DE2345801A1 - PYRIDINIUM SALT - Google Patents

Description

PATENT LAWYERS

DR. - ING. H . F 1 NC Κ Ε. ----... ^ ₁ orp ιη -? ^

Dl PL.-I N G. H. B O r-R ..-:.:. ' ' ear. L - /. ·

DIPL.-ING. S, STAEGLR

Folder 9665 - Dr, K / by Case IMS-Phillips-1

COMMONWEALTH SCIENTIFIC AIiD INDUSTRIAL

ORGANIZATION

Campbell / Australia

Pyridinium salts

Priority: 11.9-72 - Australia

The invention relates to new pyridinium salts which Have useful fungicidal properties & uf processes for the preparation of these salts and to methods and compositions for controlling the growth of fungi.

The invention particularly relates to new pyridinium salts the general formula

wherein

Y stands for a hydrogen or halogen atom, in particular one

Chlorine or bromine atom ;

ΒΑΓ ^ 409813/1154

R stands for a straight-chain or branched-chain, substituted one or unsubstituted alkyl group, in particular an alkyl group with 1 to 12 carbon atoms and very particularly for an alkyl group having 5-10 carbon atoms; a substituted or unsubstituted cycloalkyl group, in particular a cycloalkyl group having 5 to 10 carbon atoms; or an aralkyl group, especially a benzyl or phenethyl group;

R 'represents a hydrogen or halogen atom, in particular a chlorine or bromine atom; a sulfonate group; an azido group; a group of the formula -NH-SO ₂ -RvI (where R ^ is a substituted or unsubstituted aryl group or a straight or branched chain, substituted or unsubstituted alkyl group); a group of the formula -SCN (lower alkyl) ₂ ; a group of the formula -CH (CN) -R ₂

S.
(where R _{2 is} -COOH, -COO (lower alkyl) or -NII-CO-NH ₉ )

or a group of the formula -NH-R ", -S-R" or -0-R "(where R" is a hydrogen atom, a substituted or unsubstixed, straight-chain or branched-chain alkyl, alkenyl or alkynyl group, a substituted or unsubstituted one Aryl or aralkyl group or a cyano group) stent; and

A for an anion, especially a chloride or bromide ion, stands.

Typical substituents included in the alkyl, alkenyl, alkynyl, Cycloalkyl, aryl or aralkyl groups are introduced are halogen groups, especially chlorine or bromine groups and nitro, lower alkoxy, pyridyl, carboxyl or furyl groups.

It can be seen that when R ^{1 represents} a sulfonate group (-S0, ^e ) in the above general formula, the anion Α ^β is absent .

It is clear to one skilled in the art that by removing a proton from a compound, the

40 9 8 f. 3 ^ 1 1 "5

general formula I a conjugated Iii.inba.se Ia is formed .

Yes

It is also clear that when R ^{1 is} a group of the formula -XH, in which X is -S- or -0-, a base Ib is formed by removal of a proton, as indicated below.

H . R · HR

CX., _T , G

₂ N XH K, N V>:

R R Ib

Since these compounds can be used either in the form of the salt or in the form of the base, references are intended to compounds of the general formula I are understood in such a way that both the salt and the base are meant.

Typical compounds of the general formula I are those in which Y stands for a hydrogen ^{atom, R 1 stands} for a chlorine atom and R for an n-butyl, isobutyl, n-hexyl, cyclohexyl, n-heptyl, n- Octyl or n-nonyl group. In addition, those compounds should be mentioned in which Y stands for a Brornaton, R, 'stands for a chlorine atom and R stands for an n-hexyl or n-octyl group. Other typical compounds are mentioned in the following examples.

