DD151253A5 - FUNGICIDAL AGENT - Google Patents

Abstract

The invention relates to fungicidal compositions containing a solid or liquid traegerstoff and a glycol aldehyde-N, O-acetal of general formula I, in which R & exp1! an optionally substituted aryl radical; R & exp2! Hydrogen, an optionally substituted alkyl, arylalkyl or aryl radical; R & exp3! represents an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, arylalkyl, heteroarylalkyl, aryl or heteroaryl radical and for the case where m = O, R & exp3! additionally also denotes hydrogen or a trialkylsilyl radical and X represents oxygen or sulfur; Y for oxygen, sulfur or NR & exp4 !; n for O or 1; m for O or 1; Az for optionally alkyl- or halogen-substituted 1,2,4-triazole, imidazole or pyrazole and R & exp4! is hydrogen, an alkyl or alkoxy radical and its salts and metal complex compounds.

Description

Glycol aldehyde NjO acetals, their preparation and use as fungicides

The new fungicides can be used in agriculture as pesticides.

The present invention relates to novel glycol aldehyde-Ν, Ο-acetals, processes for their preparation, fungicides containing these agents, and methods of controlling harmful fungi with these agents.

Characteristic of the known technical solutions

It is known that the L- (2 '- (2'',4''-Dichlorphenyl -) - 2 ^f - (2 "-propenyloxy ^-) - ethyl) -lH-imidazole (GB-PS 590 13:18) has a fungicidal effect. Its effect, however, especially against mildew and rust fungi is insufficient. Therefore, it is not very suitable in practice for use as a plant protection product to control harmful fungi,

Object of the invention

The aim of the invention is the development of fungicidal agents with improved efficacy in fungi, but the crops are not damaged.

Explanation of the essence of the invention

The invention has for its object to provide new chemical compounds with fungicidal activity.

It has now been found that the new glycol aldehyde-N, 0-acetals of the general formula

: 2 2 1 6

o.z. 0050/033897

ΈΓ

az

in which

R is an optionally substituted aryl radical

ο R is a hydrogen, an optionally substituted

Alkyl, arylalkyl or aryl radical

R is an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, arylalkyl, heteroarylalkyl, aryl or heteroaryl radical and in the case where m = 0, fr additionally also denotes hydrogen or a trialkylsilyl radical and

X for oxygen or sulfur

Y is oxygen, sulfur or NR η is 0 or 1 m is 0 or 1

Az represents optionally alkyl (e.g., methyl) or halo-substituted (e.g., by chlorine) '1,2,4-triazole, imidazole, or pyrazole and

R is hydrogen, an alkyl (1-4 C-atoms) or alkoxy radical (1-4 C-atoms)

and its salts and metal complex compounds have excellent fungicidal activity.

In formula I, R is, for example, an optionally substituted aryl radical having 6 to 12 carbon atoms, in particular an optionally substituted phenyl or naphthyl radical.

221 SS Q.

- 3 - O.Z. OO5O / O33897

Examples of suitable substituents of the aryl radical are: halogen, in particular fluorine, chlorine or bromine; nitro; a straight-chain alkyl radical having 1 to 10 carbon atoms, a branched or cyclic alkyl radical having 3 to 10 carbon atoms; an alkoxy or alkylthio radical having 1 to 5 carbon atoms, a haloalkyl, haloalkoxy, haloalkylthio or haloalkylsulfonyl radical having up to 4 carbon atoms and up to 9 halogen atoms, in particular fluorine or chlorine; an alkoxyalkyl or alkylthioalkyl radical having 2 to 6 carbon atoms, for example, an ethoxypropyl or a methylmercaptomethyl radical; an optionally substituted phenyl radical having 6 to 11 carbon atoms; an optionally substituted in particular in the 4-position

J5 aryloxy, arylalkyloxy or arylazorest, for example, a 4- (4'-chlorophenoxy), 4- (2 ', 4'-dichlorophenoxy), 4- (4 ^f -trifluoromethylphenoxy) radical or a 4- (4 'Chlorophenylazo) or 4- (3'-fluorophenylazo) radical; an optionally substituted arylthio, arylsulfinyl or arylsulfonyl

20 rest; an optionally substituted arylalkyl radical,

in particular an unsubstituted or substituted benzyl radical; a straight-chain alkenyl radical having 2 to β or a branched alkenyl radical having 3 to 7 carbon atoms; a straight-chain alkynyl radical having 2 to 4 or a branched alkynyl radical having 3 to 6 carbon atoms; fused rings, in particular from the classes of aromatics and heterocycles, for example, fused optionally substituted benzo, benzofuro- or pyridino radicals.

