FR2485010A1 - COMPLEX SALTS OF LACTAM OR THIOLACTAM AND HEAVY METAL HALIDE OR HALIDE, PROCESS FOR THE PREPARATION THEREOF AND USE THEREOF - Google Patents

Abstract

THE INVENTION CONCERNS NEW SUBSTANCES, IN PARTICULAR COMPLEX SALTS OF LACTAMES OR THIOLACTAMS AND HALOGENIDES OR NITRATES OF HEAVY METALS, A PROCESS FOR THEIR PREPARATION AND THEIR USE. IN ACCORDANCE WITH THE INVENTION, THE COMPLEX SALTS OF MILK OR THIOLACTAMS AND HALOGENIDES OR NITRATES OF HEAVY METALS COMPLY WITH THE FOLLOWING GENERAL FORMULA: (CF DRAWN IN BOPI) ME CU, ZN, MN, HG, NI; Y O, S; X CL, BR, NO; M 1.2; N 3.5; P 2.4; K 0.1; A 1,2,3,4; R H, -CH-CCL, CH, CH THE COMPOUNDS IN QUESTION HAVE HIGH FUNGICIDE ACTIVITY AND ARE APPLICABLE IN AGRICULTURE AND INDUSTRY.

Description

The present invention relates to novel substances

  especially the complex salts of lactams or thio-

  lactams and halides or nitrates of heavy metals,

  a process for their preparation and their application.

  It is well known that metalliferous complexes

  have an important place in the global assortment of

  chemical means of plant protection. For example, for example

  ple, one of the most important groups of fungal-

  are various compounds of copper, which they mamesen associates-

  with other active ingredients are widely used

  for the fight against plant diseases.

  However, the LD50 for CuC12.2H20 is 43 mg / kg in mice, and the LD50 for copper chloroxide is

of 72-100 mg / kg.

  Compounds of the following general formula are known: = SnCl 4 (I)

  (Japanese Patent Application No. 7584589, 1975).

  However, data on pesticide properties

of these compounds are absent.

  It was therefore proposed to broaden the range of fungicides

  antiseptics and disinfectants of the seeds, possessing

  lower toxicity for warm-blooded animals.

  The solution is to propose new ones

  compounds, especially complex salts of lactams or thio-

  lactams and halides or nitrates of heavy metals, in accordance with the invention, with the following general formula: ## STR2 ##

N - R

j

X. KH20

  (II) Me Me = CuII, Zn, Mn, HgII, NiII; Y = O, S; X = Cl, Br, NO3; m = 1.2; n = 3.5; p = 2.4; K = 0.1; a = 1,2,3,4; R = H, -CH-CCl3, CH3, C6H5I

OH

  As the most active compounds, it is recommended

  complex salts of lactams and halides or nitro-

  heavy metals, corresponding to the following general formula:

boasts:

C =

  ## STR2 ## wherein R 1 is CH 2 OH, Ni 2 x = Cl, Br, NO 3 R = HP 2 CH 2 Cl 3, n = 3.5, K = O, 1, a = 1.2; p = 2

  Typical compounds, corresponding to the formulas

  mentioned are: 1. mercury-N- (1-hydroxy-2,2,2-trichloroethyl) -pyrrolidone chloride; 2. mercury-N- (1-hydroxy-2,2,2-trichloroethyl) -caprolactam chloride; 3. di-pyrrolidone-copper dibromide 4. tricaprolactam-copper (II) dichloride monohydrate; 5. tetrapyrrolidone-di-copper (II) tetrachloride; 6. dicaprolactam-copper (II) dichloride; 7. di-pyrrolidone zinc dichloride; 8. dicaprolactamozinc dichloride; 9. mono-N-methyl-pyrrolidone zinc dichloride; Di-N-methyl-pyrrolidone-zinc dichloride; 11. mono-N- (1-hydroxy-2,2,2-trichloroethyl) pyrrolidone-copper (II) dichloride;

  12.d- / N- (1-hydroxy-2,2,2-trichloroethyl) pyridine diol

  rolidono / -zinc; 13. Di (thio-pyrrolidone) -civil (II) dichloride; 14. di (thiopyrrolidone) zinc dichloride; Monocaprolactam-copper (II) monohydrate monohydrate dichloride; 16. di (N-phenylpyrrolidone) copper (II) dichloride; 17. dipyrrolidone nickel (II) dinitrate monohydrate;

  18. dinitrate monohydrate of dicaprolactamickel (II).

  The compounds of the general formula cited are essentially

  basically crystalline substances at

  precise, soluble in polar solvents.

