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
  • C14C1/00—Chemical treatment prior to tanning
  • C14C1/06—Facilitating unhairing, e.g. by painting, by liming
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
  • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
  • C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
  • C07C323/12—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
  • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
  • C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
  • C07C323/15—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being unsaturated and containing rings other than six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
  • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
  • C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
  • C07C323/16—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
  • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
  • C07C323/17—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a ring other than a six-membered aromatic ring of the carbon skeleton
• • 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
  • C14C1/00—Chemical treatment prior to tanning
  • C14C1/06—Facilitating unhairing, e.g. by painting, by liming
  • C14C1/065—Enzymatic unhairing
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
  • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/14—The ring being saturated

Definitions

• the present invention relates to a method for removing horny substances from the skins of dead animals, characterized in that the skins of dead animals with at least one substance of the general formula I
• R 1 , R 4 are the same or different and selected from hydrogen, C 6 -C 4 aryl and C 1 -C 2 alkyl, unsubstituted or substituted by one or more SH or OH groups
• R 2 , R 3 are the same or different and selected from hydrogen, C 6 -C aryl and CrC ⁇ 2 alkyl, unsubstituted or substituted with one or more SH or OH groups
• at least one radical R 2 or R 3 being different from hydrogen or R 1 and R 4 are different from hydrogen, and where in each case two vicinal radicals R 1 to R 4 together can mean alkylene
• X 1 , X 2 , X 3 and X 4 selected from OH, SH and NHR 5 , where in the case that R 1 to R 4 contains at least one sulfur atom, at least one X 1 to X 4 means SH, and for the case that R 1 to R 4 contains no sulfur atom mean at least two X 1 to X 4 SH.
• US Pat. No. 1,973,130 describes the use of numerous organic sulfur compounds, in particular in the presence of lime (column 1, line 40), for depilating, for example, calf skins.
• Ethyl mercaptan in particular, is a malodorous reagent, and waste water containing ethyl mercaptan is difficult to process, which prevents use in the water workshop.
• FR 1,126,252 describes the depilation of animal skins by the action of water-soluble thiols, in particular thioglycolamide (example 1) or thiogiycerin (example 2) in the presence of ammonium sulfate at a pH of 7-8 on animal skins.
• DE 21 31 630 shows that agents consisting of at least 0.25% by weight dimer-captobutanediol and about 0.01 to 40% by weight of a water-soluble guanidine compound and a pH of less than 12 on guinea pigs can be used to depilate them, or on human cornea to remove calluses without causing skin irritation in guinea pigs or even erythremia (malignant growths in the red blood cell education system). The epidermis remains intact in the treatment described in DE 21 31 630.
• EP-A 0 095 916 discloses the use of formulations comprising aminoethanethiol and 1,4-dimercaptobutanediol and an aminoguanidine or diguanide compound in order to eliminate unwanted human body and facial hair.
• page 2 line 1 it is taught that small thiol molecules are preferred for quick hair removal because they penetrate the skin faster. The epidermis is retained in the treatment described in EP-A 0 095 916.
• EP-A 0 096 521 discloses the use of formulations comprising, for example, 1,4-dimercaptobutanediol and an aminoguanidine or diguanide compound, in order to eliminate unwanted human body and facial hair. The epidermis is retained in the treatment described in EP-A 0 096 521.
• collagen can be modified by opening S-S bridges in the collagen by reaction with dithioerythrol and subsequent chlorination with chloroacetamide or chloroacetic acid, see. for example E. Heidemann, "Fundamentals of Leather Manufacturing", E. Roether KG Druckerei und Verlag, Darmstadt 1993, page 253. Protein solutions can also be preserved by adding dithioerythrol or dithiothreitol. The preservation is based on a kind of protection against oxidation because dithioerythrol is usually first oxidized instead of the protein SH groups.
• the task was to provide a method for removing horny substances from the skins of dead animals. There was also the task of providing bare feet, ie skins of dead animals from which horny substances were removed. There was also the task of providing compounds with the aid of which horny substances were removed Skinning dead animals can be removed, as well as a suitable manufacturing process.
• horny substances are understood to be calluses, feathers, parts of nails and claws, and in particular hair of animals.
• the skins of dead animals can still contain residues of meat from the dead animals concerned. It is essential to the invention that they contain horny substances.
• the amount of home substance based on the total weight of the skin or of the fur or of the fur, is not critical.
• the method according to the invention is suitable both for removing large amounts of home substance and, for example, for removing small hair residues.
• Animal skins are understood to mean at least one whole animal skin or at least a part of a skin of at least one dead animal. Of course, one can also treat skins or pieces of skin of several dead animals according to the invention.
