DE2320528A1 - PROCESS FOR THE PRODUCTION OF ACETYLENES - Google Patents

Description

FARBWERKE HOECHST AG formerly Master Lucius & Brüning

File number:

Date: April 10, 1973 Dr. Kl / stl

HOE 73 / F 110

A process for Ji ersteilung of acetylenes

It has been found that acetylenes of the formula I

r-

A-C = C-I-X - C ac C + -

(I)

in which A is an aromatic carbocyclic or heterocyclic Radical or a functionally modified carboxy group, B an aro-. matic carbocyclic or heterocyclic radical and X is a is a divalent link that has at least one aromatic contains carbocyclic or heterocyclic radical, and η is zero or 1, can be prepared if compounds of the formula II

A -

(H)

in which A, B, X and η have the meanings given above and R is a lower alkyl or an optionally substituted phenyl group, in an inert solvent with a Base implements.

Under an aromatic carbocyclic radical are in particular To understand residues derived from benzene, naphthalene, anthracene, phenanthrene and pyrene. As stated below, a large number of compounds of the formula II are known or accessible which are unsubstituted or mono- or multiply

### 048/1104

contain substituted aromatic radicals and the invention Implementation. An aromatic heterocyclic radical is to be understood as meaning, in particular, radicals derived from furan, thiophene, Pyridine, 1,3, ^ - oxdiazole, 1,2,3-triazole, benzofuran, benzoxazole, Benzimidazole, Benzthiazole and the corresponding naphtho analogs of the mentioned benzo-pinion-ring heterocycles, furthermore from indole, Derive quinoline and isoquinoline. These radicals can also be substituted one or more times.

Halogen, preferably, are particularly preferred as substituents Chlorine, bromine or fluorine atoms, lower alkyl or alkoxy groups, optionally functionally modified carboxy or Sulfo groups, nitro, amino, mono and dialky! Amino groups with preferably lower alkyl groups, acylaminoy preferably lower ones Alkanoy! Amino groups and optionally esterified hydroxyl groups preferably lower alkanoyloxy groups.

Insofar as the expression “lower” or “low molecular weight” is used in connection with aliphatic radicals, radicals with 1 to ¹ J carbon atoms are intended to be used in particular.

Under a functionally altered or modified carboxy group such derivatives should be understood where from one carbon atom emanates three bonds to heteroatoms, like in the nitrile group, and further in particular compounds that contain an oxo group that bonds to a heteroatom, as in ester, amide and acid halide groups. In the foreground of interest here are ester groups of the formula

- CO - OR ¹

in which R is a lower alkyl or a phenyl group, which in turn is replaced by halogen, especially chlorine atoms, hydroxy, lower alkoxy and especially amino, mono and dialky amino groups and trialkylammonium groups are substituted, the Alkyl substituents on the nitrogen atom are preferably 1 to 4 carbon contain atoms, furthermore amide groups of the formula

409845/1104

-CO - HR ² R ³

in which R and R are hydrogen atoms or lower alkyl groups mean.

In analogy to this are under a functionally modified Sulpho group, in particular sulphonic acid esters and amides Formulas

-SO ₂ -OR ¹ 'and -SO ₂ -NR ² R ³

to understand in which R ₁ R and R ^- ^ the above meaning! to have. Such functionally modified groups can also be subsequently converted into one another or also into the. convert free acids.

Under a divalent link that is at least one aromatic contains carbocyclic or heterocyclic radical, are in line with the above, in particular groups of the formulas ".

- <Q- - {3-TV- j ~ \ - ™ ~

/ ~ \ _ NN NN - ^ S- ^ "ι -AjL-- or J { ; 1

I ⁴

to understand, which can optionally be combined. R stands for a lower alkyl or the phenyl group.

As a radical R, the splitting off of the sulfone group as sulfination do not prevent aliphatic and aromatic carbocyclic Radicals are preferred, such as, in particular, lower alkyl groups or

409845/1104

benenfalis once or twice, in particular by halogen, in particular Chlorine or bromine atoms., Nitro, lower alkoxy or lower Alkanoy! Amino groups substituted phenyl groups. Especially, preferred R radicals are methyl, ethyl, phenyl, 3- or iJ-nitrophenyl, 2-, 3- or. 4-chloro- or bromophenyl, i | ~ acetaminophenyl, 2-, 3-bath Ij-methoxyphenyl 'or S

As a solvent which is inert under the reaction conditions for the inventive Reaction, protic and aprotic, preferably polar solvents can be used, especially ethers such as diethyl ether, Diisopropyl ether, tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, Ethyl ^ (glycol monomethyl ether, monoethyl ether or glycols "Diine thy lather, nitriles such as acetonitrile, propionitrile or higher Nitriles, amides such as dimethylformamide, dimethylacetamide, diethylacetmide, Hexamethyl phosphoric acid trisamide or tetramethyl urea, also dimethyl sulfoxide, but also tertiary alcohols such as tert. Butanol.

The amount of solvent is not critical. It just has to be sufficient so that the system remains easy to stir. The starting and end products can therefore be in dissolved and / or suspended form. Generally the amount of solvent is about 1 up to about 30 parts by weight, based on the vinyl sulfone compound of Formula II. ■ "" ■

As inorganic or organic bases for splitting off des-sulfinate can be used, for example: alkali and alkaline earth hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide or barium hydroxide, and also alkali or alkaline earth metal hydrides such as Sodium hydride, alkali amides such as sodium amide, sodium methyl acetamide, Alkali, alkaline earth or aluminum alcoholates such as potassium tert-butoxide, Sodium methylate, sodium ethylate or aluminum ethylate.

The bases are generally used in approximately equivalent amounts, excesses of up to about 20 %, preferably about 5 to about 10 %, being possible. To suppress side reactions, it is also possible to work with a base deficit, dispensing with complete conversion. - . _}

409845/1

The reaction temperature is selected according to the reactivity of the starting compound and sensitivity of the resulting acetylene derivative in the range of about - 30 to about + 15O ⁰ C, preferably from 0 to about 120 ° C. The duration of the reaction depends on the reactivity of the vinyl sulfone compounds and the reaction temperature chosen, it is between a few minutes and several days.

The starting compounds of the formula II are known or according to known methods (G. Jones "The Knoevenagel Reaction" in "Organic Reactions Vol. Ijj, John Wiley & Sons Inc. New York, London, Sidney 1967, p. 204 ff., Especially p. 257) accessible, for example from CH-acidic sulfony compounds and aldehydes according to Reaction equations

OH..

I ^d

C-B

H'

A-C = CH-B

^H 2 °

B-CH

SO

B-C = CH-A

C-A

so,

+ H ₂ O

or when using dialdehydes

A-CH, / ' SO,

H ₂ CB

⁺ f ° 2 R

or when using a disulfone ^ ^υ u η _ χ _ ην η

A-C = CH-X-CH = C-B

^ SO ₉ SO ₉

, 2 _f 2

R R

f ° 2

A-CH = C-X-C = CH-B

R R

409845/1104

- O - '

The unsaturated sulfones are easily in a known manner from the corresponding halomethyl compounds and sulfinates accessible. . It is therefore possible in the course of the invention Sulfinate split off in the manufacturing process, optionally after work-up, again for the synthesis of the intermediate product to use. So there are fiction according to Acetylerß from halogen

. t.

methy! compounds and aldehydes, so from easily in large-scale Degree of accessible basic building blocks, gev / onnen, from which the large Scope of application of the invention results.