0 9 8 13/1154 ^{BAD mmmL}

The compounds according to the invention in which Y is a hydrogen atom, R ^{1 is} a halogen atom and R is as defined above, can be prepared by reacting an N-substituted cyanoacetamide of the formula II with a phosphorus halide or phosphorus oxyhalide under known reaction conditions converts, whereby a compound of the formula III is formed:

(ID

A (HD

A typical procedure uses the N-substituted cyanoacetamide dissolved in an organic solvent such as chloroform, followed by phosphorus oxychloride to dissolve is admitted. The reaction mixture is then refluxed on a steam bath for approximately 2 hours. before then the product is collected and recrystallized.

k -

4098 13/1154 BAD R

The compounds of the formula III can then be in the 3-position are halogenated and / or the 6-Halogenüubstituönt can then be replaced with other radicals represented by R 'using known techniques so that other compounds of general formula I are obtained. Typical procedures are in the following Examples given.

It was found that the compounds according to the invention have broad antifungal activity and that the above-mentioned typical compounds are completely effective at 1 inhibit spore germination of Monolinia fructicola up to 100 ppm, an infection of Phytophthora cinnamoini in lupine seeds at a concentration of 1-8 ppm fight and infection by Fusarium oxynporum Tomato seedlings and by Rhlzoctonia solani in Baui ^ wollsämlingen prevent if they are introduced into the soil in an amount of θ kg / ha.

The invention therefore also relates to a method for combating fungal infestation in plants, and much thereby it is stated that the fungi, the plants, the soil or the plant seeds with an effective amount a compound of formula I treated.

The amount of the compound of general formula I, which for Achieving the desired control when carrying out the method according to the invention is necessary, can easily can be determined by simple experiment, for example, quantities of specific compounds included in this general Formula drop and which can be used to control the growth of fungi mentioned earlier.

According to the invention, compositions for The control of the growth of fungi proposed using an inert carrier and an effective amount of a compound of the general formula I. The compositions of the invention can be either liquid or solid

- 5 409813/1154 '

JJjS ₁ IiT

be as you wish. The exact wording can be used accordingly the method of application, the desired or necessary degree of control and the type of fungus to be controlled can be changed. The most beneficial compositions for The control of specific fungi can easily be carried out by a person skilled in the art based on routine experiments considering the teachings of the present invention and the various factors identified above.

The compositions can be formulated with solid inert carriers such as finely divided talc or silica to make powder compositions. she can also be formulated with vermiculites or the like, in which case granular compositions are obtained. Alternatively, liquid inert carriers, such as vegetable or mineral oils, can be used to make spray compositions to manufacture. Furthermore, the compositions according to the invention can, in addition to the compounds of the general formula la and, in addition to an inert carrier, contain other active components that make up the formulation and facilitate the use of the compositions such as emulsifiers, dispersants and wetting agents.

An example of the manner in which the compounds according to the invention are used is formulation into a composition for spraying Bauai wool plants before harvest. A compound of the invention is incorporated into a known spray composition which also contains a defoliant, and containing the composition, both ak tive agents can then be sprayed umwollpflanzen on B &, and to achieve a protection against fungi simultaneously to defoliate the plants.

The invention is illustrated in more detail by the following examples.

- 6 -4 0 9,813 / 1154 "

example 1

9.8 g (0.1 mol) of N-methyl-cyanoacetamide was dissolved in 50 ml of chloroform, and then 15.3 g (0.1 col) of phosphorus oxychloride was added. The reaction mixture was refluxed on a steam bath for 2 hours, during which time the product 2-amino-6-chloro-5-cyano-1-rαethyl--4-methylamino-pyridinium chloride (compound 1 of T & b. 1) crystallized out. It was collected and recrystallized from methanol to give 9.4 g (80 %) of a pale yellow solid. Mp 250 ⁰ C, C 41.51 (41.21); H 4.26 (4.32); N 24.11 (24.03); Cl 30.3 (30.4).

Higher homologs in this series were soluble in chloroform and were made by removing the solvent in vacuo and isolated by treating the residue with cold methanol.

Other compounds of formula III in which Hai stands for chlorine and R has the meaning given in Table 1 below, were prepared in a similar manner.

Examples 2 to 6 illustrate the halogenation of compounds of the formula III in the 3-position and the substitution in the 6-position.

