US3442898A - Hydroxyaryl-pyrimidines,process for their preparation and their use - Google Patents

Hydroxyaryl-pyrimidines,process for their preparation and their use Download PDF

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US3442898A
US3442898A US364818A US3442898DA US3442898A US 3442898 A US3442898 A US 3442898A US 364818 A US364818 A US 364818A US 3442898D A US3442898D A US 3442898DA US 3442898 A US3442898 A US 3442898A
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benzene
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Christian Luethi
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BASF Schweiz AG
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Ciba AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/30—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/34—One oxygen atom
    • C07D239/36—One oxygen atom as doubly bound oxygen atom or as unsubstituted hydroxy radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3462—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C08K5/47—Thiazoles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/30—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing heterocyclic ring with at least one nitrogen atom as ring member
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B5/00—Preserving by using additives, e.g. anti-oxidants
    • C11B5/0042—Preserving by using additives, e.g. anti-oxidants containing nitrogen
    • C11B5/0064—Heterocyclic compounds containing nitrogen in the ring
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds

Definitions

  • the compounds of this invention are especially useful as stabilizers for organic materials, and particularly for the protection of the organic materials from the eifects of ultraviolet radiation.
  • the present invention provides new, valuable, hydroxyaryl-pyrimidines which, like for instance the compound of the formula in which A, A and A" are identical or different and each represents a benzene or naphthalene radical which is linked directly through a cyclic carbon atom to the pyrimidine ring and which contains a hydroxyl group in vicinal position to the bond to the pyrimidine ring;
  • R, R and R" and R' are identical or diiferent and each represents a hydrogen or halogen atom, an alkyl group or a benzene or naphthalene radical bound directly through a cyclic carbon atom to the pyrimidine ring;
  • a 1, 2 or 3
  • b, c, d, e and f 0, 1 or 2, the sum (a+b +c+d+e+f) being 3.
  • the compounds of the general Formula 2 include, for example, those which correspond to the formula Q r am in which W, W, W and W are identical or different and each represents a hydrogen atom or a halogen atom, especially chlorine, or an alkyl group, for example methyl, octyl or stearyl, or a benzene radical of the formula U0 where U to U are identical or different and each represents a hydrogen atom, a halogen atom for example chlorine, a possibly etherified hydroxyl group, for example an alkoxy group such as --OCH OC(CH 01' a hydroxyalkoxy group such as O-CH CH -OH,
  • Particularly valuable compounds of the general Formula 2 are those which correspond to the formula in which T represents :a hydrogen or chlorine atom, an alkyl group with, for example, 1 to 4 carbon atoms or a phenyl group, and V represents a hydrogen or chlorine atom, an alkyl group which preferably contains 1 to 4 carbon atoms, a phenyl group or a benzene radical of the formula Qr-O in which U represents an alkyl group which is advantageously of low molecular weight and contains no more than 4 carbon atoms, or a group of the formula 7 of the formulae in which T and V, are identical or different and each represents a hydrogen or chlorine atom, a lower alkyl group with at most 4 carbon atoms, especially a methyl group, or a phenyl group; Q represents a hydrogen atom, an alkyl group with up to 18 carbon atoms, a lower alkenyl or hydroxyalkyl group with up to 4 carbon atoms, a carbalkoxyalkyl
  • the new hydroxyaryl-pyrimidines of the above Formula 2 are obtained by known methods, for example by reacting in an anhydrous medium in the presence of a Friedel- Crafts catalyst, especially aluminum chloride, and in an inert organic solvent, halogenopyrimidines of the formula where R, R, R" and R' are identical or difi'erent and each represents a hydrogen or halogen atom, an alkyl group or a benzene or naphthalene radical bound directly through a cyclic carbon atom to the pyrimidine ring; a:l, 2 or 3; and d, e and 1 each is 0, 1 or 2, the sum (a+d+e+f) being 3, and compounds of the benzene or naphthalene series containing :a possibly etherified hydroxyl group in vicinal position to the resulting bond to the pyrimidine ring, and if desired further compounds of the benzene or naphthalene series in such a manner
  • the starting materials used in the above-described processes for the reaction with the halogenopyrimidines are compounds of the benzene series that contain in vicinal position to the resulting bond to the pyrimidine ring an etherified hydroxyl group, especially a lower alkoxy group such as methoxy, this etherified hydroxyl group in ortho-position to the resulting bond to the pyrimidine ring is split, especially when the reaction is performed at an elevated temperature, so that also from these starting materials the hydroxyarylpyrimidines of the Formula 2 are obtained.
