DE1283593C2 - Nematode repellants with a content of nickel compounds - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Int. Cl .:

A Ol η-11/00

GERMAN

PATENT OFFICE

PATENT LETTERING

German class: 451-11 / 00

Number:

File number:

Registration date:

P 12 83 593.7-41 (J 28210)

May 25, 1965

November 21, 1968

August 21, 1969

Display day:

Issue date:

The patent specification corresponds to the patent specification

Nematodes can cause extensive damage to many plant species. Some nematodes can attack the roots of the plants, while others attack the stems, leaves or buds of the plants can attack, even tubers and seeds can be attacked. The result of the attack through Nematodes is that the plants, seeds or tubers are at least severely weakened, therefore very become sensitive to disease and can even be destroyed,

Many attempts have been made to destroy nematodes in crop areas or controlled by applying agents known as nematocides to the crop areas. One known class of nematocids that are commercially available are the halogenated Hydrocarbons such as l, 2-dibromo-3-chloropropane and mixtures of 1,2-dichloropropene and 1,2-dichloropropane.

From the German Auslegeschrift 1111 872 is the use of the nickel salt of phenyldithiocarbamic acid known for controlling nematodes.

In order to be satisfactory, the means used may, apart from good nematocider Efficacy, not have excessive phytotoxic effects and must not be harmful on the soil of the crop area or on the crops on the crop area in which they are applied, work.

According to the invention, nematodes in a crop area are controlled or destroyed by Apply to this crop area of one or more nickel compounds from the group Nickel sulfate, nickel borate, nickel cyanide, nickel phosphate, nickel nitrate or nickel dialkyl dithiocarbamate having 4 or more carbon atoms in the alkyl group. These dithiocarbamate compounds have the formula:

CC 00

R ¹

R ²

N-

Ni

wherein R ¹ and R ^{2 are} both alkyl groups.

Among the dithiocarbamate compounds which are preferred for use in the invention, may be mentioned nickel di-n-hexyldithiocarbamate, nickel di-n-butyldithiocarbamate, nickel di-2-ethylhexyldithiocarbamate. Of these, nematode control agents containing nickel compounds are used

Patented for:

International Nickel Ltd., London

Representative:

Dipl.-Chem. Dr. rer. nat. W. J. Berg

and Dipl.-Ing. Otto F. Stapf, patent attorneys,

8000 Munich

Named as inventor:

Carroll Alonzo Hochwalt, Upper Montclair;
Patricia Jean Sazegar, New York, NY
(V. St. A.)

Claimed priority:
V. St. v. America May 25, 1964
(370 104, 370 124)

the di-n-hexyl and di-n-butyl compounds are particularly preferred. When the nickel compound used Which is sulfate, boride, cyanide, phosphate, or nitrate, it is often because of the cost of the Compounds desirable to use them in the form of a hydrated salt. So can it Sulphate as hexahydrate, cyanide as tetrahydrate, phosphate as monohydrate and nitrate as Hexahydrate can be used. Mixtures of the nickel compounds of the invention used can can be applied if desired.

The nickel compounds used in the invention destroy nematodes in the soil of the crop area, and the method of application should be such that at least most of the applied nickel compound is introduced into the soil. The term "soil" is so closed understand that it includes growth media used for the purpose of nutrition and maintenance of plant growth be used. The compounds exhibit nematocidal activity in amounts as low as 0.05 parts per million soil, measured as the amount of nickel. Preferably, the opposite of the Soil applied nickel concentration of 0.1 to 20 parts per million, although more preferred the lower limit of concentration 1 part per

909 634/236

Million, or sometimes 5 parts per million. To relate this amount to the actual weight of the compound to be applied, it can be assumed that a volume of soil of area 4050 m ' ² and 15.24 cm depth, which is an average cultivable depth, is approximately 907 000 kg, so that to create a concentration of 1 part nickel per million 0.907 kg nickel per 4050 m ^{2 of} soil will have to be used.

The application of the nickel compounds can be carried out in any conventional manner. The compounds can be used alone or they can be used in the presence of either solid inert carrier of the conventionally used in nematocidally active preparations Type or with a liquid inert carrier. Typical solid inert Carriers are silica and clay, for example kaolin dust. You can in the present a carrier which is not inert, can be used. So they can be applied together with a fertilizer, which is the name of the various types of soil fertilization (top dressing), which can be applied to the ground are included. Nickel compounds, which are soluble in water can be applied as water solutions, these Compounds primarily sulfate, borate, cyanide, phosphate and nitrate and the hydrates of these are. Where the solubility in water is too low to allow ready-made formation of solutions, nematocidally active preparations can be in the form of a wettable powder (for wet processes) applied to the soil, such preparations containing the nickel compound with an inert solid carrier and wetting agent. This type of preparation is special Value for the dithiocarbamate compounds. Preparation process for nematocidally active preparations, which contain an inert solid carrier with or without a wetting agent are well known.