The acetylene derivatives formed when the process according to the invention is carried out crystallize out in some cases during or after the end of the reaction and are isolated by suction. In other cases, when using water-soluble solvents for working up, the reaction mixture is diluted with water, weakly acidified - if this is necessary for the formation of a filterable precipitate - and the acetylene derivative is obtained by suction. In the case of water-insoluble! ¹ Solvent itfird the Reaktidnsmischung expediently first with water or dilute acid gewaschenlgHlHHiil and the solvent distilled off in vacuo. The reaction product can be separated from unreacted starting material and residues by recrystallization, chromatography or sublimation in vacuo.

The importance of the process according to the invention is based on its simplicity and, as can be seen from the possible variations and combinations of CH-acidic component and aldehyde component, on its diversity. Thus , according to this process, acetylene derivatives can be produced in a simple manner, which are otherwise only accessible in a complicated way or not at all so far.

The invention therefore also relates to new acetylenes Formula I, where A, B, X and η have the meanings mentioned,

409845/1104

- 7 -
however, if η stands for zero, A is a carboxy or sulfo group optionally functionally modified by halogen, in particular chlorine, bromine or fluorafoins, lower alkyl or alkoxy groups, acyl, especially lower alkanoyl groups, nitro, Amino, lower mono- or dialkylamino groups or acyl, in particular lower alkanoylamino groups, substituted naphthyl groups, an anthryl, phenanthry1 or pyrenyl group or a group of the formula

N-N -

v ■ ■ · ν. / V ~ / ^or \ ₀ /

II 5

in which R has the meaning given above and R- ^ and R Hydrogen or halogen, especially chlorine atoms, lower

5 6

Alkyl or alkoxy groups or phenyl groups or R and R together mean a fused benzene ring,

Y is a group of the formula '_ ..

-CH =, - _{N =} or M'SN '_ τ

in which R 'is a hydrogen atom or a lower alkyl group, which is optionally substituted by a hydroxyl, cyano or phenyl group and T ^ a colorless anion, preferably halide, in particular chloride, bromide or iodide, lower alkyl sulfate, especially methosulfate, or aryl sulfonate, especially phenyl or toluenesulphonate means

Z is a group of the formula

- O -, - S - or -NR ⁸ - -

8 7
in which R has the meanings given for R ',

and B has the meanings mentioned for A and furthermore for an optionally by halogen, in particular chlorine, bromine or Fluorine atoms, lower alkyl or alkoxy groups, optionally

409845/1104

functionally modified carboxy or sulpho groups, acyl, in particular lower alkanoyl groups, nitro, amino, lower mono- or dialkylamino groups or acyl, especially lower alkanoylamino groups substituted phenyl group or a functionally modified carboxy group, in particular a cyano group.

If η stands for 1, A can also mean a phenyl group, optionally substituted as indicated.

The radicals A are, for example:

4-cyanophenyl 2-benzoxazolyl 2- (5-methyl) benzoxazolyl 2- (6-Methy1) -benzoxazoly1 2- (5.6-Dimethyl) -benzoxaz.olyl 2- (5.7-dichloro) -benzoxazoly1 2-naphth £ 1.2-d7oxazoly1 2-naphth ^ 2.3-d? Oxazolyl 2-benzthiazolyl

2-Benzimidazolyl '--.- ·

2- (1-methyl) benzimidazoly1

2- (1,3-dimethyl) benzimidazoly1 2- (5-Phenyl) - £ i.3.i {7-oxadiazolyl or

2-Benzofuryl · ·

and for B

3-chlorophenyl 4-chlorophenyl Ί-methoxycarbonyl-phenyl 3. ¹ 1.5-trimethoxy phenyl, ^ -Cyanophenyl 4-N, N-Dimethylaminopneny1 ¹ I-Ni tr ophenyl 1-naphthyl

409845/1104

- Q - ·

9-anthryl

9-phenanthryl

3-pyrenyl

2-benzofuryl

J | - (2-phenyl) -1.2.3-triazolyl or 2-naphthol ..2-

The invention thus specifically relates, inter alia, to the following compounds:

1-cyano-2- (1-naphthyI) acetylene

1-cyano-2- (3-pyrenyl) acetylene

l-cyano-2- (2-benzofuryl) acetylene, l-cyano-2- (2-riaphth / 1,2-d7oxazolyl) acetylene 1- ( ² J-cyano phenyl) -2- (9-anthryl) acetylene li | -Bis- £ t4-cyanophenyl) äthinyl7-benzene A ^ '- Bis- ^ IT ^ -cyanophenyD-äthinylJ-biphenyl 1- (2-benzoxazolyl) -2- (4-cyanophenyl) acetylene 1- ^ 2- (5.7-Dichlorobenzoxazolyl) _- 7-2- (4-cyanophenyl) acetylene 1- ^ 2- (1-Methy Ib enzimidazoly 1 ) l-2 ~ (^ -cy anopheny 1) -acetylene l- ( 2-naphth ^ 2.3-d7oxazolyl) -2- (4-cyanophenyl) acetylene 1- (2-benzthiazolyl) -2 - (^ - cyanophenyl) acetylene 1.iJ-bis- ^ 2-naphth £ 2.3-d7oxazolyl) -äthinyl7-benzene ft.i | ^| -Bis- £ t2-naphth ^ 2.3 ~ d7oxazolyl) -äthinyl7-biphenyl 1- (2-naphth / 2.3-d7oxazolyl) -2- (3-chlorophenyl) acetylene 1- (2-naphthZ2.3-dJ ^ cazolyl) -2- (4-chlorophenyl) acetylene 1- (2-NaphthZ * 2.3-dJOxasoly 1) -2- (1-naphthy 1) -acetylene 1- (2-Naphth / ^. 3-d7oxazolyl-2- ( I-anthryl) acetylene 1- (2-naphth ^ «3-d7oxazolyl) -2- (3-pyrenyl) acetylene

l ~ (2-Naphth ^ 2.3-d7oxazdlyl) -2-Zi- (2-phenyl-1.2.3-triazolyl) J-acetylen 1- (2-naphth / fl. 2-d7oxazoly 1 ) -2-j? \ - (2-pheny 1-1.2.3-triazoly 1 ^ -acetylene

1- (2-Benzoxazoly1) -2- (3-chloropheny1) acetylene 1- (2-Benzoxasolyl) -2- (ii-chlorophenyl) acetylene 1- C 2-Benzoxazoly 1) -2- (* J-ni nitrophenyl 1) -acety len 1- (2-benzoxazolyl) -2- (3,4,5-trimethoxyphenyl) acetylene l ~ £ 2- (5-phenyl-1.3. ¹ t-oxdiazolyl) J7-2- (l-naphthyl )-acetylene

I-Z2- (5-Pheny 1-1.3. ^I * -oxdiazolyl) J-2- (4-cyanopheny 1) -acetylene

1- (2-Naphthel.2-47oxazoly1) -2- (9-phenanthry1) acetylene

409845/1104

- ίο -

1- (2-Benzoxazolyl) -2- (9-phenanthryl) acetylene ; L-ZT2- (1-methylbenzimidazoly 1) 7-2- (9-phenanthryl) acetylene 1- (2-Benzinddazolyl) -2- (9-phenanthryl) acetylene 1- (2-Benzthiazoly1) -2- (9-phenanthry1) acetylene

l- £ 2- (5-Pfreny 1-1.3.1-oxdiazolyl) J-2 - # - (2-pheny 1-1.2.3- triazoly 1) 1-

acetylene -

1,2-bis (2-naphth £ 1,2-d7oxazolyl) acetylene

1- (2-Benzimidazolyl) -2-if4- (2-phenyl-1,2.3-triazolylJ7-acetylene 1- ^ 2- (1-Me thy lbenzimidazolyl) J-2- / ii- (2-pheny 1-1.2.3 ^ rIaZoIyI), / -

acetylene and 1- (4-cyanophenyl) -2- (9-phenanthryl) acetylene.

