CA1292735C

CA1292735C - Organic compounds

Info

Publication number: CA1292735C
Application number: CA000547519A
Authority: CA
Inventors: Reinhard Pedrazzi
Original assignee: Sandoz AG
Current assignee: Clariant Finance BVI Ltd
Priority date: 1986-09-23
Filing date: 1987-09-22
Publication date: 1991-12-03
Anticipated expiration: 2008-12-03
Also published as: EP0262095A2; JP2579643B2; EP0262095A3; JPS63108071A; ZA877166B; DE3767105D1; EP0262095B1; DE3632307A1

Abstract

Abstract A compound which in one of the possible tautomeric forms corresponds to formula I

Description

l~Z~35 Case 150-5122 IMPROVEMENTS IN OR RELATING TO ORGANIC COMPOUNDS
_ This invention relates to disazo compounds containing sul-phonic acid groups and salts thereof and to a process for their preparation, which compounds are suitable for use as direct dyes as such or in form of dyeing preparations.

According to the invention there is provided compounds which in one of the possible tautomeric forms correspond to formula I

7 ~ N = N ~ NHCO ~ N = N ~ \~ R3 (S3H)2 Rl HO

or a salt thereof, in which the sulphonic acid groups are in the 5,7- or 6,8-positions of the naphthyl radical, R1 is hydrogen, chlorine, methyl, methoxy, -NHCOCH3 or -NHCONH2, R2 is hydrogen, methyl or methoxy, and R3 is -NHCN or -NHCONH2, or a mixture of such compounds each of which is in free acid or salt form.

12~92735 - 2 - Case 150-5122 The sulphonic acid groups on the naphthyl radical are pref-erably in the 6,8-positions.
R1 is preferably R1a, where R1a is hydrogen, methyl or methoxy. More preferably it is R1b, where R1b is hydrogen or methyl.
R2 is preferably R2a, where R2a is hydrogen or methoxy.
R3 is preferably -NHCN.

Most preferred are compounds of formula I in which R1 is R1b, R2 is R2a, R3 is -NHCN, and the sulphonic acid groups are in the 6,8-positions.

A compound of formula I is in free acid form, alkali metal salt form such as lithium, sodium or potassium salt form, or un-substituted or substituted ammonium salt form, or may also be in mixed salt form. Any substituted ammonium cation may be derived from a primary, secondary or tertiary amine. For example, the following amines are suitable:- mono-, di- or tri-methyl-, -ethyl-, -propyl- or -butyl-amine; mono-, di- or tri-ethanol-, -propanol- or -isopropanol-amine; N-methyl-N-hydroxyethylamine, N-methyl-N,N-di(hydroxyethyl)amine, N-ethyl-N-hydroxyethoxyethyl-amine, morpholine, piperidine, piperazine, N-hydroxyethylmorpho-line, N-hydroxyethylpiperazine, N-aminoethylpiperazine; ethylene-diamine, hexamethylenediamine; dimethylaminopropylamine, diethyl-aminopropylamine, diethylene glycol amine, diglycol amine and 3-methoxypropylamine.

Also suitable as amines are polyglycol amines. They can be prepared, for example, by reacting ammonia, alkyl- or hydroxy-alkylamine with alkylene oxides.
Any substituted ammonium ion may also be a quaternary ammonium ion derived from ammonium compounds which preferably contain one or two quaternary ammonium ions. Examples are tetra-methyl-, tetraethyl-, trimethylethyl-, dimethyl-di(2-hydroxy-propyl)-, trimethylhydroxyethyl-, tetrahydroxyethyl- and tri-methylbenzyl-ammonium hydroxide.

12~Z735 - 3 - Case 150-5122 The compounds of formula I or a mixture thereof may be pre-pared by reacting the diazonium salt of one or more aminoazo com-pounds of formula II, ~ N = N ~ NHC0 ~ NH2 II
(S3H)2 Rl in which the positions of the sulpho groups and R1 and R2 are as defined above, with a compound which in one of the possible tautomeric forms cor-responds to formula III, in which R3 is as defined above, or a mixture of compounds of formula III.

Diazotisation and coupling reaction may be effected in ac-cordance with known methods.
Diazotisation conveniently is carried out in a medium con-taining a mineral acid, preferably hydrochloric acid, at 0-20C.
Coupling conveniently is carried out at pH 4-12, preferably 6-9.

The starting compounds of formulae II and III are either known or may be prepared in accordance with known methods from available starting compounds.

