DE2442239A1 - AMINONITRILE, METHOD FOR THEIR MANUFACTURE AND THEIR USE AS FUNGICIDES - Google Patents

Description

Case: S-1-128 897 C (F-12 710)

SUMITOMO CHEMICAL COMPjWY, LIMITED
Osaka, Japan

"Aminonitriles, process for their preparation and their Use as fungicides "

Priority: September 5, 1973, Japan, No. 100 547/73

January 17, 1974, Japan, No. 8 358/74

January 21, 1974, Japan, No. 9 450/74

January 23, 1974, Japan, No. 10 554/74

January 23, 1974, Japan, No. 10 555/74

The invention relates to the subject matter characterized in the claims.

Specific examples of compounds of the invention are given in Ta * - Belle I summarized. The invention also includes the various Stereoisomers and optical isomers.

50981 1/1197

ORIGINAL! KSPEGTED

Table I.

Link _,

Formula properties

CH ₂ = CHCh ₂ -NH-CH ₂ -CN ^κ Ρ · 20 75-76 ^o C

n ^ ⁵ · ⁰ 1.4489

Ch ₂ = CH-CH ₂ -NH-CH-CN
j CHa
:. ^ CHNHCH ₂ CN Kp. 24 78-79 ° C CH ₃ CH ₃ CH ₂ CHNICh ₂ CN
I. 1.4432 CH ₃
J CH ₃ Kp. 18th 77-79 ° C CH ₂ = CH-CH ₂ -NH-C-CN CH ₃
j 21. 5 CH ₃ CHs-C-NHCH ₂ CN ⁿ D CH ₂ = CH-CH ₂ -NH-Ch-CN I.
CH ₃
CH3CHzCHNHCHCN Kp. 21 79-8O ° C CH ₂ CH ₃ CH ₃ CHs ⁿ D 1.4407 CH ₃ -CH = CH-CH2-NH-CH-CN Kp. 20th 82-83 ⁰ C CHs ⁿ D 5 1.4395 I.4267 4 ⁵ I.4319 ⁿ D ⁵ I.4302 η ²³ '
ⁿ D 5 1.4293

509811/1197

link

No.

formula

properties

10 11

13th

16

17 18 19

20th

CH ₃ CH ₂ Ch ₂ CHNHCHCN
II
CH ₃ CH ₃ n ²³
n _D CH ₃
I.
Ch ₃ CH ₂ CHNHC-CN
II n ^23
n D CH ₃ CH ₃ CH ₃ Ch ₂ CHNHCHCN
I i
CH ₃ C ₂ Hs 4 ³ CH ₃ '*' -
. .CHNHCHCN
CH 3 ^ I
CH ₃ 4 ³ . n-Cι0H ₂ 1NH-CH-CN
I.
CH ₃ n-Cl ₂ H ₂₅ NH-CH-CN
I.
CH ₃ CH ₃
I.
nC I ₂ H ₂₅ NH-C-CN
I. • 28.0
ⁿ D I.
CH ₃ nC I ₂ H ₂₅ NH-CH-CN
I. _n 23.0 I.
CH ₂ CH ₃ ^D. n-Cl ₂ H ₂₅ NH-CH-CN "23.0 I.
CH ₂ CH ₂ CK ₃ ^D. n -C12H25NH-CH-CN _n 23.0 |. / CH ₃
CH.
CH ₃ ! 1-CmH ₂₉ NH-CHz-CN p.

1.4248

1.4221

1.4321

1.4258

1.4452

1.4480

1.4488

1.4495

1.4508

I.4492

53.0-54.5 ⁰ C

50981 1/1197

link

Formula properties

n-Ci., H _{2 9} NH-CH-CN p ..

CH ₃

n-Cι eH37NH-CH-CN f.

CH ₃

/ CH ₂ CH = CH ₂ 22.5 Ci-CH ₂ CH ₂ CH ₂ CN ⁿ D

II CH ₂ CN
0

^ CH ₂ CH = CHCH ₃ 23.0

2k CACH ₂ CH ₂ CH ₂ CN ^. ⁿ D

II ^ CH ₂ CN
O

.CH ₂ CH = CH ₂ 25.5 CACH ₂ CH ₂ CH ₂ CN ⁿ D

W ^X CHCN
O j.
CH ₃

^ CH ₂ CH = OH _{2 n} 26.0

CACH ₂ CH ₂ CH ₂ CN. CH ₃

Il \ l

0 CCN
CH ₃

/ CH ₂ CH = CH ₂ 23.0 CACH ₂ CH ₂ CH ₂ CN. " ⁿ D

II ^ CH ₂ CH ₂ -CN
0

^ CH ₂ CH = CH ₂ 20.5 C ₂ H ₅ CN ^ ⁿ D

Jl ^ CH ₂ CN
0

/ CH ₂ CH = CH ₂ 22.0 _Λβ UC ₃ H ₇ Cli ^ ⁿ D 1.4690

^ O

509811/1197

Connection no.

formula

properties

CH ₃ I.

CH ₃ CCN II O

CH ₃

CH ₂ CH = CH ₂ CH ₂ CN

n-CsHiiCN O

/ CH ₂ CH = CH ₂

CH ₂ CN

28.0

1.4709

1.11662

/ CH ₂ CH = CH ₂ -C ₁ iH ₂₃ CN

M ^X CH ₂ CN O

27.5
D.

1.11670

33

CH ₂ CH = CH ₂

n-Ci7H35CN

II ^x CH ₂ CN

CH ₃ CH ₂ CHCN

CJl

-CH ₂ CH = CH ₂ CH ₂ CN

CACH ₂ CH ₂ CN

CH ₂ CH = CH ₂ CH ₂ CN

F. 54.5-55.0 ⁰ C

rip ° 1.4872

rip ² · ⁵ I.4978

Ct

I / CH ₂ CH = CH ₂ CH ₃ CHCN.

II XH ₂ CN O njp * i.4915

-CH ₂ CH = CH ₂

M ^x CH ₂ CN O ^Kp *

1.4669

0.28

■ CH ₂ CH-CH ₂ CH ₂ CN

F, 50.0-51.0 C

509811/1197

link

No formula properties

il ^x CH ₂ CN
O

. / CH ₂ CH = CH ₂ 27.0. , _RfiQ CH ₃ CHCH ₂ CN. ⁿ D i.fööy

II ^X CH ₂ CN

CA O p. _0l5 112-116 C

^Cl « ² 7 x 5, hoop / CH ₂ CH = CH ₂ ⁿ D ± .Hoy ^

CH ₃ C-CN.

