DE19649831A1 - Glycine ester or amide derivative solvents for agrochemicals - Google Patents

Abstract

The use of N-substituted glycine ester or amide derivatives of formula R2R3N-CH2-CO-R1 (I) is claimed as formulation auxiliaries for agrochemical active agents (II). R1 = OR4 or NR5R6; R4 = 1-6C alkyl or 2-6C alkenyl; R5 = H, 1-6C alkyl or 2-6C alkenyl; R6 = 1-6C alkyl or 2-6C alkenyl; or NR5R6 = pyrrolidino, piperidino, 4-methylpiperazino or morpholino; R2 = H, 1-6C alkyl or 2-6C alkenyl; R3 = 1-6C alkyl or 2-6C alkenyl; or NR2R3 = pyrrolidino, piperidino, 4-methylpiperazino or morpholino. Also claimed is a plant treatment composition containing at least one compound (I), at least one agent (II) and auxiliaries.

Description

The present invention relates to the new use of certain α-amino Acid derivatives as formulation aids for agrochemical active ingredients.

It has already become known that numerous organic substances Have the formulation of agrochemical active ingredients used. For example N-methyl-pyrrolidone can be used as a solvent to prepare ver to produce a wide variety of organic active ingredients. The characteristics of this formu But aids are not satisfactory in every respect. So with help of N-methyl-pyrrolidone concentrates of agrochemical active ingredients horse riding. When diluting these formulations with water or when applying the However, diluted spraying agents tend to be only slightly soluble, especially in water substances for crystallization. This can be done either in the ready to use Spraying agents or undesired separation on the nozzles of the spraying devices used form endings.

Furthermore, it has already become known that the azole derivatives mentioned below are fungicidally active and can be applied to plants and / or their habitat in the form of aqueous spray liquors:
1- (4-chlorophenyl) -4,4-dimethyl-3- (1,2,4-triazol-1-yl-methyl) -pentan-3-ol,
1- (4-chlorophenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) butan-2-one,
1- (4-chlorophenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) butan-2-ol,
1- (4-phenylphenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) butan-2-ol,
1- (4-fluorophenyl) -1- (2-fluorophenyl) -2- (1,2,4-triazol-1-yl) -ethan-1-ol,
1- (1,2,4-triazol-1-yl) -2- (2,4-dichorphenyl) hexan-2-ol,
1 - ([bis- (4-fluorophenyl) methylsilyl] methyl) -1H- (1,2,4-triazole),
1- (4-chlorophenyl) -2- (1,2,4-triazol-1-yl) -4,4-dimethylpent-1-en-3-ol,
1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) -4,4-dimethylpent-1-en-3-ol,
1- (4-chlorophenyl) -1- (1-cyclopropyl-ethyl) -2- (1,2,4-triazol-1-yl) -ethan-1-ol,
1- (4-chlorophenyl) -3-phenyl-3-cyano-4- (1,2,4-triazol-1-yl) butane and
1- [3- (2-chlorophenyl) -2- (4-fluorophenyl) oxiran-2-ylmethyl] -1H- (1,2,4-triazole)
(cf. EP-A 0 040 345, DE-C 2 201 063, DE-C 2 324 010, EP-A 0 015 756, US-A 4 551 469, EP-A 0 068 813, DE-A 2 838 847, DE-A 3 010 560, DE-A 3 406 993, DE-A 2 821 971 and EP-A 0 196 038).

However, the production of practical formulations of these substances is in some Difficult cases.

It has now been found that α-amino acid derivatives of the formula

in which
R ¹ for the radicals -OR ⁴ or

stands in what
R ^{4 represents} alkyl having 1 to 6 carbon atoms or alkenyl having 2 to 6 carbon atoms,
R ^{5 represents} hydrogen, alkyl having 1 to 6 carbon atoms or alkenyl having 2 to 6 carbon atoms and
R ^{6 represents} alkyl having 1 to 6 carbon atoms or alkenyl having 2 to 6 carbon atoms, or
R ⁵ and R ⁶ together with the nitrogen atom to which they are attached represent a radical of the formula

stand,
R ^{2 represents} hydrogen, alkyl having 1 to 6 carbon atoms or alkenyl having 2 to 6 carbon atoms and
R ^{3 represents} alkyl having 1 to 6 carbon atoms or alkenyl having 2 to 6 carbon atoms,
or
R ² and R ³ together with the nitrogen atom to which they are attached represent a radical of the formula

stand,
can be used as formulation auxiliaries for agrochemical active ingredients.

It is extremely surprising that α-amino acid derivatives of the Formula (I) is very suitable for the formulation of agrochemical active ingredients, because the use of these acid derivatives was due to the prior art of Tech nik not foreseeable. Above all, it was not to be expected that α-amino acid derivatives Formula (I) can act as a formulation aid instead of N-methyl-pyrrolidone.  

