WO1989004595A2 - Ectoparasiticides - Google Patents

Ectoparasiticides Download PDF

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Publication number
WO1989004595A2
WO1989004595A2 PCT/US1988/003905 US8803905W WO8904595A2 WO 1989004595 A2 WO1989004595 A2 WO 1989004595A2 US 8803905 W US8803905 W US 8803905W WO 8904595 A2 WO8904595 A2 WO 8904595A2
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compound
num
percent
coumaphos
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PCT/US1988/003905
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WO1989004595A3 (en
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Sylvester D. Folz
Douglas L. Rector
Joel L. Kirkpatrick
Natu R. Patel
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The Upjohn Company
Chevron Research Company
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    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • 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
    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
    • A01N47/44—Guanidine; Derivatives thereof
    • 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
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
    • C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
    • C07C257/14—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/12—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C279/00—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
    • C07C279/18—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of guanidine groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
    • C07D263/28—Nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

This invention concerns N,N,N',N'-tetramethyl-N''-(3,4-dichlorophenyl)guanidine; 2-[(2,4-dimethylphenyl)imino]-3-methyloxazolidine or N-(3-chloro-4-methylphenyl)-N',N'-dimethylacetamidine and its acid addition and quaternary salts; or a compound, including acid addition and quaternary salts thereof, of formula (I), and a method for combating acarids by applying a parasitological amount of said compounds.

Description


  
 



   ECTOPARASITICIDES
SUMMARY OF THE INVENTION
 This invention pertains to new para substituted phenoxybutyne derivatives, a new N-phenylcarboxylic acid amidine, a new phenylguanidine, a new iminoxazolidine and to their use for the control of animal ectoparasites of the acarid group.



   The new para substituted phenoxybutyne derivatives of the present invention have the structural formula I and include 4-(4   fluorophenoxy) -2-butyn-1-ol    methylcarbamate and   4- (4-fluorophenoxy-      2-butyn- 1-yl)    cycloproprionate.



   The new N-phenylcarboxylic acid amidine of the present invention is   N' - (3-chloro-4-methylphenyl) -N,N-dimethylethanimidamide,    also known as N- (3-chloro-4-methylphenyl) -N' ,N' -dimethylacetamidine and has the structural formula A.



   The new guanidine of the present invention is N,N,N',N'   tetramethyl-N"-(3,4-dichlorophenyl)guanidine    and has the structural formula B. The new phenylguanidine exhibits unexpected onset of action and unanticipated ectoparasiticidal efficacies.



   The new iminoxazolidine of the present invention is 2-[(2,4dimethylphenyl)imino]-3-methyloxazolidine and has the structural formula C. The new iminoxazolidine exhibits unexpected onset of action and unanticipated ectoparasiticidal efficacies.



  BACKGROUND OF THE INVENTION
 Known phenoxybutyne compounds include:
 Cyclopropane carboxylic acid esters and related derivatives (pyrethrins and related derivatives are known as insecticides and acaricides see for example PCT Int. Appln. WO 81/2892 Al, 15 October 1981, CA 96:103724a; Jpn Kokai Tokyo Koho JP 55/53243 [80/53243]; 18
April 1980, CA 93:204151e; Ger. Offen. DE 2851428, 13 June 1979, CA 91:192892r; Ger. Offen. DE 2418950, 31 October 1974, CA 82:72566e;
Ger. Offen. DE 2150779, 27 April 1972, CA 77:5201r; Ger. Offen. DE 2128465, 16 December 1971, CA 76:72208r, Ger. Offen. DE 2108779, 16
September 1971, CA 75:151556k; Ger. Offen. DE 2108784, 16 September 1971, CA 75:151553g; Ger. Offen. DE 2038958, 18 February 1971, CA 75:64037y.



   Additionally alkynyl phenylacetals are also known as insecticides. Examples are described in Jpn. Kokai Tokyo Koho Jp 62/5938 A2 [87/5938], 12 January 1987, CA 106:156065t; Ger. Offen. DE 3524204  
Al, 16 January 1986, CA   104:206927g;   
 Various herbicidal bonded compounds including 4-(2,4-dichloro   phenoxy-2-butyn-l-yl)    acetate are described in Brit. 827,372 Feb. 3, 1960, CA 54 14188g.



     4-[[(methylamino)carbonylloxy]-2-butynoic    acid phenyl ester is described in Eur. Pat. Appln. EP 101   023A1,    22 Feb. 1984, CA 101   (3) :23346r.   



     4-(phenoxy-2-butyn-l-yl)    acetate is described in B.S.



  Thyagarajan,   K.K.    Balasubramania and R. Bhima Rae, Tetrehedron,   23    1892-9 (1967), CA   66(21):945-15j.   



   US Patent 3,378,437   claimedsthe    acaricidal effects of   N- (2-methyl.4-chlorophenyl) -N' ,N' -dimethylformamidine    and noted the acaricidal effects are closely bound to the specific configuration of substituents in the phenyl radical.   N-(3-chloro-4-methylphenyl)-      N',N'-dimethylformamidine    was disclosed and reported that the compound exhibited zero (0%) per cent lethal effects on acarides (spider mites) in the postembryonal stage and on ova. See Example 2,
US Patent 3,378,437.



   U.S. Patent 3,502,720, a divisional of "437", claimed N-(2   methyl-4-chlorophenyl)-N '-dimethylformamidine.   



     N- (2-methyl-4-chlorophenyl) -N', N' -dimethylformamidine    is commonly known as chlordimeform. Toxicity to   Boophilus      microolus    of formamidine acaricides (including chlordimeform) and related compounds and modification of toxicity by certain insecticide synergists is reported by CO Knowles and WJ Roulston in J. Econ.



  Entomol., 1973, 66(6), 1245-51; CA 80:79107y (1974).



   GB 1,251,935 discloses   N-(3-chloro-4-methylphenyl)-N',N'-    diethylacetamidine and reports that it and other N-phenylcarboxylic acid amidines of Formula I, where R, R' and R" together contain at least 4 carbon atoms, exhibit strong acaricidal properties (higher than the phenyl-amidines known from the prior art, for example N   3, 4-dichlorophenyl-N' N' -dimethylacatamidine),    particularly against acarids which, as animal ectoparasites, infest domesticated animals such as cattle, sheep and rabbits.



     N' - (4-chloro-2-methylphenyl) -N,N-dimethylethanimidamide    and 20 other compounds are disclosed in Effects of Diazepam and
Chlordimeform Analogs on the German and the American Cockroaches,
Pestic. Biochem. Physiol. 1986, 26(3), 253-62; CA 106: 1787f (1987).  



   US Patents 3,284,289 and 3,487,156 discloses preparations for combating pests, especially for combating undesired plant growth and harmful micro-organisms, insects, acarids and nematodes, where preparations contain as active substance a compound of the general formula A', in which R preferably represents a halogen atom or a lower alkyl or alkoxy radical, or a phenoxy radical that may be substituted by a halogen atom or a lower alkyl of alkoxy radical or represents the group -CH3 or   -N02,    n represents the integer 1 or 2,
R1 and R2 represent the methyl or ethyl radical, and R3 represents hydrogen or the methyl radical, or the salts of these compounds.



   US Patent 3,487,156 and 3,284,289 specifically disclose N-(3,4   dichlorophenyl) -N' ,N' -dimethylacetamidine    and   N- (3-chloro-4-    methylphenyl)-N',N'-dimethylformamidine.



   Other generic patent disclosures of various formamidines and/or acetamidines include US Patents 3,462,536, 3,462,357, 3,781,357 and 3,867,448 as well as the disclosures in Derwent 08647R and 91447R
C.



   Known acetamidines include the compounds of Appendix A. CA
Registry Numbers, if known, and References to each are listed.



   Known phenylguanidines include the compounds of Appendix B. CA
Registry Numbers, if known, and References to each are listed.



   U.S. Patent 3,686,199 discloses N-substituted-2-aryliminooxazolidines of Formula I, in which R denotes a halogen atom, or an optionally halogen-substituted lower alkyl, alkenyl or alkoxy radical, R' denotes an alkyl, alkenyl or alkenyl radical containing up to 7 carbon atoms, the alkenyl radical optionally being substituted at the double bond by 1 or 2 chlorine or bromine atoms, and n denotes 0, 1 or 2, and salts thereof, which possess acaricidal properties, especially against those strains of ticks which show resistance to phosphoric acid esters. In addition, 2,4dimethylaniline is disclosed at col 3, line 45 as a starting material.

 

   U.S. Patent 2,902,356 discloses a class of 2-phenylimino-3alkyloxazolidines, and to herbicidal compositions and methods employing the compounds disclosed.



   Known iminoxazolidines include the compounds of Appendix C. CA
Registry Numbers, if known, and References to each are listed.  



  DETAILED DESCRIPTION OF THE INVENTION
 The phenoxybutyne compounds of this invention, including acid addition and quaternary salts, are represented by Formula I wherein X is a halogen atom, preferably a fluoro atom; Y is selected from (a)
C1-C3 alkyl; (b) cyclopropyl; or (c)   -NR1R2    wherein R1 and R2, being the same or different, are hydrogen or C1-C3 alkyl.



   Y is preferably cyclopropyl or methylamino (-NHCH3).



     C -C    means the carbon content of various hydrocarboncontaining moieties is indicated by a prefix designating the minimum and maximum number of carbon atom in the moiety. Thus C1-C3 alkyl refers to alkyl of one to 3 carbon atoms, inclusive or methyl, ethyl, propyl, and isopropyl.



   Halogen atom (halo) refers to a bromo, chloro, iodo or fluoro atom.



   It has surprisingly been found that the compounds of Formula I have an unexpected spectrum of ectoparasiticidal activities and exhibit a more rapid onset of action compared to other ectoparasiticides known in the art, including for example the formamidines.



   The new N-phenylcarboxylic acid amidine of the present invention is   N' - (3-chloro-4-methylphenyl) -N,N-dimethylethanimidamide,    also known as   N- (3 -chloro-4-methylphenyl) -N' ,N' -dimethylacetamidine.   



   The new phenylguanidine of the present invention is   N,N,N',N'-      tetramethyl-N" - (3,4- dichlorophenyl) guanidine.   



   The new iminoxazolidine of the present invention is 2-[(2,4   dimethylphenyl) imino] -3 -methyloxazolidine.   