  Mercury salts, for example, are white crystalline substances, cupric chloride salts-green crystalline substances, bromide salts

  cupric-crystalline substances of brown color.

  The proposed compounds have the essential properties

  Gicides and disinfectants of the seeds.

  The invention also relates to a preparation process

  complex salts of lactams or thiolactams and halogens

  or heavy metal nitrates of the general formula

  mentioned above, according to which, a lake is

  tame or thiolactam of general formula: C y (C225

N R

R = H, -CH- CCl3, CH3, C6H5

  OH Y = 0, S; n = 3.5 and a halide or nitrate of a heavy metal of general formula: Me x2. K H20, Me = CuII, Zn, Mn, HgII, NiI x = Cl, Br, NO3; K = 0; 2; 6 in an organic solvent, at a temperature of 20 to 80 C,

  with subsequent isolation of the product concerned.

  The invention furthermore aims at providing a fungicidal agent containing

  as the active substance, complex salts of lac-

  or thiolactams and halides or nitrates of

  heavy metals of the general formula indicated above, on the basis of

  0.01-99.5% by weight in combination with an excipient. It is advantageous to use the fungicides containing

  as the active substance the mercury-N- (1-

  hydroxy-2,2,2-trichloroethyl) pyrrolidone, mercury-chloro

  N- (1-hydroxy-2,2,2-trichloroethyl) caprolactam, the

  dipyrrolidone-copper (II) dibromide, monohydric dichloride

  tricaprolactam-copper hydrate (II).

  The proposed agents exhibit high activity

  fungicide and are antiseptics and disinfectants ef-

seeds.

  A very important property of the agents in question, which allows their use in agriculture and industry,

  is their high fungicidal activity.

  The compounds which are the subject of the invention possess a toxic

  Quite low for warm-blooded animals. Thus, the LD50 for the mercuric complexes, established in the mouse,

  is 380 mg / kg, and for the cupric compounds of 1000-

1200 mg / kg.

  The process for preparing the compounds proposed is

  preferably implemented in the following manner.

  To a corresponding lactam or thiolactam, in absolute ethanol or acetone, at room temperature or at the boiling point of the solvent, with stirring, an alcoholic or acetonic solution is respectively added.

  halide or nitrate of a heavy metal. It acts

  at room temperature or at room temperature.

  solvent for 30 minutes or 1 hour and allowed to stand for one day at room temperature. The corresponding complex is precipitated and separated by filtration, or separated by evaporation of the solvent. The precipitate

  is usually washed either with a cold solvent or with

ther sulfuric.

  For all synthesized compounds, the

  infrared spectra. The most preferred adsorption bands

  characteristics are: NH: 3290 cm 1, C: 1640 cm -1.

  For compounds containing sulfur V N-C = S: -1

1550 cm.

  For tricaprolactam-copper (II) compounds, the

  dichloride monohydrate and dipyrrolidone-dichloride

  (II), the spectrographic analysis was carried out according to the powder method and the X-ray analysis according to the single-crystal method. The single crystals of these compounds have been shown to have the following structure. Dipyrrolidone-copper (II) dichloride is a dimer of the formula: ## STR2 ## Cl4 (v) Cu2 CH2

0 4

  and its structure has the covalent character.

  Tricaprolactam-copper (II) dichloride monohydrate is actually a polymer whose monomer has the structure: Cu [K ++ [u KC3], K = caprolactam, 61 [u 3C13 2 and has the ionic character. The water molecule obviously

  loses during the growth of the single crystal in alcohol.

  The proposed fungicides can be used in the control of crop diseases caused by

  Phytophotora infestans, Botrytis cinerea,

  cillium dahliae, Sphacropsis malorum, Coniothyrium diplodial-

  the, Fusarium moniliphorme, Venturia inaequalis, Aspergillus niger. The proposed agents are active in the fight against

  mold-stimulating complexes, against helminth

  thosporiosis of barley, the solid niello of wheat, the phy-

  tophtorosis of tomatoes and potatoes, rice

  niose of the potato. The proposed agents are used by seed treatments, by spraying the plants,

by introduction into the soil.

  In addition, the agents in question may be applied for the protection of non-metallic

  biological destruction due to fungi: Chaetomium glo

  bosum, Penicillium cyclopium, Paecilomuces varioti, Tricho

  derma viride, Cladosporium herbarum, by impregnation of

  non-metallic materials (cotton fabric, natural leather) with

solutions of active ingredients.

