US3519414A - Algaetoxic,synergistic compositions of aza - 1 - cycloheptenes and quaternary ammonium compounds and method of use - Google Patents
Algaetoxic,synergistic compositions of aza - 1 - cycloheptenes and quaternary ammonium compounds and method of use Download PDFInfo
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- US3519414A US3519414A US602485A US3519414DA US3519414A US 3519414 A US3519414 A US 3519414A US 602485 A US602485 A US 602485A US 3519414D A US3519414D A US 3519414DA US 3519414 A US3519414 A US 3519414A
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- Prior art keywords
- cycloheptene
- aza
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- water
- compounds
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- 239000000203 mixture Substances 0.000 title description 34
- 230000002195 synergetic effect Effects 0.000 title description 16
- 238000000034 method Methods 0.000 title description 13
- 150000003856 quaternary ammonium compounds Chemical class 0.000 title description 6
- 150000001875 compounds Chemical class 0.000 description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 28
- 239000000243 solution Substances 0.000 description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 22
- 125000004432 carbon atom Chemical group C* 0.000 description 20
- 125000000217 alkyl group Chemical group 0.000 description 19
- 235000019441 ethanol Nutrition 0.000 description 17
- 150000003839 salts Chemical class 0.000 description 17
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 description 16
- -1 Z-tetradecylamino-l-aza-l-cycloheptene Chemical compound 0.000 description 15
- 241000195493 Cryptophyta Species 0.000 description 14
- ZIFWLRRQTNRMCW-UHFFFAOYSA-N N-dodecyl-3,4,5,6-tetrahydro-2H-azepin-7-amine Chemical compound C(CCCCCCCCCCC)NC1=NCCCCC1 ZIFWLRRQTNRMCW-UHFFFAOYSA-N 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 13
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- 239000003208 petroleum Substances 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 description 6
- 150000001933 cycloheptenes Chemical class 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 230000001476 alcoholic effect Effects 0.000 description 5
- 229960001927 cetylpyridinium chloride Drugs 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 4
- 229940027983 antiseptic and disinfectant quaternary ammonium compound Drugs 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- LHJGJYXLEPZJPM-UHFFFAOYSA-N 2,4,5-trichlorophenol Chemical compound OC1=CC(Cl)=C(Cl)C=C1Cl LHJGJYXLEPZJPM-UHFFFAOYSA-N 0.000 description 3
- MSJLMQTXVKCUCD-UHFFFAOYSA-M 2-dodecylisoquinolin-2-ium;bromide Chemical compound [Br-].C1=CC=CC2=C[N+](CCCCCCCCCCCC)=CC=C21 MSJLMQTXVKCUCD-UHFFFAOYSA-M 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- DNXIQMQGKSQHPC-UHFFFAOYSA-N 7-methoxy-3,4,5,6-tetrahydro-2h-azepine Chemical compound COC1=NCCCCC1 DNXIQMQGKSQHPC-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 3
- 229940073608 benzyl chloride Drugs 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 229940093915 gynecological organic acid Drugs 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- FFJMLWSZNCJCSZ-UHFFFAOYSA-N n-methylmethanamine;hydrobromide Chemical class Br.CNC FFJMLWSZNCJCSZ-UHFFFAOYSA-N 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000011345 viscous material Substances 0.000 description 3
- 239000001888 Peptone Substances 0.000 description 2
- 108010080698 Peptones Proteins 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 239000003619 algicide Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- LBOGZEQDXVHCJL-UHFFFAOYSA-N cyclohepten-1-amine Chemical class NC1=CCCCCC1 LBOGZEQDXVHCJL-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 235000019319 peptone Nutrition 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QAQSNXHKHKONNS-UHFFFAOYSA-N 1-ethyl-2-hydroxy-4-methyl-6-oxopyridine-3-carboxamide Chemical compound CCN1C(O)=C(C(N)=O)C(C)=CC1=O QAQSNXHKHKONNS-UHFFFAOYSA-N 0.000 description 1
- PKKDWPSOOQBWFB-UHFFFAOYSA-N 2,4-dichloro-6-[(3,5-dichloro-2-hydroxyphenyl)methyl]phenol Chemical compound OC1=C(Cl)C=C(Cl)C=C1CC1=CC(Cl)=CC(Cl)=C1O PKKDWPSOOQBWFB-UHFFFAOYSA-N 0.000 description 1
- LYOFHYLVYHTGBK-UHFFFAOYSA-N 4-chloro-1,5-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=C(Cl)C=CC(C)(O)C1 LYOFHYLVYHTGBK-UHFFFAOYSA-N 0.000 description 1
- WFJIVOKAWHGMBH-UHFFFAOYSA-N 4-hexylbenzene-1,3-diol Chemical compound CCCCCCC1=CC=C(O)C=C1O WFJIVOKAWHGMBH-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 238000009631 Broth culture Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000195585 Chlamydomonas Species 0.000 description 1
- 241000195649 Chlorella <Chlorellales> Species 0.000 description 1
- 240000009108 Chlorella vulgaris Species 0.000 description 1
- 235000007089 Chlorella vulgaris Nutrition 0.000 description 1
- 241000725101 Clea Species 0.000 description 1
- MDNWOSOZYLHTCG-UHFFFAOYSA-N Dichlorophen Chemical compound OC1=CC=C(Cl)C=C1CC1=CC(Cl)=CC=C1O MDNWOSOZYLHTCG-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- JFIOVJDNOJYLKP-UHFFFAOYSA-N bithionol Chemical compound OC1=C(Cl)C=C(Cl)C=C1SC1=CC(Cl)=CC(Cl)=C1O JFIOVJDNOJYLKP-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- XRWMGCFJVKDVMD-UHFFFAOYSA-M didodecyl(dimethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC XRWMGCFJVKDVMD-UHFFFAOYSA-M 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- ACGUYXCXAPNIKK-UHFFFAOYSA-N hexachlorophene Chemical compound OC1=C(Cl)C=C(Cl)C(Cl)=C1CC1=C(O)C(Cl)=CC(Cl)=C1Cl ACGUYXCXAPNIKK-UHFFFAOYSA-N 0.000 description 1
- 229960003258 hexylresorcinol Drugs 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002054 inoculum Substances 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- 230000017066 negative regulation of growth Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000013207 serial dilution Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings 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
- C07D223/12—Nitrogen atoms not forming part of a nitro radical
-
- 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
- A01N43/46—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom rings with more than six members
Definitions
- This invention relates to the use of certain compounds for the purpose of preventing the development of algae. More particularly, this invention relates to the algaetoxic use of compounds having the formula:
- R is an alkyl group having from 10 to 18 carbon atims; and addition salts thereof.
