US3502720A - N-(2-methyl-4-chlorophenyl)-formamidines - Google Patents

N-(2-methyl-4-chlorophenyl)-formamidines Download PDF

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US3502720A
US3502720A US594361A US3502720DA US3502720A US 3502720 A US3502720 A US 3502720A US 594361 A US594361 A US 594361A US 3502720D A US3502720D A US 3502720DA US 3502720 A US3502720 A US 3502720A
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Prior art keywords
chlorophenyl
methyl
acaricidal
mites
ova
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Expired - Lifetime
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US594361A
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Horst Arndt
Walter Steinhausen
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Bayer Pharma AG
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Schering AG
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Priority claimed from US332255A external-priority patent/US3378437A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
    • C07D295/195—Radicals derived from nitrogen analogues of carboxylic acids
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/52—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing groups, e.g. carboxylic acid amidines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings

Definitions

  • This invention relates to acaricidal agents, more particularly to compounds which are selectively toxic to acarids, such as mites in all stages of development.
  • the acaricidal agents of the invention are harmless to insects. They destroy mites without damaging insects that may prey on the mites.
  • the acaricidal agents of the invention are highly effective against mite eggs in their later stages of development. They are therefore useful in the treatment of plants long after their infestation by mites.
  • the acaricidal agents of the invention may be prepared by conventional methods.
  • an N-formylated monoor dialkylamine is reacted with an equivalent amount of phosphorus oxychloride in the presence of an inert organic solvent at a temperature between 20 and 100 C., and the equivalent amount of 2- amino-S-chlorotoluene is added to the reaction mixture.
  • the ensuing second reaction yields the amidinium salt which is converted to the free base by conventional methods.
  • the best time and temperature to be selected for the second reaction varies somewhat for the several compounds of the invention, but is readily determined by preliminary small scale tests.
  • EXAMPLE 1 15.4 parts by weight of phosphorus oxychloride were slowly added with stirring to 7.4 parts by weight of dimethylformamide dissolved in 50 parts by weight of ethylene chloride. The addition period was about thirty to forty minutes and the temperature was allowed to rise to 45 C. To the solution then were subsequently added 14.2 parts by weight of Z-amino-S-chlorotoluene while stirring was continually maintained and the temperature of the reaction mixture was allowed to rise to C. After completion of the 2-amino-5-chloroto1uene addition, the mixture was stirred for two additional hours at about 65 C. C. Then the temperature of the solution was adjusted to about 5 C.
  • Representative acaricidal agents of the invention when prepared by the above method have the following characteristic properties.
  • the acaricidal compounds of the invention may be applied singly or in mixtures with each other and with other pesticidal agents. They may constitute the active ingredient of dusting compositions, or they may be applied to mites in fogging or spraying compositions.
  • the acaricidal agents of the invention When incorporated in liquid compositions, may be dispersed in an inert liquid medium to form a suspension or emulsion.
  • the salts of the formamidine derivatives of the invention with strong acids, such as hydrochloric acid, are soluble in water. The salts are specifically toxic to mites, and their aqueous solutions may be incorporated liquid acaricidal compositions.
  • Solid compositions based on the acaricidal agents of the invention may include conventional solid diluents and carriers such as limestone, kaolin, chalk, talcum, lattaclay and other clays. Surfactants when admixed to such compositions enhance their elfectiveness in a manner known in itself.
  • EXAMPLE 2 Effects on acarides in the postembryonal stage and on ova Bush beans in the late two-leaf stage and infected with spider mites of the species Tetranychas urticae Koch in all stages of development were sprayed with aqueous suspensions or emulsions of various formamidine derivatives and with aqueous solutions of formamidine derivative salts in different concentrations.
  • the liquids were applied to the potted plants while the same were standing on a rotating turntable.
  • a spray gun equipped with a glass nozzle was employed.
  • the pressure at the gun was 0.5 kg./cm.
  • the amount of liquid applied to three plants per pot was between 50 and 60 milliliters and was sufficient for complete wetting of the plants. Excess liquid ran off in drops.
  • R is a member of the group consisting of hydrogen and alkyl having one to four carbon atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • 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)

