FR2543404A1 - FUNGICIDAL COMPOSITION CONTAINING A 3,5-DINITRO-4-CHLOROBENZOIC ACID DERIVATIVE WITH SYNERGISTIC ACTION - Google Patents

Abstract

THE PRESENT INVENTION CONCERNS NEW FUNGICIDE COMPOSITIONS WITH SYNERGIC ACTION COMPRISING AS FIRST ACTIVE INGREDIENT A 3,5-DINITRO-4-CHLOROBENZOIC ACID DERIVATIVE AND AS A SECOND ACTIVE INGREDIENT A BODY OF THE GROUP CONSTITUTED BY I-1,2 DIMETHYLN-N-N-N-1. -PHENYLENE-BIS (THIOCARBAMOYL) -BIS (CARBAMATE); II A DERIVATIVE OF BENZIMIDAZOLE; III A PYRIMIDINYLMETHANOL DERIVATIVE; AND IV A DERIVATIVE OF 1,2,4-TRIAZOLE.

Description

-1 -

  The present invention relates to conppai L-

  tions, synergistic fungicides containing; a derivative of 3,5dinitroï-chlorobenzvuque acid de f orimule a l néral e

COO-R

0 N

1002 NO

  as one of the active ingredients, while the other component is chosen from the group consisting of dimethyl (NN '-l 1 i, 2-phenylenebis (thiocarbamoyl) l-' bis (carbamate)) a benzimidazole derivative of formula- (II) -N

N NH-0 OCH

  Ri 1 a pyrimidinylmethanol derivative of formula (III) 'OR

R 3-CR

(II

  and a derivative of 1,21,4-triazole-deformule (IV) -2- I

R C R 7 (IV)

R 6

  o the weighted ratio of the active ingredient of formula-

  (I) to the other component chosen from the group consisting of dimethyl (N, N'-l 1,2-phenylene-bis (thiocarbamoyl) l -bis (carbamate)) and the compounds of formulas (II), ( III)

and (IV) is 1: 2 to 14: 1.

In formula (I)

  R represents a C 1 to C 6 alkyl group.

  In formula (II) R 1 represents a hydrogen or a group of formula 0 o C NH CH (a)

I 49

  In formula (III) R 3 and RÈ are similar or different and represent a phenyl group optionally substituted by a halogen. In formula (IV) R 5 represents a hydrogen, a phenyl group or a

  phenoxy group optionally substituted by a phe-

  nyle or halogen, or a benzyl group substituted by halogen; R 6 represents hydrogen or phenyl substituted by a trifluoromethyl group; and R 7 represents a phenyl or one of the groups of formulas C 4 H 9 (c) -C O C 4 H 19 '(d) OR -.e -3- and o L i o

  R 8 represents a C 1 to C 0 alkyl group.

  The compositions of the invention are useful in a variety of cultures against a number of

  mushrooms according to the needs of application processes

  tion, for example to prepare or sow seeds or

  for the treatment of the plant reserve.

  A type of active ingredients of the compositions

  fungicides of the invention, namely methyl and iso-

  propyl-3,5-dinitro-4-chlorobenzoate and their activity

  quickly against Alternaria cleraceae and Sclerotinia fructi-.

  cola is published in U.S. Patent No. 2,841,522.

  The fungicidal action of dimethyl (N, N'-l 1,2-phenylene-

  bis (thiocarbamoyl) l-bis (çarbamate) is described in Hungarian patent n 169,283 We also know the compounds of formulas (II), (III) and (IV) containing a

  heteroaromatic ring with a higher number of a-

tomes of nitrogen.

  The preparation and fungicidal activity of systemic fungicides of formula (II) are published in US Pat. Nos. 3,631,176 and 3,657,443 while data on the active ingredients of formula (III) are described in English Patent No.

  1,218,623 and that the data of those of formula (IV) the-

  are in U.S. Patent No. 3,912,752.

  -4- The 3,5-dinitro chlorobenzoate-contact esters acting on several sites have not been used at all in practice bie qls -q e soint dea compo

  The main reason, also observed-

  by the Applicant, is that these compounds, which are

  also very effective in the fields, are harmful for.

  the plant to be protected when applied at optimum doses It is therefore necessary to take into account when using it a significant risk of phytotoxicity

  problems have also arisen with the use of fungus

  systemic cides with a specific site of action.

  The compounds of formulas (II), (III) and (IV) as well as

  dimethyl-NN N '-l 12-phenylene-bis (thiocarbamoyl) l-

  bis (carbamate)) metabolizing to methyl- (1 H) -benzimi-

  dazol-2-ylcarbamate which in turn falls under formula (II) were excellent fungicides at the start However after 1960 we saw more and more articles appearing on the resistance of fungi to such compounds which

  develops after several applications.

  Resistance of fungi to benzimida-

  zoles is reviewed in S Go Georpoules: Antifungal

  Compounds, in: Sisler: Development of Fungal Resis-

  tance to Fungicides, New York 1977, pp 493-495 The same source gives 42 references on resistance by

  mutation that develops as a result of fungicide sys-

  witnesses having several specific sites of action.

  Considering that despite the severe possibilities of resistance, the use of systemic fungicides provides several advantages in control processes,

  it would not be reasonable to eliminate them from the pro-

  practical plant protection In addition, the experts

  continuously undermine usage at the current hour

  tual and even in the future of these fungicides One cannot overlook the extraordinary benefits due to the properties

  systemic The search for a solution to problems-

  -5- resistance therefore continues in an ever more intensive manner. Cea effrs'; de "recherche: S O ou md tense ;: to discover the processes aimed at: delaying the development of genes with greater resistance; moderate

  change the combination of potatoes

  pathogenic pulation; and moderate the increase in the resistant strain of the effective population From,

  possible modes of action, discovery and adaptation

  Combination plant cultivation technique

  fungicide-based fungicides with multiple specific sites of action look promising

  As a result of these efforts, the compositions have been developed.

  combined fungicides from manufacturers of protective agents

  tion of plants, for example Epidor Ede from Rohm and Haas Co (containing 10% by weight of benomyle and 62% by weight of mancozeb) or Trimidal from

  Eli & Lilly Co (containing 8% by weight of nuari-

  mol and 32% by weight of maneb) as well as other compounds

  The Hungarian patent no. 158 608 also concerns

  ment a composition containing 2,3-dihydro-6-methyl-.

  1,4-oxathiine-6-carboxanilide having an action site -

  specific in combination with 8-hydroxyquinoline or

  its metal salts having several specific action sites

specific.

  During research by the de-

  mzideresse, we first examined the activity of

  compounds of formula (I) then that of combinations of

  active ingredients These latest studies aimed to determine

  undermine the usefulness of compounds of formula (I) with a function

  known systemic gicide The activity of

  applied of formula (I) in liquid medium against several species of fungi within concentration limits of 0.1 to 1000 ppm of the active ingredient The results

  obtained are summarized in Table 1.