- the cycloheptene compounds of the present invention have been found to possess high levels of algaetoxic activity, in the form of solutions, emulsions or suspensions.
- Solvents such as acetone, isopropanol and propylene glycol, per se or in admixture with each other or with other liquids such as water, may be used to form solutions.
- Dispersions or emulsions with water or other non-solvents for the compounds can be used, if desired.
- the compounds of this invention may be employed along with any conventional ingredients, for example, with other substances having microbiological activity, such as other algaestats or algaecides.
- the compounds of this invention may be formulated with or without conventional carriers to obtain the desired concentrations and to facilitate use.
- the algaetoxic agents or suspensions, emulsions or solutions thereof are added to the water system to be protected,.
- Streams, ponds, swimming pools, water cooling towers, irrigation ditches and reservoirs are examples of water systems which can be protected with the active algaetoxic agents of this invention.
- Class 1 quaternary compounds having the following structural formula:
- R is an alkyl group having from about 12 to 20 carbon atoms and X is a halogen
- Class 2 quaternary compounds formed from benzyl halide and a compound having the structural formula:
- R is a member selected from an alkyl group having from about 8 to 18 carbon atoms and an alkylene group having from about 8 to 18 carbon atoms;
- Class 3 quaternary compounds having the structural formula:
- Class 4 quaternary compounds having the structural formula:
- R3N X- wherein R is an alkyl group having from 12 to 16 carbon atoms and X is a halogen.
- the quaternary compounds useful in accordance with this invention are viscous to solid, colorless to amber-like and soluble in water and the common alcoholic solvents, such as ethyl alcohol.
- the Class 1 quaternaries are soluble in petroleum ether; whereas, the others are not.
- compositions containing the cycloheptene agents of this invention and the aforeindicated quaternary compounds are prepared and used in substantially the same manner as the compositions without the quaternary compounds.
- the ratio of cycloheptene to quaternary compound may vary over wide limits. We have found that a range of ratios of 16 to l to 0.12 to 1 by weight of the cycloheptene to that of the quaternary compound exhibits a synergistic activity. Higher or lower ratios could be used but the activity would probably represent the activity of the larger active component in the system. We presently prefer to use a ratio of 1 to 1.
- Solutions of the cycloheptene and quaternary compound, for example, in alcohol, are colorless to light amber in color depending upon the concentrations of these materials.
- Mixtures of the cycloheptene and quaternaries themselves are generally viscous, when freshly-prepared, but solidify partially or completely, on standing at ambient room temperatures over a period of a week or more. Some mixtures are solid even when freshly prepared. The mixtures are water-White to amber in color and soluble in water and common alcoholic solvents.
- Mixtures of Class 1 quaternaries and cycloheptene compounds are completely soluble in petroleum ether, whereas the other mixtures are not soluble in that solvent.
- Algaestatic tests were conducted using Chlorella vulgaris ATCC 9765 and ChlamydOmonas pseudaglo'e ATOC 12235 as test organisms. Both organisms were grown in ATCC peptone broth and Allens medium continuously illuminated with 150 foot candle light from a 30 watt, cool white, fluorescent (Gen. Electric) tube for a period of 30 days. The temperature of incubation was 25 C. Dilutions of compounds in broth were accomplished by first preparing two-fold serial alcoholic dilutions from 0.1% alcoholic solutions of test compounds. Aliquots (0.1 m1.) of the alcoholic two-fold serial dilutions were added to 50 ml. Fernbach fiasks containing 20 ml. of culture media.
- Inocula were prepared from seven day old ATOC peptone broth cultures by diluting with the same sterile broth to transmittance (530 mu) in a Lumetron colorimeter, model 401A. Each test flask received one drop (0.05 ml.) of inoculum. Flasks were incubated for 30 days and the minimal inhibitory concentration of the two-fold serial concentration series recorded as shown in Table I below.
- l ATCC broth Yeast ext. (Dlfco) 1 g.; Beef ext. (Difco) 1 g.; Tryptose (Diico) 2 g.; Glucose 10 g.; to 1,000 m1.
- Examples 7-11, inclusive, give data showing the inhibitory concentrations of 2-laurylamino-l-aza-cycloheptene and Z-tetradecylamino-l-aza-cycloheptene, per se, and in Hyaomine 3500:
- No. 3231 is 2-laurylamino-l-aza-l-cycloheptene.
- No. 4258 is Z-tetradecylamino-l-aza-l-cycloheptene.
- Acetoquat CPC is cetyl pyridinium chloride, marketed by Aceto Chemical Co., Flushing, N.Y. It is a white solid, with a melting point of 83 C., and is soluble in water and alcohol but insoluble in petroleum ether.
- Cetyl pyridinium bromide has a MP. of 61-62 C. It is soluble in alcohol and dioxane, sparingly soluble in cold water, soluble in water at 30 C. and insoluble in petroleum ether.
- Hyamine 3500 is a mixture of N-alkyl dimethyl benzylammonium chlorides, marketed by Rohm & Haas, Philadelphia, Pa.
- the alkyl groups contain from 12 to 16 carbon atoms. This product is available commercially as a 5 and solution in Water and alcohol, The
- quaternary compound is obtained by evaporating the solvents on the steam bath.
- the product is a nearly colorless soft, slightly tacky, very viscous material which is soluble in alcohol and water, and insoluble in petroleum ether.
- Isothan DL-l is a mixture of dialkyl dimethyl ammonium bromides, marketed by Onyx Chemical Co., Jersey City, NJ.
- the alkyl groups contain from 10' to 16 carbon atoms in the ratio in which they are derived from the fatty acids present in coconut oil. This product is available commercially as a 75% solution in isopropanol.
- the quaternary compound was obtained by evaporating the solvent on the steam bath. It is a soft, very viscous material, soluble in alcohol and water, and in petroleum ether.
