DE2554866A1 - FUNGICIDAL COMPOSITION - Google Patents

Description

255A866

PATENT LAWYERS

Dipl.-Ing. P. WIRTH Dr. V. SCHMIED-KOWARZIK DipL-lng. G. DANNENBERG Dr. P. WEINHOLD Dr. D. GUDEL

281134 β FRANKFURT AM MAIN

TELEPHONE (0611)

287014 GR. ESCHENHEIMER STRASSE 39

Caset FP / M-7-185 Wd / Eh

MITSUBISHI CHEMICAL IM) USTRIES

LIMITED 5-2, Marunouchi 2-chome

... Chiyoda-rku-. ---, - - ,.

Tokyo / Japan

Fungicidal composition

The present invention relates to a fungicide for agricultural purposes.

Many fungicides are already known, but some of them should not be used for environmental reasons as they contribute to environmental pollution.

3in the intensive search for one suitable for agriculture Fungicide, which has very good fungicidal properties, but only

609825 / 100Ö

has a low toxicity, it has now been found that urazole derivatives have an excellent fungicidal effect demonstrate.

The present invention thus provides a new fungicide which has a 1,2-substituted 4- (3 ', 5'-dichlorophenyl) urazole as an active ingredient contains the following general formula:

In this formula, R ₁ and Rp can have the same or different meanings and each stand for an alkyl, alkenyl or alkynyl group, an aryl group which may optionally have at least one substituent, an acyl, alkylcarbamoyl, alkoxy carbonyl, alkylthiocarbamoyl or (alkylthio) thiocarbamoyl group, or together they form an alkylene group with 3 to 8 carbon atoms, which can contain a methyl radical in branching; X and Y can also have the same or different meanings and represent oxygen or sulfur.

According to preferred embodiments of the present invention, have the above-mentioned alkyl, alkenyl, alkynyl and acyl groups about 1 to 6, especially 1 to 4 carbon atoms. The same also applies to such groups within the organic radicals mentioned (for example in the aloxycarbamoyl group). the The aryl group is preferably a phenyl radical.

It has already been found that some 1,2,4-substituted urazole derivatives have fungicidal, herbicidal and insecticidal properties. However, the compounds of the above general formula are new and show excellent fungicidal properties

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Effectiveness against various plant diseases are not pathogenic to the host plant and not or only slightly toxic to humans and fish.

The fungicide according to the invention is "particularly suitable for combating of rice sheath blight disease, of botrytis gray mold, rice brown spot disease (rice brown spot disease)., Sclerotinia rot and Alternaria leaf spot disease and prevents in some cases JLen ^ gJLeiqhz_seite_zj ^ i ^ od. .._. ^ _

The connection which is suitable according to the invention can be different Weris-e- to be produced.

A salt of -4 - ("5 *, 5 * -Dichlorphenyl) -urazole will take a few hours at room temperature to elevated temperature with an alkyl ' halide in a solvent such as dimethylformamide, Alcohol or acetone, reacted and delivers the desired product. ·

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In the above formulas, R and R can be the same or different The meaning "have and stand for an alkyl, alkenyl, alkynyl, acyl, alkoxycerbonyl or alkoxythiocarbonyl group; M stands for an alkali or alkaline earth or the group NH- » and X is a halogen.

By changing the molar ratio of the reactants and the type of alkyl halide, mono- and di-substituted ones Get derivatives and disubstituted derivatives with different substituents.

60 9 82 571 & Q0

Way B

In a solvent such as dimethylformamide, acetone or tetrahydrofuran, 4- (3,5-dichlorophenyl) urazole becomes in the presence a basic catalyst such as triethylamine or pyridine, several hours "at room temperature to elevated temperature reacted with an isocyanate or a thioisocyanate and provides the corresponding 1-mono- or 1, 2-di-alkylcarbainoylbezw. alkylthiocarbamoyl derivatives.

HHNCX ₁ - N -

¹ I ~ ϊ RHNCX ₁ - N - - "

In these formulas, H stands for an alkyl group and X ₁ for oxygen or sulfur.

As in route A, mono- or disubstituted derivatives can also be used here can be produced selectively by varying the proportion of the participants.

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Way G

A solution of 1,2-substituted 4- (3 ', 5' -Dichlorophenyl) -urazole in a solvent such as xylene or cumene is treated with phosphorus pentasulfide under reflux for several hours to produce the mono- or dithio derivative.

R ₁ -N -

In these formulas, gen.

and

the above meanings

By varying the ratio of participants in the reaction, you can selectively monothio- or dithiourazole can be produced.

Way D

To a solution of 1,2-substituted 1-alkoxycarbony! Hydrazine in a solvent such as benzene, toluene or xylene, a stoichiometric amount of 3,5-dichlorophenyl isoeyanate in small aliquots added to the 1,2-substituted 1-alkoxycarbonyl-2- (3 ', 5'-dichlorophenyl) hydrazine to make that through

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Distilling off the solvent is precipitated, filtered off and dried; then it is stirred and heated in an aqueous solution of potassium hydroxide or sodium alcoholate dissolved, cooled and treated with an acid, whereby 1,2-substituted 4- (3 ', 5'-dichlorophenyl) urazole precipitated will.

-N-
I. 0 Il - CNH R ₂ -N-COOR "

■ In these! "Orrnels R ^ and. R2 have the meanings given above, and R "represents a lower alkyl group.