g ^X CH ₂ CN Kp. ₀ 8O-82 ° C

Cl

/ CH ₂ CH = CH ₂ 27.5, Hg ₇₂ CH ₃ CH ₂ CH ₂ CHCNv. ⁿ D ^{x> y} '

j » ^X CH ₂ CN,

Br bp _0a2 108-109 ° C

/ CH ₂ CH = CH ₂ 27.0 ^ BrCH ₂ CH ₂ CN. ⁿ D xoj.hu

II ^X CH ₂ CN

O 'bp _{0 12} 123-126 ° C

^ CH ₂ CH = CH ₂ n ² ^ * ⁰ 1 «S4 ^ 4

il ^ CH ₂ CN
O

rip ³ " ⁵ 1.5532 / CH ₂ CH = CH ₂

II ^X CH ₂ CN
O

/ CHzCH = CHz F. 82.0-83.O ⁰ C

-J

| 1 NCH ₂ CN
O

CA F. 64.0-64.5 ⁰ C

CHzCH = CH ₂

5098.11 / 1197

link

formula

properties

47

49

50

52

53

54

CH ₂ CH = CH ₂

I! ^ CH ₂ CN

Ci,

CH ₃

/ Λ

CN

| l

CH ₂ CH = CH ₂

CH ₂ CH-CH ₂

CH ₂ CN

CII ₃ CH ₃ '

CH ₃ O-

CN,

-CH ₂ CH = CH ₂

NO ₂

NO ₂

- / il ^ CH ₂ CN 0

^ CH ₂ CH = CH ₂ ^ CH ₂ CN

-CH 2 CH = CH 2 CH ₂ CN ^

/ CH ₂ CH = CH ₂ ^ CH ₂ CN

"C = CH-CH2NHCH2CN

CN,

Il

Cl

24.5
D.

¹ D

F.

_Ί
1.

1.5332

1.5310

F. 66.0-66.5 ⁰ C

I.5692

1.4823

50981 1/1197

Connection no.

formula

2A42239

Properties

55

56 57

0 11 C (CHz) ₂ CH ₂ Ci,

C = CH-CH ₂ -N-CH ₂ -CN

HC = C-CH ₂ -NH-CH ₂ CN

IC (CH ₂ ) ₂ CH ₂ Cä

HC = C-CH ₂ -N-CH ₂ -CN

26.0

26.0 D

27-5 D.

1.4988

In the process according to the invention, 1 mole of the carbonyl compound is used of the general formula III first in a solvent such as water, an alcohol, ethyl acetate, dioxane, tetrahydrofuran, Dissolved dimethyl sulfoxide, dimethylformamide or ligroin, barrels is the preferred solvent. Then 1.2 mol of the amine of the general formula II, optionally in the presence of sodium hydrogen sulfite, and with cooling or heating in entered the solution with stirring. An aqueous solution of 1 mol of potassium cyanite is then added with stirring. After finished The reaction mixture is left to stand. The resulting aminonitrile of the general formula VI separates out in pure form and in high yield as an oil. This oil is separated and dried, and it can be further purified by distillation under reduced pressure. To manufacture

50981.1 / 1197

Development of the aminonitriles of the general formula I, in which R _{1 is} an acyl radical, 0.11 mol of the aminonitrile of the general formula VI formed is admixed with 0.11 mol of a tertiary amine in an inert solvent. Specific examples of tertiary amines that can be used are triethylamine, pyridine, Ν, Ν-dimethylaniline, N, N-diethylaniline and N-methylmorpholine. Triethylamine is preferred. Specific examples of solvents that can be used are benzene, toluene, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, acetone, methyl isobutyl ketone and ethyl acetate. Toluene is preferred. The acid chloride of the general formula V is added dropwise to the mixture with stirring and at a temperature from about 0 C to the boiling point of the solvent used. After the addition has ended, the reaction mixture is stirred for a while. The reaction mixture is then cooled, washed successively with water, a dilute aqueous alkaline solution and a dilute aqueous mineral acid solution , dried over a drying agent such as calcium chloride, sodium sulfate or magnesium sulfate, and evaporated under reduced pressure.The residue is distilled under reduced pressure the corresponding N-acylglycinonitrile of the general formula I is obtained in high yield.

Specific examples of the method used according to the carbonyl compounds of the general formula III are formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, diethyl ketone, ethyl propyl ketone, ethyl isopropyl ketone, methyl butyl ketone, ethyl butyl

509811/1197

ketone, propyl butyl ketone and isopropyl butyl ketone.

Specific examples of amines used according to the process are listed below:

C10H21NH2 (straight or branched) C ₁₂ H ₂₅ NH ₂ (C ₁₁₁ H ₂₃ NH ₂ (C ₁₆ H ₃₃ NH ₂ (Cj ₈ H ₃₇ NH ₂ (CH ₂ = CH-CH ₂ -NH ₂ CJl (H) C = CH-CH ₂ -NH ₂ Ct

CH ₂ = C-CH ₂ -NH ₂

CHj-CH = CH-CH ₂ -NH ₂

CH,

I.
CHt-C-CHt-MH,

CiCH t-CH-CK-CHt-NH, (C. "

CH ₁₁ NHt (CiHiTNH ₁ (. CHsC-CHt-NHt CH _t -C = C-CHt-NHt

-NKt

VNHt

509811/1187

Specific examples of usable hydrogen sulfites are Sodium and potassium hydrogen sulfite. Specific examples for Usable cyanides are sodium and potassium cyanite.

Specific examples of usable acid chlorides of the general formula V are listed below;

C ₂ H ₅ COCJl

C 3H ₇ COCi, (unbranched or branched)

C ₁₁ H ₉ COCi, (")

C ₅ HnC (DCiL (")

C ₆ H ₁₃ COCi, (")

C ₈ Hi ₇ COCi, ('")

Ci oH 21COC Jl (")

Ci ₁₁ H ₂₉ COCJl (")

Ci ₆ H ₃₃ COCJl (")

CJI-CH ₂ -CH ₂ -COCJi

Br-CH ₂ -CH ₂ -COCi,

CH ₃ -CHBr-COCi,

CH 3-C (Br ₂ ) -COCi,

CJl-CHg-CHCJl-COCJl

CJI-CH ₂ -CH ₂ -CH ₂ -COCjI-

CH ₃ -CHCJI-CH ₂ -COCjI

CH ₃ -CH ₂ -CHCjI-COCJI

Br-CH ₂ -CH ₂ -CH ₂ -COCJ ?,

CH ₃ -CH ₂ -CHBr-COCJl.

CJI ₂ Ch-CH ₂ -CH ₂ -COCJI
CJICH ₂ -CH ₂ -Ch ₂ -CH ₂ -COCJI
CJLCH ₂ - (CH ₂ )! o-COCi,

509811/1197

COCJl

O ₂ M

CE ₃

Br

ca- " ^v

CH ₃

OCH ₃

COCA

The compounds of the general Foaraael Έ are valuable agricultural clieffilkalieji ra with a broad and strong fungicidal effect. This Mirüoaiig is surprising because homologous compounds such as those in HeIv. Chim. Acta, Vol. Hh (1961), S, 1237, ¥ S-PSen 3 1? 4 975 ujiö 3 202 6?% Midmonths., Vol. 93 (1962), p. 469, do not have this description .