- Nalquat G8-11 is a mixture of 1-(2-hydroxyethyl)-2- alkylimidazolines, quaternized by means of benzyl chlo ride, marketed by Nalco Chemical Co., Chicago, Ill.
- the alkyl groups contain from 11 to 17 carbon atoms.
- This product is available as a 60% solution and the quaternary compound is obtained by evaporating the solvent on the steam bath.
- the compound is a nearly colorless to amber, very viscous material, soluble in alcohol and water but insoluble in petroleum ether.
- a coordinate point (sample preparation) reading Column 4 and Row 5 would correspond to 0.625 meg/ml. of the column component and 1.25 meg/ml. of the row component and a total for the two component mixture of 1.875 meg/ml.
- Enhancement action rather than an additive effect may be determined by relating the relative activities of each component in terms of a single component.
- Example 8 it required 2.5 mcg./ml. 3231 and 1.25 mcg./ ml. Hyamine 3500 for complete inhibition of growth.
- the Column 1, Row 1 coordinate sample resulted in complete inhibition in which case the sample contained 0.078 meg/ml. Hyamine 3500 and meg/ml. This corresponds to an approximate (1.25/.117) 11-fold increase in activity for this particular combination.
- Active cycloheptenes and quaternary compounds in accordance with this invention may be prepared in accordance with known procedure.
- the cycloheptenes may be prepared by condensation of the appropriate alkylamines with O-methylcaprolactim (3,4,5,6-tetrahydro-2H-azepin-7-ol methyl ether), in accordance with the following representation:
- EXAMPLE 12 Preparation of 2-laurylaminol -azal-cycloheptene O-methylcaprolactim (38 g.) and 55 g. of Formonyte D616 (Foremost Food and Chemical Company), a commercial grade of laurylamine were charged into a 250 ml. flask fitted with a sealed stirrer, a thermometer and an adapter connected to a condenser for condensation of the methanol generated during the reaction.
- the agitated contents of the flask were heated gradually over a period of seven hours from 138 to 185. About 6.5 ml. of methanol were collected.
- the resulting brown oil was distilled at a pressure of 5 mm.
- the compound is soluble in isopropanol and acetone. It disperses in water; such dispersions froth abundantly. Solutions in dilute acids are excellent foamers.
- the hydrochloride of the compound is a white, crystalline solid; M.P. 148-149.
- the solvent is removed on the steam bath or under reduced pressure, leaving the salts as oily or resinous or crystalline products, which, in certain cases, can be rec ystallized.
- inorganic acids hydrochloric acid, sulfuric acid, phosphoric acid.
- organic acids examples include acetic acid, lactic acid, benzoic acid.
- phenols 2,4,5-trichlorophenol, p-chlorom-xylenol, hexylresorcinol.
- EXAMPLE 13 Z-Iaurylamino-l-aza-l-cycloheptene hydrochloride 2-laurylamino-l-aza-l-cycloheptene (8.4 g.) ice-water (60 g.), alcohol (30 ml.) and cone. hydrochloric acid 38% (4 g.) were mixed in a beaker. The resulting solution was poured into a dish and the solvents were allowed to evaporate spontaneously overnight. A white solid resulted which was freed of adhering moisture by suction filtration. It was dried at a pressure of 4 mm. at room temperature. The hydrochloride was recrystallized from a mixture of hexane and isopropanol. The recrystallized material had a M.P. of 148-149.
- EXAMPLE 15 Salt of 2-laurylamino-l-aza-l-cycloheptene with 2,4,5-trichlorophenol
- 2-laurylamino-l-aza-l-cycloheptene (0.7 g.) and 2,4,5- trichlorophenol (0.5 g.) were dissolved in 5 ml. of methanol.
- the solution was freed of the methanol on the steam bath.
- the resulting salt is a tacky, slightly colored resin. It is insoluble in water and soluble in isopropanol.
- EXAMPLE 16 Salt of 2-laurylamino-l-aza-l-cycloheptene with 2,2- methylenebis(3,4,6-trichlorophenol), G-11 2-laurylamino-l-aza-l-cycloheptene (0.7 g.) and 6-11 (1.02 g.) were dissolved in 5 ml. of methanol. The solution was freed of the methanol on the steam bath. The resulting salt is a hard, yellowish resin, insoluble in water and soluble in isopropanol.
- Quaternary compounds useful in accordance with this invention may be prepared by reaction of the suitable tertiary amines with the appropriate halo compounds.
- the reaction is carried out preferentially at elevated temperatures of about 50-150 in the absence, or in the presence, of solvents. Eventually, the condensation is allowed to take place in an autoclave, especially when halo compounds with low boiling points, are being employed. Usually, the yields are quantitative or nearly quantitative. No further purification is necessary for the intended uses although in the cases of solid reaction products crystallization is possible.
- Examples 17-20, inclusive, give details of the preparation of specific members of the aforementioned four classes of quaternary compounds, each preparation being typical of the class.
- EXAMPLE 21 One gram of 2-laurylamino-1-aza-1-cycloheptene and one gram of cetylpyridinium chloride were mixed and finely ground in mortar. A white solid resulted; M.P. starts to sinter at about 47; melts at about 75. The mixture is soluble in alcohol, propylene glycol, and in water; partially soluble in petroleum ether.
- the resulting mixture is a very viscous oil, changing slowly to an oily solid. It is soluble in water; concentrated solutions are turbid; dilute solutions are limpid; it is partially soluble in petroleum ether at room temperature; solutions in alcohol or isopropanol are clear.
- EXAMPLE 23 One gram of Z-laurylamino-l-aza-l-cycloheptene and one gram of the compound contained in Nalquat G811 were dissolved in 5 ml. of methanol. The solvent was evaporated on the steam bath. The remaining product is a viscous oil, changing slowly to an oily solid.
- Solutions in alcohol, isopropanol or propylene glycol are clea'. Depending on the concentration, solutions in water are turbid or clear. The mixture is not soluble in petroleum ether.
- EXAMPLE 24 Oneg ram of 2-laurylamino-l-aza-l-cycloheptene and one gram of the compound contained in Isothan DL-l were dissolved in 5 ml. of methanol. The solvent was evaporated on the steam bath. The remaining product is a viscous, nearly colorless oil, changing slowly to an oily solid. It is clearly soluble in alcohol, propylene glycol or isopropanol. Concentrated solutions in water are turbid; dilute solutions are very slightly hazy. It is soluble in petroleum ether.
