US3488358A - Certain 1,1 - dihydroperfluoroalkylpyridinium trifluoromethane sulfonates - Google Patents
Certain 1,1 - dihydroperfluoroalkylpyridinium trifluoromethane sulfonates Download PDFInfo
- Publication number
- US3488358A US3488358A US620665A US3488358DA US3488358A US 3488358 A US3488358 A US 3488358A US 620665 A US620665 A US 620665A US 3488358D A US3488358D A US 3488358DA US 3488358 A US3488358 A US 3488358A
- Authority
- US
- United States
- Prior art keywords
- certain
- fluorocarbon
- dihydroperfluoroalkylpyridinium
- antimicrobial
- quaternary
- 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.)
- Expired - Lifetime
Links
- 125000002827 triflate group Chemical class FC(S(=O)(=O)O*)(F)F 0.000 title 1
- 150000001875 compounds Chemical class 0.000 description 13
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 12
- 239000004599 antimicrobial Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 150000003839 salts Chemical group 0.000 description 8
- 230000000845 anti-microbial effect Effects 0.000 description 7
- -1 ethyl alcohol) Chemical class 0.000 description 6
- 241001465754 Metazoa Species 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 241000233866 Fungi Species 0.000 description 3
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 description 3
- 229960001927 cetylpyridinium chloride Drugs 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 231100000225 lethality Toxicity 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 210000002966 serum Anatomy 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100001274 therapeutic index Toxicity 0.000 description 2
- 230000000699 topical effect Effects 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 2
- YBVIGZGPYGVIDI-UHFFFAOYSA-M 1-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl)pyridin-1-ium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C[N+]1=CC=CC=C1 YBVIGZGPYGVIDI-UHFFFAOYSA-M 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 244000063299 Bacillus subtilis Species 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- 241000222122 Candida albicans Species 0.000 description 1
- 241000282472 Canis lupus familiaris Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 241000194022 Streptococcus sp. Species 0.000 description 1
- 206010052428 Wound Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 229940064004 antiseptic throat preparations Drugs 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 229940095731 candida albicans Drugs 0.000 description 1
- NFCRBQADEGXVDL-UHFFFAOYSA-M cetylpyridinium chloride monohydrate Chemical compound O.[Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 NFCRBQADEGXVDL-UHFFFAOYSA-M 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000002324 mouth wash Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/20—Quaternary compounds thereof
Definitions
- This invention relates to antimicrobial (e.g. antibacterial and antifungal) substances and to compositions containing them. More particularly, it relates to fluorocarbon quaternary salts and compositions thereof.
- fluorocarbon quaternary salts are known to be useful and active antimicrobials.
- Certain fluorocarbon quaternary salts have also been known previously e.g., (see U.S. Patents 2,727,923, 2,759,019, 2,764,602 and 2,764,603). These have been shown to be surface active compounds with unusual properties, but their use as antimicrobials has not been disclosed. Indeed, the fluorocarbon quaternary salts, particularly those with larger fluorocarbon groups (e.g. above C F would be expected to have little or no antimicrobial activity since such fluorocarbon groups normally reduce or obviate pharmaceutical activity.
- the present invention relates to a novel class of fluorocarbon quaternary salts (containing relatively large fluorocarbon groups) which are not only unexpectedly active antimicrobials, but which, as will be shown, are much safer for certain applications than previously known quaternary antimicrobials.
- the high degree of safety of the compounds of the invention as antimicrobials is of major importance in various areas of use.
- An example of this is topical application to wounds of domestic animals or pets. Since the wounded area is likely to be licked 'by the animal, it is important that the antimicrobial be as non-toxic as possible while 3,488,358 Patented Jan. 6, 1970 ice still retaining its effectiveness.
- Another area in which safeness is important is in oral antiseptics such as mouth washes.
- the relative safety of compounds for therapeutic uses is commonly measured as a Therapeutic Index, i.e. the ratio of effectiveness to lethality. In the present case, this can be measured as the ratio of the effectiveness against microorganisms to the lethality against test animals.
- the compounds of this invention may be applied directly and alone to the tissue or material to be treated or conventional carriers or diluents may be incorporated with them before application.
- the choice of carrier or diluent and the concentration of the active ingredient are determined by the use of the composition.
- compositions are usefully employed as ointments which are not readily removed from the treated area by movement or rubbing.
- Other pharmaceutical carriers which can be used are organic solvents (such as alcohols, e.g. ethyl alcohol), Water (to dissolve or suspend the active ingredient), solid inert materials such as talc, bentonite, kieselguhr, diatomaceous earth, and the like, emulsifying agents, etc.
