AU606802B2 - Synergistic fungicidal compositions containing two or three active ingredients - Google Patents

Description

r, -i Form COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952-69 COMPLETE SPECIFICATION

(ORIGINAL)

oil'4 8 2 Class Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: o Published: Priority Related Art: Name of Applicant: ESZAKMAGYARORSZAGI VEGYIMUVEK Address of Applicant: Sajobabony, H-3792, Hungary Actual Inventor: Address for Service KAROLY BALOGH, IMRE CSATLOS, ZSOLT DOMBAY, SANDOR GAAL, GUSZTAV GAL, ERZSEBET GREGA, MARIANNA GYORI, JOZSEF HORVATH, ROZSA HUSZAR, JOZSEF KARSAI, MAGDOLNA MAGYAR, JOZSEF NEU, MARGIT NEU, CSABA PAVLISCSAK, ENDRE SEBESTYEN, GYULA TARPAI, ISTVAN VARGA ANDRAS VARGA XEWbGX3eh g Watermark Patent Trademark Attorneys 50 QUEEN STREET, MELBOURNE, AUSTRALIA, 3000.

Complete Specification for the invention entitled: SYNERGISTIC FUNGICIDAL COMPOSITIONS CONTAINING TWO OR THREE ACTIVE

INGREDIENTS

The following statement is a full description of this invention, including the best method of performing it known to US SYNERGISTIC FUNGICIDAL COMPOSITIONS CONTAINING TWO OR THREE ACTIVE INGREDIENTS The invention relates to synergistic fungicidal compositions containing two or three active ingredients.

The compositions according to the invention can widely be used in case of cereals (wheat, barley, corn, rice), field crops (beans, peas, soya, potato, sunflower), plantations cotton, sugar beet, flax), fruits (apples, vine), ornamental plants pink) 0 o 000 to control pathogenic fungi e.g. different smut fungi, o o fusarium species, powdery mildew, downy mildew, grey 0 0 o mould, scab etc.

The compositions according to the invention o o contain in a total amount of 10 90 by weight and in a ratio of (10:1) (1:10) and (10:1:1) (1:10:10), o o respectively, 2-(0-/substituted alkyl/-2-thio-l,3,2- -oxathia phospholane derivative of formula R -CH-0. s P-0-CH-CH-X (I) I I R -CH-S 2

R

3

R

4 i wherein

R

1

R

2

R

3 and R 4 stand independently from each other for hydrogen, alkyl having 1 to 6 carbon atoms, alkenyl having 2 to 6 carbon atoms, alkynyl having 2 to 6 carbon atoms, A4485-803-KY 11~ 2 0000 OC 00 0000 0io o a o 0 *0 Soc 00 C I O o a 0 0 0)0 0300 0 3 0 1 0 0 0 0 00 B a0 0 0 0 000 9 0 a o 9 a X is halogen or hydrogen, alkyl having 1 to 6 carbon atoms or mercapto and a manganese and zinc complex of 8-quinolinolato- -dimethyl-dithiocarbamate complex (Mn:Zn 1:1) and/or benomyl (l-butyl-carbamoyl-benzimidazole-2-methyl-carbamate) as active ingredients in admixture with known solid or liquid carriers and other additives, preferably emulsifying, dispersing and wetting agents.

The 2-0-(substituted alkyl)-2-thio-l,3,2- 10 -oxathiaphospholane derivatives of formula are known from Hungarian Patent Application No. 1650/87 and can be used to control different pathogenic fungi of cultivated plants paprika, tomato, wheat, corn, sunflower, sugar beet, cotton), e.g. Alternaria 15 spp., Fusarium spp., Phytophthora infestans, powdery mildew.

The manganese and zinc complex of 8-quinolinolato- -dimethyl-dithiocarbamate (Mn+Zn 1:1) and its fungicidal activity is described in the HU-PS No. 171,736.

20 The known composition containing said complex as active ingredient (Kelokarb 80 WP) can be used for treating winter wheat sowing-seeds in an amount of 2 kg/to.

The composition containing benomyl as active ingredient (Chinoin Fundazol 50 WP) can be used e.g.

in autumn and spring cereals against powdery mildew of cereals and fusarium rot of cereals, in sugar beet against cercospora leaf spot, in alfalfa against downy mildew of alfalfa, against different plate diseases 3 of sunflower, in orchards e.g. in apples and pears against powdery mildew, monilia and scab in strawberry, raspberry, in vine against grey mould, in vegetables, e.g. in paprika, cucumber and root vegetables against powdery mildew, in ornamental plants, e.g. in pink against fusarium, botrytis and penicillium either alone or in combination with other known fungicides, e.g.

Quinolate V-4X, Dithane M-45, Orthocid 50 WP, Daconil 10 During our experiments it has been investigated o o howthe fungicidal activity of 2-(0-substituted alkyl)- S-2-thio-l,3,2-oxathiaphospholane-derivatives changes Swhen admixing it with other, known, commercially available compositions. Different seeds (winter wheat, autumn S° 15 and spring barley, corn, sunflower, soya, cotton, sugar 0n beet, rice, pears), tubers potato) or shoots .o apple, vine) were treated with compounds of formula with known fungicides and with the mixture thereof.

After seed dressing, spraying and treatment of the 20 soil the amount of the germinated plants, the length 0 of the roots, the rate of the infection and the yield were determined and it has been found that the activity of compounds of formula is generally the same as that of other known compositions, however, the activity of the combinations is significantly increased. Particular good activity has been observed when combining the compound of formula with Kelokarb which results in an increase of the activity spectrum and with i 4 benomyl, which results in a significant decrease of the effective dose of benomyl having systemic activity.

The present invention therefor provides synergistic fungicidal compositions containing two or three active ingredients in a total amount of 10 90 by weight and in a ratio of (10:1) (1:10) and (10:1:1) (1:10:10), respectively, 2-(O-substituted alkyl)- -2-thio-1,3,2-oxathia-phospholane derivative of formula S. 10 wherein R 1

R

2

R

3

R

4 and X are the same as mentioned above and Mn+Zn complex of 8- -quinolinolato-dimethyl-dithiocarbamate and/or benomyl in admixture with solid or liquid carriers and optionally with other additives, preferably emulsifying, dispersing or wetting agents.

0o A carrier in a composition according to the invention is any material with which the active ingredient is formulated to facilitate application to the locus to be treated, which may for example be a plant, seed or soil, or to facilitate storage, transport or handlinp.

A carrier may be a solid or a liquid including a material which is normally gaseous but which has been compressed Sto form a liquid and any of the carriers normally used in formulating pesticidal and fungicidal compositions may be used.

Suitable solid carriers include e.g. synthetic silicates, diatomaceous earth, talc, kaolin siliceous earth etc.

L I 5 Suitable liquid carriers include e.g. optionally halogenated hydrocarbons, aromatic hydrocarbons, dimethyl formamide, vaseline oil.

Agricultural compositions are often formulated and transported in a concentrated form which is subsequently diluted by the user before application. The presence of small amount of a carrier which is a surface- -active agent facilitates this process.

A surface-active agent may be an emulsifying oa 0 agent, a dispersing agent or a wetting agent; it may be nonionic or ionic. Preferably e.g. fatty alcohol- S-polyethylene glycol ether, the mixture of dodecylbenzene sulfonic acid-Ca salts and polyoxyethylene alkyl phenols, cresol-formaldehyde condensate, sulfite Ive onnder etc.

,otfo 15 are used. The compositions of the invention may for -0 4 o0:. example be formulated as wettable powders, dusts, granules, solutions, emulsifiably concentrates, emulsions, suspensions, suspension concentrates. The emulsifiably concentrates, wettable powders and dusts are preferred.

20 The invention further provides a method of controlling pests and fungi, which comprises applying a composition according to the invention in a sufficient amount to the plant.

The preferred compounds of formula used as one of the active ingredients in the composition according to the invention are summarized in Table

I.

h -6 Table I No. RRRRx n23 1 2 3 4o 0 a 4 0 6 aa 1.

2.

3.

4.

6.

7.

8.

9.

11.- 12.

13.

14.

16.

17.

19.

21.

22.

H

H

H

CH 3 CH 3 CH 3

H

H

H

H

H

H

H

H

H

CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3

H

H

H

H

H

H

CH 3 CH 3 CH 3

H

H

H

H

H

H

CH 3 CH 3 C 1H 3

H

H

H

H

H

H

H

H

H

H

H

H

H

CH 3 C

H

3 CH 3

H

H

H

H

H

H

CH

3 CH 3 C

H

3

H

H

H

H

H

H

H

H

H

H

H

H

H

CH 3

CH

3 CH 3

H

H

H

H

H

H

C 11 3 1.5602 1.5057 1.5971 1.5702 1.5804 1.5906 1. 5004 1.5902 1.5908 1.5503 1.5603 1.5704 1.5572 1.5704 1.5804 1.5724 1. 5904 1 .5908 1 .5422 1. 5627 1.5828 1.5422 -7- Table I contd. No. R R 4 Xn2 23. CH 3 H H CH 3 Br 1.5623 24. CH 3 H H CH 3 1 1.573B H CH 3 H CH 3 cl 1.5422 26. H CH 3 H CH 3 Br 1.562B 27. H CH 3 H CH 3 1 1.5923 28. H H CH 3 CH 3 Cl 1.5524 29. H H CH 3 CH 3 Br 1.5623 H H CH 3 CH 3 1 1.5729 31. H CH 3 C H 3 CH 3 Cl 1.5672 32. H CH 3 C H 3 CH 3 B r 1 .6264 33. H CH 3 CH 3 CH 3 1 1.5962 34. CH 3 CH 3 CH 3 H cl 1.5762 CH 3 CH 3 CH 3 H Br 1.5804 36. CH 3 CH 3 CH 3 H 1 1.5960 37. CH 3 H CH 3

CH

3 Cl 1.5878 38. CH 3 H CH 3 Cid 3 Br 1.5906 39. CH 3 H CH 3 CH 3 3 1.5908 CH 3 CH 3 H CH 3 cl 1.5670 41. CH 3

CH

3 H CH 3 Br 1.5702 42. CH 3 CH 3 H CH 3 Cl 1.5706 43. CH 3 CH 3 CH 3 CH 3 Cl 1.5662 -08- Table I.

(contd. No. R 4 RXn 23 1 2 3f4 o 'a o 'a 0 'a 'a 'a 'a 0 0 'a o ~o 'a a"a 'a 'a 'a 0"a0 'a ~0 0', o 0 'a 'a 0 03 o 'a o 'a 'a 'a "a-o 'a 00 o 'a 0 4601 6 0',40 00 00 0 1 I I 44.

46.

47.

48.

49.

50.

51.

52.

53.

54 55.

56 57.

58 59.

61.

62.

63.

