GB2088359A - Aryl Sulphones - Google Patents

Abstract

Naphthyl sulphones of the formula: <IMAGE> wherein Yn represents 0 to 4 substituents each independently selected from Cl, OR and SO3H where R is C1-4 alkyl; X is CN, CH2NH2, CONH2, CO2H or CO2R; R<1> is H or C1-4 alkyl; R<2> is H, C1-4 alkyl, cycloalkyl, or optionally substituted phenyl; a and b are each independently 0 or 1 and a+b is 1 or 2. The above sulphones are valuable dyestuffs intermediates and as appropriate to an individual structure can serve as diazo or coupling component. When X is CH2NH2 the sulphones of formula (1) can be used to produce valuable cellulose reactive dyes by reaction of the NH2 group with conventional reagents for the introduction of a cellulose reactive group before or after the sulphone or formula (1) is converted to a dyestuff.

Description

SPECIFICATION Aryl Sulphones This invention relates to aryl sulphones particularly alkyl/naphthyl sulphones useful as dyestuffs intermediates.

U.K. Patent 453443 gives the preparation of various phenyl SO2-alkyl compounds with substituents on both the phenyl and alkyl groups.

These compounds are said to have uses as dyestuffs intermediates but there are no details in this or any other source as to how this is achieved.

Berichte 44 page 3628 discloses compounds such as

which have been evaluated in chemotherapy (see Chemical Abstracts 46 6192).

Chemical Abstracts 511064 discloses compounds such as p-naphthyl . SO2CH2CH2X where X is CO2CH3,CN, CONY2.

We have now discovered a novel class of naphthyl suiphones of especial use as dyestuff intermediates.

According to the present invention there are provided naphthyl suiphones of the formula:

wherein Yn represents 0 to 4 substituents each dependently selected from Cl, OR and SO3H where R is C14 alkyl; X is CN, CH2NH2, CONH2, CO2H or CO2R; R' is H or C14 alkyl; R2 is H, C 1-4 alkyl, cycloalkyl, or optionally substituted phenyl; a and b are each independently 0 or 1 and a+b is 1 or2.

As examples of the C14 alkyl groups represented by R, R' and R2 there may be mentioned methyl, ethyl, isopropyl and n-butyl.

As examples of cycloalkyl groups represented by R2 there may be mentioned cyclohexyl and methyl cyclohexyl.

As examples of optionally substituted phenyl groups represented by R2 there may be mentioned chlorophenyl, sulphophenyl, disulphophenyl and methyl phenyl.

The more conveniently available naphthyl sulphones of formula (1) are often those in which Yn is a single Cl or OR group or such groups in combination with 1, 2 or 3 SO3H groups or in which Yn is 1, 2 or 3 SO3H groups or Yn represents no substituents. The most readily available OR groups are OCH3 or especially OC2H5.

Preferred naphthyl sulphones of formula (1 ) have one or more of the following features: (a) R1 is CH3 or especially H; (b) R2 is phenyl or especially H; (c) Yn represents the substituents as in the more conveniently available naphthyl sulphones described above; (d) X is CN, CH2NH2, COOH or COOR where R is CH3 or C2Hs.

The nature of the groups present in the naphthyl sulphonesofformula (1 ) naturally influence how it may be used as a dyestuffs intermediate e.g. as diazo or as a coupling component. Also the substituents influence the character of the dyestuff which may be formed from the naphthyl sulphonesofformula (1). For example the presence of water solubilising substituents e.g. SO3H or COOH groups especially when in salt form will confer water solubility which may be desirable or may need to be avoided if the derived dyestuff is to be used as a disperse dyestuff or pigment.

The following are examples of naphthyl sulphones of formula (1).

(1) Capable of Being Used as Diazo Components 5-(2-cyanoethylsulphonyl)-2-naphthylamine-1 sulphonic acid; 5-(3-aminopropylsulphonyl)-2-naphthylamine1-sulphonic acid; 5-(2-carboxylethylsulphonyl)-2- naphthylamine-1-sulphonic acid.

(2) Capable of Being Used as Coupling Components 6-(2-cyanoethylsulphonyl)-2-naphthol-l - sulphonic acid; 6-(2-cyanoethylsulphonyl)-2-naphthol; 6-(2-carboxyethylsulphonyl)-2-naphthol.