The use of amino acid derivatives of formula (I) in aqueous formu A number of products are based on solid agrochemical active ingredients Advantages. The α-amino acid derivatives of the formula (I) to fabrics that are easy to handle and also available in larger quantities are. Furthermore, the solvent qualities of the substances of formula (I) are just in aqueous systems excellent.

It is also advantageous that α-amino acid derivatives of the formula (I) in crop protection have no undesirable side effects.

The α-amino acid derivatives that can be used according to the invention are represented by the formula (I) generally defined.

R ¹ represents the radicals -OR ⁴ or

wherein
R ⁴ preferably represents straight-chain or branched alkyl having 1 to 4 carbon atoms or straight-chain or branched alkenyl having 2 to 4 carbon atoms,
R ⁵ preferably represents hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms or straight-chain or ver branched alkenyl having 2 to 4 carbon atoms and
R ⁶ preferably represents straight-chain or branched alkyl having 1 to 4 carbon atoms or straight-chain or branched alkenyl having 2 to 4 carbon atoms,
or
R ⁵ and R ⁶ together with the nitrogen atom to which they are attached represent a radical of the formula

stand.

R ² preferably represents hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms or straight-chain or branched alkenyl having 2 to 4 carbon atoms.

R ³ preferably represents straight-chain or branched alkyl having 1 to 4 carbon atoms or straight-chain or branched alkenyl having 2 to 4 carbon atoms.

Also stand
R ² and R ³ also preferably together with the nitrogen atom to which they are attached, for a radical of the formula

Α-Amino acid derivatives of the formula (I) in which
R ¹ for the radicals -OR ⁴ or

stands in what
R ^{4 represents} methyl, ethyl, propyl, isopropyl, n-butyl, 2-methyl-propyl, tert-butyl or allyl,
R ^{5 represents} hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, 2-methyl-propyl, tert-butyl or allyl and
R ^{6 represents} methyl, ethyl, propyl, isopropyl, n-butyl, 2-methyl-propyl, tert-butyl or allyl,
or
R ⁵ and R ⁶ together with the nitrogen atom to which they are attached represent a radical of the formula

stand
R ^{2 represents} hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, 2-methyl propyl, tert-butyl or allyl and
R ^{3 represents} methyl, ethyl, propyl, isopropyl, n-butyl, 2-methyl-propyl, tert-butyl or allyl, or
R ² and R ³ also preferably together with the nitrogen atom to which they are attached, for a radical of the formula

stand.  

As examples of α-amino acid derivatives of the formula which can be used according to the invention (I) the substances listed in Table 1 below are mentioned.

Table 1

The α-amino acid derivatives of the formula (I) which can be used according to the invention are known or can be prepared by methods known in principle (cf. Gazz. Chim. Ital. 84, 896 (1954), J. Gen. Chem. USSR (Engl. Transl .) 31, 743 (1961) and Formaco Ed. Sci. 11, 113 (1956)). This gives α-amino acid derivatives of the formula (I) by

• a) Haloacetyl halides of the formula
  in which
  Hal ¹ and Hal ² independently of one another represent chlorine or bromine,
  with compounds of the formula
  HX (III),
  in which
  X for the residues -OR ⁴ or
  stands in what
  R ⁴ , R ⁵ and R ^{6 have} the meanings given above,
  if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent at temperatures between 0 ° C. and 120 ° C.,
  or
• b) Haloacetic acid derivatives of the formula
  in which
  R ¹ and Hal ^{1 have} the meanings given above, with amines of the formula
  in which
  R ² and R ^{3 have} the meanings given above,
  if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent at temperatures between 0 ° C. and 120 ° C.

The compounds required as starting materials in the above reactions Formulas (II) to (V) are known.

In the present context, agrochemical active ingredients are all for To understand plant treatment usual substances. May be mentioned Fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, plants growth regulators and plant nutrients.  

