US3453256A

US3453256A - Disthiazolylazo dyes containing a bis (arylene aminoethyl) sulfone connecting linkages

Info

Publication number: US3453256A
Application number: US560076A
Authority: US
Inventors: John I Dale; Max A Weaver
Original assignee: Eastman Kodak Co
Current assignee: Novartis Corp
Priority date: 1966-04-28
Filing date: 1966-06-24
Publication date: 1969-07-01
Anticipated expiration: 1986-07-01
Also published as: NL6706046A; US3446791A; US3485813A; BE697491A

Description

United States Patent US. Cl. 260-158 11 Claims ABSTRACT OF DISCLOSURE Disazo compounds containing two thiazolyl-azo-aniline moieties joined by the group CH CH SO CH CH which is attached to the nitrogen atom of each aniline coupling component. The disazo compounds are useful as dyes for hydrophobic textile materials.

This invention relates to novel water insoluble, symmetrical and unsymmetrical disthiazolylazo compounds and, particularly, to disthiazolylazo dyes for hydrophobic textile fibers, yarns and fabrics.

The disthiazolylazo compounds of the invention are characterized by the general formula wherein R represents a thiazolyl radical having the structure wherein X represents hydrogen, alkyl, e.g. methyl, ethyl; substituted alkyl such as halogenoalkyl, e.g. chloromethyl, trifluoromethyl, cyanoalkyl, e.g. cyanoethyl, nitroalkyl, e.g. nitroethyl, hydroxyalkyl, e.g. hydroxyethyl; alkoxyl, e.g. methoxyl; alkanoylamino, e.g. acetamido; nitro; halogeno, e.g. chloro, bromo; cyano; al-kylsulfonyl, e.g. methylsulfonyl; substituted al-kylsulfonyl, e.g. cyanoethylsulfonyl; carbamoyl; aryl, e.g. phenyl; benzamido; benzylamino; N-alkylbenzylamino, e.g. N-phenylmethylamino; alkoxycarbonyl, e.g. ethoxycarbonyl; hydroxyl; alkanoyl, e.g. acetyl; formyl; sulfamoyl; N-alkylsulfamoyl; alkylsulfonamido, e.g. methylsulfonamido, ethylsulfonamido; dialkylsulfonamido, e.g. dimethylsulfonamido, dicarboxylicacidimido, e.g. succinimido; thiocyanato; alkylthio, e.g. methylthio; benzoxy; benzoyl; combinations thereof; and m represents 0, 1 or 2;

R and 'R may be the same or diiferent and represent monocyclic carbocyclic aromatic groups of the benzene series having the structure wherein Y may be the same or different in R and R and represents hydrogen, alkyl, e.g. methyl, ethyl; alkoxyl, e.g. methoxyl; alkanoylamino, e.g. acetamido; halogeno, e.g. chloro, bromo; benzamido; alkylsulfonamido, e.g. methylsulfonamido, ethylsulfonamido, combinations thereof; and n represents 0, 1, 2 or 3.

Preferably, the alkyl radicals of the substituents represented by and Y are lower alkyl, e.g. from 1 to about 4 carbon atoms.

R and R may be the same or different and represent hydrogen or an alkyl radical, preferably lower alkyl, i.e.

froml to 4 carbon atoms, being unsubstituted or substituted such as hydroxyal'kyl, e.g. hydroxyethyl, polyhyhydroxyalkyl, e.g. 2,3 dihydroxypropyl, alkoxyalkyl, e.g. methoxyethyl, cyanoalkyl, e.g. cyanoethyl, cyanoalkoxyalkyl, e.g. p-cyanoethoxyethyl, alkanoyloxy alkyl, e.g. acetoxyethyl, al-koxycarbonylalkyl, e.g. ethoxycarbonylethyl, halogenoalkyl, e.g. chloroethyl, u-chloropropyl, bromoethyl, hydroxyhalogenoalkyl, e.g. B-hydroxy-a-chloropropyl, alkylsulfonylalkyl, e.g. methylsulfonylethyl, alkyl- OCOOCH CH e.g. CH OCO-OCH CH carbarnoylalkyl, e.g. carbarnoylethyl; alkylcarbamoylalkyl, e.g. ethylcarbamoylethyl; dicarboxylic acid imidoalkyl, e.g. succinimidoethyl; aryl, e.g. benzyl; phenoxyalkyl, e.g. 18- phenoxyethyl; alkylsulfonamidoalkyl, e.g. methylsulfonamidoethyl; carbamatoalkyl, e.g. carbamatoethyl; and the like.