  The indicated compounds outperform in effectiveness

  with respect to the above-mentioned diseases or are

  of reference products such as terephthalide disulfide

  tramethylthiuram (TMETD), ethyl mercury chloride, hexa

  chlorobenzene, the zinc salt of ethylene-bis-dithio-

  carbamic acid, salicylanilide, 1-hydroxy-diphenyl, poly-

  carbacine. The agents which are the subject of the invention can be used as such or in combination with other fungicides, for example

  example, with vitavaxe, TMTD, zineb.

  The fungicidal agents proposed are preferably

  this, in the form of solutions, suspensions, wettable powders

  and granules. The active substance concentration of

  positions is 0.01-99.5% by mass.

  The preparation of the compositions is carried out by a generally known method-that is, by mixing or grinding the proposed complex salts with the excipient, for example water, acetone, ethyl alcohol, amorphous silica,

high dispersity, kaolin.

  Thus, to prepare a wettable powder, one brews

  the proposed complex salts, a mixture of alkaryl ethers

  polyethylene glycol, alcohol-sulphitic vinasse,

  amorphous silica of high dispersity and kaolin.

  To prepare the granules, the salts are dissolved

  plexes cited above in acetone, add hydroxide

  of silicon, stir and remove the acetone.

  To prepare solutions, the salts are dissolved

  proposed plexes in a suitable solvent: water, acetone,

Ethyl alcohol.

  Other features and advantages of the invention

  will be better understood by reading the description that will

  follow several concrete examples of its realization.

EXAMPLE 1

  Preparation of mercury-N- (1-hydroxy-2,2-chloride,

2 trichloroethyl) pyrrolidone.

  1.2 g of corresponding pyrrolidone are added in absolute ethanol to 1.36 g of HgCl 2 in absolute ethyl alcohol and the mixture is boiled for 8 hours. The alcohol is evaporated, a white precipitate remaining is washed several times

  with cold alcohol. 2.4 g of product (yield

  95%) with a melting temperature of 133-135 C.

  structure of the compound obtained is confirmed by the

  and infrared spectra.

  Analysis: Found,%: C, 13.89; H, 1.87; N, 2.79 calculated for C6H8C15NO2H,%: C, 14.27;

H, 1.59; N, 2.78.

EXAMPLE 2

  Preparation of mercury-N- (1-hydroxy-2,2-chloride,

2-trichloroethyl caprolactam.

  To 1.3 g corresponding lactam in absolute ethanol

  1.36 g of HgCl 2 are added to the absolute alcohol. We

  boil the mixture for 8 hours, the mixture is evaporated

  cool, the remaining white precipitate is washed several times with cold alcohol and 2.4 g of product is obtained (yield

  %) having a melting temperature of 129 to 130 OC.

  Analysis: Found,%: C 15.10; H, 2.05; N, 2.50;%, C, 15.70; H, 2.65; N, 2.62; for

C08H12C15NO2Hg.

EXAMPLE 3

  Preparation of monocaprolactam copper (II) dichloride and tricaprolactam copper (II) dichloride monohydrate. To 22.6 g of caprolactam in absolute ethanol is added at room temperature 17.1 g of CuCl 2 .2H 2 O in absolute alcohol, the mixture being stirred for one hour. A yellowish precipitate forms at rest, which is filtered off and washed with alcohol

  cold. The precipitate weight is 11.2 g (28% yield).

  The melting temperature of the product obtained is 210-212 C.

  The product obtained corresponds to the formula:

CH2 CH2 CH2

CH2 CH.CuCl2 (VI)

C2 C2 -2

  o Analysis: Found:%: C 29.48; H, 4.65; N, 5.53; C1, 27.98;

Cu 25.64.

  Calculated,%: C 29.03; H, 4.44; N, 5.65; C1, 28.63;

Cu 35.81, for C6 11NOC12Cu.

  Infrared spectra: N 3380 cm -1, 1490 cm -1

V C1640 cm-.

CO

  A green precipitate forms in the so-

  mother, washed several times with sulfuric ether

  that cold. The weight of the precipitate is 16 g (yield 40 ").

  The melting temperature of the product is 78-80 C.

duit is a compound of formula:

CH2 CH2 __CH

| NH.CuCl₂H₂O (VII)

CH CH 0 3

  Analysis: Found,%: C, 44.32; H, 6.99; X 8.46; Cu 13.51;

C1 14.05.

  Calculated, in S: C 43.90; H, 7.11; N, 8.54; Cu 13.01; Cl 14.43, for C H N 0 C12Cu.