R is, for example, hydrogen, a straight-chain alkyl radical having 1 to 10 or a branched alkyl radical having 3 to 8 carbon atoms, an optionally substituted aryl or arylalkyl radical having 6 to 12 carbon atoms in the aryl part and '1 to 2 carbon atoms in the alkyl part.

O.Z. OO5O / O33897

^: '' R is, for example hydrogen, an optionally substituted alkyl radical, which for example, be unbranched, and may consist of 1 to 10 carbon atoms such as a methyl, ethyl, n-propyl, n-pentyl or n-decyl radical, or branched and may comprise 3 to 10 carbon atoms such as an isopropyl, a 2-methyl-propyl-l- or a 3j3-dimethyl-n-butyl-lrest, R is, for example, an unbranched or branched alkenyl or alkynyl with 2 or 3 to 10 carbon atoms, such as for example a propen-2-yl-l, propin-2-yl-l or a penta-l, 3-dien-yl-1 radical or R is, for example a cyclic alkyl or alkenyl radical having 3 to 6 ring carbon atoms, such as for example a cyclopropyl, cyclobutyl, cyclohexen-2-yl-l or cyclohexyl radical, R is furthermore an optionally substituted arylalkyl, heteroarylalkyl, aryl or heteroaryl radical 1 to 2 carbon atoms in Alkyltei l and 6 to 12 carbon atoms in the aryl moiety or 5 to 6 ring atoms in the heteroaryl moiety, of which 1 to 3 heteroatoms may be, for example, oxygen, nitrogen or sulfur, such as an optionally substituted phenyl, benzyl, phenylethyl, naphthyl, naphthylmethyl -, furanyl, thienyl, thienylmethyl, isoxazolyl, isoxazolylmethyl, imidazolyl, imidazolylmethyl, triazolylmethyl, pyrazolylmethyl, pyridyl or pyrimidinyl.

Examples of substituents for the radicals mentioned for R ^J are: halogen, such as fluorine, chlorine, bromine or iodine; Nitro or cyano groups; lower alkyl; Halogenoalkyl, alkoxy, alkylthio or haloalkyloxy radicals having 1 to 4 carbon atoms and 1 to 9 halogen atoms, such as, for example, methyl, trifluoromethyl, methoxy, methylthio, ethyl, ethoxy, tetrafluoroethoxy or an n-propyl or tert-butyl radical;

- 5 - O.Z. OO5O / O33897

Hie tog sip such as in a phenacyl radical; gen. "" in particular in the 4-aryl substituted aryloxy, arylalkyloxy or Arylthioreste such as a 4-CMor-phenoxy, a 2,4-dichlorophenoxy or a 4-chloro-pnenylthiorest.

The new glycolaldehyde-N, 0-acetal and loading their ^derivatives: Sitting a center of asymmetry in the acetal carbon atom and, depending on the nature of R ^ more asymmetric centers. By conventional methods, the optically pure enantiomers or diastereomers can be obtained. They are covered by the invention. As fungicides, it is possible to use both the pure enantiomers or the uniform diastereomers, as well as those usually used in the synthesis.

15 falling mixtures.

The compounds of formula II

f 20 R ^ OC-CH ₂ -OH II

az

1 2

in which R, R and Az have the meanings explained above, can be prepared by reducing the Verbindüngen of the general formula III

R ² O-

R-Lo-C- CO R ^D III Az.

2 2 16 5 0

- 6 - O.Z. OO5O / O33897

-ip

in which R, R and Az have the meanings explained above and B is hydrogen, an alkyl or alkoxycarbonyl radical having in each case 1 to 4 C atoms, the reduction being carried out optionally in the presence of a solvent or diluent, if appropriate in US Pat Presence of a reaction accelerator with complex hydrides or in the presence of a catalyst with hydrogen takes place.

The acid derivatives of the general formula III required as starting materials are known.

, For the synthesis of the esters of formula III can be used two different production methods, which are described in DE-OS 27 20 654 and 28 46 127. A direct synthesis of the acids is described in DE-OS 28 46 038.

The reduction of the acids to the alcohols of the formula II can be carried out catalytically with hydrogen on Adkins catalysts by known processes (see, for example, Cornils and E. Zilly in Methodicum Chimicum Vol. 5, p. 6l, Thiemeverlag, Stuttgart, 1975). ,

The acids, the esters and the mixed anhydrides of the formula III can be converted into the alcohols of the formula II by the known methods of reduction with complex hydrides, for example BH, NaBH _n or LiAlH _n (compare WG Brown in Organic Reactions Vol 469, J. Wiley, New York 1951 and B. Cornils and E. Zilly in Methodicum Chimicum Vol. 5, p. 67).

