CZ300772B6 - Boric, salicylic acid or derivatives thereof and silver complex compounds, process of their preparation and composition for killing moulds, fungi and woodborers containing such compounds - Google Patents

Abstract

The invented process for preparing a complex compound of boric acid, salicylic acid or derivatives thereof and silver of the general formula I, in which X = H, NHi2, NHC(=O)R, wherein the group R denotes hydrogen, or generally alkyl containing 1 to 8 carbon atoms, is characterized in that there is prepared under perpetual stirring a solution of boric acid (one molar unit) and salicylic acid (two molar units) or a derivative thereof in a polar solvent, whereby the concentration of the salicylic acid or the derivative thereof in the solution is in the range of 0.2 to 50 percent by weight and the solution is prepared at a temperature ranging from 0 degC to boiling point of the polar solvent. Subsequently, one molar unit of lunar caustic is added under perpetual stirring to the solution of the boric acid and salicylic acid or a derivative thereof in the polar solvent, the resulting solution is cooled down to a temperature in the range of 0 to 25 degC and the obtained white complex precipitate is the filtered off and dried at a temperature ranging from 25 to 80 degC. The above-indicated composition is suitable for killing moulds, fungi and woodborers.

Description

(57) Annotation;

In the process for preparing complex compounds of boric acid, salicylic acid or its derivatives and silver of general formula! Where X = H, NH _3, NHC (= O) R, where R is H, or generally Ci to C _alkyl stirring prepare a solution of boric acid (one molar unit) and salicylic acid (two molar units) or a derivative thereof in a polar solvent, wherein the concentration of salicylic acid or a derivative in the solution ranges from 02 to 50% by weight and the solution is prepared at a temperature of 0 ° C to the boiling point of the polar solvent. Thereafter, to the solution of boric acid and salicylic acid or a derivative thereof in a polar solvent is added, with stirring, one molar silver bisulfate, the resulting solution is cooled to 0 to 25 ° C, and the resulting white complex precipitate is then filtered and dried at 25 to 80 ° C. The above formulation is suitable for controlling mold, fungi and wood-destroying insects.

Complexes of boric acid, salicylic acid or its derivatives and silver, process for their preparation and preparation for controlling fungi, fungi and wood-destroying insects containing these compounds

Technical field

The present invention relates to novel complex compounds of boric acid, salicylic acid or derivatives thereof and silver, to a process for their preparation and to a composition for controlling fungi, fungi and wood-destroying insects containing these compounds.

BACKGROUND OF THE INVENTION

Silver and its compounds are very effective agents against fungi or disinfectants in general. The mechanism of action of silver, which is mainly applied in colloidal form, is not exactly known. As regards the monovalent silver compounds, is known to be effective it has concentrations of these ions in the region of 10 ^-12 mol.dm ** (overview of silver and its compounds, e.g., Comprehensive Inorgcmic Chemistry, vol. 3, JC Bailar, Jr. , et al., Eds., Pergamon Press, Oxford, 1973). There are also marketed organometallic silver compounds which also exhibit these properties. It is, for example, silver salicylate (X = H) or its amine derivative (X = NH2), i.e. the aminosalicylic acid salt described by the general formula A. Or it is a silver salt of the sulfonamide, for example sulfadiazine, represented by the formula B. non-metal compounds of both series (A, B) exhibit biological effects, for example 4-aminosalicylic acid exhibits potent antibacterial effects (for example, see The Merck Index, An Encyclopedia by Chemicals, Drugs, and Biologicals, 12 ^lh Edition, Merck Research Laboratories, 1996), which probably can be attributed to internal form ammonium salts of ⁽⁺ H3N-C 6 H ₃ (OH) -COO). The disadvantage of the compounds A and B is that they are essentially pigments which diffuse poorly into the treated material and can dust off the surface of the treated material.

It is also well known that an effective agent against wood-destroying pests is boric acid or its borax salt, a compound which, even in the wild (e.g. in plant roots), acts as a protective agent against fungi, fungi and wood-destroying insects. A disadvantage of both of the above-mentioned boron compounds is that they are water-soluble so that protection of the material exposed to water is not long-lasting. Boric acid esters, such as boric acid ester and glycerin, have similar effects but are less soluble in water and well soluble in alcohol (Sciarra, Elliot, J. Am. Pharm. Assoc. (Sci. Ed.)). 49, 116 (1960)). However, the biological activity, especially against molds, is low, and where the material is already attacked by mold, neither boric acid nor borax eliminates it.

