IL35271A - 1,1,1-trichloroethane derivatives,their preparation and their use as pesticides - Google Patents

1,1,1-trichloroethane derivatives,their preparation and their use as pesticides

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IL35271A
IL35271A IL35271A IL3527170A IL35271A IL 35271 A IL35271 A IL 35271A IL 35271 A IL35271 A IL 35271A IL 3527170 A IL3527170 A IL 3527170A IL 35271 A IL35271 A IL 35271A
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methyl
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IL35271A
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Boehringer Sohn Ingelheim
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
    • C07D213/72—Nitrogen atoms
    • C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
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    • C07D217/02—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with only hydrogen atoms or radicals containing only carbon and hydrogen atoms, directly attached to carbon atoms of the nitrogen-containing ring; Alkylene-bis-isoquinolines
    • C07D217/04—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with only hydrogen atoms or radicals containing only carbon and hydrogen atoms, directly attached to carbon atoms of the nitrogen-containing ring; Alkylene-bis-isoquinolines with hydrocarbon or substituted hydrocarbon radicals attached to the ring nitrogen atom
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    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/06—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/06—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
    • C07D233/08—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms with alkyl radicals, containing more than four carbon atoms, directly attached to ring carbon atoms
    • C07D233/12—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms with alkyl radicals, containing more than four carbon atoms, directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
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    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
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    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members 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
    • C07D233/91—Nitro radicals
    • C07D233/92—Nitro radicals attached in position 4 or 5
    • C07D233/95—Nitro radicals attached in position 4 or 5 with hydrocarbon radicals, substituted by nitrogen atoms, attached to other ring members
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    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
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    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D249/18—Benzotriazoles
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    • 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
    • C07D295/04—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 with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/12—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 with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
    • C07D295/125—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 with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/13—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 with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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    • 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
    • C07D295/20—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 carbonic acid, or sulfur or nitrogen analogues thereof
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    • C07D295/22—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 with hetero atoms directly attached to ring nitrogen atoms
    • C07D295/28—Nitrogen atoms
    • C07D295/30—Nitrogen atoms non-acylated

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  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
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Description

1,1,1-Trichloro-ethane derivatives, their preparation and their use as pesticides C.H. BOBHRINGER SOHN, 0.33371 - 2 - 35271/2 This invention relates to novel ί,-t,lTtrichloro-ethane derivatives having interesting biocidal properties. - 3 - 35271/2 (wherein R represents group (in which R? represents ■ ! · · - 4 - 35271/2 hydrogen or .halogen atom or a .thiocyono group, an alkyl group , (wherein R.0 represents a hydrogen atom or a methyly 18 , 2-hydroxjrethyl« 3 0 0 II II ■C-SR •C-R ■C-OR 21 22 group in which represents a hydrogen or chlorine atom; R~,_ represents Zri, , R , represents a hydrogen atom, alkyl group with from - 6 - 35271/2 1 to 10 carbon atoma or a phenyl or 2,4-dichlorophenoxymethyl group; R_. represents a hydrogen atom, an alkyl group Li , .with from 1 to 12 carbon atoms (optionally substituted by from 1 to 3 halogen atoms or methoxy group) or a cyclohexyl, or phenyl gro phenyl group (optio atoms), an alkyl gro an >,:-. . ..·. allyl group; 84 represents a hydrogen atom or a methyl or ethyl group; R . represents a methyl or ethyl group; R26 represents a methyl ot ethyl group; and m is 2 or 3) - 7 - 35271/2 The compounds of formula I and their salts possess . various interesting biocidal or biostatic properties. Thus they may be suitable for' the control of various phytopathogenic and human-pathogenic fungi and bacterial such as for example powdery mildews, species of Aspergillus , species of Xanthomonas , Pseudomonas and Fusaria, and for the control of animal and human-pathogenic worms and protozoa. Compounds of formula I wherein ^ represents a hydrogen atom and preferably represents group b) in which R-, represents hydrogen Rg represents hydrogen, bromine or chlorine and ^ represents chlorine or bromine; group t) in which Rlg preferably represents a hydrogen atom, GH3-, NO- , -CN, ■ 0 ^NH » , ■ -C , -CH -CH -OH, -OR,.., - re especially suitable for the control of powdery mildews.