-

Methyl 3,5 dinitro-4-

chlorpbenzoate

Ethyl 3,5-dinitro-4-

chlorobenzoate

n-propyl 3,5-dinitro-4-

alorobenzoate

Isopropyl 3,5-dinitro-

4-chlorobenzoate

tert-butyl-3,5-dinitro-

4 é 7 Elorobenzoate

n-amyl 3 5-dinitro-4-

alorobenzoate

n-octyl 3,5-dinitro-4-

  Ehlorobenzoàte Note: insufficient octyl-ester. l 2 table 1

Alter Relmintho Asper-

  naria sporium gillus solani turcicum niger

Colleto Tricho Relmintho-

  trichum thecium sporium lindomu roseum carbon thianum Fusarium

grami: P'ea-

rum 1

-1 100-10

-1 100-10

1-0.1 100-10

-1 1000-100

-10 1,000,100

1000-4100> 1000

-1 -10 -10

1000-1100

-10

> 1000

-I-011

I-011 I-011 -1 -1 -10 -1 -1 -1 -1 -10

1000-100

> 1000

-1 10-1

pretty 10-1

I-011 100-10

-1 100-10

-10 100-10

1000-100 1000-100

  m> 1000> 1000> 1000> 1000> 1000> 1000 -> l 000 was not studied in more detail because its activity had rn Ln 41- U 4 C> J, - -7- Other studies have been carried out to determine the optimum weight ratio of the active ingredients of the compositions of the inventio: aisique: -la: effective dosage of these compositions Surprisingly, it has been observed that a synergy appears when using

  defined weight ratios of active ingredients.

  The invention therefore relates to fungicidal compositions with synergistic action which, in addition to a 3,5-dinitro-4-chlorobenzoic acid derivative of formula (I) where R represents a C 1-6 alkyl group, contain (i) the dimethyl (N, N'-l 1,2-phenylene-bis (thiocarbamoyl) l -bis (carbamate); or (ii) a benzimidazole derivative of formula (II) where R 1 represents a hydrogen or a group of formula ( a); or

  (iii) a pyrimidinylmethanol derivative of formula (III).

  o R 3 and R 4 are similar or different and represent

  feel a phenyl group optionally substituted by a halogen; or (iv) a 1,2,4-triazole derivative of formula (IV) o R 5 represents a hydrogen, a phenyl group, a phenoxy group optionally substituted by a

  phenyl or halogen, or a benzyl group

  titrated by a halogen, R 6 represents a hydrogen

  or a trifluoromethylphenyl group, and R 7 represents

  feels a phenyl or one of the groups (c), (d) and (e) o 8 represents a C 1 & C 4 alkyl group, the weight ratios of the active ingredient of formula (I) to n ' any other active ingredient being

1: 2 to 14: 1.

  The 3,5-dinitro-4-chloroben- acid derivatives

  zoique of formula (I), representing one of the active ingredients of the fungicidal compositions with synergistic action according to the invention, are esters where R represents an alkyl group containing from 1 to 6, preferably from 1 to

  4 carbon atoms, the best removing a methyl group or.

  ethyl. In the cmposésa of úorm Da, (III) R 3 and R may be similar or different and represent a phenyl group optionally substituted by 1 or 2

  halogen atoms Preferably R 3 and R 4 represent ::.

  a halogen-substituted phenyl group which is:

  preferably chlorine and / or fluorine.

  In the compounds of formula (IV), R 5 can

  represent -a hydrogen, a phenyl group, a phenoxy group optionally substituted by a phenyl or a halogen, or a benzyl group substituted by one or two halogen atoms where the halogen is preferably chlorine R 6 can represent a halogen or a group

  trifluoromethylphenyl and R 7 represents a phe-

  nyle or one of the groups (c), - (d) and (e) In the group

  of formula (d), the butyl group is preferably tert-

  In group (e), R represents an al-

  coyle containing from 1 to 4, preferably from 2 to 3 atoms-

of carbon -

  The weight ratio of the active ingredient of formula (I) to any other active ingredient in the synergistic compositions of the invention is

between 1: 2 and 14: 1.

  Within these limits, the weight ratio of the

  laid of formula (I) with dimethyl- (N, N'-l 1,2-phenylene-

  bis (thiocarbamoyl) l-bis (carbamate)) is preferably

  from 1: 3 to 3: 1; the weight ratio of compounds of form

  mule (I) to the compounds of formula (II) is preferably

  from 1: 2 to 6: 1; the weight ratio of compounds of form

  mule (I) to the compounds of formula (III) is preferably from 1: 1 to 14: 1; and the weight ratio of the compounds of

  formula (I) to the compounds of formula (IV) is preferably

from 1: 2 to 14: 1.

  the form of application of the compositions of the invention can be adjusted to the given target and to the necessities of their use. It can be an agent.

  of formulation in the form of a -powder -or-: an- asua -

  pension; a solid or liquid spraying agent: useful for treating a plant supply; a concentrate

  emulsifiable, dust, etc. For preparation -

  compositions, liquid: and / or solid supports, auxiliary materials and / or other can be used

  additives according to the required formulation and generally-

  used in the practice of preparing plant protection agents The total content of ingredient

  active composition can vary from 5 to 85%.

  On the basis of the Applicant's experiences, Table 2 brings together the best combinations of compounds against a given species of fungi, the best synergistic ratios of the active ingredients, the average doses of application in relation to the content

  total active ingredient and character formulations

  useful for a given application.

Table 2

  Species of Reports of Reports of Mushroom Formulation Combinations of Ingredients at Medium to

tii: s syner the content to-

gales tale en ing-

  Active ingredient Preparation against Fusarium, Tilletia, etc.

liethyl 3, 5-dinitro-4-chloro-

benzoate: methyl 111-benzimi-

dazol-2-ylcarbamate

1: 2-2: 1

0.9 kg / tornne

Agent disin-

fectant pel-

the icon

at 30%

  Preparation against Fusarium, Tilletia, etc. Preparation against Botrytis, Fusarium

Rhizoctonia, Tri-

chothecium, etc.

Plasmopara

  and ructor P Jlasmopara vit ic ola liethyl 3, 5-dinitro-4-chloro benzoate: 1- (4-clhlorophenoxy) 1,13: triazol-1 -y)) - 2-but anol

Ethyl 3,5-dinitro-4-chloro-

  benzoate: dimethyllIl, Nt-l 1,2-1: -: phér l'èzi-bis (thiocarba 1:31 Moy) 1bis (carbamate "l n-Propy J 3, 5-dinitro-4 cho

îobenzoate: c- (2-ehlorophe-

nyl) -ca- (4-chlorophenyl) -5-

pyrimid inylmet hanoli

Isopropyl 3,5-dinitro-4-

chlorobenzoate: c- (2,4-di-

chlorophenyl) -c-phenyl-5-

pyrimid inylmethanol J

3: 1-5.7: 1

  1,) 25: 1 l-4: 1 'Aegenta ndépsin 0,55 kg / tnne lic 0.55 kg / tnneà 30% 1,0 kg / tonne

Agent disin-

fectant pel-

  at 30 56 1.0 kg / hectare 50 56 Fold 0.75 kg / hectare 40% FW Ln C> this Table 2 (Continued) in d Recos-ts of Formulation Reports Species of ingredients ac medium dose to

  mushroom Combinations tif syner the content to-

fungus gales tale ingreat-

active dient

Fusarium spp.

Fusarium spp,

Fusarium spp.

Fusarium spp.

