EP4379067B1 - Iridoidderivate und ihre verwendung in einem gerbverfahren - Google Patents

Iridoidderivate und ihre verwendung in einem gerbverfahren

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Publication number
EP4379067B1
EP4379067B1 EP22306769.5A EP22306769A EP4379067B1 EP 4379067 B1 EP4379067 B1 EP 4379067B1 EP 22306769 A EP22306769 A EP 22306769A EP 4379067 B1 EP4379067 B1 EP 4379067B1
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EP
European Patent Office
Prior art keywords
aliphatic group
hydrogen atom
tanning
compound
formula
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EP22306769.5A
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English (en)
French (fr)
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EP4379067A1 (de
Inventor
Loic FONTAINE
Thomas Lecourt
Alexandra Le Foll
Stéphane MARCOTTE
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Centre National de la Recherche Scientifique CNRS
Universite de Rouen
Hermes Sellier SAS
Institut National des Sciences Appliquees de Rouen
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Centre National de la Recherche Scientifique CNRS
Universite de Rouen
Hermes Sellier SAS
Institut National des Sciences Appliquees de Rouen
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/08—Chemical tanning by organic agents

Definitions

  • the present invention relates to the field of tanning. More particularly, the present invention relates to particular iridoid derivatives and their use in a tanning process. It also relates to a process for cross-linking collagen using such iridoid derivatives.
  • the invention is set out in the appended set of claims.
  • Natural tannins have long been used in processes for tanning hides and stabilizing collagen.
  • Tanning mixtures are mainly composed of polyphenolic tannins, which are divided into two classes: condensed tannins and hydrolysable tannins.
  • the effectiveness of tanning is usually reflected by its ability to stabilize collagen, namely to limit collagen denaturation and impart good resistance to enzymatic hydrolysis.
  • Collagen stabilization can be assessed by measuring the increase in shrinkage temperature, which is correlated to the collagen denaturation temperature.
  • the polyphenolic tannins give rise to a shrinkage temperature around 75-85°C.
  • Other parameters can also be considered for assessing the effectiveness of tanning, such as the mechanical resistance of the hide and its sensory parameters, such as hide filling and suppleness.
  • genipin can be obtained from the fruit of Gardenia jasminoides or Genipa americana. Genipin allows to stabilize collagen and to reach shrinkage temperatures of 80°C (Zhang et al., JALCA, 2011, 106, 121). Genipin has also been used in combination with an aluminum-based tanning (Ding et al., JALCA, 2008, 103, 377), which resulted in a soft and full leather having a shrinkage temperature of 92°C.
  • Genipin has also been used to cross-link gelatin (Taylor et al., JALCA, 2009, 104, 79). Genipin is readily available in large quantities and is a known food coloring agent. However, using genepin in a tanning process leads to a dark blue color, which can be undesirable.
  • WO2009/065915 describes a tanning method using aglycone derivatives of iridoids and seco-iridoids, different from genipin.
  • Such derivatives which can be extracted from olive leaves, are hydrolyzed forms and aglycone forms of oleuropein.
  • the mixture obtained by extraction of the leaves in the presence of endogenous enzyme or by the use of acid is not purified and comprises polyphenolic compounds and compounds derived from hydrolyzed oleuropein, such as (4E)-4-formyl-3-(-1-formyl-2-methoxy-2-oxoethyl)hex-4-enoic acid.
  • Document US 2017/080040-A1 discloses a decoction of olive leaves which can be used in the treatment of tanning hides and which comprises an aqueous composition containing at least from about 500 mg/L to about 3,000 mg/L of oleuropein, from about 100 mg/L to about 300 mg/L of hydroxytyrosol, from about 90 mg/L to about 280 mg/L of tyrosol, from about 400 mg/L to about 1,800 mg/L of elenolic acid.
  • the inventors have demonstrated that particular derivatives of the genipin could be easily prepared in few steps, and used in a tanning process.
  • the inventors have shown that such tanning agents were at least as effective as genipin, but advantageously, did not lead to a dark color of the hide.
  • the derivatives can be produced in high amounts starting from genipin, and their high purity allows to use low amounts of tanning mixture.
  • the present invention relates to the use of a compound represented by the following formula (I), in a tanning process: wherein:
  • R 1 is a hydrogen atom or -C(O)-(C 1 -C 12 aliphatic group), preferably a hydrogen atom or -C(O)-(C 1 -C 6 alkyl).