• dead animals are not only understood to mean slaughtered or otherwise killed animals, but also those animals which have died as a result of accidents, for example traffic accidents or fights with conspecifics or other animals, or due to natural causes such as age or illness ,
• the skins of dead animals are usually skins of cattle, calves, pigs, goats, sheep, lambs, elk, game such as deer or roe deer, and also birds such as ostriches, fish or reptiles such as snakes.
• R 1 , R 4 are the same or different and selected
• C 6 -C 14 aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9- Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyI, particularly preferably phenyl,
• C 1 -C 2 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-decyl or n-dodecyl, particularly preferably CrC-alkyl such as methyl, ethyl, n-propyl, iso Propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl;
• CrC ⁇ 2 alkyl substituted with one or more hydroxy or thiol groups such as hydroxymethyl, 2-hydroxyethyl, 1, 2-dihydroxyethyl, 3-hydroxy-n-propyl, 2-hydroxy-iso-propyl, ⁇ -hydroxy-n- Butyl, ⁇ -hydroxy-n-decyl, HS-CH 2 -; HS- (CHJ Z - or HS- (CH 2 ) 3 - and especially hydrogen.
• hydroxy or thiol groups such as hydroxymethyl, 2-hydroxyethyl, 1, 2-dihydroxyethyl, 3-hydroxy-n-propyl, 2-hydroxy-iso-propyl, ⁇ -hydroxy-n- Butyl, ⁇ -hydroxy-n-decyl, HS-CH 2 -; HS- (CHJ Z - or HS- (CH 2 ) 3 - and especially hydrogen.
• R 2 , R 3 are the same or different and selected
• C 6 -C 14 aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9- Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl,
• CrC 12 alkyl such as 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-decyl or n-dodecyl, particularly preferably CC 4 -alkyl such as methyl, ethyl, n-propyl, iso- Propyl, n-butyl, isobutyl, sec-butyl and tert-butyl, very particularly preferably methyl,
• CrCi 2 alkyl substituted with one or more hydroxy or thiol groups such as hydroxymethyl, 2-hydroxyethyl, 1, 2-dihydroxyethyl, 3-hydroxy-n-propyl, 2-hydroxy-iso-propyl, ⁇ -hydroxy-n-butyl , ⁇ -hydroxy-n-decyl, HS-CH 2 -; HS- (CH 2 ) 2 - or HS- (CH 2 ) 3 -.
• At least one radical R 2 or R 3 is different from hydrogen, or R 1 and R 4 are different from hydrogen.
• R 2 and R 3 are different from hydrogen.
• R 1 , R 2 and R 3 are different from hydrogen.
• R 1 , R 2 , R 3 and R 4 are different from hydrogen.
• two vicinal radicals R 1 to R 4 may together represent C 3 -C ⁇ 0 alkylene such as - (CH 2) 3 -, - (CH 2) 2 -CH (CH 3) -, - (CH 2) 2 - CH (C 2 H 5 ) -, - (CH 2 ) 4 -, - (CH 2 ) 5 -, - (CH 2 ) 6 -, preferably C 3 -C 5 alkylene; in particular - (CH 2 ) 3 -, - (CH 2 ) 2 -CH (CH 3 ) -, - (CH 2 ) 2 -CH (C 2 H 5 ) -, - (CH 2 ) -, - (CH 2 ) 5 - and form a ring.
• C 3 -C ⁇ 0 alkylene such as - (CH 2) 3 -, - (CH 2) 2 -CH (CH 3) -, - (CH 2) 2 - CH (C 2 H 5 ) -
• R 1 and R 2 together to mean - (CH 2 ) 4 - or - (CH 2 ) 5 - to form a cyclopentenyl or cyclohexenyl system. It is also possible for R 2 and R 3 together to be a - (CH 2 ) 4 - or - (CH 2 ) s group to form an optionally 1,2-dimethylenecyclopentane system or an optionally substituted 1,2- Dimethylene cyclohexane system.
• X 1 , X 2 , X 3 and X 4 are selected from OH, SH and NHR 5 , where in the case that R 1 to R 4 contains at least one sulfur atom, at least one X 1 to X 4 means SH, and for that Case that R 1 to R 4 contains no sulfur atom, mean at least two X 1 to X 4 SH.
• at least one of the compounds 1.1 to I.9 is used:
• Corresponding alkali metal and alkaline earth metal salts include, in particular, the mono- and disodium salts, mono- and dipotassium salts and potassium sodium salts of the compounds of the general formula I, as well as the corresponding calcium and magnesium salts.
• Corresponding ammonium and phosphonium salts include NH 4 + salts and primary, secondary, tertiary and in particular quaternary mono- and diammonium salts and phosphonium salts. Mixtures of compounds of the general formula I and their corresponding alkali metal, alkaline earth metal, ammonium or phosphonium salts can of course also be used.
