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Publication numberUS2957010 A
Publication typeGrant
Publication dateOct 18, 1960
Filing dateAug 28, 1958
Priority dateAug 28, 1958
Publication numberUS 2957010 A, US 2957010A, US-A-2957010, US2957010 A, US2957010A
InventorsJames M Straley, Ralph R Giles
Original AssigneeEastman Kodak Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Quaternary ammonium salts of anthraquinone dye compounds
US 2957010 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

*' tats Patented Oct. 18, 1960 QUAI'ERNARY AlVIlVIONIUM SAELTS F ANTI-IRA- QUINONE DYE COMPOUNDS 8 Claims. (Cl. 260-377) This invention relates to new anthraquinone com- .pounds and their application to the art of dyeing or coloring.

It is well known that polyacrylonitrilefibers are difficult to dye in deep, fast shades without the use of special dyeing techniques, such as, for example, the use of pressure, carriers or the so-called cuprous ion technique involving the use of acid wool dyes. Each of these methods involves one or more disadvantages. The use of pressure involves the use of pressure equipment which is more expensive than the equipment used where no pressure is involved. The use of carriers involves the expense of providing the carriers. Also, when carriers are employed operations for the recovery of the carrier for reuse are involved and these recovery operations add to the expense of the dyeing operation.

While many variations in the cuprous ion technique have been proposed all sufier some disadvantage. One of the chief disadvantages of this method is the fact that it is almost impossible to restrict the amount of copper absorbed to such a low degree that serious browning of the dyed fabric upon exposure to light does not occur.

It is an object of the present invention to provide blue anthraquinone dyes which yield dyeings 'on polyacrylonitrile textile materials which have excellent fastness to light and washing. A further object is to provide watersoluble anthraquinone dye compounds which can be applied to polyacrylonitrile textile materials'in Water solutions. Another object is to provide new quaternary anthraquinone dye compounds capable of dyeing polyacrylonitrile textile materials deep blue shades.

The new anthraquinone compounds of the present in--- vention by means of which the objects of the invention can be accomplished are the quaternaryanthraquinone compounds having the formula:

fi N H2 C H (3 I C O N 0 11112 1?- 0 N R2 1 wherein R and R each represents an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, a p-methoxyethyl group or a fi-ethoxyethyl group, R represents an alkyl group, n represents 2, 3 or 4, X- is an anion and wherein taken together also represent a morpholinyl group or a piperidyl group.

Ethylene, tn'methylene, propylene, tetramethylene and Z-methyl trimethylene:

for example, are illustrative of the alkylene radicals represented by C H The new quaternary anthraquinone compounds of the present invention are prepared by quaternizing the anthraquinone compounds having the general formula:

(I? NHa C H C C ON CnHZnN wherein n, R, R and have the meaning previously assigned to them. These compounds which are valuable dyes for polyacrylonitrile fibers, especially modified polyacrylonitrile fibers, are new compounds and are described and claimed in our copending application Serial No. 757,680, filed August 28, 1958.

The anthraquinone compounds having the formula designated II are conveniently prepared by condensing the acid chloride of the appropriate 1-arnino-2-bromo-4- carboxyanilinoanthraquinone with a primary amine having the formula:

have the meaning previously assigned to them. The acid chloride of the 1-amino-2-bromo-4-carboxyanilinoanthraquinone compound is prepared by known methods.

Quaternization of the anthraquinonecompounds having the formula designated II may be carried out in an inert solvent using the known quaternizing agents. A dialkyl sulfate, an alkyl chloride, an alkyl bromide, an alkyl iodide, an aralkyl chloride, an aralkyl bromide or an alkyl ester of para-toluene sulfonic acid, for example, can be employed. Specific quaternizing agents include, for example, dimethyl sulfate, diethyl sulfate, dipropyl sulfate, dibutyl sulfate, ethyl bromide, ethyl chloride, methyl iodide, ethyl iodide, n-butyl iodide, lauryl iodide, benzyl chloride, benzyl bromide, methyl p-toluene sulfonate, ethyl p-toluene sulfonate, n-propyl p-toluene sulfonate and n-butyl p-toluene sulfonate.

