DE2853354A1 - PROCESS FOR THE MANUFACTURING OF PYRIDON DYES - Google Patents

Description

DR. BERG DIPL.-fNG. STAFF DIPL.-ING. SCHWaBE DR. DR. SANDMAIR

PATENTANWÄLTE Postfach 860245 8000München 86 28 53354

Attorney's file: 29 75 ¹¹ December 11, 1978

CTPA-GFIGY AG
Basel, Switzerland

Process for the preparation, of pyridone dyes

Case P-117? 3 / TLF 1193 / +

· »(089) 98 82 72 Telegrams: Bank accounts: Hypo-Bank Munich 4410122 850

988273 BERGSTAPFPATENT Munich (BLZ 70020011) Swift Code: HYPO DE MM

988274 TELEX: QOQQ / Q / A / Ad Bayen Vereinsbank Munich 453100 (bank code 70020270) 983310 0524560 BERG d ^β «3 O If oil U 4 {JT Postscheck Munich 65343-808 (bank code 70010080)

Case 8-11723 / ILF 1193 / +

Process for the preparation of pyridone dyes

The present invention relates to a new process for the preparation of pyridone dyes in general Formula 1). These dyes are the subject of DE-OS 2808825, and they are in photographic materials for example usable as filter or antihalation dyes.

DE-OS 2808825 describes a process for the preparation of pyridone dyes of the formula

(D ι ι ²

\ / \ AA / ^R 3
• «« ·

I I Il I

»1 ^E 4 H ₆

where R _{1 is} hydrogen, an optionally substituted alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radical or an optionally substituted amino group, R_, R, and R independently of one another are each hydrogen, halogen, alkoxy or optionally substituted alkyl or cycloalkyl as well R ₅ and R independently of one another each represent hydrogen or an optionally substituted alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radical, or R and R _ß together with the nitrogen atom to which they are bonded form a 5- or 6- membered nitrogen-containing heterocyclic ring, or R ₃ and R ₁ - together with the stick-

substance atom a 5- or 6-membered nitrogen-containing heterocyclic ring or R- and Rg together with the nitrogen atom a 5- or 6-membered nitrogen-containing heterocyclic ring or R, and Rt- together with the nitrogen atom and R _c and R _c together with the Nitrogen atom form two nitrogen-containing heterocyclic rings, Y is hydrogen, hydroxyl, -CN, -COOR ^, -CONRyRg, -COR ^ or an optionally substituted alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radical and Z is -CN-, -COORg-, -CONRnR ₁ Q- * -S0, ®- or -CORq group, where R ^, Rg, Rq and R-, _Q are each independently hydrogen or an optionally substituted alkyl, aralkyl, cycloalkyl , Aryl or heterocyclic radical which is characterized in that one is a hydroxypyridone of the formula

AA

⁰ Ϊ

OH

wherein Y, Z and R- have the meanings given with an N, N - disubstituted 4-aminoaniline of the formula

^H 2 ^N \ / X / ^R 3

• ·

I Il. ,

(3) V ^s Λ

■ ί ^Η -

where Rp to Rg have the meanings given, condensate sated.

The present invention is a new process for the preparation of dyes of the formula (1), which is characterized in that a hydroxypyridone of the formula (2) with an N, N-disubstituted 4-

909848 / 049f

Nitrosoaniline of the formula

i <

^R 4 \

in which Rp to Rg have the meanings given, condensed.

The terms lower alkyl and lower alkoxy, such as Used throughout this patent specification are alkyl or alkoxy radicals having 1 to 6 carbon atoms.

The optionally substituted alkyl radicals represented by Y and R- to R-, _Q are preferably lower alkyl groups or substituted lower alkyl radicals, and specific examples of such radicals are methyl, ethyl, n-propyl, η-butyl, n-octyl, n- Decyl and n-dodecyl, hydroxy lower alkyl such as ß-hydroxymethyl, lower alkoxyalkyl with 1 to β carbon atoms in the alkoxy and alkyl radical such as [B- (methoxy or ethoxy) ethyl and 7-methoxypropyl, cyanni ed eralkyl such as cyanine ethyl, carbamoylmethyl, carbethoxymethyl and called acetylmethyl.

Examples of aralkyl radicals represented by Y, R- and R ^ to R ₁₀ are benzyl and β-phenylethyl.

