CA1289469C - Oxypyridinium salts and agents for combating microbes - Google Patents
Oxypyridinium salts and agents for combating microbesInfo
- Publication number
- CA1289469C CA1289469C CA000522967A CA522967A CA1289469C CA 1289469 C CA1289469 C CA 1289469C CA 000522967 A CA000522967 A CA 000522967A CA 522967 A CA522967 A CA 522967A CA 1289469 C CA1289469 C CA 1289469C
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- Prior art keywords
- alkenyl
- substituted
- formula
- alkyl
- unsubstituted
- Prior art date
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/65—One oxygen atom attached in position 3 or 5
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Environmental Sciences (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Pest Control & Pesticides (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
- Pyridine Compounds (AREA)
- Steering Control In Accordance With Driving Conditions (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Disclosed are microbicidal compositions contain-ing, as active ingredient, an effective amount of an 0-substituted 3-oxypyridinium salt of the formula I
where R1 is unsubstituted or substituted alkyl, alkenyl or alkynyl, R2 is unsubstituted or substituted alkyl, alkenyl or alkynyl, phenylalkyl or phenoxyalkyl, and X?
is an anion of an. acid. Also disclosed is a method of combating microbes outside the crop protection sector.
Disclosed are microbicidal compositions contain-ing, as active ingredient, an effective amount of an 0-substituted 3-oxypyridinium salt of the formula I
where R1 is unsubstituted or substituted alkyl, alkenyl or alkynyl, R2 is unsubstituted or substituted alkyl, alkenyl or alkynyl, phenylalkyl or phenoxyalkyl, and X?
is an anion of an. acid. Also disclosed is a method of combating microbes outside the crop protection sector.
Description
12894~9 Oxypyridinium salts and a~ents for_ combating microbes .
The present invention relates to a microbicidal composition containing 0-substituted 3-oxypyridinium salts for combating microbes, and a method of combatin~ mi-crobes.
More particularly, the present invention pro-poses a microbicidal composition for combating algae, bacteria or fungi of the non-phytopathogenic type, out-side the crop protection sector. This composition which contains a toxic amount of an 0-substituted 3-oxypyridinium salt of the formula:
[ ~~Rl ~
where R1 is an alkyl, alkenyl or alkynyl radical which is unsubstituted or substituted by at least one alkoxy, cycloalkoxy, phenylalkoxy or halogen, and has a total of 8 to 20 carbon atoms, R2 i8 unsubstituted or halogen-substituted alkyl, alkenyl or alkynyl of up to 8 carbon atoms, or one of the groups -(CH2)1 2~Ar, -(CH2)2 50CH21CHCH2Ar or -(CH2)2 6-0-Ar R
where Ar is l-naphthyl, 2-naphthyl, biphenyl or phenyl, phenyl being unsubstituted or substituted by F, Cl, Br, NO2~ 3CF3, CN~ Cl-13~alkYl~ C2_4-alkenyl or Cl 2-alkoxy and R is H, Cl-C2-alkyl, C3-C5-alkenyl or Cl-C5-alkoxy and X~ is F0, C10, B~0 or I0 or an anion which is the equivalent of an acid, have proved to have a good microbicidal action.
,'~i ~1 , , ~289469 - la -Examples of meanings for R are branched or straight-chain octyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, P 2 10alkYl-O-cs lgalkyl~ -0-cyclohexyl or -0-C3-C5-alkylphenyl with a total of 10 to 20 carbon at-oms. 2 Examples of meanings for R are Cl-C4-alkyl, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, allyl, 2-chloropropenyl, 2-bromopropenyl, 3-chloro-propenyl, but-2-en-1-yl, 2-methylpropenyl, 3-chlorobut-2-en-1-yl, propargyl or the radicals -(CH2)1 2-Ar or -(CH2)2 6-OAr, Ar denoting unsubstituted phenyl or phenyl containing one to three halogen substituents, such as 4-fluorophenyl, 3- or 4-chlorophenyl,4-bromophenyl, 3,4-dichlorophenyl, 2,4-dichlorophenyl, 2,6-dichloro-phenyl, and 2,4,6-dichlorophenyl.
/
..
. ;.
~289~69 ~ASF Aktiengesellschaft 2 O.Z. 0050/38~12 Examples of meanings for ~ are Cl~, ~r~ or an anion which is one equivalent of an acid, such as phenylsulfonic acid, p-methylphenyl-sulfonic acid or one equivalent of the sulfuric acid anion.
5 The 0-substituted 3-oxypyridinium salts of the formula I are obtained by reacting a compound of the formula R2X II, 1O where R2 and X have the above meanings, With an 0-substituted 3-oxypyridine derivative of the formula ~0--R1 ~NJ III, where R1 has the above meanings.
The reaction is carried out in bulk or if desired in the presence of an15 inert solvent or diluont at from 20 to 150, pref0rably 50 to 150, CC. The starting material of the formula III is advantageously reacted with up to 10 times the molar amount Ibased on III) of the alkylating agent of the 40rmula II.
20 Examples of preferred inert solvents or diluents are aliphatic or aromatic hydrocarbons or halohydrocarbons, such as pentane, cyclohexane, heptane, benzene, toluene, chlorobenzene and dichloro-benzenes; aliphatic ketones such as acetonQ, methyl ethyl ketone, diethyl ketone and cyclopentanone;
ethers such as diethyl ether, methyl tert-butyl ether, dimethoxyethane, 25 tetrahydrofuran and dioxane; esters such as ethyl acetate; nitriles SUCh as acetonitrile; amides such as dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone; and mixtures of these solvents.
Most of the starting materials of the formulae II and III are known, and 30 some are commercially available; tho~e that are not may be produced analogously to examples given in the literature Ifor III, for example, see Chem. ~er., 116, 239~, 1993).
When R3 is not hydrogen, the novel 0-substituted 3-oxypyridinium salts may 35 pOS5QSS a chiral carbon atom at R1 and/or R2. The optically pure enantiomers and diastereomers may be obtained by conventional methods. The present invention encompasses both these compounds in pure form and mixtur0s thereof. Not only the pure enantiomers and homogeneous diastereomers, but also the mixtures thereof which are usually obtained on 40 synth~sis are effective.
