CA1201716A - 1-substituted imidazole-5-carboxylic acid derivatives, their preparation and their use as biocides - Google Patents

1-substituted imidazole-5-carboxylic acid derivatives, their preparation and their use as biocides

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Publication number
CA1201716A
CA1201716A CA000440172A CA440172A CA1201716A CA 1201716 A CA1201716 A CA 1201716A CA 000440172 A CA000440172 A CA 000440172A CA 440172 A CA440172 A CA 440172A CA 1201716 A CA1201716 A CA 1201716A
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Canada
Prior art keywords
denotes
formula
c1
carboxylic acid
plants
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CA000440172A
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French (fr)
Inventor
Thomas Maier
Roland Schmierer
Klaus Bauer
Hermann Bieringer
Helmut Burstell
Burkhard Sachse
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Hoechst AG
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Hoechst AG
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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D233/00Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54Heterocyclic 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
    • C07D233/66Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/90Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES, AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/501,3-Diazoles; Hydrogenated 1,3-diazoles

Abstract

Abstract of the disclosure:

The invention relates to imidazole-5-carboxylic acid derivatives in which the imidazole ring is substitu-ted in the 1-position by a 2,6-dialkylphenyl radical and which have the formula in which X = O, S or N.
The compounds are obtained from appropriately sub-stituted bisformyl esters, either by reacting the latter with formamide or with ammonium acetate or by subjecting aminomethylene compounds prepared from the bisformyl est-ers to an intramolecular condensation reaction.
The new substances can be used as biocides, in particular herbicides, fungicides and growth regulators.

Description

~%~

- 2 -HOE 82/F ~01 It ;s known that 1-benzhydrylimidazole-5-carboxy-lic acid d~rivatives possess fungicidal and also herbici-dal activity (German Offenlegungsschrift 2,732,531).
It has now been found, surprisingly, tha~ imida-zole-S-carboxylic acid derivatives in which ~he 1-position of the imidazole ring is substituted by a ~,6-dialkylphe-nyl rad;cal, ;.eO der;vatives of 1~t2,6-d;alkylphenyl)-imida~ol~-5-carboxylic acid, wh;ch, moreover~ can be pre-pared more easily than the àbove 1-ben~hydryl compounds, are also very good fungicides and also display remarkable herbicidal and growth-regulating properties~ and that it is furthermore poss;ble to obtain 1-substituted im;dazole-S-carboxyl;c acid derivatives in a simpler manner than that hitherto described.
The present invention therefore relates to 1-sub-stituted ;midazole-5 carboxylic acid derivatives of the forrnula tI) R 2 ~ C ~ X _ ;~1 t I ) in ~hich X is ~, S or Nr particularly 0~
R1 denotes hydrogen~ phenyl, C2- to C6~alkenyl, preferablY C3-alkenylj or C1- to C12-alkyl, in particular C1- to c6-alkyl, it being possible ,or the alkyl group to be monosubstituted to trisu~-stitu~ed - also ~ith different substituents - pre-ferably monosubstituted, by C1- to C6-alkoxy, in particular C~- or C2-alkoxy or C1- to C3-d;alkyl-am;no or by halogen, and two îdent;cal or d;ffer-ent radicals R1 being a~tached to N if X = N.
If X ~ O or S, R1 can also represent the cation of a metal of the Io II or VII group of the peri-odic system, for instance 7n, Cu or Mn, preferabLy an alkal; metal cation, or ammonium.
R2 denotes a radical of the formula ~II) ,~
<~)6~ tII~
/~

în ~h;ch R3 and ~4 îndependently of one another represent a C1~ to C4-alkyl group and the R5s are ;dentical or different radicals be-long;ng to the ~roup compr;s;ng hydrogen, C~- to C4-alkyl, C1 to C4-alkoxy and halogen, prefer-ably hydrogen and alkyl, but part;cularly hydro-` gen.
2~ The follo~ing may be mentioned as preferred radi-cals R2: 2,6-dimethylphenyl, 2-methyl-6 ethylphenyl, 2,4,6-tr;methylphenyl, 3-chloro-2rb-dim~thylphenyl, 2,6-d;isopropylphenyl and 2,6-diethylphenyl.
The invention also reLates to processes for the preparation of the new compounds and to their use as bio-cides, in particular fungicides, herbicides and growthregulators~
The start;ng mater;als for the synthesis of the compounds~ accord;ng to the invention, of the formula I
in ~hich R2 has the meaning indicated above and also those in which ~ additionally represents an alkyL group having 1 to 12, preferably 1 to 6, carbon atoms or a radi-cal of the formulae III or IV

( R6 ~ ~: H-- ~

5 ~ (R )5 CIII) ~IY) in wh;ch the R6s are ;dentical or different radicals de-notin~ hydrogen, halogen, C1- to C~-alkoxy or C1- to C~-alkyl, are b;sformyl esters or the enol form thereof of the formulae ~V~ or tVa), respectively n ~ oR7 ~ o~7 ~ - h~ 2 N~