The compounds according to the invention as herein* before defined may be prepared by conventional processes A preferred method of synthesis comprises reacting a 1 compound of formula 0 R, -C-NH-CH-R 27 II CC1 (wherein represents a group easily removable as an anion, preferably a chlorine or bromine atom) with a secondary amine of formula R2-H (wherein is as hereinbefore defined).
The reaction is conveniently performed in the presence of proton acceptor, preferably a tertiary aliphatic amine, such as triethylamine . In the case of reactions with stronger basic amines ^'^' an excess °f the amine ma^ serve as acid acceptor. It is convenient to carry out the reaction in the presence of a suitable solvent, such as for example acetone, ether, tetrahydrofuran, methylene chloride or dimethylformamide; lower aliphatic alcohols are also suitable solvents.
Compounds of formula I wherein R represents the may for example be obtained by reaction of a piperazine derivative with a compound of formula as described above; alternatively they may be obtained by conversion of a compound of formula into a compound of formula by reaction with a suitable reagent (e.g. NHC^; acylation agent, isocyanate etc.).
The starting compound of formula III, or the salts thereof, may for example, be prepared by reacting a compound of formula R1-CO-NH-CH-R27 ιτ cci3 with piperazine at exactly defined pH-values . If the work is performed at a higher pH-value than is optimal in each case, symmetrical disubstitution products of formula predominate in the roduct. At lower H-values , no reaction will take place. Compounds of formula III and their salts may be used as starting products for a great number of asymmetrically substituted piperazines and are therefore valuable intermediate products for the production of biocidally active ingredients.
Compounds according to the invention of formula (wherein R^ and R are as hereinbefore defined) may, for example, be prepared by reacting a morpholine of formula with a compound of formula R. -C0-NH- in the 1 presence of an acid acceptor; alternatively, they may be prepared by reacting a bis-(2-chloroethyl)ether of formula (wherein R^^ is as hereinbefore defined) with a compound of formula (wherein R^ is as hereinbefore defined) .
The compound of formula I obtained by any of the processes may, if desired, be subsequently converted into their salts.
The processes described above for the preparation of the new compounds constitute further features of the present invention.
According to a still further feature of the present invention there are provided biocidal compositions comprising a compound of formula I, as hereinbefore defined, or a salt thereof in association with a carrier. The composition according to the invention may contain solvents, diluents, wetting agents, adhesives, emulsifiers and/or dispersing agents conventionally used in the art and may, for example, be formulated as suspensions, dusting powders, granulates, solutions, emulsion-concentrates, emulsions or sprays. The composition according to the invention may optionally also contain one or more further biocidal agents .
For use, the concentration of the compound according to the invention as hereinbefore defined in the biocidal composition is preferably from 0.00001 to 1%, especially 0.001 to 0.5%. However, dusting powders and ULV preparations may advantageously contain higher concentrations of an active ingredient according- to the invention as hereinbefore defined.
According to yet a further feature of the present invention there is provided a method of preventing or inhibiting the growth or proliferation of parasitic pests or organisms which comprises applying to a site infested with or susceptible to infestation by the parasitic organisms an effective amount of a compound according to the invention as hereinbefore defined. The compound according to the invention may be applied to the said site in the form of a biocidal composition according to the invention as hereinbefore defined.
The parasitic pests or organisms the growth or prolifeation of which may be prevented or inhibited by means of the compounds according to the invention include various phytopathogenic and human-pathogenic fungi and bacteria, such as for example powdery mildews, species of Aspergillus , species of Xanthomonas , Pseudomonas and h I - 13 - 35271/2 For example, powdery mildew may be controlled well by treatment of the leaves of infected plants with an effective amount of the compound of Example 3 or of Qompounds Nos. 14, 15, 18, 21, 22, 23, 24, 27, 32, 35, 43, or 44 of Table 1. The compound of Example 10 may, for example, be used in the soil treatment of mildew, since it has a systemic effect. The compounds of Example 11 and Compounds Nos. 33, 34 and 41 of Table 1 may be used to control powdery mildew by leaf-treatment or by soil-treatment.
