Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
  • C07C309/45—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
  • C07C309/46—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton having the sulfo groups bound to carbon atoms of non-condensed six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
  • C07C309/29—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings
  • C07C309/32—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings containing at least two non-condensed six-membered aromatic rings in the carbon skeleton
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
  • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
  • D06L4/60—Optical bleaching or brightening
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
  • Y10S8/916—Natural fiber dyeing
  • Y10S8/918—Cellulose textile

Definitions

• Patented July 23, 1968 3,394,173 brightening agent to be fully satisfactory, also draw sutfi' O ICAL BRIGHTENERS OF THE ciently from a laundering bath containing the same onto STILBENE SERIES cellulosic and the like textile materials, preferably Heinrich Hausermann, Riehen, Switzerland, assignor to with the chlorine-yielding bleaching agent present in the J. R. Geigy A.G., Basel, Switzerland bath.
• X represents alkyl of from 1 to 5 carbon atoms, and preferably methyl or ethyl; lower alkoxy-lower alkyl,
• the present invention concerns new optical brighteners e.g. fi-methoxyor ethoxy-ethyl or 'y-methoxy-propyl;
• the m and n represent 0 0 aforesaid organic fibers optically brightened by a 9" which brighteners, for the first time, combine:
• each of R1 and R2 represent different or preferably impart a neutral whlte shade Wnh a blmsh or possbly identical radicals selected from the group consisting of very light violet hue, which appears very faintly pinkish O to the naked eye, but not a greenish hue, to the brightened 6 d y textile materials.
• each of R and R represents hydrogen, lower alkyl, lower alkoxy, hydroxy-lower alkoxy or lower alkoxy-lower alkoxy, and
• X is as previously defined herein.
• the content of brightener is preferably 0.005 to 0.5% by weight calculated on the weight of the detergent mixture.
• Suitable detergents contain as wash-active substances, e.g. anionic compounds, e.g. alkali metal salts, particularly sodium salts of higher fatty acids, alkali metal alkyl-aryl-sulfonates, especially dodecylbenzene sulfonate or tetrapropylbenzene sulfonate,
• non-ionogenic was-active compounds are fatty alcohol polyglycol ethers or alkylphenol polyglycol ethers.
• the detergents can contain the additives usual in the textile finishing industry such as water-soluble phosphates, silicates, carbonates, sulfates such as sodium sulfate water softeners, foam stabilizers and/ or textile softeners.
• the stilbene compounds according to the invention can be used without undue loss of brightening effect in detergents containing chlorine-yielding bleaching agents.
• Such bleaching agents are, for instance, open or cyclic compounds containing the group N-Cl such as N.N- dichloroisocyanuric acid, chlorohydantoins or N-chloroaryl sulfonic acid amides such as N-chloro-p-toluene sul- SOgH fonic acid amide or N-chloroalkyl sulfonic acid amides as well as such alkali metal or alkaline earth metal hypochlorites which are stable in solid state, e.g. lithium or calcium hypochlorite, these agents can be contained in the detergents and washing liquors, whereas hypochlorites which are instable in a solid state such as sodium or potassium hypochlorite can be used in the washing liquors.
• N-Cl such as N.N- dichloroisocyanuric acid, chlorohydantoins or N-chloroaryl sulfonic acid amides
• the brightening agents according to the invention draw well from an aqueous solution of the type described above onto organic fibers containing hydroxyl groups, such as cellulose, particularly cotton, and lend to this material a pleasing pure white, bluish fluorescent appearance.
• organic fibers containing hydroxyl groups such as cellulose, particularly cotton, and lend to this material a pleasing pure white, bluish fluorescent appearance.
• the brightened fibers have a content of 0.001 to 0.5% of brightening agent, calculated on the weight of the fibers.
• Brighteners according to the invention are produced by a process which is illustrated by the diagram below.
• the new brightening agent of Formula I are advantageously isolated from the reaction mixture in the form of their alkali metal salts.
• dialkyl sulfate to form the corresponding l-alkyl-sulfonyl)-2-methyl-4-chloro benzene
• starting materials of Formula II in which X represents alkyl are obtained from 1 alkylsulfonyl 2- methyl-4-chloro-benzene by nitration as mentioned above, starting materials in which X represents lower alkoxyalkyl are obtained in an analogous manner, alkoxy-alkylating the above mentioned sulfinic acid in lieu of alkylating the same.