'P 18 35 3 4 2 -1

  Infrared spectra: 0, N3300 cm -1, 15.10 cm -1,

C1615 cm-1. -

CO

EXAMPLE 4

  Preparation of tricapro- monohydrate dichloride

lactam-copper (II) (II process).

  To a solution of 339 g of caprolactam in 400 ml of absolute ethanol having a temperature of 40 ° C., a solution of 171 g of CuCl 2 is added. 2H20 at 40 C,

  in 500 ml of absolute ethanol, and the mixture is boiled for

  one hour. The alcohol is removed, an oil remains, sulfuric ether is added, and the oil crystallizes. The melting temperature of the product obtained is 80-82 C,

yield 88%.

  Analysis: Found,%: C, 44.43; H, 6.94; N, 8.41; C1, 13.98;

Cu 13.37.

  Calculated,%: C, 43.90; H, 7.11; N, 8.54; C1, 14.43;

Cu 13.01, for C 18H 35N 3o4Cl 2Cu.

EXAMPLE 5

  Preparation of di (N-phenylpyrrolidone) dichloride

copper (II).

  To 3.22 g of phenylpyrrolidone in absolute ethanol, brought to the boil, 1.71 g of CuCl.sub.2.2H.sub.2 O in absolute ethanol are added. We leave the solution at rest

  for one day at room temperature, then evaporate.

  Brown crystals are obtained. The weight is 4 g

  demoent 84%), the melting temperature is 195 C with decency.

  Analysis: Found,%: C 52.85; H, 4.57; N, 5.99; Cu 14.20;

C1 15.04.

  Calculated; in%: C 52.52; H, 4.81; N, 6.13;

  Cu 14.00; C1 15.54, for C20H22N2O2Cl2Cu. Infra-spectra

red CN 3000 cm-1, QCO 1630 cm-1.

EXAMPLE 6

  Preparation of di-thiopyrrolidone-copper dichloride

vre (II).

  To 1 g of thiopyrrolidone in acetone is added

  With stirring at room temperature, 1.68 g of CuCl 2 is added, freshly calcined in acetone with stirring. A gray colored precipitate forms, which is washed several times with cold acetone. 2.85 g (68% yield) are obtained,

  having a melting temperature of 142 to 143 C.

Analysis:

  Found,%: C 28.04; H, 3.97; N 8.07, Cu 18.82.

  Calculated,%: C, 28.49; H, 4.15; N 8.31; Cu 18.99

for C8H14N2S2C12Cu.

EXAMPLE 7

  Preparation of dipyrrolidone-copper (II) dibromide

  To a solution of 8.5 g of pyrrolidone in absolute ethanol at a temperature of 40 ° C., 11.2 g of CuBr 2 in absolute ethanol are added. Bring the mixture to a boil

  and leave at rest for one day at room temperature

  ature. Evaporate the alcohol, brown crystals remain. We

  19.5 g (68% yield) having a temperature of

from 99 to 100 C.

  Analysis: Found: C, 24.33; H, 3.43; N, 6.96; Cu 16.27 Calculated,%: C, 24.40; H, 3.56; N, 7.14; Cu 16.40,

for CsH14N202Br2Cu.

EXAMPLE 8

  Preparation of dipyrrolidone-copper (II) dichloride

  To 17 g of pyrrolidone in absolute ethanol is added

  under heating 17.1 g of CuCl 2 .2H 2 O in abstained ethanol

  solved. Stir at room temperature for one hour.

  There is a green precipitate that is washed several times by

  the téthanol. 29.5 g (98%) of product having a time

  melting temperature of 125 to 128 C.

  Analysis: Found,%: C, 31.18; H, 4.18; N, 9.36; Cu 21.17 Calcd.% C 31.48; H, 4.59; N, 9.18; Cu 20.98;

for C8H14N202Cl2Cu.

EXAMPLE 9

  Preparation of mono-N-methyl-pyrrolidone dichloride

No. zinc.

  To 1.95 g of N-methylpyrrolidone in absolute ethanol

  After stirring at room temperature, 5.2 g are added

  of ZnCl2.4H2O in absolute ethanol. It is stirred at room temperature

  ambient temperature for one hour, the alcohol being evaporated.

  It remains a light yellow colored oil that crystallizes at

* rest. 6.2 g of product are obtained (yield 62%).

Analysis:

  Found,%: C, 25.46; H, 4.17; N 6.08; Zn 27.05.

  Calculated in%: C 25.53; H, 3.83; N, 5.96; Zn 26.85,

for C 5H 9NOCl 2 Zn.

EXAMPLE 10

  Preparation of dipyrrolidone monohydrate dinitrate

nickel (II).

