DE1519474A1 - Optical brighteners - Google Patents

Description

FARBWERKE HOECHST AG.

- Expl. I

Ai a ίϊ>. uezemD

Plant ι ur. s _C h / s ₀

to the patent application Fw

Frankfurt (M) -Hoechst

December 23, 1965

49b1

Optical resolution Munfs.mi ftp I

Hs is already known, derivatives of benzoxazoil as optical Use whitening agents. So are z.ü. in the literature CX, ß-L) i * benzoxazolyl- (2) -ethylenes for lightening synthetic Fibers, e.g. those made from cellulose esters, especially cellulose acetate, from polyesters such as polyethylene glycol terephthalate. lat, polyamides or polyvinyl chloride have been described.

It has now been found that colorless or almost colorless, fluorescent derivatives of 4- / ~ uenzoxazolyl- (2 ^l ) _ / - naphthoic acid- (1) of the general formula

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Fw 4901

in which Y is a carboxyl, an esterified carboxyl, a carboxamide, a carboxonitrile group and A the radicals R ^ and I ^ hydrogen, a low molecular weight, up to to 4 carbon atoms containing Mkyigruppe or together in the adjacent position a condensed hydroaroraatic lüng mean, can be used very well as an optical brightening agent.

The new connections are characterized by a very strong one Fluorescence power and good lightfastness when lightening fiber materials and foils, especially made of polyester of the acetylated polyethylene glycol terephthalate type "- cellulose, polyamide, polyvinyl chloride and polyacrylonitrile the end.

Those according to the present invention as a lightening agent Benzoxazoles of the general formula I to be used can be prepared in various ways, for example by taking o-aminophenols of the general formula

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II

with acid chlorides of 4-carbalkoxx-naphthoic acid- (1) or ^ -Cyan-naphthoic acid-O) of the formula CItIp X ⁼ COOK) »

UOÜC- / VX X = CüOR

■ = CN

III

in which R is a low molecular weight up to 4 carbon atoms Alky! group containing means, uüisetzt, the obtained N'-Acvl compound in the general formula ■

-X IV

zweckniiüJiρ, in a Inertgasatmospiiäre, preferably nitrogen, in iiochsiedenden solvents vorteilliaft at temperatures oberivnIb '2, "K3 ^Q C _t preferably 215-220 °' C. ₁ gegebenenf alls-ln * U? ^ emvart of catalysts heated and with elimination of wet, formed 4-y_ iienzoxazolyl-C2 ') __ 7 ~ naphthoic acid-Ct) esters or nitriles of the formula

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Fw 4901

-X

optionally after saponification to the free acid £ V _# X «COOiI) and conversion into the carboxylic acid chloride, converted into 4 - / _ 3enzojcazolyl- (2 ') __ 7" naphthoic acid (1) esters, amides and hydrazides.

Another possibility of preparing the 4- ^ iienzoxazo.lyl-C2 ^f J_7 -naphthoic acids (V, X ■ COOH) consists in the condensation of 1 mol of the dichloride of the naphthalene dicarboxylic acid (1,4) (VI) with 1 mole of the o-amino-phenoiq (II) in the presence of acid-binding agents, 3 tertiary amines such as dimethyl aniline, to the N-acyl compounds (VII) _f

R ₁
MOlC- * V-COOH I ^ T "CO · / A-GOCl-

VI

VII

which after saponification of the SJiurechloridrestes by heating in an inert gas atmosphere, advantageously nitrogen, in high-boiling Solvents, e.g. 1,2,4-Triehiorbenzoi on internal temperatures of over 200 ° C, preferably 215 to 220 ° C, optionally in the presence of zinc chloride in the corresponding

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den 4- / ~ Öeaz.Qxa: zolyl- (2V) _7-naphthoic acid (1 ..) (V, X = C0.0H) can be transformed. From this, the . Corresponding derivatives obtained in a manner known per se will..

