CA2106830A1 - Basic dyes based on amides of j-acid (1-hydroxy-6- aminonaphthalene-3-sulfonic acid) and amides of j-acid - Google Patents
Basic dyes based on amides of j-acid (1-hydroxy-6- aminonaphthalene-3-sulfonic acid) and amides of j-acidInfo
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- CA2106830A1 CA2106830A1 CA002106830A CA2106830A CA2106830A1 CA 2106830 A1 CA2106830 A1 CA 2106830A1 CA 002106830 A CA002106830 A CA 002106830A CA 2106830 A CA2106830 A CA 2106830A CA 2106830 A1 CA2106830 A1 CA 2106830A1
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- alkyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/36—Oxygen or sulfur atoms
- C07D207/40—2,5-Pyrrolidine-diones
- C07D207/404—2,5-Pyrrolidine-diones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. succinimide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D211/56—Nitrogen atoms
- C07D211/58—Nitrogen atoms attached in position 4
-
- 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
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/24—Monoazo dyes prepared by diazotising and coupling from coupling components containing both hydroxyl and amino directing groups
- C09B29/28—Amino naphthols
-
- 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
- C09B31/08—Disazo dyes from a coupling component "C" containing directive hydroxyl and amino groups
-
- 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
- C09B44/00—Azo dyes containing onium groups
- C09B44/02—Azo dyes containing onium groups containing ammonium groups not directly attached to an azo group
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
- Cosmetics (AREA)
- Paper (AREA)
Abstract
Abstract of the Disclosure: There are described dyes of the formula
Description
21 068 3 ~ O.Z. 0050/43631 ~ASIC DYES BASED ON AMIDES OF J-ACID (1-HYDROXY-6-AMINONAPHTHALENE-3-SULFONIC ACID) AND
AMID~S OF J-ACID
The Pr~ent inVentiOn re1at~ tO nOV~1 dY~8 Of the fOrmU1a I
N = N ~ R~
I ~ R
~ ~3 where th~ ring A may bo benzofused, Rl Cl-Cl3-alkyl, bonzyl, 2-chloroothyl, substituted or unaubstituted phonyl, Cl-C8-alkanoyl, ~ubztituted or un~ubstituted benzoyl or a radical of the formula Q9 Qs N
(~ ) --CO-- Ll-- N ~ Ql N ~ N
¦~ Q2 ntAn0) Or N N~
whero L1 1~ Cl-C3-alkylene, n i~ 0 ôr 1, Ql~ Q2 and Q3 aro idontic~l or dif~er~nt and each i8 ind~p~nd~ntly of th~ others hydrogen or u~subatituted or hydroxyl-substituted Cl-C8-alkyl, which mAy bfi int~rrupted by from 1 to 3 oxyg~n ~tom~ in ~th~r function, or Q~ and Q~, tog~thor with ~ho nitrogen atom ~oining them togeth~r, are a 5- or 6-~emb0rod aaturatad het~rocyclic r~dic~l whJoh ~ay aontain nitrogen or o~yg~n ac further hotoro atom, . .
- .
.- .
21û683~
AMID~S OF J-ACID
The Pr~ent inVentiOn re1at~ tO nOV~1 dY~8 Of the fOrmU1a I
N = N ~ R~
I ~ R
~ ~3 where th~ ring A may bo benzofused, Rl Cl-Cl3-alkyl, bonzyl, 2-chloroothyl, substituted or unaubstituted phonyl, Cl-C8-alkanoyl, ~ubztituted or un~ubstituted benzoyl or a radical of the formula Q9 Qs N
(~ ) --CO-- Ll-- N ~ Ql N ~ N
¦~ Q2 ntAn0) Or N N~
whero L1 1~ Cl-C3-alkylene, n i~ 0 ôr 1, Ql~ Q2 and Q3 aro idontic~l or dif~er~nt and each i8 ind~p~nd~ntly of th~ others hydrogen or u~subatituted or hydroxyl-substituted Cl-C8-alkyl, which mAy bfi int~rrupted by from 1 to 3 oxyg~n ~tom~ in ~th~r function, or Q~ and Q~, tog~thor with ~ho nitrogen atom ~oining them togeth~r, are a 5- or 6-~emb0rod aaturatad het~rocyclic r~dic~l whJoh ~ay aontain nitrogen or o~yg~n ac further hotoro atom, . .
- .
.- .
21û683~
- 2 - o.Z. 0050/43631 An~ 1~ the equivalont of an an~on, and Q~ and Q5 are identical or different and ~ach i8 indopendently of th~ oth~r Cl-C~3-alkyl, which may be interrupted by fro~ 1 to 4 oxygen atoms in ether function, by imino or by Cl-C~-alkyl-imino group~ and may be ~ubstituted by amino, by a 5- or 6-me~bered ~turated or aromatic heterocyclic radic~l which contains a nitrogen atom and may contain a further hetero atom : 10 selected ~rom the group consisting of nitrogen, oxygen and ~ulfur, or by ~ub~tituted or un~ub-atituted C5-C7-cyclozlkyl, ~ubAtitutsd or unsubotitutod phenyl, ~ubstituted or unsub~tituted C5-C7-cycloalkyl or unsubstituted or methyl-substituted piporid;nyl, and Q~ may aloo be hydrogen, R~ i~ hydroga~ or Cl-C~-alkyl or Rl and R' togother are a radical of th~ formula CO-L2 or Co-L3-Co, whero L2 i~ C3-C~-al~ylen~ and ~3 i~ C~-C3-alkylene, ~inyle~e or 1,2-phenylene, R3 and R~ ar~ idont~cal or different and each i8 inde-; pendently of the othor C~-Cl3-alkyl, which may bo int~rruptod by from 1 to 4 oxyg~n atoms in ether ` 25 function or by from 1 to 4 ~mlno group3 which may bs ; suhstitutQd by Cl-C~-alkyl or ~-hydroxy-Cl-C8-alkyl, whic~ may b~ lnt~rrupted by from 1 to 3 oxyg~n ato~
~ othor funciton, a~d may be sub~tituted by ~ydroxyl, by am~no, by a 5- or 6-m-~bored saturated or aro~Atlc ~etorocyclic radlcal whlch centain~ a nitrog~n ato~ and m~y contain a ~urth-r hetero atom oel~cted fr#~ t~c group con~isting of nitrogen, oxygon a~d ~ul~ur, or by ~ub~tituted or un~ubsti-- tuted C5-C7-cycloalkyl, sub~t~tut~d or un~u~atitutedphenyl, subotitutQd or unsub0titutod C5-C7-cycloalkyl or un~ubstitutod or m thyl-~ub~tituted pip~ridlnyl, and R3 may al~o be hydrog-n, .
., . ~ , :
2106~3~
~ othor funciton, a~d may be sub~tituted by ~ydroxyl, by am~no, by a 5- or 6-m-~bored saturated or aro~Atlc ~etorocyclic radlcal whlch centain~ a nitrog~n ato~ and m~y contain a ~urth-r hetero atom oel~cted fr#~ t~c group con~isting of nitrogen, oxygon a~d ~ul~ur, or by ~ub~tituted or un~ubsti-- tuted C5-C7-cycloalkyl, sub~t~tut~d or un~u~atitutedphenyl, subotitutQd or unsub0titutod C5-C7-cycloalkyl or un~ubstitutod or m thyl-~ub~tituted pip~ridlnyl, and R3 may al~o be hydrog-n, .
., . ~ , :
2106~3~
3 o.Z. OOS0/43631 Rs is hydrogen, Cl-C~-alkyl, Cl-C~-alkoxy, C,-Cs-alkan-oylamino, halogen, nitro, cyano, un~ubstituted or Cl-C~-alkyl-~ubstituted phenylazo or a radical of th~
formula (~) -- NH--CO-- Li-- N
Q2 n (An~
(Q3) ~
(~) - o - L~ N - Q:
¦ Q2 n(An~
( Q3 ) n or (~) --C~ . X-- L4-- N-- Q' Q2 n ( An~
(Q3) n w~ore X i~ oxygon or imino, a~d ~ ia C2-C~-al~ylene, and Q~, Q2, Q3, n and A~ ar~ oach as defined ~bove, a~d RC ia hydrogen, Cl-C~-alkyl, Cl-C~-alkoxy, halogen, nitro or cya~o, with th~ provlso that at lea~t ono guat~rnizablo or guato~nary group i8 pr~ont in tho ~012cule, thQ uae t~-r~o~ for dyoing or prlnting poly~oric matorial, and no~ol amid~ o J-acid.
It ia an o~oct of the prosen~ inv~ntlon to provid~ novol ba~ic azodyos having a coupling c~mponent of tho ~erios of tho ~do~ of J-aoid (l-hydroxy-6-a~lnonaphthalono-3-aulfonic acid). Th- novol dyos shall bo advantageou~ for dy~ng or printing poly~oric matari-al, in particular paper. Th- dyoing~ o~tain~d ~hall havo good l~-ua~/~orvice proportie~.
