WO2011095449A1

WO2011095449A1 - Method for solubilizing hydrophobic active ingredients in an aqueous solution

Info

Publication number: WO2011095449A1
Application number: PCT/EP2011/051292
Authority: WO
Inventors: Bernd Bruchmann; Holger TÜRK; Daniel SCHÖNFELDER; Monika Haberecht; Dietmar Appelhans; Victor Boyko
Original assignee: Basf Se
Priority date: 2010-02-05
Filing date: 2011-01-31
Publication date: 2011-08-11
Also published as: EP2531548A1; CN102741327A; CN102741327B

Abstract

The invention relates to a method for solubilizing hydrophobic active ingredients in an aqueous medium, characterized in that at least one hyperbranched polymer (A) is used as an auxiliary agent and can be obtained by reacting at least one hyperbranched polymer compound with at least one primary or secondary amino group per molecule (a), selected from (a1) hyperbranched polyamides and (a2) hyperbranched polyureas, having (b) at least one mono-, di-, or oligosaccharide.

Description

Process for solubilizing hydrophobic drugs in an aqueous medium

The present invention relates to a process for the solubilization of hydrophobic active substances in an aqueous medium, characterized in that at least one hyperbranched polymer (A) is used as auxiliary which is obtainable by reacting at least one hyperbranched polymeric compound having at least one primary or secondary amino group per Molecule (a) selected from

(a1) hyperbranched polyamides and

(a2) hyperbranched polyureas,

With

(B) at least one mono-, di- or oligosaccharide.

Furthermore, the present invention relates to hyperbranched polymers (A) obtainable by reacting at least one hyperbranched polymeric compound having at least one primary or secondary amino group per molecule (a) selected from

(a1) hyperbranched polyamides and

(a2) hyperbranched polyureas,

With

(B) at least one mono-, di- or oligosaccharide

in the liquid phase.

The present invention furthermore relates to complexes comprising at least one hyperbranched polymer according to the invention and at least one hydrophobic active substance, and to a process for the preparation of complexes according to the invention. Furthermore, the present invention relates to a process for the preparation of hyperbranched polymers according to the invention.

In many cases it is necessary to solubilize hydrophobic substances, for example hydrophobic agents, in water without chemically altering the active substance as such. For this it is possible, for example, to prepare an emulsion, wherein the active substance in question is in the oil phase of the emulsion. However, such an approach is not possible with many pharmaceutical agents or pesticides, especially those to be transported with a body fluid or in a vegetable juice. Emulsions can break under the action of high shear forces. In addition, sterilization to obtain the emulsion is not possible in many cases.

It is known, for example, from DE-A 33 16 510 that it is possible to dissolve hydrophobic pharmaceutically active substances in solvent mixtures of ethanol and water and propylene glycol or polyethylene glycol and to process these into, for example, parenterally applicable formulations. Such solvent mixtures contained in the Usually 15 to 30 wt .-% ethanol. However, efforts are often made to avoid such high levels of alcohol in the treatment of sick people.

It is also known to solubilize active substances based on 1,4-dihydropyridines with phospholipids, especially liposome phospholipids in water, see, for example, EP 0 560 138 A. However, liposome phospholipids are exposed to the same degradation mechanisms as endogenous cell membrane lipids. Depending on the pH and ionic strength of the medium, liposome transport systems prepared in this way have only limited shelf life. In particular, by the shearing forces occurring in the intravenous administration of the active substances liposomal transport systems can be easily destroyed.

Furthermore, in many cases too high concentrations of the solubilizing agent and of the active substance in the liver or spleen are observed as undesired transport from the blood vessels into the surrounding tissue and a slow release of the encapsulated active substance only after a short time due to the dynamic structure the lipid bilayer. The difficult sterilizability is another reason why liposomes are not suitable for all applications in drug delivery. Further systems for solubilizing hydrophobic active ingredients are known, for example, from WO 2007/125028.

From WO 2007/0601 19 hyperbranched polylysines are known, and their use as solubilizers is proposed. However, their solubilization properties of hydrophobic substances are inadequate for many purposes and can be improved.

From WO 2006018125 highly branched polyamides and their use for the production of moldings, films, fibers and foams are known.

WO 2006/087227 discloses combinations of at least one hydrophobic active ingredient and hyperbranched nitrogen-containing polymers, for example polyureas. However, their solubilization properties of hydrophobic substances are inadequate for many purposes and can be improved.

From D. Appel Hans et al., Biomacromolecules 2009, 10, 1 1 14 and D. Appel Hans et al., Molecular Bioscience 2007 ^', 7, 373 is known that one associated with oligosaccharides may employ hyperbranched polyethyleneimines to complex pharmaceutical substances ,

A disadvantage of the known systems for solubilizing hydrophobic active ingredients in aqueous media is that they solubilize only small amounts of active ingredient can. In addition, many of the unfunctionalized hyperbranched polymers used, such as many polyamides and polyureas, are often not water-soluble or water-dispersible per se, so they are not suitable for solubilization in aqueous media. Furthermore, polyethylenimine-containing solubilizers have the disadvantage that, owing to the amino groups which are still numerous even after the functionalization, they have polar structures which are unsuitable for solubilizing hydrophobic active substances.

It is an object of the present invention to provide an improved process for the solubilization of hydrophobic active substances which does not have the disadvantages known from the prior art. Another object was to provide transport systems which avoid the disadvantages known from the prior art. Accordingly, the method defined above was found.

By solubilization is meant that in an aqueous medium hydrophobic, that is insoluble or poorly soluble as such, drug can be distributed molecularly dispersed. This can be done, for example, by complexing or coating the relevant hydrophobic active ingredient.

For the purposes of the present invention, aqueous medium is understood as meaning, for example, water, solvent mixtures of water and at least one organic solvent such as, for example, methanol, ethanol, ethylene glycol, propylene glycol, polyethylene glycol, isopropanol, 1,4-dioxane, Ν, Ν-dimethylformamide, aqueous sugar solutions such as aqueous glucose solution, aqueous salt solutions such as aqueous saline or aqueous potassium chloride solutions, aqueous buffer solutions such as phosphate buffer, or especially plant juices or human or animal hydrous body fluids such as blood, urine and spleen fluid.

Preferably, aqueous medium is understood as meaning pure (distilled) water, aqueous saline solution, in particular physiological saline solution, or solvent mixtures of water with at least one of the abovementioned organic solvents, the proportion of organic solvent not being 10% by weight of the relevant aqueous medium exceeds.

Active substances within the meaning of the present invention may also be referred to as effect substances and are substances which have, for example, an action as plant protection agents, for example as insecticide, herbicide or fungicide, preferably as insecticide and fungicide, or as fluorescence agent or pharmaceutical effect For example, as a cardiovascular or anti-osteoporosis or as a cytostatic. Pigments are not active substances in the sense of the present invention.

Examples of suitable cardiovascular agents are, for example, those of the formula I.

The variables or radicals are defined as follows: stands for N0 ₂ , CN or COOR ¹ , where

is C 1 -C 4 -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, unsubstituted or mono- or polysubstituted with C 1 -C 3 -alkoxy, for example, methoxy, ethoxy, n-propoxy, iso-propoxy; Examples of substituted radicals R ¹ are, for example, methoxymethyl, ethoxymethyl, 2-methoxyethyl.

CO-NH-C ₃ -C ₇ -cycloalkyl or COOR ² , wherein

is selected from Ci-Cio-alkyl, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. Pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; particularly preferably C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, in particular methyl-unsubstituted or mono- or polysubstituted with C 1 -C 3 -alkyl Alkoxy, trifluoromethyl, N-methyl-N-benzylamino or CH 2 -C 6 H 5. Examples of substituted radicals R ² are, for example, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2,2,2-trifluoroethyl. selected from CN, ω-hydroxyalkyl, preferably co-hydroxy-C 1 -C 4 -alkyl, in particular hydroxymethyl and 2-hydroxyethyl, or C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso Butyl, sec-butyl and tert-butyl. identical or different and selected from NO 2, halogen, in particular fluorine, chlorine or bromine, C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert. Butyl, C 1 -C 4 -alkoxy, for example methoxy, ethoxy, n-propoxy, iso -propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy; Benzoyl, acetyl, O-CO-CH3, trifluoromethyl or 2- (4-methylbenzyloxy). m is selected from integers in the range of zero to two, preferably one or two.

Particularly suitable active pharmaceutical ingredients are, for example, nifedipine, nimodipine (1,4-dihydro-2,6-dimethyl-4- (3'-nitrophenyl) -pyridine-3-β-methoxyethyl ester-5-isopropyl ester, known from DE 28 15 278). , Nisoldipine, nitrendipine, felodipine and amodipine.

In the context of active ingredients, hydrophobic is understood to mean that the solubility in distilled water at 20 ° C. is preferably below 1 g / l, more preferably below 0.1 g / l.

