US2266823A - Water-soluble azo dyes from aminoaryloxy-acyl-diamines - Google Patents
Water-soluble azo dyes from aminoaryloxy-acyl-diamines Download PDFInfo
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- US2266823A US2266823A US345171A US34517140A US2266823A US 2266823 A US2266823 A US 2266823A US 345171 A US345171 A US 345171A US 34517140 A US34517140 A US 34517140A US 2266823 A US2266823 A US 2266823A
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- acid
- sulfonic acid
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- 239000000987 azo dye Substances 0.000 title description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 48
- 238000004043 dyeing Methods 0.000 description 21
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- 239000001257 hydrogen Substances 0.000 description 19
- 239000002253 acid Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 15
- 239000000975 dye Substances 0.000 description 13
- 150000002431 hydrogen Chemical class 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- -1 4- (4'-amino-phenoxy-acetylamino) -1-aminobenzene Chemical compound 0.000 description 10
- 239000003086 colorant Substances 0.000 description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 9
- 229910052736 halogen Inorganic materials 0.000 description 9
- 150000002367 halogens Chemical class 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 230000008878 coupling Effects 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- 239000000835 fiber Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 229920000297 Rayon Polymers 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 4
- 239000002964 rayon Substances 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- 238000009967 direct dyeing Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000004627 regenerated cellulose Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 241000947840 Alteromonadales Species 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- 241001621335 Synodontidae Species 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000982 direct dye Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002790 naphthalenes Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 1
- WZZBNLYBHUDSHF-DHLKQENFSA-N 1-[(3s,4s)-4-[8-(2-chloro-4-pyrimidin-2-yloxyphenyl)-7-fluoro-2-methylimidazo[4,5-c]quinolin-1-yl]-3-fluoropiperidin-1-yl]-2-hydroxyethanone Chemical compound CC1=NC2=CN=C3C=C(F)C(C=4C(=CC(OC=5N=CC=CN=5)=CC=4)Cl)=CC3=C2N1[C@H]1CCN(C(=O)CO)C[C@@H]1F WZZBNLYBHUDSHF-DHLKQENFSA-N 0.000 description 1
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 1
- QPKNFEVLZVJGBM-UHFFFAOYSA-N 2-aminonaphthalen-1-ol Chemical compound C1=CC=CC2=C(O)C(N)=CC=C21 QPKNFEVLZVJGBM-UHFFFAOYSA-N 0.000 description 1
- UYEMGAFJOZZIFP-UHFFFAOYSA-N 3,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC(O)=C1 UYEMGAFJOZZIFP-UHFFFAOYSA-N 0.000 description 1
- SFBLEQLFKYMMRJ-UHFFFAOYSA-N 5-amino-4-phenylpyrazol-3-one Chemical class O=C1N=NC(N)=C1C1=CC=CC=C1 SFBLEQLFKYMMRJ-UHFFFAOYSA-N 0.000 description 1
- WVRYXJXPKJMSON-UHFFFAOYSA-N 5-chloronaphthalene-2-carboxylic acid Chemical compound ClC1=CC=CC2=CC(C(=O)O)=CC=C21 WVRYXJXPKJMSON-UHFFFAOYSA-N 0.000 description 1
- XECRVULUEJSGBY-UHFFFAOYSA-N 5-hexylbenzene-1,3-diol Chemical compound CCCCCCC1=CC(O)=CC(O)=C1 XECRVULUEJSGBY-UHFFFAOYSA-N 0.000 description 1
- GQSBPRQSYUGPIP-UHFFFAOYSA-N 5-propoxybenzene-1,3-diol Chemical compound CCCOC1=CC(O)=CC(O)=C1 GQSBPRQSYUGPIP-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 229940126657 Compound 17 Drugs 0.000 description 1
- 241000630665 Hada Species 0.000 description 1
- 241000699670 Mus sp. Species 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229940126142 compound 16 Drugs 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- HDVRLUFGYQYLFJ-UHFFFAOYSA-N flamenol Chemical compound COC1=CC(O)=CC(O)=C1 HDVRLUFGYQYLFJ-UHFFFAOYSA-N 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- OIPPWFOQEKKFEE-UHFFFAOYSA-N orcinol Chemical compound CC1=CC(O)=CC(O)=C1 OIPPWFOQEKKFEE-UHFFFAOYSA-N 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DIORMHZUUKOISG-UHFFFAOYSA-N sulfoformic acid Chemical compound OC(=O)S(O)(=O)=O DIORMHZUUKOISG-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
- C09B35/50—Tetrazo dyes
- C09B35/56—Tetrazo dyes of the type
Definitions
- This invention relates to new direct tetrakisazo dyes, and especially to such dyes in which the first components are a class of amino-aryloxyacyl-diamines, to improved dyeings'produced by the new compounds and to methods of manufacturing.
