IE49101B1 - Substituted n-propargyl-anilines,processes for their preparation,and their use as fungicides - Google Patents

Substituted n-propargyl-anilines,processes for their preparation,and their use as fungicides

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Publication number
IE49101B1
IE49101B1 IE2071/79A IE207179A IE49101B1 IE 49101 B1 IE49101 B1 IE 49101B1 IE 2071/79 A IE2071/79 A IE 2071/79A IE 207179 A IE207179 A IE 207179A IE 49101 B1 IE49101 B1 IE 49101B1
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formula
carbon atoms
chj
alkyl
propargyl
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IE2071/79A
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IE792071L (en
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Bayer Ag
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Priority claimed from DE19782847287 external-priority patent/DE2847287A1/en
Priority claimed from DE19792927461 external-priority patent/DE2927461A1/en
Application filed by Bayer Ag filed Critical Bayer Ag
Publication of IE792071L publication Critical patent/IE792071L/en
Publication of IE49101B1 publication Critical patent/IE49101B1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/88—Carboxylic acid amides having nitrogen atoms of carboxamide groups bound to an acyclic carbon atom and to a carbon atom of a six-membered aromatic ring wherein at least one ortho-hydrogen atom has been replaced
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three 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
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen

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

Abstract

Die Erfindung betrifft neue substituierte N-Propargyl-aniline, mehrere Verfahren zu ihrer Herstellung und ihre Verwendung als Fungizide. Die neuen Verbindungen der Formel in welcher R' bis R6 und die in der Beschreibung angegebene Bedeutung besitzen, können zum Beispiel dann erhalten werden, wenn man N-Propargyl-aniline mit Säurechloriden oder -bromiden bzw. -anhydriden in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines Säurebindemittels umsetzt. Daneben gibt es noch andere Verfahren. Als Pflanzenschutzmittel können die erfindungsgemäßen Wirkstoffe mit besonders gutem Erfolg zur Bekämpfung von Oomyceten, z. B. gegen Phytophthora infestans eingesetzt werden.

Description

The present invention relates to certain new substituted N-propargyl-anilines, to a process for their preparation and to their use as fungicides.
It has already been disclosed that halogenoacetanilides, for example N-chloroacetyl-N-(2,6-dimethylphenyl)-alanine and -glycine alkyl esters, can be employed with good success for combating fungal plant diseases (see DTOS (German Published Specification) 2,350,944 and U.S. Patent Specification 3,780,090). Their action is, however, not always entirely satisfactory, especially if low amounts and lov; concentrations are used, in particular when combating species of Phytophthora.
The present invention now provides, as new compounds, the substituted N-propargyl-anilines of the general formula R1 CH - C= C - Rs (I) in which R1 represents hydrogen, alkyl or halogen, R represents hydrogen or alkyl, R3 represents hydrogen or alkyl, R represents hydrogen or alkyl, R^ represents hydrogen, alkyl, halogen or optionally substituted phenyl, R^ represents a furyl, tetrahydrofuryl, thiophenyl or tetrahydrothiophenyl radical, an optionally alkylsubstituted isoxazolyl radical, an optionally cyanoor thiocyano-substituted alkyl, alkenyl or alkynyl radical, a dihalogenoalkyl radical or a -CH.-Az, ·7 -7 7 -ch2-or7, -ch2-sr7 -or7, -sr7, -ch2-oso2r7, -ch2-or7, -ch2-sr7 wherein group , 48101 - 2 R7 represents an optionally substituted alkyl, alkenyl, alkynyl or alkoxyalkyl radical, and Az represents pyrazol-l-yl, 1,2,4-triazol-l-yl or imidazol-l-yl.
They exhibit powerful fungicidal properties.
Preferably, in formula (I), R1 represents hydrogen, straight-chain or branched alkyl with 1 to 4 carbon atoms, fluorine, chlorine or bromine, x h R , RJ and R each represent hydrogen or straightchain or branched alkyl with 1 to 4 carbon atoms, R5 represents hydrogen, straight-chain or branched alkyl with 1 to 4 carbon atoms, halogen or phenyl which is optionally substituted by halogen, by alkyl with 1 to 4 carbon atoms or by nitro, R® represents furyl, tetrahydrofuryl, thiophenyl, tetrahydrothiophenyl, optionally methyl- or ethyl-substituted isoxazolyl, optionally cyano- or thiocyanosubstituted alkyl with 1 to 4 carbon atoms, optionally cyano- or thiocyano-substituted alkenyl or alkynyl with in either case 2 to 4 carbon atoms, dihalogenoalkyl with 1 to 2 carbon atoms (preferred halogen atoms being fluorine and chlorine) or a -CHj-Az, -CH--OR7. -CH^-SR7. -OR7, -SR7, -CH2-OSO2R7, -COOR7 or -Ο^-Ο-όΛ group, Az represents pyrazol-l-yl, l,2,*Htriazol-l-yl or imidazol-l-yl, and γ R represents optionally halogen- (especially fluorine-, chlorine- and bromine-), cyano- or thiocyano-substituted alkyl with 1 to 4 carbon atoms, optionally halogen(especially fluorine-, chlorine- or bromine-), cyano- or thiocyano-substituted alkenyl or alkynyl with in either case 2 to 4 carbon atoms, or alkoxyalkyl with 1 to 4 carton atoms in each alkyl part. - 3 The invention also provides a process for the preparation of a substituted N-propargyl-aniline of the general formula (I) in which (a) an N-propargyl-aniline of the general formula (II), in which .
R to R have the above-mentioned meanings, is reacted with an acid chloride or acid bromide or acid anhydride of the general formula R6-C-Cl(Br) (Ilia) n 0 or (R6-C-).O (Illb), It n0 in which R^ has the above-mentioned meaning, in the presence of a diluent and, if appropriate, in the presence cfan acid-binding agent, or (b) an anilide of the general formula II o in which R1 to R^ and R^ have the above-mentioned meanings, is reacted with a propargyl halide of the general formula Hal-CH-CTc-R5 (V), in which k ς R and R have the above-mentioned meanings and 48101 - 4 Hal. represents chlorine or bromine, in the presence of an acid-binding agent and, if appropriate, in the presence of an organic diluent, or in an aqueous-organic two-phase system in the presence of a phase transfer catalyst, or (c) a halogenoacetanilide of the general formula R* . CH - C = C - RS < (VI), £ - CH,. - Hal' in which ι 5 R to RJ have the above-mentioned meanings and Hal’ represents chlorine, bromine or iodine, is reacted with a compound of the general formula B - X (VII), in which 7 X represents Az or the -OR or -SR' group, Az and 7 R having the above-mentioned meanings and B represents hydrogen or an alkali metal, if appropriate in the presence of a diluent and, if appropriate, in the presence of an acid-binding agent, or (d) a hydroxyacetanilide of the general formula R* (VIII), in which .
R to R have the above-mentioned meanings, (1) is reacted, if appropriate after activation by means of an alkali metal, with a halide of the general formula Hal' - R8 (IX), 9 10 1 - 5 in which Hal' has the above-mentioned meaning and 7 7 R represents the radical R' or the group -SC^R. wherein γ R has the above-mentioned meaning, in the presence of a diluent and, if appropriate, in the presence of an acid-binding agent, or (2) is reacted with dihydropyrane of the formula in the presence of a diluent and, if appropriate, in the presence of a catalyst, or (e) an N-propargyl-anilide of the general formula R* in which 1 h 6 R to R and R have the above-mentioned meanings, is reacted, in a manner which is in itself known, with an alkali metal hypohalite in the presence of a diluent.
The new substituted K-propargyl-anilines exhibit powerful fungicidal properties. Surprisingly, the com20 pounds according to the invention exhibit a substantially greater action than the N-chloroacetyl-N-(2,6-dimethylphenyl) -alanine and -glycine alkyl esters known from the state of the art.
