US20030162836A1 - Hydroxydiphenyl ether compounds - Google Patents

Hydroxydiphenyl ether compounds Download PDF

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Publication number
US20030162836A1
US20030162836A1 US10/281,011 US28101102A US2003162836A1 US 20030162836 A1 US20030162836 A1 US 20030162836A1 US 28101102 A US28101102 A US 28101102A US 2003162836 A1 US2003162836 A1 US 2003162836A1
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alkyl
hydrogen
respect
compounds
ether linkage
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Werner Holzl
Wolfgang Haap
Dietmar Ochs
Karin Puchtler
Marcel Schnyder
Surendra Kulkarni
Arakali Radhakrishna
Mangesh Sawant
Asawari Mahtre
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Priority to US10/816,967 priority patent/US7105577B2/en
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/075—Ethers or acetals
    • A61K31/085—Ethers or acetals having an ether linkage to aromatic ring nuclear carbon
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
    • A01N31/16—Oxygen or sulfur directly attached to an aromatic ring system with two or more oxygen or sulfur atoms directly attached to the same aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/04—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aldehyde or keto groups, or thio analogues thereof, directly attached to an aromatic ring system, e.g. acetophenone; Derivatives thereof, e.g. acetals
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A61K8/347—Phenols
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/35—Ketones, e.g. benzophenone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P1/00—Drugs for disorders of the alimentary tract or the digestive system
    • A61P1/02—Stomatological preparations, e.g. drugs for caries, aphtae, periodontitis
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00—Drugs for dermatological disorders
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00—Drugs for dermatological disorders
    • A61P17/16—Emollients or protectives, e.g. against radiation
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/04—Antibacterial agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q15/00—Anti-perspirants or body deodorants
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/005—Antimicrobial preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
    • C07C43/295—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/46—Friedel-Crafts reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
    • C07C47/575—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
    • 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
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial 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
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/263—Ethers
    • 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
    • C11D7/3227—Ethers thereof

Definitions

  • the present invention relates to the use of hydroxydiphenyl ether compounds as antimicrobially active substances, to certain new compounds of this type and to processes for the preparation of these compounds.
  • halogenated diphenyl ether compounds have an excellent antimicrobial activity. These compounds are therefore widely used, for example as active substances for the antimicrobial finishing of medical items and household articles, as detergent additive and in the hygiene sector, for example in soaps or dental hygiene products. Such halogenated compounds are described in DE 2538016. However it is desirable to be able to provide non-halogenated agents which are highly effective antimicrobial agents. Polymeric materials can be antimicrobially finished by incorporating halogenated diphenyl ether compounds, the active substances being, as a result of their excellent migration properties, constantly conveyed to the surface of the corresponding material (“slow release”). For certain industrial applications, this effect is undesired since the long-term effect of antimicrobially finished materials such as textiles, paper, plastics, cellulose sponges etc. is reduced at the same time.
  • the object of the present invention is thus to provide non-halogenated hydroxydiphenyl ether compounds for use as antimicrobially active substances and which, at the same time, are stable to migration.
  • the present invention provides the use of hydroxydiphenyl ether compounds of the following formula
  • R 1 and R 2 are independently of each other hydrogen, hydroxy, C 1 -C 20 alkyl, C 1 -C 7 cycloalkyl, C 1 -C 6 alkylcarbonyl, C 1 -C 20 alkoxy, phenyl or phenyl-C 1 -C 3 -alkyl;
  • R 3 is hydrogen, C 1 -C 20 alkyl or C 1 -C 20 alkoxy
  • R 4 is hydrogen, C 1 -C 20 alkyl, hydroxy substituted C 1 -C 20 alkyl, C 5 -C 7 cycloalkyl, hydroxy, formyl, acetonyl, C 1 -C 6 alkylcarbonyl, C 2 -C 20 alkenyl, carboxy, carboxyC 1 -C 3 alkyl, C 1 -C 3 alkylcarbonylC 1 -C 3 alkyl or carboxyallyl;
  • R 2 is hydrogen, C 1 -C 20 alkyl, hydroxy substituted C 1 -C 20 alkyl or C 1 -C 6 alkylcarbonyl;
  • R 1 and R 3 are independently of each other hydrogen, C 1 -C 6 alkylcarbonyl or C 1 -C 20 alkyl;
  • R 4 is hydrogen, C 1 -C 20 alkyl, hydroxy substituted C 1 -C 20 alkyl, C 1 -C 7 cycloalkyl, hydroxy, formyl, acetonyl, C 1 -C 6 alkylcarbonyl, C 2 -C 20 alkenyl, carboxy, carboxyC 1 -C 3 alkyl, C 1 -C 3 alkylcarbonylC 1 -C 3 alkyl or carboxyallyl;
  • R 1 is hydrogen, C 1 -C 6 alkyl carbonyl or C 1 -C 20 alkyl;
  • R 4 is hydrogen, C 1 -C 20 alkyl, hydroxy substituted C 1 -C 20 alkyl, C 5 -C 7 cycloalkyl, hydroxy, formyl, acetonyl, C 1 -C 6 alkylcarbonyl, C 2 -C 20 alkenyl, carboxy, carboxyC 1 -C 3 alkyl, C 1 -C 3 alkylcarbonylC 1 -C 3 alkyl or carboxyallyl;
  • R 2 and R 3 are independently of each other hydrogen, C 1 -C 6 alkyl carbonyl or C 1 -C 20 alkyl;
  • C 1 -C 20 alkyl is straight-chain or branched alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, iso-pentyl, tert-pentyl, hexyl, cyclohexyl, heptyl, octyl, isooctyl, nonyl or decyl and the like.