• Reactive derivatives of organic carboxylic acids of the formula mainly anhydrides, chloride or bromides of these acids, (sometimes also ketenes), and also organic half esters of carbonic acid of the formula in the latter case mainly the chloroformic or bromoformic acid esters of lower alkanols, are used as acylating agents.
• chlorides and bromides of aromatic carboxylic acids in particular benzoic acid chlorides or-bromides the ring of which is substituted by lower alkoxy groups and/or lower alkyl groups particularly in one of the orthoand/or the paraposition, are preferred.
• aromatic carboxylic acid chlorides and bromides are 4-methoxyor 4-ethoxy-benzoyl chloride or bromide, 3-methyl-4-methoxy or 2,4-dimethoxy-benzoyl chloride or bromide, Z-methoxy- 4-methylor 2-eth0xy-4-methylbenzoyl chloride or bromide, 2-methoxy-4-ethylor 2-ethoxy-4-ethy1- benzoyl chloride or bromide, 2-methoxy-4,5-dimethylor 2-ethoxy- 4,5'dimethylbenzoyl chloride or bromide, or 3,4,5-trimethoxy-benzoyl chloride or bromide.
• the diaminostilbene compounds of Formula V or VII are advantageously acylated in the presence of tertiary organic nitrogen bases, optionally in the presence of inert organic solvents and, preferably, in the absence of water, at a temperature of about 20-120 C., in particular between 80 and 100 C.
• Suitable tertiary nitrogen bases are, mainly, pyridine and its homologues, trilower alkylamines, triethylenediamine and di-lower alkyl anilines; examples of inert organic solvents are optionally halogenated or nitrated aromatic hydrocarbons.
• the reaction solution is clarified and the sodium salt of the 2 methyl-4-chlorobenzene-lsulfinic acid is salted out with 15% of solid sodium chloride (calculated on the total weight of the reaction mixture).
• 106 parts of the sodium salt of the aforesaid sulfinic acid precipitate upon cooling in the form of white, easily water-soluble crystals which are separated by filtration.
• the free sulfinic acid is obtained from a concentrated aqueous solution of the sodium salt by addition of an excess of hydrochloric acid, and has a melting point of 91.
• 106 parts of the sodium salt of the above mentioned sulfinic acid are dispersed in 130 parts of water and heated up to 7075. At this temperature, 160 parts of dimethyl sulfate are added within minutes while the pH value of the mixture is adjusted to 8 to 8.5 by simultaneous addition of a sufi'icient amount of aqueous sodium hydroxide solution. After the addition of dimethyl sulfate,
• SOBNB SOJNB 40 parts of 4,4-diamino-6,6-dimethylsulfonyl-stilbene- 3,3'-disulfonic acid [intermediate (a)] are suspended in 400 parts by volume of anhydrous pyridine and a solution of 40 parts of 2-ethoxy-4-methylbenzoyl chloride in parts of anhydrous toluene is added while stirring. The mixture obtained is then refluxed for 2 hours at 100-110". At the end of this time, another solution of 40 parts of 2-ethoxy-4-methylbenzoyl chloride in 50 parts of anhydrous toluene is added dropwise and the mixture is heated for another 2 hours at 100-110".
• the reaction product separates out as a yellowish mass which becomes solid when cold.
• the crude product is purified by first washing with benzene, drying for a short time, suspending it in 1200 parts by volume of 5% sodium carbonate solution, heating the suspension at 7080 while stirring, again cooling, filtering off the yellowish product of the above formula, washing with 2.5 sodium chloride solution and drying at 80 in vacuo. In this way, a pale yellow water-soluble powder is obtained the diluted aqueous solution of which has a blue fluorescence in daylight. If uncolored cellulose fibers are treated with aqueous solutions of the product, then a beatuiful, neutral white effect is obtained on the strata mentioned.
• the product has remarkable stability to agents giving off chlorine which enables both optical and chemical bleaching to be performed in one bath. Another advantage of the product is that it has the property to draw onto cellulose fibers also in the presence of non-ionogenic washing agents.
• reaction mixture is stirred at the same temperature and pH for an additional hour. After cooling to 10, the reaction product is filtered off with suction and washed with water. 2-methyl-4-chlorobenzene-l-methyl sulfone, which is thus obtained in a yield of about forms colorless crystals and melts at 70.