,,: - : . . ., : , : . - -: ~
., .
formula (~) -- NH--CO-- Li-- N
Q2 n (An~
(Q3) ~
(~) - o - L~ N - Q:
¦ Q2 n(An~
( Q3 ) n or (~) --C~ . X-- L4-- N-- Q' Q2 n ( An~
(Q3) n w~ore X i~ oxygon or imino, a~d ~ ia C2-C~-al~ylene, and Q~, Q2, Q3, n and A~ ar~ oach as defined ~bove, a~d RC ia hydrogen, Cl-C~-alkyl, Cl-C~-alkoxy, halogen, nitro or cya~o, with th~ provlso that at lea~t ono guat~rnizablo or guato~nary group i8 pr~ont in tho ~012cule, thQ uae t~-r~o~ for dyoing or prlnting poly~oric matorial, and no~ol amid~ o J-acid.
It ia an o~oct of the prosen~ inv~ntlon to provid~ novol ba~ic azodyos having a coupling c~mponent of tho ~erios of tho ~do~ of J-aoid (l-hydroxy-6-a~lnonaphthalono-3-aulfonic acid). Th- novol dyos shall bo advantageou~ for dy~ng or printing poly~oric matari-al, in particular paper. Th- dyoing~ o~tain~d ~hall havo good l~-ua~/~orvice proportie~.
,,: - : . . ., : , : . - -: ~
., .
4 - o.z. OOS0/43631 We havo found that thi~ ob~ect i~ achieved by the dye~ of tho formula I defined at the b~ginning.
Any alkyl or alkylene appear~ng in the abovemen-tioned formula may be straight-chain or branchod.
Any sub~tituted phenyl appoar~ng in the abovemen-tioned formula may have a~ substituent~ for exa~ple Cl-C~-alkyl, Cl-C~-alkoxy or halogen, in particular chlorine or bromine. The number of substituents in ~ub~tituted phenyl i8 in genoral ~rom 1 to 3.
Any substituted C~-C7-cycloal~yl appearing in the abovemontion~d formula may havo as sub~tituent for example Cl-C~-alkyl or Cl-C~-aminoalkyl, in which oase cycloalkyl i~ in gen~ral substitutod by from 1 to 3 alkyl groups and/or a single aminoalkyl group~
Any mothyl-sub~tituted p~p~r$dinyl appearing in the abov~-ntion~d fon~ula has in gonor~l from 1 to 4 mothyl gsoup~, su~tituted 4-pipsridinyl being preferred.
A Cl-Cl3-alkyl R3, R4, Q~ or QS which i~ ~ubetituted by a 5- or 6-m~m~ered hetorocyclic rad~cal which contains a nitrogon at~ and may contain a further hetoro atom soloctod from tho group con~istin~ of nitrogen, oxygen and sulfur, 9U~ kable ~ubstitue~ts are ~aturated or aro~atic radlcal~, ~uch a~ pyrrolidlnyl, piporidinyl, morphol$nyl, piporazinyl, N-(C1-C~-al~yl)piperazinyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, i~ooxazolyl, thi&zolyl or i~othiazolyl.
Ql co~binod wlth Q~ and tho nitrogon ato~ ~oining thom tog-th r to ~onm a 5- or 6-m~mborod ~aturatod hotorocycllc radical whioh may contain nitrog~n or oxyg~n a~ furthor hotoro atom can b~ ~or ~xu~ple pyrrolidinyl, p~poridi~yl, ~orpholinyl, pip~ra~lnyl or N-~Cl-C~-alkyl)-~lperazinyl.
Any ~uh~titutod alkyl appearin~ in the abovemen-tion~d formula contaln~ in g-n~ral on~ or two ~ubatitu~nt~.
R, R, R3 , R~ , R3 , R~ , Ql , Ql , Q3 Q~ and Q' are , - - .
. .
2106~30 each for example methyl, ethyl, propyl, iaopropyl, butyl, i~obutyl, ~ec-butyl or tert-butyl R~, R3, R4, Ql, Q', Q3, Q~ and Q5 may each also be for example pentyl, isopentyl, neopentyl, tert-pentyl, h~xyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl or isooctyl.
Rl, R3, R~, Q~ and QS may each also bo for example nonyl, i~ononyl, dscyl, lsodecyl, undecyl, dodecyl, tridecyl, 3,5,5,7-tetramethylnonyl, isotridecyl (the above de~ignations isooctyl, i~ononyl, isodecyl and isotridecyl are trlvial name~ derived from the oxo process alcohols - cf UllmaDna En~yklopadie der tech-ni~chen Chemle, 4th Edition, Volume 7, page~ 215 to 217, and Volume 11, page~ 435 and 436), bonzyl, 1- or 2-phenylethyl, phenyl, 2-, 3- or 4-mothylphenyl, 2,4-dimethylph-nyl, 2-, 3- or 4-mothoxyphonyl, 2,4-di_e~hoxy-phenyl, 2-, 3- or 4-chlorophonyl or 2,4-dichlorophe~yl R' may al80 be for examplo formyl, acetyl, propi-onyl, butyryl, isobutyryl, pent~noyl, hexanoyl, hepta-noyl, octanoyl, 2-othylhexanoyl, benzoyl, 2-, 3- or 4-mothylbenzoyl, 2,4-dimethylbenzoyl, 2-, 3- or 4-methoxy-bonzoyl, 2,4-dimothoxybo~zoyl, 2-, 3- or 4-chlorobonzoyl or 2,4-dichlorobo~zoyl R3, R~, Q~ and Q5 ~ay ~ach al~o ~ for oxample 2-aminoethyl, 2- or 3-aminopropyl, 2- or 4-am~nobutyl, - 5-aminopentyl, 6-am~nohqxyl, 7-uminoheptyl, 8-aminoo~tyl, 3-aza-3-mothylbutyl,4-aza-4-m thylp~ntyl,3-aza-3-ethyl-pentyl, 4-aza-4-ethylhexyl, 5-amino-3-azapontyl, 6-amino-3-azah xyl, 6-amlno-4-azahexyl, 7-ami~o-4-azaheptyl, 8-amlno-3,6-dlazaoctyl, 3-a~inoprop-2-yl, 8-amino-4-(2-aminoothyl~octyl, 2-(pyrrol~dln-1-yl)~thyl, 2- or 3-(pyrrolidin-1-yl)propyl, 2-(piporldin-l~yl)~thyl, 2- or 3-~plporidin-1-yl)propyl, 2-(morpholin-4-yl)ethyl, 2- or 3-( rpholin-4-yl)propyl, 2-(pipora~in-1-yl)ethyl, 2- or 3-(plp~razin-1-yl)propyl, 2-(4-mothylpip-razin-1-yl)othyl, 2- or 3-(4-m thylpiperazin-1-yl)propyl, 2-(imldazol-1-yl)othyl, 2- or 3-(lmidazol-1-yl)propyl, "
~.. . , , , :
, . , ' , : , ` '' ' ` ' .
Any alkyl or alkylene appear~ng in the abovemen-tioned formula may be straight-chain or branchod.
Any sub~tituted phenyl appoar~ng in the abovemen-tioned formula may have a~ substituent~ for exa~ple Cl-C~-alkyl, Cl-C~-alkoxy or halogen, in particular chlorine or bromine. The number of substituents in ~ub~tituted phenyl i8 in genoral ~rom 1 to 3.
Any substituted C~-C7-cycloal~yl appearing in the abovemontion~d formula may havo as sub~tituent for example Cl-C~-alkyl or Cl-C~-aminoalkyl, in which oase cycloalkyl i~ in gen~ral substitutod by from 1 to 3 alkyl groups and/or a single aminoalkyl group~
Any mothyl-sub~tituted p~p~r$dinyl appearing in the abov~-ntion~d fon~ula has in gonor~l from 1 to 4 mothyl gsoup~, su~tituted 4-pipsridinyl being preferred.
A Cl-Cl3-alkyl R3, R4, Q~ or QS which i~ ~ubetituted by a 5- or 6-m~m~ered hetorocyclic rad~cal which contains a nitrogon at~ and may contain a further hetoro atom soloctod from tho group con~istin~ of nitrogen, oxygen and sulfur, 9U~ kable ~ubstitue~ts are ~aturated or aro~atic radlcal~, ~uch a~ pyrrolidlnyl, piporidinyl, morphol$nyl, piporazinyl, N-(C1-C~-al~yl)piperazinyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, i~ooxazolyl, thi&zolyl or i~othiazolyl.
Ql co~binod wlth Q~ and tho nitrogon ato~ ~oining thom tog-th r to ~onm a 5- or 6-m~mborod ~aturatod hotorocycllc radical whioh may contain nitrog~n or oxyg~n a~ furthor hotoro atom can b~ ~or ~xu~ple pyrrolidinyl, p~poridi~yl, ~orpholinyl, pip~ra~lnyl or N-~Cl-C~-alkyl)-~lperazinyl.
Any ~uh~titutod alkyl appearin~ in the abovemen-tion~d formula contaln~ in g-n~ral on~ or two ~ubatitu~nt~.
R, R, R3 , R~ , R3 , R~ , Ql , Ql , Q3 Q~ and Q' are , - - .
. .