The growth of Aspergillus niger is, for example, inhibited by the compound of Example 9 and by Compounds Nos. 3, 7, 8, 9, 12, 21, 26, 27, 29, 43, 45, 46 and 48 of Table 1 and No. 4 of Table 8.
For the control of Fusarium oxysp the compound of Example 8 or Compounds Nos. 21, 43, 44, 45, 46 or 48 of Table 1 may, for example, be used.
For the control of Pseudomonas mors-prunorum, Compounds Nos. 40, 43, 46 or 48 of Table 1 may, for example, be used.
For the control of Xanthomonas malv.. the compound of Example 8 or Compounds Nos. 26, 43, 45, 46 or 48 of Table 1 may, for example, be used.
For the control of Pythium ultim. , the compounds of Examples^ and \ or compounds nos . J&( j¾ $ or %3 of Table 1 may for example be used. The compounds of Examples 7 8 ' · . . , . .. jfi and fi may also be used for the control of Rhlzoctonia solani .
Examples of biocidal compositions according to the invention (i) Dusting powder.
Composition: , 1 % of active ingredient according to the invention 98% of talcum 1 % of methylcellulose ■ In order to produce the dusting agent, the components are ground homogeneously. (ii) Suspension powder ..
Composition:' ·:. ■ " Z ' '■■■·. '·.■■· "."0· '· · •s % of active ingredient according to the invention 55% of kaolin · · ■ % of colloidal silicic acid 9%. of lignin sulfonate (dispersing agent) 1%. of sodium- tetrapropylenebenzenesulfonate (wetting agent) ·'.'', ' · or 80% of active ingredient according to the invention ' 8% of calcium ligninsulfonate % of colloidal silicic acid , ' ; % of sodium sulfate /. ■ : . 2% of diisobutyl naphthalene sodiumsulfonate The components are ground. Before use, the powder is suspended in. water in such a way that a biocidal composition is obtained, the active ingredient, concentration of which amounts to from 0.0001 to 0.5%. (iii) Emulsion concentrate Composition: , % of active ingredient according to the invention % of sodium tetrapropylenebenzenesulfonate (anionic emulsifier) % of nonylphenolpolyglycol ether (nonionic ■ . emulsifier) ■ 32.5% of propyleneglycol 32.5% of N-methylpyrrolidone The components are processed in ,the usual way.
The emulsion-concentrate is diluted with water for use in order' to obtain a biocidal composition having. ' . an active ingredient content of from' 0.00001 to 0.5%. . · (iv) Sprays ' " Composition: . '· '■ ' 0.05% of active ingredient according to the invention 0.10% of sesame oil ;" .00% of N-methylpyrrolidone ' ·- ' 89.85% of frigene The mixture of the components serves for use of the active ingredient according to the invention in form of aerosols .
The following non-limiting examples illustrate the preparation of compounds according to the invention as hereinbefore defined.
Example 1 A solution of 2.5 g of N-(l,2,2,2-tetrachloroethyl)-methacry-lamide is added dropwise with stirring to a mixture of 1.13 g of N-methy1-cyclohexylamine, 1.2 g of triethylamine and 25 ml of tetrahydrofuran. After standing for one hour at room temperature, the triethylamine hydrochloride is filtered off under suction, the filtrate evaporated in vacuo and the remaining liquid residue dissolved in hexane.
The hexane solution is treated with active charcoal, filtered and evaporated in vacuo. The oily, weakly-yellow product is dried at 0.5 Torr/50°C.
Analysis : calc: 47.7 % C 6.5 % H 8.6 % N found: 47.5 % C 6.5 % H 8.3 % N Exam le 2 To a solution of 3 g of N-phenyl-cyanamide in 50 ml of tetrahydrofuran is added dropwise at room temperature a solution of 6.7 g of N-(l,2,2,2-tetrachloroethyl)-pivalamide; After stirring for one hour at room temperature, the precipitated triethylamine hydrochloride is filtered off under suction, the filtrate is evaporated in vacuo and the semi-solid residue is extracted with warm hexane three times. The compound remains in the form of colourless crystals .
M.P. 121 - 124°C.
Example 3 To a solution of 7.44 g of N-methyl-4-bromoaniline and 4.2 g of triethylamine in 60 ml of tetrahydrofuran is added dropwise with stirring a solution of 8.4 g of N- (1,2, 2,2-tetrachloroethyl )-formamide in 40 ml of tetrahydrofuran.