- Direct dyes are those which dye the cloth directly from a water bath. without subsequent treatment. These colors, numerous examples of which are recordedin the literature, are very useful because they are substantive to cellulose and possess bright shades which are moderately fast to light. These products are very fugitive to washing. The dyeings'show considerable loss in strength when washed and they impart an undesirable stain in washing to associated uncolored or differently colored fibers; It is therefore desirable to provide direct colors which possess good washing fastness and do not stain other associated fibers.
- diazo colors have been improved by providing substantive diazotizable colors, diazotizing the direct colors on the fiber and then developing with suitable coupling components. These diazo colors are faster to washing but duller in shade than the corresponding direct colors.
- objections to developed diazo colors is the considerable shade change which usually results on development and the relatively high expense for materials and processing to be borne by th dyer who must carry out the development.
- Another object of the invention is to provide direct dyeings which are capable of being aftertreated by simple procedures.
- Another object of the invention is to provide dyes which will show little if any shade change by such after-treatment.
- Another object is to provide dyeings 'havx pound hereinafter to be described, making direct dyeings and thereafter appropriately” treating the direct dyeings with formaldehyde to form a formaldehyde complex on the fiber.
- Y compounds of the above general formula are amine substituted coupling components of the benzene and naphthalene series represented by the following formulae in which one D is -hydroxy and the other is hydrogen; the M'w-hich is meta to hydroxy is sulfonic acid and the other M is hydrogen; R is from the group consisting of hydrogen, car- .boxy and sulfonic acid; RF" is one of a group 'consistingof methyl and carboxy; R" is one compoundhayingtwozp im rrarylam nei roup T edisazo'compound etnazetized anine
- the product was isolated byihea'ting: hes1urry;to;60?65- sa t n cslowly .to,.a5.-.%r am-the volume; filtering a d d yi n an qyemat .75? fl didy, powder hada red-brown frziThedy'e is repr'esented'by the. formula.
- the dye is represented by the formula III. SOsNa N803 H G- EXAMPLE
- 12.9 parts of 3-(4-amino-phes'noxy-acetylamino)-1-amino-benzene 12.9 parts of 1 4- (4'-amino-phenoxy-acetylamino) -1-aminobenzene, and for 25.2 parts of 2-amino-5-naphthol-T-sulfonic acid, 37.? parts of 2-(3'-amino- I 'benzoyl-amino)-5 naphthol-7-sulfonic acid, another product was made.
- Thedrypowder was red-brown in appearance.
- the dyeing was scarlet having ex- The after-treatment y' be e aifreshfs cellent washing fastness and good discharge properties. 4 j
- the dye is represented by the formula NaOS NH
- the treated dyeings which are made in accord- I ance with the invention have better washing fast- Superior dyeings are more economical fact that the dyeing operations are simpler, a
- Resorcinol is the preferredend component of this class.
- modifications of the invention which give dyeings having an exceptionally good balance of the improved properties.
- Such modifications are those in which the Y components are amino naphthol sulfonic acid and the hereinbefore indicated derivatives thereof and the amino-phenyl-pyrazolones and their derivatives; and the X components are represented by the formulae NH: G -ea?
- the many X components which can be used to make products having the general properties of those hereinbefore described are onyl amino) l-l-amino benzene -3- sulfonic acid,
- -HN-Aryl-NH2 is one of a group-consisting of radicals' of the a benzene and. naphthalene series represented by thejformula.
