Patented Nov. 9, 1948 2,453,420 ‘

uNlTEosrATEs PATENT OFFICE‘

MORPHOLINE SALTS 0F SULFONATED AZO DYE‘ COMPONENTS AND THEIR. PREPARA-l

HaroldlGfGreig, ‘Princeton, N. J., assignor to , ‘ Radio Corporation of America, a‘corporation‘ ‘ of Delaware . No Drawing. Application December 21, 1944, 3 Serial No. 569,264 , I 14 Claims. (01.260-247) . 1‘ “ 2 a . ‘The present invention relates to _morpholine ‘dye components, while they provide the desired salts of the sulfo acids‘ of cyclic organic com water solubility, have a number of disadvantages.‘ pounds having a sulfonic acid group linked to a Thus the sodium salts have a tendency when dried ring carbon atom thereof and tea process of ‘pro to darken, ‘ a phenomenon which ‘is particularly ducing the same. i “ “ ' ' “ ‘ " noticeable Where the component contains a ‘plu It is known that azo dyestuffs are‘prepared by; rality ‘of sulfonic acid groups. ‘ Suchdarkening . diazotizing an aromatic ‘ and coupling the ‘ is apt to b‘e‘reflected in the ?nal color of the dye» resulting diazonium compound‘ with‘ an ‘azo cou stuff and may result in a distortion, of the shade. pling componentx‘The diazotizable em - of the dye. ployed are primary aromatic amines of the ben ‘(in the other hand, if it be desiredrto avoid the zene, , anthracene and the like series. darkening, particularly whenutilizing the poly, The azo coupling componentaon the other hand, sulfonic‘ acids, by only partially neutralizing the.» are usually phenols or’compounds having a re component, if the component be employed in a active methylene group ‘such as pyrazjolones, ‘ ‘ dry composition, the acidity imparted to the com acetoacetic acid arylides and‘t‘he like, ‘ V‘ ‘ " ‘position may have a deleterious effect thereon. ‘The majority of the azo ,dye components are Assuming, ‘for instance, that the composition , not per se soluble in water. ,It is, therefore, cus contains a stabilized diazo amino compound and tomary practice‘ to ‘include in such ‘components, an incompletely neutralized sulfonated coupling, water-solubilizing groups, particularly sulfonio ‘component, thecomposition due to the acidity acid groups. The components are then utilized in -'¢ = of the coupling component is liable to decompo the form of the alkali metal, particularly the sition of the diazo amino compound with attend sodium salts. , . , , ant premature coupling. On the other hand, if The azo dyestuffs are utilized not only in the the composition contains a diazotizable amine, a dyeing of ?bers but also in other arts such as in nitrite and an incompletely neutralized ,sulfo color photography for the production of photo nated coupling component, the acidity thereof is graphic dyestuff images and in electrolytic‘ re apt to cause premature diazotization and cou cording methods for the formation‘ of dyestu?" pling. images. When using the ‘azo dyes in these var Again, in effecting neutralization of azo dye, ious arts, it is often desirable to produce the dyes components containing a plurality of sulfonic acid from compositions containing‘ the desired com 30 groups, it is necessary to utilize theexact amount ponents in the dry state. For instance, it has ‘ of alkali if the product is to be isolated by dry been recommended to employ a composition for ing, since otherwise the excess alkali remains in dyeing and printing comprising‘ a stabilized diazo the dry product. If the alkali be added in water amino compound and a coupling compound and solution to the product, the same becomes so to regenerate the diazonium compound for cou 35 soluble in water as to prevent efficient isolation pling by treating the composition with an acid. by the salting out method. It has also been suggested to provide a composi ‘I have now discovered that not only these, dis; , tion of a diazotizable amine,‘a nitrite and a cou advantages in ‘the sodium salts of sulfonated pling component to dissolve the same in water and cyclic organic azo dye components