DD160762A3 - MEANS FOR CHEMOTHERAPY OF VIRUSES OF CULTURAL PLANTS - Google Patents

Abstract

The invention relates to compositions for the chemotherapy of crops based on 2,4-DIOXOHEXAHYDROTRIAZIN-based crops, which are characterized by the fact that they contain thiadiazoles, oxazoles and / hydrazones substituted as synergists in addition to the usual auxiliaries and traitors. The synergistic increase of the antiphytoviral Effects of the comnination partners, virus-related yield depressions are reduced to a greater extent than by the individual drugs or even completely avoided. The spectrum of influenceable viruses is expanded. In addition, various combinations of the state of health of vegetatively propagated plants (seedlings) is noticeably improved. The formation of preventable viruses is counteracted by the application of the combination preparations according to the invention to a greater extent than was hitherto possible. Surfactants, adhesives and other formulating agents are added to the active compound combinations according to the invention.

Description

Title of the invention

Agent for chemotherapy against virus crops

Field of application of the invention

The invention relates to compositions for the chemotherapy of crops of the crops, which are obtained by combining different active ingredients with the addition of conventional excipients and carriers.

Characteristic of the known technical solutions

In recent years, a larger number of preparations have become known which inhibit the multiplication of plant viruses. These include analogues of purine and pyrimidine bases or of corresponding nucleosides and nucleotides as well as analogs of intermediates for the biosynthesis of the corresponding bases and nucleosides, also antibiotics from microorganisms and higher plants and polyanions, including polyacrylic acid. In addition, an attempt was made antiphytovirale effects and side effects of natural and synthetic plant hormones or otherwise growth regulators, fungicides, especially of%, System fungicides, insecticides and herbicides, 'i in these cases, in low, non-damaging the plants:;. Quantities of use can be used to harness for antiphytoviral chemotherapy.

Apart from some triazines and of Hypericum by "foratum isolated antibiotic preparation Imanin (Bo _T byr, Chimioprofilaktika 1 terapija wirusnych bolesnei rastenii, Isdatelstwo Naukowa dumka, Kiev 1976) is

none of the antiphytoviral preparations of the groups cited became known for a field test of greater magnitude. The main reasons for the low practical application are:

1) too strong phytotoxicity '

2) excessive warm-blooded toxicity

3) .uneconomic substance synthesis or extraction

4) too little effect _;

5) too little difference between dose curativa and dose toxica. '

Hydrogenated triazines alone, and of these especially 2,4-Dioxohexahydrotriazin (DD-PS 115 566), have withstood extensive testing. In about 50 practical trials with consumer potatoes (virus coverage 10 to 30%) on about 1000 ha of treated field surface, a highly significant average yield of about 10 % was obtained (Schuster et al., Journ. Potato Res. 1979). Thus, by treatment with neither phytotoxic nor vertebrate-toxic DHT in potato populations, about 50 to 60 % of the virus-induced yield depressions could be compensated. In other crops, such as tomato, additional income of about the same order of magnitude was achieved. Recently, good results have also been achieved by antiphytoviral thioureas (DD-PS 142 788), ureas (DD-PS 141 968) and guanidines (DD-PS 139 921), it being noteworthy that some viruses other than DHT are affected , Even though some of these new antiviral compounds have reached the efficacy of DHT, it has not surpassed any of the preparations. The reason for this is to seek that as a result of the close intertwining of viral replication with basic metabolic processes of the plant host, including its nucleic acid and protein budget, encounters great difficulties to slow down a viral replication step as much as possible without at the same time side effects Host processes occur.

228 75 4 5

Object of the invention

The aim of the invention is, while avoiding plant damage, to increase the efficacy of the chemotherapy of plant-derived virions beyond that achieved.

Presentation of the essence of the invention

The invention is based on the object, by the common use of different chemical species, of achieving an antiviral effect of a corresponding preparation which is significantly above the effect of the individual components and also substantially exceeds their summed effect.

The object is achieved in accordance with the invention in that 2,4-dioxohexahydro-1,3,5-triazine is used together with substituted thiadiazoles of the general formula I, oxazoles of the general formula II and / or hydrazones of the general formula III.

