DE2331444A1 - NEW STYRYL BENZOXAZOLE, PROCESS FOR THEIR PRODUCTION AND THEIR USE AS AN OPTICAL LIGHTENING AGENT - Google Patents

Description

FARBWERK © HOECHST AKTIENGESELLSCHAFT 2331444

formerly foreman Lucius 8t Brüniiig

File number: HOE 73 / F 173

Date: June 19, 1973

New styryl-benzoxazoles, processes for their preparation and their use as optical brightening agents

2-Styryl-benzoxazoles and their use as optical brightening agents for organic materials are already known (DTPS 1,444,014).

The present invention relates to colorless to pale yellow 2-styryl-benzoxazole derivatives which are in solution fluoresce between about 40 and 450 nm and the formula (1)

(D

1 2

in which R and R are hydrogen or halogen atoms or a lower alkyl, lower alkoxy, phenyl or cycloalkyl group with k to 8 carbon atoms or R and R together are an alkylene group with 3 or 4 carbon atoms

40988 ^ ^{/ 1387/2}

31444

or an anhondensiorton dsn ^ olring, ii gin hydrogen or halogenated or a lower alkyl or alkoxy group, X is an optionally substituted by non-chrosnophoric radicals te lower alkoxy, acyloxy or acyl «mirio group and Y is a optionally «functionally modified carboxyl group or

1 2 mean a lower alkanoyl group, R ixnd R are here preferably in the 5- or 6-position and R in the 6-position.

Preference is given to compounds of the formula (1) in which R and

2
R represents hydrogen or chloratorae, a lower alkyl group optionally substituted by a carboxy, lower carboalkoxy, lower alkoxy, hydroxyl or phenyl group, cyclohexyl, lower alkoxy or phenyl group

1 2
or R and R together are an alkylene radical with 3 or h carbon

3 substance atoms or an attached benzene ring, R. V / reagent or chlorine atom or a lower alkyl or Alkoxy group, X a Gi * uppe dei 'Formol

-O-A-Z or -Q-Ac

mean in which A is a lower alkylene group, Z is a hydrogen or chlorine atom, a hydroxy, lower ail: o :: y-, lower carboalkoxy-, lower dialky3.arain.o-, lower trialkylaintnonium-, Carboxy or cyem group, G for an oxygen atom or one; -NH group and Ac for a possibly by a chlorine atom, a lower alkoxy, lower dialkylamino- or lower trialkylammonium group substituted lower ones Alkanoyl or the benzoyl radical, and Y is a cyano group or a remainder of the formulas

-COOM, COOR ¹ , -C _{ς r} , -C. _{6 7}

^ ⁵ R ^x KH-KR ³ R or -CO-R ^

4 means, in soft M a colorless cation, R a group the formula

-Q-T

40988A / ^1367/3

means in which Q is a lower alkylene or phenylene radical and T is a hydrogen atom, a lower alkoxy, hydroxy, lower dialkylamino or lower trialkylammonium group represent, L stands for an oxygen or sulfur atom, R and R for hydrogen atoms, lower alkyl groups through lower alkoxy, hydroxy, lower dialkylamino or lower trialkylammonium substituted lower alkyl groups or R and R together with the nitrogen atom represent a hydrogenated, 5- or 6-membered, optionally an oxygen atom or represent another nitrogen atom-containing ring and R is a lower alkyl group, and in particular Ver

1 2
bonds in which R and R are hydrogen or chlorine atoms, methyl or ethyl groups or together a trimethylene or

3 tetramethylene group or a fused-on benzene ring, R a hydrogen or chlorine atom or a methyl or methoxy group, X is a lower alkoxy group or an ethoxy group substituted by a lower alkoxy or hydroxy group, a lower alkanoylamino, benzoylamino, lower alkanoyloxy or benzoyloxy group optionally substituted by a chlorine atom and Y represents a cyano, carboxy, lower carboalkoxy or carbonamide group, the carboalkoxy radical being through Hydroxy, lower dialkylamino or lower trialkylaramonium radicals and the carbonamide nitrogen through lower alkyl groups, which in turn can be substituted by hydroxy, lower dialkylamino or lower trialkylammonium groups can be, where these lower alkyl groups also together form a 6-membered one, optionally through an oxygen group or another Can represent nitrogen atom interrupted ring. The term "lower" used in connection with aliphatic radicals is intended to mean groups with up to 4 l · carbon atoms describe.

A functionally modified carboxy group is initially to be understood as meaning its salts with colorless cations, where Alkali metal or ammonium units are preferred, furthermore those derivatives in which one carbon atom has three bonds having to heteroatoms, especially the cyano group, the

4 0 9 ö b 4/1 3 B 7 Λ

Carboxylic acid ester group or the carboxylic acid amide or hydrazide group.

The 2-styryl-benzoxazole derivatives according to the invention can be synthesize by various methods. Preferred processes for their production are explained below:

Condensation of a phosphono compound of the general formula (2)

.1

(2)

with substituted benzaldehydes of the general formula (3)

(3)

at temperatures between about 0 and 100 ° C. in organic solvents in the presence of basic condensing agents. In the

12 3 formulas (2) and (3) the radicals R ₅ R, R, Y and X have the meaning given for formula (1); R and R stand for identical or different, preferably lower, alkyl groups, cycloalkyl groups with 4-8 C atoms or phenyl radicals, optionally bonded to the P atom via an O atom. Since the

8 9
Residues R and R 'do not occur in the end product, their chemical nature is not critical with regard to the process product.