Examples of fungicides are:
Aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine, azaconazole, azoxystrobin,
Benalaxyl, benodanil, benomyl, benzamacril, benzamacrylic isobutyl, bialaphos, binapacrylic, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,
Calcium polysulfide, capsimycin, captafol, captan, carbendazim, carboxin, carvone, quinomethionate (quinomethionate), chlobenthiazone, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cymoxanil, cyphodaminazol, cypodaminazol, cypodinconol
Debacarb, dichlorophene, diclobutrazole, diclofluanide, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazole M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithoxionon, dodemone dodemone, dodemone
Ediphenphos, Epoxiconazole, Etaconazole, Ethirimol, Etridiazole,
Famoxadone, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzon, fluazinam, flumetover, fluoromid, fluquinconazole, flurprimolol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusilazolutol, flusulfazolutol, flusulfazolutol, flusilazolutol, flusilazolutol, flusilazolutolol Fosetyl sodium, fthalide, fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazole-cis, furmecyclox,
Guazatin,
Hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iminoctadinealbesilate, Iminoctadine triacetate, Iodocarb, Ipconazol, Iprobefosufen (IBP), Iprodione, Irumamycin, Isoprothiolan, Isovaledione,
Kasugamycin, Kresoxim-methyl, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclozolin, Myclobutanil,
Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,
Ofurace, Oxadixyl, Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin,
Paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidon, propamocarb, propanosine sodium, propiconazole, propineb, pyrazophos, pyrifenox, pyroxyilonil, pyroxyilonil
Quinconazole, quintozcen (PCNB),
Sulfur and sulfur preparations,
Tebuconazole, tecloftalam, tecnazene, Tetcyclacis, tetraconazole, thiabendazole, Thicyofen, Thifluzamide, Tthiophanate-methyl, thiram, Tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, Triazbutil, triazoxide, tri chlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
Uniconazole,
Validamycin A, vinclozolin, viniconazole,
Zarilamid, Zineb, Ziram as well
Dagger G,
OK-8705,
OK-8801,
α- (1,1-dimethylethyl) -β- (2-phenoxyethyl) -1H-1,2,4-triazole-1-ethanol,
α- (2,4-dichlorophenyl) -β-fluoropropyl-1H-1,2,4-triazole-1-ethanol,
α- (2,4-dichlorophenyl) -β-methoxy-methyl-1H-1,2,4-triazole-1-ethanol,
α- (5-methyl-1,3-dioxan-5-yl) -β - [[4- (trifluoromethyl) phenyl] methylene] -1H-1,2,4-triazol-1-ethanol,
(5RS, 6RS) -6-hydroxy-2,2,7,7-tetramethyl-5- (1H-1,2,4-triazol-1-yl) -3-octanone,
(E) -α- (methoxyimino) -N-methyl-2-phenoxy-phenylacetamide,
{2-Methyl-1 - [[[1- (4-methylphenyl) ethyl] amino] carbonyl] propyl} carbamic acid 1-isopropyl ester
1- (2,4-dichlorophenyl) -2- (1H-1,2,4-triazol-1-yl) ethanone-O- (phenylmethyl) oxime,
1- (2-methyl-1-naphthalenyl) -1H-pyrrole-2,5-dione,
1- (3,5-dichlorophenyl) -3- (2-propenyl) -2,5-pyrrolidinedione,
1 - [(diiodomethyl) sulfonyl] -4-methyl-benzene,
1 - [[2- (2,4-dichlorophenyl) -1,3-dioxolan-2-yl] methyl] -1H-imidazole,
1 - [[2- (4-chlorophenyl) -3-phenyloxiranyl] methyl] -1H-1,2,4-triazole,
1- [1- [2 - [(2,4-dichlorophenyl) methoxy] phenyl] ethenyl] -1H-imidazole,
1-methyl-5-nonyl-2- (phenylmethyl) -3-pyrrolidinol,
2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-1,3-thiazole-5-carboxanilide,
2,2-dichloro-N- [1- (4-chlorophenyl) ethyl] -1-ethyl-3-methyl-cyclopropanecarboxamide,
2,6-dichloro-5- (methylthio) -4-pyrimidinyl-thiocyanate,
2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide,
2,6-dichloro-N - [[4- (trifluoromethyl) phenyl] methyl] benzamide,
2- (2,3,3-triiodo-2-propenyl) -2H-tetrazole,
2 - [(1-methylethyl) sulfonyl] -5- (trichloromethyl) -1,3,4-thiadiazole,
2 - [[6-Deoxy-.4-.O- (4-O-methyl-β-D-glycopyranosyl) -α-D-glucopyranosyl] amino] - 4-methoxy-1H-pyrrolo [2,3- d] pyrimidine-5-carbonitrile,
2-aminobutane,
2-bromo-2- (bromomethyl) pentandinitrile,
2-chloro-N- (2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl) -3-pyridinecarboxamide,
2-chloro-N- (2,6-dimethylphenyl) -N- (isothiocyanatomethyl) acetamide,
2-phenylphenol (OPP),
3,4-dichloro-1- [4- (difluoromethoxy) phenyl] -1H-pyrrole-2,5-dione,
3,5-dichloro-N- [cyan - [(1-methyl-2-propynyl) -oxy] methyl] benzamide,
3- (1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,
3- [2- (4-chlorophenyl) -5-ethoxy-3-isoxazolidinyl] pyridine,
4-chloro-2-cyan-N, N-dimethyl-5- (4-methylphenyl) -1H-imidazole-1-sulfonamide,
4-methyl-tetrazolo [1,5-a] quinazolin-5 (4H) -onm,
8- (1,1-dimethylethyl) -N-ethyl-N-propyl-1,4-dioxaspiro [4.5] decane-2-methanamine,
8-hydroxyquinoline sulfate,
9H-xanthene-9-carboxylic acid 2 - [(phenylamino) carbonyl] hydrazide,
bis- (1-methylethyl) -3-methyl-4 - [(3-methylbenzoyl) oxy] -2,5-thiophene dicarboxylate,
cis-1- (4-chlorophenyl) -2- (1H-1,2,4-triazol-1-yl) cycloheptanol,
cis-4- [3- [4- (1,1-dimethylpropyl) phenyl-2-methylpropyl] -2,6-dimethylmorpholine hydrochloride,
Ethyl - [(4-chlorophenyl) azo] cyanoacetate,
Potassium hydrogen carbonate,
Methane tetrathiol sodium salt,
Methyl 1- (2,3-dihydro-2,2-dimethyl-1H-inden-1-yl) -1H-imidazole-5-carboxylate,
Methyl N- (2,6-dimethylphenyl) -N- (5-isoxazolylcarbonyl) -DL-alaninate,
Methyl N- (chloroacetyl) -N- (2,6-dimethylphenyl) -DL-alaninate,
N- (2,3-dichloro-4-hydroxyphenyl) -1-methyl-cyclohexane carboxamide,
N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-furanyl) acetamide,
N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-thienyl) acetamide,
N- (2-chloro-4-nitrophenyl) -4-methyl-3-nitro-benzenesulfonamide,
N- (4-cyclohexylphenyl) -1,4,5,6-tetrahydro-2-pyrimidinamine,
N- (4-hexylphenyl) -1,4,5,6-tetrahydro-2-pyrimidinamine,
N- (5-chloro-2-methylphenyl) -2-methoxy-N- (2-.oxo-3-oxazolidinyl) acetamide,
N- (6-methoxy) -3-pyridinyl) cyclopropanecarboxamide,
N- [2,2,2-trichloro-1 - [(chloroacetyl) amino] ethyl] benzamide,
N- [3-chloro-4,5-bis (2-propynyloxy) phenyl] -N'-methoxymanimidamide,
N-formyl-N-hydroxy-DL-alanine monosodium salt,
O, O-diethyl- [2- (dipropylamino) -2-oxoethyl] ethylphosphoramidothioate,
O-methyl-S-phenyl-phenylpropylphosphoramidothioate,
S-methyl-1,2,3-benzothiadiazole-7-carbothioate,
spiro [2H] -1-benzopyran-2,1 '(3'H) -isobenzofuran] -3'-one.