In the general formula

I N-N ·

Il I! I R1 - CC - R ₂

R 1 and R _2, by themselves or in any variation, represent an amino group which may be substituted or unsubstituted by äliphatic, substituted aromatic, substituted aromatic, cycloaliphatic and unsaturated aliphatic radicals, or an alkyl or substituted alkyl group, phenyl and substituted phenyl groups, heterocyclic groups and the adamantyl group, which in the specific case may be such that R 1 and R _{2 are} an amino, allylamino, propylamino, nano, cyclohexylamino, benzylamino, phenylamino, 4 -Chlorphenylamino-, u ~ and ß-Naphtylamino-, methyl, tert-butyl, benzyl, 2-hydroxyphenyl, 4-Mtrophenyl-, may be 4-rPyridyl group.

IL ö / Ό

In the general formula II

mean

R = alkyl, hydroxyalkyl or phenyl groups R1 = alkyl, phenyl, hydroxyl, carboxyl groups R'2 == / KHg- »guanyl-, alkylthiocarbamoylhydrazino-, N-substituted aminomethyl groups, furthermore hydrazone of glyoxylic acid, acetone, aldoses , N-alkylisatines, halogenated benzaldehydes, pyridinaldehydes, ferrocerialdehydes, aminoacetophenone, N-substituted acetophenones, polyhydroxyacetophenones and methoxyacetophenone, as well as salts and adducts of these substances. ' '· ....

In the general formula

Hl "R ¹ R ³

, , '.'; '. '. '.. ^^ C = N-N = C'

R- and Rj are simultaneously or in any variation for H, SH, CN, CH3 groups, furthermore pyridyl, pyridyl-N-oxide, N-alkylpyridinium, quinolyl, quinolyl-N-oxide, N Alkylchinolinium, quinoxalyl, isoquinolyl, isoquinolyl, N-oxide, N-alkylisoquinolinium, benzothiazolyl, naphthyl, phenyl, p or m (N-substituted-aminophenyl), pN-alkylnitrosaminophenyl, styryl - And alkyl, nitro, halogen, hydroxy or alkoxy-substituted compounds of the type mentioned, and

228754 5

or. j »

alkyl

SLJ-

N-ilkyl

C ₆ H ₅

to

CrH ₁ -

(Y = 0 or = FN = 0 (NH ₂ ) 2)

(X =

R3 and R4 each individually or in any variation for H, OH, SH, S-alkyl, S-alkenyl, S-aralkyl, NH ^ NH-alkyl, NR-aralkyl, alkoxy, S- Alkyl, morpholino, pyridyl, quinolyl, quinoxalyl groups.

These compounds may be used in the form of their complexes with heavy metal ions such as Cu ^ ⁺ and Zn2 ⁺ ions, optionally together with other anions and additional ligands. The synergists according to general formulas I, II and III influence an event in the replication cycle of the virus which either precedes or follows the DHT-influenced event, such as by virus-synchronous cultures in protoplasts or by synchronous cultures in intact leaves Differential temperature inoculation method according to Dawson, Schlegel and Lung (Virology 65, 565-573, 1975) can be detected. As a result of the combination of. DHT with the listed synergists is considerably increased, in each case the antiphytoviral action of DHT. Conversely, the antiviral effect of the respective combination partner also increases. This synergistic effect, in many cases, makes it possible to reduce the application rates of the substances, which often improves both the dose-toxicity dose-to-dose-curative ratio and can reduce vertebrate and human toxicity. In addition, the range of chemotherapeutically detectable viruses is extended. Resistance to chemotherapeutic agents will be

because high levels of resistance to co-inbryltone preparations could only be produced by multiple mutations, the greater the range of available DHT combination partners, the more viruses can be affected, and the lower one will be at a suitable level Rotation of the drug combinations the risk of developing against. Chemotherapeutic drug resistant strains, so that in this respect with the inventive combinations considerable port steps have been achieved.

The active ingredients to be combined are mixed with inert diluents and with suitable formulation agents and processed into wettable powders, pastes, emulsion concentrates, etc. The formulation and application of the combinations according to the invention can be carried out by the known and customary methods. It has proved to be advantageous if the active substance content accounts for 10 to 90 % of the agent, which is dispersed shortly before use with water to spray liquors or in water-soluble compounds to spray solutions.,. , -

Combination partner 1 'and combination partner 2 may be combined in a common preparation which may further contain surfactants, adhesives and / or other formulating agents.

However, combination partner 1 and combination partner 2 can also be processed separately into preparations which may each contain surfactants, adhesives and / or further formulating agents. , In. In these cases, preparations 1 and 2 may be designed so that they are combined prior to application to the plants in tank mixes and then co-applied. However, they can also be designed so that a separate application takes place.