The condensation components (2) are produced, for example, by the reaction of 2-halomethylbenzoxazoles (prepared, for example, according to Elderfield, Heterocyclic Compounds, Vol. J5, p. 420 ff) with phosphorous acid trialkyl esters obtain. / 5

The processes mentioned are advantageously carried out in indifferent ways Solvents, for example hydrocarbons such as toluene or Xylene or alcohols, such as methanol, ethanol, isopropanol, Butanol, glycol, glycol ethers such as 2-methoxyethanol, hexanol, Cyclohexanol, cyclooctanol, and ethers such as diisopropyl ether, dioxane, tetrahydrofuran, and also in formamides and N-methylpyrrolidone. Dipolar ones are particularly suitable organic solvents such as dimethylformamide and dimethyl sulfoxide.

Strongly basic compounds can be used as condensation agents, such as alkali or alkaline earth metal hydroxides, Alkali or alkaline earth amides, preferably potassium hydroxide, sodium hydroxide, potassium tert-butoxide or sodium ethoxide, forner the alkali compounds of dimethyl sulfoxide and alkali hydrides and optionally alkali metal dispersions.

The reaction temperature depends on the type of

is about 0
wise between about 10 and about 8o C.

Starting materials between about 0 and about 100 ° C, preferably

As phosphono compounds of the general formula (2) can those are used which are derived from the following o-aminophenols:

/ 6 40988W 1 367

233HU

H COOC-CH ₂

NH ₂

Cl NH ₅

OH

NH,

H ₈

OH

H ₈ C

NHo

OH H ₈ C- '

NH ₀

OH

H ₃ C- (T

NH.

OH

H,

NH ₀

OH

1367

OH

OH

CH, ι

C «H _K -C

NH ₂

OH

NH ₀

OH

Substituted benzaldehydes of the general formula (3) can be used will:

H'

OCH ₃ CN CH,

, 0CH ₂ -CH ₅

, OCH ₂ -CH ₂ -CH ₂ -CH ₃ 'O) -CN

CH ₂ -CH ₂

00GH ₃

0, -CH ₂ -CH ₃

-CH ₂ -CH ₂ -O-CH ₂ -CH ₃

/ CH ₃ O-CH CH,

COOCH ₂ -Cn ₃

H ₂ -CH ₂ -O-CH ₃

40988 ^ / 1367 /8th

233U44

CH ₂ -CH-CH ₃

-CN P-CH ₂ -CH ₂ -O-CH ₂ -CH ₃

VToV-COOCH ₂ -CH _{3 H} / V ^

0-CH ₂ -COOCH ₃

0-CH ₂ -COOCH ₃

COOCH,

-CH ₂ -CH ₂ -COOCH ₃

0-CH ₂ -COOC ₂ H ₅

y.o:

0-CH ₂ -CH ₂ -N _x

CN

0-CH ₂ -COOCH ₃

^X Cr \ O / —COO-CHp -CIL -O-CE,

₂ -CH ₂

OCH,

COOCH,

Cl

CH ₅

OCH,

H ₃ CO

COOCH,

OCH ₃

CN OCH, 0 II 0-C-CH,

Another important possibility of preparing the 2-styryl-benzoxazoles according to the invention consists in the reaction of substituted o-aminophenols of the formula (k)

with activated derivatives, in particular the acid halides, of cinnamic acids of the formula (5)

HO-C-CH = CH - (()> - Y (5)

12 3

in which R, R, R, X and Y have the meaning given under (1), to the corresponding acylamino compounds and their cyclization in the presence of acidic catalysts.

The acylation of the o-aminophenols is preferably carried out in inert solvents in the presence of tertiary organic bases such as triethylamine, pyridine, dimethylaniline or hexahydro-dimethylaniline at temperatures between room temperature and about 140.degree. C., preferably 60 to 130.degree. the Acylamino compounds isolated in the usual way can be used in inert organic solvents such as o-dichlorobenzene, 1,2, Ί-trichlorobenzene, Trichlorobenzene mixtures, o (-chloronaphthalene or methyl benzoate, in the presence of catalytic amounts of acidic catalysts, such as p-toluenesulfonic acid, zinc chloride, Polyphosphoric acid or boric acid at temperatures of about 180 ° to about 250 ° C, preferably 200 to 220 ° C, below Elimination of water to be cyclized to benzoxazoles.

40988 ^ / 1367

233HU '

AIc o-Amino-phonoio can already be heard at the first demonstration demonstration in Frago.

As Zirat acids of the general Fortael (5) the f oil can send, vrerdcn:

HOOC-CH =

QCIL OCH ₃
HO OC- CK "= C! I- / O \ - C CO CH ₃

CH, -CH ₇

^ ₃

CH ₂ -CHg- CH ₃

nooc - cii: - cii- (0 / - HOOC-CII-CH

CH _n -COOOH.

-COOCIL

) - CII ₂ - CH ₂ - 0 - CH ₂ - CH ₃

HOOC-CH = CH- (O ) - Ci? Q-CHp -CLV-O-CIL, -CiI-H00C-CH = - CII- (O / ~ ^CC0CII 2 " ^CH 2 - ° - ^Cii 2

OCH.

HOX-CH-CH

δ -CN HOOC-CH = CH- (O

fl
NII-C-CIL

C ₂ H ₅

CIi

H ₃ CO

) CIL

} I00C-CH = .- CII- / O / - ^CIr

H ₅ C

H-C-CIL

cn

H?