can be avoided to impregnate material ‘withthe composition for but ‘that, salts manifesting; properties not‘pos-ll use in facsimile recordings. When these pro sessed by__the sodium salts are obtained if ‘the posals are adopted, the compositions must meet sulfonated component be neutralized in whole or certain tests, For instance, they must’ ‘readily ‘ in part by means of morpholine. , 1 dissolve in water, they must be stable‘ prior to dis 45 ‘ The morpholine salts do not have the undesir solution in water, and particularly when utilized able tendency to darken possessed by the sodium in the formation of azo dyestufi images in pho salts. They can be prepared andisolated with- ‘ tography and in facsimile recording, they must . out difficulty since any excess of morpholine em provide a background stable to light and storage. ployed in the preparation of the salts can be The sodium salts of the sulfonic ‘acids of azo 50 volatilized I therefrom at low temperatures. , 2,453,430 3 It is accordingly an object of the present inven l-amino-2.4-disulfo-8-hydroxynaphthalene hav tion to‘ produce sulfonated cyclic organic com ing the formula pounds in which at least one of the sulfonic acid 0H NHZ groups is neutralized by morpholine. A further object of this invention is the prepa ration of sulfonated phenol in which at least one sulfonic acid group is neutralized by morpholine. A further object of this invention is a naphthol sulfonic acid in which at least one of the sulfonic acid groups is neutralized by morpholine. 10 A further object of this invention is a phenol 24amino-8-naphthol-6-sulfonic acid» . containing a plurality of sulfonic acid groups, 1-phenylamino-4-aminobenzene-2-sulfonic acid each of which is neutralized with morpholine. TliLamino-2-naphthol-4-sulfonic acid A further object of this invention. is naphthol _ 1;;-aminobenzenee3vi-sulionic‘ acid polysulfonic acids in which allof the sulfonic acid-a I531. 1:1,.-aminobenzene-4-sulfonic acid groups are neutralized with morpholine. 1é-amino42.5-dichlorobenzene-4esu1fonic acid . A‘ further object of this invention is a phenol, 1-methyl-2-aminobenzene-5-sulfonic acid containing a plurality of sulfonic acid groups-at, ‘ ;l-lmetliyb‘i-aminobenzene-Z-sulfonic acid least one of which is neutralized by morpholine 4t4"-diaminodiphenyl=-2.2'edisulfonic acid having and another an alkali such as an alkali metal or the formula ‘ an organic amine. ' ' Another object of this invention is chromo tropic acid the sulfonic acid groups of whichare; I neutralized by means of morpholine. s'oln, SIOaH ,The ‘morpholine salts of the cyclic organic 25 4.4,’ -diamino-3 .3 ’ -dimethyl-6.6' -disulfod,iphenyl compounds having a sulfonic acid group linked 1-naphthylamine-2—sulfonic acid. to a ‘ring’ carbon atom thereof can be simply pre 1-naphthylamine-4-sulfonic _ acid pared in 'a number of ways. For instance, the 1-naphthylamine-dsulfonic_ acid sulfonic acid may be slurried withan amount of Z-naphthylamine-l-sulfonic acid morpholine in excess of that theoretically re 2-naphthylamine,-5—sulfonic. acid, ‘ quired to neutralize the sulfonic acid groups pres 2-naphthylaminee3.6edisu1fonic, acid. ent ‘and suflicient to give a smooth, uniformly . 2-naphthylamine-5.7-disulfonic acid . wet paste. The excess of morpholine is then re 44.’ -'dia'minodiphenyl.-3.3f -disulfonic. acid, moved by volatilization at a temperature between 1-aminor2-nitrobenzene-4esulfonic_ acid" about 65 to ‘70° C. "In this way, all of the sill Z-aminodiphenyl-‘If-sulfonic acid,v fonic‘acid groups in the component are, neutral, 4.4,f -d_iamino.diphenylj-2esulfonic, acids ized by the morpholine. ‘ 4-aminodiplienylaminee2esu1ionic acid‘ , As an alternative, one mol of the sulfonic acid 1—naphthylamine-4éacetyl-amino-7ksulfonic acid. is‘ reacted with an amount of morpholine theoe 1 .4~diaminobenzene-6.-su1f onic _ acid, retically necessary to neutralize the sulfonic acid.‘ G-amino-1.