JP2002526515A - Method for producing 4,4'-dihalogen-o-hydroxydiphenyl compound - Google Patents

Abstract

  (57) [Summary] Disclosed are halogenation of diphenyl compounds (step 1a) or reaction of p-halophenol with p-dihalobenzene (step 1b), acylation of dihalogen compounds in a Friedel-Crafts reaction (second step), This is a four-step process for producing a 4,4'-dihalogen-o-hydroxydiphenyl compound of formula (1) by oxidation (third step) and hydrolysis (fourth step) of the acyl compound. The compounds of the formula (1) are used for protecting organic materials and substances from microorganisms.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD OF THE INVENTION

 The present invention provides a compound of formula (1):

[0002]

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(Wherein Hal is a halogen atom)
The present invention relates to a process for the preparation of o-hydroxydiphenyl compounds and to the use of these compounds for protecting organic materials and substances from microorganisms.

[0004]

[Prior art]

The preparation of the 4,4'-dihalogen-o-hydroxydiphenyl compound is usually carried out by using 2-
It is carried out by diazotization of amino-4,4'-dichlorodiphenyl ether (compound of formula (2)) followed by hydrolysis:

[0005]

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[0006]

However, since various chemical reactions can occur at the same time, the yield obtained by this preparation method is insufficient.

[0007]

[Means for Solving the Problems]

Accordingly, an object of the present invention is to provide an economical method for producing a 4,4'-dihalogen-o-hydroxydiphenyl compound in which undesirable simultaneous reactions are suppressed.

[0008] This object is achieved in the present invention by a four-step reaction. Here, in the first step, corresponding to the following reaction scheme, a diphenyl compound is halogenated or p-halophenol is used. reacting with p-dihalophenol in the presence of copper and / or copper salts; in a second step, the dihalogen compound is acylated in a Friedel-Crafts reaction; in a third step, the acyl compound is oxidized; In a fourth step, the oxidized compound is hydrolyzed:

[0009]

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In the above scheme, R is C ₁ -C ₈ alkyl; unsubstituted C ₆ -C ₁₂ aryl; unsubstituted or substituted by one to three halogen atoms or hydroxy;
To three halogen atom, a C ₁ -C ₅ alkyl or C ₁ -C ₈ alkoxy, or C ₆ -C ₁₂ aryl which is substituted by a combination thereof; and Hal is a halogen atom.

C ₁ -C ₈ alkyl is a branched or unbranched alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, 2-ethylbutyl, n-butyl Pentyl, isopentyl, 1-methylpentyl,
1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl,
Isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3
-Methylheptyl, 2-ethylhexyl or n-octyl.

C ₁ -C ₈ alkoxy is a linear or branched group, for example methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy or octyloxy.

[0013] Halogen is fluoro, bromo or, preferably, chloro.

In formulas (6) and (7) of the above reaction scheme, R is C ₁ -C ₄ alkyl, preferably methyl.

If the halogen is preferably chlorine, the chlorinating agent used in reaction step 1a is, for example, sulfuryl chloride, or preferably gaseous chlorine. This reaction is
Preferably, dibenzothiophene, methyl sulfide, propyl sulfide, phenyl sulfide,
It is carried out in the presence of a catalyst, such as a Lewis acid such as aluminum chloride, or a mixture of these compounds. A particularly suitable catalyst for the novel chlorination reaction is a mixture of propyl sulfide and equimolar amounts of aluminum chloride.

[0016] The temperature for the reaction of the first step can be selected from a wide range (for example, -10 to 50 ° C). This reaction is preferably performed at a temperature of 0 to 40 ° C.

[0017] Reaction times are also in a wide range. This reaction is generally performed for 1 to 48 hours, preferably 2.5 to 10 hours.

The reaction of step 1b is usually carried out at a temperature of from 120 to 200 ° C., preferably from 130 to 170 ° C., and the phenol compound of the formula (4a) and the dihalogen compound of the formula (4b) are formed in a stoichiometric ratio. It must be present and the alkali hydroxide must be present in less than an equivalent (20-80% of theory).

The copper catalyst used is preferably a copper salt conventionally used in Ullman synthesis, such as copper (II) oxide, copper (I) oxide, copper carbonate, basic copper carbonate, copper chloride (I )
, Copper (II) chloride, copper (I) bromide, copper (II) bromide or copper sulfate.