Its diene compound and 4- (3 ', 5'-dichlorophenyl) -urazole are subjected to a Diels-Alder reaction in the presence of an oxidizing agent such as lead nitrate, lead acetate or N ₂ O / * and yield H-; 5 ⁱ , 5'-Dichlorphenyl-1,2,3> 6-tetrahydropyridazine-1,2-dicarboximide, which is then added in a solvent such as ethyl acetate, tetrahydrofuran, acetic acid or alcohol, and in the presence of a catalyst such as Pd ^ C or Pt ^ O the desired compound is hydrogenated.

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Il

In this I ¹ OrUIeIn. can-, H; "to R- have the same or different meanings ^: R are each for · hydrogen or. a ^; methyl group.,

In a solution of. 1,2-suJbstitui-ertem; iÄ alkoxy car bony! Hydrazine in an ionizing medium such as benzene, toluene, xylene or cumene, a stoichiometric amount of 3,5-dichloro-phenyl isothiocyanate is added dropwise to make 1.2 - ^ substituted 1-alkoxy- '
to prepare carbonyl-2- (3 ', 5'-dichlorophejaylthiocarbamoyl) hydrazine; the reaction mixture thus obtained then becomes some
Refluxed for hours to about 10 hours or slightly more to provide the desired monothiourazole product.

- NH

+ SCN

^R 2 - N-COOR _H S.
- N-CNH R ₂ - N-COOR

Ί ^l 2

1 2

In these I-formulas, R · and R have the meanings given above.

Bithiourazole derivatives are produced in a similar way, 1,2-substituted 1-alkoxycarbonylhydrazine being used.

Way G

A salt of 4- (3 ¹ , 5'-dichlorophenyl) urazole is stirred for half an hour to several hours at a temperature from room temperature to 200 ° with an alkylene dihalide in a solvent such as water, an alcohol, dimethylformamide, tetrahydrofuran or Benzene, implemented.

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N
I. O Cl M - N - ^ > M - fl O Cl

In these formulas, A stands for an alkylene group with 3 to 8 carbon atoms, which can contain a methyl radical in branching; X is a halogen; M for a metal or an amine, which can be monovalent or divalent; and X ¹ for 2 when H is monovalent, or for 1 when M is divalent.

The preparation of the compounds used as active ingredients according to the invention is illustrated in more detail by the examples below. .

example 1

In a suspension of 3.2 g of the dipotassium salt of 4- (3 ', 5'-dichlorophenyl) urazole in 20 ecm of dried Ii, !! - dimethylformamide 2.9 g of methyl iodide are added, whereupon the reaction mixture Was heated to 60 ° to 70 ° with stirring for 1 hour. After this the !!, !! - dimethylformamide had been distilled off in vacuo, the mass was poured into 200 ecm of water to form the solid material precipitate, which was then recrystallized from ethanol

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and provided 2.6 g of 1,2-dimethyl-4- (3 ', 5'-dichlorophenyl) urazole. The yield was 95%.

Melting point and elemental analysis of the product are from the table I see.

Example 2

In a. Solution of 2.5 g of 4- (3 ', 5'-dichlorophenyl) urazole and 1 g of tri äfhyj p-TTi j p., J η 10ecm. Ν ,, ϊί-Dimethylfprmamid were ^j with stirring ί, ΐ g Xthylchlorformiat. dripped. Then the reaction was taking an hour. Stirring continued at room temperature. The reaction mass was mixed with water to precipitate crystals, which were then filtered and recrystallized from acetone-ethanol. 2.3 g of 1-ethoxycarbonyl-4- (3 ', 5'-dichlorophenyl) urazole were obtained in 72% yield.

Example 3

In a solution of 2.6 g of 1-methyl-4- (3 ', 5'-dichlorophenyl) urazole - prepared by reacting 4- (3 ^f , 5'-dichlorophenyl) urazole and methyl bromide in equimolar amounts - and 1.0 g of triethylamine in 10 ecm Ν, Ν-dimethylformamide were added with stirring at room temperature 0.8 g of acetyl chloride in small portions. After the addition was completed, the reaction was carried out for 2 hours with stirring in a water bath. The solvent was distilled off in vacuo and the mass was poured into water to precipitate crystals. The crystals thus obtained

60982ßV1ÖÖÖ

were recrystallized from ethanol and yielded 2.3 g of 1-methyl-2-acetyl-4- (3 ', 5'-dichlorophenyl) urazole; Yield = 76 #.

Example 4

A solution of 2.5 g of 4- (3 ', 5'-dichlorophenyl) -urazole in 10 ecm N, !! - Dimethylformamide was mixed with a drop of triethylamine, followed by stirring at room temperature 0.8 g of methyl isocyanate were added dropwise. The reaction was continued for an hour under the same conditions, and then * · - became the reaction mixture poured into water to precipitate crystals, which are filtered and recrystallized from acetone-ethanol became. 2.1 g of 1-methylearbamoyl-4- (3 ', 5'-dichio: phenyl) urazole obtained; Yield = $ 68.

example 5

A solution of 2.7 g of 1,2-dimethyl-4- (3 ', 5'-dichlorophenyl) urazole in 25 ecm of xylene was mixed with 4.4 g of phosphorus pentasulfide and refluxed for 8 hours with stirring. After cooling and filtering, the piltrate was condensed in vacuo. The residue was recrystallized from ethanol and yielded 1.4 g of 1,2-dimethyl-4- (3 ', 5'-dichlorophenyl) -dithiourazole; Yield = 47 °.

