WO2009115392A1 - Sels d’imidazolium utilisés comme stabilisateurs d’enzymes - Google Patents

Sels d’imidazolium utilisés comme stabilisateurs d’enzymes Download PDF

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Publication number
WO2009115392A1
WO2009115392A1 PCT/EP2009/052057 EP2009052057W WO2009115392A1 WO 2009115392 A1 WO2009115392 A1 WO 2009115392A1 EP 2009052057 W EP2009052057 W EP 2009052057W WO 2009115392 A1 WO2009115392 A1 WO 2009115392A1
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Prior art keywords
washing
cleaning agent
protease
agent according
alkaline protease
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PCT/EP2009/052057
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German (de)
English (en)
Inventor
Ursula Huchel
Timothy O' Connell
Elke Veit
Daniela Lowis
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Henkel Ag & Co. Kgaa
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Publication of WO2009115392A1 publication Critical patent/WO2009115392A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/60—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by oxygen or sulfur atoms, attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38663—Stabilised liquid enzyme compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3281—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/34—Organic compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/96—Stabilising an enzyme by forming an adduct or a composition; Forming enzyme conjugates

Definitions

  • the present invention relates to detergents and cleaning compositions containing imidazolium salts, which act as protease inhibitors and are thus suitable enzyme stabilizers.
  • enzymes in detergents and cleaners have been established in the art for decades. They serve to extend the range of services of the funds concerned according to their specific activities. These include in particular hydrolytic enzymes such as proteases, amylases, lipases and cellulases. The first three hydrolyze proteins, starches and fats and thus contribute directly to soil removal. Cellulases are used in particular because of their tissue effect.
  • Another group of washing and cleaning agent enzymes are oxidative enzymes, in particular oxidases, which, if appropriate, in combination with other components, are preferably used to bleach soiling or to produce the bleaching agents in situ.
  • enzymes which are subjected to constant optimization, further enzymes are constantly being made available for use in detergents and cleaners in order to be able to optimally address particular soiling, such as pectinases, ⁇ -glucanases, mannanases or other hemicellulases (glycosidases) Hydrolysis in particular of special vegetable polymers.
  • soiling such as pectinases, ⁇ -glucanases, mannanases or other hemicellulases (glycosidases) Hydrolysis in particular of special vegetable polymers.
  • One goal in the development of detergent formulations is to stabilize the enzymes contained, especially during storage. This is understood as protection against various unfavorable influences, such as denaturation or decay due to physical influences or oxidation.
  • One focus of these developments is the protection of the contained proteins and / or enzymes against proteolytic cleavage. This can be done by the construction of physical barriers, such as by encapsulation of the enzymes in special enzyme granules or by packaging the means in two- or multi-chamber systems.
  • the other many pathway is to add chemical compounds that inhibit the proteases and thus act collectively as stabilizers for proteases and the other proteins and enzymes contained. It must be reversible protease inhibitors, since the protease activity only temporarily, especially during the storage, but not be suppressed during the cleaning process.
  • Polyols in particular glycerol and 1,2-propylene glycol, benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are established as reversible protease inhibitors in the prior art.
  • These include, in particular, derivatives having aromatic groups, for example ortho, meta or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or esters of the abovementioned compounds (see above).
  • a particularly good protection results when boric acid derivatives are used together with polyols, since they can then form a complex stabilizing the enzyme.
  • peptide aldehydes that is, oligopeptides with reduced C-terminus, especially those of 2 to 50 monomers are described for this purpose.
  • peptidic reversible protease inhibitors include ovomucoid and leupeptin.
  • specific, reversible peptide inhibitors and fusion proteins from proteases and specific peptide inhibitors are used for this purpose.
  • enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and - propanolamine and mixtures thereof, aliphatic carboxylic acids up to C 12 , such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also established for this purpose. Certain organic acids used as builders are capable, as disclosed in WO 97/18287, of stabilizing an enzyme in addition to their builder function.