Further details regarding reaction step 1b can be found in DE-OS-2,242,519.

The acylation reaction (second step) is usually performed in the presence of a Lewis acid such as aluminum chloride. The Lewis acid is used in this case in a molar amount of 1 to 3 times, preferably 1.25 to 2 times, based on the acyl halide compound of the formula (5). A suitable acylating reagent for this reaction is an acyl halide, preferably acetyl chloride. Other suitable acylating agents are, for example:

[0022]

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In this case, the Lewis acid and the acylating reagent are preferably used in equimolar amounts. The reaction is carried out in a halogenated solvent, preferably a solvent conventionally used in Friedel-Crafts reactions, such as methylene chloride or ethylene chloride.

In a particular embodiment of the invention, the acylation reaction is used in equimolar amounts,
It is carried out in the presence of acetyl chloride and aluminum chloride.

The reaction time is of lower importance in this reaction step and can be in a wide range (for example, 1
１８18 hours).

The halogenation reaction (first step) and the acylation reaction (second step), and the chlorination reaction optionally repeated, are preferably carried out in the same reaction vessel, and thus a one-pot reaction (one-step reaction) pot reactions).

The oxidation of the acyl compound of formula (6) to the compound of formula (7) (Bayer-Villiger oxidation) can be carried out with various oxidizing agents. Suitable oxidizing agents are, for example: an equimolar mixture of dilute peracetic acid and acetic anhydride in the presence of a catalytic amount of perchloric acid; an excess of 3-chloro-perbenzoic acid in water; A mixture of dilute peracetic acid, acetic anhydride and sulfuric acid; persulfuric acid; a mixture of concentrated sulfuric acid, acetic anhydride and hydrogen peroxide; m-chloroperbenzoic acid (MCPBA); A mixture of trifluoroacetic acid and dichloromethane; a mixture of sodium perborate and trifluoroacetic acid; a mixture of formic acid, hydrogen peroxide, acetic anhydride, phosphorus pentoxide and acetic acid; a mixture of acetic acid, hydrogen peroxide, acetic anhydride and pentaacetic acid. A mixture of phosphorus oxides; a mixture of K ₂ S ₂ O ₈ , sulfuric acid and a 1: 1 water / methanol mixture; a mixture of acetic acid and the potassium salt of monoperoxomaleic acid; trichloromethylene, mono A mixture of potassium salt of peroxomaleic acid and sodium hydrogen sulfate; a mixture of maleic anhydride, acetic anhydride, hydrogen peroxide and trichloromethane; a mixture of maleic anhydride, a urea-hydrogen peroxide complex and acetic acid; Monoperphthalate.

Preferably, a mixture of concentrated sulfuric acid, acetic anhydride and hydrogen peroxide is used for this oxidation.

If necessary, a commercially available wetting agent may be added to the oxidizing agent.

The reaction time can be in a wide range from about 1 to about 24 hours, preferably 1 to 5 hours.

[0031] The reaction temperature ranges from -20 ° C to about 80 ° C. This reaction is preferably performed at room temperature.

The subsequent hydrolysis of the desired formula (1) to 4,4′-dihalogen-o-hydroxydiphenyl ether proceeds quantitatively.

The 4,4′-dihalogen-o-hydroxydiphenyl compounds prepared according to the present invention are insoluble in water, but soluble in dilute sodium hydroxide and potassium hydroxide solutions and in virtually all organic solvents. It is. Thanks to their solubility preconditions, they have a great variety of applications for fighting microorganisms, especially bacteria, and for protecting organic materials and substances from microorganisms. Thus, they are particularly suitable for the disinfection, deodorization and general antibacterial treatment of the skin, mucous membranes and all coat appendages (hair), in particular for the disinfection of hands and wounds.

These are therefore body care products such as shampoos, baths, hair care products, liquid and bar soaps (based on synthetic surfactants and salts of saturated and / or unsaturated fatty acids), lotions and creams Deodorants, other aqueous or alcoholic solutions, such as skin cleansing solutions, wet cleansing tissues,
Suitable as an antibacterial active in oils or powders.

The invention therefore also relates to a body care product comprising at least one compound of the formula (1) and a cosmetically compatible carrier or auxiliary.

The novel body care products may contain from 0.01 to 15% by weight, preferably from 0.5 to 10% by weight, of a compound of the formula (1), furthermore cosmetically compatible, based on the total weight of the composition It is characterized by containing an auxiliary agent which can be used.

