DE2363459A1 - 7-Amino-quinoline cpds. - for use as optical brighteners, dyes, colour formers in copying and in printing pastes - Google Patents

Abstract

New 7-amino-quinoline cpds. (I) have the formula: (in which R1 and R2 are H, opt. Cl-, Br-, CN-, OH-, 1-4C alkoxy- or 1-4C carboxylic ester-substd. 1-6C alkyl or benzyl or R1 can be joined with R2 or with the 6-position of aromatic ring A to a 5- or 6-membered ring, opt. including a heteroatom; R3 is a CN, carboxylic ester or carbamide gp. or a N-heterocyclic gp. opt. quaternised at the N; R4 is OH or amino; the aromatic ring A and the heterocyclic gp. possible for R3 can be substd. by Cl, Br, OH, CN, Alkyl, aryl, aralkyl, alkoxy, alkylthio, aryloxy or arylthio gps. with 1-8C, carboxyl, sulphonic ester or sulphonamide gps.). Cpds. (I) are useful as dyes, optical brighteners, colour formers for copying processes and for the prodn. of printing pastes.

Description

Our reference: 0.Z. 30 275 E. 6700 Ludwigshafen, December 17th, 1973

Novel Fluorescent Quinoline Compounds The invention relates to quinoline compounds of formula I.

V ■ '· ■ ■

in the

12th
R and R for hydrogen, optionally substituted by chlorine, bromine, cyano, hydroxy, alkoxy with one to four carbon atoms or a carbon ester group with one to four carbon atoms

1 2 with one to six carbon atoms or benzyl, where R with R or with position 6 of the aromatic.Ring A to form a five- or six-membered ring, optionally including one Heteroatoms, can be connected,

Br for a cyano, carbon ester or carbonamide group or a nitrogen-containing heterocyclic radical, optionally quaternized on nitrogen,

R stands for hydroxy or amino and both the aromatic ring A and the heterocyclic radical possible for Br as further substituents chlorine, bromine, hydroxy, cyano, alkyl, aryl, aralkyl, alkoxy, alkylthio, aryloxy, Arylthio groups with one to eight carbon atoms per hydrocarbon radical, carboxyl, sulfonic acid ester or sulfonamide can carry.

The "compounds of formula I are colorless to red substances, which, especially in organic solvents, show a strong blue to green fluorescence. The colorless to pale yellow heterocyclically substituted representatives of this class of compounds, the color depends on the pH. Because of These properties can be used in a variety of technical areas, for example as optical brighteners, dyes, Color formers are used for copying processes or for the production of printing pastes.

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Preferred radicals for R and R are in detail methyl, ethyl, n-propyl, cyclohexyl, chloroethyl, hydroxyethyl, 2-methoxyethyl, Phenyl and benzyl and among these in particular methyl and ethyl.

12th
In the event that R and R are connected to one another to form a ring, the pyrrolidine, the piperidine and the morpholine ring are preferred.

Among the radicals for R ^ are the cyano group and the heterocyclic group Remainders are particularly preferred. Examples of suitable carbon ester and carbon amide groups for R ^ are: Carboxylic acid methyl ester, carboxylic acid ethyl ester, carboxylic acid i-butyl ester, Carboxylic acid n-hexyl ester, carboxamide, Carboxylic acid methylamide, carboxylic acid ethylamide, carboxylic acid anilide, Carboxylic acid p-toluidide.

Examples of heterocyclic radicals for Br are: pyrrole, pyrazole, imidazole, thiazole, oxazole, 1,2,4-triazole, 1,3,4-thiadiazole, benzimidazole, benzthiazole, benzoxazole, pyridine, quinoline, pyrimidine, quinazoline and Quinoxaline. For quaternizing the nitrogen in the Br radical, alkyl with one to four carbon atoms and benzyl are particularly suitable. Preferred further substituents for the aromatic ring A are specifically methyl, ethyl, methoxy, ethoxy, chlorine and bromine.

Of particular technical importance are the connections of the

Formulas

K ₃ C

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^; ₂ χ Γ

N ^ NH.

ν O.Z. 30th 275 2
H 36 3459 / N ⁵ ^ H, C C. Wn ,. D. "^ N ^ H, C y

OH

ZnGl

0H ^CH 3

ZnCl-

N-CH,

ZnCl.