64 CH 3 CH 3

H

CH 3

H

H

H

H

CH 3 CH 3 CH 3

H

H

H

H

H

CH 3

H

H

CH 3 CH 3 CH 3 CH 3

H

H

CH 3

H

H

H

CH 3 CH 3

H

H

H

H

H

H

CH 3

H

CH 3

H

CH 3 CH 3

H

H

H

CH 3

H

H

H

CH 3 CH 3

H

HI

C H1 3

H

H

H

H

CH 3

H

H

CH 3 CH 3 CH 3 C

H

3 CH 3 C

H

3 CH 3 CH 3 C Hd 3 CH 3 C

H

3

H

H

H

FH

C 2 H 5 C 2 H 5

H

C 2 H 5

H

c 2 H 5 B r

H

H

H

H d

H

C H 3

H

CH 3

H

5CH

H

S 2H5

H

H

H

H

1 .5708 1 .5706 1 .5529 1.5006 1.5706 1 .5604 1.5448 1 5253 1 .5224 1.5352 1 .5352 1. 5529 1.5572 1.5369 1.5352 1.-5539 1.5816 1 .5726 1.5614 1. 5252 1.5234 ii i- i I 1 9 Table I.

(contd.) 0 0 0 '0 0 0 0 *0 '4 00 0 O Q' 0 00' 00 0 eo a &4 003 0 S0 0 o o o 040 0 Q4 0 0 a oo '400 '4 '4000 Oa $0 *o '4 '4 I006 00 -a «o o 23 No. R 1

R

2

R

3

R

4 X n

D

CH

3

CH

3

CH

3

C

3

H

7 H 1.5362 66. CH 3

C

3

CH

3

C

2

H

5 H 1.5372 67. H H H i-C 3

H

7 H 1.5518 The fungicidal compositions according to the invention are illustrated by the following non- -limiting examples. In the Examples unless otherwise stated the amounts of the components are always given 15 in by weight.

Example 1 Wettable powder (10 WP) In a laboratory blender 9 of compound 1 of Table I (hereinafter I/1) is sprayed under stirring onto 25 of Sipernat 50 (synthetic silicate carrier), thereafter 1 of benomyl or zinc, manganese complex of 8-quinolinolato-dimethyl-dithiocarbamate as active ingredient, 55 of kaolin as carrier, 2 of Netzer IS (aliphatic sulfonic acid Na-salt) as wetting agent, 3 of Dispergiermittel 1494 (cresol/formaldehyde condensate) and 5 of sulfite waste powder as dispersing agents are added. Thereafter the mixture thus obtained

I--

10 is homogenized under stirring and finely ground in a laboratory biting cross mill (type Alpine 63 C).

The wettable powder thus obtained contains compound I/1 and benomyl or zinc, manganese complex of 8- -quinolinolato-dimethyl-dithiocarbamate in a total amount of 10 and in a ratio of 9:1.

Following the above procedure but using any other compound of Table I and benomyl or zinc, manganese o complex of 8-quinolinolato-dimethyl-dithiocarbamate similar 10 WP compositions may be obtained.

Example 2 Wettable powder (20 WP) In the apparatus according to Example 1, 2 15 35 of kaolin and 40 of silicic acid as carriers, of compound I/1, 5 of benomyl or 8-quinolinolatoo -dimethyl-dithiocarbamate complex as active ingredients, fatty alcohol sulfate and 2.5 of ligninsulfonate-Ca-salt as wetting agents are admixed and further the procedure of Example 1 is followed. The wettable powder thus obtained contains the two active ingredients in a total amount of 20 and in a ratio of 3:1.

Example 3 Wettable powder (45 WP) In the apparatus according to Example 1 of compound I/1 is sprayed onto 45 of Sipernat carrier and 15 of benomyl or zinc, manganese 11 t complex of 8-quinolinolato-dimeti;l-dithiocarbamate as active ingredient, 2 of Netzer IS as wetting agent, 3 of dispergiermittel 1494 and 5 of sulfite waste powder as dispersing agents are added and further the procedure of Example 1 is followed. The wettable powder thus obtained contains the two active ingredients in a total amount of 45 and in a ratio of 2:1.

Following the above procedure but using any other compound of Table I similar 45 WP compositions 0 oo ."000 10 containing two active ingredients may be obtained.

o o °Example 4 o Wettable powder (50 WP) The procedure of Example 3 is followed but 15 40 of Sipernat 50 carrier, 25 of any compound of Table I and 25 of benomyl or zinc, manganese complex of 8-quinolinolato-dimethyl-dithiocarbamate are used.

The wettable powder thus obtained contains the active ingredients in a total amount of 50 and in a ratio 20 of 1:1.

0 0 Example Wettable powder (50 WP) In the apparatus according to Example 1 45 of siliceous earth as carrier, 5 of compound I/l, 45 of 8-quinolinolato-dimethyl-dithiocarbamate as active ingredients, 2.5 of ligninsulfonic acid Ca-salt and 2.5 of fatty alcohol sulfate as wetting 12 agents are admixed and further the procedure of Example 1 is followed, the wettable powder thus obtained contains compound I/1 and zinc, manganese complex of 8- -quinolinolato-dimethyl-dithiocarbamate active ingredients in a total amount of 50 and in a ratio of 1:9.

Example 6 Wettable powder (50 WP) o 10 In the apparatus according to Example 1 of Sipernat 50 and 30 of kaolin as carriers, of compound I/1 and 40 of benomyl as active ao0 ingredients, 2 of Netzer IS as wetting agent, 3 0 of Dispergiermittel 1494 and 5 of sulfite waste powder as dispersing agent are admixed and further the procedure o of Example 1 is followed. The wettable powder thus obtained contains compound I/1 and benomyl as active ingredients in a total amount of 50 and in a ratio of 1:4.

O, 0 0 Example 7 Wettable powder (55 WP) In the apparatus according to Example 1 of Sipernat 50 and 25 of siliceous earth as solid carriers are admixed, thereafter 5 of compound I/1 is sprayed onto it, then the mixture thus obtained is admixed with 50 of zinc, manganese complex of 8-quinolinolato-dimethyl-dithiocarbamate or benomyl r- 0 4 4444 4444 0 0 0 40 4 4 o 61 0 e ait a e o 4 1 44* 4 a 13 as active ingredient, 2 of Netzer IS as wetting agent, 3 of Dispergiermittel 1494 and 5 of sulfite waste powder as dispersing agents are added and homogenized and ground in Alpine 63 C mill. The wettable powder thus obtained contains compound I/1 and benomyl or zinc, manganese complex of 8-quinolinolato-dimethyldithiocarbamate in a total amount of 55 and in a ratio of 1:10.

Following the above procedure but using any 10 other compound of Table I similarly 55 WP compositions, containing two active ingredients may be obtained.

Example B Wettable powder (60 WP) In the apparatus according to Example 1 20 of compound I/1 is sprayed onto 15 of Wessalon S (synthetic silicate) as carrier and 15 of siliceous earth as further carrier, 40 of benomyl or zinc, manganese complex of 8-quinolinolato-dimethyl-dithiocarbamate as further active ingredient, 2 of Netzer IS as wetting agent, 3 of Dispergiermittel 1494 and of sulfite waste powder as dispersing agents are added and further the procedure of Example 1 is followed.

The wettable powder thus obtained contains the two active ingredients in a total amount of 60 and in a ratio of 1:2.

-14 Example 9 Wettable powder (80 WP) In the apparatus according to Example 1 11 of Sipernat 50 as carrier, 40 of compound I/8 _,nomyl or and 40 of zinc, manganese complex of 8-quinolinolato- -dimethyl-dithiocarbamate as active ingredients, 2 of Netzer IS as wetting agent, 3 of Dispergiermittel 1494 and 4 of sulfite waste powder as dispersing agents are admixed and further the procedure of Example 9c4 10 1 is followed. The wettable powder thus obtained contains So the two active ingredients in a total amount of 80 o°n and in a ratio of 1:1.

00 04 Following the above procedure but using instead of compound I/8 compounds 1, 9, 13, 15, 21, 24, 26, o o15 29 or 33, similarly 80 WP compositions containing two o ive ingredients may be obtained.

o c* Example Oily suspension (50 FW) In a mixture containing 25 of compound I/1 as active ingredient, 40 of vaseline oil (technical grade), 8 of Emulsogen M (fatty alcohol-polyethylene glycol ether) and 2 of Atlox 4856 B (mixture of dodecylbenzene sulfonic acid Ca-salt and polyoxyethylene alkyl phenols) as emulsifying agents 25 of benomyl or zinc, manganese complex of 8-quinolinolato-dimethyl- -dithiocarbamate) is suspended and the mixture obtained finely ground in a laboratory ball mill. The oily sus- 15 pension thus obtained contains compound I/1 and benomyl or zinc, manganese complex of 8-quinolinolato-dimethyldithiocarbamate as active ingredients in a total amount of 50 and in a ratio of 1:1.

Following the above procedure but using instead of compound I/1 compounds 2, 3, 4, 5, 6, 7, 11, 12, 14, 16, 17, 18, 19, 20, 22, 23, 25, 27, 28, 31, 32 of Table 1, similarly 50 FW compositions containing two active ingredients may be obtained.

S° Example 11 Oily suspension (50 FW) sa o In the mixture containing 40 of compound I/l, as active ingredient 40 of technical grade vaseline oil, 8 of Emulsogen M and 2 of Atlox 4856 B as emulsifying agents, 10 of benomyl as active ingredient is suspended and further the procedure of Example 0 oi is followed. The oily suspension thus obtained contains compound I/1 and benomyl as active ingredients 20 in a total amount of 50 and in a ratio of 4:1.

Following the above procedure but using any other compound of Table I, and benomyl as active ingredients, similarly 50 FW compositions may be obtained.

Example 12 Oily suspension (60 FW) In the mixture containing 40 of compound I/l, as active ingredient 30 of technical grade 16 vaseline oil, 7 of Emulsogen M and 3 of Atlox 4856 B as emulsifying agents 20 of benomyl or zinc, manganese complex of 8-quinolinolato-dimethyl-dithiocarbamate) as active ingredient is suspended and further the procedure of Example 10 is followed. The oily suspension thus obtained contains compound I/1 and benomyl or zinc manganese complex of 8-quinolinolato-dimethyl- -dithiocarbamate as active ingredients in a total amount of 60 and in a ratio of 2:1.

Exaple 13 Wettable powder (20 WP) In the apparatus according to Example 1 of compound I/1 is sprayed onto 75 of siliceous earth as carrier thereafter 7.5 of benomyl and 10 0o of zinc, manganese complex of 8-quinolinolato-dimethyl- -dithiocarbamate as active ingredients, 2.5 of lignine t s" I sulfonic acid Ca-salt and 2.5 of fatty alcohol sulfate as wetting agents are added and further the procedure 20 of Example 1 is followed. The wettable powder thus obtained contains the three active ingredients (compound I/l, benomyl, zinc, manganese complex of 8-quinolinolato- -dimethyl-dithiocarbamate in a total amount of 20 and in a ratio of 1:3:4.

Example 14 Wettable powder (45 WP) In the apparatus according to Example 1 Illr- wu~-~U~ 17 a a a i ao a a~ a a, a a a a go a Q a hM a of compound I/1 is sprayed onto 50 of siliceous earth as carrier, thereafter 10 of benomyl and 30 of zinc, manganese complex of 8-quinolinolato-dimethyl- -dithiocarbamate as active ingredients, 2.5 of ligninsulfonic acid Ca-salt and 2.5 of fatty alcohol sulfate as wetting agents are added and further the procedure of Example 1 is followed. The wettable powder thus obtained contains the three active ingredients in a total amount of 45 and in a ratio of 1:2:6.