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Example 6

In a solution of 1.6 g of 1,2-Dimethylätiioxycarbonylhydrazine in 25 ecm of benzene were added in small portions to 1.9 g of 3,5-dichlorophenyl isocyanate with stirring at room temperature. By Evaporation of the benzene in vacuo gave crystals of 1,2-dimethyl-1-ethoxycarbonyl-2- (3 ', 5'-dichlorophenylcarbamoyl) hydrazine obtain; F = 161-163 °.

Elemental analysis C ₁₂ H. | , -ITgO ^ Cl ₀ :

H N Cl

-Calculated, ■ # 45.01 4.7-2- -1-3.12-22-, - 15

Found, <f » 45.12 4.78 13.21 22.03

The product thus obtained was reacted with an equimolar amount of sodium methoxide in methanol under reflux for 6 hours. After cooling, Jasser was added to the reaction mixture to precipitate crystals, which were filtered and recrystallized from ethanol to give 1.0 g of 1,2-dimethyl-4- (3 ', 5'-dichlorophenyl) urazole; Yield = 37 ⁰ M ? = 209-211 °.

Element ar analysis C _A H _Q lT ^ 0 _o Cl _o :

H Ή Cl

Calculated, γά 43.82 3.31 15.33 25.87 Found, #> 43.49 3.30 15.42 25.81

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-H-

Example 7

The procedure of Example 6 was followed using 3,5-dichlorophenyl isothiocyanate repeated. The product was 1,2-Mmethyl-1-ethoxycarbonyl-2- (3 ', 5'-dichlorophenylthiocarbamoyl) · obtained hydrazine; P = 147-149 °.

42 , 86 4, 50 1 2 , 50 21 , 09 9 , 54 42 , 91 4, 47 1 2 , 42 21 , 13 9 , 59

Elemental Analysis C. pH <| cßJLo — 2—2—

__C HN Cl Calculated, fo Found, $>

The compound was refluxed in cumene for 10 hours to give 1.8 g of 1,2-dimethyl-4- (3 ^f , 5'-dichlorophenyl) monothiourazole; Yield = 64 70.

Example 8

A drop of triethylamine was first added to a solution of 3.2 g of 1-ethoxycarbonyl-4- (3 ', 5'-dichlorophenyl) urazole in 10 ecm Ν, ΙΤ-dimethylformamide, and then, with stirring at room temperature, 0.85 g isopropyl isocyanate was added dropwise. The conditions were maintained for 1 hour and then the reaction mixture was mixed with Viasser. The crystals precipitated in this way were filtered and recrystallized from ethanol, yielding 3.0 g of 1-ethoxycarbonyl-2- (isopropylcarbamoyl) -4- (3 ', 5'-dichlorophenyl) urazole; Yield = 75 °.

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Example 9

In a solution of 10.8 g of phenylhydrazine and 10.1 g of triethylamine in 60 ecm benzene was stirred within 20 minutes a solution of 10.9 g of ethyl chloroformate in 40 ecm of benzene was added dropwise, while maintaining the mixture at a temperature of 10-15 °.

The reaction was continued stirring for 1 hour "at room temperature. After water was stirred, allowed to -the S-Saf-i-onsiai _Sohung-r are --bi-ss-iöfe- ■ DIEP-has-en-of The aqueous phase, which contained the triethylamine hydrochloride formed during the reaction, was removed. The organic phase was dried over anhydrous sodium sulfate. At room temperature, 18.8 g of 3,5-dichlorophenyl isocyanate were then added dropwise to the benzene solution and the mixture heated to reaction on a water bath.

The benzene was distilled off in vacuo, and an oily product was obtained, which was mixed with 200 ecm of 5% aqueous potassium hydroxide and heated to reflux for about 2 hours. After cooling and filtering, the filtrate was mixed with concentrated hydrochloric acid, and the precipitated crystals were filtered and recrystallized from ethanol. 23.2 g of 1-henyl-4- (3 ', 5 ^! -Dichlorophenyl) -urazole were obtained; Yield = 72 #; P> 250 °.

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Elemental Analysis C ^ »HrJU

- .. ■ .- ■■ ■ ■ ■ G .H N- Cl

Calculated ,? ° -52 ^ 19 2 ·, 82 13.04 22.01. Found $ 52.42 2.87 12.95 21.88

A mixture of 3.2 g of the above product, 20 ecm of N, N-dimethylformamide and 0.6 g of potassium hydroxide in 5 ecm of water Stirred for 30 minutes at room temperature and yielded a potassium salt, which was mixed with 1.4: g of methyl iodide and a further hour ... fine room temperature .... £ erüta

water was poured into the mixture and it precipitated Crystals were separated off and recrystallized from ethanol. The product would be 1 "-Phenyl-2-methyl-4- (3 ', 5'-dichlorophenyl) -urazole obtain. .

Example 10 _:

In a suspensipn. 29 g of disodium 4 ^ (3 ', 5'-dichlorophenyl) -urazol dried in 200 cc !!, ^ - dimethylformamide was added 26.4 g of 1,4-Mbrompentan, and the obtained mixture WUR de _T 1 hour Stir heated to reflux. After the ΪΤ, Ν-Diinethylforinamid had been removed in vacuo, the residue was poured into 500 ecm of water and gave a solid material, which was filtered off and recrystallized from ethanol. 23.2 g of 1,2-pentamethylene-4- (3 ', 5'-dichlorophenyl) urazole were obtained; Yield = 74 f ° _t

60 9 8 25/1000

255A866

Example 11

In a suspension of 2.85 g of 4- (3 ', 5'-dichlorophenyl) urazole 0.7 g of 1,3-butadiene were absorbed, and then 6.7 g of lead tetraacetate were dissolved in 100 ecm of dichloromethane over a period of 30 minutes added dropwise while the suspension was stirred and kept at a temperature of 0 ° to 5 ° with cooling. After further After stirring for 2 hours, the dichloroethane was in vacuo distilled off at a temperature below 30 °.