—naphtho1-3-sulfonic acid. groups present, the reaction being effected in a 8-’amino.-1rnaphthol-2Ardisulfonic acid‘ closed vessel such as a ball mill by means of. which 8-amino,,-. l.-naphthol,-3.6-disulfonic . acid thorough mixing of the reactants can be‘ accom-. 3-amino-2-naphthol-7~sulfonic acid= plished. The reaction mixture is then dried at l-naphthylamine-3.6.8etrisulfonic. acid.v a low temperature such as that given ‘above. The ratio of the sulfonic acid to the morpholine and the - like: varies depending upon the particular sulfonic; Examples'of sulfonated cyclic organic coupling acid utilized and the results desired. If, for 'eX-H components the morpholine; salts or which are ample; the acid is a disulfonic acid and it is desired; cont‘einplated'by the present invention are: to neutralize only one sulfonic acid group, then 2-hydroxynaphthalene-6-sulfonic acid: one mol of the sulfonic acid is utilized for one 2#hydroxynaphthalene-8esulfonic acid‘ mol of morpholine. If, however, the disulfonic 1e.hydroxy.-.8 --,- aminomaphthalene-B?edisulfonic' acid is to be completely neutralized, then at least, acid : . - two mols of morpholine are used for each mol of a1.8-dihydroxyv-naphthalene-3;6-disulfonic acid, the acid. In a similar way, when using atri 55 1-hydroxy-naphthalene-3.6-disulfonic, acid: sulfonic acid, it is possible to neutralize one, two. 1-hydroxy->8;-~amino-naphthalene-ii?edisulfonio or all three of the acid groups present. acid havingthe formula Furthermore, by a proper proportioning of'the. reactants, the acids may be converted into mixed. ' NHz (‘3H salts of ' morpholine and another, neutralizing, 60 agent such as an alkali metal, i. e., sodium, potas sium or the like, or’ an organic amine such as an alkylamine, i. e., ethylamine, propylamine, butyl: amine, dimethylamine, diethylamine, and the like, an arylamine such as aniline, phenylmethylamine, orlthe’likesor an alkylolamine such as mono. 1-hydroxy-8-acetylamino naphthalene-ii?edisul ethanolamine, diethanolamine, triethanolamine, fonic acid propanolamine, dipropanolamine; dibutanol~ ‘ l-hydroxy-éleaminq naphthalene - 6.7‘- disulfonic, amine‘ and'the like. ' ' acid‘ The sulfonic acids of any of the diazot‘zable" 70 1.7-dihydroxy naphthalene-3.6-disulfonic acid“ aromatic amines may be neutralized by means 1 =hydroxynaphthalene-3 .6. 8-trisulfonic acid of morpholine in the manner stated above. ‘Ex. 1.3-dihydroxynaphthalene—5.’7-disulionic acid‘: amples of ' diazotizable aromatic amines which 1.5+dihydroXynaphthalene-2.7-disulfonic acid? may be. treated for the purpose.of-neutralizingthei 1.5'Ldihydroxynaphthalene-3.7-disulfonic acidf sulfonic acid groups with morpholine are: 75 1.7-dihydroxynaphthalene~3.G-disulfonic acid $453,430

l-hydroxy-?amino‘ ‘naphthalene '-'3.6 -?disulfonic1 ‘ 1 molofdia'zotized naphthionic acid+1 mol of: acid . l “ l ‘ ‘diiso propanolamine v a i 2-naphthol-3.6-disulfonic acid 1 mol‘of diazotized‘naphthionic‘ acid-l-l mol of 2-naphthol-6.8-disulfonic acid. monoethanolamine ‘‘ ‘ i 8-hydroxyquinoline-5isulfonic acid . ‘1 mol of diazotized naphthionic acid+1 mol of 1- (N-phenyl) —naphthylamine-8-su1fonic acid] morpholine ‘ “ v 1- (4' -sulfophenyl) ~3-methyl-5-pyrazolone hav H mol of diazotizedf alpha naphthylamine-4.8 ing the formula‘ ‘ ‘ ‘ ‘ . “ v , disulfonic acid+1 mol of diethanolamine ISOaH¢ ‘7 H mol of diazotized alpha‘ naphthylamine-4.8 10 disulfonic acid-I-Z moles of diethanolamine ‘ mol of diazotized alpha naphthylamine-5-sul ionic acid-I-l mol of diethanolamine H mol of diazotized beta naphthylamine-?-sul ‘ fonic acid-H mol of diethanolamine ‘ /'IlI\ 16 1 mol of diazotized naphthylamine-3.6-disulfonic 0=0 N acid+1 mol of diethanolamine ‘mol of diazotized naphthionic acid+1 mol ‘of Hz é‘ C—CH3ll cyclohexylamine 1- (4'-sulfophenyl) -3-carboxy-S-pyrazolonev ‘ mol of dia‘zotized naphthionic acid-l-l mol'of“ 6.6’-ureylene~di-(1-naphtholr-3-sulfonic acid) 20 2.5-dihydroxy-dicyclohexylamine-B'-carboxylic 6.6’-amino-di(1-naphthol-3-sulfonio acid) acid > ‘ ‘ ‘ ‘ 8-acetylamino-1enaphthol-a?