Example Wettable powder (55 WP) In the apparatus according to Example 1 5 of compound I/1 as active ingredient is sprayed 15 onto 25 of siliceous earth and 10 of Sipernat as carriers thereafter 10 of benomyl and 40 of zinc, manganese complex of 8-quinolinolato-dimethyl- -dithiocarbamate as active ingredients, 2 of Netzer IS as wetting agent, 3 of Dispergiermittel 1494 and 20 5 of sulfite waste powder as dispersing agents are added and further the procedure of Example 1 is followed.

The wettable powder thus obtained contains the three active ingredients in a total amount of 55 and in a ratio of 1:2:8.

Following the above procedure but using any other compound of Table I similarly WP compositions, containing three active ingredients may be obtained.

.77 18 0' a C 00 0 0a 0 00 o 0 00 0 0 0 0 00 *r 4t Example 16 Wettable powder (80 WP) In the apparatus according to Example 1 of compound I/1 is sprayed onto 11 of Sipernat as carrier and thereafter 20 of benomyl and 50 of zinc, manganese complex of 8-quinolinolato-dimethyl- -dithiocarbamate as active ingredients, 2 of Netzer IS as wetting agent, 3 of Dispergiermittel 1494 and 4 of sulfite waste powder as dispersing agents are added and further the procedure of Example 1 is followed.

The wettable powder thus obtained contains the three active ingredients in a total amount of 80 and in a ratio of 1:2:5.

15 Example 17 Emulsifiable concentrate (20 EC) In a flask equipped with a stirrer 70 of xylene, 20 of a compound I/1 as active ingredient, of alkyl phenyl polyethylene glycol ether and 5 of alkyl polyglycol ether as emulsifying agents are added under stirring, stirred until clear solution is obtained and optionally filtered. The emulsifiable concentrate thus obtained contains the compound I/1 in an amount of 20 Following the above procedure but using any other compound of Table 1, similarly 20 EC composition may be obtained.

0-2 19 "0 o co So0o o Soo o o 0 0 0 00 00 00 0* 0 0 #0 0 Example 18 Emulsifiable concentrate (50 EC) In the apparatus according to Example 17 of compound I/1 is admixed with 5 of polyethylene glycol (Carbovax 1000, polymerisation grade of 1000) and with 10 of the adduct of ethylene oxide and di(isohexyl-isoheptyl) phenol as emulsifying agents thereafter the emulsion thus obtained is completed to 100 with benzene. The emulsifiable concentrate thus obtained contains 50 of active ingredients.

Following the above procudere but using any other compound of Table 1 similarly 50 EC compositions may be obtained.

The activity of the fungicidal compositions 15 according to the invention containing two or three active ingredients has been tasted on various plants, against different fungi under laboratory and field conditions in comparison with known fungicidal compositions. The experiments and results thereof are shown in the following biological Examples.

Example 19 Fungicidal activity against bunt smut on winter wheat seeds The composition according to the invention containing two active ingredients was tested under laboratory conditions on winter wheat (variety of MV-8) against bunt smut (Tilletia spp).

20 The seeds were infected with 0.2 of bunt smut spore, thereafter seed dressed using compound I/1 (2-(0-2'-chloroethyl)-2-thio-1,3,2-oxathiaphospholane, in form of a composition prepared according to Example 17), Kelokarb 80 WP (80 of zinc, manganese complex of 8-quinolinolato-dimethyl-dithiocarbamate, Agrocit WP (50 of l-butyl-carbamoyl-benzimidazole-2-methylcarbamate) and the combinations thereof. The following treatments were carried out: Untreated control Compound I/1 1 kg/to seed Agrocit 50 WP 2 kg/to 0 og Kelokarb 80 WP 2 kg/to o o0 .oo Compound I/i. 0.25 kg/to Agrocit 50 WP 1.5 kg/to o 15 Compound I/i. 0.50 kg/to Agrocit 50 WP 1.0 kg/to Compound I/1. 0.75 kg/to Agrocit 50 WP 0.5 kg/to 0 Compound I/l. 0.25 kg/to Kelokarb 80 WP 1.5 kg/to Compound 0.50 kg/to Kelokarb 80 WP 1.0 kg/to 10.) Compound I/l. 0.75 kg/to Kelokarb 80 WP 0.5 kg/to Bo0. Seed impressions were made for every treatment respectively, f* using 4 x 100 seeds and 5 and 10 days/later the sporulao o tion ratio was determined on every impression. The results obtained are summarized in Table II.

21 Table II.

oa00 4 0 eo o o 0I 4 0 a 00 0 Q 0 S00 0 No. of the Rate of the sporulation in treatments on the 5th day on the 10th day after treatment 1. 75.3 82.9 2. 12.4 20.1 3. 19.7 28.3 4. 22.4 30.1 6.8 19.1 6. 3.8 7.3 7. 8.4 13.1 8. 9.7 18.3 9. 0.6 2.4 10. 2.9 5.6 The data of the Table II clearly show that the compound I/1 alone and the two known commercially available seed dressing agents are less active against bunt smut than the combinations thereof. Particularly active is the composition according to the invention containing compound I/1 and zinc, manganese complex of 8-quinolinolato-dimethyl-dithiocarbamate in a ratio of 1:2 (treatment No. 9).

i 22 Example Fungicidal activity against diseases of winter barley at germ stage The experiments were carried out on winter 2 barley (variety of GK-Szeged) in plots of 20 m 2 The intrinsic infection of seeds caused by Fusarium spp.

was 19 The seed dressing was carried out by -2'-chloroethyl)-2-thio-4-methyl-1,3,2-oxathiophospholane (compound 1/7 in form of composition of Example 17), Kelokarb 80 WP, Dithane M 45 (80 of /zinc, manganese/ o. ethylene-bis(dithiocarbamate)) and by the combination S, of these compositions. The treatments were as follows: 0 .o Untreated control o 00 Compound 1/7. 1 kg/to seed Kelokarb 80 WP 2 kg/to Dithane M-45 1.25 kg/to S° Compound I/7. 0.25 kg/to Kelokarb 80 WP 1.5 kg/to Compound 0.50 kg/to Kelokarb 80 WP 1.0 kg/to Compound 1/7. 0.75 kg/to Kelokarb 80 WP 0.5 kg/to Compound I/7. 0.25 kg/to Dithane M-45 0.9375 kg/to Compound 1/7. 0.50 kg/to Dithane M-45 0.625 kg/to 10.) Compound 1/7. 0.75 kg/to Dithane M-45 0.3125 kg/to 200 seeds per treatment were incubated in wet chamber, thereafter the number of germinated healthy seeds wa determined. In field experiments the number of the emerging plants was determined at the 2-4 leaves stage of the barley plants on a section of 3x5 m.

1__ 23 The results obtained are summarized in Table

III.

Table III.

0oo o t oo0000 o& O 00 0e 0 0 0 0 00 0 0 oP O 0 0* 0o0o i 0000 No. of the Germination Infection No. of plants treatment in Fusarium Alternaria per m spp. spp.

.0 1. 95.5 19.0 31.0 52.4 100.0 2. 99.5 3.7 4.5 54.8 104.6 3. 99.0 4.1 5.2 54.9 104.8 4. 99.5 5.3 6.8 53.7 102.5 5. 99.0 1.3 0 56.3 107.4 6. 99.0 0.5 0 56.9 108.6 7. 99.5 0.5 0 56.6 108.0 8. 99.5 2.0 3.0 55.9 106.7 9. 99.5 0 0 56.7 108.2 10. 99.0 0.5 0 56.7 108.2 The data of Table III clearly show that compound I/7 neither alone nor in combination with the other two commercially available seed dressing agents is phytotoxic to the seeds. The combinations protect the seeds against the pathogenic fungi and increase the emergence in comparison with the treated control as well as with the compositions containing only a single active ingredient.

I 24 Example 21 Fungicidal activity against diseases of corn at germ stage The experiments were carried out on hybride seed (variety of Pi 3747) in plots of 20 m2 The instrinsic infection of seeds caused by Fusarium spp was 23 and the capability of germinating was 94 The seed dressings were carried out by 2-(0-2'-chloroethyl)-2-thio-4,5-dimethyl-1,3,2-oxathiaphospholane (compound 1/16, in form of composition of Example 17), BF-51 90 WSC (90 of 3-isononyl-oxy- 0° propyl-ammonium-methylphosphonate), TMTD (50 of tetra- 0 methyl-tiurame disulfide), Kelokarb 80 WP and by the combinations of these compositions. The treatments 0 0 15 were as follows: Untreated control Compound 1/16, 1 kg/to seed TMTD 2 kg/to BF-51 90 WSC 1.1 1/to Kelokarb 80 WP 2 kg/to Compound 1/16 0.5 kg/to TMTD 1 kg/to Compound 1/16 0.5 kg/to BF-51 90 WSC 0.55 1/to 00 0 Compound 1/16 0.5 kg/to Kelokarb 80 WP 1.0 kg/to 200 seeds per treatment were incubated in wet chamber and the rate of infection was determined under laboratory conditions.

~31_ 25 200 seeds per treatment were sown on field plots and at 2-leaves stage of the plants the number of plants emerging from 200 seeds was determined. The results obtained are summarized in Table IV.

Table IV.

1)00 00B Ci ciI 1)0 ci "0 ci ci 0 ci 0 o no ci o 00 Sp No. of treatments 1.

2.

3.

15 4.

5.

6.

7.

8.

Infection Fusarium Penicillium Aspergillus pieces/200 seeds spp. spp. spp.

No. of emerged plants 23.0 5.3 7.9 5.7 7.5 1.5 0 2.0 17.0 2.1 6.8 4.2 6.5 0 0 0 100 104.9 102.2 104.4 101.7 108.3 109.4 108.8 The data of Table IV. clearly show that compound 1/16 in combination with the three different, commercial seed dressing materials protects the seeds of corn against fungal infection and increases the emergence 26 Example 22 Fungicidal activity against diseases of sunflower at germ stage The experiments were carried out on sunflower seeds (variety of GK 70) in plots of 20 m2 using 200 pieces of seed in every treatment. The seed dressings were carried out by 2-(0-1'-methyl-2'-chloroethyl)- -2-thio-4,5-dimethyl-l,3,2-oxathiaphospholane (compound 1/34, in form of composition of Example 17), Sandofan 25 WP (25 2-methoxy-N-(2-oxo-l,3-oxazolidine-3-yl)- -acet-2,6-oxylidide), Apron 35 SD (35 of DL-N-(2,6- -dimethyl-phenyl)-N-(2'-methoxy-acetyl)-alanine methylester), Kelokarb 80 WP and by the combinations of these compositions. The treatments were the following: Untreated control Sandofan 25 WP 2 kg/to seed Apron 35 SD 3 kg/to Compound 1/34. 0.5 kg/to Kelokarb 80 WP 2.0 kg/to Compound 1/34 0.25 kg/to Sandofan 25 WP 1 kg/to Compound 1/34 0.50 kg/to Apron 35 SD 1.5 kg/to Compound 1/34 0.50 kg/to Kelokarb 80 WP 1.0 kg/to When evaluating the experiments the values of infection were determined in laboratory conditions and in field the number of plants emerging from 200 seeds was determined at the 2-leaves stage. The results obtained are summarized in Table V.