The disthiazolylazo compounds of the invention are prepared by coupling the conventional diazonium salts of compounds having the formula (II) RNH with unsymmetrical coupling components having the formula wherein R and \R may be the same or different and R and R may be the same or dilferent but either R must be different from R or R must be different from R or with symmetrical coupling components having the formula wherein R =R and R ='R and wherein R, R R R and R are defined as set forth above with reference to Formula I.

The unsymmetrical couplers of Formula III are prepared by reacting one mole of an appropriately substituted aryl amine with one mole of divinylsulfone in the presence of a catalyst such as acetic acid and contacting the reaction product, a vinylsulfonylethyl arylamine, with one mole of a different aryl amine, as set forth in the following illustrative sequence:

mula I wherein R and R are the same or different and R and R are the same or different but either R must be diflerent from R or R must be different from R and are defined as set forth in Formula I.

The symmetrical couplers of Formula IV are prepared by reacting two moles of an appropriately substituted aryl amine with one mole of divinylsulfone in the presence of 3,453,256 3 4 acetic acid catalyst, as set forth in the following illus- Preparation of symmetrical dyes native Sequence: Example 1.An amount of 2.90 g. 5-nitro-2-aminothiazole was dissolved at room temperature in 25 ml. H O

Ram R2) 11 /R2(0r R3) and 13.5 ml. conc. H 50 This solution was cooled to ZArN (C 2= )1 AYN S01 5 C. and 1.54 g. NaNO in 10 ml. H 50 was added H C2134 below 0 C. The solution was stirred 10 min. and added to a solution of 3.88 g. of coupler A in 20 ml. 1:5 acid wherein Ar=R =R and R =R and wherein R R, R (5 parts acetic acidzl part propionic acid) cooled in an and R are defined above in Formula 1, ice water bath. After 30 min. the solution was drowned The following examples will serve to illustrate the prep- 10 in water, filtered and the precipitated dye washed with aration of representative couplers and disthiazolylazo water and air dried. It dyed polyester fibers bright bluecompounds of the invention. As will be seen from the exviolet shades having good light fastness and outstanding amples, the substituents X, Y, R and R set forth in Forsublimation fastness. It had the formula:

| C2115 CzHs Example 2.-Nitrosyl sulfuric acid was prepared by dismula I serve primarily as auxochrome groups to control solving 1.62 g. NaNO in 12 ml. conc. H 50 below 80 the color of the disthiazolylazo compound. C. The solution was cooled to 15 and 25 ml. 1:5 acid 25 was added below C. After further cooling to -2. Preparanon of Symmemcal couplers 5.60 g. 2-amino-5-bromothiazole hydrobromide was added below 3 C. followed by ml. 1:5 acid below 5 C. After stirring for 1 /2 hr. at 5 to +5 C. the solution was added to 4.20 g. of coupler B in 25 ml. 1:5 acid dwmylgulfol? 5 fi i acld? a g chilled in an ice water bath. The solution was neutralized was re or e O uene an ace 10 were with ammonium acetate to brown on Congo red paper removed under VaFuum a the res idue taken up in 150 and after 1 hr. drowned in Water. The precipitated dye ml. of ethanol, This solution was chilled for 2 hrs. at near was filtered, washed with Water and air dried It d 0 C- ti Whlte Crystallme Pmduct was collected by polyester and cellulose acetate red-violet shades and filtration. Yield: 21.4 g. M.P. 58-61. It had the strucshowed excellent sublimation fastness on polyester fibers.

Preparation of bis[2-(N-ethyl-m-toluidino)ethyl]sulfone.-A mixture of 27.0 g. N-ethyl-m-toluidine, 11.8 g.

ture: It had the formula:

C2H4OH HOCaHt Br-L =N N/ \N N=N 131' C2H4SO2C2HI Ha Ha 02H 0,115 Example 3.--A diazonium solution was prepared from 2.90 g. 2-amino-5-nitrothiazole as in Example 1. This solution was added to a solution of 4.20 g. of coupler B CH3 0111450301114 H dissolved in 25 ml. 1:5 acid. After 1 hour the solution was drowned in water and filtered. The dye which was thus obtained gave blue-violet shades on polyester fibers Preparation of bis[2-(N-B-hydroxyethyl-m-toluidino) with good light fastness and excellent sublimation fast- Coupler A ethyl]sulfone.--The above procedure was repeated, subness. It had the formula:

l J cn1.on Hooper OZN =NN N N=N NO:

