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Publication numberUS3442898 A
Publication typeGrant
Publication dateMay 6, 1969
Filing dateMay 4, 1964
Priority dateMay 4, 1963
Publication numberUS 3442898 A, US 3442898A, US-A-3442898, US3442898 A, US3442898A
InventorsChristian Luethi
Original AssigneeCiba Ltd
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Hydroxyaryl-pyrimidines,process for their preparation and their use
US 3442898 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent US. Cl. 260-251 12 Claims ABSTRACT OF THE DISCLOSURE New hydroxyaryl-pyrirnidines are provided which may be represented by the general formula h- N( J )d l a a I (A!) O C RIII (RV)6 )c N=O 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 different 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, and b, c, d, e and each :0, 1 or 2, the sum (w-l-b+c+d+e+f) being 3.

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, and b, c, d, e and f each =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,

-O-CH CH -CH -OH or O-CH --CH0HCH OH; an alkenyloxy group such as -O--CH CH=CH or O--CH CH=CHCH a phenylalkoxy group such as benzyloxy; furthermore a 2,3-epoXy-propoxy group; a carboxyalkoxy group which may be esterified with an alkanol, such as -0-CH COOH and an alkyl or alkenyl group such as, for example, methyl, octyl, stearyl, allyl or propenyl; a sulfonic acid group or carboxyl group, or an acyl radical of a monocarboxylic acid, for example acetyl; a=1, 2 or 3, and b, c, d, e and 1 each =0, 1 or 2, the sum (a+b+c+d+e+f) being 3.

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 group with up to 6 carbon atoms or a benzyl group, and U represents a lower alkyl group with up to 4 carbon atoms.

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 that hydroxyphenyl-pyrimidines of the above formula are obtained.

As examples of halogenopyrimidines of the Formula 11 there may be mentioned:

2-chloropyrimidine, 4-chloropyrimidine, 2,4-dichloropyrimidine, 4,6-dichloropyrimidine, 2,4,6-trichloropyrimidine, 2,4,5,6-tetrachloropyrimidine, 2-chloro-4,6-methylpyrimidine, 2-phenyl-4-methyl-6-chloropyrimidine, 2-naphthyl-4,6-dichloropyrimidine, 2,4-diphenyl-6-chloropyrimidine, 2,4-dichloro-6-phenylpyrimidine, 2,4,6-trichloro-5-phenylpyrimidine, 2,4-dichloro-6-amylpyrimidine.

As examples of compounds of the benzene or naphthalene series that contain in vicinal position to the resulting bond to the pyrimidine ring a possibly etherified hydroxyl group and yield, for example, the hydroxyaryl radicals A, A and A" in the formula 2 or a hydroxybenzene radical of the formula in which U to U have the same meanings as in Formula 3, there may be mentioned the following compounds:

l,3-dihydroxy-benzene 1-hydroxy-3-methoxy-benzene 1-hydroxy-3-ethoxy-benzene 1,3-dimethoxy-benzene 1,3-diethoxy-benzene 1,3-dihydroxy-4-methyl-benzene 1,3-dimethoxy-4-methyl-benzene 1,3,5-trihydroxy-benzene 1-hydroxy-4-chlorobenzene 1-hydr0xy-3-methyl-benzene 1-hydroxy-4-methyl-benzene 1-hydr0xy-3,4-dimethyl-benzene l-hydroxy-naphthalene [a-naphthol] Z-hydroxy-naphthalene [fl-naphthol] 1,5-dihydroxynaphthalene 1,7-dihydroxynaphthalene 2-hydroxy-naphthalene-3,6-disulfonic acid 2-hydroxy-naphthalene-6,S-disulfonic acid 1-chloro-3-methoxy-benzene 1-chloro-4-methoxy-benzene 1-methyl-3-methoxy-benzene l-methy1-4-methoxy-benzene 1-n-propyl-3-methoxy-benzene 1-methoxy-4-propenyl-benzene [anethol].

When 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-epoxypropane) or with chloroacetic acid.