Eb are combined können'auch more than two combination partners in a preparation which is characterized in that a combination partner is the Dioxohexahydrotriazin. With regard to the addition of surfactants, ¹ adhesive and / or other formulation auxiliaries, the combination: to Präparätionen or the preparation of separate preparations

2287 5 4 5

The explanations concerning the two combinations apply mutatis mutandis. The. spray mixtures according to the invention uriel solutions can be applied with the usual spraying equipment. They are suitable for an additional combination with insecticides, fungicides and other pesticides in tank mixes.

In general, application rates of from 0.25 to 10 kg / ha suffice to achieve adequate protection against yield losses due to virus attack. The application rate is considerably lower than that which would be required if the combination partners were used alone.

embodiments

To characterize the enhanced antiphytoviral effects of the preparation combinations, whole plant tests on solanaceae were used in particular. Frequently occurring plant viruses were used as test viruses which, on the one hand, infect the respective host system and, on the other hand, permit a perfect concentration determination for serological Y / ege. In the basic experiment, using an abrasive (carborundum powder, grain size 500), the two lower, intact leaves of Nicotiana tabacum 'Samsun' plants having formed 5 to 7 leaves were inoculated with potato X virus. Each 2 days before and 2 and 7 days after the inoculation, the test plants were treated with solutions or suspensions containing the individual preparations or preparation combinations in the concentrations indicated in the working examples and 0.2 % Fekama adhesive (Buna-latex adhesive). They were sprayed to drip point. This corresponds, under practical conditions, to an application of 600 1 spray solution or broth per hectare of oil. As a control, a number of plants were inoculated in the manner described with the same virus. The spraying was carried out with the same solvent-water mixture with the addition of 0.2 % Fekama adhesive, but without active ingredients

 5 to 7 days after the inoculation, the virus concentra-

228 7 54 5

in the upper inoculated leaf and 12 to 20 days after inoculation in higher-leaved leaves separated from the uppermost inoculated leaf by at least 2 leaves, serologically in the precipitate drop test using dilution end point determination (geometric dilution, respectively) 1: 1 with physiological saline solution until no virus is serologically detectable), determined plant- and leaf-wise separately (G. Schuster, 'Arch. Phytopath and Plant Protection 1 , 1971, 171-187 and V3, 1977, 231- 241). Each experimental member comprised at least 10 individual plants.

The virus concentration found in the leaves of each plant was expressed in numbers of values. In this case, value 0 means that even in a 1: 1 diluted (^ output) pressed juice no virus was detectable 'was. The value 1 shows that after a single dilution in the ratio 1: 1 no more virus ^N could be detected, "*" the value 2, that after two dilutions no virus precipitate occurred, / etc. For comparison of the experimental subjects received results with those of the control, averages were formed from the individual numerical values, which corresponded to the smear values found in the control plants. were compared. In the following Ta.bellen is the percentage, the virus concentration, which was found in the test member in comparison to the control (control '= 100 %) was found. This value is called the reduction coefficient (RK). RK = 8 means, for example, that in the test element the average virus concentration is reduced to 8 % of that of the control wa.r,...

The significance of the differences found was checked in the t-Teat. The test result was indicated next to the differences expressed in percentages in symbols. , , .

These say: · ''

228754 5

+: 1 f '= T) ? 0 , 1 5'ί

: 0.1 % = ρ

P - U "be: 2 '; _: ,' Probability '

The significance of the reduction of the proportion of eye cuttings with viral symptoms after treatment with antiphytoviro.len preparations or Kombi nn.tionen invention (Example 4) was determined according to S. Koller by comparing the observed in two healings frequencies. The results were described with the already mentioned symbols.

The experiments carried out and evaluated in the manner described are shown in their results in 4 example series.