   The compounds of this invention are especially good for the control of animal ectoparasites acarid parasites of the order acarina such as ticks and particularly ticks of the Boophilus, Hyalomma,
Amblyomma, Rhipicephalus, Dermacentor; Ixodes,   Haemaphysalis    and
Anocener genera. Additionally certain insect pests particularly insects of the Ctenocephalides, Xenopsylla, Pulex, Echidnophaga,
Ceratophyllus genera, are also susceptible to control by the compounds of this invention.



   The phenoxybutyne compounds of this invention (Formula I) are readily prepared by reacting the appropriate phenoxide   (II)    with 4chloro-2-butyn-l-ol (III) to prepare the intermediate butyne-l-ol (IV) which is reacted with the appropriate acylating agent (V) (Chart  
A).



   The reactions of Scheme A are carried out in the presence of a suitable solvent, for example, ethers, hydrocarbons and chlorinated hydrocarbons. A catalyst such as   1, 4-diazabicyclo [2.2.2] octane    (DABCO) can be added to enhance the yield/rate of second reaction when he acylating agent is an isocyanate. In instances that the acylating agent is an acylhalide the reaction is advantageously carried out in the presence of bases such as triethylamine, pyridine, sodium carbonate, and the like. When the base is pyridine, pyridine can also serve as a solvent.



   The acaricidal agent,   N' - (3-chloro-4-methylphenyl) -N,N-      dimethylethanimidamide,    can be prepared by conventional methods. In a preferred procedure, 3-chloro-4-methylaniline is reacted with an equivalent amount of dimethylacetamide in the presence of a suitable solvent and phosphorous oxychloride. The phosphorous oxychloride reacts with the amide to form an intermediate dichloro amine which then reacts with the 3-chloro-4-methylaniline to give the acaricidal    agent of the invention, N - ( 3 - N- (3-chloro-4-methylphenyl) -N' ,N' -    dimethylacetamidine. The phosphorous oxychloride can be replaced by other inorganic acid halides such as thionyl chloride, phosphorous pentachloride, thiophosphoryl chloride, phosphorous trichloride, phosgene, silicon tetrachloride, tin tetrachloride, and the like.



  The reaction is carried out in the presence of a suitable solvent, for example ethers; hydrocarbons, such as benzene, toluene and xylene; and halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene and tetrachloroethylene.



     N' - (3-chloro-4-methylphenyl) -N,N-dimethylethanimidamid.e    has a basic character. It can be used as the free base or in the form of is salts, for example as a hydrochloride, sulfate, phosphate, nitrate or acetate.



     2-[(2w4-dimethylphenyl)imino]-3-methyloxazolidine    can be prepared by conventional methods. See U.S. Patent 3,686,199 which is incorporated herein by reference.



   The following detailed examples describe how to prepare the compounds of the invention and is to be construed as merely illustrative, and not limitations of the preceding disclosure in any way whatsoever. Those skilled in the art will promptly recognize appropriate variations from the procedure both as to reactants as  well as to reaction conditions and techniques.



  Preparation No. 1 Preparation of   4-(4-fluorophenoxy)-2-butyn-l-ol   
 To 87.43   gm    (0.42 mole) of a 25 % w/w solution of sodium methoxide in methanol and 30 ml of toluene, is added 47.08 gm (0.42 mole) of 4-fluorophenol with stirring. The solution is stirred for 30 minutes. The methanol is removed by distillation until the distilling head temperature reaches   105 C.    The solution is cooled.



  To the solution is added 39.62 gm (0.38 mole) of   4-chloro-2-butyn-1-    ol. The solution is heated at reflux for 1 hr. then stirred at room temperature for 16 hours. The reaction mixture is then extracted with water (1 x 100 ml), then 10% sodium hydroxide (1 x150 ml), then water again (1 x 100 ml), and finally with a saturated sodium chloride aqueous solution "brine" (1   xl00    ml). The organic layer is dried with magnesium sulfate and the solvent removed in vacuo to yield   4-(4-fluorophenoxy)-2-butyn-1-ol    as a liquid (97% purity by   VPC).   



  Example 1 Preparation of   4-(4-fluorophenoxy)-2-butyn-1-ol    methylcarbamate, Compound No. 1.



   To 28.83 gm   (o.16.      mole).    of   4-(4-fluorophenoxy)-2-butyn-1-ol    (Preparation No. 1), in glyme (DME) is added 15.3 gm (0.27 mole) methylisocyanate with stirring at   0 C.    A trace of   DABCO    catalyst is added, the reaction sealed and set aside at room temperature for four months. TLC shows the reaction to be complete. The solvent is removed in vacuo and the residual liquid is vacuum distilled to give the title compound, boiling at   143-144 C;    100% pure by VPC.

 

   Analysis Calcd: C, 60.76; H, 5.10; N, 5.90
 Found: C, 61.46; H, 5.31; N, 5.97
Examnle 2 Preparation of.   4- (4-fluorophenoxy-2-butynl-yl)    cycloproprionate, Compound No. 2.



   A solution of 3.0 gm (0.017 mole) of   4-(4-fluorophenoxy)-2-    butyl-l-ol, 2.5 gm (0.022 mole of cyclopropionyl chloride, 7 ml of triethylamine and 15 ml of ethyl acetate is refluxed 2 hr. The reaction mixture is washed with water. The organic layer is separated and dried. Evaporating the solvent gives 3.3 gm of the title compound as a liquid.



  Examnle 3 Preparation of   N- (3-chloro-4-methylphenyl) -N' ,N'      dimethylacetamidine;    Compound No. 3
 To a solution of 38.23 gm (0.27 mole) of 3-chloro-4-methylani  line, 23.52 gm (0.27 mole) of dimethylacetamide and 500 ml of ethylene dichloride is added 41.40 gm (0.27 mole) of phosphorous oxychloride dropwise with stirring at such a rate as to keep the temperature    < 20 C    with an ice bath. After the phosphorous oxychloride addition is completed, the reaction mixture is stirred 15 min at room temperature then warmed slowly to reflux. The reaction mixture is maintained at reflux 3 hr, then chilled to 50C.

  To the cold reaction mixture is added 300 ml of a 10% sodium hydroxide dropwise keeping the temperature    < 200 C.    After completing the sodium hydroxide addition the mixture is stirred 1 hr and then set aside for 16 hr.



  The mixture is separated. The organic layer is washed with water (1 x 300 ml), and then brine (2 x 200 ml). The organic layer is then dried (Mg S04) and evaporated in vacuo. The residue is vacuum distilled to give the title compound as a clear yellow oil; 18.20 gm (34%), boiling range   85-89"C/0.09    mm, 100% pure by VPC.



  Analysis Calcd: C, 62.70; H, 7.18; N, 13.29
 Found: C,   62.78;    H, 7.00; N, 13.09
Example 4 Preparation of N,N,N',N'-tetramethyl-N"-(3,4dichlorophenyl)guanidine; Compound No. 4
 To a solution of 22.08 gm (0.19 mole) of tetramethylurea, in 150 ml of dichloroethane is added 29.13 gm (0.19 mole) of phosphorus oxychloride at such a rate as to maintain the temperature  <  350C.



  After competing the addition of phosphorus oxychloride, a solution of 30.79 gm (0.19 mole) of 3,4-dichloroaniline in 150 ml of dichlorethane is added at such a rate as to keep the reaction temperature  <    650 C.   The reaction mixture is stirred 1 hr at ambient temperature and then refluxed for 8 hours. The reaction mixture is cooled to 50C and 6N sodium hydroxide is added dropwise until the aqueous layer has a pH-10. The layers are separated. The aqueous layer is extracted (2 x 75 ml) with dichlorethane. The combined organic layers are washed with brine and then dried with magnesium sulfate. The solvent is removed in vacuo and the residue partitioned between benzene and water.

  The organic layer is separated, dried with magnesium sulfate and concentrated in vacuo to give 13.89 gm of   N,N,N' ,N'-tetramethyl-N11.(3,4-dichlorophenyl)guanidine,    bp 132    C/1.4    mm (96% by VPC).



  Example 5 Preparation of 2-[(2,4-dimethylphenyl)imino]-3methyloxazolidine; Compound No. 5  
 Part A:
 To 47.36 gm (0.29 mol) of   2,4-dimethylphenylisothiocyanate    in 400 ml of acetonitrile is added 21.78 gm (0.29 mol) of 2methylaminoethanol dropwise with stirring at ambient temperature.



  The solution is stirred 48 hours then evaporated in vacuo to give a clear amber oil. The oil is partitioned between ethyl acetate and water. The ethyl acetate layer is separated, dried over Na2S04 and evaporated in vacuo to give   l-(2,4-dimethylphenyl)-3-(2-    hydroxyethyl)-3-methylthiourea which is used without further purification in part B.



   Part B:
 The   1-(2,4- dimethylphenyl)-3-( 2 -hydroxyethyl)-3 -methylthiourea    of Part A is dissolved in 400 ml of benzene and 200 ml of absolute ethanol, and 38.99   (O.f8    mol) of yellow mercuric oxide added in batches. The reaction mixture is refluxed for 45 min. and then stirred at room temperature for 16 hours. The reaction mixture is filtered. The filtrate is concentrated in vacuo. The crude product is vacuum distilled to give 2-[(2,4-dimethylphenyl)imino]-3methyloxazolidine, bp   120-122"C/0.25    mm.



   The active compounds of the invention or its salts may be applied singly or in mixtures with other pesticidal agents such as pyrethrins, carbamates, organophosphates, chlorocarbons, and avermectin/milbemycins. They may constitute the active ingredient of dusting compositions, or it may be applied to ticks 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 compound can also be administered in a dip, shampoo, sustained release device for example a flea/tick collar, implant, ear tag or tail clip.



   Accordingly, the new active compounds or their salts may be converted into the formulations customary in practice, such as, for example, solutions, emulsions, suspensions, powders, pastes, and granulates. These are prepared in known manner, e.g. by mixture of the active compound with extenders, e.e. liquid solvents and/or carrier substances, possibly with the use of surface active agents, ie. emulsifiers and/or dispersing agents, it being possible e.g. in the case of the-use of water as extender, that organic solvents may be used as auxiliary solvents. As solvents, e.g. the following are  suitable aromatic (e.g. xylene, benzene, orthodichlorbenzene, trichlorobenzene), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, ethanol, isopropanol, butanol), strongly polar solvents, such as dimethylformamide, N-methylpyrrolidone-(2), dimethyl sulphoxide, and water.