  • Arylpyrimidines of the Formula 2 containing hydroxybenzene radicals containing in ortho-position to the bond to the triazine ring a hydroxyl group and in addition an etherified hydroxyl group are also obtained when in arylpyrimidines with hydroxybenzene radicals containing in ortho-position to the bond to the triazine ring a hydroxyl group and are substituted by a further hydroxyl group subsequent etherification is performed by a known method, for example with an alkylhalide such as propyl-, isopropylor n-octyl-bromides, with dialkylsulfates such as diethylsulfate, with phenylalkylhalides such as benzylchloride, with alkenylhalides such as allylbromide or with ethylene chlorohydrin, glycerol-a-chlorohydrin or epichlo- .rohydrin (1 -chloro 2,3-epoxy
  • the new hydroxyaryl-pyrimidines of the above composition are suitable for use as stabilizers for a wide va riety of organic materials, more especially as agents affording protection from ultraviolet radiation.
  • the present invention further includes a method of protecting organic materials from the harmful effects of heat, air and especially ultraviolet radiation, with the use of a new hydroxyaryl-pyrimidine of the Formula 2.
  • the stabilizer especially the light filter, is incorporated with a substrate to protect it from attack by ultraviolet rays, so as to prevent a change in one or more physical properties, for example discoloration, impairment of the tear strength, embrittlement or the like and/ or chemical reactions triggered off by ultraviolet rays, for example oxidation.
  • the incorporation may take place before or during the manufacture of the substrate or subsequently by a suitable operation, for example by a fixing operation similar to a dyeing process.
  • the light filter is incorporated with a substrate in order to protect one or more other substances contained in the substrate, for example dyestuffs, assistants or the like.
  • the protection of the substrate described under (A) above may be achieved at the same time.
  • the light filter is incorporated with a filter layer for the purpose of protecting a substrate placed directly underneath or at some distance from it (for example in a shop window) from the attack by ultraviolet rays.
  • the filter layer may be solid (a film, foil or dressing) or semi-solid (a cream, oil or wax).
  • the process for protecting organic materials from the harmful effects of heat, air and especially ultraviolet rays consists in incorporating a new hydroxyaryl-pyrimidine of the Formula 2 with, or fixing it on, the organic material to the protected itself or a substrate containing the said material or a filter layer placed on top of the material to be protected.
  • Textile materials quite generally, which may be in any desired form eg in the form of fibers, filaments, yarns, woven or knitted fabrics or as felt, and all articles manufactured therefrom; such textile materials may consist of natural materials of animal origin, such as wool or silk, or of vegetable origin such as cellulose materials from cotton, hemp, flax, linen, jute and ramie; also of semi-synthetic materials such as regenerated cellulose, for example rayon, viseoses including spun rayon, or synthetic materials available by polymerization or copolymerization, for example polyacrylonitrile, polyvinyl choride or polyolefines such as polyethylene and polypropylene, or those which are accessible by polycondensation, such as polyesters and above all polyamides.
  • animal origin such as wool or silk
  • vegetable origin such as cellulose materials from cotton, hemp, flax, linen, jute and ramie
  • semi-synthetic materials such as regenerated cellulose, for example rayon, viseoses including spun rayon
  • the protective agent already with a spinning mass, for example is viscose spinning rnass, acetylcellulose spinning mass (including cellulose triacetate) and to add it to masses destined for the manufacture of fully synthetic fibers, such as polyamide melts or polyamide melts or polyacrylonitrile spinning masses, before, during or after the poly-condensation or polymerization respectively.
  • a spinning mass for example is viscose spinning rnass, acetylcellulose spinning mass (including cellulose triacetate) and to add it to masses destined for the manufacture of fully synthetic fibers, such as polyamide melts or polyamide melts or polyacrylonitrile spinning masses, before, during or after the poly-condensation or polymerization respectively.
