US3119809A - Basic dyestuffs - Google Patents

Description

United States Patent Ofifice 3,119,809 Patented Jan. 28, 1964- The importance of the polyacrylonitrile fibers has greatly increased in recent years and has led to intensive research in dyestuff chemistry with the object of discovering new dyestuffs for these fibers and practical methods of application. The principal dyeing methods for polyacrylonitrile fibers are (a) The cuprous ion method for dyeing with acid dyestuffs,

(b) The dyeing method with disperse dyestuffs,

(c) The dyeing method with basic dyestuffs.

Disperse dyestuffs give only light shades on polyacrylonitrile fibers and, even so, only a comparatively small number of the dyestuffs of this class are suitable. By means of the cuprous ion method it is possible to produce heavier shades, but its practical application is rather too complicated for the textile colorist. Dyeing with basic dyestuffs, however, has the advantage of being a relatively simple method of application and it gives dyeings of high all-round fastness, in particular of excellent wet fastness and very good light fastness. For these reasons the basic dyestuffs have become the preferred class for polyacrylonitrile fibers, though at the same time they have the great disadvantage that it is very difficult to obtain level dyeings and prints with them, especially in the case of light shades.

Most of the well drawing basic dyestuffs possess such high aifinity for polyacrylonitrile fibers by virtue of their positive charge that they are taken up by the fiber much too rapidly. In consequence the dyed goods have a flec-ked appearance and are of no further value for practical use. This undesirable effect is a very great obstacle to successful dyeing, especially as the unlevel dyeings given by basic dyestuffs on polyacrylonitrile fibers cannot be stripped or topped satisfactorily.

The surprising discovery has now been made that basic dyestuffs which contain at least one aminooxide group possess good affinity for polyacrylonitrile fibers at temperatures below 100 C. and therefore are very well suited for the dyeing and printing of shaped articles of polyacrylonitrile or of copolymers and other materials which contain polyacrylonitrile as the essential component.

These dyestuffs combine the advantages of the basic dyestuffs (high affinity for polyacrylonitrile fibers, excellent light and wet fastness) with those of the disperse dyestuffs (excellent level dyeing at all depths, even the lightest shades).

The mechanism of dyeing on polyacrylonitrile fibers with the dyestuffs containing aminooxide groups probably involves the formation of a salt, in which the aminooxide group acts as a cation and combines with the acid groups present in the polyacrylonitrile. This hypothesis is supported by the following experiment. When a polyacrylonitrile fiber is treated with a cationic agent prior to dyeing it loses its capacity for absorbing basic dyestuffs (it is then called blocked polyacrylonitrile), while it can still be dyed with disperse dyestuffs which are only dissolved and diffused in the fiber.

In contrast to the normal disperse dyestuffs, the dyestuffs containing aminooxide groups do not dye blocked polyacrylonitrile but behave in this respect like basic dyestuffs.

Owing to the semi-polar oxygen linkage the basic character of the nitrogen atom in the aminooxide group of the disclosed dyestuffs is considerably weakened; as a result of this reduced basicity they level considerably better than the corresponding oxygen-free dyestuffs.

This invention relates to new basic dyestuffs sulfonic acid groups, free from carboxylic acid and which contain at least one grouping of the general formula wherein X denotes the direct linkage, an oxygen atom or a nitrogen atom substituted by a hydrogen atom or an organic radical,

R a divalent organic radical, and

R and R each a monovalent organic radical or together with N a heterocyclic ring.

The process for the production of the new basic dyestuffs consists in converting a tertiary amine of the formula R (II) wherein:

A denotes the radical free from carboxylic acid or sulfonic acid groups of a dyestuif or of a compound capable of dyestuif formation and X, R R and R possess the aforestated meanings into the aminooxide compound by treatment with an oxidizing agent and converting this compound, when A represents the rad-ical of a compound capable of dyestuff formation, into a dyestuif by a suitable reaction.

The following are enumerated as examples of suitable dyestuif radicals: radicals of the ainthraquinone, phthalocyanine, triphenylrnethane, cyanine, perinone, naphthoquinone, nitro, ox-azine, thiazine, indigo, qu-inophthalone and, in particular, those of the azo dyestutf series. The compounds capable of dyestuff formation are preferably those which can be converted into azo dyestulfs by reaction with a diazonium salt, or compounds which contain a diazotizable amino group or a substituent capable of con version into such a group and upon diazotization can be coupled with a coupling component, further those which can be converted into dyestuifs by condensation. The azo coupling reaction is accomplished by the known method, preferably in a weakly alkaline to acid medium which may be buffered if necessary.

The reaction of the tertiary amine with the oxidizing to give the corresponding aminooxide compound is conducted preferably in an inert solvent or, if necessary, in aqueous suspension or solution, preferably at elevated temperature and with an excess of oxidizing agent.