  • C 1 -C 20 alkoxy is straight-chain or branched alkoxy radicals such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, pentyloxy, iso-pentyloxy, tert-pentyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy or decyloxy and the like.
  • C 1 -C 6 alkyl carbonyl is straight-chain or branched carbonyl radicals such as acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl or pivaloyl and the like.
  • Hydroxy substituted C 1 -C 20 alkyl is hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyheptyl, hydroxyoctyl, hydroxynonyl or hydroxydecyl and the like.
  • R 1 and R 2 are independently of each other hydrogen, C 1 -C 20 alkyl, C 1 -C 6 alkyl carbonyl or C 1 -C 20 alkoxy;
  • R 3 is hydrogen, C 1 -C 10 alkyl or C 1 -C 20 alkoxy
  • R 4 is hydrogen, C 1 -C 20 alkyl, hydroxy, formyl, acetonyl, allyl, carboxymethyl, carboxyallyl, hydroxy substituted C 1 -C 20 alkyl or C 1 -C 6 alkyl carbonyl;
  • R 2 is hydrogen, C 1 -C 20 alkyl, hydroxy substituted C 1 -C 20 alkyl or C 1 -C 6 alkyl carbonyl;
  • R 1 and R 3 are independently of each other hydrogen, C 1 -C 6 alkyl carbonyl or C 1 -C 20 alkyl;
  • R 4 is hydrogen, C 1 -C 20 alkyl, hydroxy, formyl, acetonyl, allyl, carboxymethyl, carboxyallyl, hydroxy substituted C 1 -C 20 alkyl or C 1 -C 6 alkyl carbonyl;
  • R 1 is hydrogen, C 1 -C 6 alkyl carbonyl or C 1 -C 20 alkyl;
  • R 4 is hydrogen, C 1 -C 20 alkyl, hydroxy, formyl, acetonyl, allyl, carboxymethyl, carboxyallyl, hydroxy substituted C 1 -C 20 alkyl or C 1 -C 6 alkyl carbonyl;
  • R 2 and R 3 are independently of each other hydrogen, C 1 -C 6 alkyl carbonyl or C 1 -C 20 alkyl; with the proviso that compounds wherein OH is in the para position with respect to the ether linkage and R 1 and R 3 are both hydrogen and R 2 is methoxy or methyl; or a compound wherein OH is in the para position with respect to the ether linkage R 2 is hydrogen, R 1 is isopropyl and R 3 is methyl are excluded.
  • novel compounds are of formula (1) wherein when OH is in the ortho position with respect to the ether linkage and R 2 , R 3 and R 4 are hydrogen and R 1 is C 1 -C 20 alkyl.
  • these novel compounds are of formula (1) wherein when OH is in the ortho position with respect to the ether linkage and R 2 , R 3 and R 4 are hydrogen and R 1 is C 1 -C 5 alkyl.
  • Compounds of particular interest include the following:
  • these novel compounds are of formula (1) wherein when OH is in the meta position with respect to the ether linkage and R 2 , R 3 and R 4 are hydrogen and R 1 is C 1 -C 5 alkyl.