KCO ₀ K ₀

HOOC-CK.-CI

O)-

A09884 / 1367

233U44

The reaction products of the above processes can Of course, other known conversions can be carried out, e.g. starting from carboxy-containing molecules lead to compounds with functionally modified carboxy groups or the conversion of such groups into other groups of this type or in the free acids or their salts.

Furthermore, for example, chloromethyl groups can be introduced or methyl groups can be oxidized in a known manner. as well Successful Halpgenationen and further implementations of the introduced Halogen atoms, e.g. the exchange of chlorine or bromine for the -C = N group.

Those substituted by acylamino groups in the styryl radical (X = N-acyl) compounds according to the invention can also be obtained in this way that one compounds of the general formula (6)

CH = CH

(6)

in which R

3
R ^ and Y those given in the formula (1)

Have meaning, for example reduced with etched iron or other metallic reducing agents in the presence of water-miscible organic solvents to the primary amino compounds (in formula (1) X = NH ₀ ) and these are reacted in the usual manner with acylating agents.

The new compounds according to the invention have due to their Fluoreszenzvormögens a wide field of application. Above all they serve for the optical brightening of the most diverse synthetic, semi-synthetic and natural organic high molecular weight materials.

I * 0 9 8 bu I 1 3 6 7

233UU

Among synthetic organic high molecular materials are polymerization, polycondensation and polyaddition products as well as their aftertreatment products, ζ B:

Polymers based on &, ß-unsaturated carboxylic acids, from Olefin hydrocarbons or halogenated hydrocarbons (such as polyolefins, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, etc.),

Polycondensates based on bi- or polyfunctional compounds with condensable groups, their homo- and mixed condensation products (such as polyester, polyamides, maleinate resins, Polycarbonates, silicone resins, etc.),

Polyaddition products, such as crosslinked or uncrosslinked Polyurethanes and epoxy resins.

Cellulose esters, for example, are semisynthetic organic materials and ethers, nitrocellulose, regenerated cellulose and casein-based plastics.

Natural organic materials that can be optically brightened include protein materials such as wool, silk and leather; Cellulosic materials like cotton, paper, wood pulp in finely divided form; also rubber, gutta-percha or balata.

The organic materials to be optically brightened can be used in the various processing states (raw materials, semi-finished products or finished products), e.g. as plates, sheets, moldings, chips, granulates, foams; Films, Foils, lacquers, tapes; Threads, fibers e.g. in the form of endless threads, staple fibers, flakes, yarns, hanks, twisted yarns, Nonwovens, felts, wadding, textile fabrics, composites and knitted; also as powders, putties, pastes, waxes, adhesives and fillers, etc.

/ 13

40988 4/1367

The new optical brighteners can of course also be used wherever organic materials are used type indicated above can be combined with inorganic materials in some form.

However, the compounds of the invention are preferred for used for the optical brightening of fibers, textiles and plastics.

The water-soluble cationic compounds according to the invention are particularly suitable for the optical brightening of homopolymers and copolymers of acrylonitrile, in particular of the commercially available copolymers with a minimum content of about 85 % acrylonitrile units.

Water-insoluble compounds according to the invention, which are particularly suitable for the optical brightening of polyester and Polyamide fibers, as well as regenerated cellulose fibers and equipped with synthetic resins for the purpose of easy care Cellulose and regenerated cellulose fibers are suitable alone as well as in a mixture with synthetic fibers, can be dissolved in organic Solvents are used or in aqueous dispersion, advantageously with the aid of dispersants. Soaps, polyglycol ethers, which differ from fatty alcohols, fatty amines or alkylphenols derive cellulose sulfite waste liquors or condensation products of optionally alkylated naphthalenesulfonic acids with formaldehyde in question.

The compounds of the invention are distinguished in particular by the fact that they can be used in the presence of oxidative and reductive bleaching agents, such as hydrogen peroxide, sodium hypochlorite and sodium chlorite, and sodium dithionite, without impairing the optical brightening · The optical brightening agent may with other finishing agents for the purpose of effect of improvement or Simplification of procedures can be combined. Such tools are

/ 14

409884/1367

e.g. retarders, carriers, dispersants, plasticizers, oleophobic and hydrophobic compounds, preparation agents, Emulsifiers or detergents and wetting agents. In addition, points the lightened fiber material, particularly polyester of the polyethylene glycol terephthalate type, is excellent Lightfastness. Highly brilliant, red-tinged to green-tinged lightening effects with an extraordinarily high degree of whiteness are achieved.

Because the compounds of the formula (1) according to the invention also with the exhaust and thermosol processes - as described below - in almost all temperature ranges between 60 and 240 C can be used and on the Most important fibers produce brilliant effects, they can be seen as universally applicable.

Particularly good lightening effects are sometimes also obtained when the compounds according to the invention are combined with other optical brighteners. Such combinations are in particular then of interest if you want to achieve nuance shifts in the lightening effects. Excellent effects will be e.g. in the combination of the compounds according to the invention with known benzoxazole brighteners of the following constitutions achieved:

R R

where R stands for identical or different substituents in the series lower alkyl, alkoxy, carboalkoxy, carboxy groups or hydrogen or halogen, especially chlorine, atoms.

Brighteners of the coumarin type, naphthotriazole type or distyrylarenes are also very suitable as mixing components.