• Preferred mono- and diammonium salts have as cations those of the formula N (R 7 ) (R 8 ) (R 9 ) (R 10 ) + , where R 7 to R 10 are each the same or different and selected from hydrogen, CrC ⁇ 2 alkyl , Phenyl or CH 2 -CH 2 -OH. Examples include tetramethylammonium, tetraethylammonium, methyldiethanolammonium and n-butyldiethanolammonium.
• Preferred mono- and diphosphonium salts have cations of the formula P (R 7 ) (R 8 ) (R 9 ) (R 10 ) + , where R 7 to R 10 are as defined above.
• X 1 and X 4 each represent SH.
• At least one is preferred, and at least two groups X 1 to X 4 are particularly preferred hydroxyl groups.
• variables are selected as follows:
• R 1 and R 4 each represent hydrogen, R 2 represents methyl,
• R 3 is hydrogen or methyl
• X 1 and X 4 are SH
• X 2 and X 3 are OH.
• an amount of 0.1 to 5% by weight of at least one compound of the general formula I, based on the skin or salt weight of the skin of dead animals, is sufficient. 0.5 to 2.5% by weight are preferred, 0.75 to 1.5% by weight are particularly preferred.
• the treatment according to the invention of animal skin with at least one compound of the general formula I is preferably carried out in the liming or the Schwöde, specifically under hair-destroying or under hair-preserving conditions.
• the usual concentration of about 4% by weight Na 2 S or NaHS or even slightly more it is possible in the liming or Schwöde with a concentration of less than 1% by weight Na 2 S or NaHS the same or better effect with regard to the removal of horny substances.
• a compound of the general formula I is used in the liming together with thiols known from the tannery, such as mercaptoethanol or thioglycolic acid. Less than 0.5% by weight of mercaptoethanol or thioglycolic acid is preferably used.
• hides are treated in an aqueous liquor.
• the liquor ratio can be from 1:10 to 10: 1, preferably 1: 2 to 4: 1, particularly preferably up to 3: 1, based on the skin weight or salt weight of the skins.
• the process according to the invention can be carried out at pH values from 7 to 14, preferably from 8 to 13 and particularly preferably from 9 to 12.5.
• lime is not used.
• one or more inorganic basic alkali metal compounds are added, for example one or more hydroxides or carbonates of alkali metals, preferably of sodium or potassium and very particularly preferably of sodium.
• suitable inorganic basic alkali metal compounds are alkali metal silicates.
• Basic amines for example ammonia, methylamine, dimethylamine, ethylamine or triethylamine, or combinations of alkali metal compounds and one or more basic amines can also be added.
• the method according to the invention can be carried out in vessels customary in tanning, in which ashing is usually carried out.
• the treatment method according to the invention is preferably carried out in rotatable drums with flow-breaking internals.
• the speed is usually 0.5 to 100 / min, preferably 1.5 to 10 / min and particularly preferably up to 4.5 / min.
• the pressure and temperature conditions for carrying out the method according to the invention are generally not critical. Carrying out at atmospheric pressure has proven to be suitable; a pressure increased up to 10 bar is also conceivable. Suitable temperatures are 10 to 45 ° C, preferably 15 to 35 ° C and particularly preferably 25 to 30 ° C.
• At least one compound of the general formula I can be metered in at the start of the process according to the invention, but first the skin or the skins can also be soaked first under basic conditions and only after a while at least one dithiol mixture according to the invention can be metered. Dosing can be done in one step, i.e. the total amount of dithiol mixture according to the invention is metered in one step; However, dithiol mixture according to the invention can also be metered in portions or continuously.
• the process according to the invention can be carried out in a period of 10 minutes to 48 hours, preferably 1 to 36 hours and particularly preferably 3 to 15 hours.
• tanning agents that are customary in tanning, for example phosphines, such as, for example, to carry out the process according to the invention.
• the method according to the invention makes it possible to produce excellently hairless pelts. It is surprising that the epidermis is completely or at least largely detached after a short treatment period.
• the process according to the invention is carried out in the presence of at least one enzyme.
• Exo- and endopeptidases are preferred. These can be representatives of the main classes of proteases, for example serine proteases, cysteine proteases, metalloproteases and acid proteases.
• serine proteases examples include trypsin, chymotrypsin, elastase, thrombin, plasmin, subtilisin and acrosine.
• cysteine proteases are papain, bromelain and cathepsin B.
• metalloproteases are carboxypeptidase and ACE (angiotensin conversion enzyme).
• acidic proteases are pepsin and HIV protease.
• Serine proteases such as trypsin, chymotrypsin, subtilisin and proteinase K and variants of the above-mentioned enzymes are particularly suitable in the context of the present invention.