  • Compounds of particular interest include the following:
  • R 1 is C 1 -C 5 alkyl; for example the compound of formula
  • R 4 is C 1 -C 5 alykl, for example the compound of formula
  • these novel compounds are of formula (1) wherein when OH is in the meta position with respect to the ether linkage and R 2 and R 4 are hydrogen and R 1 and R 3 are C 1 -C 5 alkyl.
  • Compounds of particular interest include the following:
  • Another aspect of the present invention is a process for the preparation of compounds of formula (1) wherein when OH is in the ortho position with respect to the ether linkage and R 2 , R 3 and R 4 are hydrogen and R 1 is C 1 -C 20 alkyl, compounds of formula (1) wherein when OH is in the meta position with respect to the ether linkage and R 2 , R 3 and R 4 are hydrogen and R 1 is C 1 -C 20 alkyl and compounds of formula (1) wherein when OH is in the para position with respect to the ether linkage and R 2 and R 4 are hydrogen and R 1 and R 3 are C 1 -C 20 alkyl.
  • the process comprises reacting a susbstituted phenol with an ether substituted halogenphenol in the presence of alkali and a catalytically active quantity of copper or of a copper compound, and the resulting alkyloxybenzol compound is then heated in the presence of hydrogen halide and acid in order to convert the alkyloxy group to a hydroxy group.
  • An example of the reaction scheme is shown below, wherein R represents one of the groups R 1 , R 2 or R 3 .
  • Preferred combinations of reagents include 2-C 1 -C 20 alkyl substituted phenols and 2-methoxy-bromophenol.
  • reagents include 2-C 1 -C 20 alkyl substituted phenols and 3-methoxy-bromophenol.
  • reagents include 2,5-C 1 -C 20 dialkyl substituted phenols and 4-methoxy-bromophenol.
  • Preferred bases are hydroxides/carbonates from group 1 ⁇ 2 metals.
  • the alkali required for the reaction can be added in different forms.
  • the substituted phenol can be reacted in the form of alkali phenolate.
  • the reaction may be also carried out in the presence of a solvent such as an aliphatic ether containing 6 or more carbon atoms and boiling at a temperature above 130° C. and also ethers of polyglycols such as di- and tri-ethylene gylcol and in high boiling solvents as Pyridin, DMF, DMA, DMSO, Toluene, Xylene etc.
  • a solvent such as an aliphatic ether containing 6 or more carbon atoms and boiling at a temperature above 130° C. and also ethers of polyglycols such as di- and tri-ethylene gylcol and in high boiling solvents as Pyridin, DMF, DMA, DMSO, Toluene, Xylene etc.
  • General catalysts for Ullmann condensation are Cu, Cu 2 Cl 2 , bas. CuCO 3 /CuCl 2 , CuO or Cu 2 O. Copper or copper compounds are used in known manner as catalysts for example in quantities of from 0.1 to 2.5% based on the halogenphenol.
  • the reaction temperatures are generally from 150° C. to 200° C. whilst the reaction times vary from 1 to 16 hours. The reaction may be carried out under elevated pressure.
  • Suitable reagents used in the demethylation step include hydrogen bromide.
  • Suitable acids used in the demethylation step include acetic acid.
  • General reagents are AlCl 3 , BCl 3 , BF 3 , HBr, Hl, preferably pyridinium ⁇ HCl.
  • reaction can be worked up in the usual way. Unreacted starting materials can be separated off by distillation, optionally under vacuum.
  • a further aspect of the invention includes other certain compounds described by formula (1) which are novel.
  • R 1 , R 2 and R 3 are hydrogen
  • R 4 is in the meta position with respect to the ether linkage and is C 1 -C 6 alkyl carbonyl.
  • Compounds of particular interest include the following:
  • Compounds of particular interest include the following:
  • a further aspect of the present invention is another process for the preparation of compounds of formula (1) wherein when OH is in the meta position with respect to the ether linkage and R 1 , R 2 and R 3 are hydrogen and R 4 is in the para position with respect to the ether linkage and is C 1 -C 6 alkyl carbonyl and also for compounds of formula (1) wherein when OH is in the ortho position with respect to the ether linkage and R 1 , R 2 and R 3 are hydrogen and R 4 is in the meta position with respect to the ether linkage and is C 1 -C 6 alkyl carbonyl.
  • the process comprises reacting an acyl chloride with a phenoxyphenol, such as meta-phenoxyphenol or ortho-phenoxyphenol, in the presence of activated zinc at a temperature of between 70° c. to 80° C.