The residue was successively j ^^^

0.1-n-nitric acid, aqueous Oji-n-sodium hydroxide and washed again with water and recrystallized from ethyl acetate. 2.8 g of N- (3 ', 5'-dichlorophenyl) -1,2,3,6-tetrahydropyridazine-1,2-dicarboximide were obtained; Yield = $ 82; 3? = 167-168 °. Blementar analysis C ^ pSq ^ P- ^ Si? -

C H H Eq

Calculated, $> 48.34 3.04 H, 09 23.79 Found, # 48.31 3.01 14.25 23.82

Sun was 1.5 g of the product thus obtained in 50 ecm of ethyl acetate dissolved, whereupon in the presence of 0.1 g of a 5 5bigen Pd-C catalyst as long as hydrogen under normal pressure the solution was passed until no more hydrogen absorption could be determined. After filtering off the catalyst the ethyl acetate was distilled off in vacuo. 1.4 g of 1,2-pentamethylene-4- (3 ', 5'-dichlorophenyl) urazole were obtained as the product; Yield = $ 95.

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Example 12

A solution of 5.7 g of 1,2-trimethylene-4- (3 ^f , 5'-dichlorophenyl) urazole - prepared according to the method of Example 10 - and 4.4 g of phosphorus pentasulfide in 50 ecm of xylene was stirred for 4 hours heated to reflux. The reaction mixture was then allowed to cool and the solid material which precipitated out was filtered off. The solvent was evaporated in vacuo and the residue was recrystallized from ethanol. 2.5 g of 1,2-trimethylene-4- (3 ', 5'-dichlorophenyl) monothiourazole were obtained'; «Yield - = ■ 41 -i ° * -—— ■ --— ~ - - ~ - ~~ -""^., ^^ - ^ __ ^^ _ ^^ ^, ^« «* _T,. -..--

Example 13

2 g (0.01 mol) of 3,5-dichlorophenyl isothiocyanate were shaken in small amounts with a solution of 1.7 g of 1,2-pentamethylene-1-ethoxycarbonylhydrazine, 1,2-pentamethylene-1-ethoxycarbonyl- 2- (3 ', 5'-dichlorophenylthiocarbamoyl) hydrazine in quantitative yield. The reaction mixture was sampled and the solvent removed to precipitate crystals; P = 128-130 °.
Slementar analysis C ₁₁ -IL _n Cl ₀ IUO ₀ S:

C H Bi Cl S

Calculated, $ 47.88 5.09 11.17 18.84 8.25 Found, j6 47.85 5.06 11.22 18.75 8.48

The reaction mixture containing the above product was left for 8 hours heated to reflux, cooled and treated with petroleum ether

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thins. The crystals so precipitated were filtered off with Washed petroleum ether and crystallized from ethanol-benzene. They provided 2.5 g of 1,2-pentamethylene-4- (3 ', 5'-dichlorophenyl) monothiourazole; Yield = 77%.

Example 14 :

There were. 2 g of 3,5-Diehlorphenylisocyanat with a solution of ¹ »74 g ^1, 2-ylene vTe.trameth-1- (ethylthio) thiocarbonyl shaken in 10 cc of benzene. Here, crystals became the following

Cl

ρ = 147-149 ⁰ .
Element ar analysis

Calculated,
Found,

.IL

Cl

42.63 42.58

4.35, 10.65 17.98 24.39 4.31 10.62 18.04 24.33

The reaction mixture containing the crystals was treated according to the procedure of Example 13 to yield 2.4 g of 1,2-tetramethylene-4- (3 ', 5'-dichlorophenyl) dithiourazole; Yield = $ 65>.

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Various compounds that are suitable active ingredients for the fungicide according to the invention are shown below Table I summarized.

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Connection

No.

cn

to co N> GTI

O O O

structure

CH, NC ₂ H ₅ N.

Table I.

Melting point, ⁰ g

275-276.5

189-192

209-211

115-117

Element ar analysis, ° />

(3)

39.05 ί 2.05

38.95] 2.02

41.56 i 2.71

41.46; 2.68

43.82 J3.31

£ 3.57 J3.29

45.85; 3.85 45.83) 3.81

01

17.08 28.82

17.21 28.85

16.16 27.26

16.22 27.31

15.33 25.87

15.19 26.02

14.58 24.61

Η, 47 24.55

example

1 bo

Table I (continued)

Connection No.

O CD CD ISO OI

structure

Melting point, C.

90-91

83-85

92-92.5

109-111

91-94

Elemental analysis, ^a / o

(3)

. ' H

Cl

47.70; 4.34 13.91 23.47 47.54 [4.31 13.87 23.52

47.70 j 4.34 13.91 23.47 47.81: 4.30 13.87 23.41

49.38 4.78 13.29 22.43

j
49.27; 4.69 13.27 22.14

47.70 j 4.34 13.91 23.47

47.53 U, 22 13.99 23.56

ι '

50.92 j 5.19 12.73 21.47

51.21 [ 5.20 12.69 21.57

example

ro icn

Connection, no.