  As solid carriers substances, three are mentioned: natural mineral powders (e.g. kaolins, aluminas, talcum, chalk), synthetic inorganic carrier substances (e.g. highly dispersed silicic acid, silicates); as emulsifier: both non-ionic and anionic or carionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ether, alkyl sulphonates and aryl sulphonates, quaternary ammonium salts with longer alkyl radicals; as dispersing agents, e.g.



  lignin, sulphite waste liquors and methyl cellulose.



   The formulations contain, in general, from 0.1 to 95, preferably 0.5 to 90, per cent by weight active compound. The application concentrations may be prepared from the formulation by dilution with water. They may, depending on the application form, be varied within a fairly wide range, and are generally from 10 to 50,000 ppm (w/w), preferably between 100 and 10,000 ppm.



   The acaricidal properties of the active compounds of the invention, and the use of the compounds have been evaluated against ticks and fleas and have been evaluated in accordance with the following procedures; the results are set forth in Tables I to XI.



  Procedure I Effects against coumaphos resistant adult females of the Southern cattle tick,   Boophilus      microolus    that have detached naturally from cattle.



   Each compound of the invention: 4-(4-fluorophenoxy)-2-butyn-lol methylcarbamate, (Cpd   #1);      4- (4-fluorophenoxy-2-butyn-l-yl)    cycloproprionate, (Cpd &num;2);   N- (3-chloro-4-methylphenyl) -N' ,N'    dimethylacetamidine, (Cpd &num;3);   N,N,N',N' -tetramethyl-N"-(3, 4-      dichlorophenyl) guanidine,    (Cpd &num;4);   2-[(2,4- dimethylphenyl) imino]-3-    methyloxazolidine, (Cpd &num;5);   N- (4-chloro-2-methylphenyl) -N' ,N' -    dimethylacetamidine, (Cpd &num;6); N-(3,4-dichlorophenyl)-N',N'-dimethylcyclo-propyl formamidine, (Cpd &num;7); N-(4-chloro-2-methylphenyl)
N',N'-dimethylpropanimidamide, (Cpd &num;8); N-(3-chloro-4-methylphenyl)   N' ,N' -dimethylpropanimidamide,    (Cpd &num;9); 

  Coumaphos [phosphorothioic acid O-(3-chloro-4-methyl-2-oxo,-2-H-l-benzopyran-7-yl)   O,O-diethyl    ester],   N,N,N' ,N' tetramethylNfl(4chloro2methylphenyl)guanidine,     
Cpd   #59G;    X,N,N',N'-tetramethyl-N"-(3-chloro-4-methylphenyl)- guanidine, Cpd &num;60A;   N,N,N' ,N' -tetramethyl-N"-(2-chloro-6-methyl-    phenyl)guanidine, Cpd &num;60B;   N,N,N' ,N' -tetramethyl-N"-(3-chloro-    phenyl)guanidine, Cpd   #60E;      N,N,N' ,N' -tetramethyl-N"- (2,4-dichloro-    phenyl)guanidine, Cpd &num;60F;   N,N,N' ,N' -tetramethyl-N"-(3 ,5-dichloro-       phenyl)guanidine, Cpd &num;60H;

   and N, N,N,N' ,N' -tetramethyl-N'1-(2,5-      dichlorophenyl) guanidine,    Cpd   #61A;      N,N,Ns,N' -tetramethyl-N"- (nitro-    phenyl) guanidine, Cpd &num;10;   N,N,N(',N' -tetramethyl-N" -phenyl    guanidine, Cpd  & um;11;

  N,N'-dimethyl-N"-(4-chloro-2-methylphenyl)guanidine, Cpd &num;12;   N, N, N' ,N' -tetramethyl-N"- (4-chlorophenyl) guanidine,    Cpd &num;13;   N,N,N'      , N' -tetramethyl-N"-(4 -methylphenyl) guanidine,    Cpd   #14;    2phenylimino-3-methyl-oxazolidine, Cpd   61G;      2- [ (3-chlorophenyl) imino] -      3-methyloxazolidine,    Cpd   #62C;      2- [(3, 4-dichlorophenyl) imino] -3-    methyloxazolidine, Cpd &num;64G; and   2-[(4-chloro-2-methylphenyl)imino]-    3-methyloxazolidine is formulated as an emulsifiable concentrate containing 20% active ingredient, 70% xylene and   108    Triton X-100.



  Formulations are mixed with water and tested at concentrations of   t.O,    0.1 and   0.01%    W/V active ingredient; the lesser concentrations are obtained by serial dilutions of the   1ç08    concentration. Prior to treating, ticks are washed in tap water, dried and placed into groups of 5. The weight of each group is determined. For testing, a group of 5 ticks is placed into a beaker containing 25 ml of test solution, stirred for 30 seconds and then poured through a screen that retains the ticks. Drained ticks are placed on paper towels to dry and then placed (5 ticks/petri dish) in a plastic petri dish lined with
Whatman No. 1 filter paper. Each dish is covered with a lid, and placed in a desiccator jar containing saturated solutions of KC1 (85% relative humidity).

  The desiccator jar is held in an incubator at approximately 27 C for oviposition. At 2 weeks post-treatment, ticks are discarded, and the eggs weighed and placed in vials. Each vial is closed by securing organdy cloth over the end and then returned to the incubator. At 6 weeks post-treatment, percent egg hatch is determined by counting egg shells and unhatched eggs for 10 subsamples from each vial. Other groups of 5 ticks are dipped in emulsions of the solvent at concentrations equivalent to those used with test compounds and represent solvent controls. Other groups of ticks are not dipped and represent non-treated controls.



   The reproduction of each group of ticks is determined as  follows:
 Reproduction - Weight eggs laid(g) X (%Hatch) x (20,000*)
 Index Weight ticks(g) * - 1 gram of eggs usually produce 20,000 larvae
 The mean reproduction of treated ticks is compared with the mean reproduction of the solvent control to provide a measure of the inhibition of reproduction (% control) as follows: % Control -   Repros    Index Control - ReDrod. Index Treated X (100)
 Reprod. Index Controls
The results of the trial are reported in Tables I and IA.



  Procedure II Southern Cattle Tick (Larval) Study
 Compounds are evaluated against larvae of the southern cattle tick, B.   microolus.   



   Stock solutions of test compounds are prepared by dissolving 10 mg technical compound in 5 ml acetone. Three to seven concentrations (2-fold or 10-fold dilutions, depending on study) are prepared for each compound. The test solution (0.25 ml) is added to a l-dram glass vial containing Whatman No. 1 filter paper (13 sq cm). Vials are left open in a hood for 24 hrs to allow the solvent to evaporate and then capped and stored at   4"C    until testing. Concentrations of drug are expressed as either percent of drug in the drug/solvent mixture (Table II) or micrograms of drug per square centimeter of filter paper lining of the vial (Table III).



   Twenty tick larvae are added to each vial and held at room temperature. At 4 or 24 hrs post-treatment, mortality is determined.



   The results are reported in Tables II-III.



  Procedure III Brown Dog Tick and Lone Star Tick (Larvae)
 Compounds are evaluated against larvae of the brown dog tick   (Rhipicephalus      sancuineus)    and lone star tick   (Amblaomma    americanum) and adult R.   sanauineus    and Dermacentor variabilis. Stock solutions of test compounds are prepared by dissolving 10 mg technical compound in 10 ml acetone. Serial dilutions (10-fold) are made to obtain lower concentrations. Test solutions are drawn into disposable glass (Pasteur) pipettes, 2.6 ml in size, held for 20 seconds and then the solution dispensed. Concentrations of drugs are expressed as either percent in the drug/solvent mixture (Table V) or micrograms per square centimeter of tube surface (Table IV).

  Pipettes are allowed to dry 18 to 24 hours and then the large end of each pipette is  covered with organdy cloth and secured with a rubber band. Tick larvae (10 per pipette) are aspirated into the pipettes through the tapered ends and then the tapered ends sealed with dental wax.



  Treated and control pipettes containing larvae are held at 23 +   l0C    and  > 90% with a 14 hr light, 10 hr dark period. At 4 or 24 hrs posttreatment, larval mortality is determined. The results are reported in Tables IV-IX.



  Procedure IV Cat Flea Study
 Compounds are tested for contact activity against adult cat fleas   (Ctenocenhalides    felis). Stock solutions are prepared by dissolving 20 mg technical compound in 1 ml acetone. Serial dilutions (10-fold) are made to obtain desired concentrations. One dram vials are lined with filter paper (13 sq cm) and then 0.25 ml of test solution is added to a vial. Concentrations of drug are expressed as either percent in the drug/solvent mixture (Table X) or micrograms per square centimeter of tube surface (Table XI). Vials are left open for 24 hrs to allow solvent to evaporate.

 

   Twenty adult fleas are added to each vial. Vials are capped and held at 23 +   10C    and  > 90% RH with 14 hr light, 10 hr dark photoperiod. At 2-24 hrs post-treatment, percent mortality is determined. The results are reported in Tables X-XI.



   The insecticidal properties of the compounds, and the use of the compound has been evaluated against ticks and fleas.  



   TABLE I
 Compounds Evaluated Against Adult   Boophilus    microDlus
 Evaluation of Tick Reproduction After Compound Exposure
 Reproduction* Percent
Treatment Dose   (*)    Index Control
Time: 6 weeks
Amitraz 1.0 0c 100
Coumaphos 1.0 462bc 91
Compound No. 1 1.0 1639bC 67
Compound No. 3 1.0 185b 96
Compound No. 4 1.0   174hub    65
Compound No. 5 1.0   Oc    100
Placebo --- 4977a 0
 (LSD - 1933) *Reproduction index - number surviving larvae per gram of tick.



  Within each dose, reproduction indices followed by the same letter are not significantly different at P < 0.05.  



   TABLE IA
 Evaluation of Adult   Boonhilus    microplus Reproduction   Potentiai   
 After Compound Exposure
Time: 6 weeks
 Reproduction* Percent
Treatment Dose (%) Index Control
Amitraz 0.1   0c    100
Coumaphos 0.1 1720bC 73
Compound &num;4 0.1 3839ab 40
Compound &num;5 0.1 176 97
Placebo --- 6404a 0
 LSD 2922 * Reproduction index - number surviving larvae per gram of tick; a,b Reproduction indices followed by the same letter are not significantly different at   P < 0.05.     



   TABLE IS
Parasite: Booohilus   microplus    larvae
Time: 4 hr.