BASF Aktiengesellschaft 3 O.Z. 0050/3~l2 The example which follows illustrates the preparation of the novel compounds:
PreDaration examDle ~OC 14H29 a) Starting material ~ ~ C14N29Br ~ ~ C14N29 100 9 11.U~ moles~ of 3-hydroxypyridine in 500 ml of dimethylsulfoxide lDMSO) is stirred at room temperature (20C) with 87.~ 9 ll.56 moles) of KOH powder under a nitrog-n blanket. After about 30 minutes, 360 9 tl.3 30 moles~ of tetradecyl bromide is added dropwise and the mixture is stirred for a further ~ hours at room temperature. The reaction mixture is then poured into 1 liter of water and extracted three times, each time with 500 ml of methylene chloride. The combined extracts are washed twice with 1 liter of water, dried with Na2SO~ and concentrated. Filtration over silica 35 gel with n-pentane and methyl chloride gives 1~ 9 of product A tm.p.
36C).
b~ Pyridinium salt formation BrCH2-~ > ~4H29 A a 12~39469 OASF Aktiengesellschaft ~ O.Z. 0050/38~12 11.5 9 (0.0~ mole) of 3-tetradecyloxypyridine A is stirred with 5 ml (0.0 mole) of benzyl bromide for 20 minutes at 100 to 120C. After the mixture has cooled to room temperature it is suspended in pentane and the suspension is suction filtered. The filtrate is washed with pentane and 5 dried: 16.8 9 of pyridinium salt 0, m.p. 129C ~compound no. 23).
The compounds listed in the table below may be obtained analogously:
. Z. 0050/38412 - 5 - B~SF ~tiengesellschaft c~
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7. 0050/3841~ - 7 - B~SF Alctiengesell8chaft o o o ._ ~
I ~ ~
o ~o ,~
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C~ o o C~
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~ ~v ~
- ~ y y y ~ y y y y y y y y y ~ T ~ ~ ~ T ~ , c ~ c c ~ a c a ~ ~ ~ ~ :C ~ ~ ~ ~ ~ ~ 5 ~
' ' r ' r ' Y l l l u~ ~ t~ X O~ O ~ o ~
Z .
1289~6~
7~ 0050/3841~ - 8 - B~SF A~tiengesellschaft c~
O
,~ u~
o _, ~:
., ~ c~
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C~ O ~ U~ C~ O ~ C~ C`J ~ C~
~ ~ ~ 3 c~ c~ 3 ~ a a Y Y Y Y a a C~ C~l ~ ~ C~l ~
Y ~ y y ~ y3 U~
:r ~ ~ c~
~o ~ v c~
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c~ Y T c~ 3 a v ~ a 3 x 3:
T I I T I 1 ~ ~ c~l ~ ~ ~ ~ c~ ~ ~ ~ c~
^ ^ ^ ^ c~ v v -c~ u v ~ a a v a ~a a e~ ~
V ~ ~ V ~ _ _ ~ ~ ~ _ _ _ _ _ _ ~ C`~ ~ ~ e~
^ ^ ^ ^ c~ v c~ c~ v v c~ v c~ v v c~ c~ v v v c`
v v v v v v v v v r 3~ v v v v v v ^ ^ ^ ~ ^ ^
T ~ v O O O O O O
I I I I I I O O
~ c~ v v c~ c~ 8 ~ v ~7 c~ ~ ~ ~ ~ ~ ~ ~ ~ ~
_ _ _, _ _ _ _ _ _ _ _ _ _ _ _ _ ~ ,~, ~, c~ ~ ~ ~ ,.~, c~ v v v c~ c~ v v l l l l l l l l `D r~ O -- C~ X ~ O _ C~l ~ ~ u~ ~O t~ CO O~
:, , , .
1289~69 . 0050/38412 - 9 - B~SF ~tiengesellschaft ~D ~ ~ O
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C~l q ~3 ~ Y ~ 2 ~ C`l ~ ~ ~ ~ ~ ~ C~
2 2 2 2 ~ 3~ :~ 2 :~
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Y Y t~ ~ ~ ~ 2 :~
~ ~ ~ V V t~
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Y, C~
u~ 2 ~ 2 --' ~ ~ .......... 2 ~ 2 2 :C 2 ~
_ ~ ' r ' rr~
IY I I ~ ~t ~ ~ ~ 2 ~ 2 2 rr ' Y YY ~Y
o o 7 , , ~ , o, 7 o, ol ~
C~ U ~ ~ ~ 2 2 5~ , 2 ~
ll llllllll ll O -- ~ ~ ~ U~ `D 1~ 0~ O~ O --z x c~ oD X co X X o~ a~
12~39469 Characteristic lH-NMR-data Compound Solvent Chemical shift in ppm no.
46 d6-DMSO s 5.9 [24~; broad dd 8.15 [lH~;
broad d 8.30 ~14~, d 8.90 ~1HJ;
s 9.25 L1H~
69 d6-DMSO s 5.92 ~2H~, dd 8.10 [lH~;
broad d 8.28 ~lHl; d 8.92 [lH~;
s 9-28 rlH
87 d6-DMSO s 4.35 ~3HJ; dd 8.05 [lH¦;
broad d 8.20 L1HJ; d 8.62 ~lH¦;
s 8.92 [lH~
The compounds of formula I and their use as fungicides in the crop protector sector exclusively are claimed per se in copending Canadian patent application no. 512,548 filed on June 26, 1986.
In accordance with the invention, it has how-ever been found and proved that the compounds of formula I are also suitable for combating algae, bacteria and fungi outside the crop protection sector, for example for disinfecting water in air-humidifying units, cooling-water circulation systems, water injection systems and for oilfields, swimming baths, laundries, and in prepara-tions used for disinfection in the food sector, dairies, breweries, hospitals, etc. The treatment of raw hides and leather is also worthy of mention.
- ~, ' ' --- 10~ --The microbicidal agents generally contain from 0.1 to 95, and preferably from 0.5 to 90, wt~ of active ingredie t., /
':'''~' ..........
~X894~9 BASF Aktiengesellschaft ~ . 0~5C 3 The compounds according to the invention may be con-verted into the usual formulations, e.g. solutions, emul-sions, suspensions, dusts, powders, pastes and granules.
The application forms depend entlrely on the purpose for 05 which the agents are belng used; at all events they must ensure a fine and uniform distributlon of the active ingredients. The formulations are prepared in conventional manner, e.g., by extending the active ingredlent with solvents and/or carriers, if desired using emulsifiers and dispersants. Where water is used as diluent, other organlc solvents may also be employed as auxlliary solvents. Sult-able compounds for preparlng such formulatlons are sol-vents such as aromatlcs (e.g., xylene, benzene), chlorlnated aromatlcs (e.g., chlorobenzenes), paraffins (e.g., petroleum fractlons), alcohols (e.g., methanol, butanol), amlnes (e.g., ethanolamlne, dlmethylformamlde), and water; carrlers such as natural rock flours (e.g., kaollns, dlatomaceous earth, talc, chalk) and synthetic rock flours (e.g., hlghly dlsperse slllclc acld, 8111-cates); emulslflers such as nonlonlc and anionlc emulsify-lng agents (e.g. polyoxyethylene-fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); and dlspersants such as llgnln, sulflte waste llquors and methyl cellulose.