- mixtures of the azacycloheptenes with the quaternary ammonium compounds with a diiferent ratio then 5:5, as for instance 1:9 or 9.1 have properties similar to those described above.
- a method for preventing the development of algae which comprises applying to the locus to be protected an algaestatically effective amount of a member selected from the group consisting of (a) a quaternary compound having the following structural formula:
- R is an alkyl group having from about 12 to 20 carbon atoms and X is a halogen
- R' is a member selected from an alkyl group having from about 8 to 18 carbon atoms and an alkylene group having from about 8 to 18 carbon atoms;
- R is an alkyl group having from 12 to 16 carbon atoms and X is a halogen
- R is an alkyl group having from 12 to 16 carbon atoms and X is a halogen, in synergistic admixture with a cycloheptene selected from the group consisting of 2-lauryl-amino-1-aza-l-cycloheptene, and acid addition salts or phenol addition salts thereof.
- cycloheptene is selected from the group consisting of Z-tetradecylaminol-aza-l-cycloheptene and its acid addition salts or phenol addition salts thereof.
- the quaternary compound is a mixture of dialkyl dimethyl ammonium bromides having from 12 to 16 carbon atoms in the alkyl groups and the cycloheptene is 2-laurylamino-1-aza-1- cycloheptene.
- the quaternary compound is a mixture of 1-(2-hydroxyethyl)-2-alkylimidazolines having from 11 to 17 carbon atoms in the alkyl group, quaternized by means of benzyl chloride, and the cycloheptene is 2-laurylamino-l-aza-l-cycloheptene.
- the quaternary compound is a mixture of N-alkyl dimethylbenzyl ammonium chlorides wherein alkyl has from 10 to 16 carbon atoms and the cycloheptene is 2-laurylamino-l-azal-cycloheptene.
- the quaternary ammonium compound is a mixture of dialkyl dimethyl ammonium bromides having from 12 to 16 carbon atoms in the alkyl groups, and the cycloheptene is Z-tetradecylamino-l-aza-l-cycloheptene.
- the quaternary compound is a mixture of l-(2-hydroxyethyl)-2-alkylimidazolines having from 11 to 17 carbon atoms in the alkyl groups, quaternized by means of benzyl chloride, and the cycloheptene is Z-tetradecyl-l-aza-1-cycloheptene.
- the quaternary compound is a mixture of N-alkyl dimethyl benzyl ammonium chlorides having from 10 to 16 carbon atoms in the alkyl group, and the cycloheptene is Z-tetradecylamino-1-aza-1-cycloheptene.
- a composition for preventing the development of algae which comprises the synergistic admixture set forth in claim 1.
- a composition for preventing the development of algae which comprises the synergistic admixture set forth in claim 2.
- a composition for preventing the development of algae which comprises the synergistic admixture set forth in claim 3.
- a composition for preventing the development of algae which comprises the synergistic admixture set forth in claim 4.
- a composition for preventing the development of algae which comprises the synergistic admixture set forth in claim 5.
- a composition for preventing the development of algae which comprises the synergistic admixture set forth in claim 6.
- a composition for preventing the development of algae which comprises the synergistic admixture set forth in claim 7.
- a composition for preventing the development of algae which comprises the synergistic admixture set forth in claim 8.
- a composition for preventing the development of 3,197,495 7/1965 Strycker -..'.J' 260-440 algae which comprises the synergistic admixture set forth 1 3,130,124 .4/ 1964 Ferris et a1. 16742 in claim 9. 1 I
- a composition for preventing the development of FOREIGN A EN algae, which comprises the synergistic admixture set forth 5 774,111 9 Ca da. in claim 10, 1, 1,367,799 6/1964 France.
Description
United States Patent US. Cl. 7167 20 Claims ABSTRACT OF THE DISCLOSURE A new class of algaecides is described. They have the formula CHz-CHz RNH-(I? CH2 NCH2-(JH2 wherein R is an alkyl group having from 10 to 18 carbon atoms; and addition salts thereof.
Also described is the synergistic effect that 2-laurylamino-l-aza-l-cycloheptene and Z-tetradecylamino-l-azal-cycloheptene, and their respective addition salts with inorganic and organic acids and phenols, exhibit with numerous quaternary ammonium compounds.
This invention relates to the use of certain compounds for the purpose of preventing the development of algae. More particularly, this invention relates to the algaetoxic use of compounds having the formula:
wherein R is an alkyl group having from 10 to 18 carbon atims; and addition salts thereof.
The cycloheptene compounds of the present invention have been found to possess high levels of algaetoxic activity, in the form of solutions, emulsions or suspensions. Solvents such as acetone, isopropanol and propylene glycol, per se or in admixture with each other or with other liquids such as water, may be used to form solutions. Dispersions or emulsions with water or other non-solvents for the compounds can be used, if desired.
Also, if desired, the compounds of this invention may be employed along with any conventional ingredients, for example, with other substances having microbiological activity, such as other algaestats or algaecides.
For practical use as algaetoxic agents, the compounds of this invention may be formulated with or without conventional carriers to obtain the desired concentrations and to facilitate use. In use, the algaetoxic agents or suspensions, emulsions or solutions thereof are added to the water system to be protected,. Streams, ponds, swimming pools, water cooling towers, irrigation ditches and reservoirs are examples of water systems which can be protected with the active algaetoxic agents of this invention.
So far as concerns the amount of algaetoxic agent to be employed, this is subject to various considerations, such as the type of water to be treated. Generally, as little as 5 mcg./ml. will be suflicient to inhibit the growth of algae. In any event, it will be understood by those skilled in the art that a quantity of'algaetoxic agent, sufficient to yield at least the minimal inhibitory concentration of agent in the water system to be protected, should be used.