27 Table V.

U4O oar a Os.. a 'S a eB o a *P ar No. of Infection No. of emerged plants treat- Botrytis spp. Alternaria spp. pieces/200 seeds merts 1. 29.0 16.0 152 100.0 2. 19.0 11.0 158 103.9 3. 18.0 12.0 158 103.9 4. 15.0 11.0 156 102.6 20.0 11.0 157 103.4 6. 7.0 3.0 169 111.2 7. 5.0 7.0 170 111.8 8. 5.0 4.0 174 114.5 The data of Table V. clearly show that the activity of compound 1/34 and the three commercially available compositions alone is inferior to that of the combinations of these materials. The composition 20 containing compound of Formula and zinc, manganese complex of 8-quinolinolato-dimethyl-dithiocarbamate in a ratio of 1:2 (treatment No. 8) shows a particular good activity, i.e. the infection has significantly been reduced and the emergence has significantly been increased.

l 28 Example 23 Fungicidal activity against diseases of soya at germ stage The experiments were carried out in 4 replicate in plots of 2 m 2 The seed dressings were carried out by 2-(0-n-propyl)-2-thio-l,3,2-oxathia-phosphulane (compound 1/46, in form of composition of Example 17), Kolfugo 25 FW (25 of 2-methoxycarbonyl-amino-benzimidazole), Orthocid 50 WP (50 of N-trichloro-methyl- 10 thio-tetrahydrophtalimide), Kelokarb 80 WP and by the S, combinations of these materials. The treatments were as follows: Untreated control 5 Compound 1/46 1.0 kg/to seed Kolfugo 25 FW 3.0 1/to Orthocid 50 WP 2.0 kg/to Kelokarb 80 WP 2.0 kg/to i Compound 1/46 0.375 kg/to Kolfugo 25 FW 1.5 1/to Compound 1/46 0.50 kg/to Orthocid 50 WP 1.0 kg/to Compound I/46 0.25 kg/to Kelokarb 80 WP 1.5 kg/to Compound 1/46 0.50 kg/to Kelokarb 80 WP 1.0 kg/to Compound 1/46 0.75 kg/to Kelokarb 80 WP 0.5 kg/to Just before the sowing the seeds were also treated witn Nitrofix vaccine in an amount of 2.0 kg/to.

The germination was determined on 200 seeds in laboratory conditions. By the field experiments the emergence as well as the number of the root tubers and the crop r *t

I

29 were determined. The results obtained are summarized in Table VI.

Table VI.

neon o n o @4 00 en ne *r a *4 4 p a.

44 04 9 No. of Germinating Emergence Weight of Crop (kg/m 2 treat- root tubers ments g/30 plants 10 1. 92.0 74.0 0.053 1.15 2. 95.0 81.0 0.049 1.16 3. 94.0 78.0 0.037 1.19 4. 94.0 82.0 0.040 1.22 5. 95.0 80.0 0.046 1.19 15 6. 97.0 86.0 0.047 1.20 7. 97:0 88.0 0.049 1.24 8. 96.0 85.0 0.045 1.22 9. 98.0 91.0 0.047 1.27 97.0 86.0 0.044 1.23 The data of Table VI clearly show that the combinations of compound 1/46 and the three commercially available seed dressing agents increase the germination the emergence as well as the crop in comparison with the untreated control and with the treatments carried out by compositions containing only a single active ingredient without any decreasing in the number of Rhizobium tubers. The composition according to the Ce..

Ce a i -Ilil--IYlti 30 invention containing compound of formula and zinc, manganese complex of 8-quinolinolato-dimethyl-dithiocarbamate in a ratio of 1:2 (treatment No. shows a particularly good activity.

Example 24 Fungicidal activity against diseases of cotton at germ stage The experiments were accomplished in glass house. The seed dressings were carried out by -2'-SH-ethyl)-2-thio-l,3,2-oxathiaphospholane (comt, pound 1/56, in form of composition of Example 17), S Quinolate 15 (15 of copper oxyquinolate), Topsion tiureido M 70 WP (70 of 1,2-bis-(3-methoxycarbonyl )-benzene), Kalokarb 80 WP and by the combinations of the materials.

The treatments were the following: Untreated control Compound 1/56 1 kg/to seed Quinolate 15 2 kg/to Topsin-M 70 WP 2 kg/to j Kelokarb 80 WP 2 kg/to Compound 1/56 0.15 kg/to Quinolate 15 1 kg/to Compound 1/56 0.70 kg/to Topsin-M 70 WP 1 kg/to Compound 1/56 0.25 kg/to Kelokarb 80 WP 1.5 kg/to Compound 1/56 0.50 kg/to Kelokarb 80 WP 1.0 kg/to Compound 1/56 1.0 kg/to Kelokarb 80 WP 0.5 kg/to 31 200 seeds were sown per treatment and the emergence of cotton plants was determined. The results obtained are summarized in Table VII.

Table VII.

No. of treatments Emergence

GINO

000 0 *Oo 00 0 o *o 0 0 0 00 0 00 Ot 0 4 00 @4 o o 43.0 68.0 69.0 70.0 61.0 83.0 88.0 87.0 96.0 94.0 The data of Table VII clearly show that the 20 compound 1/56 and the three commercially available compositions possess less activity alone against the disease of cotton at germ stage than the combinations of these materials. The composition containing compound of formula and the zinc, manganese complex of 8-quinolinolato-dimethyl-dithiocarbamate in ratios of 1:2 and 2:1 (treatment Nos. 9 and 10) is particularly effective.

L_

~w 32 Example Fungicidal activity against fungal diseases of spring barley The experiments were carried out in plots 10 m 2 and for the seed dressings 2-(0-n-butyl)-2-thio- -4,5-dimethyl-1,3,2-oxathiaphospholane (compound 1/63, in form of composition of Example 17), Baytsn F (15 of l-(4-chlorophenoxy)-l-(1H-1,2,4-triazol-l-yl)-3,3- -dimethyl-2-butanone 2 of 2-(2-furyl)-benzimidazole), o1o 10 Trifumine 30 WP (30 of 4-chloro-trifluoro-N-l-(1H- Kelokarb 80 WP and the combinations of these materials o were used. The treatments were as follows: o t Untreated control Baytan F 2.0 kg/to seed 0 0 Trifumine 30 WP 5.0 kg/to Kelokarb 80 WP 2.0 kg/to Compound 1/63 1.0 kg/to Compound 1/63 0.5 kg/to Baytan F 1.0 kg/to A g 20 Compound 1/63 0.75 kg/to Trifumine 30 WP 2.5 kg/to a" 0 Compound 1/63 0.5 kg/to Kelokarb 80 WP 1.0 kg/to The effect of the treatments was determined on a section of 10 x 1 m by determining the emergence at earing of corn, the rate of infection, caused by powdery mildew and Helminthosporium, on every leaf level from which the infection index was determined using the following scale: 33 0 no symptom 1 5 or less infection 2 6-10 infection 3 11-25 infection 4 26-50 infection 51-75 infection 6 76-100 infection wherein the values of infection mean the ratio of the surfaces of healthy and infected leaves and the average values of leaf-surfaces belonging to four leaf-levels ooco o0 covered by mycelia respectively. On the basis of the o a 0 0 data obtained the infection index was calculated 0 o0 *o using the following equation: O a i x fi a F. sooo 1 wherein a. is the infection value according to the above scale, f. is the frequency thereof and n is the number of the plants.

The results obtained are summarized in Table soo.

0 0VIII.

00 VIII.

34 Table VIII.

No. of Number of Infection index Yield treatments sprang plants Helmintho- Powdery to/ha per m sporium mildew 1. 56.1 1.88 2.93 4.77 2. 57.3 1.43 0.83 5.06 3. 56.4 1.43 2.20 4.78 4. 56.6 1.79 2.46 4.80 56.8 1.65 1.94 4.88 6. 59.4 1.03 0.03 5.36 o 7. 57.7 1.14 1.20 5.12 8. 57.9 1.57 1.89 5.01 The data of table VIII clearly show that by o400 the use of the composition containing two active ingredients the emergence of the spring barley can be in- ,I 0 creased, the rate of the infection caused by powdery mildew and Helminthosporium can be reduced in comparison with the untreated control and with the treatments carried out by a composition containing only one active ingredient. Due to these effects enhanced crop can also be obtained.

I-

35 Example 26 Fungicidal activity against fungal diseases of winter barley The experiments were carried out on plots 2 of 50 m The seeds of the winter barley were infected by loose smut. To get protection against the loose smut (Ustilago nuda) and against powdery mildew of barley (Erysiphe graminis hordei) seed dressings were carried out using 2-(0-2'-bromoethyl)-2-thio-l,3,2- -oxathiaphospholane (compound 1/2, in form of composioC tion of Example 17), Milstem (500 g/l of 0 -2-ethyl-amino-6-hydroxy-4-methyl-pyrimidine), Kelokarb 80 WP and with the combinations of these materials.

O 3 0 The treatments were as follows: o oo Untreated control Compound I/2 1 kg/to seed Milstem 5.0 1/to Kelokarb 80 WP 2.0 kg/to Compound 1/2 0.5 kg/to Milstem 3.0 I/to Compound 1/2 0.75 kg/to Milstem 2.0 1/to Compound 1/2 0.25 kg/to Milstem 4.0 1/to Compound 1/2 0.25 kg/to Kelokarb 80 WP 1.5 kg/to Compound I/2 0.50 kg/to Kelokarb 80 WP 1.0 kg/to 10.) Compound 1/2 0.75 kg/to Kelokarb 80 WP 0.5 kg/to 11.) Compound I/2 0.5 kg/to Kelokarb 80 WP 1.0 kg/to Milstem 2.5 1/to 36 12.) Compound 1/2 0.25 kg/to Kelokarb 80 WP 1.5 kg/to Milstem 3.0 1/to 13.) Compound I/2 1.0 kg/to Kelokarb 80 WP 0.75 kg/to Milstem 1.0 1/to The phytotoxic effects of treatments were evaluated by determining the emergence at the 2-4 leaves stage of barley. The rate of infection caused by powdery mildew was determined at flowering, using the scale and the infection index described in Example The rate of infection caused by smut fungi was evaluated at flowering by determining the number of ears. The results obtained are summarized in Table

IX.

Table IX.

pieces/plot mildew ao o 1. 53.6 50.5 3.64 2. 56.7 3.3 2.11 o 3. 54.8 49.3 0.85 4. 55.0 8.7 3.13 55.2 6.5 0.49 6. of No of emerged No. of ears Infection treat- plants per m infected by indes F.

ments loose smut for powdery pieces/plot mildew 0 0 1. 53.6 50.5 3.64 2. 56.7 3.3 2.11 3. 54.8 49.3 0.85 4. 55.0 8.7 3.13 55.2 6.5 0.49 6. 56.3 5.3 0.56 37 Table IX.

(contd.) No. of treatments 7.

8.

9.

10.

11.

12.

15 13.

No. of emerged plants per m No. of ears infected by loose smut pieces/plot Infection indes F.

for powdery mildew o .0 0 3 03 0 o. a 0 0 o a o o 0I Oo 300 0 00 00 K 0 t a a, 54.9 56.9 57.8 56.9 57.7 57.2 56.9 10.2 2.3 0.0 0.0 0.0 3.0 0.0 0.68 2.91 2.30 2.02 0.57 0.51 0.66 0oo 0 00 D c o o a 00 0 0 0 The data of Table IX clearly show that none of the compositions containing two or three active ingredients is phytotoxic to the winter barley as the values of emergence are in all cases higher than that of the untreated control. The compositions containing two or three ingredients provide protection for winter barley against both powdery mildew and loose smut. Such simultaneous effect cannot be obtained by the use of compositions containing only one active ingredient.