2106~30 each for example methyl, ethyl, propyl, iaopropyl, butyl, i~obutyl, ~ec-butyl or tert-butyl R~, R3, R4, Ql, Q', Q3, Q~ and Q5 may each also be for example pentyl, isopentyl, neopentyl, tert-pentyl, h~xyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl or isooctyl.
Rl, R3, R~, Q~ and QS may each also bo for example nonyl, i~ononyl, dscyl, lsodecyl, undecyl, dodecyl, tridecyl, 3,5,5,7-tetramethylnonyl, isotridecyl (the above de~ignations isooctyl, i~ononyl, isodecyl and isotridecyl are trlvial name~ derived from the oxo process alcohols - cf UllmaDna En~yklopadie der tech-ni~chen Chemle, 4th Edition, Volume 7, page~ 215 to 217, and Volume 11, page~ 435 and 436), bonzyl, 1- or 2-phenylethyl, phenyl, 2-, 3- or 4-mothylphenyl, 2,4-dimethylph-nyl, 2-, 3- or 4-mothoxyphonyl, 2,4-di_e~hoxy-phenyl, 2-, 3- or 4-chlorophonyl or 2,4-dichlorophe~yl R' may al80 be for examplo formyl, acetyl, propi-onyl, butyryl, isobutyryl, pent~noyl, hexanoyl, hepta-noyl, octanoyl, 2-othylhexanoyl, benzoyl, 2-, 3- or 4-mothylbenzoyl, 2,4-dimethylbenzoyl, 2-, 3- or 4-methoxy-bonzoyl, 2,4-dimothoxybo~zoyl, 2-, 3- or 4-chlorobonzoyl or 2,4-dichlorobo~zoyl R3, R~, Q~ and Q5 ~ay ~ach al~o ~ for oxample 2-aminoethyl, 2- or 3-aminopropyl, 2- or 4-am~nobutyl, - 5-aminopentyl, 6-am~nohqxyl, 7-uminoheptyl, 8-aminoo~tyl, 3-aza-3-mothylbutyl,4-aza-4-m thylp~ntyl,3-aza-3-ethyl-pentyl, 4-aza-4-ethylhexyl, 5-amino-3-azapontyl, 6-amino-3-azah xyl, 6-amlno-4-azahexyl, 7-ami~o-4-azaheptyl, 8-amlno-3,6-dlazaoctyl, 3-a~inoprop-2-yl, 8-amino-4-(2-aminoothyl~octyl, 2-(pyrrol~dln-1-yl)~thyl, 2- or 3-(pyrrolidin-1-yl)propyl, 2-(piporldin-l~yl)~thyl, 2- or 3-~plporidin-1-yl)propyl, 2-(morpholin-4-yl)ethyl, 2- or 3-( rpholin-4-yl)propyl, 2-(pipora~in-1-yl)ethyl, 2- or 3-(plp~razin-1-yl)propyl, 2-(4-mothylpip-razin-1-yl)othyl, 2- or 3-(4-m thylpiperazin-1-yl)propyl, 2-(imldazol-1-yl)othyl, 2- or 3-(lmidazol-1-yl)propyl, "
~.. . , , , :
, . , ' , : , ` '' ' ` ' .
cyclopontyl, cyclohoxyl, cycloheptyl, 3-amino~othyl-3,5,5-trimothylcycloh2xyl or 2, 2, 6, 6 - tetra-methylpiperidin-4-yl R3, R4, Ql, Q~, Q3, Q~ and Q~ may oach al~o bs for example 2-methoxyethyl, 2-othoxy~thyl, 2-propoxyothyl, 2-i~opropoxyethyl, 2-butoxyethyl, 2- or 3-methoxypropyl, 2- or 3-ethoxypropyl, 2- or 3-propoxypropyl, 2- or 3-butoxypropyl, 2- or 4-methoxybutyl, 2- or 4-ethoxybutyl, 2- or 4-propoxybutyl, 3,6-dioxaheptyl, 3,6-dioxyoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7-d~oxa~onyl, 2- or 4-butoxybutyl, 4,8-dioxadocyl, 3,6,9-triexadecyl or 3,6,9-trioxaund~cyl R3, R~, Q~ a~d Q5 may each al~o be fo~ oxample 3,6,9-trioxadodecyl, 3,6,9,12-tetraoxatridocyl or 3,6,9,12-tstraoxatotradocyl R3 and R~ may each al~o b~ for examplo 4-hydroxy-2-msthyl-3-az~butyl, 4-hydroxy-3-hydroxym0thyl-2-~athyl-3-az~butyl, 5-hydroxy-2-m~thyl-3-azapontyl, 5-hydroxy-3-(2-hydroxy~thyl)-2-mothyl-3-azapentyl, 8-hydroxy-2-methyl-3-aza-6-oxaoatyl, 11-hydroxy-2-mothyl-3-aza-6,9-dioxaund-cyl, 8-hydroxy-3-(5-hydroxy-3-oxapentyl)-2-methyl-3-aza-6-oxaoctyl or ll-hydroxy-3-(8-hydroxy-3,6-dloxaoctyl)-2-methyl-3-aza-6,9-dioxaundscyl R5 and R' may a~h al~o bo for ox~mple mothoxy, ethoxy, propoxy, i~opropoxy, butoxy, i~obutoxy, soc-butoxy, fluorlne, chlorin- or bro~ino R5 may also be for examplo acotylamino, pro~lonylamlno, butyrylamlno, iao~utyrylam~no, pontanoyl-~mtno~ phonylazo or 2-, 3- or 4-methylphonyla~o R3, R~, Q', Q2 a~d Q3 may each also be for oxumple 2-hydroxyQthyl, 2- or 3-hydroxyet~yl or 2- or 4-hydroxybutyl ~ for exa~plo mothylon~, ethylon~ or 1,2- or 1,3-pro~ylonQ
L' is for example 1,2- or 1,3-propylone or 1,2-, 2,3- or 1,4-butylone " , , .' .: : ; . ` ` .
, ~ , .
- ~ : : : : :
,: `
2106~30 - 7 - o Z~ 0050/43631 L3 is for example ethylone or 1,2- or 1,3-propylene The equivalent An~ of an anlon i~ derived for example from tho following anion~ fluorldo, chlorido, bromido, iodido, formate, acotato, propionate, mono-, di-or trichloroacetate, lactato, mothoxyacetato, citrate, succinato, mothane~ulfonate, bonzone~ulfonate, 2- or 4-mothylbonzonesulfonato or naphthalono~ulfonate Prof~renco i8 given to dyos of tho formula I
wh-r- R~ i~ C,-C~-alkanoyl, bonzoyl or a radical of tho formula (~
--CO--CH2-- N n Ql ¦ Q2 n(An~
(Q3) n where Ql, Q2~ Q3~ An and n are each a~ definod above, or R~ and R~ aro togoth-r a radlcal of tho formula Co-L3-Co, where L3 i8 ethyl n-, vinylono or 1,2-phonylone, and R2 i~
hydrog-n Pref~ronc- i8 furthor givon to dye~ of tho formula I wher-R3 i~ hydrog-n and R' lc Cl-C~3-alkyl which i8 intorruptod by 1 or 2 oxyg-n atomJ in th r function, by imino or Cl-C~-alkylimino groupe and/or sub-tltut-d by amino or by a 5- or 6-m mb-r-d caturat-d or aromatic hoterocy~lic radical whlch containc on- or two nitrogen atoms Particular pr-f-r-nco i8 gi von to dyo~ of the formula I wh-r- Rl io ac-tyl - Pr-fer nc- ic furth-r given to dyo~ of the formula I wh-r- R' i~ Cl-C~-alkyl, Cl-C~-alkoxy, C~-C~-alkanoylamino or ph-nylazo and R' 1~ hydrog-n Th- nov-l bacic azo dy-~ of the formula I ~an be o~taln-d in a conv-ntlonal mann-r Ono option 1~ for exampl- to dlazotlze an anilin-of th- formula II
,, , ~ ~ ., ' . . . . .' ,. ' ' ` ......... . ! ' ''~ ~' '"' ' ''' ''` ' , ' ' .' ''' " ' ' ' ' .
' ' ' ' ' ' ' ~ ' ' ' ' - 8 - O.Z. ~OSO/43631 ~NH2 (II), where R5, R6 and the ring A are ~ach a~ defined above, in a conventional manner and couple it with a naphthalene derivative of the formula III
~H
Rl ~III), 7O2 Rq N~ R2 N
~ R3 whsro ~', R2, R3 and R~ ar- each a~ dofinod abov~
Tho~o dye~ of th~ for~ula I whi~h contain a guaternary riadical aro advantagaously obtain2d by firat proparing tha noutral azo dyo iand then guaternizing it wlth a Cl-C~-alkyl~no oxide or wlth a compound of the formula IV
Q6_y (IV), wher~ Q5 i8 unsub~titut-d or hydroxyl-~ub~tituted Cl-C~-alkyl and Y 1~ a l-avlng group, for oxacplQ chloride, br d do, iodldo, m tho~ulfato, etho~ulfate, benzenesul-fonat~ or a- or 4-methylb~nz-n-~ulfonato Some of tho naphthalone derivativ~ of the formula III ar- know~ per ~o; ~oo for ~xampl~ EP-A-537 535 Tho ba~ic a~o dyec of the formula I according to tho inv~ntion can be uaod alono, mixod with on~ another or mixod with othor cationic or anlo~lc co~pound~ in the for~ of th~r solut~on~ or i~ th- form of powders or granulo~ Th~y aro advant~goous for dy~lng or printing polym-rlc matorial, in partlcular pap-r ~tock, but al~o : ~ - ~ . . - . :
.. . . ..