10

00 ΙΌ OI

11

12th

13th

structure

CH ₅ CON HN

HN

Cl

Table I (continued)

Melting point, C.

n.

30 (4)

142-146

133-135

193-194

Elemental analysis,

^; H

Cl

53.64 5.90 11.73 19.79 53.58 5.79 11.73 19.67

45.85 ^, 85 ^u »58 24.61

45.90 3.81 14.55 24.68

47.70 4.34 13.91 23.47

47.35 4.34 13.87 23.51

41 , 69 ψ , 45 14th , 59 24, 61 226-228 41 , 65 b , 43 14th , 58 24, 60

43 , 73 P. , 00 1 3 , 90 23, 47 43 , 68 H , 02 1 3 , 88 23, 54

example

ro cn cn

Connection No.

15th

cd 16.

17th

18th

19th

structure

CH ₅ CON CH ₃ CGN

C ₂ H ₅ CON

Table I (continued) Elemental Analyae,

Melting point, C.

226-227

257-260

185-188

211-213

220-222

43.09
42.98

39.62
39.49

:H

2.36

, 42

', 66
', 59

Cl

43.66 2.75 12.73 21.48 43.53 2.77 12.69 22.00

46.94 3.66 11.73 19.80

,1

46.79 5.58 11.65 19.76

41.53 2.85 13.21 22.29 41.49 f, 84 13.09 22.34

10.77 18.17

10.75 18.19

18.49 23.29

18.47 23.45

At-

4 co

Connection

No.

20th

co 21.

22nd

23

24

structure

CH ₃ NHCN-

CH-NHCN

-> Il

CH-CON-

Table I (continued)

Melt elemental analysis, ° / o ^{K :? J}

point, ⁰ C

202-205

138-140

117-119

85.5-86.5

134-135

45.59 3.51 13.29 22.43

45.60; 3.57 13.24 22.59

47.29
47.26

43.39

13.97 12.73 21.48 3.95 12.69 21.53

! 3.34 12.65 21.35

43.33 | 3.31 12.68 21.30

C. H 1 N Cl S 40.02 3.08 1 9.45 19.69 40.14 3.07 1 9.42 19.71 43.73 3.00 1 3.90 23.47 43.68 3.00 3.87 23.49

At-

Connection

No.

P. 26

structure

CH ₃ N

CH _x NHCN- -> 0

OH-NHON ■> ti S

CH ₃ N-

(0H-) ₂ NS0 ₂ N

Table I (continued) Elemental analysis,

Melting point, C.

151-153

187-189

125-127

119-121

163-165

39.57
39.51

Cl

41.66 p, 18 17.67 22.36 41.69 Mo ¹ 7.59 22.43

^, 04 ^, 01

43 , 35 B. , 08 1 1 , 67 1 9, 69 43 , 34 I.
Ϊ , 08 1 1 , 56 1 9, 71

39 65 ? , 03 16 , 82 21 , 28 9, 62 39 67 'i , 00 16 , 78 21 , 20 9, 69

35.98 p, 30 15.26 19.31 8.73 36.11 ^, 29 15.23 19.33 8.74

11 , 54 1 9 , 47 1 7, 60 11 , 56 1 9 , 57 1 9, 81

Connection

No.

30th

O CO 00 ΙΌ

32

33

Table I (continued)

structure

0 C ₂ H ₅ OCN

iC, H ₇ NHCN 0

CH ₀ = CH-CH ₀ N 2 ² I.

CH ₉ = CH-CH ₅ N

CHSC-CH ₂ N = C-CH ₂ N

Melting point, C.

175-177

173-175

82-83

128-129.5

46.4-4 46.50

44.68 44.70

51.55 51.59

52.19 52.22

Elemental analysis,

Cl

3.30 12.50 21.09

3.28 12.47 21.11

4.00 13.90 17.59

4.02 13.86 17.62

4.02 12.88 21.74

4.05. 12.84 21.83

2.82 13.04 22.01

2.89 13.05 22.08

example

Connect ·.

No.

34

35

structure

Table I (continued) C! H . N 50
46 21
21 01 S. At- / px
plays Enamel
point ♦ 0 i
I,
53.59 ^; 3
53.16 Ϊ3 , 30
, 27 12,
12, , 09
, 23 9 101-102.5

246-248

125-127

37.42 J1.92 16.03 27.05 12.23 37.35 1.86 16.00 27.03 12.16

£ 41.39, 13 14.48 24.43 11.05

41 , 18 P. , 10 14th , 51 24, 38 11 , 06 39 , 22 i , 96 13th , 72 23, 16 20th , 94 39 , 23 , 79 13th , 68 23, 20th 20th , 89

SK) CJI

Connection, no.

structure

Table I (continued)

Enamel slement analysis,

Point, ⁰ C 0

134-136

116-118

142-143.5

Cl

48.61 2.72 11.34 28.70 48.27 i 2.75 11.22 28.59

54.87 ^ 3.74 12.00 20.25 55.02 ^ 3.77 11.81 20.17

46.17 53.17 16.69 24.78 46.00 ^ 3.09 16.34 24.56

example

10

OO CD CJ)

CM

I Q)