/ 15

409884/1367

The lightening of the fiber material with the aqueous or possibly organic brightener liquor takes place either in the exhaust process at temperatures of preferably about 60 to 150 C or under thermosoling conditions, the textile material with the brightener solution or dispersion by impregnation and Squeezing or spraying to a moisture content of about 50 to 120%, based on the dry weight of the goods, is brought. The textile material is then subjected to a temperature treatment for about 10 to about 300 seconds, preferably subjected to dry heat at about 120 to about 2 ^ 0 C. This thermosoling process can also be used with other finishing operations, e.g. finishing with synthetic resins for the purpose of the ease of care. The inventive Brighteners are characterized by high resistance to the usual catalysts and additives such as magnesium chloride or zinc nitrate or polyethylene dispersions.

The 2-styryl-benzoxazoles according to the invention of the general Detergents can also be added to formula (1). These can contain the usual fillers and auxiliaries, such as alkali silicates, Alkali polyphosphates and polymetaphosphates, alkali borates, alkali salts of carboxymethyl cellulose, foam stabilizers, such as alkanolamides of higher fatty acids or complexing agents such as soluble salts of ethylenediaminetetraacetic acid or diethylenetriaminepentaacetic acid, as well as chemical bleaching agents such as perborates or percarbonates. Very good results are also obtained with perborate detergents in the presence of perborate activators. Even the usual Disinfectants used in detergents impair the healing effect of the compounds according to the invention not.

Furthermore, the compounds according to the invention can have high molecular weight organic materials before or during their deformation. will. For example, you can use them during manufacture of films, foils, tapes or form bodies

/ 16

40983W13R7

Add pressing dimensions or in the spinning mass before spinning to solve. Suitable compounds can also be used before the polycondensation or polymerization, as in the case of polyamide-6, polyamide-6,6 or linear polyesters of the polyethylene glycol terephthalate type, the low molecular weight starting materials be added

Compounds according to the invention, which by or preferably two carboxy or carboalkoxy groups are substituted, linear polyester molecules and synthetic polyamides by an ester or amide bond, if under suitable conditions these materials or preferably their Starting materials are added. In this way, they draw brighteners anchored in the substrate through a chemical bond is characterized by an extremely high resistance to sublimation and solvents.

Olefinically unsaturated compounds according to the invention which, in addition to the fluorescent system, have at least one contain polymerizable olefinic double bond, can be used for the production of fluorescent polymers or polymer mixtures by maintaining the fluorescent system as such or in a mixture with other monomeric or polymeric vinyl compounds polymerized. These fluorescent polymers can then be mixed with non-fluorescent polymers been. Such optically brightened polymers are characterized by a high degree of whiteness. In addition, is due the chemical anchoring of the brightener molecules with the polymers ensures high resistance to sublimation and solvents.

The amount of the compounds to be used according to the invention general formula (1), based on the material to be optically brightened, can be used depending on the area of application and the desired effect fluctuate within wide limits. It can be done through simple advance

/ 17

A09884 / 1367

233U44

search can be easily determined and is generally between about 0.01 and about 2 %,

The following examples explain the invention in more detail. The temperatures are given in degrees Celsius «

/ 18th

409884/1367

1 t

-S

-Λ

233U44

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C "\ CO CO co p \ η co

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ν * τ "

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§ δ

iS G B (S IiI

8 B Β'δ ^

CM CM CV CM CM OS

M C

CM3 ~ <1 m W M IOO

t> ι ι

SftCQ "I O

f o ^ ο ο

egg

Β "^

co 5

B S 444 ^ 444 4

η η V ¹ Pi η pi co co '«ο

S B B 8 g 8 B 5 B

Office

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MKKHHHHUMHRHMHHM MH

HM K I

β "β" β β "β" β "β" ιΓ ιΓβ "β" 8 "V

H M

409884/1367

example 1

1915 S 2-chloromethyl-5,6-dimethyl-benzoxazole, 56 ml of triethyl phosphite and 8k ml of dimethylformamide (hereinafter: OMF) are heated to 120 to 150 ° C. for k hours. The excess triethyl phosphite and most of the DMP are then distilled off in vacuo. The residue from evaporation of 2- (diethoxyphosphonomethyl) -5,6-dimethyl-benzoxazole is mixed with 16.1 g of 3-methoxy-4-cyano-benzaldehyde and 100 ml of DMF and this solution is put into a suspension at 25 to 30 ° C 6.1 g sodium hydroxide in 250 ml DMF. After stirring at 25 ^° C. for 20 minutes, the reaction mixture is stirred into 2 l of water and immediately adjusted to pH 6 with hydrochloric acid. The yellowish precipitate is filtered off with suction, washed and then recrystallized from 600 ml of butanol. Mp 227-228 ° C; the yield is 17.5 g of compound (104).

Example 2

In order to obtain 2- (3'-methoxy-4 ¹ -carbomethoxy-styryl) -5,6-dimethyl-benzoxazole, the process of Example 1 is repeated, but instead of 3-methoxy-d-cyano-benzaldehyde, 1 ° - »^ S 3-methoxy-4-carbomethoxy-benzaldehyde used. After recrystallization from 330 ml of butanol, 20 g of the verb. (I09); mp. 198.5 to receive I99,5 ⁰ C.

Example 3

In the same way as in Example 1, the corresponding phosphono compound is obtained from 16.6 g of 2-chloromethylbenzoxazole, which on condensation with 19.4 g of 3-methoxy-4-carbomethoxybenzaldehyde gives 21.6 g of crude product (101). By stirring with sodium carbonate solution and recrystallization from isopropanol, 119.5 give the compound (101) in crystals of mp. 120.5 to ⁰ C.

