US3129261A - Dialkylhalobenzylalkylbenzyl nonphytotoxic quaternary ammonium compounds - Google Patents
Dialkylhalobenzylalkylbenzyl nonphytotoxic quaternary ammonium compounds Download PDFInfo
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- US3129261A US3129261A US35112A US3511260A US3129261A US 3129261 A US3129261 A US 3129261A US 35112 A US35112 A US 35112A US 3511260 A US3511260 A US 3511260A US 3129261 A US3129261 A US 3129261A
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- Prior art keywords
- chloride
- quaternary ammonium
- compounds
- parts
- chlorine
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- 150000003856 quaternary ammonium compounds Chemical class 0.000 title description 5
- 231100001184 nonphytotoxic Toxicity 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims description 31
- 244000141359 Malus pumila Species 0.000 description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- 235000011430 Malus pumila Nutrition 0.000 description 15
- 235000015103 Malus silvestris Nutrition 0.000 description 15
- -1 trichloro-benzyl groups Chemical group 0.000 description 15
- 239000000460 chlorine Substances 0.000 description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 13
- 231100000674 Phytotoxicity Toxicity 0.000 description 13
- 229910052801 chlorine Inorganic materials 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 240000003768 Solanum lycopersicum Species 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000002688 persistence Effects 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 206010039509 Scab Diseases 0.000 description 6
- 230000000844 anti-bacterial effect Effects 0.000 description 6
- 230000035784 germination Effects 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 241000213004 Alternaria solani Species 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 5
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 5
- 150000001450 anions Chemical group 0.000 description 5
- 230000003385 bacteriostatic effect Effects 0.000 description 5
- 230000008029 eradication Effects 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 5
- 230000003902 lesion Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 241000266363 Stemphylium sarciniforme Species 0.000 description 4
- 235000021016 apples Nutrition 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 235000013399 edible fruits Nutrition 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- YZIFVWOCPGPNHB-UHFFFAOYSA-N 1,2-dichloro-4-(chloromethyl)benzene Chemical compound ClCC1=CC=C(Cl)C(Cl)=C1 YZIFVWOCPGPNHB-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 241000233866 Fungi Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 241000228452 Venturia inaequalis Species 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000000855 fungicidal effect Effects 0.000 description 3
- 230000000885 phytotoxic effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 2
- IRSVDHPYXFLLDS-UHFFFAOYSA-N 2,4-dichloro-1-(chloromethyl)benzene Chemical compound ClCC1=CC=C(Cl)C=C1Cl IRSVDHPYXFLLDS-UHFFFAOYSA-N 0.000 description 2
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 244000081841 Malus domestica Species 0.000 description 2
- ZNLGXVGEBIFRCO-UHFFFAOYSA-N N-benzyl-N-methyltetradecan-2-amine Chemical compound CC(N(C)CC1=CC=CC=C1)CCCCCCCCCCCC ZNLGXVGEBIFRCO-UHFFFAOYSA-N 0.000 description 2
- 244000046052 Phaseolus vulgaris Species 0.000 description 2
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 2
- 241000233622 Phytophthora infestans Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 125000006177 alkyl benzyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 2
- CWMKBBGMKGWRMJ-UHFFFAOYSA-N n-benzyl-n-methyltridecan-1-amine Chemical compound CCCCCCCCCCCCCN(C)CC1=CC=CC=C1 CWMKBBGMKGWRMJ-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 231100000208 phytotoxic Toxicity 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- RLGVDTCKJKBXOC-UHFFFAOYSA-N (3,4-dichlorophenyl)methanamine;hydrochloride Chemical compound Cl.NCC1=CC=C(Cl)C(Cl)=C1 RLGVDTCKJKBXOC-UHFFFAOYSA-N 0.000 description 1
- UBJKMVAYDQUJSJ-UHFFFAOYSA-N 1,2,4-trichloro-5-(chloromethyl)benzene Chemical compound ClCC1=CC(Cl)=C(Cl)C=C1Cl UBJKMVAYDQUJSJ-UHFFFAOYSA-N 0.000 description 1
- NJQRKFOZZUIMGW-UHFFFAOYSA-N 1,3,5-trichloro-2-(chloromethyl)benzene Chemical compound ClCC1=C(Cl)C=C(Cl)C=C1Cl NJQRKFOZZUIMGW-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-M 2-methylbenzenesulfonate Chemical compound CC1=CC=CC=C1S([O-])(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 description 1
