CH640875A5 - Process for preparing pyridone dyes - Google Patents

Description

The present invention relates to a new process for alkoxy radicals having in particular 1 to 6 carbon atoms.

Preparation of pyndone dyes of the general formula The represented by Y and R] to R [q, if appropriate

Y R-substituted alkyl radicals are preferably lower alkyl groups

I I 25 pen or substituted lower alkyl radicals, and as special additives

\ / \ A A / 3 play for such residues are methyl, ethyl, n-propyl, n-butyl,

n-octyl, n-decyl and n-dodecyl, hydroxy-lower alkyl such as ß-hydroxymethyl, lower alkoxyalkyl with 1 to 6 carbon

I! II I

f ^ \ / -i \ atoms in the alkoxy and alkyl radical such as β- (methoxy or eth

O I 0 î N 30 oxy) ethyl and y-methoxypropyl, cyano-lower alkyl such as cyan

- ^ methyl, carbamoylmethyl, carbäthoxymethyl and acetyl-

R. R,

1 4 Rß called methyl.

• r. . . ..., Examples of wormR.hydrogens represented by Y, Ri and R3 to R10 are optionally substituted Al-aralkyl radicals, benzyl and β-phenylethyl.

kyl-, aralkyl-cycloalkyl-aryl or heterocyclic radical 35 As ßd id ffir dnen represented by y and R] to R10 or an optionally substituted amino group is R2, cycloalkyl radical and cyclohexyl. The optionally substituted arylre-alkoxy or optionally substituted alkyl or cyclogens represented by Y, R, and R3 and R4, independently of one another, each represent hydrogen, halogen, big R, are also phenyl or optionally substituted alkyl, and R5 and R ^, independently of one another, per water - Phenyireste, and as specific examples of such residues be substance or an optionally substituted alkyl, Aral- 4o Tol j chlorophenyl, methoxyphenyl and Äthoxyphe-kyl-, Cycloalkyl-, Aryl- or heterocychschen residue represent j Die du4 YR] and R5 bis R10, or R5 and R6 together with the nitrogen atom to which they are optionally substituted heterocyclic radicals are bonded, form a 5- or 6-membered nitrogen-containing * 5 and 6-membered heterocyclic ring, and as a heterocyclic ring, or R3 and R5 together with ë2ielle Bd ide for such residues, the 2.P id j 2_Thiazo_ the nitrogen atom a 5- or 6-membered nitrogen-containing 45 £ j.pj ridf j and i.Morpholinyi, which are each given heterocyclic ring or R4 and R5 are substituted together with n'enfaiis).

the nitrogen atom is a 5- or 6-membered nitrogen-containing piperide, morpholine, piperazine and pyrrolidine as a gene heterocyclic ring or R3 and R5 together with Bdpiele for 5th and 6th-membered heterocyclic rings

the stack offatom as well as R5 and R6 together with the na by linking R5 and R6 with the stick

Nitrogen atom, two nitrogen-containing heterocyclic rings, or R and R with the nitrogen atom or R4

bSlY hydrogen hydroxyl, -CN, -COOR7 and R6 are formed with the nitrogen atom.

grgefeTff! substlr ^ r Z is preferably -CN, -COOR, 1 or

Alkyl, aralkyl, cycloalkyk aryl or heterocyclic _C0NRnR12, where R "and R12 are hydrogen or alkyl with

The rest and Z represent a -CN-, ^ COOR ^, -CONR9R10- or j to 3 carbon atoms.

-COR9 group, where R7R8, R9 and R, 0 independently 55 of particular interest is the method according to the invention

yonemanderje hydrogen or an optionally also further for the production of dyes of the formula (1),

tuiert A kyl-, aralkyl-, cycloalkyl- aryl- or heterocych- in which R is hydrogen, alkyl having 1 to 6 carbon atoms represent the rest is characterized in that in Alk l_ and Alko t> Phenylj benzyl, ß-Phenyläthyl man em Hydroxypyndon of the formula ^ or cydohexyl; r2 hydrogen) chlorine, alkyl, hydroxyalkyl