Example 2

3.37 g (0.01 mol) of 2-amino-6-chloro-5-cyano-1-n-hexyl-4-nhexylamino-pyridinium chloride (compound II of Tab. 1) were dissolved in methanol, and then 1.0 g (0.01 mol) of triethylamine and 0.8 g (0.011 mol) of n-butylamine were added. The solution was refluxed for 1 hour, and after cooling 2.5 g (60 % yield) of 2-amino-6-n-butylamino-5-cyano-1-n-hexyl-4-n-hexylamino- pyridinium chloride (compound 42 from Tab. 2). Mp 179-180 ° C; G 64.88 (64.6); H 9.81 (9.78); K 17.11 (17.1).

- 7 409813/1154

Other derivatives using similar Veise other pyridinium salts and andtror amines and amides are given in Tab. 2.

Example 3

3.2 g (0.01 mol) of S-amino-in-butyl- ^ n-butylamino-S-chloro- -5-cyano-pyridinium chloride (compound 6 from Tab. 1) were dissolved in hot water, and then 1.5 g (0.012 mol) of sodium sulfite was added. After cooling, 2.8 g (85 % yield) of 2-amino-1-n-butyl-4-n-butylamino-S-cyano-pyridinium-betaine-δ-sulfonate (compound 60 from Tab. 3) crystallized out and were filtered off. Mp 240 to 245 ⁰ C with decomposition; C 51.31 (51.51); H 6.76 (6.79); N 16.70 (17.17); S 9.9 (9.8).

Other derivatives made in a similar way (it could be aqueous alcohol in the case of less water soluble ones Starting materials are used) are given in Tab. 3.

Example 4

^ »85 g (0.01 mol) of 2-amino-6-chloro-5-cyano-1-n-decyl-4-n- decylamino-pyridinium-chlorld (compound 16 from Tab. 1) were suspended in water , and then 1.8 g (0.012 mol) of bromine was added to the rapidly stirring suspension, which was heated on a water bath for 30 minutes. After cooling, 4.5 g (75 % yield) of 2-amino-3-bromo-ö-chloro-S-cyano-in-decyl ^ -n-decylamino-pyridinium bromide (compound 70 from Tab. 4) filtered off and recrystallized from Ätha nol. Mp 166-168 ⁰ C; C 51.62 (51.27); H 7.31 (7.40); N 9.20 (9.20).

Other derivatives that were prepared in a similar manner are listed in Tab.

Example 5

(a) 2.3 g (0.01 mol) 2-A2iino-6-chloro-5-cyano-1-methyl-4-

- 8 - ■
40981 3/1154

methylamino-pyridinium chloride (compound 1 of Table 1) were dissolved in water, and then 0.92 g (0.01 mol) of thioglycolic acid and 2.0 g (0.02 mol) of triethylamine were added. After 30 minutes, 1.5 g (60 % yield) of 2-amino-5-cyano-1-methyl-4-methylamino-pyridinium-betaine-6-thioglycolate (compound 74 from Tab. 5) were filtered off. Fp> 240 ⁰ C.

(b) 3.15 g (0.01 mol) of 2-amino-1-n-butyl-4-n-butylamino-6- chloro-5-cyano-pyridinium chloride (compound 6 from Tab. 1), 1.24 g (0.01 mol) of benzyl mercaptan and 1.0 g (0.01 mol) of triethylamine were dissolved in dimethylformamide and ^{heated to 100 °} C. for 1 hour. The dimethylformamide was evaporated, ethanol was added and 2.0 g (50 % yield) of 2-amino-6-benzylmercapto-1-n-butyl- ^ -n-butylamino-S-cyano-pyridinium chloride (compound 75 of Tab. 5), which was recrystallized from methanol. Fp 145-147 ⁰ C.

(c) 4.5 g (0.01 mol) of 2-amino-6-chloro-5-cyano-1-n-octyl--4-n-octylamino-pyridinium chloride (compound 14 from Table 1) were dissolved in dimethylformamide, and then 2.2 g (0.01 mol) of sodium diethyldithiocarbamate were added, whereupon the solution was refluxed for 60 minutes. The solution was cooled and filtered, after which the solvent was evaporated. Methanol was added, and then 1.6 g (30 % yield) of 2-amino-5-cyano-δ-diethylthiocarbamylthio-yn-octyl-n-octylaminopyridinium chloride (compound 80 from Tab. 5) were filtered off and off Recrystallized methanol. Mp 124-126 ⁰ C.