- 241000589155 Agrobacterium tumefaciens Species 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 244000144730 Amygdalus persica Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 235000002566 Capsicum Nutrition 0.000 description 1
- 241000990232 Curtobacterium flaccumfaciens pv. flaccumfaciens Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 241000588698 Erwinia Species 0.000 description 1
- 241000588694 Erwinia amylovora Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 208000031888 Mycoses Diseases 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000233614 Phytophthora Species 0.000 description 1
- 241000758706 Piperaceae Species 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 241000317942 Venturia <ichneumonid wasp> Species 0.000 description 1
- 241000567019 Xanthomonas vesicatoria Species 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- TXBLKKRHROKVJJ-UHFFFAOYSA-M benzyl-[1-(2,4-dichlorophenyl)tridecyl]-diethylazanium chloride Chemical compound [Cl-].C(CCCCCCCCCCC)C(C1=C(C=C(C=C1)Cl)Cl)[N+](CC)(CC)CC1=CC=CC=C1 TXBLKKRHROKVJJ-UHFFFAOYSA-M 0.000 description 1
- ZKKPKOSQFCSZBZ-UHFFFAOYSA-M benzyl-dimethyl-(1-phenyltridecyl)azanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1C[N+](C)(C)C(CCCCCCCCCCCC)C1=CC=CC=C1 ZKKPKOSQFCSZBZ-UHFFFAOYSA-M 0.000 description 1
- 150000005524 benzylchlorides Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 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
- 231100000162 fungitoxic Toxicity 0.000 description 1
- 230000002464 fungitoxic effect Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- SQJAYMROZIRKIK-UHFFFAOYSA-N n-benzyl-n-ethyltetradecan-1-amine Chemical compound CCCCCCCCCCCCCCN(CC)CC1=CC=CC=C1 SQJAYMROZIRKIK-UHFFFAOYSA-N 0.000 description 1
- YYWIIBCNNNOJQP-UHFFFAOYSA-N n-benzyl-n-methyldecan-1-amine Chemical compound CCCCCCCCCCN(C)CC1=CC=CC=C1 YYWIIBCNNNOJQP-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UYDLBVPAAFVANX-UHFFFAOYSA-N octylphenoxy polyethoxyethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCO)C=C1 UYDLBVPAAFVANX-UHFFFAOYSA-N 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000004763 spore germination Effects 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
Definitions
- R is hydrogen or an alkyl group of one to four carbon atoms
- R is an alkyl group of 9 to 15 carbon atoms
- the total number of carbon atoms in R and R being not over 16 carbon atoms
- Y and Y are hydrogen or chlorine, at least one of these being chlorine
- Y is hydrogen or chlorine
- the total number of chlorine atoms in the phenyl group carrying the Y substituents being not over three
- n is an integer with a value of one to two
- X is an anion.
- a class of preferred compounds has one methyl substituent and one long alkyl group on this benzyl group.
- alkyldimethylbenzyl ammonium salts wherein the alkyl group is long-chained, usually dodecyl. These give good fun gicidal action under favorable conditions, but those with alkyl groups providing good solubility for proper ap plication lack persistence and those with longer alkyl groups providing better persistence lack fungitoxicity. At the rates of application needed for good control of scab, these salts cannot be frequently applied Without causing undesirable effects. Thus, under conditions of severe infection or under unfavorable weather conditions, such salts lack the required balance.
- Quaternary ammonium salts which meet the above strict requirements have been defined by the structural Formula I given above. by reacting a tertiary amine (II) R Cn Zn'l'l N-CHg C am-r R with a polychlorobenzyl halide Cl0flzhalogen l Y1 Y2 This may be desirably done in an inert organic solvent,
- acetone such as acetone, methyl hexyl ketone, acetonitrile, nitrornethane, ethyl acetate, benzene, toluene, or a naphtha.
- Temperatures for reaction lie between 25 and 150 C.
- the quaternary ammonium salt precipitates as 'it is formed and can be separated and freed of solvent.
- solvent may be distilled from the reaction mixture to leave a residue which can be used as obtained or may be purified as by precipitation, extraction, charcoaling, or recrystallization.
- Example 1 There are mixed 25 parts of dodecylbenzyldimethylamine, 16.1 parts of 2,4-dichlorobenzyl chloride, and 100 CH3 C 3 CIOGHr-ITP-CH; own
- dodecylbenzyldiethylamine for the do-decylbenzyldimethylamine.
- dodecylbenzyldiethyl-2,4-dichlorobenzylammonium chloride is similar in properties to the above compound. It is quite as safe on tender foliage and about as fungitoxic.