  • R 2 is a C 1 -C 12 aliphatic group, preferably a C 1 -C 6 alkyl.
  • R 4 is -C(O)-CH 2 -R 5 , where R 5 is a hydrogen atom or -O-C(O)-(C 1 -C 12 aliphatic group), preferably a hydrogen atom or -O-C(O)-(C 1 -C 6 alkyl).
  • R 6 is hydrogen
  • R 7 is -OH or -O-C(O)-(C 1 -C 12 aliphatic group), preferably -OH or -O-C(O)-(C 1 -C 6 alkyl).
  • R 8 is -OH.
  • R 9 is a hydrogen atom or -O-C(O)-(C 1 -C 6 alkyl).
  • said compound of formula (I) is one of the following compounds:
  • said compound of formula (I) is one of the following compounds:
  • a use according to the invention is a use for tanning a hide or a skin.
  • a use according to the invention is a use in a method for manufacturing a leather or a leather substitute.
  • a use according to the invention is a use for tanning a collagen-containing material.
  • the present invention also relates to a compound of formula (I) per se, as defined herein, with the proviso that the compound is not one of the following compounds:
  • Another object of the present invention is a process for cross-linking collagen in a material comprising a step of contacting said material with a compound of formula (I) as defined herein.
  • said material is a hide or skin.
  • C x -C y in which x and y are integers, as used in the present disclosure, means that the corresponding chemical group comprises from x to y carbon atoms. If, for example, the expression C 1 -C 6 is used, it means that the corresponding chemical group may comprise from 1 to 6 carbon atoms, especially 1, 2, 3, 4, 5 or 6 carbon atoms. If, for example, the expression C 2 -C 5 is used, it means that the corresponding chemical group may comprise from 2 to 5 carbon atoms, especially 2, 3, 4, or 5 carbon atoms.
  • aliphatic refers to a non-aromatic, saturated or unsaturated, cyclic or acyclic (preferably acyclic), linear or branched hydrocarbon chain.
  • C 1 -C 12 aliphatic refers to an aliphatic having 1 to 12 carbon atoms.
  • the aliphatic may be an alkyl, an alkenyl, or an alkynyl.
  • alkyl refers to a saturated, acyclic, linear or branched hydrocarbon chain.
  • C 1 -C 6 alkyl refers to an alkyl having 1 to 6 carbon atoms. Examples of alkyl (or C 1 -C 6 alkyl) include, for instance, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, or hexyl.
  • alkenyl refers to an unsaturated, acyclic, linear or branched hydrocarbon chain, having at least one carbon-carbon double bond.
  • C 2 -C 6 alkenyl refers to an alkenyl having 2 to 6 carbon atoms. Examples of alkenyl (or C 2 -C 6 alkenyl) include for instance, ethenyl, propenyl, butenyl, pentenyl, or hexenyl.
  • alkynyl refers to an unsaturated, acyclic, linear or branched hydrocarbon chain, having at least one carbon-carbon triple bond.
  • C 2 -C 6 alkynyl refers to an alkynyl having 2 to 6 carbon atoms. Examples of alkynyl (or C 2 -C 6 alkynyl) include, for instance, ethynyl, propynyl, butynyl, pentynyl, or hexynyl.
  • aryl refers to a mono- or bi-cyclic aromatic hydrocarbon having from 6 to 12 carbon atoms.
  • aryl includes phenyl, biphenyl, or naphthyl.
  • the aryl is a phenyl.
  • the present invention relates to the use of a compound represented by the following formula (I), in a tanning process: wherein:
  • stereoisomer refers to compounds which have identical molecular formulae as identified herein but which differ in the layout of their atoms in space. Stereoisomers which are not mirror images of each other, are designated as “diastereoisomers”, and stereoisomers which are non-superposable mirror images of each other are designated as "enantiomers” or “optical isomers”. “Stereoisomers” refer to racemates, enantiomers and diastereoisomers.
  • the compound of formula (I) as defined herein is a compound of formula (III), a compound of formula (IV), or a mixture thereof: wherein, in formulae (III) and (IV):
  • the compound of the invention is a compound of formula (III) or a mixture (in particular, a racemic mixture) of a compound of formula (III) and a compound of formula (IV). More preferably, the compound of the invention is a compound of formula (III).