(V) tVa) in ~hich R2 represents the radicals mentioned above and R7 represents one of thP radicals R1 defined abovef pre~erably methyl or ethyl and especially ethyl~ but not H~ a meta~ or ammoniumO These esters can be prepared 12(?17i6 readily by known processes from the corresponding amines by N-alkylating the latter with halogenoacetic acid esters in the presence of organic or inorganic bases, then N~
formylating the products ~ith formic acid and then carry-;ng out a C-formylation ~ith formic ac;d esters in the presence of strong bases such as sodium hydride or alkali metal ~lcoholates.
In addition to the known processO ~hich, however, ;s tedious, three process variants are available fQr the preparation of the 1~substituted imidazoLe-5-carboxylic ac;d der;vat;ves from the b;sformyl esters:
In process variant a) the b;sformyL esters (V) or (Va) are reacted w;th a carboxam;de having 1 to 3 carbon atoms, most su;t2bly formamide, wh;ch acts at the same t;me as the solvent, advantageously in the presence of strong ac;ds, preferably us;ng molar quanti~ies of strong m;nera( acids, such as concentrated hydrochloric ac;d, at temperatures of 50 to 25û, preferably 120 to 170C, to g;ve the ;midazoles. The progress of the react;on can be foLlowed easily by means of chromatography~
In variant b) the compounds of the struc.ure tV) or t~a) are reacted with a 5-fold to 30-fold, advanta~e-ously 10-fold to 20-fold, molar excess of ammon;um acet-ate ;n a 5 to 50-fold, especially 20 to 40-fold, molar amount of glacial acetic acid at temperatures of sa ~o 1~0C, particularly advantageously at the boiling point of the react;on mixture.
In process c) the am;nomethyLene compounds VI

7~6 ~ ~R

R - t~
H ~ ~ ~ tVI~

~ l~t~
which can be prepared readily by known processes from the compounds ~V~ or (Va~ by reaction wi~h ammon;a or ammonium salts are subjected generally without ~he necessity for S them to be ;solated, to an intramolecular condensat;on reaction which is carried out at such a temperature that the product is removed by distillation at the same time.
It is particularly advantayeous to regula$e the pressure in the d;st;llation at such a level that distillation can be carr;ed out at a bath temperature of 130 to 250C.
S;nce products conta;ning ~he radical ~R7 ~bear-;ng in mind the limitation in respect of R7 ind;cated above) are formed ;n all cases, this radical is, if de-sired, substituted or modified in accordance with gener-ally kno~n methods by other radicals out of those men-tioned for X and R1, for example by saponificat;on, trans-esterlf;cation or am;dation. F;nally, ;f appropr;a~e, the poss;bil;ty of forming a salt or complex salt of, or quaterniz;ng, the imidazole rin~ which has a basic re-~0 act;on~ can also be exploited by reacting the product in aknown manner w;th organic or inorclan;c acids, with metals of the groups Ib~ IIb, Ivb or VlII of the periodic system~
for example Cu~ Zn or Sn, or with alkyl or phenacyl halides.
In ~eneral, the desired compounds are ob~a;ned ;n ~S ~ery high purity and in good yielcls by the procedure ac-cording to ~he ;nvention~ This was surprising and could L'7~6 not have been foreseen. It ~ou~dO on the contraryr have been expected that the ester grouping -oR7, which is chemically relatively labile, would be destroyed by saponi-fication or by amide formation~ even before the cycliza-tion reaction, under the conditions of the reaction, suchas, for exarnple~ heating to relatively high temperatures with molar amounts of concentrated hydrochloric acid ;n formanlicle.
Compared with the known method for the preparation of 1-substituted ;midazole-5-carboxyl;c ac;d derivatives~
in ~hich the b;sformyl compounds are cycl;zed to give the 2-mercapto compound by means of potassium th;ocyanate w;th eliminat;on of the N-formyl group~ and the mercapto ~roup is then removed by oxidation in a second react;on stage ~R~ G. Jones, J. Am. Chem. Soc. ~1 (1949), 6~4~, the pro-cedure claimed const;tutes a considerable ;mprovement, since a single-stage reaction takes the pLace of the two-stage reaction, the elimination of two aux;liary groups, ~hich is unsatisf3ctory from an economic point of viewf ~Q is avoided and, last but not least, the inevitable forma-tion of undesirable by-products does not take place.
As already mentioned, the new 1-subst;tuted ;mi-dazole-5-carboxyl;c acid derivatives can be used as b;o-cides. They are d;stinguished by an excellent fungicidal act;on~ Fungo-d pathogens wh;ch have already penetrated into the plant t;ssue can be successfully combated in a curat;ve rnanner. Th;s is part;cularly ;mportant and ad-vantageous ;n the case of fungal cl;seases ~n;ch can no ~onger be combated effect;vely using the otherw;se custorn-~ZQ~7:~6 ary fungicides after infestation has taken place. ThPspectrum of action of the new compounds embraces a large number of different phytopathogenic fungi, such as, for example, Piricular;a oryzae, Plasmopara viticola, various species of rust and above all Venturia inaequalis~ Cerco-spora beticola and powdery mildew fungir in the cultiva-tion of fruit, vegetables, cereals and ornamental plants.
The compounds are also su;table for use in tech-n;cal fields, for example in wood preservatives, as pre-servatives in paints and in coolant-lubricants for metal ~ork;ng or as preservatives in drilling and cutting oils.
The agents can be used as wettable powders, emul-sifiable concentrates, sprayable solutions, dusting agents~
dressing agents~ dispersions, granules or microgranulesr in the customary formulations~
Wettable powders are preparations ~hich can be uniformly dispersed in ~ater and which, as well the act-;ve compound, also contain~ in addition, if ap'propriate, to a d;luent or inert substance, wett;ng agents, for ex ample polyoxethylated alkylphenols, polyoxethylated fatty alcohols, alky'lsulfonates or al~ylphenylsulfonates, and d;spers;ng agents, for example sodium ligninsulfonate, sodium 2,2'-d;naphthylmethane-6~6'-disulfona~e, sod;um dibutylnapthalenesulfonate or the sodium salt of oleyl-~ethyltaur;de. They are prepared ;n a customary manner,for example by gr;nd;ng and mixing the co~ponentsO
~mulsifiable concentrates can be prepared, for .
example~ by d;ssolving the act;ve compound in an inert or~an;c solvent~ for example bu~anol, cyclohexanone, di-71~

