NZ198768A - Wood preservative compositions containing triazolyl methyl ketals - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number 1 98768 1 98768 | Priority ..M'JP.-Af ! Conr,p!cC3 Easeiflcation FBed^7.'/?.?' ] Publication SJato; - - I258 • ■ ■ 0 • • rr, t. vn:.\ [lz\ « • • a fv*% ^ Patents Form No. 5 NEW ZEALAND PATENTS ACT 195 3 COMPLETE SPECIFICATION "VJOOD PRESERVATIVES" 'A -t/WEBASF AKTIENGESELLSCHAFT, a German Joint company organised and existing under the laws of the Federal Republic of Germany, of 6700 Ludwigshafen Federal Republic of Germany hereby declare the invention, for which I-/we pray that a patent may be granted to me/us , and the method by which it is to be performed, to be particularly described in and by the following statement:- (fojfosved by pape f A > o r 7 > r. y o / o u lA O.Z. 0050/034733 WOOD PRESERVATIVES The present invention relates to a wood preservative containing a triazolyl methyl ketal as active ingredient.

- Gorman Laid-Opon Applloo.t>-ion -DE-OS 2,551,560 dioc-looco the *tee of 1 (bota apyl) ^tllcyl 1H-1 ^0,4-trlaaolc kcfealo as fungicides ■In agpioultupo fop oombating phytopathogonte-fung-fcn ,IPhi" fnitipoimi:!a ■may also be employed on animalo and human beingo suffering from— diooaooc oauood by pathogonio mloroorganiomo4 We have now surprisingly found that triazolyl methyl ketals where R is alkyl of 2 to 3 carbon atoms, have a very good action on wood-discoloring fungi, wood-rot fungi and wood-destroying fungi. The compounds l-[2-(2,4-dichlorophenyl)-4-ethyl-l,3-dioxolan--2-yl-methyl]-lH-l,2,4-triazole (compound A) and l-[2-(2,4-di-20 chlorophenyl )-4-propyl-l,3-dioxolan-2-yl-methyl 3-1H-1,2,4-triazole (compund B) are particularly effective. The broad spectrum of action of the active ingredients in wood preservation could not have been foreseen, because other, prior art, triazole derivatives employed in agriculture, such as l-(4-chlorophenoxy)-3,3-dimethyl--1-(1H-1,2,4-triazol-l-yl)-2-butanone (compound 1) (Ciprrnian Ln1.flwQpea of the formula CI H0C-CH f R 17 OCT 385 198768 ' ' - 2 - O.Z. 00500/031733 ApyllouLtlon DE-03 2,g01,0(j3^ and bis-phenyl-(3-trifluoromethyl-phenyl)-l-(l,2,4-triazolyl)-methane (compound 2), are virtually ineffective on wood-discoloring and wood-rot fungi, in spite of the fact that they have an excellent fungicidal action on phytopathogenic fungi.

For instance the following wood- and paint-discoloring fungi, wood-rot fungi and wood-destroying fungi may be combated with the wood preservatives according to the invention: Pullularia (Aureobasidium pullulans), Sclerophoma pityophila, Ceratocystis 10 spec., Paecilomyces variotii, Hormiscium spec., Stemphylium spec., Phoma violacea, Cladosporium herbarum, Trichoderma viride, Chaetomium globosum, Humicola grisea, Merulius lacrimans, Coniophora puteana, Lentinus lepideus, Lenzites trabea, Trametes versicolor, Stereum hirsutum, and Pomes annosus.

The novel active ingredients may be used in formulations, such as solutions, emulsions, pastes and oil dispersions. The formulations generally contain from 0.1 to 90, and preferably from 0.25 to 50, wt56 of active ingredient. The application rates depend on the effect desired, and range from 0.5 to 8 g of active ingre- p dient per m of wood surface to be preserved, or 50 to 4,000 g of ■3 active ingredient per nr of wood. Paints contain for example 0.5 to 2 wt% of active ingredient. To protect wood-base materials, the active ingredients may be added as an emulsion or simply mixed with the adhesive, for instance in amounts of from 2 to 6 wt£.