Examples are shown in Examples 1, as in secondarily infected Jiicotiana tabacurn. 'Saasun' leaves, by treatment with combinations of 2,4-dioxohex -: hycrotriaine with combination partners according to the invention, potato X virus concentrations are more potent has been reduced as by the first or the respective second combination partner alone. There. Both the first Ko.mb.inationspartner (2,4-Dioxohexahydrotriazin .- DHT) and many eggs inventively used as »further Kombinatlonspartner agents, applied in optimal concentration, the concentration of the potato virus X already reduce so much alone that the virus was no longer fermentable with the serological methods used, the concentration of the combination partners was so greatly reduced to indicate the combination effect that when the first or the second combination partner was used alone, only a 25 % -20 % reduction in the virus concentration , Thus, RK 75 % ^± 20 ^ was expected to be used. Accordingly, only 1 to 5 Ό of the usual application rates were used by Combination Partner 1 (DHT) in the case of agents used as the second combina- tion partner in

- ro ¹ .-

2 2 Ö 7 5 4 5

Question, was the application rate also in many cases, but not usually lowered so much.

i ''

In results column 1 (= E 1) 'the. Tables each indicate the percentage of virus concentration found after application of the greatly reduced concentration of DKT compared to the water or solvent control. Column 2 ('= E 2) contains the corresponding data after the sole use of combination partner 2. Results column 3 (- E 3) shows in which iv.aße with combined use of the partners, the virus kon, ζ Ent. Tion tion, related to that of the respective Waaser- or -losungsrnittelkontrolle, is reduced. Result pal-. te, 4 (= E 4) relates the virus concentration found in the leaves of the plants treated with the respective preparation combination to the virus concentration found in the plants treated with DHT alone. Result column 5 (= S 5) includes the. the combined treatment, the virus concentration found in the alone with Kombinationspartner treated plants virus concentration. The results indicated show that the combinatorial agents synergistically enhance their antiviral effects. Even if the one partner or if both partners in the chosen: ·. Concentration when used alone did not cause any or only very little antiphytoviral effects were in the combination antiviral effects before z.T. to a considerable extent. If both partners are combined in optimal application rates, the viral multiplication is accordingly largely or completely suppressed. '

Similarly good synergistic effects as the ones cited in Example ¹ . Preparation combinations also resulted in secondarily infected leaves in the combinations of 2,4-dioxohexahydrotriazine with the following combination partners according to the invention:

3-Zthiazole-2-aldehyde-S-ethyl-isithiosemicarbazone, p-phenylamino-phenylglyoxylic acid nitrile (S-methyl-isothiosemicarbazone), quinoline-2-aldehyde-S-n-butyl-isothiosemicarbazone,

2287 5 Λ 5

yl / tliy.larrrino-phenylglyoxylic acid nitrile S-thyl-i.nothioniocarbazone, 6-Ni troohiriol ir.i -? - aldehyde-o-eta1-isothiosemicarbazone, quinoline-2-aldehyde-iodomethylate- thiosemicarbazone, 2-i-Viethyl- (1-thiocarbamyl-omomethylene) -1,2-dihydroisoquinoline, 1-methyl-2- (thiocarbamoylazomethylene) -1,2-dihydro-quinoline, N-im-aminoacetophenone, i-.S-diphenyl- oxazol-2-yl-hydrazone J-o-ribosylamine, o-pluorobenzaldehyde [4,5-diphenyl-oxazol-2-yl] -hydrazone, 5-amino-3-p-benzylidene-hydrazino-phenyl-4-cyano-isoxazole, 2 -Anil ino-5-methyl-. 1,3,4-thiadiazole, 2-3-benzyl-5-amino-1,3,4-thiadiazole, 2-amino-1'-n-tert-butyl-i. 3,4-thiadiazole, 1-benzocKinone monoguanyl hydrazone. ',,

? Example series 2 is shown with a selection in the same arrangement as in Example 1 row that by the invention the concentration of the preparations combinations Karto.ffel-X virus often in inoculated leaves _in: greater;. Measurements may be reduced by sole use of the 1st combination partner (DHT) or the 2nd combination partner. This is significant because, on the one hand, viral replication in the inoculated leaf is generally more difficult to influence than in secondarily infected leaves and, on the other hand, drastic restriction of virus replication in the inoculated leaf can severely limit or prevent the migration of viruses into other leaves or other parts of plants. The latter is often achieved by increasing the concentration of both combination partners, which had been reduced more or less strongly for the detection of combination effects (see above).

Similarly, good synergistic effects, such as those in Example Series 2, of prepubation rate combinations also resulted in combinations with the combination partners of this invention in inoculated sheets:

Ohinoliri-aldehyde-N-oxide-S-allyl-isothiosemicarbazone, pyridine-4-adahydrate-j 4. S-diphenyl-oxazol-P-yl-yl-hydrazone, pyridine-4-aldehyde-chloro-thiosemicarbazone-ζ-chloride Complex, 1-methyl-2- (thiocarbamoylazo-methylene) -1,2-dihy- ^v

2 L b / b A

dro-pyridine, .N-n-butylsatin-3- | 4,5-diphenyl-oxazol-2-yl-4-hydride, perrocene-aldehyde-4,5-diphenyl-oxazol-2-yl-hydrazine, 2-benzenylamino-5- (2-hydroxyphenyl) -1,3,4-thiadiazole.