Particularly preferred substituted N-propargyl-anilines 12 3 of the formula (I) are those in which R , R and R represent hydrogen, methyl, ethyl, isopropyl, sec.-butyl and tert.-butyl, R1 alternatively representing chlorine or - 6 4 5 bromine, R represents hydrogen, methyl or ethyl, R represents hydrogen, methyl, ethyl, phenyl, bromine, chlorine or iodine and R^ represents 2-furyl, 2-thienyl, 2-tetrahydrofuryl, 5-methylisoxazol-3-yl, methoxymethyl, ethoxy5 methyl, allyloxymethyl, propargyloxymethy1, ethoxymethoxymethyl, methyimercaptomethyl, methoxy, ethoxy, methylmercapto, methylsulphonyloxymethyl, methoxycarbonyl, ethoxycarbonyl, dichloromethyl, pyrazol-1-yl-methyl, imidazol-l-yl-methyl, 1,2,4-triazol-l-yl-methyl and tetra10 hydropyran-2-yloxy-methyl.
In addition to the compounds mentioned later in the preparative examples, the following compounds of the general formula R2 _ Table 1 (I) may R1 ✓ - N 'x R3 be specifically mentioned: R* CH - C = C - R! (I) rRi 0 R1 R* R* Rs R« CH, 6-CH, H H H -U CH, 6-CH, H H H -CHZ OCH, CH, 6-CH, H H H \zzN CH, 6-CH, H H H /N=) -CHs-NQ CH, 6-CH3 H H H -a CH, 6-CH, H H H -ch2oc2k, CH, 6-CH, H H H -0¾-O-CHZ-0C2 H, . 49101 R1 R2 R5 Ε5 R6 CHj 6-CH, Η Η Η CHj 6-CH, Η Η Η u CHj 6-CHj Η Η Η u CHj 6-CH, Η Η Η Q CHj 6-CH, Η Η Η -CHj SCH, CHj 6-CH, Η Η Η -CHjSCjH, CHj 6-CHj Η Η Η -CHC1z CHj 6-CH, Η Η Η -COOCH, CHj 6-CH, Η Η Η -ch2 oso2 ch. CHj 6-CH, Η Η CHj CHj 6-CH, Η Η CHj -ch2 OCH, /N^l CHj 6-CH, Η Η CH, -CH2 -N /Νη CHj 6-CHj Η Η CH, -ch2-n /=N CHj 6-CH, Η Η CHj -ch2 -n_j CHj 6-CHj Η Η CHj -CH20C2Hj CHj 6-CH, Η Η CHj -CH20CH20C2Hj CHj 6-CH, Η Η 0¾ 0¾ 6-CHj Η Η CHj CH, 6-CHj Η Η 0¾ -Φ R1 R2 R3 R5 R6 CH, 6-CH, H H CH, CH, 6-CH, H H CH, -0¾ SOT, CH, 6-CH, H H CH, -CHjSCjH, CH, 6-CH, H H CH, -CHClj CH, 6-CH, H H CH, -COOCH, CH, 6-CH, H H CH, -CH20S02CH, CH, 6-CH, H CH, H CH, 6-CH, H CH, H -OT20CH, /N=1 CH, 6-CH, H CH, H CH, 6-CH, H CH, H -0¾ -t/j /= » CH, 6-CH, H CH, H -ch2 -n^_( CH, 6-CH, H CH, H -CH2OC2H, Cit, 6-CH, H CH, H -CHi -O-CHj, -( CH, 6-CH, H CH, H -0¾ 0-/ \ '0—/ CH, 6-CH, H CH, H -U CH, 6-CH, H CH, H -U CH, 6-CH, H CH, H -σ CH, 6-CH, H CH, H -0¾ SOT, OT, 6-CH, H CH, H -0¾ 302¾ . 49101 R1 R2 R3 R* Rs R6 CH, 6-CH, H CH, H -CHC12 ch. 6-CH, H CH, H -COOCH, CH, 6-CH, H CH, H -(¾ 0S02 CH, CH, 6-CH, H H Br -u CH, 6-CH, H H Br -0¾ OCH, /N=| CH, 6-CH, H H Br -0¾ -ν I \=N CH, 6-CH, H H Br -CHa-H_| CH, 6-CH, . H H Br /=N -CH2-if^J CH, 6-CH, H H Br -ch2 0C2 h. CH, 6-CH, H H Br -0¾ -0-0¾ -0C2H, CH, 6-CH, H H Br -C^-Q CH, 6-CH, H H Br -σ CH, 6-CH, H H Br -u CH, 6-CH, H H Br -U CH, 6-CH, H H Br -CH2SCH, CH, 6-CH, H H Br -0¾ SC^ R’ R* R» R* RJ R* CHj 6-CH, H H Br -CHC12 CHj 6-CH, H H Br -C00CH, CHj 6-CH, H H Br -CH20S02CH, CHj 6-CH, H CH, Br -σ CHj 6-CH, H CH, Br -CHg OCH, /NA CHj 6-CH, H CH, Br -ch2-n 1 CHj 6-CH, H CH, Br CH, 6-CH, H CH, Br -CH2-N_j CH, . 6-CH, H CH, Br -CH20C2H, CHj 6-CH, H CH, Br -CH2-O-CHS-0C2 H, CH, 6-CH, H CH, Br •o CH, 6-CH, H CH, Br -Q CH, 6-CH, H CH, Br -U CH, 6-CH, H CH, Br -U CHj 6-CH, H CH, Br -CHg SCH, CH, 6-CH, H CH, Br -CHjSCjH, R1 R* R3 R* Rs R* CH, 6-CHj H CHj Br -CHC1Z CHj 6-CHj H CHS Br -COOCHj CH, 6-CHj H CHj Br -CH2 0S02 CHs CHj 6-CHj H H Cl . -y CHj 6-CHj H H Cl -CH2 OCHj CH, 6-CHj H H Cl /Ny -CH2 -N I \=.H CHj 6-CHj H H Cl -CHz- CH, 6-CHj . H H Cl /=·Ν CHj 6-CHj H H Cl -CH20C2H, CH, 6-CHj H H Cl -01.,0-0¾ -OC2Hj CH, 6-CHj H H Cl CHj 6-CHj H H Cl -u CHj 6-CHj H H Cl -U CHj 6-CHj H H Cl -y CH, 6-CHj H H Cl -CHj.SCHj CHj 6-CHj H H Cl -CHj,-S-C2Hs R1 R2 R3 R4 R5 R6 ΟΙ, 6-CH, !I a Cl -CHC1, CH, 6-CH, H H Cl -COOCH, CH, 6-CH, H H Cl -CH, OSO, CH, CH, 6-CH, H H I -u CH, 6-CH, H H I -CH, OCH, CH, 6-CH, H H I -CH, -Ν I \=.N CH, 6-CH, H H I CH, 6-CH, H H J /= N -CH, -N_| CH, 6-CH, H H 1 -CH,OC,H, CH, 6-CH, H H I -CH, O-CH,-0C,H, CH, 6-CH, H H I -"°O CH, 6-CH, H H I -y CH, 6-CH, H H I -y CH, 6-CH, H H I -y CH, 6-CH, H H I -CH,SCH, CH, 6-CH, H H I -CH,-S-C,H, CH, 6-CH, H H I -COOCH, CH, 6-CH, H H I -CHjOSOjCH, 910 1 R1 R2 R3 R* Rs R« CH, 6-Cj Hj H H H -O CHj 6-C2Hj Η H H -ch2och3 CHj 6-C2Hj H H H -CHj-N^ CHj 6-Cj.Hj H H H ,N=l -ch2-n_J CHj 6-C2H, H H H -CH20C2H5 CHj 6-Cj.H, H H H -CH2 0SO2 CH, CHj 6-C2H, H H H -CHC12 CHj 6-C2H5 H H H -COOCH, CHj 6-C2Hj- H H H -U CHj 6-C2Hj H H H -CH2SCH, CHj 6-C2H, H H H -ch2oO CHj 6-C2H, H CH, H -U CHj 6-CzH5 H CH, H -CH20CHj CHj 6-C2Hj H CH, H /H=i -ch2-n I VzN CHj 6-C2H, H CH, H /N=i -ch2-n_J CHj 6-C2Hj H CH, H -CHjOCjH, CHj 6-C2H, H CH, H -CH20S02CH, CHj 6-C2H, H CH, H -chci2 CHj 6-ςΗ, H CH, H -COOCH, Κ1 - J/| - ί'Λ r-3 R* P? R6. CH, 6-¾¾ H CO, H CH, 6-¾¾ H CH, H -0¾ SCH, CH, 6-¾¾ H OT, H CH. 6-Cj H, H H CH, -o CH, 6-¾¾ H H CH, -CHjOCH, /Ν=η CH, 6-CjH, H H CH, -CH,-M \=xN CH, 6-0,¾ H H CH, /N=] -CHa-Nj CH, 6-¾¾ H H CH, -CHjOC^ CH, 6-0,¾ H H 0¾ -CH,0S0,CH, CH, 6-¾¾ H H CH, -CHCl, CH, 6-¾¾ H H 0¾ -COOCH, CH, 6-¾¾ H H (¾ -u CH, 6-¾¾ H H CH, -0¾ SCH, CH, 6-CtH, H H OT, -OT, oQ CH, 6-¾¾ H H Br -u . CH, 6-¾¾ H H Br -0¾ OCH, CH, 6-¾¾ H H Br /N—1 CH, 6-¾¾ H H Br -OTa-N^l - J5 - R1 R‘ R5 R4 R5 R6 CH, 6-CjH, H Η Br -CHjOCgHj CHj 6-C2H, Η Η Br -CH2OSO2CH, CH, 6-C2H, Η Η Br -chci2 CH, 6-C2H, Η Η Br -COOCH, ' CHj 6-C2Hi Η Η Br -u CHj 6-C2H, Η Η Br -CH2SCH, CH, 6-C2H, Η Η Br -ch,«Q CH, 6-C2Hs Η CH, Br -u CH, 6-CjH, Η CH, Br -CH20CH, CH, 6-C2H, Η CH, Br -ch2-/ 1 V=-NZN=I CH, 6-C2H, Η CH, Br -ch2-n 1 \=J CH, 6-C2H, Η CH, Br -CH20C2Hj CH, 6-C2H, Η CH, Br -C$>0S02CH, CH, 6-C2H, Η CH, Br -CHC12 CH, 6-C2H, Η CH, Br -COOCH, CH, 6-C2Hj Η CH, Br -Q CH, 6-C2H, Η CH, Br -CHjSCH, CH, 6-C2Hj Η CHj Br R1 R4 Rs R* R9 R« CH, 6-CjH, H H Cl -u CHj 6-CgH, H H Cl -cs^oca, CHj 6-CjH, H H Cl -CHj-/^ CHj 6-¾¾ H H • Cl -CHj-ίί^-j CHj 6-¾¾ H H Cl -0¾ OC2Hj CH, 6-¾¾ H H Cl -CHjOSOjCH, CH, 6-¾¾ H H Cl -CHClg CH, 6-¾¾ H H Cl -COOCH, CH, 6-¾¾ H H . Cl -Q CH, 6-¾¾ H H Cl -CH2 SCH, CH, 6-¾¾ H H Cl CH, 6-¾¾ H H I -u CH, 6-¾¾ H H I -CHg OCH, CH, 6-¾¾ H H I -CHg-Ν I \j=.N CH, 6-¾¾ H H I /N=l -CHg -M i CH, 6-¾¾ H H I -CH20C2Ej CH, 6-¾¾ H H I -CHgOSOgCH, CH, 6-¾¾ H H I -CHClg CH, 6-¾¾ H H I -COOCH, 9 10 1 R1 0 R r? r - H5 R6 . CH, 6-¾¾ H H 1 ~xr- CH, 6-C2H, H H X -(¾ SCH, CH, 6-C2H, H H I °O CjjH, 6-C2H, H H H -U c2h. 6-C2 H, H H H -CH2 OCH, c2h. 6-C2H, H H H -CH, c2h, 6-¾¾ H H . H -CH2-N_J c2h, ' 6-¾¾ H H H -ch2oc2h, c2h, 6-¾¾ H H H -CH20S0jCH, c2h. 6~C2H, H H H -chci2 ·< c2h. 6-¾¾ H H H -COOCH, · c8h, 6-C2Hj H t H H -Q Ciljj. 6-¾¾ H H H -CH2SCH, CZH, 6-C2Hs H H H c2h, 6-¾¾ H CH, H -C5' C2K, 6-¾¾ H CH, H H -CH2-OCH3 /11=, c2h, 6-C2Hi H CH, -(¾-N 1 \=H ,N=i c2h, 6-¾¾ H CH, K -Οί,-Ν Η1 If K5 1? I? K6 CtH, 6-¾¾ H ra, H -CH20C2Hj C.H, 6-¾¾ H CHj H -ch2csc2ch. C2H, 6-¾¾ H CHj H -chci2 σ,Η, 6-¾¾ H CH, H -COOCHj ¢,¾ 6-¾¾ H CHj H -y CjHj 6-¾¾ H ch. H -(¾ SCH, C2H, 6-¾¾ H CH, H -®2-0-O CjjHj 6-¾¾ H H CH, -[i~D CzH, 6-¾ K5 H H CH, -CH2 OCH, /Ν=η C2H, 6-¾¾ H H CH, -ch2 -k /Ν=η CiH, 6-¾¾ H H CH, -ch2-n_ 1 CzH, 6-¾¾ H H CH, -CH20C2H, C2H, 6-¾¾ H H CH, -CH20S02CHj C2Hs 6-¾¾ H H CH, -CHC1, c2h. 6-¾¾ H H CH, -COOCH, · c2h, 6-¾¾ H •H CH, -y cta, 6-¾¾ H . H CH, -CH2SCH, 0,¾ 6-c2h5 H H 0¾ -σκ,-ο-θ 'o-7 R1 R2 R3 R* R9 R® Ο,Η, 6-0,¾ H H Br -U Ο,Η, c2h, 6-0,¾ 6-0,¾ H H H H Br Br -ct,ock, /N=l -CH^I c2h, 6-0,¾ H H Br /Ifq -CH,-N_j ^2¾ 6-0,¾ H H Br «CHj OC2 Kg 0,¾ 6-0,¾ H H Br -CH,OSO,CH, 0,¾ 6-0,¾ H H Br -CHC1, *s 0,¾ Hg H H Br -COOCH, · -a 0,-¾ 6-0,¾ H ,H Br 0,¾ 6-0,¾ H H • Br -CH,SCH, 0,¾ 6-0,¾ H H Br C,HS 6-0,¾ H CH, Br -u 0,¾ 6-0,¾ H CH, Br -CH,OCH, ^¾ 6-0,¾ H CH, Br ,N=1 -CH,-N 1 \=-H 0,¾ 6-0,¾ H 0¾ ' Br ,N=-| -CHa-VJ 0,¾ 6-0,¾ H CH, Br -CH,OC,H, 0,¾ 6-0,¾ H CH, Br -Oi,OSO,CHj 0,¾ 6-0,¾ H CH, Br -CHC1, 0,¾ 6-0,¾ H CH, Br -COOCH, ' Τ ir ? ?/ P? F? K6 0,¾ 6-0,¾ H .0¾ Br -Q Ci Hi 6-0,¾ H 0¾ Br -CH, SCH, 0,¾ 6-0,¾ H CH, Br -™·°Ό 0,¾ 6-0,¾ H H Cl -u 0,¾ 6-0,¾ H H Cl -CH,0CH, 0,¾ 6-0,¾ H H Cl Λτ=1 -CH,-N 1 0,¾ 6-C2H5 H H • · Cl 0,¾ 6-0,¾ H H Cl -ra, oc, ¾ 0,¾ 6-0,¾ H H Cl -ra, oso, ch. 0.¾ 6-0,¾ H H Cl -raci. 0,¾ 6-0,¾ H ' H Cl -COOCH, · 0,¾ 6-0,¾ H . H Cl -Q ^¾ 6-0,¾ H H Cl -CH, SCH, 0,¾ H H Cl -ra,of~A o—' 0,¾. 6-0,¾ H H I -u 0,¾ 6-0,¾ H · H X -CH,CCH, 0,¾ 6-0,¾ H H I -CH, -N ] V=.N 0,¾ 6-¾¾ H H I -CH.-H 491°1 Ft1 R2 R3 r'1 . R3 ......R6 C2 H, 6-C2H, H ’ H I -CK20C2H5 c2h, 6-C2Hs H H I -ch2 oso2 ch3 C2Hj 6-Cj.Hj H H I -chci2 C2Hs 6-C2Hj H H I -COOCH, · Cjit, 6-C2H5 H .H I -σ c2h, 6-C2Hj H H I -CH2SCHj C2Hs 6-C2Kj H H I If, for example 2 ,6-dimethy1-1 I-propargyl-aniline and furane-2-earboxylic acid chloride are used as starting materials in process variant (a), the course of the reaction can be represented by the following equation: If, for example, 2,6-dimethyl-N-(2-furoyl)-aniline and propargyl bromide are used as starting materials in process variant (b), the course of the reaction can be represented by the following equation: If, for example, 2,6-dimethyl-N-propargyl-chloroaeetanilide and pyrazole are used as starting materials in process variant (c), the course of the reaction can be represented by the following equation: If, for example, 2,6-dimethyl-N-propargyl-hydroxyacetanilide and ethoxymethyl chloride are used as starting materials in process variant (d)(1), the course of the reaction can be represented by the following equation: CHj/CHi-C=CH N «, XC-CH,-0-H + C1-CHz-0-C2H3 I base •HCl - 23 /CH, α-« CHj -C=CH CH, (J-CHa-0-CH,-0-C2 Hj 0 If, for example, 2,6-dimethyl-N-propargyl-hydroxyacetanilide and 3,4-dihydro-2H-pyrane are used as starting materials in process variant (d)(2), the course of the react ion can be represented by the following equation: CH.
G un, ^CHj-CSCH •N -0-H .catalyst—=*.
CHjzch2-c=ch If, for example, 2,S-dimethyl-N-(2-furoyl)-Npropargyl-aniline and potassium hypobromite are used as starting materials in process variant (e), the course of 10 the reaction can be represented by the following equation: CH. a un. 13 ^,CHt-C=Ca H . 0' KOBr ~=W - 24 The formula (II) provides a general definition of the N-propargyl-anilines required as starting materials in carrying out the process variant (a) according to the invention. In this formula, R1, R2, R^, R1* and R^ preferably have those meanings which have already been mentioned as preferred in connection with the description of the compounds of the formula (I).