-210~830 g o.Z. 0050/43631 cellulose, cotton, leather, ba~t fibers, hemp, flax, si~al, juta, coir or straw.
For the preparation of formulations of the novel dye~ of the formula I attention must be drawn in particu-lar to the use of polymer~ such a~ polyacrylic acid~,polyacrylic acid derivative~, polyvinylamine~, polyvinyl-amides, polyvinyl acetates, polyvinyl alcohol~, polyvinylpyrrol~donea, polysiloxanes or copolymers of the respectivo monomers. It i8 similarly po~ible to use oligomors of ethyleneimino, athylens oxide or propylene oxido or dorivatives thoreof.
The dyoa ars preferably usable in tha production of pulp-colored, sized or unsized paper. They can like-w~se be u~ed for coloring paper by the dip method.
The dyeing of paper, leather or cellulose i~
effect-d in a convontional ~anner.
Tho novel dyos or formulations thereof cause virtually no, if any, sta~ning of tho waste water from papermaking, which i8 particularly favor~ble for keeping water coursos cloan. Thoy are highly ~ubstantive, do not marblo whon applied to paper, and aro ~ubstantially p~-insens~tiv~. Th- dyoing~ on papor are notabla for good lightfa~tna~. On prolong-d exposure to light the shade c~ango~ on-tono.
Tho dy-d pap-r, which ie readily bleachable, i~
wot-fa~, not only to watQr but al~o to ~ilk, liguid soap, ~odlu~ chlorido 801ution~, fruit ~uices or ~w -tQnod mlnoral wator and, owing to its good alcohol fa~tnoa~ al~o faet to alcoholic bever~ge0.
Tho novol dyo~ can also be used for dyeing, padding or printing polyacrylonltrile textile~ or anion-lcally modif~ed polyamldo or polyo~ter t-xtiles.
The pros-nt invontion further provid~a novel sulfonumides of tho formula IIIa 2 1 0 6 8 3 !J
- 10 - O.Z. 0050/~3631 (;) H
,~ I~
¦ ~ R4 ~ (IIIa), ~ ~<3 0 where L3 i9 C2-C3-alkylane, vinylene or 1,2-phenyleno and R3 and R~ are identical or differ~nt and each i~ inde-pendently of the other C~-C~3-alkyl, whiah may be interrupted by from 1 to 4 oxyg~n atom~ in ethor function or by from 1 to 4 imino groups which may bo sub6titu~ ed by ~l-C~-alkyl or ~-hydroxy-Cl-C~-alkyl, wh~ch may ba intorrupted by from 1 to 3 oxygsn ato~
in ~ther function, a~d may be ~ub~titu~ed by hydroxyl, by amino, by a S- or 6-member~d satur~ted or aromatic h~terocyclic radical which contains a nitrog~n atom and ~ay contain a ~urthor hetero ato~
Qolocted fro~ tho group ~onEi~ting of nit~ogen, oxyge~ and sulfur, or by sub~tltutod or un~ub~ti-tuted Cs-C,-cyclo~lkyl, ~b~titut~d or un~ub~tituted phenyl, ~ub~titutsd or un~ub~titutod C5-C7-aycloalkyl or un~ubstitut-d or ~othyl-_ubst~tutod piperidinyl, and R3 mny also bo hydrogon, w~th tho proviso th~t at loast one quatornizable group i~
pr-aent in th- molecule.
Preforenc~ is givo~ to t~o~3 ~ulfonamidas of tho formul~ IIIa whore R3 i~ hydrogen and R~ is ~l-Cl3-alkyl which ha~ at loa~t one guaternizable nitroge~ ato~.
~mbodiment~ of th~ lnv-~t~on will now bo ~oro p~rticularly do8cribed by way of ~xamplc. Perc~ntaqe~ aro by woight.
~XANP~E 1 30 g o~ 1,2-diaminopropan- w~re admlx~d Bt 20C
with 8.5 g (0.025 mol) of N-~cetyl-~-acid chloridc, and - , - .
2106~3~
tho mlxturo was stirred at room t~mperaturo for 60 h The resulting oil wa~ diluted with 200 ml of water, ad~usted to pH 8 with hydrochloric acid, and admixed at pH 7 5-8 with 3 75 g (0 025 mol) of diazotizod p-aminoacotanilide 5 The pH wa~ kopt con~tant wlth aquoou~ sodlum carbonato ~olution The solut~on of th~ diazonium salt wa~ prepared as follows 3.75 g (0 025 mol) of p-aminoacetanilide were stirred at 0-3C w~th 50 ml of water and 12 5 ml of 30 %
strength by weight hydrochloric acid over 30 min and then admixed with 65 g of ~ce Th- diazotization wa~ carried out by th- dropwl~- addltion of 7 5 ml of 23 ~ ~trength by weight agueous sodlum nltrite solut~on The reaction mlxtur- wa~ stirr-d at 0-3C for a further 2 h and then us-d for th- coupllng r~aotlon ,'!
Flltration wlth suctlon and drylng yielded 9 5 g (76 ~) of th- dy- of th- formula N
OH
N ~ .:
H2N-CH (CH3) -cH2-NH-so2 NH-COCH3 ~ Amax 502 nm (ln 85 % str-ngth by w lght ac~tic acid) ; ~XAMPL~ 2 3 08 g (0 02S 1) of o-anisldln- woro dissolved in 50 ml of wator and 7 ml of 38 % str-ngth by weight hydroohlorlc acid and admix-d at 0C wlth 17 3 ml of 10 ~
~tr~ngth by w ight agu-ou~ sodlum nltrlt- solutlon, and tho mixtur- wa~ ~tirred at 0C for a furth-r 20 min and clarifi-d with act~v- charcoal Th- r-~ultlng solution of the diazonium ~alt wa~ r-actod with an eguimolar amount of ~ulfonamide a~ do~crib-d in Bxampl- 1 Th- dy- of th- formula . ` . ' ' : ' . ! ~ `
. , - , . .
- 2~633-J
- 12 - O.Z. 0050/43631 ~OC~3 N
ll OH
H2N-C.~1 ( CH, ) -CH2-NH- SOz NH -COCH3 was i~olated in a 62 % yiol~ (14.4 g).
Amax: 501 nm (in 85 % ~trenyth by weight acot~c acid) EXANæ~ 3 8.5 g (0.025 mol) of N-ac~tyl-J-acid chloride wer~ addsd at 20C to 30 g of N,N-dimethylethylenediamine and the mixturo was stirred at room t~mperature for 60 h.
Th~ r~oulting oil wa~ dllutod w~t~ 200 ml of water, brought to pH 8 wlth hydrochlorlc acid and coupled at p~ 7.5-8 with 4.93 g (0.025 mol) of dtazotized p-amino-b~nzone. Tho p~ w~- k-pt conotant with agueou~ ~odium carbonato ~olutio~.
Prop~ration of the diazonium ~alt of p-amino-i . benz-n-: 4.93 g (0.025 l) o~ p-am~nobonzeno were dis~olved in 30 ml of wat6r ~d 10 ml of 30 % ~trength by woight hydrochlorlc acid, th- mixtur- wa~ ~tirr~d at roo~
t~mpera~ure ~or 15 ~i~, wa~ ad~ix-d with 150 g of i~e-water acd at 15C ~ll at onGo w~th 7.5 ~l of 23 % ` .
tron~th by w lght aqueo~o ~od~um nltrlte Holution, tlrr-d at 15C or a urther 2 ~ and th~n ~larifi~d.
The r~ulting ~olutlon of tho diazon~um ~lt was reactod wlt~ an ~guimolar amount of oul~ona~ido a~
~ desGr~bed in Bxamplo 1.
f ~lltratlo~ wlth ~uGtlon a~d drylng yield~d 19.4 g ~ 70 %) of th~ dye of t~- formula ~ .
,~ `
- 13 - O.Z. 0050/43631 N
N ; :
ll OH
(CH3) 2 N-CH2 -CH2-NH-SO~ ~ NH-COCH3 ~mfix: 506 nm (in 85 % ~trength by welght acetic acid) The ~ame method gives the dye~ of the formula zl jO2 ll~ted below in th~ table. ~;
'' ,' : - . .. . - . :: . .
: .
14 2 1 0 6 8,~.~ . ooso/4363l I .~ . ~[~
_ _ _ _ _ :' `. o o o o o o o ~o ,~ I IU lU I IUIUIUIU~S,I
~3 _ _ _ _ _ _ _ :'.'. ' I z I I I I l-z~lzlZ~
- ~ Z -z C~ l .~, ~,~ Z ~ [ Z ~ ~ Z ~ U U Z~ U U . .
