juice and 454 g Glucose consisted. This fermentation medium was divided into aliquots of 200 ecm and placed in 0.47 liter pots, which contained sufficient quantities of the fungicides under consideration and dissolved in acetone: water (1: 1: 2), that 5 ppm and 20 ppm dilutions of the fungicide were present. One ml of a yeast suspension (Saccromyces cerevisiae), which contained 3 10 'cells per ml Each sample was added and the pots were closed with a cork containing a glass tube and "Tygon" tubing contained. The free end of the tubing was inserted into an inverted 150 ecm Shell introduced. The carbon dioxide evolved displaced the water in the bowl and the time was measured to form 125 ml of CO «. The following results were achieved:

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Table XII

Fungicide

ppm hours required to form 125 ml of CO _n

Example 17 5
20th

Commercial prod. 5
20th

control

<24

<24

> 120

> 120

<24

The compounds of the invention show no phytotoxicity when sprayed on plants at doses in which excellent control of phytopathogenic fungi is achieved.

None of these compounds shows any insecticidal or acaricidal activity, so that no damage to beneficial insects through these compounds is to be expected.

The compounds according to the invention are anthelmintic Effect. For example, they are good for combating pinworms and Aspicularis tetraptera Syphacia obvelata suitable.

The 4- (2-methylenaminophenyl) -3-thioallophanates of the invention are very effective agricultural fungicides and can be applied in various ways, for example on the seeds, in the soil or via the foliage.

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In general, these fungicides are used to protect agricultural crops or other plants used in the desired type of application and in effective amounts. . ,,

The 3-thioallophanates can be used as fungicides in technical or in neat form or as a formulation such as solutions. In this context the invention also provides a method for producing a fungicidal preparation, in which one or more compounds of the formula I with one or more additives, as are customary used for formulations of fungicides, mixed.

The compounds of the invention are usually from a diluent, which is generally a Carriers are included or they are formulated so that they can be used for later distribution or dissemination are suitable as pesticides. For example, these thioallophanates can be used as wettable powders, emulsifiable Concentrates, powdered preparations, granular formulations, aerosols or flowable emulsion concentrates are formulated. With such formulations the compounds are stretched with a liquid or solid carrier and, if appropriate, become suitable surfactants incorporated.

409830/1 US

In general, and especially when used for spraying the foliar apparatus, it is advantageous that the formulations auxiliaries, such as emulsifiers, wetting agents, • spreading agents, dispersants, adhesives, adhesives and the like in accordance with general agricultural practice. Such Aids are known and are described, for example, in the publication by John W. McCutcheon, Inc. "Detergents and Emulsifiers "1971 Annual.

In general, the compounds of the invention have somewhat limited solubility, but they can in certain solvents such as dimethylformamide, pyridine or dimethyl sulfoxide and diluted these with water Solvents are dissolved. The concentration of the solution can vary between 2 to 50%, with a range from 5 to 25% is preferred.

For the production of the emulsifiable concentrates can the compounds in a suitable organic solvent or a mixture of such solvents together with an emulsifier, which enables the pesticide to be dispersed in water. the The concentration of the active ingredient in emulsifiable concentrates is usually 10 to 25% and for flowable emulsion concentrates up to about 75%. ■

A wettable powder suitable for spraying can be prepared by mixing the compound with a finely divided powder

409830/1 1 45

Solid, such as clay, inorganic silicates and carbonates or silica mixes and wetting agents, adhesives and / or dispersants are incorporated into such mixtures. The concentration of the active ingredients is in Such formulations generally range from 20 to 98%, preferably from 40 to 75%. A typical one wettable powder is obtained by adding 50 parts of the compound of Example 1, 4-5 parts of a synthetic precipitated hydrated silica (Hi-SiI vR) and Mixes 5 parts of a commercially available sodium lignosulfonate (Mar asper seVjy N-22). With a different formulation becomes a kaolin clay (bard) in place of the synthetic silica in the wettable powder was used and yet another formulation was 25% of the synthetic silica by a synthetic sodium silicoaluminate (Zeolex®7) replaced.