12 ~9 ~ 9 BAS~ AXtiengesellscha~ 12 - J-Z` 0050 3Q! _ The active lngredients per se are low-foam biocides. A
significant increase in the effectiveness of biocidal preparations containing these compounds is achieved by adding tri-C6_12-alkylmethylammonium salts, preferably in 05 amounts of from 20 to 40 wt%, based on the weight of compounds of the general formula I.
The compounds according to the invention whlch are contalned in such preparatlons are effectlve agalnst a large number o~ mlcroorganlsms, for example:
Staphylococcus aureus, Escherichia coll, Klebsielle pneumoniae, Citrobacter freundli, Proteus vulgaris, Pseudomonas aeruglnosa, Desulfovibrlo desulfuricans, Streptovertlcllllum rubrlretlculi, Asperglllus nlger, Asperglllus verslcolor, Penlcllllum funlculosum, Penlcllllum expansum, Penicllllum glaucum, Paecllomyces varlotll, Trlchoderma vlrlde, Chaeto~lum globosum, Candlda alblcans, Trlchophyton mentagrophytes, Geotrlchum candldans, Monllla sltophlla, Scenedesmus quadrlcauda, Chlorella vulgarls, Nostoc muscorlum, Osclllatorla llmosa und Anabaena constrlcta.
Usual use concentrations are 0.01 to 2% of active lngredlent, based on the welght of the material to be protected; when the actlve ingredlents are used for treatlng water or in the productlon of oil, ln swlmmlng baths, coollng towers, alr humldlfylng unlts or ln the paper lndustry, amounts o~ 5 to 250 ppm are sufflclent.
Ready-to-use dlslnfectant solutlons contaln, for example, from 0.5 to 10 wt% actlve ingredlent. The actlve lngredlents may also be mlxed wlth other, prlor art, mlcroblcldes. In many cases a synerglstlc effect is produced.
~2~39~i9 BASF .~tiengesellscha~t l` ~ o~33'~' Examples of such active ingredients are:
2-(thiocyanomethylthio)-benzthlazole 1-[2-(2~4-dichlorophenyl)-2-(2-propenyloxy)-ethyl]-lH-imidazole 05 2,4,5,6-tetrachloroisophthalodlnitrile methylenebisthiocyanate tributyltin oxide, naphthenate, benzoate, salicylate mercaptobenzthlazole 1,2-~enzisothiazolone and lts alkall metal salts alkall metal compounds of N'-hydroxy-N-cyclohexyl-dlazenium oxlde 2-(methoxy-carbonylamlno)-benzlmidazole 2-methyl-3-oxo-5-chlorthlazolin-3-one trihydroxymethylnitromethane glutardialdehyde chloroacetamide polyhexamethylene blsguanlde 5-chloro-2-methyl-4-isothiazolin-3-one + magnesium salts 3,5-dimethyltetrahydro-1,3,5-2H-thiadiazine-2-thione hexahydrotriazine N,N-methylolchloroacetamide 2-n-octyl-4-lsothiazolin-3-one oxazolidines bisoxazolidines 2,5-dihydro-2,5-dialkoxy-2,5-dialkyl~uranes dlethyldodecylbenzylammoniumchloride dimethyloctadecyldlmethylbenzylammonlum chlorlde dimethyldidecylammonium chlorlde dimethyldidodecylammonlum chloride trimethyltetradecylammonlum chloride benzyldimethylalkyl-(12_C18)-ammonium chloride dichlorobenzyldimethyldodecylammonium chloride cetylpyridinium chloride cetylpyrldinium bromide 12~39469 ~ASF Aktien~esellscha~t - 14 - ~.Z. I~050~3 cetyltrimethylammonium chloride laurylpyridinium chloride laurylpyridinium bisulfate benzyldodecyldi(beta-oxyethyl)-ammonium chloride O5 dodecylbenzyltrimethylammonium chloride n-alkyldimethylbenzylammonium chloride (alkyl radical: 40% C12, 50% C14, 10% C16) lauryldimethylethylammonium ethylsulfate, n-alkyldimethyl-(l-naphthylmethyl)-ammonium chloride (alkyl radical: 98% C12, 2% C14) cetyldimethylbenzylammonium chloride lauryldimethylbenzylammonium chloride lX89~6~
8ASF Aktiengesellschaft 15 O.Z. OOS0/38412 Use ExamDle 1 A~q~~l action on areen alqaQ
The active ingredients were added to a phosphate-rich nutrient solution5 suitable for favoring the propagation of the unicellular Chlorella vulgaris genus of green algae in amounts of 10, 7.5, 5, 2.5 and 1 parts by weight per million parts of nutrient solution. 100 ml of this nutrient solutionlactive ingredient mixture, and of nutrient solution on its own (control~, were introduced into 300 ml Erlenmeyer flasks. The nutrient 10 solution had been inoculated with a suspension of Chlorella vulgaris prior to the addition of the active ingredient; the cell density was adjusted to 106 cells/ml of nutrient solution. The flasks were kept for 1~ days at room temperature and with the admission of light, after which time the action was assessed.
The results show that the algae were well combated by compounds 6, 7, 9, 11, 25, 27, 32, ~0, ~6, 50, 56, 6~, 69 and 79 at rates of 10, 7.5, 5, 2.5 and 1 parts by weight per million parts of nutrient solution.
20 Use Ex~mDle 2 Ynaicidal action on AsDeraillus nia~r The active ingredients were added to a nutrient solution ideally suited for promoting the growth of the fungus Aspergillus niger in amounts of 25 100, 75, 50, 25 and 10 parts by weight per million parts of nutrient solution. 20 ml portions of the nutrient solution thus treated were placed in 100 ml glass flasks and inoculated with 0.3 mg of Aspergillus fungus spores. The flasks were heated for 120 hours at 36C, after which the degree of fungus spread - predominantly on the surface of the nutrient 30 solution - was assessed.
The results show that compounds 6, 7, 9, 11, 13, 1~, 22, 23, 25, 27, 28, 30, 32 and ~0, at rates of 100, 75, 50, 25 and 10 parts per million parts of nutrient solution, had a good fungicidal action (9OZ).
