US3369013A - Disazo dyes - Google Patents

Disazo dyes Download PDF

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Publication number
US3369013A
US3369013A US471456A US47145665A US3369013A US 3369013 A US3369013 A US 3369013A US 471456 A US471456 A US 471456A US 47145665 A US47145665 A US 47145665A US 3369013 A US3369013 A US 3369013A
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United States
Prior art keywords
solution
tolylene
disazo
dyes
acid
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Expired - Lifetime
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US471456A
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English (en)
Inventor
Max A Weaver
Iii John I Dale
James M Straley
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Eastman Kodak Co
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Eastman Kodak Co
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Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US471456A priority Critical patent/US3369013A/en
Priority to BE683220D priority patent/BE683220A/xx
Priority to DE19661619423 priority patent/DE1619423A1/de
Priority to CH1010466A priority patent/CH460984A/fr
Priority to GB31244/66A priority patent/GB1156173A/en
Application granted granted Critical
Publication of US3369013A publication Critical patent/US3369013A/en
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Expired - Lifetime legal-status Critical Current

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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
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/02—Disazo dyes
    • C09B31/04—Disazo dyes from a coupling component "C" containing a directive amino group
    • C09B31/043—Amino-benzenes
    • 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
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
    • C09B62/507—Azo dyes
    • C09B62/513—Disazo or polyazo dyes
    • 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
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/78—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with other reactive groups
    • C09B62/82—Azo dyes
    • C09B62/83—Disazo or polyazo dyes