Examples of suitable cytostatic agents are doxorubicin and paclitaxel.

Other suitable active pharmaceutical ingredients are those which are active against osteoporosis, inflammation or rheumatism.

Further suitable pharmaceutical active substances in the context of the present invention are hormones, proton pump inhibitors, statins, proteasome inhibitors,

Analgesics and cholesterol lowering drugs. Examples of suitable fungicidal active compounds which can be solubilized by the process according to the invention include:

Acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl;

Amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamine, tridemorph;

Anilinopyrimidines such as pyrimethanil, mepanipyrim or cyrodinyl;

Antibiotics such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin and

streptomycin;

Azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinitroconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prochloraz, prothioconazole, tebuconazole, tetraconazole, triadimefon, Triadimol, triflumizole, triticonazole;

2-Methoxybenzophenone, as described in EP 0 897 904 by the general formula I, z. Eg metrafenone;

Dicarboximides such as iprodione, myclozoline, procymidone, vinclozolin; Dithiocarbamates such as Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propineb, Polycarbamate, Thiram, Ziram, Zineb;

Heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboximine, oxycarboxine, cyazofamide, dazomet, dithianone, famoxadone, fenamidone, fenarimarol, fuberidazole, flutolanil, furametpyr, isoprothiolanes, mepronil, nuarimol, picobezamide, probenazoles, proquinazide , Pyrifenox, Pyroquilon, Quinoxyfen, Silthiofam; Thiabendazoles, thifluzamide, thiophanate-methyl, tiadinil, tricyclazoles, triforins;

Nitrophenyl derivatives such as binapacryl, dinocap, dinobutone, nitrophthalic-isopropyl;

Phenylpyrroles such as fenpiclonil and fludioxonil;

unclassified fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropamide, chlorothalonil, cyflufenamid, cymoxanil, diclomethine, diclocymet, diethofencarb, edfenphos, ethaboxam, fenhexamide, fentin acetate, fenoxanil, ferimzone, fluazinam, fosetyl, fosetyl-aluminum, Iprovalicarb, hexachlorobenzene, metrafenone, pencycuron, propamocarb, phthalides, toloclofos-methyl, quintozene, zoxamide;

Strobilurins as described in WO 03/075663 by the general formula I, for example azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin;

Sulfenic acid derivatives such as captafol, captan, dichlofluanid, folpet, tolylfluanid;

Cinnamic acid amides and analogs such as dimethomorph, flumetover, Flumorp;

6-Aryl- [1,2,4] triazolo [1,5-a] pyrimidines, as described, for. In WO 98/46608, WO 99/41255 or WO 03/004465 are each described by the general formula I;

Amide fungicides such as cyclofenamide and (Z) -N- [α- (cyclopropylmethoxyimino) -2,3-difluoro-6- (difluoromethoxy) benzyl] -2-phenylacetamide. Examples of herbicides include:

1, 3,4-thiadiazoles such as buthidazole and cyprazole;

Amides such as allidochlor, benzoylpropyl, bromobutide, chlorthiamide, dimepiperate, dimethenamid, diphenamid, etobenzanide, flampropmethyl, fosamine, isoxaben, meta-zachlor, monalides, naptalame, pronamide, propanil;

Aminophosphoric acids such as bilanafos, buminafos, glufosinate-ammonium, glyphosate, sulfosates;

Aminotriazoles such as amitrole, anilides such as anilofos, mefenacet;

Aryloxyalkanoic acid such as 2,4-D, 2,4-DB, Clomeprop, dichlorprop, dichlorprop-P, dichloroprop-P, fenoprop, fluroxypyr, MCPA, MCPB, mecoprop, mecoprop-P, napropamide, napropanilides, triclopyr ;

Benzoic acids such as Chloramben, Dicamba;

Benzothiadiazinones such as bentazone;

Bleachers such as Clomazone, Diflufenican, Fluorochloridone, Flupoxam, Fluridone, Pyrazoate, Sulcotrione;

Carbamates such as carbetamide, chlorobufam, chlorpropham, desmedipham, pheneadipham, vernolates; Quinolinic acids such as Quinclorac, Quinmerac;

Dichloropropionic acids such as Dalapon;

Dihydrobenzofurans such as ethofumesates;

Dihydrofuran-3-οη such as flurtamone;

Dinitroanilines such as benefin, butraline, dinitramine, ethalfluralin, fluchloralin, isopropalin, nitralin, oryzalin, pendimethalin, prodiamines, profluralin, trifluralin, dinitrophenols such as bromofenoxime, dinoseb, dinosebacetate, dinoterb, DNOC, minoterb acetate;

Diphenyl ethers such as acifluorfensodium, aclonifen, bifenox, chloronitrofen, difenoxuron, ethoxyfen, fluorodifen, fluoroglycofenethyl, fomesafen, furyloxyfen, lactofen, nitrofen, nitrofluorfen, oxyfluorfen;

Dipyridyls such as cyperquat, difenzoquat methyl sulfate, diquat, paraquat dichloride;

Imidazoles such as isocarbamide;

Imidazolinones such as imazamethapyr, imazapyr, imazaquin, imazethabenzmethyl, imazethapyr, imazapic, imazamox;

Oxadiazoles such as methazoles, oxadiargyl, oxadiazon;

Oxiranes such as tridiphanes;

Phenols such as bromoxynil, loxynil;

Phenoxyphenoxypropionic acid esters such as clodinafop, cyhalofopbutyl, diclofopmethyl, fenoxapropethyl, fenoxaprop-p-ethyl, fenthiapropethyl, fluazifopbutyl, fluazifop-p-butyl, haloxyfopethoxyethyl, haloxyfopmethyl, haloxyfop-p-methyl, isoxapyrifop, propaquizafop, quizalofopethyl, quizalofop-p-ethyl, Quizalofoptefuryl;

Phenylacetic acids such as chlorfenac;

Phenylpropionic acids such as chlorophenprophe-methyl;

ppi agents (ppi = preplant incorporated) such as benzofenap, flumicloracpentyl, flumi- oxazine, flumipropyne, flupropacil, pyrazoxyfen, sulfentrazone, thidiazimine;

Pyrazoles such as Nipyraclofen;

Pyridazines such as Chloridazon, Maleic hydrazide, Norflurazon, Pyridate;

Pyridinecarboxylic acids such as clopyralid, dithiopyr, picloram, thiazopyr;

Pyrimidyl ethers such as pyrithiobacic acid, pyrithiobacsodium, KIH-2023, KIH-6127;

Sulfonamides such as flumetsulam, metosulam;

Triazole carboxamides such as triazofenamide;

Uracils such as bromacil, lenacil, terbacil;

Benazoline, Benfuresate, Bensulide, Benzofluor, Bentazone, Butamifos,

Cafenstrole, Chlorthaldimethyl, Cinmethylin, Dichlobenil, Endothall, Fluorbentranil, Mefluidide, Perfluidone, Piperophos, Topramezone and Prohexandione-Calcium;

Sulfonylureas such as amidosulfuron, azimsulfuron, bensulfuronmethyl,

Chlorimuronethyl, chlorosulfuron, cinosulfuron, cyclosulfamuron,

Ethametsulfuronmethyl, Flazasulfuron, Halosulfuronmethyl, Imazosulfuron,

Metsulfuron methyl, nicosulfuron, primisulfuron, prosulfuron, pyrazosulfuronethyl, rimsulfuron, sulfometuronmethyl, thifensulfuronmethyl, triasulfuron,

Tribenuronmethyl, triflusulfuron methyl, tritosulfuron; Cytogenetic agents of the cyclohexenone type such as alloxydim, clethodim,

Cloproxydim, cycloxydim, sethoxydim and tralkoxydim. Very particularly preferred cyclohexenone-type herbicidal active compounds are: tepraloxydim (compare AGROW, No. 243, 3.1.195, page 21, caloxydim) and

2- (1 - [2- (4-chlorophenoxy) propyloxyimino] butyl) -3-hydroxy-5- (2H-tetrahydrothiopyran-3-yl) -2-cyclohexene-1-one and of the sulfonylurea type:

N - (((4-methoxy-6- [trifluoromethyl] -1, 3,5-triazin-2-yl) amino) carbonyl) -2- (trifluoromethyl) benzenesulfonamide. Examples of suitable insecticides include:

Organophosphates, such as acephates, azinphos-methyl, chlorpyrifos, chlorfenvinphos, diazinone, dichlorvos, dimethylvinphos, dioxabenzofos, dicrotophos, dimethoates, disulfonate, ethion, EPN, fenitrothion, fenthione, isoxathione, malathion, methamidophos, methidathion, methyl parathion, Mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidone, phorates, phoxim, pirimiphos-methyl, profenofos, prothiofos, primiphos-ethyl, pyraclofos, pyridaphenthione, sulprophos, triazophos, trichlorofon; Tetrachlorovinyl, vamidothione carbamates such as alanycarb, benfuracarb, bendiocarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, indoxacarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, triazamates;