  • fibrous materials not being textile materials they may be of animal origin such as feathers, hairs and pelts or hides and leathers made from the latter by natural or chemical tanning, as well as manufactured goods made therefrom; also materials of vegetable origin such as straw, wood, woodpulp or fibrous materials consisting of densified fibrous materials, more especially paper, cardboard or hardboard, as well as finished products made from the latter. Also paper pulps used in the manufacture of paper (for example hollander pulps).
  • Coating and dressing agents for textiles and papers for example those basedon starch or casein or on synthetic resins, for example from vinylacetate or derivatives of acrylic acid.
  • Lacquers and films of diverse composition for example those from acetylcellulose, cellulose propionate, cellulose butyrate or mixed cellulose esters for example cellulose aoetate-i-butyrate and cellulose acetate-l-propionate; also nitrocellulose, vinylacetate, polyvinyl chloride, polyvinylidene chloride, copolymers of vinyl chloride and vinylidene chloride, alkyl lacquers, polyethylene, polypropylene, polyamides, polyacrylonitrile, polyesters and the like.
  • Another way of using the hydroxyaryl-pyrimidines is their incorporation with wrapping materials, more especially the known transparent foils of regenerated cellulose (viscose) or acetylcellulose. In this case it is as a rule advantageous to add the protective agent to the mass from which these foils are manufactured.
  • Natural or synthetic resins for example epoxy resins, polyester resins, vinyl resins, polystyrene resins, alkyd resins, aldehyde resins such as formaldehyde condensation products with phenol, urea or melamine, as well as emulsions of synthetic resins (for example oil-in-water or Water-in-oil emulsions).
  • synthetic resins for example oil-in-water or Water-in-oil emulsions.
  • synthetic resins reinforced with glass fibers and laminates made therefrom for example epoxy resins, polyester resins, vinyl resins, polystyrene resins, alkyd resins, aldehyde resins such as formaldehyde condensation products with phenol, urea or melamine, as well as emulsions of synthetic resins (for example oil-in-water or Water-in-oil emulsions).
  • synthetic resins reinforced with glass fibers and laminates made therefrom for example epoxy resins, polyester resins, vinyl resin
  • Hydrophobic substances containing oil, fat or wax such as candles, floor polishes, floor stains or other wood stains, furniture polishes, especially those destined for the treatment of light-colored, possibly bleached, wood surfaces.
  • Natural rubber-like materials such as rubber, balata, gutta percha or synthetic, vulcanisable materials such as polychloroprene, olefinic polysulfides, polybutadiene or copolymers of butadiene+styrene (for example Buna S) or butadiene-l-acrylonitrile (for example Buna N) which may further contain fillers, pigments, vulcanisation accelerators and the like, and in whose case the addition of the hydroxyaryl-pyrimidines aims at delaying the ageing and with it at preventing any changes in the plasticity properties and embrittlement.
  • vulcanisable materials such as polychloroprene, olefinic polysulfides, polybutadiene or copolymers of butadiene+styrene (for example Buna S) or butadiene-l-acrylonitrile (for example Buna N) which may further contain fillers, pigments, vulcanisation accelerators and the
  • Cosmetic preparations such as perfumes, dyed or undyed soaps and bath salts, skin and face creams, powders, repellants and especially sunburn oils and creams.
  • hydroxyaryl-pyrimidines are suitable as protective agents not only for undyed but also for dyed or pigmented materials; in this application the protection extends also to the dyestuffs, whereby in some cases very substantial improvements of the fastness to light are achieved. If desired, the treatment with the protective agent and the dyeing or pigmenting process may be combined.
  • the amount of the stabilizer, especially light filter, to be incorporated with the material to be treated may be varied within rather wide limits, for example from about 0.01 to 10%, preferably from 0.1 to 2%, of
  • EXAMPLE 1 22 parts of resorcinol and 11 parts of 2,4,5,6-tetrachloropyrimidine are dissolved at room temperature in 300 parts of nitrobenzene and while cooling with ice 10.5 parts of anhydrous aluminum chloride are added in portions, while preventing the temperature from rising above 20 C. The batch is stirred from 3 hours at room temperature and then further at 65 to 70 C. until the HClliberation diminishes. The dark solution is then mixed with a mixture of 400 parts of water, 100 parts of ice and 50 parts of concentrated hydrochloric acid; the precipitated solid substance and the nitrobenzene phase are decanted with water until they are approximately free from acid and together subjected to steam distillation.