The stirring is continued for 2 hours at room temperature and the triethylamine hydrochloride which separates is suction filtered off, the filtrate is evaporated in vacuo and the residue is crystallized by treating it with hexane.
The crude product is recrystallized from methanol.
M.p. 130 - 131°C.
Example 4 - 19 - 35271/2 7.2 g of N-(l,2t2,2-tetrachloroethyl)-benzamide are dissolved in 50 ml of tetrahydrofuran. A solution of 5 g of N-proparg l-3,4-dichloroaniline and 2.6 g of tri-ethylamine in 30 ml of tetrahydrofuran is added dropwise at room temperature with stirring. Stirring is continued for one hour, the tetrahydrofuran is distilled off in vacuo and the solid residue is recrystallized from benzene.
Colourless crystals; m.p.: 122-124°C.
Example 5 CC1. 3 A solution of 34.4 g of piperazine in 200 ml of water is adjusted by means of addition of 2 N hydrochloric acid to a pH-value of 4.0, ca. 500 ml of hydrochloric acid being required. A solution of 84 g of N- (1, 2, 2, 2-tetrachloroethyl) formamide in 200 ml of acetone and a concentrated aqueous solution of 80 g of sodium acetate are simultaneously added dropwise with vigorous stirring. The sodium acetate is added in such amounts that the pH-value of the solution is 4.0 — 0.1. After the addition has been finished, stirring is continued for 15 minutes at room temperature. After filtering off a small quantity of precipitated Ν,Ν'-bis- (1-formamido-2, 2, 2-trichloroethyl)-piperazine, the solution is mixed, with cooling to 5°C, with 200 ml of 20% sodium hydroxide solution. 200 ml of methylene chloride are then added; the aqueous phase is separated and saturated with potassium carbonate. A colourless, crystalline precipitate separates which is suction filtered and recrystallized from acetone. The compound is soluble in water. M.p. 122 - 123°C The hydrochloride is obtained from the base N- (1,2, 2,2-tetrachloroethyl)piperazine with the calculated quantity of hydrochloric acid after careful evaporation in vacuo.
M.p. 182°C (decomp.) Example .6 g of pulverized N- (2-chlorophenyl )-piperazine mono- hydrochloride monohydrate are suspended in a mixture of 50 ml of tetrahydrofuran and 5.1 g of triethylamine . A solution of 5.3 g of N- (1 , 2 , 2 , 2-tetrachloroethyl )-formamide is added dropwise at room temperature with stirring. The mixture .is stirred for a 2 further hours at room temperature and for 1 hour at 65°C. The triethylamine hydrochloride obtained is removed by suction filtration; the filtrate is evaporated in vacuo and the residue is crystallized by treatment with ethanol. The crude product is recrystallized from ethanol/water . M.p. 153-155°C. 7 Example $f To a well-stirred mixture of 3.2 g of bromine and 40 ml of water is added dropwise a solution of 1.4 g of potassium cyanide in 15 ml of water. When the bromine colour has vanished, 5.2 g of N-[(l-forrnamido-2,2,2-trichloro)-ethyl]- piperazine are added to the bromocyan solution in several small portions with stirring. Subsequently, 2.06 g of sodium carbonate are added and the reaction mixture is stirre for 2 hours at room temperature. The precipitate is suction filtered and dried at room temperature. For purification, Colourless crystals are obtained,, M0p0 109-110°C. 8 Example V6 2 To a solution of 2.6 g of N- [ ( 1-formamido-2 , 2 , 2- trichloro) - ethyl] -piperazine in 20 ml of tetrahydrofuran are added dropwise at 50°C, with vigorous stirring, 0.76 g of carbon disulfide in 10 ml of tetrahydrofuran and, subsequently, ml of 2N sodium hydroxide solution. The reaction mixture is stirred for 1 hour at room temperature, the tetrahydro¬ furan is distilled off at 40°C bath temperature in vacuo and the residue is triturated with isopropyl ether, suction filtered, and dried at room temperature. The sodium dithiocarbamate is obtained in the form of yellowish crystals.