The compounds which can be prepared according to the invention show in solid and dissolved state, usually very strong fluorescence. Depending on the absorption and fluorescence behavior, they can be used as fluorescent dyes, Scintillators or for various purposes of photography (sensitizers) or electrophotographic reproduction be used. In particular, however, the new acetylene derivatives used as an optical brightening agent for a wide variety of natural and synthetic organic materials are, preferably for fibers, foils, films and moldings made of polyesters, polyamides, cellulose acetates, polyolefins and / or Polyacetals. This use is also possible in paints.

If the acetylenes contain nitro groups, there are generally no Fluorescence. However, these compounds are suitable as intermediates for the preparation of the corresponding amino compounds, the fluoresce vividly. The nitro group can be reduced here Conversion of known methods into the amino group without the acetylene bond is attacked.

Subsequent connections are of course also possible with these connections Conversions are possible which do not attack the acetylene group, for example the acylation of an amino group or the conversion a functionally converted acid group into another or into the free acid as well as quaternations.

409845/1104

The invention therefore also relates to the use of the new compounds of the formula I as optical brighteners. For this purpose, among the compounds of the formula I which contain only one acetylene bond, preference is given to those in which one of the groups A and B is an aromatic system such as phenyl, cyanophenyl, naphthyl, anthryl, phenanthryl, pyrenyl and the other a heterocyclic system such as benzoxazolyl, methyl or DimethyIbenzoxazolyl, chlorine or. Dichlorobenzoxazolyl, phenylox ^ diazolyl, benzimidazolyl, methyl or dimethylbenzimidazolyl, benzofuryl, benzthiazolyl or naphthoxazolyl mean. ■ -

Among the compounds of the formula I which contain two triple bonds, are those preferred, those as A are one of the just mentioned heterocyclic systems included. .

In particular, the following are suitable as optical brighteners:

1- (9-Anthryl) -2- (2-benzoxazolyl) acetylene 1- (2-Benzoxazdly1) -2- (3-pyreny1) acetylene 1- ( ¹ -Cy anophenyl) -2- £ 2- ( 6 ~ me thy lbenzoxazolyl) 7-acetylene 1- £ 2- (6-methy lbenzoxazoly I) J-2- (3-pyrenyl) acetylene 1- ^ 2- (5.7-dichlorobenzoxazoly 1) ^ - 2- (1 naphthyl) -acety len l- £ 2- (5-phenyl-1.3. ¹ l-oxdiazolyl) _(7-2- (3-pyrenyl) acetylene 1- (2-Benzimidazoly1) -2- (3-pyreny1) -acetylene 1- (2-Benziiaidazolyl) -2- ( ¹ -cyanophenyl) -acetylene < 1- £ 2- (1-Methy lbenziinidazoly1) J-2- (3-pyreney 1) -acetylene 1- (2 -Benzofuryl) -2- (3-pyreny 1) -acetylene 1- (3-Pyreny1) -2- (2-naphth £ i.2-d7oxazoly1) acetylene

1.3-Dime thy l-2- £ "(1-naphthyl) -äthiny XJ -benzimidazolini um-mono-

methyl sulfate

1- (2-Benzofuryl) -2- (4-cyanophenyl) acetylene 1- (3-pyrenyl) -2- (4-cyanophenyl) acetylene 1- (2-Naphthri.2-d7oxazolyl) -2- ( ¹ 1-cyanophenyl) acetylene 1- (2-naphth £ 2.3-47 oxazolyl) -2- (1-naphthyl) acetylene 1- (2-naphthZri.2-d7oxazolyl) -2- (1-naphthyl) acetylene 1- (2-NaphthZ "1.2 ~ 47oxazolyl) -2- (3-chlorophenyl) acetylene 1- (2-Benzoxazolyl) -2- (9-phenanthryl) acetylene

A098A5 / 1104

1- (2-Benzmidazoly1) -2- (9-phenanthry1) acetylene

l-iT2- (l-methylbenzimidazolyl) _< 7-2- (9-phenanthryl) aceJ | ien 1,3-dimethy1-2 -β. 9-phenanthryl) -äthinyl7-benzimidazolinium-mono-

methyl sulfate

l- (2-NaphthZTl.2-d7oxazolyl) ^! ~ 2- (3. ^I l.5-trimethoxyphenyi) -acetylene 1- ^ 2- (5-methylbenzoxazoly1) J -2- (Ί-cyanopheny1) -acetylene 1-Z ~ 2 ~ (5-methylbenzoxazoly 1) 7 -2- (3-pyrenyl) -acetylene 1 ~ £ * 2- (5.6-dimethylbenzoxazoly I) J -2- (4- cy anopheny l) -acetylene li | -Bis- / C2- (5.6-dimethylbenzoxazolyl) -äthinyl7-benzene Ί, Ί '-Bis- £ ί- (5.6-dimethy lbenzoxazoly 1) -äthinyl7-bipheny 1 I-Z2- (5.6-dimethy Ibenzoxazoly 1) 7-2- (3-pyreny 1) -acetylene l .iJ-Bis-Ca-benzthiazolyl-ethhinyD-benzene.

Preferred among these are:.

1- (2-Benzoxazolyl) -2- (3-pyrenyl) acetylene. 1- ^ 2- (6-methylbenzoxazoly1) 7-2- (3-pyrenyl) acetylene 1-Z "2- (5.6-dimethylbenzoxazoly 1) 7-2- (3-pyrenyl) acetylene li | -Bis- £ 2- (5.6-Dimethylbenzoxazolyl) -äthinyl7-benzene 1- ^ 2- (5-Phenyl-1. 3. ^ -oxdiazoly 1) 7-2- (3-pyrenyl) -acetylene 1- (2-Benzimidazoly 1) - 2- (3-pyrenyl) acetylene -l- ^ 2- (l-methylbenzimidazolyl) 7-2- (3-pyrenyl) acetylene Ir (2-Benzofury 1) -2- (3 ~ pyreny 1) -acetylene 1- (3-pyrenyl) -2- (2-naphth ^ l 2-d7 oxazoly 1) -acetylene l- / f2- (l-methylbenzimidazolyl) 7-2- (9-phenanthryl) -acetylen1- (2-benzoxazolyl) -2- (9-phenanthryl) -acetylene 1- (2-benzimidazoly1) -2- (9-phenanthranyl) -acetylene (2-naphthri.2-d7oxazolyl) -ethinyl-biphenyl

409845/1104

MANUFACTURING EXAMPLES

Example 1: 1- (9-Anthryl) -2- (2-benzoxazolyl) acetylene

17.5 g (38 mmol) of 1-phenylsulfonyl-1- (benzoxazol-2-yl) -2- (anthracen-9-yl) -ethylene with a melting point of 222 ° -223 ° C. are added together with 4.1 g (36 , 5 mmol) potassium tert-butoxide in 180 ml of tert. Butanol heated under reflux for 7 hours with stirring. The mixture is allowed to cool to room temperature, and the product which has precipitated is filtered off with suction and washed with acetonitrile. After drying, 11.0 g of 1- (9-anthryl) -2- (2-benzoxazolyl) acetylene are obtained which, after recrystallization from acetonitrile / dimethylformamide (1: 1), melts at 197.degree.-198.degree.
Yield: 91 # d. Th.