ZnCl

The quinoline compounds of the formula I can by reaction of ο-nitrobenzaldehydes of the formula II with methylene-active compounds of formula III and reduction of the reaction products are prepared. The reaction takes place via compounds of the Formula IV according to the following scheme:

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, 2 s

Ai

II

CHO

⁺ A

NO ₂ R ^D R

III

R-

Yes

R denotes oxygen or an NH group , R ⁵ denotes NH ₀ , OH or O-alkyl.

4- 'S
R and R together can also stand for nitrogen.

The formula Ia represents the quinoline compounds of the formula I to be added tautomeric quinolone compounds.

The nitrobenzaldehydes of the formula II can be suitable m-Nitrodialkylamineh can be obtained.

Examples of aldehydes that may be mentioned in detail are: 2-nitro-4-dimethylamino, -benzaldehyde, 2-nitro-4-diethylaminobenzaldehyde, 2-nitro-4-N-methyl-N-ß-chloroethylamino-benzaldehyde, 2-nitro-4-dimethylamino-benzal-p-toluidine and 2-nitro-4-dimethylamino-benzaldehyde oxime.

Examples of methylene-active compounds of the formula III include Consider malonic acid dinitrile, cyanoacetamide, malonic acid diethyl ester and cyanoacetic acid ethyl ester. Methylene-active compounds, the compounds of the formula I with R ^ = heterocyclic! rest lead, are e.g. 2-Cyanmethylquinazolon- (4), 2-Cyanmethylbenzimidazole, 2-cyanomethyl-1-methylbenzimidazole, benzimidazoiyl-2-acetic acid ethyl ester, Benzthiazolyl-2-acetic acid amide, 2-cyanomethylbenzthiazole, 4-pyridyl-thioacetmorpholide, 2-cyanomethylpyridine, Benzimidazolyl-2-acetic acid ethyl ester, N-methylbenz- "- · imidazolyl-2-acetic acid methyl ester.

50 9 826/1009 ORIGINAL INSPECTED

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The Knoevenagel condensation of the o-nitrobenzaldehydes of the formula II with the methylene-active compounds of the formula III to give the compounds of the formula IV can, according to the "Organic Reactions" (1942), 1, pages 210-266 and (1967), 15, pages 204 to 599 and in "Organikum" (1968), pages 444 to 447 Methods are carried out. The resulting, crystalline, orange to deep red colored compounds of Formula IV can be determined according to the methods of "Houben-Weyl" organic chemistry "Volume XI (1957), 1» pages 36I to 490 described Reduce methods, the resulting amines immediately ring closure in the quinoline compounds of the formula Skip over.

An alternative method of preparation for the compounds of formula I is that the o-nitrobenzaldehydes Formula II or derivatives of them in which the aldehyde function is protected - e.g. by NOH, N-alkyl or N-aryl - ' first reduced to aminobenzaldehydes and then with a methylene-active compound of the formula III with simultaneous Ring closure condensed to the compounds of the formula Ia. Corresponding aminobenzaldehydes are e.g. 2-amino-4-dimethylamino-benzaldehyde, 2-amino-4-diethylaminobenzaldehyde, 2-amino-4-diethylamino-benzal-p-toluidine, 2-amino-4-dimethylamino-benzal-n-butylamine.

The reducing agents used for this reaction are expediently those which are effective in the neutral to alkaline range, such as iron (II) hydroxide, sodium sulfide and sodium dithionite. The ring closure with the active methylene compound is for example in the melt of the components or the addition of a diluent such as acetic acid, corresponding alcohols, Äthylendiglykol, trichlorobenzene, dimethylformamide, N-methylpyrrolidone at temperatures of 20 to 25O ⁰ C. Any protective group introduced for the aldehyde function is split off during the reaction of the o-aminobenzaldehydes.

The compounds of formula I with B? in the meaning of a nitrogen-containing heterocyclic radical can also be prepared from the compounds of formula I with R · ⁵ in the Bedeiiung of cyan, Car-

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bonester or carbonamide by reaction with in the ortho position substituted aromatic amines of the formula

to win. The following groups, for example, come into consideration as ortho-position HZ substituents: OH, SH, NHp, NH-alkyl, NH-aryl, CONH ₂ , CONH-alkyl. Particularly suitable o-substituted aromatic amines are, for example, o-phenylenediamine, N-methyl-o-phenylenediamine, ο-aminothiophenol, ο-aminophenol, 4-methyl-o-phenylenediamine, 4-methoxy-o-phenylenediamine, 4-chloro-o-phenylenediamine, 4,5-dimethyl-o-phenylenediamine, anthranilamide, o-aminobenzoic acid-N-methylamide.