  • subtilisin-type proteases (subtilases, subtilopeptidases, EC 3.4.21.62) occupy an outstanding position due to their favorable enzymatic properties such as stability or pH optimum. They are attributed to the serine proteases due to the catalytically active amino acids. They act as nonspecific endopeptidases, that is, they hydrolyze any acid amide linkages that are internal to peptides or proteins. Their pH optimum is usually in the clearly alkaline range. For an overview of this family, see for example the article "Subtilases: Subtilisin-like Proteases" by R.
  • subtilisin enzymes edited by R. Bott and C. Betzel, New York, 1996.
  • Subtilases become natural formed by microorganisms; Of these, in particular, the subtilisins formed and secreted by Bacillus species are to be mentioned as the most important group within the subtilases.
  • WO 92/19707 A1 discloses meta-substituted phenylboronic acids.
  • Para-substituted phenylboronic acids as protease inhibitors are disclosed in EP 478050 A1.
  • the protease-inhibiting effect of complexes of boric acids and boric acid derivatives with aromatic compounds is disclosed in EP 511456 A1.
  • WO 95/29223 A1 discloses the same effect of substituted naphthalene boronic acids.
  • WO 96/21716 A1 cites the five applications cited above and discloses that all the protease inhibitors listed therein are also suitable for the specific purpose of stabilizing enzymes in detergents and cleaners. A selection of particularly efficient stabilizers thereof discloses WO 96/41859 A1.
  • the boric acid derivatives have a significant disadvantage: many of them, such as borate, form undesirable by-products with some other detergent ingredients, so that they are in the concerned funds are no longer available for the desired cleaning purpose or even remain as an impurity on the laundry.
  • the imidazolium salt according to the invention is preferably a salt which contains as imidazolium cation a compound of general formula (I)
  • R1, R2, R3, R4 and R5 independently of one another represent trifluoromethyl, hydrogen, alkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl, heteroalkyl, heterocycloalkyl, alkoxy, alkoxyalkyl, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, alkanoyl, alkanoyloxy, alkoxycarbonyl, Alkylaminocarbonyl, alkylsulfanylcarbonyl, hydroxy, hydroxyalkyl, hydroxycarbonyl, amino, alkylamino, aryl, arylalkyl, aryloxy, arylamino, arylsulfanyl, arylsulfinyl, arylsulfonyl, arylcarbonyl, arylcarbonyloxy, aryloxycarbonyl, arylamino
  • R 1 and R 4 independently of one another represent optionally substituted alkyl, aryl, arylalkyl, alkylcarbonylalkyl or arylcarbonylalkyl and R 2, R 3 and R 5 independently of one another represent hydrogen or optionally substituted alkyl.
  • R1 and / or R4 preferably both R1 and R4, comprise an aromatic radical.
  • R1 and R4 are independently optionally substituted phenyl, phenyl-C., _ 6 alkyl or phenylcarbonyl-C., _ 6 alkyl, and the radicals R2, R3 and R5 independently represents hydrogen or optionally d-6-alkyl.
  • R 1 is an optionally substituted phenacyl radical and / or R 4 is an optionally substituted phenylmethyl radical.
  • the imidazolium cation is a compound of the formula (II) or (III)
  • said compounds may also be monosubstituted or polysubstituted.
  • substituents are preferably selected from alkyl, halogen, in particular chlorine, bromine, iodine or fluorine, hydroxy, hydroxyalkyl, hydroxycarbonyl, alkoxy, alkoxyalkyl, alkoxycarbonyl, amino, alkylamino and dialkylamino.
  • the anion of the imidazolium salt is preferably selected from halide, especially chloride, boron, iodide or fluoride, sulfate, sulfite, nitrate, bicarbonate and deprotonated organic acids, more preferably it is a halide, especially bromide.
  • the washing or cleaning agent according to the invention preferably contains at least one protease.
  • Alkyl means according to the invention is preferably C ⁇ alkyl.
  • C ⁇ -alkyl according to the invention each independently represents all saturated linear and branched alkyl radicals with up to 18 C atoms, where Ci- 6 alkyl radicals are preferred.