The nickel compounds according to the invention can be used in a simple manner of the compounds or preparations containing the same against the surface of the Consist in the soil of the plant area or in the injection of the compounds or preparations, which contain them in the ground. Such solutions can be introduced into the soil using a soil probe or a digger. However, it is mostly useful, in the simplest of terms the compounds or preparations on the soil surface before plowing or otherwise Cultivating the crop area by spraying or dusting.

The nickel compounds used in the invention are potent nematocides, but it is of course, that they do not all have the same effectiveness against any particular nematode, some being more effective than others.

Some examples of the invention will now be given.

example 1

The effectiveness of various compounds which can be used in the invention was determined against one species of Panagrellus, a potent Saprozoic nematode, all in one aqueous medium. The nematodes were raised in a culture medium, using the Baermann funnel techniques, to ensure the freedom from nutrient contamination and to ensure age uniformity, separated and locked Test tubes placed containing 10 milliliters of the chemical dosage under test contained. Between 50 and 75 nematodes were placed in each tube. Every investigation went in duplicate with test tests carried out in the same way in tap water became. In the absence of the nematocid, the nematodes at least lived under the test conditions 7 days without adding food. The nematodes became microscopic for a period of time observed from 9 days to the rate of killing and the end point of killing to hold on. Panagrellus are characterized by constant and effective movement, so they allow easy identification of live and dead nematodes. In addition, multiply the species rapidly undergoes parthenogenesis, and the technique of investigation permits observation the effect of the nematocides on the reproductive behavior and also on the animals of various kinds Ages.

The investigations were carried out using different nickel compounds at different Concentrations carried out pie examinations, which are carried out with a series of examinations are listed in Table I below, while the results of others are more similar Series of examinations, which are carried out with a different time, in Table II are held.

Table I.

dosage I day 2 days Percent/ \ btö (ung 7 days y days Chemical agent Share Niekel 35 KX) KX) 100 per million 0 45 3 days 5 days 80 95 Nickel sulfate hexahydrate 10 0 10 100 100 60 90 1 100 100 50 55 99 100 0.1 0 75 15th 50 75 85 Nickel-di-n-propyldithio- 1,000 0 10 100 100 17th 80 carbamate (comparison) 100 0 5 80 90 15th 75 10 0 0 10 17th 15th 75 1 5 10 0.1 0 10

continuation

Chemical agent dosage
Parts of nickel ITag 2 days Percent kill 5 days 7 days 9 days per million 99 100 3 days 100 95 99 Nickel-di-n-butyldithio- 1,000 7th 100 100 100 75 95 carbamate 100 0 100 100 100 80 95 10 0 92 100 90 60 87 1 0 70 90 80 35 70 0.1 90 100 70 100 99 100 Nickel-di-n-hexyldithio- 1,000 10 100 100 100 92 99 carbamate 100 0 97 100 85 85 85 10 0 90 100 92 90 92 1 0 70 97 97 85 85 0.1 10 100 85 100 100 100 Nickel-di-2-ethylhexyl- 1,000 0 92 100 90 60 92 dithiocarbamate 100 0 47 97 25th 20th 90 10 0 20th 50 20th 20th 75 1 0 7th 25th 7th 7th 70 0.1 100 100 10 100 100 100 Nickel-phenyl-dithio- 1,000 100 90 100 100 100 100 carbamate (German 100 0 10 100 15th 25th 75 Interpretation document 1111 872) 10 0 0 15th 0 10 50 1 0 0 0 0 10 45 0.1 0 0 0 5 10 15th Untreated control - 5

Table Il

Chemical agent dosage
Parts nickel per million 2 days Percent kill
4 days 7 days Nickel borate Ni (BO ₂ ) * 50
5 70
40 100
50 100
100 ■ Nickel nitrate hexahydrate 50
5 99
45 100
85 100
92 Nickel cyanide tetrahydrate 50
5 32
10 100
80 100
95 Nickel phosphate monohydrate 50
5 100
82 100
99 100
100 Nickel sulfate hexahydrate 50
5 100
82 100
99 100
100 Untreated control - 2 10 20th

The results obtained with nickel di-n-butyldithiocarbamate and nickel di-n-hexyldithiocarbamate and with nickel sulfate (especially the 90 "/ () mortality in the 9-day study at a concentration of only 0.1 part nickel per million) show that the compounds are special have good effectiveness and are superior to the compound known from German Auslegeschrift 1111 872 are.

Example 2

A nematocidally active formulation was made as a wettable powder by mixing nickel di-n-hexyldithiocarbamate with a formulation consisting of 92 "/» synthetic silica pigment, about 4% sodium lignosulfate anionic surfactant and about 4 "/» nonionic surfactant a polyoxyethylene condensate with polyoxypropyl glycol. The resulting 50 % wettable powder production was further expanded to a 10% dust preparation with Continental clay.