Cyclohexyl may be mentioned as an example of a cycloalkyl radical represented by Y and R- to R-, _Q. The optionally substituted aryl radicals represented by Y, R- and R ₁ - to R ₁₀ are preferably phenyl or optionally substituted phenyl radicals, and specific examples of such radicals are phenyl, tolyl, chlorophenyl, methoxyphenyl and ethoxyphenyl. The optionally substituted heterocyclic radicals represented by Y, R ₁ and Rt- to R ₁₀ are preferably 5- and 6-membered heterocyclic rings, and specific examples of such radicals are 2-pyridyl, 2-

909848/8497

-J-

Thiazolyl, 1-piperidinyl and 1-morpholinyl, which respectively are optionally substituted, mentioned.

Piperidine, morpholine, piperazine and pyrrolidine may be mentioned as examples of 5- and 6-membered heterocyclic rings, which by: linking Rj- and Rg with the nitrogen atom, or R, and R ₅ with the nitrogen atom or R ^ and Rg with the Nitrogen atom are formed.

Z preferably represents -CN, -COOR -, -, or -CONR-, -, R-, ο, where R -, -, and R-, ρ are hydrogen or alkyl with Represent 1 to 3 carbon atoms.

The process according to the invention is also of particular interest for the preparation of dyes of the formula (1) in which R _{1 is} hydrogen, alkyl having 1 to 6 carbon atoms, hydroxyalkyl having 1 to 6 carbon atoms, alkoxyalkyl having 1 to 6 carbon atoms in the alkyl and alkoxy radicals, Phenyl, benzyl, ß-phenylethyl or cyclohexyl, Rp hydrogen, chlorine, alkyl, hydroxyalkyl or alkoxy each with 1 to 6 carbon atoms, R, hydrogen, alkyl or alkoxy with 1 to 6 carbon atoms, and R hydrogen or alkyl with 1 to 6 carbon atoms R ₅ and R _{6 are} hydrogen, alkyl or hydroxyalkyl with 1 to 6 carbon atoms, alkoxyalkyl with 1 to 6 carbon atoms in the alkyl and alkoxy radical, carboxyalkyl with 1 to 3 carbon atoms in the alkyl radical, ß-methylsulfonamidoethyl or sulfo-n-butyl , Y is hydrogen, cyano, carbomethoxy, carbethoxy, carbonamido or alkyl having 1 to 6 carbon atoms and Z is cyano, carbomethoxy, carbethoxy or carbonamido. Preferred dyes according to the invention are those of the formula

CH.

(5) T.

9098487.049?

/ to

wherein R is, hydrogen, alkyl with 1 to 6 carbon atoms or hydroxyalkyl with 2 to 4 carbon atoms, as well as Rc and Rg each alkyl with 1 to 4 carbon atoms, Hydroxyalkyl with 2 to 4 carbon atoms or sulfo-n-butyl are, or R ^ and Rg together with the nitrogen atom ,, to which they are bound form a piperidine, morpholine, piperazine or pyrrolidine ring, and in particular those of the formula (5) in which R-, alkyl having 1 to 6 carbon atoms and Rj- and Rg are each ethyl or are hydroxyalkyl of 2 to 4 carbon atoms.

The dyes of the formula (5) are obtained by condensation of a hydroxypyridone of the formula

</ V \ h

wherein R-, has the meaning given, with an N, N-di substituted 4-nitrosoaniline of the formula

wherein R ₁ - and Rg have the meanings given.

The reaction is advantageously carried out in a solvent, preferably acetone, ethane oil or acetic acid, with or without external heating. The dyes can easily be isolated in a conventional manner, for example by Precipitation with water.

The nitrosoanilines of the formula (4) are expediently obtained in accordance with the methods described in "Organic Syntheses - Collected" Volume II ", page 223, described method from the anilines corresponding to them.

The nitrosoanilines are obtained by reacting the

S09848 / 849?

Anilines of the formula ^

ι ²

where Rp to R ^ have the meanings given, with sodium nitrite in a solution of these anilines in concentrated hydrochloric acid at temperatures of at most 8 ^° C.

The hydroxypyridones of the formula (2) are obtained according to the method described in British Patent No. 1,256,095 explained method, also as in "Heterocyclic Compounds - Pyridines and its Derivatives - Part 3 [Heterocyclische Compounds - Pyridine and its derivatives - Part 3] "» published by Klinsberg and published by Interscience, described.