  • reaction mixture is decomposed with 250 parts by volume of 2 N-hydrochloric acid, the organic phase is washed approximately acid-free by decantation, and the nitrobenzene is removed by steam distillation. After suctioning and drying, there are obtained 22 to 24 parts of the yellow crude product of the formula HO C :C-Cl
  • N C O l. 1
  • the desired product is extracted with benzene and the benzene is then distilled off.
  • the residue is recrystallized twice from aqueous alcohol with the aid of active carbon and yields the light-yellow product of the Formula 16, melting at 143 to 145 C.
  • EXAMPLE 4 16 parts of aqueous aluminum chloride are added portionwise at 0 to 5 C. while cooling with ice to a solution of 11 parts of resorcinol and 18 parts of 2,4,6-trichloropyrimidine in 250 parts of nitrobenzene. The whole is stirred for 2 hours at 0 to 5 C., then for 3 hours at 8 to 12 C. and then overnight at room temperature. The yellow-brown solution is then decomposed with 300 parts of water, parts of ice and 250 parts by volume of 2 N-hydrochloric acid, and the organic phase is washed approximately acid-free by decantation with water. The batch is steam-distilled, and the yellow precipitate is suctioned oif and dried and yields 16 parts of the crude product. From the latter the monoresorcinyl-pyrimidine of the formula TCl melting above 300 C.
  • halogenopyrimidine A and resorcinol (10 to 20% excess over the calculated amount) are suspended in the solvent B (15 to 20 times the amount referred to resorcinol) at 0 to 5 C., 1.1 mols (per mol of resorcinol) of anhyrous aluminum chloride are added, while keeping the temperature below 5 C. The batch is then stirred until a temperature of 20 to 25 C. has been reached,
  • the starting hydroxyprimidine required to make the above 2-chloro-4,6-diphenylpyrimidine is obtained by diazotizing 2-amino-4,6-diphenylpyrimidine with a concen- Final product:
  • the 2-chloro-4,G-diphenylpyrimidine used as starting material for compound 27 is manufactured in a similar manner, except that the batch is refluxed for 20 hours.
  • the ether residue is worked up by being extracted with petroleum ether.
  • the extraction residue (about EXAMPLE 6 A mixture of 10 parts of 2-chloro-4,6-dimethylpyrimidine, 13 parts of para-methylanisole and parts of dichlorobenzene is cooled to 0 to 5 C., and 16 parts of anhydrous aluminum chloride are added in portions.
  • the temperature is then raised to C. and the batch stirred at this temperature for 24 hours, poured over 500 parts of a mixture of ice and water, and the organic phase passes over; it melts at 139 to 140 C.
  • the resorcinolpyrimidine A and anhydrous potassium hydroxide are dissolved at about C. in methylcellosolve (4 to 6 times the amount referred to A).
  • the bromide B (equivalent amount referred to potassium hydroxide) is then added to the above solution and the temperature is raised every half hour by 10 C., until a distinct brightening and crystallization sets in.
  • T final the batch is stirred for another 2 to 4 hours, then cooled and the ether C so formed is suctioned 01f. It melts a few degrees below the analytically pure compound.
  • N C ⁇ (21) n-Oetyl- 80-90 (31) 8687 bromide. N-C
  • N C-Opropyl (22) n-Oetyl- -90 76 (33) 96-98 bromide. N-C
  • N C-Ooetyl 110 O-oetyl H5CC ⁇ /CH -0-octyl (24) n-Propyl- 85-90 60 NCCH (35) 1271% bromide.
  • Octyl-O -c 011 N CCH; (26) Benzyl- 80-90 85 (39) 125-127 bromide.