Inert solvents that can be employed in the quaternization reaction include, for example, dimethyl formamide, acetone, ethylene glycol monoethyl ether, isopropanol, n-butanol, chlorobenzene and nitrobenzene.

Inasmuch as the new quaternary anthraquinone compounds of the present invention are water soluble they are applied to the polyacrylonitrile textile material from their solution in water, preferably at the boil. The property of water solubility is of real practical importance because dyes are almost exclusively applied from an :capable." It is: interesting to note that no significant dif- 1Q thraquinone were suspended in 100 cc. of dry 'o-dichlorothionyl chloride was removed by passing a stream of dry grams of 3-dimethylaminopropylamine and 2.26 grams of anhydrous sodium acetate were addedand'the reaction aqueous dyebath. Because the dyes are water soluble d th with hot water and dried at 110 C. 11.3 the manufacturer thereof is relieved from the costly procgrams of product identical with that prepared in Example ess of preparing mixes or dispersions that will form lwere bt i d,

suspensions of finely divided solids and the dyer is relieved from the necessity of adding'othersubstances, for example, in order to prevent the suspension or emulsion from breaking. If the dye suspension or emulsion breaks, uneven dyeing of the goods results and the dye fails to deliver the full money value of which it is Example 3 Example 1 was repeated using 1 gram of 1-arnino-2- bromo-4-p-carboxyanilinoanthraquinone and 4 grams of N- (Z-aminoethyl) piperidine. 1-amino-2-bromo-4-p- N- 2- piperidylethyl) carboxamido] anilinoanthraquinone having the formula:

ferences appear to depend upon thecharacter' of the I B quaternizing agent used.

The following examples illustrate the/compounds of our invention and their manner of preparation.

H H: Example 1 E l H One gram of l-amino-2-br0mo-4-o-carboxyanilinoan- O thraquinone was suspended in cc. of dry chlorobeng g zene. Two cc. of thionyl chloride were added and the reaction mixture obtained was heated on a steam bath, 20 with stirring, until a clear solution was obtained and no further color change toward the red occurred. The solution thus obtained was cooled to 80 C., diluted with an equal volume of n-hexane and cooled to20 C. The acid chloride thus prepared was recovered by filtration,

was obtained as 'a blue solid. It dyes polyacrylonitrile textile materials blue shades which have excellent fastness to light and wet processing.

Example 4 5 Example 2 was repeated using-3.3 grams of'3-(4'-morwashed with n-hexane and sucked dried. The acid chlophohnwpropylamme ride product thus obtained was added to 3.5 cc. of 3-di- H2 H1 methylaminopropylamine and the resulting mixture was 'v warmed on a steam bath to complete solution. The re- H2NCH2CH2OH2N 0 action mixture was then poured into five times its volume of water and the reaction product which precipitated was H1 H1 recovered by filtration and dried at 110 C. 0.95 gram in place of 3-dimethylaminopropylamine.

l-ammo-2-bromo-4-o C O NCHZOHQO H2N\ O amlmoanthraqurnone of 1-amino-2-br0mo-4-o-l I-(3-dimethylaminopropyDcar- 4O wasobtained as a blue solid. It dyespolyacrylonitrile bOXamldO] allililloanthfaqulnone having the formula: textile materials blue shades which have excellent fastness 0 to light and wet processing. it I Br Example 5 Example 2-was repeated using 3 grams of o lit CH; OH; H H CH3 1 rhNcnzdnomN ONCHzCHzCHzN CH:

in place of 3-dimethylaminopropylamine. was obtained as a blue solid which dissolved readily in -warm .dilute HCI. It dyes polyacrylonitrile fibers blue H (3H3 CH;

shades. havlllg eXcellellt fastfless t0 llght and Wet P 1-an1in0-2-bromo-4-o- OONOHQCHCHQN anilinoanthraquinone cessing.

Example 2 was obtained as a blue solid. It dyes polyacrylonitrile textile materials blue shades which have excellent fastness to light and wet processing.