methylformamide, xylene or h;gher-bo;l;ng aromatic com-pounds or hydrocarbons, with the addition of one or more emulsifiers. In the case of liquid active compounds, the quota of solvent can also be completely or partially omit-S ted~ The following are examples of emulsif;ers which canbe used: calcium alkylarylsulfonates~ such as Ca dodecyl-benzenesulfonate~ or nonionic emulsi~iers, such as fatty acid esters of polyglycols, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers~ propylene oxide/ethylene ox;de condensat;on products, fatty alcohol/propylene ox-ide/ethylene oxide condensat;on products~ alkyl polyglycol ethers, fatty acid esters of sorbitan, fatty ac;d esters of polyoxethylenesorbitan or esters of polyoxethylenesor-bitol Dusting agents can be obtained by grinding the act;ve compound w;th f;nely divided solid substances, for example talc, natural clays, such as kaol;n, bentonite or pyrophillite, or diatomaceous earth.
Granules can be prepared e;ther by atomizintJ the active compound onto an adsorptive granulatecl inert mate-r~al or by applying con~entrat;ons of active compound by means of b;nders, for example polyv;nyl alcohol, sodium polyacrylate or mineral oils~ to ~he surface of carriers, such as sand, kaollnite or a granulated inert material~
Su;table active compounds can also be granulated in the ~manner customary for the preparation of fertil;zer gran ules, ;f des;red as a mixture ~;th fertili2ers~
The concentrat;on of act;ve compound in wettable powders is, for example~ about 10 to 90% by weigh~; the 7~6 remainder up to 100% by weight is somposed of custornary formulation ingredients. Xn the case of emulsifiable con-centra-tes the concentration of ac;ive compound can be about 10 ~o 80% by ~eight~ Formulations in the form o~
dusts contain ;n most cases S to 20~ by weight of active compound, wh;le sprayable solut;o~s contain about 2 to 20X by weight~ In ~he case of granules, the content of active compound depends in some cases on whether the act~
ive compound is in a liquid or solid form and on the gran-ula~ing auxiliaries, fillers and ~he like which are used.
In add;tion, the active compound formulations men-tioned can contain the adhesives, we~ting agents, dispers-ing agents, emulsifiers, penetration agents, solvents, fillers or carriers Hhich are cus~omary in a particular case~
For appl;cation, the concentrates present in a commercially available form are opt;onally diluted in a customary manner, for example in the case of wettable powders, emulsifiable concentrates, dispersions and, in some cases, also microgranules, by means of water. For-mulations in the form of dusts and ~ranulated Formulations and also sprayable solut;ons are usually not diluted fur-ther ~;th additional inert substances before use.
M;xtures or mixed formùlations containing other active compounds, such as, for example, insecticides~ aca-ricides, herbicides, fertilizers, ~ro~tth regula~ors orfun~;cides, are also possible if appropriate Particu-larly in the case of m;xtures with fungicid~s, it is also possible in sorne cases to achieve synergis-tic increases in activity.

A few examples of formulations may be listed be-l o~ :
A dusting agent is obta;ned by m;x;ng 10 parts by ~/e;ght of active cornpound and 90 parts by we;ght of talc or an inert substance and comminuting the mixture in a beaker mill.
A wettable powder which can be dispersed readily ;n water is ootained by mix;ng 25 parts by weight of act-;ve compound, 64 parts by we;ght of kaolin-contain;n3 quartz as an inert material, 10 parts by weight of pot-assium ligninsulfonate and 1 part by weight of sodium sa~t of oleylmethyltauride as a ~etting and dispersing agent, and ~rindin~ the mixture in a pin mill~
A dispersion concentrate which can be readily dis-persed in water is obtained by mixing 20 parts by weight of act;ve compound ~;th 6 parts by~ eight of an alkylphe-nol polyglycol ether ~Triton X 207~, 3 parts by weight of ;sotridecanol polyglycol eth~r (8 FO) and 71 parts by ~0 we;~ht of a paraff;n;c m;neral o;l tbo;ling range, for exarnple, approx. 255 to above 377~)~ and ~r;nd;ng the m;xture to a fineness less than 5 microns in an attrition ball mill.
` An emulsifiable concentrate is obtained fro~ 15 parts by weight of active compound, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of ox-ethylated nonylphenol (10 E0) as emulsifier~
Surprisingly, however, the cornpounds according to the invention also possess an excellent herbicidal ac~ion 7~

... . ~ .

