DK149809B - 1-ALKYL-SUBSTITUTED PYRAZOLD DERIVATIVES - Google Patents
1-ALKYL-SUBSTITUTED PYRAZOLD DERIVATIVES Download PDFInfo
- Publication number
- DK149809B DK149809B DK333679AA DK333679A DK149809B DK 149809 B DK149809 B DK 149809B DK 333679A A DK333679A A DK 333679AA DK 333679 A DK333679 A DK 333679A DK 149809 B DK149809 B DK 149809B
- Authority
- DK
- Denmark
- Prior art keywords
- formula
- substituted
- compounds
- acid
- alkyl
- Prior art date
Links
Classifications
-
- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C233/04—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C233/07—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring
-
- 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
- C07D231/14—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 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
- C07D231/16—Halogen atoms or nitro radicals
-
- 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
Description
149$O9 i o$ 149 O9 in o
Den foreliggende opfindelse angår hidtil ukendte 1-al-kylsubstituerede pyrazolderivater, der er anvendelige som mellemprodukter til syntese af substituerede N-pyrazolylme-thyl-halogenacetanilider, der har herbicide egenskaber.The present invention relates to novel 1-alkyl-substituted pyrazole derivatives useful as intermediates for the synthesis of substituted N-pyrazolylmethyl-haloacetanilides having herbicidal properties.
5 Det er allerede kendt, at man kan anvende 2,6-diethyl- -N-methoxymethyl-chloracetanilid til selektiv ukrudtsbekæmpelse jf. R. Wegler, Chemie der Planzenschutz- und Schad-lingsbekåmpfungsmiddel, bind 5, side 255, Springer-Verlag (1977). Denne forbindelse er imidlertid ikke altid tilstræk-10 kelig virksom og har ikke altid en fuldt ud tilfredsstillende selektivitet.5 It is already known that 2,6-diethyl-N-methoxymethyl chloroacetanilide can be used for selective weed control, cf. R. Wegler, Chemie der Planzenschutz- und Schadlingingsmomfungfungmid, Volume 5, page 255, Springer-Verlag ( 1977). However, this compound is not always sufficiently effective and does not always have a fully satisfactory selectivity.
Endvidere kendes der fra DE offentliggørelsesskrift nr.Furthermore, DE publication publication no.
2.648.008 1-substituerede pyrazolylmethyl-halogenmethylacet-anilider, der kan anvendes til selektiv ukrudtsbekæmpelse.2,648,008 1-substituted pyrazolylmethyl-halomethylacet anilides which can be used for selective weed control.
15 Disse forbindelser har imidlertid heller ikke altid en fuldt tilfredsstillende selektivitet.15 However, these compounds also do not always have a fully satisfactory selectivity.
Der er nu tilvejebragt hidtil ukendte substituerede py-razol-derivater med formlen (I)Newly substituted pyrazole derivatives of formula (I) are now provided.
20 R1 \ N R20 R1 \ N R
— \ I- \ I
-CH—Y (I) r2>=A> hvori 25 R betyder alkyl med 1-8 carbonatomer, halogenalkyl med indtil 2 carbonatomer og indtil 3 halogenatomer, alkoxyalkyl med 1-4 carbonatomer i alkyIdelen og 1-4 carbonatomer i alk-oxydelen eller eventuelt med halogen, alkyl med 1-4 carbonatomer, halogenalkyl med indtil 2 carbonatomer og indtil 30 3 halogenatomer, alkoxy med indtil 2 carbonatomer, alkylthio med indtil 2 carbonatomer, cyano og/eller nitro substitueret phenyl, 12 3 R , R og R er ens eller forskellige og betyder hydrogen eller alkyl med 1-4 carbonatomer, og 35 y betyder chlor, brom, alkylsulfonyl med 1-4 carbonatomer i 2 149809-CH-Y (I) r 2> = A> wherein R is alkyl of 1-8 carbon atoms, haloalkyl of up to 2 carbon atoms and up to 3 halogen atoms, alkoxyalkyl of 1-4 carbon atoms in the alkyl moiety and 1-4 carbon atoms of the alkoxy moiety. or optionally with halogen, alkyl of 1-4 carbon atoms, haloalkyl of up to 2 carbon atoms and up to 3 halogen atoms, alkoxy of up to 2 carbon atoms, alkylthio of up to 2 carbon atoms, cyano and / or nitro substituted phenyl, 12 3 R, R and R is the same or different and means hydrogen or alkyl of 1-4 carbon atoms, and 35 y means chlorine, bromine, alkylsulfonyl of 1-4 carbon atoms in 2 149809
OISLAND
alkyldelen eller eventuelt med alkyl med 1-4 carbonatomer og/eller halogen substitueret phenylsulfony1, eller syreadditionssalte deraf.the alkyl moiety or optionally with alkyl of 1-4 carbon atoms and / or halogen substituted phenylsulfonyl, or acid addition salts thereof.
De 1-alkylsubstituerede pyrazolderivater med formlen (I) 5 kan fremstilles ved, at pyrazoler med formlen (II) R1 ·>=Β\ N—Η (K) R, 10 hvori 12 3 R , R og R har den ovenfor angivne betydning, omsættes med aldehyder med formlen (III) 15 O = CH - R (III) hvori R har den ovenfor angivne betydning, eventuelt i nærværelse af et opløsningsmiddel, og de derved dannede pyrazolderivater med formlen (IV) 20The 1-alkyl-substituted pyrazole derivatives of formula (I) 5 can be prepared by the fact that pyrazoles of formula (II) R 1> = Β \ N - Η (K) R 10 wherein 12 3 R, R and R have the meaning given above is reacted with aldehydes of formula (III) O = CH - R (III) wherein R is as defined above, optionally in the presence of a solvent, and the pyrazole derivatives of formula (IV) thus formed
R’ RR 'R
N—CH — OH (IV) R2 ' ^ R3 25 hvori 12 3 R, R , R og R har den ovenfor angivne betydning, enten direkte eller eventuelt efter isolering omsættes med et halogeneringsmiddel eller et sulfonyleringsmiddel, eventuelt i nærværelse af et opløsningsmiddel. Forbindelserne 30 med formlen (I) fremkommer herved i reglen som syreadditionssalte.N-CH - OH (IV) R 2 'R 3' wherein 12 3 R, R, R and R have the meaning given above, either directly or optionally after isolation, are reacted with a halogenating agent or a sulfonylating agent, optionally in the presence of a solvent. The compounds 30 of formula (I) are thus generally obtained as acid addition salts.
De her omhandlede, 1-alkylsubstituerede pyrazolderivater med formlen (I) egner sig som mellemprodukter til syntese af hidtil ukendte substituerede N-pyrazolylmethyl-halogenacetani-35 lider, der har herbicide egenskaber.The present 1-alkyl-substituted pyrazole derivatives of formula (I) are suitable as intermediates for the synthesis of novel substituted N-pyrazolylmethyl-haloacetanilides having herbicidal properties.
0 3 1498090 3 149809
Overraskende overgår de substituerede N-pyrazolylmethyl--halogenacetanilider, der kan fremstilles ud fra de her omhandlede pyrazolderivater med formlen (I) ved omsætning med halogenacetanilider, ved samme ukrudtsvirkning det kendr 5 te 2,6-diethyl-N-methoxymethyl-chloracetanilid og de ovennævnte kendte pyrazolmethyl-halogenmethylacetanilider med hen syn til selektiv herbicid virkning. De her omhandlede forbindelser udgør således som mellemprodukter til syntese af herbicider med høj værdi et væsentligt teknisk fremskridt.Surprisingly, the substituted N-pyrazolylmethyl-haloacetanilides which can be prepared from the present pyrazole derivatives of formula (I) by reaction with haloacetanilides outperform the known 2,6-diethyl-N-methoxymethyl-chloroacetanilide by the same weeding effect. the above-known known pyrazole methyl haloethylacetanilides with respect to selective herbicidal activity. Thus, the compounds of this invention constitute significant technical advances as intermediates for the synthesis of high value herbicides.