'C-C = C .0 /

C ₂₈ H ₁₃ NO Z519.17

Absorption max .: 413 nm molecular weight: found. 319 (mass spectrometry)

^r c

2220 cm *

Example 2: 1- (2-Benzoxazolyl) -2- (1-naphthyl) acetylene

4.1 g (10 mmol) of 1-phenylsulfonyl-1- (benzoxazol-2-yl) -2- (naphthyl-yl) -ethylene (melting point 170 ° -171 ° C.) are converted into a solution of 1 at room temperature G (8.9 mmol) of potassium tert-butoxide in 50 ml of dimethylformamide and stirred for 4 hours. It is then poured onto ice and neutralized with glacial acetic acid. This gives 1.0 g of l- (2-benzoxazolyl) -2- (l-na # fchyl) acetylene, which after recrystallization from acetonitrile at 114 ° - 115 ⁰ C melts.

409845/1104

Yield; 37 # d. Th.

C ₁₉ H ₁₁ NO /269.37

Absorption max .: 342 mn Molecular weight: found. 269 (mass spec.)

2220 cm " ¹

Example 3: 1- (2-Benzoxazolyl) -2- (3-Pvrenvl) -acetylene

5 g (10.3 mmol) of 1-phenylsulfonyl-1- (benzoxazol-2-VI) -2- (pyrene-3-yl) -ethylene (melting point 191 ° -192 ° C.) are suspended in 30 ml of dimethylformamide and 0.4 g (10 mmol) of powdered sodium hydroxide is added while stirring. After stirring for one hour at room temperature, it is filtered off with suction, washed with water and dried. 2 g of 1- (2-benzoxazolyl) -2- (3-pyrenyl) acetylene are obtained, which melts at 194 ° C. after recrystallization from acetonitrile / dimethylformamide.
Yield:. '57 $> d. Th.

C-C = C

-: 2225

C ₂₆ H ₁₃ NO /343.47

Absorption max. 378 nm. Molecular weight: found. 343 (mass spec.)

Example 4: 1.4 bis (2-benzoxazolyl-ethereal) -benzene

3.3 g (5.1 mmol) 1,4-bis - / ^ - phenylsulfonyl-β- (2-benzoxazolyl) -ethenyl-7-benzene the formula

A0984S / 1104

(M.p. 289 ° -. 290 ⁰ C) at 0 ⁰ C to a suspension of 1 "25 g (11.2 mmol) of potassium tert-butoxide in 50 ml dimethylformamide. After stirring for 7 hours at 0 ^° C., the precipitated product is filtered off with suction, washed with acetonitrile and dried. 0.8 g of 1,4 ~ bis (2-benzoxazolyl-ethinyl) -benzene, which melts ^{at 53O 0 C after recrystallization from dioxane, is obtained.} Yield; 44 # d. Th.

₂ /560.47

Absorption max .: 344 nm Molecular weight: found 360 (mass spec.)

2220

Example 5: '1- (4-Cyanophenyl) -2- / 2 ~ - (6-methyl-benzoxazolyl2 7-

acetylene

4 g (10 mmol) of l-phenylsulfonyl-l- (6-methylbenzoxazol-2-yl) -2- (4-cyanophenyl) -ethylene (melting point 178 ° C.) are dissolved in 15 ml of dimethylformamide and cooled to ^{0 ° C.} and 1.2 g (10.7 mmol) of potassium tert-butoxide were added. It is stirred for 4 hours at this temperature, then poured onto ice and neutralized with glacial acetic acid. It is filtered off with suction, washed with water and ethanol and dried. This gives 1.3 g of 1- (4-cyanophenyl) -2- / 2 "- acetylene (6-methyl-benzoxazolylJ7 ~, which after recrystallization from acetonitrile at 211 ⁰ C melts yield; 50 # of theory...

-CN

409845/1104

C ₁₇ H ₁₀ N ₂ O /258.27 absorption max ^ 326 nm

Molecular weight: found 258 (mass spec.)

Example 6; 1- / 2- (6-methyl-benzoxazolyl) 7-2- (3-pyrenyl) -

acetylene .

2.5 g (5 mmol) of 1-phenylsulfonyl-1- (6-methylbenzoxazol-2-yl) -2- (pyrene-3-yl) -ethylene (melting point 186 ° C.) are suspended in 20 ml of dimethyl sulfoxide and with 0.5 g (5.3 mmol) of sodium methylacetamide were added. The mixture is then ^{stirred for 2 hours at 80 °} C., cooled to room temperature, acidified with glacial acetic acid and filtered off with suction. After washing with water, it is dried. 1.2 g of 1- / 2- (6-methylbenzoxazolylJ7 ~ 2- (3-pyrenyl) acetylene are obtained which, after recrystallization from acetonitrile, melts at 167 ° C. Yield; 67% of theory.

H ₃ CC ₂₆ H ₁₆ NO / 3 "57» 4 /

Maximum absorption 379 nm

Molecular weight: found 357 Vc = C ^{s 21} ^ ° ^cnrl (mass spec.)

Example 7: 1- / 2- (5.7-dichlorobenzoxazolvl27-2- (9-anthrvl) -

acetylene

5.2 g (10 mmol) l-Phenylsülfonyl-l- (5.7-dichlorobenzoxazole-2-yl) -2- (anthracene-9-yl) - ethylene (m.p. 209 ⁰ C.) And 1.1 g (9 , 8 mmol) potassium tert-butoxide are tert with 45 ml. Butanol was stirred for 5 hours at 8O ⁰ C. It is then cooled to room temperature, with

409845/110 *

Glacial acetic acid acidified and suctioned off. After washing with water and drying gives acetylene 1.9 gl ~ / 2- (5.7-dichloro-benzoxazolyl27-2- (9-anthryl), which melts after recrystallization from dimethylformamide at 210 ^0C.
Yield: 49 $ d. Th.

Cl

C ₂₃ H ₁₁ Cl ₂ NO /388.2/

Absorption maw 419 nm Molecular weight: found 388 (mass spec.)

Example 8:

1- / 2 * - (5.7 dichlorobenzoxazole 27-2- (1-naphthyl) ■ acetylene

4.7 g (9.8 mmol) of 1-phenylsulfonyl-1- (5.7-dichlorobenzoxazol-2-yl) -2- (naphth-1-yl) -ethylene (m.p. 184-185 ° C) v / ground stirred together with 0.6 g (10.7 mmol) of potassium hydroxide in 20 ml of dimethyl sulf oxide for 20 hours. It is then filtered off with suction, washed with water and dried. 0.6 g of 1- / 2- (5.7-dichlorobenzoxazolyl27-2- (1-naphthyl) acetylene is obtained, which, after recrystallization from acetonitrile, melts at 156 ° C. Yield: 18% of theory -

C ₁₉ H ₉ Cl ₂ NO /338.27

Absorption maxi; 345 nm molecular weight: found 338 (mass spec.)