  To 1.7 g of pyrrolidone in absolute ethanol is added under heating 2.91 g of Ni (NO 3) 2.6H 2 O in absolute ethanol. Stirred at a temperature of 78 ° C. for one hour, the mixture is cooled, the alcohol is evaporated, and it remains

  colored crystals in green. We obtain 3 g of product

  81%), the melting point being 55-57 ° C.

  Analysis: Found,%: C, 25.96; H, 4.82; N 14.98 Calculated, as%: C, 25.88; H, 4.31; N, 15.09 for C8H16N4NiO9.

EXAMPLE

  Preparation of dinitrate monohydrate dicaprolac-

tamo-nickel (II).

  To 2.26 g of caprolactam in absolute ethanol is added under heating 2.91 g of Ni (NO 3) 2.6H 2 O in absolute ethanol. The mixture is stirred at 78 ° C. for one hour, cooled, the alcohol is evaporated off, and the crystals remain green. 3.9 g of product are obtained

  (91% yield), the melting temperature being 91-93 C.

  Found,%: C, 33.77; H, 5.50; N, 12.85.

  Calculated,%: C, 33.72; H, 5.62; N 13,11, for

12 24N4NiO9.

EXAMPLE 12

  The effectiveness of cupric compounds in the control of phytophtorosis in potatoes and tomatoes has been studied. We water the potato and tomatoes with a

  aqueous suspension prepared from the wet powder

  the amount of liquid being 500-600 l / hectare.

  To prepare the wettable powder, one brews 50 parts

  by weight of tricaprolactate dichloride monohydrate

  mo-copper (II), 3 parts by weight of a mixture of polyethylene glycol alkaryl ethers, 3 weight parts of alcohol-sulphite vinasse, 10 parts by weight of silica

  amorphous high dispersity and 34 parts by weight of kao

  flax until the formation of a homogeneous mixture.

  The effectiveness of fungicides is characterized by

  degree of disease progression (%) and by the method of "do-

  is the only effect "(inhibition of the disease,%) The experimental data are processed by the statistical method.

  confidence intervals calculated at p - 0.05, are equal to 12

  t%. The fungicide content of the liquid is expressed as active ingredient (p. Table I summarizes the indices of efficacy for the case of maximum disease progression

  on control plants without spraying. The effectiveness of

  cacity of the product against phytophtorosis of the apple of ter-

  and tomatoes at a concentration of 0.02-0.005% cal-

  in active substance. The treatment is done. QUA

  the size of the plot being 20 m. We

  makes four sprinkles of the potato and tomatoes

  your. As a control is used the zinc salt of ethylene-bisdithiocarbamic acid and a mixture of zinc salts and ethylene-bis-dithiocarbamic acid manganese. The

  The results are summarized in Table 1.

EXAMPLE 13

  Test of the agents to fight against the spores of

  Coniothyrium diplodiella and Sphaeropsis malorum.

  The test is carried out by the hanging drop method. We draw with a pencil of wax three equal circles on the glass object. We place in each circle

  0.1 ml of the agent solution, the drops are dried at room temperature

  room temperature, then seed a spore suspension

  mushroom (density of 150 to 200 spores in the field of

  microscope). The glasses are placed in a human chamber

  mide. After twenty-four hours the number of germinated spores is calculated. We perform the test at a concentration

  0.03%. Compounds 5.15 completely inhibit germination

  nation of Coniothyrium diplodiella spores and significantly reduce the germination

Sphaeropsis malorum (Table 2).

EXAMPLE 14

  The activity of the agents against the mold-stimulating complex is determined by the method of spreading the seeds germinated on filter paper moistened in Petri dishes. They are kept at room temperature for seven days. The percentage of seeds affected with the mold, the germination capacity of the seeds and the influence of the agents on the size of the seedlings are then determined. Agents do not yield to the control - 80% TMTD,

  as to the activity against the stimulating agents of self-

  do not diminish the germinability of the seeds and do not have a negative effect on the size of the seeds.

plantuies (Tables 3, 4).

EXAMPLE 15

  The activity of Barley Helminthosporiosis agents is determined by the seeding of infected seeds.

  with the fungus Helminthosporium sativum, then treated

  by the agent to be studied at a rate of 2 g / kg, in the germs

  moist sand beaches, where they are maintained at a

  between 22 and 24 C for 14 days. The germination capacity of the seeds and the infestation are then determined.

  these plants of helminthosporiosis. High activity has been

  agents against leafminer disease following

tests (Table 5).