Description

United States Patent 3,502,720 N-(2-METHYL-4-CHLOROPHENYL)- FORMAMIDINES Horst Arndt, Unna, and Walter Steinhausen, Grossburgwedel, Germany, assignors to A. G. Schering, Berlin, Germany No Drawing. Original application Dec. 20, 1963, Ser. No. 332,255, now Patent No. 3,378,437, dated Apr. 16, 1968. Divided and this application Nov. 15, 1966, Ser.
Int. Cl. C07c 123/00 US. Cl. 260-564 8 Claims ABSTRACT OF THE DISCLOSURE N-(2-methyl-4-chlorophenyl)-formamidine derivatives of the formula R2 destroy mites in all stages of development when R is hydrogen or alkyl having not more than four carbon atoms, and R is such alkyl.
This invention relates to acaricidal agents, more particularly to compounds which are selectively toxic to acarids, such as mites in all stages of development.
This application is a division of our copending application Ser. No. 332,255, filed Dec. 20, 1963, now Patent No. 3,378,437.
We have found that basic compounds of the formula the acaricidal effect, or at least in a substantial reduction 1 of the effect.
,The acaricidal agents of the invention are harmless to insects. They destroy mites without damaging insects that may prey on the mites.
The acaricidal agents of the invention are highly effective against mite eggs in their later stages of development. They are therefore useful in the treatment of plants long after their infestation by mites.
The acaricidal agents of the invention may be prepared by conventional methods. In a preferred procedure, an N-formylated monoor dialkylamine is reacted with an equivalent amount of phosphorus oxychloride in the presence of an inert organic solvent at a temperature between 20 and 100 C., and the equivalent amount of 2- amino-S-chlorotoluene is added to the reaction mixture. The ensuing second reaction yields the amidinium salt which is converted to the free base by conventional methods. The best time and temperature to be selected for the second reaction varies somewhat for the several compounds of the invention, but is readily determined by preliminary small scale tests.
The following example is illustrative of specific conditions which will yield acceptable results, but it will be understood that the invention is not limited to the process by which the acaricidal agents are produced.
EXAMPLE 1 15.4 parts by weight of phosphorus oxychloride were slowly added with stirring to 7.4 parts by weight of dimethylformamide dissolved in 50 parts by weight of ethylene chloride. The addition period was about thirty to forty minutes and the temperature was allowed to rise to 45 C. To the solution then were subsequently added 14.2 parts by weight of Z-amino-S-chlorotoluene while stirring was continually maintained and the temperature of the reaction mixture was allowed to rise to C. After completion of the 2-amino-5-chloroto1uene addition, the mixture was stirred for two additional hours at about 65 C. C. Then the temperature of the solution was adjusted to about 5 C. by external cooling, and a strong base such as sodium hydroxide solution or triethylamine was added with vigorous stirring to maintain the pH at 11-11.5. The ethylene chloride layer was separated, washed with water, and dried over sodium sulphate, followed by evaporation of the solvent under diminished pressure which yielded as residue 16.7 parts by weight of an oily liquid, nearly percent of the theoretical amount; B.P. 156-157 C./0.4 mm. 72 1.5885 and d 1.105.
The elementary analysis corresponded to that of the compound C H N Cl N (2 methyl-4-chlorophenyl)- N,N-dimethylformamidine:
Found (percent): C, 61.50; H, 7.11; N, 14.53. Calculated (percent): C, 61.06; H, 6.66; N, 14.26.
Representative acaricidal agents of the invention when prepared by the above method have the following characteristic properties.
N (2 methyl-4-chlorophenyl)-N'-methylformamidine:
M.P. 85-87 C.
N (2 methyl 4 chlorophenyl) -N',N' dimethylfor-mamidine: B.P. l56157 C./0.4 mm. n =1.5885; d =1.l05
N (2 methyl-4-chlorophenyl)-N,N'-diethylformamidine: Oil n =l.572; a =1.702
N (2-methyl-4-chlorophenyl)-N-n-propylformamidine:
M.P 73-75 C.
N (2-methyl-4-chlorophenyl)-N,N-di-n-propylformamidine: Oil n =l.5545; d =LO25 N (2 methyl-4-chlorophenyl)-N'-isobutylformamidine:
M.P. 81-82 C.
N (2 methyl 4 chlorophenyl)-N'-se c.-butylformamidine: M.P. 42-44 C.
The melting points indicated herein are uncorrected, and were taken on materials recrystallized from hexane.