Any resulting compound of formula I may be used in the form of the solution as obtained, however, this solution may also be converted into a solid by spray-drying. Furthermore, the conven-tional method of isolation used for dyestuffs, salting out of the solution, filtering off and drying, is also suitable.

1~29Z735 - 4 - Case 150-5122 The type of cations associated with the sulpho groups in a compound of formula I may be influenced in different ways depend-ing on the preparation process. One possibility consists in filtering off the diazonium salt which is obtained in the above S process, and washing it with water. The solid diazonium compound is then added to an aqueous slurry or solution of the coupling component, which contains a basic salt, lithium-, sodium-, potas-sium- or ammonium-hydroxide, one or more organic amines or a quat-ernary ammonium compound. Another method consists in converting the compound of formula I, which is obtained by diazotisation and coupling and is isolated in the sodium salt form, into free acid form by using a mineral acid, preferably hydrochloric acid, then filtering and washing with water; the compound is subsequently neutralised and thus converted into the desired alkali metal salt or ammonium salt. Any type of mixed salt form may be obtained by effecting partial conversion into free acid form and/or by step-wise neutralisation.
The salt-changing method, conversion of one salt form into another, can also be used.

If diazotisation takes place using alkyl nitrites, dinitro-gen trioxide or mixtures of nitric oxide and oxygen instead of alkali metal nitrite, it is possible to produce solutions of the end products which are free from metal ions. If desired, corre-sponding salts may be obtained by adding a cation-donating base or by adding an amine.

The compounds according to the invention in form of their water-soluble salts are useful for dyeing or printing hydroxy group- or nitrogen-containing organic substrates. For example, they are suitable for dyeing or printing fibres, threads or tex-tiles produced therefrom, which consist of or contain polyamide or cellulose materials, such as cotton, in accordance with known methods; cotton is preferably dyed by the exhaust method, for ~Z~Z735 - 5 - Case 150-5122 example from a long or short liquor, at room temperature to boil-ing temperatures.
Printing is effected by means of impregnation with a print-ing paste which is prepared by known methods.
The new dyestuffs can also be used for dyeing or printing leather, preferably chrometanned types of leather, as well as glass or glass products consisting of variable chemical components in accordance with known methods. Furthermore, the dyestuffs are suitable for the preparation of inks in accordance with conven-tional methods.
The compounds of formula I are especially suited for dyeing or printing paper in accordance with known methods, e.g. for the preparation of sized or unsized paper dyed in the stock. They may also be used for dyeing paper by the dipping process.
The dyeings and prints obtained (especially those on paper) have good fastness to usage.
The compounds of formula I may be used as such or may also be used in the form of dyeing preparations, which are preferably used for dyeing paper. Suitable liquid, preferably aqueous, con-centrated dyeing preparations may be made in accordance with known methods, advantageously by dissolving in suitable solvents, op-tionally adding an adjuvant, e.g. a hydrotropic compound or a sta-biliser. The possibility of producing such stable, aqueous concen-trated preparations in the course of the dyestuff synthesis with-out intermediate isolation of the dyestuff is particularly advan-tageous. In this process, coupling takes place for example in the presence of appropriate amines and in particular in the presence of quaternary ammonium hydroxides which serve to introduce corre-sponding cations as defined above, and optionally in the presence of further hydrotropic adjuvants.
Suitable hydrotropic adjuvants are for example low molecular weight amides, lactones, alcohols, glycols or polyols, low molecu-lar weight ethers or hydroxyalkylation products, as well as ni-triles or esters; among these the following compounds are prefera-bly used:- Methanol, ethanol, propanol; ethylene-, propylene-, lZ92~35 - 6 - Case 150-5122 diethylene-, thiodiethylene- and dipropylene- glycol; butanediol;
~-hydroxypropionitrile, pentamethylene glycol, ethylene glycol monoethyl- and -propylether, ethylene diglycol monoethylether, triethylene glycol monobutylether, butyl polyglycol, formamide, dimethylformamide, pyrrolidone, N-methylpyrrolidone, glycol ace-tate, butyrolactone, urea and ~-caprolactam.
Hydrotropic compounds are described e.g. by H. Rath and S.
MUller, in Melliand Textilberichte 40, 787 (1959) or by E.H.
Daruwalla in K. Venkataraman, The Chemistry of Synthetic Dyes, Vol. VIII, pages 86-9Z (1974).
The additional content of a hydrotropic compound further im-proves the stability on storage of the dyestuff preparation, and the solubility of the dyestuff employed.
An example of a suitable liquid dye preparation is (all parts are by weight):-100 parts of a compound of formula I in water-soluble salt form, 1-100, preferably 1-10, parts of an inorganic salt, 100-800 parts of water, 0-500 parts of one of the hydrotropic compounds as defined above.
Depending on the salt form used, the liquid dye preparation may be a suspension or is preferably a true solution. The prepara-tions are stable and can be stored for a long period of time.
Similarly, the compounds of formula I may be made into solid, preferably granulated dyeing preparations in accordance with known methods, advantageously by granulating as described in French Patent Specification No. 1.581.900.