In addition to the unexpected and unobvious algaetoxic properties of the compounds of this invention, a further ice surprising finding has been made by us. We refer to the finding that 2- laurylamino-l-aza-l-cycloheptene and Z-tetradecylamino-l-aza-l-cycloheptene, and their respective addition salts with inorganic and organic acids and phenols, have the property of exhibiting synergistic algae toxic effects with certain quaternary ammonium compounds. The quaternary ammonium compounds referred to are the following:
Class 1: quaternary compounds having the following structural formula:
N R CH 8 wherein R is an alkyl group having from about 12 to 20 carbon atoms and X is a halogen;
Class 2: quaternary compounds formed from benzyl halide and a compound having the structural formula:
?H2CH2OH /NCH2 RC N-CH:
where R is a member selected from an alkyl group having from about 8 to 18 carbon atoms and an alkylene group having from about 8 to 18 carbon atoms;
Class 3: quaternary compounds having the structural formula:
CH3 R OHzC Hs wherein R is an alkyl group having from 12 to 16 carbon atoms and X is a halogen; and
Class 4: quaternary compounds having the structural formula:
R3N X- wherein R is an alkyl group having from 12 to 16 carbon atoms and X is a halogen.
The quaternary compounds useful in accordance with this invention are viscous to solid, colorless to amber-like and soluble in water and the common alcoholic solvents, such as ethyl alcohol. The Class 1 quaternaries are soluble in petroleum ether; whereas, the others are not.
Compositions containing the cycloheptene agents of this invention and the aforeindicated quaternary compounds are prepared and used in substantially the same manner as the compositions without the quaternary compounds.
The ratio of cycloheptene to quaternary compound may vary over wide limits. We have found that a range of ratios of 16 to l to 0.12 to 1 by weight of the cycloheptene to that of the quaternary compound exhibits a synergistic activity. Higher or lower ratios could be used but the activity would probably represent the activity of the larger active component in the system. We presently prefer to use a ratio of 1 to 1.
Solutions of the cycloheptene and quaternary compound, for example, in alcohol, are colorless to light amber in color depending upon the concentrations of these materials. Mixtures of the cycloheptene and quaternaries themselves, are generally viscous, when freshly-prepared, but solidify partially or completely, on standing at ambient room temperatures over a period of a week or more. Some mixtures are solid even when freshly prepared. The mixtures are water-White to amber in color and soluble in water and common alcoholic solvents. Mixtures of Class 1 quaternaries and cycloheptene compounds are completely soluble in petroleum ether, whereas the other mixtures are not soluble in that solvent.
In order to illustrate the algaetoxic activity of the compounds falling within the scope of this invention, there is presented below a series of test results. It is understood that these results are reported solely by way of illustration and are not in any way intended to be construed as a limitation of the present invention. All degrees are Centigrade unless otherwise stated.
Algaestatic tests were conducted using Chlorella vulgaris ATCC 9765 and ChlamydOmonas pseudaglo'e ATOC 12235 as test organisms. Both organisms were grown in ATCC peptone broth and Allens medium continuously illuminated with 150 foot candle light from a 30 watt, cool white, fluorescent (Gen. Electric) tube for a period of 30 days. The temperature of incubation was 25 C. Dilutions of compounds in broth were accomplished by first preparing two-fold serial alcoholic dilutions from 0.1% alcoholic solutions of test compounds. Aliquots (0.1 m1.) of the alcoholic two-fold serial dilutions were added to 50 ml. Fernbach fiasks containing 20 ml. of culture media. Inocula were prepared from seven day old ATOC peptone broth cultures by diluting with the same sterile broth to transmittance (530 mu) in a Lumetron colorimeter, model 401A. Each test flask received one drop (0.05 ml.) of inoculum. Flasks were incubated for 30 days and the minimal inhibitory concentration of the two-fold serial concentration series recorded as shown in Table I below.
lllll++++ EXAMPLE 10 No. 3231 N alguat G-8-11:
lllll+ lllll++ llll|l++ TABLE I..ALGAESTATIO (MINIMAL INHIBITORY CONCENTRATIONS) OF AZA- GYCLOHEPTENE DERIVATIVES. (MCG./ML.).
Chlorella. Chlamydomonus vulaaris pseudagloe Example No. Allens A.T.C.C. Allen's 1 A.'I.C.C.
1 2-decylamlno-l-aza-l-cycloheptene 2. 5 2. 6 5. 0 2. 5 2 Z-tetradecylamino-1-aza-1-cycloheptene 2. 5 2. 5 2. 5 2. 5 3 2-hexadecylamino-l-aza-l-cycloheptene 2. 5 2. 5 2. 5 2. 5 4 2(1-methyldecylamino)-1-aza-1-oycloheptene 2. 5 2. 5 2. 5 2. 5 5 2-laurylamino-1aza-1-cycloheptena 1. 25 1. 25 1. 25 1. 6.. 2-octadecylamino-1-aza-1-cycloheptene 5. 0 5. 0 5. 00 5. 00
l ATCC broth=Yeast ext. (Dlfco) 1 g.; Beef ext. (Difco) 1 g.; Tryptose (Diico) 2 g.; Glucose 10 g.; to 1,000 m1.
dist. water, pH 7 5 Allen's mediuin=Allen, M. 13., Archiv nu Mikrobiologie, news 1952).
Examples 7-11, inclusive, give data showing the inhibitory concentrations of 2-laurylamino-l-aza-cycloheptene and Z-tetradecylamino-l-aza-cycloheptene, per se, and in Hyaomine 3500:
lllll+ Illl-lilll-l- III- EXAMPLE 11 N 0. 4258 Hyanine 3500:
lllll'illlll+++ In order that Examples 7-11, inclusive, may be easily and fully understood, the following codes are given:
No. 3231 is 2-laurylamino-l-aza-l-cycloheptene.
No. 4258 is Z-tetradecylamino-l-aza-l-cycloheptene.
Acetoquat CPC is cetyl pyridinium chloride, marketed by Aceto Chemical Co., Flushing, N.Y. It is a white solid, with a melting point of 83 C., and is soluble in water and alcohol but insoluble in petroleum ether.
Cetyl pyridinium bromide has a MP. of 61-62 C. It is soluble in alcohol and dioxane, sparingly soluble in cold water, soluble in water at 30 C. and insoluble in petroleum ether.
Hyamine 3500 is a mixture of N-alkyl dimethyl benzylammonium chlorides, marketed by Rohm & Haas, Philadelphia, Pa. The alkyl groups contain from 12 to 16 carbon atoms. This product is available commercially as a 5 and solution in Water and alcohol, The
quaternary compound is obtained by evaporating the solvents on the steam bath. The product is a nearly colorless soft, slightly tacky, very viscous material which is soluble in alcohol and water, and insoluble in petroleum ether.