- R' is from the group consistingof hydrogen, halogen, carboxy and sulfonic acid
- R" is from the group consisting ofihydrogen'; halogen, alkyl having 1 to"6 carbons an'dthe correspondinga-lkoxy groupsxn'isl to 2";'m'is:1 to.2; and- Z is" one of i a group corrsistingjof amino and the and; each: Y; is: oneof; 8.21 group represented: by;
- -H represents the coupling position; on e Dis hydroxy and the other is hydrogen; the M which. is meta. to hydroxy is sulionic acid and the. other M is. hydrogen; R is fromthe group. consisting, of. hydrogen, car-boxy, and sulfonic.
- An azo compound of the groupconsistingof' the acids and the alkali metal salts thereof which in their acid form are represented by the formula wherein .-.HN-Aryl.NHz is one of a group con sisting of radicals of thebenzene and naphthaleneseries represented by the formula and m V HN z I (R') n in which each R is one of a group consisting-of hydrogen, lowerv alkyl and alkoxy, carboxy, sulfonic acid and halogen; R is-from the group consisting-of hydrogen, halogen, carboxy and sulfonic acid; R" is/fromthegroup consistingof hydrogen, halogen -lower' alkyl andthe corresponding alkoxy groups; n is..1 to 2; m-is1'to-2; and Z is one of a group consisting of amino and the radical and each Y is one of.
- R is from a. group consisting of hy- D drogen, ha1ogen, alkyl having 1 to 6 carbons, the
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Description
Patented Dec. 23, 1941 ARYLOXY-ACYL-DIAMINES ChiIes E. Sparks and James W. Libby, Jr., Wilmington, Del., assignors to E. I. du Pont de Nemours & Company, Wilmington, Del., a cornotation of Delaware No Drawing. Application July 12, 1940,
' Serial No. 345,171
17 Claims.
This invention relates to new direct tetrakisazo dyes, and especially to such dyes in which the first components are a class of amino-aryloxyacyl-diamines, to improved dyeings'produced by the new compounds and to methods of manufacturing.
Direct dyes are those which dye the cloth directly from a water bath. without subsequent treatment. These colors, numerous examples of which are recordedin the literature, are very useful because they are substantive to cellulose and possess bright shades which are moderately fast to light. These products are very fugitive to washing. The dyeings'show considerable loss in strength when washed and they impart an undesirable stain in washing to associated uncolored or differently colored fibers; It is therefore desirable to provide direct colors which possess good washing fastness and do not stain other associated fibers.
Heretofore poor washing fastness has been improved in the so-called diazo colors by providing substantive diazotizable colors, diazotizing the direct colors on the fiber and then developing with suitable coupling components. These diazo colors are faster to washing but duller in shade than the corresponding direct colors. Among the objections to developed diazo colors is the considerable shade change which usually results on development and the relatively high expense for materials and processing to be borne by th dyer who must carry out the development.
It is among the objects ofthis invention to provide azo dyes which combine the advantages of simplicity of application and freedom from shade change upon dyeing of the direct colors with the washing fastness of the diazo colors. Another object of the invention is to provide direct dyeings which are capable of being aftertreated by simple procedures. Another object of the invention is to provide dyes which will show little if any shade change by such after-treatment. Another object is to provide dyeings 'havx pound hereinafter to be described, making direct dyeings and thereafter appropriately" treating the direct dyeings with formaldehyde to form a formaldehyde complex on the fiber.
The new compounds ar represented in general by the formula I OOH and
in whichl i. is from the group consisting of hydrogen, halogen, carboxy and sulfonic acid; R" 'is from the group consisting of hydrogen, halogen, alkyl having 1 to 6 carbons and the corresponding alkoxy groups; m is'l to 2'; and Z is one of a group consisting of amino and the radical j The Y compounds of the above general formula are amine substituted coupling components of the benzene and naphthalene series represented by the following formulae in which one D is -hydroxy and the other is hydrogen; the M'w-hich is meta to hydroxy is sulfonic acid and the other M is hydrogen; R is from the group consisting of hydrogen, car- .boxy and sulfonic acid; RF" is one of a group 'consistingof methyl and carboxy; R" is one compoundhayingtwozp im rrarylam nei roup T edisazo'compound etnazetized anine p d appearance 3 light tajstness.