As o-anvinophenols (II,) it is possible, for example, to use we rdeni

o-AminophenQlj S-Amino ^ -hydroxy-toluene ,, 4-Amino-3-hydroxytoluene, J-amino-2-hydroxy-toluene, 5-amino-4-hydroxy-1,2-xylene, 4-amino-5-hydroxy-1,3-xylene, 5-amino-4-hydroxy-1,, 3'xylene ^ 3-Amino-4 ^ i) ydroxy-1 -text, butyl -benzene., 5-Amino-6'hydroxy'-hydrindene, 5, ü, 7,8-Tetrahyd.ro-1 -amino-2-naphthol, -5.0J7.8

As 4-carbalkoxy-naphthoic acids (] ) (.1-11> X *. COOR) there may be mentioned;

4-carbomethoxy "η aphthoesaur.e- (1)> 4-carboethoxy-naphthoic acid-jCi ) -f 4» carbopropoxy-naphthoic acid- (l) _t 4-carb ^ isQ- propoxy-naphthoic acid-C.1) , 4-Carbo-butoxy-naphthoic acid- (r), 4 "Carb-iso-buto.xy-naphthoic acid- (1)»

This Ilalbeste? can by saponification of the appropriate Naphthalene-1 ^ "• dicarboxylic acid ester with half an equivalent an alkali * or ordalkali hydroxide in a simple manner

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getting produced.

/ VIs alcoholic or phenolic compounds, which can be used for the esterification of the 4 - / _ uenzoxazolyl- (2 ') _ 7-naphthoic _{acids (V 1} , X = COOLI), are also mentioned:

Single and multivalent aliphatic jcycloaliphatic, ar a Ir-φ phatic alcohols, phenols, naphthols, etc. such as methanol,

Ethanol, n-propanol, isopropanol, n-butanol, tert. liutanol ,, Octanol, cyclohexanol, 2-, 3-, ^ -Methylcyclohexanol, 2-chloroethanol- (1), 1-chloropropanol- (2), glycol, propanediol- (1,2), n-autandiol- (1,3) and - (1,4), 2-methyl-n-butan-diol-Ci, 3), n-hexanediol (2.5), glycerine, pentaerythritol, diethylene glycol, TriUthyleneglykol, Glykolmonomethyläther ^ Glykolmono.üthyläther, Glycol mono-n-butyl ether, 3-methoxy-n-butanol- (V)., Glycid, phenol, o-, m- and p-cresols, xylenols., Benzyl alcohol, 2-phenylethanol- (1), 4-isopropylbenzyl alcohol, 2-dimethylaminoethanol- (l), 2-diethylamino-ethanol-ii) ,, 2-di-n-butylamino * ethanol- (1) , .1-Diiaethylamino-propanol-C ^).

As amines which are used to produce the 4- / ~ "benzo; xazolyl- (2 ') _7-naphthoic acid (1) -amides Find use., Can also belong to a wide variety of series, for example the aliphatic, cycloaliphatic, araliphatic, aromatic

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see and heterocyclic series. There are also amino compounds in consideration of the other sub-substituents such as Contain hydroxy or S, whore groups. In detail are called:

Ammonia, methyl, ethyl, n-propyl ", n-üutyl-, iso-ßutyl-, Dimethyl-, dijithyl- and di ~ n ~ butylamine, cyclohexylamine, Ethanol and IHiijihanolamine, ß-methoxy-ethylamine, aminoessific acid, MethylaminoessiBSäure, 2-Amino-uthan-sulfonic acid, 2-methylaminoethane sulfonic acid, ß-l-methylaminoethylamine, Aniline, aniline-3- and «-4-sulfonic acid, N-methylaniline, Üenzyl- and ß-phenylethylamine, N-methyl-N-benzylamine, piperidine, Morpholine and i'iperazine "

The 4 - / _ ~ uenzoxazolyl- (2 ^l ) _7-naphtho- (1) -nitriles can also be obtained from the carbonamides of the general formula

-CONU ₂ VIII

by F: in effect * of water-releasing agents such as z.d. Phosphorus oxychloride or phosphorus pentoxide, optionally in The presence of organic solvents can be produced.