10 De usymmetrisk substituerede pyrazolderivater med formlen (I) optræder på grund af tautomere strukturer i de til fremstillingen anvendte udgangsforbindelser i to isomere former, der formelmæssigt kan anskueliggøres som følger: rVn' ?The asymmetrically substituted pyrazole derivatives of formula (I) occur due to tautomeric structures of the starting compounds used in the preparation in two isomeric forms which can be formally illustrated as follows: rVn '?
M-icH-V og il-icH-YM-icH-V and il-icH-Y
H2 R3 (a) (S) 20 Isomerforholdet bestemmes i det væsentlige af pyrazol- substituenternes art. Desuden kan forbindelserne med formlen (I) foreligge som optiske isomere (jf. det med markerede carbonatom). Por det meste fremkommer der dog blandinger, der indeholder alle isomere. Formlen (I) omfatter både de 25 stillingsisomere og de optiske isomere.The H2 isomer ratio is determined essentially by the nature of the pyrazole substituents. In addition, the compounds of formula (I) may exist as optical isomers (cf. the labeled carbon atom). For the most part, however, mixtures containing all isomers appear. Formula (I) comprises both the 25 position isomers and the optical isomers.
Det ovenfor anførte om strukturisomere og optiske isomere af pyrazolderivaterne med formlen (I) gælder analogt for forbindelserne med formlen (IV) og for de substituerede N-pyra-zolyl-methyl-halogenacetanilider med den nedenfor anførte for-30 mel (V). Formlerne (IV)og(V) omfatter ligeledes både stillingsisomere og optiske isomere.The above-mentioned structural isomers and optical isomers of the pyrazole derivatives of formula (I) apply analogously to the compounds of formula (IV) and to the substituted N-pyrazolylmethyl-haloacetanilides having the formula (V) listed below. Formulas (IV) and (V) also include both position isomers and optical isomers.
Forbindelserne med (XV) står i kemisk ligevægt med deres udgangsforbindelser og kan derfor kun isoleres i enkelttilfælde .The compounds of (XV) are in chemical equilibrium with their starting compounds and can therefore only be isolated in single cases.
35 149809 4 o35 149809 4 o
Ganske særligt foretrukne er de forbindelser med formlen (I), hvori R betyder methyl, ethyl, n-propyl, isopropyl, isobutyl, sek.butyl, n-butyl, trifluormethyl, chlormethyl, dichlormethyl, trichlormethyl, tribrommethyl, phenyl, chlor- 5 phenyl, dichlorphenyl, methylphenyl, dimethylphenyl eller 12 3 chlormethylphenyl eller nitrophenyl, R , R og R er ens eller forskellige og betyder hydrogen eller methyl, og Y betyder chlor, brom, methylsulfonyl, phenylsulfony1, p-methyl-sulfonyl eller p-bromphenylsulfonyl.Particularly preferred are those compounds of formula (I) wherein R is methyl, ethyl, n-propyl, isopropyl, isobutyl, sec-butyl, n-butyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, tribromomethyl, phenyl, chloro-5 phenyl, dichlorophenyl, methylphenyl, dimethylphenyl or chloromethylphenyl or nitrophenyl, R, R and R are the same or different and mean hydrogen or methyl and Y means chlorine, bromine, methylsulfonyl, phenylsulfonyl, p-methylsulfonyl or p-bromophenylsulfonyl.
to Hydroxypyrazol-derivaterne er alment defineret ved form- 12 3 len (IV). I denne formel betyder R, R , R og R fortrinsvis de grupper, der allerede fortrinsvis er nævnt i sammenhæng med beskrivelsen af de her omhandlede pyrazolderivater med formlen (I).the two Hydroxypyrazole derivatives are generally defined by formula (IV). In this formula, R, R, R and R preferably represent those groups which are already preferably mentioned in the context of the description of the pyrazole derivatives of formula (I).
15 Anvendes der f.eks. pyrazol og acetaldehyd som udgangs forbindelser og thionylchlorid som halogeneringsmiddel, kan reaktionsforløbet ved fremstillingen af de her omhandlede pyrazolderivater med formlen I gengives ved følgende reaktionsskema: 20 "~\-H + CH3-CH0 -5*- J^N-Ah-OH S0C1?-· >.15 For example, if pyrazole and acetaldehyde as starting compounds and thionyl chloride as halogenating agent, the course of the reaction in the preparation of the present pyrazole derivatives of formula I can be represented by the following reaction scheme: 20 "~ \ -H + CH3-CH0 -5 * - J ^ N-Ah-OH SO ? - ·>.
[=N\ ?H’ 25 j_^N-CH-C1 x HC1[= N \ H '25 µ N-CH-C1 x HCl
De herved som udgangsforbindelser nødvendige pyrazoler er defineret alment ved formlen (II). I formlen (II) betyder , 2 3 30 R og R fortrinsvis de grupper, der allerede fortrinsvis er nævnt i sammenhæng med beskrivelsen af de her omhandlede forbindelser med formlen (I).The pyrazoles required as starting compounds are generally defined by formula (II). In formula (II), R 2 and R 2 preferably represent the groups already mentioned preferably in connection with the description of the compounds of formula (I).
Forbindelserne med formlen (II) er almindelig kendte forbindelser inden for den organiske kemi. Som eksempler herpå 35 kan der nævnes pyrazol, 4-chlorpyrazol, 3-methylpyrazol, 5- o 5 1A 9 8 O 9 -methylpyrazol, 3,5-dimethylpyrazol, 4-chlor-3,5-dimethylpy-razol og 4-methoxypyrazol.The compounds of formula (II) are generally known compounds in organic chemistry. Examples of these include pyrazole, 4-chloropyrazole, 3-methylpyrazole, 5- o 5 1A 9 8 0 9 -methylpyrazole, 3,5-dimethylpyrazole, 4-chloro-3,5-dimethylpyrazole and 4-methoxypyrazole. .
De endvidere som udgangsforbindelser nødvendige aldehyder er alment defineret ved formlen (III). I denne formel betyder 5 R fortrinsvis de grupper, der allerede fortrinsvis er nævnt i sammenhæng med beskrivelsen af de her omhandlede forbindelser med formlen (I).Furthermore, the aldehydes needed as starting compounds are generally defined by formula (III). In this formula, 5R preferably means the groups already mentioned preferably in the context of the description of the compounds of formula (I).
Forbindelserne med formlen (III) er almindelig kendte forbindelser inden for den organiske kemi. Som eksempler herpå 10 kan der nævnes: acetaldehyd, propionaldehyd, n-butyraldehyd, isobutyraldehyd, methoxyacetaldehyd, chloral, benzaldehyd, 3,4-dichlorbenzaldehyd, 1,1-dichloracetaldehyd, chloracetaldehyd, acrolein, crotonaldehyd, propynal, bromal, valeriane-aldehyd, cyclopropanal, cyclopentanal og cyclohexanal.The compounds of formula (III) are commonly known compounds in organic chemistry. Examples of 10 include: acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, methoxyacetaldehyde, chloral, benzaldehyde, 3,4-dichlorobenzaldehyde, 1,1-dichloroacetaldehyde, chloroacetaldehyde, acrolein, crotonaldehyde, propynal, propynal, cyclopropanal, cyclopentanal and cyclohexanal.