/ 20 40988W1367

Example 4

To dissolve 23.5 g of sodium in 1 l of abs. 151 g of m-cresotinic acid amide are added to ethanol. In addition, one adds 139 S n-Butyl bromide is added, the mixture boils under for 14 hours Reflux, distilled off part of the ethanol and diluted with 2.5 l of water. The precipitated product is suctioned off and washed with water. 188 g of 2-butoxy-4-methylbenzamide are obtained as a colorless crystal mass of crude melting point. 132 to 135 C.

187 g of 2-butoxy-4-methylbenzamide are heated to 80 to 100 ° C. with 350 ml of phosphorus oxychloride for 40 minutes. The reaction mixture is broken down with 4 kg of ice water. The separated colorless crystalline material is filtered off, washed with water and after drying on the oil pump distilled (Kp _o _ 134 to

ο *

I36 C). 161.5 g of 2-butoxy-4-methyl-benzonitrile are obtained in this way (Ep 30 ° C).

l6O, 7 g of 2-butoxy-4-methyl-benzonitrile g in 1 1 of carbon tetrachloride with N-bromosuccinimide and 1.9 15315 S azoisobutyronitrile under UV irradiation 30 minutes 76 ⁰ C heated. Succinimide is filtered off with suction at 60 ° C. and the filtrate is evaporated to dryness. 228 g of 2-butoxy-4-broramethylbenzonitrile are obtained.

228 g of the bromomethyl compound are dissolved in 385 ml of glacial acetic acid and refluxed with 38O g of water and 136 g of hexamethylenetetramine for 1 hour. 100 ml of hydrochloric acid are added dropwise to the boiling solution to adjust the pH to 3. After a further 15 minutes of boiling time, the reaction mixture is diluted with 1.7 l of water. The oily deposited 3-butoxy-4-cyano-benzaldehyde is obtained as a viscous oil by shaking with chloroform and evaporation (195 g of approx. 49 % pure content).

195 g of crude 3-n-butoxy-4-cyano-benzaldehyde are mixed with 200 ml Pyridine and 89 g of malonic acid were heated to 75 to 110 ° C. for 6 hours. The reaction mixture is stirred into water and hydrochloric acid / 21

409884/1367

and isolates the crude 3-butoxy-4-cyano-cinnamic acid by suction filtration and washing with water. As a result of accidents from sodium carbonate solution after treatment with activated carbon with hydrochloric acid, 66 g of 3-n-butoxy - ** - cyanocinnamic acid are obtained as a colorless powder with a melting point of 2Jk up to 237 ° C.

26.4 g of 3-n-butoxy-4-cyano-cinnamic acid are converted into the acid chloride with 8.2 ml of thionyl chloride in 100 ml of toluene and then with a mixture of 14.5 g of 4-amino-5-hydroxy-1,2 -xylene, I3.0 ml of N, N-dimethylaniline and 80 ml of dioxane reacted. After five hours of heating at 80 ° C., the reaction mixture is freed from toluene with steam. The precipitated acylation product is filtered off with suction and washed with dilute hydrochloric acid and water. One obtains 37 g of olive green powder of melting point 152-156 · ⁰ C (after purification I60 to L6L ° C).

37 g of acylation product are heated under nitrogen in 180 ml of trichlorobenzene with 0.3 g of zinc chloride to an internal temperature of 205 ° to 215 ° C. for 70 minutes. 120 ml of trichlorobenzene are distilled off. The residue is allowed to crystallize with the addition of 80 ml of diisopropyl ether. 23.3 g of benzoxazole are isolated by suction. After recrystallization from toluene and butanol, yellow long-fiber crystals with a melting point of 186 to 186.5 ° C. are obtained: 2- (3'-n-butoxy-4 ¹ -cyanostyryl) -5,6-dimethylbenzoxazole (106 ).

The substances mentioned in the table (IOP, (102), (103), (104), (105), (107) and (109) can be synthesized.

Example 5

To a 75 ° C warm dispersion (partially solution) of 75 g 2- (3-methoxy-4'-carboeethoxy-styryl) -5,6-dimethyl-benzoxazole in 1.5 l of ethanol (95 Sig) gives «to a solution of 21 g of potassium hydroxide in 25 g of water. After 30 minutes of cooking you start Add water and distill off ethanol. The desired

Carboxylic acid (HO) is finally in the heat with 30 ml

/ 22

409884/1367

Acetic acid precipitated; the pale yellow flaky precipitate filtered off with suction and washed with water. 71.1 g of 2- (3'-methoxy-4 ¹ -carboxy-styryl) «5» 6-dimethyl-benzoxazole (110) are obtained in the form of a light yellow powder with a melting point of 243 to 243 _{t of} 5 C.

Example 6

1718 g of 2- (3'-methoxy-4 ¹ -carboxy-styryl) -5,6-dimethyl-benzoxazole (110) are reacted in 150 ml of chlorobenzene with 4.5 ml of thionyl chloride to form the acid chloride. After removing the excess thionyl chloride, 8.8 g of n-butylamine are added. 4-hour heating at 80 C followed by a steam treatment in the presence of hydrochloric acid * from the cooled residue to 20.4 g of crude 2- (3 '-methoxy-'4 ^f butylamino-carbonyl-styryl) -5,6-dimethyl -benzoxazole (112) are sucked off. After recrystallization from butanol and methylene glycol is the mp. At 168-169 ⁰ C.

