EP1119540A1 - Process for the preparation of 4,4'-dihalogen-o-hydroxydiphenyl compounds - Google Patents

Process for the preparation of 4,4'-dihalogen-o-hydroxydiphenyl compounds

Info

Publication number
EP1119540A1
EP1119540A1 EP99970076A EP99970076A EP1119540A1 EP 1119540 A1 EP1119540 A1 EP 1119540A1 EP 99970076 A EP99970076 A EP 99970076A EP 99970076 A EP99970076 A EP 99970076A EP 1119540 A1 EP1119540 A1 EP 1119540A1
Authority
EP
European Patent Office
Prior art keywords
compound
copper
process according
formula
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP99970076A
Other languages
German (de)
English (en)
French (fr)
Inventor
Armando Di Teodoro
Werner Hölzl
Dieter Reinehr
Rudolf Zink
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Original Assignee
Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Spezialitaetenchemie Holding AG, Ciba SC Holding AG filed Critical Ciba Spezialitaetenchemie Holding AG
Priority to EP99970076A priority Critical patent/EP1119540A1/en
Publication of EP1119540A1 publication Critical patent/EP1119540A1/en
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/50—Preparation of compounds having groups by reactions producing groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
    • 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

Definitions

  • the present invention relates to a process for the preparation of 4,4'-dihalogen-o-hydroxy- diphenyl compounds of formula
  • Hal is a halogen atom, and to the use of these compounds for protecting organic materials and objects from microorganisms.
  • this invention has for its object to provide an economic process for the preparation of 4,4'-dihalogen-o-hydroxydiphenyl compounds in which undesirable concurrent reactions are suppressed.
  • This object is achieved in accordance with this invention by a four-step reaction, where in the first step a diphenyl compound is halogenised or p-halophenol is reacted with p-dihalophenol in the presence of copper and/or copper salts; in the second step the dihalogen compound is acylated in a Friedel-Crafts reaction; in a third step the acyl compound is oxidised, and in a fourth step the oxidised compound is hydrolysed, corresponding to the following reaction scheme:
  • R is CrC 8 alkyl which is unsubstituted or substituted by 1 to 3 halogen atoms or hydroxy; unsubstituted C 6 -C 12 aryl; or C 6 -C 12 aryl which is substituted by 1 to 3 halogen atoms, d-Csalkyl or CrC 8 alkoxy, or their combinations; and Hal is a halogen atom;
  • CrC 8 alkyl is branched or unbranched alkyl, for example methyl, ethyl, propyl, isopropyl, n- butyl, sec-butyl, isobutyl, t-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1 ,3-di- methylbutyl, n-hexyl, 1 -methylhexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3-tetramethylbutyl, 1-methyl- heptyl, 3-methylheptyl, 2-ethylhexyl or n-octyl.
  • C C 8 Alkoxy is straight-chain or branched radicals, for example methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy or octy
  • Halogen is fluoro, bromo or, preferably, chloro.
  • R is C C 4 alkyl and, preferably, methyl.
  • the chlorination agent used for reaction step 1a is, for example, sulfuryl chloride or, preferably, gaseous chlorine.
  • the reaction is preferably carried out in the presence of a catalyst, such as dibenzothiophene, methyl sulfide, propyl sulfide, phenyl sulfide, a Lewis acid, such as aluminium chloride, or mixtures of these compounds.
  • a particularly suitable catalyst for the novel chlorination reaction is a mixture of propyl sulfide and an equimolar amount of aluminium chloride.
  • the temperature for the reaction of the first step can be chosen from within a wide range, for example from -10 to 50°C.
  • the reaction is preferably carried out at a temperature from 0 to 40°C.
  • the reaction times are also within a wide range.
  • the reaction is normally carried out over 1 to 48 hours, preferably over 2.5 to 10 hours.
  • step 1 b is usually carried out at temperatures from 120 to 200, preferably from 130 to 170°C, it being necessary for the phenol compound of formula (4a) and the dihalogen compound of formula (4b) to be present in a stoichiometric ratio, and the alkali hydroxide must be present in less than equivalent amount (20 to 80 % of theory).
  • the copper catalysts used are preferably the copper salts conventionally used for the Ullmann synthesis, for example copper(ll) oxide, copper(l) oxide, copper carbonate, basic copper carbonate, copper(l) chloride, copper(ll) chloride, copper(l) bromide, copper(ll) bromide or copper sulfate.
  • the acylation reaction (2 nd step) is usually carried out in the presence of a Lewis acid, such as aluminium chloride.
  • the Lewis acid is used in this case in 1 to 3, preferably 1.25 to 2, molar amount, based on the halogenated acyl compound of formula (5).
  • a suitable acylation reagent for this reaction is an acyl halide, preferably acetyl chloride.
  • agents are, for example, H 5 C—
  • Lewis acid and acylation reagent are preferably used in equimolar amounts.
  • the reaction is carried out in the solvents conventionally used for Friedei-Crafts reactions, such as halogenated solvents, preferably methylene chloride or ethylene chloride.