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.

Accordingly, 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.

Quite generally, there are three different ways of using the new products, either separately or in combinations:

(A) 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.

(B) 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.

(C) 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).

Thus, 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.

As organic materials that can be protected there may be mentioned:

(a) 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. In the case of semisynthetic materials it is of advantage to incorporate 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.

(b) Other 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).

(c) 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.

((1) 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.

(e) 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). In this case it is of advantage to add the protective agent before or during the polymerization or polycondensation respectively. Furthermore, there may be mentioned synthetic resins reinforced with glass fibers and laminates made therefrom.

(f) 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.

(g) 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.

(h) Cosmetic preparations such as perfumes, dyed or undyed soaps and bath salts, skin and face creams, powders, repellants and especially sunburn oils and creams.

It goes without saying that the 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.

Depending on the kind of material to be treated, demands made on the efiiciency and durability and other requirements, 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

the weight of the material which is to be directly protected from the harmful effects of heat, air and especially ultraviolet rays.

Unless otherwise indicated, parts and percentages in the following examples are by weight. The melting points are not corrected.

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. The precipitated product of the formula HOO -01 EXAMPLE 2 16 parts of anhydrous aluminum chloride are added in portions at 3 to 5 C. to a solution of 21.8 parts of 2,4,5, 6 tetrachloropyrimidine in 100 parts of nitrobenzene, whereupon in the course of 60 minutes at 0 to 5 C. a solution of 11 parts of resorcinol in 150 parts of nitrobenzene is dropped in. The whole is stirred for 2 hours at 0 to 5 C. then for 3 hours at 8 to 12 C. and finally overnight at room temperature. The 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.

C H O N Cl .Calculated (percent): C, 41.20; H, 1.85; N, 9.40; Cl, 36.5. Found (percent): C, 40.93; H, 1.73; N, 9.60; CI, 36.3.

EXAMPLE 3 While cooling a solution of parts of resorcinol and 11 parts of 2,4,6-trichloropyrimidine in 400 parts of nitrobenzene with ice, 14 parts of anhydrous aluminum chloride are added portionwise at a rate such that the temperature always remains below 20 C. The temperature is then raised to to C. and stirring is continued until the evolution of HCl has noticeably slowed down. The dark solution is then mixed with a mixture of 600 parts of water, 150 parts of ice and 60 parts of concentrated hydrochloric acid, and the organic phase is washed approximately acid-free by decantation with water. The nitrobenzene and excess resorcinol are removed by steam distillation and the yellow product of the Formula 1 is suctioned off and dried.

To free the crude product (22.5 parts) from incompletely substituted matter it is extracted with 200 parts of hot ethyl acetate and the residue is twice recrystallized from aqueous dimethylformamide; it melts above 300 C.

C H O N .Calculated (percent): N, 6.93; Cl, 0.0. Found (percent): N, 7.10; Cl, 0.3.

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.

C H O N Cl.Calculated (percent): C, 58.11; H, 3.35; N, 8.47; Cl, 10.72. Found (percent): C, 58.00; H, 3.12; N, 8.27; Cl, 10.65.

EXAMPLE 5 The compounds shown in the following table were manufactured as follows:

The 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,

stirred on at this temperature for 2 to 4 hours and then gradually heated until a strong evolution of hydrogen chloride sets in, and finally stirred until this evolution ceases (8 to 30 hours). The batch is allowed to cool, poured over a mixture of ice and water, the organic phase is washed with water until a weakly acid reaction is reached, and the solvent is then driven off by steam distillation. The residue consists of a crude product which in most cases melts only a few degrees below the analytically pure product.

consists of starting material which can be used again. When the petroleum ether extract is concentrated, 2- chloro-4, 6-diphenylpyrimidine crystallizes out in a yield of 35%; it melts at 115 to 116 C.

C H N Cl.--Calculated (percent): C, 72.05; H, 4.16; N, 10.50; Cl, 13.29. Found (percent): C, 72.36; H, 4.20; N. 10.45; Cl, 13.32.