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The acid chlorides of the 4-carbalkoxy-naphthoic acids (1) (III, X = COOR) can in a manner known per se, e.g. by reacting the 4-carbalkoxy-naphthoic acid (1) with Thionyl chloride.

The implementation of the o - / \ minophenols (II) with the acid chlorides φ of the 4-carbalkoxy-naplvthoe.säuren- (1) and 4-cyano-naphthoe-

acid- (i) is advantageous in an organic solvent, e.g. toluene or chlorobenzene, in the presence of a tertiary aase to bind the hydrochloric acid that is split off, e.g. dimethylaniline, at an elevated temperature, preferably about 5'J to 100 ° C. When cooling the reaction mixture If the acylamino compound (IV) crystallizes out, it is filtered off with suction and the adhering material is removed by steam distillation Freed solvent.

The conversion of the N-acyl compounds (IV) into the benzoxazoles (V) is carried out in high-boiling solvents. 1 »2,4-trichlorobenzene is particularly suitable as such or mixtures of trichlorobenzenes. The internal temperature of the reaction mixture should be above 200 ° C., preferably from 215 to 220 ° C. Compounds can be used as catalysts like zinc chloride or p-toluenesulfonic acid.

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The compounds of the formula (I) obtained according to the invention can also be converted into each other by the following reactions: The nitriles (Y = CN) can be converted by heating in alcohols in the presence of hydrogen chloride into the carboxylic acid esters (Y = COOR, R = low molecular weight alkyl radical) convert. The esters can e.g. from the methyl ester (Y = COOCU.,) By transesterification with another, up to 4 Alcohol containing carbon atoms, optionally can be substituted, in the presence of the alcoholate this Alcohol.

The lightening agents according to the present invention can be used in a manner known per se, either in the form of solutions in water or in the form of aqueous dispersions, optionally with the aid of dispersants. They can also be used in the form of solutions in organic solvents. The required quantities, which can fluctuate within wide limits, can easily be determined through preliminary tests. They are from 0.001 to _2%%, preferably 0.01 to 0.5% _r bez.ogen on weight.

The compounds can also be used together with chemical bleaching agents, e.g., oxidative or reductive, such as sodium chlorite, Sodium dithionite, sodium borohydride, can be used. Further

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these new compounds can be added to commercial detergents to beautify the laundry, whereby Good lightening effects can be achieved on polyester fibers even at washing temperatures below the boiling point. Farther they can also be added to spinning and .tJießmassen serve for the production of artificial fibers, threads, films or other structures. The following examples are intended to support the show versatile application possibilities without this however would be limited to that.

example 1

A polycaprolactam fabric bleached in the usual way is used in a liquor ratio of 1:20 with about 1.5 g / l of an aqueous Treated dispersion of the compound XVII at üO ° for 30 minutes. 1.5 g / l of a quaternary fatty acid derivative are added to the rinse bath and the tissue is added to it for 30 minutes post-treated at a temperature of 40 °.

In addition to increasing the whiteness by 9.4 %, this method of working produces a soft and smooth feel to the fabric. In this and the following examples, the light remission was measured with a Zeiss Blrepho device at a wavelength of 40 °, rough against MgO (= 100%).

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Connection XI can also be used in the same way will.