The active ingredients are applied by brushing, spraying, atomizing, dipping, or by pressure impregnation or diffusion methods. s 7 c cress 1987 6 8 - 3 - O.Z. 00500/034733 To Increase the spectrum of action, or to achieve special effects, the novel active ingredients may also be combined with other active ingredients. Mixtures with the following compounds are particularly favorable: organotin compounds, such as tributyltin oxide and tributyltin benzoate methylene bis-thiocyanate alkyl-dimethyl-benzylammonium chloride cetylpyridinum chloride 10 chlorinated phenols, such as tetra- and pentachlorophenol tetrachloroisophthalic acid dinitrile 2-halobenzoic acid anilide N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide N,N-dimethyl-N'-phenyl-(N-fluoromethylthio)-sulfamide N-phenyl-N,N'-dimethyl-N'-fluorodichloromethylthiosulfonyl-dIamide methyl benzimidazole-2-carbamate 2-thiocyanomethyl-thiobenzothiazole copper naphthenate copper-8-oxyquinoline alkali metal and metal salts of N'-hydroxy-N-cyclohexyldiazenium oxide mercaptobenzothiazole N,N-dimethyl-N'-(dichlorofluoromethylthio)-sulfamide p-chlorophenyl-3-propargyl-formal 3-iodo-2-propynyl-butyl-carbamate. 198768 - 4 - O.Z. 00500/034733 EXAMPLE 1 To prepare an oily wood preservative containing 1% of active ingredient, 1 part (by weight) of compound A Is first dissolved, with slight heating, in 55 parts of a gasoline fraction rich in aromatics. Subsequently, 10 parts of an alkyd resin is added, and the mixture is made up, at room temperature, to 100 parts with white spirit.

Oily wood preservatives containing 0.25 to 5 wt# of active Ingredients A and B are prepared analogously.

To obtain water-resistant impregnation finishes, water repellents may be added to the oily wood preservatives. Examples of suitable substances are zinc stearate, aluminum stearate, and waxes. Color effects may also be obtained by incorporating inorganic or organic pigments or oil-soluble dyes Into the formulations.

To protect wood against fungus attack, usually from 50 to 200 ml of the oily wood preservatives given in Example 1 is 2 applied per m of wood surface, by brushing, spraying or dipping. EXAMPLE 2 Disc-shaped filter papers having a diameter of 13 mm and a thickness of 1 mm are impregnated with 0.2 ml solutions In acetone containing 200, 100, 50, 25 and 12.5 parts of active ingredient per million parts of solution (ppm). The discs are then placed on a 2% malt extract agar in Petri dishes which have been inoculated with spores of the wood-discoloring fungi Pullularia pullulans and. Trichoderma viride (green wood mold). The dishes are then incubated for 3 days at from 22° to 24°C. After this period, the fungi * 198768 - 5 " O.Z. 00500/034733 In the control dishes are well developed; the fungicidal action of the active ingredients is assessed from the fungus-free zones (halos) which have formed round the papers discs, as follows: - no halo = no fungicidal action + small halo < 2 mm = slight fungicidal action ++ average halo 2-6 mm = good fungicidal action +++ large halo > 5 ram = excellent fungicidal action. a) Pullularia pullulans Active ingredient ppm of active ingredient in solution 200 100 50 25 12.5 A +++ +++ +++ +++ +++ B +++ +++ +++ +++ +++ 1 + - - - - 2 + .

■ - -■ - - Control (no active Ingredient) b) Trlchoderma viride Active ingredient • • . ppm of 200 active 100 Ingredient in 50 25 solution 1.2.5 A ; +++ ++ ++ + + B 1 +++ ++ ++ + + 2 Control (no active ingredient) « 198768 - 6 - O.Z. 00500/034733 EXAMPLE 3 Active ingredients A and B and comparative agents 1 and 2 are dissolved in acetone and added, in amounts of 40, 20 and 10 ppm, to a liquid, 5% malt extract agar. The agar is poured into Petri dishes, and, after it has solidified, the nutrient agar (containing the fungicides) Is centrally inoculated with the mold and sap-stain fungus Chaetomium globosum. After the dishes have been incubated for 5 days at 25°C, the spread of the fungus colonies on the nutrient medium is assessed against the control (no active 10 ingredient added): 0 = no fungus growth (fungus mycelium killed) 1 = slight furigus growth (up to one third of the surface of the agar covered) 3 = average fungus growth (up to two thirds of the surface of the agar covered) = uncontrolled fungus growth (surface of agar completely covered) Active ... ppm of active Ingredient in nutrient agar ingredient 40 20 10 A 0 0 1 B 0 0 1 1 5 5 5 2 3 5 5 Control (no active ingredient) 5 1 98768 o.z. 00500/034733 Active ingredients A and B and dissolved in acetone and added, in amounts of 80, 40, and 20 ppm, to a 5% malt extract agar as described in Example 3» The agar is poured into Petri dishes and, after it has solidified, the nutrient agar (containing the fungicides) is centrally Inoculated with mycelium of the wood--destroying fungi Coniophora puteana and Trametes versicolor.