* or alkoxy, each with 1 to 6 carbon atoms, R3 water

I serstoff, alkyl or alkoxy with 1 to 6 carbon atoms,

\ - ^ * \ and R4, hydrogen or alkyl with 1 to 6 carbon atoms

T • (2) men is, R5 and R6 with hydrogen, alkyl or hydroxyalkyl with

65 1 to 6 carbon atoms, alkoxyalkyl each having 1 to 6

f \ carbon atoms in the alkyl and alkoxy radical, carboxyalkyl

® 1 OH with 1 to 3 carbon atoms in the alkyl radical, ß-methyl sulfone

Amidoethyl or sulfo-n-butyl, Y is hydrogen, cyano,

1 carbomethoxy, carbäthoxy, carbonamido or alkyl with 1

640875

up to 6 carbon atoms and Z is cyan, carbomethoxy, carb-ethoxy or carbonamido.

Preferred dyes produced by the process according to the invention are those of the formula

NC.

\

CH.

✓ \

V

»

\

/

—N

A V

10th

/ \ »4

I I

• i

\ / •

I.

H.

/ R3

A V

(8th)

(5)

wherein R] is hydrogen, alkyl having 1 to 6 carbon atoms or hydroxyalkyl having 2 to 4 carbon atoms, and R5 and Rg are each alkyl having 1 to 4 carbon atoms, hydroxyalkyl having 2 to 4 carbon atoms or sulfo-n-butyl,

wherein R2 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. 15 The hydroxypyridones of the formula (2) are obtained by the method described in British Patent Specification No. 1 256 095, and furthermore as in «Heterocyclic Compounds - Pyridine and its Derivatives - Part 3 [Heterocyclic compounds - Pyridine and its derivatives - Part 3] », Published by Klinsberg and published by Interscience.

Specific examples of the hydroxypyridones are: 2,6-dihydroxy-3-cyan-4-methylpyridine, 1- (methyl or ethyl) -3-cyan-4-methyl-6-hydroxypyridone-2,1- (ß- Hydroxyethyl or y-methoxypropyl) -3-cyan-4- (methyl, phe-

or Rs and Rg together with the nitrogen atom to which they are 25 nyl ° the ethyl) -6-hydroxypyridone-2,1- (phenyl or anisyl) -

are bound to form a piperidine, morpholine, piperazine or pyrrolidine ring, and in particular those of the formula (5), in which Rj is alkyl having 1 to 6 carbon atoms and R5 and Rß are each ethyl or hydroxyalkyl having 2 to 4 carbon atoms.

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

NC.

CH, I -

0 '

\ * \

I II

(6)

V

I.

R_

\

OH

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

ON,

V \

l I

^ /

VC5

6

(7)

3-cyan-4- (methyl or phenyl) -6-hydroxypyridone-2, l-phenyl-3- (carbonamido or carbäthoxy) -4- (methyl or phenyl) -6-hydroxypyridone-2,2, 6-dihydroxy-3- (carbäthoxy or carbodiäthylamido) -4-methylpyridine, 2,6-dihydroxy-3- (car-3o bonamido or carbäthoxy) -pyridine, 2,6-dihydroxy-3-car-bonamido-4-phenylpyridine , 2,6-dihydroxy-3-cyan-4-carbon amidopyridine, 2,6-dihydroxy-3-cyan-4- (carbomethoxy or carbäthoxy) pyridine, ethyl-2,6-dihydroxy-3-cyanopyridyl-4 -acetate, 2,6-dihydroxy-3-cyanopyridyl-4-acetamide, 2,6-di-35 hydroxy-3,4-di- (carbethoxy) pyridine, 2,6-dihydroxy-

3-carbonamido-4-carboxy-pyridine, ethyl-2,6-dihydroxy-isonicotinate, 2,6-dihydroxy-isonicotinamide, 2,6-dihydroxy-isonicotinic acid diethylamide and 2,6-dihydroxy-3-cyano-

4-ethoxycarbonyl-1-methylpyridine.

The procedure for the preparation of the dyes

Formula (1) according to the method according to the invention is particularly valuable in the synthesis of water-soluble or hydrophilic dyes, because the isolation and / or purification of these dyes is difficult.