  • cycloalkyl is preferably C 3-8 -cycloalkyl.
  • C 3-8 -cycloalkyl independently of one another in each case denotes all cyclic alkyl radicals having 3 to 8 C atoms, preferably having 5 to 6 C atoms, where the radicals may be saturated or unsaturated , in particular for cyclopentyl, cyclohexyl or cyclopentadienyl.
  • alkenyl is preferably C 2 -18 -alkenyl C.
  • C 2 -alkenyl is, independently of one another, independently of all linear and branched alkyl radicals having up to 18 carbon atoms and containing at least one double bond, where C 2 . 6 -alkenyl radicals are preferred.
  • Alkynyl means according to the invention is preferably C 2. 18 alkynyl.
  • C 2. 18 -alkynyl according to the invention in each case independently of one another for all linear and unbranched alkyl radicals having up to 18 carbon atoms, containing at least one triple bond, wherein said C 2 _ 6 alkynyl radicals are preferred.
  • C2. 6 -alkynyl according to the invention for all linear and unbranched alkyl radicals having up to 6 carbon atoms, containing at least one triple bond, in particular ethynyl, propynyl, i-propynyl, and all Isomers of butynyl, pentynyl and hexynyl.
  • Heteroalkyl according to the invention in each case independently of one another for all saturated and mono- or polyunsaturated, linear or branched alkyl radicals containing at least one, preferably exactly one heteroatom, in particular selected from O, S and N, wherein the sum of C and Heteroatoms preferably up to 18, more preferably up to 6, is.
  • Heterocycloalkyl according to the invention is in each case independently of one another for all cyclic alkyl radicals which contain at least one, preferably exactly one, heteroatom, in particular selected from O, S or N, wherein the ring is preferably from three to eight membered, more preferably five to six membered , Examples of these are tetrahydrofuranyl, tetrahydrothiophenyl, pyrrolidinyl, 2- Thiazolinyl, tetrahydrothiazolyl, tetrahydrooxazolyl, piperidinyl, piperazinyl, morpholinyl and thiomorpholinyl.
  • Alkoxy means according to the invention is preferably C-1 8 alkoxy.
  • C 1 8 alkoxy in the present invention are each independently, all saturated and unsaturated, linear and branched alkyl radicals having up to 18 carbon atoms via an oxygen atom are attached, wherein said C 1-6 - alkoxy radicals are preferably de-alkoxy in the present invention are each independently, all saturated and unsaturated, linear and branched alkyl radicals having up to 6 C-atoms, which via an oxygen atom, are bonded, in particular for methoxy and ethoxy.
  • C-M ⁇ -alkylsulfanyl in each case represents, independently of one another, all saturated and unsaturated, linear and branched alkyl radicals having up to 18 C atoms which are bonded via a sulfur atom , said C
  • _ 6 alkylsulfanyl is according to the invention for all saturated and unsaturated, linear and branched alkyl radicals having up to 6 carbon atoms bonded via a sulfur atom , in particular for methysulfanyl and ethylsulfanyl.
  • Alkylsulfinyl means according to the invention is preferably C 1-18 alkylsulfinyl, C 1 -18 alkylsulfinyl according to the invention is in each case independently of one another for all saturated and unsaturated, linear and branched alkyl radicals having up to 18 carbon atoms, which has a SO- group are bonded, said C
  • alkylsulfonyl radicals are preferably C 1 _ 6 -AI kylsu If i nyl stands according to the invention for all saturated and unsaturated, linear and branched alkyl radicals having up to 6 carbon atoms, which an SO group are bonded, in particular for methylsulfinyl and ethylsulfinyl.