  • a phenoxyphenol such as meta-phenoxyphenol or ortho-phenoxyphenol
  • This acyl compound then undergoes a “Fries rearrangement” in the presence of aluminium chloride at a temperature of 145° C. to 150° C., producing an acylated phenol.
  • R 6 is C 1 -C 6 alkylcarbonyl.
  • These compounds may also be amenable by direct acylation of phenols with catalysts such as Lewis acids as AlCl 3 , ZnCl 2 , FeCl 3 , BCl 3 , BF 3 , transition metal trifluorosulfonates (eg. Sc(OTf) 3 ) in inert solvents as EDC, CH 2 Cl 2 , CS 2 or nitrobenzene.
  • catalysts such as Lewis acids as AlCl 3 , ZnCl 2 , FeCl 3 , BCl 3 , BF 3 , transition metal trifluorosulfonates (eg. Sc(OTf) 3 ) in inert solvents as EDC, CH 2 Cl 2 , CS 2 or nitrobenzene.
  • these novel compounds are of formula (1) wherein when OH is in the meta position with respect to the ether linkage
  • R 1 , R 2 and R 3 are hydrogen
  • R 4 is in the para position with respect to the ether linkage and is C 1 -C 5 alkyl.
  • Compounds of particular interest include the following:
  • a further aspect of the present invention is another process for the preparation of compounds of formula (1) wherein when OH is in the meta position with respect to the ether linkage and R 1 , R 2 and R 3 are hydrogen and R 4 is in the para position with respect to the ether linkage and is C 1 -C 20 alkyl.
  • the process comprises reacting an acyl chloride with meta-phenoxyphenol in the presence of activated zinc at a temperature of between 70° c. to 80° C.
  • the hydroxyl group undergoes acylation, as shown in the scheme below:
  • This acyl compound then undergoes a “Fries rearrangement” in the presence of aluminium chloride at a temperature of 145° C. to 150° C., producing an acylated phenol.
  • This acylated phenol is then refluxed in the presence of amalgamated zinc, hydrochloric acid and a solvent such as toluene, to yield the end product.
  • R 6 is C 1 -C 19 alkyl.
  • the hydroxydiphenyl ether compounds according to the invention are thermally stable and antimicrobially effective compounds of low volatility and having a severely reduced tendency to migrate. They are therefore suitable for the antimicrobial finishing of polymeric compounds, for example in plastics, rubbers, paints, surface coatings, (textile) fibres which are exposed to a microbially contaminated environment.
  • polymers derived from ⁇ , ⁇ -unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates,
  • polyurethanes derived from polyethers, polyesters and polybutadienes having terminal hydroxyl groups on the one hand and aliphatic or aromatic polyisocyanates on the other, and precursors thereof,
  • polyureas polyimides, polyamide-imides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles,
  • crosslinked polymers derived from aldehydes on the one hand and phenols, urea or melamine on the other hand such as phenol-formaldehyde resins, urea-formaldehyde resins and melamine-formaldehyde resins,
  • alkyd resins polyester resins and acrylate resins
  • natural polymers such as cellulose, natural rubber, gelatine, and derivatives thereof modified chemically in a polymer-homologous manner, such as cellulose acetates, cellulose propionates cellulose butyrates, or the cellulose ethers, such as methylcellulose; and also rosins and derivatives.
  • the invention thus also provides a composition comprising
  • the invention also relates to a process for the antimicrobial finishing of an organic material, which comprises adding at least one compound of the formula (1) thereto, and to the use of the compound of the formula (1) for the antimicrobial finishing of polymeric materials.
  • the amount of antimicrobial active substance to be used depends on the organic material to be antimicrobially finished and on the intended use of the material finished in this way.
  • the composition according to the invention generally comprises, per 100 parts by weight of component (A), from 0.01 to 15 parts by weight, in particular from 0.05 to 10 parts by weight, and especially from 0.1 to 5 parts by weight of the antimicrobial active substance (component (B)).
  • the antimicrobial active substance (component (B)) can also be a mixture of two or more compounds of the formula (1).
  • the compositions according to the invention can, in addition to the compounds according to the invention, also comprise other additives, for example antioxidants or light protection agents.
  • incorporación into the organic polymers for example into the synthetic organic, in particular thermoplastic, polymers can take place by adding the hydroxydiphenyl ether compound according to the invention and, if desired, other additives by the methods customary in the art. Incorporation can expediently take place before or during shaping, for example by mixing the pulverulent components or by adding the antimicrobial active substance to the melt or solution of the polymer, or by applying the dissolved or dispersed compounds to the polymer, if desired with subsequent evaporation of the solvent.