^{2225 cnf}

^fl

A098A5 / 110A

Example 9;

1- / 2- (5.T-dichlorobenzoxazolyl ^ ZS-- (5-pyrenyl) -acetylene

2.3 g (4.1 mmol) of l-phenylsulfonyl-1- (5.7-dichlorobenzoxazol-2-yl) -2- (pyrene-3-yl) -ethylene (melting point 221 ° -222 ° C.) are added to the 200 ml of dimethyl sulfoxide dissolved and mixed with 0.2 g (5 mmol) of powdered sodium hydroxide while stirring. The mixture is stirred for hours at room temperature, poured onto ice, neutralized with glacial acetic acid, filtered off with suction, washed with water and dried. 1 g of 1- / 2- (5.7-dichlorobenzoxazolylJ_7-2- (3-pyrenyl) acetylene, which, after recrystallization from dimethylformamide, melts at 238 ° C. is obtained.
Yield: 59 f ° d. Th.

Cl

C ₂₅ H ₁₁ Cl ₂ NO / 412.37

Absorption max ^ 380 nm Molecular weight: found. 411 (mass spec.)

2220 cnf ¹

Example 10: 1- / 2-C 5-phenyl-1. 3.4-oxdiazolyl27-2- (9-anthryl) -

acetylene

2 g (4.1 mmol) of l-phenylsulfonyl-l- (5-phenyl-1,3,4-oxadiazol-2-yl) -2- (anthracene-9-yl) -äthylen (mp. 180 ⁰ C) in 15 ml of dimethyl sulfoxide suspended and then treated with 0.25 g (4.5 mmol) of potassium hydroxide. The mixture is stirred for 20 hours at room temperature, poured onto ice, acidified with 2N hydrochloric acid, filtered off with suction, washed neutral and dried. There remain 0.8 g of 1- / 2- (5-phenyl-1.3.4-oxdiazolylJ> 7 ~ 2- (9-anthryl) acetylene selected from acetonitrile / dimethylformamide (1: 1 melts) recrystallized at 203 ⁰ C .
Yield: 56 fo d. Th.

409848/1104

C ₂₄ H ₁₄ N ₂ O /546.47

Absorption max ^ 409

Molecular weight: found 346 y * c = c ^{: 2220 cnfl} (mass spec.)

Example 11: 1- / 2 "- (5-Phenyl-1.3.4-OXdJaZoIvIjT - ^ - * (3-pyrenyl) -

acetylene

0 »9 g (22.5 mmol) of powdered sodium hydroxide are suspended in 50 ml of dimethyl sulfoxide. To this suspension a 100 ⁰ C hot solution of 14.2 g (27.7 mmol) of 1-phenylsulfonyl-l- (4-phenyl-l.3.4-oxadiazol-2 ~ yl) -2- (pyrene-3- yl) -ethylene (m.p.

v & imgthyl sulfoxide
230 ⁰ C) in 100 ml DMSC \ was added. The mixture is stirred for 15 minutes, acidified with glacial acetic acid and filtered off with suction. After washing with water and acetonitrile and subsequent drying left 7.3 g of 1 - / - (5-phenyl-l.3.4-oxdiazolJJ-2- (3-pyrenyl) acetylene, which melts, after recrystallization from dimethylsulfoxide at 200 ⁰ C .

Yield: 71 $ d. Th. Based on sulfonyl compound,

88 io d. Th., Based on sodium hydroxide used

N N

C ₂₆ H ₁₄ N ₀ O £ 570.47

Absorption max ^ 372 nm 'V ^ csC ^ ² ^ x 90 cm " ¹

Example 12: 1- C2-Benzimidazolyl) -2- (3-pvrenyl) acetylene

4.7 g (9.7 mmol) of l-phenylsulfonyl-l- (benzimidazol-2-yl) -2- (pyrene-3-yl) -äthylen (m.p. 195 ° -. 196 ⁰ C) at 60 ⁰ C. dissolved in 35 ml of dimethyl sulfoxide and treated with 2 g (21 mmol) of sodium methylacetamide. After stirring for 3 hours at 60 ^° C., the mixture is poured onto ice, acidified with glacial acetic acid and filtered off with suction.

409845/1104

20 *

After washing with water and drying, 3 g of 1- (2-benzimidazolyl) -2- (3-pyrenyl) acetylene remain, which melts at 261 ° C. after recrystallization from acetonitrile / dimethylformamide (1: 1).
Yield: 91 $ d. Th., ^ W ^ X

UQ

C ₂₆ H ₁₄ N ₂ /342.4J

Absorption max ^ 383 nm

Molecular weight: found 342 ^^ _CsC i 2190 cm " ¹

(mass spec.)

Example 13: 1- (2-Benzimidazolyl) -2- (4- cvanophenyl) -acetylene

8.5 g (76 mmol) of potassium tert-butoxide are introduced into 100 ml of dimethyl sulfoxide with stirring. Then, at room temperature, 15.2 g (39.5 mmol) of l-phenylsulfonyl-l- (benzimidazol-2-yl) -2- (4-cyanophenyl) -äthylen (m.p. 203 ° - 205 ⁰ C.) Was added and
Stirred for 3 hours. It is poured onto ice water, acidified with glacial acetic acid, filtered off with suction and washed with water. The still moist product is suspended in 50 ml of acetonitrile, filtered off with suction again and dried. 6.5 g of 1- (2-benzimidazolyl) -2- (4-cyanophenyl) acetylene are obtained, which melts at 253 ° C. after recrystallization from dimethylformamide.
Yield t 68 $ d. Th.

/ 243.37

Absorption max ^ 330 nm
Molecular weight: 243
(mass spec.)

409845/1104

»21- -

Example 14: 1- (2-Benzimidazolyl) -2- (1-naphthyl) -acetylene

7 g (65 mmol) of potassium tert-butoxide are added under stirring at 80 ⁰ C to 100 ml of dimethylsulfoxide and then with 12.5 g (50 mmol) of l-phenylsulfonyl-l- (benzimidazol-2-yl) -2 - (naphth-lyl) -ethylene (melting point 277 ° C) added. The mixture is stirred at 80 ° C. for one hour and then poured onto ice. After acidification with glacial acetic acid, it is filtered off with suction, washed with water and dried. After dispersing in 50 ml of acetonitrile, filtration with suction and drying, 6.5 g of l- (2-benzimidazolyl) -2- (l-naphthyl) acetylene, which melts after recrystallization from acetonitrile at 197 ⁰ C. ' Exploits 81 # d. Th.

Ci ₉ H ₁₂ N ₂ /268.27

Absorbance measure3V 541 nm Molecular weight: found 268 (mass spec.)

^: 2180 cm " ¹ (weak)

Example 15: l - ^ - (l-Methvlbenzimidazolylj7-2- (l-naphthyl) -

acetylene

8.1 g (50 mmol) l- <benzimidazol-2-yl) -2- (naphth-1-yl) acetylene (mp. 197 ⁰ C) and 1.5 g07,5 mmol) of sodium hydroxide with 120 ml Water is added. 100 ml of acetone are added to this mixture while stirring, so that a clear solution is formed. 5.6 ml (4.8 g; 58 mmol) of dimethyl sulfate are added to this solution, a product beginning to precipitate after a short time. The mixture is stirred for a further 2.5 hours, filtered off with suction, washed neutral with water and dried. This gives 8 g of l- / 2 ~ - (l-MethylbenzimidazolylJ [7-2- (l-naphthyl) acetylene, which after recrystallization from i-propanol at 122 ⁰ C melts yield: 95 # of theory...

409845/1104

Absorption max .: 343 nm

Molecular weight: gef, 282 Vc ^ C * ^{2180 οπΓ1} ( ^seh ? ^Scnwacn ) (mass spect.)