The acaricidal compounds of the invention may be applied singly or in mixtures with each other and with other pesticidal agents. They may constitute the active ingredient of dusting compositions, or they may be applied to mites in fogging or spraying compositions. When incorporated in liquid compositions, the acaricidal agents of the invention may be dispersed in an inert liquid medium to form a suspension or emulsion. The salts of the formamidine derivatives of the invention with strong acids, such as hydrochloric acid, are soluble in water. The salts are specifically toxic to mites, and their aqueous solutions may be incorporated liquid acaricidal compositions.
Solid compositions based on the acaricidal agents of the invention may include conventional solid diluents and carriers such as limestone, kaolin, chalk, talcum, lattaclay and other clays. Surfactants when admixed to such compositions enhance their elfectiveness in a manner known in itself.
The acaricidal properties of the formamidine derivatives of the invention, and the use of the compounds in the protection of plants against parasitic mites are illustrated in the following Examples which also show the results of comparison tests performed with other compounds closely related to those of the invention but not encompassed within the scope of the appended claims.
EXAMPLE 2 Effects on acarides in the postembryonal stage and on ova Bush beans in the late two-leaf stage and infected with spider mites of the species Tetranychas urticae Koch in all stages of development were sprayed with aqueous suspensions or emulsions of various formamidine derivatives and with aqueous solutions of formamidine derivative salts in different concentrations.
The liquids were applied to the potted plants while the same were standing on a rotating turntable. A spray gun equipped with a glass nozzle was employed. The pressure at the gun was 0.5 kg./cm. The amount of liquid applied to three plants per pot was between 50 and 60 milliliters and was sufficient for complete wetting of the plants. Excess liquid ran off in drops.
The iethal effects of the sprayed liquid on the postembryonal mite population, and on the ova was assessed after seven days, except in the case of N-(2-methyl-4- chlorophenyl)-N,N'-dimethylformamidine, in which results were evaluated after 14 days.
4 EXAMPLE 3 Effects on ova of dilferent ages The eifects of N-(2-rnethyl-4-chlorophenyi)-N,N'- dimethylformamidine on ova of T etranychus urticae Koch were evaluated in a test based on the method of S. C. Hoyt, J. of Econ. Entomol. 54 (1) 12-16, 1961. Circular disks of 18 mm. diameter were cut from bean leaves by means of a tubular laboratory cork borer. The leave disks were placed in open Petri dishes on foam plastic pads saturated With water which kept the disks from wilting. Ten adult females of Tetranychus urticae Koch were placed on each disk, and were removed after one day. On average, they left fifty eggs on each disk.
The eggs were sprayed with aqueous emulsions containing different amounts of the acaricidal agents. Spraying was performed by means of a conventional apparatus (dosing balance of M. Ehlers, Nachrichtenblatt des Pflanzenschutzdienstes, 5 (4) -62, 1953'). Ova that had not hatched eight days after the beginning of the test were considered dead.
The percentages of dead ova in batches sprayed with emulsions containing the acaricidal agent in different concentrations at different periods after iaying are listed below.
Age of ova, days Concentration of active agent in ppm. 0-1 1-2 2-3 3-4 4-5 Obviously, many modifications and variations of the present invention are possible in the light of the above teachings. It is therefore to be understood that the invention may be practiced otherwise than as specifically disclosed.
What is claimed is:
1. An acaricidal compound of the formula wherein R is a member of the group consisting of hydrogen and alkyl having one to four carbon atoms, and
Gone. Efiect, lethal, percent Compound Percent V Postembr. Ova
N-(Z-methyM-chlorophenyl)-N-methylformamidine 3 33 $8 0. 01 100 N-(imethylA-chlorophenyl)-N,Ndimethylformamidine b :22
N-(2-methyl-4-chlorophenyl)-N',N-dimethylformamidinium chloride 0. 100 0. 02 100 N-(2-methyl-4-chlorophenyl)-N,N-diethylfermamidine N-(2-methyl-4-chlorophenyl)-N',-n-propylformamldine b 3g N-2-methyl-4-chlorophenyl)-NN-di-n-prepylfortma1nidine 22 N-(2-methyl-4-chlorophenyl)-N'-isobutylfm'm ml in 3g N-(2-methyl-4-ehlorophenyl)-N-sec.-butylformamidine b; 38 N-phenyl-N,Ndimethylformamidine 0 0 As is evident from the above tabulation, acaricidal effects are closely bound to the specific configuration of substituents in the phenyl radical.
R is alkyl having between one and four carbon atoms.
2. N-(2-methyl-4-chlorophenyl) N methylformamidine.
US594361A 1963-12-20 1966-11-15 N-(2-methyl-4-chlorophenyl)-formamidines Expired - Lifetime US3502720A (en)