These compounds are valuable as direct dyes for oel-lulosicmaterials, such as cotton, regenerated cellulose rayon and similar dyeable substances; "They produce dyeings in bright shades. Superior washing fastness without loss of brightne'ss or marked changed of shade is attained by atter-treating the dyeings with formaldehyde,
thus, providing a class of dyes which give dyeings in bright shades having superior washing fastness; good discharge properties and other properties desired in dyeings, and dyes which can be operated to. make dyeings by simple: and economical methods.
This. invention will :be, more, fully set forth in the following more detailed description which includes examples. that are given as illustrative embodiments of the invention and not. as. limitations. thereof". Parts. are expressed in. parts; by weight unless otherwise noted;. I
EXAMPLE, I
Aslumy me amine: par s. of V f m pbe w -acetylamino) .;-ami ..m e eneq n- 300 arts qfgwater was; acidified with 9.1- arts of hydro hlo ic; a id and-stirred; to :a omp es 1ution, Thesolutionwascooled to 0- C. by adding ce and th n; ek azotized. y addin pa ts f sodium nitrite; with good agitation. The temperature was held at 0-5" C. for one-half hour and; a; 1disti not test for excess nitrite, was maintained; to. comple e. the; t trzq izatiom A.;so1ut.i0n1 wasjmade by: diss lvin 252 pa s of; 2ramino?5rnapht lolr'Z-sulf acid; in a water solution of;soda,-ash containing 400 Parts of water and 5 .7j:par ts of soda ash. 'Ifhis solution; was;,coo1ed: t0 0 C 31.8 partsof soda, ash were)dissolved, in; ithesolution and. the solution of ztliegtetrazoiwas :slowly added whilst maintaining :theitemp'erature; at;v 0-5? G; The mixture was then: stirred onehourafter all; the; tetrazo had been added.
The product of coupling was isolated by heat,- :ing1to 609-? (3., slowly salting to 5% of the volume, stir-ring; one-half: hour longer and ,filterrin ;v c
'l he -press cake "wasslurried with 700 parts of water, and .13 .8;parts;of hydrochloric acid were added 'IFhe mixturewas. cooled, to 5 C. and tetr'azotiz edby adding 6.9. parts of sodium nitrite and maintaining a strong testfor excess nitrite andfa temperature of 5-l0 C; for. one hour..
solution composed of 16:5"parts of resorcinol and 150' parts ofwater was cooled to 0C; by'ad- "ding about -'-parts Mice and 37 parts of soda ash were "addedi The tetrazo slurry-was-slowlyruninto the solu- -'tion-ofresorcinobwhilst maintaining goodagitationand a-te'mperature of 50 -5 0. andthenithe mixture was stirred onechour after the tetrazo had all been added. The productwas isolated byihea'ting: hes1urry;to;60?65- sa t n cslowly .to,.a5.-.%r am-the volume; filtering a d d yi n an qyemat .75? fl hadny, powder hada red-brown frziThedy'e is repr'esented'by the. formula.
on. Whendyed. on cotton or regenerated cellulose fibers and treated with formaldehyde as hereinafter described, the dyeing was'abordeaux shade havingexcellent fastnessto washing and good discharge-properties. Y r 1 The fibers were dyed and after-treated as follows: A dyebath was made by dissolving 0.3 g. of the product in 100 cc. of waterat 190-200=F.,
adding 0.2g. of sodium carbonate to assist the solution. The bath was diluted with .stirring to a total volume of 500 cc. withwater at approximately 160 F. and-40' cc.-io f.a 10% solution of Glaubers salt were added. 'A 10 g.-piece of rebath. The temperature of the dye bath was then raised to 180?-l90"F. in the course of fifteen minutes and the piece was held in' the bath at that temperature for one hour with stirring'atj frequent intervals. At the end of one hour,=the
dyeing was removed and rinsedin coldwater. 7
bath as follows:..