In example series 3 it is shown by means of different inventive / appropriate middle combinations that also difficult inhibiting :; bare viruses, e.g. the tobacco mosaic virus, by appropriate. Medium combinations are much more inhibited than can be achieved by the individual combination partners alone. Accordingly, the range of chemotherapeutically detectable viruses can be extended by means of agent combinations according to the invention.

Example series 4 shows that combination preparations are also superior to virus-infected carbo-tofoli plants and lead to considerable treatment success. Of pregerminated potato tubers, -2 to 4 cuttings were used by standardized cuts, i. Germs, each with an equal piece of tuber tissue, removed. These were planted out according to the standards applicable to the determination of seedlings and used for small plantlets. From. The eyecups of each tuber served as one untreated control. The. Others were repeatedly treated at weekly intervals with antiviral preparations. In this way, the greatest possible identity was ensured with regard to virus stocking and gene stock of control and experimental member. 6 to 8 weeks after preparation, the plants treated with the preparations according to the invention, such as the controls, were scored for the appearance of virus symptoms. After scoring, the plantlets were cultured for a further 2 to 3 weeks. Under the chosen conditions tuber formation began during this time. About 9 weeks after the start of the experiment, the experiments had been completed. The nodules of 20 plants each of a test element were harvested separately and weighed * ...

From the values given in example series 4, it can be seen that

ZZÖ7DA D

lehjj that with suitable agent combinations according to the invention, the number of eye cuttings of the potato with virus symptoms can be reduced more than by treatment alone with one of the two combination partners. The more the number of symptom-bearing eye cuttings was reduced, the more the nodule weight was increased. The virus-related negative influences on nodule population and nodule growth could thus be reduced by treatment with an agent alone. This means that by erfxndungsgemäße combinations of preparations even in virus-infected potato plants yield-producing processes can be better stabilized v / earth than by individual preparations.

Example pure 1

Increased Inhibition of the Potato X Virus in Nicotina Tabacum Secondarily Infected Leaves Samsun ¹ (= virgin tobacco) by combinations of DHT with combination partners of the invention.

Combination partner of DHT

Concentration solution

Subst. DHT average hiol / 1 mol / 1 x) or%

e,

xx)

RK and significance

DHT / L Sub / L Kb / L Kb / DHT Kb / Sub

p-CMethoxy-benzylidene-hydrazino) -phenylglyoxylsäure-

nitrile-S-metiiyl-isothiosemicarbazone

iyridin-3-aldehyde-S-ethyliso-5x10 "thiosemicarbazone

2-hydroxy-i-naphtaldehyd-S-methyl-isothiosemicarbazone

25x10 '

Ac

38

5x10 "

5x10

10 "

-3

5x10 " ^J 25x10

3-p-decyloxy-m-methoxy-benzaldehyde 5x10 ^J 5x10 acetone S-ethylisothiosemi

phenylcarbazone

Cu complex of 1-ethylisatin-S-ethyl-isothiosemi

phenylcarbazone

Pyridine-2-aldehyde-chloro

methylate thiosemicarbazon-

^ -4

, -5

Ac

Mgl

Etb.

Ac

2x10 "

5x10

" ⁴ 82 *

54 ·

89 *

64 *

60 *

3 ⁺⁺⁺ -50 ·

O*

51 "

23

O*

Continuation of example series 1

Copper acetate complex of quinoline-2-aldehyde-S-propyl-isothiosemicarbazone p-phenylamino-phenylglyoxylic acid 1-nitrilo-semicai'baaone ~ m-diethanolaminoacetoplienone semicarbazone

m-The thanolaminoac e t ophe non-4-phenyl-semicarbazone m-diethanolaminoacetophenone-4-benzyl-semicarbazone 1-ethyl-2-thioisatin-3-semicarbazo.n

2-Morpholino-5-fp- (benzylidenehydrazino) -phenyl-1,3-4-thiadiazole

2-guanidino-4,5-di-n-propyl-hydrochloride

2,5-Dib.-hydroxybenzaldehyde - (4,5-diphenyl-oxazol-2-yl-hydrazone)

5x10 '