- the above compound dodecylbenzyldimethyl-2,4-dichlorobenzylammonium chloride, has ED values of 1-10 p.p.m. against Alternaria solani and Monolinia fructicola, and of less than 1 p.p.m. against Stemphilz'um sarcz'naeforme.
- This compound is also highly active against such typical pathogens as Agrobacterium tumefaciens (plant galls), Erwinia amylovora (fire blight), Erwinia carolovora (vegetable soft rot), Xanllzomonas phaseoli (bean blight), Xanlhomonas prum' (bacterial soft spot of plum and peach), Corynebacterium flaccumfaciens (bacterial wilt of beans), and Xanthomonas vesicatoria (bacterial spot of peppers and tomatoes).
- Agrobacterium tumefaciens plant galls
- Erwinia amylovora fire blight
- Erwinia carolovora vegetable soft rot
- Xanllzomonas phaseoli bean blight
- Corynebacterium flaccumfaciens bacterial wilt of beans
- Xanthomonas vesicatoria bacterial spot
- the above prepared compounds give very favorable values in standard antibacterial tests.
- they are effectively bacteriostatic at 1/ 100,000 against S. typhosa and bactericidal at the same dilution.
- bactericidal at l/ 200,000.
- Apple whips were sprayed with solutions containing 0.75 pound per 100 gallons of the above compounds at oneweek intervals for a period of four weeks. No evidence of phytotoxicity was observed even though the whips were held under humid conditions.
- Apples were treated with a solution contaim'ng one pound of the above compounds per 100 gallons of water. The apples were stored for 24 hours under high humidity, then dried, and stored for seven days. No stains developed on the apples. At the same time, apples thus treated H with dodecyldimethylbenzylammonium chloride developed ghost rings or brown stains.
- Another method of evaluation distinguishes the action of dodecylbenzyldimethyl 2,4-dichlorobenzylamn1onium chloride and the like from that of dodecylbenzyldimethylbenzylammonium chloride and of dodecyldimethylbenzylammonium chloride as comparison compounds.
- spores are obtained from lesions of leaves fom the eradication test by washing leaves having lesions with water and collecting spores. These spores are applied to standard coated slides such as used in the slide spore germination test. The inoculated slides are stored under conditions favorable for germination for 24 hours and then examined.
- Example 2 There are mixed 30.3 parts of dodecylbenzyldimethyl amine, 20 parts of 3,4-dichlorobenzyl chloride, and 120 parts of acetone. The mixture is stirred and heated under reflux for 2.5 hours. Solvent is evaporated to give 38.1 parts of a viscous oil, which contains 21.2% of chlorine and 3% of nitrogen (theory 21.3% and 2.8% respectively for dodecylbenzyldimethyl-3,4-dichlorobenzylammonium chloride).
- the above compound evaluated by the slide-germination method, has an ED value of less than 5 p.p.m. against Alter/zaria solarzi, Monolirzl'a fructicola, and Stemp/zylium mieforme. It shows no phytotoxicity when applied to young tomato plants in aqueous sprays containing 0.1% or even 1% of the compound.
- This compound shows superior performance in controlling tomato late blight (Phytophthora infestarzs), requiring only 29 p.p.m. to give an ED value. It has unusual persistence in tests in which plants are sprayed with water to simulate rain.
- the above compound is bacteriostatic against S. lyp/zosa at 1/ 100,000 and against S. aureus, Micrococcus pyogenes, var. aureus, at 1/ 400,000. It is bactericidal against S. zyphosa at 1/ 10,000 and against S. aureus at 1/400,000.
- Example 3 There are mixed 26.1 parts of nonylbenzyldimethylamine, 19.6 parts of 3,4-dichlorobenzyl chloride, and parts of acetone. The mixture is heated at reflux temperatures for 3.5 hours and cooled in an ice bath. Solid forms and is collected, washed with cold acetone and dried to give 25.3 parts of a product which by analysis corresponds to nonylbenzyldimethyl-3,4dichlorobenzy1- ammonium chloride. The chlorine content found is 23.9% (23.3% theory) and the nitrogen content is 3.0% (3.1% theory).
- nonylmethylbenzyldimethyl-3,4-dichlorobenzylammonium salts where the anion is chloride, bromide, acetate, sulfate, methylsulfate, or the like, are somewhat more active than the above nonylbenzyl compound and quite safe on foliage.
- nonylethylbenzyldimethyldichlorobenzylammonium chloride or bromide and nonylbutylbenzyldimethyldichlorobenzylammonium chloride or bromide are both elfective in controlling fungi and bacteria which attack growing plants and are also safely used thereon, even with repeated applications.