The rinsed dyeing from the above operation '5 generated cellulose rayon was wet out with water, squeezed partially dry and entered into'the dye .y i, e 'H. N=N' OCHrC-HN N=N i was entered into 500 cc.of:water at 130-140 F. and 10 cc. of 10% formaldehyde (25 cc. of approximately 37% formaldehydebyweight dilutedto 250 cc. with water) were added. The dyeing was 5 held in the bath at this temperature for twenty minutes and then removed, rinsed and dried. -The after-treatment may also be done in the dye bath. This is the preferred procedure because of its economy and ease of application. It is carried out as follows: At the end of the dyeing period and without removing the dyeing, 10 cc. of 10% formaldehyde are added to the dye bath and the bath is maintained at about 130-140 F. for about 20 minutes. After twenty minutes or for such other time as is necessary to form a formaldehyde complex with the dye, it is rinsed and dried. EXAMPLE II By following the procedure of 'Example I, except substituting 41.7 parts of"2-(4'-amino-3'- sulfophenylamino) -5-naphthol-7-su1fonic acid for 25.2 parts of 2'-amino-5-naphthol-7-su1fonic acid, another product was made. l The dried product was dark brown in appear- 25 ance. When dyed on regenerated cellulose rayon from a water bath and after-treated with formaldehyde as directedin Example. I, the dyeing was a rubine shade-possessing excellent washing fastness-and'good discharge'properties.. I
The dye is represented by the formula III. SOsNa N803 H G- EXAMPLE By following the procedure of Example I and substituting for 12.9 parts of 3-(4-amino-phes'noxy-acetylamino)-1-amino-benzene, 12.9 parts of 1 4- (4'-amino-phenoxy-acetylamino) -1-aminobenzene, and for 25.2 parts of 2-amino-5-naphthol-T-sulfonic acid, 37.? parts of 2-(3'-amino- I 'benzoyl-amino)-5 naphthol-7-sulfonic acid, another product was made.
} Thedrypowder was red-brown in appearance. When dyed on regeneratedlcellulose rayon and after-treated withgformaldehyde as directed in Example-I, the dyeing was scarlet having ex- The after-treatment y' be e aifreshfs cellent washing fastness and good discharge properties. 4 j The dye is represented by the formula NaOS NH The treated dyeings which are made in accord- I ance with the invention have better washing fast- Superior dyeings are more economical fact that the dyeing operations are simpler, a
smaller number of operations is required and the operations are more easily controlled.
Minor variations in the processes of coupling.
known to those who are skilled in the art can be made. Likewise variations in the concentration, temperature and duration of the after-treating processes can be made to suit special circumstances. Any alkali-metal salts can be used instead of the sodium salts and any of the halogen derivatives can be used instead of the chloro derivatives in making the compounds.
Resorcinol is the preferredend component of this class. There are various modifications of the invention which give dyeings having an exceptionally good balance of the improved properties. Such modifications are those in which the Y components are amino naphthol sulfonic acid and the hereinbefore indicated derivatives thereof and the amino-phenyl-pyrazolones and their derivatives; and the X components are represented by the formulae NH: G -ea? As other illustrations of the many X components which can be used to make products having the general properties of those hereinbefore described are onyl amino) l-l-amino benzene -3- sulfonic acid,