15 Ved gennemførelsen af den anførte fremstillingsmetode er det desuden nødvendigt at anvende halogenerings- eller sulfo-nyleringsmidler som reaktionskomponent. På tale som halogene-ringsmidler kommer fortrinsvis phosphor- og svovlhalogenider, især chlorider og bromider. Hertil hører fortrinsvis thionyl-20 chlorid, sulfurylchlorid, phosphortrichlorid, phosphortribro-mid, phosphoroxychlorid og phosphorpentachlorid. Desuden kan der fortrinsvis nævnes phosgen. På tale som sulfonylerings-midler kommer fortrinsvis alkyl- og arylsulfohalogenider. Hertil hører fortrinsvis methylsulfochlorid, benzensulfochlorid, 25 p-toluensulfochlorid og p-bromphenylsulfochlorid.In addition, in the implementation of the preparation method stated, it is necessary to use halogenating or sulfonylating agents as a reaction component. Speaking as halogenating agents are preferably phosphorus and sulfur halides, especially chlorides and bromides. Preferably there are thionyl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus tribromide, phosphorus oxychloride and phosphorus pentachloride. In addition, phosgene may preferably be mentioned. Speaking as sulfonylating agents are preferably alkyl and aryl sulfohalides. Preferably include methyl sulfochloride, benzenesulfochloride, p-toluenesulfochloride and p-bromophenyl sulfochloride.
På tale som opløsningsmidler ved den anførte omsætning kommer fortrinsvis organiske opløsningsmidler, der er indifferente over for pyrazol eller de anvendte halogenerings- og sulfonyleringsmidler. Hertil hører fortrinsvis ethere, såsom 30 diethylether eller tetrahydrofuran, aromatiske og aliphatiske carbonhydrider, såsom benzen, toluen, xylen eller cyclohexan, halogenerede carbonhydrider, såsom chloroform, methylenchlorid, carbontetrachlorid, 1,1,1-trichlorethan, 1,2-dichlorethan, 1,1,2-trichlorethylen eller chlorbenzen, samt formamider, især 35 dimethylformamid.Speaking as solvents in the stated reaction, preferably organic solvents which are inert to pyrazole or the halogenating and sulfonylating agents used are present. Preferably, ethers such as diethyl ether or tetrahydrofuran include aromatic and aliphatic hydrocarbons such as benzene, toluene, xylene or cyclohexane, halogenated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, 1,1,1-trichloroethane, 1,2-dichloroethane, 1 , 1,2-trichloroethylene or chlorobenzene, and formamides, especially dimethylformamide.
6 o 1498096 to 149809
Reaktionstemperaturerne kan ved. gennemførelsen af den anførte omsætning varieres inden for et større område. I almindelighed arbejdes der mellem -70 og +50°C, fortrinsvis ved -20 til +30°C.The reaction temperatures can at. the implementation of the listed revenue is varied within a larger area. Generally, between -70 and + 50 ° C are employed, preferably at -20 to + 30 ° C.
5 Ved gennemførelsen af den anførte omsætning anvendes der pr. mol pyrazol med formlen (II) fortrinsvis 0,5 til 2,0 mol aldehyd med formlen (III), og det dannede hydroxypyrazolderi-vat med formlen (IV) omsættes direkte eller efter forudgående isolering med 0,5-5 mol halogenerings- eller sulfonylerings-10 middel. Forbindelserne med formlen (I) fremkommer derved i form af deres hydrohalogenider og kan således direkte isoleres ved gængse metoder. Det er imidlertid også muligt at frigøre forbindelserne med formlen (I) fra deres hydrohalogenider på gængs måde, f.eks. ved behandling med stærke baser. Eventuelt 15 kan der derefter på kendt måde fremstilles et andet syreadditionssalt, f.eks. ved opløsning af en forbindelse med formlen (I) i et egnet indifferent opløsningsmiddel og tilsætning af syren. Isoleringen foregår i almindelighed ved simpel fra-filtrering af reaktionsprodukterne.5 For the purpose of carrying out the stated turnover, per year. moles of pyrazole of formula (II) preferably 0.5 to 2.0 moles of aldehyde of formula (III), and the hydroxypyrazole derivative of formula (IV) formed is reacted directly or after prior isolation with 0.5-5 moles of halogenation or sulfonylating agent. The compounds of formula (I) thus appear in the form of their hydrohalides and thus can be directly isolated by conventional methods. However, it is also possible to liberate the compounds of formula (I) from their hydrohalides in conventional manner, e.g. when treated with strong bases. Optionally, then, in a known manner, another acid addition salt can be prepared, e.g. by dissolving a compound of formula (I) in a suitable inert solvent and adding the acid. The isolation is generally carried out by simple filtration of the reaction products.
20 Ved en foretrukken udførelsesform for den anførte omsæt ning kan man ud fra forbindelser med formlen (I), hvori Y betyder chlor, ved den almindelig kendte.halogenombytning (Finkelstein-reaktionen), f.eks. ved behandling med kalium-bromid eller kaliumiodid i acetone, fremstille de tilsvarende 25 bromider og iodider.In a preferred embodiment of the above reaction, compounds of formula (I) wherein Y is chlorine can be obtained by the commonly known halogen exchange (Finkelstein reaction), e.g. by treatment with potassium bromide or potassium iodide in acetone, prepare the corresponding 25 bromides and iodides.
Til fremstilling af syreadditionssalte af forbindelserne med formlen (I) kommer alle stærke syrer på tale. Hertil hører fortrinsvis hydrogenhalogenidsyrerne, f.eks, saltsyre og hydrogenbromidsyre, især saltsyre, endvidere phosphorsyre, 30 salpetersyre, svovlsyre, mono- og bifunktionelle carboxylsyrer og hydroxycarboxylsyrer, f.eks. eddikesyre, maleinsyre, ravsyre, fumarsyre, vinsyre, citronsyre, salicylsyre, sor-binsyre samt sulfonsyrer, f.eks. p-toluensulfonsyre og 1,5-naphtalendisulfonsyre.For the preparation of acid addition salts of the compounds of formula (I), all strong acids are discussed. Preferably these include the hydrogen halide acids, for example, hydrochloric acid and hydrobromic acid, especially hydrochloric acid, in addition phosphoric acid, nitric acid, sulfuric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, e.g. acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and sulfonic acids, e.g. p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid.
35 7 14980935 7 149809
OISLAND
De her omhandlede, substituerede pyrazolderivater med formlen (I) egner sig som mellemprodukter til syntese af substituerede N-pyrazolylmethyl-halogenacetanilider, der har herbicide egenskaber. De substituerede N-pyrazolylmethyl--halogenacetanilider med formlen (V) X2 χΐ F /ΐ^=ί"Κ CH—Ν' «Τ»-N V=^R2 (V) v R3 Λ 10 Y3 \ A C — CH, HalThe present substituted pyrazole derivatives of formula (I) are suitable as intermediates for the synthesis of substituted N-pyrazolylmethyl haloacetanilides having herbicidal properties. The substituted N-pyrazolylmethyl-haloacetanilides of formula (V) X2 χΐ F / ΐ ^ = ί "Κ CH-Ν '" Τ »-N V = ^ R2 (V) v R3 Λ 10 Y3 \ A C - CH, Hal
BB
12 3 hvori R, R , R og R har den ovenfor angivne betydning, 12 3Wherein R, R, R and R have the meaning given above,
Hal betyder halogen, og X , X og X er ens eller forskellige 15 og betyder hydrogen eller alkyl, kan fremstilles ved at omsætte pyrazolderivater med formlen (I)Hal represents halogen and X, X and X are the same or different and represent hydrogen or alkyl can be prepared by reacting pyrazole derivatives of formula (I)
r1|=-n Rr1 | = -n R
20 N—CH—Y (DN-CH-Y (D
R3 12 3 hvori R, R , R , R og Y har den ovenfor angivne betydning, 25 med halogenacetanilider med formlen (VI) x2/Γ „ O-\ (VI) C - CH2 - Hal 30 X ϋ 0 o 8 U38 03 12 3 hvori Hal, X , X og X har den ovenfor angivne betydning, i nærværelse af et syrebindende middel og eventuelt i nærværelse af et organisk opløsningsmiddel, idet pyrazolderi-vaterne med formlen (I) fortrinsvis anvendes i form af hy-5 drohalogenid-salte.R3 12 3 wherein R, R, R, R and Y have the meaning given above, with haloacetanilides of formula (VI) x2 / Γ 'O- \ (VI) C - CH2 - Hal 30 X ϋ 0 o 8 Wherein Hal, X, X and X are as defined above in the presence of an acid-binding agent and optionally in the presence of an organic solvent, the pyrazole derivatives of formula (I) being preferably used in the form of hydrohalide. salts.