Examples of bactericides are:
Bromopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, Kasuga mycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.

Examples of insecticides, acaricides and nematicides are:
Abamectin, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Arnitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,
Bacillus thuringiensis, 4-Bromo-2- (4-chlorophenyl) -1- (ethoxymethyl) -5- (trifluoro methyl) -1H-pyrrole-3-carbonitrile, Bendiocarb, Benfuracarb, Bensultap, Betacyflu thrin, Bifenthrin, BPMC, Brofenprox , Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chlo ethocarb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlormephos, N - [(6-Chloro-3-pyridinyl) -methyl] -N'-cyano-N-methyl- ethane amide, chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin, clofentezin, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,
Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Etho prophos, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Fluazuron, Flucycloxuron, Flucythrinat, Flufenxurophone, Flufenoxurion, Fufonxxuron, Flufenoxuron, Flufenoxuron, Fufionxuron, Fufionxuron, Fufionxuron, Fufionxuron, Fufionxuron, Fufionxuron, Fufionxuron, Fufionxuron, Fufionxuron, Fufone
HCH, heptenophos, hexaflumuron, hexythiazox,
Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin,
Lamda-cyhalothrin, Lufenuron,
Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos, Metamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,
Naled, NC 184, Nitenpyram
Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,
Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenophos, Promecarb, Propaphos, Propoxur, Prothiophos, Prothoat, Pymetrozin, Pyr rachmethrinophin , Pyridaben, pyrimidifen, pyriproxifen,
Quinalphos,
Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,
Tebufenozide, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomenhrononium, Triomenethriazonium, Tri
Vamidothione, XMC, xylylcarb, zetamethrin.

Examples of herbicides are:
Anilides such as B. Diflufenican and Propanil; Arylcarboxylic acids, such as. B. dichloropicolinic acid, dicamba and picloram; Aryloxyalkanoic acids, such as. B. 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr; Aryloxy-phenoxy alkanoic acid esters, such as. B. diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; Azinones, such as B. Chloridazon and Norflurazon; Carbamates, e.g. B. Chlorpropham, Desmedipham, Phenmedipham and Propham; Chloroacetanilides such as e.g. B. Alachlor, Acetochlor, Butachlor, Metaza chlorine, Metolachlor, Pretilachlor and Propachlor; Dinitroanilines such as e.g. B. Oryzalin, Pendimethalin and Trifluralin; Diphenyl ether, such as. B. acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; Ureas, such as B. chlorotoluron, diuron, fluometuron, isoproturon, linuron and metha benzothiazuron; Hydroxylamines, such as. B. Alloxydim, Clethodim, Cycloxydim, Sethoxydim and Tralkoxydim; Imidazolinones, e.g. B. Imazethapyr, Imazametha benz, Imazapyr and Imazaquin; Nitriles such as B. bromoxynil, dichlobenil and ioxynil; Oxyacetamides such as e.g. B. Mefenacet; Sulfonylureas, such as. B. Ainido sulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifen sulfuron-methyl, triasulfuron and tribenuron-methyl; Thiol carbamates such as e.g. B. butylates, cycloates, dialallates, EPTC, esprocarb, molinates, prosulfocarb, thio bencarb and triallates; Triazines, e.g. B. Atrazin, Cyanazin, Simazin, Simetryne, Terbutryne and Terbutylazin; Triazinones such as e.g. B. hexazinone, metamitron and metribuzin; Others, such as B. aminotriazole, benfuresate, bentazone, cinmethy lin, clomazone, clopyralide, difenzoquat, dithiopyr, ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac, sulphosate and tridiphane.