Boric acid (H3BO3) is known to be a weak monobasic acid, limited in water permeability, not acting as a proton donor but as a Lewis acid. Salicylic acid, or derivatives thereof, form tetraedic complexes with boric acid at a ratio of 1: 1 or 2: 1 (Reaction in the boric acid-salicylic acid system. Grundsteins, V., Svarcs, E., Inst. Neorg,

Khim., Riga, USSR, Latvijas PSR Zinatnu Akademijas Vestis, Kimijas Serija (1978). (2), pp. 131-5. ISSN: 0002-3248), where the characteristic vibrations of B-0 in the tetrahedral complex are in the range of 980 to 975 cm ¹ . In these complexes, the proton may be replaced by another cation. For example, there is a work where, in boron and 4-methyl- and 4-hydroxysalicylic acid complexes, the proton is replaced by a silver cation (Lokenbaha, M, et al, Inst. Neorg Khim., Riga, USSR Latvijas PSR Zinatnu Akademijas Vestis, Kimijas Serija (1986), (6), 667-9, ISSN: 0002-3248). Further, for example, complexes of boron and salicylic acid and its derivatives (bearing halogen, alkyl, haloalkyl, aralkyl such as benzoyl and aryl) as salts (with H ⁺ , Li ⁺ , Na ⁺ , K ⁺ , Ag ⁺ , etc.) are salts. also described in U.S. Patent 4,767,688 (1988), where the disclosed compounds are used as additives to xerographic toners (Charge Control Additives).

The disinfectant has also a significant disinfection effect, the so-called basic dyes, where the chromophore has a positive charge, which is compensated by a simple anion. The most well-known representative is, for example, Crystal Violet, or Gentian Violet (toxic studies: H. C. Hodge et al., Toxicol. Appl. Pharmacol. 22, 1 (1972)). These are compounds that bind to a phosphate group in a microorganism and thus prevent the formation of adenosine triphosphate and thus cell nutrition. Indeed, all tetraalkyl- or tetraaryl-ammonium compounds act by this mechanism, so all basic dyes (for an overview of basic dyes, see Color Index, 4th Edition on Line, The

Society of Dyers and Cofourists). A disadvantage of these ammonium compounds generally is that they are well soluble in water and can therefore be washed out of the treated material by the action of water. Moreover, the environmental resistance of these compounds (oxidation, light decomposition, etc.) is not great, so protection is not long-term. Ammonium compounds do not act against wood decaying insects.

The disadvantages of the prior art solutions are thus either the insolubility of the active compounds and the impossibility of saturating the treated material, or, conversely, the high water solubility and their easy washing out of the treated material. In addition, the activity of the individual compounds is specific, i.e. it only acts against some species of harmful microorganisms, as described above. These drawbacks are overcome by the formulation of the present invention.

SUMMARY OF THE INVENTION

The present invention relates to novel complex compounds of boric acid, salicylic acid or derivatives thereof and silver of formula (1),

wherein X = H, NH ₃ , NHC (= O) R, wherein R is H, or generally C 1 to C 8 alkyl.

The present invention further provides a process for the preparation of a complex compound of formula (I) which comprises mixing a molar unit of boric acid and two molar units of salicylic acid or a derivative thereof in a polar solvent with stirring, wherein the concentration of salicylic acid or a derivative thereof. the solution is in the range of 0.2 to 50% by weight, and the solution is prepared at a temperature ranging from 0 ° C to the boiling point of a polar solvent, then one molar is added to the solution of boric acid and salicylic acid or a derivative thereof in the polar solvent. silver nitrate unit, the resulting solution is cooled to 0 to 25 ° C and the resulting precipitate of complex is then filtered off and dried at 25 to 80 ° C.

In a preferred embodiment, a solution of boric acid and salicylic acid or a derivative thereof in a polar solvent is prepared at room temperature.

In a preferred embodiment, the polar solvent is selected from the group consisting of water, ethanol, 1-propanol, 2-propanol, acetone or mixtures thereof.

In a preferred embodiment, the silver nitrate is added in the form of a solution having a silver nitrate concentration of 0.2 to 91% by weight in a solvent selected from the group consisting of water, ethanol or a mixture thereof prepared at a temperature of 0 ° C to the boiling point of the solvent. Preferably, the silver nitrate solution is prepared at room temperature.

In another preferred embodiment of the invention, the silver nitrate is added as a solid.