Example 16: 1- / 2- (1-methylbenzimidazolylJ7--2 - (3-pyrenyl) -

acetylene

2.5 g (5 mmol) of l-phenylsulfonyl-l- (l-methylbenzimidazol-2-yl) -2- (pyrene-3-yl) -äthylen (mp. 235 ° C) v / ground at 80 ⁰ C in 50 ml of dimethyl sulfoxide are dissolved, then 0.5 g (5.2 mmol) of sodium methylacetamide are added and the mixture is stirred at this temperature for 1 hour. It is then poured onto ice, acidified with 2N hydrochloric acid, filtered off with suction and washed neutral with water. After drying, 1 g of 1- / 2- (1-methylbenzimidazolylJ7-2- (5-pyrenyl) acetylene is obtained, which, after recrystallization from acetonitrile, melts at 176 ° C. Yield: 56% of the theory.

CH ₃

C ₂₆ H ₁₆ N ₂ /356.37 absorption max ^ 380 nm

Molecular weight: found 356 ~] / η =: π * ^{2180 cnri} ( ^{senr weak} )

(mass spectrum »)

409845 / Ί10Α

Example 17: 1,3-Dimethyl-2- / Tl-naphthyl) -äthinyJ7-benzimide-

azolinium monomethyl sulfate

0.7 g (2.5 mmol) of l- (l-methylbenzimidazol-2-yl) -2- (naphth-1-yl) acetylene (melting point 122 ° C.) are dissolved in 25 ml of dioxane and mixed with 0 , 3 ml (0.4 g; 3.2 mmol) of dimethyl sulfate are added. When heated to 50 ^° C., a product already begins to precipitate. The mixture is stirred for a ^{further 1 hour at 50 °} C., filtered off with suction and washed with dioxane. After drying, 0.7 g of 1,3-dimethyl-2- / xlnaphthyl) ethinyl-7-benzimidazolinium monomethyl sulfate, which melts at 263 ° C. after recrystallization from ethanol. Yield; 58 $ d. Th.

O ₃ SO-CH ₃

(C ₂₁ H ₁₇ N ₂ ) O ₅ SOCH ₃ ⁰ /408.467 absorption max ,: 352 nm

2200 cm ¹ (very thick)

Example 18: 1- (2-Benzofuryl) -2- (3-pyrenyl) acetylene · ■

5 g (10.4 mmol) of 1-phenylsulfonyl-1- (benzofuran-2-yl) -2- (pyrene-3-yl) -äthylen (mp. 175 ⁰ C) together with 1 g (10.5 mmol ) Sodium methylacetamide in 100 ml of dimethyl sulfoxide was stirred for 24 hours at room temperature. It is filtered off with suction, washed neutral with water and dried. 1.7 g of 1- (2-benzofuryl) -2- (3-pyrenyl) acetylene are obtained, which melts at 135 ° C. after recrystallization from acetonitrile.
Yield: 48 % of theory Th.

409845/1104

C ₂₆ H ₁₄ O /342.47

Absorption max .: 404 nm Molecular weight: found 342 (mass spec.)

²²⁰⁰

Example 19:

1,4-bis- / 2- (5-methylbenzoxazolyl) ~ ethinyl7- benzene

6.7 g (10 mmoles) of 1,4-bis- / i-phenylsulfonyl-β- (5-methylbenzoxazol-2-yl) -ethenyl-7-benzene the formula

^{C = CH}

SO ₂ -C ₆ H ₅

-CH = C-C 1 \ 0

C ₆ H ₅ SO ₂

(Mp. 281 ° C) are suspended in 75 ml of anhydrous dimethylformamide and mixed rapidly at 0 ⁰ C under intensive stirring, 2> 4 g (21.5 mmol) of potassium tert-butoxide. After stirring for three hours at 0 ^° C., the mixture is poured into 1000 ml of ice water. After acidification with dilute acetic acid, the precipitate formed is filtered off with suction. 0.9 g of 1,4-bis- / 2- (5-methylbenzo3tazolyl) -äthinyl7-benzene are obtained, which melts at 321 ° C. after recrystallization from dimethylformamide / dioxane (1: 1). Yield: 23 % of theory Th.

C ₂₆ H ₁₆ N ₂ O ₂ /388.47

Calculated: C 80.4 $ S; H 4.16 f ₀ ; found: C 80.3 §S; H 4.2 f>;

Absorption max »: 348 nm Molecular weight: found. 388 (mass spec.)

N N

7.2
7.3

409845/1104

- 25 -

Example 20: 1- (2-Benzthiazolyl) -2- (3-pyrenyl) acetylene

5 g (10 mmol) of 1-phenylsulfonyl-1- (benzthiazol-2-yl) -2- (pyrene-3-yl) -ethylene (Sclimp. 203 ⁰ C) are dissolved in 100 ml of dimethylformamide and at 0 ° C with 1.2 g (10.7 mmol) of potassium tert-butoxide were added. The mixture is stirred for 5 hours at 0 ^° C., then poured into 300 ml of ice water, acidified with 2N acetic acid and the precipitate which has separated out is filtered off with suction. After drying and chromatography on silica gel (eluent: chloroform), 1.1 g of 1- (2-benzthiazolyl) -2- (3-pyrene3rl) acetylene, which melts at 153 ° C., are obtained.
Yield: 30 # d. Th.

C = C

C ₂₅ H ₁₃ NS /359.47

Absorption max. 382 nm Molecular weight: found. 359 (mass spectrum,)

Example 21: 1- (4-Cyanophenyl) -2- (3 ♦ 4.5-trimethoxyphenyl) -

acetylene

2.18 g (5.0 mmoles) of 1-Phenylsulf onyl-1- (4-cyanophenyl) -2- (3.4.5-trijnethoxyphenyl) -äthylen (mp. 166 ⁰ C) of the formula

OCH ₃

NC-tf}} - C = CH ~ tf ^ -OCH ₃

OCH ₃

dissolved in 8 ml of anhydrous dimethylformamide, 0.70 g (6.2 mmol) of potassium tert-butoxide are stirred at 45 ° C. for 4 hours. After cooling, the mixture is poured into 150 ml of water, this is weakly acidified with 2N HCl and the resulting water Sucked off precipitate. After washing with water and

409845/1104

Drying at room temperature gives 1.4 g of a product from which 1- (4-cyanophenyl) -2- (3.4.5-trimethoxyphenyl.) Acetylene can be isolated by chromatography on 50 g of silica gel. When eluting with chloroform or benzene, 460 mg of pure product are obtained from. Mp. 140 ° -142 ° C, corresponding to a yield of 31 i ° d. Th.

) CH ₃

NC-

/293.317

Calculated: C 73.70 fc, H 5.15 #; N 4.78 fi

found : C, 74.1 #; H $ 5.3; N $ 5.1

Absorption spectrum: "\ _r (in DMF) 320 nm

Example 22:

1- (9- anthyl) -2- (2-naphth / T.2-d7oxazolyl) acetylene

2.56 g (5.0 mmol) of 1-phenylsulfonyl-1 - ^ - naphth / 1 ^ - ^ oxazolyl ·) -2- (9-anthryl) -ethylene (Limp. 207 ° - 209 ° C) of the formula

are brought into solution in 30 ml of anhydrous dimethylformamide with gentle heating. After cooling to room temperature (25 ° C) are one 0.60 g (5.4 mmol) potassium tert-butylate and stirred for 4 hours at 25 ⁰ C. The precipitated product is filtered off with suction; is isolated 1.30 g of pure 1- (9-anthryl) -2- (2-naphth / l.2-d7oxazolyl) acetylene mp 220 ° -. 223 ⁰ C, corresponding to a yield of 70 $ d. Th.