  • Another method of incorporating the mixtures according to the invention into polymers involves adding the former before or during polymerization of the corresponding monomers or before crosslinking.
  • mixtures according to the invention can also be added to the organic polymers to be finished in the form of a masterbatch which comprises these compounds, for example, in a concentration of from 2.5 to 25% by weight.
  • the resulting antimicrobially finished polymer compositions can be converted into shaped articles, for example fibres, films, tapes, sheets, multi-wall sheets, containers, tubes and other profiles, by conventional methods, for example by hot pressing, spinning, extrusion or injection moulding.
  • the hydroxydiphenyl ether compounds of the formula (1) are also suitable for the antimicrobial finishing of undyed and dyed or printed fibre materials made, for example, of silk, wool, polyamide, polyester or polyurethane, and in particular of cellulosic fibre materials of all types.
  • Such fibre materials are the natural cellulose fibres, such as cotton, linen, jute and hemp, and also pulp and regenerated cellulose.
  • the hydroxydiphenyl ether compounds according to the invention are also suitable for the antimicrobial finishing of hydroxyl-group-containing fibres which are present in mixed fabrics, for example, of mixtures of cotton with polyester fibres or polyamide fibres.
  • the hydroxydiphenyl ether compounds of the formula (1) are also suitable for incorporation into non-wovens.
  • Non-woven is a type of fabric that is not spun and woven into a cloth, but instead bonded together. According to the ISO definition it is a manufactured sheet, web, or batt of directionally or randomly orientated fibres, bonded by friction, and/or adhesion.
  • Nonwoven textiles are widely used in disposable as well as durable goods, such as baby diaper, feminine hygiene, adult incontinence, wipers, bed linings, automotive industries, medical face masks, air and water filtration, home furnishing and geotextiles.
  • Such materials can be fabricated by different techniques, such as spunbonding, melt blown, carded thermal bonding and carded chemical bonding, dry and/or wet laid and needlefelts. Because of the nature of such applications, increasingly the market is demanding products with specific properties such as antimicrobial efficacy.
  • one or more compounds of the formula (1) are advantageously applied to the textile fibre material in an amount of from 0.01 to 20% by weight, preferably 0.1-3% by weight, and in particular from 0.25 to 2% by weight, based on the weight of the fibre material, in a process analogous to dyeing.
  • hydroxydiphenyl ether compounds according to the invention can be applied to the fibre material and fixed to the fibre in different ways, in particular in the form of aqueous dispersions or printing pastes.
  • the textile fibre materials finished using the compounds of the formula (1) according to the invention have an excellent and long-lasting antimicrobial protection.
  • An antimicrobial textile treatment formulation has, for example, the following composition:
  • hydroxydiphenyl ether compounds according to the invention can be also be used in paper finishing, printing thickeners containing starch, varnishes and paints.
  • the hydroxydiphenyl ether compounds according to the invention are also useful for the disinfection and general antimicrobial treatment, such as deodorising, of the skin, mucous membrane and hair, preferably for the disinfection of hands and wounds.
  • the hydroxydiphenyl ether compounds according to the invention are useful for the preservation of cosmetic and household products against microbial spoilage.
  • these compounds are suitable as an antimicrobial active substance in personal care products as shampoos, bath- and shower additives, hair-care products, liquid and bar soaps, lotions and cremes, deodorants, other aqueous or alcoholic solutions, for example cleaning solutions for the skin, moist cleaning sheets, oils and powders.
  • a further subject of the present invention is therefore a personal care composition
  • a personal care composition comprising at least one compound of the formula (1) and cosmetically tolerable carriers or auxiliaries.
  • the personal care composition according to the present invention comprises 0.01 to 15, preferably 0.5 to 10% b.w. of the hydroxydiphenyl ether compounds of formula (1) and cosmetically tolerable carriers or auxiliaries.
  • the personal care composition according to the invention can be formulated as a water-in-oil or oil-in-water emulsion, as an oil-in-alcohol lotion, as a vesicular dispersion of an ionic or non-ionic amphiphilic lipid, as a gel, solid stick, aerosol formulation or a surfactant based formulation, such as a soap or skin cleanser.
  • the cosmetically compatible auxiliary preferably contains 5 to 50% of an oil phase, 5 to 20% of an emulsifier and 30 to 90% of water.
  • the oil phase can in this case contain any oil suitable for cosmetic formulations, e.g. one or more hydrocarbon oils, a wax, a natural oil, a silicone oil, a fatty acid ester or a fatty alcohol.