38 Example 27 Fungicidal activity against disease of sugar beet at germ stage Under laboratory conditions sugar beet seeds were treated using 2-(0-2'-chloroethyl)-2-thio-l,3,2- -oxathiaphospholane (compound I/1, in form of composition of Example 17), Kelokarb 80 WP, BenguinoX (1,4- -benzoquinone-N-benzoyl-hydrazone-oxime) and with the combinations of these materials. The treatments were as follows: 0 0i 004s 0 0 <10 0 0 0 0 00~ f C 4 00 0, 0 0 D u o 0 oo 000 0~r O 0 0 0 pa o r* o i o o Untreated control Compound I/1 125 g/to seed Compound I/1 250 g/to Compound I/1 500 g/to Compound I/1 1000 g/to Kelokarb 80 WP 2.0 kg/to Benguinox 50 g/to Benguinox 100 g/to Benguinox 200 g/to 10.) Benguinox 400 g/to 11.) Benguinox 800 g/to 12.) Benguinox 800 g/to Compound I/1 125 g/to 13.) Compound I/1 125 g/to Benguinox 400 g/to 14.) Compound I/1 250 g/to Benguinox 400 g/to Compound I/1 250 g/to Benguinox 200 g/to 16.) Compound I/1 500 g/to Benguinox 200 g/to 17.) Compound I/1 500 g/to Benguinox 100 g/to il 111~ 4.

39 18.) Compound I/1 1000 g/to Benguinox 100 19.) Compound I/1 1000 g/to Benguinox 50 Compound I/1 500 g/to Kelokarb 80 WP Benguinox 50 g/to 21.) Compound I/1 250 g/to Kelokarb 80 WP Benguinox 50 g/to 22.) Compound I/i 750 g/to Kelokarb 80 WP Benguinox 50 g/to 23.) Compound I/1 250 g/to Kelokarb 80 WP .0 Benguinox 200 g/to 24.) Compound I/1 500 g/to Kelokarb 80 WP Benguinox 400 g/to g/to g/to 1.0 kg/to 0.75 kg/to 0.5 kg/to 0.5 kg/to 0.25 kg/to o oo 0 0 00 0 0 a 0 0 0 0 O V 00 0a a o 00 0 u u 10 treated seeds were sown in every pot and the temperature thereof was kept at 6 8 OC and the water-content at 70 90 to provide favourable life conditions for pathogenic fungi of sugar beets at the germ stage (Pythium spp, Rizochtonia spp). The compositions were evaluated on the basis of emergence The results obtained are summarized in Table X.

Table X.

No. of treatments Emergence 37.9 49.8 Table X.

(contd No. of treatments Emergence 0 r GC 0

-O

00 63.1 69.4 52.3 57.6 36. 40.7 43.2 53. 2 60.9 88.6 87. 9 83.2 81.6 84.1 85.2 81 .3 82.5 90.2 87 .1 89 .3 80.4 87.6 1 41 The data of Table X clearly show that the value of emergence significantly increases after carrying out seed dressing with a composition containing compound I/l, with Kelokarb or with Benguinox. However, this effect may further be enhanced if the seed dressings are carried out with the compositions according to the invention containing two or three active ingredients.

4 0 0 0 4 0I ,0 03 00 0 C7 0 0 0 00 Example 28 Fungicidal activity against diseases of rice at the germ stage The experiments were carried out on plots of 25 m 2 For seed dressing 2-(0-2'-chloroethyl-2-thio- 15 -1,3,2-oxathiaphospholane (compound I/1 in form of composition of Example 17), Tachigaren 70 (70 of Kelokarb 80 WP and the combinations of these materials were used. The treatments were as follows: Untreated control Compound I/1 1.0 kg/to seed Tachigaren 70 3.0 kg/to Kelokarb 80 WP 2.0 kg/to Compound I/1 0.5 kg/to Tachigaren 70 1.5 kg/to Compound I/1 0.75 kg/to Tachigaren 70 1.0 kg/to Compound I/1 0.5 kg/to Kelokarb 80 WP 1.0 kg/to Compound I/1 0.5 kg/to Kelokarb 80 WP 1.0 kg/to Tachigaren 70 1.0 kg/to t i 7 r ~-17 42 The plants were evaluated at 2-leaves stage by determining the number of plants in a section of x 1 m in every plot, determining the length of plants.and the yield after harvesting.

The results obtained are summarized in Table Table XI.

0 0 0 0 0n 0 4444o o o 0 0 4.0 0 0 00 0 0 0 0 00 0 0j 000 t No. of No. of Length Yield treatments plants cm to/ha 1. 55.2 5.5 4.02 2. 58.9 5.8 4.17 3. 60.3 5.8 4.20 4. 58.6 5.6 4.11 5. 62.9 5.9 4.49 6. 66.3 5.9 4.30 7. 61.8 5.7 4.35 8. 68.8 5.9 4.58 The data of Table XI clearly show that all treatments improve the emergenc of rice, promote the initial growth of the young plants and enhance the yield.

tI r <1 43 4-00 44r 4J .i 0i r0 44 u 00 Obo O 4o 4 44 0 4D 0 4 Example 29 Fungicidal activity against diseases of sunflower at germ stage The sunflower plants emerging from the treated seeds were examined in plots of 20 m 2 The seed dressings were carried out with 2-(0-2'-chloroethyl)-2-thio-l,3,2- -oxathiaphospholane (compound I/l, in form of composition of Example 17), Kelokarb 80 WP, Ju-Knol (gibberelinic acid boric acid) and with the combination of these materials. The treatments were as follows: Untreated control Compound I/1 1.0 kg/to Kelokarb 80 WP 2.0 kg/to Ju-Knol 5.11 g/to Compound I/1 0.5 kg/to Kelokarb 80 WP 1.0 kg/to Ju-Knol 5.11 g/to Compound I/1 0.25 kg/to Kelokarb 80 WP 1.5 kg/to Ju-Knol 5.11 g/to Compound I/1 0.75 kg/to Kelokarb 80 WP 0.5 kg/to Ju-Knol 5.11 g/to Compound I/1 0.25 kg/to Ju-Knol 5.11 g/to Compound I/1 0.50 kg/to Ju-Knol 5.11 g/to Compound I/1 0.75 kg/to Ju-Knol 5.11 g/to 11.) Compound I/1 1.00 kg/to Ju-Knol 5.11 g/to The germination was determined on 200 seeds in wet chamber. In the field best 200 seeds were sown.

At the first leaf stage the number of the emerging -2 44 plants and at the 6-8 leaves stage the length thereof was determined, the results obtained are summarized in Table XII.

Table XII.

0 r 0000 ^00" 0a 0 00 0 0 0 tI tl CT a e i a 0 00 4 0 f 0 00 0 0 00© 00 0 4I O D 0 00 00 0 o o 040 0 0041 0 1 *04 0 No. of Germination No. of plants/ Average length treat- plot of plants, cm ments 1. 89 136 38.2 2. 94 142 41.7 3. 95 143 40.3 4. 97 142 44.2 5. 97 150 52.8 6. 96 146 48.7 7. 97 145 51.2 8. 96 141 46.1 9. 97 143 48.2 10. 96 143 49.7 11. 97 144 48.6 The data of Table XII clearly show that when the fungicidal compositions according to the invention (containing two or three active ingredients) are used in combination with Ju-Knol (germinating promoter) the number of the sunflower plants increases significantly and the initial growth thereof is also improved.

I

*74 Example Fungicidal activity on seed potato Seed dressings of seed-potato were carried out by 2-(0-1'-methyl-n-butyl)-2-thio-1,3,2-oxathiaphospholane (compound 1/62 in form of Example 17), Kelokarb 80 WP, Sayfos 80 (dimethyl-diamino-triazinyl- -methyl-dithiophosphate), Rhizolex 25 FL (2,6-dichloro- -p-tolyl-0,0-dimethyl-phosphorothioate) and with the combination of these materials. The treatments were as follows: Untreated control Compound 1/62 1.0 kg/to Kelokarb 80 WP 2.0 kg/to Sayfos 80 1.0 kg/to Rhizolex 25 FL 1.0 1/to oo. Compound I/62 0.5 kg/to Kelokarb 80 WP 1.0 kg/to 0 Q Compound 1/62 0.5 kg/to Rhizolex 25 FL 0.5 1/to Compound I/62 0.25 kg/to Sayfos 80 0.25 kg/to Compound 1/62 0.50 kg/to Sayfos 80 0.50 kg/to 10.) Compound 1/62 1.0 kg/to Sayfos 80 1.0 kg/to oo" 11.) Compound 1/62 0.5 kg/to Kelokarb 80 WP 1.0 kg/to 0 Sayfos 80 1.0 kg/to 12.) Compound 1/62 0.75 kg/to Kelokarb 80 WP 1.0 kg/to Sayfos 80 0.75 kg/to 13.) Compound 1/62 1.0 kg/to Kelokarb 80 WP 1.0 kg/to Sayfos 80 0.5 kg/to -46 The compositions were sprayed onto the seed- -potatoes and when the length of the shoots was 5 8 cm the ratio (in of the stocks infected by aphids (plant louses) thereafter the rate of rhizoctonic mouldering were determined on 100 underground shoots using the scale of 0 6 and infection index described in Example 25. After the harvesting the yield was also determined. The results obtained are summarized in Table XIII.

1 treat- aphids in of rhizoctonic to/ha ments shoots 1. 23 0.14 50.7 2. 24 0.06 52.3 3. 25 0.11 50.9 4. 5 0.16 50.1 23 0.04 54.9 6. 26 0.05 53.4 7. 25 0.02 56.1 8. 9 0.13 50.9 9. 6 0.09 51.3 0 0.07 53.2 11. 0 0.06 52.3 12. 0 0.06 54.0 13. 3 0.04 53.9 1 -47 The data of Table XIII clearly show that the compositions containing compound 1/62 together with one or two other active ingredients protect the potato against the early aphid infection and inhibit the rhizoctonic stem mouldering.

Example 31 Fungicidal activity against diseases of oil flax at germ stage The oil flax plants sprang from treated seeds were examined in plots of 20 m2. The seed dressings were carried out with 2-(0-1'-methyl-2'-chloroethyl)- -2-thio-l,3,2-oxathiaphospholane (compound I/10, in 0 form of composition of Example 17), Kelokarb 80 WP, Agrocit 50 WP, Chinufur 40 FW (40 of 2,3-dihydro- -2,2-dimethyl-7-benzofuranyl-methylcarbamate) and with the combinations of these materials. The treatments were as follows: Untreated control Compound I/10 1.0 kg/to Kelokarb 80 WP 2.0 kg/to Agrocit 50 WP 2.0 kg/to Chinufur 40 FW 5.0 1/to Compound I/10 1.0 kg/to Chinufur 40 FW 5.0 1/to Compound I/10 0.5 kg/to Kelokarb 80 WP 1.0 kg/to Chinufur 40 FW 5.0 1/to Compound I/10 0.5 kg/to Agrocit 50 WP 1.0 kg/to Chinufur 40 FW 5.0 1/to

I__

7 48 The treated seeds were sown, and the emerged plants were evaluated at the cotyledonous stage by determining the amount in of the emerged plants and of the plants attacked by flax-flea compared to the untreated control. The results obtained are summarized in Table XIV.