409845/1104

C ₂₇ H ₁₅ NU Z369.427

Calcd. ί C 87.78? S; H Found: C 87.9>; H

Absorption spectrum:

5-CsC

4.09 ^; N 3.79 # 3.8 g; N 3.7 #

(in DMF) 423 nm

Example 23: 1- (3-Pyrenyl) -2- (2-naphth / l. 2-d7oxazolyl) -

acetylene

10.7 g (20 mmol) of l-phenylsulfonyl-1- (2-naphth / I.2-d7oxazolyl) -2 - (3-pyrenyl) -ethylene (melting point 229 ° -231 ° C.) are at 90 ° C dissolved in 100 ml of anhydrous dimethylformamide. One gives 2.5 g (45 mmol) of powdered potassium hydroxide are added and stirred for 15 minutes at 100 ⁰ C. After cooling to room temperature, the reaction mixture is poured into 600 ml of water and acidified with 2N HCl to PTT. 5 The resulting precipitate is filtered off with suction and air-dried.

The resulting by-products and unreacted starting material it is separated off by repeated recrystallization from n-butanol. Remaining after three recrystallization 1.3 g of 1- (3-pyrenyl) -2- (2-naphth ^ .2-d7oxazolyl) acetylene vom Mp. 183 ° - 197 ° C, corresponding to a yield of 17 $ of theory.

C ₂₉ H ₁₅ NO /393,437

Calculated: C 88.55 #; H 3.82 #; N 3.59 # found. ί C 88.8 %; H 4.0 f ₀ ; N 3.3 f °

Absorption spectrum:

(in DMF) 398 nm

409845/1104

Example 24: 1- (3-Pyrenyl) -2 ~ (2-naphth /T.2-d 7oxazolyl) -

acetylene

2.85 g (5 mmol) of 1- (4-chlororaen3a-sulfonyl) -l- (2-naphth / T.2-d7-oxazolyl) -2- (3-pyrenyl) -ethylene (melting point 276-279 ⁰ C) are dissolved at 90 ⁰ C in 40 ml of anhydrous dimethylformamide and mixed with 0.5 g (9 mmol) of powdered potassium hydroxide. The mixture is stirred 15'Minuten "at 90 ⁰ C. After cooling to room temperature the reaction mixture in 250 ml ¥ ater 'is added and acidified with 2N HCl to Ptt third The precipitate formed is suction filtered and dried in air.

For purification, the product is chromatographed on a column with 100 g of neutral aluminum oxide, benzene is used as the eluent. Is isolated 0.64 g of pure l- (3-pyrenyl) -2- (2-naphth / l.2-d7oxazolyl) ~ acetylene, corresponding to a yield of 33 io d. Th.

The physical data are the same as in example (23).

Are obtained analogously from the p-Br-Sulf onylphenylverbiiidung (m.p. 266 ° -. ⁰ 29o C), a yield of 25 #, P-NO ₂ -SuIfonylverb. (M.p. 306 ° -. 308 ⁰ C) in a yield of 7 io.

Example 25? l-cyano-2- (9-anthryl) acetylene

-Äthylen 2.4 g (6.5 mmol) of l-cyano-l-phenylsulfonyl-2- (9-anthryl) (m.p. 200 ° - 202 C ^0th) -werben in 20 ml of anhydrous dimethylformamide. At 5 ⁰ C are added (12.5 mmol) of powdered sodium hydride in small portions with stirring over a period of 30 minutes 0.30 g.

409845/1104

It is carefully diluted with water while cooling from the outside (initially with a ΠΚ ^ Ϊ ^ / a ^ ser ^ Seinisch) and then acidified with 2N HCl. The deposited precipitate is filtered off with suction, washed with water and dried. The l-cyano-2- (9-anthryl) acetylene is obtained in pure form by recrystallization from acetonitrile (65 ml).
Yield: 0.58 g of melting point 219 ° -221 ° C., corresponding to 39 % of theory.

/ J-C = C-CN

C ₁₇ H ₉ N / 227.27

Absorption max: 406 nm Molecular weight: found 227 (mass spec.)

Example 26: 1.4-Bis ^ 2-naphthA. 2-d7oxazolyl) -äthinyl7-

benzene

1 "49 g (2.0 mmol) 1.4-3is / jT-phenylsulfonyl-.beta. (2-naphth / T.2-d7 ~ oxazolyl) -äthenyl7-benzene (m.p. 254 ° -. 256 ⁰ C) of the formula

dissolved in 40 ml of anhydrous dimethylformamide, with 0 * 50 g (4.5 mmol) of potassium tert-butoxide, stirred for 5 hours at 60 ⁰ C.

From the dark brown reaction mixture fall already during the implementation of yellowish crystals with a melting point of>

409845/1104

the end. After cooling, filtering off with suction and washing with DMF, 0.15 g of product is isolated. The yield corresponds to 16 fo d. Th.

Absorption spectrum: / ι (in DMF) 570 nm

The further compounds summarized in the table below were prepared analogously to the processes of Examples (1) - (26) obtain.

The starting material (melting point given in the table) was a phenyl vinyl sulfone, whose sulfony group on the one marked by an asterisk (in the formula of the end product) marked C-atom was bound.

409845/1104

Tabel example

27

28

29

30th

31

Surname

4.4'-dicyano-tolane

4-nitro-4 ^f -cyanotolane

4-dimethylamino-4 cyano-tolan

1- (2-Benzofuryl) -2- (4-cyanophenyl) acetylene

1- (1-Naphthyl) -2- (4-cyanophenyl) acetylene

3-chloro-4'-cyanotolan

formula

NC-

OMV

NC-Q) -

-NO _S

- ^ c-Qk

^ CH ₃ "CH *

-OK

NC-

Cl

M.p. des
Starting mat.
• ( ⁰ C)

163-168

224

132-135

146-148

151-158

138-140

M.p. des
Acetylenes
( ⁰ C)

269-271

204-209

208-210

190-192

126

86-92

Paragraph max.
nm

324

325

372

330

333

315

ro co ro ο cn

example

3.3

34

35

36

37

Surname

4-chloro-4'-cyano tolan

1- (3-pyrenyl) -2- (4 ~ cyano-phenyl) -acetylene

4-methoxycarbonyl-4'-cyanotolan

1- (2-naphth / 1.2-dJ-oxazolyl) -2- (4-cyanophenyl) acetylene

formula

Mp of the snmp. of the paragraph max.

-Cl

0
-C-OCH.

1- (2-naphth / 1.2-d7-oxazolyl) -2- (inaphthyl) acetylene

Starting mat.

168-170

196-202

138-160

165-168

158-163

Acetylenes
( ⁰ C)

162-176

195-200

96-105

256-258

133-135

■: wx

318

377

331

354

361

ω
to

cn ro co

example

38

39

40

41

42

Surname

1- (2-naphth / 1.2-d7-oxazolyl) -2- (3-chloro phenyl) acetylene

1- (2-naphth / 1.2-d7 ~ oxazolyl-2-t3.4.5 * - trimethoxyphenyl) acetylene

~ / 2- (5-methyl-benz-J7 ( A.

ayJ7 cyanophenyl) ~ acetylene

^ (53 benzoxazolyl) 7 ~ 2- (1-naphthyl) acetylene formula

Mp. Of mp. Of paragraph max.

Starting mat.