Pyrethroids such as bifenthrin, cyfluthrin, cycloprothrin, cypermethrin, deltamethrin, fenvalerate, ethofenprox, fenpropathrin, fenvalerate, cyhalothrin, lambda

Cyhalothrin, permethrin, silafluofen, tau-fluvalinate, tefluthrin, tralomethrin, alpha-cypermethrin, zeta-cypermethrin, permethrin;

Arthropod growth regulators: a) chitin synthesis inhibitors e.g. Benzoylureas such as chlorofluorazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, fluenuron, novaluron, teflubenzuron, triflumuron; Buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists such as halofenozides, methoxyfenocides, tebufenozides; c) juvenoids such as pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors such as spirodiclofen;

Neonicotinoids such as flonicamid, clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, nithiazine, acetamiprid, thiacloprid;

Furthermore, unclassified insecticides such as abamectin, acequinocyl, acetamiprid, a-mitraz, azadirachtin, Bensultap bifenazate, cartap, chlorfenapyr, chlordimeform, Cyromazine, diafenthiuron, dinetofuran, diofenolan, emamectin, endosulfan, ethiprole, fenazaquin, fipronil, formetanate, formetanate hydrochloride, gamma-HCH hydrazine methylnon, imidacloprid, indoxacarb, isoprocarb, metolcarb, pyridaben, pymetrozine, spinosad, tebufenpyrad, thiamethoxam, thiocyclam, XMC and xylylcarb.

N-Phenylsemicarbazone, as described in EP-A 462 456 by the general formula I, in particular compounds of the general formula II

wherein R ⁵ and R ⁶ independently of one another are hydrogen, halogen, CN, C 1 -C ₄ -alkyl, C 1 -C ₄ -alkoxy, C 1 -C ₄ -haloalkyl or C 1 -C ₄ -haloalkoxy and R ^{4 is} C 1 -C ₄ Alkoxy, C 1 -C ₄ haloalkyl or C 1 -C ₄ haloalkoxy, e.g. B. Compound IV wherein R ^{5 is} 3-CF 3 and R ^{6 is} 4-CN and R ^{4 is} 4-OCF ₃ .

Useful growth regulators are z. As chlormoquat chloride, mepiquat chloride, prohexadione calcium or the group of gibberellins. These include z. For example, the gibberellins GA1, GA3, GA4, GA ₅ and GA ₇ etc. and the corresponding exo-16,17-dihydro gibberellins and the derivatives thereof, for example. As the esters with Ci-C ₄ -carboxylic acids. Preferably according to the invention is the exo-16,17-dihydro-GA ₅ -13-acetate.

Preferred fungicides are in particular strobilurins, azoles and 6-aryltriazolo [1, 5a] pyrimidines, as described, for. In WO 98/46608, WO 99/41255 or WO 03/004465 are described by the general formula I there, in particular for active compounds of the general formula III,

wherein:

R ^{x is} a group NR ⁷ R ⁸ , or linear or branched C 1 -C 8 -alkyl which is optionally substituted by halogen, OH, C 1 -C 4 -alkoxy, phenyl or C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, phenyl or naphthyl, where the four last-mentioned radicals 1, 2, 3 or 4 substituents selected from halogen, OH, Ci-C4-alkyl, Ci-C4-haloalkoxy, ci C4 alkoxy and Ci-C4-haloalkyl may have;

R ⁷ , R ⁸ are each independently hydrogen, C 1 -C ⁸ -alkyl, C 1 -C 6 -haloalkyl, C 3 -C 10 -cycloalkyl, C 3 -C 6 -halocycloalkyl, C 2 -C 8 -alkenyl,

C 4 -C 10 alkadienyl, C 2 -C 8 haloalkenyl, C 3 -C 6 cycloalkenyl,

C2-C8-halocycloalkenyl, C2-C8-alkynyl, C2-C8-haloalkynyl or

C3-C6-cycloalkynyl, or

R ⁷ and R ⁸ together with the nitrogen atom to which they are attached form five- to eight-membered heterocyclyl which is bonded via N and contain one, two or three further heteroatoms from the group O, N and S as ring member and / or one or more substituents from the group halogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -haloalkenyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, C 3 -C 6 -alkenyloxy , C3-C6-haloalkenyloxy, (exo) -Ci-C6-alkylene and oxy-Ci-C3-alkyleneoxy can carry; is selected from halogen, cyano, C 1 -C 6 -alkyl, C 1 -C 4 -haloalkyl,

C 1 -C 6 -alkoxy, C 1 -C 4 -haloalkoxy and C 1 -C 6 -alkoxycarbonyl;

Halogen, Ci-C6-alkyl or Ci-C6-haloalkyl and in particular fluorine or chlorine means; is halogen, C 1 -C 4 -alkyl, cyano, C 1 -C 4 -alkoxy or C 1 -C 4 -haloalkyl and preferably represents halogen or methyl and in particular chlorine.

Examples of compounds of formula III are 5-chloro-7 4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7-4 -methylpiperazin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7-morpholin-1-yl) - 6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7-piperidin-1-yl) -6- (2,4,6 trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-chloro-7-morpholin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7-isopropylamino) -6- (2,4,6-trifluorophenyl) - [1, 2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7-cyclopentylamino) -6- (2,4,6-trifluorophenyl) - [1, 2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7,2,2,2-trifluoroethylamino) -6- (2,4,6-trifluorophenyl) - [1, 2, 4] triazolo [1,5-a] pyrimidine,

5-chloro-7-, 1,1-trifluoropropan-2-ylamino) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-chloro-7-3,3-dimethylbutan-2-ylamino) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-chloro-7-cyclohexylmethyl) -6- (2,4,6-trifluorophenyl) - [1, 2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7-cyclohexyl) -6- ( 2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-Chloro-7- (2-methylbutan-3-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7 3-methylpropan-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7-4-methylcyclohexane-1 - yl) -6- (2,4,6-trifluorophenyl) - [, 2,4] triazolo [5-a] pyrimidine,

5-chloro-7-hexan-3-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-chloro-7- (2-methylbutan-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7 3-methylbutan-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7-1-methylpropane-1 - yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-methyl-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-methyl-7- (4-methylpiperazin-1-y

pyrimidine,

5-methyl-7- (morpholin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-methyl-7- (piperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-methyl-7- (isopropylamino) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-Methyl-7- (cyclopentylamino) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimide

5-ΜβΙΙι ^ -7- (2,2,2-ίΜίΙυοΓΘίΐΊνΐ3ΐηίηο) -6- (2,4,6-ίΜίΙυο ΐΊΘηνΙ) - [1 ₁ 2,4] ίΜ3ΖθΙο [1, 5-3] - pyrimidine,

5-methyl-7- (1,1-trifluoropropan-2-ylamino) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-methyl-7- (3,3-limethylbutan-2-ylamino) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-methyl-7- (cyclohexylmethyl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine 5-methyl-7- (cyclohexyl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-Methyl-7- (2-methylbutan-3-yl) -6- (2,4,6-trifluorophenyl) - [1 _l 2 _l 4] triazolo [1,5-a] pyrimidine ₁ 5-methyl-7 - (3-methylpropan-1-νΙ) -6- (2,4,6-ίπίΙυο ΓΐΘη ^) - [1, 2,4] triazolo [1, 5-a] pyrimidine, 5-methyl-7- (4-methylcyclohexan-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-methyl-7- (hexan-3-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-Methyl-7- (2-methylbutan-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7 - (3-methylbutan-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine and 5-methyl-7- (1-methylpropane 1 -yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine.

Suitable insecticides are in particular

- arylpyrroles such as chlorfenapyr,

Pyrethroids such as bifenthrin, cyfluthrin, cycloprothrin, cypermethrin, deltamethrin, esfenvalerate, ethofenprox, fenpropathrin, fenvalerate, cyhalothrin, lambda-cyhalothrin, permethrin, silafluofen, tau-fluvalinate, tefluthrin, traomethrin, α-cypermethrin, zeta-cypermethrin and permethrin,

- fipronil,

Neonicotinoids and

Semicarbazone of formula II.

Suitable fluorescers are, for example, pyrene, uranine, rhodamine, fluoree, coumarin, allophycocyanin, naphthalene, anthracene.

In one embodiment of the present invention, the process according to the invention can be used to solubilize in a range from 0.01 to 1% by weight of hydrophobic active ingredient in an aqueous medium, preferably at least 0.1% by weight, based on the total aqueous formulation prepared according to the invention ,

To carry out the process according to the invention, one or more auxiliaries are used, of which at least one is a hyperbranched polymer (A) which is further defined below and is also referred to as hyperbranched polymer (A), polymer (A) in the context of the present invention. , Hyperbranched polymer according to the invention (A) or inventive polymer (A) is called.