A suitable granulated preparation comprises (all parts are by weight):-100 parts of a compound of formula I in water-soluble salt form, 1-100, preferably 1-10, parts of an inorganic salt, 0-800 parts of a standardising agent (preferably non-ionic, such as starch, dextrin, sugar, glucose and urea).

1~92735 - 7 - Case 150-5122 The solid preparation may contain up to 10% residual mois-ture.

Depending on the cation or cation mixture associated with the sul-phonic acid groups, the compounds of formula I possess good solu-bility properties, particularly good solubility in cold water.
Furthermore, when used in paper-making, they colour the waste water only to a slight extent or not at all. They do not mottle on paper and are substantially insensitive to filling material and pH
over wide ranges. They are only slightly inclined to give two-sided dyeing on paper. The dyeings on paper have good light fast-ness properties, after a long-term exposure to light, the shade alters tone-in-tone. The dyed papers also have very good wet fast-ness properties, they are fast to water, milk, fruit juices, sweetened mineral water and tonic water, and in addition they show good alcohol fastness properties.
The dyestuffs have good substantivity, i.e. they exhaust practically quantitatively, and show good build-up; they can be added to the paper pulp directly, i.e. without previously dissolv-ing, as a dry powder or granule, without reducing the brilliance or the yield of colour. It is advantageous to use the genuine so-lutions of the dyestuffs as given above, which are stable, of low viscosity and thus capable of being accurately measured out. Fibre materials which contain mechanical wood pulp are dyed in good, even quality with the compounds of the present invention. The dyed paper is both oxidatively and reductively bleachable, which is im-portant for the recycling of waste paper.

The following examples further serve to illustrate the in-vention. In the examples, all parts and percentages are by weight or volume unless otherwise stated, and the temperatures are in degrees centigrade.

12Z`~3S

- 8 - Case 150-5122 Example 1 43.7 Parts of the aminoazo dyestuff prepared by weakly acid coupling of diazotised 2-aminonaphthalene-6,8-disulphonic acid (30.5 parts) with 22 parts of o-anisidine-cr-methanesulphonic acid and subsequent saponification in an alkaline medium, are stirred into 400 parts water of 80. Within two hours 24 parts of 4-nitro-benzoyl chloride are added in small portions. Simultaneously, the pH is kept at 6-7 by the dropwise addition of sodium hydroxide solution. When the last portion of 4-nitrobenzoyl chloride has been added, stirring is effected for a further three hours. The dyestuff intermediate which precipitates almost quantitatively is filtered and thoroughly washed with brine.
The resulting presscake is stirred into 400 parts of water and heated to 50. Then 35 parts of crystalline sodium sulphide are added portionwise. Due to the exothermal evolution of heat the temperature of the reaction mixture increases to 65. By adding 75 parts of sodium chloride the dyestuff precipitates completely. It is filtered with suction, thoroughly washed with brine and dried.
An aminoazo compound corresponding to the formula S ~ N = N ~ NHCO ~ NH2 is obtained.
55.6 Parts of this compound are dissolved in 800 parts of water, and 27 parts of a 4N sodium nitrite solution are added.
This mixture is dropped into a preparation consisting of 200 parts of ice, 50 parts of 30% hydrochloric acid and 150 parts of sodium chloride. A dark diazo suspension is obtained which is stirred for a further one hour. Any excess nitrous acid is decomposed by add-ing one part of sulphamic acid. Subsequently, 16 parts of 2-cyanimino-4,6-dihydroxypyrimidine are added to the diazo suspen-sion. The pH is elevated to 7-8 by adding 30~ sodium hydroxide so-lution. After about two hours coupling is completed. The precipi-tated product is filtered, washed with brine and dried. The dye-stuff corresponding to the formula - g - Case 150-5122 ~ N - N ~ NHCO ~ N = N ~ \~ NHCN

is obtained showing a high colouring strength. It dyes paper a brilliant neutral-yellow shade. The resulting paper dyeings have notably good wet and light fastness properties.