The invention furthermore relates to a composition for the control of fungi, fungi and wood-destroying insects comprising, as active ingredient, at least one complex compound of the formula I, furthermore solvents and optionally suitable accompanying substances.

The compounds I described are insoluble in water. Conversely, they are soluble in mixtures of alcohol and water, the longer the aliphatic chain R the more complex the alcohol is. They are thus applied in the form of these solutions, where the active compound (complex I) diffuses into the material to be treated. After a period of time, the complex I gradually disintegrates and silver is reduced (the alcohol acts as a reducing agent to Ag ⁺ ), which is then evenly distributed in the atomic material, giving very high biological activity. Of course, silver is also insoluble in water, so it cannot be washed out of the treated material by the action of water or organic solvents. Also, boric acid and salicylic acid, or a derivative thereof, are fungicidal in the treated material. The product thus acts not only as a preventive protection of materials but also as a highly effective liquidator of harmful microorganisms.

In a preferred embodiment the formulation according to the invention as a solvent mixture of water and C ₂ to C ₃ alcohol.

Preferably, the preparation according to the invention contains colorants and stabilizers as accompanying substances. Advantageously, a colorant having a disinfectant effect, for example a basic colorant such as crystalline violet or Malachite green, can be used as the colorant.

In a preferred embodiment, the composition of the invention may be stabilized by the addition of hydrogen peroxide. Hydrogen peroxide prevents the reduction and formation of silver in solution. To prepare this preferred formulation, first prepare the desired solution of hydrogen peroxide in water, then add the alcohol and then the complex compound of formula I.

In a preferred embodiment, the composition of the present invention comprises 0.001 to 10 wt.

% of complex compound of formula 1, 25 to 98 wt. % C ₂ to C ₃ alcohol and 2 to 75 wt. water and optionally other accompanying substances such as colorants and stabilizers.

Preferably, the composition according to the invention further comprises 0.01 to 5 wt. dyes.

Preferably, a colorant having a disinfectant effect, for example a basic colorant such as Crystal Violet or Malachite Green, can be used as the colorant.

In a preferred embodiment, the formulation according to the invention can be stabilized by the addition of up to 0.6% w / w. hydrogen peroxide, based on the weight of water in the formulation;

The composition of the present invention can be used, for example, for controlling mold in households, or for preventive protection of wood, plasters or other materials that may succumb to fungi, fungi or wood-destroying insects. The colorless agent can be used with great advantage to protect plasters against painting or to protect wood against its own color coating.

EXAMPLES The Η ^kl C NMR spectra were measured on a Broker AVANCE 500 instrument at VÚOS as, Pardubice at 500.13 ('), respectively. 125.76 MHz ( ¹³ C). ^{The @ 1} H NMR spectrum was measured on a Broker AMX instrument

360 at 115.55 MHz. Samples were dissolved in DMSO-D 6. The 1 H and ¹³ C chemical shifts were relative to the solvent signal (δ = 2.55 (1 H) and 39.6 ( ¹³ C, respectively). ⁿ B chemical shifts were relative to external B (OCH3b placed in the coaxial capillary (S (' ¹ B) = 18.1)) Two-dimensional spectra (' H, 'C-COZY) were used to assign' H and ' ³ C chemical shifts 1 H, ¹³ C-HSQC and 1 H ^{, 13} C-HMBC).

Infrared spectra were measured on a FTIR-8400S Fourier Transform Infrared Spectrophotometer Shimadzu. Samples were measured in solid form in the form of KBr tablets, approximately 20 mg of sample and 60 mg of KBr were wiped in an agate mortar and pressed by a hydraulic press.

Example 1

Preparation of complex 1-1, water / ethanol reaction medium

Silver nitrate (17 g, M = 169.87) was dissolved in 80 g of distilled water at room temperature (25 ° C). In a second reaction vessel, boric acid (6.18 g, M = 0.25 g) was dissolved at room temperature

61.83) and salicylic acid (27.6 g, M = 138.12) in 120 g of denatured ethanol. An aqueous silver nitrate solution is poured into this solution with stirring. After stirring for 20 minutes, the reaction mixture was cooled to 5 ° C and the resulting snow white precipitate was filtered off and dried at 40 ° C. Yield 35.8 g complex compound of formula 1-1 ₍₈ Ci4H AGB O _6, M = 390.89), which represents a yield of 91.6%;

Example 2

Preparation of complex I-1, reaction medium water

Boric acid (6.18 g, M = 61.83) and salicylic acid (27.6 g, M = 138.12) are dissolved in 120 cm ^{3 of} distilled water at room temperature. The mixture was heated to 80 ° C and silver nitrate (17 g, M = 169.87) was added to this solution with stirring. After 20 minutes stirring, the reaction mixture was cooled to 20 ° C and the resulting snow white precipitate was filtered off and dried at 40 ° C ^P Yield 35.7 g complex compound of formula 1-1 (C ^ HgOéAgB, M = 390.89), which the yield is 91.3%.

