US3178421A - Novel bis-aryloxazolyl ethylene optical brightening derivatives - Google Patents

Novel bis-aryloxazolyl ethylene optical brightening derivatives Download PDF

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Publication number
US3178421A
US3178421A US78825A US7882560A US3178421A US 3178421 A US3178421 A US 3178421A US 78825 A US78825 A US 78825A US 7882560 A US7882560 A US 7882560A US 3178421 A US3178421 A US 3178421A
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Prior art keywords
grams
ethylene
aryloxazolyl
brightening
onium
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US78825A
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English (en)
Inventor
Konishi Kenzo
Wakae Masao
Goi Mitsuhiro
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GOVERNOR OF OSAKA PREFECTURE
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GOVERNOR OF OSAKA PREFECTURE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/62—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems having two or more ring systems containing condensed 1,3-oxazole rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups

Definitions

  • the present invention pertains to a process for the optical brightening of textile materials. More particularly, this invention relates to a series of water-soluble onium compounds which can be profitably employed in the form of aqueous solution'for the optical brightening of textile materials, such'as synthetic fibers made from polyacrylonitrile or its copolymers, polyamide, polypropylene, polyethylene or polyvinyl-acetal; artificial fibers made from viscose rayon or cellulose acetate; and natural fibers like cotton.
  • the brightening agents of'this invention comprise ,5- bis [methylene aryloxazol-yl (2)] ethylene w,w'- onium halides andtheir zinc chloride double salts, having the structural formula wherein A and A represent respectively a benzene nucleus or a naphthalene nucleus; R and R stand for respectively a hydrogen atom, a methyl group or an ethyl group; B is an onium salt-forming compound residue, and X a halogen atom.
  • the brightening agents of this invention are all watersoluble. Materials to be brightened are accordingly simply dipped in an aqueous solution of pH 2 to at a temperature ranging from room temperature to 130 C. at the highest. The material is then rinsed and dried as usual in the art.
  • the pH value and the temperature of the aqueous solution being employed are accommodated according to the property of the material being brightened.
  • Synthetic fibers made from polyacrylonitrile or its copolymers, for instance, are profitably treated in an aqueous solution of pH 2 to 7.
  • an aqueous solution of pH 6 to 8 is employed with advantage.
  • the temperature employed in this invention ranges from the room temperature to 130 C. at the highest, as stated before.
  • a pressure vessel is also employed at a temperature over 100 C.
  • the commercial temperature is confined to the range of 70 to 110 C., both because the lower temperatures prolong the dipping process and because some of the materials to be brightened cannot endure the higher temperatures. Materials soaked with the brightening solution can be steamed in a closed vessel.
  • the brightening agents of this invention can be dissolved in most of dyeing and bleaching baths, so that the material can be optically brightened simultaneously with the dyeing and bleaching process with much profit.
  • the brightening substances. of this invention can also be employed together with finishing agents such as starch 3,178,421 Patented Apr. 13, 1965 and synthetic resin and washing agents like soap and alkylaryl sulfonate.
  • the brightening operation can accordingly be performed concurrently with finishing operation including crease-proof processing or with washing operation.
  • the zinc chloride double salts of this invention can be purified in an easy and simple manner, because of their inclination to salt out. Said double salts, however, have no substantial differences in the way of employment and brightening effect from the onium salts of this invention.
  • the brightening agents of this invention possess a marked substantivity for all kinds of hydrophilic fibers and penetrate into the fibers themselves to be steadfastly fixed therewith, which is presumably due to the'cationic property of the agents.
  • the material comes to yield an excelled fastness to sun light, ultraviolet light and washing as well, exhibiting arr-intense violet-blue fluoresc'encein ultraviolet light.
  • the brightening substances of this invention are all applicableto any kind of fibers as specified before, because of the high water-solubility and aflinity for the fibers. Even those materials which are made from, for instance, polyacrylonitrile or its copolymers, and which are hard to brighten in the prior art, canbe easily treated with the products of this invention. And the form of fibers treated in this invention comprises filament, staple-fiber, yarn, textile and film.
  • onium halides of this invention one mol of u,fl-bis-[aryloxazolyl-(2)]-ethylene is reacted at 20 to C. and in the presence of sulfuric acid and chlorosulfonic acid with 2 mols of hydrogen halide and 2 mols of formaldehyde in the form of paraformaldehyde or with 2 mols of dihalogenomethyl ether to introduce the halogenomethyl group to each of the aryl rings of the ethylene compound.