By reacting the above acid chloride solution with ammonia, the carbonamide (111), with piperidine the piperidide (113) and with ß-Diethylaminoäthylamin obtained the carbonamide (114).

Example 7

27 g of 2- (3'-methoxy-4 ^l -carbomethoxy-styryl) -5,6-dimethylbenzoxazole are reacted in 240 ml of ß-dimethylaminoethanol under reduced pressure at a bath temperature of 100 ° C in the presence of sodium ß-dimethylaminoethylate ( Duration approx. 1 hour). After adding 0.2 ml of glacial acetic acid, the remaining β-dimethylethanol is distilled off in vacuo. On recrystallization from isopropanol and cyclohexane with the addition of activated charcoal and ^{fuller's earth, the evaporation residue gives 22 g of ß-dimethylaminoethyl ether of 2- (3 l} -methoxy-4 ^l -carboxy-etyryl) -5,6-dimethylbenzoxazole (II5) as a yellow crystal powder (mp 117 to II9 C).

Example β

20.1 g of the ß-dimethylaminoethyl described in Example 7

409884/1367

-23- 2331U4

esters (115) are mixed with 6.9 g of dimethyl sulfate in 180 ml of ethyl acetate and heated briefly to 60.degree. After suction and Washing with ethyl acetate gives 20 g of water-soluble quaternary salt (118) as a light yellow powder.

In the same way, dimethyl sulfate is also added to the compound (114) and the quaternary salt (119) is obtained.

Example 9

28.5 g of 3-acetamino-4-carbethoxy-cinnamic acid (see below) are mixed with 8.2 ml of thionyl chloride in 100 ml of chlorobenzene converted into acid chloride. This becomes a mixture of 13.5 g of 5-amino-4-hydroxy-1,2-xylene, 12.4 g of Ν, Ν-dimethylaniline and 80 ml of dioxane added at 80 ° C. After 4 hours of heating at 80 ° C., steam distillation is carried out and the acylation product is filtered off with suction in the residue. The acylamino compound obtained is stirred for cleaning with methanol, suction filtered again and then dried. The mp is included after cleaning 199 to 202 ° C.

34 g of acylation product are heated for 75 minutes under nitrogen in 120 ml of trichlorobenzene in the presence of 0.4 g of zinc chloride at 210 to 215 ° C. After the main amount of trichlorobenzene Has been distilled off in vacuo, 100 ml of methanol are added at about 100.degree. At 25 ° C, 20.1 g of light gray Crystals are sucked off. Obtained by recrystallization from chlorobenzene and methylglycol (with the addition of fuller's earth) one 2- (3 · acetamino - ^ - carbethoxy-styryl) -5,6-dimethyl-benzoxazole (116) as pale yellow crystals with a melting point of 238 to 239 ° C.

The required 3 ^< -acetamino-4-carbethoxycinnamic acid is synthesized in the following way: 196 g of ethyl 4-nitro-2-aminobenzoate are heated with 170 ml of acetic anhydride and 200 ml of glacial acetic acid (with the addition of 2 drops of sulfuric acid) for 30 minutes and then stirred into water. The ethyl 4-nitro-2-acetaminobenzoate is filtered off with suction, dried (yield: 220 g) and

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recrystallized from 1.5 l of ethanol (188 g of m.p. 110 to 112 ° C). By catalytic reduction with 4 g Ni catalyst in ethanol and recrystallization of the crude product from toluene, 110 g of ethyl 4-amino-2-acetaminobenzoate are obtained as large colorless crystals from shrap. 167 to 168 ° C.

To prepare 3-acetamino-4-carbethoxycinnamic acid, 110.5 g of ethyl 4-amino-2-acetaminobenzoate are mixed with 150 ml of 30 % hydrochloric acid and 400 ml of water at about 5 ° C. with 100 ml of 5N sodium nitrite Solution diazotized. This diazonium salt solution is stirred at about 17 ° C. in a mixture of 130 g of sodium acetate trihydrate in 300 ml of water, 22 g of copper (II) chloride dihydrate in 65 ml of water and 42 g of acrylic acid, in which 4, 5 g of copper (I) chloride are suspended * The brown-green mass formed during the reaction is isolated, washed and extracted with 0.5 l 10% sodium carbonate solution. After treatment with activated charcoal and kieselguhr, the clarified extracts are run into hydrochloric acid and 29.4 g of colorless 3-acetate-nino-4-carbethoxyciric acid are obtained. A sample recrystallized from glacial acetic acid has a melting point of up to 223 ° C.

Example 10

2-Nitro-4-methyl-benzoic acid ethyl ester is according to Organ * Synth., Coil. Vol. II, 441 with chromic acid in acetic anhydride-acetic acid oxidized to the diacetate of 3-nitro-4-carbethoxy-benzaldehyde. The free aldehyde obtained by saponification with sulfuric acid is then heated with malonic acid for seven hours in Pyridine (see. Example 4) to 3-nitro-4-carbethoxycinnamic acid (Mp. 216 to 217 ° C) implemented.