The present invention also provides a process for the manufacture of naphthyl sulphones of formula (1) in which X is CN which comprises reacting acrylonitrile with a naphthyl sulphinic acid of the formula:

where a, b, R', R2 and Yn have the meanings given above.

This reaction may be conveniently carried out in an aqueous medium at 40 to 750C.

The naphthyl sulphinic acids of formula (2) may themselves be obtained from the corresponding unsulphonated naphthalene compound by chlorosulphonation and reaction with sodium sulphite. If the naphthalene compound bears an amino group it may be desirable that this should be protected by acetylation, the acetyl group being removed by hydrolysis after the formation of the sulphinic acid group. Alternatively the hydrolysis may be carried out at a convenient time after reaction with acrylonitrile.

As examples of suitable naphthalene compounds for conversion to sulphinic acids there may be mentioned 2-naphthol 2-naphthol-6-sulphonic acid 2-naphthol-7-sulphonic acid 2-naphthylamine-6-sulphonic acid 2-naphthylamine-7-sulphonic acid 2-naphthylamine-1 -sulphonic acid 2-amino-5-naphthol-1-sulphonic acid 1 -amino-8-naphthol-3,6-disulphonic acid The present invention further provides a process for the manufacture of naphthyl sulphones of formula (1) in which Xis CH2NH2 which comprises reducing a naphthyl sulphone of formula (1) in which X is CN.

This reduction may be conveniently carried out by any method conventionally employed for the reduction of organic nitriles, e.g. hydrogenation under pressure with catalysts such as Raney nickel.

The present invention yet further provides a process for the manufacture of naphthyl sulphones of formula (1 ) in which Xis COOH or CONH2 which comprises hydrolysing a naphthyl sulphone of formula (1 ) in which Xis CN.

The formation of COOH or CONH2 depends on the conditions used for the hydrolysis as is well known. For example hydrolysis by strong sulphuric acid (9599%) close to ambient temperature tends to yield CONY, whereas more dilute acids e.g. sulphuric acid of 75% or less at higher temperatures e.g. 50-1 000C yields COOH.

The present invention a!so provides a process for the manufacture of naphthyl sulphones of formula (1) in which X is COOR where R is lower alkyl which comprises esterifying a naphthyl sulphone of formula (1 ) in which Xis COOH with a lower alkanol ROH.

This esterification may be carried out under conditions conventionally used for the esterifying carboxylic acids e.g. the acid may be boiled with an excess of alkanol and the water formed removed by distillation.

The present invention provides an alternative processforthe manufacture of naphthyl sulphones of formula (1) in which Xis COOR which comprises reacting an alkyl acrylate ROOC CHCH2 with a naphthyl sulphinic acid of formula (2) as given above.

This reaction may be carried out as described above for the similar reaction with acrylonitrile.

Examples of suitable acrylates include methyl and ethyl acrylates.

The products from all the above processes may be isolated by conventional procedures and in some instances may be used e.g. converted to dyestuffs without isolation.

The naphthyl sulphones of formula (1 ) are valuables as intermediate for the manufacture of dyestuffs especially azo dyestuffs and such dyestuffs form a further feature of the present invention.

The naphthyl sulphones of formula (1 ) are usually converted to azo dyestuffs by one of two conventional methods viz.

In those instances where they are capable of coupling e.g. the compounds listed above as such they may be coupled with the diazonium salt from any conventional diazotisable aromatic amine.

In other instances where the naphthyl sulphone of formula (1) bears a diazotisable amino group i.e. R1 and R2 are H this may be diazotised and coupling carried out with any conventional coupling component. If desired the diazotisable naphthyl sulphone of formula (1 ) could be coupled with a second naphthyl sulphone of formula (1 ) which was capable of coupling.

These diazotisations and coupling procedures may be carried out by conventional well established methods.

The azo dyestuffs of the present invention may be characterised by the presence of one of two groups viz.

where a, b, X and Yn have the meanings defined above.

These dyes may be represented as

wherein A is the radical of a diazotisable aromatic amine ANY2, or

wherein E is the radical of a coupling component EH.