EXAMPLE 16

  The tests of the activity of the agents against the solid nielle of spring wheat are conducted. Seeds of spring wheat are seeded with chlamydospores of

  the solid niella at a rate of 7 g / kg, then treated with

  at a rate of 2 g / kg semi-dry, and sow in the chamq. The size of the plots is 15 m, the treatment being carried out three times. The germination power of the wheat field was determined during the period

  vegetative growth, and the percent of seed infestation

  with the solid niello as well as the harvesting of wheat on a

  have been determined during the maturing period.

  is lying. High activity of drugs against

solid niello (Table 6).

EXAMPLE 17

  Action of agents against phytophtorosis of tomatoes.

  The tests are carried out on tomatoes aged 2-3 weeks. The compound is used at a concentration of 0.1% of active substance. After treatment with the agents, the plant is inoculated with an aqueous suspension of the spores of the

fungus Phytophtora infestans.

  The degree of evolution of the disease is determined by the five-point scale, the inhibition of the following disease

Abbott's formula (Table 7).

EXAMPLE 18

  The activity of the compound vis-à-vis the mushrooms Bo-

  Cinetea, Fusarium moniliforme, Venturia inaequales, Aspergillus niger, Verticillium dahliae has been studied on

  the mycelium of the fungi indicated.

  Agents are dissolved in acetone and sterile are introduced into the apple dextrose agar.

  melted earth which is then poured into the Petri dishes.

  The cookie is the TMTD. The concentration of the agents in the medium is 0.003% of active substance. After 18-20 hours, the agar plate is inoculated with the flaps of the mycelium of the aforementioned fungi and maintained at

  temperature of 25-26 OC for four days.

  At the end of this period, the

  the colonies of the fungi to be studied, and then

  the percent inhibition of fungal mycelium growth by Abbott's formula compared with

the witness.

  Percent inhibition = A - C. 109, o A - growth

  this mushroom colonies for the witness; C - growth

  colonies of the fungus with the agent.

  The results are shown in Tables 8.9.

EXAMPLE 19

  The antiseptic activity of the drugs was studied by the method described in Example 16. As objects

  for testing, fungi causing

  sissure of non-metallic materials: Chaetomium globosum,

  Penicillium cyclopium, Paecilomuces variofi, Trichoderma vi-

period (Table 10).

EXAMPLE 20

  The antiseptic activity of the compounds on samples of cotton fabric (unfinished cotton wool) is studied by the following method. The tissue is treated with antiseptics under laboratory conditions. The drugs are first dissolved in acetone, the tissue is immersed in solutions of various agent contents for 15 minutes,

  then press and dry. The control is hydroxy diphenyl

  nyle. The dosage of the agent represents 2% of the weight of the fabric. In the mold mildew resistance test, the samples treated with the agents are sterilized in a

  drying oven at a temperature of 70 C for 20 minutes

  your. Then we hang them on the rack in a desiccator

  intervals of five cm. We try separately the samples

  antiseptic and non-antiseptic samples. We

  uniformly sprinkle the samples with a suspension

  spores. To prepare the suspension, use the following fungi: Chaetomium globosum, Penicillium

  Cyclopium, Paecilomuces varioti, Stachybotrys atra, Penicill-

lium brevi-compactium.

  The tests are carried out at a temperature of 28 C and

  the relative humidity of the air being 98%. The duration of the ex-

  period is 28 days. We examine samples

10.20 and the 28th day.

  The growth of mold is evaluated on the

Scale & five points:

  O - complete absence of growth.

  I - the growth is visible under the microscope 2-25% of the surface is covered with mold 3-.50% "e 4-75% t n n"

-100 ""

  The data are summarized in Table 11.

EXAMPLE 21

  The testing of the antiseptic activity of the agents on

  samples of natural leather is made by the following method

  tout: sterile cowhide is made antiseptic by stirring it with fat, at a temperature of 70 ° C,

  This mixture is then rubbed with no remains in the leather for reasons of

  its 20% of the weight of pressed leather. As a control, use is made of hydroxy-diphenyl. The test of resistance to

  mold is produced in the following manner. Samples

  antiseptic leather, and samples without antiseptics (controls) are infested with

  spores on the flower side and on the dulcuir flesh side. Leather samples made antiseptic, infested with spores, are placed in a desiccator and are surrounded with samples of the non-antiseptic leather affected by

mold on two sides.

  The experiment lasts 28 days at a temperature of 28 OC,

  the relative humidity being 98%.

  The determination is made after 10, 20 and 29 days. The degree of infestation is evaluated at the five-point scale, described in Example 18. The results are

summarized in Table 12.