Specific examples of the hydroxypyridones are: 2,6-dihydroxy-3-cyano-4-methylpyridine, 1- (methyl or ethyl) -3-cyano-4-methyl-6-hydroxypyridone-2, 1- (ß-hydroxyethyl or γ-methoxypropyl) -3-cyano-4- (methyl, phenyl or ethyl) -6-hydroxypyridon-2, l- (phenyl or Anisyl) -3-cyano-4- (methyl or phenyl) -6-hydroxypyridon-2, 1-Phenyl-3 ~ (carbonamido or carbethoxy) -4- (methyl or phenyl) -6-hydroxypyridone-2, 2,6-dihydroxy-3- (carbethoxy or carbodiäthylamido) -4-methylpyridine, 2,6-dihydroxy-3- (carbonamido or carbethoxy) pyridine, 2,6-dihydroxy-3-carbonamido-4-phenylpyridine, 2,6-dihydroxy-3-cyano-4-carbon amidopyridine, 2,6-dihydroxy-3-cyano-4- (carbomethoxy or carbethoxy) pyridine, ethyl-2,6-dihydroxy-3-cyanopyridyl-4-ac etat, 2,6-dihydroxy-3-cyanopyridyl-4-ac etamide, 2,6-dihydroxy-3,4-di (carbethoxy) pyridine, 2,6-dihydroxy-3-carbonamido-4-carbethoxypyridine, Ethyl 2,6-dihydroxyisonicotinate, 2,6-dihydroxy-isonicotinamide, 2,6-dihydroxyisonicotinic acid diethylamide and 2,6-dihydroxy-3-cyano-4-ethoxycarbonyl-1-methylpyridine.

909848 / Θ49Τ

The procedure for the preparation of the dyes of the formula (I) by the method according to the invention is special valuable in the synthesis of water-soluble or hydrophilic dyes, for isolation and / or purification these dyes is difficult.

Furthermore, the present process is advantageous when R-, in the formulas (1) and (2) is hydrogen ..

The process according to the invention is also obtained a purer dye, and this is particularly advantageous as the dyes are specifically used in photographic Material to be used.

Table I gives examples of dyes of the formula prepared by the process according to the invention

(9)

CH.

I!

I. R.

Table I.

Color
material ^R i V ^R 6 A. ^C 2 ^H 5 CH ₃ CH ₃ B. ^C 2 ^H 5 C ₂ H ₄ OH C "H" OH
2 4 C. C ₂ H ₄ OH C ₂ H ₄ OH C ₂ H ₄ OH D. H C ₂ H ₄ OH C ₂ H ₄ OH E. CH ₃ ^CH 3 C ₄ H ₈ SO ₃ Na

909848/8497

Example . "

Dye A ; 17.8 g of 3-cyano-1-ethyl-6-hydroxy-4-methylpyridone-2 and 16.8 g of 4-dimethylaminonitrosobenzene are stirred together in 100 ml of acetic acid for thirty minutes at room temperature. The mixture is diluted with water and the dyestuff which has precipitated out is washed until the wash liquid with water is colorless the dyestuff is dried in vacuo to give 20.0 g of dye A provides as a green solid. melting point:. 192-3 ⁰ C. λ _max (MeOH) 585, 405 nm.

Produced in a similar way:

Dye B- : melting point 176-7 ⁰ C,

(MeOH) 591, 408 nm

Dye C : melting point 184-5 ° C,

^ max ( ^Me0H ) 588, 410 nm

Dye D ; Melting point 189-9O ⁰ C,

X _max (MeOH) 584, 415 nm

Dye E ; 0.82 g of 3-cyano-6-hydroxy-1,4-dimethylpyridone-2 and 1.478 g of N-methyl-N-4-sulfobutyl-4-nitrosoaniline (sodium salt) are in 5 ml of acetic acid stirred together. The dye is precipitated from ether and washed with ether. This gives 2.20 g of dye F. as a brown solid, which decomposes at temperatures above 140 ^0C.

^{X (Me0H) 588> 410} *** '

9098Α8 / ΘΑ97

Claims (7)