In one embodiment of the present invention, hyperbranched polymer (A) has an average molecular weight M _w in the range of 1,000 to 100,000 g / mol, preferably 1,500 to 50,000 g / mol. The average molecular weight can be determined, for example, by gel permeation chromatography (GPC).

In one embodiment of the present invention hyperbranched polymer (A) has a polydispersity (M _w / M _n ) in the range from 1 to 50, preferably 1, 1 to 30, particularly preferably 2 to 15. Polymer (A) is obtainable by reacting at least one hyperbranched polymeric compound having at least one primary or secondary amino group per molecule (a), in the context of the present invention also referred to as hyperbranched compound (a), which is selected from

(a1) hyperbranched polyamides and

(a2) hyperbranched polyureas, with

(B) at least one mono-, di- or oligosaccharide.

Hyperbranched compounds (a) and thus also the hyperbranched polymers (A) prepared therefrom are molecularly and structurally nonuniform. They differ, for example, by their molecular non-uniformity of dendrimers and are produced with considerably less effort. An example of the molecular structure of a hyperbranched compound based on an AB 2 molecule can be found, for example, in WO 04/20503 on page 2. For the structure (distribution of the branches, etc.) applies to the polymers used, for example, in the context of the present application, based on an A2 + B _y strategy (with y> 3), analogous, s. for example J.-F. Stumbe et al., Macromol. Rapid Commun. 2004, 25, 921. For the definition of dendrimers and hyperbranched polymers, see also PJ Flory, J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chemistry - A European J. 2000, 6 (14), 2499. For the purposes of the present invention, hyperbranched compounds are preferably understood to mean those polymeric compounds (a) or polymers (A) , which have a degree of branching DB in the range of 10 to 99.9%, preferably 20 to 90% and particularly preferably up to 80%. The degree of branching DB is defined as

DB [%] = 100 - (T + Z) / (T + Z + L) where T is the average number of terminal monomer units, Z is the average number of branched monomer units, and L is the average number of linear monomer units per molecule polymeric compound (a) or polymer (A). For definition of DB, see H. Frey et al., Acta Polym. 1997, 48, 30. Amino groups in the context of the present invention are primary amino groups, ie Nh groups, or secondary amino groups, preferably NHR ⁹ groups with R ⁹ selected from C 1 -C 6 -alkyl, in particular methyl or ethyl, or C 3 -C 7 -alkyl. Cycloalkyl or d-Ce-alkylene-Nh, preferably C2-C4-alkylene-N H2 or C2-C4-alkylene- (NH-C2-C4-alkylene) wN H2 or C3-C7-cycloalkylene-N H2 understood, where w is a number in the range of 1 to 10, preferably in the range of 1 to 3, and is preferably C2-alkylene (CH 2) 2 which may be incorporated at any position of a hyperbranched polyamide (a1) or hyperbranched polyurea (a2).

Examples of R ⁹ are methyl, CH ₂ -NH ₂ , ethyl, CH ₂ -CH ₂ -NH ₂ , propyl, (CH ₂ ) ₃ -NH ₂ , butyl, (CH ₂ ) 4 -NH ₂ , n-hexyl, ( CH ₂ ) 6-N H2, cyclohexyl and para-cyclohexylene-NH ₂ . In this case, hyperbranched polyamide (a1) or hyperbranched polyurea (a2) may have only primary amino groups or only secondary amino groups or primary and secondary amino groups.

In one embodiment of the present invention, hyperbranched polyamide (a1) or hyperbranched polyurea (a2) has at least two primary or secondary amino groups per molecule.

In the context of the present invention, hyperbranched polyamides (a1) are understood to mean those hyperbranched polyamides which can be prepared by polycondensation of monomers A2 and B3, A2 being, for example, dicarboxylic acids or suitable derivatives, such as mono- or di-C 1 -C 4 -alkyl esters of Dicarboxylic acids or anhydrides and under B3 tri- or higher-functional amines understand variant (A), wherein the above-mentioned tri- or higher-functional amines are selected from compounds having 3 or more than 3 amino groups per molecule selected from primary and secondary amino groups, preferably from Nh groups and NHR ⁹ groups. Tri- or higher-functional amines may, in addition to the primary or secondary amino groups, also have further functional groups, such as, for example, tertiary amino groups.

Preferred dicarboxylic acids used as monomer A2 are, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, undecane-a, co-dicarboxylic acid, cis- and trans-cyclohexane-1,2-dicarboxylic acid, cis- and trans- Cyclohexane-1, 3-dicarboxylic acid, cis- and trans-cyclohexane-1, 4-dicarboxylic acid and derivatives thereof, such as mono- and dialkyl esters, acid chlorides or anhydrides.

Preferred tri- or higher functional primary or secondary amines are, for example, tris (2-aminoethyl) amine, tris (2-aminopropyl) amine, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, bis (hexamethylene) triamine and derivatives thereof, as well as alkoxylated and aminated higher functional Alcohols, such as Jeffamin® T products. Jeffamin® T are trifunctional polyether polyols with terminal primary amino groups. They are prepared starting from a trifunctional alcohol initiator which is reacted with ethylene oxide and / or propylene oxide and the terminal hydroxyl groups obtained in this step are subsequently converted into amino groups.

In another embodiment, A2 is understood as meaning, for example, diamines and B3 tri- or higher-functional polycarboxylic acids or derivatives thereof, such as anhydrides, mono-, di- or tri-C 1 -C 4 -alkyl esters of tri- or higher-functional polycarboxylic acids, variant (B ).

Examples of preferred diamines are ethylenediamine, propylenediamines (1,2-diaminopropane and 1,3-diaminopropane), 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,8-diaminooctane and isophoronediamine.

Suitable tri- or higher-functional carboxylic acids are, for example, trimesic acid, trimellitic acid, pyromellitic acid, butanetricarboxylic acid and cyclohexane-1,3,5-tricarboxylic acid and derivatives thereof, such as mono- and dialkyl esters, acid chlorides or anhydrides.

In another embodiment of the present invention, hyperbranched polyamides (a1) are understood to mean those hyperbranched polyamides which can be obtained by self-condensation of functional carboxylic acids of, for example, type AB2, where in the case of hyperbranched polyamides (a1) A is a carboxylic acid having two identical or different carboxylic acids different functional groups B stands. B can be chosen in this context, for example, OH, SH and NH2. Preferably, B2 is two NH 2 groups. Examples of suitable AB2-type functional carboxylic acids are cysteine, serine and especially lysine.

In another embodiment of the present invention, hyperbranched polyamides (a1) are understood as meaning hyperbranched polyamides which can be obtained by self-condensation of functional carboxylic acids, for example of type AB2, where in the case of hyperbranched polyamides (a1) B is a carboxylic acid with a further, of COOH different functional group A stands. A can be chosen in this context, for example, OH, SH and NH2. Examples of such suitable AB2-type functional carboxylic acids are glutamic acid and aspartic acid.

In this case, amino acids can each be used as racemates or in enantiomerically pure form, in particular as L-isomer. Hyperbranched polyamides (a1) may comprise one or more further condensed condensates, for example in the case of variant (A) one or more aliphatic or aromatic or cycloaliphatic diamines or, in the case of variant (B), for example one or more dicarboxylic acids.

In one embodiment of the present invention, hyperbranched polyamides (a1) have an average molecular weight M _w in the range from 800 to 100 000 g / mol, preferably in the range from 1 000 to 75 000 g / mol. Hyperbranched polyamides (a1) and processes for their preparation are disclosed, for example, in WO 2006/018125 and the literature cited therein.

In one embodiment of the present invention, hyperbranched polyamides (a1) are selected from hyperbranched polylysines (a3).

Hyperbranched polylysines (a3) in the context of the present invention are understood to mean uncrosslinked polymers which have lysine as the monomer component.

In one embodiment of the present invention, hyperbranched polylysine (a3) may comprise up to 20 mol% of lysine-different monomer building blocks, for example aspartic acid or glutamic acid or one or more other dicarboxylic acids, for example adipic acid or succinic acid.

In one embodiment of the present invention, hyperbranched polylysines (a3) have an average molecular weight M _w in the range from 1,000 to 750,000 g / mol, preferably in the range from 3,000 to 100,000 g / mol.

In one embodiment of the present invention hyperbranched polylysine (a3) may have a degree of branching in the range of 10 to 99.9%, preferably 20 to 99%, and most preferably up to 95%.

In the context of the present invention, "uncrosslinked" in connection with hyperbranched polylysine (a3) is understood to have a lower degree of crosslinking than polylysines having the same molecular weight M _w , which are obtainable by polycondensation of free lysine base.