- Example 4 In the same way as in Example 2, there are reacted 33 parts of dodecylmethylbenzyldimethylamine and 19.6 parts of 3,4-dichlorobenzyl chloride in parts of acetone. After removal of solvent, there is obtained 51 parts of a yellow oil which corresponds in composition to OH: CH3 312 25 C1 CH:ITICH2 I C1 .7. CH ⁇
- the chlorine content is 21.3% and the nitrogen content is 2.7%.
- This compound gives an ED value of 1 to 10 p.p.m. against Alternaria solani, Monolinia fructicola, and Stemphylium maeforme.
- this compound was both bacteriostatic and bactericidal to S. typhosa at 1/ 100,000 and was both bacteriostatic and bactericidal to S. aureus at 1/800,000.
- Example 5 A trichlorobenzyl chloride is prepared by chloromethylating a commercial trichlorobenzene which contains about 70% 1,2,4-trichlorobenzene and 30% 1,2,3-trichlorobenzene. This benzyl chloride is mainly 2,4,5-trichlorobenzyl chloride.
- aqueous sprays of the above compound it may be desirable to take it up with a small proportion of a non-ionic wetting agent such as octylphenoxypolyethoxyethanol to ensure good dispersion on foliage.
- a non-ionic wetting agent such as octylphenoxypolyethoxyethanol
- Example 6 The method of Example 1 is followed to react dodecylmethylbenzyldimethylamine and 2,4-dichlorobenzylchloride to form dodecylmethylbenzyldimethyl-Z,4-dich1orobenzylammonium chloride, 2. yellow oil, which contains 21.0% of chlorine and 2.7% of nitrogen. The yield is practically quantitative.
- This compound has an ED value of about l-lO p.p.m. against Monolinia fructicola and between 10 and 50 against Alternaria solani and Stemphylium mimeforme.
- the compound eradicates completely 70% of the lesions of Venturia inaequalis on apple seedlings. It has a protective value of 87% and a 93% value in persistence tests.
- the above chlorides may be converted into other salts by exchanging the chloride ion for other anions, such as sulfate, methyl sulfate, acetate, phosphate, benzenesulfonate, toluenesulfonate, naphthalenesulfonates, or like anions.
- other anions such as sulfate, methyl sulfate, acetate, phosphate, benzenesulfonate, toluenesulfonate, naphthalenesulfonates, or like anions.
- emulsion concentrates For example, the above quaternary ammonium compounds can be taken up with about an equal volume of isopropanol.
- This solution ('80 parts) is mixed with 16 parts of Xylene or an aromatic naphtha and 4 parts of a solventand water-soluble alkylphenoxypolyethoxyethanol wetting agent to provide a self-emulsifying composition.
- such emulsion concentrate may contain from about 20% to about 60% of a defined quaternary ammonium salt, about 40% to of organic solvent for said salt, and 0% to 10% of a non-ionic emulsifier soluble in the solvent-salt mixture.
- a non-ionic emulsifier soluble in the solvent-salt mixture.
- alkylphenoxypolyethoxyethanols there may be used ethylene oxide condensates of long-chained alcohols, mercaptans, fatty acids, hydroxy esters or amines or mixed ethylene oxide-propylene oxide condensates of these and similar materials.
