CA2169195A1 - Thiocarbamoyl compounds used as antimicrobial agents - Google Patents
Thiocarbamoyl compounds used as antimicrobial agentsInfo
- Publication number
- CA2169195A1 CA2169195A1 CA002169195A CA2169195A CA2169195A1 CA 2169195 A1 CA2169195 A1 CA 2169195A1 CA 002169195 A CA002169195 A CA 002169195A CA 2169195 A CA2169195 A CA 2169195A CA 2169195 A1 CA2169195 A1 CA 2169195A1
- Authority
- CA
- Canada
- Prior art keywords
- formula
- methyl
- compounds
- phenyl
- methoxyacrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/716—Esters of keto-carboxylic acids or aldehydo-carboxylic acids
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/18—One oxygen or sulfur atom
- C07D231/20—One oxygen atom attached in position 3 or 5
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
- C07D231/56—Benzopyrazoles; Hydrogenated benzopyrazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
Abstract
The application relates to novel thiocarbamoyl compounds of the formula (I)
Description
2 1 69 ~ 9~
LeA30240PCT - 1-Thioca~bamoyl compounds ~ rl~JL~T~
The application relates to novel thiocarbamoyl compounds, to their preparation and to their use for protecting industrial materials.
Thiocarbamoyl compounds and their use in the protection of materials are S known and are described for example in (DE 4 117 385). These compounds, however, have the disadvantage that they do not in all cases have an adequate microbicidal action and, furthermore, are washed out of the materials to be protected. Consequently, long-term protection is not ensured by these known compounds.
The application therefore relates to the novel thiocarbamoyl compounds ofthe formula (I) OH
R-(CH2)n ~, R' \l-- N N (I) ~- N ~ R2 in which R', R2 and R3, in each case independently of one another, represent hydrogen 15or methyl, and R4 represents cyclopentyl or cyclopentenyl, n represents the number 0 or 1, and their metal salt complexes and acid addition products.
Particularly preferred compounds of the formula (I) are those in which R', R2 - 21 ~ib~5 and R3 represent hydrogen and n represents the number 0 and, in particular, the compound of the formula (I) in which R', R2, R3 represent hydrogen, n represents the number 0, R4 represents cyclopentyl.
The compounds of the formula (I) are obtained by reacting formyl acid 5 derivatives of the formula (II) R--(CH2)n CH--COOR
(II) in which n, R3 and R4 have the meanings given above and R represents methyl, ethyl, n-, i-propyl or n-, i-, s- or t-butyl with thiosemicarbazides ofthe formula (III) -NH2-NH-CS-NRIR2 (III) if desired in the presence of a diluent or solvent and/or of a base.
In this reaction, from 0.8 to 1.0 mol of thiosemicarbazide is preferably added per mole of a-formylacetic acid derivative.
Bases added are preferably sodium hydroxide, potassium hydroxide or potassium tert.-butylate, preferably in approximately equimolar amounts.
Suitable solvents or diluents are in particular alcohols such as ethanol or aromatic hydrocarbons such as toluene.
The condensation reaction is carried out within a relatively large temperature range. The thiosemicarbazone formation which takes place initially is carried out at temperatures from 20 to 110C, preferably from 60 to 90C. The cyclocondensation reaction which takes place after the addition of base is performed at temperatures from 20 to 100C, preferably from 20 to 40C.
The 1-thiocarbamoyl compounds of the formula (I) according to the invention are isolated from the reaction mixtures by known methods. The general procedure is to free the reaction mixtures from the solvent and to treat the residue with aqueous hydrochloric acid. The pyrazoles which precipitate in this S procedure are separated off by filtration with suction. However, it is also possible to pour the reaction mixture directly into a large excess of dilute hydrochloric acid and to filter off the pyrazoles which are deposited as a precipitate.
The thiosemicarbazides of the formula (III) are known or are obtainable by generally known preparation methods.
The formyl acid derivatives of the formula (II) are novel and are likewise a subject of the application.
They are obtained by formylating esters of the formula (IV~
R4-(CH2)n-CH2-CooR (I~
in which R4, n and R have the meaning given above with bases, for example NaH, in solvents or diluents, such as cyclohexane and DMF, for example, with amine acid esters, such as methyl or ethyl esters.
The formyl acid derivatives of the formula (II) are also obtained by hydroformylating corresponding o"B lln~tllrated esters by generally known methods, as described for example in EP-417,597 or DE-2,643,205.
The active compounds ofthe formula (I) and the compositions accordingto the invention have a strong microbicidal action and can be employed in practice for combatting unwanted microorganisms. The active compounds of the formula (I) and the compositions according to the invention are suitable for protecting 216~195 industrial materials ~in~t infestation and destruction by unwanted mlcroorganlsms.
Industrial materials in the present context are non-living materials which have been prepared for use in industry. Industrial materials which are to be protected S by active compounds according to the invention ~in~t microbial change or destruction can be, for example, adhesives, sizes, paper and card, textiles, leather, wood, coating compositions and articles made of plastic, cooling lubricants and other materials which may be infested or decomposed by microor~ni~m.c. In the context of the materials to be protected it is also 10 possible to mention sections of production plants, for example cooling water circuits, which may be adversely affected by multiplication of microor~ni.~m~
In the context of the present invention, industrial materials which may be mentioned with prefcle,lce are adhesives, sizes, papers and cards, leather, wood, coating compositions, cooling lubricants and heat-transfer fluids, particularly 15 preferably coating compositions.
Microor&~ni~m~ which can cause degradation of or a change in industrial materials are, for example, bacteria, fungi, yeasts, algae and slime organisms.
The active compounds and compositions according to the invention preferably act ~&~in~t fungi, especially moulds, wood-discolouring and wood-destroying 20 fungi (Basidiomycetes) and ~in~t slime or~ni~m~ and algae.
Microorganisms of the following genera may be mentioned by way of example:
Alternaria, such as Alternaria tenuis, Aspergillus, such as Aspergillus niger, Chaetomium, such as Chaetomium globosum, 25 Coniophora, such as Coniophora puetana, Lentinus, such as Lentinus tigrinus, Penicillium, such as Penicillium glaucum, Polyporus, such as Polyporus versicolor, Aureobasidium, such as Aureobasidium pullulans, . 5 Sclerophoma, such as Sclerophoma pityophila, Trichoderma, such as Trichoderma viride, Escherichia, such as Escherichia coli, Pseudomonas, such as Pseudomonas aeruginosa, 5 Staphylococcus, such as Staphylococcus aureus.
Depending on their particular physical and/or chemical properties, the active compounds of the formula (I) can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and very fine capsules in polymeric substances.
10 These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is, liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surface-activeagents, that is, emulsifying agents and/or dispersing agents, and/or foam-forming agents. In the case of the use of water as an extender, organic solvents15 can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, 20 such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, as well as water; by liquefied gaseous extenders or carriers are meant liquids which are gaseous at ambient temperature and under atmospheric pressure, for 25 example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers there are suitable: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, alumina and silicates; as solid 30 carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example non-5 ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters,polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as albumen hydrolysisproducts; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.
10 Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Other additives can be mineral and vegetable oils.
15 It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarindyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrientssuch as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The active compounds of the formula (I) according to the invention are 20 preferably employed for protecting coatings ~in.~t infestation and destruction by unwanted microorganisms.
In the present context, a coating is to be understood as being a coat produced on a substrate by coating materials. The coating can have penetrated to a greater or lesser extent into the substrate. It may comprise one or more layers 25 and be prepared by processes such as brushing, spraying, dipping, flow coating or the like.
The compounds of the formulae (I) are incorporated into the coating 21691q5 compositions or into intermediates for the preparation of the coating composi-tions by conventional methods, for example by mixing the active compounds with the other components.
Coating compositions according to the invention therefore contain, in addition S to at least one fungicidal active compound of the formula (I), generally conventional coating components in, for example, liquid, paste-like or pulverulent form, e~mples being - colorants, such as pigments or dyes, preferably pigments. Examples are titanium dioxide, zinc oxide and iron oxide.
10 - binders, for example oxidatively drying alkyd resins, vinyl polymers and vinyl copolymers, acrylic polymers and acrylic copolymers, polymer powders, novolaks, amino resins, polyester resins, epoxy resins, silicone resins, isocyanate resins, preferably vinyl polymers and vinyl copolymers, acrylic polymers and acrylic copolymers and other binders which can be used in water-dilutable coating materials.
In addition, the coatings contain if desired the following additives - fillers, for example heavy spar, calcite, dolomite and talc, - solvents, for example alcohols, ketones, esters, glycol ethers and aliphatic and aromatic hydrocarbons, 20 - and thickeners and thixotropic agents, dispersants and wetting agents, driers, anti~ikinn in g agents, levelling agents, antifoaming agents, corrosion inhibitors, UV absorbers, fragrances, antistatics, antifreezes.
The following coating compositions or intermediates in the preparation of coating compositions may preferably be mentioned:
21~g~5 - Sizes and adhesives based on the known animal, vegetable or synthetic raw materials.
- Polymer dispersions, such as latex dispersions or dispersions based on other polymers.
5 - Starch solutions, starch dispersions or starch slurries or other products based on starch, for example printing thickeners.
- Slurries of other raw materials such as colour pigments (e.g. iron oxide pigments, carbon black pigments, titanium dioxide pigments) or slurries of fillers such as kaolin or calcium carbonate.