g \C2H4S 020g stituting N-[i-hydroxyethyl-m-toluidine for N-ethyl-m-toluidine for N-ethyl-m-toluidine. The product had the struc- Example 4.A diazonium solution was prepared from ture: 4.96 g. 2-amino-5-bromothiazole hydrobromide as in Ex- CIHLOH B00111, ample 2 and added to a solution of 3.88 g. of coupler A Q in 25 ml. 1:5 acid. The dye was obtained in the manner described in Example 2. It gave red shades on polyester :H4S OgCzHl CH3 H3 and cellulose acetate fibers which showed outstanding OzHr Example 5.A diazonium solution was prepared from Preparation of unsymmetrical couplers 4.00 g. of 2-amino-5-thiocyanato-thiazole according to the procedure of Example 38. It was added to a solution fmxmre i z fiY f of 3.88 g. bis [Z-(N-ethyl-m-toluidino)ethyl]sulfone in 25 l mm me, 5 mm m1. 5 acid The dye was completed as in Example 3 8 acld and 50 ml. toluene was refluxed for 24 hrs. The toluand gave red-violet dyeings on cellulose acetate and polyeue and acetic acid were removed under vacuum and the ester fibers showing excellent sublimation fastness on the latter. It had the formula:

Example 6.-Nitrosylsulfuric acid was prepared from residue crystallized from ethanol. The product had the 1.44 g. NaNO and 10 ml. concentrated H 80 below structure: 80 C. The solution was cooled to 15 and ml. 1:5 acid added below 20 C. The solution was further cooled to 0 C. and 2.00 g. Z-aminothiazole was added. After 02H: &

stirring for 1.5 hours at -5 C. to +5 C. the solution was added to a solution of 3.88 g. -bis[2-(N-ethyl-m- 20 toluidino)ethyl]sulfone in ml. 1:5 acid. Neutraliza- A C2H4SO2C2H4 1 tion to a brown color on Congo Red paper with ami 1 CouplerC monium acetate was followed by coupling for 2 hours.

The reaction mixture was drowned in wate rand the precipitated dye filtered and washed with Water. It dyed cel- 25 A mixture 29.9 g. 2,5-dimethoxy-N-ethyl-N-fi-vinylsullulose acetate and polyesters red shades with excellent fonyl-ethylaniline, 13.7 g. N-fi-hydroxyethylaniline, 5 ml. sublimation fastness on polyesters. The dye had the acetic acid and 50 ml. toluene was refluxed together for formula: 24 hrs. The toluene and acetic acid were removed under I /C2Ha can I s N=N N\ /N N=N 5/ 0211480262 4 H3 H3 The disthiazolylazo compounds illustrated in the followreduced pressure and the viscous oil obtained was used ing table are prepared by the procedure illustrated in without further purification. The coupler had the formula: Examples 1 through 6, above. Thus, the appropriate CHQO compounds of Formula II are coupled with suitable com- 02H, 1100x0114 pounds of Formula IV to obtain the compounds of Form- Q ula I wherein, R =R R'-=R and the thiazolylazo 02H SO C H4 groups are identically substituted. (mm 4 2 2 Coupler D TABLE Example X R R R'-, R Color 7 5-N01 m-Tolylene -CH1CHON Violet. 8 5-NO1 -.do -CH2OH2O1 Do. 9 fi-Noz -CHzCH2 CH3 D0. CH:CH:OCOCH: D0,

0 0 CH; 11 5-Noz. ..dO --CHzCH2 I D0.

0 O CH;

Do. 3 I DO. CHgCHnCONHz Do. CHgCHzSOaCHa D0.

16 5-N0g ..do --CH2CH2N D0.

11 5-NO: ..do -oHloH,o CONHQ Do; 18- Phenylene -C1H5 Do. 19- d0 CHBOH2OH Do. 20- m-Chlorophenylene- -O H Do. 21 o-Chlorophenylene. H Red. 22- o-Tolylene H Red 23, 2-0 OHM-CH phenylene C;H; Blue. 24 2-0 OH3-5-NHC 0 CH3 pheuyleue- OZH Do. 25 2,5-dl-O OH; phenylene C,Hs Red. 26 m-Tolyl Red. d Red. Red. Violet Red. Violet. Red Red R Preparation of unsymmetrical dyes applied thereto by conventional dye methods. The com- Example amount of 290 pounds have high affinity for cellulose ester, polyester, and thiazole was dissolved in 25 ml. of water and 13.5 ml. nylon fi1?erS'Whenthe dlsthlalzolylazo.Compounds are used conc. H SO This solution was cooled to 10 C. and for dyemg Such y f f mammals they Should ba 154 NaNO2 in 10 com H2804 was added below 5 free of water-solubihzing groups such as sulfo and car- 0 C. The Solution was stirred 10 min. and added to a boxyl. In general, the dyes have excellent fastness, for solution of 4.08 g. of coupler C in 25 ml. 1:5 acid. After Example! to light Washing! gas (atmospheric fumes) and 30 m solution was drowned in water The precipsublimation. The dyes are outstandingly sublimation reitated dye was filtered, washed with water and air dried. sistal'lt 0n Pf y It dyed polyesters, cellulose acetate and nylon bright red- 10 AS d s rl ed above, the present compounds have the dish blue shades. It showed excellent sublimation fastness characteristic structure of Formula I. This distinctive when dyed on polyesters and had the formula: structure imparts unexpected properties to the compounds,