By the use of the appropriate dialkylarninoalkylamine and by following the procedure described hereinbefore, such as that described in Example 1, .l-amino-2-bromo-4- o [N- (2 -"dimethylaminoethyl)carboxamido]anilineanthraquinone, 1 amino 2 bromo-4-m-[N-(3-dirnethylaminopropyl) carboxamido] anilinoanthraquinone, l-amino 2 bromo 4 p [N (3 dimethylaminopropyl)- carboxarnidol anilinoanthraquinone, l-amino-2-bromo-4- o [N (3 diethylaminopropyl)carboxamido] anilinoanthraquinone, l-amino-2-bromo-4-m-[N-(Z-diethylaminoethyl) carboxamido] anilinoanthraquinone Ten grams of 1-amino-2-bromo-4ro-carboxyanilinoanbenzene. 3.4 cc. of 'thionyl chloride were added and the temperature of the reaction mixture wasgradually raised to 80 C. over'a period of about 1.5 hours and .held at this temperature for one hourwhile stirring. .Excess air through the reaction mixture at C.- C. After 65 cooling the reaction mixture to room-temperature 2.8

mixture was stirred at 70 C. C; for one-hour. The reaction mixture wascooled and-the product which precrprtated was recovered by filtration, washed with n-hexane H 1-amino-2-bromo-4-p-(C ONCH3CH2CH2N anilinoanthraquinone C Ho (11) 1- amino 2 bromo-4 o [N (3 di p hydroxyethylaminopropyl) carboxamido] anilinoanthraquinone, 1- amino 2 bromo 4 m [N (4 diethylamino nbutyl)carboxamido] anilinoanthraquinone, 1 amino 2- bromo 4 m [N (4 dimethylamino n butyl)car boxamido]anilinoanthraquinone, 1-amino-2-bromo-4-o- [N (3 di 13 methoxyethylamino n propyl)carboxamido] anilinoanthraquinone and 1-amino-2-bromo-4-o- [N (3 di 13 ethoxyethylamino n propyl)carboxamido] anilinoanthraquinone were prepared.

Other primary amines having the Formula III that can be used to prepare the anthraquinone compounds having the formula II include, for example, Z-di-n-propylaminoethylamine, 2-diiso propylaminoethylamine, 2-di-n-butylaminoethylamine, 2-(di-B-hydroxyethylamino)ethylamine, 2-(di-B-ethoxyethylamino)ethylamine, 3-(di 6 hydroxybutylamino)propylamine, 4-(di )8 hydroxyethylamino)- butylamine and 4-(4-morpholino)propylamine.

The anthraquinone compounds having the Formula II can be applied to polyacrylonitrile textile materials from an aqueous dyebath in the same manner that water-insoluble cellulose acetate dyestufis are commonly applied to cellulose acetate textile materials. Thus they may be directly applied to the polyacrylonitrile textile material undergoing coloration in the form of an aqueous suspension which can be prepared by grinding them to a paste in the presence of a sulfonated oil, soap, sodium lignin sulfonate, or other suitable dispersing agent and dispersing the resulting paste in water. In this method of dyeing the dye in finely divided condition is intimately dispersed in water and applied directly to the fiber.

Example 6 1.5 gram of the product obtained in accordance with the procedure described in Example 1 was dissolved in 15 cc. of dimethylformamide. One cc. of dimethyl sulfate was added and the reaction mixture resulting was heated at 75 C.-80 C. for 45 minutes. Upon cooling, the reaction mixture was diluted with three times its volume of hexane and the liquid was decanted from the sticky solid. The solid was dissolved in 25 cc. of water, heated to boiling and 1.5 to 2 grams of sodium chloride were added. On cooling to room temperature the solid present in the reaction mixture was recovered by filtration, washed well with a 5% aqueous solution of sodium chloride and then dried at 60 C. in vacuo. The dye product obtained is believed to have the following structure:

a 1-amino-2-bromo-4-po NC 11.0 11.01am

Example 7 0.4 gram of the dye product obtained in accordance with the procedure described in Example 1 and 3 cc. of dimethyl sulfate were warmed together on a steam bath. The resulting solution obtained was dull brown in color. After cooling, the solution was diluted with four times its volume of ether resulting in the precipitation of a sticky solid. The sticky solid was washed with ether and the ether was removed by decantation. The residue reof water, 1 gram of salt was added and after cooling,

the product was recovered by filtration, washed well with an aqueous salt solution and dried. The product obtained is identical tothat of Example 6. It dyes Verel and Orlon textile materials beautiful blue shades having excellent fastness to light and washing.