EXAMPLE 22

  Testing of compounds against phytophtorosis of

  mates is made on tomato plants Aged 2-3 weeks after transplanting. Repeat the experiment three times. The compound is tested at the active substance concentration of 0.1% by weight, the liquid flow being 3-6 ml per plant. One hour after treatment with the agents, the plants are inoculated with an aqueous suspension of the spores of the fungus Phytophthora infestans. The concentration of

  zoospores in the suspension is 50,000 in 1 ml of water.

  After infestation, plants are placed in a room

  wet for 24 hours. Inhibition of the evolution of the

  Ladie is calculated by Abbott's formula.

  The results are given in Table 14.

TABLE i

  Fungicidal Activity Agents Against Tomato and Potato Phytophthora Active Ingredient of Agent 4 Zinc Salt

of ethyl acid

ene-bis

  thiocarbamic Concentration of active principle, in% by mass 0, O2 0,01 0,005 0,02 0,01 0,005 Inhibition of the disease,%

phytophlore

  pink toros of tomato toast

100

95

83 86

95

96 97

84 80

  mixture of zinc salts and ethylene-bis thiocarbamic acid manganese evolution of the disease for control (no spraying) 0.02 0.01

-0.005

92

TABLE 2

  Fungicidal activity of Sphaeropsis malorum and Coniothyrium diplodiella spore agents Active principle Concentration Percent of agent spores in principle sprouted

active in% Sphaeropsis Coniothy-

mass malorum rium di-

plodiella

0.03 1.2 0

0.03 2.5 O

  Witness (distilled water) - 76.5 80.8

TABLE 3

  Results of Fungicide Tests Against Compounds

  Mold stimulator plexus Agent active principle Standard of

consumption

tion, g / kg

germinal

  native, Studies of wheat, mold,

TMTD & 80%

Ethyl chloride

  mercury Witness 9 'ratory magnitude

planting

the stem, root cm cm 8 8 9 11

8 9

? 9

248S010

TABLE 4

  Test results of fungicidal agents against the mildew stimulator complex principle Consumption standard Active laboratory testing of agent, wheat g / kg size of A seedlings oe -A tR 0 root stem 14'44 cm, cm ,, 1 2 78 i 5 8

2 2 84 5 5 7

80% TMTD 2 87 1 5 9

  Ethylmercury Chloride 2 85 O 5 8 Control - 88 12 6 8

TABLE 5

  Results of the tests for fungicides against barley grass blemospermosis Principle Standard of practice Active vegetation experiments 1977 summation 1978 the agent, g / kg I 14 14 4: R 4 S> * 4.r 4 o 4 o (J 0} 4 f 14 2 TMrD at 80%

Chloride

Thylmercury Witness

43 32.0 100 51.0

40.0 98 63.0

62 8.0 100 5.0

51 14.0

42 92.0

6.0 88.0

TABLE 6

  Fungicidal Trial Results as a Treatment of Spring Wheat Seeds (Against Solid Kernels) Active Principle Standard of Experience

consume-

mation

befor-

parts, g / kg 2 s2 80% TMrD

Hexachloroben-

zene at 30%

Chloride

  thylmercury Witness j 0 u t4 O h 'O * l O 0w z

> 0

O., - 1 OH

0 -H 0

Fa eP

2 78

2 81

2 89

2 81

a> 4 0

ti-

ge, cine,

0 9 10

0 7 9

w _w _

ti-

ge "cine, cm em

O 9 10

0 8 8

0 7 9

  Field experience at ri H o AH 0 * r> + U ri 0, 9 1.35 6.0

0 11 9 86 0 45.5

2 84 0 7 7 73 0.29

- 80 2 9 9 100 31.9

  id e. O-P o o-% O 49.9 47.2 29.8 c

TABLE 7

  Results of trials of fungicidal preparations against phytophtorosis of tomatoes Inhibition of the evolution of the disease,% 2

Ethylene acid zinc salt

  bis-dithiocarbam disease course for the control 94.2 68.6

TABLE 8

  Results of the fungicidal agents test on fungal mycelium

  Principle Concentration, Inhibition of growth

  active principle of active mycelium, fungi and% by mass bacteria,% Botrytis Verticillium cinerea dahliae 15 11

TMTD at 80%

* 0.003

OP 003

0.003 0.003 0.003 0.003

OP 003

0.003 0.003 0.003

0, 003

0.003 0.003 0.003 Active ingredient

TABLE 9

  Results of the test on the fungicidal activity of sea salts

  N- (hydroxy-2,2,2-trichloroethyl) lactams Principle Percent inhibition of mycelial growth

  active Bot. Fus.moni- Ven.inae- Asp.ni- Green.