• Variants include, inter alia, mutants which have arisen from insertion (s), deletion (s) and point mutation (s) and which have modified, in particular advantageous properties, in comparison to the protease which was assumed in each case. Examples of changed properties are thermostability, higher affinity for the animal skin (substrate) to be converted enzymatically, (higher) substrate specificity and shifting the pH optimum into the desired pH range. Fragments of the aforementioned proteases are also referred to as variants in the sense of the present invention.
• variants are produced recombinantly using the customary methods described, for example, in "Molecular Cloning - A Laboratory Manual” by Sambrook, Fritsch and Maniatis (1989) in a suitable bacterial or fungal host system.
• Proteases of the four main classes serine, cysteine, metallo- and acid proteases
• specific keratinolytic activity and mixtures of these enzymes are very particularly preferred.
• enzymes which hydrolyze peptide bonds are also to be understood as commercially available enzyme formulations. Examples of such products are Alcalase 3.0t, Pyrase 250 MP, conc.
• PTN 3.0 type p from the company Novozymes, Prozym 6 from TFL, pancreatin from Nordmark A, Pancreatina enzyme PEC from Scientific Protein Laboratory, Alprolase 3m, Basozym® L10 and Basozym® S20 from BASF Aktiengesellschaft, Batinase (manufacturer: Genencor), Proleather ( Manufacturer: Amano), Protease L 660 (manufacturer: Genencor), Esperase, Alcalas 2.4L and Savinase (manufacturer: Novo Nordisk), and Pruafect 4000L from Genencor.
• the amount of enzyme used is usually expressed in Löhlein-Volhard units (LVEs). Usually you do not dose pure enzyme, but use diluted formulations that can be solid or liquid.
• LVEs Löhlein-Volhard units
• the LVEs are determined by titrimetric methods known per se, which are based on the breakdown of casein by an enzyme formulation to be investigated or an enzyme to be investigated and the subsequent titration of the released carboxyl groups with 0.1 N NaOH.
• One LVE corresponds to 0.00575 ml 0.1 N NaOH.
• the enzyme or enzymes are generally used in concentrations which are at least a factor of 10, preferably 100, particularly preferably 1000, smaller than the amount of compound I.
• one or more enzymes are used, one usually does not dose the pure enzyme, but rather one or more solid or liquid enzyme-containing formulations.
• solid formulations also contain inorganic or organic solids or mixtures thereof.
• inorganic solids are NaCI, Na 2 SO ⁇ kieselguhr, NaHCO 3 , Na 2 CO 3 or kaolin, concrete, clay minerals;
• Suitable organic solids are, for example, polysaccharides such as starch and modified starch or urea.
• Solid formulations can also contain substances with a reduced action, such as NaHSO 3 .
• Liquid formulations contain at least one liquid solvent or dispersant, for example water or mixtures of water and organic solvent.
• pelts produced by the process according to the invention are extremely suitable for the production of leather.
• further processing as usual in tanning, of pelts produced by the process according to the invention, ie pickling, optionally decalcification, pimples, chrome-free tanning or chrome tanning, retanning and dressing, it is observed that pelts produced by the process according to the invention are converted into leather with an improved area yield and less swelling damage can process further, compared to leather which is produced from pelts which have been depilated with the aid of, for example, Na 2 S, NaHS, thioglycolic acid or aminethanol.
• Another object of the present invention are therefore pelts which are obtainable by the process according to the invention.
• the present invention further relates to compounds of the general formula I.
• R 1 , R 4 are the same or different and selected
• C 6 -C 14 aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryi, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9- Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl,
• C ⁇ C ⁇ alkyl such as 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, isOHexyl, sec.-hexyl, n-decyl or n-dodecyl, particularly preferably dC 4 -alkyl such as methyl, ethyl, n-propyl, iso- Propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl;
• CrC 12 alkyl substituted with one or more hydroxyl or thiol groups such as hydroxymethyl, 2-hydroxyethyl, 1, 2-dihydroxyethyl, 3-hydroxy-n-propyl, 2-hydroxy-isopropyl, ⁇ -hydroxy-n- Butyl, ⁇ -hydroxy-n-decyl, HS-CH 2 -; HS- (CH 2 ) 2 - or HS- (CH 2 ) 3 - and especially hydrogen.
• R 2 , R 3 are the same or different and selected
• C 6 -C 14 aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl , preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl,
• CrC ⁇ 2 alkyl such as 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, isOHexyl, sec.-hexyl, n-decyl or n-dodecyl, particularly preferably CrC 4 -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl and tert-butyl, very particularly preferably methyl,
• C ⁇ -Ci 2 alkyl substituted with one or more hydroxy or thiol groups such as hydroxymethyl, 2-hydroxyethyl, 1, 2-dihydroxyethyl, 3-hydroxy-n-propyl, 2-hydroxy-iso-propyl, ⁇ -hydroxy-n -Butyl, ⁇ -hydroxy-n-decyl, HS-CH -; HS- (CH 2 ) 2 - or HS- (CH 2 ) 3 -.