Definitions

  • This invention relates to new water insoluble disazo compounds useful as dyes for textile fibers, yarns and fabrics.
  • the invention is directed to dyestuffs wherein the disazo component is preferably free of the vinylsulfonyl group.
  • the disazo compounds of the invention have the following general formula wherein R represents an azobenzene group preferably free of the vinylsulfonyl group, wherein the aromatic groups of the azobenzene radical include phenyl and substituted phenyl such as alkylphenyl, e.g. o,'n1,p-tolyl; alkoxyphenyl, e.g. o,m,p-methoxyphenyl; halophenyl, e.g. o,m,p-chlorophenyl; nitrophenyl, e.g. o,m,pnitrophenyl; alkylsulfonylphenyl, e.g.
  • o,m,p-methylsulfonylphenyl alkylsulfonamidophenyl, e.g. o,m,p-methylsulfonamidophenyl; di(alkylsulfonyDphenyl, e.g. 2,5-di(methylsulfonyl)phenyl; dicar'boxylicacidimidophenyl, e.g. 0,-m-succinimidophenyl; fluoroalkylphenyl, e.g. trifluoromethylphenyl; acylamidophenyl; e.g.
  • o,m,p-acetamidophenyl cyanophenyl, e.g. o,m,p-thiocyanophenyl; ralkylthiophenyl, e.g. o,m,pcarboxamidophenyl; benzamidophenyl; thiocyanophenyl, e.g. o,m,p-thiocyanophenyl;; alkylthiophenyl, e.g. o,m,pmethylthiophenyl; benzoxyphenyl, e.g. o,m,p-benzoxyphenyl; benzaminophenyl, e.g.
  • o,m,p-benzaminophenyl benzylaminophenyl, e.g. o,m,p-benzylaminophenyl; N-alkylbenzaminophenyl, e.g. N-phenylmethylaminophenyl; formylphenyl, e.g. o,m,p-formylphenyl; carbalkoxyphenyl, e.g. o,m,p-carbethoxyphenyl; benzoylphenyl, e.g. o,m,p benzoylphenyl;
  • R represents a monocyclic carbocyclic aromatic group of the benzene series including phenylene and substituted phenylene such as phenylene; alkylphenylene, e.g. o,m,- tolylene; alkoxyphenylene, e.g. o,m-methoxyphenylene, halophenylene, e.g. o,m-chlorophenylene; alkylsulfonylphenylene, e.g. o,m-methylsulfonylphenylene; alkylsulfonamidophenylene, e.g.
  • o,m-methylsulfonamidophenylene di(alkylsulfonyl)phenylene, e.g. 2,5-di(methylsulfonyl)- phenylene; dicarboxylicacidimidophenylene, e.g. o,m-succinimidophenylene; acylamidophenylene, e.g. o,m-acetamidophenylene; benzamidophenylene; thiocyanophenylene, e.g. o,m-thiocyanophenylene; alkylthiophenylene, e.g.
  • benzoxyphenylene e.g. o,mbenzoxyphenylene
  • benzaminophenylene e.g. o,m-benzaminophenylene
  • benzylaminophenylene e.g. o,m-benzylaminophenylene
  • N-alkylbenzarninophenylene e.g. o,m- N-phenylmethylaminophenylene
  • carbalkoxyphenylene e.g. o,m-carbethoxyphenylene
  • benzoylp'henylene e.g. o,m-benzoylphenylene
  • R represents hydrogen or an alkyl radical including unsubstituted alkyl, preferably lower alkyl, i.e. from 1 to 4 carbon atoms, and substituted alkyl such as hydroxyalkyl, e.g. hydroxyethyl; polyhydroxyalkyl, e.g. glyceryl [CH(OH)CH(OH)CH OH]; alkoxyalkyl, e.g. methoxyethyl; cyanoalkyl, e.g. cyanoethyl; cyanoalkoxyalkyl, e.g. fi-cyanoethoxyethyl; acyloxyalkyl, e.g.
  • acetoxyethyl carbalkoxyalkyl, e.g. carbethoxyethyl; halogenoalkyl, e.g. chloroethyl; hydroxyhalogenoalkyl, e.g. fi-hydroxy-chloropropyl; alksulfonylalkyl, e.g. methylsulfonylethyl;
  • R represents a monocyclic carbocyclic aromatic radical of the benzene series, e.g. unsubstituted phenyl and substituted phenyl such as represented by R and R above, e.g. alkylphenyl, alkoxyphenyl, etc.
  • R and R substituents attached to the R, R and R groups serve primarily as auxochrome groups to con trol the color of the disazo compound.
  • disazo compounds in general can be expected to be superior to similar dyes containing the vinylsulfonyl or vinylsulfonylethyl group when tested by methods such as described in the A.A.T.C.C. Technical Manual, 1964 edition, depending in part upon the particular dye used and the fiber being dyed.
  • the coupling components having the Formula II are prepared by the following method:
  • the disazo compounds can be used for dyeing textile materials including synthetic polymer fibers, yarns and fabrics giving a variety of fast shades including red, orange, yellow and violet when applied there-to by conventional dye methods.
  • the disazo compounds have mod erate to good alfinity for cellulose ester and polyamide fibers.
  • the disazo compounds When used for dyeing such hydrophobic materials, they should be free of watersolublizing groups such as sulfo and carboxyl.
  • the dyes have good fastness, for example, to light, washing, gas (atmospheric fumes) and sublimation.
  • N-ethyl-N-;8-vinylsulfonylethylm-toluidine 27 g. of N-ethyl-m-toluidine, 23.6 g. divinylsulfone, ml. acetic acid and "100 ml. toluene were mixed together and refluxed with stirring for 12 hours. The solvent was removed under reduced pressure and the product distilled under vacuum at 157159 C./ 0.35 mm. The product has the structure:
  • CitH4SO2CH CH7 Q N i CH3
  • a solution of divinylsulfone, 'N-ethyl-1nchloroaniline and toluene was refluxed to prepare the product which has the structure:
  • the coupling solution was neutral-ized to brown on Congo Red paper with ammonium acetate and allowed to couple for two hours and was then washed, filtered and dried.
  • the product dyes nylon, cellulose acetate, and polyester fibers bright orange shades of excellent fastness.
  • the dye has the structure:
  • Example 2 1:5 acid.
  • the solution was stirred for two hours and then added to a solution of 2.39 g. N-ethyl-N-;3vinylsulfonylethylaniline in 75 ml. 1:5 acid.
  • the coupling solution was neutralized to brown on Congo Red paper with ammonium acetate and allowed to couple for two hours and was then washed, filtered and dried.