Dust-like preparations are obtained by mixing the 3-thioallophanates with finely divided inert solids, which can be organic or inorganic in nature, mixes. Suitable materials of this type are botanical Flours, silicon dioxide, silicates, carbonates and clays. A convenient way of working for making a such dust consists in diluting a wettable powder with a finely divided carrier. Usually Powdered concentrates containing 20 to 80% active ingredients are produced and afterwards for use at a concentration of 1 to

10% diluted.

409830/1 145

The 3-thioallophanates can be used as fungicides by usual Methods are used, such as by spraying of various kinds (high-gallonage hydraulic sprays, low gallonage sprays), by air pressure atomized sprays and sprays and powdery preparations in the atmosphere. The dilution and dosage when using depends on the type of device used, the method of application and the diseases to be controlled, yes the effective amount is typically from about 0.11 to 27 kg / ha (0.1 lb to 25 lbs. per acre) of active ingredient.

As a seed protection agent, the amount of fungicide applied to the seed is usually one dose from about 6 g to 1.25 kg per 100 kg of seeds. When used in seeds, the fungicide can be incorporated into the soil or applied to its surface, with dosages from 0.11 to 27 kg / ha be used. As a foliar fungicide, the growing plant at a dose of 0.27 to 11 kg / ha.

Fungicides with the fungicides according to this invention, in particular with each of the individual fungicides according to the Examples 1 to 43, which can be combined, include the following fungicides:

409830/1 US

a) Dithiocarbamates and their derivatives such as iron (III) dimethyldithiocarbamate, Zinkditnethyldithiocarbamat, Manganäthylenbisdithiocarbamat and its coordination product with zinc ion, zinc ethylene bisdithiocarbamate, Zinc propylene bisdithiocarbamate, sodium methyldithiocarbamate, Tetramethylthiuram disulfide, Complex of zinc ethylene bisdithiocarbamate and polyethylene diuram disulfide,

3,5-dimethyl-1,3,5-2H-tetrahydrothiadiazin-2-thione and Mixtures of these fungicides among themselves and mixtures

with copper salts;

b) nitrophenol derivatives such as
Dinitro (1-methylheptyl) phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethyl acrylate, and 2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate;

c) heterocyclic compounds such as N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthiophthalimide, 2-heptadecyl-2-imidazoline acetate, 2-Octylisottiiazolon-3, 2,4-dichloro-6- (o-chloroaniline) -s-triazine, Diethyl phthalimidophosphorothioate, 4-butyl-l, 2,4-triazole,

5-Amino-1-JJfc> .is (dimethylamino) phosphinyl-3-phenyl-1,2,4-triazole,

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S-ethoxy-S-trichloromethyl-l ^^ - thiadiazole, 2,3-dicyano-1,4-dithiaanthraquinone,

2-thio-1,3-dithio- [4,5-b] quinoxaline,

Methyl l- (butylcarbamoyl) -2-benziipidazole carbamate,

2- (4'-thiazolyl) benzimidazole,

4- (2-chlorophenylhydrazono) -3-raethyl-5-isoxazolone,

Pyridine-2-thiol-1-oxide, 8-hydroxyquinolinic acid and its metal salts,

2,3-Dihydro-5-carboxanilido-6-methyl-1,4-oxathiine-4,4-dioxide,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine,