  • the acylation reaction is carried out in the presence of acetyl chloride and aluminium chloride, which are used in equimolar amounts.
  • the reaction time is of subordinate importance for this reaction step and may vary within a wide range, for example from 1 to 18 hours.
  • the halogenation reaction (first step) and the acylation reaction (second step) as well as the optionally repeated chlorination reaction are preferably carried out in the same reaction vessel and are thus one-pot reactions.
  • Suitable oxidants are for example: equimolar mixture of dilute peracetic acid and acetic anhydride in the presence of a catalytic amount of perchloric acid; excess of 3-chloro-perbenzoic acid in water; di-peroxydodecane diacid (DPDDA); mixture of dilute peracetic acid and acetic anhydride and sulfuric acid; persulfuric acid; mixture of concentrated sulfuric acid, anhydrous acetic acid and hydrogen peroxide; mixture of m-chloroperbenzoic acid ( CPBA), trifluoroacetic acid and dichloromethane; mixture of sodium perborate and trifluoroacetic acid; mixture of formic acid, hydrogen peroxide, acetic anhydride, phosphoropentoxide and acetic acid; mixture of acetic acid, hydrogen per
  • a mixture of concentrated sulfuric acid, anhydrous acetic acid and hydrogen peroxide is preferably used for the oxidation.
  • a commercially available wetting agent may be added to the oxidant.
  • reaction times may be within a wide range from about 1 to about 24 hours, preferably from 1 to 5 hours.
  • the reaction temperature ranges from -20°C to about 80°C.
  • the reaction is preferably carried out at room temperature.
  • the 4,4'-dihalogen-o-hydroxydiphenyl compounds prepared according to this invention are insoluble in water, but are soluble in dilute sodium hydroxide solution and potassium hydroxide solution and in virtually all organic solvents. Thanks to these solubility preconditions they have very versatile applicability for fighting microorganisms, in particular bacteria, and for protecting organic materials and objects from microorganisms. They are thus particularly suitable for the disinfection, deodorisation and the general antimicrobial treatment of the skin, mucosae and all integumentary appendages (hair), very particularly for the disinfection of hands and wounds.
  • body-care products for example shampoos, bath additives, hair-care products, liquid and solid soaps (based on synthetic surfactants and salts of saturated and/or unsaturated fatty acids), lotions and creams, deodorants, other aqueous or alcoholic solutions, for example cleansing solutions for the skin, moist cleansing tissues, oils or powders.
  • body-care products for example shampoos, bath additives, hair-care products, liquid and solid soaps (based on synthetic surfactants and salts of saturated and/or unsaturated fatty acids), lotions and creams, deodorants, other aqueous or alcoholic solutions, for example cleansing solutions for the skin, moist cleansing tissues, oils or powders.
  • this invention also relates to body-care products containing at least one compound of formula (1 ) and to cosmetically compatible carriers or auxiliaries.
  • the novel body-care product comprises 0.01 to 15 % by weight, preferably 0.5 to 10 % by weight, based on the total weight of the composition, of the compound of formula (1 ) as well as cosmetically compatible auxiliaries.
  • the body-care product contains other components besides the compound of formula (1 ), for example sequestrants, colourants, perfume oils, thickeners or consistency regulators, emollients, UV absorbers, skin protectives, antioxi- dants, additives for improving the mechanical properties, such as dicarboxylic acids and/or the Al, Zn, Ca, Mg salts of C 14 -C 22 fatty acids, and, optionally, additional antimicrobial active substances.
  • sequestrants for example sequestrants, colourants, perfume oils, thickeners or consistency regulators, emollients, UV absorbers, skin protectives, antioxi- dants, additives for improving the mechanical properties, such as dicarboxylic acids and/or the Al, Zn, Ca, Mg salts of C 14 -C 22 fatty acids, and, optionally, additional antimicrobial active substances.
  • the novel body-care product may be formulated as water-in-oil or oil-in-water emulsion, as alcoholic or alcohol-containing formulation, as vesicular dispersion of a ionic or non-ionic amphiphilic lipid, as gel, solid stick or as aerosol formulation.
  • a water-in-oil or oil-in-water emulsion comprising the compound of formula (1 ) contains as cosmetically compatible auxiliaries preferably 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, for example one or several hydrocarbon oils, wax, natural oil, silicone oil, fatty acid ester or fatty alcohol.
  • Preferred mono- or polyols are ethanol, isopropanol, propylene glycol, hexylene glycol, glycerol and sorbitol.
  • compositions of this invention may be present in different cosmetic formulations.
  • 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, foot
  • composition of an antimicrobial soap is, for example, as follows:
  • stearic acid 1 to 10 % by weight of stearic acid, ad 100% of soap base, for example the sodium salts of tallow fatty acid and coconut fatty acid or glycerols.
  • composition of a shampoo is, for example, as follows:
  • composition of a deodorant is, for example, as follows:
  • caprylic/capric triglyceride 6 % by weight of caprylic/capric triglyceride, 4 % by weight of glycerol, 0.2 % by weight of di-sodium EDTA, 1.0 % by weight of citric acid (20%), and 65.8-70.8 % by weight of water.
  • caprylic/capric triglyceride 4 % by weight of caprylic/capric triglyceride
  • this invention relates to an oral composition, containing
  • the novel oral composition may be, for example, a gel, paste, cream or an aqueous formulation (mouth-wash).
  • the novel oral composition can furthermore contain compounds which release fluoride ions which are effective against caries formation, for example inorganic fluoride salts, such as sodium, potassium, ammonium or calcium fluoride, or organic fluoride salts, such as amine fluorides, which are known under the tradename Olafluor.
  • the compounds of formula (1 ) used according to this invention are furthermore suitable for the antimicrobial treatment of textile fibre materials.
  • textile fibre materials are undyed and dyed or printed fibre materials, for example of silk, wool, polyamide, polyester, polypropylene or poly- urethanes and, preferably, cellulose-containing fibre materials of all kinds.
  • Such fibre materials are, for example, natural cellulose fibres, such as cotton, linen, jute and hemp, and cellulose and regenerated cellulose.
  • Particularly suitable textile fibre materials are those consisting of cotton.
  • the compounds of formula (1) are also suitable for preserving cosmetic products, such as shampoos, bath additives, hair- care products, liquid and solid soaps (based on synthetic surfactants and the salts of saturated and/or unsaturated fatty acids), lotions and creams, deodorants, other aqueous or alcoholic solutions, e.g. cleansing solutions for the skin, moist cleansing tissues, oils or powders, and household products, for example washing and cleaning formulations, such as liquid and powder detergents or softeners.
  • cosmetic products such as shampoos, bath additives, hair- care products, liquid and solid soaps (based on synthetic surfactants and the salts of saturated and/or unsaturated fatty acids), lotions and creams, deodorants, other aqueous or alcoholic solutions, e.g. cleansing solutions for the skin, moist cleansing tissues, oils or powders, and household products, for example washing and cleaning formulations, such as liquid and powder detergents or softeners.
  • the compounds of formula (1) used according to this invention are also suitable for the antimicrobial finishing of synthetic materials, for example polyethylene, polypropylene, polyure- thane, polyester, polyamide, polycarbonate, latex and the like. Areas of application for these are typically floorings, plastic coatings, plastic container materials and packaging materials; kitchen and bathroom utensils (e.g. brushes, shower curtains; sponges, bathroom mats), latex filter materials (air and water filters), plastic articles which are used in the medical field, for example bandaging materials, syringes, catheters and the like, so-called medical devices, gloves and mattresses.
  • synthetic materials for example polyethylene, polypropylene, polyure- thane, polyester, polyamide, polycarbonate, latex and the like. Areas of application for these are typically floorings, plastic coatings, plastic container materials and packaging materials; kitchen and bathroom utensils (e.g. brushes, shower curtains; sponges, bathroom mats), latex filter materials (air and water filters), plastic articles which are used in the medical field, for example
  • Paper for example sanitary papers, can also be antimicrobially finished with the novel compounds of formula (1).
  • nonwovens for example diapers, sanitary towels and pads, tissues for hygienic and household use.
  • the hydroxyphenyl-1 ,3-propanediones can, in particular, also be used in household and all- purpose cleaners used for cleaning and disinfecting hard surfaces.
  • the composition of a cleaning agent is, for example, as follows:
  • Beside preserving cosmetic and household products it is also possible to preserve and antimicrobially finish technical products, such as paper treatment liquors, printing thickeners consisting of starch or cellulose derivatives, paint systems and paints.
  • the compounds of formula (1 ) are also suitable for the antimicrobial wood treatment and for the antimicrobial treatment and finishing of leather.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Paper (AREA)
  • Cosmetics (AREA)
  • Detergent Compositions (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
EP99970076A 1998-10-06 1999-09-27 Process for the preparation of 4,4'-dihalogen-o-hydroxydiphenyl compounds Ceased EP1119540A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP99970076A EP1119540A1 (en) 1998-10-06 1999-09-27 Process for the preparation of 4,4'-dihalogen-o-hydroxydiphenyl compounds