Chlorcholine chloride and ethephon are examples of plant growth regulators called.

Examples of plant nutrients are customary inorganic or organic Fertilizer to supply plants with macro and / or micronutrients called.

The α-amino acid derivatives of the formula (I) can preferably be used for the formulation of fungicidally active azole derivatives of the formula

in which

• a) R ⁹ for
  stands,
  R ^{7 represents} tert-butyl and
  R ^{8 represents} hydroxy,
  or
• b) R ^{9 represents} 4-fluorophenyl,
  R ^{7 represents} 2-fluorophenyl and
  R ^{8 represents} hydroxy,
  or
• c) R ^{9 represents} 2,4-dichlorophenyl,
  R ^{7 represents} n-butyl and
  R ^{8 represents} hydroxy,
  or
• d) R ⁹ for
  stands,
  R ^{7 represents} phenyl and
  R ⁸ stands for cyano,
  or
• e) R ^{9 represents} 4-chlorophenyl,
  R ⁷ for
  stands and
  R ^{8 represents} hydroxy,
  and or
  of the formula
  in which
• a) Y is -CH (OH) and
  R ^{10 represents} chlorine or phenyl,
  or
• b) Y stands for CO and
  R ^{10 represents} chlorine,
  and or
  of the formula
  in which
  R ^{11 represents} hydrogen or chlorine,
  and or
  1 - ([Bis- (4-fluorophenyl) methylsilyl] methyl) -1H- (1,2,4-triazole) of the formula
  and or
  1- [3- (2-chlorophenyl) -2- (4-fluorophenyl) oxiran-2-ylmethyl] -1H- (1,2,4-triazole) of the formula
  

Examples of azole derivatives of the formulas (V1) to (X) are:
1- (4-chlorophenyl) -4,4-dimethyl-3- (1,2,4-triazol-1-yl-methyl) -pentan-3-ol of the formula

1- (4-fluorophenyl) -1- (2-fluorophenyl) -2- (1,2,4-triazol-1-yl) -ethan-1-ol of the formula

1- (1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) hexan-2-ol of the formula

1- (4-chlorophenyl) -3-phenyl-3-cyano-4- (1,2,4-triazol-1-yl) butane of the formula

1- (4-chlorophenyl) -1- (1-cyclopropyl-ethyl) -2- (1,2,4-triazol-1-yl) -ethan-1-ol of the formula

1- (4-chlorophenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) butan-2-ol of the formula

1- (4-phenylphenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) butan-2-ol of the formula

1- (4-chlorophenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) butan-2-ol of the formula

1- (4-chlorophenyl) -2- (1,2,4-triazol-1-yl) -4,4-dimethylpent-1-en-3-ol of the formula

1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) -4,4-dimethylpent-1-en-3-ol of the formula

1 - ([Bis- (4-fluorophenyl) methylsilyl] methyl) -1H- (1,2,4-triazole) of the formula

1- [3- (2-chlorophenyl) -2- (4-fluorophenyl) oxiran-2-ylmethyl] -1H- (1,2,4-triazole) of the formula

The active ingredients of the formulas (VI) to (X) and their use for combating Testing phytopathogenic fungi are known (cf. EP-A 0 040 345, US-A 4 551 469, EP-A 0015756, EP-A 0068813, DE-A 3406993, DE-C 2324010, DE- C 2 201 063, DE-A 2 838 847, DE-A 3 010 560, DE-A 2 821 971 and EP- A 0 196 038).  

The α-amino acid derivatives of the formula (I) are suitable for the formulation of agro chemical agents, i.e. for the production of concentrated formulations or ready to use by diluting with water Spraying agents.

The present invention therefore also relates to formulations and sprays prepared therefrom which

• at least one α-amino acid derivative of the formula (I),
• - at least one agrochemical active substance and
• - additives

contain.

Preference is given to plant treatment agents (= formulations and spray compositions prepared therefrom) which

• at least one α-amino acid derivative of the formula (I),
• - At least one azole derivative of the formulas (VI) to (X) and
• - additives and, if appropriate, further agrochemical active ingredients

contain.