A measure of the degree of crosslinking is, for example, a comparison of the gel content of the polylysines in question, ie. H. the insoluble in 24-hour storage under water at a temperature of 23 ° C, converted in percent.

Hyperbranched polylysines (a3) and processes for their preparation are disclosed, for example, in WO 2007/0601 19. In the context of the present invention, the term hyperbranched polyureas (a2) also encompasses substances which, in addition to urea groups, may also have urethane groups and optionally further functional groups, for example amino groups. Urethane groups are preferably O-alkyl or O-alkenyl urethane groups, wherein the alkyl or alkenyl group has one to 18 carbon atoms. Preference is given to O-alkyl urethane groups which are obtainable by reaction of an isocyanate group with a monoalcohol which has been used as blocking agent. Hyperbranched polyureas (a2) are obtainable in various ways, for example by direct reaction of isocyanates with polyamines, of urea with polyamines or by Reaction of dialkyl carbonates with polyamines. However, hyperbranched polyureas (a2) in the context of the present invention are preferably obtainable by reacting a blocked polyisocyanate with polyamines, as described in WO 03/066702. Further preparation processes are described, for example WO 2005/044897 A1 describes the synthesis of suitable hyperbranched polyureas (a2) from organic carbonates, for example diethyl carbonate (A2 monomer), and polyfunctional amines, for example triamines (B3 monomers). WO 2005/075541 describes the synthesis of hyperbranched polyureas from urea or urea derivatives (A2 monomers) and polyfunctional amines, for example triamines (B3 monomers).

Hyperbranched polyureas (a2) are preferably obtainable by a process comprising the reaction of an at least difunctional blocked di- or polyisocyanate with at least one at least difunctional primary and / or secondary amine with elimination of the blocking agent.

The at least difunctional blocked diioder polyisocyanates required as starting material can be prepared, for example, by reaction of di- or polyisocyanates with aliphatic, araliphatic or aromatic alcohols, preferably monoalcohols.

Suitable monoalcohols are preferably linear or branched aliphatic monoalcohols, such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol, isobutanol or 2-ethyl-1-hexanol or araliphatic monoalcohols, such as benzyl alcohol or phenylethanol. Particularly preferred are the linear or branched aliphatic monoalcohols and benzyl alcohol. Especially preferred are linear aliphatic monoalcohols having 1 to 18, preferably 1 to 6 carbon atoms.

At least difunctional amines used in the preparation of hyperbranched polyureas (a2) are selected from compounds containing at least two ethane groups carry reactive amine groups. Compounds having at least two amine groups reactive with urethane groups include, for example, ethylenediamine, N-alkylethylenediamine, propylenediamine, 2,2-dimethyl-1,3-propanediamine, N-alkylpropylenediamine, butylenediamine, N-alkylbutylenediamine, hexamethylenediamine, N-alkylhexamethylenediamine, toluenediamine , Diaminodiphenylmethane, diaminodicyclohexylmethane, phenylenediamine, cyclohexyldiamine, diaminodiphenylsulfone, isophoronediamine, 2-butyl-2-ethyl-1, 5-pentamethylenediamine, 2,2,4- or 2,4,4-trimethyl-1,6 hexamethylenediamine, 2-aminopropylcyclohexylamine, 3 (4) -aminomethyl-1-methylcyclohexylamine, 1, 4-diamino-4-methylpentane, amine-terminated polyoxyalkylene polyols (for example Jeffamine® from Huntsman Corporation), aminated polytetramethylene glycols , N-aminoalkylpiperidines, ammonia, bis (aminoethyl) amine, bis (aminopropyl) amine, bis (aminobutyl) amine, bis (aminopentyl) amine, bis (aminohexyl) amine, tris (aminoethyl) amine, tris (aminopropyl) amine, Tris (aminohexyl) amine, Trisa- Minohexane, 4-aminomethyl-1, 8-octamethylenediamine, N '(3-aminopropyl) -N, N-dimethyl-1, 3-propanediamine, Trisaminononan or melamine. Furthermore, any mixtures of at least two of the compounds mentioned can be used. Preferred at least difunctional primary and / or secondary amines are at least difunctional primary amines, more preferably difunctional aliphatic primary amines, in particular isophoronediamine.

Suitable di- or polyisocyanates are known aliphatic, cycloaliphatic, araliphatic and aromatic di- and polyisocyanates. Of these, preferably 4,4'-diphenylmethane diisocyanate, mixtures of monomeric diphenylmethane diisocyanates and oligomeric diphenylmethane diisocyanates (polymeric MDI), tetramethylene diisocyanate, tetramethylene diisocyanate trimers, hexamethylene diisocyanate, hexamethylene diisocyanate trimers, isophorone diisocyanate (IPDI), isophorone diisocyanate trimer, 2,4-tolylene diisocyanate (2,4-TDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 2,6-tolylene diisocyanate (2,6-TDI), or triisocyanatotoluene. For the construction of hyperbranched polyureas (a2), particular preference is given to:

Diisocyanates or polyisocyanates, in particular oligo-or polyisocyanates, which consist of aliphatic, cycloaliphatic, araliphatic and aromatic, preferably aliphatic, di- or polyisocyanates by linking by means of urethane, allophanate, urea, biuret, uretdione, amide, Isocyanurate, carbodiimide, uretonimine, oxadiazinetrione or iminooxadiazinedione structures, preferably by means of isocyanurate structures. These oligo-or polyisocyanates usually have an average NCO functionality of 2.1 to 4.9, preferably 2.9 to 4.4, in particular 3.4 to 3.9. The average molecular weight M _w is preferably in the range from 300 to 3000 g / mol, preferably from 400 to 1500 g / mol, in particular from 500 to 800 g / mol. In one embodiment of the present invention, such hyperbranched polyureas (a2) are selected, in the synthesis of which monofunctional aliphatic, aromatic or aromatic amines have been added as chain terminators. Suitable monofunctional amines are primary alkylamines, preferably Ci-Ci8-alkyl amines, and particularly preferably Jeffamin® M products (M1000 and M2010).

Jeffamin® M products are Huntsman Corporation's monofunctional polyether polyols with terminal primary amino groups. They are prepared starting from a monoalcohol initiator which is reacted with ethylene oxide and / or propylene oxide and whose terminal hydroxyl group obtained in this step is subsequently converted into an amino group.

Hyperbranched polyamides (a1) or hyperbranched polyureas (a2) are in one embodiment so constructed that they are not soluble in water per se, that is less than 1 g / l are soluble in water at 23 ° C, preferably less than 0.1 g / l.

The above-described polymeric compound (a) is reacted with

(b) at least one mono-, di or oligosaccharide, in the context of the present invention also individually as monosaccharide (b), disaccharide (b) or oligosaccharide (b) or in short also called saccharide (b), wherein such reactions are selected by which saccharide (b) is linked to polymeric compound (a). In the context of the present invention, monosaccharides (b) are understood as meaning natural or synthetic simple sugars which may have one or more protective groups, for example acetyl, benzyl or acetonide. Preferably, monosaccharides (b) have no protective groups. Preferred monoascarides (b) are pentoses, for example arabinose, xylose or ribose, and hexoses, in particular galactose, mannose or glucose, furthermore hexoses, such as fructose and sorbose.

In the context of the present invention, disaccharides (b) are understood to mean natural or synthetic double sugars which may have one or more protective groups, for example acetyl, benzyl or acetonide. Preferably, disaccharides (b) have no protecting groups.

Preferred disaccharides are granulated sugar, milk sugar (lactose) and maltose (maltose). In the context of the present invention, oligosaccharides (b) are understood as meaning natural or synthetic polyurosugars having from 3 to 50, preferably to 25 and particularly preferably to 20, monosaccharide units per molecule which may have one or more protective groups, for example acetyl, benzyl or acetonide. Preferably, oligosaccharides (b) have no protecting groups.

Oligosaccharides (b) are generally water-soluble, for example dissolve in distilled water at 20 ° C and atmospheric pressure at least 10 g / l, preferably at least 20 g / l, more preferably at least 100 g / l.

Saccharide (b) may preferably be present as a hydrate.

Particularly preferred saccharides (b) are monosaccharides (b), disaccharides (b) and oligosaccharides (b) with 3 saccharide units per molecule, ie trisaccharides (b).

In disaccharides (b) and oligosaccharides (b), the saccharide units may be the same or different, respectively. In oligosaccharides, the saccharide units may also be substantially the same, for example glucose units, and only a few, for example up to 10 mol%, preferably up to 20 mol%, are not glucose units.

In disaccharide (b) or oligosaccharide (b), the saccharide units are preferably linked together by glycosidic bonds.

In one embodiment of the present invention, in polymer (A) mono-, di- or oligosaccharide (b) is glycosidically linked to hyperbranched polymeric compound (a), in particular via an amino group. In the context of the present invention, glycosidic means that the attachment takes place via the aldehyde function or the ketone functionality of the relevant saccharide (b). In this case, the glycosidic bond may be reversibly or irreversibly linked.