It has furthermore been found that compounds of the formula I are obtained if a compound of the formula

2 2 1 6 S ö

- 7 - O- ^ζ · OO5O / O33897

C-CH ₀ -OH Ii

az

5 or their alkali, alkaline earth or quaternary ammonium salts a) with an alkylating agent of the formula IV

R ³ L IV

or

  b) with an acid derivative of the general formula V

15 W - + -! ^ R ^ V

or

c) reacting with an isocyanate of the formula VI,

r3_N = C = X VI

1 2 λ

in which R, R, Az, R, X, Y and η have the meanings explained above and L is a nucleus-displaceable precipitate

25 gang group, optionally in the presence of a Lö-

or in the presence of inorganic or organic bases, if appropriate with the addition of a reaction accelerator at temperatures between 0 and 12O ⁰ C reacted.

2 21 SSO ..

- 8 - O.Z. 0050/033897

¹ AIs nucleophilically displaceable leaving groups L are mentioned, for example: halogen, such as chlorine, bromine or iodine; · alkyl sulfate such as methyl sulfate; optionally substituted Alkylsulfonyloxyreste such as methanesulfonyloxy or Trifluormethansulfonyloxyreste or Arylsulfonyloxyreste as the Methylphenylsulfonyloxyrest. Furthermore, nucleophilically displaceable leaving groups L are particularly suitable for the acid derivatives. of the formula V, for example, azoles such as imidazole or triazole and acyloxy groups as mentioned in Säureanhydrideη.

Suitable inorganic or organic bases which, if appropriate, can also be used as acid-binding agents are, for example, alkali metal and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide; Alkali carbonates such as potassium or sodium carbonate; Alkali hydrides such as sodium hydride; Alkali or alkaline earth alcoholates such as sodium methylate, magnesium methylate or sodium isopropylate, or tertiary amines such as trimethylamine, triethylamine, N, N-dimethylaniline, Ν, Ν-dimethylcyclohexylamine, N-methylpiperidine or pyridine; Azoles such as 1,2,4-triazole or imidazole. However, other common bases can be used.

With special bases such as alkali metal hydrides such as sodium hydride or lithium alkyls such as butyl lithium or with alkali metal or alkaline earth metal such as sodium methylate, the alcohols of the formula II can also be first converted into their alkoxide salts and then reacted as such.

The solvents or diluents include, for example, halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene; aliphatic or aromatic hydrocarbons such as cyclo. hexane, petroleum ether, benzene, toluene or xylenes; Esters, such as ethyl acetate; Amides such as dimethylformamide; nitrites

- 9 - O.Z. OO5O / O338S7

such as acetonitrile; Sulfoxides, such as dimethylsulfoxide; Ketones such as acetone or methyl ethyl ketone; Ethers such as diethyl ether, tetrahydrofuran or dioxane or corresponding Geraische.

As a reaction accelerator, for example, metal halides such as potassium iodide; crown ethers; Quaternary ammonium compounds such as tetrabutylammonium iodide or acids or 'combinations of these reaction accelerators in question.

It has furthermore been found that compounds of the formula I are obtained when compounds of the formula VII

R ¹ OC-CH ₀ OZ 'VII

15 Az

1 2 wherein R, R and Az have the meanings explained above

and OZ is a nucleophilic displaceable leaving group, with a nucleophilic compound of the formula VIII 20

HOR ³ VIII

wherein R- ^{5 has} the meaning described above, or with the alkali metal or alkaline earth metal salt optionally in the presence of a solvent or diluent, optionally in the presence of an inorganic or organic base and optionally in the presence of a reaction accelerator at temperatures between 0 and 120 ° C. As examples of the mentioned nucleophilically displaceable leaving groups of the formula OZ, mention may be made, for example, of the trifluoroacetyloxy radical; Alkyloxycarbonyloxyreste, alkyl or Arylsulfonyloxyreste, for example the Methansulfonyloxy-, the trifluoromethylsulfonyloxy or the Methylphenylsulfonyloxygruppe.

221650

- ίο - ο. ζ. 0050/033897

The compounds of the formula VII can be prepared from the alcohols of the formula II by reaction with the corresponding acid halides or acid anhydrides by customary methods.

"The alkali or alkaline earth salts of the nucleophilic compound of formula VIII may also be prepared first with particular bases such as alkali metal hydrides such as sodium hydride or lithium alkyl such as butyllithium or alkali or alkaline earth alcoholates such as sodium methylate and thereafter reacted.

For the solvents or diluents, the inorganic or organic bases and for the reaction accelerator ", the statements made above apply.

The reactions described above are generally carried out at temperatures between 0 and 150 ° C in a period of 1 to 60 hours, without pressure or under pressure, continuously or discontinuously.