10 - Concrete additives based, for example, on molasses or ligninsulphonates.
- Bitumen emulsions.
- Precursors and intermediates of the chemical industry, for example in the production and storage of dyes.
- Inks or water colours.
15 - Emulsion paints for the coatings industry.
- Layers and finishes.
The effectiveness and the spectrum of action of the active compounds of the formulae (I) and/or the compositions, precursors or, quite generally, formulations which can be produced therefrom can be increased by adding, if 20 desired, further antimicrobially active compounds, fungicides, bactericides, herbicides, insecticides or other active compounds for enlarging the spectrum of action or for obtaining particular effects such as, for example, additional protection against insects. These mixtures may possess a broader spectrum of action than the compounds according to the invention.
25 In this context, synergistic effects are obtained in many cases, i.e. the activity of the mixture is greater than the activity of the individual components.
Examples of particularly advantageous co-components are the following compounds:
Tnazoles such as:
21691~5 .~ g amitrole, azocyclotin, BAS 480F, bitertanol, difenoconazole, fenbuconazole, fenchlorazole, fenethanil, fluquinconazole, flusilazole, flutriafol, imibenconazole, isozofos, myclobutanil, metconazole, epoxyconazole, paclobutrazol, penconazole, propioconazole, (~)-cis- 1-(4-chlorophenyl)-2-(lH- 1,2,4-triazol- 1-yl)-cycloheptanol, tetraconazole, triadimefon, triadimenol, triapenthenol, triflumizole, triticonazole, uniconazole and the metal salts and acid adducts thereo Imidazoles such as:
imazalil, pefurazoate, prochloraz, triflumizole, 2-(1-tert-butyl)- 1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol, thiazolecarboxanilides such as 2',6'-dibromo-2-methyl-4-trifluoromethoxy-4'-trifluoromethyl- 1,3-thiazole-5-carboxanilide, 1-imidazolyl- 1-(4'-chlorophenoxy)-3,3-dimethylbutan-2-one and the metal salts and acid adducts thereof.
M ethyl (E)- 2- [2- [6- (2- cyanophenoxy)pyrimidin- 4- yloxy]phenyl~ 3 -methoxyacrylate, methyl (E)-2-[2-[6-(2-thioamidophenoxy)pyrimidin-4-yloxy]phenyl]- 3- methoxyacrylate, methyl (E)- 2- [2- [6- (2-fluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate,methyl(E)-2-[2-[6-(2,6-difluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate,methyl (E)-2- [2- [3-(pyrimidin-2-yloxy)phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2- [2- [3-(5-methylpyrimidin-2-yloxy)-phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2- [2- [3-(phenyl-sulphonyloxy)phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[3-(4-nitrophenoxy)phenoxy]phenyl]-3-methoxyacrylate, methyl (1~)- 2- [2- phenoxyphenyl] - 3 - methoxyacrylate, methyl (E)- 2- [2- (3, 5-dimethylbenzoyl)pyrrol- 1-yl]-3-methoxyacrylate, methyl (E)-2- [2-(3-methoxyphenoxy)phenyl]-3-methoxyacrylate,methyl(E)-2-[2-(2-phenylethen-1-yl)-phenyl]-3-methoxyacrylate, methyl (E)-2-[2-(3,5-dichlorophenoxy)-pyridin- 3- yl]- 3- methoxyacrylate, methyl (~)- 2- (2- (3- ( 1 ,1 , 2, 2-tetrafluoroethoxy)phenoxy)phenyl)- 3- methoxyacrylate, methyl (~)- 2-(2- [3-(alpha- hydroxybenzyl)phenoxy]phenyl)- 3- methoxyacrylate, methyl (~)- 2- (2- (4-phenoxypyridin-2-yloxy)phenyl)-3-methoxyacrylate, methyl (_)-2-[2-(3-n-21 6~1 95 propyloxyphenoxy)phenyl] 3- methoxyacrylate, methyl (E)- 2- [2- (3 -isopropyloxyphenoxy)phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[3-(2-fluorophenoxy)pehnoxy]phenyl]- 3- methoxyacrylate, methyl (E)- 2- [2- (3-ethoxyphenoxy)phenyl]-3-methoxyacrylate, methyl (~)-2-[2-(4-tert.-butyl-pyridin-2-yloxy)phenyl]-3-methoxyacrylate, methyl (_)-2- [2- [3-(3-cyanophenoxy)phenoxy]phenyl]-3-methoxyacrylate, methyl (~)-2-[2-(3-methylpyridin-2-yloxymethyl)phenyl]-3-methoxyacrylate, methyl (E)-2- [2- [6-(2- methylphenoxy)pyrimidin- 4- yloxy]phenyl] - 3- methoxyacrylate, methyl (E)-2- [2-(5-bromopyridin-2-yloxymethyl)phenyl]-3-methoxyacrylate, methyl (E)-2-[2-(3-(3-iodopyridin-2-yloxy)phenoxy)phenyl]-3-methoxyacrylate, methyl(E)-2-[2-[6-(2-chloropyridin-3-yloxy)pyrimidin-4-yloxy]phenyl]-3-methoxy-acrylate,(E),(l~)methyl-2- [2-(5,6-dimethylpyrazin-2-ylmethyloximinomethyl)-phenyl]- 3- methoxyacrylate, (E)methyl- 2- {2- [6-(6- methylpyridin- 2-yloxy)pyrimidin-4-yloxy]-phenyl}3-methoxyacrylate, (E),(E)methyl-2- {2-(3-methoxyphenyl)methyloximinomethyl]phenyl}3-methoxyacrylate, (E)methyl-3 2- ~2-(6-(2-azidophenoxy)-pyrimidin-4-yloxy]phenyl}3-methoxyacrylate, (E),(E)methyl-2- {2- [6-phenylpyrimidin-4-yl)-methyloximinomethyl]phenyl}3-methoxyacrylate, (E), (E)methyl- 2- {2- [(4- chlorophenyl)-methyloximinomethyl]phenyl}3-methoxyacrylate, (E)methyl-2-{2-[6-(2-n-propylphenoxy)- 1,3,5-triazin-4-yloxy]phenyl}-3-methoxyacrylate, (E), (E)methyl- 2- {2- [(3- nitrophenyl)methyloximinomethyl]phenyl}- 3-methoxyacrylate;
succinate dehydlv~.,ase inhibitors such as:
fenfuram, furcarbanil, cyclafluramid, furmecyclox, seedvax, metsulfovax, pyrocarbolid, oxycarboxin, shirlan, mebenil (mepronil), benodanil, flutolanil (Moncut); naphthalene derivatives such as terbinafine, naftifine, butenafine, 3-chloro-7-(2-aza-2,7,7-trimethyl-oct-3-en-5-ine);
sulphenamides such as dichlofluanid, tolylfluanid, folpet, fluorfolpet, captan, captofol; benzimidazoles such as carbendazim, benomyl, furathiocarb, fuberidazole, thiophonate-methyl, thiabendazole or salts thereof;
morpholine derivatives such as tridemorph, fenpropimorph, falimorph, dimethomorph, dodemorph, aldimorph, fenpropidin and their salts with arylsulphonic acids, for example p-toluenesulphonic acid and p-dodecylphenyl-sulphonic acid;
dithiocarbamate, cufraneb, ferbam, mancopper, mancozeb, maneb, metam, 5 metiram, thiram zeneb, ziram;
benzothiazoles such as 2-mercaptobenzothiazole;
benzamides such as 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide;
boron compounds such as boric acid, boric esters, borax;
formaldehyde and formaldehyde donor compounds such as benzyl alcohol 10 mono-(poly)-hemiformal, oxazolidines, hexa-hydro-S-triazines, N-methylolchloroacetamide, paraformaldehyde, nitropyrin, oxolinic acid, tecloftalam;
tris-N - (cyclohexyldiazeniumdioxy)- aluminium, N - (cyclo-hexyldiazeniumdioxy)-tributyltin and K salts, bis-N-15 (cyclohexyldiazeniumdioxy)-copper;
N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N - octyl- isothiazolin- 3- one, N - octyl- isothiazolin- 3- one, 4, 5-trimethylene- isothiazolinones, 4, 5-benzisothiazolinones, N - methylolchloro-acetamide;
20 aldehydes such as cinnamaldehyde, formaldehyde, glutaraldehyde, ~-bromo-cinnamaldehyde;
thiocyanates such as thiocyanatomethylthiobenzothiazole, methylenebisthiocyanate, etc.;
quaternary ammonium compounds such as benzyldimethyltetradecylammonium 25 chloride, benzyldimethyldodecylammonium chloride, didecyldimethylammonium chloride;
iodine derivatives such as diiodomethyl p-tolyl sulphone, 3-iodo-2-propinyl alcohol, 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2,3-diiodo-2-propenyl-ethylcarbamate, 2,3,3-triiodoallyl alcohol, 3-bromo-2,3-diiodo-2-30 propenyl alcohol, 3-iodo-2-propinyl n-hexylcarbamate, 3-iodo-2-propinyl cyclohexylcarbamate, 3-iodo-2-propinyl phenylcarbamate;
phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophen, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol and the alkali metal and alkaline earth metal salts thereof;
microbicides with an activated halogen group, such as chloroacetamide, 5 bronopol, bronidox, tectamers such as 2-bromo-2-nitro-1,3-propanediol, 2-bromo-4'-hydroxy-acetophenone, 2,2-dibromo-3-nitrile-propionamide, 1,2-dibromo-2,4-dicyanobutane, ~-bromo-~-nitrostyrene;
pyridines such as 1-hydroxy-2-pyridinethione (and their Na, Fe, Mn, Zn salts), tetrachloro-4-methylsulphonylpyridine, pyrimethanol, mepanipyrim, dipyrithion, 1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2(1H)-pyridine;
metal soaps such as tin, copper, zinc naphthenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate;
metal salts such as copper hydroxycarbonate, sodium dichromate, potassium dichromate, potassium chromate, copper sulphate, copper chloride, copper borate, zinc fluorosilicate, copper fluorosilicate;
oxides such as tributyltin oxide, Cu2O, CuO, ZnO;
dialkyldithiocarbamates such as Na and Zn salts of dialkyldithiocarbamates, tetramethylthiuram disulphide, potassium N-methyl-dithiocarbamate;
nitriles such as 2,4,5,6-tetrachloroisophthalodinitrile, disodium cyano-dithioimidocarbamate;
quinolines such as 8-hydroxyquinoline and Cu salts thereof;
mucochloric acid, 5-hydroxy-2(5H)-furanone;
LeA30240PCT - 1-Thioca~bamoyl compounds ~ rl~JL~T~
The application relates to novel thiocarbamoyl compounds, to their preparation and to their use for protecting industrial materials.