Venturia in-

aequalis

Venturia in-

aequali s

M 4 ethy 3, 5-dinitro-4-chloroben-

zoate: methyl 1 H-benzimidazol-2-

ylcarbama te

Miethyl 3, 5-dinitro-4-chloroben-.

zoate: 11 4-chlorophenoxy) 3.35.

dimethyl-1- (1 H-1,24-triazol-1-

yl) -2-but custard

Methyl 3, 5-dinitro-4-chloroben-

zoatesi, 2-l (2,4-dichloropheenyl) -

4 -propyl- 11,3-dioxolan-2-yll -

methyl-l H-1,2,4-tria zole

Methyl 3, 5-dinitro-4-chloroben-

zoate: 1- (diphenyl) -3-tri fluoro-

  methyl- (phenyl) methyl-1 H-1,2,4-.

tria zole

Methyl 3, 5-dinitro-4-chloroben-

  zoate: 1,2-l (2,4-dichiloro-phé nyl) -

4-ethyl-1,2-dioxolan-2-, yllme-

thyl-l H-1,2,4-tri azole

Methyl 5 5-dinitro-4-chloroben-

zoate: l-? 4-phenylphenox y) -5.3-

  dimethyl-1- (1 Hl-1,2,4-triazoll-1 yl.) -2-butanol

3: 1-5,, 7: 1

*: 1-8: 1

: 1-4: 1

: 1-4: 1

6.6: 1-12.5: 1

6.6: 1-12.5: 1

  1.0 kg / hectare 0.9 kg / hectare 1.0 kg / hectare 1.0 kg / hectare 1.2 kg / hectare 1.2 kg / hectare% P FN P% PM% PM% EC

% CE

  1,) LNI c P -.1 to Table 2 (Continued) Report of Formulation Report Species of gredients medium acdose a

  mushroom Combinations tif syner the content to-

  giques tale en in--, active ingredient Ventur'i & aequalis in-f Peronospora manshurica

Ustilago op.

Ustilago op.

Methyl 3, 5-dinitro-4-chloro-

  benzotte: a- (2-chloroph 6 niyl) L-25 oe- (4-chlorophenyl) -5-pyrimidi 6,61,5 nylmethanol

benzoate: 1- (2,4-dichloroben-

1,2,4-triazol-1-yl) -2-butanol

1: 2 191: 1

Ethyl 3,5-dinitro-4-Chloro-

  benzoate:% _ (2-chlorohenyl) o 2: 1 14: 1 e (4-f luorophenyl) -5 -P Yrimidi nylmethanol

Ethyl 3, 5-dinotro-4-chloro-

  benzoate: l- (4-chloropheroxy) 2: 1 14: 1

tria zol-1 -yl) -2-butanol.

  1.2 kg / hectare 2.1 kg / hectare 1.5 kg / ton 1.5 kg / ton% EC% Pmi

Powder

aiflfectante

Powder

sinflectante

at 40%

  I Ln I -13- An extraordinary advantage of the compositions of the invention is that their production and application enriches the range of pesticides with new highly effective plant protection agents with a broad field of activity which pollute the biosphere less. the basis for the reduction in the application dose due to synergy Another advantage comes from the fact that

  farmers don't have to give up sys-

  well known witnesses slowly stagnating as a result of

resistance issues.

  The compositions of the invention and their activity

  fungicide are specified by the following examples

  which in no way limit the scope of the invention.

Example 1

  To disinfect winter wheat seeds

  to sow, we prepare film-disinfectants

  milk containing a total of 30% of active ingredients

  in suspension using methyl-3,5-dinitro-4-

  chlorobenzoate (DNCB-Me) with methyl-1 H-benzimidazol-

  2-yl carbamate (CARBENDAZIM) or 1- (4-chlorophenoxy) -

  1- (1 H-I-1,2,4-triazol-1-yl) -3,3-dimethyl-2-butanol (2 RIADIIi EIOL) in the combinations given in the Table The reports of the active ingredients are presented

in Tables 4, 5 and 6.

-14-

Table 3

Active ingredient / combination A B

DCNB-Me + CARBENDAZIM 30% -

  DCNB-Me + TRIAD Ih ENOL 30% 5 Ethylene glycol 7% 7% Cresol-formaldehyde condensation product 6% 6% 1-film forming polymer Mowilit DM-21 16% 16% o Antifoaming agent type Silicon SRE 1% 1 % Rhodamin dye 2 B 4 2% 2% Water for ion exchange 38% 58% à We study the activity of compositions A and B

  under laboratory conditions and under the conditions

  we find in the fields against diseases

  germination of winter wheat.

  A fraction of winter wheat seeds to be sown of the MV 8 species severely infected with Fusarium spp is infected with 0.2% by weight of Tilletia sporules before disinfection The seeds infected with Fusarium spp or the Fusarium spp are disinfected and Tilletia with the doses of the compositions studied as it is

see in Tables 4, 5 and t.

  We submit to a laboratory examination the

  seeds infected with Fusarium spp and disinfected.

  In each treatment, 200 seeds are placed on a selective propagation medium of Papaviza and incubated under a diffuse light at 20-22 O for -days. The percentage of growth is determined, then the percentage of the extent is evaluated under the microscope. of

Fusarium spp.

  -35 We perform these exams in 8 parallel and -15-

  summarize the average results in Table 4.

Table 4

  z 7 Activity against Fusarium Dose kg / ton Sprout Extent of infection DNCB-Ple + CARBENDAZIII (% due to Fus arium spp (%)

0.1 + 0.8 102.5 121.0

0.3 + 0.6 1.73.5

0.45 + 0.45 106.6 3.0 O

0.6 + 0.3 107.7 2.5.5

0.8 + 0.1 105.6 22.1

0.6 101.7 36.0

0.9 103.9 25,, 2

0.6 102.4 18.2

0.9 104.1 15.5

  Untreated control 100 62 Dose kg / tonne - Spread Extent of infection (%) due to Fusarium spp (% o)

0.1 + 0.3 101.535

0.3 + 0.2 105.2 1.5

0.45 + 0.15 107.2 O

0.6 40.1 108.8 2.2

0.8 + 0.05 107?, 5 18.1

096 101.7 36.0

O, 9 103.9 25.2

0.3 103.3 10.5

0.4 103.8 8.5

  Untreated witness 100 62 -16- The seeds also infected with Tilletia are subjected & field experiments on 2 m 2 plots in a randomized block arrangement in 3 parallels The seeds are sown on November 28 with spacing between the rows 12 cm in an amount of 60 g per plot; 150 seeds are sown with a seeder in the third row of each plot in order to assess phytotoxicity This assessment is made on April 10 of the following year by determining the number and height of the plants raised and judging the state

  plants by general impression We evaluate the activity

  vity against Tilletia at the time of full ripening by examining each ear and determining the number of ears

  healthy and the number of ears infected with Tilletia Les ta-

  Bleaux 5 and 6 show the average results of the 3 paral-

the the.

Table 5

  Phytotoxicity study Dose kg / tonne -E Emergence Height of DNCB-Me + CARBENDAZIM () plants (%) 0.1 + i 0.8 J 97.6 101.5

0.5 + 0.6 139.0 103.7

0.45 + 0.45 140.2 106.2

0.6 + 0.3 105.1 102.2

0.8 + 0.1 98.3 96.6

0.6 107.5 98.8

0.9 98.3 95.2

0.6 100.2 105.2

0.9 109.4 102.2

  Untreated control 100.0 100.0 Dose kg / tonne Emergence Height of plants DNCB 4 Me + TRIADIMENOL (% (%

0, # 1 + 0.3 105.0 100.5

0.3 + 0.2 127.4 108.0

0.45 + 0.15 145.5 108.6

0.6 + 0.1 106.4 102.5

0, e 8 + 0.05 9914 99.5

0.6 10-7.5 98.8

09 98.3 95.2

0.3 100-, 2 105.2

0.04 111.5 104.5

Untreated control 100.0 100.0

Table 6

  Activity against Til Jletia Dose kg / tonne Healthy ears Infected ears DNCB-Me + C RBENDAZIM pieces / plot pieces / plot

0.1 + 0.8 912.7 3.7

0.3 + 0.6 1247.5 1.3

0.45 + 0.45 1511, é 2 1.7

0.6 + 0.3 1147?, 8 0.0

0.8 + 0.1 956.3 10.0

0.6 1024.7 6.3

0.9 10.79.7 5.3

0.6 92-714 1894.