5x10

5x10

5x10

5x10

10 '

5x10 '

-5

-4

Ac

Ac

56 '

33

60 *

6O

63 '

25x10 "^ Ac 29 ⁺⁺⁺ 43 ⁺ 25x10 "" ^ Ac 100 · 95 ' 25 * 10-5 ad 19 ⁺⁺⁺ 31 ⁺ 25χ1Ο "" ⁵ Ac 23 ⁺⁺⁺ 36 ⁺ 5x10 ~ ⁴ Eth 49 * 99 · ' 25x1O ~ ⁵ H ₂ O 47 ⁺ 33+

132 *

27

7 ⁺⁺⁺ 26 '

69 * 69 '73'

9 ⁺⁺⁺ 50 * 30 ⁺⁺

70 * 44

45 · 65 '

37 ⁺ 17

Continuation of example series 1

m-guanidino-ace.topiienone- 5x1O ~ ° 25x10 "- ^ Ac 16 OO ⁺ OO *

(4,5-diphenyl-oxazol-2-yl-r _;

hydrazone) hydrochloride

2.4-dihydroxy acetophenone 5x1O ~ ³ 25x10 "" ^ _ Ac 19 ⁺⁺⁺ 78 ⁺⁺⁺ 77 * 14 * 18 "

(4.5-diphenyl-oxazol-2-yl

hydrazone)

5-Fneny 1-4-oxo-2-amino- 10 " ² 25x10""^ H ₉ O 21 ^-rn " ^r 49 " ¹ " 14 " ^t " ^t " ^{t '64} * 28 *

2 4,5-dihydrooxazole

4-Me thoxyacetophenone- (4.5-5x10 "" ³ 5x10 ""' ⁴ ' Ac 60 * 100 * 43 ⁴ 71 * 43 ⁺

diphenyl-oxazol-2-yl-. ·,

hydrazone)

4 · 5-diphenyl-1-oxazol-2-y-1

imino-glyoxylic acid 2-anilino-5-adamantyl-1,3,4-thiadiazole 2-anilino-5-benzyl-1,3,4-thiadiazole

2-Allylamino-5-p-nitrophenyl- 0.1%

1,3,4-thiadiazole 2-y-naphthyl-1-amino-1,3,4-thiadiazole

_.- 3 _ / i 5x10 ^J 5x10 Ac 60 * 136 * 32 ⁺⁺ 54 * 24 ⁺⁺ N 0.1% 25x10 " ⁵ Ac 33 ++ _{32 ++} 11 ⁺⁺⁺ 3 · 35 * a • v 0.1% 25x10 "^ Ac ⁵⁰⁺ 74 * 43 ++ 80 * 58 · U 4? 0.1% 25x10 ~ 5 0.1% 25x10 " ⁵ Ac Ac 33 ⁺⁺ 67 * 89 ' ₁₃ +++ 39 · 24 * 19 ⁺ 12

Port setting of example series

2- (4 -ChloraniIino ^f) -5 - adamantyl-1.3 · 4-thiadiazole 1,4-Napht-oc hinon monoguanyl hydrazone Tiioron-guanylhydrazone

0.1 % 25x10 "

5x10

" ³ Ac Ac Ac

29 100 ·

74 · 26 ⁺⁺⁺ 52 * 35 *

43 8 29 * 20 '

76 * 26 ⁺⁺ 26 '

Ac Eth.

Mgl

Water acetone, 5 % in H ₂ O ethanol, 5% in H ₂ O methyl glycol, 2 % in H ₂ O.

xx)

DHT based on solvent control

Substance (Sp. D "" "" "

Combination " " " " "

Combination " . ." DHO?

Combination "

"Substance (3p.1 or 6)

Example series 2

Increased inhibition of potato X virus in inoculant t eη (primary infected) leaves of Nicotiana tabacum ^f Samsun ^s (= virgin tobacco) by combining DHi? with combination partners according to the invention. Abbreviations as in example series 1.