In one embodiment of the present invention, various saccharides (b) are attached to the same hyperbranched polymer (a). Here, various saccharides may be, for example, a disaccharide (b) and an oligosaccharide (b) derived from the same sugar moiety, for example, glucose or mannose, or a monosaccharide (b) and a disaccharide (b) derived from derived from the same sugar unit, or a monosaccharide (b) and an oligosaccharide (b) derived from the same sugar unit. In one variant, various saccharides (b) are attached to the same hyperbranched polymer (a), for example two different monosaccharides (b) or two different disaccharides (b) or two different polysaccharides (b). In one embodiment of the present invention, on average at least one terminal amino group per molecule hyperbranched polymeric compound (a) is linked to one molecule saccharide (b), preferably at least two amino groups per molecule hyperbranched polymeric compound (a) with one molecule saccharide (b ) connected.

In one embodiment of the present invention, the primary or secondary amino groups of hyperbranched polymeric compound (a) are quantitatively linked to saccharide (b), preferably at least 90 mol%.

In another embodiment of the present invention, 10 to 90 mol% of the primary or secondary amino groups of hyperbranched polymeric compound (a) are linked to saccharide (b). Quantitatively associated with saccharide (b) Nh groups are linked to two molecules of saccharide (b) per Nh group.

Quantitatively linked with saccharide (b) NHR ⁹ groups are linked to one molecule of saccharide (b) per NHR ⁹ group.

When polymeric compound (a) is quantitatively linked to saccharide (b), it means that two molecules of saccharide (b) are linked to each Nh and one molecule of saccharide (b) to each NHR ⁹ group. In one embodiment of the present invention, hyperbranched polymer (A) of the invention is contacted with one or more hydrophobic drugs and aqueous medium, for example by mixing. The mixing can be done, for example, by stirring with conventional stirrers or with high-speed stirrers. Other suitable methods are the use of ultrasound or intensive shaking. The mixing is preferably carried out in several stages, by bringing first, for example, inventive hyperbranched polymer (A) with an aqueous medium and then with one or more hydrophobic active ingredients in contact. In one embodiment of the present invention, hyperbranched polymer (A) and hydrophobic active ingredient are used in a mass ratio ranging from 1: 1 to 1000: 1, preferably 1: 1 to 100: 1.

In one embodiment, hyperbranched polymer (A) is stirred with aqueous medium and then with one or more active substances. The mixing can be carried out at temperatures in the range of 0 ° C to 100 ° C and - if one wants to apply increased pressure - even at temperatures up to, for example, 150 ° C. The reaction is preferably carried out under normal pressure and at temperatures in the range from 15 to 70 ° C., preferably in the range from 20 to 50 ° C.

In one embodiment of the present invention, upon completion of the mixing, unsolubilized hydrophobic drug is separated, for example, by filtration or centrifugation. Another object of the present invention are water-soluble or dispersible hyperbranched polymers (A), ie water-soluble or water-dispersible hyperbranched polymers (A) which are obtainable by reacting at least one hyperbranched polymeric compound (a) selected from

(a1) hyperbranched polyamides and

(a2) hyperbranched polyureas,

With

(B) at least one mono-, di- or oligosaccharide.

With polymers (A) according to the invention, the process according to the invention for solubilization can be carried out particularly well.

Water-soluble or water-soluble in connection with polymer (A) according to the invention is understood to dissolve at least 10 g / l in distilled water at 20 ° C. and normal pressure, preferably at least 20 g / l, more preferably at least 100 g / l.

Water-dispersible polymers are understood as meaning those polymers (A) which do not dissolve in water, but which can be processed into dispersions which do not form a sediment detectable with the naked eye within at least two hours at room temperature. Polymers (A) bound to stationary phases in columns are not water-dispersible in the sense of the present invention.

The remaining terms are as defined above. In one embodiment of the present invention, oligosaccharides (b) are selected from compounds composed of three to 20 monosaccharide units per molecule, which may be the same or different.

In one embodiment of the present invention, hyperbranched polymers (A) according to the invention have an average molecular weight M _w in the range from 1000 to 100 000 g / mol, preferably from 1 500 to 50 000 g / mol. The mean molecular weight For example, weight can be determined by gel permeation chromatography (GPC).

In one embodiment of the present invention, hyperbranched polymer (A) according to the invention has a polydispersity (M _w / M _n ) in the range from 1.1 to 30 and more preferably from 2 to 15.

In one embodiment of the present invention, mono-, di- or oligosaccharide (b) is glycosidically linked to hyperbranched polymeric compound (a), in particular via an amino group.

In one embodiment of the present invention, hyperbranched polyamides (a1) are selected from hyperbranched polylysines (a3). Another object of the present invention is a process for the preparation of hyperbranched polymers (A) according to the invention, also referred to in the context of the present invention as a preparation process according to the invention. The preparation process according to the invention is characterized in that at least one hyperbranched polymeric compound (a), selected from

(a1) hyperbranched polyamides and

(a2) hyperbranched polyureas,

With

(B) at least one mono-, di- or oligosaccharide

in the liquid phase under conditions of a reductive amination.

By "in the liquid phase" is meant that the reaction or linking of hyperbranched polymeric compound (a) with saccharide (b) is carried out in molten hyperbranched compound (a) or preferably in solution.

Suitable solvents are, for example, protic and aprotic organic solvents, for example tetrahydrofuran, dichloromethane, chloroform and alcohols, for example ethanol, isopropanol and methanol. Particularly suitable solvent is water.

Reductive aminations are known as such. Without wishing to prioritize any particular theory, the reductive amination in the present invention may be illustrated as being a multistage reaction wherein, in a first step, hyperbranched compound (a) is substituted with a primary or tertiary compound secondary amino group under reaction with the aldehyde group or keto group of saccharide (b) forms an imine selected from aldimines and ketimines, which is then reduced in a second step to an amine.

In one embodiment of the present invention, the reducing agents used are hydrides or hydride complexes, in particular LiBH ₄ or NaBH ₄ or NaBHsCN.

In one embodiment of the present invention, the reducing agent used is a borane-Lewis base complex. Suitable Lewis bases are, for example, thioethers, cyclic and non-cyclic ethers and aliphatic or aromatic amines and also heteroaromatics. Examples of thioethers are dimethyl sulfide and diethyl sulfide. Examples of suitable non-cyclic ethers are, in particular, bis-C 2 -C 10 -dialkyl ethers in which the alkyl radicals are different or preferably identical, for example diethyl ether, diisopropyl ether and di-n-butyl ether. Examples of cyclic ethers are tetrahydrofuran (THF) and tetrahydropyran. Example of aliphatic amines is tert-butylamine. Examples of tertiary amines are, in particular, tri-C 1 -C ₄ -alkylamines, for example triethylamine, furthermore bicyclic amines, for example [2,2,2] -diazabicyclooctane (Dabco). Examples of aromatic amines are in particular tertiary aromatic amines such as Ν, Ν-dimethylaniline and Ν, Ν-diethylaniline. Examples of heteroaromatic compounds are in particular pyridine, 2-picoline and 5-ethyl-2-methylpyridine.

In one embodiment of the present invention, the reducing agent selected is ascorbic acid in an acetic acid / acetate buffer. In another embodiment, an acetic acid / acetate buffer without additional reducing agent is used to link saccharide (b) to amino group via an imine intermediate and subsequent reduction, known from D. Bahdra, A.K. Yadav, S. Bhadra, N.K. Jain International Journal of Pharmaceutics 2005, 295, 221-223 and P.V. Kumar et al. Journal of Drug Targeting 2006, 14, 546-556.

Particularly preferred as Lewis base heteroaromatic amines in which at least one nitrogen atom is part of the heteroaromatic system, for example pyridine, substituted with, for example, Ci-C ₄ alkyl, or particularly unsubstituted tuiert. Very particularly preferred is the borane-Lewis base complex BH3-pyridine, abbreviated in the literature as BH3 ^* Py.

In one embodiment of the present invention, hyperbranched polymeric compound (a) and saccharide (b) are used in proportions such that the molar ratio of primary or secondary amino groups to saccharide (b) is in the range of 1: 0.5-1: 20, preferably 1: 1-1: 10. In one embodiment of the present invention, saccharide (b) and reducing agent are used in a molar ratio ranging from 1: 1 to 1: 3, most preferably equimolar. It can be controlled with the help of any excess used, which and how many amino groups you want to implement. If only the primary amino groups are to be reacted, stoichiometric use of saccharide (b) and reducing agent, based on primary amino groups, is sufficient. If secondary amino groups are also to be reacted, reducing agent and saccharide (b) are each added stoichiometrically to the sum of primary and secondary amino groups from hyperbranched polymeric compound (a). If you want to implement all secondary amino groups with, you need a high excess of reducing agent.