As additional agrochemical active ingredients, which in addition to the azole derivatives of For (VI) and (X) may be present, fungicides, bactericides, insects  Ticides, acaricides and nematicides preferred in question. Examples of such additional Lichen active ingredients are mentioned in the previous lists.

As additives that are present in the preparations according to the invention surface active substances, organic diluents, acids, Cold stabilizers and adhesives in question.

Nonionic, anionic, cationic and zwitterionic emulsifiers are suitable as surface-active substances. These substances include reaction products of fatty acids, fatty acid esters, fatty alcohols, fatty amines, alkyl phenols or alkylarylphenols with ethylene oxide and / or propylene oxide, as well as their sulfuric acid esters, phosphoric acid monoesters and phosphoric acid di-esters, as well as reaction products of ethylene oxide with propylene oxide Alkyl sulfonates, alkyl sulfates, aryl sulfates, tetra-alkyl ammonium halides, trialkyl aryl ammonium halides and alkyl amine sulfonates. The emulsifiers can be used individually or in a mixture. Reaction products of castor oil with ethylene oxide in a molar ratio of 1:20 to 1:60, reaction products of C ₆ -C ₂₀ fatty alcohols with ethylene oxide in a molar ratio of 1: 5 to 1:50, reaction products of fatty amines with ethylene oxide in a molar ratio of 1: 2 to 1:20, reaction products of 1 mole of phenol with 2 to 3 moles of styrene and 10 to 50 moles of ethylene oxide, reaction products of 1 mole of phenol with 2 to 3 moles of vinyl toluene and 10 to 50 moles of ethylene oxide, reaction products of C ₈ - C ₁₂ - Alkylphenols with ethylene oxide in a molar ratio of 1: 5 to 1:30, alkylglycoside, C ₈ -C ₁₆ alkylbenzene sulfonic acid salts, such as. B. calcium, monoethanol, ammonium, di-ethanol ammonium and tri-ethanol ammonium salts.

The emulsifiers from the group of alkylaryl polyglycol ethers used in practice are often mixtures of several compounds. In particular, these are mixtures of substances which differ in the degree of substitution on the phenyl ring connected to the oxyethylene unit and the number of oxyethylene units. As a result, fractional numbers as averages are also calculated for the number of substituents on the phenyl ring. Examples include substances for which the following average compositions result:

Organic diluents which can be used in the preparations according to the invention gene all polar and non-polar commonly used for such purposes  organic solvents. Preference is given to ketones, such as methyl isobutyl ketone and cyclohexanone, also amides, such as dimethyl form amide also cyclic compounds, such as N-methyl-pyrrolidone, N-octyl pyrrolidone, N-dodecyl-pyrrolidone, N-octyl-caprolactam, N-dodecyl-caprolactam and γ-butyrolactone, in addition strongly polar solvents, such as dimethyl sulfoxide, also aromatic hydrocarbons, such as xylene, and also esters, such as propy lenglycol monomethyl ether acetate, adipic acid dibutyl ester, acetic acid hexyl ester, Heptyl acetate, tri-n-butyl citrate and di-n-butyl phthalate esters, and also alcohols, such as ethanol, n- and i-propanol, n- and i-butanol, n- and i-amyl alcohol, benzyl alcohol and 1-methoxy-2-propanol.

The acids in the preparations according to the invention can all be customarily used for inorganic and organic acids which can be used for such purposes be. Aliphatic and aromatic hydroxyl are preferred carboxylic acids such as citric acid, salicylic acid, tartaric acid and ascorbic acid.

As cold stabilizers in the preparations according to the invention, all the usual substances suitable for this purpose may be included. Preferably in The question is urea, glycerin and propylene glycol.

All of the usual adhesives can be used in the preparations according to the invention Suitable substances are used for this purpose. Preferably considered come adhesives such as carboxymethyl cellulose, natural and synthetic pul verige, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and Lecithins, and also synthetic phospholipids. Other additives can mine ralic and vegetable oils.  

The concentrated formulations according to the invention can also ent water hold. From the concentrated formulations, the addition of Prepare ready-to-use water spray.

In the concentrated formulations, the concentration of α-amino acid Derivative of formula (I) can be varied within a wide range. in the generally the concentration of α-amino acid derivative is between 10 and 90% by weight, preferably between 15 and 85% by weight.

The ratio of agrochemical active ingredient to α-amino acid derivative Formula (I) can be varied within a certain range. Generally mine is the weight ratio of agrochemical active ingredient to α-amino acid derivative of the formula (I) between 1: 1 and 1:25, preferably between 1: 2 and 1:20.

The amounts of other active ingredients or additives can be found in the inventions preparations according to the invention can be varied within a relatively wide range. They are of the order of magnitude as is customary in such preparations the case is.