Thiocarbamoyl compounds and their use in the protection of materials are S known and are described for example in (DE 4 117 385). These compounds, however, have the disadvantage that they do not in all cases have an adequate microbicidal action and, furthermore, are washed out of the materials to be protected. Consequently, long-term protection is not ensured by these known compounds.
The application therefore relates to the novel thiocarbamoyl compounds ofthe formula (I) OH
R-(CH2)n ~, R' \l-- N N (I) ~- N ~ R2 in which R', R2 and R3, in each case independently of one another, represent hydrogen 15or methyl, and R4 represents cyclopentyl or cyclopentenyl, n represents the number 0 or 1, and their metal salt complexes and acid addition products.
Particularly preferred compounds of the formula (I) are those in which R', R2 - 21 ~ib~5 and R3 represent hydrogen and n represents the number 0 and, in particular, the compound of the formula (I) in which R', R2, R3 represent hydrogen, n represents the number 0, R4 represents cyclopentyl.
The compounds of the formula (I) are obtained by reacting formyl acid 5 derivatives of the formula (II) R--(CH2)n CH--COOR
(II) in which n, R3 and R4 have the meanings given above and R represents methyl, ethyl, n-, i-propyl or n-, i-, s- or t-butyl with thiosemicarbazides ofthe formula (III) -NH2-NH-CS-NRIR2 (III) if desired in the presence of a diluent or solvent and/or of a base.
In this reaction, from 0.8 to 1.0 mol of thiosemicarbazide is preferably added per mole of a-formylacetic acid derivative.
Bases added are preferably sodium hydroxide, potassium hydroxide or potassium tert.-butylate, preferably in approximately equimolar amounts.
Suitable solvents or diluents are in particular alcohols such as ethanol or aromatic hydrocarbons such as toluene.
The condensation reaction is carried out within a relatively large temperature range. The thiosemicarbazone formation which takes place initially is carried out at temperatures from 20 to 110C, preferably from 60 to 90C. The cyclocondensation reaction which takes place after the addition of base is performed at temperatures from 20 to 100C, preferably from 20 to 40C.
The 1-thiocarbamoyl compounds of the formula (I) according to the invention are isolated from the reaction mixtures by known methods. The general procedure is to free the reaction mixtures from the solvent and to treat the residue with aqueous hydrochloric acid. The pyrazoles which precipitate in this S procedure are separated off by filtration with suction. However, it is also possible to pour the reaction mixture directly into a large excess of dilute hydrochloric acid and to filter off the pyrazoles which are deposited as a precipitate.
The thiosemicarbazides of the formula (III) are known or are obtainable by generally known preparation methods.
The formyl acid derivatives of the formula (II) are novel and are likewise a subject of the application.
They are obtained by formylating esters of the formula (IV~
R4-(CH2)n-CH2-CooR (I~
in which R4, n and R have the meaning given above with bases, for example NaH, in solvents or diluents, such as cyclohexane and DMF, for example, with amine acid esters, such as methyl or ethyl esters.
The formyl acid derivatives of the formula (II) are also obtained by hydroformylating corresponding o"B lln~tllrated esters by generally known methods, as described for example in EP-417,597 or DE-2,643,205.
The active compounds ofthe formula (I) and the compositions accordingto the invention have a strong microbicidal action and can be employed in practice for combatting unwanted microorganisms. The active compounds of the formula (I) and the compositions according to the invention are suitable for protecting 216~195 industrial materials ~in~t infestation and destruction by unwanted mlcroorganlsms.
Industrial materials in the present context are non-living materials which have been prepared for use in industry. Industrial materials which are to be protected S by active compounds according to the invention ~in~t microbial change or destruction can be, for example, adhesives, sizes, paper and card, textiles, leather, wood, coating compositions and articles made of plastic, cooling lubricants and other materials which may be infested or decomposed by microor~ni~m.c. In the context of the materials to be protected it is also 10 possible to mention sections of production plants, for example cooling water circuits, which may be adversely affected by multiplication of microor~ni.~m~
In the context of the present invention, industrial materials which may be mentioned with prefcle,lce are adhesives, sizes, papers and cards, leather, wood, coating compositions, cooling lubricants and heat-transfer fluids, particularly 15 preferably coating compositions.
Microor&~ni~m~ which can cause degradation of or a change in industrial materials are, for example, bacteria, fungi, yeasts, algae and slime organisms.
The active compounds and compositions according to the invention preferably act ~&~in~t fungi, especially moulds, wood-discolouring and wood-destroying 20 fungi (Basidiomycetes) and ~in~t slime or~ni~m~ and algae.
Microorganisms of the following genera may be mentioned by way of example:
Alternaria, such as Alternaria tenuis, Aspergillus, such as Aspergillus niger, Chaetomium, such as Chaetomium globosum, 25 Coniophora, such as Coniophora puetana, Lentinus, such as Lentinus tigrinus, Penicillium, such as Penicillium glaucum, Polyporus, such as Polyporus versicolor, Aureobasidium, such as Aureobasidium pullulans, . 5 Sclerophoma, such as Sclerophoma pityophila, Trichoderma, such as Trichoderma viride, Escherichia, such as Escherichia coli, Pseudomonas, such as Pseudomonas aeruginosa, 5 Staphylococcus, such as Staphylococcus aureus.
Depending on their particular physical and/or chemical properties, the active compounds of the formula (I) can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and very fine capsules in polymeric substances.
10 These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is, liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surface-activeagents, that is, emulsifying agents and/or dispersing agents, and/or foam-forming agents. In the case of the use of water as an extender, organic solvents15 can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, 20 such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, as well as water; by liquefied gaseous extenders or carriers are meant liquids which are gaseous at ambient temperature and under atmospheric pressure, for 25 example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers there are suitable: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, alumina and silicates; as solid 30 carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example non-5 ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters,polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as albumen hydrolysisproducts; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.
10 Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Other additives can be mineral and vegetable oils.
15 It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarindyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrientssuch as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The active compounds of the formula (I) according to the invention are 20 preferably employed for protecting coatings ~in.~t infestation and destruction by unwanted microorganisms.
In the present context, a coating is to be understood as being a coat produced on a substrate by coating materials. The coating can have penetrated to a greater or lesser extent into the substrate. It may comprise one or more layers 25 and be prepared by processes such as brushing, spraying, dipping, flow coating or the like.
The compounds of the formulae (I) are incorporated into the coating 21691q5 compositions or into intermediates for the preparation of the coating composi-tions by conventional methods, for example by mixing the active compounds with the other components.
Coating compositions according to the invention therefore contain, in addition S to at least one fungicidal active compound of the formula (I), generally conventional coating components in, for example, liquid, paste-like or pulverulent form, e~mples being - colorants, such as pigments or dyes, preferably pigments. Examples are titanium dioxide, zinc oxide and iron oxide.
10 - binders, for example oxidatively drying alkyd resins, vinyl polymers and vinyl copolymers, acrylic polymers and acrylic copolymers, polymer powders, novolaks, amino resins, polyester resins, epoxy resins, silicone resins, isocyanate resins, preferably vinyl polymers and vinyl copolymers, acrylic polymers and acrylic copolymers and other binders which can be used in water-dilutable coating materials.
In addition, the coatings contain if desired the following additives - fillers, for example heavy spar, calcite, dolomite and talc, - solvents, for example alcohols, ketones, esters, glycol ethers and aliphatic and aromatic hydrocarbons, 20 - and thickeners and thixotropic agents, dispersants and wetting agents, driers, anti~ikinn in g agents, levelling agents, antifoaming agents, corrosion inhibitors, UV absorbers, fragrances, antistatics, antifreezes.
The following coating compositions or intermediates in the preparation of coating compositions may preferably be mentioned:
21~g~5 - Sizes and adhesives based on the known animal, vegetable or synthetic raw materials.
- Polymer dispersions, such as latex dispersions or dispersions based on other polymers.