3- [beta- (2'-sulfo -4' amino-phenoxy-propionylaminoH-l-amino-benzene, V 4-[gamma-(2'- oarboxy -4'- amino-ph enoxy-bu-,
tyrylamino) l-l-amino-benzene,
7 amino) l-1 amino-2,5-dimethoXy-benzene,
RIIII' acid,
1 components are mentioned;
1,3-di(2'-'chlo"ro -4'- amino -5"- methyl-phenoxy-l acetylamino) -benzene, 7
l-(4'-amino phenoxy acetylamino) -2-methoxy- 4-amino-naphthalene-fi sulfonic acid,
1,4-di[alpha-('3'- amino phenoxy butyrylamino) ]-naphthalene-5-carboxylic acid,
1-(4'- amino-phenoxy-acetylamino) -4-' amino-5'- methoxy-naphthalene-7-sulfonic acid,
2-(3'-amino phenoxy acetylamino) -4-amino= naphthalene-S-sulfonic acid,
l-(4'-amino-phenoxy acety1amino)-.4l-'amino-8- '1 chloro-naphthalene-6-carboxylic acid,
1-(3- amino -6- methyl-phenoxy-acetylamino) 3-amino-benzene-5-carboxylic acid,
5 l-[alpha-(4'- amino phenoxy acetylamino) 1-4- amino-2,5-dichloro benzene, and
1-(2'-amino phenoxy acetylamino)-B-aminm fo-phenylamino) -5-naphtho1-7-sulfonic acid, 1-
(Bf-amino-benzoylamino) 5 -naphthol-7 -sulfonicacid, 1 amino 2 methoxy-naphthalene-6-sulfom'c acid, l-amino-8-chloro-naphthalene-B-sulfonic acid, l-amino-naphthalene-6-carboxylic thol-7-sulfonic acid, 2-(3-amino-4'-propoxy-5' chloro-benzoylamino)-5-napthol-'7-sulfonic acid, 1-(3'-amino-5'-carboXy-phenyl) -5-pyrazolone3- carboxylic acid, 1- (3 amino-5-sulfo phenyl) -5- pyrazolone-3-carboxylic acid, 1(3'-amino-4'- ch1oro-5'-ethyl-phenyl) -5 pyrazolone-3-carboxylic acid, 1 -(3'-amino-5-bromo-benzoylamino) 5-naphthol-7-sulfonic acid, '1-(4'-amino-3'-carboxy-phenyl) -5-methyl-p yrazo1one, 2-(4'-methoxy-3'-amino-benzoylamino) -5-naphthol-'7. sulfonic acid, 2!-(4'-amino-benzoylamino)-5-naphthol-7-sulfonic acid, and 2-,[4'+methoxy-3'(4' amino-benzoylamino) benzoylaminol 5 naphthol-7-su1fonic acid.
As illustrations of other-variations of the end 5-methyl-1,3-dihydroxy-benzene, 3,5-dihydroXy-benzene-l-carboxylic acid, 3,5-dihydroxy-benzene-l sulfonic acid,
1,3,5-tri-hydroxy-benzene, 1-methoxy-3,5-dihydroxy benzene, 1 --propoxy- 3,5-dihydroxy benzene and 1-hexyl-3,5-dihydroxy benzene.
From the foregoing disclosure it will be recog- 2-amino-3@-methy1-5-naphthol-.7 -sulfonic' radical in; which: Q; 1810118} 011 a--,.group.-- consisting of? branched and straight chain1aliphatic.:hydrocarbon-- radicals having 1 to 6 carbons; each R is; from the group consisting of hydrogen,- alkyl having. 1. to 6 carbons,v the, corresponding; alkoxy; groups, carb'oxy, sulfonic. acid and ha1ogen; ;R" isone of a. group consisting-of hydrogen, alkyl. having 1 to-6 carbons, the'correspondingialkoxy groups, hydroxy; sulfonicacid and carboxy;
-HN-Aryl-NH2 is one of a group-consisting of radicals' of the a benzene and. naphthalene series represented by thejformula.
whereinR' is from the group consistingof hydrogen, halogen, carboxy and sulfonic acid; R" is from the group consisting ofihydrogen'; halogen, alkyl having 1 to"6 carbons an'dthe correspondinga-lkoxy groupsxn'isl to 2";'m'is:1 to.2; and- Z is" one of i a group corrsistingjof amino and the and; each: Y; is: oneof; 8.21 group represented: by;
thefollowingiormulae NlI:
wherein -H represents the coupling position; on e Dis hydroxy and the other is hydrogen; the M which. is meta. to hydroxy is sulionic acid and the. other M is. hydrogen; R is fromthe group. consisting, of. hydrogen, car-boxy, and sulfonic.
acid; -R"" is one of a group consisting of methyl andcarboxy; and.R""" is one of a group cone sistingof. hydrogen, alkyl and alkoxy; said -com-. pound containing at least one solubilizing group.