• Η · Η (D p. PP

SO

co

(O I. H CM to ^ - O CM in ιη O CM O <τ> χ— CM τ— to Ο CQ t O O | VO I. LTi O | CM VD oil VD ^ · Ο | Ε 00 - · H CM CTv ·. CVJ CVJ κ CM • ι , ■> CM ·> «Ν H to to • to H CM I. CVJ H τ— I. τ— H σ » Ι cn o | CM γ— CM o | ^ · CM oil CM C— CM ο | Τ Τ * - I. , l * f \ CVJ to ΙΤ co τ— ^ O 00 Ln CTi -P is; τ— O t— to c— , - O CO t— Ο he" Γ \ Ι O Wl to to Wl 00 VD Wl 00 (D -Φ to T ^ to CVJ CM T ^ T ^ t— a οΤ Τ ™ " τ— Oil ^T ~ oil ο | ^ ~ ^τ ~ H Ε W. cn X— ι— 1- O ιη CO τ— VD in CM VD ιη ΓΟ tn Vt ·. *> to to ■ «φ ιη in f5 N O -P CM to VD to CT * c— (D O CM VD CM O CTi vo -P O CtT 00 cn _τ _ ^ _- to co Ph
O O "* ■ Ln ιη Ln Ln 1 H H H <D -p (D E. H H Q) , Q O 3 CD CQ P

■ p to

O =

U ΰ U © -His;

CM

KN

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ORIGINAL INSPECTED

CVJ

H I Φ

O Pj

m ω

α)

φ S. φ

VO

to

CVJ

O Ο

to

CVl

oil cn to CM VO in Oil to to to CM cn wT O cn CM

T o I

t- T-

in ^

CVJ CJ

co to

CM CM

CM

to to

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609825/1060 co

Connection, no.

structure

Table I (continued) Elemental analysis,

Melting point _t ⁰ C

246-248

164-165.5

199-200.5

168-170

: H

Cl

51.23 4.60 12.80 21.60 5.1.58 Λ, 28 12.64 21.60

43.72 3.00 13.91 23.47 10.61 43.68 2.97 13.86 23.51 10.63

45.58 5.51 13.29 22.43 10.14 45.44 MO 13.21 22.19 10.00

example

(2)

11

12th

13th

λ ττ τντ Tt , 97 12th , 72 21 , 47 9 , 71 13th 1 cn —13—13—: ₅ c cn 47.28 , 86 12th , 70 21 , 53 9 , 64 . . ... CO 47.22 b

Connection No.

^ 54

Table I (continued)

structure

Melting point,

>

Elemental analysis,

At-

Cl

43.38 3.34 12.65 21.34 19.30
43.29 3.30 12.58 21.33 19.27

14th

, 29

(4) 54.87 5.74 12.00 20.25
: 3.77 12.12 20.15

Footnotes:

(1) Known connection

(2) The connection was made according to the example given

(3) The values on the top row have been calculated, the values

(4) refractive index

manufactured.

found on the bottom line.

^ 554866

Of the compounds listed in Table I, the following are preferred as active ingredients for the invention

Fungicide used:

1-methyl-2-acetyl-4 - (3 ', 5'-dichlorophenyl) urazole, 1-methyl-2-ethyl-4- (3', 5'-dichlorophenyl) urazole, 1-methyl-2 -n-propyl-4- (3 ', 5'-dichlorophenyl) urazole, 1-methyl-2-isopropyl-4- (3', 5'-dichlorophenyl) urazole, 1,2-dimethyl 1-4- ( 3 ', 5' -dichlorophenyl) urazole, 1-methyl-2-phenyl-4- (3 ^f , 5 ^! -Dichlorophenyl) urazole,

¹ j 2 "( 1" - ^^ yltzimethylene) -A- (3 *, 5 '-dichlorophenyl) -urazole,

1,2- (1 "-Methyltetramethylene) -4- (3 ', 5'-dichlorophenyl) -urazole and 1,2-pentamethylene-4- (3 ', 5'-dichlorophenyl) urazole.

The 1,2-substituted 4- (3 ', 5'-dichlorophenyl) urazole derivatives can be applied as such to the plants to be treated. Appropriately, however, they are before application diluted with a common tool and processed into an emulsion, a wettable powder or a dust.

All materials customary for fungicides can be used as auxiliaries, such as, for example, liquid or solid carriers, emulsifiers, dispersants, distributors, penetrants or surface-active agents.

Examples of liquid carriers suitable according to the invention are various solvents such as water; an alcohol like

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Methyl alcohol, ethyl alcohol and ethylene glycol; Ketones like Acetone, methyl ethyl ketone and cyclohexanone; Ether, such as methyl ether, Dioxane and cellosolve; aliphatic hydrocarbons such as gasoline and kerosene; aromatic hydrocarbons, such as Benzene, toluene, xylene, solvent naphtha. and methylnaphthalene; halogenated hydrocarbons such as dichloromethane, trichlorobenzene and carbon tetrachloride; Acid amides, v / ie dimethylformamide; Esters such as ethyl acetate, butyl acetate; Aliphatic acid glycerides, and nitriles such as acetonitrile.

Examples of solid supports suitable according to the invention are clay, Kaolin, bentonite, talc, diatomaceous earth, gypsum, vermiculite, Clay, sulfur, white carbon and carboxymethyl cellulose. These solid supports can be used singly or as mixtures of two or more compounds.

Suitable surface-active agents are, for example, the non-ionic types such as polyoxyethylene alkylaryl ethers and polyoxyethylene sorbitol monolaurate; the cationic types such as alkyldimethylbenzylammonium chloride and alkyl pyridinium chloride; anionic types such as alkylbenzenesulfonate, lignin sulfonate, and sulfates a higher alcohol; and anphoteric types such as alkyldimethylbetaine and dodecylaminoethylglycine.

