DE2360705A1 - HYDRO-INSOLUBLE COMPOUNDS, PROCESS FOR THEIR PRODUCTION AND THEIR USE AS COLORS - Google Patents

Description

FARBWERKE HOECHST AG formerly Master Lucius & Brüning File number: HOE 73 / F 377

Date: December 5, 1973 Dr. St / stl

Water-insoluble compounds, process for their preparation and their use as dyes

The present invention relates to new water-insoluble compounds the ty-amino-ljS-naphthalimide series, process for their Manufacture and their use as dyes.

The new compounds have the general formula I.

NH-R ₁ (I)

in which R _{1 is} an aliphatic or an eyeIoaliphatic radical which is optionally substituted by aromatic or heterocyclic radicals and which contains at least one hydroxyl group, and Rp is an aromatic or heterocyclic radical '.

The new compounds can be produced in such a way that that one mole of an M-halogen-1,8-naphthalic anhydride

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with one mole of an aromatic or heterocyclic amine of formula (II)

H ₂ N - R ₂ (II)

wherein R _{2 has} the abovementioned meaning, to a compound of the formula III

(III)

with R _{2 of} the above meaning and the substituent Hai for ^ a halogen atom, preferably chlorine or bromine, and then the compound of the formula (III) with a further mole of an amine of the formula (IV)

H ₂ N - R ₁ (IV)

in which R has the above meaning, implemented, with the last reaction stage at least two moles of the amine of formula (IV) used, but particularly advantageously one mole of the amine of the formula (IV) in the presence of at least one equivalent of one acid binding agent, such as sodium carbonate, ■ Sodium bicarbonate or magnesium oxide.

The process is carried out in such a way that the 4-halo-1,8-naphthalic anhydride, preferably the chlorine or bromine compound, is first mixed with the aromatic or heterocyclic amine of the formula (II), advantageously in water, glacial acetic acid or an aprotic solvent , such as dimethyl sulfoxide, N-methylpyrrolidone, phosphoric acid tris- (M, N-dimethyl) -amide or. an alkylated on the nitrogen aliphatic acid amide such as dimethylformamide or Dimethy! acetamide, to 130 ° C, and heated to temperatures of 50 to 150 ⁰ C followed by _3, preferably 80

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an amine of the formula (IV), if appropriate in excess, to temperatures of 50 to 200 ^° C., preferably 80 to 130 ^° C., is heated.

As amines of the formula Rp-NH particularly those of the benzene or come · naphthalene contemplated by halogen atoms such as fluorine, chlorine or bromine atoms, alky! Groups, in particular having 1 to h carbon atoms, alkoxy groups such as methoxy, ethoxy or Propoxy groups, tri fluorine thy 1, carbalkoxy, carbamyl, alkylsulfone, sulfamyl or acyl groups can be substituted, as well as aminoheterocycles of different structures.

As aliphatic amines of the formula (IV) that contain at least one hydroxyl group contain straight-chain or branched alkyl amines with 1 to 16 carbon atoms, in particular with 2 to 6 carbon atoms "into consideration, which by aromatic radicals such as phenyl or naphthyl radicals, or by heterocyclic radicals, which are also quite or partially hydrogenated, for example pyridine, piperidine, morpholine, pyrazole, 'imidazole, triazole, thiazole, Thiodiazole, pyrimidine, furan, piperazine or azabicyclononane residues can be substituted. Come as cycloaliphatic radicals for example hydroxycyclopentyl, hydroxy-cyclohexyl, hydroxyalkyl ! Cyclohexyl or hydroxy - halocyclohexyl radicals into consideration.

The new compounds of the formula (I) represent new dyes and are particularly suitable for the manufacture of fluorescent products in daylight Suitable for pigments. They can also be used advantageously for the mass coloring of plastics, resins, oils, waxes and paper as well as in printing inks, paints and varnishes and for spin dyeing of polyacrylonitrile. ,

In addition, they are also valuable preliminary products for manufacturing of textile dyes, for example acidic or cationic Dyes.

Of the compounds of the formula (I), the compounds of the formula (V)

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(V)

in which FL denotes a phenylene or naphthylene radical, which is replaced by chlorine, bromine, alkyl groups with 1 to 4 carbon atoms, alkoxy groups with 1 to 4 carbon atoms, carboxamide, cyano, nitro, sulfonamide, alkylsulfone groups with 1 to 6 carbon atoms, ethylamino - Or benzoyl amino groups substituted by chlorine or methyl groups, or denotes the triazolyl radical or the bensimidazolyl radical and R, a straight-chain or branched alkylene radical with 1 to 16 carbon atoms, preferably with 2 to 10 carbon atoms, in particular with 2 to 6 carbon atoms, the may contain a phenylene or naphthylene radical or a cyclohexylene radical or an oxygen atom as an intermediate member, or denotes a cyclohexylene radical, where R ₁ contains at least 1 hydroxyl group bonded in the aliphatic or cycloaliphatic part,

a preferred embodiment of the present invention. In particular, however, the compounds of formula (VI)