Depending on the appearance of the body care product, other components besides the compound of formula (1), such as sequestering agents, coloring agents, balms, thickeners or consistency regulators, emollients,
UV absorbers, skin-protective agents, antioxidants, dicarboxylic acids and / or C ₁₄ -C ₂₂ fatty acid Al, Zn, Ca, additives for mechanical property improvements such as Mg salts, as well as additional antimicrobial optionally Contains sexually active substances.

The novel body care products include gels, as water-in-oil or oil-in-water emulsions, as alcoholic or alcohol-containing formulations, as vesicular dispersions of ionic or nonionic amphiphilic lipids, It may be formulated as a solid stick or as an aerosol formulation.

The water-in-oil or oil-in-water emulsions containing the compounds of the formula (1) are preferably cosmetically compatible auxiliaries, preferably 5 to 50% oil phase, 5 to 20% emulsifier and 30% ~ 90
% Water.

The oil phase in this case comprises any oil suitable for cosmetic formulations, for example one or several hydrocarbon oils, waxes, natural oils, silicone oils, fatty acid esters or fatty alcohols. Good. Preferred mono- or polyols are ethanol, isopropanol, propylene glycol, hexylene glycol, glycerin and sorbitol.

The compounds of the present invention may be present in various cosmetic formulations. Examples of particularly suitable formulations are: skin care products, for example skin cleansing and cleansing products in the form of soap bars or liquid soaps, detergents or cleaning pastes; bath products, for example liquids ( Bubble baths, milk, shower products) or solid bath products such as bath pearls and bath salts; Skin care products, such as skin emulsions, multi-use emulsions or skin oils; Care products, such as day makeup or facial cream in the form of powder cream, white powder (loose and compressed), rouge or cream makeup, eye care products such as eye shadow products, mascara, eyeliner, eye cream or Eye fix cream; lip care products such as lipstick,
Lip gloss, lip liner; nail care products such as nail polish, nail polish remover, nail hardener or cuticle remover; feminine hygiene products, such as feminine hygiene cleaning lotions or sprays; foot care products, eg Foot bath, foot powder, foot cream or foot balms, special deodorants and antiperspirants or products for scraping skin thickening; sun milk, lotions, creams, oils, sunscreen or tropical (
sunscreens, pre-sun products or post-sun products, such as tropicals); tanning products, for example self-tanning creams; depigmenting products, for example skin bleaching or lightening products; An insect repellent, such as an insect oil, lotion, spray or stick; a deodorant, such as a deodorant spray, a non-aerosol spray, a deodorant gel, stick, or a roller; an antiperspirant, such as an antiperspirant stick. Products for cleansing and treating dirty skin, such as synthetic detergents (solid or liquid), products for peeling or scraping, or peeling masks; chemical hair removal products, for example hair removal powder, liquid hair removal Products, creamy or pasty hair removal products, hair removal gels or aerosol foams; Shaving products, such as shaving soaps, foaming shaving creams, non-foaming shaving creams, shaving foams and gels, pre-shaving products for dry shaving, post-shaving or after-shave lotions; Incense, such as perfume (Eau de Cologne), eau de toilette (Ea
u de Toilette), Eau de Parfum, Parfum de Toilette (
Parfum de Toilette, perfume), balm or fragrance cream; products for oral and dental hygiene and dentures, such as toothpaste, toothpaste gel, toothpaste, mouthwash concentrate, anti-plaque mouthwash, denture cleaning products Cosmetic formulations for hair treatments, such as hair cleansers in the form of shampoos, hair conditioners, hair care products, such as pretreatment products, hair tonics, hair styling creams and gels, pomades, hair rinse,
Deep conditioning treatment, intensive hair care treatment,
Products for hair setting, for example, permanent waver (hot wave, mild wave, cold wave), products for straightening hair, liquid hair fixatives, hair foam, hair spray, bleaching agents, for example hydrogen peroxide Solutions, bleaching shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, temporary, semi-temporary or durable hair dyes, products containing autoxidative dyes, or natural hair dyes such as henna or chamomile.

The composition of the antimicrobial soap is, for example, as follows: 0.01 to 5% by weight of the compound of formula (1), 0.3 to 1% by weight of titanium dioxide, 1 to 10% by weight Stearic acid, up to 100% soap base such as tallow fatty acid and coco fatty acid or the sodium salt of glycerin.