If in the compounds of general formula I the remainder

S0S811 / 11S7

R _n . means a halomethyl group, these compounds have a strong herbicidal effect. However, if the radical R_ denotes a haloalkyl radical in which the alkyl radical contains 2 or more carbon atoms, the herbicidal effect disappears completely and the compounds have a strong fungicidal effect. This finding is surprising.

The precursors of the general formula I can be used to combat a wide variety of pathogenic plant fungi. Examples of these pathogenic fungi are Fusarium oxysporum f. Lycoporsici, the causative agent of wilt disease in tomatoes, Fusarium oxysporum f. Raphani, the pathogen that causes the yellowing of Japanese radish, Fusarium oxysporum f. Cucumerinum, the causative agent of wilt disease in cucumbers, and Verticillium albo-atrum , oxysporum spp the causative organism of verticillium wilt on eggplants, Fusarium the excitation of yellowing of strawberries, Fusarium oxysporum f. vasinfectuni, the excitation dor wilt in cotton, Pythium., the excitation of root Brandes in vegetables, Corti ciur.i rolfsii, Rhizoctonia solani , the causative agent of the root fire in vegetables and cotton, and Helicobasidium mompa, the causative agent of a root cranes it with sweet potatoes * the compounds of general formula I are not cides only good Bodenfunigi-, but also valuable leaf fungicides, for example oryzae to Boltämpfung of Pyricularia, the pathogen the leaf spot disease of rice, Cochliobolus miyabeanus, a fungus also infects rice, Pellicularia sasakii, the causative agent of Roisblattschoidenfäule, Xanthomonas oryzae, sigmoid He1minthosporium, Gibber fujikuroi, Puccinia spp ·, Ustilago spp.

509811/1197

Sphaerotheca fuliginea and Erysiphe graminis, the causative agents of powdery mildew in vegetables and cereals, Pseudoperonospora spp. and Piasmopana spp., Phytophthora infestans, the causative agent of late blight in potatoes and brown rot in tomatoes, Colletotrichum spp. and Gloeosporium spp., the causative agent of anthracnose in vegetables and fruit trees, Sclerotinia spp., Botrytis spp., the causative agent of gray mold rot in vegetables, strawberries and grapes, Sclerotinia cinerea, the causative agent of Monilia cinerella in peaches kikuchiana in grapes, Phakopsora ampelopsidis, Alternaria, the causative organism of black spot on pears, Alternaria mali, the causative organism of Blattfleckenlcranlcheit in apples, Venturia inaequalis, the causative organism of apple scab, Sclerotinia mali, the causative organisms of flowers mildew in apples and Elsinoe fawcetti, the pathogen of scab on citrus trees.

The compounds of the general formula I also show a strong antimicrobial activity against other microorganisms than pathogenic plant fungi. The compounds of the invention can therefore also be incorporated into wood, bamboo, fiber and paper products. The compounds can also be used as preservatives in cosmetics, paints and synthetic resins, and for combating slime in paper mills.

Another advantage of the compounds of the invention, in addition to their broad-spectrum fungicidal action, is their very low level

! § •• 11/111?

acute toxicity to warm-blooded animals. They also generate no skin irritation at the concentrations used in practice.

The compounds of the invention have fungicidal activity against both Gram-positive and Gram-negative bacteria. Another advantage is that the compounds of the invention are colorless or nearly colorless. The connections can therefore used for purposes where colored compounds cannot be used.

The compounds of general formula I can be the to be protected Substances, for example fiber products, in particular Mixed yarns made of cellulose or viscose, masses that contain synthetic synthetic resins such as polyamides or polyvinyl chloride, Paints containing casein, inorganic or organic pigments, thickeners made from starch or cellulose derivatives, Oils, compounds containing polyvinyl alcohol for the anti-crease finish of fabrics, cosmetics, such as soaps or creams, Ointments, powders or tooth powders, are incorporated, The compounds of general formula I can also be in the form of a Aerosols, a solution in an organic solvent for impregnating wood and as emulsions can be used. Furthermore, the compounds can be used in the form of aqueous suspensions to protect perishable substances such as leather and paper, can be used together with a wetting agent or dispersing agent. Preferably the compounds of the general formula I for disinfecting washed products and for protection

509811/1197

of the products used against microorganisms. To this end the compounds of general formula I are in the form of liquid preparations with an active ingredient content of 0.1 to 500 ppm used, but concentrations outside this range can also be used.

The compounds of general formula I are soluble in most organic, hydrophilic and hydrophobic solvents. Examples of these solvents are benzene, xylene, diethyl ether, dioxane, acetone, methyl isobutyl ketone, cyclohexanone, isophorone, Chloroform, trichloroethane, ethylene glycol monomethyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, dimethylformamide, Dimethyl sulfoxide, acetonitrile and methylnaphthalene

In practice, the compounds of general formula I can be used either alone or together with carriers and / or diluents and / or auxiliaries, for example in the form of dusts, wettable powders, emulsifiable concentrates, Granules, oil sprays, aerosol preparations and incense can be used.

The carrier substances can be solid, liquid or gaseous. Examples for solid carriers are clay, talc, diatomaceous earth, bentonite, kaolin, terra alba and vermiculite. Examples of liquid Carriers are water, alcohols, ketones, benzene, xylene, toluene, naphtha, petroleum ether and kerosene. Examples of gaseous Carriers are the fluorocarbons and chlorocarbon

509811/1197

Substances, liquefied natural gas, methyl chloride, vinyl chloride, dimethyl ether, Nitrogen and carbon dioxide. These preparations can be made by spraying, dusting or injecting in the form of a aqueous solution or undiluted.

The compounds of general formula I can also be used together with other chemicals, for example with blasticidin-S, kasugamycin, polyoxin, validamycin, cellqcidin, 3- / 2- (3,5-dimethyl-2-oxocyclohexyl) -2-hydroxyethyl7- glutarimide, streptomycin, griseofulvin, pentachloronitrobenzene, pentachlorophenol, hexachlorobenzene, trichloronitromethane, 1,1,1-trichloro-2-nitroethane, dichlorodinitromethane, trichloronitroethylene, 1,1,2,2-tetrachloro-cyanoethane, methylene-bis Dichloro - ^ - nitroaniline, zinc-ethylene-bis-dithiocarbamate, zinc-dimethyldithiocarbamate, manganese (II) -ethylene-bis-dithiocarbamate, bis (dimethylthiocarbamoyl) -disulphide, 2,4,5f6-tetrachloroisophthalonitrile, -1,4-naphthoquinone, tetrachlorop-benzoquinone, p-dimethylaminobenzene-diazo-sodium sulfonate, 2- (1-methylheptyl ) -k , 6-dinitrophenyl crotonate, 2-heptadecylimidazoline acetate, 2,4-dichloro-6- ( o-chloroanilino) -S-triazine, dodecyl / fjuanidine acetate, 6-methyl-2,3-quinoxaline-dithiol-cyclic S, S-dithiocarbonate , 2,3-ghinoxaline-dithiol-cyclic S, S-dithiocarbonate, N-trichloromethylthio-4-cyclohexene-1,2-dicarboxyloid, N- (1, 1, 2, 2-tetrachloroethylthio) -4-cyclohexene 1,2-dicarboximide, N- (dichlorofluoromethylthio) -N- (dimethylsulfamoyl) aniline, 1,2-bis (3-niethoxycarbonyl-2-thioureido) benzene, 1,2-bis (3-ätlioxycarboxiyl-2) -thiouroido) -benzene, 2-amino-1, 3 '' - thiadia: - 'ol, 2-aniino-5-mercapto-1, 3 , 4-thiadiazole, o-phonylphenol,