  • the "salts" of the compounds of the invention include usual salts formed from inorganic or organic acids or bases as well as quaternary ammonium salts. More specific examples of suitable acid salts include hydrochloric, hydrobromic, sulfuric, phosphoric, nitric, perchloric, fumaric, acetic, propionic, succinic, glycolic, formic, lactic, maleic, tartaric, citric, palmoic, malonic, hydroxymaleic, phenylacetic, glutamic, benzoic, salicylic, fumaric, toluenesulfonic, methanesulfonic, naphthalene-2-sulfonic, benzenesulfonic hydroxynaphthoic, hydroiodic, malic, steroic, tannic etc. More specific examples of suitable basic salts include sodium, lithium, potassium, magnesium, aluminum, calcium, zinc salts.
  • R 1 is a hydrogen atom, a C 1 -C 12 aliphatic group, aryl, -C(O)-(C 1 -C 12 aliphatic group), -C(O)-(aryl), -CH 2 -O-(C 1 -C 12 aliphatic group), or -CH 2 -O-(aryl), said aliphatic groups being each independently optionally substituted by an aryl, a halide, -OH, -O-(C 1 -C 12 aliphatic group), - N(C 1 -C 12 aliphatic group)(C 1 -C 12 aliphatic group), -O-C(O)-(C 1 -C 12 aliphatic group), -C(O)-O-(C 1 -C 12 aliphatic group), -C(O)-NH-(C 1 -C 12 aliphatic group), -NH-C(O)-(C 1 -C 12 aliphatic group
  • R 1 is a hydrogen atom, a C 1 -C 12 aliphatic group, aryl, -C(O)-(C 1 -C 12 aliphatic group), -C(O)-(aryl), -CH 2 -O-(C 1 -C 12 aliphatic group), or -CH 2 -O-(aryl), said aliphatic groups being each independently optionally substituted by an aryl.
  • a preferred C 1 -C 12 aliphatic group substituted by an aryl is a methyl substituted by a phenyl, namely a benzyl.
  • R 1 is a hydrogen atom, a C 1 -C 12 aliphatic group, aryl, -C(O)-(C 1 -C 12 aliphatic group), -C(O)-(aryl), -CH 2 -O-(C 1 -C 12 aliphatic group), or -CH 2 -O-(aryl), said aliphatic groups being each unsubstituted.
  • a preferred C 1 -C 12 aliphatic group in R 1 is a C 1 -C 6 alkyl.
  • R 1 is a hydrogen atom, a C 1 -C 12 aliphatic group, -C(O)-(C 1 -C 12 aliphatic group), -CH 2 -O-(C 1 -C 12 aliphatic group), said aliphatic groups being each independently optionally substituted by an aryl.
  • R 1 is a hydrogen atom or -C(O)-(C 1 -C 12 aliphatic group).
  • R 1 is a hydrogen atom, a C 1 -C 6 alkyl group, -C(O)-(C 1 -C 6 alkyl), -CH 2 -O-(C 1 -C 6 alkyl group), said alkyl groups being each independently optionally substituted by phenyl.
  • R 1 is a hydrogen atom or a -C(O)-(C 1 -C 6 alkyl) such as -C(O)-CH 3 .
  • R 1 is -C(O)-(C 1 -C 6 alkyl), such as -C(O)-CH 3 .
  • R 2 is a hydrogen atom or a C 1 -C 12 aliphatic group. More particularly, R 2 may be a hydrogen atom or a C 1 -C 6 alkyl group.
  • R 2 is a C 1 -C 12 aliphatic group, more preferably a C 1 -C 6 alkyl, such as a methyl.
  • the compound of formula (I) is such that:
  • the compound of formula (I) is such that:
  • R 5 is a hydrogen atom, a C 1 -C 6 alkyl group, -OH, or -O-C(O)-(C 1 -C 6 alkyl group).
  • R 5 is a hydrogen atom or -O-C(O)-(C 1 -C 12 aliphatic group), more preferably a hydrogen atom or -O-C(O)-(C 1 -C 6 alkyl), even more preferably, a hydrogen atom or -O-C(O)-CH 3 .
  • R 5 ' is a hydrogen atom, a C 1 -C 6 alkyl group, -OH, or -O-C(O)-(C 1 -C 6 alkyl group).
  • R 5 ' is hydrogen atom, -OH, or -O-C(O)-CH 3 . More preferably, R 5 ' is -OH.