Example 3

A test soil was prepared by mixing 1 part by weight of soil heavily infested with tuberous nematodes (Meliodogyna hapla) embedded in tomato root tissue with 8 parts of ordinary pot soil. The resulting mixture of infested soil was then allowed to recover for 2 weeks to allow the nematode larvae to hatch _:

possible and the emergence of the entire nematodes from the initial tomato root tissue, which used for culture production. During the recovery process was

the soil is thoroughly turned one day on the next, in order to obtain a highly uniform and homogeneous mixture of infested soil.

1 kg samples of the test soil were tumbled mixed with the nematocidally active formulation of Example 2 in amounts corresponding to about 17, 34 and 68 kg of the nickel compound per 4050 m ^{2, i.e.} H. in amounts of 2.92, 5.85 and 11.7 parts per million nickel. The soil mixture was kept in a closed container for 48 hours. The treated soil was then placed in dishes and stored for an additional 5 days. At the end of this period, half of the trays were planted with tomato seedlings and the other half of the trays were planted with sugar beet seeds.

Similar 1 kg soil samples were treated in a similar manner with nickel sulfate hexahydrate, again in amounts corresponding to about 17, 34 and 68 kg of nickel compound per 4050 m ² , ie in amounts of approximately 4.2, 8.4 and 16.8 parts nickel per million.

Control pots of infested soil, which did not contain any nickel compound , and additional test pots, which were made with equivalent percentages of commercially available nematocides (1,2-di- bromo-3-chloropropane and a mixture of 1,3-dichloropropane and 1,2-dichloropropene) were also prepared in a similar manner.

The plants were observed regularly for a period of 4 to 6 weeks. At the end of this time it could be seen that the plants growing in untreated soil were very badly damaged as a result of the nematode infestation. Examination of the plants showed, when they were removed from the pots , that practically no root system was present. On the other hand , the plants which grew in a soil treated with the nickel compounds according to the invention showed vigorous growth with little incidence of phytotoxicity, which can be ascribed to the compound. The examination of the roots of the plants for nematode infestation further showed that the plants were better protected than the plants which grew in a soil which had been treated with one of the commercially available nematocids.

Example 4

A field test was carried out in a slightly acidic, sandy, clay mud bed alluvial soil that was known to be severely infested with root-nodal nematodes from year to year, including nickel di-n-butyldithiocarbamate, nickel sulfate hexahydrate, nickel nitrate hexahydrate and the two commercially available nematocides mentioned in Example 3 were used. The nickel dithiocarbamate was prepared as a 25% wettable powder in the manner described in Example 2 and the commercially available nematocides were used as recommended by the preparation. Two days before the soil treatment, approximately 38 mm of water was applied by surface irrigation to bring the soil water content to an appropriate level. The materials were suspended in water and continuously introduced into the ground to a depth of approximately 15 cm using a soil probe. The packing wheel effectively covered the ground immediately behind the probe injector and gently pressed it into place immediately after the injection. One week after the soil treatment, the soil was planted with cucumbers, turnips and beets. The soil temperature was approximately 21 ^° C. at the time of treatment and also at the time of planting with the specified crops. The area had to be watered during the growing season because the growing season in question was dry.

The emergence of the seedlings and the growth of the emerged plants were observed over a period of months. It was observed that a severe infestation of root-nodal nematodes developed in the untreated soil during the growth period. To test the extent of the nematode infestation, 30 to 40 fully developed individual plants were carefully lifted from the ground. The adherent soil was carefully removed and the identified root system was then carefully examined for the extent and degree of nematode gall or damage. The infestation of the individual plants was assessed according to a system from 0 to 5, with 0 indicating that there were no root galls or damage, and 5 indicating very severe nematode infestation. An overall assessment or evaluation of all plants tested was taken together, this in turn divided by the maximum total infection and based on 100 as the maximum total infection evaluation to maintain a "root-node index". The results obtained using the various concentrations are given in Table III below.

Table III

plant chemical dose
kg per 4050 m ² Infested plants
% Root node index White beets Nickel di-n-butyldithiocarbamate 68
34 7th
10 1.4
2 17th 72 40 Nickel sulfate hexahydrate 68
34
17th 25th
16
10 5
3.3
2 untreated area - 85 42