Elemental Analysis of Complex 1-1

Element %C % H % Ag Calculated 43 2.05 27.6 2.77 Complex 1-1, prepared according to Example 1 41.00 ± 0.13 1.89 ± 0.01 22.4 2.44 Complex 1-1, prepared according to Example 2 44.43 ± 0.02 2.19 ± 0.04 21.9 1.99

The formation of complex 1-1 was confirmed by infrared spectroscopy, where new peaks with frequencies of 991 and 978 cm “ ¹ ν (Β (ΟΧ) ₄ )“ _ω , characteristic for tetragonal alignment, appear in the spectrum. The following infrared spectrum is identical for samples I-1 whether prepared according to Example 1 or 2.

io

FTIR (KBr): 1659 cm ^-1 in (C = O), 1609 cm ^-1 in (C = C), 1468 cm ^-1 in (CH), 1348 cm -1 δ (Ο-Ο) + v (CO), 1269 cm ^-1 , 1244 cm ^-1 , 1136 cm -1 ¹ δ (Ο-Η) + in (CO), 1060 cm ^-1 in (CO, 999 cm ¹ and 970 cm ^-1 in (B (OH) «) - _M , 876 cm ^-1 , 825 cm ^-1 , 770 cm ^-1 d (CH), 754 cm ^-1 and 694 cm ^-1 δ (Ο-Η).

Further, the structure of complex 1-1 was confirmed by NMR spectroscopy.

Salicylic acid:

Ο ^, ΟΗ 'A ^OH H NMR: 6.94 m (H, H-6); 6.98 m (1H, H-4); 7.52 m (1H, H-5); 7.84 m (lH, H-7); 11.3 bs (1H, COOH).

¹³ C NMR: 113.1 (C-2); 117.3 (C-4); 119.3 (C-6); 130.5 (C-7); 135.8 (C-5); 161.5 (C-3); 172.3 25 (CI).

Complex 1-1:

'HNMR: 6.89 m (IH, H-3); 6.94 m (1H, H-6); 7.48 m (1H, H-5); 7.80 m (1H, H-7).

¹³ CNMR: 115.5 (C-2); 118.1 (C, t); 118.9 (C-6); 129.3 (C-7); 134.8 (C-5); 159.1 (C-3); 163.9 (CI).

δ (Β) = 3.1.

Example 3

Synthesis of complex 1-2, water / ethanol reaction medium

Ag

1-2

AgNO ₃ (17 g, M = 169.87) was dissolved in 80 g distilled water at room temperature (25 ° C). In a second reaction vessel, H3BO3 (6.18 g, M = 61.83) and aminosalicylic acid 410 (30.6 g, M = 153.13) were dissolved in 120 g of denatured ethanol at 75 ° C. AgNO ₃ aqueous solution was poured into this solution with stirring. The reaction mixture was stirred for 30 minutes, then cooled to 5 ° C and the resulting greyish precipitate was filtered off and dried at 40 ° C. Yield: 41.1 g of complex of formula 1-2 (C ₁₁ H ₁₀ N ₂ O ₆ AgB, M = 420.92), which represents 98% yield.

Example 4

Synthesis of complex 1-2, reaction medium water

H3BO3 (6.18 g, M = 61.83) and 4-aminosalicylic acid (30.6 g, M = 153.13) are dissolved in 120 cm ^{3 of} distilled water at room temperature. The mixture was heated to 80 ° C and AgNO ₃ (17 g, M = 169.87) was added to this solution with stirring. After stirring for 20 minutes, the reaction mixture was cooled to 20 ° C and the grayish precipitate formed was filtered off and dried at 40 ° C. Yield: 40 g of a complex of formula 1-2 (Ci4H _g AGB O _6, M = 390.89), which represents a 95% yield.