(VI)

~ ^B

in which R ^ denotes the phenylene radical, which is replaced by chlorine, methyl, Ethyl, methoxy or ethoxy groups can be substituted, or for

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represents the triazolyl radical, A represents the phenylene or cyclohexylene radical or represents an oxygen atom, B represents a hydrogen atom or the hydroxyl group, k represents the number O or 1, ρ represents the number O or 1 tmd m, η and q are the same or different and each for the number 1, 2, 3 or 4, where the sum of (m + η + q) is a maximum of 10, preferably is 6., B is, however, necessarily a hydroxyl group if q = 0,

particularly preferred compounds with advantageous properties.

In particular, however, these compounds have the present Invention of the new compounds of formula (VII)

(VII)

HN-AIk-OH.

in which Alk is a straight-chain or branched alkylene radical with 2 to 6 carbon atoms and ζ denotes the number 1, 2 or 3,

proved to be particularly important representatives of the present application.

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Compared to the dyes known from the Russian patent specification 306 l6o, which are produced by reacting * {- aminonaphthalic acid- (N-phenyl) - or - (N-naphthyl) -imide can be obtained with epichlorohydrin and because of the technically very unsatisfactory accessibility the starting products (nitration of acenaphthene, oxidation of 5-nitroacenaphthene with subsequent reduction and Condensation reaction), the poor yields and insufficient purity, the ecological problems and the large amount of solvent used can only be produced very uneconomically, have the Dyes according to the invention due to their simple, basically one-step and excellent yields and purities reproducible manufacturing process is a crucial economic one Advantage on.

Compared to those from US Patents 2,415,373 and 2 β 017 known dyes of the Jj-Hydroxyalkylamino-ljS-naphthalic acid-N-alkyl- and -N-cycloalkyl-imide series have the new dyes usually better lightfastness and increased fluorescence intensity.

After familiarization with the production of daylight luminous pigments Customary resin combinations, the dyes according to the invention are also distinguished by a considerably better one Authenticity to aromatic solvents.

The dyes according to the invention are therefore the known dyes clearly superior and represent a considerable technical advance.

The following examples serve to illustrate the invention. The parts are parts by weight.

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example 1

- 7 -

116.0 parts of ^ -chloronaphthalic anhydride and 98.5 parts of as-m-xylidine are introduced successively into 500 parts of N-methyl pyrrolidone and the mixture is heated to 130 to 135 ° C. until a chromatographic test shows the complete absence of the starting product ( approx. 8 hours). It is then cooled to 70 ° C., diluted with 650 parts of methanol and further cooled to room temperature. After suction filtration, washing with methanol and water and drying at 8O ⁰ C 157 parts is obtained ^ -Chlornaphthalsäure-mxylidid of formula

Cl

b. Other ways of making the chlorine-naphthalimides are the following:

2200 parts of glacial acetic acid ** 65 parts H- chloronaphthalic anhydride and 25 parts asymmetric ^ m-XyIidin are dissolved, the mixture was heated 8 hours to 110 to 120 ⁰ C, then cooled, filtered off with suction, washed neutral with water and dried at 80 C. 518 parts (77 % of theory) of 4-chloronaphthalic acid-m-xylidide of the above formula are obtained.

232.5 parts JJ-chloronaphthalic anhydride, 125 parts as.-m-xylidine ₅ 5 parts of acetic acid and 1000 parts of Wassc be heated ⁰ C in a stirred autoclave 10 hours at 13O to IIIo, the reaction mixture according to relax by blowing with steam from the excess XyIidin free, suctioned , washed and dried. 322 parts of M-chloronaphthalic acid m-xylidide of the above formula are obtained.

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16.8 parts of ίί-chloronaphthalic acid-m-xylidide of the above formula are added to 30 parts of monosthanolanine; this mixture is ^{stirred at 100 °} C. for 8 hours. Then 500 parts of water are added, the whole thing is stirred for some time and the precipitated product is filtered off with suction, washed neutral and dried. 15 parts of a dye of the formula are obtained

HO- (CH ₂ ) ₂ -NH

Its absorption maximum in dimethylformamide as a solvent is 438 nm, its fluorescence maximum in DMF is 523 nm. Melting point: 223 to ⁰

The dye gives in finely dispersed form on acetyl cellulose, Polyester or polyamide fibers brilliant, greenish yellow colorations. By incorporating them into plastic masses, such as Acetyl cellulose, polystyrene or aminoplasts are obtained Greenish-yellow colored products of high brilliance. By incorporation into spinning solutions of polyacrylonitrile in dimethylformamide the dry spinning process gives greenish yellow colored fibers with good fastness properties.

e. 88.8 parts of toluenesulfonamide and 6.7 parts of paraformaldehyde are combined with 1.3 parts of the under section d. obtained dye mixed and melted together at 160 ° C. In the clear yellow melt is added to 21.8 parts of melamine, stirred for 10 to 15 minutes at 160 ° C. and carried at this temperature then in portions 21.7 parts of paraformaldehyde a. The mixture is then stirred for a further 15 minutes.