Examples of suitable solvents are alcohols, such as methanol, ethanol, propanol, isopropanol, ketones such as acetone, methylethyl ketone, acetic acid esters and other esters, formic acid, acetic acid and propionic acid. Suitable oxidizing agents are e.g. hydrogen peroxide, chromic acid, per acids (peracetic acid, persulfuric acid), per salts (persulfates, perborates, percarbonates), the various manganese oxides and nitric acid, nitrous oxides, halogens and hypohalogenites. Also, the technique of anodic oxidation can be employed.

The basic dyestuffs formed are separated by one of the standard basic operations such as filtration, evaporation and filtration, precipitation with a suitable agent and filtration.

The new basic dyestuifs are suitable for the production of full shades by dyeing and printing processes on materials composed of polymers containing more than acrylonitrile such as polyacrylonitrile, e.gfOrlon (registered trade mark) and copolymers of 95% acrylonitrile and vinyl acetate or methyl acrylate or methyl methacrylate.

The dyestuffs containing a group of Formula I as well as their salts are applied to best advantage form aqueous, preferably weakly acid, suspension at high temperature, preferably in presence of dispersing agents of non-ionic, anionic or cationic character. The dyestuffs are equally suitable for application by higher temperature processes in closed dyeing machines under pressure. The dyeings and prints obtained on polyacrylonitrile materials possess good fastness to light, washing, water, milling, perspiration, sea water, pleating and heat setting, and even in the lightest depths they are very level.

With the dyestuffs conforming to the definition blended fabrics containing polyacrylonitrile fiber as one of the components can be successfully dyed while the wool, cotton or viscose in the blend is reserved.

The new dyestuffs also have-affinity for synthetic polyamidefibers, e.g. Perlon, Rilsan (registered trademarks), nylon; cellulose ester fibers, e.g. cellulose acetate and cellulose triacetate; and terephthalic acid ester fibers, e.g. Terylene, Dacron (registered trademarks), on which they give yellow, orange, red, violet or blue shades. On these fibers also they possess excellent fastness to light, washing, water, sea water, perspiration, pleating, pressing, heat setting, gas fumes and chlorine, and a number of them are dischargeable to white. They reserve cotton, viscose and wool to a great extent and in cases where slight staining of these fibers occurs it can be largely cleared by treatment with hydrosulfite. Certain of the new dyestuffs are suitable for the coloration of lacquer media, oils, synthetic resins and man-made fibers in the mass.

In the following examples the parts and percentages are by weight and the temperatures in degrees centigrade. The melting points are uncorrected.

EXAMPLE 1 parts of the tertiary amine of the formula CH2C113 are dissolved in 20 parts of ethyl alcohol and reacted with 20 parts of 34% hydrogen peroxide at 60. On completion of oxidation, which can be followed by observing the consumption of the oxidizing agent, the reaction mass containing the crude aminooxide compound is evaporated almost to dryness. 300 parts of water and 12 parts of hydrochloric acid are added to give a clear solution which is added to a previously prepared diazo solution of 14 parts of l-aminol-nitrobenzene, 30 parts of 30% hydrochloric acid, 200 parts of water and 7 parts of sodium nitrite at 5. On completion of coupling, which can be accelerated by the addition of sodium acetate, the precipitated red dyestutf chlorohydrate is filtered olf, washed neutral and dried. The crude product which is obtained in excellent yield melts at l69-170 and is practically pure. If desired, it can be recrystallized from glacial acetic acid, upon which it melts at 175. In this way a dyestuff of low solubility in water is obtained which dyes polyacrylonitrile fibers from aqueous acetic acid suspension in level red shades of good fastness to light, washing, perspiration, sublimation, pleating, pressing, water, sea Water, gas fumes and bleaching.

When the 14 parts of 1-amino-4-nitrobenzene in Example l'are replaced by 17.5 parts of 1-amino-2-chloro-4- nitrobenzene, a dyestufi is obtained which crystallizes out of glacial acetic acid in the form of red needles with a melting point at 159-160". The elementary analysis gives the values calculated for the hydrochloride.

When the 14 parts of l-amino-4-nitrobenzene in Example 1 are replaced by 13 parts of 1-amino-4-chlorobenzene, a dyestutf is obtained which crystallizes from glacial acetic acid in fine orange needles with a melting point at 155-l56. Here also the analysis gives the values calculated for the hydrochloride.

When the 14 parts of 1-amino-4-nitrobenzene in Example l are replaced by 20 parts of l-amino-4-dimethylaminosulfonylbenzene, a dyestutf is obtained which crystallizes out of glacial acetic acid in attractively formed yellow chips with a melting point at l47l48. The elementary analysis gives the values calculated for the hydrochloride.