Combination partner of the DHQ? concentration

Subst. Mol / 1

DHT mol / 1

Solvent x>

xx)

RK and significance

or.% 3 4 DHT / L Sub / L Kb / L Kb / DHT Kb / Sub 1 2 , 5 6 7 8th 9

Cu complex of 1-EthyIi- 5x10 "

satin-S-ethyl-isothiosemicarbazone

Copper acetate complex of 5x10 quinoline-2-aldehyde-S-n-butylisothiosemicärbazon

Pyridine-2-aldehyde-chloromethylate-thiosemicarbazone-ZnCl2 ~ complex

Isoquinoline-1-aldehyde-chloromethylate-thiosemicarbazone m-diethanolamino-acetophenone semicarbazone

i-ethyl-thioisatin-semicarbazone

x) xx): cf. Example 1

-3

25x10

25x10 '

, -5

5x10

, -4

5x10

5x10

5x10 "

, -3

82 * 72 · 73 "

75 *

106 · ₅₇ + ₊

133 * 63- '·· 76 * 47'

142 * 56

30 ⁺⁺⁺ 41 ⁺⁺ 42 *

96-68 ⁺ 90 "71 *

55 ⁺⁺ 37 ⁺⁺⁺ 35 ⁺⁺⁺ 67 '

98 * 36

+++ 63

36

Continuation of sample series 2

.6 7 8

2-methylmercapto-5-fp- (2-5x10 "^ 25x10" ^ Eth 87 * 105 ° 43 ⁺⁺⁺ 49 ⁺⁺

nydroxy-benzylidene-hydrazono) -

phenyl] -1.3 · 4-thiadiazol

p- (benzylidene-hydrazono) -phenyl-glyoxylic-nitrile- (morpho-

lino) -thiocarbonyl-hydrazone D-glucose (4,5-diphenyloxazole-atryl-hydrazone) D-arabinose (4,5-diphenyloxazol-2-yl-hydrazone)

2 - (^ - phenylethylaminomethyl) - 5x10 '

4,5-diphenyl-oxazole 2-anilino-5-adamantyl-1,3 · 4-thiadiazole 2-anilino-5- (4 · -nitropheny1) -1,3,4-thiadiazole 2-anilino-5-benzyl-1,3,3-thiadiazole

2-allylamino-5-p-nitrophenyl-1-r3 4-tert-hiadiazole

-5X1O "" - ³ 5x10 "^ Ac 92 " 96 · 43 +++ 47+ ⁴⁵⁺ • 5 * 10-3 ₅ x10- Eth 82 ' 88 * 45 +++ 42 ⁺⁺⁺ I 5x1O ~ ³ 5x10 "^" Eth 82 * 63 ⁺⁺ 44 +++ 54 ⁺⁺ 71 * ro 5x1O ~ ³ Eth 82 * 55 ⁺⁺ _{55 ++} 67 * 100 * OO 0.1 % 25 * 10-5 Ac W 68 * ⁴⁸⁺ 68 ⁺ 71 * cn 0.1% 25x10 "^ Ac 71 * 78 * 63 * 88 * 80 * : &> 0.1% 25x10 "^ Ac 129 * 95 ' 6O ⁺ 46 ⁺ 63 ^# 0.1 % 25x1O "" ⁵ Ac 121 * 147 ' 49 ⁺ 40 ++ 33 ⁺

he

Continuation of sample series 2

2- (4 x -Chloranilino) -5-aäa-

mantyl-1.3.4-tiiiadiazol

1 ^ -. Benzoquinone-bis-guanyl

hydrazone

1.4-naphth ochinon mono-

guanyl hydrazone

Tiloron-guanylhydrazone

" ³

5x1O " ³ 25x10" ⁵ Ac

5x10 "- * 25x10" ^ Ac

f.2 <r 1Ό6 *

89 · 42 ⁺⁺⁺ 32 ⁺⁺⁺ 88V

36

90 *

118 *

75 '

If you like it, you have 3 * '

Increased inhibition of the tobacco mosaic virus by combinations of DHT according to the invention with suitable preparations, demonstrated by the reduction of local lesion formation on Nicotiana glutinosa. Abbreviations as in example series 1.

Combination solvent of the DH ¹ I concentration solution

Subst. DHT middle mol / 1 mol / 1 χ)

RK and significance

ϋί.

e,

DHT / L Sub / L Kb / L Kb / DHT Kb / Sub

1,3-diphenylpyrazoldione-S-5x10 ^ ethyl-isothiosemicarbazone quinoline-4-aldehyde-chloro-5x10 "" ^ methylate-thiosemicarbazone

, 2-Morpb.olino-5- [p- (pyridine-5x10 '' - ^ (2) -aldehyde-hydrazono) -phenyl] -1,3,4-thiadiazole