Example 2 When according to the method described in Example 1, 19 parts of aniline-Gr-methanesulphonic acid are used instead of 22 parts of o-anisidine-Gs-methanesulphonic acid the dyestuff cor-responding to the formula ~ N - N ~ NHCO ~ N = N ~ NHCN

is obtained which dyes paper a brilliant greenish-yellow shade.
The dyeings show good light and wet fastness properties.

Examples 3 to 16 By a method analogous to that of Examples 1 and 2 using ap-propriate starting compounds, further compounds of formula I may be prepared which are listed in the following Table. In the last column of this Table the shade of the paper dyeing obtained with each of the listed dyestuffs is indicated, whereby a is greenish-yellow, b is neutral-yellow, and c is weakly reddish yellow.
These paper dyeings show good light and wet fastness properties.

- lZ9Z735 - 10 - Case 150-5122 Table S03H on the shade Ex. No. naphthyl ring Rl R2 R3 on paper in the positions 3 6,8 CH3 H -NHCN b 4 do. do. CH3 do. b do. do. OCH3 do. c 6 do. -NHCOCH3 H do. c 7 do. -NHCONH2 H do. c 8 5,7 H H do. a 9 do. CH3 H do. b do. H OCH3 do. b 11 do. -NHCOCH3 H do. c 12 6,8 H H -NHCONH2 a 13 do. H OCH3 do. b 14 do. CH3 H do. b 5,7 H H do. a 16 do. H OCH3 do. b - 11 - Case 150-5122 In accordance with the preparation method as described in Examples 1 and 2, the compounds of Examples 1 to 16 are obtained and isolated in sodium sa1t form. They may, depending on the reaction and isolation conditions, or by reacting the sodium salts in accordance with known methods also be obtained in free acid form or in other salt forms, for example those salt forms or mixed salt forms containing one or more cations indicated in the description above.

Example 17 The dyestuff prepared according to the method given in Example 1 is stirred into 200 parts of water prior to drying, and is mixed with 20 parts of 30% hydrochloric acid. After having stirred for a longer time, the dyestuff, in free acid form, is filtered off and is added into 15 parts of triethanolamine. The dyestuff dissolves whilst releasing heat. This solution is adjust-ed to 90 parts by adding water to give a dyestuff solution which is storage-stable and ready for use.

Example 18 If in Example 17 lithium hydroxide solution is used instead of triethanolamine, a liquid aqueous dye preparation is obtained which contains the dyestuff according to Example 1 in the lithium salt form.
By a method analogous to that described in Examples 17 and 18 the dyestuffs of Examples 2 to 16 may also be converted into liquid aqueous dyeing preparations showing high stability on storage.
In the following examples the application of the compounds of this invention as well as of liquid aqueous dyeing preparations thereof is illustrated.

Application Example A
70 Parts of chemically bleached sulphite cellulose obtained from pinewood and 30 parts of chemically bleached sulphite cellu-~Z92735 - 12 - Case 150-5122 lose obtained from birchwood are ground in a hollander in 2000 parts of water. 0.2 Parts of the dyestuff of Example 1 or 2 are sprinkled into this pulp or 1.0 parts of the liquid dyestuff pre-paration according to Example 17 or 18 are added to this pulp.
After mixing for 20 minutes, paper is produced from this pulp. The absorbent paper obtained in this manner is dyed a neutral-yellow shade (greenish-yellow shade, respectively). The waste water is practically colourless, and the paper dyeing shows good light and wet fastness properties.

Application Example B
0.5 Parts of the dyestuff of Example 1 or 2 are dissolved in 100 parts of hot water and cooled to room temperature. This solu-tion is added to 100 parts of chemically bleached sulphite cellu-lose which have been ground in a hollander with 2000 parts of water. After thorough mixing for 15 minutes, sizing takes place in the usual way with resin size and aluminium sulphate. Paper which is produced from this material is of neutral-yellow shade (green-ish-yellow shade, respectively) and has good waste water, light and wet fastness properties.