  • An onium salt-forming compound such as pyridine, picoline, lutidine and trialkylamine, is then added.
  • Thiourea and its derivatives and trihydroxyalkylamine are not employed in this invention as onium saltfor-ming agents, since the resulting product is colored.
  • Another method for preparing the onium halides of this invention is to react at ⁇ 20 to 80 C. and in the presence of sulfuric acid and chlorosulfonic acid one mol of a,B-bis-[aryloxazolyl-(2)]-ethane with 2 mols of hydrogen halide and2 mols of formaldehyde in the form of paraformaldehyde or with 2 mols of dihal-ogenomethyl ether to introduce the halogenomethyl group to each of the aryl rings of the starting material.
  • An onium saltforming agent as specified before is added.
  • the resulting product is then oxidized in water or in an organic medium, preferably in glacial acetic acid, at 50 to C. with a mild oxidant like mercuric acetate, mercuric oxide, hydrogen peroxide or nitrobenzene toproduce the desired halide of this invention.
  • the halogenomethylating reaction as specified above is performed mucheasier with sodium chloride or sodium bromide than with hydrogen chloride, since the reaction takes place with the hydrogen halide formed in the mixture by said salt with sulfuric acid.
  • the double salts of this invention are derived from the final products as specified above by dissolving in an aqueous solution thereof equi-molar zinc chloride. The purity of the product is improved merely by repeate filtration and recrystallization.
  • Example 2 To a mixture of 467 grams of 98 percent sulfuric acid and 36 grams of paraformaldehyde are added dropwise at 0 to 5 C. 292 grams of chlorosulfonic acid. The paraformaldehyde being completely dissolved with stirring, 29.2 grams of n p-bis-[S-methyl-benzoxazolyl-(2)]- ethane and then 58.4 grams of sodium chloride are added portionwise. The mixture is then stirred at to C. for 48 hours, and poured in ice Water. The precipitate is filtered, washed and dried, yielding a white crystalline substance having the formula 5 grams of the product thus obtained are then dissolved in 350 grams of chlorobenzene at 125 to 130 C. 3.5 grams of active carbon are added. The solution is filtered while hot. To the filtrate are then added 98 grams of pyridine. The miXIUI? i Stirred for 24 hours at C.
  • the resulting slurry residue is filtered, rinsed with chlorobenzene, and then benzene, and dried, yielding pyridinium salt almost quantitatively.
  • the product is purified by dissolving in methanol, decolorizing with active carbon, and recrystallizing with acetone.
  • Example 3 7 grams of the onium compound prepared according to Example 1 are dissolved in 210 cc. of water. 37 grams of 48 percent zinc chloride and 24.2 grams of sodium 'chloride, both dissolved in 170 cc. of water, are then added at 10 C. The mixture is allowed to precipitate at room temperature, and the precipitation product is filtered and dried, producing a pale yellow double salt of one mol of onium halide and one mol of zinc chloride. Yield is 97 percent for theoretical.
  • the resulting fabric is then treated for 60 minutes at 75 C. at a bath ratio of 1:50 in an aqueous solution containing per liter 2 grams of sodium chlorite and adjusted to pH 3 with 2 grams of 80 percent formic acid. After being rinsed, the material is further treated for 20 minutes at 50 C. in a bath ratio of 1:40 in an aqueous solution containing per liter one gram of sodium bisulfite. The material is then rinsed and dried, yielding a pronounced whiteness.
  • Example 6 Polyacrylonitrile fabrics are padded in an aqueous solution containing per liter grams of the double salt preparation obtained according to Example 3. The material is then squeezed until the entire weight is reduced to twice the original, steamed at 105 C. for 10 minutes in a closed vessel, and treated with sodium chlorite for minutes at 95 C. in a manner as illustrated in Example 5. After being rinsed, the material is further treated at 50 C. for 20 minutes in a bath ratio of 1:40 with 0.1 percent sodium bisulfitc. The material is then rinsed and dried, producing an enhanced whiteness almost similar to that whiteness obtained according to Example 4.
  • Example 7 Polyvinylacetal fabrics are treated in a bath ratio of 1:50 for 60 minutes at 75 C. in a bath containing per liter 0.01 gram of one-bis-[S-methyl-methylene-benzoxazolyl-(2)]-ethylene-w,w'-dipicolinium chloride and adjusted to pH 8 with a small quantity of sodium carbonate. The material is then treated with sodium chlorite and sodium bisulfite in a manner as illustrated in Example 5. The whiteness obtained is markedly improved.
  • Example 8 250 parts of nonionic washing agent consisting of a condensation product of 40 mols of polyoxymethylene and one mol of oleyl alcohol, are dissolved in water with 3.5 parts of the onium compound prepared according to Example 1 and 31.5 parts of sodium sulfate'to make a 0.1 percent onium compound solution.
  • Polyacrylonitrile fabrics are washed for 80 minutes at 20 C. with said aqueous solution in a bath ratio of 1:50.
  • the resulting material yields a more pronounced whiteness than the material merely treated with the washing agent containing no onium compound.
  • each of R and R is a member selected from the group consisting of hydrogen, methyl and ethyl;
  • B is a radical selected from the group consisting of pyridine, picoline, lutidine and trialkyl amine, and
  • X is halogen