Dyeing Example (a) The following procedure is used for dyeing polyester fibers. A dyebath is prepared with 3000 parts of water, 10 parts of emulsified chlorobenzene and 0.5 part of a dyeing preparation made by intimately grinding 35 parts of the dyestuff of Example 1 paragraph 1, with 20 parts of sodium dinaphthylmethane-disulfonate, 20 parts of a fatty alcohol sulfonate and 25 parts of anhydrous sodium sulfate. At room temperature 100 parts of the polyethyl eneterephthalate fiber Dacron are entered into the bath, the temperature increased to 100 and this temperature maintained for 1 hour. The goods are then removed, rinsed with water and dried. The scarlet dyeing obtained is fast to light, washing and pleating. Wool is to a great extent reserved and the slight stain which is left can be easily cleared with hydrosulfite.

Cellulose acetate is dyed as follows. A dyebath is prepared with 1 part of the aforedescribed dyeing preparation, 6 parts of a fatty alcohol sulfonate and 3000 parts of water. 100 parts of cellulose acetate are entered at room temperature, the dyebath heated to in 1 hour and held at this temperature for a further hour. After this time the dyeing process is completed. The goods are removed, rinsed and dried. The scarlet dyeing is fast to light, gas fumes and washing and can be discharged to white.

Dyeing Example (b) A suitable procedure for dyeing polyacrylonitrile fibers is as follows. 35 parts of the dyestufi obtained according to Example 1 and 65 parts of dextrin are intimately ground to give a dyeing preparation, 1 part of which is suspended in 3000 parts of water at room temperature and the suspension acidified with 5 parts of acetic acid. parts of a scoured fabric of polyacrylonitrile fiber is entered at 50, the dyebath brought to the boil in 30 minutes and dyeing continued at this temperature for 1 hour. The dyed fabric is subsequently rinsed, soaped for 20 minutes in a boiling bath containing 1 gram per liter of a nonionic detergent, rinsed and dried. A deep red dyeing of good fastness to light, washing, water, milling, perspiration, sea water, pleating and heat setting is obtained.

EXAMPLE 2 22 parts of the amine of the formula CH; -CH3 are dissolved in 20 parts of ethyl alcohol and reacted with 20 parts of 34% hydrogen peroxide. On completion of oxidation, which can be followed from the consumption of the oxidizing agent and the increasing water-solubility of the product, the reaction mass containing the crude aminooxide compound is diluted with 200 parts of water and added to a previously prepared diazo solution of 18.5 parts of 1-amino-2.4-dinitrobenzene, 80 parts of concentrated sulfuric acid, 7 parts of sodium nitrite and 240 parts of ice. By the addition of 40 parts of sodium acetate the coupling reaction is completed. The precipitated red dyestuff is filtered off, Washed and dried. In the crude state it melts at 161-163 and dyes polyacrylonitrile fibers in violet shades.

When 1-diazo-2.4-dinitrobenzene is coupled with the coupling component used in Example 1 which has the formula CH2CH2NO (CH9: another violet dyestuff is obtained with melting point EXAMPLE 3 The dilute solution of the coupling component obtained according to the particulars given in Example 2 is added to a previously prepared diazo solution of 21 parts of 1- amino-2.6-dichloro-4-nitrobenzene, 80 parts of concentrated sulfuric acid, 7 parts of sodium nitrite and 240 parts of ice. Coupling is completed by the addition of 40 parts of sodium acetate, and the precipitated brown dyestufi? is filtered off, Washed and dried. In the crude state it melts at 152-154 and dyes polyacrylonitrile fibers in deep redbrown shades.

When l-diazo-2.6-dichloro-4-nitrobenzene is coupled with the coupling component used in Example 1, a yellow-brown dyestutf is obtained Which melts in the crude state at 110-111.

EXAMPLE 4 27 parts of the tertiary amine of the formula CH2CH2N(CH;4)2 Q \CH2CH2N(CH3)2 are reacted in 20 parts of methyl or isopropyl alcohol with 40 parts of 34% hydrogen peroxide at 60. On completion of oxidation, which :can be observed from the consumption of the oxidizing agent and the increasing water-solubility of the product, the reaction mass is diluted with 200 parts of water and added to a previously pre- The crude product, which is obtained in excellent yield, melts at 125-126 and is practically pure. It dyes polyacrylonitrile fibers in scanlet shades of very good fastness properties.

In place of the 27 parts of the tertiary amine used above, equivalent amounts of the tertiary amines listed below can be employed to give other scarlet dyestuffs with similar dyeing properties.

When the coupling component produced according to Example 2 is coupled with 1-diazo-4-nitrobenzene, using the process described in Example 4, a red dyestutf is obtained which melts at 118-120 and dyes polyaorylonitrile fibers in very bright red shades having excellent fastness properties.

Further valuable basic dyestufis which can be produced according to the details given in Examples 1 to 4 are described in the following table; they conrespond to the pared diazo solution of 17.5 parts of l-annno-2-chloro-4- farmula nitrobenzene, 3 0 parts of 30% hydrochloric acid, 200 x parts of water and 7 par-ts of sodium nitrite at 5. On completlon of coupling, which can be accelerated by the 45 addition of sodium acetate, the precipitated red dyestufi chlorohydrate 1s filtered off, washed neutral and drled.