. C~ ~- ~ Z Z,~ Z~
_ . _ _ _ _ _ ~ ~ Z o o,, U o o o,~ o~
_ _ _ _ ~ _ _ .~' ~ :
~''' ' ',' . ',. ' ' '', 1,. ' ' . , ' - 15 - O.Z. 0050/43631 2106830 :
O ~ ~ r~ O
. t, ~ ~ ~, t. ~, ~' r ~
¦ ` ¦ ~ u ~
~ Z ~ ~ Z ~ ~ ~
_ O O _ O Z Z _ ~
~ ~ Q ~, .~
1:: ~ ~ ~r ~ c ~r ~
~ Z . . . . _ _ . C~ ' X ~ q _~ ~ r _ E~
' ~
' i~. ~ . ` . ` - ,'.' ..... ' ... : . . . . . .
.' ' ' ~ '....... , ' . . ' ' ; ' , ' '` ~ '` ' ~'` ' ` ' '` ' , , 2106~3~
- 16 - O.Z. 0050/43631 ~XAMPLE 20 8.2 g (0.05 mol) of N-acetyl-N-methyl-p-phenyl-enediamin~ were dissolv~d in a mixture of 100 g of ice, 125 ml of 30 % ~trength by welght hydrochloric acid and 12.5 ml of water. The addition of 12.5 g of ice wa~
followed at 0-5C by the addition of 15 ml of 23 %
qtrength by weight aqueous sodium nitrite ~olution, after which the mixture wa~ ~tirred at 0-5C for a further hour and then clarified.
The resulting solution of the diazonium ~alt wa~
reacted with an eguimolar amount of aulfonamide as described in Example 1.
Filtra~ion with suction and drying yielded 17 g - (66 %) of ~he dye of the formula CH3Co-N ~
ll OH
H2N-CH(CH3)-CH2-NH-50, NH-COCH3 Amax: 488 nm (in 85 ~ ~tr~ngth by weight acetic acid) ~XAMPL~ 21 382 g (1.6 mol) of J-acid w~re di~olvad in 1000 g of wat-r und 1000 g of ac~tone and the ~olution wac ~d~u~tod to p~ 7 with 90 ml o~ 50 % strength by w~ight ~odiu~ hydroxide ~olution. 339 g (3 mol) of chloroacotyl chlorido wer~ added dropwise at 0-5C over 3 h, during whlch th~ p~ w~s mainta~n~d at 6.1 with 20 %
~trongth by w-ight aqueous ~odium carbonate solution.
Then tho acotone and water wero diotilled off undor roduced pre~ur~ to lonve a ro~idual ~olumo of 1000 ml.
Aft~r 500 ml of wat~r had been added, a p~ of 2.7 wa~ set with concentr~ted hydrochloric acid, and ~he precipitated chloroacotyl-~-acid wa~ i~olatod.
66.~ g (0.2 mol) of th- chloroac-tyl-J-acid - . . . . . . .
: ',~ , . . , ' . ' ' : ' , ': . . : ' :
- 17 - o Z 0050/43631 obtained a~ de~cribed above were added to 104 ml of pho~phoryl chlorid~ and 40 ml of N,N-dimethylacetamid~ at 25-30~C and l~ft at that tempe~aturo for a furthor 18 h Aft~r precipitation in ~ce-water the ~ul~onyl ~hloride was ioolated, ta~en up in ethyl acetate, dried over sodium sulfate and evaporatod to dryne~ in a rotary evaporator 13 4 g (0 04 mol) of chloroacetyl-J-acid chloride were added at 25-30C to 50 g of ethanolamine, and the mixtur~ wa~ stirred at room temperature for 18 h, then pourod onto 250 g of ice and ad~u~t~d to p~ 7 5 with 70 g of 30 % strength by weight hydrochloric acid Tho 801u-tion wa~ coupled with 0 04 mol of diazotized p-aminoacet-anilido a~ d-~cribed in Example 1 Yield 18 2 g (82 %) of the dye of the formula C~3CO-N~ ~
N
ll OH
NOC2N~-NN-SOI NN -Co-CNz-NH-C2HqON
~max 488 (in 85 % ~trength by w~lght acotic acid) ~XAMPLB 22 16 7 g (O OS mol) of chloroacetyl-J-acid chloride wer- add-d at 25-30C to 60 g of 1,2-diaminopropan~, and th- mlxtur- wa~ ~tlrred at room t~mperature for 18 h, thon pour-d onto 250 g of lc~ and ad~u~ted to p~ 7 5 with 70 g of 30 ~ ~tr~ngth by welght hydrochloric acld Tho solution was coupl~d with O OS mol of diazotized p-a~inoac~t nilid~ a~ d~cribad in Bxample 1 Yield 17 g (54 ~) of the dye of the formula ..
.. . . . .. . . .
; ~ - , . , . .~ . . ; . , : . . . .
.
., ~ .'~ ~ '' . " , ' . .
2106~3{) - 18 - O. Z . 0050/43631 ~H CO-~H
II OH
H~N-CH (CH .) -CH2-~ SO~/~ NH-CO-C:~Z-NH-C~2-CH (C~ 2 Amax: 499 nm (i~ 85 % strength by w~ight acetic acidl 20 g (0.2 mol) of nuccinic anhydride w~o di~-~ol~ed i~ 50 g of N,N-dim~thylacetamide and admixod at 50C with 23.8 g (0.1 mol) of J-acid. After a further 1.5 h at 70C tho ~ixturo W~8 cool~d down to 30C, admix~d with 76.7 g (0.5 mol) of pho~phoryl chloride and stirr~d at room temporatur~ for 18 h. ThQ sulfonyl chlor~do w~a isolatod ~y hydroly~is in ~ce-wator, ilt~r-ing with suction ~nd eubaequ~nt ta~up of th~ filter ro~iduo in ~t~yl cetat~. Drying OVQr ~odiu~ oul~ate and r~movi~g the 801v~nt under rodu~d pr~ure yield~d 31. 5 g (93 %) of the ~ulfonyl chlorida.
The ~ulfo~yl chlorido wa~ first convorted into the amido n~d t~n into th~ dyo, both 8top8 being carried out as d~ocr~bod in Exu~ple 1.
Saltl~g out yioldod 40.3 g (99 ~) o~ the dy~ of ~ho formula N :~
ll OH
HzN-CH ICH~ ~ -CHz-NH-SOz l~
Amnx: 502 n~ (in 85 % ~tr~ngth ~y welght ac~tic acid~.
'' - - .- '' ' - ' '' ' . ' ' ' ' ", ' :' ~ ~ . ' , ' :- ,~, .... . . .
~, ............... ~ , ~ ,
L' is for example 1,2- or 1,3-propylone or 1,2-, 2,3- or 1,4-butylone " , , .' .: : ; . ` ` .
, ~ , .
- ~ : : : : :
,: `
2106~30 - 7 - o Z~ 0050/43631 L3 is for example ethylone or 1,2- or 1,3-propylene The equivalent An~ of an anlon i~ derived for example from tho following anion~ fluorldo, chlorido, bromido, iodido, formate, acotato, propionate, mono-, di-or trichloroacetate, lactato, mothoxyacetato, citrate, succinato, mothane~ulfonate, bonzone~ulfonate, 2- or 4-mothylbonzonesulfonato or naphthalono~ulfonate Prof~renco i8 given to dyos of tho formula I
wh-r- R~ i~ C,-C~-alkanoyl, bonzoyl or a radical of tho formula (~
--CO--CH2-- N n Ql ¦ Q2 n(An~
(Q3) n where Ql, Q2~ Q3~ An and n are each a~ definod above, or R~ and R~ aro togoth-r a radlcal of tho formula Co-L3-Co, where L3 i8 ethyl n-, vinylono or 1,2-phonylone, and R2 i~
hydrog-n Pref~ronc- i8 furthor givon to dye~ of tho formula I wher-R3 i~ hydrog-n and R' lc Cl-C~3-alkyl which i8 intorruptod by 1 or 2 oxyg-n atomJ in th r function, by imino or Cl-C~-alkylimino groupe and/or sub-tltut-d by amino or by a 5- or 6-m mb-r-d caturat-d or aromatic hoterocy~lic radical whlch containc on- or two nitrogen atoms Particular pr-f-r-nco i8 gi von to dyo~ of the formula I wh-r- Rl io ac-tyl - Pr-fer nc- ic furth-r given to dyo~ of the formula I wh-r- R' i~ Cl-C~-alkyl, Cl-C~-alkoxy, C~-C~-alkanoylamino or ph-nylazo and R' 1~ hydrog-n Th- nov-l bacic azo dy-~ of the formula I ~an be o~taln-d in a conv-ntlonal mann-r Ono option 1~ for exampl- to dlazotlze an anilin-of th- formula II
,, , ~ ~ ., ' . . . . .' ,. ' ' ` ......... . ! ' ''~ ~' '"' ' ''' ''` ' , ' ' .' ''' " ' ' ' ' .