-disulfonic acid 1 mol of diazotized naphthionic acid+1 mol of 2.6-diaminopyridine disulfonic acid p-hydroxy cyclohexenyl glycine 1 mol of diazotized‘ naphthionic acid-l-l mol of The morpholine salts of the amines may be 25 dibutylamine I ‘ employed as‘ such for diazotization and subse 1 mol of diazotized naphthionic acid+1‘ mol of quent coupling orlthey may be employed in the di-Z-ethylhexylamine ‘ ‘ form of the ‘stabilized vdiazo“ amino compounds. mol of diazotized naphthionic acid-l-limol of Any of the aforesaid amines ‘after diazotization 4-sulf0-2eamino benzoic acid ‘ ‘ ‘ may be stabilized by reacting the diazonium com~ 30 1 mol of tetrazotized dianisidine+2 mols pound in‘an alkaline solution with an alkyl," an 4-sulfo-2-amino benzoic acid ‘ aryl or a heterocyclic amine. Examples of such mol of diazotized naphthionic acid+lmol Of amines serving to stabilize the diazonium com alpha-hydroxy pyrrolidine ‘ pounds are: 1 ‘ mol of diazotized naphthionic acid-H mol of 35 ethanolamine gamma-hydroxy piperidine mol of diazotized naphthionic acid-l-l mol of diethanolamine ‘ ‘ sarcosine carbazole-Z-sulfonic acid ‘ diisopropanolamine mol of diazotized naphthionic ‘acid-l-l‘ mol of alpha-carboxy pyrrolidine ‘ ‘ morpholine ‘ 40 cyclohexylamine ‘ 1 mol of diazotized naphthionic acid+2 mols of morpholine ' 2-5-dihydroxy-dicyclohexylamine - 3? - carboxylic acid The following examples will serve to illustrate‘ p-hydroxy cyclohexenyl glycine ‘ my invention although it is to be understood that methyl glucaminei ‘ 45 the invention is not limited thereto: ‘ alph-a-carboxy pyrrolidine Esample ‘I alpha-l-alpha-Z-dicarboxy pyrrolidine carboxy-piperidine 1 mol of chromotropic acid‘in the form of a ' loiponic acid ‘ ‘ ?nely ground dry powder is slurried‘ with 5.5 mols beta-carboxy-piperidine 50 of morpholine until a smooth, thick paste‘ is tetrahydroquinoline obtained‘. This pastels stirred at room tempera piperidine ture until the mix has become uniform and thor carbazole oughly wet throughout. The excess morpholine diglycolamino acid “ is then driven off by heating the‘ composition to a temperature of 65 to 70° C.‘ The product thus‘ benzyl-xylamine ‘ 55 4-sulfo-2-amino benzoic acid obtained is then ground for further use. ‘When dibenzylamine-disulfonic acid dissolved in the ratio of .03 gram mols per liter,

taurine ‘ ' ‘ itggives 'a solution‘ having a pH of about 9.5. cyclohexylamino-acetic acid The product obtained is the di-morpholine salt morpholine ‘ ‘ ‘ of chromotropic acid and has the following 60 2-methylamino-4-sulfo benzoic acid formula: ‘ i p methyl mannamine dimethylamine diethylamine dibutylamine Examples ‘of stable‘ diazoamino compounds illustrative of those which I have employed in carrying out the invention are ‘the following: 1 mol of tetrazotized' benZidine-3y.3'-disulf0nic 70 acid-l-Z moles of diethanolamine‘ ‘ l‘mol of diazotized naphthionic acid+1 mol of

diethanolamine ‘ > i 1 mol of‘diazoti'zed naphthionic acid+2 moles of 1 mol of R‘ acid is ?ne1y‘g1fouhd in a ball ‘mill diethanolamine ‘ l ‘ n l I‘ with 1“ mol-of morpholine, at room temperature. 9%335136

. Stirring should be continued untilf'the‘fmass ‘has naphthionic 'gac'id "stabilized with morpholine, the‘ become uniform and thoroughly ‘wet throughout. sulfonic acid group of the naphthionic acid being Theiproduct after drying is'ithe'mono-morpholine neutralized by means’ of morpholine. ' ‘ salt of R acid and has the followingiformulat EmampUZe'I/III . . The procedure is vthe same as in Example ‘I except that the chromotropic acid is Ireplaced 'by. 2-naphthy1amine-3.G-disulfonic acid. Example VIII The procedure is the .same as in Example I except that the chromotropic acid is replaced by 4.4’-diaminostilbene-2.2'.