Isothan DL-l is a mixture of dialkyl dimethyl ammonium bromides, marketed by Onyx Chemical Co., Jersey City, NJ. The alkyl groups contain from 10' to 16 carbon atoms in the ratio in which they are derived from the fatty acids present in coconut oil. This product is available commercially as a 75% solution in isopropanol. The quaternary compound was obtained by evaporating the solvent on the steam bath. It is a soft, very viscous material, soluble in alcohol and water, and in petroleum ether.
Nalquat G8-11 is a mixture of 1-(2-hydroxyethyl)-2- alkylimidazolines, quaternized by means of benzyl chlo ride, marketed by Nalco Chemical Co., Chicago, Ill. The alkyl groups contain from 11 to 17 carbon atoms. This product is available as a 60% solution and the quaternary compound is obtained by evaporating the solvent on the steam bath. The compound is a nearly colorless to amber, very viscous material, soluble in alcohol and water but insoluble in petroleum ether.
The code identifying the concentrations represented by integers from to 8 in Examples 7-11, inclusive, is given below:
Meg/m1. 8 1O 7 5 6 2.5 5 1.25 4 0.625 3 0.312 2 0.156 1 0.078 0 0.000
For ease of presentation the combinations in Examples 7 to 11, inclusive, are presented in coordinate graphic form with corresponding growth and complete inhibition notations.
A coordinate point (sample preparation) reading Column 4 and Row 5 would correspond to 0.625 meg/ml. of the column component and 1.25 meg/ml. of the row component and a total for the two component mixture of 1.875 meg/ml.
Enhancement action rather than an additive effect may be determined by relating the relative activities of each component in terms of a single component. Thus in the case of the No. 3231 and Hyamine 3500 test, Example 8, it required 2.5 mcg./ml. 3231 and 1.25 mcg./ ml. Hyamine 3500 for complete inhibition of growth. On an activity basis 2.5 3231:;125 Hyamine 3500 or 1 unit Hyamine 350002 units of 3231. The Column 1, Row 1 coordinate sample resulted in complete inhibition in which case the sample contained 0.078 meg/ml. Hyamine 3500 and meg/ml. This corresponds to an approximate (1.25/.117) 11-fold increase in activity for this particular combination.
Active cycloheptenes and quaternary compounds in accordance with this invention may be prepared in accordance with known procedure.
The cycloheptenes may be prepared by condensation of the appropriate alkylamines with O-methylcaprolactim (3,4,5,6-tetrahydro-2H-azepin-7-ol methyl ether), in accordance with the following representation:
As an illustrative example of the preparation of an active cycloheptene we give the following example:
EXAMPLE 12 Preparation of 2-laurylaminol -azal-cycloheptene O-methylcaprolactim (38 g.) and 55 g. of Formonyte D616 (Foremost Food and Chemical Company), a commercial grade of laurylamine were charged into a 250 ml. flask fitted with a sealed stirrer, a thermometer and an adapter connected to a condenser for condensation of the methanol generated during the reaction.
The agitated contents of the flask were heated gradually over a period of seven hours from 138 to 185. About 6.5 ml. of methanol were collected.
The resulting brown oil was distilled at a pressure of 5 mm.
B.P. C. Weight G. (1) 118-200 3.4
(2) 200210 69.4 Residue 6.2
Fraction 2 congealed on standing to a white, soft solid;
AnaIysis.Calcd. for C H N (percent): C, 77.07; H, 12.94. Found (percent): C, 77.31; H, 12.90.
The compound is soluble in isopropanol and acetone. It disperses in water; such dispersions froth abundantly. Solutions in dilute acids are excellent foamers.
The hydrochloride of the compound is a white, crystalline solid; M.P. 148-149.
Analysis.-Calcd. for C1 H3 1N2Cl (percent): C, 68.21; H, 11.77; Cl, 11.19. Found (percent): C, 67.96; H, 11.72; Cl, 11.13.
Solutions of the hydrochloride in water foam.
Following the above procedure, in general, the other active cycloheptenes were prepared, with the characteristics as noted in Table 2.
TABLE 2 Physical appear- Analysis ance of the freshly C.P., Compound distilled product; B.P., C. 0. mi Percent Calcd. Found 2-de0y1amino-l-aza-l-cycloheptene Oil 185-189/5mm 1. 4905 g 73.12 33 1 .78 1 Q-(l-methyldecylamino)1aza-1-cycloheptene Oil 164-190/3nm1 1. 4872 76.62 72.51 12. 86 1 51 2-tetradecylamino-l-aza-1-cycloheptene Solid 205-220/3 111111.- 61 7g. 1 2-hexadecylamino-l-aza-1-cycloheptene do 230245/3 mm 54 ..{g[ 73.50 7%. 1 l8 1 Z-Qctadeeylamino-l-aza-l-cycloheptene .do 1 -72 X Melting point.
0.078 meg/ml. 3231 and a total of 0.156 meg/ml. total active component. In terms of Hyamine 3500 then this Salts of the active cycloheptenes of this invention may be prepared by dissolving equimolecular amounts of the sample contained 0.078 mcg./ml.+0.039 mcg./ml.=0.l17 azacycloheptenes and an inorganic acid, or an organic acid, or a phenol, including bis-phenols, in about a threefold amount of methanol, ethanol or isopropanol. In the case of bisphenols the ratio of the azacycloheptenes to bis-phenol can be 1:1 or 2:1.
The solvent is removed on the steam bath or under reduced pressure, leaving the salts as oily or resinous or crystalline products, which, in certain cases, can be rec ystallized.
Examples of inorganic acids: hydrochloric acid, sulfuric acid, phosphoric acid.
Examples of organic acids: acetic acid, lactic acid, benzoic acid.
Examples of phenols: 2,4,5-trichlorophenol, p-chlorom-xylenol, hexylresorcinol.
Examples of bis-phenols: 2,2'-methylenebis-(4-chlorophenol), 2,2'-methylenebis(4,6-dichlorophenol), 2,2- methylenebis (3,4,6-trichlorophenol, 2,2'-thiobis (4,6-dichlorophenol) Detailed description for the preparation of representative salts is given below in Examples 13-16, inclusive.