  Treatment Rate (%) Percent Mortalitv
Coumaphos 1.0 100
Compound 2 1.0 80
Compound 1 1.0 100
Compound 3 1.0 100
Compound 5 1.0 100
Compound 6 1.0 90
Compound 7 1.0 90
Compound 8 1.0 0
Compound 9 1.0 90
Compound 64H 1.0 100
Compound 62C 1.0 90
Compound 64G 1.0 100
Compound 61E 1.0 0
Compound 4 1.0 100
Compound 59G 1.0 80
Compound 60A 1.0 80
Compound 60B 1.0 80
Compound 60E 1.0 90
Compound 60F 1.0 100
Compound 60H 1.0 90
Compound 61A 1.0 30
Acetone Control --- 0  
 TABLE   IIB   
Parasite:   Boophilus      microslus    larvae
Time: 4 hrs.



  Treatment Rate Rate Unit ReD Mean % Mortality
Coumaphos 0.1 Percent 3 100
Compound 1 0.1 Percent 3 83
Acetone Control   - -      -- -    3 13
 TABLE IIC
Parasite:   Boophilus      microplus    (larvae)
Time: 4 hr.



   Mean
 Percent
Treatment Rate Rate Unit Rep Mortalitv
Acetone Control -- --- 3 13
Coumaphos 0.1 percent 3 67
Compound &num;3 0.1 percent 3 90
Compound 5 0.1 percent 3 10
Compound 59G   0.1    percent 3 57
Compound 60F   0.1    percent 3 33
Compound 61G 0.1 percent 3 90
Compound 64G   0.1    percent 3 67  
 TABLE   IID   
Parasite:   Boophilus      microDlus    (larvae)
Time: 4 hr.



   Mean
 Percent
Treatment Rate Rate Unit Ren Mortalitv
Coumaphos 0.01 percent 3 67
Compound &num;3 0.01 percent 3 73
Compound &num;4 0.01 percent 3 80
Coumaphos 0.10 percent 3 100
Compound &num;4 0.10 percent 3 97
Coumaphos 1.00 percent 3 100
Compound &num;4 1.00 percent 3 93
Acetone Control ---   - - -    3 23
Coumaphos 1.00 percent 3 100
Compound   61G    0.01 percent 3 0
Compound 61G 0.10 percent 3 90
Compound 61G 1.00 percent 3 100
 TABLE   IIE   
Parasite:   Boonhilus      microplus    (larvae)
Time: 10   hr.   



   Mean
 Percent
Treatment Rate (50) Mortalitv
Coumaphos 0.1 70 &num;5 0.1 50   #62C    0.1 70 &num;64G 0.1 10
Acetone Control --- 0  
 TABLE IIIA
Parasite:   B.microDlus    larvae
Time: 4 hrs.



   Mean
 Percent
Treatment Rate Rate unit Rep. Mortality
Coumaphos 3.85 mcg/sq/cm 3 30
Compound &num;4 3.85 mcg/sq/cm 3 57
Coumaphos 38.5 mcg/sq/cm 3 93
Compound &num;4 38.5 mcg/sq/cm 3 97
Coumaphos 385 mcg/sq/cm 3 100
Compound &num;4 385 mcg/sq/cm 3 97
Acetone Control ---   -- -    3 40
 TABLE IIIB
Parasite: B.   microplus    larvae
Time: 4 hrs.



   Mean
 Percent
Treatment Rate Rate unit   Rend.    Mortality
Coumaphos 3.85 mcg/sq/cm 3 83 59G 3.85 mcg/sq/cm 3 73
Coumaphos 38.5 mcg/sq/cm 3 93 59G   38.5    mcg/sq/cm 3 90
Coumaphos 385 mcg/sq/cm 3 87 59G 385 mcg/sq/cm 3 100
Acetone Control --- --- 3 3 0  
 TABLE IIIC
Parasite: B.   microplus    larvae
Time: 4 hrs.



   Mean
 Percent
Treatment Rate Rate unit   Res.    Mortalitv
Coumaphos 3.85 mcg/sq/cm 3 100
Compound &num;4 3.85 mcg/sq/cm 3 83
Coumaphos 38.5 mcg/sq/cm 3 100
Compound &num;4 38.5 mcg/sq/cm 3 97
Coumaphos 385 mcg/sq/cm 3 100
Compound   X4    385 mcg/sq/cm 3 90
Acetone Control --- --- 3 0  
 TABLE IIID
Parasite:   Boophilus    microplus (larvae)
Time: 4 hr.



   Mean
 Percent
Treatment Rate Rate Unit Rep Mortalitv
Acetone Control --- --- 3 0
Amitraz 4.81 mcg/sq cm 3 0
Chlordimeform 4.81 mcg/sq cm 3 0
Coumaphos 4.81 mcg/sq cm 3 90
Compound &num;3 4.81 mcg/sq cm 3 83
Compound &num;4 4.81 mcg/sq cm 3 37
Amitraz 9.63 mcg/sq cm 3 3   Ghlordimeform    9.63 mcg/sq cm 3 0
Coumaphos 9.63 mcg/sq cm 3 93
Compound &num;3 9.63 mcg/sq cm 3 100
Compound &num;4 9.63 mcg/sq cm 3 70
Amitraz 19.25 mcg/sq cm 3 3
Chlordimeform 19.25 mcg/sq cm 3 0
Coumaphos 19.25 mcg/sq cm 3 100
Compound &num;3 19.25 mcg/sq cm 3 97
Compound &num;4 19.25 mcg/sq cm 3 87
Amitraz 38.50 mcg/sq cm 3 10
Chlordimeform 38.50 mcg/sq cm 3 0
Coumaphos 38.50 mcg/sq cm 3 100
Compound &num;3 38.50 mcg/sq cm 3 100
Compound #4 38.50 mcg/sq cm 3 100  
 TABLE IIIE
Parasite: B.   microolus    larvae
Time: 4 hrs.



   Mean
 Percent
Treatment Rate Rate Unit Rep Mortalitv
Coumaphos 3.85 mcg/sq/cm 3 93
Compound &num;10 3.85 mcg/sq/cm 3 30
Compound &num;11 3.85 mcg/sq/cm 3 17
Compound &num;12 3.85 mcg/sq/cm 3 27
Compound &num;4 3.85 mcg/sq/cm 3 87 60H 3.85 mcg/sq/cm 3 7
Coumaphos 38.5 mcg/sq/cm 3 100
Compound &num;10 38.5 mcg/sq/cm 3 100
Compound &num;11 38.5 mcg/sq/cm 3 73
Compound &num;12 38.5 mcg/sq/cm 3 87
Compound &num;4 38.5 mcg/sq/cm 3 100
Compound &num;5 38.5 mcg/sq/cm 3 100 60H 38.5 mcg/sq/cm 3 97
Coumaphos 385 mcg/sq/cm 3 100
Compound &num;10 385 mcg/sq/cm 3 100
Compound &num;11 385 mcg/sq/cm 3 97
Compound &num;12 385 mcg/sq/cm 3 93
Compound &num;4 385 mcg/sq/cm 3 100
Compound &num;5 385 mcg/sq/cm 3 100 60H 385 mcg/sq/cm 3 100
Acetone Control --- --- 3 3  
 TABLE IIIF
Parasite:   Boophilus      microplus    larvae
Time: 

  :   4 hrs.   



  Treatment Rate Rate Unit Rep Mean % Mortalitv
Acetone Control --- --- 3 3
Coumaphos 3.85 MCG/SQ CM 3 100
Compound 1 3.85 MCG/SQ CM 3 90
Compound 3 3.85 MCG/SQ CM 3 87
Coumaphos 38.50 MCG/SQ CM 3 100
Coumaphos 38.50 MCG/SQ CM 3 97
Coumaphos 385.00 MCG/SQ CM 3 100
Compound 1 385.00   NCG/SQ    CM 3 100
Compound 3 385.00 MCG/SQ CM 3 100
Amitraz 38.50 MCG/SQ CM 3 53
Chlordimeform 38.50 MCG/SQ CM 3 17
Coumaphos 38.50 MCG/SQ CM 3 100
Compound 1 38.50 MCG/SQ CM 3 67
Compound 3 38.50 MCG/SQ CM 3 97
Amitraz 19.25 MCG/SQ CM 3 67
Chlordimeform 19.25 MCG/SQ CM 3 0
Coumaphos 19.25 MCG/SQ CM 3 100
Compound 1 19.25 MCG/SQ CM 3 60  
 TABLE IIIG
Parasite:   Boophilus      microolus    (larvae)
Time: 24 hr.



   Mean
 Percent
Treatment Rate Rate Unit Rep Mortalitv
Acetone Control ---   - - -    3 0
Amitraz 9.63 mcg/sq cm 3 93
Chlordimeform 9.63 mcg/sq cm 3 93
Coumaphos 9.63 mcg/sq cm 3 100
Compound &num;5 9.63 mcg/sq cm 3 97
Amitraz 19.25 mcg/sq cm 3 93
Chlordimeform 19.25 mcg/sq cm 3 100
Coumaphos 19.25 mcg/sq cm 3 100
Compound &num;5 19.25 mcg/sq cm 3 100
Amitraz 38.50 mcg/sq cm 3 90
Chlordimeform 38.50 mcg/sq cm 3 100
Coumaphos 38.50 mcg/sq cm 3 100
Compound &num;5 38.50 mcg/sq cm 3 100
 TABLE IIIH
Parasite:   Boophilus      micronlus    (larvae)
Time: 4 hr.



   Mean
 Percent
Treatment Rate Rate Unit Rep Mortalitv
Acetone Control --- --- 3 0
Amitraz 38.50 mcg/sq cm 3 17
Chlordimeform 38.50 mcg/sq cm 3 0
Coumaphos 38.50 mcg/sq cm 3 100
Compound &num;3 38.50 mcg/sq cm 3 97  
 TABLE   Ill-I   
Parasite: B.   microplus    larvae
Time: 4 hrs.