After the dishes have been incubated for 5 days at 25°C, the spread of the fungus colonies on the nutrient medium is assessed 10 against the control (no active Ingredient added): 0 = no fungus growth (fungus mycelium killed) 1 = slight fungus growth (up to one third of the surface of the agar covered) 3 = average fungus growth (up to two thirds of. the surface of the agar covered) = uncontrolled fungus growth (surface of agar completely covered) Active ... ppm of active Ingredient in nutrient agar ingredient Coniophora puteana Trametes versicolor 80 40 20 80 40 20 A 0 0 0 0 0 0 B 0 0 0 0 0 1 Control (no active ingredient) j » EXAMPLE 4 1 987 6$ - 8 - O.Z. 00500/034733 The results of these experiments show that the prior art fungicidal triazole derivatives 1 and 2 have no, or only a very slight, action on fungi in wood, whereas the fungicidal triazole derivatives A and B surprisingly have a very good fungicidal action on fungi which attack wood.

EXAMPLE 5 parts by weight of compound B is dissolved in a mixture consisting of 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 to 10 moles of ethylene oxide with 1 mole of oleic acld-N-monoethanolamide, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 2 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the solution into water and uniformly distributing It therein, an aqueous dispersion of the active ingredient is obtained.

EXAMPLE 6 To determine the activity on the wood-destroying fungi Coniophora puteana and Trametes versicolor, pine sapwood blocks 2 measuring 50x25x15 mm were coated at a rate of 100 g/m of wood surface with oily wood preservative formulations containing 1 vt% of active ingredient B. After the treated blocks had been stored for 4 weeks, they were placed, together with untreated blocks, In glass dishes containing the fungi Coniophora puteana or Trametes versicolor in a nutrient agar. The dishes were then incubated in an atmospheric laboratory at 22°C and a relative humidity of 7055. After

Claims (4)

» - 9 - 198768 O.Z. 00500/034733 3 months, the fungus mycelium attaching to the blocks was removed and the blocks were dried. The degree of wood destruction was then ascertained. Active ingredient ... % of active ingredient in the formulation Degree of fungal attack after a test period of three months Coniophora Trametes puteana versicolor 10 B Control (solvent only, without active Ingredient 3a/4b 1 4a Rating: 1 undamaged 2a slight local attack 2b slight overall attack 3a severe local attack 3b severe overall attack 4a local complete destruction 4b overal complete destruction. 20 1987o8 10 o.z. 00500/034733 r (k P/ What we claim Is:

1. A wood preservative comprising a solid or liquid carrier and a triazolyl methyl ketal of the formula CI clC^0H2-Cl I I H0C-CH d f 10 where R is alkyl of 2 or 3 carbon atoms.

2. A process for protecting wood against discoloration and destruction by fungi, wherein the wood is treated with a triazolyl methyl ketal of the formula CI ciCS^-cvO \ — ft N—'0 0 I I H-C-CH 1 R 20 where R is alkyl of 2 or 3 carbon atoms.

3. A wood preservative as claimed in claim 1 substantially as described herein with reference to any one of the Examples.

4. A process for protecting wood against discoloration and destruction by fungi, as claimed in claim 2 substantially as herein described with reference to any one of the Examples. BALDWIN, SON & CAREY -ATTOTNEYS for THE APr-i 'OA :TS N.Z. PA?;:*-.- 16J£f\'S?04