In one embodiment of the present invention, the preparation process according to the invention is carried out at temperatures in the range from zero to 100.degree. C., preferably from 15 to 70.degree.

The reaction time has proven to be suitable for one hour to two weeks, it being possible to choose the reaction time as a function of the temperature. The lower the temperature, the longer the reaction time is chosen.

The reaction pressure at which one carries out the preparation process according to the invention is not critical per se. Preferably, one selects normal pressure. In one embodiment of the present invention, the preparation process according to the invention is carried out at a pH in the range from 3 to 10, preferably from 6 to 9 and particularly preferably from 8 to 9. In order to adjust the pH, it is possible to use known buffers For example, acetate buffer or borate buffer. In one embodiment of the present invention is dispensed after completion of the chemical reaction for the preparation of inventive hyperbranched polymer (A) to a purification.

In another embodiment of the present invention, cleaning is carried out after a finished chemical reaction to produce hyperbranched polymer (A) according to the invention. Such purification may involve, for example, evaporation of solvent and liberated Lewis base. Purification may further include separation of inorganic salts due, for example, to buffers used. It is possible to work up by methods known per se, for example by chromatography, reprecipitation, filtration, particle size-dependent separation processes such as, for example, ultrafiltration or by dialysis. Another object of the present invention are complexes comprising at least one inventive hyperbranched polymer (A) and at least one hydrophobic active ingredient. Complexes are to be understood as meaning not only complexes in the sense of complex theories, but also inclusion compounds or other aggregates of hydrophobic active ingredient and inventive hyperbranched polymer (A), without preference being given to a particular theory.

Complexes according to the invention may comprise, for example, one or more molecules of hydrophobic active ingredient and one or more molecules of hyperbranched polymer (A) according to the invention, ie they need not comprise exactly one molecule of hydrophobic active ingredient and exactly one molecule of hyperbranched polymer (A) according to the invention. Furthermore, complexes according to the invention may contain water or other constituents / additives contained in the formulation. Another object of the present invention is a process for the preparation of complexes of the invention. For the preparation of complexes according to the invention, it is possible to proceed by mixing at least one hydrophobic active ingredient and at least one hyperbranched polymer (A) according to the invention, for example by one of the abovementioned processes, preferably in the presence of water.

Another object of the present invention are aqueous formulations containing at least one complex according to the invention, for example in concentrations of 0.01 to 400 g / l, more preferably from 0.015 to 100 g / l.

Complexes according to the invention and thus aqueous formulations according to the invention can be used, for example, as crop protection agents or for the production of medicaments, depending on the hydrophobic active ingredient used.

The invention will be explained by working examples.

terms:

DBTL: di-n-butyltin dilaurate

Jeffamin® M-1000: monofunctional polyether polyol with terminal primary amino group, average molecular weight M _w approx. 1000 g / mol, Huntsman Corporation

General remarks: Hyperbranched polyamides (a1) and hyperbranched polyureas (a2) were analyzed by gel permeation chromatography with a refractometer as detector. Hexafluoroisopropanol (HIFP) or water was used as mobile phase, polymethyl methacrylate (PMMA) was used as the standard for determining the molecular weight.

The determination of the amine number was carried out according to DIN EN 13717.

The hyperbranched polymers (A) according to the invention were analyzed by gel permeation chromatography using a refractometer as detector.

The dialysis was performed with dialysis tubing of the CelluTransRoth VSeries from Carl Roth GmbH & Co, Karlsruhe / Germany. Used were types with MWCOs (molecular weight cut-offs) of 1000 g / mol, unless stated otherwise.

I. Preparation of Hyperbranched Polyamides (a1)

1.1 Preparation of Hyperbranched Polyamide (a1 .1) In a reaction vessel equipped with stirrer, internal thermometer, reflux condenser and

Nitrogen inlet tube was provided, 362 g of tetraethylene were submitted. While stirring, 238 g of adipic acid dimethyl ester were added over a period of one hour so that the internal temperature was about 100 ° C. After the addition, the reaction mixture was heated to 140 ° C and stirred at 140 ° C for one hour. Then, the reflux condenser was replaced with a descending condenser-type condenser and distilling off the methanol liberated in the reaction. After 150 minutes, the amount of distillate collected was 17.1 g of methanol. Thereafter, the reaction was terminated by cooling to room temperature. The resulting hyperbranched polyamide (a1 .1) was obtained as a viscous, yellow oil.

Analytical data (GPC in HFIP): M _n = 6,300 g / mol; M _w = 14,300 g / mol

Amine numbers: primary amine: 120 mg KOH / g (a1 .1), secondary amine: 381 mg KOH / g (a1.1). I.2 Production of Hyperbranched Polyamide (a1 .2)

In a reaction vessel equipped with stirrer, internal thermometer, reflux condenser and nitrogen inlet tube, 343.9 g of tris (2-aminoethyl) amine were introduced. With stirring, 256.1 g of adipic acid dimethyl ester were metered in over a period of two hours so that the internal temperature was about 100.degree. After the addition, the reaction mixture was heated to 140 ° C and stirred at 140 ° C for 90 minutes. Then the reflux condenser was against a descending radiator Receptacle replaced and started with distilling off the liberated during the reaction of methanol. After 2 hours, 14.3 g of methanol were collected as distillate. Thereafter, the reaction was terminated by cooling to room temperature. The hyperbranched polyamide (a1 .2) thus obtained was obtained as a viscous, yellow oil.

Analytical data (GPC in HFIP): M _n = 5,400 g / mol; M _w = 10,700 g / mol;

Amine numbers: primary amine: 346 mg KOH / g (a1 .2), secondary amine: 50 mg KOH / g (a1.2). I.3 Preparation of Hyperbranched Polyurea (a2.1)

Step 1: In a reaction vessel equipped with stirrer, internal thermometer, reflux condenser and nitrogen inlet tube, 1903.9 g of trimeric hexamethylene diisocyanate were introduced while gassing with dry nitrogen and heated to 80 ° C. with stirring. Then, with constant stirring over a period of 5 hours, 751.1 g of anhydrous n-butanol was added so that the temperature of the reaction mixture did not exceed 80 ° C. After completion of the addition, it was stirred for one hour at 80 ° C and then cooled to room temperature. Step 2: In a reaction vessel equipped with stirrer, internal thermometer, descending condenser condenser and nitrogen inlet tube, with dry nitrogen gassing, 255 g of the reaction product of Step 1 were treated with 50.2 g of isophoronediamine, 294.8 g of Jeffamine® M 1000 and 0.1 g DBTL offset. The reaction mixture was heated to 170 ° C. with constant stirring and stirred at 170 ° C. for 90 minutes, with n-butanol liberated during the reaction being distilled off. During the reaction, the amine consumption in the reaction mixture was monitored by titration of aliquots with 0.1N HCl, and the conversion was thus determined as a percentage of the theoretically possible conversion. After reaching a conversion of 68% was cooled to room temperature and thereby the reaction was stopped. Hyperbranched polyurea (a2.1) was obtained in the form of a yellow-colored, highly viscous liquid.

Analytical data (GPC in HFIP): M _n = 10,200 g / mol; M _w = 37,700 g / mol;

Amine number: primary amine 26 mg KOH / g (a2.1). I.4 Preparation of Hyperbranched Polylysine (a3.1)

In a reaction vessel equipped with stirrer, internal thermometer, descending condenser and nitrogen inlet tube, 1000 g of L-lysine monohydrochloride was added with 219.1 g of NaOH, 150 g of water and 0.1 g of DBTL. The reaction mixture was heated with stirring to 150 ° C and stirred for a period of 5.5 h at 150 ° C, wherein the resulting water was distilled off from the reaction mixture. After distilling off 312 g of water, the pressure in the reaction vessel was lowered to 200 mbar and the temperature was increased to 170.degree. distill off res water. The mixture was stirred for 30 minutes at 170 ° C and then cooled to room temperature and thereby broke the reaction.

Hyperbranched polylysine (a3.1) was obtained as a yellow solid.

Analytical data (GPC in water): M _n = 14,300 g / mol, M _w = 1 18,000 g / mol,

Amine number = n.b.

I.5 Preparation of Hyperbranched Polylysine (a3.2)

In a reaction vessel equipped with stirrer, internal thermometer, descending condenser and nitrogen inlet tube, 1000 g of L-lysine monohydrochloride was added with 219.1 g of NaOH, 150 g of water and 0.1 g of DBTL. The reaction mixture was heated with stirring to 150 ° C and stirred for a period of 5.5 h at 150 ° C, wherein the resulting water was distilled off from the reaction mixture. After distilling off 230 g of water, the pressure in the reaction vessel was lowered to 200 mbar and the temperature was increased to 170 ° C. in order to distill off further water. The mixture was stirred for 30 minutes at 170 ° C and then cooled to room temperature and thereby broke the reaction.