  • the compound of formula (I) is such that:
  • the compound of formula (I) is such that:
  • R 3 and R 4 form together a chain of formula (II) as defined herein, wherein R 6 , R 7 , R 8 , and R 9 are each independently a hydrogen atom, -OH, or -O-C(O)-(C 1 -C 12 aliphatic group).
  • the compound of formula (I) can be represented as follows: wherein R 1 , R 2 , R 6 , R 7 , R 8 , and R 9 are as defined herein.
  • stereochemistry of the compound of formula (I-II) may be as follow: wherein R 1 , R 2 , R 6 , R 7 , R 8 , and R 9 are as defined herein.
  • the compound of the invention is a compound of formula (III-II) or a mixture (in particular, a racemic mixture) of a compound of formula (III-II) and a compound of formula (IV-II). More preferably, the compound of the invention is a compound of formula (III-II).
  • each stereogenic center that is not defined encompasses both (R) and (S) configurations.
  • R 6 , R 7 , R 8 , and R 9 are each independently a hydrogen atom, -OH, or -O-C(O)-(C 1 -C 6 alkyl group).
  • At least one (preferably at least two) among R 7 , R 8 , and R 9 are not hydrogen atoms.
  • R 6 is hydrogen
  • R 7 is hydrogen, -OH or -O-C(O)-(C 1 -C 6 alkyl), for instance hydrogen, -OH or -O-C(O)-CH 3 .
  • R 7 is -OH or -O-C(O)-(C 1 -C 12 aliphatic group).
  • R 7 is -OH or -O-C(O)-(C 1 -C 6 alkyl), more preferably -OH or -O-C(O)-CH 3 .
  • R 7 is -O-C(O)-(C 1 -C 12 aliphatic group), for instance -C(O)-CH 3 .
  • R 8 is hydrogen or -OH.
  • R 5 is -OH.
  • R 9 is a hydrogen atom, -OH, or -O-C(O)-(C 1 -C 6 alkyl), preferably a hydrogen atom, -OH or -O-C(O)-CH 3 .
  • R 9 is a hydrogen atom or -O-C(O)-(C 1 -C 12 aliphatic group).
  • R 9 is a hydrogen atom or -O-C(O)-(C 1 -C 6 alkyl), more preferably a hydrogen atom or -O-C(O)-CH 3 .
  • R 9 is -O-C(O)-(C 1 -C 12 aliphatic group), for instance -C(O)-CH 3 .
  • the compound of formula (I) (or of formula (I-II)) is such that R 3 and R 4 form together a chain of formula (II) wherein:
  • the compound of formula (I) (or of formula (I-II)) is such that:
  • the compound of formula (I) (or of formula (I-II)) is such that R 3 and R 4 form together a chain of formula (II) wherein:
  • the compound of formula (I) (or of formula (I-II)) is such that:
  • the compound of formula (I) is one of the following compounds:
  • the compound of formula (I) is one of the following compounds:
  • the compound of formula (I) used in the present invention is one of the following known compounds:
  • the compound of formula (I) used in the present invention is one of the following compounds:
  • the compound of formula (I) is not one of the following compounds (including any stereoisomer thereof):
  • Compounds of the invention can be prepared by any suitable technique known to the skilled artisan.
  • compounds of the invention can be prepared as detailed in the examples.
  • such compounds can be prepared starting from genipin, and by subjecting genipin to a succession of suitable synthetic reactions, such as oxidation, reduction, dihydroxylation, and/or acylation.
  • a tanning process may comprise or not a pre-tanning step.
  • the compound of formula (I) according to the invention may be used as a pre-tanning agent and/or tanning agent in a process comprising a pre-tanning step.
  • it may be chosen from the group consisting of: polyphenolic extract for various vegetable, mainly gallnut, quebracho, oak, metal salt of chromium, iron, zirconium, titanium, aluminum, mainly with chloride and sulfate as counter ion, and synthetics chemicals like formol, glutaraldehyde, oxazolidine, zeolite, formol phenol (and derivate like cresol, phenol sulfonic acids) condensate, formol bisphenol (A, B, S and F) condensate, formol melamine condensate, and a mixture thereof.
  • the compound of formula (I) according to the invention may be used as a tanning agent in a tanning process not comprising a pre-tanning step.
  • the tanning process may in particular be a process for tanning a collagen-containing material, and more particularly for tanning a hide or a skin.
  • said collagen-containing material or said hide or skin, is treated (typically, contacted) with one or more compounds of formula (I), or a composition comprising the same.