De ved denne omsætning som udgangsforbindelser anvendte halogenacetanilider er defineret alment ved formlen (VI).The haloacetanilides used in this reaction as starting compounds are generally defined by formula (VI).
I denne formel betyder Hal fortrinsvis halogenerne fluor, 12 3 chlor eller broiji, især chlor eller brom. X , X og X er 10 ens eller forskellige og betyder fortrinsvis hydrogen samt ligekædet eller forgrenet alkyl, især methyl, ethyl, isopropyl, isobutyl, sek.butyl eller tert.butyl.In this formula, Hal preferably means the halogens fluorine, chlorine or bromine, especially chlorine or bromine. X, X and X are the same or different and preferably represent hydrogen as well as straight or branched alkyl, especially methyl, ethyl, isopropyl, isobutyl, sec-butyl or tert-butyl.
Halogenacetaniliderne med formlen (VI) er almindelig kendte forbindelser inden for den organiske kemi eller kan 15 fremstilles ved kendte metoder.The haloacetanilides of formula (VI) are commonly known compounds in organic chemistry or may be prepared by known methods.
Ved omsætningen af de her omhandlede substituerede pyrazol-derivater med formlen (I) med halogenacetaniliderne med formlen (VI) kan der som opløsningsmidler anvendes alle indifferente, med vand ublandbare organiske opløsningsmidler. Her-20 til hører fortrinsvis ethere, såsom diethylether, aromatiske carbonhydrider, såsom benzen, toluen eller xylen, halogenerede carbonhydrider, såsom methylenchlorid, carbontetrachlorid, chloroform eller chlorbenzen, og estere, såsom eddikesyre-ethylester.When reacting the substituted pyrazole derivatives of formula (I) with the haloacetanilides of formula (VI) herein, all inert, water-immiscible organic solvents can be used as solvents. Preferably, these include ethers such as diethyl ether, aromatic hydrocarbons such as benzene, toluene or xylene, halogenated hydrocarbons such as methylene chloride, carbon tetrachloride, chloroform or chlorobenzene, and esters such as acetic acid ethyl ester.
25 Den ovenfor beskrevne omsætning til fremstilling af substituerede N-pyrazolylmethyl-halogenacetanilider gennemføres i nærværelse af syrebindende midler. Som sådanne kan der anvendes alle gængse syrebindende midler. Hertil hører fortrinsvis uorganiske baser, f.eks. alkalimetalhydroxider 30 og alkalimetalcarbonater.The reaction described above for the preparation of substituted N-pyrazolylmethyl-haloacetanilides is carried out in the presence of acid binding agents. As such, all common acid binding agents can be used. This includes preferably inorganic bases, e.g. alkali metal hydroxides and alkali metal carbonates.
Reaktionstemperaturerne kan ved gennemførelsen af den ovenfor beskrevne omsætning til fremstilling af substituerede N-pyrazolylmethyl-halogenacetanilider varieres inden for et større område. I almindelighed arbejdes der mellem -70 og 35 9 o 149309 +100°C, fortrinsvis mellem -20 og +80°C.The reaction temperatures can be varied within a larger range in carrying out the reaction described above for the preparation of substituted N-pyrazolylmethyl-haloacetanilides. Generally, between -70 and 35 ° C are operated at + 100 ° C, preferably between -20 and + 80 ° C.
Ved gennemførelsen af den ovenfor beskrevne omsætning anvender man fortrinsvis pr. mol halogenacetanilid med formlen (VI) 0,5 til 2,0 mol pyrazolylderivat med formlen (I) 5 samt 1-10 mol syrebindende middel. Isoleringen af forbindelserne med formlen (V) foregår på gængs måde.In carrying out the above-described turnover, it is preferably used per 0.5 to 2.0 moles of pyrazolyl derivative of formula (I) and 1-10 moles of acid binding agent. The isolation of the compounds of formula (V) is carried out in the usual manner.
Ifølge en foretrukken udførelsesform gennemføres den ovenfor beskrevne omsætning til fremstilling af substituerede N-pyrazolyl-halogenacetanilider med formlen (V) i et tofase- 10 system, f.eks. vandig natrium- eller kaliumhydroxid/toluen-eller methylenchlorid, eventuelt .under tilsætning af 0,01-1 mol af en fase-transfer-katalysator, f.eks. ammonium- eller phosphoniumforbindelser, f.eks. benzyl-dodecyl-dimethyl-ammo-niumchlorid ("Zephirol").In a preferred embodiment, the above-described reaction is carried out to prepare substituted N-pyrazolyl haloacetanilides of formula (V) in a two-phase system, e.g. aqueous sodium or potassium hydroxide / toluene or methylene chloride, optionally, with the addition of 0.01-1 mole of a phase transfer catalyst, e.g. ammonium or phosphonium compounds, e.g. benzyl dodecyl dimethyl ammonium chloride ("Zephirol").
15 De substituerede N-pyrazolylmethyl-halogenacetanilider med formlen (V) udmærker sig ved siden af en god total herbicid virkning fremfor alt ved deres selektive anvendelsesmuligheder ved vigtige kulturplanter, såsom bomuld, roer, majs, soya, jordnødder og grønsager. De egner sig 20 først og fremmest til anvendelse før-emergens, men udviser også en virkning ved anvendelse efter emergens.The substituted N-pyrazolylmethyl-haloacetanilides of formula (V) are distinguished by a good total herbicidal action, above all, by their selective uses in important crops such as cotton, beets, corn, soy, peanuts and vegetables. They are primarily suitable for pre-emergence use, but also exhibit an effect on post-emergence use.
De gode herbicide virkninger af de substituerede N-pyra-zolyl-halogenacetanilider med formlen (V) fremgår af det efterfølgende eksempel.The good herbicidal effects of the substituted N-pyrazolyl-haloacetanilides of formula (V) are shown in the following example.
25 Liste over virksomme stoffer? I de efterfølgende eksempler undersøges de nedenfor angivne virksomme stoffer for deres herbicide virkning.25 List of active substances? In the following examples, the active substances listed below are examined for their herbicidal activity.
C2H5C2H5
30 fi-t CHj-OOH30 CH-OOH
(A) ft ^C-CH,C1 C2H5 5 2 35 (kendt fra US-patent nr. 3.442.945) o 149809 ίο c2h5 'N=l(A) ft ^ C-CH, C1 C2H5 5 2 35 (known from U.S. Patent No. 3,442,945)
,-( 2 5 CH~-N, - (2.5 CH ~ -N
(B) ^ ^C-CH-Cl 5 C2H5 5 2 (kendt fra DE-offentliggørelsesskrift nr. 2.648.008) /_J:2H5 CH2-N Ί o (c) ^ \ C-CH-Cl c2h5 3 (kendt fra DE-offentliggørelsesskrift nr. 2.648.008) 15 _/¾ C0-CH,C1 (V-,)(B) ^^ C-CH-Cl 5 C2H5 5 2 (known from DE Publication No. 2,648,008) / _J: 2H5 CH2-N Ί o (c) ^ \ C-CH-Cl c2h5 3 (known from DE Publication No. 2,648,008) 15 _ / ¾ C0-CH, C1 (V-,)
2 5 CH3 N«J2 5 CH3 N «J
2020
CHCH
03 .C0-CH,C1 <c„-n CH3 C,H.03 .CO-CH, C1 <c „-n CH3 C, H.