To separate the new compounds from the reaction mixtures, the procedure is conventional. In general, the products thus obtained require no further purification, but they can be further purified by known methods such as recrystallization, extraction, distillation or chromatography.

If desired, the alcohols of the formula II or the compounds of the formula I prepared according to the processes described above are then converted by known methods into their plant-tolerated salts or into their metal compex compounds.

221 SSO

- Ii - ο.ζ. 0050/033897

  The salts which may be mentioned are in particular the non-phytotoxic salts, for example the acid addition salts hydrochlorides, bromides, sulfates, nitrates, phosphates, oxalates or dodecylbenzenesulfonates.

For the metal complex compounds, the complex compounds of the alcohols of the formula II or of the compounds of the formula I with heavy metal salts, in particular of zinc, copper, manganese, iron or nickel, for example with zinc chloride, copper (II) chloride, copper (II) sulfate, manganese II-chloride, iron (II) chloride or nickel (II) bromide.

The preparation of the novel compounds of the formula I is illustrated by the following examples:

embodiments Example 1:

H - C-CH_OH.

I ²

100 g of 2- (2 ', V-dichlorophenoxy) -2- (1', 2 ', 4'-triazole-1') are added to a mixture of 115 ml of trimethyl borate and 50 ml of absolutely dry tetrahydrofuran (THF). yl) -acetic acid and then added dropwise at 25-3O ° C under nitrogen 50 ml of borane-dimethyl sulfide complex to. The mixture is stirred overnight at room temperature (20 ° C), added dropwise with cooling about .100 ml of methanol and the solution evaporated after completion of gas evolution. The residue is dissolved in ethyl acetate

221650

, - 12 - O.Z. OO5O / O33897

Lind with water and then shaken with a little 1 normal aqueous sodium hydroxide solution. After drying and evaporation of the organic phase, 70 g (74 % of theory) of 2- (2 ^f , 4'-dichlorophenoxy) -2- (l ', 2', H'-triazole-l ^T -yl) - ethanol (# 1) of melting point 125-127 ° C (from diisopropyl ether).

Example 2

2.8 g of lithium aluminum hydride are abs. In 50 ml. Suspended tetrahydrofuran and slowly with a solution of -.35.1 g of 2- (4'-phenylphenoxy) -2- (l ', 2', 4'-triazol-l ^! -Yl -) - acetate tert-butyl ester in 150 ml abs. THP offset. After stirring overnight, the excess LiAlH ^ is first decomposed with ethyl acetate, then with aqueous sodium chloride solution. The resulting voluminous precipitate is filtered off with suction and washed well with tetrahydrofuran. The organic phase is dried and evaporated. The white crystalline residue is boiled twice with diisopropyl ether. 25 g is obtained 2- (4'-phenylphenoxy -) - 2- (I ^1, 2 ', 4 ^{triazol-l'-yl!)} Ethanol (no. 2) of melting point 95 to 100 ⁰ C.

2 21650

- 13 - OZ 0050/033897

'"Example 3

H is 0-C-CH-OH

To a solution of 21.7 S chloroformate in 50 ml abs. Tetrahydrofuran is at -5 ° C, a solution of triethylammonium salt of 2- (4'-chlorophenoxy) -2- (l ', 2', 4 '-triazol-1 ^T -yl) acetic acid in 300 ml of abs. Tetrahydrofuran - prepared from 50.7 g of 2- (4'-chlorophenoxy) -2- (l ', 2', 4'-triazol-l'-yl) acetic acid and 20.2 g of triethylamine - added dropwise. After half an hour stirring at -5 ° C and then send at room temperature (20 ° C), the precipitated triethylammonium chloride is filtered off with suction and the organic filtrate at 10-15 C in portions to a solution of 19 g Natriu borohydride in 200 ml least. Given water.

After stirring overnight, it is neutralized with dilute hydrochloric acid and the tetrahydrofuran is removed in vacuo. The remaining aqueous phase is extracted four times with 200 ml of CHpCHp. The combined organic phases are concentrated .. After trituration of the residual crystals in diisopropyl ether, 32 g of 2 after drying (4'-chlorophenoxy -) - 2- (l ^T, 2 ', 4'-triazol-1'-yl ) -ethanol (# 3) of melting point 108-110 ° C

30 calc .: F .:

C 4 H 17 N 14 Cl 50 ,1 4 2 17 , 5 15 , 7 50 3 , 5 > 2 , 0

- 14 - O.Z. OO5O / O33897

"Example 4

H Cl- / Q VO-C-CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -CH ₂ -Ch

8.9 S 2- (4'-chlorophenoxy) -2- (1 ', 2', V-triazol-1'-yU-ethan-1-ynol is treated with 32 g of n-pentyl chloride, 32 g of an aqueous 50% strength by weight (wt.%) sodium hydroxide solution and 2 g of tetrabutylammonium hydrogen sulfate and vigorously stirred for 4 hours at 6O ⁰ C. the reaction mixture is extracted with 500 ml methylene chloride, the organic phase is washed six times with J5 100 ml of water, getrockent and evaporated.