509811/1197

N- (3 '^' - dichlorophenylJ-maleimide, Ν- (3 * _t 5'-dichlorophenyl) succinimide, N- (3 ', 5 ^l -dichlorophenyl) -itaconimide, 3- (3 «, 5" -dichlorophenyl ) -5f5-dimethyloxazoline-2,4-dione, 2,3-dihydro-5-carboxanilide-6-methyl-1,4-oxathiin-4,4-dioxide, 2,3-dihydro-5-carboxanilide-6- methyl-1, ^ - oxathiin, i- (Nn-butylcarbamoyl) -2-methoxycarbonylaniinobenzimidazole, 0, O-diisopropyl-S-benzylthiophosphate, 0-ethyl-S, S-diphenyldithiophosphate, O-butyl-S-benzyl-S- ethyldithiophosphate, O-ethyl-0-phenyl-O- (2, h , 5-trichlorophenyl) -phosphate, 0, O-dimethyl-0- (3-methyl-U-nitrophonyl) -thiophosphate, S- / 1 ^ - Bis-iethoxycarbonylJ-ethyiy-OjO-dimethyl-dithiophosphate, 0,0-dimethyl-S- (N ~ methylcarbamoylmethyl) -dithiophosphate, 0,0-diethyl-0- (2-isopropyl-6-raethyl-4-pyriraidyl) - thiophosphate, 3 »4-dimethylphenyl-N-methylcarbamate, iron methanarsonate, ammonium iron methanarsonate, 2-chloro-h, 6-bj.s- (ethylamino) -S-triazine, 2, ^ f-dichlorophenoxyacetic acid and its salts and esters, 2- Methyl-4-chlorophenoxyacetic acid and its salts and esters, 2,4,6-trichlo phenyl-4'-nitrophenyl ether, sodium pentachlorophenolate, N- (3 »^ - dichlorophenyl) propionamide, 3- (3 *, 4'-dichlorophenyl) -1,1-dimethylurea, <? (» ör »ß- ' ^I ^ di ^> ] - ^uor -i2,6-dinitro-N, N-di-n-propyl-p-toluidine, 2-chloro-2 ¹ , 6'-diethyl-N- (methoxymethyl) acetamide, 1- Naphthyl-N-methylcarbamate, methyl-N- (3 »4-dichlorophenyl) -carbamate, ^ -chlorobenzyl-Ν, Ν-dimethylthiocarbamate, NjN-diallyl-S-chloroacetamide, 0-ethyl-0- (3-diethyl-6 -nitrophenyl) -N-sec-bvitylphosphorothioamidate, Sn-butyl-S- (p-tort, -butylbenzyl) -N- (3-pyridyl) -iinidothiocarbonate, Sn-Hcptyl-S '- (p-tert. -butj ^ lbenzyl) -N- (3-pyridyl) · imidodithioca "bonate, 5-ethoxy-3-trichloromethyl-1,2, ^ - and 3-hydroxy-5-ynethylisoxazole.

50981 1/1197

The compounds of the general formula I can also be used as a mixture with each other and in combination with other agricultural chemicals such as fungicides, nematocides and acaricides or used with fertilizers.

The compounds of the general formula Σ can be used in pure form and in the absence of any other additives will. They can also be used together with other inert components such as carriers, for example in the form of solutions in organic solvents. The to be treated Materials and substances can be coated, mixed or impregnated with the compounds of the general formula I will.

The examples illustrate the invention. Parts, percentages and proportions relate to weight, unless otherwise stated "

Example i

10 ₉ k g of sodium hydrogen sulfite werden.in 50 ml of a 6 percent

drop by e

dissolved aqueous formaldehyde solution. The solution obtained is given in N ei nen 200 ml four-necked flask / over 1 hour with stirring and at a temperature of 10 C to 5 g 6 g of allylamine. Then the mixture is 30 Mi-. utes stirred at room temperature (about 20 to 30 ° C). A solution of 6.5 g of potassium cyanide in 50 ml of water is then added dropwise over the course of 1 hour at room temperature. After stirring for a further 1 hour, the solution is left to stand. The oil layer that separates out is separated off, dried over sodium sulfate.

509811/1197

net and distilled under reduced pressure. Yield 8.6 g of N-allylglycinonitrile with a boiling point of 75 to 76 ° C / 2O Torr; njp »° 1.4489,

Example 2

1 mol of sodium hydrogen sulfite and 300 ml of water are placed in a four-necked flask. The mixture becomes slow with stirring mixed with 1 mol of acetaldehyde. After stirring for a further 30 minutes, 1.1 mol of n-decylamine are slowly added, and the mixture is stirred for a further 30 minutes. Then with stirring 330 ml of an aqueous solution containing 1 mol of potassium cyanite are added dropwise. After stirring for 1 hour, the solution is left to stand. The separated upper layer is washed twice with 200 ml of water and dried over sodium sulfate. After filtering off excess n-decylamine is distilled off from the filtrate under reduced pressure. It remains in 95 percent

27 bags of N-n-decyl-öf-methylglycinonitrile; η '1.4452.

Example 3

In a 100 ml four-necked flask 4.8 g N-Allylglycinonitril, 5t & S TKiäthylamin and 50 ml of toluene are introduced. 7.1 g of 4-chlorobutyryl chloride are added dropwise to the mixture at room temperature with stirring. After stirring for 1 hour at 60 ° C., the solution is cooled and washed successively with water, 5% sodium hydroxide solution and 5% hydrochloric acid. The toluene solution is then dried over sodium sulfate and evaporated under reduced pressure. The residue is distilled under reduced pressure. Yield 9f4 g of 4-chloro-N-cyanmethyl-N-allylbutyrylamide with a boiling point of 145 to 148 ° C./2 torr;

509811/1197

1.4952. -

Example 4

7/0 g (0.04 Mol) submitted p-chlorobenzoyl chloride and 50 ml of toluene. Then the solution is at room temperature with stirring with 4.3 g (0.04 mole) N-allyl glycinonitrile and 3.8 g (0.048 mole) pyridine offset. After stirring for 1 hour, the solution is successively mixed with water, 5 percent sodium hydroxide solution and 5 percent hydrochloric acid as well as water washed. The toluene solution is dried over sodium sulfate and evaporated under reduced pressure. It 9.26 g of a crystalline product remain, which is recrystallized from a mixture of diisopropyl ether and n-hexane. Yield 8.0 g of pure N-allyl-N-p -chlorobenzoylglycinonitrile from 82 to 83 ° C.