- the fluorocarbon quaternary salts of the invention can also be dispersed in pressure sensitive adhesives for use in surgical tapes, drapes, etc. In such cases, the adhesives can also be considered to be pharmaceutical extending media.
- 1,1 dihydroperfluorooctyl trifluoromethanesulfonate (5.3 g., 0.010 mole) was added dropwise to a stirred solution of 1.8 g. (0.022 mole) of pyridine in ml. 2-butanone at reflux temperature. After heating for an additional two days, the mixture was concentrated to dryness. The oily residue was triturated with ether to .aiford a solid which was collected and recrystallized twice from chloroform to afford 1.4 g. (23%) of N-(1,1-dihydroperfluorooctyl)pyridinium trifluoromethanesulfonate having the structure:
- the 1.1 dihydroperfluorooctyl trifluoromethanesulfonate used in the foregoing preparation was prepared according to the method described by Hensen (J. Org. Chem, vol. 30, p. 4322, 1965) utilizing 1,1-dihydroperfluorooctyl alcohol.
- the effectiveness of the perfluorooctyl pyridinium salt as an antimicrobial was evaluated against four bacteria (Staphylococcus aureus, Streptococcus sp. 104 Escherichio coli and Bacillus subtilis) and two fungi (Aspcrgillus niger and Candida albicans) using a variation of the agar plate diffusion method of Vincent and Vincent (Proc. Soc. Expty. Biol. Med. 55: 162-164) using culture media based on the synthetic glucose-salts medium of Davis and Mingioli (Jour. Bact. 66: 129-136). Both serum free cultures and cultures with serum or blood were tested with each microorganism.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Pyridine Compounds (AREA)
Description
United States Patent 3,488,358 CERTAIN 1,1 DIHYDROPERFLUOROALKYL- PYRIDINIUM TRIFLUOROMETHANE SUL- FONATES Jerry E. Robertson, North Oaks, Minn., assignor to Minnesota Mining and Manufacturing Company, St. Paul, Minn., a corporation of Delaware No Drawing. Filed Mar. 6, 1967, Ser. No. 620,665 Int. Cl. C07d 31/26, 31/48 U.S. Cl. 260-2943 2 Claims ABSTRACT OF THE DISCLOSURE Certain fluorocarbon quaternary salts, a process for their preparation and compositions containing thesalts are disclosed. These salts are shown to have antimicrobial properties.
BRIEF SUMMARY OF THE INVENTION This invention relates to antimicrobial (e.g. antibacterial and antifungal) substances and to compositions containing them. More particularly, it relates to fluorocarbon quaternary salts and compositions thereof.
Various quaternary salts are known to be useful and active antimicrobials. Certain fluorocarbon quaternary salts have also been known previously e.g., (see U.S. Patents 2,727,923, 2,759,019, 2,764,602 and 2,764,603). These have been shown to be surface active compounds with unusual properties, but their use as antimicrobials has not been disclosed. Indeed, the fluorocarbon quaternary salts, particularly those with larger fluorocarbon groups (e.g. above C F would be expected to have little or no antimicrobial activity since such fluorocarbon groups normally reduce or obviate pharmaceutical activity. The present invention relates to a novel class of fluorocarbon quaternary salts (containing relatively large fluorocarbon groups) which are not only unexpectedly active antimicrobials, but which, as will be shown, are much safer for certain applications than previously known quaternary antimicrobials.
It is an object of the present invention to provide a novel class of quaternary compounds.
It is another object of the present invention to provide novel antimicrobial compositions comprising certain new fluorocarbon quaternary compounds in a pharmaceutical medium.
It is another object of the invention to provide a new method of combatting microbes comprising contracting them with a fluorocarbon quaternary compound.
Still other objects of the invention will become apparent to those skilled in the art from the following detailed description.
DETAILED DESCRIPTION In accordance with the various aims and concepts of the present invention, there are provided fluorocarbon substituted quaternary compounds of the formula:
wherein m is 5-7. These compounds are conveniently prepared by treating pyridine with an alkylating agent, such as in an inert solvent, usually at an elevated temperature.
The high degree of safety of the compounds of the invention as antimicrobials is of major importance in various areas of use. An example of this is topical application to wounds of domestic animals or pets. Since the wounded area is likely to be licked 'by the animal, it is important that the antimicrobial be as non-toxic as possible while 3,488,358 Patented Jan. 6, 1970 ice still retaining its effectiveness. Another area in which safeness is important is in oral antiseptics such as mouth washes.
The relative safety of compounds for therapeutic uses is commonly measured as a Therapeutic Index, i.e. the ratio of effectiveness to lethality. In the present case, this can be measured as the ratio of the effectiveness against microorganisms to the lethality against test animals.