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Coloring (AREA)
  • Detergent Compositions (AREA)
US78825A 1960-01-09 1960-12-28 Novel bis-aryloxazolyl ethylene optical brightening derivatives Expired - Lifetime US3178421A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP71760 1960-01-09
JP3026360 1960-07-02
JP4228560 1960-10-15

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US3178421A true US3178421A (en) 1965-04-13

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US (1) US3178421A (de)
CH (2) CH460786A (de)
DE (1) DE1419312A1 (de)
GB (1) GB967360A (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4033976A (en) * 1975-10-28 1977-07-05 Imc Chemical Group, Inc. Copper-oxazoline complex

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2463264A (en) * 1942-12-23 1949-03-01 Ciba Ltd Derivatives of cyclic amidines and process of making same
US2482392A (en) * 1945-12-15 1949-09-20 Rolfe E Whitaker Machine for trimming branches from standing trees
US2488289A (en) * 1949-11-15 Process for making a
US2620282A (en) * 1952-12-02 Fibrous synthetic material of
US2646355A (en) * 1948-12-01 1953-07-21 Ciba Ltd Process for brightening foodstuffs containing carbohydrates
US2809123A (en) * 1955-03-04 1957-10-08 Geigy Ag J R Fibrous synthetic material of improved whiteness
US2842545A (en) * 1958-07-08 Process for the manufacture of
US2873206A (en) * 1955-12-20 1959-02-10 Ciba Ltd Process for the optical brightening of polyester fibers
US2910472A (en) * 1958-05-13 1959-10-27 Ciba Ltd Process for producing certain substituted benzoxazoles
GB835892A (en) * 1955-06-17 1960-05-25 Ciba Ltd Manufacture of diaryloxazole derivatives
US3019221A (en) * 1959-06-15 1962-01-30 American Cyanamid Co Styryl-bisbenzimidazole brighteners

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2488289A (en) * 1949-11-15 Process for making a
US2620282A (en) * 1952-12-02 Fibrous synthetic material of
US2842545A (en) * 1958-07-08 Process for the manufacture of
US2463264A (en) * 1942-12-23 1949-03-01 Ciba Ltd Derivatives of cyclic amidines and process of making same
US2482392A (en) * 1945-12-15 1949-09-20 Rolfe E Whitaker Machine for trimming branches from standing trees
US2646355A (en) * 1948-12-01 1953-07-21 Ciba Ltd Process for brightening foodstuffs containing carbohydrates
US2809123A (en) * 1955-03-04 1957-10-08 Geigy Ag J R Fibrous synthetic material of improved whiteness
GB835892A (en) * 1955-06-17 1960-05-25 Ciba Ltd Manufacture of diaryloxazole derivatives
US2873206A (en) * 1955-12-20 1959-02-10 Ciba Ltd Process for the optical brightening of polyester fibers
US2910472A (en) * 1958-05-13 1959-10-27 Ciba Ltd Process for producing certain substituted benzoxazoles
US3019221A (en) * 1959-06-15 1962-01-30 American Cyanamid Co Styryl-bisbenzimidazole brighteners

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4033976A (en) * 1975-10-28 1977-07-05 Imc Chemical Group, Inc. Copper-oxazoline complex

Also Published As

Publication number Publication date
CH377776A (de) 1964-02-14
DE1419312A1 (de) 1970-02-19
CH460786A (de) 1968-08-15
GB967360A (en) 1964-08-19

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