The concentrated formulations according to the invention are produced according to usual methods. In general, the procedure is to start with one Produces concentrate by the at temperatures between 10 and 30 ° C. assembles the required components in any order and homogeneously mixed and the resulting mixture filtered if necessary. For the production the ready-to-use spray is given the concentrated formulation if necessary with stirring and / or pumping with the desired amount Water mixed so that the formulation in water evenly and finely dispersed is distributed.  

It is also possible to then add the α-amino acid derivative of the formula (I) add if the concentrate with water to the ready-to-use spray is diluted.

Both for the preparation of the concentrated formulations and for the preparation The position and application of the ready-to-use spraying agents can all be done usually use suitable mixers and sprayers for this purpose.

The invention is illustrated by the following examples.

Manufacturing examples example 1

A mixture of 492.2 g of methyl chloroacetate, 2,000 g of N-methyl-butylamine and 5,500 ml of methanol is heated under reflux for 24 hours. Subsequently the reaction mixture is evaporated under reduced pressure, the ver remaining residue in water and extracted with methylene chloride. After this Washing the combined organic phases with water is reduced Concentrated pressure and then distilled. In this way 444.1 g of N- (n- Butyl) sarcosic acid methyl ester.

Example 2

731.5 g of diethylamine are added dropwise to a mixture of 564.5 g of chloroacetyl chloride and 2,000 ml of tert-butyl methyl ether within 2 hours with stirring and cooling. The reaction mixture is stirred for a further 16 hours at room temperature, then the precipitate which has precipitated is filtered off and washed with cold tert-butyl methyl ether. The organic phase is washed first with 100 ml of 10% hydrochloric acid and then with a little cold water. The mixture is then concentrated and distilled under reduced pressure. 571.5 g of chloroacetic acid-N, N-diethylamide are obtained in this way. From this, α-diethylamino-acetic acid-diethylamide is obtained by further reaction with diethylamine.
104 ° C at 10 mbar

Example 3

In a mixture of 149.5 g of chloroacetic acid-N, N-diethylamide and 200 ml of tert-butyl methyl ether, 182.9 g of morpholine are added with stirring at room temperature within 2 hours. The reaction mixture is then heated to 100 ° C. and stirred at this temperature for 2 hours. The precipitated solid is then suctioned off. The remaining organic phase is washed with water, then concentrated under reduced pressure and distilled. In this way, 125.4 g of 4-morpholino-acetic acid-N, N-diethylamide are obtained.
Bp. 103 ° C at 0.5 mbar.
The substances listed in Table 2 below are also produced by the methods given above.

Table 2

Manufacture of formulations Example I

To make a concentrated formulation
4.15 parts by weight of 1- (4-chlorophenyl) -4,4-dimethyl-3- (1,2,4-triazol-1-yl-methyl) pentan-3-ol of the formula

50.00 parts by weight of an emulsifier which was prepared by reacting 1 mol of a mixture of linear alcohols having 9 to 11 carbon atoms with 6 mol of ethylene oxide (= emulsifier A), and
45.85 parts by weight of the compound of the formula

mixed at room temperature and stirred into a homogeneous liquid.

Example II

To make a concentrated formulation
5.40 parts by weight of the compound of the formula (VI-a),
50.00 parts by weight of emulsifier A (see Example I) and 44.60 parts by weight of the compound of the formula

mixed at room temperature and stirred into a homogeneous liquid.

Example III

To make a concentrated formulation
5.36 parts by weight of the compound of the formula (VI-a),
50.00 parts by weight of emulsifier A (see Example I) and
44.64 parts by weight of the compound of the formula

mixed at room temperature and stirred into a homogeneous liquid.  

Example IV

To make a concentrated formulation
5.10 parts by weight of the compound of the formula (VI-a),
50.00 parts by weight of emulsifier A (see Example I) and
44.90 parts by weight of the compound of the formula

mixed at room temperature and stirred into a homogeneous liquid.

Example V

To make a concentrated formulation
5.34 parts by weight of the compound of the formula (VI-a),
50.00 parts by weight of emulsifier A (see Example I) and
44.66 parts by weight of the compound of the formula

mixed at room temperature and stirred into a homogeneous liquid.  

Example VI

To make a concentrated formulation
5.37 parts by weight of the compound of the formula (VI-a),
50.00 parts by weight of emulsifier A (see Example I) and
44.63 parts by weight of the compound of the formula

mixed at room temperature and stirred into a homogeneous liquid.

Example VII

To make a concentrated formulation
5.42 parts by weight of the compound of the formula (VI-a),
50.00 parts by weight of emulsifier A (see Example I) and
44.58 parts by weight of the compound of the formula

mixed at room temperature and stirred into a homogeneous liquid.

Usage example

To test the biological properties, the in Examples I to VII listed formulations with water to the desired concentration diluted. The resulting spray liquids are sprayed onto wheat or Sprayed barley plants. It turns out that the spray liquids are very different have good plant tolerance and excellent fungicidal activity.