-disulfonic acid. . It has been stated above that the morpholine salts possess properties which are not exhibited by the corresponding sodium salts. It has been .1 mol of G acid in- the form :of a?nelygroundj found, for instance, that the morpholine salt of dry powder is slurried with about -5 rnolswof an azo component couples much more quickly _morpholine to form a thick paste. uAfter‘stirring= than thesodium salt, particularly ,if coupling at room temperature to make theipasteuniform, . takesplace ‘under acid conditions or if acid con it is heated to a temperature of 65 to '70°:'C. to ditions‘ prevail prior {to ,coupling. Apparently remove excess morpholine. The dry ‘di-mor the acid splits the 'morpho'l'ine which then acts pholine salt of Cream is thus ‘obtained. - r ' ‘ as a coupling aid to cause the ‘coupling to proceed at a more rapid rate than if ‘the sodium salt were ' " ‘Example IV U 1 , used or if no morpholine were‘ present. _ .75 mol of diisopropanolamine ‘.isdissolved in The pertinency .of i this observation has-been. 5.74 mols of morpholine. '1 mol of-chrornotropic demonstrated by tests, particularly in the -prepa-. acid in a dry, ?nely groundycondition 'is slurried ration .of dye images in facsimile recording. In with the morpholine solution.“ The product is such methods, a traveling web or band impreg~ then dried at atemperature of about 70° C.. A‘ nated with azo dye components is caused-to pass product having a dark gray color is-thus obtained. through an electrolytic cell the anode of whichis This product is the mixed salt of diisopropanol-. a‘ ‘printer bar. Acid conditions prevail at the amine and morpholineof the formula: . . printer bar so that ifa diazotizable amine or~a stabilized diazo amino compound is present, a ' \ OH ‘nu I . diazonium compound capable of coupling is pro duced under the acid conditions. In tests car ried out with a naphthionic acid as'th'e diazotiz able amine and chromotropic acid in theform ‘of its sodium salt as the coupling agent/dye vIforma 40 tion did not take place until after the paper ‘had traveled several inches beyond the -printer'bar. However, when using , the ‘morpholine ‘salt of chromotropic acid in lieu of the sodium salt, color develops almostas'soon as the paper leaves v the printer bar. This test emphasizes’the fact Example “V that the morpholine salt is much more amenable 1 mol of naphthionic acid is slurried with an to couplingthan the sodium salt, a factor which excess‘of morpholine until a smooth, thick paste is of the greatest importance in producing ‘dye is obtained. This paste is stirredat-roomtem images in color photography or in facsimile perature until the mixture has become thoroughly 50 recording. ' l ‘ wet throughout. ‘The excess morpholine is then Where azo dye components vare employed for driven off by heating the compositionlto a tem— the purpose of producing localized dye images as, perature vof about ‘70° .C. The product thus for instance, in photography or in facsimiles obtained is the morpholeum salt of .naphthionic recording, the components are incorporated uni formly throughout the ?lm or throughout the acid. I. ExampleI VI i _ traveling Web or band. After dye formationfthe components which have ‘not been developedin 1 mol of sodium naphthionate'is diazotized with color should be removed. It is, however, difficult 1 mol of sodium nitrite at a temperature of 5'~to to remove the components completely. 1 Often 10° C. ~ \ ‘ _ times the residual components remaining cause by means of 280 cc. of 38% hydrochloric acid. a darkening of the ‘background of the v?lm or The diazotization compound‘ precipitates as a recording material, particularlywhen exposed to thick, creamy slurry. The product is stirred for light or when stored for long periods‘of time. v‘.