Table XIV.

QC, 0 O0 'e' o 0) 00 0 4 No. of treat- Emergence Amount of plants attacked ment by flax-flea 1. 100 100 2. 132 104 3. 124 109 4. 139 109 5. 97 6. 147 0 7. 161 0 8. 173 2 The data of Table XIV. clearly show that the compositions containing compound I/10 together with one or two other active ingredient show a significantly higher activity in comparison with the compositions containing only one active ingredient and with the untreated control.

49 Example 32 Fungicidal activity on autumn wheat The fungicidal activity of the compositions according to the invention against powdery mildew of cereals and fusarium rot of ear was examined on winter 2 wheat in plots of 20 m The treatments were carried out at flowering with Kelokarb 80 WP, Chinoin Fundazol WP (50 of l-butyl-carbamoyl-benzimidazol-2-methyl- -carbamate), compound I/1 (in form of composition of Example 17) and with the combinations of these mateo rials. The treatments were as follows: Untreated control Chinoin Fundazol 50 WP 1.0 kg/ha o 0 Kelokarb 80 WP 2.0 kg/ha Compound I/1 2.0 kg/ha Compound I/1 1.0 kg/ha Kelokarb 80 WP 1.0 kg/ha Compound I/1 0.5 kg/ha Kelokarb 80 WP 1.0 kg/ha Compound I/1 1.75 kg/ha Chinoin Fundazol 50 WP 0.5 kg/ha Compound I/1 1.50 kg/ha Chinoin Fundazol 50 WP 0.75 kg/ha Compound I/1 0.25 kg/ha Chinoin Fundazol 50 WP kg/ha Compound I/1 0.5 kg/ha Chinoin Fundazol 50 WP 0.5 kg/ha Kelokarb 80 WP 2.0 kg/ha 11.) Compound I/1 0.75 kg/ha Chinoin Fundazol 50 WP kg/ha Kelokarb 80 WP 1.5 kgfha

__J

50 12.) Compound I/1 1.0 kg/ha Chinoin Fundazol 50 WP kg/ha Kelokarb 80 WP 1.0 kg/ha The rate of infection caused by powdery mildew was evaluated prior to and two weeks after the treatments using the scale and infection index described in Example The activity against fusarium rot of ear was determined at milky ripening stage on a section of 5 x 1 m 2 by determining the amount of the infected o o "ears after harvesting, the intrinsic infection of 200 200 grains was also determined. The results ob- 0 0 o tained are summarized in Table XV.

Table XV.

Table XV.

6 0 4 a o o o 0 0 KI 0 o aa 04 a 0 e eo oe o o 0 0 No. of Infection index Fusarium infection treatments for Powdery mildew on ears grains 1. 2.60 7.60 39.0 2. 1.03 3.20 11.0 3. 2.72 3.50 16.0 4. 1.11 2.40 12.0 5. 1.28 1.20 6. 1.33 1.40 7. 0.54 0.74 51 51 Table XV.

(contd.) No. of Infection index Fusarium infection treatments for Powdery mildew on ears grains 0400 0t 0 o .o j "0 001 0 0 0 0a 0 0 0 0 0 000 0 00* 0 P 0 0000 0 0 0 f 8. 0.22 0.53 9. 0.81 1.10 10. 0.46 0.51 11. 0.33 0.39 12. 0.25 0.31 The data of Table XV clearly show that the synergistic fungicidal compositions according to the invention containing compound I/1 and zinc, manganese complex of 8-quinolinolato-(dimethyl-dithiocarbamate) in a ratio of 1:1 and 1:2 and containing compound I/1 and benomyl in a ratio of and contain- 20 ing compound I/1, benomyl and said complex in a ratio of significantly decrease the rate of infection caused by powdery mildew and Fusarium spp.

Example 33 Fungicidal activity against apple trees The fungicidal activity was examined in plots containing 5 apple trees against powdery mildew of -1 52 apple and apple scab. The first spraying was carried out at red-bud stage and repeated every 10-14 days, using Karathane LC (350 g/l, of 6-(1-methyl-heptyl)- -2,4-dinitrophenyl-crotonate) Chinoin Fundazol 50 WP, 2-(0-2'-chloroethyl)-2-thio-5-methyl-oxathiaphospholane (compound 1/4, in form of composition of Example 17) and the combinations of these materials. The treatments were as follows: Untreated control Karathane LC 0.5 1/ha Chinoin Fundazol 50 WP 1.0 kg/ha .O.o Kelokarb 80 WP 2.0 kg/ha Compound I/4 1.0 kg/ha Compound I/4 0.5 kg/ha Karathane LC 0.25 1/ha o° 15 Compound I/4 0.5 kg/ha Chinoin Fundazol 0.5 kg/ha Kelokarb 80 WP 1.5 kg/ha °o Compound 1/4 0.75 kg/ha Chinoin Fundazol 0.5 kg/ha Kelokarb 80 WP 1.5 kg/ha o The rate of infection was evaluated at the stage when the fruits were as big as a green nut and 0 r after the last spraying sing the scale and infection index described in Example 25. The calculated and found results are summarized in Table XVI.

A

53 Table XVI.

No. of Infection by apply scab Powdery mildew treat- leaf fruit Infection Infection ments index 1. 28.5 68.7 97.2 1.16 2. 27.2 67.9 29.7 0.32 3. 7.9 12.5 33.5 0.56 4. 4.7 11.9 96.9 1.25 7.6 13.1 38.9 0.60 6. 7.4 14.0 13.5 0.19 7. 4.2 10.3 18.2 0.27 8. 2.9 8.2 15.9 0.23 The data of Table XVI show that while Karathene O ;LC is effective only against powdery mildew and Kelokarb WP only against apple scab, the compositions according to the invention containing compound of Formula benomyl and zinc, manganese complex of 8-quinolinolato-dimethyl-dithiocarbamate in a ratio of -(1l5:1:3) exhibit activity against both fungi. The 0o combination of Formula and Karathane LC show also good activity.

54 Example 34 Fungicidal activity on vine The activity of compositions according to the invention was examined on vine culture consisting 25 double vine stocks grown as wall-fruit against peronospora, powdery mildew and grey mould.

The treatments against peronospora were repeated in the period between the 6-8 leaves stage and emergence in every 14 days. The time of protection against the grey mould is defined plant phenologically: a the treatment should be carried out after flowering o° oat the time of closing of clusters and emergence. The 0 seed dressings were carried out using -2'-chloroethyl)-2-thio-l,3,2-oxathiaphospholane (com- 0 o 15 pound I/10, in form of composition of Example 17), Chinoin Fundazol 50 WP, Thiovit S (80 of sulfur), SKelokarb 80 WP and the combinations of these materials.

0 0 The treatments were as follows: Untreated control Thiovit S 3.0 kg/ha Kelokarb 80 WP 2.0 kg/ha Chinoin Fundazol 50 WP 1.5 kg/ha Compound I/10 1.0 kg/ha Compound I/10 1.0 kg/ha Thiovit S 2.0 kg/ha Compound I/10 1.0 kg/ha Chinoin Fundazol 50 WP kg/ha Compound 1/10 1.0 kg/ha Chinoin Fundazol 50 WP kg/ha hlb- i 55 Compound 1/10 0.5 kg/ha Chinoin Fundazol 50 WP kg/ha Compound I/10 0.5 kg/ha Chinoin Fundazol 50 WP kg/ha Kelokarb 80 WP 1.0 kg,na 11.) Compound I/10 0.75 kg/ha Chinoin Fundazol 50 WP 0.75 kg/ha Kelokarb 80 WP 1.5 kg/ha Whern evaluating the activity the foliage was investigated in case of peronospora and the clusters of vine in case of grey mould using the scale and infection index described in Example 25. The results obtained o are summarized in Table XVII.

oa 0 Table XVII 999 9 9 09 0* *0 ot No. of Infection index treatments treatments Peronospora Powdery mildew Grey mould on leaves on leaves on clusters 20 1. 1.82 3.93 0.50 2. 1.89 0.33 0.52 3 0.41 3.41 0.48 4. 1.35 0.22 0.28 0.48 0.26 0.37 6. 0.42 0.11 0.35 7. 0.29 0 0.11 8. 0.30 0.04 0.18 9. 0.46 0.02 0.14 56 Table XVII (contd.) 0, 0 o 0iI: 0,~ o 0 o 0 43 00 0 0 00 4 0 0*t 0S 0 44 0( 0* 4D 0 403 440 No. of Infection index reatments Peronospora Powdery mildew Grey mould on leaves on leaves on clusters 0.18 0.09 0.20 11. 0.11 0,08 0.18 The data of Table XVII clearly show that the compositions according to the invention containing compounds of formula and benomyl in a ratio of and compound of formula benomyl and 8-quinolinolato-dimethyl-dithiocarbamate Zn, Mn complex in a ratio of show good activity against the fungal diseases of vine. The most harmful infections could not develop' on vine after the treatments carried out with said compositions.

When determining the fungicidal effect also the acaricidal activity against vine mites was examined on 100-100 leaves. It has been found that the compositions according to the invention possess a valuable acaricidal activity, too, especially the combination No. 6 (compound of formula I+Thiovit S) provides good activity.

S- 57 Example Fungicidal activity against diseases of winter wheat at germ stage The tests were carried out on seeds having 92 of germinating ability (variety of Jubilejnaja and an intrinsic infection caused by Fusarium spp.

of 10.5 The seed dressings were carried out with composition of Example 7 and for comparison Quinolate V-4X (15 of cooper-oxyquinolate 50 of 2,3-dihydro- -6-methyl-5-carboxanilido-l,4-oxathiino was used.

000 After emergence, at the 2-4 leaves stage oao of wheat, the number of emerged plants was determined S' on a section of 5x1 m and the length of 100 plants 00 00 0 °15 located beside each other was also determined in every plot. Under laboratory conditions the rate of 0 infection of 200-200 seeds was also examined after 0 0 a 10-day incubation carried out in wet chamber at The results obtained are summarized in Table

XVIII.

0e 0 a a a .00 0 0 a a 0 0 *0 0 0 0 0 0 0* a a 00 0 00 000 000 0 0 00 0 0 0 0 0 0 0 0 0 0 0 3, 0 0 3 0 3 Table ~vfi~ Treatments Dose Laboratory conditions Field conditions (kg/to) Fusarium spp. Alternaria No. of Length infection infection plants of p'ants per m cm Untreated control -10.5 20.5 51.4 7.9 WP of Example 7 1.0 6.5 0.5 53.5 0.1 WP of Example 7 2.0 1.0 0 58.5 8.3 VIP of Example 7 3.0 0 0 57.2 Quinolate V-4X 2.0 1.0 0.5 57.8 8.1

I

59 The data of Table XVIII clearly show that the composition according to the invention is as active seed dressing agent in a dose of 2.0 kg/to as the widely used known Quinolate V-4X.

Example 36 Fungicidal activity against Fusarium rot of winter wheat On plots of 40 m 2 winter wheat (variety of MV-8) was sprayed at flowering using compositions of Example 12 (diluted with 500 1/ha of water) and for comparison Kolfugo 25 FW (25 of 2-(methoxycarbonyl-amino)-benzimidazole). After harvesting the rate of Fusarium infection was determined using the infection index described in Example 25. The intrinsic infection was also determined. The results obtained are summarized in Table XIX.