120-141

OCH ₅
OCH ₃ 188-190

OCH ₃

> C = C-OX

-CM

4,4'-bis / 2- (5-

Methyl-benzoxazolyl) -

athinyl7-biphenyl 166

138

Acetylene

111-114

318-320

215

106

300

nm

364

370

324

344

346

Example

43

44

45

46

47

Surname

1- / 5- (5-methyl-benzoxazolyl27-2- (3-pyrenyl) -acetylene

1- / 2- (5,6-dimethylbenzoxazolylJ7-2 - (. 4-cyanophenyl )-acetylene

1.4-bis- / 2- (5.6-

Dimethvl-benzoxazo-

Iyl) -äthinyl7-benzene

1- / 2- (5.6-Tue-

methyl-benzoxa-

zolylJ7-2- (l-

naphthyl) -

acetylene

4.4 ^f -Bis- / 2- (5.6-

dimethyl-benzoxazοIyI) -äthinyl7-biphenyl

formula

M.p. des
j starting mat,

MP of the paragraph max.

nm

379

351

σ
co
οο
• ροή

example

48

49

50

51

52

Surname

1- / 2- (5.6-Dimethylbenz oxazolyl_) 7-2- (3-pyrenyl) acetylene

1.4-bis- (2-benz-

thiazolyl-ethinyl} -

benzene

1- (2-Benzthiazo-IyI) -2- (naphthyl) acetylene

2,6-bis- / ~~ (benzox ~ azciyl-2 »J-äthiny] / · naphthalene

l- (9-phenanthryl-):

(2-benzoxazolyl) -

acetylene

formula

Mp. Of mp. Of paragraph max.

Starting mat
¹ C)

223

301

160

299-300

153-154

Acetylene

198

288

112

328-300

161

nm

380
and
408

354

350

example

Surname

2,5-bis- / Tl-naphthyl) äthinyX2-T, 3,4-oxdiazole

2,5-bis- / T3-pyrenyl) äthiny 37 ^ 1,3,4-oxdiazole

1,4-bis- (4-cyanophenylethinyl) -benzene

l-pyrene-3'-yl-2-cyanoacetylene formula

M.p. des
Starting mat.

N-N

207-208

M.p. des
Acetylenes

Abs. Max "

nm

165

288-289

267-268

-C = C-

C = C-

-CN

188

279

263

83

326

368

example

Surname

1- (9-anthryl) -2- (2-naphth / 2 ", 3-d7

oxazolyl) acetylene

1- (1-naphthyl) -2- (2-naphth / 2F, 3-d7

oxazolyl) acetylene

4,4'-bis- (2-naphth / T, 2-d7oxazolyl-

äthinyl) -biphenyl formula

Schnp. Of the shrap. of
Starting mat. Acetylene

180-134 235-241

174-177 ISO-ISl

139-440 3CO-3O3

Section.

nm

423

348

364

cn ro oo

. APPLICATION EXAMPLE

Example I; .

A fabric made of polyethylene glycol terephthalate was impregnated with an aqueous liquor which, in dispersed form, was 0.6 g / l the compound of formula A contained.

The textile material treated in this way was squeezed between rollers until it contained only 60 % of its dry weight of liquid and then subjected to a hot air ^{treatment at 180 °} C. for 30 seconds. After the treatment, the fabric had an excellent degree of whiteness according to Berger / WG = Y + 3 (Z-XJ7 of 140 compared to 67 of the untreated material

on.

ί -

The dispersion used was obtained in the usual way by that in a solvent, here dimethylformamide, the compound A is clearly dissolved with heating and this solution after Addition of a dispersant was stirred into water.

Example II;

A yarn made of polyethylene glycol terephthalate was treated with an aqueous liquor which contained 0.04 wt. The 6O ⁰ C warm liquor was heated with the tissue for 30 minutes to 120 * C and held for 30 minutes at this temperature. After the liquor had cooled down, the goods were rinsed thoroughly and then dried. After the treatment, the yarn exhibited a very high degree of whiteness compared to the untreated material.

409845/1104 "

In the same way the connections were made

and

checked «The table shows the results.

Tabel

link concentration
in the fleet
(By weight so I. Whiteness
after
Berger A ■ 0.04 139 B- 0.06 140 C. 0.06 130 Raw material 67

Example III;

A fabric made of 2 1/2 acetate was treated on a tree dyeing machine of conventional design in a liquor ratio of 1:20 with an aqueous liquor which contained 0.2 wt. The cold liquor with the fabric was ^{heated to 85 °} C. within 30 minutes and left at this temperature for 45 minutes. After the liquor had cooled down, the goods were rinsed and dried.

409845/1104

The whiteness measurement brought the following result (whiteness according to Berger):

link B: 149 link C: 145 Raw material: ■ 70 example IV:

A fabric made of polyethylene glycol terephthalate was impregnated from perchlorethylene in which 0.5 g / l of compound A was dissolved. The textile material treated in this way was squeezed between rollers to a residual moisture of 60 tfo. The fabric was then subjected to a treatment with hot air of 18O ⁰ C for 30 seconds. After this treatment, the fabric had an excellent whiteness of 135 (WG according to Berger) compared to 67 of the untreated material.

409845/1104

Claims (1)

Claims 1. Process for the preparation of acetylenes of the formula I. »C 4-X - C a c4- B (I) in which A is an aromatic carbocyclic or heterocyclic radical or a functionally modified carboxy group, B is an aromatic carbocyclic or heterocyclic radical and X is a divalent link which contains at least one aromatic carbocyclic or heterocyclic radical, and η is zero or 1, characterized in that a compound of the formula II (II) - * ■ η in which A, B, X and η have the abovementioned meanings and R is a lower alkyl or an optionally substituted phenyl group, is reacted with a base in an inert solvent. 2, compounds of the formula I in which X is a divalent link of the formula f \ J ~ L V N-N N-N Jl IL or // \\ 409845/1104 Ii in which R stands for a lower alkyl or phenyl group, η stands for zero or 1, where, when η stands for zero, A is optionally represented by halogen atoms, lower alkyl or alkoxy groups. optionally functionally modified carboxy or sulfo groups, acyl, nitro, amino, lower mono- or dialkyamino groups, substituted naphthyl groups, an anthryl, phenanthryl or pyrenyl group or a group of the formula , 5 ^B "\ / ^or Ii 5 6 in which R has the above meaning and R and R atoms, n
or phenyl groups or R and R together are fused on Hydrogen or halogen atoms, lower alkyl or alkoxy groups or phenyl groups, etc.
Benzene ring mean Y is a group of the formula -CH =, -N = or in which R 'is a hydrogen atom or a lower alkyl group, which is optionally substituted by a hydroxyl, cyano or phenyl group and T ~ is a colorless anion, and Z is a group of the formula .. .. - 0 -, - S - or -NR ⁸ - 8 7 in which R has the meanings mentioned for R ', and B has the meanings mentioned for A and furthermore for an optionally by halogen atoms, lower alkyl or Alkoxy groups, optionally functionally modified carboxy or SuIfo ^ groups, acyl, nitro, amino, lower mono or dialky! amino groups substituted phenyl group, and if η stands for 1, A additionally stands for an optionally functionally modified carboxy group or an optionally substituted by halogen atoms, lower alkyl or alkoxy groups, optionally functional functionally modified carboxy group or an optionally 409845/1104 modified carboxy or sulfo groups, acyl, nitro, amino, lower mono- or dialkylamino substituted phenyl group. 3. Use of nitro group-free compounds according to claim 2 as optical brighteners. 409845/1104