' ' ' ' ' ' ' ~ ' ' ' ' - 8 - O.Z. ~OSO/43631 ~NH2 (II), where R5, R6 and the ring A are ~ach a~ defined above, in a conventional manner and couple it with a naphthalene derivative of the formula III
~H
Rl ~III), 7O2 Rq N~ R2 N
~ R3 whsro ~', R2, R3 and R~ ar- each a~ dofinod abov~
Tho~o dye~ of th~ for~ula I whi~h contain a guaternary riadical aro advantagaously obtain2d by firat proparing tha noutral azo dyo iand then guaternizing it wlth a Cl-C~-alkyl~no oxide or wlth a compound of the formula IV
Q6_y (IV), wher~ Q5 i8 unsub~titut-d or hydroxyl-~ub~tituted Cl-C~-alkyl and Y 1~ a l-avlng group, for oxacplQ chloride, br d do, iodldo, m tho~ulfato, etho~ulfate, benzenesul-fonat~ or a- or 4-methylb~nz-n-~ulfonato Some of tho naphthalone derivativ~ of the formula III ar- know~ per ~o; ~oo for ~xampl~ EP-A-537 535 Tho ba~ic a~o dyec of the formula I according to tho inv~ntion can be uaod alono, mixod with on~ another or mixod with othor cationic or anlo~lc co~pound~ in the for~ of th~r solut~on~ or i~ th- form of powders or granulo~ Th~y aro advant~goous for dy~lng or printing polym-rlc matorial, in partlcular pap-r ~tock, but al~o : ~ - ~ . . - . :
.. . . ..
-210~830 g o.Z. 0050/43631 cellulose, cotton, leather, ba~t fibers, hemp, flax, si~al, juta, coir or straw.
For the preparation of formulations of the novel dye~ of the formula I attention must be drawn in particu-lar to the use of polymer~ such a~ polyacrylic acid~,polyacrylic acid derivative~, polyvinylamine~, polyvinyl-amides, polyvinyl acetates, polyvinyl alcohol~, polyvinylpyrrol~donea, polysiloxanes or copolymers of the respectivo monomers. It i8 similarly po~ible to use oligomors of ethyleneimino, athylens oxide or propylene oxido or dorivatives thoreof.
The dyoa ars preferably usable in tha production of pulp-colored, sized or unsized paper. They can like-w~se be u~ed for coloring paper by the dip method.
The dyeing of paper, leather or cellulose i~
effect-d in a convontional ~anner.
Tho novel dyos or formulations thereof cause virtually no, if any, sta~ning of tho waste water from papermaking, which i8 particularly favor~ble for keeping water coursos cloan. Thoy are highly ~ubstantive, do not marblo whon applied to paper, and aro ~ubstantially p~-insens~tiv~. Th- dyoing~ on papor are notabla for good lightfa~tna~. On prolong-d exposure to light the shade c~ango~ on-tono.
Tho dy-d pap-r, which ie readily bleachable, i~
wot-fa~, not only to watQr but al~o to ~ilk, liguid soap, ~odlu~ chlorido 801ution~, fruit ~uices or ~w -tQnod mlnoral wator and, owing to its good alcohol fa~tnoa~ al~o faet to alcoholic bever~ge0.
Tho novol dyo~ can also be used for dyeing, padding or printing polyacrylonltrile textile~ or anion-lcally modif~ed polyamldo or polyo~ter t-xtiles.
The pros-nt invontion further provid~a novel sulfonumides of tho formula IIIa 2 1 0 6 8 3 !J
- 10 - O.Z. 0050/~3631 (;) H
,~ I~
¦ ~ R4 ~ (IIIa), ~ ~<3 0 where L3 i9 C2-C3-alkylane, vinylene or 1,2-phenyleno and R3 and R~ are identical or differ~nt and each i~ inde-pendently of the other C~-C~3-alkyl, whiah may be interrupted by from 1 to 4 oxyg~n atom~ in ethor function or by from 1 to 4 imino groups which may bo sub6titu~ ed by ~l-C~-alkyl or ~-hydroxy-Cl-C~-alkyl, wh~ch may ba intorrupted by from 1 to 3 oxygsn ato~
in ~ther function, a~d may be ~ub~titu~ed by hydroxyl, by amino, by a S- or 6-member~d satur~ted or aromatic h~terocyclic radical which contains a nitrog~n atom and ~ay contain a ~urthor hetero ato~
Qolocted fro~ tho group ~onEi~ting of nit~ogen, oxyge~ and sulfur, or by sub~tltutod or un~ub~ti-tuted Cs-C,-cyclo~lkyl, ~b~titut~d or un~ub~tituted phenyl, ~ub~titutsd or un~ub~titutod C5-C7-aycloalkyl or un~ubstitut-d or ~othyl-_ubst~tutod piperidinyl, and R3 mny also bo hydrogon, w~th tho proviso th~t at loast one quatornizable group i~
pr-aent in th- molecule.
Preforenc~ is givo~ to t~o~3 ~ulfonamidas of tho formul~ IIIa whore R3 i~ hydrogen and R~ is ~l-Cl3-alkyl which ha~ at loa~t one guaternizable nitroge~ ato~.
~mbodiment~ of th~ lnv-~t~on will now bo ~oro p~rticularly do8cribed by way of ~xamplc. Perc~ntaqe~ aro by woight.
~XANP~E 1 30 g o~ 1,2-diaminopropan- w~re admlx~d Bt 20C
with 8.5 g (0.025 mol) of N-~cetyl-~-acid chloridc, and - , - .
2106~3~
tho mlxturo was stirred at room t~mperaturo for 60 h The resulting oil wa~ diluted with 200 ml of water, ad~usted to pH 8 with hydrochloric acid, and admixed at pH 7 5-8 with 3 75 g (0 025 mol) of diazotizod p-aminoacotanilide 5 The pH wa~ kopt con~tant wlth aquoou~ sodlum carbonato ~olution The solut~on of th~ diazonium salt wa~ prepared as follows 3.75 g (0 025 mol) of p-aminoacetanilide were stirred at 0-3C w~th 50 ml of water and 12 5 ml of 30 %
strength by weight hydrochloric acid over 30 min and then admixed with 65 g of ~ce Th- diazotization wa~ carried out by th- dropwl~- addltion of 7 5 ml of 23 ~ ~trength by weight agueous sodlum nltrite solut~on The reaction mlxtur- wa~ stirr-d at 0-3C for a further 2 h and then us-d for th- coupllng r~aotlon ,'!
Flltration wlth suctlon and drylng yielded 9 5 g (76 ~) of th- dy- of th- formula N
OH
N ~ .:
H2N-CH (CH3) -cH2-NH-so2 NH-COCH3 ~ Amax 502 nm (ln 85 % str-ngth by w lght ac~tic acid) ; ~XAMPL~ 2 3 08 g (0 02S 1) of o-anisldln- woro dissolved in 50 ml of wator and 7 ml of 38 % str-ngth by weight hydroohlorlc acid and admix-d at 0C wlth 17 3 ml of 10 ~
~tr~ngth by w ight agu-ou~ sodlum nltrlt- solutlon, and tho mixtur- wa~ ~tirred at 0C for a furth-r 20 min and clarifi-d with act~v- charcoal Th- r-~ultlng solution of the diazonium ~alt wa~ r-actod with an eguimolar amount of ~ulfonamide a~ do~crib-d in Bxampl- 1 Th- dy- of th- formula . ` . ' ' : ' . ! ~ `
. , - , . .
- 2~633-J
- 12 - O.Z. 0050/43631 ~OC~3 N
ll OH
H2N-C.~1 ( CH, ) -CH2-NH- SOz NH -COCH3 was i~olated in a 62 % yiol~ (14.4 g).
Amax: 501 nm (in 85 % ~trenyth by weight acot~c acid) EXANæ~ 3 8.5 g (0.025 mol) of N-ac~tyl-J-acid chloride wer~ addsd at 20C to 30 g of N,N-dimethylethylenediamine and the mixturo was stirred at room t~mperature for 60 h.
Th~ r~oulting oil wa~ dllutod w~t~ 200 ml of water, brought to pH 8 wlth hydrochlorlc acid and coupled at p~ 7.5-8 with 4.93 g (0.025 mol) of dtazotized p-amino-b~nzone. Tho p~ w~- k-pt conotant with agueou~ ~odium carbonato ~olutio~.
Prop~ration of the diazonium ~alt of p-amino-i . benz-n-: 4.93 g (0.025 l) o~ p-am~nobonzeno were dis~olved in 30 ml of wat6r ~d 10 ml of 30 % ~trength by woight hydrochlorlc acid, th- mixtur- wa~ ~tirr~d at roo~
t~mpera~ure ~or 15 ~i~, wa~ ad~ix-d with 150 g of i~e-water acd at 15C ~ll at onGo w~th 7.5 ~l of 23 % ` .
tron~th by w lght aqueo~o ~od~um nltrlte Holution, tlrr-d at 15C or a urther 2 ~ and th~n ~larifi~d.
The r~ulting ~olutlon of tho diazon~um ~lt was reactod wlt~ an ~guimolar amount of oul~ona~ido a~
~ desGr~bed in Bxamplo 1.
f ~lltratlo~ wlth ~uGtlon a~d drylng yield~d 19.4 g ~ 70 %) of th~ dye of t~- formula ~ .