2; An azo compound of the groupconsistingof' the acids and the alkali metal salts thereof which in their acid form are represented by the formula wherein .-.HN-Aryl.NHz is one of a group con sisting of radicals of thebenzene and naphthaleneseries represented by the formula and m V HN z I (R') n in which each R is one of a group consisting-of hydrogen, lowerv alkyl and alkoxy, carboxy, sulfonic acid and halogen; R is-from the group consisting-of hydrogen, halogen, carboxy and sulfonic acid; R" is/fromthegroup consistingof hydrogen, halogen -lower' alkyl andthe corresponding alkoxy groups; n is..1 to 2; m-is1'to-2; and Z is one of a group consisting of amino and the radical and each Y is one of. a :grouprepresentedoby the wherein -H represents the coupling position; following formulae i one D is hydroxy and the other ishydrogenrthe M which is meta to hydroxy is sulfonic acid and o o the other M is hydrogen; R' is from the group consisting of hydrogen, carboxy, and sulfonic (R'""'). acid; R"" is one of a group consisting of methyl and carboxy; and R"" is one of a group consisting of hydrogen, alkyl and alkoxy; said compound containing at least one solubilizing group.
3. An azo compound of the group consisting of NH! I the acids and the alkali metal salts thereof which in their acid form are represented bythe formula (RI). mm
i 1 NH:
M NH: H
NHC
5 M (lg n 12" wherein R, is from a. group consisting of hy- D drogen, ha1ogen, alkyl having 1 to 6 carbons, the
40 corresponding alkoxy groups and halogen; m is 1 to 2; one D is hydroxy and the other is hy-t drogen; the M which is meta to hydroxy is sul- M (3 0 IYOO-CHz-E-HN D N SOINB no N SO;Na
and I HO i F I N=NOOH OH 1 I uu =N/ 5. The compound represented by the formula it a on Ionic acid and the other is hydrogen. NHC 4. The compound represented by the formula.
nefromazldehydaandumetalcomplex ofa I6.{Thecomlpoundirepresenlredirby the formula; compound or claim 1. Y
' NaOgS NaOzS 7. The formaldehyde complex of alcempound 14. The formaldehyde ai'jld nlletal complex of a of claim 1. compound of claim 2. I
8. The formaldehyde complex of acompound 15. The formaldehydeandfmetal complex of a of claim 2. 1 compound of claim 4.
9. The formaldehyde complex of a compound 16. The formaldehyde and metal complex of a of claim 3. compound of claim '5. v 1
10. The formaldehyde complex {of a compound 17. The formaldehyde and metal complex of a of claim 4. l compound of claim 6.
11. The formaldehyde complex "of a compound 30 i of claim 5- 7 CHILES/E. SPARKS.
12. The formaldehyde and metal complex of a JAMES W. LIBBY, JR compound of claim 6. l
Certificate of Correction Patent No. 2,266,823. December 23, 1941.
CHILES E. SPARKS, ET AL.
It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows: Page 1, second column, line 8, in the formula, for Aryl-NH read ArylNH page 2, second column, line 17, for the Word changed read change; page 3, last formula thereon, for
page 7, first column, line 15, for
and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.
Signed and sealed this 19th day of May, A. D. 1942.
[SEAL] HENRY VAN ARSDALE,
Acting Commissioner of Patents.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US345171A US2266823A (en) | 1940-07-12 | 1940-07-12 | Water-soluble azo dyes from aminoaryloxy-acyl-diamines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US345171A US2266823A (en) | 1940-07-12 | 1940-07-12 | Water-soluble azo dyes from aminoaryloxy-acyl-diamines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2266823A true US2266823A (en) | 1941-12-23 |
Family
ID=23353857
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US345171A Expired - Lifetime US2266823A (en) | 1940-07-12 | 1940-07-12 | Water-soluble azo dyes from aminoaryloxy-acyl-diamines |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2266823A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2428302A (en) * | 1943-04-09 | 1947-09-30 | Owens Corning Fiberglass Corp | Colored glass fiber product |
-
1940
- 1940-07-12 US US345171A patent/US2266823A/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2428302A (en) * | 1943-04-09 | 1947-09-30 | Owens Corning Fiberglass Corp | Colored glass fiber product |
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