   Mean
 Percent
Treatment Rate Rate unit Rep. Mortalitv
Amitraz 0.6 mcg/sq/cm 3 0
Chlordimeform 0.6 mcg/sq/cm 3 0
Coumaphos 0.6 mcg/sq/cm 3 0
Compound &num;4 0.6 mcg/sq/cm 3 0 59G 0.6 mcg/sq/cm 3 0 60E   0.6    mcg/sq/cm 3 0 60F 0.6 mcg/sq/cm 3 0
Amitraz 1.2 mcg/sq/cm 3 0
Chlordimeform 1.2 mcg/sq/cm 3 0
Coumaphos 1.2 mcg/sq/cm 3 27
Compound &num;4 1.2 mcg/sq/cm 3 20 59G 1.2 mcg/sq/cm 3 0 60E 1.2 mcg/sq/cm 3 0 60F   1.2    mcg/sq/cm 3 0
Amitraz 2.4 mcg/sq/cm 3 0
Chlordimeform 2.4 mcg/sq/cm 3 0
Coumaphos 2.4 mcg/sq/cm 3 60
Compound &num;4 2.4 mcg/sq/cm 3 0   59G    2.4 mcg/sq/cm 3 0 60E 2.4 mcg/sq/cm 3 0 60F 2.4 mcg/sq/cm 3 0
Amitraz 4.8 mcg/sq/cm 3 7
Chlordimeform 4.8 mcg/sq/cm 3 0
Coumaphos 4.8 mcg/sq/cm - 3 93
Compound &num;

  ;4 4.8 mcg/sq/cm 3 10 59G 4.8 mcg/sq/cm 3 0 60E 4.8 mcg/sq/cm 3 0 60F 4.8 mcg/sq/cm 3 0
Amitraz 9.6 mcg/sq/cm 3 43
Chlordimeform 9.6 mcg/sq/cm 3 0  
 TABLE III-I (continued)
 Mean
 Percent
Treatment Rate Rate unit Rep. Mortalitv
Coumaphos 9.6 mcg/sq/cm 3 83
Compound &num;4 9.6 mcg/sq/cm 3 70 59G 9.6 mcg/sq/cm 3 0 60E 9.6 mcg/sq/cm 3 13 60F 9.6 mcg/sq/cm 3 7
Amitraz 19.2 mcg/sq/cm 3 7
Chlordimeform 19.2 mcg/sq/cm 3 0
Coumaphos 19.2 mcg/sq/cm 3 100
Compound &num;4 19.2 mcg/sq/cm 3 97 59G 19.2 mcg/sq/cm 3 63 60E 19.2 mcg/sq/cm 3 60 60F 19.2 mcg/sq/cm 3 87  
 TABLE IIIJ
Parasite:   Booohilus      microplus    (larvae)
Time: 24 hr.



   Mean
 Percent
Treatment Rate Rate Unit Rep Mortalitv
Acetone Control --- --- 3 0
Amitraz 4.81 mcg/sq cm 3 43
Chlordimeform 4.81 mcg/sq cm 3 0
Coumaphos 4.81 mcg/sq cm 3 100
Compound &num;3 4.81 mcg/sq cm 3 90
Amitraz 9.63 mcg/sq cm 3 77
Chlordimeform 9.63 mcg/sq cm 3 23
Coumaphos 9.63 mcg/sq cm 3 100
Compound &num;3 9.63 mcg/sq cm 3 97
Amitraz 19.25 mcg/sq cm 3 67
Chlordimeform 19.25 mcg/sq cm 3 0
Coumaphos 19.25 mcg/sq cm 3 100
Compound #3 19.25 mcg/sq cm 3 93
Amitraz 38.50 mcg/sq cm 3 53
Chlordimeform 38.50 mcg/sq cm 3 17
Coumaphos 38.50 mcg/sq cm 3 100
Compound &num;3 38.50 mcg/sq cm 3 83
Compound #5 38.50 mcg/sq cm 3 97  
 TABLE   IIIK   
Parasite:   Boophilus      microplus    (larvae)
Time: 24 hr.



   Mean
 Percent
Treatment Rate Rate Unit Rev Mortalitv
Acetone Control --- --- 3 7
Amitraz 2.41 mcg/sq cm 3 97
Chlordimeform 2.41 mcg/sq cm 3 80
Coumaphos 2.41 mcg/sq cm 3 100
Compound &num;3 2.41 mcg/sq cm 3 100
Amitraz 4.81 mcg/sq cm 3 93
Chlordimeform 4.81 mcg/sq cm 3 77
Coumaphos 4.81 mcg/sq cm 3 100
Compound &num;3 4.81 mcg/sq cm 3 100
Amitraz 9.63 mcg/sq cm 3 93
Chlordimeform 9.63 mcg/sq cm 3 93
Coumaphos 9.63 mcg/sq cm 3 100
Compound &num;3 9.63 mcg/sq cm 3 100
Amitraz 19.25 mcg/sq cm 3 93
Chlordimeform 19.25 mcg/sq cm 3 100
Coumaphos 19.25 mcg/sq cm 3 100
Compound &num;3 19.25 mcg/sq cm 3 100
Amitraz 38.50 mcg/sq cm 3 90
Chlordimeform 38.50 mcg/sq cm 3 100
Coumaphos 38.50 mcg/sq cm 3 100
Compound &num;3 38.50 mcg/sq cm 3 100  
 TABLE IV
Parasite: Amblvomma americanum larvae
Time: 4 hrs.



   Mean
 Percent
Treatment Rate Rate unit Rep. Mortalitv
Amitraz 3.85 mcg/sq/cm 3 13
Chlordimeform 3.85 mcg/sq/cm 3 3
Coumaphos 3.85 mcg/sq/cm 3 17
Compound &num;4 3.85 mcg/sq/cm 3 27 59G 3.85 mcg/sq/cm 3 0 60E 3.85 mcg/sq/cm 3 3 60F 3.85 mcg/sq/cm 3 0
Compound &num;13 3.85 mcg/sq/cm 3 0
Compound   *14    3.85 mcg/sq/cm 3 7
Amitraz 38.5 mcg/sq/cm 3 37
Chlordimeform 38.5 mcg/sq/cm 3 7
Coumaphos 38.5 mcg/sq/cm 3 33
Compound &num;4 38.5 mcg/sq/cm 3 83   59G    38.5 mcg/sq/cm 3 27 60E 38.5 mcg/sq/cm 3 47 60F 38.5 mcg/sq/cm 3 10
Compound   *13    38.5 mcg/sq/cm 3 10
Compound   *14    38.5 mcg/sq/cm 3 37
Amitraz 385 mcg/sq/cm 3 27
Chlordimeform 385 mcg/sq/cm 3 100
Coumaphos 385 mcg/sq/cm 3 43
Compound &num;4 385 mcg/sq/cm 3 100 59G 385 mcg/sq/cm 3 97 60E 385 mcg/sq/cm 3 100 60F 385 mcg/sq/cm 3 100
Compound &num;

  ;13 385 mcg/sq/cm 3 100
Compound   *14    385 mcg/sq/cm 3 100
Acetone Control --- --- 3 7
Compound &num;3 3.85 mcg/sq/cm 3 37
Compound &num;3 38.50 mcg/sq/cm 3 47
Compound   3    385 mcg/sq/cm 3 97
Compound &num;1 3.85 mcg/sq/cm 3 37  
 TABLE IV   (conttd)   
Parasite: Amblvomma americanum larvae
Time: 4 hrs.



   Mean
 Percent
Treatment Rate Rate unit   Reo.    Mortalitv
Compound &num;1 38.50 mcg/sq/cm 3 50
Compound &num;5 385 mcg/sq/cm 3 77
 TABLE VA
Parasite: Amblvomma americanum larvae
Time: 4 hr.



   Mean
 Percent
Treatment Rate Rate Unit   Rep    Mortalitv
Acetone Control --- --- 3 3
Amitraz 0.01 percent 3 7
Coumaphos 0.01 percent 3 0
Compound &num;1 0.01 percent 3 33
Amitraz 0.10 percent 3 20
Coumaphos 0.10 percent 3 0
Compound &num;1 0.10 percent 3 83
Amitraz 1.00 percent 3 20
Coumaphos 1.00 percent 3 0
Compound &num;1 1.00 percent 3 97
Compound   X3    0.01 percent 3 30
Compound &num;3 0.10 percent 3 40
Compound &num;3 1.00 percent 3 30
Compound   X4    0.01 percent 3 37
Compound &num;4 0.10 percent 3 60
Compound &num;4 1.00 percent 3 70  
 TABLE VB
Parasite: Amblvomma americanum (larvae)
Time: 24 hr.

 

   Mean
 Percent
Treatment Rate Rate Unit   Ren    Mortalitv
Acetone Control --- --- 3 10
Amitraz 0.1 percent 3 100
Coumaphos 0.1 percent 3 100
Compound &num;3   0.1    percent 3 100
Amitraz 1.0 percent 3 100
Coumaphos   1.0    percent 3 100
Compound &num;3 1.0 percent 3 100
Coumaphos 0.01 percent 3 93
Compound &num;4 0.01 percent 3 50
Compound #4 0.10 percent 3 93
Compound #4 1.00 percent 3 100
Amitraz 0.01 percent 3 100
Compound &num;5 0.1 percent 3 100
Compound &num;5 1.0 percent 3 90  
 TABLE VIA
Treatment Rate Rate Unit Rep Mean % Mortalitv
Parasite:   Rhioicenhalus      sanguineous    larvae
Time: 4 hrs.



  Acetone Control --- --- 3 0
Amitraz 0.0001 percent 3 0
Coumaphos 0.0001 percent 3 3
Compound &num;1 0.0001 percent 3 0
Amitraz 0.0010 percent 3 3
Coumaphos 0.0010 percent 3 0
Compound &num;1 0.0010 percent 3 10
Amitraz 0.0010 percent 3 3
Coumaphos 0.0010 percent 3 23
Compound &num;1 0.0010 percent 3 10
Amitraz 0.1000 percent 3 0
Coumaphos 0.1000 percent 3 23
Compound &num;1 0.1000 percent 3 67
Amitraz 1.0000 percent 3 0
Coumaphos 1.0000 percent 3 13
Compound &num;1 1.0000 percent 3 90
Compound &num;3 0.0001 percent 3 10
Compound &num;3 0.001 percent 3 3
Compound &num;3 0.01 percent 3 40
Compound &num;3 0.10 percent 3 87
Compound &num;3 1.0 percent 3 57
Compound &num;4 0.000001 percent 3 7
Compound &num;4 0.00001 percent 3 3
Compound &num;4 0.0001 percent 3 17
Compound &num;4 0.0100 percent 3 73
Compound &num;4 0.1000 percent 3 90
Compound &num;

  ;4 1.0000 percent 3 93
Amitraz 0.000001 percent 3 0
Coumaphos 0.000001 percent 3 0
Amitraz 0.00001 percent 3 0
Coumaphos 0.00001 percent 3 10  
 TABLE VIB
Parasite:   Rhipicephalus    sanauineus (larvae)
Time: 24 hr.