Use ExamDle 3 Action on TrichoDhvton mentag~oDhvtes and Candida albicans The active ingredients were added to a nutrient solution suited for 40 promoting the growth of the fungi Trichophyton mentagrophytes and Candida albicans in amounts of 100, 50, 25, 12, 6, 3 and 1.5 parts per million parts of nutriQnt solution. 10 ml portions of this nutrient solution/active ingredient mixture were introduced into sterile test tubes and inoculated with one drop of a spore suspension containing 106 conidia 1~89~9 ~ASF Aktiengesellschaft 16 O Z 0050/38412 or spores After 120 hours incubation, samples were taken f~om those tubes showing no visible evidence of fungus growth, and transferred to a fungus nutrient medium The dilution stage was ascertained at which no more fungus growth occurred after transferral of a sample to the nutrient 5 medium The results show that compounds ~, 5, 6, ?, 9, 11, 12, 13, 1~, 22, 23, 25, 27, 2~, 29, 30, 32, ~0, ~ 6, 50, 56, 6~, 69 and 87, when applied at rates of 1 5 to 25 ppm, had a good fungicidal action Use ExamDle ~
aa~tericid~L actio~ Qn Sta~h~LocoçÇUs 3l;ULLL~LiLh~ coli and ProtevS~
15 The bacteria kill values were ascertained as follows 5 ml of a dilution of the agents in water was introduced into sterile test tubes and 5 ml of a doubly concentrated nutrient broth w-s added and mixed, The trial solutions contained 200, 100, 50, 25, t2, 6 and 3 parts by weight per million parts of nutrient broth The tube contents were then 20 inoculated by dding one drop of 16-hour old broth cultures (1 10 dilution) of the bacteria Staphylococcu3 aureus, Escheria coli and Proteus vulgaris, and the tubes were incubated for 2~ hours at 37C The dilution stage was ascertained at which no more bacterial growth occurred after transf~rral of a sample to the nutrient medium The results show that compounds ~, 5, 6, 7, 11, 1~ and 23, at rates of from 6 to 50 ppm, had a good fungicidal action Use Ex~mDle 5 30 Action on the funai Paecilomvces variotii Aureobasidium Dullulans and Geotrichum candidans The active ingredients were added to a nutrient solution suited for promoting the growth of the fungi Paecilomyces variotii, Aureobasidium 35 pullulans and Geotrichum candidans in amounts of 100, 50, 25, 12, 6, ~ and 1 5 parts by weight per million parts of nutrient solution 10 ml portions of this nutrient solution/active ingredient mixture were introduced into sterile test tubes and inoculated with one drop of a spore suspension containing lo6 conidia or cells After 120 hours' incubation samples were 40 taken from those tubes showing no vi~ible evidence of fungus growth and transferred to a fungus nutrient meJium The dilution stage was ascertained at which no more fungus growth occurred after transferral of a sample to the nutrient medium 12894~i~
6ASF Aktiengesellschaft 17 O.Z. 0050/38412 The results show that compounds 4, 5, 6, 7, 9, 11, 12, 13, 14. 22, 23, 25, 26, 2~, 29, 30, 32, 40, ~1, 46, 5fi and 76, when applied at rates of from 1.5 to 12 ppm, had a good fungicidal action.
The present invention relates to a microbicidal composition containing 0-substituted 3-oxypyridinium salts for combating microbes, and a method of combatin~ mi-crobes.
More particularly, the present invention pro-poses a microbicidal composition for combating algae, bacteria or fungi of the non-phytopathogenic type, out-side the crop protection sector. This composition which contains a toxic amount of an 0-substituted 3-oxypyridinium salt of the formula:
[ ~~Rl ~
where R1 is an alkyl, alkenyl or alkynyl radical which is unsubstituted or substituted by at least one alkoxy, cycloalkoxy, phenylalkoxy or halogen, and has a total of 8 to 20 carbon atoms, R2 i8 unsubstituted or halogen-substituted alkyl, alkenyl or alkynyl of up to 8 carbon atoms, or one of the groups -(CH2)1 2~Ar, -(CH2)2 50CH21CHCH2Ar or -(CH2)2 6-0-Ar R
where Ar is l-naphthyl, 2-naphthyl, biphenyl or phenyl, phenyl being unsubstituted or substituted by F, Cl, Br, NO2~ 3CF3, CN~ Cl-13~alkYl~ C2_4-alkenyl or Cl 2-alkoxy and R is H, Cl-C2-alkyl, C3-C5-alkenyl or Cl-C5-alkoxy and X~ is F0, C10, B~0 or I0 or an anion which is the equivalent of an acid, have proved to have a good microbicidal action.
,'~i ~1 , , ~289469 - la -Examples of meanings for R are branched or straight-chain octyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, P 2 10alkYl-O-cs lgalkyl~ -0-cyclohexyl or -0-C3-C5-alkylphenyl with a total of 10 to 20 carbon at-oms. 2 Examples of meanings for R are Cl-C4-alkyl, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, allyl, 2-chloropropenyl, 2-bromopropenyl, 3-chloro-propenyl, but-2-en-1-yl, 2-methylpropenyl, 3-chlorobut-2-en-1-yl, propargyl or the radicals -(CH2)1 2-Ar or -(CH2)2 6-OAr, Ar denoting unsubstituted phenyl or phenyl containing one to three halogen substituents, such as 4-fluorophenyl, 3- or 4-chlorophenyl,4-bromophenyl, 3,4-dichlorophenyl, 2,4-dichlorophenyl, 2,6-dichloro-phenyl, and 2,4,6-dichlorophenyl.
/
..
. ;.
~289~69 ~ASF Aktiengesellschaft 2 O.Z. 0050/38~12 Examples of meanings for ~ are Cl~, ~r~ or an anion which is one equivalent of an acid, such as phenylsulfonic acid, p-methylphenyl-sulfonic acid or one equivalent of the sulfuric acid anion.
5 The 0-substituted 3-oxypyridinium salts of the formula I are obtained by reacting a compound of the formula R2X II, 1O where R2 and X have the above meanings, With an 0-substituted 3-oxypyridine derivative of the formula ~0--R1 ~NJ III, where R1 has the above meanings.
The reaction is carried out in bulk or if desired in the presence of an15 inert solvent or diluont at from 20 to 150, pref0rably 50 to 150, CC. The starting material of the formula III is advantageously reacted with up to 10 times the molar amount Ibased on III) of the alkylating agent of the 40rmula II.
20 Examples of preferred inert solvents or diluents are aliphatic or aromatic hydrocarbons or halohydrocarbons, such as pentane, cyclohexane, heptane, benzene, toluene, chlorobenzene and dichloro-benzenes; aliphatic ketones such as acetonQ, methyl ethyl ketone, diethyl ketone and cyclopentanone;
ethers such as diethyl ether, methyl tert-butyl ether, dimethoxyethane, 25 tetrahydrofuran and dioxane; esters such as ethyl acetate; nitriles SUCh as acetonitrile; amides such as dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone; and mixtures of these solvents.