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US59436166A 1966-11-15 1966-11-15

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3864497A (en) * 1970-12-01 1975-02-04 Boots Pure Drug Co Ltd Acaricidal and insecticidal 1,5-diphenyl-3-methyl-1,3,5-triazapenta-1,4-diener
US3928623A (en) * 1974-03-11 1975-12-23 Stauffer Chemical Co Method of controlling insects using certain formamidine compounds containing trihalomethyl groups
DE2708616A1 (en) * 1976-03-01 1977-09-08 Ciba Geigy Ag PROCESS FOR THE PREPARATION OF N- (2-METHYL-4-CHLOROPHENYL) FORMAMIDE DERIVATIVES
US4053595A (en) * 1975-12-11 1977-10-11 Mobay Chemical Corporation Synergistic composition for the control of insects
US4056570A (en) * 1975-05-07 1977-11-01 Stauffer Chemical Company Acylformanidine insecticidal and miticidal compounds
US4087523A (en) * 1975-10-20 1978-05-02 American Cyanamid Company Insecticidal pyrethroid compositions
US4130662A (en) * 1976-03-12 1978-12-19 Stauffer Chemical Company Acylformanidine insecticidal and miticidal compounds
US4186195A (en) * 1976-07-14 1980-01-29 Sandoz, Inc. Virus insecticide composition
US4237168A (en) * 1979-06-11 1980-12-02 The Dow Chemical Company N-(4-Chloro-2-methylphenyl)-N-hydroxy methanimidamide and its pesticidal use
US4454127A (en) * 1975-10-20 1984-06-12 American Cyanamid Co. Insecticidal pyrethroid compositions
US4612395A (en) * 1976-03-01 1986-09-16 Ciba-Geigy Corporation Process for the production of N-(2-methyl-4-chlorophenyl)-formamidine derivatives
WO1989004595A3 (en) * 1987-11-19 1989-07-27 Upjohn Co Ectoparasiticides
US6818662B2 (en) * 2002-05-28 2004-11-16 Taisho Pharmaceutical Co., Ltd. Pharmaceutical composition

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3073851A (en) * 1957-12-04 1963-01-15 Hoffmann La Roche Formamidines of primary amines
US3119831A (en) * 1959-07-10 1964-01-28 Ici Ltd N-2-pyridyl-n'-(n-octyl or n-dodecyl)-formamidine
US3189648A (en) * 1962-04-11 1965-06-15 Du Pont Process for preparing n, n-dialkyl-n'-arylamidines
US3394397A (en) * 1964-12-23 1968-07-23 Ciba Ltd Nu-4-bromo-2-methylphenyl-nu', nu'-dimethylformamidine and process for preparing thesame

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3073851A (en) * 1957-12-04 1963-01-15 Hoffmann La Roche Formamidines of primary amines
US3119831A (en) * 1959-07-10 1964-01-28 Ici Ltd N-2-pyridyl-n'-(n-octyl or n-dodecyl)-formamidine
US3189648A (en) * 1962-04-11 1965-06-15 Du Pont Process for preparing n, n-dialkyl-n'-arylamidines
US3394397A (en) * 1964-12-23 1968-07-23 Ciba Ltd Nu-4-bromo-2-methylphenyl-nu', nu'-dimethylformamidine and process for preparing thesame

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3864497A (en) * 1970-12-01 1975-02-04 Boots Pure Drug Co Ltd Acaricidal and insecticidal 1,5-diphenyl-3-methyl-1,3,5-triazapenta-1,4-diener
US3928623A (en) * 1974-03-11 1975-12-23 Stauffer Chemical Co Method of controlling insects using certain formamidine compounds containing trihalomethyl groups
US4056570A (en) * 1975-05-07 1977-11-01 Stauffer Chemical Company Acylformanidine insecticidal and miticidal compounds
US4087523A (en) * 1975-10-20 1978-05-02 American Cyanamid Company Insecticidal pyrethroid compositions
US4454127A (en) * 1975-10-20 1984-06-12 American Cyanamid Co. Insecticidal pyrethroid compositions
US4053595A (en) * 1975-12-11 1977-10-11 Mobay Chemical Corporation Synergistic composition for the control of insects
DE2708616A1 (en) * 1976-03-01 1977-09-08 Ciba Geigy Ag PROCESS FOR THE PREPARATION OF N- (2-METHYL-4-CHLOROPHENYL) FORMAMIDE DERIVATIVES
US4612395A (en) * 1976-03-01 1986-09-16 Ciba-Geigy Corporation Process for the production of N-(2-methyl-4-chlorophenyl)-formamidine derivatives
US4130662A (en) * 1976-03-12 1978-12-19 Stauffer Chemical Company Acylformanidine insecticidal and miticidal compounds
US4186195A (en) * 1976-07-14 1980-01-29 Sandoz, Inc. Virus insecticide composition
US4237168A (en) * 1979-06-11 1980-12-02 The Dow Chemical Company N-(4-Chloro-2-methylphenyl)-N-hydroxy methanimidamide and its pesticidal use
WO1989004595A3 (en) * 1987-11-19 1989-07-27 Upjohn Co Ectoparasiticides
US6818662B2 (en) * 2002-05-28 2004-11-16 Taisho Pharmaceutical Co., Ltd. Pharmaceutical composition

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