7~6 in the pre~emergence and post-emergence techniques against annual and perennial ~eeds. Depending on the dose, this results in ;nhibition of plant gro~h or complete destruc~
tion of the plants~
S The species which can be combated include econo~
mically important grass-like weeds, such as Se~aria (fox-tail), Digitaria (fingergrass), Echinochloa (cockspur srass), Alopecurus tslender foxtail)~ Avena (wild oats)~
Cyperaceae (cyperaceae) and Agropyron (couchgrass) and Sorghum (sorghum). In addition, dicotyledonous ueeds of economic importance, such as Matr;caria ~chamomile), Chrysanthemum (chrysanthemum), ~maranthus ~amaranth), Galium ~cleavers), Abutilon (China jute) and Sida, are also controlled. In add;tion, at herbic;dally effective applicat;on rates the new compounds protect many species of crop plants, so that they can be employed in important major crops, such as, for example, mai~e, rice, cereals~
soya, cotton and rape~ for selectively combatin~ undesir-able plant growth.
Thus it is possible, for example, to combat e~fect;vely by means of the new agents cockspurgrass and amaranth in maize or f;ngergrass, foxtail, China jute and Sida in soya and cotton crops; but it is also possible to use the new compounds successfully for combating important weeds, such as, for example~ cockspurgrass~ ~ild oats, slender foxtail.~ cyperaceae species and cleavers, in cereal crops and in r;ce.
~ epending on the dosage used, typical growth-re~ulating effec~s can also be achieved using the ne~d ~2~

compounds; thus i~ ;s poss;ble, for examp~e, to affect the growth of the plants, and also the const;tuents of the plants. The compounds are therefore suitable as gro~th regula~ors in crops of useful plants~ such as, for example, cereals, maize~ sugar caneD tobacco, rice and sorghum~ On the other hand, it is also possible ~o con-trol plantat;ons~ for instance cultivated lawns~ or plant communities on the edges of paths and roads and also orna-mental plants.
In this respect the compoLInds according to the ;nvent;on can also be advantageously combined with known gro~th regulators, such as, for example, chloroethylphos-phonic ac;d.
When used as fungicides, the application rate of the compounds according to the invention is generally 0.125 to 1.0 kg/hectare. When used as growth regulators, concentrat;ons between 0.15 and 5.0 kg/hectare, prefer ably 0.5 to 2.5 kg/hectare, are suitabLe.
The follo~ing examples serve to illustrate the ;n~ention further:
Preparation examples Exampl~ 1 (Example of process variant 2) Ethyl 1-~2~6-d;ethylphen~l)-;m;dazole-S-carboxylate 17~8 g tO.06 mole) of ethyl 2-(2,6-diethyl N-formylan;lino)-~-hydroxyacrylate were heated w;th stir-ring together with 1D ml of concentrated hydrochloric acid and 50 ml of formamide for 8 hours at an oil bath ., .

temperature of 160C (internal temperature 140C). After cooling, the product ~as extracted by shaking with a mix ~2~
, ture o, 100 mL of wa~er and 100 ml of diisopropyl ether, the organic layer was separated off and the aqueous phase was extracted once more with diisopropyl ether. The com b;ned organic phases ~ere dried over sodium sulphate and S evaporated~ 14.~ g ~90X of theory~ of the titLe compound were obtained in the form of a colorless oîl of boiling po;nt 145C/0.01 mm Hg.
H-NMR ~oO MHz, COCl3) ~ = 1006 (t, J ~ 7.5 Hz, 6H, Ph-CH2~C~3)~ 1.14 ~t~ J - 7.5 Hz, 3H, -OCH2-C~3); 2-23 (q, J =
7.5 Hz, 4H, Ph-C~); 4.10 (q, J ~
705 Hz, 2H, -O-CH2_); 7.1-7.~
~m, 3H, Ph); 7.50, 7.85 ppm t2s, each 1H, imidazole) Example 2 (Example of process variant b~
Methyl 1-t2-ethyl~S~methylphenyl)-im;dazole S-carboxylate _ A m;x.ture of 15 g tO~06 mole) o~ methyl 2-t2-ethyl-6-methyl-N-formylanilino~-acrylate, 65 ~ of ammonium acet-ate and 100 ml of glacial acet;c acid was kept at reflux ~0 temperatur~ for 8 hours, a further 50 g of ammonium acet-ate were then added and the mixture was allowed to react for a further 4 hours under the same cond;tions. 300 ml water were then added to the react;on mixture, which was extracted t~;th twice 100 ml of toluene. The organic 2 phase was drie~ over sodium sulfate, concentrated and chromatographed over silica gel~ 9.2 g ~67X of colorless tablets of meltin~ point 56 to 57C were obtained.
1H~MR (~ MH~, cocl33 ~ O5 ~t, J = 7.5 Hz, 3H, Ph-CH2~CH3); 1.95 (s, 3~1~ Ph-CH3~;

12~?17 1 6 2025 ~q, J - 7.5 H~.9 2H, Ph-CH

3.70 (s~ ~H~ -OCH3); 7.1-7.3 (m~ 3H, Ph); 7.500 7.88 ~2SD
each 1H~ imida20le) ppm.
Example 3 ~Example of process variant c) Ethyl 1-(2~6-diethylphenyl)-imîdazole~S~carboxylate __ _ _ _ _ _ _ __ __ 5.5 9 tO.g19 mole) of the b;sformyl compound em-ployed in Example 1 were heated for 1 hour a~ b5 to 70C
together with 10 9 (0.1 mole) of ammonium carbonate in 1~ 100 ml of xylene. During th;s time ammonium carbonate is evolved by subl;mation, and the aminomethylene compound is formed. In order to remove the excess ammonium car~
bonate co~pletely from the reaction mixture, the tempera-ture is then increased to 120C. The m;xture is allowed to cool, the solvent is removed in vacuo and the residue ;s heated ;n a h;gh vacuum ~0.01 mm Hg~, the desired ethyl 1-(2,~-diethylphenyl)-imidazole-5 carboxylate distilling off from 130C~ Yield 4.3 9 (80%).
Examples ~ to 28 The compounds listed ;n the table below were pre-pared by the processes described in Examples 1 to 3. Col-umn 3 o~ the table shows the appropr;ate process. In the event that the rad;cals ;nd;cated. under -X-RI are other ~han -OCH3 or -OC2H5, these rad;cals werP introduced in accordance w;th known processes via the particular acid, ~Ihich is obtained by saponifyins the ester ~X~R1=OH).