  • Alkylsulfonyl is preferably according to the invention
  • C 1 -C 4 -alkylsulfonyl in each case independently of one another represents all saturated and unsaturated, linear and branched alkyl radicals having up to 18 C atoms which are bonded via an SO 2 group, preference being given to C 1 -C 6 -alkylsulfoxydyl radicals
  • Ci- 6 alkylsulfonyl is according to the invention for all saturated and unsaturated, linear and branched alkyl radicals having up to 6 C-atoms which 2 group are bonded via a SO, especially methylsulfonyl and ethylsulfonyl.
  • alkanoyl is preferably Ci-i ⁇ -alkanoyl.
  • Ci-i ⁇ -alkanoyl is, independently of one another, independently of all saturated and unsaturated, linear and branched alkyl radicals having up to 18 C atoms which are bonded via a carbonyl group
  • _ 6 alkanoyl radicals are preferably C ⁇ g-alkanoyl according to the invention for all saturated and unsaturated, linear and branched alkyl radicals having up to 6 carbon atoms, which are bonded via a carbonyl group. in particular for methycarbonyl and ethylcarbonyl. 8th
  • alkanoyloxy is preferably according to the invention
  • C ⁇ - alkanoyloxy according to the invention are each independently, all saturated and unsaturated, linear and branched alkyl radicals having up to 18 carbon atoms which are bonded via a carbonyloxy group, where Ci- 6 alkanoyloxy radicals are preferred.
  • cis- 6- alkanoyloxy represents all saturated and unsaturated, linear and branched alkyl radicals having up to 6 carbon atoms which are bonded via a carbonyloxy group, in particular methanoyloxy, ethanoyloxy, n-propanoyloxy and i-propanoyloxy.
  • alkoxycarbonyl is preferably C 1-10 -alkoxycarbonyl.
  • C 1-18 -alkoxycarbonyl in accordance with the invention in each case independently of one another for all saturated and unsaturated, linear and branched alkyl radicals having up to 18 C atoms which have an oxycarbonyl group are bonded, where Ci- 6 alkoxycarbonyl radicals are preferred Ci. 6 - alkoxycarbonyl accordance with the invention for all saturated and unsaturated, linear and branched alkyl radicals having up to 6 carbon atoms, which are bonded via an oxycarbonyl group, especially for methoxycarbonyl and ethoxycarbonyl.
  • Alkylaminocarbonyl means according to the invention is preferably C 1 -18 alkylaminocarbonyl C 1 -18 -.
  • Alkylaminocarbonyl according to the invention are each independently one The inocarbonyl group which is mono- or disubstituted by a saturated or unsaturated, linear or branched alkyl radical having is substituted by up to 18 carbon atoms, wherein mono- or disubstituted by C 1-6 alkyl groups substituted aminocarbonyl radicals, in particular monomethylaminocarbonyl, diemethylaminocarbonyl, monoethylaminocarbonyl and diethylaminocarbonyl, are preferred.
  • alkylsulfanylcarbonyl is preferably C-M ⁇ -alkylsulfanylcarbonyl.
  • C- MS -alkylsulfanylcarbonyl in each case independently of one another is saturated and unsaturated, linear and branched alkyl radicals having up to 18 carbon atoms and having a thiocarbonyl group
  • C 1-6 -alkylsulfanylcarbonyl radicals are preferred according to the invention C.
  • C 1-6 -alkylsulfanylcarbonyl represents all saturated and unsaturated, linear and branched alkyl radicals having up to 6 C atoms which are bonded via a thiocarbonyl group , in particular methylthiocarbonyl and ethylthiocarbonyl.
  • alkylamino preferably stands for (C 1-8 -alkyl) -NH.
  • (C 1-8 -alkyl) NH 4 independently of one another in each case represents all saturated and unsaturated, linear and branched alkyl radicals having up to 18 C atoms which have a hydrogenamino group wherein (C 1 -6 -alkyl) NH is preferred.
  • NH 3 represents all saturated and unsaturated, linear and branched alkyl radicals having up to 6 C atoms which have a Hydrogenamino group are bonded, in particular for CH 3 NH and C 2 H 5 NH.
  • dialkylamino preferably represents di- (C 1-18 -alkyl) N.