Some of the N-propargyl-anilines of the formula (II) are known (see U.S. Patent Specifications 3,555,377 and **,001,325); they can all be obtained in accordance with known processes, for example by reacting corresponding anilines with propargyl halides of the formula (V) or with the corresponding propargyl sulphonates, for example mesylates or tosylates, in the presence of an acid-binding agent, for example sodium carbonate or potassium carbonate, if appropriate in the presence of an inert organic solvent, for example ethanol, at temperatures between 20° and 15O°C; an excess of aniline can also be employed, and this is preferred.
N-Propargyl-anilines of the formula (II), in which R1* represents methyl, can also be obtained by reacting the corresponding anilines with acetylene in the presence of copper acetylide under pressure (see, in this context, Liebigs Ann. Chem. 596, 1 (1955))· The following may be mentioned as examples of the starting materials of the formula (II): R1 Rz R3 R* R5 CH, 6-CH, H H H C2H5 6-C2 H, H H H c2h, 6-CH, H H H C(CH,), H H H H CH, 3-CH, H H H CH, 5-CH, H H H Cl 6-CH, H H H Cl 6-C(CH, ), H H H CH, 3-CH, 6-CHj H H CH, 6-CH, H CH, H C2H, 6-C2H, H CH, H c2h, 6-CH, H CH, H CH, 6-CH, H C2H, H C2H, 6-C2H, H C2Hs H c2h, 6-CH, H C2H, H CH, 6-CH, H H CH, c2h, 6-Cj.H, H H CH, c2h, 6-CH, H H CH, ch. 6-CH, H H O c2h, 6-C2H, H H O c2h, 6-CH, H H CH, 6-CH, H CH, CH, C2H, 6-C2H, H CH, CH, c2h, 6-CH, H CH, CH, The formulae (Ilia) and (111b) provide a general definition of the acid chlorides or bromides and acid anhydrides also to be used as starting materials for process variant (a) according to the invention. In these formulae, Rb preferably has those meanings which have already been mentioned as preferred in connection with the description of the compounds of the formula (I). - 26 The acid chlorides or bromides and acid anhydrides of the formulae (Ilia) and (Illb) are generally known compounds of organic chemistry.
Formula (IV) provides a general definition of the 5 anilides required as starting materials in carrying out process variant (b) according to the invention. In this formula, R1, R2, R3 and R6 preferably have those meanings which have already been mentioned as preferred in connection with the description of the compounds according to the invention, of the formula (I).
The anilides of the formula (IV) can be obtained in a generally known manner by reacting corresponding anilines with an acid chloride or bromide or an acid anhydride of the formulae (Ilia) and (Illb) in accordance with the con15 ditions of process variant (a), in the presence of an inert organic solvent, for example toluene or methylene chloride, if appropriate in the presence of an acidbinding agent, for example potassium carbonate or triethylamine, or in the presence of a catalyst, for example dimethylformamide, at temperatures between 0° and 100°C (see also the preparative examples given later).
The following may be mentioned as examples of the starting materials of the formula (IV): R1 R* R3 R® CH, 6-CH, H CiH, 6-CH, H -U CgH, 6-CgH, H -U - 27 'Ή CH, 3-CH, 6-CH, -U Cl 6-CH, H -U CH, 6-CH, H -CH2-0-CH C2H, 6-CH, H -CH2-0-CH c2h, 6-Cj.H, H -ch2-o-ch CH, 3-CH, 6-CH, -ch2-o-ch Cl 6-0¾ H -ch2 -o-ch CH, 6-CH, H -COOCH, c2h, 6-CH, H -COOCH, c2h, 6-¾¾ H -COOCH, CH, 3-CH, 6-CH, -COOCH, Cl 6-CH, H -COOCH, CH, 6-CH, H -Q C2H5 6-CH, H -"-Ο c2h, 6-¾¾ H CH, 3-CH, 6-CH, /y AJ Cl 6-CH, H -€j CH, 6-CH, H /=&T C2H, 6-CH, H Z=N -0¾ -N | 'H—! R1....... - 28 - . . ν. .-7. R6 . 7 . R2 . Rr......... ¢,¾ 6-0,¾ H CH, 3-0¾ 6-0¾ /= N Cl 6-CH, H -'MJ /=1 CH, 6-0¾ H ¢,¾ 6-CH, H -CH.-Q C,H, 6-0,¾ H -Q CH, 3-CH, 6-CH, -CH.-Q Cl 6-CH, H CH, 6-CH, H -CH,-O-SO, CH, 0,¾ 6-CH, H -CH,-O-SO, CH, C,H, 6-0,¾ H -CH,-O-SO, CH, CH, 3-CH, 6-CH, -0¾-O-SO, CH, Cl 6-CH, H -(3¾ -O-SO, CH, CH, 6-CH, H -CHCl, CjH, 6-CH, H -CHCl, C,H, 6-0,¾ H -CHCl, CH, 3-CH, H -CHCl, Cl 6-CH, H -CHCl, CH, 6-CH, H -OC,Hj 0,¾ 6-0¾ H -00,¾ 0,¾ 6-0,¾ H -00,¾ CH, 3-CH, 6-0¾ -00,¾ Cl 6-CH, H -00,¾ R1 . . R2 . -29- . . . . JR3 . . . ../ ... CH, 6-CH, H -U C2H, 6-CH, H -Q c2h, 6-C2H, H CH, 3-CH, 6-CH, Cl 6-CH, H -C7J CH, 6-CH, H -ch2-o-ch2-o-c2h. 0,¾ 6-CH, H -ch2-o-ch2-o-c2h. c2h3 6-C2H, H -ch2-o-ch2-o-c2h. CH, 3-CH, 6-CH, -ch2-o-ch2-o-c2h. Cl 6-CH, H -ch2-o-ch2-o-c2h, CH, 6-CH, H C2H, 6-CH, H -C8.-0-O c2h, 6-C2H, H CH, 3-CH, 6-CH, · -0¾-°^ Cl 6-CH, H The formula (V) provides a general definition of the propargyl halides also to be used as starting materials for process variant (b) according to the invention. In 4 5 this formula, R and R preferably have those meanings which - 30 have already been mentioned as preferred ill connection with the description of the compounds of the formula (1).