Analytical data (GPC in HFIP): M _n = 1 .370 g / mol, M _w = 2,800 g / mol,

Amine number = 378 mg KOH / g (a3.2) II. Preparation of hyperbranched polymers (A) according to the invention

II.1 Production of Hyperbranched Polymer According to the Invention (A1 .2-1-1)

In a 1 liter flask, 10 g of hyperbranched polyamide (a1.2), corresponding to 61.8 mmol of NH 2 groups, were dissolved in 350 ml of aqueous 0.1M sodium borate buffer and stirred for one hour at room temperature. Thereafter, 222.7 g (618 mmol) of D (+) - maltose (b.1) were added with vigorous stirring. Thereafter, it was heated to 50 ° C. Complete dissolution of D (+) - maltose (b.1) was achieved. After adding 77.3 ml of an 8M solution of borane-pyridine complex in THF (618 mmol), the reaction mixture was stirred at 50 ° C for 7 days. The reaction mixture was dialyzed for 4 days against double distilled water and freeze-dried the resulting product. According to the invention, hyperbranched polymer (A1 .2-1-1) was obtained as a white amorphous product with a yield of 20% (10 g).

II.2 Production of hyperbranched polymer according to the invention (A1 .2-1 -2)

In a 1 liter flask, 10 g of hyperbranched polyamide (a1.2), corresponding to 61.8 mmol of NH 2 groups, were dissolved in 100 ml of aqueous 0.1M sodium borate buffer and stirred for one hour at room temperature. Thereafter, 22.3 g (61.8 mmol) of D (+) - maltose (b.1) were added with vigorous stirring. Thereafter, it was heated to 50 ° C. Complete dissolution of D (+) - maltose (b.1) was achieved. After adding 7.8 ml of an 8M solution of borane-pyridine complex in THF (61.8 mmol), the reaction mixture was stirred at 50 ° C for 7 days. The reaction mixture was dialyzed for 4 days against doubly distilled water and freeze-dried the resulting product. This gave hyperbranched polymer according to the invention (A1 .2-1 -2) as a white amorphous product with a yield of 10% (3.2 g). II.3 Production of hyperbranched polymer according to the invention (A3.1 -1 -1)

In a 1 liter flask, 5 g of hyperbranched polylysine (a3.1) was dissolved in 350 ml of aqueous 0.1 M sodium borate buffer and stirred for half an hour at room temperature. Thereafter, 277 g (769 mmol) of D (+) - maltose (b.1) were added with vigorous stirring. Thereafter, the mixture was heated to 50.degree. Complete dissolution of D (+) - maltose (b.1) was achieved. After adding 96 ml of an 8M solution of borane-pyridine complex in THF (769 mmol), the reaction mixture was stirred at 50 ° C for 7 days. The reaction mixture was dialyzed for 4 days against double distilled water and freeze-dried the resulting product. A hyperbranched polymer (A3.1 -1 -1) according to the invention was obtained as a white amorphous product with a yield of 30% (18.1 g).

11.4 Preparation of Inventive Hyperbranched Polymer (A3.1-1-2) In a 1 liter flask, 5 g of hyperbranched polylysine (a3.1) were taken up in 50 ml of aqueous 0.1M sodium borate buffer and stirred for half an hour at room temperature. Thereafter, 27.7 g (76.9 mmol) of D (+) - maltose (b.1) were added with vigorous stirring. Thereafter, it was heated to 50 ° C. Complete dissolution of D (+) - maltose (b.1) was achieved. After adding 9.6 ml of an 8M solution of borane-pyridine complex in THF (76.9 mmol), the reaction mixture was stirred at 50 ° C for 7 days. The reaction mixture was dialyzed for 4 days against double distilled water and freeze-dried the resulting product. According to the invention, hyperbranched polymer (A3.1-1-2) was obtained as a white amorphous product with a yield of 21% (7.0 g).

11.5 Preparation of hyperbranched polymer (A2.1-1 -2) according to the invention

In a 1 liter flask, 10 g of hyperbranched polyurea (a2.1), corresponding to 4.64 mmol of NH 2 groups) were dissolved in 50 ml of aqueous 0.1M sodium borate buffer and stirred for one hour at room temperature. Thereafter, 1.67 g (4.64 mmol) of D (+) - maltose (b.1) were added with vigorous stirring. Thereafter, it was heated to 50 ° C. Complete dissolution of D (+) - maltose (b.1) was achieved. After adding 0.58 ml of an 8M solution of borane-pyridine complex in THF (46.4 mmol), the reaction mixture was stirred at 50 ° C for 7 days. The reaction mixture was dialyzed for 4 days against double distilled water and freeze-dried the resulting product. According to the invention, hyperbranched polymer (A2.1 -1 -2) was obtained as a white amorphous product in a yield of 30% (3.5 g). III. Solubilization Experiments - Operating Procedure for the Solubilization of Pyrene with Hyperbranched Polymer (A2.1-1-1) According to the Invention 100 mg of hyperbranched polymer (A2.1-1-1) according to the invention were weighed into a 50 ml beaker and dissolved in 9.9 g of distilled water , Subsequently, 100 mg of pyrene was added to the batch to obtain a supersaturated solution. The mixture was then stirred for 24 h at room temperature using a magnetic stirrer. After one hour of rest, excess (ie, not solubilized) active ingredient was separated by centrifugation. The clear solution thus obtained was then examined for its active ingredient content by means of UV spectroscopy. The wavelength of the UV spectroscopic measurement was 334 nm.

The results of the solubilization experiments are summarized in Table 1.

Table 1: Solubility of pyrene [mg / l] in water without or with hyperbranched polymer (A)

Hyperbranched polymer pyrene

without 0.1

(A2.1 -1 -1) 12.9

Claims

claims

A process for the solubilization of hydrophobic active substances in an aqueous medium, which comprises using as auxiliary agent at least one hyperbranched polymer (A) obtainable by reacting at least one hyperbranched polymeric compound having at least one primary or secondary amino group per molecule (a) , chosen from

(a1) hyperbranched polyamides and

(a2) hyperbranched polyureas, with

(B) at least one mono-, di- or oligosaccharide.

A method according to claim 1, characterized in that hyperbranched polymer (A) has an average molecular weight M _w in the range of 1 .000 to 100,000 g / mol.

A method according to claim 1 or 2, characterized in that hydrophobic active substances are selected from crop protection agents and pharmaceutically active substances.

4. The method according to any one of claims 1 to 3, characterized in that one selects hydrophobic agents from insecticides and fungicides.

5. The method according to any one of claims 1 to 4, characterized in that one selects oligosaccharides from compounds which are composed of three to 20 monosaccharide units per molecule, which may be the same or different.

Method according to one of claims 1 to 5, characterized in that hyperbranched polyamides (a1) are selected from hyperbranched polylysines (a3).

Water-soluble or water-dispersible hyperbranched polymers (A) obtainable by reacting at least one hyperbranched polymeric compound having at least one primary or secondary amino group per molecule (a) selected from

(a1) hyperbranched polyamides and

(a2) hyperbranched polyureas,

at least one mono-, di- or oligosaccharide. Hyperbranched polymers (A) according to claim 7, characterized in that one selects oligosaccharides from compounds which are composed of three to 20 monosaccharide units per molecule, which may be identical or different.

Hyperbranched polymers (A) according to claim 7 or 8, characterized in that they have an average molecular weight M _w in the range of 1 .000 to 100.00 g / mol.

Hyperbranched polymers (A) according to any one of claims 7 to 9, characterized in that mono-, di- or oligosaccharide (b) is glycosidically bound to hyperbranched polymeric compound (a).

Hyperbranched polymers (A) according to any one of claims 7 to 10, characterized in that hyperbranched polyamides (a1) are selected from hyperbranched polylysines (a3).

A process for preparing hyperbranched polymers (A) according to any one of claims 7 to 1 1, characterized in that at least one hyperbranched polymeric compound having at least one primary or secondary amino group per molecule (a), selected from

(a1) hyperbranched polyamides and

(a2) hyperbranched polyureas,

With

(B) at least one mono-, di- or oligosaccharide

in the liquid phase under conditions of a reductive amination.

A method according to claim 12, characterized in that one carries out the reductive amination with the aid of a borane-Lewis base complex.

A method according to claim 12 or 13, characterized in that one carries out the reductive amination with the aid of a borane-pyridine complex.

A complex comprising at least one hyperbranched polymer (A) according to any one of claims 7 to 11 and at least one hydrophobic active ingredient.

An aqueous formulation comprising at least one complex according to claim 15. Process for the preparation of complexes according to Claim 15, characterized in that at least one hyperbranched polymer (A) and at least one hydrophobic active substance are mixed with one another.