Elemental Analysis of Complex 1-2

Element %C % H % N % Ag % B Calculated 39.91 2.38 6.65 25.62 2.57 Complex 1-2, executed according to Example 3 38.83 ± 0.02 2.30 ± 0.02 6.72 ± 0.04 21.2 2.34 Complex 1-2, prepared according to Example 4 35.38 ± 0.04 2.12 ± 0.07 6.50 ± 0.05 23.25 2.07

The formation of complex 1-2 was confirmed by infrared spectroscopy, where new peaks with a frequency of 991 and 968 cm ^-1 in (B (OX) ₄ ) _and characteristic for tetragonal alignment appear in the spectrum. The following infrared spectrum is identical for samples 1-2, whether prepared according to the procedure of Example 3 or 4.

FTIR (KBr): 3484 cm ⁴ and 3311 cm ⁴ in (NH 2), 1682 cm ¹ in (C = O), 1600 cm ⁴ in (C = CC) + δ (ΝΗ), 1462 cm ⁴ in (CH), 1323 cm ⁴ δ (Ο-Η) + in (CO), 1304 cm ^-1 in v (CN), 1146 cm ⁴ δ (Ο-Η) + in (CO), 1068 cm ¹ in (CO), 991 cm ⁴ and 968 cm ⁴ ν (Β (ΟΗ) 4), 879 cm ⁴ , 849 cm ⁴ , 769 cm ⁴ , 764 cm ⁴ and 694 cm ⁴ δ (Ο-Η).

Further, the structure of complex 1-2 was confirmed by NMR spectroscopy.

Complex 1-2:

1 H NMR: 5.41 bs (2H, NH ₂ ); 6.03 d (lH, H-4); 6.20 dd (1H, H-6); 7.48 d (lH, H-7).

¹³ C NMR: 101.3 (C-4); 104.9 (C-2); 107.1 (C-6); 130.7 (C-7); 153.9 (C-5); 160.9 (C-3); 164.7 (CI).

δ ( ^π Β) = 2.9.

Example 5

Synthesis of 4-acetamido-2-hydroxy-benzoic acid

4-Amino-2-hydroxybenzoic acid (7.66 g; M = 153.14; 0.05 mol) is stirred in 50 cm ^{3 of} water, the pH is adjusted to 6 (10% aqueous NaOH) to give a solution. Acetic anhydride is gradually added to the solution in approximately 0.5 cm ³ , where the total acetic anhydride consumption is 7.1 cm ³ (m = 102.09; d = 1.081; n = 0.075 mol). The reaction temperature is 60 ° C, the reaction pH is still maintained at 6 to 7 by the addition of 10% NaOH solution. The reaction takes 5 hours, the acylation progress is tested by Ehrlich reagent. After completion of the reaction, the mixture was cooled to room temperature and the pH was lowered to 3.5 (by adding conc. 35% HCl). The precipitate formed is filtered on a Buchner filter, the filter cake is redissolved in 20 cm ^{3 of} acetone and after 20 minutes of vigorous stirring, re-precipitated with water, filtered again and dried at 40 ° C. Yield 8.84 g of chromatographically pure product (C 9 H 9 NO 4; M = 195.18), which represents a yield of 90.58%.

TLC: solid phase: ALUGRAM SIL G / UV ₂₅₄ (MACHERY-NAGEL), mobile phase: 2-propa30 nol / 1-propanol / ethyl acetate / water = 2/4/1 / 3 by volume.

Formation of the N-acetyl derivative was confirmed by infrared spectroscopy, the disappearance of vibration v (NH) 3495 cm ^"1 and appears peaks characterizing secondary amine 1672 cm ^-1 v (C = O) Amide I and 1539 cm ^-1 v (NH) Amide II.

FTIR (KBr): 3312 cm ^-1 in (NH), 1672 cm ^-1 in (C = O) amide I., 1651 cm ^-1 in (C = O) in the carboxyl, 1599 cm ^-1 in (C = CC) + δ (ΝΗ), 1539 cm ^-1 in (NH) amide II., 1456 cm ^-1 in (CH), 694 cm ^{-1 in} δ (ΟH).

Example 6

Synthesis of complex 1-3, acetone / water reaction medium

C10 = c

Aq

1-3 t

ch ₃

4-Acetamido-2-hydroxybenzoic acid (3.9 g; M = 195.18; 0.02 mol) is dissolved with H ₃ BO ₃ (0.62 g, M = 61.83; 0.01 mol) in 50 cm ^{3 of} acetone with the addition of 4 cm ^{3 of} water. To this solution was added a solution of AgNO ³ (1.7 g; M = 169.87; 0.01 mol) in 5 cm ^{3 of} water. The reaction mixture was stirred at room temperature (25 ° C) for 1 hour and then at 35 ° C for 1 hour. A white-gray precipitate gradually emerges from the reaction mixture. Subsequently, the reaction mixture is cooled to 0-5 ° C, the precipitate of complex 1-3 is filtered off and dried at 40 ° C. Yield of complex 1-3 (C18HuNjOgAgB,

M-504.99) is 1.63 g, which represents a 32% yield.