4 l, 8 g of 3-nitro-4-carbethoxycinnamic acid (95 % ± g) are converted into cinnamic acid chloride with 12.3 ml of thionyl chloride in 150 ml of toluene, the toluene solution of which is then mixed with 21.7 g of 5-amino-4- hydroxy-l, 2-xylene reacted in 100 ml of dioxane and 11.5 ml of N, N-dimethylaniline. The after a steam distillation in

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Residue incurred orange leaflets of the acylamino compound (Schrap. 237-238 ⁰ C) is cyclized by 90 minutes in 200 ml .Erhitzen trichlorobenzene with 0.3 g of cinnamoyl chloride at about 210 C. After distilling be trichlorobenzene at about 100 ° C 250 ml of ethanol stirred in. By suction at 20 ° C to 47.9 g of crystals gets graustichige of 2- (3-nitro-4 · ¹ -carbäthoxy-styryl) -5,6-dimethylbenzoxazole (mp. I73 to 176 ⁰ C).

18.3 g of the nitro compound are dissolved in 1 ^ 0 ml of methyl glycol, with 5.8 g of water, 1.8 g of glacial acetic acid and 20 g of iron powder Heated for 6 hours at 140 ° C bath temperature. Another 200 ml of methylglycol are added and the iron slurry is filtered hot away. By evaporating the piltrate, 16 g of 2- (3 * -amino-4'-carbethoxy-styryl) -5,6-dimethyl-benzoxazole (melting point I71 to 172 ° C., greenish-yellow crystals).

With benzoyl chloride in dioxane and pyridine it is in high yield 2- (3'-Benzoylamino-4'-carbethoxy-styryl) -5,6-dimethyl-benzoxazole (II7) obtained from melting point 219 to 221 ° C. as crystal powder.

i
Example 11

A fabric made of polyethylene glycol terephthalate was treated with a liquor which contained 1 g / l of the optical brightener of the formula (105) in dispersed form. The textile material impregnated in this way was squeezed between rollers until it contained only 80 % of its dry weight in liquid, and then subjected to a hot air treatment at 190 ^° C. for 30 seconds. After the treatment, the fabric exhibited an excellent degree of whiteness compared to the untreated material.

The compounds (102), (104), (106), (107) and (109) can be used in approximately the same way.

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Example 12

A knitted fabric made of polyethylene glycol terephthalate was impregnated with a liquor made of perchlorethylene which, in dissolved form, contained 1 g / l of the optical brightener of the formula (10 * 0. The textile material treated in this way was squeezed between rollers until it was only 80 % of its dry weight in liquid and then exposed to a hot air treatment at 180 ° C.

Compared to the raw material, this treatment gives an excellent shade of white with very good lightfastness. The compounds (103) »(105), (106), (107) and (108) can be used in approximately the same way.

Example 13

A yarn made of polyethylene glycol terephthalate was treated in a liquor ratio of 1:25 in a liquor which contained 0.1 % of the optical brightener of the formula (109) and 1.2 g / l sodium chlorite. The pH of the liquor was adjusted to pH 3 »5 with formic acid. The cold liquor was ^{heated to 85 °} C. within 30 minutes and then kept at this temperature for 30 minutes. After renewed heating to 120 ° C., the goods were treated for a further 30 minutes under these conditions. After rinsing and drying, the yarn exhibited excellent whiteness.

The inventive Compounds (101), (102), (10Ό, (105), (106), (107), Uo3) and (110) can be used.

example ik

A fabric made of polyethylene glycol terephthalate was in a liquor ratio of 1:20 with a wash liquor that 6 g / l a detergent containing the following composition, treated

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233HU

50 % sodium tripolyphosphate 6 % sodium metasilicate

k% carboxymethyl cellulose, containing salt, viscosity in 5-star solution at 20 ° C 1500 cP (Höppler viscometer)

10 % adduct of 8 moles of ethylene oxide with technical isotridecyl alcohol (from the oxo synthesis)

0.05 # optical brightener of the formula (110) remainder to 100 tf: Glauber's salt and water

The fabric was washed at 60 ° C. for 10 minutes, then rinsed and dried. This treatment was up to 10 times repeated. The fabric showed a clear increase in whiteness compared to the only prewashed material (without brightener).

With the same degree of whiteness, the compounds (103), (104) and (105) can be used *

Example 15

A knitted fabric made of polyamide 6 was treated in a ratio of 1:30 with a liquor which contained 0.2 % of the optical brightener of the formula (104). The pH of the liquor was adjusted to k with oxalic acid. The cold liquor was slowly heated to boiling temperature and the substrate was treated therein for 30 minutes. The goods were then rinsed and dried. A very strong improvement in the degree of whiteness is obtained compared with the raw material.

Instead of the connection (10 * t), the connections (109), (111) and (112) can also be used.

Example 16

A tissue made of cellulose-2 1/2 acetate was after a conventional pre-wash in a ratio of 1:20 on the reel skid

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a liquor treated, the 0.2% (based on the weight of the Goods) of the compound (10 * 0. The fabric was treated in this solution for 45 minutes at 80 ° C and then as Usually rinsed and dried. The material showed a significant improvement in whiteness. Instead of the connection (104) The connections can be as successful as possible (102), (105) and (112) can be used.

Example 1?

In each case 50 g of bleached Baumwo11 jerseys were given to one Plotting ratio of 1:20 treated with aqueous liquors which, based on the weight of the goods, are composed as follows was:

0.25 % of the compound (110) 5.0 g / l Glauber's salt

2.0 g / l of a commercially available plasticizer of the ethanolamine ester type of a technical long-chain fatty acid (on average C * <■) .

The treatment was started below 40 ° C, the temperature within 15 minutes of bringing in the goods 60 C and treated at this temperature for a further 30 minutes.