The viscous melt is post-hardened at 160 ° C. for three hours and, after cooling, comminuted, then in a ball mill grind wet and dry. It becomes one that way

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brilliant green-yellow fluorescent pigment obtained, which can be incorporated in the usual way in paints, parbene _s plastics, etc.

For example, 10.8 parts of the pigment obtained in this way can be used with 27 parts of a lacquer based on acrylate resin and 8 parts Incorporate xylene in the manner customary in the art, giving brilliant, greenish yellow, strongly colored coatings obtained, which have good solvent fastness.

Examples 2 to 6

If in Example Id) the monoethanolamine is replaced by an aliquot amount of one of those listed in Table 1 below Amines and works in the manner indicated in Example Id are also used for the production of very strong daytime luminous pigments excellently suitable dyes with greenish yellow fluorescence in high yields and excellent quality,

TABEL! example

Amine

yield

- CH ^ -

CH - CH.

OH

"96,

- (CH _{2) 2} - 0 - (CH _{2) 2} - OH

- OH

- OH

96.3 %

94.5 %

9-8.0 Jf

9 ^, 0 %

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Example 7

a. 277 parts of il-bromonaphthalic anhydride, 89 parts of 3-amino-l ₃ 2, i »- triazole and 1000 parts of dimethylformamide are heated ^{to 130 ° C. for 6 hours.} Mach addition of 650 parts of methanol and cooling to room temperature is filtered off, washed with methanol and water and dried at 8O ⁰ C. This gives 330 parts of 4-naphthalsäure- (l ⁸ _J 2 _J 4 ^{t t} -triazolyl-3 ') - imide of the formula

If you use the same amounts of instead of Dimethyiformamids Dimethyl sulfoxide, N-methyl acetamide or phosphoric acid trisdimethylamide, the compound is thus obtained in the same yield

b. 17.2 parts of 4-Bromnaphthalsäure- ^(f l, 2 x, 4 "-triazolyl-3 ') imide and 50 parts of monoethanolamine are heated for 12 hours 75 to 8O ⁰ C, let the melt obtained in 500 parts of water, shrinks and the excreted compound of the formula

- NH

Aspirated, washed with water until the colorless drain and dried.

18 parts of a greenish yellow fluorescent dye are obtained (Absorpt.-max ". (In DMF) = 435 µm; fluorescence max. (DMF) = 524 am.)

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Example 8

-In the same way as described in Example 1 or 7, you can compounds of the formula (I) are prepared according to the invention, if one uses the amines of the formula (II) listed in Table 2 below in aliquot amounts and the so with the in Table 2 yields of compounds of formula (III) obtained in a manner analogous to that described in Example Id., with one of the amines mentioned in Examples 1 to 6 and falling under the formula (IV).

Table 2

Example Amine of Formula (II) "Preparation Yield

according to example '*

CH.

- Cl

, (la) 87 _S 5 (lc) 97 (la) 85

(la) '

98.2 %

CN

OCH.

(la) (la) (la)

85.0 %

92.5 %

91.7

Br

(la)

98.6 %

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CONH,

(la) 97.8 %

OCH.

(la) 91.5 %

NH

NH

(lc) 98.9 %

CHv '.CH ₇ 3

CH.

(lc) .97.7 %

H H

Cl

(lc) 95> 3

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Claims (3)

HOE 73 / F 377 claims 1. Compounds of the formula (I) NH-R ₁ (I) in which R ^ one optionally by aromatic or heterocyclic Substituted aliphatic or cycloaliphatic radicals A radical which contains at least one hydroxyl group and Rp is an aromatic or heterocyclic radical. 2. Process for the preparation of the compounds mentioned in claim 1, characterized in that first 1 mole of a ^ I-halogen-1,8-naphthalic anhydride with one mole of an amine of the formula HpN - Rp, in which Rp has the meaning given in claim 1 has, reacted and the compound of the formula thus obtained Halin which R _{2 has} the meaning given in claim i and Hal is a halogen, then with one mole of an amine of the formula H ₃ N - R ₁ , in wi
has meaning, implements. Formula H ₀ N - R., in which R _{4 has} the description given in claim 1 3. Use of the compounds mentioned and defined in claim 1 or of the compounds prepared according to claim 2 for coloring plastics, resins, oils .. waxes, varnishes, printing pastes _s paints or paper. '509-826 / 0795 ^: BATH ORIGINAL