  • the product dyes nylon, cellulose acetate and polyester fibers bright shades of orange.
  • the product has the structure:
  • Example 3 The diazonium solution of Example 1 was added to a solution of 5.46 g. N-ethyl-N-vinylsulfonylethyl-m-chloroaniline in 150 ml. 1:5 acid.
  • the coupling solution was neutralized to brown on Congo Red paper with ammonium acetate and allowed to couple for two hours.
  • the coupling solution was then washed, filtered and dried.
  • the product obtained dyes nylon, cellulose acetate and polyester fibers deep shades of orange.
  • the dye has the struc ture:
  • Example 4 3.14 g. 3 acetamido 4-amino-2,5-dimethoxyazobenzone were diazotized using the same procedure and quantities of sodium nitrite, cone. sulfuric acid and 1:5 acid as in Example 2.
  • the diazonium solution was added to a solution of 2.53 g. N-ethyl-N-fl-vinylsulfonylethyl-m-toluidine in ml. 1:5 acid.
  • the solution was neutralized to brown on Congo Red paper with ammonium acetate and allowed to couple for two hours.
  • the coupling solution was then washed, filtered and dried.
  • the product obtained dyes nylon and polyester fibers deep shades of red.
  • the dye has the structure:
  • Example 5 4.62 g. 4-amino-3-chloroazobenzene were diazotized using the same procedure and quantities of reagents as described in Example 1. The resulting diazonium solution was added to a solution of 5.06 g. N-ethyl-N-fi vinylsulfonylethyl-m-tol-uidine in 200 ml. 1:5 acid. The solution was neutralized to brown on Congo Red paper with ammonium acetate and allowed to couple for two hours. The coupling solution was then washed, filtered and dried. The product dyes nylon a bright red shade with good fastness properties. The product has the structure:
  • Example 6 2.25 g. 4-amino-2,3-dimethylazobenzene were diazotized using the procedure described in Example 2 and the resulting solution was added to a solution of 2.86 g. N-fl-hydroxyethyl-N-B-vinylsulfonylethyl-rn-anisidine in 50 ml. 1:5 acid. The solution was neutralized to brown on Congo Red paper with ammonium acetate and allowed to couple for two hours. The coupling solution was washed,
  • the product dyes cellulose acetate and nylon red shades.
  • the dye has the structure:
  • the disazo compounds of the following table are made have varying utility as dyes.
  • the degree of utility varies, for example, depending upon the material being dyed and the formula of the disazo compound. Thus, for example, all the dyes will not have the same degree of utility for the same material.
  • the substituents on the R, R and R radicals serve primarily as auxochrome groups to control the color of the disazo compound.
  • Polymeric linear polyester materials of the terephthalate type are illustrative of the linear aromatic polyester textile materials that can be dyed with the new diazo compounds of our invention.
  • the terephthalate fibers sold under the trademarks Kodel, Dacron, and Terylene," for example, in the form of filaments, yarn and fabric, for example, are illustrative of the polyester textile mate- R1 rials that can be dyed.
  • Kodel polyester fibers are more wherein A and B are optionally substituted as described particularly described in U.S. Patent 2,901,446. Dacron in the table. and Terylene polyester fibers are described, for example,
  • the disazo compounds of the invention may be used for dyeing hydrophobic fibers such as linear polyester, cellulose ester, acrylic, polyamide, etc., fibers in the manner described in U.S. Patents 2,880,050, 2,757,064, 2,782,187 and 2,043,827.
  • the following examples illustrate methods by which the disazo compounds of the invention can be used to dye polyester textile materials.
  • 0.1 g. of the dye is dissolved in the dye pot by warming in 5 cc. of ethylene glycol monomethyl ether. A 2% sodium-N-methyl-N-oleyl taurate and 0.5% sodium lignin sulfonate aqueous solution is added, with stirring, until a fine emulsion is obtained. Water is then slowly added to a total volume of 200 cc. 3 cc. ofDacronyx (a chlorinated benzene emulsion) are added and 10 grams of a textile fabric made of Kodel polyester fibers are entered. The fabric is worked 10 minutes without heat and then for 10 minutes at 80 C. The dye bath is then brought to the boil and held at the boil for one hour.
  • Dacronyx a chlorinated benzene emulsion
  • the fabric is rinsed in warm water, then scoured in aqueous 0.2% soap, 0.2% soda ash solution. After scouring, the fabric is rinsed with water and dried.
  • the disazo compounds of the invention are Waterinsoluble, they can be applied from aqueous dispersions in the manner of the so-called dispersed dyes. However, coloration can be effected, for example, by incorporating the disazo compounds into the spinning dope and spinning the fiber as usual.
  • the disazo compounds of our invention in U.S. Patent 2,465,319.
  • the polymeric linear polyester materials disclosed in U.S. Patents 2,945,010, 2,957,745 and 2,989,363 for example, can be dyed.
  • the linear aromatic polyester materials specifically named have a melting point of at least 200 C.
  • Nylon in fiber, yarn and fabric form, is representative of polyamides which can be dyed with the disazo compounds.
  • a disazo compound of the general formula R1 RN N--R1-NC 31148 0 7 C H: C H:
  • R an azobenzene radical free of a vinylsulfonyl group