  • N CCH
  • EXAMPLE 9 A suspension of 31 parts of compound (28) and 11.2 parts of potassium hydroxide in 400 parts of acetone is mixed with a solution of 15 parts of potassium carbonate in 25 parts of water. At 35 to 40 C. in the course of one hour the reaction mixture is mixed dropwise with a solution of 32.3 parts of diethylsulfate in 80 parts of acetone. The suspension is stirred on for 4 hours at 35 to 40 C. and then refluxed for 2 hours. The cooled reaction mixture is poured into 2000 parts of water, adjusted with dilute hydrochloric acid to pH 5, suctioned and thoroughly rinsed with water. The dried crude product (35 parts) is then boiled with 350 parts of benzene benzene and cooled, to yield ll parts of the compound of the formula melting at 181-183 C.
  • the compound of the Formula 19 was converted in a similar manner with the aid of dimethylsulfate into the compound of the formula C I-I N O .-Calculated (percent): C, 71.98; N, 7.00. Found (percent): C, 71.66; H, 5.07; N,
  • EXAMPLE 10 17 parts of bromoacetic acid methyl ester in 100 parts of acetone are dropped at 20 C. into a suspension of 15.5 parts of the compound (28) and 14 parts of anhydrous potassium carbonate in 400 parts of acetone, and the temperature is raised and maintained for 3 days at reflux.
  • the crude product obtained by precipitation with Water is taken up in benzene and precipitated with methanol. Repetition of this operation yields the product of the formula and filtered; the filtrate is concentrated to parts and while hot mixed with 250 parts of alcohol.
  • the precipitated product (27 parts) is dissolved in a minimum of melting at 186-188 C.
  • EXAMPLE 12 Light permeability in percent Exposed for 100 hours Wavelength in my Unexposed in a fadeometer Similar results are obtained with the compound of Formulas l, 18, 19, 20, 21, 26 to 31, 37, 39, 41, 47, 48 to 51.
  • EXAMPLE 13 10,000 parts of a polyamide in chip form, prepared from caprolactam in known manner and pigmented with 0.3% of titanium dioxide, are mixed with 50 parts of the compound of the Formula 31 or 45 in a tumbler for 12 hours and then melted in an oil fired boiler at 300 to 310 C. after having displaced the atmospheric oxygen from it by means of superheated steam. After stirring for half an hour the melt is expressed with nitrogen under atmospheres (gauge) pressure through a spinneret. The filaments thus obtained are tested for their light fastness by being exposed for 120 hours to a xenone lamp. The measure of the degradation of the macromolecules under the influence of light is the relative viscosity of the polyamide fiber dissolved in concentrated sulfuric acid. This test shows that filaments not containing the compound of Formula 31 or 45 are much more strongly affected by light than filaments that contain the said compound.
  • EXAMPLE 14 A paste from 100 parts of polyvinyl chloride, 59 parts by volume of dioctylphthalate and 0.2 part of the compound of Formula 18 is rolled to and fro on a calender at 150 to 155 C. to form a foil. The resulting polyvinyl chloride foil absorbs completely in the ultraviolet region from 280 to 360 mg.
  • the compound of the Formula 18 may be replaced by the compound of the Formulas 1, 16, 20, 29, 30, 31, 35, 37, 38, 40, 43, 44 or 45.
  • EXAMPLE A mixture of 100 parts of polyethylene (Alkathene 18 WNG 14) and 0.2 part of the compound of Formula 1, 15 or 18 is rolled to and fro on a calender at to C. to form a foil which is then pressed at 130 C.
  • the polyethylene foil obtained in this manner is practically impermeable to ultraviolet light within the region from 280 to 380 mu.
  • EXAMPLE 16 A mixture of 100 parts of polypropylene and 0.2 part of the compound of the Formulas 17, 29, 30, 31, 37, 38, 43, 44 or 45 is made into a sheet on a calender at C. which sheet is then pressed at 230 to 240 C. under a maximum pressure of 40 kg. per square centimeter to form a panel 1 mm. thick.
  • the panels obtained in this manner are impermeable to ultraviolet light within the region from 280 to 370 mu.