  • Preferred mono- or polyols are ethanol, isopropanol, propylene glycol, hexylene glycol, glycerol and sorbitol.
  • any conventionally usable emulsifier can be used for the cosmetic composition according to the invention, for example one or more ethoxylated esters of natural derivatives, e.g. poly-ethoxylated esters of hydrogenated castor oil; or a silicone oil emulsifier, e.g. a silicone polyol; an optionally ethoxylated fatty acid soap; an ethoxylated fatty alcohol; an optionally ethoxylated sorbitan ester; an ethoxylated fatty acid; or an ethoxylated glyceride.
  • ethoxylated esters of natural derivatives e.g. poly-ethoxylated esters of hydrogenated castor oil
  • silicone oil emulsifier e.g. a silicone polyol
  • an optionally ethoxylated fatty acid soap e.g. a ethoxylated fatty alcohol
  • an optionally ethoxylated sorbitan ester an
  • the cosmetic composition may also comprise further components, e.g. emollients, emulsion stabilisers, skin humectants, skin tanning accelerators, thickeners, such as xanthan, moisture-retention agents, such as glycerol, preservatives, perfumes and colourings.
  • emollients e.g. emollients, emulsion stabilisers, skin humectants, skin tanning accelerators, thickeners, such as xanthan, moisture-retention agents, such as glycerol, preservatives, perfumes and colourings.
  • the preparation of the cosmetic composition can be effected by physically mixing the antimicrobial(s) with the auxiliary by customary methods, for example by simply stirring the individual components together.
  • Cosmetic formulations include a very wide range of cosmetic products. Suitable products are, for example, especially the following:
  • skin-care products for example skin washing and cleansing products in the form of bars of soap or liquid soaps, syndets or washing pastes,
  • bath products for example liquid (foam baths, milks, shower products) or solid bath products, such as bath pearls and bath salts;
  • skin-care products such as skin emulsions, multiple emulsions or skin oils
  • decorative body-care products for example face make-ups in the form of day or powder creams, face powders (lose and compressed), rouge or cream make-ups, eye-care products, for example eye shadow products, mascara, eyeliners, eye creams or eye-fix creams; lip-care products, for example lipstick, lip gloss, lip liner, nail-care products, such as nail varnish, nail varnish remover, nail hardeners or cuticle removers;
  • feminine hygiene products such as feminine hygiene washing lotions or sprays
  • foot-care products for example foot baths, foot powders, food creams or foot balms, special deodorants and antiperspirants or products for scrubbing off callouses;
  • sunscreens such as sun milks, lotions, creams, oils, sunblockers or tropicals, pre-sun products or after-sun products;
  • suntanning products for example self-tanning creams
  • depigmenting products for example products for bleaching or lightening skin
  • insect repellents for example insect oils, lotions, sprays or sticks;
  • deodorants for example deodorant sprays, non-aerosol sprays, deodorant gels, sticks or roll-ons;
  • antiperspirants for example antiperspirant sticks, creams or roll-ons;
  • products for cleansing and treating impure skin for example syndets (solid or liquid), peeling or scrubbing products or peeling masks;
  • chemical depilatory products for example depilatory powders, liquid depilatory products, creamy or pasty depilatory products, depilatory gels or aerosol foams;
  • shaving products for example shaving soap, foaming shaving creams, non-foaming shaving creams, shaving foams and gels, preshaving products for dry shaving, aftershaves or aftershave lotions;
  • scents for example perfumes (Eau de Cologne, Eau de Toilette, Eau de perfume, perfume oils or perfume creams;
  • products for oral and dental hygiene as well as for dentures for example toothpastes, tooth gels, tooth powders, mouth-wash concentrates, anti-plaque mouth-washes, denture cleaning products or denture adhesion products;
  • cosmetic formulations for hair treatment for example hair washes in the form of shampoos, hair conditioners, hair-care products, for example pretreatment products, hair tonics, hair styling creams and gels, pomades, hair rinses, deep conditioning treatments, intensive hair care treatments, hair setting products, for example waving agents for perms (hot wave, mild wave, cold wave), hair straightening products, liquid hair fixatives, hair foams, hair sprays, bleaching agents, for example hydrogen peroxide solutions, bleaching shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, temporary, semitemporary or permanent hair dyes, products containing self-oxidising dyes, or natural hair dyes, such as henna or camomile.