<* - (Phenyl) -o ^ - (2,4-dichlorophenyl) -5-pyrimidinylmethanol,

cis-N- [l, l, 2,2-tetrachloroethyl) thio] -4-cyclohexene-1,2 * dicarboximide,

3- Γ2- (3,5-dimethyl-2-oxycyclohexyl-2-hydroxy-glutarimide, Dehydroacetic acid,

N- (l, l, 2,2-tetrachloroethylthio) -3a, 4,7,7a-tetrahydrophthalimide,

5-butyl-2-ethylamino-4-hydroxy-6-methylpyrimidine, 4-cyclododecyl-2,6-dimethylacetate and morpholine and
6-methyl-2-oxo-1,3-dithiolo (4,5-b) -quinoxaline;

d) various halogenated fungicides such as tetrachloro-p-benzoquinone, 2,3-dichloro-1,4-naphthoquinone, 1,4-dichloro-2,5-dimethoxybenzene, 3,5,6-trichloro-o-anisic acid, 2,4,5, fj-tetrachloroisophthalonitrile, 2,6-dichloro-4-nitroaniline,

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2-chloro-1-nitropropane, polychlomitrobenzenes such as pentachloronitrobenzene and tetrafluorodichloroacetone _tll

e) fungicidal antibiotics such as griseofulvin,
Kasugamycin and streptomycin;

f) copper-based fungicides such as copper-I-oxide,

basic copper (II) chloride, basic copper carbonate, copper naphthenate and Bordeaux mixture; and

g) various fungicides such as diphenyl,

Dodecylguanidine acetate, phenyl mercury acetate,

. N-ethylmercury-1,2,3-, 6-tetrahydro-3,6-endomethane-3,4,5,6,7,7-hexachlorophthalimide,

Phenylquecks ilb ermonoethano lammoniumlac tat, p-dimethylaminobenzene diazo sodium sulfonate, Me thy1i sοthiacyanat, l-thiocyano-2,4-dinitrobenzene 1-phenylthiosemicarbazide, Nickel compounds, calcium cyanamide,

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Sulphurous limestone, Sulfur and 1,2-bis (3-methoxycarbonyl-2-thioureido) benzene.

1.1

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Claims (34)