• At least one radical R 2 or R 3 is different from hydrogen, or R 1 and R 4 are different from hydrogen.
• R 2 and R 3 are different from hydrogen.
• R 1 , R 2 and R 3 are different from hydrogen.
• R 1 , R 2 , R 3 and R 4 are different from hydrogen.
• two vicinal radicals R 1 to R 4 may together be alkylene, substituted or unsubstituted, C 3 -C ⁇ preferably 0 alkylene such as - (CH 2) 3 -, - (CH 2) 2 -CH (CH 3) -, - (CH 2 ) 2 -CH (C 2 H 5 ) -, - (CH 2 ) 4 -, - (CH 2 ) 5 -, - (CH 2 ) 6 -, preferably C 3 -C 5 alkylene; in particular - (CH 2 ) 3 -, - (CH 2 ) 2 -CH (CH 3 ) -, - (CH 2 ) 2 -CH (C 2 H 5 ) -, - (CH 2 ) 4 -,
• R 1 to R 4 together represent alkylene, they form a ring. It is possible for R 1 and R 2 together to mean - (CH 2 ) 4 - or - (CH 2 ) 5 - to form a cyclopentenyl or cyclohexenyl system. It is also possible for R 2 and R 3 together to be a - (CH 2 ) 4 - or - (CH 2 ) 5 group, with the formation of an optionally 1,2-dimethylenecyclopentane system or an optionally substituted 1, 2-Dimethylencyclohexansystems.
• X 1 , X 2 , X 3 and X 4 are selected from OH, SH and NHR 5 , where in the case that R 1 to R 4 contains at least one sulfur atom, at least one X 1 to X 4 means SH, and for that Case that R 1 to R 4 contains no sulfur atom, mean at least two X 1 to X 4 SH.
• Corresponding alkali metal and alkaline earth metal salts include, in particular, the mono- and disodium salts, mono- and dipotassium salts and potassium sodium salts of the compounds of the general formula I, as well as the corresponding calcium and magnesium salts.
• Ammonium salts or primary, secondary, tertiary and in particular quaternary mono- and diammonium salts and phosphonium salts can also be mentioned.
• Mixtures of compounds of the general formula I and their corresponding alkali metal or alkaline earth metal salts or ammonium or phosphonium salts can of course also be used.
• Preferred mono- and diammonium salts have as cations those of the formula N (R 7 ) (R 8 ) (R 9 ) (R 10 ) + , where R 7 to R 0 are each the same or different and selected from hydrogen, C
• Preferred mono- and diphosphonium salts have cations of the formula P (R 7 ) (R 8 ) (R 9 ) (R 10 ) + , where R 7 to R 10 are as defined above.
• X 1 and X 4 each represent SH.
• At least one is preferred, and at least two groups X 1 to X 4 are particularly preferred hydroxyl groups.
• Particular examples of compounds of general formula I according to the invention are the compounds of formulas 1.1 to I.9
• R 1 and R 4 each represent hydrogen, R 2 represents methyl, R 3 represents hydrogen or methyl, X 1 and X 4 each represent SH, X 2 and X 3 each represent OH.
• the present invention further provides a process for the preparation of compounds of the general formula I according to the invention, also referred to below as the production process according to the invention. To carry out the production process according to the invention, the starting point is conjugated diene of the general formula II
• Step (a) in the presence of a catalyst with at least one peroxide to the bisepoxide.
• Step (b) is then reacted with bisepoxide in the presence of at least one basic catalyst with at least one nucleophile.
• Preferred conjugated dienes of the general formula II are dienes of the formulas 11.1 to II.9
• step (a) It is possible to isolate and purify bisepoxide from step (a). In a preferred embodiment, however, the isolation of bisepoxide from step (a) is dispensed with and the procedure is continued according to step (b).
• the reaction in stage (a) takes place in the presence of a catalyst which is obtainable
• Y 1 different or identical and selected from monovalent anions, R 12 O “ , F “ , CI “ , Br “ ,
• -, NCS “ , N 3 -, l 3 -, R 12 COO-, R 12 SO 3 ' , R 12 SO 4 " , OH “ , CN “ , OCN “ , N0 3 “ , Cl0 4 “ , PF 6 “ , BPh 4 “ with Ph phenyl and F 3 CSO 3 " .
• CI " and acetate are particularly preferred.
• Y 2 is a divalent anion, particularly preferably SO 4 2 " and HPO 2" .