30 ,_( ,CO-CH,Cl (V-3) " M „Nh-π30, _ (, CO-CH, Cl (V-3) "M" Nh-π
2 5 έΗj «“I2 5 έΗj «“ I
149809 11 o149809 11 o
Eksempel AExample A
Præ-emergens-testPre-emergence test
Opløsningsmiddel: 5 vægtdele acetoneSolvent: 5 parts by weight acetone
Emulgator: 1 vægtdel alkylarylpolyglycolether 5 Til fremstilling af et hensigtsmæssigt præparat af virksomt stof blandes 1 vægtdel virksomt stof med den angivne mængde opløsningsmiddel, den angivne mængde emulgator tilsættes, og koncentratet fortyndes med vand til den ønskede koncentration.Emulsifier: 1 part by weight of alkylaryl polyglycol ether 5 To prepare a suitable composition of active substance, 1 part by weight of active substance is mixed with the indicated amount of solvent, the indicated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Frø af forsøgsplanterne udsås i normal jord og vandes ef-10 ter 24 timer med præparatet af virksomt stof. Derved holdes vandmængden pr. arealenhed hensigtsmæssigt konstant. Koncentrationen af virksomt stof i præparatet spiller ingen rolle, afgørende er kun den anvendte mængde virksomt stof pr. arealenhed. Efter 3 ugers forløb bedømmes planternes beskadigelses-15 grad i procent beskadigelse i sammenligning med udviklingen af ubehandlede kontrolplanter. Herved betyder 0% ingen virkning (som ubehandlet kontrol), og 100% betyder total udryddelse.Seeds of the test plants are seeded in normal soil and watered after 24 hours with the active ingredient preparation. This keeps the amount of water per day. appropriately constant area unit. The concentration of active substance in the preparation does not matter, decisive is only the amount of active substance used per day. unit area. After 3 weeks, the damage rate of 15 plants is assessed as a percentage of damage compared to the development of untreated control plants. By this, 0% means no effect (like untreated control) and 100% means total extinction.
Resultaterne af dette forsøg er anført i de efterfølgen-20 de tabeller A til C.The results of this experiment are given in the following Tables A through C.
12 14980912 149809
ω 8 8 ° ° 8 Sω 8 8 ° ° 8 S
SS
.% 8 ° 8 5 8 8 i* s i H p O o o o o a « 'r 2 2 oo 952 9 9.% 8 ° 8 5 8 8 i * s i H p O o o o o a «'r 2 2 oo 952 9 9
ri ri COCO «Ο W CO COri ri COCO «Ο W CO CO
<D P<D P
> ,"5 C M-l S O O O O 0 2 3 ov o\ CO Ό O o i-i 0 a flj sf s s SS s 8 jj So 88 88 S O to>, "5 C M-l S O O O O 0 2 3 ov o \ CO Ό O o i-i 0 a flj sf s s SS s 8 yy So 88 88 S O to
-P-P
I 1 03 'ri <8 o o o o o o <fi |j'^o\ocoacsco , 2 itf (tfI 1 03 'ri <8 o o o o o o <fi | j' ^ o \ ocoacsco, 2 itf {tf
Η SOΗ SO
(DM(DM
Λ g , g J.3 8 ° 8 ° S ° ffl to &Λ g, g J.3 8 ° 8 ° S ° ffl to &
MM
AiAi
S „ S 8 SS SSS "S 8 SS SS
<D -ri *” »* *“ *“<D -ri * ”» * * “*“
0} M0} M
8 to 88 88 88 Ή O T- «- T- ·* «—! ϋ Λ w a P : r£ 0) «3 in ιλ ιλ c; rjjJZ % % *8 to 88 88 88 Ή O T- «- T- · *« -! ϋ Λ w a P: r £ 0) «3 in ιλ ιλ c; rjjJZ%% *
o) tjiv m es ift Μ ιΛ Mo) tive m es ift Μ ιΛ M
> CD> CD
SS* s h-SS * s h-
O <H PO <H P
to O Ό <··.to O Ό <··.
.* P C (*> N. * P C (*> N
r si έ έr si έ έ
OISLAND
13 14980913 149809
Tabel BTable B
Præ-emergens-testPre-emergence test
Virksomt kg/ha % Virkning stof Sinapis Galinsoga Stellaria Lolium (V-2) 2,5 0 100 100 100 (B) 2,5 40 100 90 90 10 (kendt) 14 149809 t Φ ο ο ο ο ο ο ο Τ <* ** « Μ _ _ π Ο Ο Ο Ο ο ο (ΰ φ \0 s 'd Η Ο Ο Q Ο ο Ο I * Λ -α ο ο eg Ο β qj w > w (U _ _ iri ο o 2 2 2 2 M O) CB O CO O to •Η T- T“ æ J s ° s s s sActive kg / ha% Impact substance Sinapis Galinsoga Stellaria Lolium (V-2) 2.5 0 100 100 100 (B) 2.5 40 100 90 90 10 (known) 14 149809 t Φ ο ο ο Τ Τ * ** «Μ _ _ π Ο Ο Ο Ο ο ο (ΰ φ \ 0 s' d Η Ο Q Ο ο Ο I * Λ -α ο ο eg Ο β qj w> w (U _ _ iri ο o 2 2 2 2 MO) CB O CO O to • Η T- T “æ J s ° ssss
-¾ 0 03 Hi <D-¾ 0 03 Hi <D
f g “S §§ 88 88 HQ) G r“ 0) Di -jj Λ U ^ (d <D o κ § ,sf g “S §§ 88 88 HQ) G r“ 0) Di -jj Λ U ^ (d <D o κ §, s
fc 1 SS SS S Sfc 1 SS SS S S S
P4 HP4 H
U 4J (ti s i 8 S || || id r~ r- r- r- +) .0) inU 4J (ti s i 8 S || || id r ~ r- r- r- +) .0) in
1-0 λ ·λ S inw incQ1-0 λ · λ S inw incQ
£ 81¾ ci «- ts ^ c? - £ § *£ 81¾ ci «- ts ^ c? - £ § *
x -p <h <? Tx -p <h <? T
ags o § ± 4 > οι m, ·>* x *· *“*ags o § ± 4> οι m, ·> * x * · * “*
OISLAND
15 14980915 149809
Resultaterne, der er anført i tabel A, viser, at det virksomme stof (V-2), der kan fremstilles ud fra den her omhandlede forbindelse (1), er bedre egnet til selektiv u-krudtsbekæmpelse i Sinapis og bomuld end sammenligningsfor-5 bindeisen (A), der er kendt som et godt herbicid. Forbindelsen (V-3) overgår sammenligningsforbindelsen (A) ved bekæmpelse af ukrudt i roer.The results listed in Table A show that the active substance (V-2), which can be prepared from the compound (1) hereof, is better suited for selective weed control in Sinapis and cotton than Comparative Comparison 5. the binder ice (A), which is known as a good herbicide. Compound (V-3) outperforms Comparative Compound (A) by controlling weeds in beets.
Værdierne i tabel B viser tydeligt, at det virksomme stof (V-2), der kan fremstilles ud fra den her omhandlede 10 forbindelse (1), er bedre egnet til selektiv ukrudtsbekæmpelse i Sinapis end forbindelsen (B), der er beskrevet i DE offentliggørelsesskrift nr. 2.648.008 som forbindelse 8.The values in Table B clearly show that the active substance (V-2) which can be prepared from the present compound (1) is better suited for selective weed control in Sinapis than the compound (B) described in DE Publication No. 2,648,008 as connection 8.
Da Sinapis (sennep) står som repræsentant for den nært beslægtede Brassica (raps), kan det sluttes, at det virksomme 15 stof (V-2), der kan fremstilles ud fra det her omhandlede mellemprodukt (1), tåles bedre af alle Brassica-arter end det til sammenligning anvendte virksomme stof.Since Sinapis (mustard) is representative of the closely related Brassica (rapeseed), it can be concluded that the active substance (V-2), which can be prepared from the intermediate product (1) hereof, is better tolerated by all Brassica species other than the active substance used for comparison.