Shade of Dyeing Example R :1 y R5 B5 on Poly- No. acrylonitrile Fibers CHzCHrNO(CH3)z Red. CH2CH2N O(CH2CH:4)2 D0, -CHg-OHgNO(CH2 GHa)2- D0. CHzCHzNO(CH2-OH3)2--- D0. CH2GHzNO-(CHQCHQ)2 D0. Ol-I2CH2NO(CH2CHs)2 Scarlet CH2CHg-NO-(CH1CHa)2 D0.

CHzCI-I2NQ(CH2CHsg2 Red. CHzCI'Iz-NO(CH2CH3 2---, D0. -CH2CHZNO(CH2CH3)2 Scarlet. CHzCHr-NO(CH2CH3)2... D0. CHQ,CH2NO,(CH2CH3)2--- Red.

CHzCH2 2-CHa)2 Scarlet CH2OH2NO(CH2-CHa)2 Red; -CH2CH2NO-(CH2-OH3)2 Scarlet (l0 CHz-OHzNO(CH2CH )2 Red. 4-chloropl1enyl CHz-CH2NO(CHzCHa)2 Orange 4-cyanophenyl CHzOI-Iz-NO(CH5CH;)2... D0. 4-methylsulfonylpheny1.- CHrCI-l2NO(CHzCH3)z D0. 4-dimethy1amin0sulfo- -CH2CH2NO(CHzCHs)2. Do.

nylphenyl. 4-methyla1ninosulfo- 1T FT -CHnCH2N 0 (CH3): Do.

nylphenyl. 4-trifluoro-methylphenyL CH CH N0 (CH3)z. 4-nitro-2-ch1orophenyl- CH1CH-NO (CH3) 2 1 4-nitro-2-bromophenyl 4-nitro-2-cyanopheny1 2.4dinitr0-phenyl 1 4-nitro-2.G-diehlorophenyl- 2.4-dieyano-phenyl 1 H Th iazol Benzothiazolyl-Z H Shade of Dyeing Example R4 2 1 R R11 on Poly- No. ucrylonitrilc Fibers 5-nitrothiazolyl-2 -CH2CH2N0 (CH3) z fi-uitrobenzothiazolyl-Z.. s -CHzCHz a)2- fi-methylsulfonylbenzo- -CH2CH2NO (0113);-

thiazolyl-2. fi-dimethylaminosulio- -CH CH -NO(CH3); Do,

nylbenzothiayzolyl-Z. fi-methylaminosulfonyl- CHzCHr-NO(CII3)2 Do.

bcnzothiazolyl-2. Emethoxybenzotbiazolyl-L. CHCHz-NO(CH3)2 Scarlet fi-methylbenzothiazolyl-2. GHgCH -NO(Cl-Iz)z.- D0. 5-acetyl-thienyl-2 H Violet 3-nitro-5-acetyl-thienyl-2 Blue. 2-chlorophenyl 11 Yellow Z-trifluoromethylphenyL- Do. 2-nitrophenyl Red. 2.4.6-trinitrophenyl. Do. 2.4-dichlorophenyl Orange 4-acetylphenyl Red. do Do. Do. Do. Do. Do. Do. Do. -C1l CH NO(ClI3)z..- Do. t do -CI-I OH;NO(CII3)..- Do. 4-nitro-2-bromophenyL. t CII CH NO(CH:)2--- Do. 4-nitro2.G-dibromophenyl CH2CH1NO(C1I3)2... Brown do -CII2CHZNO(CII3 Do. i-nitro-lcyanophenyh CIl CH NO(CIIa)1. Rod.

CQII-|NO(C3U7)2-- Do. C2II-]NO(C|HI5)Z- D0. -CH1NO(CII3)2 D0.

EXAMPLE 66 EXAMPLE 67 parts of ternary mum of the formula 56 parts of the red dyestuff obtained according to Example 66 are dissolved in 1000 parts of chlorobenzene and /C132CH3 200 parts of methyl alcohol at boiling temperature. 40 C parts of dlmethyl sulfate are dropped into the clear red CHPCHPMCHM solution with vlgorous stirring, upon which the solution are dissolved in 20 parts of ethyl alcohol and reacted with 20 parts of 34% hydrogen peroxide at 60". On completion of oxidation, which can be followed from the consumption of the oxidizing agent, the reaction mixture containing the crude aminooxide compound is diluted with parts of acetic acid. The clear solution obtained is added to a previously prepared diazo solution of 18 parts of 6-methoxy-2-aminobenzothiazole, 250 parts of 100% sulfuric acid, 250 parts of water and 7 parts of sodium nitrite at 5. On completion of coupling, the reaction mass is charged onto 750 parts of ice and with vigorous stirring about 500 parts of 30% sodium hydroxide solution are added to adjust the pH value to 5. The precipitated red dyestuff is filtered off, Washed neutral with dilute salt solution, and dried. The crude product is obtained in excellent yield and is practically pure. It dissolves in water with a fine red coloration and dyes polyacrylonitrile fibers by the process described in Dyeing Example b in level red shades of good fastness to light, washing, perspiration, sublimation, pleating, pressing, water, sea water, gas fumes and bleaching.