  • hair setting products for example waving agents for perms (hot wave, mild wave, cold wave), hair straightening products, liquid hair fixatives, hair foams, hair sprays, bleaching agents, for example hydrogen peroxide solutions, bleaching shampoos, bleaching creams, bleaching powders, bleaching paste
  • An antimicrobial soap has, for example, the following composition:
  • soap base for example the sodium salts of tallow fatty and coconut fatty acid or glycerols.
  • a shampoo has, for example, the following composition:
  • a deodorant has, for example, the following composition:
  • the oral hygiene composition may comprise an additional antibacterial enhancing agent, for example an anionic polymeric polycarboxylate, a dehydrated polyphosphate salt, a compound which provides a source of fluoride ions, a polishing material, including siliceous material or sodium bicarbonate, an orally acceptable vehicle, including a water-phase with humectant, thickeners, surface-active agents and a flavoring or sweetening material.
  • an additional antibacterial enhancing agent for example an anionic polymeric polycarboxylate, a dehydrated polyphosphate salt, a compound which provides a source of fluoride ions, a polishing material, including siliceous material or sodium bicarbonate, an orally acceptable vehicle, including a water-phase with humectant, thickeners, surface-active agents and a flavoring or sweetening material.
  • the oral hygiene composition according to the invention contains from 0.003 to 5% by weight based on the total weight of the composition, of antimicrobial or a mixture of antimicrobials.
  • the preparation of the oral hygiene composition can be effected by physically mixing the antimicrobial(s) with the other ingredients by customary methods, for example by simply stirring the individual components together, then mixing further under vacuum.
  • An oral care formulation has, for example, the following composition:
  • the oral hygiene composition may be in various forms of presentation including the form of a gel, paste, cream or mouthwash.
  • hydroxydiphenyl ether compounds according to the invention are useful as household cleaners for the cleaning and disinfection of hard surfaces.
  • a detergent has, for example, the following composition:
  • Candida albicans ATCC 10231 Candida albicans ATCC 10231
  • test substances are dissolved in ethanol, and a dilution series of the compound of the formula (102) in agar are prepared.
  • Anaerobic bacteria and dermatophytes are activated on agar-plates, and washes off with Mueller-Hinton bouillon. Aerobic bacteria are activated in Mueller-Hinton bouillon overnight. The test germ suspension are diluted with Mueller-Hinton bouillon to a density of McFarland standard 0.5.
  • the minimum inhibitory concentration (MIC) is given as the lowest concentration which shows clear inhibition compared with the control.
  • M.S. (141) 4-((3-Methyl butyl)- phenoxy)3-(3-methyl butyl)phenol Procedure I, II, IV & III/VII — 1. 1 H-NMR 2.
  • M.S. (142) 4-(4-Nonyl phenoxy)- phenol Procedure I, II, IV & III/VII 50-51 1. 1 H-NMR 2.
  • M.S. (143) 4-(2-Methylethyl-4-(2- phenylethyl)phenoxy)- phenol Procedure I, II, IV & III/VII — 1. 1 H-NMR 2.
  • M.S. (144) 4-(4-Propionyl phenoxy)phenol Procedure I, II & IV — 1.
  • M.S. (160) 2-(Dodecanoyl-5- phenoxy phenol Procedure V, VI A/VI B & III/VII — 1. 1 H-NMR 2.
  • M.S. (161) 3-[4-(2-methyl ethyl)]phenoxy phenol Procedure I & IV — 1. 1 H-NMR 2.
  • M.S. (162) 4-(2-methylethyl-4- ethyl)phenoxy phenol Procedure I, II, IV & III/ VII — 1. 1 H-NMR 2.
  • Zinc amalgam was prepared from 12 g of Zn dust, 0.9 g of mercury (II) chloride in 20 ml water and 2-3 ml HCl conc . This was added to the solution of keto compd 1.5 g (5.28 mmol) in 25 ml of toluene & 20 ml HCl conc . HCl gas bubbled into reaction mixture for 2 hr. 50 ml of toluene was added and toluene layer separated and washed with water. Solvent distilled off under reduced pressure to get the product.