• the product is dried at 75 under reduced pressure to yield 62 parts (99% of the theoretical amount) of crude 2-methyl-4-chloro-5-nitrobenzene-1- methyl su fone. This product melts at 127-130".
• the pure product (M.P. 137) is obtained in a yield of about by recrystallization from ethanol, 10 parts of ethanol for every part of crude Z-methyl-4-chloro-5-nitrobenzene-lmethyl sulfone being required.
• a thick slurry is formed which is filtered off by suction and the obtained crude product is purified in the following manner:
• the wet filter cake is dissolved in 250 parts of hot water, cooled down to 25 to 35, clarified by filtration, the filtrate is then salted out (n) diethylamino-sulfonyl at 60 to 70" with 55 parts of soiid sodium chloride and pyrrolidino-sulfonyl cooled to 10.
• the sodium salt of the 2-nitro-4- (p) piperidino-sulfonyl methylsulfonyl-S -methy1benzene-1-sulfonic acid is ob- (q) morpholino-sulfonyl tained in nearly colorless crystals.
• the product is filtered 5 (r) 2,6-dimethylmorpholino-sulfonyl otf and dried at 80 under reduced pressure.
• the reaction mixture is of 60 Paris of 2,44imeth0xybenl0yl Chloride in 300 stirred for 1 hour at 35.
• the separation of the new stii- Parts of anhydrous toluene are added-
• Powder 15 obtained Thereafter an aqueous solution of 2.4 parts of Sodium the dlluted aqueous solution of which has a blue fluorescarbonate is added and then the iron residue is filtered off cence,in daylight hot and is washed with hot water until the filtrate gives no product can be used for the bnghenmg of cellulose more diazo reaction.
• the yellowish solution is acidified fibers (39mm fabnc can be chefmcany and Ppticany with 15 parts by volume of 30%-hydrochloric acid, whereone Step b the P of brighten by 4,4'-diamino-6,6-dimethylsulfonyl-stilbene-3,3-disuli a i foni: acid Separates as a Slightly cream colored precipi mg liquor with and without bleachers giving off chlorine tate. This intermediate product is filtered off, washed with 50 the product glves beautiful neutral white effectsamount).
• CH3 SOQNB 803KB CH1 Products having a similar effect are obtained by replac- 14.5 parts of dry disodium salt of 4,4-diamino-6,6-diing the 40 parts of 4,4-diamino-6,6-dimethylsulfonyl-stilmethylsulfonyl-stilbene-3,3'-disulfonic acid are suspended bene-3,3'-disulfonic acid by an equimolar amount of one 60 in 125 parts by volume of abs.
• Example 3 By replacing the parts of 2-methoxy-4,5-dimethylbenzoyl chloride in Example 3 by equimolar amounts of the acid chlorides given in the second volume of the fol lowing Table I and using 14.5 parts of the 4,4-diaminostilbene 3,3'-disulfonic acid employed in said example or replacing the same by an equimolar amount of one of the intermediates (b) to (s) inclusive obtained as described after Example 1, while otherwise following the procedure given in the said example, corresponding end products 10 are obtained which are almost colorless to slightly yellowish powders of similar brightening properties as the products of Examples 1 to 3.
• Products having a similar action are obtained by using 6.5 parts of 2-acetyloxy-4-methylbenzoyl chloride or an equivalent amount of the acid chloride given in the second column of the following Table II, and also using 5.26 parts of 4,4 diamino-6,6' dimethylsulfonyl-stilbene-3,3-disulfonic acid employed in said Example 51 or replacing the latter acid by an equimolar amount of or of the intermediates (b) to (s) inclusive given after Example 1, and as stated in the third column of Table II by directly saponifying the resulting product, in the man- 13 14 ner described in Example 51, or by replacing in the Exwith sodium sulfite in a mixture of ethanol and water, ample 51, the ethylene chlorohydrin by an equimolar in the manner as described in Example 1 for the producamount of the bromides listed in the third column of the tion of the disodium salt of the corresponding methyl following Table II.
• Example 2 the 52.6 parts of 4,4'-diamino-6, acylating agent (used in Example 51) by one of the acyl- 6' di methylsulfonyl stilbene 3,3 disulfonic acid ating agents used in Examples 1 to 50 inclusive, and/or are replaced by 58.8 parts of 4,4'-diamino-6,6'-bis-diby replacing in Example 61 the parts of dimethylmethyl-sulfarnido-stilbene-disulfonic acid, the d-sodium amine by an equimolar amount of one of the amines salt of
• This product is isolated from its aqueous solu- TABLE 111 tion by salting out with 15% of solid sodium chloride (calculated on the total weight of the solution).