cinerea liforme qualis ger dahliae

1 100 100 100 100 100

2 63 33 100 35 _100

TMTD -100 100 100 100 100

TABLE 10

  Antispecific activity of fungicidal preparations Concentration of active ingredient 0.003% Active principle Percent inhibition of growth of prep fungi Ch.gio-P.cyclo- P.varioti Tr. Viride ration bosum pium

1 100 100 100 89

2 1i00 100 100 100

3 100 100 86 80

  Salycylanilide 100 98 100 80 Hydroxydiphenyl 100 100 100 100 Tests of

TABLE 11

  fungicidal preparations on the antiseptic activity Principle ConcentraRecording time, active days in 10 20 30 the prep-principle active ration,% index state in points in mass (average of 9)

1 2,0 0 0 0

2 2,0 0 0 0

3 2,0 0 0 1

hydroxy

  diphenyl 2.0 0 0 0 Control - O 2 4

TABLE 12

  Test of fungicidal preparations on antiseptic activity on samples of natural leather Principle Concentration Recording time, active days in principle 10 20 30 active prep,% prepactio,% in point state (average 9) mass ration

1 20 O O O

2 20 0 0 0

3 20 O 0 1

hydroxydi-

phenyl 20 0 0 O Control 2 3 5

TABLE 13

  Results of the test of fungicidal preparations against phytophtosis of tomatoes Active principle Inhibition of the evolution of the preparation phytophtorosis of tomatoes,%

17 86

18 95

  Dichloride tricaprolactam monohydrate copper (II) 100 Zineb 100 Evolution of disease for control 75%

Claims (8)

  1 - Complex salts of lactams or thiolactams and halides or nitrates of heavy metals, characterized in that they correspond to the following general formula: Me m C, y (CH2N R N ___ R   o Me = Cu II, Zn, Mn o X = Cl, Br, NO 1 m = 1.2; n = 3.5 a = 1,2,3,4; R = H, - CH-CC13,   ! Xp.KH20 to HgII, NiI, Y = OS; P = 2.4; K = 0.1; CH3, C6H5   OH 2 - complex salts of lactams and halides or nitrates of heavy metals according to claim 1,   characterized in that they correspond to the following general formula: vante: r Me il Me = Hg R = H, C - O C; H2) n N .. R CuII, NiII; -CH - CC13, Xp.KH 20 a X = n = C1, Br, NO3; 3.5; K = 0.1; a = 1.2.3; p = 2   3 - Mercury-N- (1-hydroxy-2,2,2-trichloroethane chloride   ethyl) pyrrolidone according to claim 1.   4 - Mercury-N- (1-hydroxy-2,2,2-trichloroethane chloride   ethyl) caprolactam according to claim 1.   T'T - dipyrrolidone copper (II) dibromide, next claim 1.   6 - Tricaprolactam copper dichloride monohydrate (II) according to claim 1.   7 - Process for the preparation of the complex salts of   lactams or thiolactams and halides or nitrates   heavy metals, according to claim 1, characterized   in that a lactam or a thiolactam of the general formula is reacted: C y (CH 2) I   R = R = H, -CH- CCl3, CH3, C6H5, Y = OS; n = 3.5; OH   with a halide or the nitrate of a heavy metal of general formula: Me x2.k H20, where Me = CuII, Zn, Mn, HgII Ni x = C1, Br, NO3, k = 0.2.6 in a solvent organic and a temperature of 20 to 80 C,   with subsequent isolation of the product concerned.   8 - Fungicidal preparation containing an active ingredient   and an excipient, characterized in that as an   it contains the complex salts of lactams or thio-   lactams and halides or nitrates of heavy metals,   according to claim 1, in a proportion of 0.01-99.5% by weight.   9 - fungicidal preparation according to claim 8, characterized in that it contains as active ingredient mercury-N- (1-hydroxy-2,2,2-trichloroethyl) chloride; pyrrolidone.   - Fungicidal preparation according to claim 8, characterized in that as an active ingredient it contains mercury-N- (1-hydroxy-2,2,2-trichloroethyl) caprolactam chloride. 11 - fungicidal preparation according to claim 8, characterized in that t & title of active ingredient it contains   dipyrrolidone-copper (II) dibromide.   12 - Fungicidal preparation according to claim 8, characterized in that as active principle it contains   tricaprolactam-copper (II) dichloride monohydrate.