(d) 3.7 g (0.01 mol) of 2-amino-6-chloΓO-5-cyano-1-n-hexyl- -4-n-hexylamino-pyridinium chloride (compound 11 from Tab. 1) were dissolved in ethanol, and then 1.1 g (0.01 mol) of thiophenol and 1.0 g (0.01 mol) of triethylamine were added. The solution was left to stand at room temperature for 16 hours left and poured into ice-cold water, whereupon

- 9 409813/1154 '

then 2.3 g (50 % yield) of 2-amino-5-cya: no-1-n-hexyl-4-n-hexylamino-6-phonylmercaptopyridinium chloride (compound 78 from Tab. 5) were filtered off. Mp 227-228 ° C.

Analogous compounds were made by similar- procedures, as described in Examples 5 (a), (b), (c) and (d). They are listed in Tab. 5.

Example 6

(A) 3.2 g (0.01 mol) of a-amino-in-butyl- ^ n-butylamino-e- -chloro-5-cyano-pyridinium chloride (compound 6 from Tab. 1) were in hot water dissolved, 4.0 g (0.04 mol) of triethylamine was added and the solution was refluxed on a boiling water bath. After 2 hours, 2.0 g (75 % yield) of 2-amino-1-n-butyl-4-n-butylamino-5-cyano-pyridin-6-one (compound 87 from Tab. 6) had precipitated. This product was filtered off. Mp 177-179 ° C.

(b) 2.6 g (0.01 mol) of 2-amino ~ 6-chloro-5-cyano-1-ethyl-4-ethylaminopyridinium chloride (compound 2 from Tab. 1) were dissolved in water, and then 0.03 moles of sodium sulfide was added. 2.0 g (90 % yield) of 2-amino-5-cyano-i-ethyl ^ -äthylaminopyridin-ö-thione (compound from Tab. 6) precipitated immediately and were filtered off. Mp 190-192 ⁰ C.

(c) 2.3 g (0.01 mol) of 2-amino-6-chloro-5-cyano-1-methyl-4-methylamino-pyridinium chloride (compound 1 from Tab. 1) were dissolved in water, and then 0.66 g (0.01 mol) of malononitrile and 2.0 g (0.02 mol) of triethylamine were added. After a few minutes, 1.7 g (75 % yield) of 2-amino-5-cyano-1-methyl-4-methylamino-6-carbormidoctanomethylpyridinium chloride (compound 83 from Tab. 6) crystallized out. Fp> 240 ⁰ C.

A number of analogous conjugate bases made according to the above The processes described under (a), (b) and (c) are listed in Table 6.

- 10 -

409813/1154

Example 7

0.8 g (0.012 mol) of sodium azide were added to an aqueous solution containing 2.6 g (0.01 mol) of 2-amino-6-chloro- -5-cyano-1-ethyl ~ 4-ethylaminopyridinium chloride (compound 2 from Tab. 1) was added, whereupon the solution was left to stand for 2 hours at room temperature and cooled. 2.0 g (70 % yield) of 2-amino-6-azido-5-cyano-1-ethyl-4-ethylaminopyridinium chloride crystallized out. Mp 164-165 ⁰ C

Example 8

3.2 g (0.01 mol) of 2-amino-1-n-butyl-4-n-butylamino-6-chloro -5-cyano-pyridinium chloride (compound 6 from Tab. 1) were dissolved in dry dimethylformamide dissolved, then 0.06 g (0.01 mol) of sodium methoxide was added and the mixture was refluxed for 60 minutes and filtered. Then the solvent was evaporated. The solid was recrystallized from acetone to give 1.0 g (30 % yield) of 2-amino-1-n-butyl-4-butylamino-5-cyano-6-methoxypyridinium chloride. Mp 187-189 ⁰ C

- 11 -

/ • 09813/115

Tabel

Compounds of the formula:

¹ M '