I Example 8 Example 6.was repeated using 1.5 cc.. of methyl-ptoluene sulfonate instead of dimethyl sulfate. Upon working up the reaction mixture in accordance with the procedure described in Example 6, a dyestuif which dyes Verel and Orlon beautiful blue shades having excellent resistance to light and washing was obtained. 'The dyeings obtained are indistinguishable from the dyeings obtained withthe dyestuffs of Examples 6 and 7. The dyeing was carried out in accordancev with the dyeing procedure described hereinafter.

Example 9 Example 11 One gram of 1-amino-2-bromo-4-m-[N-(2-diethylaminoethyl)carboxamido] anilinoanthraquinone was dissolved in 20 cc. ofacetone, 1' cc. of dimethyl sulfate was added and the acetone was removed by heating on a steam bath. The sticky product obtained was ground with hexane following which the hexane was removed by decantation and the residue remaining was allowed to airdry. The solid thus obtained was dissolved in 10 cc. of boilingw'ater and. precipitated by the'addition of 1 gram of sodium chloride. The reaction product was recovered by filtration, washed well with an aqueous salt solution and dried. The 'dyestulf obtained in accordance with this example yields blue dyeings on Verel and Orlon textile materials which have good fastness to light and washing.

Example ,12

1 amino 2 bromo 4 p [N (2 piperidylethyl)- carboxamido]anilinoanthraquinone was quaternized with dimethyl sulfate using the procedure described in Example 6. The quaternized dye compound obtained dyes polyacrylom'trile textile materials, such as Verel and Orlon, blue shades having good fastness to light and washing.

Example 13 anilinoanthraquinone was quaternized with dimethyl sulfate using the procedure described in Example 6. The quaternized dye compound obtained dyes polyacrylonitrile textile materials, such as Verel and Orlon, blue shades having good fastness to light and washing.

Example 14 Example 6was repeated using 1-amino-2-bromo-4-0[N- (3 di B hydroxyethylaminopropyl)carboxamido]- anilinoanthraquinone instead of the dye product of Exmaining after the ether decantation was boiled in 10 cc. ample 1. The quaternized dye compound obtained dyes polyacrylonitn'le textile materials, such as Verel and Orlon; blue shades having good fastness to light and washing.

1 Example 15 Example 6 was'repeatedusing the dye: compound of Example 4, l a mino'i-bromol-o [N (3 4'-morpholinopropyl)-carboxamido]-anilinoanthraquinone, instead of the dye product of Example l. The quaternized dye compound obtained dyes polyacrylonitrile textile materials,

such as-Verel and-"Orlon, blue shades'hain'ng" good CH: e H l 1-an1mo-2-bromo-4-o- C ONCHiGHCHaN 'CHa was quaternized with dimethylsulfate using the procedure described in Example 6. The quaterm'zed dye compound obtained dyes polyacrylonitrile textile materials, such as Verel and Orlon, blue shades having good fastness to light and washing.

Example 18 1 amino 2 bromo 4 o [N (3 diethylaminopropyl)carboxamido] anilinoanthraquinone was quaternized with dimethyl sulfate using the procedure described in Example 6. The quaternized dye compound obtained dyes polyacrylonitrile textile materials, such as Verel and Orlon, blue shades having good fastness to light and washing.

The following example illustrates how the quaternized anthraquinone compounds of the invention can be applied to polyacrylonitrile textile materials. These compounds are particularly useful in connection with the dyeing of modified polyacrylonitrile textile materials, such as Verel.