cn . cn : I
.e 6 . E E E
O ` ~.~ C~ ~ O j ~ ~3 0 0 0 ~ 0 Q
m J

., C~
Q
~ ~ X, ., V ~
O C ~ O
O ~- X Z

~ ~ , C`; , m ~ n u~ u~
"= T ~ '~ 1 X

X o oo O ~ O O u c ~ _ 2 t_~ ~
~-- .
r~

C~ U U
~, , .
~ ~ n ~ r~ r~ ~ n ~ I --' -- I
c :~ X ~ N ~ C`~l ~ O ~ L'`~ 0 ~ O . t~ r~
w Z

Obtained xample - ~ ~ in~~accord- , No. ' ~ 0 ~ ~ f XR1 ance~~ith NJ ~`.p. ~), or ~.p. ~) R R ExampLe No~

~3' R~ ft- XF3 17 C2;~5 C2i~ H O CH(CH3) . 1C C2i~5 C2l~5 H O-CH2-CH-CH2 ~ OiL
~ C~1~5 C21~5 H -(C~12)7-c~3 ;~ ~. C2~5 C l! H -Cll2-cll2-D ~H3 2~ .c2~ 2 5 H o~Cl~2-cl~2-N(c2~
22 - i-C3H7 i-C3t~? UH ~ 232 ~3 i C3H7 i 3 7 OCH3 1 128 - 30 24 i C3~l7 i-C3H7 ~C21~5 3 129 - 30 . i 3 7 i C3 7 H ( 2)2 ~ OiL
C3H7 i C3~7 H C-C~(CH3)2 ~ 95 27 i-~H7 3 7 ~ o_(CI~2)2-CH~CH3)2 28 . ~-C3~l7 i-C3i~7 H N-(C2H5)2 ~ diL

-" ~2~

' 18 -Bi~logical examples Example 1 Wheat plants in the three leaf stage are strongly inocula~ed with conidia of wheat powdery mildew (Erysiphe graminis) and are placed in a greenhouse at 20C and a relative humidity of 90 to 95%. 3 days after inoculation~
the plants are sprayed until dripping wet w;th the com-pounds to be tested in active compound concentrations of 500~ 25û and 125 g/liter of spray liquor. After an ;n-cubat;on time of 10 days, the plants are examined forat~cack by wheat po~dery mildew. The degree of attack is expressed ;n X of leaf area attacked~ relative to untrea-ted, infested control plants ~- 100% attack). Table I
shows the results~
Table I

Compound accord- X of leaf area attacked by-wheat powdery milriew at ing~t'o Example ... mg of active ~ompound/li'ter of spray liquor-No. , 500 ~

,~ . O O
1a . tl O n 16' O . O O
17 0 O ~ O

23 t~ O

.6 0 ~ D O

untreated, inf,ested plants ~o ... .~ ... , -, . .

~2~716 Example II
B3rley plants in the three-leaf stage are strongly inoculated with conidia of barley powdery mildew ~Erysi-phe graminis sp. horde;) and are placed in a greenhouse at 20C ancl a re'ative humid;ty of 90 to 95%. 3 days after ;noculation, the plants are sprayed until dr;pping wet with the co~pounds to be tested in active compound concentrations of 500, ~50 and 125 mg/li~er of spray L;quor. After an incubat;on time of 10 days, the plants are exam;ned for attack by barley powdery m;ldewD The degree of attack ;s expressed as % of leaf area attacked, relative to untreatedO infested rontrol plants (= 100%
attack)O The result is shown in Table IIo Table II

Compo~nd YO of leaf area attacked by barley po~dery mildew at ~cording to mg-of acti~e compounJ/liter of spray Liquo-r Example No.

~5 0 . O O
~6 0 0 ~7 D 0 0 18 ~ ~
23 ' 0 D

26 0 ~ U

` untreated, 10 infested plants 7~6 Example III
Cucumber plants (variety Delikatess) ;n the two~
leaf sta~e are inoculated strongly ~ith a conidia suspen-sion of curcubits powdery mildew ~Erysiphe cichoracearum).
S After the spore suspens;on has dried on for 30 minutes, the plants are placed in a greenhouse at 22C and 90%
relat;ve hum;dity. 3 days after infestat;on, the plants are sprayed untiL dripping wet with the substances tv be tested in the active compound concentrations mentioned in Table III. Assessment is carried out after 10 days.
The degree of attack ;s expressed as % of leaf area at-tacked, relative to untreated, infested control plants t- 100X attack). The result is shown in Table III~
Table III

Compound ~ % of leaf area attacked by curcubits powdery mildew according to at ... mg of active compound/liter of spray liquor Exampl~ No.
500 250 1~5 ~5 0 D
16 ~ o 0 1~ D 0 n 23 0 ~ 0 0 ~ 0 ~5 ~ ~ ` 0 ~7 0 0 untreated, ;nfested plants ~00 .... .. , , .. ;