This gives β g of 2- (4'-chlorophenoxy) -2- (1 ', 2', 4'-triazole-1'-yD-ethyl-1-n-pentyl-ether (No. 4) as colorless analytically pure oil.

Q H N Cl

calculated: 58.1 6.5 13-5 11.4 Found: 58.2 6.4 13.8 11.3

Example 5

O CH

^H ii 1 ³

-O-C-CH O-C-C-CH,

30 ^w I cm ^:

221650

  - 15 - 0.2. OO5O / O33897

2.2 g of sodium hydride are suspended in 150 ml of absolute tetrahydrofuran and washed with a solution of 20 g of 2- (4'-chlorophenoxy) -2- (1 ^!, 2 ', 4'-triazol-1-yl). After stirring for 1 hour at room temperature, 10 g of pivalic acid chloride are added dropwise, and after stirring overnight, 20 ml of water are added dropwise, then the reaction mixture is taken up in 500 ml of CH 2 Cl 2, washed with water, dried and concentrated after filtration through silica gel to obtain 17 g of 2,2-Dimethylpropionsäure- [. 2 '- (V' -chlorphenoxy) -2 ^- (l '', 2 '', 4 '' - triazol-l ^T '-yl ) -ethyl] ester (no. 5) of melting point 82 to 84 ⁰ C.

Example 6 15

H ?

O-C-CH_-O-C-NH

N 20

To a solution of 22 g of 2- (2 '-, 4'-dichlorophenoxy) -2- (1, ^2!', 4'-triazol-l'-yl) ethanol.in 150ml abs. THF is added 9.6 g of phenyl isocyanate and stirred for 6 hours at room temperature (20 C) after. After removal of the solvent, the residue is stirred with diisopropyl ether; 25 g (80 % of theory) of N-phenyl- [2- (2 ', 4'-dichlorophenoxy) -2- (1', 2 ', 4-triazol-1-yl) -ethyl-1 are thus obtained ] -carbamate (# 6) of melting point 105-107 ° C

Accordingly, for example, the following compounds

of the general formula I.

""Table 1

cs

^RJ

az

η m

7 4-Cl-C ₆ H ₄ - H 8th H-Cl-C ₆ H ₄ - H 9 4-Cl-C ₆ H ₄ - H 10 4-Cl-C.H, -D 4 H 11 4-Cl-CH, - D H H 12 4-Cl-C ₆ H ₄ - H 13 2,4-Cl ₂ -C ₆ H ₃ - H 14 2,4-Cl-C ₆ H- H

Ir τ Ii pn η U TT

2,4-Cl-C ₆ H-H 2,4-Cl _? -C, u. H

1,2,4-triazole-1-yl -

ti

I!

Il 11 If

0 0 0 0

0 0 0 0

0 0

1 0 0

0

1

1

OH

CH ₂ -CH = CH ₂

CH.

-Cl

Cl

Cl

^CH 3 CH ₂ -CH = CH ₂

CH.

-Cl

Cl

CHo t ·>

-C-CH,

CH ₃

20

/ pp

oil oil

I.547O oil

55-57

87-90 68-70 oil

61-63 87-88

92-94

O to UJ

2 2165 0

O.Z. OO5O / O33897

VD H OJ

OO

co

I co

O co

as

t-ct \

rH OO

m Ln

O O OJ Qm Q

in

OJ Q

OO

ro

cc;

Mon.

κ ι ca ο -ο -ο

O = Ο CM

OO

CO

OO

CC

OO W

CG ο O I

O = O OY

OJ

OO

CC rH OO OO

ο ca ca cc ι mo ο

O OJO w

ca ι ο

O C I

ε c χ

O O

O O

I IO O

O O O.-ι Ο

ro

ca

I I O I

ι ο ο ο

pH

H O

CO • HL ₁

OJ

CC

te ca ca ca ca ca

ca

I i

I ca m VD ln ca ln ca m ca in ca I I OJ I OJ I OJ I VO CG O cc VO cc VO ca VD ca VD . = 3- O O I O  - = r CG O I vD O VO O VO O VD O CC I cc cc 1 - = r ca I O I O I I O I I O I I O! I VO ln VO VO VO VD O I I - = r - = r - = r Mon. OJ O OJ O OJ O I σ \ O rh OJ OO I I I rh OJ OJ OJ OJ "Xo OJ O O O I sr I I - = r CO _ _ co i-I OJ OJ