N o H C H 2 l l l t OiN N=N N N N=N NO:

(\3 CzHiS OzC H; 5

Example 38.-An amount of 1.62 g. sodium nitrite was including the above-described light fastness and sublimaadded to 12 ml. conc. H 50 below 80 C. The solution 20 tion resistance. Thus, we have found the compounds of was cooled to C. and 25 ml. 1:5 acid added below the invention to have excellent properties as dyes when C. After further cooling to l0 C., 4.00 g. 2-aminotested by methods such as described in the A.A.T.C. Tech- 4-methyl-5thiocyanatothiazole was added followed by an nical Manual, 1964 edition.

additional ml. 1:5 acid. After stirring at -5 to 3 for The compounds of the invention can be used for dyeing 1% hr. in the solution was added to 4.36 g. of coupler D. 25 hydrophobic fibers such as linear polyester, cellulose ester, in 20 ml. 1:5 acid. The reaction mixture was neutralized acrylic, polyamide, etc., fibers in the manner described to brown on Congo red paper with ammonium acetate in US. Patents 2,880,050, 2,757,064, 2,782,187 and and allowed to couple 2 hr. The solution was drowned 2,043,827. The following example illustrates a method by in water and the precipitated dye was filtered, washed with which the compounds of the invention can be used to dye water and air dried. It dyed polyester fibers red-violet polyester textile materials.

shades having excellent sublimation fastness. It had the 0.1 g. of the dye is dissolved in the dye pot by warming formula: in 5 cc. of ethylene glycol monomethyl ether. A 2% so- CH3 OH; I N 01110 N 02115 HOCIHI NO s N-N N N Qua: s oN CgHtSQaCzH; OCH;

The disthiazolylazo compounds illustrated in the 01- dium-N-methyl-N-oleyl taurate and 0.5% sodium lignin lowing Table are prepared by the procedure of Examples sulfonate aqueous solution is added, with stirring, until 37 and 38. Thus the appropriate compounds of Formula a fine emulsion is obtained. Water is then slowly added II are coupled with suitable couplers of Formula III to to a total volume of 200 cc. Then, 3 cc. of Dacronyx obtain the compounds of Formula I wherein R R R (a chlorinated benzene emulsion) are added and 10 grams and R can be the same or different and the thiazolylazo of a textile fabric made of Kodel polyester fibers are groups are identically substituted. entered. The fabric is worked 10 minutes without heat and Ex. X R R2 R R Color 39 S-NOZ- m-Tolylene C H, -CH,OH Phenyleue Violet.

40 4-OF; m-Chlorophenylene C H CN CHgCHgN m-Tolylenc.-. Red.

41 4-CHi o-Chlorophenylene H CH CHi0GONH .----do Red.

4-CO2C2H5 o-Tolylene H C 11 do Red. 4-NHOOOH3 2-0OH -5-CH;pheny1ene CHzCHgCl CZHE .-d0 Red.

None... 2-0GH;-5NHCOCH; pheny1ene CHZCHZO CH; 02H; ...-do Red.

i 45 4-CH3, 54 3011 m-OCHmhenylene CHQCHZOCOCHQ 0 H; ..-do Red.

COOH;

46 MIN Phenylene CILCH N 0 H; .(10 Violet.

CO Hz 47 SSON m-Clphenylene CHQCHZOOQCZH 0 H; .do Red.

49 &SO20H:- -do CHzOHzSOQCH! 0211. do Red.

50 4-phenyld0 CHZCHQCONH: CHzCHzCONHz --.do Red.

The disthiazolylazo compounds of the invention can be then for 10 minutes at 80 C. The dye bath is then used for dyeing textile materials, including protein and brought to the boil and held at the boil for one hour. synthetic polymer fibers, yarns and fabrics, giving a variety Following this, the fabric is rinsed in warm water, then of fast brilliant red to blue shades, including violet, when scoured in aqueous 0.2% soap, 0.2% soda ash solution.