  • collagen refers to naturally occurring collagens or modified collagens.
  • collagen as used herein also refers to collagens prepared using recombinant techniques.
  • the term collagen includes collagen, collagen fragments, collagen dispersion obtained from hide grinding and various purification steps (e.g. enzymatic or acidic hydrolysis), collagen fibers obtained through precipitation of dispersed or soluble collagen (e.g. salt, brine or ammoniac precipitation), collagen-like proteins, triple helical collagen, alpha chains, monomers, gelatin, trimers and combinations thereof.
  • Recombinant expression of collagen and collagen-like proteins is known in the art (see in particular EP 1,232,182 ; US 6,428,978 ; US 8,188,230 ).
  • the collagen can be a chemically-modified collagen, a truncated collagen, unmodified or post-translationally modified, or amino acid sequence-modified collagen.
  • the collagen can be plant-based collagen.
  • a collagen solution can be fibrillated into collagen fibrils.
  • collagen fibrils refer to nanofibers composed of tropocollagen or tropocollagen-like structures.
  • a recombinant collagen can comprise a collagen fragment of the amino acid sequence of a native collagen molecule capable of forming tropocollagen (trimeric collagen).
  • a recombinant collagen can also comprise a modified collagen or truncated collagen having an amino acid sequence at least 70, 80, 90, 95, 96, 97, 98, or 99% identical or similar to a native collagen amino acid sequence.
  • the collagen fragment can be a 50 kDa portion of a native collagen.
  • the collagen-containing material refers to a material comprising or consisting of collagen.
  • the collagen-containing material may be from any origin, in particular from an animal (e.g. goat, bovine such as calf, cow or cattle, ovine such as sheep or lamb, reptile such as crocodile or lizard, or fish such as trout or salmon).
  • said collagen-containing material is a hide or a skin.
  • the hide or skin may be from any animal, (e.g. goat, bovine such as calf, cow or cattle, ovine such as sheep or lamb, reptile such as crocodile or lizard, or fish such as trout or salmon).
  • the treating or contacting step may be carried out under classical conditions known to the skilled artisan.
  • the collagen-containing material in particular, said hide or skin
  • the collagen-containing material may be contacted with said one or more compounds of formula (I) in an aqueous solution, optionally comprising further auxiliary agents such as, proteins, peptides, protein hydrosylates, polyamines, pH buffer, sodium chloride, sodium sulfate, sodium citrate, ammonium chloride, naphthalene sulfonic polymer, preservatives, or slippery agent.
  • concentration of compound(s) of formula (I) in the aqueous solution is typically comprised between 0.1 wt% and 40 wt%, preferably between 0.5% and 25%.
  • the pH of the aqueous solution may be within a range from 1 to 15, preferably from 7 to 11. Said pH may be adjusted by using a buffer, such as a carbonate or phosphate buffer.
  • the treating or contacting step may be carried out at a temperature comprised between 4 °C and 70 °C, preferably between 20 °C and 50 °C, more preferably between 30 °C and 40 °C.
  • the treating or contacting step may be carried out for a duration comprised between 1 hour and 90 hours, preferably between 15 hours and 50 hours.
  • the compound(s) of formula (I) may be used in a tanning process in combination with other tanning agents, such as mineral, vegetal, organic or enzymatic tanning agents (e.g.
  • polyphenolic extract for various vegetable, mainly gallnut, quebracho, oak, metal salt of chromium, iron, zirconium, titanium, aluminum, mainly with chloride and sulfate as counter ion, and synthetics chemicals like formol, glutaraldehyde, oxazolidine, zeolite, formol phenol (and derivate like cresol, phenol sulfonic acids) condensate, formol bisphenol (A, B, S and F) condensate, formol melamine condensate, and a mixture thereof).
  • the tanning step can be carried out in a tanning drum, a reactor or any other adapted device.
  • compounds of formula (I) used according to the invention allow to obtain a high-quality leather or leather substitute.
  • said leather or leather substitute may:
  • the shrinkage temperature may in particular be suitable to shave leather and to prepare the step of tanning (i.e. the step subsequent to the pre-tanning, if present in the tanning process).
  • the high-quality grain and leather surface may in particular be suitable for aniline finishing, and be characterized by a very low shrinking of the grain.
  • Another object of the present invention is a process for cross-linking collagen in a material comprising a step of contacting said material with a compound of formula (I) as defined herein.