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US20050203179A1 (en) * 2002-04-12 2005-09-15 Bernhard Banowski Use of hydroxydiphenyl ether derivatives as arylsulfatase-inhibitors in deodorants and antiperspirants
WO2007009879A1 (en) * 2005-07-15 2007-01-25 Ciba Specialty Chemicals Holding Inc. Preservatives
US7858666B2 (en) 2007-06-08 2010-12-28 Mannkind Corporation IRE-1α inhibitors
CN103589757A (zh) * 2013-02-04 2014-02-19 中国海洋大学 一种溴代联苯醚衍生物的制备方法与作为抗菌剂的应用

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GB2357968A (en) * 2000-12-18 2001-07-11 Ciba Sc Holding Ag Use of hydroxy diphenylethers as disinfectants
WO2002050008A2 (en) * 2000-12-20 2002-06-27 Warner-Lambert Company Llc Non-halogenated phenoxy and/or benzyloxy phenols and antimicrobial compositions containing them
US20030207945A1 (en) 2001-12-20 2003-11-06 Harper David Scott Non-halogenated phenyl substituted phenols, antimicrobial compositions containing the same, and methods of using the same
FR2826574B1 (fr) * 2001-06-29 2005-08-26 Oreal Compositions contenant un derive d'hydroxydiphenyl ether inhibant le developpement des odeurs corporelles
FR2826571B1 (fr) * 2001-06-29 2005-10-07 Oreal Compositions contenant un derive d'hydroxydiphenyl ether inhibant le developpement des odeurs corporelles
FR2826572B1 (fr) * 2001-06-29 2005-10-07 Oreal Compositions contenant un derive d'hydroxydiphenyl ether inhibant le developpement des odeurs corporelles
FR2826570B1 (fr) * 2001-06-29 2005-08-26 Oreal Compositions contenant un derive d'hydroxydiphenyl ether inhibant le developpement des odeurs corporelles
FR2826573B1 (fr) * 2001-06-29 2005-10-07 Oreal Compositions contenant un derive d'hydroxydiphenyl ether inhibant le developpement des odeurs corporelles
WO2003031382A2 (en) * 2001-10-09 2003-04-17 Ciba Specialty Chemicals Holding Inc. Process for the preparation of hydroxydiphenyl ether compounds
CN1642890A (zh) * 2002-03-19 2005-07-20 西巴特殊化学品控股有限公司 苯甲醇衍生物
EP1366763A1 (de) * 2002-05-28 2003-12-03 Ciba SC Holding AG Hydroxydiphenyletherverbindungen als Entzündungshemmer
EP1366757A1 (de) * 2002-05-28 2003-12-03 Ciba SC Holding AG Verwendung von Hydroxydiphenyletherverbindungen zur Behandlung der Haut
EP1369038A1 (de) * 2002-06-05 2003-12-10 Ciba SC Holding AG Körperpflegemittel
DE10236610A1 (de) * 2002-08-09 2004-02-19 Beiersdorf Ag Kosmetische und/oder dermatologische Wirkstoffkombinationen
EP2178532A2 (de) * 2007-05-22 2010-04-28 Wisconsin Alumni Research Foundation Antibakterielle wirkstoffausrichtung von genompflege-schnittstellen
EP2539305B1 (de) * 2010-02-27 2017-02-15 The United States of America, as represented by The Secretary, Department of Health and Human Services Antimikrobielle chrysophaentin-verbindungen zur hemmung des ftsz-proteins
WO2015172678A1 (en) * 2014-05-12 2015-11-19 The Procter & Gamble Company Method of laundering fabric
CN107827716A (zh) * 2017-09-28 2018-03-23 大连天源基化学有限公司 1‑(4‑苯氧苯氧基)‑2‑丙醇生产中釜残的处理方法
CN111315858B (zh) * 2017-11-14 2021-12-24 宝洁公司 颗粒状抗微生物衣物洗涤剂组合物

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US20050203179A1 (en) * 2002-04-12 2005-09-15 Bernhard Banowski Use of hydroxydiphenyl ether derivatives as arylsulfatase-inhibitors in deodorants and antiperspirants
WO2007009879A1 (en) * 2005-07-15 2007-01-25 Ciba Specialty Chemicals Holding Inc. Preservatives
US20090036543A1 (en) * 2005-07-15 2009-02-05 Werner Holzl Preservatives
US7858666B2 (en) 2007-06-08 2010-12-28 Mannkind Corporation IRE-1α inhibitors
US8614253B2 (en) 2007-06-08 2013-12-24 Mannkind Corporation IRE-1α inhibitors
US9241942B2 (en) 2007-06-08 2016-01-26 Mannkind Corporation IRE-1α inhibitors
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CN103589757A (zh) * 2013-02-04 2014-02-19 中国海洋大学 一种溴代联苯醚衍生物的制备方法与作为抗菌剂的应用

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