In some instances the naphthyl sulphone of formula (1) will be capable of coupling twice to yield dyes with a characteristic group

Such dyes which are also a feature of the present invention may be represented as

where A has the meaning given above and A' is the radical of a diazotisable aromatic amine A'NH2. A' may be the same or different to A.

It is usually preferred that A and A' in formulae (5) and (8) are phenyl or naphthyl groups which may be substituted with atoms or groups conventional in the azo dyestuffs art including aryl azo groups in which instances of the dyes of formula (5) are dis- or poly-azo dyes and those of formula (8) are poly-azo dyes.

It is usually preferred that the coupling component EH which provides E in formula (6) is of the naphthol, naphthylamine or aminonaphthol series especially when bearing 1 to 3 SO3H groups. Also preferred are coupling components of the nitrogen heterocyclic series e.g.

pyrazolones or pyridones especially 6hydroxypyrid-2-ones. Further preferred coupling components are acetoacetanilides, phenols and para coupling amines of the benzene series.

In some instances the group E will contain an aryl azo substituent and can be derived from coupling components EH themselves formed by coupling once onto a material capable of coupling twice.

When the dyestuffs of formulae (5), (6) and (8) are free from water solubilising groups, e.g. when Yn represents no substituents and X is CN or CO2R, they are of value as disperse dyestuffs for colouring synthetic textile materials such as cellulose acetate or polyethylene terephthalate.

A particularly preferred class of azo dyes of the present invention are cellulose reactive dyestuffs derived from naphthylhsulphones of formula (1 ) in which X is CH2NH2. Before or after its use in the manufacture of an azo dyestuff such a naphthyl sulphone may be reacted with conventional reagents for the introduction of cellulose reactive groups into amino compounds whereby the CH2NH2 is converted to CH2NHQ where 0 is a cellulose reactive group.

The cellulose reactive group Q may be any conventional cellulose reactive group, for example preferred groups include fluoro-, chloro- and bromo-triazinyl, halo pyridinyl, halodicyanophenyl and halopyrimidinyl.

The reactive dyestuffs may be represented by formulae (5), (6) or (8) in which X is CH2NHQ.

Such dyes will usually bear water solubilising substituents such as SO3H or salts thereof.

The dyes of the present invention bearing the reactive group Q usually show a number of advantages over related known reactive dyes.

They often have good resistance to bleaching agents and can be used in discharge processes where they discharge without significant residual stain. They also often show good resistance to acid hydrolysis i.e. to "acid-bleeding" especially when 0 is a dichlorotriazinyl group.

When the naphthyl sulphones of formula (1) in which X is CH2NH2 are reacted with the reagent to introduce the cellulose reactive group 0 before it is used in the formation of an azo dyestuff the resulting products are novel and form a further feature of the present invention. These products have the formula:

wherein R', R2, Yn, a and b have the meanings given in connection with formula (1) and Q is a cellulose reactive group.

The invention is illustrated by the following Examples in which parts and percentages are by weight unless otherwise indicated.

Example 1 22.3 parts of 2-naphthylamine-1 -sulphonic is added to 11 6 parts of chlorosulphonic acid over 1 hour maintaining the temperature below 350C.

The reaction mixture is stirred at 350C for 20 hours then drowned into ice/water maintaining the temperature below 1 00C. The resulting precipitate of 5-chlorosulphonyl-2 naphthylamine- 1 -sulphonic acid is filtered and washed with 10% brine. The filter cake is added portionwise to a stirred mixture containing 25.2 parts of sodium sulphite and 200 parts of water, maintaining the pH at 7-8 by addition of sodium hydroxide solution as necessary and the temperature at 25-300C by the addition of ice as necessary. After stirring 1 hour 85 parts of 36% hydrochloric acid is added dropwise and the resulting precipitate is filtered and washed with 100 parts of 25% brine.The filter paste is then slurried in 100 parts of water and the pH is adjusted to 7-8 by the addition of sodium hydroxide solution to give a solution of sodium-6 amino-5-sulphonaphthalene- 1 -sulphinic acid.