  0.9 951, t 9 17, '7 Control infected with Tilletia 804.7 151.7 Control untreated 935.0 14.0 O -18- Dose kg / tonne Healthy ears "infected udders DNCB-Me + T-RADIPFENOL pieces / plot pieces / plot

G, 1 + 0.3 957.7 10.0

0.3 + 0.2 1346.5 4.2

0.45 + 0.15 1,439.3 0.0

0.6 + 0.1 986.1 3.0

0.8 + 0.05 1012.8 9.6

0.6 1024.7 6.3

0.9 1079.7 5.3

0.3 901.5 12.0

0.4 924.7 12.7

  Control infected with Tilletia 804.7 151.7 Untreated control 933.0 14.0 It can be said on the basis of these experiments that in the laboratory the activity against Fusarium spp is synergistic at doses of 0.3 + 0.6 ; 0.45 + 0.45; and

  0.6 + 0.3 kg / tonne, i.e. by treating with a ratio

  port of 1: 2 to 2: 1 of the active ingredients by comparison with the activity of DNCB-Me or CARBENDAZIM used separately However disinfections with DNCB-Me + TRIADIMENOL present at doses of 0.3 + 0, 2 and 0, 45 + 0.15 kg / tonne, i.e. dealing with a ratio

  1.5: 1 to 3: 1 of active ingredients superior activity

  lower than expected from separate compounds used

  The percentage of growth is also improved by this treatment. In field experiments, all the numbers of plants raised, the height of the plants, the number and extent of infection of the ears.

  are very supportive when dealing with doses and

  ports of the active ingredients mentioned above.

-19-

Example 2

  For research of laboratory activity

  against Botrytis cinerea, Fusarium graminearum, Rhizocto-

  nia solari and Trichothecium roseum damaging the shoots as well as for the study of the activity on the emergence in the greenhouse and the field condition of pea seeds, a disinfectant in plastic dispersion is prepared

  containing a total of 30% active ingredients in use

  reading ethyl-3,5-dinitro-4-chlorobenzoate (DNCB-Et) with dimethylN, N '- (l 1,2-phenylene-bis (thiocarbamoyl) l -bis (carbamate)) (THIOOHANATEMETHYL) La content of the compositions is given in Table 7, while the studied ratio of the active ingredients and the results

  are summarized in Tables 8, 9, 10 and 11

  plant the pea seeds of species BR-52 with the

  fungicidal compositions tested in known manner.

Table 7

  Ingredients Content (%) DNCB-Et + THIOPIWNATE-Mi ETHYL 31.5 (industrial quality of 96% by weight) Dispersing agent 1494 10 Ethylene glycol 12 Polyvinyl alcohol Vinarol ST 8 Antifoaming agent L 051 1 Thodamin BSA 1150 0.4 Water for ion exchange 37.1 Laboratory experiments The activity against fungi under laboratory conditions is studied using the method

  diffusion on agar as follows.

  We have 32 ml of an aqueous medium of apple

  agar soil in 15 cm diameter petri dishes

-20-

  meter and each time 8 ml of freezing medium is placed there

  dried with the suspension of sporules of the fungus studied.

  The agar medium contains 3 parts by weight of culture medium with one part by weight of sporule suspension. The concentration of the sporule suspension is adjusted to 15-50 sporules per ml in the field of vision by microscopic adjustment. Round holes are prepared. of 10 mm in diameter on the agar plates solidified in the boots In each hole is deposited with a pipette 0.2 ml of an aqueous medium of the fungicide containing the active ingredients tested in the amount

  and the report presented in the tables for

  evaluation The cultures are incubated at temperature

  constant of 25-26% C, then the inhibitory action is evaluated

  tion on the fungal colony by measuring the radius of the zones of inhibition The results are presented to

table 8.

Table 8

  Diffusion test on agar Ingredient report Total quantity active ingredients of DMOB-Et ingredients: THIOPHIAN TE active METHYL ppm

1: 3,200

1: 1,200

3: 1200

1: 3,300

1: 1,500

3: 1 O

1: 3400

1: 1 4,000

3: 1400

1: 0 200

1: 0 300

1: 0 40 Q

0: 1200

0: 1300

0: 1400

  Radius in mm of the inhibition zone Botrytis' Fusarium Rhizoctonia Trichothecium cinerea grani nearum solani roseum

13 9 10 12

14 10 12 14

14 il il 15 il 10 16

16 10 12 17

il 13 17 16 9 il 16

17 9 1 to 16

19 10 14 18

12 4 4 8

14 6 6 10

16 77 it

12 76 3

13 8 7 5

9 7 8 '

  tg C. tu -1 -22- We can say on the basis of table 8 that concentrations of 200, 300 and 400 ppm of the compositions containing DNCBEt / THIOPH Ai ATE-4 IETHYL in ratios of 1: 3 to 3: 1 are much more effective in particular against Fusarium graminearum, Rhizoctonia solani and Tri- chothecium roseum than expected on the base

  of the activity of the same doses of the active ingredients.

  We also search in the conditions of

  laboratory the extent of seed infection disin-

carried out as follows.

  200 seeds are disinfected each time

  teas in sterile petri dishes on paper-

  wet filter After incubation at 18 C for 8 days, the number of seeds infected with the agent is determined

  pathogenic The results are given in Table 9.

  Dose kg / ton Number of seeds infected on the basis of aOO seeds DNOBEt + Alternaria Ascohyta Fusarium Penicillium

  + THIO Pfi ANATE-MEPHYL spp spp spp spp-

011 O'q 190 0.5

0.25 0.75 0.5

0.5 0.5

0.75 0.25

Ojq 0.1 190 1.5 1

0975 2 2.5 3.0 3.0

1 1 90 1100 2.0

0.75 1.5 1.5 2.5 3% 5

1,190 110 2 O 2.5

Untreated 12 O 810 5.0 9.0 C>

Table 9

  -24- It can be seen from Table 9 that,

  although the active ingredients DNCB = Et and THICPHINATE-

  NETHYL may well inhibit the growth of pathogens infecting seeds during incubation, we obtain a state completely free of agents

  pathogens only with DNCB-Et / THIPHÀNATE-? ETHYL combinations containing the active ingredients in a report

from 1: 1 to 3: 1.

  Greenhouse experiments The aim is to determine the action of disinfecting agents on the rate of emergence of pea seeds. Thus, pea seeds to be sown of the BR-52 species are disinfected with the compositions containing

  DNCB-And with THIOPHANATE-METHYL in pre-

  in Table 10 and we sow 100 seeds each time

  disinfected in a propagation box filled with plant soil in 4 parallels The seeds are covered with soil and the number of plants raised is determined on the 7th, 14th and 21st days after sowing The results are

given in Table 10.

Table 10

  * Doe kgtonn Number of beds raised from Number of plants raised by DNCB-Et + THIO 4100 seeds rapr utmonontaé PRAN & TE-m ETHYL 7 th day 14 day 2 day

011 0.9 168 293 299 129.4

0.25 0.75 209 307 508 133.3

0.5 095 262 320 320 138.5

0.75 0.25 259 316 316 136.8,

0.9 0.1 263 361 to 77 119.9

0.75 -156 280 280 121, P 2

I 218 258 281 121.6

0.75 138 263 2'71 117.3

I 162 2-71 277 119.9

  * No 102 223 231 100.0 treated M q.n 41. LY CD 9% N) U -26- Although the difference in lifting speed

  be low, however, based on the number of plan-

  When lifted, the difference between the activity of the same doses of combinations containing the two active ingredients and separate treatments is surprisingly high. The combinations containing the active ingredients

  in a ratio of 1: 3 to 3: 1 are synergistic.