The components are particularly advantageously ^{reacted at temperatures above 100 °} C. in the melt in bulk or in the presence of a correspondingly high-boiling inert solvent, optionally with the addition of suitable catalysts, such as boric acid, or else in a phosphoric acid or polyphosphoric acid melt.

The quinoline compounds of the formula I with B? meaning a nitrogen-containing, heterocyclic radical can in a manner known per se by alkylation, for example with esters of lower aliphatic or araliphatic alcohols with strong acids, such as dimethyl sulfate, diethyl sulfate, methyl p-toluenesulfonate , methyl iodide, benzyl chloride , in the quaternary, soluble color salts be transferred, which is expediently carried out at temperatures of 20 to 160 ° C and optionally in a solvent or diluent. Alternatively, to prepare these quaternary salts, in a known manner (cf. DT-OS 2 142 411), the heterocyclic substituted methylene-active component can also first be alkylated and then condensed with an aminobenzaldehyde, for example one of the abovementioned ones.

In the following exemplary embodiments, the production of the

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Quinoline compounds according to the invention in more detail explained. The parts and percentages given relate to weight. Parts of space relate to parts by weight like that Liter to kilogram.

example 1

CHO

2-nitro-4-dimethylaminobenzaldehyde

720 parts of phosphorus oxychloride are added dropwise at room temperature to a solution of 498 parts of m-nitrodimethylaniline in 1,800 parts by volume of dimethylformamide. The mixture is then heated to 75 to 80 ° C. over the course of an hour and stirred at this temperature for 6 hours. After cooling, the solution is poured into ice water and blunted with sodium acetate solution. The deposited precipitate is filtered off with suction, washed and recrystallized from acetone. 385 parts of aldehyde are obtained in the form of long yellow-orange needles with a melting point of 115 to 116 ^° C.
Analysis; ^c g ^H io ^N 2 ° 3
At · .: -C 55.66 H 5 * 19 N 14.43
Found: 56.0 5.3 14.9
The structure is further confirmed by IR and NMR spectra.

Example 2

CHO

2-amino-4-dimethylamino-benzaldehyde

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9.7 parts of the nitroaldehyde from Example 1 are dissolved in hot 50% ethanol and poured into a boiling solution of 100 parts of iron (II) sulfate heptahydrate in 500 parts by volume of water. Then cook for 1 minute. With thorough stirring, 1J50 parts by volume -conc. Ammonia was added in 10 volume portions at an interval of J> 0 to 40 seconds. It is refluxed for a further 10 minutes and filtered hot. The filter residue is washed with 500 parts by volume of hot water. The aldehyde which crystallizes from the cooled piltrate is filtered off with suction, dried and recrystallized from methylcyclohexane. Yield 6 parts of colorless flakes, melting point 83 to 85 ^° C. Analysis; C ₉ H ₁₂ N ₂ O

Ber. •
e C. 65 , 83 H 7th , 37 0 9 , 74 N 17, 06 Found • 66 , 0 7th , 5 9 , 9 17, 0 example ? ^ CHO H ₅ C ₂ f J '"NO ₂

2-nitro-4-diethylaminobenzaldehyde

38 parts of m-nitro-diethylaniline are introduced into a mixture of 48 parts of phosphorus oxychloride in 120 parts of dimethylformamide. After stirring for 6 hours at 60 ° C., the mixture is poured into ice water, blunted, and the precipitate which has separated out is filtered off with suction, washed and recrystallized from acetone. This gives 12 parts of 2-nitro-4-diäthylaminobenzaldehyd of melting point 75 to 77 ⁰ C.

Example 4

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2-nitro-4-dimethylamine-3benzal-p-toiuidine

194 parts of the aldehyde from Example 1 are dissolved in hot ethanol and, after the addition of II5 parts of p-toluidine and 5 drops of conc. Hydrochloric acid boiled for an hour. The red azomethine which crystallizes out after cooling is filtered off with suction and dried. Yield 255 parts Melting point 114 to 116 ⁰ C. are obtained analogously from the aldehyde of Example 3, the Schiff base, which melts at 65-66 ⁰ C, in 86 $ yield.