  • N-di- (C 1-18 -alkyl) N is, according to the invention, independently of each other all saturated and unsaturated, linear and branched alkyl radicals having up to 18 C -atoms, which are bonded via a (Ci_i8 alkyl) amino group, where di (CI_ 6 alkyl) N is preferable.
  • the two alkyl groups may be the same or different from each other in this case.
  • di- (C 1-6 -Alkyl) N is according to the invention for all saturated and unsaturated, linear and branched alkyl radicals having up to 6 carbon atoms which are bonded via a (C 1 -6 -alkyl) amino group, in particular for (CH 3 ) 2 N and (C 2 Hs) 2 N.
  • aryl is preferably C 6-10 -aryl.
  • C 6-10 -ArYl is according to the invention, in particular also in C 6-10 aryl-C 1-12 -alkyl, C 6-10 aryl Oxy, C 1-10 arylamino, C 6-10 arylsulfanyl, C 6-10 - Arylsulfonyl, C ⁇ -io-arylsulfoxidyl, C ⁇ -io-arylcarbonyl, C ⁇ -io-Arylcarbonyloxy, C ⁇ -io-aryloxycarbonyl, C ⁇ -io-arylaminocarbonyl and C ⁇ -io-Arylsulfanylcarbonyl, preferably phenyl or naphthyl, particularly preferably phenyl.
  • Heteroaryl is according to the invention, in particular also in heteroaryl-d-12-alkyl, heteroaryloxy, heteroarylamino, heteroarylsulfanyl, heteroarylsulfonyl, heteroarylsulfoxidyl, heteroarylcarbonyl, heteroarylcarbonyloxy, heteroaryloxycarbonyl, heteroarylaminocarbonyl and heteroarylsulfanylcarbonyl, unless stated otherwise, for at least one heteroatom selected from O, S and N-containing aromatic radical having from 5 to 10, preferably 5 or 6, ring members, preferably selected from furanyl, thienyl, thiophenyl, pyrrolyl, isopyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, isothiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl , Benzofurany
  • alkyl radical may be saturated or unsaturated, branched or unbranched.
  • Preferred radicals are benzyl, phenylethyl, naphthylmethyl and naphthylethyl.
  • Amino stands for any substituted or unsubstituted amino group, in particular -NH 2 , -NH (C 1-18 -alkyl), -N (C 1-18 -alkyl) 2 , -NH (C 6-10 -) ArYl) or -N (C 6-10 -ArYl) 2 , more preferably -NH 2 .
  • Ammonium refers according to the invention for any substituted or unsubstituted ammonium group, in particular NH 3 ⁇ +), -NH 2 (C 1-18 alkyl) ⁇ +), -NH (C 1- 18 -alkyl) 2 ⁇ + ) or -N (C 1-18 -alkyl) 3 (+) , 10
  • Sulfato is in particular -O-S (O) 2 -OR
  • sulfo is -S (O) 2 -OR
  • amidosulfo is -O-S (O) 2 -NR 2
  • phosphato for -O-P (O) (OR) 2
  • phosphono for -P (O) (OR) 2
  • amidophosphono for -OP (O) (NR 2 ) 2 or -O-P (O) (OR ) (NR 2 )
  • R are each independently H, M ⁇ +) , Ci-i ⁇ -alkyl, C ⁇ -io-aryl or C 1-18 -alkyl C 6, 10 -aryl.
  • Imidazolium salts to be used according to the invention are preferably present in the compositions according to the invention in an amount of up to 20% by weight, more preferably in amounts of from 0.001 to 10% by weight, in particular from 0.01 to 5% by weight, especially from 0.1 to 2 wt .-%.
  • a detergent or cleaning agent according to the invention are all means that are suitable for washing or cleaning of particular textiles and / or solid surfaces. Suitable ingredients for this purpose are detailed below.
  • a protease is to be understood as meaning all enzymes which are capable of hydrolyzing acid amide linkages of proteins.
  • the proteases are also detailed below.