5 - Starch solutions, starch dispersions or starch slurries or other products based on starch, for example printing thickeners.
- Slurries of other raw materials such as colour pigments (e.g. iron oxide pigments, carbon black pigments, titanium dioxide pigments) or slurries of fillers such as kaolin or calcium carbonate.
10 - Concrete additives based, for example, on molasses or ligninsulphonates.
- Bitumen emulsions.
- Precursors and intermediates of the chemical industry, for example in the production and storage of dyes.
- Inks or water colours.
15 - Emulsion paints for the coatings industry.
- Layers and finishes.
The effectiveness and the spectrum of action of the active compounds of the formulae (I) and/or the compositions, precursors or, quite generally, formulations which can be produced therefrom can be increased by adding, if 20 desired, further antimicrobially active compounds, fungicides, bactericides, herbicides, insecticides or other active compounds for enlarging the spectrum of action or for obtaining particular effects such as, for example, additional protection against insects. These mixtures may possess a broader spectrum of action than the compounds according to the invention.
25 In this context, synergistic effects are obtained in many cases, i.e. the activity of the mixture is greater than the activity of the individual components.
Examples of particularly advantageous co-components are the following compounds:
Tnazoles such as:
21691~5 .~ g amitrole, azocyclotin, BAS 480F, bitertanol, difenoconazole, fenbuconazole, fenchlorazole, fenethanil, fluquinconazole, flusilazole, flutriafol, imibenconazole, isozofos, myclobutanil, metconazole, epoxyconazole, paclobutrazol, penconazole, propioconazole, (~)-cis- 1-(4-chlorophenyl)-2-(lH- 1,2,4-triazol- 1-yl)-cycloheptanol, tetraconazole, triadimefon, triadimenol, triapenthenol, triflumizole, triticonazole, uniconazole and the metal salts and acid adducts thereo Imidazoles such as:
imazalil, pefurazoate, prochloraz, triflumizole, 2-(1-tert-butyl)- 1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol, thiazolecarboxanilides such as 2',6'-dibromo-2-methyl-4-trifluoromethoxy-4'-trifluoromethyl- 1,3-thiazole-5-carboxanilide, 1-imidazolyl- 1-(4'-chlorophenoxy)-3,3-dimethylbutan-2-one and the metal salts and acid adducts thereof.
M ethyl (E)- 2- [2- [6- (2- cyanophenoxy)pyrimidin- 4- yloxy]phenyl~ 3 -methoxyacrylate, methyl (E)-2-[2-[6-(2-thioamidophenoxy)pyrimidin-4-yloxy]phenyl]- 3- methoxyacrylate, methyl (E)- 2- [2- [6- (2-fluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate,methyl(E)-2-[2-[6-(2,6-difluorophenoxy)pyrimidin-4-yloxy]phenyl]-3-methoxyacrylate,methyl (E)-2- [2- [3-(pyrimidin-2-yloxy)phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2- [2- [3-(5-methylpyrimidin-2-yloxy)-phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2- [2- [3-(phenyl-sulphonyloxy)phenoxy]phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[3-(4-nitrophenoxy)phenoxy]phenyl]-3-methoxyacrylate, methyl (1~)- 2- [2- phenoxyphenyl] - 3 - methoxyacrylate, methyl (E)- 2- [2- (3, 5-dimethylbenzoyl)pyrrol- 1-yl]-3-methoxyacrylate, methyl (E)-2- [2-(3-methoxyphenoxy)phenyl]-3-methoxyacrylate,methyl(E)-2-[2-(2-phenylethen-1-yl)-phenyl]-3-methoxyacrylate, methyl (E)-2-[2-(3,5-dichlorophenoxy)-pyridin- 3- yl]- 3- methoxyacrylate, methyl (~)- 2- (2- (3- ( 1 ,1 , 2, 2-tetrafluoroethoxy)phenoxy)phenyl)- 3- methoxyacrylate, methyl (~)- 2-(2- [3-(alpha- hydroxybenzyl)phenoxy]phenyl)- 3- methoxyacrylate, methyl (~)- 2- (2- (4-phenoxypyridin-2-yloxy)phenyl)-3-methoxyacrylate, methyl (_)-2-[2-(3-n-21 6~1 95 propyloxyphenoxy)phenyl] 3- methoxyacrylate, methyl (E)- 2- [2- (3 -isopropyloxyphenoxy)phenyl]-3-methoxyacrylate, methyl (E)-2-[2-[3-(2-fluorophenoxy)pehnoxy]phenyl]- 3- methoxyacrylate, methyl (E)- 2- [2- (3-ethoxyphenoxy)phenyl]-3-methoxyacrylate, methyl (~)-2-[2-(4-tert.-butyl-pyridin-2-yloxy)phenyl]-3-methoxyacrylate, methyl (_)-2- [2- [3-(3-cyanophenoxy)phenoxy]phenyl]-3-methoxyacrylate, methyl (~)-2-[2-(3-methylpyridin-2-yloxymethyl)phenyl]-3-methoxyacrylate, methyl (E)-2- [2- [6-(2- methylphenoxy)pyrimidin- 4- yloxy]phenyl] - 3- methoxyacrylate, methyl (E)-2- [2-(5-bromopyridin-2-yloxymethyl)phenyl]-3-methoxyacrylate, methyl (E)-2-[2-(3-(3-iodopyridin-2-yloxy)phenoxy)phenyl]-3-methoxyacrylate, methyl(E)-2-[2-[6-(2-chloropyridin-3-yloxy)pyrimidin-4-yloxy]phenyl]-3-methoxy-acrylate,(E),(l~)methyl-2- [2-(5,6-dimethylpyrazin-2-ylmethyloximinomethyl)-phenyl]- 3- methoxyacrylate, (E)methyl- 2- {2- [6-(6- methylpyridin- 2-yloxy)pyrimidin-4-yloxy]-phenyl}3-methoxyacrylate, (E),(E)methyl-2- {2-(3-methoxyphenyl)methyloximinomethyl]phenyl}3-methoxyacrylate, (E)methyl-3 2- ~2-(6-(2-azidophenoxy)-pyrimidin-4-yloxy]phenyl}3-methoxyacrylate, (E),(E)methyl-2- {2- [6-phenylpyrimidin-4-yl)-methyloximinomethyl]phenyl}3-methoxyacrylate, (E), (E)methyl- 2- {2- [(4- chlorophenyl)-methyloximinomethyl]phenyl}3-methoxyacrylate, (E)methyl-2-{2-[6-(2-n-propylphenoxy)- 1,3,5-triazin-4-yloxy]phenyl}-3-methoxyacrylate, (E), (E)methyl- 2- {2- [(3- nitrophenyl)methyloximinomethyl]phenyl}- 3-methoxyacrylate;
succinate dehydlv~.,ase inhibitors such as:
fenfuram, furcarbanil, cyclafluramid, furmecyclox, seedvax, metsulfovax, pyrocarbolid, oxycarboxin, shirlan, mebenil (mepronil), benodanil, flutolanil (Moncut); naphthalene derivatives such as terbinafine, naftifine, butenafine, 3-chloro-7-(2-aza-2,7,7-trimethyl-oct-3-en-5-ine);
sulphenamides such as dichlofluanid, tolylfluanid, folpet, fluorfolpet, captan, captofol; benzimidazoles such as carbendazim, benomyl, furathiocarb, fuberidazole, thiophonate-methyl, thiabendazole or salts thereof;
morpholine derivatives such as tridemorph, fenpropimorph, falimorph, dimethomorph, dodemorph, aldimorph, fenpropidin and their salts with arylsulphonic acids, for example p-toluenesulphonic acid and p-dodecylphenyl-sulphonic acid;
dithiocarbamate, cufraneb, ferbam, mancopper, mancozeb, maneb, metam, 5 metiram, thiram zeneb, ziram;
benzothiazoles such as 2-mercaptobenzothiazole;
benzamides such as 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide;
boron compounds such as boric acid, boric esters, borax;
formaldehyde and formaldehyde donor compounds such as benzyl alcohol 10 mono-(poly)-hemiformal, oxazolidines, hexa-hydro-S-triazines, N-methylolchloroacetamide, paraformaldehyde, nitropyrin, oxolinic acid, tecloftalam;
tris-N - (cyclohexyldiazeniumdioxy)- aluminium, N - (cyclo-hexyldiazeniumdioxy)-tributyltin and K salts, bis-N-15 (cyclohexyldiazeniumdioxy)-copper;
N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N - octyl- isothiazolin- 3- one, N - octyl- isothiazolin- 3- one, 4, 5-trimethylene- isothiazolinones, 4, 5-benzisothiazolinones, N - methylolchloro-acetamide;
20 aldehydes such as cinnamaldehyde, formaldehyde, glutaraldehyde, ~-bromo-cinnamaldehyde;
thiocyanates such as thiocyanatomethylthiobenzothiazole, methylenebisthiocyanate, etc.;
quaternary ammonium compounds such as benzyldimethyltetradecylammonium 25 chloride, benzyldimethyldodecylammonium chloride, didecyldimethylammonium chloride;
iodine derivatives such as diiodomethyl p-tolyl sulphone, 3-iodo-2-propinyl alcohol, 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2,3-diiodo-2-propenyl-ethylcarbamate, 2,3,3-triiodoallyl alcohol, 3-bromo-2,3-diiodo-2-30 propenyl alcohol, 3-iodo-2-propinyl n-hexylcarbamate, 3-iodo-2-propinyl cyclohexylcarbamate, 3-iodo-2-propinyl phenylcarbamate;
phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophen, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol and the alkali metal and alkaline earth metal salts thereof;
microbicides with an activated halogen group, such as chloroacetamide, 5 bronopol, bronidox, tectamers such as 2-bromo-2-nitro-1,3-propanediol, 2-bromo-4'-hydroxy-acetophenone, 2,2-dibromo-3-nitrile-propionamide, 1,2-dibromo-2,4-dicyanobutane, ~-bromo-~-nitrostyrene;
pyridines such as 1-hydroxy-2-pyridinethione (and their Na, Fe, Mn, Zn salts), tetrachloro-4-methylsulphonylpyridine, pyrimethanol, mepanipyrim, dipyrithion, 1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2(1H)-pyridine;
metal soaps such as tin, copper, zinc naphthenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate;
metal salts such as copper hydroxycarbonate, sodium dichromate, potassium dichromate, potassium chromate, copper sulphate, copper chloride, copper borate, zinc fluorosilicate, copper fluorosilicate;
oxides such as tributyltin oxide, Cu2O, CuO, ZnO;
dialkyldithiocarbamates such as Na and Zn salts of dialkyldithiocarbamates, tetramethylthiuram disulphide, potassium N-methyl-dithiocarbamate;
nitriles such as 2,4,5,6-tetrachloroisophthalodinitrile, disodium cyano-dithioimidocarbamate;
quinolines such as 8-hydroxyquinoline and Cu salts thereof;
mucochloric acid, 5-hydroxy-2(5H)-furanone;
4, 5- dichlorodithiazolinone, 4, 5-benzodithiazolinone, 4, 5-trimethylene~lithi~701inone, 4,5-dichloro-(3H)-1,2-dithiol-3-one, 3,5-dimethyl-tetrahydro- 1,3,5-thiadiazine-2-thione, N-(2-p-chlorobenzoylethyl)-hexaminium chloride, potassium N-hydroxymethyl-N'-methyl-dithiocarbamate, 2-oxo-2-(4-hydroxy-phenyl)acethydroximic chloride, phenyl 2-chloro-cyano-vinyl sulphone, phenyl 1,2-dichloro-2-cyano-vinyl sulphone;
Ag, Zn or Cu-containing zeolites alone or included in polymeric active compounds.