After this treatment, the goods were dried in the usual way.

An excellent degree of whiteness was obtained. The compounds (102), (1O4) and (112) can be used.

Example 18

A fabric made of polyacrylonitrile fibers is treated in a ratio of 1:20 with a liquor containing 1 g / l sodium chlorite

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-29- 2331U4

and contains 0.2% of the compound (II9) in dispersed form. The pH of the liquor is adjusted to 3.5 with sulfuric acid. The material is bleached for 1 hour at 80 ° C., heated to 100 ° C. in 20 minutes and the material is treated under these conditions for 30 minutes. It is then rinsed and dried in the usual way.

Also with the compounds (119) _f (H *) and (II8) an excellently bleached and optically brightened product is obtained.

/ 30 409884/1367

Claims (1)

HOE 73 / F LTo Patent claims: 1. Compounds of the formula CH = CH R ' 1 2
in which R and R are hydrogen or halogen atoms or a lower alkyl, lower alkoxy, phenyl or cycloalkyl group with k to 8 carbon atoms or R and 2
R together is an alkylene radical with 3 or k carbon atoms or a fused benzene ring, R a hydrogen or halogen atom or a lower alkyl or alkoxy group, X a lower alkoxy, acyloxy or acylamino group optionally substituted by non-chroraophoric radicals and Y an optionally functionally modified carboxy group or a lower alkanoyl group. 1 2 2. Compounds according to claim 1, in which R and R represent hydrogen or chlorine atoms, a _{lower alkyl group optionally substituted by a carboxy, lower carboalkoxy t} lower alkoxy, hydroxy or phenyl group, a cyclohexyl, lower alkoxy or a phenyl group 1 2
or R and R together are an alkylene radical having 3 or 4 carbon atoms or a fused-on benzene ring, R is a hydrogen or chlorine atom or a lower alkyl or alkoxy group, X is a group of the formula .0-A-Z or -G-Ac 409884/1367 mean in which A is a lower alkylene group, Z for a hydrogen or chloratora, a hydroxy, lower alkoxy, lower carboalkoxy, lower dialkylamino, trialkyl lower ammonium, carboxy or cyano group, G for an oxygen atom or an -NH group and Ac for one optionally by a chlorine atom, a lower alkoxy, lower dialkylamino or lower trialkylmonium group substituted lower alkanoyl or the benzoyl radical, and Y is a cyano group or a radical of the formulas -COOM, COOR, -C ^ ς / ·, -C ^ _ (■ ^ NR ⁵ R ^ NH-NR ⁵ R 7th
or -CO-R means in which M is a colorless cation, R is a group of the formula -Q-T means in which Q is a lower alkylene or phenylene radical and T is a hydrogen atom, a lower one Alkoxy, hydroxy, lower dialkylamino or lower trialkylammonium group represent, L stands for an oxygen or sulfur atom, R and R for hydrogen atoms, lower Alkyl groups, substituted by lower alkoxy, hydroxy, lower dialkylamino or lower trialkylammonium groups 5 6 tuted lower alkyl groups or R and R together with the nitrogen atom contain a hydrogenated, 5- or 6-membered one, optionally containing an oxygen atom or another nitrogen atom *
Alkyl group means 7 represent a ring containing a material atom and R is a lower one 1 2 3. Compounds according to claim 1, in which R and R are hydrogen or chlorine atoms, methyl or ethyl groups or together a trimethylene or tetrainothylene group or a ChI 3
condensed benzene ring, R a hydrogen or chlorine 40988W 1 367 atom or a methyl or methoxy group, X a lower one Alkoxy group or a through a lower alkoxy or Ethoxy group substituted by hydroxyl group, one optionally lower alkanoylamino substituted by a chlorine atom, Benzoylamino ·, lower alkanoyloxy or lenaoyloxy group and Y stands for a cyano, carboxy, lower carboalkoxy odor carboiiainidgruppe, the carboalkoxy radical by hydroxy, lower dialkylamino or lower trialkylaramonium radicals and the carbonamide nitrogen lower alkyl groups, which in turn are replaced by hydroxy, lower Dialkylamino or lower trialkylaramonium groups substituted can be, can be substituted, these lower alkyl groups also together form a G-membered, ge & e optionally can represent a ring interrupted by an oxygen or further nitrogen atom. 1 2 k. Compounds according to claim 1, in which R and R are in the 5- or 6-position and R in the 6'-position. 5. A method for the production of pre-bindings according to claim 1, characterized in that phosphono compounds of the general formula (2) (2) 1 2 '
in which R and R have the meanings given above 8 9
and R and R denote identical or different alkyl, cycloalkyl or phenyl radicals optionally bonded to the P atom via an O atom, with substituted benzaldehydes of the general formula (3) / 33 40988W 1 367 233UU (3) in which R, X and Y are those given above. Have meaning using alkaline condensing agents condensed in inert organic solvents * 6. Process for the preparation of compounds according to claim 1, characterized in that substituted ο-aminophenols of the general formula (k) OH 1 2 in which R and R have the meanings given above, with the acid halides of the cinnamic acids of the formula (5) HOOC-CH = CH - <( nY (5) in which R, X and Y have the abovementioned meaning, converts them to the corresponding acylamino compounds and these cyclized in the presence of acidic condensing agents at temperatures between about 180 and about 250 C with elimination of water. / 34 409884/1367 233UU 7. Use of the compounds according to claim 1 as optical brighteners. 40988A / 1367