The formation of complex 1-3 was confirmed by infrared spectroscopy, where new peaks with a frequency of 874 and 834 cm ^-1 in (B (OX) ₄ ) _M characteristic for the tetragonal alignment appeared in the spectrum.

FTIR (KBr): 3275 cm ¹ (NH), 1668 cm ^-1 v (C = O) Amide I, 1593 ^cm-1 (C = O) vkarboxylu, 20 at 1550 cm ¹ (C = CC) + δ (ΝΗ), 1539 cm ^-1 in (NH) amide II., 1497 cm ^-1 , 1431 cm ^-1 , 1377 cm

1165 cm ^-1 , 874 and 834 cm ^-1 in (B (OX) 4) -as and 694 cm ^-1 δ (Ο-Η).

Example 7

Synthesis of 4-hexanoylamino-2-hydroxy-benzoic acid

4-Amino-2-hydroxybenzoic acid (7.66 g; M = 153.14; 0.05 mol) is stirred in 50 cm ^{3 of} water, the pH is adjusted to 6 (10% aqueous NaOH) to give a solution. Dissolve 6,78 cm ³ (0,055 mol; M = 116,16; d = 0,93) together with 7,63 cm ^{3 of} triethylamine (0,055 mol; M = 101, d = 0,728) in 25 cm ^{3 of} acetone and cooled to 0 ° C. The acid is converted into the active form by addition of 5.24 cm @ ^{3 of} ethyl chloroformate (0.055 mol; M = 108.52; d = 1.139). After 5 minutes of vigorous stirring in the cold, the mixture is filtered through frit # 2, washed with 20 cm ^{3 of} acetone and transferred to a pre-prepared solution of 4-amino-235 hydroxybenzoic acid. The mixture was stirred at room temperature for 30 minutes. The reaction is then run for an additional 3 h at 60 ° C. After completion of the reaction (tested with Ehrlich reagent), the pH was adjusted from 6 to 3.0 by adding conc. 35% HCl. The resulting precipitate is filtered on a Bichner filter, the filter cake is resuspended in 20 cm ^{3 of} acetone, and after 20 minutes of vigorous stirring, the product is re-precipitated with distilled water and filtered again and dried at 40 ° C. The yield of chromatographically pure product is 10.23 g (C 11 H 11 NCl; M = 251.28), which represents 81.42%.

TLC: solid phase: ALUGRAM SIL G / UV ₂₅₄ (MACHEREY-NAGEL), mobile phase: 2-propanol / 1-propanol / ethyl acetate / water = 2/4/1/3 by volume.

The formation of the N-hexanoyl derivative was confirmed by infrared spectroscopy, where the vibration of 5 in (NH) 3495 cm ^-1 disappears and the characteristic vibration of the alkyl chain of 2983 cm ^-1 in (CH ₃ ) as,

2962 cm v _(CH2) as, 2860 cm ¹ (CH ₃₎ peaks specific to secondary amines in 1672 cm ¹ (C = O) Amide I and 1539 cm ^-1 v (NH) Amide II.

FTIR (KBr): 3312 cm ^-1 in (NH), 2983 cm -1 in (CH 3) as, 2962 cm ^-1 in (CH 2) as, 2860 cm ^-1 in (CH ₃ ) s, io 1672 cm ^-1 in (CH ₃ ) C = O) amide I., 1651 cm ^-1 in (C = O) in carboxyl, 1599 cm ^-1 in (C = CC) and δ (ΝΗ),

1539 cm ^-1 v (NH) Amide II., 1456 ^cm-1 (CH), 783 ^cm-1 RO (CH2), 694 ^cm-1 5 (OH).