Example IV
Appie stocks of the variety EM IX ;n the fcur-leaf stage are strongly infested with a conidia suspen-sion of apple powdery mildew ~Podosphaera leucotricha)~
The plants are then moved ;nto an a;r-cond;tioned cha~ber at 20C and a relative hum;dity of approx. 100X ~or 16 hours. They are then placed in a greenhouse at Z2C ancl a relat;ve humidity of 85%~ 3 days after infestation, the plants are sprayed un~il dripping wet with the com-pounds to be tested in ~he act;ve compound concentrationsmentioned in Table IVo The powdery mildew attack is as-sessed after 2 to 3 weeks, and the degree of attack i5 expressed as a % of leaf area attacked, relative to un-treated, infested control plants t= 100% attack). Table IV shows the results~
Table IV

Compound % of leaf area attacked by apple powdery mildew at ~according~to ... mg of active co~pound/liter of spray liquor Example No. 1000 5D0 ~5D 1~;
~0 12 Q n o o ~7 o 0 0 0 untreated, infested plants 1DC

Example V
EM IX apple stocks in the -four-leaf stage were treated until dripping ~et with the compounds to be tes-ted in appl;cation concentrations of S00~ 250 and 125 m0 of active compound/liter of spray l;quor~ After the coat~
ing of active compound had dried on~ the plants were 1~?1~716 strongly infested with conidia of apple scab tVenturia inaequalis)~ and were placed in a dripping we~ state in an air-conditioned chamber haYing a ~empera~ure of 22C
and a relati~e hum;dity of 100%o After an infestation time of 48 hours, the plants were then moved into a green-house at 1~DC and a relat;ve humid;ty of ~5 to 100%.
They ~ere examined for attack by apple scab ~Venturia inaequalis) after an incuba~ion time of 1i days~ Assess ment was carried out in the customary manner by visual inspection. The degree of attack was expressed as % of leaf area attacked, relative to untreated, infested plants, and ;s shown in Table V.
Table V

15 Compound % scab attàck at .. mg af açtive compound/liter according to of spray ~-iqu~r Example No. 50~ 250 125 16 0 0 o 1 a 2.n 2S n . a ~6 O n ~7 0 O ` O
;nfe~ted, untreated ~lants 10 2~
ExampLe VI
l~heat plants were treated ~ith the compounds to be tested ;n application concentrat;ons of S00, 250 and 125 m~ of active compound/liter of spray liquor. After 3~2~7~

the coating of active compound had dried on~ the plants were inoculated with spores of whea~ brown rust (Puccinia tritic;na~, and were placed in a dripping wet state ;n an air-conditioned chamber at 20C and 100% relative humi~
ditya 24 hours later the plants were brough~ back into a greenhouse and were examined there 1~ days after inocu~
lation for attack by wheat brown rus~. The degree of attack was expressed as % of leaf area attacked, relative to untreated~ ;nfested control plants t- 100% attack).
~0 Table VI sho~s the good action of the new compoundsY
Table VI

Compound- - X of leaf area at-tacked by brown rust at .0 mg according~to~ of active compound/liter of-spray liquor Example No. 5~0 250 ~25 ~5 ~ a . o 16 ~ 0 ~7 Q a ` o untreated~ -infested plants 1D0 Example VII
Seeds of weeds and grass l;ke ~ee~s are sown in sandy loam 50i l in plastic pots (diameter 9 cm) and are lightly covered with soiL. The compounds to be tested~
formulated as wettable powders or emulsion concentrates, were sprayed onto the surface of the soiL in the form of aqueous suspens;ons or emulsions. The quantity of water appl;ed peP pot was equ;vaLent to 600 literlhectare. Af-ter the treatmentS the test pots ~ere placed in a green-- ~4 house and the test plants were cultivated under good con-ditions for gro~th (temperature 23 to 25C; relative humidity ~0 ~o 80%). After approx~ 3 weeks, the pLant damage was assessed in accordance with the follo~ling rat-in~:
0 = no act;on 3 = 40 to 60% dama~e 1 = 0 to 20% damage 4 -- 6G to ~0% damage 2 ~ 20 to ~iO% dama0e 5 = 80 to 100~ ~amage The assessment numbers of the herb;cidal activity of the new compounds are listed ;n Table VII. The figures show that the substances possess an excellent herbicidal act;on in the pre-e~ergence technique against both mono-cotyledonous and dico~yledonous weeds.
Table VII ``

Compoun~ Dose (kg of Herbicidal act;vity in the pre-emergence according active substarn~ce technique for to Example per hectare) No. AMR GAA SAL CY~

'2.'4 5 5 4 S
9 2.~ 5 5 3 ' 5 11 2.4 !i 5 4 4

4 4 5 2.4 5 - 4, 5 5 17 ~.4 S 5 5 5 1~3 2~4 5 . 5 4 5 Z!O` 2.4- ` 5 5 5 2:~ 2~ 4 . ~i 2 5 2 ~3 2, 4 . S ~ 5 - 5 Abbreviations:
AMR = Amaranthus retroflexus SAL - Setaria Lutescens ~AA = GaLium aparine CYI = Cyperus ir;a ~2~ L716 Example VIII
Young cereal plants (~hea~, barley and rye) in the 3-lPaf stage in tray tests in a greenhouse were sprayed until dripping wet ~ith the compounds to be tes~ed in the active compound concen~rations ekg/hectare~ indica~ed in Table VIII. The comparison compound employed was 2-chloro-ethyltr;methylammonium chloride. When the untreated con-trol plants had reached a height of growth of about ~5 cm, the growth of all the plants ~as measured and the inhibi-tion of growth was calculated as a % of the groll~h of thecontrol plants~ Addit;onally, the phytotoxica action of the compounds was observed. The resul~s are listed in Table VIII. In quoting the inh;bition of growth, 100%
denotes cessation of growth and 0% denotes gro~th corre-sponding to that oF the untreated control plants.
Table VIII