  • Said material may in particular be a hide or skin.
  • Genipin 1 (5 g, 22.1 mmol) was suspended in dichloromethane (90 mL) under an argon atmosphere. Pyridine (5.5 mL, 68.0 mmol, 3 eq) followed by acetic anhydride (12.5 mL, 132.2 mmol, 6 eq) were added to the mixture while stirring at room temperature. The reaction was followed by TLC (cyclohexane/AcOEt 7/3).
  • R f 0.44 (SiO 2 , cyclohexane/AcOEt 7/3).
  • the obtained yellow oil was purified by silica gel chromatography (dichloromethane/ethyl acetate 1/1) to afford a mixture of both regioisomers 3a and 3b (85:15) as a yellow oil (1.76 g, 5.11 mmol, 79 %, 1 H NMR purity > 95%).
  • the proportion of 3a vs 3b depends on the reaction time. The longer the reaction was, the more 3b was formed.
  • R f 0.23 (SiO 2 , cyclohexane/AcOEt 1/1).
  • R f 0.31 (SiO 2 , cyclohexane/AcOEt 1/1).
  • R f 0.23 (SiO 2 , cyclohexane/AcOEt 1/1).
  • Potassium carbonate (0.31 g, 2.25 mmol, 3 eq)
  • potassium ferricyanide(III) 1.234 g, 3.75 mmol, 5 eq
  • potassium osmate(VI) dihydrate 0.011 g, 0.03 mmol, 0.04 eq
  • quinuclidine 0.006 g, 0.05 mmol, 0.07 eq
  • the suspension was cooled to 0 °C and a solution of 5 (0.189 g, 0.75 mmol) in THF (2 mL) was added.
  • the orange suspension was vigorously stirred at 0 °C for 4h and sodium sulfite (0.470 g, 4.5 mmol, 6 eq) was introduced.
  • the reaction mixture was allowed to return to room temperature and, after 30 minutes, filtered over a short pad of celite.
  • the aqueous layer was extracted with EtOAc. Combined organic layers were washed with HCl aqueous solution (1M), saturated aqueous NaHCO 3 and brine, dried over MgSO 4 and evaporated under reduced pressure.
  • the yellow oil obtained was purified by silica gel chromatography (cyclohexane/ethyl acetate 4/6) to afford the targeted diol 6 (0.085 g, 0.30 mmol, 40%, 1 H NMR purity > 95%) as a yellow oil.
  • R f 0.18 (SiO 2 , cyclohexane/ethyl acetate 1/1).
  • Collagen powder (200 mg) was immersed in ultrapure water (3 mL, 1500% w/w) in a vial for rehydration. After 24 hours, the rehydrated collagen was filtered and rinsed with ultrapure water.
  • the tanning compound (10 mg, 5% w/w) was weighed into a brown vial and dissolved in a carbonate buffer solution of pH 10 (1M, 3 mL, 1500% w/w). The rehydrated collagen powder was then added. The sealed vial was heated at 37°C for 48 h with moderate stirring. The collagen powder was finally filtered and thoroughly rinsed with ultrapure water (ca. 20 mL).
  • Shrinkage temperatures were measured by Differential Scanning Calorimetry (DSC). The temperatures shown in Table 1 are average values.
  • Table 1 Tanning compound Shrinkage Temperature Colour of the collagen powder Collagen Powder 60 °C Cream-white Genipin 83 °C Dark blue Compound 2 (comparative) 83 °C Dark blue Compound 5 (comparative) 79 °C Dark green Compounds 3a + 3b (85/15) 74 °C Yellow-Orange Compound 4 75 °C Yellow-Orange Compound 6 74 °C Yellow-Orange Compound 7 74 °C Yellow-Orange Compound 8 74 °C Yellow-Orange
  • the previous protocol is repeated with compounds 6a and 6b.
  • a parameter chosen among the tanning time (Table 2), the temperature (Table 3), the tanning agent content (Table 4) or the buffer solution (Table 5) is modified.
  • the influence of the said parameter is assessed by comparing the shrinkage temperatures.
  • Tables 2 to 5 show that the compounds of the invention are versatile tanning agents, which can be used in various conditions. Moreover, Table 4 shows that a limited amount, e.g 5%, of the tanning agent is needed to give optimum tanning. When compared to WO2009/065915 and Schrmür and Meyer (IULTCS Congress Dresden, 2019), which describe the use of iridoids extracts, the compounds of the invention can be used in a much lower amount, which allows a lower organic content of the effluent.