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  • Organic Chemistry (AREA)
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US471456A 1965-07-12 1965-07-12 Disazo dyes Expired - Lifetime US3369013A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US471456A US3369013A (en) 1965-07-12 1965-07-12 Disazo dyes
BE683220D BE683220A (en:Method) 1965-07-12 1966-06-27
DE19661619423 DE1619423A1 (de) 1965-07-12 1966-07-11 Verwendung von Disazofarbstoffen zum Faerben von Faeden und Fasern aus hydrophoben Polymeren
CH1010466A CH460984A (fr) 1965-07-12 1966-07-12 Procédé de préparation de composés diazoiques
GB31244/66A GB1156173A (en) 1965-07-12 1966-07-12 Disazo Dyes containing a Vinylsulphone Group

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Application Number Priority Date Filing Date Title
US471456A US3369013A (en) 1965-07-12 1965-07-12 Disazo dyes

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US3369013A true US3369013A (en) 1968-02-13

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BE (1) BE683220A (en:Method)
CH (1) CH460984A (en:Method)
DE (1) DE1619423A1 (en:Method)
GB (1) GB1156173A (en:Method)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5493010A (en) * 1993-03-24 1996-02-20 Bayer Aktiengesellschaft SO2 -containing fiber-reactive azo dyestuffs
US20060035262A1 (en) * 2000-05-09 2006-02-16 Biosearch Technologies, Inc. Dark quenchers for donor-acceptor energy transfer
US20090259030A1 (en) * 2008-04-01 2009-10-15 Biosearch Technologies Stabilized nucleic acid dark quencher-fluorophore probes
US8637658B2 (en) 2001-08-27 2014-01-28 Applied Biosystems, Llc Non-fluorescent quencher compounds and biomolecular assays

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB779781A (en) * 1952-06-09 1957-07-24 Hoechst Ag Water insoluble dyestuffs and a process for producing fast dyeings and prints therewith

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB779781A (en) * 1952-06-09 1957-07-24 Hoechst Ag Water insoluble dyestuffs and a process for producing fast dyeings and prints therewith

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5493010A (en) * 1993-03-24 1996-02-20 Bayer Aktiengesellschaft SO2 -containing fiber-reactive azo dyestuffs
US8946404B2 (en) 2000-05-09 2015-02-03 Biosearch Technologies, Inc. Dark quenchers for donor-acceptor energy transfer
US20060035262A1 (en) * 2000-05-09 2006-02-16 Biosearch Technologies, Inc. Dark quenchers for donor-acceptor energy transfer
US20100021922A1 (en) * 2000-05-09 2010-01-28 Biosearch Technologies, Inc. Dark quenchers for donor-acceptor energy transfer
US20110092679A1 (en) * 2000-05-09 2011-04-21 Biosearch Technologies, Inc. Dark Quenchers For Donor-Acceptor Energy Transfer
US20110178280A1 (en) * 2000-05-09 2011-07-21 Biosearch Technologies, Inc. Dark quenchers for donor-acceptor energy transfer
US8410255B2 (en) 2000-05-09 2013-04-02 Biosearch Technologies, Inc. Dark quenchers for donor-acceptor energy transfer
US10301349B2 (en) 2000-05-09 2019-05-28 Biosearch Technologies, Inc. Dark quenchers for donor-acceptor energy transfer
US8440399B2 (en) 2000-05-09 2013-05-14 Biosearch Technologies, Inc. Dark quenchers for donor-acceptor energy transfer
US8633307B2 (en) 2000-05-09 2014-01-21 Biosearch Technologies, Inc. Dark quenchers for donor-acceptor energy transfer
US9139610B2 (en) 2000-05-09 2015-09-22 Biosearch Technologies, Inc. Dark quenchers for donor-acceptor energy transfer
US9018369B2 (en) 2000-05-09 2015-04-28 Biosearch Technologies, Inc. Dark quenchers for donor-acceptor energy transfer
US8637658B2 (en) 2001-08-27 2014-01-28 Applied Biosystems, Llc Non-fluorescent quencher compounds and biomolecular assays
US8674094B2 (en) 2008-04-01 2014-03-18 Biosearch Technologies, Inc. Stabilized nucleic acid dark quencher-fluorophore probes
US8466266B2 (en) 2008-04-01 2013-06-18 Biosearch Technologies, Inc. Stabilized nucleic acid dark quencher-fluorophore probes
US9803240B2 (en) 2008-04-01 2017-10-31 Biosearch Technologies, Inc. Stabilized nucleic acid dark quencher-fluorophore probes
US20090259030A1 (en) * 2008-04-01 2009-10-15 Biosearch Technologies Stabilized nucleic acid dark quencher-fluorophore probes

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Publication number Publication date
BE683220A (en:Method) 1966-12-01
GB1156173A (en) 1969-06-25
CH460984A (fr) 1968-08-15
DE1619423A1 (de) 1971-05-13

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