Example 8 15

Synthesis of complex 1-4, ethanol / water reaction medium

C5H11 o = c

Ag ⁺

1-4 _ C5H11

4-Hexanoylamino-2-hydroxybenzoic acid (2.51 g; M = 251.28; 0.01 mol) is dissolved together with H ₃ BO ₃ (0.31 g, M = 61.83; 0.005 mol) in 20 cm ^{3 of} ethanol. To this solution is added a solution of AgNO ₃ (0.85 g; M = 169.87; 0.005 mol) in 5 cm ^{3 of} ethanol and 1 cm ^{3 of} water. The reaction mixture was stirred for ten minutes at room temperature (25 ° C) and then at 60 ° C for twenty minutes. A white-gray precipitate gradually emerges from the reaction mixture. The reaction mixture was then cooled to 0 to 0

5 ° C, the precipitate of the 1-4 complex is filtered off and dried at 40 ° C. The yield of Complex 1-4 (C ₂₆ H ₃₀ N ₂ O ₈ AgB, M = 617.21) was 1.55 g, representing a yield of 50.2%.

The formation of complex 1-4 was confirmed by infrared spectroscopy, where new peaks with a frequency of 871 and 835 cm ^-1 in (B (OX) ₄ f _{and with} characteristic for tetragonal alignment appear in the spectrum.

FTIR (KBr) 3286 ^cm-1 (NH), 2953 cm ^-1 v (CH3) as, 2930 cm ^-1 v (CH2) as, 2870 cm ^-1 v (CH3) s, 1664 ^cm-1 ( C = O) amide I., 1593 cm ^-1 in (C = O) in carboxyl, 1550 cm ^-1 , 1523 cm ^-1 , 1497 cm ^-1 , 1434 cm ^-1 in (CH) scissor vibrations, 1373 cm ^-1 , 871 and 835 cm ^-1, 783 cm ¹ <a (CH2), 694 cm ^-1 δ (Ο-Η).

Example 9

Preparation of P1-1 g of denatured alcohol containing 96% ethanol is mixed with 50 g of water, in which 0.4 g of the silver complex compound of the formula I-1 is dissolved in this solution. This solution is very suitable for controlling mold in households (eg on wet walls) or for preventive protection of wood, eg window frames. The liquid preparation must be used within 24 hours of mixing the components. The silver content of the preparation is 0.094 g, which represents 0.0936% by weight, relative to the total weight of the preparation. The boron content of the preparation is 0.01024 g (0.0102% by weight). The above elements were determined by atomic emission photometry with inductively coupled plasma (Laboratory of Atomic Spectrometry, Faculty of Chemical Technology, University of Pardubice).

Example 10

PI-2 io

Water of 40 g is mixed with 10 g of 3% H2O2. To this solution is added 50 g of denatured alcohol (96%), in which 0.4 g of the complex silver compound of formula 1-1 is dissolved with stirring. This solution is very suitable for controlling mold in households (eg on wet walls) or for preventive protection of wood, eg window frames. The preparation is also very suitable for disinfection. The liquid preparation should be used within 2 years of mixing the components. The silver content of the preparation is 0.0936% by weight, based on the total weight of the preparation. The boron content of the preparation is 0,0102% by weight,

Example 11

The PI-3 g of denatured alcohol containing 96% ethanol is mixed with 50 g of water, in which 0.4 g of the complex silver compound of formula I-1 and 0.01 g of Crystal Violet (CL 42555) are dissolved with stirring. Said solution is very suitable for preventive protection of wood, eg wooden structures. The liquid preparation must be used within 24 hours of mixing the components. The silver content of the preparation is 0.0936% by weight, based on the total weight of the preparation. The boron content of the preparation is 0.0102% by weight.

Example 12

P2-1 g of denatured alcohol with an ethanol content of 96% is mixed with 50 g of water, in which 0.4 g of the silver complex compound of the formula I-2 is dissolved with stirring. Said solution is very suitable for disinfecting objects where fungi and molds are present, preferably before painting. The liquid preparation must be used within 24 hours of mixing the components. The silver content of the formulation is 0.0768 g, which is 0.0765% by weight based on the total weight of the formulation. The boron content of the preparation is 0,01024 g (0,01% by weight),

Example 13

P2-2 g of denatured alcohol containing 96% ethanol is mixed with 50 g of water, in which 0.1 g of the complex silver compound of formula 1-2 and 0.01 g of Malachite green (CL 42000) are dissolved with stirring. This solution is very suitable for preventive protection of plasters against painting. The liquid preparation must be used within 24 hours of mixing the components. The silver content of the composition is 0.025% by weight, based on the total weight of the composition. The boron content of the preparation is 0.0025% by weight.