Som det endvidere fremgår af resultaterne i tabel C, har halogen-acetaniliderne (V-l) og (V-2) ved ukrudtsbekæm-20 pelse i hvede, bomuld, majs og roer bedre selektive herbicide egenskaber end den kendte sammenligningsforbindelse (C).Further, as can be seen from the results in Table C, the halogeno-acetanilides (V-1) and (V-2) in weed control in wheat, cotton, maize and beet have better selective herbicidal properties than the known Comparative Compound (C).
Den ved de anførte forsøg påviste overlegenhed af de ud fra de her omhandlede mellemprodukter fremstillelige halogen-acetanilider i forhold til et anerkendt, godt virksomt han-25 delsprodukt til samme indikation og i forhold til konstitutionelt lignende forbindelser, der er kendt fra DE offentliggørelsesskrift nr. 2.648.008 må betegnes som absolut overraskende.The above tests demonstrated the superiority of the halogen-acetanilides prepared from the intermediates in question with respect to a recognized, well-functioning commercial product for the same indication and in relation to constitutionally similar compounds known from DE publication no. 2,648,008 must be described as absolutely surprising.
OISLAND
149809 16149809 16
FremstillingseksemplérFremstillingseksemplér
Eksempel 1 5 /“Ί 5 Cl-CH-x HC1Example 1 5 / ““ 5 Cl-CH-x HCl
Til 340 g (5 mol) pyrazol i 1200 ml methvlenchlorid sættes dråbevis ved 0-5°C i løbet af 1 time 250 g (5,7 mol) acetalde-10 hyd. Der efteromrøres i ca. 1 time ved 0°C. Det derved dannede N-(1-hydroxyethyl)-pyrazol isoleres ikke. Reaktionsopløsningen sættes derimod direkte dråbevis ved 0-5°C i løbet af 1 time. til 1250 g (10,5 mol) thionylchlorid. Der efteromrøres i 1 time ved 20°C og inddampes derefter i vakuum ved 40°C. Efter tilsæt-15 ning af 300 ml methylenchlorid inddampes der på ny. Remanensen destilleres i vakuum. Der fås 620,3 g (75% af det teoretiske udbytte) N-(1-chlorethyl)-pyrazol-hydrochlorid med et kogepunkt på 55°C ved 18 mm Hg.To 340 g (5 moles) of pyrazole in 1200 ml of methylene chloride is added dropwise at 0-5 ° C over 1 hour 250 g (5.7 moles) of acetaldehyde. Stir for approx. 1 hour at 0 ° C. The N- (1-hydroxyethyl) pyrazole thus formed is not isolated. In contrast, the reaction solution is added dropwise at 0-5 ° C over 1 hour. to 1250 g (10.5 mol) of thionyl chloride. Stir for 1 hour at 20 ° C and then evaporate in vacuo at 40 ° C. After adding 300 ml of methylene chloride, evaporate again. The residue is distilled in vacuo. 620.3 g (75% of theoretical yield) of N- (1-chloroethyl) -pyrazole hydrochloride having a boiling point of 55 ° C is obtained at 18 mm Hg.
Omsætning af forbindelsen (1) til det tilsvarende substi-20 tuerede N-pyrazolylmethyl-halogenacetanilid med formlen .CH, U ^-1 > tt CHsiCl 25 C2Hs g '42,3 g (0,2 mol) 2-ethyl-6-methyl-chloracetanilid og 36,8 g (0,22 mol) N-(1-chlorethyl)-pyrazol-hydrochlorid opløses i 200 ml methylenchlorid. Efter tilsætning af 0,5 ml 30 "Zephirol" (50% vandig opløsning af benzyl-dodecyl-dimethylam-moniumchlorid) dryppes blandingen under stærk omrøring til en opløsning af 80 g (2 mol) natriumhydroxid i 80 ml vand, hvorved reaktionsblandingen opvarmes til tilbagesvaling. Der vi-dereomrøres i ca. 3 timer, indtil reaktionsblandingen er af-35 kølet til stuetemperatur. Den organiske fase fraskilles, va- o 149809 17 skes neutral med vand, tørres over natriumsulfat og inddampes i vakuum,Reaction of the compound (1) to the corresponding substituted N-pyrazolylmethyl haloacetanilide of the formula .CH, U1-1> tt CHsiCl 25 C2Hs g '42, 3 g (0.2 mole) methyl chloroacetanilide and 36.8 g (0.22 mol) of N- (1-chloroethyl) pyrazole hydrochloride are dissolved in 200 ml of methylene chloride. After adding 0.5 ml of 30 "Zephirol" (50% aqueous solution of benzyl-dodecyl-dimethylammonium chloride), the mixture is dripped with vigorous stirring to a solution of 80 g (2 moles) of sodium hydroxide in 80 ml of water, thereby heating the reaction mixture to reflux. Stirring for approx. 3 hours until the reaction mixture is cooled to room temperature. The organic phase is separated, neutralized with water, dried over sodium sulfate and evaporated in vacuo.
Der fås en farveløs olie som remanens, der gennemkrystal-liserer efter nogen tid. Udbytte: 29 g (47,5% af det teoreti-5 ske) 2-ethyl-6-methyl-N-(pyrazol-l-yl-eth-l-yl)-chloracetanilid i form af hvide krystaller med et smeltepunkt på 74°C. Stoffet kan renses ved flere ganges omkrystallisation fra diethylether og har da et smeltepunkt på 84°C.A colorless oil is obtained as residue which crystallizes after some time. Yield: 29 g (47.5% of theory) 2-ethyl-6-methyl-N- (pyrazol-1-yl-eth-1-yl) -chloroacetanilide in the form of white crystals, m.p. 74 ° C. The substance can be purified by several times recrystallization from diethyl ether and then has a melting point of 84 ° C.
Fremstilling af udgangsforbindeIsen:Preparation of the starting connection:
10 J10 J
,—/ /H (VI-1) €r< \ xc - CH- Cl c2h5 δ 15, - // H (VI-1) € r <\ xc - CH- Cl c2h5 δ 15
Til 135,2 g (1 mol) 2-ethyl-6-methyl-anilin i 1QQ0 ml toluen sættes 152 g (1,1 mol) kaliumcarbonat. Hertil sættes dråbevis under omrøring 113 g (1 mol) chloreddikesyrechlorid.To 135.2 g (1 mole) of 2-ethyl-6-methyl-aniline in 1 ml of toluene is added 152 g (1.1 mole) of potassium carbonate. To this, 113 g (1 mole) of chloroacetic acid chloride are added dropwise with stirring.
Efter at den eksoterme reaktion er klinget af, efteromrøres 20 der i 2 timer under tilbagesvaling. Derpå filtreres reaktionsblandingen, og filtratet inddampes i vakuum til 500 ml. De derved dannede krystaller fraskilles ved sugning og vaskes med petroleumsether. Der fås 202,9 g (96,2% af det teoretiske udbytte) 2-ethyl-6-methyl-chloracetanilid i form af hvide kry-25 staller med et smeltepunkt på 120°C.After the exothermic reaction is quenched, 20 is refluxed for 2 hours under reflux. The reaction mixture is then filtered and the filtrate is evaporated in vacuo to 500 ml. The crystals thus formed are separated by suction and washed with petroleum ether. 202.9 g (96.2% of theoretical yield) of 2-ethyl-6-methyl-chloroacetanilide in the form of white crystals having a melting point of 120 ° C are obtained.
Eksempel 2 [=N\ N - CH - Cl x HC1Example 2 [= N \ N - CH - Cl x HCl
30 1=^ CH= 1 CH
30 ✓ x CH, CH,30 ✓ x CH, CH,
Til 204 g (3 mol) pyrazol opløst i 400 ml methylenchlorid sættes dråbevis ved 0-5°C 220 g (3,2 mol) isobutyraldehyd, 35 Efter endt tilsætning efteromrøres der i yderligere 2 timerTo 204 g (3 moles) of pyrazole dissolved in 400 ml of methylene chloride is added dropwise at 0-5 ° C 220 g (3.2 moles) of isobutyraldehyde, after completion of the addition, stir for a further 2 hours.