Field experiences

  We are studying seeds for sowing peas

  affected by species BR-52 on plots of 4 m 2

  in a block arrangement randomized into 4 parallels.

  We sow a total of 200 seeds on April 3 with a space of 40 cm between the rows, a space of 5 cm between the stems, at a depth of 5 cm. We count the plants raised at the development stage 2 to 4 leaves on the 19th.

  May The results are presented in Table 11.

Table 11

  Dose kg / ton Average number of% of plants raised by DNCB-Et + plants raised compared to the number of THIOPHANATE pieces / plot seeds sown control

* I-ETHYL

_, i i i i,

0.1 0.9 145.5 72.7 113.5

0.25 0.75 148.2 74.1 115.6

0.5 0.5 151.2 76.6 119.5

0.75 0.25 153.0 76.5 119.0

0.9 -0.1 146.5 73.2 114.3

0.75 142.5 71.2 111.2

I 144.8 72.4 113.0

0.75 139.5 69.7 108.8

I 140.2 70.1 109.4

  No 128.2 64.1 100.0 treated -27- During field experiments, the doses

  1 kg / tonne DNCB-Et / THIOPHANATE- combinations

  METHYL containing the active ingredients in a report

  1: 3 to 3: 1 gives the best results.

Example 3

  To study activity against Plasmopara

  destructor (onion downy mildew), we prepare samples

  tones of wettable powder (PH) of 50%) by weight containing n-propyl3,5-dinitro-4-chlorobenzoate

  (DNCB-Pr) with a- (2-chlorophenyl) -a- (4-chlorophenyl) -

  -pyrimidinylmethanol (PHENARINOL) according to the composition

  presented in A and B in Table 120 The experiment is conducted

  biological awareness in a randomized layout on

  plots of 500 m 2 in 2 parallel We sow an oi-

  gnon of the species "Aroma" on April 12 in an amount of 4.5 kg / ha The treatments are carried out with the fungicide at the beginning of the formation of the head (July 21),

  then twice during head training (July 29-

  let and August 10), using a "Maruyama" machine of the air carburetor type, using 500 liters / ha

  of water and the combinations of the active ingredients

  managed according to the doses given in table 13 of the samples

  Let A and B be as shown in Table 12.

-28-

Table 12

  Ingredients / content Industrial quality DNCB-Pr at% purity Industrial quality PHENARI Mi O at 98% purity Synthetic silicate Ultrasil VN 3 Tensiofix BCZ, wetting agent

of the alkyl sulfate type

  polyglycol ether Dispergator HG, anionic dispersant Ultrazine Na, dispersing agent of the lignin-sodium sulfonate type Kaolin A B

52.63%

L

51.02%

% 3%%

29.37%

% 2%

6.21%

  73% The evaluation is carried out approximately 2 weeks after the last spraying using an evaluation scale ranging from 0 to 6 for 10 x 10 plants in

each plot.

  The scale used to assess the extent of leaf infection is as follows: 0 O free from infection 1 infection less than 5% 2 = infection 6 to 10% 3 = infection 11 to 25% 4 = 26 to 50% infection = 51 to 75% infection

6 = 76 to 100% infection.

  For the evaluation, the number of infected plants is calculated as a percentage (F%) of the total number -29-

  of plants studied and the index of the extent is determined

  due to infection (infection index) using the following equation:

a a x f.

  l - n o F = infection index ai = individual values of the infection evaluation scale fi = number of plants belonging to the various values of the infection evaluation scale (frequency)

  n = total number of plants studied.

  The lower the value of Fi, the more the

  position is effective The results of this experiment

are summarized in Table 13.

Table 13

  Dose kg / hectare Number of plants (pieces) belonging to DNCB-Pr + on the evaluation scale F F.

PHENARIMOL

  O I 2 3 4 5 b 0.9 0.1 l il 34 32 6 10 7? O 89 1.91 0.85 + 0.15 14 41 32 9 3 I O 86 1, b 49

0, # 8 0, O 2 29 38 33 O O O O 71 1.04

  0.75 + 0.25 34 51 14 I O O O 66 0.82

0, 3 24 38 19 9 7 O 97 2.28

O 9 31 31 1? 3 9 O 91 2.01

0.2 I 26 2-9 18 12 12 2 99 2.60

O 0.3 9 37 31 9 6 8 O 91 1.90

  Witness no 4 16 31 16 '1? 18 3 96 3.30 treaty o no LM c- -31- We can say from table 13 that

  DNCB-Pr when used with PHENARIMOL fucked

  Minimize the extent of infection due to onion downy mildew When using a rate of 1 kg / ha the most effective combination ratio pre-

  feeling the best synergy is 3: 1 to 5.7: 1.

Example 4

  To examine the activity against Plasmopara viticola (downy mildew), a spherical concentrate of aqueous suspensions containing a total of 40% by weight of active ingredients is prepared using isopropyl-3,5-dinitro- 4-chlorobenzoate (DNCB-i Pr)

  with m- (2,4-dichlorophenyl) -a-phenyl-5-pyrimidinyl-

  methanol (TRIARINOL) according to the content presented in the ta-

  bleau 14 The reports of the active ingredients are given

  born in the dose column of Tables 15 and 16.

Table 14

  Ingredients / Content DNCS-i Pr + 2 RIARIMO 10 L 40.0% Ethylene glycol 8% Emulsifying agent Tensiofix XN 6 2% Emulsifying agent Tensiofix CD 5 1.5% Emulsifying agent Pluriol PE 10500 2.5% Antifoaming agent Silicon SRE 1.0% Kelzan S 0.1% Water for ion exchange 44.9% The biological experiment is carried out with a 20-year-old plantation of the Italian tiesling vine species from the Lenz-Moser estate in two parallels On

  has sixty vines in rows on a par-

  that of 180 m 2 A total of 8 sprays are carried out with the fungicide (at the shoot stage of 20 to 25 cm, -32- when the bunch is lengthened, at the start of flowering, at the end of flowering, at the state of berries the size of a pea, before the closure of the cluster, at the closure of the cluster and the budding) with a quantity of water of 1000 liters / ha by means of a gun

  manual spraying of a Steyer-Puch apparatus-

  Haflinger equipped with a Tee-Jet D-7 spraying t-ste With the compositions tested, 3 kg / ha of sulfur-containing composition Kolosul 80 WP and 1.6 liters / ha of Ekalux insecticide are applied to the plant, which are ineffective

against vine downy mildew.

  The budding evaluation of the grape clusters is carried out by examining 4 x 50 clusters and 10 x 5 feet in each plot. The untreated control is evaluated by examining 2 x 10 feet. The extent of infection of the leaf is also determined. and the cluster as well as the extent of the burn of the leaf and the berry The values of F: o and F are calculated using the method, the rating scale and the equation given in l Example 3 The results are presented

in Tables 15 and 16.

  Dose kg / hectare Number of feet (pieces) belonging to DNOB-i Pr + on the evaluation scale F% F burn TRIARIMOL i

1 O 1 2 3 4 5 6 M

  Figure 15 Examination of the extent of leaf infection 1 C)

2 O O O O 56

0 O O O O 12

0 O O O O O

0 O O O O O

4 1 O O O 60

3 O O O O 50

1 O O O O 20

0 O O O O 16

  0.60 0, '74 0.56 0.22, 3, 5, 2 (O 9 t 8 + 011

: 1 0.6 + 0.15

Ot 5 + 01.2

0.4 + 0.3

018 -

1 99 0.5 iàLoin non \ .W \.% L

0 O 2 6 1 2 to

0 O 100

rla Ln ui -Pl C> P.