To a solution of 3.6 g of the sodium salt in 60 ml of ethanol is added dropwise with stirring a solution of 0.7 g of zinc chloride in 50 ml of ethanol. The solution is stirred for 30 minutes at room temperature and mixed with 150 ml of water. The precipitate is suction filtered, washed with water and dried at 50°C. M.p. 250°C (decomp.).
Example L CHO To a solution of 3.4 g of N-formylpiperazine and 6.3 g of N-(l,2,2,2-tetrachloroethyl)-formamide in 75 ml of tetra¬ hydrofuran is added dropwise with stirring a solution of 3.2 g of triethylamine in 25 ml of tetrahydrofuran.
Stirring is continued for 2 hours at ■ room temperature, the triethylamine hydrochloride which forms is removed by suction filtration and the tetrahydrofuran is distilled in vacuo. The remaining crude product is recrystallized from ethanol.
M.p. 98 - 101°C.
Example y£ CH- A solution of 3,9 g of N-( 1-formamido-2 , 2 , 2-trichloro-ethyl) piperazine in 10 ml of tetrahydrofuran is heated to boiling for 2 hours after addition of 1.22 g of acetic anhydride.
The cooled solution is poured on ice and the precipitated semi-solid product is extracted with 5 x 15 ml of methylene chloride. The extract is dried over sodium sulfate and ■ The crude product is recrystallized from isopropanol/hexane. M.p. 149 - 150°C. 17.2 g of piperazine are dissolved in water. By addition of 2 N hydrochloric acid, the pH-value of the solution is adjusted to 2.0. 42 g of pulverized N-( 1 , 2 , 2 , 2- tetra-chloroethyl) -formamide in small portions and a concentrated aqueous sodium acetate solution are simultaneously added with vigorous stirring in such a manner that the pH-value is 2.0 — 0.1. Subsequently the solution is saturated carefully with potassium carbonate. The oil which separates is taken up in ethanol. After standing for 12 hours, a slight precipitate of ,Ν' -bis [ ( 1-formamido-2 , 2 , 2- trichloro) ethyl] -piperazine forms. It is filtered off. The ethanol is distilled off in vacuo and the semi-solid residue is recrystallized from ethanol/water.
M.p. 77 - 80°C.
The carbamic acid is not soluble in dilute alkalis. 12 Example 1ft -CHO To a solution of 2.6 g of N- [ ( 1-formamido-2 , 2 , 2-trichloro) ethyl] -piperazine and 1.1 g of triethylamine in 30 ml of methyl ethyl ketone is added dropwise with. stirring a solution of 1.6 g of tetrahydrofurfuryl chloroformate in ml of methyl ethyl ketone. The mixture is heated to boiling for 10 minutes, cooled off and poured into ice-water. The oil which separates is extracted with benzene and the extract is washed with water, dried with sodium sulfate and evaporated in vacuo. The oily crude product crystallizes when triturated with hexane.
M.p. 72 - 75°C. 2.6 g of N- [( 1-formamido-2 , 2 , 2-trichloro)ethyl] -piperazine are dissolved in 5 ml of 2 N hydrochloric acid. The solution is cooled to 5°C and a solution of 0.97 g of potassium cyanate in 20 ml of water is added. After stirring for 30 temperature , suction filtered, washed with water and dried below 50°C.
M.p. 175 - 176°C. 14 Example & CH--NH-CO- N-CH-NH-CHO W Γο a solution of 2.6 g of N- [ ( 1-formamido-2 , 2 , 2-trichloro) ethyl] -piperazine in 10 ml of absolute tetrahydrofuran are added 0.71 ml of methyl isocyanate. The mixture is allowed to stand for 18 hours at room temperature, the tetrahydrofuran is distilled off in vacuo and the solid residue is recrystallized from isopropanol/hexane.
M.p. 166 - 167°C (decomp.).
The compounds listed in Tables 1 to 14, which follow, have been prepared by methods analogous to those described above.
Table Compounds of formuL CHO Table 1 (continued) Table 1 (continued) - 30 - 35271/2 Table 1 (continued) Table 1 (continued) Table 1 ( continued) Table 2 Compounds of formula CH3-CO-NH-CH-R2 CCl. - 36 - 35271/2 Table 6 Table 8 Compounds of formula (CH ) C-C0-NH-CH-Ro CC1.