The auxiliaries can be used alone or as a mixture of two or more compounds.

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Emulsions can be prepared by adding 10 to 50 wt. Parts of an active ingredient, 10 to 40 Sew "parts of a solvent and 5 to 20 parts by weight of a surfactant processed into a concentrate, which is then diluted with water to a predetermined concentration and applied to the Plant or the soil is applied, e.g. by spraying.

Wettable powders can contain 10 to 50 parts by weight of active ingredient, 10 to 40 parts by weight of solid carrier and 5 to 20 parts by weight of a surface-active agent. The powder can be diluted with water before use.

Dust-like compositions can contain 1 to 5 parts by weight of active ingredient and from 95 to 99 parts by weight of a solid carrier.

The fungicides according to the invention can together with one or several other active ingredients, such as insecticides, miticides or other! fungicides, can be used that make the fungicidal Do not impair the properties of the compounds according to the invention.

The fungicide according to the invention can be applied either to the foliage or to the arable soil. The dosage "is in general 500 to 1500 ppia when treating the foliage and 50 g to 300 g per 100 m when treating the arable soil.

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It has been found that the fungicide according to the invention have a broad spectrum of activity as fungicides, particularly well for Prevention of certain plant diseases used

the fruits, such as apples and grapes, and vegetables, such as tomatoes, cucumbers, beans and rice plants; Such diseases are e.g. rice husk meltau, botrysis gray mold, Rice brown spot, Alternaria leaf spot, and Sclerotinia rot. It was also found that the fungicide is also effective against two or more diseases at the same time, is exceptionally low in toxicity for humans and fish, and one ■ has low-- phytotoxicity, --——— «■ —- = -—- ---.- ·.-....., -, - ■ -.—, -

The present invention is further illustrated by the compositions and experiments set out below. Unless otherwise indicated, all parts mentioned are parts by weight.

Composition 1 - dust

The following ingredients were mixed and made into a fine one

Powdered dust:

Connection No. 3 3 parts

Mixture of clay and talc 97 parts

Instead of Compound No. 3, Compound No. 40 was used for the preparation the powdery composition is used.

Composition 2 - Wettable Powder

The following components were mixed and made into one wettable powder processed:

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Connection ITr. 17 20 parts

Mixture of clay and

Diatonic earth 75 parts

Sodium alkylbenzenesulfonate 3 parts

Polyoxyäthylennonylphenylätiier 2 parts

Instead of compound no. 17, compound 4-2 became the Manufacture of the wettable powder used.

Composition 3 - emulsion

The following components were - with stirring - & u - a · processed:

Connection No. 34 50 parts

Xylene 40 parts

Polyoxyäthylennonylphenyläther 6 parts

Sodium alkylbenzenesulfonate 4 parts

Instead of compound no. 34, compound no. 41 was also used to prepare the emulsion.

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2554868

Experiment 1: Preventive action against hot-bowl lüeltau rice plants (culture: Kinmaze) that had sprouted 5 Ms of 6 leaves, grew in 9 cm pots in a greenhouse and had been cut back to a height of 20 to 30 cm, y / urden sprayed with suspensions of the wettable powder, which contained the active ingredients in different concentrations; the dosage was 20 cesi per pot. After air drying, the plants were inoculated with the pathogenic mycelium of Pellicularia sasakii , which had been cultivated on fallow bran for 7 days.

The pots were covered with polyvinyl chloride boxes to prevent moisture loss and placed in a chamber maintained at 25-27 ° for incubation. After 20 days, the severity of the disease infestation was determined.

The same procedure was repeated with ice plants that had not been treated with the active ingredient.

Then the preventive value was calculated according to the Yiirkstoffes following equation:
Preventive value in $

_ (A) - Severity of the infestation, treated

Severity of the infestation, untreated (corresponds to A)

The results are shown in Table II.

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Table II 500 ppm 250 ppm link
No. Preventive Vfert, % 97.4 86.3 3 1000 ppm 81.4 70.8 4th 100 74.3 68.5 5 93.2 80.5 75.5 6th 79.6 78.0 64.8 9 92.0 89.6 85.3 10 76.3 .... 79., 6,. , .._ 73 _t 1 _, _ __14 ..... _.-. 91.4 72.9 60.4 ¹ 5 , £ 5.4 ... 79.3 70.4 16 79.6 89.7 83.4 17th 82.4 64.8 60.3 19th 97.5 81.6 70.4 20th 73.2 92.2 84.6 21 78.9 92.0 82.1 22nd 98.4 95.7 84.2 26th 99.3 " 85.2 71.4 27 98.4 72.4 63.5 28 86.3 81.8 73.2 29 83.5 72.4 68.8 30th 92.6 81.6 73.2 32 83.2 69.7 72.4 33 93.4 93.2 85.5 34 85.6 88.0 82.1 35 99.3 79.4 61.8 36 91.4 82.6

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Table II (continued)

link
No. Preventive value, % 500 ppm 250 ppm 41 1000 ppm 98.6 89.2 42 100 97.3 88.4 44 100 85.3 76.4 45 92.1 95.3 86.6 46 99.0 72.3 65.8 47 85.4 91.2 84.6 48- 99.4 - 72.0 --.- ^ 49 - ■ 83.4 - - 75.8 63.0 50 79.4 92.4 89.6 51 98.6 83.7 70.0 52 90.8 86.3 72.5 53 91.4 93.2 85.3 97.4

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Experiment 2; Preventive Effect on Cucumber Gray Mold Cotyledons of cucumber seedlings (culture: Sagamihanziro) were immersed in aqueous suspensions of the wettable powder containing the active ingredients in different concentrations, and then air-dried. The cotyledons were inoculated with the pathogenic mycelium of Botrytis cinerea and incubated in a chamber kept at 25 ° with humidity. After 7 days, the severity of the disease was determined.