• alkali metal cations for example Li +, Na +, K +, Rb + and Cs +, in particular Na + and K +
• R 13 to R 16 are each the same or different and selected from hydrogen, benzyl, C ⁇ - C ⁇ 2 alkyl such as 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 or n-decyl, particularly preferably CC-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl isobutyl sec-but
• R 6 different or preferably the same and selected from branched or preferably unbranched CrC 20 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n -Pentyl, iso-pentyl, sec.-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-octyl, n-decyl, n-dodecyl , n-tetradecyl, n-hexadecyl, n-octa-decyl and n-eicosyl, preferably unbranched CrC 12 -alkyl, such as methyl, ethyl, n-propyl,
• R 12 preferably stands for
• CC 20 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-dimethyl-propyl, iso-amyl, n-hexyl, isOHexyl, sec.-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-Eicosyl, preferably unbranched d -CC 2 alkyl such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-he
• substituted CrC 20 alkyl such as ⁇ -cyclohexylpropyl, 2-cyclohexylethyl;
• C 3 -C 2 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred,
• C 6 -C aryl for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl
• manganese compounds used according to the invention are manganese (II) sulfate, manganese (II) acetate, manganese (II) chloride, manganese (II) perchlorate or potassium hexachloromanganate (IV) K 2 MnCl 6 . It is possible that manganese compounds used in accordance with the invention have water of crystallization and / or water of hydration, such as, for example, Mn (OAc) 2 -4 H 2 O, MnSO 4 -H 2 O, Mn (CIO 4 ) 2 -6 H 2 O, MnCl 2 - 4 H 2 O.
• use is made in the range from 0.001 to 0.1, particularly preferably 0.005 to 0.01, equivalents of manganese compound, based on the conjugated diene of the general formula II.
• ligand L of the general formula III based on manganese, are used, preferably 1.1 to 2 equivalents.
• Suitable coligands are those compounds which are derived from monocarboxylic acids, di- or polyvalent carboxylic acids or diamines, i.e. Monocarboxylic acids, di- or polyvalent carboxylic acids and diamines themselves, and in the case of monocarboxylic acids, di- or polyvalent carboxylic acids in particular their corresponding alkali metal salts.
• coligands are derived from monocarboxylic acids or di- or polyvalent carboxylic acids whose pKa value or pK a 1 value in water at 25 ° C. is below 7.
• coligands are derived from oxalic acid (IV.1), dihydroxyfumaric acid (IV.2), tartaric acid (IV.3), maleic acid (IV.4), squaric acid (IV.5), 2-sulfobenzoic acid (IV .6) and N (p-toluenesulfonyl) glycine (IV.7):
• Another very particularly preferred coligand is 1, 2-diaminocyclohexane, both the isomer mixture and the respective cis and frans isomers in enriched form being suitable.
• coligands are used as a mixture of monocarboxylic acids and alkali metal salt of the monocarboxylic acid in question.
• coligands are used as a mixture of di- or polyvalent carboxylic acid and alkali metal salt of the di- or polyvalent carboxylic acid in question.
• 0.1 to 5 equivalents, preferably 0.5 to 1 equivalent, of coligand are used, based on manganese.
• diene of the general formula II is reacted with at least one peroxide, preference being given to using up to 4 equivalents of peroxide per equivalent of CC double bond. But you can also use more peroxide. It is particularly preferred to use at least one equivalent of peroxide per equivalent of CC double bond.
• the peroxide used can preferably be organic peroxides, in particular tert-butyl hydroperoxide, cumene hydroperoxide, 1,3-diisopropyl monohydro peroxide, 1-phenylethyl hydroperoxide. Hydrogen peroxide (H 2 O 2 ) is particularly preferred as the peroxide.
• hydrogen peroxide it is used as an aqueous solution, for example as a 30% by weight or 50% by weight solution, the content of reactive H 2 O 2 of which is determined by known methods, for example by titration can.
• up to 3 preferably up to 2.1 equivalents of peroxide are used per equivalent of C 1 -C double bond.
• ligand L of the general formula III and coligand are first mixed with conjugated diene of the general formula II and peroxide and then manganese compound is added.
• ligand L of the general formula III is first mixed with coligand and conjugated diene of the general formula II and manganese compound and then peroxide is added.
• a complex compound is first prepared by contacting the manganese compound and ligand L and coligand of the general formula III, which is then mixed with conjugated diene of the general formula II and then with peroxide.
• a complex compound is first prepared by contacting manganese compound and ligand L of the general formula III, which is then mixed with conjugated diene of the general formula II and coligand and then with peroxide.
• a complex compound of the formula [LMn ( ⁇ -O) 3 MnL] X is first prepared by contacting the manganese compound and ligand L of the general formula III, which is then combined with conjugated diene of the general formula II and coligand and then mixed with peroxide.
• a complex compound is first prepared by contacting the manganese compound and ligand L and coligand of the general formula III, which is then mixed with conjugated diene of the general formula II and then with peroxide, with peroxide in two portions admits at least 2 hours apart.
• the process according to the invention is carried out in a solvent or a mixture of solvents.