Most of the starting materials of the formulae II and III are known, and 30 some are commercially available; tho~e that are not may be produced analogously to examples given in the literature Ifor III, for example, see Chem. ~er., 116, 239~, 1993).
When R3 is not hydrogen, the novel 0-substituted 3-oxypyridinium salts may 35 pOS5QSS a chiral carbon atom at R1 and/or R2. The optically pure enantiomers and diastereomers may be obtained by conventional methods. The present invention encompasses both these compounds in pure form and mixtur0s thereof. Not only the pure enantiomers and homogeneous diastereomers, but also the mixtures thereof which are usually obtained on 40 synth~sis are effective.
BASF Aktiengesellschaft 3 O.Z. 0050/3~l2 The example which follows illustrates the preparation of the novel compounds:
PreDaration examDle ~OC 14H29 a) Starting material ~ ~ C14N29Br ~ ~ C14N29 100 9 11.U~ moles~ of 3-hydroxypyridine in 500 ml of dimethylsulfoxide lDMSO) is stirred at room temperature (20C) with 87.~ 9 ll.56 moles) of KOH powder under a nitrog-n blanket. After about 30 minutes, 360 9 tl.3 30 moles~ of tetradecyl bromide is added dropwise and the mixture is stirred for a further ~ hours at room temperature. The reaction mixture is then poured into 1 liter of water and extracted three times, each time with 500 ml of methylene chloride. The combined extracts are washed twice with 1 liter of water, dried with Na2SO~ and concentrated. Filtration over silica 35 gel with n-pentane and methyl chloride gives 1~ 9 of product A tm.p.
36C).
b~ Pyridinium salt formation BrCH2-~ > ~4H29 A a 12~39469 OASF Aktiengesellschaft ~ O.Z. 0050/38~12 11.5 9 (0.0~ mole) of 3-tetradecyloxypyridine A is stirred with 5 ml (0.0 mole) of benzyl bromide for 20 minutes at 100 to 120C. After the mixture has cooled to room temperature it is suspended in pentane and the suspension is suction filtered. The filtrate is washed with pentane and 5 dried: 16.8 9 of pyridinium salt 0, m.p. 129C ~compound no. 23).
The compounds listed in the table below may be obtained analogously:
. Z. 0050/38412 - 5 - B~SF ~tiengesellschaft c~
_. ,~ ~o I cr- I ~ ~ ~ ~o u~
~D X Cr~
_ :~ `D `D
X
~ ~ Y T~ :~
C~l y y y o o ~: 3 ~ Y 'i' ~, Y, ~ ~ ~ Y
YYY~YYY~ YY
- lo o - o ~ ~ ~ ~ ~ ~ ~ ~ - - - -l yyy l yyyyyyy l yy 1~ ~ Cl C ~ C: ~ Ct R 1: C ~
,. Z_ _ _ _ __ ' , ~ ,.
.
128~469 ~ 7. 0050/~8412 - 6 - B~SF ~ktiengesellschaft c~ u~
C~` ~`3 u~
~ J ~ x _ _ _ _~
~: ~
~ ~ ~ c~
Y Y Y l I q y ~ y :~ x ~ ~
~ I I I o o o Sl) ~
Y~ 3~ , rr 7~S'S'S'Y
~ y ~
~ a I I I ~ I ~ c ~
.
.~
~O 1~ X ~ o -- ~ ~ ~ U~ o -- ~ ~ ~r .
:
7. 0050/3841~ - 7 - B~SF Alctiengesell8chaft o o o ._ ~
I ~ ~
o ~o ,~
:~: o~ U~
x ~ ~ ~ ~ ~ ~ ~ ~ m c~ a~
~ Y
C~ o o C~
C~ Y Y Y Y Ci~ Y Y ~ S~
v v 3 ~ _ _ X _ N C~
~ ~v ~
- ~ y y y ~ y y y y y y y y y ~ T ~ ~ ~ T ~ , c ~ c c ~ a c a ~ ~ ~ ~ :C ~ ~ ~ ~ ~ ~ 5 ~
' ' r ' r ' Y l l l u~ ~ t~ X O~ O ~ o ~
Z .
1289~6~
7~ 0050/3841~ - 8 - B~SF A~tiengesellschaft c~
O
,~ u~
o _, ~:
., ~ c~
~ u~
c~ T
C~ O ~ U~ C~ O ~ C~ C`J ~ C~
~ ~ ~ 3 c~ c~ 3 ~ a a Y Y Y Y a a C~ C~l ~ ~ C~l ~
Y ~ y y ~ y3 U~
:r ~ ~ c~
~o ~ v c~
~, ~, v v ~ a ~
c~ Y T c~ 3 a v ~ a 3 x 3:
T I I T I 1 ~ ~ c~l ~ ~ ~ ~ c~ ~ ~ ~ c~
^ ^ ^ ^ c~ v v -c~ u v ~ a a v a ~a a e~ ~
V ~ ~ V ~ _ _ ~ ~ ~ _ _ _ _ _ _ ~ C`~ ~ ~ e~
^ ^ ^ ^ c~ v c~ c~ v v c~ v c~ v v c~ c~ v v v c`
v v v v v v v v v r 3~ v v v v v v ^ ^ ^ ~ ^ ^
T ~ v O O O O O O
I I I I I I O O
~ c~ v v c~ c~ 8 ~ v ~7 c~ ~ ~ ~ ~ ~ ~ ~ ~ ~
_ _ _, _ _ _ _ _ _ _ _ _ _ _ _ _ ~ ,~, ~, c~ ~ ~ ~ ,.~, c~ v v v c~ c~ v v l l l l l l l l `D r~ O -- C~ X ~ O _ C~l ~ ~ u~ ~O t~ CO O~
:, , , .
1289~69 . 0050/38412 - 9 - B~SF ~tiengesellschaft ~D ~ ~ O
o~ ~ o æ _ _ .. .