Example 5

2-amino-4-dimethylarninobenzal-p-toluidine

28 parts of the nitroazine from Example 4 are dissolved in 400 parts by volume of boiling ethanol and a hot mixture of 46 parts of sodium sulfide in 46 parts by volume of water / ethanol 1: 1 is added. After a short time, the red solution brightens and yellow crystals precipitate, which are filtered off with suction and washed with water and ethanol. 12 parts of pale yellow needles which melt at 167 to 168 ° C. are obtained.
Analy se: C ₁ ^ H ₁ qN-,

Ber.s C 75.85 H 7.5β 16.59

Found: 75.7 7.9 16.6

Analogously, from 2-nitro-4-diethylaminobenzal-p-toluidine, the amine with a melting point of 124 to 127 ° C. is obtained in a yield of 40 ^.

Example 6

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2-amino-3-cyano-7-dimethyldminoquinoline

12.6. Parts of 2-amino-4-dimethylaminobenzal-p-toluidine are dissolved in 250 parts by volume of hot ethanol, 7 parts of malonitrile and 10 parts of glacial acetic acid and 1 part of piperidine are added. It is boiled until the solution is pure yellow, then cooled and suctioned off. The precipitate is triturated with ammonia water and recrystallized from ethylene glycol monomethyl ether. Yield 4.5 parts of pale yellow crystals, melting point 241 to 243 ^° C.
Analysis; ^c i2 ^H 12 ^N 4
Ber.j C 67.9 H 5.7 N 26.4
Found: ■ 67.9 5.6 26.6

The same compound is obtained if one uses 2-nitro-4-dimethylamino-tfc-cyanocinnamic acid nitrile (Melting point 149 ° C, from the aldehyde of Example 1 and malodinitrile in ethanol with piperidine acetate catalysis in $ 82 yield) with iron in glacial acetic acid reductively cyclized.

The above compound from the amino aldehyde of Example 2 is also prepared by condensation with malodinitrile in glacial acetic acid, mp 238 ⁰ C.

The dilute colorless solution of the substance fluoresces intensely blue in daylight and makes synthetic fibers optically light.

Example 7

^ -Cyan ^ -dimethylaminoquinolone- ^) ■

13 parts of 2-amino-4-dimethylaminobenzal-p-toluidine are stirred with parts by volume of ethyl cyanoacetate at 160 ° C. for 3 hours. After cooling, it is diluted with ethanol and filtered off with suction. 10 parts of pale yellow crystals with a melting point of 328 to 334 ° C. are obtained. The structure of the nitrile is confirmed by analysis, IR and NMR spectrum.
The substance optically brightens synthetic fibers.

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Example 8

Ö.2. 30 275

2303459

N '

CONH ₂

j
j

NH ₂

2-Amino-7-dimethylaminoquinoline-j $ -carboxamide

4.2 parts of cyanoacetamide and 12.6 parts of the azine from Example 5 are dissolved in glacial acetic acid and refluxed for 0 minutes. The deposited precipitate is filtered off with suction, washed with ammonia water and recrystallized from ethanol. Yield 2 parts, melting point 260 to 261 ^° C.
The compound is suitable for lightening synthetic fibers.

Example 9

3-carboethoxy-7-dimethylaminoquinolone- (2)

12.6 parts of the azine from Example 5 are boiling in 50 parts Malonic acid diethyl ester entered, refluxed for 8 hours, after cooling, diluted with ethanol and filtered off with suction. 7.5 parts of the above ester with a melting point of 258 to 240 ° C. are obtained, The substance dissolves in dioxane with a strong blue fluorescence and lightens synthetic fiber materials.

Example 10

COHN-

-CB

INSPECTED

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- 12 -

^{12.6 parts of the azine from Example 5 are left at 150 °} C. for 6 hours with 8 parts of diethyl malonate and 5 drops of piperidine. After recrystallization from dimethylformamide, 3 parts of colorless crystals with a melting point of 350 ° C. are obtained. Analysis; ^c i9 ^H iQ ^N 3 ° 2

Calc .: C 71.01 H 5.96 0 9.96 N 13.08 Found; 70.8 5.7. 10.2 13.3 Equivalent weight by perchloric acid titration Ber. 321, found 3I9

Example 11

7-dimethylamino-3 / b "enzthiazolyl- (2) 7-quinolone- (2)

55 parts of «^ (Benzthiazolyl-2 ') - β- (2'-nitro-4 ¹ -dimethylaminophenyl). acrylamide is added in 500 parts by volume of half-concentrated hydrochloric acid at 90 ⁰ C with stirring with 70 parts of zinc dust in 2 hours ^ The precipitated sparingly soluble zinc double salt is ^{suctioned off together with unused zinc at 60 0} C and washed with a little acetone. It is then dissolved in hot dimethylformamide, filtered, made alkaline with ammonia and filtered off with suction. After recrystallization from dimethylformamide yellow needles obtained long, melting at 348-349 C ^O. .