   Mean
 Percent
Treatment Rate Rate Unit Rep Mortalitv
Acetone Control   -- -      - -    3 0
Amitraz 0.1 percent 3 87
Coumaphos 0.1 percent 3 100
Compound &num;1 0.1 percent 3 93
Amitraz   f.O    percent 3 90
Coumaphos   1.0    percent 3 100
Compound   #1    1.0 percent 3 100
Compound &num;4 0.01 percent 3 97
Compound &num;4 0.1 percent 3 100
Compound &num;4 1.0 percent 3 100
Amitraz   O.01    percent 3 97
Coumaphos 0.01 percent 3 100
Compound &num;3 0.1 percent 3 100
Compound &num;3 1.0 percent 3 100
Compound &num;5 0.1 percent 3 100
Compound &num;5 1.0 percent 3 100  
 TABLE VII
Parasite: Adult R.   sanguineous   
Time: 24 hrs.



   Mean
 Percent
Treatment Rate Rate unit   Reo.    Mortality
Carbaryl 385 mcg/sq/cm 1 100
Compound  & um;4 385 mcg/sq/cm 1 100
Acetone Control --- --- 1 0
 TABLE   VIIIA   
Parasite: Adult Rhipicephalus   sanguineous   
Time: 24 hrs.



   Mean
 Percent
Treatment Rate Rate unit Rep. Mortality
Baygon 1.0 percent 1 100
Compound #4 1.0 percent 1 20
Acetone Control --- --- 1 0
 TABLE VIIIB
Parasite: Adult Rhipicephalus   sanauineus   
Time: 3 hrs.



   Mean
 Percent
Treatment Rate Rate unit   Res.    Mortalitv
Acetone Control   - - -    --- 1 0
Baygon 1.0 percent 1 100
Compound &num;3 1.0 percent 1 80  
 TABLE IX
Parasite: Adult Dermacentor variabilis
Time: 24 hrs.



   Mean
 Percent
Treatment Rate Rate unit Rev. Mortalitv
Carbaryl 385 mcg/sq/cm 1 40
Compound &num;4 385 mcg/sq/cm 1 40
Acetone Control --- --- 1 0
 TABLE X
Parasite: Adult   Ctenocephalides    felis
Time: 3 hr.



   Mean
 Percent
Treatment Rate Rate Unit Number Mortality   Acetone Control - - - - - - 1 9   
Baygon 1.0 percent 1 100
Carbaryl 1.0 percent 1 46
Compound &num;3 1.0 percent 1 100
Compound &num;4 1.0 percent 1 100  
 TABLE XIA
Parasite: Adult C. felis
Time: 2 hrs.



   Mean
 Percent
Treatment Rate Rate unit Rep. Mortality
Baygon 3.85 mcg/sq/cm 2 82
Carbaryl 3.85 mcg/sq/cm 3 38
Compound &num;10 3.85 mcg/sq/cm 3 0
Compound &num;4 3.85 mcg/sq/cm 3 13 59G 3.85 mcg/sq/cm 3 10 60H 3.85 mcg/sq/cm 3 7 60E 3.85 mcg/sq/cm 3 5 60F 3.85 mcg/sq/cm 3 20
Compound &num;13 3.85 mcq/sq/cm 3 7
Compound &num;14 3.85 mcq/sq/cm 3 5
Baygon 38.5 mcg/sq/cm 3 98
Carbaryl 38.5 mcg/sq/cm 3 43
Compound &num;10 38.5 mcg/sq/cm 3 8
Compound &num;4 38.5 mcg/sq/cm 3 42   59G    38.5 mcg/sq/cm 3 83 60H 38.5 mcg/sq/cm 3 38 60E 38.5 mcg/sq/cm 3 10 60F 38.5 mcg/sq/cm 3 87
Compound &num;13 38.5 mcq/sq/cm 3 10
Compound &num;14 38.5 mcq/sq/cm 3 7
Baygon 385 mcg/sq/cm 3 100
Carbaryl 385 mcg/sq/cm 3 35
Compound &num;10 385 mcg/sq/cm 3 7
Compound &num;4 385 mcg/sq/cm 3 100
Compound &num;

  ;3 385 mcg/sq/cm 3 100 59G 385 mcg/sq/cm 3 95 60H 385 mcg/sq/cm 3 100 60E 385 mcg/sq/cm 3 100 60F 385 mcg/sq/cm 3 100
Compound &num;13 385 mcq/sq/cm 3 93
Compound &num;14 385 mcq/sq/cm 3 100
Acetone Control ---   -- -    3 0  
 TABLE XIB
Parasite: Adult C. felis
Time: 24 hrs.



   Mean
 Percent
Treatment Rate Rate unit Rep. Mortality
Baygon   3.85    mcg/sq/cm 2 100
Carbaryl 3.85 mcg/sq/cm 3 93
Compound &num;10 3.85 mcg/sq/cm 3 2
Compound #4 3.85 mcg/sq/cm 3 20
Compound &num;1 3.85 mcg/sq/cm 3 13 59G 3.85 mcg/sq/cm 3 22 60H 3.85 mcg/sq/cm 3- 8 60E 3.85 mcg/sq/cm 3 23 60F 3.85 mcg/sq/cm 3 30
Compound #13 3.85 mcq/sq/cm 3 15
Compound &num;14 3.85 mcq/sq/cm 3 12
Baygon 38.5 mcg/sq/cm 3 98
Carbaryl 38.5 mcg/sq/cm 3 100
Compound &num;10 38.5 mcg/sq/cm 3 20
Compound &num;4 38.5 mcg/sq/cm 3 75 59G 38.5 mcg/sq/cm 3 100 60H 38.5 mcg/sq/cm 3 98 60E 38.5 mcg/sq/cm 3 75 60F 38.5 mcg/sq/cm 3 82
Compound &num;13 38.5 mcq/sq/cm 3 88
Compound &num;14 38.5 mcq/sq/cm 3 38
Baygon 385 mcg/sq/cm 3 100
Carbaryl 385 mcg/sq/cm 3 100
Compound &num;10 385 mcg/sq/cm 3 15
Compound &num;

  ;4 385 mcg/sq/cm 3 100   59G    385 mcg/sq/cm   3.    100 60H 385 mcg/sq/cm 3 100 60E 385 mcg/sq/cm 3 100 60F 385 mcg/sq/cm 3 100
Compound &num;13 385 mcq/sq/cm 3 100
Compound &num;14 385 mcq/sq/cm 3 100
Acetone Control --- --- 3 10  
 TABLE XIB (Cont'd)
Parasite: Adult C. felis
Time: 24 hrs.



   Mean
 Percent
Treatment Rate Rate unit ReD. Mortality
Compound &num;1 38.5 mcg/sq/cm 3 17
Compound &num;3 38.5 mcg/sq/cm 3 100
Compound &num;1 385 mcg/sq/cm 3 98
Compound &num;3 385 mcg/sq/cm 3 100
 TABLE XIC
Parasite: Adult   Ctenocenhalides    felis
Time: 24 hr.



   Mean
 Percent
Treatment Rate Rate Unit Rep Mortalit
Acetone Control --- --- 3 0
Baygon 385.00 mcg/sq cm 3 100
Carbaryl 385.00 mcg/sq cm 3 100
Compound &num;5 385.00 mcg/sq cm 3 100
Compound &num;4 305.00 mcg/sq cm 1 100
 TABLE XID
Parasite: Adult   Ctenocenhalides    felis
Time: 24 hrs.



   Mean
 Percent
Treatment Rate Rate Unit Number Mortal it
Acetone Control --- --- 1 9
Carbaryl 385 mcg/sq/cm 1 100
Compound &num;5 385 mcg/sq/cm 1 92
Compound   #61G    385 mcg/sq/cm 1 92  
 APPENDIX A
Known Amidines
EMI38.1     
   cA   
Registry # R1   R2      R3      R4    R5 References 51366-917   Cl    2-CH3 CH3 CH3 CH3 1
Mixture with none 3-CH3NHCO CH3 CH3 CH3 88695-45-8 Br H CH3 CH3 CH3 2 88695-46-9 CH3 H C2R5 CH3 CH3 2e 94793-29-0 F H CH3 CH3 CH3 2d 36171-98-9 CH3 2,6-(CH3)2 CH3 CH3 CH3 3 36192-30-0 I H CH3 CH3 CH3 2d,3 36192-57-1 (HCl salt of 36192-30-0) I H CH3 CH3 CH3 3 36199-40-3 (quaternary salt of 36191-98-9) CH3 2,6-(CH3)2 CH3 CH3 CH3 3 36209-64-0
HC1 salt of 36171-98-9 CH3 2,6-(CH3)2 CH3 CH3 CH3 3 13181-52-7   C1    H CH3 CH3  

   CH3 4 13356-83-7 (perchlorate salt)   C1    3-C1 CH3 CH3 CH3 4a,4b,10 79489-69-3 CH3 H   C2R5    C2H5 C2H5 5 27472-10-2 (free base of 13356-83-7)   C1    H CH3 CH3 CH3 2a,2b,2c,2d,    6a,6b,4a    54796-29-1 CH3 H CH3 CH3 CH3 2a,2b,2c,2d,
 2e,6a,6b 3239-93-8   C1    3-C1 CH3 CH3 CH3 7a,7b,4a,8 3239-95-0   C1    3-C1 CH3 C2H5 C2H5 8  
Known Amides
EMI39.1     

CA   Registry    # R1 R2 R3   R4    R5 References 56531-97-6   C1    2-CH3 CH3 CH3 CH3 9 31734-97-1   C1    3-CH3 C2H5 C2H5 C2H5 7b 31735-00-9   C1    2-CH3 C2H5 C2H5 C2H5 7b 31735-02-1 CH3 3-C1 C2H5 C2H5   C2R5    7b 31801-95-3   Cl    3-C1 C2H5 C2H5 C2H5 

   7b 31802-01-4 Cl 3-C1 CH3 C2H5 C2H5 7b,8 31802-05-8 Cl 3-CH3 CH3 C2H5 C2H5 7b
H 3-C1 CH3 CH3 CH3 8
Cl H CH3 CH3 CH3 10 (Perchlorate salt of 13181-52-7)
C1 Cl 2-C1 CH3 CH3 CH3 11
H H H CH3 CH3 CH3 12  
   AMIDINE    REFERENCES 1. W.G. Duncombe, Rhodesia   Agr.    J. 70, 115-18 (1973); Chem. Abstr.



   80:79102t.