Table XIX.

Treatments Dose Fusarium spp.

1/ha Infection index Intrinsic infection F. 1 Untreated control 1.12 19.75 FW of Example 12. 0.5 0.85 10.2

I_

1- -i 60 Table XIX.

(contd.) Treatments Dose Fusarium spp.

1/ha Infection index Intrinsic infection F 1 FW of Example 12. 1.0 0.41 60 FW of Example 12. 1.5 0.10 Kolfugo 25 FW 1.5 0.58 94' 9 4 09 4 c 4 op 4.

4 '0 4 4 a9 041 4 4 The data of Table XIX clearly show that the 15 composition according to the invention provide a better protection even in a dose 1.0 1/ha against both Fusarium rot of ear and intrinsic infection caused by Fusarium spp. than the widely usedKolfungo 25 FW in a dose of 1.5 1/ha.

Example 37 Fungicidal activity against late blight of potato On plots of 75 m 2 potato (variety of Gracia) was sown and when starting the budding, the plants were sprayed with composition according to Example using 500 1/ha of spray, and for comparison with Dithane M 45 (80 of manganese, zinc-ethylene-bis- 61 (dithiocarbamate) against late blight of potato (Phytophtora infestans). The treatments were repeated four times, in every 14 days. The evaluation was carried out 2 weeks after the last treatment using the scale and infection index described in Example 25. The results obtained were summarized in Table XX.

Table XX.

C'C

o ')C a i C. ai o ao OC4 I I l D I) Treatments Dose Infection index 1; kg/ha F.

Untreated control 2.37 FW according to Example 10 2.0 0.84 FW according to Example 10 3.0 0.59 50 FW according to Example 10 4.0 0.52 Dithane M-45 2.0 0.98 The data of Table XX clearly show that the composition of Example 10 posseses a higher activity against Phytophtora inf. even at a dose of 2 1/ha than the widely used Dithane M-45 at the same dose.

62 Example 38 Fungicidal activity against disease of corn at germ stage In plots of 15 m 2 treated corn (variety of P.3732) were sown. the treatments were carried out with compositions of Examples 5 and 6 and for comparison the combination of Orthocid 50 WP (50 of N-trichloro-methylthio-tetrahydrophtalimide) and Agrocit 50 WP (50 of 1-butyl-carbamoyl-benzimidazole- -2-methylcarbamate) were used. The evaluation was carried out at the 2 and 4 leaves stage by determining the number of the emerged plants from 100 seeds.

At the 2-leaves stage the length of the plants and under laboratory conditions the germinati.ig as well as the intrinsic infection caused by Fusarium spp.

(on 200 seeds) were also determined. The results obtained are summarized in Table XXI.

.4 r toc J Oo oa o a a o a a B 0 \1 e oo a I^ a* o^ a s 0o ao o0 S 0 6t 0 0 0 03 S 0 a* ao p a a. aa Table XXI.

Treatments Dose Laboratory conditions Field conditions kg/to Germination Fusarium spp. Emerged plants Length of Sinfection, plants cm, Untreated control

WP

according to Example 5 1.0

WP

according to Example 5 2.0

WP

according to Example 5 4.0

WP

according to Example 6 1.0 98.5 99.0 98.5 97.5 98.0 10.5 5.5 1.0 1.0 2.5 82.5 90.0 94.0 94.0 92.5 7.9 100 8.3 101 8.6 105 7.9 109 8.5 100 Table XXI.

(contd. Treatments Dose Laboratory conditions Field conditions kg/to Gerzmination Fusarium spp. Emerged plants Length of %infection, %plants cm,

WP

according to Example 6 2.0 99.0 0 95.0 8.9 1*00

WP

according to Example 6. 4.0 98.0 0 95.0 8.3 109 Orthocid WP 1.0 99.0 4.5 90.5 8.0 105 Agrocit

WP

2

I

The data of Table XXI clearly show that the compositions according to Example 5 and 6 possess the same or better activity than the known Orthocid WP and Agrocit 50 WP compositions. these compositions effectively protext the plants against phatogenic fungi, increase the emergence and promote the growth of seedlings.

Example 39 Fungicidal activity against powdery mildew a 0" of apple o' In apple culture on 10-10 apple trees a the fungicidal activity of composition of Example 6 130 was examined against powderey mildew of apple (Rhodo- 0 sphaery leucotricha). For comparison treatments with composition Example 18, Sulfur 900 WP (900 g/1 of 00 sulfur) and Chinoin Fundazol 50 WP (50 of benomyl) were carried out. For the spraying 100 litre/ha spray 0. .0 was used and 9-times in every 14 days between the period of the "mouse ear" stage and beginning of ripeno *ing. The evaluation was accomplished 10 days after the last treatment on 250 250 shoots using the scale and infection index described in Example i i r, 66 Table XXII.

o. r

O

'3

B

O

JI

Treatments Dose Rate of infection 1; kg/ha Infection Infection index

F.

Untreated control 100

WP

according to Example 6 2.0 28 0.61

WP

according to Example 6 1.5 35 0.74 50 EC according to Example 18 2.0 71 1.15

EC

according to Example 18 1.5 76 1.20 Sulfur 900 FW 4.0 85 1.40 Chinoin Fundazol 50 WP 2.0 57 1.02 Chinoin Fundazol 50 WP 1.5 61 1.04 The data of Table XXII clearly show that the composition of Example 6 possess the best activity against powdery mildew of apple and that this composio 00 0000 0 Abbb. ii I LL~_ 67 ooo000 o ft 00e *4i 0 a a 6 o 04t 0 0 4 Q oa 9*o Q OI 00 (L 9 0o 4 0 00 O 0 0 4l W 00 0 0 4t 0 tion containing compound I/1 having contact activity and benomyl having systemic activity is a synergistic fungicide.

Example Fungicidal activity against grey mould of vine In plots of 30 m 2 the fungicidal activity of composition according to Example 11 was tested against grey mould of vine (Botrytis cinerea). For comparison Rovral 25 FW (25 of 1-isopropyl carbamoyl- -3-(3,5-dichlorophenyl)-hydantoine), Chinoin Fundazol 50 WP and composition of Example 18 were used. The treatments were carried out 7-times after the end of flowering in every 10-14 days, using 1000 litre/ha of spray. The evaluation was carried out in the middle of August and at the end of September on 4x50 clusters per plot, using the scale described in Example to determine the rate of infection and from the values obtained the infection index was also determined.

The results obtained are summarized in Table XXIII.

68

I

Table XXIII.

Qa 00 a 0** 000 00 0 00 0 O 00 0 00 000 0 0 0 00 00 4 Treatments Dose Infection index F.

i 1; kg/ha in the middle at the end of August of September Untreated control 0.31 0.51 WP according to Example 11 1.0 0.17 0.26 50 WP according to Example 11 2.0 0.06 0.09 Rovral 25 FW 2.0 0.08 0.13 Chinoin 15 Fundazol 50 WP 2.0 0.13 0.20 50 EC according to Example 18 2.0 0.22 0.35 The data of Table XXIII clearly show that the activity of composition of Example 11 surpasses that of the compositions containing these active ingredients alone, so the composition containing benomyl and compound I/1 possess synergistic activity.

Example 41 Fungicidal activity against apple scab On plots, consisting 5 apple trees, the fungicidal activity of composition of Example 5 against 4_ i ;;i a~ r U 69 apple scab (Venturia inaequalis) was examined. For comparison Polyram Combi (80 of zinc-polyethylene- -thiuram-disulfide complex), Kelokarb 80 WP and composition according to Example 18 were used. The spraying of apple trees (variety of Starking), having medium trunk, were sprayed with 1000 1/ha of spray in the period between the "mouse ear" state and start of ripening 10-times in every 14 days. When the first and second shoots appear on 100 leaves per plot the rate of infection in and the infection index were determined according to Example 25. The rate of in- 0 o a fection was similarly determined in the middle of August 0 00 on 50 apples per plot. The results obtained are summao o rized in Table XXIV.

0 0 00 4 0 O0 <a O B< E L)

<D

L -iL- L __II~ 000 0 0 0 00 00 900 000 0 0 0 0 4 0 0 0 4 a a o 3 a a O fi o so D 0 0 OCO O Table XXIV.

Treatments Dose Rate of infection 1; kg/ha on leaves on fruits S F F. F.

1 1 Untreated control -86.0 1.6 46.0 1.32 35.0 0.44 WP according to Example 4 3.2 3.0 0.05 16.0 0.19 2.0 0.02 WP according to Example 4 2.4 5.0 0.08 27.0 0.25 5.0 0.05 WP according to Example 4 1.6 17.0 0.31 30.0 0.38 15.0 0.16 Polyram Combi 2.0 23.5 0.35 32.0 0.39 15.0 0.16 Kelokarb 80 WP 2.0 21.0 0.37 33.0 0.34 13.0 0.18 EC according to Example 18 3.2 29.0 0.41 40.0 0.39 20.0 0.20 S71 The data of Table XXIV clearly show that the composition of Example 4 possesses a higher activity against apple scab in a dose of 2.4-3.2 kg/ha than the widely used Polyram Combi or the active ingredients thereof used alone.

Example 42 Fungicidal activity against diseases of winter wheat at germ stage The experiments were carried out on winter V-o 2 wheat (variety of MV-8) on plots of 20 m The seeds having germinating ability of 91 and intrinsic infection caused by Fusarium spp. of 22 were treated with the composition according to Example 14, and for comparison Kolfugo 25 FW and Dithane M-45 were used. After seed dressing 270 kg seeds were sown per o ha in a depth of 6 cm. When evaluating, under laboratory conditions the rate of infection was determined after an incubation carried out with a sterile culture medium of type Papavizas and in wet chamber, respectively. Evaluating the field experiments the number of Sthe emerged plants on a section of 5x1 m and the length thereof were determined. The results obtained are summarized in Table XXV.

a aSS C a a, C a as a C S S a a as a a S S S S a aa S S 0 0 S 0 0 a o Sp .0 1 Table XXV.

Treatments Dose Laboratory exp. Field nxp.

1;k/t usarium spp. Alternaria No. of Length infection infextion plants of plant per m cm Untreated control 22.0 30.5 51.2 7.9 WP according to Example 14 1.0 3.5 2.0 53.9 8.4 WP according to Example 14 2.0 0.5 0.0 60.4 8.9 WP according to Example 14 3.0 0.0 0.0 51.4 7.9 Kolfugo 25 FW 2.0 Dithane M-45 1.0 2.5 0.5 50.2 8.9 c 7 i i 73 The data of Table XXV clearly show that the activity of composition in a dose of 1.0 kg/to according to Example 14 is quite the same as the combination of the widely used Kolfugo 25 FW and Dithane M-45. The most favourable result was obtained at a dose of 2.0 kg/to of composition according to Example 0000 aaoo o oa 00 0r 0 00( 0 0O 0 0D o0 '4 440 44 0 00 0 00O 00 0 0.40 0 0000 0014, 14 04 Example 43 Fungicidal activity against diseases of corn at germ stage Under glass house conditions the activity of composition of Example 15 on corn seeds (variety of Pioneer 3747SC) was examined in comparison with 15 Kelokarb 80 WP, Chinoin Fundazol 50 WP and composition of Example 18.