Preparation examples

1. Dusts

In each case 3 parts of Compounds (i) and (43) and 97 parts of clay are mixed with each other, are obtained 2 dusts with 3 percent active ingredient content. The dusts can be used as such or by incorporation into the soil.

2. Dusts

Each 4 parts of the connections (3) and (45) and 96 parts Talc are premixed together. There are 2 dusts

509811/1197

obtained, each containing h percent of the active ingredient. These dusts can be used as such or as a dressing agent.

3 »Wettable Powder

50 parts each of the compounds (h) and (51), 5 parts of a calcium alkylbenzenesulfonate as a wetting agent and 5 parts of diatomaceous earth are thoroughly mixed with one another. Wettable powders with a 50 percent active ingredient content are obtained. These preparations can be used in the form of a dilute aqueous solution or undiluted for spraying or soaking.

k, emulsifiable concentrate

50 parts each of compounds (i) and (48), 35 parts of xylene and 1.5 parts of a polyoxyethylene phenyl phenol adduct are thoroughly mixed together. There are 2 emulsifiable concentrates each with 50 percent active ingredient content. the Preparations can be sprayed in the form of diluted aqueous solutions.

5. Granules

5 parts each of compounds (5) and (50), 93 »5 parts clay and 1.5 parts of Gosenol are thoroughly kneaded with water, granulated and dried. There are granules with each 5 percent active ingredient content received. These granules can be used immediately be used.

509811/1197

6. Oil spray

In each case 0.5 parts of the compounds (2) and (49) are with 99.5 parts of kerosene mixed into oil spray, each containing 0.5 percent active ingredient. This oil spray can sprayed or injected as such.

7. Dusts

2 parts each of the connections (7), (11), (15) »(21), (23) and (29) and 98 parts of clay are thoroughly mixed together. 6 dusts with 2 percent active ingredient content each are obtained. These dusts can be used as such will.

8. Wettable powder

50 parts each of the connections (14) and (36), 5 parts of one Alkylbenzenesulfonate as a wetting agent and 45 parts of diatomaceous earth have been thoroughly mixed together. There will be 3 wettable Powder received with 50 percent active ingredient content each. These powders can be sprayed in the form of dilute aqueous solutions will.

9. Emulsifiable concentrate

50 parts each of the connections (13), (18) and (42), 35 parts Xylene and 15 parts of a polyoxyethylene phenylphenol adduct are thoroughly mixed together. 3 emulsifiable concentrates with 50 percent active ingredient content each are obtained « These preparations can be pre-injected in the form of dilute aqueous solutions «

509811/1197

- 2k -

10. Granules

5 parts each of the compounds (8), (16) and (2k), 90 parts of quartz flour, 4.95 parts of calcium lignin sulfonate and 0.05 part of sodium alkylbenzenesulfonate are thoroughly mixed with one another, thoroughly kneaded with water, granulated and dried. 3 granules are obtained each with 5 percent active ingredient content. These granules can be used as such or together with water or incorporated into the soil.

11. Oil spray

In each case 0.5 parts of the connections (17) and (2 6) are with 99j5 parts of kerosene mixed. 2 oil spray agents are obtained, each containing 0.5 percent active ingredient. The oil spray media can be sprayed, injected or in the form of a Aerosols are nebulized.

The biological activity of the compounds of general formula I is illustrated in the experimental examples below.

Experimental example 1

Preventive treatment against the pathogen causing yellowing of Japanese radish (Fusarium oxysporum f. Raphani)

2 A plastic tub with a surface of 0.1m is provided with Garden soil filled. Then the garden soil is filled with soil "infected with Fusarium oxysporum f. Raphani" at a depth mixed up to 5 cm. 50 Wase-40 radish seeds nichi are sown on the surface and covered with garden soil. Then an aqueous solution of an emulsifiable

509811/1197

Concentrate of the compound to be tested applied in an amount of 300 ml per container. The crane infestation is examined in the greenhouse after a month's cultivation and the percentage of healthy seedlings is calculated according to the following equation:

Number of healthy seedlings per

Percentage of healthy _ treated area.

Seedlings. ~ Number of germinations in untreated

ter and non-infected area

The results are summarized in Tables II to VI.

509811/1197

- 26 Table II

Te s t connection

Concentration, ppm

Percentage, healthy seedlings

Phytotoxicity

(D (2) (3) (4) (5)

CH ₃

H VNH-CH-CN

(1)

(2)

200 200 200 200 200

500

500

NHC00CH ₃

(3)

500

infected and untreated area 'uninfected and untreated area

100.0 89.3 98.0 92.7 96.7

22.0

16.0

86.7

0.0 100.0

Remarks:

(1) HeIv. Chim. Acta, Vol. Hk (196I), page 1237

(2) U.S. Patent 3,117 ^

(3) benomyl; see R. Wegler, Chemistry of Plant Protection and Pest Control Agents, Springer Verlag 1970, Vol. 2,

p. 117

- not phytotoxic + phytotoxic

509811/1197

Table III

Test connection <H ViIiICHQJ Concentration,
ppm (D 200 Percentage,
healthy seeds
ling Phyto-
toxicity - . (6) ! CH ₃ 200 86.7 - 65.3 "- (7) ! / CIl-) ₂ N-CHCN
^V CH 3- ^ / (2) 200 100.0 - (8th) COSlICuH ₉ (n) 200 94.7 76.7 - (9) ! ^ Il VkHCOOCH ₃ (3) 200 100.0 - (10) 200 91.3 ~ 0.0 -
100.0 (11) infected and untreated
area
uninfected and untreated
delte area 200 100.0 (12) 200 100.0 - (13) 500 96.7 73.3 500 500

Remarks!