,~ `
- 13 - O.Z. 0050/43631 N
N ; :
ll OH
(CH3) 2 N-CH2 -CH2-NH-SO~ ~ NH-COCH3 ~mfix: 506 nm (in 85 % ~trength by welght acetic acid) The ~ame method gives the dye~ of the formula zl jO2 ll~ted below in th~ table. ~;
'' ,' : - . .. . - . :: . .
: .
14 2 1 0 6 8,~.~ . ooso/4363l I .~ . ~[~
_ _ _ _ _ :' `. o o o o o o o ~o ,~ I IU lU I IUIUIUIU~S,I
~3 _ _ _ _ _ _ _ :'.'. ' I z I I I I l-z~lzlZ~
- ~ Z -z C~ l .~, ~,~ Z ~ [ Z ~ ~ Z ~ U U Z~ U U . .
. C~ ~- ~ Z Z,~ Z~
_ . _ _ _ _ _ ~ ~ Z o o,, U o o o,~ o~
_ _ _ _ ~ _ _ .~' ~ :
~''' ' ',' . ',. ' ' '', 1,. ' ' . , ' - 15 - O.Z. 0050/43631 2106830 :
O ~ ~ r~ O
. t, ~ ~ ~, t. ~, ~' r ~
¦ ` ¦ ~ u ~
~ Z ~ ~ Z ~ ~ ~
_ O O _ O Z Z _ ~
~ ~ Q ~, .~
1:: ~ ~ ~r ~ c ~r ~
~ Z . . . . _ _ . C~ ' X ~ q _~ ~ r _ E~
' ~
' i~. ~ . ` . ` - ,'.' ..... ' ... : . . . . . .
.' ' ' ~ '....... , ' . . ' ' ; ' , ' '` ~ '` ' ~'` ' ` ' '` ' , , 2106~3~
- 16 - O.Z. 0050/43631 ~XAMPLE 20 8.2 g (0.05 mol) of N-acetyl-N-methyl-p-phenyl-enediamin~ were dissolv~d in a mixture of 100 g of ice, 125 ml of 30 % ~trength by welght hydrochloric acid and 12.5 ml of water. The addition of 12.5 g of ice wa~
followed at 0-5C by the addition of 15 ml of 23 %
qtrength by weight aqueous sodium nitrite ~olution, after which the mixture wa~ ~tirred at 0-5C for a further hour and then clarified.
The resulting solution of the diazonium ~alt wa~
reacted with an eguimolar amount of aulfonamide as described in Example 1.
Filtra~ion with suction and drying yielded 17 g - (66 %) of ~he dye of the formula CH3Co-N ~
ll OH
H2N-CH(CH3)-CH2-NH-50, NH-COCH3 Amax: 488 nm (in 85 ~ ~tr~ngth by weight acetic acid) ~XAMPL~ 21 382 g (1.6 mol) of J-acid w~re di~olvad in 1000 g of wat-r und 1000 g of ac~tone and the ~olution wac ~d~u~tod to p~ 7 with 90 ml o~ 50 % strength by w~ight ~odiu~ hydroxide ~olution. 339 g (3 mol) of chloroacotyl chlorido wer~ added dropwise at 0-5C over 3 h, during whlch th~ p~ w~s mainta~n~d at 6.1 with 20 %
~trongth by w-ight aqueous ~odium carbonate solution.
Then tho acotone and water wero diotilled off undor roduced pre~ur~ to lonve a ro~idual ~olumo of 1000 ml.
Aft~r 500 ml of wat~r had been added, a p~ of 2.7 wa~ set with concentr~ted hydrochloric acid, and ~he precipitated chloroacotyl-~-acid wa~ i~olatod.
66.~ g (0.2 mol) of th- chloroac-tyl-J-acid - . . . . . . .
: ',~ , . . , ' . ' ' : ' , ': . . : ' :
- 17 - o Z 0050/43631 obtained a~ de~cribed above were added to 104 ml of pho~phoryl chlorid~ and 40 ml of N,N-dimethylacetamid~ at 25-30~C and l~ft at that tempe~aturo for a furthor 18 h Aft~r precipitation in ~ce-water the ~ul~onyl ~hloride was ioolated, ta~en up in ethyl acetate, dried over sodium sulfate and evaporatod to dryne~ in a rotary evaporator 13 4 g (0 04 mol) of chloroacetyl-J-acid chloride were added at 25-30C to 50 g of ethanolamine, and the mixtur~ wa~ stirred at room temperature for 18 h, then pourod onto 250 g of ice and ad~u~t~d to p~ 7 5 with 70 g of 30 % strength by weight hydrochloric acid Tho 801u-tion wa~ coupled with 0 04 mol of diazotized p-aminoacet-anilido a~ d-~cribed in Example 1 Yield 18 2 g (82 %) of the dye of the formula C~3CO-N~ ~
N
ll OH
NOC2N~-NN-SOI NN -Co-CNz-NH-C2HqON
~max 488 (in 85 % ~trength by w~lght acotic acid) ~XAMPLB 22 16 7 g (O OS mol) of chloroacetyl-J-acid chloride wer- add-d at 25-30C to 60 g of 1,2-diaminopropan~, and th- mlxtur- wa~ ~tlrred at room t~mperature for 18 h, thon pour-d onto 250 g of lc~ and ad~u~ted to p~ 7 5 with 70 g of 30 ~ ~tr~ngth by welght hydrochloric acld Tho solution was coupl~d with O OS mol of diazotized p-a~inoac~t nilid~ a~ d~cribad in Bxample 1 Yield 17 g (54 ~) of the dye of the formula ..
.. . . . .. . . .
; ~ - , . , . .~ . . ; . , : . . . .
.
., ~ .'~ ~ '' . " , ' . .
2106~3{) - 18 - O. Z . 0050/43631 ~H CO-~H
II OH
H~N-CH (CH .) -CH2-~ SO~/~ NH-CO-C:~Z-NH-C~2-CH (C~ 2 Amax: 499 nm (i~ 85 % strength by w~ight acetic acidl 20 g (0.2 mol) of nuccinic anhydride w~o di~-~ol~ed i~ 50 g of N,N-dim~thylacetamide and admixod at 50C with 23.8 g (0.1 mol) of J-acid. After a further 1.5 h at 70C tho ~ixturo W~8 cool~d down to 30C, admix~d with 76.7 g (0.5 mol) of pho~phoryl chloride and stirr~d at room temporatur~ for 18 h. ThQ sulfonyl chlor~do w~a isolatod ~y hydroly~is in ~ce-wator, ilt~r-ing with suction ~nd eubaequ~nt ta~up of th~ filter ro~iduo in ~t~yl cetat~. Drying OVQr ~odiu~ oul~ate and r~movi~g the 801v~nt under rodu~d pr~ure yield~d 31. 5 g (93 %) of the ~ulfonyl chlorida.
The ~ulfo~yl chlorido wa~ first convorted into the amido n~d t~n into th~ dyo, both 8top8 being carried out as d~ocr~bod in Exu~ple 1.
Saltl~g out yioldod 40.3 g (99 ~) o~ the dy~ of ~ho formula N :~
ll OH
HzN-CH ICH~ ~ -CHz-NH-SOz l~
Amnx: 502 n~ (in 85 % ~tr~ngth ~y welght ac~tic acid~.
'' - - .- '' ' - ' '' ' . ' ' ' ' ", ' :' ~ ~ . ' , ' :- ,~, .... . . .
~, ............... ~ , ~ ,
Claims (6)
1. Dyes of the formula I
(I), where the ring A may be benzofused, R1 is C1-C13-alkyl, benzyl, 2-chloroethyl, substituted or unsubstituted phenyl, C1-C8-alkanoyl, substituted or unsubstituted benzoyl or a radical of the formula or where L1 is C1-C3-alkylene, n is 0 or 1, Q1, Q2 and Q3 are identical or different and each is independently of the others hydrogen or unsubstituted or hydroxyl substituted C1-C8-alkyl, which may be interrupted by from 1 to 3 oxygen atoms in other function, or Q1 and Q2, together with the nitrogen atom joining them together are a 5- or 6-membered saturated heterocyclic radical which may contain nitrogen or oxygen as further hetero atom, An° is the equivalent of an anion, and Q4 and Q5 are identical or different and each is independently of the other C1-C13-alkyl, which may be interrupted by from 1 to 4 oxygen atoms in other function, by imino or by C1-C4-alkyl-imino groups and may be substituted by amino, by a 5- or 6-membered saturated or aromatic heterocyclic radical which contains a nitrogen atom and may contain a further hetero atom selected from the group consisting of nitrogen, oxygen and sulfur, or by substituted or unsub-stituted C5-C7-cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubsti-tuted C5-C7-cycloalkyl or unsubstituted or methyl-substituted piperidinyl, and Q4 may also be hydrogen, R2 is hydrogen or C1-C4-alkyl or R1 and R2 together are a radical of the formula CO-L2 or CO-L3-CO, where L2 is C3-C4-alkylene and L3 is C2-C3-alkylene, vinylene or 1,2-phenylene, R3 and R4 are identical or different and each is inde-pendently of the other C1-C13-alkyl, which may be interrupted by from 1 to 4 oxygen atoms in ether function or by from 1 to 4 imino groups which may be substituted by C1-C4-alkyl or .omega.-hydroxy-C1-C8-alkyl, which may be interrupted by from 1 to 3 oxygen atoms in ether function, and may be substituted by hydroxyl, by amino, by a 5- or 6-membered saturated or aromatic heterocyclic radical which contains a nitrogen atom and may contain a further hetero atom selected from the group consisting of nitrogen, oxygen and sulfur, or by substituted or unsubstituted C5-C7-cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted C5-C7-cycloalkyl or unsubstituted or methyl-sub-stituted piperidinyl, and R3 may also be hydrogen, R5 is hydrogen, C1-C4-alkyl, C1-C4-alkoxy, C2-C3-alkan-oylamino, halogen, nitro, cyano, unsubstituted or C1-C4-alkyl-substituted phenylazo or a radical of the formula , , or , where X is oxygen or imino, and L4 is C2-C4-alkylene, and Q1, Q2, Q3, n and An° are each as defined above, and R5 is hydrogen, C1-C4-alkyl, C1-C4-alkoxy, halogen, nitro or cyano, with the proviso that at least one quaternizable or quaternary group is present in the molecule.