Table 13 The following compound according to the invention has also been prepared: CI 38.6%. found: C 44.2% H 3.9% N 6.0% CI 38.4%

Claims (9)

1. CLAIMS 1·.· >l,l,l-Trichloro-ethane. compounds of the general formula R -CO-NH-CH- cci5 (I) wherein R^ represents a hydrogen atom; an alkyl group with from 1 to 17 carbon atoms, a methyl group substituted by 1 to 3 halogen atoms; an alkenyl group with 2 or 3 carbon atoms; or an ethoxy, phenyl or cx-(2,5-dichl.orophenoxy)-ethyl group; and R2 represents one of the following disubstituted amino groups a) to o): a) - rr R 4 (wherein R„ represents an allyl, cyclohexyl, 2-propynyl, ! ■ l-methyl-2-propynyl or 2-cyanoethyl group and R^ represents an alkyl group with from 1 to 4 carbon atoms or an allyl or 2-cyanoethyl group); b) - NX (wherein R,. represents a . group (in which repres a , hydrogen or .halogen atom or a thiocyano group, an .-.Ikyl: group with from 1 to <1 carbon lkoxy group with' from 1 to 4 car /' '.·. v.-, or a 'cnrboxv /*roup; R0 and Rr represents each a hydrogen or halogen atom and R.^ represents an alkyl group with from 1 to 4 carbon atoms, optionally substituted by a hydroxy or cyan'o group; or an allyl , 2-propynyl, benzyl or cyano group) c) (CH2)n (wherein n is 2, 4 or 6), (wherein R ^ represents a methyl group) ; - 54 - 35271/2 f ) (wherein R-a represents a hydrogen atom or a methyl, NH , 2-hydroxyethyl- NHft S 0 ■C-SR 20 21 ■C-OR 22 0 -R ■C-N' 23 .or, . "(CH2)m - N-^R25 grou R2, Xr26 in which represents a hydrogen or chlorine atom; I*2Q represents Zn^, represents a hydrogen atom, an alkyl group with from 1 to 10 carbon atoms or a. phenyl or 2,4-dichlorophenoxymeth l group, represents a hydrogen atom, an alkyl group with from 1 to 1 ■ 12. carbon atoms (optionally substituted by from 1 halogen atoms or methoxy groups)or a cyclohexyl, «.Hy4. or phenyl group 1*23 represents a hydrogen atom, a phenyl group (optionally r substituted by 1 or 2 halogen atoms), an alkyl group with an from 1 to 4 carbon atoms or anfecnayl or/ally1 group; represents a hydrogen atom or a methyl or ethyl group; R^^ represents a methyl or ethyl group; l^^ represents a methyl or ethyl group; and m is 2 or 3) their salts.
2. Compounds as claimed in claim 1 wherei represents a hydrogen atom.
3. Compounds as claimed in claim 1 or claim 2 wherein. (_ R2 represents one of the groups b) (R^ representing hydrogen, Rg representing hydrogen bromine or chlorine and R^ representing chlorine or bromine) , X)T g) and ¾~ as defined in claim 1. disclosed. 5. A process for the preparation of compounds as / claimed in claim 1 which comprises reacting a compound of formula 0 R,-C-NH-CH-R_- 1 I 27 II cci3 (wherein represents a group easily removable as an anion) with a secondary amine of formula R2H wherein is as defined i claim 1. 6. A process as claimed in claim 5 wherein the reaction is effected in the presence of a proton acceptor. 7. A process as claimed in claim 5 or claim 6 wherein the reaction is effected in the presence of a solvent. 8. A process as claimed in claim 5 substantially as herein described. 9. A process for the preparation of compounds as claimed claim 1 wherein R represents the group jp) as defined claim 1 which comprises reacting a compound of formula a reagent suitable for the introduction of the group herein described. 11. A process for the preparation of compounds as t claimed in claim 1 wherein represents the group e) as defined in claim 1 which comprises reacting a bis- (2- chloroethyl) ether of formula (wherein R_^ is as defined in claim 1) with a compound of formula R, -C0-NH-CH-NH 1 2 VIII CC13 (wherein R^ is as defined in claim 1). 12. A process as claimed in claim 11 substantially as * herein described. 13. A process as claimed in any of claims 5 to 13 wherein a compound of formula I obtained is subsequently converted into a salt thereof. 1