Patent claims: 1. Compound of formula R N = C-Y __L -NHCNHC-X, - in which XR ^{1 is} O- or R ¹ S and R ¹ a) a straight-chain or branched alkyl radical with 1 to 12 carbon atoms, b) an alkyl radical with 1 to 12 carbon atoms substituted by halogen or methoxy groups, c) an alkenyl radical with 2 to 12 carbon atoms, d) an alkynyl radical with 3 to 12 carbon atoms, e) a phenyl radical, f) a phenyl radical substituted by halogen, methyl, methoxy or nitro groups, g) a benzyl radical or h) is a benzyl radical substituted by halogen, methyl, methoxy or nitro groups; 409830/114 Y is a heterocyclic radical with 5 or 6 members, the heteroatom 0, S or N or a
Combination of two or more of these heteroatoms and a total of up to 3 Hejteroatomen, the heterocyclic radical through
Acetoxymethyl, chlorine, methyl or nitro groups can be substituted; R is hydrogen or a methyl radical; Z is halogen, methyl, methoxy or nitro and η is 0 to 3. 2. Compound according to claim 1, characterized in that R is hydrogen. 3. A compound according to claim 1, characterized in that XR ^{1 is} O-, where R ^{1 is} an alkyl radical having 1 to 12 carbon atoms. 4. A compound according to claim 1, characterized in that XR ^{1 is} O-, where R ^{1 is} an alkyl radical having 1 to 6 carbon atoms. 5. A compound according to claim 1, characterized in that R is hydrogen and X is a methoxy group. 409830/1 U5 6. A compound according to claim 1, characterized in that Y is a 2-furyl, 5-isothiazolyl, 1-methylpyrryl, 2-pyridyl, 2-pyrryl, 4-thiazolyl or 2-thienyl radical is. ί.ι 7. A compound according to claim 6, characterized in that R is hydrogen. 8. A compound according to claim 7, characterized in that X in the formula Γ R ¹ O-, where R ^{1 is} an Alk ^ lrest with 1 to 12 carbon atoms. 9. A compound according to claim 7, characterized in that XR ^{1 is} O-, where R ^{1 is} an alkyl radical having 1 to 6 carbon atoms. 10. A compound according to claim 7, characterized in that X is a methoxy group. 11. The compound methyl 4- | _2- (furfurylideneamino) phenyIj-3-thioallophanate. 12. The compound methyl 4- | _2- (thenylideneamino) phenyl-3-thioallophanate. 409830/1145 13. Process for the preparation of the compound of formula xr N = CH NHGNHC-X ti It S O ¹ w characterized in that a compound of the formula with a compound of the formula 0 SCN-C-X in the presence of a solvent and 0.5 to 20 mol% of a tertiary amine which has an ionization _{constant in the range from 5 χ 10 -3 to} 5 _x χο ~ ⁵ at 25 ° C, where in this formula X, Z and η have the same meaning as in claim 1 and W is hydrogen, acetoxymethyl, chlorine, methyl or nitro. 409830/1 U5 14. The method according to claim 13, characterized in that it is used for the preparation of the compound of the formula VII, in which W is hydrogen, is used. 15. The method according to claim 13, characterized in that that it is used for the preparation of the compound of formula VII in which η is 0. 16. The method according to claim 13, characterized in that it is used for the preparation of the compound of the formula VII, in which W is hydrogen and η 0, is used. 17. The method according to claim 13, characterized in that that it is used for the preparation of a compound of formula VII in which X is methoxy. 18. The method according to claim 13, characterized in that it is used for the preparation of a compound of the formula VII in which X is ethoxy. 19. The method according to claim 13, characterized in that it is used for the preparation of the compound 4-j_2- (furfurylideneamino) phenylj-3-thioallophanate
will. 20. The method according to any one of claims 13 to 19, characterized in that the tertiary amine is triethylamine is used, 409830/1145 21. Fungicidal formulation, characterized in that it contains one or more compounds of the formula I according to claim 1 and at least one in fungicidal Preparations contains usual excipients. 22. Formulation according to claim 21, characterized in that the excipient is a (1) Solvent for the compound (s) of the formula I, (2) solid diluent, (3) emulsifier, (4) adhesive, (5) dispersants, (6) wetting agent or a (7) is a means of spreading. 23. Formulation according to claim 22, characterized in that that it is an emulsifiable concentrate in water, with a solvent and an emulsifying agent as an auxiliary available. 24. Formulation according to claim 22, characterized in that it is a wettable powder and as excipients contains a finely divided solid and a wetting agent. 25. Formulation according to claim 22, characterized in that it is a powdery composition and contains a finely divided solid as an aid. A09830 / 1145 26. Formulation according to one of claims 22 to 24, characterized in that the compound (s) of the formula I is or are _{one or more compounds according to claims 2 to 10 UnCl 1 12.} 27. Formulation according to one of claims 22 to 24, characterized in that the compound (s) of the formula I methyl 4-Γ2- (furfurylideneamino) phenylJ-3-thioallophanate is or are or contains or contains. 28. Method of controlling phytopathogenic fungi in a place where arable crops exist or arise, characterized in that one gives this place a fungicidally active Amount of at least one of the compounds according to claim 1 supplies. 29. The method according to claim 28, characterized in that the fungi belong to the group of Ascomycetes. 30. The method according to claim 28, characterized in that the mushrooms belong to the group of the Fungi Imperfecti. 409830/1145 31. Methods of controlling phytopathogens Mushrooms according to one of claims 28 to 30, characterized in that the fungicide is a compound of Formula '... K = CH-Y KHCNHC-X Il 1! in which X is a methoxy group and Y has the meaning defined in claim 1. 32. The method according to claim 31, characterized in that Y is a 2-furyl, 5-isothiazolyl, 1-methylpyrryl, 2-pyridyl, 2-pyrryl, 4-thiazolyl or 2-thienyl group is. 33. The method according to any one of claims 29 to 31, characterized in that the fungicide methyl-4-Q2- (furfurylideneamino) phenyI ^ Is -3-thioal1ophanate. 34. The method according to any one of claims 29 to 34, characterized in that the fungicidal compound used for soaking the soil or treating the seed. 409830 / 1U5