The new dyestufi has the formula rapidly changes color to blue.

After a short time quaternation is completed. The reaction mass is allowed to cool and the precipitate formed is filtered off, washed with chlorobenzene and dried.

The crude product is obtained in excellent yield and is practially pure. It dissolves in water with a brilliant blue coloration and in concentrated sulfuric acid with a yellow coloration. Applied to polyacrylonitrile fibers by the method described in Dyeing Example b, it gives brilliant blue shades of excellent fastness to light, washing, perspiration, pressing, water, sea Water, gas fumes and bleaching, and reserves wool present in the dyebat h. The dyeings are very level, being markedly superior in this respect to dyeings of the constitutionally similar dyestuffs produced from the same diazo compound and diethylaminobenzene as coupling component.

The new dyestuif has the formula HaC-O Further valuable basic dyestufis which can be produced according to the details given in Examples 66 and 67 are .l a. i

described in the following table; they correspond to the formula 10 sulfonic acid and/or carboxylic acid groups or of fre dyestuffs acids of 2:1 metal complex dyestuifs free from sulfonic and carboxylic acid groups; with these ions the x 69 l s resulting dyestuffs are insoluble both in water and oramone 5 ganic solvents and are valuable for use as pigments.

l Some of the coupling compounds used in the foregoing y 9 examples are new. They can be produced, for example,

Shade of Example Dyeing on No. R 2 y Rs Rn Polyacryloilitrile Fibers NInethylbenzotl1iaz0lyl-2 N-ethylbenzothiazolyl-2- N-benzylbeuzthiazo1y1-2- N-methyl-6-meth0xy-benzothia- CHzCH2NO-(CH3)L Do: -CHzOHzNO-(GH3)2 D0. CHgCH2NO(CHa)a Do. -CH2C}I2NO'(OH3)L D0. Methyl. OH OH:NO(CH3)2. Do. Methoxy CHzCH2-NO D0. H CHzCHzNO( D0. H CHzCHzNO D0. H -CHzCHzNO(OHa)2---- D0.

11 do -CHzCH2-NO(CHa)2. Do. do H -CHzCH2-NOC(CH:4)2 -CH2CHz-NO-(CH3)2- Do. N-etihygfl-rnethoxybenzothiall Ethyl OH2CH2-NO(OH3)2. Do.

20 Nethyl-thiazolyl-2- H clo. -CH2CH2-NO(CH3)L Violet. 86 N-methyl-thiazolyl-Z- do CHzCHzNO-(CHa)2 Do. 87 N11ict1h2yl-6-methoxy-benzothia- II CHz--CHzNOz(CH2)2 Ethyl Bule.

zo y 88" d0 H H CH CHzNO(C2H5)z OHzCH1NO(CzH5)z- D0. 89 N-mlelihyl-fi-ethoxy-benzothia- H H CH2CHaNO(CnH5)z. CHgC1'I2NO(C2H5)L---- D0.

20 y -2-. N n11et1hyl-6-methylbenzothia- H H CHz-CH2-NO(C2H5)2 OH-CH NO(G H5)z... D0.

y -2-. N-ruethylthiazolyl-2- OH2CHzNO(OH3)z Violet. N-ethylthiazolyl-2-. CH -CH-NO (CHi)g Do.

zo yl-2-. N-methylthiazolyl-2- Methyl... H .d0 CH2CHr-NO(CH3)Z Violet.