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

A purer dye is also obtained by the process according to the invention, and this is particularly advantageous since the dyes are used especially in photographic material 50.

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

CH ~

5

40

45

I.

55 NC.

\ ^ \

\ /

1 I

A / \

R,

wherein R5 and R6 have the meanings given.

The reaction advantageously takes place in a solvent,

preferably acetone, ethanol or acetic acid, without or in particular with heating from the outside. The dyes can be easily isolated in the usual way, e.g. by precipitation with water.

The nitrosoanilines of the formula (3) are expediently obtained according to the method described in “Organic Syntheses - Collected Volume II”,

Page 223, described method from the 65 corresponding dye to the anilines.

The nitrosoanilines are obtained by reacting the anilines A of formula B.

V

(5)

R,

c, h

2n5

c, h

2n5

R5

ch3

c2h4oh r6

ch3

c2h4oh

640 875

Table I (continued)

dye

C D E

ri c.h4oh h

ch3

Rs

QH4OH QH4OH CH3

r6

c2h4oh c2h4oh

C4H8S03Na

^ max (MeOH) 585.405 nm. Similarly prepared:

Dye B s Dye C Dye D

Melting point 176-7 ° C,

(MeOH) 591.408 nm melting point 184-5 ° C, Ä-max (MeOH) 588.410 nm melting point 189-90 ° C, ^ max (MeOH) 584.415 nm

example

Dye A: 17.8 g of 3-cyan-1-ethyl-6-hydroxy-4-methyl-pyridone-2 and 16.8 g of 4-dimethylaminonitrosobenzene are stirred together in 100 ml of acetic acid for thirty minutes at room temperature. It is diluted with water and the precipitated dye is washed with water until the washing liquid is colorless. The dye is dried in vacuo to give 20.0 g of dye A as a green solid. Melting point: 192-3 ° C.

Dye E: 0.82 g of 3-cyano-6-hydroxy-l, 4-dimethylpyridone-2 and 1.478 g of N-methyl-N-4'-sulfobutyl-4-nitrosoaniline (sodium salt) are mixed in 5 ml at room temperature for four hours Es-15 acetic acid stirred together. The dye is precipitated from ether and washed with ether. 2.20 g of dye E are obtained as a brown solid which decomposes at temperatures above 140.degree. Xmax (MeOH) 588.410 nm.

C.

Claims (11)