- R is selected from the class consisting of hydro gen and alkyl groups of not over four carbon atoms
- R is an alkyl group of 9 to 15 carbon atoms, the total number of carbon atoms in R and R being not over 16 carbon atoms
- Y and Y are selected from the class consisting of hydrogen and chlorine, at least one of these being chlorine
- Y is selected from the class consisting of hydrogen and chlorine, the total number of chlorine atoms on the phenyl group carrying the Y substituents being two to three
- n is an integer with a value of one to two
- X is an anion from the class consisting of chloride and bromide.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US35112A US3129261A (en) | 1960-06-10 | 1960-06-10 | Dialkylhalobenzylalkylbenzyl nonphytotoxic quaternary ammonium compounds |
| GB19830/61A GB975926A (en) | 1960-06-10 | 1961-06-01 | Pesticidal compounds |
| BE604811A BE604811A (fr) | 1960-06-10 | 1961-06-09 | Nouveaux composés d'ammonium quaternaire, non phytotoxiques |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US35112A US3129261A (en) | 1960-06-10 | 1960-06-10 | Dialkylhalobenzylalkylbenzyl nonphytotoxic quaternary ammonium compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3129261A true US3129261A (en) | 1964-04-14 |
Family
ID=21880717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US35112A Expired - Lifetime US3129261A (en) | 1960-06-10 | 1960-06-10 | Dialkylhalobenzylalkylbenzyl nonphytotoxic quaternary ammonium compounds |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US3129261A (fr) |
| BE (1) | BE604811A (fr) |
| GB (1) | GB975926A (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100228035A1 (en) * | 2002-04-05 | 2010-09-09 | University Of South Alabama | Functionalized Ionic Liquids, and Methods of Use Thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2097640A (en) * | 1933-03-27 | 1937-11-02 | Ici Ltd | Quaternary ammonium compounds |
| GB647258A (en) * | 1942-09-04 | 1950-12-06 | Parke Davis & Co | Quarternary ammonium compounds and preserving and disinfecting compositions containing them |
| US2569803A (en) * | 1949-06-29 | 1951-10-02 | Rohm & Haas | Bis (alkylbenzyl) dimethyl ammonium halides |
| CH285479A (fr) * | 1948-04-07 | 1952-09-15 | D Innovations Chimiques Sinnov | Procédé de préparation d'un mélange de chlorures de diméthyl-benzyl-dodécylbenzyl-ammonium. |
| US2664444A (en) * | 1951-11-20 | 1953-12-29 | Winthrop Stearns Inc | N-(n-dodecyl)-n-(3,4-dichlorophenethyl)-n, n-dimethyl-ammonium compounds |
| US2691676A (en) * | 1952-06-02 | 1954-10-12 | Sterling Drug Inc | N, n-di-(n-octyl)-n-methyl-n-(3, 4-dichlorobenzyl) ammonium chloride and process for preparing the same |
| US2694715A (en) * | 1949-12-20 | 1954-11-16 | California Research Corp | Process of producing quaternary ammonium salts and products thereof |
| US2763589A (en) * | 1953-02-24 | 1956-09-18 | Us Rubber Co | Fungicidal compositions of n-phenylchlorophthalamic acids and derivatives thereof and method of applying to plants |
| US2787573A (en) * | 1951-05-21 | 1957-04-02 | Pennsylvania Salt Mfg Co | Pesticidal compositions and their use |
-
1960
- 1960-06-10 US US35112A patent/US3129261A/en not_active Expired - Lifetime
-
1961
- 1961-06-01 GB GB19830/61A patent/GB975926A/en not_active Expired
- 1961-06-09 BE BE604811A patent/BE604811A/fr unknown
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2097640A (en) * | 1933-03-27 | 1937-11-02 | Ici Ltd | Quaternary ammonium compounds |
| GB647258A (en) * | 1942-09-04 | 1950-12-06 | Parke Davis & Co | Quarternary ammonium compounds and preserving and disinfecting compositions containing them |
| CH285479A (fr) * | 1948-04-07 | 1952-09-15 | D Innovations Chimiques Sinnov | Procédé de préparation d'un mélange de chlorures de diméthyl-benzyl-dodécylbenzyl-ammonium. |
| US2569803A (en) * | 1949-06-29 | 1951-10-02 | Rohm & Haas | Bis (alkylbenzyl) dimethyl ammonium halides |
| US2694715A (en) * | 1949-12-20 | 1954-11-16 | California Research Corp | Process of producing quaternary ammonium salts and products thereof |
| US2787573A (en) * | 1951-05-21 | 1957-04-02 | Pennsylvania Salt Mfg Co | Pesticidal compositions and their use |
| US2664444A (en) * | 1951-11-20 | 1953-12-29 | Winthrop Stearns Inc | N-(n-dodecyl)-n-(3,4-dichlorophenethyl)-n, n-dimethyl-ammonium compounds |
| US2691676A (en) * | 1952-06-02 | 1954-10-12 | Sterling Drug Inc | N, n-di-(n-octyl)-n-methyl-n-(3, 4-dichlorobenzyl) ammonium chloride and process for preparing the same |
| US2763589A (en) * | 1953-02-24 | 1956-09-18 | Us Rubber Co | Fungicidal compositions of n-phenylchlorophthalamic acids and derivatives thereof and method of applying to plants |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100228035A1 (en) * | 2002-04-05 | 2010-09-09 | University Of South Alabama | Functionalized Ionic Liquids, and Methods of Use Thereof |
| US8674135B2 (en) * | 2002-04-05 | 2014-03-18 | University Of South Alabama | Functionalized ionic liquids, and methods of use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| GB975926A (en) | 1964-11-25 |
| BE604811A (fr) | 1961-11-11 |
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