Hcoo, CHI -coo: C2H5COO-, C3HTCOO- ClCH COO-, C H COO, the lactate, oxalate, tartrate or citrate ion. When produced with these ions the dyestuffs are sufliciently soluble in Water to be applicable to polyacrylonitrile fibers from aqueous solution. Anion 9 can also represent a caproate, enanthate, caprylate, pelargonate, caprate, undecylate, laurate, myristate, palmitate, stearate, arachidate, oleate, elaidinate, erucate, linoleate or linolenate ion; in such cases the dyestuffs are less soluble in water but are soluble in organic solvents, e.g. acetone, methylene chloride and dimethyl formamide, and are suitable for dyeing cellulose acetate, cellulose triacetate and polyacrylonitrile in the mass, as well as polyacrylonitrile from aqueous dispersion. Finally, anion 9 can also represent a phosphotungstate, phosphomolybdate, phosphotungstomolybdate, silicomolybdate or silicotungstate ion or the anionic form of dyestuffs containing from the corresponding hydroxy components according to the scheme can be detected from the conclusion of the exothermic reaction, the liquid mass is run into a mixture of 400 11 parts of ice and 100 parts of water and the reaction mixture adjusted to the pH value of by the addition of dilute sodium hydroxide solution. The precipitated oil is then separated and distilled with vacuum. Its boiling 12 are dissolved in 20 parts of ethyl alcohol and reacted with 20 parts of 34% hydrogen peroxide at 60. On completion of oxidation, which can be checked by observing the consumption of the oxidizing agent, the reacpoint is at 133-135 at 14 Torr. The yield is almost 5 tion mass containing the crude aminooxide compound is quantitative. 184-parts of the N-ethyl-N-chloroethylevaporated to dryness with vacuum and added to 300 aminobenzene obtained and 400 parts of 40% dimethylparts of water containing 12 parts of 30% hydrochloric amine solution are mixed in an autoclave for 20 hours at acid. A clear solution is formed which is added to a 140. On cooling, the reaction mixture is drawn ofi in previously prepared diazo solution of 17.5 parts of 1- a separating funnel and the organic phase distilled with amino-Z-chloro-4-nitrobenzene, 30 parts of 30% hydrovacuum. Its boiling point is 85-86 at 0.03 Torr. The chloric acid, 200 parts of water and 7 parts of sodium yield is practically quantitative. nitrite at 5. On completion of coupling, which can be The following table gives details of further valuable speeded up by the addition of sodium acetate, the precipitertiary amines which can be produced according to the tated red dyestufi? chlorohydrate is filtered off, washed particulars presented in the foregoing. neutral and dried. The crude product is obtained in excellent yield and high purity; it melts at 116-120". It Formula Boiling pressure can be recrystallized if desired from glacial acetic acid to Point, in Torrgive a dyestufl. of low water-solubility which dyes polyacrylonitrile fibers from aqueous colloidal solution in 143444 1344 level red shades of excellent fastness properties. l-(N-tektlhyl-N-dimethylarninoethyl)-ami.uo-3- m 143 14 15 When 1-d1azo-2-chloro-4-nitrobenzene is coupled with THC -)8l'1Z8I10 .1 N.N-hi -(ehloroetl1yl)-an1inobcnzone. 109-170 14-15 the coupllng comlmnent 0f the formula l-N.N-bis-(cliloroethyl)-an1ino-3-methylbenzene 1S0182 13-14 l-N.N-bis-(ehloroethyl)-amino-3-chl0roben- I O GHQ-C11;

zone 198-200 13-14 20 CH; T/ 1-(N-cthyl-N-diethylaminocthyl)-amino-3- c IIZ (3 II2 N (3 I12 methylbenzene 161-162 14 1-(N-isobutyl-N-chloroethyl)-amino-benzene 144-146 13-14 N C 1I2 C H2 (N-mothyl-N-chloroethyl) amino-hen zene 127-128 12- 1-(N-ctl1yl-N-dibutylaminoethyl)-amin0- 0 UPC H3 3-methyl-benzene 145-116 0. 01 1-(N-isobutyl-N-dimethylaminoethyl)-arnino- 3O 1-8%3fetiw'tnaiaittsisnnaaiasiasnaf- 14-15 a red dyestufi which melts at 135- 40 is obtained.

benzene n n n nn n. 129-130 14-15 The two following tables g1ve details of further amino- 116-118 0.06 Oxide dyestuffs of the formulae l-N.N-bis-(dirnethylaminoethyl)-amino-3- chlorobenzene 171-172 13-14 N .N-his-(dimethylaminoethyl)- mmo- R11 R12 139-140 13-14 R" methylbenzenei 93-94 01 1 (alkyl) 2N O-Rm- -N=N- -N/ N-ethyl-N-diethy oethyl-aminoben zene 159-160 13-14 1-(N-ethyl-N-2'-piperidinoethyl)-amin0-3- R methlyllicrnzzgnem.iuffttiii 133-134 0.09 1- N-et 1y --'-morp 10 y o y -arn methyl-benzene 152-155 0.02 and R10 EXAMPLE 110 26 parts of the tertiary amine of the formula (ZflkYDQNO-R15-N=NR I CH2CH N They are characterized in the tables by the symbols CH 0 alkyl, 10 11, 12 13 and 14 15, R16: and 17 2 respectively, and by the shade of the dyeings obtained CHZ-CHZ with them on polyacrylonitrile fibers.

Shade 0! Dyeing R10 R11 R12 R13 R11 on Polyacrylonitriie Fibers (CHZ);4-HNOZS- H Methyl--. Yellow-orange. (CH1)a-HNOzS H --do D0. -(CHz)1-HNOzS----- H Do.

Red-orange o. Yellow-orange.

Red.

Red-orange.