[t one hour to make itzmore amenable to ?ltration. has been found that this tendency to-background The ?lter cake obtained upon ?ltration is reslur darkening, while being very pronounced‘ where" ried in water until a smooth pasteis obtained. the sodium salts are employed,..is materially This paste is added slowly at 10 to 15° C. over lessened where the morpholine saltsare utilized. a one-hour period with rapid agitation to an The ' morpholine salts therefore appear to be excess of morpholine while maintaining a tem much ‘more stable to the action of light and air perature of 10 to 15° C. in an ice bath to mini 70 than v‘are the corresponding : sodium salts. The mize decomposition. The reaction is complete superiority of the morpholine-salts in this respect when all of the diazonium compound has been is of ‘very great importance wheredyeimages'are ‘ added. Excess morpholine'Tis removed by heat locally formed, since it serves to agreatfextent ing the composition to a temperature-of- about ' to overcome the problempresente‘d :byrthe diffi 70° C. There is thus obtained the 'diazotized 75 culty of removing the components :fromth‘ose 2,453,430 9 , 10 , portions of a ?lm or recording paper which serve 8. The process of producing a morpholinium as a background for the dye images. salt of a naphthol polysulfonic acid which com Various modi?cations of my invention will prises reacting 1 mol of the acid with at least occur to persons skilled in the art and I therefore 1 mol of morpholine at a temperature sufficient ‘ do not intend to be limited in the patent granted to volatilize any excess morpholine. except as required by the prior art and the ap 9. The process as de?ned in claim 7 wherein pended claims. ‘ the naphthol sulionic acid is chromotropic acid. I claim: 10. The process as de?ned in claim 7 wherein 1. The process of producing a, morpholiniurn the amount of morpholine‘employed is that theo salt of a sulfonated cyclic organic compound 10 retically necessary to convert all of the sulfonic having a. sulfonic acid group directly linked to a acid groups of the naphthol polysulfonic acidinto ring carbon atom, which comprises reacting at their morpholinium salts. ‘ ‘ least one mol of the sulfonated cyclic organic 11., The process of producing a morpholinium compound with at least one mol of morpholine salt of chromotropic acid which comprises react at a temperature su?cient to volatilize any excess ing 1 mol of the acid with at least 1 mol of morpholine. i morpholine at a temperature between 65 and 2. A naphthol sulfonic acid in which at least 70° C. . , one sulfonic acid group is neutralized by means 12. The process of producing the di-morpho of morpholine. ‘ linium salt of chromotropic acid which comprises 3. Naphthol polysulfonic acids in which at least reacting one mol of the acid with an ‘excess over one sulfonic acid group is neutralized by means 2 mols of morpholine at a temperature of 65 to of morpholine. 70° C. i ‘ ‘r i ‘ 4. Naphthol polysulfonic acids in which at least '13. Naphthionic acid, the sulfonic acid group one sulfonic acid group is neutralized by a mem of which is neutralized by morpholine. ber selected from the class consisting of alkali 14. A phenol containing the grouping metals and alkylolamines and at least one other sulfonic acid group is neutralized by. means of morpholine. 5. Naphthol disulfonic acids in which both sulfonic acid groups are neutralized by mor 30 the sulfur atom of which is directly linked to a ‘ pholine. ring carbon atom. 6. A compound of the following constitution: HAROLD G. GREIG. REFERENCES CITED The following references are of record in the ?le of this patent: UNITED STATES PATENTS Number Name Date 40 826,279 Schirmacher ______July 17, 1906 1,975,340 Winker ______‘ ______Oct. ‘2, 1934 2,124,594 Schmelzer ______‘__- July‘ 26, 1938 2,125,087 Schmelzer _, ______July 26, 1938 2,132,405 Schmelzer ______Feb. 118, 1941 45 7. The process of producing a morpholinium, 2,306,471 Solomon ______Dec. 29, 1942 salt of a naphthol sulfonic acid which comprises reacting 1 mol of the acid with at least 1 mol of FOREIGN PATENTS morpholine at a temperature sufficient to vola Number Country Date tilize any excess morpholine. 180,884 ‘Switzerland ______Feb. 4 1, 1936