Example 19 16.7 milligrams of the dye product of Example 6 were dissolved in 200 cc'. of 'Water and '5 grams of Verel polyacrylonitrile textile material in fabric form were added. The temperature was/raised to 90 C.-95 C. and cc. of a 5% aqueoussolution offormic or acetic acid were added. The temperaturewas maintained at 90 C.95 C. for lhour; 'The goods were then removed from the dye bath, 'rinsed in hot-Water and allowed to dry. The Verel polyacrylonitrile textilematerial was dyed a blue color which"was*fast,:-forexample, toilight-and washing. The blue dyeing showed no break upon 20 hours exposure in a fadeometer. Further, in-a standard AATCC No. 3 wash test for synthetic materials no loss in color occurred and no staining of the undyed multifiberlnylon, cellulose acetate, cotton, silk,-viscose and wool) fabric took place. Similar results are obtained when an Orlon 42 polyacrylonitrile textile material is dyed. This procedure is applicable to polyacrylontrile textile materials generally. The textile material can be, for example, in fabric, yarn, filament or fiber form.

The primary amine compounds having the Formula III used in preparing the new anthraqu-inone compounds having the Formula II appear to include new as well as old compounds. Many of these amines are specifically disclosed in the prior art'. Those not specifically disclosed can be prepared by the-methodsused to prepare the known compounds The preferred amine B-dimethylaminopropylamine is anarticle of'commerce.

Three general processes by which primary amines having the Formula III can be perpared are set forth hereinafter:

- ]anilinoanthraquinone (1) An amine having theformula:

/R HQN R1 '(IV) is condensed with a chloroalkylnitrile having the formula: Cl( CH CN, and the product obtained is "reduced by sodlum-alcohol or with hydrogen over'Raney nickel to give the desired product:

/R 'mNwHmHN (2) Potassium phthalimide is-condensed with adi- 'brornoalkyl compound having the formula: Br(CH Br to obtain"C H (CO) N(CH Br which is treated with which is hydrolyzed withdilute mineral acid to give the desired product. Method 2'is the well-known Gabriel synthesis.

(3) A secondary amine is added to an unsaturated -nitrile, e.g-. methacrylonitrile, andthe product hydrogenated to the primary amine:

R1 CH: R1 CH:

CH3 CH3 HzNcHfl lHClHaN and CH3 HaNCHqHCHzN as used herein have the meaning previously assigned to them, whilex is 1,2 or 3'and z is 2, 3 or 4.

' The 1 amino Z-brorno-Lcarboxyanilinoanthraquinone compounds used in the preparation of the new anthraquinonc compounds having the Formula II can be prepared bythe procedure "described in. Berichte," vol. 49,

9 page 2167 (1916), wherein the preparation of l-amino-Z- bromo-4-o-carboxyanilinoanthraquinone is described.

As previously indicated, there appears to be no significant difference in the dyeing properties of the new quaternized anthraquinone compounds of the invention regardless of the quaternizing agent used. However, from the standpoint of ease of manipulation and economy we prefer to use dimethyl sulfate.

We claim:

1. The anthraquinone compounds having the formula:

wherein R and R each represents a member selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, a ,B-methoxyethyl group and a B-ethoxyethyl group, R represents an alkyl group, n represents a small whole number from 2 to 4, X is an anion and wherein taken together represent a member selected from the group consisting of a morpholinyl group and a piperidyl group.

2. The anthraquinone compounds having the formula:

wherein R, R and R each represents an alkyl group having 1 to 4 carbon atoms, X- is an anion and n represents a small whole number from 2 to 4.

3. The anthraquinone compounds having the formula:

(I) NH: C

R X H CONCHICHQCHIN wherein R, R and R each represents an alkyl group having 1 to 4 carbon atoms and X- is an anion.

is 4. The anhraquinone compounds having the formula:

wherein R, R and R each represents an alkyl group having 1 to 4 carbon atoms.

5. The anthraquinone compound having the formula:

if) NH:

I N HQ bogomomomfirwnm 6. The anthraquinone compound having the formula: (III) NH:

O Br s OF 7. The anthraquinone compound having the formula:

cogomomcmlfwiflm References Cited in the file of this patent UNITED STATES PATENTS 2,716,655 Boyd Aug. 30, 1955 FOREIGN PATENTS 855,541 Germany Nov. 13, 1952 UNITED STATES PATENT OFFICE CERTIFICATION OF CORRECTION Patent No. 2,957,010 October 18, 1960 James M. Straley et a1.