The propargyl halides of the formula (V) are generally known compounds of organic chemistry.
The formula (VI) provides a general definition of the halogenoacetanilides required as starting materials in carrying out process variant (c) according to the invention. In this formula, R1, R2, R3, R4 and R5 preferably have those meanings which have already been mentioned as preferred in connection with the description of the compounds of the formula (I).
Some of the halogenoacetanilides of the formula (VI) are known from U.S. Patent Specification 4,001,325. Those which have not hitherto been described in the literature can be obtained in accordance with the process described in the said U.S. specification and in analogy with process variant (a), by reacting N-propargyl-anilines of the formula (II) with halogenoacetic acid halides.
The formula (VII) provides a general definition of the compounds additionally to be used as starting materials for process variant (c) according to the invention. In this formula, Az and R? preferably have those meanings which have already been mentioned as preferred in connection with the description of the compounds of the formula (I). B preferably represents hydrogen, sodium or potassium.
The compounds of the formula (VII) are generally known compounds of organic chemistry.
The formula (VIII) provides a general definition of the hydroxyacetanilides required as starting materials in carrying out process variant (d) according to the invention. In this formula, R1, R2, R3, R4 and R5 preferably have those meanings which have already been mentioned as preferred in connection with the description of the compounds of the formula (I). 9101 - 31 The hydroxyacetanilides of the formula (VIII) can be obtained in a manner which is generally known, by saponifying acyloxyacetylanilides of the general formula R* in which R^· to R^ have the above-mentioned meanings and R^ represents alkyl with 1 to 4 carbon atoms, with sodium hydroxide solution or potassium hydroxide solution or with an alkali metal alcoholate of a lower alcohol, for example sodium methylate or sodium ethylate, at temperatures between 20° and 40°C, and, after acidification, isolating the compounds of the formula (VIII) in the usual manner.
The acyloxyacetanilides of the formula (XI) can be obtained in a generally customary and known manner, by, for example, replacing the reactive substituent Hal* in halogenoacetanilides of the formula (VI) by reaction with a lower alkanecarboxylic acid, the acid preferably being employed in the form of an alkali metal salt or alkaline earth metal salt thereof, or by reacting N-propargyl-anilines of the formula (II) with corresponding acyloxyacetyl halides.
The halides additionally to be used as starting materials for process variant (d)(1) according to the invention are defined by the formula (IX). In this formula, R and Hal' preferably have the preferred meanings mentioned above.
The halides of the formula (IX) are generally known compounds of organic chemistry.
Dihydropyrane, additionally to be used as a start49101 - 32 ing material for process variant (d)(2) according to the invention, is also a known compound of organic chemistry.
The formula (Ia) provides a general definition of the N-propargyl-anilides required as starting materials in carrying out process variant (e) according to the invention. These are compounds according to the invention in which R^ represents hydrogen.
Preferred diluents for the reaction according to process variant (a) are inert organic solvents. These include, as preferences, ketones, such as diethyl ketone and especially acetone and methyl ethyl ketone; nitriles, such as propicnitrile and especially acetonitrile; ethers, such as tetrahydrofuran or dioxan; aliphatic or aromatic hydrocarbons, such as petroleum ether, benzene, toluene or xylene; halogenated hydrocarbons, such as methylene chloride, carbon tetrachloride, chloroform or chlorobenzene, and esters, such as ethyl acetate.
Process variant (a) can, if appropriate, be carried out in the presence of an acid-binding agent (hydrogen halide acceptor). Any of the customary acid-binding agents can be used for this purpose. These include, as preferences, organic bases, such as tertiary amines, for example triethyiamine, or such as pyridine, as well as inorganic bases, for example alkali metal hydroxides and alkali metal carbonates. If appropriate, a catalyst, such as dimethylformamide, can also be used.
In carrying out process variant (a), the reaction temperatures can be varied within a substantial range.
In general, the reaction is carried out at from 0° to 120°C, preferably from 20° to 100°C.
In carrying out process variant (a) equimolar amounts are preferably used. The isolation of the compounds of the formula (I) is carried out in the usual manner.
Suitable diluents for the reaction according to process variant (b) are any of the inert organic solvents. These include, as preferences, ethers, such as diethyl ether, - 33 dioxan or tetrahydrofuran; aromatic hydrocarbons, such as benzene, toluene or xylene; halogenated hydrocarbons, such as methylene chloride, carbon tetrachloride, chloroform or chlorobenzene; esters, such as ethyl acetate; ketones, such as methyl isobutyl ketone; nitriles, such as acetonitrile; and dimethylformamide or dimethylsulphoxide.
The reaction according to process variant (b) is carried out in the presence of an acid-binding agent. Any of the customary acid-binding agents can be used for this purpose. They include, as preferences, inorganic bases, for example alkali metal hydroxides and alkali metal carbonates .
In carrying out process variant (b), the reaction temperatures can be varied within a substantial range. In general, the reaction is carried out at from -70° to +100°C, preferably from -20° to +80°C.
In carrying out process variant (b) according to the invention, preferably 1 to 1.5 moles of propargyl halide of the formula (V) are employed per mole of anilide of the formula (IV). The compounds of the formula (I) are isolated in the usual manner.
In a preferred embodiment, the reaction according to process variant (b) is carried out in a two-phase system, for example aqueous sodium hydroxide solution or potassium 25 hydroxide solution/toluene or methylene chloride, with the addition of 0.1 - 1 mol of a phase transfer catalyst, for example an ammonium compound or phosphonium compound, benzyl-dodecyl-dimethyl-ammonium chloride and triethyl-benzyl-ammonium chloride being mentioned as 30 examples (see also the preparative examples given later).
Preferred diluents for the reaction according to process variant (c) are inert organic solvents. These include, as preferences, the solvents already mentioned in connection with process variant (a).
The reaction according to process variant (c) can, if - 34 appropriate, be carried out in the presence of an acidbinding agent. Any of the customarily usable inorganic or organic acid-binding agents can be added, such as alkali metal carbonates, for example sodium carbonate, potassium carbonate and sodium bicarbonate, or such as lower tertiary alkylamines, cycloalkylamines or aralkylamines, for example triethylamine or dimethylbenzylamine, or such as pyridine and diazabicyclooctane. Preferably, an excess of the azole is used.
The reaction temperatures in process variant (c) can be varied within a substantial range. In general, the reaction is carried out at from 20° to 15O°C, preferably at 60° to 120°C. In the presence of a solvent, the reaction is advantageously carried out at the boiling point of the particular solvent.