C~l q ~3 ~ Y ~ 2 ~ C`l ~ ~ ~ ~ ~ ~ C~
2 2 2 2 ~ 3~ :~ 2 :~
Y ~ Y ~ Y Y
~ o~
2 :~ ^
. . 2 ~ t~ ~ ~D `D `O `O
Y Y t~ ~ ~ ~ 2 :~
~ ~ ~ V V t~
~ ~ y y y y y Y ~
Y, C~
u~ 2 ~ 2 --' ~ ~ .......... 2 ~ 2 2 :C 2 ~
_ ~ ' r ' rr~
IY I I ~ ~t ~ ~ ~ 2 ~ 2 2 rr ' Y YY ~Y
o o 7 , , ~ , o, 7 o, ol ~
C~ U ~ ~ ~ 2 2 5~ , 2 ~
ll llllllll ll O -- ~ ~ ~ U~ `D 1~ 0~ O~ O --z x c~ oD X co X X o~ a~
12~39469 Characteristic lH-NMR-data Compound Solvent Chemical shift in ppm no.
46 d6-DMSO s 5.9 [24~; broad dd 8.15 [lH~;
broad d 8.30 ~14~, d 8.90 ~1HJ;
s 9.25 L1H~
69 d6-DMSO s 5.92 ~2H~, dd 8.10 [lH~;
broad d 8.28 ~lHl; d 8.92 [lH~;
s 9-28 rlH
87 d6-DMSO s 4.35 ~3HJ; dd 8.05 [lH¦;
broad d 8.20 L1HJ; d 8.62 ~lH¦;
s 8.92 [lH~
The compounds of formula I and their use as fungicides in the crop protector sector exclusively are claimed per se in copending Canadian patent application no. 512,548 filed on June 26, 1986.
In accordance with the invention, it has how-ever been found and proved that the compounds of formula I are also suitable for combating algae, bacteria and fungi outside the crop protection sector, for example for disinfecting water in air-humidifying units, cooling-water circulation systems, water injection systems and for oilfields, swimming baths, laundries, and in prepara-tions used for disinfection in the food sector, dairies, breweries, hospitals, etc. The treatment of raw hides and leather is also worthy of mention.
- ~, ' ' --- 10~ --The microbicidal agents generally contain from 0.1 to 95, and preferably from 0.5 to 90, wt~ of active ingredie t., /
':'''~' ..........
~X894~9 BASF Aktiengesellschaft ~ . 0~5C 3 The compounds according to the invention may be con-verted into the usual formulations, e.g. solutions, emul-sions, suspensions, dusts, powders, pastes and granules.
The application forms depend entlrely on the purpose for 05 which the agents are belng used; at all events they must ensure a fine and uniform distributlon of the active ingredients. The formulations are prepared in conventional manner, e.g., by extending the active ingredlent with solvents and/or carriers, if desired using emulsifiers and dispersants. Where water is used as diluent, other organlc solvents may also be employed as auxlliary solvents. Sult-able compounds for preparlng such formulatlons are sol-vents such as aromatlcs (e.g., xylene, benzene), chlorlnated aromatlcs (e.g., chlorobenzenes), paraffins (e.g., petroleum fractlons), alcohols (e.g., methanol, butanol), amlnes (e.g., ethanolamlne, dlmethylformamlde), and water; carrlers such as natural rock flours (e.g., kaollns, dlatomaceous earth, talc, chalk) and synthetic rock flours (e.g., hlghly dlsperse slllclc acld, 8111-cates); emulslflers such as nonlonlc and anionlc emulsify-lng agents (e.g. polyoxyethylene-fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); and dlspersants such as llgnln, sulflte waste llquors and methyl cellulose.
12 ~9 ~ 9 BAS~ AXtiengesellscha~ 12 - J-Z` 0050 3Q! _ The active lngredients per se are low-foam biocides. A
significant increase in the effectiveness of biocidal preparations containing these compounds is achieved by adding tri-C6_12-alkylmethylammonium salts, preferably in 05 amounts of from 20 to 40 wt%, based on the weight of compounds of the general formula I.
The compounds according to the invention whlch are contalned in such preparatlons are effectlve agalnst a large number o~ mlcroorganlsms, for example:
Staphylococcus aureus, Escherichia coll, Klebsielle pneumoniae, Citrobacter freundli, Proteus vulgaris, Pseudomonas aeruglnosa, Desulfovibrlo desulfuricans, Streptovertlcllllum rubrlretlculi, Asperglllus nlger, Asperglllus verslcolor, Penlcllllum funlculosum, Penlcllllum expansum, Penicllllum glaucum, Paecllomyces varlotll, Trlchoderma vlrlde, Chaeto~lum globosum, Candlda alblcans, Trlchophyton mentagrophytes, Geotrlchum candldans, Monllla sltophlla, Scenedesmus quadrlcauda, Chlorella vulgarls, Nostoc muscorlum, Osclllatorla llmosa und Anabaena constrlcta.
Usual use concentrations are 0.01 to 2% of active lngredlent, based on the welght of the material to be protected; when the actlve ingredlents are used for treatlng water or in the productlon of oil, ln swlmmlng baths, coollng towers, alr humldlfylng unlts or ln the paper lndustry, amounts o~ 5 to 250 ppm are sufflclent.
Ready-to-use dlslnfectant solutlons contaln, for example, from 0.5 to 10 wt% actlve ingredlent. The actlve lngredlents may also be mlxed wlth other, prlor art, mlcroblcldes. In many cases a synerglstlc effect is produced.