Very particular preference is given to mixtures with azaconazole, bromuconazole, cyproconazole, dichlobutrazol, diniconazole, hexaconazole, metaconazole, penconazole, propiconazole, tebuconazole, methyl (E)-methoximino[a-(o-tolyloxy)-o-tolyl)]acetate, methyl (E)-2-{2-[6-5 (2-cyanophenoxy)pyrimidin-4-yloxy]phenyl~3-methoxyacrylate, methfuroxam, carboxin, fenpiclonil, 4-(2,2-difluoro- 1,3-benzodioxol-4-yl)- lH-pyrrol-3-carbonitrile, butenafine, im~7~lil, N-methyl-isothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, N-octylisothiazolin-3-one, benzisothiazolinones, N-(2-hydroxypropyl)-amino-methanol, benzyl alcohol (hemi)-formal, 10 glutaraldehyde, omadine, dimethyl dicarbonate.
Furthermore, highly effective mixtures are also prepared with the following active compounds:
Fungicides:
acypetacs, 2-aminobutane, ampropylfos, ~nil~7ine, benalaxyl, bupirimate, 15 quinomethionate, chloroneb, chlozolinate, cymoxanil, dazomet, diclomezine, dichloram, diethofencarb, dimethirimol, diocab, dithianon, dodine, drazoxolon, edifenphos, ethirimol, etridiazole, fenarimol, fenitropan, fentin acetate, fentin hydroxide, ferimzone, flu~7in~m, fluromide, fllls~llf~mide, flutriafol, fosetyl,fthalide, furalaxyl, guazatine, hymexazol, iprobenfos, iprodione, isoprothiolane, 20 metalaxyl, methasulfocarb, nitrothal- isopropyl, nuarimol, of urace, oxadiyl,perflurazoate, pencycuron, phosdiphen, pimaricin, piperalin, procymidone, propamocarb, propineb, pyrazophos, pyrifenox, pyroquilon, quintozene, tar oils, tecnazene, thicyofen, thiophanate-methyl, tolclofos-methyl, triazoxide, trichlamide, tricyclazole, triforine, vinclozolin.
25 Insecticides:
Phosphoric esters such as azinphos-ethyl, azinphos-methyl, a- 1(4-chlorophenyl)-4-(O-ethyl, S-propyl)phosphoryloxy-pyrazole, chlorpyrifos, coumaphos, demeton, demeton-S-methyl, diazinon, dichlorvos, dimethoate, ethoate, ethoprophos, etrimfos, fenitrothion, fenthion, heptenophas, parathion, . 2169195 parathion-methyl, phosalone, phoxim, pirimiphos-ethyl, pirimiphos-methyl, profenofos, prothiofos, sulfprofos, triazophos and trichlorphon;
carbamates such as aldicarb, bendiocarb, a-2-(1-methylpropyl)-phenyl methylcarbamate, butocarboxim, butoxycarboxim, carbaryl, carbofuran, 5 carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, pirimicarb, promecarb, propoxur and thiodicarb;
organosilicon compounds, preferably dirnethyl(phenyl)silyl-methyl 3-phenoxybenzyl ethers such as dimethyl-(4-ethoxyphenyl)-silylmethyl 3-phenoxybenzyl ether or (dimethylphenyl)-silyl-methyl 2-phenoxy-6-10 pyridylmethyl ethers such as, for example, dimethyl-(9-ethoxy-phenyl)-silylmethyl 2-phenoxy-6-pyridylmethyl ether or [(phenyl)-3-(3-phenoxyphenyl)-propyl](dimethyl)-silanes such as, for example, (4-ethoxyphenyl)-[3-(4-fluoro-3-phenoxyphenyl-propyl]dimethyl-silane, silafluofen;
15 pyrethroids such as allethrin, alphamethrin, bioresmethrin, byfenthrin, . cycloprothrin, cyfluthrin, decamethrin, cyhalothrin, cypermethrin, deltamethrin, alpha-cyano-3-phenyl-2-methylbenz,vl 2,2-dimethyl-3-(2-chloro-2-trifluoromethylvinyl)cyclopropanecarboxylate, fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, permethrin, resmethrin and 20 tralomethrin;
nitroimines and nitromethylenes such as 1- [(6-chloro-3-pyridinyl)-methyl]-4,5-dihydro-N-nitro- lH-imidazol-2-amine (imidacloprid), N-[(6-chloro-3-pyridyl)methyl-]N2-cyano-N'-methylacetamide (NI-25);
abamectin, AC 303, 630, acephate, acrinathrin, alanycarb, aldoxycarb, aldrin, 25 amitraz, azamethiphos, Bacillus thuringiensis, phosmet, phosphamidon, phosphine, prallethrin, propaphos, propetamphos, prothoate, pyraclofos, pyrethrins, pyridaben, pyridafenthion, pyriproxyfen, quinalphos, RH-7988, rotenone, sodium fluoride, sodium hexafluorosilicate, sulfotep, sulphuryl fluoride, tar oils, teflubenzuron, tefluthrin, temephos, terbufos, tetrachlor-30 vinphos, tetramethrin, 0-2-tert-butyl-pyrimidin-5-yl o-isopropyl phosphorothiate, thiocyclam, thiofanox, thiometon, tralomethrin, triflumuron, trimethacarb, vamidothion, Verticillium ~ ~c~nii, XMC, xylylcarb, benfuracarb, . 2169195 bensultap, bifenthrin, bioallethrin, MERbioallethrin (S)-cyclopentenyl isomer, bromophos, bromophos-ethyl, buprofezin, c~ fos, calcium polysulphide, carbophenothion, cartap, quinomethionate, chlordane, chlorfenvinphos, chlorfluazuron, chlormephos, chloropicrin, chlorpyrifos, cyanophos, beta-5 cyfluthrin, alpha-cypermethrin, cyophenothrin, cyromazine, dazomet, DDT, demeton-S-methyl sulphone, diafenthiuron, dialifos, dicrotophos, diflu-benzuron, dinoseb, deoxabenzofos, diaxacarb, disulfoton, DNOC, empenthrin, endosulfan, EPN, esfenvalerate, ethiofencarb, ethion, etofenprox, fenobucarb, fenoxycarb, fensulphothion, fipronil, flucycloxuron, flufenprox, flufenoxuron, 10 fonofos, formetanate, formothion, fosmetl~ n, furathiocarb, heptachlor, hexaflumuron, hydramethylnon, hydrogen cyanide, hydroprene, IPSP, i~70fos, isofenphos, isoprothiolane, isoxathione, iodfenphos, kadethrin, lindane, malathion, mecarbam, mephosfolan, mercurous, chloride, metam, metarthizium, anisopliae, methacrifos, methamidophos, methidathion, 15 methiocarb, methoprene, methoxychlor, methyl isothiocyanate, metholcarb, mevinphos, monocrotophos, naled, neodiprion, sertifer NPV, nicotine, omethoate, oxydemeton-methyl, pentachlorophenol, petroleum oils, phenothrin, phenthoate, phorate;
Molluscicides:
20 Fentin acetate, metaldehyde, methiocarb. Niclosamide, thiodicarb, trimethacarb.
Algicides:
Copper sulphate, dichlororphen, endothal, fentin acetate, quinoclamine.