<- ^ v ^ V-1

-1

produced according to example 1

R. methyl %
the end
prey Fp
( ⁰ C) analysis C. H N Cl product
connect
No. ethyl 80 250 41.51
(41.21) 4.26
(4.32) 24.11
(24.03) 30.3
(30.4) 1 n-propyl 80 > 250 2 Isopropyl 75 215-217 3 Alkyl 40 196-197 49.89
(49.81) 6.51
(6.27) 19.25
(19.37) 4th n-butyl 60 192-194 5 Isobutyl 85 230-231 52.88
(53.16) 6.94
(7.01) 17.99
(17.71) 22.7
(22.4) 6th 50 237-239 . 7th

V9 L L / C L 8607

-O cn Ul 4> Previous year ro I. O VO OD t product O ρ * OO connect
manure
No. H ω H, J-, O Φ O to O) φ I. I. I. ^ I. φ ty * Φ 3 ö O Jt ¹ , O H O O φ N φ O O Φ H H φ I. H O 4th C + O O S. H H H H Φ Φ C + P- H χ 0 H V ^ PO -J C + H ■ Hj · H Ul H Ul -ο ro cn CO VX σ * ^
φ> VJl O Ul Ul Ul O O ro O O O ü C "^. Ω O O dm H PO
J Φ I _ ^ ro ro ro ro ro ro ro ro _ ^ νΟ ro Previous year Previous year _A O O VX ~ 0 PO cn O Previous year co VJl
j ⁴ ^ vji co -O V L. ro ro ro ro ro UlUl ro ro _i O Ό iv> νθ ro VX VX -A -OCO O 4> ~ 0 ν— ' 00 ro ° vo ro ~ ^ O co O cn cn UlUl uiui UlUl ro ro J> 4> _i _A coco CO-J cn cn vx ro VjJ O -OVX vjj ro Ui CO uiui OCO ro4> -P-VD ro vji VX-i .P-O vD op cn vx -P-Ul VOVO VOvO 'coco Q * cn en cn cno cn-p- ro-i VOVO -AVO • P - P- OO vo co OvO -AVX O-4 VO he » et ⁰ ^ -A -A
VJIUl O -a ^ ^. ocn 4> -P- _a _i
tv »ro VXVX -A -A
VJIUl -A -A cn cn VJi-O - <IU1 £ -ro OO .j. ro VO OO -P - P- -ocn Ui νθ
■ - s 00-p- ovji -P-3 OCO :: _, -J. -A • ^ - ^ -X -A ro ro COCO • P - P- VJlUl cn cn VO OO ο - »· ~~ * UJ cn - ' Ui -P- ro co COO

P σ * φ H

CA Φ C +

Table compounds of the formula:

O CD OO

Cl

manufactured according to the example

Starting
connect
manure
No. Respondents R. R " H Cyano product
connect
manure
No. %
the end
prey Fp
(° c) 1 ammonia methyl n-propyl 19th 70 > 240 1 Cyanamide methyl Allyl 20th 20th > 240 1 n-propylamine methyl Furfuryl 21 80 > 240 1 Allylamine methyl Benzyl 22nd 70 > 240 1 Furfurylamine methyl p-toluenesulfonyl 23 60 > 240 1 Benzylamine methyl n-octyl 24 80 > 240 1 p-toluenesulfonamide methyl n-dodecyl 25th 90 > 240 . 1 n-octylamine methyl 26th 60 203-205 :. 1 n-dodecylamine methyl 27 80 210-214

Table 2 (continued)