The composition of the shampoo is, for example, as follows: 0.01-5% by weight of the compound of formula (1), 12.0% by weight of sodium laureth-2-sulfate, 4.0% by weight Cocoamidopropyl betaine, 3.0% by weight NaCl, and up to 100% water.

The composition of the deodorant is, for example, as follows: 0.01-5% by weight of the compound of formula (1), 60% by weight of ethanol, 0.3% by weight of perfume oil and up to 100% Water of.

Examples of O / W emulsions: (a): 0.01 to 5% by weight of a compound of formula (1), 12% by weight of glycerin stearate, 6% by weight of paraffin oil, 6% by weight of capryl / Caprine Liglyceride, 4% by weight glycerin, 0.2% by weight disodium EDTA 1.0% by weight citric acid (20%), and 65.8-70.8% by weight water.

(B): 0.01 to 5% by weight of the compound of formula (1), 3.5% by weight of PEG-30 dipolyhydroxystearate, 10.0% by weight of paraffin oil, 4% by weight Capryl / Capric Liglyceride, 4% by weight dicapryl ether, 0.2% by weight disodium EDTA 3.4% by weight glycerin, and 69.9-74.9% by weight water.

In another aspect, the present invention relates to an oral composition comprising 0.01 to 15% by weight, based on the total weight of the composition, of a compound of formula (1), and also an orally compatible adjuvant. About.

Examples of oral compositions: 10% by weight sorbitol, 10% by weight glycerin, 15% by weight ethanol, 15% by weight propylene glycol, 0.5% by weight sodium lauryl sulfate, 0.25% by weight Of sodium methylcocoyl taurat
e), 0.25% by weight of a polyoxypropylene / polyoxyethylene block copolymer, 0.10% by weight of peppermint fragrance, 0.1-0.5% by weight of a compound of formula (1), and 48.6% by weight %Water of.

The novel oral composition may be, for example, a gel, a paste, a cream or an aqueous formulation (mouthwash).

The novel oral composition may further comprise a compound that releases fluoride ions effective for caries formation, for example, an inorganic fluoride salt such as sodium, potassium, ammonium or calcium fluoride, or Brand name Olafluor
And organic fluoride salts such as amine fluorides known under the category of Fluorine.

The compounds of the formula (1) used according to the invention are furthermore suitable for the antimicrobial treatment of textile fiber materials. These materials are, for example, undyed and dyed or printed fiber materials of silk, wool, polyamide, polyester, polypropylene or polyurethane, and preferably all types of cellulose-containing fiber materials. Such fibrous materials are, for example, natural cellulosic fibers such as cotton, linen, jute and hemp, as well as cellulose and regenerated cellulose. Particularly suitable textile fiber materials are those consisting of cotton.

The compounds of formula (1) may also be used alone or in combination with other antimicrobial substances, in shampoos, baths, hair care products, liquid and bar soaps (synthetic surfactants and saturated and / or unsaturated fatty acids). Lotions and creams, deodorants, other aqueous or alcoholic liquids, for example, skin cleansing liquids, wet cleansing tissues, cosmetic products such as oils or powders, and household products, It is also suitable for storing cleaning and cleaning formulations, for example liquid and powdered detergents or softeners.

The compounds of formula (1) used in the present invention are also suitable for antibacterial finishing of synthetic materials, for example polyethylene, polypropylene, polyurethane, polyester, polyamide, polycarbonate, latex and the like. Areas of these applications are typically flooring, plastic coatings, plastic container materials and packaging materials; kitchen and bathroom household items (eg, brushes, shower curtains; sponges, bathroom mats), latex filter materials (air and air). Water filter),
Plastic products used in the medical field, for example so-called medical devices such as bandages, syringes, catheters, gloves and mattresses.

Paper, for example, toilet paper, can also be antimicrobial surfacing with the novel compounds of formula (1).

The invention also allows nonwoven fabrics, such as diapers, sanitary napkins and pads, tissue for hygiene and domestic use, to be antimicrobial finished according to the invention.

The present hydroxyphenyl-1,3-propanedione can be used in particular for domestic and general-purpose cleaners used for cleaning and disinfecting hard surfaces.