Red.

EFF

m'F/i Do: Yellow-Oran g0. Red-orange.

Shade of Dyeing on Example No. Alkyl R15 Rm 17 y ylonitrile Fibers Yellow. Do. Do. Do. do Do. (CHz)zCO-HN 4-hy lroxy-phenyl Do. (CHz)zSOz-HN ..dO D0. (CH2)2O-COHN 2-acetylamino-4-hydroxypl1enyl. Do. -CH2-OO- 4-dimethylaminonaphthyl-(1). Violet. CH2CO 4'-diethylaminophenyl Ruby CHzCO-- d CH2CO CH2CO OH2CO -CH2CO- CH2CO -CHCO Further examples are the dyestuffs of the formulae:

| 021-15 150 [(OH3)gN0(CHz)g-]z=NOzSC -N=NC N Yellow-orange.

C2135 OH;

I 2 151 [(CH3)2'NO(CH2)2]FN-'O2SC (32 152 HsMN0-(OH2)aHNO2S-C -N=N-N\ p0.

CgH4-N0 M EXAMPLE 3 1 part of a dyeing preparation vmade according to the polyacrylonitrile staple fiber yarn are immersed in the liquor at 50. The machine is closed, the inside temperature increased to 130 and dyeing continued at this c 've Ex 1 nd c inin 5 is: 5 28 g; f Eg ig e 1 a Oma g 3 of temperature for 30 minutes under pressure. A brilliant,

y level-dyed blue shade of high tinctor-ial strength is ob- HO O OH tained which shows excellent fastness properties.

I II I Dyeings of similarly high all-round fastness are obtained with anthraquinone dyestuffs of, e.g., the following formula SlO2NHCHzCHzNO-(CHQ-OHg): R Rm I I II I OzN O NH R24 R10 is suspended in 3000 parts of water at room temperature with 5 parts of acetic acid. The suspension is run into a high temperature dyeing machine and parts of O Shade of Example Dyeing on NO. R18 R19 R20 R21 R22 R23 R24 R25 Polyacrylonitrile Fibers 154 Ami11o Cl H NII'CHZCHZNO(CH3CH3): H H H H Blue. 155 .d0 Br H NHCHgCH -NO(CH CHz) H H H II Do. 156 o (R19 and R10 together) Amino H H H H D0.

/3 /NCH2CH;NO

CO (-CH CH 157 OH H H NHCH;CH;NO-(CHzCH3)g NO; H H OH Green-blue.

15s Amino" 11 H NHC -SO NH H H H H Violet-blue.

CHz-CH NO(CH CHs)2 159 OH H H NH-CH2CH1NO on 11 H No, Blue.

x-CH3): 160 Amino" C'Fa t. H -NI-ICHzCHzNO(CH;0119 H H H H Green-blue.

1&3

Shade of Example Dyeing (In No. R18 R19 R20 R2: R22 R23 R24 R1: y fylonilrlie Fibers 161 OH H H -HN N01 H H 011 Green-blue.

| S102 NH-CH CI-I NO(C H acrylonitrile fiber and subsequently steamed for 30 min- EXAMPLE 162 utes in a star steamer or in a pressure steamer at 7 lbs.

1 part of the dyeing preparation made up as described per sq. in. pressure. The level blue print obtained has in Example 1 with the dyestuff of the formula very good fastness to light and rubbing.

is dispersed with 10 parts of acetic acid in 3000 parts of water at room temperature. 200 parts of a blended EXAMPLE 173 fabr'c cont 'n'ng 607 01 r lonitrile fiber and 407 cotton in fi g g g at and dyed 2 When polyacrylonltrlle fabrics are dyed from a neutral minutes at 0 under Pressure The Synthetic fibsr is or Weakly acid bath according to the details of Example dyed in a deep, level reddish-yellow shade while the cot- 1 with a dyesmfi of the formula ton is reserved. 9

Dyeings having similar fastness properties are obtained 011 when, for example, the following dyestuffs are used: I

No, (HsCHzO)2NO-CH1CH2OON=NQ 1 R24 11 --so N C Q N G 2* Shade of Dyeing Example No. R25 R21 R28 on Polyaerylollitrile Fibers CHiCI-I1NO(CHz-CH3)z. H Yellow. CH -CH -NO(CH,CHa)z- CH3.. D0. cH2-0H2N0Pom-Crisis... CzII- Do. -cHT-cH N0(0H 0H3)2 CH Do. CHZCHZNO(-CHZCH3)Z.- -c rr Beddisll-yellow. --CH OH NO(OH CHa)z -0H D0. cH -cHr-N0(cH2CHa)i CH;CH,NOPom-Cum.-. II Yellow.

(I311: 170 CII;CHNO-(CH;CH3)1 C2H5 CIIJ D0.