Compou,n,d, CQncentration % inhibition of gro~th for Phyto-according to applied toxic E)(ample No. (kcJ/hectare) wheat Barley. Rye - act;on 17 5~ oa 24 36 31 no 2^50 18 3~ 27 damage i3 ~ ~ 5,~0 ~5 ~1 ~9 ~
- 2~50 ~1 39 29 damage '~ 5~D0 27 3~ 31 no ~ 2.5D 25 30 3~ damage -Comparison ~ 2~ 5~ 27 B 10 no - - -~25 2~ 0 o dama~e 1) (2-Chloroethyl)-trimethylamnlonium chloride 7i~

Example XX
Inhibi~;on of growth in water rice Rice plants were cultivated in small plots (2m x 2m) and were treated with the compounds indicated during the stage of max;rnum t;llering. The substances can either be applied by spraying or put ;nto the water~
3 weeks after treatment, the growth of all the plants was measured and the inhibition of growth was cal-culated as a % of the growth of the control plants. Not~-;ce was also taken of possible phytotoxic damage causedby the compounds. The results are l;sted ;n Table IX.
In quoting the ;nh;bition of growth, 100% denotes cessa-tion of growth and 0% growth corresponding to that of the control.
Table IX

Compound Concentrat;on % inhib;tion Phytotoxic asc~rding to âpplied of grow~th action Example No. (kg/hectare) no 1 25 15 damage 0.62 1~

13 2~5 - ~5 1,25 21 0~62 17 damage ., 17 2~5 ~3 no 1,25 22 dan;age 0.62 20 71~

- 2~ -Example X
M;xtur~s with chloroethylphosphon;c ac;d - synergist;c ef~ects~
Young cereal plants twheat~ barley and rye) ;n the 3-leaf stage in tray tests in a greenhouse were spray~d until dripping wet with the test substancPs and m;xtures indicated.
~ hen the untreated control plants had reached a height of growt~ of about 55 cm, the yrowth of all the plants was measuled and the inhibi~ion of growth was cal-culated as a X of the growth o~ the control plants~ The phytotox;c action of the compouncls was also observed.
The results are listed ;n Table X. In quoting the ;nhib~
;tion of growth, 100% denotes cessat;on of growth and 0%
denotes growth corresponding to that of the untreated con-trol plants.
~able X

Compound Concentration Inhibition of growth Phytotoxic according to applied (g/ha~in (~) for action Example No. abinitio Wheat Barley Rye Chloroethyl-phosphonic ac;d ~A) 2S0 0 0 0 no damage 7 + A 800 + 250 20 15 15 13 800 5 5 5 no 13 + A 800 + 250 18 14 16 damage ~

17 800 9 4 3 no 17 ~ A 8Q0 ~ 250 19 14 1~ dam3ge . ~ ,.

~2~

~ 2~ -It can be seen from Table X that the co~ponents of the mixture are not effective or only very slightly ef~ect;ve ;n the concentrat;ons tested. If, however, the substances are applied togeth~rO the action is increased very greatly. This unexpected synergism permits a marked reduction ln the application rates.