The compounds XI and XVII listed in Example 1 as well as their preliminary products can be produced in the following way will: ·

23 parts by weight of naphthalene-1,4-dicarboxylic acid nionomethyl ester (Melting point 150.5 to 151.0 ° C) are in 87 parts by weight Toluene with 1 u, 4 parts by weight of thionyl chloride implemented at 80 ° C. After removing the excess Thionyl chloride is left the still warm solution of the acid ■ Chloride to a mixture of 14.1 preheated to 75 ° C Parts by weight of 5-amino-4-hydroxy-1,2-xylene, 12.7 parts by weight of diinethylani lin and 70 parts by weight of toluene are added dropwise and stir at 75 ° C. for a further 3 hours. The unusual one Acylamino compound is filtered off and with cyclohexane and Washed methanol or freed from adhering solvent by steam distillation. Heated to form a ring silt the dried acylamino compound (32.7 parts by weight, melting point 253 to 257 ° C.) is 72 parts by weight !, 2,4-trichlorohenzene and 0.1 part by weight of zinc chloride in Nitrogen atmosphere at 215 to 220 ° C for about 2 hours (Internal temperature), 48 parts by weight of methanol are added during cooling. The crystallized denzoxazole

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derivative (X) is sucked off and twice with 25 weight, share cyclohexane washed and dried. 29.5 is obtained Parts by weight of crude product. ,

After recrystallization from toluene with the addition of activated charcoal, the pure methyl 4- / 5 ', b'-methyl-benzoxazolyl- (2') -7-1-naphthoate is obtained (X) from melting point 1b7 to 108 ° C.

The naphthalene-1,4-dicarboxylic acid raonomethyl ester used above can be produced in the following ways:

48.8 parts by weight of naphthalene-1,4-dicarboxylic acid dimethyl ester from [solidification point 04.9 ° C are in 200 parts by volume Dissolved methanol warm, at 40 ° C., the mixture is left with thorough stirring a solution of 8 parts of sodium hydroxide in 25 parts by weight Add dropwise hater and stir under reflux for half an hour after. Two thirds of the methanol are then distilled off. The residue is t> 00 parts by weight Added water and concentrated with a mixture of 35 parts by weight. Acidified hydrochloric acid and 100 parts by weight of water. The precipitated precipitate is filtered off with suction, washed free of hydrochloric acid and treated with a solution of 30 parts by weight of sodium hydrogen carbonate in 000 parts by weight of water stirred, the saponification products dissolving while

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unreacted dimethyl ester remains undissolved and filtered off will. The carboxylic acid is concentrated by acidification with a mixture of 35 parts by weight. Hydrochloric acid and 50 parts by weight of water precipitated again, filtered off with suction, washed with water and dried. 40 parts by weight of crude ilal ester are obtained, which are obtained by recrystallization 1000 parts by weight of toluene cleans. The one from the FiItrat crystallizing naphthalene - !, 4-dicarboxylic acid monomethyl'-ester is sufficiently pure after drying and melts clear at 150.5 to 151 ° C. Yield: 29 parts by weight of ilal ester; Equivalent weight titrated 229 (calc, 230).

The methyl esters IX and XI listed in the table can in an analogous manner using the o-aminophenol and 5-Amino-4-hydroxy-hydrindens are shown.

50 parts by weight of compound X are in 800 parts by volume Ethanol (9ö Ug) suspended. At 80 ° the mixture is left with stirring a solution of 102 parts by weight of potassium hydroxide in 25 parts by volume Add water dropwise and reflux for a further 2 hours. 500 parts by volume of ethanol are distilled off. The residue is concentrated with 25 parts by volume. Hydrochloric acid is added, the carboxylic acid precipitating. After diluting with 1000 parts by weight of water is stirred for 1 hour, filtered off with suction and washed with water. 47 parts by weight are obtained

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4- / 5 ', ü'-Dimethylbenzoxazolyl- (2') _ 7-naphthoic acid- (1) from melting point 280 to 282 ° C (XIII). The carboxylic acid XII can be obtained analogously starting from the compound IX will.

From 41.2 parts by weight of the carboxylic acid XIII, 21.3 parts by weight of thionyl chloride and 450 parts by volume of toluene, W becomes the carboxylic acid chloride XV (melting point 159 to 10 ° C.) in

produced in a known manner. After removing the Excess thionyl chloride is passed into the toluene solution ammonia in excess, the carbonamide XVI fills in as a colorless precipitate. The precipitated product

is sucked off by .Vapor distillation of the adhering Freed toluene, suctioned off again and then stirred with a dilute sodium carbonate solution to remove any remaining residues ^ to pull out the carboxylic acid. Do thorough washing

and drying gives 3 ¹ J parts by weight of compound XVI of melting point 280 to 282 ° C.