In carrying out process variant tc) preferably 1 to 2 moles of the compound of the formula (VII) and, if appropriate, 1 to 2 moles of acid-binding agent, are employed per mole of the compound of the formula (VI).
The compounds of the formula (I) are isolated in the customary manner.
Preferred diluents for the reaction according to the invention, in accordance with process variant (d), are inert organic solvents. These include, as preferences, the solvents already mentioned in connection with process variant (a).
The reaction according to process variant (d)(1) can, if appropriate, be carried out in the presence of an acidbinding agent. Any of the customarily usable inorganic or organic acid-binding agents can be added. These include, as preferences, the compounds already mentioned in connection with process variant (a).
The reaction temperatures in process (d)(1) can be varied within a substantial range. In general, the reaction is carried out at from 20° to 150°C, preferably 4S>101 - 35 at the boiling point of the solvent, for example from 60° to 100°C.
In carrying out process variant (d)(1), 1 mole of halide of the formula (IX) and, if appropriate, 1 to 2 moles of acid-binding agent are preferably employed per mole of the compound of the formula (VIII), if appropriate after adding 1 to 2 moles of a strong base, for example, an alkali metal hydride. To isolate the end product , the reaction mixture is freed from the solvent and water and an organic solvent is added to the residue. The organic phase is separated off and worked up in the usual manner.
According to a preferred embodiment of process (d)(1), the procedure is to start from a hydroxyacetanilide of the formula (VIII), convert the latter, in a suitable inert solvent, to the alkali metal alkanolate by means of an alkali metal hydride or alkali metal bromide, and react the alkanolate, without isolation, immediately with a halide of the formula (IX), whereby the compound of the formula (I) is obtained in one process step, with elimination of alkali metal halide.
The reaction according to process variant (d)(2) can, if appropriate, be carried out in the presence of a catalyst. Preferably, hydrogen chloride is used for this purpose (see J. Am. Chem. Soc. 69, 2,246 (1947); ibid. 70, 4,187 (1948)).
The reaction temperatures in process variant (d)(2) can be varied within a substantial range. In general, the reaction is carried out at from 0° to 100°C, preferably from 20° to 60°C.
Preferably, equimolar amounts are used when carrying out process variant (d)(2) according to the invention. The compounds of the formula (I) are isolated in the customary manner.
Possible diluents for the reaction according to process variant (e) are water, and organic solvents which 48101 - 36 are inert towards alkali metal hypohalite. These include, as preferences, alcohols, such as methanol or ethanol, ethers, such as diethyl ether, dioxan or tetrahydrofuran, and also two-phase mixtures, for example ether/water. The reaction temperatures in process variant (e) can be varied within a substantial range. In general, the reaction is carried out at from 0° to 100°C, preferably from 0° to 40°C.
In carrying out process variant (e), preferably l to 1.5 moles of hypohalite are employed per mole of the compound of the formula (Ia), the alkali metal hypohalite being produced in situ from the corresponding halogen and the alkali metal hydroxide (see Houben-Weyl, volume V/2a, pages 608-610 (1977)). The end products are isolated in the usual manner.
The active compounds according to the invention exhibit a powerful microbicidal action and can be employed in practice for combating undesired micro-organisms. The active compounds are suitable for use as plant protection agents.
Fungicidal agents in plant protection are employed for combating Plasmodiophoromycetes, Oomyc'etes, Chytridiomycetes, Zygomycetes, Ascony cetesBasidiony cetes and Deuteromycetes.
The good toleration, by plants, of the active compounds, at the concentrations required for combating plant diseases, permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil.
As plant protection agents, the active compounds according to the invention can be used with particularly good success for combating Oomycetes, for exainple against the causative organism of blight and brown rot of tomato and potato (Phytophthora infestans). It should be particularly emphasised that the active compounds according to the invention not only develop a protective action, but - 37 also have a curative/eradicative action. Furthermore, they possess systemic properties. Thus, it is possible to protect plants against fungal attack when the active compound is fed to the above-ground parts of the plant via the soil and the root or via the seed.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, foams, pastes, soluble powders, granules, aerosols, suspension-emulsion concentrates, seed-treatment powders, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances, coating compositions for use on seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils, as well as ULV cold mist and warm mist formulations.
These formulations may be produced in known manner, for example by mixing the active compounds with extenders, that is to say liquid or liquefied gaseous or solid diluents or carriers, optionally with the use of surface-active agents, that is to say emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.
As liquid diluents or carriers, especially solvents, there are suitable in the main, aromatic hydrocarbons, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their.ethers and esters, ketones, such a3 acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethyl49101 - 38 sulphoxide, as well as water.
By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
As solid carriers there may be used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates. As solid carriers for granules there may be used crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks.
As emulsifying and/or foam-forming agents there may be used non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydrolysis products. Dispersing agents include, for example, lignin sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain from 0.1 to - JQ 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight.
The active compounds according to the invention can be present in the formulations or in the various use forms as a mixture with other known active compounds, such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, bird repellants, growth factors, plant nutrients and agents for improving soil structure.
The active compounds can be used as such or in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-fco-use solutions, emulsions, suspensions, powders, pastes and granules They may be used in the customary manner, for example by watering, immersion, spraying, atomising, misting, vapor15 ising, injecting, foaming, brushing on, dusting, scattering dry dressing, moist dressing, wet dressing, slurry dressing or encrusting.
Especially in treatments of parts of plants, the active compound concentrations in the use forms can be varied within a substantial range. They are, in general, from 1 to 0.0001% by weight, preferably from 0.5 to 0.001%.
In the treatment of seed, amounts of active compound of 0.001 tc 50 g, preferably 0.01 to 10 g, are generally employed per kilogram of seed.
For the treatment of soil, active compound concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are generally employed at the place of action.
The present invention also provides a fungicidal composition containing as active ingredient a compound of the present invention in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surfaceactive agent.
The present invention also provides a method of combating fungi which comprises applying to the fungi, or to a habitat thereof, a compound of the present in49101 - 4θ vention alone or in the form of a composition containing as active ingredient a compound of the present invention in admixture with a diluent or carrier.
The present invention further provides crops protected from damage by fungi by being grown in areas in which immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier.
It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.
The fungicidal activity of the compounds of this invention is illustrated by the following bioteat Examples.
In these Examples, the compounds according to the present invention are each identified by the number (given in brackets) of the corresponding preparative Example, which will be found later in this specification.
Example A Phytophthora test (tomato)/protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether Water: 95 parts by weight The amount of the active compound required for the desired concentration of the active compound in the spray liquid was mixed with the stated amount of solvent and the concentrate was diluted with the stated amount of water which contained the stated amount of emulsifier.
Young tomato plants with 2 to 4 foliage leaves were sprayed with the spray liquid until dripping wet. The plants remained in a greenhouse for 24 hours at 20 deg.C and at a relative atmospheric humidity of 70%. The tomato plants were then inoculated with an aqueous spore suspension of Phytophthora infestans. The plants were brought into a moist chamber with an atmospheric humidity of 100% and a temperature of 18-20 deg.C. 9 10 1 - 41 After 5 days the infection of the tomato plants was determined. The assessment data were converted to percent infection: 0% meant no infection; 100% meant that the plants were totally infected.
In this test, for example, the following compounds exhibited a very good action, which was significantly superior to that of the compounds known from the prior art: (1), (2) and (6).
Example B Phytophthora test (tomato)/systemic Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether Water: 95 parts by weight The amount of active compound required for the desired concentration of the active compound in the watering liquid was mixed with the stated amount of solvent and the concentrate was diluted with the stated amount of water which contained the stated amount of the emulsifier.
Tomato plants grown in standard soil and having to 4 foliage leaves were watered three times in the course of one week with 10 ml of the watering liquid, having the stated concentration of active compound, per 100 ml of soil.