Table 16

  Examination of the extent of cluster infection Dose kg / hectare Number of clusters (pieces belonging to DNCB-i Pr * on the evaluation scale F% F Burning TRIARI__ _ __ __ __ __ _ __ __ __ _i ( o M

TRIABIMOL O O 1 2 5 4 5 6

  0.8 + 0.1 158 8 25 9 O O O 21 0.42 10.1

  0.6 + 0.15 180 4 16 O O O O 10 0.18 O

0.5 + 0.2 184 4 12 O O O O 8 0.14 O

0.4 + 0.3 182 16 2 O O O O 9 0.11 O

  0.8 98 12 20 42 28 O O 51 1,> 45 8.3

  1.0 112 24 29 20 15 O O 44 1.01 i 15.7

0.5 118 23 20 29 10 O O 41 0.95 O

  0.7 153 19 14 il 5 0 O 23.5 0.46 O Witness no 49 148 58 564 OO '75, 5 2, 59 O treaty fla US w% -W -P -35- We prove by these experiences that 0.7 kg / ha of the combinations containing DNCB-i Pr and TRIARIMOL in a ratio 1.25: 1 to 4: 1 is more effective against downy mildew than would be expected from the activity total of active ingredients.

Example 5

  To examine activity against Fusarium infection of the ear of winter wheat, using methyl-3,5-dinitro-4-chlorobenzoate (DNCB-Me) with methyl-l H-benzimidazoli 2 -ylcarbamate (CARBENDAZIM),

  1- (4-chlorophenoxy) -3,3-dimethyl-l- (1 H-1,2,4-

  triazol-1-yl) -2-butanone (TRIADIMEFON) -, 1-l 2- (2,4-

  dichlorophenyl) -4-propyl-1,3-dioxolan-2-yll methyl-1 H-

  1,2,4-triazole (PROPICONAZOLE) and 1-ldiphenyl- (3-

  trifluoromethyl) -phenyll-methyl-IH-1, 2,4-triazole (FLUOTR Ii EZOLE), wettable powder (PM) compositions are prepared containing a total of 70% by weight of active ingredients according to the table of active ingredients are presented

18, 19, -20 and 21.

Table 17

  17 The reports in the Ingredient / Content tables A B C D

DNCB-Ne + CARBENDAZIM (ma-

industrial quality

it at 95% purity)

DNCB-Me + TRIADIMEFON (ma-

industrial quality

  it & 95% purity) DNCB-Me + PROPICONAZOLE

(industrial quality materials-

  trielle at 95% purity) DNCB-Me + FLUTRIMEZOLE

(industrial quality materials-

  trielle at 95% 'purity) Synthetic support Cab-O-Sil Atlox dispersing agent 486 73.7 73.7 73.7 753.7

10 10 10

3 3

  -36- Table 17 (Continued) Ingredients / Content ABCD Wetting agent Atlox 4995 3 3 3 3 Dispersing agent Polyphon O 4 4 4 4 Kaolin support 6.3 6, 5 6.3 6.3 The biological experiment is carried out with a

  winter wheat species (Jubilejnaja-50) in areas

  those of 10 m in 4 parallel We treat

  fungicide with a volume of water of 600 liters / ha at the end of the ear formation We assess the extent

  infection of the ears due to Fusarium spp under review

  2 x 100 ears in each plot about 10 days

after spraying.

  The harvest of the plots after the harvest is determined, then an average sample of the seed harvest is taken and the total extent of seed infection due to Fusarium spp is determined on the basis of 2 x 100 seeds by examining the crop. under a microscope after incubation on Papaviza medium at 20 C for 8 days (A prior surface disinfection is carried out when the extent of the infection is evaluated

  internal) The results of this experiment are summarized

  més in tables 18, 19, 20 and 21.

Table 18

  Dose kg / hectare Extent of Fusarium spp infection (%) Importance of DNCB-Me + harvest CARBEND ZIM E-pi Seed (total) Seed (internal) kg / 10 m 2

0.85 + 0.15 01.20 6.50 4.25 6.55

0.80 + 0.20 0950 8.20 6,, 50 6.42

0.75 + 0.25 1.00 9, 50 7.00 6.44

0.25 7.30 18.20 15.25 6.11

0.50 6.50 16.00 11.75 6.0 e O 1

0.9 5.00 13.25 11.50 6.10

  1.8 -4.25 11.50 a.m. 11.50 3.13 Witness no 1-1.50 38.75 51, i 25 5.52 treated M Ln 4- LM & I CD 8%% -W -13

Table 19

Dose kg / hectare DNOB-Me +

TRIADIMEFON

0.85 + 0.05

0.80 + 0.10

Where? 5 + 005

0.15 i 0.20

0 IC) -

1.8 -

  Untreated control Extent of Fusarium spp infection (%) Harvest size kg / 10 m 2 Seed (total) Seed (internal) Ear 0.25 0.05 4.50 4.50 4.00

41> 25

1 I-50

6.0 4.5 2.0 8.5 8.0

1 3.25

  11.50 38.75 3.5 3.0 1.5 6 'e O, 0 11.5 11.5

31 2 5

  6.35 6.62 6.6-7 6.15 6.22 6.10. , 52 Co ru vi & N U 4 C> 0%

Table 20

  Dose kg / hectare Extent of infection due to Fusarium spp () Importance of DNCB-Me + harvest 2 PROPICON ZOLE Epi Seed (total) Seed (internal) kcg / îo m

0.85 + O 0.5 5.0 9.0 5.0 6.45

0.80 + 0.20 3.5 '4, 5 3.5 6.42

0.75 + 0.25 1.0 15.5 3.25 6.15

0.25 -7.0 e 14.5 18.5 5.75

0.30 6.5 12.5 15.5 5.90

0.9 5.0 13.25 11.5 6.10

1.8 -4.25 11.50 11.5 3.13

  Control no I 1, 50 38.75 31.25 5.52 treated 1. ul Ln 4 c

Table 21

  Dose kg / hectare Extent of infection due to & Fusarium spp fl Importance of DNCB-Me + harvest FLUOTRIMEZOLE Epi Seed (total) Seed (internal) kg / 10 am

0.85 + 0.15 3.5 9.5 8.0 5.95

0.80 + 0.20 2.5 6.0 7.0 6.05

0.75 + 0.25 1.5 6.5 7.5 6.15

0.25 6.5 15.5 12.5 5, .85

0.50 9.0 19.0 16.0 5.62

0.9 5.0 15.2 e 11.5 6.10

1.8 -4, P 25 111.50 11.50

  Untreated control 11, D 50 5.8.75 51.25 5.52 NU Ln at -41 - Exemnole 6 To examine the activity against Venturia inaequalis (apple scab), using 3,5-methyl-dinitro -4-chlorobenzoate (DNCB-Me) and 1-l 2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolan-2-yll-

  methyl-1 H-1,2,4-triazole (ETACONAZOLJE), 1- (4-phenyl-

  phenoxy) -3,3-dimethyl -l- (1 H-1,2,4-triazol-1-yl) -2-

  butanol (BITERTANOL) and a- (2-chlorophenyl) -a- (4-

  chlorophenyl) -5-pyrimidinylmethanol (PHENARIMOL), emulsifiable concentrates are respectively prepared containing a total of 20% by weight of active ingredients according to table 22 The reports of the active ingredients

  are presented in the dose column of Table 23.