  2. a. J. Oszczapowicz,   E    Raczynska, and J. Osek,   Mags.    Reson.



   Chem. 24, 9-14 (1986); Chem. Abstr. 105:114543w.



   b. J. Oszczapowicz, J. Osek, W. Krawczyk, and B. Kielak, J.



   Chromatogr. 357, 93-9 (1986); Chem. Abstr.   105:71834x.   



   c. J. Oszczapowicz and E. Raczynska J. Chem. Soc. Perkin
 Trans 2, 1643-6 (1984); Chem. Abstr.   102:148618c.   



   d. J. Oszczapowicz, J. Osek, and E. Dolecku, J. Chromatogr.



   315, 95-100 (1984); Chem. Abstr.   102:84808e.   



   e. J.T. Gupton,   JOP.    Idoux, R. Leonard and G. DeCrescenzo,
 Svnth   Commun.    13, 1083-93 (1983); Chem. Abstr.   100:67951n.   



  3. A.   Iovchev    and D. Dzharov,   Farmatsiva    (sofia), 21(6), 17-20
 (1971); Chem. Abstr. 76:153521g.



  4. a. C.J. Counselman, U.S. 3,496,270, 17 Feb. 1970; Chem. Abstr.



   72:90102y.



   b. D. Duerr, H. Aebi and L.   Ebner,    U.S. 3,284,289, 8 Nov.



   1966; Chem. Abstr. 66:28499f.



  5. B.W. Hansen and E.B. Pedersen, Liebigs Ann. Chem. (8), 1485-91
   (1981);    Chem. Abstr. 95:168952x.



  6. a. M.J. Cook, A.R. Katritzky and S. Nadji, J. Chem. Soc.,
 Perkin Trans 2, 211-14 (1976); Chem. Abstr. 84:104830w.



   b.   E.B.    Pedersen and S.O. Lawessow, Acta Chem.   cant.,    Ser. B,
 B 28 1045-54 (1974); Chem. Abstr. 82:125258g.



  7. a. M. Ogata and H. Matsumoto, Heterocvcles 11, 139-47 (1978);
 Chem. Abstr. 91:39418w.



   b. E. Enders, W. Stendel and H. Wollweber, Brit. 1,251,935, 3
 Nov. 1971; Chem. Abstr. 74:125127f.



  8. H.J. Gerjovich, U.S. 3,189,648, June 15, 1965; Chem. Abstr.



      63:9960b.   



  9. Y. Ozoe and F. Matsumura,   Pestic.    Biochem.   Phvsiol.    26, 253-62,
 (1986); Chem. Abstr. 106:1787f.



  10. CIBA, Belg. 629, 317, Oct. 21, 1963; Chem. Abstr.   60:14443f.   



  11. Shell, Brit. 1,018,308, Jan. 26, 1966; Chem. Abstr. 64, 17499c.



  12. Badische Anilin-  & Soda-Fabrik Akt-Ges, Ger. 1,078,568, Mar. 31,
 1960; Chem. Abstr. 55:16570i.  



   APPENDIX B
Known phenylguanidines
EMI41.1     

 CA   Registry    #   R1      R2    R3 R4   R5    R6 References 1104513-79-3 CH3 CH3 CH3 CH3 2-C1 5-Cl 1 104513-78-2 CH3 CH3 CH3 CH3 2-Cl 4-Cl 1 10513-77-1 CH3 CH3 CH3 CH3 2-C1 H 1 101787-20-6 CH3 CH3 CH3 CH3   4-CH3    H 2 (picrate) 94811-69-5 CH3 CH3 CH3 CH3 3-F H 3   94793-35ç8    CH3 CH3 CH3 CH3 4-I H 3 94793-34-7 CH3 CH3 CH3 CH3 3-Br H 3 90595-37-2 CH3 CH3 CH3 CH3 3-C1 H 1,3,4,5 90595-34-9 CH3 CH3 CH3 CH3   3-CH3    H 6,3 73749-82-3 CH3 CH3 CH3 CH3 H H 7 (trifluoroacetic acid salt) 73749-81-2 CH3 CH3 CH3 CH3 H H 7 70683-36-2 CH3 CH3 CH3 CH3   2,4-(CH3)2      6-CH3    8 (perchlorate salt) 70683-35-1 CH3 CH3 CH3 CH3 H H 8 (perchlorate salt) 

   67947-18-6 CH3 CH3 CH3 CH3 H H 9 (benzenesulfonate salt) 56638-46-1 CH3 CH3 CH3 CH3 H H 10 (HI salt) 56499-89-9 CH3 CH3 CH3 CH3 4-C1 H 11 54708-02-0 CH3 CH3 CH3 CH3 2-C1 6-C1 12 45725-23-9 CH3 CH3 CH3 CH3 H H None 41079-13-4 C2H5 C2H5   C2R5      C2R5    H H 13,14 30543-50-1 C2H5 C2H5 CH3 CH3 H H None   (pirate)    26953-03-7 CH3 CH3 CH3 CH3 2,4-(CH3)2   6-CH3    15  
 APPENDIX B (Cont'd)
 Known phenylguanidines
 CA
Registry #   R1      R2      R3      R4    R5   R6    References 26953-02-6 CH3 CH3 CH3 CH3 2-CH3 6-CH3 15 26953-01-5 CH3 CH3 CH3 CH3 2-CH3 4-CH3 15 26953-00-4 CH3 CH3 CH3 CH3 2-CH3 H 15,16,17 23006-17-9 CH3 CH3 CH3 CH3 H H 18 (picrate salt) 20815-39-8 CH3 CH3  <RTI  

    ID=42.6> CH3,    CH3 4-Br H 3,16,17 20815-38-7 CH3 CH3 CH3 CH3 4-C1 H 1,3,4,6,11,
 16,17,19 20815-37-6 CH3 CH3 CH3 CH3 4-F H 3,16,17,19 20815-36-5 CH3 CH3 CH3 CH3 4-CH3 H 3,6,4,10,15,
 16,17,20 17826-39-0 CH3 CH3 CH3 CH3 2,4-(C1)2 5-Cl 21 2556-43-6 CH3 CH3 CH3 CH3 H H 6,3,4,22
None CH3 CH3 CH3 CH3 4-NO2 H 23
None C2H5 C2H5 C2R5 C2H5 4-C1 3-C1 24  
 KNOWN PHENYLGUANIDINE REFERENCES 1. B. Nogaj, P. Pruszynski and M. Mackowiak, Ser. Fiz. (Uniw. im.



   Adama Mickiewicza Poznaniu), 54 (Radio Microwave Spectrosc.)
 605-9 (1985); Chem. Abstr. 105:152448b.



  2. H. Bredereck and K. Bredereck. Chem. Ber. 94, 2278-95 (1961);
 Chem. Abstr. 55:27372g; 3. J. Oszczapowicz, J. Osek and E. Dolecka. J. Chromatogr.   315    95
 100 (1984); Chem. Abstr. 102:84808e; 4. J. Oszczapowicz and J. Osek. Pol. J. Chem. 57. 93-8   (1983):   
 Chem. bstr. 101:22890w; 5. H. Eilingsfeld,   G.    Neubauer, M. Seefelder and H. Weidinger. Ber.



     97    1232-45 (1964); Chem. Abstr. 61:2995g; 6. J. Oszczapowicz, E. Raczynska and J. Osek. Magn. Reson. Chem.



   24(1), 9-14 (1986); Chem. Abstr. 105:114543w; 7. C. Rabiller, G. Ricolleau, M.L. Martin and G.J. Martin. Nouv. J.



     Chem      4    35-42 (1980); Chem. Abstr. 92:214441t; 8. H.O. Kalinowski and H. Kessler. Chem. Ber. 112, 1153-67 (1979);
 Chem. Abstr. 91:56184j; 9. A. Factor, D.B.G. Jaquiss and V. Mark. U.S. 4,093,589, 6 June
 1978; Chem. Abstr. 89:164463; 10. H.O. Kalinowski and H. Kessler.   Org.      Mags.    Reson. 7, 128-36
 (1975); Chem. Abstr. 83:95825y; 11. T. Kitagaki, K. Kobayshi, T. Inouo -, E. Yoshinaga and H. Ito.

 

   Japan 7,509,846, 16 Apr. 1975; Chem. Abstr. 83:127548d; 12. T. Jen, H. Van Hoeven, W. Groves, R.A. McLean and B. Loev. J.



   Med. Chem.   18    90-9 (1975); Chem. Abstr.   82:106189b;    13. D.B.G. Jaquiss. U.S. 3,763,099, 2 October 1973; Chem. Abstr.



   79:79518n; 14. Bayer A.-G. Ger. 1,170,931, May 27, 1964; Chem. Abstr. 61:6955c; 15. D. Leibfritz. Chem. Ber. 108, 3014-24 (1975); Chem. Abstr.



   83:192056f; 16. H. Kessler, D. Leibfritz and C. Burk. Tetrehedron 26, 1805-20
 (1970); Chem. Abstr. 73:44666h; 17. H. Kessler and D. Liebfritz. Tetrehedron 25, 5127-45 (1969);
 Chem. Abstr. 72:11870w; 18. K. Itoh, A. Nozawa and Y. Ishii. Tetrehedron Lett., 1421-3
 (1969); Chem. Abstr. 71:21769p;  
 REFERENCES   (Cont1 d.)    19. H. Kessler. Tetrehedron Lett., 2041-5 (1968); Chem. Abstr.



   69:66789v; 20. H. Kessler and D. Leibfritz. Tetrehedron Lett., 427-30 (1969);
 Chem. Abstr. 70:96398x; 21. Farbenfabriken Bayer A.-G. Neth. Appl. NL 6,615,767, 10 May
 1967, Chem. Abstr. 68:68760g; 22.   V.    Mark. US 4,358,613, 9 November 1986; Chem. Abstr. 98:71507e; 23. Badische Anilin-  & Soda-Fabrik A.-G. Ger. 1,125,908, March 22,
 1962; Chem. Abstr. 57:4616d; 24 Bayer   A. -C.    Ger. 1,089,210, Appl. June 8, 1959; Chem. Abstr.



      56:14167e;    25. P.A. Argabright and V.J. Sinkey. Chem.  & Ind. 857 (1966); Chem.



   Abstr. 65:3773g.  