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:

NO- X2 Yield X1-C CH Initial halogeno- Solvent Reaction in Recrystalllzed N" of M.P., pyrimidine (A) (B) temp., 0. percent from N=CX; ether C.

2,4-dichloro- N itro- 65-70 77 Aqueous HO (19) 315-317 pyrimidine. benzene. alcohol.

X1, X1: "OH; R3=H 2-ch10ro-4,6-di- Chloro- 65-70 83 do H0 (20) 163-164 methylprimibenzene. l dine.

X =0H; X2, xl=cna 2,4-diehloro-6- Tetra- 80 87 Aqueous di- H0 (21) 342-343 phenylpyrimichloromethyllormdine. ethane. amide.

X1, X2= OH; X3=

2,4-diphenyl-6- Chloro- 85 98 do OH (22) 245 chloropyrimidine. benzene.

x1, Xl=-; X3= OH 2-methyl-4,G-di- Tetra- 80-90 70 ..-..do H0 (23) 320-326 chloropyrimidine. chloroethane.

X1=CII3 X2, X3: -OH

2-phenyl-4-rnethyl- Chloro- 85-90 83 Aqueous H0 (24) 189-191 ti-ehloropyrimibenzene. alcohol. I dine.

i=- 2=C t; s=

2-methy1-4-phenyl- Nitro- 05-70 95 .....do H0 (25) 181-183 G-chloro-pyrirnibenzene. dine.

X|=-CH3; X3: ;X3= --OH 2-chloro-4-methyl- .....do 65-70 92 do H0 (26) 102-103 fi-phenyl-pyrimidine.

X1: OH; Xz=--CH X3= 2-chloro-4,6-dido 65-70 abt. 50 do H0 27 227 229 phenylpyrimidine.

X1: OH; X7, X3=

2,4-dichloro-6- .do.. 68 Dioxane H0 (28) 329-330 methylpyrimiwater dine.

X1, Xg= 0H; X3=-CH3 The Z-methyl 4 phenyl--chloropyrimidine (initial chloropyrimidine used for preparing compound 25) can be manufactured thus:

A mixture of 21.2 parts of 2-methyl-4-phenyl-6-hydroxypyrimidine, 200 parts of phosphorus oxychloride and 15 parts of dimethylaniline is refluxed for 2 hours; the excess of phosphorus oxychloride is then distilled 01f under reduced pressure and the residue poured over ice. The mixture is extracted with ether and the dried ether phase evaporated to dryness. 2-methyl-4-phenyl-6-chloropyrimidine is expelled (in a yield of 86%) by steam distillation and melts at 57 to 58 C.

.C HgN Cl.Ca1culated (percent): N, 13.69; C1, 17.32. Found (percent): N, 13.36; C1, 1693.

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.

C H ON .Calculated (percent): C, 72.87; H, 6.59; N, 13.08. Found (percent): C, 72.96; H, 6.56; N, 13.05.

1 2 EXAMPLE 7 The following compounds listed in the following table are prepared thus:

The resorcinolpyrimidine A and anhydrous potassium hydroxide (theoretical amount needed to convert for every resorcinyl residue one hydroxyl group into potassium phenolate) 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. At this temperature (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. For analysis these products were recrystallized from benzene+alcohoL Resorein- T Yield ylpyrimi- Organ. final, in N of M.P., dine (A) bromide (B) 0. percent Ether (C) ether C.

(19) n-Propyl- 80-90 75 N--CH (29) 155-160 bromide.

Propyl-O- C\ /CH N=C -Op 0p H4. Q

(20) .do 80-90 87 /CH: (30) 123-124 Propyl-OC\ /CH g) N=C\ (21) n-Oetyl- 80-90 (31) 8687 bromide. N-C

Octyl-OC\ /CH N=C-Ooetyl HO (22) 11-Propyl- 7U 45 (32) 156-157 bromide. NC

N=C-Opropyl (22) n-Oetyl- -90 76 (33) 96-98 bromide. N-C

s N=C-Ooetyl 110 O-oetyl H5CC\ /CH -0-octyl (24) n-Propyl- 85-90 60 NCCH (35) 1271% bromide.