(1) HeIv ₀ Chim _o Acta, Vol. Kh (1961), p. 1237

(2 ) _{monthsh e9} Bd ₀ 93 (Ί96Ι), p. ^ 69

(3) Bonomyl

not phytotoxic + phytotoxic

509811/1197

Table IV

Test connection

Concentration, ppm

Percentage, healthy seedlings

Phytotoxicity

(15) (16) (17) (18) (19) (20) (21) (22)

Ch ₂ CH ₂ IJHCHCN

I cn

I / CH ₃

CH ₃

CONHCi ₁ H ₉ (η)

-Ν _Λ

(D

(2)

200 200 200 200 200 200 200 200 200

500

500

infected and uri-treated

area

uninfected and untreated

delte area

86.7 92.7 88.0 93.3 96.3 89.4 98.0 86.7 92.7

22.0

88.0

0.0 100.0

Remarks:

(1) U.S. Patent 3

(2) benomyl

- not phytotoxic + phytotoxic

509811/1197

Table V

Test connection Concentration,
ppm Percentage,
healthy seeds
ling Phyto-
toxicity 100.0 (23) 500 89.3 - (24) 500 86.7 (25) 500 94.7 - (26) 500 92.7 (27) 500 88.0 (28) 500 93.3 (29) 500 88.0 -. ' (30) 500 96.7 (31) 500 91.3 (32) 500 89.4 (33) 500 96.7 (34) 500 98.0 (35) 500 99.3 (36) 500 16.7 + (1) 500 Vz / NxB ₂ Ci
Il
ο. 22.0 + CS,
) ν ^ CH ₂ CN (2) 500 V = / ^X CCCJl ₃
(ι 83.4 Il
0
CONHCi ₄ H ₉ (Ii)
ι (3). 500 Γ j VnHCOOCH ₃ 0.0
100.0 - Infected and untreated -
area
uninfected and untreated.
direct area

509811/1197

Remarks:

(1) (2) Japan. Patent Publication No. 1 ^ 33/1971 (3) Benomyl - non-phytotoxic + phytotoxic

509811/1197

Table VI

2U2239

Test connection C ₆ H ₅
ι Concentration,
ppm 200 Percentage,
healthy seeds
ling Phyto-
toxicity (43) CJL-Cn ₂ CON-CH-CN
ι 200 92.7 - (44) I.
CH ₃ 200 98.0 (45) C ₁ H ₉ (η) 200 99.3 (46) ι
CH ₃ -CON-CH-CN
j 200 99.3 (47) 1
C2H5 200 96.7 - (48) C0NHC «» H9 (η) 200 93.3 (49) | T VnHC00CH3 200 93.3 ' (50) 200 94.7 - (51) 200 96.7 (52) 200 92.7 (53) 500 91.3 (D 8.0 500 (2) 16.0. 500 Ο) ' 77.3. - - infected and untreated
area
uninfected and untreated
delte area 0.0 -
100.0 -

Notes see

1) U.S. Patent 3,2h7

2) Acta PoI ₉ Pharm. J Vol. 27 (ij (ΐ97θ), .. β. Bonomyl

509811/1197

It can be seen from the results that the compounds of the invention have a significantly higher protective effect as known compounds of similar structure and the well-known fungicide benomyl.

Experimental example 2

Protective effect against leaf spot disease in rice (Piricularia oryzae)

Rice plants of the Kinki No. 33 variety are used in flower pots with a diameter of 9 cm drawn to the ^ leafy stage. Then they are with an aqueous solution of an emulsifiable concentrate of the compound to be examined in a Sprayed quantity of 10 ml per flower pot. A day later, a spore suspension of Piricularia is placed on the rice plants oryzae sprayed on. The number of spots on the leaves is determined 5 days later. The results are in the tables VII to XI summarized.

509811/1197

Table VII

Test connection Concentration,
ppm Number of spots
per sheet Phyto-
toxicity 6.5 - 78.2 (1) 500 3.2 (2) 500 10.8 92.6 (3) 500 5.1 (4) 500 7.2 (5) 500 82.4. - CH ₃ (D 500 ( H VnH-CH-CN CH ₃ (2) 500
/ - \ I O y-CH ₂ CHoNHCHCN
\ γ ~ τ / infected and untreated -
area

Remarks:

(1) HeIv. Chim. Acta, Vol. Hh (I96I), p. 1237

(2) U.S. Patent 3,117,975

- not phytotoxic
+ phytotoxic

509811/110 '/

Table VIII

Te s tν e rbindung Concentration,
ppm Number of spots
per sheet Phyto-
toxicity 4.2 (6) 500 8.3 (7) 500 2.1 (8th) 500 7.3 (9) 500 12.8 (10) 500 5.7 (11) 500 10.5 (12) 500 3.8 (13) 500 53.3 CH _3
r CH ₃ \ I
XHj ₂ -N-CH-CiJ (D. 500 60.9 CH ₃ Ot ₂ CH ₂ CH ₂ NHCH ₂ CK (2) 500 62.7 infected and untreated
area

Remarks:

(1) Monatsh., Vol. 93 (1962), p. 469

(2) J. Sci. Ind. Research, Vol. I7B (1958), pp. - not phytotoxic

+ phytotoxic

50B811 / 11Ö?

Table IX

Test connection Concentration,
ppm Number of spots
per sheet Phyto-
toxicity 2.3 (14) 500 1.6 (15) 500 4.2 (16). 500 0.5 (17) 500 3.2 (18) 500 2.6 (19) 500 2.1 (20) 500 6.5 (21) 500 1.6 (22) ' 500 67.2 ~ (ι ^ y-CH ₂ CH ₂ NHCH-CN (1) 500
V = Z / I / CH ₃
CH
CII ₃ 70.5 CH ₃ CH ₂ CH ₂ CH ₂ nhai ₂ CN (2) 500 72.8 infected and untreated -
area

Remarks:

(1) U.S. Patent 3,220,674

(2) J. Sci. Ind. Research, Vol. I7B (1958), p. 11 - not phytotoxic

+ phytotoxic

509811/1197

Table X - 2442239 ■ Phyto-
toxicity 2.3 (2) 500 Number of spots,
per sheet 4.6 Concentration,
ppm 18.4 Test connection 500 infected and hairless «· -
Area 8.7 (23) 500 10.6 (24) 500 15.7 (25) 500 6.3 (26) 500 15.7 (27) 500 6.1 (28) 500 10.6 (29) 500 12.3 (30) 500 7.7 (31) 500 5.6 (32) 500 9.2 (33) 500 50.3 + (34) 500 (35) 500 (36) (1) 500 42.8 + f """" ¹ V CH CN - \ = z / ^N CCH ₂ CA
I!
O 58.2 - CJl / fc ~~ \ ^ CH ₂ CN i
■ I Il
O

Remarks:

(1) , (2) Japanese Patent Publication No. 1% 33/1971 - non-phytotoxic + phytotoxic

509811/1197

Table XI

Test connection Concentration,
ppm Number of spots,
per sheet Phyto-
toxicity 5.7 (43) 500 4.2 (44) 500 4.8 (45) 500 3.5 (46) 500 1.4 ~ (47) 500 1.9 (48) 500 2.3 (49) 500 9 1 (50) 500 ' 2.7 (51) , 500 1.8 (52) 500 4.3 (53) 500 78.1 C ₆ H ₅ (1) 500
-1 CJI-CH ₂ CON-Ch-CN
I. I.
CH ₃ 80.8 infected and untreated -
area

Remarks:
(1) U.S. Patent 3,247,206
- not phytotoxic
+ phytotoxic

509811/1197

It can be seen from the results that the compounds of the invention have a higher protective effect than that Comparison compounds.