  • EXAMPLE 17 A solution of 0.2 part of the compound of Formula 17 in 1.8 parts of monostyrene is mixed with 0.5 part of a cobalt naphthenate monostyrene solution (containing 1% of cobalt). 40 parts of an unsaturated polyester resin based on phthalic acid-l-maleic acid-l-ethyleneglycol in monostyrene are then added and the whole is stirred for 10 minutes. 1.7 parts of a catalyst solution (methylethyl ketone peroxide in dimethylphthalate) are then dropped in and the thoroughly mixed mass, which should be as free from air as possible, is cast between two panes of glass. After about 20 minutes, the 1 mm.
  • a catalyst solution methylethyl ketone peroxide in dimethylphthalate
  • polyester panel has solidified sufiiciently to enable it to be taken out of the mould. It is impermeable to ultraviolet light within the region from 280 to 380 m and shows no signs of yellowing after a 1000 hours test with a xenone lamp. When the com-pound 17 is omitted, the xenone test reveals yellowing after onyl 5 00 hours.
  • the compound 17 may be replaced by the compound of the Formula 20, 29, 30, 31, 37 or 38.
  • the compound of the formula Q being hydrogen.
  • N C ⁇ Q OH 10.
  • the compound of the formula OH CH; OH HgCOOC-CHIO OH 0 CH CH N C 40 a o CHr-COOCH:
  • Nci 0 ALEX MAZEL Primary Examiner.
  • HaC-( H:)1 0B R. V. RUSH Assistant Examiner.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
US364818A 1963-05-04 1964-05-04 Hydroxyaryl-pyrimidines,process for their preparation and their use Expired - Lifetime US3442898A (en)

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CH563263A CH448083A (de) 1963-05-04 1963-05-04 Verwendung von neuen Hydroxyaryl-pyrimidinen bei Verfahren zum Schützen von nicht-textilen organischen Materialien

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Cited By (15)

* Cited by examiner, † Cited by third party
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US4493726A (en) * 1980-12-23 1985-01-15 Ciba Geigy Corporation Phenylpyrimidines as antidotes for protecting cultivated plants against phytotoxic damage caused by herbicides
US4648896A (en) * 1982-11-15 1987-03-10 Ciba-Geigy Corporation 2-aryl-4,6-dihalopyrimidines as antidote for protecting cultivated plants from phytotoxic damage caused by herbicides
US4698091A (en) * 1982-06-08 1987-10-06 Ciba-Geigy Corporation 2-phenylpyrimidines, 2-naphthylpyrimidines and 2-heterocyclylpyrimidines as safeners for protecting cultivated plant against phytotoxic damage caused by herbicides
JPS63227879A (ja) * 1987-02-27 1988-09-22 チバーガイギ　アクチエンゲゼルシヤルト ポリエステル繊維材料染色物の光化学的安定性を向上させる方法
US4895981A (en) * 1987-02-27 1990-01-23 Ciba-Geigy Corporation Process for improving the photochemical stability of dyeings on polyester fibre materials
GB2278115A (en) * 1993-05-17 1994-11-23 Ciba Geigy Ag Coating compositions stabilized against damage by light heat and oxygen
EP0711804A2 (de) 1994-11-14 1996-05-15 Ciba-Geigy Ag Kryptolichtschutzmittel
US20030105276A1 (en) * 2001-10-12 2003-06-05 Tadros Safwat E. Multilayer, weatherable compositions and method of manufacture thereof
US20030124358A1 (en) * 2001-11-09 2003-07-03 General Electric Company Multi-layer, weatherable compositions and method of manufacture thereof
US6630527B2 (en) 2001-10-19 2003-10-07 General Electric Company UV stabilized, impact modified polyester/polycarbonate blends, articles, and methods of manufacture thereof
US6706215B1 (en) 1993-05-17 2004-03-16 Ciba Specialty Chemicals Corporation Coating compositions stabilized against damage by light, heat and oxygen
AU2002231759B2 (en) * 2001-05-25 2006-08-03 P&G Clairol, Inc. 1,3-dihydroxybenzene derivatives and colorants containing said compounds