• a solvent liquid organic or inorganic liquids can be used at the reaction temperature which, under the conditions, do not or only in negligible proportions with the reactants and product, i.e. for example, bisepoxide.
• Suitable are, for example, -C 4 alkanols such as methanol, ethanol, n-propanol, isopropanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone (MIBK), acetonitrile, halogenated hydrocarbon such as, for example Methylene chloride, chloroform, 1, 1, 2,2-tetrachloroethane and water. Mixtures of water and acetonitrile, mixtures of water and methanol and mixtures of water and acetone are particularly suitable.
• so much solvent or mixture of solvents is used that the concentration of bisepoxide does not exceed 50% by weight, preferably 5 to 15% by weight.
• the production process according to the invention is carried out without having previously immobilized the catalyst on one or more solid support materials such as, for example, silica gel or aluminum oxide.
• the production process according to the invention is carried out at temperatures in the range from -50 to 100 ° C., preferably from
• the production process according to the invention is carried out at a pressure in the range from 1 to 200 bar, preferably at 1 to 100 bar, particularly preferably at normal pressure up to 10 bar.
• the production process according to the invention is carried out at a pH from 1 to 7, preferably from 3 to 5 to.
• the reaction time is 1 minute to 24 hours, preferably 30 minutes to 20 hours.
• reaction vessels are suitable as reaction vessels for the practice of the production process according to the invention, for example tubular reactors and stirred tanks, with stirred tanks being able to be operated batchwise or continuously and tubular reactors preferably continuously.
• the production process according to the invention gives solutions of bisepoxide.
• the solutions of bisepoxide obtainable according to the invention can contain small amounts of monoepoxide, for example of the formula V.1 or V.2,
• solutions of bisepoxide which are obtainable according to step (a) described above are used and isolation and purification operations are dispensed with.
• step (b) bisepoxide prepared in step (a) is reacted with at least one nucleophile in the presence of at least one basic catalyst.
• nucleophile Compounds with an atom with at least one lone pair of electrons and at least two acidic hydrogen atoms are preferably suitable as the nucleophile.
• H 2 S is particularly suitable, furthermore H 2 O and compounds of the general formula H 2 NR 5 in the event that at least one of the radicals R 1 to R 4 carries SH groups.
• the nucleophile is H 2 S.
• mixtures of different nucleophiles can also be used.
• step (b) is reacted with 1 to 10 equivalents, preferably with 1 to 2 equivalents of nucleophile, preferably with H 2 S, based on one equivalent of epoxy group.
• Step (b) of the production process according to the invention is carried out in the presence of at least one basic catalyst.
• Basic alkali metal salts and ammonium salts are suitable as basic catalysts, for example alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen sulfides, ammonium hydroxides.
• alkali metal cations are Li + , Na + , K + , Rb + and Cs + , in particular Na + and K + .
• ammonium ions are not only unsubstituted NH 4 + , but also mono- and up to four times alkylated ammonium, for example N (R 13 ) (R 14 ) (R 15 ) (R 16 ) + , where R 13 to R 16 are each the same or different and selected from hydrogen, benzyl, CrC 12 alkyl such as 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, isOHexyl, sec.-hexyl or n-decyl, particularly preferably CC 4 -alkyl such as Methyl, ethyl, n-
• At least one basic catalyst in stage (b) is preferably selected from alkali metal hydrogen sulfide, alkali metal hydroxide and benzyltri ⁇ rC ⁇ -alkyammonium hydroxide, very particularly preferred are sodium hydrogen sulfide, potassium hydrogen sulfide, sodium hydroxide, potassium hydroxide and benzyltrimethylammonium hydroxide.
• stage (b) is carried out at a pressure in the range from 1 to 200 bar, preferably at 1 to 100 bar, particularly preferably at 1 to 10 bar.
• stage (b) is carried out at a temperature in the range from -50 to 100 ° C., preferably from -30 to 80 ° C., particularly preferably from -10 to 60 ° C., very particularly preferably from 15 to 35 ° C.
• stage (b) of the production process according to the invention is carried out at a pH of 8 to 13, preferably 9 to 11.
• a solution of bisepoxide obtainable after step (a) of the process according to the invention is used, nucleophile, preferably H 2 S, is added, then at least one basic catalyst is added and the mixture is allowed to react.
• step (b) of the two-step process according to the invention further solvent, selected from the solvents listed under step (a) above, can be added in step (b) of the two-step process according to the invention.
• the reaction time is 10 minutes to 4 hours, particularly preferably 0.5 hours to 2 hours.
• reaction vessels are suitable as reaction vessels for carrying out stage (b) of the production process according to the invention, for example tubular reactors and stirred tanks, it being possible to operate batched tanks continuously or continuously, and tubular reactors preferably continuously. Continuously operated stirred tank cascades are also conceivable as suitable vessels.