Test example 3 Protective effect on powdery mildew of cucumber (Sphaerotheca fuliginea)

Cucumber plants of the Kaga Aonaga-fushinari variety are grown in flower pots with a diameter of 9 cm until the beginning of the first real leaf stage. The leaf is then pinched off, and an aqueous solution of a wettable powder of the compound to be examined in an amount of 10 ml per flower pot is sprayed onto the cotyle. One day later, the leaf is sprayed with a spore suspension of Sphaerothica fuliginea. The disease is examined after ~ \ k days. The percentage of infected leaf area in relation to the total leaf area is then calculated and the results are evaluated as follows:

Disease number Disease infestation, infected leaf area, 0 no colonies 1 less than 2 2 less than 30 3 less than 60 k less than 95 5 over 95

509811/1197

2U2239

Then the number of leaves is that of the disease number and the disease infestation is calculated according to the following equation:

ν ι ν. · J. -u .ρ 11 (E crane text number χ number of leaves) _Λ _._

Disease hex sbef all = ^J = ~ -r τ-ζ - ■: ■ ■ ■ χ 100

5 χ total number of sheets

The results are summarized in Tables XII to XVI. . .

509811/1197

- ko -

Table XII

Test connection

Concentration, ppm

Disease infestation

Phytotoxicity

(D (2) O) (4) (5)

CH ₃
H V -NH-CH-CN

CH ₃ CH ₂ QI ₂ NHCHCN

(D

200 200 200 200 200 200

1.7

8.3

5.0

11.7

13.3

88.3

(2)

200

96.7

infected and untreated area

100.0

Remarks:

(1) HeIv. Chim. Acta, vol. Hh (1961), p. 1237

(2). U.S. Patent 3,174 - non-phytotoxic + phytotoxic

509811/1197

Table XIII

Test connection Concentration,
ppm Disease
infestation Phyto-
toxicity 11.7 (6) 500 8.3 (7) 500 3.3 (8th) 500 25.0 (9) 500 5.0 (10) 500 13.3 dl) 500 11.7 (12) 500 3.3 (13) 500 81.7 CH ₃ (D, 500 '"■ / ^ CH) ₂ N-CH-CN
CH 3 / I 88.3 CH 3 CH ₂ Ql ₂ CH ₂ NHCH ₂ CN (2) 500 100.0 infected and untreated -
area

Remarks:

(1) Monatsh., Vol. 93 (1958), p. 469

(2) J. Sci. Ind. Research, 17B, 11 (1958) - not phytotoxic

+ phytotoxic

509811/1197

Table XIV

Test connection Conc ent ration ,
ppm Crane ever -
infestation Phyto-
toxicity 25.0 (14) 500 5.0 (15) 500 11.7 (16) 500 3.3 - (17) 500 8.3 (18) 500 11.7 (19) 500 13.3 (20) "500 5.0 (21) 500 8.3 (22) 500 81.7 (/ ^ CH ₂ CH ₂ NH ClI-CN (1) 500 CH ₃ 100.0 infected and untreated
area

Remarks:
(1) U.S. Patent 3,220,674
- not phytotoxic
+ phytotoxic

S09811 / 1197

Table XV

Test connection Concentration, ..
ppm Illness s—
infestation Phyto-
toxicity 1.7 "■ - (23) 500 11.7 81.7 + (24) 500 25.0 (25) 500 5.0 100.0 (26) 500 3.3 - (27) 500 16.7 (28) 500 13.3 (29) 500 16.7 (30) 500. 8.3 (31) 500 11.7 (32) 500 *
13.3 (33) 500 5.0 (34) 500 3.3 (35) 500 5.0 (36) 500 96.7 + (1) 500 \ zrJ ^X CCH ₂ CS,
Il Il
O α
/ Γ ~ λ / CIl ₂ CN (2) 500 Il
O infected and untreated -
area

Remarks:

(1), (2) Japanese Patent Pre-Publication No. H33 / 1971 - not phytotoxic

phytotoxic

509811/1197

- hk -

Table XVI

Test connection

Concentration _t ppm

Disease

Post-toxicity

(43) (44) (45) (46) (47) (48) (49) (50) (51) (52) (53)

(I)

250 250 250 250 250 250 250 250 250 250 250 250

CJI-Ch ₂ COI-CH-CII

CH ₃

infected and uitilbeliiandelte area

3.3 1.7 1.7 5.0 8.3

11.7 8.3 5.0 1.7 3.3 5.0

96.7

l © 0.0

Noticesia s
(1) U.S. Patent 3

■ - niclit pliytotoxiscia

+ pihytoitoxiscli

509811/1197

From the tables it can be seen that the compounds of
Invention have a much higher protective effect
than the comparison compounds.

Experimental example 4

Protective effect against the causative agent of black spot disease with pears (Alternaria kikuchiana) "

An aqueous solution of a wettable powder of the compound to be investigated is applied to the leaf buds of pears
20-Seiki variety injected at the rate of 30 mg per bud. One day later, the new leaves are pinched off, infected with Alternaria kikuchiana spores and incubated in a greenhouse. The disease is examined after another 7 days. The results are summarized in Tables XVII through XXI.

509811/1197

Table XVII

Test connection Concentration,
ppm 500 Number of spots
per sheet Phyto-
toxicity 2.7 500 5.6 500 1.2 500 8.8 - 500 7.6 500
500 54.3
62.5 - (D (D
(2) (2) · —— . 78.2 - (3) and untreated <4) (5) i CH ₃
/ H VnH-CH-CN
¹ CH ₃ (/ Y-CH ₂ CH ₂ NHCHCN infected
area

Remarks:

(1) HeIv. Chim. Acta, vol. Hk (1961), p. 1237

(2) U.S. Patent 3,117/4,975

- not phytotoxic
+ phytotoxic

509811/1197

Table XVIII

Test connection Concentration,
ppm Number of spots
per sheet Phyto-
t oxicitat (6) 500 5.6 - (7) 500 10.3 (8th) . 500 8.2 ~ (9) 500 1.6 (10) 500 2.3 (11) 500 8.5 (12) 500 10.6 (13) 500 3.7 CH ₃
/ CH ₃ \ J (1) 500
j ^ CH ₂ K-CH-CN
* CH ι I 40.3 CH ₃ CH ₂ Qi ₂ CT ₂ KHCH ₂ CN (2) 500 39.4 infected and untreated
area 43.5 -

Anraerkunijon:

(1) Monatsh., Vol. 93 (1962), p. H69

(2) J. Sci. Ind. Research, Vol. I7B (1958), pp. 11 - not phytotoxic

+ phytotoxic

509811/1197

Table XIX

Test connection Concentration,
ppm 1 I / CH ₃ (1) 500
CH
XH ₃ Number of spots
per sheet Phyto-
toxicity (14) 500 - infected and untreated -
area 6.1 _-. (15) 500 15.0 (16) 500 3.2 (17) 500 4.3 (18) 500 8.5 (19) 500 6.4 (20) 500 2.7 (21) 500 11.0 - (22) * 500 5.0 U y -CH2CH2KHCHr-CN 26.8 38.2. -