Claims (7)

1. Use of α-amino acid derivatives of the formula
in which
R ¹ for the rest -OR ¹ or
stands in what
R ^{4 represents} alkyl having 1 to 6 carbon atoms or alkenyl having 2 to 6 carbon atoms,
R ^{5 represents} hydrogen, alkyl having 1 to 6 carbon atoms or alkenyl having 2 to 6 carbon atoms and
R ^{6 represents} alkyl having 1 to 6 carbon atoms or alkenyl having 2 to 6 carbon atoms, or
R ⁵ and R ⁶ together with the nitrogen atom to which they are attached represent a radical of the formula
stand,
R ^{2 represents} hydrogen, alkyl having 1 to 6 carbon atoms or alkenyl having 2 to 6 carbon atoms and
R ^{3 represents} alkyl having 1 to 6 carbon atoms or alkenyl having 2 to 6 carbon atoms,
or
R ² and R ³ together with the nitrogen atom to which they are attached represent a radical of the formula
stand,
can be used as formulation auxiliaries for agrochemical active ingredients. 2. Use according to claim 1, characterized in that one uses α-amino acid derivatives of the formula (I) in which
R ¹ for the radicals -OR ⁴ or
stands in what
R ^{4 represents} straight-chain or branched alkyl having 1 to 4 carbon atoms or straight-chain or branched alkenyl having 2 to 4 carbon atoms,
R ^{5 represents} hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms or straight-chain or branched alkenyl having 2 to 4 carbon atoms and
R ^{6 represents} straight-chain or branched alkyl having 1 to 4 carbon atoms or straight-chain or branched alkenyl having 2 to 4 carbon atoms,
or
R ⁵ and R ⁶ together with the nitrogen atom to which they are attached represent a radical of the formula
stand,
R ^{2 represents} hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms or straight-chain or branched alkenyl having 2 to 4 carbon atoms and
R ^{3 represents} straight-chain or branched alkyl having 1 to 4 carbon atoms or straight-chain or branched alkenyl having 2 to 4 carbon atoms
or
R ² and R ³ together with the nitrogen atom to which they are attached represent a radical of the formula
stand. 3. Use according to claim 1, characterized in that one uses α-amino acid derivatives of the formula (I) in which
R ¹ for the radicals -OR ⁴ or
stands in what
R ^{4 represents} methyl, ethyl, propyl, isopropyl, n-butyl, 2-methyl propyl, tert-butyl or allyl,
R ^{5 represents} hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, 2-methyl-propyl, tert-butyl or allyl and
R ^{6 represents} methyl, ethyl, propyl, isopropyl, n-butyl, 2-methyl propyl, tert-butyl or allyl,
or
R ⁵ and R ⁶ together with the nitrogen atom to which they are attached represent a radical of the formula
stand,
R ^{2 represents} hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, 2-methyl-propyl, tert-butyl or allyl and
R ^{3 represents} methyl, ethyl, propyl, isopropyl, n-butyl, 2-methyl-propyl, tert-butyl or allyl, or
R ² and R ³ also preferably together with the nitrogen atom to which they are attached, for a radical of the formula
stand. 4. Use according to claim 1, characterized in that fungicides, Insecticides, acaricides, nematicides, herbicides and / or plant growth regulators are used as agrochemicals. 5. Use according to claim 1, characterized in that azole derivatives of the formula
in which

• a) R ⁹ for
  stands,
  R ^{7 represents} tert-butyl and
  R ^{8 represents} hydroxy,
  or
• b) R ^{9 represents} 4-fluorophenyl,
  R ^{7 represents} 2-fluorophenyl and
  R ^{8 represents} hydroxy,
  or
• c) R ^{9 represents} 2,4-diehlorphenyl,
  R ^{7 represents} n-butyl and
  R ^{8 represents} hydroxy,
  or
• d) R ⁹ for
  stands,
  R ^{7 represents} phenyl and
  R ⁸ stands for cyano,
  or
• e) R ^{9 is} 4-chlorophenyl, R ^{7 is}
  stands and
  R ^{8 represents} hydroxy,
  and or
  of the formula
  in which
• a) Y is -CH (OH) and
  R ^{10 represents} chlorine or phenyl,
  or
• b) Y stands for CO and
  R ^{10 represents} chlorine,
  and or
  of the formula
  in which
  R ^{11 represents} hydrogen or chlorine,
  and or
  1 - ([Bis- (4-fluorophenyl) methylsilyl] methyl) -1H- (1,2,4-triazole) of the formula
  and or
  1- [3- (2-chlorophenyl) -2- (4-fluorophenyl) oxiran-2-ylmethyl] -1H- (1,2,4-triazole) of the formula
  

6. Plant treatment agent, characterized by a content of

• - at least one α-amino acid derivative of the formula (I) according to claim 1,
• - at least one agrochemical active ingredient and
• - additives.

7. Composition according to claim 6, characterized by a content of at least an azole derivative of the formulas (VI) to (X) as an agrochemical active ingredient material.