~2~39~i9 BASF .~tiengesellscha~t l` ~ o~33'~' Examples of such active ingredients are:
2-(thiocyanomethylthio)-benzthlazole 1-[2-(2~4-dichlorophenyl)-2-(2-propenyloxy)-ethyl]-lH-imidazole 05 2,4,5,6-tetrachloroisophthalodlnitrile methylenebisthiocyanate tributyltin oxide, naphthenate, benzoate, salicylate mercaptobenzthlazole 1,2-~enzisothiazolone and lts alkall metal salts alkall metal compounds of N'-hydroxy-N-cyclohexyl-dlazenium oxlde 2-(methoxy-carbonylamlno)-benzlmidazole 2-methyl-3-oxo-5-chlorthlazolin-3-one trihydroxymethylnitromethane glutardialdehyde chloroacetamide polyhexamethylene blsguanlde 5-chloro-2-methyl-4-isothiazolin-3-one + magnesium salts 3,5-dimethyltetrahydro-1,3,5-2H-thiadiazine-2-thione hexahydrotriazine N,N-methylolchloroacetamide 2-n-octyl-4-lsothiazolin-3-one oxazolidines bisoxazolidines 2,5-dihydro-2,5-dialkoxy-2,5-dialkyl~uranes dlethyldodecylbenzylammoniumchloride dimethyloctadecyldlmethylbenzylammonlum chlorlde dimethyldidecylammonium chlorlde dimethyldidodecylammonlum chloride trimethyltetradecylammonlum chloride benzyldimethylalkyl-(12_C18)-ammonium chloride dichlorobenzyldimethyldodecylammonium chloride cetylpyridinium chloride cetylpyrldinium bromide 12~39469 ~ASF Aktien~esellscha~t - 14 - ~.Z. I~050~3 cetyltrimethylammonium chloride laurylpyridinium chloride laurylpyridinium bisulfate benzyldodecyldi(beta-oxyethyl)-ammonium chloride O5 dodecylbenzyltrimethylammonium chloride n-alkyldimethylbenzylammonium chloride (alkyl radical: 40% C12, 50% C14, 10% C16) lauryldimethylethylammonium ethylsulfate, n-alkyldimethyl-(l-naphthylmethyl)-ammonium chloride (alkyl radical: 98% C12, 2% C14) cetyldimethylbenzylammonium chloride lauryldimethylbenzylammonium chloride lX89~6~
8ASF Aktiengesellschaft 15 O.Z. OOS0/38412 Use ExamDle 1 A~q~~l action on areen alqaQ
The active ingredients were added to a phosphate-rich nutrient solution5 suitable for favoring the propagation of the unicellular Chlorella vulgaris genus of green algae in amounts of 10, 7.5, 5, 2.5 and 1 parts by weight per million parts of nutrient solution. 100 ml of this nutrient solutionlactive ingredient mixture, and of nutrient solution on its own (control~, were introduced into 300 ml Erlenmeyer flasks. The nutrient 10 solution had been inoculated with a suspension of Chlorella vulgaris prior to the addition of the active ingredient; the cell density was adjusted to 106 cells/ml of nutrient solution. The flasks were kept for 1~ days at room temperature and with the admission of light, after which time the action was assessed.
The results show that the algae were well combated by compounds 6, 7, 9, 11, 25, 27, 32, ~0, ~6, 50, 56, 6~, 69 and 79 at rates of 10, 7.5, 5, 2.5 and 1 parts by weight per million parts of nutrient solution.
20 Use Ex~mDle 2 Ynaicidal action on AsDeraillus nia~r The active ingredients were added to a nutrient solution ideally suited for promoting the growth of the fungus Aspergillus niger in amounts of 25 100, 75, 50, 25 and 10 parts by weight per million parts of nutrient solution. 20 ml portions of the nutrient solution thus treated were placed in 100 ml glass flasks and inoculated with 0.3 mg of Aspergillus fungus spores. The flasks were heated for 120 hours at 36C, after which the degree of fungus spread - predominantly on the surface of the nutrient 30 solution - was assessed.
The results show that compounds 6, 7, 9, 11, 13, 1~, 22, 23, 25, 27, 28, 30, 32 and ~0, at rates of 100, 75, 50, 25 and 10 parts per million parts of nutrient solution, had a good fungicidal action (9OZ).
Use ExamDle 3 Action on TrichoDhvton mentag~oDhvtes and Candida albicans The active ingredients were added to a nutrient solution suited for 40 promoting the growth of the fungi Trichophyton mentagrophytes and Candida albicans in amounts of 100, 50, 25, 12, 6, 3 and 1.5 parts per million parts of nutriQnt solution. 10 ml portions of this nutrient solution/active ingredient mixture were introduced into sterile test tubes and inoculated with one drop of a spore suspension containing 106 conidia 1~89~9 ~ASF Aktiengesellschaft 16 O Z 0050/38412 or spores After 120 hours incubation, samples were taken f~om those tubes showing no visible evidence of fungus growth, and transferred to a fungus nutrient medium The dilution stage was ascertained at which no more fungus growth occurred after transferral of a sample to the nutrient 5 medium The results show that compounds ~, 5, 6, ?, 9, 11, 12, 13, 1~, 22, 23, 25, 27, 2~, 29, 30, 32, ~0, ~ 6, 50, 56, 6~, 69 and 87, when applied at rates of 1 5 to 25 ppm, had a good fungicidal action Use ExamDle ~
aa~tericid~L actio~ Qn Sta~h~LocoçÇUs 3l;ULLL~LiLh~ coli and ProtevS~
15 The bacteria kill values were ascertained as follows 5 ml of a dilution of the agents in water was introduced into sterile test tubes and 5 ml of a doubly concentrated nutrient broth w-s added and mixed, The trial solutions contained 200, 100, 50, 25, t2, 6 and 3 parts by weight per million parts of nutrient broth The tube contents were then 20 inoculated by dding one drop of 16-hour old broth cultures (1 10 dilution) of the bacteria Staphylococcu3 aureus, Escheria coli and Proteus vulgaris, and the tubes were incubated for 2~ hours at 37C The dilution stage was ascertained at which no more bacterial growth occurred after transf~rral of a sample to the nutrient medium The results show that compounds ~, 5, 6, 7, 11, 1~ and 23, at rates of from 6 to 50 ppm, had a good fungicidal action Use Ex~mDle 5 30 Action on the funai Paecilomvces variotii Aureobasidium Dullulans and Geotrichum candidans The active ingredients were added to a nutrient solution suited for promoting the growth of the fungi Paecilomyces variotii, Aureobasidium 35 pullulans and Geotrichum candidans in amounts of 100, 50, 25, 12, 6, ~ and 1 5 parts by weight per million parts of nutrient solution 10 ml portions of this nutrient solution/active ingredient mixture were introduced into sterile test tubes and inoculated with one drop of a spore suspension containing lo6 conidia or cells After 120 hours' incubation samples were 40 taken from those tubes showing no vi~ible evidence of fungus growth and transferred to a fungus nutrient meJium The dilution stage was ascertained at which no more fungus growth occurred after transferral of a sample to the nutrient medium 12894~i~
6ASF Aktiengesellschaft 17 O.Z. 0050/38412 The results show that compounds 4, 5, 6, 7, 9, 11, 12, 13, 14. 22, 23, 25, 26, 2~, 29, 30, 32, 40, ~1, 46, 5fi and 76, when applied at rates of from 1.5 to 12 ppm, had a good fungicidal action.
Claims (4)
1. A process for combating algae, bacteria or fungi of the non-phytopathogenic type, outside the crop protection sector, wherein the microorganisms or the ob-jects threatened by attack by the microorganisms are treated with a toxic amount of an 0-substituted 3-oxypyridinium salt of the formula I, where:
R1 is a radical alkyl, alkenyl or alkynyl, said radical R1 being unsubstituted or substituted by at least one alkoxy, cycloalkoxy, phenylalkoxy or halogen, and having a total of 8 to 20 carbon atoms, R2 is an unsubstituted or halogen-substituted alkyl, alkenyl or alkynyl having up to 8 carbon atoms, or is one of the groups -(CH2)1_2-Ar, , -(CH2)2_6-O-Ar, where Ar is 1-naphthyl, 2-naphthyl, biphenyl or phenyl, phenyl being unsubstituted or substituted by F, Cl, Br, NO2, CF3, CN, C1-13-alkyl, C2-4-alkenyl or C1-2-alkoxy, and R3 is H, C1-C2-alkyl, C3-C5-alkenyl or C1-C5-alkoxy;
and X? is F?, Cl?, Br? or I? or an anion which is the equivalent of a non-phytotoxic acid.