• peroxide from stage (a) which has not reacted in step (b) can be trapped by possibly excess nucleophile such as H 2 S.
• solutions of isomer mixtures or corresponding salts of isomer mixtures are obtained, which are also an object of the present invention.
• Compounds I according to the invention or their corresponding salts can be isolated from solutions according to the invention of isomer mixtures or of corresponding salts of isomer mixtures by methods known per se, for example neutralizing, distilling off the solvent or solvents. In order to obtain particularly pure compound II according to the invention, distillation can be carried out, for example under reduced pressure.
• a special subject of the present invention are isomer mixtures of compound VI, containing in the range of
• Isomer mixtures of compound VI according to the invention contain compounds which can be imaged in the Fischer projection as follows:
• Isomer mixtures of compound VI according to the invention can contain corresponding salts of erythro-VI and threo-VI.
• threo-VI is present as a racemate.
• Isomer mixtures of compound VI according to the invention can contain small amounts of hydroxythiol, for example of the general formulas VII.1 or VII.2
• the corresponding salts include, in particular, the mono- and disodium salts, mono- and dipotassium salts and potassium sodium salts of dithiols of the general formula VI, as well as the corresponding calcium and magnesium salts.
• the ammonium salts or primary, secondary, tertiary and in particular quaternary mono- and diammonium salts should also be mentioned.
• Preferred mono- and diammonium salts have as cations those of the formula N (R 13 ) (R 14 ) (R 15 ) (R 16 ) + , where R 13 to R 16 are in each case identical or different and selected from hydrogen, CC 12 -alkyl , Phenyl or CH 2 -CH 2 -OH. Examples include tetramethylammonium, tetraethylammonium, methyldiethanolammonium and n-butyldiethanolammonium.
• the present invention further provides aqueous solutions containing an isomer mixture of the general formula VI according to the invention.
• Aqueous solutions according to the invention can be obtained, for example, by dissolving the isomer mixture or corresponding salt according to the invention in water.
• Aqueous solutions according to the invention preferably have a solids content of 0.1 to 50% by weight.
• the yield of the desired bisepoxide VIII.1 was 94.5%.
• the pressure is kept at 6 bar by continuously pressing in H 2 S.
• the lines of the HPLC pump are then rinsed with 50 ml of acetonitrile. After the reaction had ended, which was noticeable as the temperature subsided, the autoclave was depressurized and excess H 2 S was removed over a period of 14 hours by passing N 2 through the reaction mixture.
• Chromatographic methods for example gas chromatography, are suitable as an analytical and preparative method for separating the isomers. Suitable conditions are e.g.
• the skin of a South German cattle is first placed in a barrel at 28 ° C. with 200% by weight of water and 0.2% by weight of C 15 H 3 O- (CH 2 -CH 2 -O) 7 -H for 10 minutes pre-soaked with gentle stirring.
• the liquor is drained and then with 100 wt .-% water, 0.2 wt .-% C 15 H 31 -O- (CH 2 -CH 2 -O) 7 -H and 0.5 wt .-% Na 2 CO 3 soaked for 19 hours with occasional stirring.
• the fleet is then drained.
• the softened hides of southern German cattle are fleshed green (about 4 mm thick) and the croupons of the hides are cut into pieces of skin weighing 2.5 kg each.
• Papain formulation is papaya peptidase I, EC 3.4.22.2, a gray-white to pale yellow powder that is obtained by drying and pulverizing the milk juice (latex) of immature papayas.
• the barrels are operated for a further 45 minutes at 5 revolutions / minute. A further 40% by weight of water is then metered in. After 10 hours at 23 to 27 ° C with periodic operation at 3 revolutions / minute for 5 minutes each hour, the experiments are ended by draining off the liquors and washing the pelts obtained twice for 15 minutes with 150% by weight of water become.
• the pelts treated according to the examples according to the invention are assessed with regard to swelling, quality of the scars and removal of the epidermis.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Detergent Compositions (AREA)
• Cosmetics (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=34559672

Family Applications (1)

Country Status (7)

Families Citing this family (4)

Family Cites Families (7)

• 2003
  • 2003-11-17 DE DE10353746A patent/DE10353746A1/de not_active Withdrawn
• 2004
  • 2004-11-12 EP EP04797857A patent/EP1687454A1/de not_active Withdrawn
  • 2004-11-12 WO PCT/EP2004/012850 patent/WO2005049870A1/de not_active Application Discontinuation
  • 2004-11-12 BR BRPI0416389-3A patent/BRPI0416389A/pt not_active Application Discontinuation
  • 2004-11-12 CN CNA2004800338614A patent/CN1882706A/zh active Pending
  • 2004-11-12 US US10/579,714 patent/US20070124868A1/en not_active Abandoned
  • 2004-11-17 AR ARP040104235A patent/AR046930A1/es unknown

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events