(I), where the ring A may be benzofused, R1 is C1-C13-alkyl, benzyl, 2-chloroethyl, substituted or unsubstituted phenyl, C1-C8-alkanoyl, substituted or unsubstituted benzoyl or a radical of the formula or where L1 is C1-C3-alkylene, n is 0 or 1, Q1, Q2 and Q3 are identical or different and each is independently of the others hydrogen or unsubstituted or hydroxyl substituted C1-C8-alkyl, which may be interrupted by from 1 to 3 oxygen atoms in other function, or Q1 and Q2, together with the nitrogen atom joining them together are a 5- or 6-membered saturated heterocyclic radical which may contain nitrogen or oxygen as further hetero atom, An° is the equivalent of an anion, and Q4 and Q5 are identical or different and each is independently of the other C1-C13-alkyl, which may be interrupted by from 1 to 4 oxygen atoms in other function, by imino or by C1-C4-alkyl-imino groups and may be substituted by amino, by a 5- or 6-membered saturated or aromatic heterocyclic radical which contains a nitrogen atom and may contain a further hetero atom selected from the group consisting of nitrogen, oxygen and sulfur, or by substituted or unsub-stituted C5-C7-cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubsti-tuted C5-C7-cycloalkyl or unsubstituted or methyl-substituted piperidinyl, and Q4 may also be hydrogen, R2 is hydrogen or C1-C4-alkyl or R1 and R2 together are a radical of the formula CO-L2 or CO-L3-CO, where L2 is C3-C4-alkylene and L3 is C2-C3-alkylene, vinylene or 1,2-phenylene, R3 and R4 are identical or different and each is inde-pendently of the other C1-C13-alkyl, which may be interrupted by from 1 to 4 oxygen atoms in ether function or by from 1 to 4 imino groups which may be substituted by C1-C4-alkyl or .omega.-hydroxy-C1-C8-alkyl, which may be interrupted by from 1 to 3 oxygen atoms in ether function, and may be substituted by hydroxyl, by amino, by a 5- or 6-membered saturated or aromatic heterocyclic radical which contains a nitrogen atom and may contain a further hetero atom selected from the group consisting of nitrogen, oxygen and sulfur, or by substituted or unsubstituted C5-C7-cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted C5-C7-cycloalkyl or unsubstituted or methyl-sub-stituted piperidinyl, and R3 may also be hydrogen, R5 is hydrogen, C1-C4-alkyl, C1-C4-alkoxy, C2-C3-alkan-oylamino, halogen, nitro, cyano, unsubstituted or C1-C4-alkyl-substituted phenylazo or a radical of the formula , , or , where X is oxygen or imino, and L4 is C2-C4-alkylene, and Q1, Q2, Q3, n and An° are each as defined above, and R5 is hydrogen, C1-C4-alkyl, C1-C4-alkoxy, halogen, nitro or cyano, with the proviso that at least one quaternizable or quaternary group is present in the molecule.
2. Dyes as claimed in claim 1, wherein R1 is C2-C4-alkanoyl, benzoyl or a radical of the formula , where Q1, Q2, Q3, An° and n are each as defined in claim 1, or R1 and R2 are together a radical of the formula CO-L3-CO, where L3 is ethylene, vinylene or 1,2-phenylene, and R2 is hydrogen, C1-C4-alkyl or phenyl.
3. Dyes as claimed in claim 1, wherein R3 is hydrogen and R4 is C1-C13-alkyl which is interrupted by 1 or 2 oxygen atoms in ether function, imino or C1-C4-alkylimino groups and/or substituted by amino or by a 5- or 6-membered saturated or aromatic heterocyclic radical which contains one or two nitrogen atoms.
4. Dyes as claimed in claim 1, wherein R3 is C1-C4-alkyl, C1-C4-alkoxy, C2-C4-alkanoylamino or phenylazo and R6 is hydrogen
5. The use of the dyes of claim 1 for dyeing or printing polymeric material.
6. Sulfonamides of the formula IIIa (IIIa), where L3 is C2-C3-alkylene, vinylene or 1,2-phenylene and R3 and R4 are identical or different and each is inde-pendently of the other C1-C13-alkyl, which may be interrupted by from 1 to 4 oxygen atoms in ether function or by from 1 to 4 imino groups which may be substituted by C1-C4-alkyl or .omega.-hydroxy-C1-C8-alkyl, which may be interrupted by from 1 to 3 oxygen atoms in ether function, and may be substituted by hydroxyl, by amino, by a 5- or 6-membered saturated or aromatic heterocyclic radical which contains a nitrogen atom and may contain a further hetero atom selected from the group consisting of nitrogen, oxygen and sulfur, or by substituted or unsubstituted C5-C7-cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted C5-C7-cycloalkyl or unsubstituted or methyl-substituted piperidinyl, and R3 may also be hydrogen, with the proviso that at least one quaternizable group is present in the molecule.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4235154.5 | 1992-10-19 | ||
| DE4235154A DE4235154A1 (en) | 1992-10-19 | 1992-10-19 | Basic dyes based on amides of I-acid (1-hydroxy-6-aminonaphthalene-3-sulfonic acid) and amides of I-acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2106830A1 true CA2106830A1 (en) | 1994-04-20 |
Family
ID=6470775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002106830A Abandoned CA2106830A1 (en) | 1992-10-19 | 1993-09-23 | Basic dyes based on amides of j-acid (1-hydroxy-6- aminonaphthalene-3-sulfonic acid) and amides of j-acid |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0594037B1 (en) |
| JP (1) | JPH06220340A (en) |
| CA (1) | CA2106830A1 (en) |
| DE (2) | DE4235154A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4133514A1 (en) * | 1991-10-10 | 1993-04-15 | Basf Ag | SULPHONAMIDES DERIVED FROM 1-HYDROXY-6-AMINONAPHTHALINE-3-SULPHONIC ACID (I-ACID) |
| DE4403667A1 (en) * | 1994-02-07 | 1995-08-10 | Basf Ag | Basic dyes based on amides of 1-hydroxy-6-aminonaphthalene-3-sulfonic acid and their intermediates |
| GB9921929D0 (en) * | 1999-09-16 | 1999-11-17 | Avecia Ltd | Compound |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE537535C (en) * | 1931-11-05 | Hans Ussmueller Metallwarenfab | Line guide | |
| DE2724079A1 (en) * | 1977-05-27 | 1978-12-07 | Bayer Ag | AZO DYES |
| DE2915323A1 (en) * | 1978-04-26 | 1979-11-08 | Sandoz Ag | BASIC OR CATIONIC MONOAZO OR DISAZO COMPOUNDS CONTAINING SULPHONIC ACID GROUPS |
| DE3114089A1 (en) * | 1981-04-08 | 1982-10-28 | Bayer Ag, 5090 Leverkusen | SULPHONIC ACID-CONTAINING CATIONIC AZO DYES, THEIR PRODUCTION AND THEIR USE |
| GB8421551D0 (en) * | 1984-08-24 | 1984-09-26 | Ici Plc | Water-soluble dye |
| DE3529968A1 (en) * | 1985-08-22 | 1987-02-26 | Basf Ag | METHOD FOR DYING PAPER |
-
1992
- 1992-10-19 DE DE4235154A patent/DE4235154A1/en not_active Withdrawn
-
1993
- 1993-09-23 CA CA002106830A patent/CA2106830A1/en not_active Abandoned
- 1993-10-12 EP EP93116483A patent/EP0594037B1/en not_active Expired - Lifetime
- 1993-10-12 DE DE59307424T patent/DE59307424D1/en not_active Expired - Lifetime
- 1993-10-18 JP JP5259907A patent/JPH06220340A/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| EP0594037B1 (en) | 1997-09-24 |
| DE4235154A1 (en) | 1994-04-21 |
| JPH06220340A (en) | 1994-08-09 |
| EP0594037A1 (en) | 1994-04-27 |
| DE59307424D1 (en) | 1997-10-30 |
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