Column 1, line 27, for "the carrier-SQ" Also," read the "carriers. Also, column 3, line 40, for "l-o-N" read 4o[N column 7, line 65, for "polyacrylontrile" read polyacrylonitrile column 8, line 2, for "perpared" read prepared column 9, line 10, for "anhraquinone" read anthraquinone Signed and sealed this 25th day of April 1961.

(SEAL) Attest:

ERNEST W. SWIDER' DAVID L. LADD Attesting Officer Commissioner of Patents

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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3036078 *Dec 21, 1959May 22, 1962Ciba LtdWater-soluble salts of anthraquinone dyestuffs
US3234234 *May 1, 1962Feb 8, 1966Ciba Ltd1, 8 diamino-2, 7-dibromo-4, 5-di-succinimido anthraquinone
US3253877 *May 24, 1963May 31, 1966Eastman Kodak CoAcrylonitrile-vinyl chloride copolymer textile materials dyed with black cationic dyestuffs
US3274198 *Jun 14, 1963Sep 20, 1966Gen Aniline & Film CorpQuaternary anthraquinone dyestuffs
US6359052Aug 1, 2000Mar 19, 2002Jack Wesley Trexler, Jr.Polyester/platelet particle compositions displaying improved dispersion
US6384121Dec 1, 1999May 7, 2002Eastman Chemical CompanyPolymeter/clay nanocomposite comprising a functionalized polymer or oligomer and a process for preparing same
US6417262Dec 1, 1999Jul 9, 2002Eastman Chemical CompanyHigh barrier amorphous polyamide-clay nanocomposite and a process for preparing same
US6486252Jun 22, 1999Nov 26, 2002Eastman Chemical CompanyNanocomposites for high barrier applications
US6486253Dec 1, 1999Nov 26, 2002University Of South Carolina Research FoundationPolymer/clay nanocomposite having improved gas barrier comprising a clay material with a mixture of two or more organic cations and a process for preparing same
US6486254Dec 1, 1999Nov 26, 2002University Of South Carolina Research FoundationColorant composition, a polymer nanocomposite comprising the colorant composition and articles produced therefrom
US6548587Jun 14, 2000Apr 15, 2003University Of South Carolina Research FoundationPolyamide composition comprising a layered clay material modified with an alkoxylated onium compound
US6552113Dec 1, 2000Apr 22, 2003University Of South Carolina Research FoundationPolymer-clay nanocomposite comprising an amorphous oligomer
US6552114May 13, 2002Apr 22, 2003University Of South Carolina Research FoundationProcess for preparing a high barrier amorphous polyamide-clay nanocomposite
US6586500May 30, 2001Jul 1, 2003University Of South Carolina Research FoundationPolymer nanocomposite comprising a matrix polymer and a layered clay material having an improved level of extractable material
US6596803Jun 29, 2001Jul 22, 2003Amcol International CorporationLayered clay intercalates and exfoliates having a low quartz content
US6610772Aug 2, 2000Aug 26, 2003Eastman Chemical CompanyPlatelet particle polymer composite with oxygen scavenging organic cations
US6653388Dec 1, 1999Nov 25, 2003University Of South Carolina Research FoundationPolymer/clay nanocomposite comprising a clay mixture and a process for making same
US6713547Mar 6, 2002Mar 30, 2004University Of South Carolina Research FoundationProcess for preparing high barrier nanocomposites
US6737464May 30, 2000May 18, 2004University Of South Carolina Research FoundationPolymer nanocomposite comprising a matrix polymer and a layered clay material having a low quartz content
US6777479Aug 2, 2000Aug 17, 2004Eastman Chemical CompanyPolyamide nanocomposites with oxygen scavenging capability
US6828370May 30, 2001Dec 7, 2004Amcol International CorporationIntercalates and exfoliates thereof having an improved level of extractable material
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Classifications
U.S. Classification552/249, 544/162, 544/156, 8/654, 546/204
International ClassificationC09B1/20
Cooperative ClassificationC09B1/207
European ClassificationC09B1/20K