Example 14

Preparation P3-1

50 g of denatured alcohol with an ethanol content of 96% are mixed with 50 g of water, in which 0.4 g of the complex silver compound of the formula 1-3 is dissolved with stirring. Said solution is very suitable for disinfecting objects where fungi and molds are present, preferably before painting. The liquid preparation must be used within 24 hours of mixing the components. The silver content of the formulation is 0.085 g, which is 0.085% by weight based on the total weight of the formulation. The boron content of the preparation is 0.0085 g (representing 0.0085% by weight).

Example 15

P3-2 g of denatured alcohol containing 96% ethanol is mixed with 10 g of water, and 0.05 g of the complex silver compound 1-3 is dissolved in this solution with stirring. This solution is very suitable for the protection of thin wood materials, such as plywood or wrapping paper for industrial goods. The liquid preparation must be used within 24 hours of mixing the components. The silver content of the preparation is 0.01 g, which is 0.01% by weight, based on the total weight of the preparation. The boron content of the preparation is 0.001 g (representing 0.001% by weight).

Example 16

P4-1 g of denatured alcohol with an ethanol content of 96% is mixed with 10 g of water, in which 0.2 g of the complex silver compound of the formula 1-4 and 0.01 g of Crystal violet (Cl 42555) are dissolved with stirring. This solution is very suitable for preventive protection of wooden structures, eg window frames, against the actual color coating. The liquid preparation must be used within 24 hours of mixing the components. The silver content of the formulation is 0.035 g, which is 0.035% by weight based on the total weight of the formulation. The boron content of the preparation is 0.0035 g (representing 0.0035% by weight).

Claims (19)

40 PATENT CLAIMS 1. Complex compounds of boric acid, salicylic acid or derivatives thereof and silver of general formula I: Ag wherein X = H, NH _2, NHC (= O) R, where R is H, or generally Ci _to C _alkyl. (I) _ I 1 _ 2. A process for the preparation of a complex compound of formula (I), characterized in that a solution of one molar boric acid unit and two molar units of salicylic acid or a derivative thereof in a polar solvent is prepared with stirring, wherein the concentration of salicylic acid or a derivative thereof is 0. The solution is prepared at a temperature ranging from 0 ° C to the boiling point of a polar solvent, then one molar unit of silver nitrate is added to the solution of boric acid and salicylic acid or a derivative thereof in the polar solvent under stirring. the solution is cooled to 0 to 50 ° C 25 ° C and the resulting precipitate of the complex is then filtered off and dried at 25-80 ° C. io A process according to claim 2, characterized in that a solution of boric acid and salicylic acid or a derivative thereof in a polar solvent is prepared at room temperature. The process according to claim 2 or 3, wherein the polar solvent is selected from the group consisting of water, ethanol, 1-propanol, 2-propanol, acetone or mixtures thereof. Process according to any one of claims 2 to 4, characterized in that the silver nitrate is added in the form of a solution having a silver nitrate concentration ranging from 0.2 to 91% by weight in a solvent selected from the group consisting of water, ethanol or a mixture thereof. a temperature in the range of 0 ° C to the boiling point of the solvent. 6. The process of claim 5 wherein the silver nitrate solution is prepared at room temperature. Process according to any one of claims 2 to 4, characterized in that silver nitrate 25 is added in the form of a solid. 8. A composition for controlling fungi, fungi and wood-destroying insects, characterized in that it contains at least one complex compound of the formula I as active ingredient, furthermore solvents and, if appropriate, suitable accompanying substances. Composition according to Claim 8, characterized in that it contains a mixture of water and a C ₂ to C ₃ alcohol as solvent. Composition according to claim 8 or 9, characterized in that it contains colorants and stabilizers as accompanying substances. 11. A composition according to claim 10, wherein the dye is a basic dye. Composition according to claim 11, characterized in that the basic dye is Crystal 40 violet or Malachite green. 13. The composition of claim 10, wherein the stabilizer is hydrogen peroxide. 14. A composition according to claim 9, characterized in that it comprises from 0.001 to 10 wt. % of a plexic compound of formula I, 25 to 98 wt. % C ₂ to C ₃ alcohol and 2 to 75 wt. water and optionally accompanying substances. Preparation according to claim 14, characterized in that it contains colorants and stabilizers as accompanying substances. 16. The composition of claim 15, further comprising 0.01 to 5 wt. dyes. 17. The composition of claim 16, wherein the dye is a basic dye. A composition according to claim 17, wherein the basic dye is Crystal Violet or Malachite Green. A composition according to any one of claims 15 to 18, characterized in that it comprises up to % 0.6 wt. hydrogen peroxide, based on the weight of water in the formulation.