Further the dyestufi of the formula:

i CH:

171 H -NII SOzN\ Yellow.

CII C II;N 0 (C2l1' EXAMPLE 172 or 30 parts of the dyeing preparation made as described in Example 1 with the dyestuif of the formula Ho 0 011 60 (CHa)2NO-CH:O-N=

CH: or

I ll om 0 NH@ (ammo-4:11

is suspended with parts of thiodiglycol and 10 parts of acetic acid in hot water and the suspension mixed with a gum tragacanth thickening :1000 to give 1000 parts @113 of printing paste. This is applied to a fabric of polyor II (In The dyestufl of the formula Last paragraph CH3 t I Cz s O2N- -N=N N\ C2H4NO (CHm EXAMPLE 19 C 2 4-NO (C2 a gives blue prints.

The dyestufi of the formula applied according to the process described in Example 172 gives full, level orange prints with very good fastness properties.

Formulae of representative dyestuffs of the foregoing examples are as follows:

EXAMPLE 1 Paragraph 2 c1 I C2H5 O2N- N=N N\ C2H4NO (CH3) 2 EXAMPLE 2 N02 CH3 O2N N=N N\ C 2H4N 0 (CH3) 2 EXAMPLE 3 Paragraph 1 C1 CH I I C2H5 OzN -N=N- N\ C :JL-NO (CH3) 2 Cl Paragraph 2 I C H 2 5 OzN- -N=N- -N\ CZH-A-NO(CH3)2 C1 EXAMPLE 4 /OH -OHz-NO(OH3)a CH2CHz-NO (CH No. 3 of the table C1 CH3 /Cz s 0 Hz 0 Hr-C N EXAMPLE 28 CzH4-NO (CH3)?! EXAMPLE 29 O zN- -N=N N\ EXAMPLE 59 B l C H5 I I /C 2 5 Cz 4N O s) 2 EXAMPLE 60 B 1' C H:

02N N=N -N\ C2H4 0(C 3)2 B r EXAIMPLE 61 C 2H4- 0 3) 2 B 1 EXAMPLE 62 C N C H3 I I /C 2 5 C 2H4-N 0 3) 2 EXAMPLE 76 a G9 I N C H I I Anion 1130-0- N=NN C zHA-NO (CH3) 2 19 20 EXAMPLE 84 wherein; @2115 n is one of the numerals 1 and 2; 69 l m is one of the numerals and 1; N 6 9 q is one of the numerals 0 and 1; J on p is one of the numerals 0 and 1; R300 5 O q being at most equal to p.

z A- 3): 2. The basic dyestuff of the formula EXAMPLE 85 (I11 I N CH i i a m O r s N N Cam-browns): 3. The basic dyestuff of the formula EXAMPLE 86 15 CH 01 Q s 02H N CH: l 01H5 Anions o2N- N=N N\ N H CH (I31 C2 4 NO( 1):

ozHp-No (C2115) 2 EXAMPLE 87 4. The basic dyestuff of the formula fi Q N CH3 02H; e I e N 1130-0 S N=NON\ Anion /C2HB s;

CzHt-NO (02115), S /-N=N- N EXAMPLE 109 CH M-N 0 (CH3) 1 1 5. The basic dyestuff of the formula N CH: C H

CN K J- =NON/ Anion C2115 s C 2H4-NO (CH3) 2 O 2N N--N N\ EXAMPLE 110 02H4-N0 (CH1); (:1 CH3 I 6. The basic dyestufi of the formula OaNGN=N N\ 0Hl-01 I1 C2H4li]\ /0 (IN CH3 C H 0 CH2-CH2 0 N a 5 Having thus disclosed the invention what I claim is: 2 G V 1. Basic dyestufl of the formula czHr-NO nu-( m n;

2 O Cn-lHin-l 11 H) l /C2H5 0 m 1 N=N -N\ Anion CH e! 3 ozHt-N wmn l T m S/ in References Cited in the file of this patent UNITED STATES PATENTS 2,238,485 Dickey et a1 Apr. 15, 1941 OTHER REFERENCES Costa: Gazctta Chimica Italiana, 1959, pages 1050- 1065.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 119,809 January-- 28 1964 Bruno J 0 Ha Nicolaus It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 4 lines 60 to 63; the formula should appear as shown below instead of as in the patent:

a -cH columns 7 and 8, in the table second column line 6 thereof for "nylbenzothiayzolyl2" read nylbenzothiazolyl-2 columns 9 and l0 in the table second column, line 34 thereof for N-"methyltriazolyl--2-".read N-methylthiazolyl2- columns 13 and 14 in the second tahle second column opposite Example No, 151 the right-hand portion of the formula should appear as shown below instead of as in the patent:

lines 60 to 67, the left-hand portion of the formula column 15,

as in the patent:

should appear as shown below instead of HO O OH Signed and sealed this 20th day of October 1964.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents

Claims (1)

1. BASIC DYESTUFF OF THE FORMULA