3,453,256 9 10 After scouring, the fabric is rinsed with water and dried. having the formula Accordingly, since the disthiazolylazo compounds of the invention are water-insoluble, they can be applied from aqueous dispersions in the manner of the so-called dispersed dyes. However, coloration can also be effected, u

for example, by incorporating the compounds into the spinning dope and spinning the fiber as usual. The com- WheTeDm Y 13 Pydfogen, lower y lower Q y pounds of the invention are not equivalent as dyes. The chlorlne, bromlne, alkanoyltlmlnol benzamldo, degree of dye aflinity varies, for example, depending upon or lower alkylsulfonamldog and n 15 1 the material being dyed and the formula of the disthia- R2 and R3 are the same or dlffefent and-each 1S Py zolylazo compound. Thus, for example, all the dyes will lower y or lower alkyl substltuted wlth ynot have the same degree of afiinity for the same material. droxy, lower alkoxy, lf lowef alkanoyloxy, lower For example, the substituents X, Y and the substituents R alkoxycarbonyl, chlorfnfe, Promme, alkylsul and R as mentioned above, serve primarily as auxofonyl, carbamoyl, smfcllllmldoiPhtha1lm1d0,PheI1XY, chrome groups to control the color of the disthiazolylazo lower alkylsulfonamldo, phenylcarbamoylpxy. compound. 2. A compound as defined 1n clalm 1 wherein sald Polymeric linear polyester materials of the terephthalate thlazolyl radlcal has the Structure type are illustrative of the linear aromatic polyester textile N materials that can be dyed with the new compounds of Xk our invention. The terephthalate fibers sold under the trademarks Kodel, Dacron, Terylene, for example, S

are illustrative of the polyester textile materials that can wherein X is hydrogen, lower alkyla lower alkanoylamino, be y Kodel Polyester fibers are more Partlclllafly nitro, chlorine, bromine, cyano, lower alkylsulfonyl, lower s r d n Patent 29 Dacron and Tel'ylene cyanoalkylsulfonyl, carbamoyl, benzamido, lower alkoxypolyester fibers are descrlbed, for example, in US. Patent carbonyl, lower alkanoyl, formyl, sulfamoyl, alkylsul- 2,465,319. The polymeric linear polyester materials disfonamido, thiocyanato, lower alkylthio, or benzoyl.

closed in US. Patents 2,945,010, 2,957,745, and 2,989,363 3. A compound as defined in claim 1 wherein for example can be dyed. The linear aromatic polyester R is 5 -nitro-2-thia zolyl, 5-chloro-2 -thiazolyl, S-bromomaterials specifically named have a melting point of at 30 24111810134, 5-thlocyanato 2 4111320134, 5 tllfllloroleast 200 C. methyl 2 thiazolyl, or 5 lower alkylsulfonyl-Z-thi- Nylon, in fiber, yarn and fabric form, is representative Y of polyamides which can be dyed with the disthiazolylazo R and R each 15 pphenylene lower alkylpphenylene,

compounds lower alkoxy p phenylene, chloro-p-phenylene, or

We claim} 3 lower alkanoylamino-p-phenylene; and

R and R each is lower alkyl, lower hydroxyalkyl,

A compound havmg the formula lower chloroalkyl, lower bromoalkyl, lower alkanoyloxy-lower alkyl, or lower cyanoalkyl.

| 4. A compound as defined in claim 1 having the RN=N-R -N-oHl0HlsolOH30HN-R -N=N-R 40 formula N /C2Hb ems I olN /N=N N NQ =N NO: s 8

C2H4SO202H4 3} H3 H3 wherein 5. A compound as defined in claim 1 having the R is a thiazolyl radical; formula R and R are the same or diiferent and each is a group ogHloH H 0 02134 I I l 1 Bl s N=N N /N -N=N S B! (I) \C2H4S 0202114 (13 Ha H:

6. A compound as defined in claim 1 having the formula 7. A compound as defined in claim 1 having the 8. A compound as defined in claim 1 having the formula 9. A compound as defined in claim 1 having the formula 03H N N N N N N 3/ \s/ 021135030111 Ha CH3 10. A compound as defined in claim 1 having the formula 11. A compound as defined in claim 1 having the formula CH3 N CHaO N CH3 CaHg HOCxH; 1 NUS S N: N\ /N N=N 3 SUN CzH4SOzCgH4 CH3 References Cited UNITED STATES PATENTS 2,955,901 10/ 1960 Kruckenberg 260-158 XR 3,177,198 4/1965 Weis et a1. 260-158 XR 3,287,347 11/1966 Hahn et al. 260-158 3,380,990 4/1968 Wallace et a1 260-158 3,380,991 4/1968 Dale et al 260-158 FLOYD D. HIGEL, Primary Examiner.

US. Cl. X.R.