■ PATENTANWÄLTE _M0 NCHEN 80 ■ MAUERKIRCHERSTRMB Claims . . - v. Process for the preparation of dyes of the general formula i ■■ i \ ι R W wherein R-, hydrogen, an optionally substituted alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radical or an optionally substituted amino group, Rp, R ^ and R / are each independently hydrogen, halogen, alkoxy or optionally substituted alkyl or Cycloalkyl and Rp- and Rg each independently represent hydrogen or an optionally substituted alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radical or R ₁ - and Rg together with the nitrogen atom to which they are bonded represent a 5- ° the 6-membered nitrogen-containing heterocyclic ring, or R, and R ₁ - together with the nitrogen atom form a 5- or 6-membered nitrogen-containing heterocyclic ring or R- and Rg together with the nitrogen atom a 5- or 6-membered nitrogen-containing heterocyclic ring or R-, and R ^ together with the nitrogen atom and R ₁ - and Rg together with the nitrogen atom are two nitrogen-containing heterocyclic Ri Form nge, Y hydrogen, hydroxyl, -CN, -COOR ₁₇ , -CONRyRg, -COR ₇ or an optionally substituted alkyl, aralkyl, cycloalkyl, aryl or heterocyclic ©: radical and Z is a -CN-, -COOR ₉ -, -CONR ₉ R ₁₀ -, -SO®- or -COR ₉ group, where R ^, R _Q , R ₉ and R ₁₀ are each independently hydrogen or an optionally substituted alkyl, aralkyl, cycloalkyl , Aryl or heterocyclic radical represent, by condensation ORIGINAL INSPECTED of a hydroxypyridone of the formula • " wherein Y, Z and R _{1 have} the meanings given, with a Ν, Ν-disubstituted aniline according to the process of DE-OS 2808825, characterized in that an N, N-disubstituted 4-nitrosoaniline of the formula A Λ • · I Il used, wherein R to R have the meanings given. 2. Process for the preparation of dyes according to claim 1, characterized in that R ₁ to R ₁ and Y are each hydrogen, alkyl with 1 to 6 carbon atoms, hydroxyalkyl with 1 to 6 carbon atoms, alkoxyalkyl with 1 to 6 carbon atoms each in the alkyl and Alkoxy radical, cyanoalkyl with 1 to 6 carbon atoms in the alkyl radical, carbamoylmethyl, carbethoxymethyl or acetylmethyl, R ₁ and R- to R, _Q each benzyl or / 3-phenylethyl, R, to R each cyclohexyl, R ₁ and Rj. To R ₁ each optionally substituted phenyl or optionally substituted 5- or 6-membered heterocyclic rings are R_ and R or R_ and R or R and R- with the nitrogen atom to which they are bonded 4 D are, form a piperidine, morpholine, piperazine or pyrrolidine ring, Y is also hydroxyl, -CN, -COOR or -COOR ₁ R, - and Z is -CN, -COOR ₁ or -CONR R, where R ₁ and R ₁ "are hydrogen or alkyl of 1 to 3 carbon atoms. 3. Process for the production of dyes according to claim 1, characterized in that R-, hydrogen, alkyl with 1 to 6 carbon atoms, hydroxyalkyl with 1 to 6 carbon atoms, alkoxyalkyl with 1 to 6 carbon atoms each in the alkyl and alkoxy radical, phenyl, benzyl , ß-phenylethyl or cyclohexyl, R _{2 is} hydrogen, chlorine, alkyl, hydroxyalkyl or alkoxy each with 1 to 6 carbon atoms, R, hydrogen, alkyl or alkoxy with 1 to 6 carbon atoms, and R is hydrogen or alkyl with 1 to 6 carbon atoms, R ₅ UQd R _{6 are} each hydrogen, alkyl or hydroxyalkyl with 1 to 6 carbon atoms, alkoxyalkyl with 1 to β carbon atoms in the alkyl and alkoxy radical, carboxyalkyl with 1 to 3 carbon atoms in the alkyl radical, ß-methylsulfonamidoethyl or sulfo-n-butyl, Y is hydrogen, cyano, carbomethoxy, carbethoxy, carbonamido or alkyl having 1 to 6 carbon atoms and Z is cyano, carbomethoxy, carbethoxy or carbonamido. 4. Process for the preparation of dyes according to Claim 3 of the formula wherein R, hydrogen, alkyl with 1 to 6 carbon atoms or hydroxyalkyl with 2 to 4 carbon atoms, R ₁ - and Rg are alkyl with 1 to 4 carbon atoms, hydroxyalkyl with 2 to 4 carbon atoms or sulfon-butyl or R _c and R _r together with the nitrogen atom, D b to which they are bound, a piperidine, morpholine, Form piperazine or pyrrolidine ring, characterized in that a hydroxypyridone of the formula 48/0 I Il o'V \ » - I. wherein R- has the meaning given with an N, N-disubstituted 4-nitrosoaniline of the formula in which R ₁ - and Rg have the meanings given, condensed. 5. The method according to claim 1, characterized in that the condensation reaction takes place in a solvent. 6. The method according to claim 5, characterized in that the solvent used is acetone, ethanol or acetic acid begins. 7. The method according to claim 6, characterized in that that one brings heat from the outside to the effect during the condensation reaction. §09848 / 049?