The plants treated in this way were inoculated, after the treatment, with an aqueous spore suspension of Phytophthora infestans. The plants were brought into a humidity chamber at an atmospheric humidity of 100% and a temperature of 18 to 20 deg.C. After 5 days, the infection of the tomato plants was determined. The assessment data obtained were converted to percent infection. 0% denoted no infection and 100% denoted that the plants were totally infected.
In this te3t, for example, the following compounds exhibited a very good action, which was significantly superior to that of the compounds known from the prior art: (1), (2) and (6).
Preparative Examples Example 1 CH. ‘j CH2 - C = CH ti (1) Process variant (a) .9 g (0.1 mol) of 2,6-dimethyl-N-propargyl-anilir.e and 8 g (0.1 mol) of pyridine in 100 ml of tetrahydrofuran were heated to the boil and 13 g (0.1 mol) of furane-2carboxylic acid chloride were added cautiously. The reaction mixture was stirred for 15 minutes under reflux and was then concentrated by distilling off the solvent in vacuo. The residue was taken up in methylene chloride and the solution was washed with water.
The organic phase was separated off, dried over scdium sulphate and concentrated. The residue crystallised after trituration with petroleum ether. 22.5 ε (89% of theory) of 2,6-dimethyl-N-(2-furoyl)-N-propargyl-aniline of melting point 1O9~H2°C were obtained.
Preparation of the starting material CH2 - C—CH 2,6-Dimethyl-N-propargyl-aniline was prepared by reacting 2,6-dimethyl-aniline with propargyl bromide in accordance with the data in the literature (see U.S. Patent Specification 4,001,325).
Process variant (b) 21.5 g (0.1 mol) of 2,6-dimethyl-N-(2-furoyl)49101 - 43 aniline and 0.5 g of triethy1-benzyl-ammoniunt chloride were dissolved in a two-phase mixture of 5θ ml of 50% strength sodium hydroxide solution and 250 ml of toluene and 13.1 g (0.11 mol) of propargyl bromide were added dropwise at 20° to 35°C, with vigorous stirring. The mixture was stirred for 2 hours at 20°C, and the organic phase was separated off, washed repeatedly with water, dried over sodium sulphate and concentrated by distilling off the solvent in vacuo.
The residue crystallised after trituration with petroleum ether. 21 g (83% of theory) of 2,6-dimethyl-N-(2furoyl)-N-propargylaniline of melting point 110-112°C were obtained.
Preparation of the starting material 60 g (0.46 mol) of furane-2-earboxylic acid chloride were added dropwise at 0° to 10° C to a solution of 55.7 g (0.46 mol) of 2,6-dimethyl-aniline and 46.5 g (0.46 mol) of triethylamine in 500 ml of methylene chloride, whilst stirring. Stirring was continued for 2 hours at 20°C and the salt produced was filtered off. The filtrate was repeatedly washed with water, dried over sodium sulphate and concentrated by distilling off the solvent in vacuo. The residue was recrystallised from cyelohexane/toluene. 78.4 g (79% of theory) of 2,6-dimethyl-N-(2-furoyl)-aniline of melting 25 point 119-122°C were obtained.
Example 2 (¾ - C=CH - CHZ - 0 - CH3 (2) - 44 Process Variant (b) g (0.155 mol) of ,?,6-dimethyl-N-methoxyacetylaniline and 0.3 g of triethyl-benzyl-ammonium chloride were dissolved in a two-phase system mixture of 100 ml of 50% strength sodium hydroxide solution and 250 ml of toluene, and 19 g (0.016 mol) of propargyl bromide were added with vigorous stirring. The mixture was stirred for 4 hours, and the toluene phase was then separated off, washed repeatedly with water, dried over sodium sulphate and concentrated by distilling off the solvent in a waterpump vacuum. The residue was distilled in a high vacuum. 26.5 g (74% of theory) of 2,6-dimethy1-N-methoxyacetyl-Npropargyl-aniline of boiling point l40°C/0.5 ram Hg and melting point 49-51°C were obtained.
Preparation of the starting material g (0.5 mol) of methoxyacetyl chloride were added dropwise at 5° to 15°C to a solution of 61 g (0.5 mol) of 2.6- dimethylaniline and 50.5 g (0.5 mol) of triethylamine in 250 ml of toluene, whilst stirring and cooling.
Stirring was continued for 2 hours at 20°C, the mixture was filtered, the filtrate was concentrated and the residue was taken up in water. It was extracted with methylene chloride and the extract was dried over sodium sulphate and concentrated by distilling off the solvent. The residue was distilled in a high vacuum. 55 g (57% of theory) of 2.6- dimethy1-N-methoxyacetyl-aniline of boiling point 122-132°C/O.l mm Hg and melting point 6l-63°C were obtained. Example 3 - 45 Process variant (e) g (0.063 mol) of bromine were added dropwise at -5°C to a solution of 22.4 g (0.4 mol) of potassium hydroxide in 100 ml of water. The mixture was allowed to warm to 0°C and at this temperature a solution of l6.6 g (0.05 mol) of 2,6-dimethyl-N-methoxyacetyl-N-propargylaniline (see Example 2) in 150 ml of ether was added dropwise, with vigorous stirring. After stirring for one hour at 20°C, the ether phase was separated off, again washed with water, dried over sodium sulphate and concentrated by distilling off the ether. The residue crystallised after trituration with petroleum ether. 10.1 g (6556 of theory) of 2,6-dimethyl-N-(3-bromopropargyl)-Nmethoxyacetyl-aniline of melting point 53-54°C were obtained.
Example 4 Process variant (c) A mixture of 13.2 g (0,05 mol) of 2,5-diethyl-Mpropargyl-chloroacetanilide and 13.6 g (0.2 mol) of imidazole was stirred, as a melt, at 120°C for 30 minutes. The reaction mixture was then added to water and the precipitate was filtered off and thoroughly washed with viater. After recrystallisation from diisopropyl.ether/ethyl acetate, g (68% of theory) of 2,6-diethyl-N-(imidazol-l-ylacetyl)-N-propargyl-aniline of melting point 129-131°C were obtained.
Preparation of the starting material • 49101 - Ho The preparation was carried out by reacting :,6diethyl-ani)ine with propargyl bromide in the presence of potassium carbonate and reacting the resulting 2,6-diethylpropargylaniline with chloroacetic acid chloride or chloro5 acetic anhydride in accordance with the data in the literature (see U.O. Patent Specification 4,001,525).
The following compounds of the general formula were obtained analogously to the above Examples (in the 10 table that follows, the physical properties are melting points in °C, boiling points in °C/mm Hg or refractive indices). - 47 tx. No.