Output a
connect
manure
No. Reaction
Attendees R. R " product
verb in-
iung the end
prey Fp
( ⁰ C) 1 Glycine methyl Carboxymethyl 28 80 > 240 2 2-bromoethylamine ethyl 2-bromoethyl 29 80 > 240 2 Furfurylamine ethyl Furfuryl 30th 80 > 240 2 2-picolylamine ethyl 2-picolyl 31 • 75 233-234 3 - Furfurylamine n-propyl Furfuryl 32 75 225 4th n-butylamine Isopropyl n-butyl 33 85 188-190 4th Furfurylamine Isopropyl Furfuryl 34 85 202 6th n-butylamine n-butyl n-butyl 35 80 224 6th Furfurylamine n-butyl Furfuryl 36 80 248 6th n-octylamine n-butyl n-octyl 37 60 228-229 6th Glycine n-butyl Carboxymethyl 38 80 > 240 10 Cyanamide Cyclopene
tyl Cyano 39 70 > 240 11 Methylamine n-hexyl methyl 40 30th 228-230 11 Furfurylamine n-hexyl Furfuryl 41 50 > 240 11 n-butylamine n-hexyl n-butyl 42 60 179-180 11 n-hexylamih n-hexyl n-hexyl 43 70 159-160 11 n-octylamine n-hexyl n-octyl 44 50 148-151 12th Methylamine Cyclo
hexyl methyl 45 60 205-207

tr: OO O

Table 2 (continued)

gangly
rbin-
ng
• Reaction
Attendees R. R " methyl Cyano • ρ ι
• p-Ü
-tiflbO
O ti Ü %
the end
prey Fp
(° c) P ^- (U ρ U
<> t3 & Cyano * - * M ri
U O) 3 U
CU >Ti'Z 14th ammonia n-octyl H ethyl 46 90 231-233 14th Methylamine n-octyl n-propyl 47 80 156 14th Cyanamide n-octyl n-butyl 48 90 226 14th Ethylamine n-octyl Furfuryl 49 '80 209-211 14th n-propylamine n-octyl n-hexyl 50 80 170-172 14th η-butylamine n-octyl n-octyl 51 80 158-160 14th Furfurylamine n-octyl H 52 50 192-194 14th n-hexylamine n-octyl 53 60 140-142 14th n-octylamine n-octyl 54 50 154-156 16 ammonia n-decyl 55 60 240 17th Cyanamide Benzyl 56 80 > 240 '

• P-O CO

Tabel. Compounds of the formula:

.TU x '«* NjX ^ _S0 O

NH

produced according to example 3

I.
OT
faO I R. I.
-P I L, the end
prey Fp analysis C. H N S. Output
verbJLn
duhg
No. methyl Product
connect
manure N 85 > 240 39.27
(39.67) 4.26
(4.16) 22.76
(23.13) 13.0
(13.2) 1 ethyl 57 80 > 240 2 Isopropyl 58 80 > 240 4th n-butyl 59 80 240-245 51.31
(51.51) 6.76
(6.79) 16.70
(17.17) 9.9
(9.8) 6th Isobutyl 60 90 > 240 7th Cyclohexyl 61 60 > 240- 56.95
(57.12) 6.85
(6.92) 14.61
(14.80) 8.2
(8.5) 12th n-octyl 62 80 240-241 14th 63

Table compounds of the formula:

Br

r '■>

/ CN

Cl

-P-O CD

manufactured according to the example

Starting R. Y product αϊ r ρ
(° c) link
No. n-propyl Chiorο link
No. yield 125-128 3 Isopropyl Sulfonate 64 80 > 240 59 n-butyl Chioro 65 60 178-180 6th n-hexyl Chloro 66 60 182-184 11 n-octyl Chioro 67 50 166-167 14th n-nonyl Chloro 68 90 169-171 15th n-decyl Chioro 69 70 166-168 16 Benzyl Chloro 70 75 136-138 17th Benzyl Cyanamino 71 70 > 240 56 72 80

Table compounds of the formula:

.egg

manufactured according to the example

Starting
link
No. R. X Benzyl product
link
No. %
yield Fp
(° C) 1 methyl Carboxymethyl 73 40 145-147 1 methyl Benzyl 74 80 > 240 6th n-butyl Carboxymethyl 75 50 145-147 6th n-butyl Dimethylthio
carbamoyl 76 50 > 240 6th n-butyl Phenyl 77 70 169-171 11 n-hexyl Phenyl 78 50 227-228 12th Cyclohexyl Diethylthio
carbamoyl 79 50 227-229 14th n-octyl 80 30th 124-126

NH.

cn ■ t-

Table compounds of the formula:

, R H

V /

NH.