640 875 2nd PATENT CLAIMS 1. Process for the preparation of pyridone dyes of the general formula Y I R " Z \ / \ /% / R3 i I ! , R " c / v \) vy5 R-, (1) 1 \ R4 6 where R! Is hydrogen, an optionally substituted alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radical or an optionally substituted amino group, R2, R3 and R4 independently of one another are each hydrogen, halogen, alkoxy or optionally substituted alkyl or cycloalkyl and R5 and R6 each independently represent hydrogen or an optionally substituted alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radical or R5 and R6 together with the nitrogen atom to which they are attached form a 5- or 6-membered nitrogen-containing heterocyclic ring, or R3 and R5 together with the nitrogen atom form a 5- or 6-membered nitrogen-containing heterocyclic ring or R4 and R6 together with the nitrogen atom form a 5- or 6-membered nitrogen-containing heterocyclic ring or R3 and R5 together with the nitrogen atom and R5 and R6 together form two nitrogen-containing heterocyclic rings with the nitrogen atom, Y water toff, hydroxyl, -CN, -COOR7, -CONR7R8, -COR? or an optionally substituted alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radical and Z is a -CN, -COOR9, -CONR9R, 0- or -COR9 group, where R7, R8, R9 and R10 each independently represent hydrogen or an optionally substituted alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radical, characterized in that a hydroxypyridone of the formula Rio and Y each are hydrogen, alkyl having 1 to 6 carbon atoms, hydroxyalkyl having 1 to 6 carbon atoms, alkoxy-alkyl each having 1 to 6 carbon atoms in the alkyl and alkoxy radical, cyanoalkyl having 1 to 6 carbon atoms in the Al-5 alkyl radical, carbamoylmethyl, carbäthoxymethyl or acetyl-methyl, Ri and R3 to Rio each benzyl or ß-phenylethyl, R | to Rio are each cyclohexyl, R, and R5 to Rio are each optionally substituted phenyl or optionally substituted 5- or 6-membered heterocyclic rings, R5 and R6 or R3 and io R5 or R4 and R6 with the nitrogen atom to which they are attached are a piperidine, morpholine, piperazine or pyrrolidine ring, Y furthermore hydroxyl, -CN, -COOR | j or -CONRiiRi2 and Z-CN, -COORii or-CONR i (R12, where Ri i and R] 2 are hydrogen or alkyl having 1 to 3 carbon atoms. 3. A process for the preparation of dyes according to claim 1, characterized in that in formula (1) R, hydrogen, alkyl having 1 to 6 carbon atoms, hydroxyalkyl having 1 to 6 carbon atoms, alkoxyalkyl each 201 to 6 carbon atoms in the alkyl and alkoxy radical, phenyl, benzyl, β-phenylethyl or cyclohexyl, R2 hydrogen, chlorine, alkyl, hydroxyalkyl or alkoxy each having 1 to 6 carbon atoms, R3 hydrogen, alkyl or alkoxy having 1 to 6 carbon atoms, and R4 is hydrogen or alkyl with 251 to 6 carbon atoms, R5 and R6 are each hydrogen, alkyl or hydroxyalkyl with 1 to 6 carbon atoms, alkoxyalkyl with 1 to 6 carbon atoms each in the alkyl and alkoxy radical, carboxyalkyl with 1 to 3 carbon atoms in the alkyl radical, Are methylsulfonamidoethyl or sulfo-n-butyl 3o, Y is hydrogen, cyan, carbomethoxy, carbethoxy, carbonamido or alkyl having 1 to 6 carbon atoms and Z is cyan, carbomethoxy, carboethoxy or carbonamido. 4. A process for the preparation of dyes according to claim 1 of the formula 40 Y Z 1 V \ i II (2) CH ncv AV <"V- ^ 5 ! i 0 • 0 R Y (5) 45 OH 1. wherein Y, Z and R] have the meanings given, with an N, N-disubstituted 4-nitrosoaniline of the formula in which R] is hydrogen, alkyl having 1 to 6 carbon atoms or hydroxyalkyl having 2 to 4 carbon atoms, R5 and Rg alkyl having 1 up to 4 carbon atoms, hydroxyalkyl with 2 Are 50 to 4 carbon atoms or sulfo-n-butyl or R5 and R6 together with the nitrogen atom to which they are attached form a piperidine, morpholine, piperazine or pyrrolidine ring, characterized in that a hydroxypyridine of the formula 55 ON R \ / \ / 3 • 9 I II (3) , R " y v "5 l4 CH, i. NC. 60 wherein R2 to R6 have the meanings given, condensed. 2. A process for the preparation of dyes according to claim 1, characterized in that in formula (1) Rj to 'W \ • • I IJ 0 ^ Y noh I. R (6) 65 wherein R] has the meaning given, with an N, N-di-substituted 4-nitrosoaniline of the formula 3,640,875 ON / • where Y, Z and R! have the meanings given with ^^. an N, N-disubstituted 4-nitrosoaniline of the formula i y d '(7) ^ / \ / R5 r \ 5 I2 6 ON \ / 3 where R5 and R6 have the meanings given, JJJ ^ (3) densifies. • • 5. The method according to claim 1, characterized in 10 ^ / 5 that the condensation reaction in a solvent I ^ he follows. R 6. The method according to claim 5, characterized in that 4 is used as the solvent acetone, ethanol or acetic acid. 15 worjn r2 to Rfi have the meanings given, con- 7. The method according to claim 6, characterized in that during the condensation reaction heat from the P idon dyes are in photographic material. outside influence. Uen, for example, as a filter. or antihalation dyes reversible. 20 The terms lower alkyl or lower alkoxy, such as .., "", ■, rx-x • ", wegs used in this patent mean alkyl or.