OISLAND
U9809 18 ved 0°C, og derefter dryppes opløsningen ved 0-5°C til 750 g (6,3 mol) thionylchlorid. Reaktionsblandingen får derpå lov at antage stuetemperatur og efteromrøres derefter i 12 timer.At 0 ° C, then the solution is dropped at 0-5 ° C to 750 g (6.3 moles) of thionyl chloride. The reaction mixture is then allowed to reach room temperature and then stirred for 12 hours.
Derpå afdrives opløsningsmidlet i vakuum, og remanensen op-5 tages i carbontetrachlorid og krystalliseres. Krystallerne frafiltreres, moderluden inddampes, og remanensen krystalliseres. Det således fremstillede faste stof forenes med den første fraktion og udrøres med 200 ml carbontetrachlorid.The solvent is then evaporated in vacuo and the residue taken up in carbon tetrachloride and crystallized. The crystals are filtered off, the mother liquor is evaporated and the residue is crystallized. The solid thus prepared is combined with the first fraction and stirred with 200 ml of carbon tetrachloride.
Derefter frafiltreres der, vaskes med 100 ml carbontetrachlorid, 10 og det faste stof tørres ved 40°C i vakuum. Der fås 530 g 1-(1'-chlorisobutyl)-pyrazol-hydrochlorid (91% af det teoretiske udbytte) med et smeltepunkt på 110-114°C.Then filter off, wash with 100 ml of carbon tetrachloride, and dry the solid at 40 ° C in vacuo. 530 g of 1- (1'-chloroisobutyl) -pyrazole hydrochloride (91% of theory) is obtained, mp 110-114 ° C.
Eksempel 3 15 /N=jExample 3 15 / N = j
Cl-CH — I x HC1Cl-CH - I x HCl
Til 68 g (1 mol) pyrazol i 400 ml methylenchlorid sættes 20 der dråbevis ved 0-5°C i løbet af 1 time 175 g (1,2 mol) chloral. Der efteromrøres i 3 timer ved 25°C, og krystallisatet fraskilles ved sugning. Moderluden inddampes, og der fraskilles et yderligere krystallisat ved sugning. De forenede krystallisa-ter opløses i methylenchlorid og sættes ved 10°C i løbet af 25 1/2 time til 250 g (2,1 mol) thionylchlorid i 500 ml methylen chlorid. Der efteromrøres i 18 timer ved stuetemperatur. Derpå inddampes reaktionsblandingen ved 50°C i vakuum. Til rema- nensen sættes 200 ml chloroform, og der inddampes på ny. Efter tilsætning af 200 ml carbontetrachlorid udkrystalliserer pro-30 duktet. Det fraskilles ved sugning og tørres. Der fås 178 g (66% af det teoretiske udbytte) IJ-(1,2,2,2-tetrachlorethyl)--pyrazol-hydrochlorid med et smeltepunkt på 95°C.To 68 g (1 mole) of pyrazole in 400 ml of methylene chloride 20 is added dropwise at 0-5 ° C over 1 hour 175 g (1.2 mole) of chloral. Stir for 3 hours at 25 ° C and the crystallate is separated by suction. The mother liquor is evaporated and a further crystallize is extracted by suction. The combined crystallisates are dissolved in methylene chloride and added at 10 ° C over 25 1/2 hours to 250 g (2.1 mole) of thionyl chloride in 500 ml of methylene chloride. Stir for 18 hours at room temperature. Then, the reaction mixture is evaporated at 50 ° C in vacuo. Add 200 ml of chloroform to the residue and evaporate again. After the addition of 200 ml of carbon tetrachloride, the product crystallizes. It is separated by suction and dried. 178 g (66% of theoretical yield) of IJ- (1,2,2,2-tetrachlorethyl) -pyrazole hydrochloride are obtained having a melting point of 95 ° C.
På tilsvarende måde fremstilles de i tabel I anførte forbindelser.Similarly, the compounds listed in Table I are prepared.
3535
OISLAND
19 14980919 149809
Tabel ITable I
RV>v ? I -CH Y (I)RV> v? I -CH Y (I)
5 R2/ JR2 / J
R3 __ 123 Smeltepunkt (°C)R3 123 123 Melting point (° C)
Eks. nr. R_R R R Y Kogepunkt (°C)_ 10 4 -CH3 CH3 Cl CH3 Cl Olie (xHCl) 5 -CH3 H Cl H Cl kp:60-62/20nib (xHCl) 6 -C2H5 H H H Cl Olie (xHCl) 7 -n-C,H7 Η Η H Cl olie (xHCl) 15 01 8 -CH3 Η Η H Br .kp; 6o“65/2oinb 9 -CH3 Η Η H Cl kp:50-55/20mbEx. No. R_R RRY Boiling point (° C) _ 10 4 -CH3 CH3 Cl CH3 Cl Oil (xHCl) 5 -CH3 H Cl H Cl bp: 60-62 / 20nib (xHCl) 6 -C2H5 HHH Cl Oil (xHCl) 7 - nC, H7 Η Η H Cl oil (xHCl) 15 01 8 -CH3 Η Η H Br .kp; 6o “65 / 2oinb 9 -CH3 Η Η H Cl kp: 50-55 / 20mb
Ved den i beskrivelsen beskrevne fremgangsmåde fremstilles 20 de i den efterfølgende tabel II anførte mellemprodukter med formlen (IV).In the process described in the description, the intermediates of formula (IV) listed in the following Table II are prepared.
Tabel II 25 R’V-» *Table II
-I-IN
N-CH—OH (IV) R3 30N-CH-OH (IV) R3
Elcs· r R1 R2 R3 Fysiske _ konstanter IV-1 CH3 HH H ikke isoleret IV-2 i-C3H7 HH H ikke isoleretElcs · r R1 R2 R3 Physical constants IV-1 CH3 HH H not isolated IV-2 i-C3H7 HH H not isolated
35 IV-3 -CC13 Η Η H smp:109°CIV-3 -CC13 Η Η H mp: 109 ° C
IV-4 CH3 CH3 Cl CH3 smp: 39-44 °CIV-4 CH3 CH3 Cl CH3 mp: 39-44 ° C
0 20 1498090 20 149809
Ud fra de her omhandlede forbindelser med formlen (I) fremstilles der analogt med eksempel 1 ved omsætning med halogen-acetanilider med formlen (VI) de i den efterfølgende tabel (III) anførte forbindelser.From the present compounds of formula (I), by analogy with Example 1, by reaction with haloacetanilides of formula (VI), the compounds listed in the following Table (III) are prepared.