Resorcin- T Yield ylpyrimi- Organ. final, in N of M.P., dine (A) bromide (B) 0. percent Ether (C) ether C 25 n-Octyl- 85-90 83 (36) 103-104 bromide.

aCC CH (26) n-Propyl- 85-90 ebt. (37) 126-127 bromide.

HO Propyl-O- --C )CH N=C-CH;

(26) 11-Octyl- 85-90 (38) 77-78 bromide:

Octyl-O -c 011 N=CCH; (26) Benzyl- 80-90 85 (39) 125-127 bromide.

N=CCH;

(28). n-Butyl- 85-90 72 H0 (40 129.130

bromide: /N-C:OH: Butyl-O C CH (28) Allyl- -65 CH; (41) 148-149 bromide. HO H,C=CHCH10 -o CH -o-cm-cn=cm (28) n-Octadeeyl- 90-95 98 CH; (42) 110.412

bromide. HO Octadeeyl0 -o CH O-octadeeyl H EXAMPLE 8 C H N O M.P. 9910l C.Calculated (per- By using in Example 7 a double to triple excess over 60 cent)! Found (D 0 the calculated amount of the bromide (B) and of potassium hydroxide, and the corresponding bromides are used, the following tri-ethers of compound (21) are ob- C, 77.92; H, 9.10; N, 3.95. Found (percent): C, 77.82; H, 9.09; N, 4.00.

melting at 88 to 89 C.

C H N O .Calculated (percent): C, 77.92; H, 9.10; N, 3.95%. Found (percent): C, 77.99; H, 9.21; N, 3.96.

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.

C H N O .Calculated (percent): C, 68.83; H, 6.05; N, 7.65. Found (percent): C, 68.66; H, 6. 07; N, 7.65.

When the mother liquor is chromatographed on alumina (activity I), the benzene fraction yields the compound of the formula melting at 159-161 C. (10 parts).

C H N O .Calculated (percent): C, 70.0; H, 6.6; N, 7.1. Found (percent): C, 70.0; H, 6.6; N, 7.3.

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.

C H N O .--Calculated (percent): C, 60.79; H, 4.88;

5 N, 6.17. Found (percent): C, 60.60; H, 5.00; N, 6.30.

1 7 EXAMPLE 11 A mixture of 8.1 parts of ethylene chlorohydrin and 20 parts of methylcellosolve is added dropwise at 85 to 90 C. within one hour to a solution of 15.5 parts of the compound (28) and 5.6 parts of potassium hydroxide in 40 parts of methylcellosolve and the whole is stirred for 6 hours at 90 C. After cooling, the precipitated product of the formula is suctioned off, washed with methanol, then with 0.1 N-hydrochloric acid and finally with water and dried (10.5 parts). After three recrystallizations from aqueous dimethylformamide the product melts at 250 to 255 C. C H N O .-Calculated (percent): C, 63.40; H, 5.30; N, 7.10. Found (percent): C, 63.40; H, 5.50; N, 7.10.

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. 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.

What is claimed is:

1. A hydroxyphenyl-pyrimidine of the formula wherein T is a member selected from the group consisting of hydrogen, chlorine, lower alkyl and phenyl, V is a member selected from the group consisting of hydrogen, chlorine, lower alkyl, phenyl and the radical of the formula U is a member selected from the group consisting of lower alkyl and the radical of the formula and Q, Q, and Q each is a member selected from the group consisting of hydrogen, alkyl, lower alkenyl, hydroxy(lower)alkyl, carb(lower) alkoxy(lower)alkyl and 20 pheuy1(10wer)a1kyl, at least one of the two symbols Q and 8. The compound of the formula Q being hydrogen.