Helbicides:
25 acetochlor, acifluorfen, aclonifen, acrolein, alachlor, alloxydim, ametryn, amidosulfuron, amitrole, ammonium sulfamate, anilofos, asulam atrazine, aziptrotryne, benazolin, benfluralin, benfuresate, bensulfuron, bensulphide, bentazone, benzofencap, ben~thi~7--ron, bifenox, bilanafos, borax, dichlorprop, dichlorprop-P, diclofop, diethatyl, difenoxuron, difenzoquat, diflufenican, .
dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethipin, dimethylarsinic acid, dinitramine, dinoseb, dinoseb, dinoseb acetate, dinoseb, bromacil, bromobutide, bromofenoxim, bromoxynil, butachlor, butamifos, fuenachlor, butralin, butylate, carbetamide, CGA 184927, chlormethoxyfen, 5 chloramben, chlorbromuron, chlorbutam, chlorfurenol, chloridazon, chlorimuron, chlornitrofen, chloroacetic acid, achloropicrin, chlorotoluron, chloroxuron, chlorprepham, chlorsulfuron, chlorthal, chlorthiamid, cinmethylin, cinofulsuron, clethodim, clomazone, clomeprop, clopyralid, cyanamide, cyanazine, dinoseb acetate, dinoterb, diphenamid, dipropetryn, diquat, dithiopyr, diduron, DNOC, PPX-A 788, DPX-E96361, DSMA, eglinazine, endothal, EPTC, esprocarb, ethalfluralin, ethidimuron, ethofumesate, fenoxaprop, fenoxaprop-P, fenuron, flamprop, flamprop-M, flazasulfuron, fluazifop, fluazifop-P, fluchloralin, flumeturon, fluorocgycofen,fluoronitrofen, flupropanate, flurenol, fluridone, flurochloridone, fluoroxypyr,15 cycloate, cycloxydim, 2,4-D, daimuron, dalapon, dazomet, 2,4-DB, desmedipham, desmetryn, dicamba, dichlorbenil, isoproturon, isouron, isoxaben, isoxapyrifop, lactofen, lenacil, linuron, LS830556, MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, mefenacet, mefluidide, metam, metamitron, metazachlor, methaben7tl i~1ron, methazole, methoproptryne, 20 methyldymron, methylisothiocyanate, metobromuron, fomosafen, fosamine, furyloxyfen, glufosinate, glyphosate, haloxyfop, hexazinone, imazamethabenz, imazapyr, im~7~quin, imazethapyr, ioxynil, isopropalin, propyzamide, prosulfocab, pyrazolynate, pyrazolsulfuron, pyrazoxyfen, pyributicarb, pyridate,quinclorac, quinmerac, quinocloamine, quizalofop, quizalofop-P, S-23121, 25 sethoxydim, sifuron, simazine, simetryn, SMY 1500, sodium chlorate, sulfometuron, tar oils, TCA, metolachlor, metoxuron, metribzin, metsulfuron, molinate, monalide, monolinuron, MSMA, naproanilide, napropamide, naptalam, neburon, nicosulfuron, nipyraclofen, norflurazon, orbencarb, oaryzalin, oxadiazon, oxyfluorfen, paraquat, pebulate, pendimethalin, 30 pentachlorophenol, pentaochlor, petroleum oils, phenmedipham, picloram, piperophos, pretilachlor, primisulfuron, prodiamine, proglinazine, propmeton, prometryn, propachlor, tebutam, tebuthiuron, terbacil, terbumeton, 21691~5 terbuthylazine, terbutryn, tlli~7~fluoron, thifensulfuron, thiobencarb, thiocarbazil, tioclorim, tralkoxydim, tri-allate, triasulfuron, tribenzuron, triclopyr, tridiphane, trietazine, trifluralin, IBI-C4874 vernolate, propanil, propaquizafop, propazine, propham.
S The wei~ht ratios of the active compounds in these active compound combinations can be varied within relatively wide ranges.
The active compound combinations preferably receive the active compound of the formula (I) to the extent of from 0.1 to 99.9%, in particular 1 to 75%, and with particular preference 5 to 50%, the remainder up to 100% being made up by one or more of the above-mentioned co-components.
The microbicidal compositions or concentrates which are used to protect the industrial materials contain the active compound or the active compound combination in a concentration of 0.01 and 95% by weight, in particular 0. lto 60% by weight.
The application concentrations of the active compounds or active compound combinations to be used depends on the nature and occurrence of the microorganisms to be combatted and on the composition of the material to be protected. The optimum quantity for use can be determined by series of tests.
In general, the application concentrations are in the range from 0.001 to 5% by weight, preferably from 0.05 to 1.0% by weight, based on the material to be protected.
The active compounds and compositions according to the invention make it possible in an advantageous manner to replace the microbicidal compositions which have been available to date by more effective compositions. They exhibit good stability and, advantageously, have a broad spectrum of action.
The Examples which follow serve to illustrate the invention. The invention is 216~1~5 not limited to the Examples.
2 1 6 q I 9 5 Prepa~ation examples Example 1 a~ N NH2 8 g of ethyl 2-formyl-2-cyclopentylacetate, prepared from the commercial 5 2-cyclopenteneacetic acid by esterification and formylation by known methods, were refluxed for 4 hours in 70 ml of ethanol with 3.9 g of thiosemicarbazide, 4.8 g of potassium tert.-butylate were added, and the mixture was allowed to stand for about 12 hours. Pouring onto ice/ 10% HCl gives 2.5C of the target compound of meltingpoint m.p.: 160C.
10 Example 2 OH S
~--~ N ~ N H
Analogously to Example 1, the compound of melting point m.p. 152C is obtained.
Example 2 OH S
~ INNJ~NH2 40.7 g of ethyl 3-cyclopentylpropionate are placed in 400 ml of DMF at from O to 5C, and 14.4 g of sodium hydride (80% in oil) are added. After dropwise addition of 200 ml of ethyl formate, the mixture is stirred at 25C for 24 h. The mixture is stirred into 1.6 1 of 10% HCI, extracted with 800 ml of methylene 2iG~1~5 chloride and distilled. 19.7 g (41%) are obtained of ethyl 2-formyl-3-cyclopentylpropionate of boiling point 117C/ 12 mm.
9.7 g of the oil obtained were heated under reflux in 80 ml of ethanol with 4.47 g of thiosemicarbazide for 4 h, 5.5 g of potassium tert-butylate were addedS at 25qC, and the mixture was stirred for 24 h. The mixture was then introducedinto 250 ml of 10% HCl to give, after recryst~lli7~tion from ethanol, 5 g (45%) ofthe target compound of meltingpoint 157C.
Ag, Zn or Cu-containing zeolites alone or included in polymeric active compounds.
Very particular preference is given to mixtures with azaconazole, bromuconazole, cyproconazole, dichlobutrazol, diniconazole, hexaconazole, metaconazole, penconazole, propiconazole, tebuconazole, methyl (E)-methoximino[a-(o-tolyloxy)-o-tolyl)]acetate, methyl (E)-2-{2-[6-5 (2-cyanophenoxy)pyrimidin-4-yloxy]phenyl~3-methoxyacrylate, methfuroxam, carboxin, fenpiclonil, 4-(2,2-difluoro- 1,3-benzodioxol-4-yl)- lH-pyrrol-3-carbonitrile, butenafine, im~7~lil, N-methyl-isothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, N-octylisothiazolin-3-one, benzisothiazolinones, N-(2-hydroxypropyl)-amino-methanol, benzyl alcohol (hemi)-formal, 10 glutaraldehyde, omadine, dimethyl dicarbonate.
Furthermore, highly effective mixtures are also prepared with the following active compounds:
Fungicides:
acypetacs, 2-aminobutane, ampropylfos, ~nil~7ine, benalaxyl, bupirimate, 15 quinomethionate, chloroneb, chlozolinate, cymoxanil, dazomet, diclomezine, dichloram, diethofencarb, dimethirimol, diocab, dithianon, dodine, drazoxolon, edifenphos, ethirimol, etridiazole, fenarimol, fenitropan, fentin acetate, fentin hydroxide, ferimzone, flu~7in~m, fluromide, fllls~llf~mide, flutriafol, fosetyl,fthalide, furalaxyl, guazatine, hymexazol, iprobenfos, iprodione, isoprothiolane, 20 metalaxyl, methasulfocarb, nitrothal- isopropyl, nuarimol, of urace, oxadiyl,perflurazoate, pencycuron, phosdiphen, pimaricin, piperalin, procymidone, propamocarb, propineb, pyrazophos, pyrifenox, pyroquilon, quintozene, tar oils, tecnazene, thicyofen, thiophanate-methyl, tolclofos-methyl, triazoxide, trichlamide, tricyclazole, triforine, vinclozolin.