• the purified product forms a slightly yellowish powder, the aqueous solution of which exhibits in daylight a pronounced bluish fiuorescense.
• chloroformic acid ethyl ester is added dropwise at 7580 while stirring to the solution of the sodium salt of 4,4'-bis-(p-aminobenzoylamino) 6,6 dimethylsulphonyl stilbene 3,3- disulphonic acid and the acid liberated is neutralised with sodium carbonate solution.
• the reaction product is precipitated in a form which can be filtered by the addition of sodium chloride.
• Example 62 Products of similar good brightening properties, and especially of good fastness to chlorine are obtained by repeating Example 62, and using 4,4-diamino-6,6-dimethylsulfonyl stilbene-3,3'-disulfonic acid or one of the other starting acids listed following Example 1 under (b) to (s) inclusive, or 4,4-diamino-6,6'-bis-dimethyl- SOzCHa (iii) an equimolar amount of one of the aeylating agents listed in Examples 4 to 50, inclusive, or by an equimolar amount of one of the acetoxy-substituted acyl halides and chloroformates listed in examples 51 to with subsequent saponification or with subsequent reaction with ethylene chlorohydrin as in Example 51 or one of the bromides listed in Examples 55, 56, 58, 59 and 60.
• EXAMPLE 64 Cotton cretonne fabric is washed for 20 minutes at 60 (liquor ratio 1:30) in a washing liquor which contains, per liter, 5 g. of a washing agent of the composition:
• EXAMPLE 65 A mixture of 4.7 parts of sodium chloride, 0.3 part of lithium hypochlorite and 0.011 part of the brightening agent mentioned in Example 2 are dissolved at 60 in 1000 parts of water. If uncolored cotton cretonne fabric is treated for 20 minutes at 60 with this solution, liquor ratio 1:30, then after rinsing and drying, cotton fabric 01 a high degree of whiteness is obtained.
• EXAMPLE 66 10 parts of white cotton household linen are washed for 30 minutes at 40 in 200 parts of a washing liquor which contains 5 g. per liter of nonylphenol polyglycol ether (with 12 ether oxygen atoms) and 0.005 g. of the brightener obtained according to Example 1, and then rinsed and dried.
• the cotton goods so washed have a considerably more white appearance than a comparative sample washed in the same liquor without brightener.
• a brightening effect which is equally good for practical purposes is attained if the washing is performed in a washing liquor which contains 6 g. per liter of a nonionogenic washing agent of the composition:
• An optical brightener which in its free acid form is of the formula SOgX CO-R:
• each of R and R represents a member selected from the group consisting of (lower alkyl)-, (lower alkoxy)-, R -(lower alky1)-, R -(alkoxy)-wherein the alkoxy moiety has from 2 to 4 carbon atoms,
• radicals R and R the substituent R represents a member selected from a group consisting of hydroxy, lower alkoxy, hydroxy-loweralkoxy, phenoxy, chlorophenoxy, bromophenoxy, lower alkyl phenoxy and lower alkoxy-phenoxy,
• R represents a member selected from the group consisting of hydrogen, fluorine, chlorine, bromine, lower alkyl, lower alkoxy, hydroxy-lower alkoxy and lower alkoxy-lower alkoxy,
• R represents hydrogen, fluorine, chlorine, bromine, lower alkyl, lower alkoxy, hydroxy-lower alkoxy or lower alkoxy-lower alkoxy.
• p represents one of the integers 1 and 2
• q represents an integer ranging from 1 to 3
• optical brightener which in the free acid form is of the formula:
• optical brightener which in the free acid form is of the formula:
• optical brightener which in the free acid form is of the formula:
• optical brightener which in the free acid form is of the formula:

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Detergent Compositions (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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• 1963
  • 1963-12-20 CH CH1571363A patent/CH433249A/de unknown
• 1964
  • 1964-12-18 GB GB51648/64A patent/GB1031750A/en not_active Expired
  • 1964-12-18 US US419566A patent/US3394173A/en not_active Expired - Lifetime
  • 1964-12-18 DE DE19641443980 patent/DE1443980A1/de active Pending
• 1968
  • 1968-05-13 US US728782A patent/US3506657A/en not_active Expired - Lifetime

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