To the above aqueous solution of sodium-6 amino-5-sulphonaphthalene- 1 -sulphinic acid is added 15.6 parts of sodium dihydrogen orthophosphate and the mixture is stirred until a solution is formed. 6 Parts of acrylonitrile is added and the solution is stirred at 45--500C for 6 hours, after which time 5 parts of carbon is added and the mixture is stirred for a further hour. After screening the filtrate is cooled to room temperature and 36% hydrochloric acid is added until the pH is acid to Congo Red. The insoiuble 5 (2-cyanoethylsulphonyl)-2-naphthylamine-1 sulphonic acid is isolated by filtration and dried.

34 Parts of 5-(2-cyanoethylsulphonyl)-2 naphthylamine-1-suiphonic acid as prepared above is added to mixture of 180 parts of acetic acid and 240 parts of acetic anhydride. 1 8.5 Parts of tri-n-butylamine is added, the mixture is heated to 800C and stirred for 2 hours. The resulting solution is transferred to an autoclave and 1 2 parts of sodium acetate and 5 parts of Raney nickel is added and the mixture is hydrogenated at 80"C and 100 atmospheres for 12 hours. After cooling, the reaction mixture is discharged from the autoclave and Raney nickel is removed by filtration.The filtrate is concentrated by evaporation and the residue is dissolved in 200 parts of ethanol. 35 Parts of 36% hydrochloric acid is added dropwise to the solution and the resulting insoluble 5-(3-acetylaminopropyl sulphonyl)-2-acetylaminonaphthalene-1 - sulphonic acid is isolated by filtration, washed with ethanol and dried.

To a mixture containing 20.6 parts of potassium hydroxide in 1 50 parts of water is added 42.8 parts of 5-(3-acetylaminopropyl sulphonyl)-2-acetylaminonaphthalene-1 - sulphonic acid. The mixture is heated to the boil and stirred under reflux for 8 hours. The resulting solution is cooled to room temperature and screened. The filtrate is cooled to below 1 50C and 36% hydrochloric acid is added to adjust the pH to 7. The resulting precipitate of 5-(3-aminopropylsulphonyl)-2-naphthylamine-1 -sulphonic acid is isolated by filtration washed with water and dried.

Example 2 A suspension of 3.8 parts of 5-(3-aminopropyl sulphonyl)-2-naphthylamine-1-sulphonic acid in 1 50 parts of water and 5 parts of hydrochloric acid (36 Tw) is stirred at 0--5 OC and diazotised by the addition of 0.77 parts of sodium nitrite dissolved in 6 parts of water. After stirring at O- 50C for 1 hour, slight excess of nitrous acid is removed by addition of 10% aqueous sulphamic acid solution as required.

The diazo suspension is added to a solution of 3.2 parts of 3-carboxy-1 -(4-sulphophenyl)-5- pyrazolone in 1 50 parts of water at pH 8.0 and 0--5 OC. The mixture is stirred at 0--5 OC for 3 hours, filtered and dried at 450C.

5.2 Parts of the monazo compound prepared above is dissolved in 200 parts of water at pH 11.0 and 0--5 OC. The solution is added dropwise to a suspension prepared by adding a solution of 1.6 parts of cyanuric chloride in 30 parts of acetone to 100 parts of water and 50 parts of ice.

During the addition the temperature is kept at O- 50C and the pH maintained at 8-9 by simultaneous addition of 10% aqueous sodium hydroxide solution as required. After stirring for 1 hour the pH of the solution is adjusted to 6.5, screened, and the dyestuff precipitated by addition of 60 parts of sodium chloride. The dyestuff is filtered off, the damp precipitate intimately mixed with 2 parts of a mixture of 1 part of disodium hydrogen orthophosphate and 2 parts of potassium dihydrogen orthophosphate, and finally dried at 20do.

When applied to cellulose textile materials the dyestuff gives bright greenish yellow shades with good fastness to washing and to light.

Claims (1)

1. Claim

   1. Naphthyl sulphones of the formula:

   wherein Yn represents 0 to 4 substituents each independently selected from Cl, OR and SO3H where R is C14 alkyl; X is CN, CH2NH2,CONH2,CO2HorCO2R; R1 is H or Cur 4 alkyl; R2 is H, C14 alkyl, cycloalkyl, or optionally substituted phenyl; a and b are each independent 0 or 1 and a+b is 1 or2.