  • Example 3 Tanning of calf hide with compounds 3a and 3b
  • the tanning 3a + 3b compound (600 mg, 5% w/w) was dissolved in a citric acid - sodium hydrogenophosphate buffer solution of pH 7.4 (40 mL, 300% w/w).
  • the delimed calf hide (5 cm x 5 cm, 12 g) was then added.
  • the tanning solution was agitated and heated at 35 °C in a shaking water bath. After 48 h, the tanned hide was thoroughly rinsed with water and added in a solution of gallnut (retanning agent, 1.6 g, 13% w/w) in water at pH 7 (40 mL, 300% w/w).
  • T S Shrinkage temperature

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Claims (17)

  1. Verwendung einer Verbindung dargestellt durch die folgende Formel (I) in einem Gerbverfahren: wobei:
    - R1 ein Wasserstoffatom, eine C1-C12 aliphatische Gruppe, Aryl, -C(O)-(C1-C12 aliphatische Gruppe), -C(O)-(Aryl), -CH2-O-(C1-C12 aliphatische Gruppe), oder -CH2-O-(Aryl) ist, wobei die aliphatischen Gruppen jeweils unabhängig voneinander optional substituiert sind durch ein Aryl, ein Halogenid, -OH, -O-(C1-C12 aliphatische Gruppe), -N(C1-C12 aliphatische Gruppe)(C1-C12 aliphatische Gruppe), -O-C(O)-(C1-C12 aliphatische Gruppe), -C(O)-O-(C1-C12 aliphatische Gruppe), -C(O)-NH-(C1-C12 aliphatische Gruppe), -NH-C(O)-(C1-C12 aliphatische Gruppe), -NH-C(O)-NH-(C1-C12-aliphatische Gruppe), -NH-C(O)-O-(C1-C12-aliphatische Gruppe), -O-C(O)-NH-(C1-C12-aliphatische Gruppe) oder -O-C(O)-O-(C1-C12-aliphatische Gruppe)
    - R2 ein Wasserstoffatom oder eine C1-C12 aliphatische Gruppe ist,
    - R3 -CH2 -C(O)H oder -CH2 -CH2-OH ist,
    - R4 -C(O)-CH2-R5 oder -CH(OH)-CH2-R5 ' ist, wobei R5 und R5' jeweils unabhängig voneinander ein Wasserstoffatom, eine C1-C12 aliphatische Gruppe, -OH, oder -O-C(O)-(C1 - C12 aliphatische Gruppe), sind
    oder R3 und R4 bilden zusammen die folgende Kette der Formel (II): wobei R6, R7, R8 und R9 jeweils unabhängig voneinander ein Wasserstoffatom, -OH, oder -O-C(O)-(C1-C12 aliphatische Gruppe) sind,
    oder ein Salz davon.
  2. Verwendung nach Anspruch 1, wobei R1 ein Wasserstoffatom oder -C(O)-(C1-C12 aliphatische Gruppe), bevorzugt ein Wassertoffatom oder -C(O)-(C1-C6 Alkyl) ist.
  3. Verwendung nach Anspruch 1 oder 2, wobei R2 eine C1-C12 aliphatische Gruppe, bevorzugt ein C1-C6 Alkyl ist.
  4. Verwendung nach einem der Ansprüche 1 bis 3, wobei R4 -C(O)-CH2-R5 ist, wobei R5 ein Wasserstoffatom oder -O-C(O)-(C1-C12 aliphatische Gruppe), bevorzugt ein Wasserstoffatom oder -O-C(O)-(C1-C6 Alkyl) ist.
  5. Verwendung nach einem der Ansprüche 1 bis 4, wobei, R6 Wasserstoff ist.
  6. Verwendung nach einem der Ansprüche 1 bis 5, wobei R7 -OH oder -O-C(O)-(C1-C12 aliphatische Gruppe), bevorzugt -OH oder -O-C(O)-(C1 -C6 Alkyl) ist.