25 Insecticides:
Phosphoric esters such as azinphos-ethyl, azinphos-methyl, a- 1(4-chlorophenyl)-4-(O-ethyl, S-propyl)phosphoryloxy-pyrazole, chlorpyrifos, coumaphos, demeton, demeton-S-methyl, diazinon, dichlorvos, dimethoate, ethoate, ethoprophos, etrimfos, fenitrothion, fenthion, heptenophas, parathion, . 2169195 parathion-methyl, phosalone, phoxim, pirimiphos-ethyl, pirimiphos-methyl, profenofos, prothiofos, sulfprofos, triazophos and trichlorphon;
carbamates such as aldicarb, bendiocarb, a-2-(1-methylpropyl)-phenyl methylcarbamate, butocarboxim, butoxycarboxim, carbaryl, carbofuran, 5 carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, pirimicarb, promecarb, propoxur and thiodicarb;
organosilicon compounds, preferably dirnethyl(phenyl)silyl-methyl 3-phenoxybenzyl ethers such as dimethyl-(4-ethoxyphenyl)-silylmethyl 3-phenoxybenzyl ether or (dimethylphenyl)-silyl-methyl 2-phenoxy-6-10 pyridylmethyl ethers such as, for example, dimethyl-(9-ethoxy-phenyl)-silylmethyl 2-phenoxy-6-pyridylmethyl ether or [(phenyl)-3-(3-phenoxyphenyl)-propyl](dimethyl)-silanes such as, for example, (4-ethoxyphenyl)-[3-(4-fluoro-3-phenoxyphenyl-propyl]dimethyl-silane, silafluofen;
15 pyrethroids such as allethrin, alphamethrin, bioresmethrin, byfenthrin, . cycloprothrin, cyfluthrin, decamethrin, cyhalothrin, cypermethrin, deltamethrin, alpha-cyano-3-phenyl-2-methylbenz,vl 2,2-dimethyl-3-(2-chloro-2-trifluoromethylvinyl)cyclopropanecarboxylate, fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, permethrin, resmethrin and 20 tralomethrin;
nitroimines and nitromethylenes such as 1- [(6-chloro-3-pyridinyl)-methyl]-4,5-dihydro-N-nitro- lH-imidazol-2-amine (imidacloprid), N-[(6-chloro-3-pyridyl)methyl-]N2-cyano-N'-methylacetamide (NI-25);
abamectin, AC 303, 630, acephate, acrinathrin, alanycarb, aldoxycarb, aldrin, 25 amitraz, azamethiphos, Bacillus thuringiensis, phosmet, phosphamidon, phosphine, prallethrin, propaphos, propetamphos, prothoate, pyraclofos, pyrethrins, pyridaben, pyridafenthion, pyriproxyfen, quinalphos, RH-7988, rotenone, sodium fluoride, sodium hexafluorosilicate, sulfotep, sulphuryl fluoride, tar oils, teflubenzuron, tefluthrin, temephos, terbufos, tetrachlor-30 vinphos, tetramethrin, 0-2-tert-butyl-pyrimidin-5-yl o-isopropyl phosphorothiate, thiocyclam, thiofanox, thiometon, tralomethrin, triflumuron, trimethacarb, vamidothion, Verticillium ~ ~c~nii, XMC, xylylcarb, benfuracarb, . 2169195 bensultap, bifenthrin, bioallethrin, MERbioallethrin (S)-cyclopentenyl isomer, bromophos, bromophos-ethyl, buprofezin, c~ fos, calcium polysulphide, carbophenothion, cartap, quinomethionate, chlordane, chlorfenvinphos, chlorfluazuron, chlormephos, chloropicrin, chlorpyrifos, cyanophos, beta-5 cyfluthrin, alpha-cypermethrin, cyophenothrin, cyromazine, dazomet, DDT, demeton-S-methyl sulphone, diafenthiuron, dialifos, dicrotophos, diflu-benzuron, dinoseb, deoxabenzofos, diaxacarb, disulfoton, DNOC, empenthrin, endosulfan, EPN, esfenvalerate, ethiofencarb, ethion, etofenprox, fenobucarb, fenoxycarb, fensulphothion, fipronil, flucycloxuron, flufenprox, flufenoxuron, 10 fonofos, formetanate, formothion, fosmetl~ n, furathiocarb, heptachlor, hexaflumuron, hydramethylnon, hydrogen cyanide, hydroprene, IPSP, i~70fos, isofenphos, isoprothiolane, isoxathione, iodfenphos, kadethrin, lindane, malathion, mecarbam, mephosfolan, mercurous, chloride, metam, metarthizium, anisopliae, methacrifos, methamidophos, methidathion, 15 methiocarb, methoprene, methoxychlor, methyl isothiocyanate, metholcarb, mevinphos, monocrotophos, naled, neodiprion, sertifer NPV, nicotine, omethoate, oxydemeton-methyl, pentachlorophenol, petroleum oils, phenothrin, phenthoate, phorate;
Molluscicides:
20 Fentin acetate, metaldehyde, methiocarb. Niclosamide, thiodicarb, trimethacarb.
Algicides:
Copper sulphate, dichlororphen, endothal, fentin acetate, quinoclamine.
Helbicides:
25 acetochlor, acifluorfen, aclonifen, acrolein, alachlor, alloxydim, ametryn, amidosulfuron, amitrole, ammonium sulfamate, anilofos, asulam atrazine, aziptrotryne, benazolin, benfluralin, benfuresate, bensulfuron, bensulphide, bentazone, benzofencap, ben~thi~7--ron, bifenox, bilanafos, borax, dichlorprop, dichlorprop-P, diclofop, diethatyl, difenoxuron, difenzoquat, diflufenican, .
dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethipin, dimethylarsinic acid, dinitramine, dinoseb, dinoseb, dinoseb acetate, dinoseb, bromacil, bromobutide, bromofenoxim, bromoxynil, butachlor, butamifos, fuenachlor, butralin, butylate, carbetamide, CGA 184927, chlormethoxyfen, 5 chloramben, chlorbromuron, chlorbutam, chlorfurenol, chloridazon, chlorimuron, chlornitrofen, chloroacetic acid, achloropicrin, chlorotoluron, chloroxuron, chlorprepham, chlorsulfuron, chlorthal, chlorthiamid, cinmethylin, cinofulsuron, clethodim, clomazone, clomeprop, clopyralid, cyanamide, cyanazine, dinoseb acetate, dinoterb, diphenamid, dipropetryn, diquat, dithiopyr, diduron, DNOC, PPX-A 788, DPX-E96361, DSMA, eglinazine, endothal, EPTC, esprocarb, ethalfluralin, ethidimuron, ethofumesate, fenoxaprop, fenoxaprop-P, fenuron, flamprop, flamprop-M, flazasulfuron, fluazifop, fluazifop-P, fluchloralin, flumeturon, fluorocgycofen,fluoronitrofen, flupropanate, flurenol, fluridone, flurochloridone, fluoroxypyr,15 cycloate, cycloxydim, 2,4-D, daimuron, dalapon, dazomet, 2,4-DB, desmedipham, desmetryn, dicamba, dichlorbenil, isoproturon, isouron, isoxaben, isoxapyrifop, lactofen, lenacil, linuron, LS830556, MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, mefenacet, mefluidide, metam, metamitron, metazachlor, methaben7tl i~1ron, methazole, methoproptryne, 20 methyldymron, methylisothiocyanate, metobromuron, fomosafen, fosamine, furyloxyfen, glufosinate, glyphosate, haloxyfop, hexazinone, imazamethabenz, imazapyr, im~7~quin, imazethapyr, ioxynil, isopropalin, propyzamide, prosulfocab, pyrazolynate, pyrazolsulfuron, pyrazoxyfen, pyributicarb, pyridate,quinclorac, quinmerac, quinocloamine, quizalofop, quizalofop-P, S-23121, 25 sethoxydim, sifuron, simazine, simetryn, SMY 1500, sodium chlorate, sulfometuron, tar oils, TCA, metolachlor, metoxuron, metribzin, metsulfuron, molinate, monalide, monolinuron, MSMA, naproanilide, napropamide, naptalam, neburon, nicosulfuron, nipyraclofen, norflurazon, orbencarb, oaryzalin, oxadiazon, oxyfluorfen, paraquat, pebulate, pendimethalin, 30 pentachlorophenol, pentaochlor, petroleum oils, phenmedipham, picloram, piperophos, pretilachlor, primisulfuron, prodiamine, proglinazine, propmeton, prometryn, propachlor, tebutam, tebuthiuron, terbacil, terbumeton, 21691~5 terbuthylazine, terbutryn, tlli~7~fluoron, thifensulfuron, thiobencarb, thiocarbazil, tioclorim, tralkoxydim, tri-allate, triasulfuron, tribenzuron, triclopyr, tridiphane, trietazine, trifluralin, IBI-C4874 vernolate, propanil, propaquizafop, propazine, propham.
S The wei~ht ratios of the active compounds in these active compound combinations can be varied within relatively wide ranges.
The active compound combinations preferably receive the active compound of the formula (I) to the extent of from 0.1 to 99.9%, in particular 1 to 75%, and with particular preference 5 to 50%, the remainder up to 100% being made up by one or more of the above-mentioned co-components.
The microbicidal compositions or concentrates which are used to protect the industrial materials contain the active compound or the active compound combination in a concentration of 0.01 and 95% by weight, in particular 0. lto 60% by weight.
The application concentrations of the active compounds or active compound combinations to be used depends on the nature and occurrence of the microorganisms to be combatted and on the composition of the material to be protected. The optimum quantity for use can be determined by series of tests.