Claims (13)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A l-substituted imidazole-5-carboxylic acid derivative of the formula (I) (I) in which X is 0, S or N, R1 denotes hydrogen, phenyl, C2- to C6-alkenyl or C1- to C12-alkyl, it being possible for the latter to be substituted up to three C1- to C6-alkoxy groups or C1- to C3-dialkylamino groups or by halogen, and, if X = N, two identical or different radicals R1 are attached to N, or, if X = 0 or S, R1 also represents an agriculturally acceptable metal cation or ammonium, and R2 denotes a radical of the formula (II) (II) in which R3 and R4 independently of one another represent a C1- to C4-alkyl group, and the R5s denote identical or different radicals belonging to the group comprising H, C1- to C4-alkyl, C1- to C4-alkoxy and halogen.
2. A l-substituted imidazole 5-carboxylic acid derivative of the formula (I) as claimed in claim 1 wherein X denotes O, R1 denotes H, (C1-C6)alkyl, an alkali metal cation or ammonium;
R2 denotes 2,6-di(C1-C3-alkyl)-phenyl.
3. A l-substituted imidazole 5-carboxylic acid derivative of the formula (I) as claimed in claim 1 wherein R3 denotes CH3, R4 denotes C2H5, R5 denotes H and XR1 denotes OH.
4. A l-substituted imidazole 5-carboxylic acid derivative of the formula (I) as claimed in claim 1 wherein R3 denotes C2H5, R4 denotes C2H5, R5 denotes H and XR1 denotes OH.
5. A l-substituted imidazole 5-carboxylic acid derivative of the formula (I) as claimed in claim 1 wherein R3 denotes C2H5, R4 denotes C2H5, R5 denotes H and XR1 denotes ONa.
6. A l-substituted imidazole 5-carboxylic acid derivative of the formula (I) as claimed in claim 1 wherein R3 denotes C2H5, R4 denotes C2H5, R5 denotes H and XR1 denotes O-CH(CH3)2.
7. A process for the preparation of a compound of the formula (I) of claim 1 starting from a bisformyl ester or the enol form thereof of the formulae (V) or (Va), respectively, (V) (Va) in which R2 is as defined in claim 1 and R7 has the definition of R1 in claim 1, other than H, a metal or ammonium, which comprises either a) reacting the bisformyl ester with a carboxamide containing 1 to 3 carbon atoms, or b) reacting the bisformyl ester with a 5-fold to 30-fold molar excess of ammonium acetate in a 5-molar to 50-molar amount of glacial acetic acid at temperatures of 50 to 180°C, or c) subjecting the aminomethylene compound which can be prepared from a bisformyl ester (V) by reaction with ammonia or ammonium salts and which has the formula (VI) (VI) in which R2 and R7 have the meanings indicated above, to an intramolecular condensation reaction, carried out at a temperature such that the product distils off at the same time, after which, if required, the radical -OR7 is modified or substituted by radicals indicated for X and R1 in claim 1.
8. A process as claimed in claim 2 wherein R7 represents methyl or ethyl.
9. A process as claimed in claim 8 wherein R7 represents ethyl.
10. A process as claimed in claim 7(a) wherein the bisformyl ester is reacted with the carboxamide in the presence of a strong acid at a temperature of 50 to 250°C.
11. A process for combating harmful fungi, which comprises applying an effective amount of a compound according to formula I
of claim 1 to these harmful fungi or to the plants, areas or substrates which have been attacked.
12. A process for combating weeds, which comprises applying an effective amount of a compound according to formula I of claim 1 to these weeds or to the cultivated area.
13. A process for regulating the growth of useful plants, which comprises applying an effective amount of a compound according to formula I of claim 1 to the plants to be treated.
CA000440172A 1982-05-07 1983-11-01 1-substituted imidazole-5-carboxylic acid derivatives, their preparation and their use as biocides Expired CA1201716A (en)

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US4782053A (en) * 1986-09-23 1988-11-01 Shell Internationale Research Maatschappij B.V. Fungicidal compositions
US4808213A (en) * 1986-08-27 1989-02-28 Hoechst Aktiengesellschaft 2,3,6-substituted phenylimidazole derivatives and the use thereof as growth regulators

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DE3217094C2 (en) * 1982-05-07 1989-12-14 Hoechst Ag, 6230 Frankfurt, De
AT41848T (en) * 1984-06-05 1989-04-15 Hoechst Ag Plant growth regulating agents.
DE3442690A1 (en) * 1984-11-23 1986-05-28 Hoechst Ag Salts of 1-phenyl-imidazole-5-carboxylic acids, a process for their preparation and their use as growth regulators
DE3444918A1 (en) * 1984-12-08 1986-06-12 Hoechst Ag 1-phenyl-imidazole-5-carboxylic acid derivatives, as growth regulators, to a process for their preparation and their use
GB8502398D0 (en) * 1985-01-31 1985-03-06 Shell Int Research Imidazole derivatives
DE3514116A1 (en) * 1985-04-19 1986-10-23 Hoechst Ag New cyclohexyl and cyclohexenylimidazolverbindungen, methods for their manufacture and their use as plant growth regulators
DE3515094C2 (en) * 1985-04-26 1988-05-05 Hoechst Ag, 6230 Frankfurt, De
DE3537290A1 (en) * 1985-10-19 1987-04-23 Hoechst Ag 1,2,5-substituted imidazole compounds, processes for their manufacture and their use as growth regulators
DE3608143A1 (en) * 1986-03-12 1987-09-17 Hoechst Ag 1-phenylimidazolcarbonsaeureamide as growth regulators their production and their use
DE3614364A1 (en) * 1986-04-28 1987-10-29 Hoechst Ag 1-phenyl-imidazole compounds, processes for their preparation and their use as growth regulators
GB8617083D0 (en) * 1986-07-14 1986-08-20 Shell Int Research Imidazole derivatives
GB8617791D0 (en) * 1986-07-21 1986-08-28 Shell Int Research Fungicides
GB8629169D0 (en) * 1986-12-05 1987-01-14 Ici Plc Chemical compounds
AT133408T (en) * 1986-12-16 1996-02-15 Zeneca Ltd Pyrrole derivatives and their use in agriculture
US4762850A (en) * 1987-03-24 1988-08-09 Smithkline Beckman Corporation Dopamine-beta-hydroxylase inhibitors
US4835154A (en) * 1987-06-01 1989-05-30 Smithkline Beckman Corporation 1-aralykyl-5-piperazinylmethyl-2-mercaptoimidazoles and 2-alkylthioimidazoles and their use as dopamine-βhydroxylase inhibitors
IL84809A (en) * 1987-11-06 1992-12-01 Ciba Geigy Process for the synthesis of 1-substituted imidazole- 5-carboxylic acids and derivatives thereof

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US4808213A (en) * 1986-08-27 1989-02-28 Hoechst Aktiengesellschaft 2,3,6-substituted phenylimidazole derivatives and the use thereof as growth regulators
US4782053A (en) * 1986-09-23 1988-11-01 Shell Internationale Research Maatschappij B.V. Fungicidal compositions

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EP0137868B1 (en) 1987-08-12

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