Table 22

  Ingredients / Content A (o / & B (% f C (% DNCB-Prle + ETA ONAZOLE 20

DNCB-Mie + I 3 ITERTANOL 20-

  DNCB-Me + PHUANRIIIOL 20 53 cyclohexarone solvent 20 40

xylene based filler 50 58 -

  Atlox 4858 emulsifier 3 Atlox 8916 emulsifier 3,5 Atlox 4851 emulsifier 3,5

Solvent based on isophorone 30 -

  Tensiofix D-120 3.5 emulsifier

  Tensiofix-AS 3.5 emulsifying agent -

  Tensiofix B emulsifier -7425 5.0 -

  Solvent HA 30 Arcopal emulsifier N 080 5.0 Emulsifier Emulsogen EL 1.5 Emulsifier Sapogenate T-180 3.5 -42- The biological experiment is carried out in two parallels with a 20-year-old apple plantation. Jonathan cultivated in 1/2 ha plots with 7.5 x 4.5 m ties Fungicide sprays total 9 times in the

  growing season at intervals of 1 to 2 sec-

  with a water volume of 1000 liters / ha using a Kertitox Na-10 sprayer fitted with a Tee-Jet spray head. The extent of leaf infection on 10 trees is evaluated twice. the end of the first and second growth of shoots On

  examine 100 leaves of each tree We assess the extent

  due to fruit infection and extent of blight on 10 trees before harvest 50 fruits from each tree are examined. Results are 23.

Table 23

  presented in the table Dose kg / hectare Extent of burn Extent of burn of infection of DNCB-Ne + leaves of fruit fruits

ETACONAZOLE

at the at the 2nd evaluation,%

I + 0.15 O 7.2 2.2 O

1.25 + 0.1 O 8.2 2.3 O

1.50 + 0.075 1.4 9.8 2.7 10.5

1.50 + 14.6 32.3 12.5 10.7

2 9.5 9.5 10.2 20.4

0.15 10.4 28.5 5.0 O

0.2 9.3 26.4 4.7 10.0

  Untreated control 27.4 62.6 41.5 O -43- Table 23 (Continued) ui ,,,, Extent of in Scope of Burn Dose kg / hectare fection of DNCB-Me infection + leaves of fruit fruit

BITERTANOL (%) (O /)

1 st to 2 nd assessment,%

I + 0.15 O 5.3 1.9 O

1.25 + 0.10 O 8.0 2.2 O

1.50 + 0.075 5.1 11.2 2.7 10.0

1.50 14.6 32.3 12.5 10.7

2 9.5 9.5 10.2 2,094

0.15 5.3 21.5 3.8 O

0.20 5.9 19.9 2.8 11.1

  Untreated control 27.4 62.6 41.5 O Dose kg / hectare Scope of in Scope of Burn DNCB-NX fection of infection of PHENARIBIOL leaves of fruit fruits

PHENIARIMIOL

  at the 1 st at the 2 nd () (%) evaluation,% 1 + 0.15 O 5.5 2.1 o

1.25 + 0.10 O 6.3 3.2 O

1.50 + 0.075 2.3 9.5 2.3 10.8

1.50 14.6 32.3 12.5 10.7

2.0 9.5 9.5 10.2 20.4

0.15 6.8 22.4 4.6 O

0.20 7.2 18.6 3.1 11.3

  Untreated witness 27.4 62.6 41.5 O -44- We can say from Table 23 that the

  rates of 1.15 to 1.55 kg / ha of combinations of ingredients

  active teeth studied, i.e. DNCB-Me with either ETACONAZOLE, BITERTANOL or PHENARIMOL, have a synergistic action against Venturia inaequalis when

* the ratio of active ingredients is from 6.6: 1 to 12.5: 1.

Example 7

  To review activity against Peronospora

  manshurica (soybean late blight), using methyl-

  3,5-dinitro-4-chlorobenzoate (DNCB-Iie) with 1- (2,4-

  dichlorobenzyl) -3,3-dimethyl-1 - (1 H-1,2,4-triazol 1-yl) -

  2-butanol (DICLOBENTRAZOLE), a wettable powder (PM) composition is prepared containing 70% by weight of the active ingredients according to table 240.

  active ingredients are shown in Table 25.

Table 24

  Ingredients / Content DNCB-Me + DICHLOBENTRAZOLE 70% Synthetic support Cab-O-Sil 15% Wetting agent Netzer IS 5% Dispersing agent "Dispergiermittel SI" 6% Dispersing agent Polyphon O 6% -

  We conduct the biological experiment on so Ja -

  of the Ewans type Fungicide treatments are carried out using the compositions tested 3 times (at a height of cm of the soybean, at the start of flowering and at full

  flowering) The sprays are carried out with a

  400 liters of water per hectare using an agricultural machine

  RAH-14-K-10 type school The evaluation is carried out on

  x 10 plants on the 16th day following the last milking

  The results are calculated according to the evaluation scale.

  luation and the equation given in Example 3 The extent

  Dose kg / hectare Number of feet (pieces) aprarten Rnt Burn DNGB-Me + at FOIO pi scale

DICLOBENTRAZOLE 000

0 1 2 3 4 5 E>

  p P P r_ P O Fi- e P 91 M CD a, Z Fi ct e Fi F-J M O 1-0-1 ct ru ct \. n O 0 p ct O P. O O F% P. F "F-J O I, O O ct CD M O Fi CD t 3 CD ct

Table 25

1 O

+ 1 1) 6

+ 1 IP 4

+ 1 1) 2

+1 90

+ 0.8

33 38

62 30

71 22

25

27 42

0 38

he 33

22 29

37 26

  il 0 O 0 O 0 O 0 O 6 O 0 O 1 O 0 O 0.36 0.35 1.23 2.16 1.86 1.36 1.29 3.6, 6 9.8 17.6 7.9 0, 5 1 Il 1.3 1 93 -% A \ -n da 11 2.1 Untreated witness 0 O 40 41 il 8 O 100 2 8? -46-

  In the case of a 2.1 kg / ha dose of the

  total active ingredients, biological activity is most favorable when the ratio of DNCB-Me to DICLOBENTRAZOLE is from 1: 2 to 1.1: 1 The activity of the combination exceeds the effect measured separately from the same

doses of active ingredients.

Example 8

  To find activity against Ustilago sp.

  (late blight) using methyl-3,5-dinitro-4-chloro-

  benzoate (DNCB-Me) with a- (2-chlorophenyl) -a- (4-

  fluorophenyl) -5-pyrimidinylmethanol (NUARIMOL) or with

  1- (4-chlorophenoxy) -3,3-dimethyl-1- (IH-1,2,4-triazol-

  1-yl) -2-butanol (TRIADINENOL) respectively, disinfectant powder compositions are prepared containing a total of 40% by weight of the active ingredients according to Table 26 The ratios of the active ingredients are

shown in Table 27.