In general, the application concentrations are in the range from 0.001 to 5% by weight, preferably from 0.05 to 1.0% by weight, based on the material to be protected.
The active compounds and compositions according to the invention make it possible in an advantageous manner to replace the microbicidal compositions which have been available to date by more effective compositions. They exhibit good stability and, advantageously, have a broad spectrum of action.
The Examples which follow serve to illustrate the invention. The invention is 216~1~5 not limited to the Examples.
2 1 6 q I 9 5 Prepa~ation examples Example 1 a~ N NH2 8 g of ethyl 2-formyl-2-cyclopentylacetate, prepared from the commercial 5 2-cyclopenteneacetic acid by esterification and formylation by known methods, were refluxed for 4 hours in 70 ml of ethanol with 3.9 g of thiosemicarbazide, 4.8 g of potassium tert.-butylate were added, and the mixture was allowed to stand for about 12 hours. Pouring onto ice/ 10% HCl gives 2.5C of the target compound of meltingpoint m.p.: 160C.
10 Example 2 OH S
~--~ N ~ N H
Analogously to Example 1, the compound of melting point m.p. 152C is obtained.
Example 2 OH S
~ INNJ~NH2 40.7 g of ethyl 3-cyclopentylpropionate are placed in 400 ml of DMF at from O to 5C, and 14.4 g of sodium hydride (80% in oil) are added. After dropwise addition of 200 ml of ethyl formate, the mixture is stirred at 25C for 24 h. The mixture is stirred into 1.6 1 of 10% HCI, extracted with 800 ml of methylene 2iG~1~5 chloride and distilled. 19.7 g (41%) are obtained of ethyl 2-formyl-3-cyclopentylpropionate of boiling point 117C/ 12 mm.
9.7 g of the oil obtained were heated under reflux in 80 ml of ethanol with 4.47 g of thiosemicarbazide for 4 h, 5.5 g of potassium tert-butylate were addedS at 25qC, and the mixture was stirred for 24 h. The mixture was then introducedinto 250 ml of 10% HCl to give, after recryst~lli7~tion from ethanol, 5 g (45%) ofthe target compound of meltingpoint 157C.
Claims (9)
1. Thiocarbamoyl compounds of the formula (I) (I) in which R1, R2 and R3, in each case independently of one another, represent hydrogen or methyl, and R4 represents cyclopentyl or cyclopentenyl, n represents the number 0 or 1, and their metal salt complexes and acid addition products.
2. Compounds of the formula (I) according to Claim 1, in which R1, R2 and R3 represent hydrogen and n represents the number 0.
3. Compound ofthe formula (I) accordingto Claim 1, in which R1, R2 and R3 represent hydrogen, n represents the number 0, R4 represents cyclopentyl.
4. Method of protecting industrial materials, characterized in that compounds of the formula (I) according to Claim 1 are applied to the materials to be protected or mixed with them.
5. Composition for protecting industrial materials, comprising at least one compound of the formula (I) according to Claim 1.
6. Use of compounds ofthe formula (I) accordingto Claim 1 for protecting materials against infestation and destruction by unwanted microorganisms.
7. Process for the preparation of compounds of the formula (I), characterized in that formyl acid derivatives of the formula (II) (II) in which n, R3 andR4 have the meanings given in Claim 1 and R
represents methyl, ethyl, n-, i-propyl or n-, i-, s- or t-butyl are reacted with thiosemicarbazides of the formula (III) NH2-NH-CS-NR1R2 (III) if desired in the presence of a diluent or solvent and/or of a base.
represents methyl, ethyl, n-, i-propyl or n-, i-, s- or t-butyl are reacted with thiosemicarbazides of the formula (III) NH2-NH-CS-NR1R2 (III) if desired in the presence of a diluent or solvent and/or of a base.
8. Formyl acid derivatives of the formula (II) (II) in which n, R3 and R4 have the meaning given in Claim 1 and R represents methyl, ethyl, n-, i-propyl or n-, s- or t-butyl.
9. Process for the preparation of compounds of the formula (II) (II) in which R3, R4 and R have the meanings given in Claim 8, characterized in that esters of the formula (IV) R4-(CH2)n-CH2-COOR (IV) in which R4, n and R have the meaning given above are formylated with bases, in solvents or diluents, with amine acid esters.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4326904.4 | 1993-08-11 | ||
| DE4326904 | 1993-08-11 | ||
| DE19944411243 DE4411243A1 (en) | 1994-03-31 | 1994-03-31 | 1-thiocarbamoyl-5-hydroxy-1,2-diazine derivs. |
| DEP4411243.2 | 1994-03-31 | ||
| PCT/EP1994/002534 WO1995004722A1 (en) | 1993-08-11 | 1994-07-29 | Thiocarbamoyl compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2169195A1 true CA2169195A1 (en) | 1995-02-16 |
Family
ID=25928504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002169195A Abandoned CA2169195A1 (en) | 1993-08-11 | 1994-07-29 | Thiocarbamoyl compounds used as antimicrobial agents |
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| Country | Link |
|---|---|
| EP (1) | EP0713485B1 (en) |
| JP (1) | JPH09501422A (en) |
| KR (1) | KR100346811B1 (en) |
| CN (1) | CN1082049C (en) |
| AT (1) | ATE165089T1 (en) |
| AU (1) | AU684541B2 (en) |
| BR (1) | BR9407232A (en) |
| CA (1) | CA2169195A1 (en) |
| CZ (1) | CZ289324B6 (en) |
| DE (1) | DE59405727D1 (en) |
| DK (1) | DK0713485T3 (en) |
| FI (1) | FI960588A (en) |
| HU (1) | HU215275B (en) |
| NO (1) | NO305556B1 (en) |
| PL (1) | PL181247B1 (en) |
| WO (1) | WO1995004722A1 (en) |
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| DE19510058A1 (en) * | 1995-03-20 | 1996-09-26 | Bayer Ag | Thiocarbamoyl compounds |
| WO2005070206A1 (en) * | 2004-01-23 | 2005-08-04 | Ishihara Sangyo Kaisha, Ltd. | Pest control composition and method of controlling pest |
| US8486293B2 (en) * | 2009-10-30 | 2013-07-16 | E I Du Pont De Nemours And Company | Hydrogen fluoride-HFC-254eb azeotrope and its uses |
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| DE4117385A1 (en) * | 1991-05-28 | 1992-12-03 | Bayer Ag | USE OF 1-THIOCARBAMOYL-5-HYDROXY-PYRAZOLES AS MICROBICIDES, NEW 1-THIOCARBAMOYL-5-HYDROXY-PYRAZOLES AND METHOD FOR THE PRODUCTION THEREOF |
-
1994
- 1994-07-29 HU HU9600300A patent/HU215275B/en not_active IP Right Cessation
- 1994-07-29 AU AU76101/94A patent/AU684541B2/en not_active Ceased
- 1994-07-29 DE DE59405727T patent/DE59405727D1/en not_active Expired - Fee Related
- 1994-07-29 AT AT94926134T patent/ATE165089T1/en not_active IP Right Cessation
- 1994-07-29 EP EP94926134A patent/EP0713485B1/en not_active Expired - Lifetime
- 1994-07-29 CZ CZ1996396A patent/CZ289324B6/en not_active IP Right Cessation
- 1994-07-29 PL PL94312966A patent/PL181247B1/en unknown
- 1994-07-29 CA CA002169195A patent/CA2169195A1/en not_active Abandoned
- 1994-07-29 KR KR1019960700644A patent/KR100346811B1/en not_active IP Right Cessation
- 1994-07-29 JP JP7506206A patent/JPH09501422A/en not_active Ceased
- 1994-07-29 WO PCT/EP1994/002534 patent/WO1995004722A1/en active IP Right Grant
- 1994-07-29 BR BR9407232A patent/BR9407232A/en not_active IP Right Cessation
- 1994-07-29 DK DK94926134T patent/DK0713485T3/en active
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1996
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| CZ289324B6 (en) | 2002-01-16 |
| DE59405727D1 (en) | 1998-05-20 |
| CZ39696A3 (en) | 1996-05-15 |
| AU684541B2 (en) | 1997-12-18 |
| KR100346811B1 (en) | 2002-11-30 |
| PL312966A1 (en) | 1996-05-27 |
| EP0713485B1 (en) | 1998-04-15 |
| JPH09501422A (en) | 1997-02-10 |
| EP0713485A1 (en) | 1996-05-29 |
| CN1128993A (en) | 1996-08-14 |
| NO960271D0 (en) | 1996-01-23 |
| AU7610194A (en) | 1995-02-28 |
| FI960588A0 (en) | 1996-02-08 |
| NO960271L (en) | 1996-01-23 |
| HU215275B (en) | 1998-11-30 |
| NO305556B1 (en) | 1999-06-21 |
| HU9600300D0 (en) | 1996-04-29 |
| HUT73562A (en) | 1996-08-28 |
| WO1995004722A1 (en) | 1995-02-16 |
| PL181247B1 (en) | 2001-06-29 |
| DK0713485T3 (en) | 1998-12-07 |
| CN1082049C (en) | 2002-04-03 |
| FI960588A (en) | 1996-02-08 |
| BR9407232A (en) | 1996-09-24 |
| ATE165089T1 (en) | 1998-05-15 |
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