Remarks:
(1) U.S. Patent 3,220,667k
- not phytotoxic
+ phytotoxic

509811/1197

Table XX

Test connection Concentration,
ppm Number of spots
per sheet Phyto-
toxicity (23) 500 1.2 - (24) 500 10.9 (25) 500 24 7 ■ ·· ■ j (26) 500 8.9 (27) 500 6.2 - (28) 500 12.8 (29) 500 16.4 (30) 500 20.5 (31) 500 7.6 (32) 500 15.6 (33) 500 13.7 (34) 500 8.8 (35) 500 5.6 (36) 500 2.7 / ^r \ _N ( ^CH2CN
, Yry CCH ₂ CJl
■ Il (1) 500 81.4 + Il
O CA
y- λ / CH ₂ CN (2) 500 73.8 + Il
O infected and untreated
area 84.8

Notes:

(1), (2) Japanese Patent Publication No. 1 ^ 33/1971 - non-phytotoxic
+ phytotoxic

509811/1197

Table XXI

Test connection C ₆ H ₅ Concentration,
ppm Number of spots
per sheet Phyto-
toxicity (43) I.
Ci ₁ -CH ₂ CON-OI-CN
I. 500 3.6 - (44) CH ₃ 500 3.2 (45) 500 1.8 (46) 500 1.3 - (47) 500 1.5 (48) 500 4.3 - (49) 500 3.9 (50) 500 6.9 - (51) "500 5.5 - (52) 500 2.3 (53) 500 2.7 (1) 500 68.1 infected and untreated -
area 71.9 -

Remarks:
(1) U.S. Patent 3,2k7,206
- not phytotoxic
+ phytotoxic

509811/1197

From the tables it can be seen that the compounds of the invention have a higher protective effect than the comparison compounds.

Experimental example 5

Protective effect against Sclerotinia sclerotiorum in beans *

Taisho-leintoki beans are used in flower pots pulled to the first true leaf stage with a diameter of 9 cm. Then the plants are placed in an amount of 5 flower pots per area in a room that is sealed with a plastic film. Then the too un-

The investigating compound was smoked in an amount of 100 mg per m for 15 hours. The plastic film is then removed and the leaves are inoculated with Sclerotinia sclerotiorum 17 hours after the smoking treatment. The disease is examined after h days. The percentage of infected leaf area in relation to the total leaf area is calculated and the results are evaluated as follows:

Kr anJc i t s number Disease infestation, infected leaf area, 0 no disease 1 clot infection around the inoculum 2 less than 20 3 less than kO H less than 6o 5 over 60

509811/1197

Then the number of leaves, nQ to n., Becomes that of the disease number corresponds, counted, and the crane is infested calculated using the following equation:

Cranes χ tsbe fall = O i 5 χ

5 χ η

The results are summarized in Table XXII.

509811/1197

Table XXII Disease
infestation Phyto-
toxicity 3.3 - Test connection Amount used,
mg / m- ' 8.3 (23) 100 16.7. (24) 100 11.7 (25) 100 5.0 (26) 100 6.7 - (27) 100 13.3 (28) 100 13.3 (29) 100 11.7 , (30) 100 8.3 (31) 100 11.7 .. ■ (32) '100 3.3 (33) 100 5.0 (34) 100 6.7 (35) 100 88.3 + (36) 100 j ν , CH ₂ CN
X = J ^N CCH ₂ CJt
II
O ^: (1) 100 CJl ts.o + \ σΖ / ^ CCCJIs
I.
0 100.0 (2) 100 infected and untreated
area

Notes:

(1), (2) Japan. Patent Publication No. 1433/1971 - not phytotoxic + phytotoxic

50981 1/1197

It can be seen from the results that the compounds of the invention have a higher protective effect than the comparison compounds.

Test Example 6 Protective action against slime formation in paper mill water

10 e of the compounds (i) to (13) and (23) to (53) are dissolved in 100 ml of water each time. 5 <1 of each solution are diluted with 1 liter of hot water from a paper mill. 5 ml of the resulting solution are further diluted with 2 liters of white water. In each case 100 ml of the test solution obtained are mixed with 10 g of grape sugar, 1 g of peptone, 0.05 g of magnesium sulfate and 0.01 g of calcium chloride, sterilized by heating and treated with Bacillus | Sp. inoculated, taken from the slime of a paper mill

earth. An increase in the bacilli was not observed, While a vigorous increase was observed within 24 hours of untreated samples «

It can be seen from the experiments that the compounds of the general formula I have a significantly higher fungicidal and bactericidal activity than their homologues.

509811/1117

Claims (1)

■ - 55 - .Pat en t claims 1. Aminonitriles of the general formula I R ₂ R ₃ R., in which R _{1 is} a hydrogen atom or a radical of the general formula R-C- Aiobei ΙΪ denotes an optionally halogen-substituted C _p -alkyl radical or an optionally substituted phenyl rust of the general formula represents, in which X represents a halogen atom, a nitro group, a C _1. -alkyl or C. _.- alkoxy radical and η has the value 0 or an integer from 1 to 5 and X is the same or different when η is an integer greater than 1, R _? an optionally halogen-substituted C "_-alkenyl group, a C verzveigtkettigen" _ _f radical, an unbranched or verzveigtkettigen C alkyl radical, a Cp "alkynyl group or a C --Cycloalkylrest and R" and R. Vasserstoffatonie or C ₁ -alkyl j . 2. Aminonitriles according to claim 1 of the general formula I-a I (I-a) R ₂ NH - C - CN 50981 ^ X1197 in which R ₂ , R ~ and R ^ have the meaning given in claim 1 « 3. N-allyl glycinonitrile of the formula CH ₂ = CH-CH ₂ -NH-CH ₂ -CN k, N-isobutyl-fX-methylglycinonitrile of the formula CHj CH ₃ CH ₂ . I. CH - NH - CH - CN CH ₉ 5. N-Allyl-N- (3'-butyroyl) -glycinonitrile of the formula COCH ₂ CH ₂ CH ₂ CA I CH ₂ "= CH - CH ₂ -N-CH ₂ -CN 6. Process for the preparation of the compounds according to claim 1, characterized in that an amine of the general formula II is used in a manner known per se R ₂ NH ₂ (II) with a carbonyl compound of the general formula III R ₃ -CO-R ^ (III) condensed, the resulting Schiff base of the general formula IV 50981 1/1197 reacts with hydrogen cyanide and optionally the resulting Aminonitrile of the general formula VI R ₂ NHC-CN with an acid chloride of the general formula V R-C-CL (V) J ti 0 condensed in the presence of a tertiary amine. 7. Use of the compounds according to claim 1 as fungicides. 509811/1197 ORIGINAL INSPEGTED