The composition of the cleaning agent is, for example, as follows: 0.01 to 5% of the compound of formula (1), 3.0% of octyl alcohol 4EO, 1.3% of fatty alcohol C ₈ -C ₁₀ polyglucoside 3.0% isopropanol, water up to 100%.

In addition to preserving cosmetic and household products, specialty products such as paper processing solutions, printing thickeners consisting of starch or cellulose derivatives, coating systems and paints are preserved and antibacterial. It is also possible to finish.

The compounds of the formula (1) are also suitable for the antibacterial treatment of wood and for the antibacterial treatment and finishing of leather.

The present invention is described in more detail by the following non-limiting examples.

Example 1: Reaction step 1a Reaction scheme:

[0062]

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170 g of diphenyl ether was put in a container and melted at 30 to 40 ° C. with stirring. Next, 4.7 g of dipropyl sulfide and 4.8 g of aluminum chloride were added.
The chlorination was performed by introducing chlorine at 35-40 ° C. until the reaction mixture was chlorinated to the desired degree. The reaction was monitored by gas chromatography or HPLC. The reaction mixture was separated by distillation and the monochlorodiphenyl ether could be recycled. Once the chlorination has been continued to the extent of di- and trichlorine (content, 80% dichlorine and 20% trichlorine), the reaction mixture can be used directly for acylation.

Example 2: Acylation (second reaction step): Reaction scheme:

[0065]

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Aluminum chloride 2 was added to 520 g of ethylene chloride at 20 to 25 ° C. while stirring.
90 g were added. 170 g of acetyl chloride were added dropwise at 25-40 ° C over 15-20 minutes and the mixture was stirred at 40 ° C for 10 minutes. Over a period of one hour, a solution of 239 g of 4,4'-dichlorodiphenyl ether in 400 g of ethylene chloride was added dropwise to the mixture. The reaction mixture was kept at 40 ° C. (± 2 ° C.) for 4 hours and then added to a mixture of 2500 ml of ice water and 350 ml of 34% HCl (required thorough stirring). The phases were separated at 15-20 ° C. Ethylene chloride was removed from the organic phase by distillation.

The residue consisting of the crude acyl derivative (= 300 g) was washed with isopropyl alcohol 100
It was dissolved in 0 g at 70 ° C. and purified by filtration using a small amount of activated carbon. With stirring, 350 ml of water were added at 60 ° C. The solution was cooled slowly and crystallization started at 45 ° C. due to the addition of seed crystals. The solution was stirred for 15 hours and the crystals were collected at 25 ° C. by filtration and washed with a mixture consisting of 210 g of isopropyl alcohol and 70 ml of water. Drying under vacuum at 50 ° C. gives a formula with a melting point of 65-66 ° C. (
192.5 g of a light beige crystalline product of 101c) were obtained.

Example 3: Bayer-Villiger oxidation reaction scheme:

[0069]

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130 g of acetic acid (100%) is placed in a container and, while cooling, concentrated H ₂ SO ₄ 31
g at 15-20 ° C. At this temperature, 30 g of hydrogen peroxide (50%) was added to the mixture over 30 minutes. This reaction solution was added to 180 g of acetic acid (100%) and 87 g of concentrated H ₂ SO ₄ at 20 to 25 ° C. to obtain the acetyl compound 70 of the formula (101c).
g was dissolved and added dropwise over 1 hour to the prepared solution. This mixture is
By stirring at 0 to 25 ° C for 3 hours and slowly heating to 45 ° C, the formula (1)
The phenol ester of the compound of 01d) was completely hydrolyzed. This temperature was maintained for 2 hours and then the reaction mixture was added to a mixture consisting of 130 g of water and 360 g of toluene, bringing the final temperature to 25-30 ° C. The phases were separated, the organic phase was washed with water until neutral and the toluene was removed by distillation. The remaining residue weighed 143 g and consisted of the crude product of formula (101). Recrystallization from petroleum ether 80/110 gave the pure product in the form of colorless crystals with a melting point of 74-75 ° C.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A61K 7/40 A61K 7/40 4L033 7/50 7/50 4L055 C07C 43/295 C07C 43/295 A C11D 3 / 48 C11D 3/48 D06M 13/165 D06M 13/165 D21H 17/11 D21H 17/11 21/36 21/36 // C07B 61/00 300 C07B 61/00 300 (81) Designated countries EP (AT, BE , CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA , GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, TZ, UG, ZW ), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN , CR, CU, CZ, DE, DK, DM, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI , SK, SL, TJ, TM, TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Reiner, Dieter Deutsche D-79400 Inventor Zink, Rudolf Zeher-41 Switzerland 06 Telville Nerkenstrasse 19 F-term (reference) 4C083 AC022 AC102 AC122 AC132 AC171 AC302 AC422 AC522 AC782 AC792 AD052 CC23 CC24 CC25 CC33 CC38 CC41 DD22 DD27 DD31 DD33 DD41 4H003 AC05 AC08 DA01 DA02 DA05 EB06 ED02 ED28 FA34 A42AC12 AB AC43 AC44 AC48 BA05 BA09 BA30 BA32 BA36 BA37 BA52 BB12 BC10 BC19 BC31 BD70 BE03 BE32 BE53 GP06 GP12 GP22 4H011 AA02 BA01 BB03 BC03 BC06 BC19 DA10 DC05 DD07 DH15 DH16 4H039 CA61 CD10 CD20 4L033 AA02 AB08 FA30 GA27 GA29