The above procedure was repeated - where - at - jedocii - the cotyledons have not been treated with the active substances.

-Then the preventive Y / ert was made according to the equation of the experiment 1 calculated.

The results are shown in Table III.

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Tabel III 500 ppm 250 ppm Preventive value, $> 93.2 91.8 ν er d muting
Fr. 1000 ppm 98.2 95.4 2 96.5 95.4 90.6 3 * 100 91.5 82.3 7th 96.2 98.6 92.0 8th 98.4 72.3 69.8 11 100 , .. 90 * 4. ... _ 83. ,, 4 12th 83.2 98.6 95.3 13 · 97.3 82.6 80.4 18th 100 76.4 63.5 23 97.4 96.3 91.5 24 83.2 73.2 65.4 25th 100 92.4 86.3 31 85.4 98.0 92.1 37 100 92.3 88.5 40 100 95.7 90.4 41 96.4 82.4 72.3 42 100 86.4 80.8 43 86.2 79.0 68.4 45 92.5 89.3 82.1 49 85.3 80.4 73.8 50 98.6 85.0 72.9 51 85.3 53 91.6

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Experiment 3 '· Preventive effect Gegan over rice brown spot sick ness

Rice plants ("Culture: Kinmaze") that have sprouted 4 to 5 leaves and grown in 9 cm pots in a greenhouse sprayed with suspensions of the wettable powder containing the "active ingredients contained in predetermined concentrations; the dosage was 20 ecm per pot.

After drying in air, the plants were inoculated with a suspension containing pathogenic spores of Cochliobolus miyabeanuswas , and incubated in a humid chamber with atmospheric humidity at 25 ° to 27 °. After 48 hours , the number of spots ("lesions") was determined.

The procedure was repeated with ice plants that did not match the active substances had been treated

Then the preventive value was calculated according to the following equation:

Preventive value in $

_ (A) - number of spots treated "

Number of spots, untreated (corresponds to A)

The results are summarized in Table IV.

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Table IV Preventive-7 / ert, $ 125 ppm 62.5 ppm link
Ur. 250 ppm 92.6 86.7 3 500 ppm 99.1 81.9 72.4 8th 100 92.6 95.2 89.4 13th 97.4 98.0 72.5 63.2 comparison 100 91.3 S-dichlorosuccinimide 98.6 became N-3, * As a comparison connection

used.

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Experiment 4: Protection against gray mold on white beans

Y / eisse bean plants that had sprouted 2 leaves were made sprayed with suspensions of the wettable powder from the test compounds and air dried. The dosage was 25 ecm per plant.

Then a leaf was inoculated with a 6 mm agar disc which contained pathogenic myceus from Botrytis cinerea and incubated for 4 days at 23 ° in a chamber with atmospheric humidity.

The protection value was calculated according to the equation of experiment 1.

The results are shown in Table V.

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Table V link
Ur. Protection value, 40 100 41 96 42 89.7 43 78. 45 100 46 93.3 47 "72 51 75

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Claims (6)

Patent claims: (T) Fungicidal composition, characterized in that it contains an effective amount of a compound of the following general formula and a carrier: where in this formula X and Y each represent oxygen and / or sulfur; S ₁ and R _{2 can have the} same or different meanings and represent an alkyl, alkenyl or alkynyl group is an aryl group which can in particular contain at least one alkyl or halogen substituent, acyl, alkylcarbamoyl, alkoxycarbonyl, alkylthiocarbamoyl or (alkylthio) thiocarbamoyl group, and R ₁ and R ₂ together represent an alkylene group with 3 to Can form 8 carbon atoms, which can contain a methyl radical in the side chain. 609825/1000 2. Composition according to claim 1, characterized in that in the formula IX for oxygen and Y for oxygen or sulfur, R ₁ and Rg can have the same or different meanings and each represent an alkyl, alkenyl, alkynyl, phenyl , Acyl, alkylcarbamoyl or alkoxycarbonyl group and R., and Rp in. Side chain can contain a methyl radical. 3. Composition according to claim 1, characterized in that that in the formula I X for oxygen and Y for oxygen or sulfur and R ^ one methyl group and Rp one Is methyl, ethyl, phenyl or acetyl group. 4. Composition according to claim 1, characterized in that that they contain an effective amount of 1-methyl-4- (3 ^f , 5'-dichlorophenyl) urazole, 1,2-dimethyl-4- (3 ', 5'-dichlorophenyl) urazole, or 1-methyl-2 -phenyl-4- (3 ', 5'-dichlorophenyl) urazole and a carrier. 5. Composition according to claim 1, characterized in that it contains an effective amount of 1,2-trimethylene-4- (3 ', 5'-dichlorophenyl) urazole, 1,2-tetramethylene-4- (3', 5 ' dichlorophenyl) urazole, 1,2-pentamethylene-4- (3 ·, 5'-dichlorophenyl) urazole or 1,2-trimethylene-4- (3 ', 5'-dichlorophenyl) thiourazole and a carrier . 609825/1000 255A866 6. A method for combating fungal infestation, characterized in that fungi which are pathogenic for plants are treated with a lethal dose of a fungicidal composition according to Claims 1 to 5. S09825 / 100U