Application Example C
An absorbent length of unsized paper is drawn at 40-50 through a dyestuff solution having the following composition:
0.5 parts of the dyestuff of Example 1 or 2 or of the liquid dye preparation according to Example 17 or 18, 0.5 parts of starch, and 99.0 parts of water.
The excess dyestuff solution is squeezed out through two rollers. The dried length of paper is dyed a neutral-yellow (greenish-yellow) shade.
The dyestuffs or liquid dyestuff preparations of the remain-ing examples may also be used for dyeing paper according to Appli-cation Examples A to C. The resulting paper dyeings are dyed a yellow shade. They have good general fastness properties.

lZ9Z~35 - 13 - Case 150-5122 Application Example D (leather) 100 Parts of intermediately dried chrome velours leather are agitated for one hour at 50 in a vessel with a liquor consisting of 400 parts of water, 2 parts of 25% ammonium hydroxide solution and 0.2 parts of a conventional wetting agent. Then the liquor is run off. To the agitated still wet chrome velours leather 400 parts of water of 60 and 1 part of 25% ammonium hydroxide solu-tion are added. After the addition of 5 parts of the dyestuff of Example 1 dissolved in 200 parts of water, dyeing is effected dur-ing 90 minutes at 60. Subsequently, 50 parts of 8% formic acid are slowly added to adjust to an acidic pH, and agitating is con-tinued for a further 30 minutes. The leather is then rinsed, dried and prepared in the normal way giving a leather evenly dyed in a yellow tone with good light fastness properties.
By a method analogous to that described in Application Example D the compounds according to Examples 2-16 may be used for dyeing leather Application Example E ( cotton) To a dyebath consisting of 3000 parts of demineralised water, 2 parts of sodium carbonate and 1 part of the dyestuff of Example 1, 100 parts of pre-wetted cotton fabric are added at 30.
After the addition of 10 parts of Glauber's salt, the dyebath is heated to the boil within 30 minutes whereby, at a temperature of 50 and 70, at each of these stages a further 10 parts of Glauber's salt are added. Dyeing is continued for a further 15 minutes at the boil followed by the addition of a further 10 parts of Glauber's salt. The dyebath is then cooled down. At 50 the dyed fabric is removed from the dye liquor, rinsed with water and dried at 60. A neutral-yellow cotton dyeing is obtained having good light and wet fastness properties.
In a similar manner as described in Application Example E
the compounds of Examples 2-16 may be used for dyeing cotton.

Claims

1. A compound which in one of the possible tautomeric forms corresponds to formula I

or a salt thereof, in which the sulphonic acid groups are in the 5,7- or 6,8-positions of the naphthyl radical, R1 is hydrogen, chlorine, methyl, methoxy, -NHCOCH3 or -NHCONH2, R2 is hydrogen, methyl or methoxy, and R3 is -NHCN or -NHCONH2, or a mixture of compounds of formula I each of which being in free acid or salt form.

2. A compound according to Claim 1, in which the sulphonic acid groups are in the 6,8-positions of the naphthyl radical.

3. A compound according to Claim 1, in which R1 is hydrogen or methyl.

4. A compound according to Claim 1, in which R2 is hydrogen or methoxy.

5. A compound according to Claim 1, in which R3 is -NHCN.

-15 - Case 150-5122

6. A compound according to Claim 2, in which R1 is hydrogen or methyl, R2 is hydrogen or methoxy, and R3 is -NHCN.

7. A process for the preparation of a compound of formula I, defined in Claim 1, or a mixture of compounds of formula I
comprising reacting the diazonium salt of one or more aminoazo compounds of formula II, II

in which the positions of the sulpho groups and R1 and R2 are as defined in Claim 1, with a compound which in one of the possible tautomeric forms cor-responds to formula III, III

in which R3 is as defined in Claim 1, or a mixture of compounds of formula III.

8. A storage-stable, liquid aqueous dyeing preparation con-taining a compound of formula I, defined in Claim 1, or a mixture thereof, in water-soluble salt form.

9. A process for dyeing or printing hydroxy group- or nitro-gen-containing organic substrates comprising applying to the sub-strate a compound of formula I, defined in Claim 1, or a mixture thereof, in water-soluble salt form, as dyeing or printing agent.

- 16 - Case 150-5122

10. A process according to Claim 9, wherein said substrate is paper, leather or a textile material containing or consisting of polyamide or cellulose materials.

11. A process according to Claim 10, wherein said substrate is paper.

12. A process for the preparation of inks comprising employ-ing a compound of formula I, defined in Claim 1, or a mixture thereof.