WO2010081625A2 (en) 2009-01-19 2010-07-22 Basf Se Organic black pigments and their preparation
US9923148B2 (en) 2002-10-30 2018-03-20 Udc Ireland Limited Electroluminescent device
JP2024045108A (ja) * 2018-10-05 2024-04-02 三星ディスプレイ株式會社 表示装置及び表示装置に含まれる光吸収剤

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US3361749A (en) * 1964-12-15 1968-01-02 Haco A G Certain n-pyrimidyl anthranilic acid derivatives

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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4493726A (en) * 1980-12-23 1985-01-15 Ciba Geigy Corporation Phenylpyrimidines as antidotes for protecting cultivated plants against phytotoxic damage caused by herbicides
US4698091A (en) * 1982-06-08 1987-10-06 Ciba-Geigy Corporation 2-phenylpyrimidines, 2-naphthylpyrimidines and 2-heterocyclylpyrimidines as safeners for protecting cultivated plant against phytotoxic damage caused by herbicides
US4648896A (en) * 1982-11-15 1987-03-10 Ciba-Geigy Corporation 2-aryl-4,6-dihalopyrimidines as antidote for protecting cultivated plants from phytotoxic damage caused by herbicides
JPS63227879A (ja) * 1987-02-27 1988-09-22 チバーガイギ　アクチエンゲゼルシヤルト ポリエステル繊維材料染色物の光化学的安定性を向上させる方法
US4895981A (en) * 1987-02-27 1990-01-23 Ciba-Geigy Corporation Process for improving the photochemical stability of dyeings on polyester fibre materials
US6706215B1 (en) 1993-05-17 2004-03-16 Ciba Specialty Chemicals Corporation Coating compositions stabilized against damage by light, heat and oxygen
GB2278115A (en) * 1993-05-17 1994-11-23 Ciba Geigy Ag Coating compositions stabilized against damage by light heat and oxygen
GB2278115B (en) * 1993-05-17 1997-08-06 Ciba Geigy Ag 2-(2-Hydroxyphenyl)-1,3-pyrimidine derivatives and their use as stabilizers for coating compositions
US5753729A (en) * 1993-05-17 1998-05-19 Valet; Andreas Coating compositions stabilized against damage by light, heat, and oxygen
EP0711804A2 (de) 1994-11-14 1996-05-15 Ciba-Geigy Ag Kryptolichtschutzmittel
US5597854A (en) * 1994-11-14 1997-01-28 Ciba-Geigy Corporation Latent light stabilizers
AU2002231759B2 (en) * 2001-05-25 2006-08-03 P&G Clairol, Inc. 1,3-dihydroxybenzene derivatives and colorants containing said compounds
US20030105276A1 (en) * 2001-10-12 2003-06-05 Tadros Safwat E. Multilayer, weatherable compositions and method of manufacture thereof
US7297409B2 (en) 2001-10-12 2007-11-20 Sabic Innovative Plastics Ip Bv Multilayer, weatherable compositions and method of manufacture thereof
US6630527B2 (en) 2001-10-19 2003-10-07 General Electric Company UV stabilized, impact modified polyester/polycarbonate blends, articles, and methods of manufacture thereof
US20030124358A1 (en) * 2001-11-09 2003-07-03 General Electric Company Multi-layer, weatherable compositions and method of manufacture thereof
US7090926B2 (en) 2001-11-09 2006-08-15 General Electric Company Multi-layer, weatherable compositions and method of manufacture thereof
US9923148B2 (en) 2002-10-30 2018-03-20 Udc Ireland Limited Electroluminescent device
US11289658B2 (en) 2002-10-30 2022-03-29 Udc Ireland Limited Electroluminescent device
US11968893B2 (en) 2002-10-30 2024-04-23 Udc Ireland Limited Electroluminescent device
WO2010081625A2 (en) 2009-01-19 2010-07-22 Basf Se Organic black pigments and their preparation
JP2024045108A (ja) * 2018-10-05 2024-04-02 三星ディスプレイ株式會社 表示装置及び表示装置に含まれる光吸収剤
US12289992B2 (en) 2018-10-05 2025-04-29 Samsung Display Co., Ltd. Display apparatus and light absorber included in display apparatus

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BE647377A (de) 1964-10-30
GB1029045A (en) 1966-05-11
CH448083A (de) 1967-12-15
NL6404860A (de) 1964-11-05

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