  APPENDIX C
EMI45.1     

 Known Iminoxazolidines
CA Registry   App ln   
Number   R1    R2   R3    References   Cmod.#    27151-09-3 4-Cl H CH3 1 None 14728-03-1 4-C1 3-C1 CH3 2,4 64G 2933-49-5 H H CH3 3 61G 99184-28-8 2-C1   3,4-(C1)2    CH3 4 None 93690-92-7 H H CH3 5 (HCl salt) 99860-49-8 4-C1 3-C1 C2H5 4 None 33385-14-7 2-C1 6-CH3   C3R7    6 None 33385-17-0 2-C1 6-CH3   C2R5    6 None 33385-18-1 2-CF3 4-C1   C4R9    6 None 33385-19-2 2-CF3 4-C1 C3H7 6 None 33385-21-6 2-CH3 6-C1   C4R9    6 None 33482-51-8 2-C1 6-C1   C4R9    6 None 33482-52-9 2-C1 6-C1   C3R7    6 None 33482-53-0 2-C1 6-C1 C2H5 6 None 33482-54-1 2-CF3 6-C1   C2R5   

    6 None 100253-39-2 3-CH3 4-CH3 CH3 4 None 21709-17-1 2-CH3 4,6-(CH3)2 CH3 lb,6 None 21709-19-3 2-C1 6-C1 CH3 lb,6 None 21709-21-7 4-C1 2,6-(CH3)2 CH3 lb,6 None 21709-58-0 2-CH3 6-CH3 CH3 lb,3a,6 None 21709-61-5 2-C1 6-CH3 CH3 lb,6 None 21794-96-7 2-C1 6-CH3 CH3 Ib None (fumarate salt) 21794-98-9 4-C1 2,6-(CH3)2 CH3 lb None (fumarate salt) 21794-99-0 2-CH3 6-CH3 CH3 lb None (fumerate salt)  
 APPENDIX C (Cont'd)
 Known Iminoxazolidines
CA Registry   App    In.



  Number R1   R2    R3 References Cmpd. & um; 100614-61-7 3-Cl 4-C1 C4H9 4 None 33587-44-9 2-CF3 H CH3 6 None 33587-59-6   2-CH3    H CH3 6 None 33587-60-9   2-CH3    5-CH3 CH3 6 None 33652-46-9 2-CH3 6-CH3 CH3 6 None 33652-47-0 2-CH3 H CH3 6 None (fumarate)
None H H CH2CH2Cl 7 None
None H H Ph 8 None
None 4-Br H CH3 4,9 None
None 4-C1 3-C1   C4R9    4 None
None 4-C4Hg H C2H5 4 None
None 4-C1 H CH3 4 None
None 4-C1 3-C1 1-C3H7 4 None
None H H CH3 4 None
None 4-CH3   3-CR3    CH3 4 None  
   IMINOXAZOLID INE    REFERENCES 1. a) G.H. Smith, U.S. 3,536,489, 27 Oct 1970, Chem. Abstr.



   74:369289.



   b) Farbenfabriken Bayer A.-G. Fr. 155 5972, 31 Jan 1969; Chem.



   Abstr. 73:45496q; Chem. Abstr.   73:14861a    2. Farbenfabriken Bayer A.-G. Belg. 632,578, 20 Nov 1968; Chem.



   Abstr. 61:8321e.



  3. a) A. deJong, and H. van Dam, Eur. J. Med. Chem. - Chim. Ther.



   17(2), 117-24 (1982); CA 97:91286q.



   b) G. Dousse, H. Lavayssiere and J. Satge,   Helv.    Chem. Acta,
 59, 2961-71 (1976); CA 86:899458q.



   c) K. Adachi, A. Mikawa, I. Horie, H. Shiraishi, U.S.



   3,967,965, 6 July 1976; CA 83:155728f.



   d) G. Dousse, H. Lavayssiere, J. Satge, J. Organomet. Chem.

 

   88, C35-C37 (1975); CA 83:58964x.



   e) A. Botta, US 3,950,367, 13 April 1976; CA 81:63364q.



  4. R.W. Leckenbaugh, US 2,902,356, 1 Sept 1959; CA   54:811g.   



  5. B. Adcock, A. Lawson and D.H. Miles, J. Chem. Soc.   5210-7   
 (1961); CA 56:11578h.



  6. Farbenfabriken Bayer   A.-G.,    DE 1963193, 24 June 1971; CA
 75:98554e.



  7. G.R. Pettit, D.S. Blonda and R.A. Upham, Can. J. Chem. 43, 1798
 802 (1965); CA 63:5528g.



  8. 0. Mitsunobu, T. Oashi, M. Kikuchi and T. Mukaiyama, Bull. Chem.



   Soc. Japan. 39, 214-19 (1966); CA 64:15780b.



  9. F.B. Dains, R.L. Brewster, I.L. Malm, A.W. Miller, R.V. Maneval
 and J.A. Sultzaberger, J. Am. Chem. Soc. 47, 1981-89 (1925); CA
 19:2481.



  10. F.B. Dains, E.J. Joss and F.E. Stubbs, Univ. Kansas Sci. Bull.



   20, 161-7 (1931); CA 26:2717.  



  FORMULA
EMI48.1

Claims

CLAIMS 1. N,N,N',N'-tetramethyl-N"-(3,4-dichlorophenyl)guanidine; 2-[(2,4 dimethylphenyl)imino] -3-methyloxazolidine; N-(3-chloro-4-methylphenyl)--N',N'-dimethylacetamidine and its acid addition and quaternary salts; or a compound, including acid addition and quaternary salts thereof of the formula EMI49.1 wherein X is a halogen atom; Y is selected from (a) C1-C3 alkyl; (b) cyclopropyl; or (c) -NR1R2 wherein R1 and R2, being the same or different, are hydrogen or C1-C3 alkyl.
2. A compound of Formula I, acid addition salt or quaternary salt, according to Claim 1 wherein X is a fluoro atom.
3. A compound of Formula I, acid addition salt or quaternary salt, according to Claim 1 wherein X is a fluoro atom and Y is -NR1R2 wherein R1 and R2, being the same or different, are hydrogen or C1-C3 alkyl.
4. A compound of Formula I, acid addition salt or quaternary salt, according to Claim 1 wherein X is a fluoro atom and Y is -NHCH3.
5. A compound of Formula I, acid addition salt or quaternary salt, according to Claim 1 wherein X is a fluoro atom and Y is cyclopropyl.
6. A compound of Claim 1 selected from the group consisting of 4 (4-fluorophenoxyl)-2-butyn-l-ol methylcarbamate, 4-(4-fluorophenoxyl)-2-butyn-l-yl cycloproprionate, N,N,N' ,N' -tetramethyl-N"-(3,4- dichlorophenyl)guanidine, 2-[(2,4-dimethylphenyl)imino]-3-methyl- oxazolidine, or N- (3-chloro-4-methylphenyl) -N' ,N' -dimethylacetamidine.
7. A method for combating acarids which comprises applying to the area whereon the said effect is desired a parasitological amount of N,N,N',N'-tetramethyl-N"-(3,4-dichlorophenyl)guanidine; 2-[(2,4 dimethylphenyl) imino] -3 -methyloxazolidine or N-(3-chloro-4 methylphenyl)-N',N'-dimethylacetamidine and its acid addition and quaternary salts; or a compound, including acid addition and quaternary salts thereof, of the formula EMI50.1 wherein X is a halogen atom; Y is selected from (a) C1-C3 alkyl; (b) cyclopropyl; or (c) -NR1R2 wherein R1 and R2, being the same or different, are hydrogen or C1-C3 alkyl.
8. The method according to Claim 7 wherein the compound is of Formula I and X is a fluoro atom.
9. The method according to Claim 7 wherein the compound is of Formula I and X is a fluoro atom and Y is -NR1R2 wherein R1 and R2, being the same or different, are hydrogen or C1-C3 alkyl.
10. The method according to Claim 7 wherein the compound is selected from the group consisting of 4-(4-fluorophenoxyl)-2-butyn-1-ol methylcarbamate, 4-(4-fluorophenoxyl)-2-butyn-1-yl cycloproprionate, N,N,N' ,N' -tetramethyl-N"- (3 ,4-dichlorophenyl)guanidine, 2-[(2,4 dimethylphenyl) imino] -3-methyloxazolidine, or N-(3-chloro-4methylphenyl)-N',N'-dimethylacetamidine.
PCT/US1988/003905 1987-11-19 1988-11-08 Ectoparasiticides WO1989004595A2 (en)

Applications Claiming Priority (18)

Application Number Priority Date Filing Date Title
US12301287A 1987-11-19 1987-11-19
US12301187A 1987-11-19 1987-11-19
US12303087A 1987-11-19 1987-11-19
US12302887A 1987-11-19 1987-11-19
US123,028 1987-11-19
US123,012 1987-11-19
US123,030 1987-11-19
US123,011 1987-11-19
US18180488A 1988-04-15 1988-04-15
US18246788A 1988-04-15 1988-04-15
US18180688A 1988-04-15 1988-04-15
US18191188A 1988-04-15 1988-04-15
US181,806 1988-04-15
US182,467 1988-04-15
US181,911 1988-04-15
US181,804 1988-04-15
US25568388A 1988-10-11 1988-10-11
US255,683 1988-10-11

Publications (2)

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WO1989004595A3 WO1989004595A3 (en) 1989-07-27

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Cited By (3)

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WO2000042031A2 (en) * 1999-01-14 2000-07-20 Bayer Corporation Substituted 2-arylimino heterocycles and compositions containing them, for use as progesterone receptor binding agents
US6353006B1 (en) 1999-01-14 2002-03-05 Bayer Corporation Substituted 2-arylimino heterocycles and compositions containing them, for use as progesterone receptor binding agents
US6900202B2 (en) * 2000-03-21 2005-05-31 Daiichi Suntory Pharma Co., Ltd. Di-substituted imineheterocyclic compounds

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Publication number Priority date Publication date Assignee Title
WO2000042031A2 (en) * 1999-01-14 2000-07-20 Bayer Corporation Substituted 2-arylimino heterocycles and compositions containing them, for use as progesterone receptor binding agents
WO2000042031A3 (en) * 1999-01-14 2000-11-09 Bayer Ag Substituted 2-arylimino heterocycles and compositions containing them, for use as progesterone receptor binding agents
US6353006B1 (en) 1999-01-14 2002-03-05 Bayer Corporation Substituted 2-arylimino heterocycles and compositions containing them, for use as progesterone receptor binding agents
US6900202B2 (en) * 2000-03-21 2005-05-31 Daiichi Suntory Pharma Co., Ltd. Di-substituted imineheterocyclic compounds

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