R1 R2 Rs R* Rs Physical Ri properties /=7 CH, 6-¾¾ Η Η H -CH2-N^_J CH, 6-CH, Η H CH, -U 129-31 110-12 7 CH, 6-CH, H H H /= 120-21 ί 8 CH, 6-CH, H H H -CH2-H 137-40 9 CH, 6-CjH, H H H -u 88 10 CH, 6-CH, H H Br -U 138-40 11 CH, 6-CH, H H CH, -(¾ -O-CH, n": 1-5362 b.pt. 125Ό. 12 CaH, 6-C2H, H H H -CHZ -O-CH, 74 13 CH, 6-CH, H H H -CHCla 114-15 14 CH3 6-0¾ H H H Vo 98-99 15 Cl 6-CH3 H H H -CH2-O-CH3 80 yH=si 1 6 CH3 6-CH3 H H H -CH.-N 93-942 \=J - 48 Physical R1 R2 R3 R4 R5 R6 properties ch3 ch3 6-CH3 6-CH3 H H CHj ch3 H Br -CHjOCHj -CHjOCHj Oil Oil ch3 6-CH3 H ch3 Η 84-86 ch3 6-CH3 H ch3 H -ch2-/| 129-30 ch3 6-CH3 H ch3 H V 87-89 ch3 6-CH3 H ch3 H -COOCH3 63-65 ch3 6-CH3 H CHj HCH2O 235-37(xHCl) ch3 6-CH3 H ch3 H /=» -ch2-nJ 273-74 ch3 6-CH3 H ch3 H -CHjCeOjCHj Oil ch3 6 "CHj H ch3 H -ch2o-Q Oil ch3 6-CHj H ch3 H -chci2 81-82 CH3 6-CH3 H CHj H -ch2sch3 n21:1-5470 D ch3 6-CH3 H ch3 H -ch2-scn 69-70 ch3 6-CH3 H ch3 H -CICHjXHj n28:1-5272 D Ex. MO. R1 R2 R3 R4 R5 g Physical R properties 31 ch3 6-CH3 H ch3 H n23:1.5150 D 32 ch3 6-CH3 H ch3 H -ch=ch-ch3 n22,5:1»3377 D 33 ch3 6-CH3 H ch3 H -C3H7-n 23 n :1 -5102 D 34 CH3 6-CH3 H CH3 H -ch2oc3h7 n22,5:1.5088 D 35 ch3 6-CH3 H ch3 H -C3h7-i 70-72 36 ch3 6-CH3 H H H -cooch3 61-62 37C2H5 6-C2H5 H H H υ 96-97 38CH3 6-CH3 H H H n20:1-5290 39 C2H5 6-c2H5 H H Br -CH2OCH3 55-57 40 CH3 6-CH3 H H H -a^oa^c^H 56-60 41 ch3 6-CH3 H H H -CH2SCH3 n20:1-5637

Claims (5)

CLAIMS; 1. Or 2 that are hereinbefore specifically mentioned in Examples 14 and 17-41. 10. A composition according to claim 6, in which the active compound is according to claim 9. - 58 11. A method according to Claim 7, in which the active compound is according to claim 9. 12. Harevested Crops according to claim 8, when protected by the application of a compound according 1 2 3 1 to 4 carbon atoms or nitro. R 8 represents tetrahydrofuryl, thiophenyl, tetrahydrothiophenyl, optionally methyl- or ethylsubstituted isoxazolyl, and optionally cyano- or 15 thiocyano-substituted alkyl with 1 to 4 carbon atoms and alkenyl and alkynyl each with 2 to 4 carbon atoms, and represents the groupings -CH 2 — Az, -CH 2 -OR 8 , -CH 2 -SR 7 , -OR 7 , CH 2 -OSO 2 R°, -COOR' and —CH 2 -( - 51 wherein 7 fi R and R represent halogen-, cyano and thiocyanosubstituted alkyl with 1 to 4 carbon atoms and alkenyl and alkynyl, with in each case 2 to 4 5 carbon atoms, which are optionally substituted by the indicated alkyl substituents and represents alkoxyalkyl with 1 to 4 carbon atoms in each alkyl part and furthermore R can additionally represent unsubstituted alkyl 10 with 1 to 4 carbon atoms, and Az represents pyrazol-l-yl) 1,2,4-triazol-l-yl and imidazol-l-yl. 1 2 3 4 6 R , R , R , R and R represent hydrogen and alkyl with 1 to 4 carbon atoms, and furthermore R 1 additionally represents halogen and R 8 additionally represents halogen and phenyl which 10 is optionally substituted by halogen, alkyl with
1. Substituted N-propargyl-anilines of the general formula 5 in which
2. Any one of the compounds according to claim 1 that are hereinbefore specifically mentioned 15 in Table 1 or in Examples 1 to 13, 15 and 16.
3. Process for the preparation of substituted N-propargyl-anilines of the general formula in which
4. 5 20 R , R , R , R and R represent hydrogen and alkyl with 1 to 4 carbon atoms, and furthermore R·^ additionally represents halogen and R 5 additionally represents phenyl with which is - 52 optionally substituted by halogen, alkyl with 1 to 4 carbon atoms and nitro, and halogen, R 6 represents tetrahydrofuryl, thiophenyl, tetrahydrothiophenyl, optionally methyl- Oder ethyl5 substituted isoxazolyl, and optionally cyano- or thiocyano-substituted alkyl with 1 to 4 carbon atoms and alkenyl and alkynyl each with 2 to 4 carbon atoms, and represents the groupings CH CH-Az, -CH-OR CHSR OR' -OSOjR -COOR' and -CH15 wherein 7 8 R and R represent halogen-, cyano- and thiocyanosubstituted alkyl with 1 to 4 carbon atoms and alkenyl and alkynyl, with in each case 2 to 4 carbon atoms, which are optionally substituted by the indicated alkyl substituents and represents alkoxyalkyl with 1 to 4 carbon atoms in each alkyl part, and furthermore R can additionally represent unsubstituted alkyl with 1 to 4 carbon atoms, and Az represents pyrazol-l-yl, 1,2,4-triazol-l-yl and imidazol-l-yl, characterized in that a) N-propargyl-anilines of the formula in which to R 5 have the abovementioned meaning, are reacted with acid chlorides or acid bromides or acid 5 anhydrides of the formulae R 5 -C-Cl(Br) (Ilia) or (Illb) in which 10 R 6 has the abovementioned meaning in the presence of a diluent and, if appropriate, in the presence of an acid-binding agent, or b)anilides of the formula (IV) in which 13 6 R to R and R have the abovementioned meaning are reacted with propargyl halides of the formula Hal CH—C»C R 5 (V) in which 4 5 R and R have the abovementioned meaning and Hal represents chlorine or bromine, in the presence of an acid-binding agent and, if 10 appropriate, in the presence of an organic diluent, or in an aqueous-organic two-phase system in the presence of a phase transfer catalyst; or, in the case of some compounds of the formula (I) in that c) halogenacetanilides of the formula - 55 in which R^ to R^ have the abovementioned meaning and Hal' represents chlorine, bromine or iodine are reacted with compounds of the formula B(VII) in which X B SR' group and represents Az and the -OR or represents hydrogen or an alkali metal and 8 R and R have the abovementioned meaning, 10 if appropriate in the presence of a diluent and, if appropriate, in the presence of an acid-binding agent, or d) hydroxyacetanilides of the formula (VIII) 15 in which R 1 to r5 have the abovementioned meaning (1) are reacted, if appropriate after activation by means of an alkali metal, with halides of the formula Hal'-R 9 (IX) - 56 in which Hal* has the abovementioned meaning and ο 8 8 R represents the radical R or the group -SOjR > wherein Q 5 R has the abovementioned meaning, in the presence of a diluent and, if appropriate, in the presence of an acid-binding agent, or (2) are reacted with dihydropyrane of the formula 10 in the presence of a diluent and, if appropriate, in the presence of a catalyst, or e) N-propargyl-anilides according to the invention, of the formula - 57 in which 14 6 R to R and R have the abovementioned meaning are reacted, in a manner which is in itself known, with aqueous alkali metal hypohalite solutions. 5 4. A process for the preparation of a compound according to claim 1, substantially as described in any one of Examples 1 to 4. 5. Compounds according to claim 1, whenever prepared by a process according to claim 3 or 4. 10 6. A fungicidal composition containing as active ingredient a compound according to claim 1 or 2 in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent. 15 7. A method of combating fungi which comprises applying to the fungi, or to a habitat thereof, a compound according to Claim 1 or 2, alone or in the form of a composition containing said compound as active ingredient in admixture with a diluent or carrier. 20 8. Harvested crops protected from damage by fungi by being grown in areas in which immediately prior to and/or during the time of the growing a compound according to Claim 1 or 2 was applied alone or in admixture with a diluent or carrier. 25 9. Any one of the compounds claimed in claim
5. To claim 1.
IE2071/79A 1978-10-31 1979-10-30 Substituted n-propargyl-anilines,processes for their preparation,and their use as fungicides IE49101B1 (en)

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