BASE

manufactured according to the example

Starting
link
No. R. XH Product-
link
No. %
yield Fp
( ⁰ C) _λ
(Basenforin) 1 methyl Hydroxy 81 80 > 240 1 methyl Mercapto 82 80 > 240 1 methyl Dicyanomethyl 83 75 > 240 1 methyl Carboethoxy-.
cyanomethyl 84 60 > 240 2 ethyl Mercapto 85 90 190-192 2 ethyl Carboamido
cyanoraethyl 86 70 227-228 6th n-butyl Hydroxy 87 75 . 177-179 6th η-butyl Mercapto 88 80 173-175 11 n-hexyl Mercapto 89 70 103-104

O O Λ C Q Π I

The antifungal activity of typical inventive Compounds results from the results which are given in Table 7 below.

Tabel

Ö I

O cd

!> cdH

• Η Ο hOÖ ο

3H-P Ο)

Θ ο ο U

• Η β ρ

ω ο U ft

Ni IS ¹ HW

cd CM

ο Φ Xl-H-H ■ Ρ S Cl

O -P

ft

5 h ß Ö Ο) ο cd H • Ρ HO -HO

N
-HH ίί χι ο cd

S co pq

e ω

ρ U ro "

-HOS

cd to η ιο>,

tm ο cd

13 14 17 23 27 36 42 44 46 59 67 78

50 % inhibition of spore germination of M. fructicola <5 ppm ++

> 5 ^ 50 ppm + '. > 50 ppm

Protection of lupine seedlings from infection by P. cinnamomi

<L 2 ppm ++

> 2 <8 ppm +

;> 8 ppm

- 21 -

A O 9 813/1154

INSPECTED

Infection of cotton seedlings by Rh. Solani 100 % protection at 16 kg / ha (soil application) ++ 50 % protection at 16 kg / ha (soil application) +

Infection of tomato seedlings by F. oxysporum 100 % protection at 8 kg / ha (soil application) ++ 50 % protection at 8 kg / ha (soil application) +

- 22 -

409813/1 15Λ

Claims (1)

Claims R represents a straight-chain or branched-chain, substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; or an aralkyl group ; R ^{1 represents} a hydrogen or halogen atom; a sulfonate group; an azido group; a group of the formula -NH-SOp-R ^ j (where R ^ is a substituted or unsubstituted aryl group or a straight or branched chain, substituted or unsubstituted alkyl group); a group of the formula -SCN (lower alkyl) ₂ ; S is a group of the formula -CH (CN) -R ₂ (in which R _{2 is} -COOH, -COO (lower alkyl) or -NH-CO-NH ₂ ) or a group of the formula -NH-R ", -SR "or -0-R" (where R "is a hydrogen atom, a substituted or unsubstituted, straight or branched chain alkyl, alkenyl or alkynyl group, a substituted or unsubstituted aryl or aralkyl group or a cyano group); and A ^{e stands} for an anion. 2 «compounds of the general formula III - 23 - A 0 9 8 1 3/1 1 5 A «Ν \ ^CN in ¹ λ ^θ wherein Hal represents halogen; R has the definition given in claim 1. 3. Process for the preparation of the compounds of the general formula I of claim 1, characterized in that that a compound of the general formula II ^ ^{R. N} CO II CN wherein R is as defined in claim 1 with a phosphorus halide or a phosphorus oxyhalide (phosphorous halide or oxyhalide) converts to a compound of the general formula III of claim 2 to produce, whereupon the compound of general formula III is halogenated in the J position and / or reacted in such a way that the 6-halogen substituent is replaced by other radicals of the formula R '. 4. The method according to claim 3, characterized in that the compound of general formula II in an organic Solvent is dissolved that phosphorus halide or phosphorus oxyhalide (phosphorous halide or oxyhalide) is added to the solution and the mixture is heated to reflux. - 24 40981 3/1 1 5A Use of the compounds according to Claim 1 for combating an attack by fungi on plants by treating the fungus, the plants, the soil or the seeds of the plants with an effective amount of the compound. OR.-lMö.H.FINCKE.DIPL-l.iö.H.uOHIi WPWNG. 3rd STAEGEB - 25 - 409813/1154