2-guanidino-4,5-di-n- '5

/ propyl oxazole hydrochloride

x) xx): cf. example series

3 xi Ö

, -2

15x10

-3

15x10

15x10

Ac

H ₂ O

Ac *

H ₂ O

120 *

70 * 40 ⁺⁺⁺ 5O ⁺ 57 '71 * 60 * 6? ⁺ 109 '119 * 87 * 68 ⁺ , 74'

83 ⁺ 60 * 67 ⁺ 120 *

Example series 4s

Increased reduction in the number of cuttings of the potato with virus symptoms and a marked increase in the RnoTlcb.engewbb by means of inventive combinations of preparations with DHT (0.1 .-%) compared to the treatment with individual preparations. The eye cuttings obtained from potato sources with a high proportion of natural viral infections were superinfected with potato X virus. A = variety Astilla, S = variety Salut.

combination partners

Virus stock%

DHT Komb.p combination U = u = u = DHT s combination.p 100% 100% 100% 100% = 100%

nodule weight

DHT Comb.p combination u = u = U = DHT = Comb.p 100% 100% 100% 100% = 100%

m-guanidino-aceto-A-phenone {J4,5-diphenyloxazolyl (2) -hydrazone]

hydrochloride, 0.1% S

2-anilino-5-adamantyl-1, 1,3,4-thiadiazole

0.1% S

64 ⁺ 89 * 49 ⁺⁺ 77 * 56 ⁺ 117 ⁺ 104 * 153 ⁺ 68 ⁺ 92 · 52 ⁺ 76 ' 57 ⁺ 109 * 102 * 123 * 71 " 95 * 54 ⁺⁺ 76 · 1.11 · 102 * 15O ⁺

69+ 94. 53 ++ 34-

ΙΟ? ' 101 * 119 *

* 118 *

Claims (2)

invention claim 1. An agent for the chemotherapy of crops by using conventional excipients and excipients based on 2,4-dioxohexahydro-1,3,5-triazine, characterized in that they are substituted as synergists thiadiazoles of the general formula I, oxazoles of contain general formula II and / or hydrazones of general formula III, v / obei> in the general formula ! I R ₁ -C CR ₂ / S. R ₁ and R ₂ at the same time or in any variation an amino group which is substituted or unsubstituted by aliphatic, substituted aliphatic, aromatic, substituted aromatic, cycloaliphatic and unsaturated aliphatic radicals, further an alkyl or substituted alkyl group, phenyl and substituted phenyl Groups, heterocyclic groups and the adamantyl group, in the general formula II R = alkyl, hydroxyalkyl or phenyl groups, R -] = alkyl, phenyl, hydroxyl, carboxyl, R ₂ = NH ₂ , guanyl, Alkylthiocarbamoylhydrazino-, N-substituted aminomethyl groups, further hydrazone of glyoxylic acid, acetone Aldoses, N-alkylisatines, halogenated benzaldehydes, pyridinaldehydes, ferrocene aldehydes, aminoacetophenone, N-substituted acetophenones, polyhydroxyacetophenones and methoxyacetophenone, as well as salts and adducts of these substances. 228 7 54 5 and in the general formula III. R ₁ ; ^ R3 G = N-N = C R2 R4 R _{1 and} .'R ₂ alone or in any variation H, SH, CN- ', CH3 groups _v furthermore pyridyl, pyridyl-N-oxide, N-alkyl-.pyridinium, quinolyl, quinolyl-N oxide, N-alkylquinolinium, quinoxalyl, isoquinolinyl, isoquinolyl, N-oxide, N-alkylisquinoline, benzthiazolyl, naphthyl, phenyl, p or m (N-substituted aminophenyl) -, pN -Alkylnitrosaminophenyl-, styryl and alkyl, nitro, halogen, hydroxy or alkoxysubs.tituierte compounds of the type mentioned, as well as Alkyl alkyl = 0 (Y = 0 or -NW = C (WH ₂ ) ₂ ). (X = and R3 and / or R4, is H, OH, SH, S-alkyl, S-alkenyl, S-aralkyl -, - NH _2, NH-alkyl, NH-aralkyl, alkoxy, S-AIR * kyl - ,. Morpholino-, pyridyl, quinolyl, chihoxalyl groups mean, whereby also complexes with heavy metal ions such as Cu · and Zn ions ¹ , optionally together with other anions and additional ligands, are used. VT I 2. Means according to item 1, characterized in that the preparations used in addition to the Wirkatoffkombinatiönen invention also surfactants, adhesives and other formulants and optionally excipients to form granules.