continuation

10

plant chemical dose Infested plants Root node index kg per 4050 m ² % White beets Nickel nitrate hexahydrate 68 20th 9.3 34 18th 2.2 17th 6.3 1.2 1,2-dibromo-3-chloropropane 17th 73 40 untreated area - 53 44.8 Beetroot Nickel di-n-butyldithiocarbamate 68 20th 13th 34 41 16.5 17th 15th 12.5 Nickel sulfate hexahydrate 68 15th 10 34 8th 5 17th 15th 12.2 untreated area - 83 46 Nickel nitrate hexahydrate 68 43 21.2 34 30th 133 17th 40 17.6 1,2-dibromo-3-chloropropane 34 27 23.2 untreated area - 78 49 Cucumber Nickel di-n-butyldithiocarbamate ' 68 0 0 34 27 13.5 17th 0 0 Nickel sulfate hexahydrate 68 6th 6.7 34 0 0 17th 13th 8th untreated area - 100 77.5 Nickel nitrate hexahydrate 68 0 0 34 0 0 17th 0 0 untreated area - 78 33 1,2-dibromo-3-chloropropane 68 67 16 34 67 17.5 17th 53 24 1,3-dichloropropane 68 27 5.3 and 1,2-dichloropropane 34 46 10 17th 53 10.7 untreated area - 60 18.7 okra Nickel sulfate hexahydrate 68 75 42 34 78 67 17th 92 43 Nickel nitrate hexahydrate 68 94 37 34 88 48 17th 71 46 untreated area 100 68 1,2-dibromo-3-chloropropane 68 78 54 34 67 50 17th 91 59 untreated area - 100 69

The application of 17, 34 and 68 kg of nickel di-n-butyldithiocarbamate per 4050 cm- corresponds adding about 2.35, 4.7 and 9.4 parts per million nickel while using the same weights Specify nitrate concentrations of approximately 3.8, 7.6 and 15.2 parts nickel per million. It consisted no adverse effect on the germination or emergence of the cucumber seedlings as a result of the

Treatment with any of the nickel compounds. It was also found that in the case of the cucumber fruit, which was harvested daily for the market after maturity shows a noticeable improvement Yield was obtained compared to the plants grown in the same manner in the same field were obtained in the previous years without soil treatment against nematodes. This ver

909 634/236

The improvement in the yield was the control of the root nodal nematodes created by the invention attributable to.

The okra plant is very sensitive to nematode infestation. The plant was later than that other index plants described above are planted in the growing season, at a time when the soil was warmer. In addition, there was a period of 3 to 4 months between planting time and observing the plants for root node damage at what time the plants are deep were rooted. The particular soil under consideration developed a type of compact solid ground at a depth of about 20 cm. The roots of the plants penetrate the hard subsoil, but this effectively stops the downward migration of the nematocid. It it was observed that the strongest nematode infestation found in okra was approximately at and below the height of the solid subsurface. In this context, the attack on plants was at 100% untreated test areas, and very high root node indices, were found in these plots detected. On the other hand, the root node indices for study plots were those with nickel compounds were treated, very much lower (with only one exception) than the untreated Test parcels. The okra plants, which in the soil protected by the nickel compounds grew, thrived, and the fruit yield was significantly higher than in the unprotected test plots. The nickel compounds showed superior protection against nematodes in comparison to the commercially available nematocids. The root crops of beetroot and white beet were not harvested until November. The yield of marketable vegetables and goods was very good in the nickel-protected plots, and the vegetables were well developed and of high quality Quality. It was observed that the plants which grew in plots, those with nickel compounds were protected, had a very good seed stand, although okra seedling damage occurred in untreated test parcels. These observations showed that there was no tendency regarding phytotoxicity, on the part of the nickel compounds in those used by the program Quantities occurred.

Example 5

This example illustrates that while the compound used in the invention · ■ is very are effective nematocids, a very closely related compound that might be expected to be it is satisfactory, namely nickel chloride,

ίο not satisfied.

Nickel chloride hexahydrate was tested under the conditions given in Example 1 and it was found that contradicting results were obtained and that in one case 200 parts per million of nickel introduced as NiCl ₂ · 6H ₂ O was required to to achieve a 98% kill of Panagrellus after 7 days. It was also found that under the conditions given above in Example 1, nickel chloride hexahydrate was much less effective than a commercially available halogenated hydrocarbon nematocide and that a further concentration corresponding to 34 kg per 4050 m ^{2 was} required in order to reduce the To create the root knot index in tomatoes, and that a concentration corresponding to 68 kg per 4050 m ^{2 was} necessary in order to create a reduction in the root knot index in beets, compared to untreated test examinations.

Claims (2)

Patent claims: 1. Nematode control agent with a content of nickel compounds, characterized by a content of at least a compound from the group consisting of nickel sulfate, nickel borate, nickel cyanide, nickel phosphate, Nickel nitrate or nickel dialkyl dithiocarbamate with 4 or more carbon atoms in the Alkyl group. 2. Agent according to claim 1, characterized in that the alkyl groups of the dithiocarbamate are n-hexyl, η-butyl or 2-ethylhexyl groups. Considered publications:
German interpretative document no., 1 Ul 872. IM UUW * 11. M · BundMdriHkcrei lertla