Analysis: Ber. N 13.08 S 9.96 * ^;
Found 13.1 9.9

The compound gives synthetic fibers a brilliant yellow color. The used Acrylic acid amide is prepared as follows: 97 parts of 2-nitro-4-dimethylaminobenzaldehyde are combined with 96 parts Benzthiazolyl-2-acetic acid amide dissolved in ethanol and 15 parts Glacial acetic acid and 9 parts. Piperidine added. After 1 hour

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Cooking is vacuumed in the cold. 2363459

Yield 113 parts, melting point 149-152 ° C.

The same fluorescent dye can be obtained in the following way; 9 parts of the nitrile from Example 7 are stirred with J parts of o-aminothiophenol in 100 parts of polyphosphoric acid at 150 ^° C. for 6 hours. After cooling to 100 ^° C., 300 parts of water are added dropwise and the pH is adjusted to 8 with ammonia. The deposited precipitate is filtered off with suction and recrystallized from dimethylformamide. The yield is 10 parts. Identity with the above compound was established by thin layer chromatograms and melting point.

Example 12 ■

2-Amino-3 / T-methylbenzimidazolyl- (2) 7-7-dimethylaminoquinoline

34 parts are CjL- ^{(I'-methylbenzimidazolyl-2!)} -S-S- (2 ^{t-nitro-4'-dimethylaminophenyl)} -acrylsäurenitril dissolved in dimethylformamide at 60 ° C in the presence of Raney Nickel until the end of hydrogen absorption hydrogenated. The hydrogenation batch is mixed with 2N hydrochloric acid, filtered and brought to pH 3 to 4 with aqueous sodium acetate solution. The above compound crystallizes out as a yellow hydrochloride (melting point 223 to 229 ° C., yield 21 parts). This salt stains polyacrylonitrile in bright yellow tones. If the aqueous solution of the Hydrochl & zrids with ammonia made weakly alkaline, the base coat, which melts after recrystallization from ethylene glycol monomethyl ether at 247-251 ⁰ C. .
Analysis: ^c iq ^H ia ^N 5

Calc .: C 71.9 H 6, O ₃ N 22, O _{7 0R | G} " _SPE CT _E D Gef.-i 71.6 6.2 22.2

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0, Z. yo 275

The compound dissolves in alcohol colorless with strong blue fluorescence. It is suitable for the optical brightening of synthetic fibers. A solution of the substance in acetic acid colors textile fibers made of polyacrylonitrile in yellow, green fluorescent shades at.

If the solution of the quinoline derivative in toluene is enclosed in microcapsules and applied to the surface of paper as a coating, then one obtains when writing on an acidic
Yellow color on the receiver side. The acrylonitrile derivative used above was prepared as follows.

58 parts of ^2-nitro-z l-dimethylaminobenzaldehyde are dissolved in hot ethanol, with parts 5I l-methyl-2-cy.anmethylbenziinidazol and added 5 parts of piperidine. After 2 hours of boiling, 95 parts of red needles crystallize after cooling, at 192 ° C
melt.

Analysis; ^c iq ^H 17 ^N 5 ° 2

Calc .: C 65.7 H 4-, 93 0 9.21 N 20.16
Found:. 65.8 5.0 9.6 20.1

Example 13

12.6 parts of the azine from Example 5 are dissolved in glacial acetic acid at room temperature, and 7.9 parts of 2-cyanomethylbenzimidazole are added. After stirring overnight, a yellow precipitate separates out of the initially red solution , which is filtered off with suction and washed with ammonia water. After recrystallization from dimethylformamide, 13 parts of yellowish crystals which ^{melt at 326 to 330 °} C. are obtained.

The substance colors polyacrylonitrile from an acid bath in luminous yellow tones.