R1 is a radical alkyl, alkenyl or alkynyl, said radical R1 being unsubstituted or substituted by at least one alkoxy, cycloalkoxy, phenylalkoxy or halogen, and having a total of 8 to 20 carbon atoms, R2 is an unsubstituted or halogen-substituted alkyl, alkenyl or alkynyl having up to 8 carbon atoms, or is one of the groups -(CH2)1_2-Ar, , -(CH2)2_6-O-Ar, where Ar is 1-naphthyl, 2-naphthyl, biphenyl or phenyl, phenyl being unsubstituted or substituted by F, Cl, Br, NO2, CF3, CN, C1-13-alkyl, C2-4-alkenyl or C1-2-alkoxy, and R3 is H, C1-C2-alkyl, C3-C5-alkenyl or C1-C5-alkoxy;
and X? is F?, Cl?, Br? or I? or an anion which is the equivalent of a non-phytotoxic acid.
2. A process as set forth in claim 1, wherein use is made o f a compound of formula I as de-fined in claim 1, where R1 is dodecyl, R2 is allyl, benzyl or monochlorobenzyl, and X is chloride or bromide.
3. A microbicidal composition of the non-phyto-pathogenic type, outside the crop protection sector, com-prising a toxic amount of a compound of formula I as de-fined in claim 1 as active ingredient, in admixture with a diluent or carrier adapted for use in non-plant appli-cations.
4. A microbicidal composition of the non-phyto-pathogenic type, outside the crop protection sector, com-prising a toxic amount of a compound of formula I as de-fined in claim 1, where R1 is dodecyl, R2 is allyl, benzyl or monochlorobenzyl, and X is chloride or bromide, in ad-mixture with a diluent or carrier adapted for use in non-plant applications.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3614706.0 | 1986-04-30 | ||
| DE19863614706 DE3614706A1 (en) | 1986-04-30 | 1986-04-30 | AGENTS FOR COMBATING MICROBES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1289469C true CA1289469C (en) | 1991-09-24 |
Family
ID=6299906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000522967A Expired - Lifetime CA1289469C (en) | 1986-04-30 | 1986-11-14 | Oxypyridinium salts and agents for combating microbes |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0244509B1 (en) |
| JP (1) | JPH07116004B2 (en) |
| AT (1) | ATE57815T1 (en) |
| AU (1) | AU591201B2 (en) |
| CA (1) | CA1289469C (en) |
| DE (2) | DE3614706A1 (en) |
| ES (1) | ES2018649B3 (en) |
| GR (1) | GR3001077T3 (en) |
| IL (1) | IL80662A0 (en) |
| NO (1) | NO174253C (en) |
| NZ (1) | NZ218320A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU5837900A (en) * | 1999-07-23 | 2001-02-13 | Bioparken As | Control of crustacean infestation of aquatic animals |
| AU5838000A (en) * | 1999-07-23 | 2001-02-13 | Bioparken As | Novel juvenile hormone analogues and their use as antifouling agents |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU178379A (en) * | ||||
| DE532396C (en) * | 1929-04-20 | 1931-08-27 | I G Farbenindustrie Akt Ges | Process for the preparation of N-methyl compounds of the pyridine series |
| US2728775A (en) * | 1954-01-11 | 1955-12-27 | Sadolin & Holmblad As | n-cetyl-3 hydroxypyridinium chloride |
| GB1339764A (en) * | 1971-03-29 | 1973-12-05 | Ici Ltd | Pyridine derivatives |
| GB1420533A (en) * | 1971-09-27 | 1976-01-07 | Cheminova As | Pyridine derivatives having juvenile hormone activity |
| US4220577A (en) * | 1978-04-20 | 1980-09-02 | Givaudan Corporation | Iodopropargyl pyridyl and picolinyl ethers and thioethers as paint fungicides |
| DE3522905A1 (en) * | 1985-06-27 | 1987-01-08 | Basf Ag | O-SUBSTITUTED 3-OXYPYRIDINIUM SALTS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES FOR PLANT PROTECTION |
-
1986
- 1986-04-30 DE DE19863614706 patent/DE3614706A1/en not_active Withdrawn
- 1986-11-14 CA CA000522967A patent/CA1289469C/en not_active Expired - Lifetime
- 1986-11-17 IL IL80662A patent/IL80662A0/en not_active IP Right Cessation
- 1986-11-18 NZ NZ218320A patent/NZ218320A/en unknown
- 1986-11-24 EP EP86116270A patent/EP0244509B1/en not_active Expired - Lifetime
- 1986-11-24 ES ES86116270T patent/ES2018649B3/en not_active Expired - Lifetime
- 1986-11-24 AT AT86116270T patent/ATE57815T1/en not_active IP Right Cessation
- 1986-11-24 DE DE8686116270T patent/DE3675386D1/en not_active Expired - Lifetime
- 1986-11-26 AU AU65695/86A patent/AU591201B2/en not_active Ceased
- 1986-11-28 JP JP61282218A patent/JPH07116004B2/en not_active Expired - Lifetime
- 1986-11-28 NO NO864791A patent/NO174253C/en unknown
-
1990
- 1990-11-15 GR GR90400920T patent/GR3001077T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0244509A1 (en) | 1987-11-11 |
| NO864791L (en) | 1987-11-02 |
| ES2018649B3 (en) | 1991-05-01 |
| IL80662A0 (en) | 1987-02-27 |
| GR3001077T3 (en) | 1992-04-17 |
| NZ218320A (en) | 1988-11-29 |
| DE3675386D1 (en) | 1990-12-06 |
| JPS62258304A (en) | 1987-11-10 |
| AU6569586A (en) | 1987-11-05 |
| NO174253C (en) | 1994-04-06 |
| AU591201B2 (en) | 1989-11-30 |
| EP0244509B1 (en) | 1990-10-31 |
| JPH07116004B2 (en) | 1995-12-13 |
| NO174253B (en) | 1993-12-27 |
| DE3614706A1 (en) | 1987-11-05 |
| ATE57815T1 (en) | 1990-11-15 |
| NO864791D0 (en) | 1986-11-28 |
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