  • the compounds relevant to the invention form a complex with the protease to be inhibited / stabilized according to the invention.
  • the active site of the protease is blocked by a compound which is not hydrolyzable by this enzyme and is not available for hydrolysis of other proteins present. This is a reversible bond, i. for a balance between association and dissociation.
  • the equilibrium coefficient of this reaction is called the inhibition constant or K.
  • the first advantage of the compounds relevant to the invention over the prior art, in addition to their lower volume requirement compared with the polyols, is that they have favorable inhibition constants with respect to the proteases which can be used in detergents and cleaners. This applies, for example, to serine proteases, but also to metalloproteases.
  • the inhibitors thus bind reversibly, ie they do not undergo solid and not too loose transient interactions with the enzyme.
  • the majority of the protease-relevant protease is thus present during storage in the form of a protease-inhibitor complex.
  • the protease and possibly other proteins contained, in particular other enzymes are protected in this way against proteolysis by this enzyme (stabilized against proteolysis).
  • the agent according to the invention with water 1 1
  • the binding equilibrium shifted towards dissociation, so that the complex dissolves and the majority of the invention relevant protease is proteolytically active.
  • the compounds relevant to the invention are functioning protease inhibitors and thus enzyme stabilizers for detergents and cleaners in accordance with the task formulated.
  • the second advantage of the invention relevant compounds over the prior art is that they have as elements only C, H, N and O and optionally halides and / or sulfur and in particular are free of boron. Thus, they do not form the undesirable boron-derived by-products with other detergent or cleaning ingredients.
  • the compounds mentioned probably act as reversible inhibitors because, similar to the substrate of the proteases, they are structurally adapted to the conditions of the binding pocket.
  • basically all proteases can be inhibited by the compounds relevant to the invention, so that they are suitable according to the invention as protease inhibitors.
  • a washing or cleaning process in which a protease is inhibited which is inhibited and / or stabilized with a compound described above;
  • washing or cleaning agent for washing and / or cleaning textiles and / or hard surfaces; such as
  • those detergents or cleaners are preferred in which the stabilizing compound has an inhibition constant (Ki) of 0.01 to 10 mM, preferably 0.1 to 5, particularly preferably 0.5 to 2, with respect to the protease contained. 12
  • the inhibition constant K 1 can be determined in the following way: For the characterization of a reversible inhibitor of the enzymatic activity, the inhibition constant K 1 is a characteristic and decisive variable. K 1 describes the equilibrium between enzyme, inhibitor and enzyme-inhibitor complex for reversible binding. The enzyme-inhibitor complex is catalytically inactive and inhibits the reaction by reducing the concentration of free enzyme that is still available for binding of substrate.
  • the ki is accordingly defined as:
  • [E], [I] and [El] denote the respective molar equilibrium concentrations of enzyme (E), inhibitor (I) and the enzyme-inhibitor complex (El). According to this definition, a substance with a small Ki is a good inhibitor under the respective test conditions.
  • K is made on the basis of the activity test of the protease in the presence of the corresponding inhibitor.
  • the established Michaelis-Menten kinetics are used to determine the enzymatic parameters K m and k cat in the presence of various concentrations of the inhibitor.
  • K 1 is obtained .
  • K using the Cheng-Prusoff equation (Equation 2) via the IC 50 - value are determined.
  • the determination of the IC 5 o-value is performed by determining the proteolytic activity on a substrate in the presence of various concentrations of inhibitor and fitting of the experimental data to a sigmoidal dose-response with variable slope equation (pseudo-Hill slopes). It is the value of half the inhibitor concentration that would be needed to achieve complete inhibition.
  • [S] is the substrate concentration in the assay and K d is the equilibrium dissociation constant for the substrate, which in IC 50 can be set to be identical to K m for the substrate.
  • the protease is especially in a content of 2 .mu.g to 20 mg per g of the composition, preferably from 5 ⁇ g to 17.5 mg per g of the agent, more preferably from 20 ⁇ g to 15 mg per g of the agent, most preferably from 50 ⁇ g to 10 ⁇ g of the agent.