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O.Z. 30 275

The quinoline compound can also be obtained by the following method will be provided:

44 parts of sodium dithionite are dissolved in water at 50 ⁰ C and 100 ⁰ C to a hot solution of 16 parts of φ - (2-benzimidazolyl ¹⁾ SS ^(! 2-nitro-4'-dimethylaminophenyl) acrylonitrile in dimethylformamide dropwise. Subsequently, 3 hours at 100 ⁰ C is stirred with 200 parts by volume of 2N sulfuric acid and stirred for 1 hour at 60 ° C. After cooling, it is made slightly alkaline with ammonia and filtered off with suction.

Yield 6 parts, melting point 330 to 332 ° C. Analysis: ^c i8% 7 ^ 5

Calc .: C 71/26 H 5.6 N 23.09
Found s 70.6 5.6 23.0

The acrylonitrile derivative required was prepared analogously to Example 12 in Ethylene glycol monomethyl ether produced. Melting point 269 271 ° C, N calc. 21.02, N found. 21.2

Example 14

2-Amino-> 3 / r-methylbenzimidazolyl- (2) 7-7-diethylaminoquinoline

14 parts of 2-amino-4-diethylaminobenzal-p-toluidine are reacted analogously to Example I3 with 8.5 parts of 1-methyl-2-cyanomethylbenzimidazole in glacial acetic acid. After recrystallization from ethanol, 4 parts with a melting point of 195 to 198 ^° C. are obtained. When dissolved in acetic acid, the substance colors polyacrylonitrile in bright yellow tones.

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Example 15

3 / Benz imidazo lyl ^ / ^ - dimethylamino-quinolone- (2)

12.6 parts of the azomethine from Example 5 are carefully fused with 10.2 parts of benzimidazolyl-2-acetic acid ethyl ester. The rapidly solidifying melt is recrystallized from dimethylformamide, long, pale yellow needles with a melting point above 350 ^° C. being obtained. -

Analysis; ^C l 8 ^H l6 ³ H 5 , 3 0 5 , 26 N 18th , 41 Ber.s C 71 , 03 5 ,1 5 , 6 18th , 5 Found 5 71 ,1

The substance fluoresces intensely blue in daylight in dilute solution. It gives polyacrylonitrile a brilliant color from an acid bath yellow on.

Example 16

3 / r-Methylbenzlmidazolyl-27-7-dimethylamino-quino "ion- (2)

25 parts of the azomethine from Example 5 are boiled with 12 parts of 1-methylbenzimidazolyl-2-acetic acid ethyl ester in 50 parts by volume of N-methylpyrrolidone until the reaction is complete. After cooling, it is filtered off with suction and washed with methanol. One obtains 23 T <
melts.

holds 23 parts of the above compound at 305-307 ° C

509826/1009 ORIGINAL INSPECTED

The substance optically brightens synthetic fibers.

Analyzes ^c iq ^h i8 ⁿ 4 °

Calculated: C 71.67 H 5.70 N 17.60

Found s 71/7 6.0 17.6

Example I7

2363459 tz 30 275

12.6 parts of the azine from Example 5 are refluxed for 10 minutes with 13.9 parts of quinazolinone (4) -2-acetic acid ethyl ester in 20 parts by volume of N-methylpyrrolidone and worked up as in the example. 14 g of yellow crystals which ^{melt above 500 °} C. are obtained.

Analysis: ^c iq ^h i6 ⁿ 4 ° 2

Calcd. C 68.66 H 4.85 N 16.86
Found 68.9 5 * 2 17.0

Example 18

H 0

ZnCl-

11 parts of 4-pyridylthioacetmorpholide are in 40 parts of i-propanol dissolved, then treated with 4.1 parts of anhydrous sodium acetate and 19 parts of dimethyl sulfate. After adding 4.1 parts 2-Amino-4-dimethylaminobenzaldehyde is refluxed for 2 hours, cooled and diluted with water. With sodium acetate solution a pH of 4.5 is set and the dye with

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a sodium chloride-zinc chloride solution precipitated after drying at 40 ° C in a vacuum drying cabinet, 9 parts of the melting point 297 to 303 ° C isolated. ^ ■

The new compound gives polyacrylonitrile a brilliant reddish tinge yellow tones.

Example 19

ZnCl.

--CH,

k parts of the compound from Example 14 are dissolved in benzene with heating, k parts of dimethyl sulfate are added and the mixture is stirred ^{at 90 ° C. for 5 minutes.} Of the. The precipitate which separates out after cooling is filtered off with suction and, for further purification, dissolved in water, filtered with charcoal and precipitated with sodium chloride-zinc chloride solution.