EXAMPLE 13 Z-Iaurylamino-l-aza-l-cycloheptene hydrochloride 2-laurylamino-l-aza-l-cycloheptene (8.4 g.) ice-water (60 g.), alcohol (30 ml.) and cone. hydrochloric acid 38% (4 g.) were mixed in a beaker. The resulting solution was poured into a dish and the solvents were allowed to evaporate spontaneously overnight. A white solid resulted which was freed of adhering moisture by suction filtration. It was dried at a pressure of 4 mm. at room temperature. The hydrochloride was recrystallized from a mixture of hexane and isopropanol. The recrystallized material had a M.P. of 148-149.
It is difiicultly soluble in water at room temperature and readily soluble in acetone.
EXAMPLE 14 Acetic acid salt of 2-laurylamino-1-aza-l-cycloheptene 2-laurylamino-1-aza-1-cycloheptene (1.4 g.) was dissolved in 5'ml. of methanol; glacial acetic acid (0.3 g.) was added. The resulting solution was freed of the solvent on the steam bath. The acetic acid salt resulted as a heavy oil of a slightly amber color. It is soluble in water; these solutions froth abundantly. It is soluble in ethanol, isopropanol and insoluble in petroleum ether.
EXAMPLE 15 Salt of 2-laurylamino-l-aza-l-cycloheptene with 2,4,5-trichlorophenol 2-laurylamino-l-aza-l-cycloheptene (0.7 g.) and 2,4,5- trichlorophenol (0.5 g.) were dissolved in 5 ml. of methanol. The solution was freed of the methanol on the steam bath. The resulting salt is a tacky, slightly colored resin. It is insoluble in water and soluble in isopropanol.
EXAMPLE 16 Salt of 2-laurylamino-l-aza-l-cycloheptene with 2,2- methylenebis(3,4,6-trichlorophenol), G-11 2-laurylamino-l-aza-l-cycloheptene (0.7 g.) and 6-11 (1.02 g.) were dissolved in 5 ml. of methanol. The solution was freed of the methanol on the steam bath. The resulting salt is a hard, yellowish resin, insoluble in water and soluble in isopropanol.
Substitution of the salts of the active aminocycloheptenes in any of the foregoing examples results in substantially the same algaetoxic effects as those secured with the corresponding aminocycloheptenes.
Quaternary compounds useful in accordance with this invention may be prepared by reaction of the suitable tertiary amines with the appropriate halo compounds.
The reaction is carried out preferentially at elevated temperatures of about 50-150 in the absence, or in the presence, of solvents. Eventually, the condensation is allowed to take place in an autoclave, especially when halo compounds with low boiling points, are being employed. Usually, the yields are quantitative or nearly quantitative. No further purification is necessary for the intended uses although in the cases of solid reaction products crystallization is possible.
Examples 17-20, inclusive, give details of the preparation of specific members of the aforementioned four classes of quaternary compounds, each preparation being typical of the class.
EXAMPLE 17 Class 1.Dilauryldimethylammonium bromide (corresponding to Isothan DL-l l-bromododecane (9.9 g.) and N,N-dimethyl-1-aminododecane (8.5 g.) were agitated and heated at 110-115 for minutes. A soft, slightly yellowish solid resulted. It is soluble in water. Concentrated solutions are hazy; dilute solutions are limpid. These solutions froth abundantly.
EXAMPLE 18 Class 2.1-(2-hydroxyethyl-1 (or 3 )-benzyl-2- undecylimidazolinium chloride EXAMPLE 19 Class 3.-Lauryldimethylbenzylammonium chloride This compound was prepared according to 0. Westphal and Dietrich Jerchel, Ber. 73 B, 1002.
l-chlorododecane (17.6 g.), N-dimethylbenzylamine (11.8 g.) and 10 ml. of alcohol were agitated and heated for 45 hours at 90. The alcohol was then distilled in vacuum. The residue was dissolved in hot ethyl acetate and the quaternary salt was precipitated by ethyl ether. Yield: quantitative. The compound is a very tacky oil, soluble in water, dilute acids and dilute alkali.
EXAMPLE 20 Class 4.Cetylpyridinium chloride This compound was prepared according to P. Karrer et al., Helv. Chim. Acta, 21, 233 (1938).
Tenth molar amounts of pyridine and l-chlorohexaadecane were heated in an autoclave for 15 hours at After cooling, the crystals were filtered and washed with ether; M.P., after recrystallization from benezene, 83.
Examples 21-24, inclusive, give illustration examples of specific typical synergistic compositions of this invention.
EXAMPLE 21 One gram of 2-laurylamino-1-aza-1-cycloheptene and one gram of cetylpyridinium chloride were mixed and finely ground in mortar. A white solid resulted; M.P. starts to sinter at about 47; melts at about 75. The mixture is soluble in alcohol, propylene glycol, and in water; partially soluble in petroleum ether.
9 EXAMPLE 22 One gram of 2-laurylamino-1-aza-1-cycloheptene and one gram of the compound contained in Hyamine 3500 were dissolved in 5 ml. of methanol and concentrated to dryness on the steam bath.
The resulting mixture is a very viscous oil, changing slowly to an oily solid. It is soluble in water; concentrated solutions are turbid; dilute solutions are limpid; it is partially soluble in petroleum ether at room temperature; solutions in alcohol or isopropanol are clear.
EXAMPLE 23 One gram of Z-laurylamino-l-aza-l-cycloheptene and one gram of the compound contained in Nalquat G811 were dissolved in 5 ml. of methanol. The solvent was evaporated on the steam bath. The remaining product is a viscous oil, changing slowly to an oily solid.
Solutions in alcohol, isopropanol or propylene glycol are clea'. Depending on the concentration, solutions in water are turbid or clear. The mixture is not soluble in petroleum ether.
EXAMPLE 24 Oneg ram of 2-laurylamino-l-aza-l-cycloheptene and one gram of the compound contained in Isothan DL-l were dissolved in 5 ml. of methanol. The solvent was evaporated on the steam bath. The remaining product is a viscous, nearly colorless oil, changing slowly to an oily solid. It is clearly soluble in alcohol, propylene glycol or isopropanol. Concentrated solutions in water are turbid; dilute solutions are very slightly hazy. It is soluble in petroleum ether.