2. The compound of the formula.

H N-(J 5 OH HOG-.. CH

\ Q-om-o c\ N=C 01 l Ha The compound of the formula 9. The compound of the formula OH; OH

N=C\ Q OH 10. The compound of the formula HO OH CH: CH N 1 4. The compound of the formula Q 0H 0H Nzc N(. 2 Hw-CHT-QHT-OQQ \CH OCHrCHzOH H: 11. The compound of the formula 5. The compound of the formula OH CH; OH HgCOOC-CHIO OH 0 CH CH N=C 40 a o CHr-COOCH:

6. The compound of the formula 12. The compound of the formula 0 CH3 I l,\ I Hc=0-c 011 0 11 OH /N 0\ N:()\ l HOQC/ \CH N=O O C3115 hav' am ltin t of 159-161 C. 7. The compound of the formula mg e g pom References Cited UNITED STATES PATENTS 3,361,749 1/1968 Matter et a1. 260256.4 0H

Nci 0 ALEX MAZEL, Primary Examiner. HaC-( H:)1 0B R. V. RUSH, Assistant Examiner.

US. 01. X.R. 252-3 00, 40s

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3361749 *Dec 13, 1965Jan 2, 1968Haco A GCertain n-pyrimidyl anthranilic acid derivatives
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4493726 *Apr 20, 1983Jan 15, 1985Ciba Geigy CorporationPhenylpyrimidines as antidotes for protecting cultivated plants against phytotoxic damage caused by herbicides
US4648896 *Nov 7, 1983Mar 10, 1987Ciba-Geigy Corporation2-aryl-4,6-dihalopyrimidines as antidote for protecting cultivated plants from phytotoxic damage caused by herbicides
US4698091 *Jul 3, 1985Oct 6, 1987Ciba-Geigy Corporation2-phenylpyrimidines, 2-naphthylpyrimidines and 2-heterocyclylpyrimidines as safeners for protecting cultivated plant against phytotoxic damage caused by herbicides
US4895981 *Mar 24, 1989Jan 23, 1990Ciba-Geigy CorporationProcess for improving the photochemical stability of dyeings on polyester fibre materials
US5597854 *Nov 9, 1995Jan 28, 1997Ciba-Geigy CorporationLatent light stabilizers
US5753729 *Jun 7, 1996May 19, 1998Valet; AndreasCoating compositions stabilized against damage by light, heat, and oxygen
US6630527Oct 19, 2001Oct 7, 2003General Electric CompanyUV stabilized, impact modified polyester/polycarbonate blends, articles, and methods of manufacture thereof
US6706215Jun 23, 1997Mar 16, 2004Ciba Specialty Chemicals CorporationCoating compositions stabilized against damage by light, heat and oxygen
US7090926Oct 2, 2002Aug 15, 2006General Electric CompanyMulti-layer, weatherable compositions and method of manufacture thereof
US7297409Oct 12, 2001Nov 20, 2007Sabic Innovative Plastics Ip BvMultilayer, weatherable compositions and method of manufacture thereof
US20030105276 *Oct 12, 2001Jun 5, 2003Tadros Safwat E.Multilayer, weatherable compositions and method of manufacture thereof
US20030124358 *Oct 2, 2002Jul 3, 2003General Electric CompanyMulti-layer, weatherable compositions and method of manufacture thereof
EP0711804A2Nov 6, 1995May 15, 1996Ciba-Geigy AgLatent light stabilizers
WO2010081625A2Dec 28, 2009Jul 22, 2010Basf SeOrganic black pigments and their preparation
Classifications
U.S. Classification544/334, 252/403, 544/335, 252/589
International ClassificationC07D239/26, D06M13/35, C07D239/30, C08K5/3462, C09K15/30, C08L21/00, C08K5/47, C08L77/00, C11B5/00, C07D239/36
Cooperative ClassificationC07D239/36, C09K15/30, D06M13/35, C08L21/00, C07D239/26, C11B5/0064, C08K5/47, C07D239/30, C08K5/3462
European ClassificationC08L21/00, C09K15/30, D06M13/35, C08K5/3462, C11B5/00H6, C08K5/47, C07D239/36, C07D239/26, C07D239/30