Yield 5 parts, melting point 235 to 2 ^ O ⁰ C. The substance stains polyacrylonitrile in brilliant yellow shades. ■

Example 20

SO

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5 parts of the quinolone derivative of Example 1.1 are mixed with 30 parts p-toluenesulfonate for 1 hour at l40 to 150 ⁰ C stirred. After cooling, it is diluted with benzene and filtered off with suction. For further purification, it is recrystallized from water. To obtain dark red crystals, melting at 258 bis.262 ⁰ C and dyeing polyacrylonitrile in brilliant orange shade.

Example 21 . '

CH ₃ SO ₄

8 parts of the quinolone of Example 16 are mixed in 20 parts by volume of dimethylformamide at 80 ⁰ C with 10 parts of dimethyl sulfate, after, before going over it falls solution, the dye salt upon cooling. It is suctioned off and washed with a little acetone.
Yield 9 parts of yellow crystals, melting point 311-313 ° C. The compound gives polyacrylonitrile a brilliant yellow color.

ORlQINAL INSPECTED

50 98 267 IU-09

_ 90 _

Claims (1)

- 20 - 0..Z-. 30 P. 75 Claims _ / Ij quinoline compounds of the formula in the 1 2
R and R for hydrogen, optionally substituted by chlorine, bromine, cyano, hydroxy, alkoxy with one to four carbon atoms or a carbon ester group with one to four carbon atoms, alkyl with one to six carbon atoms or benzyl, where R with 2
R or can be linked to position 6 of the aromatic ring A to form a five- or six-membered ring, optionally including a hetero atom, R ^ for a cyano, carbon ester or carbonamide group, or a nitrogen-containing, optionally quaternized on nitrogen, heterocyclic group Rest, R stands for hydroxy or amino and where both the aromatic Ring A as well as the heterocyclic radical possible for Fr as further substituents chlorine, bromine, hydroxy, cyano, Alkyl, aryl, aralkyl, alkoxy, alkylthio, aryloxy, Wear arylthio groups with one to eight carbon atoms per hydrocarbon residue, carboxyl, sulfonic acid ester or sulfonamide can. . 2 ". Quinol compounds according to claim 1, characterized in that R and R stand for methyl and ethyl. 5. quinoline compounds according to claim 1 and 2, characterized in that Br stands for cyano. 4. quinoline compounds according to claim 1 and 2, characterized in that Fr is a pyrrole, pyrazole, imidazole, thiazole, oxazole, 1,2,4-triazole, Ι, ^ Λ-thiadiazole, benzimidazole , Benzthiazole, benzoxazole, pyridine, quinoline, pyrimidine, quinazoline or quinoxaline radical. 509826 / 100-9 - 21 - -.21 - O.Z, 30 275 5. quinoline compounds according to claim 4, characterized in that the Ir radical is quaternized on a nitrogen by alkyl having one to four carbon atoms or benzyl. 6. The connections of the formulas and 7. Process for the preparation of quinoline compounds according to Claim 1, characterized in that compounds of the formula CHO with compounds of the formula CH ₂ - Η? c- R ^D R. 4 «κ- in which R for oxygen or an NH group, W for amino 4 'S
Hydroxy or O-alkyl and R and R ^ together optionally stand for nitrogen, condensed with one another with reduction and ring closure and the reaction products optionally quaternized under nitrogen. 8. A process for the preparation of quinoline compounds according to claim 1, characterized in that compounds of the Formula ■ - 509826/1009 - 22 - - dd - OZ 3C 275 with compounds of the formula CH ₂ -; < Kv condensed with ring closure and the reaction products optionally quaternized under nitrogen. 9 · Process for the preparation of quinol in compounds according to claim 1, in which B? has the meaning of a nitrogen-containing heterocyclic radical, characterized in that quinoline compounds according to Claim 1, in which Br stands for cyano , carbon ester, carbonamide, with compounds of the formula H2 implements, whereby Z is O, S, NH, N-alkyl, N-aryl, CONH or CON-alkyl, and the reaction products are optionally qua ternized on nitrogen. 10. Use of quinoline compounds according to claim 1 as dyes, optical brighteners, color formers for copying processes and for the production of printing pastes. BASF Aktiengesellschaft 509 826/1009