4. A process for the preparation of compounds as claimed in claim 1 substantially as herein described in any of 14. Examples 1 to . 1
5. Compounds as claimed in claim 1 when prepared by a 1
6. Biocidal compositions comprising a compound as claimed in claim 1 in association with a carrier. 1
7. Compositions as claimed in claim 16 in the form of ί suspensions, dusting powders, granulates, solutions, emulsion-concentrates, emulsions or sprays. 1
8. Compositions as claimed in claim 16 or. claim 17 which contain one or more further biocidal agents . 1
9. Compositions as claimed in claim 16 substantially as herein described. 20. Biocidal compositions substantially as herein describee in any of Examples (i) to (iv). 21. A method of preventing or inhibiting the growth of ¾¾: a non-human host proliferation of parasitic pests or organisms/ which comprises applying to a site infested with or susceptible to infestation by the parasitic pests or organisms an effective amount of a compound as claimed in claim 1. 22. A method as claimed in claim 21 wherein the compound as claimed in claim 1 is applied to the said site in the form of a composition as claimed in any of claims 16 to 20. 23. A method as claimed in claim 22 wherein the said composition contains from 0.00001 to 1% by weight of a compound as claimed in claim 1. 24. A method as claimed in claim 23 wherein the said V - 59 - 35271/2 25. A method as claimed in any of Claims 21 to 24 wherein the parasitic pests or organisms are phytopathogenic fungi or bacteria or animal-pathogenic worms or protozoa. 26. A method as claimed in Claim, 25 wherein the parasitic organisms are powdery mildews or species of Aspergillus . Xanthomonas . Pseudomonas or Fusaria. 27. A method as claimed in Claim 21 substantially as herein described.
IL35271A 1969-09-11 1970-09-10 1,1,1-trichloroethane derivatives,their preparation and their use as pesticides IL35271A (en)

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US3846430A (en) * 1968-01-12 1974-11-05 Bruneau & Cie Lab 1-(2-methoxy-phenyl)-4-{8 2-(4-fluoro-benzamido)-ethyl{9 -piperazine
US3878223A (en) * 1973-03-12 1975-04-15 Abbott Lab N-Substituted acrylamides
SE7500769L (en) * 1974-02-19 1975-08-20 Ciba Geigy Ag
DE2439610C2 (en) * 1974-08-19 1986-01-23 V&yacute;skumn&yacute; ústav agrochemickej technologie, Bratislava-Predmestie Fungicides based on N- (1-formamido-2.2.2-trichloroethyl) -morpholine
AT352119B (en) * 1975-07-29 1979-09-10 Celamerck Gmbh & Co Kg PROCESS FOR PRODUCING NEW IMIDAZOL OR. TRIAZOLE DERIVATIVES
US4146646A (en) * 1976-02-12 1979-03-27 Fisons Limited Bis-amide fungicidal compounds
JPS52106836A (en) * 1976-03-02 1977-09-07 Kureha Chem Ind Co Ltd N-trichloroacetyl-n#-chlorobenzoylhydrazine derivatives and germicide s for agriculture and horticulture containing thereof
FR2399408A1 (en) * 1977-08-03 1979-03-02 Ugine Kuhlmann DICHLOROACETAMIDE AND TRICHLOROACETAMIDE DERIVATIVES HERBICIDE ANTIDOTES
JPS5859975A (en) * 1981-10-06 1983-04-09 Kureha Chem Ind Co Ltd N-(1-triazol-(1)-yl-2,2,2-trichloroethyl)-substituted amide derivative and controlling agent against powdery mildew containing said derivative
PT77219B (en) * 1982-08-24 1986-02-04 May & Baker Ltd PROCESS FOR THE PREPARATION OF BENZAMIDE DERIVATIVES
US4452626A (en) * 1982-09-20 1984-06-05 Shell Oil Company Herbicidal 4-(benzotriazol-1-yl)phenoxy)alkanoic acids, esters and salts
WO2003004476A1 (en) * 2001-07-02 2003-01-16 Ciba Specialty Chemicals Holding Inc. Aminoalkyl-substituted benzotriazoles and triazoles as metal deactivators
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