^RJ

cn

az

η m

R-

1,2,4-triazol-1-yl

20

/ mp

20

., 584O

30 31 32 ο ί ι c ^ π x> ro ro I Il Ω Ω Ω 6 ^Η 3 ~ OH ₃ ^C 6 ^H 5 H Il Il pyrazolyl 33 2,4-Cl 2- ^C 6 ¹ V H imidazolyl 34 2,4-Cl 6 ^Η 3 ~ H M 35 2,4-Cl 2-C H It 36 4-Cl-C 6 ^Η 4 - H 1,2,4-Trla 37 H-Cl-C 6 ^Η 4 - H Il 38 4-C ₆ H ₅ - ^C 6 V H Il 39 4-C ₆ H ₅ -C ₆ V H Il 40 -c T) C ₆ H "-1j-N) - H Il 41 C ₆ H ₅ ! H Il 42 3-FC ₆ H ₄ H It 43 3-CF ₃ - C ₆ H T H Il 44 (ο H Il (O

0 0 0 0 0 0

0 0 0

0 0

0 0 0 0 0 1

0 0 0

0 0

0 0

ο o

0 0

0 0

CH CH ₂ -CH = CH ₂

CH ₂ -OCH

CH ₂ - <g> -C

CH ₂ -

-F

H H

H H

1.5375 1.5240 1.5950

1.5800 145 ° (Z)

71-72 1,5108 124-126 116-117

O U) OJ CO VD

No. R ¹

cn

nt

az

X Y η m

H 1,2,4-triazol-1-yl-00

H-

cn

/ pp

96-98

114-116

113-114

Λ ⁰¹ 1.5562 O.Z. ci> - ^/ O O VJl O / ~ \ 1.5661 OJ U) OD Il 1.5661 ti 74-76

- 20 - O.Z. OO5O / O33897

"The novel compounds and their salts and metal complex compounds are distinguished by outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Ascomycetes and Basidiomycetes. They are sometimes systemically effective and can be used as foliar and soil fungicides.

Of particular interest are the fungicidal compounds for controlling a variety of fungi on various crops or their seeds.

• Crops are to be understood in this context in particular wheat, rye, barley, oats, rice, maize, cotton, soya, coffee, sugarcane, fruit and ornamentals in horticulture, and vegetables such as cucumbers, beans and cucurbits.

The new compounds are particularly suitable for controlling the following plant diseases:

Erysiphe graminis (powdery mildew) in cereals,

Erysiphe cichoriacearum (powdery mildew) on cucurbits,

Podosphaera leucotricha on apples,

Uncinula necator on vines, 25 Erysiphe polygoni on beans, Sphaerotheca pannosa on roses, Puccinia species on cereals, Rhizoctonia solani on cotton, and

Helminthosphorium species on cereals, 30 Ustilago species on cereals and sugarcane, Rhynchosporium secale on cereals, Venturia inaequalis (apple scab), Mycosphaerella musicola on bananas.

2 2 18 5 0

- 21 - O.Z. OO5O / O33897

Use occurs before or after infection of the plants or seeds by the fungi.

The new substances can be converted into the customary formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The forms of application depend entirely on the intended use; they should in any case ensure a fine and even distribution of the active substance. The formulations are prepared in a known manner, e.g. by stretching the active substance with solvents and / or excipients, if appropriate using emulsifiers and dispersants, it being possible to use other organic solvents as auxiliary solvents in the case of the use of water as diluent. Substitutes such as aromatics (eg xylene, benzene), chlorinated aromatics (eg chlorobenzenes), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol), amines (eg ethanolamine, dimethylformamide) and Water; Carriers such as ground natural minerals (e.g., kaolins, clays, talc, chalk) and ground synthetic minerals (e.g., fumed silica, silicates); Emulsifiers, such as nonionic and anionic emulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkyl sulfonates, and aryl sulfonates), and dispersants such as lignin, safflower pastes, and methyl cellulose.

The fungicidal compositions generally contain between 0.1 and 95 wt.% Active ingredient, preferably between 0.5 and 90.

, The application rates are in the manner of the desired effect between 0.01 and 3, but preferably between 0.01 and 1 kg of active ingredient per hectare.

- 22 - 0.2. OO5O / O33897

The compositions or the ready-to-use preparations prepared therefrom, such as solvents, emulsions, suspensions, powders, dusts, pastes or granules are used in a known manner, for example by spraying, atomizing, dusting, scattering, pickling or pouring.

Examples of such preparations are:

I. Mixing 90 parts by weight of the compound of

Example 1 with 10 parts by weight of N-methylpyrrolidone and obtains a solution which is suitable for use in the form of very small drops.