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP98811002 1998-10-06
EP98811002 1998-10-06
PCT/EP1999/007158 WO2000020366A1 (en) 1998-10-06 1999-09-27 Process for the preparation of 4,4'-dihalogen-o-hydroxydiphenyl compounds
EP99970076A EP1119540A1 (en) 1998-10-06 1999-09-27 Process for the preparation of 4,4'-dihalogen-o-hydroxydiphenyl compounds

Publications (1)

Publication Number Publication Date
EP1119540A1 true EP1119540A1 (en) 2001-08-01

Family

ID=8236372

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99970076A Ceased EP1119540A1 (en) 1998-10-06 1999-09-27 Process for the preparation of 4,4'-dihalogen-o-hydroxydiphenyl compounds

Country Status (11)

Country Link
EP (1) EP1119540A1 (ko)
JP (1) JP2002526515A (ko)
KR (1) KR20010075572A (ko)
CN (1) CN1321142A (ko)
AU (1) AU5982199A (ko)
BR (1) BR9914265A (ko)
IL (1) IL141947A0 (ko)
RU (1) RU2220946C2 (ko)
SK (1) SK4542001A3 (ko)
WO (1) WO2000020366A1 (ko)
ZA (1) ZA200102818B (ko)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1369038A1 (en) * 2002-06-05 2003-12-10 Ciba SC Holding AG Personal care products
EP2436754A1 (de) * 2011-09-30 2012-04-04 Basf Se Antimikrobielle Reinigungszusammensetzung
CN104803873B (zh) * 2015-03-26 2016-09-07 洪湖市一泰科技有限公司 一种傅克反应中Al资源的回收再利用方法
CN109541069A (zh) * 2018-12-20 2019-03-29 上海开米科技有限公司 一种洗涤剂中4,4-二氯-2-羟基二苯醚含量的检测方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1051823A (ko) * 1964-02-14
DE3839758A1 (de) * 1988-10-24 1990-04-26 Bayer Ag Substituierte 2-aminothiazole
IL123015A (en) * 1997-02-05 2003-07-06 Ciba Sc Holding Ag Process for the preparation of ortho-substituted halophenols, some new intermediates and disinfectants for protecting organic materials from attack by microorganisms comprising compounds prepared by said process
EP0887333B1 (en) * 1997-06-25 2001-11-14 Ciba SC Holding AG Process for the production of halogeno-o-hydroxydiphenyl compounds

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0020366A1 *

Also Published As

Publication number Publication date
IL141947A0 (en) 2002-03-10
KR20010075572A (ko) 2001-08-09
BR9914265A (pt) 2001-06-26
CN1321142A (zh) 2001-11-07
AU5982199A (en) 2000-04-26
WO2000020366A1 (en) 2000-04-13
ZA200102818B (en) 2001-11-15
RU2220946C2 (ru) 2004-01-10
JP2002526515A (ja) 2002-08-20
SK4542001A3 (en) 2001-09-11

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