55
Tabel IIITable III
r /M—rR1 x!v-<x’ io R)—^a2 cv) 0-0¾—Hal lr / M-rR1 x! v- <x '(R) - ^ a2 cv) 0-0¾-Hal l
Smeltepunkt 15 El!S' X1 X2 X3 R R1 R2 R3 Hal (°C) n jr« _______ M_ ___ V-2 CH3 6-CH3 H CH3 Η Η H Cl 90 V-3 C2H5 6-C2H5 H CH3 Η Η H Cl 80 20 V-4 CH3 6-CH3 H CH3 Η Η H Cl 95 (xHCl)Melting point 15 El 'X1 X2 X3 R R1 R2 R3 Hal (° C) n yr «_______ M_ ___ V-2 CH3 6-CH3 H CH3 Η Η H Cl 90 V-3 C2H5 6-C2H5 H CH3 Η Η H Cl 80 20 V-4 CH3 6-CH3 H CH3 Η Η H Cl 95 (xHCl)
De nødvendige udgangsforbindelser med formlen (VI) fremstilles ved den i eksempel 1 angivne metode:The necessary starting compounds of formula (VI) are prepared by the method of Example 1:
OISLAND
21 14980921 149809
Tabel IVTable IV
WW
X3/ c - (:¾ - HalX3 / c - (: ¾ - Hal
OISLAND
gfcs. χΐ_X2 X3 Hal | Smeltepunkt 10 vi - 2 CH3 6-CHs H Cl 148 VI - 3 C2H3 6-C2H3 H Cl 133 VI - 4 i-Cj H7 Η H Cl 79 VI - 5 tert.-C4H9 Η H Cl 96 15 vi - 6 c2H3 Η H Cl 103GFC. χΐ_X2 X3 Hall | Melting point 10 vi - 2 CH3 6-CHs H Cl 148 VI - 3 C2H3 6-C2H3 H Cl 133 VI - 4 i-Cj H7 Η H Cl 79 VI - 5 tert.-C4H9 Η H Cl 96 15 vi - 6 c2H3 Η H Cl 103
Vi - 7 CH3 Η H Cl 109 vi - 8 CH3 3-CH3 ‘ H Cl 135Vi - 7 CH3 Η H Cl 109 vi - 8 CH3 3-CH3 'H Cl 135
Vi - 9 CK3 5-CH3 H Cl 154 20 Vi - 10 CH3 4-0¾ 6-CHs Cl 177 VI - 11 c2H3 4-CH3 6-CH5 Cl 134 vi - 12 sek.-C4H9 Η H Cl Olie VI - 13 Η Η H Cl 132 25Vi - 9 CK3 5-CH3 H Cl 154 20 Vi - 10 CH3 4-0¾ 6-CHs Cl 177 VI - 11 c2H3 4-CH3 6-CH5 Cl 134 vi - 12 sec-C4H9 Η H Cl Oil VI - 13 Η Η H Cl 132 25
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2835158 | 1978-08-10 | ||
| DE19782835158 DE2835158A1 (en) | 1978-08-10 | 1978-08-10 | SUBSTITUTED PYRAZOLE DERIVATIVES AND METHOD FOR THE PRODUCTION THEREOF |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK333679A DK333679A (en) | 1980-02-11 |
| DK149809B true DK149809B (en) | 1986-10-06 |
| DK149809C DK149809C (en) | 1987-03-23 |
Family
ID=6046746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK333679A DK149809C (en) | 1978-08-10 | 1979-08-09 | 1-ALKYL-SUBSTITUTED PYRAZOLD DERIVATIVES |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0008056B1 (en) |
| JP (1) | JPS5524184A (en) |
| BR (1) | BR7905110A (en) |
| DE (2) | DE2835158A1 (en) |
| DK (1) | DK149809C (en) |
| HU (1) | HU182849B (en) |
| IL (1) | IL57996A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ238917A (en) * | 1990-07-20 | 1994-04-27 | Buckman Labor Inc | Microbicidal compositions containing a 1-hydroxymethylpyrazole derivative |
| USD602486S1 (en) | 2007-08-31 | 2009-10-20 | Apple Inc. | Electronic device |
| USD615083S1 (en) | 2008-04-07 | 2010-05-04 | Apple Inc. | Electronic device |
| USD684571S1 (en) | 2012-09-07 | 2013-06-18 | Apple Inc. | Electronic device |
| USD681032S1 (en) | 2012-09-11 | 2013-04-30 | Apple Inc. | Electronic device |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3293261A (en) * | 1964-07-06 | 1966-12-20 | Norwich Pharma Co | 1-isopropyl-3-phenyl-5-aminopyrazole |
| DE1296637B (en) * | 1964-11-04 | 1969-06-04 | Merck Ag E | 4- (3-Piperazinopropyl) pyrazoles, their salts and processes for their preparation |
| DE1620016C3 (en) * | 1966-07-02 | 1979-08-30 | Merck Patent Gmbh, 6100 Darmstadt | 3- (Piperazinoalkyl) pyrazoles and processes for their preparation |
| ZA71331B (en) * | 1970-02-19 | 1971-10-27 | Upjohn Co | Organic compounds and process |
-
1978
- 1978-08-10 DE DE19782835158 patent/DE2835158A1/en not_active Withdrawn
-
1979
- 1979-07-30 DE DE7979102705T patent/DE2960836D1/en not_active Expired
- 1979-07-30 EP EP79102705A patent/EP0008056B1/en not_active Expired
- 1979-08-07 IL IL57996A patent/IL57996A/en unknown
- 1979-08-08 JP JP10033279A patent/JPS5524184A/en active Granted
- 1979-08-09 DK DK333679A patent/DK149809C/en not_active IP Right Cessation
- 1979-08-09 BR BR795110A patent/BR7905110A/en unknown
- 1979-08-10 HU HU79BA3829A patent/HU182849B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| IL57996A0 (en) | 1979-12-30 |
| DK149809C (en) | 1987-03-23 |
| IL57996A (en) | 1983-03-31 |
| DK333679A (en) | 1980-02-11 |
| EP0008056B1 (en) | 1981-09-16 |
| HU182849B (en) | 1984-03-28 |
| EP0008056A1 (en) | 1980-02-20 |
| BR7905110A (en) | 1980-05-06 |
| DE2960836D1 (en) | 1981-12-03 |
| DE2835158A1 (en) | 1980-02-21 |
| JPS649317B2 (en) | 1989-02-16 |
| JPS5524184A (en) | 1980-02-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2055836C1 (en) | Derivatives of pyrazole or their salts with bases | |
| JP2813895B2 (en) | 3-Substituted phenylpyrazole derivatives or salts thereof, process for producing the same, and herbicides | |
| JP3044402B2 (en) | Herbicidal carboxamide derivatives | |
| CA1283116C (en) | Herbicidal 4-benzoyl-1-alkyl(alkenyl)-pyrazoles | |
| US4432994A (en) | Pesticide compounds, compositions and methods | |
| JP3478830B2 (en) | Pyrazole derivatives | |
| US4230481A (en) | Pyrazole derivatives useful as a herbicidal component | |
| BR112018011518B1 (en) | METHOD OF PRODUCTION OF AROMATIC STARCH DERIVATIVE | |
| RU1837768C (en) | Method for insect control | |
| CS204050B2 (en) | Means for protection of cultural plants against damaging by the herbicide active thiolcarbamates and/or acetanilides and method of making the n-dichloracetyl-1,2,3,4-tetrahydrochinaldine | |
| DK149809B (en) | 1-ALKYL-SUBSTITUTED PYRAZOLD DERIVATIVES | |
| HUT61534A (en) | 3,5-dioxo-3,4,5,6-tetrahydro-1,2-oxazine derivatives, herbicidal, acaricidal and plant growth regulating composition comprising such compounds as active ingredient, process for applying the composition and for producing the active ingredients, as well as 2-nitro-4-(trifluoromethoxy)-benzoic acid intermediate | |
| KR20020077414A (en) | Perfluoroisopropylbenzene derivatives | |
| JPS6219402B2 (en) | ||
| CN102438980A (en) | Method for producing 2-halogenomethylphenyl acetic acid derivatives | |
| US4098894A (en) | Triphenyl-1,2,3-triazolyl-(1)-methanes, and compositions and methods for combating fungi and bacteria employing them | |
| JPH0575746B2 (en) | ||
| JP2003113168A (en) | Nematocidal trifluorobutene derivative | |
| HU196955B (en) | Process for producing substituted phenyl-hydrazine derivatives | |
| JPH02256646A (en) | (hetero)aryloxynaphthalene derivative, preparation thereof, new (hetero)aryloxynaphthylamine therefrom, and use of said amine as herbicide | |
| US5623076A (en) | Process for the preparation of chloromethylpyridines | |
| US4369056A (en) | Substituted pyrazolylmethyl-haloacetanilide compounds and herbicidal compositions | |
| JPH0822853B2 (en) | Pyrazole-4-carboxylic acids and method for producing the same | |
| JP3116171B2 (en) | Method for producing pyrazole derivative, intermediate thereof, and method for producing the same | |
| JPH01230562A (en) | Phenyltriazole derivative and insecticide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PBP | Patent lapsed |