II. 20 parts by weight of the compound of Example 2 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole of oleic N-monoethanolamide, 5 parts by weight of calcium dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water to obtain an aqueous dispersion containing 0.02 wt. % Of the active ingredient.

III. 20 parts by weight of the compound of Example 3 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the investment product of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water to obtain an aqueous dispersion containing 0.02 wt.% Of the active ingredient.

22 1 SSO

- 23 - O.Z. OO5O / O33897

'Iv. , 20 parts by weight of the compound of Example 4 are ^"1 dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction of boiling point 210 to 28O ° C and 10 parts by weight of the adduct of 40 moles of ethylene oxide

1 mole of castor oil exists. By pouring and finely distributing the solution in 100.00 parts by weight of water to obtain an aqueous dispersion containing 0.02 wt. % Of the active ingredient

 10

V. 20 parts by weight of the compound of Example 1 are the with 3 parts by weight of the sodium salt of diisobutylnaphthalenesulfonic acid, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite liquor and 60 parts by weight of powdered

, Mix the silica well and grind in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water to obtain a spray mixture containing 0.1 wt.% Of the active ingredient. 20

VI. 3 parts by weight of the compound of Example 2 are intimately mixed with 97 parts by weight of finely divided kaolin. This gives a dust containing 3 wt. % Of the active ingredient.

VII. 30 parts by weight of the compound of Example 3 are intimately mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. This gives a preparation of the active substance with good adhesion.

VIII. 40 parts by weight of the compound of Example 4 are mixed with 10 parts of sodium salt of a Phenolsulfonsäu-

2 21BSO

- 24 - O.Z.0050 / 033897

'. **. Re-urea-formaldehyde condensates, 2 parts of silica gel and 48 parts of water intimately mixed. A stable aqueous dispersion is obtained. By diluting with 100,000 parts by weight of water to obtain an aqueous dispersion containing 0.04 wt. % Active ingredient.

IX. 20 parts of the compound of Example 1 are intimately mixed with 2 parts of calcium dodecylbenzenesulfonic acid, 8 parts of fatty alcohol polyglycol ether, 2 parts of sodium salt of a Phenolsulfonsäureharnstoff-formaldehyde condensate and 68 parts of a paraffinic mineral oil. This gives a stable oily dispersion.

The agents according to the invention may also be present together with other active substances in these application forms, e.g. Herbicides, insecticides, growth regulators and fungicides, or mixed with fertilizers and applied. In the case of mixing with fungicides, in many cases enlargement of the fungicidal active substance spectrum is obtained.

The following list of fungicides with which the compounds according to the invention can be combined is intended to illustrate, but not limit, the possible combinations.

Fungicides which can be combined with the compounds according to the invention are, for example:

Dithiocarbamates and their derivatives, such as ferridimethyldithiocarbamate, zinc dimethyldithiocarbamate, manganese ethylenebisdithiocarbamate, manganese-zinc-ethylenediamine-bis-dithiocarbamate,

221 SSO

- 25 - O.Z. OO5O / O33897

* "Prong thylenebisdithiocarbamate,. ^N

Tetramethylthiuramdisulfide,

Ammonia complex of zinc (N-N-ethylene to dithiocarbamate) and

NjN'-polyethylene-bis-thiocarbamyl-disulfide, zinc-iN-N'-propylene-bis-dithiocarbamate),

Ammonia complex of zinc (N, N'-propylene-bis-dithiocarbaniate) and N, N ^l -polypropylene-bis (thiocarbamoyl) -disulfide;

Nitroderivate, like

Dinitro- (l-methylheptyl) -phenylcrotonat, 2-sec-butyl-4 _J 6-dinitrophenyl-3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate;

heterocyclic structures, such as N-trichloromethylthio-tetrahydrophthalimide, N-trichloromethylthio-phthalimidj 2-heptadecyl-2-imidazoline acetate ₎ 2,4-dichloro-6- (o-chloroanilino) -s-triazine ₃ Ο, Ο-diethyl-phthalimidophosphonothioate , 5-amino-1- (bis (dimethylamino) -phosphinyl) -3-phenyl-1,2,4-triazole,

2,3-dicyano-l, 4-di thioanthrachinon, 2-thio-l, 3-dithio- (4 _J 5-b) -quinoxaline ₃

1- (butylcarbamoyl) -2-benzimidazo1-carbaminsäuremethylesterj

2-Me thoxycarbonylamino-benzimidazo I, 2-Rhodanmethylthio-benzothiazole, 4- (2-Chlorphenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thio-l-oxide, 8-hydroxyquinoline or its copper salt,