Table 26

Ingredients / Content A (f%) B (%,

DNCB-Me + NUARINOL 40 -

DNCB-Me + TRIADIMENOL 40

Wetting agent Tinovetin B 2 -

Dispersing agent Dispergator HG 5 -

Polyvinyl alcohol

Nowiol 30/88 4 -

"Horna Queens Milori" dye

Blau "1.5 -

  Kaolin 47.5 40.25 Synthetic support Ultrasil VN 3 5 Wetting agent Netzer IS 2.5 Dispersing agent Ultrazine Na 6.0 Polyvinyl alcohol Rhodoviol 14/120 2.5 Dextrin 2.5 Dye Rhodamin BBA 1150 1.25 -47- On disinfects GK-59 barley seeds for sowing infected with Ustilago sp (downy mildew) with

  the compositions tested, then they are sown in

  those of 50 m 2 with a distance of 12 cm between the rows, at a depth of 5 cm in a block arrangement randomized into 4 parallels We sow seeds exactly over a 2-meter stretch of the eighth row of each plot We evaluate the phytotoxicity at the development stage 2 to 4 leaves of barley in

  counting the plants raised from 150 seeds se-

  measured over the 2 meter area and measuring the height

  ered olants We assess the infection by downy mildew at the time of flowering by counting the smoky ears found in the plots, and we also study by the germination of the sporules The results

  of this experience are summarized in Table 27.

Table 27

  2 O Dose kr / ton Number of Height Number of ears NCB-Ne + medium plants infected D Ni CB-Mle + lve NUARIHOL lve NUARIOL (pieces) (cm) (pieces)

I + 0.5 117.8 8.6 O

1.25 + 0.25 113.3 8.6 O

1.40 + 0.10 114.0 8.5 O

1.40 110.3 8.2 44

1.80 97.5 8.0 15.3

0.5 114.8 8.5 5.0

0.7 114.5 8.5 1.8

  Untreated control 109.0 8.6 97.5 -48- Table 27 (Continued) Dose kg / ton Number of Height Number of ears DNCB-Me + infected medium plants raised TRIADIMENOL: (pieces) (cm) (pieces)

I + 0.5 118.5 8.3 O

1.25 + 0.25 119.3 8.7 O

1.40 + 0.1 118.1 8.4 O

1.40 110.3 8.2 44

1.80 97.5 8.0 15.3

0.5 115.4 8.3 4.3

0.7 115.0 8.1 0.5

  Untreated control 109.0 8.6 97.5 Using a dose of 1.5 kg / ton of combinations, infection of the ears by mildew is fully combated when the ratio of DNCB-Me to NUARIMOL or TRIADIMENOL, respectively, is 2: 1

at 14: 1.

-49-

Claims (2)

CLAIMS -   I Fungicide compositions with synergistic action   a gic comprising as a first active ingredient a   riveted 35,5-dinitro-4-chlorobenzoic acid of formula (I) C 000-R 02 N NO 2   Cl (I) or R represents a C 1 -C 6 alkyl group; and as a second active ingredient a group body consisting of -   (i) dimethyl (N, N'-l 1,2-phenylene-bis (thiocarbamoyl) l-   bis (carbamate)); (ii) a benzimidazole derivative of formula (II) N NH-C-OCH I R 1 O   o R 1 represents a hydrogen or a group of formula (a) O _ C N C 4 H 9 (a) (iii) a pyrimidinylmethanol derivative of formula (III) -50- OH 3 C R 4 (III)   "'1-t. Ns +>" N o R 3 and R 4 are similar or different and represent a phenyl group optionally substituted by a halogen; and (iv) a 1,2,4-triazole derivative of formula (IV) R 5 (IV)   2 O o R 5 represents a hydrogen, a phenyl group, a phenoxy group optionally substituted by a phenyl, a   halogen, or a benzyl group substituted by a ha- logene,   R 6 represents a hydrogen or a trifluoromethyl group   phenyl and R represents phenyl or one of the groups   pes of formulas o I i C C 4 H 9 (c) C 4 H 9   -C C 4 H 9 (d) OH and -51- Cl y-orci (e) 0 / i I Rs LLR 8 o R 8 represents a C 1 -C 4 alkyl group; and the weight ratio of the active ingredient of formula (I) to the other active ingredient chosen from the group   consisting of dimethyl (N N '-1,2-phenylene-bis (thio-   carbamoyl) l-bis (carbamate) and the compounds of formulas   (II), (III) and (IV) is 1: 2 to 14: 1.   2 fungicidal composition with synergistic action according to claim I comprising a total of 5 to 85% by weight of the active ingredients.   3 Synergistic fungicidal composition   according to claim 1 containing a compound of   mule (I) o R denotes a C 1 -C 4 alkyl group,   preferably a methyl or ethyl group.   4 fungicidal composition with synergistic action according to claim 1 containing a compound of formula   (III) o R 3 and R 4 represent a phenyl group substantially   killed by a halogen, the halogen atom being an atom fluorine and / or chlorine.   Synergistic fungicidal composition according to claim 4 containing a compound of formula   (III) o R 3 and R 4 represent a chlorophenyl group.   6 fungicidal composition with synergistic action according to claim 4 containing a compound of formula   (III) o R 3 represents a chlorophenyl group and R 4 represents has a fluorophenyl group.   -52- 7 Fungicide composition with synergistic action   according to claim 1 containing a compound of   mule (IV) o R 5 represents a hydrogen, a phe-   nyle or a phenoxy group optionally substituted by a phenyl group or a chlorine atom, or a group   benzyl substituted by one or two chlorine atoms.   b Synergistic fungicidal composition   according to claim I containing a compound of   mule (IV) o R represents a group of formula (e) Cl t '\ Cl (e) O O i R 8   o R 8 represents an ethyl or propyl group.   9 Synergistic fungicidal composition   according to claim 1 comprising a compound of   mule (I) and dimethyl (N, N '1,2-rhénylène-bis (thio-   carbamoyl) l-bis (carbamate)) in a weight ratio from 1: 3 to 3: 1.   10 Synergistic fungicidal composition   according to claim 1 comprising a compound of   mule () and a compound of formula (II) in a ratio weight from 1: 2 to 6: 1.   11 Synergistic fungicidal composition   according to claim I comprising a compound of   mule (I) and a compound of formula (III) in a report. weight from 1: 1 to 14: 1.   12 Synergistic fungicidal composition   according to claim 1 comprising a compound of   mule (I) and a compound of formula (IV) in a ratio -53- by weight from 1: 2 to 1 '4: 1.   13 Process for the preparation of fungicidal compositions with synergistic action in which the active ingredients taken in a weight ratio of 1: 2 to 14: 1 are mixed with a derivative of 5,5-dinitro-4-chlorobenzoic acid of formula (I) COO-R ff (I) 02 02   Cl o R represents a C 1 to C 6 alkyl group and a compound chosen from the group consisting of   dimethyl (N, N'-l 1,2-phenylene-bis (thiocarbamoyl) l-bis-   (carbamate), a benzimidazole derivative of formula (II) N <N NH-CO Cli (II) R 1 o R 1 represents a hydrogen or a group of formula (a), 3 OO = C NH C 4 H 9 ( a) a pyrimidinylmethanol derivative of formula (III) '_:, - '** - _ -54- IH R 3 R 4   I (III) o R 3 and R 4 are similar or different and represent   a phenyl group optionally substituted by a halo   gene, and a 1,2,4-triazole derivative of formula (IV) N NR 1 7 R 5 C 7   I R 6 o R 5 represents a hydrogen, a phenyl group, an optionally substituted phenoxy group rar a phenyl or a   halogen, or a benzyl group substituted by a halo- uncomfortable,   R 6 represents a hydrogen or a trifluoromethyl group   phenyl, and R 7 represents a phenyl or one of the groups (c), (d),: C C 4 H 9   o O (c) c C 4 H 9 I- OH (d) (IV) -55- and (e) Cl Cl (e) o R 8 represents a C 1 to C 4 alkyl group, with supports, vehicles and other auxiliary and additive materials generally used for the preparation of protective compositions for plants.