The solut ons of the products of Examples 21 to 24, in water, froth abundantly. Turbid or hazy solution can be made limpid by the addition of small amounts of acids, as for instance acetice acid.
In general, mixtures of the azacycloheptenes with the quaternary ammonium compounds with a diiferent ratio then 5:5, as for instance 1:9 or 9.1 have properties similar to those described above.
The foregoing illustrates the practice of this invention, which, however is not to be limited thereby, but is to be construed as broadly as permissible in view of the prior art and limited solely by the appended claims.
What is claimed is:
1. A method for preventing the development of algae, which comprises applying to the locus to be protected an algaestatically effective amount of a member selected from the group consisting of (a) a quaternary compound having the following structural formula:
R CH3 1 R/ CHa wherein R is an alkyl group having from about 12 to 20 carbon atoms and X is a halogen;
(b) A quaternary compound formed from benzyl halide and a compound having the structural formula:
where R' is a member selected from an alkyl group having from about 8 to 18 carbon atoms and an alkylene group having from about 8 to 18 carbon atoms;
wherein R is an alkyl group having from 12 to 16 carbon atoms and X is a halogen; and
wherein R is an alkyl group having from 12 to 16 carbon atoms and X is a halogen, in synergistic admixture with a cycloheptene selected from the group consisting of 2-lauryl-amino-1-aza-l-cycloheptene, and acid addition salts or phenol addition salts thereof.
2. The method of claim 1, wherein the cycloheptene is selected from the group consisting of Z-tetradecylaminol-aza-l-cycloheptene and its acid addition salts or phenol addition salts thereof.
3. The method of claim 1, wherein the quaternary compound is a mixture of dialkyl dimethyl ammonium bromides having from 12 to 16 carbon atoms in the alkyl groups and the cycloheptene is 2-laurylamino-1-aza-1- cycloheptene.
4. The method of claim 1, wherein the quaternary compound is a mixture of 1-(2-hydroxyethyl)-2-alkylimidazolines having from 11 to 17 carbon atoms in the alkyl group, quaternized by means of benzyl chloride, and the cycloheptene is 2-laurylamino-l-aza-l-cycloheptene.
5. The method of claim 1, wherein the quaternary compound is a mixture of N-alkyl dimethylbenzyl ammonium chlorides wherein alkyl has from 10 to 16 carbon atoms and the cycloheptene is 2-laurylamino-l-azal-cycloheptene.
6. The method of claim 1, wherein the quaternary compound is cetyl pyridinium chloride and the cycloheptene is 2-laurylamino-l-aza-l-cycloheptene.
7. The method of claim 2, wherein the quaternary ammonium compound is a mixture of dialkyl dimethyl ammonium bromides having from 12 to 16 carbon atoms in the alkyl groups, and the cycloheptene is Z-tetradecylamino-l-aza-l-cycloheptene.
8. The method of claim 2, wherein the quaternary compound is a mixture of l-(2-hydroxyethyl)-2-alkylimidazolines having from 11 to 17 carbon atoms in the alkyl groups, quaternized by means of benzyl chloride, and the cycloheptene is Z-tetradecyl-l-aza-1-cycloheptene.
9. The method of claim 2, wherein the quaternary compound is a mixture of N-alkyl dimethyl benzyl ammonium chlorides having from 10 to 16 carbon atoms in the alkyl group, and the cycloheptene is Z-tetradecylamino-1-aza-1-cycloheptene.
10. The method of claim 2, wherein the quaternary compound is cetyl pyridinium chloride and the cycloheptene is Z-tetradecylamino-l-aZa-1-cycloheptene.
11. A composition for preventing the development of algae, which comprises the synergistic admixture set forth in claim 1.
12. A composition for preventing the development of algae, which comprises the synergistic admixture set forth in claim 2.
13. A composition for preventing the development of algae, which comprises the synergistic admixture set forth in claim 3.
14. A composition for preventing the development of algae, which comprises the synergistic admixture set forth in claim 4.
15. A composition for preventing the development of algae, which comprises the synergistic admixture set forth in claim 5.
16. A composition for preventing the development of algae, which comprises the synergistic admixture set forth in claim 6.
17. A composition for preventing the development of algae, which comprises the synergistic admixture set forth in claim 7.
18. A composition for preventing the development of algae, which comprises the synergistic admixture set forth in claim 8.
11 12 v 19. A composition for preventing the development of 3,197,495 7/1965 Strycker -..'.J' 260-440 algae, which comprises the synergistic admixture set forth 1 3,130,124 .4/ 1964 Ferris et a1. 16742 in claim 9. 1 I
20. A composition for preventing the development of FOREIGN, A EN algae, which comprises the synergistic admixture set forth 5 774,111 9 Ca da. in claim 10, 1, 1,367,799 6/1964 France.
' References Cited UNITED STATES PATENTS 3,212,963 10/1965 Wehner "167-22 10 3,201,593 9/1965 Lindaberry 71-67 US. 01. x11. 3,200,128 8/1965 Wagner 260296 71-88, 121
GOT TS, Primary Examiner c. L. MILLS, Assistant Examiner
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US60248566A | 1966-12-19 | 1966-12-19 |
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US3519414A true US3519414A (en) | 1970-07-07 |
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US602485A Expired - Lifetime US3519414A (en) | 1966-12-19 | 1966-12-19 | Algaetoxic,synergistic compositions of aza - 1 - cycloheptenes and quaternary ammonium compounds and method of use |
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US3807983A (en) * | 1971-04-02 | 1974-04-30 | Akzona Inc | Quaternary ammonium aquatic herbicides |
US3856961A (en) * | 1970-01-02 | 1974-12-24 | Betz Laboratories | Slime control composition containing bromonitrostyrene and its use |
US6028113A (en) * | 1995-09-27 | 2000-02-22 | Sunburst Chemicals, Inc. | Solid sanitizers and cleaner disinfectants |
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US3130124A (en) * | 1959-12-21 | 1964-04-21 | Chem Lab Products Inc | Algaecide stick composition |
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US3856961A (en) * | 1970-01-02 | 1974-12-24 | Betz Laboratories | Slime control composition containing bromonitrostyrene and its use |
US3807983A (en) * | 1971-04-02 | 1974-04-30 | Akzona Inc | Quaternary ammonium aquatic herbicides |
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