  • the stabilizer is contained in agents according to the invention in particular in a content of up to 50 mg per g of the agent, preferably up to 10 mg, more preferably up to 7 mg, most preferably up to 5 mg per g of the agent. It is further preferred that the stabilizer is contained in a content of 0.01 to 100 ⁇ K, (based on the protease contained), preferably 0.1 to 10 ⁇ K 1, more preferably 1 to 5 ⁇ K 1 .
  • the molar ratio of stabilizer to protease is preferably in the range from 1: 1 to 1000: 1, in particular from 1: 1 to 500: 1, particularly preferably from 1: 1 to 100: 1, very particularly preferably from 1: 1 to 20 :1.
  • an agent according to the invention may contain at least one further stabilizer, in particular a polyol, such as glycerol or 1,2-ethylene glycol, and / or an antioxidant.
  • a further stabilizer in particular a polyol, such as glycerol or 1,2-ethylene glycol, and / or an antioxidant.
  • the protease stabilized or reversibly inhibited according to the invention is preferably a serine protease, in particular a subtilase, more preferably a subtilisin.
  • Subtilisin may be a wild-type enzyme or a subtilisin variant, wherein the wild-type enzyme or the starting enzyme of the variant is preferably selected from one of the following:
  • alkaline protease PB92, subtilisin 147 and / or 309 The alkaline protease PB92, subtilisin 147 and / or 309 (Savinase)
  • the alkaline protease from Bacillus lentus preferably from Bacillus lentus (DSM 5483), the alkaline protease from Bacillus alcalophilus (DSM 11233),
  • alkaline protease from Bacillus sp. (DSM 14392) or at least one of them
  • alkaline protease from Bacillus gibsonii (DSM 14393) or at least one to
  • the protease is a variant with a point mutation in the range of positions 95 to 103 (count according to subtilisin 309), preferably with an insertion of a single amino acid between position 99 and 100, more preferably starting from subtilisin 147 and / or 309 (subtilisin 309), or a variant thereof.
  • the protease is a variant having a point mutation in position 217 (count according to the wild type protease from Bacillus amyloliquefaciens, BPN '), preferably with a substitution of a single amino acid in this position, more preferably with the amino acid substitution X217L, most preferably starting from the wild type protease from Bacillus amyloliquefaciens (BPN '), or a variant thereof.
  • the protease is a variant having an amino acid change relative to a starting protease homologizable with the Bacillus lentus alkaline protease in one or more of the following positions: 3, 4, 36, 42, 43, 47, 56 , 61, 69, 87, 96, 99, 101, 102, 104, 114, 118, 120, 130, 139, 141, 142, 154, 157, 188, 193, 199, 205, 21 1, 224, 229, 236, 237, 242, 243, 250, 253, 255 and 268 in the enumeration of the Bacillus lentus alkaline protease, preferably with an amino acid change from the parent molecule in one or more of the following positions: 3, 4, 43, 61; 15
  • Agents according to the invention may contain, in addition to the protease, one or more further enzymes, in particular from the following group: one or more further proteases, amylases, hemicellulases, cellulases, lipases and oxidoreductases.
  • the amylase is preferably an ⁇ -amylase.
  • the hemicellulase is preferably a ⁇ -glucanase, a pectinase, a pullulanase and / or a mannanase.
  • the cellulase is preferably a cellulase mixture or a one-component cellulase, preferably or predominantly an endoglucanase and / or a cellobiohydrolase.
  • the oxidoreductase is preferably an oxidase, in particular a choline oxidase, or a perhydrolase.
  • Agents according to the invention preferably comprise at least one complexing agent and / or builder substances, the builder being in particular a zeolite builder, and / or a nonionic surfactant, the nonionic surfactant preferably being a hydroxy mixed ether, and / or optical Brightener, wherein the optical brightener is diphenyl compounds, in particular distyryl biphenyl derivatives, and / or stilbentriazine derivatives.