  7. Verwendung nach einem der Ansprüche 1 bis 6, wobei R8 -OH ist.
  8. Verwendung nach einem der Ansprüche 1 bis 7, wobei R9 ein Wasserstoffatom oder -O-C(O)-(C1-C6 Alkyl) ist.
  9. Verwendung nach Anspruch 1, wobei die Verbindung eine der folgenden Verbindungen ist:
  10. Verwendung nach Anspruch 1, wobei die Verbindung eine der folgenden Verbindungen ist:
  11. Verwendung nach einem der Ansprüche 1 bis 10 zum Gerben eines Fells oder einer Haut.
  12. Verwendung nach einem der Ansprüche 1 bis 10 zum Gerben eines kollagenhaltigen Materials.
  13. Ein Verfahren zur Herstellung von einem Leder oder einem Lederersatz umfassend die Verwendung nach einem der Ansprüche 1 bis 10.
  14. Eine Verbindung dargestellt durch die folgende Formel (I): wobei:
    - R1 ein Wasserstoffatom, eine C1-C12 aliphatische Gruppe, Aryl, -C(O)-(C1-C12 aliphatische Gruppe), -C(O)-(Aryl), -CH2-O-(C1-C12 aliphatische Gruppe), oder -CH2-O-(Aryl) ist, wobei die aliphatischen Gruppen jeweils unabhängig voneinander optional substituiert sind durch ein Aryl, ein Halogenid, -OH, -O-(C1-C12 aliphatische Gruppe), -N(C1-C12 aliphatische Gruppe)(C1-C12 aliphatische Gruppe), -O-C(O)-(C1-C12 aliphatische Gruppe), -C(O)-O-(C1-C12 aliphatische Gruppe), -C(O)-NH-(C1-C12 aliphatische Gruppe), -NH-C(O)-(C1-C12 aliphatische Gruppe), -NH-C(O)-NH-(C1-C12-aliphatische Gruppe), -NH-C(O)-O-(C1-C12-aliphatische Gruppe), -O-C(O)-NH-(C1-C12-aliphatische Gruppe) oder -O-C(O)-O-(C1-C12-aliphatische Gruppe)
    - R2 ein Wasserstoffatom oder eine C1-C12 aliphatische Gruppe ist,
    - R3 -CH2-C(O)H oder -CH2-CH2-OH ist,
    - R4 -C(O)-CH2-R5 oder -CH(OH)-CH2-R5' ist, wobei R5 und R5' jeweils unabhängig voneinander ein Wasserstoffatom, eine C1-C12 aliphatische Gruppe, -OH, oder -O-C(O)-(C1-C12 aliphatische Gruppe) sind
    oder R3 und R4 bilden zusammen die folgende Kette der Formel (II): wobei R6, R7, R8 und R9 jeweils unabhängig voneinander ein Wasserstoffatom, -OH, oder -O-C(O)-(C1-C12 aliphatische Gruppe) sind,
    oder ein Salz davon,
    mit der Maßgabe, dass die genannte Verbindung nicht zu den folgenden Verbindungen gehört:
  15. Die Verbindung nach Anspruch 14, die wie in einem der Ansprüche 2 bis 9 definiert ist.
  16. Ein Verfahren zum Vernetzen von Kollagen in einem Material, umfassend einen Schritt des Inkontaktbringens des Materials mit einer Verbindung, wie in einem der Ansprüche 1 bis 10 definiert.
  17. Das Verfahren nach Anspruch 16, wobei das Material ein Fell oder eine Haut ist.
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US6150081A (en) 1997-12-24 2000-11-21 Fuji Photo Film B.V. Silver halide emulsions with recombinant collagen suitable for photographic application and also the preparation thereof
US6428978B1 (en) 1998-05-08 2002-08-06 Cohesion Technologies, Inc. Methods for the production of gelatin and full-length triple helical collagen in recombinant cells
JP2003513659A (ja) 1999-11-12 2003-04-15 ファイブローゲン、インコーポレーテッド 動物コラーゲン及びゼラチン
EP2062985A1 (de) 2007-11-23 2009-05-27 N-Zyme BioTec GmbH Mittel und Verfahren zur Gerbung von Häuten und Fellen
WO2015173705A1 (en) * 2014-05-15 2015-11-19 Pesle Livio Decoction of olive leaves
IT201600081688A1 (it) * 2016-08-03 2018-02-03 Tannow S R L Impiego di acque di vegetazione olearia nell'industria conciaria
CA3008850A1 (en) 2017-06-29 2018-12-29 Modern Meadow, Inc. Yeast strains and methods for producing collagen
CA3012006A1 (en) 2017-07-31 2019-01-31 Modern Meadow, Inc. Yeast strains and methods for controlling hydroxylation of recombinant collagen
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