The acid chloride XIV can, starting from the carboxylic acid XII, can be obtained in an analogous manner.

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32 parts by weight of the carboxylic amides XVI are with 107 parts by weight Ph.o-sphoroxychlo. rid-cooked 75 minutes languiter reflux (internal temperature 1os ⁰ C). The cooled reaction mixture is poured onto about 1000 parts by weight of His. The precipitated compound is filtered off with suction and washed with water. After drying, 30 parts by weight of crude product of melting point 205 to 200 ° C. The 4- / ~ 5 ^f, ü'-Üimethyl-benzoxazolyl (2 *) _ 7-naphthoic-1-riitril XVII can φ

be purified by recrystallization from ßutanol and then melts at 2ü9 to 210 ° C.

Example 2

Incidentally bleached polyethylene glycol terephthalate fabric is treated in a liquor ratio of 1:20 with 0.15 g / l of an aqueous dispersion of the compound X at 98 ° for 30 minutes. The goods undergo this treatment a significant increase in the degree of whiteness. The preparation of the compound X is described in Example 1.

- Example 3

A polyethylene glycol terephthalate fabric bleached in the usual way is in a liquor ratio of 1:20 with 0.15 g / l one aqueous dispersion of compound X at 120 ° for 30 minutes treated. This treatment increases the remission of 83.4 to 95.4 i.

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game 4

liin 'l'olyäthylenglykolterephthalatgewebe bleached with an aqueous dispersion which isodecylsulfobernsteinsaures sodium and 10 g / l of the compound X includes, padded, squeezed off to a residual moisture bu I and then treated for 1 minute at 18O ° C in the mutual flow of hot air. The goods treated in this way experience a significant increase in whiteness.

lieispicl 5

liin bleached fabric made of acetylated cellulose is treated in a liquor ratio of 1:20 with 0.15 g / l of an aqueous dispersion of compound XI for 30 minutes at a temperature of 70.degree. The remission of the tissue is improved from 8 0.0 to 8 <3 %.
The preparation of the compound XI is mentioned in Example 1.

Example Q

An unbleached copolymer fabric with a minimum content of 85 l of acrylonitrile is used in a 1:20 liquor ratio 0.0 g / l sodium chlorite 100 Ug at pll 3.5 (set with Sulfuric acid,) and 0.2 g / l of an aqueous dispersion of the compound XI 9J minutes at a temperature of 80 to 85 ° C treated. Through this action one obtains a remission

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Increase from 78.4 to 91.2 5.

The products XVIII and XIX listed in the table are also suitable for lightening polyacrylonitrile fibers. They can be made on the following table:

33.1 parts by weight of the methyl ester X are added to 300 parts by weight ß-Dimethylariino-ethanol under a slight vacuum from about 200 Torr with stirring and slow distillation δ to 7 hours at a bath temperature of about 110 ° C warmed up. As a catalyst for the transesterification, 0.4 parts by weight of sodium β-dimethylaminoethylate are added in four portions as a solution (5 to 10 ecm). Distilled last all the remaining ß-üimethylamino-ethanol from and the residue crystallizes from ethanol with the addition of Activated charcoal. 33.8 parts by weight of crude product are obtained in this way. Further recrystallization gives pure β-dimethylamino-ethyl ester XVIII from melting point 108 to 110 ° C.

23.3 parts by weight of compound XVIII are dissolved in 300 Divide by volume of ethyl acetate in the heat. Be at 30 ° then 8 parts by weight of dimethyl sulfate added with stirring, whereby an almost colorless crystal pulp is created. It is briefly brought to the boil, cooled and filtered off with suction. The filter residue is four

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times covered with 25 parts by volume of ethyl acetate. . 28.5 parts by weight of almost colorless quaternary salt XIX are obtained.