As antimicrobial agents, the compounds of this invention may be applied directly and alone to the tissue or material to be treated or conventional carriers or diluents may be incorporated with them before application. The choice of carrier or diluent and the concentration of the active ingredient are determined by the use of the composition.
For treatment of topical infections in mammals, e.g. in dogs or other domestic animals, the compositions are usefully employed as ointments which are not readily removed from the treated area by movement or rubbing. Other pharmaceutical carriers which can be used are organic solvents (such as alcohols, e.g. ethyl alcohol), Water (to dissolve or suspend the active ingredient), solid inert materials such as talc, bentonite, kieselguhr, diatomaceous earth, and the like, emulsifying agents, etc. The fluorocarbon quaternary salts of the invention can also be dispersed in pressure sensitive adhesives for use in surgical tapes, drapes, etc. In such cases, the adhesives can also be considered to be pharmaceutical extending media.
The following will illustrate the preparation of the compositions of the invention and their antimicrobial effectiveness.
1,1 dihydroperfluorooctyl trifluoromethanesulfonate (5.3 g., 0.010 mole) was added dropwise to a stirred solution of 1.8 g. (0.022 mole) of pyridine in ml. 2-butanone at reflux temperature. After heating for an additional two days, the mixture was concentrated to dryness. The oily residue was triturated with ether to .aiford a solid which was collected and recrystallized twice from chloroform to afford 1.4 g. (23%) of N-(1,1-dihydroperfluorooctyl)pyridinium trifluoromethanesulfonate having the structure:
e C) )v-ormormomcmsm The melting point of this compound was -1115 and the results of analytical tests thereon were as follows:
Calcd for C13H7F15NCF3O3S: C, 27.5; H, 1.5. Found: C, 27.6; H, 1.3.
The 1.1 dihydroperfluorooctyl trifluoromethanesulfonate used in the foregoing preparation was prepared according to the method described by Hensen (J. Org. Chem, vol. 30, p. 4322, 1965) utilizing 1,1-dihydroperfluorooctyl alcohol.
The effectiveness of the perfluorooctyl pyridinium salt as an antimicrobial was evaluated against four bacteria (Staphylococcus aureus, Streptococcus sp. 104 Escherichio coli and Bacillus subtilis) and two fungi (Aspcrgillus niger and Candida albicans) using a variation of the agar plate diffusion method of Vincent and Vincent (Proc. Soc. Expty. Biol. Med. 55: 162-164) using culture media based on the synthetic glucose-salts medium of Davis and Mingioli (Jour. Bact. 66: 129-136). Both serum free cultures and cultures with serum or blood were tested with each microorganism. For purposes of comparison an identical set of tests were run utilizing the well known and highly active antimicrobial compound cetyl pyridinium chloride (ref. The Merck Index of Chemicals and Drugs, Published by Merck and Co., Inc.-, Rahway, N.J., Seventh Edition, 1960, p. 227). The perfluorooctyl pyridinium salt was found to be significantly more active against the bacteria than the cetylpyridinium chloride and slightly less active against the fungi.
Comparing the same two compounds as to their acute 2. A compound according to claim 1 wherein m is 6.
:oxicity in rate it was found that the LD (oral) of the perfluorooctyl pyridinium salt is 1159 mg./kg. and that References Cited he LD (oral) of the cetylpyridinum chloride it 538 FOREIGN PATENTS ng./kg. Thus the efl'ective safety (Therapeutic Index) 5 of the perfluorooctyl pyridinium salt is very significantly 1,059,278 2/1907 Great Brltalllgreater than that of the cetylpyridinium chloride against 90th bacterial and fungi, particularly the former. HENRY JI ES, Primary Examiner What is claimed is: 1. A quaternary compound of the formula: 10 Asslstant Exammer O Il-CH (CF -OF, CF3SO3 US. Cl. X.R. A 424263 wherein m is 5-7.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US62066567A | 1967-03-06 | 1967-03-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3488358A true US3488358A (en) | 1970-01-06 |
Family
ID=24486856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US620665A Expired - Lifetime US3488358A (en) | 1967-03-06 | 1967-03-06 | Certain 1,1 - dihydroperfluoroalkylpyridinium trifluoromethane sulfonates |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3488358A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1059278A (en) * | 1963-08-12 | 1967-02-15 | Colgate Palmolive Co | Textile treating compounds |
-
1967
- 1967-03-06 US US620665A patent/US3488358A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1059278A (en) * | 1963-08-12 | 1967-02-15 | Colgate Palmolive Co | Textile treating compounds |
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