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

2J3-dihydro-5-carboxanilido-6-methyl-l, 4-oxathiin,

2- (puryl- (2)) -benzimidazole, 35-piperazine-1,4-diyl-bis (2,2,2-trichloro-ethyl) -foniiamide),

- 26 - O.Z. 0050/033897

2- (thiazolyl- (4) -benzimidazole, 5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine, 'bis-Cp-chlorophenyl-S-pyridinemethanol, 1,2-bis (3-ethoxycarbonyl -2-thioureido) benzene, 1,2-bis (3-niethoxycarbonyl-2-thioureido) benzene _J

and various fungicides, such as dodecylguanidine acetate,

3- (3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl) glu-10-taramide,

Hexachlorobenzene, N-dichlorofluoromethylthio-N ¹ , N'-dimethyl-N-phenyl-sulfur

acid diamide, 2,5-dimethyl-furan-3-carboxylic acid anilide, 2,5-dimethyl-3-dicarboxylic acid cyclohexylamide, 2-methylbenzoic acid anilide, 2-iodo-benzoic acid anilide,

1- (3,4-dichloroanilino) -1-fluoromethyl-2,2,2-trichloroethane,

2,6-dimethyl-N-tridecyl-morpholine or its salts, 20 2,6-dimethyl-N-cyclododecyl-morpholine or its salts.

DL-methyl-N- (2,6-dimethyl-phenyl) -N-furoyl (2) alaninate,

DL-N- (2,6-Dimethyl-phenyl) -N- (2'-methoxyacetyl) -alanine RAE

methyl ester, di-isopropyl 5-nitro-isophthalate,

1- (1 ', 2', M'-triazolyl- ¹ ) -l- (4'-chlorophenoxy) -3,3-dime

thyl-butane-2-one,

l- (l ', 2 ^f -, 4'-triazolyl-l') - l- (4'-chlorophenoxy) -3,3-dimethyl

butylbutan-2-ol, 30 N- (2,6-dimethylphenyl) -N-chloroacetyl, D, L-2-aminobutyrolac-

volume,

N- (n-propyl) -N- (2,4,6-trichlorphenoxyethyl) -N'-iraidazolyl-

urea.

22165Ü

-.27 - ° · ^ζ · ΟΟ5Ο / Ο33897

sulfur

N- (1,1,2,2-tetrachloroethylthio) -tetrahydrophthalimide 2-cyano-N- (ethylaminocarbonyl) -2- (methoxyimino) -acetamide. For the following experiment that was from the GB-PS .

No. 5,118,590 discloses known L- (2 '- (2 ", 4" -dichlorophenyl) -2'-_ (2 "-propenyloxy) ethyl-1H-imidazole (active ingredient A).

Trial effect against wheat powdery mildew

Leaves of potted wheat seedlings of the cultivar "Jubilar" are sprayed with aqueous emulsions of 80 % (Ge-weight percent) of active ingredient and 20 % emulsifier and dusted after drying of the spray coating with oidia (spores) of wheat powdery mildew (Erysiphe graminis var. Tritici) , The test plants are then placed in the greenhouse at temperatures between 20 and 22 ° C and 75 to 80 % relative humidity. After 10 days, the extent of mildew development is determined.

25

2 16 5 0

- 28 - O.Z. OO5O / O33897

»Active substance Infestation of the leaves after spraying with

.. # Active Ingredient Broth 0.025 0.012 0.006

11

10 13

15

19 21

36

15 38

39 kS A

0 0 0 0 0 2 0 1 1 0 0 2 0 0 0 0 0 2 0 0 0 0 0 GL 0 0 0 0 0 1 0 0 0 0 0 0 0 1. 2-3 CVI 3 4

20

O = no fungal attack, graded to 5 = total infestation

35

Claims (1)

- 29 - ° · ^ζ · ΟΟ5Ο / Ο33897 * "Claim for invention A fungicidal composition characterized by a content of a solid or liquid carrier and a glycolaldehyde-N, O-acetal of the general formula R ² .az in which R is an optionally substituted aryl radical R is hydrogen, an optionally substituted alkyl, arylalkyl or aryl radical R is an optionally substituted alkyl, Al-. kenyl, alkynyl, cycloalkyl, cycloalkenyl, arylalkyl, heteroarylalkyl, aryl or heteroaryl and in the case that m = 0, R additionally also hydrogen or a trialkylsilyl radical and X is for. Oxygen or sulfur Y for oxygen, sulfur or NR η for 0 or 1
m for 0 or 1 Az for optionally alkyl or halogenated 1,2,4-triazole, imidazole or pyrazole and ü
R is hydrogen, an alkyl or alkoxy radical stands as well as its salts and metal complex compounds.
30