Example 7

A similarly light polycaprolactaia fabric is in a liquor α ratio 1 ·: 20 with

1., 2 p / l sodium jithionite 0.8 fi / 1 sodium pyrophosphate and . 0, T5g / l of an aqueous dispersion of the Compound XI

treated at 00 C for 30 minutes. The mission value the goods increase through this treatment from 7.5 to 87.5 S-

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TASELL II

I ¹ J -

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Formula Mr

Constitution focus

-COO Cj I

100-101 ° C

-COiJCJiI

10? - 1O8 ^u C

O,.

138-13y ° C

274-275.5 ° C

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Tw 4 9ί>?

l'ornel no.

constitution

Melting point

COÜii 280 - 282 ^υ C.

-C

159-160 ° C

-C

159 - ■

-C

280-28 2 ° C

, I ₃ C

209-210 C

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Formula No.

Constitution melting point

XVIII

-COO-CiI_-ClL ₇ IN \

CH-

108-110 ° C

OSO-CH

175-203 C.

N,

-COiIN-CiI ₉ -CH,

SO ₃ Il

-CO-N-CH ₇ -CH ₇ -SO-H L £ · j

CiL '

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ii ₃ c ^/ ! UC
I. - 22 - 2 3 ' Fw 4 901 F ο rme 1 No. Λ constitution - Melting point XXII ^ll 3 ^C - / \ -Ct) -NiI-CiI ₂ -CiI . ,, ₃ " - b O XXIII - ^) - CO-N- ₂ - i 2
O ™ 3. O

XXIV

ti ₂ C

/ U ₂ C, I ₂ C

ON-CiI -CiI -S3 il ti ^{L l} . ■

ii ₂ c:

CtI ₃ SO ₃ Il

009808/1696

Claims (4)

■ 151W74 - 2 3 -. 'Fw 4 9ü1 P Λ T U M T Λ N S P Il ίϊ € ϋ Π 1) Use of colorless or almost colorless, fluorescent derivatives of the 4 - / _ Benzoxazolyl- ( ^2f ) _7 «naphthoic whore- (1) of the all-in-one standard formula in which Y a carboxyl, an esterified carboxyl, cine carboxamide, a carboxonitrile group and the residues! tj and R _{7 are} hydrogen, a low molecular weight, up to 4 carbon atoms containing A-IKy group or together in an adjacent position a fused hydroaromatic Ring mean as an optical brightening agent. 2) Optical Aufhellunpsnittel, nekennzeichnet by a content of colorless or near colorless, fluorescent derivatives of 4- / i5enzoxazolyl- (2 ^L) _ / "naphthoesüure- (V) of the allpeincincn l'Ornel I in which Y is a carboxyl, an esterified carboxyl, a carboxamide, a 00 9808/16 98 - 24 - Fw 4Dt) I Carboxylic acid nitrile group and the radicals R ₁ and R- denote hydrogen, a low molecular weight alkyl group containing up to 4 carbon atoms or together in an adjacent position a fused hydrochloric acid ring. 3) Process for the optical brightening of textiles and foils, characterized in that they are coated with colorless bw. almost colorless, fluorescent derivatives of the 4 - / "" IiCnZOXaZoIyI-I. ^ ') _7 ~ naphtho-esic acid- (1) the general Formula 1, in which Y is a carboxyl, an esterified carboxyl, a carboxylic acid anide, a carboxylic acid nitride group and the Ueste K, and K ^ hydrogen, a low molecular weight, Alkylgrupp.e containing up to 4 carbon atoms or together in an adjacent position denote a fused hydroaromatic ring. 4) Method according to claim S, characterized in that textile materials or films made of linear polyesters of the iOlyüthylenterephthaiats type acetyüerter cellulose, polyamide, polyvinyl chloride and / or polyacrylonitrile are subjected to ßehandlunq. . 0Π9808 / 1698