Claims (20)

[Claims] 1. A method for producing a 4,4'-dihalogen-o-hydroxydiphenyl compound, comprising the following reaction scheme: Wherein R is unsubstituted or substituted by 1-3 halogen atoms or hydroxy, C ₁ -C ₈ alkyl; unsubstituted C ₆ -C ₁₂ aryl;
By 3 to 3 halogen atoms, C ₁ -C ₅ alkyl or C ₁ -C ₈ alkoxy, or C ₆ -C ₁₂ aryl substituted by a combination thereof; and Hal is a halogen atom) Halogenating the diphenyl compound (step 1a) or reacting p-halophenol with p-dihalobenzene in the presence of copper and / or copper salt (step 1b), and subjecting the dihalogen compound to a Friedel-Crafts reaction A method comprising acylating (second step), oxidizing the acyl compound (third step), and subsequent hydrolysis (fourth step). 2. The method according to claim 1, wherein R is C ₁ -C ₄ alkyl. 3. The method of claim 2, wherein R is methyl. 4. The method according to claim 1, wherein the halogen is chloro. 5. The method according to claim 4, wherein the chlorination (step 1a) is performed using elemental chlorine. 6. The process according to claim 5, wherein the chlorination is carried out in the presence of a mixture consisting of propyl sulfide and an equimolar amount of aluminum chloride. 7. The copper catalyst used in the reaction step 1b is copper (II) oxide, copper (I) oxide, copper carbonate, basic copper carbonate, copper (I) chloride, copper (II) chloride, bromide. Copper (I),
The method according to any one of claims 1 to 6, wherein the method is copper (II) bromide or copper sulfate. 8. The process according to claim 1, wherein the acylation reaction (second step) is carried out in the presence of acetyl chloride and aluminum chloride, which are used in equimolar amounts.
The method described in the section. 9. The method according to claim 8, wherein the acylation reaction is performed in the presence of a halogenated solvent. 10. The process according to claim 1, wherein the halogenation (first step) and the acylation (second step) are performed as a one-pot reaction. 11. The method according to claim 1, comprising performing the oxidation (third step) using a mixture of concentrated sulfuric acid, acetic anhydride and hydrogen peroxide as a solvent.
The method described in the section. 12. The reaction time of the oxidation is from 1 to about 24 hours, the oxidation comprising:
The method according to claim 11, which is performed at room temperature. 13. Use of a compound produced by the method according to any one of claims 1 to 12 for protecting organic materials and organic matter from attack by microorganisms. 14. Use of a compound of formula (1) for antibacterial treatment of skin, mucous membranes and hair. 15. Use of a compound of formula (1) for the antimicrobial treatment of textile fiber materials. 16. Use of a compound of formula (1) in cleaning and cleaning formulations. 17. Use of a compound of formula (1) for the antimicrobial finishing of plastics materials, paper, nonwovens, wood or leather. 18. Use of a compound of formula (1) for preserving a cosmetic product. 19. A compound of the formula (1) of 0.01 to 15% by weight, based on the total weight of the composition.
A) body care product comprising a compound of formula (I)) and cosmetically compatible auxiliaries. 20. 0.01 to 15% by weight of the formula (1) based on the total weight of the composition.
An oral composition comprising a compound of formula (I) and orally compatible auxiliaries.