  • bromoacetophenone or chloroacetophenone are abs. In 60 ml. Under N 2 is heated to about 70 0 C and 0.06 mol of imidazole derivative in 15 ml of abs. Ethyl acetate was added dropwise.
  • the proteolytic residual activity of the Bacillus lentus alkaline protease F49 (according to WO 95/23221 A1) is determined in the presence of these compounds.
  • the following substances showed inhibition of proteolytic activity to a residual activity of less than 60%.
  • the proteolytic activity of the tested protease was reduced to a residual activity of 55% at a use concentration of 1 OmM.
  • the proteolytic activity of the tested protease was reduced to a residual activity of 49% at a use concentration of 1 OmM.
  • the basic formulation is a liquid detergent having the following composition (all figures in percent by weight): 0.3-0.5% xanthan gum, 0.2-0.4% anti-foaming agent, 6-7% 20
  • Glycerine 0.3-0.5% ethanol, 4-7% FAEOS, 24-28% nonionic surfactants, 1% boric acid, 1-2% sodium citrate (dihydrate), 2-4% soda, 14-16% coconut oil.
  • Fatty acids 0.5% HEDP, 0-0.4% PVP, 0-0.05% optical brightener, 0-0.001% dye, balance: demineralized water.
  • protease activity (handle-protease units) indicated in HPE is according to van Raay, Saran and Verbeek, according to the publication "For the determination of the proteolytic activity in enzyme concentrates and enzyme-containing detergents, rinses and cleaners" in Tenside (1970), Volume 7, pp. 125-132.
  • the storage is carried out for various periods of time in airtight containers at 30 0 C.
  • the initial values for the proteolytic activity of the agent in question are compared with the values determined after storage.

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Abstract

L’invention se rapporte à des agents lavants et nettoyants contenant des sels d’imidazolium agissant comme des inhibiteurs de la protéase et formant donc des stabilisateurs d’enzymes appropriés.
PCT/EP2009/052057 2008-03-18 2009-02-20 Sels d’imidazolium utilisés comme stabilisateurs d’enzymes WO2009115392A1 (fr)

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DE200810014760 DE102008014760A1 (de) 2008-03-18 2008-03-18 Imidazolium-Salze als Enzymstabilisatoren
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US10760036B2 (en) 2014-12-15 2020-09-01 Henkel Ag & Co. Kgaa Detergent composition comprising subtilase variants
EP3106508A1 (fr) 2015-06-18 2016-12-21 Henkel AG & Co. KGaA Composition détergente comprenant des variantes de subtilase
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WO2019201793A1 (fr) 2018-04-17 2019-10-24 Novozymes A/S Polypeptides ayant une activité de liaison des hydrates de carbone dans des compositions détergentes et leur utilisation pour réduire les plis de textiles ou de tissus
WO2020188095A1 (fr) 2019-03-21 2020-09-24 Novozymes A/S Variants d'alpha-amylase et polynucléotides codant pour ceux-ci
WO2020207944A1 (fr) 2019-04-10 2020-10-15 Novozymes A/S Variants polypeptidiques
WO2021037895A1 (fr) 2019-08-27 2021-03-04 Novozymes A/S Composition détergente
WO2021053127A1 (fr) 2019-09-19 2021-03-25 Novozymes A/S Composition détergente
WO2021064068A1 (fr) 2019-10-03 2021-04-08 Novozymes A/S Polypeptides comprenant au moins deux domaines de liaison aux hydrates de carbone
EP3892708A1 (fr) 2020-04-06 2021-10-13 Henkel AG & Co. KGaA Compositions de nettoyage comprenant des variantes de dispersine
WO2022074037A2 (fr) 2020-10-07 2022-04-14 Novozymes A/S Variants d'alpha-amylase
WO2022171780A2 (fr) 2021-02-12 2022-08-18 Novozymes A/S Variants d'alpha-amylase
WO2022268885A1 (fr) 2021-06-23 2022-12-29 Novozymes A/S Polypeptides d'alpha-amylase

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