After seed dressing the rate of infection was determined on 200-200 seeds after an incubation on a Papavizas culture medium. 10-10 treated seeds 20 were thereafter sown into pots in 8 replicates and the emergence and the length of the emerged plants were determined 14 days after the sowing.

The results obtained are summarized in Table

XXVI.

lr 100 4 a 0 4 C 4 a 4 a 0 0 000 0 0 a 000 00 C 00 0 0 0 0 0 4 4 C 0 0 0 00 000 000 0 00 0 S fl 0 0 0C~ 0 0 0 0 0 o 0 00 0 0 0 0 0 0 0 0 0 0')0 00 Table XXVI.

Treatments Dose Fusarium spp. Emergence Length of plants 1; kg/to infection %cm% Untreated control -44.0 72 19.5 100 WP according to Example 15 1.0 7.0 79 20.6 106 WP according to Example 15 1.5 0.0 85 21.5 110 WP according to Example 15 2.0 0 90 22.0 113 Kelokarb 80 WP 1.4 6.0 00 20.3 104 Chinoin Fundazol 50 WP 2.2 2.0 07 20.8 107 EC according to Example 18 2.2 7.0 63 18.1 93 u 75 The data of Table XXVI clearly show that the composition of Example 15 possesses a higher activity than the compositions containing the same active ingredients alone, i.e. the composition has synergistic activity.

Example 44 Fungicidal activity against fusarium rot of pink o o Under glass house conditions on plots of m the fungicidal activity of composition of Example 13 was examined against fusarium foot rot of pink.

o; For comparison Kelokarb 80 WP, Chinoin Fundazol 50 WP and composition of Example 18 were used.

o, 15 The number of Fusarium spp germs of the S soil (9500 thereafter on 50 pink cuttings the rate of infection of the propagating material (4 was determined. Thereafter the compositions were admixed with the soil and the planting was carried out.

20 The evaluation was carried out 5, 7, 9 and 11 weeks after the planting by determining the rate of infection. The results obtained are summarized in Table

XXVII.

0 0 0000 0 00 0 0 000 0 0$ 000 0 0 00 0 0 0 0 0 00 0000 000 0 000 ~o Table XXVII.

Treatments Dose Rate of infection, gmi/rn 2 5 weeks 7 weeks 9 weeks 11 weeks Untreated control -0 6.95 8.57 9.86 WP according to Example 13 5.0 0 3.92 4.66 5.75 WP according to Example 13 10.0 0 1.90 2.73 3.04 WP according to Example 13 20.0 0 1.32 2.20 2.82 Kelokarb 80 WP 5.0 0 6.23 7.30 9.46 Chinoin Fundazol WP 8.0 0 5.26 5.66 6.43 EC according to Example 18 8.0 0 4.05 5.55 6.60

M

77 The data of Table XXVII clearly show that the activity of composition of Example 13 is significantly higher at the same dose 4 g/m 2 which corresponds to 20 g/m 2 of 20 WP, to 5 g/m 2 of 80 WP and to 8 ml/m 2 of 50 EC) than that of the compositions containing the same active ingredients alone.

The same results were obtained when using the composition of Example 13 in less doses.

S 10 Example Fungicidal activity against diseases of O peas at germ stage .o The experiments were carried out in plots of 40 m 2 on peas (variety of Frila) using for seed 15 dressing composition of Example 15, Chinoin Findazul o o 50 WP, and Dithane M-45. The germinating activity of seeds to be treated was 95% When evaluating the treatments under laboratory conditions the rate of infection was determined on 200-200 seeds per treato.0i 20 ment after a 10-day incubation in sterile wet chamber.

a Q S° Under field condition the number of the emerged plants at the 2-leaves stage of peas and the number of the infected plants were determined. The yield data after the harvesting was also determined. The results obtained are summarized in Table XXVIII.

8a9 a C C a a a a a a 499 099 a 9 9 a 9 9 0 9 9 9 a 99 0 9 0 a a 9 9 94 a a a a 9 9 0 a 9 a a 9 999 99 9 Table XXVIII.

Treatments Dose Infection of seeds No. of plants Crop kg/to Fusarium Ascolupta Aspergil- Penicil- Clodos- Emerged Infected to/ha spp. spp. lus spp. hium spp. porium spp.

Untreated control 10.7 2.5 5.5 18.0 9.5 33.7 0.4 4.63 WP according to Example 15 1.0 1.0 0 1.5 0 0 39.0 0 4.79 WP according to Example 15 1.5 0.5 0 1.0 0 0 43.6 0 5.10 WP according to Example 15 2.0 0 0 0 0 0 44.2 0 5.09 Chinoin Fundazol WP 1.0 Qithane M-45 1.5 1.0 0 1.0 0 0 39.8 0 4.88 -79- The data of Table XXVIII learly show that the activity of composition of Exaiple 15 is the same in a dose of 1.0 kg/to as the activity of the combination of Chinoin Fundazol 50 WP and Dithane in a higher dose. The composition of Example 15 protects the seeds against fungal attack, increases the number of emerged plants as well as the crop.

Example 6 o"0o 10 Fungicidal activity on cotton 0 0 o o Under glass house conditions the fungicidal o o° activity of composition of Example 16 was examined on cotton in comparison of Chinoin Fundazol 50 WP and Dithane M-45. After seed dressing 10-10 treated 0 15 seeds were sown in plot and 14 days after sowing the S* emergence and length of the plants were determined.

So°° The results are summarized in Table XXIX.

Table XXIX.

0. 0 0 0 Treatments Dose Emergence Length of the plants kg/to cm Untreated control 62.0 13.2 100.0 80 WP according to Example 16 1.0 83.0 15.1 114.4 WP according to Example 16 2.0 92.0 15.0 119.7 j i UIUYL 80 Table XXIX.

(contd.) Treatments Dose Emergence Length of the plnts kg/ cm WP according to Example 16 3.0 85.0 14.3 108.3 Chinoin Fundazol 10 50 WP 1.0 Dithane M-45 1.5 81.0 14.9 112.9 00 The data of Table XXIX clearly show that the composition according to Example 16 even at a dose 15 of 1.0 kg/to possesses higher activity than the widely Soo' used compositions in 1.5-fold higher dose. Due to oo the fungicidal effect against the diseases of cotton at germ stage the initial growth of the plant improves.

20 Example 47 Fungicidal activity against the diseases of soya at germ stage The fungicidal activity on soya (variety of Pi 1677) was examined in plots of 20 m The seeds were treated with compositions of Example 15 and for comparison with Chinoin Fundazol 50 WP and Dithane The germination under laboratory conditions and under field conditions on a section of 10x1 m anii c 81 the number of the emerged plants were determined at the cotyledonous stage and when the first tergeminal appeared. After the harvesting the yield data were also determined. The results obtained are summarized in Table XXX.

0 0 0 0 o o 0 0 00 0o 0 0 00* 009 0 0 0 0 0 0 0 0 0 9 9 00 4 0 0 0 0 00 0 0 0 9 0 0 0 0 0 0 000 00 9 Table XXX.

Treatments Dose kg/to Germin~ation No. of emerged plants first second evaluation Length of plants cm Yield to/ha Untreated control WP according to Example 15 WP according to Example 15 WP according to Example 15 Chinoin Fundazol WP Oithane M-45 1.0 2.0 3.0 82.0 86.0 92.0 81 .0 15.1 16.9 17.4 17.0 15.3 9.10 17.0 9.05 17.3 9.00 3.22 3.30 3.45 3.35 17.1 9.00 1.0 1.5 86.0 16.6 16.9 9.00 33 3.38 -83 The data of Table XXX clearly show that the composition of Example 15 improve the germination and emergence and yield without influencing the length of soya plants.

Example 48 Fungicidal activity on sunflower The fungicidal activity of compositions O. according to Examples 6, 11 and 16 was examined on *ooo 10 sunflower in a plot of 2 ha. For comparison the com- S position of Chinoin Fundazol 50 WP and Dithane o" was used. The compositions were applied by areal spraying (using helicopter, type KA-26) at the time of formation of plates and flowering, the amount of spray .o 15 was 70 1/ha. The evaluation was carried out prior o4 to desiccation on 10x50 plants and the rate of infection in was determined on the basis of scale described in Example 25. The results obtained are summarized in Table XXXI.

20 The data of Table XXXI clearly show that 40 4 the composition of Ekample 6 possesses a higher activity than the known compositions and compositions of Examples 11 and 16 are as effective as the known compositions.

ii rb 060 0 00 0 0 0 0 00 0 0 0 0 0 0 00 0 0 0 0 00 .0 .00 0 0 a 0 0 P 0 0 0 0 00 0~0 Table XXXI.

Treatments Dose Infection 1; kg/ha Scierotinia Botrytis Total scierotiorum cinerea infection on plates on plates on plates Untreated control -3.5 22.5 26.0 WP according to Example 6 3.0 1.0 3.5 WP according to Example 11 3.0 2.5 8.7 11.2 WP according to Example 16 2.0 2.0 9.2 11.2 Chinoin Fundazol 50 WP Dithane M-45 +2.0 2.3 9.5 11.8

Claims (4)

1. Synergistic fungicidal compositions contain- ing two or three active ingredients which comprises in an effective amount and in a ratio of (10:1) (1:10) and (10:1:1) (1:10:10) respectively 2-/O-(substituted alkyl)-2-thio-l,3,2-oxathiaphospholane of formula (I) R -CH-0O I SR 1 //P-0-CH-CH-X (I) I R -CH-S 2 R R -wherein RI, R 2 R 3 and R 4 stand independently from eacn other for hydrogen, alkyl having 1 to 6 carbon atoms, alkenyl having 2 to 6 carbon atoms, alkynyl having 2 to 6 carbon atoms, X is halogen or hydrogen, alkyl having 1 to 6 carbon atoms or mercapto and a zinc and manganese complex of B-quino- linolato-dimethyl-dithiocarbamate and/or benomyl as active ingredients in admixture with known carriers and/or additives.

2. Synergistic fungicidal composition as claimed in Claim 1 which comprises in an effective amount and in a ratio of (10:1) (1:10) compound 86 of formula (I) R -CH-0 S 1 1 I P-0-CH-CH-X 2 R 3 R 4 (I) 4404 0.,04 00 0 4 00 40 0 4 4 40 0 44 44 440 0 44 44 o 4 40 0 0 4 4 04 4 ~g 4 a 444 A wherein R 1 R 2 R 3 R 4 and X are the same as men- tioned in Claim 1 and a zinc and manganese (1:1) complex of 8-quinolinolato-dimethyl-dithiocarbamate 10 as active ingredients.

3. Synergistic fungicidal composition as claimed in Claim 1, which comprises in an effective amount and in a ratio of (10:1:1) (1:10:10) a com- pound of formula (I) R 1 -CH-0 S 1- 1 I ,P-0-CH-CH-X R 2 -C R 3 R

4 (I) 4 4 a ,~4 t a 4 20 wherein R 1 R 2 R 3 R 4 and X are the same as mentioned in claim 1 and a zinc and manganese complex of 8-quinolinolato-dimethyl-dithiocarbamate and benomyl. DATED this 29th day of May 1989. ESZAKMAGYARORSZAGI VEGYIMUVEK WATERMARK, PATENT TRADEIAE ATTORNEYS 50 QUEEN STREET MELBOURNE. VIEC. 3000.